Homework 6 (Due Date Mar.

2, 2011)

Chapter 5.
P5.1, P5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.13, 5.14, 5.16, 5.18, 5.20, 5.22, 5.23, 5.30,
P5.45

P5.1) Beginning with Equation (5.5), use Equation (5.6) to eliminate Vc and Vd to

arrive at the result wcycle = nR(Thot – Tcold)1n Vb/Va.

V 
w ab   n R Thot ln b 
 Va 

w bc  n C V,m Tcold  Thot 

V 
w cd  n R Tcold ln d 
 Vc 

w da  n C V,m Thot  Tcold    w bc

V  V 
w total   n R Thot ln b   n R Tcold ln d 
 Va   Vc 

Thot Vc -1  Tcold Vb -1 and Tcold Va -1  Thot Vd -1

Solving the last two equations for Thot and equating the results yields:

Vb -1 Va -1
Thot  Tcold  Tcold
Vc -1 Vd -1

Therefore:

Vb Va V V
 or c  b
Vc Vd Vd Va

V  V  V 
w total   n R Thot ln b   n R Tcold ln d   n R Thot  Tcold  ln b 
 Va   Vc   Va 

P5.2) Consider the reversible Carnot cycle shown in Figure 5.2 with 1 mol of an ideal
gas with CV = 3/2R as the working substance. The initial isothermal expansion occurs

at the hot reservoir temperature of Thot = 600°C from an initial volume of 3.50 L (Va)

to a volume of 10.0 L (Vb). The system then undergoes an adiabatic expansion until

the temperature falls to Tcold = 150.°C. The system then undergoes an isothermal

compression and a subsequent adiabatic compression until the initial state described

by Ta = 600.°C and Va = 3.50 L is reached.

a. Calculate Vc and Vd.

b. Calculate w for each step in the cycle and for the total cycle.

c. Calculate  and the amount of heat that is extracted from the hot reservoir to do

1.00 kJ of work in the surroundings.

a) Vc results from an adiabatic expansion:

Be careful here. Heat capacity at constant volume gives dU= CvdT
Internal energy can be given dU= dq + dw
But for adiabatic systems dq=0. Therefore dU = dw = -pdV
Set these definitions equal to each other.
CvdT = -pdV
Now substitute the ideal gas law
CvdT = -nRT/V dV
Put temperature on the Heat Capacity part of the equation

1 1
C V   dT  n R ln dV
T V

Integrate both sides and here’s what you get.

Thot V
C V ln   n R ln c
Tcold Vb

Solving for Vc yields:

Remember Cv = 3/2 R for an ideal gas and n=1.

Thot V
C V ln   n R ln c
Tcold Vb

 T  
Vc  Vb Exp  32  ln cold   10.0 L  Exp  32  ln
423.15 K   29.64 L
 Thot   873.15 K  
Vd can be obtained by using the relationship of two isothermal processes:

Va V
n R T ln  n R T ln d
Vb Vc

Va Vc 29.64 L   3.5 L 
Vd    10.4 L
Vb 10.0 L 
b) The work for each of the four steps:
a → b, isothermal expansion, w = -q, U = 0:

w  n R Thot ln
Vb
 
 1 mol  8.314472 J mol 1 K 1  873.15 K   ln
10.0 L  7.62 kJ
Va 3.5 L 
b → c, adiabatic expansion, q = 0, U = w:

 
w  C V ΔT  32  8.314472 J mol 1 K 1  423.15 K - 873.15 K    5.61 kJ

c → d, isothermal compression, w = -q, U = 0:

w   n R Tcold ln
Vd
 
 1 mol  8.314472 J mol 1 K 1  423.15 K   ln
10.4 L   3.68 kJ
Vc 29.64 L
d → a, adiabatic compression, q = 0, U = w:

 
w  C V ΔT  32  8.314472 J mol 1 K 1  873.15 K - 423.15 K   5.61 kJ

The total cycle:

w tot  w a b  w bc  w cd  w d a  7.62 kJ  5.61 kJ  3.68 kJ  5.61 kJ  - 3.94 kJ

q ab  q cd 7.62 kJ   - 3.68 kJ 
c) ε    0.517
q ab 7.62 kJ 
The amount of heat extracted is:

q ext 
1.0 kJ  - 7.62 kJ 
 1.93 kJ
- 3.94 kJ 
P5.3) Using your results from Problem P5.2, calculate q, U, and H for each step in

the cycle and for the total cycle described in Problem P5.2.

a→b ΔU  ΔH  0 because T  0 q   w  7.62  10 3 J

b→c ΔU  w  5.61  10 3 J because q  0

ΔH  ΔU  n R T  9.35 103 J

c→d ΔU  ΔH  0 because T  0 q   w  3.69  10 3 J

d→a ΔU  w  5.61  10 3 J because q  0

ΔH  ΔU  n R T  9.35 103 J

q total  7.62  10 3 J  3.69  10 3 J  3.93  10 3 J   w total

ΔU total  ΔH total  0

P5.4) Using your results from Problems P5.2 and P5.3, calculate S, Ssurroundings, and

Stotal for each step in the cycle and for the total cycle described in Problem P5.2.

a→b ΔS  ΔSsurroundings 

q reversible 7.62  103 J


 8.73 J K -1 ΔS total  0
T 873 K 

b→c ΔS  ΔSsurroundings  0 because q reversible  0

ΔS total  0

c→d ΔS  ΔSsurroundings 

q reversible  3.692  103 J


 8.73 J K -1 ΔS total  0
T 423 K 

d→a ΔS  ΔSsurroundings  0 because q reversible  0

ΔS total  0

For the cycle, ΔS  ΔSsurroundings  ΔS total  0 .

P5.5) Calculate S if the temperature of 1 mol of an ideal gas with CV = 3/2 R is

increased from 150. to 350. K under conditions of (a) constant pressure and (b)

constant volume.

a) S at p = constant:
Tf T T
ΔS  C p,m ln  n R  C V,m  ln f  52 n R ln f
Ti Ti Ti


 52  1 mol  8.314472 J mol 1 K 1  ln  350 K   17.6 J K 1
150 K 
b) S at V = constant:
Tf T T
ΔS  C V,m ln  n C V,m ln f  32 n R ln f
Ti Ti Ti


 32  1 mol 8.314472 J mol1 K 1  ln  350 K   10.6 J K 1
150 K 

P5.6) One mole of N2 at 20.5°C and 6.00 bar undergoes a transformation to the state

described by 145°C and 2.75 bar. Calculate S if

CP,m 2
3 T 5 T
 30.81  11.87  10  2.3968  10
J mol 1 K1 K K2

3
8 T
1.0176  10
K3

ΔS  nR ln
pf
n 
f T
C p,m

dT  1 mol  8.314472 J mol 1 K 1  ln
2.75 bar  
pi Ti
T 6.00 bar 
 T T 
2
T 
3

 30.81  11.87  10 3  2.3968  10 5    1.0176  10 8   
418.15 K   T
 K K K d J K 1
 1 mol 
293.65 K
T K

 
 6.48 J K 1  30.81  ln
 418.15  1
293 .65
J K  11.87  10  418.15  293.65J K 
3 1

 
1
2
 1
 
 2.3968  10 5 418.15 2  293.65 2 J K 1   1.0176  10 8  418.15 3  293.653 J K 1
3

      
 6.48 J K  10.89 J K  1.48 J K  1.06 J K 1  0.16 J K 1  16.8J K 1
1 1 1
  
P5.7) One mole of an ideal gas with CV = 3/2 R undergoes the transformations described in the

following list from an initial state described by T = 300. K and P = 1.00 bar. Calculate q, w, U, H,

and S for each process.

a. The gas is heated to 450. K at a constant external pressure of 1.00 bar.

b. The gas is heated to 450. K at a constant volume corresponding to the initial

volume.

c. The gas undergoes a reversible isothermal expansion at 300 K until the pressure

is half of its initial value.

a) Vi  

n R Ti 1 mol  8.314472 J mol 1 K 1  300 K  
 2.49  10 -2 m 3
pi 10 5 Pa  

Vf 
Tf
Vi 
450 K   2.49  10 -2 m 3  3.74  10 -2 m 3
 
Ti 300 K 

   
w  p external ΔVi  10 5 Pa  3.74  10 -2 m 3  2.49  10 -2 m 3  1.25  10 3 J

3
 
ΔU  n C V,m ΔT  1 mol   8.314472 J mol 1 K 1  150 K   1.87  10 3 J
2

q  ΔH  ΔU - w  1.87  10 3 J   1.25  10 3 J   3.12  10 3 J

T  3    450 K  
  1 mol     1  8.314472 J mol K   ln 
1 1
ΔS  n C p,m ln  f   8.43 J K
-1

 Ti   2    300 K  

b) w = 0 since V = 0

3
 
ΔU  q  n C V,m ΔT  1 mol   8.314472 J mol 1 K 1  150 K   1.87  10 3 J
2
5
 
ΔH  n C p,m ΔT  1 mol   8.314472 J mol 1 K 1  150 K   3.12  10 3 J
2
 T   3   450 K  
ΔS  n CV,m ln  f   1 mol      8.314472 J mol 1 K 1   ln    5.06 J K
-1

 Ti  2   300 K  

c) U = H = 0 since T = 0

V 
w reversible  q  n R T ln f  
   1 mol  8.314472 J mol 1 K 1  300 K   ln 2 
 Vi 
 1.73  10 3 J

ΔS 
q reversible

1.73  10 3 J 
 5.76 J K -1
T 300 K 

P5.8) Calculate Ssurroundings and Stotal for part (c) of Problem P5.7. Is the process

spontaneous? The state of the surroundings for each part is T = 300. K, P = 0.500 bar.

The gas undergoes a reversible isothermal expansion at 300 K until the pressure is

half of its initial value.

ΔSsurroundings 
q


 1.73  10 3 J 
 5.76 J K -1
T 300 K 

ΔS total  ΔS  ΔSsurroundings  5.76 J K -1  5.76 J K -1  0 , it is spontaneous.

P5.13) One mole of an ideal gas with CV,m = 5/2 R undergoes the transformations

described in the following list from an initial state described by T = 250. K and P =

1.00 bar. Calculate q, w, U, H, and S for each process.

a. The gas undergoes a reversible adiabatic expansion until the final pressure is half

its initial value.

b. The gas undergoes an adiabatic expansion against a constant external pressure of

0.500 bar until the final pressure is half its initial value.
 c. The gas undergoes an expansion against a constant external pressure of zero bar

until the final pressure is equal to half of its initial value.

a) The gas undergoes a reversible adiabatic expansion until the final pressure is half

its initial value. q = 0 because the process is adiabatic.

1 1 1  1

1 
Tf  Vf  T   pi  T  p  T   pi  
    f    and  f    i  ,  f    
Ti  Vi   Ti   pf   Ti   pf   Ti   pf 

 7
 1 
 5
Tf  1.00 bar  7  2
 2.00 
 
  5 7  0.820
Ti  0.500 bar 

Tf  0.820   250 K   205 K

5

ΔU  w  n C V,m ΔT  1 mol   8.314472 J mol 1 K 1  205 K - 250 K   935 J
2

7

ΔH  n C p,m ΔT  1 mol    8.314472 J mol 1 K 1  205 K - 250 K   1310 J 
2

Since this process is adiabatic, dq = 0. Therefore dU = dw and work W = ∆U = -935 J

S = 0, since qreversible = 0.

b) The gas undergoes an adiabatic expansion against a constant external pressure of

0.500 bar until the final pressure is half its initial value. q = 0 because the process is

adiabatic.

T T 
n C V,m Tf  Ti   n R p external  f  i 
 pf pi 

 n R p external   n R p external 
Tf  n C V, m    Ti  n C V,m  
 pf   pi 
  n R p external 
 n C V,m  
pi
Tf  Ti  
 n R p external 
 n C V,m  
 pf 
 5

 1 mol   8.314472 J mol 1 K 1    
1 mol  8.314472 J mol 1 K 1  0.500 bar  
 250 K   
2 1.0 bar  
5

 1 mol   8.314472 J mol 1 K 1    1

1 mol  8.314472 J mol K  0.500 bar  
1

2 0.5 bar  
 
 214 K

5
 
ΔU  w  n C V,m ΔT  1 mol   8.314472 J mol 1 K 1  214 K - 250 K   748 J
2
7
 
ΔH  w  n C p,m ΔT  1 mol   8.314472 J mol 1 K 1  214 K - 250 K   1050 J
2

p  T 
ΔS   n R ln f   n C p,m ln f 
 pi   Ti 
 0.500 bar  

 1 mol  8.314472 J mol 1 K 1  ln  
 1.0 bar  
 214 K  
7

 1 mol   8.314472 J mol 1 K 1  ln  
2  250 K  
 5.76 J K -1  4.52 J K -1  1.24 J K -1

c) The gas undergoes an adiabatic expansion against a constant external pressure of

zero bar until the final pressure is half its initial value.

T = w = 0, therefore, U = H = 0 and q = U - w = 0.

p   0.500 bar  
ΔS   n R ln f  
  1 mol   8.314472 J mol 1 K 1  ln   5.76 J K -1
 pi   1.0 bar  

P5.14) The standard entropy of Pb(s) at 298.15 K is 64.80 J K–1 mol–1. Assume that

the heat capacity of Pb(s) is given by

 
C P,m Pb, s   22.13  0.01172 T  1.00  105
T2
J mol 1 K 1 K K2

The melting point is 327.4°C and the heat of fusion under these conditions is 4770. J

mol–1. Assume that the heat capacity of Pb(l) is given by

C P,m Pb,l   32.51  0.00301 T

1
JK mol1 K

a. Calculate the standard entropy of Pb(l) at 500°C.

b. Calculate H for the transformation Pb(s, 25°C)  Pb(l, 500°C).

a)

600.55 K 773.15 K
C p,m ΔH fusion C p,m
Sm  Pb,,773 K   Sm  Pb,s,298.15 K    T/K  d T/K     d T/K 
600.55 K 
298.15 K
Tfusion T/K 
600.55 K
 22.13   0.01172  T/K   1.00  10  T /K 5 2 2
  4770 J mol 1 
  d  T/K  
298.15 K T/K   600.55 K 
773.15 K
 32.51   0.00301 T/K  d T/K
   
600.55 K T/K 
  64.80 J mol 1 K 1    20.40 J mol 1 K 1    7.94 J mol 1 K 1    7.69 J mol 1 K 1 
 100.8 J mol 1 K 1

b)

600.55 K 773.15 K
H total   C p,m dT/K   ΔH fusion  C dT/K 
solid liquid
p, m
298.15 K 600.55 K

  
 8918 J mol 1  4770 J mol 1  5254 J mol 1   
1
 18.94  10 J mol 3

P5.16) One mole of a van der Waals gas at 27°C is expanded isothermally and

reversibly from an initial volume of 0.020 m3 to a final volume of 0.060 m3. For the
 
van der Waals gas, U / V T  a / V m2. Assume that a = 0.556 Pa m6 mol–2, and

that b = 64.0  10–6 m3 mol–1. Calculate q, w, U, H, and S for the process.

Vf
 U 
ΔU     dV
Vi 
V  T

For a van der Waals gas:

 1 1 
ΔU  a   

 Vm,i Vm,f 

As shown in Example Problem 3.5.

 1 1 
ΔU  a   

 Vm,i Vm,f 

 

ΔU  0.556 Pa m 6 mol  2    
1
3

1
  
  1 mol  18.5 J
 0.020 m 0.060 m 3 

 V  b  
Vf Vf Vf
dV dV  1 1 
w    p dV  R T  a V  R T ln f   a   
Vi Vi
Vm  b  Vi
2
 Vi  b    Vf Vi 

   0.059936 
w   8.314472 J mol 1 K 1  300.15 K   ln 
 0.019936 
 
  
 0.556 Pa m 6 mol  2  
1
0.060 m 3

0.020
1
m
  2.73  10 3 J
 
3 

 

pi 
RT a
 2 
 

8.314472 J mol 1 K 1  300.15 K  0.556 Pa m 6 mol 2 
 1.237  10 5 Pa

Vi  b  Vi 
0.019936 m 3 
0.020 m 3 2
 

pf 
RT a
 2 
 

8.314472 J mol 1 K 1  300.15 K  0.556 Pa m 6 mol 2 
 4.146  10 4 Pa

Vf  b  Vf 0.059936 m 3
 
0.060 m 3 2
 

ΔH  ΔU  ΔpV   ΔU  p f Vf  p i Vi
    
 18.5 J   4.146  10 4 Pa  0.060 m 3  1.237  10 5 Pa  0.020 m 3  32.1 J   
q  ΔU  w  2.73  10 3 J

ΔS 
q reversible


2.73  10 3 J 
 9.10 J K -1
T 300.13 K 

P5.18) The amino acid glycine dimerizes to form the dipeptide glycylglycine

according to the reaction

2Glycine(s)  Glycylglycine(s) + H2O(l)

Calculate S, Ssurroundings, and Suniverse at T = 298 K. Useful thermodynamic data are:

Glycine Glycylglycine Water


H f kJ mol 1  –537.2 –746.0 –285.8

S°(J K–1 mol–1) 103.5 190.0 70.0

The standard entropy for this reaction is:

     
ΔSreaction   ν i Sf,i  2  103.5 J K -1 mol1  190 J K -1 mol1  70 J K -1 mol1  53 J K -1 mol-1
i

The standard enthalpy for this reaction is:

ΔH reaction   ν i H f,i  2   537.2 kJ mol 1    746 kJ mol 1   - 285.8 kJ mol 1   42.6 kJ K -1 mol
-1

And the entropies for the surroundings and universe:

ΔSsurroundings 
- dq  H reaction
 
- 42.6 kJ mol-1 
 142.95 J mol-1 K 1
T T 298.0 K 

   
ΔSuniverse  ΔSreaction  ΔSsurroundings  53 J K -1 mol-1  - 142.95 J K -1 mol-1  89.95 J mol -1 K 1

P5.20) Consider the formation of glucose from carbon dioxide and water, that is, the

reaction of the following photosynthetic process: 6CO2(g) + 6H2O(l)  C6H12O6(s) +

6O2(g). The following table of information will be useful in working this problem:
T = 298 K CO2 (g) H2O (l) C6H12O6(s) O2(g)

 1
H f kJ mol –393.5 –285.8 –1273.1 0.0

S° J mol–1 K–1 213.8 70.0 209.2 205.2

C P,m J mol1 K 1 37.1 75.3 219.2 29.4

Calculate the entropy and enthalpy changes for this chemical system at T = 298 K and

T = 330. K. Calculate also the entropy of the surrounding and the universe at both

temperatures.

The standard entropy and enthalpy and heat capacity for this reaction are:

ΔSreaction (298 K )   ν i Sf,i

i

 1  209.2 J K mol 1   6   205.2 J K -1 mol 1 

-1

  6  70.0 J K -1 mol 1    6   213.8 J K -1 mol 1   262.4 J K -1 mol -1

ΔH reaction (298 K )   ν i H f,i

i


 1   1273.1 kJ mol 1  6   0 kJ mol 1  
 
  6    285.8 kJ mol 1   6    393.5 kJ mol 1  
 2802.7 kJ mol -1

 
C p, reaction (298 K )  1  219.2 J K -1 mol 1  6   29.4 J K -1 mol 1  

  6   75.3 J K mol -1 1
   6  37.1 J K -1
mol 1

 278.8 J K mol -1 -1

At 330 K the entropy and enthalpy for this reaction are then:
T 

ΔS reaction (330 K )  ΔS reaction

( 298 K )  C p,reaction

ln f 
 Ti 

  
  262.4 J K -1 mol -1   278.8 J K -1 mol -1   330 K 
 ln   290.7 J K mol
-1 -1

 298.15 K 

ΔH reaction (330 K )  ΔH reaction (298 K )  C reaction Tf  Ti 

   
 2802.7 kJ mol -1   278.8 J K -1 mol -1  330 K  298.15 K   2793.8 kJ mol -1
And the entropies for the surroundings and universe:

-dq H reaction  2793.8 kJ mol 

-1

ΔSsurroundings     8.47  103 J mol-1 K 1

T T  330 K 
ΔSuniverse  ΔSreaction  ΔSsurroundings   290.47 J K -1 mol-1    8.47  103 J mol -1 K 1 
 8.76  103 J mol-1 K 1

P5.22) One mole of an ideal gas with CV,m = 3/2 R is transformed from an initial state

T = 600. K and P = 1.00 bar to a final state T = 250. K and P = 4.50 bar. Calculate

U, H, and S for this process.

3
 
ΔU  n C V,m ΔT  1 mol   8.314472 J mol 1 K 1  250 K  600 K    4.36  10 3 J
2

5
ΔH  n Cp,m ΔT  1 mol    8.314472 J mol 1 K 1    250 K  600 K    7.27  103 J
2

p   Tf 
ΔS   n R ln  f   n CV,m ln  
 pi   Ti 
  4.50 bar  
  1 mol   8.314472 J mol 1 K 1   ln  
 1.00 bar  
5   250 K  
 1 mol      8.314472 J mol 1 K 1   ln  
2   600 K  
 12.5 J K -1  18.2 J K -1   30.7 J K -1

P5.23) 15.0 g of steam at 373 K is added to 250.0 g of H2O(l) at 298 K at constant

pressure of 1 bar. Is the final state of the system steam or liquid water? Calculate S

for the process.

Assume that the final state is liquid water. If this is not the case, the calculated

temperature will be greater than 373 K.

 n steam ΔHvaporation  n steam C Hp, 2mO Tf  Tisteam   n H 2O C Hp,m2O Tf  TiH 2O  0  

Tf 
n steam C Hp,2mO Tisteam  n H 2O C Hp,m2O TiH 2O  n steam ΔHvaporation 
n steam C H 2O
p, m  n H 2O C H 2O
p, m 
  


15.0 g

  75.291 J mol 1 K 1  373 K  
-1 

  18.02 g mol  
 
   250.0 g   75.291 J mol 1 K 1  298 K 
 
  18.02 g mol -1  
   
   
  
15.0 g

  40650 J mol 1
-1 

Tf    18.02 g mol    333 K
   250.0 g  


15.0 g
 18.02 g mol -1

  75.291 J mol 1 K 1  
18.02 g mol -1 

  75.291 J mol 1 K 1  

    

S is calculated from the steam. It consists of condensing the steam at 373 K and

cooling the resulting water to 333 K.

ΔH vaporation  Tf 
ΔS   n  n Cp,mln 
Tvaporation  Tvaporation 
 
  40650 J mol     333 K  
1
 15.0 g 15.0 g 
 18.02 g mol-1    75.291 J mol K   ln  373 K 
1 1
  -1 

 18.02 g mol   373 K     
  -90.7 J K 1    7.11 J K 1    97.8 J mol 1 K 1

S is calculated for water. It consists of heating the water from 298 K to 333 K.

 T 
ΔS  n Cp,mln  f 
 Tfusion 
 250.0 g    333 K  
 -1 
  75.291 J K -1 mol 1   ln    116 J K
1

 18.02 g mol    298 K  

    
ΔS total  0 J K 1  116 J K 1  97.8 J K 1  18.2 J K 1 

The process is spontaneous!

P5.30) Calculate Ssurroundings and Stotal for the processes described in parts (a) and

(b) of Problem P5.13. Which of the processes is a spontaneous process? The state of

the surroundings for each part is as follows:

a. 250. K, 0.500 bar

b. 300. K, 0.500 bar

Ssurroundings = 0 for a) and b) because q = 0.

a) ΔS total  ΔS  ΔSsurroundings  0 J K -1   0 J K -1   0 J K 1 Process is not

spontaneous.

b) ΔS total  ΔS  ΔSsurroundings  1.24 J K -1   0 J K -1   1.24 J K 1 Process is

spontaneous.

P5.45) From a DSC experiment it is determined that for the denaturation of a protein
H = 640.1kJ mol–1 at Tm = 340 K and P = 1 bar. Calculate S for this denaturation at
T = 340 K and P = 1 atm. Determine the entropy and enthalpy changes at T = 310 K
assuming CP = 8.37 kJ K–1 mol–1 is independent of temperature between T = 310. K
and T = 340. K.
The entropy of denaturation at 340 K can be calculated as:

ΔS den 340 K  
ΔH den


640100 J mol -1 
 1882.6 J K -1 mol -1
T 340 K 
The entropy of denaturation at 310 K is:
340 K
ΔC p 310 K
1
ΔS den 310 K   ΔS den 340 K    dT  ΔS den 340 K   ΔC p  dT
310 K
T 340 K
T

 310 K  
  
ΔSden 310 K   1882.6 J K -1 mol -1  8.37 kJ K -1 mol -1 ln    1109.4 J K -1 mol -1
 340 K  
The enthalpy of denaturation at 310 K is:
 
ΔH den 310 K   ΔS den 310 K   310 K   1109.4 J K -1 mol -1  343.9 kJ K -1 mol -1
 Dq reveresible  P   1
Q1. Prove dS     dV  CV dT (*).
T  T V  T
Hint: Use Dqreversible = dU – Dw and (U/V)T = T(P/T)V – P.

 U   U  
Dqreversible = dU – Dw =   dV    dT   PdV (1).
 V  T  T V 
Since (U/V)T = T(P/T)V – P,
Eq.(1) becomes Dqreversible
  P    P 
= T    P dV  CV dT  PdV = T   dV  CV dT .
  T V   T V

Dq reveresible  P   1
Thus dS     dV  CV dT
T  T V  T

Q2. For ideal gas, show that dS is the exact differential using (*) (assume that Cv
depends only on T.)

To prove that dS is the exact differential is to prove

   S      S  
         ,
 T  V  T  V  V  T  V  T

 S   P   P  nR
According to Eq. (*),      , for an ideal gas where    ,
 V  T  T  V  T  V V

 
 2P 
   S        nR    0 .
       T  V  
2 
 T  V  T  V  T    V
 V

 S  Cv
According to Eq. (*),    , assume that Cv depends only on T, then
 T  V T

   S      Cv  
          0
 V  T  V  T  V  T   T

   S      S  
          0 , dS is exact.
 V  T  V  T  T  V  T  V
  C
Q3. Prove dS  dV  v dT (**) from equation eq. (*) above. Then,
 T
prove eq. (5.22) in the text using eq. (**) assuming that  and , Cv are constant.

 V 
 
 P   P   V   T  P 
         (3.8),
 T  V  V  T  T  P  V  
 
 P  T

Dq reveresible  P   1
dS     dV  CV dT (*) becomes
T  T V  T

 C
dS  dV  v dT (**), proved.
 T
Assuming ,  and Cv are constants,
 
Vf Tf
Cv Tf
S   dS  Vi  dV  Ti T dT   (Vf  Vi)  Cv ln Ti (5.22), proved.