Solutions to Exercises: Chapter 10

10.1 Use the chemical potential of an ideal gas in (10.1.9) and obtain the barometric
formula (10.1.10). Use the barometric formula to estimate the boiling point of water an
altitude of 2.50 km above the sea level. Assume an average T = 270 K.

Answer At equilibrium the chemical potential in a gravitational field obeys the

equation:
µ k (h) = µ k (0) − M kgh

The chemical potential of an ideal gas is µ k (p,T) = µ 0k (T) + RTln( p / p 0 ) . If we denote

the pressure at a height h by p(h), and use this in the above equation, we obtain:

µ 0k (T) + RTln( p(h)/ p0 ) = µ 0k (T) + RTln( p(0)/ p0 ) − Mk gh

which give the barometric formula:

p(h) = p(0)e −M k gh/RT

For the atmosphere, we may use the molar mass of N 2 for Mk.

(0.0289kg.mol −1 )(9.8m.s −2 )2500m

−
(8.314J.K −1 .mol −1 )(270K)
P = 1.0atm e = 0.73atm

Using the Clausius-Clapeyron equation we see that:

 0.73  40.6x10 3 J.mol −1  1 1

ln  = − 
1.0  8.314J.K −1  373.15 T1 

Solving for T1 =364.2K = 91.05˚C as the approximate boiling point of water at an

altitude of 2.5 km :

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 Solution Manual/ Kondepudi & Prigogine Chapter 10 2

10. 2 What heater coil is run at a voltage of 110V and it draws 2.0 amp current. If its
temperature is equal to 200˚C, what is the rate of entropy production due to this coil.

Answer
d iS VI (110V)(2.0A) J
= = = 0.46
dt T 473 Ks

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10.3 Calculate the equilibrium constants at T = 25.0˚C for the following electrochemical
reactions using standard potentials in Table 10.1.
(i) Cl2(g) + 2Li(s) -----> 2Li+ + 2Cl-
(ii) Cd(s) + Cu2+ -----> Cd2+ + Cu(s)
(iii) 2Ag(s) + Cl2(g) ------> 2Ag+ + 2Cl-
(iv) NaCl(s) -----> Na+ (aq) + Cl-

Answer

(i) The half-reactions and the corresponding potentials are:

1
Cl 2 + e − − − > Cl − 1.360 V
2
Li − − > Li + + e − -(-3.045)V

Hence V0 = (1.360+3.045)V = 4.405 V. Since 2 electrons are transferred in this

reaction, the equilibrium constant is:

K = e 2FV 0 /RT = 8.31x10148

Similarly, for
(ii) V0 = 0.741, K = e 2FV 0 /RT = 1.12x10 25

(iii) V0 = 0.561, K = e 2FV 0 /RT = 9.24x1018

(iv) V0 = 4.074, K = e 2FV 0 /RT = 5.36x10137

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 Solution Manual/ Kondepudi & Prigogine Chapter 10 3

10.4 Consider the reaction Ag(s) + Fe3+ + Br- ----> AgBr(s) + Fe2+ which is not in
equilibrium and hence can be used generate a EMF. The "half-cell" reactions that
correspond to the oxidation and reduction in this cell are,
Ag(s) + Br- ----> AgBr(s) + e- V0 = –0.071 V
Fe3+ + e- ----> Fe2+ V0 = 0.771 V
(a) Calculate V0 for this reaction.
(b) What is the EMF for the following activities: aFe3+ = 0.98 , aBr-= 0.30, aFe2+ = 0.01 at
T= 298.15
(c) What will the EMF be when T=0.0˚C ?

Answer
(a) The V0 for this reaction is the sum of the two half-cell potentials:
V0 = -0.071+0.771 = 0.700V
(b) The EMF can be obtained using the Nernst equation (10.2.20):
RT  a Fe2+  RT  0.01 
V = V0 − ln = 0.700V − ln = 0.79V.
nF  (a Br− ) (a Fe3+ )  F  0.30x0.98 
(c) At T = 273 K, the above formula gives V = 0.78V. So the change in the EMF of a
cell due to a change of T is very small.

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10.5 The K+ concentration inside a nerve cell is much larger than the concentration
outside the cell. Suppose the potential difference across the cell membrane is 90mV.
Assuming that the system is in equilibrium estimate the ratio of concentration of K+
inside and outside the cell. (The actual value is about 90 mV)

Answer
Using equation for the membrane potential we can write:
RT  m in 
φ out − φin = ln k+out 
F  m k+ 
From this it follows that:
k+ = Exp  (φ
m in out −φ in )F   90x10−3 x9.648x10 4 
=  = 33.22
Exp
m out  RT   8.314x298
k+
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 Solution Manual/ Kondepudi & Prigogine Chapter 10 4

n(0) −x 2 /4Dt
10.6 Verify that n(x,t) = e
2 πDt
is the solution of the diffusion equation (10.3.11). Using Mathematica or Maple plot this
solution for various values of t for one of the gases listed in Table 10.2. (assume n(0)=1).
This gives you an idea of how far a gas will diffuse in a given time. Obtain a simple
expression to estimate the distance a molecule will diffuse in a time t, given its diffusion
coefficient D.

∂n(x,t) ∂2 n(x, t)
Answer We need to show that n(x) is the solution of: =D
∂t ∂x2
The derivative with respect to t is:
∂n n(0)  1 1 −x2 /4Dt 1 x2 1 −x 2 /4Dt 
= − e + e
∂t 2 πD  2 t 3/2 t 4D t 2 

n(0) e −x /4Dt
2
 1 x2 
=  − 2 + 4Dt  (A)
2 πD t 3/2

Similarly the second derivative with respect to x is:

∂n n(0) (−2x) −x 2 /4Dt
= e
∂x 2 πDt 4Dt
∂ 2n n(0)  (−2) (−2x) (−2x)  −x2 /4Dt
2 = 2 πDt  4Dt + 4Dt 4Dt  e
∂x
n(0) e −x /4Dt 1  −1 x 2 
2

= + (B)
2 πD t 3/2 D  2 4Dt 
 Solution Manual/ Kondepudi & Prigogine Chapter 10 5

We see that multiplying (B) by D gives (A). Hence the given n(x,t) is the solution of
∂n(x,t) ∂2 n(x, t)
=D .
∂t ∂x2

Mathematica Code for the diffusion of CO 2:

===========================================================
(* Difusion of CO2 in air*)
Clear[x];
d=0.16*10^-4;t=50;
Plot[(1/(2*Sqrt[Pi*d*t]))Exp[x^2/(4*d*t)], {x,0.1,0.1}]

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10.7 Compute the diffusion current corresponding to the barometric distribution
n(x) = n(0)e −gMx/RT

∂n
Answer According to Fick' s law (10.3.7), the diffusion current J N = −D . For the
∂x
above n(x), the diffusion current is:
∂ Dn(0)gM −gMx/RT
J N = −Dn(0) e −gMx/RT = e .
∂x RT
This upward current is balanced by the downward current due to gravity.
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10.8 Using (10.4.9) and the ideal activity a(θ) = n(θ)/ntot for the dipole orientation,
obtain the equilibrium expression (10.4.10). Give an explicit expression for the function
F(T) in terms of µ0 and C.

Answer Using the given expression for the affinity in (10.4.9) we find that at
equilibrium:
 n(θ) 
µ 0 (T) + RTln  + gφ(θ) = C
 n tot 
in which C is a constant. This leads to:
 n(θ)  C − µ 0 (T) gφ(θ)
ln  = −
 n tot  RT RT
 Solution Manual/ Kondepudi & Prigogine Chapter 10 6

From this equation it follows that:

−gφ(θ)
n(θ) = n tot F(T)e RT

C−µ o (T)
in which F(T) = e RT
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10.9 The electric dipole moment of water is 6.14x10-30Cm. In an electric field of
10.0V/m, find the fraction of molecules oriented with respect to the field in the range
10˚<θ<20˚ when T=298K.

The fraction "x" of the molecules whose dipoles are oriented in the interval 10˚<θ<20˚ is
given by:
20

∫
n tot F(T) e acos(θ) sin(θ)dθ

x= 10
180
n tot F(T)
∫0 eacos(θ) sin(θ)dθ
in which a=pE/RT, where p=6.14x10-30NA and E=10.0Vm-1.

∫
1
The integral e acos(θ) sin(θ)dθ = − e acos(θ) . The value of a = 1.49x10-8. So the
a
above ratio can be written as:

x = a1
e[
1 acos(20)
− e acos(10)
=
]
6.73x10 −10
= 2.26x10 −2
[ ]
−8
e acos(180) − e acos(0) 2.98x10
a