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PROPERTIES OF COMPOUNDS:

Compounds of Tin
1.

Stannic oxide (SnO2) It is prepared by heating tin strongly in air


SnO2

Sn + O2

It can also be prepared by heating metastannic acid obtained by the action of conc. HNO 3
on tin.
Sn + 4HNO3 (conc.) H2SnO3 + 4NO2 + H2O

H2SnO3

SnO2 + H2O

It occurs in nature as tin stone. It is a white solid insoluble in water and is amphoteric in
nature. With NaOH it forms Na2SnO3. It is used for making enamels and glazes for tiles,
pottery etc. It is also used as a polishing powder.
2.

Stannous oxide (SnO). It is prepared by heating stannous oxalate

SnC2O4

SnO + CO + CO2

Oxidation of SnO to SnO2 is checked by CO.


It is a grey solid which oxidises readily to SnO2 when heated in air.
2SnO + O2

2SnO,

It is amphoteric in nature and reacts both with acids and alkalies. With NaOH it forms
Na2SnO2.
3.

Stannous chloride (SnCl2) When Sn is heated with HC1 (conc.) SnCl2 is formed
Sn(s) + HCl(conc.)

SnCl2(aq.) + H2(g)

On concentrating the resulting solution, crystals of SnCl22H2O are obtained. When


this is heated basic tin chloride is obtained.
SnCl2 . 2H2O(s)

Sn(OH)Cl + HC1 + H2O

To obtain anhydrous SnCl2, heat Sn in dry HC1 gas.

Sn + 2HC1

SnCl2 + H2

(i) It exists as a anhydrous (white powder, m.p. = 520 K, rhombic solid) as well as
dihydrate SnCl2.2H2O (white, m.p. = 480 K, monoclinic) and is used as a strong
reducing agent in conc. HC1 in laboratory.

SnCl2 also reduces HgCl2


2HgCl2 + SnCl2
Hg2Cl2 + SnCl2

Hg2Cl2 + SnCl4
2Hg + SnCl4

(ii) It is precipitated as hydroxide by an alkali.


(iii) It forms addition compounds with NH3 such as SnCl2. NH3 and SnCl2.2NH3.
4.

Stannic chloride, SnCl4. It is obtained by the action of Cl2 on molten Sn


Sn + 2C12

SnCl4

It can also be obtained by distilling tin with mercuric chloride.

Sn + 2HgCl2
SnCl4 + 2Hg
(i) It is a colourless fuming liquid (b.p 388 K) soluble in water.
It is used as a strong reducing agent in laboratory. It is also used as a mordant in dyeing.
(ii) It can exist as SnCl4.5H2O and with excess water it is hydrolysed to form basic
chloride and ultimately stannic acid (H2SnO4).
SnCl4 + H2O

Sn(OH)Cl + HCl

Sn(OH)Cl + 3H2O

Sn(OH)4 or H2SnO4 + 3HC1

Its hydrolysis is prevented by HCl which forms complex anion [SnCl6]2


(iii) It forms double salts with NH3, N2O, PC15 e.g., SnCl4.4NH3.
It is used as a mordant and tinning agent.
Compounds of Lead
(i) Lead oxide (Litharge), PbO. It is prepared by heating the nitrate.

2Pb(NO3)2

2PbO + 4NO2 + O2

It exist in two varieties yellow form (messicot) and red form (litherage). Yellow form is
prepared by gently heating lead in air while fusion yield red form. It is insoluble in water
and amphoteric in nature.
It dissolves in NaOH to form sod. plumbite.

PbO + 2NaOH
Na2PbO2 + H2O

It can be reduced with various reducing agents (C, H2, CO etc.) to lead.
It is used in paints and varnishes, for making flint glass, for making lead (II) salts and
for glazing pottery.
(ii) Lead dioxide, PbO2. It is prepared by heating Pb3O4 (2PbO + PbO2) with dilute HNO3

Pb3O4 + 4HNO3

2Pb(NO3)2 + 2H2O + PbO2

It is amphoteric in nature and dissolve in NaOH to form sodium plumbate.

2NaOH + PbO2
Na2PbO3 + H2O
It is a powerful oxidising agent. It reacts with cone. HCl on warming to give PbCl4.
It is a chocolate brown solid insoluble in water and nitric acid. It is a powerful
oxidizing agent. It is amphoteric in nature and is used in lead storage batteries and in safety
matches.
(ii) Minium or Sindhur or Red lead, Pb3O4. It is prepared by heating PbO in air to above 673 K.
6PbO + O2

373 K

2Pb3O4

It is a red crystalline solid insoluble in water.


It is a mixed oxide PbO2 + 2PbO and reacts with HNO3 to form Pb(NO3)2 and PbO2
Pb3O4 or 2PbO.PbO2 + 4HNO3

Pb(NO3)2 + 2H2O + PbO2

It is a strong oxidising agent. It liberates chlorine with cone. HCl and O 2 with conc.
H2SO4
Pb3O4 + 8 HCl

2Pb3O4 + 6H2SO4

3PbCl2 + 4H2O + Cl2

6PbSO4 + 6H2O + O2

It is used as a protective paint in iron, steel and silver mirrors and in glass industry.
(iv) Lead chloride, PbCI2. It can be prepared by treating a salt of lead with dil. HCl.
Pb(NO3)2 + 2HC1

PbCl2 + 2HNO3

It can also be obtained by dissolving lead(II) oxide or lead (II) carbonate in HCl. It is
soluble in hot water but precipitate out in cold water. It is soluble in conc. HCl due to the
formation of a complex, tetrachloroplumbate (II) ion.

PbCl2 + 2HC1
H2[PbCl4]
It also reacts with hot lime water to give Pb(OH)Cl which is used as white pigment.

PbCl2 + Ca(OH)2

Pb(OH)Cl + CaO + HCl

(v) Lead tetrachloride, PbCl4. It is obtained by warming PbO2 with conc. HCl.
Catalysts:
TiCl3

(1)

Used as Ziegler Natta catalyst


V2 O5

(2)

SO 2

Converts

SO3

to

H 2SO4

in the contact process for making

MnO 2

(3)

KClO3

Used as a catalyst to decompose

O2

to give
NH 3

(4)

Fe

Used in Haber Bosch process for making

FeCl3

(5)

CCl 4

Production of

CS2

from

Cl2

and

FeSO 4 & H 2 O2

(6)

Fentons reagent
PdCl2

(7)

Wacker process for converting


C 2 H 2 H 2 O PdCl 2 CH 3CHO 2HCl Pd

(8)

Pd

For hydrogenation (Phenol

Cylohexanone)

(9)

Pt/PtO

Adams catalyst used for reduction


SO 2 SO3

(10) Pt

contact process

(11) Pt

Cleaning car exhaust fumes

CH3 2 SiCl2
(12) Cu

In manufacture of

(13) Cu/V

Oxidation of cyclohexanol

CuCl 2

Cl2

(14)

Deacon process for making

from HCl

(15) Ni

Raney nickel for reduction of organic compounds

Compounds of Iron
FeSO 4 ,7H 2 O

Ferrous sulphate (Green vitriol),


It occurs in nature as copperas commonly known as hara Kasis.
Preparation

H 2SO 4

i)

By dissolving scrap Fe in dil.


H 2SO 4

ii) From kipps waste which contains ferrous sulphate with some free

the latter is

FeSO 4

neutralised with scrap iron forming

and hydrogen.

iii) By the action of air and water on iron pyrites. The solution is treated with scrap iron to
Fe2 SO 4 3

H 2SO 4

remove

and to reduce

FeSO 4

to

2 FeS2 7O2 2 H 2 O 2 FeSO4 H 2

Properties
FeSO 4

i)

Hydrated and anhydrous

are green and white in colour respectively. It is


MgSO 4 .7H 2 O

isomorphous with epsom salt,


exposure to air.

ZnSO 4 .7H 2 O

and

. It effervesces on

FeSO 4

ii)

iii)

Light green crystals of


to air, due to oxidation.
On heating at

3000 C

lose water and turn brown is h-yellow on exposure


FeSO 4

it gives anhydrous

(Colourless) which on further

Fe 2 O3 SO 2 and SO 3

heating gives
iv)

Like others at

,
3000 C

HNO3

it takes up

forming brown coloured double

Fe NO SO 4

compound,
(v)

nitroso ferrous sulphate (Ring test for nitrates).

It decolourises acidified potassium permanganate and turns acidified dichromate


green (reducing character).

(vi) It forms double salts with sulphates of alkali metals with general formula
R 2SO 4 .FeSO 4 .6H 2O

. With ammonium sulphate, it forms a double salt known as

FeSO 4 . NH 4 2 SO 4 .6H 2O

ferrous ammonium sulphate or Mohrs salt,

. It does not
SO 24

Fe2 , NH 4

effervesce. It ionises in solution to give

and

ions.

Fe 2 O3

Ferric oxide,
i)

It occurs in nature as haematite.


Fe 2 O3

ii)
iii)

H 2O

is a red powder, insoluble in

H 2O

and not acted upon by air or

It is amphoteric in nature and reacts with acids and alkalies.


H2

iv)

It is reduced to iron by

,C and CO.
CO 2

v)

It is used as a catalyst in the oxidation of CO to

in the Bosch process.

FeCl3

Ferric chloride,
Preparation
Fe OH 3

FeCl3 .6H 2 O
i)Hydrated ferric chloride
or ferric oxide in dil. HCl.

can be prepared by dissolving iron,

Cl2

ii)Reaction of Fe with dry

FeCl3

gives anhydrous

Properties
H 2O

i)Anhydrous salt is dark red, deliquescent compound and highly soluble in


ii)

Its aqueous solution is acidic due to hydrolysis.

iii)

On heating above 7500C it gives

FeCl 2
H 2S

iv)

It oxidizes

S,SO 2

to

Cl2

and

H 2SO 4 ,SnCl 2

to

.
SnCl 4

to

Na 2S2 O 3

and

Na 2S4 O 6

to

Copper, Silver and Gold : Coinage metals.


These metals are commonly called as coinage or currency metals. Their general electronic

n 1 d10 ns1
configuration is

. These show variable valencies +1, +2, and +3.

Gradation in properties
i)

The nobility increases from copper to gold.

ii) The affinity for oxygen also decreases from Cu to Au.


iii) Copper forms a large number of salts followed by silver followed by gold.
iv)The ease with which the salts of these elements are reduced increases from Cu to Au.
Cyanide complex of iron:
Fe2 K 4 Fe CN 6 Fe2 II Fe II CN 6
Ferroferrocyanide (White)
Fe 2 K 3 Fe CN 6 Fe3 II Fe III CN 6
Ferroferricyanide (Turnbulls Blue)
Fe3 K 4 Fe CN 6 Fe4III Fe II CN 6
Ferriferrocyanide ( prussian blue )
Fe3 K 3 Fe CN 6 Fe III Fe III CN 6
Ferriferricyanide ( Brown )

Compounds of Copper
CuSO 4 .5H 2 O

Copper sulphate, cupric sulphate or blue vitriol,

. (Nila Thotha)

Preparation
i)

By treating copper scrap or turnings, cuprous oxide, cupric oxide or malachite with
H 2SO 4

1
Cu H 2 SO4 O2 air CuSO4 H 2O
2
CuFeS2

ii) By roasting copper pyrites,

in air.

Properties
i)

It has 5 molecules of water of crystallisation; all of which can be removed on heating,


CuSO 4

to form colourless

H 2O

(again coloured with

).

ii) At high temperature it forms cupric


oxide.

CuSO4.5H2O

exposure

Pentahydrate
(blue)

CuSO 4.3H2O
Trihydrate
(pale blue)

100 C

CuSO4

Anhydrous
(white)

2370 C

CuSO 4.H2O
Monohydrate
(bluish white)

K 2SO 4 .CuSO 4 .6H 2 O

iii) It forms double salts with alkali sulphates, e.g.


NH 4 OH

(iv) When treated with


, it first forms precipitate of cupric hydroxide copper (II)
sulphate (Schweitzers reagent), used for dissolving cellulose in the manufacture of
CuSO4 2 NH 4OH Cu (OH ) 2 NH 4 2 SO4

artificial silk.
(v) It reacts with KCN forming a complex compound

K 3 Cu CN 4

2CuSO4 4 KI Cu2 I 2 2 K 2 SO4 I 2

(vi) It liberates iodine from soluble iodides.

.
CuSO 4

(i) Used in the preparation of Bordeaux mixture (


kill moulds and fungi on wines.

solution + lime) which is used to

(ii) Used in electroplating, electrotyping, calico printing and dyeing.


Compounds of Silver
AgNO3

Silver Nitrate, Lunar Caustic,


. Silver nitrate is prepared by dissolving the metal in
dilute nitric acid and crystallizing the solution.
(i) Silver nitrate forms large rhombic plates (m.p. 485 K) very soluble in water. On heating
it gives metallic silver and nitrogen dioxide.
2AgNO3 2Ag 2NO 2 O 2

(ii) It gives a black stain when it comes in contact with skin or cloth due to its reduction to
metallic silver. (Finely divided silver is black in colour). Its use as a caustic is based on
this oxidizing property of silver nitrate.
Na 2S2 O 3

(iii) With sodium thiosulphate. With a very dilute solution of


, Silver nitrate gives a
white precipitate which quickly changes colour to yellow, brown and finally black due
to formation of silver sulphide.

S2 O32 2Ag Ag 2S2 O3 (white ppt.)


Ag 2S2 O3 H 2 O Ag 2S H 2SO 4

With a concentrated solution of sodium thiosulphate, silver nitrate gives no


precipitate. This is because silver thiosulphate formed is readily soluble in excess of
sodium thiosulphate forming a complex salt.
Ag 2S2 O3 3S2 O32 2 Ag S2 O3 2

Uses of Silver Nitrate.


(i) As marking ink and in hair dyes.
(ii)In medicine, in dilute solutions as caustic for granular lids and unwanted skin growth.
(iii) For preparing silver halides used in photography.
(iv) In silvering of mirrors.
(v) As a reagent in the laboratory.
Cl , Br and I

(vi) In volumetric analysis for the estimation of halides (


cyanides.

), thiocyanates and

Silver Fluoride, AgF. It can be prepared by dissolving the oxide or carbonate of silver in
H2O

hydrofluoric acid and crystallizing when crystals of the monohydrate, AgF.


obtained. It is use for disinfecting water.

, are

Silver Chloride, AgCl. It occurs in as horn silver. It is easily obtained as a white precipitate
by adding a double chloride to a silver salt solution. The precipitate is insoluble in water and
concentrated acids but easily dissolves in aqueous ammonia, alkali-cyanides and sodium
thiosulphate solution due to the formation of complex salts in each case.
AgCl 2NH 4 OH
AgCl 2KCN

Ag NH 3 2 Cl 2H 2 O

K Ag CN 2 KCl

AgCl 2Na 2S2 O3

Na 3 Ag S2 O3 2 NaCl

In fact a series of thiosulphate complexes of silver are produced.


Ag S2 O 3

These are :

. Ag S2 O 3 2

Silver chloride may be reduced to metallic silver by fusing it with sodium or potassium
carbonate, or by reduction with nascent hydrogen from zinc and dilute sulphuric acid, by
heating it in a current of hydrogen, or by boiling with caustic soda and glucose.
NH 3

Dry silver chloride also absorbs ammonia forming compounds such as AgCl.
3NH 3

2AgCl.

3NH 3

and AgCl.

. However, in aqueous solution the complex is only

Ag NH 3 2 Cl

.
Silver Bromide, AgBr
Preparation by adding a silver salt solution to soluble bromide solution
Properties
i)

It is insoluble in water and conc. Acid but soluble in excess of strong solution of
NH 4 OH

ammonia (cf. AgCl is soluble in dilute solution of


solution).

NH 4 OH

, Agl is insoluble in

ii) Silver halides are also soluble in KCN and hypo solutions
iii) On heating, it melts to red liquid.
iv) It is used as the light sensitive material in photographic films. It is the most sensitive
AgX to photo-reduction.
Zinc, Cadmium and Mercury

n 1 d10 ns 2

(a) These are the elements of group 12 having electronic configuration


and
+2 oxidation state. In these elements the d-subshell is full, hence these are regarded as
non-transition elements which is evident from the following characteristics.
(i)

They do not show variable valency except mercury

(ii) Many of their compounds are white.


(iii) Their melting and boiling points are very low.
(b) Unique structure of mercurous ion : Unlike Zn and Cd, Hg exhibits +1 well as +2
Hg 22

oxidation state. Thus mercurous ion exists as

Hg

and not as

(c) Structure of mercurous ion It consists of two atoms linked by a covalent and

Hg Hg

Hg

and explains the diamagnetic character of mercurous ions if it was

(presence of an unpaired electron in 6s orbital), mercurous salt should have been


paramagnetic.
(d) Anomalous behaviour of mercury,
(i)

It is liquid at ordinary temperature while Zn and Cd are solids.

(ii) It is less electropositive than hydrogen and therefore does not displace hydrogen
from acids while Zn and Cd does.
(iii) It does not form hydroxide or peroxide, while Zn and Cd do so
(vi) Mercuric oxide, on heating, gives, metallic mercury and oxygen while oxides of
Zn and Cd are stable towards heat.
NH3 , HgCl 2

(v) is covalent while zinc and Cd chlorides are ionic. With

gives a white

Hg(NH 2 )Cl

ppt. of

, while Zn and Cd salts form complex ions,

M NH 3 4

Compounds of mercury
Hg 2 Cl2

Mercurous chloride,

(Calomel). Preparation :

(i) By adding dilute hydrochloric acid to a mercurous salt solution, usually mercurous
nitrate, a white precipitate of mercurous chloride is formed.
Hg 2 NO3 2 2HCl Hg 2 Cl 2 2HNO3

(ii) It can be obtained by passing sulphur dioxide through the solution of mercuric chloride.
2HgCl 2 2H 2 O SO 2 Hg 2Cl 2 H 2SO 4 2HCl

Properties :
(i) It is an amorphous, tasteless, odourless white powder. It is sparingly soluble in water. It
is non-poisonous.
(ii) Onheating, it decomposes into mercuric chloride and mercury.
Hg 2 Cl2 2HgCl2

(iii) It turns black when treated with ammonium


hydroxide. The black substance is a mixture
of mercury and mercuric amino chloride
Uses :
(i) As a purgative in medicine
(ii) For making calomel electrodes.

Hg2Cl 2 + 2NH4OH

Hg

NH 2
+Hg + NH 4Cl+2H 2O
Cl
Black

HgCl2

Mercury (II) Chloride or Mercuric Chloride, Corrosive Sublimate,

(i) it may be prepared by heating mercury in a current of chlorine.


(ii) It is commercially prepared by heating mercuric sulphate with an equal quantity of sodium
chloride in the presence of a litte manganese dioxide.
Properties.
(i) It is a colourless, crystalline substance, which gives a 5.8% solution in water at ordinary
temperature. It is covalent compound an does not give the usual reactions of the chloride
ion.
(ii) It is dangerous poison.

Hg 2Cl2
(iii) With stannous chloride, it gives a white precipitate of mercurous chloride
finally reduced to metallic mercury (grey).

which is

(iii) With potassium iodide, it gives a scarlet precipitate soluble in excess of potassium
iodide forming Nesslers solution.

HgI 2 2 KI K 2 HgI 4
(iv)

Nesslers solution is used test ammonium ion as following


NH +4 +2[HgI 4 ]2- +4OH - HgO.Hg(NH 2 )I +7I - +3H 2O

In the above reaction

HgO.Hg(NH 2 )I

is called iodide of millons base

Uses.
(i) It is violent poison, the fatal dose being 0.2-0.5g. A 0.1% solution of mercuric chloride is
used as antiseptic for sterilizing bands and instruments of surgery.
(ii) It is also used as apreservative for wood and hides.
(iii) Mercuric chloride also finds use in the preparation of dry cells.
Potassium dichromate

K 2Cr2 O 7

Potassium dichromate is a very important chemical used in leather industry and as an


oxidant for preparation of many azo compounds. Dichromates are generally prepared from

FeCr2 O4
chromate, which in turn are obtained by the fusion of chromite ore
with sodium
or potassium carbonate in free access of air. The reaction with sodium carbonate occurs as
follows :

4FeCr2 O 4 8Na 2CO3 7O 2 8Na 2 CrO 4 2Fe 2O 3 8CO 2

The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give
Na 2 Cr2 O7 .2H 2O

a solution from which orange sodium dichromate,

can be crystallised.

2Na 2 CrO 4 2H Na 2Cr2O 7 2Na H 2 O

Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with potassium chloride.
Na 2 Cr2 O7 2KCl K 2 Cr2 O7 2NaCl

Orange crystals of potassium dichromate crystallise out. The chromates and


dichromates are interconvertible in aqueous solution depending upon pH of the solution.
The oxidation state of chromium in chromate and dichromate is the same.
2CrO 24 2H Cr2O 72 H 2 O

Cr2 O 72 2OH 2CrO 42 H 2 O


CrO 24

The structures of chromate ion.

are shown in the figure.

Sodium and potassium dichromates are


strong oxidising agents. Potassium dichromate
is used as a primary standard in volumetric
analysis. In acidic solution, its oxidising action
can be represented as follows :
Cr2 O 27 14H 6e 2Cr 3 7H 2O(E 1.33V)

Potassium permanganate

Cr

KMnO4

2O

and the

Cr2O 72

dichromate ion,

2-

O
O

Chromate ion

Cr

O
O

Cr

Dichromate ion

MnO 2

Potassium permanganate is prepared by fusion of

with an alkali metal hydroxide and

KNO3

K 2 MnO4

an oxidising agent like


. This produces the dark green
disproportionates in a neutral or acidic solution to give permanganate.

which

2MnO2 4KOH O 2 2K 2 MnO4 2H 2 O

3MnO 24 4H 2MnO 4 MnO 2 2H 2O


MnO 2

Commercially it is prepared by the alkaline oxidative fusion of


electrolytic oxidation of manganate (VI).
Fusedwith KOH. oxidised
with air or KNO3

Electrolytic oxidation in

alkaline solution
MnO24

MnO4
Manganate ion
permanganate ion

MnO 42 ;
Manganateion

MnO 2

It has two physical properties of


considerable interest : its intense colour
and its weak temperature dependent
paramagnetism.

are given below :


1.

Mn

Mn

O
O

Tetrahedral
manganate
(green) ion

Tetrahedral
permanganate
(purple) ion

In acid solutions :

(a) Iodine is liberated from potassium iodide :


10I 2MnO 4 16H 2Mn 2 8H 2 O 5I 2

(b)

Fe 2

Fe 3

ion (green) is converted to


2

5Fe MnO 8H Mn

A few important oxidising reactions of


KMnO4

followed by the

(yellow) :
4H 2O 5Fe3

(c) Oxalate ion or oxalic acid is oxidised at 333 K :


5C 2 O 42 2MnO 4 16H 2Mn 2 8H 2 O 10CO 2

(d) Hydrogen sulphide is oxidised , sulphur being precipitated :


H 2S 2H S2
5S2 2MnO 4 16H 2Mn 2 8H 2 O 5S

(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid :

5SO32 2MnO 4 6H 2Mn 2 3H 2 O 5SO 42

(f) Nitrite is oxidised to nitrate :


5NO 2 2MnO 4 6H 2Mn 2 5NO 3 3H 2O

2.

In neutral or faintly alkaline solutions.


(a) A notable reaction is the oxidation of iodide to iodate :
2MnO 4 H 2 O I 2MnO 2 2OH IO3

(b) Thiosulphate is oxidised almost quantitatively to sulphate :


8MnO 4 3S2O32 H 2 O 8MnO 2 6SO 24 2OH
MnO2

(c) Manganous salt is oxidised to


catalyses the oxidation :

; the presence of zinc sulphate or zinc oxide

2MnO 4 3Mn 2 2H 2O 5MnO 2 4H

Besides its use in analytical chemistry, potassium permanganate is used as a


favourite oxidant in preparative organic chemistry. Its uses for the bleaching of wool,
cotton, silk and other textile fibres and for the decolourisation of oils are also dependent
on its strong oxidising power.

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