Chapter 11 - Section B - Non-Numerical Solutions

11.6 Apply Eq. (11.7):

T
i

_
(nT)
n
i
_
P,T,n
j
= T
_
n
n
i
_
T,P,n
j
= T

P
i

_
(nP)
n
i
_
P,T,n
j
= P
_
n
n
i
_
T,P,n
j
= P
11.7 (a) Let m be the mass of the solution, and dene the partial molar mass by:
m
i

_
m
n
i
_
T,P,n
j
Let M
k
be the molar mass of species k. Then
m =

k
n
k
M
k
= n
i
M
i
+

j
n
j
M
j
( j = i )
and
_
m
n
i
_
T,P,n
j
=
_
(n
i
M
i
)
n
i
_
T,P,n
j
= M
i
Whence, m
i
= M
i
(b) Dene a partial specic property as:

M
i

_
M
t
m
i
_
T,P,m
j
=
_
M
t
n
i
_
T,P,m
j
_
n
i
m
i
_
T,P,m
j
If M
i
is the molar mass of species i ,
n
i
=
m
i
M
i
and
_
n
i
m
i
_
T,P,m
j
=
1
M
i
Since constant m
j
implies constant n
j
, the initial equation may be written:

M
i
=

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

V
1
= V + x
2
dV
dx
1
and

V
2
= V x
1
dV
dx
1
Because V =
1
then
dV
dx
1
=
1

2
d
dx
1
Whence,

V
1
=
1

x
2

2
d
dx
1
=
1

_
1
x
2

d
dx
1
_

V
2
=
1

+
x
1

2
d
dx
1
=
1

_
1 +
x
1

d
dx
1
_
585
11.9 For application of Eq. (11.7) all mole fractions must be eliminated from the given equation by the
relation x
i
= n
i
/n:
nM = n
1
M
1
+n
2
M
2
+n
3
M
3
+
n
1
n
2
n
3
n
2
C
For

M
1
,
_
(nM)
n
1
_
T,P,n
2
,n
3
= M
1
+n
2
n
3
C
_
1
n
2

2n
1
n
3
_
n
n
1
_
T,P,n
2
,n
3
_
Because n = n
1
+n
2
+n
3
,
_
n
n
1
_
T,P,n
2
,n
3
= 1
Whence,

M
1
= M
1
+
n
2
n
3
n
2
_
1 2
n
1
n
_
C and

M
1
= M
1
+ x
2
x
3
[1 2x
1
]C
Similarly,

M
2
= M
2
+ x
1
x
3
[1 2x
2
]C and

M
3
= M
3
+ x
1
x
2
[1 2x
3
]C
One can readily show that application of Eq. (11.11) regenerates the original equation for M. The
innite dilution values are given by:

i
= M
i
+ x
j
x
k
C ( j, k = i )
Here x
j
and x
k
are mole fractions on an i -free basis.
11.10 With the given equation and the Daltons-law requirement that P =

i
p
i
, then:
P =
RT
V

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

i
y
i
Z
i
.
11.11 The general principle is simple enough:
Given equations that represent partial properties

M
i
,

M
R
i
, or

M
E
i
as functions of com-
position, one may combine them by the summability relation to yield a mixture property.
Application of the dening (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 x
1
by x
1
= n
1
/(n
1
+n
2
):
nH = 600(n
1
+n
2
) 180 n
1
20
n
3
1
(n
1
+n
2
)
2
Form the partial derivative of nH with respect to n
1
at constant n
2
:

H
1
= 600 180 20
_
3n
2
1
(n
1
+n
2
)
2

2n
3
1
(n
1
+n
2
)
3
_
= 420 60
n
2
1
(n
1
+n
2
)
2
+40
n
3
1
(n
1
+n
2
)
3
Whence,

H
1
= 420 60 x
2
1
+40 x
3
1
Form the partial derivative of nH with respect to n
2
at constant n
1
:

H
2
= 600 +20
2 n
3
1
(n
1
+n
2
)
3
or

H
2
= 600 +40 x
3
1
586
(b) In accord with Eq. (11.11),
H = x
1
(420 60 x
2
1
+40 x
3
1
) +(1 x
2
)(600 +40 x
3
1
)
Whence, H = 600 180 x
1
20 x
3
1
(c) Write Eq. (11.14) for a binary system and divide by dx
1
: x
1
d

H
1
dx
1
+ x
2
d

H
2
dx
1
= 0
Differentiate the the boxed equations of part (a):
d

H
1
dx
1
= 120 x
1
+120 x
2
1
= 120 x
1
x
2
and
d

H
2
dx
1
= 120 x
2
1
Multiply each derivative by the appropriate mole fraction and add:
120 x
2
1
x
2
+120x
2
1
x
2
= 0
(d) Substitute x
1
= 1 and x
2
= 0 in the rst derivative expression of part (c) and substitute x
1
= 0
in the second derivative expression of part (c). The results are:
_
d

H
1
dx
1
_
x
1
=1
=
_
d

H
2
dx
1
_
x
1
=0
= 0
(e)
11.13 (a) Substitute x
2
= 1 x
1
in the given equation for V and reduce:
V = 70 +58 x
1
x
2
1
7 x
3
1
Apply Eqs. (11.15) and (11.16) to nd expressions for

V
1
and

V
2
. First,
dV
dx
1
= 58 2 x
1
21 x
2
1
Then,

V
1
= 128 2 x
1
20 x
2
1
+14 x
3
1
and

V
2
= 70 + x
2
1
+14 x
3
1
587
(b) In accord with Eq. (11.11),
V = x
1
(128 2 x
1
20 x
2
1
+14 x
3
1
) +(1 x
1
)(70 + x
2
1
+14 x
3
1
)
Whence, V = 70 +58 x
1
x
2
1
7 x
3
1
which is the rst equation developed in part (a).
(c) Write Eq. (11.14) for a binary system and divide by dx
1
: x
1
d

V
1
dx
1
+ x
2
d

V
2
dx
1
= 0
Differentiate the the boxed equations of part (a):
d

V
1
dx
1
= 2 40 x
1
+42 x
2
1
and
d

V
2
dx
1
= 2 x
1
+42 x
2
1
Multiply each derivative by the appropriate mole fraction and add:
x
1
(2 40 x
1
+42 x
2
1
) +(1 x
1
)(2 x
1
+42 x
2
1
) = 0
The validity of this equation is readily conrmed.
(d) Substitute x
1
= 1 in the rst derivative expression of part (c) and substitute x
1
= 0 in the second
derivative expression of part (c). The results are:
_
d

V
1
dx
1
_
x
1
=1
=
_
d

V
2
dx
1
_
x
1
=0
= 0
(e)
11.14 By Eqs. (11.15) and (11.16):

H
1
= H + x
2
d H
dx
1
and

H
2
= H x
1
d H
dx
1
588
Given that: H = x
1
(a
1
+b
1
x
1
) + x
2
(a
2
+b
2
x
2
)
Then, after simplication,
d H
dx
1
= a
1
+2b
1
x
1
(a
2
+2b
2
x
2
)
Combining these equations gives after reduction:

H
1
= a
1
+b
1
x
1
+ x
2
(x
1
b
1
x
2
b
2
) and

H
2
= a
2
+b
2
x
2
x
1
(x
1
b
1
x
2
b
2
)
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:
x
1
d

H
1
dx
1
+ x
2
d

H
2
dx
1
= 0
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:
_
x
y
_
z
=
_
x
y
_
w
+
_
x
w
_
y
_
w
y
_
z
_
(nM)
n
i
_
T,P,n
j
=
_
(nM)
n
i
_
T,V,n
j
+
_
(nM)
V
_
T,n
_
V
n
i
_
T,P,n
j
Whence,

M
i
=

M
i
+n
_
M
V
_
T,n
_
V
n
i
_
T,P,n
j
or

M
i
=

M
i
n
_
M
V
_
T,n
_
V
n
i
_
T,P,n
j
By denition,

V
i

_
(nV)
n
i
_
T,P,n
j
= n
_
V
n
i
_
T,P,n
j
+ V or n
_
V
n
i
_
T,P,n
j
=

V
i
V
Therefore,

M
i
=

M
i
+(V

V
i
)
_
M
V
_
T,x
11.20 Equation (11.55) 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. (11.53) and (11.54) are:
_
ln

i
P
_
T,x
=

V
R
i
RT
and
_
ln

i
T
_
P,x
=

H
R
i
RT
2
The summability and Gibbs/Duhem equations take on the following forms:
G
R
RT
=

i
x
i
ln

i
and

i
x
i
d ln

i
= 0 (const T, P)
589
11.26 For a pressure low enough that Z and ln are given approximately by Eqs. (3.37) and (11.35):
Z = 1 +
BP
RT
and ln =
BP
RT
then: ln Z 1
11.28 (a) Because Eq. (11.92) 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
=
G
E
RT
+ x
2
d(G
E
/RT)
dx
1
ln
2
=
G
E
RT
x
1
d(G
E
/RT)
dx
1
Substitute x
2
= 1 x
1
in the given equaiton for G
E
/RT and reduce:
G
E
RT
= 1.8 x
1
+ x
2
1
+0.8 x
3
1
whence
d(G
E
/RT)
dx
1
= 1.8 +2 x
1
+2.4 x
2
1
Then, ln
1
= 1.8 +2 x
1
+1.4 x
2
1
1.6 x
3
1
and ln
2
= x
2
1
1.6 x
3
1
(b) In accord with Eq. (11.11),
G
E
RT
= x
1
ln
1
+ x
2
ln
2
= x
1
(1.8 +2 x
1
+1.4 x
2
1
1.6 x
3
1
) +(1 x
1
)(x
2
1
1.6 x
3
1
)
Whence,
G
E
RT
= 1.8 x
1
+ x
2
1
+0.8 x
3
1
which is the rst equation developed in part (a).
(c) Write Eq. (11.14) for a binary system with

M
i
= ln
i
and divide by dx
1
:
x
1
d ln
1
dx
1
+ x
2
d ln
2
dx
1
= 0
Differentiate the the boxed equations of part (a):
d ln
1
dx
1
= 2 +2.8 x
1
4.8 x
2
1
and
d ln
2
dx
1
= 2 x
1
4.8 x
2
1
Multiply each derivative by the appropriate mole fraction and add:
x
1
(2 +2.8 x
1
4.8 x
2
1
) +(1 x
1
)(2 x
1
4.8 x
2
1
) = 0
The validity of this equation is readily conrmed.
(d) Substitute x
1
= 1 in the rst derivative expression of part (c) and substitute x
1
= 0 in the second
derivative expression of part (c). The results are:
_
d ln
1
dx
1
_
x
1
=1
=
_
d ln
2
dx
1
_
x
1
=0
= 0
590
(e)
11.29 Combine denitions of the activity coefcient and the fugacity coefcients:

f
i
/x
i
P
f
i
/P
or
i
=

i
Note: See Eq. (14.54).
11.30 For C
E
P
= const., the following equations are readily developed from those given in the last column
of Table 11.1 (page 404):
H
E
= C
E
P
T and S
E
=
_
G
E
T
_
P,x
= C
E
P
T
T
Working equations are then:
S
E
1
=
H
E
1
G
E
1
T
1
and S
E
2
= S
E
1
+C
E
P
T
T
H
E
2
= H
E
1
+C
E
P
T and G
E
2
= H
E
2
T
2
S
E
2
For T
1
= 298.15, T
2
= 328.15, T = 313.15 and T = 30, results for all parts of the problem are
given in the following table:
I. II. For C
E
P
= 0
G
E
1
H
E
1
S
E
1
C
E
P
S
E
2
H
E
2
G
E
2
S
E
2
H
E
2
G
E
2
(a) 622 1920 4.354 4.2 3.951 1794 497.4 4.354 1920 491.4
(b) 1095 1595 1.677 3.3 1.993 1694 1039.9 1.677 1595 1044.7
(c) 407 984 1.935 2.7 1.677 903 352.8 1.935 984 348.9
(d) 632 208 2.817 23.0 0.614 482 683.5 2.817 208 716.5
(e) 1445 605 2.817 11.0 1.764 935 1513.7 2.817 605 1529.5
(f) 734 416 3.857 11.0 2.803 86 833.9 3.857 416 849.7
(g) 759 1465 2.368 8.0 1.602 1225 699.5 2.368 1465 688.0
591
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
RT
= A
12
n
1
n
2
n
+ A
13
n
1
n
3
n
+ A
23
n
2
n
3
n
Differentiation with respect to n
1
in accord with Eq. (11.92) yields [(n/n
1
)
n
2
,n
3
= 1]:
ln
1
= A
12
n
2
_
1
n

n
1
n
2
_
+ A
13
n
3
_
1
n

n
1
n
2
_
A
23
n
2
n
3
n
2
= A
12
x
2
(1 x
1
) + A
13
x
3
(1 x
1
) A
23
x
2
x
3
Similarly, ln
2
= A
12
x
1
(1 x
2
) A
13
x
1
x
3
+ A
23
x
3
(1 x
2
)
ln
3
= A
12
x
1
x
2
+ A
13
x
1
(1 x
3
) + A
23
x
2
(1 x
3
)
(b) Each ln
i
is multiplied by x
i
, and the terms are summed. Consider the rst terms on the right of
each expression for ln
i
. Multiplying each of these terms by the appropriate x
i
and adding gives:
A
12
(x
1
x
2
x
2
1
x
2
+ x
2
x
1
x
2
2
x
1
x
1
x
2
x
3
) = A
12
x
1
x
2
(1 x
1
+1 x
2
x
3
)
= A
12
x
1
x
2
[2 (x
1
+ x
2
+ x
3
)] = A
12
x
1
x
2
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.
(c) For innite dilution of species 1, x
1
= 0: ln
1
(x
1
= 0) = A
12
x
2
+ A
13
x
3
A
23
x
2
x
3
For pure species 1, x
1
= 1: ln
1
(x
1
= 1) = 0
For innite dilution of species 2, x
2
= 0: ln
1
(x
2
= 0) = A
13
x
2
3
For innite dilution of species 3, x
3
= 0: ln
1
(x
3
= 0) = A
12
x
2
2
11.35 By Eq. (11.84), written with M G and with x replaced by y: G
E
= G
R

i
y
i
G
R
i
Equations (11.31) and (11.35) together give G
R
i
= B
i i
P. Then for a binary mixture:
G
E
= BP y
1
B
11
P y
2
B
22
P or G
E
= P(B y
1
B
11
y
2
B
22
)
Combine this equation with the last equation on Pg. 394: G
E
=
12
Py
1
y
2
From the last column of Table 11.1 (page 404): S
E
=
_
G
E
T
_
P,x
Because
12
is a function of T only: S
E
=
d
12
dT
Py
1
y
2
By the denition of G
E
, H
E
= G
E
+ T S
E
; whence, H
E
=
_

12
T
d
12
dT
_
Py
1
y
2
Again from the last column of Table 11.1: C
E
P
=
_
H
E
T
_
P,x
This equation and the preceding one lead directly to: C
E
P
= T
d
2

12
dT
2
Py
1
y
2
592