Chapter 12 - Section B - Non-Numerical Solutions

12.2 Equation (12.1) may be written: y

i
P = x
i

i
P
sat
i
.
Summing for i = 1, 2 gives: P = x
1

1
P
sat
1
+ x
2

2
P
sat
2
.
Differentiate at constant T:
d P
dx
1
= P
sat
1
_
x
1
d
1
dx
1
+
1
_
+ P
sat
2
_
x
2
d
2
dx
1

2
_
Apply this equation to the limiting conditions:
For x
1
= 0 : x
2
= 1
1
=

1

2
= 1
d
2
dx
1
= 0
For x
1
= 1 : x
2
= 0
1
= 1
2
=

2
d
1
dx
1
= 0
Then,
_
d P
dx
1
_
x
1
=0
= P
sat
1

1
P
sat
2
or
_
d P
dx
1
_
x
1
=0
+ P
sat
2
= P
sat
1

1
_
d P
dx
1
_
x
1
=1
= P
sat
1
P
sat
2

2
or
_
d P
dx
1
_
x
1
=1
P
sat
1
= P
sat
2

2
Since both P
sat
i
and

i
are always positive denite, it follows that:
_
d P
dx
1
_
x
1
=0
P
sat
2
and
_
d P
dx
1
_
x
1
=1
P
sat
1
12.4 By Eqs. (12.15), ln
1
= Ax
2
2
and ln
2
= Ax
2
1
Therefore, ln

1

2
= A(x
2
2
x
2
1
) = A(x
2
x
1
) = A(1 2x
1
)
By Eq. (12.1),

1

2
=
y
1
x
2
P
sat
2
y
2
x
1
P
sat
1
=
_
y
1
/x
1
y
2
/x
2
__
P
sat
2
P
sat
1
_
=
12
r
Whence, ln(
12
r) = A(1 2x
1
)
If an azeotrope exists,
12
= 1 at 0 x
az
1
1. At this value of x
1
, lnr = A(1 2x
az
1
)
The quantity A(1 2x
1
) is linear in x
1
, and there are two possible relationships, depending on the
sign of A. An azeotrope exhists whenever | A| | lnr|. NO azeotrope can exist when | A| < | lnr|.
12.5 Perhaps the easiest way to proceed here is to note that an extremum in ln
1
is accompanied by the
opposite extremum in ln
2
. Thus the difference ln
1
ln
2
is also an extremum, and Eq. (12.8)
becomes useful:
ln
1
ln
2
= ln

1

2
=
d(G
E
/RT
dx
1
Thus, given an expression for G
E
/RT = g(x
1
), we locate an extremum through:
d
2
(G
E
/RT)
dx
2
1
=
d ln(
1
/
2
)
dx
1
= 0
691
For the van Laar equation, write Eq. (12.16), omitting the primes ():
G
E
RT
= A
12
A
21
x
1
x
2
A
where A A
12
x
1
+ A
21
x
2
Moreover,
d A
dx
1
= A
12
A
21
and
d
2
A
dx
2
1
= 0
Then,
d(G
E
/RT)
dx
1
= A
12
A
21
_
x
2
x
1
A

x
1
x
2
A
2
d A
dx
1
_
d
2
(G
E
/RT)
dx
2
1
= A
12
A
21
_

2
A

x
2
x
1
A
2
d A
dx
1

x
1
x
2
A
2
d
2
A
dx
2
1

d A
dx
1
_

2x
1
x
2
A
3
d A
dx
1
+
x
2
x
1
A
2
__
= A
12
A
21
_

2
A

2(x
2
x
1
)
A
2
d A
dx
1
+
2x
1
x
2
A
3
_
d A
dx
1
_
2
_
=
2A
12
A
21
A
3
_
A
2
(x
2
x
1
)A
d A
dx
1
+ x
1
x
2
_
d A
dx
1
_
2
_
=
2A
12
A
21
A
3
_
A + x
2
d A
dx
1
__
x
1
d A
dx
1
A
_
This equation has a zero value if either A
12
or A
21
is zero. However, this makes G
E
/RT everywhere
zero, and no extremum is possible. If either quantity in parentheses is zero, substitution for A and
d A/dx
1
reduces the expression to A
12
= 0 or A
21
= 0, again making G
E
/RT everywhere zero. We
conclude that no values of the parameters exist that provide for an extremum in ln(
1
/
2
).
The Margules equation is given by Eq. (12.9b), here written:
G
E
RT
= Ax
1
x
2
where A = A
21
x
1
+ A
12
x
2
d A
dx
1
= A
21
A
12
d
2
A
dx
2
1
= 0
Then,
d(G
E
/RT)
dx
1
= A(x
2
x
1
) + x
1
x
2
d A
dx
1
d
2
(G
E
/RT)
dx
2
1
= 2A +(x
2
x
1
)
d A
dx
1
+(x
2
x
1
)
d A
dx
1
+ x
1
x
2
d
2
A
dx
2
1
= 2A +2(x
2
x
1
)
d A
dx
1
= 2
_
(x
1
x
2
)
d A
dx
1
A
_
This equation has a zero value when the quantity in square brackets is zero. Then:
(x
2
x
1
)
d A
dx
1
A = (x
2
x
1
)(A
21
A
12
)A
21
x
1
A
12
x
2
= A
21
x
2
+A
12
x
1
2(A
21
x
1
+A
12
x
2
) = 0
Substituting x
2
= 1 x
1
and solving for x
1
yields:
x
1
=
A
21
2A
12
3(A
21
A
12
)
or x
1
=
(r 2)
3(r 1)
r
A
21
A
12
692
When r = 2, x
1
= 0, and the extrema in ln
1
and ln
2
occur at the left edge of a diagram such
as those of Fig. 12.9. For values of r > 2, the extrema shift to the right, reaching a limiting value for
r = at x
1
= 1/3. For positive values of the parameters, in all of these cases A
21
> A
12
, and the
intercepts of the ln
2
curves at x
1
= 1 are larger than the intercepts of the ln
1
curves at x
1
= 0.
When r = 1/2, x
1
= 1, and the extrema in ln
1
and ln
2
occur at the right edge of a diagram
such as those of Fig. 12.9. For values of r < 1/2, the extrema shift to the left, reaching a limiting
value for r = 0 at x
1
= 2/3. For positive values of the parameters, in all of these cases A
21
< A
12
,
and the intercepts of the ln
1
curves at x
1
= 0 are larger than the intercepts of the ln
2
curves at
x
1
= 1.
No extrema exist for values of r between 1/2 and 2.
12.7 Equations (11.15) and (11.16) here become:
ln
1
=
G
E
RT
+ x
2
d(G
E
/RT)
dx
1
and ln
2
=
G
E
RT
x
1
d(G
E
/RT)
dx
1
(a) For simplicity of notation, omit the primes that appear on the parameters in Eqs. (12.16) and
(12.17), and write Eq. (12.16) as:
G
E
RT
= A
12
A
21
x
1
x
2
D
where D A
12
x
1
+ A
21
x
2
Then,
d(G
E
/RT)
dx
1
= A
12
A
21
_
x
2
x
1
D

x
1
x
2
D
2
(A
12
A
21
)
_
and ln
1
= A
12
A
21
_
x
1
x
2
D
+ x
2
_
x
2
x
1
D

x
1
x
2
D
2
(A
12
A
21
)
__
=
A
12
A
21
D
_
x
1
x
2
+ x
2
2
x
1
x
2

x
1
x
2
2
D
(A
12
A
21
)
_
=
A
12
A
21
x
2
2
D
2
(D A
12
x
1
+ A
21
x
1
) =
A
12
A
21
x
2
2
D
2
(A
21
x
2
+ A
21
x
1
)
=
A
12
A
2
21
x
2
2
D
2
= A
12
_
A
21
x
2
D
_
2
= A
12
_
D
A
21
x
2
_
2
= A
12
_
A
12
x
1
+ A
21
x
2
A
21
x
2
_
2
ln
1
= A
12
_
1 +
A
12
x
1
A
21
x
2
_
2
The equation for ln
2
is derived in analogous fashion.
(b) With the understanding that T and P are constant, ln
1
=
_
(nG
E
/RT)
n
1
_
n
2
and Eq. (12.16) may be written:
nG
E
RT
=
A
12
A
21
n
1
n
2
nD
where nD = A
12
n
1
+ A
21
n
2
693
Differentiation in accord with the rst equation gives:
ln
1
= A
12
A
21
n
2
_
1
nD

n
1
(nD)
2
_
(nD)
n
1
_
n
2
_
ln
1
=
A
12
A
21
n
2
nD
_
1
n
1
nD
A
12
_
=
A
12
A
21
x
2
D
_
1
A
12
x
1
D
_
=
A
12
A
21
x
2
D
2
(D A
12
x
1
) =
A
12
A
21
x
2
D
2
A
21
x
2
=
A
12
A
2
21
x
2
2
D
2
The remainder of the derivation is the same as in Part (a).
12.10 This behavior requires positive deviations from Raoults law over part of the composition range and
negative deviations over the remainder. Thus a plot of G
E
vs. x
1
starts and ends with G
E
= 0 at
x
1
= 0 and x
1
= 1 and shows positive values over part of the composition range and negative values
over the remainder, with an intermediate crossing of the x
1
axis. Because these deviations are usually
quite small, the vapor pressures P
sat
1
and P
sat
2
must not be too different, otherwise the dewpoint and
bubblepoint curves cannot exhibit extrema.
12.11 Assume the Margules equation, Eq. (12.9b), applies:
G
E
RT
= x
1
x
2
(A
21
x
1
+ A
12
x
2
) and
G
E
RT
(equimolar) =
1
8
(A
12
+ A
21
)
But [see page 438, just below Eq. (12.10b)]: A
12
= ln

1
A
21
= ln

2
G
E
RT
(equimolar) =
1
8
(ln

1
+ln

2
) or
G
E
RT
(equimolar) =
1
8
ln(

2
)
12.24 (a) By Eq. (12.6):
G
E
RT
= x
1
ln
1
+ x
2
ln
2
= x
1
x
2
2
(0.273 +0.096 x
1
) + x
2
x
2
1
(0.273 0.096 x
2
)
= x
1
x
2
(0.273 x
2
+0.096 x
1
x
2
+0.273 x
1
0.096 x
1
x
2
)
= x
1
x
2
(0.273)(x
1
+ x
2
)
G
E
RT
= 0.273 x
1
x
2
(b) The preceding equation is of the form from which Eqs. (12.15) are derived. From these,
ln
1
= 0.273 x
2
2
and ln
2
= 0.273 x
2
1
(c) The equations of part (b) are not the reported expressions, which therefore cannot be correct. See
Problem 11.11.
12.25 Write Eq. (11.100) for a binary system, and divide through by dx
1
:
x
1
d ln
1
dx
1
+ x
2
d ln
2
dx
1
= 0 whence
d ln
2
dx
1
=
x
1
x
2
d ln
1
dx
1
=
x
1
x
2
d ln
1
dx
2
694
Integrate, recalling that ln
2
= 1 for x
1
= 0:
ln
2
= ln(1) +
_
x
1
0
x
1
x
2
d ln
1
dx
2
dx
1
=
_
x
1
0
x
1
x
2
d ln
1
dx
2
dx
1
(a) For ln
1
= Ax
2
2
,
d ln
1
dx
2
= 2Ax
2
Whence ln
2
= 2A
_
x
1
0
x
1
dx
1
or ln
2
= Ax
2
1
By Eq. (12.6),
G
E
RT
= Ax
1
x
2
(b) For ln
1
= x
2
2
(A + Bx
2
),
d ln
1
dx
2
= 2x
2
(A + Bx
2
) + x
2
2
B = 2Ax
2
+3Bx
2
2
= 2Ax
2
+3Bx
2
(1 x
1
)
Whence ln
2
= 2A
_
x
1
0
x
1
dx
1
+3B
_
x
1
0
x
1
dx
1
3B
_
x
1
0
x
2
1
dx
1
ln
2
= Ax
2
1
+
3B
2
x
2
1
Bx
3
1
or ln
2
= x
2
1
_
A +
3B
2
Bx
1
_
= x
2
1
_
A +
B
2
(1 +2x
2
)
_
Apply Eq. (12.6):
G
E
RT
= x
1
x
2
2
(A + Bx
2
) + x
2
x
2
1
(A +
3B
2
Bx
1
)
Algebraic reduction can lead to various forms of this equation; e.g.,
G
E
RT
= x
1
x
2
_
A +
B
2
(1 + x
2
)
_
(c) For ln
1
= x
2
2
(A + Bx
2
+Cx
2
2
),
d ln
1
dx
2
= 2x
2
(A + Bx
2
+Cx
2
2
) + x
2
2
(B +2Cx
2
) = 2Ax
2
+3Bx
2
2
+4Cx
3
2
= 2Ax
2
+3Bx
2
(1 x
1
) +4Cx
2
(1 x
1
)
2
Whence ln
2
= 2A
_
x
1
0
x
1
dx
1
+3B
_
x
1
0
x
1
(1 x
1
)dx
1
+4C
_
x
1
0
x
1
(1 x
1
)
2
dx
1
or ln
2
= (2A +3B +4C)
_
x
1
0
x
1
dx
1
(3B +8C)
_
x
1
0
x
2
1
dx
1
+4C
_
x
1
0
x
3
1
dx
1
ln
2
=
_
2A +3B +4C
2
_
x
2
1

_
3B +8C
3
_
x
3
1
+Cx
4
1
ln
2
= x
2
1
_
A +
3B
2
+2C
_
B +
8C
3
_
x
1
+Cx
2
1
_
695
or ln
2
= x
2
1
_
A +
B
2
(1 +2x
2
) +
C
3
(1 +2x
2
+3x
2
2
)
_
The result of application of Eq. (12.6) reduces to equations of various forms; e.g.:
G
E
RT
= x
1
x
2
_
A +
B
2
(1 + x
2
) +
C
3
(1 + x
2
+ x
2
2
)
_
12.40 (a) As shown on page 458, x
1
=
1
1 + n
and

H = H(1 + n)
Eliminating 1 + n gives:

H =
H
x
1
(A)
Differentiation yields:
d

H
d n
=
1
x
1
dH
d n

H
x
2
1
dx
1
d n
=
_
1
x
1
dH
dx
1

H
x
2
1
_
dx
1
d n
where
dx
1
d n
=
1
(1 + n)
2
= x
2
1
Whence,
d

H
d n
= H x
1
dH
dx
1
= H
E
x
1
d H
E
dx
1
Comparison with Eq. (11.16) written with M H
E
,

H
E
2
= H
E
x
1
d H
E
dx
1
shows that
d

H
d n
=

H
E
2
(b) By geometry, with reference to the following gure,
d

H
d n
=

H I
n
Combining this with the result of Part (a) gives:

H
E
2
=

H I
n
From which, I =

H n

H
E
2
Substitute:

H =
H
x
1
=
H
E
x
1
and n =
x
2
x
1
696
Whence, I =
H
E
x
1

x
2
x
1

H
E
2
=
H
E
x
2

H
E
2
x
1
However, by the summability equation, H
E
x
2

H
E
2
= x
1

H
E
1
Then, I =

H
E
1
12.41 Combine the given equation with Eq. (A) of the preceding problem:

H = x
2
(A
21
x
1
+ A
12
x
2
)
With x
2
= 1 x
1
and x
1
= 1/(1 + n) (page 458): x
2
=
n
1 + n
The preceding equations combine to give:

H =
n
1 + n
_
A
21
1 + n
+
A
12
n
1 + n
_
(a) It follows immediately from the preceding equation that: lim
n0

H = 0
(b) Because n/(1 + n) 1 for n , it follows that: lim
n

H = A
12
(c) Analogous to Eq. (12.10b), page 438, we write:

H
E
2
= x
2
1
[A
21
+2(A
12
A
21
)x
2
]
Eliminate the mole fractions in favor of n:

H
E
2
=
_
1
1 + n
_
2
_
A
21
+2(A
12
A
21
)
n
1 + n
_
In the limit as n 0, this reduces to A
21
. From the result of Part (a) of the preceding problem,
it follows that
lim
n0
d

H
d n
= A
21
12.42 By Eq. (12.29) with M H, H = H

i
x
i
H
i
. Differentiate:
_
H
t
_
P,x
=
_
H
t
_
P,x

i
x
i
_
H
i
t
_
P,x
With
_
H
t
_
P,x
C
P
, this becomes
_
H
t
_
P,x
= C
P


i
x
i
C
P
i
= C
P
Therefore,
_
H
H
0
d(H) =
_
t
t
0
C
P
dt H = H
0
+
_
t
t
0
C
P
dt
697
12.61 (a) From the denition of M: M
E
= x
1
x
2
M (A)
Differentiate:
dM
E
dx
1
= M(x
2
x
1
) + x
1
x
2
dM
dx
1
(B)
Substitution of Eqs. (A) & (B) into Eqs. (11.15) & (11.16), written for excess properties, yields
the required result.
(b) The requested plots are found in Section A.
12.63 In this application the microscopic state of a particle is its species identity, i.e., 1, 2, 3, . . . . By
assumption, this label is the only thing distinguishing one particle from another. For mixing,
S
t
= S
t
mixed
S
t
unmixed
= S
t
mixed

i
S
t
i
where the total emtropies are given by Eq. (5.42). Thus, for an unmixed species i , and for the mixed
system of particles,
S
t
i
= k ln
i
= k ln
N
i
!
N
i
!
= 0 S
t
mixed
= k ln
N!
N
1
! N
2
! N
3
!
Combining the last three equations gives: S
t
= k ln
N!
N
1
! N
2
! N
3
!
From which:
S
R
=
S
t
R(N/N
A
)
=
S
t
kN
=
1
N
ln
N!
N
1
! N
2
! N
3
!
=
1
N
(ln N!

i
ln N
i
!)
ln N! N ln N N and ln N
i
! N
i
ln N
i
N
i
S
R

1
N
(N ln N N

i
N
i
ln N
i
+

i
N
i
) =
1
N
(N ln N

i
x
i
N ln x
i
N)
=
1
N
(N ln N

i
x
i
N ln x
i


i
x
i
N ln N) =

i
x
i
ln x
1
12.66 Isobaric data reduction is complicated by the fact that both composition and temperature vary from
point to point, whereas for isothermal data composition is the only signicant variable. (The effect
of pressure on liquid-phase properties is assumed negligible.) Because the activity coefcients are
strong functions of both liquid composition and T, which are correlated, it is quite impossible without
additional information to separate the effect of composition from that of T. Moreover, the P
sat
i
values
depend strongly on T, and one must have accurate vapor-pressure data over a temperature range.
12.67 (a) Written for G
E
, Eqs. (11.15) and (11.16) become:

G
E
1
= G
E
+ x
2
dG
E
dx
1
and

G
E
2
= G
E
x
1
dG
E
dx
1
Divide through by RT; dene G
G
E
RT
; note by Eq. (11.91) that

G
E
i
RT
= ln
i
Then ln
1
= G + x
2
dG
dx
1
and ln
2
= G x
1
dG
dx
1
Given:
G
E
x
!
x
2
RT
= A
1/k
with A x
1
A
k
21
+ x
2
A
k
12
698
Whence: G = x
1
x
2
A
1/k
and
dG
dx
1
= x
1
x
2
d A
1/k
dx
1
+ A
1/k
(x
2
x
1
)
d A
1/k
dx
1
=
1
k
A
(1/k)1
d A
dx
1
=
1
k
A
1/k
A
(A
k
21
A
k
12
) and
dG
dx
1
= x
1
x
2
A
1/k
k A
(A
k
21
A
k
12
)+A
1/k
(x
2
x
1
)
Finally, ln
1
= x
2
2
A
1/k
_
(A
k
21
A
k
12
)x
1
k A
+1
_
Similarly, ln
2
= x
2
1
A
1/k
_
1
(A
k
21
A
k
12
)x
2
k A
_
(b) Appropriate substitition in the preceding equations of x
1
= 1 and x
1
= 0 yields:
ln

1
= A
1/k
= (A
k
12
)
1/k
= A
12
ln

2
= A
1/k
= (A
k
21
)
1/k
= A
21
(c) Let g
G
E
x
1
x
2
RT
= A
1/k
= (x
1
A
k
21
+ x
2
A
k
12
)
1/k
If k = 1, g = x
1
A
21
+ x
2
A
12
(Margules equation)
If k = 1, g = (x
1
A
1
21
+ x
2
A
1
12
)
1
=
A
21
A
12
x
1
A
12
+ x
2
A
21
(van Laar equation)
For k = 0, , +, indeterminate forms appear, most easily resolved by working with the
logarithm:
ln g = ln(x
1
A
k
21
+ x
2
A
k
12
)
1/k
=
1
k
ln
_
x
1
A
k
21
+ x
2
A
k
12
_
Apply lH opitals rule to the nal term:
d ln
_
x
1
A
k
21
+ x
2
A
k
12
_
dk
=
x
1
A
k
21
ln A
21
+ x
2
A
k
12
ln A
12
x
1
A
k
21
+ x
2
A
k
12
(A)
Consider the limits of the quantity on the right as k approaches several limiting values.
For k 0, ln g x
1
ln A
21
+ x
2
ln A
12
= ln A
x
1
21
+ln A
x
2
12
and g = A
x
1
21
A
x
2
12
For k , Assume A
12
/A
21
> 1, and rewrite the right member of Eq. (A) as
x
1
ln A
21
+ x
2
(A
12
/A
21
)
k
ln A
12
x
1
+ x
2
(A
12
/A
21
)
k
For k , lim
k
(A
12
/A
21
)
k
0 and lim
k
ln g = ln A
21
Whence g = A
21
except at x
1
= 0 where g = A
12
For k +, lim
k
(A
12
/A
21
)
k
and lim
k
ln g = ln A
12
Whence g = A
12
except at x
1
= 1 where g = A
21
If A
12
/A
21
< 1 rewrite Eq. (A) to display A
21
/A
12
.
699
12.68 Assume that Eq. (12.1) is the appropriate equilibrium relation, written as
x
e

e
P
sat
e
= x
e

e
P
sat
e
= y
e
P e EtOH
Because P is low, we have assumed ideal gases, and for small x
e
let
e

e
. For volume fraction

e
in the vapor, the ideal-gas assumption provides
v
e
y
e
, and for the liquid phase, with x
e
small

l
e
=
x
e
V
l
e
x
e
V
l
e
+ x
b
V
b

x
e
V
l
e
x
b
V
b

x
e
V
l
e
V
b
b blood
Then
V
b
V
e

l
e

e
P
sat
e

v
e
P
volume % EtOH in blood
volume % EtOH in gas

V
e
P
V
b

e
P
sat
e
12.70 By Eq. (11.95),
H
E
RT
= T
_
(G
E
/RT)
T
_
P,x
G
E
RT
= x
1
ln(x
1
+ x
2

12
) x
2
ln(x
2
+ x
1

21
) (12.18)
_
(G
E
/RT)
T
_
x
=
x
1
x
2
d
12
dT
x
1
+ x
2

12

x
2
x
1
d
21
dT
x
2
+ x
1

21
H
E
RT
= x
1
x
2
T
_
_
_
d
12
dT
x
1
+ x
2

12
+
d
21
dT
x
2
+ x
1

21
_
_
_

i j
=
V
j
V
i
exp
a
i j
RT
(i = j ) (12.24)
d
i j
dT
=
V
j
V
i
_
exp
a
i j
RT
_
a
i j
RT
2
=
i j
a
i j
RT
2
H
E
= x
1
x
2
_

12
a
12
x
1
+ x
2

12
+

21
a
21
x
2
+ x
1

21
_
Because C
E
P
= d H
E
/dT, differentiate the preceding expression and reduce to get:
C
E
P
R
= x
1
x
2
_
x
1

12
(a
12
/RT)
2
(x
1
+ x
2

12
)
2
+
x
2

21
(a
21
/RT)
2
(x
2
+ x
1

21
)
2
_
Because
12
and
21
must always be positive numbers, C
E
P
must always be positive.
700