IN I ROI>UC l'JON

We have already learnt th<.' gmcral ( haradcristks of p hlock clements and the first two
namely 1cosagcns (horon group) and tctragcns (carbon group) in the previous unit. In
it we learn the remaining p block groups, pnictogcns, chalcogcns, halogens and inert

Group 15 (Nitrogen group) elements:

About 78 % of earth atmosphere contains dinitorgen (N) gas. It is also present in earth
rust as sodium nitrate (Chile saltpetre) and potassium nitrate (Indian saltpetre). The 11th
ost abundant element phosphorus, exists as phosphate (fluroapatite, chloroapatite and
ydroxyapatite). The other elements arsenic, antimony and bismuth are present as sulphides
d are not very abundant.
.1.2 Physical properties:
Some of the physical properties of the group 15 elements are listed below
iat>le 3.1 l'hys1ca1 properties ot group IS elements
Nitro en Phos horus Arsenic Antimon Bismuth
Physical state at Solid Solid Solid Solid
Gas
293K
Atomic Number 7 15 33 51 83
14N, ISN 3lp 7sAs 121
Sb 209Bi
Isoto es
Atomic Mass 30.97 74.92 121.76 209.98
14
( .mol· 1at 293 K)
Electronic [Ar]3d 10 4s2 [Kr ]4d 10 5s 2 [Xe] 4£1 4
[He]2s 22p3 [Ne]3s 23p3
confi ration 4p3 5p3 5d 10 6s26p 3
Atomic radius (A) 1.55 1.80 1.85 2.06 2.07
Density (g.cm·3at 1.82 (white
5.75 6.68
1.14 X 10-3 9.79
293 K) phosphorus)
oint (K) 63 317 Sublimes at 904 544
77 554 889 1860 1837
.1.3 Nitrogen:
reparation:

Nitrogen, the principal gas of atmosphere (78 % by volume) is separated industrially from
iquid air by fractional distillation
Pure nitrogen gas can be obtained by the thermal decomposition of sodium azide about
75 K
► 2 Na+ 3N 2
2NaN 3 ---•

57
 lt can also be obtained by 0X1d1sing ammonia using bromine water
8NH 1 + 3Br2 ► 6NH 1Br + N2

l'ropcrlics
Nitrogen gas is rather incrt.1errestrial nitrogen contains 14.5% and 0.4% of nitrogen 14
and mtrogrn 15 respectively. The later is used for isotopic labelling. The chemically Inert
character of nitrogen is largely due to high bonding energy of the molecules 225 cal mol • (916
kj mo\ 1). lntcrcstingly the triply bonded species is notable for its less reactivity in comparison
with other iso-electronic triply bonded systems such as -C=C-, C=O, X-O=N, X-N=C, -Ge.,
and -0:N. 'These groups can act as donor where as dinitrogen cannot. However, it can form
complexes with metal (M~ N=N) like CO to a less extent
'\ne only reaction of nitrogen at room temperature is with lithium forming Li 3N. With
other c\ements, nitrogen combines only at elevated temperatures. Group 2 metals and 'Ih
forms ionic nitrides.
6Li + N2 - - - ) 2Li 3N
3Ca + N rcdhot ) Ca N
2 3 2

2B + N2 bnght red hot )

2BN
Direct reaction with hydrogen gives ammonia. This reaction is favoured by high pressures
and at optimum temperature in presence of iron catalyst. This reaction is the basis of Haber's
process for the synlhesis of ammonia.
IN + -3H__,,.
2~
-
2
NH 3 ~H r = -46.2 kJ mo! -l
2 2
With oxygen, nitrogen produces nitrous oxide at high temperatures. Even at 3473 K
nitrous oxide yield is only 4.4%.

Uses of nitrogen
l • Nitrogen is used for the manufacture of ammonia, nitric acid and cal\ium cyanamide etc.

2. Liquid nitrogen is used for producing low temperature required in cryosurgery and so·
· 1preservation .
. 1og1ca ' m
b10
3.1.4 Ammonia (NH 3)
Preparation:
Ammonia is formed by the hydrolysis of urea.
NH 2CONH 2 +H 2O ► 2NH3 +CO,

Ammonia is prepared in the laboratory by heating an ammonium salt with a base.

Nll 1 -t Oll ~ NII,+ II O

2NII ICI + Cao--) CuCI, + 2Nll, + ILO

8
-►-
It
,:
111 ,l s< 1
,,cp,ucd h) hnt111g ,1 met.ii mt11d
\lg N 611 0 ~
lll h ,n1f'n f;Jllnl "
111

I\

lM •(Olf)
n at ly t a
NII
l• t
d rrc n oV< r lro
1
. . h,,tr1,tlh 111,11111 ,1, 1u1, d t,, p,,ssmg nitrog( n nn d I ) rog f quilibnurn)
II '" illl . O t ttainmcnt o c
· of K O ,rnd Al l \ i, ,dM) used to increase the rate a bt incd from
JI ,.. uiu 111 ired 1s o a
,,ii.1 ' •()ll ,1tn1 prr~sur r. In the ,1ctu,1l process the h} drogcn rcqu
11
•1,"r,(ll-.
· uid nilHlgcn f rom 1·rul t10na
. ,.l·u1st1·11 ation o fl iqut'd.
air.
. f•'I" g.t~ • ~
\\ ,l , •
rr01 1 Ii<~ . readily hque• fi e d by
i, 1s a pungent smel1ing gas and is Hghter than air. It can 0
_...1 C Liquid
1
11111011 1
. . . o d fr zes at - I •
1..Aut .itniosphenc pressure. 1he hqu1d boils at -38 4 C an ee h
:it ,ll'l, 9 . 1 ·ated throug s trong
;1111 n
onll• resembles water in. its phvsical
' properties.
. 1e. it is_high Yassocr 1·n J Volume o wa
f ter)
1
•Jrogen bonding. Ammoma rs extremely soluble m water (102 Vo ume
In ,, oc.. and -6omm
;1t~0 . pressure. • 1 ted In these
At Jow temperatures two soluble hydrate NH3 .RO
- and 2NH.,.H,O are rso a :
us solutions a1so
1
n,oiecules ammonia and water are linked by hydrogen bonds. n aqueo
arnnionia may be hydrated in a similar manner and we call the same as (NH_,.H,O)
NH + H 2 0 ~ ~ 4- + OH-
3

The dielectric constant of ammonia is considerably high to make it a fairly good ionising

Jvent like water.

50
2NH,~NH 4 - + NH 2 -
K =[NH -][NH -] =10-30
-5o0c -1 2

2H 20~H _
, 0-+ OH-
4
K250c = [H,O~][OH- ]= 10..j

Chemical Properties
Action of heat: Above S00°C ammonia decomposes into its elements. The decomposition may
be accelerated by metallic catalysts like Nickel, Iron. Almost complete dissociation occurs on

continuous sparking.
>'iOO'C >N, + 3H,
- -
Reaction with air/oxygen: Ammonia does not burn in air but burns freely in free oxygen with
a yellowish flame to give nitrogen and steam.
4NH3 + 302 ~ IN.: .J.. 6H.:0

In presence of catalyst like platinum, it burns to produce nitric oxide. This process is used for
e manufacture of nitric acid and is known as ostwalds process.
4NH, + 50: ~ 4NO + 6H,O

h
educing property·· A mmoma . acts as a re ducing agent. It reduces the metal oxides to metal
en passed over heated metallic oxide.

59
 1'l•I ,, " I I 11 I I

l' l II I 1 l Ill I 11111111111,11111 1l1 1111 ,, llt h I

Rt'h{ ' " ,, th hhb \\ 11 I\ 11, 11 .. I \\II I I " ,,,
\ ,, 11 In,, II I ,11 11 11 1!1 111 I 11 11 1 Ih l 11 1I, ,, 1 ,1 \ 11 1

~\ ,t ,... ,,\lth,hhidth ' m,1,h\,uu\ \ 111111 ,, 11 \ 1 ,, 1,t \,111, 1lil11111, 111d ltl1,11,l1 11 ,
11,111 II• dillt 11111 111,d, I dill I 111
11 ' "I' Ill 1 1 Il
l ,, ,,
,''i ,, ,, ,,,\1' I I 11\1
1111,!11
,,

, '.\ , I' I l\ I

'(•'\ll,l'I

F0rm~til)ll ,)t .uni'-ks ,md nit ri,ks: \\ 11 h st Intl!'. ,•k, I 11 1

?~":- ::Yt.' '1' ,'t.,ls sn,h s,,,lirnn, ,'1\ll\\lll\1,\ rm ll\S ,1111ld1•s
,1S
,,-.1:.-.' ~: ~:-. .-ms ,ntri,ks ,nth nwt.,ls lik,• m.w1wsn1111 . lh H lion or 1111111011) I wllh lfU
•'
2'\.! - "'\11 , , 'N.,Nl I, I 11 ,

2"\.lL~ i\k ,N , 1 .'\11,

' -'
"1th metallic salts: Ammc,ni:1 reacts with nwl:1\lil' snits lo g1w 1111•1,II hyd111x1d, .. ,
in ..-.:se l"'f Fe 1 or forming l'l)lllpkxt'S (in l',\St' Cu)
Fe~- - 3";\H / + 30H- ___:q ,'ctOll) , I ."\NII/

cu> - -l'.\'H ~-.:. lC11tNHJ~ l"

T etramnminecoppcrt \\)ion
ta coordinntion complc,)
Formation of amines: Ammonia forms ammonnted compounds hy ion dipoll' allra<Jion,
Eg. :caCl:.8:l\~ J In this, the negative ends of ammonia dipole is a\\radc<l \o <,a1 ' ion,

I: can also act as a ligand and form coordination compounds such as\ <:o( NI l )J 11 , \ Ag(NII
1
For example when excess ammonia is added to
aqueous solution copper sulphate a deep blue colour ••
compound [Cu(NH)J+ is formed.

Structure of ammonia
Ammonia molecule is pyramidal in shape N-H
bond distance is 1.016 A and H-H bond distance QH
is l.645 A with a bond angle 107°. The structure •
of ammonia may be regarded as a tetrahedral with Figure 3.1 Structure of ammon~

60
 Ill 11111• I I I
I, 1 /1111)<; d, d I, I py, ,, (
I,, ,, "''' 111 ,,,
I
1111 ,11 ( ( I I I( I II
I ,11<' I'
,111' I I 11 //1( f11
:111 f',
I
11 II
' III1 I
11 l
,
:\'I I
ll
I I, '
11 1f ul ll
•''tr• l111' I I
icl is p1cp,11l'd hy /it',1 I, I 1/11,1 ,1/1111111,1 , 1
,, ti 11 /" '' 1, ,/l11r1 1,r 1,rlwm 11 /r
\ Ill 1, ,ll 1d ,
• 11 •111.if :-11lpl1111
ll I fl
•'I "N o 1 , II ,,so , , 1, w;,, 1 ,
11
J<,
,
, tcnwcr,1t111t' ,~ kepi
,1., low .1., 110 .,,. ,., , 11><. lo •,vo, I I , 11111 111 ,1,1IH111 ,,f 111tr11 a ,rl If , c1 1
II It
l1111ii11g l1q111< I w/ 111 '1 I O1011! ('c/ ' I, ' ',. / c11<1,•(Jfal11tltm
lrr)g,n
, ·~ ti> ,1 I',
, u, w ,, >y lll l'p rt «.
11kfl~l •
,.,,, . • /mhislor11
1cdd11l'lotlic <I t<· o111po,1f1011 of 11Jlf1< acid.
,1u1\ll,1 \\
1/INo. > /4No ' ' 211 , <) 1 ()1
·p ar.ifiou
llu.'rd.il rndhod o f pn
1a
(()JI I
in large sc-dcs u . 11 ( lwald ,,c, procec,~. Jn thi<; mclh<Jd ammrm •
Nitrk ,1od prep.ir • ed ' ' • liJ g
}~
• d pa«.'icd into
/ /O tim • · Of ·,ur. ,/111s mixture 1.c, preheated an
, .
, m1xl'd ab ou
//.ibcrsprocl'ss1s cs • c temperature nses
1•,ict w11/i platinum gauze. 'Jh
in .
tn>1 11
w he re they com e
. r.1/r~t chamber co
'
n
, I ul Ihc rapi.d catalytic ()xidation of ammon
ia
rhe 1 •1 ' ct:1 /li c ga uz ,, br mgs a JO
I I J7'11' nnd th.e rn • d' .d
rl> ,1 Ii()ll .., • . 1 o f N O , w hich th en oxi-u'i's, cd 10 nh.,rogcn 10x1 c.
.,,Irin..g in the lormal101
re'-~ /20 kJ
4 NII1 1 507- ➔ 4NO i- 61 // ) +
02
2NO I 0 2- > 2N
It reacts
ed th roug h a serie s of adsorption towers.
produced is pass
11ie nitrogen dioxide ox id e fo rm ed is bleached by blowing
air.
id. Nitr ic
11•1tJ1
water to give nitric ac 21-INO + NO
3N 02 + I-1 2O ~ 3

pronerties water
86 °C . Th e ac id is co mpletely miscible with
lourless. It boils at ). Fuming nitric acid
Pure nitric acid is co HNOJ' Bo iling po in t 120.5 °C
rming a co nstant bo iling mixture (98% su nl ight or on being heated
, into
Jti s on ex po su re to
ogen. It decompose
contains oxides of nitr
and oxygen.
nitrogen dioxide, water + 21-1 2 0 + 0 2
4HN03 ----➔ 4N02 .
ted so lu tio n be co m es yellow on standing
tra
re acid or its concen
Due to this reaction pu g ag ent. H ence the oxidation st
ate
ox id is in
, nitric acid acts as an action with metals.
Xitric
In most of the reactions eld hy dr og en in its re
wer one. It doesn't yi
changes from +5 to a lo g agent.
acid, an oxid izing agent and an nitratin
acid can act as an ox ides to form salts and
water
ba ses an d ba sic
acids it reacts with
As an acid: Like other + H ,0
0 ----➔ Zn(N03 ) 2
ZnO + 2HN 1

O i }1 + N O + 5 H 0
----➔ 3Fe(NO _
3FeO + l 0HN 3
 sulphur phosphorus and
As un o~idhin~ agcnl: llw 11011111t:l,tls like 1..,ir 1loll, '

(' I lllNO, , 211 <> 1 '1NO I CO2

s I 'IINO, ) 11 1so . I 2NO

p I "'OIINO, ➔ ,lf I ,PO. I 411 .0 I 20NCJ2
I

Jl2 i I0HNO1 - - ) 61110, f !ONO + 21120

HNO, 1 F, ~ HF t N0 1 F
3H 2S + 2HN01 ~ 3S + 2NO + 4Il20

As an nitrating agent: In organic compounds replacement of a -H atom wi th No ,s uf

referred as nitration. For example.
C6H6 + HN03 11,so, ➔ C6HsN02 + H20
Nitration takes place due to the formation of nitronium ion
HNO 3 + H 2 SO 4 ~ N 0 2+ + H 20 + HS04-
Action of nitric acid on metals
All metals with the exception of gold, platinum, rhodium, iridium and tantalum rea
with nitric acid. Nitric acid oxidises the metals. Some metals such as aluminium, iron, cob
nickel and chromium are renderep passive in concentrated acid due to the formation of ala
of their oxides on the metal surface, which prevents the nitric acid from reacting Wi\\\;
metal.

With weak electropositive metals like tin, arsenic, antimony, tungsten and molybde
nitric acid gives metal oxides in which the metal is in the higher oxidation state and the
is reduced to a lower oxidation state. The most common products evolved when nitric
reacts with a metal are gases NO 2, NO and H 2O. Occasionally N 2, NH OH and NH 3 are
2
formed.
+5 +4 +3
HN03 N0 2 HN0 2

The reactions of metals with nitric acid are explained in 3 steps as follows:

Primary reaction: Metal nitrate is formed with the release of nascent hydrogen
M + HN03 ~ MN0 3 + (H)

Secondary reaction: Nascent hydrogen produces the reduction products of nitric acid.
HN03 + 2(H) ~ HN0 + H 202
Nitrous acid

HN03 + 6(H) ~ NH 20H + 2H 20

Hydroxylrumne

HN03 + 8(H) -----1 NHl + 3H20

Ammonia

2HN0 3 + 8(H) -----1 HN02 1 2 + 4H 20

Hypo nitrous acid
 (eaction: The sec
ond aq pro duc ts ,,·11
.. 1 let de;
d
.• ,-1 cum pr, c or react to give final pro uctc;
e1t1.. , . of the sec ondar)':
fi osit1on
.c01'1P "l BN O,
!Jt "I
➔ llNO 2 ... No 11 ()

hJ1JJJPJes:
ng
er reacts ·with nitric acid in the followi ma nne r
copP
3Cu + 6HN03 ~ 3Cu (N03\ + 6(H)
6(H) + 3HN 03 ~ 3HNO 2 + 3H 2 0
3H N02 ~ HN03 + 2NO + H20
overall reation

[3eu ~HNOJ ----+~cNo.~1._+ 2NO +!Hto/

nitr oge n dioxide
The concentrated acid has a ten den cy to form
[-c1:_ + 4HNOJ ~ Cu(NOlll.+ 2N02 + 2H4.0 ]
owing way
,\Iagnesium reac ts with nitric acid in the foll
J
4Mg + 8H N03 ~ 4Mg(N03 ) 2 + 8[H
HN 03 + 8(H) ~ NH3 + 3H2 O
HN 03 + NH3 ~ NH 4 N03
overall reaction
& M~ + lOHNO.J. _ 4Mg(N_0 3) 2 +-N Hi NO.l + 3HioJ

the acid is diluted we get N2 0 _ 0_ _) _+_ N_o o/

_ +_s_H_--..
_ ~
_ 0
(.-4-M_g_+~ l o_HN -M
- -4 - g(N
2
3 2 2
3

es of nitric add:
in the pre par atio n of aquaregfa.
Nitric acid is use d as a oxi dis ing age nt and
.,)
ofnitric acid are use d in pho tog rap hy (Ag
NO 3) and gun pow der for firearms. (NaNO
Salts

aluate yourself:
ed) with zinc.
pro duc ts form ed in the reac tion of nitr ic acid (both dilute and con cen trat
rite the
-- -- -- -- -- -- -

63
 l. 7 Allotropic forms of phosphorus:
Phosphorus has several allotropic modification
which the three forms namely white, red and black
osphorus are most common. . .
ll

~I&
The freshly prepared white phosphorus 1s
lourless but becomes pale yellow due to formation
a layer of red phosphorus upon standing. Hence it
also known as yellow phosphorus. It is poisonous
nature and has a characteristic garlic smell. It
ows in the dark due to oxidation which is called Figure 3.2 Structure of white
osphorescence. Its ignition temperature is very low phosphorus
d hence it undergoes spontaneous combustion in air
room temperature to give P2O5•
The white phosphorus can be changed into red phosphorus by heating it to 420 °C in
e absence of air and light. Unlike white phosphorus it is not poisonous and does not show
osphorescence. It also does not ignite at low temperatures. The red phosphorus can be
nverted back into white phosphorus by boiling it in an inert atmosphere and condensing
e vapour under water.
The phosphorus has a layer structure and also acts as a s~miconductor. The four atoms in
hosphorus have polymeric structure with chains of P4 linked tetrahedrally. Unlike nitrogen
sP is less stable than P-P single bonds. Hence, phosphorus atoms are linked through single
onds rather than triple bonds. In addition to the above two more allotropes namely scarlet
d violet phosphorus are also known for phosphorus.
- -------------- ---------------~

Figure 3.3 Structure of red phosphorus

.1.8 Properties of phosphorus

Phosphorus is highly reactive and has the following important chemical properties
eaction with oxygen: Yellow phosphorus readily catches fire in air giving dense white
mes of phosphorus pentoxide. Red phosphorus also reacts with oxygen on heating to give
osphorus trioxide or phosphorus pentoxide.

67
 I' ()

()
PO

I'()
,
Re 1,1 on ,uth dtlot1nc Pho phoru rca ti. with c.hlortn lo form In n I p
) l t'i \lolcntl} at mom temper lure, whtlc r d ph ph r I r

P 6C I ➔

P, IOCI ~

Rea" tion ,, ith alkali: '\cllm, phosphorus reacts,, 1th alkali on bo1lmg m an mert atmo ph
1beratmg phosphine. Here pho~phorus act as reducing agent.
P, 3~a0H 3H O--) 3>iaH PO +- Pll 1 i
sod h t'<lrh~h• l'M m

Reaction with nitric acid: When phosphorus is treated with cone. 111tnc acid 1t 1s ox1d1sed
pho,phoric acid. 'This reaction is catalysed by iodine crystals.
p4 + 20IINO --) 4Hl04 + 20NO, + 4H,0
Ortho phosphonc 0<1d

Reaction with metals: Phosphorus reacts w1th metals like Ca and Mg to give phosphide
Metals like sodium and potassmm react with phosphorus VJgorously.
P4 + 6Mg --) 2Mgl2
Magnesium pho,ph1<l<

P4 + 6Ca--) 2Cal2
Calcium pho,ph1<lc

P4 + 12Na --) 4Nal

So<hum phosphide

U~es of phosphorus:
I. The red phosphorus is used in the match boxes
2. It is also used for the production of certain alloys such as phosphor bronze

3.1.9 Phosphine (PH,)

Phosphine is the most important hydride of phosphorus
Preparation:
Phosphine is prepared by action of sodium hydroxide with white phosphorus in an
atmosphere of carbon dioxide or hydrogen.
f'4 ➔ JNaOII t 311 20 ~ 3NallyPO, + PH 1 i
,uJ111111 h) p,, pllll,ph11,· l'h,,-plunc

Phosphine is freed from phosphine dihydride{P) I) by passing through a

mixture. 'Ihe dihydride condenses while phosphine does not.

68
 l I' fll l.O • 'PH ~t OH

' ; ,.1r-.·J 1U l'll l\' h.ll Ill

b\ hr.1tm~ rh o...phon.ms ,ind .
.' ro.,... ~ PH, '
4H :P (\ ~ .__.....~-~H ...
' ~.:" ",

l P' rt ic.'i-: 1
~·"" ~-:ti rn rish sm ell It 1s slig htJY sl1luH e . .., ,, .1ter an d ~
· -~•,,u '.fSS, r. .1isL 1wus gas
1 "it h rotten 9.5 K ·
a col ou rle ss liq uid at 18S Ka nd fn:·c>ze~ ~0.:: sl1:1~ ut 13
··.~ ·.:· ,,u s tc:st. It c1.mde11ses to
•. , H".i,i .,, ··"
. .
·· · . -:ii pn1pc rti es: . . in .ib sen ce ot air at
1Jt.f11h •
osp
.
hm e de co mp os es mt o its elements wh en he ate d
l . bilitY: Ph . .
,rf'l.U 11tJ ..Jc'c •
cu rre nt 1s pa sse d thr ou gh 1t.
.,.,.,, . n tn c '-
- ' 1.'i" 1\ Jc' . .. P~ - bH:
4PH.~ ;n .

or o~·vge n it bu rns to :oiY

; , e me ta rho sP ho ri. .:
ate d ,d th air , ...
A

. n·. \\"hen phosphine is he

....busno
1.lh< '

P.,0 0 T 6H.0

P~O•c , 6H :O ~ \ka4H PO3 .!. -SH.O

r>lK>..-r!l.'11, ~.-;;i

salts wi th halogen ad ds .
;.we nature: Ph osp hin e is weak
ly ba sic an d for ms ph os ph on ium
PH .+ HJ --4 PH .I
~
-·
PH➔l -j- H: O .l PH; + H, o- - r
Ph<.'-<rnm.,

e ph os ph oru s pe n ta ha lid es.

imam ,dth halogens to giv
PH 3 + 4CI: ~ PCl 5 - 3HC1
sal t so lut ion s.
ine pre cip ita tes so me me tal as ph os ph ide from their
Reducing pro pe rty : Ph os ph
3H X0 1
3A gN O, --- PH 3 ~ A g 3P -
.
ion co mp ou nd s wi th Jev ,is acids such as bo ro n tri ch lor ide
It forms coordinat
BC! -P H J~ [Cl 3 B ~: PH 3
J
Coor<hmttoo compound

69
 I h,11
u~c of phor.phlnc.
Phm.phm I u d i r pr
1tgl\i.:slugc mok Ina hp
., 1111xtur of .11 nun rl>td
hbcr.1tcs phm,phm and ac. tyl n wh
,ca 111c hbcratcd phosphine catchc: fir
signal to the approac.hmg ~hip h1 i kn

3. J. IO Phosphorous trkhloride and pentachlonde

Phosphorous trichloride:
Preparation:
When a slow stream of chJorme 1s passed over w te u«L~J

is formed. It can also be obtained by treating white phosp

p4 + 850Cll - - - - 4PC1 -t- 4S0 - 2

Properties
When phosphorous trichloride is hydrolysed with cod \t,a er • gr,

PCI -1-3H~O--, H PO -3HO

This reaction involves the coordination of a ,~ater mo.ecu e ~ --

the phosphorous atom following by elimination of HCI whic 15 s~-:n.c..r

This reaction is foJlowed by two more steps to give P OH or H PO

HPOCI 2 + H2 0---► H PO C - HC

Hl02CI + H20 ► H PO - HC

Similar reactions occurs with other molecules that contain, akoho , and

3C2H .OH+ PCl. -----

► 3C H.Cl - H PO
3C2H~COOH + PCI ► 3C H COCl - H PO

0
 1,uhlnilcl
t,or•''i
~11'r 1,1l, •• d, 1 " , ,1 , , l h111, 111.11 11,,
r
,,f ,] 111 ll"lfll , 1tl1111n flf) I( ', l
1 11
I , c,,( th Pf( 1
I fc11
1 tL (t1lhlod,h,
,1 .. l,c"
1

~(!f'I
,•r ,,fl I wit I1 t.:Xl css
II ~ tn',tll'l t hlor irw,
1
I'< I •
tih1ndc l!i oht.1111cd.
,, ,, 11 ,en 1,tl
111' I ~ I igun: \ -, St u tur of
I ,,,fl pCI' I Cl --> PC!
phosphorus tru.. hloridL
lertics
1prol
~rll'i'tl . g phosphorous pcntachloridc, it
( . hi . and chlorine.
11e.111n phosphorus tnc
011 . onde
ses ,nto
J,, (1111p0 • PCI S (g) ----) PC]l (g) t Cl l ( g) .
(I tu,,)

rnd
us pentachloride reacts with water to give phosphoryl chloride •
hosphoro .
P horic acid.
(,rthophosp
POCl3 + 3H 2O ~ H 3 PO4 + 31!Cl
Overall reaction
PCl5 + 4H 2O ~ 11 3PO 4 -1- 51ICI

rous pentachloride reacts with metal to give metal chlorides. It also chlorinates
phosph0
. pounds similar to phosphorus trichloride.
organic com
2Ag + PCI'i - - - • 2AgCl + PC13
Sn + 2PC15 - -- • SnCl,. + 2PC1 3
C H 50H + PCl 5 ► C2H 5Cl + HCl + POC13
2
C H COOH+ PCl5 - - - • C2 H 5 COC1 + HCl + POC13
2 5

Uses of phosphorus pentachloride

Phosphorous pentachloride is a chlorinating agent p
and is useful for replacing hydroxyl groups by chlorine o~ ~o
atom.
3,1, 11 Structureofoxides and oxoacids ofphosphorus
Io I
P-1-o~p
Phosphorous forms phosphorous trioxide,
phosphorous tetra oxide and phosphorous pentaoxides /----P--...j
. In phosphorous trioxide four phosphorous atoms
Figure 3.6 Structure of P.. 0 6
lie at the corners of a tetrahedron and six oxygen
atoms along th e edges. The P-0 bond distance is J 65.6

71
 Name Formula
H

U"d
~
,
.. ). H-P-OH

0
0
Orthop osph.r
HPO HO-P-OH
aad

H
0 0
H -pophosphonc
H p_Q HO- P-P-OH
acid -

HO OH

0
one
H.PO HO-P-OH

OH
0 0
phospbonc
HPO_ HO-P-0- P-OH
d -

HO OH
 '

'

\ \ \ l

' ', ,, -.: \,~ ~:h'\\\' ,\ll,•,I, II "1" I II ,,. l'I l,11111!11 I, 111 111 I Ill
I,, II,· I

: ,' '\ , , , ,' ,11l1'hhi,, \ 11~1 ,·l,·n1.•11t ''" f' 11 llh 11 11 1 1 1'11111111111 I 111 111
,, ' '
' ' ' \ \ ....•,
\. \
l1 I
.. ' \ ,\II \•' ' , , , ' 'd '\, ,, ,, ,.,,, ht 1, \\ ' II I \ 11111111 ) I " " l II ' I 11111
\
II "II I I

· ,Hhl,, ulrhu, 111.,~,·, 111• ,il,,,,,1 l(,(,''.,,,1lll\l, '" 111111111 11, \

,,,,· .. '., ~''-'':, '
'', , : , ~ - · : l\l , '\ \~I~,\ ~ ~lll1 •h.\t,~ ,,:, 1•:--111 11 , ,•1 •s,,111 1 ll ) 11ul .iil1il11d1 ( d 111 111

' ,, ~: ':-,' ;' i , :,.,' 1\l 111 th, \ , 1 1, ,11\1, .1sh,·~ I he .,,h •1 t I< 111< 111 111 tlit •1 ,1111• 1

., .- ,,t't--u h' lllhl .,~ :-,·knhk~. h ' ll1 11 hi,·, cl, ,il,,,,1~,, ,1 Ii .1il1•h1.t, ,,, ,

I'
\ '
) ' llU\)11 r; n:,;1\. ,d l'll'j','11 \C:- ,,t the g1,1111' le, c l,•111l·111s ,,c 11,t, ii 11, Iii l ,Iii

,;(,\tt' ,\(
Oz,aea

G.1s
......
l.1hk , , PhHll,ll p1op, 1lu·~ ol ! 1onp lh, I nu 111

Sohd Sohd
Nhttlua
Solid Solid
: 31\'.
Atonuc Number 8 16 34
opes lt1Q "S 1111se 11,1 It

Atomac Mass
15.99 3206 8.9 1 60
(g.mo1 at 293 K)

Electronic [ArJJd'" 4s (X I
configuration [He)2s 2p4 [Ne)3s 3p4 4 4 5d 68 6p
 '"' '" " ' ll l .\' I I
I II I ,u
l\•11~ I\ ( \ Ill II
I \ Ill I I

HH III

IH I rI

l>, l'n.n atmn: ·1 Ill' ,\I mnsplll't <' ,1 nd w.111' 1 1rn11.1111J. \ 11{, ,tt ,d H~,y,, 1,y 111.1 , qf , ,1 ,v, , 1
\ h)st tlw wnrld\ rnl k l llll l,1in l 011 1hi111·d oxyg(.'11 l11d11 ,I 11.ally 1 ,x,i~t 11 1 1
l)f
1
fr,1dio1ul d1st11l,1tion of hqm•f rl'd ai,. l11 tht l.1hrn .,tor y, 11xyg. 11 1•1 prqi.irt d >/ ,
folk)wing Tlh'thnds.
lhe <.kcomposition of hydrngt·n pcrnx 1dl' in tlw f>J<",<'11' c qf 1,,at.ily t ( 11, (;
oxidation with potassium pl'rnrn nganale.
211 ,0, , ~ 211 _,() I 0,

51 1_,(\ I 2M n0,i I (lll

1
>50 1 I 81 1}) I 2M11 1

The thermal decomposition of certain metall ic.. oxide.·!-. or o.xoani<111i, give•, m.:yg"n
21lgO 11
> 211g I o,
28a0 2 -" > 2Ba0 I 07
2KCI03 M,~o, ) 2KCI I 30 2
2KN03 ~ 2KN0 2 ~ 0 2
Properties

Under ordinary condition oxygen exists as a diatomic gas. Oxygen is param<1..gnef

nitrogen and fluorine, oxygen form strong hydrogen bonds. Oxygen exists in two allc
forms namely dioxygen (O ) and ozone or trioxygen (OJ Although negligible amc ·
ozone occurs at sea level it is formed in the upper atmosphere by the action of ultr
light. In the laboratory ozone is prepared by passing electrical discharge through oxy,
a potential of 20,000 V about 10% of oxygen is converted into ozone it gives a mixture
as ozonised oxygen. Pure ozone is obtained as a pale blue gas by the fractional d1sf
liquefied ozonised oxygen.
02 2(0)
Oxygen atomic oxygen

0 2+(0) ;::==:: 0 3
Ozone

The ozone molecule has

a bent shape and symmetrical
with delocalised bonding Figure 3.8 Structure of ozone
betweenathe_oxvQen.a
 I ,ror'e'
IL 11 J . ' .'
,.,11 ,, 111 jca I ptopc rt Ic~ of OX) ,
, ~ lht gen and
11" , uid non-mc t.11s to form 02011( <1,n
1 ,f,l1~' OX1dcs w· (f V ti
,, ,11t. 1 of (1X)'gcn ou. lll s .,1 toom I • ith onH <'lrn-. I
cniper ", n I u h
11,1 11 01 to t c I ,1lu1c Senne f I ,
,1 1,111:1 r. ,))' nnd m,1dc lt',t(
Xot 1c n, o c r ,I( 11 " m
'(1111 • I 111H . 1
1
' \.,i~•r'' tali:- un.1fkctcd undl'r s,1111'c cond111 _ll,1 ly Wllh oxy,
,,11 f ,ne' on • gen at room l mp r
l,,11f' o .• and when ~rt thr powd<.·r on fir,.-., h<.'at .'is l'b These finely divided met aI re k
l, ,111,orJl l • J crated .1 •
,1 1 hL't 1.llll•
l
ozone 1s a powe c. I uurmg a reaction
thC O1 rru oxid" ··
1
1'
()tlc11Hfif i<.1ns "here oxygen Will not react 'F~111g agent and it reacts with many
substc1nce
1~ t· · · or exa I .
·
~Jl'1c 'JhiS rc,1ction is quan Itattve and can b mp e, it oxidises potassium 10d1de to
J i1C•
e used for e t' .
,,1~11 03 -t 2KJ + H O s imation of ozone.
i ~ 2KOH+ 0 +I
e is commonly used for oxidati on of organic i '
ozo!l ..
the oxid1smg power of fluorine and . compounds. In acidic solution ozone
. alkal'me solution. atomic oxygen. The rate of decomposition of
e''-ee ds ps sharpl Ym
d
<,ione ro
•-e''
en is one of the essential component fi th .
J. Ot'/g . or e survival of living organisms.
z. It is used in weldmg (oxyacetylene welding)
. ui· d oYVgen
3, 11q ,~, is used as fuel in rockets etc ...

Allotr0phic forms of sulphur

3,2, 1
ine as well as amorphous all otrophi c 1orms.
c The Cn'Stall'me
Sulphur exists in crystall
form includes r~ombic sulph~r (a sulphur) and monoclinic sulphur(~ sulphur). Amorphous
allotropic form mcludes plaSt ic sulphur (y sulphur), milk of sulphur and colloidal sulphur.

,Rhombic sulphur also known as a sulphur, is the only thermodynamically stable allotropic
form at ordinary temper ature and pressure. The crystals have a characteristic yellow colour
and composed of S8 molecules. When heated slowly above 96 °C, it converts into monochnic
sulphur. Upon cooling below 96 °C the Pform converts back to a form. Monoclinic sulphur
also contains S8 molecules in addition to small amount of S6 molecules. It exists as a long
needle like prism and is also called as prismatic sulphur. It is stable between 96 °C - 119 °C
and slowly changes into rhombic sulphur.

When molten sulphu r is poured into cold water a yellow rubbery ribbon of plastic sulphur
is produced. They are very soft and can be stretched easily. On standing (cooling slowly) it
slowly becomes hard and changes to stable rhombic sulphur.

Sulphur also exists in liquid and gaseous states. At around 140 °C the monodink· sulphur
melts to form mobile pale yellow liquid called A sulphur. The Yapour owr the liquiJ sulphur
consists of 90 % of s s & s and small amount of mixture of S,.• S1• S1, S; mole~ules.
S' ~ 6

75
 3.2.2 Sulphur JfoxfJc
Prep.u ,1tion
From sulphur: A li1rge-scalc prouuction ° stJ!phur dioxide is done by burnin g su)Ph1.1
.1 (

Ahout 6 8% of sulphur is oxidised to SO,.

r 1~
s + o, ~ SO ,
2S + 30~~ 2S0 3
From sulphides: When sulphide ores such as galena (PbS), zinc ble nd e (ZnS)
are roas
. Ip hur d"10x1"d e 1s. l"b
au.su t d
1 era e . Large amounts of sulphur dioxid.e required for manuf ~.
att...
of sulphuric add and other industrial purpose is prepared by this method.
2ZnS + 30 2 ~ 2Zn0 + 2S0 2
4FeS2 + 110 2 ~ 2Fe 20 3 + 8S0 2
Laboratory preparation: Sulphur dioxide is prepared in the laboratory
treating a meta.I
metal sulphite with sulphuric acid
Cu+ 2H 2 S0 4 ~ CuSO" + S0 2 + 2H 2 0

Properties:
Sulphur dioxide gas is found in volcanic eruptions. A large amount of sulphu
r dioxide
is released into atmosphere from power plants using coal and oil and coppe
r melting pla
It is a colourless gas with a suffocating odour. It is highly soluble in water and
it is 2.2 ti
heavier than air. Sulphur dioxide can be liquefied (boiling point 263 K) at
2.5 atmosp
pressure and 288 K.
Chemical properties
Sulphur dioxide is an acidic oxide. It dissolves in water to give sulphurous
acid.
so2 + H20 ~ H2S03
Sulphurous acid

Reaction with sodium hydroxide and sodium carbonate: Sulphur dioxide reacts
with so ·
hydroxide and sodium carbonate to form sodium bisulphite and sodium sulph
ite respec fa
S0 2 + NaOH ~ NaHS0 3
Sodium b1Sulph11c

2S02 + Na 2 C03 + H20 ~ 2NaHS0 + CO

3 2
2 NaHS03 ~ Na 2S03 + H 0 + S0
2 2
Sodium sulphll~

Oxidising property: Sulphur dioxide, oxidises hydrogen sulphide to sulphur and

magnesif
to magnesium oxide.
2H,S +SO ,~ 3S -r 2H,O
- - -
2Mg + so 2 ~ 2Mgo + s
 Ill d,I J
,,,r.rn !\
lid
I "-<l 110 (I ti () ti(
,llun pcrm.u1g11n11 and dt hn m I t Mn
I\MnO 4iSO
• (

II 0
K SO "MnSO H SO
K (rO ,so H SO 4 ➔

K SO 4 Cr (SO ) H0
h ol}gen: Sulphur dioxide 1s ox1d1sed to sulphur trioxide upon heating W1lb
· ts
,10° "It h temperature. 1his reaction · used for the manufacture of sulphuric a 1d by
Jtl' 111 h18
,,.~(0 rocc~s .
•'\,0taJ P 2SO .(g) + 0 (g) ,' 0< ► 2S0 (g)
. action of sulphur dioxide: In presence of water, sulphur d1ox1de bleaches coloured
..p,-~,dt•·tk11gsponges and straw into colourless due to its reducing property.
"-o0'· ~1 • so:? + 2H 20 ~ H 2sO J + 2(H)
X + 2(H) ~ XH 2
(olourcd
folourte,.

. r the bleached product (colourless) is allowed to stand in air, it is reox1d1sed

t,iowe"e ' . . . . d
h ric oxygen to its ongmal colour. Hence bleaching action of sulphur d1ox1 e 15
bf atrnosp e
ttl11Porary.

L~e~ · used m
ioxide 1s · s1"lk, wool etc...
. bleach"mg hair,
sulphur d
J. be used for disinfecting crops and plants in agriculture.
2- It can
of sulphur dioxide:
Stfllcture 0
In sulphur dioxide, sulphur ••
5
atom u nd ergoes sp2 hybridisation.
• •• •• .. -o~ 'o··••
Adouble bond arises between S
and O due to pn- dn overlapping.
e
Figure3.9 Structure of sulphur dioxide.

l.l.3 Sulphuric acid: (H2SO4)

Preparation:
Sulphuric acid can be manufactured by lead chamber process, cascade procas or contact
process. Here we discuss the contact process.
Manufacture of sulphuric add by contact proceu:
The contact process involves the following steps.
l Initially sulphur dioxide is procluced by bwning sulphur or ire& PJill In oxygen/air.
 s I () ➔ S<)
,~h;S, I 110

11 Sulphm dioxide for med 1s oxidised to sulphui tnoxidc by air in th c presence of ll

s11d1 .1~ \ ,0 , or platinised asbestos.

iii. 'The sulphur trioxide 1s absorbed in concentrated sulp~uri~ a~id ~nd produ<.es
(H ,S/)) . 'The oleum is converted into sulphuric acid by dtlutmg it with Water.

S03 + H2S04----7 H2S20 7 H20 ) 2H2S04

To maximise the yield the plant is operated at 2 bar pressure and 720 K. The sui
acid obtained in this process is over 96 % pure.

Physical properties:
Pure sulphuric acid is a colourless, viscous liquid (Density: 1.84 g/mL at 298 I<:).
boiling point and viscosity of sulphuric acid is due to the association of molecules to
through hydrogen bonding.
The acid freezes at 283.4 K and boils at 590 K. It is highly soluble in water and has
affinity towards water and hence it can be used as a dehydrating agent. When dissolved in
it forms mono (H2S04.H2 0) and dihydrates (H2S04.2H2 0) and the reaction is exother
The dehydrating property can also be illustrated by its reaction with organic comp
such as sugar, oxalic acid and formic acid.

C12 H 22 O, 1 + H2 SO4 ----> 12C + H 2SO4 .11H 2 O

Sucrose

HCOOH + H 2SO4 ----> CO+ H 2SO4 .H 2 O

Fonmc acid

(COOH) 2 + H 2SO4 ----> CO+ CO 2 + H 2 SO 4 .H 2O

Oxalic acid

Chemical Properties:
Sulphuric acid is highly reactive. It can act as strong acid and an oxidising agent.
Decomposition: Sulphuric acid is stable, however, it decomposes at high temperatw
sulphur trioxide.
H 2S04 ~ H20 + S03

Acidic nature: It is a strong dibasic acid. Hence it forms two types of salts namely sul?
and bisulphates.

H2SO4 + NaOH ~ NaHSO4 + H,,O

sodium bisulphate -

H2SO4 + 2NaOH ~ Na 2SO4 + 2H 2O

sodium sulphate

Ammonmm sulphate

Oxidising property: Sulphuric acid is an oxidising agent as it produces nascent oJW

shown below.
 11 II 11 ( I I

' I, !lit Ill 11, 11 I I 11h11 ,, 1tl ,1, ,, I ' " I 11

111d l11 d l,11 I I II 111d pll11 JIil"'"
11 ' 11L•f1 Vt ly

I ' \ 11 SI I ' l I~ ( I t) 1111 1 rr1

" I , 11 Sc i I ) \ 1., ,() 1) 111>

I '◄ I Ill 11 St ) I \ 1111 tn I I osn , ,I I I 0

11.K I II Sil I > S<> I 'II ,() Is

'I II ➔ So 1:1 11 ,11 1 1
ll ,St> 1 1 '1111, ' S ()1 1 '11 ,0 I 111

ll ,hid r1• H Is wil 1

.,.,1,1!'''''11·,h ,ud11b:
l11•1S11lpl1111
1i1u•1(11111·11 • . i111ct,d,i;:111dgivcli diffcrcntproductdepen<ling
,, . I 1111..; ,1111 •\ •' ( OIi
. r,,11 .
I > I,httt\\" .,dd
1 (l•
•',1,,1<' ll'.h Is w1lh 111d,ds ljkc 1111• a 1111111111,un,
. . 1,111, to give corresponding
.
111

.111111,SO, > ZnSO,, 111 21

1
.1 A1 J 11 1so •I
1 > Al 2 (<..'
' ) <J 4 ) I I 31 I 2 I'
respective
Jh>I .-,mc,·11lr,11c.l sulpluiric aci,I reacts with copper and lead to give the
•, ,~ slH>W II bclO\iV,
,illl'h,1 Ii ~ •• Cu I 21 l,SO,, - ➔ CuSO4 + 2H2O + S02 j
Pb I 211 1SO,1 - ➔ PbSO 4 -1 zH 2O + so 2 j
sulphuric 11,·id doesn't react with noble metals like gold, silver and platinum.
R<''tion with salts: It reacts with different metal salts to give metal sulphates and bisulphates.
KCI, I l2SO,1 ----➔ KHSO 4 + HCI
KNO + II2SO 4 ----➔ K.HSO 4 + HN0 3
3

Na CO + H2SO 4 ----➔ Na 2SO 4 + H20 + CO 2

----➔
2 3
2
2NaBr + 3H SO 4 2NaHSO 4 + 2H 20 + Br2 + S0
2

eaction with organic compounds: It reacts organic compounds such as benzene to give

i ulphonic acids.
C H + H SO 4
2
~ C6H5S0 3H + H20
6 0
Benzene Benzene sulphonic acid

'ses of sulphuric acid:

I. Sulphuric acid is used in the manufacture of fertilisers, ammonium sulphate and super
phosphates and other chemicals such as hydrochloric acid, nitric acid etc ...
'l. It is used as a drying agent and also used in the preparation of pigments, explosives etc ..
 e;;_

I I.,

l'lh\\
11 1 \\111\

I
••h h ,,

1111111 II
II\ I\\ II I I I I I II
I \\
,.,, h111I
\l h \l\\i 11 11 I

1111
h 'I I' I I
1

11111\11111

'I I II
11

11 I\ 111\11 1 ld111 !i ll
I II I •I
1,h l

Ii " I
tql liltl l

1d11ll 11 11
1il1111 ,,11 11I 1ill'l,t1

II III I I I I I I
II
II
I Ill

II I "I II t I
ti 11 lu ,I, I • 1
II d
I II I ' I'' I 11,11
11 1111' I, ,d
I• I
'
I\ 11 I I 11 i 11 11 I II I I I
I
I It I
ll 11111111 1111,li II
I \I 1111 111 11111 ii I

I'I,,,, I I I I II I 11 If I " 1I l
I ,,1 1111'1111,
I \I 1111 111 li•II ti I

,, ''t Im~ ,., ,,,,,,,hi \tl ,,ll'hm

1111, ,111 11 1\\\111 \11111\ 1 1 \ \I 1, l, I 11 11 111, q l l11q111t 111111 ,1 11 1 I l 11d1tl 11 11 l1 II id, :;(llllt' H ld,,lik

,,11•1\1,h•\1 11111 ,lt1hl,•11h ,, hi ' 11 , I 1111\\ '' 111 111, 1,,1 '" ,ii 111111 ,ill •"'"} . 1111 , . !he li t•(• •ll11[
I \ 1111 I 1\,h \lhl i 11111111 Ii, I,,,I Iii.\

\ 11 \, 111 ,,,,, "Iii. ,11 ,,1111,l1111 ,, 11 1111t,,1, "' 111 1111, i 11 1• · ,,.1,•,•11 l 11 l11 w

Stru l\arc
Nm M I ala tJormuh,
0
11
s OH
110
0
11

~"'1\l\\11 I\ \\ "'
11 SU, HO s 11
OH
0
s
11

lh1P•ad1 hu1h ,ld \l

1 ll ,S,ll , HO S- OH
11
0
0 0
HS.O, 11 11
l llthl,mous 11dd
HO S- S-OH
0 0
11 11
l)a~ulphun,u~ \\.t\l H.s.n HO - S- S- OH
lll p, l\1sul1,hu1ous ll td 11
0
 \ ' :"\.

t,1 (7)

.. ~, ' ,, -.
'' 0 ~ 0 ~ \..)
'-'
.. ... ' ...
. '.'
'"" '-'-

\.'
' 0 0

0
'-....-". '
.
-.. ~'\.,' ,... ,"'
9•" ... ,"~

_... ... '

. ..' ' '\
HO s a 0
... - ...

a 0
'
.- .....)
'
HO s 0 0 s OH
0 0

a 0
•
,, ....... ~ ........ \. -~. " \. HO s OH
0 0

0 0
HO S-{S)n S OH
0 0