ZCT 214/2

THERMODYNAMICS
Chapter 6
Combined first and second laws

1
 1. Introduction
 The analytical formulation of the first law of
thermodynamics in differential form;

dQ = dU + dW (6-1)

 The second law states that for a reversible process

between two equilibrium states;

dQ = T dS (6-2)

2
 The work in a reversible process, for a PVT
system;

dW = P dV
(6-3)
 The combined first and second law for a PVT
system in a reversible process;

T dS = dU + P dV (6-4)
3
Note that
 Eqn (6-1) can be applied for reversible and
irreversible processes
 Although eqns (6-2) and (6-3) are true for a
reversible process, eqn (6-4) is not restricted
to a process at all, as it only expresses the
properties of a system in two equilibrium
states

4
 If a system undergoes an irreversible process between
two equilibrium states,
 the term Tds in eqn (6-4) cannot be identified with the term
dQ in eqn (6-1)
 The term PdV in eqn (6-4) cannot be identified with the
term dW in eqn (6-1)
 Consider an irreversible process in which adiabatic
stirring work is done on a system kept at constant
volume
 Tds ≠ 0 but dQ = 0
 PdV = 0 but dW ≠ 0

5
 2. T and v independent
 From eqn (6-4);

ds =
1
(du + P dv )
T
 consider u as afunction of T and v;

 ∂u   ∂u 
du =   dT +   dv (6-5)
 ∂T  v  ∂v  T
1  ∂u  1  ∂u  
ds =   dT +   + P  dv
T  ∂T  v T  ∂v  T  6
 and also may express s in terms of V and T;

 ∂s   ∂s 
ds =   dT +   dv (6-6)
 ∂T  v  ∂v  T

7
 1  ∂u  1  ∂u    ∂s   ∂s 
ds =   dT +   + P  dv ds =   dT +   dv
T  ∂T  v T  ∂v  T   ∂T  v  ∂v  T

 By comparing the two equations;

 ∂s  1  ∂u 
  =   (6-7)
 ∂T  v T  ∂T  v

 ∂s  1  ∂u  
  =   + P  (6-8)
 ∂v  T T  ∂v  T 
8
  ∂s  1  ∂u   ∂s  1  ∂u  
  =     =   + P 
 ∂T  v T  ∂T  v  ∂v  T T  ∂v  T 

• Differentiating partially eqn (6-7) wrt v and

eqn (6-8) wrt T and then combining them;

 ∂  ∂s    ∂  ∂s   ∂ s
2
∂ s
2

    =    = =
 ∂v  ∂T  v  T  ∂T  ∂v  T  v ∂v ∂T ∂T ∂v


1 ∂ u 2
 1  ∂ u   ∂P   1
2
 ∂u  
  =  +  − 2   + P 
 
T  ∂v ∂T   
T  ∂T ∂v   ∂T  v  T  ∂v  T 
9
 1  ∂ 2u  1  ∂ 2 u   ∂P   1  ∂u  
  =  +  − 2   + P 
 
T  ∂v ∂T   
T  ∂T ∂v   ∂T  v  T  ∂v  T 

 which simplifies to;

 ∂u   ∂P  Tβ
  = T  − P = −P
 ∂v  T  ∂T  v κ
(6-9)

*refer also to eqn (2-42)

10
  ∂u   ∂u   ∂u   ∂P 
du =   dT +   dv   = T  − P
 ∂T  v  ∂v  T  ∂v T  ∂T  v

 ∂u 
 since   = cv ,
 ∂T  v
eqn (6-5) can be written as follows;

  ∂P  
du = c v dT + T   − P  dv
  ∂T  v 
(6-10)

11
 ∂u   ∂P  Tβ
  = T  − P = −P
 ∂v  T  ∂T  v κ

 From chapter 4 eqn.(4.6), using the first law alone;

 ∂u    ∂v 
c P − c v =   + P   
 ∂v  T   ∂T  P
(6-11)

 Using eqn (6-9) and eqns (2-22) and (2-42);

 ∂P   ∂v  β 2
Tv
c P − cv = T     = (6-12)
 ∂T  v  ∂T  P κ
12
 ∂s  1  ∂u   ∂s  1  ∂u    ∂u   ∂P  Tβ
  =     =   + P    = T  − P = −P
 ∂T  v T  ∂T  v  ∂v  T T  ∂v  T  ∂
 T
v  ∂T v κ

 ∂u 
 From eqns (6-7), (6-8), (6-9) and   = cv ;
 ∂T  v

 ∂s  cv
  =
 ∂T  v T (6-13)

 ∂s   ∂P 
  =   (6-14)
 ∂v  T  ∂T  v
13
  ∂s   ∂s 
ds =   dT +   dv
 ∂T  v  ∂v  T

 From eqn (6-6), using eqns (6-13) and (6-14);

cv  ∂P 
ds = dT +   dv
T  ∂T  v

 ∂P 
T ds = c v dT + T   dv
 ∂T  v (6-15)

14
  ∂s  cv  ∂s   ∂P 
  =   =  
 ∂T  v T  ∂v  T  ∂T  v

 By equating the mixed partial second derivatives of s

wrt v and T for eqns (6-13) and (6-14);

 ∂c v   ∂2P 
  = T  2 
 ∂v  T  ∂T  v (6-16)

For any substance for which the pressure is a linear

function of temperature at constant volume,
 ∂2P 
  = 0 and cv is independent of volume
 ∂T 2 
 v 15
 3. T and P independent
 In terms of enthalpy;

h = u + Pv
 The combined first and second laws can be written as;

T ds = du + P dv

ds =
1
(dh − v dP )
T
16
ds =
1
(dh − v dP )
T

 considering h as a function of T and P;

 ∂h   ∂h 
dh =   dT +   dP
 ∂T  P  ∂P  T (6-17)

1  ∂h  1  ∂h  
ds =   dT +   − v  dP
T  ∂T  P T  ∂P  T 
17
 1  ∂h  1  ∂h  
ds =   dT +   − v  dP
T  ∂T  P T  ∂P  T 

 but
 ∂s   ∂s 
ds =   dT +   dP
 ∂T  P  ∂P  T (6-18)
 By comparison;
 ∂s  1  ∂h 
  =  
 ∂T  P T  ∂T  P (6-19)

 ∂s  1  ∂h   (6-20)
  =   − v 
 ∂P  T T  ∂P  T  18
 ∂s  1  ∂h   ∂s  1  ∂h  
  =     =   − v 
 ∂T  P T  ∂T  P  ∂P  T T  ∂P  T 

 If eqn (6-19) is differentiated wrt P and eqn (6-20) is

differentiated wrt T and then equated;

 ∂h   ∂v 
  = −T   + v = − βvT + v
 ∂P  T  ∂T  P
(6-21)

19
  ∂h   ∂h   ∂h   ∂v 
dh =   dT +   dP   = −T   + v = − βvT + v
 ∂T  P  ∂P  T  ∂P  T  ∂T  P

 ∂h 
 since   = cP , eqn (6-17) can
 ∂T  P
be written as follows;

  ∂v  
d h = c P dT − T   − v  dP
  ∂T  P 
(6-22)

20
 ∂h   ∂v   ∂s  1  ∂h   ∂s  1  ∂h  
  = −T   + v = − βvT + v   =     =   − v 
∂
 T
P  ∂T P ∂ ∂
 T P T  T  P  ∂P  T T  ∂P  T 

 From eqn (6-21) and  ∂h  = c ;

 ∂T  P
P

 ∂s  cP
  =
 ∂T  P T (6-23)

 ∂s   ∂v 
  = −  (6-24)
 ∂P  T  ∂T  P
21
  ∂s   ∂s   ∂s  cP  ∂s   ∂v 
ds =   dT +   dP   =   = − 
 ∂T  P  ∂P  T  ∂T  P T  ∂P  T  ∂T  P

 Hence
 ∂v 
T ds = c P dT − T   dP
 ∂T  P
(6-25)
 By equating the mixed second-order partial
derivatives of s

 ∂c P  ∂ v 2

  = − T  2 

 ∂P  T  ∂T P
(6-26)
22
 4. P and v independent
 In the same way, equations for partial
derivatives of entropy s wrt P and v can be
obtained;
 ∂s  c v  ∂T  cv κ
  =   = (6-27)
 ∂P  v T  ∂P  v T β

 ∂s  c P  ∂T  cP
  =   = (6-28)
 ∂v  P T  ∂v  P T vβ
23
 and

 ∂T   ∂T 
T ds = c P   dv + c v   dP
 ∂v  P  ∂P  v

(6-29)

24
 5. The T ds equations
 The three expressions for T ds derived are;

 ∂P 
T ds = c v dT + T   dv (6-30)
 ∂T  v

 ∂v 
T ds = c P dT − T   dP (6-31)
 ∂T  P

 ∂T   ∂T 
T ds = c P   dv + c v   dP (6-32)
 ∂v  P  ∂P  v
25
 The T ds equations can be use to
 compute the heat flow in a reversible process,
 provide relations between pairs of variables in a
reversible adiabatic process in which s is a
constant and ds = 0

26
  ∂P 
T ds = c v dT + T   dv
 ∂T  v

 As an example, eqn (6-30) can be used to compute

the incease in temperature of a solid or liquid when it
is compressed adiabatically;
βT
T ds = 0 = c v dTs + dv s
κ
βT
dTs = − d vs
κc v (6-33)

 If the volume is decreased, dvs becomes –ive and

 dTs becomes +ive if β +ive and
 dTs becomes –ive if β -ive 27
  ∂v 
T ds = c P dT − T   dP
 ∂T  P

 If the increase in pressure rather than the decrease in

volume is specified , the temperature change can be
found from eqn (6-31);

T ds = 0 = c P dTs − β v T dPs

βvT
dTs = d Ps (6-34)
cP
28
  ∂v 
T ds = c P dT − T   dP
 ∂T  P

 If temperature is kept constant, there must be a

heat flow out of the system; this heat is
calculated by using eqn (6-31) setting
dT = 0 and T ds = dq;

dq = − β v T dPT (6-35)

29
example 6.1:
Consider an adiabatic compression of 10-3
kilomole of liquid He4 which decreases the
volume by 1%. Given that;
 T = 6 K, P = 19.7 atm,
 v = 2.64×10-2 m3 kilomol-1

 κ = 9.42×10-8 m2 N-1, β = 5.35×10-2 K-1,

 cv = 9950 J kilomol-1 K-1 and
 cP = 14760 J kilomol-1 K-1

remain constant during the compression.

30
from eqn (6-33);

βT
dTs = − d vs
κc v

=−
(5.35 × 10 )(6)(2.64 × 10 )(− 0.01)
−2 −5

(9.42 × 10 )(9.95 × 10 )
−8 3

−5
= 9 × 10 K

31
if pressure on 10-3 kilomole of He4 is increased by
1%, then from eqn (6-34);

βvT
dTs = d Ps
cP

=
(5.35 × 10 )(2.64 × 10 )(6 )(19.7 )(1.01 × 10 )(0.01)
−2 −5 5

(1.48 × 10 )
4

= 1.1 × 10 −5 K

 The temperature changes during adiabatic

processes are very small (helium is a rather soft
solid with large β and small κ)
32
 βT
T ds = cv dTs + dvs
κ

The heat that flow out of the same sample of He4

so as to keep the temperature constant during an
isothermal process for the same change in volume can be
computed by eqn (6-30);

 ∂P  β
dq = T   dvT = T dvT
 ∂T  v κ

= (6 )
(5.35 × 10 )(2.64 × 10 )(− 0.01)
−2 −5

(9.42 × 10 )
−8

−1
= −0.9 J kilomol
33
 T ds = cP dTs − β v T dPs

For an isothermal increase in pressure;

dq = − β v T dPT
( )( ) ( )
= − 5.35 × 10 − 2 2.64 × 10 −5 (6 )(19.7 ) 1.01 × 10 5 (0.01)
= −0.17 J kilomol −1

end example
34
 The pressure needed to decrease the volume of
a substance adiabatically can be found from
eqn. (6-32);

 ∂T   ∂T 
T ds = 0 = c P   dv + c v   dP
 ∂v  P  ∂P  v
cP cv κ
= d vs + d Ps
βv β
35
  ∂T   ∂T 
T ds = 0 = c P   dv + c v   dP
 ∂v  P  ∂P  v
cP cv κ
= d vs + d Ps
βv β

so that

1  ∂v  cv
−   =κ
v  ∂P  s cP (6-36)

κ
κs = (6-37)
γ

 where κs is the adiabatic compressibility

36
6. Properties of a pure substance
 From eqn (6-31);
cP  ∂v 
ds = dT −   dP
T  ∂T  P
 and from eqn (6-22);
  ∂v  
d h = c P dT + v − T    dP
  ∂T  P 
37
 cP  ∂v    ∂v  
ds = dT −   dP d h = c P dT + v − T    dP
T  ∂T  P   ∂T  P 

 The entropy and enthalpy in terms of an arbitrary reference

state P0, v0 and T0 are;

T cP P  ∂v 
s = ∫T0 T
dT − ∫
P0
  dP + s 0
 ∂T  P
(6-38)

T P   ∂v  
h = ∫T0
c P dT + ∫
P0
v − T 

  dP + h0 (6-39)
 ∂T  P 

38
  ∂c P   ∂ 2v 
  = − T  2 

 ∂P  T  ∂T P

 Integrating eqn (6-26) with P at the constant

temperature T;
P  ∂ 2v 
c P0 = c P + T ∫P0

 ∂T 2

 dP

P
(6-40)

 The entropy and enthalpy of a system can be

determined from its equation of state and its specific
heat capacity as a function of temperature
39
example 6.2:
In a particular range for pressure and temperature, the
equation of state for a substance is given as follows;

Pv P RT C
=1 − C′ 4 or v= − 3
RT T P T
where C and C′ are constants.

Find the expression for the change in enthalpy and

entropy for the substance in an isothermal process.

40
 Use eqn (6-39):
isothermal
T P   ∂v  
h = ∫T0
c P dT + ∫ P0
v − T 

  dP + h0
 ∂T  P 

 As the substance is in an isothermal process,

dT = 0;
  ∂v  
(h2 − h1 )T
2
= ∫1
v − T 

  dPT
 ∂T  P 
41
 RT C   ∂v  
(h2 − h1 )T
2
v= − 3
P T
= ∫
1
v − T 

  dPT
 ∂T  P 

 ∂v  R 3C
  = + 4
 ∂T  P P T

  R 3C  
(h2 − h1 )T
2
= ∫1


v − T  + 4   dPT
 P T P 
2  RT C RT 3C 
= ∫
1  P
− 3 −
T
− 3  dPT
P T 
2 4C 
− T 3  dPT = − T 3 (P2 − P1 )T
4C
= ∫1  
42
 RT C
v= − 3
P T

 Use eqn (6-38):

isothermal
T cP P  ∂v 
s = ∫ T0 T
dT − ∫P0
  dP + s 0
 ∂T  P

 ∂v   R 3C 
(s 2 − s1 )T
2 2
= − ∫
1
  dPT = −
 ∂T  P ∫
1
 + 4  dPT
P T 

 P2 
(s 2 − s1 )T = − R ln  − 4 (P2 − P1 )T
3C
 P1 T T
43
End