Chemistry Physical II

DAY NINE
Physical and
Chemical
Equilibrium
Learning & Revision for the Day
u Equilibrium State u Equilibria Involving Chemical u Equilibrium constant

Processes (Kp and K c ) and their
u Equilibria Involving Physical
Factor Affecting Equilibrium Significance
Processes u
Equilibrium is a general term which applies not only to chemical reactions but applies
to physical changes as well, e.g. ice and water are in equilibrium at 0°C and atmospheric
pressure.
Equilibrium State
In a reversible reaction, the point at which there is no further change in concentration
of reactants and products, is called equilibrium state. It gives rise to a constant vapour
pressure because of an equilibrium in which the number of molecules leaving the liquid
equals the number returning to liquid from the vapour.
Some important features of equilibrium state are
(i) Equilibrium is attained in a closed container. PREP
(ii) Rate of forward reaction = Rate of backward reaction.
(iii) At equilibrium, concentration of reactants and products becomes constant.
MIRROR
Your Personal Preparation Indicator
Concept of Dynamic Equilibrium u No. of Questions in Exercises (x)—

u No. of Questions Attempted (y)—
Equilibrium is always dynamic in nature, i.e. the reaction does not stop but goes on
u No. of Correct Questions (z)—
forward and backward directions with equal speed. In other words, the equilibrium (Without referring Explanations)
state is a dynamic balance between the forward and backward reaction.
e.g. solid s liquid (physical equilibria) u Accuracy Level (z / y × 100)—
H2O (s) s H2O (l ) (273 K, 1 atm) u Prep Level (z / x × 100)—
N2O 4 (g) s 2NO2 (g) (chemical equilibria)

In order to expect good rank in JEE, your
Catalyst helps in attaining the state of equilibrium quickly without changing the state of Accuracy Level should be above 85 & Prep
Level should be above 75.
equilibrium.
DAY NINE PHYSICAL AND CHEMICAL EQUILIBRIUM 101
Equilibria Involving Types of Chemical Equilibrium

Physical Processes On the basis of physical state of reactants and products,
The characteristic of system at equilibrium are better equilibrium may be of the following two types:
understood by physical processes. 1. Homogeneous equilibria, in which reactants and
products are in same phase, e.g.
This may be attained by the following ways
N2 (g) + 3H2 (g) → 2NH3 (g)
1. Solid-liquid equilibrium
Ice s Water CH3COOH(l ) + C2 H5OH(l ) s CH3COOC2 H5(l ) + H2O(l )
Rate of melting of ice = rate of freezing of water 2. Heterogeneous equilibria, in which reactants and
products are in different phase, e.g.
2. Liquid-gas equilibrium
CaCO3 (s) s CaO(s) + CO2 (g)
Water s Water vapours
Rate of evaporation of water NH4 HS(s) s NH3 (g) + H2S(g)
= rate of condensation of water vapours
3. Solid-gas equilibrium
Law of Chemical Equilibrium
Certain solids on heating directly change from solid into At a given temperature, the product of concentrations of the
vapour state (sublimation). reaction products raised to the respective stoichiometric
coefficient in the balanced chemical equation divided by the
Naphthalene s Naphthalene
(solid) (vapour) product of concentrations of the reactants raised to their
individual stoichiometric coefficients has a constant value.
Henry’s Law This is known as ‘‘law of chemical equilibrium.’’
The equilibrium between the molecules in the gaseous state aA+bB s cC + dD
and the molecules dissolved in the liquid under pressure is Rate of forward reaction (R f ) ∝ [A] a [B]b
governed by Henry’s law which states that the mass of a gas
∴ R f = k f [A] a [B]b
dissolved in a given mass of a solvent at any temperature is
proportional to the pressure of the gas above the solvent. Rate of backward reaction (Rb ) ∝ [C]c [D]d
General Characteristics of Equilibrium ∴ Rb = kb [C]c [D]d

Involving Physical Processes At equilibrium, k f [ A]a [ B]b = kb [C ]c[D]d
General characteristics of equilibrium involving a physical kf [C ]c[D]d
process are as follows: k = =
kb [ A]a [ B]b
(i) At equilibrium, all the measurable properties of the
system remain constant. where, k f = rate constant for forward reaction
(ii) Equilibrium is attained only in a closed system at a kb = rate constant for backward reaction
given temperature. The above expression is also known as law of chemical
(iii) Equilibrium is dynamic in nature, i.e. the opposing equilibrium.
processes do not stop but take place simultaneously and pc ⋅ pd
For a gaseous reaction, K p = Ca Db
with the same rate. p A ⋅ pB
(iv) The physical equilibrium is chracterised by constant where, K p = equilibrium constant in terms of partial pressure.
value of one of its parameter (such as melting point) at a
given temperature.
(v) The magnitude of these parameters at any stage shows Equilibrium Constants (K p and
the extent of physical process upto which it has K C ) and their Significance
proceeded before reaching equilibrium.
The ratio of the concentrations of the products raised to the
power of their stoichiometric coefficients to the
Equilibria Involving concentrations of reactants raised to the power of their
Chemical Processes stoichiometric coefficients at equilibrium state is called the
The rate of reversible reactions at which the concentration of equilibrium constant (K ).
the reactants and products do not change with time is known The equilibrium constant (K ) can be expressed in three ways:
as chemical equilibrium. 1. Equilibrium constant in terms of molar concentration( KC ).
Active mass = molar concentration (mol/L)
[C]c ⋅ [D]d
e.g. H2 + I2 q 2HI KC =
[ A]a ⋅ [B]b
PCl5 q PCl3 + Cl2
102 40 DAYS ~ JEE MAIN CHEMISTRY DAY NINE
2. Equilibrium constant in terms of partial pressure ( K p ). Equilibrium constant in terms of activities, K a

pCc pdD aCc × adD
Kp = Ka =
paA pbB aaA × abB
3. Equilibrium constant in terms of mole fraction ( K χ ). Activity = activity coefficient × molality (or molarity)
χ cC ⋅ χ dD i.e. a=γ×m
Kχ =
χ aA ⋅ χ bB
Characteristics of Equilibrium Constant
Significance of equilibrium constants are as follows : (i) Equilibrium constant (K p or K C ) does not depend on
(i) If K C > 103 , products predominate over reactants. In pressure, volume, concentration and catalyst but
other words, if K C is very large, the reaction proceeds depends only upon temperature.
almost in all the way to completion. (ii) Equilibrium constant for a given reaction is independent
(ii) If K C < 10 −3 , reactants predominate over products. In of the reaction mechanism.
other words, if K C is very small, the reaction proceeds (iii) Equilibrium constant depends on stoichiometric
hardly at all. coefficient, e.g.
(iii) If K C is in the range 10 −3 to 103 , appreciable

K C1
• H2(g) + I2(g) s 2HI(g); K C1
concentration of both reactants and products are present.
KC
Equilibrium constant helps in predicting the direction in 1 1 2
• H2 (g) + I2 (g) s HI(g); KC = K C1
2 2 2
which given reaction will proceed at any stage. For this
KC
purpose, we find out reaction quotient. 3 1 1 1 1
• HI (g) s H2 (g) + I2 (g); KC3 = =
It is defined as the ratio of the molar concentration or reaction 2 2 K C2 K C1
quotient partial pressure of the product species to that of
(iv) If a reaction is multiplied by n, the rate constant, K C
reactant species at any stage in the reaction.
becomes (K C )n. n can be fractional also (+ve only).
For a general reaction, aA + bB s cC + dD
c d
(v) If K 1 be equilibrium constant for P s Q and K 2 be
[C] [D]
QC = equilibrium constant for R s S, equilibrium constant
[ A]a[B]b for P + R s Q + S is K 1 K 2 .
pCc . pdD (vi) For exothermic reactions, K C decreases with increase in
and Qp =
paA . pbB temperature. For endothermic reactions, K C increases
with increase in temperature. For reactions having zero
At any stage of the reaction,
heat energy, temperature has no effect.
(i) if QC > K C , the reaction will proceed in the direction of
reactants (reverse reaction).
Significance of ∆G and ∆G° in
(ii) if QC < K C , the reaction will proceed in the direction of
the products. Chemical Equilibria
(iii) if QC = K C , reaction mixture is already at equilibrium. l
∆G for a reactions under any set of conditions is related to
its value under standard conditions, i.e. ∆G° by the
Relation between K p , K C and K χ equation,
∆ng
K p = K C (RT ) ∆G = ∆G °+2.303 RT log Q
∆ng l
Under equilibrium condition, for same number of moles of
K p = K χ ( p)
reactants and products.
R = gas constant, T = temperature in Kelvin Q = K p = K C = K and ∆G = 0
∆ng = gaseous moles of products – gaseous moles of reactants ∴ ∆G ° = −2.303 RT log K
Hence, Significance of ∆G° are given below:
(i) If ∆ng = 0, K p then = K C (no units for both K C and K p) (i) If ∆G ° < 0, log K > 1 ⇒ K > 1
∆ng
(ii) If ∆ng = + ve, then K p > K C (unit of K C is (mol L−1 ) and Therefore, forward reaction is spontaneous.
∆ng (ii) If ∆G ° > 0, log K < 1 ⇒ K < 1
that of K p is (atm) )
Therefore, backward reaction is spontaneous.
∆ng
(iii) If ∆ng = −ve then K p < K C (unit of K C is (L mol−1 ) and (iii) If ∆G° = 0, log K = 0, ⇒ K = 1
∆ng Therefore, reaction is at equilibrium.
that of K p is (atm) )
DAY NINE PHYSICAL AND CHEMICAL EQUILIBRIUM 103
NOTE Relation between Degree of Dissociation and Density 2. Effect of Pressure

Degree of dissociation (α) of a gaseous compound is
related to its vapour density by At high pressure, reaction goes from higher number of moles
to lower number of moles or from higher volume to lower
D−d
α= volume and vice-versa.
d( y − 1)
(i) If ∆ng =0, no effect on equilibrium due to pressure change.
Here, D = molar density before dissociation / initial density (ii) If ∆ng > 0, the increase in pressure favours backward
d = density after dissociation/density of the gaseous reaction.
mixture (iii) If ∆ng < 0, the increase in pressure favours forward
y = number of moles of products reaction. (∆ng = number of moles of gaseous products –
molecular weight number of moles of gaseous reactants).
Density of gas =
2
3. Effect of Temperature
Molecular weight = Density of gas × 2
At high temperature, reaction goes to endothermic direction
MO = D × 2 or MC = d × 2
while at low temperature reaction goes to exothermic direction.
Here, The equilibrium constant for an endothermic reaction (positive
MO = Observed molecular weight [Abnormal] ∆H) increases as the temperature increases.
MC = Calculated molecular weight [Theoretical] K ∝ T ; if ∆H ° = + ve (endothermic)
1
K ∝ ; if ∆H ° = − ve (exothermic)
Factors Affecting Equilibrium T
(Le-Chatelier’s Principle) 4. Effect of Catalyst
The principle states that change in any of the factors that
A catalyst increases the rate of forward reaction as well as the
determine the equilibrium conditions of a system, will
rate of backward reaction, so it does not affect the equilibrium
cause the system to change in such a manner, so as to
and equilibrium constant.
reduce or to counteract the effect of the change.
Different factors affecting equilibrium are discussed 5. Effect of Inert Gas
below: At constant volume, there is no effect of addition of inert gas. At
constant pressure, when inert gas is added, reaction goes from
1. Effect of Concentration Change lower number of moles to higher number of moles.
The concentration stress of an added reactant or product
is relieved by net reaction in the direction that consumes Application of Le-Chatelier Principle
the added substance. e.g.
The Le-Chatelier’s principle is applicable to physical as well as
A+Bs C chemical equilibria. Some of its applications are mentioned below:
(i) If we increase the concentration of either A or B
(reactants), the equilibrium goes in the direction that
1. To Chemical Equilibria
consumes A or B, i.e. forward direction. Haber’s processes of synthesis of ammonia
(ii) If we increase the concentration of C (product), the N2 (g) + 3 H2 (g) q 2 NH3 (g); ∆H = – ve
equilibrium goes in the direction that consumes C, To get better yield of ammonia, required conditions are:
i.e. backward direction. l
High pressure as ∆ng = − ve
(iii) If we remove C (product), the equilibrium goes in the l
Low temperature as reaction is exothermic
direction in which its concentration increases, i.e. l
High concentration of reactants
forward direction.
l
Removal of NH3
(iv) If any of the species is in solid or liquid state, its
addition does not alter the original equilibrium. 2. To Physical Equilibria
Sweet substances cause tooth decay because on Some of the application for physical equilibria is as follows:
fermentation these produce H+ ions which combine
(i) Effect of pressure on melting point
with OH– ions and shift the equilibrium in forward
(ii) Ice-water equilibrium,
direction.
Demineralisation Ice (s) s water (l)
Ca 5(PO 4 )3 OH (s) An increase in pressure favours the melting of ice into water
Remineralisation
because Vice > Vwater . Therefore, on increasing pressure, more
5Ca2 + (aq ) + 3PO34− (aq ) + OH−(aq )
and more ice will melt.
104 40 DAYS ~ JEE MAIN CHEMISTRY DAY NINE
(ii) Effect of pressure on solubility of gases (iii) Effect of temperature on solubility of solids
Gas + solvent s solution Solute + solvent s solution ; ∆H = + ve
An increase in pressure always favours the dissolution An increase in temperature always favours endothermic
of gas in the solvent. Therefore, solubility of gas reaction, therefore solutes having endothermic
increases with increase in pressure. dissolution show an increase in their solubility with
temperature and solutes having exothermic dissolution
The amount of gas dissolved per unit volume of
(dissolution of lime in water) show a decrease in their
solvent is directly proportional to its pressure (Henry’s
solubility with temperature.
law), i.e. m ∝ p.
DAY PRACTICE SESSION 1
FOUNDATION QUESTIONS EXERCISE

1 In a chemical reaction, the rate constant for the 6 The standard Gibbs energy change at 300 K for the
backward reaction is 7.5 ×10– 4 and the equilibrium reaction, 2A g B + C is 2494. 2 J.
constant is 1.5. The rate constant for the forward At a given time, the composition of the reaction mixture is
reaction is 1 1
[ A ] = , [B ] = 2 and [C ] = . The reaction proceeds in the
(a) 5 × 10–4 2 2
(b) 2 × 10–3 [R = 8.314 JK / mol, e = 2.718 ] ª JEE Main 2015
(c) 1.125 × 10−3 (a) forward direction because Q > KC
(d) 9.0 × 10–4 (b) reverse direction because Q > KC
2 56 g of N 2 and 6 g of H 2 were kept at 400°C in 1 L (c) forward direction because Q < KC
(d) reverse direction because Q < KC
vessel. The equilibrium mixture contained 27.54 g of
NH 3 . The approximate value of KC for the above 7 For the reaction,
reaction in mol – 2 L2 is
2NO 2(g) s 2NO(g) + O 2(g)
(a) 0.128 (b) 0.118
[KC = 1.8 ×10−6 at 184°C, R = 0.00831 kJ/(mol K)]
(c) 0.148 (d) 0.008
when K p and KC are compared at 184°C it is found that
3 The concentration of CO 2 which will be in equilibrium (a) whether K p is greater than, less than or equal to KC
with 2.5 ×10–2 mol L–1 of CO at 100°C. For the reaction depends upon the total gas pressure
FeO (s ) + CO (g ) s Fe (s) + CO 2 (g ); KC = 5.0 will be (b) K p = KC
(a) 0.5 × 10–1 mol L–1 (b) 1.25 × 10–1 mol L–1 (c) K p is less than KC
(c) 2 × 10–2 mol L–1 (d) None of these (d) K p is greater than KC
4 1.1 moles of A are mixed with 2.2 moles of B and the 8 For the reaction,
mixture is kept in a 1 L flask till the equilibrium, CO(g) + Cl 2(g) s COCl 2(g), the K p /KC is equal to
A + 2B s 2C + D is reached. At equilibrium, (a) 1/RT (b) RT
0.2 mole of C is formed. The equilibrium constant of the
(c) RT (d) 1.0
above reaction is
(a) 0.0002 (b) 0.004 9 For the following reaction in gaseous phase
1
(c) 0.001 (d) 0.003 CO + O 2 → CO 2 . KC /K p is
2
5 In aqueous solution, the ionisation constants for carbonic
(a) (RT )1/ 2 (b) (RT )−1/ 2
acid are K 1 = 4.2 × 10 −7 and K 2 = 4.8 × 10 −11 (c) (RT ) (d) (RT )−1
Select the correct statement for a saturated 0.034 M 10 For the reaction,
solution of the carbonic acid. ª AIEEE 2010
1
(a) The concentration of CO 2− SO 2(g ) + O2(g ) H SO 3 (g )
3 is 0.034 M 2
−
(b) The concentration of CO 2−
3 is greater than that of HCO 3 if K p = KC (RT )x where, the symbols have their usual meaning
+ −
(c) The concentration of H and HCO 3 are approximately then the value of x is (assuming ideality) ª JEE Main 2014
equal 1 1
(a) −1 (b) − (c) (d) 1
(d) The concentration of H+ is double that of CO 2−
3 2 2
DAY TEN
Ionic
Equilibrium
u Weak and Strong Electrolytes u Ionisation of Water

u Degree/Dissociation u pH Scale
u Various concepts of Acids and Bases and their u Solubility of Sparingly Soluble Salts
Ionisation u Buffer Solution
The equilibrium concept also extends to ionic reactions. There it is known as ionic
equilibrium and applied as equilibrium between dissociated and undissociated form of an
ionic reaction of weak acid, weak base, hydrolysis reaction etc.
Weak and Strong Electrolytes

1. Weak electrolytes dissociate partially in the solutions and such solutions are poor
conductor of electricity. e.g. CH3COOH, H3 PO 4 , H3 BO3 , NH4OH, HCN etc.
2. Strong electrolytes dissociate completely into their ions in solution and such
solutions are very good conductor of electricity. e.g. HCl, H2SO 4 , NaOH, KOH, NaCl,
KCl etc.
Ionisation of Electrolytes PREP

Separation of an electrolyte into their ions either on fusion or dissolution is called MIRROR
ionisation or dissociation. Your Personal Preparation Indicator
NaCl(aq ) → Na + (aq ) + Cl− (aq ) u No. of Questions in Exercises (x)—
(Usually the term dissociation is used for weak electrolyte and ionisation for strong u No. of Questions Attempted (y)—
electrolyte). u No. of Correct Questions (z)—
(Without referring Explanations)
The solution of weak electrolytes contain ions, which are in equilibrium with unionised
molecules. u Accuracy Level (z / y × 100)—
CH3COOH - CH3COO − + H+ u Prep Level (z / x × 100)—
−
NH4OH - NH4+ + OH
This equilibrium is known as ionic equilibrium and is dynamic in nature. Accuracy Level should be above 85 & Prep
114 40 DAYS ~ JEE MAIN CHEMISTRY DAY TEN
This law holds good only in case of weak electrolytes. The

Degree/Dissociation
l
value of K can be calculated only in dilute solutions of

l
The fraction of total number of moles undergoing ionisation weak electrolytes.
is called degree of ionisation or dissociation (α ). Alternately,
the fraction of the amount of an electrolyte present in the
solution as free ions is called degree of ionisation (α ).
Various Concept of Acids and
α=
number of moles of electrolyte dissociated ionized as ions Bases and their Ionisation
total number of moles of electrolyte dissolved An acid is that whose aqueous solution tastes sour, turns blue
litmus red, neutralises bases and so on. On the other hand,
l
The extent of ionisation depends upon the strength of bond
the aqueous solution of a base tastes bitter, turns red litmus
and extent of solution of ions obtained.
blue, neutralises acid and so on.
Various factors influencing degree of ionisation/
dissociation are as follows: 1. Arrhenius Theory
(i) For strong electrolyte, α = 1 at normal dilution while According to Arrhenius theory, acids are substances that
for most of the polar covalent compounds, i.e. weak dissociates in water to give hydrogen ions H+ (aq) and bases
electrolytes, α <<< 1. are substances that produce hydroxyl ions OH− (aq).
(ii) Degree of ionisation of an electrolyte increases with
Limitations of Arrhenius theory are as follows:
polarity of the solvent.
(iii) The degree of ionisation of an electrolyte decreases (i) Free H+ and OH− ions do not exist in water.
with increase in concentration of the electrolyte. (ii) The concept is limited to aqueous solutions only.
(iv) The degree of ionisation rises with raise in (iii) It cannot explain the acidic character of certain
temperature of the solution. substances which don’t contain free H+ ions like, AlCl3,
(v) The addition of species possessing a common ion to BF3 and basic character of substances which don’t
that of weak electrolyte causes a decrease in the contain free OH− ions. NH3 , PH3 .
degree of dissociation of weak electrolyte.
2. Bronsted-Lowry Concept
Ostwald’s Dilution Law According to Bronsted-Lowry concept, acids are proton
It states that degree of dissociation of weak electrolyte is donors while bases are proton acceptors. A conjugate pair of
inversely proportional to the square root of concentration or acid and a base differs by a proton.
directly proportional to the square root of volume containing Conjugate base
one mole of the solute.
1 K HCl+ H2O → H3O + + Cl−
α∝ , α= = KV Acid Base
C C
Conjugate acid
where, α = degree of dissociation The substances which behave both as an acid and a base are
V = volume containing 1 mole of weak electrolyte called amphiprotic. e.g. H2O, HSO3− , HS − etc.
K = dissociation constant
Conjugate base of weak acid is strong or vice-versa.
NOTE
Ostwald’s dilution law is applicable only to weak electrolytes NOTE • The strength of acid depends upon the nature of solvent. e.g.
because for strong electrolytes, H2SO 4 , HClO 4 , HNO 3 and HCl, all have same strength in
α~
− 1, i.e. Ka → ∞ water due to levelling effect of water.
• In acetic acid solvent, the order of their acidic strength is
Various applications of Ostwald’s dilution law are as follows:
HClO 4 > H2SO 4 > HCl > HNO 3 .
l
To calculate the value of dissociation constant (K ) of the Limitations of Bronsted-Lowry concept are as follows:
weak acids and weak bases, by determining the degree of
λ  (i) The protonic definition cannot be used to explain the
dissociation (α ) from conductance measurement  V  at reactions occurring in the non-protonic solvents such as
λ  ∞ COCl2 , SO2 , N2O 4 etc.
any concentration C. (ii) This concept cannot explain the reactions between some
l
To calculate the degree of dissociation, α of weak acids and acidic oxides (such as CO2 , SO2 , SO3 ) and basic oxides
bases by knowing the value of K. (such as CaO, BaO, MgO) which take place even in the
For weak acid, put [ A + ] = [H+ ] and K = K a absence of the solvent, e.g. CaO + SO3 → CaSO 4
Similarly for weak bases, (iii) BF3 , AlCl3 etc., do not have any hydrogen and hence,
[B − ] = [OH− ] and K = K b cannot give a proton but are known to behave as acids.
DAY TEN IONIC EQUILIBRIUM 115
3. Lewis Concept Here, K w is called the ionic product of water and is defined as
the product of molar concentration of H+ ions and OH− ions
According to Lewis concept acids are the substances which
Kw
accept a pair of electrons to form a coordinate bond and bases K =
55. 55
are the substances which donate a pair of electrons to form
coordinate bond. where, K = ionisation constant
Following species can act as Lewis acids are l
Value of K w depends upon temperature as it is equilibrium
constant. If temperature increases, value of K w also increases.
(i) Molecules in which central atom has incomplete
octet e.g. BF3 , AlCl3 , FeCl3 etc. l
For dissociation of weak acids in water, K a is called acid
(ii) Molecules in which the central atom is either non-metal ionisation constant.
cation or metal cation with empty d-orbital. CH3COOH + H2O e CH3COO − + H3O + ;
(d-block elements)
[CH3COO − ] [H3O + ]
e.g. Si X 4 , GeX 4 , PX 3 , TiCl4 , H+ , Ag + etc. Ka =
(CH3COOH)
Lewis bases should satisfy following conditions are
l
Similarly, for a weak base, K b is called base ionisation
(a) Octet should be complete and central atom should be
constant.
more electronegative.
•• •• [NH+4 ][OH− ]
(b) Lone pair/pairs should be present, e.g. NH3 , H2O, NH4OH e NH+4 + OH− ; K b =
•• •• •• (NH4OH)
R—OH, R — O R etc.
•• ••
(c) Negatively charged species, e.g. CN − , OH− , Cl− etc.

Relation between K a and K b
l
Relation between acid dissociation (K a) and base
Limitations of Lewis concept are as follows:
dissociation (K b ) constants is
(i) The strength of Lewis acids and bases is found to
K a × Kb = K w
depend on the type of reaction, it is not possible to
arrange them in any order of their relative strength. where, pK a = − log K a, pK b = − log K b and pK w = − log K w
(ii) It does not explain the behaviour of protonic acids l
Many acids are capable of furnishing more than one
which do not form coordinate bond such as HNO3 , HCl, protons in water. Such acids are called polybasic or
H2SO 4 etc. polyprotic acids, e.g. H2SO 4 , H3 PO 4 etc.
(iii) Catalytic activity of Lewis acid cannot be explained l
The first ionisation constant (K a1 ) is always greater than the
because the catalytic activity of many acids is due to second ionisation constant (K a ).
their tendency to furnish H+ . Lewis acid does not do 1
so.
pH Scale
It is used to express and compare the acidic and basic
Relative Strength of Mono Acidic Bases strength of a solution. pH is defined as the negative logarithm
Relative strength of mono acidic bases (or mono basic acids) of H3O + ion concentration (in moles per litre) present in it.
of equimolar concentrations can be given as
Thus, pH = − log [ H3O + ]
Strength of base (BOH)1 K b1 α1
= = Similarly, pOH = − log [OH− ]
Strength of base (BOH)2 K b2 α2
pH + pOH = 14
Strength of acid (HA)1 K a1 α1 Relation between pK a and pK b is given as:
= =
Strength of acid (HA)2 K a2 α2 pK a + pK b = 14 = pK w
pH scale range is 0 to 14 and it depends upon the value of
where, K a and K b are the dissociation constants of acid and
K w . As temperature increases, value of pH decreases at 25°C.
base respectively.
Following observations are seen with solutions:
Ionisation of Water (i) pH of very dilute (~10 −8 M or lower) acids or bases is

nearly 7 but not 7 (i.e. not simply – log [acid or base])
l
Pure water is a weak electrolyte and is ionised according to
due to ionisation of water.
following equation.
(ii) pH of strong acids with concentration > 1 M is never
H2O(l ) + H2O(l ) 1 H3O + (aq ) + OH− (aq )
negative, it is zero only.
At 25°C, for pure water [H3O + ] = [OH −] = 10 −7 mol/L
NOTE Greater the value of Ka or Kb smaller is the value of pKa and
K w = [H3O + ][OH− ] = 10 −14 pKb and stronger is acid or base.
116 40 DAYS ~ JEE MAIN CHEMISTRY DAY TEN
pH of Mixtures of Acid and Bases l

The salts other than halides, sulphates, nitrates of metals
fall into salts of weak acid and base category, e.g.
The rules for determining the pH of mixtures of acids and
CH3COONH4 etc.
bases are as follows:
Kw 1
(i) If strong acid or strong base remains unused, calculate the For such salts, K h = , pH = 7 + [pK a − pK b ]
K a × Kb 2
concentration or molarity of H+ ions and OH− ions left in
the solution and then calculate the pH or pOH accordingly. NOTE There is no effect of dilution on the hydrolysis of salts of weak
(ii) If weak acid or weak base is left behind or remains acid and weak base because pH and Kh are all independent of
unused, a buffer (acidic or basic) is formed. Calculate concentration, C.
the concentration of salt formed (millimoles of salt
formed/volume of solution) and the concentration of Solubility of Sparingly
weak acid or weak base left behind. Use the buffer
equation to calculate the pH of the solution.
Soluble Salts
Lattice enthalpy and solvation enthalpy play an important
(iii) If acids or bases are completely neutralised, then salt is
role in deviding the solubility of the salts in particular solvent.
formed. Calculate the concentration of the salt formed
For a salt to be able to dissolve in a particular solvent, the
and use the hydrolysis equation to calculate the pH of
the solution. solvation enthalpy must be higher than its lattice enthalpy.
NOTE • pH value of a solution decreases on heating because

ionisation of water is an endothermic process. pH of boiling
Solubility Product
water is 6.5625, although it is neutral. It is defined as the product of molar concentration of its ions
• When pH decreases by one unit, H+ ion concentration in a saturated solution, each concentration terms raised to the
increases by a factor of 10. Similarly, when pH decreases by power equal to the number of ions produced on dissociation
two units, H+ ion concentration increases by a factor of 100. of one molecule of electrolyte.
Ax B y 1 x A + + yB −
Hydrolysis of Salts ∴ K sp = [ A + ]x [B − ] y
and pH of their Solutions e.g. A2 X 3 → 2 A3 + + 3 X 2 −
2S 3S
l
The process of salt hydrolysis is actually the reverse
process of neutralisation. The reaction of an anion or cation K sp = [ A3 + ]2 [ X 2 − ]3
of the salt with water accompanied to produce acidic and K sp = (2 S )2 (3 S )3
basic solution is called salt hydrolysis. Salt hydrolysis ∴ K sp = 108 S 5
affects the pH of the solution.
Saturated solution
l
Salts of strong acids and strong bases (i.e. neutral salts) do BaSO4(s) in water
Ba2+ (aq) + SO–4(aq)
not undergo hydrolysis are called neutral salt, e.g. NaCl, S S
CaSO 4 etc. If such salt is dissolved in water, pH of the K sp = [S ] [S ]
solution remains 7. K sp = S 2
l
Salt of a strong acid and weak base, e.g. NH4Cl are called where, S = molar solubility, K sp = solubility product
acidic salts. Such salts undergo cationic hydrolysis. pH of
NOTE If the ionic product exceeds the value of the solubility product
acidic salt solution will be less than 7. of a sparingly soluble salt then precipitation will occur.
For such salts, [H3O+] = K h × C
Kh =
Kw
or pH = 7 −
1
[ pK b + log C] at 25°C
Common Ion Effect
Kb 2 l
It states that if to the solution of a weak electrolyte, a
where, K h = hydrolysis constant solution of strong electrolyte is added which furnishes an
K b = ionisation constant for weak base ion common to that furnished by the weak electrolyte, the
C = molar concentration of salt. ionisation of the weak electrolyte is suppressed.
l
Salt of strong base and weak acid, e.g. NaNO2 , NaCN, e.g. NH4OH r NH4+ + OH−
CH3COONa are termed as basic salts. Such salts undergo l
If NH4Cl or NaOH is added to NH4OH solution, the above
anionic hydrolysis. pH of basic salt solution will be more equilibrium will shift to the left due to high concentration
than 7. of common ion and therefore, the ionisation of NH4OH is
K
For basic salts, [OH− ] = K h × C or K h = w further suppressed.
Ka l
In IInd group of qualitative analysis, H2S is passed in the
1
pH = 7 + [ pK a + log C] at 25°C presence of HCl. This is due to the fact that HCl suppresses
2 the ionisation of weakly dissociated H2S. Due to this only
DAY TEN IONIC EQUILIBRIUM 117
sulphides of II group radicals are precipitated. Sulphides (b) A buffer solution having pH more than 7 is called basic
of III, IV etc., groups are not precipitated because of their buffer. Weak base with its salt of strong acid gives basic
high solubility product. buffer.
−
l
The common ion effect is also used for almost complete e.g. NH4OH + NH4Cl, C 6H5NH2 + C 6H5NH+ 3 Cl
precipitation of a particular ion as its sparingly soluble salt,
with very low value of solubility product for gravimetric
estimation.
Henderson’s Equation for Buffer Solution
[salt]
For acidic buffer; pH = pK a + log
[acid]
Buffer Solution
The solution, which maintains its pH constant or [salt]
For basic buffer; pOH = pK b + log
reserve acidic or basic nature even upon addition of [base]
small amounts of acid or base is called buffer solution. The
ability of buffer solution to resist changes in pH on addition
of acid or base is called buffer action.
Buffer Capacity
A buffer solution should exhibit following characteristics: Buffer capacity is quantitatively defined as the number of
moles of acid or base added to 1 L in of buffer solution to
(i) Buffer solutions possess a definite pH value.
change the pH by unity.
(ii) Their pH value remains constant on keeping long or
dilution. number of moles of acid
/ base added to 1 L of buffer
(iii) The pH value is not changed on the addition of a strong Buffer capacity =
acid in acidic buffer and a strong base in basic buffer. change in pH
Two types of buffer are as follows: Buffer capacity is maximum when
(a) A buffer solution pH of which is less than 7 is called (a) [ salt] = [acid], pH = pK a for acidic buffer
acidic buffer. Weak acid with its salt of strong base gives
(b) [ salt] = [base], pH = pK b for basic buffer
acidic buffer.
e.g. CH3COOH + CH3COONa; HCN + NaCN Greater the buffer capacity, larger is its capacity to resist the
change in pH value.

1 Of the given anions, the strongest Bronsted base is 5 The ionic product of water at 310 K is 2.7 × 10 −14. What is
(a) ClO − (b) ClO −3 (c) ClO −2 (d) ClO −4 the pH of neutral water at this temperature?
2 Four species are listed below: (a) 7.0 (b) 5.98 (c) 6.78 (d) 4.58
I. HCO 3−
II. H 3 O +
III. HSO −4
IV. HSO 3F 6 Dissociation constant of a weak acid is1 × 10−4.
Which one of the following is the correct sequence of their Equilibrium constant of its reaction with strong base is
acidic strength? (a) 1 × 10−4 (b) 1 × 1010 (c) 1 × 10−10 (d) 1 × 104
(a) IV<II<III<I (b) II<III<I<IV 7 The pH of the neutralisation point of 0.1 N ammonium
(c) I<III< II<IV (d) III<I<IV<II hydroxide with 0.1 N HCl is
3 Three reactions involving H 2PO 4– are given below: (a) 8 (b) 6 (c) 7 (d) 9
I. H3PO 4 + H2O → H3O+ + H2PO 4– 8 NaOH is a strong base. What will be pH of 5.0 × 10−2M
II. H2PO 4– + H2O → HPO 42– + H3O+
NaOH solution ? (log 2 = 0.3) ª JEE Main (Online) 2013
(a) 14.00 (b) 13.70 (c) 13.00 (d) 12.70
III. H2PO 4– + OH– → H3PO 4 + O 2–
In which of the above does H2PO 4– act as an acid? 9 What is the pH of a 10−4 M OH − solution at 330 K, if Kw at
ª AIEEE 2010 330 K is 10 −13. 6? ª JEE Main (Online) 2013
(a) Only II (b) Both I and II (a) 4 (b) 9.0 (c) 10 (d) 9.6
(c) Only III (d) Only I 10 How many litres of water must be added to 1 L of an
4 The pKw of a neutral solution at 50°C is 13.36, what aqueous solution of HCl with a pH of 1 to create an
would be the pH of the solution at this temperature? aqueous solution with pH of 2? ª JEE Main (Online) 2013
(a) 7.63 (b) 7.00 (c) 6.68 (d) 7.96 (a) 0.1 L (b) 0.9 L (c) 2.0 L (d) 9.0 L
DAY TWELVE
Redox
Reactions
u Electronic Concept of u Oxidation Number u Balancing of Redox Reactions

Oxidation and Reduction u Redox Reactions
Redox reactions involve both oxidation and reduction simultaneously. Originally, the term
oxidation was used to describe the addition of oxygen to an element and reduction was used
to describe the removal of oxygen from an element.
Electronic Concept of Oxidation and Reduction

Loss of electron by an atom is called oxidation or de-electronation, while gain of electron by
an atom is called reduction or electronation.
1. Oxidants or oxidising agents are the substances which oxidise other and itself, get
reduced by gaining electrons (i.e. their oxidation number decreases during a reaction).
2. Reductants or reducing agents are the substances which reduce other and itself by get
oxidised losing electrons (i.e. their oxidation number increases during a reaction).
Some Important Oxidants

Some important oxidants used in oxidation are given below:
Molecules of most electronegative elements such as O2 , O3 , halogens.
PREP
l
l
Oxides of metals and non-metals such as MgO, CaO, CrO3 , H2O, CO2 etc.
l
The compounds having either of an element in their highest oxidation state such as MIRROR
K2Cr2O7 , KMnO 4 , HClO 4 , H2SO 4 , HNO3 , FeCl3 , HgCl2 , KClO3 etc.
l
Permanganate ion acts as strong oxidising agent and in acidic medium, it always produces u No. of Questions in Exercises (x)—
5 electrons per formula unit irrespective of the reducing agent. u No. of Questions Attempted (y)—
Some Important Reductants
Some important reductants used in reduction are given below: u Accuracy Level (z / y × 100)—
u Prep Level (z / x × 100)—
l
All metals such as Na, Al, Zn etc. and some non-metals, e.g. C, S, P, H2 etc.
l
Metallic hydrides such as NaH, LiH, KH, CaH2 and halogen acids such as HCl, HBr, HI. In order to expect good rank in JEE, your
Accuracy Level should be above 85 & Prep
l
The compounds having either of an element in their lowest oxidation state such as H2C2O 4 , Level should be above 75.
FeSO 4 , Hg2Cl2 , Cu2O, SnCl2 etc.
DAY TWELVE REDOX REACTIONS 133
Equivalent Weights of Oxidising Agent (OA) or e.g. 10 FeSO 4 + 2KMnO 4 + 8H2SO 4 → 2 MnSO 4
Reductant Oxidant
Reducing Agent (RA)
Molar mass of OA / RA agent + 5Fe2 (SO 4)3 + K2SO 4 + 8H2O
EOA/RA =
Number of electrons lost or gained per These are further divided into two types :
formula unit of RA / OA (i) Combination reactions in which two atoms or
H2O2 is both oxidising and reducing agent but its equivalent molecules (in their zero oxidation state) combine
weight as either oxidising or reducing agents are the same, together and one gets oxidised while the other gets
i.e. 17. reduced.
0 0 +4 −2
C + O2 → C O2
Oxidation Number Reductant Oxidant
The real or imaginary charge, which an atom appears to have (ii) Displacement reactions in which an atom or ion in a
in its combined state is called oxidation number of that atom.
compound is replaced by other atom or ion. These are
further divided in two types.
Rules for Assigning Oxidation Number (a) Metal displacement reactions in which metal with
l
The oxidation number of an element in its elementary state low reactivity is displaced by metal with high
and a compound is zero. e.g. H in H2 , S in S8. reactivity.
l
Oxidation number of an ion is equal to the electrical charge
CuSO 4 + Zn → Cu+ ZnSO4
present on it.
Oxidant Reductant
l
Oxidation number of fluorine is always −1 in all of its
(b) Non-metal displacement reactions in which
compounds.
non-metal is displaced.
l
The oxidation number of alkali metals is always +1 and
those of alkaline earth metals is +2. 2 Na + 2H2O → 2NaOH+ H2
Reductant Oxidant
l
Oxidation number of hydrogen is +1 except in ionic
hydrides, where it is −1. 2. Intramolecular redox reactions are the reactions
l
Two oxidation numbers of N are −3 and +3, when it is that involve oxidation of one element of a compound as
bonded with less electronegative and more electronegative well as reduction of other element of the same
atoms, respectively. compound. Decomposition reactions are also called
intramolecular redox reactions, but to be a redox
l
Oxidation number of oxygen is −2 except in
OF2 (+2), O2 F2 (+1), peroxides (−1) and superoxides (−1/2). reaction, it is essential that one of the products of
decomposition must be in the elemental state. e.g.
l
The oxidation number of halogens is always −1 in metal
∆
halides. (NH 4)2 Cr2O7 → N2 + Cr2O3 + 4H2O
l
In interhalogen compounds, the more electronegative
element out of the two halogens gets the oxidation number 3. Auto-redox or disproportionation reactions are the
of −1. reactions that involves oxidation and reduction of the
same element.
l
Oxidation number of metals in amalgams and carbonyls,
e.g. [Fe(CO)5] is zero. e.g. Cl2 + 2OH− → ClO − + Cl− + H2O
NOTE Valency of an element is always a whole number. It can neither

be zero nor fractional. While oxidation number may be positive Balancing of Redox Reactions
or negative. It can be zero or fractional.
Following two methods are used to balance the redox
reactions:
Redox Reactions
The reaction, which involves oxidation and reduction as its 1. Ion Electron Method
two half reactions is called redox reaction. A redox change This method involves the following steps :
occurs simultaneously. l
Write redox reaction in ionic form.
Redox reactions are of following three types : l
Split redox reaction into oxidation half and reduction half
1. Intermolecular redox reactions are the reactions that reactions.
involve the reaction between two substances, one of l
Balance atoms of each half reactions by using simple
them is oxidant and other is reductant. multiples.
134 40 DAYS ~ JEE MAIN CHEMISTRY DAY TWELVE
l
For balancing H and O, if the reaction is carried out in 2. Oxidation Number Method
acidic medium add H+ ion and H2O to the appropriate The method involves the following steps :
sides, similarly for basic medium add OH− and H2O to the l
Assign oxidation number to the atoms in the equation and
appropriate sides. write separate equations for atoms undergoing oxidation and
l
Balance the charge on both the sides and multiply one or reduction.
both half reactions by suitable number to equalise l
Find the change in oxidation number in each equation and
number of electrons in both equations. make the change equal in both the equations by multiplying
with suitable integers.
l
Add the two balance half-reactions and cancel common
terms.
l
After adding both the equations complete the balancing by
balancing H and O.

1 Which of the following is not a reducing agent? 9 The oxidation number of an element in a compound is
(a) SO 2 (b) H2O 2 (c) CO 2 (d) NO 2 evaluated on the basis of certain rules. Which of the
2 In which of the following reaction, nitric oxide acts as a following rules is not correct in this respect?
reducing agent? (a) The oxidation number of hydrogen is always +1
(a) 4NH3 + 5O 2 → 2NO + 6H2O (b) The algebraic sum of all the oxidation numbers in a
(b) 2NO + 3I2 + 4H2O → 2NO 3− + 6I− + 8H+ compound is zero
(c) 2NO + H2SO 3 → N2O + H2SO 4 (c) An element in the free or the uncombined state bears
(d) 2NO + H2S → N2O + S + H2O oxidation number zero
(d) In all its compounds, the oxidation number of fluorine is −1
3 Which one of the following cannot function as an
oxidising agent? ª JEE Main (Online) 2013 10 The oxidation number of sulphur in S 8 , S 2F2 and H 2S
−
(a) I (b) S(s) (c) NO −3 (aq) (d) Cr2O 2−
7
respectively are
(a) 0, +1and −2 (b) +2, +1and −2
4 In which of the following reactions, hydrogen is acting
(c) 0, + 1 and + 2 (d) −2, + 1 and − 2
as an oxidising agent ?
(a) With iodine to give hydrogen iodide 11 In which of the following, the oxidation number of oxygen
(b) With lithium to give lithium hydride has been arranged in increasing order?
(c) With nitrogen to give ammonia (a) BaO2 < KO2 < O3 < OF2
(d) With sulphur to give hydrogen sulphide (b) OF2 < KO2 < BaO2 < O3
5 The compound that can work both as an oxidising as (c) BaO2 < O3 < OF2 < KO2
well as reducing agent is (d) KO2 < OF2 < O3 < BaO2
(a) KMnO 4 (b) H2O 2 (c) Fe 2 (SO 4 ) 3 (d) K 2Cr2O 7
12 In the reaction,
6 MnO −4
is a good oxidising agent in different medium
3Br2 + 6CO23− + 3H2O → 5Br − +BrO3− + 6HCO−3
changing to
(a) bromine is oxidised and the carbonate radical is
MnO 4− → Mn2+ → MnO 24 − → MnO 2 → Mn2O 3
reduced
Change in oxidation number respectively, are (b) bromine is reduced and the carbonate radical is
(a) 1, 3, 4, 5 (b) 5, 4, 3, 2 oxidised
(c) 5, 1, 3, 4 (d) 2, 6, 4, 3 (c) bromine is neither reduced nor oxidised
7. The oxidation numbers of phosphorus in Ba(H 2PO 2 )2 (d) bromine is both reduced and oxidised
and xenon in Na 4 XeO 6 respectively are
(a) +3 and +4 (b) +2 and +6 (c) +1 and +8 (d) −1 and −6
13 The largest oxidation number exhibited by an element
depends on its outer electronic configuration.With which of
8 In which of the following pairs, there is greatest difference the following outer electronic configurations, the element
in the oxidation number of the underlined elements? will exhibit largest oxidation number?
(a) N O 2 and N2O 4 (b) P2O 5 and P4O10
(a) 3d1 4s 2 (b) 3d 3 4s 2 (c) 3d 5 4s1 (d) 3d 5 4s 2
(c) N2O and NO (d) S O 2 and SO 3
DAY THIRTEEN
Electrochemistry
u Metallic and Electrolytic u Electrochemical Cell u Batteries

Conduction u Electrochemical Series u Fuel Cells
u Electrolysis u Nernst Equation and its u Corrosion and its
u Kohlrausch’s Law Applications Prevention
The study of the chemical reactions which take place in a solution at the interface of an
electron conductor and an ionic conductor is considered under the branch of chemistry
namely as electrochemistry.
Metallic and Electrolytic Conduction

The substance which can conduct electricity are called conductors. On the basis of
species that conduct electricity (current), conductors are of two types :
(i) Metallic or electronic conductors can conduct current by transfer of free electrons.
This process is known as metallic conduction.
(ii) Electrolytic conductors can conduct current by the mobility of ions. This process is
known as electrolytic conduction.
Conductance in Electrolytic Solutions

l
The power of an electrolyte to conduct electric current is called conductance or
conductivity. Just like metallic conductors, electrolytic solutions also obey Ohm’s law.
l
Reciprocal of resistance is called conductance, G.
G=
1
= . Its unit is mho or (Ω −1 ) or Siemens (S).
1 PREP
resistance R MIRROR
Conductivity or Specific Conductance (κ)
l
The resistance of any conductor varies directly as its length (l) and inversely as its
u No. of Questions in Exercises (x)—
l l u No. of Questions Attempted (y)—
cross-sectional area (a), i.e. R ∝ or R = ρ u No. of Correct Questions (z)—
a a
where, ρ is called the resistivity or specific resistance.
l
If l = 1 cm and a = 1 cm2 then R = ρ u Accuracy Level (z / y × 100)—
1 l
∴ κ= = × conductance (G)
ρ a In order to expect good rank in JEE, your
140 40 DAYS ~ JEE MAIN CHEMISTRY DAY THIRTEEN
l l
Limiting molar conductivity or infinite conductivity
where, = cell constant, it is determined with the help of
a (Λ °m or Λ °m ) is defined as the molar conductivity of
conductivity bridge, where a standard solution of KCl is electrolyte when concentration of electrolyte approaches
used. zero (i.e. at infinite dilution).
l
The unit of specific conductance (κ) is ohm –1 cm−1 or S cm –1 .
Electrolysis
Molar Conductivity (Λ m ) l
Electrolysis is a process of decomposition of an electrolyte
It is the conducting power of all the ions produced by one by the passage of electricity through its aqueous solution or
gram mole of an electrolyte in a given solution. molten state. As a result cations move towards cathode
while anions towards anode.
κ × 1000
Thus, Λm = l
The reduction and oxidation changes occurs at respective
molarity
electrodes during electrolysis. Oxidation occurs at anode
The units for molar conductivity while reduction occurs at cathode.
= ohm−1 cm2 mol−1 or S cm2 mol−1 An electrolytic solution usually consists of more than two
l
ions. When electrolysis is done then all the ions are not
Equivalent Conductivity ( Λ eq ) discharged at electrodes simultaneously. Certain ions are
liberated at the electrodes in prefer to other.
It is the conducting power of all the ions produced by one gram For cations, which is stronger oxidising agent is discharged
equivalent of an electrolyte in a given solution. at cathode.
κ × 1000 K + ,Ca2 + , Na + , Mg2 + , Al3 + , Zn2 + , Fe2 + , H+ , Cu2 + , Ag + , Au3+
Thus, Λ eq = . The units for equivalent conductivity
normality →
Increasing order of decomposition
= ohm−1 cm2 (g - eq)−1 or S cm2 (g - eq)−1
For anions, which is stronger reducing agent is liberated at
Equivalent as well as molar conductivity ∝ dilution and anode.
specific conductivity ∝
1 SO24 , NO23 − ,OH− ,Cl− , Br − , I−
dilution →
Increasing order of discharge
Variation of Molar and Equivalent
Conductivities with Concentration Faraday’s Laws of Electrolysis
Strong electrolytes, like KCl, have high value of conductance 1. According to First Law of Faraday The amount of
even at low concentration and there is no rapid increase in chemical change produced is proportional to the quantity
their equivalent or molar conductance on dilution and can be of electric charge passing through an electrolytic cell.
represented by Debye-Huckel-Onsager equation, w ∝ Q , w = ZQ . w = Zit
1
where, w = mass of the metal deposited/gas liberated (in
Λ m= Λ m
° − AC 2
grams);
where, Λ m = molar conductivity Q = charge (in Coulomb)
Λ°m = limiting molar conductivity i = current (in amperes), t = time (in second)
A = Debye-Huckel constant Z = electrochemical equivalent.
C = concentration equivalent wt.  atomic wt. 
= Equivalent wt. = valency 
KCl
96500 C  
(strong electrolyte) l
1 Faraday = charge of one mole of electrons
1F = 6. 022 × 1023 × 1. 6 × 10 –19 = 96500 C (approx.)
Λm Λm
CH3COOH
l
Number of gram equivalents = Number of Faradays of
electricity, other forms of Faraday first law expression
(weak electrolyte)
E Q M
are w = ZQ = × Q = ×
F F Z
√C √C it M
Variation of Λ m with C for strong and weak electrolytes = ×
F Z
l
In case of weak electrolytes, like acetic acid, have a low l
One Faraday or 96500 C or 1 mole of electron cause the
value of conductance at high concentration and there is a reduction of 1 mole of monovalent cation or 1/2 mole
rapid increase in the value of equivalent conductance of divalent cation.
(molar conductance) with dilution.
DAY THIRTEEN ELECTROCHEMISTRY 141
2. According to Second Law of Faraday The number

of equivalents of any substance produced by a given
2. Galvanic or Voltaic Cells
quantity of electricity during electrolysis are same. It is a device in which a redox reaction used to convert
w A EA chemical energy into electrical energy.
=
w B EB Cu(s) + 2 Ag + (aq ) s Cu2 + (aq ) + 2 Ag(s)
where, w A = deposited mass of substance A,
E A = equivalent weight of A, Electrode and Half-Cell
w B = deposited mass of substance B,
A strip of metal, M called electrode is immersed in a solution
E B = equivalent weight of B.
containing the metal ion M n+ , this combination of the metal
electrode and solution is called a half-cell.
Kohlrausch’s Law Three kinds of interactions are possible between metal atom
It states that molar conductance at infinite dilution for any on the electrode and metal ion in solution.
electrolyte is the sum of contribution of its constituent ions,
i.e. anions and cations.
l
A metal ion M n+ may collide with the electrode and
undergo no change.
Λ°m = Λ°a + Λ°c
l
A metal ion M n+ may collide with the electrode, gain n
e.g. Λ°mCH3COOH → Λ°mCH3COO − + Λ°mH+ electrons and be converted to a metal atom M. The ion is
Λ°mAl 2(SO 4)3 → 2 × Λ°mAl 3+ + 3 × Λ°mSO 24− reduced.
M n+ (aq ) + ne − → M (s)

Reduction
Applications of Kohlrausch’s Law l

A metal atom M on the electrode may lose n electrons and
l
For the determination of equivalent/molar enter the solution as ion M n+ . The metal atom is oxidised.
conductivity at infinite dilution. Oxidation
M (s) M n+ (aq) + ne–
l
For the determination of degree of dissociation.
Degree of dissociation (α ) Electrolytic cell Voltaic or Galvanic cell
molar conductance at a given concentration
= Anode Cathode Anode
molar conductance at infinite dilution Cathode
Λcm Sign + – – +
α=
Λ∞m Electron flow out in out in
l
For the calculation of dissociation constant of a weak electrolyte. Half-reaction oxidation reduction oxidation reduction
Cα 2 Some different types of electrodes are as follows :

Ka= = Cα 2 [ QFor weak electrolyte, α <<< 1]
1 −α
1. Normal hydrogen electrode is the primary reference
Here, K a = equilibrium dissociation constant electrode and is used normally to know the electrode
C = molar concentration of weak electrolyte potential of a half-cell in galvanic all.
l
For the determination of solubility of sparingly soluble salt. 2. Standard hydrogen electrode is the hydrogen electrode in
κ × 1000 which the pressure of H2 gas is maintained at 1 atm and
Solubility =
Λ°m concentration of H+ ions is 1M.
3. Calomel electrode is an another generally used reference
Electrochemical Cell electrode but it is an secondary reference electrode.
A cell is an arrangement in which two electrodes are fitted in Calomel is the common name for mercury (I) chloride.
the same electrolyte or in which two different electrolytes are 1
joined by a salt-bridge. Hg + Cl − → Hg 2Cl2 + e −
2
Cells are of the following two types:
Salt-Bridge
1. Electrolytic Cells It is a U-shaped tube containing a gel permeated with a
It is a device in which electrolysis (chemical reaction solution of an inert electrolyte such as NH 4NO 3 . The ions of
involving oxidation and reduction) is carried out by using the inert electrolyte do not react with the other ions in the
electricity or in which conversion of electrical energy into solutions and they are not oxidised or reduced at the
chemical energy is done. electrodes. The salt-bridge is necessary to complete the
H+ electrical circuit and to maintain electrical neutrality in both
H2SO 4 (l ) s H2O(g) + O2 (g) + dil. H2SO 4 compartments (by flow of ions).
(Acidified /dil.)
Difference between Electrolytic and EMF of a Galvanic Cell

Electrochemical Cells In electrochemical cell, the electrodes in different half-cells
The main points of difference between these two cells are : have different reduction potential. This difference in electrode
l
The device in which electrolysis (chemical reaction potential of electrodes due to which electrons flow from anode
involving oxidation and reduction) is carried out by using to cathode is called electromotive force or cell potential of a
electricity or in which conversion of electrical energy into cell. This is the driving force for all cell reactions.
chemical energy is done is called electrolytic cell while
galvanic or voltaic cell is a device in which redox reaction Electrode Potential and Standard
is used to convert chemical energy to electrical energy.
Electrode Potential
l
In ‘electrolytic cell’, anode is positive electrode, while cathode
is negative electrode. On the other hand, in ‘galvanic cell’
l
If we connect two different electrodes, electrons will flow
anode is negative electrode and cathode is positive electrode. from the electrode of higher negative electric charge density
In both the cells, anode is always the site of oxidation and to the electrode with a lower negative electric charge
cathode is of reduction. density. A property closely related to the density of
l
In electrolytic cell, ions are discharged at both the electrodes, negative electric charge is called the electrode potential.
while in galvanic cell ions are discharged only at cathode. Potential difference between the metal and the metal ion in
l
In electrolytic cell, both the electrodes are fitted in same which electrode is dipped is called electrode potential
compartment, while in galvanic cell both the electrodes are denoted as E.
fitted in different compartments. l
In the standard state, when pressure is 1 atm, (latest IUPAC
correction use 1 bar) temperature is 298 K and
concentration is 1M, electrode potential is called standard
e– e– e– e– electrode potential denoted as E °.
Partition
l
According to international convention, if the
+ _ _ + standard electrode potential of a half-cell is 0.34 V,
it means it is the standard reduction potential E ° n+ ,
M /M
n+
of the half-cell M / M with half-cell reaction
M n+ + ne − → M.
° °
l
If Eox = xV, then E red = − xV
Anode Cathode Anode Cathode °
(a) Electrolytic cell (b) Voltaic or galvanic cell
l
Ecell or Ecell is the potential difference between the two
(emf is applied to cell) (emf is generated by cell) half-cells. Since, the potential difference is the driving force
for electrons, it is also called the electromotive force (emf)
Representation of a Cell of the cell or the cell potential or the cell voltage.
Consider the Daniell cell with following cell reaction:
l
The SI unit of cell potential is the volt (V) and the potential
2+ 2+ of a galvanic cell is defined as the positive quantity.
Zn(s) + Cu (aq ) → Zn (aq ) + Cu(s)
° ° °
Ecell = Eox + E red ,
In writing a cell diagram, following points are considered. We
divide the cell into two half-cells. Ecell = Eox + E red
The anode The cathode

l
Standard Hydrogen Electrode, SHE used as a reference
electrode. Its reduction potential is taken as zero. It is
Reaction Oxidation takes place Reduction takes place
represented as Pt, H2 (1 atm) | H + (1 M) or H + (1M)|H2
Zn( s ) → Zn 2 + (aq ) + 2e − Cu2 + (aq ) + 2e − → Cu(s )
(1 atm), Pt depending upon whether it acts as anode or
Terminal Negative Positive
cathode respectively.
Side LHS RHS
l
The difference between the potential required for the
Diagram Zn (s ) / Zn2 + (aq ) Cu2 + (aq ) / Cu (s)
evolution of gas and the standard electrode potential of that
Complete cell diagram may be represented as follows: gas is called over voltage/over potential.
Anode Salt-bridge Cathode
half-cell half-cell
Electrochemical Series
Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s) The arrangement of metals in decreasing order of tendency to
lose electrons (e − ) is called electrochemical series or it is the
Electrons flow this way
Phase Phase
boundary boundary
series in which the elements are arranged on the basis of the 2. To find Gibb’s free energy change
values of their standard reduction potential at 25°C. ∆G ° = – n E cell
°
F
Element Electrode reaction Standard electrode ∆G ° = standard Gibbs free energy change
(Reduction) reduction potential E°
(Volt)
Li Li+ + e– Li – 3.05
Relationship between Cell Potential
K K+ + e– K – 2.925 and Gibbs Energy Change ( ∆G)
2+ –
Ca Ca + 2e Ca – 2.87 l
In an electrochemical cell, maximum work done (∆G) is
Na Na+ + e– Na – 2.714 given by ∆G = − nF × Ecell
Mg Mg2+ + 2e– Mg – 2.37 where, F = Faraday’s constant
Al Al3+ + 3e– Al – 1.66 n = number of moles of electrons transferred.
Increasing strength of oxidising agent
Increasing strength of reducing agent

Increasing tendency for oxidation
Increasing tendency for reduction
Zn Zn2+ + 2e– Zn – 0.7628 l

A galvanic cell does electrical work by transferring
Cr Cr3+ + 3e– Cr – 0.74 electrical charge through an external circuit. When small
Fe Fe2+ + 2e– Fe – 0.44 amount of current is drawn from the cell then
Cd Cd+ + e– Cd – 0.403 − ∆G = Welec.
Ni Ni2+ + 2e– Ni – 0.25 For spontaneous reactions,
Sn Sn2+ + 2e– Sn – 0.14 ∆G = −ve
H2 2H+ + e– H2 0.00 ∴ Ecell = + ve
Cu Cu2+ + 2e– Cu + 0.337 (i) If ∆G of the system is positive then the process would be
–
I2 I2 + 2e– 2I + 0.535 possible only if the surrounding do electrical work on the
Ag Ag+ + e– Ag + 0.799 system (as in electrolysis).
2+ –
Hg Hg + 2e Hg + 0.885 (ii) If ∆G of the system is negative then the system does
Br2 Br2 + 2e– 2Br – + 1.08 electric work on the surroundings (as in galvanic cells).
Cr2 Cl2 +2e– 2Cl– + 1.36 For a voltaic cell, the work is done on the surroundings,
Au Au 3+
+ 3e –
Au + 1.50 thus given a negative sign. Hence,
F2 F2 + 2e– 2F – + 2.87 ∆G = Wmax = − nFEcell
and the standard free energy (∆G° ) is given by,
Nernst Equation and ∆G ° = − nFEcell
°
its Applications l
° ), free energy
The relation between cell potential (Ecell
(∆G° ) and equilibrium constant (K C ) is given by,
The relationship between electrode potential and
concentration of solution is called Nernst equation. ∆G ° = − 2.303 RT log K C
° 2.303 RT as ∆G ° = nFE °cell

E cell or EMF = E cell – log Q
nF 2.303 RT
and ° =
Ecell log K C
where, n = total number of electrons lost or gained nF
1F = 96500 C, T = 298 K, R = 8.314 J/K/mol l
If two half-reactions having potentials E1° and E2° are combined
[O. S. ]
Q = reaction coefficient of overall reaction =
[R. S.] to give a third half-reaction having a potential E3°, then
where, [O.S.] = concentration of oxidised state ∆G3° = ∆G1° + ∆G2°
[R.S.] = concentration of reduced state
or − n3 FE3° = − n1 FE1° − n2 FE2°
At T = 298 K, the Nerst equation becomes,
°
E cell = E cell –
0.0591
log Q or n3 E3° = n1 E1° + n2 E2°
n
n1E1° + n2E2°
The emf of a standard cell does not change with temperature. or E3° =
Weston cell is a common example of standard cell. n3
There are two important applications of Nernst equation are:
1. To find equilibrium constant Batteries
At equilibrium, E cell = zero A cell or a battery (arrangement of 1 or more cells connected
in series) is basically a galvanic cell and used where the
° 0.0591
∴ E cell = log K chemical energy of redox reaction is converted into electrical
n energy.
where, K = equilibrium constant.
There are two types of batteries. l

The half-cell reactions, when the battery is being used
up are:
1. The Primary Batteries At anode Pb(s)+ SO24− → PbSO 4 (s)+ 2e −
The battery in which the cell reaction occurs only once and At cathode PbO2 (s)+ SO24− + 4H + + 2e − → PbSO 4 (s) + 2 H2O
the battery becomes dead after use over a period of time
Overall reaction Pb(s) + PbO2 (s)+ 4H+(aq )+2SO24−(aq )
and cannot be reused again, e.g. dry cells like Leclanche
cell, mercury cell etc. Hence, primary batteries are not → 2PbSO 4 (s)+ 2H2O
rechargeable. e.g. dry cell, mercury cell, etc. The reaction is reversed during charging.
During charging following reactions occur :
(i) Dry Cell or Leclanche Cell At anode PbSO 4 (s)+ 2H2O → PbO2 (s)+ SO24− +4H+ + 2e −
It is also called primary voltaic cell. The electrode reactions
At cathode PbSO 4 (s)+ 2e − → Pb(s)+ SO24−
involved in this cell are :
Overall reaction 2PbSO 4 (s)+2H2O
At anode Zn (s) → Zn2 + + 2e –
→ Pb(s)+ PbO2(s)+4H+ + 2SO2−
At cathode MnO2 + NH+4 + e − → MnO(OH)+ NH3 4
l
Each cell gives an emf of about 2-V and in motor vehicles a
The cell potential is 1.6 V.
12-V battery of six cells is usually used. The lead-acid battery
produces 80–120 kJ per kilogram.
(ii) Mercury Cell
l
Mercury cell, suitable for low current devices like
hearing aids, watches.
Fuel Cells
l
Fuel cells are another means by which chemical energy may be
l
The electrode reactions for the cell are : converted into electrical energy. Energy can be obtained
At anode Zn(Hg)+2OH– → ZnO(s) + H2O + 2e − indefinitely from a fuel cell as long as outside supply of fuel is
maintained, e.g. H2  O2 fuel cell.
At cathode HgO + H2O + 2e − → Hg(l ) + 2OH–
l
This cell was used as a primary source of electrical energy on
The overall cell reaction is
the moon flights. The overall cell reaction produces water,
Zn(Hg) + HgO(s) → ZnO(s) + Hg(l ) which was used for drinking by the astronauts.
The half-reactions are
2. Secondary Batteries At anode 2H2 (g)+ 4OH− (aq ) → 4 H2O(l )+ 4 e −
These are also called reversible galvanic or voltaic cell. At cathode O2 (g)+ 2H2O(l )+ 4 e − → 4OH− (aq )
They are rechargeable because on charging reaction becomes
Overall cell reaction 2H2 (g)+ O2 (g) → 2H2O(l )
reverse, e.g. lead accumulator (lead storage) battery, nickel
cadmium cell etc. l
The efficiency of the fuel cell is the ratio of change in Gibbs
energy ∆G to the heat of combustion ∆H and mathematically
can be given as,
Lead Accumulator (Lead-Storage Battery)
∆G
l
In lead accumulator the electrodes are made of lead and η= × 100
∆H
the electrolyte consists of dilute sulphuric acid. The
electrodes are usually cast from a lead alloy containing where, η = thermodynamic efficiency of a fuel cell
7–12% of antimony (to give increased hardness and ∆H = heat of combustion
°
corrosion resistance) and a small amount of tin (for better ∆G = work done = − nFEcell
casting properties).
l
The electrodes are coated with a paste of lead (II) oxide Corrosion and its Prevention
(PbO) and finely divided lead; after insertion into the
l
Corrosion is basically an electrochemical phenomenon. A
electrolyte a ‘forming’ current is passed through the cell metal is oxidised by loss of electrons to oxygen and form
metal oxide, e.g. conversion of iron to rust [Fe2O3 ⋅ xH2O] , the
to convert the PbO on the negative plate into a sponge of
tarnishing of silver (due to formation of Ag2S), development of
finely divided lead. On the positive plate the PbO is
a green coating on copper and bronze.
converted to lead (IV) oxide (PbO2 ).
l
Corrosion of iron, known as rusting, occurs in the presence of
water and oxygen.
At anode 2Fe (s ) → 2Fe2 + (aq ) + 4e – Fe2O3 + xH2O → Fe2O3 ⋅ xH2O

+ Hydrated ferric
At cathode O2 (g ) + 4H (aq ) + 4 e → 2H2O (l )
–
oxide (rust)
The overall reaction Rusting of iron can be prevented by the following methods.
2Fe (s ) + O2 (g ) + 4H+ (aq ) → 2Fe2 + (aq ) + 2H2O (l ) (i) Barrier protection through coating of paints or
l
Fe2+ ions further oxidised by atmospheric oxygen to Fe3+ electroplating.
ions and form hydrated ferric oxide [Fe2O3 ⋅ xH2O]. (ii) Galvanisation or coating of surface with tin metal.
2+ +
4 Fe + O2 + 4 H2O → 2Fe2O3 (s ) + 8H (aq ) (iii) By the use of antirust solutions.

1 Conductance (unit Siemen’s) is directly proportional to 8 X g of silver is plated out on a serving tray by electrolysis
area of the vessel and the concentration of the solution in of a solution containing silver in +1 oxidation state for a
it and is inversely proportional to the length of the vessel, period of 8.0 h at a current of 8.46 A. What is the area of
then the unit of constant of proportionality is the tray if the thickness of silver plating is 0.00254 cm?
(a) S m mol –1 (b) S m2 mol –1 [Given, density of silver = 10.5 g cm −3 ]
(c) S–2 m2 mol (d) S2 m2 mol –2 (a) 10 .7 × 104 cm 2 (b) 1.02 × 104 cm2
(c) 4.1 × 10 cm
3 2
(d) 10.2 × 104 cm2
2 Resistance of 0.2 M solution of an electrolyte is 50 Ω. The
specific conductance of the solution is 1.3 S m −1. If 9 A current of 2 A is passed for 5 h through a molten tin
resistance of the 0.4 M solution of the same electrolyte is salt to deposit 22.2 g tin. What is the oxidation state of tin
260 Ω, its molar conductivity is ª AIEEE 2011 in salt ? [At. wt. of Sn = 118.69 g]
(a) 6250 Sm2 mol −1 (b) 6.25 × 10−4 Sm2 mol −1 (a) +2 (b) +5 (c) +3 (d) +4
(c) 625 × 10−4 Sm2 mol −1 (d) 62.5 Scm2 mol −1 10 In the electrolytic cell, flow of electrons is from
3 Resistance of 0.2 M solution of an electrolyte is 50 Ω. The (a) cathode to anode in solution
specific conductance of the solution of 0.5 M solution of (b) cathode to anode through external supply
same electrolyte is 1.4 S m −1 and resistance of same (c) cathode to anode through internal supply
solution of the same electrolyte is 280 Ω.The molar (d) anode to cathode through internal supply
conductivity of 0 . 5 M solution of the electrolyte in
11 When the sample of copper with the zinc impurity is to be
S m 2 mol−1 is ª JEE Main 2014
purified by electrolysis, the appropriate electrodes are
(a) 5 × 10−4 (b) 5 × 10−3 (c) 5 × 103 (d) 5 × 102
Cathode Anode
4 The equivalent conductance of NaCl at concentration (C) (a) pure zinc pure copper
and at infinite dilution are λ C and λ ∞ ,respectively. The (b) impure zinc pure copper
correct relationship between λ C and λ ∞ is given as (c) impure zinc impure sample
(Where, the constant B is positive) ª JEE Main 2014 (d) pure copper impure sample
(a) λC = λ ∞ + (B)C (b) λC = λ ∞ − (B)C
12 Λom (NH4OH) is equal to ……….
(c) λC = λ ∞ − (B) C (d) λC = λ ∞ + (B) C
(a) Λom (NH 4OH) + Λom (NH 4Cl) − Λo(HCl)
5 How many Faraday’s are required to reduce 1 mole of
(b) Λom (NH 4C l) + Λom (NaOH) − Λo(NaCl)
BrO –3 to Br – ?
(c) Λom (NH 4C l) + Λom (NaCl) − Λo (NaOH)
(a) 3 (b) 5 (c) 6 (d) 4
(d) Λom (NaOH) + Λom (NaCl) − Λo (NH 4Cl)
6 Two Faraday of electricity is passed through a solution of
13 For the reaction,
CuSO4.The mass of copper deposited at the cathode is
1
(atomic mass Cu = 63 . 5 u) ª JEE Main 2015 H 2(g ) + AgCl (s ) → H + (aq ) + Cl – (aq ) + Ag(s )
2
(a) 0 g (b) 63.5 g (c) 2 g (d) 127 g
occurs in the galvanic cell
7 A solution of copper sulphate (CuSO4 ) is electrolysed for
10 min with a current of 1.5 A. The mass of copper (a) Ag| AgCl(s) | KCl(aq) || AgNO 3 (aq)|Ag(s)
deposited at the cathode (Atomic mass of Cu = 63 u ) is (b) Pt | H2 (g) | HCl (aq) || AgNO 3 (aq) | Ag(s)
(c) Pt | H2 (g) | HCl(aq) || AgCl(s)|Ag(s)
ª JEE Main (Online) 2013
(a) 0.3892 g (b) 0.2938 g (c) 0.2398 g (d) 0.3928 g (d) Pt | H2 (g) | KCl(aq) || AgCl(s)|Ag(s)
DAY FOURTEEN
Chemical
Kinetics
u Rate of a Reaction u Molecularity u Effect of Temperature on

u Rate Law and Rate Constant u Differential and Integral forms Rate of Reaction
u Order of Reaction of Different Order Reactions u Collision Theory
Chemical kinetics is the branch of chemistry which addresses the rate of chemical
reaction. It includes the investigations of how different experimental conditions can
influence the speed of a chemical reaction and yield information about the reaction
mechanism and transition rates.
Rate of a Reaction
The rate or speed or velocity of a reaction is the rate of change of concentration of
reactants or products in unit time.
A→B
Rate of reaction can be defined in two ways
∆[ A] ∆[B]
1. Average rate of reaction, rav = – =
∆t ∆t
The units of rate of a reaction are mol L−1 s −1 or mol L−1 min −1 .
2. Instantaneous rate of reaction ( rinst ) can be calculated from rav in the limit ∆t → 0 and PREP
is represented as rinst = –
d[ A] d[B]
=
MIRROR
dt dt
No. of Questions in Exercises (x)—
In general for a reaction, aA + bB → cC + dD
u

1 d[ A ] 1 d[B] 1 d[C] 1 d[D]
Rate = – =– =+ =+ u No. of Correct Questions (z)—
a dt b dt c dt d dt (Without referring Explanations)
Accuracy Level (z / y × 100)—

Factors Affecting the Rate of Reaction
u

The rate of chemical reaction depends upon a number of factors such as
(i) concentration (ii) nature of reactants In order to expect good rank in JEE, your
(iii) temperature (iv) presence of catalyst Level should be above 75.
(v) exposure to radiations
154 40 DAYS ~ JEE MAIN CHEMISTRY DAY FOURTEEN
step. The atoms, molecules or ions participating in this step

Rate Law and Rate Constant decide the molecularity, e.g.
According to law of mass action, ‘‘the rate of a chemical HBrO3 + 6HI → HBr + 3H2O + 3I2
reaction is directly proportional to the product of effective
concentrations of reacting species, each raised to a suitable This reaction takes place through following steps:
power which may or may not be equal to the respective Slow
HBrO3 + HI → HBrO2 + HIO
stoichiometric coefficients.’’ (Rate determining step)
For a general reaction, Fast
HBrO2 + 4HI → HBr + 2H2O + 2I2
aA + bB → Products; Rate = k [ A]a[B]b
Fast
where, k is rate constant or velocity constant or specific HIO + HI → H2O + I2
reaction rate. The above expression is called rate law. Hence, two molecules participate in slowest step, the
l
Rate law cannot be deduced from balanced equation. It is reaction is bimolecular type.
obtained experimentally.
NOTE • Order of reaction may change with the condition such as
l
Rate constant of reaction (k ) is defined as the rate of pressure, temperature etc., whereas molecularity does not
reaction when the concentration of each reactant is taken as change.
unity. • Molecularity is always a whole number. It can never be zero,
l
Unit of k in terms of concentration, negative or fraction whereas, order of a reaction may be
whole number, fractional, zero or even negative.
Rate = k [ A] n
mol
=k
 mol 
n
Differential and Integral forms of
L ⋅ time  L 
Different Order Reactions
∴ Unit of k = (mol)1 − n ⋅ Ln − 1 s −1
where, n = order of reaction Zero Order Reaction
Reactions in which the concentration of reactants do not
Order of Reaction change with time and the concentration, rates remain
The sum of the powers of the reacting species that are constant throughout, are said to be zero order reactions.
involved in the rate law expression for the reaction represents R → P
the order of the reaction.
− d [R]
For the reaction, aA + bB → cC + dD Rate = = k [R]0
dt
dx
According to law of mass action, = k [ A]a[B]b The integrated rate equation is given as:
dt
dx [C ]t – [C ]0
According to rate law (rate equation), = k [ A]α [B]β k =–
dt t
Overall order of reaction = α + β where, C 0 = initial concentration of the reactant
The order of reaction can only be determined by experiments. C t = concentration of the reactant at any time t
l
Half-life of a reaction is the time required to reduce the
Molecularity concentration of the reactant to half of its initial value.
l
Molecularity is defined as the number of ions or molecules l
Half-life for zero order is given as:
or atoms taking part in an elementary process of the
[C]
reaction mechanism. t 1 /2 = 0
2k
l
In case of simple reactions, known as elementary reactions,
the molecularity is simply the sum of molecules of different where, k = rate constant, t 1 /2 = half-life period
reactants as represented by balanced equation, e.g. l
For a zero order reaction, half-life period is directly
(i) Unimolecular reaction N2O 4 (g) → 2NO2 (g) proportional to the initial concentration of reactant and
units of rate constant and rate of reaction are same, i.e.
(ii) Bimolecular reaction 2HI(g) → H2 (g) + I2 (g) mol L−1 s −1 .
(iii) Trimolecular reaction
2NO(g) + O2 (g) → 2NO2 (g) First Order Reaction
The first order reaction is defined as “the reaction in which
l
In case of complex reactions, i.e. the reactions involving
the rate is determined by the change of one concentration
more than one step the rate determining step is the slowest
term of the reactant only”.
DAY FOURTEEN CHEMICAL KINETICS 155
For first order reaction, l

When one of the reactants is present in large excess, the
R → P second order reaction confirms to the first order and is
called pseudo unimolecular reaction, e.g. hydrolysis of
− d[R]
Rate = = k [R] ester in acidic medium.
dt H + /H O
CH3COOC2 H5  
2
→ CH3COOH + C2 H5OH
Integrated rate equation is given as:
This is also known as pseudo first order reaction.
2.303 a
t= log Rate = k[CH3COOC2 H5]
k (a – x)
where, t = time, a = initial concentration Effect of Temperature on
k = rate constant,
(a–x) = concentration of a after time ‘t’
Rate of Reaction
l
It has been found that for a chemical reaction with rise in
l
Half-life of first order reaction is given as: temperature by 10°, the rate constant is nearly doubled.
0.693
t 1 /2 = , t 1 /2 = half-life period l
The effect of temperature is usually expressed in terms of
k temperature coefficient.
l
The unit of rate constant for first order reaction is s −1 . l
The value of temperature coefficient for most of the
1 reactions lies between 2 to 3.
l
For any reaction, half-life period, t 1 /2 ∝ n − 1
a
where, a = initial concentration, n = order of reaction Arrhenius Theory
l
Rate equation for first order gas phase reactions The temperature dependence of the rate of a chemical
2.303 p0 reaction can be accurately explained by Arrhenius equation.
k = log
t p0 − pt k = Ae – E a / RT ...(i)
where, p0 = initial pressure, pt = pressure after time t
k k
l
In a sequence of reactions, A →
A
B →
B
C. [B] is –Ea
maximum when, Slope =
log k 2.303 R
2.303 k 
t = log10  B 
(k B − k A )  kA
1/T
A plot between log K and 1/T
Second Order Reaction
The reaction is said to be of second order if its reaction rate is Here, k = rate constant
determined by the variation of two concentration terms of A = Arrhenius constant or frequency factor
reactants. E a = activation energy
1 x  It explains that the products are formed through the
Its rate equation can be represented as k =
l
, when

t  a(a − x)  intermediates or activated complex.
both the reactants are same. l
Arrhenius equation is based on two theories of reaction
The unit of rate constant for second order reaction is rates, collision theory and transition state theory.
mol−1 L s −1 . Since, k = Ae − E a / RT and E a is always positive, thus, k
l
Reactions of third and higher orders are rare. This is due to always increases with temperature.
the fact that the chances of three molecules of coming to a Due to this rate always increases with temperature whether
single point simultaneously, i.e. probability of trimolecular the reaction is exothermic or endothermic.
collisions is much less as compared to unimolecular or l
When, T → ∞, k = Ae 0 or rate constant becomes equal to
bimolecular collisions. Arrhenius or frequency factor. (For free radical reaction
l
Sometimes the rate of reaction decreases as the E a = 0, thus k = A and k becomes independent of
concentration of one of the constituent is increased, such temperature).
reactions are known as negative order reactions. e.g.
transformation of ozone into oxygen, i.e.
2O3 → 3O2
Activation Energy
l
The minimum amount of energy required for a chemical
1 d [O ]2
rate = − [O3 ] = k 3 = k [O3 ]2 [O2 ]−1 reaction to occur is called activation energy. It is
2 dt [O2 ] represented by E a.
156 40 DAYS ~ JEE MAIN CHEMISTRY DAY FOURTEEN
Activation energy does not depend on temperature, volume, d log k E

=
l
l
This reaction is also written as
pressure etc., but gets affected by the presence of catalyst. dT RT 2
l
Catalyst increases the rate of reaction by providing l
When log k is plotted against 1 / T, we get a straight line
alternative path of lower activation energy to the reactants. which is represented by Arrhenius equation as
A → B ∆H < 0, i.e. exothermic reaction Ea
log k = log A −
2.303 RT
l
Enzyme catalysed reaction are faster than the
metal catalysed reaction because they have lower activation l
The intercept of this line is equal to log A and slope is equal
energy. Threshold energy is independent of temperature, Ea
to − . Therefore, E a = −2.303 R × slope
but E a shows temperature dependence. 2.303 R
Reaction path
without catalyst –5.0
–6.0
–7.0 – Ea
Energy of Slope =
Potential energy
Energy of activation log k –8.0 2.303 R

Reaction activation without –9.0
path with with catalyst
Reactants –10.0
catalyst catalyst
–11.0
∆H –12.0
Products –13.0
Reaction coordinate 1.3 1.4 1.5 1.6

(1/T )
Effect of catalyst on activation energy
Plot of log k vs 1/T
Calculation of Activation Energy

Activation energy can be calculated by knowing the rate Collision Theory
constants at two different temperatures, assuming that E a and According to collision theory, the reactant molecule are
A remains constant. assumed to be hard spheres and reaction is postulated to
Taking log of both the sides in Arrhenius equation, we get occur when molecules collide with each other.
E
ln k = ln A − a l
The collisions among the reacting species which results in
RT the products are known as the effective collisions.
Now, if the values of rate constant at temperatures T1 and T2 l
The species taking part in the chemical reaction must have a
are k1 and k2 respectively then
certain minimum energy known as threshold energy (E ° ).
E
ln k1 = ln A − a …(i) l
Threshold energy = activation energy (E a)
RT1
+ average energy of molecules.
Ea
ln k2 = ln A − …(ii) l
If we assume that the rate of reaction is equal to rate of
RT2
collisions per unit volume or per unit time multiplied by
Subtracting the Eq. (i) from (ii), we get fraction of collisions then the rate constant is given by the
Ea  Ea  E E expression.
ln k2 − ln k1 = − − − = a − a
RT2  RT1  RT1 RT2 k = Z AB e − E a / RT
k2 E a  1 1  E T − T1  where, Z AB = collision frequency factor of reactants A and B

ln = − = a  2
k1 
R T1 T2  R  T1T2  l
When steric factor is considered the rate of reaction is given
as:
k2 E a  T2 − T1 
log =   [Here, T2 > T1 ] Rate = PZ AB e − E a / RT
k1 2.303 R  T1T2 
where, P is probability or steric factor.
l
This relation is used when rate constants at two different
temperatures are given.
DAY FIFTEEN
Adsorption and
Catalysis
u Concept of Adsorption u Langmuir Adsorption Isotherm

u Freundlich Adsorption Isotherm u Catalysis
The surface of a solid has the tendency to attract and retain the molecules of the phase with
which it comes into contact. These molecules remain only at the surface and do not go
deeper into the bulk. The accumulation of molecular species at the surface rather than in
the bulk of a solid or liquid is called adsorption.
Concept of Adsorption
l
The solid substances on the surface of which adsorption occurs is called adsorbent. The
molecular species that get adsorbed on the solid surface due to intermolecular attractions
are called adsorbate.
l
Rate of adsorption decreases with time whereas rate of absorption remains constant
with time.
l
If the concentration of an adsorbate at the surface of adsorbent is more than in the bulk of
the adjoining phases, it is called positive adsorption.
l
If concentration of an adsorbate at the surface of adsorbent is less than in the bulk of the
adjoining phases, it is called negative adsorption. PREP
l
The removal of the adsorbed substance from a surface is called desorption. MIRROR
l
Sorption is a process in which adsorption and absorption take place simultaneously and Your Personal Preparation Indicator
it is difficult to determine the relative extent of adsorption and absorption, e.g. dyes get
u No. of Questions in Exercises (x)—
adsorbed as well as absorbed on the cotton fibres.
Physisorption and Chemisorption (Without referring Explanations)
In physisorption, the particles of the adsorbate are held to the surface of the adsorbent by
u Accuracy Level (z / y × 100)—
physical forces such as van der Waals’ forces while in chemisorption, the molecules of the
adsorbate are held to the surface of the adsorbate by chemical bonds.
DAY FIFTEEN ADSORPTION AND CATALYSIS 167
Comparison between Physisorption and l

Freundlich gave an empirical relationship between the
Chemisorption quantity of gas adsorbed by unit mass of solid adsorbent
and pressure at a particular temperature.
Physisorption Chemisorption
Weak van der Waals’ forces are Strong chemical bonds are
l
The extent of adsorption is measured as x/ m,
present. present. where m is the mass of adsorbent and x is the mass of
adsorbate. At low pressure, x/ m varies linearly with p.
It decreases with increase in It first increases with increase in
x x 1
temperature. temperature and then decreases. = kp1/n or log = log k + log p
Heat of adsorption is low and it Heat of adsorption is high and it
m m n
is in the range of 20-40 kJ/mol. is in the range of 40-400 kJ/mol. x
At low pressure, = kp
It is reversible process. It is an irreversible process. m
It is an instantaneous process. It may be rapid or slow. x
At high pressure, = kp°
∆S is always negative. ∆S is positive for endothermic m
process.
In this, multilayer adsorption In this, single layer adsorption
occurs and thus, adsorbed layer occurs. Thus, adsorbed layer is x
x x = kp°
is several molecules thick. only unimolecular in thickness. 1/n m
m = kp
m Saturation
NOTE As the particles of the adsorbate are held on surface, ∆H and x pressure, ps
∆S both are negative and ∆H > T∆S. This is true in beginning. = kp
m
As adsorption proceeds, ∆H decreases and T∆S increases and p
ultimately, ∆H = T∆S and ∆G = 0. This state is called Freundlich adsorption isotherm
adsorption equilibrium. This is called Freundlich adsorption isotherm at constant
temperature.
Factors Affecting Adsorption of Gases l
Freundlich isotherm fails at high pressure and is only for
on Solids physical adsorption.
Adsorption depends upon the following factors:

1. Nature of Adsorbent A gas is adsorbed in different Langmuir Adsorption Isotherm
amounts on different adsorbents. Hydrogen is strongly To overcome the limitation of Freundlich adsorption isotherm,
adsorbed on nickel surface while it is weakly adsorbed Langmiur developed a new isotherm. It is represented as :
on alumina surface under identical conditions. x ap
2. Nature of Adsorbate Generally, the more liquefiable a = (a and b are constants)
m 1 + bp
gas, the more readily will it be adsorbed. Easily
x a
liquefiable gases such as NH3 , HCl, Cl2 , SO2 , etc., are At very high pressure, (bp >> 1) =
readily adsorbed than permanent gases, such as m b
x
O2 , H2 , N2 etc. At very low pressure, (bp << 1) = ap
m
3. Specific Area of Adsorbent It is the surface area of
adsorbent available for adsorption per gram of the
l
In case of chemisorption, x/ m initially increases with
adsorbate. Greater the surface area of the solid, larger temperature and then decreases.
would be its adsorbing capacity. l
At low temperature, x/m is small. As temperature is
4. Temperature Low temperature value favours physical increased, the molecules of the adsorbate gain energy and
adsorption but at high temperature, it decreases. In become equal to activation energy. Therefore, initially, x/m
increases with rise in temperature.
chemisorption, extent of adsorption first increases and
then decreases. The graph between extent of adsorption ( x / m) and
temperature T is called adsorption isobar.
5. Pressure of Gas At a given temperature, the extent of
adsorption will increase with the increase of pressure of
the gas.
p = constant
x x
m p = constant m
Freundlich Adsorption Isotherm
l
The variation in the amount of gas adsorbed by the
adsorbent with pressure at constant temperature can be T T
expressed by curve termed as adsorption isotherm. Physical adsorption Chemical adsorption
168 40 DAYS ~ JEE MAIN CHEMISTRY DAY FIFTEEN
Inhibitors are the substances which can make the catalyst

Adsorption from Solutions
l
inactive, e.g. Mg2+ acts as an activator for many enzymes

l
Solids adsorbs dissolved substances from solutions. For −
while C2O2−
4 and F act as inhibitors as they form complex
example, adsorption of colour impurities by activated
carbon in decolourising of solutions. with Mg2+ .
l
Freundlich adsorption isotherm and Langmuir adsorption NOTE • The catalytic poisoning is specific in nature.
isotherm are also applicable to adsorption from solutions.
x • In former case, catalyst surface is regenerated by scratching
Freundlich adsorption isotherm, = kC1/ n (n > 1) the surface while in later, catalyst surface is regenerated by
m
chemical treatment.
x aC
Langmuir adsorption isotherm, =
m (1 + bC)
Homogeneous and
Langmuir adsorption isotherm is applicable only to
chemisorption. Heterogeneous Catalysis
(i) In homogeneous catalysis, reactants and catalyst should
Characteristics of Adsorption be in same phase.
NO( g )
l
Adsorption is specific and selective phenomenon which e.g. 2SO2 (g) + O2 (g) → 2SO3 (g)
strictly refers to the existence of a higher concentration of
any particular component at the surface of a liquid or a (ii) In heterogeneous catalysis, reactants and catalyst are in
solid phase. different phase.
Finely
l
Adsorption is accompanied with decrease in free energy N2 (g) + 3H2 (g) → 2NH3(g)
of the system. In adsorption, there is a decrease in divided Fe( s )
entropy of the system.
As, ∆G < 0 and ∆S < 0, Activity and Selectivity of Solid Catalysts
Therefore, ∆H < 0 (∆H = ∆G + T∆S ) 1. Activity of catalyst depends upon the strength of
Thus, adsorption is always an exothermic process. chemisorption to a large extent.
l
The atoms or molecules of a solid surface have 2. Selectivity of a catalyst is its ability to direct a reaction to
unbalanced or residual attractive forces on the surface, yield a particular product. e.g.
which can hold adsorbate particles together. Thus, the Ni
adsorbed atoms or molecules can be held on the surface (i) CO(g) + 3H2 (g) → CH4 (g) + H2O(g)
of a metal by physical van der Waals’ forces or chemical Cu
forces due to residual valence bonds. (ii) CO(g) + H2 (g) → HCHO(g)
Adsorption is not very pronounced unless an adsorbent Cu/ZnO −Cr 2O3

(iii) CO(g) + 2H2 (g) → CH3OH (g)
l
possesses a large surface area for a given mass. Various

types of charcoals, silica gels, metal, etc., are used as NOTE The catalytic reaction that depends upon the pore structure of
adsorbents. Appreciable adsorption also takes place on the catalyst and the size of the reactant and product molecules
some smooth surfaces, such as those of platinum and glass. is called shape-selective catalysis.
l
Charcoal and other solids increased power of adsorption
on heating at low pressure with various gases or in air or Characteristics of Catalysts
vacuum at temperature varying from 350-1000°C. Such
treated charcoal is called activated charcoal and the
l
They become temporarily involved in a reaction providing
process is called activation. an alternative reaction path of lower activation energy than
that for the uncatalysed reaction.
l
They catalyse both forward and backward reactions to the
Catalysis same extent and thus have no effect on the equilibrium
l
The catalyst changes the rate of reaction by providing an constant.
alternate path of different activation energy. They l
The catalyst remains unchanged in amount and chemical
themselves remain chemically and quantitatively composition at the end of the reaction. It may undergo some
unchanged after the reaction. The phenomenon is known
physical change.
as catalysis.
l
In certain reactions, the rate of the reaction is dependent on
l
Promoters are the substances which can increase the
the concentration of the catalyst, e.g. rate of inversion of
efficiency of a catalyst. These are also known as
co-enzymes or activators. cane sugar is dependent on the concentration of H+ used as
catalyst.
DAY FIFTEEN ADSORPTION AND CATALYSIS 169
l
Rate of the reaction in certain heterogeneous reaction varies Mechanism for all enzyme catalysed reactions are
with surface area of the catalyst. Hence, finely divided E +S 2 ES (fast, reversible)
metals are preferred in the form of catalyst.
ES → E + P (slow, rate determining)
l
The catalyst does not initiate the reaction and are specific in
their action, e.g. starting from H2 and CO, three different 1. Autocatalysis is the phenomenon in which one of the
products are possible using different catalysts as products formed during the reaction acts as catalyst
Ni for the reaction. For example,
CO(g) + 3H2 (g) → CH4 (g) + H2O(g)
2KMnO 4 + 5H2C2O 4 + 3H2SO 4 →
Cu/ ZnO-Cr2O3
CO(g) + 2H2 (g) → CH3OH(g) K2SO 4 + 2MnSO 4 + 8H2O + 10CO2
Cu
CO(g) + H2 (g) → HCHO In this reaction, Mn2 + ions act as autocatalyst.
250 ° C
2. Induced catalysis is the type of catalysis, one reaction
influences the rate of other reaction which does not
Enzyme Catalysis and its Mechanism occur under ordinary condition. For example, the
Enzymes are biochemical catalysts. They are proteins and reduction of HgCl2 by oxalic acid is slow but becomes
extremely specific in nature. For example, faster if reduction is made in mixture of KMnO4 and
Urease HgCl2 , where both are reduced. Reduction of KMnO4
NH2CONH2 + H2O → 2NH3 + CO2
thus, induces the reduction of HgCl2 .

1 Adsorption is a surface phenomenon because 5 Which of the following is the variation of physical
(a) adsorbent has large surface area adsorption with temperature?
(b) chemical compounds formed are not on the surface of
adsorbent
Adsorption
Adsorption
(c) only the surfaces of the adsorbent have unutilised valencies (a) (b)
(d) None of the above
2 Which one of the following characteristics is not correct for T T
physical adsorption?
(a) Adsorption on solids is reversible
Adsorption
Adsorption
(b) Adsorption increases with increase in temperature (c) (d)

(c) Adsorption is spontaneous
(d) Both enthalpy and entropy of adsorption are negative
T T
3 Which of the following statements is incorrect regarding
physisorption? 6 In the Freundlich adsorption equation x/m = kp1/n, the
value of n is
(a) It occurs because of van der Waals’ forces
(a) always greater than one
(b) More easily liquefiable gases are adsorbed readily
(b) always smaller than one
(c) Under high pressure, it results into multimolecular layer on (c) always equal to one
adsorbent surface (d) greater than one at low temperature and smaller than
(d) Enthalpy of adsorption (∆H adsorption ) is slow and positive one at high temperature
4 Amount of gas adsorbed per gram of adsorbent increases 7 For a linear plot of log ( x /m ) versus log p in a
with pressure, but after certain limit is reached, adsorption Freundlich adsorption isotherm, which of the following
becomes constant. It is due to statements is correct? (k and n are constants)
(a) multilayers are formed (a) 1/n appears as the intercept j
JEE Main 2016
(b) desorption takes place (b) Only 1/n appears as the slope
(c) temperature is increased  1
(c) log   appears as the intercept
n
(d) absorption also starts
(d) Both k and 1/n appear in the slope term
DAY SIXTEEN
Colloidal State
u Distinction Among True u Preparation of Colloids u Properties of Colloidal

Solutions, Colloids and u Purification of Colloidal Solutions
Suspension Solutions u Emulsions
u Classification of Colloids
A colloid is a heterogeneous system in which one substance is dispersed as very fine

particles in another substance called dispersion medium. Colloidal particles are larger
than simple molecules but small enough to remain suspended.
Distinction Among True Solutions,

Colloids and Suspension
l
Depending upon the size of dispersed particles, there are three different types of
solutions viz. true solutions, suspensions and colloidal solutions. In true solutions,
the dispersed particles are present as single molecule or ion. The size of the dispersed
particles is less than 1 nm. True solutions are homogeneous.
l
In colloidal solution, colloidal particles have an anormous surface area per unit mass
as a result of their small size. It is heterogeneous. In suspension, the size of dispersed
particles is more than 1000 nm. It is also heterogeneous.
Classification of Colloids PREP

Depending upon whether the dispersed phase and the dispersion medium are solids, MIRROR
liquids or gases, eight types of colloidal systems are possible. These are as follows: Your Personal Preparation Indicator
Dispersed Dispersion u No. of Questions in Exercises (x)—

Colloidal system Examples
phase medium u No. of Questions Attempted (y)—
Foam Gas Liquid Soda water, froth, shaving cream u No. of Correct Questions (z)—
Solid sol Gas Solid Foam, rubber, cork, pumice stone
Aerosol Liquid Gas Fog, mist, cloud u Accuracy Level (z / y × 100)—
Emulsion Liquid Liquid Milk, hair cream u Prep Level (z / x × 100)—
Solid emulsion (gel) Liquid Solid Butter, cheese
Aerosol of solids Solid Gas Dust in air, smoke Accuracy Level should be above 85 & Prep
Sol Solid Liquid Paint, ink, colloidal gold
Solid sol Solid Solid Ruby glass, gemstones, alloys, rock salt
DAY SIXTEEN COLLOIDAL STATE 175
l
On the basis of appearance, colloids are classified as follows :
(i) The colloidal systems, in which the dispersion medium is
Preparation of Colloids
a liquid or gas, are called sols. They are called hydrosol or Lyophilic colloids may be prepared by simply warming the
aquasol, if the dispersion medium is water. When the solid with the liquid dispersion medium. On the other hand,
dispersion medium is alcohol or benzene, they are lyophobic colloids have to be prepared by special methods.
accordingly called alcosol or benzosol. Substances are converted into colloidal solutions by the
following two methods:
(ii) The colloidal systems, in which the dispersion medium is
gas are called aerosols.
1. Dispersion Methods
The colloids can be classified into positive or negative
These methods involve the breaking of bigger particles to the
colloids according to the charge present on the dispersed size of colloidal particles.
phase particles.
The various dispersion methods are:
l
On the basis of affinity of phase, colloids are classified as
follows : (i) Electrodisintegration method (Bredig’s arc method), this
process involves dispersion as well as condensation. By
(i) Lyophilic colloids represent such colloidal systems in
this method, colloidal solutions of metals like gold, silver
which the particles of dispersed phase have great affinity
etc., are obtained.
for the dispersion medium.
These are reversible colloids, e.g. gum, gelatin, rubber, (ii) Peptisation involves the conversion of freshly prepared
proteins etc. precipitate into colloidal solution by adding suitable
electrolyte. The suitable electrolyte is known as
(ii) Lyophobic colloids represent such colloidal systems in
peptising agent. e.g.
which particles of the dispersed phase have no affinity for
the dispersion medium. Fe(OH)3 + FeCl3 → Fe(OH)3 Fe3+ + 3Cl−
Fresh ppt. Electrolyte Colloid
These are irreversible e.g. sols of metals and their
insoluble compounds like sulphides and oxides. 2. Condensation or Chemical Methods
If water is the dispersion medium, the terms used are These methods involve the growing of size of the dispersed
hydrophilic and hydrophobic colloids. phase or the size of colloidal particles.
Lyophobic colloids are less stable due to the presence of (i) By double decomposition
electric charge on their particles.
As2O3 + 3H2S → As2S3 + 3H2O
l
On the basis of molecular size, colloids are classified as follows: Colloidal solution
(i) Multimolecular colloids are the colloids in which (ii) By hydrolysis
colloidal particles consist of aggregate of atoms or small
FeCl3 + 3H2O → Fe(OH)3 + 3HCl
molecules with diameter less than 10 −9 m or 1 nm, Colloidal solution
e.g. a sol of gold, a sol of sulphur. (iii) By oxidation
(ii) Macromolecular colloids are the colloids in H2S+ 2HNO3 → 2H2O + 2NO2 + S
Colloid
which colloidal particles themselves are large molecules, In periodic precipitation, these reactions are carried out in
e.g. starch, proteins, enzymes, nylon etc. gel medium. As a result of this, rings or layers of precipitates
(iii) Associated colloids or micelles are the substances which are formed at definite intervals.
behave as normal electrolytes at low concentration but as
colloids at higher concentration. This is because at higher
concentration, they form associated particles called
Purification of Colloidal Solutions
micelles, e.g. soap and synthetic detergents. The following methods are commonly used to purify the
colloids:
The concentration above which micelle formation occurs
is called CMC (Critical Micelle Concentration) and the (i) Dialysis It is the process of removing small molecules or
temperature above which micelle formation occurs is ions from a sol by diffusion through a semipermeable
called Kraft temperature. membrane. In this process, impure colloidal solution is
placed in a bag of semipermeable membrane, dipping in
NOTE • In polydisperse colloids, the colloidal particles are of water, the ions diffuse through membrane. Ferric
different sizes while in monodisperse colloids, all the hydroxide sol can be purified by this method.
colloidal particles are more or less of identical size.
• The colligative properties of colloidal systems are low due to (ii) Electrodialysis If dialysis is carried out under the
aggregation. Hence, all colloidal solutions exhibit very low influence of electric field, it is called electrodialysis. This
osmotic pressure, very small elevation in boiling point and speeds up the migration of ions to the opposite
depression in freezing point. electrodes.
176 40 DAYS ~ JEE MAIN CHEMISTRY DAY SIXTEEN
(iii) Ultrafiltration Separation of sol particles from the liquid Protective Action of Lyophilic Colloids
medium and electrolytes by filtration through an ultrafilter is
As lyophobic sols are unstable (e.g. Au, Ag) and get easily
called ultrafiltration.
precipitated, the addition of lyophilic colloids like gums,
(iv) Ultra-centrifugation In ultra-centrifuge, the colloidal soaps etc., makes it difficult to precipitate. The process is
particles settle down at the bottom and impurities remain in
known as protection and the lyophilic colloids are termed
the solution.
as protective colloids.
NOTE Gold Number It is the minimum weight (in mg) which

Properties of Colloidal Solutions must be added to 10 mL of standard red gold sol so that
The important properties of the colloidal solutions are given no coagulation of it takes place when 1 mL of 10% NaCl
below: solution is rapidly added to it.
(i) Brownian Movement Colloidal particles are always in a state
of rapid random motion (zig-zag movement) which is termed Emulsions
as Brownian movement.
These are the colloidal solutions of two immiscible liquids
(ii) Tyndall Effect When a strong and converging beam of light is or partially immiscible liquid in which the liquids act as
passed through a colloidal solution, its path becomes visible the dispersed phase as well as the dispersion medium.
due to scattering of light by particles. It is called Tyndall effect.
There are two types of emulsions:
(iii) Electrophoresis The phenomenon, involving the migration of
(a) Oil in water type, e.g. milk in which tiny droplets of
colloidal particles under the influence of electric field
liquid fat are dispersed in water.
towards the oppositely charged electrode, is called
electrophoresis. (b) Water in oil type, e.g. stiff greases, in which water
being dispersed in lubricating oil.
l
Sedimentation potential or Dome effect is the reverse of
electrophoresis. It is set up when a particle is forced to During the preparation of emulsion, a small amount of
move in a resting liquid. some substances such as soap, gum, agar and protein etc.,
are added to stabilise the emulsion. These substances are
l
Electrophoretic mobility of colloidal particles is the
known as emulsifying agents.
distance travelled by particles in one second under a
potential gradient in one volt per cm. Since, different
colloids have different mobilities, so this method is used Charateristics of Emulsion
for separation of proteins, nucleic acids, polysaccharides l
Emulsions can be broken into constituent liquids by
etc. heating, freezing, centrifuging or chemical destruction
(iv) Coagulation or Flocculation The precipitation of particles of of emulsifying agent.
the dispersed phase in a sol is known as coagulation. The l
They show Brownian movement and Tyndall effect.
minimum amount of an electrolyte required to l
These can be diluted with any amount of the dispersion
cause precipitation of one litre of a colloidal solution is called medium.
coagulation value or flocculation value. The reciprocal
of coagulation value is regarded as the coagulating power. NOTE • Surfactants are the substances which get preferentially
(v) Hardy-Schulze Rule Higher the valency of the active ion, the absorbed at the air-water, oil-water and solid-water
greater will be its power to precipitate the sol. interfaces.
e.g. order of coagulating power is • C15H31COO −Na+ is an anionic surfactant, C18 H37 NH+3 Cl −
is cationic surfactant and Cn H 2 n+ 1 (OCH2CH2 ) x OH is
Al3+ > Ba2+ > Na+
non-ionic surfactant.
PO34− > SO24− > Cl−

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DAY NINE

u Equilibrium State u Equilibria Involving Chemical u Equilibrium constant

Concept of Dynamic Equilibrium u No. of Questions in Exercises (x)—

N2O 4 (g) s 2NO2 (g) (chemical equilibria)

Equilibria Involving Types of Chemical Equilibrium

General Characteristics of Equilibrium ∴ Rb = kb [C]c [D]d

2. Equilibrium constant in terms of partial pressure ( K p ). Equilibrium constant in terms of activities, K a

(iii) If K C is in the range 10 −3 to 103 , appreciable

NOTE Relation between Degree of Dissociation and Density 2. Effect of Pressure

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

u Weak and Strong Electrolytes u Ionisation of Water

Weak and Strong Electrolytes

Ionisation of Electrolytes PREP

This law holds good only in case of weak electrolytes. The

value of K can be calculated only in dilute solutions of

(c) Negatively charged species, e.g. CN − , OH− , Cl− etc.

Ionisation of Water (i) pH of very dilute (~10 −8 M or lower) acids or bases is

pH of Mixtures of Acid and Bases l

NOTE • pH value of a solution decreases on heating because

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

u Electronic Concept of u Oxidation Number u Balancing of Redox Reactions

Electronic Concept of Oxidation and Reduction

Some Important Oxidants

NOTE Valency of an element is always a whole number. It can neither

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

u Metallic and Electrolytic u Electrochemical Cell u Batteries

Metallic and Electrolytic Conduction

Conductance in Electrolytic Solutions

2. According to Second Law of Faraday The number

M n+ (aq ) + ne − → M (s)

Applications of Kohlrausch’s Law l

Cα 2 Some different types of electrodes are as follows :

Difference between Electrolytic and EMF of a Galvanic Cell

The anode The cathode

Increasing strength of reducing agent

Zn Zn2+ + 2e– Zn – 0.7628 l

° 2.303 RT as ∆G ° = nFE °cell

There are two types of batteries. l

At anode 2Fe (s ) → 2Fe2 + (aq ) + 4e – Fe2O3 + xH2O → Fe2O3 ⋅ xH2O

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

u Rate of a Reaction u Molecularity u Effect of Temperature on

u No. of Questions Attempted (y)—

Accuracy Level (z / y × 100)—

u Prep Level (z / x × 100)—

step. The atoms, molecules or ions participating in this step

For first order reaction, l

Activation energy does not depend on temperature, volume, d log k E

Energy of activation log k –8.0 2.303 R

Reaction coordinate 1.3 1.4 1.5 1.6

Calculation of Activation Energy

k2 E a  1 1  E T − T1  where, Z AB = collision frequency factor of reactants A and B

u Concept of Adsorption u Langmuir Adsorption Isotherm

Comparison between Physisorption and l

Adsorption depends upon the following factors:

Inhibitors are the substances which can make the catalyst

inactive, e.g. Mg2+ acts as an activator for many enzymes