Environ. Sci. Technol.
1988,22,382-387
Octanol-Water Partition Coefficients of Polychlorinated Biphenyl Congeners
Darryl W. Hawker” and Des W. Connell
School of Australian Environmental Studies, Griffith University, Nathan, Queensland, Australia 4 1 11
Octanol-water partition coefficients (KO,)for 13 poly-
chlorinated biphenyl (PCB) congeners were accurately
determined by the generator column technique. These
values were used to confirm a highly significant linear
relationship between log KO, and the logarithm of the
relative retention time on a nonselective gas chromato-
graphic stationary phase. The total surface areas (TSA)
for all the PCB congeners were determined by assuming
planar molecules, van der Waal’s radii for component at-
oms, and appropriate values for solvent radius, bond an-
gles, and distances. The TSA was highly significantly
correlated with log KO,and the relationship used to cal-
culate log KO,values for all the PCB congeners. Further
development of these relationships gave an expression for
aqueous solubility which can be used to calculate the
solubility for those PCB’s where appropriate data are
available.
Introduction
Polychlorinated biphenyls (PCB’s) were recognized as
significant environmental contaminants in 1966, and since
that time, their ubiquitous presence in biotic adipose
tissues has been established (1,2). There is now consid-
erable interest in evaluating the potential environmental
behavior of the PCB’s, and other compounds, by utilization
of their physicochemical characteristics.
A key parameter in assessing the potential environ-
mental behavior of such lipophilic chemicals is the octa-
nol-water partition coefficient Wow)(3). The determi-
nation of KO,is recommended in the OECD chemical
hazard evaluation program (4), and it has been used with
considerable success in estimating bioconcentration factors,
soil and sediment organic carbon-water partition coeffi-
cients, toxicities, and aqueous solubilities (5-11). The use
of KO,with the PCB’s is limited because inconsistent
values have been reported for some PCB congeners while
for many of the compounds these values have not been
determined.
A number of techniques have been used to measure KO,
values. The first was the shake-flask method in which the
concentrations of the compound are measured in octanol
and water, shaken together until equilibrium is attained.
However, the water concentrations may be inaccurate due
to formation of molecular aggregates and the analytical
difficulties inherent in the measurement of the extremely
low aqueous equilibrium concentrations (12). Measure-
ments and estimates based upon reverse-phase high-per-
formance liquid chromatography and thin-layer chroma-
tography (RP-HPLC and RP-TLC) have achieved mod-
erate success for other groups of lipophilic compounds but
require the use of empirical correction factors in the case
of PCB’s (12-17). Reliable and consistent KO,values for
a number of PCB congeners have been obtained by the
generator column technique, which obviates problems such
as colloidal suspensions, absorption, and volatilization of
the solute (18,19). With this technique an octanol solution
of the compound is sorbed to a solid support in a column,
and the quantity of the compound in a mobile phase of
water or octanol-saturated water which is passed through
is determined (20). The log KO,values of some PCB’s
determined by this technique have been shown to be lin-
382 Environ. Sci. Technol., Vol. 22, No. 4, 1988
early related to the logarithms of their relative retention
times (a)on GC analysis with a nonselective (C-87) sta-
tionary phase (18) by
log KO, = 1.40 log a + 5.54 (1)
Although the compounds employed were all ortho sub-
stituted except for biphenyl, it would be expected that a
and KO,would generally increase with chlorine substitution
number, and so this relationship provides a possible means
of estimation of KO,values for all 209 PCB congeners, as
well as biphenyl.
Octanol-water partition coefficients have been correlated
with molecular properties such as molar refraction, para-
chor, and connectivity indices (21-23) and also indirectly
estimated from a base value with additive fragmental
constants for chlorine or separate constants for chlorine
in the ortho, meta, and para positions. Such approaches
with PCB congeners have proven relatively unsuccessful.
However, some success has been recently achieved in
relating log KO,to calculated molar volumes (24). Also,
total surface area (TSA), which is a function of molar
volume, has been found to have a linear relationship with
log KO,for compounds such as polyaromatic hydrocarbons
and alkyl- and halobenzenes (23-26).
Thus the aims of our work were as follows: first, to
measure KO,values for some PCB congeners by the gen-
erator column method and to confirm the linear relation-
ship between log KO, and log a;second, to determine a
relationship between TSA and log KO,and to use this to
predict the log KO,values of all the remaining PCB isomers
and congeners.
Materials and Methods
The l-octanol used was purchased from Sigma Chemical
Co., St. Louis, MO, with a stated purity of >99%. The
PCB congeners were obtained from Ultra Scientific Inc.,
Hope, RI, and the purity as determined by GC analysis
was >95%. Water was deionized and then distilled while
the n-hexane employed was twice fractionally distilled
through a helice-filled glass column of approximately 10
theoretical plate efficiency.
The KO,determinations was made with both modified
and nonmodified generator column techniques (19, 20).
The mobile phase was pumped with a Waters Associates
Model 510 HPLC pump at a flow rate of 0.2 mL min-’
connected with stainless steel tubing, 0.051-cm id., to the
generator column constructed from stainless steel (48 cm
X 0.4 cm id.) and half filled with solid support. The
column eluant was collected in a preweighed receiving
flask, reweighed, and extracted (efficiency >go%) with a
Waters Associates (3-18 reverse-phaseSep-Pak column (19,
27). Aqueous concentrations were then determined by
injection of an aliquot (10 pL) of the hexane eluant (5 mL)
from the Sep-Pak column into a Tracor Model 560 GC
equipped with an electron capture detector (63Ni,350 “C)
and linearizer. Peak areas were quantified on a HP 3390A
integrator, and concentrations were determined by com-
parison with the peak areas of standard hexane solutions
of the congener of interest. To ensure the highest possible
accuracy, fresh standard solutions were regularly made up.
Relative retention times (2,4,5-trichlorobiphenyl= 1)
of a series of PCB congeners were measured on a 3 % (w/ w)
0013-936X/88/0922-0382$01.50/0 0 1988 American Chemical Society
 -
Table I. Logarithms of Octanol-Water Partition
Coefficients and Relative Retention Times of
Polychlorinated Biphenyls 8.0 -
compound log KO, log a4
-
2,2’,6,6’-tetra 5.48 0.02
2,2’,5,6’-tetra 5.46 0.08
2,2’,3,3’-tetra 5.55 0.24 7.0 -
2,3,5,6-tetra 5.94 0.19
2,3,4,5-tetra 6.18 0.32
2,3’,4,4’-tetra 6.31 0.35 -
3,3’,4,4’-tetra 6.21 0.39
2,2’,4,6,6’-penta 5.37 0.18
2,3,3’,4,4’-penta 5.82 0.63 6.0 -
2,2‘,3,3‘,6,6‘-hexa 5.76 0.54 -D0
2,2’,3,3’,4,5’,6,6’-octa 7.21 0.75
2,2’,3,3’,4,4’,5,5’-octa 7.67 1.00 -
2,2’,3,3‘,4,4‘,5,6,6’-nona 7.52 1.13
Relative to 2,4,5-trichlorobiphenyl. 5.0 -
C-87 hydrocarbon (Alltech Associates, Deerfield, IL) on -
Chromosorb W (SO/lOO mesh) glass column (2.75 m X 0.3
cm id.), isothermally at 270 “C. The series of 13 PCB’s
was selected so as to contain a great deal of structural 4.0 -
variation and cover a wide range of lipophilicity (see Table
I). It included seven tetrachlorobiphenyls with from zero
(3,3’,4,4’-)to four (2,2’,6,6’-)
ortho-substituted chlorines -1.5 -1.0 -0.5 0 0.5 1.0 1.5 2.0
and also two substituted on one ring only, together with log rx
six other congeners containing five, six, eight, and nine Figure 1. Plot of log KO, versus log a using our experimental data
chlorine substituents. (A)and that of Miller (0)(78) and showing the linear regression line
represented by eq 2.
Results
Table I contains the log Kowand log a values determined
for our selected PCB congener series. The reference
compound, 2,4,5-trichlorobiphenyl,for the relative reten-
tion time data is the same as was used by Miller (18). This
compound was not available to us, but its retention time
under our gas chromatographic conditions was calculated
by utilizing the presence of 2,2/,3,3/,6,6/-hexachlorobiphenyl
in both experimental sets of compounds.
A plot of log KO,against log a for the experimental data
from Table I and Miller’s data is presented in Figure 1.
The linear regression equation is
log KO,= 1.47 log a + 5.52 (2)
r = 0.951 Sy,z= 0.332
This equation is very similar to that derived from Miller’s
data (18) (eq 1) and demonstrates a highly significant
relationship betwen log KO,and log a.
Figure 2 contains the above log KO,data, together with
further PCB generator column derived data from Wood-
burn (19) for a total of 46 congeners (37individual com-
pounds), plotted against the TSA of the molecules with
a 0’ dihedral angle between the phenyl rings, on the basis
of calculations by Armstrong (28,29). Regression analysis 0
yields I I I I I I I I I I I I I I I
log KO,= (3.41X 10-’)TSA - 2-20 (3)
r = 0.959 Sy,x= 0.319

Discussion
The theoretical basis for a linear relationship between
log KO,and log a has been developed by Wasik et al. (30).
The high significance ( r = 0.951, Sy,x= 0.332,n = 30) of
the relationship between these parameters with our ex-
perimental results for selected diverse PCB congeners
suggests that log KO,values for other PCB’s could be es-
timated with reasonable precision from such a relationship.
It must be emphasized however that it would be expected
Table 11. log KO,Values for PCB Congeners
congener substitution TSA,b congener substitution TSA,b
no. patterna ~ 1 0 - 2 0m2 log KO, no. patterna X ~ O - ~ m2
O log KO,
0 biphenyl 184.43 4.09 75 2,4,4’,6- 241.85 6.05
1 2- 195.45 4.46 76 2,3’,4’,5’- 244.35 6.13
2 3- 201.95 4.69 77 3,3’,4,4’- 251.02 6.36
3 4- 202.12 4.69 78 3,3’,4,5- 250.85 6.35
4 2,2’- 200.80 4.65 79 3,3’,4,5’- 252.77 6.42
5 2,3- 210.34 4.97 80 3,3’,5,5’- 254.51 6.48
6 2,3’- 212.97 5.06 81 3,4,4’,5- 251.02 6.36
7 2,4- 213.14 5.07 82 2,2’,3,3’,4- 246.36 6.20
8 2,4‘- 213.14 5.07 83 2,2’,3,3‘,5- 248.10 6.26
9 2,5- 212.97 5.06 84 2,2’,3,3’,6- 241.60 6.04
10 2,6- 206.46 4.84 85 2,2’,3,4,4’- 249.16 6.30
11 3,3’- 219.47 5.28 86 2,2’,3,4,5- 247.07 6.23
12 3,4- 217.73 5.22 87 2,2’,3,4,5’- 248.99 6.29
13 3,4‘- 219.64 5.29 88 2,2’,3,4,6- 242.48 6.07
14 3,5- 219.47 5.28 89 2,2’,3,4,6’- 242.48 6.07
15 4,4‘- 219.81 5.30 90 2,2’,3,4’,5- 250.90 6.36
16 2,2’,3- 215.69 5.16 91 2,2‘,3,4‘,6- 244.40 6.13
17 2,2’,4- 218.50 5.25 92 2,2’,3,5,5’- 250.73 6.35
18 2,2’,5- 218.32 5.24 93 2,2’,3,5,6- 241.60 6.04
19 2,2’,6- 211.82 5.02 94 2,2’,3,5,6’- 244.23 6.13
20 2,3,3’- 227.86 5.57 95 2,2‘,3,5‘,6- 244.23 6.13
21 2,3,4- 226.11 5.51 96 2,2‘,3,6,6’- 232.06 5.71
22 2,3,4’- 228.03 5.58 97 2,2’,3,4’,5’- 248.99 6.29
23 2,3,5- 227.86 5.57 98 2,2’,3,4’,6’- 244.40 6.13
24 2,3,6- 221.35 5.35 99 2,2’,4,4’,5- 251.79 6.39
25 2,3‘,4- 230.66 5.67 100 2,2’,4,4’,6- 247.20 6.23
26 2,3’,5- 230.49 5.66 101 2,2’,4,5,5’- 251.62 6.38
27 2,3’,6- 223.99 5.44 102 2,2’,4,5,6’- 254.12 6.16
28 2,4,4’- 230.83 5.67 103 2,2’,4,5’,6- 247.03 6.22
29 2,4,5- 228.74 5.60 104 2,2’,4,6,6’- 234.87 5.81
30 2,4,6- 224.16 5.44 105 2,3,3’,4,4’- 259.41 6.65
31 2,4’,5- 230.66 5.67 106 2,3,3’,4,5- 259.24 6.64
32 2,4’,6- 224.16 5.44 107 2,3,3’,4’,5- 261.15 6.71
33 2,3’,4’- 228.75 5.60 108 2,3,3’,4,5’- 261.15 6.71
34 2,3‘,5’- 230.49 5.66 109 2,3,3’,4,6- 254.65 6.48
35 3,3‘,4- 235.25 5.82 110 2,3,3’,4’,6- 254.65 6.48
36 3,3’,5- 236.99 5.88 111 2,3,3’,5,5’- 262.90 6.76
37 3,4,4’- 235.42 5.83 112 2,3,3’,5,6- 253.76 6.45
38 3,4,5- 233.33 5.76 113 2,3,3’,5’,6- 256.39 6.54
39 3,4’,5- 237.16 5.89 114 2,3,4,4’,5- 259.41 6.65
40 2,2’,3,3’- 230.58 5.66 115 2,3,4,4’,6- 254.82 6.49
41 2,2’,3,4- 231.47 5.69 116 2,3,4,5,6- 250.10 6.33
42 2,2’,3,4’- 233.38 5.76 117 2,3,4‘,5,6- 253.93 6.46
43 2,2’,3,5- 233.21 5.75 118 2,3’,4,4’,5- 262.04 6.74
44 2,2‘,3,3‘- 233.21 5.75 119 2,3’,4,4’,6- 257.45 6.58
45 2,2‘,3,6- 226.71 5.53 120 2,3‘,4,5,5‘- 263.78 6.79
46 2,2’,3,6’- 223.71 5.53 121 2,3’,4,5’,6- 259.20 6.64
47 2,2‘,4,4’- 236.19 5.85 122 2,3,3’,4’,5’- 259.24 6.64
48 2,2’,4,5- 234.10 5.78 123 2,3,4,4’,5’- 262.04 6.74
49 2,2’,4,5’- 236.01 5.85 124 2,3’,4’,5,5’- 261.87 6.73
50 2,2’,4,6- 229.51 5.63 125 2,3’,4’,5’,6- 255.37 6.51
51 2,2’,4,6’- 229.51 5.63 126 3,3‘,4,4‘,5- 266.63 6.89
52 2,2’,5,5’- 235.84 5.84 127 3,3‘,4,5,5‘- 268.37 6.95
53 2,2’,5,6’- 229.34 5.62 128 2,2’,3,3’,4,4’- 262.13 6.74
54 2,2’,6,6’- 217.18 5.21 129 2,2’,3,3’,4,5- 261.96 6.73
55 2,3,3’,4- 243.63 6.11 130 2,2’,3,3’,4,5’- 263.88 6.80
56 2,3,3’,4’- 243.63 6.11 131 2,2’,3,3’,4,6- 257.37 6.58
57 2,3,3’,5- 245.38 6.17 132 2,2’,3,3’,4,6’- 257.37 6.58
58 2,3,3’,5’- 245.38 6.17 133 2,2’,3,3’,5,5’- 265.62 6.86
59 2,3,3’,6- 238.87 5.95 134 2,2’,3,3’,5,6- 256.49 6.55
60 2,3,4,4’- 243.80 6.11 135 2,2’,3,3’,5,6’- 259.12 6.64
61 2,3,4,5- 241.72 6.04 136 2,2’,3,3’,6,6’- 246.95 6.22
62 2,3,4,6- 237.13 5.89 137 2,2’,3,4,4’,5- 264.76 6.83
63 2,3,4’,5- 245.55 6.17 138 2,2’,3,4,4’,5’- 264.76 6.83
64 2,3,4’,6- 239.04 5.95 139 2,2’,3,4,4’,6- 260.18 6.67
65 2,3,5,6- 236.24 5.86 140 2,2’,3,4,4’,6’- 260.18 6.67
66 2,3’,4,4‘- 246.44 6.20 141 2,2’,3,4,5,5’- 264.59 6.82
67 2,3‘,4,5- 246.26 6.20 142 2,2’,3,4,5,6- 255.46 6.51
68 2,3‘,4,5‘- 248.18 6.26 143 2,2’,3,4,5,6’- 258.09 6.60
69 2,3’,4,6- 241.68 6.04 144 2,2’,3,4,5’,6- 260.00 6.67
70 2,3’,4’,5- 246.26 6.20 145 2,2’,3,4,6,6’- 247.84 6.25
71 2,3’,4’,6- 239.76 5.98 146 2,2’,3,4’,5,5’- 266.51 6.89
72 2,3’,5,5’- 248.01 6.26 147 2,2‘,3,4‘,5,6- 259.29 6.64
73 2,3’,5’,6- 241.50 6.04 148 2,2‘,3,4‘,5,6‘- 261.92 6.73
74 2,4,4’,5- 246.43 6.20 149 2,2’,3,4’,5’,6- 260.00 6.67

384 Environ. Sci. Technol., Vol. 22, No. 4, 1988

Table I1 (Continued)
congener substitution TSA: congener substitution TSA:
no. pattern‘ X ~ O - ~ m2
O 1% KO, no. pattern’ ~ 1 0 - 2 0m2 log KO,
150 2,2’,3,4’,6,6’- 249.76 6.32 180 2,2’,3,4,4’,5,5’- 280.37 7.36
151 2,2’,3,5,5’,6- 259.12 6.64 181 2,2’,3,4,4’,5,6- 273.15 7.11
152 2,2’,3,5,6,6’- 246.95 6.22 182 2,2‘,3,4,4‘,5,6‘- 275.78 7.20
153 2,2’,4,4’,5,5’- 267.39 6.92 183 2,2’,3,4,4’,5’,6- 275.78 7.20
154 2,2’,4,4’,5,6’- 262.81 6.76 184 2,2’,3,4,4’,6,6’- 265.53 6.85
155 2,2’,4,4’,6,6’- 252.56 6.41 185 2,2’,3,4,5,5’,6- 272.98 7.11
156 2,3,3‘,4,4‘,5- 275.01 7.18 186 2,2’,3,4,5,6,6’- 260.81 6.69
157 2,3,3‘,4,4‘,5’- 275.01 7.18 187 2,2’,3,4’,5,5’,6- 274.89 7.17
158 2,3,3’,4,4’,6- 270.64 7.02 188 2,2’,3,4’,5,6,6’- 264.64 6.82
159 2,3,3’,4,5,5’- 276.76 7.24 189 2,3,3’,4,4’,5,5’- 290.61 7.71
160 2,3,3’,4,5,6- 267.62 6.93 190 2,3,3’,4,4’,5,6- 283.40 7.46
161 2,3,3’,4,5’,6- 272.17 7.08 191 2,3,3’,4,4’,5’,6- 286.03 7.55
162 2,3,3’,4’,5,5’- 276.76 7.24 192 2,3,3’,4,5,5’,6- 285.14 7.52
163 2,3,3‘,4’,5,6- 296.54 6.99 193 2,3,3’,4’,5,5’,6- 285.14 7.52
164 2,3,3’,4’,5’,6- 270.25 7.02 194 2,2’,3,3’,4,4’,5,5’- 293.34 7.80
165 2,3,3’,5,5’,6- 271.28 7.05 195 2,2’,3,3’,4,4’,5,6- 286.12 7.56
166 2,3,4,4‘,5,6- 267.79 6.93 196 2,2’,3,3’,4,4’,5,6’- 288.75 7.65
167 2,3‘,4,4’,5,5‘- 277.64 7.27 197 2,2’,3,3’,4,4’,6,6’- 278.50 7.30
168 2,3’,4,4’,5’,6- 273.06 7.11 198 2,2’,3,3’,4,5,5’,6- 287.87 7.62
169 3,3’,4,4’,5,5’- 282.23 7.42 199 2,2’,3,3’,4,5,6,6’- 275.70 7.20
170 2,2’,3,3’,4,4’,5- 277.74 7.27 200 2,2’,3,3’,4,5’,6,6’- 277.62 7.27
171 2,2‘,3,3‘,4,4’,6- 273.15 7.11 201 2,2’,3,3’,4,5,5’,6’- 287.87 7.62
172 2,2’,3,3’,4,5,5’- 279.48 7.33 202 2,2’,3,3’,5,5’,6,6’- 276.73 7.24
173 2,2’,3,3’,4,5,6- 270.35 7.02 203 2,2’,3,4,4’,5,5’,6- 288.75 7.65
174 2,2’,3,3’,4,5,6’- 272.98 7.11 204 2,2’,3,4,4’,5,6,6’- 278.50 7.30
175 2,2’,3,3’,4,5’,6- 274.89 7.17 205 2,3,3‘,4,4’,5,5’,6- 299.00 8.00
176 2,2’,3,3’,4,6,6’- 262.73 6.76 206 2,2’,3,3’,4,4’,5,5’,6- 301.73 8.09
177 2,2’,3,3’,4,5’,6’- 272.26 7.08 207 2,2’,3,3’,4,4*,5,6,6’- 291.48 7.74
178 2,2’,3,3’,5,5’,6- 274.01 7.14 208 2,2’,3,3’,4,5,5’,6,6’- 290.59 7.71
179 2,2’,3,3’,5,6,6’- 261.84 6.73 209 decachlorobiphenyl 304.45 8.18
‘Using the numbering system of Zell et al. (40). *With planar molecules.

because it is nonselective and can be operated at high
temperatures (31). For small values of log a there is a close
correspondencebetween experimental log a values on C-87
and those calculated for Apiezon L (which has McEEeynolds
constants close to those of C-87). But with larger log a
values there is an increasing disparity (32). Retention
times of all PCB congeners on (2-87 are thus difficult to
predict from results obtained with Apiezon L and more
difficult with more diverse stationary phases. Therefore,
the relationship expressed by eq 2 can only be effectively
used for estimation of unknown log KO,values, where the
relative retention time is measured directly on (2-87 sta-
tionary phase.
Partition coefficients are related to the free-energy
change on transfer between two phases. Also for groups
of chemically similar compounds there is much empirical
evidence to suggest that log KO,values are related to the
aqueous solvent cavity size or the size of the solute mol-
ecule (23,33-35). For example, a linear relationship be-
tween molar volume (cm3 mol-’) and log KO, has been
found for 17 ortho-substituted PCB congeners (27).
However, the molar volumes were calculated by the Le Bas
method with a constant increment for chlorine regardless
of position. Such calculations cannot account for variations
in substitution patterns between isomers that have been
observed to have marked effect on log KO,(see Table I).
Pearlman (36)has indicated that there is in general, little
difference between the use of surface area and the use of
volume for these correlations. Surface area computations
with a range of compounds have proven reliable estimates
of log KO,values and are also sensitive to structural var-
iation (24, 26, 35, 37).
The experimental log KO,determinations for a series of
tetrachlorobiphenyls (Table I) reveal that the values are
smallest for the fully ortho substituted isomers and
greatest for the isomer with no o-chlorines and extend over
almost 1order of magnitude. To facilitate the comparison
of TSA with log KO,and encompass such variation, it is
appropriate to accentuate the difference in TSA between
these isomers. This was achieved by consideration of the
surface areas of PCB molecules in a planar configuration,
with a Oo dihedral angle between the phenyl rings. In this
configuration, much of the exposed surface area of ortho
substituents, particularly chlorine, is reduced by mutual
occlusion. It is emphasized that for most PCB congeners
this planar conformation is a hypothetical one that cannot
exist in reality because of excessive steric ortho-ortho
interactions.
Surface areas of all PCB congeners have been calculated
by Armstrong ( 2 4 2 9 )on the basis of a computer program
using the van der Waals radii of component atoms, zero
solvent radius, and appropriate bond distances and angles.
The interplanar angle can be arbitrarily specified, and thus,
an accurate computation of the TSA for all congeners in
a planar configuration can be obtained (see Table 11). In
addition, we have found using a program originally written
by Hermann (QCPE No. 225) (35)that areas comparable
to those listed in Table TI are obtained with similar input
data.
A plot of geherator column derived log KO, values
against TSA, in a planar configuration, is shown in Figure
2, yielding a significant linear relationship, expressed by
eq 3 (r = 0.959, S,,% = 0.320, n = 46), for PCB’s ranging
from the parent biphenyl to decachlorobiphenyl and con-
taining all levels of ortho substitution. The outlying points
in Figure 2 do not always represent those congeners for
which forced planarity is a poor model. This suggests that
this relationship could be used to provide reasonable es-
timates of previously unknown log KO,values of PCB
congeners. The calculated log KO,values of all the PCB
congeners are shown in Table 11. It is noteworthy that
these data include values for non-ortho-substituted PCB’s,
Ehviron. Sci. Technol., Vol. 22, No. 4, 1988 385
 which are not present to any significant extent in com-
mercial products but have been shown to be the most toxic
(38).
The inadequacy of the fragmental constant approach to
prediction of log KO,values is revealed by consideration
of the TSA data. For example, TSA increases on sub-
stitution in the 2-, 3-, and 4-positions of biphenyl are 11.0
X 17.5 X and 17.7 X m2,respectively, and
with 2,2’-dichlorobiphenyl, TSA takes into account o-
chlorine overlap and is not merely the sum of biphenyl and
two ortho contributions. In addition, allowance is made
for overlap with adjacent chlorine substituents (e.g., 3,4-
dichlorobiphenyl). However, there are few examples of
systematic increases in surface area with chlorine substi-
tution, one being biphenyl, 3-chlorobiphenyl, 3,3’-di-
chlorobiphenyl, 3,3’,5-trichlorobiphenyl,and 3,3’,5,5‘-
tetrachlorobiphenyl. TSA calculations thus provide for
a greater precision in recognizing subtle variations between
PCB congeners.
Of the experimentally determined log KO,values, only
those for 2,3,4,5-tetra- (6.18) and 2,2’,3,3’,6,6’-hexachloro-
biphenyl (5.76) have been measured before, and the values
obtained in that study were 5.72 and 6.63, respectively (33).
There is little reliable partition coefficient data concerning
most PCB’s, and much of that we have used in deriving
our correlation. In order to judge the validity and pre-
dictive utility of eq 3, however, the calculated log Kowvalue
of 4,4‘-dichlorobiphenyl (5.30) may be compared with
published values of 5.58 (IO),4.82 (12),4.92 (14),5.36 (In,
and 5.33 (19) and that of decachlorobiphenyl (8.18) with
previous values of 8.26 (18) and 8.20 (19). Agreement is
quite reasonable considering that the partition coefficients
differ by 3 orders of magnitude.
The aqueous solubility of these compounds is also of
interest. Knowledge or reliable estimates of log Kowpro-
vide a method for determination of maximum aqueous
solubilities. Relationships between the logarithm of
maximum aqueous solubility [log S (mol L-l)] and parti-
tion coefficient were originally theorized to be of an inverse
linear form (11,24,39). Including a term to account for
the crystal lattice interactions of solids, equations of the
following general form were proposed:
log KO, =
-log ”-(
s + 2.303R 1- %) - log yo* - log vo* (4)
where AS, is the entropy of fusion (J K-l mol-l), R is the
gas constant (8.314 J K-l mol-l), T M is the melting point
(K) of the solid solute, T i s the system temperature (K),
yo* is the activity coefficient in water-saturated octanol,
and Vo*is the molar volume of water-saturated octanol
(126.6 X L mol-’) (33).
These derivations, possessing a negative unitary slope,
assume a constant value of log yo*. Recently, it has been
found that for PCB’s and chlorobenzenes log yw (the
aqueous activity coefficient) and hence log S together with
log yo* are linearly related to solute molar volume due to
increasing size and nonideality (33). On this basis, it has
been proposed that log KO,to log S correlations should
have a slope slightly greater than -1, in agreement with
experimental correlations where the slope is commonly of
the order of -0.8 (11,24).
Using PCB solubility data from Miller (I@, log KO,is
related to log S for these compounds by
log KO, = -0.795
2.303R
(1 - %)]+ 0.960
(5)
388 Environ. Sei. Technol., Vol. 22, No. 4, 1988
For compounds that are liquid at the system temperature,
the melting point T M is set equal to T and hence the
entropic term (ASf/2.303R)(l - TM/T) reduces to zero.
Correlating these log S - (ASf/2.303R)(1- TM/T)data
with TSA values from Table 11, an expression for solubility
in terms of TSA results (r = 0.949, S,,x = 0.464, n = 17):
log S = (-4.13 X 10-’)TSA +- (1 - $) + 3.48
2.303R
(6)
Assuming the entropy of fusion to be approximately 54.8
J K-l mol-l (18),then the maximum aqueous solubility of
a PCB congener can be estimated from its melting point
and TSA (Table 11) with eq 6.
Calculated solubilities compare favorability to published
data. The value for 4,4’-dichlorobiphenyl (1.95 X mol
L-l) is in good agreement with literature solubilities of 2.78
X (IO),2.51 X (41),and 3.59 X mol L-l (42).
There is similar agreement between the calculated solu-
bility of decachlorobiphenyl (1.62 X mol L-l) and
published values of 1.49 X (18), 3.21 X 10-l’ (41),and
8.02 X mol L-I (43).
Conclusions
These results indicate that there is a direct linear rela-
tionship between log KO,and log a,when a nonselective
gas chromatographic stationary phase is used, expressed
by eq 2. It is suggested that this relationship could be used
to obtain the KO,values for all the PCB congeners if the
relative retention times are available.
Also, a relationship between log KO,and TSA has been
established for a diverse group of PCB congeners by cal-
culating TSA for molecules in which the two phenyl rings
are coplanar, Le., eq 3. This equation has been used to
calculate the log KO,values for all of the PCB congeners.
On the basis of this and other relationships, an expression
for water solubility of the PCB’s was developed, Le., eq 6.
In addition, it is suggested that this method could be
used for prediction of log KO,values for other groups of
compounds such as polybrominated biphenyls and poly-
halodibenzodioxins and -furans. However, constants for
the appropriate equation need to be established initially
from experimental log KO,values for a small number of
compounds from each group.
Acknowledgments
We gratefully acknowledge the helpful assistance of
David Armstrong, University of Wisconsin, for providing
PCB surface area data.
Registry No. 1, 2051-60-7; 2, 2051-61-8; 3, 2051-62-9; 4,
13029-08-8; 5, 16605-91-7; 6, 25569-80-6; 7, 33284-50-3; 8,
34883-43-7; 9, 34883-39-1; 10, 33146-45-1; 11, 2050-67-1; 12,
2974-92-7; 13, 2974-90-5; 14, 34883-41-5; 15, 2050-68-2; 16,
38444-78-9; 17, 37680-66-3; 18, 37680-65-2; 19, 38444-73-4; 20,
38444-84-7; 21, 55702-46-0; 22, 38444-85-8; 23, 55720-44-0; 24,
55702-45-9; 25, 55712-37-3; 26, 38444-81-4; 27, 38444-76-7; 28,
7012-37-5; 29, 15862-07-4; 30, 35693-92-6; 31, 15862-07-4; 32,
38444-77-8; 33, 38444-86-9; 34, 37680-68-5; 35, 37680-69-6; 36,
38444-87-0; 37, 38444-90-5; 38, 53555-66-1; 39, 38444-88-1; 40,
38444-93-8; 41, 52663-59-9; 42, 36559-22-5; 43, 70362-46-8; 45,
70362-45-7; 46, 41464-47-5; 47, 2437-79-8; 48, 70362-47-9; 49,
41464-40-8; 50, 62796-65-0; 51, 68194-04-7; 52, 35693-99-3; 55,
74338-24-2; 56, 41464-43-1; 57, 70424-67-8; 58, 41464-49-7; 59,
74472-33-6; 60, 33025-41-1; 62, 54230-22-7; 63, 74472-34-7; 64,
52663-58-8; 67, 73575-53-8; 68, 73575-52-7; 69, 60233-24-1; 70,
32598-11-1; 71, 41464-46-4; 72, 41464-42-0; 73, 74338-23-1; 74,
32690-93-0; 75, 32598-12-2; 76, 70362-48-0; 78, 70362-49-1; 79,
41464-48-6; 80, 33284-52-5; 81, 70362-50-4; 82, 52663-62-4; 83,
60145-20-2; 84, 52663-60-2; 85, 65510-45-4; 86, 55312-69-1; 87,
38380-02-8; 88, 55215-17-3; 89, 73575-57-2; 90, 68194-07-0; 91,
68194-05-8; 92, 52663-61-3; 93, 73575-56-1; 94, 73575-55-0; 95,
38379-99-6; 96, 73575-54-9; 97, 41464-51-1; 98, 60233-25-2; 99,
38380-01-7; 100,39485-83-1;101,37680-73-2;102,68194-06-9;103,
60145-21-3; 106,70424-69-0;107,70424-68-9;108,70362-41-3; 109,
74472-35-8; 110,38380-03-9; 111,39635-32-0; 112,74472-36-9; 113,
68194-10-5; 114,74472-37-0;115,74472-38-1;116,18259-05-7; 117,
68194-11-6; 118,31508-00-6;119,56558-17-9; 120,68194-12-7;121,
56558-18-0; 122,76842-07-4;123,65510-44-3;124,70424-70-3;125,
74472-39-2; 126,57465-28-8;127,39635-33-1;128,38380-07-3; 129,
55215-18-4;130,52663-66-8;131,61798-70-7; 132,38380-05-1;133,
35694-04-3; 134,52704-70-8; 135,52744-13-5; 137,35694-06-5;138,
35065-28-2; 139,56030-56-9;140,59291-64-4;141,52712-04-6;142,
41411-61-4; 143,68194-15-0;144,68194-14-9;145,74472-40-5; 146,
51908-16-8; 147,68194-13-8; 148,74472-41-6; 149,38380-04-0;150,
68194-08-1; 151,52663-63-5;152,68194-09-2;153,35065-27-1; 154,
60145-22-4; 155,33979-03-2;156,38380-08-4;157,69782-90-7;158,
74472-42-7; 159,39635-35-3;160,41411-62-5;161,74472-43-8; 162,
39635-34-2; 163,74472-44-9;164,74472-45-0; 165,74472-46-1; 166,
41411-63-6; 167,52663-72-6;168,59291-65-5; 169,32774-16-6;170,
35065-30-6; 171,52663-71-5;172,52663-74-8; 173,68194-16-1;174,
38411-25-5; 175,40186-70-7;176,52663-65-7;177,52663-70-4;178,
52663-67-9; 179,52663-64-6;180,35065-29-3;181,74472-47-2;182,
60145-23-5; 183,52663-69-1;184,74472-48-3;185,52712-05-7;186,
74472-49-4; 187,52663-68-0;188,74487-85-7;189,39635-31-9; 190,
41411-64-7; 191,74472-50-7;192,74472-51-8;193,69782-91-8; 195,
52663-78-2; 196,42740-50-1;197,33091-17-7;198,68194-17-2;199,
52663-73-7; 201,52663-75-9; 202, 2136-99-4; 203,52663-76-0; 204,
74472-52-9;205,74472-53-0;206,40186-72-9;208,52663-77-1; 209,
2051-24-3; BP, 92-52-4; 2,2‘,6,6‘-CB, 15968-05-5; 2,2‘,5,6‘-CB,
41464-41-9; 2,2’,3,3’-CB, 38444-93-8; 2,3,5,6-CB, 33284-54-7;
2,3,4,5-CB, 33284-53-6; 2,3’,4,4’-CB, 32598-10-0; 3,3’,4,4’-CB,
32598-13-3; 2,2’,4,6,6’-CB, 56558-16-8; 2,3,3’,4,4’-CB, 32598-14-4;
2,2’,3,3‘,6,6‘-CB, 38411-22-2; 2,2‘,3,3‘,4,5‘,6,6‘-CB, 40186-71-8;
2,2‘,3,3’,4,4‘,5,5’-CB, 35694-08-7;2,2’,3,3’,4,4’,5,6,6’-CB,52663-79-3;
1-octanol, 111-87-5.
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Received for review March 3,1987. Revised manuscript received
September 21,1987. Accepted November 11,1987. Wegratefully
acknowledge the receipt of an Australian Marine Sciences and
Technology grant to carry out this work.
Environ. Sci. Technol., Vol. 22, No. 4, 1988 387