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Name: NAUMAN MITHANI

Student no.: 301016320; group C

Course: CHEM 316

Object: Expt. 3: GAS CHROMATOGRAPHY lab

report

Due date: 13-3-2008


! "!

ABSTRACT:

The first part of this series of "Gas Chromatography" experiments explored

the retention times of individual substances, in a BTEX mixture, based on their

boiling points; it was deemed that retention time is proportional to boiling point.

Secondly, 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 carrier

gas flow rate. By the variation of temperatures, it was determined that higher

temperatures increased resolution but not significantly, and that it must be kept

constant. With the aid of internal standards, the concentrations of the constituents 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-xylene: 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 identification) 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 the stationary

phase. Each constituent of the mixture has a characteristic affinity for the immobile

adsorbing substance and the solvent, and so adsorbs/de-adsorbs 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 eluent is known as the mobile phase and the

opposite as stationary phase. These rates are dependant on physical factors, which this

series of experiments seeks to explain.

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 experiment measures the effect of the speed of the

carrier gas’ flow rate on the retention times (rate of ad/desorption) of the analyte’s

constituents. The second section measures the effects of the column’s temperature on

the retention times, the selectivity (affinity for the stationary to the mobile phase of

the constituents in comparison with one another) of the analyte’s constituents and

resolution. The third seeks to quantify the concentrations of the analyte’s constituents.

The analytes were a BTEX (mixture of benzene, toluene, ethylbenzene,

xylenes) standard and gasoline, dissolved in hexanes with 1,000 ppm bromobenzene.
! $!

EXPERIMENTAL:

The solvent is hexanes, each standard/sample contains 1000 ppm

bromobenzene as internal standard.

The was experiment was commenced by running a sample of hexanes and

collecting the chromatogram data. The oven temperature was set at 55 oC and 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 chromatogram data of these

standards, a 1000 ppm standard of BTEX (mixture of benzene, toluene, 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) measured. 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 20 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 experiment was

concluded once a sample of gasoline (with 1000 ppm bromobenzene internal

standard) was run under the same conditions.


! %!

DATA and RESULTS:

---------------- Section 1 ----------------

boiling point
(oC)
hexanes 69
benzene 80
toluene 110
ethylbenzene 136
p-xylene 138
m-xylene 138
o-xylene 143
bromobenzene 155

! graph depicting retention times (min.) for the compounds analysed under

typical conditions
! &!

! sample chromatogram of toluene standard under intial conditions: oven

temperature 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

temperature 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 flow rate N conc.


H (=L/N) k'
(cm/s) (m/min.) (toluene) (ppm)

15 9 68672 0.0004369 0.261


20 12 60666 0.0004945 0.259 541.882
25 15 212450 0.0001412 0.258 544.349
30 18 57875 0.0005184 0.255 510.601
40 24 149077 0.0002012 0.256 540.185
50 30 88685 0.0003383 0.252 538.355

! 0.003004926 13.858
!/avg. (%) 1.170092396 2.590
! t $2
where N = # R &
"W %

L
H= ; where L = 30 m
N

tr ' tm
k'=
tm

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 ret. Time peak


area % velocity (m/min)
no. (min.) width

1 3.717 0.058 0.0058 8.07102502


2 3.95 0.038 87.1926 7.594936709
BTEX 15 (9 m/min.) 3 4.058 0.059 12.506 7.392804337
4 4.164 0.058 0.1482 7.204610951
5 4.979 0.076 0.1474 6.025306286

1 0.101 0.074 0.0041 297.029703


2 0.868 0.095 0.0873 34.56221198
3 2.698 0.054 0.0022 11.11934766
4 2.885 0.033 88.5829 10.39861352
BTEX 20 (12 5 2.961 0.042 10.632 10.13171226
m/min.) 6 3.633 0.059 0.1319 8.257638315
7 4.836 0.042 0.1665 6.203473945
8 5.008 0.05 0.138 5.990415335
9 5.46 0.07 0.0117 5.494505495
10 6.282 0.088 0.2434 4.775549188

1 2.221 0.057 0.0021 13.50742909


2 2.382 0.038 99.3624 12.59445844
3 2.996 0.026 0.1217 10.01335113
BTEX 25 (15
m/min.) 4 3.992 0.032 0.1527 7.51503006
5 4.135 0.075 0.1266 7.255139057
6 4.506 0.066 0.0108 6.657789614
7 5.193 0.049 0.2236 5.77700751

1 2.013 0.086 99.6203 14.90312966


2 2.526 0.042 0.0709 11.87648456
3 3.362 0.025 0.0892 8.923259964
BTEX 30 (18
m/min.) 4 3.481 0.063 0.0739 8.618213157
5 3.793 0.062 0.0065 7.909306617
6 4.364 0.038 0.1389 6.874427131
7 5.554 0.075 0.0003 5.401512423

BTEX 40 (24 1 1.46 0.066 99.5079 20.54794521


m/min.) 2 1.834 0.019 0.0935 16.35768811
3 2.467 0.04 0.2164 12.16051885
4 2.645 0.026 0.0001 11.34215501
5 2.779 0.021 0.0084 10.79525009
6 3.24 0.047 0.1731 9.259259259
! *+!

7 3.904 0.05 0.0002 7.68442623


8 4.086 0.042 0.0002 7.342143906
9 4.645 0.036 0.0001 6.458557589

1 1.189 0.081 99.4619 25.2312868


2 1.489 0.02 0.1018 20.14775017
3 1.989 0.034 0.2361 15.08295626
4 2.242 0.021 0.0094 13.3809099
BTEX 50 (30 5 2.591 0.032 0.1891 11.5785411
m/min.) 6 3.135 0.09 0.0007 9.56937799
7 3.28 0.033 0.0002 9.146341463
8 3.725 0.044 0.0002 8.053691275
9 5.098 0.043 0.0003 5.884660651
10 5.215 0.055 0.0002 5.752636625
Toluene ; hexanes
! **!

He flow rate
u (m/min.) H (=L/N)
(m/min.)

9 7.594 0.0004369
12 10.390 0.0004945
15 12.590 0.0001412
18 14.903 0.0005184
24 20.547 0.0002012
30 25.231 0.0003383

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 general trend of Van

Deemter plots is not followed.


! *#!

---------------- Section 2 ----------------

! GC 2: Q1, Q3

peak ret. Time peak avg. ret.


area (%) k' Rs avg. Rs
no. (min.) width times
1 0.396 0.036 0.002 -0.821
2 1.9 0.075 0.0022 -0.139 27.099
3 2.208 0.078 88.3848 4.026
BTEX 35
4 2.295 0.025 11.4625 0.039 1.689
at 2.588 11.416
5 2.643 0.023 0.0004 0.197 14.500
35 oC
6 2.845 0.089 0.0022 0.288 3.607
7 3.338 0.056 0.1421 0.512 6.800
8 5.08 0.101 0.0038 1.301 22.191
1 2.013 0.086 99.6203
2 2.526 0.042 0.0709 0.255 8.016
BTEX 55 3 3.362 0.025 0.0892 0.670 24.955
at 4 3.481 0.063 0.0739 0.729 3.585 2.705 12.192
55 oC 5 3.793 0.062 0.0065 0.884 4.992
6 4.364 0.038 0.1389 1.168 11.420
7 5.554 0.075 0.0003 1.759 21.062
1 0.474 0.029 0.0004
2 1.62 0.019 99.402
3 1.847 0.018 0.1132 0.140 12.270
BTEX 75 4 2.159 0.045 0.2622 0.333 9.905
at 5 2.314 0.02 0.0101 0.428 2.598 4.769 14.603
75 oC 6 2.526 0.022 0.21 0.559 10.095
7 2.823 0.033 0.0004 0.743 10.800
8 3.87 0.055 0.0007 1.389 23.795
9 5.751 0.068 0.0011 2.550 30.585
1 1.865 0.065 99.4107
2.065 9.068
BTEX 35 to 2 2.264 0.023 0.1119 0.214 9.068
75 3 2.778 0.067 0.2584 0.490 11.422
at 4 2.994 0.02 0.0104 0.605 4.966
35 to 75 oC 5 3.285 0.049 0.2066 0.761 8.435
(20 oC/min. 6 3.433 0.149 0.0007 0.841 1.495
3.693 7.330
then constant 7 3.65 0.071 0.0006 0.957 1.973
at 75 oC for 3 8 4.035 0.031 0.0002 1.164 7.549
min.) 9 4.518 0.032 0.0002 1.423 15.333
10 4.854 0.058 0.0005 1.603 7.467

When a sample’s 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 components in
! *$!

the BTEX mixture (though hexane is the solvent). Temperature programming allows

for better separation of components of a mixture, as lower boiling point components

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 lower b.p.

components are more accurately separated, the resolution is high but when 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).


! *%!

---------------- Section 3 ----------------

! GC 3: Q2

peak ret. time peak conc.


area (%)
no. (min.) width (ppm)
1 1.832 0.049 99.8777
2 2.248 0.067 0.0161
3 2.563 0.179 0.0025
BTEX 100
4 2.763 0.162 0.027
5 3.257 0.02 0.0715
6 3.702 0.177 0.0052
1 1.691 0.037 0.0517
2 1.842 0.058 99.6747
3 2.256 0.043 0.0533
BTEX 500 4 2.767 0.034 0.1197
5 2.991 0.035 0.0051
6 3.263 0.081 0.0945
7 3.707 0.034 0.001
1 1.845 0.063 99.355
2 2.125 0.06 0.0003
3 2.257 0.033 0.1217 536.8
4 2.771 0.024 0.1547 682.4
BTEX 5 2.835 0.023 0.1285 566.8
1000 6 2.991 0.035 0.0109 48.1
7 3.274 0.048 0.2267 1,000.0
8 3.649 0.109 0.0006
9 4.035 0.03 0.0002
10 4.855 0.083 0.0014
1 1.632 0.072 0.5554
2 1.854 0.066 98.6733
3 2.125 0.021 0.0019
4 2.262 0.02 0.2003
5 2.676 0.023 0.0018
BTEX
2000 6 2.778 0.115 0.4041
7 3.274 0.074 0.1614
8 3.65 0.076 0.0004
9 3.736 0.028 0.0003
10 4.036 0.027 0.0002
11 4.855 0.052 0.001
! *&!

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 (based on

the known concentration of the bromobezene internal standard of 1000 ppm, as shown

previously).

" Benzene: 536.8 ppm

" Toluene: 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


! *'!

conc.
abundance component
(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 longer its retention time, since the molecule is not so much

in the more mobile gaseous phase.

! GC 1: Q5

o-xylene was relatively easier to separate from the the meta and para forms;

but the meta and para forms of xylene were more difficult to separate from

ethylbenzene since there is a lesser difference amongst the boiling points of these than

with o-xylene.

---------------- Section 3 ----------------

! GC 3: Q1

An internal standard is used as a reference; it is a substance, the relevant

characteristics, properties of which are known quantifiably. Signals and readings of

unknowns are measured against 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

the compounds tested. The variation of carrier gas flow rate saw 40 cm/s to be the

most viable rate, providing the lowest H-value. By varying the temperatures, it was

determined that resolution was raised slightly as lower boiling fractions e.g. hexanes

and bezene were prevented from contributing to the chromatogram. Lastly, 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

resolved) and o-xylene: 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.