Chemosphere, Vol. 31, No. 2, pp. 2687-2705, 1995
l'erg~o.
Copyright © 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0045-6535/95 $9.50+0.00
0045°6535(95)00140-9
PHYSICAL,
SPECTRAL
OF
ALL
AND
209
CHROMATOGRAPHIC
INDIVIDUAL
PCB
PROPERTIES
CONGENERS
M i c h a e l Bolgar*, J a m e s Cunningham, R u s s e l l Cooper, R i c h a r d K o z l o s k i and
Jack Hubball, A c c u S t a n d a r d Inc., 25 S c i e n c e Park, N e w Haven, CT 06511 and;
Don P. Miller, T e r r y Crone, H a r r y Kimball, A n i t a Janooby, B a r r y M i l l e r
and B i l l y Fairless, USEPA, R e g i o n 7, E n v i r o n m e n t a l S e r v i c e s Division, Kansas
City, K a n s a s 66115.
(Received in Germany 1 March 1995; accepted 28 April 1995)
ABSTRACT :
Physical, spectral and chromatographic data for all 209 individual PCB congeners is presented. The individual congeners were synthesized and then isolated
and purified.
Recent emphasis on the source of the toxicity of commercial PCB
formulations has increased the need for a complete set of the PCB congeners.
Through the use of two capillary GC columns: 40% octadecyl/ 15% phenyl methyl siloxane and 50% phenyl methyl siloxane, it was possible to separate 201 PCB congeners with only four unresolved pairs. The data compiled in this study for all 209
congeners will aid in the identification of selected individual components of
these environmental pollutants. The use of this data also presents the opportunity for the improved quantification of the commercial PCB formulations.
INTRODUCTION:
Polychlorinated biphenyls
s p e c t r u m of a n a l y t i c a l
(PCB'S) h a v e b e e n the subject of a b r o a d
and e n v i r o n m e n t a l
The c o m b i n a t i o n of t h e i r w i d e s p r e a d use,
studies over the p a s t 25 years.
environmental persistence,
p r o p e r d i s p o s a l has led to e c o s y s t e m c o n t a m i n a t i o n on a g l o b a l
Of p a r t i c u l a r
interest
is the h i g h p o t e n t i a l
t h r o u g h the food chain,
pounds by humans.
for b i o a c c u m u l a t i o n
(1-4).
of PCB's
(5,6).
found in h u m a n blood,
M o r e importantly,
p o i s o n i n g s via PCB i n g e s t i o n h a v e b e e n d o c u m e n t e d
Commercial
and im-
r e s u l t i n g u l t i m a t e l y in the i n g e s t i o n of these com-
PCB r e s i d u e s are f r e q u e n t l y
tissue and b r e a s t m i l k
level
PCB p r o d u c t s
several
adipose
i n s t a n c e s of h u m a n
(7).
(Aroclor ~, C h l o r p h e n ~, K a n n e c h l o r ~ and
F e n c l o r TM) c o n t a i n m a n y of the p o s s i b l e PCB congeners;
and recent r e s e a r c h
has f o c u s e d on the p r e m i s e that the t o x i c i t y of t h e s e p r o d u c t s
can be esti-
m a t e d by the i d e n t i f i c a t i o n and q u a n t i f i c a t i o n of s e l e c t e d PCB c o n g e n e r s
ii) .
The m o s t
(8-
toxic c o n g e n e r s are those w h i c h can adopt a c o p l a n a r configu-
ration s i m i l a r to that of 2 , 3 , 7 , 8 - T C D D
most toxic PCB c o n g e n e r s
(10,12).
In this regard,
s t u d i e d to date are IUPAC #77,
the three
126 and 169.
Addi-
tional c o n g e n e r s w h i c h p o s s e s s a p a r t i a l l y p l a n a r c o n f i g u r a t i o n are also of
interest,
and Y a n g et al
responsible
(10)
for b i o l o g i c a l
l i s t e d 19 such PCB c o n g e n e r s
activity.
t h o u g h t to be
The c h l o r i n e s u b s t i t u t i o n p a t t e r n com2687
2688
mon to all of these congeners is the lack of chlorines in the ortho positions.
This congener-specific toxicological premise has provided the moti-
vation for the development of analytical procedures which y i e l d reliable
separations.
This task is made more difficult in "real world" environmental samples
by the presence of interfering compounds
(e.g. DDT, DDE) which are often
present at m u c h higher concentrations than the target compounds.
quently,
Conse-
two basic approaches have been developed to improve the separation
of these multicomponent pollutants.
The first approach employs the pre-
parative separation of the extract or mixture followed by analysis using
high resolution or m u l t i - d i m e n s i o n a l GC.
The second approach relies on the
direct characterization of the extract or mixture via a congener-specific
high resolution GC column
(13-15) or multi-dimensional GC
(16-18).
Both approaches require the use of accurate, w e l l - c h a r a c t e r i z e d spiking, calibration and QC solutions.
These solutions contain the appropriate
PCB congeners to determine elution patterns,
establish response factors,
monitor the efficiency of clean-up and recovery procedures.
These ap-
proaches require all the congeners present in the commercial products and
are facilitated by the availability of all 209 PCB congeners.
This report describes the first preparative isolation of all 209 individual PCB congeners from synthetic mixtures subsequently providing the
opportunity to determine the physical characteristics of the entire set.
Data obtained on these compounds include melting points,
high resolution
gas chromatography retention indices on two columns of differing selectivity,
electron capture detector response factors, matrix isolated FT/IR
spectra and electron impact mass spectra.
MATERIALS
AND
METHODS
:
A. Chemicals: The 2-,3-,
and 4-chloroanilines,
3,5-, and 3,4-dichloroanilines,
2,4,6,-,
2,4,5-,
2,6-,
2,5-,
2,4-,
2,3-,
and 2,3,4-
trichloroanilines as well as 2,3,5,6- and 2,3,4,5-tetrachloranilines were
purchased from A l d r i c h Chemical Co.
and 1,2-dichlorobenzene,
1,2,4-,
Benzene,
1,2,3-,
chlorobenzene,
1,4-,
1,3,5-trichlorobenzene,
1,3-,
1,2,4,5-
tetrachlorobenzene and pentachlorobenzene were p u r c h a s e d from Aldrich
Chemical Co.
2,3,5-,
Isoamyl nitrite was obtained from Eastman Organic Chemicals.
2,3,6-,
3,4,5-trichloroanilines, 2,3,4,6-tetrachloroaniline,
1,2,3,4- and 1,2,3,5-tetrachlorobenzene were prepared at AccuStandard's
laboratories using standard methods.
B. Synthesis Schemes: All 209 congeners were synthesized by one or
more of the following schemes outlined in Figure i.
C. Isolation and Purification: All reaction products were isolated as
2689
Cl,.
CI.
CI,.
Cl,.
CI
la
lib ~ )
CI.
CI,.
+e
NH=
CI.
RONO~,
(m = 0-5, n = 1-5, R = aliphatic)
CI,.
CI.
CI,.
DMF, heat
CI
CIm
~>
CI,.
+
CI.
CI.
+
(m = 1-5, n = 1-5)
(CH=CO)=O
3a
3b
CI
H°
H=N
(CH=CO)=O
CI=
NH= I :>
H=N
CIm
~
N=H--((
CI
~
})-((
CI
aqHONO
)~-- NH= ^ ^. > Cl ~
CI-
-Cl
CI
CI
H.
CI
CI
CI
I
.q o o
N=
NH=
CI.
Cir.
HsPO4
CI
Cl~
(m = 1-5, n = 1-5)
(m = 1-5, n = 1-5)
6
CI
CI
CI
CI +
CI
A
CI
e
z
CHsCH2MgBr
THF
~'
CI
Figure 1. Synthesis schemes for all 209 PCB congeners
la
lb
2
3a
3b
4
5
6
CI
CI
NH= Cu=Cl=:>
~ _ .
/~-----~
CI
CI= ~'
CI
CI
/~
Gomberg - Bachman reaction
Cadogan modification of Gomberg - Bachman reaction
UIImanreaction
Chlorination of benzidine followed by dearnination
Chlorination of benzidine followed by Sandmeyer reaction
Chlorination
Sandmeyer reaction
Gdgnardcoupling
CI
Cl.+1
2690
the m e t h y l e n e
subsequently
chloride
passed
ing a d s o r b e n t s :
appropriate
were
silica
solvent
stripped
one or m o r e
soluble
through
gel,
solvents
The r e s i d u e s
containing
alumina,
Florisil
system.
to d r y n e s s
fractions.
a column
The
fractions
and the r e s id u e s
such as acetone,
and/or
TM
Hewlett
jector
Packard
and a N i c k e l
0.25mm x
25~m
fused s i l i c a
0.25~m
5890 GC e q u i p p e d
63 e l e c t r o n
h e l i u m as the c a r r i e r
(2 min.)
to 300°C
splitless
jector
mode.
of the
calculated
PCB c o n g e n e r s
(OCN) .
The
relative
of each
set at 250°C
were
response
silica
x
capillary
sample was
(by weight)
obtained
One
in the
i00 ng/~L.
respectively.
relative
using
from 150°C
for 5 m i n u t e s .
the a u t o s a m p l e r
computed
factors
siloxane
a 25M x 0 . 2 5 ~
fused
in-
a 50M x
was p r o g r a m m e d
and 300°C,
to O C N u s i n g v a l u e s
1 was
methyl
at 30 p s i g h e a d p r e s s u r e
and h e l d at 300°C
The c o n c e n t r a t i o n
were
2 was
temperature
w e r e m a d e via
on a
split/splitless
Column
siloxane
operated
The oven
injections
and d e t e c t o r
naphthalene
gas.
methyl
were
at 5°C/minute,
(I.0~L)
tion times
substituted
Both columns
from
or toluene.
substituted
Column
an
congeners
runs w e r e p e r f o r m e d
detector.
15% p h e n y l
(Quadrex Corp.).
f i l m 50% p h e n y l
(Quadrex Corp.).
microlitre
capture
using
target
and
follow-
crystallized
methanol
w i t h an autosampler,
film 40% octadecyl,
capillary
the
fractionally
D. Chromatography: All gas c h r o m a t o g r a p h i c
distilled
of the
charcoal
containing
hexane,
were
one or m o r e
The
The
in-
reten-
to o c t a c h l o r o -
for the c o n g e n e r s
from i n t e g r a t e d
peak
were
ar-
eas.
E. Gas Chromatography~Mass Spectrometry: All mass
tained
on a H e w l e t t
selective
each
Packard model
detector.
PCB c o n g e n e r
5% p h e n y l
(i00 n g / ~ L
substituted
methyl
chemstation
software
DOS b a s e d
impact
samples.
1.0 ~L samples
column
The M S D was
spectra
ob-
of
A 25M x 0 . 2 5 m m x 0 . 2 5 ~ m
capillary
and autotuned
mass
were
to a HP 5 9 7 1 A mass
to inject
concentration).
all
Electron
was u s e d
siloxane
u s e d to c h r o m a t o g r a p h
standard.
5890 GC i n t e r f a c e d
An a u t o s a m p l e r
spectra
(Quadrex
controlled
using
DFTPP
were obtained
film
Corp.)
was
by a HP
as the t u n i n g
over
the r a n g e
of 50-
520 amu.
F. M a t r i x Isolated Gas C h r o m a t o g r a p h y ~ F o u r i e r Transform Infrared Spectrometry: A M a t t s o n
Scientific
ate the IR spectra.
model
5 8 9 0 A GC
equipped
with
controlled
interfaced
a broadband
by a Pixel
tion detector.
25°C/min,
then
Fifty
a Mattson
computer.
Sirius m o d e l
and s a m p l e
The GC was
c o l u m n was
was
nanograms
at 5°C/min,
GC/FT-IR
employed
100 F T - I R
with
f r o m 50°C
and h e l d at 320°C
PCB was
used
The
to generPackard
spectrometer
s y s t e m was
a flame
a 30M x 0 . 3 2 m m x 0 . 2 5 ~ m
i0 p s i g u s i n g h e l i u m / a r g o n
of each
was
a Hewlett
chamber.
equipped
The GC oven was prograr~ned
to 320°C
umn h e a d p r e s s u r e
gas.
to
instrument
MCT detector
The a n a l y t i c a l
(J&W S c i e n t i f i c ) .
Matrix-Isolated
The C r y o l e c t
injected
(i min)
ionizafilm DB-5
to 120°C
for 7 m i n u t e s .
(98.5/1.5%)
on-column.
at
Col-
as the carrier
The c o l u m n
el-
2691
fluent was split with 80% going to the Cryolect
for spectral analysis and
20% going to the FID for quantitation and measurement
of retention times.
G. Melting points: All melting points were obtained on a Fisher Johns
melting point apparatus.
The melting point was determined by rapidly el-
evating the temperature to a point 20-25°C below the approximate melting
point and then raising the temperature at a rate of l-2°C/minute.
ing points were corrected using melting point standards
RESULTS
AND
The melt-
(Aldrich).
DISCUSSION:
Synthesis
Schemes:
The synthesis of all 209 PCB congeners proceeded via
the schemes presented in the Materials
specific reaction scheme(s)
& Methods Section.
Table I lists the
used in synthesizing each congener.
Table 1. Reaction scheme(s) needed to synthesize each individual PCB congener
BZ#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
Compound
2-Chlorobiphenyl
3-Chlorobiphenyl
4-Chlorobiphenyl
2,2'-Dichlorobiphenyl
2,3-Dichlon>biphenyl
2,3'-Dichlorobiphenyl
2,4-Dichlorobiphenyl
2,4'-Dichlorobiphenyl
2,5-Dichlorobiphenyl
2,6-Dichlorobiphenyl
3,3'-Dichlorobiphenyl
3,4-Dichlorobiphenyl
3,4'-Dichlorobiphenyl
3,5-Dichlorobiphenyl
4,4'-Dichlorobiphenyl
2,2',3-Tnchlorobiphenyl
2,2',4-Tdchlorobiphenyl
2,2',5-Trichlorobiphenyl
2,2',6-Tdchlorobiphenyl
2,3,3'-Tdchlorobiphenyl
2,3,4-Trichlorobiphenyl
2,3,4'-Trichlorobiphenyl
2,3,5-Tdchlorobiphenyl
2,3,6-Tdchlorobiphenyl
2,3',4-Trichlorobiphenyl
2,3',5-Trichlorobiphenyl
2,3',6-Tdchlombiphenyl
2,4,4'-Trichlorobiphenyl
2,4,5-Trichlorobipheny(
2,4,6-Trichlorobiphenyl
2,4',5-Trichlorobiphenyl
2,4',6-Trichlorobiphenyl
2',3,4-Trichlorobiphenyl
2',3,5-Tdchlorobiphenyl
3,3',4-Tdchlorobiphenyl
3,3',5-Tdchlombiphenyl
3,4,4'-Tdchlombiphenyl
3,4,5-T dchlorobiphenyl
3,4',5-Tdchlorobiphenyl
2,2',3,3'-Tetrachlorobiphenyl
2,2',3,4-Tetmchlorobiphenyl
2,2',3,4'-Tetra~lo mbiphenyl
2,2',3,5-Tetrachlorobiphenyl
2,2',3,5'-Tetmchlo robiphenyl
2,2',3,6-Tetrachlorobiphenyl
2,2',3,6'-Tetrachlorobiphenyl
2,2',4,4'-TetmchtorobLphenyl
2,2',4,5-Tet rachlorobiphenyl
2,2',4,5'-Tetrachlorobiphenyl
2,2',4,6-Tetrachlorobiphenyl
Reaction Scheme
la, lb
la, lb
la, lb
la, lb, 2
la, lb
1¢ lb
ls, lb
lb, 2, 5
la, Ib
la, Ib
2
la, Ib
la, Ib
la, Ib
la, Ib, 2
la, Ib
Is, Ib
la, lb
la, Ib,2
la, Ib, 2
la, Ib
la, Ib, 2
Is, Ib
ls, Ib
la, Ib, 2
la, Ib, 2
la, lb, 2
la, lb, 2, 5
la, lb
la, Ib
la, lb, 2
la, Ib, 2
la, lb, 2
la, lb, 2
la, lb
la, Ib
la, Ib
la, Ib
la, Ib
la, lb, 2
la, lb
la, lb
la, lb
la, lb
1¢ lb, 2
la, lb, 2
2
1¢ lb
la, lb
la, lb, 2
BZ#
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
Compound
2,2',4,6'-Tetmchlorobiphenyl
2,2',5,5'-Tetrachlorobiphenyl
2~',5,6'-Tetrachlorobiphenyl
2~',6,6'-Tetrachlorobiphenyl
2,3,3',4-Tetrachlorobiphenyl
2,3,3',4'-Tetmchlorobiphenyl
2,3,3',5-Tetrachlorobiphenyl
2,3,3',5'-Tetrachlorobiphenyl
2,3,3',6-Tetmchlorobiphenyl
2,3,4,4'-Tetrachlorobiphenyl
2,3,4,5-Tetmchlorobiphenyl
2,3,4,6-Tetmchlorobiphenyl
2,3, 4',5-Tetmchlorobiphenyl
2,3, 4',6-Tetrachlorobiphenyl
2,3,5,6-Tetmchlorobiphenyl
2,3',4,4'-Tetmchlo robiphenyl
2,3',4,5-Tetnachlorobiphenyl
2,3',4,5'-Tetmchlo robiphenyl
2,3',4,6-Tetmchlorobiphenyl
2,3',4',5-Tetrachlorobiphenyl
2,3',4',6-Tetmchlorobiphenyl
2,3',5,5'-Tetrachlorobiphenyl
2,3',5',6-Tetmchlombiphenyt
2,4,4',5-Tetmchlombiphenyl
2,4,4',6-Tetmchlombiphenyl
2',3,4,5-Tetmchlorobiphenyl
3,3',4,4'-Tetrad~lorobiphenyl
3,3',4,5-Tetmchlorobiphenyl
3,3',4,5'-Tetmchlorobiphenyl
3,3',5,5'-Tetmchlorobiphenyl
3,4,4',5-Tetrachlorobiphenyl
2,2',3,3',4-Pentachlorobiphenyl
2,2',3,3',5-Pentachlorobiphenyl
2,2',3,3',6-Pentachlorobiphenyl
2,2',3,4,4'-Pentachlorobiphenyl
2,2',3,4,5-Pentachlorobiphenyl
2,2',3,4,5'-Pentachlorobiphenyl
2,2',3,4,6-Pentachlorobiphenyl
2,2',3,4,6'-Pentachlorobiphenyl
2,2',3,4',5-Pentachlorobiphenyl
2,2',3,4',6-Pentachlorobiphenyl
2,2',3,5,5'-Pentachlorobiphenyl
2,2',3,5,6-Pentachlorobiphenyl
2,2',3,5,6'-Pentachlorobiphenyl
2,2',3,5',6-Pentachlorobiphenyl
2,2',3,6,6'-Pentachlorobiphenyl
2,2',3',4,5-Pentachlorobiphenyl
2,2',3',4,6-Pentachlorobiphenyl
2,2',4,4',5-Pentachlorobiphenyl
2,2',4,4',6-Pentachlorobiphenyl
Reaction Scheme
la, lb, 2
la, lb, 2
la, lb, 2
la, lb, 2
la, lb, 2
la, lb, 2
2
la, lb
2
la, lb
la, lb
la, lb
2
la, lb,2
la, lb
la, 1b, 2
la, lb,2
la, I b, 2
la, lb
la, 1b, 2
la, lb
la, lb, 2
la, lb
la, lb, 2
1==,lb
la, lb, 2
lb, 2
lb
la, lb
la, 3a
la, lb
ls, Ib
la, Ib
la, Ib
la, Ib
la, lb
la, lb
1b, 2
lb, 2
la, lb
la, lb, 2
la, lb
lb, 2
la, lb, 2
la, lb
la, lb
lb, 2
lb, 2
la, lb
lb, 2
2692
Table I. Reaction scheme(s) needed to synthesize each individual PCB congener (continued)
BZ#
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
Compound
Reaction S c h e m e
2,2',4,5,5'-P(mtachlorobiphenyl
2,2',4,5,6'-Pentachlombiphenyl
2,2',4,5',6-Pent~chlorobiphenyl
2,2',4, 6,6'- Pen tachlo robiphenyl
2,3,3',4,4'-Pentachlombiphenyl
2,3,3',4,5-Pentachlorobiph='ny~
2,3,3',4',5-Pentachlorobiphenyl
2,3,3',4,5'-Pentachlorobiphenyl
2,3,3',4,6-P='ntachlorobiphenyl
2,3,3',4',6-Pentachlorobiphenyl
2,3,3',5,5'-Pentachlorobiphenyl
2,3,3',5,6-Pentachlorobiphenyl
2,3,3',5',6-Pentachlorobiphenyl
2,3, 4,4',5-Pentacldorobiphenyl
2,3,4,4',6-Pentachlorobiph='nyl
2,3,4,5,6-Pentachlorobipheny/
2,3,4',5,6-Pentachlorobiphenyl
2,3',4,4',5- Pentachlo robiphenyl
2,3',4,4',6-Pwttachlorobiphenyl
2,3',4,5,5'-Pet'dachlorobiphenyl
2,3',4,5',6-Pentachlorobiphenyl
2',3,3',4,5-Pentachlorobiphenyl
2',3,4,4',5- Peo tachlo robiphe ny|
2',3,4,5,5'-Peotachlorobiphenyl
2',3,4,5,6'- Pentachlo mbiphenyl
3,3',4, 4',5- Pentachlo roblphenyl
3,3',4, 5,5'- Pen tachlo mbiphenyl
2,2',3,3',4,4'-Hexachlorobiphenyl
2,2',3,3',4,5-Hexachlorobiphenyl
2,2',3,3',4,5-Hexachlorobiphenyl
2,2',3,3',4,6-H='xachlorobiphenyl
2,2',3,3',4,6'-Hexachlorobiphenyl
2,2',3, 3',5,6' -H exachlo robiphenyl
2,2',3,3',5,6-Hexa~hlorobiphenyl
2,2',3,3',5,6'-Hexachlo robipher, yl
2,2',3,3',6,6'-Hexachlorobiphenyl
2,2',3,4,4',5-Hexacldorobiphenyl
2,2',3,4,4', 5'-Hexachlo mbiphe nyl
2,2',3,4,4',6-H='xachlorobiphenyf
2,2',3,4,4',6'-Hexachlo mbiphenyl
2,2',3,4,5,5'-Hexachlorobiphenyl
2,2',3,4,5,6-Hexachlorobiphenyl
2,2',3,4,S,6'-Hexachlorobiphenyf
2,2',3,4,5',6-Hexachlorobiphenyl
2,2',3,4,6,6'-Hexachlorobiphenyl
2,2',3,4',5,5'-H='xachlorobiphenyl
2,2',3,4',5, 6-H='xachlorobiphenyf
2,2',3,4',5,6'- Hexachlo robiphenyl
2,2',3,4',5',6-Hexachlo robiphertyt
2,2',3,4',6,6'-Hexachlo robiphenyl
2,2',3,5,5',6-Hexaddorobiphenyl
2,2',3,5,6,6'-Hexach/orobiphenyl
2,2',4,4',5, 5'-Hexachlo robiphenyl
2,2',4,4',5, 6'-Hexachlo robiphenyl
2,2',4,4',6,6'-Hexachlorobiphenyl
Gas C h r o m a t o g r a p h i c
int e r n a l
standard
tive
response
data
from this
retention
piled
comparison
OCN.
study
data.
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
1gO
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
obtained
Compound
This was
of r e l a t i v e
done
integrated
areas
by M u l l i n
factors
between
(OCN)
each
times
in this
as the
and rela-
a comparison
calculated
specific
lb
lb
lb, 2
lb
lb, 6
la, lb
lb, 2
lb, 2
1b, 2
lb, 2
lb, 6
lb
lb, 2
lb, 2, 3b
lb
lb
lb
lb
lb
lb
Ib
lb, 2
lb, 2
lb
lb
la, lb
lb, 2
lb, 2
lb
la, lb
1a, 1b
lb, 2
lb, 2
1=', lb,2
1=', 6
lb, 2
la, lb, 2
1b, 2
lb, 2
lb, 2
lb, 2
lb
lb, 2
lb
Ib
lb, 2
lb, 2
1=', lb, 2
lb
lb, 2
lb, 2
lb
1b
4
chosen
and co-workers
used
were
was
retention
to f a c i l i t a t e
on the two GC c o l u m n s
The r e s p o n s e
Reaction S c h e m e
2,3,3',4,4',5-Hexachlorobiphenyl
2,3,3',4,4',5'-Hexachlo robiphenyl
2,3,3',4,4',6-Hexachlorobiphenyl
2,3,3',4,5,5'-Hexachlorob~phenyl
2,3,3',4,5,6-Hexachlorobipheny(
2,3,3',4,5',6~Hexachlorobiphenyl
2,3,3',4',5,5'-Hexachlorobiphenyl
2,3,3',4',5,6-Hexachlorobiphenyl
2,3,3',4',5',6-Hexachlorobipheny]
2,3,3',5,5',6-Hexachlorobiphenyl
2,3,4,4',5,6-Hexachlorobiphenyl
2,3',4,4',5,5'-Hexachlorobiphenyl
2,3',4,4',5',6-Hexachlo robiphenyl
3,3',4,4',5,5'-Hexachlorobiphenyl
2,2',3,3',4,4',5-Heptachlo robiphenyl
2,2',3,3',4,4',6-Heptachlombiphenyl
2,2',3,3',4,S,5'- Heptach/orobiphenyl
2,2',3,3',4,5,6-HeptachJorobiphenyl
2,2',3,3',4,5,6'-Heptachlorobiphenyl
2,2',3,3',4,5',6-Heptachlorobiphenyl
2,2',3,3',4,6,6'- Heptachlorobiphenyl
2,2',3,3',4',5,6- Heptachlo robiphe nyl
2,2',3, 3',5,5',6- Heptachlo robiphenyl
2,2',3,3',5,6,6'-Heptachlorobiphenyl
2,2',3,4,4',5,8'-Heptachlorobiphenyl
2,2',3,4,4',5,6-Heptachlorobiphenyl
2,2',3,4,4',5,6'-Heptachlorobiphenyl
2,2',3,4,4',5',6-Heptachlo robiphenyl
2,2',3,4,4',6,6'-Heptachlorobiphenyl
2,2',3,4,5,5',6-Heptachlorobiphenyl
2,2',3,4,5,6,6'-Heptachlorobiphenyl
2,2',3,4',5, 5',6- Hep tachlo robiphenyl
2,2',3,4',5,6,6'- Heptachlo robiphenyl
2,3,3',4,4',5,5'-Heptachlorobiphenyl
2,3,3',4,4',5,6-Heptachlorobiphenyl
2,3,3', 4, 4', 5',6- Heptachlorobiphenyl
2,3,3',4,5,5',6-Heptachlorobiphenyl
2,3,3',4',5,5',6- Heptschlorobiphenyl
2,2',3, 3',4,4',5, 5' -Octad'dorobiphenyl
2,2',3,3',4,4',5,6-Octachlo robiphenyl
2,2',3,3',4,4',8',6-Octachlorobiphenyl
2,2',3,3',4,4',6,6'-Octachlorob~phectyl
2,2',3,3',4,5,5',6-Octachlo robiphenyl
2,2',3,3',4,5,6,6'-Octachlorobiphenyl
2,2',3,3',4,5',6,6'-Octachlorobiphenyl
2,2',3,3',4,5,5',6'-Octachlorobiphenyl
2,2',3,3',5, 5',6,6'-Octach|orobiph en yl
2,2',3,4,4',5,5',6-Octachlorobiphenyl
2,2',3,4,4',5,6,6'-Octachlorobipheny(
2,3, 3',4,4',5,5',6-Octachlorobiphenyl
2,2',3,3',4,4',5,5',6-Nonachlorobiphenyl
2,2',3,3',4,4',5,6,6'-Nonachlorobiphenyl
2,2',3,3',4,5,5',6,6'-N onachlorobiphenyl
2,2',3,3',4, 4',5, 5',6, 6' -Decachlo robiphenyl
Octachloronaphthalene
and that p u b l i s h e d
to OCN.
of the
Data:
for the c o m p i l a t i o n
factor
times
relative
BZ#
la, lb
1-, lb, 2
la, lb, 2
lb
la, lb, 2
1=,, lb, 2
1=,, lb, 2
la, lb, 2
la, lb, 2
1=', lb, 2
la, lb, 2
lb, 2
1=', lb, 2
lb, 2
lb, 2
1=', lb, 2, 6
lb, 2
la, lb, 2
1=', lb, 2
1=,, lb, 2
1=', lb, 2
la, lb, 2
lb, 2
1,,, lb, 2
1=', lb
1=', lb
1=', lb
lb, 2
1=', lb
1=', lb, 2
la, lb, 2
lb, 2
la, 2
1,=, lb, 2
la, lb
lb, 2
1=,, lb
lb
1=', lb, 2
lb
1=', lb, 2
la, lb, 2
la, lb, 2
1=', lb, 2
la, lb, 2
lb
la, lb
lb, 2
1b, 2
lb
la, lb, 2
1=', lb
2
1b
lb, 2
between
(19).
All
study were
com-
via
a direct
PCB c o n g e n e r
and
2693
Table II lists the relative retention times and response factors for
the 209 PCB congeners compiled on data obtained by using the octadecyl/phenyl substituted siloxane phase column.
Table II.
Relative Retention ~mes and Response Factors for 209 PCB congeners obtained on the
octadecyVphenyl siloxane column
cong.
#
ndatlve
retention
Umo
relative
response
factor
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
0.2776
0.2728
0.2617
0.2769
0.3357
0.3288
0.3216
0.3379
0.3190
0.2838
0.3859
0.3925
0.3929
0.3666
0.4003
0.3966
0.3840
0.3774
0.3441
0.4518
0.4533
0.4631
0.4259
0.3917
0.4376
0.4338
0.3896
0.4488
0.4314
0.3716
0.4437
0.4027
0,4539
0.4227
0.5159
0.4866
0.5247
0.5048
0,4954
0.5188
0,5143
0.5063
0.4816
0.4985
0.4520
0,4S84
0.4950
0.4905
0.4865
0.4342
0.4500
0.4789
0.4386
0.0170
0.0050
0.0365
0.0705
0.3225
0.1830
0.3205
0.1925
0.2140
0.2040
0.5450
0.1340
0.0666
0.1229
0.0695
0.2720
0.2648
0.1855
0.1536
0.4289
0.6817
0.50,55
0.4690
0.4568
0.4100
0.2985
0.1219
0.4525
0,3945
0.4700
0,3337
0.3685
0.3545
0.2855
0.1978
0.1887
0.1820
03106
0,1725
0,4236
0.5205
0.4326
0.3479
0.3784
0.G~78
0.2676
0.3681
0.3041
0.2937
0.2966
0.2570
0.2376
0.220g
cong.
#
reldve
retention
Ume
relatlve
response
~
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
76
76
77
76
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
10~
103
104
105
0.4029
0.5732
0.5816
0.5422
0.5475
0.5028
0.5847
0.5579
0.4982
0.5541
0.5184
0.4943
0.5665
0.5478
0.5321
0.4816
0.5614
0.5142
0.5282
0.4776
0.5601
0.4963
0.55Se
0.6461
0.6250
0.6149
0.5835
0.6351
0.6352
0.6007
0.5663
0.6230
0.6699
0.6140
0.5.549
0.5742
0.5901
0.5591
0.5815
0.5488
0,5359
0.5465
0.5052
0.6114
0.5495
0.5990
0.5407
0.5~I0
0.5483
0.5285
0.4814
0.7009
0,1636
0.1636
0.5390
0.4305
0.4694
0.4936
0.7310
0.8185
0.7465
0,4475
0.5090
0.5900
0.4646
0.8000
0.8190
0.3925
0.4OO5
0.420Q
0.3535
0.3140
0.4084
0.4935
0.3731
0.2708
0.3384
02796
0.3~24
0.3410
0.5590
0.4215
0.3605
0.5,930
0.5975
0.5966
0.5127
0.3708
0.4085
0.3417
0.3735
0.370g
0.2774
0.3467
0.2265
0.3969
0.3564
0.3677
0.5871
0.3675
0.2888
0.3590
0.2375
0.894,9
cong.
#
rd~Ive
retention
time
rdetlve
response
factor
cong.
#
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
15.5
156
157
0.6740
0.6693
0.6666
0.6095
0.6276
0.6331
0.6036
0.5896
0.6857
0.6249
0.6223
0.6204
0.6746
0.6055
0.6403
0.5693
0.6840
0.6701
0.6636
0.6106
0.7519
0.7196
0.7496
0.7271
0.7142
0.6678
0.6783
0.6788
0.6.592
0.6391
0.6038
0.7153
0.7236
0.6594
0.6603
0.7060
0.6707
0.6582
0.6461
0.6037
0.6889
0.6516
0.6219
0.6524
0.5906
0.6384
0.5924
0.6988
0.6351
0.5773
0.79.53
0.7978
0.a~'35
0.6000
0.760g
0.74g0
0.5925
0.5975
0.5810
0.49gQ
1.0308
1.5120
1.1155
0.6104
0.4979
0.5465
0,5336
0.5000
0.5336
0.5295
0.5167
0.4895
0.4880
O.5459
0.8120
0.6815
0.6090
0.6057
0.5065
0.5086
0.4682
0.3865
0.3198
0.7810
0.6305
0.6250
0.4809
0.7655
0.8870
0.5297
0.6848
0.4166
0.4199
0.4892
0.3875
0.3897
0.3095
0.4576
0.3068
0.4649
0.3785
0.3030
1.0072
0.8927
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
190
200
201
2G2
203
204
205
206
207
208
209
relative
retention
time
0.7302
0.7603
0.7288
0,6912
0.7341
0.7239
0.7185
0.6853
0.7450
0.7717
0.6981
0.8496
0.8348,
0.7751
0.8000
0.7780
0.7584
0.7356
0.6992
0.7661
0.7261
0.6863
0.8092
0.7692
0.7402
0.7479
0.6852
0.7552
0.7077
0.7393
0.6730
0.8849
0.8425
0.8150
0.8038
0.8087
0.9139
0.8778
0.8477
0.7876
0.8371
0.7959
0.7747
0.8386
0.7616
0.8511
0.7831
0.g217
0.9458
0.8803
0.8668
0.9691
relative
mponse
factor
0.8893
1.0350
1.0324
0.8336
0.7025
0.6869
0.6335
0.6811
0.9129
0.6685
0.5905
0.6~M4
0.8690
0.6662
0.8307
0.8976
0.6256
0.6627
0.4857
0.6225
0.7030
0.7900
0.8209
0.9125
0.6025
0.6716
0.4775
0.9687
0.7384
0.5456
0.3850
1.0ggQ
0.9e16
0.8974
0.8965
0.8175
0.9205
0.7907
0.7536
0.6006
0.7956
0.7225
0.5040
0,7158
0.4056
0.8933
0.e867
0.9222
1.0150
1.3085
0.8188
0.8217
2694
The retention data is further categorized in Table III into subgroups according to the degree of chlorination.
cates several general trends.
A review of these two tables indi-
The retention times of the congeners in-
creases with the degree of chlorination which is consistent w i t h published
Table III. Relative retention to OCN of congeners subgrouped via chlorine substitution on the
octadecyl/phenyl siloxane column
Monochlorobiphenyls
Cong. it Structure
1
2-CI
2
2-CI
3
4-CI
Dichlorobiphenyts
Cong. it Structure
4
2,2'
10
2,6
9
2,5
7
2,4
5
2,3'
5
2,3
8
2,4'
14
3,5
11
3,3'
12
3,4
13
3,4'
15
4,4'
RRT
0.2769
0.2838
0.3190
0.3215
0.3288
0.3357
0.3374
0.3666
0.3859
0.3925
0.3929
0.4003
Trichlorobiphenyls
Cong. it Structure
19
2,2',6
30
2,4,6
18
2,2`,5
17
2,2',4
27
2,3',6
24
2,3,6
16
2,2',3
32
2,4',6
34
2`,3,5
23
2,3,5
29
2,4,5
22
2,3,4'
26
2,3',5
25
2,3',4
31
2,4',5
28
2,4,4'
20
2,3,3'
21
2,3,4
33
2',3,4
36
3,3',5
39
3,4',5
38
3,4,5
35
3,3',4
37
3,4,4'
RRT
0.3441
0.3716
0.3774
0.3840
0.3896
0.3917
0.3966
0.4027
0.4227
0.4259
0.4314
0.4631
0.4338
0.4376
0.4437
0.4488
0.4518
0.4533
0.4539
0.4866
0.4954
0.5048
0.5159
0.5247
Tetrachlorobiphenyls
Cong. # $tru©ture
54
2,2` ,6,6'
50
2,2',4,6
53
2,2',5,6'
51
2,2',4,6'
45
2,2`,3,6
46
2,2',3,6'
73
2,3',5',6
52
2,2`,5,5'
43
2,2',3,5
69
2,3',4,6
49
2,2',4,5'
48
2,2',4,5
47
2,2`,4,4'
65
2,3,5,6
75
2,4,4',6
62
2,3,4,6
RRT
0.4029
0.4342
0.4386
0.4500
0.4520
0.4584
0.4776
0.4789
0.4816
0.4815
0.4865
0.4905
0.4950
0.4943
0.4963
0.4982
RRT
02726
0.2728
0.2817
Tetrxchloroldphenyls (©on't)
Cong. it Structure
RRT
0.4985
44
2,2',3,5'
0.5028
59
2,3,3',6
0.5063
42
2,2",3,4'
0.5142
71
2,3',4',6
0.5143
41
2~,3,4
0.5184
64
2,3,4',6
0.5188
40
2~',3,3'
0.5282
72
2,3',5,5'
0.5321
68
2,3',4,5'
0.5422
57
2,3,3',5
0.5475
58
2,3,3',5'
0.5478
67
2,3',4,5
0.5541
63
2,3,4',5
0.5579
61
2,3,4,5
0.5598
76
2',3,4,5
0.5601
74
2,4,4',5
0.5614
70
2,3',4',5
0.5665
66
2,3',4,4'
0.5732
55
2,3,3',4
0.5816
56
2,3,3',4'
0.5835
80
3,3',5,5'
0.5847
60
2,3,4,4'
0.6149
79
3,3',4,5'
0.6250
78
3,3',4,5
0.6351
81
3,4,4',5
0.6461
77
3,3',4,4'
Pentuchlorobiphenyls
Cong. # Structure
104
2,2',4,6,6'
96
2,2`3,6,6'
103
2,2',4,5',6
94
2,2',3,5,6'
100
2,2',4,4',6
95
2,2`,3,5',6
102
2,2`,4,5,6'
93
2,2',3,5,6
98
2,2`,3',4,6
88
2,2',3,4,6
91
2,2',3,4',6
84
2,2',3,3',6
121
2,3',4,5',6
89
2~',3,4,6'
92
2,2',3,5,5'
113
2,3,3',5',6
90
2~',3,4',5
101
2~,4,5,5'
99
2,2`,4,4',5
83
2,2`,3,3',5
112
2,3,3',5,6
119
2,3',4,4',5
109
2,3,3',4,6
(IUPAC # 108)
86
2,2',3,4,5
125
2',3,4,5,6'
97
2,2`,3',4,5
87
2,2`,3,4,5'
117
2,3,4',5,6
116
2,3,4,5,6
85
2~',3,4,4'
115
2,3,4,4',6
110
2,3,3',4',6
111
2,3,3',5,5'
RRT
0.4914
0.5052
0.5285
0.5359
0.5407
0.5465
0.5483
0.5488
0.5495
0.5549
0.5591
0.5663
0.5693
0.5742
0.5815
0.5896
0.5901
0.5910
0.5990
0.6007
0.6036
0.6055
0.6095
0.6099
0.6106
0.6114
0.6140
0.6204
0.6223
0.6230
0.6249
0.6276
0.6331
Pentachlorobiphenyls
Cong. # Structure
82
2,2`,3,3',4
120
2,3',4,5,5'
124
2',3,4,5,5'
108
2,3,3',4,5'
(IUPAC # 107)
107
2,3,3',4',5
(IUPAC # 109)
123
2',3,4,4',5
106
2,3,3',4,5
118
2,3',4,4',5
122
2',3,3',4,6
114
2,3,4,4',5
105
2,3,3',4,4'
127
3,3',4,5,5'
126
3,3',4,4',5
0.6701
0.6740
0.6746
0.6840
0.6851
0.7009
0.7196
0.7519
Hexachlorobiphenyls
Cong. # Structure
155
2,2',4,4',6,6'
150
2 ~2',3,4',6,6'
152
2,2`,3,5,6,6'
145
2,2",3,4,6,6'
136
2,2",3,3',6,6'
148
2,2',3,4',5,6'
154
2,2',4,4',5,6'
151
2,2`,3,5,5',6
135
2,2',3,3',5,6'
144
2,2`,3,4,5',5
147
2,2`,3,4',5,6
149
2,2`,3,4',5',6
143
2,2`,3,4,5,5'
134
2,2',3,3',5,6
139
2~,3,4,4',6
140
2 ~',3,4,4',6'
131
2,2`,3,3',4,6
142
2,2',3,4,5,6
132
2~',3,3',4,6'
133
2~',3,3',5,5'
165
2,3,3',5,5',6
146
2,2`,3,4',5,5'
t61
2,3,3',4,5',6
168
2,3',4,4',5',6
153
2,2',4,4',5,5'
141
2,2`,3,4,5,5'
130
2,2`,3,3',4,5'
137
2,2',3,4,4',5
164
2,3,3',4',6',6
138
2,2',3,4,4',5'
163
2,3,3',4',5,6
129
2,2`,3,3',4,5
160
2,3,3',4,5,6
158
2,3,3',4,4',6
166
2,3,4,4',6,6
128
2,2',3,3',4,4'
159
2,3,3',4,5,5'
162
2,3,3',4',5,5'
167
2,3',4,4',5,5'
156
2,3,3',4,4',5
157
2,3,3',4,4',5'
169
3,3',4,4',5,5'
RRT
0.5773
0.5906
0.5924
0.6037
0.6038
0.6219
0.6351
0.6384
0.6391
0.6451
0.6516
0.6524
0.6582
0.6592
0.6594
0.6603
0.6678
0.6707
0.6783
0.6788
0.6853
0.6889
0.6912
0.6981
0.6988
0.7060
0.7142
0.7153
0.7185
0.7236
0.7239
0.7271
0.7288
0.7302
0.7450
0.7496
0.7603
0.7641
0.7717
0.7953
0.7978
0.8460
RRT
0.6352
0.6403
0.6636
0.6666
0.6693
Heptucldoroblpheayl
Cong. # Structure
188
2,2',3,4',5,6,6'
184
2,2',3,4,4',6,6'
179
2,2`,3,3',5,6,6'
176
2,2`,3,3',4,6,6'
186
2,2',3,4,5,6,6'
178
2,2',3,3',5,5',6
175
2,2`,3,3',4,5',6
187
2,2`,3,4',5,5',6
182
2,2`,3,4,4',5,6'
183
2,2`,3,4,4',5',6
185
2,2`,3,4,5,5',6
174
2~',3,3',4,5,6'
181
2,2",3,4,4',5,6
177
2,2",3,3',4',5,6
171
2,2",3,3',4,4',6
173
2,2",3,3',4,5,6
172
2,2',3,3',4,5,5'
192
2,3,3',4,5,5',6
193
2,3,3',4',6,5',6
191
2,3,3',4,4',5,6
170
2,2',3,3',4,4',5
190
2,3,3',4,4',5,6
189
2,3,3',4,4',5,5'
Octachlorobiphenyle
Cong. # Structure
202
2,2`,3,3',5,5',6,6'
200
2,2`,3,3',4,5',5,6'
(IUPAC #201)
204
2,2',3,4,4',5,6,6'
197
2,2`,3,3',4,4',6,6'
199
2,2`,3,3',4,6,6,6'
(IUPAC # 200)
198
2,2`,3,3',4,5,5',5
201
2,2",3,3',4,4',5',6
(IUPAC # 199)
196
2,2",3,3',4,4',5',6
203
2,2`,3,4,4',5,5',6
195
2,2',3,3',4,4',5,6
194
2,2`,3,3',4,4',5,5'
205
2,3,3',4,4',5,5',5
Nonachlorobiphenyls
Cong. # Structure
208
2 ~',3,3',4,5,5',6,6'
207
2 ~',3,3',4,4',5,6,6'
206
2 ~',3,3',4,4',5,5',6
RRT
0.5730
0.6852
0.6863
0.6992
0.7077
0.7261
0.7356
0.7393
0.7402
0.7479
0.7552
0.7584
0.7692
0.7661
0.7751
0.7780
0.8000
0.8038
0.8087
0.8150
0.8348
0.8425
0.8849
RRT
0.7616
0.7747
0.7831
0.7850
0.7959
0.8371
0.8386
0.8477
0.8511
0.8778
0.9139
0.9217
RRT
0.8188
0.8803
0.9458
Decachlofobiphenyl
Cong. i t Structure
210
2,2",3,3',4,4',5,5~,6,6 '
Relative m t m t i o n of congenem to
Octachloronaphthakme on C , column
RRT
0.9691
2695
results.
first.
Within
Within
each
subgroup,
geners w h i c h
are
elut e b e f o r e
substituted
other
next
congeners
higher
tion.
chlorine
This
tablished
ers
retention
grouping
the r e t e n t i o n
by M u l l i n
with
substituted
the n u m b e r
overlapping
of
into
a gaussian-like
the s u b s t i t u t i o n
conforms
(19)
the con-
instances,
by c o n g e n e r s
follows
data
et al
in m o s t
subgroups,
times
elute
chlorines),
the
distribupattern
to the g u i d e l i n e s
and Ballschmitter
of
es-
and c o - w o r k -
(20).
These
guidelines
are also
on a 50% p h e n y l
substituted
r e v i e w of T a b l e
IV r e v e a l s
gener peak
similar
shifts,
to t h o s e
lack of p e a k
phase
used
polar
shifting
dipole
stationary
phase
Tables
study possesses
to e n s u r e
target
(78% c y a n o p r o p y l
IV a l s o
Duplicate
the o c t a d e c y l / p h e n y l
ECD was
reliability
These
was monitored
However,
result
siloxane
revealed
of the d i f f e r e n c e s
acteristics
suggests
as w e l l
that
identifying
for c o r r o b o r a t i n g
conjunction
with
of all
response
209
Excellent
columns
are
column.
The
stationary
containing
a strong
a highly
and a trifluoropropyl
a n d the results
factors
congeners
siloxane
linearity
over a r a n g e
response
factors
were
throughout
for the 209
were made
columns
that
calculated
on b o t h
in o r d e r
of r e s p o n s e
exceeding
of < 4% for the same c o n g e n e r
for the
of the
relative
on the same
the s t u d y a n d e x h i b i t e d
of the r e s p o n s e
column versus
in c o l u m n
to
column.
a R S D of < 1%
of this,
patterns
retention
data.
or r e l a t i v e
the r e s p o n s e
(21).
for
response
charThis
factors
o n l y be m e a n i n g f u l
a specified
factors
of i n d i v i d u a l
retention
of the E C D
and may
column
This m a y be a
flow rates,
within
on the
siloxane
variations.
of r e s p o n s e
absolute
the i d e n t i f i c a t i o n
obtained
50% p h e n y l
d i me n s i o n s ,
system dependent
substitution
In s p i t e
factors
the
some c o n s i d e r a b l e
at a s s i g n i n g
is h i g h l y
chlorine
ing p a r a m e t e r s .
subgroups
A study using
and the 50% p h e n y l
as the v a r i a b i l i t y
attempts
to PCB c o n g e n e r s
con-
injections.
a comparison
the same c o n g e n e r
groups
is on-going;
the r e l a t i v e
of results.
O C N and s h o w e d v a r i a t i o n s
octadecyl/phenyl
type
that n e i t h e r
substitution)
groups)
injections
for b o t h
concentration.
for 50 r e p l i c a t e
list
siloxane
established
OCN response
fact
acceptor.
A
of a few i n d i v i d u a l
substituent
to the
obtained
IV and V.
of the c h l o r i n a t e d
substituent
electron
patterns
- Tables
in a f u t u r e paper.
II a n d
PCB congeners.
patterns
on the o c t a d e c y l
(electron-accepting
be p u b l i s h e d
phase
the e x c e p t i o n
m a y be a t t r i b u t e d
phase
to the e l u t i o n
siloxane
that w i t h
or a s t r o n g
stationary
applicable
methyl
the e l u t i o n
obtained
in this
permanent
will
followed
can be c o r r e l a t e d
Overall,
and p u b l i s h e d
positions,
are
congeners
(>three
the c o n g e n e r
exhibit
substituted
distribution
the c o n g e n e r s .
These
Throughout
which
subgroups
in the o,o'
congeners.
in the o , m p o s i t i o n s .
individual
the o r t h o - s u b s t i t u t e d
the m u l t i c h l o r i n a t e d
should
congeners
for
set of w o r k be u s e f u l
when
used
in
2696
Table IV.
Relative Retention Times and Response Factors for 209 PCB Congeners obtained on
the 50% phenyl methyl siloxane column
cong.
#
relnUve
retention
time
reletive
renporme
factor
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
0.1541
0.1906
0.1959
0.2176
0.2659
0.2565
0.2368
0.2637
0.2376
0,2137
0.3114
0.3184
0,3214
0,2749
0.3325
0.3496
0.3162
0.3160
0.2922
0.4002
0.3918
0.4114
0.3439
0.3282
0.3676
0.3664
0.3301
0.3781
0.3487
0 .2824
0,3774
0,3431
0.3977
0.3486
0.4664
0,4141
0.4798
0,4399
0,4279
0.5020
0.4803
0.4660
0.4279
0.4641
0.4146
0.4318
0,4315
0.4331
0.4302
0.3660
0.4000
0.4280
0.3964
0.0377
0.0055
0.0192
0.0439
0.5948
0.2746
0.5537
0.2614
0.3027
0.3199
0.0572
0.1519
0.0689
0.1504
0.0676
0.3770
0.3375
0.2129
O. 1853
0.6624
1.0293
0.8207
0.6532
0,6624
0.5507
0.3687
0.2474
0.5894
0.5142
0.6515
0.39g0
0.4885
0.4654
0.3553
0,1851
0.1886
0.1694
0,3624
0,1637
0.4736
0,6765
0.4780
0.3861
0.3814
0.0970
0.2761
0.3945
0.3100
0.2919
0.3221
0.2765
0.2426
0,2345
cong.
#
relative
retention
Ume
rdetive
response
factor
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
1O0
101
102
103
104
105
0.3667
0.5412
0.5573
0.4861
0.5024
0.4651
0.5541
0.5014
0.4323
0.4991
0.4773
0.4314
0.5217
0.4907
0.4675
0.4121
0.5186
0.4776
0.4642
0.4229
0.5038
0.4248
0.5155
0.6298
0.5900
0.5736
0.5168
0.6078
0.6372
0.5804
0.5608
0.6030
0.5850
0.5991
0.5169
0.5607
0.5465
0.5278
0.5415
0.5129
0.5019
0.5220
0.4844
0.5868
0.5095
0.5527
0.4772
0.5492
0.5117
0.4726
0.4380
0.6995
0,1590
0,9152
0,7340
0,5212
0,6532
0.6069
0.9982
1.0040
0,9619
0.5418
0.6611
0.8003
0.6246
0.5184
0.5687
0.5985
0.5144
0,6140
0.4856
0.4297
0.5554
0.7101
0,5745
0.3100
0.4787
0.3546
0.4517
0.3833
0.7192
0.4929
0.3890
0.8331
0.8602
0.7795
0.7043
0.4517
0.4879
0.3966
0.4550
0.4090
0.3217
0.3995
0.2417
0.4290
0.4088
0.4468
0.4157
0.3677
0.3015
0.3789
0.2557
0.9660
cong.
#
rdaUve
retention
time
reloUve
renponse
factor
cong.
#
relative
retention
time
relative
response
factor
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
1,52
153
154
155
156
157
0.6476
0.6414
0.6416
0.5721
0.6150
0.5832
0.5694
0.5565
0.6635
0,5873
0.5810
0,5864
0.6487
0.5626
0.5915
0.5061
0.6750
0.6421
0.6365
0.5889
0.7531
0.6944
0.7709
0.7354
0.7137
0.6622
0.6890
0,6544
0.6577
0.6280
0.6034
0.7030
0.7216
0.6305
0.6388
0.6974
0.6571
0.6527
0.6234
0.5812
0.6635
0,6264
0.5785
0.6395
0.5574
0,6190
0.5739
0.6729
0.59~
0.5106
0.8041
0.8151
0.9936
0.7512
0.9565
0.9744
0,6990
0.7311
0,7377
0.6701
1.0832
1.2680
1.1636
0.8155
0.5859
0.7024
0.6598
0,6216
0.6168
0,6437
0.6447
0.5840
0.5300
0.6801
0.9759
0.8229
0.7144
0.7290
0.5429
0.6160
0.5260
0.4359
0.3429
0.9388
0.7129
0.7889
0.5389
0.9475
1.1715
0.6338
0.7690
0.5080
0.4599
0.5350
0.4409
0.4015
0.3369
0,5419
0.3439
0.4875
0.4071
0.3439
1.0155
0.8609
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
0.7236
0.7443
0.7189
0.6629
0.7555
0,7204
O.7237
0,6600
0.7364
0,7645
0,6728
0.8714
0.8669
0.7885
0.8072
0.7986
0.7758
0.7259
0.6969
0.7829
0.7196
0,6874
0.8164
0,7681
0.7267
0,7379
0.6502
0.7589
0.7092
0.7324
0.6414
0.9119
0.8667
0.8285
0.8069
0.8249
O,957O
0.9216
0.8718
0.7882
0.8575
0.8206
0.7778
0.8635
0.7653
0.8688
0.7735
O.9627
0,9944
0.9033
0.8917
1.0140
0.9735
1.2165
1.2833
1.0795
O.8955
0.8060
0.6960
0.8240
1.1420
0.7545
0.7305
0.7275
0.8300
0.6655
0.8700
0.9821
0.6455
0.7220
0.5435
0.6302
0.6155
0.4149
0,8625
1,0699
0.6788
0.7326
0.5784
1.1595
0.9045
0.6026
0.4616
1.1412
1.0605
0.8235
0.9475
0.8115
0,8759
0.7625
0.7374
0,5876
0.8610
0.7640
0.5024
0,7190
0,4305
1.0050
0.9730
0.9735
1.0310
1.3795
0.8646
0,2655
2697
Table V.
Relative etention to OCN of PCB congeners subgrouped via chlorine substitution
on the 50% phenyl methyl siloxane column
Monochloroldphenyls
Cong. # Structure
1
2-CI
2
2-CI
3
4-CI
RRT
0.1541
0.1906
0.1959
Dlchlorobiphenyls
Cong. # Structure
10
2,6
4
2,2`
7
2,4
9
2,5
6
2,3'
8
2,4'
5
2,3
14
3,5
11
3,3'
12
3,4
13
3,4'
15
4,4'
RRT
0.2137
0.2176
0.2368
0.2375
0.2565
0.2637
0.2659
0.2749
0.3114
0.3184
0.3214
0.3325
Trichlorobiphenyb
Cong. # Structure
30
2,4,6
19
2,2`,6
18
2,2',5
17
2,2',4
24
2,3,6
27
2,3',6
32
2,4',6
23
2,3,5
34
2',3,5
29
2,4,5
16
2,2',3
26
2,3',5
25
2,3',4
31
2,4',5
28
2,4,4'
21
2,3,4
33
2',3,4
20
2,3,3'
22
2,3,4'
36
3,3',5
39
3,4',5
38
3,4,5
35
3,3',4
37
3,4,4'
RRT
0.2824
0.2922
0.3160
0.3162
0.3282
0.3301
0.3431
0.3439
0.3486
0.3487
0.3496
0.3664
0.3676
0.3774
0.3781
0.3918
0.3977
0.4000
0.4114
0.4141
0.4279
0.4399
0.4664
0.4798
Tetrachlorobipheny~
Cong. # Structure
50
2,2`,4,6
54
2,2`,6,6'
53
2,2',5,6'
51
2,2',4,6'
69
2,3',4,6
45
2,2',3,6
73
2,3',5',6
75
2,4,4',6
43
2,2',3,5
52
2,2',5,5'
49
2,2',4,5'
65
2,3,5,6
RRT
0.3660
0.3667
0.3964
0.4000
0.4121
0.4146
0.4229
0.4248
0.4279
0.4280
0.4302
0.4314
Tetrachloroblphenyls (con't)
Cong. # Structure
RRT
47
2~',4,4'
0.4315
46
2,2`,3,6'
0.4318
62
2,3,4,6
0.4323
48
2,2',4,5
0.4331
44
2,2`,3,5"
0.4641
72
2,3',5,5"
0.4642
59
2,3,3',6
0.4651
42
2,2`,3,4'
0.4660
68
2,3',4,5'
0.4675
64
2,3,4',6
0.4773
71
2,3',4',6
0.4776
41
2,2',3,4
0.4803
57
2,3,3',5
0.4861
67
2,3',4,5
0.4.907
63
2,3,4',5
0.4991
40
2,2`,3,3'
0.5020
61
2,3,4,5
0.5014
58
2,3,3',5"
0.5024
74
2,4,4',5
0.5038
76
2`,3,4,5
0.5155
80
3,3',5,5'
0.5168
70
2,3',4',5
0.5186
66
2,3',4,4'
0.5217
55
2,3,3',4
0.5412
60
2,3,4,4'
0.5541
56
2,3,3',4'
0.5573
79
3,3',4,5'
0.5736
78
3,3',4,5
0.5900
81
3,4,4',5
0.6078
77
3,3',4,4'
0.6288
Pentmchlorobiphenyls
Cong.# Structure
104
2,2`,4,5,6'
103
2,2',4,5',5
100
2,2`,4,4',6
96
2,2'3,6,6'
94
2,2',3,5,6'
121
2,3',4,5',6
98
2,2`,3',4,6
102
2,2`,4,5,6'
93
2,2',3,5,6
88
2,2',3,4,5
95
2,2`,3,5",6
91
2,2`,3,4',6
92
2,2',3,5,5'
90
2,2`,3,4',5
101
2,2',4,5,5"
99
2,2,4,4',5
113
2,3,3',5',6
89
2,2',3,4,6'
84
2,2',3,3',6
119
2,3',4,4',6
112
2,3,3',5,8
109
2,3,3',4,6
(IUPAC # 108)
83
2,2',3,3',5
116
2,3,4,5,6
111
2,3,3',5,5'
86
2,2',3,4,5
RRT
0.4380
0.4726
0.4772
0.4844
0.5019
0.5061
0.5095
0.5117
0.5129
0.5169
0.5220
0.5278
0.5415
0.5465
0.5492
0.5527
0.5565
0.5607
0.5608
0.5626
0.5694
0.5721
0.5804
0.5810
0.5832
0.5850
Pentachlorobiphenyls (con't)
Cong. # Structure
RRT
117
2,3,4',5,6
0.5864
97
2,2',3',4,5
0.5868
115
2,3,4,4',6
0.5873
125
2',3,4,5,6'
0.5889
120
2,3',4,5,5'
0.5915
87
2,2`,3,4,5"
0.5991
85
2,2`,3,4,4'
0.6030
110
2,3,3',4',6
0.6150
124
2',3,4,5,5'
0.6365
62
2,2`,3,3',4
0.6372
107
2,3,3',4',5
0.6414
(IUPAC # 107)
108
2,3,3',4,5"
0.6416
(IUPAC # 109)
123
2',3,4,4',5
0.6421
106
2,3,3',4,5
0.6476
118
2,3',4,4',5
0.6487
114
2,3,4,4',5
0.6635
122
2',3,3',4,5
0.6750
127
3,3',4,5,5"
0.6944
105
2,3,3',4,4'
0.6995
126
3,3',4,4',5
0.7531
Hexachlorobiphqmyls
Cong. # Structure
155
2,2',4,4',6,6'
150
2,2`,3,4',6,6'
152
2,2',3,5,6,6'
148
2,2',3,4',5,6'
145
2,2',3,4,6,6'
154
2,2`,4,4',5,6'
136
2,2`,3,3',6,6'
151
2,2',3,5,5',6
144
2,2',3,4,5',6
147
2,2`,3,4',5,5
135
2,2`,3,3',5,6'
139
2,2`,3,4,4',6
140
2,2',3,4,4',6'
149
2,2',3,4',5',6
143
2,2',3,4,5,6'
133
2,2',3,3',5,5'
142
2,2',3,4,5,6
134
2,2`,3,3',5,6
165
2,3,3',5,5',6
131
2,2',3,3',4,6
161
2,3,3',4,5",6
146
2,2',3,4',5,5"
168
2,3',4,4',5',6
153
2,2',4,4',5,5'
132
2,2',3,3',4,6'
141
2,2`,3,4,5,5'
137
2,2`,3,4,4',5
130
2,2',3,3',4,5'
160
2,3,3',4,5,6
163
2,3,3',4',5,6
158
2,3,3',4,4',6
164
2,3,3',4',5',6
129
2,2',3,3',4,5
166
2,3,4,4',5,6
159
2,3,3',4,5,5'
RRT
0.5106
0.5574
0.5739
0.5785
0.5812
0.5902
0.6034
0.6150
0.6234
0.6264
0.6280
0.6305
0.6388
0.6395
0.6527
0.6544
0.6571
0.6577
0.6600
0.6622
0.6629
0.6635
0.6728
0.6729
0.6890
0.6974
0.7030
0.7137
0.7189
0.7204
0.7236
0.7237
0.7354
0.7364
0.7443
Hexachlorobiphenyls (con't)
Cong. # Structure
RRT
162
2,3,3',4',5,5"
0.7555
167
2,3',4,4',5,5"
0.7645
128
2,2`,3,3',4,4'
0.7709
156
2,3,3',4,4',5
0.8041
157
2,3,3',4,4',5'
0.8151
169
3,3',4,4',5,5"
0.8714
Hepta©hlorobiphenyls
Cong. # Structure
188
2,2',3,4',5,8,6'
184
2,2`,3,4,4',6,6'
179
2,2',3,3',5,6,6'
176
2,2',3,3',4,6,6'
186
2,2',3,4,5,6,6'
178
2,2',3,3',5,5",6
175
2,2`,3,3',4,5",6
182
2,2`,3,4,4',5,6'
187
2,2`,3,4',5,5",6
183
2,2`,3,4,4',5',6
185
2,2`,3,4,5,5',6
181
2,2`,3,4,4',5,6
174
2,2`,3,3',4,5,6'
177
2,2`,3,3',4',5,6
171
2,2',3,3',4,4',6
173
2,2`,3,3',4,5,6
192
2,3,3',4,5,5',6
180
2,2`,3,4,4',5,5'
193
2,3,3',4',5,5",6
191
2,3,3',4,4',5",6
190
2,3,3',4,4',5,6
170
2,2`,3,3',4,4',5
189
2,3,3',4,4',5,5'
RRT
0.6414
0.6502
0.6874
0.6969
0.7092
0.7196
0.7259
0.7267
0.7322
0.7379
0.7589
0.7681
0.7758
0.7829
0.7885
0.7986
0.8069
0.8164
0.8249
0.8285
0.8667
0.8669
0.9119
Octachlorobiphenyls
Cong. # Sbucture
202
2,2`,3,3',5,5',6,6'
204
2,2',3,4,4',5,6,6'
200
2,2',3,3',4,5',6,6'
(IUPAC #201)
197
2,2`,3,3',4,4',6,6'
199
2,2`,3,3',4,5,6,6'
(IUPAC # 200)
198
2,2`,3,3',4,5,5',6
201
2,2',3,3',4,4',5',6
(tUPAC # 199)
203
2,2`,3,4,4',5,5",6
196
2,2',3,3',4,4',5",6
195
2,2',3,3',4,4',5,6
194
2,2',3,3',4,4',5,5'
205
2,3,3',4,4',5,5",6
Nonamhlorobiphenyls
Cong. # Structure
208
2,2',3,3',4,5,5',6,6'
207
2,2',3,3',4,4',5,6,6'
206
2,2`,3,3',4,4',5,5",6
Decachlorobiphmtyl
Cong. # Structure
210
2,2`,3,3',4,4',5,5",6,6'
RRT
0.7653
0.7735
0.7778
0.7882
0.8206
0.8575
0.8635
0.8688
0.8718
0.9216
0.9570
0.9627
RRT
0.8917
0.9033
0.9944
RRT
1.0140
Gas Chromatography/Mass Spectrometry: The m a s s s p e c t r a of PCB's have
b e e n s t u d i e d by n u m e r o u s
have b e e n identified:
distribution pattern
ters,
investigators
(1,22-24),
and a n u m b e r of features
I. Ion c l u s t e r s w i t h the e x p e c t e d c h l o r i n e
isotope
for e a c h s u b g r o u p i n g 2. P r o m i n e n t odd e l e c t r o n clus-
c o n s i s t i n g of the p a r e n t
ion c l u s t e r and those g e n e r a t e d by the loss
2698
of an even n u m b e r
of c h l o r i n e
loss of an o d d n u m b e r
even
electron
assume
chlorinated
substitution
am o n g
the
PCB
large
(M-35)
(M-70)
oms w e r e
The
ions
there
found
Within
intensity
peaks
have
a tendency
four o r t h o
chlorines
> no o r t h o
at-
the h i g h e s t
and M-C12
isomers
to d e c r e a s e
lows,
chlo-
and M-C12 ions.
of the r e m a i n i n g
ortho
to the
an isomer
three
of the M-C1
mass
among
chlorine
to h a v e
of M-C1
are
compared
containing
In
the same
differences
or two o,o'
intensity
of d i f f e r -
having
ions.
PCB's
rine atoms
in the m a s s
of the base
of c h l o r i n a t i o n ,
group,
4. D o u b l y
ion cluster.
congeners
relatively
M-C12
in the PCB.
the data was
to p e r c e n t a g e s
the M-C1
and m a i n l y
efficiencies
isomers,
in the p a r e n t
degree
as
fol-
chlorines
> two o,o
> one o r t h o
chlorine
chlorines.
The a b o v e
trends
can be u n d e r -
in terms
of the
stabilities
stood
the p a r e n t
ions.
ions
A key
and t h e i r
factor
the s t a b i l i t y
ions
is the steric
resulting
from the
chlorine
in the a b i l i t y
of an iso-
hindrance
interaction
atoms.
to at-
configuration
the a m o u n t
of
An i n c r e a s e
of the rings
tain a c o - p l a n a r
creases
of
daughter
in d e t e r m i n i n g
of the
mer g r o u p
ort h o
of r e s o n a n c e
insta-
bilization.
PCB's
having
chlorines
have
cause
steric
strong
the
The r e l a t i v e
variable
abundance
the effect
in i o n i z a t i o n
comparing
clusters
spectra
generated
intensity
determined
charged
by the
of these
by the na-
ion species
of the m o r e
highly
PCB's.
To r e d u c e
reduced
3. E l e c t r o n
atoms.
are h i g h l y
appreciable
ences
peak
of c h l o r i n e
clusters
ture of the o r t h o
which
atoms.
after
four o r t h o
small M - C 1
ions be-
hindrance
losing
only
is still
one chlo-
Figure 2. Ordering of the relative intensities of the
M-35 mass spectral peak of the hexachlorobiphenyl
isomers by the number of ortho chlorines and the
number of meta chlorines adjacent to those ortho
chlorines
PCB
ISOMER
3,3',4,4',5,5'
2,3',4,4',5,5 ~
2,3,3',4,4',5
2,3,3',4,5,5'
2,3,3',4',5,5'
2,3,3',4,4',5'
2,3,3',4,4',6
2,3,4,4',5,6
2,3,3',4',5,6
2,3,3',4,5,6
2,3',4,4',5',6
2,3,3',4,5',6
2,3,3',4',5',6
2,3,3',5,5',6
2,2',4,4',5,5'
2,2',3,4,4',5'
2,2',3,4,4',5
2,2',3,4',5,5'
2,2',3, 4, 5,5'
2,2',3,3',4,4'
2,2',3,3',4,5
2,2',3,3',4,5'
2,2',3,3',5,5'
2,2',4,4',6,6'
2,2',3,4,4',6
2,2',3,4',5',6
2,2',3,4,5',6
2,2',3,4,4',6'
2,2',3,4',5,6'
2,2',3,4,5,6'
2,2',3,4',5,6
2,2',3,5,5',6
2,2',3,4,5,6
2,2',3,3',4,6'
2,2',3,3',4,6
2,2',3,3',5,6'
2,2',3,3',5,6
2,2',4,4',6,6'
2,2',3,4',6,6'
2,2',3,4,6,6'
2,2',3,3',6,6'
2,2',3,5,6,6'
NUMBER OF
NUMBER
ADJACENT
RELATIVE OF ORTHO ORTHO-META
% M-35
CHLORINES CHLORINES
0.17
0.55
0.46
0.50
0.61
0.70
0.61
0.74
0.87
0.99
1.07
1.26
1.35
1.71
5.90
11.47
12,59
15,58
18,09
22,61
28,93
29,02
37,03
10,18
1@99
16,78
18,93
19,72
21,74
22,06
22,96
24,69
26.42
28,20
29.33
29.99
38.43
1.48
2.10
2.55
2.67
3.04
0
2 (o,o)
2 (o,o')
0
0
2699
rine,
so t h e r e
PCB's
having
to h a v e
is l i t t l e
three
a gain
relative
exhibit
weak M-C1
driving
force
having
intensity
number
rine pair),
by the
stability
formation
of the
each g r o u p
intensity
This
grouping
losing
an o r t h o
chlorine
chlorine
atoms.
to e l e c t r o n
isomers
is not
seen
one or no o r t h o
is not
The
impact
also
destroys
the r e l a t i v e
between
PCB isomers
In some
cases,
substitution
in PCB's
chlorines
sufficient
where
ortho
(i.e.
Aroclor
products
the PCB c o n g e n e r s
contain
nyl.
occur
These
2000-1250
bands
c m -I, C=C
Of the t h r e e
determining
Matrix
isolated
identify
strongest
the
has
lists
of the
the m e l t i n g
literature
spectra
CI
//--~
-Cl
/'~----~
>
two o,o c h l o r i n e s
groups
spectral
gained
nor
(22).
peak
due
The d i f f e r e n c e s
T a b l e VII
ortho
substitution.
differences
in m e t a
of PCB c o n g e n e r s
(25-27).
bands
The
spectra
associated
cm -I, C - H
cm -I, b e n d i n g
T a b l e VI
and
of all
with biphe-
stretching;
and d e f o r m a t i o n s .
c m -I is the m o s t
PCB c o n g e n e r s
pattern
provided
which
useful
for
of all
points
of T a b l e VII
these published
that
of the
to
five
e a c h congener.
for the c r y s t a l l i n e
melting
indicate
can be u s e d
is a c o m p i l a t i o n
with
is a c o m p i l a t i o n
and a survey
with
209
associated
obtained
(28-35)
of all
values.
in
distinguish
isomers.
spectra
4000-2000
loss of
pattern
hindered
can h e l p
in t h e i r
among
in
in r e m o v i n g
sterically
is identical,
absorption
congener.
points
in g o o d a g r e e m e n t
the
•
for the less
from 1 2 0 0 - 3 0 0
wavelengths
thir d of the c o n g e n e r s ;
are
increases
congeners.
FT/IR
individual
M e l t i n g Points:
can be ex-
in the p r e f e r e n t i a l
absorption
the
o , m chlo-
of the C1 s u b s t i t u t i o n
and 1 2 5 0- 2 5 0
its own u n i q u e
absorption
This
3) w h i c h
the e n e r g y
studied
in the regions:
the r a n g e
individual
each c o n g e n e r
having
infrared
the m a j o r
stretching;
regions,
The
have been
ions.
~
in d i s t i n g u i s h i n g
M a t r i x Isolated GC/FT-IR:
commercial
chlorine
(figure
of d i f f e r e n c e s
substitution
into groups
of the r e l a t i v e
CI
CI
/~-~
/~------~
among
of the M - 3 5 mass
on the b a s i s
can be d i v i d e d
atom.
since
has b e e n n o t e d
m a y be of v a l u e
little
The g r e a t e r
to result
the d i f f e r e n c e s
intensity
and have
is apparent.
ion
a chlorine
random rearrangement
which
larger
combinations
meta
incmasedstabUi~oftheparentPCBion
those h a v i n g
stabilized
of the M-C1
Formation of a chloroniumion leadingto the
Figure 3.
chlorine
The o r d e r i n g
an a d j a c e n t
of a c h l o r o n i u m
ion u p o n
ortho
of c h l o r i n a t i o n
chlorines.
having
the
be e x p e c t e d
atom.
ions w i t h i n
the g r e a t e r
In contrast,
would
and show a correspondingly
they are a l r e a d y
or four or two o,o'
chlorines
chlorines
The r e m a i n i n g
the same d e g r e e
of the M - C 1
stabilization.
or two o,o'
stabilization
ions.
to lose a c h l o r i n e
of o r t h o
plained
of M-C1
ions b e c a u s e
having
three
in r e s o n a n c e
chlorines
in r e s o n a n c e
abundance
PCB's
gain
ortho
209
congeners
congeners.
A review
for a p p r o x i m a t e l y
reveals
that
and
one-
our results
2700
Table VI.
Selected Matrix Isolated FT/IR absorption bands for all 209 PCB congeners
Congener
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
3O
31
32
33
34
35
36
37
38
39
4O
41
42
43
44
45
46
47
48
49
5O
51
52
53
54
55
56
57
58
59
6O
61
62
63
64
68
66
67
68
69
7O
71
72
Absorpl~on Band Intensity
Strong
>
Weak
750.2
756,9
1482,4
752,6
759.3
756,3
1469.8
757.6
1463
1428.3
722.5
1467.6
1098.3
1561.9
1097.4
756,7
1463.9
758.9
754.9
781,1
1444.5
1094.9
1414.1
1433.9
1463.3
1458,7
786
1469.1
1458.2
833,1
1460.6
787,7
1461.9
757,4
1465,8
1561.4
1466
1434.7
1097
1441.6
1444.1
837,2
758,9
1450.2
1434.7
779.7
1465.7
1456.9
1459.9
757.8
1435.5
1463.5
1434.4
798.5
1446.5
1449.3
1555,3
785,2
1434.1
1447.2
1414.9
1422.8
1495.2
1437,1
700,3
1463.4
1459.1
847.5
845.3
1460.4
789.7
1558.3
699.5
698,7
760,9
762.6
699.3
1463
817.4
1471,1
1101
698
1597.2
761,4
803.9
761,3
815.1
1411.8
821,1
1463,3
1431,5
1451.8
1450,1
1452,4
699,4
1181,3
1109.2
1103.8
1434.2
1098.7
699.8
1544,7
1098.2
1433.7
758.5
1562,1
737,2
1592.4
1098
1546
1498.9
782.6
1365.9
1444,5
1412.7
1033,5
757
1435.5 I
791.9 I
1075
1100.1
1546.9
790.4 '
1102.2
1444.2
1434.2
1359,3
1036.2
1414.4
1560,1
1442,7
1093.1
1350.4
1345.5
1121
787,7
1392
817.9
1453.6
805.7
1446.8
1033.8
1439,5
808.5
1471.3
1477.7
1097.6
1467,1
1453.2
1467.8
700
830,7
700
781
780.3
1033.2
785
806.5
1477.7
787.7
758
1100,9
779,8
1398,6
700
804.2
766,2
698,5
836.9
1032.2
1444,3
816,5
1092.7
1581.2
1499.6
780.2
1136,4
1590.9
786.5
807,7
815.2
761.3
1559.2
1407.2
757
787
1388,1
1102
1386.6
1412.9
1107.4
760.1
1106.7
1429.9
820.2
817.9
793.7
777.6
789.5
787,1
1576,8
1387,6
786,6
816.1
708.4
697.9
830,1
1498
1062.8
1107.9
886.8
1482,6
1580,7
1139.8
1435
1487.9
1039.9
1597,9
834
1462.1
1410
1040
1107.8
1098,5
766.4
761.5
1468
1138,3
1475.7
1596
1488.4
810.7
1590,3
1019
794,9
1561.2
1364.9
785.9
1554.3
1385.9
1604
1464,8
695,3
738.6
1048.5
698,2
1027
1440,1
1035.9
809.2
1138,4
786,2
1015.2
1377.6
804.5
1420.3
1436.3
1452
1123.5
788.5
1177.6
1563.6
1588.7
1347.5
843.7
1582.5
1107.2
1456,6
1099.4
1564.3
743
1136,3
1125,9
1570.4
709,8
836,2
766.5
819.8
1416.2
1094,7
680.9
1036.1
697.2
1569.2
1372.1
1105.2
781.1
1104
A b s o r p t i o n Band Intensity
>
Weak
Strong
Congener
No.
771.7
1570,6
1009,4
1064.6
1044.9
825.2
825,2
1008 !
815,5
1441.9
1566.3
1139,5
832.3
697.9
1007.1
1035,8
1105,8
816,5
1444
702
837,2
1494,2
1121
763.5
787.6
696.6
1561.6
1006.7
1447.1
1371.1
833.1
1114,5
1041,3
1045,3
1553.6
712
1376,5
813,5
827.9
1041,5
1177.6
1417.3
1557.6
755.3
1440,5
811,7
817.8
735,8
1018.3
1373.7
780.3
1026.9
780.5
1084.2
1178.3
752,2
697 I
1585,3
812,6
1363,4
824,5
770.4
1040.2
1181.4
1380,2
777.7
789.6
1597
787.7
824.2
1136.2
1569.9
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
789.7
1458.9
1099,2
757.8
1464.3
1546.9
806.4
1559.6
1433.3
1439.2
1413.3
1434.2
1440,9
1409,7
1444.8
1346.1
1430,2
850,4
1438,4
1475.1
1395
1408.9
816.2
1429.6
1445.7
848.7
1456.6
800
1457,8
1438,3
1439.8
1436
1443.3
1412.5
1480
806.1
704
1435.9
1555
719
1568.4
1413,9
1342.6
701.5
1495.6
1455.2
1431
1470.3
854.7
1430.5
1431.3
1433.8
1419.8
1432.6
1545,8
1434.3
1410.5
1413
1412.3
1431.8
1557,2
735.9
1043,7
1179.4
1413.5
1440,9
1424,4
1426.5
1421
1353.4
1404,9
1344.6
1409.5
1413.7
1099.1
1583,2
1430.2
1137,1
1436.9
1590.2
1589.3
1098,8
1415.8
787.6
1044.6
794.7
1350,2
819.3
1424.4
791.7
1416
846.7
1101
741,5
794.3
1033.6
796.8
1417.9
1431.2
1450,6
1432.7
1101.2
793,1
851.8
1416
1136.5
1348.9
1138.7
1567.2
1343.4
1177.1
1414.6
1390.4
814.3
1496.4
1419.5
1351.2
1059.1
1094.3
853,4
1565.4
1596
785,9
810.5
1544.1
790.1
811.9
808.1
1184.9
1348.3
818.1
1345.9
1181.1
1125,9
1397
1417.2
1430.4
1350,8
805.7
801.7
804,4
1348,4
742
1349
1433.5
1346.6
1568.5
1088.8
1447.5
1544.8
816.8
811.7
1552.9
805,8
1543.8
791
1386
1178.5
1108.8
759.3
1101.2
743
1435.4
819.7
809,3
1036.1
678.2
1436.2
1180,8
1437,3
789.2
1413.8
801
1580.1
1075,4
781
1097.6
836.6
1355.6
1400
821.4
1427,2
1430,5
1037.4
1377.8
1063.6
1178.3
1346.7
747
1329,8
1385.8
1142.5
1447.1
808.9
1564,9
1544.7
1365.7
817.6
1434,6
1033,8
1420,9
796,9
1420
1390.4
1425,4
811.7
835.2
1071.1
1181.1 II
813.5
789 8
1368.1
1346,6
859.3
1099.7
1329.2
798.3
1428.2
780.5
1600.9
1016.9
1544.4
1378
1033.6
1369.9
1481.1
1129.9
808.7
753.9
1041
812.4
1179
736.9
1363.7
761.8
1368.6
1109.6
1107,8
832.6
1044.2
1385,8
1436.6
1179,6
1060,4
1547,3
1098.2
1098.6
1144.2
1096.8
818.8
1579.4
787.5
698.4
1415.9
1357.9
1415
813.8
1568. I
1165.1
1377.5
738,4
1097.6
1386,4
677.8
1051
1579.3
1430.4
801,3
1164,7
1483
814.3
817.9 '
1144.7
1586.1
1356
788.6
1460.3
740.1
1365.5
1378.2
1049.4
812.3
1049.3
1106.6
1054
1108.7
1366.3
1474,6
1387.6
1436.5
1099.1
796
811.1
830,8
1430.5
812.9
1363
786.6
1434
1378.6
1373.3
1179.2
1558.3
785.3
817.2
1178.7
1179.7
1570.4
778.8
1389,7
1178,8
1390.4
1166.2
780.7
1098.9
812.2
889,6
785.6
1107.3
1547,2
1480.7
1477.8
1371.2
795.3
1036.2
789.3
1036,1
1594,5
824,4
1135.9
8(79.5
708.3
701.9
1018.4
821.6
1372.6
1095.5
824.7
1544.9
1569.8
1372.5
817.3
1110.7
1102.3
1547.2
1359,7
1416.2
817.5
735.6
1361.9
788.9
875.9
869
1167
1369,9
1407.2
821.4
1180.2
819.6
1576.3
819.1
690,9
1565
818
1572
2701
Table VI.
Selected Matrix Isolated FT/IR absorption bands for all 209 PCB congeners (con't)
Congener
No.
Abeorp~n
Strong
146
147
148
149
150
151
152
153
154
155
156
157
158
159
16o
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
1470.6
1400.1
1409.8
1436
854.3
1393.9
1397.6
1449
1434
1577.9
1413
1426.7
1414.5
1404.2
722.1
1409.5
816.1
1400.5
1425.9
1078,5
1329,3
1431
1420.5
1423.1
1409.5
1419.8
1346
1352.6
1418.1
1407.8
1423.8
1401.7
Table VII.
Cong.
1416,8
848.2
857.6
1475.5
1430.9
1099
782
1455.1
818.9
817.1
1136.5
810.1
1343.6
1342.7
1328.2
1567
1546.2
1383.9
818.9
724.6
1379.4
1066
1552.1
1538.1
1181
1347
1409.6
737.2
1182A
1343
1343
1378.9
Band Intm~lty
;
Weak
1079.3
1482.5
1588.4
1181
819,1
1409.5
675.6
1087.1
1105,5
1419.1
1343.6
1353.9
820.1
809.9
1349.6
1341.1
1413.9
729.8
1180.2
1385.1
1353,2
1471.2
1367.4
808
794.4
806.2
1382.6
1328
814.6
1389.2
1180.6
1367
Congener
No.
1146
1386.1
1126.7
1049.4
1549.1
1045.7
1436
1148.2
1578.6
1550
1036.5
1167.5
1132.2
1569.5
1381,7
810.1
1391.9
1066.6
808,6
1569
751,4
813.3
862.3
1357.3
1348.4
1177.8
841
1384.7
1345.5
823.7
898.5
686.7
1389
1167
1371.9
1392.9
1374.3
10e7.4
797.4
1048,9
1083.8
859,3
773
789.4
1037.6
1595.2
1366.7
1595.8
1367.7
1479.6
1371
812
737.4
1553
822.3
1529.8
666.3
818.3
1558.4
1372.7
1380.7
1124.8
813.8
1166.5
1393.9
1062.6
1413
1330.3
1406.5
1424.2
1413.5
1353.6
1353.8
1398.2
1400.1
1406.6
1329.8
1415
1365.7
1373.2
1403.1
1372.9
1402.4
1403.4
1360.8
1353.6
1403.8
1403.3
1406.4
1356.1
1365.7
1370
1378.4
1374,4
1343
1345,5
1358.8
1399.2
1469.7
1390.9
1349.7
1133.8
813
1330.6
1363.3
1468.4
859.8
817.6
731.2
1341.1
1327.1
1167.5
1349.9
1328.3
1341.6
814
1353.8
1329.2
1338
1338.3
1331.3
1329.6
817.8
1327.5
1354.6
1338
1338.9
1326.3
1095.2
813.2
1353.2
803.9
800.7
1095.6
1346.9
1381,1
782.4
1389.1
1587.8
1339.8
1368.4
1405.7
1350
724.2 i
1181.8
1350.8
1350.8
1564.4
1331.1
1411.6
1368,3
1377.3
1073.6
1333.9
1353.2
1383.9
1331.3
1357.9
1409.3
829.4
Melting points for all crystalline PCB congeners
Structure
CAS No.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
200
Al:~orption B a n d I n b m s i t y
Strong
~
Weak
2-ChJorobiphenyl
3-Chlorobiphenyl
4-Chlorobiphenyl
2,2'-Dichiorobiphenyl
2,3-Dichlorobiphenyl
2,3'-Dichlorobiphenyl
2,4-Dichlorobiphenyl
2,4'-Dichlorobiphenyl
2,5-Dichlorobiphenyl
2,6-Dichlorobiphenyl
3,3'-Dichlorobiphenyl
3,4-Dichlomb~phenyl
3,4'-Dicldombiphenyl
3,5-Dichlombiphenyl
4,4'-Dichlorobiphenyl
2,2',3-Trichlorobiphenyl
2,2',4-Trichlo robiphenyl
2,2',5-Trichlo robJphe nyl
2,2',6-Tdchlorobiphenyl
2,3,3'-Trichlorobiphenyl
2,3,4-Trichlorobiphenyl
2,3,4'-Tl~.hlorobiphenyl
2,3,5-Trk:hlorob~phenyl
2,3,6-Tdchlorobiphenyl
2,3',4-Tdchlorobiphenyl
2,3',5-Tdchlorobiphenyl
2,3',6-Tdchlo robiphenyl
2,4,4'-Trichk)mbiphenyl
2,4, 5-Tdchlorob~phen yl
2,4,6-Trichlorob~phenyl
2,4',5-Tdchlorobiphenyl
2,4',6-Trichlorobiphenyl
2',3,4-Trichlorobiphenyl
2',3,5-Trichlorobiphenyl
3,3',4-Trichlo robiphenyl
2051-60-7
2051-61-8
2051-62-9
13029-08-8
16605-91-7
25569-80-6
33284-50-3
34883-43-7
34883-39-1
33146-45-1
2060-87-1
2974-92-7
2974-90-5
34883-41-6
2050-68-2
38444-78-9
37680-66-3
37680-65-2
38444-73-4
38444-84-7
56702..46-0
38444-85-3
55720-44-0
5870Q-,45-9
65712-37-3
38444-81-4
38444-76-7
7012-37-5
15862-07-4
35693-92-6
16606-02-3
38444-77-4
38444-86-9
37680-68-5
37680-69-6
M~ng Point "C
MellingPoint "C
(Cormct~:l)
I,.i~rature
3 0 - 31.5
oi
76 - 78
60 - 61
oil
oil
oil
44 - 45
oil
35 - 36
2 9 - 30
48 - 50
oil
32 - 33
150 - 152
oil
oil
44 - 46
90 * 92
43 - 44.5
IOQ - 103
72 - 73
3 9 - 40
56 - 57
36 - 37
42 - 43
oil
58 - 59
77 - 78
62 - 63
64.5 - 65
55 - 56
61 - 62
57 - 58
65.5 - 67
34 1 33 - 34 sl
oil I, 16 - 17 31
77.7 1, 77 - 78 31
60.5 1, 59 - 60 31
27.7 - 28.2 =
oil I
24.1 - 24.4 =, 24 - 25 =t
461
22 - 23 ~
35 - 36 1
29 I
49 - 50 z, 48 - 49 =
oil
361, 31 - 3 2 aa
149 - 150
28.1 - 28.8 u
73 - 73.2 =
41
57 - 58
78 - 79
62.5 - 64.5 1
63.5 - 64.51
60.1 - 60.4 aa
58 t
1048.1
1410.7
847.2 i
1352.2
1548.8
1350
1569.6
1408.6
1328.5
1167.7
1369
771.6
1350.6
817.6
726.1
1401.5
1342
806.4
802.8
1356.8
1401.3
1181.7
685.3
1169
1169
1383,4
1331,1
1327.5
1341.5
816.5
1062.4
696.9
1401
1348.4
1066.5
1368.6
1587.2
1357.5
1373.9
1098.8
1437.6
908.7
672.2
840.3
1387.9
1547.8
1569.3
819
852.3
1368
1335.7
1336.2
749
1073.9
1169
745.6
760.6
1393.5
1550.1
727.3
805.6
693.6
691,3
760.8
2702
Table VII.
Cong.
No.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
Melting points for all crystalline PCB congeners (con't)
Structure
3,3',5-Tdchlorobiphenyl
3,4,4'-Tdchlorobiphenyl
3,4,5-Tdchlorobiphenyl
3,4',5-TIk~hlombiphenyl
2,2',3,3'-Tetrachlorobiphenyl
2,2',3,4-Tetrachlorobiphenyl
2,2',3,4'-Tetrachlorobiphenyl
2,2',3,5-Tetrachlorobiphenyl
2,2',3,5'-Tetmchlorobiphenyl
2,2',3,6-Tetrachlorobiphenyl
2,2',3,6'-Tetmchiorobiphenyl
2,2',4,4'-Tetrachlorobiphenyl
2,2',4,5-Tetrachlorobiphenyl
2,2',4,5'-Tetmchlorobiphenyl
2,2',4,6-Tetrachlorobiphenyl
2,2',4,6'-Tetrachlombiphenyl
2,2',5,5'-Tetrachlorobiphenyl
2,2',5,6'-Tetrachlorobiphenyl
2,2',6,6'-Tetrachlorobiphenyl
2,3,3',4-Tetrachlorobiphenyl
2,3,3',4'-Tetrachlorobiphenyl
2,3,3',5-Tetrachlorobiphenyl
2,3,3',5'-Tetmchlorobiphenyl
2,3,3',6-Tot r a c h l o r o b i p h e n y l
2,3,4,4'-Totrachlorobiphenyl
2,3,4,5-Tetrachlorobiphertyl
2,3,4,6-Tetrachlorobiphenyl
2,3,4',5-Tetrachlorobiphenyl
2,3,4',6-Tetrechlorobiphenyl
2,3,5,6-Tetmchlorobiphenyl
2,3',4,4'*Tetrachlorobipheny|
2,3',4,5-Tetrachlombiphenyl
2,3',4,5'-Tetrachlorobiphenyl
2,3',4,6-Tetrachlorobiphenyl
2,3',4',5-Tetmchlorobiphenyl
2,3',4',6-Tetmchlorobiphenyl
2,3',5,5'-Tetmchlorobiphenyl
2,3',5',6-Tetmchlorobiphenyl
2,4,4',5-Tetrachlorobiphenyl
2,4,4',6-Tetrachlorobiphenyl
2',3,4,5-Tetrachlorobiphenyl
3,3',4,4'-Tetrachlorobiphenyl
3,3',4,5-Tetnachlorobiphenyl
3,3',4,5'-Tetrechlorobiphenyl
3,3',5,5'-Tetrachlorobiphenyl
3,4,4',5-Tetrachlorobiphertyl
2,2',3,3',4-Perdachlorobipheny|
2,2',3,3',5-Pentachlorobiphenyl
2,2',3,3',6-Pentachlorobiphenyl
2,2',3,4,4'-Pentachlorobiphenyl
2,2',3,4,5-Pentachlorobiphenyl
2,2',3,4,5'-Perttachlorobiphenyl
2,2',3,4,6-Pentachlombiphenyl
2,2',3,4,6'-Pentachlorobiphenyl
2,2',3,4',5-Pentachlorobiphenyl
2,2',3,4',6-P~ntachlorobiphenyl
2,2',3,5,5'-Perttachlorobiphenyl
2,2',3,5,6-Pentachlorobiphenyl
2,2',3,5,6'-PentachlorobJphenyl
2,2',3,5',6-Pentachlorobiphenyl
2,2',3,6,6'-Pentachlorobiphenyl
2,2',3',4,5-Pentachlorobiphenyl
2,2',3',4,6-Pentachlorobiphenyl
2,2',4,4',5-Perttachlorobiphenyl
2,2',4,4',6-Pentachlorobiphenyl
2,2',4,5,5'-Pentachlorobiphenyl
2,2',4,5,6'- P e n t a c h l o r o b i p h e n y l
2,2',4,5',6- P e n t a c h l o r o b i p h e n y l
2,2',4,6,6'-Pentachlorobiphenyl
2,3,3'.4,4'-Pentachlorobiphenyl
2,3,3',4,5-Pentachlorobiphenyl
2,3,3',4',5-Pentachlorobiphenyi
2,3,3',4,5'-Pentachlorobiphenyl
2,3,3',4,6-Pentachlombiphenyl
C A S No.
38444-87-0
38444-90-5
53555-66-1
38444-88-1
38444-93-8
52663-59-9
36559-22-5
70362-46-8
41464-39-5
70362-45-7
41464-47-5
2437-79-8
70362-47-9
41464-40-8
62796-65-8
68194-04-7
35693-99-3
41464-41-9
15968-05-5
74338-24-2
41464.43-1
70424-87-8
41464-49-7
74472-33-6
33025-41-1
33284-53-8
54230-23-7
74472-34-7
52663-58-8
33284-54-7
32598-10-0
73557-53-8
73575-52-7
60233-24-1
32598-11-1
41464-46-4
41464-42-0
74338-23-1
32690-93-0
32598-12-2
70362-48-0
32598-13-3
70362.49-1
41464-48-8
33284-52-5
70362-50-4
52663-62-4
60145-20-2
52663-60-2
65510-45-4
55312-69-1
38380-02-8
55215-17-3
73575-57-2
68194-07-0
68194-05-8
52663-81-3
73575-56-1
73575-85-0
38379-99-8
73575-54-9
41464-51-1
60~33-25-2
38380-01-1
39485-83-1
37680-73-2
68194-06-9
60145-21-3
56558-16-8
32598-14-4
70424-69-0
70424-68-9
70362-41-3
74472-35-8
Melting Point "C
(Corrected)
78 - 79
8 8 - 90
71 - 7 1 . 5
8 7 - 88
123 - 124
48 - 50
68 - 69
45 - 46
47.5 - 48.5
8 0 - 81
125 - 126
45.5 - 46
86 - 87
66 - 67
4 7 - 48
oil
85.5 - 86.5
101 - 103
197 - 1 9 8
85.5 - 86.5
98 - 99
87 - 88
125 - 126
oil
144.5 - 146.5
85.5 - 9 0 . 5
78 - 79
88 - 90
8 7 - 88
76 - 78.5
124 - 126
62 - 63.5
9 2 - 93
5 2 - 54
104 - 105
3 6 - 37
106 - 107.5
70 - 72
127 - 1 2 9
62 - 63
134 - 135
180 - 181
118 - 120
121 - 123
171 - 173
160 - 163
118 - 120
8 3 - 84
109 - 1 tO
47.5 - 48.5
8 5 - 86
110 - 112
66 - 66.5
85 - 86
51 - 5 3
62 - 63
6 0 - 61
96 - 97.5
8 2 - 83
9 3 - 94
119 - 120
78 - 79
94 - 95
59 - 60
oil
78 - 79
71 - 7 2
69 - 70
8 7 - 88
116.5 - 117.5
8 5 - 86
9 6 - 97
120 - 122
7 0 - 71
M e l t i n g Point "C
Literature
86.8 - 8 7 . 8 ==
88
121 - 122 ~
6 8 - 7 0 t, 6 8 . 5 7 0 2
4 9 - 5 0 28
125.5 - 127 28
41 - 4 2 1
6 6 - 6 8 . 5 ~, 6 5 - 6 6 , 5 28
8 6 . 5 - 8 7 1, 8 5 - 8 6 . 5 ~
103 - 104.5 2a
198 1
9 6 - 9 7 2B
127.5 - 129 ~
142 I
9 2 - 9 2 . 5 1 91 s
79 1
124 i, 127 - 128 2
104 I, 104 - 105 2
oil 28
105.5 - 106.5 ~
125
177 - 178 28
119 - 120 28
164 1
119 - 120.5 1
112 - 114 i
oil
9 8 . 5 - 100 i
8 7 . 5 - 8 2 . 5 =8
7 6 - 7 7 21
117 - 118.5 2s, 101 - 105 1
121 - 122 ~
2703
Table VII.
Cong.
No.
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
Melting points for all crystalline PCB congeners (con't)
StTucture
2,3,3',4',6-Pentachlorobipheny~
2,3,3',5,5'-Pentachlorobiphenyl
2,3,3',5,6-Pentachlorobiphenyl
2,3,3', 5',6- Pentachlo robiphenyl
2,3,4,4',5-Pentachlorobiphenyl
2,3,4,4',6-Pentachlorobiphenyl
2,3,4,5,6-Pentadnlorob4phenyl
2,3,4',5,6-Pentachlorobiphenyl
2,3',4,4',5- Pen tachlo robiphenyl
2,3',4, 4',6- Pen tachlo robiphenyl
2,3',4,5,5'-Pentachlorobiphenyl
2,3',4,5',6-Pentachlombipheny~
2',3,3',4,5- Pentachlorobiphenyl
2',3,4,4',5-Pentachlo robiphenyl
2',3,4,5,5'-Pentachlo robiphenyl
2',3,4,5,6'-Pentachlorobiphenyl
3,3',4,4',5- Pentmchlo robiphenyl
3,3',4,6, 5'- Pentachlo robiphenyl
2,2',3,3',4,4'-Hexachlo mbiphenyl
2,2',3,3',4,5-Hexachlombiphenyl
2,2',3, 3',4,5'.Hexachlo robiphenyl
2,2',3,3',4,6-Hexachlombiphenyl
2,2',3,3',4,6'-Hexachlorobiphenyl
2,2',3,3',5, 5'-Hexachlo robiphenyl
2,2',3,3',5,6-Hexachlorobiphenyl
2,2',3,3',5,6'-Hexachlorobiphenyl
2,2',3,3',6,6'-Hexachlorobiphenyl
2,2',3,4,4',5-Hexachlorobiphenyl
2,2',3,4,4',5'-Hexachlorobiphenyl
2,2',3,4,4',6-Hexachlorobiphenyl
2,2',3,4,4',6'-Hexachlorobiphenyf
2,2',3,4,5,5'-Hexachlorob~ph~nyl
2,2',3,4,5,6 -Hexachlo robiphenyt
2,2',3,4,5,6'-Hexachloro biphenyl
2,2',3,4,5',6-Hexachlombiphenyl
2,2',3,4,6,6'-Hexacldorobiphenyl
2,2',3,4',5, 5'-Hexachlo robiphenyl
2,2',3,4',5,6- Hexachlorobiphenyl
2,2',3,4',5,6'-Hexachlorobiphenyl
2,2',3, 4',5',6 -Hexachlo robiphe nyl
2,2',3,4',6,6'-Hexachlorobiphenyl
2,2',3,5, 5', 6-Hexacldorobipheny'l
2,2',3,5,6,6'-Hexach~orobiphenyl
2,2',4,4',5,5'-Hexachlorobiphenyl
2,2',4, 4',5,6'-Hexechlo robiphenyl
2,2',4,4',6,6'-Hexachlorobiphenyl
2,3,3',4,4',5-Hexachlorobiphenyl
2,3,3',4,4',5'-Hexachlorobiphenyl
2,3,3',4,4',6-Hexachlorob~phenyl
2,3,3',4,5,5'-Hexachlorobiphenyl
2,3,3',4,5,6-Hexachlombiphectyl
2,3,3',4,5',6-Hexach~orobiphenyl
2,3,3',4',5,5'-Hexachlorobiphenyl
2,3,3',4',5,6-Hexachlorobiphenyl
2,3,3',4',5',6-Hexachlorobiphenyl
2,3,3',5,5',6-Hexachlorobiphenyl
2,3,4,4',5,6-Hexachlombiphenyl
2,3',4, 4',5,5'-Hexachlo mbiphenyl
2,3',4,4',5',6-Hexachlo robiphe nyl
3,3',4,4',5, 5'-Hexachlo robiphe nyl
2,2',3,3',4,4',5-Heptachlo robiphenyl
2,2',3, 3',4,4',6- Heptachlo robiphenyl
2,2',3, 3',4,5, 5'- Heptachlo mbiphenyl
2,2',3,3',4,5,6-Heptachlorobiphenyl
2,2',3,3',4,5,6'- Heptachlorobiphenyl
2,2',3,3',4,5',6- Heptachlo mbiphenyl
2,2',3,3',4,6,6'- Heptachlo mbiphenyl
2,2',3,3',4',5,6- Heptachlo mbiphenyl
2,2',3,3',5, 5',6- Heptachlo robiphenyl
2,2',3,3',5,6,6'- Heptachlombiphenyl
2,2',3,4,4', 5,5'- Heptachlo robiphenyl
2,2',3,4,4',5,6-Heptaddombiphe~yl
2,2',3, 4,4',6,6'-Heptachlo robiphenyl
2,2',3,4,4',6',6-Heptachlorobipher~l
C A S No.
38380..03-9
39635-32-0
74472.-36-9
68194-10-5
74472.-37-0
74472-38-1
18259-05-7
68194-11-6
31508-00.5
56558-17-9
68194-12-7
56558-18-0
76842-074
65510-44-3
70424-70-3
74472-39-2
57465-28-8
39635-33-I
38380.07-3
55215-18.4
52663-66-8
61798-70-7
38380-05-1
35694-04-3
52704-70-8
52744-13.5
38411-22-2
35694-06-5
35065-28-2
56030-56-9
59291-64-4
52712-04-5
41411-51-4
68194-15-0
68194-14-9
74472-40-5
51908-16-8
68194-13-8
74472-41-5
38380-04-0
68194-08-1
52663.53.5
68194-09-2
35065-27-1
60145-22-4
33979-03-2
38380.08-4
69782-90-7
74472-42-7
39635-35-3
41411-62-5
74474-43-8
39635.-34-2
74472-44-9
74472-45.0
74472.46-1
41411-63.5
52663-72-8
59291-65-5
32774-16.5
35065-30-6
52663-71-5
52663-74-3
68194-16-1
38411-25-8
40186-70-7
52663.55-7
52663-70-4
52663-67-9
35065-29-3
35065-29-3
74472-47-2
60145-23-5
52663-69-1
Mel~ng Point "C
(CorrectKI)
Mel~ng Point "C
Lit*mture
6 3 - 55
107-107.5
91.93
5 6 - 57
9 8 - gg
64.5 - 65
122-125
167 - 171
111 - 1 1 3
7 6 - 77
131 - 133
9 3 - 94.5
117 - 118
134 - 135
116 - 117
126 - 127
160 - 161
152 - 153
150 - 152
IOQ - 104
114-116
135 - 137
116-118
127 - 128
132 - 133
102 - 103
112-113.5
81-82
79 - 80
75.5 - 77
68-69
8 8 - 89
134 - 135
89-90
72-74
136 - 137
8 8 - 90
136 - 138
80.5 - 81
78 - 7 9
76-77
98 100
126 - 127
102 - 103.5
6 8 - 70
111-113
129.5 - 131
161 - 162
110 - 112
149 - 150
92-92.5
105 - 106
143 - 144
121 - 123
9 2 - 94
151 - 152
164 - 167
125 - 127
108.5-109.5
208-210
136.5 - 138.5
116.5 - 118.6
135 - 137
204 -205
124 - 125
121 - 123
IOQ - 103
1 5 2 - 154
110-112
129 - 131
112.5-114
125 - 126
107.5 - 109.5
93 - 95
oil t
105 ~
98 - g9 t
123 I, 1 2 4 - 1 2 5 ~
112-113 x
128 - 129 t
114-114.5 t
7 7 - 78 t, 78.5 - 8 0 a°
78.5 - 80 1
69.5-71
I
134 - 137
oil
-
103 - 104 1
112.51,112-
113 al
97-100 t
160 - 165 ~e
110-111 I
201 - 2 0 2 1
134.5 - 135.5 1
130.5 - 130.7 I
100-110
~
2704
Table VII.
Cong.
No.
Melting points for all crystalline PCB congeners (con't)
Structure
CAS No.
184
2,2',3,4,4',6,6'-Heptachlorobiphenyl
185
2,2',3,4,5,5',6-Heptachlorobiphenyl
186
2,2',3,4,5,6,6'-Hoptachtorobiphenyl
187
2,2',3,4',5,'5',6- Heptachlo mbiphe nyl
188
2,2',3,4',5,6,6'- Heptachlo robiphenyl
189
2,3,3',4,4',5,5'-Heptachlorobiphenyl
190
2,3,3',4,4',5,6-Heptachlorobiphenyl
191
2,3, 3', 4,4',5',6- Heptachlo robiphenyl
192
2,3,3',4,5,5',6-Heptacldorobil~enyl
193
2,3,3',4',5,5',6- Heptachlo robiphenyl
194
2,2',3,3',4,4',5, 5'-Octachlorobiphenyl
195
2,2',3,3',4, 4',5,6-Oct,,chlo robiphen yl
196
2,2',3,3',4,4',5',6-Octachlorobiphenyl
197
2,2',3,3',4,4',6,6',Octachlorobiphenyl
198
2,2',3,3',4,5,5',6-Octachlorobiphenyl
199
2,2',3,3',4,5,6,6'-Octachlorobiphenyl
(IUPAC #200)
200
2,2',3,3',4,5',6,6'-Octachlombiphenyl
(IUPAC #201)
201
2,2',3,3',4,5,5',6'-Octachlorob~phenyl
(IUPAC #199)
202
2,2',3, 3',5,5',6,6'-Octachlorobiphenyl
203
2,2',3,4,4', 5, 5',6-Ocbu:~lo robiph eny{
204
2,2',3,4,4', 5, 6,6'-Octachlombiphenyl
205
2,3,3',4,4', 5, 5',6-Octachlombipheny/
206
2,2',3,3',4,4',5,5',6-N onacldorobil~enyl
207
2,2' ,3,3',4,4',5,6,6'-N onacldorobiphenyl
208
2,2',3,3',4,5,5',6,6'-Nonachlorobiphenyl
209
2,2',3,3',4,4',5,5',6,6'-Decachlorobiphenyl
Melting Point "C
(Corrected)
74472-48-3
52712-05-7
74472-49-4
52663-68-0
74487-85-7
39635-31-9
41411-64-7
74472-50-7
74472-51-8
69782-91-8
35694-08-7
52663-78-2
42740-50-I
33091-17-7
68194-17-2
52663-73-7
171
138
155
170
127
137
195
175
40186-71-8
141 - 143
52663-75-9
157 - 158
2136--994
52663-76-0
74472-52-Q
74472-53-0
40186-724)
52663-79-3
52663-77-1
2051-24-3
157
111
175
197
115
117
148
195
104
134
162
122
150
198
105
135
163
124
Mel~ng Point "C
Literature
116-118
~
112.5 - 114.5
-
174
141
157
172
129
139
197
176
- 159
- 113
- 179
- 199
202- 204
213 - 215
180 - 181
318 - 320
156 - 157 1, 159 - 160
'
126 - 128 '
132'
161
'
305.6, 310 1
CONCLUSIONS:
The s y n t h e s i s and the s u b s e q u e n t c o m p i l a t i o n of c h r o m a t o g r a p h i c ,
tral and p h y s i c a l
more accurate
data of all 209 PCB c o n g e n e r s will p r o v i d e a m e a n s
specfor the
i d e n t i f i c a t i o n of b i o l o g i c a l l y a c t i v e and toxic congeners.
a d d i t i o n to i m p r o v i n g the q u a l i t a t i v e aspect of PCB analysis,
also aid in the q u a n t i f i c a t i o n of these compounds.
ACKNOWLEDGMENT :
For t h e i r help,
g u i d a n c e and m o t i v a t i o n we t h a n k all those w h o h a v e
c o n t r i b u t e d to this p r o j e c t
e s p e c i a l l y Daniel Abramowitz,
D o n n a Bedard,
M a t t h e w Bolgar,
J o h n Brown,
B r i a n Bush,
Ishak Ferosie,
Otto Hutzinger,
T h e o d o r e Lynn,
Robert Checkosky,
J o h n Mahon,
Silva T e r d j a n i a n and K e n n e t h Wnuk.
S t e v e n Safe,
In
this data will
Juliet Terdjanian,
2705
REFERENCES
1.
2.
3.
4.
5.
6.
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8.
9.
10.
ii.
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20.
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25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
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