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CONTENTS
No. No.

PHYSICAL CHEMISTRY
1. Chemical Kinetics 1
2. Nuclear Chemistry 5
3. Thermodynamics 6
4. Thermochemistry 12
5. Chemical Equilibrium 14
6. Ionic Equilibrium 18
7. Electrochemistry 25
8. Liquid Solution 30
9. Solid State 34

ORGANIC CHEMISTRY

10. Alkane 38
11. Alkene 39
12. Alkyne 41
13. Alkyl halide 42
14. Comparision SN1 & SN2, E1 & E2 44
15. Alcohol 45
16. Ether 48
17. Carbonyl compounds 49
18. Grignard Reagent 50
19. Carboxylic acid 51
20. Est er 52
21. Amide 55
22. Amine 56
23. Benzene 59
24. Organic Reagent 60
25. Organic Name Reaction 67
26. Addition Polymers 71
27. Condensation Polymers 72
28. Carbohydrates 73
29. Amino acids & Proteins 75
INORGANIC CHEMISTRY
30. Alkali Metal 76
31. Alkaline Earth Metals 79
32. Boron Family 82
33. Carbon Family 85
34. Nitrogen Family 87
35. Oxygen Family 89
36. Halogen Family 91
37. Nobel Gas 92
38. Metallurgy 93
39. Coordination Chemistry 97
40. d-Block 100
41. Salt Analysis 102
Rate of disappearance of reactant (appearance of products)
Rate of reaction (ROR) =
Stoichiometric coefficient of reac tant (products)

For a reaction :

aA + bB cC + dD

1 d[A] 1 d[B] 1 d[C] 1 d[D]


Instantaneous rate :
a dt b dt c dt d dt

Relationship between rate of reaction and rate of disappearence of reactant (rate of appearance of product).

1 [A ] 1 [B] 1 [C] 1 [D]


Average rate :
a t b t c t d d t

Graphical method for determining rate :

[R]2 [R]1 ([P]2 [P]1 )


Avg. Rate = t2 t1 t2 t1

OA OA
Instantaneous rate = – = + = ± slope of tangent
OB OB

Important kinetic expression for reaction of type A B :

Order Zero 1st 2nd nth

Differential Rate = k Rate= k[A] Rate = k[A] 2


Rate = k[A] n
rate law

[A]0 1 1 1 1 1
Integrated [A 0 ]–[A]= kt kt = In kt = [A ] [A ]0 kt =
[A] (n 1) [A ]n [A]n0
1 1

rate law

[A ]0 ln 2 1 1 2n 1 1
Half life (t1/2) t 1/2 = t 1/2 = t 1/2 = [A ] k t 1/2 = k (n 1) [A ] n 1
2k k 0 0

(t 3/4) t 3/4 =1.5 t 1/2 t 3/4 = 2 t 1/2 t 3/4 = 3 t 1/2 t 3/4 = (2 n–1 + 1) t 1/2

1
Graphs of various order
1
Order Rate vs [A] [A] vs t log [A] vs t vs t
[A ]

Zero order

First order

Second order

Where
[A]0 initial concentration
[A] concentration at time t
t1/2 time taken for initial concentration of reactant to finish by 50%
t3/4 time taken for initial concentration of reactant to finish by 75%
Monitoring Kinetics Experimently :
The kinetics of reaction can be followed (i.e. order, rate constant etc. can be established) by measuring a
property which changes with time.
e.g. (i) Total pressure in a gaseous reaction.
(ii) Volume of a reagent (Acidic, Basic, oxidising or reducing agent)
(iii) Volume of a gaseous mixture (V)
(iv) Optical rotation (R)
For a Reaction -
An nB
t = 0 c 0 c0 conc. at t = 0
t = t c–x nx ct conc. at t = t
t= 0 nc c conc. at t =
For any measurable property X proportional to the concentration of reaction mixture at various times,
following relations can be expressed.
In terms of -
(i) X0 and x (ii) X0 and Xt (iii) X and Xt (iv) X0, Xt, and X

1 X0 1 (n 1) X 0 1 (n 1) X 1 X X0
k = t ln X x k= ln k = ln k = ln
0 t nX 0 X t t n(X X t ) t X Xt
where
x amount of reactant reacted in time 't'.
X0 measured property at t = 0
Xt measured property at t = t
X measured property at t =

2
Examples : (For Monitoring Kinetics Experimently)
(i) Inversion of cane sugar :
C12H22O11 (aq) + H2O C6H12O6(aq) + C6H12O6(aq)
H

Sucrose Glucose Fructose


dextro-rotatory dextro-rotatory laevo-rotatory
(+66.5°) (+52.5°) (–92°)

(Laevo-rotatory)

2.303 r r0
k log
t r rt
r0 = rotation at time, t = 0
rt = rotation at time, t = t
r = rotation at time, t =
(ii) Acidic hydrolysis of ethyl acetate :

CH3COOC2H5 + H2O CH3COOH + C2H5OH


H

2.303 V V0
k log
t V Vt

V0 = Volume of NaOH solution used at time, t = 0


Vt = Volume of NaOH solution used at time, t = t
V = Volume of NaOH solution used at time, t =
Note : Here NaOH acts as a reagent. Acetic acid is one of the product the amount of which can be found by
titration against standard NaOH solution. But being an acid-catalysed reaction, the acid present originally
as catalyst, also reacts with NaOH solution.

Important characteristics of first order reaction :


t1/2 is independent of initial concentration.
In equal time interval, reactions finishes by equal fraction.
t = 0 t = t t = 2t t = 3t ....
Reactant conc. a0 a 0x a 0x a 0 x ........
2 3

x = fraction by which reaction complete in time 't'.

k
Graph of ln[A] vs t is straight line with slope =
2.303
Graph of [A] vs t is exponentially decreasing.
Zero order :
• t1/2 of zero order is directly proportional to initial concentration.
• In equal time interval, reaction finishes by equal amount.
t = 0 t = t t = 2t t = 3t .....
C0 C0 – x C0 – 2x C0 – 3x ....
• Graph of [A] vs t is straight line.
[A ]0
A zero order reaction finishes in t
k
Temperature dependence :
– Arrhenious equation : k = A.e–Ea/RT
– E a = minimum energy over and above the avg. energy of reactant which must be possesed by reacting
molecule for collision to be succesful.
– A = frequency factor - proportional to number of collisions per unit volume per second.
3
– e = Fraction of collision in which energy is greater than Ea.
–Ea/RT

– A and Ea are constant i.e. do not vary with temperature


Ea
ln k = ln A –
RT
Graph : Graphical determination of Ea.

k T 10
Temperature coefficient =
kT

By default T = 298 K

k2 Ea 1 1
Variation of rate constant with temparture ln
k1 R T1 T2

Endothermic and exothermic reactions :

H = E af – E ab

Parallel reaction :

(i) Rate = (k1 + k2 ) [A] - (differential rate law)


k1 [B ]
(ii) k2 [C ]
0 .6 9 3
(iii) t1/2 =
k1 k2
k1 k2
(iv) % of B = 100 ; % of C = 100
k1 k2 k1 k2
(v) [A] = [A]0 e –(k 1 k2 )t

Pseudo-order reaction :
Rate law rate = k [A]m [B]n
Pseudo rate law :
rate = k1 [A]m
[B] assumed constant in two cases :
(i) B in large excess (ii) B CATALYST

4
NUCLEAR CHEMISTRY

All nuclear reactions are first order :


Two types of nuclear reaction : ( a ) Artifical radioactivity (b) Radioactivity (spont.)
First order
N0
t = 2.303 log Decay constant
Nt
N0 Initial nuclei
Nt Nuclei at 't'
dN t
Activity = A t = = N t ; Nuclei/sec.
dt
A t = Rate of decay

ln 2
t1
2

decay = 2 He
4 Particles at high velocity

Z X
A A 4
Z 2 Y
To size of large nuclei

decay = 01 e at high velocity


A
Z X
A
Z+1 P + –1/ e
n
# To ratio.
P
# Nuclear change in decay
1
0 n 1
1 P 0
1 e
-decay :
Photons from excited nuclei after – or – decay
No effect on n/p ratio
High energy e/m radiation.
1
Mean life , tavg =
Parallel decay :
t = 0 N0
t = t N 0 –x–y
eff. = 1 + 2

1 1 1
= +
t eff. (t 1/2 )1 (t1/2 )2

No dependence on temp.

5
THERMODYNAMICS

THERMODYNAMICS :
Study of heat and work interaction between system and surrounding.
A macroscopic science.
Thermodynamic laws are experimentally verified.

Important terms and concepts in thermodynamics.


System - Portion of universe under investigation.
Surrounding - Anything apart from system.
Boundary - Real or hypothetical line or surface between system and surrounding.
Wall - A real boundary.
Rigid wall - Immovable wall (w = 0)
Non-rigid wall - Movable wall (w 0)
Adiabatic wall - Insulated wall (q 0)
Diathermic wall - Non-insulated wall (q 0)
State variable - Variable which defines state of system.
State of system - A condition defined by fixed value of state variables.
State of thermodynamic equilibrium - A condition in which state variables do not vary with time.
Extensive state variable : State variable whose value depends upon size of system.
Examples - mass, volume, charge, mole etc.
Intensive state variable : State variable whose value does not depends upon size of system.
Examples - concentration, density, temperature etc.
Path variable :
Heat : Mode of energy transfer between system and surrounding due to temperature difference.
Work : Mode of energy transfer bet ween system and surrounding due to difference in
generalized force.(Net force).
THE FIRST LAW
(i) Energy of universe is conserved
(ii) Internal energy (U) of a system is state function.
(iii) U=q+w
U = Increase in internal energy of system.
q = Heat absorbed by the system
w = work done on the system

(iv) In a cyclic process U=0


Cyclic

If a cyclic process involves n steps with heat absorbed and work done on the system, q i and w i
respectively, then -

i n i n i n
U qi wi qi wi 0
Cyclic i 1 i 1 i 1

Qnet = – Wnet (in a cyclic process)


6
(v) If two states 1 and 2 are connected by n paths involving q i and w i, heat and work respectively, then
U = q1 + w1 = q2 + w2 = .............. qn + wn
(vi) q and w are path dependent quantities (indefinite quantities) but there sum is a definite quantity ( U).
Enthalpy : A state function defined by first law
H = U + PV
(i) Enthalpy is (pressure volume energy + internal energy of system)
(ii) Enthalpy is also called heat content of system.
Heat absorbed at constant volume and constant pressure.

qV U Heat absorbed by a system in isochoric process is equal to change in internal energy of system.

qp H Heat absorbed at constant pressure by a system is equal to change in enthalpy.

Enthalpy change :
For General process -
H = U + P2V2 – P1V1 ...........(i)
For Isobaric change -
H = U + P V ..........(ii)
For Isochoric change -
H = U + V( P) .........(iii)
For a differential change
dH = dU + PdV + VdP .........(iv)
Ideal gas processes : (See table page no. 11)
Enthalpy of phase transition
H va p = heat absorbed at constant temperature and pressure to convert one mole liquid into it's vapours.
= molar enthalpy of vapourisation.
Hfusion= heat absorbed at constant temperature and pressure to convert one mole solid into liquid.
= molar enthalpy of fusion.
Hsublimation = heat absorbed at constant temperature and pressure to convert one mole solid into it's vapours.
= molar enthalpy of sublimation.
H = U + P(V f – V i) since phase transtions are isobaric and isothermal processes.
Relationship between H and U for phase transtions.
For vapourisation H vap = Uvap + RT
For sublimation Hsublimation = Usublimation + RT
For fusion Hfusion U fusion
Heating curve at constant pressure :

(Reversible, isobaric vapourisation at boiling point.)

(Reversible, isobaric, melting at melting point.)

7
Enthalpy of reaction ( r H) : The enthalpy of reaction is heat exchanged at constant pressure and
temperature to convert the stoichiometric amount of reactant into product with specified physical state
according to balanced chemical reaction at constant temperature and pressure.
for aA + bB cC + dD

r
H = q P = enthalpy of reaction

r
H = (cH C + dH D – aH A – bH B ) where H A, H B , H C, H D are molar enthalpies of A,B,C and D.
Relationship between H and
r
U
r

r
H = r
U + n g RT (for ideal gas)

r
H = r
U + P(V f – V i ) (for non ideal conditions)
The stoichiometric coefficient of solids and liquids in not considered in calculation of ng
(because VS ~ VL << Vg)
Standard state for
(i) Ideal gas : 1 bar pressure ; any temperature.
(ii) Solid / Liquid : 1 bar pressure ; any temperature.
(iii) Solute : Molar concentration of 1 mole/L at P = 1 bar.
Standard enthalpy, internal energy change for reaction.

r
H° and r
U° are change in thermodynamics function of a system under standard conditions.

SECOND LAW
Spontaneous process :
• A process which takes place on it's own without any external help.
• Spontaneous process Irreversible process Natural process.
Second law : During a spontaneous process.
• S universe > 0
S system + Ssurr.> 0
• S is a state function. S is measure of disorder of a system.
(A) Change in entropy of system is given by :
dq rev .
dS system =
T
(i) Entropy change for ideal gas process :

T2 V2
• S = nCv ln + nR ln V
T1 1

(ii) Entropy change for system in phase transition :

H vap.
• S vap. =
Tb

H fusion
• Sfusion. =
Tf

H sublim ation
• S sublimation =
TSub.

8
(iii) Entropy change of system for a chemical reaction :
For a reaction -
• aA + bB cC + dD

r S cS c dS D aS A bS B

SA, SB,SC and SD are molar absolute entropies which is obtained by third law.
(B) Entropy change in surrounding :

–q actual
(i) Ideal gas process : S surr.
T

– H
(ii) Phase transition : S surr.
T

rH
(iii) Chemical reaction : S surr.
T

For reversible processes : S system + S surr. = 0


S system = - S surr.

For irreversible processes : S system + S surr. > 0


S total ! 0

Prediction of sign of S from inspection :


r

(i) If ng > 0 ; r
S > 0.
(ii) If Solid liquid "
# S > 0
liquid gas $
r

(iii) If cyclisation taken place r


S < 0.

Gibb's function : G = H – TS
G= H–T S For isobaric change
G = – T( STotal)
( G)T,P % 0 Process spontaneous
(A) Change in G for phase transition :
(i) For reversible phase transitions : G = 0.
(ii) For irreversible phase transition : GP,T = HP,T – T SP,T
(B) Change in G for chemical reaction :
aA + bB cC + dD

r
G = cGC + dG D –aGA – bGB .....(i)

r
G = r
H – T rS .....(ii)

r
G = r
G° + RT ln Q .....(iii)
Where, Q Reaction quotient

9
G / G° and state of chemical equilibrium :

At equilibrium :

• G = 0 Gproduct = Greactant

• G° = –RT ln Keq.

• At equilibrium the system gibb's function is at minimum value.

Difference between G and


r r
G° :

r
G = change in Gibb's function when all the reactants and products have arbitrary activities.

r
G° = change in Gibb's function when all the reactants and products are at unit activities.

All gases at 1 bar pressure.

All solute at molar concentration 1 M.

Factors on which r
G° depends -

(i) Stoichiometric coefficients of a balanced chemical reaction.

(ii) the temperature.

(iii) the r
G° is independent of actual pressure or concentration of reactants or products.

Gibb's function and non-PV work :

– ( G)T, P
= Wmax

decrease in Gibb's function at constant temperature and pressure is equal to maximum non-PV work
obtainable from system reversibly.

– G = –
r r
H + T rS

Decrease in Gibb's function = heat given out to surrounding + T rS.

10
IDEAL GAS PROCESSES :

Process Expression Expression U H Work on


for w for q PV-graph

V2 V2
Reversible w nRT ln q nRT ln 0 0
V1 V1
isothermal
process P1 P1
nRT ln q nRT ln
P2 P2

Irreversible w Pext V2 V1 q Pext V2 V1 0 0


isothermal
nRT nRT
process Pext
P2 P1

Isobaric w Pext V2 V1 q H nC P T U nC V T H nCP T


process = – nR T

Isochoric w 0 q U nC V T U nC V T H nCP T
process

Reversible w nC V (T2 T1 ) q 0 U nC V T H nCP T


P2 V2 P1 V1
adiabatic = PV =constant
1
process TV =constant
–1

TP 1– /
=constant

Irreversible w nC V (T2 T1 )

adiabatic P2 V2 P1 V1
1
process

&C
P2 V2 P1 V1
T2
Polytropic w q dT U nC V T H nCP T
process n 1
V
T1

&1
R
T2
R( T2 T1 ) dT
w n
n 1 T1

V2 = Final volume V1 = Initial volume


P2 = Final pressure P1 = Final pressure
11
THERMOCHEMISTRY

r
H = q P = Heat of reaction at constant pressure

r
E = r
U = q V = Heat of reaction at constant volume.
For mix. of reacting ideal gases at constant Temperature :

r
H = r
U + ' ng) RT.
Exothermic Reaction :
HP > HR UP > U R
r
H > 0
r
U > 0
Endothermic Reaction :
HP < HR UP < UR
r
H < 0
r
U < 0
Reversible Phase Transition
Isothermal and Isobaric
Example :
(a) Melting or Freezing at MP
(b) Vaporisation or condensation at B.P.
(c) Sublimation at sublimation point.
(d) Interconversion of allotropic forms at Transition temperature.
Sg >> S > Ss ; Vg >> V > Vs ;
Vg >> V < Vs (Water) ; Hg >> H > Hs ;
Ug >> U > Us ; H sub >> H vap > Hfus.
At same Pressure and Temperature
Hsub = Hvap + Hfus.
For reversible phase transition.
W = – Pext [ V]
H trans
S trans. =
Ttrans
q = Htrans
Utrans = Htrans + w
H =
r
VPH (product) – VRH (Reactant)
VP, VR – Stoichiometric coefficient of reactants & products
G=
r
VPG (product) – VRG (reactants)
Determining r
H° for reaction :- 3 methods
(a) H° =
r
VP H°f (P) – VR H°f (R)
(b) r
H° = VR H°comb. (R) – VP H°comb. (P)
(c) H° =
r
Hatomisation (R) – Hatomisation (P)
H°f (Element in solid state) = 0.
H°f (CO2, g) = H°comb. (C, grap.)

12
H°f (H2O, ) = H°comb. (H2, g)
aA + bB cC + dD ; r

r
H° = change in enthalpy when
a mol of A react ; b mol of B react ; c mol of C formed ; d mol of D formed

r
G° = VP G°f (P) – VR G°f (R) OR r
G° = H° – T rS°
r

Gibbs enthalpy is function of P, T.


P( G(
T( G
H°f (H , aq) = 0
+

G°f (H+, aq) = 0


E )H | H = 0 By convention
S°m (H , aq) = 0
2
+

q = & ms dt
= & n C dt

= & C dt
m

mS = nCm = C

specific molar Total


heat heat heat
capacity capacity capacity
For strong Acid and strong base
H°neutr. = – 57.1 kJ/mol.
when 1 eq. H+ (acid) reacts with 1 eq. OH– (base)

If acid or base is weak

H°neut. = – 57.1 + Hionisation + ve

Heat evolved in SA + SB titration = (no. of eqv. of limiting reagent) × 57.1 kJ

Resonance enthalpy = R.E. < 0 = (Energy of R.H.) – (Energy of stablest R.S.)

r
H° (Actual) – H° (theoretical) = *
r
VP RE (P) – VR RE (R)

H°hydration [CuSO4, s]

H°solution [CuSO4, s] – H°solution [CuSO4 5H2O, s]

Enthalpy of atomisation :

H°atomisation (O2, g) = BE (O = O)

H°atomisation (C6H6, ) = H°vap. + 3+ (C = C) + 3+ (C – C) + 6+ (C – H) + = Bond enthalpy

H°atomisation (Fe, s) = H°sub

H°atomisation (I2, s) = H°sub + + (I – I)

13
CHEMICAL EQUILIBRIUM

At equilibrium for reaction mix. properties like P, V, T, n, magnetism, colour, density become constant.

For gaseous reactions.

KP = KC (RT ) ng

KP > KC if ng > 0
KP < KC if ng < 0
KP = KC if ng = 0

Units of KP = (atm ) ng

Units of KC = (M ) ng

Af
KP = e r H ) / RT
Ab
both K P & KC depend only on temperature for given reaction.
For pure solids & pure liquids (solvent) :
Active mass = 1 [Kinetically]
Activity = 1 [thermodynamically]
Density
Molarity = = Constant
Molar m ass
Reaction Quotient (QC / QP)
(i) Used to find direction of reaction mixture – Fwd./Bwd.
(ii) QC < KC or QP < KP FWD.
QC > KC or QP > KP BWD.
QC = KC or QP = KP Equilibrium

(iii) QP = QC (RT ) ng

If
(1) [KP >>> 1 or K C >>> 1]
or
(2) [KP <<< 1 or K C <<< 1]
no need to solve equation but use approximation.

14
In 1st case [R]eq , 0
In 2 case nd
[P]eq , 0

Degree of dissociation,
n P m V
n0 P0 m0 V0
# n, P, m, V mols, partial pressure, mass, partial volume of reactant respectively.
% dissociation = % reactant converted to product = 100
# % 1 [Equality for irreversible reaction]
Pgas Vgas n gas
X gas =
PT VT nT
For a reacting mixture of 'n' gases :
n

2VD mix = M avg. = x im i


i 1

• Mavg. & VD mix is a function of mixture composition.


• For mixture of reacting gas M avg. changes & becomes constant at equilibrium.
1
• Mavg. (or VDmix) -
moles of gases in m ixture
(VD ) i Mi nf Pf
(VD ) f Mf ni Pi
Used to find ' ' from Mavg or VD data for reactions with ng 0
• On going FWD.
If ng > 0
P( n(
Mavg. VD
If ng < 0 P n
Mavg. ( VD (
If ng = 0 P, n, M avg, VD = Constant
For a reaction with ng 0
depends on – KP or KC, Temperature, Initial concentration, Initial moles, Initial pressure, volume of vessel
For a reaction with ng = 0 ;
depends only on - KP or KC, Temperature
KP or KC depend on the way of writing a reaction :
I. R P ; KC, KP
P R ; 1/ KC, 1/ KP
II. C D ; KC' , KP'
R + C P + D ; KCKC' or KPKP'
III. R–C P–D;
KC KP
or R + D P+C; or
K C' K 'P
IV. nR nP ; (KC) or (KP)n
n

15
Relative Humidity (R.H.)

Partial pressure of water vapour


= × 100
Aqueous tension
If RH < 100% Partial pressure < Aqueous tension Unsaturated air sample
If RH ! 100% Saturated air sample

Le chetelier Principle

Case I : [R] increased Forward shift


[P] increased Backward shift
If R or P is pure solid / Pure liquid No effect.
Case II : Total P increased (or V decreased )
If ng > 0 backward
If ng < 0 forward
If ng = 0 no effect
Case III : V Increased
Same effect as P decreased
If ng > 0 forward
If ng < 0 backward
If ng = 0 no effect
Case IV : T Increased
If r
H° > 0 forward
If r
H° < 0 backward
T decreased
If r
H° > 0 backward
If r
H° < 0 forward
Case V : Using Catalyst
No effect on K C, KP or equilibrium concentration
Only time required to attain equilibrium is lesser.
Case VI : Adding inert gas at constant V.
No effect
Case VII : Adding inert gas at constant Pressure
Same effect as Pressure decrease or volume increase

Thermodynamics state of Equilibrium :


Gmix Minimum "
.
G 0 # at P, T constant
.
r

/ VPGP = / VRGR $

If G<0
r
/ VPGP < / VRGR

16
Reaction shifts forward to attain equilibrium.

If r
G> 0 / VPGP > / VRGR

Reaction shifts backward to attain equilibrium.

If r
G = 0 Equilibrium state

r
G = r
G° + RT ln(Q)

r
G° = Standard Gibbs energy of reaction (when all Reactants & Products are in standard states)

Standard State

Gas Ideal gas

Activity=Partial pressure=1 bar , 1 atm.

Solute Ideal solution

Activity = concentration = 1M

Solid/Liquid Pure activity = 1

Q contains activity of species i.e., partial pressure in bar (or atm) for gas

molarity for solute is unity for solid or liquid.

At equilibrium r
G = 0 & Q = Keq

r
G° = – RT n keq
Keq. = e r G)/ RT

For gaseous homogeneous reaction,

r
G° = –RT ln KP
For homogeneous reaction in solution phase

r
G° = –RT ln KC

BP, M.P. & Sublimation point all increase in increasing pressure

Exception – M.P. of H2O decrease on increasing pressure

Von't Hoff Equation :

d ln K P H) H) Af K P2 H) 1 1
; n KP = n ; log
r r r

dT RT 2
RT Ab K P1 2.303R T1 T2

17
ACCORDING TO STRENGTH IONIC CONDUCTORS ARE OF 2 TYPES :
1. Strong electrolyte : Those ionic conductors which are completely ionized in aqueous solution are called
as strong electrolyte.
Ex. Na+Cl –, K +Cl –, etc.
(a) Strong acid H2SO4, HCl, HNO3 HClO4, H2 SO5, HBr, HI
(b) Strong base KOH, NaOH, Ba(OH)2 CsOH, RbOH
(c) All Salts NaCl, KCl, CuSO4..........
2. Weak electrolytes : Those electrolytes which are partially ionized in aqueous solution are called as weak
electrolytes. For weak electrolytes the value of is less than one.
Ex.
(a) Weak acid HCN, CH3 COOH, HCOOH, H2CO3, H3 PO3, H3PO2, B(OH)3
(b) Weak base NH4 OH, Cu(OH)2, Zn(OH)2, Fe(OH)3, Al(OH)3

ACIDS BASES AND SALTS :


Arrhenius concept :
Arrhenius Acid : Substance which gives H+ ion on dissolving in water (H+ donor)
Ex. HNO3 , HClO4, HCl, HI, HBr, H2SO4, H3PO4 etc.
H3 BO3 is not Arrhenius acid.

Arrhenius base : Any substance which releases OH– (hydroxyl) ion in water (OH– ion donor).
First group elements (except Li.) form strong bases

Bronsted - Lowery concept : (Conjugate acid - base concept) (Protonic concept)


Acid : substances which donate H+ are Bronsted Lowery acids (H+ donor)
Base : substances which accept H+ are Bronsted Lowery bases (H+ acceptor)

Conjugate acid - base pairs :


In a typical acid base reaction

HX + B X– + HB+

Acid Conjugate base Base Conjugate acid


Ex : HC l Cl NH 3 NH4
– +

H 2 SO 4 HSO 4 H2O H3O+


HSO 4 SO 4 RNH 2 RNH 3


– 2– +

H2O OH –

18
LEWIS CONCEPT (electronic concept) :
An acid is a molecule/ion which can accept an electron pair with the formation of a coordinate bond.
Acid e– pair acceptor
Ex. Electron deficient molecules : BF3, AlCl3
Cations : H+, Fe2+, Na+
Molecules with vacant orbitals : SF4, PF3
A base is any molecule/ion which has a lone pair of electrons which can be donated.
Base (One electron pair donor)
Ex. Molecules with lone pairs : NH3, PH3, H2O, CH3OH
Anions : –
OH, H–, –NH2
IONIC PRODUCT OF WATER :
According to arrhenius concept

H2O H+ + OH– so, ionic product of water, Kw = [H+][OH–] = 10–14 at 25° (exp.)
Dissociation of water is endothermic, so on increasing temperature K w increases.
Kw increases with increase in temperature.
Now pH = –log[H+] = 7 and pOH = –log[OH–] = 7 for water at 25°C (experimental)
pH = 7 = pOH neutral "
.
pH < 7 or pOH > 7 acidic # at 25 °C
.
pH > 7 or pOH < 7 Basic $
Ionic product of water is always a constant whatever has been dissolved in water since its an equilibrium
constant so will be dependent only on temperature.
Degree of dissociation of water :

no. of moles dissociated


H2O H+ + OH– =
Total no. of moles initially taken

10 7
= = 18 × 10–10 or 1.8 × 10–7 % [at 25°C]
55.55

Absolute dissociation constant of water :

[H ][OH ] 10 7 10 7
H 2O H+ + OH– Ka = Kb = = = 1.8 × 10–16
[H 2 O] 55.55
So, pKa = pKb = – log(1.8 × 10–16 ) = 16 – log1.8 = 15.74
ACIDITY AND pH SCALE :
Acidic strength means the tendency of an acid to give H 3O+ or H+ ions in water.
So greater then tendency to give H +, more will be the acidic strength of the substance.
Basic strength means the tendency of a base to give OH– ions in water.
So greater the tendency to give OH– ions, more will be basic strength of the substance.
The concentration of H+ ions is written in a simplified form introduced by Sorenson known as pH scale.
pH is defined as negative logarithm of activity of H+ ions.

0 pH = – log a H (where a H is the activity of H+ ions)

Activity of H+ ions is the concentration of free H + ions or H 3O+ ions in a dilute solution.

19
The pH scale was marked from 0 to 14 with central point at 7 at 25 °C taking water as solvent.
If the temperature and the solvent are changed, the pH range of the scale will also change. For example
0 - 14 at 25 °C (Kw = 10–14 ) Neutral point, pH = 7
0 - 13 at 80 °C (Kw = 10 ) –13
Neutral point, pH = 6.5
pH can also be negative or > 14
pH Calculation of different Types of solutions :
(a) Strong acid solution :
(i) If concentration is greater than 10 –6 M.
In this case H+ ions coming from water can be neglected,
so [H+] = normality of strong acid solution
(ii) If concentration is less than 10–6 M
In this case H+ ions coming from water cannot be neglected.
So [H+] = normality of strong acid + H+ ions coming from water in presence of this strong acid
(b) pH of a weak acid (monoprotic) Solution :
Weak acid does not dissociated 100 % therefore we have to calculate the percentage dissociation
using Ka dissociation constant of the acid.
We have to use Ostwald's Dilution law (as have been derived earlier)

HA H+ + A–
t=0 C 0 0
[H ][A ] C 2
teq C(1 – ) C C Ka = =
[H A ] 1

Ka
If << 1 (1 – ) , 1 Ka , C 2
= (is valid if < 0.1 or 10%)
C

Ka 1
[H+] = C = C = K a C So pH = (pKa – logC)
C 2
on increasing the dilution C = ( and [H+] pH(
(c) pH of a mixture of weak acid (monoprotic) and a strong acid solution :
Weak acid and Strong acid both will contribute H+ ion.
For the first approximation we can neglect the H + ions coming from the weak acid solution and
calculate the pH of the solution from the concentration of the strong acid only.
To calculate exact pH, we have to take the effect of presence of strong acid on the dissociation
equilibrium of the weak acid.
If the total [H+] from the acid is more than 10–6 M, then contribution from the water can be neglected,
if not then we have to take [H+] from the water also.
Relative strength of weak acids and bases :
For two acids of equimolar concentrations.

Strength of acid (I) K a1


=
Strength of acid (II) K a2

( d) pH of a mixture of two weak acid (both monoprotic) solution :


Both acids will dissociate partially.
Let the acid are HA1 & HA2 and their final concentrations are C1 & C2 respectively, then

20
HA1 H+ + A1 HA2 H+ + A2
– –

t=0 C1 0 0 C2 0 0
At eq. C1(1 – 1
) C1 1
+ C2 2
C1 1
C2(1 – 2
) C2 2
+ C1 1
C2 2

K a = C1 (C 1 C2 2) (C 2 2 C1 1 )C 2
1 1
K a2 = 2
1
C 1 (1 1) C 2 (1 2)

(Since 1
, 2
both are small in comparision to unity)

K a1
K a1 = (C1 + C2 2) ; K a 2 = (C1 + C2 2) = 1
1 1 1 2
K a2 2

C 1 K a1 C 2 K a2
[H+] = C1 + C2 = + [H+] = C 1 K a1 C 2 K a2
C1 K a1 C2 K a2 C 1 K a1 C 2 K a2
1 2

If the dissociation constant of one of the acid is very much greater than that of the second acid then
contribution from the second acid can be neglected.
(e) pH of a solution of a polyprotic weak acid :
Diprotic acid is the one, which is capable of giving 2 protons per molecule in water. Let us take a
weak diprotic acid (H 2A) in water whose concentration is c M.
In an aqueous solution, following equilbria exist.
If

1
= degree of ionization of H2A in presence of HA– K a1 = first ionisation constant of H2A

2
= degree of ionisation of HA– in presence of H2A K a 2 = second ionisation constant of H2A

I step II step

H2A + H2O HA– + H3O+ HA– + H2O A2– + H3O+


at eq. c(1 – 1
) c 1(1 – 2
) (c 1
+c 1 2
) at eq. c 1
(1 – )
2
c 1 2
(c 1
+c 1 2
)

[H 3 O ][HA ] [H 3 O ] [A 2 ]
(Keq) [H2O] = = K a1 (Keq) [H2O] = = K a2
1 [H 2 A ] 2
[HA ]

(c c 1 2 )[c 1 2 )]
0 K a1 = (c 1 c 1 2 ) [c 1 (1 2 )] K a2 = 1
c(1 1) c 1 (1 2 )

[c 1 (1 2 )][ 1 (1 2 )]
[c 1 (1 2 )] 2
= ....... (i) = 1 ...... (ii)
1 1 2

Knowing the values of K a 1 , K a and c, the values of 1


and 2
can be calculated using equations (i) and
2

(ii) After getting the values of 1


and 2
, [H3 O ] can be calculated as
+

[H3 O ] T = c +
1
+ c 1 2

Finally, for calculation of pH


If the total [H3 O+] < 10 –6 M, the contribution of H 3O+ from water should be added.
If the total [H 3O+] > 10–6 M, then [H 3O+] contribution from water can be ignored.
Using this [H3O+], pH of the solution can be calculated.

21
Approximation :

For diprotic acids, K a 2 << K a 1 and 2


would be even smaller than 1

0 1– 2
, 1 and 1 + 2
,1

C 1
Thus, equation (i) can be reduced to Ka1 = 1
1 1

This is expression similar to the expression for a weak monoprotic acid.


Hence, for a diprotic acid (or a polyprotic acid) the [H3O+] can be calculated from its first equilibrium
constant expression alone provided K a 2 << K a1

SALTS :
Salts are the ionic compounds formed when its positive part (Cation) come from a base and its negative
part (Anion) come from an acid.
Classification of salts :
( 1) Simple salts
(2) Normal salt : (i) Acid salts (ii) Basic salts
( 3) Double salts
( 4) Complex salts
( 5) Mixed salts
TYPES OF SALT HYDROLYSIS :
(1) Hydrolysis of strong acid - weak base [SA - WB] type salt –
Ex. CaSO 4 , NH 4Cl, (NH 4 )2 SO 4 , Ca(NO 3) 2, ZnCl 2, CuCl2 , CaCl 2

NH 4Cl + H2O NH4 OH + HCl

NH4++Cl – + H2O NH4 OH + H+ + Cl–

NH 4+ + H2O NH4 OH + H+
Summary :

Kw Kh Kw
(1) Kh (2) h
Kb C Kb C

Kw C
(3) H Ch (4) pH = – log [H+]
Kb

1 1
pH = 7 pK b log C
2 2
(2) Hydrolysis of [WA – SB] type salt –
Ex. KCN, NaCN, K2 CO 3, BaCO3, K3PO 4
NaCN +H2O NaOH + HCN
Na + CN + H2O
+ –
Na+ + OH– + HCN
CN– + H2O HCN + OH–
Summary :

Kw Kh Kw
(1) Kh (2) h =
Ka C Ka C

22
Kw C Kw Ka
(3) [OH–] = Ch = (4) [H+] =
Ka C

(5) pH = – log [H+]

1 1
pH = 7 + pKa + log C
2 2
(3) Hydrolysis of (WA - WB) type salt :
Ex. NH 4CN, CaCO 3 , (NH 4 )2 CO 3, ZnHPO 3
Summary :

Kw Kw
(1) K h (2) h Kh = Ka K b
Ka Kb

Kw Ka
(3) [H+] = = Ka.h (4) pH = – log [H+]
Kb

1 1
pH = 7 + pKa – pKb
2 2
(4) Hydrolysis of [SA – SB] type salt –
Ex. NaCl, BaCl2, Na2SO4, KClO4 etc.
(i) Hydrolysis of salt of [SA – SB] is not possible
(ii) Solution is neutral in nature (pH = pOH = 7)
(iii) pH of the solution is 7

BUFFER SOLUTIONS :

A solution that resists change in pH value upon addition of small amount of strong acid or base (less than
1 %) or when solution is diluted is called buffer solution.
The capacity of a solution to resist alteration in its pH value is known as buffer capacity and the mechanism
of buffer solution is called buffer action.
Types of buffer solutions
(A) Simple buffer solution
(B) Mixed buffer solution
SIMPLE BUFFER SOLUTION :
A salt of weak acid and weak base in water e.g. CH3COONH4 , HCOONH4, AgCN, NH4CN.
Buffer action of simple buffer solution
1 1
pH 7 pk a pk b
2 2

MIXED BUFFER SOLUTIONS :


(a) Acidic buffer solution :

[A ]
pH = pKa + log
[HA ]
[Salt]
pH = pKa + log
[Acid]

23
(b) Basic buffer solution :
A basic buffer solution consists of a mixture of a weak base and its salt with strong acid. The best known
example is a mixture of NH4OH and NH4Cl.
Condition for maximum buffer action :
[NH4OH] : [NH 4 Cl]
1 1

1
pOH = pK b log
1

pOH = pKb and pH = 14 – pKb

SOLUBILITY (s) AND SOLUBILITY PRODUCT (K sp) :


This is generally used for sparingly soluble salts. We will be dealing with the solubilities in the following
type of solution.
Solubility product (Ksp) is a type of equilibrium constant, so will be dependent only on
temperature for a particular salt.
Simple solubility
Let the salt is Ax By, in solution in water, let the solubility in H2O = 's' M, then
AxBy xAy+ + yB –x
– xs ys 0 Ksp = (xs)x (ys)y = xx, yy.(s)x+y
Condition of precipitation
For precipitation ionic product [IP] should be greater than solubility product ksp.

24
Electrolytic cell : Converts electrical energy into chemical energy

Cathode : Na +(aq.) + e Na(s)

1
Anode : Cl (aq.)

Cl (g) + e
2 2
Deposition of material at any electrode follow faraday's law of electrolysis.
Faraday's Ist Law :
w = Z it

M
w = × it
n factor 96500
where w = mass deposite (gm)
M = molar mass
i = current (Amp.)
t = time (sec.)
Faraday's second law :

At any electrode for material deposited.


w1 w 2 w 3
E1 E 2 E 3
Note : Order of discharge potential.
Cathode : Au+3 > Ag+ > Cu +2 > Zn+2 > H 2O > Al+3 > Mg+2 > Na + > Li +

Anode : SO 24 – 3 NO 3– 3 H 2 O 3 Cl – 3 Br – 3 I –

25
PRODUCTS OF ELECTROLYSIS OF SOME ELECTROLYTES

S. Electrolyte Electrode Product obtained Product obtained


No. at anode at cathode
(i) Aqueous NaCl Pt or Graphite Cl 2 H2
(ii) Fused NaCl Pt or Graphite Cl 2 Na
(iii) Aqueous NaOH Pt or Graphite O2 H2
(iv) Fused NaOH Pt or Graphite O2 Na
(v) Aqueous CuSO 4 Pt or Graphite O2 Cu
(vi) Dilute HCl Pt or Graphite Cl 2 H2
(vii) Dilute H 2SO 4 Pt or Graphite O2 H2
(viii) Aqueous AgNO 3 Pt of Graphite O2 Ag

Electrochemical Cell : converts chemical energy into electrical energy.

E°Cell = SRPcathode – SRPAnode


= SRPcathode + SOPat anode
Half cell reaction :
Anode: Zn(s) Zn (aq.)
2
+ 2e

Cathode : Cu ( aq.)
2
+ 2e Cus

Cell reaction : Zn(s) + Cu ( aq.)


2
Zn ( aq.)
2
Cu(s)
[Zn 2 ]
Q = ; n = 2
[Cu 2 ]

26
Nearest equation :

0.059
ECell = E°Cell log Q at 298 K
n

Max electrical work done = nFE° = – G°


electrical work done = nFE = – G

DIFFERENT TYPE OF ELECTRODES/HALF CELL


Type Example Half-cell reaction Electrode potential
(reduction)

0.0591
Metal - Metal ion M/Mn+ Mn+ + ne– M(s) E = E° + log [Mn+]
n

Gas - ion Pt / H2 (P atm) H+ (aq) + e–

1 PH 2
/ H+ (XM) H (P atm) E = E° – 0.0591 log
2 2 [H ]

[Fe 2 ]
Oxidation - reduction Pt / Fe2+ , Fe3+ Fe3+ + e– Fe2+ E = E° – 0.0591 log
[Fe 3 ]

Metal - Ag/AgCl, Cl– AgCl (s) + e– E Cl / AgCl / Ag


E Cl
0
/ AgCl / Ag

insoluble salt Anion Ag (s) + Cl– 0.0591 log [Cl ]

Calomel electrode Cl–(aq)/Hg/Hg2Cl 2 Hg2Cl2(s) + 2e– E= E° –0.0591 log [Cl–]


2Hg(l) + 2Cl–(aq.)

Gibb's Helmhaltz equation :


4 G
G = H + T 4T
4 G
H = –nFE + nFT 4T P

27
'THE ELECTROCHEMICAL SERIES'
Element Electrode Reduction Reaction Standard electrode Reduction
potential E0, Volts

Li Li+ + e Li – 3.05

K K+ + e– K – 2.93

Ba Ba+2 + 2e– Ba – 2.90

Ca Ca +2 + 2e– Ca – 2.87

Na Na+ + e– Na – 2.71

Mg Mg+2 + 2e– Mg – 2.37

Al Al+3 + 3e– Al – 1.66

Mn Mn+2 + 2e – Mn – 1.18

H2 O 2H2O + 2e– H2 + 2OH– – 0.828

Zn Zn+2 + 2e– Zn – 0.76

Cr Cr+3 + 3e– Cr – 0.74

Fe Fe+2 + 2e– Fe – 0.44

Cd Cd+2 + 2e– Cd – 0.40

Ni Ni+2 + 2e– Ni – 0.25

Sn Sn +2 + 2e – Sn – 0.14

Pb Pb+2 + 2e– Pb – 0.13

H2 2H+ + 2e– H2 0

Cu Cu+2 + 2e– Cu + 0.34

I2 I2 + 2e– 2I– + 0.54

Hg Hg2+2 + 2e 2Hg + 0.79

Ag Ag+ + e– Ag + 0.80

Hg Hg+2 + 2e– Hg + 0.85

Br 2 Br2 + 2e– 2Br– + 1.08

O2 O2+ 4H++4e– 2H2O + 1.229

Cl 2 Cl2 + 2e– 2Cl– + 1.36

Au Au+3 + 3e Au + 1.50

F2 F2 + 2e– 2F– + 2.87

28
CONDUCTION IN ELECTROLYTES
Conductance Specific Molar
Conductivity Conductivity
Symbol C 5
Unit 6–1 6–1 cm–1 6 –1 cm 2 mol–1

Specific conductance of conductance of conductance of that


volume within unit volume volume which contain
electrode exactly one mole

Change with decrease with Decrease with Increase with in


concentraction decrease in decrease in decrease in
concentration concentration concentration

1
Formula C = k= =K × V
R
k = C × cell constant V = Volume of solution
contain 1 mole of electrolyte

Factors (i) nature of (i) nature of (i) nature of electrolyte


electrolyte electrolyte (ii) concentration
(ii) concentration (ii) concentration of electrolyte
of electrolyte of electrolyte
(iii) Type of cell.

KOHLRAUSEH'S LAW :
7 m (A x B y ) x y –

7 m (K 2 SO 4 ) 2 –

7 m (Na 3 PO 4 ) 3 –

7 m [Fe 2 (SO 4 ) 3 ] 2 3 –

FORMULA

(1) R=8
A
1000
(2) =k×
m
M
1000
(3) k
N
eq.

(4) for strong electrolyte m


= m – b C

29
Vapour Pressure : Pressure of any volatile substance at any given temperature.
T( V.P. (
Attractive forces ( V.P.
Raoult’s law :
Non volatile solute and volatile solvent solution.

PA = PA) X A

Colligative Properties : Properties depends on no. of particles of Non volatile solute in solution.

(1) Relative lowering of V.P. :

PA) PA nB nB
i i
P )
A nA nB nA

Where n B = mole of Non-volatile solute.


i = Vant Hoff’s factor.
(2) Elevation in B.P. :
Tb = (Tb –Tb) = i. kb × m.

RTb2
where K b
1000 v

where Tb = B.P. of pure solvent.


v
= Latent heat of vapourization per gm
Kb = molal elevation constant
M = molar mass

H vap
where =
M
v

( 3) Depression in FP.
Tf = Tf – Tf = i kf × m

RTf2
where kf =
1000 f
Tf = f.p. of pure solvent
kf = molal depression contsant
f
= latent heat of fusion per gm.
( 4) Osmotic presssure :

9 - PA) PA

9 = iC. S.T.

30
where 9 = osmotic pressure
C = molarity (mole/lit)
S = R = const. for solution.
Sol.(1) Sol (2)
If 9 1 = 92 Isotonic

If 91 > 92

Van’t Hoff factor for different Cases of solutes undergoing Ionisation and Association :

Solute Example Ionisation/association y* van'thoff abnormal


(x degree) factor mol. wt. (m 1 )
Non- urea-glucose, none 1 1 normal mol.wt.
electrolyte sucrose etc. (m 1 )

m1
Binary NaCl, KCl, HCl AB A B– 2 (1 + x)
1 x x x (1 x)
electrolyte CH 3 COOH,
A+B – FeSO 4 etc.

m1
Ternary K2 SO 4 , BaCl 2 , A 2B 2A B 2– 3 (1+2x)
1 x 2x x (1 2x)

m1
electrolyte K3 [Fe(CN) 6], AB 3 A3 3B – 4 (1+3x)
1 x x 3x (1 3x )
A2 B, AB 3 FeCl3

1 x 2 x 2m 1
Associated benzoic acid 2A A2 1
2 2 2 (2 x)
Solute in benzene

1
forming dimer A A2
(1 x ) 2 x/2

m1
any solute nA An 1 1 1
1 –1 x 1 –1 x
n n n
1
forming A An
(1 x ) n x /2
polymer An
m1
General one mole of A yB y [1+(y–1)x]
[1 (y 1)x]
solute giving
y mol of products
* number of products from one mole solute

31
Raoult’s law :
(1) Volatile binary liquid mix :
Volatile liq. A B
Mole fraction X A/Y A XB/YA liq/vapour

V.P. of pure liq. PA) PB)

Binary liquid solution :

By Raoult’s law PT = PA) X A + PB) X B = PA + PB ......(i)

By Dalton’s law PA = YAPT ......(ii)


PB = YBPT ......(iii)

Ideal and Non-Ideal solution :

Ideal solution : H solution=0

Non-Ideal solution :
(1) Solution showing +ve deviation :
F < F1 & F2
VT > V1 + V2 Hsolution> 0

(2) Solution showing –ve deviation :


F > F 1 & F2
VT < (V1 +V2 )

Hsolution < 0

32
DEVIATION FROM RAOULT'S LAW

Positive deviation Negative deviation Zero deviation


( H=+ve) ( H=–ve) ( H=0)
(i) ethanol + cyclohexane acetone + chloroform benzene + toluene
(ii) acetone + carbon disulphide benzene + chlorform n-hexane + n-heptane

(iii) acetone + benzene nitric acid + chloroform ethyl bromide + ethyl iodide

(iv) ethanol + aceton acetone + aniline chlorobenzene + bromo


benzene

(v) ethanol + water water + nitric acid

(vi) carbon tetrachloride diethyl ether +


chloroform chloroform
Azeotropic mixtures :
Some liquids on mixing form azeotropes which are binary mixture having same composition in liquid and
vapour phase and boil at a constant temperature. Azeotropic mixture cannot be separated by fractional
distillation.
Types of Azeotropic mixtures
(i) Minimum boiling Azeotropic mixtures
The mixture of two liquids whose boiling point is less than either of the two pure components. They are formed
by non-ideal solutions showing positive deviation. For example (95.5%) + water (4.5%) + water boils at
351.15 K.
(ii) Maximum boiling Azeotropic mixtures
The mixture of two liquids whose boiling point are more than either of the two pure components. They are
formed by non-ideal solutions showing negative deviation. For example HNO3 (68%) + water (32%) mixture
boils at 393.5 K.

33
Various type of Criptals :
Some Important Characteristics of Various types of Crystals
Characteristics Ionic Crystals Covalent Molecular Metallic
Crystals Crystals Crystals
Units that Cations and Atoms Molecules Positive ions in a
occupy lattice anions "sea or pond" of
points electrons.
Binding Electrostatic Shared vander Waals Electrostatic
forces attraction electrons or Dipole- attraction between
between ions dipole positively charged
ions and negatively
charged electrons.

Hardness Hard Very hard Soft Hard or soft


Graphite

Brittleness Brittle Intermediate Low Low

Melting point High Very high Low Varying from


moderate to high
Electrical Semi cond- Non-con- Ba d Good conductors
Conduction uctor due to ductor conductor
crystal impe- Graphite
rfections,con- is good
ductor in fused conductor
state
Solubility in Soluble Insoluble Soluble as Good conductors
Polar solvents well as
insoluble
Heat of NaCl(s) Graphite NH 3 (s) Cu(s)
Vaporisation 170-75 718-43 23.55 304.59
(kj mol )–1

Heat of NaCl – NH 3 (s) Cu(s)


fusion 28.45 – 5.65 13.016
(kj mol )–1

Example NaCl, KNO3 Diamond, H2 O(s), Na, Cu, Ag, Fe,


CsCl, Na 2SO 4 graphite, CO 2(s), Pt, alloys
ZnS Quartz Sulphur,
(SiO 2), Sugar,
SiC Iodine,noble
gases

34
THE SEVEN CRYSTAL SYSTEMS
Name of Axes Angles Bravais Lattices
System
1. Cubic a = b = c :;) Primitive, Face-centred,
Body centred = 3
2. Tetragonal a= b c :;) Primitive, Body centred = 2
3. Rhombohedral a = b= c :;) Primitive = 1
or Trigonal
4. Orthorhombic a b c :;) Primitive, Face-centred,
or Rhombic Body centred End centred = 4
5. Monoclinic a b c :;)< Primitive, End - centred = 2
90)
6. Triclinic a b c 90° Primitive = 1
7. Hexagonal a=b c = 90° Primitive = 1
120° Total = 14

CUBIC UNIT CELL


Unit cell Relation Packing Co-ordinatin Effective number
between fraction number of particle
r and a
a
Simple cubic r = 52 . 4 % 6 1
2
Body centred
a 3
cubic r = 68% 8 2
4

a 2
Face centred r = 74% 12 4
4
cubic

ZM
Density : d = gm / cm 3
N A xa 3
Where Z = effective number of particle
M= molar mass
NA = Avogarodro's number
a = edge length (cm)
Three dimensional close packing :
Hexagonal close packing (HCP) :
Effective number of particle = 6
Effective number of octahedral void = 6
Effective number of tetrahedral void = 12
Packing fraction
= 74% ; co-ordination number = 12
r 2
a= ;b=4 r
2 3

35
6 fold axis
9

A
7 8

B 5
4
A 3 X 6
A
2 1
B
B

A A 11 12

10

ABABAB... or hexagonal close packing (hcp) of spheres Coordination number of hcp and ccp structure

Cubic close packing (CCP) :

Effective number of particle = 4

Effective number of octahedral void = 4

Effective number of tetrahedral void = 8

Packing fraction = 74% ;

co-ordination number =12

a 2
r
4

Different type of voids and their radius ratio :

Limiting radius ratio for various types of sites

Limiting radius Coordination Structural Example

ratio = r/R Number of cation Arrangement

(Geometry of voids)

0.155 - 0.225 3 Plane Trigonal Boron Oxide

0.225 - 0.414 4 Tetrahedral ZnS, SiO 2

0.414 - 0.732 4 Square planaer –

0.414 - 0.732 6 Octahedral NaCl, MgO 2

0.732 - 1.000 8 Cubic CsCl

36
37
Cr 2 O 3 /Al2 O 3 Cr2 O 3 /Al2 O 3
Aromatization : ; CH 3
500°C
500°C
Isomerization :
Anh AlCl 3 Anh AlCl 3
Anh AlCl3 CH 3 (CH 2) 5 CH 3 CH 3 (CH 2) 6 CH 3
, H Cl , H Cl
H Cl Isooctane
(Triptane) (2,2,3-trimethyl butane)
Combustion : Pyrolysis:
3n 1
CnH 2n+2 + O2 nCO 2 (n 1)H 2 O 2CH 3 — CH 2 — CH 3 CH 3 — CH CH 2 CH 3 — CH 3 CH 4 H2
2 600 C

CH 4 2O 2 CO 2 2H 2 O CH 3 — CH 2 — CH 2 — CH 3 600 C
CH 3 — CH 2 — CH CH 2

CH 3 — CH 3
7
O 2CO 2 3H 2 O + + +
2 2

38
39
Nutshell reaction of Alkene

40
41
42
43
Comparison of S N1 and SN 2
S N1 S N2
A Kinetics 1 st order 2 nd order
B Rate k[RX] k[RX][Nu:— ]
C Stereochemistry Racemisation Inversion
D Substrate 3° > 2°> 1° > MeX MeX > 1° > 2°> 3°
E Nucleophile Not important Needs Strong Nu
F Solvent Good ionizing Faster in aprotic
G Leaving Group Needs Good LG Needs Good LG
H Rearrangement Possible Not Possible

Comparision of E1 and E2
E1 E2
A Kinetics 1 st order 2 nd order
B Rate k[RX] k[RX][B:— ]
C Stereochemistry No special geometry Anti-periplanar
D Substrate 3° > 2°> > > 1° 3° > 2° > 1°
E Base Strength Not im portant Needs Strong bases
F Solvent Good ionizing Polarity not import
G Leaving Group Needs Good LG Needs Good LG
H Rearrangement Possible Not Possible

Summary of S N 1, S N 2, E1, and E2 reactions


RX Mechanis m Nu:—/:B — Solvent Temp.

Better Nu:—
SN2 Low
H O :— , C 2 H 5 O : —
1° Polar aprotic
Strong & bulky
E2 High
base (C H 3 ) 3 C O : —
SN2 HO: — C 2 H 5 O : — L ow
Polar aprotic
E2 (C H 3 ) 3 C O: — High

(S N 1) (Solve nt (L ow)
Polar aprotic
(E1) (Solvent) (High)

SN1 Solve nt Protic L ow



E1 Solve nt Protic High

44
• Reduction
O
H3C C H CH 3 — CH 2 — OH
LiAlH 4 / H 2 O
NaBH 4 / EtOH

O OH
H3C C CH 3 H3C CH CH 3
LiAlH 4 / H 2 O
NaBH 4 / EtOH

O
H3C C Cl CH 3 –CH 2–OH
LiAlH 4 / Et 2 O

O OH
H 3C CH 2 C O C2 H5 H3C CH 2 CH 2 + C 2 H 5 OH
LiAlH 4 / Et 2 O
Na / EtOH

O
H2C CH 2 CH 3 –CH 2 –OH
LiAlH 4 / Et2 O
H3 O

O OH
H3C CH CH 2 LiAlH 4 / Et 2 O
H3C CH CH 2 H
H3 O

• By Fermentation
C 12 H 22 O 11 H2O Invertase
C 6 H 12 O 6 C 6 H 12 O 6 Zymase
2C 2 H 5 OH CO 2
sucrose Glucose Fructose zymase

2 C 6 H 10 O 5 nH 2 O nC 12 H 22 O 11 2C 6 H 12 O 6
Diastase Maltose
n H2 O
starch

45
Reagent

PCC/CH 2 Cl2
PDC/CH 2 Cl2 O O .8
Jones Reagent
H 2 CrO 4 /Aq.
H 3 C CH 2 CH 2 C H H3C CH 2 C CH 3 No reaction
Acetone
O O O .8
H 3 C CH2 CH 2 C H H3 C C OH + CH 3 C OH
O O CH 3
Cu/500°C H 3 C CH 2 CH 2 C H CH 3 CH 2 C CH 3 H3C C CH 2
Al(OBu t )3 O O
Acetone H 3C CH 2 CH 2 C H H3 C CH 2 C CH 3 -
or cyclohexanone
Lucas Reagent Cloudiness appear within five min. Immediately
HCl/ZnCl 2 upon heating after 30 mins.
at normal temp. no. reaction
Victor Mayer's Test
CH 3 CH 3
P/ I 2 C H 3 – C H 2– C H 2 – C H 2 – I H 3 C CH 2 CH I H 3C C I
CH 3
CH 3
AgNO3 C H 3– C H 2 – C H 2 – N O 2 ( C H 3 ) 3 – NO 2
H3C CH2 CH NO 2
CH3 No reaction
HNO2 H3C C H2 C NO 2
NaOH H3 C CH2 CH NO 2
N OH
Nitrolic acid N O
46
47
48
49
50
Nutshell preview and review of Carboxylic Acids
PREPARATION & REACTION

51
52
Heating effect
-Hydroxy acid
-Hydroxy acid O OH O
O O
H
+
C CH 2 CH 2 C OH
O H HO C O H2 C C C OH
H HC CH 3 H
+

H3 C CH HC CH 3 H3C CH 3
C O O CH 3 O
C OH H O O H
H
+

O O Lacitide H3 C CH CH 2 C OH CH CH C OH

Keto acid:
Hydroxy acid
O O O
O O
H 3C C C C OH H3C C CH 3
C H
+
C H2
CO 2
OH -Lactone
O O
OH O NaOH
O2 N C C OH H3C C OH
O H2
O
C H C NO 2
+

OH
O -Lactone
O H HNO 2

H
O O H O O
+

Ph CH CH C ONa Ph CH CH C H P h3 CH2 C H

53
54
Amino Acid :
O O
O O
NH 2 HO C NH C
H3 C CH OH H
+

CH CH 3 H3C CH CH CH 3 NH
C OH H2N NH 2
C NH
O
O
O
NH 2 O O C O
OH H
+

H3 C CH CH 2 C OH H3C CH CH C OH NH 2
NH
55
METHOD OF PREPARATION OF AMINE
• Hoffmann's Ammonolysis

H 3C CH 2I C 2 H 5I +
N H3 H3C C H2 I
(CH 3 CH 2 )2 NH (C 2 H 5 ) 3 N (C 2 H 5 ) 4 NI
H 3 C CH 2 Br -HX
H 3 C CH 2 NH 2

Good yield 1° Amine (If NH3 1° excess) / Not suitable for Aryl Amine)
Reactivity - R-I > R-Br > R-Cl
• Gabriel / Phthalimide Synthesis :

O O O O
C C C C OH
NH 3 K OH H2O
O N H C H 3 -I N CH 3 H 3 C NH 2 +
H
C C
+

C C OH
O O O O

2° & 3° can't be prepared : Aromatic amine can't prepared Eschweiler Blarke synthesis
• Reduction H OH
R 2 NH + C O R 2 N CH 2
H H
+

+ Na/EtO H
H3C N C LiAlH /Et O H 3 C CH 2 NH 2 R 2 N CH 3 R 2N CH 2
O C H
4 2

R CH N OH
LiAlH 4 /Et 2 O
R C H 2 NH 2 O
or Na/EtO H Formic acid act as
or B 2 H 6 /T HF reducting agent by transferring R 2 N CH 2
a hydride to the electron-deficien t
• Hoffmann Boroamide Degradation : carbon & is oxidized to C O 2
O H2O
Reductive Amination Leuckart reaction
Br2
H 3 C C NH 2 H3C N C O H 3 C NH 2 O
NH 2
KOH HO O
N H 4H C O
• Schimdt Reaction : Ph C CH 3 Ph C CH 3
O O
NMe 2
HN 3 + H 2 SO 4 H3O O
+

R C OH R N C O R NH 2 H C N Me 2
Et C Et (DM F)/
Et CH Et
• Lossen Reaction

O H2N OH H 3O
O
NaN 3 / H3O
+ +

R C Cl R N C O R NH 2 R C Cl R N C O R NH 2
H 3C C Cl
O H2N
N H2 H3O
+

H ONO + H+
R N C O R NH 2

+
H /H 2 O
R N C O R NH 2
H O/ H 2 O

+ O Cl-NH 2
+ H/H 2 O
R N C R NH 2 + H C OH R Mgx R NH 2
Sn/HCl

56
CHEMICAL PROPERTIES OF AMINES
..
Reagent R NH 2 (1°) R 2 NH(2°) R3N (3°) NH 2

+ +
+ + Cl
1. HCl R 3N NH 3 Cl
R NH 3 Cl R 2 NH 2 Cl
H
+
2. C H 3 —B r R—NH—CH3 R 2 NH —C H 3 R 3 N CH 3 Br NH CH 3

O O O O
3. No reaction
H 3 C C Cl R NH C CH 3 R2N C CH 3 NH C CH 3

O O O O
4. No reaction NH C CH 3
(C H 3 C) 2 O R NH C CH 3 R2N C C H3

O
R N SO 2 Ph
5. Ph—SO 2 C l H soluble
R 2 N S Ph
No reaction NH SO 2 Ph
NaOH O NaOH
[R N SO 2 Ph]Na+ Insoluble

6. Carbylamine Test No reaction No reaction


+
R N C +
N C

+
7. HNO=O /H + R— OH +N 2 +H C l R 2 N –N = O
+
R 3 N HON = O N 2 Cl OH
H2O

(0°— 5°C)

8. Hoffmann Mustard Oil Test

S S S KO H
1. – NH C S
C S R NH C SH R 2 N C SH 2

/HgCl 2 R–N=C=S + HgS No reaction No reaction H Cl


Ph N C S + Ph-NH 2
2. Hoffmann Test
COOEt CONH R O C NR 2 O C NH Ph
COOEt CONH R COOEt No reaction O C NH Ph
Oxamide (solid) Oxamic ester (liquid)

R'MgX R'–H+R–NHMgBr R"H +R 2 NMgBr No reaction R'H+PhNHMgBr

O N R NR 2 No reaction N Ph

Cl
O C (RNH) 2 C=O (R 2 N) 2 C=O No reaction Ph–N=C=O
Cl

O O R O
Ph–N =C=O Ph NH C N No reaction
Ph NH C NH R R Ph NH C NH Ph
Oxidation R–CH2–NH2 R2NH R3N
KMnO 4 R–CH=NH H3 O RCHO R 2 N–NR 2 No reaction
H 2 SO 5 R–CH 2 –NH–OH R 2 N–O–H R 3N = O
R C N OH
OH
R2CH–NH2 :
KMnO 4 R 2 C =NH H 3O R 2 C=O
H 2 SO 5

57
58
59
60
61
62
63
64
65
66
NUTSHELL REVIEW & PREVIEW OF

ORGANIC NAME REACTIONS

• Aldol Condensation
O O O O O
OH
H C CH 2 OH H OH
+

H C CH 2 C CH 3 H C CH 2 CH CH 3 H C C C CH 3
H H H
H
• Claisen Condensation
O O O O O O O
H 3 C C OEt EtO H
+

EtO C CH 2 C CH 3 EtO C CH 2 C CH 3 H C C C O C2 H5
OC 2 H 5 H2
OEt
• Perkin Condensation

H H O H
O O
C + HC C C C H3
H 3C C ONa
C C C OH
O HO O O H
Cinnamic acid

• Benzoin Condensation
O O OH
KC N
2 C H EtO H C CH Benzoin

CH3 CH3
• Wittig Reaction H3C C O + C H2 PPh 3
DMSO
H 3 C C C H 2 + Ph 3 P O

OH O O
Na OI
• Haloform Reaction H 3 C CH R1 H3C C R1
Na OH
CH 3 I+ R
1
C ONa
I2

H Cl H Cl O H
CH Cl 3
R N C R N C R N C Isocyanide
• Carbylamine Test KOH
H Cl H Cl

• Reimer Tiemann Reaction H


O O O H OH H
Cl O H C O
H C
+ CCl 2
CHCl 3 Cl
H
+

K OH
CCl 2
OH O
C Cl 4
C OH
K OH

H O O
• Kobe's Schimdt Reaction C
O H 125°C OH
NaOH m ajor

CO 2/H+ O
HO C
225°
OH

67
• Hofmann Bromoamide Degradation
O O O
Br 2 HO
R C NH 2 R C N Br R C N Br R N C O H2O
R NH 2 + K 2 CO 3
KO H
H

N aN 3 O
R C N N N R N C O R N H2
H3 O
O
• Curtius Reaction R C Cl
O
R NH 2
HON O H3O
H 3 N-N H 2 R C N H-N H 2 R N C O
H
+

O O
• Lossen Reaction H 2 N- OH Accl
R N C O
H3 O
R NH 2
R C Cl R C N OH or H +
H

O HN3
• Schimdt Reaction R N C O R NH 2
H3O
R C OH H 2S O 4

• Meerwein Ponndorfverly reduction A l(O Pr i) 3


OH O
Pr iO H

• Oppeneuer Oxidation (A lO B u t ) 3
O OH
M e 2C O

• Cannizzaro reaction

O O O O O O
5 0% slao +
H C H H3C C H C H H C OH + H C H H C ONa + C H 3 OH
NaOH RDS
H O H H

+ OH O
• Bayer villiger oxidation H 3C OH
O C H 3 C C O C CF 3
O
O F3C C OO H O
C (peracid)
O O C CF 3
F 3C C O
H3 C

+ OH
O OH 1,2
H3C C O
+
-H
H 3C C O H 3C C O
+
Ph — Shift

• Beckmann Rearrangement

R R' R R' O H O
C H 2S O 4
C + H2O
:N R' C N R R' C N R R' C N R
N +
OH OH 2 H
[Back (to OH)gr. m igrate]

68
• Pinacol Pincolone rearrangement
Cl

H
+
+ Ph
Cl C C Cl C C Ph
C C -H 2O — H+
OH O Ph
OH OH

• Benzylic acid rearrangement

KOH
O
+
C C O C C O C C O C C OK
O
O OH O OH OH
• Fries Rearrangement
O
O C CH 3 O
60°
H O C CH 3 (P)
AlCl 3(Anh)

H O C CH 3
Phenyl 120°
acetate O (O)
O ,P (Hydroxy acetophenone)
• Claisen Rearrangement
"If ortho position is blocked"
14
O C H2 C H C H2 O H
14
14 O C H2 C H C H2 O H
2 0 0 °C
C H2 C H C H2 H3C C H3
2 0 0 °C

C H2 C H C H2
14

• Birch Reduction
O
O R(+ M) O R C OH COOH
N a/ Na/ Na/
liq. N H 3 ; liq. N H 3 ; liq. NH 3

N a/
R H
R C C R' C C Na/
liq. N H 3 R C C H R C CNa+
H R ; liq. NH 3
(Acid-base reaction)
trans

• Gabriel Synthesis
O O O O
C C C
NH 3 KO H + C
O N H N K
CH 3 -I
N CH 3
C C C C
O O O
O O
H 3O + NH 2 — N H 2
C OH
+ CH 5 NH 2 O
C OH C
+
O NH
H 3 C NH 2
NH
C
O

69
Name Reactant Reagent Product

Clemmensen Reduction Aldehyde & Ketone Zn-Hg/conc. HCl Alkane

N +2C l OH NH 2
NaOH (phenol) Azo Dyne (Detection of
Coupling Reaction OH or NH 2 gr)
+ or HCl (Aniline)

.. NaNO 2 + HCl +
Diazotization NH 2 N NCl
0° – 5°C

H
Diels Alder Reaction or
Die ne
H
Dien ophile cyclic addition product
O
Etard reaction H 3C CrO 2 Cl2 /CS 2
H
(Benza ldehyde)

Fittig Reaction H alo benzene Na/Dry ether Diphenyl

Friedel Craft alkylation + R— X Anhydrous AlCl 3 Alkyl Benzene

O
Friedel Craft acylation +R C Cl or (RCO)2O Anhydrous AlCl 3 Acyl Benzene

Gattermann aldehyde synthesis C 6H 6 HCN+ HCl + ZnCl2/H 3 O + Benzaldehyde

Gattermann-Koch reaction C 6 H 6 (CO + HCl) anhy AlCl 3 Benzaldehyde

carboxylic acid having halogenated


Hell-Volhard-Zelinksy reaction Br 2 / red P
-hydrogen atom carboxylic acid
CH 3CH 2— N= C= S + HgS
Hoffmann mustard oil reaction primary aliphatic amine + CS 2 HgCl2 /
(black)

Hunsdiecker reaction Ag salt of carboxylic acid Br2 /CCl 4 , 80°C alkyl or aryl bromide

alkali metal salt of carboxylic alkane, alkene and


Kolbe electrolytic reaction electrolysis
acid alkyne
[(CH 3 )2CHO]3 Al +
Meerwein - Ponndorf Ketone Secondary alcohol
(CH 3 )2 CHOH

Mendius reaction alkyl or aryl cyanide Na/C 2H 5 OH primary amine

H 2 , Pd/BaSO 4, S, boiling
Rosenmund reduction acid chloride aldehyde
xylene
Raney Ni/H 2,
Sabatier-Senderens reaction Unsaturated hydrocarbon Alkane
200— 300°C
CuCl/HCl or CuBr/HBr or
Sandmeyer reaction C 6 H 5 N 2 Cl — halo or cyanobenzene
CuCN/KCN, heat

Gattermann Reaction C 6 H 5 N 2+ Cl— Cu/Hx(HBr/HBr/HBr Halobenzene

benzolytated product
Schotten-Baumann reaction (phenol or aniline or alcohol) NaOH + C 6 H 5COCl O O
O C CH3 NH C C H3

Stephen reaction alkyl cyanide SnCl2 /HCl Aldehyde

Ullmann reaction Iodobenzene Cu (heat) Diphenyl

sodium alkoxide or
Williamson synthesis alkyl halide ether
sodium phenoxide

Wurtz-Fittig reaction alkyl halide + aryl halide Na/dry ether alkyl benzene

70
ADDITION POLYMERS

S. Abbrevi Starting Nature of


Name of Polymer Properties Applications
No ation Materials Polymer
I. Polyolefins
1. Polyethylene or CH 2= CH 2 Low density Transparent, Packing material bags,
Polyethene homopolymer moderate tensile insulation for electrical
(branched chain strength, high wires and cables.
growth toughness Buckets, tubes, house
ware pipes, bottles and
toys
2. Polypropylene or CH 3CH= CH 2 Homopolymer, Harder and Packing of textiles and
Polypropene or linear, chain stronger than foods, liners for bags,
Herculon growth polyethene heat shrinkage wraps,
carpet fibres, ropes,
automobile mouldings,
stronger pipes and
bottles.
3. Polystyrene or Styron C 6 H 5 CH= CH 2 Homopolymer, Transparent Plastic toys, household
linear, chain wares, radio and
growth television bodies,
refrigerator linings.
II. Polydienes
1. Neoprene Cl Homopolymer, Rubber like, a Horses shoe heels,
H 2C CH C CH 2 chain growth superior resistant stoppers.
Chloroprene or to aerial oxidation,
2-Chloro-1,3-butadiene and oils, gasoline
etc.
2 Buna S SBR or H 2 C CH CH C H 2 Copolymer, Rubber like, a Manufacturer of tyres,
(Styrene- Butadiene, GRS 1,3-butadiene chain growth superior resistant rubber soles, water
Rubber) to aerial oxidation, proof shoes.
and C 6 H 5CH = CH 2
Styrene
and oils, gasoline
etc.
III. Polyacrylates
1. Polymethylmethacrylate PMM A C H3 Homopolymer Hard, transparent, Lenses, light covers,
(Flexiglass Lucite, H 2 C C C OOCH 3 excellent light light shades,
Acrylite or Perspex transm ission. signboards, transparent
Optical clarity domes, skylights, air
better than glass, craft windows, dentures
takes up colours. and plastic jewellery.
2. Polyethylacrylate H 2C CH CO OC 2 H 5 Homopolymer Tough, rubber like
product.
3. Polyacrylonitrile or PAN CH 2= CH— CN Homopolymer Hard, horny and Orion, acrilon used for
Orlon high melting making clothes,
materials. carpets, blankets and
preparation of other
polymers.
IV. Polyhalofins
1. Polyvinyl chloride PVC CH 2= CH— Cl Homopolymer, Pliable (easily (i) Plasticised with
chain growth moulded) polyester polymers
used in rain coats, hand
bags, shower curtains,
fabrics, shoe soles, vinyl
flooring (ii) Good
electrical insulator, (iii)
Hose pipes.
2. Polytetrafluoroethylene, PTFE F 2 C= CF 2 Homopolymer Flexible and inert (ii) For nonstick utensils
or Teflon to solvents, boiling coating (ii) Making
acids even gaskets, pump
aquaregia, stable packings, valves, seals,
upto 598 K non lubricated bearings.
3. Polymonochlorotrifluor PCTFE ClFC= CF 2 Less resistant to Similar to those of
o-ethylene heat and Teflon.
chemicals due to
presence of
chlorine atom s.

71
CONDENSATION POLYMERS
S. Abbre Starting Nature of
Name of Polymer Properties Applications
No viation Materials Polymer
I. Polyesters
1. Terylene or Dacron HO CH 2 CH 2 OH
Copolymer, Fibre crease For wash and wear
or Mylar step growth, resistant, low fabrics, tyre cords,
Ethylene glycol or Ethane-1,2-diol

linear m oisture sea belts and sails.


And
O O content, not
HO C C OH dam aged by
pests likes
moths.
Terephthalic acid or
Benzene-1,4-dicarboxylic acid

2. Glyptal or Alkyl HO C H2 CH 2 OH C opolymer, Thermoplastic, Paints and lacquers.


resin Ethylen e glycol
linear step dissolves in
growth suitable solvents
and
HOOC COOH
and solutions,
on evaporation
leaves a tough
but not flexible
Phthalic acid or
Benzene-1,2-dicarbo xylic acid

film.
II. Polyamides
1. Nylon-6,6 O O C opolymer,
HO C(CH 2 ) 4 C OH linear, step
Adipic acid growth
and
H 2 N (CH 2 )6 NH 2
Hexa methylenediamine

2 Nylon-6,10 H 2 N(C H 2 ) 6 NH 2 Copolymer, High tensile (i) Textile fabrics,


H examethylene diam in e linear, step strength, carpets, bristles for
growth abrasions brushes. (ii)
and
HOOC(CH 2 )8 COOH
resistant, Substitute of metals
somewhat in bearings (iii)
Sebacic acid

elastic Gears elastic


hosiery.
Mountaineering
ropes, tyre cords,
fabrics.
3. Nylon-6 or Perlon L NH O Hom opolym er Mountaineering
, linear ropes, tyre cords,
fabrics.
Caprolactum
Fermaldehyde resins
1. Phenolformaldehyd Phenol and Copolymer, (i) with low degree
e resin or Bakelite formaldehyde step growth polymerization for
binding glue, wood,
varnishes, lacquers.
(ii) With high
degree
polymerisation for
combs, for mica
table tops, fountain
pen barrels,
electrical goods
(switches and
plugs), gramophone
records.
2. Melamine Melamine and Copolymer, Tough, rubber Non-breakable and
formaldehyde resin formaldehyde step growth like product. non-plastic
crockery.

72
CARBOHYDRATES
• Polyhydroxy aldehyde or Ketone (cyclic hemiacetal / or hemiacetal or acetal or ketal
• Monosaccaride (CnHznOn) : single unit, can't be hydrolysed : Glucose; fructose (by glycosydic linkage)
Sucrose H3O Glucose + Fructose; maltose H 3O 2 Glucose unit

Lactose H3O Glucose + Galactose


• Polysaccaride : Contain more than monosaccaride units
(C6 H10O5) n : Starch & cellulose.

TYPE OF SUGAR

Give Test Reducing Non Reducing


1. Tollen's Reagent +ve test –ve test
2. Fehling Reagent +ve test –ve test
3. Benedict Test +ve test –ve test
4. Mutarotation Ye s No
O
5. Functional Unit C C O C C C
OH OH

O H O H

OH OR
He miacetal A cetal

O H O R

OH OR
Hemiketal K etal

6. Example All monossaccaride Dissaccaride : Sucrose


Glucose; fructose, Polysaccaride : starch cellulose
mannose, galactose,
Dissaccaride : maltose; lactose

• Mutarotation: When either form is placed in solution it slowly form the other via open chain aldehyde
form & gradual change in specific rotation until specific value is reached.
6
H2C OH H H 2C OH

H 5
O OH H O H H O H
H H
O
OH OH H C OH H
4 1
H
OH H OH OH OH
3 2
H OH H OH H OH
-D-Glucose
-D-Glucose [ ]0 = 52.1
[ ] D = + 112°
[ ]D = + 19°
• Anomer's : Difter in configuration at 1st carbon due to hemi (acetal or ketal) ring formation. The new-
symmetric carbon is referred to as Anomeic carbon.
• Epimer's : Distereomer's which differ in conformation at one chiral carbon [maltose & glucose (epimers
carbon is C 2]

73
• Sucrose : • Maltose
OH H 2 C OH H 2 C OH
O O O H H O H
H H CH2OH H
H O H H
OH OH H OH H OH H
OH CH2 H OH O OH
:
H H OH H H
OH G lycosidic
linkage
OH
-D -G lu c o se -D -F ru c to se (u n it)
G ly co sid ic lin ka g e Two a-D-Glucos e unit

• Starch : (Amylose & Amylopectin)


• Amylose : (Straight Chain) :

H 2 C OH H2 C O H
O H H O H H O H
H H
O 2 1 4 1
OH H OH H
O O O
H OH H OH
( -1,4 Glycosidic linkage)
(i) Soluble in H2O & give blue colour with I2 (ii) 10 to 20%
• Amylopectin (Branch chain) : (C6H12O5)n

H 2 C OH H 2 C OH
(C 6 H 12 O 5 )n
H O H H O H
nH 2 O Diatase
H H
OH H
4 1 C 12 H 22 O 11 (maltose)
OH H
O O O nH 2 O maltose
H OH OH O 2C 6 H 12 O 6 -D-Glucose
H
1,6-Glycosidic linkage
CH 2 Cellulose
O H H O nH 2 O Cellulose
nC 6 H 12 O 6
O -D-Glucose
n

1,4-Glycosidic linkage

• Cellulose : (Straight chain -D-Glucose unit)

H 2 C OH H OH
O H2 C OH
H
O H H O
H OH H O
1 H H
OH H OH
O OH H
H H O O
H
H OH CH 2 OH O
H OH
( -1,4-Glucosidic linkage)

74
AMINO ACIDS STRUCTURE OF
CH 3 PROTEINS
• Primary structure : The
• H3 N+ — CH 2 — COO — H 3 N + — CH— COO —
sequence in which various
amino acids are arranged in a
Glycine -A lanine

Three protein is known as the


Name of amino primary structure of a protein.
S.No. Structure of R letter
acid The number, sequence a nd
symbol
identity of amino acids in a
1. Glycine –H Gly
protein constitute primary
2 Alanine –CH 3 Ala structure of a protein.
3. Valine –CH(CH 3 )2 Val • Secondary structure : The
4. Leucine –CHCH(CH 3 )2 Leu coiling of the long strings of
CH CH 2 CH 3 amino acids in a protein is its
5. Isoleucine Ile secondary structure. The -
CH 3 helix is a common secondary
(C H 2 )3 NH C NH 2 structure. In -helix, the
6. Arginine Arg peptide chain coils and the
NH
turns of the coi l are held
7. Lysine –(CH 2 )4 NH 2 Lys
together by hydrogen bonds.
8. Glutamic acid –CH 2 CH 2 COOH Glu Another type of secondary
9. Aspartic acid –CH 2 COOH Asp structure is possible in which
10. Glutamine –CH 2 CH 2 CONH 2 Gln the protein chains are
11. Asparagine –CH 2 CONH 2 Asn stretched out. It is a -pleated
12. Threonine –CHOH.CH 3 Thr sheet structure.
13. Serine –CH 2 OH Ser • Tertiary structure : The
folding and binding of a-helix
14. Cysteine –CH 2 SH Cys
into more complex shapes
15. Methoionine –CH 2 CH 2 SCH 3 Met
illustrates the tertiary structure
16. Phenylalanine –CH 2 C 6H 5 Phe of proteins. At normal pH and
17. Tyrosine –CH 2 C 6H 4 OH (p) Tyr temperature, each protein will
CH 2 take the energet ically most
18. Tryptophan Trp stable shape. This shape is
NH specific to a given amino acids
which form proteins.
CH 2
• Quaternary protein
19. Histidine NH His structure re sult s when
N several protein molecules are
H bonded together to form a still
larger units.
20. Proline
HN COOH
Pro
COLOUR TESTS
• Biuret Test : Proteins give a
violet or blue colour with 10%
ISOELECTRONIC POINT
NaOH solution and a drop of
• In electric field these ions will migrate towards the electrodes of opposite very dilute copper sulphate.
charge (+ve ions towards cathode and -ve ions towards anode). At a The test is due to ‘–CO–NH–]
certain pH the dipolar ion exists as neutral ion and does not migrate group and is given by all
to either electrodes. This pH is known as isoelectric point of amino compounds containing this
acids. For neutral amino acids. group.
• Mil lon's Test : Mi llon's
PEPTIDES reagent is a solution of
Condensation products of two or more molecules of -amino acids is mercuric and mercurous
called peptides. nitrate in nitric acid. Protein,
• Peptide Linkage : Linkage which unites the -amino acid molecules when warmed with Mi llon's
together is called peptide linkage. It is –CO–NH– linkage. reagent, gives a white
precipitate which changes to
red.
75
Physical properties : General electronic configuration ns1.

General oxidation state +1.


Atomic/Ionic size Li < Na < K < Rb > Cs.
Density Li < K < Na < Rb < Cs
Ionisation energy Li > Na > K > Rb > Cs
Flame colour Li Na K Rb Cs
Crimsen Golden Pale Reddish Blue
red yellow violet violet
Basic nature increase down to the group

Reducing property :

Chemical properties :
With O2 Lithium forms normal oxide [Li2O]
Sodium forms peroxide (Na 2O 2)
K, Rb,Cs forms superoxide KO2,RbO2, CsO2

M2 O M(OH)
H2O

M2 O 2 M(OH) + H2O2
H2 O

MO2 M(OH) + H2O 2 + O2


2 H O

With Water M + H 2O MOH + H2

With Air

With NH3 : M + (X + Y) NH3 [Na(NH3)X]+ + [e(NH3)Y]–


ammoniated e–
Paramagnetic, blue colour excess of metal dimagnetic and copper bronze colour.
on standing Li + NH3 Li2NH (Lithmide)
M(Na/K/Rb/Cs) + NH 3 MNH2 (amide)
With Halides M + X2 MX
K, Rb, Cs forms poly halide due to large size
Carbonates : Only Li2 CO 3 decomposes

Li2CO3 Li2O + CO2

Nitrates : LiNO3 Li 2 O + NO2 + O 2

MNO3 MNO2 + O2 (M = Na/K/Rb/Cs)

76
Na2CO3 does not impart any colour to the flame but NaCl does because the thermal ionization of Na 2CO3
does not take place at the temperature of flame of the burner.

In Solvay’s process, CO2 gas is passed through saturated brine (NaCl) solution when sparingly soluble
NaHCO 3 separates out.
NH3 + H2O + CO2 NH4HCO3
NH4HCO3 + NaCl NaHCO3 + NH4Cl
The NaHCO 3 formed above is calcined to form Na 2CO 3

2NaHCO 3 Na 2 CO 3 + CO 2 + H 2O
Heat

The reactions taking place at different stages during the manufacture of Na2 CO 3 by Solvay process are
given as under :
(a) 2NH3 + CO2 + H2O (NH4)2 CO3
MgCl2 + (NH4 )2CO3 MgCO3 + 2NH4 Cl
or MgCl2 + 2NH4OH Mg(OH)2 + 2NH4Cl
(b) Ammonia recovery tower

NH4HCO3 Heat
NH3 + CO2 + H 2O

2NH4Cl + Ca(OH)2 2NH3 + CaCl2 + 2H2 O


(c) Calcination of NaHCO3
2NaHCO3 Na 2CO3 + CO2 + H 2O

(i) Efflorescence :

Na2CO3.10H 2O when exposed to air it gives out nine out of ten H2 O molecules.

Na2CO3.10H2O Na2CO3.H2 O + 9H2O

(Monohydrate)

This process is called efflorescence. Hence washing soda losses weight on exposure to air.

(ii) Hydrolysis :Aqueous solution of Na2CO3 is alkaline in nature due to anionic hydrolysis.

Na2CO3 2Na+ + CO3–2 and CO3–2 + H2O H2CO3 + 2OH


(Carbonic acid)

(e) Uses

(i) For making fusion mixture (Na2CO3 + K2CO3)

(ii) In the manufacture of glass, caustic soda, soap powders etc.

(iii) In laundries and softening of water.


(iii) NaOH is strong base

77
(iv) Reaction with non metals : no reaction with H2, N2 and C

(v) Reaction with halogens

(vi) Reaction with Metal :

78
Physical properties : General electronic configuration ns2 .

General oxidation state +2.


Atomic/Ionic size Be < Mg < Ca < Sr < Ba
Ionisation energy Be > Mg > Ca > Sr > Ba

Flame colour Ca Brick red Sr Crimson red


Ba - Apple green
Basic nature increase down to the group
Reducing property : Order of reducing property in aqueous and gaseous medium is
Be+2 < Mg+2 < Ca+2 < Sr+2 < Ba+2

Chemical properties :

With O2 M O2
MO O2
MO2
(Be,Mg,Ca,Sr,Ba, oxide) (Ca,Sr,Ba, peroxide)

With Water M + 2H2O M(OH)2 + H2


With Air In moist air, except Be all the elements converts into carbonates.
In dry air Be and Mg gives nitride and oxide both while other gives only oxides.
With NH3 : Only Ca, Sr and Ba gives blue solution of ammoniated electron.
Carbonates :

(i) Except BeCO3 , all the carbonates are stable towards heat

BeCO3 BeO + CO2

(ii) Order of decreasing stability -


BaCO3 > SrCO3 > CaCO3 > MgCO3 > BeCO3
Nitrates :
(i) Alkaline earth metals forms M(NO 3)2 type nitrates. (M –Alkaline earth metal).
(ii) All alkaline metals nitrates on heating gives oxides and NO2 + O2

M(NO3)2 Oxides + NO2 + O2

SIMILARITIES BETWEEN LITHIUM AND MAGNESIUM

(a) Both lithium and magnesium are harder and lighter than other elements in the respective groups.

(b) Lithium and magnesium react slowly with cold water. Their oxides and hydroxides are much less
soluble and their hydroxides decompose on heating. Both form a nitride by direct combination with
nitrogen, Li 3 N and Mg3 N 2 .

(c) The oxides, Li2O and MgO do not combine with excess oxygen to give a peroxide or a superoxide.

(d) The carbonates of lithium and magnesium decompose easily on heating to form the oxide and CO2 .
Solid bicarbonates are not formed by lithium and magnesium.

79
(e) Both LiCl and MgCl2 are soluble in ethanol.
(f) Both LiCl and MgCl 2 are deliquescent and crystallise from aqueous solution as hydrates,
LiCl.2H 2O and MgCl2 .8H 2O.

DIAGONAL SIMILARITY BETWEEN BERYLLIUM AND ALUMINIUM : In many of its properties,


beryllium resembles aluminium. Thus –
(a) The two elements have same electronegativity and their charge/ radius ratios.
(b) Both metals are fairly resistant to the action of acids due to a protective film of oxide on the surface.
Both metals are acted upon by strong alkalies to form soluble complexes, beryllates [Be(OH)4 ]2–
and aluminates, [Al(OH)4 ]– .
(c) The chlorides of both beryllium and aluminium

have bridged chloride structures in vapour phase.


(d) Salts of these metals form hydrated ions, Ex. [Be(OH2)4 ]2+ and [Al (OH2)6 ]3+ in aqueous solutions.
Due to similar charge/ radius ratios of beryllium and aluminium ions have strong tendency to form
complexes. For example beryllium forms tetrahedral complexes such as BeF 4 2– and [Be(C 2 O4 )2
]2– and aluminium forms octahedral complexes like AlF6 3– and [Al(C2 O4) 3 ]3– .

Among alkaline earth metals, Be and Mg do not impart any characteristic colour to the flame due to more
ionization energies.

The stability of the carbonates of alkaline earth metals increases in the order.
BeCO 3 < MgCO3 < CaCO3 < SrCO3 < BaCO3

Be2C on treatment with H2O forms CH4 while CaC2 forms C2H2.
Be2C + 2H2O 2 BeO + CH4
methane
CaC2 + 2H2O Ca(OH)2 + C 2H2
Acetylene

BeCl2 in the vapour phase above 900°C is monomeric ; below 900°C in the vapour exists as a mixture of
monomer BeCl2 and dimer Be2Cl4, in the solid state, has a polymeric structure and when dissolved in a
coordinating solvent it exists as a monomer.

Anhydrous MgCl 2 cannot be prepared by the simple heating of hydrated magnesium chloride MgCl 2 ,
6H2O, as it gets hydrolysed to magnesium oxide.

MgCl 2.6H2 O Heat MgO + 2HCl + 2H2 O

Out of the oxides of group 2 elements only BeO is extremely hard, non volatile, has high melting point
and it is amphoteric.

Anhydrous magnesium chloride (MgCl2) cannot be prepared by heating MgCl2.6H2O. since on heating
MgCl2.6H2O undergoes hydrolysis with the evolution of HCl gas.

MgCl 2.6H2 O Heat Mg(OH).Cl + H2 O

80
Analytical detection of Mg :
(i) Charcoal cavity test. On heating on a charcoal cavity with one drop of Co(NO 3)2 , a pink colour is
imparted to the residue CoO.MgO.
(ii) The salt solution when mixed with NH4Cl and NH 4OH and finally treated with soluble phosphates
forms a white precipitate of magnesium ammonium phosphate.
MgSO4 + Na 2HPO4+NH 4 OH Mg(NH 4 )PO4 +Na 2 SO 4 + H2 O
white ppt.

Hydrolith (CaH2) is calcium hydride.

Calcium cyanamide (CaCN 2 ) is prepared by heating a mixture of CaC 2 in an atmosphere of N 2 at


1270–1370K with CaF2 .

CaC2 + N 2 CaF2
1270 1370 K
CaCN 2 + C

Its trade name is Nitrolim.

Calcium cyanamide (CaCN 2 ) is a slow acting manure and is preferred to soluble compounds like NaNO 3
or (NH4)2 SO4 since it confers fertility of a permanent nature. It is a nitrogenous fertiliser and undergoes a
series of changes giving cyanamide, urea, NH3 and finally the nitrates which are assimilable by plants.
CaCN 2 + H2O + CO2 CaCO3 + H2NCN
H2NCN + H2O H 2NCONH2
Urea
H2NCONH2 + H 2O CO2 + 2NH 3

81
B 2O3 and B(OH3) are acidic, Al2O 3 and Al(OH) 3 ;Ga 2O 3 and Ga(OH) 3 are amphoteric while In 2 O3 and
In(OH)3 are basic. Thus, on moving down the group, there is gradual change from acidic to amphoteric
and then to basic character of the oxide and hydroxides of the elements.
The relative Lewis acidic strength of trihalides of boron increase in the order.
BF3 < BCl3 < BBr3 < BI3
Borazine or Borazole or inorganic benzene is B 3N3H6 .

Action of heat on orthoboric acid

(i) H 3 BO 3 HBO2 + H 2 O
100 C

Orthoboric acid Metaboric acid

(ii) 4HBO 2 160 C


H 2 B 4 O 7 + H 2O

Metaboric acid Tetraboric acid


Above 160°C, it swells up giving frothy mass and finally forms boron trioxide, B2 O3 .

Some important ores of Boron are given as under.


(i) Boric acid, H3BO3
(ii) Borax , Na 2B 4 O7 .10H 2 O
(iii) Colemanite, Ca 2 B 4 O 11 .5H 2 O
Some important minerals of aluminium are given as under.
(i) Corundum, Al 2O 3
(ii) Bauxite, Al 2 O 3.2H 2 O
(iii) Cryolite, Na 3 AlF 6
(iv) Felspar, K AlSi 3 O 8

Melting and boiling points of halides of boron decrease in the order


BI3 > BBr3 > BCl3 > BF3
Boric acid is a weak monobasic acid
B(OH)3 + 2H2O H3 O + [B (OH)4]–1
pKa = 9.25
It is difficult to titrate boric acid against NaOH solutions and the end point cannot be located correctly
However, it can be successfully titrated in the presence of polhydroxy alcohols (e.g. Glycerol, marinital,
catechol or sugar). The presence of these compounds greatly increase the acidity of boric acid.

82
Boron is complex by these compounds. These complex ions cannot interact with H+ ions as boron atom
has already acquired it’s maximum covalency of four. Consequently, boric acid in presence of polyhydroxy

alcohols can be titrated against NaOH to a definite end point.

Borax, which is normally written as Na2B4O7.10H2O, contains tetranuclear units [B 4O5 (OH)4]2– comprising
BO4 and BO3 units. Thus, borax should have been formulated as
Na 2 [B 4 O 5 (OH) 4 ].8H 2 O

Aluminium trifluoride (AlF3) is different from other trihalides of Al in being insoluble and nonvolatile. In
AlF3, the coordination number of Al is six, in AlCl3 the coordination number of Al changes from 6 to 4 as
it melts while in AlBr3 and AlI3 the coordination number remains four. In AlF3 each Al is surrounded by a
distorted octahedron of 6F atoms and 1 : 3 stoichiometry is achieved by the sharing of corner fluorine
atoms between two octahedra.

Aluminium chloride (AlCl3) in the pure and anhydrous state is a white solid but commercial samples
are yellowish due to the impurity of FeCl3.

Anhydrous AlCl3, in the crystalline state possesses a closely packed layer structure with six coordinated
aluminium octahedral arrangement.

Anhydrous AlCl3 has a very high affinity for water. On treating AlCl3 with water the Cl– ions go outside
the coordination sphere to form [Al(H2O)6]Cl3 with enthalpy of solution –330 KJ mol–1. Due to this strong
Al – O linkage hydrate cannot be dehydrated on heating to form AlCl3 .

2[Al(H2 O)6 ] Cl3 Al 2O3 + 6HCl + 9H2 O

Aluminium chloride, is a polymeric solid which exists as a dimer Al2Cl6 between 200–400°C and then
monomer up to 800°C.

Thermite welding, Aluminium has got a very high affinity for oxygen.
4Al + 3O2 2Al2O3.
H = –3230 KJ mol –1

It, therefore, displaces metals less electropositive than itself from oxides. The large amount of heat
produced is used in welding rails or heavy machinery without removing them from their position. This is
called thermite welding or Gold Schmidt’s aluminothermic process. In this process, a mixture of Ferric
oxide (3 parts) and aluminium powder (1 part) called thermite is used.

Pseudo alums are double sulphates of a divalent and a trivalent metals which crystallize with twenty four
water molecules of crystallization, for example.
(i) MnSO 4 . Al 2(SO 4 ) 3 .24H 2 O
(ii) FeSO4 . Al 2 (SO 4 ) 3 .24H 2 O
They are not isomorphous with true alums.

83
Extraction of Aluminium. Al is usually extracted from Bauxite, Al2O3.2H2O. First, bauxite is purified
from the impurities (Red bauxite contains Fe2O3 as impurity while white bauxite contains silica as impurity).
Red bauxite can be purified by Baeyer’s process or Hall’s process while white bauxite is purified by
Serpeck’s process.

Baeyer’s process, involves the roasting of the ore to convert FeO to Fe2O3 and then digested at 423K
with conc. NaOH solution for a few hours when Al2O3 gets dissolved to give a solution of [Al(OH)4] –1
The basic oxide impurities such as Fe 2O3 are not affected.
Al2O3 + 2OH–1 + 3H2O 2Al(OH)4–1
Aluminate ion

Fe2O3 left undissolved is filtered off. The treatment of Al(OH) 4 –1 . solution with a weak acid precipitate
pure Al(OH) 3 .
Al(OH)4–1 + H+ Al(OH)3 + H2O
(White ppt.)
The Al(OH)3 precipitate is removed by filtration and ignited to get alumina, Al2 O3.

Hall’s process, Involves the fusion of the ore with Na2CO3 when soluble sodium meta aluminate, NaAlO2
is produced. This is extracted with water when Fe2O3 is left as a residue.
Al2O3 + Na2CO3 2NaAlO2 + CO2
Sodium meta aluminate
The water extract is heated upto 333K and CO 2 is passed through it. Al(OH) 3 is precipitated due to
hydrolysis and is ignited to get alumina, Al2O3.
2NaAlO2 + 3H2O + CO2 2Al(OH)3 + Na2CO3

Serpeck’s process involves the heating of bauxite with coke in a current of N 2 at 2075K. The SiO2
present in the ore is reduced to silicon which volatilizes off and alumina gives aluminium nitride. This can
be hydrolysed to Al (OH)3 which on fusion gives alumina.
SiO2 + 2C Si + 2CO

Al2O3 + 3C + N2 2AlN + 3CO


Aluminium nitride
AlN + 3H2O Al(OH)3 + NH3
Electrolysis of Al2O3 to from aluminium. Pure alumina is dissolved in fused cryolite, Na 3AlF6 at 1225
K by current of 100 amperes and 6 – 7 volts to get Al. The Al obtained is purified by Hoope’s process.

Boron nitride (BN), has a structure similar to that of graphite.

Green edged flame test for borate (BO33–) ion. A mixture of C 2H5OH and BO3 3– salt with conc. H2 SO4
burns with green edge flame due to the formation of ethyl borate.
H3BO 3 + 3C2H5OH B (OC2 H5)3 + 3H2 O
Ethyl borate

Charcoal cavity test for aluminium. On heating with Na2CO3 and a drop of cobalt nitrate solution a
blue coloured residue to cobalt metaaluminate (Thenard’s blue) is obtained.
2Al3+ + Co(NO3)2 + O2 Co (AlO2 )2 + 2NO2
Blue residue

84
Inert pair effect the reluctance of ns electrons to take part in bond formation is called inert pair effect.
This effect is more pronounced in heavier elements and that too for 13, 14 and 15 group. It results in the
decrease in oxidation state by 2 units. For examples, Tl is more stable in oxidation state + 1 than the
oxidation state +3.
Gold dissolves in aqua regia forming H[AuCl4] while Pt dissolves forming H2 [PtCl6].

CO2 is a gas while SiO2 is a solid at room temperature.

Trimethylamine (CH3 )3N is pyramidal while Trisilylamine N(SiH3)3 is planar due to back bonding.

SiCl4 is a Lewis acid but CCl4 is not because carbon cannot expand it’s octet due to the absence of vacant
d-orbitals.
White Lead is chemically Pb(OH)2. 2PbCO3 and Red lead is Pb3O4.

Silicones are polymeric organosilicon compounds containing Si–O–Si linkage. They have high thermal
stability of Si–O–Si chains and are also called high temperature polymers.
General formula : (R2SiO)n. Where R = –CH3, –C2H5,–C6H 5
Catenation is the unique tendency of 14 group elements to form long chains of different sizes and
shapes. The tendency to show catenation is directly related to the strength of bond. The bond energies of
14 group elements decrease as under :
C –C Si– Si G e–Ge Sn–Sn Pb–Pb
Bond energy (KJ mole –1) 3 48 2 22 1 67 1 55 –

This is the reason why carbon forms many chains, Si, a few and Ge and Sn form practically no chains.
Carbon suboxide (C3O2) is an foul smelling gas which can be prepared by the dehydration of malonic
acid with P4 O10.

On heating upto 200°C, it decomposes into CO2 and carbon.

C3 O 2 CO 2 + 2C
200 C

The molecule is throught to have a linear structure.


O =C =C = C = O
Silicon polymers or silicones are polymeric organosilicon compounds containing Si – O – Si linkages.Their
general formula is (R2SiO) x. They may be linear, cyclic or cross linked polymers.
Mosaic gold (SnS 2 ). Stannic sulphide exists in yellow glistening scales which is used for decorative
purposes under and the name mosaic gold. It is prepared by heating mixture of tin fillings, sulphur and
NH 4Cl in a retort.

85
Sn + 4NH4 Cl (NH4)2 SnCl4 + H2 + 2NH3
2(NH 4)2 SnCl 4 + 2S SnS2 + (NH 4)2 SnCl 6 + 2NH4Cl

Tin Cry. Tin metal when bent produces a cracking noise due to rubbing of metal crystals over one

another.

Action of conc. HNO3 on tin

(a) Dilute HNO3


4Sn + 10HNO 3 4 Sn(NO 3)2 + NH4 NO3 + 3H2 O
(b) Hot conc. HNO3
Sn + 4HNO3 H2SnO3 + 4NO2 + H2O
Metastannic acid

Red lead (Pb3O4) is considered to be mixture of lead monoxide and lead dioxide and it is written as

(PbO 2 .2PbO).

Lead dioxide (PbO2). It is a brown powder obtained by the treatment of red lead with HNO3.

Pb 3O4 + 4HNO3 2Pb(NO3) 2 + PbO2 + H2


It is used as an active material of the positive plate in storage cells and finds use in match industry as an
oxidizing agent.

The main ores of lead are

(i) Glena, PbS


(ii) Cerrusite, PbCO 3
(iii) Anglesite, PbSO 4
SnCl2.2H2O on heating undergoes to form it’s basic chloride Sn(OH).Cl. The anhydrous salt, therefore, be
obtained by heating the hydrated salt.

Stannous chloride reduces mercuric chloride (HgCl2) to a white precipitate of mercurous chloride (Hg2Cl2 )

which finally turns to metallic mercury (dark grey or black).


2Hg2+ + 3Cl – + Sn2+ Hg2 Cl2 + Sn +4
Mercurous chloride
Hg2Cl2 + SnCl2 2Hg + SnCl4
Black

86
Holme’s signals. A mixture of Ca 3P2 and CaC2 on treatment with H2O forms PH3 and P2H4 along with
C2H2. The mixture burns with a bright luminous flame and it acts as a signal for approaching ships.
Ca 3P2 + 6H2O + 3Ca(OH)2 + 2PH 3
CaC2 + H2O Ca(OH)2 + C2H2
The strength and solubilities of oxyacids of 15 group elements are given as under.
HNO 3 H 3 PO 4 H 3 AsO 4 H 3 SbO 4 H 3 BiO 3
Strong We ak W eaker Amphoteric Basic
(Soluble) (Soluble) (Soluble) (Insoluble) (Insoluble)
Acidity of oxides and the solubility of 15 group oxides decreases from N to Bi. For example, N 2 O 3 ,
N2 O5,P 4O6,P4O10, As4 O6 and As4 O10 are acidic and dissolve water forming acids. Sb 4O6 and Sb 4 O10 are
weakly acidic and insoluble in water Bi2O3 is a basic oxide and is insoluble in water.
The oxoacids of phosphorus are given as under :
Formula Name of acid Oxidation of Comments about
No. phosphorus acidic nature
H 3 PO 2 Hypophosphorus +1 Weak, monobasic
acid strong reducing
agent.
H 3 PO 3 Phosphorus acid +3 Dibasic acid, strong
reducing agent.
H4P 2O 6 Hypophosphoric +4 Tetrabasic
acid
H 3 PO 4 Orthophosphoric +5 Tribasic
acid
H4P 2O 7 Pyrophosphoric +5 Tetrabasic
acid
HPO 3 Metaphorphoric +5 Monobasic
acid
NCl3 is hydrolysed with H2O to NH3 and HOCl.
NCl3 + 3H2O NH3 + 3HOCl
PCl3 is hydrolysed with water to form phosphorus acid, H3PO 3.
PCl3 + 3H2O H3PO3 + 3HCl
AsCl3 + 3H2O H3AsO3 + 3HCl

SbCl3 + H2 O SbOCl + 2HCl

BiCl3 + H2 O BiOCl + 2HCl

PCl5 on hydrolysis forms phosphoric acid, H3PO 4.


PCl5 + 4H2O H3PO4 + 5HCl
With Nessler’s reagent K2HgI4 , ammonium salts give a reddish brown ppt. of Million’s base HgO.Hg(NH2 )I

87
Phosphorescence is the glowing of white phosphorus in the dark.

Some main point of difference between white phosphorus and red phosphorus are given as under.

Property White phosphorus Red phosphorus


(i) Physical state Pale yellow soft Red Phosphorus
solid, Can be cut Dark and brittle
with knife. powder
White when freshly
cut.
(ii) Odour Garlic Odourless
(iii) Density 1.8 g/cm 3 2.1 g/cm 3
(iv) Solubility Soluble in CS2 Insoluble
(v) Ignition temp. 303K (melts under 533 K(does not melt
water at 317K) but sublimes)

(vi) With hot caustic Dissolves and PH3 No action


soda is evolved

Smoke screens, involve the use of calcium phosphide, Ca3P2. The PH3 gas obtained from Ca3P2 catches fire
to give the needed smoke.
Phosphatic slag or Thomas slag or Basic slag is obtained as a biproduct in the manufacture of steel and
is probably a double salt of tricalcium phosphate and calcium silicate.
On heating, phosphorus acid, H 3PO3 decomposes into phosphine (PH3) and phosphoric acid (H3PO4).

4H3PO3 Heat
3H3 PO 4 + PH 3

88
Tailing of mercury is due to the formation of mercury oxide when Hg reacts with ozone.
2Hg + O3 Hg2O + O2
As a result of it, mercury looses it’s meniscus and starts sticking to the glass.
The bleaching action of ozone and H2 O 2 is permanent and is due to oxidation while that of SO 2 is
temporary and is due to reduction.
Temporary hardness of water is due to the presence of bicarbonates of Ca and Mg and Permanent
hardness is due to the presence of sulphates and chlorides of Ca and Mg.
Calgon is a trade name given to sodium polymetaphosphate Na2[Na4 (PO3 )6]. It is generally employed for
softening of hard water.
10V H2O2 means that one mole of that H2O2 at N.T.P. evolves 10ml. of oxygen gas.

H2O2 is to restore the colour of old lead paintings which have been blackened due to the formation of PbS
by the action of H2S present in the air.
H2O2 H2O + [O]
PbS + 4[O] PbSO4
PbS + 4H2O2 PbSO4 + 4H2O
Black White
Antichlor action of H2O2 is due to its tendency to reduce the excess of chlorine from bleaching powder to
HCl.
H2O2 + Cl2 2HCl + O2
SO2 gas is dried by bubbling the mixture through conc. H 2SO4. It is not dried over quick lime (CaO) as it
react with it to form calcium sulphite.
CaO + SO2 CaSO3
Sodium thioshlphate Na 2S2O3.5H2O is prepared by the following methods :
(a) By boiling sodium sulphite with sulphur.

Na 2SO 3 + S Boil
Na 2S 2 O3
(b) By boiling sulphur with NaOH
4S + 6NaOH Boil
Na 2S 2O3 + 2Na2S + 3H 2 O
(c) By passing SO2 into Na2S solution.

3Na 2S + 3SO2 Boil


2Na 2S 2O3 + S
(d) By spring’s reaction
Na2 S + Na 2SO 3 + I 2 Heat Na2 S 2O3 + 2NaI

Concentrated Na2S2O3 does not give a white ppt. with AgNO3 . This is because silver thiosulphate
formed is readily soluble in excess of sodium thiosulphate forming soluble complex.
3S2O 32– + Ag 2S2 O 3 2[Ag(S 2O3) 2]3–
soluble
Sodium thiosulphate is oxidized by Cl2 to sodium sulphate.
Na 2S2O3 + Cl 2 + H2O Na2SO4 + 2HCl + S

89
Sodium thiosulphate is oxidized to sodium tetrathionate Na 2S4O6 by I2
2Na2 S2O3 + I2 Na 2S4O6 + 2NaI
Sodium tetrathionate
This reaction forms the basis of iodometric estimation of Cr2O72– and Cu2+ salts.
Sodium thiosulphate reacts with FeCl3 solution to form a violet coloured solution of ferric thiosulphate.
3S2 O 32– + 2Fe 3+ Fe 2 (S 2 O3 ) 3
Violet
The violet colour disappears quickly due to the reduction of ferric chloride by S2O32– ions,
2Fe3+ + 2S2 O32– 2Fe+2 + S4 O6 2–
Sodium thiosulphate reduces cupric salts to cuprous salts.
2CuCl 2 + 2Na 2S 2O3 2CuCl + Na 2S 4O6 + 2NaCl
Sodium thiosulphate reduces auric salts to aurous salt.
AuCl3 + 2S 2O32– AuCl + S4O62– + 2Cl–
AuCl + 2S2 O32– [Au (S2O3)2] 3– + Cl–
Neutral oxides are those which are neutral towards litmus e.g., carbon monoxide (CO), water (H2 O),
nitrous oxide (N2O) and nitric oxide (NO).
Ozone is heavier than air and is slightly soluble in water but is more soluble in turpentine oil, glacial acetic
acid and CCl 4.
H2S gas is dried by passing over CaCl2 or P2 O5 .

Sulphur trioxides (SO3) is a white crystalline solid with melting point 290K and boiling point 318K.

SO3 is prepared by the direct oxidation of SO2 with atmospheric oxygen in presence of finally divided Pt
or V2O5 at a pressure of 2atm. and temperature 700K.

2SO2(g) + O2(g) 2SO3(g)

SO3 reacts with water to produce H2SO4 and large amount of heat is evolved.
SO3 + H2O H2SO4 + heat

90
Some of the example of polyhalides are :

ICl2 , IBr2 , BrCl 2 , ClF2 , ICl 4 , BrF4 , IF6 , BrF6

ICl2 , IBr2 , BrF2 , lF4 , ClF4 , BrF4 , IF6 , BrF6 , ClF6 (Polyhalogen cation)
Pseudo halides are uninegative groups which show certain characteristics of halide ions. For example
Cyanide (CN–), Cyanate (OCN –), Thiocyanate (SCN–), Selencyanate (SeCN–), Azide (N3 –), Aziothio carbonate
(SCSN 3–) and isocyanate (ONC –).
The electron affinity values (in KJ mol–1) for 17 group element are given below :
F Cl Br I
33 3 34 9 3 25 29 6
The bond energies (in KJ mol–1) for halogens are :
F2 Cl 2 Br 2 I2
158.8 242.6 192.8 151.1
AgF is soluble in water while AgCl, AgBr and AgI are insoluble.
Test for chlorine :
(a) It is a greenish yellow gas with irritating smell.
(b) It turns starch iodide paper blue.
(c) It bleaches litmus paper and indigo solution.
Iodine is slightly soluble in water but much more soluble in KI due to the formation of KI 3.
KI + I2 KI3
The solution behaves as a simple mixture of KI and I2.
Action of silica and glass. Strong solution of HF attacks glass readily forming silicon fluoride which
gives complex fluosilicic acid, H2SiF6 with excess HF.
SiO2 + 2H2F2 SiF4 + 2H2 O
SiF4 + H2F2 H2SiF6
This is called etching of glass.
The acidic strength of the oxoacids of halogen decreases in the following order.
HClO 4 > HClO3 > HClO 2 > HClO
The chlorine oxyanion in which the central atoms has highest oxidation number will have maximum
number of oxygen atoms for participation in the extension of the -bond. Thereby the charge on the ion
is delocalized which greatly stabilizes the ion and thus decreases its tendency to accept a proton i.e.,
causes the ion to be very weak base with the result that the strength of the acid increases.
The acidity of oxoacids of different halogens having the same oxidation number decreases with the
increases in atomic numbers of the halogen

HClO > HBrO > HIO

SOME REAGENTS OR MIXTURES

Lithophone : A mixture of ZnS + BaSO4 used as white paint.


Nitrolium : Calcium cyanamide + graphite used as fertilizer.

91
The most important source of noble gases is atmosphere in which they are present in following proportions
by volume and mass:
Element Percentage Percentage
by volume by mass
He 0.0006 0.000037
Ne 0.0015 0.001
Ar 0.932 1.285
Kr 0.0001 0.00028
Xe 0.00001 0.00004

Helium is present to the extent of 2% in natural gas found in the united states and Canada.

Helium is also present in the minerals of radioactive elements uranium and thorium Ex. clevite, uranite,
thorianite, monazite, pichblende etc.

The sixth member of the zero group was discovered in 1900 by Dorn as one of the disintegration products
of radium and was named radon or nitron.
In Dewar's method, the separation of noble gases are summerized below

The viscosity of He is extermely low, about 1/100th of hydrogen gas.

92
Bunch of process to extract metal from their respective ore
Ore : Minerals from which metal can be extracted economically :

Metallurgical process :
1. Mining : Ore obtain in big lumps (less reactive)
2. Crushing/grinding/pulverization : big lumps convert into powder (more reactive)
3. Concentration : To remove matrix/gangue from ore
To increase the concenration of ore particle in ore sample.

93
5. Reduction : To obtains metal (95 to 98%) from metal oxide.

94
Thermodynamics principle of metallurgy
– The graphical representationof Gibbs energy was first used by H.I.T. Ellingham. This provide a sound basis for
considering te choice of reducing agent in the reduction of oxides. this is known as Ellingham diagram such
diagram help us in predicting the feasibility of thermal reduction of an ore.
– The critesion of feasibility is that at a given temperatue, Gibbs energy of reaction must be negative.
– At high temperature 'C' is the best reducing agent.
– At low temperature 'CO' is the best redusing agent.
– In blast fornace reduction takes plae at low temperature i.e. why CO is the reducing agent.

95
A summary of the occurence and Extraction of some Metals is presented in the following table :

Common method
Metal Occurrence Reffining Remarks
of extraction
Aluminium 1. Ba uxite, Al2 O 3.xH 2O Electrolysis of Al2 O 3 Electrolytic refining by For the extraction, a good
E°= -1.66 2. Cryolite, Na 3AlF6 dissolved in molten Hoop's cell source of electricity is
Na 3AlF6 + CaF 2 required

Iron 1. Haematite, Fe 2O 3 Reduction of the oxide Be ssemerization Temperature approaching


E°= -0.44 2. Magnetite, Fe 3O 4 with CO and coke in (impurite s has more 21 70K is required
Blast furnace affinity for O 2 as
3. Limonite, Fe 2O 3.3H 2O
compare to Fe)
4. Siderite, FeCO 3

Copper 1. Coppe r pyrites, CuFeS 2 Roasting of sulphide (i) Polling It is self reduction in a
E°= -0.34 2. Coppe r glance, Cu 2S partially and re duction (ii) Electrolytic method. specially designed
3. Malachite, converted. The reduction
takes place easily.
CuCO 3.Cu(OH) 2
Sulphuric acid leaching is
4. Cuprite, Cu 2O
a lso used in
5. Azurite, 2CuCO 3.Cu(OH) 2 hydrometallurgy from low
grade ores.

Zinc 1. Zinc blende or Sphalerite, Roasting of sulphide ore The metal may be For ZnO, carbon is better
E°= -0.76 ZnS or calcination of ZnCO 3 of purifed by fractional reducing agent then Cu
2. Calamine, ZnCO 3 followed by reduction distillation a nd Zn is obtain in vapours
3. Zincite, ZnO with coke form
ZnO+ C 1673K Zn + CO

Mg 1. Carnallite, Electrolysis of fused MgCl2 MgCl2.6 H 2O is heated in


E°= -2.36 KCl.MgCl2.6H 2O with KCl the excess current of dry
2. Magnesite, MgCO 3 HCl gas to produce
- a nhydrous MgCl2

Sn 1. Cassiterite ,SnO 2 Reduction of the SnO 2 Polling and Liquidation Ore contain impurity of
E°= -0.14 (Tin stone) with carbon. SnO 2+ 2C wolframite, FeWO 4 +
S n+ 2CO MnWO 4 (magnetic
substance)

Pb 1. Galena , PbS Roasting, then self Liquadation &


E°= -0.13 reduction or Reduction of electrolytic method.
PbO (Roaste d ore) with
carbon -
PbS+ 2PbO 3Pb+ SO 2
PbO+ C Pb+ CO
Ag 1. Argentite- Ag 2S, Hydro metallurgy Cuplation & electrolytic In hydro mettallurgy Ag
E°= 0.8 0 native Silver Ag 2S + 4NaCN method obtain in the form of dark
2NaAg(CN) 2 + N 2S a morphous ppt.
2NaAg(CN) 2 + Zn
Na 2Zn(CN) 4 + 2Ag
Au Cuplation & electrolysis In hydro mettallurgy Au
E°= 1.4 0 1. Amalgamation. method. obtain in the form of dark
Native ore
2.Cynide process a morphous ppt.

96
Addition compound

Representation of complex compound

Co-ordination number (property of metal = no. of e– pair accept by metal ion.


Denticity (property of ligand) = no. of e– pair donate by ligand
Polydentate ligand forms rings with central metal ion, ring is known as chelate ring & ligand are called
chelating ligand.

Ligand which have two doner sites (atoms) but at a time only one site (atom) donates are known as
ambidentate ligand. They are

Ex. CN– can coordinate through either the nitrogen or the carbon atom to a central metal ion.

Ligands which have two or more than two donor sites but sometimes in complex formation they do not use
all donor sites this type of ligands are called flexidentate ligand.
Ex. SO 24 , CO 23 .
Structural isomerism :
(i) Ionisation isomerism : Counter ion as a ligand & ligand act as counter ion.
[Co (H2O)5Cl] SO4 [Co(H2O)5 SO4] Cl
(ii) Hydrate isomersim : Number of water molecule inside & outside the co-ordinate sphere are
different.
[Cr(H2O)6]Cl [Cr (H2O)5 Cl] Cl2 .H2O [Cr (H2O)4 Cl2] Cl.2H2 O
(iv) Linkage : when ambidentate ligand is present in co-ordination sphere.
[NC Ag CN]– [NC Ag NC]– [CN Ag NC]–
(iv) Co-ordination isomerism : In cationic anionic complex when ligand/metal ion interchange
[Pt(NH3 )4 ] [PtCl 4] [Pt(NH3)3Cl] [Pt(NH3)Cl 3]
Stereo isomerism :
(i) Geometrical isomerism :
C.N. = 4
Tetrahedral does not show
Square planar M a b , Ma bc, Mabcd, M(AB) , M(AB) ab. Show geometrical isomerism.
2 2 2 2 2

97
C.N. = 6
Mabcdef have 15 geometrical isomerism.
Ma3b 3 have 2 geometrical isomerism [fac-Mer]
(ii) Optical isomerism : (does not have plane of symmetry)
C.N. = 4
(i) Tetrahedral Mabcd is optically active
(ii) Generally square planar is not optically active but in some case depend on ligand.
C.N. = 6
(i) Mabcdef optically active.
(ii) M ( A A )2 b2 cis is optically active but trans does not.

(iii) M ( A A )3 optically active.


Theories of co-ordination compound :
(i) Werner theory -
(a) Oxidation state of central metal ion is called primary valency satisfies by anions, represent by dotted line.
(b) Co-ordination number of central metal ion is called secondary valency satisfies by neutral molecule or
anions, represent by solid line.
(ii) Sidwik EAN Rule :
EAN = atomic number (Z) of the metal - oxidation state of metal ion + number of electrons gained from the
donor atoms of the ligands.
(iii) Valence bond theory :
(i) The metal provides vacant orbitals only after the process of hybridisation, thus vacant hybrid orbitals
are provided by the metal ion.
(ii) The empty 'd' orbitals involved in hybridisation may be inner (n-1)d or outer "nd" orbitals and these
complexes are called as Inner orbital complexes and Outer orbital complexes respectively.
(iii) If inner 'd' orbitals are involved in hybridisation, then it is through only the pairing of unpaired electrons
in the 'd' orbitals of metal ion.
(iv) Then such type of complexes will be diamagnetic or less paramagnetic and will be called as Low
spin complexes.
(v) All outer orbital complexes have paramagnetic nature and they are called as High spin complexes.
(iv) Crystal Field Theory :
In the electric field of these negative charges, the five d orbitals of the metal atom no longer have exactly
same energy. Splitting of five degenerate d-orbitals of the metal ion into sets of orbitals having different
energies is called crystal field splitting.
In octahedral

In tetrahedral

Orbitals which have same energy in a subshell are known as degenerate orbitals.

98
Crystal field stablisation energy (CFSE):

(i) For octahedral CFSE = –0.4 n t 2 g 0.6 n eg 0 + Paring energy (P.E.)

where n t 2 g = number of electron in t 2g orbitals

n eg = number of electron in eg orbitals

(ii) For tetrahedral CFSE = –0.6 n e 0.4 n t 2 t +Paring energy (P.E.)

where n t g = number of electron in t 2 orbitals

n e = number of electron in e orbitals

Factor affecting splitting

(i) Strength of ligand

(ii) Oxidation state of central metal ion

(iii) Transition series (d-series)

(iv) Geometry (number of ligands).


Strength of ligand depends upon :
(i) good donor (ii) good acceptor (iii) high negative charge (iv) Small in size

Series which shows the relative strength of ligands

I (weakest) < Br < SCN < Cl < S < F < OH < C 2 O 4 < H 2 O < NCS
– – – – 2– – – 2– –

< edta 4– < NH 3 < en < CN – < CO(strongest)

Paramagnetism = n(n 2) B.M.

Complementry colour relationship :

For example complementry colour of red is green.

99
The f-blocks elements differ from those of d-blocks elements in that they have unstable electroconfiguration

in the outer shells in comparison to that of d-blocks element.

d-block elements electronic configuration

(n–1)d 1–10 ns 1–2

Most common oxidation state +2

The colour in d-block elements is due to d-excitation while in f-block element, it is due to f-f transitions.

They show variable oxidation state due to less energy difference between ns and (n-1) d sub shell.

Most of the d-block compounds act as catalyst due to their variable oxidation state or complex formation

tendency or adsorption on their surface. Example :

contact proecess = V 2O 5

Ostwald process = Pt/Rh

Haber process = Fe2O 3 + Al2 O3 + K 2 O

Zeigter Natta = TiCl4 + (C 2H5)3 Al

Phenton reagent = FeSO 4 + H 2 O 2

Hydrogenation of Alkene = Ni/Pd

Decomposition of KClO3 = MnO2

Wilkinsion catalyst = RhCl + PPh 3

Action of heat on copper sulphate

CuSO4 .5H 2O CuSO 4 . 3H 2 O CuSO4 .H 2O CuSO 4

Bluish green White

Chemical volcano. When crystals of red coloured ammonium dichromate are heated, a violent action

takes place accompained by flashes of light and nitrogen is liberated leaving behind a dark green residue of

chromium sesquioxide (Cr 2 O3)

(NH4)2 Cr2O7 N 2 + 4H2O + Cr 2O3

Ammonium dichromate Chromium sesquioxide

100
Reactions of Cr2O7–2 :

Reaction of MnO4–

101
Definition :
The branch of chemical analysis which aims to find out the constituents of a mixture of compound is
known as Qualitative Analysis.
The identification of a substances usually involves its conversion into a new substance possessing characteristic
properties with the help of one or more substance of known composition. The substance which is used to
bring about such change is called a Reagent.

GROUP 'A' RADICALS : (Decomposition by dil.HCl/dil.H2SO4)

(1) RADICALS DETECTED WITH DILUTE HCl/DILUTE H2SO4


(I) CARBONATE (CO 32– )
All carbonates except those of alkali metals and ammonium are insoluble in H 2 O.
(i) Dilute HCl
With dilute HCl, it decomposes with effervescences due to the evolution of carbon dioxide.
CO 32– + 2H + CO2 + H 2O
The gas produces white turbidity with lime water, Ca(OH) 2 or baryta water, Ba(OH)2 .
CO 2 + Ca 2+ + 2OH– CaCO 3 + H 2O
White turbidity
CaCO 3 + CO 2 + H 2O Ca(HCO3) 2
Soluble
(II) BICARBONATE (HCO ) –
3
Dilute HCl
With dilute HCl, all bicarbonates gives effervescences due to the evolution of CO 2.
HCO 3– + H+ CO 2 + H2 O
The gas gives white turbidity with lime water or baryta water.
CO 2 + Ca(OH)2 CaCO 3 + H2 O
White turbidity

(III) SULPHIDE (S 2–)

(i) Dilute HCl or Dilute H2SO4


S2– + 2H+ H2S
(CH 3COO) 2Pb + H2 S PbS + 2CH 3COOH
Shining black
H 2S + Cd 2+ CdS + 2H +
Yellow ppt

102
(ii) Sodium Nitroprusside Solution

With sodium nitroprusside solution, ionic sulphide gives a purple colour in alkaline medium.

Na 2 S + Na 2[Fe(CN) 5 NO] Na 4 [Fe(CN) 5 NOS]


Purple colour
No reaction occurs w ith solutions of hydrogen sulphide or free gas. If however, filter paper
moistened with a solution of the reagent is made alkaline with sodium hydroxide or ammonia
solution, a purple colouration is produced with free hydrogen sulphide also.

(IV) SULPHITE (SO3 2–)

Only the sulphites of alkali metals and ammonium are soluble in water.

Dilute HCl or Dilute H2SO4


Dilute HCl or H 2SO 4 decomposes sulphites with the evolution of sulphur dioxide.
SO 32– + 2H + SO 2 + H2O
The gas can be identified
(a) By suffocating odour of burning sulphur.

(b) By green colour formation, when passed through acidified K 2 Cr 2 O 7 solution.


3SO 2 + Cr 2 O 72– + 2H + 3SO 42– + 2Cr 3+ + H 2 O
Green colour

(V) NITRITE (NO 2– )


All other nitrites except AgNO 2 (sparingly soluble) are soluble in H2 O.
(i) Dilute HCl
NO 2– + H + HNO 2
2HNO 2 H 2O + N 2O 3
3HNO 2 HNO 3 + 2NO + H 2O
2NO + O2 2NO 2
Raddish-brown

(ii) Brown ring test

When the nitrite solution is added carefully to a concentrated solution of iron (II) sulphate acidified
with dilute acetic or dilute sulphuric acid, a brown ring appears due to the formation of
[Fe(H2 O)5 NO]SO4 at the junction of the two liquids. If the addition has not been made slowly and
caustiously, a brown colouration results.

NO 2– + CH 3COOH HNO2 + CH3 COO –

3HNO 2 H2 O + HNO 3 + 2NO

FeSO 4 + 6H2 O [Fe(H 2O) 6 ]SO 4

[Fe(H 2 O) 6]SO4 + NO [Fe(H 2O) 5 NO]SO 4 + H2 O

Brown ring

103
(2) RADICALS DETECTED WITH CONCENTRATED H2SO4

(I) CHLORIDE (Cl – )

(i) Concentrated H2SO4


With concentrated H2 SO 4, chlorides gives vapours of HCl.
Cl – + H 2SO 4 HCl + HSO 4–
Vapour evolved
(a) Turns blue litmus paper red
(b) Gives white fumes of NH4Cl when a glass rod moistened with aqueous ammonia solution
is brought close to the mouth of test tube.
(ii) Chromyl Chloride Test
When a mixture containing chloride ion is heated with K2 Cr 2 O7 and concentrated H2 SO 4 ,
deep orange-red fumes of chromyl chloride (CrO 2Cl 2 ) are formed.
K2 Cr 2O 7 + 4NaCl + 6H 2 SO 4 2KHSO 4 + 4NaHSO 4 + 2CrO 2 Cl 2 + 3H 2 O
Orange-red
fumes
When chromyl chloride vapours are passed into sodium hydroxide solution, a yellow solution of sodium
chromate is formed, which when treated with lead acetate gives yellow precipitate of lead chromate.
CrO 2 Cl 2 + 2NaOH Na 2 CrO 4 + 2HCl
Yellow solution
Na 2CrO 4 + (CH 3COO) 2 Pb 2CH 3COONa + PbCrO 4
Yellow ppt
This test is given by ionic chlorides only. Chlorides of Hg , Hg22+, Pb 2+, Ag+, Sn4+ and Sb 3+ do not
2+

respond to chromyl chloride test due to their covalent character, which allows them to ionise only
slightly.
(II) BROMIDE (Br – )
(i) Concentrated H2SO4
If concentrated sulphuric acid is poured in a bromide solution, first a reddish-brown solution
is formed, later reddish-brown vapours of bromine accompany the hydrogen bromide.
2KBr + H2 SO 4 K 2SO 4 + 2HBr
2HBr + H 2SO 4 2H 2 O + SO 2 + Br 2
Reddish-brown
(ii) Manganese dioxide and Concentrated Sulphuric Acid
2KBr + MnO 2 + 2H 2 SO 4 Br 2 + K 2 SO 4 + MnSO 4 + 2H 2 O
Reddish-brown
(iii) Chlorine Water
When chlorine water is added to a solution of bromide, free bromine is liberated which colours
the solution orange-red. If CS2, CHCl3 or CCl4 is added to the solution and the liquid shaken,
the bromine dissolves in the organic solvent and after allowing to stand forms a reddish-brown
solution below the colourless aqueous layer.
2KBr + Cl 2 (water) 2KCl + Br 2
Br2 + Cl2 2BrCl
Pale yellow solution

104
(III) IODIDE (I –)
(i) Concentrated H 2SO4
2I – + 2H 2SO 4 I2 + SO 42– + 2H 2 O + SO 2
Violet vapours
(ii) Chlorine Water
2KI + Cl 2 I 2 + 2KCl
I2 + Chloroform Violet solution

(IV) NITRATE (NO3 ) –

(i) Concentrated H 2SO4


4NO 3– + 2H 2 SO 4 4NO 2­ + 2SO 42– + 2H 2 O + O 2
Reddish-brown vapours
(ii) Brown Ring Test
2NO 3– + 4H 2 SO 4 + 6Fe 2+ 6Fe 3+ + 2NO + 4SO 24– + 4H 2 O
FeSO 4 + 6H 2O [Fe(H2 O) 6 ]SO 4
[Fe(H 2O) 6 ]SO 4 + NO [Fe(H 2 O) 5 NO]SO 4 + H 2O
Brown ring
(V) ACETATE (CH3CO 2 ) –

Dilute Sulphuric Acid


On adding a small quantity of dilute H2SO4 to the acetate salt, acetic acid is produced, which
can be easily recognized by its vinegar–like odour
CH 3COO – + H+ CH 3COOH
Vinegar like odour

(VI) OXALATE (C2O4 ) 2–

Potassium Permanganate Solution


Potassium permanganate solution gets decolourized when warmed in acid solution with an
oxalate salt to 60°C. Many other organic compounds also effect the bleaching of
permanganate but if the evolved carbon dioxide is tested by the lime water reaction, the
test becomes specific for oxalates.
5(COO) 22– + 2MnO 4 – + 16H + 10CO 2 + 2Mn 2+ + 8H 2 O

GROUP 'B' RADICALS

SULPHATE (SO 42– )


Sulphates of barium, strontium and lead are practically insoluble in water, those of calcium and
mercury(II) are slightly soluble and most of the remaining metallic sulphates are soluble.
Barium Chloride Solution
On adding BaCl2 solution to a sulphate salt solution, a white precipitate of barium sulphate
(BaSO 4) insoluble in warm dilute hydrochloric acid and in dilute nitric acid but moderately
soluble in boiling concentrated hydrochloric acid is formed.
SO 42– + Ba 2+ BaSO 4
White ppt

105
ANALYSIS OF CATIONS

(1) Dry Tests

Borax Bead Test :

Na 2 B 4 O 7 2NaBO 2 + B 2 O 3

CuO + B 2O 3 Cu(BO 2 )2
Copper (II) metaborate
Microcosmic Salt Bead Test

Na(NH 4)HPO 4 NaPO 3 + H 2 O + NH 3

transparent beat
NaPO 3 + CoO NaCoPO 4
(blue bead)
Sodium Carbonate Bead Test
The sodium carbonate bead is prepared by fusing a small quantity of sodium carbonate on a platinum
wire loop in the Bunsen flame; a white, opaque bead is produced. If this is moistened, dipped into a little
KNO3 and then into a small quantity of a manganese salt (for example) and the whole heated in the oxidising
flame, a green bead of sodium manganate (Na 2 MnO 4) is formed.

MnO + Na 2CO 3 + O 2 Na 2 MnO 4 + CO 2

A yellow bead is obtained with chromium salt due to formation of sodium chromate (Na 2 CrO 4 )
2Cr 2 O 3 + 4Na 2 CO 3 + 3O 2 4Na 2 CrO 4 + 4CO 2
(2) Flame Tests

Paste of the salt and con. HCl is taken into the lower oxidising zone and colour imparted to the flame
by salts is observed; salts, particularly of group V(Ba2+, Ca 2+, Sr 2+), are identified by colours of the flame
and summariesed in table.

Colour Cation

Golden yellow Na +

Violet (Lilac) K+

Carmine–red Li +

Brick–red Ca 2 +

Apple–green Ba 2+ , Mo 2+

Green Cu 2+, (BO 33–), Tl 3+

Crimson–red S r2+

106
(3) Qualitative Analysis of Cation mixtures :

Group Group Cations ppt/colour


Reagent

I Dil. HCl Ag +, Hg 22+, Pb 2+ AgCl


Hg2Cl2 White
PbCl 2

IIA dil. HCl/H2 S Pb +2 , Cu 2+, Bi 3+, Hg 2+, Cd 2+ PbS CuS, Bi2S3, HgS, CdS

II Black Black Brown Black Yellow

IIB dil. HCl/H2 S As 3+, As 5+, Sb 3+, Sb 5+,Sn 2+, As2S3 As2S5 Sb2S3 Sb2S5 SnS SnS2
Sn 4 +
Yellow Yellow Orange Orange BrownYellow

III NH 4 Cl/NH 4 OH Al3+, Cr 3+, Fe 3+ Al(OH)3 Cr(OH)3 Fe(OH)3

White Green Brown

IV NH 4 Cl/NH 4 OH/ Ni 2+, Co 2+, Mn 2+, Zn 2+ NiS CoS MnS ZnS


H2S
Black Black Pink/Buff/Skin Dirty white

V NH4 Cl/NH 4OH/ Ba 2+, Sr 2+, Ca 2+ BaCO3 SrCO3 CaCO3


(NH 4 ) 2CO 3
White White White

VI No common Na +, Mg 2+, K + No common ppt


group reagent
Zero No common No common ppt
NH 4
group reagent (Generally identify by Nessler's reagent)

PREPARATION OF ORIGINAL SOLUTION


Transparent, aqueous solution of salt is known as original solution and it is prepared by dissolving salt/
mixture in suitable solvent. To prepare original solution, following solvents are used strictly in the order
given below:
(i) Cold Water (ii) Hot water
(iii) Dilute HCl (iv) Conc. HCl
(A) Group I (Pb , Ag , Hg ) RADICALS :
2+ + 2+
2

On adding dilute HCl to the salt solution if white precipitate is obtained, it indicates the presence of Pb 2+,
Ag + or Hg 22+ ion in the solution.

107
1 LEAD (II)

(i) Sodium Hydroxide Solution


Pb 2+ + 2OH – Pb(OH) 2
White ppt
Pb(OH)2 + 2OH – [Pb(OH) 4] 2–
Soluble
(ii) Ammonia Solution
Pb +2 + 2NH 4 OH Pb(OH) 2 + 2NH 4+
White ppt
(iii) Potassium Chromate Solution
PbCl2 is soluble in hot water and gives a yellow precipitate with K 2CrO 4. The precipitate obtained
is insoluble in acetic acid but soluble in NaOH and nitric acid.
PbCl 2 + K 2CrO4 PbCrO 4 + 2KCl
Yellow ppt (chrome yellow)
PbCrO 4 + 4NaOH Na 2 [Pb(OH) 4 ] + Na2 CrO 4
2PbCrO 4 + 2H +
2Pb 2+ + Cr 2 O 72– + H 2 O
2. SILVER (I)
(i) Dilute Hydrochloric Acid
With dilute hydrochloric acid (or soluble chlorides), a white precipitate of silver chloride is formed.
Ag + + Cl– AgCl
White ppt
With concentrated hydrochloric acid precipitation does not occur. After decanting the liquid from
over the precipitate. It can be dissolved in concentrated hydrochloric acid, when a dichloroargentate
complex is formed.
AgCl – + Cl – [AgCl 2 ] –
Soluble
On dilution with water, the equilibrium shifts back to the left and the precipitate reappears. Dilute
ammonia solution dissolves the precipitate to form the diamineargentate(I) complex ion.
AgCl + 2NH 3 [Ag(NH 3) 2 ] + + Cl –
Soluble
(ii) Ammonia solution
2Ag + + 2NH 3 + H 2 O Ag 2 O + 2NH 4+
Brown ppt
Ag 2 O + 4NH 3 + H 2 O 2[Ag(NH 3) 2] + + 2OH –
Soluble
(iii) Potassium Iodide Solution
Ag+ + I– AgI
Yellow ppt
AgI + 2CN – [Ag(CN) 2 ] – + I –
AgI + 2S 2O32– [Ag(S2O 3)2] 3– + I –

108
3. MERCURY (I)
(i) Sodium Hydroxide Solution
Hg+2
2
+ 2OH – Hg 2 O + H2O
Black ppt

Hg2O HgO + Hg

(ii) Ammonia Solution

2Hg 2Cl 2 + 4NH 4 OH

(iii) Potassium Iodide Solution


Hg+2
2
+ 2I – Hg 2 I 2
Green ppt
Hg2 I2 + 2I –
[HgI4]2– + Hg
Black ppt
Hg2I2 HgI 2 + Hg
Red ppt Black ppt
(iv) Potassium Chromate Solution
Hg+2
2
+ CrO 42– Hg 2 CrO 4
Red ppt
Hg 2CrO 4 + 2OH – Hg 2O + CrO 42– + H 2 O
Black ppt
(B) Group II A (Pb 2+, Hg 2+, Cu 2+, Bi 3+, Cd 2+) RADICALS :
The precipitates of group IIA are insoluble in yellow ammonium sulphide.

1. MERCURY (II)
HgS precipitated dissolves in aqua regia forming undissociated HgCl 2 .
3HgS + 6HCl + 2HNO 3 3HgCl 2 + 3S + 2NO + 4H 2 O
(i) Potassium Iodide Solution
Hg2+ + 2I– HgI 2
Scarlet red ppt
HgI2 + 2I – [HgI 4]2– or HgI2 + 2KI K 2[HgI4 ]
Soluble
(ii) Tin(II) Chloride Solution
2Hg 2+ + SnCl 2 Hg 2Cl 2 + Sn 4+
White Silky ppt
Hg 2Cl 2 + SnCl2 2Hg + SnCl4
Black ppt
(iii) Cobalt(II) Thiocyanate Test
Hg 2+ + Co 2+ + 4SCN – Co[Hg(SCN) 4]
Deep-blue ppt

109
2. COPPER (II)
Hot, concentrated nitric acid dissolves copper(II) sulphide, leaving behind sulphur as a white precipitate.
3CuS + 8HNO 3 3Cu 2+ + 6NO 3– + 3S + 2NO + 4H 2 O
White ppt
When boiled for long sulphur is oxidised to H 2SO 4 and a clear blue solution is obtained.
S + 2HNO3 2H + + SO 42– + 2NO
(i) Ammonia Solution
When ammonia solution is added to solution of Cu2+, a blue precipitate of a basic copper sulphate
is obtained, which is soluble in excess reagent giving deep-blue colouration of tetreamminecopper(II)
sulphate.
2Cu 2+ + SO 42– + 2NH 3 + 2H 2O Cu(OH) 2 .CuSO 4 + 2NH 4+
Blue ppt
Cu(OH) 2.CuSO 4 + 8NH 3 2[Cu(NH 3 )4 ] 2+ + SO 42– + 2OH –
Deep-blue colouration
(ii) Potassium Iodide
2Cu 2+ + 5I – Cu 2I 2 + I3–
White ppt
I 3– + 2S 2O 32– 3I – + S 4 O 62–
(iii) Potassium Hexacyanoferrate(II) solution
Cu 2+ ions give chocolate–brown precipitate with K 4[Fe(CN)6] solution.
2Cu2+ + K 4 [Fe(CN)6] Cu 2 [Fe(CN)6 ] + 4K +
Chocolate–brown ppt
(iv) Test by NaCN & KCN
2Cu 2+ + 4CN – 2Cu ICN + (CN) 2
Cyanogen
CuCN + 3CN – [Cu I(CN) 4 ]3–
3. BISMUTH (III)
(i) Sodium Hydroxide
With NaOH solution, Bi3+ give a white precipitate of bismuth(III) hydroxide.
Bi 3+ + 3OH – Be(OH) 3
White ppt
The precipitate is soluble in acids.
Bi(OH)3 + 3H + Bi 3+ + 3H 2 O
When boiled, the precipitate loses water and turns yellowish-white.
Bi(OH) 3 BiO.OH + H2O
Yellowish-white ppt
Bi(OH) 3 when reduced by tetrahydroxostannate(II) ions give black precipitate of bismuth metal.
2Bi(OH)3 + 3[Sn(OH) 4]2– 2Bi + 3[Sn(OH) 6 ]2–

110
(ii) Potassium Iodide
Bi3+ + 3I– BiI3
Black ppt

BiI3 + I– [BiI 4]–

BiI 3 + H2O BiOI + 2H + + 2I –


Orange ppt
(iii) Water

Bi 3+ + NO 3– + H 2 O diluation
BiO(NO 3 ) + 2H +
White ppt

Bi 3+ + Cl – + H 2 O diluation
BiOCl + 2H +
White ppt
4. CADMIUM (II)
(i) Ammoniaum Hydroxide
Cd 2+ + 2NH 4OH Cd(OH) 2 + 2NH 4+
White ppt
Cd(OH) 2 + 4NH 3 [Cd(NH 3 ) 4]2+ + 2OH –
(ii) Potassium Cyanide
Cd 2+ + 2CN – Cd(CN) 2
White ppt
Cd(CN) 2 + 2CN –
[Cd(CN) 4]2–
[Cd(CN) 4 ]2– + H 2 S CdS + 2H + + 4CN –
The marked difference in the stabilities of the copper and cadmium tetracyanato complexes serves
as the basis for the separation of Cu 2+ and Cd 2+ ions.

(C) Group III (Fe 3+, Al 3+, Cr 3+)

1. IRON (III)
(i) Ammonium Sulphide Solution
2Fe3+ + 3S 2– 2FeS + S
Black ppt
FeS + 2H + H2 S + Fe 2+
4FeS + 6H 2O + 3O 2 4Fe(OH) 3 + 4S
2Fe 3+
+ 3S 2–
Fe2 S 3
Fe 2S 3 + 4H +
2Fe 2+ + 2H 2 S + S
(ii) Sodium Hydroxide Solution
With sodium hydroxide solution, a reddish-brown precipitate of iron(III) hydroxide, insoluble in excess
of the reagent (distinction from aluminium and chromium) is obtained.
Fe3+ + 3OH – Fe(OH) 3
Reddish-brown ppt

111
(iii) Potassium Hexacyanoferrate(II)
4Fe3+ + 3[Fe(CN)6 ]4– Fe4 [Fe(CN) 6 ] 3
Prussian blue
Fe4 [Fe(CN) 6 ]3 + 12OH –
4Fe(OH)3 + 3[Fe(CN)6 ] 4–
Raddish-brown ppt
(iv) Potassium Hexacyanoferrate(III)
Fe 3+ + [Fe(CN) 6] 3– Fe[Fe(CN) 6 ]
Brown colouration
(v) Ammonium Thiocyanate Solution

Fe 3+ + 3SCN

2. ALUMINIUM (III)
Sodium Hydroxide Solution
Al 3+ + 3OH – Al(OH)3
White ppt
Al(OH) 3 + OH –
[Al(OH) 4]–
Soluble
[Al(OH) 4] + NH
– +
4
Al(OH) 3 + NH 3 + H2O
[Al(OH) 4] + H
– +
Al(OH) 3 + H2O
Al(OH) 3 + 3H +
Al 3+
+ 3H 2 O
3. CHROMIUM (III)
(i) Sodium Hydroxide Solution
Cr 3+ + 3OH – Cr(OH)3
Green ppt
Cr(OH) 3 + OH– [Cr(OH) 4 ]–
excess Soluble
(ii) Ammonia Solution
CrCl 3 + 3NH 4 OH Cr(OH)3 + 3NH 4Cl
Bluish-green ppt
Cr(OH)3 + 6NH 3 [Cr(NH 3) 6]3+ + 3OH–
Excess Pink colouration
(iii) Chromium Pentoxide (Chromium Peroxide, Peroxochromic Acid) Test
On acidifying the solution with dilute sulphuric acid, adding few drops of ether or amyl alcohol to
the mixture and finally adding some hydrogen peroxide, blue colouration is formed, which can be
extracted into the organic phase by gently shaking. During the reaction, chromium pentoxide is
formed.
CrO 42– + 2H + + 2H 2 O 2 CrO5 + 3H 2O
Blue colouration
in ether layer

112
Chromium pentoxide has the following structure :

Because of the two peroxide groups, the compound is often called chromium peroxide. The name
peroxochromic acid is less appropriate, because the compound does not contain hydrogen at all.
In aqueous solution, the blue colour fades rapidly, because chromium pentoxide decomposes to
chromium(III) and oxygen.
4CrO 5 + 12H + 4Cr 3+ + 7O 2 + 6H 2 O
(D) Group IV (Zn , Mn , Co , Ni )
2+ 2+ 2+ 2+

1. ZINC (II)

(i) Sodium Hydroxide Solution


Zn2+ + 2OH – Zn(OH) 2
White gelatinous ppt
Zn(OH) 2 + 2H + Zn 2+ + 2H 2O
Zn(OH)2 + 2OH –
[Zn(OH) 4 ]2–
excess
(ii) Ammonia Solution
Zn 2+ + 2NH 3 + 2H 2 O Zn(OH) 2 + 2NH 4+
White ppt
Zn(OH)2 + 4NH 3 [Zn(NH 3) 4] 2+ + 2OH –

(iii) Potassium Hexacyanoferrate(II)


3Zn 2+ + 2K + + 2[Fe(CN) 6 ] 4– K 2 Zn 3 [Fe(CN) 6 ] 2
White ppt
K 2Zn 3 [Fe(CN) 6 ] 2 + 12OH –
2[Fe(CN) 6 ] 4– + 3[Zn(OH) 4 ] 2– + 2K +
(iv) Ammonium tetrathiocyanatomercurate(II)
Zn 2+ + [Hg(SCN) 4 ]2– Zn[Hg(SCN) 4]
White ppt
2. MANGANESE (II)
(i) Sodium Hydroxide Solution
With sodium hydroxide solution, an initially white precipitate of manganese(II) hydroxide is obtained.
Mn2+ + 2OH – Mn(OH) 2
White ppt
The precipitate is insoluble in excess reagent. It rapidly oxidizes on exposure to air, becoming brown,
when hydrated manganese dioxide, MnO(OH) 2 , is formed.
2Mn(OH) 2 + O2 2MnO(OH)2
Brown ppt
(ii) Ammonia Solution
With NH 3 solution, Mn2+ gives a white precipitate of manganese (II) hydroxide.
Mn 2+ + 2NH 3 + 2H 2 O Mn(OH) 2 + 2NH 4+
White ppt
The precipitate is soluble in ammonium salts, when the reaction proceeds towards the left.
(iii) Lead dioxide and Concentrated Nitric Acid
5PbO 2 + 2Mn 2+ + 4H + 2MnO 4– + 5Pb 2+ + 2H 2 O
Purple colour

113
(iv) Sodium Bismuthate (NaBiO3) Solution
2Mn 2+ + 5NaBiO 3 + 14H + 2MnO –4 + 5Bi 3+ + 5Na + + 7H 2 O
Purple colour
3. NICKEL (II)
The black precipitate of NiS(II) is insoluble in cold dilute HCl and in acetic acid but dissolves in hot concentrated
nitric acid and in aqua regia with the separation of sulphur.
NiS + 2HNO 3 + 6H + 3Ni 2+ + 3S + 2NO + 4H 2O
NiS + HNO 3 + 3HCl Ni 2+
+ S + NOCl + 2Cl – + 2H 2 O

(i) Sodium Hydroxide Solution


Ni 2+ + 2OH – Ni(OH)2
Green ppt
Ni(OH)2 + 6NH 3 [Ni(NH 3 )6] 2+ + 2OH–
Deep–blue colouration
Ni(OH) 2 + 6NH 4 + 4OH –
+
[Ni(NH 3 )6 ] 2+ + 6H 2 O
Deep–blue colouration
(ii) Ammonia Solution
Ni 2+ + 2NH 3 + 2H 2 O Ni(OH) 2 + 2NH 4 +
Green ppt
Ni(OH)2 + 6NH3 [Ni(NH 3)6] 2+ + 2OH –
Deep-blue colouration
(E) Group V (Ba 2+, Sr 2+, Ca 2+)

1. BARIUM (II)
(i) Potassium Chromate Solution
Ba 2+ + K 2 CrO 4 BaCrO 4 + 2K +
Yellow ppt
2CrO 2–
4
+ 2H +
Cr 2 O 72– + H 2 O
(ii) Ammonium Sulphate Solution
Ba 2+ + (NH 4 )2 SO 4 BaSO 4 + 2NH 4 +
White ppt
BaSO 4 + H 2 SO 4 (conc.) Ba2+ + 2HSO 4–
(iii) Ammonium Oxalate Solution
Ba 2+ + (NH 4 ) 2 C 2 O 4 BaC 2 O 4 + 2NH 4+
White ppt
2. STRONTIUM (II)
(i) Ammonium Sulphate Solution
Sr 2+ + (NH 4 ) 2SO 4 SrSO 4 + 2NH 4+
White ppt
(ii) Ammonium Oxalate Solution
Sr 2+ + (NH 4 ) 2 C 2O 4 SrC 2 O 4 + 2NH 4+
White ppt

114
3. CALCIUM (II)

(i) Ammonium Oxalate Solution


Ca 2+ + (NH 4 ) 2C 2 O 4 CaC 2 O 4 + 2NH 4+
White ppt
(ii) Potassium Hexacyanoferrate(II) Solution
Ca 2+ + K 4 [Fe(CN) 6 ] K 2Ca[Fe(CN) 6 ] + 2K +

(F) Group VI (Na +, K +, Mg 2+)

1. MAGNESIUM (II)
(i) Ammonia Solution
Mg 2+ + 2NH 4OH Mg(OH) 2 + 2NH 4 +
White ppt
(ii) Ammonium Carbonate Solution
5Mg 2+ + 6CO 32– + 7H 2 O 4MgCO 3 .Mg(OH) 2.5H 2 O + 2HCO 3–
White ppt
NH + CO +
NH 3 + HCO
2– –

(iii) Disodium hydrogen phosphate Solution


4 3 3

Mg 2+ + NH 3 + HPO 42– Mg(NH 4 )PO 4


White ppt
Mg 2+
+ HPO 2–
4
MgHPO4
White ppt

(G) Group Zero (NH 4+)

1. AMMONIUM (NH 4+)


(i) Sodium Hydroxide Solution
All ammonium salts on heating with alkali (NaOH) gives smell of NH 3.
NH 4+ + OH – NH3 + H 2O
(a) The gas evolved can be detected by its smell.
(b) Gas evolved gives white fumes of NH4 Cl with HCl.
NH3 + HCl NH4Cl
White fumes
(c) Paper soaked in CuSO4 solution, becomes deep-blue by NH3 due to the complex formation.
CuSO 4 + 4NH 3 [Cu(NH 3 )4]SO 4
Deep-blue colouration
(d) Gas can be identified by its ability to turn filter paper moistened with mercury(I) nitrate solution
black.
2NH 3 + Hg 22+ + NO 3– Hg(NH 2 )NO3 + Hg + NH 4+
Mercury(II) amidonitrate Black ppt
white ppt
(ii) Nessler's Reagent
With Nesseler's reagent (an alkaline solution of potassium tetraiodomercurate(II), ammonium salts
form a brown precipitate or brown or yellow colouration is produced depending on the amount
of NH4+ ions present in the solution. The precipitate is a basic mercury(II) amido–iodine.

115
NH 4Cl + 2K 2 HgI 4 + 3KOH I + 4KI + 2H 2 O + 3NaI

This test can detect even traces of NH 3 present in a sample.


IRON (II)
(i) Sodium Hydroxide Solution
Fe2+ + 2OH – Fe(OH) 2
White ppt
4Fe(OH) 2 + 2H 2 O + O 2 4Fe(OH) 3
Reddish–brown ppt
2Fe(OH) 2 + H 2O 2 2Fe(OH) 3
Reddish–brown ppt
(ii) Potassium Hexacyanoferrate (II) Solution
Fe 2+ + 2K + + [Fe(CN) 6 ] 4– K 2 Fe[Fe(CN) 6]
White ppt
(iii) Potassium Hexacyanoferrate(III) Solution
Fe 2+ + [Fe(CN) 6 ]3– Fe 3+ + [Fe(CN) 6 ] 4–
4Fe3+ + 3[Fe(CN) 6]4– Fe4[Fe(CN) 6 ]3
Prussian blue
(iv) Ammonium thiocyanate Solution
With ammonium thiocyanate solution, no colouration is obtained with pure iron(II) salts (distinction from
(III) ions)
(v) Dimethylglyoxime Reagent
With dimethylglyoxime reagent soluble red iron(II) dimethyl glyoxime is obtained in ammoniacal
solution. Iron(III) salts give no colouration, but nickel, cobalt and large quantities of copper salts interfere
and must be absent.

116
Important Notes

117
Important Notes

118