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∂(n P)
∂(nT ) ∂n ∂n
T̄i ≡ =T =T P̄i ≡ =P =P
∂n i P,T,n j ∂n i T,P,n j ∂n i P,T,n j ∂n i T,P,n j
∂m
11.7 (a) Let m be the mass of the solution, and define the partial molar mass by: m̄ i ≡
∂n i T,P,n j
m= nk Mk = ni Mi + n j M j ( j = i)
k j
∂m ∂(n i Mi )
and = = Mi Whence, m̄ i = Mi
∂n i T,P,n j ∂n i T,P,n j
∂M t ∂M t
∂n i
(b) Define a partial specific property as: M̃i ≡ =
∂m i T,P,m j ∂n i T,P,m j ∂m i T,P,m j
mi 1
∂n i
If Mi is the molar mass of species i, ni = and =
Mi ∂m i T,P,m j Mi
M̄i
Because constant m j implies constant n j , the initial equation may be written: M̃i =
Mi
dV dV
11.8 By Eqs. (10.15) and (10.16), V̄1 = V + x2 and V̄2 = V − x1
d x1 d x1
dV −1 dρ
Because V = ρ −1 then = 2 whence
d x1 ρ d x1
1 x2 dρ 1 x2 dρ 1 dρ
V̄1 = − 2 = 1− = ρ − x 2
ρ ρ d x1 ρ ρ d x1 ρ2 d x1
1 x1 dρ 1 x1 dρ 1 dρ
V̄2 = + 2 = 1+ = ρ + x 1
ρ ρ d x1 ρ ρ d x1 ρ2 d x1
dρ
With ρ = a0 + a1 x1 + a2 x12 and = a1 + 2a2 x1 these become:
d x1
1 1
V̄1 = [a0 − a1 + 2(a1 − a2 )x1 + 3a2 x12 ] and V̄2 = (a0 + 2a1 x1 + 3a2 x12 )
ρ2 ρ2
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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
n M = n 1 M1 + n 2 M2 + n 3 M3 + C
n2
∂(n M) 1 2n 1 ∂n
For M̄1 , = 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
∂n
Because n = n 1 + n 2 + n 3 , =1
∂n 1 T,P,n 2 ,n 3
n2n3 n1
Whence, M̄1 = M1 + 1 − 2 C and M̄1 = M1 + x2 x3 [1 − 2x1 ]C
n2 n
One can readily show that application of Eq. (11.11) regenerates the original equation for M. The
infinite dilution values are given by:
M̄i∞ = Mi + x j xk C ( j, k = i)
RT
P= yi Z i
V i
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(b) In accord with Eq. (11.11),
H = x1 (420 − 60 x12 + 40 x13 ) + (1 − x2 )(600 + 40 x13 )
d H̄1 d H̄2
(c) Write Eq. (11.14) for a binary system and divide by d x1 : x1 + x2 =0
d x1 d x1
Differentiate the the boxed equations of part (a):
d H̄1 d H̄2
= −120 x1 + 120 x12 = −120 x1 x2 and = 120 x12
d x1 d x1
Multiply each derivative by the appropriate mole fraction and add:
(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 H̄1 d H̄2
= =0
d x1 x1 =1 d x1 x1 =0
(e)
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(b) In accord with Eq. (11.11),
d V̄1 d V̄2
(c) Write Eq. (11.14) for a binary system and divide by d x1 : x1 + x2 =0
d x1 d x1
Differentiate the the boxed equations of part (a):
d V̄1 d V̄2
= −2 − 40 x1 + 42 x12 and = 2 x1 + 42 x12
d x1 d x1
Multiply each derivative by the appropriate mole fraction and add:
d V̄1 d V̄2
= =0
d x1 x1 =1 d x1 x1 =0
(e)
dH dH
H̄1 = H + x2 and H̄2 = H − x1
d x1 d x1
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Given that: H = x1 (a1 + b1 x1 ) + x2 (a2 + b2 x2 )
dH
Then, after simplification, = a1 + 2b1 x1 − (a2 + 2b2 x2 )
d x1
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:
d H̄1 d H̄2
x1 + x2 =0
d x1 d x1
The suggested expresions do not obey this equation, further evidence that they cannot be valid.
Whence,
∂M ∂V ∂M ∂V
M̄i = M̃i + n or M̃i = M̄i − n
∂V T,n ∂n i T,P,n j ∂V T,n ∂n i T,P,n j
By definition,
∂V ∂V
∂(nV )
V̄i ≡ =n +V or n = V̄i − V
∂n i T,P,n j ∂n i T,P,n j ∂n i T,P,n j
∂M
Therefore, M̃i = M̄i + (V − V̄i )
∂V T,x
11.20 Equation (11.59) demonstrates that ln φ̂i is a partial property with respect to G R /RT . Thus ln φ̂i =
Ḡ i /RT . The partial-property analogs of Eqs. (11.57) and (11.58) are:
∂ ln φ̂i V̄ R ∂ ln φ̂i H̄iR
= i and =−
∂P RT ∂T RT 2
T,x P,x
GR
RT
= xi ln φ̂i and i xi d ln φ̂i = 0 (const T, P)
i
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11.26 For a pressure low enough that Z and ln φ are given approximately by Eqs. (3.38) and (11.36):
BP BP
Z =1+ and ln φ =
RT RT
then: ln φ ≈ Z − 1
11.28 (a) Because Eq. (11.96) shows that ln γi is a partial property with respect to G E/RT , Eqs. (11.15)
and (11.16) may be written for M ≡ G E/RT :
GE d(G E/RT )
= −1.8 x1 + x12 + 0.8 x13 whence = −1.8 + 2 x1 + 2.4 x12
RT d x1
Then, ln γ1 = −1.8 + 2 x1 + 1.4 x12 − 1.6 x13 and ln γ2 = −x12 − 1.6 x13
GE
= x1 ln γ1 + x2 ln γ2 = x1 (−1.8 + 2 x1 + 1.4 x12 − 1.6 x13 ) + (1 − x1 )(−x12 − 1.6 x13 )
RT
GE
Whence, = −1.8 x1 + x12 + 0.8 x13
RT
d ln γ1 d ln γ2
= =0
d x1 x1 =1 d x1 x1 =0
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(e)
11.29 Combine definitions of the activity coefficient and the fugacity coefficients:
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):
∂G E
E E E T
H = C P T and S = − = C PE
∂ T P,x T
H1E − G 1E T
S1E = and S2E = S1E + C PE
T1 T
I. II. For C PE = 0
(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
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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 1 n1 n2n3
ln γ1 = 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 γ2 = A12 x1 (1 − x2 ) − A13 x1 x3 + A23 x3 (1 − x2 )
ln γ3 = −A12 x1 x2 + A13 x1 (1 − x3 ) + A23 x2 (1 − x3 )
(b) Each ln γi is multiplied by xi , and the terms are summed. Consider the first terms on the right of
each expression for ln γi . 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 .
Combine this equation with the last equation on Pg. 402: G E = δ12 P y1 y2
∂G E
E
From the last column of Table 11.1 (page 415): S = −
∂T P,x
dδ12
Because δ12 is a function of T only: SE = − P y1 y2
dT
dδ12
E E E E E
By the definition of G , H = G + T S ; whence, H = δ12 − T P y1 y2
dT
∂HE
Again from the last column of Table 11.1: C PE =
∂T P,x
d 2 δ12
This equation and the preceding one lead directly to: C PE = −T P y1 y2
dT 2
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∂(G E /RT ) −H E ∂(G E /T ) −H E
11.41 From Eq. (11.95): = or =
∂T P RT 2 ∂T P T2
∂(G E /T ) (G E /T ) −H E
To an excellent approximation, write: ≈ ≈ 2
∂T P T Tmean
d M̄1E d M̄2E
= 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 M̄1E d M̄2E
For x1 = 0 = 2A and =0
d x1 d x1
d M̄1E d M̄2E
For x1 = 1 =0 and = −2A
d x1 d x1
(b) For M E = A sin(π x1 ) find:
M̄1E = A sin(π x1 ) + Aπ x2 cos(π x1 ) and M̄2E = A sin(π x1 ) − Aπ x1 cos(π x1 )
d M̄1E d M̄2E
= −Aπ 2 x2 sin(π x1 ) and = Aπ 2 x1 sin(π x1 )
d x1 d x1
The two slopes are thus of opposite sign, as required. But note the following, which is unusual:
d M̄1E d M̄2E
For x1 = 0 and x1 = 1 =0 and =0
d x1 d x1
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Pb. 11.45 (a) A 10 i 0 .. 100 xi .00001 .01 . i
2. 2 2
MEi A . xi 1 xi MEbar1i A . xi . 1 xi 2 3 . xi
MEbar2i A . xi . xi . 1 xi . 2 3. 1 xi
1.5
MEi
1
MEbar1
i
0.5
MEbar2i
0.5
0 0.2 0.4 0.6 0.8 1
xi
MEbar1i A . sin p
.x
i A.p . 1 xi . cos p
.x
i
MEbar2i A . sin p
.x
i A . p . xi . cos p
.x
i
40
30
MEi
20
MEbar1
i
MEbar2i 10
10
0 0.2 0.4 0.6 0.8 1
xi
687A
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∂(n M) ∂M
11.46 By Eq. (11.7), M̄i = = M +n
∂n i T,P,n j ∂n i T,P,n j
∂ M
At constant T and P, dM = d xk
k
∂ xk T,P,x j
∂M ∂ M ∂ xk
=
∂n i T,P,n j k
∂ xk T,P,x j ∂n i nj
n
k
− n2
(k = i)
nk ∂ xk
With xk = =
n ∂n i 1 n
nj − i (k = i)
n n2
∂M 1 ∂M 1 ∂M
=− xk + (1 − xi )
∂n i T,P,n j n k=i ∂ xk T,P,x j n ∂ xi T,P,x j
1 ∂M 1 ∂M
= − xk
n ∂ xi T,P,x j n k ∂ xk T,P,x j
∂M ∂M
M̄i = M + − xk
∂ xi T,P,x j k
∂ xk T,P,x j
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 ∂M ∂M d x2 ∂M ∂M
= + = −
d x1 ∂ x1 x2 ∂ x2 x1 d x1 ∂ x1 x2 ∂ x2 x1
dM
M̄1 = M + x2
d x1
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∂(n M E )
11.47 (a) Apply Eq. (11.7) to species 1: M̄1E =
∂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
1 1 B
−1
M̄1E = An 2 + + n1 −
n 1 + Bn 2 n 2 + Bn 1 (n 1 + Bn 2 )2 (n 2 + Bn 1 )2
Conversion back to mole fractions yields:
1 1 1 B
E
M̄1 = 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
M̄1 = Ax2 1− + 1−
x1 + Bx2 x1 + Bx2 x2 + Bx1 x2 + Bx1
Reduction yields:
B 1
M̄1E = Ax22 +
(x1 + Bx2 )2 (x2 + Bx1 )2
Similarly,
1 B
M̄2E = Ax12 2
+
(x1 + Bx2 ) (x2 + Bx1 )2
(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:
d M̄1E d M̄2E
x1 + 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 M̄iE , its value and
derivative with respect to xi become zero at xi = 1.
1 1
E ∞ E ∞
(c) ( M̄1 ) = A +1 ( M̄2 ) = A 1 +
B B
11.48 By Eqs. (11.15) and (11.16), written for excess properties, find:
d M̄1E d2 M E d M̄2E d2 M E
= x2 = −x1
d x1 d x12 d x1 d x12
At x1 = 1, d M̄1E /d x1 = 0, and by continuity can only increase or decrease for x1 < 1. Therefore the
sign of d M̄1E /d x1 is the same as the sign of d 2 M E /d x12 . Similarly, at x1 = 0, d M̄2E /d x1 = 0, and by
the same argument the sign of d M̄2E /d x1 is of opposite sign as the sign of d 2 M E /d x12 .
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11.49 The claim is not in general valid.
1 ∂V
V id =
β≡ xi Vi
V ∂T P i
1 ∂ Vi 1
id
β = xi = xi Vi βi
i xi Vi i
∂T P i xi Vi i
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