Van der Waal’s equation :

2
 P  an
 

 v2  (v – nb) = nRT
 
 Critical constants :
a 8a
Vc = 3b, PC = 2 , TC = 27 Rb
27b

THERMODYNAMICS
Thermodynamic processes :
1. Isothermal process : T = constant
dT = 0
T = 0
2. Isochoric process : V = constant
dV = 0
V = 0
3. Isobaric process : P = constant
dP = 0
P = 0
4. Adiabatic process : q=0
or heat exchange with the surrounding = 0(zero)
IUPAC Sign convention about Heat and Work :
Work done on the system = Positive
Work done by the system = Negative
1st Law of Thermodynamics
U = (U2 – U1) = q + w
Law of equipartion of energy :
f
U= nRT (only for ideal gas)
2
f
E = nR (T)
2
where f = degrees of freedom for that gas. (Translational + Rotational)
f=3 for monoatomic
=5 for diatomic or linear polyatmic
=6 for non - linear polyatmic

Page # 8
Calculation of heat (q) :
Total heat capacity :
q dq
CT =  = J/ºC
T dT
Molar heat capacity :
q dq
C=  = J mole–1 K–1
nT ndT
R R
CP =  – 1 CV =  – 1
Specific heat capacity (s) :
q dq
S=  = J gm–1 K–1
m T mdT
WORK DONE (w) :
Isothermal Reversible expansion/compression of an ideal gas :
W = – nRT ln (Vf/Vi)
Reversible and irreversible isochoric processes.
Since dV = 0
So dW = – Pext . dV = 0.
Reversible isobaric process :
W = P (Vf – Vi)
Adiabatic reversible expansion :
 T2 V2  1 = T1V1 1
Reversible Work :
P2 V2  P1V1 nR (T2  T1 )
W= =
 1  1
Irreversible Work :
P2 V2  P1V1 nR (T2  T1 )
W= = = nCv (T2 – T1) = – Pext (V2 – V1)
 1  1
P1V1 P2 V2
and use 
T1 T2
Free expansion–Always going to be irrerversible and since Pext = 0
so dW = – Pext . dV = 0
If no. heat is supplied q = 0
then E = 0 so T = 0.

Page # 9
Application of Ist Law :
U = Q + W  W = –P V
 U = Q –PV
Constant volume process
Heat given at constant volume = change in internal energy
 du = (dq)v
du = nCvdT
1 du f
Cv = . = R
n dT 2
Constant pressure process :
H  Enthalpy (state function and extensive property)
H = U + PV
 Cp – Cv = R (only for ideal gas)
Second Law Of Thermodynamics :
S universe = S system + S surrounding > 0 for a spontaneous process.
Entropy (S) :
B
dqrev
Ssystem =  T
A

Entropy calculation for an ideal gas undergoing a process :

irr
State A  State B
Sirr

P1, V1, T1 P2, V2, T2

T2 V2
Ssystem = ncv ln T + nR ln V (only for an ideal gas)
1 1

Third Law Of Thermodynamics :

The entropy of perfect crystals of all pure elements & compounds is zero
at the absolute zero of temperature.
Gibb’s free energy G) : (State function and an extensive property)
Gsystem = H system – TS system
Criteria of spontaneity :
(i) If G system is (–ve) < 0  process is spontaneous
(ii) If G system is > 0  process is non spontaneous
(iii) If G system = 0  system is at equilibrium.

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Physical interpretation of G :
The maximum amount of non-expansional (compression) work which
can be performed.
G = dwnon-exp = dH – TdS.
Standard Free Energy Change (Gº) :
1. Gº = –2.303 RT log10 K
2. At equilibrium G = 0.
3. The decrease in free energy (–G) is given as :
V2
–G = W net = 2.303 nRT log10
V1

4.  G ºf for elemental state = 0

º
5.  G ºf = Gproducts º
– GRe ac tan ts

Thermochemistry :
0 0
Change in standard enthalpy H° = Hm , 2 – Hm ,1
= heat added at constant pressure.
= CPT.
If Hproducts > Hreactants
 Reaction should be endothermic as we have to give extra heat to reactants
to get these converted into products
and if Hproducts < Hreactants
 Reaction will be exothermic as extra heat content of reactants will be
released during the reaction.
Enthalpy change of a reaction :
Hreaction = Hproducts – Hreactants
H°reactions = H°products – H°reactants
= positive – endothermic
= negative – exothermic
Temperature Dependence Of H : (Kirchoff's equation) :
For a constant pressure reaction
H2° = H1° + CP (T2 – T1)
where CP = CP (products)  CP (reactants).
For a constant volume reaction

E 02  E10  C V .dT

Page # 11
Enthalpy of Reaction from Enthalpies of Formation :
The enthalpy of reaction can be calculated by
Hr° =  B Hf°,products –  B Hf°,reactants
B is the stoichiometric coefficient.

Estimation of Enthalpy of a reaction from bond Enthalpies :

 Enthalpy required to   Enthalpy released to 

   
H =  break reactants into    form products from the 
 gasesous atoms
   gasesous atoms 
Resonance Energy :
H°resonance = H°f, experimental – H°f, calclulated
= H°c, calclulated– H°c, experimental

CHEMICAL EQUILIBRIUM
At equilibrium :
(i) Rate of forward reaction = rate of backward reaction
(ii) Concentration (mole/litre) of reactant and product becomes constant.
(iii) G = 0.
(iv) Q = Keq.
Equilibrium constant (K) :
rate constant of forward reaction Kf
K = rate constan t of backward reaction = K .
b

Equilibrium constant in terms of concentration (KC) :

Kf [ C ] c [D ] d
Kb = K =
[ A ] a [B ] b
C

Equilibrium constant in terms of partial pressure (KP ) :

[PC ] c [PD ] d
KP =
[PA ]a [PB ]b
Equilibrium constant in terms of mole fraction (Kx) :
x cC x Dd
Kx =
x aA x Bb

Relation between Kp & KC :

Kp = Kc.(RT)n.

Page # 12