COMPREHENSIVE

SELF – STUDY MATERIAL

FOR

NEET & AIIMS

CHEMISTRY - XI

Content Page

Module 3 .............................................................................................................................. 2

(1) Periodic Table ....................................................................................................... 3

(2) Chemical Bonding ............................................................................................... 47
(3) Hydrogen and Its Compounds........................................................................... 104
(4) s-Block .............................................................................................................. 138
COMPREHENSIVE
SELF - STUDY MATERIAL
FOR
NEET & AIIMS
CHEMISTRY

CHEMISTRY

Module - 3

n Periodic Table
o Chemical Bonding
p Hydrogen and Its Compounds
q s-Block

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PERIODIC TABLE
CHAPTER
08
If you memorize the periodic table it will speed you up if you're a chem-
ist, but by and large, the reason you have a periodic table is so that
you can store that information outside of your body. That way it frees
up some part of your brain to do something else.

“BILL NYE”

INTRODUCTION

T
he chapter gives an insight to the contribution made by different scientists to ar-
range the known elements in a manner which could be smooth and informative and
the elements properties could justify its position. Thus what we see in the form of
modern periodic table today follow a logical sequence of electronic configuration
capable enough to explain the trend in physical and chemical properties of the ele-
ments.
At present 118 elements are known. of them, the recently discovered elements are
man made. Efforts to synthesise new elements are continuing. With such a large
number of elements it is very difficult to study individually the chemistry of all these
elements and their innumerable compounds individually. To ease out this problem,
scientists searched for a systematic way to organise their knowledge by classifying
the elements.

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CHEMISTRY FOR NEET & AIIMS
Development of periodic table
(I) Prout's hypothesis
He simply assumed that all the elements are made up of hydrogen, so we can say that
Atomic weight of element = n × (Atomic weight of one hydrogen atom)

Atomic weight of H = 1 where n = number of hydrogen atom = 1, 2, 3,....

Drawback or Limitation :
(a) Every element can not be formed by Hydrogen.
(b) The atomic weights of all elements were not found as whole numbers.
Ex. Chlorine (atomic weight 35.5) and Strontium (atomic weight 87.5)
(II) Dobereiner triad rule
J.W. Dorbereiner pointed out that within a group of three elements having similar chemical and physical properties,
the atomic weight of the middle element is the mean of the other two. Some examples of such triads are given below.
He also pointed out the triad - iron, cobalt and nickel in which the atomic weights of the elements are almost the
same.
Some representative triads of Dobereiner
Triad Li Na K Ca Sr Ba S Se Te Cl Br I
Elements
Atomic weight 7 23 39 40 88 137 32 80 128 35.5 80 127
Mean value 23 88.5 80 81.25
Other Ex. (K, Rb, Cs), (P, As, Sb) (H, F, Cl) (Sc, Y, La).
Though it was the first successful attempt to rationalise the problem, it could not be generalised or extended.
Drawback or Limitation : All the known elements could not be arranged as triads.
(III) Newland's octet Law
John Alexander Reina newland in England made the first attempt to correlate the chemical properties of the elements
with their atomic weight. According to him -
(a) If the elements are arranged in order to their increasing atomic weights, every eighth element had similar
properties to first one like the first and eighth note in music. For example

Sa Re Ga Ma Pa Dha Ni Sa
Li Be B C N O F Na
Na Mg Al Si P S Cl K

(b) Inert gases were not discovered till then.

(c) All the elements could not be classified on this basis.
(IV) Lother meyer's curve
(a) He plotted a curve between atomic weight and atomic volume of different elements.
(b) The following observation can be made from the curve –
(i) Most electropositive elements i.e. alkali metals (Li, Na, K, Rb, Cs etc.) occupy the peak positions on the
curve.
(ii) Less electropositive i.e. alkali earth metal (Be, Mg, Ca, Sr, Ba) occupy the descending position on the
curve.
(iii) Metalloids (B, Si, As, Te, At etc.) and transition metals occupy bottom part of the curve.
(iv) Most electronegative i.e. halogens (F, Cl, Br, I) occupy the ascending position on the curve.
Note : Elements having similar properties occupy similar position on the curve.
Conclusion : On the basis of this curve Lother Meyer proposed that the physical properties of the elements are periodic
function of their atomic wt. and this become the base of Mendeleef's periodic table.

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 PERIODIC TABLE

(V) Mendeleev's Periodic Table

(a) Mendeleev's periodic law :
The physical and chemical properties of elements are the periodic function of their atomic weight
(b) Characteristic of Mendeleev's periodic table :
(i) It is based on atomic weight
(ii) 63 elements were known, noble gases were not discovered.
(iii) He was the first scientist to classify the elements in a systematic manner i.e. in horizontal rows and in
vertical columns.
(iv) Horizontal rows are called periods and there were 7 periods in Mendeleev's Periodic table.
(v) Vertical columns are called groups and there were 8 groups in Mendeleev's Periodic table.
(vi) Each group upto VIIth is divided into A & B subgroups.'A' sub groups element are called normal elements
and 'B' sub groups elements are called transition elements.
(vii) The VIIIth group was consists of 9 elements in three rows (Transitional metals group).
(viii) The elements belonging to same group exhibit similar properties.
(c) Merits or advantages of Mendeleev's periodic table :
(i) Study of elements : First time all known elements were classified in groups according to their similar
properties. So study of the properties of elements become easier .
(ii) Prediction of new elements : It gave encouragement to the discovery of new elements as some gaps were left
in it.
Sc (Scandium) Ga (Gallium) Ge (Germanium) Tc (Technetium)
These were the elements for whom position and properties were well defined by Mendeleev even before
their discoveries and he left the blank spaces for them in his table.
Ex. Blank space at atomic weight 72 in silicon group was called Eka silicon (means properties like silicon) and
element discovered later was named Germanium .
Similarly other elements discovered after mendeleef periodic table were.

Eka aluminium – Galium(Ga) Eka Boron – Scandium (Sc)

Eka Silicon – Germanium (Ge) Eka Mangense – Technetium (Tc)

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CHEMISTRY FOR NEET & AIIMS
(iii) Correction of doubtful atomic weights : Correction were done in atomic weight of some elements.

Atomic weight = Valency × Equivalent weight.

Initially, it was found that equivalent weight of Be is 4.5 and it is trivalent (V = 3), so the weight of Be was
13.5 and there is no space in Mendeleev's table for this element. So, after correction, it was found that Be
is actually divalent (V = 2). So, the weight of Be became 2 × 4.5 = 9 and there was a space between Li and
B for this element in Mendeleev's table.
– Corrections were done in atomic weight of elements are – U, Be, In, Au, Pt.
(d) Demerits of Mendeleev's Periodic Table:
(i) Position of hydrogen is uncertain. It has been placed in lA and VII A groups because of its resemblance
with both the groups.
(ii) No separate positions were given to isotopes.
(iii) It is not clear whether the lanthanides and actinides are related to IIA or IIB group.
(iv) Although there is no resemblance except valency of subgroups A and B, they have been put in the same
group.
(v) Order of increasing atomic weights is not strictly followed in the arrangement of elements in the periodic
table. For e.g. – Co (At. wt. 58.9) is placed before I (127) and Ar (39.9) before K (39).

(VI) Modern periodic table (Modified mendeleev’s Periodic Table) :

(i) It was proposed by Moseley.
(ii) Modern periodic table is based on atomic number.
(iii) Moseley did an experiment in which he bombarded high speed electron on different metal surfaces and obtained
X-rays.

He found out that Q v Z where Q= frequency of X-rays, Z = atomic number from this experiment, Moseley
concluded that the physical and chemical properties of the elements are periodic function of their atomic
number. It means that when the elements are arranged in the increasing order of their atomic number elements
having similar properties gets repeated after a regular interval. This is also known as 'Modern Periodic Law'.
(iv) Modern periodic law : The physical & chemical properties of elements are the periodic function of their atomic
number.
(v) Characteristics of modern periodic table :
(a) 9 vertical columns called groups.
(b) Ist to VIII group + 0 group of inert gases.
(c) Inert gases were introduced in periodic table by Ramsay.
(d) 7 horizontal rows called periods.
(VII) Long form / Present form of Modern periodic table :
(It is also called as 'Bohr, Bury & Rang, Werner Periodic Table)
(i) It is based on the Bohr-Bury electronic configuration concept and atomic number.
(ii) This model is proposed by Rang & Werner
(iii) 7 periods and 18 vertical columns (groups)
(iv) According to I. U. P. A. C. 18 vertical columns are named as Ist to 18th group.
(v) The co-relation between the groups in long form of periodic table and in modern form of periodic table are given
below –
IA, IIA, IIIB, IVB,VB, VIB, VIIB, VIII IB, IIB, IIIA, IVA, VA, VIA, VIIA, 0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
(vi) Elements belonging to same group having same number of electrons in the outermost shell so their properties
are similar.

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CHEMISTRY FOR NEET & AIIMS
Description of periods :
Period n Sub shell No. of elements Element Name of Period
1. 1 1s 2 1
H, 2He Shortest
2. 2 2s, 2p 8 3
Li – 10Ne Short
3. 3 3s, 3p 8 11
Na – 18Ar Short
4. 4 4s, 3d, 4p 18 19
K – 36Kr Long
5. 5 5s, 4d, 5p 18 37
Rb – 58Xe Long
6. 6 6s, 4f, 5d, 6p 32 55
Cs – 86Rn Longest
7. 7 7s, 5f, 6d, 26 87
Fr – 112Uub Incomplete

Description of Groups :
1st/IA/Alkali metals 2nd/IIA/Alkali earth metals
H = 1s 1
Be = 1s2, 2s2
Li = 1s2 , 2s1 Mg = 1s2, 2s2, 2p6, 3s2
Na = 1s , 2s 2p , 3s
2 2 6 1
Ca = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2
K = 1s2 , 2s2 2p6 , 3s2 3p6 , 4s1 (n = Number of shell)
General electronic configuration = ns1 General electronic configuration = ns2
Number of valence shell e– = 1 Number of valence shell e– = 2
13th/IIIA/Boron Family 14th/IVA/Carbon Family
B = 1s , 2s , 2p
2 2 1
C = 1s2, 2s2, 2p2
Al = 1s2, 2s 2, 2p6, 3s2, 3p1 Si = 1s2, 2s2, 2p6, 3s2, 3p2
Ga = 1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p
2 2 6 2 6 2 10 1
Ge = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p2
General electronic configuration = ns2 np1 General electronic configuration = ns2 np2
Number of valence shell e– = 3 Number of valence e– = 4
15th/VA/Nitrogen family/Pnicogen `16th/VIA/Oxygen family/Chalcogen
(Used in fertilizer as urea) (Ore forming)
N = 1s2, 2s2, 2p3 O = 1s2, 2s2, 2p4
P = 1s 2, 2s2, 2p6, 3s2, 3p3 S = 1s2, 2s2, 2p6, 3s2, 3p4
As = 1s2, 2s2, 2p6, 3s2, 3p6, 4s 2, 3d10, 4p3 Se = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p4
General electronic configuration = ns np 2 3
General electronic configuration : ns2 np4
Number of valence shell e– = 5 Number of valence shell e– = 6
17th/VIIA/Fluorine family/Halogens 18th/Zero group/Inert gases / Noble gases
(Salt forming) (Less reactive)
F = 1s2, 2s2, 2p5 Ne = 1s2, 2s2, 2p6
Cl = 1s , 2s , 2p , 3s , 3p
2 2 6 2 5
Kr = 1s2, 2s2, 3p6, 3s2, 3p6, 4s2, 3d10, 4p6
Br = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p 5 General electronic configuration = ns2 np6 (except He)
General electronic configuration = ns np 2 5
Number of valence shell e– = 8
Number of valence shell e– = 7
Ex. Which of the following elements belong to alkali metals ?
(1) 1s2, 2s2, 2p2 (2) 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s1
(3) 1s , 2s , 2p
2 2 5
(4) None of these
Sol. (2)

(vii) Important Points :

(a) 2nd period elements (Li, Be, B) Shows diagonal relationship with 3rd period elements (Mg, Al, Si) so (Li, Be, B)
are called Bridge elements. Because of same ionic potential value they shows similarity in properties.

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 PERIODIC TABLE
(Ionic potential = Charge/Radius)

Li Be B

Na Mg Al Si

(b) 3rd period elements (Na, Mg, Al, Si, P, S, Cl) are called typical elements because they represent the properties of
other element of their respective group.
(c) In 6th period all types of elements are included (s, p, d & f)
(d) No inert gas in 7th period.
(e) Normal elements present in all periods.
(f) Atomic number of last inert gas element is 86.
(g) Long form of modern periodic table can be divided into four portions.
(i) Left portion – IA & IIA – s-block.
(ii) Right portion – IIIA to VII A + 0 group – p-block.
(iii) Middle portion – IIIB to VIIB + VIII + IB IIB – d-block.
(iv) Bottom portion – IIIB – f-block elements
(h) The group containing most electro positive elements – GROUP IA.
(i) The group containing most electro negative elements – GROUP VIIA
(j) The group containing maximum number of gaseous elements–GROUP ZERO(18th)
(k) The group in which elements have generally ZERO valency – GROUP ZERO(18th)
(l) In the periodic table
Number of Gaseous elements – 11 (H, N, O, F, Cl + Noble gases)
Number of Liquid elements – 6 (Cs, Fr, Ga, Hg, Br, Uub)
Bromine is the only non-metal which exists in liquid form.
Number of Solid elements – 95 (if discovered elements are 112)
(m) No p-block elements in 1 and 7th periods.
st

(n) Ist period has all the elements in gaseous form (H, He)
(o) 0/18 group have all the elements in gaseous form.
(p) 2nd period contains maximum number of gaseous elements. They are 4 (N, O, F, Ne)
(q) IIIB/3rd group is called longest group having 32 elements including 14 Lanthanides and 14 Actinides
Sc
Y
La................Lanthanides (14)
Ac................Actinides (14)
Ex. Properties of Li is similar to :
(1) Mg (2) Na (3) Both (4) None of these
Sol. (3)

(viii) Nomenclature of elements :

(a) IUPAC gave names to elements above atomic number 100 as follows –
0 1 2 3 4 5 6 7 8 9
nil un bi tri quad pent hex sept oct enn
(b) In all the elements suffix is – ium.

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CHEMISTRY FOR NEET & AIIMS
Atomic No. IUPAC Name Symbol Elemental Name Symbol
101 Unnilunium Unu Mendelevium Md
102 Unnilbium Unb Nobelium No
103 Unniltrium Unt Lawrencium Lr
104 Unnilquadium Unq Rutherfordium Rf
105 Unnilpentium Unp Dubnium Db
106 Unnilhexium Unh Seaborgium Sg
107 Unnilseptium Uns Bohrium Bh
108 Unniloctium Uno Hassnium Hs
109 Unnilennium Une Meitnerium Mt
110 Ununnilium Uun Darmstadtium Ds
111 Unununnium Uuu Rontgenium* Rg*
112 Ununbium Uub Copernicium Cn
113 Ununtrium Uut +
114 Ununquadium Uuq * *
115 Ununpentium Uup +
116 Ununhexium Uuh * *
117 Ununseptium Uus +
118 Ununoctium UuO +

Note : - * Official IUPAC name yet to be recommended

+ Elements yet to be discovered
(ix) Merits of long form of periodic table :
(a) Position of isotopes – Atomic number of isotopes are similar, so different isotopes can be placed at same place
in periodic table.
(b) (Ar – K) (Co – Ni) (Te – I) are now in increasing order of atomic number.
(c) Lanthanides and actinides are in IIIB group.
(d) In modern periodic table diagonal line separates out metals, metalloids and non metals.
(e) Elements of same group have same general formula of electronic configuration of outer most shell.
(x) Demerits of long form of periodic table :
(a) Position of hydrogen is still controversial.
(b) 'He' is a inert gas but it has different electronic configuration than other inert gas elements.
(c) Lanthanides and actinides are still not placed in main frame.
(d) Isotopes have different physical properties but have same place in periodic table.
Ex. Each period in the periodic table starts with a subshell of new shell and ends with –
(1) Small subshell (2) Next higher shell
(3) p-subshell of the same shell (4) Different subshell of the same subshell
Sol. (3)
Ex. An element recently discovered is Uuq. What will the formula of its most stable oxide is :–
(1) MO2 (2) M2O3
(3) MO3 (4) M2O
Sol. (1)
Ex. Maximum work on periodic table related with atomic number was given by –
(1) Moseley (2) Mendeleev
(3) Aston (4) Hund
Sol. (1)

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 PERIODIC TABLE
Classification of elements
Bohr classification : Elements can be divided in four parts on the basis of electronic configuration.
(i) Inert gas elements :
(a) The elements in which Ultimate orbit is completely filled are called inert gas elements.
(b) General electronic configuration is ns2p6 (Except He = 1s2)
(c) Because of most stable configuration, they are very less reactive. Hence known as noble gas or inert g a s
element.
(d) These elements are present in '0' group or 18th group and 1 to 6th period of periodic table.
(e) Number of inert gas elements are 6(One in each period upto 6th) He, Ne, Ar, Kr, Xe, Rn
(ii) Normal or Representative elements :
(a) The elements in which ultimate orbit is incomplete, while penultimate orbits are complete are called normal
elements.
(b) Their general electronic configuration is :
IA IIA IIIA IVA VA VIA VIIA
ns 1 ns 2 ns2 np1 ns2 np2 ns2 np3 ns2 np4 ns2 np5

ns1—2 ns2np1—5

(c) These elements lies in group IA to VIIA and period Ist to 7th
(d) Elements of 2nd period known as bridge elements.
(e) Elements of 3rd period (Na, Mg, Al, Si, P, S and Cl) are called typical elements These are 7 in numbers.
(iii) Transition elements :
The elements in which both ultimate (n) as well as penultimate shells (n – 1) are incomplete either in atomic state or
in some oxidation state are called transition elements.
Note : According to this concept, Zn, Cd, Hg and Uub are not transition elements because they do not have
incomplete penultimate shell either in atomic state or in some oxidation state.
Zn = [Ar] 3d10 4s2 and Zn+2 = [Ar] 3d10
(a) group – IIIB to VIIB + VIII + IB and Periods – 4th to 7th
(b) Electronic configuration (n–1)d1–10 ns1 or 2
(c) Total number of d-block elements = 40
Total number of transition elements = 36 (Except Zn, Cd, Hg and Uub)
Note : All transition elements are d-block elements but all d-block elements are not transition elements.
(iv) Inner transition elements :
(a) The Elements in which all the three shells that is ultimate (n) penultimate (n–1) and pre or antipenultimate
(n–2) shell are incomplete are called inner transition elements.
Ex. 58Ce = [Xe] 6s2, 5d1, 4f1
(b) Electronic configuration (n – 2)f1 – 14 (n – 1) d0 or 1 ns2
(c) These are 28 in number.
(d) Group – IIIB and Period – 6th & 7th
(e) Inner transition elements are divided into two series.
(I) Lanthanide series/Rare earth elements /Lanthenones : (Ce58 – Lu71,14 elements)
The first element of this series is Cerium & not Lanthanum.
In these elements, last electron enters into 4f subshell
They are present in IIIB group and 6th period of the periodic table.
Promethium (61Pm) is the only lanthanide which is synthetic and radioactive in nature.

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CHEMISTRY FOR NEET & AIIMS
(II) Actinide series /Man made elements /Actinones (Th90 – Lw103 14 elements)
The first element of this series is Thorium & not Actinium because last electron enters into 5f subshell.
They are present in IIIB group and 7th period of the periodic table.
All the actinides are radioactive in nature. First three elements (Th, Pa, U) are found in nature while others are
synthetic in nature.After U92 i.e. from 93Np onwards elements are called transuranic elements
They are heavier than uranium and they are derived from uranium by nuclear reactions.

Ex. Classify the following elements based on Bohr's concept :

(1) [Ar] 4s2, 3d8 (2) 1s2, 2s2, 2p6, 3s 2, 3p6
(3) [Xe] 6s2, 5d1, 4f12 (4) [Rn] 7s2, 6d4, 5f14
(5) [Kr] 5s2, 4d10, 5p2
Sol. (1) Transition (2) Inert gas (3) Inner transition
(4) Transition (5) Normal element

Ex. The heaviest naturally occuring element is .............?

Sol. Uranium.
Classification on the Basis of Sub shell in which last e– enters :
(i) s-block elements :
(a) In these elements last electron enters in s - subshell.
(b) Group – IA, IIA + 0 group (He only) and Period – 1 to 7th
(c) Electronic configuration – ns1 – 2
IA group n = 1 to 7 and IIA group n = 2 to 7
(d) Total s - block elements are (14) (including H and He)
(e) Total s - block metals are (12) (excluding H), H is non-metal
(ii) p-block elements :
(a) Last e– enters in p - sub shell
(b) Group – IIIA (13) to VIIA (17) + 0 group (18) (except He) and Period – 2nd to 6th
(c) Electronic configuration – ns2 np1 – 6 and Total p - block elements – (30)
(iii) d-block elements :
(a) Last e– enters in (n – 1)d subshell
(b) Group – IIIB – VIIB, VIII, IB, IIB or group 3 to 12 (IUPAC) and Period – 4th to 7th
(c) Electronic configuration – (n –1)d1 – 10 ns1 or 2

(d) Total d - block elements – (4 0) ½

¾ If 11 2 elements are included in periodic table
Total transition elements – (36 ) ¿

(e) IIB elements (Zn, Cd, Hg, Uub) are d-block elements but not transition elements.
(iv) f-block elements :
(a) Differentiating e– enters in (n – 2) f subshell.
(b) Group – IIIB and Period – 6th and 7th
(c) From atomic number 58 - 71, 6 period ; Lanthanide series 4f1 – 14 5d0 or 1 6s2
th

90 – 103, l 7th period ; Actinide series 5f1 – 14 6d0 or 1 7s2

(d) Total number of f block elements – (28) and All the actinides are radioactive elements.
(e) Transuranic actinides are man made elements. (Np93 – Lw103)
(f) Lanthanides are found rarely on earth so these are called rare earth metals.

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 PERIODIC TABLE
Magic Numbers :
Knowing the atomic number of the first member of a group, we can write the atomic number of the subsequent
elements by adding given magic number
Group 1 2 3 4, 5, 6, 7, 8, 9, 10, 11, 12 13, 14, 15, 16, 17, 18,
IA IIA IIIB IIIA IVA VA VIA VIIA zero

I+ 2 – 8
II + 8 8 8 8
PERIOD

III+ 8 8 18 18
IV+ 18 18 18 18 18 18
V+ 18 18 18 32 32 32
VI+ 32 32 32 32 – –
VII
In group IA – Atomic number of H is 1 and atomic number of other element will be as follows –
H1 1  2 3 Li 3  8 11 Na 11  8 19 K 19  18 37 Rb 37  18 55 Cs
Magic number  
 
  
 
 

2 8 8 18 18
Determination of Period, Block, and Group of an element :
Period number: The period no. of the element can be predicted from the principal quantum no. (n) of the valence shell.
Block number: Last electron enter in which orbital is knows as block no. .
Group number: It is predicted from the number of electrons in the valence shell and penultimate shell .
(A) When atomic number is given :
Step I : 71 t Z t 58 Ÿ Lanthanoids (6th Period)
f-block

103 t Z t 90 Ÿ Actinoids (7th Period)

Group number = IIIB (largest group of periodic table)
Step II : Z = 104 to 118 (Period number = 7)
Group number = last two digits in atomic number of element
Example : Z = 104
Group no. = 4
Step III : Group number = 18 + given atomic number – atomic number of next noble gas
If the value of this formula is negative then use 32 instead of 18 in formula.
(B) When electronic configuration is given
Period number (n) = number of outermost shell/Highest shell number.
Block identification :
• If np electron present then p - block (ns2 np1–6)
group number = 12 + np electrons
• If np electron absent then s/f/d block
If (n–2)f 0 (n–1)d0 ns1–2 = s block
group number = ns electrons
If (n–2)f–14 (n–1)d0–1 ns2 = f block
group number = IIIB
• If any other configuration or (n–1) electron + ns electron
Ex. In the periodic table the elements Z = 30 is expected to be present in –
(1) IA series (2) IB group (3) IIA group (4) IIB group
Sol. (4)
Ex. In 6th period and III group of Mendeleev's periodic table 14 elements are grouped together. These elements are
known as –
(1) Alkali metals (2) Inert gasses (3) Alkaline earth metals (4) Rare earth elements

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CHEMISTRY FOR NEET & AIIMS
Sol. (4)
Ex. Uranium is a member of –
(1) Transition series (2) 3rd-period (3) Actinide series (4) 6th-period
Sol. (3)
Ex. Among the following the synthetic element is –
(1) Ga (2) Ti (3) U (4) Pm
Sol. (4)
PERIODICITY
(i) The regular gradation in properties from top to bottom in a group and from left to right in a period is called periodicity
in properties.
(a) In a period, the ultimate orbit remain same, but the number of e– gradually increases.
(b) In a group, the number of e– in the ultimate orbit remains same, but the values of n increases.
(ii) Causes of periodicity :
(a) The cause of periodicity in properties is due to the same outermost shell electronic configuration coming at
regular intervals.
(b) In the periodic table, elements with similar properties occur at intervals of 2, 8, 8, 18, 18 and 32. These numbers
are called as magic numbers.
Periodic properties
(I) Valency :
It is defined as the combining capacity of the elements. The word valency is derived from an Italian word "Valentia"
which means combining capacity.
Old concept :
Valency with respect to Hydrogen and Chlorine : Valency of H = 1 and Cl = 1.
It is defined as the number of hydrogen or Chlorine atoms attached with a particular element.
IA IIA IIIA IVA VA VIA VIIA
NaH MgH2 AlH3 SiH4 PH3 H2S H–Cl
NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl2 Cl–Cl
Valency 1 2 3 4 3 2 1
Valency with respect to oxygen : Valency of 'O' = 2
It is defined as twice the number of oxygen atoms attached with a particular atom.
IA IIA IIIA IVA VA VIA VIIA
Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl2O7
Valency 1 2 3 4 5 6 7
New concept :
This concept is based on the electronic configuration. According to this concept valency for IA to IVA group elements
is equal to number of valence shell e– and from VA to zero group, it is –
[8– (number of valence e–)].
Valency = No. of valence e– Valency = (8– no. of valence e–)

IA IIA IIIA IVA VA VIA VII 0

ns 1 ns 2 ns 2np 1 ns 2np 2 ns 2np 3 ns 2np 4 ns2np5 ns2np2
Valence shell e– 1 2 3 4 5 6 7 8
Valency 1 2 3 4 3 2 1 0

(II) Boiling points and melting points :

(i) It is a property of aggregate of atoms and not of a single atom.
i.e. why it is a molecular propertry.

13
 PERIODIC TABLE
(ii) Melting point of a solid depend on –
(a) Structure of solid (b) Chemical bond (c) Bond energy
(a) Structure of solid made up of (i) atomic solid (ii) molecular solid (iii) metallic solid.
Order of decreasing melting point is : Atomic solid > Metallic solid > Molecular solid
(b) Chemical bond among particles in solid. Order of bond strength is –
Covalent bond > Metallic bond > Vander waal bond
(c) Bond energy – Covalent solids like diamond, SiO2 etc have only covalent bonds between atoms so their bond
energy is higher than molecular or metallic solids.
(iii) In period : Along the period from left to right boiling point and melting point first increases then decreases.
Alkali metals – Crystal structure BCC (low boiling point & melting point)
Transition metals – ............"..... FCC (High boiling point & melting point)

ª Inert gases ............. Lowest boiling point & melting point (Vander waal force)
« Transition elements .......... Highest melting point
¬

ª W(Tungston) maximum melting point (3 4 1 0 ° C)

Metals « Hg(Mercury) lowest melting p oint (–38 ° C)
¬

ª Carbon (In the form of diamond) Highest melting point (37 27 ° C)

Non metals « Helium Lowest melting point (–2 70 ° C)
¬
(iv) In Group :
(a) In s-block elements boiling point & melting point decreases down the group.
Li, Na (solid) oCs, Fr (liquid)
(b) In d-block elements boiling point & melting point increases down the group (due to lanthanide contraction, zeff
increases and hence bond energy increases)
(c) In p-block elements
(i) From IIIA – IVA group boiling point & melting point decreases down the group and from VA to '0' group, boiling point
& melting point increases down the group. (Atomic or molecular weight vvander waal force)
(ii) boiling point and melting point of monoatomic molecules are lesser than diatomic molecules.
'0' group < Halogens
(iii) Atomic solid non metals like B, C and Si has higher boiling point and melting point due to strong covalent bond.
(iv) Boiling point & melting point of molecular solids are less because of weaker vander waal force among molecules Ex.
I2.
(v) Order of melting point :
Li > Na > K > Cs C > Si > Ge He < Ne < Ar < Rn
Be > Ca > Sr > Ba > Mg C > B > Si Zn > Cd > Hg
F2 < Cl2 < Br2 < I2 B > Al > Ga Cu > Au > Ag
Ex. Which of the following element have highest melting point –
(1) Al (2) Na (3) Cr (4) Zn
Sol. (3)
Ex. Which of the following element have highest melting point –
(1) Fe (2) Fr (3) W (4) Os
Sol. (3)
Ex. Which of the following element have lowest melting point –
(1) Cr (2) Fr (3) Hg (4) Zn
Sol. (3)

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CHEMISTRY FOR NEET & AIIMS
(III) Screening effect (V V) and effective nuclear charge (Zeff) :
(i) Valence shell e– suffer force of attraction due to nucleus. and force of repulsion due to inner shell electrons.
(ii) The decrease in force of attraction on valence e– due to inner shell e– is called screening effect or shielding
effect.(i.e. total repulsive force is called shielding effect.)
(iii) Due to screening effect valence shell e– experiences less force of attraction exerted by nucleus.(i.e. total attraction
force experienced by valence e– is called Zeff.)
(iv) There is a reduction in nuclear charge due to screening effect. Reduced nuclear charge is called effective
nuclear charge.
(v) If nuclear charge = Z, Then effective nuclear charge = Z – V[Where V(Sigma)= Screening constant]
So, Zeff = (Z – V)
Slater's rule to know screening constant (V) :
(a) For single e– species V= 0
(b) Screening effect (S.E.) for two e– species V= 0.30
Ex. In He (1s2)
Screening effect of one 1s e–. where V= 0.30
? Zeff = Z – V= 2 – 0.30 = 1.7
(c) Screening effect of ns and np (Outermost orbit) electron is 0.35
(d) Screening effect of (n – 1) penultimate orbit s, p, d electrons is 0.85
(e) Screening effect of (n – 2) and below all the e– present in s, p, d, f is 1.0
2, 8 , 8 , 1
Ex. Lithium 1s22s1 (Z = 3) Potassium (Z = 19)   

n–2 n–1 n
Z eff = Z–V Z eff = Z–V
Zeff on 2s1 electron = 3 – (2 × 0.85) Z eff = 19 – ( 10 × 1 + 8 × .85)
= 3 – 1.70 = 19 – 16.8
= 1.30 = 2.2

(Effective Nuclear charge of elements of second period)

Element Electronic Z Vof ns & np V(n–1) Total Effective
Configaration electron orbital Screeing nuclear
Constant charge
(a) (b) (a + b) Z*=Z – V
3
Li 1s2 2s1 3 – 0.85× 2=1.70 1.70 1.30
4
Be 1s2, 2s2 4 1× 0.35=0.35 0.85× 2=1.70 2.05 1.95
5
B 1s2,2s2,2p1 5 2× 0.35=0.70 0.85× 2=1.70 2.40 2.60
6
C 1s2,2s2,2p1 6 3× 0.35=1.05 0.85× 2=1.70 2.75 3.25
7
N 1s2,2s2,2p3 7 4× 0.35=1.40 0.85× 2=1.70 3.10 3.90
8
O 1s2,2s2,2p4 8 5× 0.35=1.75 0.85× 2=1.70 3.45 4.55
9
F 1s2,2s2,2p5 9 6× 0.35=2.10 0.85× 2=1.70 3.80 5.20
Zeff for different ions of an element :
positive charge (i) Zeff for different ions of an element
negative charge (ii) Zeff for isoelectronic species.

(i) Zeff for different ions of an element

Ex. N+ > N > N– = Zeff
(ii) Zeff of isoelectronic species
Ex. H– < Li+ < Be+2 < Be+3 (2e– species)
N–3 < O–2 < F– < Na+ < Mg+2 (10 electron species)

15
 PERIODIC TABLE
Ex. What will be the screening constant for Rb atom –
(1) 17.15 (2) 25.15 (3) 34.8 (4) 52.8
Sol. (3)
Ex. Screening effect is not observed in :-
(1) He+ (2) Li+2 (3) H (4) All cases
Sol. (4)
(IV) Atomic Radius
The average distance of valence shell e– from nucleus is called atomic radius. It is very difficult to measure the atomic
radius because –
(i) The isolation of single atom is very difficult.
(ii) There is no well defined boundary for the atom. (The probability of finding the e– is 0 only at infinity).
So, the more accurate definition of atomic radius is –
Half the inter-nuclear distance(d) between two atoms in a homoatomic molecule is known as atomic radius.
This inter-nuclear distance is also known as bond length.Inter-nuclear distance depends upon the type of bond by
which two atoms combine.
Based on the chemical bonds, atomic radius is divided into four categories –
(A) Covalent radius (B) Ionic radius (C) Metallic radius (D) Vander waal radius
(A) COVALENT RADIUS (SBCR –Single Bonded Covalent Radius)
(a) Covalent bonds are formed by overlapping of atomic orbitals.
(b) Internuclear distance is minimum in this case.
(c) Covalent radius is the half of the internuclear distance between two singly bonded homo atoms.
If internuclear distance of A–A(A2) molecule is (dA – A) and covalent radius is rA then
dA–A = rA + rA or 2rA
d AA
rA
2

1.98
Ex. In Cl2 molecule, internuclear distance is 1.98A0 so rcl = 0.99 Å
2
(d) SBCR of O, N and C etc. elements can be determined by taking H2O2, N2H4, C2H6 respectively.
Case- I Heteroatomic molecule with less electronegativity difference.
For A – B molecule electronegativities of A & B are approximately equal Ex. C – I
Electronegativity of C & I are approx equal (2.5) internuclear distance of C – I is 2.13Å
dC–I = rC + rI, ( rC is 0.77 Å)
? rI = 2.13 – 0.77 = 1.36Å
Case-II Heteroatomic molecule with more electronegativity difference :
Schoemaker and Stevenson law :
If in a diatomic molecule electronegativities of A – B have more difference. Then actual bond length will be reduced.
As per schoemaker & Stevenson– The reduction in bond length depends on the difference in electronegativities of
atoms by following manner -
dA – B = rA + rB – 0.09 (XA – XB)
Here XA is E.N. of A & XB is E.N. of B
Ex. If bond length of F2 = 1.44 Å, Bond length of H2 = 0.74Å. Find out the bond length of H – F ?
(EN of F is 4.0, EN of H is 2.1)
Sol. dH –F = rF + rH – 0.09 (XF – XH)
'
dF–F = 1.44 / 2 = 0.72 Å, dH – H = 0.72/2 = 0.37 Å
? dH–F = 0.72 + 0.37 – 0.09 ( 4.0 – 2.1)
= 1.09 – (0.09 × 1.9) = 1.09 – 0.171 = 0.919Å

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CHEMISTRY FOR NEET & AIIMS
(B) IONIC RADIUS
(i) Cationic radius :
(a) When an neutral atom loses e– it converts into cation (+ve charged ion)
(b) Cationic radius is always smaller than atomic radius because after loosing e– number of e– reduces, but number
of protons remains same, due to its Zeff increases, hence electrons pulls towards nucleus and atomic radius
decreases, moreover after loosing all the electrons from the outer most shell, penultimate shell becomes ulti-
mate shell which is nearer to nucleus so size decreases.
1
(c) Size of cation v 
Magnitude of the charg e or Zeff
Ex. (i) Fe > Fe+2 > Fe+3 (ii) Pb+2 > Pb+4 (iii) Mn > Mn+2 > Mn+3 > Mn+4 > Mn+5 > Mn+6 > Mn+7
(ii) Anionic radius :
(a) When neutral atom gains e– it converts into anion
(b) Anionic radius is always greater than atomic radius because In an anion e– are more than protons so effective
nuclear charge reduces, and inter electronic repulsion increases, which also increases screening effect. So
distance between e– and nucleus increases and size of anion also increases.
Ex. Flourine (Z=9)
F F–
Proton 9 9
e– 9 10
Z 9 9
so = =1 = 0.9 As Zeff of F– is less than F so size of F– > F
e 9 10
(iii) Size of isoelectronic species :
Those species having same number of e– but different nuclear charge forms isoelectronic series.
For isoelectronic species the atomic radius increases with decrease in nuclear charge
Species K+ Ca+2 Ar S–2 Cl–
Z 19 20 18 16 17
e 18 18 18 18 18
z 19 20 18 16 17
e 18 18 18 18 18
Order of radius : (S > Cl > Ar > K > Ca ), (N > O > F > Ne > Na > Mg > Al )
–2 – + +2 3– 2– – + +2 +3

(C) Metallic radius

(a) Half of the nuclear distance between two adjacent metallic atoms in crystalline lattice structure.
(b) there is no overlapping of atomic orbitals so, Metallic radius > Covalent radius
1
(c) Metallic radius v
Metallic bond strength
(d) More metallic radius o loose crystal packing o less bond strength
(body centred packing)
(e) Less metallic radius o Tight crystal packing FCC oHigh bond strength
(Hexagonal close packing)
(D) Vander waal’s radius
(a) Those atoms (like noble gases) which are not bonded with each other, experiences a weak attractive force to come
nearer.
(b) Half of the distance between the nuclei of adjacently placed atoms in solid state of a noble gas is Vander Waal's
radius.
(c) Vander Waal radius > Covalent radius.

17
 PERIODIC TABLE
(d) Inert gas have only Vander Waal radius.
(e) In molecules of nonmetals solid both covalent and Vander Waal radius exists.

Cl2

Cl2 Cl2 molecules

Covalent radius = 0.99 Å
Vander Wall radius = 1.80 Å

Covalent radius
Vander Waal distance

Vande r Waal radius = 2 × co valent radius

(f) Vander Waal radius > Metallic radius > Covalent radius
(g) Vander Waal force of attraction v  Molecular weight or atomic weight (in inert gases)
(h) In a period from left to right Vander Waal radius decreases.
(i) In a group of non metal from top to bottom its values increases.
Factors affecting atomic size are :
1
(a) Atomic radius v (b) Atomic radius vnumber of shells
Effective nuclear charge (Zeff)
Li > Be > B > C > N > O > F Li < Na < K< R < Cs
(c)Atomic radius v Screening effect (d) Atomic size vMagnitude of –ve charge
O < O– < O–2
1 1
(e) Atomic radius v (f) Atomic radius v
Magnitude of + ve charge Bond order
Mn > Mn > Mn > Mn
+2 +3 +4
N — N > —N N— >N N
Periodic variation of atomic size :
(i) Across a period : It decreases from left to right in a period as nuclear charge increases
Ex. Li > Be > B > C > N > O > F < Ne
(ii) In a group : It increases from top to bottom in a group as number of shell increases
Ex. Li < Na < K < Rb < Cs
Exceptions : Transition elements

Sc Ti V Cr Mn Fe Co Ni Cu Zn

 

 

Zeff ! Screening effect Zeff | Screening effect Zeff  Screening effect
Order of atomic radius –
Sc > Ti > V >Cr Mn > Fe |Co |Ni < Cu < Zn
Lanthanoide Contraction :
(a) Outermost electronic configuration of inner transition elements is
(n –2) f1 – 14, (n–1)s2p6d0–1, ns2 (n = 6 or 7)
(b) e– enters in (n – 2) f orbitals
(c) Mutual screening effect of e– is very less, because of complicated structure of f-orbital

18
CHEMISTRY FOR NEET & AIIMS
(d) Nuclear charge increases by one (+1) in lanthanoides and actinides so atomic size of these elements slightly
decreases. It is known as lanthanoide contraction.
Here Nuclear charge > Screening effect.
(e) In Ist, 2nd and 3rd transition series, Radii– 3d < 4d |5d (except IIIrd B)
IIIB IVB
size Sc Ti p size increases
increases Y Zr
} Equal due to lanthanide contraction
La Hf
Transition contraction :
IIIA oB<Al |Ga Note : While atomic size should increases down the group.
(a) At. size of Ga = At. size of Al, due to transition contraction.
(b) In transition elements nuclear charge increases by 1.
(c) but e– enters in (n –1)d orbital exerts screening effect.
(d) Screening effect of (n –1)d e– balance the nuclear charge by 85%
(e) Zeff on increasing each electron = 1 – 0.85 = 0.15
(f) Increase in nuclear charge is only 0.15 so atomic size remains almost constant.

Ex. Which of the following atom has largest size –

(1) Ba (2) Cs (3) Kr (4) Sr
Sol. (2)

Ex. Which of the following have highest vander wall's radius –

(1) F2 (2) Cl2 (3) Br2 (4) I2
Sol. (4)

Ex. What will be the distance between H and Cl atom in HCl ? If radius of hydrogen is 1A and the radius of chlorine is
0.5Å consider 'E.N. = 0.0
(1) 1.82Å (2) 1.32Å (3) 1.50Å (4) None of these
Sol. (3)
Ex. Vander waal radius is :-
(1) Twice of bond length
(2) Half of bond length
(3) Almost equal to bond length
(4) Distance between nucleus of non bonded atoms
Sol. (3)

Ex. A given compound Br2, whose inter nuclear distance is 3.2Å. What will be the radius of Br atom –
(1) 1.6Å (2) 6.4Å (3) 2.4Å (4) 4.9Å
Sol. (1)

Ex. Which of the following atom has smallest size –

(1) He (2) F (3) H (4) Li
Sol. (3)
Ionisation Potential or Ionization Energy or Ionization Enthalpy(IP/IE)
(i) Minimum energy required to remove most loosly bonded outer most shell e– in ground state from an isolated
gaseous atom is known as ionisation potential.
(Isolated o Without any bonding with other atom)

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 PERIODIC TABLE
(ii) Successive Ionisation Energy :
(a) For an atom M, successive ionisation energies are as follows -
st
M + E1 o M+ + e– E1 = I Ionisation Potential
M + + E2 o M+2 + e– E2 = IInd Ionisation Potential
M+2 + E3 o M+3 + e– E3 = IIIrd onisation Potential
Ist Ionisation Potential < IInd Ionisation Potential < IIIrd onisation Potential
(b) Electron can not be removed from solid state of an atom, it has to convert in gaseous form, Energy required for
conversion from solid state to gaseous state is called Sublimation energy.
(c) Ionisation Potential is always an endothermic process ('H = +ve)
(d) It is measured in eV/atom (electron volt/atom) or Kcal/mole or KJ/mole
Factors affecting ionisation potential :
(A) Atomic size : Larger the atomic size, smaller is the Ionisation Potential It is due to that the size of atom increases the
outermost electrons farther away from the nucleus and nucleus loses the attraction on that electrons and hence can be
easily removed.
1
Ionisation Potential v
Atomic size
(B) Effective nuclear charge ( Zeff) : Ionisation potential increases with the increase in nuclear charge between outermost
electrons and nucleus.
Ionisation Potential v Effective nuclear charge
(C) Screening effect : Higher is the screening effect on the outer most electrons causes less attraction from the nucleus and
can be easily removed, which is leading to the lower value of Ionisation Potential
1
Ionisation Potential v
Screening effect
(D) Penetration power of sub shells :
(a) Order of attraction of subshells towards nucleus (Penetration power) is -
s > p > d > f
(b) As subshell is more closer to nucleus so more energy will be required to remove e– from s-subshell in comparison
to p,d & f.
Ex. Be B
1s , 2s
2 2
1s2, 2s2 2p1
Ionisation Potential Be > B
After loosing one e–, B attains electronic configuration of Be, so IInd ionisation potential of B is more than Be.
IInd Ionisation Potential of B > Be
(E) Stability of half filled and fully filled orbitals :
(a) Half filled p3,d5, f7 or fully filled s2, p6, d10, f14 are more stable than others so it requires more energy.
Ex. N O
st
1s2, 2s2 2p3 1s2, 2s2 2p4 I Ionisation Potential order is O<N
Because of half filled p-orbitals in N, its ionisation energy (stability) is higher than O.
Ist ionisation potential order Na < Al < Mg
(b) Because s-orbital in Mg is completely filled and its penetration power is also higher than p-orbital (Al).
IInd ionisation potential order Mg+ < Al+ < Na+
(2,8,1) (2,8,2) (2,8)

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CHEMISTRY FOR NEET & AIIMS
(F) Oxidation state :

Ionisation Potential v oxidation state of an atom

Ion with high oxidation state will have high ionisation potential. Ex. Fe+3 > Fe+2 > Fe

COMPARISON OF IONIZATION ENERGY :

(i) In a group : Size increase so ionisation potential decrease.
Li Na K Rb Cs
o
Size increases, Ionisation Potential decreases
Exception :
• Ionisation Potential Ga > Al (While Ionisation Potential decreases down the group it is due to
Transition contraction)

Ionisation Potential Hf > Zr (While Ionisation Potential should decreases down

• 4d
5d the group. It is due to lanthanide contraction)
(ii) In a period : In a period atomic size decreases and zeff increases so removal of electron becomes difficult and
ionisation potential increases.
Li Be B C N O F Ne
o
atomic size decreases, zeff increases, Ionisation Potential increases.
Order of ionisation potential Li < B < Be < C < O < N < Fe < Ne

Ex. The sudden largest jump between the values of 2nd and 3rd ionisation potential of an atom would be associated
with the electronic configuration :-
(1) 1s2 2s2 2p6 3s2 3p2 (2) 1s2 2s2 2p6 3s2 3p6 3d5 4s2
(3) 1s 2s
2 1
(4) 1s2 2s2 2p6 3s2
Sol. (4)

Ex. What is the correct order of ionisation potential :

(1) 5d > 4d (2) 3d < 4d (3) 4d ~ 5d (4) All
Sol. (1)

Ex. I.E. of one of H atom is 2.18 × 10–18 J. The I.E. of H atom in kJ mole–1 is–
(1) 1505 kJ mole–1 (2) 1310 kJ mole–1
(3) 1608 kJ mole–1 (4) None
Sol. (2)

Ex. The correct order of decreasing second ionization energy of–

Li, Be, Ne, C, B
(1) Ne>B>Li>C>Be (2) Li>Ne>C>B>Be
(3) Ne>C>B>Be>Li (4) Li>Ne>B>C>Be
Sol. (4)

Ex. In which of the following element has highest value of ionisation potential–
(1) Ti (2) Zr
(3) Hf (4) None of these
Sol. (3)

21
 PERIODIC TABLE
Application of ionisation potential :
(A) Metallic and non metallic character :
Metallic o Ionisation Potential Low (Na, K, Rb etc.)
non metallic o Ionisation Potential High (F, Cl, Br etc.)

1
Ionisation Potential v
Metallic property

(B) Reactivity :

1
Re activity v
Ionisation Potential
Reactivity increases down the group as ionisation potential decreases.
(C) Reducing character :

1
Re ducing character v
Ionisation Potential
(a) IA group has minimum ionisation potential so they are strong reducing agents in gaseous state
( Li < Na < K < Rb < Cs)
(b) IA group – In Aqueous state
reducing character Li > K ~ Rb > Cs > Na
As the degree of hydration is more in Li due to high charge density.
(D) Stability of oxidation states :
(a) If the difference between two successive ionisation potential > 16eV then lower oxidation state is stable.
Ex. Na o Na+ Ist ionisation potential
42.7 eV
Na o
+
Na +2
IInd ionisation potential}
Difference of ionisation potential > 16 eV So Na+ is more stable.
(b) If the difference between two successive ionisation potential < 11 higher oxidation state is stable.
Ex. Mg o Mg+ Ist ionisation potential
7.4 eV
Mg+ o Mg+2 IInd ionisation potential}
Difference ofionisation potential < 11 eV So Mg+2 is more stable.
Al o Al+
} 12.8 eV So Al is more stable
+
Al+ o Al+2
6.0 eV So Al+3 is more stable
Al+2 o Al+3 }
Al+ is stable only in gaseous state
{ Al+3 is stable in liquid and solid state.
(E) Basic nature : It is property of elements with loosely held electrones

1
Ionisation Potential v
Basic Property

M2O > MO , Na2O > MgO , NaOH > Mg(OH)2 Cs2O > Rb2O > K2O > Na2O > Li2O
(F) To determine the number of valence electron :
Ex. Li Ist Ionisation Potential IInd Ionisation Potential
5.4 e V 75 eV
High energy difference in two successive ionisation potential shows change in energy levels ie. valence shell has
only one electron.

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CHEMISTRY FOR NEET & AIIMS
(G) Ionic nature : Ionic nature of elements decreases from left to right in a period.
1
Ionisation Potential v
Ionic nature of compound
(H) Nature of hydroxide :
In a hydroxide AOH – Nature of hydroxide depends on ionisation potential of A.
A–O–H . If ionisation potential of A is lower than oxygen, it will loose electron and will be basic
A–OH o A+ + OH–
If A has high ionisation potential than oxygen –
A – O – H o AO– + H+
then the hydroxide will be acidic in nature.
NaOH Mg(OH)2 Al(OH)3 Si(OH)4 P(OH)3 SO2(OH)2 ClOH
o
Ionisation Potential increases Acidic nature increases Basic nature decreases
Note : Ionisation potential decreases in a group so, basic nature increases.
Ex. Which of the following element is weak oxidant –
(1) Na+ (2) Mg+2 (3) Al+3 (4) None of these
Sol. (1)
Ex. Which of the following element have highest oxidising strength –
(1) F (2) Cl (3) Br (4) I
Sol. (1)
Ex. Which of the following element has lowest reducing strength –
(1) Na (2) S (3) Al (4) Si
Sol. (2)
Ex. Which of the following element has highest reducing strength –
(1) F– (2) Cl– (3) Br– (4) I–
Sol. (4)
Ex. Identify the least stable ion amongst the following
(1) Li– (2) Be– (3) C– (4) O–
Sol. (2)
Ex. Which ionisation potential (IP) in the following equation involves the greatest amount of energy–
+ – + +2 –
(1) He o He + e (2) K o K + e
+ +2 – + +2 –
(3) Li o Li + e (4) Ca o Ca + e
Sol. (3)
Electron Affinity/Electron gain enthalpy(EA/'eg H)
(i) The amount of energy released or absorbed when electron is added to the valence shell of an isolated gaseous atom
known as Electron affinity.
X + e– o X– + Electron Affinity
(ii) Mostly energy is released in the process of first Electron affinity.
X + e– o X– + Ist Electron Affinity
(iii) If Ist Electron affinity is exothermic
'eg H (electron gain enthalpy) = – ve Ist Electron affinity is mostly positive
(iv) Electron affinity of neutral atom is equal to ionisation potential of its anion.
{Energy evolved in Electron affinity to convert neutral atom to anion} = {Energy absorbed to remove e– from anion}

23
 PERIODIC TABLE

Electron Affinity

Ex. X  e – m o X –  Energy

Ionisation Potential

(v) On adding 2nd electron in anion X–

X– + e–o X–2 – IInd Electron Affinity
or X– + e– + IInd Electron Affinity o X–2 'eg H (2nd electron gain enthalpy) = + ve
(vi) II Electron affinity is endothermic process, i.e. energy has to given to introduce 2nd electron in an anion, because
nd

of repulsion between negative charge on anion (X–) and 2nd electron.IInd Electron Affinity is always negative.
Ex. O(gas) + e–o O– (gas) + 168 K.cal (exothermic)
O– + e– o O–2 – 912.7 K.cal
Net reaction O(g) + 2e– o O–2(g) Electron Affinity = – 744.7 K.cal ( endothermic)
Factors affecting electron affinity :

1
(A) Atomic size Electron Affinity v
Atomic size

1
(B) Screening effect Electron Affinity v
Screening effect

(C) Effective nuclear charge (Zeff) Electron Affinity v Zeff

Stability of completely filled or half filled orbitals :

Electron affinity of filled or half filled orbital is very less or zero.
Ex. (i) Elements (He, Ne, Ar , ....), Electron Affinity = Zero
(ii) Elements (Be, Mg, Ca, ....), Electron Affinity = Approximately Zero
(iii) Elements (N, P, As, .... ), Electron Affinity = Very less
Variation of electron affinity :
In period :
(a) Electron affinity increases along the period due to increase in zeff and decrease in atomic size.
(b) Halogens possess maximum electron affinity due to small size and maximum zeff and after gaining one electron.
They attain a stable inert gas configuration.

Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
|zero Less zero
In 2 period – Ne < Be < N < B < C < O < F
nd

In 3rd period – Ar < Mg < P < Al < Si < S < Cl

In Group :
(a) Electron affinity decreases down the group. As the size increase and attraction on additional electron is less.
(b) Electron affinity of 3rd period element is greater than electron affinity of 2nd period elements of the respective group.
F Cl
1s2, 2s22p5 [Ne] 3s23p5
Due to small size of fluorine, electron density around the nucleus increases. The incoming electron suffers more
repulsion. In case of chlorine electron density decreases due to large size, decreasing order of electron affinity

Cl > F > Br > I S> O>P > N

S > O > Se Si > C > P > N

Note : N & P have low electron affinity due to stable half filled configuration.

24
CHEMISTRY FOR NEET & AIIMS
Application of Electron affinity :
(a) Electron affinity v Oxidising nature
But F has more oxidising power than Cl because F.
(i) has high standard reduction potential.
(ii) Has high hydration enthalpy.
(iii) Low bond dissociation energy.
Difference between electronegavity and Electron Affinity :
Electronegativity Electron Affinity
1. Tendency of an atom in a molecule 1. Energy released when an electron is added to
to attract the bonded electrons neutral isolated gaseous atom
2. It regularly changed in a period 2. It does not changes regularly
3. It has no unit 3. It is measured in eV/atom or KJ mol–1 or K cal mole–1
Electronegativity (EN)
(i) The tendency of an atom to attract shared electrons towards itself is called electronegativity.
(ii) Electronegativity and Electron affinity both have tendency to attract electrons but electron affinity is for isolated
atoms. Where as electronegativity is for bonded atoms.
(iii) A polar covalent or ionic bond of A – B may be broken as
(a) A – B o A– : + B+ (Electronegativity A > Electronegativity B)
or (b) A – B o A+ + :B– (Electronegativity A < Electronegativity B)
depending on their tendency to attract bonded electron.
(iv) There is no unit of electronegativity as electronegativity is tendency of a bonded atom not an energy
(v) Pauling explained it first time.
(vi) Electronegativity of some other elements are as follows –

H In Pauling's scale, elements having

2.1 almost same electronegativity are-
Li Be B C N O F C = S = I = 2.5
1.0 1.5 2.0 2.5 3.0 3.5 4.0
N = Cl = 3.0
Na Mg Al Si P S Cl
P = H = 2.1
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Cs= Fr = 0.7
Br
0.8 2.8 Be= Al = 1.5
Rb I
0.8 2.5
Cs
0.7
Fr
0.7

Note : Small atoms are normally having more electronegativity than larger atoms.
Factors Affecting electronegativity :
(A) Atomic size
1
Electronegativity v
Atomic size
(B) Effective nuclear charge (Zeff)
Electronegativity v Z eff
(C) Hybridisation state of an atom
Electronegativity v % s character in hybridised atom
sp > sp2 > sp3
s character 50% 33% 25%
Electronegativity 3.25 2.75 2.5

25
 PERIODIC TABLE
(D) Oxidation state
Electronegativity v oxidation state
Mn+2 < Mn +4 < Mn+7
O–2 < O–1 < O < O+1 < O+2
Fe < Fe+2 < Fe+3

• s-orbital is nearer to nucleus so by increasing s-character in hybridisation state, Electronegativity also increases.
• Electronegativity does not depends on filled or half filled orbitals, because it is a tendency to attract bonded
electron, not to gain electron from out side.
Periodic table & Electronegativity :
(a) Electronegativity decreases down the group.
(b) In period on moving from left to right electronegativity increases.
Exceptions : In 'Zero' group – Electronegativity is always zero, because inert gas do not form molecule.
(c) Electronegativity of Cs and Fr are equal, it is because from 55Cs to 87Fr only one shell increases but nuclear charge
(No. of proton) increases by +32.
(d) So effect of nuclear charge balanced the effect of increase in number of shell.
Electronegativity of F > Cl but Electron affinity of Cl > F
So Fluorine is called Black sheep element.
(e) In group of IIB elements (Zn, Cd, Hg) value of electronegativity increases down the group, because of lanthanide
contraction
(f) In IIIA group, value of electronegativity increases down the group, because of transition contraction
Electronegativity of Ga > Electronegativity of Al
Application of electronegativity :
(A) Metallic and non metallic nature :
Low electronegativity o Metals
High electronegativity o Non metals
Metallic character increases down the group but decreases along a period.
(B) Bond length :

1
'EN v Here 'EN = difference in electronegativities of bonded atoms
Bond length
Ex. HF < HCl < HBr < HI
Note : HF has minimum bond length because of much difference in the electronegativities of H and F.
(C) Bond energy : By increasing difference in electronegativity of bonded atoms, bond length decreases and hence
bond energy increases
Bond energy v Electronegativity difference
HF > HCl > HBr > HI
(D) Acidic strength of hydrides :

Bond energy (Strength) v stability of molecule

Order of stability of hydrohalides and order of acidic strength
HF > HCl > HBr > HI HF < HCl < HBr < HI
In VA group –
NH3 PH3 AsH3
o
Thermal stability decreases Acidic character increases

26
CHEMISTRY FOR NEET & AIIMS
(E) Reactivity :
1
Bond energy v Stability v
Reactivity
Bond energy v Difference in electronegativities
1
Difference in electronegativities v Stability v
Reactivity

HF HCl HBr HI

o
' EN decreases, stability decreases, Reactivity increases
Note : HI is most reactive hydrohalides or strongest acid among all hydrohalides.
(F) Nature of bonds :
(a) According to Hanny & Smith formula
Ionic % = 16 (XA – XB) + 3.5 (XA – XB)2
Here XA = Electronegativity of A
XB = Electronegativity of B
If XA – XB > 2.1 Ionic % > 50% i.e. Ionic bond
If XA – XB < 2.1 Ionic % < 50% i.e. covalent bond
(b) According to Gallis
XA – XB > 1.7 Ionic
XA – XB < 1.7 Covalent
If XA = XB ; then A – B will be non polar. Ex. H—H, F—F
If XA > XB and difference of electronegativities is small then
AG —— BG bond will be polar covalent
Ex. H2O ( HG —— OG —— HG)
If XA >> XB and XA – XB difference of electronegativities is high then
A– ––— B+ bond will be polar or ionic
Ex. Na+Cl–
In HF, XA – XB = 1.9, which is more than 1.7, even then it is covalent compound.
(G) Nature of hydroxides :
(a) As per Gallis, In AOH if electronegativity of A is more than 1.7 (Non metal) then it is acidic in nature.
(b) If electronegativity of 'A' is less than 1.7 (metal) then AOH will be basic in nature
Ex. NaOH ClOH
XA 0.9 3.0
Nature Basic Acidic
(c) If XA – X0 > X0 – XH then AO bond will be more polar and will break up as
A —— OH o A+ + OH– It shows basic nature
(d) If XA – XO < XO – XH
A — O ——H o H+ + AO– It shows Acidic nature
Ex. In NaOH
XO – XNa (2.6) > XO – XH (1.4) So hydroxide is basic
In ClOH
XO – XCl (0.5) < XO – XH (1.4) So hydroxide is acidic
(H) Nature of oxides : Consider an oxide AO
If XA – XO > 2.3 Basic oxide
If XA – XO = 2.3 Amphoteric oxide
If XA – XO < 2.3 Acidic oxide

27
 PERIODIC TABLE
(a) Along a period acidic nature increases.
(b) Down the group basic nature increases
Li Be B C N O F
Na Mg Al Si P S Cl
mo
XA – XO > 2.3 XA – XO = 2.3 XA – XO < 2.3
Basic Amphoteric Acidic
ie. when in periodic table the distance between the element and oxygen increases, basic character increases.
NO2 > ZnO > K2O
o
acidic character decreases

KEY POINTS

Note: BeO, Al2O3, ZnO, SnO, PbO, SnO2, PbO2, Sb2O3 etc. are amphoteric oxides.
CO, H2O, NO, N2O etc. are neutral oxides.
Acidic strength of oxide and oxyacid v Electronegativity
B2O3 CO2 N2O5
o
EN increase, acidic nature increasse.
SO 3 ! SeO 3 ! TeO 3 HNO 3 ! H 2 CO 3 ! H 3 BO 3 HClO 4 > HBrO 4 > HIO 4
H 2 SO 4 ! H 2 SeO 4 ! H 2 TeO 4 H 3 PO 4 > H 3 AsO 4 > H 3 SbO 4 N 2 O 5 > P2 O 5 > As 2 O 5
H 2 SO 3 ! H 2 SeO 3 ! H 2 TeO 3 HOF > HOCl > HOBr > HOI N 2 O 3 > P2 O 3 > As2 O 3 > Sb 2 O 3

Acidic nature oxidation state

Acidic properties increases with increasing oxidation state of an element
HClO4 > HClO3 > HClO2 > HClO HNO3 > HNO2
H2SO4 > H2SO3 N2O5 > N2O3
SO3 > SO2 Sb2O5 > Sb2O3

(I) Hydrolysis of AX :
Where A = Other element and X = Halogen
(a) If electronegativity of X > Electronegativity of A then on hydrolysis product will be HX.
Ex. (BCl3), Electronegativity of Cl > Electronegativity of B
 
ClGG
G
H OH

B Cl + H OH o 3HCl + B(OH)3
ClG H OH
PCl3 + 3HOH o 3HCl + H3PO3
PCl3. Cl2 + H2O o 2HCl + POCl3
POCl3 + 3HOH o 3HCl + H3PO4
(b) If electronegativity of X < electronegativity of A then on hydrolysis product will be HOX (hypohalous
acid)
G
Cl
G
Ex. Cl2O G
O
Here electronegativity of O > Cl
Cl
So On hydrolysis –

ClG
– +
HO H
G
O G
+ o 2HOCl + H2O
Cl HO– H+

28
CHEMISTRY FOR NEET & AIIMS
(J) Nomenclature of inorganic compounds :
Prefix —— less electronegative element
Suffix —— More electronegative element
Ex. Cl2O(Right) OCl2(Wrong)
In Dichloroxide the electronegativity of Cl is less than 'O' i.e. why Cl is in prefix position.
OF2 Oxygen difluoride
ICl Iodine chloride
NH3 Exception (Here H is less electronegative but it is suffix)
Electronegativity Scale :
(i) Pauling Scale (Bond energy scale) :

0.208 'AB XA  XB Here 'AB is resonance energy of AB molecule

This equation gives difference in electronegativity values.
(ii) Mulliken scale : According to Mulliken electronegativity is average value of ionisation potential and electron
affinity of an element,

Ionisation Potential  Electron Affinity

Xm
2
Relation between Pauling scale & Mulliken scale
Xp = 0.336 (Xm – 0.615)
Xp = Electronegativity given by pauling Xm = Electronegativity given by mulliken
If ionisation potential and electron affinity are given in eV, then electronegativity by Mulliken on Pauling scale will
be

Ionisation Potential  Electron Affinity

Xm
5 .6
If ionisation potential and electron affinity are given in K.cal/mole then

Ionisation Potential  Electron Affinity

Xm
2 u 62.5
(iii) Allred Roschov's scale : As per Roschov, electronegativity is the force by which nucleus of an atom attracts
electron which are on the covalent radius.

Zeff u e 2
(X AR ) Electronegativity = or XP = 0.359X AR + 0.744
r2

Ex. Which of the following acid is strongest :-

(1) HF (2) HCl (3) HBr (4) HI
Sol. (4)
Ex. Which of the following order is correct for acidic property :-
(1) SiH4 > PH3 > H2S (2) SiH4 = PH3 = H2S
(3) SiH4 < PH3 > H2S (4) SiH4 < PH3 < H2S
Sol. (4)
Ex. The electronegativities of F and H are 4.0 and 2.1 respectively. The percent ionic character in H and F bond is
(1) 43 (2) 34 (3) 94 (4) 39
Sol. (1)

29
 PERIODIC TABLE
Ex. Give the correct order of electronegativity of central in following compounds –
CH3 – CH3, CH2 = CH2 , CH {CH
(a) (b) (c)
The correct order is –
(1) a > b > c (2) c > a > b (3) c > b > a (4) b > c > a
Sol. (3)
Ex. Which is the correct order of electronegativity –
(1) Cl > S > P > Si (2) Si > Al > Mg > Na (3) F > Cl > Br > I (4) All
Sol. (4)
Ex. Which of the following compound has highest value of bond length –
(1) CsF (2) CsBr (3) CsI (4) CsCl
Sol. (3)
Ex. Electronegativity increases in the order –
(1) F > O > N > Br (2) F > Br > N > O (3) F > O > Br > N (4) F > Br > O > N
Sol. (1)
Ex. The element with least electronegative nature is –
(1) Cu (2) Cs (3) Cr (4) Ba
Sol. (2)
Ex. Element of which of the following atomic numbers has lowest elecronegativity –
(1) 37 (2) 56 (3) 55 (4) 105
Sol. (3)

30
CHEMISTRY FOR NEET & AIIMS

1 18
1 2
H He
+1
–1

2 13 14 15 16 17
3 3 5 6 7 8 9 10
Li Be B C N O F Ne
+1 +2 +3 +4 +5 +2 –1
–3 +2 +4 –1/2
–4 +3 –1
etc. +1 –2
–3
0
etc.
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
+1 +2 +3 +4 +5 +6 +5 0
–4 +3 +4 +7
+1 +2 +3
–3 –2 +1
–1
3 4 5 6 7 8 9 10 11 12 etc.
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
+1 +2 +2 +2 +2 +2 +2 +2 +2 +2 +2 +2 +3 +4 +5 +6 +5 +4
+3 +3 +3 +3 +3 +3 +3 +3 +3 –4 +3 +4 +3 +2
+4 +4 +4 +4 +4 +4 +4 –3 –2 +1 0
+5 +5 +5 +5 +5 –1
+6 +6 +6
+7
37 38 49 50 51 52 53 54
Rb Sr In Sn Sb Te I Xe
+1 +2 +3 +4 +5 +6 +7 +6
+1 +2 +3 +4 +5 +4
–3 –2 +1 +2
0 0
–1
55 56 81 82 83 84 85 86
Cs Ba Tl Pb Bi Po At Rn
+1 +2 +3 +4 +5
+1 +2 +3

31
 GENERAL TREND OF DIFFERENT PROPERTIES IN THE PERIOD AND GROUPS

o
Atomic radius o Decreases
Ionisation potential o Increases
Electronegativity o Increases
Electron affinity o Increases
Covalent character of halides o Increases

o
Increases Metallic character o Decreases

o
Decreases Oxidising nature o Increases

o
G Decreases Reducing nature o Decreases

o
Decreases Screening effect o Increases

o
R
Decreases Effective nuclear charge (Zeff) o Increases

o
O Increases Valency w.r.t Oxygen o Increases

32
o
U Decreases Basic character of hydroxides o Decreases

o
Increases Basic character of hydrides o Decreases

o
P Increases Basic character of Oxides o Decreases

o
S Constant Strength of oxy acids o Increases

o
Constant Thermal stability of sulphate o Decreases

o
~ (Metals)Increases Thermal stability of carbonates o Decreases

o
~ (Non metal) Decreases (Metals) Increases Thermal stability of nitrates o Decreases

o
~ Increases Therma stability of hydroxide o Decreases
o
Decreases Density o First increases
o

~ Increases then decreases

o

p Increases Electro positivity    o Decreases

o

Increases
o

Increases
o

Increases
o

Increases
PERIODIC TABLE
CHEMISTRY FOR NEET & AIIMS

important facts to remember

1. Lowest electronegativity : Cs
2. Highest electronegativity : F
3. Highest ionisation potential : He
4. Lowest ionisation potential : Cs
5. Lowest electron affinity : Noble gases
6. Highest electron affinity : Chlorine
7. Least electropositive element : F
8. Lowest m. pt. metal : Hg
9. Highest m. pt. and b. pt. metal : W (Tungsten)
10. Lowest m. pt. and b. pt. non metal : He
11. Notorious element : Hydrogen
12. Lightest element : Hydrogen
13. Smallest atomic size : H
14. Largest atomic size : Cs
15. Largest anionic size : I–
16. Smallest cation : H+
17. Most electropositive element : Cs
18. Element with electronegativity
next to Fluorine : Oxygen
19. Group containing maximum no.
of gaseous elements in periodic table : Zero group
20. Total number of gaseous elements :
in periodic table : 11 (H, N, O, F, Cl, He, Ne, Ar, Kr, Xe, Rn)
21. Total number of liquid elements
in periodic table : 6 (Ga, Br, Cs, Hg, Fr, Uub)
22. Liquid element of radioactive nature : Fr
23. Total number of radioactive elements
in periodic table : 25
24. Volatile d block elements : Zn, Cd, Hg, Uub
25. Element containing no neutron : H
26. Most abundant element on earth : Oxygen
27. Most abundant metal on earth : Al
28. Element having maximum tendency
for catenation : Carbon
29. Non metal having highest m. pt., b.pt. : Carbon (dimond)
30. Metals showing highest oxidation number : Os (+8), Ru
31. Most electrovalent compound : CsF

33
 PERIODIC TABLE
32. Most stable carbonate : Cs2CO3
33. Strongest alkali : CsOH
34. Strongest basic oxide : Cs2O
35. Best electricity conductor among metals : Ag
36. Best electricity conductor among non metals : graphite
37. Most poisonous element : Pu (Plutonium)
38. Liquid non metals : Br
39. Element kept in water : Phosphorous
40. Elements kept in kerosene : IA group element (except Li)
41. Elements sublime on heating : I2
42. Noble metals : Au, Pt etc.
43. Amphoteric metal : Be, Zn, Al, Sn, Pb, Ga
44. Metalloids elements : Si, As, Te, At, Ge, Sb
45. Non metals having metallic lusture : Graphite, Iodine
46. Heaviest naturally occurring element : Uranium
47. Poorest conductor of electricity : Dimond
48. Hardest naturally ocurring element : Dimond
49. Lightest solid metal : Li
50. 90% of Sun mass : Hydrogen
51. Amphoteric oxides : BeO, Al2O3, ZnO, PbO, PbO2,
SnO, SnO2,
Sb2O3, As2O3, Cr2O3 etc.
52. Neutral oxides of non metals : NO, CO, H2O, N2O
53. Dry bleacher : H2O2
54. Dry ice : Solid CO2
55. Artificial explosive : TNT, RDX (Research Developed
Explosive etc.)
56. First noble prize of chemistry
was given to : Vantt Haff
57. Some isomorphous substances : FeSO4.7H2O, MgSO4.7H2O,
ZnSO4.7H2O
58 . Some effloroscent substances : Na2CO3.10H2O, MgSO4.7H2O etc.
59. First man made element : Tc43 (Technicium)
60. Smallest period : Ist (2 elements)
61. Largest period in periodic table : 6th (32 element)
62. Largest group in periodic table : IIIB (32 element)
63. Most abundant d-block metal : Fe
64. Most abundant s-block metal : Ca
65. Most stable element : Te
66. Highest density (Metals) : Os, Ir
67. Highest density (Non Metals) : Boron

34
CHEMISTRY FOR NEET & AIIMS
IMPORTANT SCIENTISTS & THEIR CONTRIBUTIONS
1. Dobereiner : Law of Triads
2. Fajans : Factors of polarisation.
3. Lavoisier : Father of chemistry, classified element into metals & non metals.
4. Glesspie - Nyholm : VSEPR Theory
5. Mendeleef : Periodic classification of elements.
6. Mosley : Concept of atomic number, modern periodic law, modern periodic table
7. Newland : Law of octaves.
8. Slater : Screening constant, Geometry of molecules.
9. Schoomaker & Stevenson : Bond length depends on difference in electronegativity
10. Lewis and Kossel : Electronic theory - octet rule
11. Rang & Warner : Long form of modern periodic table
12. Ramsay : Introduced noble gases in periodic table, Argon was discovered.
13. Seaborg : Post-Uranic elements
14. Heitler and London : Valence bond theory.
15. Hund's rule : Distribution of electrons in atomic orbitals in a sub - shell.
16. Pauling : Concept of dipole moment, valence bond theory Hybridization,
Electronegativity scale.
17. Sidgwick and powell : Hybridisation.
18. Hanny - Smith : Nature of bonds.

35
 PERIODIC TABLE

SOLVED EXAMPLE
Ex. 1 Following are the valence shell electronic Ex. 5 In Co lumn-I , ther e are given el ectronic
configurations of some elements. configurations of some elements. Match these
(i) 3s2 3p5 (ii) 3d10 4s2 with the correct metals given in Column-II :
(iii) 2s2 3p6 4s1 (iv) 1s2 2s2
Column-I Column-II
Find out the blocks to which they belong in the
(A) ns , np
2 5
(p) Chromium
periodic table ?
(B) (n – 1) d10 , ns1 (q) Copper
Ans. (i) p-block (ii) d-block
(iii) s-block (iv) s-block (C) (n – 1) d5 , ns1 (r) Krypton
Sol. The block of the elements depend on the type of (D) (n – 1) d , ns , np
10 2 6
(s) Bromine
sub-shell which receive the last electron. In case of Ans. (A) o (s) ; (B) o (q) ; (C) o(p) ; (D) o(r).
(i) it enters in 3p-subshell,
Sol. (A) ns 2 np 5 is general valence shell electron
(ii) z it enters 3d-subshell,
configuration of halogens. So this configuration
(iii) it enters 4s-subshell and
belongs to bromine.
(iv) it enters 2s-subshell.
(B) (n – 1) d1-10 ns1-2 ; This is electron configuration
Ex. 2. A M2+ ion derived from a metal in the first transition of d-block elements. As it contains (n – 1) d10ns1
metal series has four electrons in 3d subshell. What
configuration it belongs to copper.
element might M be ?
Ans. Chromium (C) (n – 1) d1-10 ns1-2 ; This is electron configuration
of d-block elements. As it contains (n – 1) d5 ns1
Sol. Electron configuration of M2+ is
configuration it belongs to chromium.
[Ar]18 4s0 3d4
(D) Noble gases has valence shell electron
? Electron configuration of M is
[Ar]18 4s1 3d5 (and not 4s2 3d4) configuration ns2 np6, so it belongs to krypton.
So total number of electrons = 24. Ex. 6 Match the metals given in Column-II with their
Hence, metal M is chromium (Cr). type given in Column-I :

Ex. 3 Find out the group of the element having the Column-I Column-II
electronic configuration, 1s2 2s2 2p6 3s2 3p6 3d 6 (A) Metalloid (p) Sulphur
4s2 .
(B) Radioactive (q) Gold
Ans. As last electron enters in d-subshell, therefore
this belongs to d-block. For d-block element the (C) Transition metal (r) Arsenic
group number is equal to the number of valence (D) Chalcogen (s) Uranium
shell electrons + number of electrons in (n-1) d-
Ans. (A) o (r) ; (B) o (s) ; (C) o(q) ; (D) o(p)
subshell.
So, group number = 6 + 2 = 8. Sol. (A) Arsenic is a metalloid because it behaves as
metal (forming cation, As3+ -AsCl3) as well as
Ex. 4 Arrange the following ions in the increasing order nonmetal (forming anion, As3– -AsH3).
of their size : Be2+ , Cl–, S2– , Na+ , Mg2+ , Br – ?
(B) Uranium is a radioactive element.
Ans. Be2+ < Mg2+ < Na+ < Cl– < S2– < Br –
(C) Those elements which in their neutral atoms or
Sol. Be2+ is smaller than Mg2+ as Be2+ has one shell in most common oxidation state have partially filled
where as Mg2+ has two shells. d-orbitals are called as transition elements. Gold in
Mg2+ and Na+ are isoelectronic species : Ionic its +3 oxidation state has electron configuration
radius v 1/nuclear charge. [Xe]54, 5d86s0 .
Cl– and S2– are isoelectronic species : Ionic radius (D) 16th group elements like oxygen and sulphur are
v 1/nuclear charge. ore forming elements and therefore are called as
Cl– is smaller than Br – as Cl– has three shells chalcogens.
where as Br – has four shells.

36
CHEMISTRY FOR NEET & AIIMS
Ex. 7 Match the metals given in Column-II with their Ex. 9 Ionisation energy and electron affinity of fluorine
type given in Column-I : are respectively 17.42 and 3.45 eV. Calculate
electronegativity of fluorine atom.
Column-I Column-II
Sol. According to Mulliken’s electronegativity (FM)
(A) Representative element (p) Cerium
(B) Lanthanide (q) Aluminium Ionisation energy + Electron affinity
=
2
(C) Coinage metal (r) Thorium
17.42 + 3.45
(D) Actinide (s) Gold = = 10.435
2
Ans. (A) o (q) ; (B) o (p) ; (C) o(s) ; (D) o(r)
Therefore, electronegativity on Pauling’s scale
Sol. (A) s-block and p-block elements are collectively
10.435
called as representative elements. As in aluminium (FP) = = 3.726
2.8
last electron enters in p-subshell ([Ne]103s23p1).
Ans. FP = 3.726
(B) Lanthanide series follows lanthanum (atomic
number 57) and starts from cerium (atomic number Ex. 10 Why the electron gain enthalpy values of
58) to lutetium (atomic number 71), fourteen 4f- series alkaline earth metals are lower (i.e. less negative) or
positive ?
elements.
Sol. The general valence shell electron configuration of
(C) Group 11- transition elements copper, silver & alkaline earth metals is ns2 (stable configuration).
gold are known as coinage metals (used for making The extra electron must enter np subshell, which is
the coins). effectively shielding by the two ns electrons and
the inner electrons. Consequently, the alkaline earth
(D) Actinides series follows actinium (atomic number metals have little or no tendency to pick up an extra
89) and starts from thorium (atomic number 90) to electron
lawrencium (atomic number 103), fourteen 5f- series
Ex. 11 Match the particulars given in Column-I with the
elements. process/metal / species given in Column-II.
Column-I Column-II
Ex. 8 The (IE 1) and the (IE 2) in kJ mol –1 of a few
elements designated by Roman numerals are (A) Isoelectronic species (p) A+(g) + energy
shown below: o A ++(g) + e– (g)
(B) Half filled orbital (q) Ar, K+, Ca++
I II III
(C) Second ionisation (r) Lutetium
IE1 403 549 1142 energy
IE2 2640 1060 2080 (D) Inner transition (s) Antimony
Which of the above elements is likely to be a element

(a) non-metal Ans. (A) o (q) ; (B) o (s) ; (C) o(p) ; (D) o(r)

(b) alkali metal Sol. (A) Species having same number of electrons but
different nuclear charge are called isoelectronic
(c) alkaline earth metal ? species. Ar, K + & Ca ++ have same number of
Ans. (a) non-metal(III) – Due to highest ionisation electrons i.e. 18 but 18, 19 & 20 number of protons
respectively.
energy, (IE1) and (IE2).
(b) alkali metal (I) – Due to lowest ionisation energy, (B) np3, (n–1) d5 and (n–2) f7 represent half filled
orbitals. Antimony has ([Kr]36 4d105s25p3).
(IE1) and there is quite high jump in (IE2) due to inert
gas configuration. (C) The energy required to remove an electron from
an univalent cation(g) is called second ionisation
(c) alkaline earth metal (II) – There is little difference energy.
in (IE1) and (IE2) and the value of (IE1) is slightly
(D) 4f and 5f- series elements are called inner
greater than(I) due to stable configuration(ns2).
transition elements because they have three outer
most shells incomplete.

37
 PERIODIC TABLE
Ex. 12 The Column-I has certain details about the
elements of s-, p- and d-block elements. Match Ex. 13 Match the type of elements / characteristic of
those with the group number of the elements the elements listed in Column-I with the correct
listed in Column-II. element listed in Column-II.

Column-I Column-II Column-I Column-II

(element / elements) (group number) (A) Highest 1st ionisation (p) Technitium
(A) An element whose fourth shell contains two energy
p-electrons (p) 8th group (B) Highest electronegativity (q) Lithium
(B) An element whose valence shell contains one (C) Synthetic element (r) Helium
unpaired p-electron (q) 12th group
(D) Strongest reducing agent (s) Fluorine
(C) An element which receives last electron in
Ans. (A) o (r) ; (B) o (s) ; (C) o(p) ; (D) o(q)
(n – 1) d-subshell (r) 14th group
Sol. (A) Helium has highest 1st ionisation energy amongst
(D) An element with the ground-state electron all the elements of periodic table because of ns2
configuration [Ar]4s23d10 ( s ) valence electron configuration and its small size of
17th group atom.
Ans. (A) o (r) ; (B) o (s) ; (C) o(p, q) ; (D) o(q) (B) Fluorine has highest electronegativity i.e. 4.0 on
Pauling scale on account of its small size.
Sol. (A) [Ar]3d104s24p2 : Fourth shell contains two
electron in 4p-sub shell i.e., 4p2. Therefore, group (C) Technitium is a man made element.
number = 10 + 4 = 14. (D) Lithium is a strongest reducing agent because
(B) Halogens (i.e. group number 17) have valence of its highest negative value of Eº due to its higher
shell electronic configuration ns2np5 and there is hydration energy on account of its small size of
one unpaired electron in p-subshell i.e., atom.

(C) The element in which last electron enters in d-

subshell belongs to d-block. For d-block elements
the group number = number of electrons in valence
shell + number of electrons in (n – 1) d-subshell.
Group number 8. Valence shell electronic
configuration is ns2(n – 1)d 6. Therefore, group
number = 2 + 6 = 8.
Like wise, group 12 is ns2(n – 1)d10. Therefore, group
number = 2 + 10 = 12.
So in group 8 and 12 last electron enters in d-subshell.
(D) For electronic configuration. [Ar]4s23d10 the
group number = 2 + 10 = 12.

38
CHEMISTRY FOR NEET & AIIMS

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. The ions O2–, F–, Na+ Mg2+ and Al3+ are isoelectronic. (C) Mn > Cr > Ti > V
Their ionic radii show (D) Ti > V > Cr > Mn
[CBSE AIPMT 2003]
6. Which of the following oxides is not expected to
(A) an increase from O to F– and then decrease
2–

react with sodium hydroxide?

from Na+ to Al3+
[CBSE AIPMT 2009]
(B) a decrease from O2– to F– and then increase
(A) B2O3 (B) CaO
from Na+ to Al3+
(C) SiO2 (D) BaO
(C) a significant increase from O2– to Al3+
(D) a significant decrease from O2– to Al3+ 7. Which one of the elements with the following outer
orbital configurations may exhibit the largest number
2. Ionic radii are [CBSE AIPMT 2004]
of oxidation states? [CBSE AIPMT 2009]
(A) inversely proportional to effective nuclear
(A) 3d , 4s
3 2
(B) 3d5, 4s1
charge
(C) 3d5, 4s2 (D) 3d2, 4s2
(B) inversely proportional to square of effective
nuclear charge 8. Amongst the elements with following electronic
(C) directly proportional to effective nuclear charge configurations, which one may have the highest
(D) directly proportional to square of effective ionisation energy ? [CBSE AIPMT 2009]
nuclear charge (A) [Ne] 3s 3p2 3
(B) [Ne] 3s23p2
(C) [Ar] 3d10, 4s2 4p3 (D) [Ne] 3s2 3p1
3. Identify the correct order of the size of the following.
[CBSE AIPMT 2007] 9. Which of the following represents the correct order
(A) Ca < K < Ar < S < Cl
2+ + 2– – of increasing electron gain enthalpy with negative
(B) Ca < K < Ar < Cl < S
2+ + – 2– sign for the elements O, S, F and Cl?

(C) Ar < Ca2+ < K+ < Cl– < S2– [CBSE AIPMT 2010]

(D) Ca2+ < Ar < K+ < Cl– < S2– (A) Cl < F < O < S

4. Which of the following electronic configuration of (B) O < S < F < Cl

an atom has the lowest ionisation enthalpy ? (C) F < S < O < Cl
[CBSE AIPMT 2007] (D) S < O < Cl < F
(A) 1s2, 2s22p5 (B) 1s2, 2s22p3
10. The correct order of the decreasing ionic radii among
(C) 1s2, 2s22p5, 3s1 (D) 1s2, 2s22p6
the following isoelectronic species is

5. The correct order of decreasing second ionisation [CBSE AIPMT 2010]

enthalpy of Ti(22), Cr(24) and Mn(25) is (A) Ca2+ > K+ > S2– > Cl–
[CBSE AIPMT 2008] (B) Cl– > S2– > Ca2+ > K+
(A) Cr > Mn > V > Ti (C) S2– > Cl– > K+ > Ca2+
(B) V > Mn > Cr > Ti (D) K+ > Ca2+ > Cl– > S2–

39
 PERIODIC TABLE

11. Identify the wrong statement in the following. 14. In which of the following options the order of
[CBSE AIPMT 2012] arrangement does not agree with the variation of
(A) Amongst isoelectronic species, smaller the property indicated against it?
positive charge on the cation, smaller is the (A) B < C < N < O (increasing first ionisation
ionic radius enthalpy)
(B) Amongst isoelectronic species, greater the (B) l < Br < Cl < F (increasing electron gain enthalpy)
negative charge on the anion, larger is the ionic (C) Li < Na < K < Rb (increasing metallic radius)
radius (D) Al3+ < Mg2+ < Na+ < F– (increasing ionic size)
(C) Atomic radius of the elements increases as one
15. The element Z = 114 has been discovered recently.
moves doen the first group of the periodic table
It will belong to which of the following family/group
(D) Atomic radius of the elements decreases as one
and electronic configuration ? [NEET 2017]
moves across from left to right in the 2nd period
(A) Halogen family, [Rn] 5f 6d 7s 7p5
14 10 2
of the periodic table
(B) Carbon family, [Rn] 5f14 6d10 7s2 7p2
12. Which of the following orders of ionic radii is (C) Oxygen family, [Rn] 5f14 6d10 7s2 7p4
correctly represented? [CBSE AIPMT 2014] (D) Nitrogen family, [Rn] 5f14 6d10 7s2 7p6
(A) H– > H+ > H (B) Na+ > F– > O2–
(C) F– > O2– > Na+ (D) Al3+ > Mg2+ > N3– 16. The correct order of atomic radii in group 13 elements
is [NEET 2018]
13. The species Ar, K+ and Ca2+ contain the same number
of electrons. In which order do their radii increase? (A) B < Ga < Al < Tl < In
[CBSE AIPMT 2015] (B) B < Al < Ga < In < TI
(A) Ar < K < Ca
+ 2+
(B) Ca < Ar < K
2+ +
(C) B < Al < In < Ga < Tl
(C) Ca < K < Ar
2+ +
(D) K+ < Ar < Ca2+
(D) B < Ga < Al < In < TI

40
CHEMISTRY FOR NEET & AIIMS

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

1. The pair of amphoteric hydroxides is 9. Which of the following substances has the least
(A) Al(OH)3, LiOH (B) Be(OH)2, Mg(OH)2 covalent character ? [2017]
(C) B(OH)3, Be(OH)2 (D) Be(OH)2, Zn(OH)2 (A) Cl2O (B) NCl3
[2005] (C) PbCl2 (D) BaCl2
10. The law of triads is applicable to a group of [2017]
2. Largest differene in radii is found in case of the pair (A) Cl, Br, I (B) C, N, O
(A) Li, Na (B) Na, K (C) Na, K, Rb (D) H, O, N
(C) K, Rb (D) Rb, Cs. 11. For d block elements the first ionization potential is
[2007, 2012] of the order [2017]
3. Which of the following statements in correct ? (A) Zn > Fe > Cu > Cr (B) Sc = Ti < V = Cr
(A) Ionic radius is proportional to atomic number. (C) Zn < Cu < Ni < Co (D) V > Cr > Mn > Fe
(B) ionic radius is inversely proportional to atomic ASSERTION AND REASON
mass.
(C) Ionic radius is inversely proportional to In each of the following questions, two statement
effectivenuclear charge. are given one is assertion and the other is reason.
(D) All are correct [2010] Examine the statement carefully and mark the correct
answer according to the instruction given below
4. The phosphate of a metal has the formula MHPO4. (A) If both the assertion and reason are true and
The formula of its chloride would be reason explains the assertion
(A) MCl (B) MCl2 (B) If both the assertion and reason are true but
(C) MCl3 (D) M2Cl3 [2010] reason does not explain the assertion
(C) If assertion is true but reason is false
5. Which of the following sequence contains atomic
(D) If assertion is false but reason in true
number of only representative elements ?
(E) Both assertion & reason are false
(A) 55,12,48,53 (B) 13,33,54,80
12. Assertion : First ionisation energy for nitrogen is
(C) 3,33,53,87 (D) 22,33,55,66
lower than oxygen.
[2010]
Reason : Across a period effective nuclear charge
6. The first ionisation enthalpy of Na, Mg and Si are decreases. [2005]
496, 737, 776 kJ/mol respectively. What will be the
13. Assertion : E° for Mn3+/Mn2+ is more positive than
first ionisation enthalpy potential of Al in kJ/mol?
Cr3+/Cr2+.
(A) > 766 kJ/mol
Reason : The third ionisation energy of Mn is larger
(B) > 496 and < 737 kJ than that of Cr. [2006]
(C) > 737 and < 766 kJ/mol
(D) > 496 kJ/mol [2013] 14. Assertion : F is more electronegative than Cl.
7. Which is correct regarding size of atom ? Reason : F has high electron affinity than Cl.
[2007]
(A) N < O (B) B < Ne
(C) V > Ti (D) Na > K [2014] 15. Assertion : Helium has the highest value of
ionisation energy among all the elements known.
8. An element (X) belongs to fourth period and
Reason : Helium has the highest value of electron
fifteenth group of the periodic table. Which one of
affinity among all the elements known. [2010]
the following is true regarding the outer electronic
configuration of (X)? It has 16. Assertion : For hydrogen like species, energy of an
(A) partially filled d orbitals and completely filled electron in a particular orbit increases with increase
s orbital in value of Z.
(B) compeletely filled s orbital and half-filled p Reason : Electronegativity decreases across a
orbitals period. [2016]
(C) completely filled s orbital and half-filled p 17. Assertion : Atomic radius of gallium is higher than
orbitals that of aluminium [2017]
(D) half-filled d orbitals and completely filled s Reason : The presence of additional d-electron offer
orbital. [2016] poor screening effect for the outer electrons from
increased nuclear charge.

41
CHEMISTRY FOR NEET & AIIMS

ANSWER KEY

EXERCISE : PART # 1
1. D 2. A 3. B 4. C 5. A 6. B 7. C 8. A 9. B 10. C 11. A 12. * 13. C
14. A,B 15. B 16. D

PART # 2
1. D 2. B 3. C 4. B 5. C 6. C 7. B 8. C 9. D 10. A 11. A 12. D 13. B
14. C 15. C 16. C 17. C

42
CHEMISTRY FOR NEET & AIIMS

EXERCISE
P-1 (NEET/AIPMT)
1. (D) :On increasing atomic number of isoelectronic species
ionic radii decreases due to increasing effective nuclear
charge (Zeff).

1 1
Radius v v
Atomic number Zeff

So, as the negative charge increasesionic radii increases

while on increasing positive charge ionic radii decreases.
Anions having higher ionic radii than the cation.
Hence, order of radii
O2– > F– Na+ > Mg2+ > Al3+

1
2. (A) : Ionic radii v
Zeff

Zeff o effective nuclear charge

this Zeff is calculated as follows :
Zeff = Z – screening constant (V)
This value of screening constant is based upon the
4PMVUJPOT number of electrons in valence shell as well as in
penultimate shell.

3. (B) : A cation has always the lesser ionic size than a

metal atom due to loss of electrons and an anion has
always the greater size than metal atom due to gain of
electrons. The given species are isoelectronic species
as they contain same number of electrons. For
isoelectronic species ionic radii

1
v
atomic number

Ion : Ca2+ K+ Ar S2 Cl
Atomic number : 20 19 18 16 17
So, the correct order of size is as
Ca2+ < K+ < Ar < Cl– < S2–

4. (C) : The electronic configuration 1s2, 2s22p5, 3s1 shows

lowest ionisation energy because this configuration is
unstable due to the presence of one electron in s-orbital.
Hence, less energy is required to remove the electron.

43
 PERIODIC TABLE
5. (A) : The amount of energy required to remove an
9. (B) : Key Idea Electron gain enthalpy, generally, increases
electron from unipositive ion is referred as second
in a period from left to right and decreases in a group on
ionisation potential.
moving downwards. However, members of III period have
In Ti, V, Cr and Mn, generally second ionisation energy
somewhat higher electron gain enthalpy as compared to
increases with increase in atomic number but second
the corresponding members of second period, because
ionisation potential of Cr is greater than that of Mn due
of their small size.
to the presence of exactly half-filled d-subshell in Cr.
O and S belong to VI A (16) group and Cl and F belong to
thus, the order of second ionisation enthalpy is
VII A (17) group. Thus, the electron gain enthalpy of Cl
Cr > Mn > V > Ti and F is higher as compared to O and S.
6. (B) : Sodium hydroxide, NaOH, being a strong alkali never Cl and F > O and S
react with a basic oxide (compound). Among the given Between Cl and F, Cl has higher electron gain enthalpy
options, B2O3 and BeO are amphoteric oxides, SiO2 is an then the F, since the incoming electron experiences a
acidic oxide and CaO is a basic oxide. Therefore, NaOH greater force of repulsion because of small size of F-
does not react with CaO. atom. Similar is true in case of O and S, i.e. the electron
gain enthalpy of S is higher as compared to O due to its
7. (C) : The sum of number of electrons (unpaired) in d- small size. Thus, the correct order of electron gain
orbitals and number of electrons in s-orbital gives the enthalpy of given elements is
number of oxidation states (os) exhibited by a d-block
O < S < F < Cl
element. Therefore.
(A) 3d3, 4s2 Ÿ OS = 3 + 2 = 5 10. (C) : Key Idea Ionic radii v charge on anion
(B) 3d , 4s Ÿ OS = 5 + 1 = 6
5 1
1
(C) 3d5, 4s2 Ÿ OS = 5 + 2 = 7 v
charge on cation
(D) 3d2, 4s2 Ÿ OS = 2 + 2 = 4
During the formation of a cation, the electrons are lost
Hence, element with 3d5, 4s2 configuration exhibits largest
from the outer shell and the remaining electrons
number of oxidation states.
experience a great force of attraction by the nucleus, i.e.
8. (A) : Key Idea Across a period, increasing nuclear charge attracted more towards the nucleus. In other words,
outweighs, the shielding, hence the outemost electrons nucleus hold the remaining electrons more tightly and
are held more and more tightly and ionisation energy. this results in decreased radii.
increases across a period while as we move down a group However, in case of anion formation, the addition of
increase in shielding outweighs the increasing nuclear electron(s) takes place in the same outer shell, thus the
charge and the removal of the outermost electron required hold of nucleus on the electrons of outer shell decrease
less energy down a group. and this result in increased ionic radii.
Electronic configuration Group Thus, the correct order of ionic radii is
[Ne] 3s 3p2 3
V S2– > Cl– > K+ > Ca2+
[Ne]3s2 3p2 IV
11. (A) : Atomic radius of the elements decreases across a
[Ar] 3d , 4s 4p
10 2 3
V
period from left to right due to increase in effective
[Ne] 3s23p1 III
nuclear charge. On moving down a group, since, number
Since, ionisation energy increases in a period and of shells increases, so atomic radius increases.
decreases in a group, [Ne] 3s23p3 configuration has the
Amongst isoelectronic species, ionic radius increases
highest ionisation energy among the given elements.
with increases in negative charge or decrease in positive
charge.

44
CHEMISTRY FOR NEET & AIIMS
12. (*) : (No option is correct.)
14. (A,B) : for option (A)
(A) H– > H+ > H
First ionisation energy is the energy required to remove
It is known that radius of a cation is always smaller than
an electron from outermost shell.
that of a neutral atom due to decrease in the number of
Hence, correct order is B < C < O < N.
orbits. Whereas, the radius of anion is always greater
For option (B)
than a cation due to decrease in effective nuclear charge.
hence, the correct order is Electron gain enthalpy is the energy required to gain an
electron in the outermost shell.
H– > H > H+
Hence, the correcct order is I < Br < F < Cl.
(B) Na+ > F– > O2–
For option (C)
The given species are isoelectronic as they contain same
number of electrons. for isoelectronic species, As we move down the group in alkali metal, metallic
radius increases Li < Na < K < Rb.
1 For option (D)
Ionic radii v
atomic number In case of isoelectronic species, as positive charge
Ion: Na F O
+ – 2– decreases or negative charge increases the ionic size of
Atomic number : 11 9 8 the species increases and vice-versa

Hence, the correct order of ionic radii is Al3+ < Mg2+ < Na+ < F–.

O2– > F– > Na+ 15. (B) : The element with atomic number, Z = 114 is flerovium
(C) Similarly, the correct option is (F1). It is a super heavy artificial chemical element. In the
O2– > F– > Na+ periodic table of the elements, it is a transactinide element
(D) Ions : Al3+ Mg2+ N3– in the p-block. It is a member of the 7th period and is the
Atomic number : 13 12 7 heaviest known member of the carbon family.
Hence, the correct order is, N > Mg2+ > Al3+
3– Electronic configuration for Z = 114 is
[Rn]86 5f14, 6d10, 7s2, 7p2
13. (C) : Ca2+ < K+ < Ar
Ar, K+ and Ca2+ are isoelectronic i.e. with same number
16. (D) : B < Ga < Al < In < Tl
of electrons, 18. For isoelectronic species ionic radii
decreases with increase in effective (relative) positive
charge. Also Ar. K and Ca belong to the same period (3rd
period).

45
 PERIODIC TABLE

EXERCISE
11. (A) The ionisation energies increase with increase in

atomic number. However, the trend is irregular among
P-2 (AIIMS)
some d-block elements. On the basis of electronic con-
figuration, the
1. (D) Both Be(OH)2 and Zn(OH)2 are amphoteric in nature.
Zn : 1s2 2s2 p6 3s2 p6 d10 4s2
2. (B) Atomic as well as ionic radii increase from Li to Fr Fe : 1s2 2s2 p6 3s2 p6 d6 4s2
due to increase in one extra shell of electron on going Cu : 1s2 2s2 p6 3s2 p6 d10 4s1
down the group.
Cr : 1s2 2s2 p6 3s2 p6 d5 4s1
Li Na K Rb Cs
IE1 follows the order : Zn > Fe > Cu > Cr
Metallic radii (pm) 152 186 227 248 265
12. (D) First ionisation energy for nitrogen is greater than
1 oxygen. N O
3. (C) rionic v
Zeff eV 14.5 13.6
4. (B) Since the phosphate of a metal is MHPO4, therefore, This is due to stable configuration of nitrogen
metal M must be divalent, i.e., M2+. As a result, the for- (half-filled 2p-orbital).
mula of its chloride is MCl2. Due to screening effect, the valence electrons
experience less attraction towards the nucleus. Due to
5. (C) Sequency (C) contains only representative elements. this, the valence shell electrons do not fell the full charge
6. (C) Na, Mg, Al and Si are in period 3 and as we move of the nucleus. The actual nuclear charge felt by the
across the period, the atomic size decreases and hence valence shell electrons is termed effective nuclear charge
ionisation enthalpy increases. So, the order is Na < Mg < and its magnitude increases in a period when we move
Al < Si from left right.
Hence, IE of Al is greater than that of Mg (737 kJ /mol) 13. (B) It is known that the value of E° becomes more
and lower than that of Si (776 kJ/mol). negative down the series. As chromium is present below
7. (B) The atomic radii of noble gases are by far the largest in electrochemical series than Mn, so Mn has more
in their respective periods. This is due to the reason that positive E° value than Cr.
reason that noble gases have only van der Waals radii. Mn o 3d5 4s2, Mn2+ o 3d5 4s0,
Cr o 3d5 4s1, Cr2+ o 3d4 4s0
8. (C) The electronic configuration of (X) can be writen as For elimination of one electron from Mn2+, more energy
X= 1s22s22p63s23p64s23d104p3 is required due to its stable configuration. That is why
So, element (X) has completely filled s and d orbitals and third ionisation energy of Mn is larger than Cr.
half filled p orbitals.
14. (C) Chlorine has high electron affinity than fluorine. The
9. (D) According to Fajan's rule :
less negative electron gain enthalpy of fluorine as com-
1 pared to chlorine is due to very small size of the fluorine
Covalent character v v size of anion
size of cation atom.
Among the given species order of size of cations
15. (C) He contains fully filled 1s2 orbital which has more
N3+ < O2+ < Pb2+ < Ba2+
penetrating effect and is very close to the nucleus and
order of size of anions O2– > Cl–.
hence has higher value of inosiation energy.
Hence the order of covalent character is
NCl3 > Cl2O > PbCl2 > BaCl2 16. (C) For hydrogen like species, energy of an electron in
BaCl2 is least covalent in nature. nth orbit is given by

2S 2 mZ2 e 4 k 2
10. (A) According to the law of triads the atomic wt of the En 
n 2h 2
middle element is arithmatic mean of I and III.
i.e., En v Z2.
At.wt of Cl + At wt of I Electronegativity increases across a period with decrease
At wt of Br =
2 in size of atoms.
17. (C) Atomic radius of gallium is less than that
of aluminium.

46
CHEMICAL BONDING
CHAPTER
09
The nature of the chemical bond is the problem at the heart of all
chemistry.

“BRYCE CRAWFORD”

INTRODUCTION

T
he attractive force which holds various constituents (atoms, ions, etc,) together in
different chemical species is called a chemical bond. Since the formation of chemical
compounds takes place as a result of combination of atoms of various elements in
different ways, it raises many questions. why do atoms combine? Why are only
certain cmbinations possible? Why do molecules possess definite shapes? To an-
swer such questions different theories and concepts have been put forward from
time to time. These are kossel-Lewls approach, valence Shell Electron Pair Repulsion
(VSEPR) Theory, Valence Bond (VB) Theory and Molecular orbital and the interpre-
tation of the nature of chemical bonds have closely been related to the developments
in the understanding of the structure of atom, the electronic configuration of ele-
ments and the periodic table. Every system tends to be more stable and bonding is
nature's way of lowering the energy of the system to attain stability .

47
CHEMISTRY FOR NEET & AIIMS

Chemical Bond
(a) A force that acts between two or more atoms to hold them together as a stable molecule.
(b) It is union of two or more atoms involving redistribution of e– among them.
(c) This process accompanied by decrease in energy.
(d) Decrease in energy DStrength of the bond.
(e) Therefore molecules are more stable than atoms.
Cause of chemical combination
1. Tendency to Acquire Minimum Energy :
(a) When two atoms approaches to each other-Nucleus of one atom attracts the electron of another atom.

Potential Energy diagram

(b) Two nuclei and electron of both the atoms repells each other.
(c) If net result is attraction, the total energy of the system (molecule) decreases and a chemical bond forms.
(d) So Attraction D 1/energy D Stability.
(e) Bond formation is an exothermic process
2. Octet Rule
Octet rule was given by Lewis & Kossel
Atoms Combines to complete an octet of electrons in their outer most orbit. Complete orbital represents to get most
stable state. Hence all atoms have a tendency to acquire octet (s2p6) configuration in their outermost orbit.
The octet may be complete in following manner:
Complete transfer of electrons from one atom to another.
Ex. NaCl, CaCl2 & MgO etc. (Ionic Bond)
Sharing of electrons between atoms.
(a) Sharing of equal number of electron between two atoms.
Ex. Cl2, N2, O2 etc., (Covalent bond)
(b) Sharing of electron pair given by only one atom
Ex. [NH3 o H+] & NH3 o BF3 (Co-ordinate Bond)
Exceptions of Octet Rule :
Transition Metal Ions
Cr3+ Mn2+ Fe2+
[Ar]3d 3 [Ar]3d5 [Ar]3d6
[2, 8, 11] [2, 8, 13] [2, 8, 14]
Pseudo Inert Gas Configuration [s2p6d10]
Zn2+ Cd2+
[Ar]3d10 [Kr]4d10

48
 CHEMICAL BONDING

Contraction of Octet (Incomplete Octet) F

×
BeF2 BF3 AlCl3 BCl3 |.
(4e) (6e) (6e) (6e) B . ×F (6 Electrons)
.

|
|×
Expansion of Octet (Due to Empty d-Orbitals)
F
PCl5 SF6 ClF3 ICI5 IF7
p p p p p F F
(10e ) (12e ) (10e ) (12e ) (14e-)
- - - -

F S F
Odd Electron Species
Ex. NO, NO2, ClO2 etc.
F (12e) F
O
N , N O
O
Compounds of Noble Gases
Noble gases which have already completed their octets (or douplet in case of He.) should not form compounds.
However, their compounds like XeF2, XeF6 & KrF2 etc., have been actually prepared.
CLASSIFICATION OF BONDS
ATTRA CTIV E FORCES

STRONG BOND W EA K INTERA CTION

Ionic Cov alent Co-ordinate Metallic Hydrogen Vander w aal's

bond bond bond bond bond Interaction

Covalent Bond
(a) A covalent bond is formed by the mutual sharing of electrons between two atoms of electronegativity
elements to complete their octet.(Except H which completes its duplet)

××
H ·· H

×
H–H

×
O=O

××

H2 molecule O O
(b) The shared pair of electrons should have opposite spins, and are localised between two atoms concerned.
(c) Shairing of electrons may occurs in three ways –
No. of electrons shared Bonded Electron pair Bond
between two atoms
2 1 Single bond (–)
4 2 Double bond (=)
6 3 Triple bond ({)
Ex. H — N — H {Three single bonds (not triple bond}

H
N {N Triple bond. (not three single bond) O = O (Double bond) H – O – H (Two single bonds.)
Co-ordinate Bond
(a) It is a covalent bond in which the shared electron pair come from one atom is called coordinate bond.
(b) Necessary conditions for the formation of co-ordinate bond are -
(i) Octet of donor atom should be complete and should have atleast one lone pair of electron.

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CHEMISTRY FOR NEET & AIIMS
(ii) Acceptor atom should have a deficiency of at least one pair of electron.
(c) Atom which provide electron pair for shairing is called donor.
(d) Other atom which accepts electron pair is called acceptor. That is why it is called donor-acceptor or dative
bond.
H F
_ _
H–N: + B–F o NH3 oBF3
_ _
H F
BF3 is electron deficient compound.
H3N NH3
+2
Metal co-ordinate compounds - [Cu(NH3)4]+2 Ÿ Cu
H3N NH3

H
+ +
Ex. NH4 ; H3N + H H N H
H
(Lowry - Bronsted acid)
-
(e acceptor)

H H
H3 O+ ; O + H+ O H+
H H
N2 O ;

KEY POINTS

Compounds in which Ionic, covalent and co-ordinate bonds are present, are as follows -
NH4Cl, CuSO4.5H2O, K4[Fe(CN)6], KNC, KNO3, etc.

Wave mechanical concept of co-valent bonding –

(a) One orbital can accommodate at the most 2 electrons with opposite spins
(b) Half filled orbital or unpaired electron orbital accepts one electron from another atom, to complete its orbital.
(c) Tendency to complete orbital or to pair the electron is an condition of covalent bond.
Completion of octet is not the essential condition of covalent bond.
(d) If the outermost orbit has empty orbitals then covalent bonds are formed in excited state.

Variable Valency in Covalent Bonds

(a) Variable valencies are shown by those elements which have empty orbitals in outermost shell.
(b) Lone pair electrons get excited in the subshell of the same shell to form the maximum number of unpaired electrons.
Maximum covalency is shown in excited state.
(c) The energy required for excitation of electrons is called promotion energy.
(d) Promotion rule – Excitation of electrons in the same orbit.

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 CHEMICAL BONDING
Ex.
(I) Phosphorus oGround state
Covalency 3 (PCl3)
3s 3p
Phosphorus oExcited state
Covalency – 5 (PCl5)
3s 3p 3d
(II) Sulphur oGround state.

3s 3p 3d Covalency - 2 (SF2)
Sulphur oExcited state
Ist excited state Covalency - 4 (SF4)
3s 3p 3d
2nd excited state Covalency - 6 (SF6)
3s 3p 3d So variable covalency of S is 2, 4, & 6.
(III) Iodine has three lone pair of electrons
(Ground state)
5s 5p 5d
So it shows three excited states – Maximum number of unpaired electrons = 7
Variable Valencies are 1, 3, 5, 7
To explain the formation of covalent bond two theories based on quantum mechanics have been proposed.
x Valence bond theory (VBT)
x Molecular orbital theory (MOT)
VALENCE BOND THEORY (VBT)
(I) Overlapping theory (II) Hybridisation theory
(I) Overlapping theory
It was presented by Heitler & London to explain how a covalent bond is formed.
The main points of theory are –
(a) To form a covalent bond overlapping occurs between half filled valence shell orbitals of the two atoms.
(b) Resulting bond acquires a pair of electrons with opposite spins to get stability.
(c) Orbitals come closer to each other from the direction in which there is maximum overlapping
(d) So covalent bond has directional character.
(e) Extent of overlapping vstrength of chemical bond.
(f) Extent of overlapping depends on two factors.
(i) Nature of orbitals – p, d and f are directional orbitals omore overlapping
s-orbital onon directional – less overlapping
(ii) Nature of overlapping –
Co-axial overlapping - extent of overlapping more.
Collateral overlapping - extent of overlapping less
Order of strength of Co - axial overlapping – p - p > s - p > s - s

• • • • • •
p-p p–s s–s
(g) As the value of n increases, bond strength decreases.
1s - 2p > 2s - 2p > 3s - 3p

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CHEMISTRY FOR NEET & AIIMS
(h) If n is same 2p - 2p > 2s - 2p > 2s - 2s
(i) Electron which is already paired in valency shell can enter into bond formation, if they can be unpaired first
and shifted to vacant orbitals of slightly higher energy of the same energy shell.
(j) This point can explain the trivalency of boron, tetravalency of carbon, pentavalency of phosphorus etc.
(k) Three types of bonds are formed on account of overlapping.
x Sigma (V) bond x Pi (S) bond x delta (G) bond
Sigma (V V) Bond
When orbitals overlaps along their inter nuclear axis, V-bond is formed Ex. The bond formed by overlapping of s - s, s -
p, p - p (axial), sp3 – s, sp2 – s, sp3 – sp3, sp3 – sp2 & sp – sp atomic orbitals.
Sigma bond

· + · · ·

S – S overlapping

Pi (S) Bond : When two p-orbitals along the lateral axis (side way), S-bond is formed.

Difference between sigma and pi-bond
S.No. Sigma-bond Pi-bond
1. A V-bond is formed by the axial overlapping A S-bond is formed by the side ways overlapping
of atomic orbitals. of orbitals.
2. V-bond formation involves overlapping of s-s, It involves overlapping of p-p orbitals.
s-p and p-p orbitals.
3. V-bond is stronger because of larger extent of S-bond is relatively weaker because of smaller
overlapping extent of overlapping.
4. The molecular orbital is symmetrical about The molecular orbital is discontinuous and consists
internuclear axis and electron cloud is present on two electron clouds below and above the internuclear
this axis axis
5. Free rotation exists around a V-bond. Free rotation does not exist around S-bonds.
6.. A sigma bond may exist either alone or A S-bond is always present along with a sigma-bond
or along with S-bonds.
7. Hybridised orbitals or unhybridised orbitals are Hybridised orbitals are never involved in S-bond.
involved in V-bond.

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 CHEMICAL BONDING
Dalta(GG)-Bond: It is special type of lateral overlapping in which all four lobs of d-orbital are overlap laterally with other
smilar d-orbital produce delta(G)-bond.

Ex. What are the total number of V & S bonds in tetracyanomethane.

Sol.

From the structure it is clear that it has 8 V and 8 S bonds.

(II) Hybridisation theory
x It is introduced by pauling and slater, to explain equivalent nature of covalent bonds in a molecule.
Consider an example of Be compound :-
If it is formed without hybridisation then -
p-s p–p
Cl —— Be ———— Cl
both the Be–Cl bonds should have different parameters and p–p bond strength > s–p bond strength.
Practically bond strength and distance of both the Be–Cl bonds are same.
This problem may overcome if hybridisation of s and p-orbital occurs.
x Definition : Mixing of different shapes and approximate equal energy atomic orbitals, and redistribution of
energy to form new orbitals, of same shape & same energy. These new orbitals are called hybrid orbitals. and
the phenomenon is called hybridisation.
Now after considering s–p hybridisation in BeCl2
p–sp sp–p
Cl ——— Be ———— Cl
bond strength of both the bonds will be equal.
Characteristic of Hybridisation :
(a) Hybridisation is a mixing of orbitals and not electrons. Therefore in hybridisation full filled, half filled and empty
orbitals may take part.
(b) Number of the hybrid orbitals formed is always be equivalent to number of atomic orbital which have taken part in
the process of hybridisation.
(c) Each hybrid orbital having two lobes, one is larger and other is smaller. Bond will be formed from large lobe.
(d) The number of hybrid orbitals on central atom of a molecule or ion = number of Vbonds + lone pair of electron.
(e) One element can represent many hybridisation state depending on experimental conditions
Ex. C showing sp, sp2 and sp3 hybridisation in its compounds.
(f) Hybrid orbitals are differentiated as sp, sp2, sp3 etc.
(g) The directional properties in hybrid orbital is more than atomic orbitals. Therefore hybrid orbitals form stronger
sigma bond. The directional property of different hybrid orbitals will be in following order.
sp < sp2 < sp3 < sp3d < sp3d2 < sp3d3
(h) Hybridize orbitals show axial overlapping & form V bond

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CHEMISTRY FOR NEET & AIIMS
Types of Hybridisation
(1) sp Hybridisation :
(a) In this hybridisation one s– & one p– orbital of an atom are mixed to give two new hybrid orbitals which are
equivalent in shape & energy known as sp hybrid orbitals.
(b) These two sp hybrid orbitals are arrange in straight line & at bond angle 180°.
(c) s-character 50%
2s 2p
Be (ground state)

2s 2p

Be (excited state)
sp hybridisation

Be atom share two electrons sp sp

with F in BeF2,

F F
(2) sp2 Hybridisation
(a) In this hybridisation one s & two p orbitals are mixed to give three new sp2 hybrid orbitals which all are in same
shape & equivalent energies.
(b) These three sp2 hybrid orbitals are at angle of 120° & giving trigonal planar shape.
(c) s-character 33.33% in each orbital.
2s 2p
B (ground state)

B (excited state)
sp2 hybrid orbitals
2 2 2
sp sp sp
B atom share 3 electrons

F F F
with 3 F atoms in BF3
(3) sp3 Hybridisation
(a) In this hybridisation one s orbital & three p orbitals of an atom of a molecule or ion, are mixed to give four new
hybrid orbitals called as sp3 hybrid orbitals.
(b) The angle between these four hybrid orbitals will be 109° 28' four electrons with 4 hydrogen atoms
2s 2p
C (ground state)
H
C
C (excited state) H H
sp3 hybridisation H
3 3 3 3
C atom share sp sp sp sp

H H H H
(c) The shape obtained from these hybrid orbitals would be tetrahedron.

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 CHEMICAL BONDING

(4) sp3d Hybridisation

(a) In this hybridisation one s orbital, three p orbitals and one d orbital are mixed to give five new hybrid orbitals
which are equivalent in shape and energy called as sp3d hybrid orbitals.
(b) Out of these five hybrid orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals are perpendicular
to the plane of three hybrid orbitals that is trigonal planar, the shape of molecule becomes is trigonal bipyramidal.
For example, PCl5 showing sp3d hybridisation
3s 3p 3d
P (ground state)

Cl

Cl P Cl

Cl

Cl
Structure of PCl5

3s 3p 3d

P* (excited state)
sp3d hybridisation

sp3d sp3d sp3d sp3d sp3d

P atom share five e with Cl
Cl Cl Cl Cl Cl

(c) In this hybridisation dz2

orbital is hybridised with s and p orbitals.
3
In this way five sp d hybrid orbitals form five sigma bond with five Cl atoms and give a molecule of PCl5, shape
of this molecule is trigonal bipyramidal.
Axial two P–Cl bonds are longer than equatorial three P–Cl bond due to repulsion between 3 equitorial b.p. of
e– and 2 axial b.p. of e–

(5) sp3d2 Hybridisation

(a) In this hybridisation, one s-orbital, three p-orbitals & two d-orbitals are mixed to give six new hybrid orbitals
known as sp3d2 hybrid orbitals.
(b) The shape of molecule obtained from above six hybrid orbitals will be symmetrical octahedral.
(c) The angle between all hybrid orbitals will be 90°.
Ex. SF6, AlF6–3, PF6–, ICl5, XeF4, XeOF4, ICl4–,
(d) Two 'd' orbital participates in the hybridisation are dx2–y2 and dz2.
3s 3p 3d
SF6 S (ground state)

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CHEMISTRY FOR NEET & AIIMS

3s 3p 3d
S (IInd excited state)

sp3d2 hybridisation

3 2 3 2 3 2
sp d sp d sp d sp d
3 2
sp3d2 sp3d2

S (after hybridisation) share 6e– with 6 F atoms

F F F F F F

(6) sp3d3 Hybridisation

(a) In this hybridisation, one s-orbital, three p-orbitals & three d-orbitals are mixed to give seven new hybrid
orbitals known as sp3d3 hybrid orbitals.

(b) In this hybridisation d-orbitals used are dxy, d x2  y2 & d z2 orbitals.

(c) These seven sp3d3 orbitals are configurated in pentagonal bipyramidal shape.
(d) Five bond angles are of 72° & ten bond angles of 90°.
(e) The following examples showing sp3d3 hybridisation –IF7 & XeF6.
F F

F F
I

F F
F
VALENCE SHELLELECTRON PAIR REPULSION THEORY (VSEPR) :
(a) Molecules having covalent bond have definite geometry as covalent bonding has directional characteristics. A
simple theory was given for the molecular shape of the covalent molecules by Gillespie and Nyholm in 1957.
(b) This theory predicts the shape of the molecule by considering the most stable configuration of the bond angles in
the molecule. This theory states
(i) Electron pairs in the valence shell of the central atom of a molecule, whether bonding or lone pairs are regarded
as occupying localised orbitals. These orbitals arrange themselves in so as to minimize the mutual electronic
repulsions.
(ii) The magnitude of the different types of electronic repulsions follows the order given below:
lone pair-lone pair > lone pair - bonded pair > bonded pair - bonded pair
(iii) The electronic repulsion between two pairs of electrons will be minimum if they are as far apart as possible.
(iv) The actual shape of the molecules containing lone pairs is a little distorted from the basic shape as in the NH3
and H2O molecules, the bond angles are not 109º28' but 107º and 104.5º respectively due to presence of one
lone pair in NH3 and two lone pairs in H2O.

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 CHEMICAL BONDING
Number of Molecule Electronic Bonding Non-bonding Molecular Example
Electron pairs Type Geometry Pair Pair (E) Geometry
2 AB2






2 0 B A B BeF2,BeCl2
Linear Linear
O C O etc

x
x
x
x

x
x

x
x
xx B

x
x
F
x x
x x

A
3 AB3 x
x
x 3 0 B B B
x

x
x

x
x
Trigonal planar
x
F
x x
F
x
Trigonal planar
x x x x

x x

x
x
N
AB2 Trigonal planar 2 1

x
x
B B O ,SO2, O3

x
x
x
O
x

x
x
x
x
Bent

xx B
H
A
4 AB4
xx xx 4 0 B B C
xx B H H
H
Tetrahedral Tetrahedral

x x

A xx
N
B B
AB3E Tetrahedral 3 1 B
H H
H
Trigonal pyramidal
x x

A xx
O

xx
x
B H
AB2E2 Tetrahedral 2 2
x
B
H
Bent

B

B

A B


B
5 AB5


5 0 PCl5


B
Trigonal bipyramidal
Trigonal bipyramidal

B
x
x

A B
AB4E Trigonal bipyramidal 4 1 B SF4
B
See saw

B
x
x

A B
AB3E2 Trigonal bipyramidal 3 2 ClF3
xx

B
T-shaped

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CHEMISTRY FOR NEET & AIIMS

B
x
x
x
A x

AB2E3 Trigonal bipyramidal 2 3 XeF2

xx
B
Linear

B
xx
x x B B
x x
A
x B B
6 AB6 x
x x 6 0 SF6
xx B
Octahedral
Octahedral

B B
A
AB5E Octahedral 5 1 B B BrF5
x x

Square pyramidal
x x

B B
A
B B
AB4E2 Octahedral 4 2 x x
XeF4
Square planar

Determination of hybridisation state

Method (I)
Count the following pair of e– around the central atom :
(a) Count all pure Vbonded electron pairs (or Vbonds)
(b) Count all lone pair of electron
(c) Count all coordinate bond.
(d) Count all negative charge.
Method (II)
To predict hybridisation following formulae may be used :
1
No. of hybrid orbital = [Total number of valence e– in the central atom + total number of
2
monovalent atoms – charge on cation + charge on anion]
1
Ex. NH 4 [ 5+ 4 – 1] = 4 sp3 hybridisation.
2
1
SF4 [6 + 4] = 5 sp3d hybridisation.
2
1
SO 24  [ 6 + 2] = 4 sp3 hybridisation.
2
( 'O' is divalent so add only charge on anion)
1
NO 3 [5 + 1] = 3 sp2 hybridisation.
2

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 CHEMICAL BONDING

If such type of e– pairs are –

two – sp hybridisation
three – sp 2 hybridisation
four – sp 3 hybridisation
five – sp 3 d hybridisation
six – sp 3 d 2 hybridisation
seven – sp 3 d 3 hybridisation
Bond length
x The internuclear distance between the two single covalently bonded atoms is called bond length or bond distance.
x If the electronegativities of both the atoms are equal, then the bond length is equal to the sum of the covalent radii
of two bonded atoms. d A – A = rA + r A
x If the electronegativities of two bonded atoms differ, then the bond length is smaller than the sum of their covalent
radii. dA – B < rA + rB
Factors Affecting Bond Length
(i) Size of Atoms
HI > HBr > HCl > HF
H2Te > H2Se > H2S > H2O
(ii) Hybridization State of The Bonded Atoms: If the s-character in hybridization state of the bonded atoms increases,
the C–H bond distance decreases.
1
Bond length v
Schracter
Ex. In C – C single bond.
sp3 – sp3 single bond length = 1.54 Å sp3 – sp2 single bond length = 1.52 Å
2 2
sp – sp single bond length = 1.51 Å sp3 – sp single bond length = 1.46 Å
2
sp – sp single bond length = 1.45 Å sp – sp single bond length = 1.37 Å
Bond length decreases in the order sp3 – sp3 > sp2 – sp2 > sp – sp
(iii) Resonance or Delocalisation of Electrons of The Bond: Bond length between atoms are changed if a molecule
shows resonance.
Due to resonance bond length affected
Ex. Benzene
C–C bond length 1.54 Å

C=C bond length 1.34 Å

But bond length is between single and double bond is = 1.39 Å
Ex. Bond length of C—O in CO2 is 1.15 Å Resonance occurs in CO2 is as follows :-
O=C=O l O– —C{O+ l O+ { C–O–
Bond length = 1.15 Å (Between double & triple bond)
Bond angle
x The angle between two bonds is known as bond angle.
Factors Affecting Bond Angle
(i) Hybridisation State of Central Atom: Compounds having different hybridisation have different bond angle.
Bond angle v % s character
Ex. BeH2 BH3 CH4
Hybridisation sp sp 2 sp 3
Bond angle 180º 120º 109º28'

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CHEMISTRY FOR NEET & AIIMS

(ii) Lone Pair of Electron: If compounds have same hybridisation states then bond angle depends on lone pair of
1
electron. Bond angle v
No. of lone pair
Ex. CH4 NH3 H2O
Hybridisation sp 3 sp 3 sp 3
Lone pair e – zero one two
Bond angle 109º28' 107º 105º
The different in bond angle is explained on the basis of following repulsion sequence
The repulsion between
lone pair-lone pair > lone pair - bonded pair > bonded pair - bonded pair
(iii) Electronegativity: When compounds having same hybridisation state of central atom and some number of lone pair
of electrons, then bond angle depends on electronegativity.
Bond angle v electronegativity
Ex. H2O > H2S
NH3 > PH3
E.N. of oxygen is more than sulphur therefore the bond angle in H2O will be more than H2S.
(iv) Size of Terminal Atoms: When size of terminal atoms increases, bond angle increases.
1
Bond angle v v size of side atom
electronegative of bonded atom
Ex. OF2 < Cl2O < Br2O
PF3 < PCl3 < PBr3
Bond Energy
x The amount of energy required to break one mole of the bond and separate the bonded atoms in the gaseous state
is known as the bond energy of that particular bond.
x B.E. is expressed in KJ mol–1 (in SI units) or in Kcal mol–1.
Factors Affecting Bond Energy
(a) Electronegativity : As the EN difference of the bonded atoms increases the bond energy increases because the
ionic nature of the bond increases.
Ex. Bond strength of hydrogen halides decreases in the order
H – F > H – Cl > H – Br > H – I
(b) Bond Order : increasing order of bond energy is
Bond energy v Bond order
C–C<C=C<C{C
(c) Hybridisation State of The Bonded Atoms :
Bond energy v s-character
Ex. –C – H < –C = H < – C { H
sp3 sp2 sp
(d) Atomic Size of Bonded Atoms : Atoms with small atomic radii form stronger bonds because the extent of overlapping
of atomic orbitals is more
Ex. B.E. of halogens is of the order
Cl – Cl > Br – Br > I – I
because their atomic sizes are in the order Cl < Br < I.
(e) Extent of Overlapping of Atomic Orbitals: A larger extent of overlapping of component atomic orbitals imparts great
strength to the bond.
(f) Repulsion Between the Lone Pairs of Electrons of Bonded Atoms:
1
Bond energy v
No. of lone pair of electron on the bonded atoms

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 CHEMICAL BONDING

Ex. the bond energies of the following single bonds having zero, one, two and three lone pair of electrons are in the
order.
xx xx xx xx xx xx
C – C > N– N> O– O > F – xFx

xx

xx

xx

xx
xx
(g) Resonance : Bond energy increase due to resonance
Ex. Use the VSEPR model to predict the geometry of the following :
(a) XeF2 (b) ClO3–
Sol. Species Structure

(a) XeF2 lone pairs occupy the equatorial positions to have minimum repulsion.

Thus it is linear.

(b) ClO3– To minimize the repulsion between lone pair and double

bond, species acquires trigonal pyramidal.

Ex. Discuss the bond angle in carbonyl halides COF2 , COCl2 , COBr2 , CO,2

Sol.

Bond angle T Ÿ COF2 < COCl2 < COBr2 < CO,2

Double bonds require more room than single bonds. Hence C = O group compresses the molecule and bond angle
decrease maximum in COF2 as bond pairs of electrons are more closer to the fluorine atoms because of high
electronegativity of fluorine. As size of halogen atoms increase and their electronegativity decreases repulsion
between bond pairs increases and therefore T increase.

Ex. Compare bond angle of OF2 , Cl2O and Br2O.

Sol. OF2 Cl2O Br2O

Bond pairs of electrons are more closer to the fluorine atoms (because of high electronegativity of fluorine). So the
Ap - Ap repulsion is more than bp - bp. Thus the F—O—F bond angle decreases to 102º from 109.5º. In Cl2O, the bond
pair are more closer to the oxygen atom because of the high electronegativity of oxygen. So the bp - bp repulsion is
more than Ap - Ap. Thus the bond angle Cl—O—Cl increases to |111º due to bp - bp repulsion and repulsion
between larger Cl atoms.
Note : The steric crowding of the larger halogen atoms also contributes in the increasing bond angles.
Ex. Which is linear PH4+ , H3S+ or NO2+ ?
(A) Phosphonium ion (PH4+) (B) Sulphonium (H3S+)
(C) Nitronium ion (NO2 ) .
+
(D) None of these
Sol. (C) Phosphonium ion (PH4 ) is tetrahedral, sulphonium (H3S+) is pyramidal, but nitronium ion (NO2+) is linear ;
+

(sp hybridisation).

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CHEMISTRY FOR NEET & AIIMS

Ex. The ONO angle is maximum in :

(A) NO3– (B) NO2+ (C) N2O4 (D) NO2

Sol. (B) (A) (B) Bond angle is 180º because of sp hybridisation of nitrogen.

(C) (D)

Ex. The triiodide ion (I3–) in which the I atoms are arranged in a straight line is stable, but the corresponding
F3– ion does not exist.
Sol. F3– and I3– are of same group. Iodine can expand its octet but F cannot and thus, in I3– octet rule is not
violated, but in F3– octet rule is violated.
Dipole moments & molecular polarity
(a) Polarity of any polar covalent bond or molecule is measured in terms of dipole moment.
(b) For measurement of extent of polarity, Pauling introduced the concept of dipole moment (P).
The product of positive or negative charge (q) and the distance (d) between two poles is called dipole moment.
G
Here - P = q × d (magnitude of charge × distance),
(c) Dipole moment is a vector quantitiy i.e. it has both magnitude as well as direction.
(d) Direction of dipole moment is represented by an arrow pointing from electro +ve to electro -ve element and from
central atom to lone pair of electrons.

or central atom lone pair electron

(e) Unit of dipole moment is Debye
1 Debye = 1 × 10–18 e.s.u. cm = 3.33 × 10–30 coulomb metre
(f) In the diatomic molecule P depends upon difference of EN i.e. PD'EN
order of P, H-F > H–Cl > H–Br > H–I
P = 0 for H–H, F–F, Cl–Cl, Br–Br, O–O
(g) For polyatomic molecule P depends on the vector sum of dipole moments of all the covalent bonds.
(h) For PCl5 and SF6, etc. m = 0 due to their symmeterical geometry.
(i) Benzene, naphthalene, diphenyl have P = 0 due to planar structure.
(j) If the vector sum is zero, than compound is non-polar compound or symmetrical compounds are non-polar.

(k) Dipole moment of H2O is 1.85 D which is resultant P of two O–H bonds.
P of H2O > P of H2S because electronegativity of oxygen is higher than sulphur.

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 CHEMICAL BONDING

(l) Angular structure of molecule have greater dipole moment.

(m) Any covalent bond which has a certain degree of polarity will have a corresponding dipole moment, though it does
not follow that compound containing such bonds will have dipole moment.

mresultant m12  m 22  2P1P 2 cos T

Ex. Write the order of the dipole moment of following compounds?

CH3Cl, CH2Cl2, CHCl3, CCl4
Sol. Right order is o CCl 4 < CHCl3 < CH 2 Cl 2 < CH 3Cl
P 0 1.02 1.55 1.93

Applications of Dipole Moment :

(a) To determine polarity and geometry of molecule :
If P = 0 compounds is non polar and symmetrical
e.g. CO2, BF3, CCl4, BeF2 etc.
If P z 0 compound will be polar and unsymmetrical.
H2O, SO2 NH3, Cl2O, CH3Cl, CHCl3 etc.

(b) To calculate % ionic character :

Experimental value of P
% Ionic character u 100
Theoritical Value of P
(c) To distinguish cis form or trans form :
(I) Dipole moment of cis isomers is normally higher than trans isomers.

eg. –

(II) If two groups have opposite inductive effect then trans-isomer will have greater dipole moment.

H Cl H Cl
C C
e.g. – C C
CH3 H H CH3

(d) To locate position of substituents in aromatic compounds.

1
PD
Bond angle

63
CHEMISTRY FOR NEET & AIIMS
(I) If same substituents are present in the symmetrical position P of benzene ring compounds will be zero.

(II) As angle between vector decreases value of P increases.

Ex. The resultant dipole moment of water is 1.85 D ignoring the effects of lone pair. Calculate, the dipole moment of each
OH bond (given that bond angle in H2O = 104°, cos 104° = – 0.25).
Sol. R2 = P2 + Q2 + 2PQ cos T
§ 1·
(1.85)2 = x2 + x2 + 2x2 ¨ - ¸
© 4¹

x2 3x 2
(1.85)2 = 2x2 – Ÿ
2 2
? x = 1.51 D
Ex. For HCl molecule observed dipole moment is 1.03 D and bond length is 1.275 Å. Calculate % ionic character.
Sol. Dipole moment = 4.8 × 10–18 × 1.275 × 10–8 = 4.8 × 1.275
1.03×100
% ionic character = | 17%
1.275 × 4.8

Ex. Why NH3 is having more dipole moment than NF3.

Sol. ,n molecule Nitrogen is more electronegative than Hydrogen. So the net dipole moment is towards. Nitrogen
atom but in NF3 molecule. Fluorine is more electronegative than. Nitrogen so the net dipole moment is towards
fluorine atoms. In NH3 the bond pair moments and lone pair moments are in the same direction while in NF3 the lone
pair moment and bond pair moments are in opposite direction.

..

N
F F
F

Ex. The geometry of SO3 and its dipole moment are :

(A) pyramidal and non-zero. (B) trigonal planar and non-zero.
(C) trigonal planar and zero. (D) T-shaped and zero.

Sol. (C)

The steric number of sulphur = 3; so hybridisation is sp2. There is no lone pair on sulphur atom, therefore, according
to VSEPR theory, the repulsions between the bond pairs of electrons will be similar. Hence the molecule will be
symmetrical (trigonal planar) with zero dipole moment.

64
 CHEMICAL BONDING
Electrovalent or Ionic bond
(a) The chemical bond formed between two or more atoms as a result of the complete transfer of one or
more electrons from one atom to another is called Ionic or electrovalent bond.
(b) Electro positive atom loses electron (group IA to IIIA)
(c) Electro negative atom gains electron (group VA to VIIA)
(d) Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond.
(e) Total number of electron lose or gained is called electrovalency.
Ex.
(i) Mg + O o Mg+2 + O–2
2, 8, 2 2, 6
2e –

electrovalency of Mg = 2
electrovalency of O = 2
–
Cl o Ca + 2Cl
(ii) +2
Ca +
2,8,8,2 2,8,7
One e –

Cl
2,8,7
One e –

electrovalency of Ca = 2
electrovalency of Cl = 1
–2
(iii) Ca + O o Ca+2 + O

2e –

electrovalency of Ca = 2
electrovalency of O = 2
(f) The force of attraction is equal in all direction so ionic bond is non-directional.
(g) A definite three dimensional structure is formed called crystal lattice.
(h) Ionic compound do not have molecular formula. It has only empirical formula.
Ex. NaCl is empirical formula of sodium chloride

Factors favouring Ionic Bonding :

(a) Ionisation Energy
Amount of energy required to remove an electron from the outermost orbit of an isolated gaseous atom to form the
+ve ion or cation. (energy absorbed)
Lesser Ionization energy oGreater tendency to form cation.

Ex. Na+ > Mg+2 > Al+3 ½

¾ Cation formation tendency
Cs+ > Rb+ > K+ > Na+ > Li+ ¿

(b) Electron Affinity

Amount of energy released when an electron is added to an isolated gaseous atom to form –ve ion (anion) energy
released.
Higher electron affinity oGreater tendency to form anion

65
CHEMISTRY FOR NEET & AIIMS

Ex. Cl– > F– > Br– > I–

F– > O–2 > N–3
(c) Lattice Energy - (Energy released)
The energy released in the formation of 1g mole electrovalent compound from isolated gaseous ions is called lattice
energy (U) of that compound.
Higher lattice energy oGreater will be the stability or strength of ionic compound.
Factors affecting lattice energy :
(i) Magnitude of charge oU Dz+ z– (Ionic charge)
Lattice energy DMagnitude of charge
NaCl MaCl2 AlCl3
Na + Mg +2 Al+3
o
– Lattice energy increases
– Size of cation decreases.

1
(ii) Size of Cation :- Lattice energy v
r+ + r-
LiCl NaCl KCl RbCl CsCl
o
– Size of cation increasing
– Size of anion is constant
– Lattice energy decreases.

Properties of Ionic Compound :

(a) Physical State – Ionic compounds are hard, crystalline and brittle due to strong electrostatic force of attraction.
Brittleness o{Same charged ions comes nearer. So they repell each other}

+ + + + + +

+ + + +
+ + +
+ + +
+ +
+ +

Attraction Repulsion
(b) Isomorphism : Different ionic compounds, having same configuration/geometry of ions are isomorphs of each
other and phenomenon is known as isomorphism
Ex. NaF, MgO, ZnSO4 · 7H2O, FeSO4 · 7H2O. All alums M2'SO · M2"(SO4)3 · 24H2O.
(c) Boiling Point and Melting Point –
Ionic compounds have high boiling point and melting point due to strong electrostatic force of attraction among
oppositely charged ions.
Melting Point : Melting point of ionic compounds
The two factors which mainly influence the melting point of ionic compound are
(i) Lattice enthalpy (ii) Polarisation
+ + + +
Cation = Na , K , Rb , Cs
M.P. v LE when OR
– –2 –3 –4 –
Anion = F , O , N , C , H
Melting point of ionic compound > covalent compound

66
 CHEMICAL BONDING

Except Giant molecules

p
Diamond, Carborundum (SiC)
Norbide (B4C), Silica (SiO2) Borazone (BN)x
Order of Hardness : Diamond > Norbide > SiC > Al2O3
(d) Conductivity – It depends on ionic mobility.
(i) In solid state - No free ions - Bad conductor of electricity.
(ii) In fused state or aqueous solution Due to free ions - Good conductor of electricity.
Conductivity Order Solid state < fused state < Aqueous solution
(e) Solubility – Highly soluble in water (Polar solvents) Ex. NaCl in water
(i) The Na+ ions get associates with - vely charged 'O' of water
(ii) And Cl– ions associates with +vely charged 'H' of water.

–
Cl

(iii) Thus charge on Na+ and Cl– decreases and electrostatic force of attraction also decreases which leads to
produce free ion.
(iv) The energy released due to interaction between solvent and solute is called solvation energy. If water is used
as solvent it is called hydration energy.
(v) For an ionic compound to be soluble in water – Hydration energy > Lattice energy
1
Lattice energy D
Solubility
Hydration energy DSolubility.
1 1
Hydration energy (H) D 
  { r+ & r– are radius of cation and anion}
r r

1 1
(vi) Hydration energy mainly depends on the cation radius because the value of is negligible in comparison to 
r r
(vii) Down the group both the lattice energy & hydration energy decreases, if decrease in lattice energy is greater
than hydration energy, solubility increases down the group and vice versa.
Factor affecting solubility
(A) Dielectric Constant of Solvent
The capacity of solvent to neutralise the charge of ionic compounds is called Dielectric constant. It is represented
by H
(i) Water has maximum dielectric constant (H= 80)
(CH3OH H= 35) , (Acetone H= 21)
(C2H5OH H= 27) , (Ether H= 4.1)
(Benzene H= 2.3)
H2O > CH3OH > CH3CH2OH > CH3COCH3 > CH3OCH3 > C6H6
(ii) Ionic compounds are more soluble in the solvents, having high dielectric constant.
(iii) H2SO4 and H2O2 have high dielectric constant but these are not a good solvent due to oxidising nature.

67
CHEMISTRY FOR NEET & AIIMS

(B) Size of Ion

(i) Keeping size of cation constant, the lattice energy decreases with the increase of anionic radius.
Hence order of solubility of LiX in water is LiF < LiCl < LiBr < LiI
1
As solubility D
lattice energy
(ii) In LiI covalent nature is more according to Fajan's rule but HE > LE therefore LiI is more soluble in water.
(iii) Keeping size of anion constant, the hydration energy decreases with the increase of cationic radius. Hence
order of solubility of MSO4 will be – BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4 ( Exception of Fajan's rule)
(iv) If size of cation and anion is very large, solubility decreases from top to bottom.
(v) Solubility decreases in a period (as ionic nature decreases and covalent nature increases)
NaCl > MgCl2 > AlCl3
TRANSITION FROM IONIC TO COVALENT BOND – FAJANS' RULE
(a) Just as a covalent bond may have partial ionic character an ionic bond may also show a certain degree of covalent
character. When two oppositely charged ions approach each other closely, the cation would attract the electrons in
the outer shell of the anion and simultaneously repel its nucleus. This produces distortion or polarization of the
anion, which is accompanied by some sharing of electrons between the ions, i.e., the bond acquires a certain
covalent character. The formation of a covalent bond between two ions may be illustrated with reference to formation
of Agl.

Ag+ Ag+ I– Ag+ ... I–

I–

distorted ion covalent character in ionic bond

separate ions
(b) Factors Influencing Ion – Deformation or Increasing Covalent Character
(i) Large Charge on the Ions :
The greater the charge on the cation, the more strongly will it attract the electrons of the anion. For example,
Al3+ can distort Cl– ion more than Na+ ion. So aluminium chloride is a covalent compound whereas NaCl, AlF3,
AgF are ionic.
(ii) Small Cation and Large Anion :
For a small cation, the electrostatic force with which its nucleus will attract the anion will be more. Moreover a
large anion cannot hold the electrons in its outermost shell, especially when they are attracted by a neighbouring
cation. Hence there will be increased covalent charcter with a small cation and a large anion, as in AgI.
(iii) Cation with a Pseudo-Inert Gas Type of Electronic Configuration :
A cation with a 18 electron in outermost shell such as Ag+ ([Kr] 4d10) polarizes anions more strongly than a
cation with a 8 electron arrangement as in K+. The 'd' electrons in Ag+ do not screen the nuclear charge as
effectively as the 's' and 'p' electron shell in K+. Thus AgI is more covalent than KI, although Ag+ and K+ ions
are nearly of the same size. Cuprous and mercurous salts are covalent.
The above statements regarding the factors, which influence covalent character, are called Fajans' rules. It can
thus be seen easily that there is nothing like a purely ionic compound or a purely covalent compound.
Polarisation power of a cation is usually called ionic potential or charge density.
Charge on cation
Ionic potential I(phi) =
Size of cation
Application of Concept of Polarisation
(a) To Determine Covalent and Ionic Character of Molecule
Covalent character
Iv
Ionic character
From left (larger size) to right (smaller size) in a period Iincreases so covalent character increases.

68
 CHEMICAL BONDING

Na+, Mg++ Al+++ Si++++

o
- charge increases
- size decreases Iincreases
- Covalent character increases with particular anion
From top to bottom in a group Idecreases so covalent, character decreases.
Li+
Na+ - Size increases (charge is fix)
K+ - Idecreases
Rb+ - Hence covalent character decreases with particular anion
Cs+
(b) To Determine Nature of Oxide

I < 2.2 (Basic oxides)

I = 2.2 to 3.2 (Amphoteric oxides)

Neutral oxides doesn't react with acid & base eg. H2O, CO etc.
Amphoteric oxides (Al2O3 etc.) reacts with acid & base

I > 3.2 (Acidic oxide)

Ex. Li2O, Na2O, K2O, Rb2O, Cs2O
o

– I decreases
– Basic character increases
(c) To Determine Conductivity of Metal Halides (MX)
If I < 2.2 MX - ionic nature

If I > 2.2 MX - covalent nature

(d) Formation of Complex Compounds
Smaller the cation, more will be the tendency of forming complex compounds.
High value of Ishows tendency of forming complex compounds.
If Iis low oNo or less tendency of forming complex compounds.
s-block metals (larger size) doesn't have the tendency to form complex compounds.
Exceptions - Li, Be, Mg (small size)
d-block metals have the tendency to form complex compounds (small in size, high charge).
1
(e) To Determine Thermal Stability of Metal Carbonates : stability D (Covalent nature)
I
1 size of cation
Thermal s v v
Pol. power ch arg e of cation

69
CHEMISTRY FOR NEET & AIIMS

More smaller the size of metal cation, its polarisation capacity increases - strength of M—O bond increases and C—
O bond decreases. So thermal stability of carbonates decreases.
CO3–2 o ' O–2 + CO2
From top to bottom thermal stability of carbonates increases (as size of cation increases)
(Ionic character increases or covalent character decreases)

For Halide, hydride & normal oxide

ª 1 º
«¬Thermal stability v size »¼ for a group

[Thermal stability v 'EN[ for a period

Thermal Stability order
For Example
BeSO4 < MgSO4 < CaSO4 < SrSO4 < BaSO4
LiNO3 < NaNO3 < KNO3 < RbNO3
LiHCO3 < NaHCO3 < KHCO3 < RbHCO3 < CsHCO3
Heating Effect
(a) Metal carbonate 
'
o metal oxide + CO2
(b) Metal hydroxide 
'
o metal oxide + H2O
(c) Metalo bicarbonate metal carbonate + CO2 + H2O
(d) Ammonium salts having CO3–2, PO4–3, SO4–2, X-anion (non oxidising or weak oxidising) gives NH3 gas
on decomposition.
Ammonium salt having Cr2O7–2, ClO3–1, NO2–1, NO3–1, (strong oxidising anion) gives N2 or N2O gas on
decomposition.
(e) Metal nitrate 
'
o metal oxide + NO2 + O2
1
Except : Na, K, Rb, Cs nitrate 
low temp.
o MNO 2  O 22

high temp. (>800°C)

M2O + N2 + O2
(f) To Explain Colour of Compounds
More the covalent character, more will be the colour intensity.
Colour density vI(Covalent character)
Ex. AgCl AgBr AgI
(White) (Light yellow (Dark yellow)
SnO2 SnS2
(White) (Yellow)

70
 CHEMICAL BONDING
Ex. AgCl is colourless whereas AgI is yellow, because of :
(A) Ag+ have 18 electron shell to screen the nuclear charge.
(B) Ag+ shows pseudo inert gas configuration.
(C) distortion of I– is more pronounced than Cl– ion.
(D) existence of d – d transition.
Sol. (C), the bigger anions are more polarised and hence their electrons get excited by partial absorption of visible
light.

s
MOLECULAR ORBITALTHEORY (MOT)
Given by hund & Mulican
(a) Two atomic orbital come nearer & then overlap each other to form two molecular orbitals (MO)
(b) Combination of two atomic orbital (AO) forms two molecular, orbital (MO):
ABMO (antibonding molecular orbital)
AO + AO
BMO (bonding molecular orbital)
(c)
Both orbitals can be filled by electrons according to Auffbau principle.
(d)
Energy of BMO < Energy of ABMO.
(e)
Order of energy in molecular orbitals of di-atomic molecules.
(i)
From H2 to N2:
V1s < V*1s < V2s < V*2s < S2pz = S2py < V2px < S *2pz = S *2py < V *2px
For N2 Molecule

^ V   pz

S S
n n n n n n
2p 2p
np
V pz
Increas i ng energy in N 2

np np
S  px

S py


np V  2 s
m ol e c u l e

np np
2 s 2 s
np
V  2s


np V  1 s

np np
1 s 1 s
np
V  1 s

71
CHEMISTRY FOR NEET & AIIMS
(ii) For O2 & F2:
V1s < V*1s ; < V2s < V*2s < V2px < S2pz = S2py < S *2pz = S *2py < V *2px
For O2 Molecule

V   p z
^
n n Bond order = ½ (8–4) = 2
S S
p x p y
np n n np n n
2p 2p
* Having two unpaired np np
electrons so paramagnetic S p x S  p y
np
V  p z

np V  2 s
Increasing energy

np np
2 s 2 s
np
V  2 s

np V  1 s

np np
1 s 1 s
np
V  1 s

V S = antibonding molecular orbital

VS= bonding molecular orbital
Nb  Na
Bond order =
2
Nb = No. of electron in bonding MO's
Na = No. of electron in antibonding MO's
(f) If bond order = 0, it means species does not exist.
(g) Bond order of 1, 2 & 3 corresponds to a single bond, double & triple bond respectively.
(h) Bond order nstability of molecule nbond length p
(i) If the molecule has one or more unpaired electron, it will be paramagnetic, while if all the electrons are paired it will
be diamagnetic.
Ex. H2 = Configuration : V(1s)2 V * (1s)0

Nb  Na 2 0
Bond order = = = 1, Hence H – H (diamagnetic)
2 2

72
 CHEMICAL BONDING

MO Electronic Configuration of Some Molecules

Molecule Total No. MO Configuration Bond Order Magnetic
or Ion of Electrons Behaviour
H2 2 (V  s)2 1 Diamagnetic
H2+ 1 (V 1s)1 0.5 Paramagnetic
H2 3 (V 1s)2, (V * 1s)1 0.5 Paramagnetic
He2 4 (V 1s)2, (V * 1s)2 0 Diamagnetic
N2 14 KK (V 2s)2, (V * 2s)2 , 3 Diamagnetic
(S 2py)2=(S 2pz)2, (V 2px)2
O2 16 KK (V 2s)2, (V * 2s)2 (V 2px)2, 2 Diamagnetic
(S 2py)2=(S 2pz)2 (S * 2py)1 (S * 2pz)1
O2+ 15 Remove one electron from 2.5 Paramagnetic
S * 2pz from O2
O22+ 14 Same as that of N2 3 Diamagnetic
O2 17 KK (V 2s)2, (V * 2s)2 (V 2px)2, 1.5 Paramagnetic
(S 2py)2,(S 2pz)2
(S *2py)2,(S *2pz)1
O22– 18 KK (V 2s)2, (V * 2s)2 (V 2px)2 1 Diamagnetic
(S 2py)2,(S 2pz)2
(S *2py)2,(S *2pz)2
F2 18 Same as above 1 Diamagnetic
Ne2 20 18 as above and (V * 2px)2 0 Diamagnetic
CO 14 Same as in N2 3 Diamagnetic
NO 15 Same as in O2+ 2.5 Paramagnetic
NO+ 14 Same as in N2 3 Diamagnetic
NO2+ 13 KK(V 2s)2 (V * 2s)2 (V 2px)2 2.5 Paramagnetic
(S 2py)1,(S 2pz)1
NO– 16 Same as in O2 2 Paramagnetic
CN 13 Same as in NO2+ 2.5 Paramagnetic
–
CN 14 Same as in N2 3 Diamagnetic

Ex. Though O2 molecule is paramagnetic yet it is a colourless gas. Why ?

Sol. It is because the energy gap between HOMO and LUMO levels in O 2 molecule is so large that radiations of visible
light cannot excite a e– from HOMO to LUMO. In fact O2 gas shows absorption in UV zone. So it is colourless.
Ex. Correct order of bond energy is:
(A) N2 > N2+ >N2– >N22– (B) N2+ >N2– >N22– >N2 (C) N2 >N2¯ = N2+ >N22– (D) N2– >N2 N2+ >N22–
Sol. (A) Bond order is directly proportional to the bond energy.
Bond order of N2 = 3 , N2+ , N2– = 2.5 N22– = 2
But N2– has more electrons in antibonding MO’s and thus N2+ is more stable than N2–. So correct order of bond
energy will be N2 > N2+ >N2– >N22–
Ex. Which of the following species have a bond order of 3 ?
(A) CO (B) CN– (C) NO+ (D) O2+
Sol. (A,B,C) Species CO, CN –, NO + are isoelectronic with 14 electrons to N 2 which has bond order of 3
10 - 4
(i.e. = 3), so their bond order will be equal to three.
3

73
CHEMISTRY FOR NEET & AIIMS
Ex. Which of the following are diamagnetic ?
(A) C2 (B) O22– (C) Li2 (D) N2+
Sol. (A,B,C) Species C2, O2 , Li2 have all the electrons paired but N2 has one unpaired electron in bonding molecular
2– +

orbital so it is paramagnetic.
Resonance
It is often observed that a single Lewis structure is inadequate for the representation of a molecule in conformity with its
experimentally determined parameters. For example, the ozone, O3 molecule can be equally represented by the structures
I and II shown below :
:

:
O O

:
O

m
12
m

pm

12
14
1p
8p

8p
8p
pm

8
12
14

12

m
m
:O: :O: : :
O :O : O O

:
:

I II III

Resonance in The O3 Molecule

(structures I and II represent the two canonical forms while the structure III is the resonance hybrid)
In both structures we have a O – O single bond and a O = O double bond. The normal O – O and O = O bond lengths are
148 pm and 121 pm respectively. Experimentally determined oxygen-oxygen bond lengths in the O3 molecule are same
(128 pm). Thus the oxygen-oxygen bonds in the O3 molecule are intermediate between a double and a single bond.
Obviously, this cannot be represented by either of the two Lewis structures shown above.
The concept of resonance was introduced to deal with the type of difficulty experienced in the depiction of accurate
structures of molecules like O3 . According to the concept of resonance, whenever a single Lewis structure cannot
describe a molecule accurately, a number of structures with similar energy, positions of nuclei, bonding and non-
bonding pairs of electrons are taken as the canonical structures of the hybrid which describes the molecule accurately.
Thus for O3 the two structures shown above constitute the canonical structures or resonance structures and their
hybrid i.e., the III structure represents the structure of O3, more accurately. This is also called resonance hybrid.
Resonance is represented by a double headed arrow.
Definition : Resonance may be defined as the phenomenon in which two or more structures involving in identical
position of atom, can be written for a particular compound
Resonance Hybrid : It is the actual structure of all different possible structures that can be written for the molecule
without violating the rules of covalence maxima for the atoms.

{
Resonance hybrid
Ex.

(i)

(ii) {

(iii) {

74
 CHEMICAL BONDING

(iv) {

Total No. of bonds formed between two atoms in all structures

• Bond order =
Total No. of resonating structures

2 +1+1
Ex. Bond order = = 1.33
3

• Resonance energy = Actual bond energy – Energy of most stable resonating structure.
• Stability of molecule D resonance energy.
• More is the number of covalent bonds in molecule more will be its resonance energy.
• Resonance energy D number of resonating structures.
HYDROGEN BOND
• An atom of hydrogen linked covalently to a strongly electronegative atom can establish an extra weak
attachment to another electronegative atom in the same or different molecules. This attachment is called a
hydrogen bond.
• To distinguish from a normal covalent bond, a hydrogen bond is represented by a broken line,
Ex. X – H ... Y where X and Y are two electronegative atoms. The strength of hydrogen bond is quite low
about 2-10 kcalmol–1 or 8.4-42 kJmol–1.
• Conditions of hydrogen bonding:
(i) The molecule must contain a highly electronegative atom linked to H-atom. (If E.N. n polarity of bond n)
(ii) The size of the electronegative atom should be small.(size p electrostatic attraction n)
Ex.
H H H H

H — N ····· H — N ····· H — N ····· H — N

H H H H

O O

• Strength of H-bond :
H .............. F bond dissociation energy = 41.8 kJ mol–1
H .............. O bond dissociation energy = 29.3 kJ mol–1
H .............. N bond dissociation energy = 12.6 kJ mol–1
• Effect of H-bond
(i) It causes the association of many molecules.
(ii) Due to hydrogen bond molecules are associated and show high molecular weight.
(iii) M.P. & B.P. of the molecules increases
(iv) Viscosity & surface tension of the molecules increases.
(v) The compounds which can form H-bond with the covalent molecules are soluble in such solvents.
Ex. : Alcohol & Ammonia are water soluble.

75
CHEMISTRY FOR NEET & AIIMS
Type of H-bonding
(a) Intermolecular (b) Intramolecular
(a) Intermolecular H-bond :
(i) This type of H-bonding takes place between two molecules.
Ex. ROH, H2O, R - OH & H2O
R R H H R H R
| | | | | | |
O – H ... O – H, O – H ... O – H, O – H ... O – H ... O – H
(ii) In such compounds molecular wt., M.P, & B.P. are high.
(iii) Extent of H-bonding n viscosity & density n.
(b) Intramolecular Bond :
(i) It is the H-bonding in the same molecule of a compound. The bonding also known as chelation.
(ii) Solubility in water, M.P. & B.P. of these compounds decreases.
(iii) The value of acid strength of acid depends on the relative stability of the acid and its conjugated base if the
intramolecular H-bonding stablises the conjugate base then, the acid strength increase and if the conjugate
acid is stabilised in this way then the acid strength decreased.
H-bond has serious consequences on the physical properties. These are –
(i) H2O is liquid at room temperature whereas H2S is gas at room temperature although H2S has greater molecular
weight.
(ii) Ice is lighter than water, although it solid because in ice H2O molecules are extending their H-bonds to full length
and six water molecules produce a cage like structure which is porous in nature leading to smaller mass and larger
volume, thus lowering the density.
(iii) Alcohols have higher boiling points than corresponding alkanes and there of the same molecular mass. This can be
explained by the intermolecular H-bonds existing among the R-OH molecules whereas ethers and hydrocarbon are
not capable to have such strong intermolecular forces. thus they have lower boling points.
H2O > R-OH > R-OH oExceptional
H2S < R-SH < R-S-R oNormal
H-bond increases
H2O > R-OH > R-O-R

B.P. increases
R-O-R o no H-bond
H2O o H-bonds
R-OH o H-bond.
(iv) Alcohol and water are miscible in any proportion due to formation of H-bonds.
(v) Ammonia is excessively soluble in water whereas other gases are partially soluble. This is due to the tremendous
capacity of NH3 molecule to generate 4-H-bonds.
NH3 > RNH2 > R2NH
(vi) Solubility order of different amines and ammonia in water follows the order NH3 > RNH2 > R2NH. This can be
explained by the capacity of these elements to form H-bonds.
(vii) KHF2 exists whereas KHCl2, KHBr2, KHI2 do not because KHF2 is constituted by 2 ions
–
i.e. K+ & HF2
–
[ ] [Cl ... H – Cl]
exist does not exist
KHF2 is a red orange coloured solid.

76
 CHEMICAL BONDING

(viii) o-nitro phenol is steam volatile and less H 2O soluble than its coresponding para isomer because in
o-nitro phenol, intra molecular H-bond exists which reduces the capacity of the molecule to produce intermolecular
H-bonds with other molecules like water. This brings interamolecular forces among the o-nitrophenol molecules
resulting into high volatility.
(ix) Acetic acid has a molecular weight of 60 in benzene and it shows a very high boiling points. This is due to
dimerization of molecule.
O – H ... O
CH3 – C C CH3
O ... H O
(x) Salicylic acid has very high acidity due to chelation of salicylate ion through the H-bond
–
O ··· H
C O

(xi) Chelation means to grab atoms in vicinity as much as possible.

(xii) Maleic acid has greater acidity than furmaric acid. This can also be explained by chelation of monomaleate anion
which has a H-bond between carboxylate anion adn the unionized carboxylic acid.

H—C O–

H—C OH

(xiii) Normally when 2 hydroxyl groups are present on the same carbon atom i.e. gem diols are unstable, but "chloralhydrate"
is a stable molecule due to formation of H-bond.
Cl ..... H — O

Cl C—C—H

Cl ..... H — O
O O
(xiv)
CH 3 C CH2 C CH 3
In the above compound, (acetyl acetone) enol form is stable because of the intramolecular H-bond.
H
O O

C C
CH3 CH3
CH

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CHEMISTRY FOR NEET & AIIMS
Ex. C2H2 is not soluble in H2O but it is highly soluble in acetone.

Sol.

In hybridisation as %S character increase electronegativity increase hence C2H2 forms H–bonds with O–atom of
acetone and get dissolved. But H2O molecules are so much associated that it is not possible for C2H2 molecules to
break that association, hence C2 H2 is not soluble in H2O.

Ex. Why SnCl2.2H2O readily loses one molecule of water at 80ºC ?

Sol. One water molecule is coordinated to lone pair of electrons on SnCl2 and the other is hydrogen bonded to coordinated
water molecules .

Ex. Why crystalline sodium peroxide is highly hygroscopic in nature.

Sol. Na2O2 forms stable hydrates on account of H-bonding.
- - -O 22 - - - - (H 2 O ) 8 - - - O 22 - - - - (H 2 O ) 8 - - -

Ex. Explain that tetramethyl ammonium hydroxide is a stronger base than that of trimethyl ammonium hydroxide.

ª CH3 º
CH3 « »
| |
« » –
CH3  N o H ˜ ˜ ˜ O  H «C H 3  N o C H 3 » O H
Sol. « »
| « | »
CH3 «
¬ CH 3 »
¼

In the trimethyl compound the O–H group is hydrogen bonded to Me3NH group and this makes it more difficult for
the OH group to ionize and hence it is a weak base.
In the tetramethyl compound, hydrogen bonding can not occur, so the OH– group ionizes easily and thus it is a
much stronger base.

VanderWaal's Forces
(a) These are the weakest type of inter molecular forces that exist among the molecules which being significant change
in physical properties.
(b) These are non-directional, non-valence cohesive forces. These attractive forces being played between the two
molecules are independent of the presence of other molecules.
(c) Solid, liquid or gaseous states of many molecules are explained on the basis of inter molecular forces other than
covalent, ionic or metallic bonds. Although inert gases do not form any type of bond but may exist in liquid and solid
states. This shows that the atoms of inert gases are attracted by each other through some type of inter molecular
forces. These intermolecular forces are called Vander Walls forces and may be of the following types:
(d) Ion-Dipole Attraction : Polar molecules are attracted by ions. The negative pole is attracted by cation and positive
pole attracted by the anion. This type of attraction is called ion dipole attraction, ion-dipole attraction is observed
generally in the process of solvation when sodium chloride (Na+ Cl–) is dissolved in water because negative poles
of water aggregate around Na+ ions and positive poles around Cl– ions.
H
+
Na ······ O
H
(e) Dipole-Dipole Attraction : The force of attraction between the oppositely charged poles of two polar molecules (for
example : H2O, H–F, NH3 etc.) is called dipole-dipole attraction. This type of attraction is weaker than the ion-dipole
attraction.

78
 CHEMICAL BONDING
O
H–Cl
·· H
·· ·· H
O

···
···
O
H H
H H
(f) Ion-Induced Dipole Attraction : When non polar molecules come in contact with ions, its electron cloud gets
polarised and the oppositely charged end of it is attracted by the ion. For example attraction between Na+ and Cl2
molecule.

Na+ + Cl – Cl o Na+ ........

(g) Dipole-Induced Dipole Attraction : This type of cohesive forces occurs in a mixture of polar and non polar
molecules. The former induce polarity in non polar molecules by disturbing their electron system. for example force
of attraction between Cl2 and H2O.
O H
+ Cl – Cl o O ........
H H H
(h) Induced-Induced Dipole : The weak intermolecular forces operating in similar non polar gaseous molecules are
called London forces. These forces are very weak in nature and exists only at low temperature. For example weak
intermolecular forces in F2, Cl2, N2, molecules and in noble gasses.

Ex. Give the order of boiling point of following

Cl2 , HCl
Sol. Cl2 – Cl2 < HCl – HCl (boiling point)
dispersion force dipole-dipole attraction
As dipole-dipole attraction is stronger than dispersion force.
Ex. Arrange the inert gases, according to their increasing order of boiling points
Sol. He < Ne < Ar < Kr < Xe (boiling point)
Because strength of van der Waal’s force increases down the group with increase in molecular mass.
Metallic bond
(a) The constituent particles of metallic solids are metal atoms which are held together by metallic bond.
(b) In order to explain the nature of metallic bond Lorentz proposed a simple theory known as electron gas model or
electron sea model.
(c) A metal atom is supposed to consist of two parts, valence electrons and the remaining part (the nucleus and the
inner shells) called kernel.
(d) The kernels of metal atoms occupy the lattice sites while the space between the kernel is occupied by valence
electrons.
(e) Due to small ionisation energy the valence electrons or metal atoms are not held by the nucleus firmly.
Therefore, the electrons leave the field of influence of one kernel and come under the influence of another kernel.
Thus the electrons are not localised but are mobile.
(f) The simulatneous attraction between the kernels and the mobile electrons which hold the kernel together is known
as metallic bond.

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CHEMISTRY FOR NEET & AIIMS
Some Special Bonding Situations :
(a) Electron Deficient Bonding
There are many compounds in which some electron deficient bonds are present apart from normal covalent bonds
or coordinate bonds which are 2c-2e bonds( two centre two electron bonds). These electron deficient bonds have
less number of electrons than the expected such as three centre-two electron bonds (3c-2e) present in diborane
B2H6, Al2(CH3)6, BeH2(s) and bridging metal carbonyls.
H H
Be Be Be
BeH2(s)
H H
H H H

H3C C CH3
Al Al
H3C C CH3 Al2(CH3)6

H H
H
But Al2Cl6 have covalent bond only and there is no electron deficient bonding as depicted in the given
structure.
Cl Cl Cl
Al Al
Cl Cl Cl
(b) Back Bonding
Back bonding generally takes place when out of two bonded atoms one of the atom has vacant orbitals
(generally this atom is from second or third period) and the other bonded atom is having some non-bonded electron
pair(generally this atom is from the second period). Back bonding increases the bond strength and decreases the
bond length. For example, in BF3 the boron atom completes its octet by accepting two 2p-electrons of fluorine into
2p empty orbital.

F
B F
F

Vacant Filled
2p-orbital 2p-orbital

(i) Decrease in B–F bond length is due to delocalised pS–pS bonding between filled p-orbital of F atom and vacant
p-orbital of B atom.
The extent of back bonding is much larger if the orbitals involved in the back bonding are of same size, for
example the extent of back bonding in boron trihalides is as follows :
BF3 > BCl3 > BBr3
There is pS-pS back bonding in boron trihalide. The extent of back bonding decreases from BF 3 to BI3 because
of increasing size of p-orbitals participating in back bonding that is from 2p(in F) to 4p(in Br).
(ii) The extent of back bonding decreases if the atom having vacant orbitals is also having some non-bonded
electron pairs on it. So among the atoms of third period the extent of back bonding follows the order
Si > P > S > Cl
1
(iii) The extent of pS-pS overlapping v
Lewis acid character

80
 CHEMICAL BONDING

Sr. No. Hybridisation Structure Bond Angle Examples

1. sp Linear F Be F 180° BeF 2

F
2. sp2 Triagonal planar B 120° BF 3
F F

H
C
3. sp3 Tetrahedral 109°28' CH 4
H H
H

Cl

Cl P Cl

Cl
4. sp3d Trigonal bipyramidal 3 orbitals-120° PCl5
2 perpendicular
Cl orbitals
Structure of PCl5

F
F F

5. sp3d2 Octahedral S 90° between SF6

all hybrid orbitals
F F
F

F F

6. sp3d3 pentagonalbipiramidal F F 5 bond angle 72° IF7

I and 10 bond
angles 90°
F F
F

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CHEMISTRY FOR NEET & AIIMS

SOLVED EXAMPLE
Ex. 1 Which of the following will be strongest Lewis Ex. 5 Which is incorrect statement ?
base ?
(A) In CF2=C=CF2 molecule all the four fluorine atoms
(A) CH3 CN (B) CH3 NH2
(C) N2 (D) None of these are not in the same plane.
Sol. (B) In CH3 NH2, hybridisation of N is sp3 while in (B) Ka2 of fumaric acid is more than Ka2 of maleic
CH3 CN hybridisation of N is sp. N2 is also sp acid due to intra molecular hydrogen bonding in
hybridised. maleic acid.
We know that in hybridisation, as s-character (C) The O–O bond length in O2[AsF4] is longer than
increases the electronegativity of atom also
increases. Due to this tendency the release of lone KO2.
pair of electrons becomes some what difficult. In (D) The bond angle order in halogen – S – halogen
methyl amine the nitrogen is in sp3 hybridisation is OSF2 < OSCl2 < OSBr2
and therefore the donation of the lone pair of
electron will be quite easier; so it is strongest Lewis Ans. (C)
base.
F pz py F
Ex. 2 Which type of hybridisation is found in H3O+ ? C C C
Sol. (A)
Sol. According to steric no. rule (s+p x+py) (s+px) (s+p +p )
F x z
F
Steric number = Number of bond pair(s) + number of As both carbon atoms are in different
lone pair(s) at central atom planes, all the four fluorine atoms are not in the
H O H
+ same plane.
H (B) maleic acid fumaric acid
So, steric number = 3 + 1 = 4. O
Thus the hybridisation of oxygen in H3O+ is sp3. O
H C C H
Ex. 3 Classify the following bonds as ionic, polar C O– O– C
covalent or covalent and give your reasons : H
(A) SiSi bond in Cl3SiSiCl3 C C O H
O
(B) SiCl bond in Cl3SiSiCl3 H H C
C
(C) CaF bond in CaF2 O
O
(D) NH bond in NH3 Due to intramolecular hydrogen bonding the maleate
Sol. (A) Covalent, due to identical electronegativity. ion gets stabilized and thus removal of second
(B) Covalent, due to less electronegativity hydrogen becomes quite difficult.
difference.
(C) I onic, due to more electro negativity (C) O2[AsF4] = O2+ B.O = 2.5
difference. KO2 = O2– B.O = 1.5
(D) Covalent, due to nearly simil ar
electronegativity. 1
Bond order v ; so O2+ has smaller
bond length
Ex. 4 (A) Which one has highest and lowest melting point
and why ? bond length than O2–
NaCl KCl RbCl CsCl (D) Greater the size of the halogen atoms greater will
(B) Why melting points of cesium halide (CsX) be the steric repulsions and thus larger will be the
decrease in the order given below ? bond angles.
CsF > CsCl > CsBr > CsI.
Ex. 6 Which of the compounds MgCO3 and ZnCO3 is
Sol. (A) NaCl will have highest lattice energy on account
of the smaller Na+ while CsCl has lowest lattice thermally more stable ? Explain.
energy on account of the larger Cs+. Hence NaCl Sol. Mg+2 has less polarising power due to inert gas
has highest melting point and CsCl has lowest
melting point . configuration while Zn+2 has higher polarising power
(B) As size of anions increase their polarisability due to pseudo inert gas configuration. A cation i.e.
increases thus their covalent character increases Zn2+ with a greater, polarising power exercise a
and melting point decrease.

82
 CHEMICAL BONDING
strong pull on the electron cloud of the neighbouring Ex. 12 Why crystals of hydrated calcium sulphate are soft
O-atom of the CO32– ion and as such the metal and easily cleaved where as anhydrous calcium
carbonate (ZnCO3) gets readily decomposed into sulphate are very hard and very difficult to cleave ?
CO2 and the oxide of the metal, ZnO. Thus ZnCO3 is Sol. With in the Ca2+ / SO42– layer the ions are held
less stable than MgCO3. together by strong electrovalent bonds but these
Ex. 7 Why is anhydrous HCl predominantly covalent in separated Ca2+ / SO42– layers are linked by relative
weak H–bond. The weak H-bonds link SO42– ion in
the gaseous state but is ionic in aqueous solution? the intermediate region.
Sol. It exists as HCl (bond formed by equal sharing of
electrons) but in aqueous solution ionises as H+ (or Ex. 13 The dipole moment of KCl is 3.336 × 10–29 Coulomb
–
H3O+) and Cl due to polarity of HCl. meter. The interionic distance in KCl is 2.6Å. Find
the % ionic character in KCl.
Ex. 8 Super oxides are coloured and paramagnetic why ?
Sol. Super oxides contain one unpaired electron in anti Sol. The theoretical dipole moment in KCl = e × d = 1.602
bonding molecular orbital and are coloured due to × 10–19 × 2.6 × 10–10 = 4.1652 × 10–29 C meter
transition of HOMO orbital electron within visible experimental dipole moment
% ionic character =
region. theoretical dipole moment
× 100 = (3.336 × 10–29/4.1652 × 10–29) × 100
Ex. 9 Of the species O 2 , O 2 , O2 and O 22 which would
have the maximum bond strength ? Ex. 14 For an ionic compound AX3 (s) formed between a
Sol. +
O2 has higher bond order i.e. 2.5 than O2(2) and metal A and a non-metal X (outermost shell
O2– (1.5) and bond strength is directly proportional configurationof X = ns2 np5). Find the enthalpy of
to bond order. formation (magnitude) of AX3(s) in k cal mol–1 with
the help of the following data. (Non-metal X is found
Ex. 10 Why BeF2 has zero dipole moment whereas H2O to exist in nature as a diatomic gas)
has some dipole moment ? 'HSublimation A(s) = 100 Kcal/mol
'H,E1 A(g) = 60 Kcal/mol
Sol. BeF2 has linear molecule and H2O has bent molecule.
'H,E2 A (g) = 150 Kcal/mol
F Be F
P=0 'H,E3 A(g) = 280 Kcal/mol
'Hdiss X2(g) = 80 Kcal/mol
'He.g X(g) = – 110 Kcal/mol
'HLattice energy A X3(s) = – 470 Kcal/mol
O

H H

Pz0

Ex. 11 A diatomic molecule has a dipole moment of 1.2 D. If

its bond distance is equal to 1.0Å then the fraction Sol.
of an electronic charge on each atom is :
(A) 25% (B) 37%
(C) 52% (D) 42% 3
Ans. (A) 'Hf = 'Hsub + 'H,.E1 + 'H,.E 2 + 'H,.E3 +
2
Sol. Assuming complete charge transfer then dipole 'Hdiss + 3 'He.g + 'HL.E
moment = (4.8 × 10–10 esu) (10–8 cm) = 4.8 D 3
= 100 + 60 + 150 + 280 + × 80 – 3 × 110 – 470
1.2 2
so % ionic character = × 100 % = 25%
4.8 = 100 + 60 + 150 + 280 + 120 – 330 – 470
= – 90 Kcal/mol

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CHEMISTRY FOR NEET & AIIMS
Ex. 15 CO forms weak bonds to Lewis acid such as BF3. In Ex. 17 There will be three different fluorine-fluorine
contrast CO forms strong bonds to transition metals. distances in molecule CF2 (C)2 CF2. Assuming
Why explain ? ideal bond angles for a particular hybridisation
Sol. CO m
V BF3 (assume no distortion due to double bonds) find
out the two smaller fluorine-fluorine distances
Transition metal CO and fill the result (in pm) in the increasing order
in your answer sheet. Round off your answer to
This is called synergic interaction and because of it
the nearest whole number.
the bond between CO and transition metal is
stronger. (Given that C–F bond length = 134 pm, C = C
bond length = 134 pm 3 = 1.73)
Ex. 16 The gaseous potassium chloride molecule has a
measured dipole moment of 10.0 D, which
indicates that it is a very polar molecule. The Sol.
separation between the nuclei in this molecule is
2.67 × 10 –8 cm. Calculate the percentage ionic
character in KCl molecule. d 1 = 2 × 134 × sin 60° pm = 231.8 pm = 232 pm
d 2 = 134 × 3 + 2 × 134 cos 60° pm = 536 pm
Sol. Dipole moment of compound would have been
completely ionic
= (4.8 × 10–10 esu) (2.67 × 10–8 cm) = 12.8 D
So % ionic character
10.0
= × 100% = 78.125 % ~ 78%
12.8

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 CHEMICAL BONDING

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. Which of the following statement is not correct for 8. Which of the following would have a permanent
sigma and pi-bonds formed between two carbon dipole moment ? [CBSE AIPMT 2005]
atoms ? [CBSE AIPMT 2003] (A) BF3 (B) SiF4
(A) Free rotation of atoms about a sigma bond is (C) SF4 (D) XeF4
allowed but not in case of a pi-bond
(B) Sigma bond determines the direction between 9. The correct sequence of increasing covalent
carbon atoms but a pi-bond has no primary character is represented by [CBSE AIPMT 2005]
effect in this regard (A) LiCl < NaCl < BeCl2 (B) BeCl2 < NaCl < LiCl
(C) Sigma bond is stronger than a pi-bond (C) NaCl < LiCl < BeCl2 (D) BeCl2 < LiCl < NaCl
(D) Bond energyies of sigma and pi-bonds are of 10. In which of the following molecules are all the bonds
the order of 264 kJ/mol and 347 kJ/mol. not equal ? [CBSE AIPMT 2006]
respectively
(A) ClF3 (B) BF3
2. Among the following, pair in which the two species
(C) AlF3 (D) NF3
are not isostructural, is [CBSE AIPMT 2004]
(A) SiF4 and SF4 (B) lO3– and XeO3 11. Which of the following species has a linear shape ?
(C) BH4 and NH4
– +
(D) PF6– and SF6 [CBSE AIPMT 2006]
3. In a regular octahedral molecule, MX6 the number (A) NO 2 (B) SO2
of X –M – X bonds at 180° is [CBSE AIPMT 2004]
(A) 3 (B) 2 (C) NO 2 (D) O3
(C) 6 (D) 4 12. The number of unpaired electrons in a paramagnetic
4. In an octahedral structure, the pair of d orbitals diatomic molecule of an element with atomic number
involved in d2sp3 - hybridisation is 16 is [CBSE AIPMT 2006]
[CBSE AIPMT 2004] (A) 2 (B) 3
d ,d (C) 4 (D) 1
(A) x 2  y2 z2 (B) d xz ,d x 2  y2
13. Which of the following is not isostructural with
(C) d z2 ,d xz (D) d xy ,d yz
SiCl4? [CBSE AIPMT 2006]
5. H2O is dipolar, whereas BeF2 is not. It is because (A) SCl4 (B) SO24
[CBSE AIPMT 2004]
(A) the electronegativity of F is greater than that of O (C) PO34 (D) NH 4
(B) H2O involves hydrogen bonding wherease BeF2
is a discrete molecule 14. The electronegativity difference between N and F is
greater than that between N and H yet the dipole
(C) H2O is linear and BeF2 is angular
moment of NH3 (1.5 D) is larger than that of NF3 (0.2
(D) H2O is angular and BeF2 is linear D). This is because [CBSE AIPMT 2006]
6. In BrF3 molecule, the lone pairs occupy equatorial (A) in NH3 as well as in NF3, the atomic dipole and
positions to minimise [CBSE AIPMT 2004] bond dipole are in the same direction
(A) lone pair-bond pair repulsion (B) in NH3, the atomic dipole and bond dipole are in
(B) bond pair-bond pair repulsion the same direction whereas in NF3 these are in
(C) lone pair-lone pair repulsion and lone pair-bond opposite directions
pair repulsion (C) in NH3 as well as NF3, the atomic dipole and
(D) lone pair-lone pair repulsion bond dipole are in opposite directions
(D) in NH3 the atomic dipole and bond dipole are in
7. Which of the following molecules has trigonal the opposite directions whereas in NF3 these
planar geometry ? [CBSE AIPMT 2005] are in the same directions
(A) IF3 (B) PCl3
(C) NH3 (D) BF3

85
CHEMISTRY FOR NEET & AIIMS
15. Which of the following is not a correct statement ? 21. According to molecular orbital theory which of the
[SBSE AIPMT 2006] following lists rank the nitrogen species in terms of
(A) The electron deficient molecules can act as Lewis increasing bond order ? [CBSE AIOMT 2009]
acids (A) N 2  N 2  N 22 (B) N 22  N 2  N 2
(B) The canonical structures have no real existence
(C) Every AB5 molecule does infact have square (C) N 2  N 22  N 2 (D) N 2  N 22  N 2
pyramid structure
(D) Multiple bonds are always shorter than 22. In the case of alkali metals, the covalent character
corresponding single bond decreases in the order [CBSE AIPMT 2009]
(A) MCl > Ml > MBr > MF
16. The correct order of C–O bond length among CO, (B) MF > MCl > MBr > Ml
CO32 , CO2 is [CBSE AIPMT 2007] (C) MF > MCl > Ml > MBr
(D) Ml > MBr > MCl > MF
(A) CO2  CO32  CO (B) CO  CO32  CO 2
23. In which of the following molecules/ions BF3, NO2– ,
(C) CO32  CO2  CO (D) CO  CO2  CO32 NH2– and H2O, the central atom is sp2 hybridised ?
[CBSE AIPMT 2009]
17. In which of the following pairs, the two species are (A) NO2– and NH2– (B) NH2– and H2O
isostructural ? [CBSE AIPMT 2007]
(C) NO2– and H2O (D) BF3 and NO2–
(A) SF4 and XeF4 (B) SO32 and NO3
24. What is the dominant intermolecular force on bond
(C) BF3 and NF3 (D) BrO3 and XeO3 that must be overcome in coverting liquid CH3OH
to a gas ? [CBSE AIPMT 2009]
18. The angular shape of ozone molecule (O3) consists
of [CBSE AIPMT 2008] (A) Hydrogen bonding
(A) 1 sigma and 2 pi-bonds (B) Dipole-dipole interaction
(B) 2 sigma and 2 pi-bonds (C) Covalent bonds
(C) 1 sigma and 1 pi-bonds (D) London or dispersion force
(D) 2 sigma and 1 pi-bonds 25. In which one of the following species the central
19. The correct order of increasing bond angles in the atom has the type of hybridisation which is not the
following triatomic species is same as that present in the other three ?
[CBSE AIPMT 2008] [CBSE AIPMT 2010]
(A) NO2  NO 2  NO 2 (A) SF4 (B) I3–
(C) SbCl52 – (D) PCl5
(B) NO2  NO 2  NO 2 26. The correct order of increasing bond angles in the
following species is [CBSE AIPMT 2010]
(C) NO2  NO 2  NO2 (A) Cl2O < ClO2 < ClO2– (B) ClO2 < Cl2O < ClO2–
(D) NO2  NO 2  NO 2 (C) Cl2O < ClO2– < ClO2 (D) ClO2– < Cl2O < ClO2
27. Which one of the following species does not exist
20. Four diatomic species are listed below in different
under normal conditions ? [CBSE AIPMT 2010]
sequences. Which of these presents the correct
(A) Be2+ (B) Be2
order of their increasing bond order ?
(C) B2 (D) Li2
[CBSE AIPMT 2008]
(A) O2  NO  C22  HE 2 28. In which of the following pairs of molecules/ions,
the central atoms have sp2 hybridisation ?
(B) NO  C22  O2  He2 [CBSE AIPMT 2010]
(A) NO2– and NH3 (B) BF3 and NO2–
(C) C22  He2  NO  O2 (C) NH2– and H2O (D) BF3 and NH2–
(D) He2  O2  NO  C22

86
 CHEMICAL BONDING
29. Which of the following has the miniumum bond 38. Which one of the following molecules contain no
length ? [CBSE AIPMT 2011] S-bond ? [NEET 2013]
(A) CO2 (B) H2O
(A) O2 (B) O22
(C) SO2 (D) NO2
(C) O2 (D) O2 39. Identify the correct order of solubility in aqueous
medium. [NEET 2013]
30. Which of the following is least likely to behave as
Lewis base ? [CBSE AIPMT 2011] (A) CuS > ZnS > Na2S (B) ZnS > Na2S > CuS
(C) Na2S > CuS > ZnS (D) Na2S > ZnS > CuS
(A) NH3 (B) BF3
(C) OH– (D) H2O 40. Which one of the following species has plane
triangular shape ? [CBSE AIPMT 2014]
31. Whcih of the two ions from the list given below,
(A) N3 (B) NO3–
have the geometry that is explained by the same
hybridisation of orbitals, [CBSE AIPMT 2011] (C) NO2–
(D) CO2

NO2 , NO3 , NH 2 , NH 4 ,SCN  ? 41. Which of the following molecules has the maximum
dipole moment ? [CBSE AIPMT 2014]
(A) NH 4 and NO3 (B) SCN  and NH 2 (A) CO2 (B) CH4
(C) NH3 (D) NF3
(C) NO2 and NH 2 (D) NO2 and NO3
42. Be2+ is isoelectronic with which of the following
32. Considering the state of hybridisation of carbon ions ? [CBSE AIPMT 2014]
atoms, find out the molecule among the following (A) H+ (B) Li+
which is linear ? [CBSE AIPMT 2011]
(C) Na+ (D) Mg2+
(A) CH3 – C { C – CH3
(B) CH2 = CH – CH2 C { CH 43. Which of the following options represents the
(C) CH3 – CH2 – CH2 – CH3 correct bond order ? [CBSE AIPMT 2015]
(D) CH3 – CH = CH – CH3 (A) O2 ! O2 ! O2 (B) O2  O2  O2
33. The pari of species with the same bond order is (C) O2 ! O2  O2 (D) O2  O2 ! O2
[NEET 2013]
44. Which of the following pairs of ions are isoelectronic
(A) O22 ,B2 (B) O2 , NO
and isostructural ? [CBSE AIPMT 2015]
(C) NO, CO (D) N2, O2
(A) CO32 ,SO32 (B) ClO3 ,CO32
34. Which of the following species contains three bond
pairs and one lone pair around the central atom ? (C) SO32 , NO3 (D) ClO3 ,SO32
[NEET 2013]
(A) H2O (B) BF3 45. Which of the following species contains equal
number of V and S-bonds ? [NEET 2016, Phase II]
(C) NH2– (D) PCl3
(A) HCO3– (B) XeO4
35. Bond order of 1.5 is shown by [NEET 2013]
(C) (CN)2 (D) CH2(CN)2
(A) O2+ (B) O2–
(C) O22 – (D) O2 46. Which of the following pairs of ions is isoelectronic
and isostructural ? [NEET 2016, Phase II]
36. Which of the following is paramagnetic ?
[NEET 2013] (A) CO32 , NO3 (B) ClO3 , CO32
(A) CO (D) O2–
(C) SO32 , NO3 (D) ClO3 ,SO32
(C) CN– (D) NO+
37. Which of the following is a polar molecule ? 47. The hybridisations of atomic orbitals of nitrogen in
NO2+, NO3– and NH4+ respectively are
[NEET 2013]
[NEET 2016, Phase II]
(A) BF2 (B) SF4
(A) sp, sp and sp
3 2
(B) sp2, sp3 and sp
(C) SiF4 (D) XeF4
(C) sp, sp and sp
2 3
(D) sp2, sp and sp3

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CHEMISTRY FOR NEET & AIIMS
48. Which one of the following compounds shows the 53. Consider the following species:
presence of intramolecular hydronge bond ? CN+, CN–,NO and CN
[NEET 2016, Phase II]
Which one of these will have the highest bond
(A) H2O2 order ? [NEET 2018]
(B) HCN
(C) Cellulose (A) CN+ (B) CN– (C) NO (D) CN
(D) Concentrated acetic acid 54. In the structure of CIF3, the number of lone pairs
of electrons on central atom 'Cl' is. [NEET 2018]
49. Consider the molecules CH4, NH3 and H2O. Which
of the given statements is false ? (A) four (B) two (C) one (D) three
[NEET 2016, Phase I]
(A) The H–O–H bond angle in H2O is larger than the 55. The correct order of N-compounds in its decreas-
H–C–H bond angle in CH4 ing order of oxidation states is [NEET 2018]
(B) Then H–O–H bond angle in H2O is smaller than (A) HNO3, NH4 Cl, NO, N2
the H–N–H bond angle in NH3 (B) HNO3, NO, NH4 Cl, N2
(C) The H–C–H bond angle in CH4 is larger than the
(C) HNO3, NO, N2, NH4 Cl
H–N–H bond angle in NH3
(D) The H–C–H bond angle in CH4, the H–N–H bond (D) NH4 Cl, N2, NO, HNO3
angle in NH3 and the H–O–H bond angle in
H2O are all greater than 90° 56. Which of the following oxides is most acidic in
nature ? [NEET 2018]
50. Predict the correct order among the following. (A) BaO (B) BeO
[NEET 2016, Phase I] (C) MgO (D) CaO
(A) lone pair -lone pair > bond pari-bond pair > lone
pair-bond pair
(B) bond pair-bond pair > lone pair-bond pair > lone
pair-lone pair
(C) lone pair-bond pair > bond pair-bond pair > lone
pair-lone pair
(D) lone pair-lone pair > lone pair-bond pair > bond
pair-bond pair
51. Which one of the following pairs of species have
the same bond order ? [NEET 2017]
(A) CO, NO (B) O2, NO+
(C) CN–, CO (D) N2, O2–

52. Magnesium reacts with an element (X) to form an

ionic compound. If the ground state electronic
configuration of (X) is 1s2 2s2 2p3, the simplest
formula for this compound is. [NEET 2018]
(A) Mg2X (B) MgX2
(C) Mg2X3 (D)Mg3X2

88
 CHEMICAL BONDING

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

1. Which of the following compounds possesses the 9. The molecule having the same hybridisation, shape
C–H bond with the lowest bond dissociation and number of lone pairs of electrons are [2009]
energy ? [2003] (A) SeF4, XeO2F2 (B) SF4, XeF2
(A) Toluene (C) XeOF4, TeF4 (D) SeCl4, XeF4
(B) Benzene
(C) n-Pentane 10. Which of the following conditions is not correct for
resonanting structures ? [2010]
(D) 2, 2 - Dimethylpropane
(A) The contributing structures must have the same
2. Which of the following are arranged in the
number of unpaired electrons.
decreasing order of dipole moment ? [2003]
(B) The contributing structures should have similar
(A) CH3Cl, CH3Br, CH3F
energies.
(B) CH3Cl, Ch3F, CH3Br
(C) The contributing structures should be so writ-
(C) CH3Br, CH3Cl, CH3F ten that unlike charges reside on atoms that are
(D) CH3Br, CH3F, CH3Cl far apart.
3. The ONO angle is maximum in [2004] (D) The positive charge should be present on the
electropositive element and the negative charge
(A) NO3 (B) NO2 on the electronegative element.
(C) NO2 (D) NO2 11. CaO and NaCl have the same crystal structure and
apporximately the same ionic radii. If U is the lattice
4. Among the following, the species having squear
energy of NaCl, the approximate lattice energy of
planar geometry for central atom are [2006]
CaO is [2010]
(i) XeF4, (ii) SF4, (iii) [NiCl4]2–, (iv) [PdCl4]2–
(A) U/2 (B) U
(A) (i) and (iv) (B) (i) and (ii)
(C) 2U (D) 4U
(C) (ii) and (iii) (D) (iii) and (iv)
12. Decreasing order of bond angle is [2011]
5. In [Ag(CN)2]–, the number of S bonds is [2006]
(A) BeCl2 > NO2 > SO2 (B) BeCl2 > SO2 > NO2
(A) 2 (B) 3
(C) SO2 > BeCl2 > NO2 (D) SO2 > NO2 > BeCl2
(C) 4 (D) 6

6. Bond length order is [2007]

13. The dipole moment is minimum in [2012]

(A) O2 < O3 < O22– (B) O2 < O22– < O3 (A) NH3 (B) NF3
(C) O22– < O3 < O2 (D) O2 = O22– > O3 (C) SO2 (D) BF3

7. Which of the following does not contain any 14. Total number of antibonding electrons present in
coordinate bond ? O2 will be [2013]
(A) 6 (B) 8
(A) H3O+ (B) BF4
(C) 4 (D) 2
(C) HF2 (D) NH 4
15. In BF3, the B–F bond length is 1.30 Å, when BF3 is
8. The correct order of diople moment is [2008] allowed to be treated with Me3N, it form an adduct,
(A) CH4 < NF3 < NH3 < H2O Me3N o BF3, the bond length of B–F in the adduct
(B) NF3 < CH4 < NH3 < H2O is [2013]

(C) NH3 < NF3 < CH4 < H2O (A) greater than 1.30 Å (B) smaller than 1.30 Å
(D) H2O < NH3 < NF3 < CH4 (C) equal to 1.30 Å (D) none of these

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CHEMISTRY FOR NEET & AIIMS
16. In O3 molecule, the formal charge on the central (A) If both the assertion and reason are true and
O-atoms is [2014] reason explains the assertion
(A) 0 (B) –1 (B) If both the assertion and reason are true but
reason does not explain the assertion
(C) –2 (D) +1
(C) If assertion is true but reason is false
17. Which of the following represents the correct bond (D) If assertion is false but reason in true
order ? [2014] (E) Both assertion & reason are false

(A) O 2  O 2 ! O 22 (B) O 2  O 22 ! O 2 23. Assertion : All F – S – F angle in SF4 is greater than
90° but less than 180°.
(C) O 22 ! O 2 ! O 2 (D) O 2 ! O 2 ! O 22
Reason : The lone pair-bond pair repulsion is weaker
than bond pair-bond pair repulsion.
18. Which of the following molecules has more than
[2004]
one lone pair ? [2016]
24. Assertion : Molecular nitrogen is less reactive than
(A) SO2 (B) XeF2 molecular oxygen
(C) SiF4 (D) CH4 Reason : The bond length of N2 is shorter than that
19. Four diatomic species are listed below in different of oxygen. [2006, 2015]
sequences. Which of these represents the correct
order of their increasing bond order ? [2016] 25. Assertion : SeCl4 does not have a tetrahedral
structure.
(A) C 22  He 2  NO  O 2
Reason : Se in SeCl4 has two lone pairs.
(B) He 2  O 2  NO  C 22 [2008]
26. Assertion : Bond energy and bond dissociation
(C) O 2  NO  C 22  He 2
energy have identical value for diatomic molecules.
(D) NO  C 22  O 2  He 2 Reason : Greater the bond dissociation energy, less
20. Hybridisation states of C in CH3+ and CH4 are reactive is the bond. [2010]
(A) sp2 & sp3 (B) sp3 & sp2
(C) sp & sp
2 2
(D) sp3 & sp3 [2017]
27. Assertion : CIF3 has T-shape structure.
Reason : It has two lone pairs arranged at 180° angle.
21. Which of the following cantain at least one lone [2012]
pair in all of its halide 28. Assertion : O2 is paramagnetic.
(A) Xe (B) Se Reason : It has one unpaired electron.
(C) Cl (D) N [2018] [2012]

22. Which is incorrect regarding S and P mixing (along 29. Assertion : Both rhombic and monoclinic sulphur
Z –axis.) exist as S8 but oxygen exists as O2. [2017]
(A) Nodal plane(s) present in ABMO
Reason : Oxygen forms pS – pS multiple bond due
(B) Nodal plane is absent in BMO
to small size and small bond length but pS – pS
(C) MO formed may have higher energy than parent
bonding is not possible in sulphur.
AO
30. Assertion : Lithium carbonate is not so stable to
(D) MO formed are asymmetric [2018]
heat. [2017]
Reason : Lithium being very small in size polarizes
ASSERTION AND REASON
large CO32  ion leading to the formation of more
In each of the following questions, two statement stable Li2O and CO2
are given one is assertion and the other is reason.
Examine the statement carefully and mark the correct
answer according to the instruction given below

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CHEMISTRY FOR NEET & AIIMS

ANSWER KEY

EXERCISE : PART - I
1. D 2. A 3. A 4. A 5. D 6. D 7. D 8. C 9. C 10. A 11. C 12. A 13. A
14. B 15. C 16. D 17. D 18. D 19. B 20. D 21. B 22. D 23. D 24. A 25. C 26. D
27. B 28. B 29. D 30. B 31. D 32. A 33. A 34. D 35. B 36. B 37. B 38. B 39. D
40. B 41. D 42. B 43. B 44. D 45. B 46. A,D 47. C 48. C 49. A 50. D 51. C 52. D
53. B 54. B 55. C 56. B

PART - II
1. A 2. B 3. D 4. A 5. C 6. A 7. C 8. A 9. A 10. C 11. D 12. A 13. D
14. A 15. A 16. D 17. D 18. B 19. B 20. A 21. A 22. B 23. C 24. A 25. C 26. B
27. C 28. C 29. A 30. A

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CHEMISTRY FOR NEET & AIIMS

EXERCISE
P-1 (NEET/AIPMT)

1. (D) Bond energy of sigma bond is greater than pi bond

thus their energies between C -atoms are 347 kJ mol–1
and 264 kJ/mol respectively.
2. (A) SiF4 and SF4 are not isostructural because SiF4 is
tetrahedral due to sp3 hybridisation of Si.
14
Si = 1s2, 2s2, 2p6, 3s23p2 (in ground state)
14
Si = 1s2, 2s22p6, 3s13p2 (in excited state)

3s 3p

sp3 hybridisation

Hence, four equivalent sp3 orbitals are obtained they are

overlapped by four p-orbitals of four fluorine atoms on
their axis. thus, it shows following structure :

F F
4PMVUJPOT or
Si Si

F F F F
F F

While SF4 is not tetrahedral but it is arranged in trigonal

bipyramidal geometry (has see saw shape) because in it
S is sp3d hybrid.

16 S 1s 2 , 2s 2 2p6 ,3s 2 3p 2x 3p1y 3p1z

(in ground state)

1s 2 , 2s 2 2p6 ,3s 2 3p1x 3p1y 3p1z 3d1xy

 

sp3 d hybridisation

92
 CHEMICAL BONDING
(in first exctation state) 6. (D) In BrF3 molecule, Br is sp3d hybridised, but its
geometry is T-shaped due to distortion of geometry from
F F F trigonal bipyramidal to T-shaped by the involvement of
lone pair-lone pair repulsion.
F S or S
F
F F F
F Br
Hence, five sp d hybrid orbitals are obtained. One
3
F
F
orbital is already paired and rest four are overlapped
with four p-orbitals of four fluorine atoms on their axis in Here, lp – lp repulsion = 0
trigonal bipyramida form. lp – lp repulsion = 4
This structure is distorted from trigonal bypyramidal to lp – lp repulsion = 2
tetrahedral due to involvement of repulsion between lone
pair and bond pair. 7. (D) IF3 has bent-T geometry

3. (A) In octahedral structure MX6, the six hybrid orbitals F

(sp3d2) are directed towards the cornes of a regular
I F
octahedral with an angle of 90°. According to following
structure of M X6, the number of X – M – X bonds at F
180° must be three.
2lp + 3 bp = sp d hybridisation
3

X PCl3 has pyramidal geometry

X X

M
P
Cl Cl
X X Cl
X
1lp + 3 bp = sp3 hybridisation
4. (A) In the formation of d2sp3 hybrid orbitals, tow NH3 has trigonal pyramidal geometry

(n – 1) d-orbitals of eg set, ie.e. (n-1) dz2 and (n  1)d x 2  y2

orbitals, one ns and three np (npx, npy and npz.) orbitals N
combine together. H H
H
5. (D) The structure of H2O is angluar of V-shape and has
sp 3-hybridisation and 104.5° bond angle. Thus, its 1 lp + 3bp = sp3 hybridisation
dipole moment is positive or more than zero. BF3 has trigonal planar geometry
O F
F B
104.5° F
H H
(μ = 0)
But in BeF2, structure is linear due to
3bp only = sp2 (hydridisation)
sp dybridisation (μ = 0)
180°
F F
8. (C)
F Be F
B Si
Thus, due to μ > 0, H2O is dipolar and due to μ = 0, BeF2
F F F F
is non-polar.
F
μ=0 μ=0

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CHEMISTRY FOR NEET & AIIMS

.. .. +
F F F F S N O
S Xe
O O O O O O
F F F .. F V-shape V-shape V-shape
μ = 0.632 D μ=0
Angular shape (due to sp2 hybridisation of central atom or ion)
(Permanent dipole moment)
' SF4 have μ > 0
12. (A) Suppose the diatomic molecule is X.
? It has permanent dipole moment.
Then, molecular orbital electronic confiugration of
9. (C) On the basis of Fajans’ rule, lower the size of cation, * *
higher will be its polarising power and higher will be 16 X V1s 2 , V1s 2 , V2s 2 , V 2s 2 , V2p 2z , S2p 2x
covalent character.
* *
1 | S2p 2y , S 2p1x | S 2p1y
? Polarising power v
size of cation Due to presence of two unpaired electrons, it shows
Covalent character v polarising power paramagnetic character.
So, the correct order is 13. (A) SCl4 is not isostructural with SiCl4 because it shows
NaCl < LiCl < BeCl2 square planar structure due to involvement of repulsion
(' The order of size of cation Na+ > Be2) between lone pair and bond pair of electrons.

10. (D) In ClF3 all bonds are not equal due to its trigonal- SO24 shows tetrahedral structure due to sp 3
bipyramidal (sp3d hybridisation) geometry hybridisation.

.. F PO34 shows tetahedral structure due to sp 3

F Cl
.. hybridisation.
F
Trigonal bipyramidal geometry NH 4 shows shows tetrahedra structure due to sp 3
BF3 and AlF3 show trigonal symmetric structure due to hybridisation.
sp2 hybridisation.
F F 14. (D)
F B and F Al N N
F F F F H H
NF3 shows pyramidal geometry due to sp3 hybridisation. F H
.. μ = 0.24 D μ = 1.47 D
N
F F F is more electronegative than N, therefore direction of
F bond is from N to F whereas N is more electronegative
3bp + 1lp than H, the direction of the bond is from H to N. Thus
whereas resultant moment of N-H bonds adds up to the

bond moment of lone pair, that of 3N-F bonds partly
11. (C) N O 2 has linear shape due to sp hybridisation of N cancel the resultant moment of lone pair. Hence, the net
dipole moment of NF3 is less than that of NH3.

in N O 2
15. (C) Generally, AB5 molecules have trigonal bipyramidal
 structure due to sp3d hybridisation but in some cases
O N O due to presence of lone pair of electrons, its geometry be
While SO2, NO2 and O3 have angular shape
–

94
 CHEMICAL BONDING
16. (D) A bond length is the average distance between the 20. (D) The molecular orbital configuration of
centres of nuclei of two bonded atoms. A multiple bond * *
(double or triple bonds) is always shroter than the O 2 (8  8  1 17) 1s 2 , V1s 2 , V 2s 2 , V 2s 2 ,
corresponding single bond.
* *
The C-atom in CO32 is sp2 hybridised as shown : V2p 2x , S2p 2y | S2p 2z , S 2p 2y | S 2p1z

O O O N b  Na 10  7
Bond order (BO) 1.5
O C O C O C 2 2
O O O * *

The C-atom on CO2 is sp hybridised with bond distance NO(7  8 15) V1s 2 , V1s 2 , V2s 2 , V 2s 2 , V2p 2x
carbon -oxygen is 122 pm. * *

  
S2p 2y | S2p2z , S 2p1y | S 2p0z
O C O mo  O { C  O mo O C { O
The C-atom in CO is sp hybridised with C–O bond 10  5
BO 2.5
distance is 110 pm. 2
:C { O+: * *

So, the correct order is C 22 (6  6  2 14) V1s 2 , V1s 2 , V 2s 2 , V 2s 2 ,

CO < CO2 < CO32 –
S2Py2 | S2pz2 , V2p 2x
17. (A) SF4 = irregular tetrahedral (sp3d, one lone pair)
XeF4 = square planar (sp3d2, two lone pairs) 10  4
BO 3
2
(B) SO32 = pyramidal (sp , one lone pair)
3

*
He 2 (2  2  1 3) V1s 2 , V1s1
NO3 =trigonal planar (sp2)
(C) BF3 = trigonla planar (sp2) 2 1 1
BO 0.5
NF3 = trigonal planar (sp2) 2 2
(D) BrO3– = pyramidal (sp3, one lone pair) Hence, order of increasing bond order is
XeO3 = pyramidal (sp3, one lone pair)
He2  O2  NO  C22
18. (D) In case of single bond, there is only one V-bond, in
21. (B) According to the molecular orbital theory (MOT)
case of double bond, there is one V and one S-bonds
while in case of triple bond, there is one V and two * *
N2(7 + 7 = 14) = V1s 2 , V1s 2 , V 2s 2 , V 2s 2 , S2p 2x
S-bonds. Thus, angular shape of ozone (O2) contains
2V and 1 S-bonds as shown below | 2p 2y , V2p z2
O
10  4
O O Bond order 3
2
* *
19. (B) According to VSEPR theory. N 2 (7  7  1 15) V1s 2 , V1s 2 , V2s 2 , V 2s 2 ,
The order of repulsion of electrons is lp-lp repulsion > *
lp-bp repulsion > bp-bp repulsion Higher the number V2p 2z , S2p 2x | 2p 2y , S 2p1x
olone pair of electrons (greater is repulsion) lower is the
bond angle and vice-versa. In NO2– one lone pair of 10  5
BO 2.5
electron is present while in NO2+ no lone pair of electron 2
is present. Hence, the correct order of bond angles is
NO2– < NO2 < NO2+

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CHEMISTRY FOR NEET & AIIMS

* * 25. (C) Key Idea Molecules having same hybridisation have

N 22 (7  7  2 16) V1s 2 , V1s 2 , V 2s 2 , V 2s 2 ,
same number of hybrid orbitals,
* *
V2p 2z , S2p2x | S2p 2y , S 2p1x | S 2p1y 
H [V  X  C  A]
2
10  6 where,
BO 2
2 V = number of valence electrons of central atom
Hence, the increasing order of bond order is, X = number of monovalent atoms
C = change on cation
N 22  N 2  N 2
SbCl52 sp3d 2 ,PCl5 sp3d
22. (D) According fo Fajans’ rule,
SF4 sp3d, I3 sp3d
1
Covalent character v
sizeof cation 26. (D) According to VSEPR theory repulsion order
v size of anion lp – lp > lp – bp > bp – bp
In the given options, cation is same but anion are Key Idea As the number of lone pair of electrons
different, Among halogens the order of size is increases, bond angle decreases due to repulsion
F < Cl < Br < I between lp – lp. Moreover, as the electronegativity of
? Order of covalent character is Hence, the order of bond angle is
MI > MBr > MCl > MF
Cl O Cl
< <
23. (D) BF3
O O Cl Cl O O
F (two lone pairs) (two lone pairs) (one lone pair)

B F Ÿ 3 V-bond, i.e. sp2 hybridisation (Cl is less electronegative as compared to O).

F 27. (B) Key Idea Molecules with zero bond order, do not
Plant structure exist.
NO2– According to molecular orbital theory,
(A) Be2+ (4 + 4 – 1 = 7)
V .. V
H  N  H Ÿ 2V-bonds +1 lone pair of electrons,
.x * *
V1s 2 , V1s 2 , V2s 2 , V 2s1
i.e., sp2 hybridisation

O 43
Bond order (BO) 0.5
H2O = 2
H H
* *
Ÿ 2V-bonds +2 lone pairs, i.e. sp3 hybridisation, Thus, (B) Be 2 (4  4 8) V1s 2 , V1s 2 , V2s 2 , V 2s 2
in BF3 and NO2– , central atom is sp2 hybridised, while
NH2, NH3 and H2O are sp3 hybridised. 44
BO 0
24. (A) In between CH 3OH molecules intermolecular 2
H-bonding exist. (C) B2( 5 + 5 = 10)
* *
H O H O H O V1s 2 , V1s 2 , V2s 2 , V 2s 2 , S2p1x | S2p1y
CH3 CH3 CH3
6 4
Intermolecular H-bond Bond order (BO) = 1
2
Hence, it is the intermolecular H-bonding that must be
overcome in converting liquid CH3OH to gas.

96
 CHEMICAL BONDING
28. (B) Key Idea For sp 2 hybridisation, there must be
Nb  Na 10  8
3V-bonds or 2V-bonds along with a lone pair of Bond order (BO) 1
2 2
electrons.
(i) NO2– Ÿ 2V + 1 lp = 3, i.e., sp2 hybridisation * *
B2 (5  5 10) V1s 2 , V1s 2 , V2s 2 , V 2s2 , S2p1x | Sp1y
(ii) NH3 Ÿ 3V + 1 lp = 4, i.e. sp3 hybridisation
(iii) BF3 Ÿ 3V + 0 lp = 3, i.e. sp2 hybridisation 64
(iv) NH2–Ÿ 2V + 2 lp = 4, i.e. sp3 hybridisation BO 1
2
(v) H2O Ÿ 2V + 2 lp = 4, i.e. sp3 hybridisation
Thus, among the given pairs, only BF3 and NO2– have sp2 Thus, O22 and B2 have the same bond order..
hybridisation. NOTE
10  7 BO of O2+ = 2.5, NO+ = 3, NO = 2.5, CO = 3, N2 = 3 and O2
29. (D) Bond order of O 2 1.5 =2
2
34. (D)
10  7
Bond order of O 2 1.5
2 (A) H2O Ÿ O
H H
10  8 (2 bp + 2 lp)
Bond order of O 22 1
2 [bp = bond pair and lp = lone pair]

10  6 F
Bond order of O 2 2
2
B
' Maximum bond order = minimum bond length. (B) BF3 Ÿ F F
? Bond length is minimum for O2+ . (3 bp + 0 lp)

30. (B) BF3 is an electron deficient species, thus behaves

(C) NH2–Ÿ
like a Lewis acid.
N
Nb  Na H H
' Bond order (2 bp + 2 lp)
2

Cl
(D) PCl3 Ÿ P
31. (D) NO2 o sp 2
Cl Cl
NO3 o sp 2 (3 bp + 1 lp)
NH 2 o sp3
Thus, in PCl3, the central P-atom is surrounded by three
NH 4 o sp3
bond pairs and one lone pair.
SCN  o sp
35. (B) Molecular orbital configuration of
NO2– and NO3– both have the same hybridisation, i.e. sp2. O2 (8  8  1 15)
4 3 2 1 * *
32. (A) H 3 C C { C  C H 3 is linear because C2 and C3 are V1s 2 , V1s 2 .V2s 2 , V 2s 2 , V2p z2 ,
sp hybridised carbon atom.
* *

33. (A) According to molecular orbital theory, S2p 2x | S2p2y , S 2p1x | S 2p0y

O22 (8  8  2 18) 10  5
Bond order (BO) 2.5
2
* * *
V1s 2 , V1s 2 , V2s 2 , V2p 2z , S2p2x | S2p 2y , S 2p2x | S 2p 2y Similarly,

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CHEMISTRY FOR NEET & AIIMS
(B) O2– ( 8 + 8 + 1 = 17) Ionic character v size of cation (if anion is same)
The order of size of cation is
N b  Na 10  7
so, BO 15 NA+ > Zn2+ > Cu2+
2 2
? The order of ionic character and hence, of solubility in
(C) O22– (8 + 8 + 2 = 18)
water is as
N b  Na 10  8 Na2S > ZnS > CuS
BO 1
2 2
40. (D) Species with sp2 hybridisation are planar triangular
(D)O2 (8 + 8 = 16) in shape. Among the given species NO3– is sp2 hybridised
10  6 with no lone pair of electrons on central atom, N. Whereas,
BO 2
2 N3, NO2– and CO2 are sp hybridised with a linear shape.
Thus, O2– shows the bond order 1.5.
36. (B) Paramagnetic species contains unpaired electrons in O
their molecular orbital electronic configuration. +
N N N N
Molecular orbital configuration of the given species is
as O O
CO (6 + 8 = 14)
* *
O N O O C O
V1s 2 , V1s 2 , V2s2 , V 2s 2 , V2p 2x | S2p 2y , V2p 2z
(All the electrons are paired so, it is diamagnetic). 41. (D) CO2 and CH4 have zero dipole moment as these are
O2 (8  8  1 17) symmetrical in nature. Between NH3 and NF3, NF3 has
greater dipole moment thought in NH3 and NF3 both, N
* * * * possesses one lone pair of electrons.
V1s2 , V1s 2 , V2s 2 , V 2s 2 , V2p 2x | S2p 2y , S 2p 2x | S 2p1y
(It contains one unpaired electron so, it is paramagnetic.) H
CN– (6 + 7 + 1 = 14) = same as CO μres μ1
NO+ (7 + 8 – 1 = 14) = same as CO O C O μ1 C μ4
μnet= 0 μ3 H
Thus, among the given species only O2 is paramagnetic H
H
37. (B) Symmetrical molecules are generally non-polar ' μres = μ1 + μ2 + μ3 = – μ4
although they have polar bonds. This is because bond
and μnet = μres + μ4
dipole of one bond is cancelled by that of the otehr, BF3,
? μnet = μ1 + μ2 + μ3 + μ4
SiF4 and XeF4 being symmetrical as non-polar. SF4 is
unsymmetrical because of the presence of a lone pair of = – μ 4 + μ4 = 0
eleectrons. Due to which it is a polar molecule. μnet = 0

38. (B) All the molecules have O-atom with lone pairs, but in .. .. μ
H2O the H-atom has no vacant orbital for S-bonding. μ4 4

That’s why it does not have any S-bond. μ3 N μ1 μ3 N μ1

In all other given molecules, the central atom because of H μ2 H F μ2 F
the presence of vacant orbitals is capable to form H F
S-bonds. Resultant of Resultant of
39. (D) Ionic compounds are more soluble in water or in 3M – H 3N – F
aqueous medium. bond lie in the same bond lie opposite to μ4
According to Fajans' rule, direction as μ4
Size of the cation increases the ionic character also Hence, μnet = + μres + μ4
increases.

98
 CHEMICAL BONDING
This is because in case of NH3, the net N–H bond dipole
is in the same direction as the direction of dipole of lone 44. (D) ClO3 , SO32
pair but in case of NF3, the directions of net bond dipole
of three –N–F bonds is opposite than that of the dipole .. ..
Cl Cl
of the then lone pair.
O O O O O O
42. (B) Isoelectronic species contain same number of
electrons. Be2+ contains 2 electrons. Among the given
options, only Li+ contains 2 electrons and therefore, it is
O O
isoelectronic with Be2+. O C N O
O O
H+ o no electron, Na+ o 10e–
Li+ o 2e–,
Number of electrons
Mg o 10e–
2+

Hence, Be2+ is isoelectronic with Li+.

CO32 6  2  24 32
43. (B) Bond order of O2 SO32 16  2  24 42
* * ClO3 4  24  1 42
O 2 2 2
V1s , V1s , V2s , V 2s 2 2
V2p 2z ( S2p 2x S2p 2y )
CO32 6  24  2 32

(S* 2p1x S* 2p1y ) NO3 7  2  24 33

Bond order number of electrons in BMO

Hence, ClO3 and SO32 are isoelectronic and are
 number of elections ABMO
pyramida in shape.
2

10  7 3 45. (B) Structure V and S bonds

15
2 2 O
* * (A) C V and - 4
O 2 V1s 2 , V1s 2 , V2s 2 , V 2s2 V2p 2z (S2p 2x S2p 2y )
S and -1
O O H
(S* 2p1x S* 2p 0y ) O
(B) C V and -4
10  5 5
Bo 2.5 S and -4
2 2 O O H
* * 2
(C) N{C–C{N V and -3
O2 V1s 2 V1s 2 , V2s 2 , V 2s 2V2p z2 (S2p x S2p 2y )
S and -4
* *
(D) H V and -6
(S 2p1x S 2p1y )
S and -4
N C C C N
10  6 4
BO 2
2 2 H
So, the correct sequence is 46. (A) and (D)
O2  O2  O2

99
CHEMISTRY FOR NEET & AIIMS

G G G
H  C { N- - - - H  C { N
Species Total number Structure Shape
of electrons HCN
ClO 3 42
.. Pyramidal
Cl
O OH
O O 3 1
.. HO 6
O HO 2 O
SO 32 42 S Pyramidal 4
O O 5 2
O O
O 3 4 5
O
1 O
CO32 32 Trigonal planar HO OH 6
n
C
O O Cellulose
O
NO 3 32 Trigonal planar In above molecules, dotted lines represent hydrogen
N bonding.
O O
49. (A) As the number of lone pair of electrons on central
Hence both options (a) and (D) are correct element increases, repulsion between those lone pair of
electrons increases and therefore, bond angle decreases.
Molecules Bond angle
47. (C)
ION Structure Hybridisation CH4 (no lone pair of electrons) 109.5°
+
NH3 (one lone pair of electrons) 107.5°
NO+2 O N O sp H2O (two lone pair of electrons) 104.45°
NO3 O
N O sp2 50. (D) According to the postulate of VSEPR theory, a lone
O pair occupies more space than a bonding pair, since it
NH+4 H sp3 lies closer to the cnetral atom. This means that the repul-
+
N sion between the different electron pairs follow the or-
H H der. lp – lp > lp – bp > bp – bp
H
51. (C) Key concept The species that have same number of
electrons have same bond order.
Thus, option (C) is correct.
48. (C) Intermolecular hydrogen bonding is present in
S peices Number of electrons
concentrated acetic acid, H2O2 and HCN while cellulose
has intra - molecular hydrogen bonding as shown below CO 6 + 8 = 14
NO 7 + 8 = 15
O H O O2 8 + 8 = 16
H3C C C CH3 NO
+
7+8 1 = 17
O H O
--
CN 6 + 7 + 1 = 14
Concentrated Acetic Acid -
8 + 8 + 1 = 17
O2

thus, both CN– and CO have equal number of electrons.

H
So, their bond order will be same.
O O 52. (D) valency factor for Mg = 2 thus formula
H H valency factor for x = 5 of comp = M3X2
O O 53. (B) CN– total e– = 14
V1s2, V*1s2, V2s2, V*2s2, S2px2 = S2py2, V2pz2
H
H2O2 BMO  ABMO 10  4
BO 3
2 2

100
 CHEMICAL BONDING
.. ..
54. (B) F – Cl – F 2 lone pair on Cl– atom O
.. N O
..
+
F
4. (A) XeF4 : It has sp3d2 hybridisation, shape is square
5 2 0 3
planar instead of octahedral due to presence of two lone
55. (C) HNO3 , NO, N 2 , NH 4 Cl
pairs of electrons on Xe atom.
56. (B) BeO due to palarisation SF4 : SF4 molecule shows sp3d hybridisation but its ex-
EXERCISE
pected trigonal bipyramidal geometry gets distorted due
P-2 (AIIMS) to presence of a lone pair of electrons and it becomes
distorted tetrahedral or see-saw with the bond angles
1. (A) Bond dissociation energy for C – H bond are given equal to 89° and 177° instead of the expected angles of
below in the given molecules : 90° and 180° respectively.
C6H5CH3 - 85 kcal/mol
C6H6 - 110 kcal/mol F .. F F F
CH3CH2CH2CH2CH3 - 98 kcal/mol

CH3 Xe S
H3C C CH3
- 92 kcal/mol F .. F F F
CH3

2. (B) The value of dipole moment of methyl halides :

3d 4s 4p
CH3F - 1.51 D ; CH3Cl - 1.56 D;
[NiCl4]2– ion : xx xx xx xx
CH3Br - 1.4 D; CH31 - 1.29 D
? CH3Cl > CH3F > CH3Br > CH3I.
sp3 hybridisation
tetrahedral shape
3. (D) The actual geometry of the NO3– ion is triogonal
planar with bond angle of 120°. Hybridisation is sp2.
4d 5s 5p
O Pd2+ ion
..
..

(4d8 5s0 5p0)

N 120°
..
O O
..

.. .. xx xx xx xx
[PdCl4]2 ion :
NO : Ideal geometry is trigonal planar, sp hybridisation
–
2
2

Cl Cl Cl Cl
with bond angle of 116°.
.. .. .. ..
N O
.. N O.. sp3 hybridisation
..

O O..
..

..
..

NO2 : Ideal geometry is trigonal planar; sp2 hybridisation

[PdCl4 ]2 ion : xx xx xx xx
with bond angle of 134°.
+. .. +. .. Cl Cl Cl Cl
N O.. N O..
..

O O.. dsp2 hybridisation

..
..

..

NO2+ : Ideal geometry is linear; sp hybridisation with

Experiments have, however, shown that 4-coordinated
bond angle of 180º .
complexes of Pd(11) are diamagnetic (n = 0). Thus it is
dsp2 hybridisation which is invovled in the formation of
[PdCl4]2– ion i.e., 4-coordinated complex of Pd(II) have
square planar geometry with n= 0 (diamagnetic).

101
CHEMISTRY FOR NEET & AIIMS
5. (C) Cyanide is considered, in a broad sense, to be the 12. (A) Compound : BeCl2 > NO2 > SO2
most potent ligand for many transition metals. the very Angle : 180° > 132° > 119.5°
high affinites of metals for cyanide can be attributed to 13. (D) BF3 has zero diple moment.
its negative charge, compactness and ability to engage
14. (A) O2(V1s)2(V*1s)2(V2s)2(V*2s)2(V2pz)2(S2p2x = S2p2y)
in S-bonding. the dicyanides [M(CN)2]– (M = Cu, Ag,
(S*2px1 = S*2py1)
Au) are linear in geometry.
Thus, there are total 6 electrons in antibonding orbitals.
1V
–C N – Thus, two cyanide ions have 4S-bonds. 15. (A) In BF3, there is back bonding in between fluorine and
2S
boron due to presence of p-orbital in boron.
6. (A) Ozone molecules is V-shaped with O – O bond length F
B F , back bonding imparts double bond
1.278 Å. F
characteristics.
Å 1
78 O .278 As BF3 forms adduct the back bonding is no longer
1 .2 Å
116.8° present and thus dhouble bond characteristic disappears.
O O
Hence, bond becomes a bit longer than earlier (1.30 Å).
The bond length is intermediate between that for a single
bond (1.48 Å as in H2O2) and for a double bond (1.21Å as 16. (D) Lewis gave the structure of O3 molecule as
1
in O2). O
1 :O: O:
Also, bond order v 2 3
bond length
Using the relation,
Hence, O2 < O22– .
Formal charge = [Total no. of valence electrons in the
free atom] – [Total no. of non-bonding (lone pair)
7. (C) Only HF2– has H-bonding [F–H......F]– rest all the
1
molecules have coordinate bonds. electron]  [Total no. of bonding (shared) electrons]
2
8. (A) In H2O, electronegativity difference is highest.
The formal charge on central O – atom i.e.,
So, diple moment is highest in H2O. CH4 is a symmetrical
tetrahedral structure and its diple moment is zero. 1
no. 1 = 6 – 2 – (6) 1
2
9. (A) SeF4 and XeO2F2, both are sp3d hybridised, trigonal 17. (D)
bipyramidal and see-saw shaped with 1 lone pair of elec-
trons each.
Ion Total MO B.O.
SF4 hss 1 lone pair, XeF2 has 3 lone pairs, XeOF4 is square
no. of configuration
pyramidal with 1 lone pair, SeCl4 has see-saw shape with
electrons
1 lone pair, XeF4 has square planar shape with 2 lone
pairs,
O2+ 15 KK V2s2 V*2s2 V2pz2 2.5
10. (C) There is no restriction that resonating structures
S2px2 = S2py2 S*2px1
should have +ve and –ve charges on atoms that are far
apart. = S*2py0

q1q 2
11. (D) Lattice energy =  O2– 17 KK V2s2 V*2s2 V2Pz2 1.5
r2
S2px2 = S2py2 S*2py2
where q1 and q2 are charges on ions and r is the distance
between them. Sicne interionic distances in CaO and = S*2py1
NaCl are similar, (larger cation has smaller anion and vice
versa) therefore, r is almost the same. Therefore, lattice O22– 18 KK V2s2 V*2s2 V2pz2 1.0
energy depends only on charge. Since the magnitude of S2px2 = S2py2 S*2px2
charge on Na+ and Cl– ions is unity and that on Ca2+ and = S*2py2
O2– ions is 2 each, therefore, the lattice energy of CaO is
four times the lattice energy of NaCl, i.e., 4U. Hence, the correct B.O. is O2+ > O2– > O22 –

102
 CHEMICAL BONDING
central atom. The distortion in shape is due to the
18. (B)
presence of one onle pair of electrons.

26. (B) Bond dissociation energy is the energy required to

F break a particular bond in one mole of a gaseous molecule.
Bond energy is the average value of dissociation energies
S Xe
of the same type of bond present in the molecule. Bond
O O F energy of C–H bond in methane is 99.2 kcal/mol. Thus.
SO2 (One lone pair) XeF2 (Three lone pair) for polyatomic molecules, average bond energy is taken
as the dissociation bond energy.
F H
Si C F
F F F H H H
SiF4 (No lone pair) CH4 (No lone pair) 27. (C) Cl F

19. (B) According to molecular orbital theory, the energy CIF3 (T–shape)
level of the given molecules are The lone pairs are at equatorial position (120° angle).
C22– o V1s2 V*1s2 V2s2 V*2s2 S2px2 S2py2 V2pz2 28. (C) Oxygen has two unpaired electrons.
B.O. = 1/2[10 – 4] = 3 So it is paramagnetic.
He2+o V1s2 V*1s1
B.O. = 1/2[2 – 1] = 1/2 = 0.5 29. (A)
NO o V1s2 V*1s2 V2s2 V*2s2 V2pz2 S2px2 S2py2 S*2px1
B.O. = 1/2[10 – 5] = 2.5 30. (A) Lithium carbonate is unstable to heat; lithium being
O2– o V1s2 V*1s2 V2s2 V*2s2 V2pz2 S2px2 S2py2 S*2px2
S*2py1 very small in size polarises a large CO32  ion leading to
B. O. = 1/2[10 – 7] = 1.5 the formation of more stable Li2O and CO2.
So, the correct order of their increasing bond order is
He2+ < O2– < NO < C22–
20. (A) Hybridisation of carbon in CH3+ is sp2 and
in CH4 its hybridisation is sp3
21. (A)
22. (B) In Bonding N.O. existing modal plane of Pz orbital is
maintained
23. (C) Due to greater lone pair - bond pair repulsions than
bond pair - bond pair repulsions, the F – S – F bond
angle decreases from 180°.

24. (A) Bond order of N2 = 3, bond order of O2 = 2. Higher

The bond order, higher is the bond dissociation energy.
i.e., higher stability or less reactivity. Thus, N2 is less
reactive than O2.
Higher the bond order, shorter is the bond length. Shorter
bond length of N2 shows its higher bond order.

25. (C) SeCl4 possesses see-saw geometry, which can be

regarded as a distorted trigonal bipyramidal structure,
having one lone pair of electrons in the basal position of
the trigonal bipyramid. See-saw geometry of SeCl4
molecules aries due to the sp 3d hybridisation of the

103
HYDROGEN AND
CHAPTER
10
ITS COMPOUNDS
Hydrogen is a light, odorless gas, which, given enough time, turns into
people.

“EDWARD ROBERT HARRISON”

INTRODUCTION

H
ydrogen, the most abundant element in the universe and the third most abundant on
the surface of the globe, is being visualised as the major future source of energy.
Hydrogen has the simplest atomic structure among all the elements around us in
Nature. In atomic form it consists of only one proton and one electron. However, in
elemental form it exists as a diatomic (H2) molecule and is called dihydrogen. It forms
more compounds than any other element. Do you know that the global concern
related to energy can be overcome to a great extent by the use of hydrogen as a
source of energy? In fact, hydrogen is of great industrial importance as we will learn
in this unit.

104
CHEMISTRY FOR NEET & AIIMS
Hydrogen is the lightest element and also the lightest gas in the periodic table.
It is the lightest non-metal. It is the simplest element in periodic table having only 1e–, 1p & no neutron.
Electronic configuration of H is 1s1
Number of e– = 1 Number of orbital = 1
Number of shells = 1 Number of subshell =1
It is discovered by Henry Cavendish & it was called inflammable element.
The name hydrogen was given by Lavoisier
HYDROGEN

Hydro (Water) Gene (Producer) or generator

means according to Lavoisier the gas which produce water on burning with oxygen.
1
H2 + O2 o H 2O
2
POSITION OF H2 IN PERIODIC TABLE
Hydrogen is the first element of Periodic table but still it could not be assigned a proper position either in Mendeleef
periodic table or in Modern periodic table because of following reasons.
It may kept in 1st/IA or 17th/VIIA group due to following reason.
RESEMBLES WITH 1ST / IAALKALI METALS
(i) Electronic configuration : Like alkali metals hydrogen also has only one electron in outer most shell.
• H = 1s1 K = 4s1

• Li = 2s1 Rb = 5s1 ns1

• Na = 3s1
(ii) Electropositive characters : Like alkali metals hydrogen also have the tendency to loose one electron
to form cation.
Ex. Na o Na+ + e–
H o H +
+ e–
(Proton)
(iii) Oxidation numbers : Like alkali metals hydrogen can also exhibit the oxidation number of +1 in most of its compound.
Ex. Na+Cl– K+Cl
H+ Cl– = +1
(iv) Reaction with electronegative elements (non-metals) : Like alkali metals H also reacts with Oxygen, Sulphur,
Halogens to form oxides, sulphides and halides respectively.
gives
O  H2O, like Na2O, K2O
o
S  
gives
o H2S, like Na2S, K2S
gives
with halogen   HX, like NaX, KX
o
(v) Liberation at Cathode :
2Na+ Cl electrolysis 2Na + Cl2
  o
(liberated at cathode) (liberated at anode)
2H Cl electrolysis (H2 + Cl2)
  o
+ –

like alkali metals H also get liberated at cathode on electrolysis.

105
 HYDROGEN AND ITS COMPOUNDS

(vi) Reducing nature : Like alkali metals H2 also have reducing nature.
CuO + H2 oCu + H2O
Due to resembling of these properties with alkali metals H can be placed in IA/group/alkali metals group.

RESEMBLES WITH HALOGEN/ VIIA/17TH

(i) Electronic configuration :
Electronic configuration of halogen H o1s1
o ns2np5
both these requires one electron to attain the stable configuration of their nearest inert gas.

H o1s1  1 o He (1s )
e less than 2


F o2p5  1 o Ne (2p )
e less than 6


Cl o 3p5  1 o Ar (3p )
e less than 6

(ii) Electronegative character : Both halogen & Hydrogen has the tendency to gain one e–.
F + e– oF—
H + e– oH–
i.e. why both will act as electronegative species.
(iii) Ionization potential : Ionization potential of hydrogen is almost similar to halogen.
(iv) Oxidation number : Both halogen & hydrogen can exhibit –1 oxidation number.
Hydrogen in metal hydride shows –1 oxidation state.
NaH oNa+ + H–
NaCl oNa+ + Cl–
(v) Diatomic molecule : Both halogen & hydrogen have the tendency to exist as diatomic molecule.
Ex. F2, Cl2 Br2, I2 & H2.
(vi) Liberation at anode : Whenever Alkali metals halides & hydrides undergoes electrolysis, both halogen and hydrogen
will liberate at anode.
2Na+ Cl– o2Na + Cl2 (anode)
2Na+ H– o2Na + H2 (anode)
(vii) Reaction with highly electropositive metals : Hydrogen reacts with highly electropositive element (i.e. s-block
elements) & forms their hydrides like their halides.
2Na + H2 o2NaH
2Na + Cl2 o2NaCl
This reaction shows oxidising character of hydrogen.
(viii) Formation of covalent compound : Both Hydrogen & halogen on reaction with non metals to form covalent
compounds like.
CH4, NH3, H2O
CCl4, NCl3, Cl2O
Conclusion : The position of hydrogen is still in controversy & no proper position is assigned to H in periodic table
i.e. why it is also called notorious or rogue elements.

106
CHEMISTRY FOR NEET & AIIMS
ISOTOPES OF HYDROGEN
There are 3 isotopes of H2
Protium or Deuterium/ Tritium
ordinary hydrogen Heavy hydrogen
Symbol 1H1 1
H2/1D2 H3/1T3
1
H2 D2 T2

Property Protium or Deuterium or Tritium

ordinary heavy hydrogen
hydrogen
Atomic number 1 1 1
Mass number 1 2 3
Exact atomic mass 1.008123 2.0142 3.0170
1 2
Symbol 1H 1 H or 21 D 3
1 H or 31 T
Molecular formula H2 D2 T2
No. of protons in
the nucleus 1 1 1
No. of neutrons in
the nucelus Nil 1 2
No. of electron 1 1 1
Electronic configu. 1s1 1s1 1s1
Relative abundance 99.984% 0.016% 10–15 %
Stability Stable Stable Unstable(Radioactive)

Properties H2 D2 T2
M.P. – 2590C – 254.30C – 252.40C
B.P. – 252.60C – 249.30C – 248.00C
Bond length (H– H) 74 pm 74 pm 74 pm
Bond energy (H—H) 436.0 KJ mol–1 443.3 KJ mol–1 446.9 KJ mol–1
Heat of fusion & vaporisation Minimum H<D<T Maximum

Isotopic effect
The effect which can change the physical & chemical properties of isotopes is called isotopic effect.
It is because of difference in mass.
In isotopic effect maximum changes occurs in physical properties like melting point, boiling point, bond energy,
while minimum changes occurs in chemical properties like state of chemical reaction etc.
Imp.Isotopic effect is found only in hydrogen isotopes. Because there is large difference in mass.

While in other isotopes like 7N14 7

N15 only a fractional mass is increased.
6
C14 6C13 6C12 o Here also only a fraction is increased
But in case of hydrogen mass increased to 2 to 3 times in their isotopes.

107
 HYDROGEN AND ITS COMPOUNDS
Ex. Isotopic effect is found in :
(a) H (b) N (c) C (d) All
Sol. (a)
Ex. Which of the following reaction is fast & why ?
(i) CH4 + Cl2 oCH3Cl + HCl
(ii) CD4 + Cl2 oCD3Cl + DCl
Sol. (i) because C–H bond energy is less in comparison to C–D bond energy.

DIFFERENT FORMS OF HYDROGEN

(I) BASED ON OXIDATION NUMBER :
There are three types of hydrogen
H+ H– H
Proton Hydride Atomic hydrogen

Number of electron 0 2 1
Oxidation number +1 –1 0
'
Formation H oH+ + e– H + e– oH– H2 o 2H
Note : In the aqueous state proton (H ) exist as H+ (H2O)n
+

Where n is a large number.

If n = 1 o H3O+
n=2 o H+(H2O)2
Ex. In the aqueous solution hydrogen ion exist as
(a) H3O+ (b) H+(H2O)2 (c) H+(H2O)n (d) All
Sol. (d)
(II) BASED ON REACTIVITY :
Hydrogen

Atomic Hydrogen

Simple atomic H Nascent hydrogen Adsorbed/Occofluded

Atomic Hydrogen
(i) Simple atomic hydrogen – It is formed by simple dissociation of hydrogen.

Favourable condition – Favourable condition are high temp & low pressure.
(ii) Nascent hydrogen – Hydrogen at the moment of its birth it called nascent hydrogen means which forms at the
instant is known as Nascent hydrogen.
It is formed only by some specific chemical reaction.
(a) Acid + Metals
Zn + H2SO4 o ZnSO4 + 2H
(b) Base + element 2NaOH + Be oNa2BeO2 + 2H
(c) C2H5OH + Alkali metal
C2H5OH + Na o C2H5ONa + H

108
CHEMISTRY FOR NEET & AIIMS

(iii) Adsorbed/Occluded hydrogens

Concentration of H is more

Adsorbed H is hydrogen present at the outer surface of metal.

Occlusion – The property of metal to adsorb any gas is called occlusion.
Reactivity order
Atomic hydrogen > Nascent hydrogen > Molecular hydrogen

(III) BASED ON NUCLEAR SPIN (NUCLEAR ISOMERS) :

(i) Ortho hydrogen – The molecular form of hydrogen having same spin of proton is called ortho hydrogen.
(ii) Para hydrogen – The molecular form of hydrogen having opposite spin of proton is called para hydrgen.
In ortho hydrogen spin of proton is same, so they will repel each other & because of this repulsion, internal
energy of ortho hydrogen increases. So ortho hydrogen has more internal energy.
Stability of ortho & para hydrogen
Stability of ortho & para hydrogen depends upon temperature condition.
At low temp : para hydrogen is more stable than ortho hydrogen while at high temp ortho hydrogen is more
stable than para hydrogen.

Ortho Para
At 25°C 75% 25%
At –253°C/20K 0 100%

KEY POINTS
(i) We can obtain 100% pure para hydrogen at low temp but can't ortho because at high temp parahydrogen will
dissociate into atomic hydrogen.
(ii) Ortho & Para hydrogen differs only in physical properties but have same chemical properites.

METHOD OF PREPARATION
(i) From acids : The metal which are placed about H2 in electrochemical series react with dil acids they liberate H2.
Ex. Fe + H2SO4 oFeSO4 + H2
(dil)
Cu + H2SO4 o× (No reaction)

109
 HYDROGEN AND ITS COMPOUNDS

Lab preparation : When impure Zn reacts with dil H2SO4 it forms H2

Zn + H2SO4 oZnSO4 + H2
(impure) (dil)

Ex. Why we use impure Zn?

Ans. Because the rate of reaction with pure Zn is very slow.
(ii) By alkalies : Only (Be, Zn, Al, Sn, Pb, Si) (Amphoteric metal) react with boiling NaOH or KOH they evolve H2.
Zn + 2NaOH oNa2ZnO2 + H2n
(sodium zincate)
2Al + 2NaOH + 2H2O oNaAlO2 + 3H2n
(sodium meta aluminat e)
Sn + 2NaOH + H2O oNa2SnO3 + 2H2n
(sodium stannate)
Pb + 2NaOH + H2O oNa2PbO3 + 2H2n
(sodium plumbate)
Si + 2NaOH + H2O oNa2SiO3 + 2H2n
(sodium silicate)
Be + 2NaOH oNa2BeO2 + H2
(sodium beryliate)
(iii) From water :
All the metals which are placed above than H2 when react with water the evolve H2.
Zn + H2O oZnO + H2n
Three type of water is used
(a) Cold water : The temperature of cold water is 7 to 25°C this water is used for highly reactive metals.
Such as Li, K, Ba, Sr, Ca, Na, means alkali metals of alkaline earth metals.
The reaction with alkali metals are vigorous to minimum the rate of reaction these metals are used in the
form of amalgam.
2Na(Hg) + H2O o2NaOH + H2n
(b) Hot water : The temperature of hot water is 25°C to 90°C. This water is used for reactive metals, such as Mg,
Al, Mn, Zn, Cr.
(c) Steam : The temperature of steam is more than 100°C. This form of water is used for very less reactive
metals like Fe, Cd, Co, Ni, Sn, Pb.
Condition for best yield of H2
(i) Cold water oWith highly reactive metals.
(ii) Hot water oWith reactive metals
(iii) Steam oWith less reactive metals.
METHOD TO PREPARE PURE HYDROGEN
(i) Electrolysis of water :To prepare pure hydrogen we use impure water (i.e. having 15-20% solution of alkali
or acid)
4H2O l 4H+ + 4OH–
at cathode 4H+ + 4e– o2H2
at anode 4OH o2H2O + O2 + 4e–
–

The SO4–2 or K+ ion present in acid or alkali does not move towards anode or cathode as their discharge potential is
higher than of OH– ions or H+ ions respectively.
(ii) By reaction of Magnesium with dil. H2SO4 :
Mg + H2SO4 oMgSO4 + H2

110
CHEMISTRY FOR NEET & AIIMS
(iii) By reaction of NaH with water :
NaH + H2O oNaOH + H2
(iv) Uyeno method : This method is used for military purpose
2Al + 2KOH + 2H2O o2KAlO2 + 3H2n
(Potassium meta aluminate)
Because by this reaction we can prepare H2 in a rapid manner.

COMMERCIALOR INDUSTRIALMETHOD TO PREPARE H2

(i) Lane process : Steam is passes over hot iron it converts into Fe3O4 & H2.
3Fe + 4H2O oFe3O4 + 4H2n
Iron is regenerated by reducing Fe3O4 into Fe by water gas (CO + H2)
2Fe3O4 + 4CO + 4H2 o6Fe + 4CO2 + 4H2O
Fe3O4 + 2CO + 2H2 o3Fe + 2CO2 + 2H2O
This process is a continuous process.

(ii) Bosch Process : In this process initially steam is passed over red hot coke then water gas is formed.
C(s) + H2O(g) 
1270
o CO(g) + H2(g)
Then water gas is mixed with more stem in presence of Fe2O3/Cr2O3 then CO will convert into O2 & we can obtain
more H2.
CO(g) + H2 + H2O(g) oCO2(g) + 2H2(g)

(iii) From Natural gas :

CnH2n+2 + nH2O onCO + (2n + 1)H2
1270
e.g. CH4(g) + H2O(g) CO(g) + 3H2(g)
Ni
water gas

PHYSICAL PROPERTIES OF HYDROGEN

(i) Hydrogen is a lightest, colourless, odourless and tasteless gas. It is sparingly soluble in water. It is inflammable and
less reactive gas.
(ii) Its f.p. (– 259.20C) and b.p. (–2520C) are very low indicating less intermolecular attraction. Due to low f.p. liquid
hydrogen is used as a cryogenic fluid (to produce low temperature).
(iii) H—H bond energy [ 104 Kcal mol–1] and 436 KJ/m
(iv) H – H bond length [ 74 pm] so H2 is less reactive and require high temp for reaction.

CHEMICAL PROPERTIES OF H2
(i) H2 is neutral in nature i.e. why it does not react with acids & bases.
(ii) LESS REACTIVE : Hydrogen is very less reactive in nature because of very high bond dissociation energy.
(iii) COMBUSTIBLE NATURE : H2 is highly combustible in nature & it burns with oxygen or air with pale blue flame to
give water.

1
H2 + O oH2O
2 2
(iv) REACTION WITH HIGHLY ELECTROPOSITIVE METALS
IA & IIA group elements are called highly electropositive metal. Whenever H reacts with these metals they form
ionic hydrides.
2Na + H2 o2NaH
CO + H2 oCaH2

111
 HYDROGEN AND ITS COMPOUNDS

(v) REACTION WITH NON-METAL

(a) Reaction with halogen
H2 + X2 o2HX
p
[F2, Cl2, Br2, I2]
order of reactivity of halogen with hydrogen
F2 > Cl2 > Br2 > I2
(b) Reaction with sulphur
H2 + S oH2S
(c) With nitrogen – (Haber process)
683K
N2 + 3H2  o 2NH3
Fe, Mo, 200atm
(vi) REDUCINGNATURE
CuO + H2 oCu + H2O
(vii) REACTION WITH CARBON MONO OXIDE
ZnO / Cr O
2H2 + CO  2 3 o CH OH (Methanol)
3
37 3K
(viii) HYDROGENATION OF UNSATURATED HYDROCARBON
C2H2 + 2H2 oC2H6
Ni / Pb / Pt
C2H4 + H2  oCH
473K 2 6

When unsaturated hydrocarbon having C = C or C {C reacts with hydrogens in the presence of Ni/Pd/Pt forms
saturated hydrocarbons.

KEY POINTS

Hydrogenation of vegetable oil.

Vegetable oils are also called polyunsaturated oils because they contain many C = C bond. When these oil are exposed
to air for a long time then double bond will get oxidized and the oil becomes. Rancid (having fowl. smell or unpleasant
test) in nature. So to avoid this vegetable oil are converted into edible fats (Vanaspati Ghee)
Ni
Vegetable oils + H2  o edible fats solid
(liquid)
This whole process is known as hydrogenation or hardening of oil.

USES OF HYDROGEN :
(1) Hydrogenation of vegetable oil to form solid fats i.e. vanaspati ghee.
(2) In liquid form as a rocket fuel. (Liquid H2 + Liquid O2)
(3) In a air ship of balloons as a mixture of Hydrogen & Helium [15% H2 + 85% He]
(4) Formation of different compounds.
Like oNH3, (Haber process) alkane, alcohol and other hydrocarbon
Ex. Describe the bulk preparation of hydrogen by electrolytic method. What is the role of an electrolyte in this process
Sol.: The electrolyte (15–20% NaOH solution) increases conductivity of water.
Cathode (iron) : Reduction of water occurs.

112
CHEMISTRY FOR NEET & AIIMS

2H2O + 2e– o 2H2 + 2OH–

Anode (nickel coated iron) : Oxidation of OH– occurs.
2OH– o H2O + 1/2 O2 + 2e–

Ex. Complete the following reactions :

'
'
(i) H2(g) + MmOn(s) o (ii) CO(g) + H2(g) o
Catalyst

'
(iii) C3H8(g) + 3H2O(g) o '
(iv) Zn(s) + NaOH(aq) o
Catalyst
'
Sol. (i) nH2(g) + MmOn(s) o mM(s) + nH2O(A)
'
(ii) CO(g) + 2H2(g) o CH3OH(A) (methanol)
Catalyst

Ni
(iii) C3H8(g) + 3H2O(g) o 3CO(g) + 7H2(g)
1270K

(iv) Zn(s) + 2NaOH(aq)  o Na2ZnO2(aq) + H2(g)

heat

Ex. Can conc. H2SO4 be used for drying H2 gas ? Justify.

Sol. Conc. H2SO4 cannot be used for drying H2 gas because H2SO4 does absorb moisture from moist H2, but the process
is highly exothermic. The heat so produced causes hydrogen to catch fire because of its inflammable nature.
Ex. Can dihydrogen act as oxidising agent ? If so give chemical reactions to support the statement.
Sol. Dihydrogen can act as oxidising agent when it forms metal hydrides.
2Li + H2 o 2LiH

HYDRIDES
The compounds of hydrogen with different elements are called hydrides.
These are of three types :
(1) IONIC/SALT LIKE/SALINE HYDRIDES
Compounds of hydrogen with s-block elements except berylium & magnesium are called ionic hydrides.
LiH, NaH, KH, RbH, CsH, CaH2, SrH2, BaH2
BeH2, MgH2 are covalent polymeric hydride.
• Structure of these hydrides are similar to rock salt, so they are also called salt like/saline hydrides.
• Down the group sizenLattice energypstabilitypMelting pointpBoiling pointp
• On electrolysis of these hydrides, hydrogen is liberated at anode.
• On reaction with water these hydrides will form hydrogen
NaH + H2O oNaOH + H2
• These hydrides forms complex hydrides which are very good reducing agents.
4LiH + AlCl3 oLiAlH4 + 3LiCl
NaBH4 oSodium borohydride
LiAlH4 oLithium aluminium hydride.
(2) METTALIC / INTERSTITIALHYDRIDES
They are the compounds of d & f-block elements.

113
 HYDROGEN AND ITS COMPOUNDS
In these hydrides hydrogen occupies interstitial sites present in metallic lattice, so they are called interstitial
hydrides.
• Properties of these hydrides are similar to parent metals, so they are also known as metallic hydrides.
• These hydrides are non. stoichiometric in nature (i.e. having variable composition)
ZrHx (x = 1.3 – 1.75)
TiHx (x = 1.8 – 2)
• Metals of group 7,8,9 donot form any hydrides so this particular part of periodic table is known as hydride gap.
(3) COVALENT/MOLECULES HYDRIDES
• They are the compounds of hydrogen with p-block elements CH4, NH3, H2O, HF, etc.
• These hydrides exist as molecules, so they are also known as molecular hydrides. There hydrides are non-conductor
of electricity.
Nomenclature – element + Suffix (ane)
PH3 oPhosphane
NH3 oAzane
H2O oOxidane
These hydrides are again divides into 3 categories.
(a) Electron deficient hydrides :
• They are the hydrides of group 13 elements.
BH3, AlH3, GaH3 – In these hydrides central element does not have complete octet. i.e. why they are called
electron deficient compounds.
(b) Electron precise hydrides – They are the hydrides of group 14 element.
Ex. CH4, SiH4, GeH4
In these type of hydrides central elements has 8e– in their outer most shell.
(c) Electron rich hydrides : These are the hydrides of group 15, 16, 17
Ex. etc.
In these hydrides lone pair are present on central dement which can be given to others. So they are c a l l e d
electron rich hydrides.
Ex. What characteristics do you expect from electron deficient hydrides with respect to their structure and chemical
reactivity ?
Sol. Electron deficient hydrides do not have sufficient number of electrons to form normal covalent bonds. They
generally exist in polymeric forms such as B2H6, B4H10, (AIH3)n, etc.
Due to deficiency of electrons, these hydrides act as Lewis acids and thus, form complex entities with Lewis bases
such as : NH3, H– ions, etc.
xx
B2H6 + 2 N H3 o [BH2(NH3)2]+[BH4]–
B2H6 + 2NaH o 2Na+[BH4]– (sodium borohydride)

Ex. Do you expect the carbon hydride of the type (CnH2n+2) to act as Lewis acid or base ? Justify your answer.
Sol. Carbon hydride of the type (CnH2n+2) are electronprecise hydrides. In other words, they have exact numbers of
electrons required to form covalent bonds. Therefore, they do not have tendency to either gain or lose electrons and
hence, they do not act as Lewis acids or Lewis bases.
Ex. Arrange the following :
(i) CaH2, BeH2 and TiH2 in order of increasing electrical conductance.
(ii) LiH, NaH and CsH in order of increasing ionic character
(iii) H–H, D–D and F–F in order of increasing bond dissociation enthalpy.
(iv) NaH, MgH2 and H2O in order of increasing reducing property.

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CHEMISTRY FOR NEET & AIIMS

Sol. (i) BeH2 is a covalent hydride, therefore, it does not conduct electricity at all. CaH2 conducts electricity in the
fused state while TiH2 conducts electricity at room temperature. Thus, the order of increasing electrical
conductance is : BeH2 < CaH2 < TiH2.
(ii) Electronegativity decreases down the group from Li to Cs, therefore, the ionic character of their hydrides also
increases in the same order, i.e., LiH, < NaOH < CsH.
(iii) F – F bond dissociation enthalpy is the minimum. This is due to high concentration of electron density around
each F atom in the form of 3 lone pairs which cause significant repulsive interactions. The bond enthalpy of D–
D bond is slightly higher than that of H–H bond. It is due to marginally smaller size of D. Thus, the bond
dissociation enthalpy increases in the order : F–F < H–H < D–D.
(iv) Ionic hydrides are powerful reducing agents. Both MgH2 and H2O are covalent hydrides but the bond
dissociation of O–H bonds in H2O is much higher than that of Mg–H bond in MgH2. Therefore, the reducing
character increases in the order : H2O < MgH2 < NaH.
Ex. How do you expect the metallic hydrides to be useful hydrogen storage ? Explain.
Sol. In some of the transition metal hydrides, hydrogen is absorbed as H atoms. Due to the inclusion of H-atoms, the
metal lattice expands and thus becomes less stable. Therefore, when such metallic hydride is heated, it decomposes
to release hydrogen gas and very finely divided metal. The hydrogen evolved in this manner can be used as a fuel.
Thus, transition metals or their alloys can act as sponge and can be used to store and transport hydrogen to be used
as a fuel.
Ex. Explain the meaning of term hydride gap.
Sol. Elements of group 7, 8, 9 of d-block do not form hydrides at all. This inability of metals of group 7, 8, 9 of periodic
table to form hydrides is referred to as hydride gap of d-block.
Ex. Explain the following :
(a) Water is excellent solvent for ionic compounds.
(b) Lakes freeze from top to bottom.
Sol. (a) Water has a high dielectric constant (78.39) due to the polar character of its molecule. Water is an excellent
solvent for many ionic as well as covalent compounds. Dissolution of ionic compounds takes place because of
ion-dipole interactions. Dissolution of molecular compounds such as alcohols, amides, urea, sugar, glucose,
honey, etc., in water takes place because of the tendency of these substances to form hydrogen bonds with
water molecules.
(b) This is due to the fact that the frozen water does not sink to the bottom but keeps floating at the surface due to
its lesser density. This provides thermal insulation to the water below it. The lesser density of ice can be
attributed to open cage-like structure on account of hydrogen bonding.
WATER (H2O )
PROPERTIES OF PURE WATER
(a) Physical properties :
(i) Pure water is colourless, tasteless and odourless. It gives bluish tinge in thick layers.
(ii) It freezes at 0°C and boils at 100°C.
(iii) Its maximum density is 1.00 at 4°C.
(iv) It is a polar molecule and has V-shaped structure. The bond angle is 104.5°.
(v) It has a high dielectric constant. The polar character of water makes it an excellent solvent for polar and ionic
substances.
(vi) It is a poor conductor of electricity.
(vii) It has the tendency to associate. It exists in the liquid state not as a single H2O molecule but as associated
molecules through hydrogen bonding. The existence of hydrogen bonding is responsible for high values of
specific heat, the latent heat of fusion and latent heat of vaporisation.
(b) Chemical properties :
(i) Water is neutral in nature. pH of the pure water is 7. It is a weak electrolyte and feebly ionises into H+ and OH– ions.
H 2O H+ + OH–

115
 HYDROGEN AND ITS COMPOUNDS

In pure water [H+] = [OH–] = 10–7 at 25°C.

(ii) With metals : it reacts with active metals and evolves hydrogen. The reaction is exothermic in the case of alkali
and alkaline earth metals.
2Na + 2H2O o2NaOH + H2
Ca + 2H2O oCa(OH)2 + H2
(iii) Reaction with non metals :
Chlorine decomposes cold water forming HCl and HClO.
Cl2 + H2O oHCl + HClO
(Hypochlorous acid )

When steam is passed over red hot coke (1000°C), water gas is formed.
C  H 2 O o CO  H 2
 

Water gas

(iv) Action on nonmetallic oxides : Acidic oxides combine with water to form acids.
CO2 + H2O U H2CO3 (Carbonic acid)
SO2 + H2O oH2SO3 (Sulphurous acid)
SO3 + H2O oH2SO4 (Sulphuric acid)
P2O5 + 3H2O o2H3PO4 (Orthophosphoric acid)
N2O5 + H2O o2HNO3 (Nitric acid)
Cl2O7 + H2O o2HClO4 (Perchloric acid)
(v) Action on metallic oxides : basic oxides combine with water to form alkalies.
Na2O + H2O o2NaOH
CaO + H2O oCa(OH)2
(vi) Action on hydrides, carbides, nitrides, phosphides : Water decomposes these compounds with liberation of
hydrogen, acetylene (or methane), ammonia, phosphine respectively.
CaH2 + 2H2O oCa(OH)2 + 2H2
CaC2 + 2H2O oCa(OH)2 + C2H2
Al4C3 + 12H2O o4Al(OH)3 + 3CH4
Mg3N2 + 6H2O o3Mg(OH)2 + 2NH3
Ca3P2 + 6H2O o3Ca(OH)2 + 2PH3
(vii) Hydrolysis : Many salts specially the salts of strong bases with weak acids,weak bases with strong acids and
weak bases with weak acids undergo hydrolysis with water.
CH3COONa + H2O o CH3COOH + NaOH
CH3COONH4 + H2O o CH3COOH + NH4OH
Halides of nonmetals are decomposed by water.
PCl5 + 4H2O oH3PO4 + 5HCl
PCl3 + 3H2O oH3PO3 + 3HCl
HARD AND SOFT WATER
A water is said to be a soft water if it produces sufficient lather with the soap and water is described as being hard if it
forms an insoluble scum before it forms a lather with soap. The hardness of natural water is generally caused by presence
of bicarbonates, chlorides and sulphates of calcium and magnesium but infact soluble salts that form a scum with soap
cause hardness.
Ca2+(aq) + 2C17H35COO– (aq) o(C17H35COO)2Ca
Mg2  (aq)  2C 17 H 3 5 COO  (aq) o( C 17 H 35 COO )2 Mg
Anion of soap Inso lub le precipitates

Soap will not produce lather with water until all the calcium and magnesium ions have been precipitated. Hard water thus
wastes soap. Hardness of water is of two types :

116
CHEMISTRY FOR NEET & AIIMS
(I) Temporary hardness
(II) Permanent hardness
(I) TEMPORARY HARDNESS : This is due to the presence of bicarbonates of calcium and magnesium.
Temporary hardness in water is easily removed by boiling, as the bicarbonates decompose readily and the
insoluble carbonates are precipitated.
Ca(HCO 3 )2 
Boil
o CaCO 3  H 2 O  CO 2
(Inso lub le )

Mg(HCO 3 )2 
Boil
o MgCO 3  H 2 O  CO 2
(Inso lub le )

Temporary hardness can also be removed by Clark's process which involves the addition of slaked lime
[Ca(OH)2].
Ca(HCO3)2 + Ca(OH)2 o 2 CaCO + 2H2O
(Inso lub le )

It is essential to add only the calculated amount of Ca(OH)2 because excess will cause artificial hardness.
(II) PERMANENT HARDNESS : Permanent hardness is introduced when water passes over rocks containing the
sulphates or chlorides of both of calcium and magnesium. This type of hardness cannot be removed by boiling
or by the addition of slaked lime.
The various water softeners are :
(i) Washing soda : It removes both the temporary and permanent hardness by converting soluble calcium and
magnesium compounds into insoluble carbonates.
CaCl2 + NaCO3 = CaCO3 + 2NaCl
CaSO4 + Na2CO3 = CaCO3 + Na2SO4
Ca(HCO3)2 + Na2CO3 = CaCO  2NaHCO 3
(Inso lub le ) (So lub le )

In place of sodium carbonate, caustic soda or sodium phosphate can also be used.
MgCl2 + 2NaOH o Mg(OH )2 + 2NaCl
(Inso lub le )

3MgSO4 + 2Na3PO4 o Mg 3 (PO 4 )2 + 3Na2SO4

(Inso lub le )

(ii) Calgon : The complex salt of metaphosphoric acid, sodium hexametaphosphate (NaPO3)6, is known
as calgon. It is represented as Na2[Na4(PO3)6]. Calcium and magnesium salts present in hard water
react with calgon to give complex salts.
2CaSO4 + Na2[Na4(PO3)6] oNa2[Ca2(PO3)6] + 2Na2SO4
2MgSO4 + Na2[Na4(PO3)6] oNa2[Mg2(PO3)6] + 2Na2SO4
(iii) Permutit process : Permutit is hydrated sodium alumino silicate
[Na2Al2Si2O8. xH2O]
[Na2O.Al2O3.2SiO2.xH2O]
Permutit also known as sodium zeolite (Na2Z). means Zeolite is Al2Si2O8.xH2O.
In this process when hard water is poured into chamber, it may contain organic impurities like
plant. This impurities can be removed by gravel.
On moving upwards hard water will react with Na2Z during this reaction Na+ ions of Na2Z will
replace Mg+2 & Ca+2 of impurities.
Na2Z + CaCl2 o2NaCl + CaZ
NaCl is dissolved in water & water becomes soft.
This soft water is fit for washing purpose but not fit for drinking purpose.
After some time when Na2Z is completely converted into CaZ. Process is stopped and for regeneration of
Na2Z. We use NaCl solution.
2NaCl + CaZ oCaCl2 + Na2Z

117
 HYDROGEN AND ITS COMPOUNDS

Hard water

NaCl solution

Na2Z Soft water

Graves

Impurities

(iv) Ion exchange resin : By this process we can remove both cation & anion of hardness.
This process contain two chamber.
(a) Cation exchange resin : This resin contains granular insoluble organic acid having giant molecules
with –COOH group.
(b) Anion exchange resin : This resin contain giant organic molecules with basic groups derived from
amines.
R–NH3+OH–
Process : When hard water is poured into first chamber the cation of hardness (Mg+2. Ca+2) removed by H+
ions of organic acid.
2R–COO H + CaCl2 o(R–COO)2Ca + 2H+ + 2Cl–
– +

+ MgSO4 o(R–COO)2Mg + 2H+ + SO4–2

+ - 2-
Impure water H ,Cl ,SO4
2+ + 2- -
Ca ,Na ,SO4 ,Cl
Dilute acid for

regeneration
regeneration

Alkali for

Cation Anion
exchanger exchanger

Waste Waste
Pure water
This water becomes soften but not used for drinking purpose because this water contain the impurity of acid. To remove
anion of hardness this acidic water then passed through another bed containing anion exchanger. This exchanger
removes anion like Cl–, SO4–2 & HCO3–.
R–NH3+OH– + H+ + Cl– oR–NH3+Cl– + H+OH
This water is free from impurities & can be used for drinking purpose.
After some times when both resin gets exhausted process is stopped.
Regeneration of resin
(i) Cation exchange resin : We use dil acid.
2H+Cl– + (R–COO)2Ca o 2R–COO–H+ + CaCl2
(ii) Anion exchange resin : We use dil NaOH solution
R–NH3+Cl– + Na+OH– oNa+Cl– + R–NH3+OH–

118
CHEMISTRY FOR NEET & AIIMS
HEAVY WATER (D2O)
METHOD OF PREPARATION
Repeated electrolysis of H2O : On electrolysis of water (impure) H2O dissociate into H+ & OH– while a fractional part of
D2O will dissociate into D+ & OD–
H2O U H+ + OH–
D2O U D+ + OD–
D+ & OD– due to more mass have less mobility i.e. why H+ & OH– will move towards cathode & anode respectively while
D+ & OD– will be in solution.
This process will repeated for six time.
PROPERTIES OF HEAVY WATER
PHYSICAL PROPERTIES :
• Heavy water is a colourless, odourless and tasteless mobile liquid.
• Nearly all the physical constants are higher than the corresponding values of ordinary water.
CHEMICAL PROPERTIES :
Heavy water is chemically similar to ordinary water. However, D2O reacts more slowly than H2O in chemical reactions.
(a) Action of metals : D2O reacts with alkali and alkaline earth metals liberates heavy hydrogen.
2D2O + 2Na o 2NaOD + D2
Sodium deuteroxide

2D2O + Ca o Ca(OD)2 + D2

Calcium deuteroxide

(b) Action with metallic oxides : D2O reacts slowly with basic oxides to form heavy alkalies.
Na2O + D2O o2NaOD
CaO + D2O oCa(OD)2
(c) Action with nonmetallic oxides : D2O reacts slowly with acidic oxides to form deutero acids.
N2O5 + D2O o 2DNO 3
Deutero nitric acid

P2O5 + 3D2O o 2 D PO

3 4
Deutero phosphoric acid

SO3 + D2O o D SO

2 4
Deutero sulphuric acid

(d) Action with metallic carbides, phosphides, nitrides, arsenides, etc. : Like H2O heavy water reacts with carbides,
phosphide nitrides, arsenides, etc. to form corresponding deutero compounds.
CaC2 + 2D2O oCa(OD)2 + C D
2 2
Deutero acetylene

Al4C3 + 12D2O o4Al(OD)3 + 3 CD 4

Deutero methane

Mg3N2 + 6D2O o3Mg(OD)2 + 2ND 3

Deutero ammonia

AlN + 3D2O oAl(OD)3 + ND 3

Deutero ammonia

Ca3P2 + 6D2O o3Ca(OD)2 + 2PD 3

Deutero phosphine

Na3As + 3D2O o3NaOD + AsD 3

Deutero ar sin e

(e) Electrolysis : A solution of heavy water containing Na2CO3 when electrolysed evolve heavy hydrogen at cathode.
2D 2 O 
Electrolysis
o 2D 2  O 2
(Cathode ) (Anode )

119
 HYDROGEN AND ITS COMPOUNDS
USES :
As a neutron moderator : Fission in uranium-235 is brought by slow speed neutrons. The substances which are used for
slowing down the speed of neutrons are called moderators. Heavy water is used for this purpose in nuclear reactors.

H2O2 (HYDROGEN PEROXIDE)

LABORATORY METHOD
In laboratory, H2O2 is prepared by adding calculated amounts of sodium peroxide to ice cod dilute (20%) solution of
H2SO4.
Na2O2 + H2SO4 oNa2SO4 + H2O2
By the action of sulphuric acid or phosphoric acid on hydrated barium peroxide BaO2.8H2O (Merck process)
(a) BaO2.8H2O + H2SO4 oBaSO4p+H2O2 + 8H2O
Anhydrous barium peroxide does not react readily with sulphuric acid (because a coating of insoluble barium
sulphate is formed on its surface which stops further action of the acid). Therefore, hydrated barium peroxide,
BaO2.8H2O must be used.
(b) 3BaO2 + 2H3PO4 o Ba3(PO4)2 + 3H2O
Ba3(PO4)2 + 3H2SO4 o 3BaSO4 + 2H3PO4
Phosphoric acid is preferred over H 2 SO 4 because soluble impurities like barium persulphate
(BaO2.8H2O –H2SO4) tends to decompose H2O2 while H3PO4 acts as preservative (negative catalyst) for H2O2.
INDUSTRIAL METHOD
(i) Auto oxidation of 2 butyl anthraquinol ( cyclic process)

OH
O
C4H9
O C4 H 9
ZZZZ
YZZZ
2
X
Z H 2O 2 +
H 2

OH O
(ii) Oxidation of isopropyl alcohol
CH3—CH—CH 3 + O2


CH3 C CH3 + H2O2
OH O
(iii) Electrolytic Process : Used 50% H2SO4 in electrolytic cell using Pt as anode graphite as cathode.
2H2SO4 o2H+ + 2HSO44
At Cathode 2H+ + 2e– oH2 n
At Anode 2HSO4– oH2S2O8 + 2e–|
Peroxo disulphhuric acid
H2S2O8 + H2O o H2SO4 + H2SO5
H2SO5 + H2O o H2SO4 + H2O2

PHYSICAL PROPERTY :
(i) Pure H2O2 is colour less, odourless liquid and impure with bluish layer.
(ii) It has more Hydrogen bonding then H2O, So order of boiling point. H 2 O 2 > D 2 O > H 2 O
(iii) It is soluble in H2O, alcohol and ether
(iv) It has bitter test and harmful for skin
(v) It is a dibasic weak acid
(vi) It has a oxidising as well as reducing property
(vii) H2O2 easily decompose in presence of light and temperature, So H2O2 always kept in dark bottles and kept at cool
places.
(viii)30% solution of H2O2 is called Perhydrol.

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CHEMISTRY FOR NEET & AIIMS

CHEMICAL PROPERTY :
1. Stability : It is unstable in nature decompose on standing and heating. It is an example of auto oxidation-reduction
Reaction ; H2O2 o H2O + O
Note : Nascent oxygen working as colourless agent

ZZZ
X
Decomposition of H2O2 ; 2H2O2 YZZZ 2H2O + O2
Note : This is retarded by R–OH, acetanilide, glycerol
2. Oxidizing nature : H2O2 is a powerful oxidant in acidic as well as in alkaline medium.

(In acid) H2O2 + 2H+ + 2e 

Fast
o 2H2O E0RP 1.77V

(In alkali) H2O + HO2– + 2e 

Slow
o 3HO
–
E0RP 0.87 V
Thus H2O2 is more powerful oxidant in acidic medium. The simple interpretation of H2O2 as oxidant can be shown by
the equation.
H2O2 oH2O + O
Following are some important examples of oxidant action of H2O2 :
(a) H2O2 oxidises black lead sulphide (PbS) to white lead sulphate (PbSO4). This reaction is used in restoring the
white colour of old paintings which have blackened due to the formation of lead sulphide by the action of H2S
present in air.
4[H2O2 oH2O + O]
PbS + 4O oPbSO4

PbS + 4H2O2 oPbSO4 + 4H2O
(b) H2O2 oxidises sulphites into sulphates.
H2O2 oH2O + O
Na2SO3 + O oNa2SO4

Na2SO3 + H2O2 oNa2SO4 + H2O
(c) H2O2 oxidises nitrites to nitrates.
H2O2 oH2O + O
Na2NO2 + O oNaNO3

Na2NO2 + H2O2 oNa2NO3 + H2O
(d) H2O2 oxidises H2S into sulphur.
H2O2 o H2O + O
H2S + O o H2O + S

H2S + H2O2 o2H2O + S
3. Reducing nature : It can also act as a reducing agent towards powerful oxidising agents.
H2O2 o2H+ + O2 + 2e–
(a) It reduces Ag2O to silver.
Ag2O + H2O2 o2Ag + H2O + O2
(b) It reduces ozone to oxygen.
H2O2 + O3 oH2O + 2O2

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 HYDROGEN AND ITS COMPOUNDS

STRUCTUREOF HYDROGEN PEROXIDE

H
O
O H–O–O–H
H
Kingzett's formula Baeyer's formula
The vapour density as determined by Victor
Meyer method at 90°C is 17. Hence, the molecular mass of H2O2 is 34. Two formulae have been suggested for hydrogen
peroxide.

H H
O
×
O O 94°
×

H
94° O
H
or

H
O 1.48Å O 7Å
0.9
7Å
111°
H 0.9
(A) (B)

The calculated value of the single bond O–O distance is 1.48Å and X-ray measurements shows what in hydrogen
peroxide, O–O bond distance is 1.46 + 0.03Å. The value of dipole moment of H2O2 is 2.1 D. This suggests that all the four
atoms do not lie in the same plane. The molecule can be pictured as lying on the spine of a book open to an angle of 111°.
The hydrogen atoms are present one on each cover and H–O bonds making angles of 94° with the O–O bond as shown
in fig. The bond distance between O–H is 0.97Å.
Precautions
(i) H2O2 can not be stored in simple glass bottles since rough surface of glass [alkali oxides present in it] excited by light
and decomposed H2O2.
So the H2O2 usually stored in coloured, paraffin wax coated, plastic bottle.
(ii) Always with H2O2 add small quantity of inhibitor or negative catalyst to stay decomposition of H2O2.
likeH3PO4, acetanilides etc.

KEY POINTS
Uses of H2O2
(i) Bleaching agent
(ii) Hair dying
(iii) H2O2 + N2H4 as Rocket propellent
(iv) H2O2 as oxidant and reductant
(v) Antiseptic

Ex. What is 'demineralised water' and how can it be obtained ?

Sol. Water which is free from all cations and anions is called demineralised water. It is obtained by passing hard water
first through cation exchange resin and then through anion exchange resin.

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CHEMISTRY FOR NEET & AIIMS
Ex. Explain the following :
(i) Soft water lathers with soap but not hard water.
(ii) Temporary hard water becomes soft on boiling.
(iii) Water can extinguish most fires but not petrol fire.
(iv) Hard water is softened before use in boilers.

Sol. (i) Hard water contains calcium and magnesium salts. These react with soap to form insoluble calcium and
magnesium salts of fatty acids, i.e., form scum and not lather.
2RCOONa (soap) + Ca2+ o (RCOO)2 Ca (insoluble) + 2Na+

2RCOONa (soap) + Mg2+ o (RCOO)2 Mg (insoluble) + 2Na+

(ii) Temporary hardness of water is due to the presence of soluble bicarbonates of calcium and magnesium. On boiling,
the bicarbonates are converted into insoluble carbonates which can be removed by filtration.
Ca(HCO3)2 (soluble) o CaCO3 p + H2O + CO2

Mg(HCO3)2 (soluble) o MgCO3 p + H2O + CO2

(iii) When water poured over petrol fire, petrol being lighter than water floats over water and thus fire spreads instead
being extinguished.
(iv) Hard water consists bicarbonates and other soluble salts of calcium and magnesium. When hard water is evaporated
in boilers, scales of precipitated carbonates of calcium and magnesium along with other salts such as sulphates,
chlorides, etc., are formed. In order to avoid the formation of scales hard water is first softened before use in boilers.

Ex. Knowing the properties of H2O and D2O, do you think that D2O can be used for drinking purposes?
Sol. Heavy water is injurious to human beings, plants and animals since it slows down the rates of reactions occuring in
them. Thus, heavy water does not support life. In fact it retards certain cellular process, such as mitosis, cell
division, etc, Thus, prolonged use of D2O leads to degeneration of tissues.
Ex. Assertion : Anhydrous BaO2 is not used for preparing H2O2.
Reason : H2O2 is prepared on large scale by air oxidation of 2-Ethyl anthraquinol.
(1) If both Assertion and Reason are true and Reason is a correct explanation of Assertion.
(2) If both Assertion and Reason are true and Reason is not a correct explanation of Assertion.
(3) If Assertion is true but Reason is false.
(4) If Assertion is false but Reason is true.
Sol. (2) Assertion : BaO2 + H2SO4 o BaSO4 p (white) + H2O2
Insoluble BaSO4 forms a thin layer around BaO2 and therefore reaction occurs slowly and finally stops. So anhydrous
BaO2, is not used.
Reason : Industrial method (Auto oxidation)

OH O
C2H5 O2 (air) C2H5
(Oxidation) + H2O2
H2 (Ni)
(Reduction)
OH O
2- Ethyl anthraquinol 2-Ehtylanthraquinone
It is cheaper method as only O2 from air and H2 are consumed.

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 HYDROGEN AND ITS COMPOUNDS
DIHYDROGEN ASA FUEL
Dihydrogen releases large quantities of heat on combustion. The data on energy released by combustion of fuels like
dihydrogen, methane, LPG etc. are compared in terms of the same amounts in mole, mass and volume, are shown in
Table
THE ENERGY RELEASED BY COMBUSTION OF VARIOUS FUELS IN MOLES, MASS AND VOLUME
Energy released on Dihydrogen Dihydrogen LPG CH4 gas Octane
combustion in kJ (in gaseous (in liquid) (in liquid
state) state) state)
per mole 286 285 2220 880 5511
per gram 143 142 50 53 47
per litre 12 9968 25590 35 34005
From this table it is clear that on a mass for mass basis dihydrogen can release more energy than petrol
(about three times). Moreover, pollutants in combustion of dihydrogen will be less than petrol. The only pollutants
will be the oxides of dinitrogen (due to the presence of dinitrogen as impurity with dihydrogen). This, of course, can
be minimised by injecting a small amount of water into the cylinder to lower the temperature so that the reaction between
dinitrogen and dioxygen may not take place. However, the mass of the containers in which dihydrogen will be kept
must be taken into consideration. A cylinder of compressed dihydrogen weighs about 30 times as much as a tank of
petrol containing the same amount of energy. Also, dihydrogen gas is converted into liquid state by cooling to 20K.
This would require expensive insulated tanks. Tanks of metal alloy like NaNi5, Ti–TiH2, Mg–MgH2 etc. are in use for
storage of dihydrogen in small quantities. These limitations have prompted researchers to search for alternative techniques
to use dihydrogen in an efficient way.
In this view Hydrogen Economy is an alternative. The basic principle of hydrogen economy is the transportation
and storage of energy in the form of liquid or gaseous dihydrogen. Advantage of hydrogen economy is that energy
is transmitted in the form of dihydrogen and not as electric power. It is for the first time in the history of India
that a pilot project using dihydrogen as fuel was launched in October 2005 for running automobiles. Initially 5%
dihydrogen has been mixed in CNG for use in four-wheeler vehicles. The percentage of dihydrogen would be
gradually increased to reach the optimum level.
Nowadays, it is also used in fuel cells for generation of electric power. It is expected that economically viable and safe
sources of dihydrogen will be identified in the years to come, for its usage as a common source of energy.

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CHEMISTRY FOR NEET & AIIMS

Preparationof hydrogen
(I) Passing steam over hot iron (Lane process)
3Fe + 4 H2O o Fe3P4 + H2 n
(II) By the action of water on hydrolith
CaH2 + H2O  o Ca(OH)2 + 3H2
(III) By the electrolysis of water
(IV) Bosch process
C(s) + H2O (g)  o CO + H2
+
H2O(g) 
FeCrO 4
o CO2 + H2
p
25 atm
H 2O
CO2 absorbed
Properties of molecular hydrogen
Metals like Pd, Pt, Ni, Co etc. adsorb large quantities of the gas due to vacancies between these atoms. This is known as
"occlusion".
Reaction with vegetable oils
473 K
Vegetable oil + H2 Ni
Vegetable gheef (Slid fat)
This process is known as "hydrogenation" or "hardening of oils"
Isotopes of hydrogen
(a) Hydrogen (Protium) (b) Deuterium (c) Tritium
1 2 3
1H or H 1H or D 1H or T
(P = 1, e = 1, n = 0) (P = 1, e = 1, n = 1 (P = 1, e = 1, n = 2)
Different forms ofhydrogen
Atomic hydrogen
H2 electricarc
o 2H
(Molecular hydrogen) (Atomic hydrogen)
Nascent hydrogen
Zn + dil.H2SO4  o ZnSO4 + 2H
Ortho and Para hydrogen
If two nuclei have same spin then it is called "Ortho H2".
If two nuclei have different spin then it is called "Para H2".
HYDRIDES
Ionic or salt like hydrides : s block
Li H, NaH, KH, RbH, SrH2, BaH2 etc.
Be & Mg hydrides are covalent in nature
Molecular or covalent hydrides : p block
NH3, PH3, H2O, CH4 etc.
Metallic or Interstitial hydrides : trasition elements

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 HYDROGEN AND ITS COMPOUNDS

In these hydrides, hydrogen atoms occupies the interstitial position of metallic latice.
La H2.87, Ti H1.8, Zr H1.9
Hydride gap = 7, 8, 9
WATER
(I) The existence of hydrogen bonding is responsible for high values o specific heat, the latent of fusion and
latent heat of vapourisation and high boiling point.
(II) Some of the covalent compounds such as alcohols, carboxylic acids and carbohydrates are soluble in water due to
formation of hydrogen bonding.
Hardness of Water
Temporary hardness of water is due to bicarbonates of Ca and Mg. It can be removed by –
(a) Boiling
(b) Clark method using CaO
Permanent hardness of water is due to chloride/sulphate of Ca and Mg. It can be removed by –
(a) Adding washing soda, Na2CO3
(b) Calgon [Na6(PO3)6]
(c) Permutit, Na2 Al2 Si2 O8. xH2O
(d) Artificial resins, RSO3H & RNH2OH
Heavy water or Deuterium oxide (D2O)
(a) It is produced by repeated electrolysis of ordinary water containing alkali.
(b) Most important use of heavy water is in nuclear reactors for slow down the speed of neutron (i.e. as a moderator)
HYDROGEN PEROXIDE
Preparation
(I) BaO2 . H2O + H2SO4  o BaSO4 + H2O2 + 8 H2O
(II) Na2O2 + 2 H2SO4  o 2 Na2SO4 + H2O2
(III) BaO2 + H2O + CO2  o BaCO3 + H2O2
(IV) Oxidation of 2 Alkyl anthraquinol
(V) Electrolysis of 50% H2SO4
Chemical properties
(a) Decomposition
2H2O2 H2O + O2
reduction
oxidation

(b) H2O2 can accept as well can donate electrons and thus it can acts as an oxidising and reducing agtent in acidic as
well as alkaline medium
(c) Oxidising properties and Reducing behaviour of H2O2 :
KMnO4/H+
O2+Mn+4
KMnO4/OH–
O2+Mn4+
2+ –
Fe /OH
Fe+3
RA
O2 2+ +
Fe /H
(I) H2O2 OA
H2O (II) H2O2 Fe+3
1/2
disproportionate H2O + O2 HOCl/H
+

O2+HCl
–
I2/OH
O2+I–
Mn +2/OH–
Mn4+

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CHEMISTRY FOR NEET & AIIMS

(e) Bleaching action

H2O2  o H2O + [O]
Structure

H
O
94°48'
O Open book structure
H
111°30'
Structure of H2O2 in the gas phase.

Tests of H2O2
(a) It liberates iodien from KI solutin in the presence of ferrous sulphate.
(b) It gives orange red colour with acidified titanium oxide due to formation of pertitianic acid.
Ti(SO4)2 + H2O2 + 2H2O  o H2TiO4 + 2 H2SO4
(c) It gives blue colour with acidicfied K2Cr2O7 and ether. The blue colour of chromium peroxide is stabilized by ether.
CrO42– + 2H+ + 2H2O2  o CrO5 + 3H2O

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 HYDROGEN AND ITS COMPOUNDS

SOLVED EXAMPLE
Ex. 1 How does the atomic hydrogen or oxy-hydrogen SiH4, GeH4, etc. have exact number of electrons to
torch function for cutting and welding purposes ? form covalent bonds and hence are called electron-
Explain. precise hydrides. All these hydrides have tetrahedral
Sol. Atomic hydrogen is produced when molecular shapes.
hydrogen is passed through an electric arc struck (iii) Hydrides of elements of group 15, 16 and 17,
between tungsten electrodes (3773–4273 K). like NH3, PH3, H2O, H2S, HF, HCl, etc. have more
electrons than required to form normal covalent
H2(g)   o H(g) + H(g) : 'H = 436.0 kJ
electric arc
bonds and hence are called electron-rich hydrides.
mol –1
The excess electron in these hydrides are present
The life span of atomic hydrogen is about 0.3 sec as lone pairs of electrons.
and therefore, it immediately gets converted into
the molecular hydrogen (H 2) liberating a large Ex. 4 Which of the following is correct for hydrogen ?
amount of energy which is used for cutting and (A) It is always collected at cathode.
welding purposes in the form of atomic hydrogen (B) Its ionization energy is very low incomparision
torch. with alkali metals.
Ex. 2 What do you understand by the term " non- (C) It can form bonds in +1 as well as in –1 oxidation
stoichiometric hydrides" ? Do you expect this type states.
of hydrides to be formed by alkali metals ? Justify (D) Its oxide is not stable.
your answer. 1 1
Sol. (C) 2Na + H2 o 2 Na H ;
Sol. These are hydrides which have low hydrogen
content. In these hydrides the ratio of the metal to
3 1
hydrogen atoms is fractional and they are called N2 + 3H2 o 2 N H 3
non-stoichiometric hydrides. Furthermore, even this
fractional ratio of atoms is not fixed but varies with Ex. 5 Metal which does not react with cold water but
the temperature and the pressure conditions. This evolves H2 with steam is :
type of hydrides are formed by d-and f-block (A) Na (B) K
elements. In these hydrides, the hydrogen atoms (C) Pt (D) Fe
occupy holes in the metal lattice. Usually some holes
Sol. (D)
always remain unoccupied and hence these metals
form non-stoichiometric hydrides. 4H2O(g) + 3Fe(s)  o Fe3O4 + 4H2 n
1000 K

Alkali metals are highly reducing as they transfer
their lone electron to the H atom, thereby, forming Ex. 6 Saline hydride are known to react with water violently
H– ions. In other words, alkali metals hydrides are producing fire, Can, CO 2, a well known fire
ionic in nature. SInce such hydrides are formed by extinguisher, be used in this case ? Explain.
complete transfer of an electron, therefore, the ratio Sol. Saline hydride (Such as NaH, CaH2, etc), react with
of metal to hydrogen is always fixed. Therefore, alkali water violently to form the corresponding metal
metals form only stoichiometric hydrides. They do hydrox ides with the evolution of dihydrogen. The
not form non-stoichiometric hydrides at all. dihydrogen gas so liberated undergoes spontaneous
combustion causing fire. This is because of
Ex. 3 What do you understand by (i) electron-deficient, exothermic nature of combustion reactions.
(ii) electron-precise, and (iii) electron rich
compounds of hydrogen ? Provide justification NaH(s) + H2O(A) o NaOH (aq) + H2(g)
with suitable examples.
CaH2(s) + 2H2O (A) o Ca(OH)2(aq) + 2H2(g)
Sol. (i) Hydrides of elements of group–13 such as BH3,
AIH3, etc., do not have sufficient number of electrons The fire so produced cannot be extinguished by
to form normal covalent bond and hence are called CO2 because it reacts with the hot metal hydride
electron-deficient hydrides. To make up this and forms formate ions
deficiency, they generally exist in polymeric forms NaH + CO2 o HCOONa
such as B2H6, B4H10, (AIH3)n, etc.
However, send (because of its stable nature) is more
(ii) Hydrides of elements of group-14 like CH4,
effective fire extinguisher in such a case.

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CHEMISTRY FOR NEET & AIIMS
Ex. 7 How can the production of dihydrogen, obtained Sol. (A) o (r) ; (B) o (p) ; (C) o (q) ; (D) o (s)
from coal gasification, be increased ? (A) Chemically heavy water is D2O, i.e. deuterium
Sol. Coal gasification is the process of producing 'syngas' oxide.
from coal and steam (B) Temporary hardness of water is due to the
1270K ( g)  H ( g)
presence of bicarbonates of calcium and magnesium
C(s) + H2O(g)  o CO
  2
and can be removed by simple boiling.
Ni syngas
Ca(HCO3)2 o ' CaCO3 p + H2O + CO2
The production of hydrogen can be increased by
the reaction carbon monooxide of syngas with steam (C) Water which produces lather with soap solution
in presence of iron chromate as catalyst at 673 K readily, is called soft water e.g., distilled water, rain
when it is oxidised to CO2. water and demineralised water. It contains no foreign
673 K ions.
CO(g) + H2O(g)  o CO2(g) + H2(g)
FeCrO 4 (D) Permanent hardness of water is due to the
presence of sulphates and chlorides of calcium and
The CO2 thus produced is removed by scrubbing magnesium and can be removed by chemical
with a solution of sodium arsenite. methods.
Ex. 8 Among NH3, H2O and HF which would you expect CaCl2 + Na2CO3 o CaCO3 p + 2NaCl
to have highest magnitude of hydrogen bonding
Ex. 11 Is demineralised or distilled water useful for drinking
and why ?
purpose ? If not, how can it be made useful ?
Sol. Strength of H–hydrogen depends upon the atomic Sol. Demineralised or distilled water is not useful for
size and electronegativity of the other atom to which drinking purpose because it does not contain even
H–atom is covalently bonded. Smaller size and useful minerals. Therefore, to make it useful for
higher electronegativity favour H-bonding. Now drinking purposes, useful minerals in proper amounts
among N,F, O atoms, atomic size of F is lowest and should be added to demineralised or distilled water.
its electronegativity is highest. Hence H–F will have
highest magnitude of H–bonding. Ex. 12 Consider the reaction of water with F2 and suggest
in terms of oxidation and reduction which species
Ex. 9 What do you understand by the term 'auto-
are oxidised/reduced ?
protolysis' of water. What is its significance ?
Sol. 2F2(g) + 2H2O(A) o O2(g) + 4H+(aq) + 4F–(aq)
Sol. Auto-protolysis refers to self ionization of water. It
may be represented as : (oxidant) (reductant)
H2O(A) + H2O(A) H3O+(aq) + OH–(aq) or 3F2(g) + 3H2O(A) o O3(g) + 6H–(aq) + 6F–
Acid1 Base2 Acid2 Base1 (aq)
Due to auto-protolysis, water acts as amphoteric (oxidant) (reducant)
substance i.e., it reacts with both acids and bases. It In these reactions, water acts as a reducing agent
acts as a base towards acids stronger than itself and gets oxidised to either O2 or O3 on the other
and as an acid towards bases stronger than itself. hand, F2 acts as an oxidising agent and gets reduced
For example, to F– ion.
H2O(A) + NH3(aq) o NH4+(aq) + OH– (aq) Ex. 13 Describe the usefulness of water in biosphere and
biological systems.
Acid1 Base2 Acid2 Base1
Sol. Water is essential for all forms of life. It constitutes
H2O(A) + H2S(aq) o H3O (aq) + HS– (aq)
+
about 65-70% of the body mass of animals and
Base1 Acid2 Acid1 Base2 plants, In comparison to other liquids, water has
high specific heat, thermal conductivity, surface
Ex. 10 Match list-I with list-II and select the correct answer
tension, dipole moment and dielectric constant, etc.
Column-I Column-II
These properties allow water to play a key role in
(A) Heavy water (p) Bicarbonates of Mg biosphere. The high heat of vaporisation and high
and Ca in water heat capacity are responsible for moderation of the
(B) Temporary hard water (q) Distilled water climate and body temperature of living beings. It is
(C) Soft water (r) Deuterium oxide an excellent solvent for transportation of minerals
(D) Permanent hard water (s) Sulphates and and other nutrients for plant and animal metabolism.
chlorides of Mg Water is also required for photosynthesis in plants
and Ca in water. which releases O2 into the atmosphere.

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 HYDROGEN AND ITS COMPOUNDS
Ex. 14 What properties of water make it useful as a solvent Ex. 17 How can saline hydrides remove traces or water
? What type of compounds can it (i) dissolve (ii) from organic compounds ?
hydrolyse ?
Sol. Saline hydrides (i.e. NaH, CaH2, etc.) react with water
Sol. Water has high dielectric constant (79.39) and high
forming their corresponding metal hydroxides with
dipole moment (1.84 D). Because of these properties,
the liberation of H2 gas. Thus traces of water present
water dissolves most of the inorganic (ionic)
compounds and many covalent compounds. That in organic solvents can be easily removed by
is why water is called a universal solvent. Ionic distilling them over saline hydrides when H2 escapes
compounds dissolve in water due to ion dipole into the atmosphere, metal hydroxide is left in the
interaction but, covalent compounds such as flask while dry organic solvent distills over.
alcohol, amines, urea, glucose, sugar, et., dissolve Alternatively, organic compounds containing traces
in water due to H–bonding.
of water can be dried by placing them in a desicator
Water can hydrolyse many metallic or non-metallic
containing saline hydrides at the bottom for a few
oxides, hydrides, carbides,nitrides,phosphides and
hours or preferably overnight.
other salts. Some of the important hydrolytic
reactions are given below. Ex. 18 Do you expect different products in solution when
CaO(s) + H2O(A) o Ca(OH)2(aq) aluminium (III) chloride and potassium chloride are
CaH2 (s) + 2H2O(A) o Ca(OH)2(aq) + 2H2(g) treated separately with (i) normal water (ii) acidified
Ca3N2(s) + 6H2O(s) o 3Ca(OH)2(aq) + 2NH3(g) water, and (iii) alkaline water ?
(ammonia) Sol. KCI is the salt of a strong acid and a strong base. It
does not undergo hydrolysis in normal water. It just
Ex. 15 What is the difference between hydrolysis and
hydration ? dissociates to give K+(aq) and Cl–(aq) ions giving
Sol. Hydrolysis refers to the reaction of salt or more neutral solution.
precisely ions of the salt to form acidic or basic water
KCl(s)  o K+(aq) + Cl–(aq)
solution. For example,
Na2CO3 + 2H2O 2Na+ + 2OH– + H2CO3 AlCl3, on the other hand, is a salt of a weak base
Al(OH)3 and a strong acid HCl. Therefore, in normal
NH4Cl + H2O H+ + Cl– + NH4OH
water, it undergoes hydrolysis, as follows giving
Hydration, refers to the addition of H2O to ions or
acidic solution.
molecules to form hydrated ions or hydrated salts.
For example, AlCl3(s) + 3H2O(A) o Al(OH)3(s) + H+(aq) +

NaCl(s) + H2O o Na (aq)  Cl (aq) Cl–(aq)
 

Hydrated ions In acidic water, both KCl and AlCl 3 undergo

ionisation.
CuSO4(s) + 5H2O(A) o CuSO45H2O(s)
Anhydrous salt Hydrated salt KCl    o K (aq) + Cl (aq)
acidified water + –

Ex. 16 Consider the following statements.

AlCl3(s)    o Al (aq) + 3Cl (aq)
acidified water 3+ –

S1 : Water at 4°C having maximum density is known

as heavy water. In alkaline water, AlCl3 reacts to form soluble
S2 : Heavy water is formed by the combination of tetrahydroxoaluminate (III) complex or
hydrogen and oxygen. metaaluminate ion, i.e. AlO–2
S3 : D2O has higher density than H2O. AlCl3(s) + 4OH–(aq) o [Al(OH)4–](aq) + 3Cl–
S4 : D2O is obtained by exhaustive electrolysis of (aq)
water.
Which of the statements are correct ?
tetrahydroxoaluminate
(A) S1 and S2 (B) S2 and S3
AlO2–(aq) + 2H2O(A)
(C) S3 and S4 (D) S2 and S4
Meltaaluminate ion
Sol. (C) S3 : Heavy water is oxide of deuterium. Its density KCl does not react and only undergoes ionisation
is 1.106 gm–3 and that of H2O is 1.00 gm–3. as K+ and Cl– ions.
S4 : Correct statement.

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CHEMISTRY FOR NEET & AIIMS
Ex. 19 What do you expect the nature of hydrides if formed Ex. 20 Assertion : H2O2 is not stored in glass bottles.
by elements of atomic numbers 15,19,23 and 44 with Reason : Alkali metal oxides present in glass catalyse
dry dihydrogen? Compare their behaviour towards the decomposition of H2O2.
water. (A) If both Assertion and Reason are true and
Sol. (i) Element with Z = 15 is a non-metal (i.e., P) and Reason is a correct explanation of Assertion.
hence forms covalent hydride (i.e., PH3). (B) If both Assertion and Reason are true and
(ii) Element with Z = 19 is a alkali metal (i.e., K) and Reason is not a correct explanation of Assertion.
hence forms saline or ionic hydride (i.e., K+ H–) (C) If Assertion is true but Reason is false.
(iii) Element with atomic number Z = 23 is a transition (D) If Assertion is false but Reason is true.
metal (i.e., V) belonging to group 3. Hence it forms Sol. (A) Assertion and reason both are correct statements
interstitial hydride (i.e. VH1.6) and the reason is the correct explanation of the
(iv) Element with Z = 44 is a transition metal (i.e. Ru) assertion.
belonging to group 8. It does not form any hydride.
Alkali metal oxide
Only ionic hydrides react with water evolving H2 2H2O2     o 2H2O + O2.
gas.
2KH(s) + 2H2O(s) o 2KOH(aq) – 2H2(g)

131
CHEMISTRY FOR NEET & AIIMS

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. The structure of H2O2 is [CBSE AIPMT 2006] 9. On heating which of the following releases CO2 most
(A) planar (B) non-planar easily ? [CBSE AIPMT 2015]
(C) spherical (D) linear (A) K2CO3 (B) Na2CO3
(C) MgCO3 (D) CaCO3
2. The correct order of the mobility of the alkali metal
ions in aqueous solution is [CBSE AIPMT 2006] 10. Solubility of the alkaline earth’s metal sulphates in
water decreases in the sequence
(A) Li+ > Na+ > K+ > Rb+
[CBSE AIPMT 2015]
(B) Na+ > K+ > Rb+ > Li+
(A) Mg > Ca > Sr > Ba (B) Ca > Sr > Ba > Mg
(C) K+ > Rb+ > Na+ > Li+ (C) Sr > Ca > Mg > Ba (D) Ba > Mg > Sr > Ca
(C) Rb+ > K+ > Na+ > Li+
11. “Metals are usually not found as nitrates in their
3. The correct order of increasing thermal stability of ores”. [CBSE AIPMT 2015]
K2CO3, MgCO3, CaCO3 and BeCO3 is Out of the following two (I and II) reasons which is/
[CBSE AIPMT 2007] are true for the above observation?
(A) BeCO3 < MgCO3 < K2CO3 < CaCO3 I. Metal nitrates are highly unstable
(B) BeCO3 < MgCO3 < CaCO3 < K2CO3 II. Metal nitrates are highly soluble in water.
(C) MgCO3 < BeCO3 < CaCO3 < K2CO3 (A) I and II are ture (B) I and II are false
(D) K2CO3 < MgCO3 < CaCO3 < BeCO3 (C) I is false but if is true (D) I is true but II is false
4. In which of the following the hydration energy is 12. In context with beryllium, which one of the following
higher than the lattice energy ? [CBSE AIPMT 2007] statements is incorrect ? [NEET 2016, Phase II]
(A) BaSO4 (B) MgSO4 (A) It is rendered passive by nitric acid
(C) RaSO4 (D) SrSO4 (B) It forms Be2 C
(C) Its salts rarely hydrolyse
5. The sequence of ionic mobility in aqueous solution (D) Its hydride is electron-deficient and polymeric
is [CBSE AIPMT 2008]
13. Which of the following statements about hydrogen
(A) K+ > Na+ > Rb+ > Cs+ (B) Cs+ > RB+ > K+ > Na+
is incorrect ? [NEET 2016, Phase I]
(C) Rb+ > K+ > Cs+ > Na+ (D) Na+ > K+ > Rb+ > Cs+
(A) Hydrogen never acts as cation in ionic salts
6. The alkali metals form salt like hydrides by the (B) Hydronium ion, H3O+ exists freely in solution
direct synthesis at elevated temperature. The (C) Dihydrogen does not act as a reducing agent
thermal stability of these hydrides decreases in (D) Hydrogen has three isotopes of which tritium is
which of the following orders ? the most common
[CBSE AIPMT 2008] 14. Which of the following statements is false ?
(A) CsH > RbH > KH > NaH > LiH [NEET 2016, Phase I]
(B) KH > NaH > LiH > CsH > RbH (A) Ca2+ ions are important in blood clotting
(C) NaH > LiH > KH > RbH > CsH (B) Ca2+ ions are not important in maintaining the
(D) LiH > NaH > KH > RbH > CsH regular beating of the heart
(C) Mg2+ ions are important in the green parts of
7. Equimolar solutions of the following were prepared plants
in water separately. Which one of the solutions will (D) Mg2+ ions form a complex with ATP
record the highest pH ? [CBSE AIPMT
2008] 15. The product obtained as a result of a reaction of
(A) SrCl2 (B) BaCl2 nitrogen with CaC2 is [NEET 2016, Phase I]
(C) MgCl2 (D) CaCl2 (A) CaCN (B) CaCN3
(C) Ca2CN (D) Ca(CN)2
8. Which one of the following is present as an active 16. Ionic mobillity of which of the following alkali
ingredient in bleaching powder for bleaching metal ions is lowest when aqueous solution of their
action ? [CBSE AIPMT 2011] salts are put under an electric field ? [NEET 2017]
(A) Ca(OCl)2 (B) CaO2Cl2 (A) Na (B) K
(C) CaCl2 (D) CaOCl2 (C) Rb (D) Li

132
 HYDROGEN AND ITS COMPOUNDS

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

1. The reagent commonly used to determine hardness ASSERTION AND REASON

of water titrimetrically is In each of the following questions, two statement
(A) oxalic acid are given one is assertion and the other is reason.
(B) disodium salt of EDTA Examine the statement carefully and mark the correct
(C) sodium citrate answer according to the instruction given below
(D) sodium thiosulphate [2003]
(A) If both the assertion and reason are true and
reason explains the assertion
2. 100 cm3 of a given sample of H2O2 gives 1000 cm3 of (B) If both the assertion and reason are true but
O2 at S.T.P. The given sample is reason does not explain the assertion
(A) 10% H2O2 (C) If assertion is true but reason is false
(B) 90% H2O2 (D) If assertion is false but reason in true
(C) 10 volume H2O2 (E) Both assertion & reason are false
(D) 100 volume H2O2 [2010]
8. Assertion : The O – O bond length in H2O2 is shorter
3. In solid ice, oxygen atom is surrounded than that of O2F2.
(A) tetrahedrally by 4 hydrogen atoms Reason : H2O2 is an ionic compound.
[2003]
(B) octahedrally by 2 oxygen and 4 hydrogen atoms
(C) tetrahedrally by 2 hydrogen and 2 oxygen atoms 9. Assertion : Sulphur is oxidised by H2O2 in presence
(D) octahedrally by 6 hydrogen atoms of Fe (III)
[2011] Reason : Fe (III) oxidises sulphur to sulphate.
[2011]
4. Predict the product of reaction of I2 with H2O2 in
basic medium. 10. Assertion : Permanent hardness of water is removed
(A) I– (B) I2O3 by treatment with washing soda.
(C) IO3– (D) I3 [2011] Reason : Washing soda reacts with soluble calcium
and magnesium chlorides and sulphates in hard
5. Strength of H2O2 is 15.18 g L–1, then it is equal to water to form insoluble carbonates.
(A) 1 volume (B) 10 volume
11. Assertion : H2O2 has higher boiling point than water.
(C) 5 volume (D) 7 volume
Reason : H 2 O 2 has stronger dipole-dipole
[2013]
interactions than that shown by water. [2015]
6. Which of the following reactions increases the
production of dihydrogen from synthesis gas ?

(A) CH 4(g)  H 2 O(g) 

1270 K
o CO(g)  H 2(g)
Ni

(B) C(s)  H 2 O(g) o CO(g)  H 2(g)

1270 K

(C) CO(g)  H 2 O(g)  o CO 2(g)  H 2(g)

673 K
Catalyst

(D) C2 H 6  2H 2 O 
1270 K
o 2CO  5H 2
Ni
[2014]

7. Which of the following reactions produces

hydrogen ?
(A) Mg + H2O (B) H2S2O8 + H2O
(C) BaO2 + HCl (D) Na2O2 + 2HCl
[2015]

133
 HYDROGEN AND ITS COMPOUNDS

ANSWER KEY

EXERCISE : PART # I
1. B 2. D 3. B 4. B 5. B 6. D 7. B 8. A 9. C 10. A 11. C 12. C 13. C,D
14. B 15. * 16. D

EXERCISE : PART # II
1. B 2. C 3. A 4. A 5. C 6. C 7. A 8. D 9. A 10. A 11. C

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CHEMISTRY FOR NEET & AIIMS 40-65*0/4

LiH > NaH > KH > RbH > CsH

EXERCISE
7. (B) All salts are soluble in water and give strong acid
P-1 (NEET/AIPMT) and weak base
SrCl2 + 2H2O o Sr(OH)2 + 2HCl
1. (B) H2O2 shows non-planar structure. It has a half opened BaCl2 + 2H2O o Ba(OH)2 + 2HCl
book like structure in which the two O–H groups lie on
MgCl2 + 2H2O o Mg(OH)2 + 2HCl
the two pages of the book.
CaCl2 + 2H2O o Ca(OH)2 + 2HCl
0.97 Å
The basic nature of alkaline earth metals generally in-
O H creases from Be to Ra. Thus, the order of basic nature of
97° these hydroxides is
1.48 Å
101.5° Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2
H O hence, pH is highest for BaCl2. (As pH increases with
basic nature)
94°
O–O single bond distance is 1.48 Å 8. (A) Ca(OCl)2, calcium hypochlorite is the active ingredi-
ent in bleaching powder which releases chlorine.
2. (D) The correct order of the mobility of the alkali metal
ions in aqueous solution is Rb+ > K+ > Na+ > Li+ due to 9. (C) Order of thermal stability is
following order of hydration energy of these ions Li+ > K2CO3 > Na2CO3 > CaO3 > MgCO3
Na+ > K+ > Rb+ and as the hydration of ion increases, Hence, MgCO3 releases CO2 most easily
mobility decreases. '
MgCO3  o MgO  CO2
1
Hydration enthalpy v
Size of cation 10. (A) Solubility of the sulphates. The sulphates becomes
less soluble as you go down the group i.e.
3. (B) Thermal stability of carbonates increases in a group Mg > Ca > Sr > Ba
as we move from top to bottom and decreases in a The magnitude of the lattice energy remains almost con-
period as we move from left to right. so the correct order stant as the size of the sulphate ion is so big that small
increase in the size of the cation from Be to Ba does not
of thermal stability of given carbonates is
make any difference. However, the hydration energy
BeCO3 < MgCO3 < CaCO3 < K2CO3 decreases from Be2+ to Ba2+ appreciably as the size of
Be, Mg and Ca are present in second group and K is the cation increases down the group. The significantly
present in first group. high solubility of MgSO4 is due to high enthalpy of
solvation of the smaller Mg2+ ions.
4. (B) Hydration energy of sulphate decreases from top to
bottom in II group. Mg2+ is smaller than other given ions 11. (C) Metals are usually not found as nitrates in their ores,
of II group, so Mg2+ is readily hydrated. MgSO4 has because metal nitrates are highly soluble in water. For
higher hydration energy than lattice energy. example, KNO3 (salt peter) would be classified as
completely soluble. Thus, KNO3 could be expected to
5. (B) The smaller the size of the ion, the greater is the dissociated completely in aqueous solution to give K+
degree of hydration, thus degree of hydration is highest and NO3– ions.
for Li+ and lowest for Cs+. Thus, Li+ holds more water
molecules in its hydration sphere and becomes largest KNO3 U K  (aq)  NO3 (aq)
in size among alkali metals and CS+ ion hold least num- The nitrate anion has three equivalent oxygen surround-
ber of water molecules. ing a central nitrogen atom. This tends to spread the
Hence, ionic mobility is highest for Cs+ (due to its small- single negative charge and make it easier for water (us-
est size in aqueous solution) and lowest for Li+. Here the ing hydrogen bonds) to separate the ions in solution.
lowest is for Na+. Thus, the order of ionic mobility in O O O
aqueous solution is
Cs+ > RB+ > K+ > Na+ N N N
O O O O O O
6. (D) As the size of the alkali metal cation increases,
thermal stability of their hydrides decreases. 12. (C) Beryllium salts are covalent in nature because of
Hence, the correct order of thermal stability of alkali metal very small size of Be2+ ion and its high polarising power,
hydrides is so it is easily hydrolysed.

135
 HYDROGEN AND ITS COMPOUNDS
e.g. BeCl2 + 2H2O o Be(OH)2 + 2HCl
EXERCISE

13. (C, D)
P-2 (AIIMS)
• For ionic salts, hydrogen never behaves as cation,
but behaves as anion (H–). 1. (D) Disodium salt of ethylenediaminetetraacetic acid has
• H3O exists freely in solution.
+ been used for the estimation of M2+ metal ions like Mg2+,
Ca2+, etc. by complexometric titrations.
• Dihydrogen acts as a reducing agent.
In this titration, indicator ions (D3– ions) form red-metal
• Hydrogen has three isotopes.
indicator comple, [MD–] with M2+ ions.
Protium (11 H)
pH=10
(i) M2
+
+ D
3-
[M2+D]-
Deuterium (12 H) metal ion Metal indicator
indicator
(Mg2+ or Ca2+) ion (blue) complex (red)
Tritium (13 H)
(ii) [M2+D]– + EDTA4–

U [M2+(EDTA)]2– + D3–
Protium is the most common isotopes of hydrogen with
(red) EDTA ion metal-EDTA (blue)
an abundance of 99.98%
complex
14. (B)
The release of the free indicator ion is marked by a change
• Ca2+ ions are very important factor in blood clot- from red (colour of [M2+D]– complex) to blue (colour of
ting. D3– ion) colour.
• Ca2+ ions are very important for maintaining the regu-
2. (C) 2H2O2 o 2H2O + O2
lar heart beating.
100 mL 1000 mL
• Mg2+ ions is present in the green parts of plants i.e.
or 1 mL of H2O2 will give 10 mL of O2 at STP Thus, its
chlorophyll.
volume strength is 10 volume.
• Mg2+ can form a complex with ATP.
3. (A) X-ray studies have shown that in ice, four hydrogen
15. (*) When calcium carbide (CaC2) reacts with nitorgen
(N2) under high temperature, it forms calcium cyanamide atoms tetrahedrally surround each oxygen atoms.
which is also called nitrolim. H
CaC 2  High
N 2 o CaCN 2  C O 1.76 Å
temperature
Calcium cyanamide H 1.00 Å
Hence, option (d) should be CaCN2 instead of Ca(CN)2. O H H
H H
thus no option is correct. O H O
H
16. (D) Key concept Morethe hydration, lesser is the ionic
mobility O
In all the alkali metals, Li+ ion is smallest. Thus, extent H H
hydration is maximum in Li+ ion. 4. (A) I2(s) + H2O2(aq) + 2OH (aq) + 2H2O(l) + O2(g)
–

i.e. the dissolution of Li+ in water occurs and get hy-

drated. Smaller the size of cation, greater is the extent of 5.6 u Strength in g L1
hydration and lesser is the ionic mobility. 5. (C) Volume strength
Eq. wt.of H 2 O 2

5.6 u 15.18
5 volumes
17
6. (C) The production of dihydrogen can be increased by
reacting carbon monoxide of syngas with steam in the
presence of iron chromate as catalyst.

CH (g )  H 2 O (g) 
673 K
o CO 2(g )  H 2(g)
Catalyst

This is called water-gas shift reaction.

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CHEMISTRY FOR NEET & AIIMS

7. (A) Alkali and alkaline earth metals react with water to

produce hydrogne gas and metal hydroxides. This is
due to their high electropositive character.
Mg + 2H2O o Mg(OH)2 + H2

8. (D) O2F2 has the similar structure as that of H2O2 but the
O – O bond length is shorter in O2F2 than in H2O2. This
is due to the high electronegativity of attached F-atoms.
H2O2 is a covalent compound.

9. (A) H2O2 oxidises sulphur to sulphate in presence of

Fe3+ ions.

10. (A) MCl2 + Na2CO3 o MCO3 p + 2NaCl

MSO4 + Na2CO3 o MCO3 p + Na2SO4
(where, M = Mg, Ca)

11. (C) H2O2 is more extensively associated by hydrogen

bonding than water.

137
S-BLOCK
CHAPTER
11
When the elements are arranged in vertical columns according to in-
creasing atomic weight, so that the horizontal lines contain analogous
elements again according to increasing atomic weight, an arrange-
ment results from which several general conclusions may be drawn.

“ DMITRY IVANOVICH MENDELEEV”

INTRODUCTION

T
he s-block elements of the Periodic Talbe are those in which the last eletron enters
the outermost s-orbital. As the s-orbital can accommodate only two electrons, two
groups (1 & 2) belong to the s-block of the periodic Table. Group 1 of the Periodic
table. Group 1 of the Periodic Table consists of the elements: lithium, sodium, potas-
sium, rubidium, caesium and francium. They are collectively known as the alkali
metals. These are so called because they form hydroxides on reaction with water
which are strongly alkaline in nature. The elements of Group 2 include beryllium,
magnesium, calcium, strontium, barium and radium. These elements with the excep-
tion of beryllium are commonly known as the alkaline earth metals. These are so
called because theiroxides and hydroxides are alkaline in nature and these metal
oxides are found in the earth’s crust.

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CHEMISTRY FOR NEET & AIIMS

The elements in which the last electron enters the outer most s - orbital are called s-block elements. The group I and II of
periodic table belongs to the s-block.

ALKALI METAL
PHYSICAL PROPERTIES :
(i) Physical State
(a) One electron in outermost sheel & General formula ns1.
(b) Francium is radioactive element.
(c) All are silvery white
(d) Light soft, malleable and dutile metals with metallic lustre.
(e) Alkali metal are paramagnetic, diamagnetic and colourless in form of ions.

(ii) Atomic Size

(a) Biggest in their repective period
(except noble gas element)
(b) Size increases from Li to Fr due to addition of an extra shell.
Li < Na < K < Rb < Cs < Fr

(iii) Softness
(a) Alkali metals are soft because of
(i) Large atomic size
(ii) BCC crystal structure (HCP in Li)
(iii) Loose packing (68 % packing efficiency)
(iv) Weak metallic bond
(b) Cs is the softest metal in s-block

1 1
Atomic size v v softness v
strength of metallic bond Melting & Boiling point

(iv) Melting point and boiling point

(a) Weak interatomic bonds are due to their large atomic radil and presence of only one valence electron hence
melting point and boiling point are low.
(b) Decreasing order of melting point and biling point is
Li > Na > K > Rb > Cs
(c) With the increase in the size of metal atom, the repulsion of the non-bonding electrons increases and therefore
melting point and boiling point decreases from Li to Cs.

(v) Electro positive character or metallic character

Electropositive v 1/Ionisation Potentical
Due to their larger sixe electron can easily be removed to form M+ ion. Electro positive property increases from Li to Cs.
(vi) Flame Test
Alkali metals and their salts gives characteristic colour to bunsen flame. The flame energy causes an excitation of
the outer most electron which on dropping back to ground state emits absorbed energy as visible light
Ex. Li-Crimson red Na-Golden yellowK-Violet
Rb-Red violet Cs-Blue
(vii) Photo Electric Effect
(a) Atomic size of K, Rb and Cs is quite large, so their ionisation potential is very low
(b) Due to very low ionisation potential their valuence shell electrons gets excited even by absorbing visible light.
That’s why Cs is used in photo cells.

139
 s-BLOCK
(viii)Standard oxidation potential
(a) All the alkali metals have high +ve values of standard oxidation potential (tendency of relasing electrons in
water or self ionic solutions)
(b) So these are good reducing agent, having upper most position in the electro chemical series.
(c) Li has highest standered oxidation potential (+3.05 eV) due to its high hydration energy . Such that is converts
into. Li+ ion by loosing one electron.
Order of standard oxidation potential of s-block element
Li > K > Ba > Sr > Ca > Na > Mg > Be
Hydration energy v charge density on ion
(ix) Hydration energy (Heat of hydration)
(a) Alkali metals salts are generally soluble in water due to hydration of cations by water molecules.
(b) Smaller the cation, greater is the degree of its hydration.
(c)

Degree of hydration decreasing

Hydration energy decreasing
Hydrated ion size decreasing
Ionic conductance increasing
(x) Reducing property
(a) Since alkali metals have high standard oxidation potential, so these are strongest reductants.
(b) Reducing property increases down the group in gaseous or molten state
Li+ < Na+ < K+ < Rb+ < Cs +
(c) But in aqueous solution order is
Li+ > K+  Rb+ > Cs + > Na+
(xi) Density
In a group atomic volume also increase along with atomic weight but atomic weight increases more than atomic
volume, so density increases from Li to Cs
Increasing order of density Li < K < Na < Rb < Cs
Exception : Density of K is less than Na. Why?
Ans. This is due to presence of vacant d-orbital in the inner shells of K (volume increases, density decreases)
CHEMICAL PROPERTIES :
(i) Reaction with NH3
(a) 2Li + NH3 o Li 2 NH  Lithimide 

2Na + 2NH 3 o 2NaNH 2 + H 2 n

(Sodamide)
(b) Solubility in liquid ammonia
(i) All the alkali metals dissolves in NH3 (Liq.) and produces blue solution.
(ii) This blue solution conducts electricity and possesses strong reducting power, due to the presence of
ammoniated electrons.
Na(s) + (x+y) NH3 o[Na(NH3)x]+ + [e(NH3)y]–
ammoniated electron
(iii) This dilute solution is paramagnetic in nature.
(ii) Reactioin with air
(a) alkali metals gets turnish in air due to the formation of oxide at their surface hence they are kept in kerosence or
paraffin oil.

140
CHEMISTRY FOR NEET & AIIMS
(b) These elements reacts with moist air to form carbonates
4Na  O2 o 2Na2O
Na2O  H2O o 2NaOH
(moist)
2NaOh  CO2 o Na2CO3  H2O
(in air)
In dry air only Li gives nitride and oxide both while other elements gives only oxides.
(iii) Reaction with oxygen
Oxide ion ª¬O º¼
2

Li forms only Li2O (Lithium oxide)

Peroxide >O 2 @
2

Na reacts with O2 to form peroxide (Na2O2)

Super oxide ª¬O 2 º¼


K, Rb and Cs forms MO2 type oxides (super oxides) in excess of O2. So super oxides are paramagnetic and coloured.
M o
O2
M2O o
O2
M2O2 o
O2
M2O2
Oxide perioxide Super
oxide

(Li2O) (Na2O2) (KO2, RbO2, CsO2)

Their stability order is

Normaloxide > Peroxide > Superoxide
(iv) Reaction with water
(a) Alkali metals react vigorously with water forming hydroxisdes with the liberation of H2.
2M  2H2O o 2MOH  H2
(b) Reactivity with water increases from Li to Cs.
Li o least reactive towards water
Na o reacts vigorously
K o reacts producing a flame
Rb, Cs o reacts explosively
(c) These metals also reacts with alcohol gives alkoxide and H2.
2Li  2C2H5OH o 2C 2H5 O Li  H2
(d) Monoxides gives strongly alkaline solution with water
M2O  H2O o 2MOH

(v) Reaction with hydrogen

Alkali metals combine with H2 forming ionic hydrides
2 M + H2 o 2MH
Hydrides of alkali metals are attcked by water to give back hydrogen
MH + H2O o MOH + H2
LiH, NaH, KH, RbH, CsH

Thermal stability decrease, Basic property increases

141
 s-BLOCK
Except Be all the alkaline metals forms MH2 type hydrides, (MgH2, CaH2, SrH2, BaH2) on heating directly with H2
BeH2 is prepared by action of BeCl2 with LiAlH4
2BeCl2 + LiAlH4 o 2BeH2 + LiCl + AlCl3
reducing agent
BeH2 and MgH2 are covalent, other are ionic.
(vi) Halides
(a) Alkali metals reacts directly with halogen to form MX
(M – alkalimetal, X – Halide ion)
(b) Ionic properties of MX increases from LiCl to CsCl
(c) LiCl is covalent in nature (due to polarisation of Cl– ion by small Li+ ion). hence it hydrolyses with water while
reast are ionic so do not hydrolyse.
(d) K, Rb and Cs halides reacts with more halogens to gives polyhalides.
KI  I2 o KI3  on
ionisation
o K   I3

CsBr  Br2 o CsBr3 o Cs  Br3

(vii) Carbonates
(a) All the alkali metals forms M2CO3 type carbonates.
(b) Except Li2CO3, all the carbonates are stable towards heat
Li2CO3 
+
o Li2O  CO 2
(c) Thermal stability of carbonates v 1/I (Ionic potential) Order of stability is
Cs2CO3 ! Rb2CO3 ! K 2CO3 ! Na 2CO3 ! Li2CO3
(viii)Nitrates
(a) Alkali metals forms MNO3 type nitrates (M - alkali metal)
(b) Stability increases from LiNO3 to CsNO3 . LiNO3 decompoes into Lithium oxide & NO2 on heating
4LiNO3 
+
Oxide
o 2Li2O  4NO2  O2
(c) Other nitrates, on heating to give nitrite and oxygen.
MNO3 
+
o 2MNO2  O2
Nitrite

(ix) Nitrides
Only Li reacts directly with N2 to form nitride which gives NH3 on reacting with water.
6Li  M2 o 12Li3N

Li3N  3H2O o 3LiOH  NH3 n

(x) Formation of Amalgam

(a) Alkali metals gives amalgam with Hg.
(b) These metals reacts with other metals to give mixed metals (alloys)
(xi) Sulphates
(a) Alkali metals forms M2SO4 type sulphates
(b) All alkali metal sulphates are ionic. Ionic properties increases from Li to Cs.
Li2SO 4  Na2SO 4  K 2SO 4  Rb2SO 4  Cs2SO 4
(c) Li2SO4 Least soluble in water.
(d) These sulphates on burning with C forms sulphides
M2SO4  4C o M2S  4CO

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CHEMISTRY FOR NEET & AIIMS

(e) Except lithium, sulphates of IA group reacrts with sulphates of trivalent metla like Fe 3 ,Cr 3 ,Al3 etc. gices
double salts called alum.
I III
M2SO4 .M2  SO4 3 .24H2O
(xii) Reaction with acids
Reacts vigorously with acids
2M  H2SO 4 o M2SO 4  H2 n

Ex. The first three elements of Group 1 have tghe following atomic structures
(a) Lithium : 3P, 4n ; 2, 1 electrons
(b) Sodium : 11p, 12n; 2, 8, 1 electrons
(c) Potassium : 19p, 20n; 2, 8, 8, 1 electrons
Which of the following features causes them to have similar properties?
(A) The same number of protons
(B) More protons than electrons
(C) Two electrons in the first shell
(D) One electron in the outermost shell
Sol. (D) One electron in the outermost shell.

Ex. Considering greater polarization in LiCl compared to theat in NaCl, which of the following statements you would
expect to be wrong ?
(A) LiCl has lower melting point than that of NaCl
(B) LiCl dissolves more in organic solvents
(C) LiCl will ionize in water more than NaCl
(D) Fused LiCl would be less conducting that fused NaCl.
Sol. (C) According to fajan’s rules, heigher the polarization, higher is the covalent caharacter. Thus LiCl is covalent
while NaCl is ionic. As a result LiCl will not ionize in water more than NaCl.

Ex. Sodium ordinarily does not show an oxidation state of +2, because of its
(A) High firs :ionization potential
(B) High second ionization potential
(C) Large ionic radius
(D) High electronegativity
Sol. (B)

Ex. Mark the false statement

(A) The electropositive character of alkali metals decreases with increase in atomic number
(B) Lithium is hard metal and cannot be cut with a knife
(C) Alkali metals are strong reducing agents
(D) Electronegativities of all alkali metals lie between 1.0 to 0.7.
Sol (A)

Anomalous Behavior of Lithium

y On account of its small size it exerts the greatest polarising effect out of all the alkali metals and ions,
consequently covalent character is developed.
y Li2CO3 is less stable, as it decomposes on heating. Li2CO3  '
o Li2O + CO2
y Li when heated in NH3 forms imide Li2NH while other alkali metals form amides. MNH2

143
 s-BLOCK
Diagonal Relationship [Li and Mg]
Lithium shows diagnal relationship with magnesium since theyhave almost the same polarizing power, i.e., charge/size
ratio
Lithium resembles magnesium in the following respects :
(i) Atomic size of Li (1.34 A) and Mg (1.36 A) are not much different.
(ii) ionic size of Li+ (0.60 A) and Mg2+ (0.65 A) are almost identical
(iii) polarizing power (i.e., ionic charge to ionic radius ratio) of Li+ and Mg2+ are about the same
(iv) electronegativities of Li (1.00) and Mg (1.20) are not much different
(v) both Li and Mg and hard metals
(vi) both decompose water only on heating
(vii) both combine with oxygen to form monoxides,
(viii) both LiOH and Mg(OH)2 are weak bases
(ix) both LiCl and MgCl2 are predominantly covalent and hence are soluble in organic solvents, such as alcohol and
pyridine
(x) both Li and Mg combine with nitrogen to form their respectively nitrides, Li3N and Mg3N2 .
(xi) carbonates, cluorids, oxalates and phospheates of both Li and Mg are sparingly soluble in H 2O.
(xii) the hydroxides and carbonates of both Li and Mg decompose on heating forming their respective oxides.
(xiii) bothe lithium and magnesium nitates on heating evolve NO2 and O2 leaving behind their oxides.
SIMILARITIES BETWEEN LITHIUMAND MAGNESIUM
(a) Both lithlum and magnesium are harder and lighter than other elements in the respective groups.
(b) Lithium and magnesium react slowly with cold water. Their oxides and hydroxides are much less soluble
and their hydroxides decompose on heating. Both form a nitride by direct combi nation with nitrogen, Li3N
and MgN2.
(c) The oxides, Li2O and MgO do not combine with excess oxygen to give a peroxide or a super oxide.
(d) The carbonates of lithium and magnesium decompose easily on heating to form the oxide and CO2. Solid
bicarbonates are not formed by lithium and magnesium.
(e) Both LiCl and MgCl2 are soluble in ethanol.
(f) Both LiCl and MgCl2 are deliquescent and crystallise from aqueous solution as hydrates,
LiCl.2H2O and MgCl2.8H2O.
Ore of alkali metals :
Since alkali metals are highly reactive metals, they do not occur in free state in nature sodium and potassium are quite
abundant in the earth’s crust with 7th and 8th position in the order of abundance of elements
• Ores of Lithium
(i) Spodumene, LiAlSi2O6 (ii) Lepidolite, (Li)2Al2(SiO3)3. (FOH)2
• Ores of Sodium
(i) Common salt or rock salt, NaCl (ii) Chile salt patre, NaNO3
(iii) Albite (Soda Feldspar), NaAlSi3O8 (iv) Glauber’s salt, Na2SO4. 10H2O
• Ores of Potassium
(i) Camallite, KCl. MgCl2. 6H2O (ii) Feldspar, KAlSi3O8
(iii) Sylvine, KCl
Ex. Alkali metals redily dissolve in liquid ammonia to give blue coloured solution. The blue colour is believed to be due to
(A) Ammoniated cations (B) Ammoniated anions
(C) Ammoniated electrons (D) Ammoniated cations and ammoniated electrons
Sol. (C)Ammoniated electrons, i.e.
Na  s    x  y  NH3 o Na  NH3  x  e  NH3  y
Blue colour

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CHEMISTRY FOR NEET & AIIMS
Ex. Choose the compound which does not poossies a peroxide group
(A) Na2O2 (B) CrO5 (C) Fe2O3 (D) BaO2

Sol. (C) Na2O2 is Na  O  O Na  ;CrO5 is

BaO2 is Ba2  
O – O  while Fe2O3 consists of only Fe3+ and O2– ions. Thus Fe2O3 does not contain a

peroxide  O – O  linkage
 

Ex. The addition of Na2CO3 to the aqueous solution of an oxide produces CO2. This reaction indicates that
(A) Oxide is basic (B) Oxide is amphoteric
(C) Oxide is that of a metal (D) Oxide is that of a non-metal
Sol. (D)
Ex. Alkali metal when exposed to air tarnish quickly due to the
(A) Formation of their hydroxides (B) Formation of their carbonates
(C) Formation of their oxides (D) All the above
Sol. (D)
Compoundsof Alkali metals
SODIUM (Na), NATRIUM
(a) Extraction : Down's Process
By Electrolysis of fused NaCl + CaCl2 + NaF
At cathode (Iron Vessel) : Na+ +e– Na(s)
At Anode (Graphite) : 2Cl– Cl2 + 2e–
(i) (CaCl2 + NaF) is used to lower Melting point (8000C) of NaCl to about 6000C.
(ii) Aqueous sodium chloride cannot be used for preparing sodium by electrolysis. Because instead of metallic
sodium, hydrogen gas will be liberated at cathode.
(b) Properties
(i) It is a crystalline soft metal.
(ii) Highly reactive, so kept in kerosene.
(iii) Na dissolves in liquid NH3 to giveblue solution.
(c) Uses
(i) In the preparation of sodium amalgam (used as reducing agent)
(ii) In sodium vapour lamp, which emits monochromatic yellow light.
(iii) As heat transfer medium in nuclear reactors.
(I) Sodium chloride NaCl
(a) Occurrence : Sea water is the main source and also found in salt lakes.
(b) Preparation :
Evaporation
(i) Sea water NaCl(2.7 – 2.9%) by solar heat
crude NaCl
(ii) It contains impurities – Na2SO4, MgCl2, CaCl2 etc.
(iii) Insoluble impurities removed by filtration.
HCl gas passed
(iv) Filtrate Pure NaCl precipitation (Common ion effect)
_ + _
HCl Cl NaCl Na + Cl
Ionic product of [Na+] [Cl–] > solubility product of NaCl hence it precipitates out.
(v) MgCl2 and CaCl2 are more soluble in water so left in solution.

145
 s-BLOCK
(c) Properties :
(i) Table salt is slightly hygroscopic due to the presence of magnesium and calcium chlorides in small amounts.
(ii) Reaction with AgNO3
NaCl + AgNO3 o NaNO3 + AgCl(white ppt.)
Reaction with K2Cr2O7 + conc. H2SO4
(iii) 4NaCl + K2Cr2O7 + 5H2SO4  '
o 4NaHSO4 + K2SO4 + 2CrO2Cl2 + 3H2O
(orange red)
(d) Uses :
(i) As a preservative for pickles, meat and fish.
(ii) For making freezing mixture with Ice.
(II) SODIUM HYDROXIDE (NaOH), CAUSTIC SODA
(a) Manufacture : By electrolysis of NaCl.
(b) Nelson Cell or Diaphragm Cell : The following reactions takes place –
_
NaCl(aq.) Na + Cl
+

_
NaOH + H2 + Cl2
H2O H+ + OH
At cathode (Perforated steel) : 2H+ + 2e– o H2(g) At anode (Carbon) : 2Cl–(aq.) o Cl2(g) + 2e–
(c) Castner – Kellner Cell : (Hg – Cathode Process)
Electrolite (Brine) NaCl Na+ + Cl–
On electrolysis –
At Cathode (Hg)
Na+ + e– o Na. and Na + Hg o Na.Hg (amalgum)
At anode (Graphite)
2Cl– o Cl2(g) + 2e– and 2Na.Hg + 2H2O o 2NaOH + H2 + 2Hg

(d) Properties :
(i) It is deliquescent white crystalline solid.
(ii) It absorbs CO2 from air forming Na2CO3.
(iii) NaOH is strong base
SiO2
Na2SiO3 + H2O
NaOH Al2O3
2NaAlO2 + H2O

(iv) Reaction with non metals : no reaction with H2, N2 and C

B
Na3BO3 (sodium borate)
Si
NaOH Na2SiO3 (sodium silicate)
P4
NaH2PO2 + PH3
(sodium hypo phosphate)

(v) Reaction with halogens

NaOH (cold/dil)
NaX + NaOX (Sodium hypo halite)
X2 NaOH (Hot/conc.)
NaX + NaOX3 (Sodium Halate)
(X2 = Cl2 , Br2, I2 )

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CHEMISTRY FOR NEET & AIIMS
(vi) Reaction with Metal

Alkali metal
No reaction
2Al + 2H2O
2NaAlO2 (Sodium meta aluminate) + H2
Be
Na2BeO2 (Sodium Berrylate) + H2
NaOH
Zn
Na2ZnO2 (Sodium zincate) + H2
Sn
Na2SnO2 (Sodium stannite) + H2
Pb
Na2PbO2 (Sodium plumbite) + H2

(vii) Reaction with ZnCl2 or ZnSO4

ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl

Zn(OH)2 + 2NaOH Na2 [Zn(OH)4]

(Soluble complex )

(viii)The hydroxides of aluminium, zinc, lead and tin, however, dissolve in excess of sodium hydroxide giving clear
solution which can also be obtained when these metals are acted upon by the concentrated solution of sodium
hydroxide.
– 2– –
Zn(OH)2 + 2OH [Zn(OH)4] Al(OH)3 + 3OH [Al(OH)6]3–
Zincate ion Aluminate ion
(e) Uses :
(i) In the manufacture of soap, rayon, dyes, paper and drugs.
(ii) In petroleum refining.

(III) SODIUM BICARBONATE OR BAKING SODA (NaHCO3)

(a) Preparation : Solvay process (Commercial Scale)
CaCO3  o  CaO + CO (In brine saturated with NH , CO is passed)
2 3 2

NH3 + H2O + CO2 

o NH HCO
4 3

NaCl + NH4HCO3 
o NH Cl + NaHCO
4 3

2NH4Cl + CaO 
o CaCl + 2NH + H O (Bye-products)
2 3 2

(b) Properties :
Hydrolysis NaHCO3 + H2O NaOH + H2CO3
Effect of heat (temp. > 100°C) 2NaHCO3 o Na2CO3 + H2O + CO2n
(Process occurs during preparation of cake)
Reaction with acids – gives CO2 NaHCO3 + HCl 
o NaCl + H O + CO n
2 2

Reaction with base NaHCO3 + NaOH 

o Na CO + H O
2 3 2

(c) Uses :
(i) In the preparation of baking powder. (ii) In the preparation of effervescent drinks.
(iii) In the fire extinguishers. (iv) As antacid medicine (removing acidity)
Ex. Based on lattice energhy and other considerations which one of the following alkali metal chlorides is expected to
have the highest melting point
(A) LiCl (B) NaCl (C) KCl (D) RbCl

147
 s-BLOCK
Sol. (B) Although lattice energy of LiCl higher than NaCl but LiCl is covalent in nature and NaCl ionic there, after
the melting point decreases as we move NaCl because the lattice energy decreases as a size of alkali metal
atom increases (lattice energy v melting point of alkali metal halide)
Ex. NaOH is prepared by the method
(A) Down’s cell (B) Castner cell
(C) Solvay process (D) Castner Kellnear cell
Sol. (D) The cell involves the following reaction,
NaCl U Na   Cl
At anode: 2Cl o 2Cl  2e o Cl2
At cathode: Na  e o Na
Na  Hg o amalgam
At anode: Na  amalgam o Na   Hg  e

At cathode: 2H2O  2e o H2 n 2OH

ALKALINE EARTH METAL
PHYSICAL PROPERTIES :
(i) Physical state
(a) Two electrons in outer most shell & General formula ns2.
(b) Radium is radioactive element
(c) All are greyish white.
(d) These metals are harder than alkali metals.
(e) These are diamagnetic and colourless in form of ions or in metal states.
(ii) Atomic size
Smaller than IA group elements, since extra charge on nucleus attracts the electron clud.
(a) Size increases gradually from Be to Ba
Be < Mg < Ca < Sr < Ba
(b) In s-block elements
Be is the smallest, Cs is the biggest
(iii) Softness
(a) These metals are slightly harder than [A group because of -
(i) Smaller atomic size
(ii) FCC, HCP crystal structures
(iii) Packing capacity 74%
(iv) Stronger metallic bond due to presence of two electrons in valence shell.
(b) Be is the hardest metal in s-block.
(iv) Melting point and boiling point
(a) Metallic bond is stronger than IA group due to smaller atomic size and two electrons in valence shell hence
melting point and boiling point are higher.
(b) Decreasing order of melting point and boiling point is
Be > Ca > Sr > Ba > Mg
(c) Melting point and Boiling point of Ca, Sr and Ba is higher than Mg because of presence of d-orbitals in the
outer most shell, which forms stronger metallic bond.
(v) Electro positive character or metallic character
Their atomic size is smaller than IA group so these are lesser electro positive than IA group. Electropositivity
increases from Be to Ba

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CHEMISTRY FOR NEET & AIIMS
(vi) Flame Test
(a) Be and Mg atoms, due to small size, bind their electrons more strongly, so are not excited to higher level, hence
no flame test.
(b) Other delements gives characteristic colour to flame
Ca-Brick red Sr-crimson red
Ba-Apple green
(vii) Photo Electric Effect
These elements do not show this property as their atomic size is small hence ionisation potential is higher than IA
group.
(viii)Standard oxidation potential
(a) They have lower values of standard oxidation potential due to their small size
(b) Increasing order of standard oxidation potential is
Be  Mg  Ca  Sr  Ba
 o
(c) Tendendy of loosing electron increases
(ix) Hydration energy (heat of hydration)
(a) Due to smaller ionic sixe and higher charge density their hydroation energy is higyh
(b) Its decreasing order is
Be 2 ! Mg2 ! Ca 2 ! Sr 2 ! Ba 2
(c) hydration energy v 1/cation size
(x) Reducing property
(a) Less reductant than alkali metals
(b) Order of reducing property in aqueous and gasesouts medium is
Be 2  Mg2  Ca 2  Sr 2  Ba 2

(xi) Density
Density increases from Be to Ba
Increasing order of density Ca < Mg < Be < Sr < Ba

CHEMICAL PROPERTIES :
(i) Reaction With NH3
(a) On increasing metal ion concentrate solution converts into bronze colour due to cluster formation of metal ions.
(b) Solubility in liquid ammonia
(i) Only Ca, Sr and Ba gives blue solution of ammoniated electron.
(ii) Be and Mg are small in size and have high ionisation potential so do not dissolves in liquid NH3.
(iii) Dark blue colour of solution becomes fade if it allowed to stand for a long time, it is because of metal amide
formation.
(iv) Blue colour of solution disappears on addition of of ammonium salt, due to NH3 formation

NH4  NH2 o 2NH3

(ii) Reaction with air

(a) Except Be, these metals are easily turnished in air, as a Layer of oxide is formed on the surface.
(b) Barium in powdered from, burst into flame on exposure to air.
(c) In moist air, except Be all the elements converts into carbonates.
(d) In dry air Be and Mg gives nitride and oxide both while other gives only oxides.

149
 s-BLOCK
(iii) Reaction with oxygen
(a) Alkaline earth metals reacts with O2 to form ‘MO’ Type oxides
M Be, Mg, Ca, Sr, Ba 
(b) But Ca, Sr and Ba due to low ionisation potential and more reacitivity, forms MO2 (peroxides) at low tempera-
ture.
Ex. CaO 2 ,SrO2 ,BaO2
(c) Peroxides are coloured due to Lattice deffect.
(d) BeO shows amphoteric property.
Mgo o weak base
CaO,SrO & BaO o Strong base
(e) Basic properties increases from Be to Ba
(f) Its stability order general oxide > Peroxide > super oxide
(iv) Reaction with water
(a) These metals reacts slowly with water gives H2 and metals hydroxides
M  2H2O o M  OH2  H2
(b) Be does not reacts with water
(c) Mg reacts only with hot water
(d) Ca, Sr, Ba reacts with cold water but not as energetically as alkali metals, order of reactivity
Ba > Sr > Ca > Mg > Be
(e) From Be(OH)2 to Ba(OH)2 basic property and stability increases.
(v) Reaction with hydrogen
Except Be all the alkaline metals forms MH2 type hydrides, (MgH2, CaH2, SrH2, BaH2) on heating directly with H2
BeH2 is prepared by action of BeCl2 with LiAlH4
2BeCl2 + LiAlH4 o 2BeH2 + LiCl + AlCl3
reducing agent
BeH2 and MgH2 are covalent, other are ionic.
(vi) Halides
(a) Alkaline metals reacts with X (Halogen) to form MX2.
Ex. BeCl2,MgCl2 ,CaCl2 etc.
(b) Ionic nature of MX2 increases from BeCl2 to BaCl2
(c) Ba burns in contact with Cl2
(d) Hydrolytic nature of these halides decreases from BeCl2 to BaCl2
(e) BeCl2 and MgCl2 are covalent in nature. Order of ionic nature
BeCl2 < MgCl2 < CaCl2 < SrCl2 < BaCl2
Solubility in water
BeCl2 > MgCl2 > CaCl2 > SrCl2 > BaCl2

(vii) Carbonates
(a) All the alkaline metals froms MCO3 type carbonates
(b) Except BeCO3, all the carbonates are stable towards heat
BeCO 3 
+
o BeO  CO 2

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CHEMISTRY FOR NEET & AIIMS

(c) Order of decreasing stability

BaCO3 > SrCO 3 > CaCO3 > MgCO3 > BeCO3
(viii) Nitrates
(a) Alkaline earth metals forms M(NO3)2 type nitrates. (M –Alkaline earth metal).
(b) Stability increases from Be NO3 2 to Ba NO3 2 but these are less stable than IA group, due to smallear
atomic size.
(c) All alkaline metals nitrates on heating gives oxides and NO2 + O2
M NO3 2 
+
o Oxidw  NO2  O 2

(d) Be NO3 2 forms a layer of BeO on its surface so reaction stops.

(ix) Nitrides
Only Be and Mg burns in N2 to give M3N2 Be3N2 ,Mg3N2 

Be3N2  6H2O o 3Be  OH2  2NH3

Mg3N2  6H2O o 3Mg  OH2  2NH3

(x) Formation of amalgam

Shows same properties as alkali matals.
(xi) Sulphates
(a) Alkaline earth metals forms MsO4 type sulphates
(b) Ionic nature of alkaline metal sulphate is increases from Be to Ba
BeSO4 < MgSO4 < CaSO 4 < SrSO 4 < BaSO4
(c) Solubility decreases from BeSO4 to BaSO4 as Be2 and Mg2 are of small size so their hydration energy is
high Hydration energy > Lattice energy.
(d) Order of solubility -

BeSO4 , MgSO4 , CaSO4 , SrSO4 , BaSO4
o
Ionic nature increases, Thermal stability increases
(xii) Reaction with acids
Freely reacts with acids and displaces hydrogen
M  2HCl o Mcl2  H2 n

(xiii)Hydrides
(a) Except be, all alkaline earth metals from hydrides MH3  on heating direcely with H2.

M  H2 o MH2
(b) BeH2 is prepared by the actioin of LiAlH4 on BeCl2
2BeCl2  LiAlH4 o 2BeH2  LiCl  Alcl3
(c) BeH2 and MgH2 are covalent while other hydrides are ionic
(d) The ionic hydrides of Ca, Sr, Ba liberated H2 at anode and metal t cathode.
Fusion
ZZZZZ
X 2
Z Ca  2H
CaH2 YZZZZ 

(e) The stability of hydrides decreases from Be to Ba.

151
 s-BLOCK
(f) The hydrides having higher reactivity for water, dissolves readily and produce hydrogen gas.
(g) The hydrides having higher reactivity for water, dissolves readily and produce hydrogen gas.
CaH2  s   2H2O o Va  OH2  2H2 n

(xiv)Carbides : BeO when heated with C at about 2000°C, Be2C is formed. The metals Mg, Ca, Sr and Ba form carbides
for the formula MC2. These carbides are formed when the metal or the metal oxide is beated with carbon in an electric
fumace.
These carbides are ionic in nature.
Be2C yields methane on hydrolysis whereas carbides of other metals yield acetylene
Be 2C  4H2O o 2Be  OH 2  CH4

CaC2  2H2O o Ca  OH2  C2H2

(xv) Complex compounds : Alkaline earth metals have a tendency to form state complexes. Their ability to form com-
plexes is more as compared to alkali meals. This is because of the smaller size and higher charge of the alkaline earth
metal ions as compared to alkali metal ions. Among the elements of group-2, beryllium and magnesium, have greater
tendency of complexation.

Ex. In alkaline earth metals, the electrons are more firmly held to the nucleus and hence
(A) Ionization energy of alkaline earth metals is greater than that of alkali metals
(B) Alkaline earths are less abundant in nature
(C) Reactivity of alkaline earth metals is greater than that of alkali metals
(D) Atoms of alkaline earth metals are bigger in size than alkali metals.
Sol. (A) Ionization energies of alkaline earth metals are greater than those of alkali metals due to increased nuclear
charge.
Ex. The ion having highest mobility in aqueous solution is
(A) Be2 (B) Mg2 (C) Ca2 (D) Ba2
Sol. (D) Though Ba2 is the heaviest ion but it is least hydrated. As a result, its size becomes lesser than any other
hydrated alkaline earth metal cation and hence has the highest ionic mobility.
Ex. Alkaline earth metal show typical characterics of
(A) Inner transition elements
(B) Noble gases
(C) Representative elements
(D) Transition elements
Sol. (C)
Ex. Which of the following is true for magnesium ?
(A) It is more electropositive than sodium
(B) It is manufactured by electrolysis of aqueous magnesium chloride
(C) It is a strong reducing agent
(D) It resembles, in chemical properties, with its diagonally placed element Boron in 13 group of the periodic Table.
Sol. (C)
Anomalous Behavior of Beryllium
y It is the hardest of all alkaline earth metal as maximum metallic bonding is there due to it’s smallest size.
y The melting and boiling points of the beryllium are the highest.
y Oxides and hydroxides of beryllium are amphoteric in nature.

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CHEMISTRY FOR NEET & AIIMS

BeO + H2SO4 o BeSO4 + H2O BeO + 2NaOH o Na2BeO2 + H2O

Be(OH)2 + 2HCl o BeCl2 + 2H2O Be(OH)2 + 2NaOH o Na2BeO2 + 2H2O
y It shows diagonal relationship with Al.
Diagonal relationship [Be and Al]
Anamalous behaviour of Be and its diagonal relationship with Al is illustrated by the following points :
(i) Unlike group -2 elements but like aluminium, beryllium forms covalent compounds.
(ii) The hydroxides of beryllium, ª¬Be  OH 2 º¼ and aluminium, ª¬ Al  OH3 º¼ are amphoteric in nature, whereas those
of other elements of group - 2 are basic in nature.
(iii) Beryllium and aluminium forms fluoro complexes in solution.
(iv) The oxides of both Be and Al, i.e, BeO and Al2O3 are high melthing insoluble solids.
(v) BeCl2 like Al2Cl6 has a bridged polymeric structure.
(vi) The salts of beryllium as well as aluminium are extensively hydrolyzed.
(vii) Be like Al, is rendered passive by concentrated HNO3
(viii) Be forms many complex like Al
(ix) Be and Al react with NaOH solution liberating H2.
(x) Halides of the two elements have similar solubilities.
(xi) The two metals do not impart colour to the bunsen flame.
DIAGONALSIMILARITY BETWEEN BERYLLIUMANDALUMINIUM
In many of its properties, beryllium resembles aluminium. Thus-
(a) The two elements have same electronegativity and their charge / radius ratios.

(b) Both metals are fairly resistant to the action of acids due to a protective film of oxide on the surface. Both
metals are acted upon by strong alkalies to form soluble complexes, beryllates [Be(OH)4]2- and aluminates,
[Al(OH)4]-.

(c) The chlorides of both beryllium and aluminium

have bridged chloride structures in vapour phase.

(d) Salts of these metals form hydrated ions, Ex. [Be(OH2)4]2+ and [Al(OH2)6]3+ in aqueous solutions. Due to
similar charge/ radius ratios of beryllium and aluminium ions have strong ten dency to form complexes. For
example beryllium forms tetrahedral complexes such as BeF42- and [ Be(C2O4)2]2- and aluminium forms
octahedral complexes like AlF63- and [Al(C2O4)3]3-
Ex. Which of the following elements will form a compound with oxygen in which one atom of the element is combined
with one atom of oxygen to form and oxide of formula MO?
(A) Be (B) Ne (C) Al (D) Cl
Sol. (A) Be forms BeO, Al forms Al2O3 ,Cl forms Cl2O7 ,cl2O,ClO2 etc. while Ne does not react.

Ex. The cation which gives a yellow precipitate with potassium chromate is
(A) SrCO 3 (B) BaCO3 (C) CaCO3 (D) MgCO3
Sol. (B) Barium gives a yellow ppt. of barium chromate with pot. chromate

153
 s-BLOCK

K 2CrO 4  Ba 2 o BaCrO 4  2K 

Ex. The atom with atomic number 12 will most likely combine chemically with the atom whose atomic number is
(A) 3 (B) 10 (C) 11 (D) 16
Sol. (D)
Ex. A piece of magnesium ribbon was heated to redness in an atmosphere of nitrogen and then cooled with water. The
gas evolved is
(A) Ammonia (B) Hydrogen (C) Nitrogen (D) Oxygen
Sol. (A)
COMPOUND OFALKALINE EARTH METALS
CALCIUM
Ores of Calcium
(i) Gypsum, CaSO4 .2H2O (ii) Lime stone, CaCO3 (iii) Marble, CaCO3
(iv) Fluorspar, CaF2 (v) Anhydrite, CaSO 4 (vi) Dolomite, CaCO3 ,MgCO3
Calcium is prepared by the electrolysis of a fused mixture of anhydrous calcuim chloride and calcium fluoride On
passing electric current, calcium is liberated at the cathode.
CaCl2 o Ca2  2Cl ....... Ionization 
At cathode: Ca2  2e o Ca
At anode : Cl o Cl  e
2Cl o Cl2
(I) Calcium oxide, Quick lime, Burnt lime (CaO)
Preparation :
It is prepared by heating lime stone (CaCO3) at 8000C
CaCO3 U CaO  CO2 'H 179.9 KJ

Condition for Good Yield :

• Since the reaction is reversible, therefore the carbon dioxide formed must be removed as soon as it is formed so that
the reaction remain in the forward direction.
• Temperatone will react with CaO to form CaSiO3.
Properties :
(i) Action of water
CaO  H2O o Ca(OH)2  15000 Caloric
(quick lime) (Slaked lime)
Paste of lime in water is called milk of lime, while its hydrate is known as lime water.
(ii) With moist chlorine :
CaO  Cl2 o CaOCl2 (Bleaching powder)
(iii) When heated with carbon, it forms calcium carbide.
0
CaO  3C 
2000 C
o CaC2  CO
Uses :
• In purification of sugar
• As basic lining in furnances.
(II) Calcium hydroxide, Slaked lime Ca(OH)2

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CHEMISTRY FOR NEET & AIIMS
Preparation :
By the action of water on quick lime.
CaO  H2O o Ca(OH)2  Heat
Means it is an exothermic reaction.
Properties :
(i) Sparingly soluble in water and its solubility decreases with increases in temperature.
(ii) Action of CO2 : Lime water turns milky on passing CO2 gas
Ca(OH)2  CO2 o CaCO3  H2O
(Milkiness)
(iii) Action of chlorine
(a) Cold Condition :
2Ca(OH)2  2Cl2 
Cold
o CaCl2  Ca(OCl)2  2H2O
(Cal. hypochlorite)
(b) Below 35° : 3Ca  OH2  2Cl2  o CaOCl2  H2O
below
35q C

(c) On gentle Heating : 6Ca  OH2  6cl2  o 5CaOCl2  H2O

Heat

(d) On Red Hot :

2Ca  OH 2  2Cl2 
Re dHeat
o 2CaCl2  Ca  ClO 3 2  6H2O
(iv) Action of Ammonia
Ca  OH2  2NH4Cl 
o CaCl2  2NH3  6H2O
Uses
• For softening of hard water.
• For purification of sugar and coal gas
• In preparation of bleaching powder, white wash, plaster etc.
(III)Calciium Carbonate (CaCO3): Calcium carbonate is found in nature as limestone, marble, coral ice land spar, calcite,
chalk, dolomitc, etc.
Preparation: It is prepared as a white powder, known as precipitated chalk by dissolving marble or limestone in hydro-
chloric acid followed by precipitation with sod. or ammonium carbonate.
CaCO3 2HCl o CaCl2  H2O  CO 2

CaCl2  NH4 2 CO3 o CaCO3  2NH4Cl

In the laboratory, it is prepared by passing CO2 through lime-water or by adding sod. or ammo carbonate solution of
CaCl2.
Ca  OH 2  CO, o CaCO3 p H2O
Properties :
(i) It is a white powder and exists in two crystalline forms: calcite and aragonite.
(ii) It is insoluble in water but dissolves in the presence of CO2 due to the formation of calcium bicarbonate.
CaCO3  H2O  CO2 o Ca  HCO3 2
(IV) Calcium Bicarbonate (Ca(HCO3)2) : It does not exist in solid state. however, its solution can be prepared by passing CO2
gas through a suspension of calcium carbonate in water. On warm ing, it decomposes to calcium carbonate along with
the evolution of carbon dioxide gas.

155
 s-BLOCK

(V) Calcium Sulphate(CaSO4) : It occurs in nature as anhydride  CaSO4  and gypsum  CaSO4 ·2H2O 
Preparation: It may be prepared by adding dilute sulphuric acid or soluble sulphate (e.g. Na2SO4) to the solution of a
calcium salt.
CaCl2  H2SO 4 o CaSO 4  2HCl )
Properties :
(i) It is a white crystalline solid. Like slaked line it is sparingly soluble in cold water andits solubility decreases
further with the increase in temperature.
(ii) In dissolves much more readiluy in dilute acids, even in acetic acid than in water. It dissolves also in ammonium
sulphate solution forming CaSO4 . NH4  SO 4H2O
(iii) Monoclinic crystals of gypsum when heated, first changes into orthorthombic form without any loss of water.
On further heating to 120°C, it loses three-fourth of its of crystallization and forms the hemihydrate,
1 1
 2CaSO4  .H2O or CaSO4 . 2 H2O  1 2 H2O
Plaster of paris is a white powder which when mixed with water takes up to water of crystallization again, thus
converted back into the dehydrate and sets to a hard mass with slight expansion. Setting takes about 10–15 minutes
and may be catalysed by the addition of common salt or delayed by the use of alum or borax.
1
CaSO 4 . H2O o
H2O
setting
CaSO 4 .2H2O 
hardening
o CaSO 4 .2H2O
2 Orthor hombic Monochlinic  gypsum 
Plaster of paris

Plaster of paris of gypsum when heated to about 200°C is converted into anhydrous calcium sulphate. The anhy-
drous from (anhydrite) is known as dead burnt because it does not set like Plaster of Paris when moistened with
water.
Ex. Setting of plaster of paris is
(A) Oxidation with atmospheric CO2 (B) Combination with atmospheric CO2
(C) Dehydration (D) Hydration to yield another
Sol. (D)Setting of plaster of paris is
1
CaSO4 . H2O  H2O
o CaSO 4 .2H2O Hardening
o CaSO 4 .2H2O
2
orthorhombic Mono orthorhombic Gypsum
The setting gis due to formation of another hydrate.
CEMENT
It is a light grey, heavy fine powder, It is a homogenous mixture of silicates and aluminates of calcium, which form more
than 90% of the cement are –
(i) Tricalcium silicate – 3CaO.SiO2
(ii) Dicalcium silicate (slowest setting component) – 2CaO.SiO2
(iii) Tricalcium aluminate (fastest setting component) – 3CaO.Al2O3
(iv) Tetracalcium alummino ferrite – 4CaO.Al2O3.Fe2O3
(i) Composition of Cement

CaO(61.5%) SiO2(22.5%)

Fe2O3(2.0%) Cement Al2O3(7.5%)

K2O(1.5%) 100% MgO(2.5%)

SO3(1.5%) Na2O(1.5%)

156
CHEMISTRY FOR NEET & AIIMS
(ii) Raw Materials
y Lime Stone – It provides CaO
y Clay – It provides Al2O3 and silica (SiO2)
y Gypsum – CaSO4 . 2H2O
(iii) Setting of cement : When water is mixed to cement and the mixture is left it becomes very hard. This
property of cement is called setting.
(iv) Mortar : It is a mixture of cement, sand and water to give a proper consistency.
(v) Concrete : A mixture of cement, Sand gravel and water is known as concrete.
(vi) Reinforced concrete cement (RCC) : When concrete is filled in beams made of iron bars, it is called RCC.
Iron imparts extra strength to the structure.
BIOLOGICAL ROLE OF DIFFERENT ELEMENTS
(1) SODIUM
It maintain O.P. of body.
It play important role to absorption of glucose, amino acids and galectose.
It is associated with chloride and biocarbonate in regulator of acid base balance.
(2) POTASSIUM
It play important role to synthesis of Ribosomes.
Regulate Intra cellular osmolality
Maintain intracellular neutrality in response to H and Na
Helps for glycogen deposit in liver and skeleta muscles
Maintain normal cardiac rhythem
Maintain smooth muscles and skeletal muscles contraction
(3) MAGNESIUM
Magnesium is essential for the activity of the various enzymes such as enzymes of glycolysis.
It is the central atom present in chlorophyll (plant pigment necessary for photosynthesis).
It is a cofactor for the breakdown of the fats and glucose.
It is essential for the synthesis of the energy currency of the cell, that is, ATP. Responsible for the stability and synthesis
of DNA.
Maintains the electrolyte balance in the body. Magnesium deficiency is associated with sleep disorder. Deficiency also
leads to abnromal heart rhythms.
(4) CALCIUM
Used to stabilize the permeability of cell membranes.
Important for structure and function of proteins.
Essential component during blood clotting.
It also brings about muscle contraction.
Calcium acts as secondary messanger during cell signaling.
Helps in proper heart and nerve functions.
Calcium is essential for strong bones and teeth.

157
 s-BLOCK

1. Active nitrogen : N(atomic nitrogen)

2. Alums : M 2 'SO 4 .M 2 '''(SO 4 ) 3 .24H 2O

M' = K + , NH 4 + , Na + etc.

M''' Cr 3 , Al3 ,Fe 3 etc.

3. Asbestos : CaMg3(SiO3)4
4. Arsine : AsH3
5. Aquaregia : Conc. HNO3 + Conc. HCl (1 : 3 part)
6. Anhydrone : Mg(CLO4)2
7. Argentoferrous galena : PbS + Ag2S
8. Borax : Na2B4O7 . 10H2O
9. Blue vitriol : CuSO4, 5H2O
10. Barytes : BaSO4
11. Baryta water : Ba(OH)2 solution
12. Baryta : BaO
13. Baking soda : NaHCO3
14. Bleaching powder : CaOCl2
15. Boranes : Hydride of borone
16. Brine : NaCl solution
17. Calgon : Na2[Na4(PO3)6]
18. Coinage metals : Cu, Ag and Au
19. Carborundum : SiC
20. Cementite : FeC
21. Caliche : NaNO3 + NalO3
22. Caustic soda : NaOH
23. Caustic potash : KOH
24. Calomel : Hg2Cl2
25. Corrosive sublimate : HgCl2
26. Deuterium : 1
H2 of D
27. D.D.T. : p-dichloro, diphenyl, trichloroethane
28. Dry ice : Solid CO2
29. Freon : CF2Cl2
30. Ferric Alum : K2SO4. Fe2(SO4)3. 24H2O
31. Fenton’s reagent : H2O2 + few drops of FeSO4
32. Fusion’s mixutre : Na2CO3 + K2CO3
33. Fluid magnesia : 12% solution of Mg (HCO)2

158
CHEMISTRY FOR NEET & AIIMS

34. Fehling solution : CuSO4. 5H2O + NaOH + Na,K tartarate

35. King of metals : Gold
36. Horn Silver : AgCl
37. Green vitriol : FeSO4.7H2O
38. Graphite : An allotrope of carbon
39. Gun powder : 75% KNO3 + 12%S + 13% charcoal (explosive)
40. Glauber salt : Na2SO4.10H2O
41. Hydrolith : CaH2
42. Heavy water : D2O
43. Hypo (sodium thiosulphate) : Na2S2O3.5H2O
44. Heavy hydrogen : D2
45. King of chemicals : H2SO4
46. Lime (quick lime or brunt lime) : CaO
47. Lead pencil : Graphite
48. Lime water : Ca(OH)2
49. Laughing gas : N2O
50. Lunar Caustic : AgNO3
51. Litharge (Masscote) : PbO
52. Lithopone : (ZnS + BaSO4), a pigment
53. Mortar : Slaked lime + sand (1 : 3 in water)
54. mica : K2O. Al2O3. 6SiO2. 2H2O
55. Mohr salt : FeSO4.(NH4)2SO4. 6H2O
56. Matte : Cu2S + FeS
57. Milk of lime : Ca(OH)2 in water
58. Minium : Pb3O4
59. Micro cosmic salt : NaNH4.HPO4. 4H2O (used in test of silicates)
60. Milk of magnesia : Paste of Mg(OH)2 in water (Antacid)
61. Magnesia : MgO
62. Marsh gas : CH4
63. Nitrolim : CaCN2 + C (a fertilizer)
64. Nascent Hydrogen : H at the moment of generation
65. Nessler’s reagent : (K2HgI4 + KOH) aqueous solution
66. Indian saltpetre, Bengal salt petre : KNO3
67. Oil of vitriol : Conc. H2SO4
68. Ozone : O3
69. Oleum : H2S2O7
70. Permutit (Zeolite) : Na2Al2SiO8.XH2O
71. Pearl ash (Potash) : K2CO3
72. Plaster of paris : CaSO4 1/2H2O or 2CaSO4. H2O

159
 s-BLOCK

73. Philospher’s wool (chinese white) : ZnO (Zinc white)

74. Phosgene : COCl2
75. Phosphine : PH3
76. Pig iron : Impure form of iron
77. Producer gas : A mixture of CO + N2 + H2
78. Quartz : SiO2
79. Refrigerant : CO2, NH3. CF2Cl2 etc.
80. Red leab : Pb3O4
81. Rochelle salt : Sodium - potassium tartarate
82. Rust : Fe2O3. xH2O
83. Sorel’s cement (Magnesia cement) : MgCl2 . 5MgO. XH2O
84. Soda - lime : NaOH + CaO
85. Soda ash : Na2CO3 (anhydrous)
86. Slaked lime : Ca(OH)2
87. Stainless steel : An alloy of Fe, Cr and C
88. Salt cake : Na2SO4 (anhydrous)
89. Super phosphate : Ca(H2PO4)+2CaSO4
90. TNT : Trinitro toluene (an explosive)
91. TNB : Trinitro benzene (an explosive)
92. Tincal : Na2B4O7.10H2O
93. Talc : 3MgO. 4SiO2. H2O or Mg2 (Si2O3)2. Mg(OH)2
94. Tritium : 1
H3(an isotope of H)
95. Water glass : Na2SiO3
96. water gas : CO + H2
97. White vitriol : ZnSO4. 7H2O
98. Wrought iron : Pure form of iron
99. Washing soda : Na2CO3.10H2O
100. Willemite \ Zincite : ZnO
101. Zinc white : ZnO
102. Zinc blend : ZnS

160
CHEMISTRY FOR NEET & AIIMS

INDUSTRIALLY IMPORTANT PROCESS

Ammonia Soda process : Manufacture of NaHCO3, Na2 Co3
(Solvay process)

Birkeland - Eyde process : Manufacture of HNO3

Bosch process : Manufacture of H2

Castner process : Manufacture of Na

Caster - Kellner Cell process : Manufacture of NaOH

Contact process : Manufacture of H2SO4

Down process : Manufacture of Na

Dow’s process : Manufacture of phenol

Deacon’s process : Manufacture of Cl2

Haber process : Manufacture of NH3

Hasenclever process : Manufacture of Bleaching powder

L.D. process : Manufacture of steel

Lead chamber process : Manufacture of H2SO4

Nelson cell process : Manufacture of NaOH

Ostwald process : Manufacture of HNO3

161
 S-BLOCK

SOLVED EXAMPLE
Ex. 1 Li has the maximum value of ionisation potential Ex. 5 The highest NaOH gives disproportionation
among alkali metals i.e.e lithium has the minimum reaction with
tendency to ionise to give Li+ ion. lithium is – (A) S (B) CO2
(A) Strongest reducing (C) SO2 (D) SO3
(B) Poorest reducing agent '
Sol. (A) 4S + 6NaOH  o Na2S2O3 + 2Na2S + 3H2O
(C) Strongest oxidisting agent
(D) Poorest oxidising agent with excess pentasulfide forms
Sol. (A) The ionisation potential value of LIthium is Na2S + 4S  o Na2S5
maximum among alkali metals i.e., its tendency to Ex. 6 Metallic magnesium is prepared by
ionise to give Li+ ions should be the minimum (A) Reduction of MgO by coke
i.e. Li should be the poorest reducing agent. But,
(B) Electrolysis of aqueous solution of Mg(NO3)
lithium is the strongest reducing agent. This is due
(C) Displacement of Mg by ion from MgSO4
to the largest value of hydration energy of Li+ ions.
solution
Ex. 2 The highest melting point among alkali metal of – (D) Electrolysis of molten MgCl2
(A) Li (B) Na Sol. (D) MgCl2 o
Electrolysis Mg+2 + 2Cl
(C) K (D) Rb
Sol. (A) Li has highest melting point among alkali (Molten) Cation Anion
–  o 2Cl + 2e , Cl + Cl 
metals. All alkali metals have low M.P. The M.P. Anode : 2Cl –
o Cl3
decrease down the group. The low M.P. are Cathode : Mg+2 + 2e– 
o Mg
attributed to their larger atomic size due to which
Ex. 7 The first ionization potential of Mg is
the binding energies of their atoms in the crystal
lattice are low. (A) Less than Al (B) More than Al
(C) Equal toAl (D) Zero
Ex. 3 Commercial common salt becomes slightly damp on Sol. (B) The first ionization potential of Mg is more than
keeping. This is due to the fact that – Al sice the electron has to be removed from
(A) Common salt is hygroscopic completely filled svalence shell of Mg.
(B) Common salt contains some impurity whichis
hygroscopic Ex. 8 Portland cement is manufactured by using–
(C) Salt is efflorescent (A) Lime stone, clay and sand
(D) Salt is crystalline (B) Lime stone, gypsum and sand
Sol. (B) Commercial common salt commonly becomes (C) Lime stone, gypsum and alumina
slightly damp on keeping because common salt (D) Lime stone, clay and gypsum
contains some impurity MgCl2 and CaCl2 which is Sol. (D) Lime stone – CaCO3
hygroscopic in nature and absorbs moisture from Clay – silica and alumina
the atmosphere. Gypsum – CaSO4.2H2O
Ex. 4 CO2 gas along with solid (Y) is obtained when Ex. 9 Gypsum CaSO4.2H2O on heating to about 120°C
sodium salt (X) is heated. (X) is again obtained when forms a compound which has the chemical
CO2 gas is passed into (Y). X & Y are –
composition represented by
(A) Na2CO3, Na2O (B) Na2CO3, NaOH
(A) CaSO4 (B) 2CaSO4.H2O
(C) NaHCO3, Na2CO3 (D) Na2CO3, NaHCO3
(C) CaSO4.H2O (D) 2CaSO4.3H2O
Sol. (C) 2NaHCO3 Heat
o Na2CO3 + H2O + CO2 Sol. (B)
(X) (Y) 120°
Na2CO3 + H2O + CO2  o 2NaHCO3 2(CaSO4.2H2O) Dehydration 2CaSO4. H2O + 3H2O
(Y) (X) Gypsum Plaster of paris

162
CHEMISTRY FOR NEET & AIIMS
Ex. 10 Which of the following compound decomposes at Ex. 13 If Na+ ion is larger than Mg2+ ion and S2– ion is larger
highest temperature – than Cl– ion, which of the following will be least
(A) SrCO3 (B) BaCO3 soluble in water?
(C) CaCO3 (D) MgCO3 (A) Sodium chloride
Sol. (B) BaCO3 decomposes at highest temp. (B) Sodium sulphate
All the carbonates decompose on heating to give (C) Magnesium chloride
CO2 and metal oxide. (D) Magnesium sulphide
MCO3  '
o MO + CO2 Sol. (D) Magnesium sulphide. Higher the lattic energy
lower the solubility. Out of the four combinations
The stability of carbonate towards heat depends
possible, the lattic energy of MgS (Bi–bivalent ionic
upon the stability of the resulting metal oxide. More
solid) is higher than those of Na2S, MgCl2 (uni-
is the stability of the resulting metal oxide lesser is
bivalent or biunivalent ionic solids) and NaCl
the stability of the carbonate towards heat and vice
(uniunivalent ionic solids) and hence MgS is the
versa.
least soluble.
Ex. 11 Potassium is kept in
Ex. 14 The cation which gives a yellow precipitate with
(A) Alcohol (B) Water potassium chromate is
(C) Kerosene (D) Liquid ammonia
(A) SrCO3 (B) BaCO3
Sol. (C) Alkali metals are highly reactive metal. They react (C) CaCO3 (D) MgCO3
with
Sol. (B) Barium gives a yellow ppt. of barium chromate
Alcohol – 2C2H5OH + 2K  o 2C2H5OK + H2 with pot. chromate.
Water – 2K + 2H2O 
o 2KOH + H2 K2CrO4 + Ba2+  o BaCrO4 + 2K+
Ammonia – K + (x + y)NH3  o [K(NH3)x]+ +
Ex. 15 Which liberates ammonia when treated with
[e(NH3)2]–
(A) Li3N (B) Mg3N2
Ammoniated cation Ammoniated electron (C) CaCN2 (D) All
But they do not react with Kerosene. Sol. (D) All nitrides react with H2O to yield NH3. Calcium
cyanamide (CaCN2) on hydrolysis also given NH3.
Ex. 12 Which of the following is used as barium metal for
getting the X-ray spectrum of the human digestive CaNCN + 3H2O  o CaCO3 + NH3
system?
(A) BaSO4 (B) BaCl2
(C) BaF2 (D) BaCO3
Sol. (A) BaSO4 is both insoluble in water and opaque to
X-rays and hence is used to get the X-ray spectrum
of the digestive system?

163
CHEMISTRY FOR NEET & AIIMS

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. The correct order of the mobility of the alkali metal

ions in aqueous solution is [CBSE AIPMT 2006] 9. “Metals are usually not found as nitrates in their
(A) Li + > Na + > K + > Rb + ores”. [CBSE AIPMT 2015]
(B) Na + > K + > Rb + > Li + Out of the following two (I and II) reasons which is/
are true for the above observation ?
(C) K + > Rb + > Na + > Li +
I. Metal nitrates are highly unstable.
(D) Rb + > K + > Na + > LI +
II. Metal nitrates are highly soluble in water.
2. The correct order of increasing thermal stability of (A) I and II are true (B) I and II are false
K2CO3, MgCO3, CaCO3 and BeCO3 is (C) I is false but II is true (D) I is true but II is false
[CBSE AIPMT 2007]
(A) BeCO3 < MgCO3 < K2CO3 < CaCO3 10. In context with beryllium, which one of the following
statements is incorrect ? [NEET 2016, Phase II]
(B) BeCO3 < MgCO3 < CaCO3 < K2CO3
(A) It is rendered passive by nitric acid
(C) MgCO3 < BeCO3 < CaCO3 < K2CO3
(B) It forms Be2C
(D) K2CO3 < MgCO3 < CaCO3 < BeCO3
(C) Its salts rarely hydrolyse
3. In which of the following the hydration energy is (D) Its hydride is electron-deficient and polymeric
higher than the lattice energy ? [CBSE AIPMT 2007]
(A) BaSO4 (B) MgSO4 11. Which of the following statement about hydrogen
is incorrect ? [NEET 2016, Phase I]
(C) RaSO4 (D) SrSO4
(A) Hydrogen never acts as cation in ionic salts
4. The sequence of ionic mobility in aqueous solution (B) Hydronium ion, H3O+ exists freely in solution
is [CBSE AIPMT 2008] (C) Dihydrogen does not act as a reducing agent
(A) K + > Na + > Rb + > Cs+ (D) Hydrogen has three isotopes of which tritium is
(B) Cs + > Rb + > K + > Na + the most common
(C) Rb + > K + > Cs + > Na+
12. The product obtained as a result of a reaction of
(D) Na+ > K + > Rb+ > Cs+
nitrogen with CaC2 is [NEET 2016, Phase I]
5. Equimolar solution of the following were prepared (A) CaCN (B) CaCN3
in water separately. Which one of the solution will (C) Ca2CN (D) Ca(CN)2
record the highest pH ? [CBSE AIPMT 2008]
(A) SrCl2 (B) BaCl2 13. Ionic mobility of which of the following alkali metal
ions is lowest when aqueous solution of their salts
(C) MgCl2 (D) CaCl2
are put under an electric field ?
6. Which one of the following is present as an active [NEET 2017]
ingredient in bleaching powder for bleaching (A) Na (B) K
[CBSE AIPMT 2011] (C) Rb (D) Li
(A) Ca(OCl)2 (B) CaO2Cl2
(C) CaCl2 (D) CaOCl2 14. Among CaH2, BeH2, BaH2, the order of ionic
character is [NEET 2018]
7. On heating which of the following releases CO2 most
easily ? [CBSE AIPMT 2015] (A) BeH2 < BaH2 < CaH2
(A) K2CO3 (B) Na2CO3 (B) CaH2 < BeH2 < BaH2
(C) MgCO3 (D) CaCO3 (C) BeH2 < CaH2 < BaH2
8. Solubility of the alkaline earth’s metal sulphates in (D) BaH2 < BeH2 < CaH2
water decreases in the sequence
[CBSE AIPMT 2015]
(A) Mg > Ca > Sr > Ba (B) Ca > Sr > Ba > Mg
(C) Sr > Ca > Mg > Ba (D) Ba > Mg > Sr > Ca

164
 S-BLOCK

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

1. The pair whose both species are used in anti-acid 8. Which of the following acids will not evolve H2 gas
medicinal preparation is on reaction with alkali metals?
(A) NaHCO3 and Mg(OH)2 (A) Hydrazoic acid (B) Perxenic acid
(B) Na2CO3 and Ca(HCO3)2 (C) Boric acid (D) None of these
(C) Ca(HCO3)2 and Mg(OH)2 [2010]

(D) Ca(OH)2 and NaHCO3 [2006]

9. Which of the following is not hygroscopic ?
2. Among the following components of cement which (A) CsCl (B) MgCl2
is present in highest amount ? (C) CaCl2 (D) LiCl [2011]
(A) Ca2SiO4 (B) Ca3SiO5
10. Which is correct order of solubility in water ?
(C) Al2O3 (D) Ca3Al2O6
(A) Ba(OH)2 < Mg(OH)2
[2007]
(B) BaCO3 > CaCO3
3. Formula of microcosmic salt is (C) CaSO4 < MgSO4
(A) Na2HPO4 (D) Ca(OH)2 Mg(OH)2 [2012]
(B) Na(NH4)HPO4
11. Bleaching powder doec not contain
(C) K2HPO4
(D) Na2PO4.K2PO4 [2009] (A) CaCl2 (B) Ca(OH)2
(C) Ca(OCl)2 (D) Ca(ClO3)2
4. The correct order of stability of the superoxides is [2013]
(A) KO2 > RbO2 > CsO2
12. Which of the following statements is incorrect ?
(B) KO2 > CsO2 > RbO2
(A) Li+ has minimum degree of hydration.
(C) CsO2 > RbO2 > KO2
(B) The oxidation state of K in KO2 is +1.
(D) RbO2 > CsO2 > KO2 [2009]
(C) Na is used to make a Na/Pb alloy.
5. Which of the following fluorides has the lowest (D) MgSO4 is readily soluble in water.
melting point ? [2014]
(A) BaF2 (B) SrF2
13. Which of the following has highest hydration energy
(C) CaF2 (D) BeF2 [2009]
?
6. Which of the following has the highest tendency to (A) MgCl2 (B) CaCl2
give the reaction, M 
(g) o M
aqueous 
(aq) ? (C) BaCl2 (D) SrCl2 [2015]
medium

(A) Na (B) Li
14. A laboratory reagent imparts green colour to the
(C) K (D) Rb [2009]
flame. On heating with solid K2Cr2O7 and conc. H2SO4
7. Beryllium and aluminium exhibit many properties
it evolves a red gas. Identify the reagent [2017]
which are similar. But the two element sdiffer in
(A) CaCl2 (B) BaCl2
(A) maximum covalency in compounds
(C) CuCl2 (D) None of these
(B) exhibiting amphoteric nature in their oxides
(C) forming covalent halides
(D) forming polymeric hydrides. [2010]

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CHEMISTRY FOR NEET & AIIMS
ASSERTION AND REASON
19. Assertion : Magnesium is extracted by the
In each of the following questions, two statement electrolysis of fused mixture of MgCl2, NaCl and
are given one is assertion and the other is reason. CaCl2.
Examine the statement carefully and mark the correct Reason : Calcium chloride acts as a reducing agent.
answer according to the instruction given below [2010]
(A) If both the assertion and reason are true and
20. Assertion : beSO4 is soluble in water while BaSO4 is
reason explains the assertion
not.
(B) If both the assertion and reason are true but
Reason : Hydration energy decreases down the
reason does not explain the assertion
group from Be to Ba and lattice energy remains
(C) If assertion is true but reason is false
almost constant. [2015]
(D) If assertion is false but reason in true
(E) Both assertion & reason are false 21. Assertion : Generally alkali and alkanline earth metals
form superoxides.
15. Assertion : Barium is not required for normal Reason : There is a single bond betwee O and O in
biological function in human. superoxides. [2016]
Reason : Barium does not show variable oxidation
state. [2003]

16. Assertion : Mg is not present in enamel of human

teeth.
Reason : Mg is an essential element for biological
function of human. [2004]

17. Assertion : Addition of NH4OH to an aqueous

solution of BaCl2 in the presence of NH4Cl (excess)
precipitates Ba(OH)2.
Reason : Ba(OH)2 is insoluble in water
[2005]

18. Assertion : In fused state, calcium chloride cannot

be used to dry alcohol or NH3.
Reason : CaCl2 is not a good dessicant.
[2009]

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CHEMISTRY FOR NEET & AIIMS

ANSWER KEY

EXERCISE : PART # I
1. D 2. B 3. B 4. B 5. B 6. A 7. C 8. A 9. C 10. C 11. C,D 12. * 13. D
14. C
PART # II
1. A 2. D 3. B 4. C 5. D 6. B 7. A 8. D 9. A 10. C 11. D 12. A 13. A
14. B 15. B 16. B 17. D 18. C 19. C 20. A 21. D

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CHEMISTRY FOR NEET & AIIMS

EXERCISE
P-1 (NEET/AIPMT)
1. (D) The correct order of the mobility of the alkali metal
ions in aqueous solution is Rb+ > K+ > Na+ > Li+ due to
following order of hydration energy of these ions
Li + > Na+ > K+ >Rb+ and as the hydration of ion increases,
mobility decreases.
1
Hydration enthalpy v
Sizeof cation

2. (D) Thermal stability of carbonates increases in a group

as we move from top to bottom and decreases in a period
as we move from left to right, so the correct order of
thermal stability of given carbonates is
BeCO3 < MgCO3 < CaCO3 < K2CO3
Be, Mg and Ca are present in second group and K is
present in first group.
3. (B) Hydration energy of sulphate decreases from top to
bottom in II group. Mg2+ is smaller than other given ions
of II group, so Mg2+ is readily hydrated MgSO4 has higher
hydration energy than lattice energy.
4. (B) The smaller the size of the ion, the greater is the
4PMVUJPOT degree of hydration, thus degree of hydration is highest
for Li+ and lowest for Cs+. Thus, Li+ holds more water
molecules in its hydration sphere and becomes largest
in size among alkali metals and Cs+ ion hold least number
of water molecules.
Hence, ionic mobility is highest for Cs+ (due to its smallest
size in aqueous solution) and lowest for Li+. Here the
lowest is for Na+. Thus, the order of ionic mobility in
aqueous solution is
Cs+ > Rb+ > K+ > Na+

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 S-BLOCK
5. (B) All salts are soluble in water and give strong acid 10. (C) Beryllium salts are covalent in nature because of
and weak base very small size of Be2+ ion and its high polarising power,
so it is easily hydrolysed.
SrCl2  2H 2 O 
o Sr(OH) 2  2HCl
e.g. BeCl2  2H 2 O 
o Be(OH)2  2HCl
BaCl2  2H 2 O 
o Ba(OH) 2  2HCl
11. (c, d) * For ionic salts, hydrogen never behaves as cation,
MgCl2  2H 2 O 
o Mg(OH) 2  2HCl
but behaves as anion (H–)
CaCl2  2H 2 O 
o Ca(OH) 2  2HCl * H3O+ exists freely in solution.
The basic nature of alkaline earth metals generally * Dihydrogen acts as a reducing agent.
increases from Be to Ra. Thus, the order of basic anture * Hydrogen has three isotopes.
of these hydroxides isOH Protium (11 H)
Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2
Hence, pH is highhest for BaCl2. (As pH increases with Deuterium (12 H)
basic nature) Tritium (13 H)
6. (A) Ca(OCl) 2, calcium hypochlorite is the active Protium is the most common isotopes of hydrogen with
ingredient in bleaching powder which releases chlorine. an abundance of 99.98%
7. (C) Order of thermal stabilty is
K2CO3 > Na2CO3 > CaCO3 > MgCO3 12. (*) When calcium carbide (CaC2) reacts with nitrogen
(N2) under high temperature, it forms calcium cyanamide
Hence, MgCO3 releases CO2 most easily
which is also called nitrolim.
'
MgCO 3  o MgO  CO 2
CaC2  N 2 High
temperature
o CaCN 2  C
Calcium cyanamide
8. (A) Solubility of the sulphates. The sulphates becomes
less soluble as you go down the group i.e. Hence, option (d) should be CaCN2 instead of Ca(CN)2.
Mg > Ca > Sr > Ba Thus no option is correct.
The magnitude of the lattice energy remains almost
constant as the size of the sulphate ion is so big that 13. (D) Key concept More the extent of hydration, lesser is
small increase in the size of the cation from Be to Ba does the ionic mobility.
not make any difference. However, the hydration energy In all the alkali metals, Li+ ion is smallest. Thus extent of
decreases from Be2+ to Ba2+ apprecipably as the size of hydration is maximum in Li+ ion.
the cation increases down the group. The significantly i.e. the dissolution of Li+ i in water occurs and get
high solubility of MgSO4 is due to high enthalpy of hydrated. Smaller the size of a cation, greater is the extent
solvation of the smaller Mg2+ ions. of hydration and lesser is the ionic mobility.
BeH 2  CaH 2  BaH 2
9. (C) Metals are usually not found as nitrates in their ores, 14. (C) 
Polarisation p Ionic charater n
o
because metal nitrates are highly soluble in water, For
example. KNO3 (salt peter) would be classified as
completely soluble. thus, KNO3 could be expected to
EXERCISE

dissociate completely in aqueous solution to give K+ P-2 (AIIMS)
and NO3 ions.

KNO3 U K  (aq)  NO 3 (aq) 1. (A) Intestine is acidic due to formation of HCl during
The nitrate anion has three equivalent oxygen digestion. Excessive acidity in the intestine creates
surrounding a cental nitrogen atom. This tends to spread problem of intestinal ulcer, gastric reflux and
the single negative charge and make it easier for water oesophagitis. The compound which reduces or
(using hydrogen bonds) to separate the ions in solution. neutralises acidity are called antacids.
O O– O– NaHCO3 + HCl o NaCl + H2O + CO2
N N N Mg(OH)2 + 2HCl o MgCl2 + 2H2O
–
O O–
–
O O O O–

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CHEMISTRY FOR NEET & AIIMS
Therefore, Li+ has maximum degree of hydration.
2. (D) Tricalcium aluminate 3CaO.Al2O3 - Calcium aluminate
cements are hydraulic cements made primarily from
13. (A) Smaller sized and highly charged ions have higher
limestone and bauxite. They are well adapted for use in
hydration energy. In the alkaline earth metals, the hydra-
refractory (high temperature resistant) concerets e.g.,
tion energy of the compact ions is greater than the large
furnace linings.
sized ions. Therefore, order of hydration energy in this
group is

3. (B) Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+.

14. (B) The reagent is BaCl2 which imparts green colour to

flame. BaCl2 forms chromyl chloride (which is red in
4. (C) Stability of superoxides increases with increase in
colour), when treated with K2Cr2O7 and conc. H2SO4.
size and electropositivity of the metal Hence, The order
is CsO2 > RbO2 > KO2. 2BaCl2 + K2Cr2O7 + 3H2SO4 o

K2SO4 + 2BaSO4 + 2CrO2Cl2 + 3H2O

5. (D) being covalent, BeF2 has the lowest melting point
Chromyl chloride
(800°C) white other fluorides melt at around 1300°C.
(red gas)

6. (B) Because of its smallest size, Li+ has highest hydration

energy and hence, the highest stability of hydrated Li+ 15. (B) Ba – [Xe]6s2
ion.
It shows oxidation state of +II only.

7. (B) Be exhibits maximum covalency of four whereas

16. (B) Enamel, the hardest substance of the body is
Al shows maximum covalency of six.
composed of fluorine not magnesium. Magnesium is an
essential element as it acts as a co-factor of many
8. (D) None of these acids evolve H2 gas with alkali metals. enzymes of glycolysis and a number of other metabolic
reactions.

9. (A) CsCl is not hygroscopic in nature while MgCl2, CaCl2

and LiCl are hygroscopic in nature. 17. (D) Ba(OH)2 is soluble in water.

10. (C) MgSO4 is readily soluble in water. The solubility of 18. (C) CaCl2 forms addition products with alcohol and
the sulphates of alkaline earth metals decreases with ammonia. (CaCl2.4NH3 or CaCl2. 4C2H5OH).
increase in size of the central metal ion. The greater
hydration enthalpies of Mg2+ ions overcome the lattice
19. (C) NaCl and CaCl2 are added to provide conductivity to
enthalpy factro and therefore, MgSO4 is more soluble in
the electrolyte and also to lower the fusion temperature
water.
of anhydrous MgCl2.

11. (D) Bleaching powder is a mixture of calcium

20. (A)
hypochlorite, Ca(OCl)2 and the basic chloride CaCl2, H2O
with some slaked lime, Ca(OH)2.
21. (D) Only K, Rb and Cs from alkali metals form superoxides
and superoxides possess three electron bond
12. (A) The hydration enthalpies of alkali metal ions
decreases with increase in ionic sizes Hence, the order is (:ö–ö:)–
Li+ > Na+ > K+ > Rb+ > Cs+.

170
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8PSL
3PVHI
8PSL