[I] :.- - •-__.

- = I
p-Block Element
POINTS TO REMEMBER (a brief concept ) /
J
- Introduction I
, p-block elements ar e placed in groups 13 to 18 of the periodic table .
, Their valence shell electronic configuration is ns 2 np 1- 6 (except helium which has 1s 2)
, Groups 13 and 14 are included in std . XI syllabus and group 15 to J8 are included in std . XII syllabu s .
• Group 15 Eleme~ts /
, Group 15 elements: Nitroge n (N), phosphorus (P), Arsenic (As) Antimony (Sb) and Bismuth (Bi)
, occurrence: Chile salt pete r (NaNO3), Potassium nitrate, Fluorapatite etc.
Electronic confi ration: ns 2 n :i
Trends in Physical and Chemical Properties
[ (al I Physical Properties:
(l ) Atomic and ionic radii: Increases down the group.
(2) Electronegati vity: decreases down the group .
I (3) Ionisation entha lpies: decrea ses down the group
(4) Non-metallic and metallic character: increases down the group for metallic.
(5) Physical appearance and density: density increases down the group.
(6) MP: increases regularly down the group.
(7) Allotropy : except Bi, all other exhibit allotropy.
(8) Conductivity: $b and Bi are good conductor of electricity.

I (b) I Chemical Properties: /

I (ii Action of air: All the elements directly react with oxygen of the air on heating with formation of corresponding
oxides.
high
N2 + 0 2 temp. 2NO
(ii) Action of oxidizing acids:
N2 + HNO 3 (conc. ) ~ No a ction
P4 + 20 HNO 3 ~ 4 H3 PO 4 + 20NO 2 + 4H 2 O
(Phosphoric acid)
AS 4 + 20 HNO 3 ~ 4H 3 AsO 4 + 20NO 2 + 4H 2 O
(Arsenic acid)
4Sb + 20 HNO 3 ~ Sb 4 O 10 + 20NO 2 + 10H 2 O
(Antimony oxide)
(ill) Action of alkalies:
N2 + alkalie s ~ No reaction
P4 + 3 NaOH + 3 H2 O ~ PH 3 + 3NaN 2 PO 2
(Phosphine) (Na-phosphite)
AS 4 + 12 NaOH ~ 4 Na 3 AsO 3 + 6H 2
2Sb + 6NaOH ~ 2 Na 3 SbO 3 + 3H2
(iv) Action of metals:
6Li + N2 ------? 2Li 3N
3Mg + N2 ------? Mg 3 N2
6Ca + P4 ------? 2Ca 3 P2
(v) Reactivity towards hydrogen: The hydrid es are colourless gases and show regular gradation in their
properties. The decrease in th e stability and solubility of hydrides is from NH 3 to BiH 3 .
(Vi) Thermal stability: The decreasing order of thermal stability is NH 3 > PH 3 > AsH 3 > SbH 4 > BiH 3
• Anomalous Nature of Nitrogen: The anomalous behaviour of nitrogen is due to small size, high Ionisation
enthal and ab sence of ct -orbitals in its valence shell.
(289)
 290
Uttam 's MHT-CET /Che .
1' m1s1ry)

• Main points of difference between N2 and other elements are -

No.
Nitrocen Other elementa ~

(i) At ordinary temp. N2 is gas Other elements are solids -

(ii) Exists as diatomic molecule. Exists as tetratomic molecules . -
(iii) Form hydrogen bonds in its hydride compounds . Do not form hydrogen bonding. -
(iv) Ha s tendency to form pn-pn bond Do not form pn-pn bonding. -
(v) Wide range of oxidation sta te . Limited number of oxidation state. -
(vi) Trihalides of N2 are unstable . Trihalides of all other elements are fairly stable. -
(vii) Does not form pentahalides Form pentahalides.

Dinitrogen
• Preparation:
(i) Commercial method: obtained by the fractional distillation of liquid air.
(ii) Lab method:
I NH 4 Cl + NaN0 2 ~ N2i + 2H 2 0 + NaCl
(ill) From Ammonium dichromate:
.1
I (NH 4 JiCr2 0 7 ~ N2 + 4H 2 0 + Cr2 0 3
3Ca0Cl2 + 2NH 3 ~ 3 CaCl2 + 3H 20 + N2
I
I (iv) From sodium or barium oxide:
I
.1
Ba(N3)2 ~ Ba + 3N2
I 2NaN3 ~ 2Na + 3N2
Properties:
I. - Colourless, odourless, tasteless, chemically inert and non -toxic gas.
- Slightly soluble in water, low freezing point and low boiling point.
I• Reactions:

I Mg3N2
Mg Li

I AlN N2
02
a
NO
• Uses: CaCN2

used for filling electric lamps.

provi~es in inert atmosphere in certain metallurgical operations
used m the manufacture of NH HNO C CN ·
3, 3, a 2, etc.
used as a refrigerant.
I ••A Compounds of Nitrogen
/ (a) Ammonia (NH
3
): j
• Preparation:
(i) By Lab method:

2NH 4 Cl + Ca(OH)i) ~ C
aCl2 + 2NH 3 + 2H 0
fil) By Manufactllrinc method: 2

N2 + 3H2 t ➔ 2NH3; AH = -46 1 kJ -1

fiii) By hydrolyais of CaCN _.th tr . mol
~ ..., • •am:
CaC2 + N2 ~ CaCN2 + C

CaCN2 + 3H20 ~ CaCO + 2NH

3 3
 29 1
p-Block Element

--;-;;;pertlet (Reactiona):

o1
N2 + H 2 0
Oi , Pt
?> NO + H 2 0
1 IOOK
CuO
Cu+ H 2 0 + N2

Cl 2 tNH,ct+N, (NH 3 in excess)

~ NC13 + HCI (C½ in excess)

NH 3 ➔ Br 2
NH 4Br + N 2
(Ammonia)
12
NH 3Nl 3 + 3HI
Na
NaNH 2 + H 2

NaOCI
NH 2NH 2 + NaCl + H 2 0

Cu 2 •
!Cu(NH 3) 4 ] 2 •

AgCl
Ag(NH 3b]Cl

2~Hgl 4 H 2N - Hg - 0 - Hg - I + 7KI + 2H 2 0
3KOH

• Uaea:
- in refrigerators
- in manufacturing of r ay on , HN0 3, NaHC0 3, nitrogenous fertilizers .

• Structure:

N~
10 1.1~ m
V
'l. H
~
0
H 101 .s
H
I r--------~
i \ (b) Nitric acid (HN0 3 ):
• Preparation:
(l) Lab method:
NaN0 3 + H 2 S0 4 ~ NaHS0 4 + HN0 3
Ill) Laree acale preparation:
Pt /Rh
4NH 3 + 50 2 SOOK 4NO + 6Hp
2NO + 0 2 2 N0 2
3NO + H 2 0 ~ 2HN0 3 + NO
 292 U1tam 's MHT-CET (Che- .
,,,LStrY)

• Properties (Reaction•):

Cu
/ '
(cone. HN0 3 )
2 C6H 5 N0 2 (
C6H6
Cu
7
(Nitrobenzene) (dil. HN0 3 )
➔
C6H2(N0 2lJCH 3 /
C6 H5 CH 3 Zn

(2 , 4 , 6-Trinitro toluene)
" (cone. HN0 3 )
7
HN0 3 Zn
C6 H5 0H C
C6H2(N0 2lJOH ( (Nitric a cid) ➔
(2 , 4 , 6-Trinitrophenol) SB
➔
C1 2H22011 P4
6(COOH}i ( ➔
(Oxalic acid)
12
'
/ N0 2 + HI0 3
(Jodie acid)

• Uaea:
used in the manufacture of nitrogen fertilizer, organic dynes , cellulose, varnishes, H2 S0 4., etc.
in dissolving metals for preparation of nitra tes, the pickling of stainless steel, etc.
/ (c} Oxide■ of Nitrogen I
(i) Ditrogen -~xide (Nl0) ; (ii) Nitric oxide (NO) :
0

:N = N--40: ~ N=N=O e GJ
N= 6: ~ :N = 0:
(Ionic) (Covalent)
(ill) Nitrogen trioxide (Nl0 3 ) : (ill) Nitrogen dioxide (NOl) :
~ N>-..120 pm
o 1oso ~ o
l l4 ~N l 86 m N 1300
o ::1/134" )lo
I I 7°
12 1 pm O
(5) DinJtrogen tetraoxide (Nl04 ) : (6) Dinitogen pentozide (Nl0 5 ):

o'\-
N 176 pm N'
~o
So
o~
N
M1200 N(34o
1,0
0
/4s pm ~~ / '\o
Phosphorus
• Allotrope• o f p.hoap.horua:
Properties White or yellow P Red P Black P
Colour White or yellow Reddish violet Black
Solubility in CS2 Soluble Insoluble Insoluble
Action of air Chemiluminescence No chemiluminescence -
Meltin g point 317 K Above 773 K -
Action of hot NaOH Forms phosphine No phosphine formed -
Phy siological effect Poisonous Non-poisonous

> t f A
 p-fJ/0(.,,f'- --

Collloound• of pho■phorua:
• suucture Preparation Properties (Reaction•)
Cl2 ,
~ - - - - , , PC1 5 + HCl
CuSO 4

PH3 - - HgC1 2

(21pho■phoru• P4 + 6Cl2 ~ 4 PC1 3

trichloride P4 + 8SOCl2 ~ 4PC1 3 + 2S 2 Cl 2 + 4SO 2 ·
(l'C~):

fJ
/ p"-..
CH 3COOH ,
Pel J ---t--,:~.....:.....::....::....::~,,. CH 3COC1 + H 3PO 3
Cl I Cl
Cl CH 3CH 2 OH ,
,, C2 H 5 Cl + H 3 PO 3
AgCN
~ - - - - ; P(CNh + AgCl
(3) Pho■phoru• P 4 + 10Cl2 ~ 4PCI 5
Pentachloride (white)
(PC1s): P4 + 10 SO 2 Cl 2 ~ 4PC1 5 + 10SO2
Cl
I .- -Cl
--t-/ : CH 3 COOH
c( __PI~ ! PCI 5- -
1------➔,,.
' CH 3 COCI + POC1 3 + HCI
···•.Cl
Cl ,____A
~g~-----
,,,' AgCI + PC13

Sn
- - - - - - ) SnC14 + PC13
H 20
. ) H 3 PO 4 + HCI
(m excess)
• Oxvacid1 of phosphorus:
No. Acid Structure Baaicity Oxidation atate of P
(11 Hypophosphorous acid 1 +1
(Phosphinic acid), H3 P0 2

(2) Ortho phosphorous acid 0 2 +3

(Phosphomic acid) II
P,H
HO / "'-oH

(3) Ortho phosphoric acid 0 3 +5

(Phosphoric acid) H3 P0 4
p
II

11
/ I"'-oH
OH
-~-r-------------+----
4
Polymetaphosphoric acid
(Glacial phosphoric acid),
(HP03)n
HO
-=--- - , - - - , ------------i
( O
II
o/j"-o
i 1
+
5

OH n
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ___,1_ _ _ _ _ _ _ _ _ _ _ _ _ _ _....__ _ _ _ _ _ _ _--1.._ _ _ _ __
 294 /Jttam 'I MIi'/ l I'. ! ((Ii ,,
~,111.1,,
};

I
11 (s1 ! Pyrophosphorou s ac id 0 0 2 i:l
(Diphosphorous acid), H 4 Pp 5
II II
I H- P- 0 - P- H
I
I I
OH
I
OH -- 1'1
I (61 Hypophosphoric ac id, 0 0 4
I
H 4 P~0 6 II II
I
HO - P - P - OH
Il I I I
I OH OH - - ,~-
0 4 15
, (71 Pyrophosphoric acid
I
1
(Diphosphoric acid). H4 PP1 II
p
/ OH
I"-oH
I
I I HO
-
fM Group 16 Elements / . .
~
1

• Elements: Oxygen (0) , Sulphur (S), Selenium (Se), Tellunum (Te) and Polonium (Po) , , .
• Occurrence: Gypsum (CaSQ 4.2H 20), Copper pyrites (CuFeS 2), Galena (PbS), Zmc blende (ZnS), Bwyt.e 11:fa.•')(J~)
j• Electronic configuration: ns 2np
4
1
• First four elements are called chalgogens (ore forming) elements
I •;@ Trends in Physical and Chemical properties /
1
(A) Physical Properties: . .
(1) Physical State and molecular structure: Oxygen is a gas while other are sohd at ordinary temperature .
(2) Atomic and Ionic radii: increases down the group.
(3) Density: increases down the group.
(4) Electro negativity: decreases down the group.
(5) MP and BP: increases on moving down the group.
(6) IE: decreases for group.
(7) Electron gain enthalpy: decrease down the group.
(8) Metallic character: increases down the group.
(9) Catenation: decreases down the group.
( 10) Allotropy: All the elements of 16 shows allotropy.
(11) Oxidation state: shows -2 , +2 , +4, +6 oxidation state.
/ (B) Chemical properties: All these elements are reactive but reactivity decreases with increa se in atomic number.
( 1) Action of air:

(2) Action of acicla:

S + 6HN03 ~ H2S0 4 + 6N02 + 2Hp
(3) Action of alkalies:
3S + 6NaOH ~ N~S0 3 + 2N~S + 3H 0
2
(4) Action of non-metals:
2S + c~ CS2 ; S + H2 ~ H2 S
/ Se + 2C½ ~ SeC½; S + 3F2 ~ SF6
/ (5) Action of metals:

I• Cu+ s~ CuS·
Dioxygen (0 2 )
Preparation:
,
Cd+ Se~ CdSe

I (aJ By thermal decompo1ition of oxygen rich elements:

n 2
Li
2KC10 3 M O 2KCJ + 30 2

Heat
2KMn04 - ----+ ~Mn04 + Mn02 + 0 2
(bJ By thermal decompo1ltion of metallic oxides:
2KNO Li
3 ----+ 2KN0 + 0
2 2

72
2Hg0fsJ 0K 2Hg + 0 2,g1 ,· 2Pb 0 Li
J 4fsJ ----+ 6Pb0 ➔- 0 2(g) 2Bao2 ~ 2Ba0 + 0
2
 p-B/ock Element 295

) sy the action of water or acicllfted

(C 2N¾O 2 + 2H 2 O ~ 4NaOH + potaaatum perman1anate on aocllum peroaide:
02
2KMnO 4 + 5N{½O 2 + 8H,2 SO
" -----+ Ki SO 4 + 2MnSO 4 + 5N¾SO 4 + 8H O + 50
cl) 1,.a1>oratory method: 2 2
l 420K
2KC1O 3 ~ 2KCI + 30 2
2

p,opertiea:
Ia) Reaction• with metal,
(i) 2Ca + 0 2 ~ 2CaO
(ii) 4Na + 0 2 ~ 2N¾O (Sodium oxide)
(ii) 2Mg + 0 2 ~ 2MgO
(iv) 4Fe + 30 2 ~ 2Fe 2 O3
(iv) 4Al + 30 2 ~ 2Al 2 O3
(b) Reaction• with non-meta11:
(i) S + O2 ~ SO 2
(iii) P4 + 50 2 ~ P4 OIO
(iii) 2C + 0 2 (limited) ~ 2CO
(iv) C + 0 2 (excess) ~ CO 2
(v) 2H 2 + 0 2 ~ 2Hp
(vi) N2 + 0 2 ~ 2NO (Nitric oxide)
fc) Reaction• with other compound■ :
1073 K
(i) 4NH 3 + 50 2 ~ 4NO + 6H 2O 700 K
(ii) 4HCl(g) + O2(g) ~ 2H 2O(g) + 2C½(g)
.. 725 K
(iu) 2SO 2(&1 + O21 g1 Pt 2SO3 (g) (iv) CS2 + 302 ~ CO 2 + 2SO 2
(v) 2ZnS + 30 2 ~ 2ZnO + 2SO 2 (vi) 2MgS + 30 2 ~ 2MgO + 2SO2
0 ~ 6CO 2 + 3H 2O
15
(vii) C6H6 +
2 2 (viii) CH 4 + 20 2 ~ CO2 + 2H 2O

7
(x) C2H6 + 202 ~ 2CO 2 + 3H 2O
• Uaea:
- Diooxygen is used by all living beings in respiration, an important constituent of rocket fuel.
- Used in making oxy-hydrogen (temperature 2800°C) and oxy-acetylene (temperature 3200°C) torches.
-As an explosive in coal mining, in metallurgical processes for removing the impurities of metals by oxidation
- In the manufacture of a large number of compounds such as phenol, sulphuric acid and nitric acid.

Clauification of oxides
(1) Simple oxides: MgO, Alp 3
(2) Mixed oxides: Pb 3O4 , Fep 4
(3) Acidic oxides : SO 2, Clp 7 , CO 2, NPs
(4) Basic oxides: N¾O, CaO, BaO
(5) Amphoteric oxides : Alp 3, ZnO
(6) Neutral oxides: CO, NO, N2 O

Ozone (03 )
• Preparation:
1
3O2~ 203; ~H = +142 kJ mor .
• Structure:
..
0
. / ~.
·.·o.. .o·
.
• Properties:
(i) PbS(s) + 4O3(g) ~ PbS04(s) + 4O2(g)
(ii) 2Klfaq) + Hp + 03(g) ~ 2KOH(aq) + I21s1 + 02(g)
(iii) Ba0 2 + 0 3 ~ BaO + 20 2
(iv) H20 2 + o3 ~ HP + 202
(v) NO1g) + O3(g) ~ N0 21 g1 + O21g1
 ef
atoc
296 Utt am 's M/-IT- CET (Chem,stry)
. P'J./

• Uses:
pre ve nts the harmful UV rays of the s um from reaching the ea rth 's s urfa ce .
used to stearlise a ir a nd wa ter.
used as bleaching age nt for s tach , fl o ur, oils, e tc .
u sed as disinfecta nt a nd germicide .
u sed in indu s try in the manufac ture of s ilk a nd syntheti c ca mphor .

Sulphur /
• Occurrence: Su lphur occurs in native state (free s tate ) as well as the combined state as
(a) Sulphide a nd (b) Sulphates
• Allotropic forms of sulphur:
( 1) Rhomic Sulphur:
Called a -sulphur or oc tahedral sulphur
It is pale yellow in colour
M .P. is 385.8 K and specific gravity 2.06.
Insoluble water but soluble CS 2 .
(2) Monoclinic sulphur :
Called (3-Sulphur or prismatic sulphur.
- M .P. is 393 Kand specific gravity 1.98
- Dissolves in CS 2 and stable above 369 K.
(3) In cycle- S 6 : The ring has chair form as follows:
s

(4) Small S 4 molecule: are unstable and exist in sulphur vapours as S 2 and 8 3 molecules.
(5) Plastic sulphur:
Called as y-sulphur
- Prepared by pouring boiling sulphur in cold water.
- Specific gravity is 1.95, no sharp M.P.
f6) Milk of sulphur :
3 Ca(OHh + l 28 ~ 2 Ca85 + Ca8 2O 3 + 3H 2O
2 CaS 5 + Ca8 2O3 + 6 HCl ~ 3 CaC1 2 + 3H 2O + 128 (Milk of sulphur)
Soluble in CS 2
Used in medicine
f7) Colloidal Sulphur :
H2S + 2HNO3 ~ 2H 2O + 2NO 2 + S (Colloidal sulphur)
N~S2O3 + 2HC1 ~ 2 NaCJ + 802 + H 2O + S (Colloidal sulphur)
(cone.)
IFl)I Compounds of Sulphur
/ (a) Sulphur Dioxide (S02 ) :

• Preparation:
(a) Laboratory methods:
Cu+ 2H2SO4 ~ CuSO4 + SO2 + 2H2O
N~S03/aqJ + 2HCl(aqJ ~ 2NaCl!aqJ + H 2O11J + SO21gJ
(b) Industrial method:
4FeS 21sJ + l 1O 21gJ ~ 2Fe O + 8SO
2 3(g) 2 /g)

• Properties:
Colourless gas, with pungent smell.
Acidic in nature .
 Elemeni
p-BlOCk

_ Soluble in water and forms H 2 S0 3 . Hence is called anhydride of sulphurous acid.

_ Liquefies at room temperature under a pressure of 2 atm and boils at 263K.
Reactions:
•
(l) Reducing agent: It reduces -
12 + S0 2 + 2 H2 0 ~ 2 HI + H2 S0 4
~Cr2 0 7 + 3S0 2 + H 2 S0 4 ~ K2 S0 4 + Cr2 (S0 4b + H2 0
2FeC13 + S0 2 + 2 H2 0 ~ 2FeCl2 + H 2 S0 4 + 2HCJ
5S0 2 + 2KMn0 4 + 2 H 2 0 ~
K2 S0 4 + 2MnS0 4 + 2H 2 S0 4
oxidizing agent (Lewis base): It oxidizes-
121
2H2S + S0 2~ 2 H 2 0 + 3S J
4FeC1 2 + S0 2 +4HC1 ~ 4FeC1 3 + 2 H 2 0 + SJ
(3) Action of alkali:
2NaOH + S0 2 ~ Na2S0 3 + 3SJ
N8.:?S0 3 + H2 0 + S0 2 ~ 2 NaHS0 3
(4) Action on non-metal:
S0 21 g) + Cl 2!gl ~ S0 2 Cl 2til
V20 s
2S0 21 g) + 0 21 g) - - - 2S0 3 !gl
• Uses: S0 2 is used
in the Manufacture of H 2S0 4.
in the refining of petroleum and sugar industry.
for fumigation , as a germicide and preserving of fruits .
as a anti-chlor, disinfectan t and preservative.
as a bleaching agent in the presence of moisture.
• Structure:

0:• pre-pre
: s 119°
~
~ • dre-dre
<J"\q:
I (bl Sulphuric acid (H 2 SO4 ):
It is called King of Chemicals.
• Manufacturing process : There are two process-
(A) Contact process : This process involves the following important steps:
(i) Preparation of SO2 :
S 8 + 80 21g1~ 8S0 2!gl
4FeS 2 + 110 2 ~ 2Fe 20 3 + 8S0 2
(ii) Oxidation of SO 2 to SO3 :
V20 s
2S0 2 (g) + 20 2(g) ;:::=== 2S0 3 ; ~H = - 196.6KJ
(iii) Dissolution of SO3 in H2 SO4:
S0 3 + H 2S0 4 ~ H 2 S 2 0 7 (oleum)
(iv) Dilution of oleum, H 2 S 2 0 7:
H2 S 2 O 7 + H2 O ~ 2H 2 S0 4 (96 to 98% pure)
(B) Lead Chamber process :A mixture of S0 2 , NO and air is treated with steam to produce H 2 SQ 4 and
nitric oxide (NO) acts as catalyst:
NO
2S0 2 + 0 2 + 2H 2 0 _ ___, 2H2S04
Different steps are:
(i) Water reacts with NO to give HNO3 :
2H 2 0 + NO~ HN0 3 + 3H+
r'
Uttam 's MHT-CET (Cherni
·"ry)
298

(ii) Sulphur oxidises to SO2 in the presence of oxygen:

S + 0 2 ~ SO 2
(iii) HNO 3 reacts with S02 and gives SO3 :
2HNO 3 + 2SO 2 - H2 O + NO + NO 2 + 2S0 3
(iv) Sulphur trioxide reacts with water to form H2 S0 4 :
SO 3 + H2 O - H2 SO 4
• Physical Properties: 4 298
A colourless , dense , oily liquid having specific gravity of 1 .8 at K.
Freezing point is 283 K and the boiling point is 611 K.
st
A dibasic acid and in aqueous solution, ionizes in two eps :
H SO 4 ~ H' + HSO 4 -, K01 > 10
2
2
~
Hso 4 ~
- K = 1 2
H' + sO4 •a2,
2
x 10-

• Chemical Properties (Reactions):

( 1) Dehydrating agent: H so
(COOH)2 H2S04 CO+ CO2+ H2O C12 H22011 2 4 12C + l lH20
(2) Oxidizing agent : Hot cone. H2SO 4 acts as an oxidizing agent.
H so ~ Hp + so + 10] C + 2H2S04 ~ CO 2 + 2S0 2 + 2H 0
2
;
P4 + 10H 2 S04 ~ P4 0 10 + 10S02 + 10H20
2
s 2+ 2H 4 SO - 3SO + 2H O
+ 6H o ~ 4H PO Zn + H2S04 ~ ZnS0 4 + H2
2 4 2 2
P4 O JO 2 3 4 Heat
2HX + H 2 SO4 X2 + SO 2 + 2H2O
Cu + 2H 2 SO 4 ~ CuSO 4 + SO 2 + 2H 2 0
(where X = Br or I)
2FeSO + 2H SO -Heat - - Fe (SO 1J + SO 2 + 2H 2O
2 4
2HI + H 2 S0 4 ~ 2H 20 + S0 2 + 12
4 2 4
(3) Sulpbonating agent: Cone. H SO acts a sulphonating agent i.e. addition of -S0 3 H group to the benzene.
2 4
(4) Action of PC1 5 : C1SO -OH + PC1 5 ----+ Cl-SO 2 Cl + POC13 + HCl
HO-SO2· OH + PCls - c1-sopH + POCl3 + HCl 2
(Sulphuryl chloride)
(Chlorosulphuric acid)
(5) Action of KC10 3 :
3KCIO3 + 3H 2SO 4 - 3KHSO 4 + HC1O 4 + 2Cl0 2 + H2 0
(6) Action on salts:
3MX + H SO 4 - 2HX + M2SO 4 (where X = F, Cl, NO 3 and M = metal)
2
• Uses: H2 SO 4 is used
in the manufac_ture of dyes'. fertilizers, detergents, explosives (T.N .T. nitroglycerine, green cotton) etc.
m the preparat10n of other important chemicals like HNO 3 , HCl, sulphates, alums, ether, etc.
in lead storage batteries, refining of petroleum.
as dehydrating agent, oxidizing agent, pickiling agent.

Oxyacids of Sulphur /

No. Name Structure Ollidation number

Sulphoxylic acid (H 2 SO 2 ) H-O-S-OH +2
0

2 Sulphurous acid (H 2 SO 3 ) HO-S - .II OH

+4

s
II +2, + 4
3 Thisul hurous acid HO-S-OH
0 0
Dithionous acid (H 2 S 2 Q 4 )
II II +3
HO-S-S-OH
0 0
II II +4
5 Pyrosulphurous acid (H 2 sp 5 ) HO-S-O-S-OH
 299
p-Block Element

sulphuric acid (H 2 SO~) HO -

r?S - OH +6
(6)
II
0

HO -
ff
S- OH
(7)
- 2, +6
II
0
0 0
Pyrosulphuric acid (oleum) (H 2 S2 0 7 )
II II
HO-S - 0-S - OH +6
(8)
II II
0 0
0
Peroxy monosulphuric acid (H 2 S0 5 )
II
H0-0-S-OH +6
(9)
II
0
0 0
Peroxydisulphuric acid (H 2 S2 0 8 )
II II
(10) HO - S- 0 - 0 - S- OH +6
II II
0 0
0 0
II II
(11) HO-S-S-OH +5
II II
0 0

•EA Group 17 Elements j

, General electronic configuration: ns2 np5

, Elements: 9 F, 17 Cl, 35 Br, 53 1, 85 At
• Occurrence: Not found in free state as they are very reactive. Found as halides, x-.
► Fluorine is found in the form of fluorospar or fluorite (CaF 2 ), cryolite (Na3 AIF 6), fluoropatite [3Ca3
(P04)2·CaF2l•
► Chlorine is the most abundant in the form of NaCl and camallite (KCl-MgC1 2 ·6H 2 0) in oceans, salt lakes ,
rock beds .
► Bromine occurs as bromide salts of alkali and alkaline earth elements. It is also obtained by oxidation of
bromide ions in sea water.
► Iodine is found in sea weeds as C and 10; in Chile saltpetre.
►
Traces of iodine are found in mineral deposits. Iodine also finds its way into animal system as thyroxin in
thyroid glands .
• Phyaical properties:
► Molecular formula and physical state: F 2 (Pale yellow gas), Cl 2 (Greenish yellow gas), Br2 (Reddish brown
liquid), 12 (Purple solid) .
► Atomic and ionic radii: Increase down the group and halogens are smallest atoms in a period.
► Ionisation enthalpy is very high and decreases down th e group.
► Electronegatiuity: Fluorine is the most electronegative element and electronegativity decreases down the
group.
► Electron gain enthalpy increases from F to Cl and then decreases to 1.
► Bond dissociation enthalpy increases from F2 to Cl 2 and then decreases in Br2 and 12 • F - F bond is
weaker than Cl - Cl because of the large repulsions of the lone pairs of F 2 which are closer than in c1 .
2
► Non-metallic character: Due to higher values of electronegativity, all halogens are typical non-metals. Non
metallic character decreases down the group . Iodine shows metallic luster.
► Density: The density of halogens increases on moving down the group. This is due to an increase in the
state of agglomerisation.
► Melti ng and boilin11 ootnu increase down the group. Halogens possess low melting and boiline: p oints.
)0

► Oxidation states: .
. . •tis the most electronegative element.
F shows only -1 madauon state as 1
- Other elements show -1 , + 1, +3 , +Sand +7 . . . .
. . f Cl B d I are observed only m fluondes, modes and oxoacids.
Higher oxidation states o , r an
• Chemical trends:
( 1) Oxidising power:
F 2 > Cl 2 > Br2 > 12
Reduction potentials decrease from F2 to 12·
A halogen oxidises a halide ion of higher atomic number.
(2) Reactions with metals and non-metals:
. al d many non-metals to form halides. The reactivity decreases as we go
► All halogens react with met s an
down the group from fluorine to iodine.
Cu+ F2 ~ CuF2; 2Al + 3Br2 ---1 Al2Br6
. - h t f the M x bond in metal halides decreases in the following order:
► Th e 1omc c arac er o -
M - F > M - Cl > M - Br > M - I
(3) Reactivity towards hydrogen: All halogens form hydrogen halides.
H2 +X2 ~2HX
(Halogen) (Hydrogen halide)
► Characteristics of hydrogen halides:
(i) Reactivity towards hydrogen F2 > Cl2 > Br2 > 12

(ii) Boiling points HF > HI > HBr > HCI

(iii) Melting points HI > HF > HBr > HCl
(iv) Bond lengths HI > HBr > HCI > HF
(v) Bond dissociation enthalpy HF > HCl > HBr > HI
(vi) Acidic strength HI > HBr > HCl > HF
(vii) Thermal stability HF > HCl > HBr > HI
(viii) Reducing power HI> HBr > HCI > HF
(4) Reactivity towards oxygen: Halogens react with oxygen to form oxides.
► Characteristics of oxides:
(i) Fluorine forms two oxides OF2 and 0 2F2 called oxygen fluorides, other halogens form oxides in which
oxidation states of these halogens range from + 1 to +7.
(ii) The higher oxides of halogens are more stable than the lower ones.
(5) Reactivity of halogens towards other halogens:
Halogens wh~n c~mbi~e ~ongst the~selves form many compounds known as interhalogen co~pounds of
th e types XX ,XX3,XX5,XX7 where X 1s a larger size halogen while X' is halogen having smaller size.
(6) Other reactions:
(i)
(ii) X2 lg) + H20(I) ~ HX(aq) + HOX(aq),
Where X = Cl or Br
(iii) 41 (aq) + 4 Htaq) + 02(g) ~ 212(s) + 2H 0(1)
2
(iv) CH 4 + 2F2 ~ C + 4HF
(v) CH 4 + CJ 2 ~CC1 4 + 4HCI
(vi) 4NaOH + 2F2 ~ 4NaF + o2 + 2H 0 (vii) 2NaOH + Cl 2 ------+ NaCl + NOCI + Hp
2
(Cold and dilute) (Chloride) (Hypochlorite)
(viii) 3NaOCJ ~ 2NaCI + NaClO
3 (ix) 6Na0Cl ~ SNaCI + NOC1 3 + Hp
(Hot) (Sodium chlorite)
(x) Cl2 + H20 ~ HCl + HOCl
HOCl ~ HCl + !OJ
(Nascent oxygen) ] Bleaching action
p-Block Element
301

AJ1o1Dalou• behaviour of Fl;;;.---

ne: ------··
!--
s,. No, Propertiea - ---
--- -
,..;::.-- _Fluorine
Reactivi tv Other element• of 2roup 17
l. More reactive
Oxidation state Less reactive
2. I
Polyhalide ion s 1, + J +3 , +5 and +7
3. Does not. form
L---- Form such as 13 , Br3 , Cl 3 , etc.

- 4.
5.
H bond formation
Behaviour of hydrogen h a lide
Strom, tendency
HF is liquid
Do not. formed
HX are gases (X = Cl, Br, T)
HF is weak acid
- Electron gai n enthalov
HX are strong acids (X Cl , Br, I)
- 6.
7. Nature of compounds
Less than chlorine
Ioni c nature, e.g. AIF3,CsF
Chlorine has more than fluorine
Covalent nature , e. g. AlC1 3
ll·m Chlorine
• Occurrence: Chlorine does not occur 1·n free s t ate due to B h · h · ·
• Some mlnerala containing chlorine are_ r ig reactivity. It occurs in combined state .
(i) Rock salt (NaCl) (ii) Carnalite (KCl·MgCl 2 , 6H 2 O)
(iii) Sylvine (KC!) (iv) Horn silver (AgCl)
Preparation:
(A) General methoda:
- By the oxidation of hydrochloric acid:
MnO 2 + 4HC1 ~ Mnc1 2 + c1 2 + 2 H 2o
PbO 2 + 4HCI ~ PbC1 2 + Cl 2 + 2H 2O
Pb 3 O4 + 8HCI ~ 3 PbC1 2 + Ci 2 + 4H 2o
2KMnO 4 + 16HCI ~ 2KCI + 2MnCl 2 + 8H 2O + 5Cl 2
K2Cr2O7 + 14HCl ~ 2KCI + 2CrC1 3 + 3Cl 2 + 7H 2 O
- By the action of mineral acid on bleaching powder (CaOCl:J:
CaOCl 2 +2HCl ~ CaC1 2 + Cl 2 + H2 O
CaOCl2 +H 2 SO 4 ~ CaSO 4 + Cl 2 + H2 O
- By the action of cone. 112 S04 on NaCl the presence of Mn02 :
2NaCI + MnO 2 + 3H 2 SO 4 ~ 2NaHSO 4 + MnSO 4 + Cl 2 + 2H 2 O
(Bl Manufacture of chlorine:
Deacon process:
4HC1 + 0 2 CuCl 2 2Cl 2 + 2H 2O
EZ.ctrolytic process: During electrolysis, solution of brine (NaCl), H2 gas is liberated at cathode,
whereas Cl 2 gas is liberated at anode.
0 Chemical propertiea (Reactiona):
NH 3 + 3Cl 2 ~ 5NaCl + NaC1O 3 + 3H 2 O
Reaction with ammonia:
(excess)
8NH 3 + 3Cl 2 ~ 6NH 4 Cl + N2
(excess)
Reaction with alkalies:
2NaOH + Cl 2 ~ NaCl + NaOCI + H2 O 6NaOH + 3Cl 2 ~ 5NaCI + NaC1O 3 + 3H 2 O
(H ot and cone .)
(Cold and dilute)
Reaction with slaked lime:
Cold
2Ca(OH'2 + 2Cl 2 - - - Ca(OClb + CaC1 2 + 2H 2 0 (Dry slaked time) (Bleaching powder)

Oxidising agent:
2FeSO + H SO 4 + Cl 2 ~ Fe 2 (SO 4 ):i + 2HC1
4 2
SO + 2H O + Cl ~ H 2 SO 4 + 2HC1 12 + 6Hp + 5Cl 2 ~ 2HlO 3 + l0HCl
2 2 2

Bi.aching agent:
Cl + H O ~ 2HCl + 10] and Coloured substance + [O] ~ Colourless substance
2 2
302 r
Utta m 's MHT-CET (Ch .
ern1.v11yJ

0
Oaea• Cl 1. - -- - - - - - - - - - - - - - - - - -- - - -- - - - -
• 2 s u sed

as bleach · .
in th ing agent m texti le a nd paper indu s try. . . CCl2 F 2 )
e manufacture of dystu ff, explos ives a nd refrigera nt such as Freon (1. e .
for
. the sten·1·1zation
. of municipa l supp ly wa te r.
in th e extractio n of metal s like Au a nd Pt.
Compounds of Halogens \
(a)
Hydroge n Chloride (Hydrochloric acid):
► Laboratory method of preparation: \
NaCl + H2 S0 4 ~ Na HS0 4 + HCl
NaHS0 4 + NaCl ~ Na,2 S0 4 + HCl
►
1

Properties: \

Colourless gas with pungent odour . . .

On liquification gives a colourless liquid (b .p.189 K) which on freezing gives white cryStalline sohd (m.p .159 l<). '
Highly soluble in water a nd gives strongly acidic solution .
~ H 3 0 {aq) + Clfaq);
7
HCl(gl + H 2 0 111 Ka = 10
Reaction with sodium:
2Na + 2HCl ~ 2NaCl + H2 (with explosion)
Reaction with ammonia (NH 3 ):
NH 3 + HCl ~ NH 4 Cl (white fumes) ,
Reaction with noble metals like gold, platinum: A mixture of three p~s of cone. _HCl and one Part of \
cone. HN0 is known as aquaregia. It is used for dissolving noble metals, hke gold, platinum. I
~ AuCI;j +NO+ 2H 0
3

Au+ 4H+ + N0 3 + 4Cl- 2 \I

3Pt + l 6H+ + 4NO; + l BCC ~ 3PtCl~- + 4NO + 8H 2 0
1
Reaction with salts: Hydrochloric acid decomposes salts of weaker acids and dissolves basic oxides and
neutralizes alkalies.
(i) NaHS0 3 + HCl ~ NaCl + H2 0 + S0 2 (ii) N82C0 3 + 2HC1 ~ 2NaCl + H 2 0 + CO 2
(iii) N82HC0 3 + HCl ~ NaCl + H2 0 + CO 2 (iv) CaO + 2HC1 ~ CaC12 + H 2 0
(v) Mg(OH)i + 2HC1 ----1 MgC1 2 + 2H 2 0 (vi) NaOH + HCl ~ NaCl + H 2 0

► Uses: HCl is used

extensively as laboratory reagent.
- to manufacture glucose from corn starch.
- in medicine and in galvanizing.
(b) Interhalo ~en Compounds:
Molecule Total no. electron Bond Lone Shape Example
pairs around X pairs pairs
XY 4 1 3 Linear CIF , CrF, BrCl, !Cl, IBr
XY3 5 3 2 T - Shap ed ClF 3, BrF 3 , IC1 3
XYs 6 5 1 Square py ramidal BrF 5 , IF 5
XY7 7 7 0 Pentagonal bi pyramidal IF7 -
{c) Oxyacids Oxoacids of Halo ens:
Name Oxidation number of X F Cl Br I
H ohalous acid , HXO +l HOF HOCl HOBr HOI
Halous acid, HX0 2 +3 HC10 2
Halie acid HX0 3 +5 HC10 3 HBr0 3 HI0 3
Perhalic acid, HX0 4 +7 HC10 4 HBr0 4 HI0 4
► Oxidizing power:
HCIO > HC10 2 > HCI0 3 > HC10 4

► Thermal stability, acidic character:

HCIO < HC10 2 < HC10 3 < HC10 4
p-Block Element 303

- Group 18 Elements (Noble Gasea)

oeoeral electronic configuration: ns2 np6
• S)ement•: 2He, 10Ne, 1sAr, 36Kr, 54 Xe, 86 Rn
•
• physical •tate: All are rnonoatornic gases.
• physical properties:
Atomic radii increases down the group.
► Ionization enthalpy is very high and decreases down the group with increase in size .
► Electron gain enthalpy is positive as noble gases have no tendency to accept the electrons .
► Melting and boiling points are very low due to weak interatomic dispersion forces.
► Liquefication tendency: Noble gases are not easily liquefied. However, the tendency for liquefication
increases on moving down the group.
►
Ability to diffuse: All noble gases are able to diffuse through glass, rubber, plastic material and some metals.
►
Solubility in water: Noble gases are slightly soluble in water and solubility increases down the group.
Chemical propertiea: Noble gases are unreactive due to
Completely filled valence shells
Large and positive electron gain enthalpy and
► Very high ionization enthalpy.
Use•:
Helium
Since its lifting power is 92% that of hydrogen, therefore it is used weather balloons and airships .
It is used as breathing mixture (or oxygen dilutant) for divers.
Mixture of 0 2 and He is used in the treatment of asthma.
Used for inflating the tyres of aeroplanes .
Neon
Neon lighting is used for advertising
- It is used for filling sodium vapour lamps.
- It is also used in beacon light as safety signal for air navigators .
► Argon
Primarily used to create an atmosphere in light bulbs, welding and fluorescent bulbs.
Used in Geiger counters, as it becomes ionized in the presence of radiation.
The ratio of 4 °K to 40Ar can be used to date the age of rocks since Ar is obtain by radioactive decay of an
isotope potassium.
► Krypton . . .
The light emitted by Kr in an electric discharge tube is used for_runway and approach lights m airports.
85
Kr is used to measure thickness of sheets of metals and plastics.
► Xenon
- It is used in electrical flash bulbs for high speed photography.
Liquid Xe is used in research laboratories for the detection of measons and gamnia photons .
► Radon
Radon is used in radiotherapy of cancer.
- It is used for research in radioactivi •
000