Chapter 11 - Section B - Non-Numerical Solutions

11.6 Apply Eq. (11.7):






n
(nT )

=T
=T
Ti
n i P,T,n j
n i T,P,n j




(n P)
n

Pi
=P
=P
n i P,T,n j
n i T,P,n j

11.7 (a) Let m be the mass of the solution, and define the partial molar mass by: m i

m
n i

T,P,n j

Let Mk be the molar mass of species k. Then

m=

 nk Mk = ni Mi +  n j M j
k

and

m
n i

T,P,n j

( j = i)

(n i Mi )
n i

Whence,

= Mi

m i = Mi

T,P,n j

(b) Define a partial specific property as: M i

If Mi is the molar mass of species i,

M t
m i

mi
Mi

ni =




M t
n i
=
n i T,P,m j m i T,P,m j
T,P,m j


n i
1
=
and
m i T,P,m j
Mi

Because constant m j implies constant n j , the initial equation may be written:

11.8 By Eqs. (10.15) and (10.16),

Because

With

V = 1

then

dV
V1 = V + x2
d x1
dV
1 d
= 2
d x1
d x1

dV
V2 = V x1
d x1

and
whence

1
1
x2 d
V1 = 2
=

d x1

x2 d
d x1



1
d

x
2
2
d x1

1
1
x1 d
V2 = + 2
=

d x1

1+

x1 d
d x1



d
1

+
x
1
2
d x1

= a0 + a1 x1 + a2 x12

and

M i
M i =
Mi

d
= a1 + 2a2 x1
d x1

1
V1 = 2 [a0 a1 + 2(a1 a2 )x1 + 3a2 x12 ]

and

these become:

1
V2 = 2 (a0 + 2a1 x1 + 3a2 x12 )

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11.9 For application of Eq. (11.7) all mole fractions must be eliminated from the given equation by the
relation xi = n i /n:
n1n2n3
C
n M = n 1 M1 + n 2 M2 + n 3 M3 +
n2







(n
M)
n
2n
1
1
For M 1 ,
= M1 + n 2 n 3 C
3
n 1 T,P,n 2 ,n 3
n2
n
n 1 T,P,n 2 ,n 3


Because n = n 1 + n 2 + n 3 ,

n
n 1

=1

T,P,n 2 ,n 3

Whence,

n1 
n2n3 
C
M 1 = M1 + 2 1 2
n
n

and

M 1 = M1 + x2 x3 [1 2x1 ]C

Similarly,

M 2 = M2 + x1 x3 [1 2x2 ]C

and

M 3 = M3 + x1 x2 [1 2x3 ]C

One can readily show that application of Eq. (11.11) regenerates the original equation for M. The
infinite dilution values are given by:
M i = Mi + x j xk C

( j, k = i)

Here x j and xk are mole fractions on an i-free basis.

11.10 With the given equation and the Daltons-law requirement that P =
P=

RT
V

 yi Z i

pi , then:

For the mixture, P = Z RT /V . These two equations combine to give Z =

11.11 The general principle is simple enough:

yi Z i .

Given equations that represent partial properties M i , M iR , or M iE as functions of composition, one may combine them by the summability relation to yield a mixture property.
Application of the defining (or equivalent) equations for partial properties then regenerates
the given equations if and only if the given equations obey the Gibbs/Duhen equation.
11.12 (a) Multiply Eq. (A) of Ex. 11.4 by n (= n 1 + n 2 ) and eliminate x1 by x1 = n 1 /(n 1 + n 2 ):
n H = 600(n 1 + n 2 ) 180 n 1 20

n 31
(n 1 + n 2 )2

Form the partial derivative of n H with respect to n 1 at constant n 2 :




n 21
3n 21
2n 31
n 31

H1 = 600 180 20
=
420

60

+
40
(n 1 + n 2 )2 (n 1 + n 2 )3
(n 1 + n 2 )2
(n 1 + n 2 )3
H 1 = 420 60 x12 + 40 x13

Whence,

Form the partial derivative of n H with respect to n 2 at constant n 1 :

H 2 = 600 + 20

2 n 31
(n 1 + n 2 )3

or

H 2 = 600 + 40 x13

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(b) In accord with Eq. (11.11),

H = x1 (420 60 x12 + 40 x13 ) + (1 x2 )(600 + 40 x13 )
H = 600 180 x1 20 x13

Whence,

(c) Write Eq. (11.14) for a binary system and divide by d x1 : x1

d H 1
d H 2
+ x2
=0
d x1
d x1

Differentiate the the boxed equations of part (a):

d H 1
= 120 x1 + 120 x12 = 120 x1 x2
d x1

and

d H 2
= 120 x12
d x1

Multiply each derivative by the appropriate mole fraction and add:

120 x12 x2 + 120x12 x2 = 0
(d) Substitute x1 = 1 and x2 = 0 in the first derivative expression of part (c) and substitute x1 = 0
in the second derivative expression of part (c). The results are:


 

d H2
d H 1
=
=0
d x1 x1 =1
d x1 x1 =0

(e)

11.13 (a) Substitute x2 = 1 x1 in the given equation for V and reduce:

V = 70 + 58 x1 x12 7 x13
Apply Eqs. (11.15) and (11.16) to find expressions for V1 and V2 . First,
dV
= 58 2 x1 21 x12
d x1
Then,

V1 = 128 2 x1 20 x12 + 14 x13

and

V2 = 70 + x12 + 14 x13

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(b) In accord with Eq. (11.11),

V = x1 (128 2 x1 20 x12 + 14 x13 ) + (1 x1 )(70 + x12 + 14 x13 )
V = 70 + 58 x1 x12 7 x13

Whence,

which is the first equation developed in part (a).

(c) Write Eq. (11.14) for a binary system and divide by d x1 : x1

d V1
d V2
+ x2
=0
d x1
d x1

Differentiate the the boxed equations of part (a):

d V1
= 2 40 x1 + 42 x12
d x1

d V2
= 2 x1 + 42 x12
d x1

and

Multiply each derivative by the appropriate mole fraction and add:

x1 (2 40 x1 + 42 x12 ) + (1 x1 )(2 x1 + 42 x12 ) = 0
The validity of this equation is readily confirmed.
(d) Substitute x1 = 1 in the first derivative expression of part (c) and substitute x1 = 0 in the second
derivative expression of part (c). The results are:
 
 
d V2
d V1
=
=0
d x1 x1 =1
d x1 x1 =0
(e)

11.14 By Eqs. (11.15) and (11.16):

dH
H 1 = H + x2
d x1

and

dH
H 2 = H x1
d x1

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Given that:

H = x1 (a1 + b1 x1 ) + x2 (a2 + b2 x2 )
dH
= a1 + 2b1 x1 (a2 + 2b2 x2 )
d x1

Then, after simplification,

Combining these equations gives after reduction:

H 1 = a1 + b1 x1 + x2 (x1 b1 x2 b2 )

and

H 2 = a2 + b2 x2 x1 (x1 b1 x2 b2 )

These clearly are not the same as the suggested expressions, which are therefore not correct. Note
that application of the summability equation to the derived partial-property expressions reproduces
the original equation for H . Note further that differentiation of these same expressions yields results
that satisfy the Gibbs/Duhem equation, Eq. (11.14), written:
x1

d H 1
d H 2
+ x2
=0
d x1
d x1

The suggested expresions do not obey this equation, further evidence that they cannot be valid.
11.15 Apply the following general equation of differential calculus:
 

 

 
w
x
x
x
=
+
y z
y w
w y y z
 









(n M)
(n M)
(n M)
V
=
+
n i T,P,n j
n i T,V,n j
V
T,n n i T,P,n j
Whence,
M
M i = M i + n
V


T,n

V
n i

or

T,P,n j

M
M i = M i n
V


T,n

V
n i

T,P,n j

By definition,

(nV )
Vi
n i

T,P,n j

V
=n
n i


+V

V
n
n i


or

T,P,n j

= Vi V

T,P,n j



M
M i = M i + (V Vi )
V T,x

Therefore,

11.20 Equation (11.59) demonstrates that ln i is a partial property with respect to G R /RT . Thus ln i =
G i /RT . The partial-property analogs of Eqs. (11.57) and (11.58) are:

ln i
P

T,x

V R
= i
RT

and

ln i
T

P,x

H iR
RT 2

The summability and Gibbs/Duhem equations take on the following forms:

GR
=
RT

 xi ln i

i xi d ln i = 0

and

(const T, P)

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11.26 For a pressure low enough that Z and ln are given approximately by Eqs. (3.38) and (11.36):
Z =1+

BP
RT

and

then:

ln =

BP
RT

ln Z 1

11.28 (a) Because Eq. (11.96) shows that ln i is a partial property with respect to G E/RT , Eqs. (11.15)
and (11.16) may be written for M G E/RT :
ln 1 =

d(G E/RT )
GE
+ x2
RT
d x1

ln 2 =

d(G E/RT )
GE
x1
RT
d x1

Substitute x2 = 1 x1 in the given equaiton for G E/RT and reduce:

GE
= 1.8 x1 + x12 + 0.8 x13
RT
Then,

d(G E/RT )
= 1.8 + 2 x1 + 2.4 x12
d x1

whence

ln 1 = 1.8 + 2 x1 + 1.4 x12 1.6 x13

ln 2 = x12 1.6 x13

and

(b) In accord with Eq. (11.11),

GE
= x1 ln 1 + x2 ln 2 = x1 (1.8 + 2 x1 + 1.4 x12 1.6 x13 ) + (1 x1 )(x12 1.6 x13 )
RT
GE
= 1.8 x1 + x12 + 0.8 x13
RT

Whence,

which is the first equation developed in part (a).

(c) Write Eq. (11.14) for a binary system with M i = ln i and divide by d x1 :
x1

d ln 1
d ln 2
+ x2
=0
d x1
d x1

Differentiate the the boxed equations of part (a):

d ln 1
= 2 + 2.8 x1 4.8 x12
d x1

d ln 2
= 2 x1 4.8 x12
d x1

and

Multiply each derivative by the appropriate mole fraction and add:

x1 (2 + 2.8 x1 4.8 x12 ) + (1 x1 )(2 x1 4.8 x12 ) = 0
The validity of this equation is readily confirmed.
(d) Substitute x1 = 1 in the first derivative expression of part (c) and substitute x1 = 0 in the second
derivative expression of part (c). The results are:


d ln 1
d x1

x1 =1

d ln 2
d x1

=0

x1 =0

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(e)

11.29 Combine definitions of the activity coefficient and the fugacity coefficients:
i

fi /xi P
f i /P

or

i =

i
i

Note: See Eq. (14.54).

11.30 For C PE = const., the following equations are readily developed from those given in the last column
of Table 11.1 (page 415):


T
G E
E
E
E
= C PE
H = C P T
and
S = 
T P,x
T 
Working equations are then:
H1E G 1E
T1

and

S2E = S1E + C PE

H2E = H1E + C PE T

and

G 2E = H2E T2 S2E

S1E =

T
T 

For T1 = 298.15, T2 = 328.15, T  = 313.15 and T = 30, results for all parts of the problem are
given in the following table:
II. For C PE = 0

I.

(a)
(b)
(c)
(d)
(e)
(f)
(g)

G 1E

H1E

S1E

C PE

S2E

H2E

G 2E

S2E

H2E

G 2E

622
1095
407
632
1445
734
759

1920
1595
984
208
605
416
1465

4.354
1.677
1.935
2.817
2.817
3.857
2.368

4.2
3.3
2.7
23.0
11.0
11.0
8.0

3.951
1.993
1.677
0.614
1.764
2.803
1.602

1794
1694
903
482
935
86
1225

497.4
1039.9
352.8
683.5
1513.7
833.9
699.5

4.354
1.677
1.935
2.817
2.817
3.857
2.368

1920
1595
984
208
605
416
1465

491.4
1044.7
348.9
716.5
1529.5
849.7
688.0

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11.31 (a) Multiply the given equation by n (= n 1 + n 2 ), and convert remaining mole fractions to ratios of
mole numbers:
nG E
n1n2
n1n3
n2n3
= A12
+ A13
+ A23
RT
n
n
n
Differentiation with respect to n 1 in accord with Eq. (11.96) yields [(n/n 1 )n 2 ,n 3 = 1]:




1 n1
n2n3
1 n1
ln 1 = A12 n 2
2 + A13 n 3
2 A23 2
n n
n n
n
= A12 x2 (1 x1 ) + A13 x3 (1 x1 ) A23 x2 x3

Similarly,

ln 2 = A12 x1 (1 x2 ) A13 x1 x3 + A23 x3 (1 x2 )

ln 3 = A12 x1 x2 + A13 x1 (1 x3 ) + A23 x2 (1 x3 )

(b) Each ln i is multiplied by xi , and the terms are summed. Consider the first terms on the right of
each expression for ln i . Multiplying each of these terms by the appropriate xi and adding gives:
A12 (x1 x2 x12 x2 + x2 x1 x22 x1 x1 x2 x3 ) = A12 x1 x2 (1 x1 + 1 x2 x3 )
= A12 x1 x2 [2 (x1 + x2 + x3 )] = A12 x1 x2
An analogous result is obtained for the second and third terms on the right, and adding them
yields the given equation for G E/RT .
x1 = 0:

ln 1 (x1 = 0) = A12 x2 + A13 x3 A23 x2 x3

For pure species 1,

x1 = 1:

ln 1 (x1 = 1) = 0

For infinite dilution of species 2,

x2 = 0:

ln 1 (x2 = 0) = A13 x32

For infinite dilution of species 3,

x3 = 0:

ln 1 (x3 = 0) = A12 x22

(c) For infinite dilution of species 1,

GE = GR

11.35 By Eq. (11.87), written with M G and with x replaced by y:

i yi G iR

Equations (11.33) and (11.36) together give G iR = Bii P. Then for a binary mixture:
G E = B P y1 B11 P y2 B22 P

G E = P(B y1 B11 y2 B22 )

or

G E = 12 P y1 y2

Combine this equation with the last equation on Pg. 402:

G E
From the last column of Table 11.1 (page 415): S =
T


Because 12 is a function of T only:

SE =

d12
H = 12 T
dT
E

By the definition of G , H = G + T S ; whence,

Again from the last column of Table 11.1:

P,x

d12
P y1 y2
dT

C PE

This equation and the preceding one lead directly to:

HE
T

P y1 y2

P,x

C PE = T

d 2 12
P y1 y2
dT 2

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11.41 From Eq. (11.95):

(G E /RT )
T

H E
=
RT 2

To an excellent approximation, write:

From the given data:

(G E /T )
T

H E
(G E /T )
2
T
Tmean

or

(G E /T )
T

H E
T2

(G E /T )
785/323 805/298
0.271
=
=
= 0.01084
T
323 298
25
1060
H E
=
= 0.01082
2
Tmean
3132

and

The data are evidently thermodynamically consistent.

11.42 By Eq. (11.14), the Gibbs/Duhem equation,
Given that

M 1 = M1 + Ax2

and

x1

d M 1
d M 2
+ x2
=0
d x1
d x1

M 2 = M2 + Ax1

then

d M 1
= A
d x1

and

d M 2
=A
d x1

d M 2
d M 1
+ x2
= x1 A + x2 A = A(x2 x1 ) = 0
d x1
d x1
The given expressions cannot be correct.

Then

11.45 (a) For

x1

M E = Ax12 x22

find

M 1E = Ax1 x22 (2 3x1 )

and

Note that at both x1 = 0 (x2 = 1) and x1 = 1 (x2 = 0),

In particular,

M 2E = Ax12 x2 (2 3x2 )

M 1E = M 2E = 0

( M 1E ) = ( M 2E ) = 0

Although M E has the same sign over the whole composition range, both M 1E and M 2E change
sign, which is unusual behavior. Find also that
d M 2E
d M 1E
= 2Ax2 (1 6x1 x2 ) and
= 2Ax1 (1 6x1 x2 )
d x1
d x1
The two slopes are thus of opposite sign, as required; they also change sign, which is unusual.
d M 2E
d M 1E
For x1 = 0
= 2A and
=0
d x1
d x1
For
(b) For

x1 = 1

d M 1E
=0
d x1

and

d M 2E
= 2A
d x1

M E = A sin( x1 ) find:
M 1E = A sin( x1 ) + A x2 cos( x1 )

and

M 2E = A sin( x1 ) A x1 cos( x1 )

d M 1E
d M 2E
= A 2 x2 sin( x1 ) and
= A 2 x1 sin( x1 )
d x1
d x1
The two slopes are thus of opposite sign, as required. But note the following, which is unusual:
For

x1 = 0

and

x1 = 1

d M 1E
=0
d x1

and

d M 2E
=0
d x1

PLOTS OF THE FUNCTIONS ARE SHOWN ON THE FOLLOWING PAGE.

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Pb. 11.45 (a)

10

A . xi

MEi

MEbar2i

0 .. 100

2.

xi

A . xi . xi . 1

xi

MEbar1i

xi . 2

3. 1

.01 . i

.00001

A . xi . 1

xi

3 . xi

xi

2
1.5
MEi
MEbar1

1
i

MEbar2i

0.5
0
0.5

Pb. 11.45 (b)

MEi

0.2

0.4

A . sin

0.6

xi

.x

0.8

(pi prints as bf p)

MEbar1i

A . sin

.x

A.p . 1

MEbar2i

A . sin

.x

A . p . xi . cos

i
i

xi . cos
p

.x

.x

40
30
MEi
MEbar1

20
i

MEbar2i

10
0
10

0.2

0.4

xi

0.6

0.8

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(n M)
M i =
n i

M
= M +n
n i
T,P,n j
  M 
dM =
d xk
xk T,P,x j
k

11.46 By Eq. (11.7),

At constant T and P,

T,P,n j

Divide by dn i with restriction to constant n j ( j = i):



M
n i

T,P,n j

1
n

M
xi

M i = M +

xk

1
=
xk
n k=i
=

  M 

T,P,n j

nk
xk =
n

With

M
n i

xk
n i

M
xk

T,P,x j

nj

(k = i)
(k = i)



M
1
+ (1 xi )
n
xi T,P,x j
M
xk

n
1

i
n n2

1
xk
n k

T,P,x j

xk
n i

n
k

n2

T,P,x j

M
xi

nj

T,P,x j

xk

M
xk

T,P,x j

T,P,x j

For species 1 of a binary mixture (all derivatives at constant T and P):

M 1 = M +

M
x1

x2

x1

M
x1

x2

x2

M
x2

x1

= M + x2



M
x1

x2

M
x2

 
x1

Because x1 + x2 = 1, the partial derivatives in this equation are physically unrealistic; however, they
do have mathematical significance. Because M = M(x1 , x2 ), we can quite properly write:




M
M
dM =
d x1 +
d x2
x 1 x2
x 2 x1
Division by d x1 yields:
dM
=
d x1

M
x1

x2

M
x2

x1

d x2
=
d x1

M
x1

x2

M
x2

x1

wherein the physical constraint on the mole fractions is recognized. Therefore

dM
M 1 = M + x2
d x1
The expression for M 2 is found similarly.
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11.47 (a) Apply Eq. (11.7) to species 1:


(n M E )
E

M1 =
n 1
n2

Multiply the given equation by n and eliminate the mole fractions in favor of mole numbers:


1
1
E
n M = An 1 n 2
+
n 1 + Bn 2 n 2 + Bn 1
M 1E = An 2



1
1
+
n 1 + Bn 2 n 2 + Bn 1

+ n1

1
B

(n 1 + Bn 2 )2 (n 2 + Bn 1 )2



Conversion back to mole fractions yields:





1
1
1
B
E

+
+
M1 = Ax2
x1
x1 + Bx2
x2 + Bx1
(x1 + Bx2 )2 (x2 + Bx1 )2
The first term in the first parentheses is combined with the first term in the second parentheses
and the second terms are similarly combined:





1
x1
1
Bx1
E

M1 = Ax2
1
+
1
x1 + Bx2
x1 + Bx2
x2 + Bx1
x2 + Bx1
Reduction yields:
M 1E = Ax22

1
B
+
(x1 + Bx2 )2 (x2 + Bx1 )2

M 2E = Ax12

B
1
+
2
(x1 + Bx2 )
(x2 + Bx1 )2

Similarly,

(b) The excess partial properties should obey the Gibbs/Duhem equation, Eq. (11.14), when written
for excess properties in a binary system at constant T and P:
x1

d M 1E
d M 2E
+ x2
=0
d x1
d x1

If the answers to part (a) are mathematically correct, this is inevitable, because they were derived
from a proper expression for M E . Furthermore, for each partial property M iE , its value and
derivative with respect to xi become zero at xi = 1.




1
1
E
E

(c)
( M1 ) = A
+1
( M2 ) = A 1 +
B
B
11.48 By Eqs. (11.15) and (11.16), written for excess properties, find:
d2 M E
d M 1E
= x2
d x1
d x12

d2 M E
d M 2E
= x1
d x1
d x12

At x1 = 1, d M 1E /d x1 = 0, and by continuity can only increase or decrease for x1 < 1. Therefore the
sign of d M 1E /d x1 is the same as the sign of d 2 M E /d x12 . Similarly, at x1 = 0, d M 2E /d x1 = 0, and by
the same argument the sign of d M 2E /d x1 is of opposite sign as the sign of d 2 M E /d x12 .
689
PROPRIETARY MATERIAL. 2005 The McGraw-Hill Companies, Inc. Limited distribution permitted only to teachers
and educators for course preparation. If you are a student using this Manual, you are using it without permission.

11.49 The claim is not in general valid.

1

id

i xi Vi

V
T

V id =

xi Vi

xi

Vi
T

i xi Vi

xi Vi i

The claim is valid only if all the Vi are equal.

690
PROPRIETARY MATERIAL. 2005 The McGraw-Hill Companies, Inc. Limited distribution permitted only to teachers
and educators for course preparation. If you are a student using this Manual, you are using it without permission.