13th Group Elements (Boron Family)
Abundance :
# B is a rare element and mainly occurs as Boric Acid(H3BO3),
Borax(Na2B4O7.10H2O) and Kernite (Na2B4O7.4H2O).
# Al is the most abundant metal and third most abundant
element in earth crust after Oxygen & Silicon.
Ionization energy :
B > Tl > Ga > Al > In
Physical Properties
# B is an extremely hard and black colored solid and has
unusually high melting point(2092oC) due to formation of a
strong lattice.
# Ga has very low melting point of 303 K (30oC) but has high
B.P.(2676K) which makes it useful for measuring high
temperature.
Q. When borax is dissolved in water :
(A) B(OH)3 is formed only
(B) [B(OH)4]– is formed only
(C) both B(OH)3 and [B(OH)4]– are formed
(D) [B3O3(OH)4]– is formed only
Ans -C
Q. The borax bead is chemically :
(A) B2O3 (B) Na2B4O7 (C) Na3BO3 (D) B2O3 + NaBO2
Ans – D
Q. On the addition of mineral acid to an aqueous solution of
borax, the compound formed is:
(A) borodihydride (B) orthoboric acid
(C) metaboric acid (D) pyroboric acid
Q. The product obtained in the reaction of diborane with
excess of ammonia at low temperature is :
(A) B2H6. NH3 (B) B2H6. 2NH3 (C) (BN)x (D) Borazine
14th Group Elements (Carbon Family)
C Si Ge Sn Pb
2nd most abundant element
# C has the highest m.p. in the group
# I.E. decreases down the group but Pb has slightly greater
I.E. than Pb due to lanthanide contraction.
Chemical Properties
1. Oxidation States
# Common oxidation states +4 and +2 (Due to inert pair effect).
# C4+ ions does not exist in aq. Solution due to high value of
( IE1 + IE2 +IE3 + IE4 ) and due to high polarising power of C4+ ion
it can easily polarise the anion and thus the compounds are
predominantly covalent .
2. Reactivity Towards Oxygen
# All members of the group form monoxides(MO) and
dioxides(MO2) type.
# SiO only exist at high temperature where it is assumed to be
formed by the reduction of SiO2 with Si.
# Oxides in higher oxidation states are acidic CO2,SiO2 and GeO2
whereas oxides of Sn& Pb are amphoteric.
# CO is neutral and GeO is acidic.
3. Reactivity Towards water
# C,Si & Ge are not affected by water.
# On passing steam over red hot coke gives water gas
C(s) + H2O(g) CO(g) +H2(g)
# Same reaction is shown by Si & Ge
Si(s) + 2H2O(g) SiO2(g) + 2H2(g)
Sn(s) + 2H2O(g) SnO2(g) + 2H2(g)
# Pb is unaffected by water but in water containing dissolved air
it is appreciably soluble forming lead hydroxide , this
phenomenon is called pulmbosolvency.
2Pb + 2H2O + O2 2Pb(OH)2
Allotropes Of Carbon
# C atoms have tendency to link with other C atoms through
covalent bonds to form chains and rings , this property is called
catenation.
# The tendency to show catenation decreases on moving down
the group.
C >>Si > Ge ~Sn
# Due to property of C to show catenation and tendency to form
pp-pp multiple bond Carbon shows allotropy.
Crystalline Allotropes
1. Diamond
# It has crystalline lattice.
#
2. Graphite
# Graphite is composed of 2-D sheets of
hexagonal rings formed by c atoms.
# In graphite 3 valence electrons of each
carbon atom are involved forming s bonds
(using sp2 hybridised orbitals) and the fourth
electron forms p bond.
# The p electrons are delocalised over the
entire sheet.
# The hexagonal layers are held through weak Vander Waal forces
and can slide over each other and hence Graphite act as dry lubricant.
Graphite is thermodynamically more stable than diamond at room
temperature.
# Due to mobile electrons graphite conducts electricity along the layer
it donot consuct across the layer.
# Diamond is a better conductor of Heat than Graphite. In fact
diamond has the highest thermal conductivity of any substance
known.
3. Fullerene
# Fullerenes are made by the heating of graphite in an electric arc
in the presence of inert gases such as helium or argon, When
electric spark is generated a soot is produced which contains
mainly C60 with smaller quantity of C70 and traces of fullerenes
consisting of even number of carbon atoms up to 350 or above.
# Fullerenes are the only pure form of Carbon
# The C60 molecule has a shape like soccer ball and is called
Buckminster fullerene or bucky balls.
# It contains 20 hexagonal rings and 12 pentagonal rings.
# A hexagonal ring can fuse with both pentagonal and hexagonal
rings but a pentagonal ring can only fuse with hexagonal rings.
# All C atoms are sp2 hybridized in Fullerene.
# The remaining electron on each carbon is delocalized in
molecular orbitals giving aromatic character to the molecule.
Compounds Of Carbon
Carbon Monoxide(CO)
# It is a colourless odourless neutral poisonous gas formed by
incomplete combustion of carbon.
# In laboratory it is prepared by dehydration of Formic acid with
conc. H2SO4.
HCOOH CO + H2O
# CO burns with a blue flame.
# CO is toxic because it forms a complex with haemoglobin in
the blood which is more stable than the complex formed by
oxygen. This prevents the haemoglobin in the red blood
corpuscles from carrying oxygen causing oxygen deficiency
leading to unconsciousness and death.
# Some important industrial fuels
Water gas – equimolar mixture of CO & H2
Producer Gas – CO + N2
Coal Gas – CO + H2+ CH4 + CO2
Carbides
# Compounds of carbon with a less electronegative element are
called carbides, these are of three types –
1. Ionic/Salt Like Carbides
2. Covalent carbides
3. Interstitial Carbides
1. Ionic / Salt like Carbides
These carbides are classified depending on the products
obtained on hydrolysis –
(i) Methanides (C4-)
These carbides on hydrolysis produces methane .
e.g. Be2C, Al4C3
(ii). Acetylides(C22-)
These carbides on hydrolysis produces Acetylene .
e.g. CaC2
CaC2 is an important chemical intermediate and is used on
industrial scale to produce calcium Cynamide.
CaC2 + N2 CaCN2 or Ca(NCN) + C
Nitrolim
Calcium Cynamide actually contains NCN2- ion .
# Calcium cynamide on further heating with C produces calcium
Cynaide
CaCN2 + C Ca(CN)2
(iii). Allylides(C34-)
These carbides on hydrolysis produces Propyne .
e.g. Mg2C3
2. Covalent Carbides
SiC and B4C are the most important .
# Both SiC and B4C are hard infusible and inert and are used as
an abrasive and shield for radiation.
# B4C is also used in break linings of cars and bulletproof
clothings.
3. Interstitial Carbides
Due to small size of C atoms , c atoms occupy the interstitial
sites in the lattice of metal and these carbides are called
interstitial carbides.
# Thee carbides are mainly formed by transition metals and
some og the lanthanides and actinides.
For e.g. Cr4C3 ,Fe3C(Cementite) TaC,WC etc.
# These carbides are refdractory in nature Ii.e. Have high
melting point)
15th Group Nitrogen Family (Pnicogens)
Nitrogen and phosphorus are non-metal, arsenic and antimony metalloid and
bismuth is a typical metal.
Oxidation States
# The common oxidation states of these elements are –3, +3 and +5. The
tendency to exhibit –3 oxidation state decreases down the group , bismuth
hardly forms any compound in –3 oxidation state.
# The stability of +5 oxidation state decreases down the group.
# Nitrogen exhibits +1, +2, +4 oxidation states also when it reacts with oxygen.
Phosphorus also shows +1 and +4 oxidation states in some oxoacids.
# In the case of nitrogen, all oxidation states from +1 to +4 tend to
disproportionate in acid solution.
For example, 3 HNO2 HNO3 + H2O + 2 NO
# Similarly, in case of phosphorus nearly all intermediate oxidation states
disproportionate into +5 and –3 both in alkali and acid.
# Nitrogen forms diatomic molecule due to its tendency to form effective pp-pp
bond, on moving down the group the strength of pis bond decreases due to
increase in size.
# Phosphorous exist as tetratomic molecules .
# The Single P-P bond is more stronger than single N-N bond.
CHEMICAL PROPERTIES
1. Reaction with Hydrogen
# All the elements form Hydrides of type MH3.
# Thermal stability decreases on moving down the group due to increase in size and
consequently the reducing character of Hydrides increases.
# M.P. Order - NH3 > BiH3 > SbH3 >AsH3 > PH3
# B.P. Order – BiH3 > SbH3 > NH > AsH3 >SbH3
# Basicity of these hydrides decreases down the group.
2. Reactivity towards Oxygen
# All these elements form two types of oxides E2O3 & E2O5.
# Acidic nature increases with increase in oxidation state .
# The E2O3 oxides of N & P are acidic, that of As & Sb amphoteric and of Bi are
predominantly basic.
3. Reactivity towards Metals
# All these elements react with metals to form their binary compounds in -3 oxidation
states.
Ca3N2 – Calcium Nitride , Ca3P2 – Calcium Phosphide
Na3As – Sodium Arsenide, Zn3Sb2 – Zinc antimonide
Mg3Bi2 -
# Nitrogen forms diatomic molecule due to its tendency to form effective pp-pp
bond, on moving down the group the strength of pis bond decreases due to
increase in size.
# Phosphorous exist as tetratomic molecules .
# The Single P-P bond is more stronger than single N-N bond.
Nitric Acid (HNO3)
Preparation
(i) Ostwald’s process-
This method is based upon catalytic oxidation of NH3 by atmospheric oxygen.
4 NH3 (g) + 5 O2 (g) (from air) 4 NO (g) + 6 H2O (g)
Nitric oxide thus formed combines with oxygen giving NO2.
2 NO (g) + O2 (g) 2 NO2 (g)
Nitrogen dioxide so formed, dissolves in water to give HNO3.
3 NO2 (g) + H2O (l) 2 HNO3 (aq) + NO (g)
NO thus formed is recycled and the aqueous HNO3 can be concentrated by
distillation upto ~ 68% by mass. Further concentration to 98% can be achieved by
dehydration with concentrated H2SO4.
Concentrated nitric acid is a strong oxidising agent and attacks most metals except
noble metals such as gold and platinum. The products of oxidation depend upon the
concentration of the acid , temperature and the nature of the material undergoing
oxidation.
(A) Metals placed above H in electrochemical series (ECS)
1. Mg, Mn cold and dilute M(NO3)2 M + 2HNO3 M(NO3)2 + H2
2. Zn, F
(a) very dilute NH4NO3 4Zn+10HNO3 4Zn(NO3)2 + NH4NO3 + 3H2O
(b) dilute N2O 4Zn + 10HNO3 4Zn(NO3)2 + N2O + 5H2O
(c) concentrated NO2 Zn + 4HNO3 Zn(NO3)2 + 2NO2 + 2H2O
Note – Sn forms NH4NO3 with dil HNO3 and Stannic acid with conc. HNO3.
(B) Metals placed below H in electrochemical series (ECS)- Cu,Ag,Hg ,Pb[Not below]
(i) dilute NO 3Pb + 8HNO3 3Pb(NO3)2 + 2NO + 4H2O.
Hg forms Hg2(NO3)2
(ii) concentrated NO2 Pb + 4HNO3 Pb(NO3)2 + 2NO2 + 2H2O
(C)Metals like Cr , Al are rendered passive due to formation of oxide film.
(D) Noble metals like Au,Pt don not react with HNO3 but dissolve in aqua regia (3 :1
mixture of HCl & HNO3)
Au + 4H+ + NO3- +4Cl- AuCl4- + NO + 2H2O
Pt + 16H+ + 4NO3- +18Cl- 3PtCl62- + 4NO + 8H2O
# Concentrated nitric acid is also oxidizes non-metals to their
corresponding “-ic’ Acid .
I2 + 10 HNO3 2 HIO3 + 10 NO2 + 4 H2O
C + 4 HNO3 CO2 + 2 H2O + 4 NO2
S8 + 48 HNO3 (concentrated) 8 H2SO4 + 48 NO2 + 16 H2O
P4 + 20 HNO3 (concentrated) 4 H3PO4 + 20 NO2 + 4 H2O
# Brown Ring Test : This test is carried out to detect the presence of
NO3- ion.
The test is usually carried out by adding dilute ferrous sulphate solution
to an aqueous solution containing nitrate ion , and then carefully
adding concentrated sulphuric acid along the sides of the test tube. A
brown ring at the interface between the solution and sulphuric acid
layers indicate the presence of nitrate ion in solution.
NO3– + 3 Fe2+ + 4H+ NO + 3Fe3+ + 2 H2O
[Fe (H2O)6]2+ + NO [Fe (H2O)5 (NO)]2+ + H2O
