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Introduction to chemical engineering thermodynamics

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You are on page 1of 8

13.1 (a) 4NH

3

(g) +5O

2

(g) →4NO(g) +6H

2

O(g)

ν =

i

ν

i

= −4 −5 +4 +6 = 1 n

0

=

i

0

= 2 +5 = 7

By Eq. (13.5),

y

NH

3

=

2 −4ε

7 +ε

y

O

2

=

5 −5ε

7 +ε

y

NO

=

4ε

7 +ε

y

H

2

O

=

6ε

7 +ε

(b) 2H

2

S(g) +3O

2

(g) →2H

2

O(g) +2SO

2

(g)

ν =

i

ν

i

= −2 −3 +2 +2 = −1 n

0

=

i

0

= 3 +5 = 8

By Eq. (13.5),

y

H

2

S

=

3 −2ε

8 −ε

y

O

2

=

5 −3ε

8 −ε

y

H

2

O

=

2ε

8 −ε

y

SO

2

=

2ε

8 −ε

(c) 6NO

2

(g) +8NH

3

(g) →7N

2

(g) +12H

2

O(g)

ν =

i

ν

i

= −6 −8 +7 +12 = 5 n

0

=

i

0

= 3 +4 +1 = 8

By Eq. (13.5),

y

NO

2

=

3 −6ε

8 +5ε

y

NH

3

=

4 −8ε

8 +5ε

y

N

2

=

1 +7ε

8 +5ε

y

H

2

O

=

12ε

8 +5ε

13.2 C

2

H

4

(g) +

1

2

O

2

(g) →(CH

2

)

2

O(g) (1)

C

2

H

4

(g) +3O

2

(g) →2CO

2

(g) +2H

2

O(g) (2)

The stoichiometric numbers ν

i, j

are as follows:

i = C

2

H

4

O

2

(CH

2

)

2

O CO

2

H

2

O

j ν

j

1 −1 −

1

2

1 0 0 −

1

2

2 −1 −3 0 2 2 0

n

0

=

i

0

= 2 +3 = 5

By Eq. (13.7),

y

C

2

H

4

=

2 −ε

1

−ε

2

5 −

1

2

ε

1

y

O

2

=

3 −

1

2

ε

1

−3ε

2

5 −

1

2

ε

1

y

(CH

2

)

2

O

=

ε

1

5 −

1

2

ε

1

y

CO

2

=

2ε

2

5 −

1

2

ε

1

y

H

2

O

=

2ε

2

5 −

1

2

ε

1

701

13.3 CO

2

(g) +3H

2

(g) →CH

3

OH(g) +H

2

O(g) (1)

CO

2

(g) +H

2

(g) →CO(g) +H

2

O(g) (2)

The stoichiometric numbers ν

i, j

are as follows:

i = CO

2

H

2

CH

3

OH CO H

2

O

j ν

j

1 −1 −3 1 0 1 −2

2 −1 −1 0 1 1 0

n

0

=

i

0

= 2 +5 +1 = 8

By Eq. (13.7),

y

CO

2

=

2 −ε

1

−ε

2

8 −2ε

1

y

H

2

=

5 −3ε

1

−ε

2

8 −2ε

1

y

CH

3

OH

=

ε

1

8 −2ε

1

y

CO

=

1 +ε

2

8 −2ε

1

y

H

2

O

=

ε

1

+ε

2

8 −2ε

1

13.7 The equation for G

◦

, appearing just above Eq. (13.18) is:

G

◦

= H

◦

0

−

T

T

0

(H

◦

0

−G

◦

0

) + R

_

T

T

0

C

◦

P

R

dT − RT

_

T

T

0

C

◦

P

R

dT

T

To calculate values of G

◦

, one combines this equation with Eqs. (4.19) and (13.19), and evaluates

parameters. In each case the value of H

◦

0

= H

◦

298

is tabulated in the solution to Pb. 4.21. In

addition, the values of A, B, C, and D are given in the solutions to Pb. 4.22. The required

values of G

◦

0

= G

◦

298

in J mol

−1

are:

(a) −32,900; (f ) −2,919,124; (i) 113,245; (n) 173,100; (r) −39,630; (t) 79,455; (u) 166,365;

(x) 39,430; (y) 83,010

13.8 The relation of K

y

to P and K is given by Eq. (13.28), which may be concisely written:

K

y

=

_

P

P

◦

_

−ν

K

(a) Differentiate this equation with respect to T and combine with Eq. (13.14):

_

∂ K

y

∂T

_

P

=

_

P

P

◦

_

−ν

dK

dT

=

K

y

K

dK

dT

= K

y

d ln K

dT

=

K

y

H

◦

RT

2

Substitute into the given equation for (∂ε

e

/∂T)

P

:

_

∂ε

e

∂T

_

P

=

K

y

RT

2

dε

e

dK

y

H

◦

(b) The derivative of K

y

with respect to P is:

_

∂ K

y

∂ P

_

T

= −ν

_

P

P

◦

_

−ν−1

1

P

◦

K = −νK

_

P

P

◦

_

−ν

_

P

P

◦

_

−1

1

P

◦

=

−νK

y

P

702

Substitute into the given equation for (∂ε

e

/∂ P)

T

:

_

∂ε

e

∂ P

_

T

=

K

y

P

dε

e

dK

y

(−ν)

(c) With K

y

≡

i

(y

i

)

ν

i

, ln K

y

=

i

ν

i

ln y

i

. Differentiation then yields:

1

K

y

dK

y

dε

e

=

i

ν

i

y

i

dy

i

dε

e

(A)

Because y

i

= n

i

/n,

dy

i

dε

e

=

1

n

dn

i

dε

e

−

n

i

n

2

dn

dε

e

=

1

n

_

dn

i

dε

e

− y

i

dn

dε

e

_

But n

i

= n

i

0

+ν

i

ε

e

and n = n

0

+νε

e

Whence,

dn

i

dε

e

= ν

i

and

dn

dε

e

= ν

Therefore,

dy

i

dε

e

=

ν

i

− y

i

ν

n

0

+νε

e

Substitution into Eq. (A) gives

1

K

y

dK

y

dε

e

=

i

ν

i

y

i

_

ν

i

− y

i

ν

n

0

+νε

e

_

=

1

n

0

+νε

e

i

_

ν

2

i

y

i

−ν

i

ν

_

=

1

n

0

+νε

e

m

i =1

_

ν

2

i

y

i

−ν

i

m

k=1

ν

k

_

In this equation, both K

y

and n

0

+νε

e

(= n) are positive. It remains to show that the summation

term is positive. If m = 2, this term becomes

ν

2

1

y

1

−ν

1

(ν

1

+ν

2

) +

ν

2

2

y

2

−ν

2

(ν

1

+ν

2

) =

(y

2

ν

1

− y

1

ν

2

)

2

y

1

y

2

where the expression on the right is obtained by straight-forward algebraic manipulation. One

can proceed by induction to ﬁnd the general result, which is

m

i =1

_

ν

2

i

y

i

−ν

i

m

k=1

ν

k

_

=

m

i

m

k

(y

k

ν

i

− y

i

ν

k

)

2

y

i

y

k

(i < k)

All quantities in the sum are of course positive.

13.9

1

2

N

2

(g) +

3

2

H

2

(g) →NH

3

(g)

For the given reaction, ν = −1, and for the given amounts of reactants, n

0

= 2.

By Eq. (13.5), y

N

2

=

1

2

(1 −ε

e

)

2 −ε

e

y

H

2

=

3

2

(1 −ε

e

)

2 −ε

e

y

NH

3

=

ε

e

2 −ε

e

By Eq. (13.28),

y

NH

3

y

1/2

N

2

y

3/2

H

2

=

ε

e

(2 −ε

e

)

[

1

2

(1 −ε

e

)]

1/2

[

3

2

(1 −ε

e

)]

3/2

= K

P

P

◦

703

Whence,

ε

e

(2 −ε

e

)

(1 −ε

e

)

2

=

_

1

2

_

1/2

_

3

2

_

3/2

K

P

P

◦

= 1.299K

P

P

◦

This may be written: rε

e

2

−2rε

e

+(r −1) = 0

where, r ≡ 1 +1.299K

P

P

◦

The roots of the quadratic are: ε

e

= 1 ±

1

r

1/2

= 1 ±r

−1/2

Because ε

e

< 1, ε

e

= 1 −r

−1/2

, ε

e

= 1 −

_

1 +1.299K

P

P

◦

_

−1/2

13.10 The reactions are written:

Mary:

2NH

3

+3NO →3H

2

O +

5

2

N

2

(A)

Paul:

4NH

3

+6NO →6H

2

O +5N

2

(B)

Peter:

3H

2

O +

5

2

N

2

→2NH

3

+3NO (C)

Each applied Eqs. (13.11b) and (13.25), here written:

ln K = −G

◦

/RT and K = (P

◦

)

−ν

i

(

ˆ

f

i

)

ν

i

For reaction (A), G

◦

A

= 3G

◦

f

H

2

O

−2G

◦

f

NH

3

−3G

◦

f

NO

For Mary’s reaction ν =

1

2

, and:

K

A

= (P

◦

)

−

1

2

ˆ

f

3

f

H

2

O

ˆ

f

5/2

f

N

2

ˆ

f

2

f

NH

3

ˆ

f

3

f

NO

and ln K

A

=

−G

◦

A

RT

For Paul’s reaction ν = 1, and

K

B

= (P

◦

)

−1

ˆ

f

6

f

H

2

O

ˆ

f

5

f

N

2

ˆ

f

4

f

NH

3

ˆ

f

6

f

NO

and ln K

B

=

−2G

◦

A

RT

For Peter’s reaction ν = −

1

2

, and:

K

C

= (P

◦

)

1

2

ˆ

f

2

f

NH

3

ˆ

f

3

f

NO

ˆ

f

3

f

H

2

O

ˆ

f

5/2

f

N

2

and ln K

C

=

G

◦

A

RT

In each case the two equations are combined:

Mary: (P

◦

)

−

1

2

ˆ

f

3

f

H

2

O

ˆ

f

5/2

f

N

2

ˆ

f

2

f

NH

3

ˆ

f

3

f

NO

= exp

−G

◦

A

RT

704

Paul: (P

◦

)

−1

ˆ

f

6

f

H

2

O

ˆ

f

5

f

N

2

ˆ

f

4

f

NH

3

ˆ

f

6

f

NO

=

_

exp

−G

◦

A

RT

_

2

Taking the square root yields Mary’s equation.

Peter: (P

◦

)

1

2

ˆ

f

2

f

NH

3

ˆ

f

3

f

NO

ˆ

f

3

f

H

2

O

ˆ

f

5/2

f

N

2

=

_

exp

−G

◦

A

RT

_

−1

Taking the reciprocal yields Mary’s equation.

13.24 Formation reactions:

1

2

N

2

+

3

2

H

2

→NH

3

(1)

1

2

N

2

+

1

2

O

2

→NO (2)

1

2

N

2

+O

2

→NO

2

(3)

H

2

+

1

2

O

2

→H

2

O (4)

Combine Eq. (3) with Eq. (1) and with Eq. (2) to eliminate N

2

:

NO

2

+

3

2

H

2

→NH

3

+O

2

(5)

NO

2

→

1

2

O

2

+NO (6)

The set now comprises Eqs. (4), (5), and (6); combine Eq. (4) with Eq. (5) to eliminate H

2

:

NO

2

+

3

2

H

2

O →NH

3

+1

3

4

O

2

(7)

Equations (6) and (7) represent a set of independent reactions for which r = 2. Other equivalent sets

of two reactions may be obtained by different combination procedures. By the phase rule,

F = 2 −π + N −r −s = 2 −1 +5 −2 −0 F = 4

13.35 (a) Equation (13.28) here becomes:

y

B

y

A

=

_

P

P

◦

_

0

K = K

Whence,

y

B

1 − y

B

= K(T)

(b) The preceding equation indicates that the equilibrium composition depends on temperature only.

However, application of the phase rule, Eq. (13.36), yields:

F = 2 +2 −1 −1 = 2

This result means in general for single-reaction equilibrium between two species A and B that

two degrees of freedom exist, and that pressure as well as temperature must be speciﬁed to ﬁx the

equilibrium state of the system. However, here, the speciﬁcation that the gases are ideal removes

the pressure dependence, which in the general case appears through the

ˆ

φ

i

s.

13.36 For the isomerization reaction in the gas phase at low pressure, assume ideal gases. Equation (13.28)

then becomes:

y

B

y

A

=

_

P

P

◦

_

0

K = K whence

1 − y

A

y

A

= K(T)

705

Assume that vapor/liquid phase equilibrium can be represented by Raoult’s law, because of the low

pressure and the similarity of the species:

x

A

P

sat

A

(T) = y

A

P and (1 − x

A

)P

sat

B

(T) = (1 − y

A

)P

(a) Application of Eq. (13.36) yields: F = 2 −π + N −r = 2 −2 +2 −1 = 1

(b) Given T, the reaction-equilibriuum equation allows solution for y

A

. The two phase-equilibrium

equations can then be solved for x

A

and P. The equilibrium state therefore depends solely on T.

13.38 (a) For low pressure and a temperature of 500 K, the system is assumed to be a mixture of ideal

gases, for which Eq. (13.28) is appropriate. Therefore,

y

MX

y

OX

=

_

P

P

◦

_

0

K

I

= K

I

y

PX

y

OX

=

_

P

P

◦

_

0

K

II

= K

II

y

EB

y

OX

=

_

P

P

◦

_

0

K

III

= K

III

(b) These equation equations lead to the following set:

y

MX

= K

I

y

OX

(1) y

PX

= K

II

y

OX

(2) y

EB

= K

III

y

OX

(3)

The mole fractions must sum to unity, and therefore:

y

OX

+ K

I

y

OX

+ K

II

y

OX

+ K

III

y

OX

= y

OX

(1 + K

I

+ K

II

+ K

III

) = 1

y

OX

=

1

1 + K

I

+ K

II

+ K

III

(4)

(c) With the assumption that C

◦

P

= 0 and therefore that K

2

= 1, Eqs. (13.20), (13.21), and (13.22)

combine to give:

K = K

0

K

1

= exp

_

−G

◦

298

RT

0

_

exp

_

H

◦

298

RT

0

_

1 −

T

0

T

__

Whence, K = exp

_

_

_

_

H

◦

298

_

1 −

298.15

500

_

−G

◦

298

(8.314)(298.15)

_

¸

¸

_

The data provided lead to the following property changes of reaction and equilibrium constants

at 500 K:

Reaction H

◦

298

G

◦

298

K

I −1,750 −3,300 2.8470

II −1,040 −1,000 1.2637

III 10,920 8,690 0.1778

706

(d) Substitution of numerical values into Eqs. (1), (2), (3), and (4) yields the following values for the

mole fractions:

y

OX

= 0.1891 y

MX

= 0.5383 y

PX

= 0.2390 y

EB

= 0.0336

13.40 For the given ﬂowrates, n

A

0

= 10 and n

B

0

= 15, with n

A

0

the limiting reactant without (II)

n

A

= n

A

0

−ε

I

−ε

II

n

B

= n

B

0

−ε

I

n

C

= ε

I

−ε

II

n

D

= ε

II

n = n

0

−ε

I

−ε

II

Use given values of Y

C

and S

C/D

to ﬁnd ε

I

and ε

II

:

Y

C

=

ε

I

−ε

II

n

A

0

and S

C/D

=

ε

I

−ε

II

ε

II

Solve for ε

I

and ε

II

:

ε

I

=

_

S

C/D

+1

S

C/D

_

n

A

0

Y

C

=

_

2 +1

2

_

×10 ×0.40 = 6

ε

II

=

n

A

0

Y

C

S

C/D

=

10 ×0.40

2

= 2

n

A

= 10 −6 −2 = 2

n

B

= 15 −6 = 9

n

C

= 6 −2 = 4

n

D

= 2 = 2

n = 17

y

A

= 2/17 = 0.1176

y

B

= 9/17 = 0.5295

y

C

= 4/17 = 0.2353

y

D

= 2/17 = 0.1176

= 1

13.42 A compound with large positive G

◦

f

has a disposition to decompose into its constituent elements.

Moreover, large positive G

◦

f

often implies large positive H

◦

f

. Thus, if any decomposition product

is a gas, high pressures can be generated in a closed system owing to temperature increases resulting

from exothermic decomposition.

13.44 By Eq. (13.12), G

◦

≡

i

ν

i

G

◦

i

and from Eq. (6.10), (∂G

◦

i

/∂ P)

T

= V

◦

i

_

∂G

◦

∂ P

◦

_

T

=

i

ν

i

_

∂G

◦

i

∂ P

◦

_

T

=

i

ν

i

V

◦

i

For the ideal-gas standard state, V

◦

i

= RT/P

◦

. Therefore

_

∂G

◦

∂ P

◦

_

T

=

i

ν

i

_

RT

P

◦

_

=

νRT

P

◦

and G

◦

(P

◦

2

) −G

◦

(P

◦

1

) = νRT ln

P

◦

2

P

◦

1

13.47 (a) For isomers at low pressure Raoult’s law should apply:

P = x

A

P

sat

A

+ x

B

P

sat

B

= P

sat

B

+ x

A

(P

sat

A

− P

sat

B

)

For the given reaction with an ideal solution in the liquid phase, Eq. (13.33) becomes:

K

l

=

x

B

x

A

=

1 − x

A

x

A

from which x

A

=

1

K

l

+1

707

The preceding equation now becomes,

P =

_

1 −

1

K

l

+1

_

P

sat

B

+

_

1

K

l

+1

_

P

sat

A

P =

_

K

l

K

l

+1

_

P

sat

B

+

_

1

K

l

+1

_

P

sat

A

(A)

For K

l

= 0 P = P

sat

A

For K

l

= ∞ P = P

sat

B

(b) Given Raoult’s law:

1 = x

A

+ x

B

= y

A

P

P

sat

A

+ y

B

P

P

sat

B

= P

_

y

A

P

sat

A

+

y

B

P

sat

B

_

P =

1

y

A

/P

sat

A

+ y

B

/P

sat

B

=

P

sat

A

P

sat

B

y

A

P

sat

B

+ y

B

P

sat

A

=

P

sat

A

P

sat

B

P

sat

A

+ y

A

(P

sat

B

− P

sat

A

)

For the given reaction with ideal gases in the vapor phase, Eq. (13.28) becomes:

y

B

y

A

= K

v

whence y

A

=

1

K

v

+1

Elimination of y

A

from the preceding equation and reduction gives:

P =

(K

v

+1)P

sat

A

P

sat

B

K

v

P

sat

A

+ P

sat

B

(B)

For K

v

= 0 P = P

sat

A

For K

v

= ∞ P = P

sat

B

(c) Equations (A) and (B) must yield the same P. Therefore

_

K

l

K

l

+1

_

P

sat

B

+

_

1

K

l

+1

_

P

sat

A

=

(K

v

+1)P

sat

A

P

sat

B

K

v

P

sat

A

+ P

sat

B

Some algebra reduces this to:

K

v

K

l

=

P

sat

B

P

sat

A

(d) As mentioned already, the species (isomers) are chemically similar, and the low pressure favors

ideal-gas behavior.

(e) F = N +2 −π −r = 2 +2 −2 −1 = 1 Thus ﬁxing T should sufﬁce.

708

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