1 THEMODYNAMICS

CHAMPIONS LECTURE SERIES

C–223
Time: 2 Hrs

Lecture Planning & Flow

No. Lecture Contents Homework of this lecture
I For JEE Main/CET Aspirants

Solve Abhyaas - VI (Level-I) with

detailed analysis a nd solut ions
(Don't just write the answer) on plane
II white sheet of paper and submit.

For JEE Advanced Aspirants

Solve Abhyaas - VI (Level - I & Level-II)

III with Detailed analysis and solutions
(Don't just write the answer) on plane
white sheet of paper and submit.
IV

VI

Has the student completed the homework of the previous lecture ? STAMP

Roll No.

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 IIT JEE / CHEMISTRY 2
THIRD LAW OF THERMODYNAMICS
The entropy of perfect crystals of all pure elements & compounds is zero at the absolute zero of temperature
.
Thus, absolute value of entropy unlike the absolute value of enthalpy for any pure substance can be calculated at
any given temperature . In standard state (298 K, 1 atm), it is standard absolute entropy S º .
T
nCdT
S = ST(K)– S0(K) =  T
0

S°m

For chemical reaction

aA + bB  cC + dH Tm TBP
T
S 0
system
= ( ni S 0m )product – ( ni S 0m )reactant
where S 0m = standard molar entropy. It can calculated using third law of thermodynamics.
Q system H system
Ssurr = =–
T T
* For a perfactly crystline substance at 0 K, entropy = 0
GIBB’S FREE ENERGY (G)
A system parameter to predict the spontaneity of chemical reaction was introduced by Gibb’s so that entropy
calculation for the surrounding need not be carried out.
It is a free energy at constant pressure.
G = H – TS
dG = dH –TdS – SdT & H = E + PV
dH = dE + PdV + VdP
 dG = dE + PdV + VdP –TdS –SdT
From Ist law of thermodynamics
dq = dE + PdV & from 2nd law , dq = TdS
dG = dq + VdP –TdS – SdT
dG = – SdT + VdP
At constant temperature, dG = VdP
nRT
For ideal gas , V =
P
RT
dGm = VmdP = dp
P
2 P2
dP
 dG m = RT  P
1 P1

P2
G m2 – G m1 = RTln
P1 , Where Gm is free energy for 1 mole

If G m1 is free energy for 1 mole in standard state and G m2 is free energy for one mole in any other state.
P P
Gm – G°m = RTln & G – G° = nRTln
1 1

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 3 THEMODYNAMICS

For the reaction, a A (g) + b B (g) C (g) + d D (g)

(G)reaction= GC + GD – GA – GB
PC
GC – G°C = cRTln  GC = G°C + cRTln PC
1
Similarly, GD= G°D + dRTln PD

GA= G°A + aRTln PA , GB= G°B + bRTln PB

(G)reaction= (G°C + cRTln PC) + (G°D + dRTln PD ) – (G°A + aRTln PA ) – (G°B + bRTln PB)

P c C .P d D
= (G)°reaction + RTln a b Greaction= G°reaction + RTlnQ
P A .P B

Gibb’s Helmholtz Equation :

dG = VdP – SdT
At constant Pressure

 dG   G 
dG = – SdT    =–S&   = – S
 dT P  T  P

G–H
& G = H – TS  =–S
T

G–H  G   G 
=   G = H + T  
T  T  P  T P

 G 
G = H + T   G = H – T S
 T  P
Sunivense = Ssystem + Ssurrounding

Q system H system

Ssurr = =–
T T
TS univ = TS system – Hsystem
Introducing a new thermodyamic function G = Gibb’s free energy (State function and an extensive property)
Gsystem = H system – TS system
 G = H – T S
Gsystem = H system – TS system .................. (ii)
Comparing equation (i) and (ii)
Gsystem = – TS universe
New 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
So, at every temparature G  0
H system S system G system = H system – TS system

+ Ve – Ve +
– Ve + Ve –
+ Ve + Ve – Ve at high temprature
– Ve – Ve + Ve at high temprature

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 IIT JEE / CHEMISTRY 4
Gº = standrad free energy change :
When the reactants under standrad conditions gets converted into products which is also under standered
condition, then the free energy change is known as Gº (it is a constant) for 1 mole at 1 bar.
At standared conditions :
G° = H° – TS°
= constant for a GIVEN REACTION
A B  C +  D
G° = (Gbb’s energy of product) – (Gibb’s energy of reactant)
G° =  G 0m,C + G 0m,D – G 0m,A –  G 0m,B , where G 0m can not be calculated as H 0m cannot be calculated.
hence, we can convert this relation in to Gibb’s energy of formation of substance.
G° = G 0f,C + G 0f,D – G 0f,A – G 0f,B

G 0f : standered Gibb’s energy of formation.

G 0f (elements in their standard states) = 0

G° = G 0f,product – G 0f,reac tan ts

For a reaction in progress
G = Gº + RT n Q
Q is reaction quotient, G > 0 backward is feasible, G < 0 forward is feasible
At equilibrium G = 0 Q=K  Gº = – RT n K at equilibrium

ILLUSTRATION-21 Ka for CH3COOH at 25ºC is 1.754 × 10-5 . At 50ºC, Ka is 1.633 × 10-5 What are Hº and Sº for the
ionisation of CH3COOH?
Solution: (Gº)298 = – 2.303RT log K = – 2.303 ×8.314 × 298 ×log (1.754 ×10-5) = 27194 J.
(Gº)323 = 2.303 × 8.314 × 323 × log ( 1.633 × 10-5) = 29605 J.
Gº = Hº – TSº 27194 = Hº – 298 Sº
29605 = Hº – 323 Sº
 Hº = – 1.55 kJ/mol Sº = – 96.44J/mol.K

ABHYAAS - VI
LEVEL - I
Gibbs free Energy
Q-1 Fill in the blanks
(i) Gibbs free energy G = ________.
(ii) G for reaction is given by ________.
(iii) For spontanus process G is _________.
(iv) For spontaneus process, if H  0 than S should be ______.
(v) If H > 0 & S  0 than G = ______.

Soln:

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 5 THEMODYNAMICS

Q-2 For the reaction between CO2 and graphite CO2 (g) + C(s) 2CO(g)
H = + 170.0 kJ and S= 170 JK-1. The reaction is spontaneous at -
(A) 298 K (B) 500 K (C) 900 K (D) 1200 K.

Soln:

Q-3 An exothermic reaction has a large positive entropy change. The reaction will be -
(A) Possible at all temperatures (B) Possible at low temperatures only
(C) impossible at all temperatures (D) Possible at high temperatures only

Soln:

Q-4 For precipitation reaction of Ag+ ions with AgCl -

(A) H =0 (B)G =0 (C)G = – ve (D) H = G

Soln:

Q-5 For the spontaniety of a reaction , which is true-

(A) G = +ve, H = + ve (B) H = +ve, S = - ve
(C) G = + ve, H = - ve (D) H = - ve, S = + ve

Soln:

Q-6 Which of the following is not a spontaneous process ?

(A) Dissolution of CuSO4 in water (B) Water flowing down hill
(C) Flow of current from low potential to high potential
(D) Reaction between H2 and O2 to form H2O

Soln:

Q-7 The occurrence of reaction is impossible if

(A) H is +ve ; S is also +ve (B) H is –ve ; S is also –ve
(C) H is –ve ; S is +ve (D) H is +ve ; S is –ve

Soln:

Q-8 For a reversible reaction at equilibrium G is -

(A) positive (B) negative
(C) zero (D) may be positive or negative

Soln:

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 IIT JEE / CHEMISTRY 6
Q-9 For a reaction A (g) + 3 B (g)  2C(g) ;  Hº = -24 kJ
The value of Gº is - 9 kJ. The standard entropy change of reaction approximately is:
(A) 5 JK–1 (B) –50 JK–1 (C) 500 JK–1 (D) 0.5 JK–1

Soln:

Q-10 For a reversible process -

(A)  Ssys.+ Ssurr.>0 (B) G > 0
(C) Ssys. = – Ssurr. (D) G < 0

Soln:

Q-11 Zeroth law is connected with

(A) Thermodynamic equilibrium (B) Isothermal process
(C) Heterogeneous system (D) None of these

Soln:

Q-12 The dependence of Gibbs free energy on pressure for an isothermal process of an ideal gas is given by

P2 V2 P V2
(A) GT = nRT ln (B) GT = nRT ln V (C) GT = nRT log 1 (D) GT = nRT log V
P1 1 P2 1

Soln:

Q-13 What is true for free energy

(A) It is very useful in predicting the spontaneity of a process
(B) It is not useful in predicting the spontaneity of a process
(C) It is uncertainly predicting the spontaneity of a process
(D) None of these

Soln:

Q-14 For a system at equilibrium

(A) G > 0 (B) G < 0 (C) G = 0 (D) None of these

Soln:

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 7 THEMODYNAMICS

Q-15 The occurrence of a reaction is impossible if

(A) H is + ve; S is also + ve but H < TS
(B) H is – ve; S is also + ve but H > TS
(C) H is – ve; S is +ve
(D) H is + ve; S is – ve

Soln:

Q-16 Equilibrium constant of a reaction is related to

(A) Standard free energy change Gº (B) Free energy change G
(C) Temperature T (D) None of these

Soln:

Q-17 For a spontaneous change, free energy change G is

(A) Positive (B) Negative
(C) Zero (D) Can be positive or negative

Soln:

Q-18 A spontaneous process is one in which the system suffers

(A) No energy change (B) A lowering of free energy
(C) A lowering of entropy (D) An increase in internal energy

Soln:

Q-19 The free energy change for a reversible reaction at equilibrium is

(A) Large positive (B) Small negative (C) Small positive (D) 0

Soln:

Q-20 A minus sign of the free energy change denotes that

(A) The reaction tends to proceed spontaneously
(B) The reaction is non-spontaneous
(C) The system is in equilibrium
(D) The reaction is very much unlikely

Soln:

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 IIT JEE / CHEMISTRY 8
Q-21 A process is spontaneous at all temperature, if
(A) H < 0 ; S < 0 (B) H < 0; S > 0 (C) H = 0; S < 0 (D) H > 0; S < 0

Soln:

Q-22 The relation between G and H is

(A) H = G - TS (B) G = H - TS (C) TS - G = H (D) H = TG + S

Soln:

Q-23 Which is not the correct relation between enthalpy (H) and intrinsic energy (E)
(A) H = E + PV (B) H = E + nRT (C) H = E - PV (D) E = H - PV

Soln:

Q-24 Which is correct

(A) G = - ve for spontaneous process (B) G = + ve for spontaneous process
(C) G = 0 for spontaneous process (D) H  0 for spontaneous process

Soln:

Q-25 H is the enthalpy change and S is the entropy change accompanying a reaction. The reaction is
most spontaneous if
(A) H and S are both negative (B) H is negative and S is positive
(C) H is positive and S is negative (D) H and S are both positive

Soln:

Q-26 For a reaction to occur spontaneously

(A) (H – TS) must be negative (B) (H + TS) must be negative
(C) H must be negative (D) S must be negative

Soln:

Q-27 The relation between G and E for a cell is G = – nFE; the cell reaction will be spontaneous if
(A) G is negative (B) G is positive (C) E is negative (D) E is positive

Soln:

Q-28 Mark the correct statement

(A) For a chemical reaction to be feasible, G should be zero
(B) Entropy is a measure of order in a system
(C) For a chemical reaction to be feasible, G should be positive
(D) The total energy of an isolated system is constant

Soln:

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 9 THEMODYNAMICS

NCERT QUESTION

Q-1 A reaction, A + B  C + D + q is found to have a positive entropy change. The reaction will be
(i) possible at high temperature
(ii) possible only at low temperature
(iii) not possible at any temperature
(iv) possible at any temperature
n
Sol :

Q-2 For the reactio at 298 K,

2A  B  C
H  400 kJ mol 1 and S  0.2 kJ K 1 mol 1
At what temperature will the reaction become spontaneous considering H and S to the constant over
the temperature range.
n
Sol :

Q-3 For the reaction

2 A  g   B  g   2D  g 
Uº  10.5 kJ and Sº  44.1 JK 1
Calculate Gº for the reaction, and product whether the reaction may occur spontaneously..
n
Sol :

Q-4 The equilibrium constant for a reaction is 10. What will be the value of G ?
R = 8.314 JK–1 mol–1, T = 300 K.
Soln:

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 IIT JEE / CHEMISTRY 10

HSC QUESTION
Q-1 The correct thermodynamic conditions for the spontaneous reaction at all temperatures are
(A) H < 0 and S > 0 (B) H > 0 and S < 0
(C) H < 0 and S < 0 (D) H < 0 and S = 0
Soln:

Q-2 For vaporization of water at 1 bar, H = 40.63 kJ mol –1 and S = 108.8 J K –1 mol –1 .
At what temperature, G = 0 ?
(A) 273.4 K (B) 393.4 K (C) 373.4 K (D) 293.4 K
n
Sol :

Q-3 Comment on spontaneity of reactions for which H is positive and S is negative.

n
Sol :

Q-4 Obtain the relationship between G0 of a reaction and the equilibrium constant.
Soln:

Q-5 Although S for the formation of two moles of water from H2 and O2 is –327JK–1, it is spontaneous.
Explain. (Given H for the reaction is –572 kJ).
Soln:

Q-6 Obtain the relation between G and S total Comment on spontaneity of the reaction.
Soln:

0
Q-7 For a certain reaction H 0 = 219 kJ and S = –21 J/K. Determine whether the reaction is spontaneous
or nonspontaneous.
Soln:

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 11 THEMODYNAMICS

Q-8 Determine whether the following reaction is spontaneous under standard state conditions.
0
 2H2O2  l  if H 0 = 196 kJ, S = –126 J/K
2 H2O  l  + O2(g) 
Does it have a cross-over temperature?
n
Sol :

Q-9 State whether followingreactions are spontaneous or not. Further state whether they are exothermic or
endothermic.
(a) H = –110 kJ and S = +40 JK–1 at 400 K
(b) H = +50 kJ and S = –130 JK–1 at 250 K
Soln:

Q-10 For a certain reaction H 0 is –224 kJ and S0 is –153 J K –1. At what temperature the change
over from spontaneous to nonspontaneous will occur?
Soln:

Q-11  C2H6(g), Kp = 3.356 x 1017

For the reaction, CH4(g) + H2(g) 
Calculate G0 for the reaction at 250C.
Soln:

Q-12 Calculate S total and state whether the reaction is spontaneous or nonspontaneous at 250C.
 Hg  l  + SO2(g),
HgS(s) + O2(g) 
0
H 0 = –238.6 kJ, S = + 36.7 J K–1
Soln:

Q-13 Calculate G for the reaction at 250C

CO(g) + 2 H 2 (g)   CH 3 OH(g), G0 = –24.8 kJ mol –1 . The partial pressures of gases
are PCO = 4 bar, PH 2  2 bar and PCH3 OH  2 bar
Soln:

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 IIT JEE / CHEMISTRY 12

ANSWERS
LEVEL - I

Q-1 (i) G = H - TS (ii) G = Gº + RT ln Qc (iii) Negative (G  0) (iv) (+ve)

(v) Positive ( G  0 )
Q-2 (D) Q-3 (A) Q-4 (C) Q-5 (D) Q-6 (C) Q-7 (D) Q-8 (C)
Q-9 (B) Q-10 (C) Q-11 (A) Q-12 (A) Q-13 (A) Q-14 (C) Q-15 (D)
Q-16 (A) Q-17 (B) Q-18 (B) Q-19 (D) Q-20 (A) Q-21 (B) Q-22 (B)
Q-23 (C) Q-24 (A) Q-25 (B) Q-26 (A) Q-27 (D) Q-28 (D)

NCERT QUESTION
Q-1 (iv)
Q-2 2000 k
Q-3 0.164 kJ, not spontaneous.
Q-4 – 5.744 kJ mol–1

HSC QUESTION
Q-1 (A) Q-2 (C)
Q-3 Non - spontaneous at all temperatures.
Q-4 Gº = – RT ln kc.
Q-5 S Total  S sys  S surrounding  1919  327  0  Hence spontaneous.
Q-6 G = – TSTotal
if
(i) STotal > 0 and G < 0, process is spontaneous.
(ii) STotal < 0 and G > 0, process is non- spontaneous.
(iii) STotal = 0 and G = 0, process is at equilibrium.
Q-7 non - spontaneous.
Q-8 (Non - spontaneous, No)
Q-9 (a) Spontaneous, exothermic (b) non - spontaneous, endothermic
Q-10 1464 k
Q-11 – 100 kJ mol–1
Q-12 STotal = + 837.4 J k–1, spontaneous reaction.
Q-13 – 29.953 kJ mol–1

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