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1.

1) Atomic Radius.

Definition:

Is the distance of closest approach of one atom to another atom in a bonding situation.

Atomic radius is half the inter-nuclear distance between two identical atoms in a bond-
ing situation.

At such a distance, the repulsive forces between nucleus-nucleus, electron-electron and

the attractive forces between nucleus-electron just balance.

Trends in Atomic Radius

I) Across the period.

Atomic radius decreases across the period.

Explanation

 On traversing the period from one element to the next, the additional electron is
added to shells with the same energy ie no new energy level is formed.

 The nuclear charge progressively increases and yet the screening/ shielding effect
of the inner complete shells remains almost constant.

 As a result the effective nuclear charge increases and electrons in the outer most
shell are pulled more strongly leading to a decrease in atomic radius.

Elements At. Electronic con-

Number figuration

Li 3 1S22S1

Be 4 1S22S2

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 B 5 1S22S22P1
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C 6 1S22S22P2

N 7 1S22S22P3

O 8 1S22S22P4

F 9 1S22S22P5

Ne 10 1S22S22P6

The diagram shows how the atomic radius changes as you go across Period 3.

The figures used to construct this diagram are based on:

metallic radii for Na, Mg and Al;

covalent radii for Si, P, S and Cl;

the van der Waals radius for Ar because it doesn't form any strong bonds.

ii) Down the group

Atomic radius increases down the group in the periodic Table.

Explanation

 On descending any group from one element to the next, electrons are being added
to shells with higher energies (i.e a new electron shell is formed)

 As a result both the nuclear charge and screening effect increase but the increase
in screening effect outweighs that due to nuclear charge.

 The effective nuclear charge therefore decreases , nuclear attraction for the outer
most electrons decreases hence increase in atomic radius.

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 Element Atomic Configuration
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Number

Li 3 1S22S1

Na 11 1S22S22P63S1

K 19 1S22S22P63S23P64S1

Rb 37 1S22S22P63S23P64S23d104P65S1

Cs 55 --------

Cation is (a positive ion) formed by the removal of one or more electrons from an atom.
A cation is smaller than the atom from which its formed.

Explanation

After the removal of one or more electrons, the number of protons in the nucleus become
greater than the number of remaining electrons, thus the proton-electron ratio increases.

As a result, the nuclear attraction for the remaining electrons increases leading to a de-
crease in cationic radius.

An anion (a negatively charged ion) is formed by gain of one or more electrons by an at-
om. The radius of an anion is bigger than that of the corresponding atom from which its
formed.

Explanation

After the gain of one or more electrons by an atom, the number of electrons present be-
comes more than the number of protons present in the nucleus thus the proton-electron ra-
tio decreases.

The nuclear attraction for the many electrons now present decreases leading to increase in
anionic radius.
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Isoelectronic ions are ions that have the same number of electrons and the same electronic
structure.

For example:

Isoelectronic ions number of electrons

1. Al3+,Mg2+, Na+, F- 10 electrons

2. S2-, Cl-, K+, Ca2+ 18 electrons

isoelctronic ions, Al3+,Mg2+,Na+, F- (ions both have 10 electrons):

 Al3+ has 13 protons, a nuclear charge of +13.

 Mg2+ has 12 protons, a nuclear charge of +12.
 Na+ has 11 protons, a nuclear charge of +11.
 F- has 9 protons, a nuclear charge of +9.

Al3+, with the largest nuclear charge will be expected to have the greatest attraction of
its electrons .

Therefore Al3+ has the smallest ionic radius i.e radius is in the order Al3+ <Mg2+ <Na+
<F-

The radius decreases as the positive nuclear charge increases. Consequently charge
densities and polarizing powers of the ions increase.

Look at the second example of isoelctronic ions, S2-, Cl-, K+, Ca2+ (ions all have 18 elec-
trons):

 S2- has 16 protons, a nuclear charge of +16.

 Cl- has 17 protons, a nuclear charge of +17.
 K+ has 19 protons, a nuclear charge of +19.

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  Ca2+ has 20 protons, a nuclear charge of +20.
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2. IONISATION ENERGY

The ionization energy of an atom measures how strongly an atom holds its electrons.

Definition:

Ionization energy( 1st ionization energy) of an element is the minimum amount of energy
required to remove an electron completely from the outer most shell of an isolated gase-
ous atom to form a unipositively charged gaseous ion.

M(g) → M+(g) + e - H= 1st ionization energy.

Second ionization energy

Is the minimum amount of energy required to remove an electron from the outer most
shell of a unipositively charged gaseous ion to form a dipositively charged gaseous ion.

M+(g) → M2+(g) + e- H= 2nd ionization energy.

The higher the value of the ionization energy, the more difficult it is to remove the elec-
tron.

As electrons are removed, the positive charge from the nucleus remains unchanged, how-
ever, the ionization energy is higher for each subsequent electron.

There is also a big increase in ionization energy for removal of an electron from an inner
shell (lower n value).

This is due to the fact that when you move to an orbital with a lower principle quantum
number, you are removing an electron which is much closer to the nucleus and is being
strongly held by the nucleus.

FACTORS AFFECTING 1ST IONIZATION ENERGY

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1) Nuclear charge of an atom.

2) Shielding / Screening effect of inner shells of electrons.

3) Atomic radius.

Electronic configuration of the outer shell

Explanation

1. Nuclear charge.

 When the nuclear charge is high, the electrons present in the outer most shell are
attracted more strongly by the nucleus.

 Therefore removing an electron from this shell requires more energy leading to
high 1st ionization energy.

 When the nuclear charge is low, the electrons present in the outer shell are attract-
ed less strongly by the nucleus.

 Therefore removing an electron from it requires less energy leading to low 1st ion-
ization energy.

2. Shielding effect of inner complete shells of electrons.

 This is the tendency of the inner electrons to screen the other outer electrons from
the nuclear attraction.

 When the screening effect is high, the effective nuclear charge for the outer most
electrons reduces.

 As such less energy is required to remove an electron from the outer most shell
leading to low 1st ionization energy.

 When the screening effect is low, the effective nuclear charge for the outer most
electrons increases.

As a result more energy is required to remove an electron from this outer shell against a
high nuclear attraction.

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 3. Atomic radius.
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If the atomic radius is small, the outer most electrons are closer to the nucleus and
are attracted more strongly by it. Thus removing an electron from this outer shell
requires more energy leading to high 1st ionization energy.

If the atomic radius is large, the outer most electrons are more distant from the
nucleus. There is less attraction from the nucleus, and an electron can be removed
easily leading to a low 1st ionization energy.

4. Electronic configuration of the outer most shell.

 When the first electron is coming from an outer sub-shell which is half full (eg. N:
1S22S22P3), a lot of energy is needed since the unpaired electrons experience min-
imum repulsion and the shell is thermodynamically stable.

 When the 1st electron is coming from an outer shell which is fully filled e.g Ne:
1S22S22P6 ,a lot more energy is needed to remove it because the shell is thermo-
dynamically more stable.

 When the 1st electron comes from a shell where electron pairing has begun e.g O:(
1S22S22P4), less energy is required because of mutual repulsion between paired
electrons.

Periodic trends in ionization energies

First ionization energies as a function of atomic number

Within each period (row) the 1st ionization energy typically increases with atomic num-
ber

Within each group (column) the 1st ionization energy typically decreases with increasing
atomic number

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The basis for these observations:

As the effective charge increases, or as the distance of the electron from the nucleus de-
creases, the greater the attraction between the nucleus and the electron.

The effective charge increases across a period, in addition, the atomic radius decreases

As we move down a group the distance from the nucleus increases and the attraction of
the electrons for the nucleus decreases.

a) 1st ionization energy generally increases across the period in the periodic Table.

Explanation

On traversing any period in the periodic Table from one element to the next, electrons are
being added to shells with the same energy as such the nuclear charge progressively in-
creases while the screening effect of the inner shells remains almost constant.

Consequently, the effective nuclear charge increases leading to a high nuclear attraction
for the outer most electrons. Thus removing the 1st electron requires more energy.

b) 1st ionization energy generally decreases down any group in the periodic Table.

Explanation

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 On descending any group from one element to the next in the periodic table, electrons are
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being added to shells with higher energy i.e an extra shell of electrons is added.

Thus both the nuclear charge and the screening effect increase but the increase in screen-
ing effect out- weighs that due to nuclear charge.

The effective nuclear charge progressively decreases leading to a decreased nuclear at-
traction for the outer most electrons hence 1st ionization energy decreases.

Explanation

 On traversing the short period, lithium to neon, the 1st ionization energy increases
in general but there is a break observed at boron and oxygen.

 Lithium, 1S22S1 has the lowest 1st ionization energy . This is because the single
electron in the outer most 2s shell is weakly held by the nucleus due to the shield-
ing effect of complete inner 1s-electrons.

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  Beryllium, 1S22S2 has a higher 1st I.E because the nuclear charge increases
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whilst the electron is being added to the same 2s shell. Above all the outer most 2s
shell is full.

 Boron , 1S22S2 2p1 loses the outer most p-electron easily despite an increase in
the nuclear charge because the shielding effect of the interposing complete inner
s-shells increases thus reducing the effective nuclear charge considerably. In ad-
dition, the 2p sub-shell is further from the nucleus than the 2s electron that is re-
moved from Be (1st I.E of Be > for B).

 There after the nuclear charge increases from boron through carbon 1S22S22P2 to
nitrogen 1S22S22P3, in line with an increase in nuclear charge while electrons are
being added to the same shell.

 At nitrogen, the 2p-subshell is half full, the three electrons being unpaired experi-
ence minimum repulsion thus thermodynamically stable.

 In the case of oxygen 1S22S22P4 ,electron is being paired in one of the 2p-orbitals
as such there is mutual repulsion between the two paired electrons. An electron
can easily be removed from this outer 2p-shell thus a decrease in 1st I.E is ob-
served.

 Further increase in ionization energy is observed on traversing the period from

oxygen to neon. This is in line with increase in nuclear charge as the 2p shell is
building up and reaches a maximum at neon, 1S22S22P6 , which has a complete
stable configuration.

A similar trend is observed on traversing the 2nd short period from sodium to argon.

NB:

In every period, noble gases have the highest 1st ionization energy. This is because noble
gases have fully filled outer most shell thus thermodynamically stable.

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 Helium : 1s2 has the highest 1st ionization energy of all atoms.
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This is because Helium atom has the smallest atomic radius therefore electrons in its out-
er most shell are closer to the nucleus and are attracted more strongly.

Also it has a stable outer most shell 1s2 .

IMPORTANCE OF IONIZATION ENERGY

Ionization energy provides a basis for understanding the chemistry of an element. The fol-
lowing information is provided:

1. Atomic number of the element .

This is given by the number of successive ionization energies an atom has got e.g sodium
with 11 successive ionization energies has atomic number 11.

2. The arrangement of electrons in the shells.

A plot of successive ionization energies of calcium shows distinct portions.

Qn.

Element 1st I.E 2nd I.E 3rd I.E 4th I.E

A 800 2400 3700 25000

B 900 1800 14800 21000

C 500 4600 6900 9500

D 1090 2400 4600 6200

E 1310 3400 5300 7500

The table below shows the 1st four ionization energies of elements A-E.

a) Which group in the periodic table does each of the following elements belong:

i) A ii) B iii) C

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 Give a reason for your answer in each case.
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Qn.

Element A B C D E F

1st I.E 1013 1000 1255 1519 418 590

2nd I.E 1904 2255 2297 2665 3067 1146

3rd I.E 2916 3389 3853 3933 4393 4916

The table below shows the successive ionization energies of elements A-F.

a) Which element is a noble gas? Give reason for your answer.

b) Which element belongs to :

i) group(i) ii) group(ii).

Give reason for your answer in each case.

Qn.

The table below shows the 1st five ionization energies in K/J per mole for elements W-Z.

Element 1st 2nd 3rd 4th 5th

W 577 1816 2745 11575 13251

X 738 1450 7730 10550 12756

Y 495 4563 6912 9540 11936

Z 1255 2297 3849 5163 13989

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 a) Identify the group to which each of the elements belong and give a reason for your an-
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swer in each case.

b) Which pair of elements will form :

i) an ionic bond between them?

ii) a covalent bond?

Qn.

The first 8 ionization energies in K/J per mole of an element Y are shown below:

1st 2nd 3rd 4th 5th 6th 7th 8th

786 1580 3230 4360 16000 20000 23600 29100

Which group in the periodic table does element Y belong? Give a reason for your answer.

3. ELECTRON AFFINITY

Non-metallic electronegative elements accept electrons to form anions with a noble gas
like structure as such the concept of electron affinity is more useful or important than
ionization energy.

Electron affinity is defined as the enthalpy change that occurs when a gaseous atom gains
an extra electron to form a univalently charged gaseous anion.

M(g) + e → M-(g) H= 1st Electron Affinity.

The electron affinity is a measure of the attraction between the incoming electron and the
nucleus. The higher the attraction, the higher the electron affinity.

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First electron affinity:

of an element is defined as the energy released when a gaseous atom gains an extra elec-
tron to form a univalently charged gaseous anion.

X(g) + e → X-(g) H= 1st electron affinity

After the gain of an electron by a gaseous atom, the negatively charged gaseous ion
formed repels any further electron.

Second electron affinity

is defined as the amount of energy absorbed/ required when a univalently charged gase-
ous anion gains an electron to form a divalently charged gaseous anion.

X-(g) + e → X2-(g) H=2nd electron affinity

First electron affinity is an exothermic process .

Explanation:

This is because the incoming electron experiences a greater attraction from the nucleus
than repulsion from the electrons already present .

Second electron affinity is an endothermic process.

Explanation:

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 This is attributed to greater repulsive force which the electron being added experiences
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from electrons already present than the attraction from the nucleus, thus work must be
done to over come the effect of repulsion. This work involves input of heat energy.

Note:

Because of the same reason, the 3rd ,4th ,5th etc electron affinity will have a positive H
sign.

FACTORS THAT DETERMINE THE VALUE OF 1st E.A

1. Nuclear charge.

2. Atomic radius.

3. Shielding/ screening effect of the inner complete shells of electrons.

4. Electronic configuration of the outer shell of an atom

Explanation

1. Nuclear charge

If the nuclear charge is high, the nuclear attraction for the incoming electron will be high.
As the atoms gains the electron, a lot of energy is released.

If the nuclear charge is low, the attraction for the incoming electron will be low leading to
a low electron affinity.

2. Atomic radius

If the radius of an atom is small, the incoming electron experiences a high attraction from
the nucleus of the atom. As such a lot of energy is given out as the atom gains the electron
giving rise to a high electron affinity.

If the radius of an atom is large, the incoming electron experiences a weak attraction
from the nucleus of the atom. As such a lot of energy is given out as the atom gains the
electron giving rise to a high electron affinity.

3. Shielding effect of the electrons in the inner shells.

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 If the screening effect of the electrons in the inner shells is high, electron being added ex-
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periences a low attraction from the nucleus leading to a low value of electron affinity.

However, if the screening effect is low, the incoming electron experiences a high attrac-
tion from the nucleus leading to a large value of electron affinity.

4. Electronic configuration of the outer shell.

If an electron is being added to an atom with a stable outer electronic configuration (i.e
half full or fully filled sub shell), the addition will not occur easily leading to a low value
of electron affinity.

Variation of electron affinity

i) Across the period.

First electron affinity generally increases on traversing any period in the periodic table.

Explanation:

In moving across from one element to the next, electrons are being added to the shells
with the same energy as a result the nuclear charge progressively increases while the
screening effect of the electrons in the inner shells remains almost constant.

The effective nuclear charge increases leading to increased nuclear attraction for the elec-
tron being added and hence an increase in 1st E.A.

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ii) Down the group.

On descending any group in the periodic table, the electron affinity decreases.

Explanation.

In moving down the group from one element to the next, electrons are being added to
shells with higher energy levels i.e an extra shell is created.

Both the nuclear charge and shielding effect increase but the increase in shielding effect is
more rapid and outweighs that due to nuclear charge as such effective nuclear charge de-
creases.

Thus electron being added experiences a weaker attraction from the nucleus leading to a
decrease in 1st E.A

1st ELECTRON AFFINITY OF HALOGENS

Element 1st E.A

Fluorine -328

Chlorine -349

Bromine -325

Iodine -295

Trend

The E.A decreases numerically from Chlorine to Iodine.

As the atomic radius increases down the group, the screening effect of the inner complete
shells of electrons increases too.

As such the electron being added experiences a weaker attraction from the nucleus lead-
ing to a decrease in 1st E.A.

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 Fluorine ,however, has a low value for its electron affinity, numerically less than that for
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chlorine.

This is due to very small atomic radius of fluorine atom, the 7 electrons in the outermost
shell are much closer to each other that they repel each other strongly hence the electron
being added experiences a great repulsive force from the electrons already present.

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Electronegativity:

is the tendency of an atom in a covalent bond to attract/pull the bonding electrons more
towards itself thereby creating partial charges.

FACTORS THAT DETERMINE ELECTRONEGATIVITY VALUES

1. Nuclear charge.

2. Atomic radius.

3. Screening effect of inner electrons.

Explanation

1. Nuclear charge.

If the nuclear charge of an atom covalently bonded to another atom is high, the nuclear at-
traction for the bonding electrons will be greater leading to a high electronegativity val-
ue.
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 If the nuclear charge is low, the attraction for the bonding electrons will be weaker lead-
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ing to a low electronegativity value.

2. Atomic radius.

If the radius of an atom is small, the bonding electrons are nearer to the nucleus and as
such experience a high nuclear attraction from the electronegative atom leading to a
high electronegativity value.

If the atomic radius is large, the bonding electrons are far from the nucleus and as such
experience a weak attraction from the nucleus leading to a low electronegativity value.

3. Shielding effect of the electrons in the inner shells.

If the screening effect of the electrons in the inner shells is high, the electrons in the co-
valent bond experience a low attraction from the nucleus leading to a low value of elec-
tronegativity.

However, if the screening effect is low, the electrons in the covalent bond experience a
high attraction from the nucleus leading to a large value of electronegativity .

VARIATION IN ELECTRONEGATIVITY

Period 3:

Element Na Mg Al Si P S Cl

Electronegativity 0.9 1.2 1.5 1.8 2.1 2.5 3.0

a) Across the period, electronegativity increases from one element to the next.

Explanation:

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 As one traverses a period from one element to the next , additional electron is added to
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shells with the same energy.

As such the nuclear charge increases progressively while the screening effect of the inner
complete shells of electrons remains almost unchanged.

As a result, the effective nuclear charge increases leading to increased nuclear attraction
for the electrons in the covalent bond and hence increase in the electronegativity.

b) Down the group electronegativity generally decreases .

Group7

Element Electronegativity

F 4.0

Cl 3.0

Br 2.8

I 2.5

On descending any group in the periodic table from one element to the next, the screening
effect of the inner complete shells of electrons out-weighs the increase in the nuclear
charge due to an extra shell added.

The effective nuclear charge decreases as such the attraction for the electrons in the co-
valent bond decreases leading to a decrease in electronegativity.

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ELECTROPOSITIVITY

This is the tendency of an atom to lose one or more electron(s) from its outer most shell to
form a positively charged ion.

Electropositive elements are those which easily lose one or more electrons to become
positively charged ions. E.g Na, Mg, Ca, K, Rb, Ba etc.

FACTORS THAT AFFECT ELECTROPOSITIVITY

1. Atomic Radius

2.Nuclear Charge

3.Shielding effect of the inner complete shells.

4.Electronic configuration.

Explanation:

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 1. Atomic radius
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If the radius of an atom is small, the outer most electrons are nearer to the nucleus and
experience a high nuclear attraction. Its then not easy for an atom to lose electrons leading
to a decrease in electro positivity.

If the radius of an atom is large, the outer most electrons are far from the nucleus and
experience a weak nuclear attraction and as a result they can easily be lost leading to an
increase in electro positivity.

2. Nuclear charge

When the nuclear charge is high, the electrons in the outer shell are attracted more strong-
ly as such removing an electron is difficult leading to a decrease in electro positivity.

When the nuclear charge is low, the electrons in the outer most shell are attracted less
strongly as such removing an electron is relatively easy leading to an increase in electro
positivity.

3. Shielding effect of inner complete shells

When the shielding effect of the inner complete shells is high, the effective nuclear
charge decreases as such electrons in the outer most shell are less attracted to the nucle-
us. Removal of these electrons is easy leading to increase in electro- positivity.

When the screening effect is low, the effective nuclear charge increases as such electrons
in the outer most shell are attracted more strongly to the nucleus. Removal of these elec-
trons is difficult leading to a decrease in electro positivity.

4. Electronic configuration

If the outer most shell is fully or half filled, it is thermodynamically stable and an electron
can not easily be lost leading to a decrease in electro positivity.

However, when electron pairing begins in one of the orbitals, the paired electrons experi-
ence mutual repulsion between them thus can easily be lost leading to an increase in elec-
tro positivity.

Variation of electro positivity

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 a) Electro positivity increases in moving down the group in the periodic table.
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Explanation:

Down any group in the periodic table ,the increase in the screening effect out-weighs that
due to nuclear charge due to an extra shell of electrons added from one element to the
next.

This decreases the effective nuclear charge as a result the attraction for the outer most
electrons reduces hence they can easily be lost leading to an increase in electro positivity.

b) Electro positivity decreases in moving across the period

Explanation

Across the period, the nuclear charge progressively increases while the screening effect of
the inner complete shells remains almost unaltered from one element to the next as addi-
tional electron is added to shells with the same energy .

This increases the effective nuclear charge as such electrons in the outer most shell are at-
tracted more strongly leading to increase in electro positivity.

Melting point is the constant temperature at which the pure solid and liquid phases of a
substance co- exist in equilibrium at a given pressure.

FACTORS THAT DETERMINE MELTING POINT

a) metals

The melting points of metals depend on the following factors:

1. The number of electrons available for metallic bonding(delocalized electrons).

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 The greater the number of electrons contributed for metallic bonding the stronger the
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bond and the higher is the melting point.

2. The atomic radius.

When the radius of a metallic atom is small, the bonding electrons are attracted more
strongly by the nucleus making the inter-atomic (element-element) bond length to be
shorter and stronger thus high melting point.

When the radius of a metallic atom is large, the metallic bonding electrons are weakly at-
tracted by the nucleus as a result the element-element bond becomes longer and weaker
leading to a low melting point.

3. The crystal structure of the element.

b) Non-metals(molecular substances)

Melting points of non-metals depend on:

 Molecular mass

 Shape of molecules

 Type of intermolecular forces of attraction.

Trends in melting points/boiling points across period 2

(Li, Be, B, C, N, O, F, Ne)

Observation:

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 The Melting point of elements in period 2 increases from lithium to carbon and then de-
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creases abruptly for the non metals nitrogen to neon.

Explanation

The increase in melting point or boiling point from Li to C is attributed to:

 Increase in number of electrons available for metallic bonding.

(1 for Li, 2 for Be, 3 for B & 4 for C)

The greater the electrons available, the stronger the bond and the higher the melting
point.

 Decrease in atomic radius from Li to C.

The smaller the atomic radius, the closer are the bonding electrons to the nucleus and thus
the shorter and stronger are the metallic bonds.

Change in the crystal structure of the elements across the period.

Li has a body centred cubic (b.c.c) structure which has its atoms less efficiently packed
than Be with hexagonal closed packed (h.c.p).

Boron and carbon have giant (macro-) molecular structure composed of large number of
covalently bonded atoms with carbon atoms more strongly bonded than boron.
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 However, the non metallic elements form simple molecular structures held by weak van
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der Waals forces of attractions as such have very low melting points.

TRENDS IN MELTING POINTS ACROSS PERIOD 3

The chart shows how the melting and boiling points of the elements change as you go across
the period. The figures are plotted in Kelvin rather than °C to avoid having negative values.

The melting points increase from Na to Si and drops abruptly for the non metallic elements
phosphorus to argon.

Melting and boiling points rise across the three metals because of the increasing strength of
the metallic bonds.

The number of electrons which each atom can contribute to the metallic bonding increases.

The atoms also get smaller(atomic radius decreases) as you go from sodium through magne-
sium to aluminium.

The nuclei of the atoms are getting more positively charged and the bonding electrons are
getting progressively nearer to the nuclei and so more strongly attracted.

Silicon has the highest melting and boiling points because it has a giant covalent structure.

Here strong covalent bonds have to be broken before it melts or boils.

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Phosphorus, sulphur, chlorine and argon have simple molecular structures held by weak van
der Waals forces of attractions . Thus their melting points are much lower.

The melting and boiling points of non metals are governed entirely by the sizes of the mol-
ecules.

Phosphorus

Phosphorus contains a smaller P4 molecules. To melt phosphorus you don't have to break
any covalent bonds - just the much weaker van der Waals forces between the molecules.

Sulphur

Sulphur consists of a larger S8 rings of atoms. The molecules are bigger than phosphorus
molecules, and so the van der Waals forces of attractions will be stronger, leading to a higher
melting and boiling point.

Chlorine

Chlorine, Cl2, is a much smaller molecule with comparatively weak van der Waals forces of

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attractions, and so chlorine will have a lower melting and boiling point than sulphur or phos-
phorus.

Trend in melting points of Group 2 elements

The melting and boiling points of g it’s roup 2 metals are higher than those of correspond-
ing group 1 elements.

Graph of physical data

Explanation of this trend

Melting points generally decrease going down Group 2.

 The Group 2 elements are all metals with metallic bonding. In metallic bonding,
metal cations in a metal lattice are attracted to delocalized electron.

 Therefore going down Group 2:

 the number of delocalized electrons remains the same .

 the charge on each metal cation stays the same at +2, but..

29
  the atoms become larger so that the positive nucleus gets further away from the
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delocalized electrons...

so the force of attraction between the delocalized electrons and the metal cations decreas-
es.

Although in general the melting point decreases going down the group, the melting point
for magnesium is anomalously low.

This is because magnesium has a different metallic structure from the other elements in
the group apart from Be:

beryllium and magnesium have a hexagonal close-packed structure (h.c.p)

calcium and strontium have a face-centred cubic structure (f.c.c) and

barium has a body-centred cubic structure (b.c.c).

2.

Solubility of ionic salts in water is governed by two energy terms:

I. Lattice energy,

II. Hydration ( solvation) energy.

Lattice energy

is the amount of energy required to break 1 mole of an ionic salt into its constituent gase-
ous ions at standard conditions.

NaCl(s) → Na+(g) + Cl-(g) H = Lattice energy

Or

Lattice energy

is the amount of energy released when 1 mole of an ionic salt is formed from its constitu-
ent gaseous ions at standard conditions.

Na+(g) + Cl-(g) → NaCl(s) H = Lattice energy.

30
 Hydration energy
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is the amount of energy released when 1 mole of gaseous ions is fully dissolved in water
at a given temperature.

Na+(g) + aq → Na+(aq) H = Hydration energy.

Hydration energy has a negative sign because it involves attraction between a charge and
water molecule which releases energy.

NB:

1. Each ion has its own hydration energy.

Mg2+(g) + aq → Mg2+(aq) HθHyd(298k) = -696kj/mol.

Na+(g) + aq → Na+(aq) HθHyd(298k) = -406kj/mol.

Cl-(g) + aq → Cl-(aq) HθHyd(298k) = -377kj/mol.

Therefore the HθHyd(298k) of NaCl = (-406 + -377) = -783kj/mol and that of MgCl2 = (-
696 + 2x-377)= -1450.

The smaller the ionic radius the higher the charge density and so the greater(more nega-
tive) the hydration energy.

2. Water is a suitable solvent for dissolving ionic salts because:

 it is a polar solvent,

 has a high dielectric constant.

 has a large dipole moment, so that ion-dipole interaction is high.

If the solvation energy of a substance is greater than its lattice energy, the substance will
dissolve exothermically in the solvent.

If the solvation energy is less than the lattice energy then the substance dissolves endo-
thermically.

31
 However, if lattice energy is much larger than hydration energy then the salt does not dis-
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solve in water.

H solution is defined as the heat change that occurs when 1 mole of an ionic salt is fully
dissolved in water at a given pressure.

NaCl(s) + aq → Na+(aq) + Cl-(aq) H = Enthalpy of solution.

Na+(g) +Cl-(g)

H lattice H hydration

NaCl(s)

H solution

Na+(aq) + Cl-(aq)

Figure shows Born-Haber cycle for solubility of NaCl.

H solution = H lattice + H hydration

NB:

Whenever this formula is being applied in calculation, the value of H lattice must be
positive. This is because the formula is only valid when the salt is being decomposed as
shown in the cycle above.

Qn1.

The lattice and hydration energies of MgCl2 are -2644 kj/mole and -2653 kj/mole respec-
tively.

i) Draw an energy diagram/ Born-Haber cycle for the solubility of MgCl2 and indicate
the energy changes that occur.

32
 ii) Calculate the enthalpy of solution of the salt.
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Qn2.

i) Using potassium iodide, draw an energy diagram/ Born Haber Cycle to show the en-
ergy changes during solubility of an ionic salt in water.

ii) The enthalpy of solution and lattice energy of potassium iodide are +21kj/mol and -
642kj/mol respectively. Calculate the hydration energy for potassium iodide.

Factors that affect lattice energy

 Ionic charge ( charge on the ion e.g Na+, Mg2+, Al3+)

 Ionic radius ( distance between the ions)

 Crystal structure of a compound.

Explanation

Lattice energy is directly proportional to the ionic charge.

 If ionic charge is large, the electrostatic forces of attraction between the opposite
charges is stronger leading to a high lattice energy.

 If ionic charge is small, the electrostatic forces of attraction between the opposite
charges is weaker leading to a low lattice energy.

Lattice energy is inversely proportional to ionic radius.

 If ionic radius is large, the electrostatic forces of attraction between the opposite
charges is weaker leading to a low lattice energy.

 On the other hand if the distance between the ions is small, the electrostatic forces
of attraction between the opposite charges is greater leading to a high lattice ener-
gy.

Variation in Lattice & Hydration energies

a) Both lattice and hydration energies increase across the period.

33
 Explanation
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Across the period, the radius of ions become increasingly smaller and as such the charge
density increases.

This implies that an ion is easily hydrated and also exerts a stronger electrostatic forces of
attraction.

b) Both lattice and hydration energies decrease on descending the group.

Explanation.

Down the group, the radius of ions become increasingly larger. As such the charge densi-
ty decreases and the ion is less hydrated and also exerts a weaker electrostatic forces of
attraction.

A relationship within the periodic table by which certain elements in the second period
have a close chemical similarity to their diagonal neighbours in the next group of the third
period.

This is particularly noticeable with the following pairs.

o Lithium and Magnesium:

o Beryllium and Aluminium:

o Boron and Silicon

Causes of diagonal relationship:

I. Similar electro negativities,

II. Similar atomic & ionic radius ,

III. Similar hydration energies,

IV. Similar electrode potentials,

34
 V. Similar charge densities & similar polarizing powers,
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VI. Similar electropositivities.

Resemblance between Li & Mg

(1) Both react directly with nitrogen to form nitrides on heating.

6Li(s) + N2(g) → 2Li3N(s)

3Mg(s) + N2(g) → Mg3N2(s)

(2) Both react with oxygen gas to form normal oxides only.

4Li(s) + O2(g) → 2Li2O(s)

2Mg(s) + O2(g) → 2MgO(s)

(3) Both their nitrates decompose on heating to form normal oxide, nitrogen dioxide and
oxygen gas.

4LiNO3(g) → 2Li2O(s) + 4NO2(g) + O2(g)

2Mg(NO3)2(g) → 2MgO(s) + 4NO2(g) + O2(g)

(4) both form carbonates that decompose on heating.

Li2CO3(s) → Li2O(s) + CO2(g)

MgCO3(s) → MgO(s) + CO2(g)

(5) Both react with carbon when heated to form ionic carbide.

4Li(s) + C(s) → Li4C(s)

2Mg(s) + C → Mg2C(s)

(6) Both form chlorides and bromides that hydrolyze slowly and are soluble in ethanol;

35
 MgCl2(s) + 2H2O(l) Mg(OH)Cl(l) + H3O+(aq) + Cl-(aq)
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The oxonium ions produced makes the resultant solution acidic.

Resemblance between Beryllium and aluminium:

(1) Both elements are passive to concentrated nitric acid.

(2) Both react with conc. alkalis (to form complex )and mineral acids .(amphoteric met-
als)

Be(s) + 2OH-(aq) + 2H2O(l) → Be(OH)42-(aq) + H2(g)

2Al(s) + 2OH-(aq) + 6H2O(l) → 2 Al(OH)4-(aq) + 3H2(g)

Be(s) + 2H+(aq) → Be2+(aq) + H2(g)

2Al(s) + 6H+(aq) → 2Al3+(aq) + 3H2(g)

(3) Both elements form chlorides which are partly covalent and exist as dimmers.

Cl Cl Cl Cl

Cl Be Be Cl Al Al

Cl Cl Cl Cl

(4) Their oxides are amphoteric as are their hydroxides.

Oxides

BeO(s) + 2OH-(aq) + H2O(l) → Be(OH)42-(aq)

Al2O3(s) + 2OH-(aq) + 3H2O(l) → 2 Al(OH)4-(aq)

BeO(s) + 2H+(aq) → Be2+(aq) + H2(g)

36
 Al2O3(s) + 6H+ (aq) → 2Al3+(aq) + 3H2O(l)
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Hydroxides

Be(OH)2(s) + 2OH- (aq) → Be(OH)42-(aq)

Al(OH)3(s) + OH- (aq) → Al(OH)4-(aq)

Be(OH)2(s) + 2H+(aq) → Be2+(aq) + 2H2O(l)

Al(OH)3(s) + 3H+(aq) → Al3+(aq) + 3H2O(l)

(5) Both their carbides hydrolyze in water to form methane gas.

Be2C(s) + 4H2O(l) → 2Be(OH)2(s) + CH4(g)

Al4C3(s) + 12H2O(l) → 4Al(OH)3(s) + 3CH4(g)

Explanation as to why the two elements (Li & Mg, Be & Al, B & Si) show resem-
blance in chemical properties:

Similar electro negativities,

similar electrode potentials,

similar hydration energies,

similar ionization energies.

their ions have similar charge densities and polarizing powers

37
 The alkali metals are solids with body centred cubic (b.c.c) arrangement.
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They have one valence electron with outer most shell electronic configuration of ns1.

They have low melting and boiling point (only one electron available for bond for-
mation).

They have the largest atomic radius and lowest ionization energy in any period.

They are highly electropositive and the most reactive metals.

The alkaline earth metals are electropositive metals with 2 valence electrons (i.e. two
electrons in their outer most shell).

The general electronic configuration of their outer shell is ns2

They have a smaller atomic radii than corresponding group 1 metals.

They have higher melting and boiling points than corresponding group 1 metals.

They have a higher 1st ionization energies than corresponding elements in group 1.

They are less electropositive, less reactive and form more covalent compounds than group
1.

1. Reaction with Hydrogen.

The more electropositive metals of group 1 & 2 react with hydrogen to form ionic hydride
except Be and Mg which form covalent hydride.

2Na(s) + H2(g) → 2NaH(s)

38
 Ca(s) + H2(g) → CaH2(s)
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The ionic hydrides are hydrolyzed by water to form hydroxide and hydrogen gas.

NaH(s) + H2O(l) → NaOH(aq) + H2(g)

2. Reaction with Water.

All group 1 metals react with water more vigorously than their group II counterparts to
form corresponding hydroxide and hydrogen gas. The vigor of reaction increases down
the group.

Explanation

These metals form positive ions in the course of their reaction. Group I lose one electron
while group II lose two electrons. Therefore less energy is required to remove one elec-
tron than two from the outer most shell as such group I metals react faster with water
than corresponding metals of group II.

As the atomic radius increases down the group, ionization energy decreases thereby in-
creasing reactivity in each group. The lower the ionization energy, the lower the activa-
tion energy for reaction and thus the faster the reaction.

 2X(s) + H2O(l) → 2XOH(aq) + H2(g). X = Li, Na, K, Rb, Cs.

 Be does not react with water.

 Magnesium has a very slight reaction with cold water, but burns in steam to form
white MgO and hydrogen gas.

Mg(s) + H2O(l) → Mg(OH)2(aq) + H2(g) (with cold water)

Mg(s) + H2O(g) → MgO(s) + H2(g) . ( with steam)

 Ca, Sr, and Ba react with increasing vigor with cold water to form corresponding
hydroxide and hydrogen gas.

X(s) + 2H2O(l) → X(OH)2(aq) + H2(g)

39
 X= Ca, Sr,& Ba.
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NB

The hydroxides of Be & Mg have low solubility in water. However the solubility of hy-
droxides increase from Ca(OH)2 through Sr(OH)2 to Ba(OH)2 .

Explanation

Down the group, the radius of the cations increase while the charge on them remains the
same. This leads to a decrease in both the lattice and hydration energies.

Therefore the increase in solubility of the hydroxides down the group is attributed to the
fact that the lattice energy of the hydroxides decrease more rapidly than the hydration en-
ergy.

As such the lattice energy is easily superseded by the hydration energy thus facilitating
solubility of the hydroxides.

See table below.

Hydroxide Solubility per 100g of water at 250c

Be(OH)2 0.00

Mg(OH)2 0.01

Ca(OH)2 0.15

Sr(OH)2 0.89

Ba(OH)2 3.32

3. Reaction with Acid.

i) Dilute and concentrated hydrochloric acid

They react similarly with group 2 metals to form corresponding salt and liberating hy-
drogen gas.

M(s) + 2H+(aq) → M2+(aq) + H2(g) M= Be, Mg, Ca, Sr, Ba.

40
 ii)Dilute sulphuric acid.
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Be reacts with hot dilute sulphuric acid to form salt and hydrogen gas.

Be(s) + 2H+(aq) → Be2+(aq) + H2(g)

Mg reacts with cold dilute to form salt and hydrogen gas.

Mg(s) + 2H+(aq) → Mg2+(aq) + H2(g)

Ca, Sr & Ba react to form a sparingly soluble sulphate which renders the reaction passive.

iii) Conc. sulphuric acid

Be reacts in the same way as with dilute sulphuric acid.

However other members of the group react with conc. sulphuric acid to form salt, sulphur
dioxide and water.

M(s) + 2H2SO4(l) → MSO4(aq) + SO2(g) + 2H2O(l) M = Mg, Ca, Sr, Ba.

iv) Nitric acid.

Be does not react with nitric acid at all conditions.

Mg reacts with dilute nitric acid to form salt and hydrogen gas.

Mg(s) + 2HNO3(aq) → Mg(NO3)2(aq) + H2(g)

Mg reacts with conc. nitric acid to form salt, nitrogen dioxide and water.

Mg(s) + 4HNO3(aq) → Mg(NO3)2(aq) + 2NO2(g) + 2H2O(l)

Ca, Sr & Ba react with nitric acid to form salt, nitrogen dioxide and water.

Ba(s) + 4HNO3(aq) → Ba(NO3)2(aq) + 2NO2(g) + 2H2O(l)

4. Reaction with Oxygen.

The s-block elements react with oxygen to form 3 types of oxides namely

 Normal oxide (O2-)

41
  Peroxide (O22-)
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 Superoxide (O2-)

All group 1 metals form normal oxide with oxygen.

4X(s) + O2(g) → 2X2O(s) X= Li, Na, K, Rb, Cs.

Elements Na to Cs in addition form peroxides of the type X2O2

2X (s) + O2(g) → X2O2(s) X= Na, K, Rb, Cs.

Elements K to Cs in addition form superoxide.

X(s) + O2(g) → XO2(s) X= K, Rb ,Cs

NB:

Li can not form higher oxides due to the fact that Li+ is very small, with high charge den-
sity & high polarizing power. Thus the larger oxides can not be accommodated around it
otherwise the compound would be highly covalent & unstable.

All group 2 metals when heated form normal oxide in oxygen.

2M(s) + O2(g) → 2MO(s) M= Be, Mg, Ca, Sr, Ba

The more electropositive metals form peroxides e.g Sr & Ba.

M(s) + O2(g) → MO2(s) M = Sr, Ba

NB:

The tendency to form peroxide increases down the group. This is because the radii of the
cations increase down the group, as such their charge densities and polarizing powers de-
crease. Therefore the larger peroxide can easily be accommodated around the cation
with least polarization forming stable lattice.

Beryllium oxide is amphoteric, shows both basic and acidic properties.

42
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The other oxides are ionic and basic in nature.

(5) Reaction with halogens.

All the metals of group 1 & 2 combine directly under heat to form chlorides.

2Li(s) + Cl2(g) →2LiCl(s)

Mg(s) + Cl2(g) → MgCl2(s)

1) Compounds of group(ii) tend to be less ionic than those of group(i).

Explanation:

 The cations of group 2 have smaller ionic radius than corresponding group 1.

 Group 2 cations are doubly charged while those of group 1 are singly charged.

 Therefore cations of group 2 have higher charge density and more polarizing
power than corresponding group 1. As such compounds of group 2 are less ionic
than corresponding group1 compounds. e.g. MgCl2 and NaCl.

2) Salts of group 2 elements are less soluble in water than the corresponding group 1
salts.

Explanation

 The cations of group 2 have smaller ionic radius than corresponding group 1.

 Group 2 cations are doubly charged while those of group 1 are singly charged.

 Therefore the lattice energy of group 2 salts are much higher than those of corre-
sponding group 1 salts.

43
 The higher lattice energy of group 2 salts make them less soluble than their corresponding
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group 1 salts.

SULPHATES OF GROUP 1 & 2

Sulphates of group 1 are white solids which are stable to heat and are readily soluble in
water.

Sulphates of group 2 are white solids and sparingly soluble in water. Their solubility de-
crease down the group.

Sulphate Solubility per 100g of water at 250c

BeSO4 43

MgSO4 36

CaSO4 0.20

SrSO4 0.011

BaSO4 0.0024

Explanation.

Down the group, the radius of the cations increase while the charge on them remains the
same. This leads to a decrease in both the lattice and hydration energies.

Therefore the decrease in solubility of the sulphates down the group is attributed to the
fact that the hydration energy of the suphates decreases more rapidly than the lattice en-
ergy down the group.

NB

44
 Solubility of the nitrates , carbonates and chromates are similar to those of the sulphates.
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CARBONATES OF GROUP 1 & 2

The carbonates of group1 metals are white solids ,readily dissolve in water and are stable
to heat except lithium carbonate which decomposes on heating.

Li2CO3(s) → Li2O(s) + CO2(g)

Explanation

Li+ ion has a very small radius giving it a high charged density and a high polarizing
power. As such the smaller oxide ion (O2-) with a similar charged density approaches the
Li+ ion with least polarization thus forming a stable oxide.

However, as the group is descended the radii of the cations increase and their charged
densities decrease. Thus they can not easily be accommodated around the smaller oxide
ion due to its high polarizing effect.

Carbonates of group 2 decompose on heating to form the metal oxide and carbondioxide
gas.

XCO3(s) → XO(s) + CO2(g) X= Be, Mg, Ca, Sr, Ba.

The thermal stability of the carbonates increases as the group is descended.

Carbonate Decomposition temp. 0C

BeCO3 100

MgCO3 350

CaCO3 900

SrCO3 1290

BaCO3 1350

45
 Explanation
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On descending the group, the charged densities of the metal cations progressively de-
crease due to increase in cationic radius.

Since an oxide is smaller than a carbonate, the decomposition of metal carbonates become
less energetically favourable down the group.

NITRATES OF GROUP 1 & 2

Group 1 nitrates (except lithium nitrate) decompose to form nitrites and oxygen.

2XNO3(s) → 2XNO2(s) + O2(g) X= Na, K, Rb, Cs.

However lithium nitrate decomposes to form metal oxide, nitrogen dioxide and oxygen.

4LiNO3(s) → 2Li2O(s) + 4NO2(g) + O2(g)

Explanation

The oxide(O2-)ion is much smaller than the NO3- ion. Li+ ion has a very small radius giv-
ing it a high charge density and a high polarizing power.

As such the smaller oxide ion (O2-) with a similar charged density approaches the Li+ ion
more closely with least polarization thus forming a stable oxide.

However, as the group is descended the radii of the cations increase and their charge den-
sities decrease. Their nitrates decompose to a relatively smaller nitrites. The decrease
from nitrate to nitrite stabilizes the compound.

COMPLEX FORMATION BY GROUP 2 CATIONS

Complex ion formation is favoured by:

 Presence of empty orbitals on the cations to accommodate the lone pairs of elec-
trons donated by ligands.

 Small radius of cation.

 High charge on the cation.

46
 E.g Be(OH)4-, Be(H2O)42+
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Beryllium cation forms complex easily due to its very small ionic radius & high charge
density.

The tendency to form complex ions decreases rapidly down the group with increasing cat-
ionic radius & decrease in the charge density of cations. This is because the attraction for
the lone pairs of electrons on the ligands decrease.

Reactions in which Be resembles other group 2 elements include:

 All burn in air to form normal oxide.

 All react with chlorine gas when heated to form chloride.

 All react with dilute hydrochloric acid liberating hydrogen gas.

Reactions in which Be differs from other group 2 metals include:

 Be reacts with conc. alkalis but others don’t.

 BeO oxide is amphoteric, reacts with both acid and alkalis. Other oxides of the
group are basic in nature.

 Be carbide reacts with water to form methane. Other members of the group don’t.

 Be forms chloride which is partly covalent and exist as dimmers. Other members
form ionic chlorides.

 Be forms only one type of oxide, the monoxide . Other members form more than
one type of oxide.

Qn.

A chloride of beryllium Z, contains 11.25% beryllium and 88.75% of chlorine.

i) Calculate the empirical formula of Z.

ii) Determine the molecular formula of Z(vapor density of Z=80).

47
 iii) Write the structural formula of Z.
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Qn.

A chloride of aluminium X, contains 20% aluminium and 80% chlorine.

i) Calculate the empirical formula of X.

ii) Determine the molecular formula of X(vapor density of X= 133.5).

iii) Write the structural formula of X.

Qn.

When 0.13g of a chloride of iron was vaporized at 600k and 1 atmosphere pressure,
20cm3 of vapor was formed.

i) Calculate the relative mass of iron chloride.

ii) Determine the molecular formula of the iron chloride.

iii) Write the structural formula of the iron chloride.

Qn.

i) Compare the reaction of beryllium and barium with sulphuric acid under various condi-
tions.

ii) Explain how the solubility and basicity of the hydroxides of the elements of group 2 in
the Periodic Table vary down the group.

Qn.

Describe the reactions, if any, between each of the following elements, Be, Mg and Ca
with:

i) warm dilute sulphuric acid.

ii) warm conc. sodium hydroxide.

48
 Ore of aluminium is called Bauxite, Al2O3.xH2O
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Impurities found in the ore are:

 Silica, SiO2

 iron(iii) oxide,Fe2O3

In order to obtain pure aluminium, the ore must first be refined to eliminate the impurities
stated above.

Purification of bauxite

The ore is roasted and then crushed to powder.

Conc. sodium hydroxide is added to dissolve the amphoteric oxide, Al2O3 and the acidic
oxide SiO2

The impurity, Fe2O3 , is eliminated by filtering off.

Aluminium is then re-precipitated as Al(OH)3.xH2O by either:

i) by adding a little prepared aluminium hydroxide to the filtrate.

Al(OH)4-(aq) → Al(OH)3(s) + OH-(aq)

ii) by bubbling CO2 gas through the filtrate to remove the excess OH- ions.

2Al(OH)4-(aq) + CO2(g) → 2Al(OH)3(s) + CO32-(aq)

The hydroxide, Al(OH)3 is heated to form aluminium (III)oxide.

2Al(OH)3 → Al2O3(s) + 3H2O(g)

Extraction of Aluminium ( By electrolysis of the fused ore)

The pure oxide is 1st dissolved in molten cryolite (sodium aluminium fluoride - Na3AlF6)
to lower its melting point.

49
 The melt is then electrolyzed at a temperature between 800-900 0c at a high current den-
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sity between graphite electrodes.

Molten aluminium sinks to the bottom at the cathode where it is tapped off while oxygen
is liberated at the carbon anode.

Cathode: Al3+(l) + 3e- → Al(l)

Anode: 2O2-(l) → O2(g) + 4e-

The electrolysis cell

Reactions of aluminium

a) Reaction with water.

Aluminium reacts slowly with steam to form the oxide and hydrogen gas.

2Al(s) + 3H2O(g) → Al2O3(s) + 3H2(g)

b) Reaction with chlorine.

Aluminium when heated reacts with dry chlorine to form a chloride which sublimes. The
chloride is predominantly covalent.

50
 2Al(s) + 3Cl2(g) → 2AlCl3(s)
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Explanation

Aluminium forms a smaller cation with high charge density & high polarizing power. It
distorts the electron cloud of surrounding anions. The larger the anion, the greater the ex-
tent of polarization. Therefore the large chloride ion is polarized greatly and as such a
covalent character is induced.

The chloride forms dimer , Al2Cl6 , at high temperature with a chloride bridge structure.
Aluminium bromide & iodide have similar structures.

c) Reaction with solution of alkalis (NaOH & KOH).

Aluminium is an amphoteric metal. It reacts with concentrated alkalis to form aluminates

complex and hydrogen gas.

2Al(s) + 2OH-(aq) + 6H2O(l) → 2 Al(OH)4-(aq) + 3H2(g)

d) Reaction with acids.

With dilute mineral acids except nitric acid, aluminium forms salt and hydrogen gas.

2Al(s) + 6H+(aq) → 2Al3+(aq) + 3H2(g)

With hot conc. H2SO4, aluminium forms salt, sulphurdioxide gas and water.

2Al(s) + 6H2SO4(aq) → Al2(SO4)3(aq) + 3SO2(g) + 6H2O(l).

Aluminium does not react with dilute nitric acid . The metal is rendered passive due to the
formation of an impervious layer of oxide.

The acidity of the hexa-aqua ions

In aqueous solution, soluble salts of aluminium i.e. AlCl3, Al2(SO4)3 etc exist as
[Al(H2O)6]3+.

The resultant solution is acidic due to hydrolysis reactions:

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white ppt

The hydroxonium ions produced make the resultant solution acidic with PH less than 7
and a white solid is formed.

If sodium carbonate solution is bubbled through aqueous solution of aluminium salts,

bubbles of a colorless gas that turns lime water milky is formed.

The oxide and hydroxide of aluminium are amphoteric. They react with both conc. alkalis
and dilute acids.

Some uses of aluminium include:

Aluminium is used for: Because

1. Aircraft light, strong, resists corrosion

2. other transport such as ships' superstruc-

light, strong, resists corrosion
tures, container vehicle bodies, tube trains

52
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light, resists corrosion, good con-

3. overhead power cables .
ductor of electricity

light, resists corrosion, good ap-

4. Saucepans
pearance, good conductor of heat

(Carbon, Silicon, Germanium, Tin, and Lead)

 All group(iv) elements have four electrons in their outermost shell with a general
outer configuration of ns2np2

n=2 for C, n=3 for Si, n=4 for Ge, n=5 for Sn n=6 for Pb etc

 Metallic character increases down the group as the radius of the atoms become larger.
Carbon and Silicon are non metals , Germanium is a metalloid ie it exhibits proper-
ties characteristics of metals and non metals. While Tin & Lead are weak metals.eg
they form amphoteric oxides

 All elements show an oxidation states of +2 and +4. The +2 oxidation state arise due
to the inability of the outer most paired ‘s’ electrons to take part in bond formation.
This is called the inert pair effect.

 The stability of the +2 oxidation state increases down the group from carbon to lead.
This is due to increasing metallic character and increasing inert pair effect as the
group is descended.eg Carbon and Silicon form extremely unstable compounds in +2
oxidation state.

53
  Germanium and tin compounds in +2 oxidation state are predominantly covalent and
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are readily oxidized ie they are powerful reducing agent.

 Lead invariably forms more stable compounds in +2 oxidation state than +4 oxidation
state. Also compounds of lead in +2 oxidation state are ionic in nature. Therefore lead
(iv) compounds are unstable, and readily decompose to +2 oxidation state.eg

2 PbO2(s) → 2PbO(s) +O2(g)

PbCl4(l) → PbCl2(s) + Cl2(g)

 The stability of +4 oxidation state decreases down the group. Carbon , silicon and
germanium form more stable compounds in +4 oxidation state than in +2. This could
explain why their compounds in +2 oxidation states are good reducing agents.


Carbon is the only member of the group whose covalency is restricted to a maximum
of +4.This is due to absence of the vacant ‘d’ orbitals. Other elements have a maxi-
mum of +6 due to the availability of vacant d-orbitals which allows them to expand
their octet.

 Hoverer, all the elements exhibit a covalency of 4 but compounds of the type M4+
or M4- are rare. This is because the sum of the first four ionization energies or
first four electron affinities would be highly endothermic. An ion of the type M 4+
would be very small with high charged density as such would exert high polariz-
ing effect on the surrounding anion thus making the compound formed highly co-
valent & unstable.

NB:

Carbon, however, being the most electronegative with the smallest atomic radius
and least number of electrons is most likely to form compounds of the type M 4+ or
M4-

 Carbon exhibit a unique property of catenation. This is the ability of an element to

form covalent bonds with its own atoms so as to produce long chains and rings.

54
  Carbon therefore form limitless hydrides, alkanes, alkenes, alkynes etc due to
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catenation. This unique property of carbon is attributed to the small atomic radius
of carbon. The electrons involved in bond formation between two carbon atoms
are closer to the nuclei and are strongly held by it thus making bonds very strong
and stable. However as you descend the group, atomic radius increases. Therefore
electrons between the atoms become more distant from the nuclei making the
bond weaker and unstable.

 The melting points of group(iv) elements decrease as the group is descended. Car-
bon, however, has a much higher melting point than others. This is because carbon
has a giant molecular (Macro-molecular) structure composed of many atoms due
to its ability to catenate. It has abnormally high melting point because large num-
ber of short and strong carbon –carbon bonds have to be broken before it melts.

Melting point then decreases gradually from silicon to lead in line with increase in atomic
radius down the group. The inter-atomic bond length (element-element bonds) become
longer and weaker thus melting point decreases.

CHEMICAL PROPERTIES OF GROUP (IV) ELEMENTS.

1.Reaction with water.

Carbon reacts with steam when heated to form carbon monoxide and hydrogen gas.

C(s) + H2O(g) → CO(g) + H2(g)

Silicon reacts with steam when heated to form silicon dioxide and hydrogen gas.

Si(s) +2H2O(g) → SiO2(s) + 2H2(g)

Germanium and Tin do not react with water at any condition.

Lead reacts slowly with soft water forming lead(ii) hydroxide.

2Pb(s) + 2H2O(l) + O2(g) → 2Pb(OH)2(s)

NB

The above reaction leads to lead poisoning and explains why lead pipes are not used for
transporting water for drinking.

55
 2. Reaction with Oxygen (air).
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a) Carbon.

When carbon is heated in limited air, carbon monoxide is formed and in excess air, car-
bondioxide is formed.

2C(s) + O2(g) → 2CO(g)

C(s) + O2(g) → CO2(g)

b) When the rest of the elements are heated with oxygen , they form dioxides except lead
which forms lead(ii) oxide.

Si(s) + O2(g) → SiO2(s)

Ge(s) + O2(g) → GeO2(s)
Sn(s) + O2(g) → SnO2(s)
2Pb(s) + O2(g) → 2PbO(s)

3. Reaction with acids.

a) Carbon is attacked by all oxidizing acids eg hot conc. Sulphuric acid and hot conc. Ni-
tric acids.

C(s) + 4HNO3(aq) → CO2(g) + 4NO2(g) + 2H2O(l)

C(s) + 2H2SO4(aq) → CO2(g) + 2SO2(g) +2H2O(l)

b) Silicon is resistant to all acids except hydrofluoric acid (HF)

Si(s) + 6HF(aq) → H2SiF6(aq) + 2H2(g)

c) Germanium, Tin and Lead are oxidized by hot conc. nitric acid

3Ge(s) + 4HNO3(aq) → 3GeO2(s) + 2H2O(l) +4NO(g)

3Sn(s) + 4HNO3(aq) → 3SnO2(s) + 2H2O(l) +4NO(g)
Pb(s) +4HNO3(aq) → Pb(NO3)2(aq) + 2H2O(l) + 2NO2(g)

56
 Lead is rendered passive in both cold dilute hydrochloric and sulphuric acids due to
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formation of insoluble salt of lead(ii) chloride & lead(ii) sulphate respectively.

However, lead reacts with hot dilute hydrochloric acid to form lead(ii) chloride and hy-
drogen gas.

Pb(s) + 2HCl(aq) → PbCl2(aq) + H2(g)

Tin reacts with hot conc. Sulphuric acid to form tin(iv) sulphate.

Sn(s) + 4H2SO4(aq) → Sn(SO4)2(aq) + 2SO2(g) + 4H2O(l)

Lead reacts with hot conc. Sulphuric acid to form lead(ii) sulphate, sulphur dioxide and
water.

Pb(s) + 2H2SO4(aq) → PbSO4(s) + SO2(g) + 2H2O(l)

This reaction is similar to Al & Chromium

4. Reaction with Alkalis

Carbon is resistant to alkalis but silicon dissolves in conc. Solution to form silicate.

Si(s) + 2NaOH(aq) + H2O(l) → Na2SiO3(aq) + 2H2(g)

( 2KOH(aq))

Germanium dissolves in conc. Alkalis to form hexa-hydroxo-germanate (iv)

Ge(s) +2KOH(aq) +4H2O(l) → K2Ge(OH)6(aq) + 2H2(g)

Ionically:

Ge(s) + 2 OH-(aq) + 4H2O(l) → Ge(OH)62-(aq) + 2H2(g)

Tin and Lead dissolve slowly in hot conc. Solution of alkalis to form hexahydroxystan-
nate(ii) and plumbate(ii) respectively.

Sn(s) +4KOH(aq) +2H2O(l) → K4Sn(OH)6(aq) + H2(g)

Pb(s) +4KOH(aq) +2H2O(l) → K4Pb(OH)6(aq) + H2(g)

57
 COMPOUNDS OF GROUP(IV) ELEMENTS
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Group(iv) elements form compounds in +2 and +4 oxidation states. The +2 oxidation

state becomes more stable while the stability of +4 decreases as the group is descended.

THE OXIDES OF GROUP 4

These elements form oxides of the type XO, wherein the element shows an oxidation
state of +2 and also of the type XO2, wherein the element shows an oxidation state of +4.

The oxides of the elements at the top of Group 4 are acidic, but acidity of the oxides falls
as you go down the Group. Towards the bottom of the Group, the oxides become more
basic - although without ever losing their acidic character completely.

The trend is therefore from acidic oxides at the top of the Group towards amphoteric ones
at the bottom.

An oxide which can show both acidic and basic properties is said to be amphoteric.

MONOXIDES

The monoxide of carbon and silicon are usually treated as neutral oxides, but in fact
carbon monoxide is very, very slightly acidic. It doesn't react with water, but it will react
with hot concentrated sodium hydroxide solution to give a solution of sodium methano-
ate.

The fact that the carbon monoxide reacts with the basic hydroxide ion shows that it must
be acidic

Those of germanium, tin and lead are amphoteric. The amphoteric monoxides ( GeO,
SnO and PbO) react with acids to give corresponding salts and alkalis to give german-
ate(ii), stannate(ii) and plumbate(ii) complex ions.

SnO(s) + 2H+(aq) →Sn2+(aq) + H2O(l)

58
 SnO(s) + 2OH-(aq) + H2O(l) →Sn(OH)42-(aq)
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Similar reactions are undergone by GeO & PbO

Alternatively:

XO(s) + 2OH-(aq) → XO22-(aq) + H2O(l)

GeO(s) + 2OH-(aq) → GeO22-(aq) + H2O(l)

SnO(s) + 2OH-(aq) →SnO22-(aq) + H2O(l)

PbO(s) + 2OH-(aq) → PbO22-(aq) + H2O(l)

They all react with concentrated hydrochloric acid.

. . . where X can be Ge and Sn, but unfortunately needs modifying a bit for lead.

Lead(II) chloride is fairly insoluble salt in water and, , it would form an insoluble layer
over the lead(II) oxide if dilute hydrochloric acid is used - stopping the reaction from go-
ing on.

However, using concentrated hydrochloric acid the large excess

of chloride ions in the concentrated acid react with the lead(II) chloride to produce a yel-
low soluble complex PbCl42-.

DIOXIDES

The first four dioxide are prepared by heating the elements in oxygen but a similar pro-
cess with lead gives lead(ii) oxide.

C(s) + O2(g) → CO2(g)

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 Si(s) + O2(g) → SiO2(s)
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Ge(s) + O2(g) → GeO2(s)

Sn(s) + O2(g) → SnO2(s)
2 Pb(s) + O2(g) → 2PbO(s)
NB

Lead(iv) oxide is made by action of hot dilute nitric acid on red lead, Pb3O4.

Pb3O4(s) + 4HNO3(aq) → PbO2(s) + 2Pb(NO3)2(aq) + 2H2O(l)

Brown solid

With warm conc. HCl, red lead reacts according to the equation:

Pb3O4(s) + 14HCl(aq) → 3H2PbCl4(aq) + Cl2(g) + 4H2O(l)

Yellow solution

Red lead is used in paints to prevent the corrosion of iron

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In the case of lead(IV) oxide, the reaction has to be done with ice-cold hy-
drochloric acid. If the reaction is done any warmer, the lead(IV) chloride
decomposes to give lead(II) chloride and chlorine gas. This is an effect of
the preferred oxidation state of lead being +2 rather than +4.

Here the acid should be cold and conc.

PbO2(s) + 4HCl(aq) → PbCl4(l) + 2 H2O(l)

If the reaction is carried out at elevated temperature, lead(iv) oxide oxidizes

chloric acid to chlorine gas.

PbO2(s) + 4HCl(aq) → PbCl2(aq) + 2 H2O(l) + Cl2(g

The dioxides will react with hot concentrated sodium hydroxide solution to
plexes of the form [X(OH)6]2-.

+2 halides

Carbon and Silicon do not form +2 halides. Those of Ge, Sn and Pb can be p
the tetra-chlorides with the free metal.

GeCl4(l) + Ge(s) → 2GeCl2(s)

SnCl4(l) + Sn(s) → 2SnCl2(s)

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PbCl4(l) + Pb(s) → 2PbCl2(s)

Tin(ii) chloride may be prepared in anhydrous form by passing dry HCl gas ov

Sn(s) + 2HCl(g) → SnCl2(s) + H2(g)

Lead(ii) chloride can also be prepared either by action of hot conc. HCl over l
passing dry hydrogen chloride gas or chlorine over heated metal.

PbO2(s) + 4HCl(aq) → PbCl2(s) + 2H2O(l) + Cl2(g)

Conditions: hot/ conc. acid,

NB: Lead(ii) chloride is more soluble in concentrated hydrochloric acid than

this observation.

Lead(ii) chloride has a high lattice energy which is not over-come on addi
However on heating, the high lattice energy is overcome and therefore lead(ii
in hot water.

Lead(ii) chloride dissolves in conc. Hydrochloric acid due to formation of a s

ra- chloroplumbate(ii) ions.

PbCl2(s) + 2Cl-(aq) → PbCl42-(aq)

Yellow solution.

+4 halides

All the elements form tetra chlorides of the type XCl4, which are covalently bo
tile liquids.

All the tetra chlorides have a tetrahedral shape in which the element is surrou
atoms.

Preparation of the tetra chlorides

CCl4

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By reacting chlorine with carbon disulphide .

CS2(l) + 3Cl2(g) AlCl3/heat CCl4(l) + S2Cl2(l)

The two liquids are separated by fractional distillation.

SiCl4 , GeCl4 & SnCl4

Are prepared by passing a stream of dry chlorine over the heated metal.

Si(s) + 2Cl2(g) → SiCl4(l)

Ge(s) + 2Cl2(g) → GeCl4(l)

Sn(s) + 2Cl2(g) → SnCl4(l)

If a stream of chlorine is passed over heated lead, only lead(ii) chloride is form

Pb(s) + Cl2(g) → PbCl2(s)

To prepare lead(iv) chloride, use ice cold conc. HCl on lead(iv) oxide.

PbO2(s) + 4HCl(aq) → PbCl4(l) + 2 H2O(l)

CCl4 does not under go hydrolysis in water. This is attributed to absence of th

orbitals.

However, other tetrachlorides under go hydrolysis in water. This is attribute

the empty d-orbitals thereby allowing the elements to expand their octet and
of more than +4. This empty d-orbitals accept lone pairs of electrons from t
water molecule thus facilitating the hydrolysis of the tetra chlorides.

SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g)

SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g)

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White solid.

GeCl4(l) + 2H2O(l) → GeO2(s) + 4HCl(g)

SnCl4(l) + 2H2O(l) → SnO2(s) + 4HCl(g)

PbCl4(l) + 2H2O(l) → PbO2(s) + 4HCl(g)

Brown solid

NB: In each case white fumes of hydrogen chloride gas is formed.

Stability of the tetrachloride

The tetrachlorides of carbon, silicon, and germanium are stable to heat, but th
decompose on heating to form di-chlorides.

SnCl4(l) → SnCl2(s) + Cl2(g)

PbCl4(l) → PbCl2(s) + Cl2(g)

HYDRIDES OF GROUP 4

CH4 Methane

SiH4 Silane

GeH4 Germane

SnH4 Stannane

PbH4 Plumbane

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The boiling points of the hydrides increase from methane down to stannane
crease in relative molecular mass. Thus the Van der Waals forces of attract
molecules together become progressively stronger as the relative molecular ma

Methane, germane and stannane do not react with sodium hydroxide, but silan
sodium hydroxide to form sodium silicate and hydrogen gas.

SiH4(l) + 2NaOH(aq) + H2O(l) → Na2SiO3(aq) + 4H2(g)

Ionically:SiH4(l) + 2OH- (aq) + H2O(l) → SiO32- (aq) + 4H2(g)

Hydrolytic behavior of hydrides of group 4

Methane does not under go hydrolysis due to absence of vacant d-orbitals.

Other hydrides are able to hydrolyse in water due to the availability of vaca
can accept electrons from the water molecules.

SiH4(l) + 4 H2O(l) → Si(OH)4(s) + 4H2(g)

GeH4(l) + 4 H2O(l) → Ge(OH)4(s) + 4H2(g)

SnH4(l) + 4 H2O(l) → Sn(OH)4(s) + 4H2(g)

 Its covalency is limited to 4 but others can have a maximum of 6. Due

cant d-orbitals in carbon but others have.

 Its unique ability to catenate. Due to its small atomic radius, the bon
tween two carbon atoms are closer to the nuclei and are attracted more

 Its unique ability to form multiple bonds such as: -C=C-, -C=C-, -C=N

 Its tetrachloride does not hydrolyze in water but tetra chlorides of oth
lyze. Due to absence of vacant d-orbitals.

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 Carbon is the only element in group 4 which forms only gaseous oxide

 Very small atomic radius of carbon atom.

 High electro- negativity of carbon atom.

 Absence of vacant d-orbitals.

 Unable to show the inert pair effect

Qn.

When dilute hydrochloric acid is added to a solution of lead(ii) nitrate, a

formed ,but if the concentrated acid is used, a much less precipitate is forme
havior and write ionic equation for the reaction.

The Hydrides of period 3

Hydride Formula

Sodium hydride NaH

Magnesium hydride MgH2

Aluminium hydride AlH3

Silane SiH4

Phosphine PH3

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Hydrogen sulphide H2S

Hydrogen chloride HCl

NaH(s) + H2O(l) → NaOH(aq) + H2(g)

SiH4(g) + 2H2O(l) → SiO2(g) + 4H2(g)

H2S(g) + 2H2O(l) → S2-(aq) + 2 H3O+(aq)

HCl(g) + H2O(l) → Cl-(aq) + H3O+(aq)

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States at room temperature:

 Fluorine, F2- yellow gas

 Chlorine Cl2 - yellow-green gas

 Bromine Br2 - red-brown liquid

 Iodine I2 - black (dark purple) solid

- sublimes to a purple vapour.

 Halogens are highly reactive non-

metals. They exist as diatomic
molecules X2 containing a covalent
bond. Due to their reactivity the el-
ements do not occur in the free
state but are always combined with
other elements.

 All the elements have 7 electrons in

their outer most shells with general
outer most electronic configuration
of ns2np5 n= 2,3,4&5

 They can complete their octet by

either gaining an electron to form
an ionic bond or sharing electrons
with other elements or themselves

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in a covalent bond.

 The melting and boiling points of

the halogens are low but increase
down the group.

Explanation

The diatomic molecules of halo-

gens are held by weak van der
Waals forces of attraction. These
forces become stronger with in-
creasing molecular weight/ masses
down the group.

In bromine and iodine, the forces

are strong enough to bind the halo-
gens to exist as liquid and solid re-
spectively. However, in fluorine
and chlorine, the forces are not
strong enough and as a result they
exist as gases.

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Bond energy is the energy required

to break a bond between two at-
oms.

Or its the energy released when a

bond is formed between two atoms.

Bond dissociation energy of the di-

atomic molecules decreases down
the group from chlorine to iodine.
However ,F2 has abnormally low
bond dissociation energy.

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This is due to small atomic radius

of fluorine atom, the non bonding
p- electrons present in F2 molecule
are closer to one another as such
repel @ other strongly thus weak-
ening the F-F bond.

The decrease in B.D.E from Cl2 to

I2 is attributed to increase in atomic
radius as the group is descended,
the bonding electrons in the halo-
gen-halogen bond are far from the
nuclei of the halogens & are at-
tracted less strongly due to the
screening effect of the inner com-
plete shells of electrons thus weak-
ening the bond progressively.

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NB: The high reactivity of fluorine may be attributed to its

low B.D.E.

E.A is the energy change when an

extra electron is added to a neutral
gaseous atom to form a negatively
charged gaseous ion.

X (g) + e- → X(g)-

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The E.A is a more useful concept

for the halogens than first ionisa-
tion energy because the halogens
need only one electron to complete
their octet and there by attain a no-
ble gas like structure.

The E.A decreases numerically

from Chlorine to Iodine. As the
atomic radius increases down the
group, the electron being added
experiences a greater repulsion
from the electrons that are already
present than the attraction experi-
enced from the nucleus due to the
screening effect of the inner com-
plete shells of electrons.

Fluorine ,however, has a low value

for its electron affinity, numerically
less than that for chlorine.

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Explanation

This is due to small atomic radius

of fluorine atom, the 7 electrons in
the outer most shell are too close to
one another therefore the electron
being added experiences a greater
repulsive force from the electrons
already present than the attraction
from the nucleus.

The electron affinity is a measure

of the attraction between the in-
coming electron and the nucleus.
The higher the attraction, the high-
er the electron affinity.

 Halogens are very good oxidizing

agents with fluorine being the
most oxidizing.

 This is because fluorine is the most

electronegative and has the highest
positive value for its standard elec-
trode potential. It oxidises water to

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oxygen.

2F2(g) + 2H2O(l) → O2(g) + 4HF(aq)

 The standard electrode poten-

tial(Eθ) becomes less positive as the
group is descended and so oxidis-
ing power decreases down the
group.

F2 > Cl2 > Br2 > I2

They all exhibit oxidation state of -

1by gaining an extra electron to
complete their octet.

Fluorine is always univalent due to

absence of vacant 'd'-orbitals.

Other elements can show higher

oxidation states due to availability
of vacant 'd'-orbitals which allows
them to expand their octet.

Reactions of halogens

In all their reactions the halogens

act as oxidising agents. Hence,
their reactivity decreases down the
group.

1.Reaction with water

a) F2 oxidises H2O to O2 gas in a

very exothermic reaction.

2F2(g) + 2H2O(l) → O2(g) + 4HF(aq)

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b) Cl2 dissolves in H2O to form

'chlorine water' which is a mixture
of two acids. No O2 is evolved.

Cl2(g) + H2O(l) → HCl(aq) + HOCl(aq)

c) Br is only slightly soluble in

H2O .

Br2(l) + H2O(l) → HBr(aq) + HOBr(aq)

d) I2 is virtually insoluble in H2O.

It is however soluble in KI solution
due to the formation of a soluble
complex the tri-iodide anion.

I2(s) + I-(aq) → I3-(aq)

I2 is sparingly soluble in water be-

cause the energy involved in dis-
rupting the weak van der Walls
forces in molecular iodine crystal
lattice and the hydrogen bonds in
water exceeds the energy changes
involving the weak attraction be-
tween iodine and water molecules.

Note:

All halogens are more soluble in

non-polar solvents such as CCl4.
Cl2 gives a colourless solution. Br2
a red solution and I2 a violet one.

2.1

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b)The acidity of the hydrides is in

the order H-F <H-Cl< H-Br< H-I.

 H-F is the weakest acid because

the H-F bond is very strong as a
result of small atomic radius and
high electronegativity of Fluorine
atom. It is weakly dissociated in
solution releasing fewer H+ ions.

 In addition, the presence of hydro-

gen bonding between HF mole-
cules and water molecules inhibits
the ionization of HF in aqueous so-
lution.

 However, as the group is descend-

ed, electronegativity decreases
whereas atomic radius increases.
As such the H- halide bonds be-
come progressively longer and
weaker. They dissociate in solu-
tion releasing more hydrogen ions.

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c) Bond energy/ enthalpy of the

hydrides generally decreases in
moving from HF to HI ie

H-F > H-Cl > H-Br > H-I.

As the halogen atom gets bigger,

the bonding pair gets more and
more distant from the nucleus. The
attraction is less, and the bond gets
weaker.

Fluorine is the most electronega-

tive atom with the smallest atomic
radius thus the H-F bond is the
most polar. Iodine is the least elec-
tronegative with the largest atomic
radius as a result the H-I bond is
the least polar. The greater the ex-

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tent of polarity, the greater the ion-

ic character in the bond and there-
fore the stronger the bond.

Differences in the chemistry

of Fluorine from other members of
its group are:

 Fluorine is always monovalent,

others show higher oxidation state.
This because fluorine lacks empty
d-orbitals but others have.

 H-F is a liquid while other hydro-

gen halides are gases at room tem-
perature. This is due to the strong
hydrogen bonds between H-F mol-
ecules as a result of high electro-
negativity of fluorine atom.

 Fluorine forms the least acidic hy-

dride whereas the hydrides of other
members are fairly more acidic in
aqueous solution. This is due to the
high strength of the H-F bond.

 Fluorine is the most reactive halo-

gen, due to its low bond dissocia-
tion energy and high electronega-
tivity.

 Fluorine forms compounds with

more ionic character due to its high
electronegativity and charge densi-
ty of the small F- ion.

79
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 Fluorine forms hydride with the

highest boiling point in aqueous so-
lution due to extensive hydrogen
bonds .

Why does Fluorine show a

difference?

o Most electronegative in the group.

o Low bond dissociation energy.

o High positive value of standard

electrode potential.

o Smallest atomic radius, F- ion has

very high charge density, high po-
larising power, high enthalpy of
hydration.

o Absence of a vacant d-orbitals.

Oxy-acids & Oxy-ions

1.Chlorate(i) acid HClO

(Chloric(i) acid)

2.Chlorate(iii) acid HClO2

(Chloric(iii) acid)

3. Chlorate(v) acid HClO3

(Chloric(v) acid)

4. Chlorate(Vii) acid HClO4

(Chloric(vii) acid)

The acidity of the oxy-anions of

80
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chlorine increases with increase in

the number of oxygen atoms at-
tached to chlorine atom. Oxygen
being more electronegative than
chlorine, withdraws electrons from
the O-Cl bond more towards itself.

This weakens the O-H bond in the

oxy-acid. The greater the number
of oxygen atoms attached the
stronger the effect and the stronger
the acid.

NB

1. Work out the oxidation state of

chlorine in each of oxyacids above
.

2. Draw the molecular structure of

each oxyacid .

Qn. Compare the reactivity of Flu-

orine and Chlorine with the follow-
ing substances( in each case illus-
trate your answer with equation)

i) Water

81
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.

GENERAL CHARACTERISTICS OF TRANSITION

ELEMENTS

137
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1. High melting and boiling points.

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Downloaded from www.mutoonline.com, More PASTPAPERS are available

ALUMS

Alums are double sulphate salts with general formula M2SO4.M2(SO4)3.24H2O

The 1st M is a group (I) metal e.g Li+, Na+, K+, NH4+, Rb+ , Cs+ etc

The 2nd M is a group (III) metal or a metal bearing a +3 charge e.g Al3+ , Cr3+, Fe3+,
Mn3+,Co3+ etc

Examples of common alums are:

Chrome alum K2SO4.Cr2(SO4)3.24H2O

Its solution in water is acidic because the chromium (iii) ions undergo hydrolysis leav-
ing the solution acidic.

The complex ion is acting as an acid by donating a hydrogen ion to water molecules in
the solution.

The water is, of course, acting as a base by accepting the hydrogen ion.

[Cr(H2O)6]3+(aq)+H2O(l) → [Cr(H2O)5OH]2+(aq) + H3O+(aq)

[Cr(H2O)5OH]2+(aq)+H2O(l) → [Cr(H2O)4 2OH]+(aq) + H3O+(aq)

[Cr(H2O)4 2OH]+(aq)+ H2O(l) → [Cr(H2O)3 3OH](s) + H3O+(aq)

Over all equation:

The accumulation of hydroxonium ions renders the resultant solution acidic.

If aqueous sodium carbonate is added, an efferverscence of a colorless gas which turns

lime water milky is formed and a greeen solid.

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2) Potash alum K2SO4.Al2(SO4)3.24H2O

3) Ammonium alum (NH4)2SO4.Al2(SO4)3.24H2O

Preparation of Chrome Alum

By bubbling sulphurdioxide gas into a solution of acidified potassium dichromate,

chrome alum is formed.

SO2 (g) + H2O(l) → H2SO3(aq)

H2SO3(aq) ↔ 2H+(aq) + SO32-(aq)

SO32-(aq) + H2O(l) → SO42-(aq) + 2H+(aq) + 2e

Cr2O72- (aq) + 14H+(aq) + 6e → 2Cr3+(aq) + 7H2O(l)

The ions present after the above reactions are in the correct proportion for the for-
mation of chrome alum on crystallizing.

Test for Cr3+ ions in solution

Use of sodium hydroxide solution:

Observation

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Dark green precipitate, soluble in excess to form deep green solution.

Equations

Use of aqueous ammonia solution:

Observation

Green precipitate slowly dissolves in excess concentrated ammonia solution to

form a purple solution.

Equations

Cr3+(aq) + 3 OH-(aq) → Cr(OH)3(s)

Cr(OH)3 (s) + 6NH3(aq) → [Cr(NH3)6]3+(aq) + 3 OH-(aq)

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Suggest similarities in the chemistry of Chromium & Lead.


Cr3+and Pb2+ form complex with sodium hydroxide solution.

Cr3+ (aq) + 3 OH- (aq) → Cr(OH)3 (s)

Cr(OH)3 (s) + 3 OH-(aq) → [Cr(OH)6] 3-(aq)

Pb2+ (aq) + 2 OH- (aq) → Pb(OH)2 (s)

Pb(OH)2 (s) + 2 OH-(aq) → [ Pb(OH)4]2-(aq)

 Both their oxides in higher oxidation states are acidic.

CrO3(s) + 2NaOH(aq)→ Na2CrO4(aq) + H2O(l)

PbO2(s) + 2NaOH(aq) → Na2PbO3(aq) + H2O(l)

 Their oxides in higher oxidation states are strong oxidizing agents.

CrO3(s) + Al(s) → Cr(s ) + Al2O3(s)

PbO2(s) + 4HCl(aq) → PbCl2(s) + 2H2O(l) + Cl2(g)

 They both form compounds with variable oxidation states ie

 Lead :+2 & +4 and Chromium: +2, +3 & +6

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 Chromium and Lead in higher oxidation states Cr6+ and Pb4+ form covalent
compounds e.g PbCl4 and CrCl6

Similarities 1.1 the chemistry of Chromium & Aluminium

1. Cr3+ and Al3+ form complex with sodium hydroxide solution.

Cr3+ (aq) + 3 OH- (aq) → Cr(OH)3 (s)

Cr(OH)3 (s) + 3 OH-(aq) → [Cr(OH)6] 3-(aq)

Al3+ (aq) + 3 OH- (aq) → Al(OH)3 (s)

Al(OH)3 (s) + OH-(aq) → [ Al(OH)4]-(aq)

2.

Atomic number is 3o.

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Its electronic configuration is :1S22S22P63S23P63d104S2

Ores of Zinc

 Zinc blende :ZnS

 Zinc calamine:ZnCO3

Extraction process from sulphide ore

The ore contains traces of lead sulphide and silica as impurities.

 Concentration

The ore is first crushed and mixed with water and oil (a frothing agent) so as to re-
move the unwanted earthly materials. The oil wets the sulphide particles and the water
wets the impurities.

Air is then blown through the mixture producing a froth. The oiled sulphide particles
float on the surface while the impurities sink to the bottom.

The ore is collected, washed and dried.

 Roasting

The concentrated ore is then heated strongly in air to form zinc oxide.

2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g)

 Reduction

Zinc oxide, limestone ( CaCO3) and excess coke are then heated in a blast furnace.

Limestone decomposes into calcium oxide and carbondioxide.

CaCO3(s) → CaO(s) + CO2(g)

The calcium oxide reacts with silica, one of the impurities to form calcium silicate
(slag).

CaO(s) + SiO2(s) → CaSiO3(l)

Coke burns to carbon dioxide, which is reduced by unburnt coke to carbon monoxide.

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The carbonmonoxide reduces zinc oxide to zinc.

C(s) + O2(g) → CO2(g)

CO2(g) + C(s) → 2CO(g)

ZnO(s) +CO(g) → Zn(l) + CO2 (g)

The slag sinks to the bottom and can be removed where as the zinc produced leaves as
vapor at the top of the blast furnace where its cooled and allowed to solidify.

REACTIONS OF ZINC

a) With air

On exposure to air, zinc develops a thin layer of zinc oxide. This layer prevents further
reaction with the oxygen present in air.

Zinc burns in air (oxygen) to form zinc oxide.

2Zn(s) + O2(g) → 2ZnO(s)

( yellow when hot and white on cooling.)

b) With water

Zinc(red hot) reacts with steam to form zinc oxide and hydrogen gas.

Zn(s) + H2O(g) →ZnO(s) + H2(g)

c) With acid

Zinc reacts with both dilute and conc. hydrochloric acid forming salt and hydrogen gas.

Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)

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Zinc reacts with dilute sulphuric acid to form salt and hydrogen gas.

Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(g)

Reaction of zinc with conc. H2SO4

produces Zinc sulphate, sulphurdioxide and water as the products.

Zn(s) + 2H2SO4(aq) → ZnSO4(aq) +2 H2O(aq) + SO2(g)

NB:

The products for the rxn with nitric acid(both dilute and conc.) are not easily defined.

d) With alkalis

Zinc react with aqueous alkalis to form zincates’ complex and hydrogen gas.

Zn(s) + 2OH-(aq) + 2H2O(l) → Zn(OH)42-(aq) + H2(g)

COMPOUNDS OF ZINC

ZINC HYDROXIDE

It is prepared as a white precipitate on addition of a little sodium hydroxide or aqueous

ammonia to a solution containing zinc ions.

Zn2+(aq) + 2OH-(aq) → Zn(OH)2(s)

White ppt

The hydroxide is amphoteric. It dissolves in excess sodium hydroxide to form sodium

zincates’ complex.

Zn(OH)2(s) + 2OH-(aq) →Zn(OH)42-(aq)

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In aqueous ammonia, zinc hydroxide dissolves forming a colorless solution of tetra

amine zinc ion.

Zn(OH)2(s) + 4NH3(aq) → Zn(NH3)42+(aq) + 2OH-(aq)

ZINC SULPHIDE

This is prepared as a white ppt on passing hydrogen sulphide through a solution of

zinc ions.

When H2S gas is passed through a solution of a metallic salt, a metallic sulphide is
formed but if the H2S is passed through an acidic solution of a metallic salt, the sul-
phide may not be formed.

Explanation:

H2S(g) + aq ↔ 2H+(aq) + S2-(aq)

Zn2+(aq) + S2-(aq) → ZnS(s)

If before bubbling hydrogen sulphide the solution is acidified, the excess H+ ions pre-
sent suppresses the formation of sulphide ions in 1st equation above and therefore the
concentration of sulphide ions will be too low to precipitate zinc sulphide.

Aqueous solution of zinc chloride is acidic due to hydrolysis of [Zn(H2O)6]2+

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ZnCl2(s) + 6H2O(l) → [Zn(H2O)6]2+ + 2Cl-(aq)

[Zn(H2O)6]2+(aq) + H2O(l) ↔ [Zn(H2O)5OH]+ (aq) + H3O+(aq),

TEST FOR ZINC IONS

1) Addition of aqueous sodium hydroxide drop wise to a solution of Zn2+ ions produces
a white ppt which dissolves in excess to form a colorless solution.

Zn2+(aq) + 2OH-(aq) → Zn(OH)2(s)

White ppt

Zn(OH)2(s) + 2OH-(aq) →Zn(OH)42-(aq) colorless solution

2) Addition of ammonia solution drop wise to a solution of zinc ions, produces a white
ppt soluble in excess to form a colorless solution.

Zn2+(aq) + 2OH-(aq) → Zn(OH)2(s)

Zn(OH)2(s) + 4NH3(aq) → Zn(NH3)42+(aq) + 2OH-(aq)

3)Addition of potassium ferrocyanide solution to a solution of Zn2+ ions produces a

white ppt. soluble in sodium hydroxide.7

4) Addition of ammonium sulphide solution produces a white ppt soluble in dilute HCl
acid.

5) Using disodium hydrogen phosphate, white ppt is formed with zinc ions.

USES OF ZINC

 Making alloys e.g. Brass is alloy of zinc and copper.

 Galvanizing iron.

Zinc is higher than iron in electrochemical(reactivity) series .

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If a galvanized piece of iron developed a small scratch and the iron is exposed, iron
does not rust.

This is because the zinc in the neighborhood of the exposed iron undergoes oxidation
in preference to iron forming a thin layer of ZnO which prevents further attack.

Ores of iron:

 Haematite , Fe2O3

 Magnetite , Fe3O4

 Iron Pyrite , FeS2

 Siderite , FeCO3

The 1st two ores are used directly but the last two must be 1s t roasted in air to convert
them to stable iron(iii) oxide. e.g

4FeS2(s) + 11 O2(g) → 2Fe2O3(s) + 8SO2(g)

4FeCO3(s) + O2(g) → 2Fe2O3 + 4CO2(g)

EXTRACTION OF IRON

Iron is extracted from its ore called haematite (Fe2O3)in a blast furnace

The raw materials used in the extraction are:

 The ore, Haematite

 Coke

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 Limestone( calcium carbonate)

 Hot air

The hot blast of air enters the blast furnace through narrow pipes called Tuyeres locat-
ed at the lower part of the furnace. The other materials are fed into the furnace from the
top.

REACTIONS TAKING PLACE IN THE BLAST FURNACE

In the presence of hot air coke burns to produce carbondioxide gas

C(s) + O2(g) →CO2(g)

As the carbondioxide ascends, it reacts with unburnt coke to form carbonmonoxide

CO2(g) + C(s) →2CO(g)

The carbonmonoxide produced reduces the ore to iron.

Fe2O3(s) + 3CO(g) ↔ 2Fe(l) + 3CO2(g)

The role of the limestone is to remove impurities like silica( SiO2)

CaCO3(s) → CaO(s) + CO2(g)

The quick lime then combines with silica and alumina present as impurities to form
slag.

CaO(s) + SiO2(s) → CaSiO3(l)

CaO(s) + Al2O3(s)→ CaAl2O4(l)

Molten iron and slag both sink to the bottom of the furnace and they can be tapped off
separately. The molten iron is at the bottom covered by slag to prevent further re-
oxidation.

The molten iron solidifies on cooling to form PIG iron.

Properties of pig iron:

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 Low melting point.

 Impure e.g. carbon, silicon, sulphur, etc.

Pig iron can be used in making gas stove, drainage pipes, Bunsen burner bases, boiler
plates etc

Purification of pig iron.

The Bessemer process:

This involves pouring the molten iron into a large tab called the converter and air is
blown into it to oxidize the impurities such as carbon, sulphur and phosphorus to their
gaseous oxides.

REACTIONS OF IRON

a) With air

Iron combines with oxygen when heated to form black solid of tri-iron tetra oxide.

3Fe(s) + 2 O2(g) → Fe3O4(s)

Iron reacts with moist cold air to form brown hydrated iron(iii) oxide or rust.

2Fe(s)+ 6H2O(l) + 3 O2(g)→ 2Fe2O3.3H2O(s)

How rusting occurs:

Rusting is an electrochemical process which takes place when different parts of iron act
as anode and cathode.

At the cathodic region:

Fe(s) → Fe2+(aq) + 2e

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At the anodic region:

2 H2O(l) + O2(g) + 4e ↔ 4OH-(aq)

If the cathodic and anodic areas are close enough, iron(ii) hydroxide is formed.

Fe2+(aq) + 2OH-(aq) → Fe(OH)2(s)

Moist air then oxidizes the iron(ii) hydroxide to rust.

2Fe(OH)2(s) + H2O(l) + 1/2 O2(g) → Fe2O3.3H2O(s)

Prevention of rusting

 Painting

 Greasing

 Galvanizing (coating with zinc)

b) With water

Heated iron reacts with steam to form black tri-iron tetra oxide.

3Fe(s) + 4H2O(g) ↔ Fe3O4(s) + 4H2(g)

c) With acid.

Iron reacts with dilute acids(HCl & H2SO4) to form hydrogen gas and iron(ii) salts.

Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g)

Fe(s) + H2SO4(aq) → FeSO4(aq) + H2(g)

Hot conc. sulphuric acid oxidizes iron to iron(iii) sulphate, sulphur dioxide and water.

2Fe(s) + 6H2SO4(aq) → Fe2(SO4)3(aq) + 3SO2(g) + 6 H2O(aq)

d) With halogens.

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Heated iron reacts with dry chlorine gas to form iron(iii) chloride.

2Fe(s) + 3Cl2(g) → FeCl3(s)

Compounds of iron

+2 oxidation state

In aqueous solution exists as [Fe(H2O)6]2+ which is a green solution. It undergoes hy-

drolysis making the resultant solution acidic.

a) Iron(ii) hydroxide

It’s a green ppt formed when sodium hydroxide solution is added drop wise to a
solution of Fe2+ solution. The ppt is insoluble in excess and turns brown due to
aerial oxidation on exposure to air .

Fe2+(aq) + 2OH-(aq) → Fe(OH)2(s)

2Fe(OH)2(s) + H2O(l) + 1/2 O2(g) → Fe2O3.3H2O(s)

NB:

Similar reaction occurs on addition of ammonia solution to aqueous Fe2+ solution

b) Hydrated iron(ii) sulphate. FeSO4.7H2O.

Its prepared by heating iron fillings with dilute sulphuric acid and crystallizing the salt

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from solution.

During the crystallization process, hydrated iron(ii) sulphate forms as green crystals.

Fe(s) + H2SO4(aq) → FeSO4(aq) + H2(g)

Action of heat on hydrated iron(ii) sulphate

On gentle heating

FeSO4.7H2O (s) → FeSO4(s) + 7H2O(g)

On further heating.

2FeSO4(s) → Fe2O3(s) + SO3(g) + SO2(g)

White fumes acidic fumes

If conc. nitric acid is added to iron(ii) sulphate, the green solution turns to yellow/
brown due to formation of iron(iii) ions.

+3 oxidation state

This is the most stable oxidation state of iron.

The soluble salts in this oxidation state exist as [Fe(H2O)6]3+ and undergo hydrolysis
in water making resultant solution acidic.

e.g. a solution of iron (iii) chloride turns blue litmus red.

The Fe3+ ion is small and highly charged. It undergoes hydrolysis in aqueous solution
to release hydrogen ions or hydroxonium ions that make the resultant solution acidic.

FeCl3(aq) → Fe3+ (aq) + 3Cl-(aq)

Fe3+(aq) + 6H2O(l) →[Fe(H2O)6]3+(aq)

[Fe(H2O)6]3+(aq) + 3H2O(l) ↔ [Fe(H2O)33OH](s) + 3H3O+(aq)

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Brown ppt

or

[Fe(H2O)6]3+(aq) ↔ [Fe(H2O)33OH](s) + 3H+(aq)

On addition of zinc powder to a brown/ yellow solution of iron(iii), the color of the so-
lution changes to green.

2Fe3+(aq) + Zn(s) → 2Fe2+(aq) + Zn2+(aq)

The resultant solution can now be titrated with acidified solution of standard potassium
permanganate.

MnO-4 (aq) + 8H+ (aq) + 5Fe2+ (aq) → Mn2+(aq)+4H2O(l) +5Fe3+ (aq)

On bubbling hydrogen sulphide gas to a solution containing Fe3+ ion, the color of the
solution changes from yellow to green with formation of a yellow solid.

H2S(g) + 2Fe3+(aq) → 2H+(aq) + 2Fe2+(aq) + S(s)

Similarities in the chemistry of Zn and Fe

1).Both metals when heated ( red hot) react with steam to form oxide and hydrogen
gas.

3Fe(s) + 4H2O(g) ↔ Fe3O4(s) + 4H2(g)

Zn(s) + H2O(g) → ZnO(s) + H2(g)

2) Both react with dilute acid (HCl & H2SO4) to liberate hydrogen gas.

Fe(s) + H2SO4(aq) → FeSO4(aq) + H2(g)

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Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(g)

3) Both metal when heated react with oxygen to form oxide.

3Fe(s) + 2 O2(g) → Fe3O4(s)

2Zn(s) + O2(g) → 2ZnO(s)

4) Both metals when heated react with chlorine to form chloride.

2Fe(s) + 3Cl2(g) → 2FeCl3(s)

Zn(s) + Cl2(g) → ZnCl2(s)

5) Both elements react with sulphur to form sulphide.

Zn(s) + S(s) → ZnS(s)

Fe(s) + S(s)→ FeS(s)

Differences in the chemistry of Zn & Fe

1) Zn dissolves in conc. alkalis forming hydrogen gas but iron does not.

Zn(s) + 2OH-(aq) + 2H2O(l) → Zn(OH)42-(aq) + H2(g)

2) Zn shows a single valency of +2 while iron exhibits variable valencies of +2 &+3.

3) Zn forms compounds that are white in color where as Fe forms compounds which
are colored.

Fe2+ -green

Fe3+ -brown

4) Iron is paramagnetic(due to unpaired electrons in the 3d-subshell) while Zn is dia-

magnetic( due to paired electrons in its 3d-subshell)

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5) Fe forms dimeric chloride, Fe2Cl6.

Cl Cl

Cl

Fe Fe

Cl Cl Cl

6) Zinc does not react with cold moist air. Iron reacts with moist air to form hydrated
iron(iii) oxide (rust).

Qn. State the similarities in the chemistry of zinc & magnesium.

Atomic number is 29

Electronic configuration:1S22S22P63S23P63d104S1

ORES OF COPPER

1. copper pyrite CuFeS2

2. malachite CuCO3.Cu(OH)2

Extraction of copper(pyrite ore)

 The ore is 1st ground to powder. The finely divided ore is then mixed with water
and oil(frothing agent). The earthly materials sink at the bottom because of their
high density whereas the ore particles float on top, where they are removed,
washed and dried.

 The ore is roasted to convert the copper pyrite to copper(i) sulphide, iron(ii) ox-
ide and sulphur dioxide.

2CuFeS2(s) +4O2(g)→Cu2S(s) +2FeO(s) +3SO2(g)

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 The solid product is transferred into a blast furnace and silica added. On strong
heating, the iron(ii)oxide reacts with silica to form slag.

FeO(s) +SiO2(s) →FeSiO3(l)

 The copper(i) sulphide reacts with air forming copper(i)oxide.

2Cu2S(s) +3O2(g) → 2Cu2O(s)+2SO2(g)

 The copper(i)oxide produced and the unroasted copper(i)sulphide react in the

heat of the blast furnace with limited air supply to form copper.

2Cu2O(s) +Cu2S(s) →6Cu(l) + SO2(g)

The copper formed solidifies on cooling and is called blister copper and contains impu-
rities . The last process in the extraction is purification of blister copper.

Extraction from malachite

 Concentration process.

The ore is ground to powder. The finely divided ore particles is mixed with water and
oil and shaken for a while.

The earthly materials (high density) sink at the bottom whereas the ore particles (low
density) float on the surface, where they are removed, washed and dried.

 The ore is roasted to form copper(ii) oxide.

CuCO3.Cu(OH)2(s) → 2CuO(s) + CO2(g) + H2(g)

 The copper(ii) oxide is reduced with carbon on heating to copper.

CuO(g) + C(s) → Cu(s) + CO2(g)

The copper formed is then purified by method of electrolysis.

Purification of Copper –Electrolysis

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or

 The anode is a block of impure copper.

 The cathode is a thin piece of pure copper

 The electrolyte is copper(ii) sulphate solution.

 When electricity is passed through the cell,

At the anode,

copper is dissolved by oxidation, Cu2+ ions go into solution.

 Cu(s) - 2e- → Cu2+(aq)

At the cathode,

 copper is deposited by reduction.

 Cu2+(aq) + 2e- → Cu(s)

 As copper ions move from the anode to the cathode

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the anode gets smaller as the cathode gets bigger

Uses of copper

Amongst other things copper is used for:

 electrical wiring. It is a very good conductor of electricity and is easily drawn

out into wires.

 domestic plumbing. It doesn't react with water, and is easily bent into shape.

 boilers and heat exchangers. It is a good conductor of heat and doesn't react
with water.

 making brass. Brass is a copper-zinc alloy. Alloying produces a metal harder

than either copper or zinc individually. Bronze is another copper alloy - this
time with tin.

 coinage. copper-colored coins, "silver" coins are also copper alloys - this time
with nickel. These are known as cupronickel alloys. UK pound coins and the
gold-colored bits of euro coins are copper-zinc-nickel alloys.

REACTIONS OF COPPER

a) With air

Copper reacts with moist air to form a green outer layer of cop-
per(ii)carbonate(protective layer).

Heated copper reacts with oxygen enriched air(below 800 oC) to form black copper(ii)
oxide.

2Cu(s) + O2(g) → 2CuO(s)

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At very high temperature> 800 oC ,copper reacts with oxygen to form copper(i)oxide.

4Cu(s) + O2(g) →2Cu2O(s)

b) With halogens.

Heated copper reacts with halogen to form copper(ii)halide.

Cu(s) + Cl2(g) → CuCl2(s)

However copper reacts with iodine to form copper(i)iodide.

c) With sulphur.

When heated, copper forms a sulphide .

Cu(s) + S(s) → CuS(s)

d) With acids.

i) Dilute nitric acid reacts with copper to form copper(ii)nitrate, nitrogen monoxide and
water.

3Cu(s) +8HNO3(aq) →3Cu(NO3)2(aq) +2NO(g) +4H2O(l)

ii) Copper reacts with concentrated nitric acid to form copper(ii)nitrate, nitrogen diox-
ide gas and water.

Cu(s) +4HNO3(aq) → Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)

iii) Copper reacts with concentrated sulphuric acid to form copper(ii) sulphate, sul-
phurdioxide and water.

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Cu(s) + 2H2SO4(aq) → CuSO4(aq) + SO2(g) + 2H2O(l)

COMPOUNDS OF COPPER

Copper shows 2 oxidation states of +1 and +2, however compounds in +1 oxidation

state are unstable.

Compounds in +2 oxidation states

This is the most stable oxidation state of copper and in aqueous solution exists as
[Cu(H2O)4]2+ which is a blue solution.

It slowly undergoes hydrolysis forming acidic solution.

[Cu(H2O)4]2+ (aq) ↔ [Cu(H2O)3OH]+ (aq) + H+(aq)

(i) Copper(ii) hydroxide

It’s a blue ppt formed when aqueous sodium hydroxide is added to copper(ii) ions.

Cu2+(aq) + 2OH-(aq) →Cu(OH)2(s)

Copper(ii) hydroxide does not dissolve in excess sodium hydroxide. However dissolves
in excess ammonia solution to form a deep blue solution.

Cu(OH)2(s) + 4NH3(aq) →[Cu(NH3)4]2+ (aq) +2OH-(aq)

Tetra- ammine copper(ii) ions

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ii) Copper (ii)chloride.

Its prepared by adding a stream of dry chlorine gas over heated copper metal.

Cu(s) + Cl2(g) → CuCl2(s)

In aqueous solution, it exists as [Cu(H2O)4]2+ .

It slowly undergoes hydrolysis forming acidic solution.

[Cu(H2O)4]2+ (aq) ↔ [Cu(H2O)3OH]+ (aq) + H+(aq)

Copper(ii) chloride dissolves in conc. hydrochloride acid to form a yellow solution of

tetra-chlorocupprate(ii) ions [CuCl4]2-

NB:

A complex ion may undergo ligand exchange whereby all its ligands are replaced by a
different ligand which is more willing to donate the pair of electrons more readily. Al-
tering a ligand around a central metal ion brings about a marked color change.

E.g. [Cu(H2O)6]2+

[CuCl4]2- excess conc. HCl

[Cu(H2O)4]2+ excess ammonia
[Cu(NH3)4]2+

Yellow Blue Deep blue

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DETERMINATION OF COPPER(II) IONS IN COPPER(II) SALTS

Method1

Applicable to any soluble salt of copper.

(starting from copper ore, dissolve the ore in dilute sulphuric acid)

Procedure:

To a solution containing copper(ii) ions is added excess potassium iodide, a white pre-
cipitate of copper(i) iodide is formed which is stained brown by the liberated iodine.

2Cu2+(aq) + 4I-(aq) → Cu2I2(s) + I2(aq)

White ppt brown soln

The amount of iodine liberated is then determined by titrating the resultant solution
with a standard solution of sodium thiosulphate using starch indicator.

2S2O32-(aq) + I2(aq) → S4O62-(aq) + 2I-(aq)

The volume of thiosulphate solution used is noted.

Treatment of results

The over all equation of reaction is obtained by adding the two equations above :

2Cu2+(aq) +2S2O32-(aq) 2I-(aq) →Cu2I2(s) + S4O62-(aq)

2moles of thiosulphate ions react with 2moles of Cu2+ ions .

Thus knowing the moles of thiosulphate ions that reacted , that of copper ions present
in the solution can be determined.

Method2

This method applies to copper(ii) iodate only Cu(IO3)2

i) Cu(IO3)2(s) + aq ↔ Cu2+(aq) + 2IO3-(aq)

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ii) IO3-(aq) + 5I-(aq) + 6H+(aq) → 3I2(aq) + 3H2O(l)

iii) I2(aq) + 2S2O32-(aq) → S4O62-(aq) + 2I-(aq)

To a solution containing copper(ii) iodate is added excess potassium iodide solution

followed by dilute sulphuric acid .

Iodine is liberated according to the equations above. The liberated iodine is then titrat-
ed with a standard solution of sodium thiosulphate using starch as indicator.

The volume of thiosulphate used is noted.

a)Write the electronic configuration of the following species (atomic

number= 25):

i)Mn

ii)Mn2+

iii)Mn3+

iv) Mn7+

b) i) State the most stable oxidation state of Mn. Give a reason for your answer.

ii) State the possible oxidation states of manganese.

iii) Explain why manganese show variable oxidation states.

c) Aqueous sodium hydroxide was added drop wise to a solution containing Mn2+
,state what was observed and write equation for the reaction that took place.

d) i) Give a formula of a compound or ion containing Mn in an oxidation state of

+7 .

ii) How do you account for the existence of the +7 oxidation state?

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e) Write equation to show the reduction of MnO4- in :

i) alkaline medium.

ii) acidic medium.

f) Discuss the chemistry of manganese and magnesium showing similarities.

Answer

i)1S22S22P63S23P64S23d5
ii) 1S22S22P63S23P63d5

iii) 1S22S22P63S23P63d4

iv) 1S22S22P63S23P6

i)The most stable oxidation state is +2. This is because after using the 4s-electrons, a
half filled 3d -orbital that is stable is left.

ii) +2, +3 , +4, +5, +6, +7.

Acidity of the oxide of manganese increases with the increasing oxidation state.

iii) The variable oxidation state of manganese is due to the fact that both the 4s and the
3d- electrons take part in bond formation.

This is because electrons are being removed from energetically similar 4s and 3d- or-
bitals.

For +2 oxidation state, only the 4s-electrons are utilized for bond formation, forming
stable Mn2+. For higher oxidation states, both the 4s and 3d- electrons are utilized.

Observation:

white precipitate, insoluble in excess and rapidly turns brown due to aerial oxidation .

Equation:

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Mn2+ (aq) + 2 OH- (aq) → Mn(OH)2 (s)

2Mn(OH)2 (s) + O2(g) → 2MnO2.H2O(s)

NB:

Similar observation & reaction occurs with aqueous ammonia solution.

d) i) MnO4-

ii)Manganese 1S22S22P63S23P64S23d5 , shows an oxidation state of +7 by using both

the 4s and 3d- electrons in the bond formation because they are energetically similar.

e)i)

MnO4-(aq) + 2H2O(l) + 3e → MnO2 (s) + 4OH- (aq) or

MnO4- (aq) + 4H+(aq) + 3e → MnO2(s) + 2H2O(l)

In alkaline condition, the change in oxidation state is from +7 to +4 since potassium

manganate (vii) is a mild oxidizing agent in alkaline medium

ii)

MnO4- (aq) + 8H+(aq) + 5e → Mn2+(aq) + 4H2O(l)

NB: KMnO4 has a wide applications in the laboratory as an oxidizing agent which
include the following:

 As an indicator in volumetric analysis to show end points of titrations.

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 To test for reducing agents e.g. sulphurdioxide.

 Estimating iron (ii) salts and oxalates.

 Preparation of gases e.g. chlorine gas is liberated when conc hydrochloric acid
is reacted with it.

NB:

Hydrochloric acid is not used to acidify KMnO4 during titration because KMnO4 is a
very strong oxidizing agent, oxidizes Cl- ions from hydrochloric acid to chlorine which
colors the whole solution pale green and difficult to estimate end point.

2KMnO4 (aq) + 16HCl(aq) → 5Cl2(g) +2KCl(aq) +2MnCl2(aq) +8H2O(l)

f)

 They both react with chlorine to form chloride when heated.

Mn(s) + Cl2(g) →MnCl2(s)

Mg(s) + Cl2(g) →MgCl2(s)

 They both react directly with nitrogen to form similar nitrides

3Mn(s) +N2(g) →Mn3N2(s).

3Mg(s) +N2(g) →Mg3N2(s)

 They both react with dilute hydrochloric acid to liberate hydrogen

gas.

Mn(s) +2HCl(aq) →MnCl2(aq)+ H2(g).

Mg(s) +2HCl(aq) →MgCl2(aq)+ H2(g)

 Manganese react with hot water to form oxide. Magnesium react

with steam in the same way.

Mn(s) +H2O(l) → MnO(s)+ H2(g)

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Mg(s) +H2O(g) → MgO(s)+ H2(g)

NB:

Confirmatory test of Manganese, Mn2+ ions in solution.

To solid manganese (II) salt is added concentrated nitric acid and

little solid lead (IV) oxide or sodium bismuthate solution and the
mixture boiled.

A purple solution forms

2Mn2+(aq) + 5 BiO3-(aq) + 14H+(aq) → 2MnO4-(aq) + 5Bi3+(aq) +

7H2O(I)

2Mn2+(aq) + 5PbO2(s) + 4H+(aq) → 2MnO4-(aq) + 5Pb2+(aq) +

2H20(1)

Reaction of Cobalt (II) ion, Co2+

The (+2) oxidation state is the most stable for simple cobalt salts;
they are colored pink . The simplest ion that cobalt forms in solu-
tion is the pink hexaaquacobalt(II) ion - [Co(H2O)6]2+.

A ligand exchange reaction involving chloride ions

If you add concentrated hydrochloric acid to a solution containing

hexaaquacobalt(II) ions, the solution turns from its original pink
colour to a rich blue. The six water molecules are replaced by four
chloride ions.

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The reaction taking place is reversible.

If you add water to the blue solution, it returns to the pink colour.

a) Sodium hydroxide solution

A blue precipitate formed insoluble in excess and turns pink on

standing

Co2+ (aq) + 2OH- (aq) → Co(OH)2(s)

With sodium hydroxide solution and hydrogen peroxide

Rather than relying on oxidation by the air, you can add an oxidis-
ing agent such as hydrogen peroxide

You get the cobalt(II) hydroxide complex when you add the sodi-
um hydroxide solution.

Addition of hydrogen peroxide produces lots of bubbles of oxygen

and a dark chocolate brown precipitate.

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The final precipitate contains cobalt in the +3 oxidation state.

4Co(OH)2 (s) + 2 H2O2 (aq) 4 Co(OH)3 (s)

b) Ammonia Solution

A blue precipitate formed which dissolves in excess to form a

brown solution and turns to a deep red -brown solution on stand-
ing in air.

Co2+ (aq) + 2OH- (aq) → Co(OH)2(s)

Co(OH)2(s) + 6NH3(aq) → Co(NH3)62+ (aq) + 2 OH-(aq)

Co(NH3)62+ (aq) → Co(NH3)63+ (aq) + e

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With ammonia solution and hydrogen peroxide

Rather than relying on oxidation by the air, you can add an oxidis-
ing agent such as hydrogen peroxide

The reaction with ammonia solution followed by hydrogen perox-

ide produces the same dark reddish-brown solution as before - only
faster. The equation for the oxidation of the ammine complex is:

Reactions of Nickel (II) Ion, Ni2+

a) Sodium hydroxide solution

A green precipitate insoluble in excess formed.

Ni2+(aq) + 2OH-(aq) → Ni(OH)2(s)

b) Ammonia Solution

A green precipitate formed which dissolves in excess to form a

blue solution

Ni2+(aq) + 2OH-(aq) → Ni(OH)2(s)

Ni(OH)2(s) + 6NH3(aq) → (Ni(NH3)62+(aq) + 2OH-(aq)

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c) Dimethylglyoxime

Test

To the solution of Ni2+ is 1st added ammonia solution drop-wise

until excess followed by a drop of dimethylglyoxime solution.

Observation

A green ppt, soluble to form blue solution and red precipitate is

formed .

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