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1.

Objective
The objective of the experiment is to use the technique of gas chromatography (GC), to
determine the enthalpy of vapourisation, H vap of cyclohexane and toluene by using the
Clausius-Clapeyron equation with measurements of the vapour pressure of the liquid at
various temperatures.
2. Background
The purpose of using GC technique in this experiment is to determine the enthalpy of
vapourisation of volatile compounds, namely toluene and cyclohexane. GC is a good
technique to use as a small amount of sample is required and it works well with impure
substances.
The capacity factor, k, is a measure of time an analyte spends in the stationary phase relative
to the time it spends in the mobile phase. It can be determined using the following equation,
(1)
where t R is the retention time, also known as the time the analyte remains in the column
from the point of injection to point of detection and t M is the void time, also known as the
time of an unretained species, which in this experiment is butane. Both t R and t M can
be obtained from the peaks found in the chromatogram.
In addition, the capacity factor, k, is the ratio of the amount of analyte in stationary phase,
n s , to the amount of the analyte in mobile phase, n M .
(2)
Assuming that the experiment is in ideal gas condition and n s n M , such that n s is
omitted, X s , the mole fraction of analyte in stationary phase is found to approximated to
give k. Thus incorporating Raoults Law and such assumptions into equation (2), simplifying
it will give us
(3)
Further manipulations were
by T and applying natural logarithms to give

done to equation (3) by dividing it

(4)

Equation (4) is then differentiated with respect to temperature, T, with assumption that the
temperature range is small, will give us
(5)
The equation is differentiated with respect to temperature, T gives us
(6)
Substituting equation (6) into (5) follow by an integration of it will give us
(7)
'

In order to find (insert H), a graph of ln

k
T

vs ln

1
T

is plotted to determine the

gradient.
3. Materials and Experimental Procedure
3.1 Materials
Chemicals
a. Butane Gas
b. Dichloromethane (DCM)
c. Cyclohexane
d. Toluene
Precaution: The chemicals used in the experiment are hazardous and flammable. Safety
goggles and gloves must be worn at all times when handling with these chemicals. Ensure
there are no sources of ignition within proximity. Avoid spilling these chemicals on the skin
and direct inhalation as the chemicals are potential carcinogens.
Instrument
a. Gas Chromatography (GC) Instrument
A thin film narrow-base column is used with a capillary of length 30cm, 0.25 m film
thickness of 5% phenyl polysilphenylene siloxane and 0.25mm inner diameter. Flame
ionization detector is used to detect the analyte, which are sensitive to hydrocarbons and low
sample volumes.
3.2 Experimental Procedures
The procedures for the experiment can be found in CBC316 AY12/13 Semester 1 Laboratory
Manual, page 69-71. Two runs were conducted instead of three runs as listed in the laboratory
manual.

4. Data Collection
1.
2. Table 1. Retention Time of Butane
3.
5. Retention Time of Butane /
min
4. Temperat
8. 2n
ure
/
d

7. 1st
ru
9. Aver
run
n
age
11. 2.0
12. 2.0
13. 2.00
10. 60
09
09
9
15. 1.9
16. 1.9
17. 1.93
14. 80
39
39
9
18.
19. Table 2. Retention Time of Dichloromethane (DCM)
20.
22. Retention Time of DCM / min
21. Temperat
25. 2n
ure
/
d

24. 1st
ru
26. Aver
run
n
age
28. 2.2
29. 2.2
30. 2.25
27. 60
57
49
3
32. 2.0
33. 2.0
34. 2.05
31. 80
56
57
7
35.
36. Table 3. Retention Time of Chlorohexanc
37.
38. Temperat
39. Retention Time / min
ure
/
42. DCM
41. Butane, tM

43. Cyclohexane, tR (cyclohexane)

45. 1
st
r
u
n

46. 2
n
d
r
u
n

47. Av
er
ag
e

54. 60

55. 2.
0
0
9

56. 2.
0
0
9

57. 2.
00
9

64. 65

65. 1.
9
8
7

66. 1.
9
8
7

74. 70

75. 1.
9
8
3

76. 1.
9
8
3

77. 1.
98
3

84. 75

85. 1.
9
6
1

86. 1.
9
6
1

87. 1.
96
1

94. 80
104.

95. 1.
9
3
9
105.

96. 1.
9
3
9
106.

85

67. 1.
98
7

97. 1.
93
9
107.

48. 1
s
t
r
u
n
58. 2
.
2
4
7
68. 2
.
1
8
9
78. 2
.
1
4
0
88. 2
.
0
9
6
98. 2
.
0
5
6
108.

49. 2
n
d
r
u
n

79. 2.
1
4
0

80. 2.
14
0

89. 2.
0
9
6

90. 2.
09
6

51. 1
s
t
r
u
n
61. 2
.
9
9
2
71. 2
.
7
6
2
81. 2
.
6
2
7
91. 2
.
5
1
3

50. Av
er
ag
e

59. 2.
2
4
8

60. 2.
24
8

99. 2.
0
5
7
109.

100.
2.057
110.

101.
2.41
7
111.

69. 2.
1
8
9

70. 2.
18
9

52. 2
n
d
r
u
n

53. Av
er
ag
e

62. 2.
9
2
2

63. 2.
99
2

72. 2.
7
6
2

73. 2.
76
2

82. 2.
6
2
7

83. 2.
62
7

92. 2.
5
1
4

93. 2.
51
3

102.
2.417
112.

103.
2.417
113.

114.
124.
125.
126.
127.

90

1.919

1.919

1.919

115.
1.900

116.
1.900

117.
1.900

2.02
2
118.
1.99
0

2.022

2.022

119.
1.992

120.
1.991

2.33
4
121.
2.26
2

2.334

2.334

122.
2.262

123.
2.262

Table 4. Retention Time of Toluene

128.
Te
mperatur
e/

Butane, tM
135.
136.
1st
2nd
r
r
u
u
n
n

137.
Avera
ge

146.
1.939

147.
1.939

131.

144.

80

145.
1.939

154.

85

155.
1.919

156.
1.919

157.
1.919

164.

90

165.
1.899

166.
1.900

167.
1.900

174.

95

175.
1.881

176.
1.882

177.
1.882

184.
0
194.

10

185.
1.865
195.

186.
1.865
196.

187.
1.865
197.

10

129.
132.
138.
1st
r
u
n
148.
2.05
6
158.
2.02
3
168.
1.99
0
178.
1.96
2
188.
1.93
7
198.

Retention Time / min


DCM
139.
2nd
r
140.
u
Avera
n
ge
149.
2.057

150.
2.057

159.
2.023

160.
2.023

169.
1.990

170.
1.990

179.
1.962

180.
1.962

189.
1.937
199.

190.
1.937
200.

133. Toluene, tR (toluene)


141.
142.
1st
2nd
r
r
u
u
n
n
151.
3.06
152.
1
3.061
161.
2.87
162.
3
2.873
171.
2.71
172.
5
2.716
181.
2.58
182.
3
2.583
191.
2.47
192.
1
2.471
201.
202.

143.
Avera
ge
153.
3.061
163.
2.873
173.
2.715
183.
2.583
193.
2.471
203.

5
204.
0

11

1.849

1.849

1.849

205.
1.834

206.
1.833

207.
1.834

1.91
3
208.
1.89
2

1.913

1.913

209.
1.890

210.
1.891

2.37
5
211.
2.29
3

2.375

2.375

212.
2.292

213.
2.293

5. Analysis of Data
214.
215.
5.1 Cyclohexane
216.
217.
Using equation (1), the values of tM and tR

from Table 3 are


'
1
k
substituted in to give k. Further calculations were done to give
and ln
T
T
1
k'
values of cyclohexane which are given in Table 5. Graph of ln
against
of
T
T
cyclohexane, as shown in Figure 1, is plotted to give the experimental H vap of
cyclohexane.
218.
'
1
k
219.
Table 5. Calculated
and ln
values of cyclohexane
T
T
220.
221.

1
T

/
10-3
K-1

223.
3.00

225.
2.96

227.
2.91

229.
2.87
231.

222.
'

ln

k
T

224.
6
.
5
2
3
226.
6
.
7
6
5
228.
6
.
9
6
2
230.
7
.
1
2
0
232.

(cyclohexane)

2.83

233.
2.79

235.
2.75
237.

238.

7
.
2
6
7
234.
7
.
4
1
2
236.
7
.
5
5
2
'

Figure 1. Graph of ln

k
T

against

1
of cyclohexane
T

239.

-6.00
2.70
-6.25

2.75

2.80

2.85

2.90

2.95

3.00

3.05

-6.50
-6.75

f(x) = 4.06x - 18.76


R = 0.99

-7.00
-7.25
-7.50
-7.75
-8.00

240.
241.
242.
243.
244.

Gradient of slope = 4059 K


H vap of cyclohexane = 4059K * 8.314 J.K-

.mol-1
245.
246.

5.2 Toluene
247.
248.

= 33747 J / mol
= 33.75 kJ / mol

Using equation (1), the values of tM and tR (toluene) from Table 4 are substituted in
1
k'
to give k. Further calculations were done to give
and ln
values of toluene
T
T

'

which are given in table 6. Graph of

ln

k
T

1
of toluene, as shown in
T
of toluene.

against

Figure 2, is plotted to give the experimental H vap


249.
1
k'
250.
Table 6. Calculated
and ln
values of toluene
T
T
251.
252.

1
T

/
10-3
K-1

254.
2.83

256.
2.79

258.
2.75

260.
2.72

262.
2.68
264.
2.65

253.

k'
ln
T
255.
6
.
4
1
4
257.
6
.
5
8
0
259.
6
.
7
4
1
261.
6
.
8
9
6
263.
7
.
0
4
6
265.
-

266.
2.61
268.

269.

7
.
1
9
2
267.
7
.
3
3
4
k'
Figure 2. Graph of ln
T

against

1
T

of toluene

270.
271.

-6.00
2.60
-6.25
-6.50
-6.75
-7.00
-7.25
-7.50
-7.75
-8.00

272.

2.65

f(x) = 4.15x - 18.16


R = 1

2.70

2.75

2.80

2.85

273.
274.
275.
276.

Gradient of slope = 4147 K


H vap of toluene = 4147K * 8.314 J.K-1.mol-1
= 34478 J / mol
= 34.48 kJ / mol

277.
278.
279.
6. Results & Discussion
280.
281.
282.
283.
284.
285.
286.
287.
289.

Question 1
H vap of cyclohexane = 33.75 kJ / mol
H vap of toluene = 34.48 kJ / mol
Question 2
H vap
kJmol-1

291.
Cyclohex
ane

288.
293.
E
xperi
294.
mental
33.75
296.
L
iteratu
297.
re
31.08
299.
300.
301.
ExperimentLiterature
Literature
302.
303.
304.
305.

ExperimentLiterature
Literature
306.
307.
308.

292.
T
oluene
295.
4.48

298.
5.88

error

of

cyclohexane

| * 100%
33.7531.08
31.08
= 8.59%
=|

error

of

toluene

| * 100%
34.4835.88
34.48
= 3.90%
=|

309.
310.
There is significant difference between the
experimental value and literature value of cyclohexane due to its rather high % error
of 8.59%. On the other hand, the % error of toluene is 3.90%, which is reasonably
acceptable, within 5%.
311.

312.
Such differences may be due to several factors.
Firstly, the experiment is assumed to be under ideal gas condition. Thus ideal gas law
was applied in order to obtain the integrated equation of Clausius-Clapeyron. Also,
the temperature range is assumed to be small. This leads to an assumption that
R nm
ln
in equation (4) remains constant therefore, causing an elimination of the
sV m
term when equation (4) is differentiated to give equation (5). The equation will no
longer be accurate for calculation of H vap , giving an inaccurate result. In
addition, there may be impurities transferred along with butane gas from the lighter
into the sample vial. While conducting the GC for detection of toluene, we found the
peak of chlorohexane in the chromatogram that is not supposed to be present as it
wasnt included into the sample vial. This may be due to the previous detection of
cyclohexane where some of the cyclohexane may be stuck on the column of the GC
instrument. As the column of the GC instrument wasnt clean after conducting the
detection of chlorohexane, peak of chlorohexane was found while conducting the
detection of toluene. Thus this gives an inaccurate result due to the impurities present.
313.
314.
315.
316.
Question 3
317.
318.
Yes, asymmetric band shapes were observed in the
chromatogram.
319.
320.
There were two peaks that are asymmetric observed
for butane when GC was conducted. This may be due to the impurities that were
transferred along with butane into the sample vial from the fuel of lighter. The relative
intensity of the two peaks are almost similar.
321.
322.
There was asymmetric peak observed in DCM when GC was conducted. This
is due to the tailing effect which is caused by strong interaction between the stationary
phase and the compound, also known as heterogeneity of the stationary surface phase.
Hence, some compound will be retained longer, causing a tailing effect towards the
end of the peak for DCM as a gradually decreasing concentration of the compound is
eluted out of the column. To overcome this, we can increase the mass transfer by
using smaller diameter packing materials, and thinner films of stationary phase. On
theotherhand,this was not apparent during the detection of toluene at 110 as
toluene was evaporated out of the column much faster due to the high temperature,
avoiding any heterogeneity of the stationary phase. Thus, tailing effect was not
observed for detection of toluene under high temperature.
323.
7. References
324.
a. CBC316 AY12/13 Semester 1 Laboratory Manual 2012, 67-71
b. Ellison, H.R. J. Chem. Educ. 2005, 82, 1086-1088
325.
c.
Zs. Papai. Journal of Chromatography A, 2002, 953, 3138
326.
327.
328.

329.