Fiziks: Maxwell Relation and Thermodynamic Potential

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Institute for NET/JRF, GATE, IIT‐JAM, M.Sc. Entrance, JEST, TIFR and GRE in Physics
Chapter - 6
Maxwell relation and Thermodynamic Potential
6.1 Maxwell Relations
Let, F  F ( x, y ) and if it is perfect differential work, then dF  Mdx  Ndy
 F   F 
Where, M    and N    , then M and N will satisfy the condition
 x  y  y  x
 M   M 
   
 y  x  x  y
Maxwell relations are relationship between two derivatives of thermodynamic variables,
and energy due to the equivalence of potential second derivative under a change of
d 2F d 2F
operation order  , where F is thermodynamic potential and x and y are
dx dy dy dx
two of its natural independent variables.
Maxwell relations are extremely important for two reasons.
First they show us that derivative of thermodynamic parameters are not all independent.
This can serve as a consistency check in both experiments and in theoretical analysis.
Maxwell relations provide a method for expressing some derivative in other ways. This
enables as to connect difficult measurable quantities to those which are readily accessible
experimentally.
The measurement of entropy and chemical potential can not be directly measurable in lab
but with the help of Maxwell relations, there thermodynamic property can be determined
theoretically.
For Maxwell relation.
Let us consider Legendre the independent variable as x , and y such that
U  U  x, y  , S   x, y  V  V  x, y 
 U   U 
So, dU    dx    dy
 x  y  y  x
 S   S 
dS    dx    dy
 x  y  y  x
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 V   V 
dV    dx    dx
 x  y  y  x
From first law of thermodynamics,
dU  TdS  PdV
 U   S   V 
   T    P 
 x  y  x  y  x  y
 U   S   V 
   T    P 
 y  x  y  x  y  x
Hence, U , V and S are perfect differential.
   U      U      V      V  
Then,                
 y  x  y  x  x  y  x  y  y  x  y  x  x  y  x  y
   S      S  
       
 y  x  y  x  x  y  x  y
   U    T   S     S     P    V     V  
          T           P    ---(1)
 y  x  y  x  y  x  x  y  y  x  y  x  y  x  x  y  y  x  y  x
Similarly,
   U    T   S     S    P   V     V  
         T           P     ---(2)
 x  y  x  y  x  y  y  x  x  y  x  y  x  y  y x  x  y  x  y
Equating equation (1) and (2),

 P   V   P   V   T   S   T   S 
                (A)
 x  y  y  x  y  x  x  y  x  y  y  x  y  x  x  y
Maxwell first relation:- Put x  T , y  V
 S   P 
   
 V  T  T V
Maxwell Second Relation:- Put, x  T , y  P
 S   V 
    
 P  T  T  P
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Maxwell Third Relation:- Put, x  S , y  V
 T   P 
    
 V  S  S V
Maxwell Fourth Relation:- Put, x  S , y  P
 T   V 
   
 P  S  S  P
Thermodynamic potential is a scalar function used to represent the thermodynamic state
of system. The concept of thermodynamic potentials was introduced by Pierre Duhem in
1886.
One main thermodynamic potential that has a physical interpretation is the internal
energy. It is energy of configuration of a given system of conservative forces. Expression
for all other thermodynamic energy potentials are derivable via Legendre transformation.
6.2 Different Types of Thermodynamic Potential and Maxwell Relation
Thermodynamic potentials are different form of energy which can be used in different
thermodynamic process .thermodynamic potentials are path independent variables, so
they are perfect differential
If F is unique Thermodynamic potential defined by variables x and y , as F  F ( x, y )
and if it is perfect differential then, dF  Mdx  Ndy
 F   F 
where, M    and N    ,
 x  y  y  x
 M   M 
then M and N will satisfy the condition    
 y  x  x  y
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6.2.1 Internal Energy U :- From the first laws of thermodynamics

dU  TdS  PdV
From Legendre transformation
 U   U 
   T,     P , from given relation one can derive Maxwell relation
 S  V  V  S
 T   P 
     (Maxwell’s Third Relation)
 V  S  S V
6.2.2 Enthalpy H ;- The enthalpy is defined as, H  U  PV
 dH  dU  PdV  VdP
From Laws of thermodynamics,
TdS  dU  PdV
dH  TdS  VdP
From Legendre transformation,
 H   H 
  T,   V
 S  P  P  S
The Enthalpy H is Extensive quantity, which can not be measured directly. Thus change
in enthalpy is more useful.
H is positive in endothermic reaction and negative in exothermic reaction.
 T   V 
From above relation, one can derive Maxwell relation,     (Maxwell’s
 P  S  S  P
Fourth Relation).
H of a system is equal to sum of non-mechanical work done on it and the heat supplied
to it.
6.2.3 Helmholtz Free Energy F : The Helmholtz free energy is defined as, F  U  TS
dF  dU  TdS  SdT
From laws of thermodynamics dU  TdS  PdV
dF  TdS  PdV  TdS  SdT
dF   PdV  SdT
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 F   F 
    P,    S
 V  T  T V
 P   S 
From above relation one can derive Maxwell relation,     (Maxwell’s First
 T V  V T
Relation).
The free Energy E , which is available energy for work in reversible isothermal process.
6.2.4 Gibbs Energy: ‘ G ’ is defined as G  H  TS .
G  U  PV  TS
dG  dU  PdV  VdP  TdS  SdT
TdS  PdV  PdV  VdP  TdS  SdT
dG  VdP  SdT
 G   G 
   V and    S
 P  T  T  P
 V   S 
From above relation one can derive Maxwell relation,       (Maxwell’s
 T  P  P T
Second Relation)
 V   S 
From above relation one can derive Maxwell relation,      (Maxwell’s
 T  P  P T
Second Relation)
Gibbs free energy is popularly known as free enthalpy.
The Gibbs free energy is Maximum amount of non-expanding work that can be extracted
from a closed system.
The maximum work will be extracted, when the system is in reversible process.
Gibbs free energy is also treated as chemical potential.
In thermodynamics, chemical potential, as partial molar free energy, is a form of potential
energy that can be absorbed or relived during a chemical reaction.
The chemical potential of a species in the minute can be defined the slope of the energy
at system with respect to a change in the no of moles.
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dG
 , where  is chemical potential, G is Gibbs energy and N is no of molecules
dN V
Example: Prove that internal energy U is given by

 F /T  
(a) U  
  1/ T  
 V
  G / T  
(b) H   
  1 / T   P
Solution: (a) F  U  TS  U  F  TS
 F 
S   
 T V
  F   F  2   F / T     F / T  
U  F T   F T   T    
 T V  T V  T V  1 / T V
 G / T  
Solution: (b) H   
  1 / T   P
G  H  TS
 G 
S   
 T  p
 G  2  G     G / T 
H  G T   T       
 T  P  T  T  P    1 / T   P
6.3 Application of Maxwell Relation
6.3.1 First T  dS equation
Let T and V are independent variable, such that S  S T , V 
 S   S 
dS    dT    dV
 T V  V  T
 S   S   S   P 
TdS  T   dT  T   dV , put    
 T V  V  T  V  T  T  v
 P 
TdS  Cv dT  T   dV .
 T V
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6.3.2 Second T  dS Equation

Let T and P are independent variable, such that S  S T , P  .
 S   S 
TdS  T   dT  T   dP
 T  P  P  T
From Maxwell relation
 S   V 
    
 P   T  P
 V 
TdS  C P dT  T   dP
 T  P
6.3.3 Third T - dS Equation
Let P, V are independent variable, such that S  S  P, V 
 S   S 
dS    dP    dV
 P  P  V V
 S   S   S   T   S   T 
TdS  T   dP  T   dV  T     dP  T     dV
 P V  V V  T V  P V  T  P  V  P
 T   T 
 CV   dP  C P   dV
 P V  V  P
6.3.4 The First Energy Equation
Let T and V are independent variable, and U  U T , V 
 U   U 
dU    dT    dV
 T V  V  T
From first law of thermodynamics.
dU  TdS  PdV
 U   S 
   T  P
 V  T  V  T
 S   P 
Using Maxwell relation, T   T 
 V T  T V
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 U   P 
   T  P
 V  T  T V
 U   U   U 
dU    dT    dV  C v dT    dV
 T V  V  T  V  T
 U   P 
   T  P
 V  T  T V
  P  
dU  C v dT   T    P dV
  T V 
6.3.5 Second Energy Equation
dU  TdS  PdV
 U   S   V 
   T    P 
 P  T  P  T  P  T
Using Maxwell relation
 S   V 
    
 P  T  T  P
 U   V   V 
   T    P 
 P  T  T  P  P  T
This is popularly known as second energy equation
Application of second energy equation:
If U is function of independent variable of T and P .
 U   U 
U  U T , P   dU    dT    dP
 T  P  P T
 U    V   V  
 dU    dT  T    P   dP
 T  P   T  P  P T 
 T   P 
Example: From relation, dU  TdS  PdV , derive Maxwell relation,     
 V  S  S V
Solution: dU  TdS  PdV
 U   U 
    P,   T
 V  S  S V
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Hence, U is exact differential

   U      U    P   T 
            
 S  V  S V  V  S V  S  S V  V  S
Example: A real gas which obey van der Waal’s equation of state are kept in container
which has temperature T0 and volume V0 . If volume of container changes to V such that
temperature of gas become T , then what is change in entropy?
Solution: Assume CV is specific heat of constant volume
For van der Waal’s gas

 a 
 P  2 V  b   RT
 V 
From first T  dS equation
 P 
TdS  CV dT    dV
 T V
 P  R
  
 T V V  b
T
dT
V
R T   V b 
dS  CV T T V V  bdV  S  CV ln  T0   R ln  V0  b   S0

0 0
where, S 0 is integration constant

Example: For van der Wall gases, prove that
 U  a
   2 , where U is internal energy.
 V  T V
Solution: From first energy equation
 U   P 
   T  P (i)
 V  T  T V
 a 
 P  2 V  b   RT
 V 
RT a
P  2
V b V
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 P  R  P 
   put the value of   in equation (i)
 T V V  b   T V
 U  a
   2
 V  T V
Example: Prove that
 C   2P 
(a)  V   T  2 
 V  T  T V
 C P    2V 
(b)    T  2 
 P  T  T P
 S 
Solution: (a) We know that, CV  T  
 T V
 CV     S      S  
  T     T    
 V T  V  T V T  T  V T V
Using Maxwell relation,
 S   P 
   
 V  T  T V
   S      P  
One can get, T     T   
 T  V T V  T  T  V
 CV   2P 
   T  2 
 V  T  T V
 S 
(b) Cp  T 
 T  p
 C P     S      S  
  T    T   
 P  T  P  T  P  T  T  P  T  P
Use Maxwell relation,
 S   V 
    
 P  T  T  P
 C P    2V 
   T  2 
 P  T  T P
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Example: If  p is thermal expansivity at constant pressure and K T is isothermal
compressibility, then prove that

 S 
(a)    V p
 P  T
 P  p
(b)   
 T V K T
TV  P2
(c) CP  CV 
KT
Solution: From Maxwell relation
 S   V  1  V 
(a)         
 P  T  T  P V  T  P
 S   1  V    S 
   V     ,     V
 P  T V  T  P   P  T
 P   S 
(b)    
 T V  V T
 P   V   T 
       1
 T V  P  T  V  P
1  V 
 
 P  1 V  T  P
   
 T V  V   T  1  V 
      
 P  T  V  P V  P T
 P  P
  
 T V KT
 S   S  CV  S 
(c) dS    dT    dV  dS  dT    dV
 T V  V T T  V T
 S  CV  S   V  CP CV  S 
         V P  
 T  P T  V T  T  P T T  V T
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Using Maxwell relation,

C P CV  P  C P CV  
  V P     V  P  P 
T T  T V T T  KT 
T V  p2
C P  CV 
KT
Example: Prove that
 P   V 
(a) CP  CV  T    
 T V  T  P
2
 V   P 
(b) CP  CV  T    
 T V  V T
 2a 
(c) For the van der Waal’s gas, prove that CP  CV  R 1  
 RTV 
 Q   Q 
Solution: (a) CP  CV     
 T  P  T V
 S   S 
 T  T  ---- (A)
 T  P  T V
S  S T , V 
 S   S   S   S   S   V 
dS    dT    dV and          
 T V  V T  T  P  T V  V  T  T  P
 S 
Put the value of   in equation (A)
 T  P
 S   S   V   S   S   V 
CP  CV  T   T     T    CP  CV  T    
 T V   V  T  T  P  T V   V  T  T  P
 P   V    S   P  
T         
 T V  T  P    V  T  T V 
 P   V 
CP  CV  T    
 T V  T  P
 P   S   P   S   P 
From Maxwell relation         . 
 T V  V T  T V  P T  V T
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 S   V   P   V   P 
From Maxwell relation       So      . 
 P T  T  P  T V  T  P  V T
 P   V   P   V   P 
CP  CV  T     Put the value of      . 
 T V  T  P  T V  T  P  V T
2
 V   P 
CP  CV  T    
 T V  V T
(b) For van der Waal’s gas
 a 
 P  2  V  b   RT ---- (B)
 V 
 a  RT
P 2   → differentiate w.r.t. to T
 V  V  b 
 P  R
  
 T V V  b
Differentiate (B) with respect to V
2a  V  RT  V  R
 3    2   
V  T  P V  b   T  P V  b
R
 V  V b
   2a
 T  P RT
 3
V  b  V
2
 P   V 
Substituting the value   ,  in equation
 T V  T  P
 R  R 
 S   V    
CP  CV  T   V  b V  b   R
   T
 V T  T  P 2a 2a  V  b 
2
RT 
 1  3 
V  b  V
2 3
 V  RT
1
R  2a   2a 
CP  CV  2
 R 1    R 1  
 2a  V  RTV   RTV 
1  3 
 V  RT
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 P   V 
Example: From CP  CV  T     ,
 T V  T  P
Prove, C P  CV  TE 2V , where E is bulk modulus of elasticity and  is coefficient of
volume expansion.
 P   V 
Solution: Let CP  CV  T    
 T V  T  P
P  P T , V 
 P   P 
dP    dT    dV
 T V  V  T
For constant pressure dP  0
 P   P 
  dT    dV
 T V  V T
 P   P   V 
      
 T V  V  T  T  P
2
 P   V 
CP  CV  T    
 V T  T  P
 P  1  V 
E  V   and    
 V  T V  T  P
2
 P  V  V 
2
V E
CP  CV  T  T   V 
2 2
  2
V  V T V  T  P V 
C P  CV  TVE 2
 H   V 
   V T  
Example Prove that  P   T  P
T
 V 
dH  TdS  VdP and put TdS  CP dT  T   dP in equation
 T  P
 V    V  
dH  CP dT  T   dP  VdP  dH  CP dT   V  T    dP
 T  P   T  P 
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Example: Over a certain range of pressure and temperature the Equation of a Certain
RT C
substance is given by the relation V  
P T3
(a) Find the change in enthalpy at constant temperature if pressure change from P1 to P2
(b) Find the change of entropy of this substance in isothermal process
  V  
(a) dH  CP dT   V  T    dP
  T  P 
for Isothermal process dT  0
  V   RT C  V  R 3C
dH   V  T    ,V   3     4
  T  P  P T  T  P P T
  V   RT C RT 3C 4C
V  T     3  3  3
  T  P  P T P T T
P2
4C 4C
dH  H 2  H1    3
dP  3  P1  P2 
P1 T T
 V 
(b) From second TdS equation TdS  CP dT  T   dP
 T  P
For Isothermal process dT  0
 V   V  R 3C
dS     dP and     4
 T  P  T  P P T
P2
R P2
3C P 3C
dS   dP   4 dP  S2  S1  R ln 2  4  P2  P1 
P1 P P1 T P1 T
 a 
Example: For Vander Waal gas  P  2 V  b   RT
 V 
R
(a) Prove that T V  b  CV for Iso-Entropic process.
(b) If pressure and Volume changes from P1 ,V1 to P2 ,V2 at constant temperature then
find Change in enthalpy
 P 
Solution: (a) From first TdS equation, TdS  CV dT  T   dV
 T V
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RT a  P  R
P  2    
V b V  T V V  b
 P 
At constant entropy dS  0  CV dT  T   dV  0
 T V
dT R dT R dV
CV  dV  0 or  0
T V b T CV V  b
R
By integration, T V  b  CV  constant
 U   P  a a
(b) From   T    P  2 dU  2 dV
 V T  T V V V
1 1
U 2  U1 T  a  
 V1 V2 
H  U  PV Hence enthalpy is point function
So, H1  U1  PV
1 1 and H 2  U 2  P2V2
1 1
H 2  H1  U 2  U1  PV
2 2  PV
1   H 2  H1 T   PV 1 1 a
2 2  PV  
 V1 V2 
Example: If Helmholtz free energy for radiation is given by
8 5 K B4 T 4
F  V
45h 3 c 3
(a) What is radiation pressure?
(b) If S is entropy of the system, prove that specific heat at constant volume is given by
CV = 3S
Solution: (a) dF   SdT  PdV
 F  8 5 K B4T 4
P    
 V  T 45h 3c 3
 F  32 5 K B4
(b) S     VT 3
 T V
3 3
45h c
 S   32 5 K B4  2  32 2 K B4  3
CV  T    T  3   VT  3   VT
 T V
3 3 3 3
 45h c   45h c 
CV  3S
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bS 3
Example: The internal energy E of a system is given by E  , where b is constant
VN
and other symbols have their usual meaning.
(a) Find the temperature of the system
(b) Find Pressure of the system
Solution: From first law of thermodynamics
TdS  dU  PdV  dU  TdS  PdV
bS 3
As, U  E 
VN
 U  3bS 2
(a) T    
 S V VN
 U   bS 3  bS 3
(b) P        2   2
 V  S  V N V N
Example: Consider an Ideal gas where entropy is given by
n U V
S   5 R ln  2 R ln 
2 n n
where n = number of moles, R = universal gas constant, U = internal energy
V = volume and  = constant
(a) Calculate specific heat at constant pressure and volume
5
(b) Prove that internal energy is given by U  PV
2
Solution: (a) From first law of thermodynamics
1 P  S  1
TdS  dU  PdV , dS  dU  dV    
T T  U V T
n 5R 1 5
   U  nRT
2U T 2
 U  5 7
CV     nR  CP  CV  R  CP  nR
 T  2 2
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5 U 5 nRT
(b) U nRT  
2 V 2 V
nRT
PV  nRT  V 
P
U 5 5
 P  U  PV
V 2 2
Example: Using the equation of state, PV  nRT and the specific heat per mole,
3R
Cv  for monatomic ideal gas
2
(a) Find Entropy of given system.
(b) Find free energy of given system
nRT 3R
dU  nCV dT , P  , CV 
V 2
TdS  dU  PdV
dU P dT dV
dS   dV or dS  nCV  nR
T T T V
3
S NR ln T  N ln V  S0 where, S 0 is constant
2
(c) F  U  TS
3nRT  3nRT 
  ln T  nRT ln V   F0 , where F0  T  S 0 is again constant
2  2 
Example: From electromagnetic theory, Maxwell found that the pressure P from an
1 1U
isotropic radiation equal to the energy density i.e., P  , where V is volume of
3 3V
the cavity, then using the first energy equation, prove that
Energy density u is proportional to T 4 .
 U   S   P 
Solution:   T   P T   P
 V T  V T  T V
1 U  P  1  U 
P  u , where u       
3 V  T V 3V  T V
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 U  T  du  1
   u and u     u
 V T 3  dT V 3
du du dT
T  4u  4
dT u T
u  T 4 =  u   T 4 , where  is a constant.
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MCQ (Multiple Choice Questions)

Q1. Which of the following is not a Maxwell’s thermodynamic relation?
 S   P   T   P 
(a)     (b)     
 V  T  T V  V  S  S V
 T   V   V   S 
(c)      (d)    
 P V  S  P  P  T  T  P
Q2. Which one of the following thermo dynamical relations is used for certain adiabatic
changes, such as the sudden compression of a liquid or sudden -stretching of a rod?
 S   V   S   P 
(a)      (b)    
 P  T  T  P  T  P  V T
 S   P   S   V 
(c)      (d)     
 T  P  V  T  P  T  T  P
Q3. Which one of the Maxwell’s thermodynamic relations given below leads to
Clausius-Clapeyron equation?
 T   P   T   V 
(a)      (b)     
 V  S  S V  P  S  S  P
 S   P   S   V 
(c)     (d)     
 V  T  T V  P  T  T  P
Q4. Which of the following is correct, if  is volume expansivity and other variables have
usual meaning in thermodynamics .
 C   C 
(a)  P   TV  2 (b)  P   TV  2
 P T  P T
 C  TV  C  TV
(c)  P    2 (d)  P   2
 P T   P T 
Q5. Which of the following can be derived by S  S (T ,V ) ?
 P   V 
(a) TdS  CV dT  T   dV (b) TdS  CP dT  T   dV
 T V  T  P
 P   V 
(c) TdS  CV dT  T   dV (d) TdS  CP dT  T   dV
 T V  T  P
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Q6. Which of the following can be derived by S  S (T , P) ?
 P   V 
(a) TdS  CV dT  T   dV (b) TdS  CP dT  T   dV
 T V  T  P
 P   V 
(c) TdS  CV dT  T   dV (d) TdS  CP dT  T   dV
 T V  T  P
Q7. For an isolated thermodynamic system, P,V , T ,U , S and F represent the Pressure,
Volume, Temperature, Internal energy, Entropy, and Helmholtz free energy respectively.
Then the following relation is true
 F   F 
(a)    S (b)    S
 T V  T  P
 U   U 
(c)   T (d)    P
 S V  V V
Q8. Which of the following thermodynamic relation will give the Maxwell relation
 S   V 
     ?
 P T  T  P
(a) dU  TdS  PdV (b) dH  TdS  VdP
(c) dF   SdT  PdV (d) dG   SdT  VdP )
Q9. Which of the following is not an exact differential?
(a) dQ , where Q heat absorbed (b) dU , where U is internal energy
(c) dS , where S is entropy (d) dF , where S is entropy
Q10. Among the following sets of Maxwell relations, which is correct? ( U -internal energy,
H -enthalpy, A -Helmholtz free energy and G -Gibbs free energy)?
 U   U   H   H 
(a) T    and P    (b) V    and T   
 V  S  S V  P  S  S  P
 G   G   A   A 
(c) P     and V    (d) P     and S   
 V T  P  S  S T  P V
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Q11. When a system is held at constant temperature and pressure in a state of equilibrium, then
it attains a minimum value of
(a) Internal energy (b) Enthalpy
(c) Helmholtz energy (d) Gibb’s free energy
Q12. Given that
H  the enthalpy of a system
T  absolute temperature and
S  entropy
G  H  TS is the Gibbs function for the system
In the case of a reversible, isothermal and isobaric process
(a) G  constant
(b) G  0 and changes with T
(c) G  0 and changes with S
(d) G changes with both T and S
Q13. The Gibb’s function G in thermodynamics is defined as,
G  H  TS
where, H is the enthalpy, T is the temperature and S is the entropy. In an isothermal,
isobaric, reversible process, G :
(a) remains constant, but not zero (b) varies linearly
(c) varies non-linearly (d) is zero
bS 3
Q14. The internal energy E of a system is given by E  , where b is a constant and other
VN
symbols have their usual meaning. The temperature of this system is equal to
2
bS 2 3bS 2 bS 3 S
(a) (b) (c) (d)  
VN VN V 2N N
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Q15. The free energy of gas of N particles in a volume V and at a temperature T is


F  Nk B T ln a0V k BT 
5/ 2

/ N , where a 0 is a constant and k B denotes the Boltzmann
constant. The internal energy of the gas is
3 5
(a) Nk B T (b) Nk B T
2 2

(c) Nk B T ln a 0V k B T 
5/ 2

/N 
3
2
Nk B T 
(d) Nk BT ln a0V / k B T 
5/ 2

Q16. The entropy S of a thermodynamic system as a function of energy E is given by the
following graph
S C
B
A
E
The temperatures of the phases A, B and C , denoted by T A , TB and TC , respectively,
satisfy the following inequalities:
(a) TC  TB  T A (b) T A  TC  TB (c) TB  TC  T A (d) TB  T A  TC
Q17. The entropy of an ideal paramagnet in a magnetic field is given approximately by
S  S0  cU 2 , where U is energy of the spin system and c is constant then which one is
correct plot between internal energy and temperature T , where   T  
U
U
(a) (b)
T
T
U U
(c) T (d)
T
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Q18. A certain system is found to have Gibbs free energy given by

 aP 
G ( P, T )  RT ln  5/ 2 
 ( RT ) 
Where a and R are constants then specific heat at constant pressure ( c p ) is given by
3 5 7 9
(a) R (b) R (c) R (d) R
2 2 2 2
Q19. Helmholtz free energy is given by F  CT 4 , where C is constant and T is temperature
in Kelvin then which one is correct relation between specific heat at constant volume CV
and entropy S is given by

3
(a) CV  2S (b) CV  4S (c) CV  3S (d) C v  S
2
Q20. If CV is the specific heat of the ideal gas then which of the following is correct for
vander wall gases for same degree of freedom .
a
(a) dU  CV dT (b) dU   dV
V2
a a
(c) dU  CV dT  dV (d) dU  CV dT  dV
V2 V2
Q21. For a van der Waal’s gas, the equation of the adiabatic curve in the variables T ,V ;
(a) T V  b  (b) T V  b 
R / CP R / CV
 constant  constant
(c) T V  b  (d) T V  b 
 R / CP  R / CV
 constant  constant
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MSQ (Multiple Select Questions)

Q22. If H is enthalpy and G is Gibbs free energy of the thermodynamic system, then which
of the following is/are correct?
(a) H  G  TS (b) H  G  TS
   G     G 
(c) H  T 2    (d) H  T 2   
 T  T  P  T  T  P
Q23. Which of the following statements is/are correct?
 U   P 
(a) The first energy equation is given by,    T  P
 V  T  T V
 U 
(b) The value of    0 , for ideal gas
 V  T
 U  a
(c) The value of    2 , for vander Waal’s gases .
 V  T V
 U   V 
(d) The second energy equation is given by,    T  P
 P  T  T  P
Q24. Which of following is/are correct for heat capacity at constant pressure CP and volume
CV ?
  U    V 
(a) CP  CV   P     
  V T   T  P
R
(b) For van der Waal’s gas CP  CV 
1  2a 1  b / V  / VRT
2
(c) van der Waal’s gas behave like a ideal at high temperature
(d) For Ideal gas CP  CV  R
Q25. Which of the following is/are correct?
 P   V   P   V 
(a) CP  CV  T     (b) CP  CV  T    
 T V  T  P  T V  T  P
2 2
 P   V   P   V 
(c) CP  CV  T     (d) CP  CV  T    
 V T  T  P  V T  T  P
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Q26. If  is volume expansivity of substance, T is isothermal compressibility and  S is

2
 P   V 
adiabatic compressibility and it is given that, CP  CV  T     , then which
 V T  T  P
one of the following is/are correct?
T  2V T  2V
(a) CP  CV   (b) CP  CV 
T T
T  2V T  2V
(c)  s  T  (d)  s  T  
CP CP
Q27. Which of the following is/are correct, if all variable have usual meaning in
thermodynamics?
 S   P   CV   2 P 
(a)     (b)    T  T 2 
 V T  T V  V T  V
 S   V   C    2V 
(c)     (d)  P   T  2 
 P T  T V  P T  T  P
Q28. One mole of oxygen is expanded from a volume, V1 to V2 at a constant temperature T . If
the gas is assumed to be a van der Waal’s gas, then
(a) the increment of the internal energy of the gas is zero
1 1 
(b) the increment of the internal energy of the gas is a  
 V1 V2 
V2  b 1 1
(c) heat exchange during the process is RT ln  a  
V1  b V2 V1 
V2  b
(d) heat exchange during the process is RT ln
V1  b
a
Q29. The free energy for a photon gas is given by, F   VT 4 , where a is a constant. The
3
entropy S and the pressure P of the photon gas are
4 a 4
(a) S  aVT 3 (b) P  T
3 3
4 4a 4
(c) S   aVT 3 (d) P  T
3 3
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Solutions
MCQ (Multiple Choice Questions) Solution
Ans. 1: (d)
Ans. 2: (a)
Solution: The sudden stretching of a wire or compression of liquid is given by,
 S   V 
    
 P  T  T  P
Ans. 3: (c)
Solution: The rate of change of temperature and pressure is given by Clausius-Clapeyron
dP L
equation, which is given as  , L is latent heat
dT T V2  V1 
This can be derived by Maxwell’s first thermodynamic relation given as,
 S   P 
   
 V  T  T V
Ans. 4: (a)
 S   V 
Solution: From Maxwell relation,      
 P T  T  P
   S      V      T S      V  
              T    
 T  P T  P  T  T  P  P  P  T  P T  T  T  P  P
 C    2V  1  V 
  P   T  2  and    
 P T  T  P V  T  P
 C 
So,  P   TV  2
 P T
Ans. 5: (a)
 S   S   S   P 
Solution: dS    dT    dV , from Maxwell relation    
 T V  V T  V T  T V
 T S 
And    CV
 T V
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 P 
TdS  CV dT  T   dV
 T V
Ans. 6: (b)
 S   S   S   V 
Solution: dS    dT    dP , from Maxwell relation      
 T  p  P T  P T  T  P
 T S 
and    CP
 T V
 V 
TdS  CP dT  T   dV
 T  P
Ans. 7: (a)
Solution: dF  SdT  PdV
Ans. 8: (d)
Solution: dG   SdT  VdP
 G   G     G      G    S   V 
    S and   V              
 T  P  P T  P  T  P T  T  P T  p  P T  T  P
And. 9: (a)
Solution: Heat exchange is path dependent, so it is not perfect differential.
Ans. 10: (b)
 H   H 
Solution: dH  TdS  VdP  V    and T   
 P  S  S  P
Ans. 11: (d)
Solution: The change in Gibb’s free energy is given as
dG  VdP  SdT
at constant P, dP  0 and at constant T, dT  0  dG  0
Thus, G  constant
Ans. 12: (a)
Solution: Enthalpy H  PV  U
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From laws of thermodynamics it is given as,

TdS  dU  PdV
So, G  U  PV  TS (i)
 dG  dU  d  PV   d TS 
 dU  PdV  VdP  SdT  TdS by equation (i)

dG  VdP  S dT (ii)
for isobaric, dP  0 and for isothermal, dT  0
so, equation (ii) becomes dG  0
 G  constant
Ans. 13: (a)
Solution: Gibb’s function is given as,
G  H  TS
And the enthalpy,
H  U  PV
G  U  PV  TS  dG  dU  d PV   d TS 
dG  dU  PdV  VdP  TdS  SdT
dG  VdP  SdT
According to question the process is isobaric i.e., dP  0 , isothermal i.e., dT  0 . So,
above equation becomes as, dG  0  G  C
Ans. 14: (b)
 E  3bS 2
Solution: TdS  dE  PdV  dE  TdS  PdV     T  T 
 S V VN
Ans. 15: (b)

Solution: F   Nk BT ln a 0V k B T 
5/ 2

/ N , F  U  TS , U  F  TS
 F   F   F 
dF   SdT  PdV      S or S     U  F T 
 T V  T V  T V
a 0Vk B5 / 2
F   Nk B T lnC T 5/ 2
 where C 
N
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 F   F 
   Nk B lnCT   Nk B T    Nk B T ln CT   Nk B T
C 5 3/ 2 5

5/ 2
T  T 5/ 2
 T V  T V
5/ 2
CT 2 2
 F  5  F  5
T   F  Nk B T  U  F  T    Nk B T .
 T  V 2  T V 2
Ans. 16: (c)
Solution: Now temperature of phase TA, TB , TC
 dS  1 C
Now,  
 dE  T S
B
dS
And will be stoped when, it will be zero for B - phase A
dE
So, TB  
E
And in C and A phases external energy of C phase is more so TC  TA
Now TB  TC  T A
Ans. 17: (c)
 U  1 1
Solution: T     i.e, U  
 S  V 2cU 2cT
Ans. 18: (b)
 G  5  ap 
Solution: S     R  R ln  5/2 
 T  p 2  (RT) 
 S  5
Cp  T   R
 T  2
Ans. 19: (c)
 F 
Solution: S     4CT 3
 T V
CV P
TdS  CV dT  PdV  dS  dT  dV
T CV
 S  CV  S 
    CV  T    CV  3S
 T V T  T V
Ans. 20: (d)
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 U   U   U 
Solution: U  U (T , V )  dU    dT    dV  dU  CV dT    dV
 T V  V T  V T
 U  a
   2
 V T V
a
So, dU  CV dT  dV
V2
Ans. 21: (b)
 a 
Solution:  P  2 V  b   RT and dU  CV dT  2 dV
a
 V  V
For adiabatic process: dQ  0  dU  pdV
a  RT a   RT 
 CV dT  dV    2 dV  CV dT  dV 
V  b V   V  b 
2
V
CV dT dV C
    V ln Tk  ln V  b 
RT V b R
V  b  Tk 
 CV / R
 T  CV / R  k  CV / R
V  b T C V /R
 k CV / R
T V  b 
R / CV
 constant .
MSQ (Multiple Select Questions)

Ans. 22: (b) and (c)
 G 
Solution: dG   SdT  VdP     S
 T  P
 G  2   G 
G  H  TS  H  G  TS , So H  G  T    H  T   
 T  P  T  T  P
Ans. 23: (a), (b) and (c)
Solution: The first law of thermodynamics is given as
dU  PdV  TdS
 U   S 
   T  P
 V  T  V  T
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 S   P 
As from Maxwell’s second relation    
 V T  T V
 U   P 
  T   P
 V T  T V
 U 
For real gas PV  nRT , so   0
 V  T
 a   U  a
For van der Wall’s  P  2  V  b   nRT , so    2
 V   V  T V
 U   S   V 
  T    P 
 P T  P T  P T
Ans. 24: (a), (b), (c) and (d)
Solution: (a) From H  U  PV , we obtain,
 H   U   V 
     P 
 T  P  T  P  T  P
Let, U  U T , V T , P   .
Let, U  U T , V T , P   . The above expression becomes
 U   U   U   U   U   V 
dU    dT    dV         
 T V  V T  T  P  T V  V T  T  p
 H   U    U    V 
     P     
 T  P  T V   V T   T  P
  U    V 
Hence, cP  cV   P     
  V T   T  P
 a 
(b) To find c p  cv for a Van der Waals gas  P  2  V  b   RT
 V 
For the Van der Waals gas, we have
 V  R
  
 T  P  RT 2a V  b  
  
V  b V3 
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R
Hence, c p  cv 
1  2a 1  b / V  / VRT
2
(c) and d) When V & T  , cP  cV  R , which is just the result for an ideal gas.
Ans. 25: (a) and (c)
Solution: S  S (T , V )
 S   S   S   S   S   V 
dS    dT    dV  T   T      
 T V  V T  T  P  T V  V T  T  P
 P   V 
CP  CV  T    
 T V  T  P
P  P (T , V )
 P   P 
dP    dT    dV , for constant pressure dP  0
 T V  V T
 P   P   V 
Put,        in above equation
 T V  V T  T  P
2
 P   V 
 CP  CV  T    
 V T  T  P
Ans. 26: (b) and (d)

2
 P   V  1  V  1  V 
Solution: CP  CV  T     , it is known     and T    
 V T  T  P V  T  P V  P T
T  2V C P T
So, CP  CV  ,we know that  
T CV  S
T  2V  T  2V T  2V
 1    s  T  S   s  T  
CV T T CV CP
Ans. 27: (a), (b) and (d)
 S   P 
Solution: From Maxwell relation,    
 V T  T  P
   S      P      T S      P  
            T    
 T  V T V  T  T V V  V  T V T  T  T V V
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 C   2 P 
 V  T  2 
 V T  T  P
 S   V 
Similarly, another Maxwell relation is given by      
 P T  T  P
   S      V      T S      V  
              T    
 T  P T  P  T  T  P  P  P  T  P T  T  T  P  P
 C    2V 
  P   T  2 
 P T  T V
Ans. 28: (b) and (d)
 U  a
Solution: (a) For vander waal’s gas,    2
 V T V
a a 1 1 
U    a  
V1 V2  V1 V2 
(b) We know that, for real gas
 a 
 P  2 V  b   RT
 V 
2 V
RT a
P  and work done W   PdV
V b V 2 V1
V b 1 1
V2 2 V
RT a
W  dW   dV   2 dV  RT ln 2  a  
V1
V b V1 V
V1  b V2 V1 
V2  b 1 1 1 1 V2  b
Now, Q  W  U  RT ln  a    a   Q  RT ln
V1  b V2 V1  V1 V2  V1  b
Ans. 29: (a) and (b)

Solution: dF  SdT  PdV
 F   F 
   S ,    P
 T V  V T
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Fiziks: Maxwell Relation and Thermodynamic Potential

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Fiziks: Maxwell Relation and Thermodynamic Potential

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Equating equation (1) and (2),

Maxwell Third Relation:- Put, x  S , y  V

6.2.1 Internal Energy U :- From the first laws of thermodynamics

From Legendre transformation,

Example: Prove that internal energy U is given by

6.3.2 Second T  dS Equation

Let P, V are independent variable, such that S  S  P, V 

Hence, U is exact differential

For van der Waal’s gas

where, S 0 is integration constant

Example: If  p is thermal expansivity at constant pressure and K T is isothermal

compressibility, then prove that

Using Maxwell relation,

Solution: (a) dF   SdT  PdV

MCQ (Multiple Choice Questions)

Q6. Which of the following can be derived by S  S (T , P) ?

Q15. The free energy of gas of N particles in a volume V and at a temperature T is

Q18. A certain system is found to have Gibbs free energy given by

and entropy S is given by

MSQ (Multiple Select Questions)

Q26. If  is volume expansivity of substance, T is isothermal compressibility and  S is

From laws of thermodynamics it is given as,

 dU  PdV  VdP  SdT  TdS by equation (i)

MSQ (Multiple Select Questions)

Let, U  U T , V T , P   . The above expression becomes

Ans. 26: (b) and (d)

Ans. 29: (a) and (b)

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