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dQ = dU + PdV (1)
dQ = TdS (2)
The internal energy dU is a perfect differential depending upon any two of the thermodynamic function
P, V. T and S. for this we obtain the perfect differential .
Perfect differential
Taken two independent variables x and y, since internal energy dU is a function of x and y then.
∂ ∂U ∂ ∂U
∂y ( ∂x ) y = ∂x ( ∂y )x (4)
x y
The Eq. (3) differentiated with respect to independent variable x and y, we get
∂U ∂S ∂V
∂x =T ∂x - P ∂x
y y y
∂ ∂U ∂T ∂S ∂ 2S ∂P ∂V ∂ 2V
= + T - - P (5)
∂y ∂x y x ∂y x ∂x y ∂y∂x ∂y x ∂x y ∂y∂x
Similarly,
∂U ∂S ∂V
=T - P
∂y x ∂y x ∂y x
2
∂ ∂U ∂T ∂S ∂ 2S ∂P ∂V ∂2V
= + T - - P (6)
∂x ∂y x y ∂x y ∂y x ∂x∂y ∂x y ∂y x ∂x∂y
The internal energy dU is a perfect differential as mention in Eq. (4). Equating Eq. (5) and Eq. (6), we get
∂T ∂S ∂ 2S ∂P ∂V ∂2V
+ T
- - P
∂y x ∂x y ∂y∂x ∂y x ∂x y ∂y∂x
∂T ∂S ∂ 2S ∂P ∂V ∂ 2V
= + T - - P (7)
∂x y ∂y x ∂x∂y ∂x y ∂y x ∂x∂y
n Eq. (7) 2nd and 3rd terms both sides cancelled and rest terms written as
∂T ∂S ∂P ∂V ∂T ∂S ∂P ∂V
- = - (8)
∂y x ∂x y ∂y x ∂x y ∂x y ∂y x ∂x y ∂y x
∂s ∂p
=
∂x y ∂y x
changing the value of parameter x =V and y=T, we get
∂s ∂p
=
∂V T ∂T V
(9)
∂T ∂v
=
∂y x ∂x y
changing the value of parameter x = s and y = p, we get
∂T ∂V
=
∂P s ∂S p
(11)
***
In addition to these four equations two more equations are added.
∂T ∂s ∂T ∂s
- =1
∂y x ∂x y ∂x y ∂y x
changing the value of parameter x = v and y = p, we get
∂T ∂s ∂T ∂s
- =1
∂p v ∂v p ∂v p ∂p v
(13)
(14)
***
6
Maxwell’s Relations
∂T ∂p
Internal Energy U dU = TdS – PdV = -
∂V s ∂S v
∂T ∂V
Enthalpy H dH = TdS + vdP ∂P = ∂S
s p
∂p ∂s
Free Energy A A = - PdV - SdT =
∂T V ∂V T
∂s ∂v
Gibb’s Function G dG = VdP- SdT = -
∂p T ∂T p
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