Ken Yokoyama

CHE 331
April 26, 2003
Dr. Rahni
Experiment 7: GC/MS Analysis of PCB congeners
Objectives
To separate and identify polychlorobiphenyl congeners by gas chromatography
and mass spectrometer (GC/MS)
Theory
GC/MS instrument gives an accurate identification of a compound. It represents a
device that separates chemical mixtures (the GC component) and a very sensitive detector
(the MS component) with a data collector (the computer component). Once the sample
solution is introduced into the GC inlet it is vaporized immediately because of the high
temperature (250C) and swept onto the column by the carrier gas (usually Helium). The
sample flows through the column experiencing the normal separation processes. As the
various sample components emerge from the column opening, they flow into the capillary
column interface. This device is the connection between the GC column and the MS.
Some interfaces are separators and concentrate the sample via removal of the helium
carrier.
The sample then enters the ionization chamber. For electron impact ionization a
collimated beam of electrons impact the sample molecules causing the loss of an electron
from the molecule. A molecule with one electron missing is represented by M+ and is
called the molecular ion (or parent ion). When the resulting peak from this ion is seen in a
mass spectrum, it gives the molecular weight of the compound. Chemical ionization
begins with ionization of methane (or other gas), creating a radical, which in turn will
impact the sample molecule to produce M.H+ molecular ions. Some of the molecular
ions fragment into smaller daughter ions and neutral fragments. Both positive and
negative ions are formed but only positively charged species will be detected.
The next component is a mass analyzer (filter), which separates the positively

charged particles according to their mass. The detector sends information to the
computer, which acts as a "clearing house". It records all the data produced, converts the
electrical impulses into visual displays and hard copy displays. The computer also drives
the mass spectrometer. Identification of a compound based on its mass spectrum relies on
the fact that every compound has a unique fragmentation pattern.
The chlorination of biphenyl can lead to the replacement of 1-10 hydrogen atoms
by chlorine. The chemical formula can be presented as C12H10-nCln, where n is the number
of chlorine atoms in the molecule. The PCBs are chlorinated hydrocarbons that are
manufactured commercially by the progressive chlorination of biphenyl in the presence
of a suitable catalyst (e.g., iron chloride). The yield is always a mixture of different
compounds and congeners. Thus, a total of 209 different chemical components may exist,
but only about 130 of these are likely to occur in commercial products or mixtures of
these compounds. Gas chromatography with packed or capillary columns is generally
used for analysis, and comparison of peak patterns, and various PCB standard
formulations are used for quantification. Different approaches are used for the summingup of individual peaks. Individual congeners are identified using GC, with mass
spectrometry.
Procedure
I.
Turn on the HP 6890 GC System and the HP 5793 Mass Selective Detector
A.
Follow the SOP to operate machine
B.
Set optimum GC and MS SIM/Scan Parameters
II.

Dry Lab
A.
Determine Polychlorobiphenyls from chromatograms
1) 2,4-Dichlorobiphenyl
2) 2,2,5-Trichlorobiphenyl
3) 2,4,4-Trichlorobiphenyl
4) 2,2,3,5-Tetrachlorobiphenyl
5) 2,2,5,5-Tetrachlorobiphenyl
6) 2,3,4,4-Tetrachlorobiphenyl
7) 3,3,4,4-Tetrachlorobiphenyl
8) 2,24,5,5-Pentachlorobiphenyl
9) 2,3,3,4,4-Pentachlorobiphenyl
10) 2,3,4,4,5-Pentachlorobiphenyl
11) 3,3,4,4,5-Pentachlorobiphenyl
12) 2,2,3,3,4,4-Hexachlorobiphenyl

13) 2,2,3,4,4,5-Hexachlorobiphenyl
14) 2,2,4,4,5,5-Hexachlorobiphenyl
15) 2,2,3,3,4,4,5-Heptachlorobiphenyl
16) 2,2,3,4,4,5,5-Heptachlorobiphenyl
17) 2,2,3,4,5,5,6-Heptachlorobiphenyl
18) 2,23,4,4,5,6-Octachlorobiphenyl
19) 2,2,3,3,4,4,5,5,6-Nonylchlorobiphenyl
20) Decachlorobiphenyl
III.

Data and analysis is on hard copy