Environmental Fate Constants for
Organic Chemicals Under
Consideration for
EPA's Hazardous Waste Identification Rule (HWIR)
Compiled and edited toy
Heinz P. Kollig
Contributors: J. Jackson Ellington
Samuel W. Karickhoff
Brenda E. Kitchens
Heinz P. Kollig
J. MacArthur Long
Eric J. Weber
N. Lee Wolfe
Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Athens, GA 30605-2720
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DISCLAIMER
The information in this document has been funded by the United States
Environmental Protection Agency. It has been subjected to the Agency's peer and
administrative review and it has been approved for publication as an EPA document.
11
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FOREWORD
As it becomes more and more obvious that many thousands of potentially hazardous
manmade chemicals find their way into ambient environments, the need for a
comprehensive understanding of the distribution of chemicals and their transport and
transformation reaches a higher level of importance. As part of this Laboratory's research
on the occurrence, movement, transformation, impact, and control of chemical
contaminants, the Chemistry Branch and the Measurements Branch determine the •
occurrence of unexpected organic chemicals in the environment, define mechanisms of
transport and abiotic transformation, and develop and apply advanced methods to predict
and measure physical and chemical transformation and equilibrium constants for use in
exposure assessment.
Under Section 301 of the Resources Conservation and Recovery Act (RCRA), EPA's
Office of Solid Waste is required to develop and promulgate criteria for identifying and
listing hazardous wastes, taking into account, among other factors, persistence and
degradability in the environment of selected chemicals. A requirement of the legislation
is for EPA to take an initial step toward defining wastes that do not merit regulation
under Subtitle C of RCRA and can be managed under other regimes. For establishing
exemption criteria, the Agency has selected some 200 chemical constituents that may
occur in the various wastes. This report explains some of the means by which these
chemicals may be transformed and provides hydrolysis degradation pathways and fate
constants for the selected chemicals.
Rosemarie C. Russo, Ph.D.
Director
Environmental Research Laboratory
Athens, Georgia
in
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ABSTRACT
Under Section 301 of the Resource Conservation and Recovery Act (RCRA), EPA's
Office of Solid Waste has identified some 200 chemicals to be listed in a proposed rule
called the Hazardous Waste Identification Rule (HWIR). This publication addresses the
189 organic? listed in the HWIR. The environmental fate constants and the chemical
hydrolysis pathways of these chemicals are listed. Chemical hydrolysis rate constants for
parent compounds and products including structural presentation of the pathways are
presented. Redox rate constants are given for selected compounds. Sorption coefficients
are presented for parents and products in terms of the octanol/water partition coefficient
and the organic-carbon-normalized sediment/water partition coefficient. The ionization
constant is given when this process affects sorption in the environmental pH range.
IV
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Table of Contents
Parti
Introduction 1
Hydrolysis 5
General 5
Halogenated Aliphatics 6
Simple halogenated aliphatics 6
Polyhalogenated aliphatics 7
Epoxides 8
Organophosphorus Esters 8
Carboxylic Acid Esters 9
Amides 9
Carbamates 10
Nitrites 10
Sorption 10
Neutral Organic Compunds 10
lonizable Organic Compounds 11
Estimated data 13
Redox 14
Abiotic Redox Trans formations of Organic Compounds 14
Convention of Writing Redox Reactions 15
Reduction 15
Oxidation 16
Descriptions of Redox State of the System 16
Eh 16
pH 17
Kinetics of Reaction in Heterogenous Systems 17
Calculation of Rate Constants 17
Reductive Processes 17
Nitroaromatics 17
Halogenated Hydrocarbons 17
Oxidative Processes 18
Aldehydes 18
Amines 18
Table 1 19
Table 2 53
References 55
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Part 2
1. Acenaphthene 61
2. Acetone 61
3. Acetonitrile 62
4. Acetophenone 63
5. Acrolein 63
6. Acrylamide 64
7. Acrylonitrile 64
8. Aldrin 65
9. Aniline 65
11. Aramite 66
14. Benz[a]anthracene 67
15. Benzene 67
16. Benzidine 68
17. Benzo[6]fluoranthene 68
18. Benzo[a]pyrene 69
19. Benzotrichloride 69
20. Benzyl alcohol 70
21. Benzyl chloride 70
23. Bis(2-chloroethyl)ether 71
24. Bis(2-chloroisopropyl)ether 72
25. Bis(2-ethylhexyl)phthalate 73
26. Bromodichloromethane 74
27. Bromomethane 74
28. Butanol 75
29. Butyl benzyl phthalate 75
30. 2-sec-Butyl-4,6-dinitrophenol 76
32. Carbon disulfide 76
33. Carbon tetrachloride 77
34. Chlordane 77
35. p-Chloroaniline 78
36. Chlorobenzene 78
37. Chlorobenzilate 79
38. 2-Chloro-l,3-butadiene 80
39. Chlorodibromomethane 80
40. Chloroform 81
41. Chloromethane 81
42. 2-Chlorophenol 82
43. 3-Chloropropene 82
45. Chrysene 83
47. o-Cresol 83
48. m-Cresol 84
49. p-Cresol 84
50. Cumene 85
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51. Cyanide 85
52. 2,4-Dichlorophenoxyacetic acid 86
53. DDD 86
54. DDE 87
55. p,p'-DDT 87
56. Diallate 88
57. Dibenz [a,/»] anthracene 88
58. 1,2-Dibromo-3-chloropropane 89
59. Dibromomethane 90
60. 1,2-Dichlorobenzene 90
61. 1,4-Dichlorobenzene 91
62. 3,3'-Dichlorobenzidine 91
63. Dichlorodifluoromethane 92
64. 1,1-Dichloroethane 92
65. 1,2-Dichloroethane 93
66. 1,1-Dichloroethylene 94
67. cis-l,2-Dichloroethylene 94
68. trans-1,2-Dichloroethylene 95
69. Dichloromethane 95
70. 2,4-Dichlorophenol 95
71. 1,2-Dichloropropane 96
72. 1,3-Dichloropropene 97
73. Dieldrin 98
74. Diethyl phthalate 99
75. Diethylstilbestrol 100
76. Dimethoate (opposite page) 100
77. 3,3'-Dimethoxybenzidine 102
78. 7,12-Dimethylbenz[a]anthracene 102
79. 3,3'-Dimethylbenzidine 103
80. 2,4-Dimethylphenol 103
81. Dimethyl phthalate 104
82. 1,3-Dinitrobenzene 105
83. 2,4-Dinitrophenol 105
84. 2,4-Dinitrotoluene 106
85. 2,6-Dinitrotoluene 106
86. Di-rc-butyl phthalate 107
87. Di-n-octyl phthalate 108
88. 1,4-Dioxane 109
89. 2,3,7,8-TCDDioxin 109
90. 2,3,7,8-PeCDDioxins 110
91. 2,3,7,8-HxCDDioxins 110
92. 2,3,7,8-HpCDDioxins 110
93. OCDD Ill
94. Diphenylamine Ill
95. 1,2-Diphenylhy drazine Ill
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96. Disulfoton 112
97. Endosulfan 113
98. Endrin 114
99. Epichlorohydrin „ 115
100. 2-Ethoxyethanol 116
101. Ethyl acetate 116
102. Ethylbenzene 117
103. Ethyl ether 117
104. Ethyl methacrylate 118
105. Ethyl methanesulfonate 119
106. Ethylene dibromide 120
107. Famphur 121
108. Fluoranthene 122
109. Fluorene 122
110. Formic acid 123
111. Furan 123
112. 2,3,7,8-TCDFuran 124
113. 1,2,3,7,8-PeCDFuran 124
114. 2,3,4,7,8-PeCDFuran 125
115. 2,3,7,8-HxCDFurans 125
116. 2,3,7,8-HpCDFurans 126
117. OCDF 126
118. Heptachlor 127
119. Heptachlor epoxide 128
120. Hexachlorobenzene 129
121. Hexachlorobutadiene 129
122. alpha-HCH 130
123. beta-HCH 131
124. Hexachlorocyclopentadiene 132
125. Hexachloroethane 132
126. Hexachlorophene 133
127. Indeno[l,2,3-cd]pyrene 133
128. Isobutyl alcohol 134
129. Isophorone 134
130. Kepone 135
132. gomma-HCH 135
134. Methacrylonitrile 136
135. Methanol 137
136. Methoxychlor 137
137. 3-Methylcholanthrene 138
138. Methyl ethyl ketone 138
139. Methyl isobutyl ketone 139
140. Methyl methacrylate 139
141. Methyl parathion 140
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142. Naphthalene .-. 141
143. 2-Naphthylamine 141
145. Nitrobenzene 142
146. 2-Nitropropane 142
147. JV-Nitroso-di-7i-butylamine 143
148. JV-Nitrosodiethylamine 143
149. JV-Nitrosodimethylamine 144
150. 7V-Nitrosodiphenylamine 144
151. JV-Nitroso-di-n-propylamine 145
152. JV-Nitrosomethylethylamine 145
153. JV-Nitrosopiperidine 146
154. JV-Nitrosopyrrolidine 146
155. Octamethyl pyrophosphoramide 147
156. Parathion 148
157. Pentachlorobenzene 149
158. Pentachloronitrobenzene 149
159. Pentachlorophenol 150
160. Phenol 150
161. Phenylenediamine 150
162. Phorate 151
163. Phthalic anhydride 152
164. Polychlorinated biphenyls 152
165. Pronamide 153
166. Pyrene 153
167. Pyridine 154
168. Safrole 154
171. Strychnine 155
172. Styrene 155
173. 1,2,4,5-Tetrachlorobenzene 156
174. 1,1,1,2-Tetrachloroethane 156
175. 1,1,2,2-Tetrachloroethane 157
176. Tetrachloroethylene 157
177. 2,3,4,6-Tetrachlorophenol 158
178. Tetraethyl dithiopyrophosphate 159
180. Toluene 160
181. 2,4-Toluenediamine 160
182. 2,6-Toluenediamine 161
183. o-Toluidine 161
184. p-Toluidine 162
185. Toxaphene 162
186. Tribromomethane 163
187. 1,2,4-Trichlorobenzene 163
188. 1,1,1-Trichloroethane 164
189. 1,1,2-Trichloroethane 165
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190. Trichloroethylene 166
191. Trichlorofluoromethane 166
192. 2,4,5-Trichlorophenol 167
193. 2,4,6-Trichlorophenol 167
194. 2,4,5-Trichlorophenoxyacetic acid 168
195. 2-(2,4,5-Trichlorophenoxy)propionic acid (Silvex) 168
196. 1,2,3-Trichloropropane 169
197. l,l,2-Trichloro-l,2,2-trifluoroethane 170
198. 1,3,5-Trinitrobenzene 170
199. 7Hs(2,3-dibromopropyl)phosphate 171
201. Vinyl chloride 172
202. Xylenes 172
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Parti
Introduction
Assessment of potential risk posed to humans by man-made chemicals in the environment
requires the prediction of environmental concentrations of those chemicals under various
environmental reaction conditions. Whether mathematical models or other assessment
techniques are employed, knowledge of equilibrium and kinetic constants (fate constants)
is required to predict the transport and transformation of these chemicals.
Under section 301 of the Resource Conservation and Recovery Act (RCRA), EPA's Office of
Solid Waste (OSW) has identified wastes that may pose a substantial hazard to human
health and the environment. RCRA requires that EPA develop and promulgate criteria
for identifying and listing hazardous wastes, taking into account, among other factors,
persistence and degradability in the environment of selected chemicals.
In the May 20,1992, Federal Register, EPA proposed two approaches for amending its
regulations under RCRA for hazardous waste identification. The proposed rule is called
the Hazardous Waste Identification Rule (HWIR). The first proposed approach would
establish Concentration-Based Exemption Criteria (CBEC) for listed hazardous wastes,
waste mixtures, derivatives, and media (including soils and ground-water) contaminated
with certain listed hazardous wastes for exiting RCRA Subtitle C management require-
ments. The second proposed approach is referred to as the Expanded CHaracteristics
Option (ECHO). It would establish "characteristic" levels for listed hazardous wastes,
waste mixtures, derivatives, and media (including soils and ground-water) contaminated
with certain listed hazardous wastes for both entering and exiting RCRA Subtitle C via
an expansion of the number of toxic constituents in the Toxicity Characteristics (TC) rule.
Under the CBEC approach, listed wastes and contaminated media meeting the estab-
lished criteria would no longer be subject to some of the hazardous waste management
requirements under Subtitle C of RCRA.
Under the ECHO approach, listed wastes and contaminated media that do not exhibit a
hazardous characteristic would not be regulated by the hazardous waste management
requirements under Subtitle C of RCRA.
The purpose of this rulemaking is to take an initial step towards defining wastes that do
not merit regulation under Subtitle C and that can and will be safely managed under
other regulatory regimes. For establishing exemption criteria, the Agency has selected
some 200 chemical constituents. The environmental fate constants and the chemical
hydrolysis pathways of the organics are listed in Part I and Part II of this report,
respectively. Inorganic compounds are not addressed in this publication.
For all organic compounds on the HWIR list, OSW requested that the Environmental
Research Laboratory-Athens (ERL-Athens):
a) identify those that do not hydrolyze.
b) identify those that do hydrolyze and list products of degradation including hydrolysis
rate constants for parents and intermediates obtained either through laboratory
experiments at ERL-Athens, literature searches, or pathway analyses.
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Fate Constants for Hazardous Waste Identification Rule
c) obtain sorption data as the organic-carbon-normalized sediment-water partition
coefficient either through laboratory experiments at ERL-Athens, literature searches,
or computational techniques.
d) to the extent-that current scientific knowledge will permit, identify those that will be
subject to other important degradation reactions and identify products of these
reactions including rate constants.
For compounds identified as having no hydrolyzable functional group (NHFG), hydrolysis
will not occur by abiotic reaction pathways in the pH range of 5 to 9 at 25°C.
The compounds identified as having non-labile functional groups (NLFG) will not
hydrolyze to any reasonable extent. Although a molecule with a non-labile functional
group contains one or more heteroatoms, they read; so slowly over the pH range of 5 to 9
at 25°C, that their half-lives will be greater than 50 years, if they react at all.
Polychlorinated biphenyls (PCBs) have been addressed here only as a class because of the
many different congeners of these compounds. The given Chemical Abstract Service
number 1336-36-3 is the number for the general class of Aroclors without designating any
specific Aroclor. Because PCBs will not hydrolyze to any reasonable extent, our Pathway
Analysis Team classified them as non-labile. The sorptive capacity, however, will be
different from congener to congener. We have found reported log K^ values ranging from
2.59 to 11.20. Therefore, a single sorption value for the class of Aroclors was not
assigned.
The chemical hydrolysis pathways of compounds with negative boiling points that exist as
gases at room temperature were not addressed in this report.
Some compounds may exist in the environment as ionized species. The transformation
pathways show these species in the neutral form for better identification. It should be
understood that both the persistence and mobility of a chemical in the environment is
influenced by many environmental factors that may change from environment to environ-
ment. The values in this document are for those conditions specified in the references.
A team of EPA scientists met several times to discuss the rates and probable pathways of
transformation for hydrolysis and redox reactions. The methods used to arrive at the
reaction products were based primarily on the team's experience with similar compounds,
their knowledge of the theory of these processes, and their understanding of structure-
activity relationships. For hydrolysis, the team's decisions are identified in Table 1 with a
zero in the Reference column. Final stable products are identified as containing either no
hydrolyzable functional group (NHFG) or a non-labile functional group (NLFG) in the
Comment column.
Literature searches were conducted afterwards to find needed fate data for the intermedi-
ate products of hydrolysis. If the literature failed to provide the required data, they were
determined in the laboratory for some compounds.
This report is composed of two parts. Part I includes text and data on chemical hydrolysis,
sorption, and redox reactions. Part II includes the chemical structures of all organic
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Parti
compounds on the HWIR list and the pathways of chemical hydrolysis of those compounds
that undergo this transformation. When a compound was identified as NHFG, the text
with the structure will say that the compound will not hydrolyze. When a compound was
identified as NLFG, the text with the structure will say that the compound will not
hydrolyze to any reasonable extent. When a compound might be subject to other abiotic
transformation processes, the text with the structure will point this out; however, these
processes have not been identified.
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Fate Constants for Hazardous Waste Identification Rule
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Parti
Hydrolysis
General
In general, hydrolysis is a bond-making, bond-breaking process in which a molecule, RX,
reacts with water forming a new R-O bond with the oxygen atom from water and cleaving
an R-X bond in the original molecule. One possible pathway is the direct displacement of
X' with HO* as shown in Equation 1.
RX + HO > ROH + HX (1)
The detailed mechanisms of hydrolytic processes are well defined and have been shown to
involve the formation of intermediates such as protonated species, anions and carbonium
ions, as well as combinations of these intermediates.
Generally, hydrolysis of organic compounds in water under pH-buffered conditions is first-
order in the concentration of the organic species ([RX]), where the rate of hydrolysis
(c"[RX]/c"0 is proportional to the concentration of pollutant RX:
(2)
Where k^, is the observed pseudo-first-order disappearance rate constant. The first-order
dependence of the disappearance rate on [RX] is important, because it means that the
half-life (t^) of the reaction described by Equation 2 is independent of [RX]. Thus, the
results obtained at a high RX concentration can be extrapolated to lower RX concentra-
tions if other reaction conditions are held constant. The half-life of the reacting compound
is given by Equation 3:
' _ In 2 _ 0.693 ,~
V* ~ 1 k~ ()
Kota "fete
where kAt can include contributions from acid-catalyzed or base-mediated hydrolysis,
nucleophilic attack by water, or catalysis by buffers in the reaction medium.
For abiotic hydrolysis, the general expression for &<*, is given by:
(4)
where ka and kb are the specific acid and base second-order rate constants, respectively; kn
is the neutral hydrolysis rate constant; and k^ and kA are the general acid-catalyzed and
base-mediated hydrolysis rate constants, respectively. In Equation 4, [H*] and [HO'] are
the hydrogen and hydroxyl ion concentrations, respectively, and [HA] and [A] are the
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Fate Constants for Hazardous Waste Identification Rule
concentrations of the ith and the/th pair of general acids and bases in the reaction
mixture, respectively.
In Table 1, ka, kb, and kn values are reported for the particular chemical at 25°C (+/-4°C).
A half-life at 25°C can be calculated by using Equation 4 to calculate k^, followed by
Equation 3 to calculate the time at 50% hydrolysis. Concentration and time units used
are molar (M) and year (Y), respectively. Products of hydrolysis are listed indented under
the parent compound, e.g., acetonitrile (parent): acetamide is the first hydrolysis product
and it then becomes an intermediate by hydrolyzing to a secondary product, acetic acid.
Both products are indented according to the order of their appearance in the hydrolysis
pathway of the original parent.
Hydrolysis rate constants that were reported in the literature at an elevated temperature
were reanalyzed with RATE28 to extrapolate the values to 25°C. These reanalyzed values
are identified by RATE in the Comment column. Those compounds that were identified
as non-hydrolyzable or non-labile were designated as 'NHFG' and *NLFG', respectively, in
the Comment column.
Halogenated Allphatlcs
Simple hologenoted oliphotics
Hydrolysis of the simple halogenated aliphatics (halogen substitution at one carbon atom)
is generally pH independent, resulting in the formation of alcohols by nucleophilic
substitution with water (Equation 1). Although a number of the simple halogenated
aliphatics are susceptible to base-mediated hydrolysis, the rate term for the base-medi-
ated process will not contribute to the overall hydrolysis rate under environmental condi-
tions.
The halogenated methanes, except for the trihalomethanes, hydrolyze by direct nucleo-
philic displacement by water (8^2 mechanism). An increase in the number of halogen
substituents on carbon increases the hydrolysis half-life because of the greater steric bulk
about the site of nucleophilic attack. The type of halogen substituent also affects
reactivity. For example, hydrolysis data indicate that the fluorinated aliphatics are much
more stable than the chlorinated aliphatics, which in turn are more stable than the
brominated aliphatics (F > Cl > Br). This trend in reactivity reflects the strength of the
carbon-halogen bond that is broken in the nucleophilic substitution reaction.
Hydrolysis of the trihalomethanes, or haloforms, is thought to occur initially by proton
abstraction and subsequent formation of the carbene, which reacts with HO~ to form
carbon monoxide and chloride ion:41
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Parti
In contrast to the halogenated methanes which have hydrolysis half-lives on the order of
years, the hydrolysis half-lives for allylic and benzylic halides are on the order of minutes
to hours. The hydrolysis of these chemicals occurs through an indirect nucleophilic
displacement by water (Sjjl mechanism). The dramatic increase in reactivity is due to the
structural features of these compounds that allow for delocalization, and thus, stabiliza-
tion, of the carbonium ion intermediate. Resonance structures can be drawn for the
allylic and benzyl carbonium ions that delocalize the positive charge over several carbon
atoms.
The lack of reactivity observed for vinyl halides and halogenated aromatics is a reflection
of the high energy pathway required for nucleophilic substitution at vinylic and aromatic
carbons. Vinyl and phenyl carbonium ions have been observed, but their formation
requires very reactive leaving groups.
Polyhalogenated aliphatics
The hydrolysis kinetics for the polyhalogenated ethanes and propanes are somewhat more
complex than for the simple halogenated aliphatics. In addition to nucleophilic substitu-
tion reactions, degradation of these compounds can occur through the base-mediated loss
of HX. Depending on structure type, elimination or dehydrohalogenation may be the
dominant reaction pathway at pEPs characteristic of ambient environments. The loss of
HX occurs through a bimolecular elimination (E2) reaction in which abstraction of the
hydrogen beta to the halogen (X) occurs simultaneously with cleavage of the C-X bond:
-U-
This process often results in the formation of halogenated alkenes, which can be more
persistent and of more concern than substitution products42.
The distribution of reaction products resulting from the hydrplytic degradation of the
polyhalogenated ethanes and propanes will depend on the relative rates for the nucleo-
philic substitution and dehydrohalogenation reaction pathways. Furthermore, because
dehydrohalogenation is pH dependent, product distribution will also be pH dependent.
A wide range of reactivity is observed for these compounds; the environmental hydrolysis
half-lives in years range over 7 orders of magnitude. For a number of the polyhalogena-
ted aliphatics, it is apparent that both neutral and base-mediated hydrolysis will occur at
ambient environmental pH values and that the relative contributions of these processes
will be dependent on the degree and pattern of halogen substitution.
As with nucleophilic substitution reactions, rates of dehydrohalogenation reactions will be
dependent on the strength of the C-X bond being broken in the elimination process.
Accordingly, it is expected that the ease of elimination of X will follow the series
Br> Cl > F.
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8 Fate Constants for Hazardous Waste Identification Rule
Epoxides
The hydrolysis of epoxides is pH dependent and can occur through acid-, neutral-, or base-
promoted processes. Because the acid and neutral processes dominate over ambient
environmental pH.ranges, the base-mediated process can often be ignored. The products
resulting from the hydrolysis of epoxides are diols, and to a lesser extent, rearrangement
products:
OH OH R,
R,— C-C
k k
R,— C-C-R4 + R,— i
k
Organophosphoms Esters
Mechanistic studies of organophosphorus esters have demonstrated that hydrolysis occurs
through direct nucleophilic displacement at the central phosphorus atom and does not
involve formation of a pentavalent intermediate with HjO or H0~ 43'44. Accordingly,
hydrolysis rates for phosphorus esters will be sensitive to electronic factors that alter the
electrophilicity of the central phosphorus atom and steric interactions that impede
nucleophilic attack. For example, substitution of sulfur (P=S) for oxygen (P=0) in the
ester moiety will reduce the electrophilicity of the phosphorus center because of the
weaker electron withdrawing effect of sulfur. Accordingly, phosphorothioate and phospho-
nothioate esters will exhibit greater stability towards neutral and base-mediated hydroly-
sis than their respective 0-substituted counterparts.
An interesting feature of the hydrolytic degradation of phosphorus esters is that carbon-
oxygen or carbon-sulfur cleavage may also occur. It is generally observed that base-
mediated hydrolysis favors P-0 cleavage, which is shown in the first chemical reaction
below, and that neutral and acid catalysis favors C-Q or C-S cleavage, which is shown in
the second reaction below. As a result, hydrolysis mechanisms and product distribution
for the organophosphorus esters will be pH dependent.
'OH •• R1O-P-O-CH2R2 + HOR,
-
9
Because hydrolysis of phosphorus esters results in the formation of phosphate mono- and
diesters, assessment of their hydrolytic activity is necessary. At any ambient environmen-
tal pH, the mono- and diesters will exist primarily as di- and monoacids, respectively.
Accordingly, base hydrolysis of the anions will not be important, but neutral hydrolysis of
these species must be considered. Hydrolysis of the dialkyl monoion to yield monoalkyl
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Parti
products proceeds at a rate approximately a factor of 10 less than that of the triester.
Hydrolysis of the resulting monoalkyl ester (dianion) proceeds at a rate of approximately
one half that of the triester. Hydrolysis of the monoester has been shown to occur
through nucleophilic attack on the phosphorus rather than carbon-oxygen cleavage66.
Carboxylic Acid Esters
Hydrolysis of carboxylic acid esters results in the formation of a carboxylic acid and an
alcohol:
Rf-C-O-Rj, + H20 F^-C-
-OH
Hydrolysis mechanisms of carboxylic acid esters have been thoroughly investigated.
Although nine distinct mechanisms have been proposed45, our comments will be limited to
the two most common mechanisms involving acyl-oxygen bond cleavage by acid catalysis
(AAC2) and base mediation (BAC2). Hydrolysis via the AAC2 mechanism involves initial
protonation of the carbonyl oxygen. Protonation polarizes the carbonyl group, removing
electron density from the carbon atom and making it more electrophilic and thus more
susceptible to nucleophilic addition by water. The base-mediated mechanism (BAC2)
proceeds via the direct nucleophilic addition of H0~ to the carbonyl group. Base media-
tion occurs because the hydroxide ion is a stronger nucleophile than water. Although
neutral hydrolysis of carboxylic acid esters does occur, the base-mediated reaction will be
the dominant pathway in most natural waters. Generally, acid hydrolysis will dominate
in acidic waters with pH values below 4.
Both electronic and steric effects can significantly alter the reactivity of carboxylic acid
esters. Because the acid-catalyzed process for both aliphatic and aromatic esters is
relatively insensitive to structural changes, observed changes in the magnitude ofk^
with structure are due primarily to changes ofkb, and to a lesser extent, kn. Based on the
mechanism for base mediation (BAC2), we would expect that electronic factors that
enhance the electrophilicity of the carbon atom of the carbonyl group would make it more
susceptible to nucleophilic attack by H0~. The electron-withdrawing groups can be
substituents of either the acyl group (RC(0)} or the alcohol portion of the ester.
Amides
Hydrolytic degradation of amides results in the formation of a carboxylic acid and an
amine:
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10 Fate Constants for Hazardous Waste Identification Rule
In general, amides are much less reactive towards hydrolysis than esters. Typically, half-
lives for amides at ambient environmental conditions are measured in hundreds to
thousands of years6. This observation can be explained by the ground-state stabilization
of the carbonyl group by the electron donating properties of the nitrogen atom:
R-C-N-R *• R-C=N—R
This stabilization is lost in the transition state leading to the formation of the tetrahedral
intermediate. The result is that the hydrolysis of amides generally requires base or acid
catalysis, both of which can compete at neutral pH.
Carbamates
A carbamate is hydrolyzed to an alcohol, carbon dioxide, and an amine:
-O-Rg *• Rjr-N-H + C02 +
Carbamates are susceptible to acid, neutral and base hydrolysis, although in most cases,
base hydrolysis will dominate at environmental conditions. In an analogous manner to
carboxylic acid ester and amide hydrolysis, electron- withdrawing substituents on either
oxygen or nitrogen will accelerate the rate of hydrolysis. The most dramatic differences in
reactivities are observed when the hydrolysis half-lives of primary (R^H, R^alkyl) and
secondary (R^alkyl, R^alkyl) carbamates are compared. The primary carbamates
hydrolyze at rates that are approximately 6 to 7 orders of magnitude faster than the
corresponding secondary carbamates.
Nitrites
Nitriles are hydrolyzed to give a carboxylic acid and ammonium ion. Hydrolysis occurs
through the intermediate amide:
R-?-
R-C-N -*. R--NH
Base-mediated hydrolysis appears to be the dominant hydrolysis pathway at pH 7.
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Parti 11
Sorption _
Neutral Organic Compounds
Partitioning between water and natural soils, sediments, and aquifer materials is an
important process affecting transformation rates, toxicity, and the ultimate disposition of
organic chemicals in the environment. Research focusing on the partitioning of neutral
organic compounds has shown that adsorption of these compounds is usually controlled by
hydrophobic interactions. As a result, the affinity that a natural sorbent has for neutral
organic solutes, in most cases, can be reliably estimated from characterization (quantifica-
tion) of the hydrophobicity of chemical and the sorbent. Organic carbon content has been
used almost exclusively as a measure of the hydrophobic nature of natural sedimentary
material (organic matter or volatile solids content has also been used but not as widely).
To quantitatively characterize the hydrophobic nature of organic compounds, researchers
have used various measurable parameters, including octanol-water partition coefficients
(Kcu,). water solubility (corrected for crystal energy), reverse phase HPLC retention, and
topological parameters of the compounds such as calculated surface area. Generally,
octanol-water partition coefficients have been used extensively for estimating the parti-
tioning of organic compounds to sedimentary materials.
lonlzable Organic Compounds
Predicting the partitioning of ionizable organic compounds is not as straightforward as for
the neutral compounds. These compounds, whether they ate acids or bases, can exist as
ions in solution depending upon the pH of the solution according to the following equa-
tions. For acids:
(5)
- [HA1
and bases:
K. = BOH (6)
[HB1
where [H+] is the hydrogen ion activity, [HA] is the neutral organic acid activity (or
concentration), [A'] is the organic acid anion activity, [B] is the neutral organic base
activity, [HB*] is the protonated organic base activity, and K0 is the acid dissociation or
ionization constant.
In general, more effort has been expended investigating the sorption of organic acids than
the sorption of organic bases. For organic acids, adsorption can be modeled to sediments,
soils, and aquifer materials in a similar manner to that of the neutral compounds, after
taking into account ionization, as long as the pH is not more than one unit above the pKa
of the compound46.
Compounds with low pKa values are more problematic. Adsorption of these compounds
occurs predominantly by the anionic species through modified hydrophobic interactions47.
Therefore, an estimate of a partition coefficient from the K^, of the neutral species would
-------
12 Fate Constants for Hazardous Waste Identification Rule
significantly overestimate the magnitude of adsorption. Jafvert et al.48 and Jafvert47 have
investigated the partitioning behavior of these and similar compounds in the octanol-
water system and in sediment- and soil-water systems. For example, Jafvert47 has
reported on the sediment-water distribution of silvex in 13 soils or sediments. If the
partition coefficients (in which the pH of the slurry is greater than 7) are regressed versus
the fraction organic carbon, a value of log KM = 1.8 is obtained for the organic-carbon-
normalized partition coefficient, KK. The log K^ of the neutral form of silvex is 3.8.
Similar results for pentachlorophenol and 4-chloro-a-(4-chlorophenyl)benzeneacetic acid
(DDA) suggest that the partition coefficient (at pH 7.0) of the anionic form of these
compounds is approximately two orders of magnitude less than the respective K^ values
of the neutral form of these compounds.
Unlike anionic organic compounds, which partition more weakly than their neutral
counterparts, organic cations tend to partition more strongly than the corresponding
unprotonated bases. Also, unlike organic anions, which partition largely through modified
hydrophobic interactions, the organic cations can undergo cation (or ligand) exchange
reactions. Pyridine, for example, is an organic base that has &pKa value of 5.3. At pH 7,
a small fraction (2.2%) will exist as an organic cation in aqueous solution. Because the
cationic species is expected to adsorb more strongly to most natural soils, sediments, and
aquifer materials than the neutral species, an organic-carbon-normalized partition
coefficient (KJ may severely underestimate the adsorption of this compound at near-
neutral pH. Because no predictive methods exist for describing the partitioning of organic
cations to natural matrices, however, the organic-carbon-normalized partition coefficient
calculated from the K^ of the neutral species (not accounting for ionization) is given in
Table 1. For virtually every sediment and aquifer material, this constant will underpre-
dict the true magnitude of adsorption of these compounds, with the error intensifying as
the organic carbon content of a sediment or aquifer material decreases.
For neutral compounds and organic bases with pKa values below 6, the organic-carbon-
normalized partition coefficients in Table 1 have been calculated using the relationship,
tog K^ = log Kw - 0.32 (7)
given by Hassett et al.49 This correlation was calculated from adsorption isotherms of 13
organic chemicals, representing several classes of compounds, using 14 different sediment
and soil samples. This correlation adequately predicts partitioning of several classes of
organic compounds, including chlorinated and nonchlorinated aromatic and alkyl hydro-
carbons. Use of this correlation will generally be valid for soils, sediments, and aquifer
materials that have organic carbon contents greater than 0.1%.
For organic acids, the pKa must be considered in the computation of the KM. The follow-
ing relationships were used according to the range ofpKa values:
PK. >9:K« = 1.05 K^™ (8)
-------
Parti 13
c *- *v s Q. ir 1 nK»-<082) 1
b < pA0 < 9. ^ = l.ODA^ __ (g)
which simplifies at pH 7 to:
_ LOS x IP"7 x ^ (1Q)
ID'7 + Ka
pKa < 6: log 4 = log *•„ - 2 (ID
For organic bases, the pKa value was considered in the computation of the Kx, where pKa
= l4-pKb. Equation (7) was used for compounds with pKa values of less than 6. For
organic bases with pK0 values larger than 6, no Kx values were calculated because the
uncertainty is too great. When a K^ value was needed for a complex ion with successive
ionization constants, the first ionization constant (pKj) was used in the computation of the
KK value. All ionization constants were computed with SPARC29.
Estimated data
Most of the log KB, values in Table 1 were computed with QSAR4 and SPARC29. QSAR is
an interactive chemical database and hazardous assessment system designed to provide
basic information for the evaluation of the fate and effects of chemicals in the environ-
ment. The QSAR4 system is a composite of databases containing measured values
obtained from the literature and a state-of-the-art QSAR model library capable of
estimating chemical properties, behavior, and toxicity, based on conventional estimation
techniques, many of which were derived from the work of Lyman et al.80 The QSAR
system contains automated estimation routines for 13 properties based upon modified
structure-activity correlations.
SPARC29 is a computational expert system that predicts chemical reactivity. The system
has the capability of crossing chemical boundaries to cover all organic chemicals and uses
algorithms based on fundamental chemical structure theory to estimate parameters.
SPARC quantifies reactivity by classifying molecular structures and selecting appropriate
"mechanistic" models. It uses an approach that combines principles of quantitative
structure-activity relationships, linear free energy theory (LFET), and perturbed molecu-
lar orbital (PMO) or quantum chemistry theory. In general, SPARC utilizes LFET to
compute thermal properties and PMO theory to describe quantum effects such as
delocalization energies or polarizabilities of TT electrons.
For example, SPARC computes the log of the octanol- water partition coefficient from
activity coefficients in the octanol (y~) and water (y^ ) phases:
-------
14 Fate Constants for Hazardous Waste Identification Rule
(12)
where M,, and Mw are solvent molecularities of octanol and water, respectively. Activity
coefficients for either solvent or solute are computed by solvation models that are built
from structural constituents requiring no data besides the structures.
A goal for SPARC is to compute log K^ values that are as accurate as values obtained
experimentally for a fraction of the cost required to measure them. Because SPARC does
not depend on laboratory measurements conducted on compounds with structures closely
related to that of the solute of interest, it does not have the inherent problems of phase
separation encountered in measuring highly hydrophobic compounds Gog K^ > 5). For
these compounds, SPARC's computed value should, therefore, be more reliable than a
measured one.
Redox
Abiotic Redox Transformations of Organic Compounds
Abiotic redox reactions will not generally mineralize large organic molecules, but the
transformations will result in daughter products with different chemical and physical
properties61. Furthermore, abiotic transformations can convert bio-resistant compounds to
more bio-susceptible compounds. For example, redox reactions can result in oxidation or
reduction of key functional groups on molecules that will render them labile to microbial
transformations and ultimately mineralization or conversion to other environmentally
innocuous components.
A large number of functional groups on organic compounds have been shown to undergo
abiotic reduction under ambient environmental conditions. In general, these redox
transformations encompass almost all chemical functional groups, utilize a large number
of organic and inorganic redox agents, and result in an almost unlimited number of
products52. Furthermore, the rates of redox reactions can be expected to span many
orders of magnitude, depending upon the reaction type and redox agents' activities.
Unfortunately, only a few of the reactions have been studied in enough detail to identify
the system redox agents and provide kinetics data.
It is not currently possible to address redox transformations for all the listed compounds
in soils, sediments and aquifer systems because of a lack of quantitative research in the
area of environmental redox reactions. For the few classes of compounds where detailed
studies have been carried out, it is possible to obtain reductive rate constants and apply
them to environmental systems63'64. In these detailed studies, kinetic expressions and the
reducing agents have been identified.
In this report, reduction of halogenated hydrocarbons and nitroaromatics, and the
autooxidation of aldehydes and amines are addressed. Estimated rate constants for
halogenated hydrocarbons and nitroaromatics are given in Table 2. These rate constants
-------
Port / 15
were computed for soil-water systems in which the solids contained 1% and 0.02% organic
carbon. The data clearly indicate the dependence of the reductive process on organic
carbon. A 50-fold increase in organic carbon from a concentration of 0.02% decreases the
half-lives by about 4 orders of magnitude for the halogenated hydrocarbons and about 1
order of magnitude for the nitroaromatics. For the QSAR computations of the halogenat-
ed hydrocarbons, either published sigma constants or estimated values were used. For
the QSAR computations of the nitroaromatics, published sigma constants were used
except for parathion and methyl parathion. For these two compounds, the sigma con-
stants were estimated from 1-methoxy-p-nitrobenzene. Rate constants for the nitroso
compounds were not computed. However, preliminary laboratory studies of some nitroso
compounds indicated half-lives of less than 1 hour. It was not possible to identify
products of degradation. We hope that the following will give the reader some insight into
this difficult and unexplored area of heterogeneous redox reactions.
Convention of Writing Redox Reactions
In the environmental literature, as well as in organic chemistry textbooks, the definitions
of oxidation-reduction are often empirical and can result in ambiguities, especially when
applied across classes of compounds62. Reactions that form new bonds with hydrogen are
often referred to as reduction, whereas those forming new bonds with oxygen are often
referred to as oxidation. Although this system may hold for specific classes of compounds,
it is not generally applicable to the myriad of chemicals of environmental importance.
The overall reaction is not given because, for the most part, the activity of the reducing or
oxidizing agent responsible for the transformation is not known. Thus it is not possible to
sum up the two half-reactions and write the overall equation.
An unambiguous method for describing redox processes is to write the chemical equation
for each half-reaction with the reactants on the left and the products oh the right,
balancing the equation by using hydrogen ions to provide needed hydrogen and hydroxide
ions or water molecules to provide needed oxygen atoms. Electrons are then added to
balance the charge (Figure 1). If electrons are added to the left side of the equation, it is
a reduction reaction. If electrons are added to the right side of the equation, it is an
oxidation reaction. Examples of half-reactions for reduction and oxidation are given
below.
Reduction
Figure 1 shows two examples of reductive transformations. The first is a two-electron
transfer reaction for the reduction of 1,2-dichloroethane to ethene and chloride. The
second is a six-electron reduction of nitrobenzene, requiring six protons that gives aniline
and water as products.
-------
16 Fate Constants for Hazardous Waste Identification Rule
HaC-CHa
+ 2e- "- HaC-CHa + 2CI'
NOa
XN + 6H+ + 6e-
Figure L Half-reactions for the reduction of 1,2-dichloroethane to
ethene and the reduction of nitrobenzene to aniline.
Oxidation
Figure 2 shows two examples of redox half-reactions. The first is a two-electron oxidation
of 1,1,2-trichloroethylene to 1,1-dichloroacetic acid, chloride, and three protons. The
second is a two-electron oxidation of benzaldehyde to benzole acid. In this reaction, water
provides the source of oxygen and results in two protons as a product.
2H20 *- CfeHCCQaH + ch + 3H+ +2e'
3-OH
H20 «- 1 + 2H+ + 2e-
Figure 2. Half-reactions for the oxidation of 1,1,2-trichloro-
ethylene to 1,1-dichloroacetic acid and the oxidation
of benzaldehyde to benzoic acid.
Descriptions of Redox State of the System
Eh
When the Eh of the heterogenous system, as measured by a platinum electrode, is above
Eh 50 mv (relative to Ag:AgCl), the reductive reaction does not occur for the halogenated
-------
Parti 17
hydrocarbons and nitroaromatics88. When the Eh of the system is below 50 mv, the
reaction occurs and the rate of reaction is independent of the magnitude of the Eh.
pH
In general, in heterogenous systems, pH effects on the rates of abiotic reductions are
minimal. This is partly because the solids tend to buffer the pH of the system66. For
example, over the pH range of 5 to 9, the rate .constant for reduction of nitrobenzene to
aniline was independent of pH. The same has been observed for the reduction of haloge-
nated hydrocarbons.
Kinetics of Reaction In Heterogenous Systems
To carry out abiotic reactions in heterogenous systems such as soils, sediments and
aquifer materials, requires an understanding of the kinetics of reaction. In these
heterogenous systems, sorption of the compounds to the solids will affect the overall
kinetics of reaction. A working model has been proposed to account for the observed
kinetics of reduction of compounds in these types of heterogenous systems54'65'56'68. The
model, which is shown below, assumes non-reactive and reactive sorptive sites on the
solids.
p.R - - P + S T - P:S
h
P*
Where P is pollutant concentration; 8 is sediment concentration (g/g); k1 and k.t are the
respective sorption-desorption rate constants to a non-reactive sink, P:S; k2 and k.e are the
respective sorption-desorption rate constants to the reactive sink, P:R; kr is the first-order
rate constant for reduction at reactive solid sites.
Calculation of Rate Constants
Reductive Processes
Nitroaromatics
Rate constants for the reduction of nitroaromatics can be calculated using the BAR based
on Hammett sigma constants reported by Wolfe et al.66 This relation provides selected,
observed first-order disappearance rate constants for nitroaromatic compounds. These
first-order rate constants have been shown by Wolfe et al.66 to correlate with the organic
carbon of the system.
Halogenated hydrocarbons
Wolfe and co-workers67'58 developed a structure reactivity relationship that associates the
reductive disappearance rate constants of halogenated hydrocarbons in anoxic sediments
with readily available molecular descriptors. The correlation is based on disappearance
-------
18 Fate Constants for Hazardous Waste Identification Rule
rate constants for the reductive transformation of 19 halogenated hydrocarbons. The
compounds span a large cross section of chemical structures that includes halogenated
methanes, ethanes, ethenes, and halogenated aromatics.
Wolfe and co-workers67'68 also corrected the rate constants for hexachloroethane for
sorption. These rate constants were obtained in 18 different sediment, soil and aquifer
samples and correlated with the organic carbon.
Oxidative Processes
Aldehydes
In general, aldehydes will undergo autooxidation to the corresponding carboxylic acids in
the presence of oxygen62-59. In sediments, soil and aquifer materials, aldehydes have been
shown to undergo such oxidations even under anoxic conditions. No comprehensive data
base of rate constants is available for these reactions and, furthermore, the autooxidation
kinetics are too complex to extrapolate precise rate constants from laboratory to field
conditions.
These reactions have been observed for a large number of aldehydes and, based on this
qualitative data base, half-lives of less than 1 year are reasonable.
Amines
In general, amines undergo rapid autooxidation62'69. Their autooxidation mechanisms and
transformation kinetics are complicated and not well understood. In the presence of
oxygen in sediments and soils, they can form covalent bonds with the organic components
of the solids and thus become bound residues. Under anoxic conditions in sediments and
soils, however, they appear to be stable for long periods of time and tend not to bind
irreversibly to the organic matter associated with the organic carbon.
No comprehensive data base of rate constants for these types of reactions has been
compiled and, furthermore, the reaction kinetics are too complex to extrapolate precise
rate constants from the laboratory to field conditions.
Because reactions have been observed for a large number of amines, it is reasonable to
assume that these compounds will undergo autooxidation in the field. Based on the
qualitative data base, half-lives for this class of compounds will be less than 1 year.
-------
TABLE 1. Chemical hydrolysis rate constants and sorptlon data for organic compounds.
Common Name
1. Acenaphthene
2. Acetone (2-propanone)
3. Acetonttrlle (methyl cyanide)
Acetamide
Acetic add
(pK.-4.65)
Ammonia
4. Acetophenone
5. Acrotein
3-Hydroxy-1 -propanal
6. Acrylarrtde
Acrylic add
(pK.-4.13)
Ammonia
7. Acrytonitrile
Acrylamlde **
Acrylic acid
(pK.-4.13)
Ammonia
8. Aldrin
9. Aniline
(benzenearrdne: pK.,-9.3)
Chemical
Abstract
Service
Na
83-32-9
67-64-1
75-05-8
60-35-5
64-19-7
7664-41-7
98-86-2
107-02-8
2134-29-4
79^)6-1
79-10-7
7664-41-7
107-13-1
79O6-1
79-10-7
7664-41-7
309-00-2
62-53-3
Sorptlon
Logrs,.
3.75
•0.588
•0.714
-1.55
-2.23
NA
1.26
-0.219
-1.3
-0.989
-1.84
NA
-0.089
-0.989
-1.84
NA
6.18
0.595
Sorptlon
Logic..
4.07
•0.268
-0.394
-1.23
-0.234
NA
1.58
0.101
-1.0
•0.669
0.161
NA
0531
-0.669
0.161
NA
6.496
0.915
Chemical Hydrolysis
k. k. kb
irV r1 irV
0
0
0
2.6E2
0
0
0
NO
0
31.5
0
0
5E2
31.5
0
0
0
0
0
0
0
0
0
0
0
6.68E8
0
1.8E-2
0
0
0
1.8E-2
0
0
0
0
0
0
45
1.5E3
0
0
0
NO
0
0
0
0
5.2E3
0
0
0
0
0
Comment
NHFQ
NHFQ
RATE
NHFG
NHFQ
NHFG
.
NHFQ
a
NHFQ
NHFQ.
RATE
a
NHFG
NHFG
NLFQ
. NHFG
Rofercncos
K«/K01./kh
/ 4/ 0
/ 4/ 0
/ 4/ 24
/ 4/ 5
/ 4/ 0
/ 01 0
1 4/ 0
/ 4/ 30
/ 29/ 0
/ 4/ 6
/ 4/ 2
/ 01 0
1 4/ 6
/ 4/ 6
/ 4/ 2
/ O'l 0
/ 71 0
1 4/ 0
-------
Common Name
m Antimony (and compound$ JiQ-S.)
n.Aramite
1 -Methyl-2-b>{1 .1 -dimethyl-
ethyf)phenoxy]ethylhydrogen8ulfite
1 -Melhyl-2lp-(1 .1 -dimethyl-
ethyl)phenoxy]ethanol
Sulfuric acid
1 -Methyl-2[p-(1 ,1 -aimetnytetnyl)-
phenoxylethanol
2-ChloroethylhydrogensuHite
Sulfuric acid
2-Chloroethanol
Hydrochloric add
Ethylene oxide
Ethylene glycol
2-Chloroethanol
Hydrochloric add
Ethylene oxide
Ethylene glyco!
12. Areenic (dntf xtifpoatriti KQ£,)
1& B«rium {«ntl COWpOwWte MAS,)
14. Benzfa]anthracene
15. Benzene
16. BenzWine
(pK.,-9.3)
17. Benzo[b]fluoranthene
18. Benzo|a|pyrene
Chemical
Abstract
Service
No.
T440^N)
140-57-8
NO
2416*30-0
7664-93-9
241640-0
NO
7664-93-9
107-07-3
7647-01-0
75-21-8
107-21-1
107-07-3
7647-01-0
75-21-8
107-21-1
T440-38-2
T440^9^
56-55-3
71-43-2
92-87-5
205-99-2
50-32-8
Sorption
LogK*
5.2
3.15
NA
3.15
NA
-0.492
NA
-1.1
-1.5
-0.492
NA
-1.1
-1.5
5.34
1.80
126
5.8
5.8
Sorption
l-OgK,,,
5.5
3.47
NA
3.47
NA
-0.172
NA
•0.792
-1.2
-0.172
NA
-0.792
-1.2
5.66
2.12
1.58
6.12
6.12
Chemical Hydrolysis
*. *n l«b
iir'r1 r1 iWr1
0
0
0
0
0
0
0
0
0
2.9E5
0
0
0
2.9E5
0
0
0
0
0
0
7.7
7.7
0
0
0
7.7
6.0E40
3.9E-2
0
21
0
3.9E-2
0
21
0
0
0
0
0
0
6.0E4
6.0E4
0
0
0
6.0E4
0
3.2E5
0
0
0
3.2E5
0
0
0
0
0
0
0
0
Comment
ff
09
NLFQ
NHFQ
NLFQ
gg
NHFQ
NHFO
NHFQ
NHFQ
• NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
References
Ko./Kn./*h
/ 29/
/ / 0
/ 4/ 0
/ 01 0
1 4/ 0
/ / 0
/ 01 0
1 4/ 3
/ 01 0
1 41 5
1 29/0
/ 4/ 3
/ 01 0
/ 4/ 5
/ 29/ 0
•f-
/ 4/ 0
/ 37/ 0
/ 4/ 0
/ 4/ 0
/ 4/ 0
{
3-
I
c?
I
-------
Coiiiiion Name
19. Benzotrichtoride
Benzole add
(pK.-4.18)
Hydrochloric BckJ
20. Benzyl alcohol
(PK.-15.1)
21. Benzyl chloride
Benzyl alcohol **
Hydrochloric acid
2& Bdfyjfctw {«mr wjiDpoufia* N-Q.&)
23. Bto(2-chloroethyl)ether
Hydrochloric add
2-(2-chtoroettioxy)8thanol
Hydrochloric add
Bfa(2-hydroxyethyl)ether
1.4-Dtoxane"
24. Sb(2-chlorolaopropyl)ether
Hydrochloric acid
(2-Hydroxylaopropyl-2-chloro-
l8opropyl)ether
0fe(2-hydroxyiaopropyl)
ether
Hydrochloric add
Chemical
Abstract
Service
No.
98-07-7
65-85-0
7647-01 -0
100-51-6
100-44r7
100-51-6
7647-01-0
744041*?
111-44-4
7647-01-0
628-89-7
7647-01-0
111-46-6
123-91-1
39638-32-9
7647-01-0
NG
72986-46-0
7647-01-0
SorpUon
LogK.
4.06
-0.11
NA
0.78
2.84
0.78
NA
0.80
NA
-0.186
NA
-1.62
-0.812
2.39
NA
2.7
1.1
NA
Solution
LogK«
4.38
1.89
NA
1.10
3.16
1.10
NA
1.12
NA
-0.154
NA
-1.30
•0.492
2.71
NA
3.0
1.4
NA
Chemical Hydrolysis
*. K, *b
ir'r1 r1 nrv1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.0E6
0
0
0
4.1 E2
0
0
0.23
0
0.28
0
0
0
0
0
0
0
0
0
0
0
0
0
• 0
0
0
0
0
0
0
0
0
0
Comment
NHFO
NHFG
NHFQ
RATE
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
See Part II.
NHFQ
b
NHFQ
NHFQ
References
K./K^/m,
/ 29/ 5
/ 4/ 0
/ 01 0
1 4/ 0
1 291 24
1 4/ 0
/ 01 0
1 1/ 3
/ 01 0
1 4/ 3
/ 01 0
1 4/ 2
/ 4/ 2
/ 4/ 0
/ 01 0
1 291 0
1 291 0
1 01 0
-------
Common Name
25. B6(2-ethylnexyl)phthalate
2-Ethylhexanol
2-Ethylhexyl hydrogen phthalate
2-Ethylhexanol
o-PhthaOc acid
(pK.-3.03)
26. Bromodichloromethane
Carbon monoxide
Hydrobromte add
Hydrochloric add
27. Bromomethane
(Flammable gas, bp-4°C)
Methano}**
Hydrobrornic add
28. Butanot
29. Butyl benzyl phthalate
Benzyl alcohol **
Butyl hydrogen phthalate
o-Phthalic add
(pK.-3.03)
n-Butanol **
n-Butanol **
Benzyl hydrogen phthalate
Benzyl alcohol -
o-Phthallc add
(pK.-3.03)
30. 2-sec-Butyl-4,6-dinttrophenol
(Dinoaeb: pK.-3.5)
31, 0«lR*i«n
-------
ffc_n Mmm
uommon name
32. Carbon disulfide
Carbonyl sulfide
Carbon dioxide
Hydrogen aulfide
(Flammable gas: bp- -60°C;
(PK.-7.0)
33. Carbon telracfitorkJe
Carbon dioxide
Hydrochloric add
34. Chlordane
2,4,5,6,7,8,8-Heptachtoro-
3a,4,7,7a-tetrahydro-4,7-
methano-1 H-lndene
35. pChtoreaniline
(pK.,-10)
36. Chlorobenzene
37. Chlorobenzilate
(PK.-13.6)
Sfo(pcriloropnenyl)nydroxy-
acetlc add (pK,-3.1)
Ap'-Dichtorobenzophenone
Ethanol
38. 2-Chtoro-1,3-butadiene
(Chloroprene)
Chemical
Abstract
Service
No.
75-15-0
463-58-1
124-38-9
7783-06-4
56-23-5
124-38-9
7647-01-0
57-74-9
5103-65-1
106-47-8
108-90-7
510-15-6
23851-46-9
90-98-2
64-17-5
126-99-8
Sorptlon
i-ogK,.
1.84
0.4
NA
NA
2.41
NA
NA
5.89
62
1.61
2.578
4.04
2.5
4.43
-0.62
1.74
Sorptlon
i-ogK..
2.16
0.7
NA
NA
2.73
NA
NA
621
6.5
1.93
2.898
4.36
4.5
4.75
-0.30
2.06
Chemical Hydrolysis
k. K, K,
M-'V' V wrv
0
NO
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
6.3E2
0
0
1.7E-2
0
0
0
0
0
0
0
0
0
0
0
3.1 5E4
4.1 E8
0
0
0
0
0
37.7
0
,
0
0
2.8E6
2.8E5
0
0
0
Comment
NHFG
NHFG
RATE
NHFG
NHFG
y
NLFG
NLFG
NLFG
ff
•
ff
NLFG
NHFG
NLFG
References
K^/K^/Hn
/ 1/ 61
/ 29 / 40
/ 01 0
1 01 0
1 371 13
/ 01 0
1 01 0
1 621 3
/ 29/ 2
/ 4/ 0
/ 71 1
/ 4/
/ 29/ 0
/ 4/ 0
/ 29/ 0
/ 4/ 0
-------
\swiiHifwti IVCHIIB
39. Chlorodibromomethane
Carbon monoxide
Hydrobromte add
Hydrochloric add
40. Chloroform
Carbon monoxide
Hydrochloric add
41. Chloromethane
(Methyl Chloride: op- -23.7°C)
42. 2-Chlorophenol
(PK.-8.4)
43. 3-Chtorbpropene
3-Hydroxypropene
Hydrochloric acid
44, Chwn*jm{aftd«»oipouixi6 N.Q&)
4S.Chrysene
Chemical
Abstract
Service
No.
124-48-1
630-08-0
10035-10-6
7647-01-0
67-66-3
630-08-0
7647-01-0
74-S7-3
95-57-8
107-05-1
107-18-6
7647-01-0
744*47*
218-01-9
Sorptlon
Log*..
NA
NA
NA
1.58
NA
NA
1.82
1.13
-0.57
NA
5.34
Sorptlon
l-ogK,.
2.23
NA
NA
NA
1.90
NA
NA
2.20
1.45
-0.250
NA
5.66
Chemical Hydrolysis
NQ
0
0
0
0
0
0
0
0
0
0
0
NQ
0
0
0
1.0E-4
0
0
0
40
0
0
0
2.5E4
0
0
0
2.74E3
0
0
0
0
0
0
0
ConvTwnt
NHFG
NHFG
NHFQ
NHFQ
NHFG
NLFQ
NHFQ
• NHFQ
NHFQ
K./K-./K,,
/ 4/ 41
/ 01 0
• 1010
1 01 0
1 37/13
/ 01 0
1 01 0
1 4/ 0
/ 4/ 5
/ 4/ 0
/ 01 0
1 4/ 0
46. Creeds (See below)
47. oCresol
(PK.-9.8)
48. mCresol
(PK.-10.0)
49. />Cresol
(PK.-10.1)
50. Cumene
95-48-7
108-39-4
106-44-5
98-82-8
1.76
1.76
1.76
3.40
2.12
2.12
2.12
3.72
0
0
0
0
0
0
0
0
0
0
0
0
NHFG
NHFG
NHFQ
NHFG
/ 4/ 1
/ 4/ 1
/ 4/ 1
/ 4/ 0
21
Sr
I
*
I
I
-------
Common Name
51. Cyanide (amenable)
Carbon dioxide
Ammonia
52. 2,4-Dtehtofophenoxyacetlc add
(2.4-D: PK.-3.1)
53. ODD
2,2-«s(4-chlorophenyl)-1-
cnloroethene
(DDMU)
Hydrochloric add
54. DDE
55. p,p'-DDT
DDE"
Hydrochloric add
56. Dlallate
Dlallate (Z-)
Dlallate (£-)
Diisopropylamlne
(pK.,-11.5)
frans-2,3-Dlchtoro-2-propene-1 -
thtol
(PK.-8.2)
cfe-2,3-Dlchloro-2-propene-1 -
thtol
(PK.-8.2)
Carbon dioxide
57. Dibenzfa,/>]antnracene
Chemical
Abstract
Service
No.
57-12-5
124-38-9
7664-41-7
94-75-7
72-54-8
1022-22-6
7647-01-0
72-55-9
50-29-3
72-55-9
7647-01-0
2303-16-4
17708-57-5
17708-58-6
108-18-9
16714-72-0
16714-71-9
124-38-9
53-70-3
Sofptlon
Log*.
NA
NA
0.68
5.89
6.47
NA
6.64
6.59
6.64
NA
4.17
3.8
3.8
0.84
2.4
2.5
NA
6.52
Sorptfon
1-ogK..
NA
NA
2.68
6.21
6.79
NA
6.956
6.91
6.956
NA
4.49
4.1
4.1
1.16
2.84
3.0
NA
6.84
Chemical Hydrolysis
k. k. kb
I/TV r1 mrV
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
29
0
0
0
2.5E-2
0
0
0
6.0E-2
0
0
0.10
3.2E-1
7.8E-2
0
0
0
0
0
0
0
0
0
2.2E4
0
0
0
3.1 E5
0
0
8E3
0
7.3E3
0
0
0
0
0
Comment
e
NHFQ
NHFQ
NLFQ
RATE
NLFO
NHFQ
NLFQ
.
NLFQ
NHFQ
RATE
RATE
NHFQ
NLFQ
NLFQ
NHFQ
. NHFQ
nmtmrmnnnm
nererences
K~l*-l**
/ / 27
/ 01 0
1 01 0
1 4/ 1
/ 4/ 24
/ 29/ 0
/ 01 0
1 71 12
/ 4/ 12
/ 71 12
/ 01 0
1 621 3
/ 29 / 24
/ 29 / 24
/ 4/ 0
/ 29/ 0
/ 29/ 0
/ 01 0
1 4/ 0
-------
M
O)
Common Name
58. 1,2-D!bromo-3-ch)oropropane
oo
UliJ*BUXl,B— I-B1;_ nnl«4
nyuroDroiMH; acto
2-Bromo-3-chtoropropanol
Hydrobromic add
Eplchlorohydrin
1 -Chloro-2,3-dihydroxy-
propane
l-Hydroxy-2,3-
propytene oxide
Qlycerol
Hydrochloric add
Qlycerol
Hydrochloric acid
2,3-Dibromo-1 -propanol
Hydrobromic add
Eplbromohydrin
1-Bromo-2.3-
dihydroxypropane
1-Hydroxy-2.3-
propytene oxide
Qlycerol
Hydrobromic add
Glycerol
Hydrochloric add
2,3-Dlbromopropene
Hydrobromic add
2-Bromo-3-chtoropropene
2-Bromo-3-hydroxypropene
Hydrobromic add
Hydrochloric add
59. Dibromomethane (melhytene bromide)
60. 1,2-Dichlorobenzene
Chemical
Abstract
Service
No.
96-124
4 /VtQC 4 ft A
10035-104
73727-394
10035-104
106494
96-24-2
556-52-5
5641-5
7647-01-0
5641-5
7647-01-0
96-13-9
10035-104
313244-7
4704-77-2
556-52-5
5641-5
10035-104
5641-5
7647-01-0
513-31-5
10035-104
16400434
598-194
10035-104
7647-01-0
74-95-3
95-50-1
Sorption
l-ogK.
1.94
MA
NA
0.17
NA
-0.53
-0.8
-1.7
-22
NA
-22
NA
1.10
NA
02
-12
-1.7
-22
NA
-22
NA
2.39
NA
1.75
1.40
NA
NA
121
3.08
Sorption
LogK..
2.26
Ikl A
NA
0.49
NA
•0210
-0.5
-1.4
-1.9
NA
-1.9
NA
1.42
NA
0.5
-0.857
-1.4
-1.9
NA
-1.9
NA
2.71
NA
2.07
1.72
NA
NA
1.53
3.40
Chemical Hydrolysis
*. *n K,
nr'r1 V M-V
0
0
0
2.5E4
0
7.7E4
0
0
0
0
0
0
1.9E4
0
7.7E4
0
0
0
0
0
0
0
0
0
0
0
0
4.0E-3
1.4
0
30.9
0.46
8.9
0
0
0
0
1.4
0
1.6E1
1.4
8.9
0
0
0
0
29
0
1.8
0
0
0
0
0
12E5
5.4E5
0
0
1.8E5
0
0
0
0
0
5.4E5
0
0
5.4E5
0
0
0
0
0
0
0
0
0
0
0
0
0
Comment
RATE
klLJC/2
NHFQ
CC
NHFQ
f
NHFQ •
NHFQ
NHFQ
NHFQ
CC
NHFQ
. cc
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
NLFQ
NHFQ
NHFQ
NLFG.w
NLFQ
References
I*./*../*,,
/ 4/ 31
/n I f\
0-1 0
1 4/ 0
/ 01 0
1 41 5
1 291 0
1 291 5
1 291 0
1 01 0
1 291 0
1 01 0
1 291 0
1 01 0
, 1 291 41
/ 4/ 0
/ 291 5
/ 291 0
1 01 0
t 291 0
1 01 0
1 291 31
/ 01 0
1 41 31
/ 29/ 0
/ 01 0
1 01 0
1 41 0
1 37/ 1
I
I
-------
Common Name
61. 1,4-Dichlorobenzene
62. 3,3'-Dichlorobenzidlne
(pK.,-11,7)
63. Dtehlorodlfluoromethane
(Freon 12: bp - -29°C)
64. 1.1-Dtohloroethane
Acetaldehyde
(bp - 20°C)
Vinyl chloride
(bp - -13.37°C)
Hydrochloric acid
65. 1.2-Dlchtoroethane
Vinyl chloride
(bp--13.37°C)
Hydrochloric add
2-Chloroethanol
Ethytene oxide
Ethytene glyool
Hydrochloric add
66. 1.1-Dichloroethylene
(Vinylidene chloride: bp - 30-32°C)
67. cfe-1,2-Dlchloroethylene
68.
-------
. Common Nonw
70. 2.4-Dtehlorophenol
(PK.-7.9)
71. 1.2-Dichtoropropane
1-Chloro-1-propene
Hydrochloric add
2-Chloropropan-1-ol
Hydrochloric add
Propylene oxide
1 ,2-Dihydroxypropane
72. 1,3-Dlchtoropropene
(mixture of iaomsrs)
cfe-1 ,3-Dtehloropropene
cfe-3-Chloro-2-propen-1 -ol
Hydrochloric acid
frans-1 ,3-Dtehtoropropene
fra/79-3-Chtoro-2-propen-1 -ol
Hydrochloric acid
73. DieWrin
cto-1 ,2,3,4.1 0,1 0-Hexachloro-
6,7-dihydroxyexo-1 ,4,4a,5,6,7,
8,8a-octahydroexo-1 ,4-endo-5,8-
dimethanonaphthalene
(Dleldrln dtol)
frar»-1,2,3I4,10,10-Hexachloro-
6,7-dlrtydroxyexo-1 ,4,4a.5,6,7,
8,8a-octariydroexo-l ,4-endo-5,8-
dlmthanonaphlhalono
(Dieldrindtol)
Chemical
Abstract
Service
No.
120-83-2
78-87-5
590-21-6
7647-01-0
19210-21-0
7647-01-0
75-56-9
57-55-6
542-75-6
10061-01-5
4643-05-4
7647-01-0
10061-02-6
4643-06-5
7647-01-0
60-57-1
64839-05-0
57345-89-8
SorpUon
Log*,,
2.49
1.67
1.7
NA
0.58
NA
-0.59
-1.38
1.43
1.8
0.23
NA
1.8
0.18
NA
5.08
32
32
SorpUon
i-ogK,,.
3.07
1.99
2.0
NA
0.90
NA
-0.27
-1.06
2.2
0.55
NA
22.
0.50
NA
5.401
3.5
3.5
Ct
(f»nl Uifri mKr
cai nyorwiy
•Is
k. K, Kb
M-'r1 r1 irv1
0
0
0
0
0
0
1.9E6
0
0
0
0
0
0
0
0
0
0
0
4.6E-2
0
0
0.46
0
17
0
40
0
0
40
0
0
6.3E-2
0
0
0
42
0
0
1.8E5
0
3E3
0
0
0
0
0
0
0
0
0
0
Comment
NLFQ
RATE
NLFQ
NHFG
f
NHFQ
NLFQ
8
NLFQ
NHFQ
8
NLFQ
NHFQ
RATE
NLFQ
NLFQ
References
K./K-,/kh
/ 4/ 0
' / 4/ 24
/ 29/ 0
/ 01 0
1 291 0
1 01 0
I 4/ 5
/ 4/ 0
14/ /
/ 29/ 0
/ 29/ 0
/ 01 0
1 29/ 0
/ 29/ 0
/ 01 0
1.71 6
/ 29/ 0
/ 29/ 0
-------
common name
74. Dtethyl phthalate
Ethanol
Ethyl hydrogen phthalate
o-Phthallc add
(pK.-3.03)
Ethanol
75. DtethylsUlbestrol
(PK.-9.3)
Chemical
Abstract
Service
No.
84-66-2
64-17-5
2306-33-4
88-99-3
64-17-5
56-53-1
SorpUon
LogK^
1.99
-0.62
2.18
-1.27
-0.62
4.09
Sorption
LogK,
2.57
-0.30
2.50
0.732
-0.30
4.96
Chemical Hydrolysis
*. H» *b
irV r1 M-V
0
0
0
0
0
0
0
0
0
0
0
0
3.1 E5
0
1.6E5
0
0
0
Convnont
RATE
NHFO
c
NHFQ
NHFQ
NHFQ
R6f6f6f1C68
K-/K-/K,
11/ 4/ 9
/ 29/ 0
/ 29/ 0
/ 4/ 0
/ 29/ 0
/ 4/ 0
ro
-------
Common Name
76. Dimelhoate
(1^ at C)
O,O-Dimetrrylphosphorodithioic add
(PK.-1.6)
Methanol -
O-Methylphosphorodithioic add
(PK.-1.5)
Methanol -
Phosphorodithiolc add (pK,-1.7)
Phosphoric add
Hydrogen auffide
/V-Methyt-2-tiydroxyaoetamicle
Q^ at P)
OMethyl-S42-(A^nethylaoetamide)P
phosphorodithiolc acid (pK.-1.6)
AMrtethyl-2-hydroxyacetamlde
O-MethytphosphofOdithtolc add
(PK.-1.5)
Methanol**
Phoaphorodtthloic add
Phosphoric add
Hydrogen auffide
Methanol**
OO
O.O-Dimethytprioapnorotntoic add
(PK.-1.6)
Methanol-
O-Methylphosphorothloic add
(PK.-1.5)
Methanol**
Phosphorothlolc add
(PK.-1.5)
Phosphoric add
Hydrogen sulfide
Af-Methyl-2-mercaptoaoetamide (pK.-8.7)
Chemical
Abstract
Service
No.
60-51-5
756-60-9
67-56-1
106191-344
67-56-1
15834-33-0
7664-38-2
778346-4
5415-94-1
2700-77-8
5415-94-1
106191-344
67-56-1
15834-334
7664-38-2
7783-06-4
67-56-1
1112-38-5
67-56-1
1111-99-5
67-56-1
13598-51-1
7664-38-2
7783-06-4
20938-74-3
SorpUon
Logic,
0.132
-2.5
-1.08
-0.7
-1.08
-3.6
NA
NA
-0.8
-0.5
•0.8
-0.7
-1.08
•3.6
NA
NA
-1.08
-3
-1.08
-4
-1.08
-5
NA
NA
-0.8
SorpUon
1-ogK,,.
0.452
•0.5
-0.764
1.3
-0.764
-1.6
NA
NA
•0.5
1.5
•O.5
1.3
•0.764
-1.6
NA
NA
-0.764
-1
-0.764
-2.0
-0.764
-3.0
NA
NA
-1.0
Cn6fVnC8f Hydrolysis
k. k. Kb
ir'r1 r1 irv1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.68
03.
0
1
0
3
0
0
0
03
0
1
0
3
0
0
0
0.2
0
1
0
3
0
0
0
4.48E6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Comment
RATE
z
NHFQ
z
NHFQ
bb
NHFO
NHFG
NLFQ
NLFO
z
, NHFQ
bb
NHFQ
NHFQ
NHFQ
z
NHFO
z
NHFQ
bb
NHFQ
NHFQ
NLFQ
References
K./K../IC,,
/ 4/ 32
• / 29/ 0
/ 4/ 0
/ 29/ 0
/ 4/ 0
/ 29/ 64
/ 01 0
1 01 0
1 291 0
1 291 0
1 291 0
1 291 0
1 41 Q
1 291 64
/ 4/ 0
/ 01 0
1 4/ 0
/ 29/ 0
/ 4/ 0
/ 29/ 0
/ 4/ 0
/ 29/ 64
/ 01 0
1 01 0
1 291 0
-------
upmmon name
77. 3,3'-Dlmethoxybenzidine
(pKb-10.3)
78. 7,12-Dlmethytbenz(8]antnracene
79. 3,3'-Dlmethylbenzldlne
(prV-9.3)
80. 2,4-Dimethylprienol
(PK.-10.1)
81. Dimethyl phthalate
Methanol "
Methyl hydrogen phthalate
Methanol"
o-Phthalte add (pk.-3.03)
82. 1,3-Dbittrobenzene
83. 2,4-Dhittrophenol
(PK.-3.3)
84. 2,4-Dhittrotoluene
85. 2,6-Dlnltrotoluene
86. Dl-fvbutyl phthalate
n-Butanol **
iT-Butyl hydrogen phthalate
rr-Butanol •*
o-PhthaJlcacid
(pK.- 3.03)
Chemical
Abstract
Service
No.
119-90-4
57-97-6
119-93-7
105-67-9
131-11-3
67-56-1
4367-18-5
67-56-1
88-99-3
99-65-0
51-28-5
121-14-2
606-20-2
84-74-2
71-36-3
131-70-4
71-36-3
88-99-3
Sofptfon
1-ogK,,.
1.49
6.64
2.55
2.29
1.20
-1.08
1.6
-1.08
-1.27
1.31
•0.09
1.68
1.40
4.37
0.503
3.43
0.503
-1.27
Sorptlon
LogK,.
1.81
6.96
2.87
2.77
152
-0.764
1.9
-0.764
0.732
1.63
1.91
2.00
1.72
4.69
0.832
3.75
0.823
0.732
Chemical Hydrolysis
k. K. Kb
M-'V' r1 «rv1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.8E6
0
9E5
0
• 0
0
0
0
0
1.2E5
0
6E4
0
0
Comment
NHFQ
NHFQ
NHFQ
NHFQ
RATE
NHFQ
c
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ.
RATE
NHFQ
C
. NHFQ
NHFQ
References
K./Ke./k,,
/ 4/ 0
/ 4/ 0
/ 4/ 0
/ 4/ 0
/ 4/ 9
/ 4/ 0
/ 29/ 0
/ 4/ 0
/ 4/ 0
/ 4/ 0
/ 4/ 0
/ 4/ 1
/ 4/ 0
/ 4/ 9
/ 4/ 0
/ 29/ 0
/ 4/ 0
/ 4/ 0
G»
-------
Common Name
87. DI-rHJctyl phthalate
n-Octanol
n-Octyl hydrogen phthalate
n-Octanol
' o-Phthalic add
(pK.- 3.03)
88. 1,4-Dtoxane
89. 2378 TCDDIoxin
90. 2378 PeCDDtoxina
91. 2378 HxCDDkMdns
92. 2378 HpCDDtoxins
93. OCDD
(Octachtorodlbenzo-p-dioxin)
94. Diphenylamlne
(pK.,-13.4)
95. 1.2-Diphenythydrazine
(p^-13.2)
Chemical
Abstract
Service
No.
117-84-0
111-87-5
5393-19-1
111-87-5
88-99-3
123-91-1
174641-6
3268-87-9
122-39-4
122-66-7
Sorpdon
Log*..
7.6
2.77
5.8
2.77
-1.27
-0.812
6.10
6.9
7.3
7.8
8.08
3.30
1.4
SorpUon
Logic,.
7.9
3.09
6.1
3.09
0.732
-0.492
6.42
7.2
7.6
8.1
8.4
3.62
1.7
Chemical Hydrolysis
*. K, *b
ir'r1 r1 nrv1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
5.2E5
0
2.6E5
0
0
0
0
0
0
0
0
0
0
Comment
RATE
NHFQ
C
NHFQ
NHFQ
NHFG
NLFQ
NLFO
NLFQ
NLFQ
NLFQ
NHFQ
NHFQ
References
K./K../^
/ 29/ 15
/ 29/ 0
• / 29/ 0
/ 29/ 0
/ 4/ 0
/ 4/ 0
/ 16/ 0
7 29/ 0
7 29/ 0
7 29/ 0
7 29/ 0
7 4/ 0
7 47 0
(ff
!
I
?
ac
i
I
-------
bonvnon Name
96. Disulfbton
(kn at C)
O.O-Dietriylphosphorodlthlolc
add (PK.-1.5)
Ethanol
O-Etnylphosphorodfthiolc
add(pK.-1.6)
Ethanol
Phosphorodithidc add
(PK.-1.7)
Phosphoric add
Hydrogen sulfide
2-Hydroxyetnytethyltriioether
(k,, at P)......
Ethanol
O-Ethyl-S42-(elhytthio)ethylI-
phosphorodithiolc add(pK.-1.6)
2-Hydroxyethylethyfthlo-
ether
O-Ethylphoaphorodlthlolc
add (PK.-1.6)
Ethanol
Phosphorodlthidc add
(PK.-1.7)
Phosphoric add
Hydrogen sulfide
O.O-Diethylphosphorothlolc add
(PK.-1.5)
Ethanol
l"^Ff lt**/ *«•/ «h
/ 4/ 6
/ 29 / 0
/ 29 / 0
/ 29 / 0
/ 29 / 0
/ 29 / 64
/ 01 0
1 01 0
1 291 0
1 291 0
/ 29 / 0
/ 29 / 0
/ 29 / 0
/ 29 / 0
/ 29 / 64
/ 01 0
/ 01 0
1 291 0
1 291 0
/oo i n
ZS 1 O
/ 29 / 0
/ 29 / 64
/ 01 0
/ 01 0
1 291 0
-------
Common Name
97. End08ulfan(End08ulfan 1 and II,
mixture)
Endosulfan 1 (alpha)
Endosulfan II (beta)
Sulfuric add
1 ,4,5.6,7.7-Hexachlore-bicydo-
(22.1 |hept-5-ene-2,3-dimethanol
(Endosulfan dtol)
98. Endrin
cfe-Endrin dtol
frans-Endrin dtol
99. Epichtorohydrin
1 -Chloro-2,3-dihydroxypropane
1-Hydroxy-2,3-propytene
oxide
Olycerol
Hydrochloric add
Olycerol
100. 2-Ethoxyethanol
(PK.-15.1)
101. Ethyl acetate
Acetic add
(pK.-4.65)
Ethanol
102. Ethylbenzene
103. Ethyl ether
Chemical
Abstract
Service
No.
115-29-7
959-98-8
33213-65-9
7664-93-9
2157-19-9
72-20-8
34015-58-2
14737-72-5
106-89-8
96-24-2
556-52-5
56-81-5
7647-01-0
56-61-5
110-80-5
141-78-6
64-19-7
64-17-5
100-41-4
60-29-7
Sorption
Log*.
4.0
4.0
NA
2.5
4.60
3.2
3.2
-053
-0.8
-1.7
•22.
NA
-2.2
-0.54
0.351
•223
-0.62
3.00
0.55
SorpUon
••ogK,,.
4.3
4.3
NA
2.8
4.92
3.5
3.5
-0210
-0.5
-1.4
-1.9
NA
-1.9
-0217
0.671
-0234
-0.30
3.32
0.870
Chemical Hydrolysis
nr'r1 V irv
0
0
0
0
0
0
0
2.5E4
0
7.7E4
0
0
0
0
3.5E3
0
0
0
0
6.1 E-2
8.9E-2
0
0
5.5E-2
0
0
30.9
0.46
8.9
0
0
0
0
4.8E-3
0
0
0
0
1.7E8
3.0E8
0
0
0
0
0
0
1.8E5
0
0
0
0
0
3.4E6
0
0
0
0
Convncnt
RATE
RATE
NHFQ
NLFQ
NLFG
NLFQ
f
•
NHFQ
NHFQ
NHFO
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
References
K-/K-./H,,
• / 29/ 6
/ 29/ 6
/ 01 0
1 29/ 0
/ 62/ 1
/ 29/ 0
/ 29/ 0
/ 4/ 5
/ 291 0
/ 29/ 5
/ .291 0
1 01 0
1 291 0
1 4/ 0
/ 4/ 5
/ 4/ 0
/ 91 0
1 41 0
1 4/ 0
21
3-
a?
Si
I
I
i1
-------
Common Name
104. Ethyl methacrylate
Methacrytlc add
(pK.-4.45)
Ethanol
10S. Ethyl methanesulfbnate
Methylsuffbnlcadd
(pK. - -0.39)
Ethanol
106. Ethytene dlbromkte
(1,2-Dibromoetnane)
Hydrobromic add
Vinyl bromide
(bp"16°C)
2-Bromoethanol
Hydrobromic acid
Ethytene oxide
Ethylene glycol
Chemical
Abstract
Service
No.
97-63-2
79-41-4
64-17-5
62-50-0
75-75-2
64-17-5
106-93-4
10035-10-6
593-60-2
540-51-2
10035-10-6
75-21-8
107-21-1
SorpUon
LogK,.
1.27
-1.53
-0.62
-0.27
-2
-0.62
1.42
NA
123
-0.35
NA
-1.1
-15
SorpUon
l-ogK,.
1.59
0.470
-0.30
0.051
0
-0.30
1.74
NA
155
-3.2E-2
NA
-0.792
-1.2
Chemical Hydrolysis
k. k. kb
nrV r1 irV
0
0
0
0
0
0
0
0
0
0
0
2.9E5
0
0
0
0
1.25E3
0
0
6.3E-1
0
0
0.1
0
21
0
1.1 E6
0
0
0
0
0
0
0
. 0
1E6
0
0
0
Coranwnt
0
NHFQ
NHFQ
RATE
NLFQ
NHFQ
RATE
NHFG
NLFQ
r
NHFQ
NLFQ
References
K-/K-./K,
/ 4/ 0
/ 4/ 0
/ 29/ 0
/ 4/ 60
/ 29/ 0
/ 29/ 0
/ 4/ 3
/ 01 0
/ 4/ 0
/ 4/ 0
/ 01 0
1 4/ 5
/ 29/ 0
I
-------
common Name
107. Famphur
Methanol-
OMethyl-O-/HN.W-
dtrnethylsulfamoyl)-
phenylphosphorothtoic add
(PK.-1.5)
Methanol**
O-fH/V.W-Dimethylsulfamoyl)-
phenylphosphorothloic acid
(PK.-1.5)
Phoaphorothioic add
(PK.-1.5)
Phosphoric add
Hydrogen sulfide
p-(W.AI-Dimethyl-
sulfamoyQpnenol
(PK.-8.4)
pK
-------
Convnon NBITIO
111. Furan
112. 2378 TCOFuran
(2,3,7,8-Tetrachlorodlbenzofuran)
113. 12378 PeCDRjran
(1,2,3,7,8-PerrtacrilorodibenzDfuran)
114. 23478 PeCDFuran
(2,3,4.7.8-Pentachlorodlbenzofuran)
115. 2378 HxCDFurans
116. 2378 HpCDFuram
117.OCDF
(Octachlorbdlbehzofuran)
118. Heptachlor
1-Hydroxychlordene
Hydrochloric add
119. Heptachlor epoxide
Heptachlor dtol
Heptachlor triol
120. Hexachlorobenzene
121. Hexachlorobutadiene
Chemical
Abstract
Service
No.
110-00-9
51207-31-9
57117-41-6
57117-31-4
39001-02-0
76-44-8
24009-05-0
7647-01-0
1024-57-3
126959-40-8
126959-41-9
118-74-1
87-68-3
Sorpdon
Log*.
1.00
6.62
6.5
6.60
7.0
7.6
8.13
5.21
4.5
NA
4.9
3.7
22
5.411
4.46
Sorptton
Log*..
1.32
6.94
6.8
6.92
7.3
7.9
8.45
5.53
4.8
NA
5.2
4.0
2.5
5.731
4.78
Chemical Hydrolysis
k. k. Kb
M-V r1 nrv1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
61
0
0
6.3E-2
3.9E-3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3.2E4
0
0
0
Comment
NHFQ
NLFQ
NLFG
NLFG
NLFQ
NLFQ
NLFQ
RATE
NLFQ
NHFQ
h
h •
NLFQ
NLFQ
NLFQ
K^/K^/k,
/ 4/ 0
/ 4/ 0
/ 29/ 0
/ 16/ 0
/ 29/ 0
/ 29/ 0
/ 29/ 0
/ 62 / 25
/ 29/ 2
/ o/ o
/ 29/0
/ 29/ 0
/ 29/ 0
/ 71 1
/ 37/ 1
-------
iXMiwnon ndmo
122. a/prta-HCH
Hydrochloric acid
1 ,3,4,5,6-pentachtorocydo-
hexene
12.3-Trichlorobenzene
1 2.4-Trichlorobenzene
Hydrochloric acid
123. teta-HCH
124. Hexachlorocyclopentadiene
1 ,1 -Dlhydroxytetrachloro-
cydopentadlene
Polymers
125. Hexachloroethane
126. Hexachlorophene
(PK.-6.1)
127. Indeno(l2.3-cd|pyrene
128. Isobutyl alcohol
(PK.-15.8)
129. Isophorone
130. Kepone
Chemical
Abstract
Service
No.
31944-6
7647-01-0
319-94-8
87-61-6
120-82-1
7647-01-0
319-85-7
77-47-4
NO
67-72-1
70-30-4
193-39-5
78-83-1
78-59-1
143-50-0
1WMNM
Sorptlon
LogK.
3.43
NA
1 3.3
3.96
3.96
NA
3.43
4.72
3.61
5.0
626
0.44
1.9
4.15
Sorptlon
1-ogK,,.
3.75
NA
3.6
428
428
NA
3.75
5.04
3.93
7.3
6.58
0.76
22
4.47
Chemical Hydrolysis
k. k. k»
M-V V I/TV1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.05
0
026
0
0
0
0
24.8
0
0
0
0
0
0
1.74E6
0
6.5E5
0
0
0
0
0
0
0
0
0
0
0
Con vim it
NHFG
NLFG
NLFG
NHFG
NLFG
J, RATE
unstable
NLFG
NLFG
NHFG
NHFG
NHFG
k, NLFG
/ 4/ 0
/ 01 0
• 1 291 2
/ 4/ 6
/ 4/ 6
/ 01 0
1 4/ 0
/ 19/ 19
/ / 0
/ / 0
/ 1/ 24
1 291 0
1 4/ 0
/ 1/ 1
/ 8/ 0
/ 4/ 0
5T
I
I
-------
x-
Conwnon Ndtno
132. ganwna-HCH
(Undane)
Hydrochloric acid
1 ,3,4,5,6-pentachtorocydo-
hexene
1 ,2,3-Trichtorobenzene
1 ,2,4-TrtehtorobenzBne
Hydrochloric add
133. Mercury (and compounds NJ&&*
134. MethacrytonHrile
Methacrylamide
Methacryllc add
(pK.-4.45)
Ammonia
135. Methanol
l
136. Methoxychlor
Hydrochloric add
2,2-a5s(jHnethoxyprtenyl)-
1,1-dlchtoroethylene
Anlsoin
Anisll *
137. 3-Methylcholanthrene
138. Methyl ethyl ketone
139. Methyl iaobutyl ketone
Chemical
Abstract
Service
No.
58-89-9
7647-01-0
319-94-8
87-61-6
120-82-1
7647-01-0
7439-97-6
126-98-7
79-39-0
79-41-4
7664-41-7
67-56-1
72-43-5
7647-01-0
2132-70-9
119-52-8
1226-42-2
56-49-5
78-93-3
108-10-1
Sorptlon
1-ogK..
3.40
NA
3.3
3.96
3.96
NA
022
0.7
-153
NA
-1.08
4.90
NA
4.1
3.9
3.38
7.0
•0.03
0.87
SorpUon
Logic.
3.72
NA
3.6
4.28
4.28
NA
0.540
1.0
0.470
NA
-0.764
5.08
NA
4.4
4.2
3.70
7.3
029
1.19
Chemical Hydrolysis
k. k, K.
ir'r1 r' irv
0
0
0
0
0
0
•
5E2
31.5
0
0
0
0
0
0
0
0
0
0
0
1.05
0
0.26
0
0
0
0
1.8E-2
0
0
0
0.69
0
0
6E3
0
0
0
0
1.73E6
0
6.5E5
0
0
0
•"
5.2E3
0
0
0
0
1.2E4
0
0
0
0
0
0
0
Conrwnont
NHFQ
NLFQ
NLFQ
NHFQ
I
I
NHFQ
NHFQ
NHFQ
NHFQ
NLFQ
m
NHFQ
NHFQ
NHFQ
NHFQ
References
K./K./kn
/ 1/ 4
/ 01 0
/ 29/ 2
/ 4/ 6
/ 4/ 6
/ 01 0
1 4/ 0
/ 29/ 0
/ 4/ 0
/ 01 0
1 4/ 0
38 / 38 / 12
/ 01 0
1 91 0
1 91 0
/ 4/ 0
/ 29/ 0
/ 65 / 1
/ 4/ 0
-------
Common Name
140. Methyl methacrytate
Methacrylic add
(pK.-4.45)
Methanol -
141. Methyl parathton
Methanol**
O-Methy1-O-(/>nrtrophenyl)-
phoaphorothtoic acid (pK.H.3)
Methanol**
CHP-NHrophenyOphosphoro-
thtoteadd(pK.-l.l)
Phoaphorothlolc add
(PK.-1.5)
Phosphoric add
Hydrogen aufflde
p-Nttrophenol
(PK.-7.0)
p-Nltrophenol
(PK.-7.0)
O.O-Dimethylphosphorothlolc add
(PK.-1.6)
Methanol**
O-Methylphosphorothioic add
(PK.-1.5)
Methanol**
Phoaphorothldc add
(PK.-1.5)
Phosphoric add
Hydrogen eulflde
142. Naphthalene
143. 2-Naphthylamine
(pKt-9.8)
mittilkl llf tlltmfl Hfl¥VMlrilllM4lril ltt^*l £f *t
Nickel \anoconpouna8 N.-O&I
Chemical
Abstract
Service
No.
80-62-6
79-41-4
67-56-1
298-00-0
67-56-1
7699-30-1
67-56-1
18429-96-4
13598-51-1
7664-38-2
77834)6-4
100-02-7
100-02-7
1112-38-5
67-56-1
1111-99-5
67-56-1
13598-51-1
7664-38-2
778SO6-4
91-20-3
91-59-8
744&02H&
SorpUon
LoflK,,.
0.74
-1.53
-1.08
2.47
-1.08
-2.5
-1.08
-5
NA
NA
12
1.2
-3
-1.08
-4
-1.08
-5
NA
NA
3.11
1.77
- ' ' '
SorptJon
LogK..
1.06
0.470
-0.764
2.79
•0.764
-0.5
-0.764
-3.0
NA
NA
1.85
135
-1
-0.764
-2.0
-0.764
-3.0
NA
NA
3.36
2.09
•
'• -'.
Chemical Hydrolysis
k. K, kb
M-V1 r1 irV1
0
0
0
NO
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.8
0
02
0
1
3
0
0
0
0
02.
0
1
0
3
0
0
0
0
1.9E6
0
0
NO
0
0
' 1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
ConwiMiit
RATE
NHFQ
NHFQ
n
NHFQ
z
NHFQ
z
bb
NHFQ
NHFQ
NHFQ
NHFQ
z
NHFQ
z
NHFQ
bb
NHFQ
NHFQ
NHFQ
NHFQ
References
l^/K^/k,
/ 4/ 24
/ 4/ 0
/ 4/ 0
/ 4/ 39
/ 4/ 0
/ 29/ 0
/ 4/ 0
/ / 0
/ 29/ 64
/ 01 0
1 01 0
1 4/ 0
•
/ 4/ 0
/ 29/ 0
/ 4/ 0
/ 29/ 0
/ 4/ 0
/ 29/ 64
/ 01 0
1 01 0
38 / 38 / 0
/ 4/ 0
of
I
-------
Common NDTM
145. Nitrobenzene
146. 2-NHropropane
147. W-Nttroso-dl-n-bulylamine
(PK.<1)
148. W-NHroaodlelhylairtne
(PK.<1)
149. M-NHreaodlmethylamlne
(PK.<1)
150. W-Nrtroaodlphenylamlne
(pK.0)
151. W-Nttroao-dl-n-propylamine
(PK.<1)
152. W-Nitroaometnyletnylanime
(PK.<1)
153. WLNttroaoplperidlne
154. W-Nltroaopyrrofldlne
155. Octameihyl pyropho«phoramide
BtofW.AfLethylarnlno)-
phoaphortc add (pK.4-2)
Chemical
Abstract
Service
No.
98-95-3
79-46-9
924-16-3
55-18-5
62-75-9
86-30-6
621-64-7
10595-954
100-75-4
930-55-2
152-16-9
27972-73-2
Sorpflon
LogK«
1.51
0^3
2.09
-0.03
0.448
2.84
1.03
1.03
-0.02
-0.57
Sorption
LogK..
1.83
0.554
2.41
0.290
0.768
3.16
1.35
1.35
0.305
-0.254
Chemical Hydrolysis
M-V r1 nrV
0
0
0
0
0
0
0
0
0
0
1.9E3
0
0
0
0
0
0
0
0
0
0
0
NQ
0
0
0
0
0
0
0
• 0
0
0
0
NQ
0
Comment
NLFQ
NHFQ
NHFQ
NHFQ
NHFQ
NHFG
NHFQ
NHFQ
NHFQ
NHFQ
NLFQ
K./K-/K,
/ 37/ 1
/ 4/ 0
/ 29/ 0
/ 29/ 0
/ 29/ 0
/ 29/ 0
/ 29/ 0
/ 29/ 0
/ 4/ 0
/ 4/ 0
/ / 34
/ / 0
-------
Common Nsnns
156. Parathion (ethyl)
Ethanol
O-Ethyl-O-{p^itrophenyO-
phosphorothlolc add (pK.-1.2)
Ethanol
O{p-Nttrophenyl)pho8phoro-
thtote add (pK.H.1)
p-Nitrophenol
(PK.-7.0)
Phopsphorotnloic add
(PK.-1.5)
Phosphoric add
Hydrogen suffide
p-Nitrophenol
(pK.-7.OJ
O.O-Diethylphosphorothiolc add
(PK.-1.5)
Ethanol
O-Ethylpnosphorothioic add
(PK.-1.5)
PhOBphorothioic add
(PK.-1.5)
Phosphoric add
Hydrogen auffide
Ethanol
157. Pentadilorobenzene
158. Pentachloronltrobenzene (PCNB)
159. Pentacnlorophenol
(PK.-4.8)
160. Phenol
(PK.-10)
Chemical
Abstract
Service
No.
56-38-2
64-17-5
15576-30-4
64-17-5
18429-96-4
100-02-7
13598-51-1
7664-38-2
7783-06-4
100-02-7
2465-65-8
64-17-5
14018-63-4
13598-51-1
7664-38-2
7783-06-4
64-17-5
608-93-5
82-68-8
87-86-5
108-95-2
Sorptton
LogK..
3.15
-0.62
-0.62
1.2
-5
NA
NA
1.2
-2
-0.62
-1.5
-5
NA
NA
-0.62
5.39
4.57
3.06
1.23
Sorptloii
1-ogK,,
3.47
-0.30
-0.30
1.85
-3.0
NA
NA
1.85
0
-0.30
0.5
-3.0
NA
NA
-0.30
5.183
4.89
5.06
1.48
CnCfnicBt Hydrolysis
k. k. Kb
nr'r1 r1 M-V
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.4
0
0.2
0
1
0
3
0
0
0
0.2
0
1
3
0
0
0
0
0
0
0
3.7E6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
COfTWIIGflt
NHFQ
z
NHFQ
z
NHFQ
bb
NHFQ
NHFQ
NHFQ
z
NHFQ
. z
bb
NHFQ
NHFQ
NHFQ
NLFQ
NLFQ
NLFQ
NHFQ
••_•_ _
noforoncvs
K«/K»/l«h
/ 4/ 21
/ 29/ 0
• / / 0
/ 29/ 0
/ / 0
/ 4/ 0
/ 29/ 64
/ 01 0
1010
1 4/ 0
/ 29/ 0
, / 29/ 0
/ 29/ 0
/ 29/ 64
/ 01 0
1 01 0
1 291 0
1 71 0
1 */ 0
/ 4/ 1
/ 4/ 1
I
I
3*
I
-------
Common Name
161. Phenylenediarrine:
1 ^-Phenylenediarrine
(pKfc-9.3)
1 ,3-Phenylenedlamlne
1 ,4-Phenylenedlamlne
(pKb-7.7)
Chemical
Abstract
Service
No.
95-54-5
108-45-2
106-50-3
SorpUon
l-ogK.
•0.1
-0.3
NA
Sorptton
t-OflK,,
02
0.05
-0.4
Chemical Hydrolysis
k. k. K,
M-'Y" r1 irv1
0
0
0
0
0
0
0
0
0
Comment
NHFQ
NHFQ
NHFQ
References
K./Kc./k,,
/ 29 / 0
/ 291 0
/ 29 / 0
-------
Common Name
162. Phorate
—A 04 BL/-H
-——"••—••— {Kjj fli r*1 £/j«——— •--
Ethanol
OEthyl-S4(ethylthlo)methylh
phoapnorodtthioic add
(PK.-1.6)
O-Ethylphosphorodlthtolc
add (PK.-1.6)
Phosphorodtthioic add
(PK.-1.7)
Phosphoric add
Hydrogen sulfide
Ethanol
Hydroxymelhyletriytthlo-
ether
Mercaptomelhylethytthtoether
aO-Diethylphosphorothtolc add
(PK.-1.5)
Ethanol
O-Ethylphospnorothioic add
(PK.-1.5)
Phosphorothioic add
(PK.-1.5)
Phosphoric add
Hydrogen sulfide
Ethanol
it\f nt Q ^^
HydroxymethytethyWitoetner
aO-Diethylphosphorodltfiioic
add(pK.-l.5)
Ethanol
O-Ethylphosphorodithtolc add
(PK.-1.6)
Ethanol
Phosphorodithioic add
(PK.-1.7)
Phosphoric add
Hydrogen sulfide
Chemical
Abstract
Service
No.
298-02-2
64-17-5
NQ
NQ
15834-33-0
7664-38-2
7783-06-4
64-17-5
15909-30-5
29414-49-1
246545-8
64-17-5
14018-63-4
13598-51-1
766448-2
778346-4
64-17-5
15909-30-5
298464
64-17-5
NQ
64-17-5
15834-334
7664-38-2
778346-4
Sorption
Log*.
2.64
4.62
-2.5
-1
-3.6
NA
NA
4.62
02
2.0
-2
4.62
-1.5
-5
NA
NA
4.62
02
•22
4.62
-1
4.62
-3.6
NA
NA
Sorption
I-OSK.,,
2.96
4.30
4.5
1.0
-1.6
NA
NA
4.30
0.5
2.3
0
4.30
0.5
-3.0
NA
NA
4.30
0.5
•02
4.30
1.0
4.30
-1.6
NA
NA
Chemical Hydrolysis
•s , "-, ">
•TV r' n/rV1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
62
0
02
1
3
0
0
0
0
0
02
0
1
3
0
0
0
0
02
0
1
0
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Comment
RATE
NHFQ
z
z
bb
NHFQ •
NHFQ
NHFQ
NLFQ
NLFQ
z
,
NHFQ
z
bb
NHFQ
NHFQ
NHFQ
NLFQ
z
NHFQ
z
NHFQ
bb
NHFQ
NHFQ
rr •£••••• n ••
no id ui iuco
/ 4/ 25
• / 29-/ 0
/ 29/ 0
/ 29/ 0
/ 291 64
/ 01 0
1 01 0
1 291 0
1 291 0
1 291 0
1 291 0
1 291 0
1 291 6
1 291 64
/ 01 0
1 01 0
1 291 0
1 291 0
1 291 0
1 291 0
1 291 0
1 291 0
1 291 64
/ 01 0
1 291 0
!
&
I
I
I
-------
i*unwTKMi mmo
163. Ptrthalte anhydride
o-Phthalic add
(pK.-3.03)
164. Porychlorinated blphenyts
(Arodors)
165. PronamkJe
3,5-Dtehlorobenzote add
(pK.-3.46)
1 ,1 -Dlmetnyl-2-propynylamine
(PK.-8.1)
166.Pyrene
167. Pyridlne
(pK.,-8.7)
168.Safrole
169, Selerturtt{and oOftlpowidft M.O^S.)
__^ ^ rt
170, saw pro OWpOttOQB N-Q,5,)
171. Strychnine and salts
(pK.,-4.7)
172. Styrene
173. 1,2,4,5-Tetrachlorobenzene
Chemical
Abstract
Service
No.
85-44-9
88-99-3
133646-3
23950-58-5
51-36-5
2978-58-7
129-00-0
110-86-1
94-59-7
fNMMt
7440**4
57-24-9
100-42-5
9544-3
SorpUon
LogK,,
-1^7
2.63
1.5
-0.63
4.92
0.34
2.34
NA
2.84
4^84
SorpUon
Logic,,
-0.62
0.732
2.95
3.5
-0.308
5.18
0.665
2.66
2.0
3.16
4.604
Chemical Hydrolysis
k. k. K.
iir'r1 V M-V
0
0
0
59
0
0
0
0
0
:
0
0
0
4.9E5
0
0
0
0
0
0
0
0
0
0
0
0
0
0
6.1 E2
0
0
0
0
0
0
0
0
_
U. RATE
NHFG
NLFG
RATE
NLFG
NHFG
NHFG
NHFG
NHFG
-
v
NLFG
NHFG
NLFG
neierences
/ 35 / 22
/ 4/ 0
/ / 0
/ 4/ 6
/ 29 / 0
/ 4/ 0
/ 38 / 0
/ 4/ 1
/ 4/24
/ 29 / 0
/ 37/ 0
/ 71 0
-------
Common Name
174. 1,1,1,2-Tetrachloroethane
1,1.2-Trichloroelhylene-
2.2,2-Tricriloroelhanol (pK.-3.7)
Hydroxyacetic add
Hydrochloric acid
Hydrochloric acid
175. 1,1,2,2-Tetrachloroethane
1 ,1 ,2-Trichtoroethylene **
Hydrochloric add
176. Tefrachloroethylene
177. 2&4,6-Tetraoh1orophenol
(PK.-5.3)
178. Tetraethyl dithtopyrophoaphate
(Sulfotep)
O.OOIetriytphosphorothlolc add
(PK.-1.5)
Ethanol
O-Ethylphosphorolhtoic add
(PK.-1.5)
Phosphorothioic add
(PK.-1.5)
Phosphoric add
Hydrogen autflde
Ethanol
179. fhaalym (and wmpotmds «.<*&)
180. Toluene
181. 2,4-Tduenedlamlne
(prV-9.0)
Chemical
Abstract
Service
No.
630-20-6
79-01-6
115-20-8
79-14-1
7647-01-0
7647-01-0
79-34-5
79-01-6
7647-01-0
127-18-4
58-90-2
3689-24-5
2465-65-8
64-17-5
14018:33-4
13598-51-1
7664-38-2
7783-O6-04
64-17-5
74404!
108-88-3
95-80-7
SorpUon
Log*,.
2.71
2.10
1.13
-4
NA
NA
2.07
2.10
NA
2.21
2.32
3.51
-2
•0.62
-1.5
-5
NA
NA
-0.62
2.43
0.02
SorpUon
1-ogK..
3.03
2.42
1.45
-2
NA
NA
2.39
2.42
NA
2.53
4.32
3.83
0
-0.30
0.5
-3.0
NA
NA
-0.30
2.75
0.337
Chemical Hydrolysis
k. k. Kb
M-'V Y" M-V
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.37E-2
0
0.65
0
0
0
5.10E-3
0
0
0
0
84
02
0
1
3
0
0
0
0
0
1.1 3E4
0
0
0
0
0
1.59E7
0
0
0
0
9E6
0
0
0
0
0
0
0
0
0
Convnont
RATE
NLFO
V
NHFQ
NHFQ
NHFQ
RATE
NLFQ
NHFQ
NLFQ
NLFQ
0
z
NHFQ
z
bb
NHFQ
NHFQ
NHFQ
NHFQ
NHFQ
References
K»/Km./kh
/ 1/ 13
/ 37/ 2
• / 29/ 0
/ 29/ 0
/ 01 0
1 01 0
1 371 13
/ 37/ 0
/ 01 0
1 371 0
1 4/ 1
/ 62/ 36
/ 29/ 0
/ 29/ 0
/ 29/ 0
/ 29/ 64
/ 01 0
1 01 0
1 291 0
1 29/ 1
/ 4/ 0
3"
!
!
!
-------
IXIffWnon nomB
182. 2,6-Toluenediamine
(pK.,-8.9)
183. o-Toluldine
(pK.,-9.3)
184. p-Toluidine
(pK.,-8.9)
185. Toxaphene (chlorinated camphenes)
186. Trlbromomethane
(Brornofbrrn)
Carbon monoxide
Hydrobromlc add
187. 1,2,4-Trlchtorobenzene
188. 1,1,1-Trichloroethane
1,1-Dichloroethytene**
(bp-31.9°C)
Acetic add
(pK.-4.73)
Hydrochloric add
189. 1,1,2-Trichloroelhane
1.1-Dichloroetriylene"
(bp-3l.9«C)
Hydrochloric add
Chtoroacetaldehyde
Hydroxyacetaldehyde
Hydrochloric add
190.Trichloroelhytene
(1,1,2-Trichtoroethylene)
Chemical
Abstract
Service
No.
823-40-5
95-53-4
106-49-0
8001-35-2
75-25-2
630-08-0
10035-104
120-82-1
71-55-6
75-35-4
64-19-7
7647-01-0
79-00-5
75-35-4
7647-01-0
107-20-0
141-46-8
7647-01-0
79-01-6
oorpuon
Log*.
0.02
1.24
1.24
4.31
2.05
NA
NA
3.96
2.16
1.79
-233
NA
1.73
1.79
NA
0.07
-1.38
NA
2.10
oorpuon
LogK..
0.337
1.56
1.56
4.63
2.37
NA
NA
4.28
2.47
2.11
•O.234
NA
2.05
2.11
NA
0.389
-1.06
NA
2.42
Chemical Hydrolysis
*. «n «b
M-'Y" r1 M-Vr1
0
0
0
0
NO
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
7.0E-2
NO
0
0
0
6.4E-1
0
0
0
2.73E-5
0
0
7E-3
0
0
0
0
0
0
2.8E4
1E4
0
0
0
2.4E6
0
0
0
4.95E4
0
0
2.6E4
0
0
0
COIIWlMlll
NHFQ
NHFQ
NHFQ
P
t
NHFQ
NHFQ
NLFQ
.
NLFQ
NHFQ
NHFQ
RATE
NLFQ
NHFQ
NHFQ
NHFQ
NLFQ
References
K./K,,/^
/ 4/ 0
' / 4/ 0
/ 4/ 0
/ 62/24
/ 4/ 1
/ 01 0
1 01 0
1 4/ 2
/ 37 / 67
/ 1/ 2
/ 4/ 2
/ 01 0
1 4/ 13
/ 1/ 2
/ 01 0
1 4/ 2
/ 4/ 2
/ 01 0
1 37/ 2
-------
common Name
191. Trfchlofofluorornethane
(Freon11:bp-24.1°C)
192. 2.4,5-Trichlorophehol
(PK.-7.1)
193. 2,4,6-Trichlorophenol
(PK.-6.4)
194. 2.4.5-Trichlorophenoxyacetlc add
(PK.-3.0)
195. 2-(2,4,5-Trichlorophenoxy)proplonlc
add (Silvex: (0K.-3.4)
196. 12.3-Trichloropropane
j , Ir
•Si
Hydrochloric acid
2,3-Dfehloro-1 -propanol
Epichtorohydrin
1 -Chloro-2,3-dlhydroxy-
propane
1-Hydroxy-2,3-
propylene oxide
Glycerol
Hydrochloric add
Glycerol
Hydrochloric add
Hydrochloric acid
2,3-Dichloropropene
2-Chloro-3-hydroxypropene
Hydrochloric acid
1 97. 1 .1 ,2-Trichloro-1 22-trtfluoro-
ethane
Chemical
Abstract
Service
No.
75-69-4
95-95-4
88-06-2
93-76-5
93-72-1
96-18-4
7647-01-0
616-23-9
106-89-8
96-24-2
556-52-5
56-81-5
7647-01-0
5641-5
7647-01-0
7647-01-0
78-88-6
5976-47-6
7647-01-0
76-13-1
Sorptlon
Logic.
2.11
2.93
225
1.43
1.74
1.66
NA
0.5
-0.53
-0.8
-1.7
-22
NA
-22
NA
NA
1.8
•0.1
NA
2.97
Sorptlon
Logic..
2.43
3.85
3.57
3.43
3.74
1.98
NA
0.8
-0210
-0.5
-1.4
-1.9
NA
-1.9
NA
NA
2.1
025
NA
329
Chemical Hydrolysis
"S i *% *"
0
0
0
0
0
0
0
0
2.5E4
0
7.7E4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.7E-2
0
0.46
30.9
0.46
8.9
0
0
0
0
0
1.8
0
0
0
0
0
0
0
0
3.6E3
0
1.8E5
0
1.8E5
0
0
0
0
0
0
0
0
0
0
Com ii6i it
NLFG.ee
NLFG
NLFG
NLFG
NLFG
RATE
NHFG
f
NHFG
NHFG
NHFG
NHFG
NHFG
X
NLFG
NHFG
NLFG
References
IC./KO./K,
/ 4/ 0
/ 4/ 1
/ 4/ 1
/ 4/ 0
/ 4/ 1
/ 4/ 6
/ 01 0
1 291 3
/ 4/ 5
/ 29/ 0
/ 291 5
1 291 0
/ 01 0
1 291 0
1 01 0
1 01 0
1 291 0
/ 4/ 0
/ 01 0
1 4/ 0
sr
I
I
I
I
-------
Common Name
198. sym-Trinrtfobenzene
(1,3.5-Trinltrobenzene)
199. 7rb(2,3-dibromopropyl)phosphate
/tr \
INJ — -
O,O(2,3-Dlbromopropy1)-
phosphoric add (PK.-0.8)
O(2,3-Dibromopropyl)-
phosphorlc add (pK.-1.3)
2,3-Oibromo-l -propanol
Phosphoric add
2,3-Dibromo-1 -propanol
Hydrobrorrtc add
Epibromohydrin
1-Bromo-2,3-
dlhydroxypropane
1-Hydroxy-2,3-
propylene oxide
Glycerol
Hydrobfomtc add
Glycerol
2,3-Dibromo-l -propanol
Hydrobromks add
2-Bromo-1 ,3-propanedlol
Glycerol
yoroDiomc aao
/L, \
W
O,O-(2,3-Dibromopropyl)-
phosphoric add (pK.-0.8)
2,3-Dibromo-1 -propanol
2-Bromo-2-propen-1 -ol
LjLJflHJxblBMtM.il II Xlllll
nyoroDrorrac aciu
200;* Vanadium
201. Vinyl chloride
(Chtoroethene: bp - -13.4°C)
Chemical
Abstract
Service
No.
99-35-4
126-72-7
5412-25-9
5324-12-9
96-13-9
7664-38-2
96-13-9
10035-10-6
3132-64-7
4704-77-2
556-52-5
56-81-5
10035-10-6
56-81-5
96-13-9
10035-10-6
4704-87-4
56-81-5
10035-10-6
5412-25-9
96-13-9
598-19-6
10035-10-6
7440-62-2
754)1-4
Sorpdon
LogK..
1.05
3.19
1.10
NA
1.10
NA
02
-1.18
-1.7
•22
NA
-22
1.10
NA
-1.4
-22
NA
1.10
0.43
M A
NA
1.04
SorpHon
Logr^
1.37
3.51
1.42
NA
1.42
NA
0.5
-0.857
-1.4
-1.9
NA
-1.9
1.42
NA
-1.1
-1.9
NA
1.42
0.75
» 1 *
NA
1.36
Chemical Hydrolysis
k. k, k,,
M-V1 r1 M-V
0
0
0
0
0
0
0
0
1.9E4
0
7.7E4
0
0
0
0
0
0
0
0
0
0
0
0
0
8.8E-2
02
1
1.4
0
1.4
0
1.6E1
1.4
8.9
0
0
0
1.4
0
2
0
0
02
1.4
0
0
0
0
3.0E5
0
0
5.4E5
0
5.4E5
0
0
5.4E5
0
0
0
0
5.4E5
0
9E5
0
0
0
5.4E5
0
0
ConvnGnt
NHFG
RATE
z
z
cc
NHFG
cc
NHFG
CC
*
NHFG
NHFG
NHFG
' cc
NHFG
q
NHFG
NHFG
z,dd
cc
NLFG
NHFG
NLFG
References
"-/K-fk,,
/ 4/ 0
/ 4/24
/ / 0
/ / 0
/ 29 / 0
/ 01 0
1 291 0
1 01 0
1 29/41
/ 4/ 0
/ 29 / 5
/ 29 / 0
/ 01 0
1 291 0
1 291 0
1 01 0
1 291 0
1 291 0
1 01 0
1 1 0
1 291 0
1 291 0
/n i t\
Of 0
'
1 1/ 0
-------
common Name
202. Xylenes
(mixture of three isomers)
o-Xytene
m-Xytene
p-Xylene
» nrttmmn «ui tJrtftl
W{ iXUWrfJOMflW .Q^.}
Chemical
Abstract
Service
No.
1330-20-7
95-47-6
108-38-3
106-42-3
744P4K*
Sorpdon
Log*.
3.02
3.09
3.12
SorpUon
Logic,.
3.34
3.41
3.44
Chemical Hydrolysis
k. k. kb
M-'V V M-V
0
0
0
0
0
0
0
0
0
0
0
0
-
Comment
NHFQ
NHFQ
NHFQ
NHFQ
7 7 0
• 7 297 0
7 297 0
7 297 0
tt>
&
5?
I
I
I
I
I
COMMENT
RATE) Hydrolysis data were extrapolated with the RATE program to obtain rate constants at 25° C (see reference #28).
NQ) A rate constant was not given In the publication or a CAS number was not assigned In the CAS Registry.
**) This product appears as a parent compound elsewhere In the alphabetically arranged table.
NA) When NA (not applicable) appears In one of the sorption columns, the compound Is either an Inorganic compound or an organic base that Is Ionized within the
environmental pH range with a pK, value greater than 6. A value cannot be computed.
Shaded rows contain Inorganic compounds which are not addressed In this work.
a) At an alkaline pH and concentrations above 2 ppm for acrylamide, cloudiness was observed in the laboratory hydrolysis experiment. Cloudiness was thought to have
been polymerization.
b) The hydrolysis rate constant was assumed to be the same as the parent compound's by analogy to M9(2-chloroetnyl)ether and Its product 2-(2- chloroethoxy)ethanol
(see text In Part II).
c) The hydrolysis rate constant was assumed to be half the parent's.
d) The hydrolysis rate constant was assumed to be the same as the one for di-n-butyl phthalate for both pathways.
e) Cyanide will not sorb onto sediments at a detectable rate.
f) The hydrolysis rate constants for 2-chloropropan-l -ol and 1 -chloro-2,3-dihydroxypropane were assumed by analogy to be the same as those of 2,3-dtehloro-1 -propanol
(see #196).
-------
g) The hydrolysis rate constant was estimated by analogy to be 0.6 of methyl methacrylate'a.
h) The hydrolysis rate constant for heptachlor epoxlde was assumed by analogy to be the same as dieldrin'a. The reaction to the final product heplachtor triol occurs
through the Intermediate heplachtor did, for which a rate estimate was assumed to be 1/10 the rate of 2-chloro-ethanol.
I) The hydrolysis rate constants were assumed by analogy to be the same as lindane's.
J) Hydrolysis of hexachlorocydopentadiene results hi the formation of l.l-dihydroxytetrachlorocyclopentadiene which is an unstable product. Its degradation leads to the
formation of polymers which cannot be identified.
k) Kepone hydrates In an aqueous medium. The sorption coefficient of the hydrated form may be orders of magnitude lower than the coefficient of the unhydrated form.
The given log values are for the unhydrated form. A value for the hydrated form cannot be estimated.
I) The hydrolysis rate constants for methaorytonltrlle and Its product methacrylamtde were assumed by analogy to be the same as those for acrytonftrile and Its product
acrylamide.
m) The product of methoxychtor, anlaoln. degrades to anlsO by autoaxkJation with an estimated haff-flfe of one hour.
n) The hydrolysis rate was determined at a pH<8.
o) The hydrolysis rate constants for tetraethyi dlftilopyrophosphate were based by analogy on the rate constants of tetraethyl pyrophosphate and tetraethyl
monothlopyropnoaphate. The rate constants of tetraethyl pyrophosphate were divided by 10 as an adjustment for the two sulfur substttuents In tetraethyl
dithtopyrophosphate.
p) Toxaphene Is produced by the chtortnatton of camphene and is a complex mixture of at least 177 C10 polychloro- derivatives. It has an approximate overall empirical
formula of C10H10CIS (The Merck Index, Eleventh Edition). Products can, therefore, not be Identified.
q) The hydrolysis rate constants for 2-bromo-1,3-propanediol were estimated by analogy to be five times those of 2.3-dfehtoropropanol'a (see #196) because of the two
hydroxide groups and the greater reactivity of bromine.
r) The hydrolysis rate constants for 2-bromoethanol were estimated by analogy to be three times larger than those of 2-chtoroetfianol because of the greater reactivity of
bromine.
s) The hydrolysis rate constants for the ds- and trans-1,3-dlchloropropene were assumed by analogy to be the same as 3-chloropropene's (#43).
t) The hydrolysis rate constants for bromodlchloromethane, cMorodibromomethane, and tribromomethane were determined In 66.67% (v/v) dtoxane/water.
u) Phthallc anhydride hydrolyzes to c-phthalte add with a half-life of less than one minute. A K,, value for the anhydride would be meaningless.
v) The hydrolysis rate constant for 2,2,2-trichloroethanol was assumed by analogy to be the same as 1,1,1 -trichloroetriane's (see #188).
w) QSAR model computations have indicated that the half-life of this hakxjenated methane is several thousand years. Its hydrolysis process was, therefore, designated
asNLFQ.
x) The hydrolysis rate constant for 2.3-dlchtoropropene was assumed by analogy to be the same as 2-bromo-3-chloropropene'8 (see #58).
I
01
-------
8
y) The tog K^, value for technical grade chlordane was calculated by averaging the measured values of the cfe- and frans- isomers. The hydrolysis rate constant given Is -^
for the ci9- isomer only. The trans- Isomer will not hydrotyze. n.
5?
z) The hydrolysis rate constant for the degradation of the organophosphorus dlester to the monoester was estimated to be smaller than the parent's by a factor of ten, c?
whereas the rate constant for the degradation of the monoester to the add was estimated to be half the rate of the parent's'. These estimated rate constants were 3
based on the average of the neutral rate constants of five organophosphorus compounds. ^
&
aa) The hydrolysis rate constants for dichtoromethane were extrapolated to 25°C from elevated temperatures. 3>
v
bb) The hydrolysis rate constant was estimated by extrapolation. Because the value was estimated, no distinction was made of the fact that hydrolysis of the
phosphorodithioic acid is slightly faster than the monoadd.
8-
cc) The hydrolysis rate constants for 2-bromo-3-chtoropropanol, 2,3-d!bromo-1-propanol, and 1-bromo-2.3-dihydroxypropane were estimated by analogy to be three times §
larger than those of 2,3-dichloro-l -propanol (see #196) because of the greater reactivity of bromine. s
f
dd) The alkaline hydrolysis pathway of the diester Is Identical to its neutral pathway.
-------
Parti
53
TABLE 2. SAR computed reductive rate constants for selected halogenated aliphatics
and nitroaromatics.
Halogenated Aliphatics
26. Bromodichloromethane
27. Bromomettiane
33. Carbon tetrachloride
39. Chlorodibromomethane
40. Chloroform
58. 1 ,2-Dibromo-3-chloropropane
59. Dibromomethane
64. 1,1-Dichloroethane
65. 1,2-Dichloroethane
69. Dichloromethane
71. 1 ,2-Dichloropropane
72. 1 ,3-Dichloropropene
106. Ethylene dibromide
125. Hexachloroethane
1 74. 1,1,1 ,2-Tetrachloroethane
1 75. 1,1 ,2,2-Tetrachloroethane
186. Tribromomethane
188. 1,1.1-Trichloroethane
189. 1,1,2-Trichloroethane
191. Trichlorofluoromethane
1 96. 1 ,2,3-Trichloropropane
1 97. 1,1 ,2-Trichloro-1 .2.2-trifluoroethane
Nitroaromatics
30. Dinoseb
82. 1 ,3-Dinitrobenzene
83. 2,4-Dinitrophenol
84. 2,4-Dinitrotoluene
85. 2,6-Dinitrotoluene
141. Methyl parathion
145. Nitrobenzene
156. Parathion
198. sym-Trinitrobenzene
Chemical
Abstract
Service No.
75-27-4
74-83-9
56-23-5
124-48-1
67-66-3
96:12-8
74-95-3
75-34-3
107-06-2
75-09-2
78-87-5
542-75-6
106-93-4
67-72-1
630-20-6
79-34-5
75-25-2
71-55-6
79-00-5
75-69-4
96-18-4
76-13-1
Chemical
Abstract
Service No.
88-85-7
99-65-0
51-28-5
121-14-2
606-20-2
298-00-0
98-95-3
56-38-2
99-35-4
1%
Organic Carbon
Wear1)
' 1.2E3
1.4E2
5.8E1
1.2E3
2.6E1
2.4E2
4.0E2
1.1 E1
4.0
8.7
5.4
6.7
1.7E2
2.8E1
7.0
7.5
1.2E3
1.5E1
5.4
5.8E1
4.3
4.0E1
1%
Organic Carbon
k(yeaV1)
5.0E3
8.0E2
2.2E3
6.6E2
8.0E2
1.2E2
3.0E2
1.2E2
2.2E3
0.02%
Organic Carbon
k(year-1)
1.9E-1
2.2E-2
9.3E-3
1.8E-1
4.2E-3
3.8E-2
6.4E-2
1.7E-3
6.5E-4
1.4E-3
8.5E-4
1.1 E-3
2.7E-2
4.5E-3
1.1 E-3
1.2E-3
1.8E-1
2.4E-3
8.5E-4
9.3E-3
6.8E-4
6.4E-3
0.02%
Organic Carbon
k(yeaO
8.8E1
1.4E2
3.9E2
1.2E2
1.4E2
2.2E1
5.2E1
2.2E1
3.9E2
-------
54 Fate Constants for Hazardous Waste Identification Rule
-------
Part I 55
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-------
56 Fate Constants for Hazardous Waste Identification Rule
13. Jeffers, P.M., L.M. Ward, LAI. Woytowitch, and NX. Wolfe. 1989. Homogeneous
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14. Leistra, M. 1970. The distribution of 1,3-Dichloropropene over the phases in soil. J.
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15. Wolfe, N.L., LA Burns, and W.C. Steen. 1980. Use of linear free energy relationships
and an evaluative model to assess the fate and transport of phthalate esters in the
aquatic environment. Chemosphere 9:393-402.
16. Sijm, D.T., H.M. Han Wever, P.J. de Vries, and A. Opperhuizen. 1989.
Octan-1-ol/water partition coefficients of polychlorinated dibenzo-p-dioxins and
dibenzofurans: Experimental values determined with a stirring method. Chemosphere
19(l-6):263-266.
17. Shiu, W.Y., W. Doucette, FARC. Gobas, A. Andren, and D. Mackay. 1988.
Physical-chemical properties of chlorinated dibenzo-p-dioxins. Environ. Sci. Technol.
22:651-658.
18. Doucette, W.J. and A.W. Andren. 1987. Correlation of octanol/water partition
coefficients and total molecular surface area for highly hydrophobic aromatic
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19. Wolfe, N.L., R.G. Zepp, P. Schlotzhauer, and M. Sink. 1982. Transformation pathways
of hexachlorocyclopentadiene in the aquatic environment. Chemosphere 11(2):91-101.
20. Callahan, M.A., M.W. Slimak, N.W. Gabel, I.P. May, C.F. Fowler, J.R. Freed, P.
Jennings, R.L. Durfee, F. C. Whitmore, B. Maestri, W.R. Mabey, B.R. Holt, and C.
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21. Faust, S.D. and H.M. Gomaa. 1972. Chemical hydrolysis of some organic phosphorus
and carbamate pesticides in aquatic environments. Environ. Lett. 3(3):171-201.
22. Hawkins, M.D. 1975. Hydrolysis of phthalic and 3,6-dimethylphthalic anhydrides. J.
Chem. Soc., Perkin Trans. 2:282-284.
23. Eadsforth, C.V. 1986. Application of reverse-phase h.p.l.c. for the determination of
partition coefficients. Pest. Sci. 17:311-325.
24. Ellington, J.J., F.E. Stancil, Jr., W.D. Payne, and C. Trusty. 1987. Measurement of
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n. Data on 54 Chemicals. U.S. Environmental Protection Agency, Athens, GA,
EPA/600/3-87/019.
25. Chapman, R.A. and C.M. Cole. 1982. Observations on the influence of water and soil
pH on the persistence of insecticides. J. Environ. Sci. Health B17(5):487-504.
26. Ellington, J.J. 1989. Hydrolysis Rate Constants for Enhancing Property-reactivity
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27. Fiskel, J., C. Cooper, A. Eschenroeder, M. Goyer, J. Perwak, K. Scow, R. Thomas, W.
Tucker, M. Wood, and A.D. Little Inc. 1981. An Exposure and Risk Assessment for
Cyanide. U.S. Environmental Protection Agency, Washington, DC, EPA-440/4-85-008.
-------
Part/ 57
28. Hamrick, K.J., H.P. Kollig, and B.A. Bartell. 1992. Computerized extrapolation of
hydrolysis rate data. J. Chem. Inf. Comput Sci. 32(5):511-514.
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30. Smith, J.H. and D.C. Bomberger. 1980. Prediction of volatilization rates of chemicals
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Afghan, B.K. and Mackay, D., Eds., Plenum Press, New York, pp. 445-451.
31. Burlinson, N.E., LA Lee, and D.H. Rosenblatt. 1982. Kinetics and products of
hydrolysis of l,2-dibromo-3-chloropropane. Environ. Sci. Technol. 16(9):627-632.
32. Grimmer, F., W. Dedek, and E. Leibnitz. 1968.1. Mitt.: Hydrolysegeschwindigkeit
und-mechanismus. Z. Naturforsch. 23(1):10-17.
33. Jungclaus, G.A. and S.Z. Cohen. 1986. Hydrolysis of Ethylene Dibromide. "Preprint
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National Meeting of the American Chemical Society, New York, NY, Paper #6.
34. Heath, D.F. and P. Casapieri. 1950. Hydrolysis of dimethylamides of phosphoric acids.
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35. Hansch, C. and A. Leo. 1979. Appendix II. Partition Coefficients. In: "Substituent
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36. Coates, H. 1949. The chemistry of phosphorus insecticides. Ann. AppL Biol.
36:156-159.
37. Banerjee, S., S.H. Yalkowsky, and S.C. Valvani. 1980. Water solubility and
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38. Karickhoff, S.W., D.S. Brown, and T.A. Scott. 1979. Sorption of hydrophobic
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40. Elliot, S., E. Lu, and F.S. Rowland. 1989. Rates and mechanisms for the hydrolysis of
carbonyl sulfide in natural waters. Environ. Sci. Technol. 23(4):458-461.
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of halogenated ethylenes. Biochem. Pharmacol. 31:1-4.
43. Hudson, R.F. 1965. Structure and Mechanism in Organophosphorus Chemistry, New
York, NY: Academic Press.
-------
58 Fata Constants for Hazardous Waste Identification Rule
44. Kirby, A.J. and S.G. Warren. 1967. The Organic Chemistry of Phosphorus, New York,
NY: Elsevier Publishing Company.
45. Ingold, C.K 1969. Structure and Mechanism in Organic Chemistry, 2nd ed., Ithaca,
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46. ScheUenberg, K., C. Leuenberger, and R.P. Schwarzenbach. 1984. Sorption of
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47. Jafvert, C.T. 1990. Sorption of organic acid compounds to sediments: Initial model
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49. Hassett, J.J., J.C. Means, W.L. Banwart, and S.G. Wood. 1980. Sorption Properties of
Sediments and Energy-related Pollutants. U.S. Environmental Protection Agency,
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50. Lyman, W.J., W.P. Reehl and D.H. Rosenblatt. 1982. Handbook of Chemical Property
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51. Wolfe N.L. and D.L. Macalady. 1992. New Perspectives in redox chemistry: Abiotic
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52. March, J. 1977. Advanced Organic Chemistry Reactions, Mechanisms and Structure.
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53. Jafvert, C.T. and N.L. Wolfe. 1987. Degradation of selected halogenated ethanes in
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54. Weber, E. J. and N.L. Wolfe. 1987. Kinetic studies of aromatic azo compounds in
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57. Wolfe, N.L., W. Peynenburg, H. d Hollander, H. Verboom, and D. v d Meent. Kinetics
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58. Wolfe, N.L., W. Peijnenburg, H. d Hollander, H. Verboom, and D. v d Meent.
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Chem. Submitted for publication, 1993.
59. Pryor, WA 1966. Free Radicals, McGraw-Hill, New York.
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Parti 59
60. Barnard, P.W.C. and R.E. Robertson. 196.1. The hydrolysis of a series of straigh-chain
alkyl methanesulphonic esters in water. Can. J. Chem. 39:881-888.
61. Elliott, 8.1990. Effect of hydrogen peroxide on the alkaline hydrolysis of carbon
disulfide. Environ. Sci. Technol. 24:264-267.
62. Ellington, J.J. and F.E. Stancil, Jr. 1988. Qctanol/water Partition Coefficients for
Evaluation of Hazardous Waste Land Disposal: Selected Chemicals. UJS.
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63. Fells, I. and E.A. Moelwyn-Hughes. 1958. The kinetics of the hydrolysis of methylene
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60 Fate Constants for Hazardous Waste Identification Rule
-------
Part II
61
1. Acenaphthene
Acenaphthene will not hydrolyze. It has no hydrolyzable functional group.
Acenaphthene
2. Acetone
Acetone will not hydrolyze; however, it may undergo other abiotic transformation processes.
H,C-C
—CH3
Acetone
-------
62
Fata Constants tor Hazardous Waste Identification Rule
3. Acetonitrile
Acetonitrile is resistant to hydrolysis. Hydroxide or hydronium is required to facilitate
hydrolysis. Hydrolysis proceeds through the intermediate amide to the final product, acetic
acid.
H3C-C-N
Acetonitrile
HO-
HgC-C-NH
Acetamide
HO'
0
HoC-C
Acetic acid
NH,
-------
Part II 63
4. Acetophenone
Acetophenone will not hydrolyze; however, it may undergo other abiotic transformation
processes.
i-CH,
Acetophenone
5. Acrolein
Acrolein undergoes a rapid addition of water across the double bond (Michael addition) to
yield 3-hydroxy-l-propanal.
H H
H2c=i-i=o
Acrolein
H2O
H H H
HO-C-C-C=O
H H
3-Hydroxy-1-propanal
-------
64 Fate Constants for Hazardous Waste Identification Rule
6. Aery lam ide
Acrylamide is an intermediate in the hydrolysis of acrylonitrile to acrylic acid. At high
concentrations of hydroxide, acrylamide polymerizes. The reported neutral hydrolysis rate
constant was determined at pH 7 by monitoring the disappearance of acrylamide from the
solution. This constant, together with the acid hydrolysis rate constant, can be used to
calculate persistence. The end product of hydrolysis is acrylic acid.
H2C=CH-C-NH2
Acrylamide
H90
B'
\
0
H2C=CH-C-OH + NH3
Acrylic acid
7. Acrylonitrile
See compounds #3 and #6. Acrylonitrile hydrolyzes to acrylic acid through the intermediate
acrylamide.
H2C-CH-C-N
Acrylonitrile
H+ HO'
JH-C-
H2C-CH-C-NH2
Acrylamide
H+ I H2O
3H-C-OH +
H2C=CH-C-OH + NH3
Acrylic acid
-------
Part II 65
8. Aldrin
The chlorinated bicyclic structure of aldrin is common to several persistent pesticides. All
aldrin chlorine atoms are either protected from nucleophilic attack (bridgehead carbon) or
are nonreactive (on the sp2 carbon). The previously reported hydrolysis rate constant for
aldrin in reference 6 was based on disappearance kinetics without confirmation of hydroly-
sis products. For this report, the hydrolysis experiments were repeated in sealed glass
ampules, and no disappearance of the aldrin was observed after 2 weeks at pH 11 and
85°C. Aldrin has been designated the assignment of NLFG.
9. Aniline
Aniline will not hydrolyze; however, it may undergo other abiotic transformation processes.
Aniline
-------
66
Fate Constants for Hazardous Waste Identification Rule
11. Aramite
The sulfite bond in Aramite is very susceptible to hydrolysis (see endosulfan, #97). Initial
hydrolysis of Aramite proceeds with cleavage of either of two sulfoxide bonds. This initial
hydrolysis yields four products, two alcohols and two hydrogen sulfites. Hydrolysis of the
hydrogen sulfites continues at a rate comparable to that of Aramite. Hydrolysis of 2-
chloroethanol is discussed with 1,2-dichloroethane, #65.
H3C-C—^V-O-CH2CH-O-S-O-CH.
,CH2CI
Aramite
H,0
HO-
H,C
IH2CH-O-S—OH + H3C
CH,
o
3H2CH-OH + HO—S-O-CH2CH2CI+CI—CHj-CHj-OH
CH3 2-Chloroethanol
2-Chloroettiythydrogensulflte
1-Methyl-2-[p-(1,1-dlmettiylethyl)phenoxy)Bthanol
1-Methy1-2-[p-(1,1-dlmethy«ethv1)phenox^e1hy(hydrogen8uime
CH
H3C-A^^V-0-CH.
CH3 ^— ' CH3
CH-OH
H2S04
Cl—CHj-CHg-OH + H2SO4
2-Chloroettianol
1 -Methy(-2-|p-(1 ,1 -dlmethylethytjphenox^ettianol
HCI
Eth^ene o>dde
HO-CHj-CHj-OH
Ettiytene glycol
-------
Part 11 67
14. Benz[a]anthracene
Benz[a]anthracene will not hydrolyze. It has no hydrolyzable functional group.
Benz[a]anthracene
15. Benzene
Benzene will not hydrolyze. It has no hydrolyzable functional group.
Benzene
-------
68 Fate Constants tor Hazardous Waste Identification Rule
16. Benzidine
Benzidine will not hydrolyze; however, it may undergo other abiotic transformation pro-
cesses.
17. Benzo[fr]fluoranthene
Benzo[6]fluoranthene will not hydrolyze. It has no hydrolyzable functional group.
Benzo[b]fluoranthene
-------
Part II 69
18. Benzo[a]pyrene
Benzo[a]pyrene will not hydrolyze. It has no hydrolyzable functional group.
Benzo[a]pyrene
19. Benzotrichloride
Hydrolysis of benzotrichloride proceeds through nucleophilic substitution of chlorine by
HjO. The halohydrin formed by this displacement is unstable and reacts further to yield
benzoic acid.
CU
Benzotrichloride
HoO
-OH
HCI
Benzoic acid
-------
70 Fate Constants for Hazardous Waste Identification Rule
20. Benzyl alcohol
Benzyl alcohol will not hydrolyze. It has no hydrolyzable functional group.
HoOH
Benzyl alcohol
21. Benzyl chloride
Hydrolysis of benzyl chloride occurs through nucleophilic displacement of chlorine by HjO.
Hydrolysis is not mediated by hydroxide.
HoCI
Benzyl chloride
H2O
H2-OH
Benzyl alcohol
HCI
-------
Part//
71
23. g/s(2-chloroethyl)ether
Hydrolysis of 6is(2-chloroethyl)ether occurs through nucleophilic displacement of chlorine
with HgO. The monochloroether formed by this reaction will undergo a second substitution
by HjO to yield 6is(2-hydroxyethyl)ether and intramolecular displacement of chlorine to
yield dioxane.
C 1C r^C ri2"~O~~C r^C r^C I
Bis(2-ch!oroethyl)ether
H90
HO-CH2CH2—O-CH2CH2CI + HCI
2 - (2-Chtoroethoxy)ethanol
HO-CH2CH2—O-CH2CH2-OH + HCI
Bis(2-hydroxyethyOether
p-Dioxane
-------
72
Fate Constants for Hazardous Waste Identification Rule
24. g/s(2-chloroisopropyl)ether
The literature hydrolysis rate constant for 6is(2-chloroisopropyl)ether seems to be question-
able. This value was estimated by analogy to 6is(2-chloroethyl)ether by Mabey et al.8 The
value for 6is(2-chloroethyl) ether was determined in aqueous dioxane at 100°C and
extrapolated to 20°C by Mabey et al.8 However, Mabey et al.8 named the compound bis(2-
chloroisopropyDether but give the Chemical Abstract Service number and structure for
&is(l-chloroisopropyl)ether. Moreover, it is questionable whether 6is(2-chloroisopropyl)ether
should be the compound on the HWIR list or whether it should be 6is(l-chloroisopropyl)-
ether. Our Pathway Analysis Team deliberated and concluded that 6is(2-chloroisopropyl)-
ether is a halohydrin and is, thus, unstable. If the intended compound on the HWIR list is
6is(l-chloroisopropyl)ether, the hydrolysis rate should be the one given by Mabey et al.8 (kn
= 3.5E-2 Y'1). However, if the intended compound is 6is(2-chloroisopropyl)ether, its half-life
is on the order of minutes because of its instability.
CH3 CH3
;i—c-o-c-<
13
Cl—C-O-C-CI
CH, CH,
Bis(2-chk>roisopropyl)ether
H9O
CHq CHq
, 3 - 3
HC—C-O-C-CI + HCI
Au nu
L/ri3 1-^3
(2-Hydroxyisopropyi-2-chloroisopropyl)ether
HO-C-O-C-
CHo CH
'3 V^3
-OH + HCI
Bis(2-hydroxyisopropyl)ether
-------
Part 11
73
25. g/s(2-ethylhexyl)phthalate
Bis(2-ethylhexyl)phthalate will hydrolyze by nucleophilic attack of HO at the ester car-
bonyl group to give 2-ethylhexyl hydrogen phthalate and 2-ethylhexanol. The monoester
will undergo further base-mediated hydrolysis to o-phthalic acid and 2-ethylhexanol.
CH2CH3
-O-CH2-CH— (CH2)3CH3
-O-CH2-CH— (CH2)3CH3
U
Bis(2-ettiylhexyl)phthalate
HO
-OH
-O-CH2-CH— (CHj>)3CH3
CH2CH3
2-Ethylhexyl hydrogen phthalate
(j)H2CH3
HO-CH2-CH—(CH2)3CH3
2-Ethylhexanol
HO
CH2CH3
HO-CH2-CH— (CH2)3CH3
2-Ethylhexanol
o-Phthalic acid
-------
74
Fate Constants for Hazardous Waste Identification Rule
26. Bromodichloromethane
Hydrolysis of bromodichloromethane occurs initially by proton abstraction followed by
formation of the carbene, which reacts with HO' to form carbon monoxide and the mineral
acids.
CHBrClj,
Bromodichloromethane
HO
CO + HCI + HBr
Carbon monoxide
27. Bromomethane
Hydrolysis of bromomethane proceeds through nucleophilic substitution of bromine
to yield methanol and hydrobromic acid.
CH3Br
Bromomethane
H2O
CH3OH
Methanol
HBr
-------
Part II
75
28. Butanol
Butanol will not hydrolyze. It has no hydrolyzable functional group.
CH3CH2CH2CH2OH
Butanol
29. Butyl benzyl phthalate
Butyl benzyl phthalate is a mixed ester formed by condensation of phthalic acid with two
different alcohols. The hydrolysis mechanism is the same as described for 6is(2-ethyl-
hexyDphthalate (#25) with the two resulting monoesters undergoing further hydrolysis to o-
phthalic acid and the corresponding alcohols.
Butyl benzyl phtnalate
—OH
-(CH2)3CH3
Butyl hydrogen phthalate
Benzyl hydrogen phthalate
HCT
-CH2-OH
Benzyl alcohol
HO'
HO—CH2CH2CH2CH3
n-Butanol
+ HO—CH2CH2CH2CH3
n-Butanol
-CH2-OH
Benzyl alcohol
-------
76 Fate Constants tor Hazardous Waste Identification Rule
30. 2-seoButyl-4,6-dinitrophenol
2-sec-Butyl-4,6-dinitrophenol will not hydrolyze; however, it may undergo other abiotic
transformation processes.
N02
2-sec-Butyl-4,6-dinitrophenol
32. Carbon disulfide
Hydrolysis of carbon disulfide occurs by nucleophilic attack of HO. The initial hydrolysis
product is carbonyl sulfide, which reacts further with HjO or HO to give carbon dioxide and
hydrogen sulfide.
Carbon disulfide
HO'
0=C=S
Carbonyl sulfide
O=C=O + H2S
Carbon dioxide
-------
Part II
77
33. Carbon tetrachloride
Hydrolysis of carbon tetrachloride occurs by reaction with HjO to yield carbon dioxide and
the mineral acid.
CCI4
Carbon tetrachloride
HoO
O=€=O
Carbon dioxide
HCI
34. Chlordane
Hydrolysis of chlordane proceeds by nucleophilic substitution of chlorine by HO' to give
2,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano-lH-indene, which will not be
susceptible to further hydrolysis.
Chlordane
H-,0
.Cl
H
2,4,5,6,7,8,8-Hep1achtoro-3a,4,7,7a-te1rahydro-4,7-methano-1H-indene
-------
78 Fate Constants for Hazardous Waste Identification Rule
35. p-Chloroaniline
p-Chloroaniline will not hydrolyze to any reasonable extent; however, it may undergo other
abiotic transformation processes.
p-Chloroaniline
36. Chlorobenzene
Chlorobenzene will not hydrolyze to any reasonable extent; however, it may undergo other
abiotic transformation processes.
Chlorobenzene
-------
Part 11
79
37. Chlorobenzilate
Hydrolysis of chlorobenzilate is analogous to the phthalate esters and proceeds through
nucleophilic attack of HO at the ester carbonyl. The resulting acid is stable in the ionic
form, but the protonated form that would exist at acidic pH values will decarboxylate with
concurrent oxidation to yield carbon dioxide andpjj'-dichlorobenzophenone. The conversion
of &is(p-chlorophenyl)hydroxyacetic acid top«p'-dichlorobenzophenone was estimated to
proceed at 10% of the hydrolysis rate of the parent.
CH
CH3
Chlorobenzilate
HO'
CH3CH2-OH
Ethanol
Bis(p-chlorophenyl)hydroxyacetic acid
p,p'-Dichlorobenzophenone
-------
80 Fate Constants for Hazardous Waste Identification Rule
38. 2-Chloro-1,3-butadiene
2-Chloro-l,3-butadiene will not hydrolyze to any reasonable extent; however, it may un-
dergo other abiotic transformation processes.
2-Chloro-1 ,3-butadiene
39. Chlorodibromomethane
Hydrolysis of Chlorodibromomethane occurs initially by proton abstraction followed by
formation of the carbene, which reacts with HO* to form carbon monoxide and the mineral
acids.
CHBr2CI
Chlorodibromomethane
H2O, HO
CO + HBr + HCI
Carbon monoxide
-------
Part II 81
40. Chloroform
Hydrolysis of chloroform occurs initially by proton abstraction followed by formation of the
carbene, which reacts with HO to form carbon monoxide and the mineral acid.
CHCIg
Chloroform
H20,HO
CO + HCI
Carbon monoxide
41. Chloromethane
Chloromethane has a negative boiling point and exists in a gaseous state at room tempera-
ture. Its hydrolysis pathway has not been addressed.
CH3CI
Chloromethane
-------
82
Fate Constants for Hazardous Waste Identification Rule
42. 2-Chlorophenol
2-Chlorophenol will not hydrolyze to any reasonable extent; however, it may undergo other
abiotic transformation processes.
2-Chlorophenol
43. 3-Chloropropene
Neutral hydrolysis of 3-chloropropene occurs through the formation of the allylic carbonium
ion, which reacts with HjO to give 3-hydroxypropene and the mineral acid.
3-Chloropropene
HO
HC=CH-CH-OH + HCI
3-Hydroxypropene
-------
Part 11 83
45. Chrysene
Chrysene will not hydrolyze. It has no hydrolyzable functional group.
Chrysene
47. o-Cresol
o-Cresol will not hydrolyze. It has no hydrolyzable functional group.
)H
H3
o-Cresol
-------
84 Fate Constants for Hazardous Waste Identification Rule
48. m-Cresol
m-Cresol will not hydrolyze. It has no hydrolyzable functional group.
m-Cresol
49. p-Cresol
p-Cresol will not hydrolyze. It has no hydrolyzable functional group.
H
-------
Part 11 85
50. Cumene
Cuinene will not hydrolyze. It has no hydrolyzable functional group.
51. Cyanide
,CH(CH3)2
Cumene
Cyanide will hydrolyze by nucleophilic attack of HgO resulting in carbon dioxide and ammo-
nia.
'CN
H20
O=C=O
Carbon dioxide
NH
-------
86 Fate Constants for Hazardous Waste Identification Rule
52. 2,4-Dichlorophenoxyacetic acid
2,4-Dichlorophenoxyacetic acid will not hydrolyze to any reasonable extent.
-OH
2,4-DicNorophenoxyacetic acid
53. ODD
The reaction of DDD occurs by the elimination of chlorine (dehydrochlorination) to give 2,2-
&is(4-chlorophenyl)-l-chloroethene (DDMU). This process will occur by reaction with either
or HO.
CHCI2
DDD
H,0
HO"
H
-CL
I + HCI
2,2-Bis(4-chlorophenyl)-1 -chloroethene
-------
Part 11
87
54. DDE
DDE will not hydrolyze to any reasonable extent; however, it may undergo other abiotic
transformation processes.
DDE
55. flp'-DDT
The reaction ofpjo'-DDT occurs in a manner analogous to that previously described for
DDD. The reaction products resulting from dehydrochlorination are DDE and the mineral
acid.
DDT
hUO
HO
I + HCI
DDE
-------
88 Fate Constants tor Hazardous Waste Identification Rule
56. Diallate
Diallate will hydrolyze by nucleophilic attack of HgO and HO at the carbonyl group result-
ing in the formation of diisopropylamine and cis- and £ra7is-2,3-dichloro-2-propene-l-thiol.
(CH3)2CHs O
^|-C-S-CH2-C=CH
(CH3)2CHX 6 Cl
Diallate
(CH3)2CHx
/N-H
(CH3)2CH
Diisopropylamine
H90
HO
+ HS-CH2-C=C-H +
Cl Cl
cis- & trans -2,3-Dichloro-2-propene-1-thiol
0=C=O
Carbon dioxide
57. Dibenz[a,/7]anthracene
Dibenz[a,/i]anthracene will not hydrolyze. It has no hydrolyzable functional group.
Dibenz[a,h]anthracene
-------
Part 11
89
58. 1,2-Dibromo-3-chloropropane
l,2-Dibromo-3-chloropropane is subject to both neutral and base-mediated hydrolysis.
Neutral hydrolysis occurs initially by nucleophilic displacement of either chlorine or bro-
mine. Nucleophilic attack at the carbon bearing the chlorine results in the formation of 2,3-
dibromopropanol, which will react further to give 2,3-dihydroxybromopropane through the
intermediate epoxide, epibromohydrin. 2,3-Dihydroxybromopropane will undergo further
hydrolysis through the intermediate epoxide, l-hydroxy-2,3-propylene oxide, which reacts
with Hp to give glycerol. Nucleophilic displacement of bromine from l,2-dibromo-3-
chloropropane gives 2-bromo-3-chloropropanol, which will react further through epoxide
intermediates eventually to give glycerol, as described previously for the hydrolysis of 2,3-
dibromopropanol.
The base-mediated hydrolysis of l,2-dibromo-3-chloropropane will occur by dehydrohalo-
genation to give two initial products, 2-bromo-3-chloropropene and 2,3-dibromo-l-propene.
2-Bromo-3-chloropropene is expected to be the major reaction product because bromine is a
better leaving group than chlorine. Both products, however, will undergo facile hydrolysis
through formation of an allylic carbonium ion, which will react with H^O to give 2-bromo-3-
hydroxypropene. This product will be stable to further hydrolysis.
FUT
12-Dibrorno-3-ctioropropane
CHz-CH-CHz + HCI
Br Br OH "" Br ul 8' Br Br
2,3-Dibromo-1-propanol 2-Bromo-3-c«oropropanol 2,3-Dibromopropene
2-Bromo-3-crtoropropene
HCI / + HBr
CH2-CH-CH2 + HBr
Br 0
Epibromohydrin
H-CH2 + HBr
Eplchtorohydrin
CHz-CH-C^
Br OH OH
1-Bromo-2,3-dihydroxypropane
HBr
1 -Hydroxy-2,3-propytene oxide
mHz *-
H
Glycerol
mHz
I
1 -CNoro-2,3-dihydroxypropane
2-Bromo-3-hydroxypropene
+ HCI + HBr
OH
1 -Hydroxy-2,3-propytene oxide
CHj-CH—CH2
OH OH OH
Glycerol
-------
90 Fate Constants for Hazardous Waste Identification Rule
59. Dibromomethane
Dibromomethane should not hydrolyze to any reasonable extent. QSAR model computa-
tions have indicated that the half-life of this halogenated methane is several thousand
years.
CH2Br2
Dibromomethane
60. 1,2-Dichlorobenzene
1,2-Dichlorobenzene will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
1,2-Dichlorobenzene
-------
Part 11
91
61. 1,4-Dichlorobenzene
1,4-Dichlorobenzene will not hydrolyze to any reasonable extent, however, it may undergo
other abiotic transformation processes.
1,4-Dichlorobenzene
62. 3,3'-Dichlorobenzidine
3,3'-Dichlorobenzidine will not hydrolyze to any reasonable extent; however, it may un-
dergo other abiotic transformation processes.
H9N
3,3'-Dich!orobenzidine
-------
92 Fate Constants for Hazardous Waste Identification Rule
63. Dichlorodifluoromethane
Dichlorodifluoromethane has a negative boiling point and exists in a gaseous state at room
temperature. Its hydrolysis pathway has not been addressed.
CCI2F2
Dichlorodifluoromethane
64. 1,1-Dichloroethane
The reaction of 1,1-dichloroethane occurs by both nucleophilic substitution and dehydro-
chlorination. The reaction products resulting from nucleophilic substitution by HjO and
HO- are acetaldehyde and HC1, whereas dehydrochlorination gives vinyl chloride and the
mineral acid.
CHgCHCIj,
1,1-Dichloroethane
H2O
HO
H-i=C-H + HgC-C-H + HCI
Vinyl chloride Acetaldehyde
-------
Part 11
93
65. 1,2-Dichloroethane
The reaction of 1,2-dichloroethane by I^O and HO" occurs by both nucleophilic substitution
and dehydrochlorination. Hydrolysis by nucleophilic substitution will lead to the formation
of 2-chloroethanol and HC1, whereas dehydrochlorination results in vinyl chloride and the
mineral acid. 2-Chloroethanol will react further producing ethylene oxide, which will hydro-
lyze by reaction with HjO to yield ethylene glycol.
CICH2CH2CI
1,2-Dichloroethane
H20,HO/ \H20,HO
Cl H
H-C=C-
J-H + HCI
Vinyl chloride
Ch-CH2-CH2-OH + HCI
2-Chloroethanol
HCI
H2C C H2
Ethylene oxide
HO-CH2-CH2-OH
Ethylene glycol
-------
94 Fate Constants tor Hazardous Waste Identification Rule
66. 1,1-Dichloroethylene
1,1-Dichloroethylene will not hydrolyze to any reasonable extent.
?'V
Cl—C=C-H
1,1-Dichloroethylene
67. c/'s-1,2-Dichloroethyiene
cis-l,2-Dichloroethylene will not hydrolyze to any reasonable extent; however, it may
undergo other abiotic transformation processes.
H-C=C-H
cis-1,2-Dichloroethylene
-------
Part II 95
68. fra/?s-1,2-Dichloroethylene
£rans-l,2-Dichloroethylene will not hydrolyze to any reasonable extent; however, it may
undergo other abiotic transformation processes.
J'
H-C=C-H
Cl
trans-1,2-Dichloroethylene
69. Dichloromethane
Hydrolysis of dichloromethane occurs by nucleophilic substitution with 1^0 (neutral hy-
drolysis) resulting in the displacement of chlorine with H0\ The resulting chlorohydrin is a
transient intermediate that immediately loses chlorine to yield formaldehyde, the final
hydrolysis product.
Dichloromethane
H20
I + HCI
H-C—H
Formaldehyde
70. 2,4-Dichlorophenol
2,4-Dichlorophenol will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
)H
2,4-Dichlorophenol
-------
96
Fate Constants for Hazardous Waste Identification Rule
71. 1,2-Dichloropropane
The reaction of 1,2-dichloropropane with 1^0 or HO will proceed through competing reac-
tion pathways (nucleophilic substitution and dehydrohalogenation). Nucleophilic substitu-
tion will occur at the primary carbon resulting in the formation of 2-chloropropanol. This
intermediate will degrade by intramolecular nucleophilic displacement of the chlorine atom
by the adjacent hydroxyl group resulting in the formation of propylene oxide. Propylene
oxide will undergo predominantly neutral hydrolysis to give 1,2-dihydroxypropane. Base-
mediated elimination of chlorine will result in the formation of 1-chloro-l-propene, which
will be stable to further hydrolysis.
1,2-Dichloropropane
H20, HO"
H2O, HO"
Cl H
T
+ HCI
1-Chloro-1-propene
OHCI
H2C C H~~C r\Q
2-Chloropropanol
HCI
O
H2C—C H—C Hg
Propylene oxide
HCI
?HOH
^~C
1 ,2-Dihydroxypropane
-------
Part 11
97
72. 1,3-Dichloropropene
Hydrolysis of 1,3-dichloropropene will occur by reaction with HjO through nucleophilic
substitution resulting in the formation of 3-chloro-2-propene-l-ol. Because the
stereochemistry about the carbon-carbon double bond is not affected in this hydrolysis
reaction, the trans isomer of 1,3-dichloropropene will give the trans isomer of the allylic
alcohol and the cis isomer of 1,3-dichloropropene will lead to the formation of the cis isomer
of the allylic alcohol.
HCCI=CH—CH2CI
1,3-Dichloropropene
Cl H Cl
H—C=C~C—H
H
cis-1,3-Dichloropropene
OHH Cl
H-C-C=C-H
H
cis-3-CWoro-2-propen-1 -ol
H-C=C-C—H
Cl
trans-1,3-Dichloropropene
OHH
H-C-i=C-H
H Cl
trans-3-Chloro-2-propen-1 -ol
-------
Fate Constants tor Hazardous Waste Identification Rule
73. Dieldrin
Hydrolysis of dieldrin will occur through nucleophilic substitution with HgO at the epoxide
moiety resulting in the formation of the diol. The diol will be stable to further hydrolysis.
H
Dieldrin diol
-------
Part 11 99
74. Diethyl phthalate
The base-mediated hydrolysis of diethyl phthalate will initially result in formation of the
monoester, which will undergo further hydrolysis to o-phthalic acid. The hydrolysis of the
monoester will occur at a rate approximately half that of the parent compound.
Diethyl phthalate
HO
J-OH
CH3CH2-OH
Ethyl hydrogen phthalate
Ethanol
-OH
-OH
+ CH3CH2-OH
o-Phthalic acid
Ethanol
-------
100 Fate Constants for Hazardous Waste Identification Rule
75. Diethylstilbestrol
Diethylstilbestrol will not hydrolyze. It has no hydrolyzable functional group.
Diethylstilbestrol
76. Dimethoate (opposite page)
Hydrolysis of dimethoate may occur through either reaction with HjO (neutral hydrolysis)
or reaction with HO' (base-mediated hydrolysis). Nucleophilic substitution by water can
occur at either the methylene carbon of the thio substituent, which gives 0,0-dimethyl-
phosphorodithioic acid and JV-methyl-2-hydroxyacetamide, or the carbon of the methoxy
substituent to give 0-methyl-S-[2-(AT-methylacetamide)]phosphorodithioic acid and metha-
nol. In either case, the diester that is formed will be much more persistent than the parent
compound. Because the diesters are ionized at pH 7, they are approximately a factor of 10
less reactive towards hydrolysis than the triesters. Hydrolysis of O,O-dimethylphosphoro-
dithioic acid will occur through formation of the monoester, 0-methylphosphorodithioic
acid, which hydrolyzes further to eventually give phosphoric acid and hydrogen sulfide.
Likewise, hydrolysis of 0-methyl-S-[2-(JV-methylacetamide)]phosphorodithioic acid will
result in the formation of the monoester, 0-methylphosphorodithioic acid, in addition to N-
methyl-2-hydroxyacetamide. Hydrolysis of the monoester, which occurs by nucleophilic
attack at the phosphorus atom, will proceed at a rate of approximately one half that of the
parent triester.
Base-mediated hydrolysis of dimethoate will occur by nucleophilic attack of HO at the
central phosphorus atom to give O,O-dimethylphosphorothioic acid and W-methyl-2-
mercaptoacetamide. Further hydrolysis of 0,0-dimethylphosphorothioic acid may occur as
previously described.
-------
Part II
101
-L
CH30-P-SH
A ACH, I
CH30_!LSH
C AH
U"
f 9
CH30-P—S-CH2-C-NH-CH3
OCHo Dimetnoate
H20
HO-CH2CNHCH3
B
I !
CH3OH CH3O-P—S-CH,CI
D H OH
H20
.HO
CH30-P-OH
HSCH2CNHCH3
IjjCNHCHg + CH3OH
D
CHgO-P-OH
K AH
CH3OH
D
HO-P-SH + CH3OH CH3O-P-SH + HO-CH2CNHCH3 HO-P-OH + CH3OH
E OH D C OH B L OH D
HO-P-OH
F AH
HO-P-SH + CHgOH
E OH D
HO-P-OH + H2S I
F OH G I
A 0,O-Dimethyiphosphorodithioicacid
B N-Methyl-2-hydroxyacetamide
C O-Methylphosphorodithioic acid
D Methanol
E Phosphorpdithioic acid
F Phosphoric acid
G Hydrogen sutfide
H O-Methyf-S-(2-(N-methylacetamide))pnosphorodithioic acid
I 0,O-Dimethylpnospnorothioic acid
J N-Methyt-2-mercaptoacetamide
K O-Metnytphosphorothioic acid
L Phospnorothioic acid
\s
HO-P-OH + H2S
F AH G
-------
102 Fate Constants tor Hazardous Waste Identification Rule
77. 3,3'-Dimethoxybenzidine
3,3'-Dimethoxybenzidine will not hydrolyze; however, it may undergo other abiotic transfor-
mation processes.
HgCO
3,3'-Dimethoxybenzidine
78. 7,12-Dimethylbenz[a]anthracene
7,12-Dimethylbenz[a]anthracene will not hydrolyze. It has no hydrolyzable functional
group.
7,12-DimethyJbenz(a]anthracene
-------
Part II 103
79. 3,3'-Dimethylbenzidine
3,3'-Dimethylbenzidine will not hydrolyze; however, it may undergo other abiotic
transformation processes.
H3C
3,3'-Dimethylbenzidine
80. 2,4-Dimethylphenol
2,4-Dimethylphenol will not hydrolyze. It has no hydrolyzable functional group.
2,4-Dimethylphenol
-------
104 Fate Constants for Hazardous Waste Identification Rule
81. Dimethyl phthalate
Dimethyl phthalate will hydrolyze by nucleophilic attack of HO' at the ester carbonyl group
resulting in methyl hydrogen phthalate and methanol, which can undergo further base-
mediated hydrolysis to o-phthalic acid.
/— O— CH
Dimethyl phthalate
HO-
i-OH
C-0-CH3
0
Methyl hydrogen phthalate
-OH
o-Phthalic acid
CH3OH
Methanol
CH3OH
Methanol
-------
Part II 105
82. 1,3-Dinitrobenzene
1,3-Dinitrobenzene will not hydrolyze; however, it may undergo other abiotic transforma-
tion processes.
N02
1,3-Dinitrobenzene
83. 2,4-Dinitrophenol
2,4-Dinitrophenol will not hydrolyze; however, it may undergo other abiotic transformation
processes.
H
N02
NO2
2,4-Dinitrophenol
-------
106 Fate Constants for Hazardous Waste Identification Rule
84. 2,4-Dinitrotoluene
2,4-Dinitrotoluene will not hydrolyze; however, it may undergo other abiotic transformation
processes.
N02
2,4-Dinitrotoluene
85. 2,6-Dinitrotoluene
2,6-Dinitrotoluene will not hydrolyze; however, it may undergo other abiotic transformation
processes.
H
2,6-Dinitrotoluene
-------
Part II 107
86. Di-n-butyl phthalate
The reaction pathway for the hydrolysis of di-n-butyl phthalate is identical to that de-
scribed previously for dimethyl phthalate (#81).
)-(CH2)3CH3
)-(CH2)3CH3
Di-n-butyl phthalate
HO"
J-OH
)-0-(CH2)3CH3
n-Butyl hydrogen phthalate
+ CH3(CH2)3-OH
rvButanol
-OH
CH3(CH2)3-OH
o-Phthalic acid
n-Butanol
-------
108 Fate Constants for Hazardous Waste Identification Rule
87. Di-ff-octyl phthalate
The reaction pathway for the hydrolysis of di-n-octyl phthalate is identical to that described
previously for dimethyl phthalate
)-0-CH2(CH2)6CH3
Di-n-octyl phthalate
HO'
i
0
C-OH
n-Octyi hydrogen phthalate
HO'
+ HO(CH2)7CH3
n-Octanol
5-OH
HO(CH2)7CH3
n-Octanol
o-Phthalic acid
-------
Part 11
109
88. 1,4-Dioxane
1,4-Dioxane will not hydrolyze. It has no hydrolyzable functional group.
1,4-Dioxane
89. 2,3,7,8-TCDDioxin
2,3,7,8-TCDDioxin will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
2,3,7,8-TCDDioxin
-------
110
Fate Constants for Hazardous Waste Identification Rule
90. 2,3,7,8-PeCDDioxins
2,3,7,8-PeCDDioxins will not hydrolyze to any reasonable extent; however, they may
undergo other abiotic transformation processes.
91. 2,3,7,8-HxCDDioxins
2,3,7,8-PeCDD
Cl
2,3,7,8-HxCDDioxins will not hydrolyze to any reasonable extent; however, they may
undergo other abiotic transformation processes.
Cr ^^ o ^^ Cl
2,3,7,8-HxCDD
92. 2,3,7,8-HpCDDioxins
2,3,7,8-HpCDDioxins will not hydrolyze to any reasonable extent; however, they may
undergo other abiotic transformation processes.
Cl
Cl
2,3,7,8-HpCDD
-------
Part II 111
93. OCDD
OCDD will not hydrolyze to any reasonable extent; however, it may undergo other abiotic
transformation processes.
94. Diphenylamine
Diphenylamine will not hydrolyze; however, it may undergo other abiotic transformation
processes.
Diphenylamine
95. 1,2-Diphenylhydrazine
1,2-Diphenylhydrazine will not hydrolyze; however, it may undergo other abiotic
transformation processes.
H
N-f
1,2-Diphenylhydrazine
-------
112
Fata Constants tor Hazardous Waste Identification Rule
96. Disulfoton
The reaction pathways for the hydrolysis of disulfoton are quite similar to those already
discussed for the hydrolysis of dimethoate (#76). Neutral hydrolysis can occur at two sites
resulting in the formation of phosphorus diesters, which will hydrolyze through the phos-
phate monoester to eventually give phosphoric acid and hydrogen sulfide. As with di-
methoate, base-mediated hydrolysis will occur by nucleophilic attack of HO at the central
phosphorus atom resulting in 2-thioethylethylthioether and 0,0-diethylphosphorothioic
acid, which will hydrolyze further to phosphoric acid and hydrogen sulfide.
-O-P-
AcH2CH3
Disulfoton
CH3CH2-0-P-SH +
A OCH2CH3
S
CH3CH2^^~P^SH "*"
c AH
B
-P-SH +
CH3CH2
-O-P-OH
H20
CHgCHaO-P-OH + CH3CH2OH
K. AH D
I H
HO-P-SH + CH3CH2OH
E AH . D
. I2O-P-SH +
c I AH
I
HO-P-SH +
HO-P-OH
L AH
B
HO-P-OH + H2S
F OH G
A 0,O-Diethylphosphorodithioic acid
B 2-Hydroxyetnytetnylthioether
C O-Ethylphosphorodithioicacid
D Ethanol
E Phosphorodithioicacid HO-.
F Phosphoric acid p AH
G Hydrogen sulfide
H O-Ethy1-S-{(2-(ethylthio)ethyl)]phosphorodithioicacid
I O,O-Dietnylphosphorothioic acid
J 2-Thioethytethytthioether
K 0-Ettylphosphorothioic acid
L Phosphorothloic acid
HO-P-OH + H2S
G
-
Ah
+ H2S
G
-------
Part II
113
97. Endosulfan
Endosulfan, which is a mixture of the alpha (Endosulfan I) and beta (Endosulfan II) iso-
mers, will hydrolyze by nucleophilic attack of I^O or HO" at the sulfur atom resulting in the
alpha and beta isomers of endosulfan diol. The ratio of the alpha to the beta isomers of
endosulfan diol will reflect the ratio of Endosulfan I to Endosulfan II in the parent com-
pound.
alpha-Endosutfan
H20\HCT
beta-Endosulfan
H2q/HCr
H2S04
Endosulfan diol
-------
114
Fate Constants for Hazardous Waste Identification Rule
98. Endrin
Hydrolysis of endrin will proceed by nucleophilic attack of HgO at the epoxide moiety result-
ing in the formation of endrin diol, which will be stable to further hydrolysis.
CL Cl
Endrin
H9O
CL Cl
Endrin diol
-------
Part II
115
99. Epichlorohydrin
Hydrolysis of epichlorohydrin will occur initially by attack of HgO at the epoxide moiety
resulting in the formation of l-chloro-2,3-dihydroxypropane. Subsequently, loss of chlorine
will occur through the intramolecular attack of HO" on the adjacent carbon to give 1-hy-
droxy-2,3-propylene oxide, which will undergo further hydrolysis by attack of HjO at the
epoxide moiety to give glycerol.
0
H2CH:HCH2CI
Epichlorohydrin
H20, H+
OH OH
HoC-CH
C I
1 -Chloro-2>3-dihydroxypropane
T
,c-c
H2C-CH—CH2
1 -Hydroxy-2,3-propylene oxide
HCI
OH OH OH
H^% Ai i Aij
ow^^/i i orio •*•
Glycerol
-------
116 Fate Constants for Hazardous Waste Identification Rule
100. 2-Ethoxyethanol
2-Ethoxyethanol will not hydrolyze. It has no hydrolyzable functional group.
C1130 n
2-Ethoxyethanol
101. Ethyl acetate
Hydrolysis of ethyl acetate will occur by acyl-oxygen bond cleavage by HgO and acid cataly-
sis and base mediation resulting in the formation of acetic acid and ethanol.
CH3-C-O-CH2CH3
Ethyl acetate
H*,H20,HO
CH3-C-OH + HOCH2CH3
Acetic acid Ethanol
-------
Part// 117
102. Ethyl benzene
Ethylbenzene will not hydrolyze. It has no hydrolyzable functional group.
Ethylbenzene
103. Ethyl ether
Ethyl ether will not hydrolyze. It has no hydrolyzable functional group.
2C Hg
Ethyl ether
-------
118 Fate Constants for Hazardous Waste Identification Rule
104. Ethyl methacrylate
Hydrolysis of ethyl methacrylate will occur by the base-mediated cleavage of the acyl-
oxygen bond resulting in methacrylic acid and etnanol.
H2C=C-C-O-CH2CH3
f^ ^J
on3
Ethyl methacrylate
HO
H2C=C-C-OH + HCX5H2CH3
CH3
Methacrylic acid Ethanol
-------
Part II 119
105. Ethyl methanesulfonate
Hydrolysis of ethyl methanesulfonate will occur in a manner analogous to the hydrolysis of
carboxylic acid esters. Nucleophilic attack of HgO at the carbon results in the formation of
methylsulfonic acid and ethanol.
O Pi
Ethyl methanesutfonate
H2O
CH3-§-OH + HOCH2CH3
Ethanol
Methylsulfonic acid
-------
120
Fate Constants for Hazardous Waste Identification Rule
106. Ethylene dibromide
The reaction of ethylene dibromide proceeds by either nucleophilic substitution or
dehydrohalogenation. Nucleophilic displacement of bromine by ftp results in 2-bromo-
ethanol, which will react further through the epoxide intermediate to yield ethylene glycol.
Dehydrohalogenation results in the formation of vinyl bromide, which will be stable to
further hydrolysis.
H70
Br Br
H2C^~Cri2
Ethylene dibromide
H20
?HBr
mt^^f^ LJ
•^\yrl
HBr
2-Bromoethanol
Br
H2C=CH +
Vinyl bromide
HBr
0
ri2C C112
Ethylene oxide
OH OH
n2C~~CH2
Ethylene glycol
HBr
-------
Part // 121
107. Famphur
The reaction pathways for the hydrolysis offamphur are similar to the organophosphorus
esters previously discussed. Both base and neutral hydrolysis can occur by nucleophilic
attack at the phosphorus atom resulting in the formation of phosphorous diesters, which
will hydrolyze through the phosphate monoester eventually to result in phosphoric acid and
hydrogen sulfide, andp-(AT^dimethylsulfamoyl)phenol.
MettBno,
O-MBlhy(-O-p-(N,N-DimethybJfanoyOpheny^hasphorothioic acid O.O-Dimettiyfchosphorolhioic acid pKN.N-DimethyteulfamoyOphBnol
O-p-(N,N-Dimefriytsu)famoyOpheny1phosphoiDtHoic add
CHsOH u
'CH, Metanol TO Melhanol
OMet^phosphoiDlhlalc acid
Phosphorothioic add p-
-------
122 Fate Constants tor Hazardous Waste Identification Rule
108. Fluoranthene
Fluoranthene will not hydrolyze. It has no hydrolyzable functional group.
Fluoranthene
109. Fluorene
Fluorene will not hydrolyze. It has no hydrolyzable functional group.
Fluorene
-------
Part II 123
110. Formic acid
Formic acid will not hydrolyze. It has no hydrolyzable functional group.
H-C-OH
Formic acid
111. Furan
Furan will not hydrolyze. It has no hydrolyzable functional group.
Furan
-------
124
Fate Constants for Hazardous Waste Identification Rule
112. 2,3,7,8-TCDFuran
2,3,7,8-TCDFuran will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
2,3,7,8-TCDFuran
113. 1,2,3,7,8-PeCDFuran
1,2,3,7,8-PeCDFuran will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
Cl
1,2,3,7,8-PeCDFuran
-------
Part 11
125
114. 2,3,4,7,8-PeCDFuran
2,3,4,7,8-PeCDFuran will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
Cl
2,3,4,7,8-PeCDFuran
115. 2,3,7,8-HxCDFurans
2,3,7,8-HxCDFurans will not hydrolyze to any reasonable extent; however, they may
undergo other abiotic transformation processes.
Cl
2,3,7,8-HxCDFuran
-------
126
Fate Constants tor Hazardous Waste Identification Rule
116. 2,3,7,8-HpCDFurans
2,3,7,8-HpCDFurans will not hydrolyze to any reasonable extent; however, they may
undergo other abiotic transformation processes.
117. OCDF
Cl
Cl
2,2,7,8-HpCDFuran
OCDF will not hydrolyze to any reasonable extent; however, it may undergo other abiotic
transformation processes.
OCDF
-------
Part II 127
118. Heptachlor
Hydrolysis of heptachlor will occur by nucleophilic substitution of HgO at the allylic-carbon-
bearing chlorine resulting in the formation of 1-hydroxychlordene, which will be stable to
further hydrolysis.
HCI
1-Hydroxychlordene
-------
128
Fate Constants for Hazardous Waste Identification Rule
119. Heptachlor epoxide
Heptachlor epoxide will hydrolyze by nucleophilic attack of HgO at the epoxide moiety
resulting in heptachlor diol. Further hydrolysis of the diol can occur by nucleophilic substi-
tution of HjO at the chlorine-bearing carbon adjacent to the hydroxyl groups. The resulting
triol will be stable to further hydrolysis.
cr ci
Heptachlor epoxide
H2O
.CI
OH
Heptachlor diol
.OH
HCI
Heptachlor triol
-------
Part II 129
120. Hexachlorobenzene
Hexachlorobenzene will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
Hexachlorobenzene
121. Hexachlorobutadiene
Hexachlorobutadiene will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
;i—c=c-c=c
I
-ci
i
Hexachlorobutadiene
-------
130
Fate Constants for Hazardous Waste Identification Rule
122. a/p/ia-HCH
The reaction of o/p/ia-HCH occurs by frans-dehydrochlorination of the axial chlorines
resulting in the intermediate 1,3,4,5,6-pentachlorocyclohexene. This cylcohexene will react
further with either 1^0 or HO through sequential dehydrochlorination steps to give a
mixture of the regioisomers, 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene.
H
alpha-HCH
H90
HO
HCI
Cl
1,3,4,5,6-Pentachlorocyclohexene
HCI
1,2,3-Trichlorobenzene
1,2,4-TricWorobenzene
HCI
-------
Part 11
131
123. bete-HCH
6eto-HCH will not hydrolyze to any reasonable extent (NLFG). The six. equatorial chlorines
do not permit initial frarcs-dehydrochlorination to yield the intermediate
pentachlorocyclohexene as occurs in the alpha- (#122.) andgamma-isomers (#132).
H
beta-HCH
-------
132 Fate Constants for Hazardous Waste Identification Rule
124. Hexachlorocyclopentadiene
Hydrolysis of hexachlorocyclopentadiene results in the formation of 1,1-dihydroxy-
tetrachlorocylcopentadiene, which is an unstable product. Its degradation leads to the
formation of polymers.
Polymers
Hexachlorocyclopentadiene 1,1 -Dihydroxytetrachlorocyclopentadiene
125. Hexachloroethane
Hexachloroethane will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
Cl—C-C-CI
i, i,
Hexachloroethane
-------
Part II
133
126. Hexachlorophene
Hexachlorophene will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
OH HO Cl
cr ci cr ci
Hexachlorophene
127. lndeno[1,2,3-ccflpyrene
Indeno[l,2,3-cd]pyrene will not hydrolyze. It has no hydrolyzable functional group.
hdeno[1,2,3-cd]pyrene
-------
134 Fate Constants for Hazardous Waste Identification Rule
128. Isobutyl alcohol
Isobutyl alcohol will not hydrolyze. It has no hydrolyzable functional group.
-------
Part II 135
130. Kepone
Kepone will not hydrolyze to any reasonable extent; however, it may undergo other abiotic
transformation processes.
132. gamma-HCH
Kepone
The reaction pathway for the hydrolysis of gamma-HCH (lindane) is identical to that de-
scribed for alpha-HCH. (#122).
1,3,4,5,6-Pentachtorocydohexene
HCI
HCI
HCI
1 ,2,3-Trichbrobenzene
1 ,2,4-Trichtorobenzene
-------
136 Fate Constants for Hazardous Waste Identification Rule
134. Methacrylonitriie
Hydrolysis of methacrylonitrile will occur by the acid-catalyzed or base-mediated hydrolysis
of the nitrile moiety to give methacrylic acid and ammonia.
QH3
H2C=C-C-N
Methacrylonitrile
H+,HO
QH3
HoC-C-CH
NH2
Methacrylamide
H2C=C-C-OH
&
Methacrylic acid
NH,
-------
Part 11
137
135. Methanol
Methanol will not hydrolyze. It has no hydrolyzable functional group.
CH3OH
Methanol
136. Methoxychlor
The products formed during aqueous hydrolysis of methoxychlor are influenced by the pH of
the system. Above pH 10,2,2-6is(p-methoxyphenyl)-l,l-dichloroethylene (DMDE) is the
only reported product. Below pH 10 a second product, anisoin, is observed. Anisoin is the
major product formed by hydrolysis when the system is below pH 8; however, it is unstable
and will oxidize to anisil. Hydrolysis is not an important pathway in further degradation of
DMDE and anisil.
H3C
/~"\ y~~\
°\ /~~?H\ 7°°*
*—f A^i \^=/
OUI3
Methoxychlor
H20
H3C
H3 + HCI
2,2-Bis(p-methoxypheny1)-l ,1 -dicttoroethytene
H3CO— ^ /— f-C— ^V-OC
H
Anisoin
Oxidation
H3C
Anisil
-------
138 Fate Constants tor Hazardous Waste Identification Rule
137. 3-Methylcholanthrene
3-Methylcholanthrene will not hydrolyze. It has no hydrolyzable functional group.
3-Methylcholanthrene
138. Methyl ethyl ketone
Methyl ethyl ketone will not hydrolyze. It has no hydrolyzable functional group.
CH3CH2-C-CH3
Methyl ethyl ketone
-------
Part 11 139
139. Methyl isobutyl ketone
Methyl isobutyl ketone will not hydrolyze. It has no hydrolyzable functional group.
(C 113)20 HC n2~"C""~"C 113
Methyl isobutyl ketone
140. Methyl methacrylate
Hydrolysis of methyl methacrylate proceeds through nucleophilic attack by HO' at the ester
carbonyl to yield methacrylic acid and methanol. The second order alkaline hydrolysis rate
constant and the corresponding calculated half-life are in the range of values reported for
esters of similar structure.
H2C=C-C-O-CH3
CH3
Methyl methacrylate
HO
H2C=C-C-OH + CH3OH
CH3 Methanol
Methacrylic acid
-------
140 Fate Constants for Hazardous Waste Identification Rule
141. Methyl parathion
Hydrolysis of methyl parathion may occur through either reaction with I^O (neutral hy-
drolysis) or reaction with HO (base-mediated hydrolysis). Nucleophilic substitution by HgO
occurs in sequence at the two methoxy carbons to yield 0-methyl-0-(p-nitrophenyl)-
phosphorothioic acid (diester) and 0-(p-nitrophenyl)phosphorothioic acid (monoester),
respectively. Loss of the second methyl group from the disubstituted ester would be at a
rate approximately a factor of 10 less than the loss of the methyl group from the triester.
Hydrolysis of the monosubstituted ester [0-(p-nitrophenyl)phosphorothioic acid] would
proceed through cleavage of the P-0 bond at a rate of approximately one-half the rate of the
parent triester. Hydroxide-ion-mediated hydrolysis of methyl parathion proceeds through
initial attack of the hydroxide ion on the phosphorus atom with displacement of the p-
nitrophenylate ion. Loss of the two methyl groups from the 0,0-dimethylphosphorothioic
acid will proceed as described above. The phosphorothioic acid generated in each hydrolytic
pathway will eventually degrade to phosphoric acid and hydrogen sulfide.
H3C
H3C
Methyl parathion
O-Methyl-O-(p-nitrophenyl)phosphorothioic acid O.O-Dimethylphosphorothioic acid p-Nitrophenol
+ CH3OH
Methanol
NQa
+ CH3OH
O-Methylphosphorothioic acid Methanol
O(p-Nitrophenyl)phosphorothioic acid J
I + CHgOH
\ Methanol ^JL-QH + CH3OH
Phosphorothioic acid Methanol
Phosphorothioic acid p-Nitrophenol
H2S
Phosphoric acid
Phosphoric acid
-------
Part II 141
142. Naphthalene
Naphthalene will not hydrolyze. It has no hydrolyzable functional group.
Naphthalene
143. 2-Naphthylamine
2-Naphthylamine will not hydrolyze; however, it may undergo other abiotic transformation
processes.
,NH5
2-Naphthylamine
-------
142 Fate Constants tor Hazardous Waste Identification Rule
145. Nitrobenzene
Nitrobenzene will not hydrolyze; however, it may undergo other abiotic transformation
processes.
N02
Nitrobenzene
146. 2-Nitropropane
2-Nitropropane will not hydrolyze; however, it may undergo other abiotic transformation
processes.
N02
CH3-CH-CH3
2-Nitropropane
-------
Part II 143
147. /V-Nitroso-di-n-butylamine
JV-Nitroso-di-n-butylamine will not hydrolyze; however, it may undergo other abiotic trans-
formation processes.
V
N
CH3(CH2)3-N-(CH2)3CH3
N-Nitroso-di-n-butylamine
148. JV-Nitrosodiethylamine
JV-Nitrosodiethylamine will not hydrolyze; however, it may undergo other abiotic
transformation processes.
N
O HgC ri2~'IM~""'O HoC Hg
N-Nitrosodiethylamine
-------
144 Fata Constants for Hazardous Waste Identification Rule
149. /V-Nitrosodimethylamine
AT-Nitrosodimethylamine will not hydrolyze; however, it may undergo other abiotic
transformation processes.
N
-N— CHJ3
N-Nitrosodimethytamine
150. N-Nitrosodiphenylamine
JV-Nitrosodiphenylamine will not hydrolyze; however, it may undergo other abiotic transfor-
mation processes.
N-Nitrosodiphenylamine
-------
Part II 145
151. /V-Nitroso-di-n-propylamine
JV-Nitroso-di-Ti-propylamine will not hydrolyze; however, it may undergo other abiotic
transformation processes.
I
CH3(CH2)2-N— (CH2)2CH3
N-Nitroso-di-n-propylamine
152. M-Nitrosomethylethylamine
JV-Nitrosomethylethylamine will not hydrolyze; however, it may undergo other abiotic
transformation processes.
V
CH3CH2-N-CH3
N-Nitrosomethylethylamine
-------
146 Fate Constants tor Hazardous Waste Identification Rule
153. /V-Nitrosopiperidine
AT-Nitrosopiperidine will not hydrolyze; however, it may undergo other abiotic transforma-
tion processes.
•
0
N-Nitrosopiperidine
154. AMSlitrosopyrrolidine
JV-Nitrosopyrrolidine will not hydrolyze; however, it may undergo other abiotic transforma-
tion processes.
A
N-Nitrosopyrrolidine
-------
Part 11
147
155. Octamethyl pyrophosphoramide
Hydrolysis of octamethyl pyrophosphoramide (OMPP) proceeds through cleavage of the P-
O-P bond. OMPP is stable to attack by the hydroxide ion and the neutral water molecule,
but is degraded under acidic conditions.
(H3C)2NX|
(HgC),!^ 'N(CHg)2
Octamethyl pyrophosphoramide
H
Bis(N,N-dimethylamino)phosphoric acid
-------
148
Fate Constants for Hazardous Waste Identification Rule
156. Parathion
Parathion is the ethyl analog of methyl parathion. The products formed and mechanisms of
hydrolysis parallel those of methyl parathion (if 141) but hydrolysis proceeds at a slower
rate typical for triethyl phosphates compared to trimethyl phosphates.
CH3CH2oJ j- \
p_0-/ V-N
CH3CH20 \=/
Parathion
HO
CH3CH2oJ
H/
0-Ethyt-0-(p-nitrophenyO
•N02 + CHgCHgOH
NO,
0-(p-Nitrophenyl)phosphorothioic acid
jhosphorothioic acid Ethanol
CH3CH2OH
Ethanol
p-Nitrophenol
CH3CH2—Ox
P-OH
0,0-Diethylphosphorothioic acid
CH3CH20XJ
JP—OH +
\\Q'
Phosphorothioic acid
CH3CH2OH
O-Ethylphosphorothioic acid Ethanol
CH3CH2OH
Ethanol
HO Jl
>-OH
HOX
Phosphoric acid
Phosphorothioic acid
H2S
HO
Phosphoric acid
-------
Part II 149
157. Pentachlorobenzene
Pentachlorobenzene will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
Pentachlorobenzene
158. Pentachloronitrobenzene
The previously reported hydrolysis rate constant for pentachloronitrobenzene (PCNB) in
reference 6 was based on disappearance kinetics without confirmation of hydrolysis prod-
ucts. For this report, the hydrolysis experiment was repeated in glass-sealed ampules. No
disappearance of PCNB was observed after 33 days at pH 11 and 85°C. PCNB has, there-
fore, been designated as NLFG.
Pentachloronitrobenzene
-------
150 Fate Constants tor Hazardous Waste Identification Rule
159. Pentachiorophenol
Pentachlorophenol will not hydrolyze to any reasonable extent; however, it may undergo
other abiotic transformation processes.
Cl
Pentachlorophenol
160. Phenol
Phenol will not hydrolyze. It has no hydrolyzable functional group.
H
Phenol
161. Phenylenediamine
The three isomers of phenylenediamine, ortho-, meta-, and para-, will not hydrolyze; how-
ever, they may undergo other abiotic transformation processes.
NH2
,NH2
1,2-Phenylenediamine
-------
Part 11
151
162. Phorate
Phorate, by virtue of having one less methylene group in the sulfide side chain, is an analog
of disulfoton. The products formed and mechanisms of hydrolysis parallel those of disulfot-
on. Phorate has a neutral hydrolysis rate of approximately 30 times that of disulfoton (#96).
CH3CH2OJ
.P-S-CH2-S-CH2CH3
CH3CH2O
CH3CH2Ox
CH3CH2O,j
'-SH
HS-CH2-S-CH2CH3 +
Mercaptomethytethylthioether
O-Ethyl-S-((ethylthio)methyl]-
phosphorodithioicacid
+ CH3CH2OH
Ethanol
CH3CH20N1
CHgCHjjO
O,O-Dietnylphosphorodithioicacid ~ ~ ^p—OH
HO-CH2-S-CH2CH3 CHgCHaO'
+ HydroxymethytetnyfthioethBr O.O-Diethylphosphorothioic acid
CH3CH20§
;;^_SH + HO-CH^S-CHaCHg
HO^ Hydro^methytethylthioether CH3CH2O f
O-Ethylphosphorodithioicacid wfT' + CH3CH2OH CH3CH2OJ
O-Ethylphosphorodithioic acid Ethanol HOX
o-Ethylphosphorothioic acid
- -
Phosphorodithioicacid Ethanol
HCX
^^^
j. /^U ^U ^U
3 2
Phosphorodithioic acid Ethanol
CH3CH2OH
Ethanol
'-OH + H2S
Phosphoric acid
'-OH H
Phosphoric acid
Phosphorothioic acid
I +CH3CH2OH
1 Ethanol
H2S
Phosphoric acid
-------
152
Fate Constants for Hazardous Waste Identification Rule
163. Phthalic anhydride
Phthalic anhydride hydrolyzes to o-phthalic acid in water. The hydrolysis occurs through
nucleophilic attack of HjO at a carbonyl carbon. The resulting ring opening yields o-
phthalic acid.
Phthalic anhydride
.C-OH
J--OH
o-Phthalic acid
164. Polychlorinated biphenyls
Polychlorinated biphenyls will not hydrolyze to any reasonable extent.
n = 1 -5
Polychlorinated biphenyls
-------
Part 11
153
165. Pronamide
The N- substituted amide bond in pronamide, formed by reaction of a carboxylic acid and
primary amine, is more resistant to hydrolysis than similar bonds formed with carboxylic
acids and alcohols such as the previously discussed acrylate and phthalate esters.
-OH
3,5-Dichlorobenzoic acid
Pronamide
HO'
H2N-C-
CH
CH3
-C-CH
1,1 -Dimethyl-2-propynylamine
166. Pyrene
Pyrene will not hydrolyze. It has no hydrolyzable functional group.
Pyrene
-------
154 Fate Constants tor Hazardous Waste Identification Rule
167. Pyridine
Pyridine will not hydrolyze. It has no hydrolyzable functional group.
Pyridine
168. Safrole
Safrole will not hydrolyze. It has no hydrolyzable functional group.
H2CH=CH2
Safrole
-------
Part II 155
171. Strychnine
Strychnine will not hydrolyze to any reasonable extent.
172. Styrene
Strychnine
Styrene will not hydrolyze; however, it may undergo other abiotic transformation processes.
H=CH2
Styrene
-------
156
Fate Constants tor Hazardous Waste Identification Rule
173. 1,2,4,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene will not hydrolyze to any reasonable extent.
1,2,4,5-TetracHorobenzene
174. 1,1,1,2-Tetrachloroethane
The hydrolysis pathway for 1,1,1,2-tetrachloroethane will proceed through competing
pathways (nucleopbilic substitution and dehydrohalogenation). Nucleophilic substitution
will occur at the monochlorinated carbon with formation of trichloroethanol. Degradation of
trichloroethanol will continue to yield glycolic acid (hydroxyacetic acid). Base-mediated
elimination of chlorine from 1,1,1,2-tetrachloroethane will result in formation of 1,1,2-
trichloroethylene.
JO1
H-C-6-CI
H Cl
1,1,1,2-Tetrachloroethane
H20y
QHCI
H-6-C-CI +
H Cl
2,2,2-Tricrtoroethanol
HCI
-CI + HCI
1,1,2-Trichloroethylene
H-i-C-OH +
H
Hydroxyacetic acid
HCI
-------
Part II 157
175. 1,1,2,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane hydrolyzes by the base-mediated elimination of chlorine to 1,1,2-
trichloroethylene. This quantitative conversion occurs in the pH range of 5-9.
J'S'
Ch-C-C-CI
H H
1,1,2,2-Tetrachloroethane
HoO HO
J'
Ch-C=C-CI
H
1,1,2-Trichloroethylene
HCI
176. Tetrachloroethylene
Tetrachloroethylene will not hydrolyze to any reasonable extent.
_
Ch-C=C-CI
Tetrachloroethylene
-------
158 Fate Constants tor Hazardous Waste Identification Rule
177. 2,3,4,6-Tetrachlorophenol
2,3,4,6-Tetrachlorophenol will not hydrolyze to any reasonable extent; however, it may
undergo other abiotic transformation processes.
Cl
I
2,3,4,6-Tetrachlorophenol
-------
Part II
159
178. Tetraethyl dithiopyrophosphate
The P-O-P bond of tetraethyl dithiopyrophosphate is very labile to attack by hydroxide,
even at concentrations of hydroxide present below pH 7. The resulting 0,0-diethyl-
phosphorothioic acid is hydrolyzed to the final products phosphoric acid and ethanol by the
mechanisms discussed in the section on hydrolysis of phosphates.
CH3CH2Oxf ?XOCH2CH3
/P-0-PN
CH3CH2O OCH2CH3
Tetraethyl dithiopyrophosphate
HO
H9O
CH3CH2Oxf
P-OH
CH3CH20
O,0-Diethylphosphorothioic acid
CH3CH20§
>-OH + CH3CH2OH
HO
O-Ethylphosphorothioic acid Ethanol
HO.
i
;P-OH
HO"
PhosphorotNoic acid
CH3CH2OH
Ethanol
nan
H.S
Phosphoric acid
-------
160
Fate Constants tor Hazardous Waste Identification Rule
180. Toluene
Toluene will not hydrolyze. It has no hydrolyzable functional group.
Toluene
181. 2,4-Toluenediamine
2,4-Toluenediamine will not hydrolyze; however, it may undergo other abiotic transforma-
tion processes.
NH2
2,4-Toluenediamine
-------
Part II 161
182. 2,6-Toluenediamine
2,6-Toluenediamine will not hydrolyze; however, it may undergo other abiotic transforma-
tion processes.
183. o-Toluidine
H,
H2N,
NH,
2,6-Toluenediamine
o-Toluidine will not hydrolyze; however, it may undergo other abiotic transformation pro-
cesses.
NH2
o-Toluidine
-------
162
Fate Constants tor Hazardous Waste Identification Rule
184. p-Toluidine
p-Toluidine will not hydrolyze; however, it may undergo other abiotic transformation
processes.
185. Toxaphene
Toxaphene is a complex but reproducible mixture of chlorinated camphene (67-69% chlorine
by weight). The mixture has been shown to contain at least 177 and up to 670 components.
The degradation rate was determined by monitoring the loss of chlorine with time during
hydrolysis rate studies.
+ HCI
-------
Part 11
163
186. Tribromomethane
Hydrolysis of tribromomethane occurs initially by proton abstraction followed by formation
of the carbene, which reacts with HO to form carbon monoxide and the mineral acid.
H
Br—C—Br
Br
Tribromomethane
H9O
HO
CO +
Carbon monoxide
HBr
187. 1,2,4-Trichlorobenzene
1,2,4-Trichlorobenzene will not hydrolyze to any reasonable extent; however, it may un-
dergo other abiotic transformation processes.
1,2,4-Trichlorobenzene
-------
164
Fate Constants for Hazardous Waste Identification Rule
188. 1,1,1 -Trichloroethane
Nucleophilic attack by HgO on the trichloro- substituted carbon yields acetic acid, while the
hydroxide-ion-mediated elimination product is 1,1-dichloroethylene. The ratio of these
products is pH dependent. Acetic acid is the major product at low values of pH, while the
amount of the hydroxide-ion-mediated elimination product, 1,1-dichloroethylene, increases
with increasing values of pH.
H?,
H-C-C-CI
H Cl
1,1,1-Trichloroethane
H2O
HO
H Cl
V ?
H—C-C-OH + H—C=C-CI + HCI
H
Acetic acid
1,1-DicNoroethylene
-------
Part//
165
189. 1,1,2-Trichloroethane
Hydrolysis of 1,1,2-trichloroethane will yield the substitution product, chloroacetaldehyde,
and the base-mediated elimination product, 1,1-dichloroethylene. The most acidic hydrogen
(dichloro-substituted carbon) is lost during elimination of chlorine to form 1,1-dichloro-
ethylene rather than 1,2-dichloroethylene. The ratio of products will be determined by the
pH of the system.
-CI
H H
1,1 ,2-Trichloroethane
H90
HO
H H
O=C-C-CI
H
Chloroacetaldehyde
H Cl
H—C=C-CI
1,1-Dichloroethylene
HCI
H H
O=C-C-OH + HCI
H
Hydroxyacetaldehyde
-------
166 Fate Constants tor Hazardous Waste Identification Rule
190. Trichloroethylene
Trichloroethylene will not hydrolyze to any reasonable extent.
I
-Cl
Trichloroethylene
191. Trichlorofluoromethane
Trichlorofluoromethane will not hydrolyze to any reasonable extent based on other
polyhalogenated methanes.
Ch- C-CI
Cl
Trichlorofluoromethane
-------
Part II 167
192. 2,4,5-Trichlorophenol
2,4,5-Trichlorophenol will not hydrolyze to any reasonable extent.
2,4,5-Trichlorophenol
193. 2,4,6-Trichlorophenol
2,4,6-Trichlorophenol will not hydrolyze to any reasonable extent.
'H
2,4,6-TricNorophenol
-------
168 Fate Constants tor Hazardous Waste Identification Rule
194. 2,4,5-Trichlorophenoxyacetic acid
2,4,5-Trichlorophenoxyacetic acid will not hydrolyze to any reasonable extent; however, it
may undergo other abiotic transformation processes.
2,4,5-Trichlorophenoxyacetic acid
195. 2-(2,4,5-Trichlorophenoxy)propionicacid (Silvex)
Silvex will not hydrolyze to any reasonable extent; however, it may undergo other abiotic
transformation processes.
I
(CH2)2-C-OH
2- (2,4,5-Trichlorophenoxy)propionic acid
-------
Part I I
169
196. 1,2,3-Trichloropropane
By analogy to l,2-dibromo-3-chloropropane (#58), the ultimate products of aqueous
degradation of 1,2,3,-trichloropropane are 2-chloro-3-hydroxy-l-propene and glycerol. The
route to the substitution product, glycerol, proceeds through intermediate haloalcohols and
halohydrins. The amount of the elimination product, 2-chloro-3-hydroxy-l-propene, will
increase with increase in hydroxide ion concentration.
H-C-C-C-H
H H H
1,2,3-Trichbropropane
H,0
Cl CI OH
H-C-C-C-H + HCI
H H H
2,3-Dichk>ro-1 -propanol
f-?'VH
H H H
Epichtorohydrin
HCI
H-C-C-C-H +
H
2,3-Dichtoropropene
J H
H-C=C-C-
H
HCI
-OH + HCI
2-ChkDfO-3-hydroxypropene
Cl OH OH
H-C-C-C—H
H H H
1 -Chk>ro-2,3-dihydroxypropare
OH OH OH
H-C-C-C-H + HCI
H H H
Glycerol
OH p
H-C-c'-Hf—H + HCI
H H H
1 -Hydroxy-2,3-propytene oxide
OH OH OH
H-C-C-C-H
H H H
Glycerol
-------
170 Fate Constants tor Hazardous Waste Identification Rule
197. 1,1,2-Trichloro-1,2,2-trif luoroethane
l,l>2-Trichloro-l,2,2-trifluoroethane will not hydrolyze to any reasonable extent; however,
it may undergo other abiotic transformation processes.
CCIF2CCI2F
1,1,2-Trichloro-1,2,2-trifluoroethane
198. 1,3,5-Trinitrobenzene
1,3,5-Trinitrobenzene will not hydrolyze; however, it may undergo other abiotic transforma-
tion processes.
O2N NO2
sym-Tri nitrobenzene
-------
Part II
171
199. Tr/s(2,3-dibromopropyl)phosphate
Hydrolysis of fris(2,3-dibromopropyl)phosphate by nucleophilic attack of HgO on the C-0
bond or hydroxide ion attack on phosphorus will yield the same products. The 2,3-dibromo-
propanol can undergo hydroxide-ion-mediated elimination to yield 2-bromo-2-propen-l-ol or
intramolecular displacement of bromine by the adjacent hydroxyl group to form
epibromohydrin. The epibromohydrin is ultimately hydrolyzed to the final product, glycerol.
The 0,0-(2,3-dibromopropyl)phosphoric acid will hydrolyze further to yield phosphoric acid
and 2,3-dibromopropanol.
HCHj
IT
Tris(2,3-dlbrorropropyO phosphate
H20
HO"
T-OH + HO-i-d-i-H
CH.CHCKr-0 A I, A
O,O-(2,3-DibromopropyOprDsphoilc add 2,3-Dibromopropanol
• HHff-
O-(2,3-Dibromopropyf)phosphoric add 2,3-Dibromopropanol
H20
Phosphoric acid
HHHh
2,3-Dibromopropanol
H-cQji-fi-H
Epibromohydrin
+ HBr
H
1-Bromo-2,3-dihydiDxypropan9
HBr
j v
-*-^1 X
2,3>OibronrDpit)p&nol
L2o
H Br H
2-Bromo-1,3-propanBdiol
OH OH OH
HO— C— C— C— H
A A A
Qlycerol
HO-C-C-C—H
A
+ HBr
2-Bromo-2-properv1-ol
H8r
HBr
OH OH OH
H-C-i-C-
A A A
Glycerol
Q
-------
172 Fate Constants tor Hazardous Waste Identification Rule
201. Vinyl chloride
Vinyl chloride will not hydrolyze to any reasonable extent; however, it may undergo other
abiotic transformation processes.
H H
H-C=C-CI
Vinyl chloride
202. Xylenes
The three isomers of xylene will not hydrolyze. They have no hydrolyzable functional grotip.
H,
H3
CH,
H,
CH3
o-Xylene
m-Xylene
CH3
p-Xylerie
------- |