SOLUTION

THERMODYNAMICS:
THEORY

PARTIAL
PROPERTIES_PART2

By : Dr Lim Ying Pei (UiTM Shah Alam)

 
dM 
dM
M1  M  x2 M 2  M  x1
EXAMPLE 11.2 dx1 dx1
Describe a graphical interpretation of eqs. (11.15) and (11.16).

Solution:  Figure 11.1 (a) shows a representative

plot of M vs. x1 for a binary system.
 The tangent line shown extend across
the figure, intersecting the edges (at x1
= 1 and x1 = 0) at points label I1 and I2.
 Two equivalent expressions can be
written for the slope of this tangent
dM M  I 2
line: dM
 and  I1  I 2
dx1 x1 dx1

 The first equation is solved for I2; it

dM with the second to give I1. dM
combines
I 2  M  x1 and I1  M   1  x1 
dx1 dx1

 Comparison 
of these expression

with
I 1  M 1 andand
eqs. (11.16)  M 2 that
(11.15)I 2show

2
 The tangent intercepts give directly the
 The limiting values are
indicated by Fig. 11.1 (b).
 For the tangent line

drawn at
x1 = 0 (pure species
M 2  M2),
2

 
and at the opposite intercept,
M 1  M1


M1  M1
 For the tangent line drawn at
 
xM1 = 1 (pure
2  M2

species 1),
and at the opposite
intercept,

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EXAMPLE 11.3
The need arises in a laboratory for 2000 cm3 of an
antifreeze solution consisting of 30 mole % methanol
in water. What volumes of pure methanol and of pure
water at 25oC (298.15K) must be mixed to form the
2000 cm3 of antifreeze, also at 25oC (298.15K)? Partial
molar volumes for methanol and water in a 30 mole
% methanol solution and their pure species molar
volumes, both
 at 25oC (298.15K), are
Methanol  1  : V1  38.632 cm 3 mol -1 V1  40.727 cm 3 mol -1

Water  2  : V2  17.765 cm 3 mol -1 V2  18.068 cm 3 mol -1

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 5

Solution:
 Equation (11.11) is written for the molar volume of the binary
antifreeze solution, and known values are substituted for the mole
fractions and partial volumes:

 
V   x i Vi
i
V  x1 V1  x2 V2
  0.3   38.632    0.7   17.765 
 24.025 cm 3 mol -1
 Because the required total volume of solution is Vt = 2000 cm3, the
total number of moles required is
Vt 2000
n   83.246 mol
V 24.025
 Of this, 30% is methanol, and 70% is water:
ni  xi n n1   0.3   83.246   24.974 mol
n2   0.7   83.246   58.272 mol

 The total volume of each pure species is V t = niVi; thus,

V1t   24.974   40.727   1017 cm 3 i
V2t   58.272   18.068   1053 cm 3
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  
 Values of V1 ,V2 and V for
the binary solution
methanol(1)/water(2) at 25oC
(298.15K) are plotted in Fig.
11.2 as functions of x1.
 The line drawn tangent to
the V vs x1 curve at x1 = 0.3
illustrates the graphical
procedure by which values of
 
V1 and V2 may be obtained.

 The curve V1 becomes
horizontal at x1 = 1 and the
curve for  becomes
horizontalVat
 
V1 and V2 2 x1= 0 or x2 = 1.
 The curves for  
V1 and V2 at
appear to be horizontal
both ends.

For the tangent line drawn 
at x1 = 0 (pure species
V2  V2 2), and

at the opposite intercept,
V1  V1

For the tangent line drawn V1  V1 1),
at x1 = 1 (pure species and
 
at the opposite intercept,
V2  V2 6
 Eq. (C), the Gibbs/Duhem equation, may be written in
derivative forms:
 
d M1 d M2
x1  x2 0 (E)
dx1 dx1
 
dM1 x dM 2
 2 (F)
dx1 x1 dx1
 
dM 2 x dM1
 1 (G)
dx1 x2 dx1
 
 When M 1 and M 2 are plotted vs. x1, the slopes
must be of opposite sign.

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 Moreover,

 

d M1  Provided lim d M
lim 0 2
is finite 
x1 1 dx
1
 x1 1 dx
1

 
Similarly,

 

d M2  Provided lim d M
lim 0 1
is finite 
x2 1 dx
1
 x 2 1 dx
1

 
 
Thus, plot of
M 1 and M 2 vs. x1 become horizontal as
each species approaches purity.

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EXAMPLE 11.4
The enthalpy of a binary liquid system of species 1
and 2 at fixed T and P is represented by the
equation
H  400 x1  600 x2  x1 x2  40 x1  20 x2 
 
H 1 and H 2
where H is in Jmol-1. Determine expressions for
as a functions of x1, numerical

values for
H 1 and
the pure species enthalpies 
H1 Hand
2 H2, and
numerical values for the partial enthalpies at
infinite dilution

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 10

Solution:
Replace x2 by 1 – x1 in the given equation for H and simplify:
H  600  180 x1  20 x13 (A)
dH
 180  60 x12
dx1

By equation (11.15), dH
H 1  H  x2
dx1


Then,
H 1  600  180 x 1  20 x 3
1  180 x 2  60 x 2
1 x2
Replace x2 by 1 – x1 and simplify:

H1  420  60 x12  40 x13 (B)

By eq. (11.16),

dH
H 2  H  x1  600  180 x1  20 x13  180 x1  60 x13
dx1

or (C)
H 2  600  40 x13
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A numerical value for H1 results by substitution of x1 =

1 in either eq (A) or (B). Both eqn. yield H1 = 400 J
mol-1.

H2 is found from either eq. (A) or (C) when x1 = 0.

The result is H2 = 600 J mol

-1.

H 1 and H 2
The infinite dilution are found from eq.
(B) and (C)
-
when x1 = 0 in eq.-
(B) and x1 = 1 in eq. (C).
The results
H1 = are:
420 Jmol -1 and H2 = 640 Jmol -1

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