elab notes library

TABLE OF content. Page …….. 1

T

CHAPTER 1 General introduction Page 2

CHAPTER 2 - Hydrogen Page…13

CHAPTER 3 Group 1 elements: Lithium, Sodium, Potassium, Rubidium, Cesium,

Francium. Page……………….22

CHAPTER 4. Group 2 Elements - Beryllium, Magnesium, Calcium, Strontium,

Barium, Radium . Page……………….29

CHAPTER 5. Group12 Elements - Zinc, Cadmium, Mercury. Page……………….38

CHAPTER 6 Group 13 Elements - Boron, Aluminium, Gallium, Indium, Thallium.

Page………………44.

CHAPTER 7 … Group 14 Elements - Carbon, Silicon, Germanium, Tin, Lead. Page…55

CHAPTER 8 Group 15 Elements- Nitrogen, Phosphorus, Arsenic, Antimony, Bismuth. Page…63

CHAPTER 9 Group 16 Elements, Oxygen, Sulphur, Selenium, Tellurium, Polonium. Page 72….

CHAPTER 10 Group 17 Elements, Fluorine, Chlorine, Bromine, Iodine, Astatine.

Page…………82

CHAPTER 11 Group 18 Elements- Helium, Neon, Argon, Krypton, Xenon, Radon

Page ……….89

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CHAPTER 1--- GENERAL INTRODUCTION:

The s-Block Elements . These are elements in which either the outermost s-orbitals are being filled or
react by losing electrons from the outermost s-orbitals . The elements that fit the two aspects of the
definition best are: (i)Hydrogen (ii), the alkali metals ( Li, Na, K, R, Cs, Fr) and (iii)the Alkali earth
metals(Be, Mg, Ca, Sr ,Ba, Ra).
Group 12 elements namely, zinc, cadmium and mercury do not fit the first part of the definition but fit the
second. We shall , therefore ,treat them as s-block elements. At this juncture, it may be worth noting that
in old literature , these elements are classified as transition elements. However, if we adopt the definition
of a transition element as one with partially filled d- or f- orbitals , either in the elemental form or one of
the commonly-occurring oxidation states ,we note that these elements do not qualify to be classified as
transition elements. Furthermore, they do not have many of the properties of transition elements, such as,
high melting and boiling points (in fact mercury is a liquid at room temperature), formation of paramagnetic
compounds or formation of coloured compounds due presence of unpaired electrons in d- or f- orbitals.
The p-Block Elements . These are elements in which the outermost p- orbitals are being filled . If a
p-block element is oxidized, electrons are removed from p or from both p- and s-orbitals of the outermost
occupied shell .The elements that fit this definition best are those elements in Groups 13 to 18.
An important point to note about s-and p-block elements is that when they take part in a chemical
reaction, the electrons involved come from or are added to the outermost energy level (i.e shell).This is an
important difference between the s&p block elements , otherwise referred to as the normal elements and the
so-called, “transition elements”. In the latter case, electrons can come from different energy levels. For
example, iron which has the electron configuration, , [Ar]3d64s2 ,forms the ferric ion ,( [Ar]3d5)3+, by
losing the two electrons in the 4s orbital and one electron from the 3d orbital .
On the other hand chlorine which has the electron configuration , [Ne]3S23P5 , attains the formal
oxidation state+7 ( e.g as in the perchlorate ion, ClO4- , by loosing the two 3S2 electrons and the five 3P5
electrons . In this case, electrons taking part in the chemical reaction come from one energy level for which,
n=3.
Table 1.1A The Periodic Table .

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 H H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

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Periods

Table 1.1b A Portion of The Periodic Table showing only the Normal
elements .
Groups

1 2 12 13 14 15 16 17 18
1 1H 2 2He
2 3Li 4Be 5B 6C 7N 8O 9F 1o Ne
3 11Na 12Mg 13Al 14Si 15P 16S 17Cl 18Ar
4 19K 20Ca 30Zn 31Ga 32Ge 33As 34Se 35Br 36Kr
5 37Rb 38Sr 48Cd 49In 50Sn 51Sb 52Te 53I 54Xe
6 55Cs 56Ba 80Hg 81Tl 82Pb 83Bi 84Po 85At 86Rn
7 87Cs 88Ra

Note: In this table, each element is preceded by its atomic No. Z.

The Lanthanides and the Actinides

57La 58Ce 59Pr 60Nd 61Pm 62Sm 63Eu 64Gd 65Tb 66Dy 67Ho 68Er 69Tm 70Yb 71Lu
89Ac 90Th 91Pa 92U 93Np 94Pu 95Am 96Cm 97Bk 98Cf 99Es 100Fm 101Md 102No 103Lr

Note: In this table, each element is preceded by its atomic No. Z.

NUMBERING OF THE GROUPS. An examination of table1.1 shows that there are eighteen vertical
columns in what is called The Periodic Table of the Chemical Elements. These columns are called groups.
Several methods have been used for naming these columns. We shall note two of the old methods mainly
because they are still present in most of the chemistry books available to the reader. We shall then show a
third method , which is recommended by International Union of Pure and Applied Chemists(IUPAC), and
which will e used in the rest of the text..

First Alternative of labeling the Groups.

In this system, hydrogen and the alkali metals are put in the first column which is called Group 1A.
The alkali earth metals are in the second column which is labeled Group 2A . Then, one moves to column
No. 13 and labels the boron sub--group elements as Group 3A . Carbon sub--group elements which are in
column number 14 are labeled as Group 4A . Nitrogen, Oxygen and fluorine sub-groups which are in
column numbers 15, 16 and 17 respectively, are labeled group 5A ,6A and 7A respectively .
Elements in column No. 18, the helium sub-group , were labeled the group zero, O, elements because of
the assumption that these elements could not form stable compounds with other chemical elements.
Whereas this is still the case for some of these elements especially helium and neon , it is definitely not true
for the heavier members. For example, Xenon forms many compounds with oxygen and fluorine such as
XeO3, XeF4, XeF6 . These days , the preferred name for these elements is “the rare gases ”, rather than
“inert gases” .
Then , one moves back to columns 8, 9, and 10 and lumps them together as the group VIII elements. The
elements in column No.11,the copper sug-roup, were labeled as 1B and those in column No 12, the zinc
sub-group, were labeled as 2B. The one moves back to column No.3 and labels these as 3B. Elements in

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Columns 4, 5, 6 and 7 are labeled as 4B, 5B, 6B and 7B respectively. In this system, the B-subgroup
elements and those in groupVIII are the ones considered as the transition elements. Modern classification
also classifies them as transition elements except those in the zinc sub-group.
This method of labeling the groups such that most of the normal elements are in the A- subgroups is
summarized in Table 1.2 below.

Table 1.2 . A Labeling of Groups so That s&p block Elements are in A- Groups.

Column No. Elements in the column(s) Label

1 H, Li,Na. K, Rb, Cs, Fr, 1A
2 Be, Mg, Ca, Sr, Ba, Ra, 2A
13 B, Al, Ga, In, Tl, 3A
14 C, Si, Ge, Sn, Pb, 4A
15 N, P, As, Sb, Bi 5A
16 O, S, Se, Te, Po 6A
17, F, Cl, Br. I, At 7A
18 He, Ne, Ar, Kr, Xe, Rn 0
8, Fe, Ru, Os, VIII
9 Co, Rh, Ir, VIII
10, Cu, Ag, Au VIII
11 Cu, Ag, Au 1B

12 Zn, Cd, Hg 2B
3 Sc, Lanthanides, Actinides, 3B
4 Ti, Zr, Hf, 4B
5 V, Nb, Ta 5B
6 Cr, Mo, W, 6B
7 Mn, Tc, Re, 7B
8, Fe, Ru, Os, VIII
9 Co, Rh, Ir VIII
10 Ni, Pd, Pt VIII

Second Alternative of labeling the Groups.

In this method, elements in columns 1,2,3,4,5,6, and 7 are labeled as the A elements. Those in
columns,8,9 and 10 are labeled the Group VIII members just as in alternative A. Elements in columns,
11,12,13,14, 15,16, and 17 are now given the label B and those in column 18 the label zero . We note here
that in both alternatives, the labeling of columns, 1, 2, 8, 9, 10, 11 ,12 and 18 is the same in the two
alternatives. This information is summarized in 1.3 below.
Some Terminology Used for chemical Elements.
In some chemical literature one comes across some terms like, base metals, platinum metals, the coinage
metals , noble metals etc. The platinum metals refer to the six metals, ruthenium, Osmium, rhodium ,iridium
palladium and platinum . The term “Noble metals” refers to metals that do not dissolve readily in
mineral acids .These include the platinum metals and gold, which was used to make crowns for the Nobles
(kings!). Base metals are metals that readily dissolve in mineral acids.

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Table 1.3 . A Labeling of Groups so that Elements in Column 1-7 are in the A Group.

Column No. Elements in the column(s) Label

1 H, Li,Na. K, Rb, Cs, Fr, 1A
2 Be, Mg, Ca, Sr, Ba, Ra, 2A
3 Sc, The Lanthnides, The 3A
Actinides
4 Ti, Zr, Hf 4A
5 V, Nb, Ta 5A
6 Cr, Mo, W 6A
7, Mn, Tc, Re, 7A
8, Fe, Ru, Os, VIII
9 Co, Rh, Ir, VIII
10, Cu, Ag, Au VIII

11 Cu, Ag, Au 1B
12 Zn, Cd, Hg 2B
13 B, Al, Ga, In, Tl, 3B
14 C, Si, Ge, Sn, Pb, 4B
15 N, P, As, Sb, Bi 5A
16 O, S, Se, Te, Po 6B
17, F, Cl, Br. I, At 7B
18 He, Ne, Ar, Kr, Xe, Rn 0

Method 3 ( RECOMMENDED IUPAC) SYSTEM OF NUMBERING GROUPS )

As can be seen from the foregoing discussion, it is not possible to tell which elements one is
referring to just by mentioning group 4B elements without indicating whether one is talking about carbon
or titanium sub-groups . The International Union of Pure and Applied Chemistry (IUPAC ) has
recommended a system which avoids this confusion by simply numbering the columns from Number 1 to
18 as shown in Table 1.1 and referring to these as the groups. In this Module, we shall follow this system.
( c ). Position of Hydrogen in the Periodic Table
A close examination of the periodic table shows that hydrogen appears in Groups 1 and 17. What is the
reason for this? We know that elements are placed in the same group if they have similar physical or
chemical properties or both .
It is known that in compounds of hydrogen where the hydrogen is co-ordinated to an electronegative
element and in particular oxygen, hydrogen is presumed to be present as the cation, H + . This is formed by
loss of the only 1s electron from the outermost orbital , the 1s-orbital . In a similar manner, the alkali
metals form compounds with less electropositive elements and especially highly electronegative elements

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like oxygen or the halogens by loss of a single electron from the outermost occupied s-orbital to form the
uni-positively charged cations, M+(M=Li, Na, K, Rb, Cs. Fr)
For this reason, hydrogen , though an none-metal , is placed in the same group as the alkali metals in
group1. Of course, the classification cannot be perfect in that, whereas the alkali metal cations , M+ , have a
rare gas core , H+ does not( it does not have any electron!).
Hydrogen is also placed in the same group as the halogens . The reason for this is that when it
combines with highly electropositive metals like the alkali metals, the alkali earths , the lanthanides or the
actinides, it forms salt-like hydrides in which hydrogen is present as the anion, H-,which has the same
number of electrons as the rare gas helium.
The halogens react similarly to form the halide ions, X- ( X= F, Cl , Br, I or At ) as shown in Table 1.4
below .

Table 1.4 Similarity of Halide ions and the Rare Gases.

Halogen Halide ion formed Isoelectronic raregas

in the reaction
:X+e X-
Fluorine, F F- Neon, Ne
Chlorine, Cl Cl- Argon. Ar
Bromine ,Br Br- Krypton, Kr
Iodine, I I- Xenon, Xe
Astatine ,At At- Radon, Rn

The similarity between hydrogen and the halogens is, thus , very obvious.

Significance of the Periodic Table.

Elements in any given group have similar arrangement of electrons in the outermost orbitals. For this
reason it is found that generally, members of one group have many similar physical and chemical
properties. We can illustrate this statement by considering two alkali metals, sodium and rubidium .
Whereas sodium is a common metal likely to be stocked in most chemistry laboratories and used for class
demonstrations , rubidium is not. It is well known that sodium reacts with water to produce hydrogen gas
,and , with chlorine to form sodium chloride, NaCl . This is a high-melting point ionic substance that
dissolves in water to form a solution which conducts electricity . The important point about similarity in
chemical and physical properties of elements of the same group is that one can make correct deductions
about an element one may never have seen . In this case if we substitute the word sodium with rubidium ,
all the statements we make will be correct even though we may never have seen this element ! E.g
Rubidium chloride is a water-soluble high-meting point ionic solid which dissolves in water to form an
electrolyte. Of course, there are cases where elements in same group have differing properties but , in these
cases, those differences can be accounted for reasonably well.
Variation of atomic and ionic sizes both (a) along a series and
(b)within a Group.

As will be noted shortly, atomic and ionic sizes play a very important role in determining the physical and
chemical properties of the chemical elements.
(a) Variation of atomic and ionic sizes along a series.

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 As one moves along a series from left to the right, both the atomic and ionic sizes decrease. This may
be seen from variation of the covalent radii of the elements of the third period.

Table 1.5 Covalent radii of 3rd. Period Elements.

Element (3) Li (4)Be (5) B 6) C (7) N (8)O (9)F (10) Ne

Covalent
radius(pm) 152 112 80 77 74 74 72 ………..

The number in bracket preceding an element is the atomic number. The reason for variation of the sizes
is that :- ( i ) The nuclear charge ( atomic number) is increasing across a series (i i ) Electrons are filling
either the same shell or the penultimate shell ( i.e n or (n-1). The pull of an electron in the outermost
occupied shell by the constantly increasing nuclear charge, therefore, increases as one moves from left to the
right. For example, when we compare lithium and fluorine which are in the same period (i.e series), we
note the following: Lithium which is at the beginning of this series has only three protons. The electron in
the outermost occupied orbital, namely 2s , is very far from the nucleus( 152pm!!) and ,therefore, is only
weakly held to the lithium atom which has a low nuclear charge. Such an electron is readily lost and we
say that lithium is a strong reducing agent. We note that by loosing this loosely held electron, the lithium
ion formed, Li+ , has the same electron configuration as the rare gas helium. The other alkali metals behave
similarly and hence, their chemistry is that of the cation M+.
When we consider fluorine which has atomic No. 9, and an electron configuration, 1s22s22p5 , we note that
the outermost electron is only 72pm from a very large nuclear charge of 9 protons. An important feature
to note about fluorine is that if it could get just one extra electron, it would have a stable octet ,just
like the rare gas, neon. It for this reason that fluorine does not only attract its own electrons but very readily
pulls electrons that are loosely held by other atoms to acquire a stable octet . An alternative way of saying
this is that fluorine is a strong oxidizing agent. Similar statements can be made about the other halogens.
Variation of ionic sizes along the Series. We have noted that atomic sizes decrease as one moves
from left to the right along a series . The same kind of tread is observed when ionic sizes are compared.
Ideally, the comparison should be made on ions of same formal oxidation state. Unfortunately, most of the
normal elements in the same period do not form stable ions of same formal oxidation state.
Furthermore, some of the ionic sizes shown in the following table are very crude estimates. In spite of this
drawback, the data finitely give a very clear picture of the way cationic sizes vary along a series as one
moves from left to the right.

Table 1.6 Ionic radii of 3rd. Period Elements.

Ion,
Ionic Li+ Be2+ B3+ C4+ N5+ O6+ F +7
Radius(pm) 68 35 23 16 13 9 8

This table shows that the higher the formal oxidation state of an ion, the smaller its radius. This increases
the polarizing power and hence, the degree of covalency for a particular type of compound formed. For
example on the basis of the ionic sizes, one can reasonably assume that the boron halides BX3 ,(X=F, Cl,
Br, I ) are more covalent than the corresponding ,BeX2 . Experimentally, this is found to be the case . For
example, whereas both BeX2 and BCl3 are hydrolysed by water, in the case of BCl3 the boron trichloride is

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irreversibly converted to B(OH)3 and gaseous HCl. On the hand BeCl2 is only partially hydrolysed and
partially ionized.

(b)Variation of atomic and ionic sizes within a group.

The radii of atoms in a given group increase as one moves down the group. The reason is that electrons
are filling shells that are further and further from the nucleus.

Table 1.7 Variation of Ionic radii o down the Groups For selected Elements

Ion Radius(pm) Ion Radius(pm) Ion Radius(pm)

Li+ 68 Be2+ 35 B 3+
23
Na+ 97 Mg2+ 66 Al3+ 51
K+ 133 Ca2+ 99 Ga3+ 62
Rb+ 147 Sr2+ 112 In3+ 81
Cs+ 167 Ba2+ 134 Tl3+ 95
Fr+ 180 Ra2+ 143

Variation in metallic Character within the periodic table.

Within a given series, the metallic character is highest at the beginning of a series and decreases as one
moves from left to the right. Thus, if we consider the elements of the third period( Li- Ne) and fourth
period( Na- Ar) we note that elements in groups 1 and 2 are typical metals whereas those in 17th and 18th
groups are typical non-metals .

Variation of metallic Character Within groups.

Within a given group, the metallic character increases as one moves down a group. This is best illustrated
by elements near the end of the various periods , eg elements in group 15.
In this group we note the following:
N— a gaseous none metallic element which forms acidic oxides.
P— a solid nonmetallic metallic element which forms acidic oxides.
As— a semi metal which forms amphoteric oxides. .
Sb and B are Metallic elements.

The Inert, “6S2” Lone Pair.

As noted above, the radii of atoms and ions in a given group increase down the group. Therefore, in the
case where elements of a given group form multiple oxidation states, one would expect the high oxidation
states to be more stable than the low ones. Whereas this is actually found to be the case among the d-block
elements, it is not so for the normal elements. Thus, it is noted that ,the elements in the 6th period members
in groups, 12, 13, 14, 15, 16, and 17, tend to form compounds in which the electron configuration,
[Xe]4f145d156S2., is retained. Perhaps for lack of better terminology, this is referred to as the inert “6S2”
lone pair . Some familiar examples are:

(i ) Thermal decomposition of HgO.

When HgO is heated to a temperature of 300oC, it decomposes to Hg and Oxygen.

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HgO(s) Δ Hg( g)+ O2(g)

Another indicator of the high tendency of mercury(II) to revert to elemental mercury is the very high
reduction potential:

Hg2+ + 2e = Hg(l) Eo = 0.8535V

In these reactions we note that , the electron configuration of elemental mercury is [Xe]4f14 5d106S2 in
which the 6s2 configuration is retained .On the other hand, the mercury (II) ion has the electron
configuration. [Xe]4f14 5d10 .
The retention of 6S2 inert lone pair appears to be the deriving force for these reactions.

(i ) STABILITY OF THALLIUM(I) OXIDATION STATE.

Thallium is in group13, and like aluminium, we may expect it to form compounds in the formal
oxidation state (III), in which the thallium (III) ion has the electron configuration, [Xe]4f14 5d10 . Actually,
such compounds are known, e.g Tl2O3. However, they seem to be thermally unstable, decomposing fairly
readily to revert to Tl(I) in which the 6S2 lone pair is retained. For example, when the oxide is heated to a
temperature of merely 100oC, it decomposes to Th2O and oxygen. Here, Tl(I) has the electron configuration
[Xe]4f14 5d106S2 . This observation is in big contrast to that of α-Al2O3. which is known to melt at 2072oC
and boil at 2980oC without decomposing. Thallium also forms the trihalides , TlF3, TlCl3 and TlBr3 , all
of which are thermally unstable as the following date show:-

Table1.8 Thermal Decomposition of Thallium Halides.

Halide, Decomposition
Temperature(oC).
TlF3, 550oC
TlCl3 40oC
TlBr3 <40oC
A compound of thallium formulated as , TlI3, has been shown to contain Tl+ and the linear trioiodide ion, [
I3]- .

(ii ) Stability Lead (IV) compounds.

Lead forms compounds in both oxidation state +2 and +4 . Those of oxidation state +2 are by far more
stable than those of oxidation state +4. The examples in Table 1.9 illustrate this .

Table1.9 Comparison of Relative Thermal Stability of Pb(II) and Pb(IV) Compounds.

Substance, Mpt oC BPt. oC

PbCl4 -5 dec105
PbCl2 501 901
PbO2 dec 290
PbO 886

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Species Electron Config ….

Elemental lead , [Xe]4f14 5d106P2

Pb2+ [Xe]4f14 5d106S2

Pb4+ [Xe]4f14 5d10

These examples suggest that lead should be readily oxidized to lead(II), and with difficulty to lead(IV).
The lead(IV) species should be readily reduced to lead(II). This is actually observed experimentally.

(iii ) Stability Bismuth (V) compounds.

Elemental Bismuth, has the electron configuration, [Xe]4f14 5d106S26P3 .
It forms compounds in both oxidation states +3 and +5. Whereas compounds of bismuth(III) in which the
metal ion, has electron configuration,
[Xe]4f14 5d106S2 are numerous, those of oxidation state +5 in which the metal ion has the electron
configuration [Xe]4f14 5d10 are few and very unstable. For example, action of extremely strong oxidizing
agents on Bi2O3, gives rather unstable product presumed to be Bi2O5. which is very unstable. It dissolves in
concentrated sodium hydroxide to form sodium bismuthate, NaBiO3, one of the strongest oxidizing agents
known. Bismuth does not form any pentahalide, not even, BiF5.

(iv ) Stability Polonium (IV) compounds.

In group 16, the elements sulphur , selenium and tellurium can be oxidized to oxidation state +6. Thus
far, no stable compounds of polonium with oxidation state higher than +4 have been reported. Burning the
element in air gives, PoO2, in which the electron configuration of Po(IV) is [Xe]4f14 5d106S2 . Here we note
that the inert “6S2” lone pair has been preserved.

DIAGONAL RELATIONSHIPS.
Elements with similar ionic potentials( the ratio charge/radius) have similar chemical and
physical properties. It is found that elements that are diagonally related have very similar ionic potentials
and, as can be expected, they have several similar physical and chemical properties. The following examples
illustrate this observation very well:-
. (1 ) : Lithium and Magnesium When these metals are heated in air, they form both the normal oxides
and the nitrides.
Δ
4Li +O2 2Li2O

2 Mg +O2 Δ 2MgO

Δ
6Li +N2 2Li3N

6Mg+2N2 Δ 2Mg3N2

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 Salts of the two elements are highly hygroscopic. No doubt, the small ionic radii of these cations are
highly polarizing.
(2 ) : Beryllium and Aluminium ;
Both beryllium and aluminium form amphoteric oxides and hydroxides which , therefore , dissolve in
both acids and bases .
The two elements form methainides,ie, carbides whose hydrolysis yields methane.

Be2C +4H2O = 2 Be(OH)2 + CH4 .

Al4C3 +12H2O = 4Al(OH)3 + 3CH4 .

Both elements form very hard , high melting point amphoteric oxides . The halides, especially the
chlorides, bromides and the iodides are typical covalent compounds that are readily hydrolyzed , so that
aqueous solutions of BeCl2 and AlCl3 are acidic .
Boron and Silicon . Both of these elements are typical non-metals which form acidic oxides , B2O3 and
SiO2 respectively. When mixed with metallic oxides and fused, they form glasses. A glass is a substance
that is difficult to crystallize and has no definite melting point , this being because of the structure of the
material . Silicates contain only the units SiO4 which are tetrahedral . They may be joined in chains, rings
or in three dimensions. Borates may contain BO3 units which are trigonal or tetrahedral BO4 units.
Borates, like the silicates, may form rings, chains or three dimensional networks . Both boron and silicon
form similar hydrides which are inflammable in air.
Essential Elements. Chemistry is one branch of science that has practical applications in any field one
cares to think about. Thus in both plant and animal life there are the so-called essential elements the reason
being that the plant or animal cannot survive without the particular element. We can illustrate this with a
few examples. The elements sodium, potassium and magnesium are essential in both animal and plant life.
Most likely you are aware that chlorophyll, the green- colouring matter in vegetation contains magnesium.
Were you aware that our skeletons and teeth contain the elements calcium and phosphorus? They are
present as a constituent of the mineral hydroxy apatite, apatite ,Ca5(OH)(PO4)3 i.e ,3Ca(PO4)2 .Ca(OH)2 .
Some of the OH groups have been replaced by fluoride ions to form the mineral, fluoro apatite .
Lack of the element called iodine leads to goitre.
The element zinc, is essential in that the functioning of many enzymes depend on this element. The
hormone insulin which catalyzes oxidation of glucose will only function in presence of zinc. The element
lithium in microgram quantities has been shown to be a cure for mental illness. Fluorine and selenium are
poisonous if taken in excess amounts . However, lack of these elements in the microgram levels required
leads to serious body disorders. For example , lack of fluorine leads to formation of weak teeth whereas too
much fluorine leads to formation of brown teeth . The muscles are made of proteins whose basic structural
units are the elements carbon, hydrogen, nitrogen and oxygen. The list is long but we can conclude this
topic by noting that most of the essential elements are normal elements.

Practical Application. What practical value does a knowledge of chemistry have?

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CHAPTER 2 - HYDROGEN

Occurrence: Hydrogen has three isotopes namely, Protium, 11H ,Deuterium, 21H ( D) and tritium 31H ,..
( T). The first two occur naturally , with relative abundances of 99.985% for protium and 0.015% for
deuterium. Tritium which is produced artificially is
radio-active with a half life of 12.65yrs. hydrogen is the most abundant element in the universe. It has been
estimated that 90% of all atoms in the universe ( or approximately 75% of the mass of the Universe) are
those of hydrogen. Although the atmosphere may contain traces of hydrogen, the element is usually found in
combined form. Water is an obvious example of compounds of hydrogen. All materials of organic origin
eg. wood, petroleum products, vegetation , animals etc contain hydrogen in a combined form. Some
properties of the three isotopes are summarized in Table 2.1 below.

Table 2. Some important properties of Dihydrogen, H2.Deuterium, D2 and Tritium , T2.

Property H2 D2 T2
Mwt 2.015650 4.028204 6.032098
BPt/K 20.39 23.67 25.04
Critical Temp/K 33.19 38.35 40.6(estimated)
Dissoc. 435.88 443.35 446.9
Energy(kJ/Mole)

PREPARATION : There are very many reactions which generate hydrogen gas. For example, all metals
and non-metals for which the reduction potential , oE ≤ O should, in principle, liberate hydrogen on their
reaction with water or acids. The alkali metals, the alkali earths , the lanthanides and the actinides with
reduction potentials of the order of –3V are particularly reactive.
The following are just a few of reactions which produce hydrogen. :-

( i )Decomposition of saline hydrides , boranes , silanes and hydrido complexes of the type [MH4]n- , such
as [BH4]- , [ AlH4] - , [GaH4]- or [ BeH4] 2-
E.g.
LiAlH4 (s) + 4H2O(l) s) Al(OH)3(s) +LiOH(aq ) +4H2(g )
( ii ) Water- decomposition of saline silicides ,E.g

Na2Si(s ) + 3H2O(l ) Na2SiO3(aq) + 3H2(g )

( iii ) Reaction of silicon with hot aqueous alkali

Si(s ) + 4NaOH (aq ) Na4SiO4(aq) + 2H2(g )

(iv ) Reaction of silicon with hot hydrohalic acid

Si(s ) + 3HCl (g ) 350oC SiHCl3(aq) + H2(g )

12
( v ) Reaction of an amphoteric element with strong alkalis
Be(s ) + 2NaOH (aq ) heat Na2BeO2(aq) + H2(g )
2M(s ) + 2NaOH (aq ) 2H2O (g) heat 2NaMO2(aq) +3H2(g

( M= Al, Ga )
Sn(s )+ 2KOH(aq) + 4H2O(l ) heat K2[Sn(OH)6] (aq) + 2H2(g )

Sn(s )+ KOH(aq) + H2O(l ) heat KHSnO2 (aq) + H2(g )

Zn(s )+ 2KOH(aq) + heat K2ZnO2 (aq) + 2H2(g )

Ge (s) + 2KOH(l) fuse K2GeO2(l ) + H2(g )

( vi ) Decomposition of water by electropositive Metals . Electropositive metals react with water to

produce hydrogen , the decomposition temperature depending on the reduction potential of the metal.
Thus, whereas highly reactive metals like the alkali metals or the heavy alkali earths react with water at
room temperature (or even lower) less electropositive ones like iron will react with water only at elevated
temperatures.
E.g
2M + 2H2O(l ) room temperature 2MOH + H2(g)
( M=, Na, K, Rb, Cs)

M + 2H2O(l ) room temperature M(OH)2 + H2(g)

( M=, Ca,Sr, Ba ,Ra)

3Fe + 4H2O(l ) Steam Fe3O4(s) + 4H2(g)

It is noteworthy that for the heavy alkali metals and the heavy alkali earths the reduction potentials are
of the order of –3V. The heat generated in reaction of such metals with either water or acids is so much
that in many cases the liberated hydrogen is usually ignited thus rendering such reactions very violent . An
example is the reaction

2Cs(s) + 2HCl(aq) 2CsCl(aq) + H2(g)

For this reason, it is very important that even for demonstration purposes, the alkali metals should be
handled with the uttermost care.
For laboratory preparation of hydrogen, one normally chooses a reaction that uses cheap reactants that
can be handled safely , eg the reaction of zinc powder or iron filings with dilute hydrochloric acid or
sulphuric acid.
For industrial manufacture of hydrogen, the method chosen does not take into account only the safety
aspect but also the economics of the process For example, in countries with cheap hydro-electricity,
hydrogen for industrial applications, eg manufacture ammonia using the Haber Process is produced by
electrolysis of water . On the other hand, in countries where electricity is expensive, hydrogen for
commercial applications is manufactured using other methods :

13
E.g (1) Thermal Decomposition of Steam On Coke

C(s) + H2O 1000oC CO(g) + H2(g)

(2) Reaction Of a Steam-Hydrocarbon Mixture at high temperature.

CH3CH2CH3(g) + 3H2O(g) 1100oC 3CO(g) + 12H2(g)

Note.( i) Both of these reactions are endothermic and ,hence, the processes are energy-consuming.
( ii ) In both cases , more hydrogen is produced by passing the CO -H2 gas mixture over an iron oxide or
nickel oxide catalyst at 400oC . Under these conditions, carbon monoxide is converted to carbon dioxide
which can be readily scrapped off from the gas mixture.
CO(g) + H2O 400oC CO2(g) + H2(g)

The degree of purification of the hydrogen thus obtained depends on the use to which the hydrogen is
intended. For instance , most of the hydrogen is used for ammonia manufacture in the Haber Process. In this
case the hydrogen must be purified such that the final product contains less than 10ppm of CO, the reason
being that CO gas poisons the catalyst.

TYPES OF HYDROGEN COMPOUNDS

Hydrogen forms different types of compounds among them the following:-
(a) Hydrides. : These are binary compounds between hydrogen and another element, usually one which is
either highly electropositive or has electronegativity close to that of hydrogen.
These include,( i ) Ionic Hydrides , ( ii) Covalent Hydrides and (iii) Interstatial Hydrides.
( b) Compounds in which hydrogen may be regarded as having a formal oxidation state +1. These
include, the hydrogen-halides ,HX(X=F, Cl, Br,I, At) and compounds in which hydrogen is co-ordinated
to highly electronegative elements like oxygen or nitrogen .
( i ) Ionic Hydrides. These are hydrides formed between hydrogen and electropositive elements such as
the alkali metals, the heavier members of the alkali earths , the lanthanides, and the actinides . These are
presumed to contain the hydride ion, H- . This view is supported by two observations. First, electrolysis of
molten hydrides (where these are sufficiently stable thermally, e.g. LiH ) yields hydrogen gas at the anode.
Second, the reaction of ionic hydrides like NaH or some complex metal hydrides such as LiAlH 4 with
even the weakest acids eg water, leads to liberation of hydrogen gas . The hydride ion has one of the
strongest ligand fields known. An important experimental observation on solid ionic hydrides is that , the
metal- metal separation distances in crystalline solids are much smaller than they are in the pure element .
as
E.g Substances Metal- metal
Distance (pm)

Elemental calcium( solid ) 394.7

Calcium Hydride, Ca H2, 360

The interpretation of this observation is that when the negatively-charged ion , H- are inserted in the
spaces formed by close-packing of metal atoms, it reduces the repulsion between any two metal nuclei .
Preparation. All the alkali metals form ionic hydrides of the type, MH , when the heavy metals are heated
in the temperature range 300-400oCin an atmosphere of hydrogen. Lithium forms the hydride only when

14
the reaction mixture (Li/H2) is heated in the temperature range 700-800oC . Table 2.2 below summarizes
some of their properties.
TABLE 2.2 SOME POPERTIES OF THE ALKALI METAL HYDRIDES , MH .
Stucture r(H-)(pm) MptoC
LiH NaCl 136 680
NaH NaCl 147 800d
KH NaCl 152 D
RbH NaCl 154 300d
CsH NaCl 152 D
key d= decomposes)
( ii ) Covalent Hydrides. These are usually formed by nonmetallic elements e.g the boranes, silanes ,
sulphur hydrides and the literally thousands of carbon hydrides such as the paraffins , alkenes , benezene
and its derivatives etc . The hydrides of carbon fall in realm of organic chemistry and will not be discussed
further.
( iii ) Interstatial (non- stoichiometric ) Hydrides. These are compounds in which the main structure of
the metallic solid is generally retained and the hydrogen atoms occupy some or all the octahedral and
tetrahedral holes. The metal : Hydrogen ratio may or may not be integral . Such hydrides are mostly by the
transition elements , e.g.Yb2.5, TH4H15, PdH0.5. Palladium forms the widest range of non-stoichiometric
hydrides in that it can absorb up to 935 times its own volume of hydrogen.

( b) Compounds in which hydrogen may be regarded as having a formal oxidation state +1

Water, H2O . Water , H2O, is by far the commonest solvent . Table 2.3 lists some of the physical
properties of this substance which is so vital in life processes. As can be seen from the boiling point data of
hydrogen compounds of the type,H2X(X= O, S, Se, Te,Po) , water ( H2O ) has an abnormally-high boiling
point considering that it has a molecular weight of only, 18 . For the other compounds, we note that the
boiling points increases with increase in molecular weight, as expected. .

Table 2.3 Some physical properties of water , deuterium and Tritium..

Property H2O D2O T2O

MWt 18.0151 20.0276 22.0315
MPtoC 0.00 3.81 4.48
BPtoC 100 101.42 101.51
Temp. of Max. 3.98 11.23 13.4
density
Max. Densityg/cc 1.000 1.1059 1.2150
Dielectric Constant 78.39 78.06
Heat of formation -285..85 -294.6
ΔHokJ/mole
Δ GokJ/mole -237.19 -243.5
[H+][OH-]/mol2 lit-2 1.008x10-14 1.95x10-15 6x10-16

15
Table 2.4 Some physical properties of the Hydrides, H2X.(X=O.S.Se,Te,Po)

H2O H2S H2Se H2Te H2Po

Mwt 18.015 34.08 80.98 129.62 211
MPt(K) 273.15 187.55 207.45 222.15 237.15
BPt(K) 373.15 312.85 331.85 369.15 410.15

The explanation for this abnormal property lies in formation of hydrogen bonds between adjacent water
molecules.
The concept of Hydrogen Bonding.

When hydrogen is bonded to a highly electronegative element and in particular, Oxygen, Nitrogen and
Fluorine, the covalent bond formed is such that, electrons are drawn mostly towards the electronegative
element , and thus leaving the hydrogen rather deficient in electrons. For example, a molecule of hydrogen
fluoride is correctly formulated as
δ+
H Fδ- rather than H F .

This emphasizes the fact that the electrons forming the covalent bond are not distributed evenly but are
displaced more towards the more electronegative fluorine atom.
A similar charge displacement takes place in a water molecule, so that B is better representation of the
structure of a water molecule than A .

H H δ+
δ
O O

H H δ+

A B

In A ,the O-H bond as drawn suggests that there is an even distribution of electrons . In fact, the real
situation is the one shown in B , where , oxygen being more electronegative attracts not only its own
electrons but even those contributed by the oxygen . This is the reason why the oxygen atom is shown as
having a slightly more negative charge and hydrogen shown as having slight positive charge.
Now consider a situation where there are millions of molecules as would be the case in water in a container.
The result is that, besides the normal covalent bond, a proton , by virtue of having some net positive charge ,
will experience attraction by anh nearby oxygen atoms that belong to other molecules , as shown in C
below.

16
 Normal covalent Covalent Bond .

H …………… O
O H
H
C
B

Hydrogen Bond

The weak attraction is referred to as Hydrogen Bonding

Whereas typical covalent bonds are within the range 100-1000kJper mole, hydrogen bonds are very much
weaker (10-50kJ/Mole) . Hydrogen Bonds become important because, whereas a single hydrogen bond is
very weak, the cumulative effect of millions of such bonds adds up to very large values because all the
solvent molecules are joined to each other either directly or indirectly through the hydrogen bonding.
This is the reason why, water must be heated to a temperature of 373.15 degrees Kelvin (100oC) to get
individual water molecules, yet H2S which has nearly double the molecular mass of water, boils at only
312.75 K. Hydrogen-bonding is insignificant in liquid hydrogen sulphide since sulphur has an
electronegativity of only 2.5 . That of hydrogen is 2.1 and that oxygen is 3.5.
Water is only one of thousands of compounds which show abnormal physical properties owing to
presence of hydrogen-binding Other examples are:-.

Carboxylic acids , RCOOH: These have vapour pressures that suggest that the acid has double the
actual molecular weight. The reason is that the acid vaporizes as a dimmer and not singly.

O………H O

R2C CR1
O H…… …..O

17
 Here, R1 and R2 represent alkyl or aryl groups.

ABNORMALLY HIGH BOILING POINT

OF HYDROGEN FLUORIDE , HF

Hydrogen fluoride has an abnormally melting point and boiling point in comparison with other
hydrogen halides
TABLE 2.5 . SOME PROPERTIES OF THE HYDROGEN HALIDES, HX(X=F, Cl, Br, I)

Mwt MPtoC BPtoC

PROPERTY
HX ( HF) 20.01 -83.1 19.54
HCl 36.46 -114.8 -84.9
HBr 80.91 -88.5 - 67
HI 127.91 -50.8 -35.38(at 4atm)

As the data in Table 2.5 show, the increase in melting points and boiling points for, HCl, HBr and HI are as
expected from their relative molar masses . On this basis, the data for HF are definitely abnormal . The
explanation lies in formation of long zig-zag chains(fig as shown below .

H 120

F
F

18
HELIX STRUCTURE OF PROTEINS . The muscles in the body are made of long polymers of amino
acids. These occur in form of helices within the tissues .The various strands are held in position by hydrogen
bonds .

WATER OF CRYSTALIZATION. Many ionic salts crystallize with water of crystallization. For
example, when solutions of magnesium sulphate , copper sulphate and calcium chloride and are
concentrated by evaporating some water, the solids that crystallize out have the compositions, MgSO4.6H2O,
CuSO4.5H2O and CaCl2.6H2O respectively. Crystals of such substances adopt the various structures
because of hydrogen bonding. For example, when CuSO4.5H2O which blue is heated to a temperature of
150oC, it loses all water of crystallization to form a white powder. Magnesium chloride, decomposes at
116oC to form oxochloride, Mg(OH)Cl.

19
CHAPTER 3 GROUP 1 ELEMENTS- Lithium, Sodium, Potassium, Rubidium, Cesium,
Francium.

Occurrence and metallurgy.

The alkali metals occur in combined form either as minerals or in the sea or lakes.
Lithium. Some of lithium minerals are, Amblygonite ,LiAl(F,OH)PO4., Lepidolite, K2Li3Al3(F,OH)
(AlSi3O10)2 Spodumene, LiAlSi2O6 ,Tourmaline, M7Al6(OH,F)4(BO3)3Si6O18(M=represents varying
amounts of Li, Na, K, Fe,Mn , Mg Ca) .
Sodium :Sodium occurs as the minerals,halite( NaCl), Cryolite, Na3AlF6 and Soda nitre, NaNO3 . In
addition, sea water and some lakes contain large quantities of dissolved solids . Over 76% of dissolved
solids in sea water are made of sodium chloride Sea water is, therefore , a very important source of
sodium and sodium compounds .In the Indian Ocean Coast of Kenya ,and indeed many other countries,
sea water is collected in shallow pools where the salt crystallizes out and harvested before all the water
dries up. The crude solid can be re-crystallized to any desired degree of purity.
Potassium, Important potassium minerals include,
Alunite, KAl3(OH)6(SO4)2 ; Kainite, KMgClSO4,3H2O;
Langbeinite, K2Mg2(SO4)2, Polyhalite, K2Ca2Mg(SO4)4,2H2O and Silvite ,
KCl .
Rubidium & Cesium . The main minerals are, Leidolite, (Lithium micas) ,
K2Li3Al3(F,OH)4(AlSi3O10)2. Sometimes ,po tassium in lithium micas is replaced by small amounts of
rubidium or cesium Pollucite , Cs2AlSi2O6 .
Metallurgy. Lithium has a relative abundance of only18ppm in the earth’s crust with the most concentrated
minerals having only between3 and 4% of lithium .The ore , must , therefore , undergo beneficiation to
render the extraction economical. For example, the metal can be recovered from spodumene , LiAlSi2O6 , by
converting it to the chloride as follows: -
( i ) Acid-Leaching : The mineral is heated to a temperature of around 1100oC. It is washed with dilute
sulphuric acid at 250 oC ,and finally with water to give a solution of lithium sulphate from which , Li2SO4
.H2O , if desired, can be crystallized. The solution is, however, normally treated with a solution of sodium
carbonate to precipitate, Li2CO3 . This is finally converted to LiCl by dissolving in HCl . Lithium metal is
obtained by electrolysis of a fused mixture of LiCl(55%) and KCl(45%) at ~ 450 oC .
( i i) Base Leaching : The concentrated ore is mixed with limestone( CaCO3) and heated to a temperature
of 1000oC. The cooled product is washed with water to remove the soluble lithium hydroxide , LiOH.
Treatment of this with concentrated hydrochloric acid gives a solution of lithium chloride from which the
solid , LiCl , can be crystallized.
SODIUM. Sodium metal is prepared by electrolysis of either fused sodium hydroxide at 330oC or a
eutectic mixture of NaCl ( 40%) and CaCl2(60%) at 580oC. Electrolysis of eutectic mixture rather than
fused sodium chloride is important because there is saving on energy costs as NaCl has a very high meting
point( 804oC) . Secondly , it minimizes the rate of anode corrosion by chlorine .
POTASSIUM. This can be obtained in a number of ways:
(i ). Electrolytic reduction of fused KOH at 360oC or better, by reduction of KCl with sodium vapour at
850oC.

Another method used for production of sodium is reduction of the Fluoride with calcium carbide .

Δ
2KF+ CaC2 CaF2+2K+2C

20
RUBIDIUM AND CESIUM. : These metals are prepared by one of several methods:
(i) Reduction of the chloride with sodium:
Among the alkali metals, sodium is the cheapest and most abundant . Hence, although the heavy alkali
metals can be obtained by other methods ( see below), in practice, they are obtained by reduction of
their chlorides with sodium vapour.

MCl Δ M + NaCl.

Other methods include

( i) Reduction of the oxides with metals like aluminium, iron , magnesium, calcium .
Δ
3Cs2O+2Al 6Cs( g) + Al2O3(s)

( i) Cesium can be obtained by reduction of the carbonate with carbon at 1000oC

2Cs2CO3 (s0 + 2C(s ) Δ 2Cs( g) + 3CO(g)

(iii) Thermal Decomposition of the azides, MN3.

All the alkali metal azides, MN3, except lithium azide, decompose when heated to a high temperature to
give the metal in a very pure form and nitrogen gas.

2NaN3 (s) Δ 2Na( l) + 3N2(g).

Note: when lithium azide is heated to a high temperature, it forms the nitride.

3LiN3 (s) Δ li3N(sl) + 4N2(g).

Position of the Alkali Metals in the periodic Table and Some General Properties.

The alkali metals are in group1 of the periodic Table. Starting with the second period, an alkali metal
occurs at the beginning of each period.
From the electron configurations of these elements ( Table 3.1) we note that , each element has one
electron in an s-orbital outside a rare gas core. A large covalent radius implies that the outermost s-electron
is weakly held to the nucleus . For this reason, these elements readily loose the outermost s-electron to form
a uni-positively cation M+,with a very stable rare gas core. Note the very large second ionization potential
for each of the alkali metals ,
which is a very clear indication that the rare gas core is very hard to disrupt (Table3.2). The ease with
which the alkali metals loose the outermost electron makes them very strong reducing agents .

21
Table3.1 The electron Configurations of the Alkali Metals.

Lithium [He]2s1
Sodium [Ne]3s1
Potassium [Ar]4s1
Rubidium [Kr]5s1
Cesium [Xe]6s1
Francium [Rn]7s1

Table3.2 . Some general Information and properties of the alkali Metals .

Element Li Na K Rb Cs Fr
(1817) (1807) (1807) (1861) (1860) (1839)
At. Wt. (z) 3 11 19 37 55 87
Relative. 18ppm 2.27% 1.84%
Abundance
MWt. 6.941 22.9898 39.098 85.468 132.905 223
Hat(kJ/mole) 161 109 90 85.8 78.7 …..
Sp.gr.(20oC) 0.534 0.971 0.862 1.532 1.873 …..
o
MPt( C) 180.54 97.81 63.25 38.89 28.40 27
BPt(oC) 1342 882.9 760 686 669 677
Cov.rad.(pm) 152 186 227 248 265
R+(pm) 68 97 133 148 167 180
HI (kJ/mole) 520.1 495.7 418.7 402.9 375.6
HII(kJ/mole) 7296 4563 3069 2640 2260
Key : HI = First ionization Energy .
HII = Second ionization Energy.

( Nb: The number shown in parenthesis below the element symbol is the year of discovery ).

Ionic sizes of the alkali metals.

In comparison with other elements, lithium has a very small ionic radius of 68 pm which compares with
that of the diagonally related magnesium of 65pm. The very small size gives lithium a very large ionic
potential ( charge/radius ratio) which in turn gives lithium some anomalous properties. Examples of these
properties are as follows:-
( i )Reaction of the metals with air. Lithium reacts with oxygen and nitrogen at room temperature or with
very slight heating to form the normal oxide ,Li2O and Lithium nitrides, Li3N , respectively . In this respect,
Lithium behaves like the diagonally-related magnesium which forms MgO and Mg3N2), respectively when
the metal is heated in air. When the other alkali metals are heated in air , they form , the normal oxides,
M2O ( M=Na, K, Rb,Cs) , the peroxides, M2O2 (M=Na,K, Rb,Cs) and, in case there is excess air, the
heavier members may also form the superoxides, MO2 (M=K, Rb, Cs).

22
( i i)Thermal stability of the hydroxides, MOH . All the hydroxides MOH( M=Na,K,Rb, Cs) vaporize
without decomposition. On the other hand when lithium hydroxide , LiOH , is heated it melts at 450oC .
When the temperature is raised to 924 oC , it decomposes to form the oxide, Li2O and water. No doubt, this
is due to the strong polarizing power of the Li+ ion.
( iii) Reaction of the metals with carbon. When heated in carbon , both lithium and sodium form the
acetylides, M2C2. The heavier members of the group form interstitial compounds.
( iv)Thermal Decomposition of the azides, MN3.
As noted above , When the alkali metal azides , MN3 (M= Na, K, Rb, Cs) , are heated , they decompose
to give very pure metal and nitrogen .The lithium azide , LiN3 , differs from the other azides in that , on
heating, it gives the nitride , Li3N, and nitrogen.
(v) Hydration of Lithium Compounds .
Whereas both lithium and the heavier members form similar compounds with oxo anions, e.g carbonates,
M2CO3, nitrates, sulphates , perchlorates, etc, the lithium compounds are different from those of the other
members of the group in that the lithium compounds cyrstalize with water which is very hard to dislodge .
And, any attempt to remove such water by heat alone leads to decomposition. This can be illustrated by
comparing the thermal effects on both crystalline lithium carbonate, triydrate and sodium carbonate,
hexahydrate . When the lithium compound is heated to 800oC, it decomposes to Li2O and CO2. On the other
hand, Na2CO3 when heated melts at 851oC without decomposition..
No doubt the high polarizing power of Li+ polarizes the carbonate ion, [CO3]2-
Alloys . All the kali metals ( except lithium) are miscible with each other in all proportions. Lithium is
only miscible with sodium and then, only if the temperature is above 380oC.
A potassium/sodium alloy with the ratio of 77.2%K and 22.8% Na has a melting point of –12.3oC. It
is used as a heat transfer agent . Another alkali metal alloy with a very low melting point is one with:-
Na………………..12%
K ………………..47%
Cs ………………41% .
This alloy has a melting point of –78oC. No other metallic system is known to have such a low melting
point.

Solutions of Alkali Metals in Liquid Ammonia, Amines and other Solvents.

The alkali metals and to a smaller extent, the heavy alkali earths(Ca, Sr, Ba), the lanthanide elements
Eu and Yb dissolve in liquid ammonia, amines and solvents like ethers to form blue-cloured solutions
when dilute. The solutions conduct electricity electrolytically meaning that the passage of a current is
made possible by mass transfer . In the case of alkali metals, the solution is believed to contain both
cations [M(solv)]+ and solvated electrons, [e(sol)]- .

M (s )dispersed M(solution ) [M(solv)]+ [e(sol)]-

in this case, the current is carried by both the electrons and the M+ ions. A broad absorption band around
15,000 Ǻ is associated with presence of free electrons since the metal ions are colourless. Very concentrated
solutions are brown-coloured.
Such solutions are decomposed by even the slightest traces of transition elements.
Hydrides . All the alkali metals form ionic hydrides of the type, MH. All of them have the rock-salt
structure . The heavy metals form hydrides when the elements are heated in the temperature range 300-
400oC. However, lithium forms the hydride only when the reaction mixture (Li/H2) is heated in the
temperature range 700-800oC . Table 3.4 below summarizes some of their properties.

23
TABLE 3.4 SOME POPERTIES OF THE ALKALI METAL HYDRIDES , MH .
Stucture r(H-)(pm) MptoC
LiH NaCl 136 680
NaH NaCl 147 800d
KH NaCl 152 D
RbH NaCl 154 300d
CsH NaCl 152 D
(key d= decomposes)
We note that the hydride ion in saline hydride has a radius of
136-152pm.
Oxides .The type of oxides formed by the alkali Metals have already been mentioned above .
All the alkali metal oxides dissolve in water readily to form strongly alkaline solutions.
What we need to note here is the nature of species formed in these reactions .

( i ) Reaction of the normal oxides, M2O with water .

The normal oxides, M2O react with water to form the hydroxide, MOH .

M2O( s )+ H2O(l) 2MOH(aq).

These hydroxides are completely ionized in water and this explains why their solutions are strongly basic.

(i i ) Reaction of the peroxides, M2O2 ,with water .

The peroxides, M2O2 , react with water to form the hydroxide, MOH and hydrogen peroxide .

M2O( s )+ 2H2O(l) 2MOH(aq) + H2O2laq).

(iii ) Reaction of the super-oxides, MO2 ,with water .

The super-oxides MO2 , react with water to form the hydroxide, MOH ,and hydrogen peroxide, H2O2 ,
and oxygen gas O2 .

2MO2 ( s )+ 2H2O(l) 2MOH(aq) + H2O2(aq). + O2 (g).

As may be expected both the peroxides and the superoxide are strongly oxidizing agents especially in
fused melts .

Hydroxides. All alkali metals form water-soluble hydroxides of the type MOH , which give strongly
alkaline solutions due to presence of OH- ions.

HALIDES,
Table 4,5 . lists the halides, MX(X=F,Cl, Br, I) of the alkali metals . As can be deduced from the melting
points, these are typical ionic substances.

24
Table3.5 The alkali Metal Halides and their Melting
Points (oC).

F Cl Br I
Li 845 605 550 449
Na 993 801 747 661
K 856 770 734 681
Rb 795 718 693 647
Cs 682 645 636 626
1.
The alkali metal halides can be prepared from reaction of the hydroxide, M(OH) or the carbonate
M2CO3, with a hydrohalic acid, HX, followed by crystallization of the resulting salt.
Sodium chloride makes up over76.5% of the dissolved solids in sea water. Large quantities of NaCl are
,therefore , recovered by simply letting the sea water collected in pools evaporate naturally. Alternatively,
salt may be recovered from vacuum- evaporation of sea water . In both cases salt is collected before all the
water evaporates. If the sea water is allowed to evaporate completely, the solid left will contain many
undesirable impurities but principally, calcium and magnesium salts.
Compounds of Oxo species .
Nitrates: Sodium nitrate ( salt petre ) and potassium nitrate are found in large deposits in Chile . Before the
discovery of the Haber Process , they served as the main source of nitrogen fertilizers. Today, nitric acid is
obtained by oxidizing ammonia catalytically on platinum gauze(The Oswald Process ) to NO which reacts
with more oxygen to form NO2 . Reaction of this with water gives nitric acid . Nitrates can be obtained by
neutralizing the acid with carbonates , sodium or potassium carbonate.

Thermal Decomposition of Alkali Metal Nitrates. When alkali-Nitrates are hated above 500oC , they
decompose to Nitrites and Oxygen.
500oC
2NaNO3 2NaNO2 + O2

If the heating is continued to 800oC, it decomposes to sodium oxide, nitrogen and oxygen.

4NaNO3 2Na2O + 2N2 + 5O2

Alkali-Metal Compounds Halogen Oxo- anions.

These include the following:- Chlorates, Bromates, iodates,. perchlorates, perbromates, periodates .

25
We take note of the chlorates. When chlorine is passed through a dilute solution of an alkali, it
disproportionates into chlorides and hypochlorite . This is the bleaching solution sold under different
trade names such as “Jik”.

2MOH+ Cl2 MCl + MClO + H2O

On the other hand, when concentrated solution of sodium or potassium

hydroxide is used , the disproportionation reaction that takes place gives
chlorate and chloride ions.
6MOH +3Cl2 5MCl+ MClO3 + 3H2O . Potassium chlorate is a major component of
the ingredients used in manufacture of matches.

26
CHAPTER FOUR GROUP 2 ELEMENTS – Beryllium, Magnesium, Calcium, Strontium, Barium,
Radium.

SECTION A Beryllium
Table 4.1 Some Properties of Beryllium.
Atomic No. 4
Relative Abundance …………………. 2ppm
Atomic weight 9.01218.
Electron Configuration [He]2s2
Specific gravity 1.848
Enthalpy of Atomization , ΔHatkJ/mole) 322
MPt(oC) 1278
BPt(oC) 2970
Reduction Potential , [Be2+] aq +2e = Be( s) Eo=1.85V
Metal covalent Radius(pm) 112
Ionic Radius(pm) ( Co-ordination No.4) 27
First ionisation Energy , ΔHI , (kJ/mole) 899.2
Second ionisation Energy ΔHII , (kJ/mole) 1757
Third ionisation Energy ΔHIII , (kJ/mole) 14800

Minerals. Beryllium occurs in at least thirty minerals but amongst them , only the following can be
exploited economically :-

Mineral formula
Beryl , 3BeO. Al2O3.6SiO2 .
Chrysoberyl , BeO.Al2O3
Phenacite ( Be2SiO4 )
4BeO.2SiO2.H2O Bertrandite
Metallurgy : Two methods are used for preparation of metallic beryllium.
( a) Electrolysis of either the fluoride mixtures NaF/BeF2 , BaF2/BeF2 or chloride mixtures such as
BeCl2/NaCl . Either of the fluoride mixtures NaF/BeF2 or BeF2/BaF2 is electrolyzed around 1350oC .
The use of eutectics is necessary because both molten beryllium chloride ,BeCl2 , and beryllium fluoride ,
BeF2 , have very low electrical conductances .
( b) Reduction of beryllium fluoride, BeF2 with Magnesium .
Beryllium metal is obtained by reduction of beryllium fluoride with magnesium metal around 1300oC .

BeF2+Mg Δ Be +MgF2

Chemical reactivity. Although the metal can react with fluorine at ordinary

27
temperature , all the other halogens react with the metal only at elevated temperatures to form the
dihalides , BeX2( X= F,Cl, Br, I) all of which are predominately covalent . It reacts with oxygen if heated
to 600oC to form the oxide, BeO , and with nitrogen if heated to 900oC to form the nitride, Be3N2. The
nitride can also be prepared by heating the metal in ammonia

8Be(s ) + O(2(s ) + N2(g )  2 BeO(s ) + 2Be3N2 (s )

.

6Be(s ) + 4NH3(g )  2Be3N2 (s )+ 6H2(g)

Beryllium oxide, BeO , adopts the wurtzite structure and, in this respect differs from the heavy Group 2
metal oxides which adopt the rock salt structure. Whereas this oxides of the heavy members are all basic,
beryllium , like the diagonally related aluminium is amphoteric . The metal itself and the oxide dissolve in
both acids and bases . For example , the metal dissolves in concentrated alkali , 3M sulphuric acid , 3M
Hydrochloric acid and in 5M hydrofluoric acid .

2NaOH (aq ) + Be heat Na2BeO2(aq) + H2(g )

Be(s ) + 2HCl(aq ) BeCl2(aq) + H2(g )

The Halides The halides of beryllium , their melting points and the boiling points are listed in Table 4.2

Table 4.2 Melting and Boiling Points for Beryllium Halides.

Be F Cl Br I
MPtoC 800 406 490 590

BPtoC 520 520

Preparation of Beryllium Halides : Elemental beryllium reacts with the halogens at elevated
temperature to form the various halides. However, unless there is a special reason to use the elements, these
halides are prepared by use of beryllium compounds . Eg whereas the fluoride can be prepared by a
reaction of the metal with fluorine , in practice, it is actually prepared by dissolving the metal oxide or
hydroxide in ammonium fluoride and decomposing the complex formed by heating to 280oC .
2NH4F2(aq) +BeO(s) (NH4)2BeF4(aq) +H2O (l)

(NH4)BeF4(s) ( 280oC) BeF2(s) + 2NH4F(sub)

The chloride and the bromide are conveniently prepared by passing CCl4 or CBr4 vapours over BeO heated
to about 800oC .
BeO(s) + CX4(g) 800oC BeX2(g) + COX2 (g ) (X=Br, Cl) .

Structure of beryllium halides. In the gaseous phase, all the beryllium halides , BeX2 , (X=F, Cl, Br ,I)
are linear molecules..

28
 X Be X

However, in the solid phase , the halides form polymeric chains in which the Be2+ ion is in approximately
at the centre of a tetrahedral environment .

X X
Be
X X

These are covalent molecules which are typical Lewis acids which dissolve in organic solvents. In water,
they are extensively hydrolyzed. Such solutions are acidic owing to presence of both HX acids and H3O+
ions produced in hydrolysis of the
beryllium(II) ion, [Be(H3O)4]+

BeX2+2H2O Be(OH)2 + 2HX

[Be(H2O)4]2+ +H2O [Be(H2O)3OH]+ + H3O+

Salts of Oxo acids : Beryllium salts of oxo acids such as nitrates and sulphates crystallize with four
molecules of water of crystallization since the maximum co-ordination number for beryllium is four, just
like the other second series elements. As noted above such solutions are acidic
ORGANOMETALLICS. All the elements of this group form organometallic compounds of the types,
RMX(X=Cl, Br, I) (R= alkyl group, M= Be , Mg, Ca, Sr, Ba) and (η5 -C5H5)2M are known . However, the
magnesium alkyl halides, otherwise known as Gignard reagents in honour of Victor Grignard who
discovered them , are by far the most important because of their applications in synthetic organic chemistry.
They are prepared by the general reaction, RX+Mg + I2(trace) and the mixture reacted in diethylether in an
atmosphere of dry oxygen-free nitrogen . The iodine is essential to initiate the reaction which must be
carried out in absolutely moisture-free ether because moisture reacts with these organometallis, sometimes
explosively. Furthermore ether is essential for the reaction to take place. The alkyl halide, RMgX is solvated
with two ether molecules ,i.e it has the composition, RMgX.2OEt2.

GROUP 2 SECTION B Mg , Ca, Sr, Ba , Ra.

OCCURRENCE

29
 .Magnesium is widely spread and relative abundance values vary widely in the rang 2.2-3.3% . The value
of 2.76% is taken as a reasonable average.
The principal magnesium minerals are :-
Brucite, Mg(OH)2 , Dolomite CaMg(CO3)2 , Epsomite MgSO4,7H2O
Ganierite, (Ni,Mg)6(OH)8Si4O18 , Magnesite, MgCO3 ,Olivine, (Mg, Fe)2SiO4,
Sepiolite,Mg4(OH)2Si6O15,6H2O, Spinel, Mg Al2O4 , Talc , Mg3(OH)2Si4O10 .
Calcium has a relative abundance of 4.66% in the earth’s crust . It is the fifth most abundant element in
the earth’s crust and hence, the third most abundant metal after aluminium(8.3%) and iron (6.2%). Perhaps
the most familiar form of clcium minerals are the carbonates which occur in different forms , eg. , Calcite
Aragonite, chalk ,CaCO3 and even the sea shells are all different forms of cacium carbonate , CaCO3 .
Other calcium minerals include the following:- Anhydrite (CaSO4) ,Dolomite, (Ca, Mg) (CO3)2; ,
Fluorite( CaF2 ) ,Apatite ,Ca5F(PO4)3 i.e ,3Ca(PO4)2 .CaF2 Gypsum, CaSO4 ,2H2O ; Scheelite, CaWO4 ;
Colemanite, Ca2B6O11 ,5H2O
The main minerals of strontium are the carbonate and sulphate minerals, strontianite, SrCO3 and
celesite , SrSO4 . The main minerals of barium are similar to those of strontium namely , the carbonate
mineral witherite, BaCO3, and the slphate mineral barite, BaSO4. Radium, which is itself radioactive, is
produced in radioactive decay.

METAURLLUGY

Elemental magnesium is obtained in one of two methods.

( a) electrolysis of either fused magnesium chloride, MgCl2 , or the partly hydrated chloride
recovered from seawater at a slightly lower temperature.
( b) Reduction of calcined dolomite .
Dolomite is mixture of calcium carbonate and magnesium carbonate in approximately equal amounts.
When this mixture is heated to a temperature of 1000oC and above , magnesium oxide, MgO , and
cacium oxide , CaO , are obtained. When this oxide

mixture is mixed with ferrosilicon and heated to a temperature of 1150oC at reduced pressure, the
following reactions take place:-

2(MgO.CaO) + FeSi 1150oC 2 Mg + Fe +Ca2SiO4

Calcium is obtained by electrolysis of molten Calcium chloride/calcium fluoride mixture . A little fluoride
is added to lower the melting point of calcium chloride . Pure calcium chloride melts at 782oC but addition
of a little calcium fluoride allows the electrolysis to be carried out at 700oC in a graphite pot with water-
cooled iron cathode .
Elemental strontium and Barium are obtained by one of two methods :-
( i ) High temperature reduction of the oxides with aluminium

3MO+ 2Al  3M + Al2O3

( ii ) Electrolytic reduction of the fused chlorides .

Radium, which is itself radioactive is obtained from radioactive decay of thorium .
. 230 Th90 226
Ra88+ 4α2

30
226 222
Ra88 Rn86+ 4α2

.Some properties of the heavy Group2 Elements are summarized in Table2.2. From this table we note that :-
(a) The chemistry of these elements is that of the bi-positively charged cation, M2+. It is noteworthy that
the reduction potentials are very close to –3V for the heavier members , and are very similar to those the
alkali metals. It is perhaps for this reason that the chemistry of the heavy alkali earths is very similar to that
of the alkali metals. For example , magnesium, like the diagonally-related lithium reacts with air to form
both the oxide and the nitride.

2Mg + O2 2 MgO

6Mg +2N2 2 Mg3N2

The heavy alkali metals react with liquid ammonia and amines to form blue solutions when dilute and
brown-coloured when concentrated. These solutions conduct electricity electrolytically .

Table4.3 ..Some properties of the heavy Group2 Elements .

Property Mg Ca Sr Ba Ra
At.No.Z 12 20 38 56 88
Relative abundance 2.76% 4.66% 384ppm 390ppm
At.wt 24.305 40.08 87.62 137.33 226.025
El.Config. [ Ne]3s2 [ Ar]4s2 [ Kr]5s2 [ Xe]6s2 [ Rn]7s2
sp.gr.(20oC) 1.738 1.55 2.63 3.62 5.5
MPt(oC) 649 839 768 727 (700)
BPt(oC) 1105 1494 1381 1850 1700
Eo(V) for -2.37 -2.87 -2.89 -2.91 -2.92
[M2+](aq) +2e =M(s)
Covalent radius(pm ) 160 197 215 222
Ionict radius(pm ) 72 100 118 135 148
ΔHat(kJ/mol) 127.4 155 158 136 113
ΔHI(kJ/mol) 738 590 549 503 509
ΔHII(kJ/mol) 1450 1146 1064 965 979
ΔHIII(kJ/mol) 7733
10540
ΔHIvkJ/mol) 13630
ΔHVI(kJ/mol)) 18000
ΔHVII(kJ/mol)) 21700
ΔHVIII(kJ/mol)) 25655
ΔHIX(kJ/mol)) 31640
ΔHX(kJ/mol)) 35460.

31
Halides of the heavy Group2 Elements.

All the heavy Group 2 Elements react with the halogens to form ionic halides of the type, MX2. Both the
melting Point and the boiling points for these halides are listed in Table 2.3 below.

Preparation and Industrial Manufacture .

As can be seen from Table 2.2, these elements are very electropositive and hence, they react readily with
the halogens to form the corresponding halides However, small laboratory preparations use cheap
procedures, e.g reaction of the carbonate with halogen halide, e.g.

MgCO3 +2HCl +6H2O MgCl2.6H2O +CO2 + H2O

Table4.4.The halides of the heavy alkali Earth Metals and their Meltng Points and Boiling points.

F Cl Br I
Mg
Ca 1423;ca2500; > 782; >1600 sld730 ;806- 784; ca1100
812
Sr 1473;2489 875;1250 643; d 515;d
Ba 1355; 2137 963;1560 847, d 740 ,
Ra 1000; 728; subl 900

Key d= decomposes; subl= sublimes; sld= slightly decomposed

Magnesium chloride is manufactured from either dolomite or the sea-water.

Oxides : All heavy alkali Earth metals are readily tarnished by air because of formation of the oxides,
MO. All of them adopt the rock-salt structure and are high-melting solids

Table4.5The oxides of the alkali Earth Metals showing their Melting Points and Boiling points.

Oxide Melting Point (oC) Boiling Point (oC)

BeO* 2530 3900
MgO 2852 3600
CaO 2614 2850
SrO 2430 3000
BaO 1918 2000

* This oxide adopts the wurtzite structure.

Note: The beryllium oxide is included here for comparison purposes. The oxides are conveniently prepared
by thermal decomposition of the carbonate . As the data in table 2.5 show, the decomposition temperature
is higher, the larger the molecular weight of the carbonate..

32
Table4.6 The Decomposition Temperatures of the alkali Earth Metal Carbonates .

Compound . Decomposition Temperature

( oC)

BeCO3 250
MgCO3 540
CaCO3 900
SrCO3 1289
BaCO3 2360

Calcium carbonate is by far the most important Group 2 metal carbonate . It is used in manufacture of glass
and Portland cement . Thermal decomposition gives lime, CaO, which is itself used for manufacture of
acetylene and sodium hydroxide.
Role of Limestone in the building Industry. When a mixture of limestone, clay and a little iron oxide is
intimately mixed and heated in the temperature range 900-1450oC, the product is what is called Portland
Cement. This can be considered as the product formed between lime, CaO , and clay , which is made of
aluminosilicates. The major compounds in Portland cement have been shown to have the approximate
compositions;-
3CaO.SiO2; 2CaO.SiO2; 3CaO.Al2O3 ; 2CaO.Al2O3 ; 4CaO.Al2O3 Fe2O3 .
This mixture is called clinker. If the clinker is ground and water added, it hardens straight away. In order to
slow the rate of hardening and thus make it workable, the clinker is mixed with about 5% by weight of
gypsum before grinding. The iron oxide has no cementing value but the oxide is deliberately added to the
limestone-clay mixture to act as flux, i.e to lower the temperature at which the cement forms.
The importance of cement in the building industry and construction of bridges cannot be stressed enough.
Hydroxides.. These are formed the oxides dissolve in water . They form strongly alkaline solutions

MO+H2O M(OH)2 .

The solubility of the hydroxide increases with increase in molecular weight

Table4.7 The The solubilities of alkali earth metal hydroxides
Substance Solubilityg/100g water at temperature shown in parenthesis
Mg(OH)2 0.0009(18) ; 0.0009 (100) (100)
Ca(OH)2 0.185 (18) (0) ; 0.0009 (100)
Sr(OH)2 0.41 (OC);21.83(100)
Ba(OH)2 .8H2O 5.16(15); 94.7( 7*)
Ra(OH)2
Although calcium hydroxide is very sparingly soluble, it is , nevertheless used for manufacture of sodium
hydroxide using the process:-

Ca(OH)2 (aq) +Na2CO3(aq) 2 NaOH + CaCO3

33
Sulphates. BeSO4 , MgSO4 and CaSO4 ,crystallize as the hydrates, BeSO4.4H2O,
MgSO4.6H2O and CaSO4.2H2O, respectively. Strontium and barium sulphates are extremely insoluble, a
property that is used in gravimetric determination of these elements or sulphates. Barium ions are extremely
poisonous . The very low solubility of barium sulphate even in acidic media makes it possible to give a
patient a suspension of barium sulphate( under the trade name “barium meal” without any harmful effect.
Once a patient has been given such a suspension, the X-ray of the stomach and the intestines is taken .It is
possible, because of the barium meal,to follow the outline of the intestines and the abdomen and detect any
place with problem, eg. ulcers.
Magnesium sulphate is given to patients with constipation under the trade name, Epsom salt .

NITRIDES. When the alkali earth metals are heated in a stream of ammonia, they form the
nitrides, M3N2. Nitrides can also be prepared by direct reaction of the metals
with nitrogen . It is noteworthy that magnesium is the most reactive and forms
the nitride at 300oC. The other metals require heating at higher temperatures,
eg, beryllium is heated in nitrogen, it forms a nitride only when the
temperature reaches 900oC.

CARBIDES : All the metals react with acetylene to form acetylides, MC2, which , on
hydrolysis gives acetylene. Magnesium reacts with graphite at 500oC to give
MC2 . In the temperature range, 500-700oC, magnesium and graphite react to
form , Mg2C3.
When lime and graphite are heated in an electric furnace to a temperature of 2000oC,
calcium carbide, CaC2, , is formed. This is probably one of the most important carbides in
industry today. Its hydrolysis gives acetylene and calcium hydroxide.
An acetylene/Oxygen flame gives a temperature of 3100oC and hence, the extensive use of this gas in
welding .
CALCIUM CYANAMIDE, CaCN2. This is prepared by heating calcium carbide in an atmosphere of
nitrogen in the temperature range, 1000-1200oC.

CaC2 + N2 Δ CaCN2 +C

Calcium Cyanamide has many industrial applications such as : -

Direct use as a fertilizer. Its hydrolysis gives cyanamide , H2NCN .

It is used as a weed killer and as a cotton defoliant.
It is used for manufacture of thiourea and melamine.

ORGANOMETALLICS. All the elements of this group form organometallic compounds of the type,
RMX( R=Alkyl group, M= Be, Mg, Ca, Sr, Ba,.X=halogen ion) and cp2M where cp=C5H5 radical . Among
the RMX compounds, the magnesium compounds are, by far , the most important. These are the so-called
Grignard reagents in honour of count Victor Grignard who developed their chemistry for which he got a
Nobel Prize in Chemistry in 1912.
Preparation: These are prepared by the reaction

34
RX+ Mg N2 RMgX( X= Cl, Br, I} . A trace of iodine is added to
Et2O
initiate the reaction. The reactivity of the alkyl halides increases in the order

I>Br>Cl. The preparation must be carried out in a dry oxygen-free atmosphere.

The alkyl halides, RMgX are solvated with two ether molecules. The product in solution is, therefore,
2OEt2. NMR studies have shown that all the species, RMgX, R2M and MX2 are all present in equilibrium.

35
CHAPTER5 GROUP 12 ELEMENTS, Zinc, Cadmium and Mercury.

Introduction: The members of the zinc form an interesting class of elements in that whereas zinc is an
essential trace element which has been discovered in at least two hundred enzymes, both cadmium and
mercury are extremely toxic. Insulin, the hormone that catalyzes oxidation of glucose functions only in
presence of zinc ions. Zinc compounds have been used for treatment of wounds for a long time.
Occurrence: The main minerals of zinc are, Franklinite, (Z,Mn)Fe2O4 , Hemimorphite,
Zn4(OH)2Si2O7,H2O , sphalerite , (Zn , Fe)S; Zinc blende(ZnS ; Wurtzite ,ZnS; Zincite, ZnO;
Smithsonite, ZnCO3 ;and Willemite, Zn2SiO4
The only important mineral of cadmium is the sulphide, Geenockite, CdS
Mercury occurs as the mineral, cinnabar. ,HgS ,
Some general properties of these elements are summarized in Table 5.1

Table5.1 Some General Properties of Group 12 Elements:

Property Zn Cd Hg
At. No. Z 30 48 80
At.Wt. 65.38 112.41 200.49
Electron Config. [Ar]3d104S2 [Kr]4d105S2 [Xe]4f145d106S2
Electronegativity 1.6 1.7 1.9
Cavalent radius(pm) 134 151 151
Ionic rad., M2+(pm) 74 95 102
Rad M+(pm) ----------- -------- 119
ΔHI(kj/Mole) 906.1 876.5 1007
ΔHII(kj/Mole) 1733 1631 1809
ΔHIII(kj/Mole) 3831 3644 3300
o
E(M2++2e=M (V) -0.7619 -0.4030 +0,8545
ΔHat(kj/Mole) 129.3 111.9 61.3
Density(g/cc) 7.14 8.65 13.534
MPt.oC 419.5 320.8 -38.9
BPt.oC 907 765 357

Among the various properties of listed in Table 5.1, the following are noteworthy:-
(a)Electron configuration . We note that the outermost electrons are in the s- orbitals. The chemistry of these
elements , therefore, involves loss of these electrons to form the cations M2+. In agreement with this, all
stable compounds of zinc and cadmium are those in which the metal is in formal oxidation state +2.
Whereas mercury also forms compounds in which the metal is in formal oxidation state +2, there is
destabilizing factor namely, the tendency to retain a “6S2” lone pair. It is for this reason that Hg(II)
compounds appear thermally unstable.
Thus, HgO 300oC Hg(g)+O2(g)

(a) Mercury forms stable M(I) cations .These contain the di-mercurous cation,

36
 (b) [Hg2 ]+ with structure , [Hg-Hg] .

(c ) The elements of this group have relative low melting and boiling points. The melting point of
mercury (-38.9oC) is the lowest for any metal .

(d ) The reduction potential data show that whereas both zinc and cadmium are reducing agents and will
readily dissolve in dilute non-oxidizing acids like HCl to liberate hydrogen, mercury does not. Mercury
does , however, dissolve in dilute nitric acid to mercurous nitrate, Hg2(NO3)2 ,and in both concentrated
nitric acid and suphuric acid to give the mercuric salts.
Metallurgy: Zinc is recovered from sulphide ores as follows:- The ore is concentrated either by
sedimentation or flotation. It is then roasted in air to convert it to the oxide, ZnO.

2ZnS(s)+3O2(g) Δ ZnO+ 2SO2

The sulphur dioxide produced is used to manufacture sulphuric acid. The zinc oxide can be treated in one of
two ways:-
(a) Electrolyticaly. In this method, zinc is leached from crude ZnO with dilute sulphuric acid . Any
cadmium present ( since cadmium is usually obtained as an impurity in processing of zinc ores) is
precipitated by adding a little zinc dust.
The clear ZnSO4 solution is electrolyzed to recover zinc which is at least 99.95% pure.
(b) Reduction of ZnO with carbon. In this procedure, a mixture of the oxide and coke is put in a retort and
heated externally with producer gas to a temperature of 1350oCwhen the zinc distills off. The disadvantage
of this method is that, reduction of the oxide does not start until a temperature of 900oC is reached .

2ZnO(s) + C (s) 1350oC Zn(g)+ CO(g)

Cadmium occurs together with Zinc. Hence, when the ZnO is dissolved in dilute sulphuric acid, both ZnSO4
and CdSO4 are formed . Treatment of this solution with zinc dist precipitates any cadmium present

CdSO4 + Zn Cd + ZnSO4

Mercury is extracted as follows:-

The sulphide ore is concentrated by flotation . It is then roasted in a current of air at 600oC when mercury
distills off .

HgS(s)+O2(g) 600oC Δ Hg(g) + SO2(g)

Alternatively, mercury may be recovered by roasting the sulphide with either scrap iron or lime.

HgS(s) +Fe(s) Δ Hg (g) + FeS(s)

37
Halides : The three elements react directly with the halogens to form the halides MX2 (X=F,Cl, Br, I) .
These are listed in 5.2 below . In addition, mercury reacts with limited amounts of chlorine, bromine and
iodine to form mercurous halides, Hg2X2.These are listed in Table 5.3 below.

Table5.2. The Halides of the type, MX2, of Group12 Elements .

Halide Mpt oC. Bpt oC.

ZnF2 872 1500
ZnCl2 283 732
ZnBr2 494 650
ZnI2 446 624
CdF2 1100 1758
CdCl2 568 960
CdBr2 567 863
CdI2 387 796
HgF2 645 650
HgCl2 276 302
HgBr2 236 322
HgI2 259 354

Two notable features of mercury(I) halides are their thermal instability and very low solubility in water. In
fact, one of qualitative tests for possible presence of mercury(I) ions is formation of a white precipitate
when dilute chloride solution is added to a solution . We stress here, “possible presence since other ions like
Ag(I) and lead(II) also give white precipitates and a confirmatory test must be carried out to ascertain
which ions are actually present .Mercury(I) halides contain the dimercury cation, [Hg-Hg]2,and not just
Hg+.

Table5.3. mercurous halides, Hg2X2 .

Compound MPt(oC) BPt(oC) Sol. Per100g H2O at temp. shown

Hg2F2 570 Dec Dec to Hg2O
Hg2Cl2 Sub 400 0.00020(25)
Hg2Br2 Sub345 0.15 (25)
Hg2I2 Sub40 Dec Very slightly soluble.

Oxides . All the three elements form the oxides, MO. These and their properties are listed in Table5.4

38
Table5.4 The Oxides of Group12 Elements
Compound MPtoC MPtoC
ZnO 1975
CdO 1500 1559(dec)
HgO 500 dec
Hg2O 100 dec

In addition to the M(II) oxide, mercury also forms the M(I) oxide. As can be seen from the table, this is also
thermally rather unstable.
Salts of Oxo anions . Zinc and cadmium react readily with dilute and concentrated nitric and sulphuric
acids to form the salts, MSO4.xH2O. Here x is the number of molecules of water of crystallization, usually 6.
Mercury is not, however, attacked by
cold non- oxidizing acids at ordinary temperature. It is ,however, attacked by hot concentrated sulphuric
acid to give mercuric sulphate if acid is in excess or mercurous sulphate if mercury is in excess .

Hg+ 2H2SO4 = HgSO4 + SO2 + 2H2O

2Hg+ 2H2SO4 = Hg2SO4 + SO2 + 2H2O2

Sulphides. As noted earlier, group 12 elements as found in their minerals as the sulphides, MS . Mercury
has a particularly high affinity for sulphur . Thus , if mercury is spilled accidentally, it is removed very
readily by putting a powder of sulphur on the floor. This very high affinity for sulphur by mercury partly
explains why mercury is so poisonous .. It will readily remove sulphur from essential amino acids like
methionine which is part of enzymes, thus denaturing them.
Organometallics. Historically, organozinc compounds are of particular interest since they were the first
organometallic compounds to be prepared by Frankland in 1849. Mercury forms unusually strong Hg-C
bonds with the methyl group to form the extremely toxic methyl mercury cation, [Hg-CH3]+. Removal of
the methyl groups from Vitamin B12, which is essential for formation of C-C bonds and prevention of
pernacious anaemia makes mercury poisoning very dangerous .

Preparation: The zinc alkyls, R2Zn, are prepared by the reaction of alkyl iodide with a Zn-Cu couple
followed by thermal decomposition of the product.

2RI+Zn(Cu) Δ R2Zn + Zn I2

The zinc alkyls and the corresponding aryls are also readily prepared from the corresponding
organomercury, organolithium and organomagnesium compounds. .

Eg. R2Hg + Zn Δ R2Zn + Hg

Organocadmium. Compounds : These are best prepared from a reaction of anhydrous halide with either,
organolithium or organomagnesium compounds.

39
 2RLi + CdX2 (X= Cl, Br, I) Δ R2Cd + 2LiX
Organomercury Compounds: These of the types, R2Hg and RHgX(X=Cl, Br, I). The main use of
organomercury compounds is in preparation of other organometallics .
Amalgams. These are compounds formed between mercury and other metals, eg, zinc amalgam, sodium
amalgam, silver amalgam, gold, amalgam, etc. The ease with which mercury forms alloys with other metals
makes it valuable in gold extraction . Thus, when powdered silicate rocks are rubbed with mercury, the
gold or any silver present combines with the mercury. When this is distilled, the mercury is converted to
vapour leaving the gold(or silver) behind.

40
CHAPTER 6 GROUP13 ELEMENTS Section A Boron.

Introduction . Boron is the first member of Group13 and occurs in many minerals among them the
following :- Colemanite ,Ca2B6O11 ,5H2O, Kernite, Na2B11O7 ,4H2O,
Datolite, Ca(OH)SiO4 , and Tourmaline, M7Al6(OH,F)4(BO3)3Si6O18 . In the last example, M represents
varying amounts of Lithium , Sodium, Potassium, iron, magnesium, manganese or calcium. Boron,which is
a typical non-metal , is diagonally related to silicon .The two form acidic oxides , B2O3 and SiO2,
respectively , which are hard to crystallize . when these oxides are melted with metal oxides , they form
form glasses. A glass is a solid in which the constituent cations and anions occur randomly within the
lattice ( unlike a crystal where such ions occur in regularly repeating patterns) , is hard to crystallize and
does not have a definite melting point .

Preparation . Elemental boron is obtained in several ways.

( 1 ) Reduction of the oxide with electropositive Metals.

B2O3+ 3Mg ( heat) 2B + 3MgO

Other electropositive metals that have been used are Li, Na, K, Be, Ca,Al, and Fe but the product is
generally armophous and usually contaminated with refractory impurities such as metal borides. .
( 2 ) Reduction of a halide with zinc.

E.g 2BCl3+ 3Zn ( heat to 900oC) 2B + 3ZnCl2. The product obtained in this procedure

way is about 96% pure.

( 3 ) Electrolytic Reduction of molten borates or tetrafluoroborates such as KBF4 in molten KCl/KF
mixture at 800oC.
The product obtained is 95% powdered boron. .
( 4 ) Reduction of volatile boron compound with hydrogen.
E.g 2BX +H2 900oC) 2B + HX ( X=Cl , Br, I) . The product obtained from this reaction
is over 99.9% pure .

( 5) Thermal decomposition of boron halides or hydrides. hydrogen.

E.g Borane 900oC B + H2. . borides hydrides, halides, oxo-species and --n ( heat
o
to 900 C MgO
Types of Boron Compounds.
There are five types of boron compounds namely:- (a ) Oxo compounds (b ) Halides and their adducts( c )
Hydrides and their derivat (d) Metal borides ives
( e ) Organoboron and B-N Compounds .
(a) Oxides .and Oxo -species
The main oxide of boron is , B2O3 . It is acidic . It is obtained either by fusing boric acid, B(OH)3 , or
by burning boron in excess air.

Condensed Oxo Species of Boron

In boron oxo species, the boron may have a co-ordination number three where it has a trigonal planar
structure E.g as in structure Ia in Figure 6. Ia below or the tetrahedral structure as in 6.1b,

41
 -3 -5

O O
O
B B
O O
O O

Fig. 6.1a Fig. 6.1b

In this respect, boron differs from the diagonally related silicon in that, all oxo species of silicon contain
the tetrahedral anion, [SiO4]4-,. Boron , like silicon has a high tendency to form condensed oxo species .
For example, the anion, [B3O6]3- present in K3B3O6 contains the rings shown in Fig.6.2

Fig.6.2
B
O O

B B
O O
O . The apparently simple anion , [B2O4]3- , present in CaB2O4 contains oxo
chains of the type shown figure6.3

O O O

42
 B B

O O Fig.6..3

Fig.6..4
O

O B O

O B O
O B

O B O

The anion, [B4O9]6- (fig.6.4 ) contains both trigonally and tetrahedrally co -ordinated borons.
Titration of Boric acid:
Boric acid is an extremely weak acid which ionizes to a very small extent .

Thus, [B(OH)3H2O] + H2O = [B(OH)4]- + H3O+ Ka= 6x10-10

For this reason, there is no definite end point when the acid is titrated with a strong base such as sodium
hydroxide . It behaves as a typical Lewis acid so that, the proton consumed during the titration does not
come from one of the OH groups but rather from water. This can be verified readily by using isotopic

43
labelling. For example, if a sample prepared using deuterated boric acid is titrated with sodium hydroxide,
no deuterium is found in the water after the titration. i.e
B(OD)3 + H2O = B(OD)3 H2O
B(OD)3 H2O + H2O = [B(OD)3 OH]- + [OH3]+

NaOH(aq ) + [B(OD)3 OH] (aq ) - + [OH3] (aq ) + . = NaB(OD)3 OH](aq) + 2H2O(l)

- -

O O

H2C CH2

H3O+

H2C CH2

O O

Figure 6.5 Anionic species formed on addition of mannitol to boric acid.

B(OD)3 H2O + H2O = [B(OD)3 OH]- + [OH3]+ .

NaOH(aq ) + [B(OD)3 OH] (aq ) - + [OH3] (aq ) + . = NaB(OD)3 OH](aq) + 2H2O(l)

If the acid is treated with a polyhydroxyl compound such as mannitol, before the titration, it behaves like a
strong acid and has a very definite end-point. The reason is that the acid forms a very stable anionic chelate
(fig 6.5) complex leaving the proton very loose.

44
HALIDES. Boron reacts with all halogens to form the halides,BX3 (X=F,Cl, Br, I) . These halides and some
of their properties are summarized in Table 6.1

Halide MPtoC BPtoC r(B-X) bond ΔHf(kJ/Mole)

length(p)
BF3 -127.1 -101 130 -1123
BCl3 -107.3 12.5 175 -408
BBr3 -46 91.3 187 -208
BI3 49.9 210 210 …

It should be noted that , whereas all the halides are formed from the reaction of the elements , many are
prepared using indirect methods. For example, BF3 is prepared from a reaction of the oxide, B2O3, with
NH4BF4 or CaF2. BF3 is normally available as the ethereate, Et2O.BF3 . It reacts with water to form two
very stable hydrates, BF3.H2O(mpt, 10.2oC) and BF3.22O(mpt, 6.4.2oC). In solution, Both are ionized to form
the species [H3O-BF3]+, [BF3(OH)]-, [H3O]+,[ BF3OH]+. BBr3 and BCl3 are prepared on a commercial scale
by halogenation of the oxide in presence of carbon at 500oC.

B2O3+ 3C +3X2 500oC 2BX3 +3CO (X=Cl, Br).

The trihalides BX3 (X=Cl, Br, I) are typical covalent molecules which are violently hydrolyzed by water .

BX3 +3H2O B(OH)3+3HX. In this respect, BF3not hydrolyzed so violently

because of a very strong B--F bond. The four trihalides are typical Lewis acids.
The B2X4 Halides. All of these halides are known. The best studied is B2Cl4
and is prepared by passing BCl3 vapours on mercury or copper discharge.

2BCl3+2Cu B2Cl4 +2CuCl

Like the trihalides, the B(II) halideshydrides are readily hydrolyzed.

Borides. These are compounds formed between boron and other elements, but mainly the metallic elements.

Preparation : There are several methods available foe preparation of borides. These include the
following:-

(a) Direct reaction between boron and the metal at high temperature.

E.g nCr + nB 1150oC CrBn

(b) Reduction of boric acid with carbon .

B2O3 +C 1600oC B4C + CO .

45
 Boron carbide, B4C is , itself. a very useful reagent for preparation of metal carbides by reducing the
metal oxides in the temperature , 1500-2000oC. E.g .

V2O5+ B2O3 +8C 1500oC 2VB +8 CO

Eu2O5+ 3B4C3 1600oC 2EuB6 +3 CO

7Ti + B2O5+ 4B4C3 2000oC 7TiB2 +3 CO

Boron carbide is very useful economically, because, besides being a good source of boron in preparation
of metal borides, it is used as a brake lining for cars. Secondly, the fibers are used to make bullet-proof
vests.
Structure of Metal Borides. Many borides have stoichiometries like
M2B, MB, MB2, MB4 , M4B, M3B2, M7B3, M3B4 , MB6 and others which tell us very little about the
actual structures of these compounds. Borides are interstitial compounds in which, the structure of
elemental boron is retained to a large extent with the incoming atoms spread in some spaces ,sometimes
regularly but in others not so regularly. Consider , as an example , the structure of CaB6. Broadly
speaking, this may be considered like the cesium chloride structure with Ca at the center of a cube where at
the corners of the cube are octahedral clusters of boron.

46
 = Ca

= Boron octahedral Cluster

Figure 6.6 An example of interstitial Structure

in Borides.

Hydrides. Boron hydrides are called boranes. An important characteristic of boranes is that they are
electron-deficient . Thus, although from the electron cofiguration of boron which is [He]2s22p1, one might
expect simple compounds like BH3., the simplest stable borane is B2H6 which has the structure; .

Figure 6.7 Diborane

H
H H

B B

H H H

47
Preparation. During the period, 1912-1936, Alfred Stock and his co-workers obtained boranes such as
B4H10 ,, B5H9 , B5H11 , B6H10 and B10H14 by action of acid on magnesium boride, MgB2. Diborane, B2H6 ,
was obtained from thermal decomposition of the higher boranes. BH3 is unstable and can only be
obtained in the gas phase by thermal decomposition of borane complexes or higher boranes .

E.g BH3PF3 Heat BH3 + PF3

Nowadays , numerous methods of preparing boranes are .known . For example , diborane is obtained
conveniently from the following reactions:-
(a) NaH + B(OCH3)3 heat( 225-275oC) = NaBH4 +3NaOCH3
( b )NaBH4 +4BF3 = 2NaBF4 + 2B2H6

NOMENCLATURE In naming boranes , the number of boron atoms is cited first and the number of
hydrogen atoms is given in parenthesis.
Table6.2 Examples of How boranes are named.
Borane Name
B2H6 Diborane(6)
B4H10 Tetraborane(10)
B5H11 Pentaborane(11)
B5H9 Pentaborane(9)
B10H12 Decaborane(12)

THE TETRAHYDRIDO SPECIES , BORATE ION, [MH4]-

( M= B , AL, GA, IN, TL) .

The tetrahydrido species [MH4]- ( M= B , Al, Ga, In, Tl) are

all reducing agents . .From a practical point of view , [BH4]- and [AlH4]- are by far the most important.
Lithium aluminium hydride , Li[AlH4] .
Lithium aluminium hydride , is a versatile reducing and hydrogenating reagent in preparation of both
organic and inorganic compounds. It is a white crystalline solid which is stable in dry air but
decomposed very violently even by any traces of moisture. The reactions must, therefore , be carried
out in rigorously anhydrous conditions .

Preparation : Reaction of Lithium hydride, LiH , with Aluminium(III) halide in ether .

3LiH + 4AlCl3 LiAlH4 + 3LiCl

Et2O

Carbaboranes. These are boranes in which, one or more BH2 units have been replaced with carbon.

48
GROUP13. Section B Aluminium,Gallium , Indium and Thallium.

Table6.3 Some properties of the heavy Group 13 elements.

Element Electron Config. MptoC BptoC

Al [Ne]3S23p1 663.37 2467
10 2 1
Ga [Ar]3d 4S 4p 29.8 2403
In [Kr]4d105S25p1 156.61 2080
Tl [Xe] 4f145d106S26p1 303.5 1457
Occurrence. Aluminium is a constituent of all clay minerals. Consequently, in addition to a few non-clay
minerals such as bauxite Al O (OH) and Cryolite, Na3AlF6 , aluminium is found in literally hundreds of
minerals. Some examples of these are,
Alunite , KAl 5(OH)6 (SO4)2 ; Andalusite ;Al 2OSiO4 ; Beryl , Be 5Al2 Si6O18
; Corundum , Al2O3 Cryolite , Na3AlF6 Dumortierite , Al8B(OH)Si3O19 .
Feldspars ,e.g.Orthoclase , KAlSi3O8 , Anorthite , CaAl2Si2O8
Garnets …. M2+M3+ (SiO4) ( M2+ = Ca2+ , Mg2+ , Fe2+ , Mn2+ ; M3+ =Al3+, Fe3+, Cr3+ )
Kaolinite, Al4(OH)8Si4O10 . Kyanite, Al2OSiO4 .Leuciteaolinite, K(AlSi2O6). Nepheline , Na(AlSiO4).
Scapolite, nNa4Cl(AlSi3O8)3+ m Ca4CO3(Ali2Si2O18)3
Sillimanite , Al2OSiO4. Spodumene , LiAlSi2O6. Spinnels ,e.g MgAl2SiO4.
Staurolite Fe(OH)2.2Al2OSiO4 ;Topaz , Al2(F,OH)2SiO4.; Zeolites eg.Na2Al2Si3O10.2H2O.
Gallium, indium and thallium occur as impurities in other major minerals. Eg. Gallium is found as an
impurity in aluminium minerals such as bauxite. Indium is usually found in association with zinc minerals.
Thallium is found in clay minerals and also in pyrites.
Preparation:- Aluminium metal is obtained by electrolysis of molten cryolite, . Na3F6. Naturally-
occurring cryolite is rare and practically all cryolite used for extraction of aluminium nowadays is
synthetic using either bauxite or enriched clays . There are two stages .
First stage : Bauxite is treated with sodium hydroxide to form sodium aluminate.

AlOOH + NaOH = NaAlO2 +H2O ..

Second Stage Dissolution of sodium aluminate in hydrogen fluoride to produce synthetic cryolite and
more aluminium hydroxide .

6HF + 3 NaAlO2 = Na3AlF6. + 3H2O + Al2O3.

Cryolite is also produced by the reaction of Na2O with AlF3 . Na2O is produced in the cells once the
reaction is in progress.

Chemical Reactivity Aluminium and gallium are amphoteric and react with both acids and bases.
Reaction with bases :
2M + 2NaOH = 2NaAlO2+ 3H2 ( M=Al, Ga)

Oxides: Table 6.4 gives some properties of the oxides, M2O3.

49
Table 6.4 some properties of the oxides, M2O3

Oxide MPtoC BPtoC

Al2O3 2072 2980
Ga2O3 1900 …
In2O3 850(volatilizes)
Tl2O3 717 Decomposes.875

Thallium forms the oxide, Tl2O with a melting point of 300oC and decomposing around 1080oC. Note :- (i )
the extremely high melting and boiling points of the aluminium oxide. (ii ) The decrease in stability of
oxidation state +3 for the element in the 6th period . This tread is also observed among the halides.
Halides . There are three types of halides namely, the trihalides, MX3. the monohalides, and the dihalides.
The MX3 and some of their properties are listed in Table 6.5 .

Table 6.5 Some properties of the Halides, MX3 (MPt and BPt in oC )

Element Fluorides Chlorides Bromides Iodides

Al Mpt 1291(sub) Mpt 190(2. 5at) Mpt 97.5) Mpt 191
BPt BPt 262 (dec) BPt 263.3 BPt 360
Ga Mpt 800 Mpt 77.9 Mpt 121.5 Mpt 212
BPt ca 1000 BPt 201.3 BPt 278.8 BPt 345
In Mpt 1170 Mpt 586 sub Mpt 436 Mpt 210
BPt >1200 BPt 600 volat BPt sub BPt

Some of the Group 13 elements form stable monohalides, MX. These are listed in table 6.6.

Table 6.6 Some properties of the Halides, MX (MPt and BPt in oC )

Element Fluorides Chlorides Bromides Iodides

Al Unstable Unstable Unstable Unstable
Ga Unstable Unstable Unstable Unstable
In Mpt 225
BPt 608
Tl Mpt 327 Mpt 430 Mpt 480 Mpt 440
BPt 655 BPt 720 BPt 815 BPt 823

50
It should be noted that both gallium and indium also form stable dihalides , MX2,which should be
formulated as M2X4 as they have the structure, X2M-MX2 .

Ga2Cl4 ( Mpt, (164oC, 535oC) , In2Cl4 ( Mpt, (235oC, 550-570 oC) ,

Aluminium and Gallium halides are typical Lewis acids , but with aluminium showing much greater
acidity. For example , in the gas phase, they exist as the dimeric species M2X6 shown in figure 6.6 below.

X X X

M M

X X X

Figure6.6 The Dimeric M2X6 ( M=Al, Ga ; X= Cl, Br, I ) in the gas phase.

When dissolved in water, they form the hexaaqua ions, [M(H2O)6]3+ ,. Aluminium salts eg.
Al2(SO4)3.12H2O , are acidic due extensive hydrolysis of the [Al(H2O)6]3+ ions .

[Al(H2O)6]3+ + H2O = [Al(H2O)5 (OH-) ]2+ + [H3O]+

Organometallics.

Preparation Aluminium alkyls, AlR3,may be prepared by the general reaction:-

2Al + 3RCl trace of I2 ¼ R4Al2Cl2 + R2Al2 Cl4

Addition of NaCl removes R2 Al2Cl4 from the reaction mixture . R2Al2 Cl4 is distilled off and reacted with
sodium metal to give AlR3 .These species are , like the halides, dimeric .
Alkyl compounds of aluminium adopt a similar structure .

The aluminium alkyls, AlR3 , react with early transition halides like TiCl4, to form alkyl halides, e.g
TiCl2R, which catalyze polymerization of olefins to long chain polymers.

51
CHAPTER7 GROUP14 ELEMENTS.. Carbon, Silicon, Germanium, Tin, Lead.

52
 Section A. Carbon
Occurrence ; carbon occurs in elemental form as Graphite and Diamond . In 1985, it was shown
that elemental carbon can exist in clusters such as C60, C70, C44, C90, etc called Fullerenes .
12 13
Carbon has two stable isotopes Isotopes C------98.89%, C---1.11%.

Allotropes, Graphite . This occurs as hexagonal sheets.

Diamond . The atoms are bonded tetragonally to form giant three-dimensional
structure.

Recent studies have shown that carbon also occurs in clusters such as ,as C60 , C40 , C60, C80, C76 , C84,etc.

Table 7.1 Some general properties of the elements .

Element C Si Ge Sn Pb

Property

Electron Config. [ He]2s22p2 [ Ne]3s23p2 [ Ar]3d104s24p2 [ Kr]4d105s25p2 [Xe]4f145d106s26p2

Mpt(oC) >3550 1410 937 231.9 237.5
Bpt(oC) 4827 2355 2830 2260 1744
Electronegativity 2.5 1.8-1.9 1.8-1.9 1.8-1.9 1.8
Cav. Radius(pm) 77 117 122 140 144

Carbon is a typical none- metal with the unusual property of forming C-C bonds in very long chains , a
property known as catenation . Catenation occurs in elements like sulphur or silicon but to a much
smaller extent . The very extensive catenation in carbon compounds is probably due to the formation of
very strong C-C single bonds of kJ/ mole. Compounds with long chains of carbons containing hydrogen ,
and in some cases also oxygen , nitrogen , halogens and phosphorus belong to the area of chemistry called
Organic Chemistry and will not be considered any further .

Some Inorganic Compounds of Carbon.

Alkali Metal and Alkali Earth carbides. The alkali metals and alkali earths react with acetylene to form
ionic carbides which react with water to give acetylene. As noted earlier, both lithium and sodium react
with carbon to form acetylides . An acetylide will also be formed when calcium oxide and carbon are heated
together at a temperature of 2000oC in an electric furnace.
Cyanamide. Formed when calcium carbide is heated in an atmosphere of N2 at 1000oC.See chapter 4.

Carbon Monoxide , CO . Carbon monoxide is formed is several reactions. E.g when carbon is burnt in
limited amount of oxygen,

2C+O2 Δ 2CO .
or when steam is passed over white hot carbon:

53
 C +H2O Δ CO+ H2

Carbon monoxide and the cyanide ion are isoelectronic. Both are very important ligands ie form stable
complexes with transition metal ions .Thus, formation of a very stable complex with the iron of hemoglobin
makes both the cyanide and carbon monoxide extremely poisonous because both combine with
haemoglobin irreversibly, thus rendering the haemoglobin unable to hold oxygen for transportation to the
tissues. Carbon monoxide is particularly dangerous because it has no smell . During the cold weather ,
people make charcoal in buildings with very poor venetrations and can breath large amounts of the gas
without realizing.

Carbon Dioxide , CO2 . Carbon Dioxide is formed when carbon or any carbon-containing materials are
burnt in excess oxygen . It is a linear molecule with the structure,

O=C=O
It has no liquid range under ordinary conditions of temperature and pressure but rather sublimes at –78oC.
Solid carbon dioxide blocks are very convenient in keeping ice cold on hot days. Carbon dioxide dissolves
in water to form carbonic acid which is only weakly ionized;

H2O+CO2 = H2CO3 ; H2CO3 + H2O = [H3O]+ + [HCO3]- . K1=4.16x10-7.

The second acid dissociation constant is four orders of magnitude lower, K2=4.84x10-11.

Section B. Silicon.

Silicon : Silicon is the second most abundant element in the earth’s crust after oxygen ( 27.2%) .It occurs in
literally hundreds of minerals and the following are only representative examples: Silica, SiO2 ; quartz ; all
clay minerals e.g Dumortierite , Al8B(OH)Si3O19 ; the feldspars ,e.g.Orthoclase , KAlSi3O8 ; Anorthite ,
CaAl2Si2O8 ; the garnets , M2+M3+ (SiO4) ( M2+ = Ca2+ , Mg2+ , Fe2+ , Mn2+ ; M3+ =Al3+, Fe3+, Cr3+ )
;Kaolinite, Al4(OH)8Si4O10 ;Kyanite, Al2OSiO4 .Leuciteaolinite, K(AlSi2O6), Nepheline ,
Na(AlSiO4).;Scapolite, nNa4Cl(AlSi3O8)3+ m Ca4CO3(Ali2Si2O18)3 Sillimanite , Al2OSiO4 , Spodumene ,
LiAlSi2O6 ,;The Spinnels ,e.g MgAl2SiO4 ; Staurolite Fe(OH)2.2Al2OSiO4 ; Topaz , Al2(F,OH)2SiO4 ;
Zeolites e.g. Na2Al2Si3O10.2H2O

Preparation : Elemental silicon can be prepared by one of several methods:

(a) Quartz or sand is reduced with high purity coke in an electric furnace in the temperature rnge
2000-2500oC. Excess sand is used to avoid formation of silicon carbide ( carborundum)

SiO2+2C = Si+2CO
2SiC +SiO2 = 3Si+2CO.

Oxygen compounds. Silicon reacts with oxygen to form silicon dioxide, SiO2, as the only stable oxide at
ordinary conditions of temperature and pressure. Silicon dioxide exists in different is crystalline forms e.g

54
cristobalite (mpt 1703oC , bpt,2230 oC ) , quartz(mpt 1610oC , bpt,2230 oC ), and tridymite, (mpt 1703oC ,
bpt,2230 oC ) .
The reason for the very high melting and boiling points is that in these crystals each silicon atom is at the
center of a regular tetrahedron with oxygens at the corners .Furthermore, this extends in the three
dimensions .Thus, we see SiO4 units extending in all dimensions. Such a lattice is extremely difficult to
break . Hence, reason for very high melting and boiling points. It is worthy noting at this point that in all
oxygen-containing silicon compounds , the silicon atom is always in oxidation state +4 and is at the center
of a regular tetrahedron with four oxygens at the corners i.e the units SiO4 are present.
An aspect of the chemistry of silicon is in formation of condensed oxo species referred when considering
the chemistry of boron.
Discrete Species . [SiO4]4 - . Discrete anions , [SiO4]4 , occur in the minerals, phenacite, Be2SiO4, and
willemite, Zn2SiO4

Condensed Silicate Anions.

1. The Disilicate anion, [Si2O7]6-

The simplest condensed silicate anion is Ciscrete Species . [Si2O7]6- such as found in the zinc mineral
hemimorphite, Zn4(OH)2Si2O7 , or the scandium mineral thortveitite, Sc2Si2O7 . The disilicate anion has two
tetrahera sharing a corner. The silicons are at the center of the tetrahedron and the oxygens are at the
corners.

Figure 7.1 A disilicate anion

2. The Trisilicate anion, [Si3O9]6- . The trisilicate anion, , isfound in the mineral benitoite, BaTiSi3O9.
It has cyclic structure with three tetrahedral sharing corners.

Figure 7.2 A trisilicate anion

3. The hexasilicate anion, [Si6O18]6- .

Another discrete cyclic anion is one with six tetrahedral sharing the corners.

55
 Figure 7.3 A hexasilicate anion

Infinite Chains . Many condensed silicate anions form long chains . Two principle types are :- ( i ) The
pyroxenes . These form sinlge single strands as showm in figure

Figure 7.4 A pyroxene chain.

( ii ) The Amphiboles. These contain double strands.

Infinite Sheet Anions . Many condensed silicate anions form two- dimensional infinite sheets.

Three Dimensional Framework Minerals. There are silicate minerals which form a three dimensional
framework e.g the felsdpars, zeolites and ultramarines fall in this class.

Halides Silicon reacts with all the halogens to form the tetrahalides, SiX4 ( X=F, Cl, Br, I) covalent.
These are typical covalent molecules which readily take up extra halogen ions to form the octahedral
anions [SiX6 ]2- and are readily hydrolyzed by water to form SiO2 and the hydrogen halide , HX.
E.g SiCl4+4H2O SiO2 + 4HCl
The tetrahalides of silicon and some of their properties are listed in Table7.2 below.
Table 7.2a The tetrahalides of silicon and some of their properties.
Halide Mpt(oC) Bpt(oC)
SiF4 -90.2 -86
SiCl4 -70 57.57
SiBr4 5.4 154
SiI4 120.5 287.5

In addition to the tetrahalides, silicon also forms other halides eg. those given in Table 7.2b
Halide MPt oC BPt oC
Si2F6 -18.7 -18.5

56
Si2Cl6 -1 145(760)
Si2Br6 95 240
Si2I6 250(dec)
Furthermore , preparative as the following examples show, the preparative routes vary ry widely .

Si+ SiCl4 red heat Si2Cl6 + higher homologs

Si2Cl6+ZnF2 Si2F6+ ZnF2

5Si2Cl6+ heat with 0.1% Nme3 Si6F14+ 4SiCl4

3Si2Cl6+ 0.1% Nme3 catalyst Si5F12+ 2Si2Cl6

HYDRIDES . Owing to the possibility of catenation, silicon forms many linear and branched hydrides,
called silanes , similar to those of carbon but with carbon replaced by silicon. Silines of the type, SinH2n+2
for n up to 8 for branched and linear species are known. A notable difference between silanes and
corresponding carbon compounds is in their thermal stabilities .Silanes are thermodynamically far less
stable than corresponding carbon compounds. Thus, they readily catch fire if exposed to air, a big contrast
to analogous carbon compounds which are indefinitely stable in air unless ignited deliberately. Table 7.3
gives some properties of a few silanes

Table 7.3. Some hydrides of silicon.

Property SiH4 Si2H6 Si3H8 n-Si4H10 i-Si4H10
MptoC -185 -132.5 117.2 -89.9 -99.1
o
Bpt C) -111.8 -14.3 53.1 108 101
Density(ToC 0.68(-186oC) 0.686(-25oC) 0.725(0oC) 0.825(0oC) -----

Preparation. There are three general methods for preparation of silanes;

( i ) Acid hydrolysis of metal silicide.
(ii ) Treatment of halide, eg. SiX4 (X= Cl, Br) with a metal hydride like NaH or complex metal hydride ,
e.g LiAlH4.,
(iii ) Direct reaction of HX or RX with Si or ferrosilicon in presence of catalyst such as Cu.

Section C. Germanium, Tin, Lead

OCCURRENCE AND METALURGY

Germanium : Germanium is found as an impurity in other minerals. Eg, it is found as a component of the
mineral, argyrodite, 4Ag2SFeS2 . The mineral germanite, 3Cu2.FeS2 . contains up to 8% germanium. Its
recovery is rather complex mainly because of its amphoteric nature , like zinc.Eg. leaching with H2SO4
followed by addition of sodium hydroxide precipitates the two elements as GeO2 and Zn(OH)2 in the when
the pH range 4 to 5.5. When this mixture is heated with in a current of HCl/Cl2 , germanium is volatilized
as GeCl4 ( MPt,-49.5 oC , BPt 83.1oC) leaving behind ZnCl2 ( MPt 283oC BPt 732oC)

57
Tin : The main mineral of tin is casterite , SnO2 , otherwise called tinstone . The naturally-occurring tin
ores contain very low concentration of the ore( 0.2-2% ). Ore concentration is, therefore , necessary before
the tin is extracted. .The concentrated ore, containing bout70% casterite is reduced with carbon in a
reverberatory furnace at about 1200-1300oC. A little limestone and fluospar( CaF2) are added to act as a
flux.

SnO2 + 2C Δ Sn +2CO

Lead Lead occurs in many minerals among them the following:- Anglesite, PbSO4 ,
Bournonite, PbCuSbS3 ,Cerussite, PbCO3 Crocoite, PbCrO4 , Galena, PbS;
Pyromorphite, Pb5,Cl(PO4)2
Vanadinite, Pb5,Cl(VO4)2 , Wulfenite, PbMoO4
Metallurgy . Galena is by far the most important mineral of lead . Low grade lead ores are first
concentrated by froth-floatation .The concentrated material is roasted in limited amount of air to form
lead(II) oxide, PbO . The lead oxide thus obtained is then reduced with carbon when the following
reactions take place :-

2PbS(s)+ 3O2(g)  2PbO(s) + 2SO2(g)

PbO(s) + 3C(s)  2Pb (l) + CO(g)

PbO + CO  2Pb + CO2

Alternatively, lead metal may be prepared as follows:-

Low silica content (i.e less than 5% ) ores with at least 70% lead are processed by heating either mixture
of the ore with lead oxide or with the mineral, anglesite, PbSO4 .

PS(s) + 2PbO(s)  3Pb (l) + SO2 (g)

PbS(s) + 2PbSO4 (s)  2Pb (l) + 2SO2(g) .

As these reactions are endothermic , the reduction must be carried out at a temperature of 750oC or
higher.

Table 7.4. The Tetrahalides of Germanium, tin and Leadand some of their properties.

The Tetrahalides MX4(X=F, Cl, Br, I) .

Element Fluoride Chloride Bromide Iodide

Ge MptoC -15(4atm) MptoC –49.5 MptoC 26.1 MptoC 144
BptoC-36.5(sub) BptoC 83.1 BptoC186.5 BptoC 440(dec)
Sn MptoC ---- MptoC –33.3 MptoC 31 MptoC 144
BptoC 705 BptoC 144 BptoC 205 BptoC 348

58
Pb MptoC 600 MptoC -15
BptoC BptoC 105(dec)

Oxides. Germanium, tin and lead form two series of oxides namely, those of the M(II ) and those of M(IV)
ions, i.e GeO, SnO and PbO on the one hand and , GeO2, SnO2 and PbO2.
Preparation : MO(M=Ge, Sn, Pb) Oxides.

The monoxides, MO (M=Ge, Sn, Pb) are formed when these elements react with limited amount of air.
They are also formed from thermal decomposition of the hydroxides, M(OH)2 , or the carbonates, MCO3.
Their Mpts and Boiling points are summarized in Table7.5 below .

Table7.5 The mon-oxides of Ge, Sn, and Pb.

Oxide MPt oC B Pt oC
GeO Sub 710 …
SnO Dec1080
PbO 886

M(IV) Oxides , MO2 (M=Ge,Sn, Pb)

All the oxides , MO2 (M=Ge,Sn, Pb) are known These are listed in Table7.6
Oxide MPt oC B Pt oC
GeO2 1150 ------
SnO2 1650 1800-1900(sub)
PbO2 290(dec)

The so-called red lead is really a mixture of lead(II) oxide, PbO , and lead (IV) oxide, PbO2 , in the ratio
2:1 i.e 2PbO,PbO2 .

Halides.
The dihalides , MX2 . All the MX2 ( M=Ge, Sn, Pb; X=F, Cl, Br, I) are all known. Both germanium and tin
form all the tetrahalides , MX4 . However, for lead, only PbF4 (mpt. 900oC ) is stable.The tetrachloride
,PbCl4 ( Mpt , -15 oC ) can be made but it is very unstable , decomposing explosively above above 50 oC .
PbBr4 is even less stable and PbI4 is not even known .
ORGANOMETALLICS . By far the most important organometallic compound of this group is
tetraethylead (TEL) , Pb(CH2CH3)4 because of its application as an antiknock agent in internal
combustion engines . When added to gasoline, the compound works as a negative catalyst in that it prevents
pre-ignition of the petroleum and thus allows for smooth burning of the fuel. Recent campaigns by
environmentalists will ,however , minimize the use of TEL in petroleum and most likely put it out of
market in the very near future, especially if an appropriate alternative is discovered.
Preparation: Several methods are available for preparation of TEL.

59
 (a) Reaction of an alkyl halide on sodium –

4Na +Pb  Na4Pb

Na4Pb + 4CH3CH2Cl  Pb(CH2CH3)4+ 4NaCl

Preparation using Grignard Reagent : The reaction of ethyl magnesium iodide , Mg CH2CH3)I , with lead
(II) chloride leads to formation of TEL

2PbCl2+M g CH2CH3)I  Pb + Pb(CH2CH3)4 + 2MgCl2 +2MgI2 .

It is believed that in this reaction , diethyl lead is formed first and then it disproportionates to elemental
lead and the product.

60
CHAPTER 8 GROUP15 ELEMENTS –

Section A Nitrogen

General Introduction: The atmospheric gases contain 78 % of Nitrogen by volume . In addition , all
animals dead or living and most plants contain nitrogen in a combined form eg as proteins or alkaloids. As
can be seen from Table below, nitrogen forms compounds in which oxidation states between –3 to +5 ,are
realized. In addition, there are compounds in which the element has fractional oxidation state, e.g , in
hydrazine, N3H , ( otherwise called hydrazoic acid) , the nitrogen has a formal oxidation state of -? .
Table 8.1 Some physical properties of Nitrogen:
Atomic Number …………………… 7
Electron Configuration : 1s22s22p3 or [He] 2s2
Melting Point (oC) -209.86
o
Boiling Point ( C) -195.8
Atomic Number, Z 7
Covalent Radius (pm) of N3- 171

Table 8.2 Some Hydrides of Nitrogen

Hydrides Name Mpt oC BptoC

N3H Hydrazoic acid -80 37

(Hydrogen azide)

NH3 Ammonia -77.7 –33.35

N2H4 Hydrazine 2 113..5

Ammonia ( NH3 ) . Ammonia is by far the single most important compound of nitrogen since it is a
primary chemical used for manufacture of other chemicals. Ammonia is actually the raw material used by
the plants to manufacture nitrogen-containing substances such as the proteins.
Preparation: We note here the preparation of ammonia. On a laboratory scale, ammonia is prepared by
treating an ammonium salt with a base e.g , when ammonium chloride is mixed with calcium hydroxide and
the solid mixture is warmed, ammonia gas is given off. The mixture may be heated dry or made slightly
damp.

2NH4Cl + Ca(OH)2 === CaCl2 + 2NH3

Another reaction that may give off ammonia is the hydrolysis of a nitride of a highly electropositive
metal, e.g magnesium nitride, Lithium nitride or calcium nitride.

Mg3N2 + 6H2O = 3Mg(OH)2 +2NH3

Ammonia is manufactured industrially in the Haber Process. In this process, a relatively pure mixture of
nitrogen and hydrogen in the molar ratio 2:3 is compressed to a pressure of 200-1000 atmospheres and high

61
temperature . in presence of an activated iron catalyst . Under these conditions, the two elements combine
to form ammonia. Although higher yields are got when the pressure is high, operating at very high pressures
makes the process very expensive. The equilibrium is favoured by low temperature but then, if the
temperature is too low , the reaction may not even take place . Whereas the ideal temperature is 450oC , in
practice, the operation is carried out in the temperature range, 400-500oC , usually at a pressure of 200-300
atmospheres. Ammonia has a pyramidal structure . It is a good σ-donor which readily replaces water
from many coordination complexes.
Eg. [Ni(H2O)6]2+ + 6NH3aq = [Ni(NH3)6]2+ +6H2O(l)

Hydrazine, N2H4, : Hydrazine is obtained by oxidizing ammonia with sodium hypochlorite, NaOCl.

2NH3 + NaOCl = N2H4 + NaCl +H2O .

It is a mild reducing agent. Eg. When an acidic solution of sodium molybdate to which some phosphate has
been added is mixed hydrazinium sulphte and the mixture warmed, characteristic blue of
molybdenum(V) is obtained . This is , indeed a standard analytical technique for determination of both
molybdenum and phosphorus.

Hydrogen azide) N3H ( Hydrazoic acid ) .

Preparation Many oxidizing agents can be used to oxidize hydrazine to hydrogen azide, otherwise called
hydrazoic acid . These include nitric acid, nitrous acid, hydrogen peroxide, chlorate etc. The acid was
prepared by Curtis in 1890 by the reaction:-

[ N2H5]+ + HNO2 ) N3H + H+ + 2H2O .

The alkali metal salts of hydrogen azide are reasonably stable thermally. For example, sodium azide ,
NaN3 , is prepared by adding powdered sodium nitrate, NaNO3 , to molten sodium amide, NaNH2, at
175oC , or passing N2O to the same molten amide at 190oC when the following reactions take place:

NaNO3 +3NaNH2 = NaN3 + NaOH +NH3

N2O +2NaNH2 = NaN3 + NaOH +NH3

Heavy metal azides are deadly explosives .Their main application is as detonators. A particularly
important one is lead azide Pb(N3)2, because of its reliability even in damp conditions. It is prepared by a
metathesis reaction,

Pb(NO3)2 +2 NaN3 = 2 Na NO3 + Pb(N3)2,

.,

Halides: Nitrogen forms only halides of the type, NX3 and , among these, only the NF3 (MPt –206.6 oC,
BPt, -129oC) is reasonably stable. The chloride, NCl3 (MPt <–40 oC, BPt, <71oC , expl 95) is extremely
unstable . The bromide and the iodide are not stable chemical species.

62
 Oxides : The various oxides of nitrogen and some of their physical
properties are listed in Table 8.3.
Table 8.3 Oxides of Nitrogen .

Oxide Name Mpt oC. BPt oC

NO Nitric Oxide – 163.6 -158.1

N2O Nitrous Oxide – 90.8 -88. 5

N2O5 Nitric anhydride 30 d 47
NO2 (N2O4) Nitrogen dioxide -11.2 21.2
N2O3 Nitrous anhydride -102 d 3.5
NO3 Nitrogen trioxide …………………………………
Both nitric oxide and nitrogen dioxide are formed in the atmosphere during thunderstorms by the reactions,

N2+O2 High electric Discharge 2 NO .

The nitric oxide combines with more oxygen in the atmosphere to form Nitrogen dioxide, NO2..
2NO+O2 = 2NO2 . Nitric oxide reacts with the moisture in the atmosphere to form nitrous acid, HNO2
and nitrogen dioxide combines with moisture to form nitric acid. These acids make rain water acidic. Other
substances make pH of rain water are, (1) the carbon dioxide released into the atmosphere when wood or
charcoal burns or when animals breath out and (2) sulphur dioxide released into the atmosphere when any
materials of organic origin materials including unrefined petroleum burn.

Nitric acid On a laboratory scale, nitric acid is prepared by heating a nitrate with
sulphuric acid e.g

KNO3+ H2SO4 HNO3+KHSO4

Industrially, nitric acid is manufactured by catalytic oxidation of ammonia on platinum wire gauze( Oswald
Process)

4NH3+ 5O2 Pt 4NO+ 6H2O

It is necessary to heat the NH3/O2 gas mixture to initiate the process . However, once the reaction has
started, it is self-sustaining and no further heating is required.
Nitric oxide reacts with more oxygen in the air to form nitrogen di-oxide , NO 2. Nitrogen dioxide reacts
with water to form the nitric acid.

2NO2 + H2O = HNO3+ 6HNO2

Nitric acid is used for manufacture of nitro compounds .which are in turn converted to explosives e.g
TNT, Nitroglycerine, Potassium nitrate , etc . Organic nitro compounds are also reduced to amines which
serve as organic dyes .
Explosives like nitroglycerine are vital in mining and road construction (used to break rocks ).

63
AQUA REGIA: This is a mixture conc.HCl and conc. HNO3 in the ratio 3:1 is used for dissolving gold.
and platinum metals.
Section B Phosphorus, Arsenic, Antimony , Bismuth.

PHOSPHORUS
Occurrence , Phosphorus occurs in many minerals among them the following:- Amblygonite
,LiAl(F,OH)PO4 , Monazite , ( Ce, La)PO4 , Triphylite, Li(Fe,Mn)PO4
Fluoroapaptie , [3Ca3(PO4)2.Ca(F,Cl) 2] , Pyromorphite, Pb5Cl(PO4)2
Vivianite, Fe3(PO4)2.8H2O, Wavellite, Al3(OH)3(PO4)25H2O,
Turquois ,CuAl6(OH)8(PO4)4 4H2O.
Arsenic occurs in many sulphide minerals, the main one being the mineral , arsenopyrite, FeSAs
.Antimony occurs as a sulphide mineral, ,Sibnite Sb2S3
Bismuth may occur in elemental form, but again, this is mainly found as the sulphide mineral,
bismuthinite, ,Bi2S3 .
Preparation , Apatites serve as the principal source of phosphorus. The skeleton is mainly made of
hydroxy-apatite . Elemental phosphorus is recovered from the phosphate rock by heating a mixture of sand,
the ore and coke to a temperature of 1400-1500oC in an electric furnace.
2Ca3(PO4)2 +6SiO2+10C 1400 6CaSiO3 +10CO +P4
1500
Note : If one wishes to recover phosphorus(V) oxide rather than elemental phosphorus, then ,only a mixture
of the ore with sand is heated .

2Ca3(PO4)2 +6SiO2 1400 6CaSiO3 + +P4O10

It is widely believed that this is actually the first stage and this phosphorus(V) oxide is the one reduced by
carbon to get elemental phosphorus. Table 8.4 blow lists some properties of phosphorus, arsenic, antimony
and Bismuth.

Table 8.4 lists some properties of phosphorus, arsenic , antimony and Bismuth.

Element Symbol Atomic Ionic radius Electron configuration.

3-
No of X , pm
Phosphorus P 15 212 [Ne]3s23p3
Arsenic As 33 222 [Ar]3d104s24p3
Antimony Sb 51 222 [Kr]4d105s25p3
Bismuth Bi 83 ----- [Xe]4f145d106s26p3

SOME COMPOUNDS OF PHOSPHOUS, ARSENIC , ANTIMONY AND BISMUTH.

Table 8.5 gives the main type hydrides formed by the heavy Group 15 elements .

64
Table 8.5 Hydrides of phosphorus, arsenic, antimony and bismuth.

Hydrides Name MptoC BptoC

PH3 Phosphine –133 –87.7

P2H4 Diphosphine………………………………………….
AsH3 Arsine –116.3 –55(d)
SbH3 Stibine –88 –17.1(752)
BiH3 Bismuthine

Phosphine, PH3 , is obtained when metal hydrides are hydrolyzed with water.

Na3P+ 3H2O = PH3 + 3 NaOH

It is a deadly poison used for extermination of rodents . The material available commercially is actually zinc
phosphide.
The stability of group15 hydrides decreases down the group. Thus both arsine, AsH3 , and stibine , SbH3
, decompose when heated to deposit silver mirrors which are used as confirmation tests for the elements.
They are produced when solutions containing these elements are made slightly acidic with HCl and a little
zinc dust is added. When the gases are passed through a test tube being heated with a burnsen burner, stibine
, being very unstable decomposes on reaching the warm part of the tube even before it passes the flame.
Arsine is more stable and decomposes on passing the flame. This is the so-called Marsh Test for these
elements.
. Unlike ammonia, both phosphine and arsine are extremely poor σ-donors and hence do not form stable
complexes with metal ions. However, when the hydrogens are substituted with either alkyl or aryl groups
to form tertiary phosphines or tertiary arsines, e.g.. triphenylphosphine, PPh3, they are both good σ-donors
which stabilizer high oxidation state of metal ions, eg [Ni(PPh3)2Cl2]+ and good -acceptors which
stabilize low oxidation states of metal ions such the complex , W(CO)4 (AsPh3)2.

OXIDES .

The following table shows the oxides of phosphorus, arsenic , antimony and bismuth.

P4O6 As4O6 Sb4O6 Bi2O3

P4O7
P4O9 Sb2O4
P4O10 As2O5 Sb2O5

The most important oxides are those of the type M2O3 and M2O5 and.

65
Phosphorus(V) Oxide , P4O10 . (MPt 420oC) This oxide is written in abbreviated form as P2O5 . It should,
however be formulated as P4O10 . This is by far the most important and most stable oxide of group15
elements. It is prepared by a variety of methods.

(a) Burning phosphorus in excess air. P4 +5O2 Δ P4O10 .

(b)Heating a mixture of phosphate rock and sand to a temperature of 1400-1500oC.

2Ca3(PO4 )2 +6SiO2 . Δ P4O10 . +6CaSiO3

Phosphorus(V) oxide dissolves in water to form orthophosphoric acid, H3PO4 .

Phosphorus(III) Oxide , P4O6 , is obtained by burning phosphorus in a limited amount of air.

Phosphorus(III) oxide dissolves in water to form phosphorous acid, H3PO3 .,Phosphorous acid has only two
ionizable hydrogens. The reason is that the third hydrogen is attached to the phosphorus , directly ie

O H
H
O= P O
H
It is thermally unstable, disproprtionating to P(V) and P(-3)

4H3PO3 Δ H4PO3 + PH3

Arsenic(III) Oxide , As4O6 is obtained when arsenic is burnt in air.

Arsenic(V) Oxide , As4O10 , is obtained by oxidizing arsenic with concentrated nitric acid , followed by
dehydration of the arsenic acid hydrates obtained.
Antimony(V) Oxide , Sb4O10 . This is obtained when antimony(III) oxide is heated under high pressure
of oxygen.
Arsenic (III) Oxide ,As4O6 , and Antimony(III) Oxide , Sb4O6 These are obtained by burning the
elements in air.
Bismuth (III) Oxide , Bi2O3 . Apparently, this is the only well-established oxide of bismuth.

Oxohalides. All the oxohalides, , X3PO (X=, F, Cl, Br, I) are known. Phosphoryl chloride, Cl3PO , is by
far, the most important. It is prepared by one of two routes.
(a ) Heating phosphorous chloride, PCl3 , in a current of air.

2PCl3 + O2 2Cl3PO .

(b) Heating a mixture of phosphorus(V) oxide , P4O10 , and phosphorus(V) chloride, PCl5 . .

P4O10 + 6PCl5 10Cl5PO

66
Oxo Acids and anions of phosphorus.
There are two important series of oxo acids of phosphorus namely, those based on phosphorus(V) and
those base on phosphorus(III).
Dissolution of phosphoric oxide, P4O10, in water gives ortho phosphoric acid, H3PO4 ., otherwise called
phosphoric acid . On the other hand, dissolution of P4O6 in water gives phosphorus acid, H3PO3. Whereas
H3PO4 is tribaisc, H3PO3 , is dibasic. The reason is that whereas phosphoric acid, H3PO4 has three
ionizable hydrogens ,

i.e O=P(OH)3 , phosphorous acid has only two, i.e,

H
O= P(OH)2 .
This is readily verified in acid-base titrations which show that there are three end-points in the titration of
H3PO4 and only two in the titration of H3PO3.
+ -
H3PO4 +H2O ⇋ H3O +[H2PO4] K1 = 7.11X10-3; pK1= 2.15 .
- + 2-
[H2PO4] +H2O ⇋ H3O +[HPO4] K2 = 6..31 X10-8; pK2= 7.20.
2- + 3-
[HPO4] +H2O ⇋ H3O + [PO4] K3 =4.22 X10-13; pK3 = 12.37

On the other hand,

+ -
H3PO3 +H2O ⇋ H3O +[H2PO3] K1 = (3.1-2.1) X10-2; pK1= 1.8.
- + 2-
[ H2PO3] +H2O ⇋ H3O +[HPO3] K2 = 1.5X10-7; pK1= 6.15

We note that in H3PO4, the second and third ionization constants are very mall in comparison
with the first ionization constant. The reason is that the second proton is being removed from a
-
singly- charged anion , [H2PO4] , whereas the third proton is being removed from a species with
two negative charges,
2-
namely, [HPO4] .
Ortho phosphoric acid is by far, the most important acid of phosphorus . For example, practically all
phosphorus fertilizers are based on this acid. Thus partial neutralization of the acid with ammonia gives
products like Diammonium phosphate ,(NH4)2HPO4 , ( DAP) or monoammonium phosphate,
(NH4)H2 (PO4) , MAP etc . There are many both linear and cyclic species of paramount industrial
importance derived from this acid. Two ortho phosphoric acid molecules condense to form pyrophosphoric
acid, H4P2O7 , (HO)2 P (O) -O-P( O) (OH)2, Three molecules condense to form a triphosphate and so on .

Phosphorous Acid ,H-P(O) (OH) 2 . Phosphorous acid, H-P(O) (OH) 2,has two ionizable hydrogens , the
third one being bonded to the phosphorus directly. .It is formed when phosphorus(III) oxide, P 4O6, is
dissolved in water or phosphorus trihalides, PX3( X= Cl, Br, I) are dissolved in water .

67
The Trihalides . All the Group 15 elements form the trihalides,, MX3 . These and some of their
properties are listed in Table, 8.6 . All the group 15 halides are covalent molecules . This is not
unexpected considering that

Table, 8.6 The trihalides , MX3, and some of their properties .

Compound MPtoC BPtoC

AsF3 -6.0 62.8
AsCl3 -8.5 130.2
AsBr3 31.2 221
AsI3 146 ≈400
SbF3 290 345
SbCl3 73.4 223
SbBr3 96.0 288
AsI3 170.5 401
BiF3 649 900
BiCl3 233.5 441
BiBr3 219 462
BiI3 408.6 542
All the trifluorides are readily prepared by the action of HF on the tri-oxides,
M2O3. In the gas phase , the trihalides, like ammonia , adopt a pyramidal
structure.
The pentahalides, MX5 .
Whereas phosphorus forms all the pentahalides, PX5, only a few pentahalides are known for the heavier
members. These are :-
Property AsF5 SbF5 BiF5 AsCl5 SbCl5
MptoC –79.8 8.3 154.4 -50dec 4
o
BPt C -52.8 141 230 ………. .140 dec
The pentafluorides are prepared by direct reaction of the element with fluorine(As, Bi) or their
oxides( As2O3, Sb2O3) .
SbCl5 is stable only below -50oC. It is made by a reaction of chlorine on the trichloride.
For bismuth, the oxidation state +5 is rather unstable because the high tendency to revert o the
configuration, [Xe]4f14 5d1o 6s2.makes the oxidation state +3 more stable than +5 for bismuth.
Gaseous pentahalides of group V have trigonal bipyramidal structures.
In the solid phase, PCl5, exists as the salt, [PCl4]+[PCl6]-. On the other hand, the bromide, PBr5, exists as the
salt, [PBr4]+[Br]- .

SOME SULPHUR COMPOUNDS OF GROUP 15 ELEMENTS :

We note that for most phosphorus-oxygen compounds, there are corresponding phosphorus-sulphur
compounds. Eg, both P4O10 and P4S10 have the same structure, which is based on the tetrahedral P4 unit .
There is an oxygen along each edge of the tetrahedron and four P=O double bonds in P4O10 and on one
hand, and , for P4S10, suplphur atoms have replaced the oxygens in P4O10 . A notable phosphorus- sulphur
compound is P4S3 which makes up to 9% of a match head the rest being KClO3,20%,Ground glass
KClO3,20%, Fe2O3 , 11%, ZnO ,7%, Glue , 10%, Water ,29%,.

68
CHAPTER 9 GROUP 16 ELEMENTS ., Oxygen, Sulphur, Selenium, Tellurium, Polonium.

Section A- Oxygen.

Table 9.1 Some physical properties of Nitrogen:

Atomic Number …………………… 8
Electron Configuration : 1s22s22p4 or [He] 2s22p4
Melting Point (oC) -218.4
o
Boiling Point ( C) -182.96
Atomic Number, Z 8
2-
Ionic Radius (pm) of O ………….. 126
Density ………………………………………………1.429/l(OoC)

69
Sp gravity liq……………………………..1.14(-182.96oC)
Oxygen is the most abundant element on the earth’s crust making up 45.5%
of the total mass. and about 21% of the gases in the atmosphere by volume.
The water bodies( oceans, seas, lakes and rivers) cover over 75% of the
surface of the earth . Since water has a molecular weight of 18, this implies
that oxygen makes up approximately 88% of the mass of the water in
masses(i.e oceans , lakes and rivers) . The dioxygen molecule is
paramagnetic owing to presence of two unpaired electrons in the anti-
bonding, pЛ*, molecular orbitals. Recall that, putting electrons in anti-
bonding molecular orbitals decreases the bond order and increases the
internuclear distance between two atoms. Such a bond actually becomes
weaker as can readily seen by considering the data for various dioxygen
species listed in Table Table 9.2
Table 9.2 Some Physical Data for various Di-oxygen species

Species O-O distance(p) No.of electrons Bond Order ν(O-O) cm-1

in anti-bonding
M.O
[O-O] + 112 1 2.5 1860
O-O ( inO2) 121 2 2 1556
[O-O] - 133 3 1.5 1145
[O-O]2- 149 4 1 770

Reactivity. Oxygen combines with nearly all elements in the periodic Table In fact, originally, the
word “oxidation” meant combination of a substance with oxygen. Of course, the term is now used with a
broader meaning.. it is a process whereby the formal oxidation state of a species has been increased.
Hydrides . These are compounds containing only two elements, one of them being oxygen. Carbon
hydrides belong to the realm of organic chemistry and will not be discussed here. Secondly, it should be
realized that if the electronegativity of the particular element is higher than that of oxygen, then it would be
more logical to think of such a substance as an oxide. This is the case with the perhaps the most important
hydride of oxygen ,namely, water. Unfortunately, traditions are extremely difficult to discard.
Water,H2O. Water is, by far, the most important hydride of group16 elements.
As noted above, oxygen is more electronegative than hydrogen, and hence, the systematic name for it
should be Hydrogen Oxide, rather than , oxygen hydride . The common name, “water” is used except
when naming co-ordination complexes containing water as a ligand, in which case one speaks of an “aqua
complex.”
Water is one substance without which life would not be possible as we know it. . In addition to water
making the bulk of material substances in oceans , lakes and rivers,
all animals and plants dead or living contain oxygen in combined form eg as proteins .

70
Table 9.3 lists some physical properties of this substance and those of the heavier isotopes, Deuterum,D ,
and Tritium, T.

Table 9.3 lists some physical properties of ordinary water heavy water.

Property H2O, D2O T2O Molecular wt 18.0151

20.0276 22.0315
Mpt.(oC) 0.00 3.81 4.48
Bpt.(oC) 100.00 101.42 101.51
Temp.of
max.density.(oC) 3.98 11.23 13.4
max.density.(g/cc) 1.000 1.1059 1.2150
Dielectric constsnt,ε, 78.39 78.06…………….
Water containing D2O rather than H2O is referred to as heavy water . It is used as a coolant and a neutron
–moderator in nuclear reactors . The very high dielectric constant for water and the fact that it is neutral
makes it the most common solvent , including a solvent for biological systems .As far as is known , all
biological reactions in living tissues take place in water . When ionic substances are dissolved, e.g, the ions
in solution are not bare but rather hold many solvent molecules . This is emphasized by writing a left
subscript “aq” after the chemical symbol.

Eg. NaCl(s) + ∞H2O(l) [Na+]aq + [Cl-]aq

Hydrogen Peroxide. H2O2 (MptoC-0.43 ; BPt 150.2 oC ) .

Hydrogen peroxide contains the peroxo anion,[O-O]2-

Preparation On labolatory scale, hydrogen peroxide is prepared by acidification of alkali metal

peroxides.
Industrially, it is manufactured by catalytically reducing 2-ethylanthraquinone with raney nickel to
quinol. The catalyst is separated by filtration and the quinol is oxidized by blowing air through the
solution when anthraquinnone and hydrogen peroxide are obtained. H2O2 is extracted with water and
concentrated at a reduced pressure to get a solution which is about 30% in H2O2.
Hydrogen peroxide is a rather unusual substance in that behaves both as an
oxidizing agent and a reducing agent in both acidic and basic media .The
following reactions will help to illustrate this.
(A) Hydrogen peroxide as an oxidizing agent:-
(i ) in acidic media .
2[Fe(CN)6]4 + H2O2 + 2H+ = 2[Fe(CN)6]3- +2H2O

(ii) in basic media

71
Mn2+ + H2O2 + 2OH- = Mn4+ + 2H2O +2O2-
(C) Hydrogen peroxide as a reducing agent in :-

( i )acidic media

2[MnO4]- + 5 H2O2 + 3H + = 2Mn4+ + 8H2O +5O2

(ii) in basic media-

2Fe3+ + 2H2O2 + 2OH- = 2Fe2+ + 2H2O +O2

We note that in most familiar reactions where oxygen is evolved, hydrogen peroxide is behaving as a
reducing agent.

Section B The heavy Group 16 …..Elements , Sulphur, Selenium, Tellurium,

Polonium
Occurrence . Sulphur has a relative abundance of 340ppm in the earth’s crust . It occurs both in
elemental form and in several sulphur compounds , e.g many metal sulphides( iron pyrites, nickel, copper,
lead, zinc , and molybdenum sulphides); sulphates, e.g gypsum, CaSO4.2H2O, barites , BaSO4 ,. Sulphur is
also found as a constituent of many organic substances. Thus , it is a constituent of the hormone insulin, a
constituent of some cytochromes and all enzymes with the amino acids, cysteine, and methionine residues
.
Allotropes of Sulphur. Sulphur occurs in many allotropic forms , in which there are Sn (n= 2, 6, 7, 8, 10,
11,12, 18, 20 ,8), species Sn , for n=6 form cyclic species . There are even larger species Table 9.4
summarises some properties of Group 16 elements.
E.g catna S6 occurs in chair form ,, 6
Selenium and Tellurium.
Occurrence. These elements are extremely rare in the earth’s crust occurring to the extent of only
0.05ppm( selenium) and 0.002ppm(Tellurium) respectively .They occur commonly in combined form with
other elements a selenides or tellurides . Selenium is one of the essential micronutrients but also very toxic
if taken beyond the proper level .
Production. The principal method of producing sulphur is the Frasch Process .This process which was
developed and perfected by Herman Frasch during the period, 1891-4 and has stood the test of time.
Basically, in this process superheated water is forced down a well using the outer concentric pipes .It melts
the sulphur which is forced to the surface through the inner tubes of the pipe using compressed hot air.
Selnium and tellurium are recovered from the anodic slimes formed when recovering copper
electrolytically.
Polonium : This is the only metallic element of group 16 elements. It has no stable isotopes and is
produced in β-decay of bismuth. It is itself unstable, losing an α–particle to produce lead.

219 210 206

83 Bi83 β 84 Po α 82Pb .

72
Table 9.4 Some properties of Group 16 elements.

Element Symbol Atomic Ionic radius Electron

No of X2-, pm config.
Sulphur S 16 184 [Ne]3s23p4
Selenium Se 34 198 [Ar]3d104s24p4
Tellurium Te 52 221 [ Kr]4d105s25p4
Polonium Po 84 …. [Xe]4f145d106s26p4

Properties .Forms of elemental sulphur; Catenation,

with sulphur at the corners .The S8 molecules form cyclic species which may be circular

puckered like

form

depending on temperature. As may be expected, the physical properties of sulphur like density, melting,
are variable because these depend on the particular allotrope that one is considering . This may be
illustrated by considering a few examples in Table 9.6.

The table 9.5 some allotropes of sulphur.

Allotrope Colour Density Mpt ( or decom point )oC

S6 red orange 2.209 d>50
α-S8 yellow 2.069 112.8
β-S8 yellow 1.94-2.01 119.6
γ-S8 light yellow 2.19 106.8.

73
cyclo-S20 pale yellow 2.016 124 d
Chemical Reactivity. Sulphur forms compounds with most of the elements in the periodic Table. Thus it
forms compounds with oxygen, hydrogen, all halogens and all electropositive metals . Like the other
elements, the reactivity increases with increase in temperature. For example, whereas the reaction with
hydrogen is very slow at 120oC, the reaction is very fast at 200oC. It ignites in fluorine even at room
temperature .The property of catenation is observed not only in elemental sulphur and selenium but also in
many other types of compounds, e.g sulphanes, halides, and oxo compounds.

HYDRIDES OF SULPHUR, SELENIUM , TELLURIUM AND POLONIUM

Some hydrogen compounds of the heavy group 16 Elements are listed in Table9.6
Hydrogen sulphide, H2S, is by far the most important hydride formed by the chalcogens, as the heavy
Group 16 elements are referred . to Both H2S and can be prepared by direct reaction of the elements or
hydrolysis of electropositive metal chalconides e.g

Na2S +2H2O = 2NaOH + H2S

and similarly for H2Se, H2Te and H2Po. In addition to the simple hydrides, there hydrides of the type,

H2Mn where M=S , Se; n is can take many values like 2, 3, 4, etc . This is due to the property of catenation
and most important for sulphur and least important for polonium.

Table 9.6 The hydrides of group16 elements and some of their properties.

Mwt Mpt (oC) Bpt (oC )

H2S Hydrogen sulphide 34.08 -85.5 -60.7
H2S2 Dihydrogen disulphide 66.14 -89.6 70.7
H2S4 Dihydrogen tetrasulphide 130.27 -85 ……………
H2S5 Dihydrogen pentasulphide 162.34 -50 50(4at)
H2Se Hydrogen selenide 80.98 -65.7 -41.3
H2Te Hydrogen Telluride 129.62 -51 -4
H2Po Polonium hydride -36 37
Halides . Sulphur , selenium and Tellurium form halides in oxidation states
1,2,3,4,5 and 6 . There are two types of halides , namely those in which there
is only one chalcogen atom(S,Se or Te). In such halides, the central atom
can have oxidation states +2, +4 and +6 . The highest oxidation state is only
achieved by sulphur and selenium and then only in the fluorides , MF6 .
The other type halides is one in which two or more chalcogens are joined together. This is due to the
property of catenation referred to earlier when discussing allotropy . Thus, sulphur and selenium form
halides of the type, MnX2( M=S, Se, X=Cl, Br) with n values between 1 and 8. It should be noted that
compounds with n values as large as 100 are known
Disulphur,dichloride , S2Cl2 ( mpt-76oC., Bpt mpt 138 oC.) , is perhaps, by far the halide with largest
practical application. It is used for vulcanization of some rubbers and ,hence, it is marketed in terms of
thousands of tones. It is prepared by direct chorination of sulphur followed by fractional distillation of the

74
products. Sulphur monochloride, is always in equilibrium with the less stable, sulphur dichloride, SCl2,
( mpt-122oC., Bpt mpt 59 oC. , starts dec at mpt 20 oC )
Tables 9.7 to 9.10 show selected examples of some halides of the heavy Group16 elements namely,
Sulphur, Selenium, Tellurium and Polonium.

Table 9..7 Halides Containing M+ Species.

Compound MPtoC BPtoC

FSSF -133 15
S=SF2 -164.6 -10.6
S2Cl2 -76 138
ClSeSeCl -85 130
BrSeSeBr .. 225d
αTe4I4 185

Table 9.8 Halides Containing M2+ Species.

Compound MPtoC BPtoC

SCl2 -122 59d
SeF2 (unstable)
SeCl2 Decomposes in
vapour
SeBr2 Decomposes in
vapour
TeCl2
TeBr2 Brown dec.
PoCl2 335 130 sub
PoBr2 270dec
PoI2 Impure from dec. of
PI4 at 200oC.

Table 9..9 Halides Containing M4 + Species ( i.e MX4).

Compound MPtoC BPtoC

SF4 -124 -40
SeF4 -13.8 >100
TeF4 sub >97
PoF4

75
SCl4
SeCl4 205 288d
TeCl4 224 380
PoCl4 300(in Cl atm) 390
SBr4
SeBr4 75d
TeBr4 380 421d
PoBr4 330(in Br atm) 360
SI4
SeI4
TeI4
PoI4 200(in N atm) ….

Table 9..10 Halides Containing M6 + Species(ie MX6).

Compound MPtoC BPtoC

SF6 -50.54 63.8
SeF6 -39(sub) -34.5
TeF6 -36 35.5

Oxides and Oxo- acids

Sulphur Dioxide, SO2, Mpt, -75.5 oC Bpt, , -10 oC

Sulphur dioxide, is produced when sulphur is burnt in air. It is also formed when sulphides like galena,
PbS , Copper sulphide, or zinc sulphide are roasted in air.
It is a colourless toxic gas with a choking smell. Burning of any material of organic origin e.g wood or
petroleum produces sulphur dioxide .This is, in fact ,one cause of atmospheric pollution as its reaction
with rain water or moisture in the atmosphere results in formation of sulphurous acid, H2SO3.
SO2 +H2O , H2SO3 .
Sulphur dioxide, SO2 , like a water molecule ,has a V-shaped structure, with OSO

angle of 119oC. At oC ,it is has a dielectric constant , ε, of 15.4 . It is a very convenient non-aqueous solvent
.
Sulphur trioxide, SO3. Mpt, 16.8 oC Bpt, , 44.52 oC .Sulphur trioxde is one of the most important
compounds in the chemical industry in that its combination with water gives sulphuric acid, . H2SO4 .
Sulphuric acid is , itself , a Primary Chemical . By a “primary chemical” we mean a chemical which is
either used as a raw material for manufacturing other chemicals or is an essential component in manufacture
of other chemicals”. Sulphuric qualifies as primary chemical because of the second part of the definition.
It is used in manufacture of the widest range of other chemicals, and for this reason , its consumption
gives an index of measuring the industrial development of a nation. It is classified as the Primary Chemical

76
No.1. One can , therefore , say that sulphur trioxide is not only the most important oxide of sulphur but
perhaps one of the most important chemical .
Preparation: Sulphur trioxide can be prepared in one of several methods:
( a ) Thermal decomposition of either ferric sulphate or ferrous sulphate :-

Fe2(SO4)3 heat Fe2O3 + 4SO3

2FeSO4 heat Fe2O3 + SO3 +SO2

( b ) Catalytic Oxidation of SO2 on Fe2O3 , V2O5 , or platinum .

2SO2+O2 V2O5 ,or Pt 2SO3

This reaction is used for manufacture of sulphuric acid in what is called the “Contact Process”. The
sulphur trioxide produced is dissolved in concentrated sulphuric acid rather than water to make fuming
sulphuric acid, otherwise called oleum .This acid is over 98% . Sulphur trioxide has a trigonal planar
structure.
It should be noted that although platinum catalyzes the oxidation of sulphur dioxide to sulphur
trioxide, vanadium(V) oxide, V2O5, is the preferred catalyst . The reason is that the platinum catalyst is
readily poisoned by impurities like sulphur or carbon monoxide.Furthermore , vanadium pentoxide is much
cheaper than platinum. Hence, there is no good reason , therefore , to use an expensive material when
there is cheaper alternative which will give the same results.

Structure : Sulphur trioxide has a trigonal planar structure.

S
O O

Oxides of Sulphur based on hydrogen peroxide ,HO-OH.

The reaction of SO3 or SO2 with O2 in presence of an electric discharge gives polymeric species with
the general formulae , SO3+x S(0 x  1). Hydrolysis of these materials gives , sulphuric acid, H2SO4 ,and
peroxomonosulphuric acid(otherwise called Caro’s acid, ( H2SO5. In this acid, one OH group of sulphuric
acid has been replaced by OOH group of hydrogen peroxide.

77
Oxohalides; These are compounds containing both oxygen and a halogen attached to the central atom, S,
Se, Te. The most stable oxohalides are those of sulphur and selenium , listed in Table 9.11. In addition to
the ones listed, there those which contain mixed halogens, e.g OSFCl.

Table 9..11 Selected Oxohalides of sulphur and Selenium.

Property OSF2 OSCl2 OSBr2 SO2F2 SeOF2 OSeCl2 OSeBr2 SeO2F2
o
Mpt C -110 -101 -50 15 10.9 41.6 -99.5
BptoC -44 76 140 125 177.2 220 -8.4
From a practical point of view, thionyl chloride, OSCl2 ,is by far the most important oxohalide. For
example, it is commonly used as a non-aqueous ionizing solvent. Secondly, it is used for preparation of
anhydrous metal chlorides, MXn.
Thus,
MXn. mH2 O + mOSCl2 = MXn + mSO2 +2mHCl
Thionyl chloride can be prepared from a reaction of PCl5 with sulphur dioxide, SO2.

PCl5 +SO2 = OSCl2+ OPCl3

CHAPTER10 GROUP17.. ELEMENTS ( Fluorine, Chlorine, Bromine, Iodine, Astatine)

The halogens and some of their properties are listed in Table 10.1

Table 10.1 The halogens and some of their properties.

Property F Cl Br I At

El.Conf. [He]2s22p5 [Ne]3s23p5 [Ar]3s104s24p5 [Kr]4d105s25p5 [Xe]4f145d106s26p5

At. No 9 17 35 53 85

At. Wt 18.9984 35.453 79.909 126.9044 210

Mpt(oC) -219. 62 –100.95 -7.2 113.5 ….

BPt(oC) -188.141 - 34.6 58.7 8 184.35 ………..

BDE 158.8 242.58 192.77 151.10 …………..

(kJ/Mol)
(Elec. Aff -332.6 -348.5 -324.7 -295.5 - 270

(kJ/Mol)
Key ; .At. No. Atomic Number
At Wt … Atomic Weight
BDE …… Bond Dissociation Energy
El.conf. ….. Electron configuration
Elec. Aff…… . Electron Affinity
Some properties of the halogens.

78
 The electron configurations of the halogens show that each element requires only one electron to attain
the stable rare gas core at the end of the series . Furthermore, the nuclear charge is very large in comparison
with that of an element at the beginning of series. A direct consequence of these facts is that a halogen is
strongest oxidizing element in any given series.
. For example, fluorine has the electron configuration 1s22s22p5 (written in abbreviated form as [He]2s22p5,
where, [He] is the electronic configuration of helium) . By taking up one electron, fluorine forms the
fluoride ion with electron configuration , 1s22s22p6 ,which is exactly like that of neon . A similar reaction
takes place for each halogen and, in summary, we can write :-
X2(g) +2e = 2X-( g ) (X=F,Cl,Br,I,At) .
The halogens, with the exception of fluorine, form a wide range of oxidation states from –1 to +7 . See
Table1 . As may be deduced from the preceding paragraph , the formal oxidation state of-1 is the most
stable for the group seventeen elements( the halogens) . Hence any species ( compound or ion) in which the
formal oxidation state of the halogen is larger than –1 is an oxidizing agent. E.g NaOCl in common
bleaches like “Jik” are oxidizing agents . KClO3 is a component of safety matches and gun-powder since it
is a strong oxidizing agent.

Table 10.2 Formal Oxidation States attained by the Halogens.

Species Formal Oxidation State of X

X- (X=Cl, Br, I ,At) -1
X2 (X=Cl,Br, I) 0
HXO(X= Cl , Br , I) +1
XF3(X=Cl,Br, I) +3
NaXO3 (X=Cl, Br, I) +5
NaXO4 (X=Cl, Br, I) +7

Fluorine. Fluorine is prepared following a procedure developed by Moissan of electrolysing KF dissolved

in HF. Fluorine is the most electronegative element and combines with practically all elements in the
periodic table with exception of helium and neon.
Chlorine.Chlorine is widely distributed in the earths crust . Most of the
dissolved substances in sea water are present as chlorides. E.g A litre of sea
water contains 27.3190g of NaCl and 4.176g of MgCl2 .
Chlorine is used in large quantities for water treatment to kill organisms in drinking water and for
bleaching wood pulp during manufacture of paper in the Kraft Process.
PREPARATION
(a) Laboratory Preparation .
On the laboratory scale, chlorine can be prepared by a variety of methods which are, in all cases using
the same principle , namely, oxidation of the chloride ion, Cl- .

Eg. MnO2 + 4HCl = Mn2+(aq) + 2Cl2 + H2O(l)

.Lead (IV) oxide, PbO2 , reacts similarly .

79
 Other reactions that give chlorine include, reaction of potassium permanganate with dilute hydrochloric
acid, reaction of oxygen with titanium chloride at high temperature, or electrolytic oxidation with a direct
current either in aqueous solutions or on chloride melts
Over the years, chlorine has been manufactured following several methods among them the following:- .
( a) Electrolysis of Molten Sodium chloride.
Chlorine is manufactured by electrolysis of fused sodium chloride/ calcium chloride mixture the
latter being added to lower the operating temperature.

(c) Electrolysis of Sodium chloride in mercury Cells- The Kastener Process .

Bromine. Occurrence and Extraction . Bromine is recovered from sea water by oxidation of the bromide
ions with chlorine

2Br- + Cl2 = Cl- + Br2

Iodine . Occurrence and Extraction . Iodine occurs in sea water as iodides from which it is accumulated
by sea weeds . Iodine is recovered from ashes of sea weeds or directly from sea water itself. Iodine has also
been found present as sodium or potassium iodate in Chilean salt peter. Iodine is one of the essential trace
elements whose deficiency causes goiter.
Astatine .Astatine does not occur naturally and is produced by bombarding bismuth with α-particles.
209
2 Bi83 +42He 211
83 At +2 1no

Reactions of the Halogens .

Oxidizing Power of the Halogens and their Compounds . As noted earlier, the position of the halogens
in the periodic Table makes them the strongest oxidants within any given series. Thus, they react with all
elements of Group2 to compounds of the type MX2.

Eg. Mg(s)+X2 (g) MgX2(s) (X=, F,Cl, Br, I) .

Furthermore , as can be seen from the following tables, all the halogens except fluorine form compounds
in which the formal oxidation states vary from –1 to +7.
When an element forms more than one formal oxidation state, the highest oxidation state possible is
usually obtained when the element reacts with fluorine, which is the most electronegative element.
E.g , excess fluorine reacts with phosphorus to form phosphorus(V) fluoride.

2P(s)+5F2 (g) 2PF5(g)

A similar reaction takes place with the other halogens but in order for the phosphorus to form P(V)
species, the reaction mixture must heated to a high temperature

2P(s)+5Cl2 (g) Δ 2PCl5(s)

2P(s)+5Br2 (l) Δ 2PBr5(s)

80
2P(s)+5I2 (g) Δ 2PI5(s)

The halogens react with the alkali metals to form ionic halides of the type MX(M=Li, Na, K, Rb ,Cs ;
X= F, Cl, Br, I). These are high –melting point ionic solids . alkali earths products of the type, MX2( M=
Be, Mg, Ca, Sr, Ba).
Oxides of the Halogens. Chlorine is by far the most important halogen.
As may be expected, all the halogen oxides are strong oxidizing agents , even stronger than the parent
halogens. Some like Chlorine(VII) oxide, Cl2O7, and even compounds drived from it is a hazardous
explosive.
Strictly-speaking, the fluorine-oxygen compounds ,F2O and F2O2should be referred to as oxygen
fluorides since fluorine is more electronegative than oxygen.

Table 10.3. Examples of Halogen Oxides.

Compound Mpt( oC) Bpt ( oC) Compound Mpt( oC) Bpt ( oC)

F2O -224 - 145 F2O2 -57 - 163

Cl2O -4 - 116 Cl2O3(a) …. ……..

ClO2 -59 11 Cl2O4 -117 44.5..

Cl2O6 35 203(extra) Cl2O7 -91.5 81
I2O5 300-350 dec ………………………………………

Iodine penta-oxide, I2O5, is used as an analytical reagent since it oxidizes CO quantitatively to CO2.

5CO + I2O5 I2 + 5CO2

The iodine is titrated with standardized sodium thiosuphate and, by working backwards, one can tell
exactly the amount of of carbon monoxide.

Dissproportionation Reacrtions of the Halogens:

The halogens X2, (X=, Cl, Br, and I) react with alkaline solutions in two distinct ways. :
( i ) Reaction with dilute alkaline solution or concentrated but cold alkaline solution gives the
hypohalite ion, XO- and the halide ion X- .

X2 + 2OH- = XO- + X- + H2O

( ii ) Reaction with concentrated alkaline solutions or hot dilute solution..

81
 This gives the halate ion, XO3- and the halide ion X- .

3X2 + 6OH- = XO3 - +5X- +3 H2O

In this reaction, the first step is exactly as in the case of reaction with dilute alkali. However, at high
temperature , and especially when the concentration of the OH- ions is high, the hypohalite ion , XO-,
disproportionates further to give the halite ion.
3XO- XO3 - +2X-

In a practical process , developed by Justus von Liebig, potassium chlorate is manufactured as

follows :-
( i ) Chlorine is bubbled through a hot suspension of calcium hydroxide.
( ii ) Next, a concentrated solution of potassium chloride is added . This precipitates the sparingly soluble
potassium chlorate . The following set of reactions take place :-

6Ca(OH)2 + 6 Cl2 heat Ca(ClO3)2+ 5CaCl2 +6 H2O

Ca(ClO3)2 + 2KCl 2 KClO3 + CaCl2

A big drawback of this process is that only a fifth of the chlorine is converted to chlorate , the rest
being converted to chloride ions.
A better process for manufacture of halate ions uses anodic oxidation of the halide ion , first to the
hypohalite ions , which, on further oxidation give the halate ions.
For example, in preparation of sodium chlorate the following reactions take place:-

Anode: Cl- ½Cl2 +e

Catode : H2O +e- ½H2 + OH-

Chlorine reacts with the OH- ions to form hypochlorite and chloride ions .

Cl2 +2 OH- - OCl- + Cl- + H2O .

Further oxidation of the hypochlorite ion gives the chlorate ion. The following reactions may be presumed
to take place:

At Anode: OCl- + 2 H2O XO3 - +4e ( i )

At cathode 4H+ +4e 2 H2 ( ii )

Adding ( i ) and ( ii ) gives the overall equation as: -

OCl- + 2H2O 2ClO3- + 2 H2

Inter-halogen Compounds.

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 The halogens combine with each other to form compounds of the types MX, MX3, MX5, and MX7,
where X is the more electronegative member and M is the heavier and less electronegative member.
Examples of such compounds are summarized below.
From data in these tables we note that, only iodine forms an interhalogen compound in which the formal
oxidation state is +7.The interhalogen compounds are ,strong oxidizing agents. E.g

W+ 6ClF WF6+ 3Cl2

The interhalogen compounds serve as ionizing non-aqueous solvents.

E.g 2ICl + AlCl3 [I2 Cl]+[AlCl4]-

The highest formal oxidation state possible for an interhalogen compound attainable is +7. The only
compound known in which this oxidation state is known is IF7.
Preparation. Whereas interhalogen compounds may be prepared by a variety of methods, the commonest
is the reaction between the elements.

E.g I2(g) +5F2 excessF2 IF5

I2(g) +7F2 excessF2 IF7

o
250-300
The same products can, of course be prepared by indirect methods.

Thus,

I2(O5g) ClF3 ,ClF3 or SF4 IF5

KF+4F2 250o IF7

Structure: The MX3 compounds are T-shaped. ; the MX5 compounds adopt a square pyramidal Structure,.
The MX7 compounds adopt pentagonal bipyramidal struture.

TABLE 10.4 THE MX COMPOUNDS

Compound MPtoC BPtoC Colour Stability at

Room
Temp.
ClF -156 -100.1 Colourless
gas
BrF Ca-33 dispr Pale unstable
brown gas
IF dispr
BrCl ca-66 Ca 5 Red
brown gas
ICl 27.2( α) 97-100 Ruby red
(13.9( β) ) cyrstals

83
IBr 41 ca116 Black Some diss.
crystals.

TABLE 10.5 THE MX3 COMPOUNDS

Compound MPtoC BPtoC Colour

ClF3 -76.3 11.8 Colourless
gas
BrF3 8.8 125.8 Straw-
coloured
liquid
IF3 Dec. Yellow
abobve solid
-28
I2Cl6 101(16atm) …….. Bright
yellow
solid

TABLE 10.6 THE MX5 AND MX7 COMPOUNDS

Compound MPtoC BPtoC

ClF5 -103 -13.1
BrF5 -60.5 41.3.5
IF5 9.4 104.5
IF7 6.5(triple 4.8(subl.
point) 1 atm)

84
HALIDES OF THE ELEMENTS .
As halogens are oxidizing agents, and especially fluorine, chlorine and bromine, they react with most of
the other chemical elements in the periodic ,with perhaps the exception of the rare gases where , only
fluorine reacts directly with Xenon to form the halides, XeF2, XeF4 and XeF6 . Whereas most halides will
be formed by direct reaction of the elements, indirect methods are normally used.

E.g TiO2 +2C +2Cl2 900-1200oC TiCl4 +2CO .

Sodium chloride, NaCl, which is a very important raw material for manufacture of sodium hydroxide
(chlorine gas is a by-product) is obtained from sea water either by solar evaporation of vacuum distillation.

CHAPTER 11- GROUP 18 ELEMENTS- THE RARE GASESGROUP 18 THE RARE GASES

Table 11.1 Some properties of the Rare Gases.

ELEMENT He Ne Ar Kr Xe At
Z 2 10 18 36 54 86
At. Wt. 4.0026 20.183 39.948 83.80 131.30 210
. MptoC - - -189.2C -156.6oC -111.9oC
272.2oC 248.67oC
BptoC -268oC - - -152.30oC -107.1oC
245.92oC 185.7oC

General Introduction.
For many years , the noble gases were referred to as
“Inert Gases” because they never form compounds with any other chemical Elements”
This definition rendered obsolete in 1962 when Bartlett showed that xenon reacts with PtF6 to form a
chemical compound, originally believed to be XePtF6, but latter showed to be [XeF+][XePtF6]- . When this
complex is mixed with ,PtF5 , and the mixture heated to 60oC, the complex, [XeF+][XePt2F11]- , is formed.
given in a book published in 1962 , the year in which the definition was demonstrated to be erroneous by
preparation of xenon fluorides . The more appropriate definition for these group 18 elements in rare gases.
Occurrence and Isolation . The rare gases occur as minor constituents of the gases in the atmosphere.
Helium has also been obtained in some natural gases, no doubt due to radioactive decay of some rocks .
neon, argon , krypton and xenon are recovered from by fractional distillation of liquid air . Thus, argon(mpt
-272.2oC, Bpt, -268oC) is major impurity in the nitrogen used for ammonia synthesis.
Chemical Compounds of the rare Gases.

In 1962,Niels Bartlett, while working with PtF6 , found that some oxygen that leaked into the vessels
resulted in formation of [O2]+ [PtF6]- . In other words, platinum(VI) had been reduced to platinum(V). The

85
oxygen molecule had been oxidized to the oxygenyl cation, O2 + . Bartlett recalled that molecular oxygen
and xenon have almost identical first ionization energies( ….kJ/mole for O2 and 1169.kJ/mole for
Xenon..). He therefore , correctly reasoned that Xenon should be oxidized by PtF6, just like the oxygen
molecule had been. This hypothesis was tested and found to give a product which was initially thought to
be XePtF6 . Although the product was shown to have a different composition, this was the genesis of the
chemistry of the rare gases. Today, many rare gas compounds are known. Table11.2 below shows a few
selected examples.

Table 11.2 Some Compounds of the Rare Gases and their properties

Ox. Formular of mpoC Structureof Form and colour Some notable

State Compound or Compound properties
complex or ion
II XeF2 129 Linear Colourless crystals Decomposed by
water to Xe& O2
IV XeF4 117 Square Colourless crystals Heat of formation,
planar ΔHf =
-284kJ/Mole
IV XeF6 49.6 Distorted Oh Colourless crystals Heat of formation,
ΔHf =
-402kJ/Mole
IV CsXeF7 Colourless Solid Decomposes
above 50oC
IV Cs2XeF8 Archemedian Yellow solid Stable to 400oC
antiprism
VI XeOF4 -46 Colourless liquid Stable
VI XeO2F2 31 Colourless crystals
VI XeO3 Colourless crystals Explosive
ΔHf
=+402kJ/Mole
VI XeO4 -35.9 Colourless gas Highly Explosive

II KrF2 Very Unstable

Preparation. XeF2 . A mixture of F2 and Xe , with xenon in excess, is heated to a temperature of in a

sealed nickel vessel. Alternatively ,a mixture of F2 and Xe is irradiated with sunlight. XeF2 is a white

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crystalline solid. It vaporizes as linear molecules. It is soluble in water in which it dissolves to the extent of
25g per litre at OoC.. Presence of the slightest traces of a base results in instant decomposition.

2 XeF2 + 2H2O 2 Xe+ 4HF+O2

Aqueous solutions of XeF2 , are a strong oxidizing agents. Eg, Cr(III) is readily oxidized to Cr(VI), Ag(I) to
Ag(II) , Cl- to Cl2 , Ce(III) to Ce(IV) and [ BrO3]- to [ BrO4]-.

XeF4 . This is best prepared by heating a xenon –fluorine gas mixture in the ratio 1:5 to a temperature of
400oC under a pressure of 6 atmospheres in a nickel vessel. It is an easily sublimed white crystalline solid
which is strong oxidizing agent, even stronger than the difluoride , XeF2. For example, it oxidizes mercury
to mercuric state, platinum to platinum(IV) and sulphur(IV) to sulphur(VI) and , in these reactions , Xe(IV)
is reduced to elemental xenon. Is violently hydrolyzed by water and at the same time, some
disproportionation takes place.

6XeF4 + 12H2O 2XeO3 + 4Xe +3O2 + 24HF

XeF6 . This is best prepared by a prolonged heating of heating a xenon –fluorine gas mixture in the ratio
1:20 to a temperature of 250- 300oC under a pressure of 50-60 atmospheres in a nickel vessel. This is an
interesting compound in that whereas the solid is colourless, it is yellow in both the liquid and gaseous
states. The compound cannot be handled in glass since it reacts with it to produce the dangerously
explosive, XeO3 .

2 XeF6 + SiO2O 2 XeOF4+ SiF4

2XeOF4+ SiO2 2 XeO2F2 + 4HF+SiF4

2XeO2F2 + SiO2 2 XeO3 + SiF4

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