8.

16
Given: Tabulated data of Cp(wt )

for Carbon tetrachloride (CCl4)

Required: Single graph plot of the constant-pressure partial molar heat capacity for both benzene and
carbon tetrachloride as a function of composition
Solution:
A basis of 100 gram solution is used to calculate for the mole percent of benzene and carbon
tetrachloride in the solution.
Table 1. Conversion of wt% to mol% ( x i )

wt%
CCl4

wt. CCl4
per 100
gram
solution

wt.
Benzene
per 100 g
solution

Moles of
CCl4 per 100
g solution

Moles of
benzene per
100 g
solution

100

1.280245807

10

10

90

0.065015279

1.152221226

20

20

80

0.130030557

1.024196646

30

30

70

0.195045836

0.896172065

40

40

60

0.260061114

0.768147484

50

50

50

0.325076393

0.640122904

60

60

40

0.390091672

0.512098323

70

70

30

0.45510695

0.384073742

80

80

20

0.520122229

0.256049161

90

90

10

0.585137507

0.128024581

100

100

0.650152786

Mole
Percent of
CCl4

CCl
(
4)

0
0.05341219
9
0.112655946
0.17874141
9
0.25292641
5
0.33679717
1
0.43238306
1
0.54232295
2
0.670112601
0.82048319
3
1

mol%
Benzene

1
0.94658780
1
0.88734405
4
0.82125858
1
0.74707358
5
0.66320282
9
0.56761693
9
0.45767704
8
0.32988739
9
0.17951680
7
0

The total mass balance equation is

100=m1 y 1+ m2 y 2
where

(Eq. 1)

mi is the mass of the substance,

wt
y i is the mass fraction (
100 ) and the substance

is CCl4 when i=1 and Benzene when i=2.

Calculating for the mass for each substance:

m1=100 y 1

(Eq. 2)
(Eq. 3)

m2=100 y 2
Since the mixture is binary,

y 1+ y 2=1

(Eq. 4)

m 2=100(1 y 1)
To get the number moles ( n ) of the substance, the mass calculated for each mass fraction is
divided by its molecular weight.
The mole fraction is calculated using the formula:

x 1=

n1
n1+ n2

and

x 2=1x 1

(Eq. 5 & 6)

Table 2. Molar Heat Capacity Data for Benzene (2)-Carbon Tetrachloride (1) System at T=20C.

^
Cp

MW mix

x1
(mol CCl4/mol)

Average Molecular
Weight
(g/mol)

0
0.053412199
0.112655946
0.178741419
0.252926415
0.336797171
0.432383061
0.542322952
0.670112601
0.820483193
1

78.11
82.15330347
86.63805509
91.6407254
97.25652959
103.6055459
110.8413977
119.1638475
128.8375239
140.2205777
153.81

Specific Heat
Capacity
(J/g C)

1.7655
1.63
1.493
1.358
1.222
1.1
1.004
0.927
0.858
0.816
0.807

Table 2 shows all the values determined to aid in calculating the

Cp

mix Cp

Specific Heat
Capacity
(J/mol C)

(J/mol C)

137.903205
133.9098847
129.3506163
124.4481051
118.8474792
113.9661005
111.2847633
110.4648866
110.5425955
114.4199914
124.12467

0
-3.25738
-7.00035
-10.9923
-15.5708
-19.2965
-20.6608
-19.9659
-18.1274
-12.1782
0

mix Cp .

From the mole fraction values taken from table 1, the average Molecular Weight is calculated
using the equation:

MW mix = x i MW i

(Eq. 7)

The molar heat capacity

Cp

is taken using by multiplying the Specific heat capacity

^
Cp

and the average molecular weight MW mix .

The

mix Cp

heat capacity (Eq. 8)

(Eq. the
8) ideal molar
is calculated by subtracting the actual molar heat capacity and

 mix Cp=Cp x i Cpi

Table 3. Partial Molar Heat Capacity of Benzene (2) - Carbon Tetrachloride (1) System at T=20C.

x1

1
Cp
- Cp 1

Cp 1

2
Cp
- Cp 2

Cp 2

0
0.053412199
0.112655946
0.178741419
0.252926415
0.336797171
0.432383061
0.542322952
0.670112601
0.820483193
1

-49.35366227
-44.37050639
-42.32712565
-40.93872832
-38.10536299
-32.46405236
-24.06312436
-14.78840084
-7.603284929
-3.423599322
0

74.77100773
79.75416361
81.79754435
83.18594168
86.01930701
91.66061764
100.0615456
109.3362692
116.5213851
120.7010707
124.12467

0
-0.594754519
-1.894422697
-3.40619081
-5.151700875
-7.880650797
-13.00989681
-21.77950415
-33.01313953
-40.91867415
-49.35366227

137.903205
137.3084505
136.0087823
134.4970142
132.7515041
130.0225542
124.8933082
116.1237009
104.8900655
96.98453085
88.54954273

After obtaining the

another set of

mix V

mix Cp

the Redlich-Kister (Eq. 9) expansion was used to calculate

values.
(Eq. 9)

mix Cp=x 1 x 2 ai ( x 1x 2 )i
i=0

The R-K expansion was truncated to the 4 th term to achieve a smaller value in the sum of the
square of the residuals. Arbitrary values were assigned for the parameters. The
the data was then subtracted from the

mix Cp

mix Cp

obtained from

obtained from the R-K expansion to obtain the residual,

which was then squared. The sum of the square of the residuals was then obtained.
Partial differentiation of Eq. 9 with respect to

x1

or

x 2 and combining the equation for

calculating partial molar volume yields:

(Eq. 10)

Cp =x 2 a { ( x x ) i+2 i x ( x x )i 1 }
Cp
1
1
2
i
1
2
1
1
2
i

Cp =x a { ( x x ) 2 i x ( x x )
Cp
(Eq. 11)
2
2
1
i
1
2
1 1
2
2

i1

The parameters obtained were using Solver in MS Excel:

a0=-83.15095649
a1= 10.68945365
a2= 6.601005722
a3= -37.88574215

Cp 1 is can be determined by adding the

can be determined by adding the

Cp 1 which is 124.12467 J/mol C and Cp 2 is

Cp 2 which is 137.903205 J/mol C.

Cp 2

Cp 1

Figure 1. Constant-Pressure Partial Molar Heat Capacity for Benzene and Carbon Tetrachloride as a
function of composition