CYL100 201314 I semester Homework 3

Handed out: August 17, 2013

Due in: August 23, 2013
Notes: 1. Unless otherwise stated, gases can be considered to behave ideally.
2. You will need a table of thermodynamic data for some of the problems. Indicate the source of your thermodynamic
data.
1. Calculate the change in the chemical potential for N2 , when the temperature changes from 298.15 K to 130 K and
pressure changes from 1 atm to 600 atm. Treat nitrogen as a van der Waals gas with a = 1.39000 L2 atm mole2
and b = 0.03913 L mole1 . Compare your result with that obtained using the following data: Hm (130 K, 1 atm) =
10.655 kJ/mol, Hm (298.15 K, 1 atm) = 15.586 kJ/mol, Hm (130 K, 600 atm) = 7.305 kJ/mol, Sm (130 K, 1 atm)
= 0.16710 kJ/mol K, Sm (298.15 K, 1 atm) = 0.19137 kJ/mol K, Sm (130 K, 600 atm) = 0.09633 kJ/mol K.
First we evaluate 1 = (Tf , pi ) (Ti , pi ), when the temperature changes from 298.15 K to T at a constant
pressure of 1 atm. The plan is simple:
(a) Get Cp (T , 1atm) and s(298.15 K, 1 atm) from a database.
R T C (T,p )
(b) Integrate s(T, pi ) = s(Ti , pi) + Ti p T i dT to obtain s(T, p = 1 atm.
RT
(c) Use the expression obtained for s(T, p = 1 atm in 1 = Tif s(T, pi )dT and integrate to get (T, p = 1 atm.
Rp
Next, we evaluate 2 = (Tf , pf ) (Tf , pi ) = pif v(Tf , p)dp. Here we encounter a difficulty. There is no
explicit expression for v(Tf , p), so the integral cannot be performed directly. There is a way out of this difficulty.
The variable
  of integration may be changed form p to v. Since the integral is performed at constant temperature,
p
dp = V
dV . Inserting this in the expression for gives
T

v(Tf ,pf )

(Tf , pf ) (Tf , pf ) =


v(Tf , p)

v(Tf ,pi )

p
V


dV
T =Tf

Note that when the variable of integration is changes, the limits of integration is chnged from pi and pf to v(Tf , pi)
and v(Tf , pi ). THe steps involved in the evaluation of the integral are:
 
p
.
(a) For the van der Waals equation of state and calculate v V
T =Tf

(b) For the vdW equation of state calculate the molar volumes v(Tf , pi ) and v(Tf , pf ). For example, to find
v(Tf , pi ), we have to solve the equation pi = f (Tf , v) for v. This would involve solving pi v 3 (pi b + RTf )v 2 +
av b = 0 for v. This equation either has three real roots or two complex and one real root. If it is the latter,
the real root is the molar volume of the gas. If all the three roots are real, the lowest root is the molar volume
of the liquid and the highest the molar volume of the gas. This root finding is best done with a computer
using some symbolic manipulation program.
(c) Perform the integral.
2. The Gibbs energy of a binary mixture of species a and species b at 300 K and 10 bar is given by the following
expression:
g = 40xa 60xb + RT (xa ln xa + xb ln xb ) + 5xa xb
[kJ/mol]
(a) For a system containing 1 mole of species a and 4 moles of species b, find Gmix and Smix .
(a) Substitute xa = 1 and xb = 1 to obtain the molar volumes of pure a and b respectively.
(b) Write the extensive Gibbs energy
G = 40na 60nb + RT (na ln

na
nb
na nb
+ nb ln
)+5
na + nb
na + nb
na + nb

(c) The chemical potentials are determined by taking the appropriate derivative


G
na
n2b
a =
= 40 + RT (ln
)+5
na T,P,nb
na + nb
(na + nb )2

b =

G
nb


= 60 + RT (ln
T,P,na

nb
n2a
)+5
na + nb
(na + nb )2

(d) The Gibbs energy of mixing is

Gmix = G(na = 1, nb = 4) (1a (xa = 1) + 42 (xb = 1))

The derivative of Gmix with respect to T gives Smix .

(b) If the pure species are mixed together adiabatically, do you think the temperature of the system will increase,
stay the same, or decrease. Explain, stating any assumptions that you make.
From Gmix and Smix we can determine Hmix . The temperature change will +ve, ve, or zero depending on
whether the Hmix is < 0, > 0, or 0.
3. (a) Calculate the entropy of mixing 3 mol of hydrogen with 1 mol of nitrogen.
This was discussed in class. xN2 = 0.25 and xH2 = 0.75
X
Smix = nR
xi ln xi
i

(b) Calculate the Gibbs energy of mixing at 25 .

Gmix = T Smix = nRT

xi ln xi

(c) At 25 , calculate the Gibbs energy of mixing 1 mol of nitrogen, 3(1 ) mol of hydrogen, and 2 mol of
ammonia as a function of . Plot the values from = 0 to = 1 at intervals of 0.2
Evaluate
X
Gmix = T Smix = nRT
xi ln xi ,
i

where N2 =

1
42 ,

H2 =

33
42 ,

and NH3 =

2
42

at intervals of 0.2 for .

(d) If
= 16.5 kJ/mol at 25 , calculate the Gibbs energy of the mixture for values of = 0 to = 1
at intervals of 0.2. Plot G versus if the initial state is the mixture of 1 mol N2 and 3 mol of H2 . (e) Calculate G
for e at p = 1 atm.
This requires you to compute the Gibbs energy of the mixture, which means that

X
X 
pi
G=
ni i =
ni i + RT ln
p
i
i
Gf (NH3 )

Note that H2 = N2 = 0 and ni = xi n.

4. The reaction SO2 (g) + 12 O2 SO3 is performed starting with 1.2 moles of SO2 , 0.8 mole of O2 , and 0.07 moles
of SO3 . At some time after you start the reaction, the extent of reaction is = 0.5. Calculate the number of moles
and the mole fractions of each component at that time.
n(SO2 ; = 0.5) = 1.2 + (1).5 = 0.7
n(O2 ; = 0.5) = 0.8 + (1/2).5 = 0.55
n(SO2 ; = 0.5) = 0.07 + (1).5 = 0.57
5. Fuel cells provide an attractive alternative energy source. They require an H2 feed stream to operate. Consider a
fuel cell based on the direct conversion of methanol to form hydrogen:
H2 O(g) + CH3 OH(g)CO2 (g) + 3 H2 (g)
The reaction is carried out at 60 and low pressure, with a feed of twice as much water as methanol. The equilibrium extent of reaction is = 0.87. How many moles of H2 can be produced per mole of CH3 OH in the feed?
What is the mole fraction of H2 ?

n(CH3 OH; = 0.87) = 1

n(H2 O; = 0.87) = 2
n(CO2 ; = 0.87) =
n(H2 ; = 0.87) = 3 = 2.61 moles
x(H2 ) =

2.61
= 0.55
3 + 2

6. Calculate the equilibrium constant at 298 K for the reaction of problem 5.

X

grxn.,298
=
i (gf )i = 3.83kJ/mol
K = exp(

grxn.,298
) = 4.69
RT

7. Calculate the equilibrium constant at 60 for the reaction of problem 5.

K333
48970
ln
=
4.69
8.314

1
1

333 298


= 2.08

K333 = 37.44
8. We wish to produce formaldehyde, CH2 O, by the gas-phase pyrolysis of methanol, CH3 OH, according to:
CH4 O(g)CH2 O(g) + H2 (g)
The relevant thermochemical data is

gf,298
hf,298
Ai
Bi
Ci
Di

CH4 O
162.0
200.7
2.211
1.222 102
3.450 106

CH2 O
110.0
116.0
2.264
7.022 103
1.877 106

H2
0
0
3.249
0.422 103
0.0.83 105

I have access to data for CP in the form A + BT + CT 2 + DT 2 . If you have CP in some other form, that will do
just fine.
(a) What is the equilibrium constant at room temperature? Would you expect an appreciable yield of product?
At 25 , we calculate the equilibrium constant, K,


52000
= 7.644 1010
K = exp
8.314 298.2

= constant?
(b) Consider the reaction at 600 and 1 bar. What is the equilibrium constant (i) assuming Hrxn

ln

K873
K298

hrxn = 84.7 kJ/mol



1
1
84700

= 22.5
=
8.314 873 298
KT = 4.63

(T )?
= Hrxn
(ii) using Hrxn

ln

K873
= 23.2
7.64 1010
KT = 8.67

9. Consider the following general gas-phase reaction:

aA(g) + bB(g)cC(g)dD(g)
The constant-pressure reactor also contains an inert species, I. Describe how the following reactor conditions affect
yield of reaction products:
We note that

K=

Y
i

xii P i = 

nC
nT
nA
nT

c 
a 

nD
nT
nB
nT

d
v
b P ,

where v = c + d a b and nT = nA + nB + nC + nD + nI . Rearranging, we have

 v c d
P
nC nD
K=
v
nT naA nbB
(a) temperature;
In an exothermic reaction, K decreases as temperature increases; therefore, the right-hand side must also decrease.
The equilibrium will shift to the left, decreasing nC and nD while increasing nA and nB . Thus, the equilibrium
conversion and potential product yield will decrease. Conversely, the equilibrium conversion of an endothermic
reaction increases with increasing temperature.
(b) pressure;

Pressure is primarily affected by the term P v . K is independent of pressure.


 c d
1
nC nD
1
=
v
v
P
KnT naA nbB
The effect of pressure will primarily depend on the sign of v. If the number of moles of products is greater than the
number of moles of reactants, v is positive. In this case, using an argument similar to that in part (a), an increase
in pressure decreases the equilibrium conversion. Conversely, if there are more reactants than products, conversion
increases with increasing pressure. This is a restatement of Le Chteliers principle.
(c) addition of inert species;

nvT

Pv
=
K


ncC ndD
naA nbB

If there are more moles of products than of reactants (v > 0), an increase of inert increases the equilibrium
conversion. Conversely, if there are more moles of reactants than of products, conversion decreases with added
inerts. If the moles of reactants equal the moles of products, there is no effect of adding inerts.
This effect can be understood on a molecular scale. If we consider a reaction with more moles of products than of
reactants, more individual species must collide (find each other) for the reaction to proceed backward as compared
to forward. Addition of an inert then makes it harder for the backward reaction relative to the forward reaction,
since the inerts make it harder for the greater number of product species to find each other. Thus, the forward
reaction will be greater than the reverse reaction relative to the case of no inert, and equilibrium conversion will be
greater.
(d) additional (nonstoichiometric) reactant in feed.
If there is a reactant in the feed, the denominator on the right-hand side of requires more conversion to satisfy the
equation
 v c d
nC nD
P
.
K=
nvT naA nbB
Thus, a reactant in the feed will increase the conversion of the other (limiting) reactant.
10. Consider the production of ammonia from the catalytic reaction of a stoichiometric feed of nitrogen and hydrogen.
The reaction temperature is 500 and the reactor pressure is 1 bar.
N2 + 3 H2 2 NH3
What is the maximum possible conversion?
Species
NH3
N2
H2

i
2
1
3

hf
46.11 kJ/mol
0
0

gf
16.45 kJ/mol
0
0

Ai
3.578
3.280
3.578

Bi
3.020 103
0.593 103
0.422 103

Di
0.186 105
0.040 105
0.083 105

At 25 , we calculate the equilibrium constant, K,


K=

2
42

1
42



2

33
42


2
P
=
exp

3

32900
8.314 298.2

= 5.81 105

(a) Take Hrxn

= constant.
We use the equation

hrxn
K
ln
=
K298
R

1
1

T
298

92220
=
8.314

KT = 6.754 105
With P = 1 bar, the extent of the reaction is e = 0.005.

(b) Take Hrxn

= Hrxn
(T ).
We use the equation

ln

K
= 24.37
K298

KT = 1.51 105
With P = 1 bar, the extent of the reaction is e = 0.003.

1
1

773 298


= 22.28

11. Consider the two equilibria,

*
A2 )

2A

*
AB
)

A + B,
and assume that the r G and therefore K is the same for both. Show that the equilibrium value of 2 is greater
than the equilibrium value of 1 ? What is the physical reason for this result?
This is straightforwardly proved.
If an enclosure at high temperature contains equal number of atoms A nad B, then, when the temperatures is
lowered, and molecules A2 , AB, B2 form, they do not form in equal numbers, but in the ratio 1:2:1.
If two socks are chosen from a box containing equal number of white and black socks, the probability that a pair
of black socks are chosen is 1/4, a pair of white, 1/4, and one black and one white, 1/2.