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Qu. Discuss TdS Equation

Ans. The relations between the thermodynamic properties of a system are traced to the combined form
of the first and second laws. The actual derivation may be done in a variety of ways. The simplest and
most methodical procedure is to make the TdS equations and the energy equations the starting point.
The three Tds equations are obtained by expressing the specific entropy as a function of the pairs of
variables, (T, V), (T, P) and (P,V) .

(i) Taking entropy S as a function of volume V and temperature T i.e. ,

S= f(V,T)
 ∂S   ∂S 
TdS = T   dT + T   dV (1)
 ∂T  V  ∂V T
The 1st term of the right side of this equation is expressed in terms of CV , the specific heat at constant

volume i.e. the volume becomes constant, hence change in volume dV = 0, now

 ∂S   T∂S   ∂Qrev 
T  =  =  = CV (2)
 ∂T  V  ∂T V  ∂T  V
Eq. (1) reduces to

 ∂S 
TdS = CV dT + T   dV (3)
 ∂V T
According to Maxwell’s relation

 ∂S   ∂P 
  =  
 ∂V T  ∂T V
Hence, Eq. (3) reduces to

 ∂P 
TdS = CV dT + T   dV (4)
 ∂T  V
This is known as 1st TdS equation.

(ii) Taking entropy S as a function of Pressure P and Temperature T. i.e.

S= f(P,T)
 ∂S   ∂S 
TdS = T   dT + T   dP (5)
 ∂T  P  ∂P T
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The 1st term of the right side of this equation is expressed in terms of C P , the specific heat at constant

pressure i.e. the volume becomes constant, hence change in pressure dP = 0, Now

 ∂S   T∂S   ∂Q rev 
T   =  =  = CP (6)
 ∂T  P  ∂T  P  ∂T P
The Eq. (5) reduces to

 ∂S 
TdS = C P dT + T   dP (7)
 ∂P  T
According to Maxwell’s thermodynamic relation

 ∂S   ∂V 
  =-   .
 ∂P T  ∂T  P
Hence Eq. (7) reduces to

 ∂V 
TdS = C P dT - T   dP (8)
 ∂T  P
This is 2nd TdS equation.

(iii) Taking entropy S as a function of Pressure P and volume V. i.e

S= f(P,V)

 ∂S   ∂S 
TdS = T   dP + T   dV (9)
 ∂P  V  ∂V  P
Now,

 ∂S   ∂S   ∂T 
 ∂P  =  ∂T   δ P 
 V  V  V
C  ∂T 
= V
T  δ P V

 ∂S   ∂S   ∂T 
  =   
 ∂V P  ∂T  P  δ V  P
C  ∂T 
= P
T  δ V  P
Putting these value in Eq. (4), Eq.(8) and Eq. (10), we get
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 ∂S   ∂S 
TdS = T   dP + T   dV
 ∂P  V  ∂V  P

 ∂T   ∂T 
TdS = CV   dP+C P   dV (10)
 δ P V  δV P
This is 3rd TdS equation.

These three TdS equations also expressed in terms of isobaric coefficient of volume expansion
1  ∂V 
βP =   (11)
V  ∂T P
And in terms of isothermal compressibility

1  ∂V 
KT = -   (12)
V  ∂P T
From Eq. (11) and Eq.(12), the ratio

 ∂V 
βP  ( )P  ∂V ∂P ∂P
= −  ∂T  = −( ) P ( )T = ( )V
KT  ( ∂V )T  ∂T ∂V ∂T
 ∂P 
The TdS equation may be written as

 ∂P  Tβ P
TdS = C V dT + T   dV = C V dT + dV (13)
 ∂T  V KT

 ∂V 
TdS = C P dT - T   dP = C P dT - TVβ P dP (14)
 ∂T 
 ∂T   ∂T  KT CP
TdS = CV   dP + C P   dV = C V dP + dV (15)
 δ P V  δV P βP β PV
The energy Equations
The change in internal energy in an infinitesimal process is given by
dU = TdS - PdV
Taking T and V as independent variable gives

 ∂U   ∂U   ∂S   ∂S 
 ∂T  dT +  ∂V  dV = T  ∂T  dT + T  ∂V  dV − PdV
 V  T  V  T
 ∂S   ∂S 
=T   dT + [T   − P]dV
 ∂T V  ∂V T
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Equating the coefficients of dV, we get

 ∂U   ∂S 
  =T   −P
 ∂V T  ∂V T
(16)
From Maxwell’s relations

 ∂U   ∂P 
  =T   −P
 ∂V T  ∂T V
In terms of isobaric coefficient of volume expansion β P and isothermal compressibility KT

 ∂U  βP
  =T −P (17)
 ∂V T KT
The Qu. (17) is called first energy equation. It is some times called the thermodynamic equation of state
because the right side can be computed from the equation of the system from measured values of β P ,

KT and P.
The 2nd energy equation is obtained on taking T and P as independent variables. From 1st law of
thermodynamics
dU = TdS - PdV .
Now,

 ∂U   ∂U   ∂S   ∂S   ∂V   ∂V 
  dT +   dP = T   dT + T   dP − P   dT − P   dP (18)
 ∂T  P  ∂P T  ∂T  P  ∂P T  ∂T  P  ∂P T
Or

 ∂U   ∂U   ∂S   ∂V   ∂S   ∂V 
  dT +   dP = [T   − P  ]dT + [T   − P  ]dP (19)
 ∂T  P  ∂P T  ∂T  P  ∂T  P  ∂P T  ∂P T
Equating the coefficients of dT and dP, we get

 ∂U   ∂S   ∂V 
  = [T   − P  ] (20)
 ∂T  P  ∂T  P  ∂T  P

 ∂U   ∂S   ∂V 
  = [T   − P   ] (21)
 ∂P T  ∂P T  ∂P T
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