G.C.E.

(A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements

p Block Elements

4.3 Group 13 elements

4.3.1 Group trends

Boron is a metalloid, and most of the boron compounds are covalent. However,
aluminium is a metal with amphoteric properties. Gallium, indium and thallium are
metals. The first member, B, of Group 13 is different from the other members due to its
smaller atomic radius. Boron shows a strong diagonal relationship with Si in Group 14.
All elements in Group 13 produce +3 oxidation state. The properties of Group 13 elements
are given in Table 4.6.

Table 4.6 Properties of Group 13 elements

**B Al **Ga **In **Tl

Ground state
electronic [He]2s22p1 [Ne]3s23p1 [Ar]3d104s24p1 [Kr]4d105s25p1 [Xe]4f145d106s26p1

configuration
Metallic radius/ pm - 143 153 167 171
Covalent radius/ pm 88 130 122 150 155
Melting point/ °C 2300 660 30 157 304
3+
Radius of M / pm 27 53 62 80 89
st
1 ionization energy/
799 577 577 556 590
kJ mol-1
2nd ionization energy/
2427 1817 1979 1821 1971
kJ mol-1
3rd ionization energy/
3660 2745 2963 2704 2878
kJ mol-1
**Not a part of current G. C. E. (A/L) syllabus

4.3.2 Aluminium
Aluminium is the third most abundant element in the earth crust. The exposed surface of
aluminium produces a layer of Al2O3. This layer makes aluminium resistant to further
reactions with oxygen. Due to this impermeable layer, Al can be considered as a non-
reactive element with air.

Reactions of aluminium
Aluminium reacts readily with O2 and halogens. Also, it reacts with N2.

With oxygen (O2) : 4Al + O2 2Al2O3

With halogen (X2): 2Al + 3X2 2AlX3

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With nitrogen (N2): 2Al + N2 2AlN

Aluminum is less reactive than Groups 1 and 2 elements. Similar to beryllium, aluminium
reacts with both acids and bases. The equations for the reactions of Al with acids and
bases are given below.

2Al(s) + 6HCl(aq) 2AlCl3(aq) + 3H2(g)

2Al(s) + 2OH ̅ (aq) + 6H2O(l) 2[Al(OH)4] ̅(aq) + 3H2(g)

Aluminium ion in aqueous solution is expected to be present as hexaaquaaluminium ion.

However, hydrolysis of Al3+ produces [Al(OH2)5(OH)]2+(pentaaquahydroxidoaluminium
ion) and then produces [Al(OH2)4(OH)2]+ (tetraaquadihydroxidoaluminium ion) as shown
below.

[Al(OH2)6]3+(aq) + H2O(l) [Al(OH2)5(OH)]2+(aq) + H3O+(aq)

[Al(OH2)5(OH)]2+(aq) + H2O(l) [Al(OH2)4(OH)2]+(aq) + H3O+(aq)

Addition of OH- ions to aluminum ions first produces a gelatinous precipitate of

aluminum hydroxide. With excess OH- ions, the precipitated aluminum hydroxide is
converted to tetrahydroxidoaluminate complex ion.

Al3+(aq) + 3OH ̅ (aq) Al(OH)3(s) (white gelatinous ppt)

Al(OH)3(s) + OH ̅ (aq) [Al(OH)4] ̅ (aq) or AlO2 ̅ (aq) + 2H2O(l)

Group 13 elements can have six electrons in their valence shell by forming three covalent
bonds due to their ns2np1 electron configuration. As a result, many of the Group 13
covalent compounds have an incomplete octet, so can act as Lewis acids to accept a pair
of electrons from a donor. These compounds with incomplete octet are called electron
deficient compounds. Both B and Al compounds with incomplete octet form dimers in
the gaseous phase to satisfy the octet rule (Figure 4.2).
Cl Cl Cl

Al Al

Cl Cl Cl

Figure 4.2 Structure of gaseous Al2Cl6

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4.4 Group 14 elements

4.4.1 Group trends

Due to the formation of covalent bond network structure, the first three elements of group
14 have high melting points. Carbon is a nonmetal, whereas silicon and germanium are
metalloids. Last two elements in the group, tin and lead are metals.

Carbon can be found in nature mainly in coal, crude oil, calcite (CaCO3), CO2 in air,
magnesite (MgCO3) and dolomite (CaCO3·MgCO3). Graphite, diamond and fullerenes
are the allotropic forms of carbon. Fullerenes are recently found, and most well-known
fullerene is C60, buckminsterfullerene (or bucky-ball). Carbon is the basis of life and the
most important element in organic chemistry. Silicon and germanium are mainly used in
the semiconductor industries. In addition, silicon is heavily used in inorganic polymer
industry.

The properties of Group 14 elements are given in Table 4.7.

Table 4.7 Properties of Group 14 elements

C **Si **Ge **Sn **Pb

Ground state
electronic [He]2s22p2 [Ne]3s23p2 [Ar]3d104s24p2 [Kr]3d105s25p2 [Xe]4f145d106s26p2
configuration
Metallic radius/ - - - 158 175
pm
Covalent radius/ 77 118 122 140 154
pm
Melting point/ °C 3730 1410 937 232 327
Radius of M /4+ - - 53 69 78
pm
**Not a part of current G. C. E. (A/L) Chemistry syllabus

4.4.2 Diamond and graphite

Diamond and graphite are composed of homoatomic (same atoms) lattice structures.
Diamond (sp3 hybridized carbon, tetrahedral) has a cubic crystalline structure. Graphite
(sp2 hybridized carbon, trigonal planar) has stacked two-dimensional carbon layers.
Carbon-carbon bonds in graphite are shorter than that of diamond (diamond 154 pm and
graphite 141 pm) due to the hybridization of carbon atoms. These two crystalline lattice
structures are hard however diamond structure is the strongest lattice. Graphite is an
electrical and a thermal conductor due to delocalizing π electrons (Figure 4.3).
Interactions between layers of carbon in graphite are weak and this makes graphite a good
lubricant.

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Figure 4.3 Delocalizing π bonds of graphite

Fullerenes are another series of carbon allotropes. In fullerenes, carbon atoms are
connected in a spherical manner. Structures of graphite, diamond and fullerene (C60) are
shown in Figure 4.4.

(a) (b) (c)

Figure 4.4 Structures of (a) graphite, (b) diamond and (c) fullerene (C60)

4.4.3 Carbon monoxide and carbon dioxide

Carbon monoxide is a colourless, odourless, highly poisonous gas. Bond enthalpy of
carbon monoxide is more than that of the C=O double bond. In carbon monoxide, CO
bond length is shorter than that of a typical C=O double bond. This suggests that the
bonding between C and O in carbon monoxide is not a typical C=O double bond. It has a
triple bond nature between the two atoms of C and O. The Lewis structure of CO is shown
in Figure 4.5.

Figure 4.5 The Lewis structure of CO

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Carbon monoxide is mostly used as a reducing agent in the production of iron. Also, CO
plays an important role in many catalytic reactions as a ligand due to the lone pair of
electrons on the C atom.

Carbon dioxide (Figure 4.6) solidifies due to London forces at low temperatures and/ or
under high pressures. Solid CO2 (dry ice) sublimes to produce gaseous carbon dioxide
under normal atmosperic conditions. It is commonly used as a freezing agent in the food
industry and to produce artificial rain.

Figure 4.6 The Lewis structure of CO2

4.4.4 Oxoacid of carbon

Oxoacid of carbon is referred to as carbonic acid (H2CO3) which is a weak acid. The bond
structure of H2CO3 is given in Figure 4.7. Carbonic acid can be prepared by dissolving
CO2 in water under pressure.

CO2(aq) + H2O(l) H2CO3(aq)

H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+(aq)

HCO3-(aq) + H2O(l) CO32-(aq) + H3O+(aq)

Figure 4.7 The bond structure of H2CO3

Hydrogen atom which is directly connected to oxygen atom can be released as a proton
to the solution by exhibiting the acidic property of carbonic acid.

Carbon dioxide reacts with bases to produce carbonates showing its acidic property. In
the presence of excess CO2 thus formed carbonates of Group 1 and 2 produce hydrogen
carbonates.

CO2(g) + 2NaOH(aq) Na2CO3(aq) + H2O(l)

Na2CO3(aq) + excess CO2(g) + H2O(l) 2NaHCO3(aq)

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4.5 Group 15 elements

4.5.1 Group trends

The first element, nitrogen of Group 15 shows different properties from the other
elements in this group (Table 4.8). Metallic character of the Group 15 elements increases
down the group. Nitrogen and phosphorous are nonmetals and show oxidation numbers
-3 to +5. Nitrogen can achieve +5 oxidation state with oxygen and fluorine. Dinitrogen,
N2 is greatly stable (inert) under normal conditions due to strong triple bond
(942 kJ mol-1). Except nitrogen, all the other elements exist as solids. The higher
electronegativity, the smaller atomic radius and the absence of d orbitals make nitrogen
different from the other elements in the group.

Table 4.8 Properties of Group 15 elements

N **P **As **Sb **Bi

Ground state
electronic [He]2s22p3 [Ne]3s23p3 [Ar]3d104s24p3 [Kr]3d105s25p3 [Xe]4f145d106s26p3
configuration
Metallic radius/ pm - - - - 182
Covalent radius/ pm 75 110 122 143 152
Melting point/ °C -210 44 (white) 613 630 271
590 (red)
Pauling 3.0 2.2 2.2 2.0 2.0
electronegativity
**Not relevant to the current G. C. E. (A/L) Chemistry syllabus

4.5.2 Chemistry of nitrogen

Nitrogen (boiling point is 195.8 °C) is slightly soluble in water under atmospheric
pressure, but the solubility greatly increases with pressure. Nitrogen does not form
allotropes. Dinitrogen shows only a few reactions and one of them is given below.

3Mg(s) + N2(g) Mg3N2(s)

Since nitrogen is an inert gas its chemical reactions occur under strong conditions. For an
instance nitrogen gas reacts with oxygen in the presence of external energy from an
elctrical spark. This reaction naturally occurs in lightening.

N2(g) + 2O2(g) 2NO2(g)

Nitrogen shows oxidation states from –3 to +5. Compounds with these oxidation states
are shown in Table 4.9.

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Table 4.9 Oxidation states of nitrogen

Oxidation Compound Formula Bond structure

state
-3 Ammonia NH3

-2 Hydrazine N2H4

-1 Hydroxylamine NH2OH

0 Dinitrogen N2
+1 Dinitrogen N2O
monoxide
+2 Nitrogen NO
monoxide
+3 Dinitrogen N2O3
trioxide

+4 Nitrogen NO2
dioxide
+4 Dinitrogen N2O4
tetroxide

+5 Nitric acid HNO3

+5 Dinitrogen N2O5
pentoxide

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4.5.3 Oxoacids of nitrogen

Nitrous acid which is unstable under normal atmospheric conditions is a weak acid. The
bond structure of nitrous acid is given in Figure 4.8.

Figure 4.8 The bond structure of nitrous acid

Nitrous acid can undergo disproportionation to produce nitric acid and nitrogen monoxide
which is a colourless gas.

3HNO2(aq) HNO3(aq) + 2NO(g) + H2O(l)

Futher reaction of nitrogen monoxide with oxygen forms nitrogen dioxide which is redish
brown in colour.

2NO(g) + O2(g) 2NO2(g)

Nitric acid (Figure 4.9) is an oily and hazardous liquid. This acid is a strong oxidizing
agent and can undergo vigorous chemical reactions.

Figure 4.9 The bond structure of nitric acid

Due to the light-induced decomposition, nitric acid produces oxygen and nitrogen
dioxide.
hν
4HNO3(aq) 4NO2(g) + O2(g) + 2H2O(l)

Due to this reason concentrated nitric acid is stored in brown colour glass bottles in
laboratories.

Oxidizing and reducing reactions of nitric acid

Dilute nitric acid reacts with metals to produce metal nitrate and hydrogen gas. In these
reactions nitric acid acts as an oxidizing agent with respect to hydrogen. When
magnesium and copper reacts with concentrated nitric acid it acts as an oxidizing agent
with respect to nitrogen.

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Mg(s) + dil. 2HNO3(aq) Mg(NO3)2(aq) + H2(g)

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

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

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

The reactions of conc. HNO3 acting as an oxidizing agent with non metals such as carbon
and sulphur are given below.

C(s) + conc. 4HNO3(l) CO2(g) + 4NO2(g) + 2H2O(l)

S(s) + conc. 6HNO3(l) H2SO4(l) + 6NO2(g) + 2H2O(l)

4.5.4 Ammonia and ammonium salts

Ammonia is a colourless gas with a strong characteristic smell. Ammonia is a basic gas
which is readily soluble in water.
NH3(g) + H2O(l) NH4OH(aq)

Ammonium hydroxide is a weak base and partially dissociates to produce ammonium

ions and hydroxide ions.

NH4OH(aq) NH4+(aq) + OH ̅ (aq)

Like any other base it reacts with dilute acids to produce aqueous salts.

2NH4OH(aq) + dil. H2SO4(aq) (NH4)2SO4(aq) + 2H2O(l)

Hydrolysis of the ammonium ion in aqueous solution produces the conjugate base,
ammonia.

NH4+(aq) + H2O(l) NH3(aq) + H3O+(l)

All amonium salts reacts with alkali to liberate amonia.

NH4Cl(aq) + NaOH(aq) NaCl(aq) + NH3 (g) + H2O(l)

Reactions of ammonia
Ammonia acts as a reducing agent with chlorine, and the products vary with the amount
of ammonia and chlorine used. In the presence of excess ammonia, chlorine produces
nitrogen gas as one of the products. However, with excess chlorine, nitrogen trichloride
is produced as one of the products, which is used for water disinfection.

excess ammonia, 2NH3(g) + 3Cl2(g) N2(g) + 6HCl(g)

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The formed HCl further reacts with unreacted ammonia to form NH4Cl. excess chlorine,

3Cl2(g) + NH3(g) 3HCl(g) + NCl3(l)

Nitrogen trichloride is a covalent chloride. It reacts with water to produce ammonia and
hypochlorous acid. Due to the ability to produce hypochlorous acid, nitrogen trichloride
is used as a water disinfecting agent.

NCl3(l) + 3H2O(l) NH3(g) + 3HOCl(aq)

Gaseous ammonia reacts with hydrogen chloride to produce a white smoke of solid
ammonium chloride. This can be used as a confirmation test for ammonia.

NH3(g) + HCl(g) NH4Cl(s)

Ammonia acts as a weak reducing agent with CuO and Cl2.

3CuO(s) + 2NH3(g) N2(g) + 3Cu(s) + 3H2O(g)

2NH3(g) + 3Cl2(g) N2(g) + 6HCl(g)

Ammonia can act as an oxidizing agent as well as an acid with metals under dry condition.

2Na(s) + 2NH3(l) 2NaNH2(l) + H2(g)

3Mg(s) + 2NH3(l) Mg3N2(l) + 3H2(g)

Thermal decomposition of ammonium salts

Some ammonium salts decompose upon heating to ammonium gas and to the acidic gas.

(NH4)2CO3(s) 2NH3(g) + CO2(g) + H2O(g)

NH4Cl(s) NH3(g) + HCl(g)

(NH4)2SO4(s) NH3(g) + H2SO4(g)*

*Prodcts of this reaction can vary with conditions.

However, anions in some ammonium salts can oxidize the ammonium ion to produce
many products upon heating.

NH4NO2(s) N2(g) + 2H2O(g)

NH4NO3(s) N2O(g) + 2H2O(g)

(NH4)2Cr2O7(s) N2(g) + Cr2O3(s) + 4H2O(g)

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Identification of ammonium salts

All ammonium salts produce ammonium gas with NaOH on warming. This gas
produces white fumes of ammonium chloride when a glass rod moistened with
concentrated hydrochloric acid.

NH4+(aq) + OH¯(aq) NH3(g) + H2O(l)

NH3(g) + HCl(g) NH4Cl(s) white fumes

Reactions of nitrate
Reaction of nitrate with iron(II)/ conc. sulphuric acid can be used to identify nitrate ion.
This test is known as brown ring test. The brown coloured [Fe(NO)]2+ ring formed in the
test tube, confirms the presence of nitrate.

2NO3ˉ (aq) + 4H2SO4(l) + 6Fe2+(aq) 6Fe3+(aq) + 2NO(g) + 4SO42ˉ (aq) + 4 H2O(l)

Fe2+(aq)+ NO(g) [Fe(NO)]2+(aq) brown colour

Nitrate reacts with Al/ NaOH to produce ammonia.

3NO3ˉ (aq) + 8Al(s) + 5OHˉ(aq) + 18H2O(l) 3NH3(g) + 8[Al(OH)4]ˉ(aq)

4.6 Group 16 elements

4.6.1 Group trends

First element, oxygen of Group 16 shows different properties to the other elements in the
group. Metallic nature increases going down the group. However, none of the Group 16
elements behaves as true metals. Both oxygen and sulphur are non-metals and other
elements in the group show metallic and nonmetallic properties. Only oxygen exists as a
gas, and other elements in the group are solids. Except for oxygen, other elements in the
group can form even-numbered oxidation states from +6 to -2. Stability of +6 and -2
oxidation states decreases down the group whereas the stability of the +4 oxidation state
increases.

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Table 4.10 Properties of Group 16 elements

O S **Se **Te **Po

2 2 10 10
Ground state [He]2s [Ne]3s [Ar]3d [Kr]4d [Xe]4f 5d106s2
14

electronic 2p4 3p4 4s24p4 5s25p4 6p4

configuration
Ionic radius X2-/ pm 140 184 198 221 -
Covalent radius/ pm 73 103 117 137 140
Melting point/ °C -218 113(α) 217 450 254
Pauling 3.4 2.6 2.6 2.1 2.0
electronegativity
1st electron gain -141 -200 -195 -190 -183
enthalpy/ kJ mol-1
X(g) + e X-(g)
2nd electron gain 844 532 - - -
enthalpy/ kJ mol-1
X-(g) + e X2-(g)
** Not a part of the current G. C. E. (A/L) Chemistry syllabus

4.6.2 Hydrides of Group 16

Group 16 elements form simple hydrides with hydrogen. All of them are covalent
hydrides. The variation of selected properties down the group of hydrides are shown in
Table 4.11.

Table 4.11 Selected properties of Group 16 hydrides

H2 O H2 S H2Se H2Te
Melting point/ °C 0.0 -85.6 -65.7 -51
Boiling point / °C 100.0 -60.3 -41.3 -4
Bond length/ pm 96 134 146 169
Bond angle/ ° 104.5 92.1 91 90

Due to the extensive hydrogen bonding, H2O shows abnormally high boiling and melting
points than the other hydrides of the group. Water is the only non-poisonous hydride
among all the other hydrides of the group.

The observed varation in bond length of covalent hydrides is due to the increase of size
of the central atom. Therefore, bond length increases down the group.

The covalent bond angle decreases as you come down in the group due to the less
repulsion of the bonding electrons as a result of electronegativity of the central atom
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decreases down the group. In H2S, H2Se and H2Te the bond angles become close to 90°.
This may also suggest that almost pure p orbitals on selenium and tellurium especially
are used for binding with hydrogen.

4.6.3 Oxygen
Oxygen has two allotropes, dioxygen (O2) and trioxygen (ozone, O3). Dioxygen is a
colourless and an odourless gas which is slightly soluble in water. Ozone has a pungent
odour. Ozone has a bond angle of 111.5°. Structure of these two allotropes are shown
below.

(a) (b)

Figure 4.10 Structure of oxygen and ozone

Catalytic decomposition of potassium chlorate and hydrogen peroxide can be used to

produce oxygen.

2KClO3(s) 2KCl(s) + 3O2(g), heating in the presence of MnO2 or Pt

2H2O2(aq) 2H2O(l) + O2(g), heating in the presence of MnO2

Metals react with dioxygen to produce metal oxides. Ozone is a powerful oxidizing agent
stronger than dioxygen. Ozone is used to disinfect water in many developed countries to
kill pathogens. Unlike chlorine, ozone does not produce any harmful byproducts in the
disinfection process.

4.6.4 Sulphur
Sulphur can be classified as it is explained below.

Sulphur

Crystalline Amorphous

Rhombic Monoclinic Plastic Colloidal Milk of

(α-Sulphur) (β –Sulphur) Sulphur

Figure 4.11 Classification of sulphur

Unlike oxygen, sulphur forms single bonds with itself rather than double bonds. The most
commonly occurring allotrope is rhombic sulphur which is referred to as α-sulphur (α-

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S8). It has a crown shape with eight-membered ring that has a cyclic zigzag arrangement
as shown below. When heated above 93 °C, α-S8 changes its packing arrangement to the
other commonly found form of monoclinic sulphur, β-sulphur (β-S8). These two forms
are allotropes of each other.

(a) (b) (c)

Figure 4.12 (a) crown form of S8 (b) Rhombic sulphur (c) Monoclinic sulphur

Crystalline form of rhombic and monoclinic sulphur consist of S8 rings in the shape of
crown. These can be packed together in two different ways to form rhombic crystals and
to form needle shaped monoclinic crystals as shown above. Below 95 °C the rhombic
form is the most stable allotropic form of sulphur.

Amorphous sulphur is an elastic form of sulphur which is obtained by pouring melted

sulphur into water. Sudden cooling of molten sulphur with open chains converts liquid
sulphur to amorphous sulphur with open chains. With time, amorphous sulphur converts
to crystalline sulphur. The amorphous form of sulphur is malleable but it is unstable.

4.6.5 Oxygen containing compounds

Water and hydrogen peroxide
Structures of H2O and gaseous H2O2 are shown in the figures below.

(a) (b)

Figure 4.13 Structures of (a) H2O and (b) H2O2

Water is the most widely used solvent. Water ionizes as follows. This is reffered to as
self-ionization of water.
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2H2O(l) H3O+(aq) + OH-(aq)

An amphiprotic molecule can either donate or accept a proton. Therefore, it can act as an
acid or a base. Water is an amphiprotic compound since it has the ability to accept and
release a proton. The amphoteric nature of water is shown below

H2O(l) + HCl(aq) H3O+(aq) + Cl-(aq)

H2O(l) + NH3(aq) NH4+(aq) + OH-(aq)

4.6.6 Hydrogen peroxide

Hydrogen peroxide (H2O2) is a nonplanar molecule. The H2O2 molecule contains two OH
groups which do not lie in the same plane and have a bent molecular shape with the bond
angle in the gaseous phase for H-O-O as 94.8°. The structure shown in Figure 4.13 is the
one that reduces with a minimum repulsion between the lone pairs found on the ‘O’ atoms.
The two H-O groups have a dihedral angle of 111.5° between each other as indicated
above in Figure 4.13.

Due to the extensive hydrogen bonding, H2O2 is a viscous liquid H2O2 can act as an
oxidizing as well as a reducing agent. It oxidizes to oxygen and reduces to water.

Reducing half-reaction;

H2O2(aq) + 2H+(aq) + 2e 2H2O(l)

Oxidizing half-reaction;

H2O2(aq) 2H+(aq) + O2(g) + 2e

Disproportionation;

2H2O2(aq) O2(g) + 2H2O(l)

Reactions of H2O2
H2O2 as an oxidizing agent;

H2O2(aq) + 2H+(aq) + 2I-(aq) I2(aq) + 2H2O(l)

H2O2(aq) + 2H+(aq) + 2Fe2+(aq) 2Fe3+(aq) + 2H2O(l)

H2O2 as a reducing agent;

2MnO4-(aq) + 5H2O2(aq) + 6H+(aq) 2Mn2+(aq) + 5O2(g) + 8H2O(l)

Cr2O72-(aq) + 3H2O2(aq) + 8H+(aq) 2Cr3+(aq) + 7H2O(l) + 3O2(g)

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4.6.7 Sulphur containing compounds

Hydrogen sulphide
Hydrogen sulphide, H2S is a colourless, toxic and acidic gas with the odour of “rotten
eggs”. H2S can be produced by reacting metal sulphides with strong acids. It dissolves in
water to produce weak acidic solutions.

Reactions of hydrogen sulphide

H2S as an acid with strong bases;

NaOH(aq) + excess H2S(g) NaHS(s) + H2O(l)

2NaOH(aq) + limited H2S(g) Na2S(s) + 2H2O(l)

H2S reacts with metals as an acid as well as an oxidizing agent;

2Na(s) + excess 2H2S(g) 2NaHS(s) + H2(g)

2Na(s) + limited H2S(g) Na2S(s) + H2(g)

Mg(s) + H2S(g) MgS(s) + H2(g)

H2S as a reducing agent;

2KMnO4(aq)+3H2SO4(aq)+5H2S(g) K2SO4(aq)+5S(s)+2MnSO4(aq)+8H2O(l)

K2Cr2O7(aq)+4H2SO4(aq)+3H2S(g) K2SO4(aq)+Cr2(SO4)3(aq)+3S(s)+7H2O(l)

2H2S(aq) + SO2(g) 3S(s) + 2H2O(l)

Sulphur dioxide
Sulphur dioxide is a colourless gas and soluble in water. Sulphur dioxide can act as an
oxidizing and a reducing agent.

Reactions of sulphur dioxide

As an oxidizing agent;

2Mg(s) + SO2(g) 2MgO(s) + S(s)

3Mg(s) + SO2(g) 2MgO(s) + MgS(s)

As a reducing agent;

5SO2(g) + 2KMnO4(aq) + 2H2O(l) K2SO4(aq) + 2MnSO4(aq) + 2H2SO4(aq)

3SO2(g) + K2Cr2O7(aq) + H2SO4(aq) K2SO4(aq) + Cr2(SO4)3 (aq)+ H2O(l)

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SO2(g) + 2FeCl3(aq) + 2H2O(l) H2SO4(aq) + 2FeCl2 (aq) + 2HCl(aq)

4.6.8 Oxoacids of sulphur

Common oxidation numbers of sulphur are -2, 0, +2, +4 and +6.

Sulphuric acid
Sulphuric acid is a strong diprotic acid. Sulphur trioxide reacts with water to produce
sulphuric acid.

SO3(g) + H2O(l) H2SO4(aq)

H2SO4(aq) + H2O(l) HSO4-(aq) + H3O+(aq)

HSO4-(aq) + H2O(l) SO42-(aq) + H3O+(aq)

Concentrated sulphuric acid can act as a dehydrating agent.

conc. H2SO4
C6H12O6(s) 6C(s) + 6H2O(g)
conc. H2SO4
C2H5OH(l) C2H4(g) + H2O(l)

Concentrated hot sulphuric acid can act as an oxidizing agent.

With metals,

2H2SO4(l) + Mg(s) SO2(g) + MgSO4(aq) + 2H2O(l)

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

With nonmetals,

S(s) + 2H2SO4(l) 3SO2(g) + 2H2O(l)

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

Dilute H2SO4 act as an acid.

H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)

H2SO4(aq) + Mg(s) MgSO4(aq) + H2(g)

Dilute sulphuric acid is a strong acid which can protonate to give two H+ ions to water as
shown below.
H2SO4(aq) + 2H2O(l) SO42-(aq) + 2H3O+(aq)

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Figure 4.14 Structure of sulphuric acid

Sulphurous acid
Due to the air oxidation of sulphurous acid, it always contains a small amount of sulphuric
acid. The reaction of gaseous sulphur dioxide and water produces sulphurous acid. The
sulphurous acid reacts with dissolved oxygen in water to produce sulphric acid. Structure
of the sulphurous acid is shown below. This acid is a weaker acid than sulphuric acid.

Figure 4.15 Structure of sufurous acid

Thiosulphuric acid
Only the salts of thiosulphuric acid are stable and thiosulphate ion can oxidize as well as
reduce to give sulphur and sulphur dioxide as its products. Thiosulphuric is a weak acid.
In aqueous solutions, thiosulphuric acid can decompose to produce a mixture of sulphur
containing products.

H2S2O3(aq) S(s) + SO2(g) + H2O(l)

Thiosulphate ion can act as a reducing agent.

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

Structures of thiosulphuric acid and thiosulphate ion are shown below. The oxidation
state of the central sulphur atom is +4 where as the terminal sulphur is zero in both
structures.

Figure 4.16 Thiosulphuric acid and thiosulphate ion

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4.7 Group 17 elements

4.7.1 Group trends

Halogens are reactive and can only be found naturally as compounds. Fluorine is the most
electronegative element and exhibits -1 and 0 oxidation states. The halogens other than
fluorine form stable compounds corresponding to nearly all values of the oxidation
numbers from -1 to +7. However, compounds of bromine with the oxidation state of +7
are unstable. Due to the smaller atomic radius, fluorine can stabilize higher oxidation
states of other elements.

Oxidizing ability of halogens decreases down the group. Fluorine is a powerful oxidizing
agent. The reactivity of halegons decreases down the group. This can be explained by
using the displacement reactions of halegons.

Cl2(aq) + 2Br-(aq) 2Cl-(aq) + Br2(aq)

Br2(aq) + 2I-(aq) 2Br-(aq) + I2(aq)

Fluorine and chlorine are gases with pale yellow and pale green colours respectively at
room temperature. Bromine is a red-brown fumming liquid and iodine is a violet-black
solid with lustrous effect.

The bond energy of F2 (155 kJ mol-1) is less than that of Cl2 (240 kJ mol-1) due to repulsion
between the non-bonded electron pairs of fluorine atoms. This is a reason for the high
reactivity of fluorine gas. Down the Group 17 bond energies show a gradual decrease
(Cl2 = 240 kJ mol-1, Br2 = 190 kJ mol-1 and I2 = 149 kJ mol-1).

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Table 4.12 Properties of Group 17 elements

F Cl Br I **At
Ground state
electronic [He]2s22p5 [Ne]3s23p5 [Ar]3d104s24p5 [Kr]4d105s25p5 [Xe]4f145d106s26p5
configuration
van der Waals 135 180 195 215 -
radius/ pm
Ionic radius X-/ pm 133 181 196 220 -
Covalent radius/pm 71 99 114 133 -
Melting point/ °C -220 -101 -7.2 114 -
Boiling point/ °C -188 -34.7 55.8 184 -
Pauling 4.0 3.2 3.0 2.7 -
electronegativity
Electron gain -328 -349 -325 -295 -
enthalpy/ kJ mol-1
X(g) + e X-(g)
**Not relevant to the current G. C. E. (A/L) Chemistry Syllabus

4.7.2 Simple compounds of Group 17

Hydrogen halides
Hydrogen halides are acidic in water. HF has the ability to produce extensive hydrogen
bonding, however, HF is a gas (boiling point 20 °C) at room temperature and under
atmospheric pressure.

Acidic nature of hydrogen halides in aqueous solutions

For HF; HF(g) + H2O(l) H3O+(aq) + F-(aq)

For other hydrohen halides (HCl, HBr and HI);

HX(g) + H2O(l) H3O+(aq) + X-(aq)

HF is a weak acid whereas the other hydrogen halides are strong acids in the aqueous
medium. HF has the high bond energy (strongest covalent bond), which makes it difficult
to dissociate in water to produce H+ ions readily. The acidic strength of hydrogen halides
increases down the Group 17. This can be explained using the same fact mentioned above.
Some selected properties of Group 17 hydrogen halides are shown in Table 4.13.

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Table 4.13 Selected properties of group 17 hydrogen halides

HF HCl HBr HI
Melting point/ °C -84 -114 -89 -51
Boiling point / °C 20 -85 -67 -35
Bond length/ pm 92 127 141 161
Bond dissociation energy/ kJ mol-1 570 432 366 298

Silver halides
Silver halides can be used to identify the halides (chloride, bromide, and iodide) using the
colour of the precipitate. Few selected properties are shown below.

Table 4.14 Silver halides of Group 17 elements

Silver halide Colour Solubility in ammonia

AgCl White Dissolves in dil. aqueous ammonia
AgBr Pale yellow Dissolves in conc. aqueous ammonia
AgI Yellow Insoluble in both dil. and conc. aqueous
ammonia

Oxides and oxoacids of chlorine

Chlorine forms several oxides and oxoanions with variable oxidation states. Some
oxoanions are strong oxidizing agents. Selected oxides of chlorine are shown in Table
4.15.

Table 4.15 Selected oxides and oxoanions of chlorine

Oxidation Formula of oxide Formula of Structure of

state oxoanion oxoanion
+1 Cl2O ClO-

+3 ClO2-

+5 ClO3-

+6 ClO3 and Cl2O6

+7 Cl2O7 ClO4-

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Chlorine forms four types of oxoacids. The acidic strength increases with the increasing
oxidation number of the chlorine atom. The stuctures and the oxidation states of oxoacids
are given in the Table 4.16.

Table 4.16 Structures of oxoacids of chlorine

HClO HClO2 HClO3 HClO4
Oxidation state +1 +3 +5 +7
Structure

Oxidizing power of oxoacids of chlorine changed as follows.

HClO > HClO2 > HClO3 > HClO4

The oxidation state of chlorine in HClO, HClO2, HClO3, HClO4 respectively are +1, +3, +5
and +7. The higher the oxidation state the stronger the acid will be. Therefore the variation
of acidic strength is HClO < HClO2 < HClO3 < HClO4.

Halides
Most covalent halides react vigorously with water. But CCl4 does not hydrolyze. Most
fluorides and some other halides are inert.

Chlorides of group 14 and 15 elements react with less water as follows.

SiCl4(l) + 2H2O(l) 4HCl(aq) + SiO2(s)

PCl5(l) + H2O(l) POCl3(aq) + 2HCl(aq)

Chlorides of group 14 and 15 elements react excess water as follows.

SiCl4 (l) + 3H2O(l) 4HCl(aq) + H2SiO3(aq)

NCl3(l) + 3H2O(l) NH3(aq) + 3HOCl(aq)

PCl3(l) + 3H2O(l) H3PO3(aq) + 3HCl(aq)

PCl5(l) + 4H2O(l) H3PO4(aq) + 5HCl(aq)

AsCl3(s) + 3H2O(l) H3AsO3(aq) + 3HCl(aq)

SbCl3(aq) + H2O(l) SbOCl(s) + 2HCl(aq)

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BiCl3(aq) + H2O(l) BiOCl(s) + 2HCl(aq)

4.7.3 Reactions of chlorine

Chlorine is less reactive than fluorine. Chlorine gas is a strong oxidizing agent. Some
reactions of chlorine act as a strong oxidizing agent are given below.

2Cu(s) + Cl2(g) 2CuCl(s)

2CuCl(s) + Cl2(g) 2CuCl2(s)

Fe(s) + Cl2(g) FeCl2(s)

2FeCl2(s) + Cl2(g) 2FeCl3(s)

excess ammonia, 8NH3(g) + 3Cl2(g) N2(g) + 6HCl(g)

excess chlorine, 3Cl2(g) + NH3(g) 3HCl(g) + NCl3(l)

Disproportionation reactions of chlorine

Chlorine is simultaneously reduced and oxidized when it reacts with water and bases.

Reaction of chlorine with water;

Cl2(g) + H2O(l) HOCl(aq) + HCl(aq)

In this reaction, zero oxidation state of chlorine (Cl2) oxidize to +1 (HOCl) and reduce
to -1 (Cl¯).

Reaction with sodium hydroxide;

With cold dilute sodium hydroxide
Cl2(g) + cold and dil. 2NaOH(aq) NaCl(aq) + NaOCl(aq) + H2O(l)

With hot concentrated/ hot dilute sodium hydroxide

above 80 °C
3Cl2(g) + conc. 6NaOH(aq) 5NaCl(aq) + NaClO3(aq) + 3H2O(l)

Reactions of oxoanions
ClO ̅ is stable at low temperatures and disproportionates at high temperature to produce
Cl ̅ and ClO3 ̅ . However, both BrO ̅ and IO ̅ are not stable even at low temperatures
and undergo disproportionation.

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Disproportionation reactions of hypochlorite

Disproportionation of hypochlorite to produce chlorate and chloride can be written as;

3ClO ̅ ClO3 ̅ + 2Cl ̅

Under acidic conditions, HOCl is more stable than ClO ̅ , which makes disproportionation
predominant under basic conditions.

4.8 Group 18 elements

4.8.1 Group trends

All group 18 elements are unreactive monoatomic gasses. Only Xe forms a significant
range of compounds. All group 18 elements have positive electron gain enthalpy because
an incoming electron needs to occupy an orbital belonging to a new shell.

Table 4.17 Properties of Group 18 elements

He Ne Ar Kr Xe
Ground state
electronic 1s2 [He]2s22p6 [Ne]3s23p6 [Ar]3d104s24p6 [Xe]4d105s25p6
configuration
Atomic radius/ pm 99 160 192 197 240
1st ionization energy/ 2373 2080 1520 1350 1170
kJ mol-1
Electron gain 48.2 115.8 96.5 96.5 77.2
enthalpy/ kJ mol-1

4.8.2 Simple compounds of group 18 elements

Compounds of xenon have oxidation numbers of +2, +4, +6 and +8. Xenon reacts directly
with fluorine. Some Xe compounds are shown in Table 4.18.

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