The p-Block Elements

Group 13 and 14
➢ P-block: General introduction
• What makes the heavier p-block elements chemistry interesting: the influence of d and
f electrons in the inner core.
• Last electron → outermost p orbital.
• Total groups in P-block- six groups, numbered from 13 to 18.
• Valence shell electronic configuration- ns2 np1-6 (except for He).
• Maximum oxidation state- the total number of valence electrons (i.e., the sum of the s-
and p-electrons).
• The important oxidation states exhibited by p-block elements are shown in Table below.

• Occurrence of oxidation states two unit less than the group oxidation- ‘inert pair effect’.
• Non-metals and metalloids exist only in- p-block.
• Non-metallic character- decreases down the group- best illustrated by the nature of
oxides they form.
• Non-metal oxides- acidic or neutral || metal oxides- basic.
• Heaviest element in each p-block group is the most metallic in nature.
• Boron (second period elements of p-groups)-max covalency is 4 eg..BF4-
• Third period elements (3s23pn) utilize the vacant 3d orbitals to expand their covalence
above four. For example, aluminium gives [AlF6]3– ion.

➢ Group 13- Boron family:

• Boron- non-metal, Aluminium- metal but shows many chemical similarities to boron.
• Gallium, Indium, Thallium and nihonium- metallic in character.
• Boron (fairly rare element, poorly abundant) occurs as orthoboric acid, (H3BO3), borax,
Na2B4O7·10H2O, and kernite, Na2B4O7·4H2O.
• Two isotopic forms of boron- 10B (19%) and 11B (81%).

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• Aluminium- third most abundant element in the earth’s crust
• Important minerals of Aluminium- Bauxite, Al2O3. 2H2O and cryolite, Na3AlF6
• Half life of its most stable isotope of Nihonium (synthetically prepared radioactive
element)- 20 seconds.
• Outer electronic configuration of B family- ns2np1.
• Refer to the following table for various physical properties of group 13 elements.

• Atomic radii order- B < Ga < Al < In < Tl.

• Boron- non-metal. Extremely hard and black coloured solid.
• Gallium- unusual low melting point (303K).
• B forms covalent bonds- Due to the small size of boron, the sum of its first three
ionization enthalpies is very high. This prevents it to form +3 ions and forces it to form
only covalent compounds.
• Relative stability of +1 oxidation state progressively- Al<Ga<In<Tl
• Boron in BF3 has only six electrons- electron deficient molecule- Lewis acid. BCl3
easily accepts a lone pair of electrons from ammonia to form BCl3NH3.

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• The tendency to behave as Lewis acid decreases with the increase in the size down the
group.
• AlCl3 achieves stability by forming a dimer

• Group 13 trichlorides on hydrolysis in water form tetrahedral M(OH)4− species where

M is sp3 hybridised.
• AlCl3 in acidified aqueous solution forms octahedral [Al(H2O)6]3+ ion. In this complex,
3d orbitals of Al are involved and the hybridisation state of Al is sp3d2.
• Boron is unreactive in crystalline form.
• Amorphous boron and aluminium metal on heating in air form B2O3 and Al2O3
respectively.
• B2O3 is acidic and reacts with basic (metallic) oxides forming metal borates.
• Al2O3 and Ga2O3- amphoteric. In 2O3 and Tl2O3- basic.

• With dinitrogen at high temperature they form nitrides.

• Boron does not react with acids and alkalies even at moderate temperature.
• Aluminium shows amphoteric character. Aluminium dissolves in dilute HCl and
liberates dihydrogen.

• Al forms a protective oxide layer on the surface when reacted with conc. nitric acid
• Dihydrogen gas is released when Al reacts with alkali.

• Group 13 elements react with halogens to form trihalides (except TlI3).

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➢ Borax:
White crystalline solid Na2B4O7.10H2O. contains the tetranuclear units [B4O5(OH)4]2−
Correct formula; therefore, is Na2[B4O5 (OH)4].8H2O.
• Borax dissolves in water to give an alkaline solution.

• Borax bead (glass like material) is obtained on heating borax.

• Borax bead test is performed to identify metaborates of many transition metals that have
characteristic colours.
• Co(BO2)2 bead is blue in color.
• Orthoboric acid:
• A weak monobasic acid.
• A protonic acid but acts as a Lewis acid
• H3BO3 is a white crystalline sparingly soluble in water but highly soluble in hot water
prepared by acidifying an aqueous solution of borax.

• It has layer structure in which planar BO3 units are joined by hydrogen bonds

• On heating, orthoboric acid above 370K forms metaboric acid, HBO2 which on further
heating yields boric oxide, B2O3.

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 • Diborane B2H6: colourless, highly toxic gas with a b.p. of 180 K. catches fire in air.

• Prepared by treating BF3 with LiAlH4

• laboratory method to prepare diborane:

• Industry method to prepare diborane:

• Boranes are readily hydrolysed by water

• Reaction of diborane with Lewis bases(L) to give borane adducts, BH3L.

• Reaction of diborane with ammonia to give borazine, B3N3H6 known as “inorganic

benzene”

➢ Structure of B2H6:

Each B atom- sp3 hybridised.

The terminal B-H bonds are normal 2-centre-2-electron bonds but the two bridge bonds are 3-
centre-2-electron bonds (banana bonds).
• Boron forms a series of hydridoborates of several metals:

➢ USES OF BORON AND ALUMINIUM AND THEIR COMPOUNDS:

• Boron fibres are used in making bullet-proof vest and light composite material for
aircraft.
• Metal borides (10B isotope) are used in nuclear industry as protective shields and
control rods.
• Industrial application of borax and boric acid- manufacture of heat resistant glasses
(e.g., Pyrex), glass-wool and fibreglass.
• Borax: used as a flux for soldering metals, and as constituent of medicinal soaps.

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 • Orthoboric acid- aqueous solution is generally used as a mild antiseptic.
• Electrical conductivity of aluminium is twice that of copper.
• Aluminium and its alloys: pipe, tubes, rods, wires, plates or foils, construction,
aeroplane and transportation industry.
➢ Group 14: Carbon family
• Members: C, Si, Ge, Sn, Pb, Fl
• Carbon- most versatile element- available as coal, graphite and diamond. In combined
state- metal carbonates, hydrocarbons and carbon dioxide gas (0.03%) in air.
• Carbon isotopes: 12C, 13C, and 14C.
• Silicon in nature- in the form of silica and silicates used in ceramics, glass and cement.
• Germanium exists only in traces. Tin occurs mainly as cassiterite, SnO2 and lead as
galena, PbS. Flerovium is a synthetically prepared radioactive element.
• Ultrapure form of germanium and silicon- used to make transistors and semiconductor
devices.
• valence shell electronic configuration- ns2np2.
• Refer to the following table for various physical properties of group 14 elements

• All members of group14 are solids

• Carbon and silicon- non-metals
• Ge- metalloid.
• Tin and lead -soft metals with low melting points.
• The common oxidation states- +4 and +2.
• Group 14 (except carbon) halides undergo hydrolysis and have a tendency to form
complexes by accepting electron pairs from donor species. For example, the species

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 like SiF62–, [GeCl6]2–, [Sn(OH)6]2– exist where the hybridisation of the central atom is
sp3d2.
• Oxides: monoxide (MO) and dioxide (MO2)
• Oxides in higher oxidation states of elements are generally more acidic than those in
lower oxidation states.
• CO2, SiO2 and GeO2 are acidic, whereas SnO2 and PbO2 are amphoteric in nature.
• CO is neutral, GeO is distinctly acidic whereas SnO and PbO are amphoteric.
• Tin decomposes steam to form dioxide and dihydrogen gas.

• These elements form covalent halides of formula MX2 and MX4 (where X = F, Cl, Br,
I).
• SnF4 and PbF4, which are ionic in nature. PbI4 does not exist.
• Ge to Pb are able to make halides of formula MX2.
• SiCl4 undergoes hydrolysis leading to the formation of Si(OH)4

➢ IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF CARBON

• Carbon forms p𝝅– p𝝅 multiple bonds with itself (allotropic forms) and with other atoms
of small size and high electronegativity.
• Carbon atoms have the tendency to link with one another through covalent bonds to
form chains and rings. This property is called catenation.
• The order of catenation is C > > Si >Ge ≈Sn.
• Allotropic forms of C: many (Diamond, graphite, and fullerenes).

➢ Diamond:
• crystalline lattice
• Hybridisation of each C: sp3
• C–C bond length is 154 pm
• Diamond is the hardest substance on the earth.
• Uses: as an abrasive for sharpening hard tools, in
making dyes and in the manufacture of tungsten
filaments for electric light bulbs.

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➢ Graphite:
• layered structure
• Layers are held by van der Waals forces and distance
between two layers is 340 pm.
• Each layer is composed of planar hexagonal rings of
carbon atoms. C—C bond length within the layer is
141.5 pm.
• Hybridisation of each C: sp2. Fourth electron forms a
bond.
• The electrons are delocalised over the whole sheet and
hence conducts electricity.
• very soft and slippery
• Uses: as a dry lubricant
• Fullerenes: cage like molecules
• Made by heating graphite in an electric arc in the
presence of inert gases such as helium or argon.
• Fullerenes are the only pure form of carbon because they have smooth structure without
having ‘dangling’ bonds.

➢ Buckminsterfullerene: C60
• Contains twenty six- membered rings and twelve five-
membered rings
• A six membered ring is fused with six or five membered
rings but a five membered ring can only fuse with six
membered rings.
• Hybridisation of each C: sp2.
• The fourth electron delocalise in molecular orbitals,
which in turn give aromatic character to molecule.
• This spherical fullerenes are also called bucky balls in
short. C60 has 60 vertices and each one is occupied by
one carbon atom and it also contains both single and
double bonds with C–C distances of 143.5 pm and 138.3 pm respectively.
• Graphite is thermodynamically most stable allotrope of carbon
• ΔfH° of graphite is taken as zero. ΔfH° values of diamond and fullerene, C60 are 1.90
and 38.1 kJ mol–1, respectively. Other (impure) forms of elemental carbon like carbon
black, coke, and charcoal.
• Uses of Carbon: embedded in plastic material form high strength, lightweight
composites- tennis rackets, fishing rods, aircrafts
• graphite is used for electrodes in batteries
• activated charcoal is used in adsorbing poisonous gases
• Coke is used as a fuel and largely as a reducing agent in metallurgy. Diamond is used
in jewellery.

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➢ SOME IMPORTANT COMPOUNDS OF CARBON AND SILICON
• Carbon Monoxide (CO): colourless,odourless and almost water insoluble gas.
• Produced by direct oxidation of C in limited supply of oxygen.

• For small scale production: dehydration of formic acid with conc H2SO4 at 373 K

• Commercial production: by the passage of steam over hot coke.

• The mixture of CO and H2 gas is known as water or synthesis gas.

• Producer gas is produced if coke is heated in air.

• CO is a powerful reducing agent.

• CO has one sigma and two 𝝅-bonds.

• Because of the presence of a lone pair on carbon, CO molecule acts as a donor.
• CO forms a complex with haemoglobin, which is about 300 times more stable than the
oxygen-haemoglobin complex.
• Carbon Dioxide (CO2): a colourless and odourless gas
• Prepared by complete combustion of carbon and carbon containing fuels in excess of
air.

➢ Laboratory method:

• On commercial scale, it is obtained by heating limestone.

• CO2 react with water to form carbonic acid, H2CO3 (a weak dibasic acid)

• H2CO3/HCO3– buffer system helps to maintain pH of blood between 7.26 to 7.42.

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➢ Photosynthesis:

• CO2 cause greenhouse effect

• Solid CO2 is called dry ice
• C-O bond length is 115 pm on CO2 due to resonance

• Silicon Dioxide, SiO2: a covalent, three-

dimensional network solid.
• Each silicon atom is covalently bonded
to four oxygen atoms.
• Each oxygen atom is covalently bonded
to another silicon atoms
• eight membered rings are formed with
alternate silicon and oxygen atoms

• SiO2 can be attacked by HF and NaOH

• Quartz is extensively used as a piezoelectric material Kieselghur, an amorphous form

of silica is used in filtration plants

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 • Silicones: organosilicon polymers having R2SiO as a repeating unit
• Starting material of silicones: RnSiCl(4–n) R is alkyl or aryl group.
• Hydrolysis of dimethyldichlorosilane, (CH3)2SiCl2 followed by condensation
polymerisation yields straight chain polymers.
• The chain length of the polymer can be controlled by adding (CH3)3SiCl

- Uses: Used as sealant, greases,

electrical insulators and for
waterproofing of fabrics.

- Being biocompatible they are also

used in surgical and cosmetic plants.

• Silicates: examples are feldspar, zeolites, mica

and asbestos
• The basic structural unit of silicates is SiO44–
• Silicate units links together to form chain, ring,
sheet or three-dimensional structures
• Man made silicates: glass and cement.
• Zeolites: aluminosilicate
• Cations present in zeolites: Na+, K+ or Ca2+
• Zeolites as a catalyst: e.g., ZSM-5 used to
convert alcohols directly into gasoline.
• Hydrated zeolites are used as ion exchangers in softening of “hard” water.

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 The p-Block Elements

Group 15 & 16
• Diversity in chemistry of p–block elements: due to their ability to react with the
elements of s–, d– and f–blocks as well as with their own.
• Group 15: nitrogen, phosphorus, arsenic, antimony, bismuth and moscovium N & P-
non-metals, As & Sb- metalloids, Bi & Mc are typical metals. (Metallic character
increases down the group).
➢ Occurrence:
• N occurs as NaNO3 (called Chile saltpetre), potassium nitrate (Indian saltpetre).
• Found in the form of proteins in plants and animals.
• P occurs in minerals of the apatite family, Ca9(PO4)6.CaX2 (X = F, Cl or OH)
• As, Sb and Bi are found mainly as sulphide minerals.
• Mc has a very short half-life and availability in very little amount.
• Refer to the following table for atomic and physical properties of group 15 elements

• All the elements of this group are polyatomic.

• Dinitrogen is a gas while all others are solids.
• Except nitrogen, all the elements show allotropy.
• Oxidation states and trends in chemical reactivity:
• Most common ox states: –3, +3 and +5.
• Bi hardly forms any compound in –3 oxidation state. The stability of +5 oxidation state
decreases down the group. The only well characterised Bi (V) compound is BiF5.
• Besides +5 oxidation state, nitrogen exhibits + 1, + 2, + 4 oxidation states also when it
reacts with oxygen.
• In the case of nitrogen, all oxidation states from +1 to +4 tend to disproportionate in
acid solution

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• P also shows +1 and +4 oxidation states in some oxoacids. nearly all intermediate
oxidation states disproportionate into +5 and –3 both in alkali and acid
• +3 oxidation state in case of As, Sb and Bi does not disproportionation.
• Max covalency of N: 4
• Heavier elements can expand their covalency due to the presence of d orbitals.
E.g. PF–6.
• Anomalous properties of nitrogen
• small size, high electronegativity, high ionisation enthalpy and non-availability of d
orbitals.
• p𝝅 -p𝝅 multiple bonds with itself and with other elements having small size and high
electronegativity (e.g., C, O).
• P, As and Sb form single bonds as P–P, As–As and Sb–Sb while Bi forms metallic
bonds in elemental state.
• N cannot form d𝝅 –p𝝅 bond as the heavier elements can e.g., R3P = O or R3P = CH2
(R = alkyl group).
• P and As can form d𝝅 –d𝝅 bond also with transition metals when their compounds like
P(C2H5)3 and As(C6H5)3 act as ligands.
• Reactivity towards hydrogen: EH3 where E = N, P, As, Sb or Bi.
• Reducing character of the hydrides increases down the group (BiH3 is the strongest
reducing agent)
• Basicity decreases in the order NH3 > PH3 > AsH3 > SbH3 > BiH3.

• Reactivity towards oxygen: two types of oxides: E2O3 and E2O5.

• the higher oxidation state of the element is more acidic in its oxide form
• N2O3 and P2O3 are acidic..As2O3 and Sb2O3 are amphoteric, Bi2O3- basic
• Reactivity towards halogens: EX3 and EX5
• Pentahalides are more covalent than trihalides.
• Trihalides of these elements except those of nitrogen are stable.
• In the case of nitrogen, only NF3 is known to be stable.
• Trihalides except BiF3 are predominantly covalent in nature
• Reactivity towards metals: Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide), Na3As
(sodium arsenide), Zn3Sb2 (zinc antimonide) and Mg3Bi2 (magnesium bismuthide).
• Dinitrogen: colourless, odourless, tasteless and non-toxic gas. b.p. 77.2 K

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 • Preparation:

➢ Laboratory method:

• Two stable isotopes: 14N and 15N.

• N2 is inert at room temperature, however at higher temperatures, it directly combines
with some metals to form nitrides

• Haber’s Process to form ammonia:

• Dinitrogen combines with dioxygen at around 2000K tempt

• Ammonia: colourless gas with a pungent odour

Preparation: from urea

➢ Small scale production:

• Large scale production: Haber process

• Shape: trigonal pyramidal

• Highly soluble in water. Its aqueous solution is weakly basic in nature

• NH3 forms ammonium salts with acids, e.g., NH4Cl, (NH4)2 SO4, etc. As a weak base,
it precipitates the hydroxides (hydrated oxides in case of some metals) of many metals
from their salt solutions.

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• NH3 can be used in in detection of metal ions such as Cu2+, Ag+

• Oxides of N: Refer the following table for names, formulas, preparation and physical
appearance of these oxides

• Refer to the following table for Lewis dot main resonance structures and bond
parameters of oxides:

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 • Nitric oxide: HNO3 colourless liquid

➢ Laboratory method:
Large scale: Ostwald’s process

• Conc nitric acid is a strong oxidising agent and attacks most metals except noble metals
such as gold and platinum.
• Products of oxidation depend upon the concentration of the acid, temperature and the
nature of the material undergoing oxidation.

• Zinc reacts with dilute nitric acid to give N2O and with concentrated acid to give NO2.

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 • Concentrated nitric acid also oxidises non–metals and their compounds.

➢ Brown Ring Test:

the ability of Fe2+ to reduce nitrates to nitric oxide, which reacts with Fe2+ to form a brown
coloured complex.

• Phosphorous: Allotropes -white, red and black.

• White phosphorus: poisonous, insoluble in water but soluble in CS2. Glows in dark
(chemiluminescence).
• It dissolves in boiling NaOH solution in an inert atmosphere giving PH3.

• White P is more reactive than red P because of angular strain in the P4 molecule (60°).
It readily catches fire in air to give dense white fumes of P4O10.-

• Red P (iron grey lustre) is obtained by heating white P at 573K in an inert atmosphere
for several days.

• Red P is odourless, nonpoisonous and insoluble in water as well as in carbon disulphide.

• Red P is much less reactive than white phosphorus.
• It does not glow in the dark
• It is polymeric, consisting of chains of P4 tetrahedra linked together
• Black phosphorus - 𝛼-black and 𝛽-black phosphorus.
• 𝛼-Black phosphorus is formed when red P is heated in a sealed tube at 803K.

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• 𝛽-Black phosphorus is prepared by heating white P at 473 K under high pressure
• Phosphine: colourless gas with rotten fish smell and is highly poisonous
• Prepared by the reaction of calcium phosphide with water or dilute HCl.

• In the laboratory: by heating white P with conc NaOH solution in an inert atmosphere
of CO2

• Pure PH3 is obtained by adsorbing impure PH3 in HI to form phosphonium iodide

(PH4I) which on treating with KOH gives off phosphine.

• The solution of PH3 in water decomposes in presence of light giving red P and H2.
• Ph3rx with CuSO4 or HgCl2 solution produce corresponding phosphides

• Phosphorus halide: two types of halides, PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl,
Br).
• Phosphorus chloride: pyramidal shape and phosphorus is sp3 hybridised.
• Obtained by passing dry chlorine over heated white phosphorus or by the action of
thionyl chloride with white phosphorus.

• Colourless oily liquid and hydrolyses in the presence of moisture

• It reacts with organic compounds containing –OH group

• PCl5: trigonal bipyramidal structure

• yellowish white powder, prepared by the reaction of white P with excess of dry chlorine

• By the action of SO2Cl2 on phosphorus

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 • PCl5 react with moist air to give POCl3 and finally gets converted to phosphoric acid

• When heated, it sublimes but decomposes on strong heating.

• Reacts with organic compounds containing –OH group converting them to chloro
derivatives.

• Finely divided metals on heating with PCl5 give corresponding chlorides.

•The three equatorial P–Cl bonds are equivalent, while the two axial bonds are longer
than equatorial bonds.
➢ Oxoacids of P:
• Refer the following table for the important oxoacids of phosphorus with their formulas,
methods of preparation and the presence of some characteristic bonds in their structures

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• Orthophophorous acid (or phosphorous acid) on heating disproportionates to give
orthophosphoric acid (or phosphoric acid) and phosphine.

• Hypophosphorous acid is a good reducing agent as it contains two P–H bonds

• Group 16: chalcogens, general electronic configuration: ns2 np4

• Oxygen, sulphur, selenium, tellurium, polonium and livermorium
• O & S- non-metals, Se & Te- metalloids, Po- metal and radioactive (Half-life 13.8
days).
• Occurrence: Oxygen forms about 46.6% by mass of earth’s crust
• Refer to the following table for atomic and physical properties of group16 elements

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• Sulphur exists primarily as sulphates such as gypsum CaSO4.2H2O, epsom salt
MgSO4.7H2O, baryte BaSO4 and sulphides such as galena PbS, zinc blende ZnS, copper
pyrites CuFeS2.
• Selenium and tellurium are also found as metal selenides and tellurides in sulphide ores
• Polonium occurs in nature as a decay product of thorium and uranium minerals.
• Livermorium is a synthetic radioactive element.
• Chemical properties:
• Oxidation state- Oxygen usually shows -2 oxidation state but +2 in OF2
• Other elements of the group exhibit + 2, + 4, + 6 oxidation states
• Bonding in +4 and +6 oxidation states is primarily covalent.
• Reactivity with hydrogen: H2E (E = O, S, Se, Te, Po).
• Refer to the following table for some properties of hydrides:

• Acidic character increases from H2O to H2Te.

• Thermal stability of hydrides decreases from H2O to H2Po.
• All the hydrides except water possess reducing property and this character increases
from H2S to H2Te.
• Reactivity with oxygen: EO2 and EO3, E = S, Se, Te or Po. Both types are acidic in
nature.
• O3 and SO2 are gases while SeO2 is solid.
• SO2 is reducing while TeO2 is an oxidising agent.
• Reactivity towards the halogens: EX6, EX4 and EX2
• Amongst hexahalides, hexafluorides are the only stable halides.
• Sulphur hexafluoride, SF6 is exceptionally stable for steric reasons
• SF4 is a gas, SeF4 a liquid and TeF4 a solid...sp3d hybridised...TBP geometry.
• The monohalides exist as dimer in nature, eg. S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
and undergo disproportionation

• Dioxygen: O2 is a colourless and odourless gas

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➢ Laboratory preparation:

• H2O2 is readily decomposed to H2O and O2 (Can be catalyzed by finely divided metals
and manganese dioxide)
• On large scale it can be prepared from water or air
• Industrially, dioxygen is obtained from air
• Three stable isotopes: 16O, 17O and 18O. O2 is unique in being paramagnetic
• Oxgyen-oxygen double bond strength is high (493.4 kJ mol–1).
• Some of the reactions of dioxygen with metals, non-metals and other compounds are
given below.

➢ Simple oxides:
• An oxide that combines with water to give an acid is termed acidic oxide (e.g., SO2,
Cl2O7, CO2, N2O5). For example, SO2 combines with water to give H2SO3, an acid.
• Non-metal oxides are acidic but oxides of some metals in high oxidation state also have
acidic character (e.g., Mn2O7, CrO3, V2O5)
(metallic oxides are basic.) The oxides which give a base with water are known as basic
oxides (e.g., Na2O, CaO, BaO). For example, CaO combines with water to give
Ca(OH)2, a base.
• In general, metallic oxides are basic. Some metallic oxides exhibit a dual behaviour. Eg
Al2O3.

• Examples of neutral oxides are CO, NO and N2O.

• Ozone: ozone layer protects the earth’s surface from an excessive concentration of
ultraviolet (UV) radiations.
• Formation of ozone from oxygen is an endothermic process

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• Pure ozone is a pale blue gas, dark blue liquid and violet-black solid
• Ozone is thermodynamically unstable with respect to oxygen. Due to the ease with
which it liberates atoms of nascent oxygen (O), it acts as a powerful oxidising agent.

• Quantitative method for estimating O3 gas: When ozone reacts with an excess of
potassium iodide solution buffered with a borate buffer (pH 9.2), iodine is liberated
which can be titrated against a standard solution of sodium thiosulphate
• Nitrogen monoxide combine very rapidly with ozone to produce NO2 and O2
• Oxygen-oxygen bond lengths in the ozone
molecule are identical (128 pm) and the
molecule is angular as expected with a
bond angle of about 117 degrees.
• Sulphur — Allotropic Forms: S8 - yellow
rhombic (𝛼-sulphur) and monoclinic (𝛃 -sulphur) forms
• Rhombic sulphur is stable at room temperature and transforms to monoclinic sulphur
when heated above 369 K.
• Rhombic sulphur: yellow in colour. Stable above 369 K It is readily soluble in CS2.
Monoclinic sulphur: prepared by melting rhombic sulphur in a dish and cooling.
• At 369 K both the forms are stable. This temperature is called transition temperature.
• At elevated temperatures (~1000 K), S2 is the dominant species and is paramagnetic
like O2.
• The S8 ring in both the forms is puckered and has a crown shape.

• Sulphur dioxide: SO2 is angular... colourless gas with

pungent smell
• Prepared when sulphur is burnt in air or oxygen
• In the laboratory: by treating a sulphite with dilute sulphuric acid

• Industrially, by-product of the roasting of sulphide ores

• Sulphur dioxide, when passed through water, forms a solution of sulphurous acid reacts
readily with sodium hydroxide solution

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• SO2 reacts readily with sodium hydroxide solution

• Sulphur dioxide reacts with chlorine to give sulphuryl chloride, SO2Cl2.

• It is oxidised to sulphur trioxide by oxygen in the presence of vanadium(V) oxide
catalyst.
• Moist sulphur dioxide behaves as a reducing agent

• Oxoacids of Sulphur: H2SO3, H2S2O3, H2S2O4, H2S2O5, H2SxO6 (x = 2 to 5), H2SO4,

H2S2O7, H2SO5, H2S2O8

Structures of some important oxoacids of sulphur

• Sulphuric acid: manufactured by the Contact Process

• The key step in the manufacture of H2SO4 is the catalytic oxidation of SO2 with O2 to
give SO3 in the presence of V2O5 (catalyst).

• The reaction is exothermic, reversible and the forward reaction leads to a decrease in
volume.
• Low temperature and high pressure are the favourable conditions for maximum yield.
• The sulphuric acid obtained by Contact process is 96-98% pure. Plant operates at a
pressure of 2 bar and a temperature of 720 K.
• It's a colourless, dense, oily liquid
• Characteristics: (a) low volatility (b) strong acidic character (c) strong affinity for water
and (d) ability to act as an oxidising agent
• In aqueous solution, sulphuric acid ionises in two steps

• H2SO4 as a dehydrating agent..charring action on carbohydrates.

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 • Both metals and non-metals are oxidised by concentrated sulphuric acid, which is
reduced to SO2.

Group 17 & 18
• Group 17: Halogens (salt producers), highly reactive non-metallic elements.
• Members: Fluorine, chlorine, bromine, iodine, astatine and tennessine (At & Ts are
radioactive elements)
• Occurrence: F & Cl are fairly abundant.
• F: mainly as insoluble fluorides (fluorspar CaF2, cryolite Na3AlF6 and fluoroapatite
3Ca3(PO4) 2.CaF2)
• Cl: deposits of dried up seas contain these compounds, e.g., sodium chloride and
carnallite, KCl.MgCl2.6H2O.
• Refer to the following table for the atomic and physical properties of G-17 elements

➢ Chemical properties:
• All the halogens exhibit –1 oxidation state
• Cl, Br, and I exhibit + 1, + 3, + 5 and + 7 oxidation states
• Higher oxidation states are realised mainly when the halogens are in combination with
F and O. e.g., in interhalogens, oxides and oxoacids

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 • Halogens react with metals and non-metals to form halides. The reactivity of the
halogens decreases down the group.
• Ready acceptance of an electron cause halogen to be the strong oxidising agents
• F2 is the strongest oxidising halogen and it oxidises other halide ions in solution or even
in the solid phase

➢ The relative oxidising power of halogens: evident from their standard electrode potentials
their reactions with water
• Fluorine oxidises water to oxygen whereas chlorine and bromine react with water to
form corresponding hydrohalic and hypohalous acids. reaction of iodine with water is
nonspontaneous
• I– can be oxidised by oxygen in acidic medium

➢ Anomalous behaviour of fluorine:

• Most of the reactions of fluorine are exothermic
• It forms only one oxoacid while other halogens form a number of oxoacids.
• HF is a liquid (b.p. 293 K) due to strong hydrogen bonding
• Halogen (X) reactivity towards hydrogen: All for HX, but affinity for hydrogen
decreases from fluorine to iodine
• HX dissolve in water to form hydrohalic acids.
• Acidic strength: HF < HCl < HBr < HI.
• Stability of these halides: H–F > H–Cl > H–Br > H–I.

• Reactivity towards oxygen: Halogens form many oxides but most of them are unstable.
• Fluorine forms two oxides OF2 and O2F2. Only OF2 is thermally stable at 298 K
• Both are strong fluorinating agents. O2F2 oxidises plutonium to PuF6
• Decreasing order of stability of oxides formed by halogens, I > Cl > Br.
• Higher oxides of halogens tend to be more stable than the lower ones.

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 • Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive oxidising agents and
tend to explode.
• ClO2 is used as a bleaching agent
• Bromine oxides- Br2O, BrO2, BrO3 are the least stable halogen oxides and are powerful
oxidizing agents.
• Iodine oxides- I2O4, I2O5, I2O7 are insoluble solids and decompose on heating. I2O5 is
a very good oxidising agent and is used in the estimation of carbon monoxide.
• Reactivity towards metals: form metal halides
• The ionic character of the halides decreases in the order MF > MCl > MBr > MI
• Halides in higher oxidation state will be more covalent than the one in lower oxidation
state. For example, SnCl4, PbCl4, SbCl5 and UF6 are more covalent than SnCl2, PbCl2,
SbCl3 and UF4 respectively.
• Reactivity of halogens towards other halogens: interhalogens of the types XX’, XX3’,
XX5’ and XX7’ where X is a larger size halogen and X’ is smaller size halogen.
• Chlorine: discovered in 1774 (greenish yellow)
• Preparation: By heating manganese dioxide with concentrated hydrochloric acid.

• Or a mixture of common salt and concentrated H2SO4 is used in place of HCl

• By the action of HCl on potassium permanganate

➢ Manufacture of chlorine:
• Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in the
presence of CuCl2 (catalyst) at 723 K

➢ Electrolytic process:
• Chlorine is obtained by the electrolysis of brine (concentrated NaCl solution)
• Properties: It is a greenish yellow gas with pungent and suffocating odour
• 2-5 times heavier than air
• can be liquefied easily into greenish yellow liquid which boils at 239 K.
• It is soluble in water.
• Chlorine reacts with a number of metals and non-metals to form chlorides

• has great affinity for hydrogen

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 • With cold and dilute alkalies chlorine produces a mixture of chloride and hypochlorite
but with hot and concentrated alkalies it gives chloride and chlorate.

• With dry slaked lime it gives bleaching powder.

• Chlorine reacts with hydrocarbons and gives substitution products with saturated
hydrocarbons and addition products with unsaturated hydrocarbons.

➢ Chlorine as oxidising agent:

• Chlorine is a powerful bleaching agent (permanent effect)

• Hydrogen Chloride: colourless and pungent smelling gas. Prepared by heating sodium
chloride with concentrated sulphuric acid

• HCl gas can be dried by passing through conc H2SO4.

• It is extremely soluble in water and ionises as follows:

• Aqueous solution is called hydrochloric acid.

• High value of dissociation constant (Ka) indicates that it is a strong acid in water. It
reacts with NH3 and gives white fumes of NH4Cl.
• Aqua regia: 3HCl + HNO3
It is used to dissolve noble metals, e.g., gold, platinum.

• Hydrochloric acid decomposes salts of weaker acids, e.g., carbonates,

hydrogencarbonates, sulphites, etc.

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• Uses: (i) in the manufacture of chlorine, NH4Cl and glucose (from corn starch), (ii) for
extracting glue from bones and purifying bone black, (iii) in medicine and as a
laboratory reagent.
• Oxoacids of Halogens: F forms only one oxo acid. HOF is known as fluoric (I) acid or
hypofluorous acid.
• Several oxo acids of other halogens are possible but only stable in aqueous solutions or
in the salt form.

• Interhalogen compounds: Of the types XX’, XX3’, XX5’ and XX7’ where X is a larger
size halogen and X’ is smaller size halogen.
• Iodine (VII) fluoride has maximum number of atoms as the ratio of radii between I and
F should be maximum (IF7).
• Prepared by the direct combination or by the action of halogen on lower interhalogen
compounds. The product formed depends upon some specific conditions.

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• These are all covalent molecules and are diamagnetic in nature. Only ClF is gas.
• Refer the following table for some properties of interhalogen compounds.

• Physical properties are intermediate between those of constituent halogens except that
their m.p. and b.p. are a little higher than expected.
• Interhalogen compounds are more reactive than halogens (except fluorine).
• Undergo hydrolysis giving halide ion derived from the smaller halogen and a hypohalite
(when XX’), halite (when XX’3), halate (when XX’5) and perhalate (when XX’7)
anion derived from the larger halogen.

• Interhalogen compounds are very useful fluorinating agents. ClF3 and BrF3 are used
for the production of UF6 in the enrichment of 235U.

• Group 18: noble gases: helium, neon, argon, krypton, xenon, radon and oganesson
• All are gases and chemically unreactive.

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• The main commercial source of helium is natural gas. Xenon and radon are the rarest
elements of the group. Radon is obtained as a decay product of 226Ra.

• Oganesson has been synthetically produced by collision of 249 Cf atoms and 48Ca ions

• Refer the following table for Atomic and Physical Properties of Group 18 Elements:

• Monoatomic, colourless, odourless and tasteless.

• Low melting and boiling points because the only type of interatomic interaction in these
elements is weak dispersion forces
• Helium has the lowest boiling point (4.2 K) of any known substance.
• The first ionisation enthalpy of molecular oxygen (1175 kJmol–1) was almost identical
with that of xenon (1170 kJ mol–1).
• A number of xenon compounds mainly with most electronegative elements like fluorine
and oxygen, have been synthesised.
• Only the difluoride (KrF2) has been studied in detail.
• Xenon-fluorine compounds: Xenon forms three binary fluorides, XeF2, XeF4 and XeF6
XeF6 can also be prepared by the interaction of XeF4 and O2F2 at 143K.

• XeF2, XeF4 and XeF6 are colourless crystalline solids and sublime readily at 298 K.
• They are powerful fluorinating agents.
• Readily hydrolysed even by traces of water. For example, XeF2 is hydrolysed to give
Xe, HF and O2.

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• XeF2 and XeF4 have linear and square planar structures respectively.
• XeF6 has seven electron pairs (6 bonding pairs and one lone pair)- distorted octahedral
structure.

• Xenon fluorides react with fluoride ion acceptors to form cationic species and fluoride
ion donors to form fluoroanions.

• Xenon-oxygen compounds:
Hydrolysis of XeF4 and XeF6 with water gives XeO3.

• Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2.

• XeO3 is a colourless explosive solid and has a pyramidal molecular structure.

• XeOF4 is a colourless volatile liquid and has a square pyramidal molecular structure.

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