CHM 373

Solutions to UPC Chapter #3

July 3, 2013

1. For ideal diatomic gases with thermally active translational and rotational motions, D = 5.
   
D ∂U 5 ∂T 5
a) Recall: U = nRT . So = nR = nR.
2 ∂T V 2 ∂T 2
 
D ∂U
b) If U = nRT and T is constant, = 0.
2 ∂V T

∂ P1
   
nRT ∂V nRT
c) According to the ideal gas law, V = . So if T is constant, = nRT =− .
P ∂P T ∂P P2
   
nRT ∂P nR ∂T nR
d) By the ideal gas law, P = . Thus, if V is constant, = = .
V ∂T V V ∂T V
"  D #   
V2T2 2 ∂S
e) According to equation 2.24, ∆S = nR ln + ln . To solve , set T1 = T0 , T2 =
V1T1 ∂V T
 
T T
T, V1 = V0 , and V2 = V . Since T is constant, = 1, and ln = 0.
T0 T0
So,  
∂S ∂ ∂ ln V ∂ ln V0 nR
= nR [ln V − ln V0 ] = nR − nR =
∂V T ∂V ∂V ∂V V
(since V0 is constant and the derivative of a constant is zero).

f) Using the chain rule,

 
∂U 5

∂U
 
∂U ∂T
 
∂T V
 nR 5
= =   = 2 = V,
∂P V ∂T V ∂P V ∂P nR 2
∂T V V
     
∂U ∂U ∂V
= = 0, and
∂P T ∂V T ∂P T
       
∂S ∂S ∂V nR nRT nRP nR
= = − 2 =− 2 =− .
∂P T ∂V T ∂P T V P P P
2. For ideal diatomic gases with thermally active translations, rotations, and vibrations, D = 7.

1
  
∂S
a) To solve , use equation 2.24, where T1 = T0 , T2 = T, V1 = V0 , and V2 = V . Since T is constant,
∂V
 T

T T
= 1 and ln = 0. So,
T0 T0
 
∂S ∂ ∂ ln V ∂ ln V0 nR
= nR [ln V − ln V0 ] = nR − nR =
∂V T ∂V ∂V ∂V V
(since V0 is constant and the derivative of a constant is zero).
 
∂S
b) To solve , use equation 2.24. Since the volume is constant, terms involving V go to zero, leaving
∂T V
 
∂S 7 ∂[ln T − ln T0 ]
= nR .
∂T V 2 ∂T
Since T0 is constant (i.e. the derivative is equal to zero),
 
∂S 7 ∂[ln T ] 7nR
= nR = .
∂T V 2 ∂T 2T
3. This problem
 seeks a general
  solution for a system with D thermally active quadratic terms in the Hamil-
∂U ∂S
tonian for and . Recalling 1a,
∂T V ∂T V
   
∂U D ∂T D
= nR = nR,
∂T V 2 ∂T V 2
D
and according to equation 1.44, CV = R. Similarly from 2b,
2
 
∂S D ∂[ln T ] D nR
= nR =
∂T V 2 ∂T 2 T
Multiplying the above result by T gives
 
∂S D nR D
T =T = nR.
∂T V 2 T 2
Thus
   
∂U D ∂S
CV = = R=T
∂T V 2 ∂T V
Rearranging this expression,
CV
dT = dSV
T
δQ
Equation 2.5 states dS = , so
T
CV δQV
dT =
T T

CV dT = δQV
 
δQ
CV =
∂T V

2
4. Using the ideal gas law, V = nRT /P and V0 = nRT0 /P0 , so

V nRT /P T P0
= =
V0 nRT0 /P0 T0 P
Substituting this expression into equation 2.25 yields
         
T P0 T T P0 T
∆S = RT + CV ln = R ln + R ln + CV ln
T0 P T0 T0 P T0
Combining like terms,
   
T P0
∆S = (CV + R) ln + R ln .
T0 P
    
∂S ∂ T 1
= (CV + R) ln = (CV + R) .
∂T P ∂T T0 T
Thus,
   
∂S 1
T =T (CV + R) .
∂T P T
 
∂S
Since T = CP , then CP = CV + R.
∂T P

5. Since there are a fixed number of molecules, dN = 0 and

   
dS dS
dS = dT + dV.
dT V,N dV T,N

From equation 2.28 ∆S = N kB ln(V /V0 ) + D

2 N kB ln(T /T0 ), we obtain
   
dS D d ln T D N kB
= N kB =
dT V,N 2 dT 2 T
   
dS d ln V N kB
= N kB =
dV T,N dV V
So,
D N kB N kB
dS = dT + dV.
2 T V
We know that P V = N kB T , so
D N kB P
dS = dT + dV.
2 T T
D
Using U = 2 N kB T , we can find an expression relating dT to dU . The derivative of U is
D D
dU =
N kB dT + kB T dN.
2 2
The problem states dN = 0 which simplifies dU ,
D 2dU
dU = N kB dT =⇒ dT = .
2 DN kB
Therefore,

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 1 P
dS =
dU + dV
T T
which is equivalent to equation 3.13 when dN = 0.

6. The chemical potential change of an ideal gas (at constant temperature), dµ = −T dS (see equations 3.35,
3.36 and the following exercise), which can be integrated to give
   
V2 V1
∆µ = −T ∆S = −kB T ln = kB T ln
V1 V2
a)
1m3
      
V1 J
∆µ = kB T ln = 1.38 × 10−23 × (300K) × ln
V2 K 10m3

∆µ = −9.53 × 10−21 J/molecule

b)      
23 molecule −21 J −3 kJ
NA ∆µ = 6.02 × 10 × −9.53 × 10 × 10
mole molecule J
kJ
NA ∆µ = −5.74
mol
c) To determine the work required to return the gas to its original volume, we must integrate −P dV from
V2 to V1 .
dV
δW = −P dV = −nRT
V

1m3
    
V1 J
W = −nRT ln = −(1mol) × 8.314 × (300K) × ln
V2 K · mol 10m3
kJ
W = 5.74
mol
Note the answers to b and c are equal in magnitude but opposite in sign. This demonstrates that the chemi-
cal potential change is equivalent to the corresponding reversible work. In other words, returning the system
back to its original state requires doing reversible work which is exactly equal to the chemical difference
between the initial and final state.

7. Gibbs phase rule: f = c − p + 2

f = number of degrees of freedom (P, T or composition of each phase)

c = number of components
p = number of phase that are in equilibrium with each other

For an ice cube in a glass of water f = 1 − 2 + 2 = 1, so P and T cannot be varied independently while
maintaining two phases in equilibrium. In other words, the two-phase region is a curve in the phase diagram,
long which P is a function of T (or conversely T is a function of P ). So, if P is varied then T is determined,
or if T is varied then P is determined.

8. If there are three phases in equilibrium in a system that contains only one component, such as pure water,
then f = 1 − 3 + 2 = 0. This implies that neither P nor T can vary while maintaining three phases in

4
equilibrium with each other. In other words, three phases can only coexist in pure water at a single point in
the phase diagram, and this point is called the “triple point”.

9. If there are three phases in equilibrium with each other in a system containing two components,
such as ethanol and water with solid, liquid, and vapor phases all in equilibrium with each other, then
f = 2 − 3 + 2 = 1. This implies that the three phase region in a two-component system is represented by a
curve for which P (T, Ξi ), or equivalently T (P, Ξi ), where Ξi is the total mole fraction of alcohol in water in
each of the three phases.

(a) The temperature can be varied while maintaining the three phases in equilibrium with each other,
but the pressure and composition of the three phases is fixed by the value of the temperature.

(b) If the pressure is constant then the three phases can only coexist at one particular temperature, in
which case the compositions of the three phases will also be fixed.

Note that, if the composition of one of the three phases had been fixed, then the phase rule would re-
quire that there is only on temperature, pressure and the composition of the other three phases which could
be present in such a two-component, three-phase equilibrium.
10. The Legendre transform of variables between two thermodynamic functions is performed by equating the
new function with the old function minus the product of the old variable and the slope of the old function
(with respect to the old variable). To transform A(T, V, Ni ) to G(T, P, Ni ),
 
dA
G(T, P, Ni ) = A(T, V, Ni ) − V
dV T,Ni
 
dA
Note that is the slope of the old function with respect to the old variable, and V is the old
dV T,Ni
variable. Since G = U − T S + P V = A + P V (obtained via Legendre transform of U), comparison of the
above expression for G implies that
 
dA
P =
dV T,Ni
11. Equation A = U − T S implies dA = dU − T dS − SdT
P
a) The fundamental equation for dU states: dU = T dS − P dV + µi dNi . When the latter expression for
dU is substituted in the expression for dA we obtain
X
dA = T dS − P dV + µi dNi − T dS − SdT

X
dA = −P dV + µi dNi − SdT

b) Since A(T, V, Ni ) we know that

    X  ∂A 
∂A ∂A
dA = dT + dV + dNi
∂T V,Ni ∂V T,Ni ∂Ni T,V,Nj 6=Ni
so
 
∂A
= −S
∂T V,Ni

5
  
∂A
= −P
∂V T,Ni
 
∂A
= µi
∂Ni T,V,Nj 6=Ni
c) The same result was obtained in problem 10 of chapter 3.
 
∂A
= −P
∂V T,Ni
An equivalent result was obtained in the Exercise 3.3 on page 105
 
∂A
= −S
∂T V,Ni
P
12. We will use the fundamental equation
Pfor enthalpy, dH = T dS + V dP + µi dNi , for parts a and b, and
Gibb’s equation, dG = −SdT + V dP + µi dNi , for parts c and d.

a)  
dH
=T
dS P,Ni

b)  
dH
=V
dP S,Ni

c)  
dG
= −S
dT P,Ni

d)  
dG
= µi
dNi P,T,Nj 6=Ni

13. We have previously calculated ∆U and ∆S for isothermal ideal gas expansion processes. These will be
used in solving parts c-e.

a) ∆U = 32 R∆T = 0
 
V2
b) ∆S = R ln = 19J/K
V1
c) ∆A = ∆U − ∆(T S) = 0 − T ∆S = −RT ln(10) = −5.7kJ

d) ∆H = ∆U + ∆(P V ) = ∆U + ∆(RT ) = 0 + 0 = 0 (note we used the ideal gas law with n = 1)

e) ∆G = ∆U + ∆(P V ) − ∆(T S) = −T ∆S = −5.7kJ

14. D = 3 for an ideal monatomic gas

   
dS dU D 3
a) CV = T = = nR = nR
dT V dT V 2 2
Note the equivalence of these two expressions for CV was established in problem 3 of chapter 3.

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b) The results obtained in problem 4 of chapter 3 imply that the total (rather than molar) heat capacities
at constant pressure and constant volume are related as follows:
 
∂S 3 5
CP = T = CV + nR = nR + nR = nR
∂T P,Ni 2 2
The same result may also be obtained by

! !
(D ( D+2
   
dH d(U + P V ) 2 nRT + nRT ) 2 nRT ) D+2 5
CP = = = = = nR = nR
dT P dT P dT dT 2 2
P P

c)       
1 dV 1 d(nRT /P ) P nR 1
αP = = = =
V dT P nRT /P dT P nRT P T
d)       
−1 dV −1 d(nRT /P ) −P −nRT 1
κT = = = =
V dP T nRT /P dP T nRT P2 P
15. a) Pure water:

g cm3 cm3
18.015 × = 18.07
mol 0.997g mol
b) When 0.1 mol ethanol is added to 10 mol of water the volume of the system changes by 5.51 cm3 , which
implies that the partial molar volume of ethanol in water is

5.51cm3 cm3
     
∂V ∆V
≈ = = 55.1
∂nethanol T,P,nwater ∆nethanol T,P,nwater 0.1mol ethanol mol
c) Pure ethanol:
g cm3 cm3
46.07 × = 58.39
mol 0.789g mol
Thus, the partial molar volume of pure ethanol (58.39 cm3 /mol) is larger than that of ethanol in water
(55.1 cm3 /mol). This suggests that there is less empty space around an ethanol molecule dissolved in liquid
water than there is around an ethanol molecule that is surrounded by other ethanol molecules (in pure liquid
ethanol).

16. The following expression is true because entropy is an extensive function, and the variables being held
constant are intensive.
X  ∂S  X
S= ni = ni S̄i
i
∂ni T,P,nj 6=ni i