[GROUP 14] - CARBON FAMILY SHIVALIK TUTORIALS

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Electronic configuration: General configuration is ns2 np2 i.e., one electron more than the corresponding members of Boron
family present in the same period.

Elements Atomic Number Electronic Configuration

2
Carbon [C] 6 2, 4 [He] 2s 2p 2

Silicon [ Si] 14 2, 8, 4 [Ne ] 3s sp 2

2

Germanium [ Ge ] 32 2, 8, 18, 4 [Ar ] 3d 10 4s 2 4p 2

Tin [ Sn] 50 2, 8, 18, 18, 4 [Kr] 4d 10 5s 2 sp 2

Lead [ Pb ] 82 2, 8, 18, 32, 18, 4 [Xe ] 4p 14 5d 10 6s 2 6p 2

Physical properties of carbon family:

(1) Atomic & Ionic Radii:- Atomic Radii of elements of carbon family are less than elements of group 13 due to greater
effective nuclear charge and on moving downward atomic size increases due to increase in no. of shells & increase of
shielding effect. The increase in atomic radii from silicon onwards is less due to poor shielding of d and f electrons
as compared to s and p electrons.
(2) Ionisation enthalpies:- Higher than those of elements of group 13 due to decrease of atomic size and increase in effective
nuclear charge. On moving downward due to increase in atomic size it goes on decreasing.
Exception:- The ionisation enthalpy of lead is expected to be less than that of tin but it is slightly more. It is due to poor
shielding effect of intervening 4‘f’ electrons in case of lead as a result it has more effective nuclear charge & high ionisation
enthalpies.
(3) Electropositive or Metallic characters:- The electropositive character is less than that of group 13 elements due
to small size and higher ionisation enthalpies. On moving downward, electropositive and metallic chraracter goes on
increasing due to increase of atomic size and decrease of ionisation enthalpy. For example carbon is non metal, silicon in
non metal, germanium is a metalloid and tin and lead are metallic in nature.
(4) Electronegativity goes on decreasing from top to bottom.
(5) Density goes on increasing from top to downward due to increase of atomic mass.
(6) Melting and boiling points:- Higher than those of elements of group 13 due to increase in nuclear charge, smaller size,
greater no. of electrons (four) available for bond formation and greater interatomic force of attraction. On moving down
the group, the Mpt and B-pt decreases due to increase of atomic size.
(7) Catenation:- Self linking of the elements or atoms mutually to form long chain of covalent bonds is called catenation
Carbon has maximum power of catenation. The catenation power depends upon element-element bond strength and size
of atom. On moving down the group bond strength keeps on decreasing and catenation tendency decrease.
C > Si > Ge > Sn > Pb. Size of carbon is very small and as a result C - C bond is quite strong.
(8) Allotropy:- All members except Pb show allotropy i.e., some members exist in more than one forms having diff. physical
properties & some chemical properties.
Carbons: Allotropic form of C are
Carbon

Crystalline Amorphous
(a) (b)
Diamond Graphite Fullerene Coke Charcoal Lamp black

Diamond: In diamond C-atom is in sp3 hybridization. Each C atom is linked to 4 carbon atom. Thus diamond has
3 dimensional network of strong covalent C-C bond length is 154 pm. [see fig (b)]
Properties:- (1) Purity:- Diamond is the purest form of carbon.
(2) Bond length:- Due to sp3 hybridisation C-C bond length is 154pm or 1.54 A0.
(3) Hardness:- Because it exists as a three dimensional network, dense packing, it is hardest substance known with
high density and high M.pt.
(4) Conductivity:- Since all electron are held up in C-C  bonds, there are no free electrons to move as such it is a
bad conductor of electricity.
(5) Transparency:- Because of its high refractive index (2.5) diamond can reflect and refract light. It is therefore,
a transparent substance.
Uses:- (1) Because of its hardness, diamond is used for cutting glass, making pores for rock drilling and for making abrasive.
(cleaning by rubbing)
(2) It is used for grinding and polishing of hard material.
(3) When diamond is cut and polished brilliant light is refracted from its surfaces. That is why diamond is useful for making
precious gems and jewellary.
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(4) Used for making dyes for drawing thin wires from metals.
Graphite:- In graphite, it occurs in nature and can be manufactured artificially by heating coke to 3273-3300K in an
electric furnance.
Structure:- In graphite, Carbon is sp2 hybridised and form hexagonal rings. It has two dimensional sheet (layered) structure
consisting of a no. of benzene rings further fused together. The various sheets are held together by weak Vander Waal forces
of attraction

340 pm

142 pm

Properties:- (1) Purity:- Like diamond, it is also the purest form of carbon.
(2) Softness:- Due to weak forces of attraction between the successive layers, one layer can slip over the other, as such it
is soft & and good lubricating agent.
(3) Conductivity:- Because three electrodes of each carbons are used in making hexagonal rings in graphite, fourth valence
electron of each carbons is free to more. This makes graphite a good conductor of heat & electricity.
(4) Opaquencess:- Graphite is a black substance and possess a metallic lusture.
Uses:- (1) It is used as a reducing agent in steel manufacutre. (2) It is used in high strength composite material.
(3) Used for making electrodes for dry cells.
(4) Graphite markes paper and is therefore called black lead. Mixed with desired quantity of wax or clay, graphite is used
for making cores of lead pencils. (5) Used in manufacuter of crucibles which can withstand high temp.
(6) Used as a moderator for fast moving neutrons in atomic reactors. (7) Used as a solid lubricant for heavy machinery.
FULLERENES:- These are cage like spheroidal molecules having molecular formula. C60 and C70 is called Robert
Buck-minister fullerness. (Similarity with Geodesic Domes build by American Architect). Other allotrophic forms of silicon
are crystalline and amorphous. Germanium are crystalline and amorphous. Tin are grey, white and rhombic.
(9) p  - p  - multiple bondings and d  -d  bonding:

SiH3
H3 Si
N
N
CH 3
H3 C

C H3
SiH3
P yra m id al Planer
(Tri met hyl ami ne ) (Trisilicylamine)

Carbon due to its small size can form p  -p  multiple bonds with C, O, N and S etc. C = C, C  C, C = O, C  N etc. due
to side wise overlapping of 2p-orbitals. While other atoms due to larger size than carbon can not from p  -p  multiple
bonds. Due to this reason, silicon can not form graphite like structure. Other elements can form p  -d  multiple bond. Fo
example, trimethyl amine is pyramidal white trisilyl amine is planar. In trimethylamine N is sp3 hybridised and fourth
sp3 hybridised orbital contains a lone pair of electron. In trisilyl amine, N is sp2 hybridised and the unhybridised p-orbital
containing a pair of electrons forms a  bond with the vacant d-orbital of silicon. This is called p  -d  bond.

Si + N Si

Vacant d orbital Filled d  p  orbital

p-orbital

Trimethyl amine is more basic due to presence of lone pair of electrons as compared to trisilylamine in which N does not
have a lone pair of a electron.
CHEMICAL PROPERTIES OF CARBON FAMILY: (1) Nature of compounds:- All elements of carbon family have
four valance electrons & it is difficult to lose or gain four electrons and thus can not from ionic compounds. Thus compounds
of carbon family are covalent in nature. Compounds of first elements carbon are of covalent nature except certain carbides
like CaC2, SiC & Al4C3 which are ionic. Similarly silicon and other elements show tetravalency as well as oxidation state of
+2 in their compounds.
Some important points are: (a) On moving down the family, tendency to show +4 oxidation state decreases while
+2 oxdn state increases. This is due to inert pair effect. s-electrons due to their greater penetration into the nucleus are
reluctant to participate in the bond formation where as p-electrons are easily available. The inert pair effect is more dominant
in tin and lead due to greater nuclear charge as a result of very high atomic no. As a result, both of them normally show
+2 oxdn state i.e., Sn+2 and Pb+4 ions. However, if sufficient energy is available, the valence electron also become available
to form +4 oxdn state. Sn = 50 2, 8, 18, 18, 5s2 sp2
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2, 8 , 18, 18 5s 2 oxdn state =+2

Sn+2 =
Inert pair

By supplying more energy ‘s’ electrons are also lost and oxdn state will be +4. Thus it is concluded that:
(i) SnCl2 and PbCl2 are more easily formed as compared to SnCl4 and PbCl4.
(ii) PbCl2 is more stable than SnCl2 due to greater magnitude of inert pair effect.
(b) Compounds with +4 oxidation state are generally covalent while those with +2 oxidation state are ionic: This is
because in +4 oxidation state, the ionic size is very small and nuclear charge is very high. As a result, polarising power of
the cation is very large & thus form covalent compounds. And in case of cation with +2 oxidation state, having bigger size
and less positive charge has low polarising power and form ionic compounds. Thus SnCl2 is an ionic solid and SnCl4 is a
covalent liquid at room temp.
(c) Maximum covalency (formation of complexes):- Since carbon does not have any 2 ‘d’ orbitals, it can show a maximum
covalency of four in its compounds. Thus, all the compounds of carbon are tetravalent. Silicon and other heavier members of
the family can show a higher covalency of six due to the availability of vacant d-orbitals which can accepts electron pairs
from the electrons donor species (i.e., anions). Thus,all of them can form complexes like [SiF6]2-, [GeF6]2-, [PbCl6]2- etc.
(2) Formation of Hydrides:- All members of cabon family combine directly or indirectly with hydrogen to form covalent
hydrides. (i) Carbon form hydrides called hydrocarbons alkanes, alkenes & alkynes.
(ii) Si and Ge form hydrides having formule SnH2n+2 (n = 1 to 8) and are called silanes having similar properties to alkanes.
(iii) Tin forms two hydrides called stannane (SnH4) and distance (Sn2H6) while lead forms plumbane PbH2 & not PbH4.
Properties of hydrides:- (a) Are covalent in nature.
(b) Act as reducing agent and their reducing strength goes on increasing moving down the group. Because M-H bond strength
decreases due to increase in size of M.
(c) Thermal stability of hydride decreases down the group.
(3) Formation of Halides:- Members of carbon family form tetrahalides MX4 (except PbBr,. and PbI4) covalent in nature
having tetrahedral shape. Non existence of PbBr4 and PbI4 is due to the fact that both Br- and I- ions are strong reducing
agents and they reduce Pb4+ to Pb+2 only PbBr2 & PbI2 are formed.
Note and Question:- CCl4 is not hydrolyzed by water while remaining halides like SiCl4 is easily hydrolysed.
CCl4 + H2O  No action SiCl4 + 4H2O  Si(OH)4 + 4HCl
This is because carbon has no d-orbital and cannot expand its co-ordination no. beyond 4 while silicon has got vacant ‘d’
orbital
& can expand its C.N. beyond 4.
Mechanism of hydrolysis:- Step-1: Lone electron pair on oxygen of water molecule is donated to the vacant d-orbital
of silicon in SiCl4 to form an addition compounds.
Cl OH
Cl Cl Cl Cl
.. H I H II Si
Si + :O Si O
H -HCl Cl
H Cl Cl
Cl Cl Cl

StepII: The addition compound loses a molecule of HCl and ,thus a Cl atom attached to silicon gets replaced by OH group.
The process gets repeated till all the four Cl atoms get replaced by OH groups to from siliicon tetrahydroxide or hydrated
siliconic acid. Carbon tetrachloride cannot be hydrolysed because carbon atom has no vacant d-orbitals to accepts electron
pairs from the H2O molecules.
Note:- (a) Except C and silicon Ge, Sn and Pb also form dihalides like SnCl2 and PbCl2. SnCl is a very good reducing agent
and reduces ferric salt to ferrous salt. 2FeCl3 + SnCl2  2FeCl2 + SnCl4
(b) CCl4 does not form hexahalides like CCl 26  while SiCl4 & GeCl4 from hexa halides like SiCl 2
6
and GeCl 2
6
because
carbon does not have vacant d-orbital.
(4) Formation of Oxides:- Elements of carbon family form two types of oxides, which can be monoxides and dioxides.
(a) Monoxides:- With the exception of silicon, other elements form monoxides like CO, GeO, SnO & PbO. CO is neutral
oxides and other oxides are basic Carbon monoxides is highly poisonous in nature.
Structure of CO: Hybrid of following structure:

- + -
: :

+    
:

: C :: O : : C : : :O : :C : O: or C O C O C O

Because the octet of carbon is not complete in its uncharged structure, it behaves as an unsaturated oxide and forms
addition compound with hydrogen (CH3OH), Chlorine (COCl2) and sulphur (COS) etc. It also forms addition compounds
called carbonyls with certain transition metals like Ni, Fe, Cr etc. having the formula Ni(CO)4 Tetracarbonyl nickel(O),
Fe(CO)5 Pentacarbonyl Iron (O) and Cr(CO)6 hexacarbonyl chromium (O).
Dioxides:- All the members form dioxides which are CO2, SiO2, GeO2, SnO2 and PbO2, CO2 is gas and reamining oxides
are crystalline solids having very high melting points.
Structure of CO2:- It is linear molecule having structure (O = C = O) in which carbon atom is linked to two oxygen atoms by
double bonds. Carbon-oxygen bond length should be 122 pm.But experimentally the bond length is found to be 115 pm.
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Therefore CO2 molecule is involved in resonance and is hybrid of following contributing structure.
-
+ + -    

: :
:
:

: :
: O :: C : : O : : O: C ::: O: :C ::: C :O: or  C C O  C O C C O
SiO2 is solid because silicon dioxide is a network solid in which each silicon atom is linked tetrahedrally to four oxygen atoms
by covalent bonds forming three dimensional network.
Explanation of the difference of structure of CO2(gas) SiO2(solid):

O O O

- O - Si – O – Si – O – Si -

O O O

- O - Si – O – Si – O – Si -

O O O

In CO2, the carbon atom is linked to oxygen atom by double bonds due to sidewise overlapping of 2p orbitals of carbon and
oxygen which have nearly same energy. Thus CO2 exists as discrete or individual molecule experiencing weak Vander Waal’s
force of atraction in them. But Si = O bonds are not possible because sidewise overlap can not take place between
3p orbital of silicon and 2p orbital of carbon due to difference in their energies. The two atoms can be linked by single bonds
forming a Giant network structure resulting in a solid.
SILICATES : These are solids containing Si - O bonds and high percentages of silicate minerals occurs in earth crusts like
Mica, clay, quartz etc.: Glass cement, bricks, tiles, porcelain etc. are all made from silicates. X-ray studies have shown that
the basic structural unit in all these silicates is the (SiO4)4- tetrahedran which is represented as
O- _

Represents oxygen

Si O- . Represents silicon

._
O- O- _ _

These SiO 4
4
tetrahedral units can occur singly or in groups sharing one oxygen atom but never by sharing edges or faces.
Depending upon number of tetrahedral units and their linkage, the silicates are classified into folowing types.
(1) Simple or orthosilicates:- These silicates have discrete (SiCl4)2- tetrahedrale.g., Zircon (ZrbiO4) &phenacite (Be2 SiO4).
(2) Pyrosilicates or Island:- One O-atom is shared between two SiO 4
4
tetrahedrons.e.g; thortvetite. Sc2Si2O7.
_ _
_ _
O O
_ _
_
.

[Si2O7.]2-
.

Si O
Si
O _
_
_ _ _ O
O O

(3) Ring or cyclic silicate:- Two O-atoms per tetrahedrals are shared having general formule of the structure or SiO 3 b g 2 n
n

_
_

_
_ . _
_
. . _ . _

_
. . _ . ._
_ _ [Si3O9.]6- _ _ _ [Si6O18]12-
. _

Examples are Wollastonite Ca3Si3O9 and Beryl Be3Al2Si6O18

(4) Chain silicate:- These are of two types single chain silicates and double chain silicates. In single chain, silicate each
tetrahedron can share two oxygen atoms having general formulae SiO 3 b g . Example are spodumene LiAl(SiO )
2 n
n 3 2

and diopside CaMg(SiO3)2.

_ _ _

_ _ _
. . .
_. _.

_ _

(Anion in single silicate chain)

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In double chain silicates, the two chains are cross-linked, forming double stranded silicates having the formula [(Si4O11)6-]n
and are called Amphiboles. Here -OH is not a part of silicate frame work. Example of this class is ASBESTOS.

_ _

.
_
. _

. _ . _ . _

. _
. _
._
. _ . _

_ _
Double silicate [(Si4O11)6- chain
(5) Sheet silicate:- The sharing of three corners i.e,. three oxygen of each tetrahedron results in an infinite two dimensional
sheet structure of the formula Si 2 O 2
5 c han shown. Example: Clay
n

. _
.
_

. _ . _ . _

. . .
. _
. _ . _ . _

. _
. _
. _
. _

. . .

(6) Three dimensional silicates:- If all the four corners i.e., all the four oxygen atoms are shareed with other tetrahedral
three dimensional network structure is obtained.
Example:- Different forms of silica such as quartz, tridymite and cristobalite. If in this three-dimensional network, part of
silicon is replaced by Al3+, this will require in corporation of other cations (Na+, K+or Ca3+) for maintaining the charge
balance. Such a three-dimensional aluminosilicates are called Feldspar and Zeolites.
Silicones: These are the synthetic organosilicon polymers containing Si-O-Si linkages having general formula (R2 SiO)n.
R can be alkyl (methyl or ethyl) or phenyl groups. Because the general formula is similar to ketone R2CO, the name silicone
has been given to these polymers.
Preparation and structure of silicons:- Silicons are of two types. Linear or cross linked in nature and are formed by the
action of SiCl4 on Grignard reagents followed by hydrolysis leading to polymerisation.
RMgCl  SiCl 4  RSiCl 3  MgCl 2 2 RMgCl  SiCl 4  R 2 SiCl 2  2 MgCl 2 R  CH 3 ,  C 2 H 5 or  C 6 H 5
Trichloro silane Dichlorosilane

a) Linear Silicons are formed by the hydrolysis of dichlorosilicans followed by polymerisation

R R R R R R
Polymer-
+2H 2 O isation
Cl Si Cl OH Si OH + OH Si OH + Third O Si O Si O
Cl Si O
-2HCl
molecule

R R R R R R

Linear Silicones

(b) Cross-linked Silicones are formed by the hydrolysis of trichlorosilicones followed by hydrolysis.
[He] 2s
R R Elements
R

O Si O Si O
Cl Si O
R R R
Polymer-
-3HCl isation
Cl Si Cl + 3H 2 O HO Si OH + HO Si OH O O O

O Si O Si C Si O
Cl OH OH

R R R

Cross-linked Silicones

Properties:- (1) Silicones containing small chains are oily liquids, with medium chains are viscous and greasy and with very
long chains are waxy and rubber like solids.
(2) They are water repellent and heat resistant and have good electrical insulating properties.
(3) They are chemically inert i.e., resistant to oxidation, thermal decomposition or to attack by organic reagents.
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Use of silicons:- (1) For making water proof papers, wool, textiles, wood etc. by coating them with a thin film of silicone.
(2) As sealants and electrical insulators. (3) As lubricants at high as well as at low temperature because there is little change
in viscosities with temp. (4) As antifoaming agents in cosmetics.
ANAMALOUS BEHAVIOUR OF CARBON: Carbon the first memeber differs from rest of the elements in many
properties due to (1) Small atomic size (2) High ionisation enthalpy and electronegativity
(3) Absence of vacant d-orbital in the valance shell (4) tendency to form multiple bonds.
The anomalous behaviour is supported by following properties:
(1) CO2 is a gas and SiO2 and other similar oxides of other elements are solids.
(2) Carbon has maximum power of catenation other have very small
(3) CCl4 is not hydrolysed, other tetrahalides like SiCl4 are hydrolysed.
(4) Carbon can form multiple bonds with carbon, oxygen and nitrogen while this tendency to form multiple bonds is less in
other members.
(5) CO2 dissolves in H2O to form H2CO3 other oxides like SiO2 is insoluble in H2O.
(6) Carbon shows maximum covalency of four and does not take part in complex formation, while remaining members
can exhibit higher covalency of six and can take part is complex formation.
TIN: Occurence: It does not occur in native state. Its chief ore is cassiterite or tin stone, SnO2.
Extraction involves following steps:-
(1) Concentration:- After crushing the ore is washed with H2O to remove sand and mud. Heavier ore particles settle down.
Magnetic impurity FeWO4 wolframite i.e., Iron tungestate is removed by magnetic separation.
(2) Roasting:- Ore is heated with excess of air to remove As and sulphur as their volatile oxides.
4As + 3O2  2As2O3 and S + O2  SO2
(3) Smelting:- Roasted ore is mixed with coke & heated in a furnance. Tin oxide is reduced to the metallic state.
SnO2 + 2C  Sn + 2CO
A little of lime is added to act as flux to remove SiO2 if still present CaO + SiO2  CaSiO3 (slag)
Molten tin is taken out and cast into blocks called block tin.
(4) Refining:- The obtained contains impurities like Fe, Pb, Cu etc.is purified by following methods.
(i) Liquation:- The impure metal is heated on the hearth of a reverberatory furnance. Low melting tin (m.p. 505K) flows down
the hearth & high melting impurities remain sticking to it.
(2) Poling:- The molten metal taken in a big container is stirred with green poles of wood. As a result, the impurities rise to
the surface and get oxidised to form a scum which can be removed.
(3) Electro-refining:- The impure metal is made anode and sheet of pure tin acts as the cathode. The electrolyte is solution of
stranous sulphate (SnSO4) containing small amount of hydro-flurosilic acid(H2SiF6) andconc. H2SO4. On passing current,
pure tin from the anode goes into the solution and an equivalent amount of the metal from the solution gets deposited on
the cathode.
Pysical porperties of Tin:- (1) Soft silvery while metal. (2) Ductile, can be rolled into thin sheets called tin foils.
(3) Tin occurs in three allotrophic forms. Grey white and rhomobic tin.
(4) When a rod made from the metal is bent, it produces a cracking sound human as tin cry due to the crystals rubbing
against each other.
USES:- (1) Electroplating of iron to resist corrosion.(2) Tining the utensils.
(3) The foils are used in making food containers.
Compounds of Tin: Stannous oxide or Tin(II) oxide (SnO): Prep:- Prepared by heating stannous oxalate in an
inert atomsphere. SnC 2 O 4  SnO  CO  CO 2 Carbon monoxide produced prevent the oxidation of SnO to SnO2.
Properties:- (1) It is greyish black solid & burns in air forming tin (IV) oxide: 2SnO + O2  2SnO2
(2) It is amphoteric in nature and reacts both wth acids and alkalies. SnO + H2SO4  SnSO4 + H2O
SnO  2 NaOH  Na 2 SnO 2  H 2 O
Sovb . s tan nite

Tin IV oxide or stannic oxide (SnO2):- It occurs in nature of cassiterite or tinstone.

Prep:- (1) By heating tin in air (Lab method): Sn  O 2 Heat
 SnO 2
(2) By heating tin with conc. HNO3 The insoluble meta stannic acid formed is filtered and heated to give stannic oxide.
b g
Sn  4 HNO 3 conc.  H 2SnO 3  4 NO 2  H 2 O
Metal stammic acid
H 2SnO 3 Heat
 SnO 2  H 2 O
Properties:- (1) While solid insoluble in water. (2) Amphoteric in nature and reacts both with acids and bases.

b g
SnO 2  2 H 2 SO 4 conc.  
 Sn SO 4 Heat
b g 2H O
2 2
SnO 2  2 NaOH Fure
 Na 2 SnO 3  H 2 O
Sodium s tan nate

USES:- (1) In making white enamals, tiles, glazes and glass. (2) Constituent of the polishing powder.
(3) Tin (II) flouride or stannous flouride(SnF2): Prep:- By dissolving tin (II) oxide (SnO) in hydroflouric acid HF
SnO + 2HF  SnF2 + H2O
Properties:- White crystalline solid soluble in water. Uses:- It is an ingredient (part )of tooth pastes to check dental decay.
(4) Tin (II) chloride or stannous chloride (SnCl2):
Prep:By dissolving tin in conc. HCl on concentration and cooling hydrated SnCl2. 2H2O is formed. Sn + 2HCl  SnCl2 + H2
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Anhydrous SnCl2 is prepared by heating tin in a current of dry HCl gas
Sn + 2HCl  SnCl2 + H2
Properties:- (1) White crytalline solid, soluble in H2O.
(2) Strong reducing agent and its solution in HCl reduces mercuric chloride firstly to mercurous chloride and then to
mercury which is formed as a block ppt.
SnCl2 + 2HgCl2  SnCl4 + Hg2Cl2 SnCl2 + Hg2Cl2  SnCl4 + 2FeCl2
It is also reduces ferric salts to ferrous salts. SnCl2 + 2FeCl3  SnCl4 +2FeCl2
Uses:- (1) As a mordant in dying [mordant is substance that fixes dyes] (2) As a reducing agent in laboratory.
(5) Stannic chloride or Tin (IV) chloride (SnCl4) : Prep:- (1) By passing Cl2 over molten tin. Sn + 2Cl2  SnCl4
(2) By passing dry Cl2 over SnCl2. SnCl2 + Cl2  SnCl4
Properties:- (1) Colourless liquid and fumes in moist air due to formation of HCl vapours formed as a result of hydrolysis.
SnCl4 + 2H2O  SnO4 + 2HCl
(2) It is hydgroscopic in nature and forms a crystalline pentahydrate etc Salt SnCl2.5H2O by absorbing a small amount of
water vapour. The hydrated salt is called butter of tin.
(3) It dissolves in organic solvents like CCl4 which suggests that the compound is covalent in nature.

(4) Dissolve is excess of conc. HCl to form hexachlorostannic acid. SnCl 4  2 HCl  Hexachloro
H 2 SnCl 6
s tan nic acid

Uses:- (1) Stannic chloride is used as a catalyst in organic reactions. (2) Used in the preparation of fire proof cotton.
(3) Ammonium hexastannite (NH4)2SnCl4 is used as a mordant in dying.
Lead: Being a reactive metal does not exist in free state. The important ores are
(1) Galena PbS (2) Anglesite PbSO4 (3) Cerrusite PbCO3.
Extracton of lead from galena:- Following steps are involved:
(1) Concentration:- The ore is crushed, powdered and is then concentrated by froth floatation process.
(2) Roasting:- Ore is heated in the presence of air partial oxdn occur.
2 PbS( s)  3O 2 ( g)  2 PbO  2SO 2 PbS  2O 2  PbSO 4
3. Reduction: It can be done in two ways: (a) Self reduction: Supply of air is cut off and more galena is added. Temp
is raised. Galena reduces both the oxides and sulphates to mettalic lead.
2 PbO  PbS  3Pb  SO 2 PbSO 4  PbS  2 Pb  2SO 2
Molten lead is taken out from the bottom of furnace.
b) Carbon reduction: Roasted ore is heated with coke and lime stone in a blast furnace. Lead oxide is reduced to lead.
PbO  C Heat  Pb  CO Lime stone CaCO3 supplies calcium oxide (lime) which removes the impurity of

silica as calcium silicate (slag) CaO  SiO 2  CaSiO 3
c) Refining: Can be done by electrorefining using an electrolyte which is a mixture of lead flourosilicates (PbSiF6)
and hydroflourosilic acid (H2SiF6). Sulphuric acid can not be used because PbSO4 formed is insoluble in water.
Physical properties: (1) Soft metal having bluish grey colour. 2. Malleable but not ductile. 3. Poor conductor of electricity.
Heat
Chemical properties: Action with air: On heating litharge PbO and red lead Pb3O4 are formed. 2 Pb  O 2  
 2 PbO
lith arg e ( yellow )

6 PbO  O 2 Heat
 / temp
 2 Pb 3 O 4
read lead

2. Action of water: Pure water has no action on lead but is corroded by water containing dissolved air due to formation
of Pb(OH)4 which is soluble in water. 2 Pb  2 H 2 O  O 2  2 Pb( OH ) 2
The degree of solubility of lead in water is called PLUMBOSO Valency. The presence of lead in drinking water is
extremly harmful. Therefore lead pipes are no longer used for carrying drinking water.
2. Action with acids: Pb  2 HCl( conc)  PbCl 2  H 2
Pb  2 H 2 SO 4 ( conc)  PbSO 4  SO 2  2 H 2 O Dil HCl and dil H2SO4 donot have any action with lead.
Dilute HNO3 gives nitric oxide and conc. HNO3 give NO2 gas with lead.
3Pb  8 HNO 3 ( dil )  3Pb( NO 3 ) 2  2 NO  4 H 2 O 3Pb  4 HNO 3 ( conc)  3Pb( NO 3 ) 2  2 NO 2  2 H 2 O
Lead dissolve in acetic acid in the presence of oxygen to form lead acetate.
2 Pb  2CH 3 COOH  1 2 O 2  (CH 3 COO) 2 Pb  H 2 O
lead acetate

Action with alkalis: Pb  2 NaOH  Na 2 PbO 2  H 2

Uses of lead: 1. In making storage batteries. 2. Certain compounds of lead like white lead, chrome lead, and chrome yellow
are used as pigments in paints. 3. Used in preparation of tetraethyl lead (T.E.L) which reduces knocking in petrol
4. Used in manufacturing of ammunition like bullets, shots etc. 5. Used in equipment for protection against radioactive rays
(  , ,  ) and X rays. 6. Used for making alloys like bell metal (Pb + Cu + Sn) & type metal (Pb + Sb + Sn)

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Compounds of lead: 1. Plumbous oxide or lead (II) or litharge (PbO):
Prep: (1). 2 Pb  O 2 1150
 K
 2 PbO Firsty on heating lead with oxygen form yellow powder at 573K called Massicot
and then on further heating PbO is formed.
2. Lab Method: 2 Pb( NO 3 ) 2 heat
 2 PbO  4 NO 2  O 2 and PbCO 3 heat  2 PbO  CO 2
Properties: 1. Yellow powder on heating changes to red. 2. Amphoteric in nature and reacts with both acids and bases.
PbO  2 HCl  PbCl 2  H 2 O PbO  2 NaOH  Na 2 PbO 2  H 2 O
3. It is reduced by H2 , C and CO to form Pb on heating.
PbO  H 2  Pb  H 2 O ; PbO  C  Pb  CO ; PbO  CO  Pb  CO 2
Uses: 1. In glazing pottery 2. Paints and varnishes. 3. in flint glass. 4. A mixture of massicot with glycerine is used for
joining broken piece of glass and stones.
II: Lead IV oxides, lead dioxides or plumbic oxide (PbO2):
Prep: 1. By warming red lead with dil HNO3: Pb 3 O 4  4 HNO 3  2 Pb ( NO 3 ) 2  PbO 2  2 H 2 O
2.. Lab method: By oxidation of lead acetate with bleaching powder in alkaline solution:
( CH 3 COO ) 2 Pb  Ca ( OH ) 2  Pb( OH ) 2  ( CH 3 COO ) 2 Ca Pb ( OH ) 2  CaOCl 2  PbO 2  CaCl 2  H 2 O
Properties: Chocolate brown powder insoluble in water. Action of heat : 2 PbO 2 573 K
 2 PbO  O 2
3.Action as oxidising agent: It oxidises HCl to Cl2, S to SO2, and H2SO4 to O2.
PbO2 + 4HCl  PbCl2 +Cl2 +2H2O. PbO2 + 2S  PbS + SO2 2PbO2 + 2H2SO4  2PbSO4 +O2 +2H2O
4. Amphoteric nature: React both with acids and bases.
PbO2 + 4HCl  PbCl2 + 2H2O PbO2 + 2NaOH  Na2PbO2 + H2O
Uses: 1. storage batteries. 2. Oxidising agent 3. Match industries.
III: Red Lead or trilead tetra oxide Pb3O4 (sindhur): Prep: by heating lead(II) oxide in excess of air at 750K.
6 PbO  O 2 750
 K
 2 Pb 3 O 4
Prop: Brilliant red powder insoluble in water. 2. Action of heat : 2 Pb 3 O 4  O 2 773
 K
 6PbO  O 2
3. As an oxidising agent: 2 Pb 3 O 4  8HCl 773
 K
 2 PbCl 2  4 H 2 O  Cl 2 A
2 Pb 3 O 4  6H 2 SO 4   773 K
 6PbSO 4  6H 2 O  O 2 A
With Conc HNO3: PbO 2 .2 PbO  4 HNO 3  2 Pb( NO 3 ) 2  PbO 2  2 H 2 O
Uses: Red protective paints for iron and steel structures. 2. Used in glass and metal industry 3. As an oxidising agent.
IV Lead (II) halides PbX2:
Prep: By adding aq. solution of a suitable halide to a soluble Pb(II) salt like lead nitrate.
Pb(NO3)2+ 2NaX  PbX2 + 2NaNO3 [X = F, Cl, Br, I]
Properties: (1) All halides except PbI2 are white crystalline solids. PbI2 is yellow.
2. All are sparingly soluble in cold water but quite soluble in hot water.
3. All dihalides are quite stable. This is supported by the fact that lead (IV) halides on heating decompose to form lead
(II) halides. For example: PbCl 4 heat
 PbCl 2  Cl 2
4. All the dihalides are somewhat ionic in character. Their ionic character decreases with the increase in size of halogen atom
i.e.PbF2 > PbCl2 > PbBr2 > PbI2
Uses: PbI2 (yellow ppt) and PbCl2 (white ppt) is used to detect Pb2+ in quantitative analysis.
V. Lead IV halide or lead tetrahalides (PbX4):
Amongst the tetrahalides of lead only PbF4 and PbCl4 are quite stable. PbBr4 and PbI4 donot exist due to insolubility of Br2
and I2 to oxides Pb(II) and Pb(IV)ion.
Prep: Lead tetrafluoride is prepared by the action of bromine triflouride (BrF3) on lead dioxide PbO2.
3PbO 2  4 BrF3  3PbF4  2 Br2  3O 2
2. Lead tetrachloride is prepared by dissolving lead dioxide in conc. HCl at 273K. PbO 2  4 HCl  PbCl 4  2 H 2 O
Properties: 1. PbF4 is a white solid while PbCl4 is a volatile liquid.
2. PbF4 is ionic solid and PbCl4 is a covalent liquid.
3. PbF4 is more stable than PbCl4 . PbCl4 on heating: PbCl 4  PbCl 2  Cl 2
4. PbF4 is not easily hydrolysed by water but PbCl4 is rapidly hydrolysed by water: PbCl 4  2 H 2 O  PbO 2  4 HCl
Pattuson’s white lead: PbCl2 on heating with lime water, Ca(OH)2 gives Pb(OH)Cl which is used as a white pigment called
Pattuson’s white lead. PbCl 2  Ca ( OH ) 2  Pb ( OH ) Cl  CaO  HCl
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