CONCEPT PHYSICAL CHEMISTRY (Part-I)

Solutions, Electrochemistry and Chemical Kinetics form the basis of physical chemistry and give an idea about the nature of
solutions, relationship between chemical energy and electrical energy in redox reactions and also the rates of reactions.

SOLUTIONS ELECTROCHEMISTRY CHEMICAL KINETICS

Expressing Concentration of Solutions Basic Terms Rate of Reaction

 Mass percentage : Grams of solute in 100 g of  Conductance : Reciprocal of resistance.  For a reaction, aA + bB  xX + yY
solution. 1 1 d[ A] 1 d[ B] 1 d[ X ] 1 d[Y ]
 Strength : Grams of solute in 1 L of solution. C  ; Unit : 1 or S Rate     
R a dt b dt x dt y dt
 Molarity : Moles of solute in 1 L of solution.  Conductivity : Conductance of 1 cm3 of the  Greater the concentration of reactants, faster is the
 Normality : Gram equivalents of solute in 1 L reaction.
conductor.
of solution.  Rate becomes double for every 10° rise in
l
 Molality : Moles of solute in 1 kg of solvent.   C  ; Unit : 1 cm 1 or S cm 1 temperature.
 Mole fraction : Moles of the component/ total a
 Greater the surface area of reactants, faster is the
 Equivalent conductivity : Conductance of a
no. of moles of all components. reaction.
 Parts per million : Mass of solute in one solution containing 1 g-equivalent of an
million (106) parts by mass of solution. electrolyte dissolved in V cm3 of the solution.
  1000 Order and Molecularity
eq  ; Unit : S cm2 eq 1
Laws Normality
 Molar conductivity : Conductance of a solution  For a rate law equation, rate = k[A]a[B]b
 Henry’s law : m = Kp or p = KHx Order of reaction = a + b.
containing 1 mole of an electrolyte dissolved in  Molecularity is the number of atoms, ions or
where KH is Henry’s constant having units of V cm3 of the solution. molecules that must collide simultaneously with
pressure.
  1000 one another to result into a chemical reaction.
 Raoult’s law :
p  ps n2 m  ; Unit : S cm2 mol 1
For non-volatile solute :   x2 Molarity
p n1  n2  Electrode potential : Tendency of an electrode to
For volatile components : lose or gain electrons when it is in contact with Integrated Rate Equation and Half-Life
pA = xAp°A ; pB = xB pB° and ptotal = pA + pB
solution of its own ions.
 Cell potential or EMF of the cell : The difference Order Integrated Half-life
rate equation t1/2 =
Types of Solutions between electrode potentials of two half-cells.
0 [A]t = –kt + [A]0 [A]0/2k
 Ideal solutions : A–B interactions are of same
magnitude as A–A and B–B interactions, Types of Cells 1 ln[A]t = –kt + ln[A]0 0.693/k
Vmix = 0 and Hmix = 0. 2 1/[A]t = kt + 1/[A]0 1/k [A]0
 Non-ideal solutions : A–B interactions are of  Electrochemical cell : Device used to convert
different magnitude than A–A and B–B chemical energy of a redox reaction into 1 [ B] [ A]
2 kt  ln 0 –
interactions, Vmix  0 and Hmix  0. electrical energy. [ A]0  [ B]0 [ A]0[ B]
– Non - i d e a l s oluti ons show ing +ve  Electrolytic cell : Device which uses electricity
1 1 2n 1  1
deviations : A–B interactions are weaker to bring about a non-spontaneous redox n (n  1) kt  
than A–A and B–B interactions, Vmix reaction. [ A]n 1 [ A0 ]n 1 k (n  1)[ A]n0 1
= +ve, Hmix = +ve and resulting vapour
 Relationship between time for different fractions of
pressure is higher than that expected.
Laws a first order reaction to complete,
– Non - i d e a l s oluti on s show i ng –ve
t3/4 or t75% = 2t1/2
deviations : A–B interactions are stronger
 Faraday’s first law : W = Zit 3
than A–A and B–B interactions, Vmix = t 87.5%  3t1/2  t 75%
W1 E1 2
–ve, Hmix = –ve and resulting vapour  Faraday’s second law :  t93.75% = 4t1/2 = 2t75%
pressure is lower than that expected. W2 E2
t96.87% = 5t1/2
 Azeotropes: Constant boiling mixtures.  Kohlrausch’s law : For an electrolyte AxBy,
t99.9% = 10t1/2
°m = x°+ + y°– or °eq = °+ + °–
Colligative Properties
Temperature Dependence of Rate of
 Colligative properties depend only on the Nernst Equation and Electrochemical Series Reaction and Effect of Catalyst
number of particles of solute dissolved in a
definite amount of solvent. These are :  Nernst equation : For the reaction :
n+ –
 Arrhenius equation : k = Ae–Ea/RT
– Elevation in boiling point : Boiling point M + ne  M, Ea  T2  T1 
k
of solution is higher than that of pure or log 2 
k1 2.303R  T1T2 
RT M
E  E  ln or
solvent. Tb = Tb – Tb° = Kb m nF [ M n ]
 Activation energy
– Depression in freezing point : Freezing
point of solution is lower than that of pure 0.0591 1 = Threshold energy – Average kinetic
E  E  log n  at 298 K
solvent. Tf = T°f – Tf = Kf m n [M ] energy of reactants
– Relative lowering of vapour pressure :  For concentration cell :  Collision theory : k = PZe–Ea/RT
p  ps n 0.0591 C where P is steric factor and Z is collision
 x2  2 (for dilute solutions, Ecell  log 2 ; Ecell  +ve if C2  C1
p n1 n <<< n ) n C1
frequency.
2 1
 Catalyst increases the rate of a reaction
p  ps n2  for dilute as well as   For a reaction in equilibrium :
   without itself undergoing any permanent chemical
ps n1  concentrated solutions  0.0591
E cell  log K at 298 K change.
– Osmotic pressure :  = CRT n
 Electrochemical series : It is the arrangement of
electrodes in order of increasing standard
van’t Hoff Factor (i) and its Significance reduction potentials.
– This series helps in comparing the relative
HAVE A LOOK !
Observed value of colligative property
i oxidizing or reducing powers, relative  Different solutions having same vapour pressure
Normal value of colligative property
activities of metals and to predict spontaneity are called isopiestic solutions.
Calculated molecular mass
 of the redox reaction.
Observed molecular mass  Deliquescent substances absorb moisture because
vapour pressure of their saturated solutions is less
 For solute undergoing association :
n than that of water vapours in air at that
  (1  i) ; i 1 Commercial Cells/Batteries temperature.
(Degree of association) n 1
 For solute undergoing dissociation :  Primary cells cannot be recharged e.g., dry cell,  Efflorescent substances lose their water of
i 1 mercury cell. crystallisation because their hydrated crystals have
  ; i 1 vapour pressure larger than that of water vapours in
(Degree of dissociation) n  1  Secondary cells can be recharged e.g., lead air.
 Modified colligative properties : storage battery, Ni–Cd storage cell.
p  ps  Association generally occurs in non-aqueous
 Fuel cells convert the energy produced during
 ix2 ; T = iK m, T = iK m; solvents (non-polar) because high dielectric
p b b f f combustion of fuels into electrical energy constant of water helps in the dissociation of the
 = iCRT directly e.g., H2–O2 fuel cell. associated molecules.