Name:

NAUMAN MITHANI
301016320; group C CHEM 316 Expt. 3: GAS CHROMATOGRAPHY lab
report
Student no.:
Course:
Object:
Due date:
13-3-2008

!
"!
ABSTRACT:
The first part of this series of "Gas Chromatography" experiments explored the r
etention times of individual substances, in a BTEX mixture, based on their boili
ng points; it was deemed that retention time is proportional to boiling point. S
econdly, the effect of flow rate of the carrier gas on isothermal separation of
the BTEX mixture was observed; 40 cm/s (24 m/min.) was deemed to be the ideal ca
rrier gas flow rate. By the variation of temperatures, it was determined that hi
gher temperatures increased resolution but not significantly, and that it must b
e kept constant. With the aid of internal standards, the concentrations of the c
onstituents of BTEX were calculated to be benzene: 536.8 ppm, toluene: 682.4 ppm
(inaccurate), ethylene + m,p-xylenes: 566.8 ppm (b.p.s are to close) and o-xylen
e: 48.1 ppm. The concentrations of these components in the gasoline sample were:
9274 ppm of benzene, 6880 ppm of toluene, 3820 ppm of ethylbenzene, 3420 ppm of
m/p-xylene, 2186 ppm of o-xylene.

!
#!
INTRODUCTION:
This series of experiments is one of the practical realisations of the concepts
of chromatography, an analytical technique of separation (and potential identifi
cation) of substances or compounds in a mixture. It involves running the analyte
in a solvent through a passageway coated with an immobile substance, known as t
he stationary phase. Each constituent of the mixture has a characteristic affini
ty for the immobile adsorbing substance and the solvent, and so adsorbs/de-adsor
bs at its characteristic rate, thus is carried out by the solvent system and/or
carrier gas at a characteristic rate. The analyte present in the solvent or elue
nt is known as the mobile phase and the opposite as stationary phase. These rate
s are dependant on physical factors, which this series of experiments seeks to e
xplain. In this particular Gas chromatography, a carrier gas (He) is used to push or
carry through the analyte, dissolved in hexane and or bromobenzene, through the
column (passageway). The different constituents of the analyte separate and are
detected by an attached flame ionization detector. The first section of the exp
eriment measures the effect of the speed of the carrier gas flow rate on the rete
ntion times (rate of ad/desorption) of the analytes constituents. The second sect
ion measures the effects of the columns temperature on the retention times, the s
electivity (affinity for the stationary to the mobile phase of the constituents
in comparison with one another) of the analytes constituents and resolution. The
third seeks to quantify the concentrations of the analytes constituents. The anal
ytes were a BTEX (mixture of benzene, toluene, ethylbenzene, xylenes) standard a
nd gasoline, dissolved in hexanes with 1,000 ppm bromobenzene.

!
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EXPERIMENTAL:
The solvent is hexanes, each standard/sample contains 1000 ppm bromobenzene as i
nternal standard. The was experiment was commenced by running a sample of hexane
s and collecting the chromatogram data. The oven temperature was set at 55 oC an
d the carrier gas (He) flow rate at 30 cm/s (18 m/min.). Subsequently, 1000 ppm
standards of benzene, toluene, ethylbenzene, xylenes (ortho, meta and para) and
bromobenzene were run singly through the column. Upon collecting the chromatogra
m data of these standards, a 1000 ppm standard of BTEX (mixture of benzene, tolu
ene, ethylbenzene, xylenes) was run. Next, the carrier gas flow rate was varied
to values of 15 cm/s (9 m/min.), 20 cm/s (12 m/min.), 25 cm/s (15 m/min.), 40 cm
/s (24 m/min.) and 50 cm/s (30 m/min.) and the respective chromatogram data(s) m
easured. The analyte was, once again, BTEX. The second section of the experiment
was commenced with resetting the carrier gas flow rate to 30 cm/s. The 1000 ppm
BTEX standard was run at varying temperatures of 35 oC, 55 oC and 75 oC. Next,
the BTEX standard was run under a linear temperature ramp of 35 oC to 75 oC at 2
0 oC/min. with the temperature then constant at 75 oC for 3 minutes. This total
run took 5 minutes. Under identical temperature ramp settings, BTEX standards of
100, 500, 1000 and 2000 ppm concentrations were run through the column. The exp
eriment was concluded once a sample of gasoline (with 1000 ppm bromobenzene inte
rnal standard) was run under the same conditions.

!
%!
DATA and RESULTS:
---------------- Section 1 ---------------boiling point (oC) hexanes benzene tol
uene ethylbenzene p-xylene m-xylene o-xylene bromobenzene 69 80 110 136 138 138
143 155
!
graph depicting retention times (min.) for the compounds analysed under typical
conditions

! ! sample chromatogram of toluene standard under intial conditions: oven temper

ature of 55 oC, carrier gas flow rate of 30 cm/s (18 m/min.)
&!
The peak at ~2 minutes is of the solvent hexane.

! ! sample chromatogram of BTEX standard under intial conditions: oven temperatu

re of 55 oC, carrier gas flow rate of 30 cm/s (18 m/min.)
!
The peak at ~2 minutes is of the solvent hexane.

!
(! GC 1: Q3
!
compound chosen: TOLUENE flow rate (cm/s) 15 20 25 30 40 50 flow rate (m/min.) 9
12 15 18 24 30 N (toluene) 68672 60666 212450 57875 149077 88685 conc. (ppm) 0.
261 0.259 0.258 0.255 0.256 0.252
H (=L/N) 0.0004369 0.0004945 0.0001412 0.0005184 0.0002012 0.0003383
k
541.882 544.349 510.601 540.185 538.355 13.858 2.590
! 0.003004926 !/avg. (%) 1.170092396
! t $2 where N = # R & "W % H= L ; N tr

tm tm where L = 30 m

k =
all quantities based containing time are evaluated in min.
concentration of toluene is calculated as follows:
area of toluene !1000 ppm area of bromobenzene where 1000 ppm is [bromobenzene]

!
)! GC 1: Q4 peak no. 1 2 3 4 5 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 1 2 3 4 5 6 7
1 2 3 4 5 6 ret. Time (min.) 3.717 3.95 4.058 4.164 4.979 0.101 0.868 2.698 2.88
5 2.961 3.633 4.836 5.008 5.46 6.282 2.221 2.382 2.996 3.992 4.135 4.506 5.193 2
.013 2.526 3.362 3.481 3.793 4.364 5.554 1.46 1.834 2.467 2.645 2.779 3.24 peak
width
!
area %
velocity (m/min) 8.07102502 7.594936709 7.392804337 7.204610951 6.025306286 297.
029703 34.56221198 11.11934766 10.39861352 10.13171226 8.257638315 6.203473945 5
.990415335 5.494505495 4.775549188 13.50742909 12.59445844 10.01335113 7.5150300
6 7.255139057 6.657789614 5.77700751 14.90312966 11.87648456 8.923259964 8.61821
3157 7.909306617 6.874427131 5.401512423 20.54794521 16.35768811 12.16051885 11.
34215501 10.79525009 9.259259259
BTEX 15 (9 m/min.)
0.058 0.0058 0.038 87.1926 0.059 12.506 0.058 0.1482 0.076 0.1474 0.074 0.0041 0
.095 0.0873 0.054 0.0022 0.033 88.5829 0.042 10.632 0.059 0.1319 0.042 0.1665 0.
05 0.138 0.07 0.0117 0.088 0.2434 0.057 0.0021 0.038 99.3624 0.026 0.1217 0.032
0.1527 0.075 0.1266 0.066 0.0108 0.049 0.2236 0.086 99.6203 0.042 0.0709 0.025 0
.0892 0.063 0.0739 0.062 0.0065 0.038 0.1389 0.075 0.0003 0.066 99.5079 0.019 0.
0935 0.04 0.2164 0.026 0.0001 0.021 0.0084 0.047 0.1731
BTEX 20 (12 m/min.)
BTEX 25 (15 m/min.)
BTEX 30 (18 m/min.)
BTEX 40 (24 m/min.)

! 7 8 9 1 2 3 4 5 6 7 8 9 10 hexanes 3.904 4.086 4.645 1.189 1.489 1.989 2.242 2

.591 3.135 3.28 3.725 5.098 5.215 0.05 0.042 0.036 0.0002 0.0002 0.0001
*+! 7.68442623 7.342143906 6.458557589 25.2312868 20.14775017 15.08295626 13.380
9099 11.5785411 9.56937799 9.146341463 8.053691275 5.884660651 5.752636625
BTEX 50 (30 m/min.)
0.081 99.4619 0.02 0.1018 0.034 0.2361 0.021 0.0094 0.032 0.1891 0.09 0.0007 0.0
33 0.0002 0.044 0.0002 0.043 0.0003 0.055 0.0002
Toluene
;

! He flow rate (m/min.) 9 12 15 18 24 30 u (m/min.) 7.594 10.390 12.590 14.903 2

0.547 25.231 H (=L/N) 0.0004369 0.0004945 0.0001412 0.0005184 0.0002012 0.000338
3
**!
solvent system: hexanes

!
*"! As can be seen from the graph and the table previously, the optimum solvent
value for H occurs at u of 20.547 m/min., corresponding to carrier gas flow rate
of 24 m/min. (40 cm/s). The first three values cannot be considered since the g
eneral trend of Van Deemter plots is not followed.

!
*#!
---------------- Section 2 ---------------!
GC 2: Q1, Q3
peak no. 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9 10 re
t. Time (min.) 0.396 1.9 2.208 2.295 2.643 2.845 3.338 5.08 2.013 2.526 3.362 3.
481 3.793 4.364 5.554 0.474 1.62 1.847 2.159 2.314 2.526 2.823 3.87 5.751 1.865
2.264 2.778 2.994 3.285 3.433 3.65 4.035 4.518 4.854 peak width 0.036 0.075 0.07
8 0.025 0.023 0.089 0.056 0.101 0.086 0.042 0.025 0.063 0.062 0.038 0.075 0.029
0.019 0.018 0.045 0.02 0.022 0.033 0.055 0.068 0.065 0.023 0.067 0.02 0.049 0.14
9 0.071 0.031 0.032 0.058 avg. ret. times
area (%) 0.002 0.0022 88.3848 11.4625 0.0004 0.0022 0.1421 0.0038 99.6203 0.0709
0.0892 0.0739 0.0065 0.1389 0.0003 0.0004 99.402 0.1132 0.2622 0.0101 0.21 0.00
04 0.0007 0.0011 99.4107 0.1119 0.2584 0.0104 0.2066 0.0007 0.0006 0.0002 0.0002
0.0005
k -0.821 -0.139 0.039 0.197 0.288 0.512 1.301 0.255 0.670 0.729 0.884 1.168 1.7
59
Rs 27.099 4.026 1.689 14.500 3.607 6.800 22.191 8.016 24.955 2.705 4.992 11.420
21.062
avg. Rs
BTEX 35 at 35 oC
2.588
11.416
BTEX 55 at 55 oC
3.585
12.192
BTEX 75 at 75 oC
0.140 0.333 0.428 0.559 0.743 1.389 2.550 0.214 0.490 0.605 0.761 0.841 0.957 1.
164 1.423 1.603
2.598
12.270 9.905 4.769 10.095 10.800 23.795 30.585 9.068 11.422 4.966 8.435 1.495 1.
973 7.549 15.333 7.467
14.603
BTEX 35 to 75 at 35 to 75 oC (20 oC/min. then constant at 75 oC for 3 min.)
2.065
9.068

3.693
7.330
When a samples constituents have wide ranging boiling points, it can be difficult
to separate them; hence the rise in resolution as the temperature is raised to
that of the boiling point of hexanes and close to that of benzene, two component
s in

!
*$!
the BTEX mixture (though hexane is the solvent). Temperature programming allows
for better separation of components of a mixture, as lower boiling point compone
nts are more accurately separated at lower temperatures and vice versa. However,
this trend is not seen clearly in the data. As the temperature rises and the lo
wer b.p. components are more accurately separated, the resolution is high but wh
en it is kept constant at 75 oC, it is reduced (this temperature is far from the
b.p.s of the heavier components of the mixture).

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*%!
---------------- Section 3 ---------------!
GC 3: Q2
peak no. 1 2 3 4 5 6 1 2 3 4 5 6 7 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 11
1.632 1.854 2.125 2.262 2.676 2.778 3.274 3.65 3.736 4.036 4.855 ret. time (min.
) 1.832 2.248 2.563 2.763 3.257 3.702 1.691 1.842 2.256 2.767 2.991 3.263 3.707
1.845 2.125 2.257 2.771 2.835 2.991 3.274 3.649 4.035 4.855 peak width 0.049 0.0
67 0.179 0.162 0.02 0.177 0.037 0.058 0.043 0.034 0.035 0.081 0.034 0.063 0.06 0
.033 0.024 0.023 0.035 0.048 0.109 0.03 0.083 0.072 0.066 0.021 0.02 0.023 0.115
0.074 0.076 0.028 0.027 0.052 conc. (ppm)
area (%) 99.8777 0.0161 0.0025 0.027 0.0715 0.0052 0.0517 99.6747 0.0533 0.1197
0.0051 0.0945 0.001 99.355 0.0003 0.1217 0.1547 0.1285 0.0109 0.2267 0.0006 0.00
02 0.0014 0.5554 98.6733 0.0019 0.2003 0.0018 0.4041 0.1614 0.0004 0.0003 0.0002
0.001
BTEX 100
BTEX 500
BTEX 1000
536.8 682.4 566.8 48.1 1,000.0
BTEX 2000

! The 1000 ppm sample of BTEX was deemed to provide the best resolution and was
*&!
therefore used in calculating the concentrations of the constituents of BTEX (ba
sed on the known concentration of the bromobezene internal standard of 1000 ppm,
as shown previously). " " " Benzene: Toluene: 536.8 ppm 682.4 ppm (27 % higher
than calculated earlier)
Ethylbenzene + m/p xylenes: 566.8 ppm (due to their approximate b.p.s, they could
not be resolved)
"
o-xylene:
48.1 ppm
!
GC 3: Q3 graph of abundance vs. ret. time of gasoline sample containing BTEX
solvent hexane; internal standard: 1000 ppm bromobenzene

! abundance component conc. (ppm)

* !
0.294
benzene
9,274
0.2181
toluene
6,880
0.1211
ethylbenzene
3,820
0.1084
m,p-xylene
3,420
0.0693
o-xylene
2,186
0.0317
bromobenzene
1,000
Concentrations: component area bromobenzene area ! [bromobenzene]

!
*(!
DISCUSSION:
---------------- Section 1 ---------------! GC 1: Q2 Generally, the greater the
molecular weight of the molecule, the higher its boiling point (b.p.) and the lo
nger its retention time, since the molecule is not so much in the more mobile ga
seous phase.
!
GC 1: Q5 o-xylene was relatively easier to separate from the the meta and para f
orms;
but the meta and para forms of xylene were more difficult to separate from ethyl
benzene since there is a lesser difference amongst the boiling points of these t
han with o-xylene.
---------------- Section 3 ---------------! GC 3: Q1 An internal standard is use
d as a reference; it is a substance, the relevant characteristics, properties of
which are known quantifiably. Signals and readings of unknowns are measured aga
inst those of the standard, the concentration of which e.g. is known, and so the
concentration of the unknown may calculated by ratios.

!
*)!
CONCLUSION:
It was observed that the ret. times were proportional to the boiling points of t
he compounds tested. The variation of carrier gas flow rate saw 40 cm/s to be th
e most viable rate, providing the lowest H-value. By varying the temperatures, i
t was determined that resolution was raised slightly as lower boiling fractions
e.g. hexanes and bezene were prevented from contributing to the chromatogram. La
stly, the concentrations of the constituents of BTEX were, against the 1000 ppm
bromobenzene internal standard, measure to be benzene: 536.8 ppm, toluene: 682.4
ppm (inaccurate), ethylene + m,p-xylenes: 566.8 ppm (b.p.s are to close to be re
solved) and o-xylene: 48.1 ppm. The concentrations of these components in the ga
soline sample were 9274 ppm of benzene, 6880 ppm of toluene, 3820 ppm of ethylbe
nzene, 3420 ppm of m/p-xylene, 2186 ppm of o-xylene.