Chapter 14 - Section B - Non-Numerical Solutions

14.2 Start with the equation immediately following Eq. (14.49), which can be modied slightly to read:
ln

i
=
(nG
R
/RT)
n
i

(nZ)
n
i
+n
ln Z
n
i
+1
where the partial derivatives written here and in the following development without subscripts are
understood to be at constant T, n/ (or /n), and n
j
. Equation (6.61) after multiplication by n can
be written:
nG
R
RT
= 2n(nB)
_

n
_
+
3
2
n
2
(nC)
_

n
_
2
n ln Z
Differentiate:
(nG
R
/RT)
n
i
= 2
_

n
_
(nB +n

B
i
) +
3
2
_

n
_
2
(2n
2
C +n
2

C
i
) n
ln Z
n
i
ln Z
or
(nG
R
/RT)
n
i
= 2(B +

B
i
) +
3
2

2
(2C +

C
i
) n
ln Z
n
i
ln Z
By denition,

B
i

_
(nB)
n
i
_
T,n
j
and

C
i

_
(nC)
n
i
_
T,n
j
The equation of state, Eq. (3.40), can be written:
Z = 1 + B +C
2
or nZ = n +n(nB)
_

n
_
+n
2
(nC)
_

n
_
2
Differentiate:
(nZ)
n
i
= 1 +
_

n
_
(nB +n

B
i
) +
_

n
_
2
(2n
2
C +n
2

C
i
)
or
(nZ)
n
i
= 1 +(B +

B
i
) +
2
(2C +

C
i
)
When combined with the two underlined equations, the initial equation reduces to:
ln

i
= 1 +(B +

B
i
) +
1
2

2
(2C +

C
i
)
The two mixing rules are:
B = y
2
1
B
11
+2y
1
y
2
B
12
+ y
2
2
B
22
C = y
3
1
C
111
+3y
2
1
y
2
C
112
+3y
1
y
2
2
C
122
+ y
3
2
C
222
Application of the denitions of

B
i
and

C
i
to these mixing rules yields:

B
1
= y
1
(2 y
1
)B
11
+2y
2
2
B
12
y
2
2
B
22

C
1
= y
2
1
(3 2y
1
)C
111
+6y
1
y
2
2
C
112
+3y
2
2
(1 2y
1
)C
122
2y
3
2
C
222

B
2
= y
2
1
B
11
+2y
2
1
B
12
+ y
2
(2 y
2
)B
22

C
2
= 2y
3
1
C
111
+3y
2
1
(1 2y
2
)C
112
+6y
1
y
2
2
C
122
+2y
2
2
(3 2y
2
)C
222
709
In combination with the mixing rules, these give:
B +

B
1
= 2(y
1
B
11
+ y
2
B
12
)
2C +

C
1
= 3(y
2
1
C
111
+2y
1
y
2
C
112
+ y
2
2
C
122
)
B +

B
2
= 2(y
2
B
22
+ y
1
B
12
)
2C +

C
2
= 3(y
2
2
C
222
+2y
1
y
2
C
122
+ y
2
1
C
112
)
In combination with the boxed equation these expressions along with Eq. (3.40) allow calculation of
ln

1
and ln

2
.
14.11 For the case described, Eqs. (14.1) and (14.2) combine to give: y
i
P = x
i
P
sat
i

sat
i

i
If the vapor phase is assumed an ideal solution,

i
=
i
, and y
i
P = x
i
P
sat
i

sat
i

i
When Eq. (3.38) is valid, the fugacity coefcient of pure species i is given by Eq. (11.36):
ln
i
=
B
i i
P
RT
and
sat
i
=
B
i i
P
sat
i
RT
Therefore, ln

sat
i

i
= ln
sat
i
ln
i
=
B
i i
P
sat
i
RT

B
i i
P
RT
=
B
i i
(P
sat
i
P)
RT
For small values of the nal term, this becomes approximately:

sat
i

i
= 1 +
B
i i
(P
sat
i
P)
RT
Whence, y
i
P = x
i
P
sat
i
_
1 +
B
i i
(P
sat
i
P)
RT
_
or y
i
P x
i
P
sat
i
=
x
i
P
sat
i
B
i i
(P
sat
i
P)
RT
Write this equation for species 1 and 2 of a binary mixture, and sum. This yields on the left the
difference between the actual pressure and the pressure given by Raoults law:
P P(RL) =
x
1
B
11
P
sat
1
(P
sat
1
P) + x
2
B
22
P
sat
2
(P
sat
2
P)
RT
Because deviations from Raoults law are presumably small, P on the right side may be replaced by
its Raoults-law value. For the two terms,
P
sat
1
P = P
sat
1
x
1
P
sat
1
x
2
P
sat
2
= P
sat
1
(1 x
2
)P
sat
1
x
2
P
sat
2
= x
2
(P
sat
1
P
sat
2
)
P
sat
2
P = P
sat
2
x
1
P
sat
1
x
2
P
sat
2
= P
sat
2
x
1
P
sat
1
(1 x
1
)P
sat
2
= x
1
(P
sat
2
P
sat
1
)
Combine the three preceding equations:
P P(RL) =
x
1
x
2
B
11
(P
sat
1
P
sat
2
)P
sat
1
x
1
x
2
B
22
(P
sat
1
P
sat
2
)P
sat
2
RT
=
x
1
x
2
(P
sat
1
P
sat
2
)
RT
(B
11
P
sat
1
B
22
P
sat
2
)
710
Rearrangement yields the following:
P P(RL) =
x
1
x
2
(P
sat
1
P
sat
2
)
2
RT
_
B
11
P
sat
1
B
22
P
sat
2
P
sat
1
P
sat
2
_
=
x
1
x
2
(P
sat
1
P
sat
2
)
2
RT
_
B
11
+
(B
11
B
22
)P
sat
2
P
sat
1
P
sat
2
_
=
x
1
x
2
(P
sat
1
P
sat
2
)
2
RT
(B
11
)
_
1 +
_
1
B
22
B
11
_
P
sat
2
P
sat
1
P
sat
2
_
Clearly, when B
22
= B
11
, the term in square brackets equals 1, and the pressure deviation from the
Raoults-law value has the sign of B
11
; this is normally negative. When the virial coefcients are not
equal, a reasonable assumption is that species 2, taken here as the heavier species (the one with
the smaller vapor pressure) has the more negative second virial coefcient. This has the effect of
making the quantity in parentheses negative and the quantity in square brackets < 1. However, if this
latter quantity remains positive (the most likely case), the sign of B
11
still determines the sign of the
deviations.
14.13 By Eq. (11.90), the denition of
i
, ln
i
= ln

f
i
ln x
i
ln f
i
Whence,
d ln
i
dx
i
=
d ln

f
i
dx
i

1
x
i
=
1

f
i
d

f
i
dx
i

1
x
i
Combination of this expression with Eq. (14.71) yields:
1

f
i
d

f
i
dx
i
> 0
Because

f
i
0,
d

f
i
dx
i
> 0 (const T, P)
By Eq. (11.46), the denition of

f
i
,
d
i
dx
i
= RT
d ln

f
i
dx
i
=
RT

f
i
d

f
i
dx
i
Combination with Eq. (14.72) yields:
d
i
dx
i
> 0 (const T, P)
14.14 Stability requires that G < 0 (see Pg. 575). The limiting case obtains when G = 0, in which
event Eq. (12.30) becomes:
G
E
= RT

i
x
i
ln x
i
For an equimolar solution x
i
= 1/N where N is the number of species. Therefore,
G
E
(max) = RT

i
1
N
ln
1
N
= RT

i
1
N
ln N = RT ln N
For the special case of a binary solution, N = 2, and G
E
(max) = RT ln 2
711
14.17 According to Pb. 11.35, G
E
=
12
Py
1
y
2
or
G
E
RT
=

12
P
RT
y
1
y
2
This equation has the form:
G
E
RT
= Ax
1
x
2
for which it is shown in Examples 14.5 and 14.6 that phase-splitting occurs for A > 2. Thus, the
formation of two immiscible vapor phases requires:
12
P/RT > 2.
Suppose T = 300 K and P = 5 bar. The preceding condition then requires:
12
> 9977 cm
3
mol
1
for vapor-phase immiscibility. Such large positive values for
12
are unknown for real mixtures.
(Examples of gas/gas equilibria are known, but at conditions outside the range of applicability of the
two-term virial EOS.)
14.19 Consider a quadratic mixture, described by:
G
E
RT
= Ax
1
x
2
It is shown in Example 14.5 that phase splitting occurs for such a mixture if A > 2; the value of
A = 2 corresponds to a consolute point, at x
1
= x
2
= 0.5. Thus, for a quadratic mixture,
phase-splitting obtains if:
G
E
> 2
1
2

1
2
RT = 0.5RT
This is a model-dependent result. Many liquid mixtures are known which are stable as single phases,
even though G
E
> 0.5RT for equimolar composition.
14.21 Comparison of the Wilson equation, Eq. (12.18) with the modied Wilson equation shows that
(G
E
/RT)
m
= C(G
E
/RT), where subscript m distinguishes the modied Wilson equation from
the original Wilson equation. To simplify, dene g (G
E
/RT); then
g
m
= Cg ng
m
= Cng
(ng
m
)
n
1
= C
(ng)
n
1
ln(
1
)
m
= C ln
1
where the nal equality follows from Eq. (11.96). Addition and subtraction of ln x
1
on the left side
of this equation and of C ln x
1
on the right side yields:
ln(x
1

1
)
m
ln x
1
= C ln(x
1

1
) C ln x
1
or ln(x
1

1
)
m
= C ln(x
1

1
) (C 1) ln x
1
Differentiate:
d ln(x
1

1
)
m
dx
1
= C
d ln(x
1

1
)
dx
1

C 1
x
1
As shown in Example 14.7, the derivative on the right side of this equation is always positive. How-
ever, for C sufciently greater than unity, the contribution of the second term on the right can make
d ln(x
1

1
)
M
dx
1
< 0
over part of the composition range, thus violating the stability condition of Eq. (14.71) and implying
the formation of two liquid phases.
14.23 (a) Refer to the stability requirement of Eq. (14.70). For instability, i.e., for the formation of two
liquid phases,
d
2
(G
E
/RT)
dx
2
1
<
1
x
1
x
2
712
over part of the composition range. The second derivative of G
E
must be sufciently negative so
as to satisfy this condition for some range of x
1
. Negative curvature is the norm for mixtures for
which G
E
is positive; see, e.g., the sketches of G
E
vs. x
1
for systems (a), (b), (d), (e), and (f ) in
Fig. 11.4. Such systems are candidates for liquid/liquid phase splitting, although it does not in
fact occur for the cases shown. Rather large values of G
E
are usually required.
(b) Nothing in principle precludes phase-splitting in mixtures for which G
E
< 0; one merely re-
quires that the curvature be sufciently negative over part of the composition range. However,
positive curvature is the norm for such mixtures. We know of no examples of liquid/liquid phase-
splitting in systems exhibiting negative deviations from ideal-solution behavior.
14.29 The analogy is Raoults law, Eq. (10.1), applied at constant P (see Fig. 10.12): y
i
P = x
i
P
sat
i
If the vapor phase in VLE is ideal and the liquid molar volumes are negligible (assumptions inherent
in Raoults law), then the Clausius/Clapeyron equation applies (see Ex. 6.5):
d ln P
sat
i
dT
=
H
lv
i
RT
2
Integration from the boiling temperature T
b
i
at pressure P (where P
sat
i
= P) to the actual temperature
T (where P
sat
i
= P
sat
i
) gives:
ln
P
sat
i
P
=
_
T
T
b
i
H
lv
i
RT
2
dT
Combination with Eq. (10.1) yields:
y
i
= x
i
exp
_
T
T
b
i
H
lv
i
RT
2
dT
which is an analog of the Case I SLE equations.
14.30 Consider binary (two-species) equilibrium between two phases of the same kind. Equation (14.74)
applies:
x

i
= x

i
(i = 1, 2)
If phase is pure species 1 and phase is pure species 2, then x

1
=

1
= 1 and x

2
=

2
= 1.
Hence, x

1
= x

1
= 1 and x

2
= x

2
= 1
The reasoning applies generally to (degenerate) N-phase equilibrium involving N mutually immis-
cible species. Whence the cited result for solids.
14.31 The rules of thumb are based on Case II binary SLE behavior. For concreteness, let the solid be pure
species 1 and the solvent be liquid species 2. Then Eqs. (14.93) and (14.92a) apply:
x
1
=
1
= exp
H
sl
1
RT
m
1
_
T T
m
1
T
_
(a) Differentiate:
dx
1
dT
=
1

H
sl
1
RT
2
Thus dx
1
/dT is necessarily positive: the solid solubility x
1
increases with increasing T.
(b) Equation (14.92a) contains no information about species 2. Thus, to the extent that Eqs. (14.93)
and (14.92a) are valid, the solid solubility x
1
is independent of the identity of species 2.
713
(c) Denote the two solid phases by subscripts A and B. Then, by Eqs. (14.93) and (14.92a), the
solubilities x
A
and x
B
are related by:
x
A
x
B
= exp
_
H
sl
(T
m
B
T
m
A
)
RT
m
A
T
m
B
_
where by assumption, H
sl
A
= H
sl
B
H
sl
Accordingly, x
A
/x
B
> 1 if and only if T
A
< T
B
, thus validating the rule of thumb.
(d) Identify the solid species as in Part (c). Then x
A
and x
B
are related by:
x
A
x
B
= exp
_
(H
sl
B
H
sl
A
)(T
m
T)
RT
m
T
_
where by assumption, T
m
A
= T
m
B
T
m
Notice that T
m
> T (see Fig. 14.21b). Then x
A
/x
B
> 1 if and only if H
sl
A
< H
sl
B
, in
accord with the rule of thumb.
14.34 The shape of the solubility curve is characterized in part by the behavior of the derivative dy
i
/d P
(constant T). A general expression is found from Eq. (14.98), y
1
= P
sat
1
P/F
1
, where the enhance-
ment factor F
1
depends (at constant T) on P and y
1
. Thus,
dy
1
d P
=
P
sat
1
P
2
F
1
+
P
sat
1
P
_
_
F
1
P
_
y
1
+
_
F
1
y
1
_
P
dy
1
d P
_
=
y
1
P
+ y
1
_
_
ln F
1
P
_
y
1
+
_
ln F
1
y
1
_
P
dy
1
d P
_
Whence,
dy
1
d P
=
y
1
_
_
ln F
1
P
_
y
1

1
P
_
1 y
1
_
ln F
1
y
1
_
P
(A)
This is a general result. An expression for F
1
is given by Eq. (14.99):
F
1


sat
1

1
exp
V
s
1
(P P
sat
1
)
RT
From this, after some reduction:
_
ln F
1
P
_
y
1
=
_
ln

1
P
_
y
1
+
V
s
1
RT
and
_
ln F
1
y
1
_
P
=
_
ln

1
y
1
_
P
Whence, by Eq. (A),
dy
1
d P
=
y
1
_
_

_
ln

1
P
_
y
1
+
V
s
1
RT

1
P
_
_
1 + y
1
_
ln

1
y
1
_
P
(B)
714
This too is a general result. If the two-term virial equation in pressure applies, then ln

1
is given by
Eq. (11.63a), from which:
_
ln

1
P
_
y
1
=
1
RT
(B
11
+ y
2
2

12
) and
_
ln

1
y
1
_
P
=
2y
2

12
P
RT
Whence, by Eq. (B),
dy
1
d P
=
y
1
_
V
s
1
B
11
y
2
2

12
RT

1
P
_
1
2y
1
y
2

12
P
RT
The denominator of this equation is positive at any pressure level for which Eq. (3.38) is likely to be
valid. Hence, the sign of dy
1
/d P is determined by the sign of the group in parentheses. For very low
pressures the 1/P term dominates and dy
1
/d P is negative. For very high pressures, 1/P is small,
and dy
1
/d P can be positive. If this is the case, then dy
1
/d P is zero for some intermediate pressure,
and the solubility y
1
exhibits a minimum with respect to pressure. Qualitatively, these features are
consistent with the behavior illustrated by Fig. 14.23. However, the two-term virial equation is only
valid for low to moderate pressures, and is unable to mimic the change in curvature and attening
of the y
1
vs. P curve observed for high pressures for the naphthalene/CO
2
system.
14.35 (a) Rewrite the UNILAN equation:
n =
m
2s
_
ln(c + Pe
s
) ln(c + Pe
s
)
_
(A)
As s 0, this expression becomes indeterminate. Application of lH opitals rule gives:
lim
s0
n = lim
s0
m
2
_
Pe
s
c + Pe
s
+
Pe
s
c + Pe
s
_
=
m
2
_
P
c + P
+
P
c + P
_
or lim
s0
n =
mP
c + P
which is the Langmuir isotherm.
(b) Henrys constant, by denition: k lim
P0
dn
d P
Differentiate Eq. (A):
dn
d P
=
m
2s
_
e
s
c + Pe
s

e
s
c + Pe
s
_
Whence, k =
m
2s
_
e
s
c

e
s
c
_
=
m
cs
_
e
s
e
s
2
_
or k =
m
cs
sinh s
(c) All derivatives of n with respect to P are well-behaved in the zero-pressure limit:
lim
P0
dn
d P
=
m
cs
sinh s
715
lim
P0
d
2
n
d P
2
=
m
c
2
s
sinh 2s
lim
P0
d
3
n
d P
3
=
2m
c
3
s
sinh 3s
Etc.
Numerical studies show that the UNILAN equation, although providing excellent overall corre-
lation of adsorption data at low-to-moderate surface coverage, tends to underestimate Henrys
constant.
14.36 Start with Eq. (14.109), written as:
ln(P/n) = ln k +
_
n
0
(z 1)
dn
n
+ z 1
With z = 1 + Bn +Cn
2
+ , this becomes:
ln(P/n) = ln k +2Bn +
3
2
Cn
2
+
Thus a plot of ln(P/n) vs. n produces ln k as the intercept and 2B as the limiting slope (for
n 0). Alternatively, a polynomial curve t of ln(P/n) in n yields ln k and 2B as the rst
two coefcients.
14.37 For species i in a real-gas mixture, Eqs. (11.46) and (11.52) give:

g
i
=
i
(T) + RT ln y
i

i
P
At constant temperature, d
g
i
= RT d ln y
i

i
P
With d
i
= d
g
i
, Eq. (14.105) then becomes:

a
RT
d+d ln P +

i
x
i
d ln y
i

i
= 0 (const T)
For pure-gas adsorption, this simplies to:
a
RT
d = d ln P +d ln (const T) (A)
which is the real-gas analog of Eq. (14.107). On the left side of Eq. (A), introduce the adsorbate
compressibility factor z through z a/RT = A/nRT:
a
RT
d = dz + z
dn
n
(B)
where n is moles adsorbed. On the right side of Eq. (A), make the substitution:
d ln = (Z 1)
d P
P
(C)
which follows from Eq. (11.35). Combination of Eqs. (A), (B), and (C) gives on rearrangement (see
Sec. 14.8):
d ln
n
P
= (1 z)
dn
n
dz +(Z 1)
d P
P
which yields on integration and rearrangement:
n = k P exp
_
P
0
(Z 1)
d P
P
exp
__
n
0
(1 z)
dn
n
+1 z
_
This equation is the real-gas analog of Eq. (14.109).
716
14.39 & 14.40 Start with Eq. (14.109). With z = (1 bm)
1
, one obtains the isotherm:
n = k P(1 bn) exp
_

bn
1 bn
_
(A)
For bn sufciently small, exp
_

bn
1 bn
_
1
bn
1 bn
Whence, by Eq. (A), n k P(1 2bn) or n
k P
1 +2bk P
which is the Langmuir isotherm.
With z = 1 +n, the adsorption isotherm is: n = k P exp(2n)
from which, for n sufciently small, the Langmuir isotherm is again recovered.
14.41 By Eq. (14.107) with a = A/n,
Ad
RT
= n
d P
P
The denition of and its derivative are:

A
RT
and d =
A d
RT
Whence, d = n
d P
P
(A)
By Eq. (14.128), the Raoults law analogy, x
i
= y
i
P/P

i
. Summation for given P yields:

i
x
i
= P

i
y
i
P

i
(B)
By general differentiation,
d

i
x
i
= P d

i
y
i
P

i
+

i
y
i
P

i
d P (C)
The equation,

i
x
i
= 1, is an approximation that becomes increasingly accurate as the solution
procedure converges. Thus, by rearrangement of Eq. (B),

i
y
i
P

i
=

i
x
i
P
=
1
P
With P xed, Eq. (C) can now be written in the simple but approximate form:
d

i
x
i
=
d P
P
Equation (A) then becomes:
d = n d

i
x
i
or = n
_

i
x
i
_
where we have replaced differentials by deviations. The deviation in

i
x
i
is known, since the true
value must be unity. Therefore,

i
x
i
= P

i
y
i
P

i
1
717
By Eq. (14.132), n =
1

i
(x
i
/n

i
)
Combine the three preceding equations:
=
P

i
y
i
P

i
1

i
(x
i
/n

i
)
When x
i
= y
i
P/P

i
, the Raoults law analogy, is substituted the required equation is reproduced:
=
P

i
y
i
P

i
1
P

i
y
i
P

i
n

i
14.42 Multiply the given equation for G
E
/RT by n and convert all mole fractions to 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
Apply Eq. (11.96) for i = 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
Introduce solute-free mole fractions:
x

2

x
2
x
2
+ x
3
=
x
2
1 x
1
and x

3
=
x
3
1 x
1
Whence, ln
1
= A
12
x

2
(1 x
1
)
2
+ A
13
x

3
(1 x
1
)
2
A
23
x

2
x

3
(1 x
1
)
2
For x
1
0, ln

1
= A
12
x

2
+ A
13
x

3
A
23
x

2
x

3
Apply this equation to the special case of species 1 innitely dilute in pure solvent 2. In this case,
x

2
= 1, x

3
= 0, and
ln

1,2
= A

12
Also ln

1,3
= A

13
Whence, ln

1
= x

2
ln

1,2
+ x

3
ln

1,3
A
23
x

2
x

3
In logarithmic form the equation immediately following Eq. (14.24) on page 552 may be applied to
the several innite-dilution cases:
ln H
1
= ln f
1
+ln

1
ln H
1,2
= ln f
1
+ln

1,2
ln H
1,3
= ln f
1
+ln

1,3
Whence, ln H
1
ln f
1
= x

2
(ln H
1,2
ln f
1
) + x

3
(ln H
1,3
ln f
1
) A
23
x

2
x

3
or ln H
1
= x

2
ln H
1,2
+ x

3
ln H
1,3
A
23
x

2
x

3
718
14.43 For the situation described, Figure 14.12 would have two regions like the one shown from to ,
probably one on either side of the minimum in curve II.
14.44 By Eq. (14.136) with

V
2
= V
2
:
V
2
RT
= ln(x
2

2
)
Represent ln
2
by a Taylor series:
ln
2
= ln
2
|
x
1
=0
+
d ln
2
dx
1

x
1
=0
x
1
+
1
2
d
2
ln
2
dx
2
1

x
1
=0
x
2
1
+
But at x
1
= 0 (x
2
= 1), both ln
2
and its rst derivative are zero. Therefore,
ln
2
=
1
2
_
d
2
ln
2
dx
2
1
_
x
1
=0
x
2
1
+
Also, ln x
2
= ln(1 x
1
) = x
1

x
2
1
2

x
3
1
3

x
4
1
4

Therefore, ln(x
2

2
) = +ln x
2
+ln
2
= x
1

1
2
_
1
1
2
_
d
2
ln
2
dx
2
1
_
x
1
=0
_
x
2
1

and
V
2
x
1
RT
= 1 +
1
2
_
1
1
2
_
d
2
ln
2
dx
2
1
_
x
1
=0
_
x
1
+
Comparison with the given equation shows that: B =
1
2
_
1
1
2
_
d
2
ln
2
dx
2
1
_
x
1
=0
_
14.47 Equation (11.95) applies:
_
(G
E
/RT)
T
_
P,x
=
H
E
RT
2
For the partially miscible system G
E
/RT is necessarily large, and if it is to decrease with increasing
T, the derivative must be negative. This requires that H
E
be positive.
14.48 (a) In accord with Eqs. (14.1) and (14.2), y
i

sat
i
P = x
i

i
P
sat
i
K
i

y
i
x
i
=

i
P
sat
i
P


sat
i

12

K
1
K
2
=

1
P
sat
1

2
P
sat
2

sat
1

sat
2
(b)
12
(x
1
= 0) =

1
P
sat
1
P
sat
2

1
(P
sat
1
)

1
(P
sat
2
)

2
(P
sat
2
)

2
(P
sat
2
)
=

1
P
sat
1
P
sat
2

1
(P
sat
1
)

1
(P
sat
2
)

12
(x
1
= 1) =
P
sat
1

2
P
sat
2

1
(P
sat
1
)

1
(P
sat
1
)

2
(P
sat
1
)

2
(P
sat
2
)
=
P
sat
1

2
P
sat
2

2
(P
sat
1
)

2
(P
sat
2
)
The nal fractions represent corrections to modied Raoults law for vapor nonidealities.
719
(c) If the vapor phase is an ideal solution of gases, then

i
=
i
for all compositions.
14.49 Equation (11.98) applies:
_
ln
i
T
_
P,x
=

H
E
i
RT
2
Assume that H
E
and

H
E
i
are functions of composition only. Then integration from T
k
to T gives:
ln

i
(x, T)

i
(x, T
k
)
=

H
E
i
R
_
T
T
k
dT
T
2
=

H
E
i
R
_
1
T

1
T
k
_
=

H
E
i
RT
_
T
T
k
1
_

i
(x, T) =
i
(x, T
k
) exp
_

H
E
i
RT
_
T
T
k
1
__
14.52 (a) From Table 11.1, p. 415, nd:
_
G
E
T
_
P,x
= S
E
= 0 and G
E
is independent of T.
Therefore
G
E
RT
=
F
R
(x)
RT
(b) By Eq. (11.95),
_
(G
E
/RT)
T
_
P,x
=
H
E
RT
2
= 0
G
E
RT
= F
A
(x)
(c) For solutions exhibiting LLE, G
E
/RT is generally positive and large. Thus and are positive
for LLE. For symmetrical behavior, the magic number is A = 2:
A < 2 homogeneous; A = 2 consolute point; A > 2 LLE
With respect to Eq. (A), increasing T makes G
E
/RT smaller. thus, the consolute point is an up-
per consolute point. Its value follows from:

RT
U
= 2 T
U
=

2R
The shape of the solubility curve is as shown on Fig. 14.15.
14.53 Why? Because they are both nontoxic, relatively inexpensive, and readily available. For CO
2
, its
T
c
is near room temperature, making it a suitable solvent for temperature-sensitive materials. It is
considereably more expensive than water, which is probably the cheapest possible solvent. However,
both T
c
and P
c
for water are high, which increases heating and pumping costs.
720