!re^
Measurement of Hydrolysis Rate Constants for
Evaluation of Hazardous Waste Land Disposal
Volume. 2. Data on 54 Chemicals
(U.S.) Environmental Research Lab., Athens, GA
PB87-227344
Au'g 37
.
on III information Resouroi
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prepay »* *
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-.' TiTcE A\D SUBTITLE
MEASUREMENT OF HYDROLYSIS RATE CONSTANTS FOR .EVALUA-
TION .OF HAZARDOUS WASTE LAND-DISPOSAL: Volume 2.
Data on 54'Chemicals
5. REPORT DATE
August 1987
6. PERFORMING ORGANIZATION CODE
J. Jackson Ellington, Frank E. Stancil, Jr., William
D..Payne* and Cheryl Trusty** .
8. PERFORMING pRGANIZATION REPORT NO.
. pf STORMING O/1G.MU.JATIQN NAME 4TJD ADC^ESS ..... r . ,
EnvironmentaT Research Laoorato.ry. U.S. Environmental
Protection Agency, Athens, GA 30613
*7echnology Allications, Inc., U.S. Environmental
Protection Agency, Athens, GA 30613
**ljn'iverr-ity of Georgia, Athpns, RA 3060?
2. SPSN'SOPiN'G .A6KNCVNAME "AND ADDRESS
10. PROGRAM ELEMENT NO.
ABWD1A
11. CONTRACT'GRANT NO.
12. SP2NSOPi\G .AGENCY-NAME AND ADDRESS
Environmental Research Laboratory - Athens, GA
Office of Research and Development
U.S. Environmental Protection Agency
Athens, GA 30513
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/01
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
To provide input data for mathematical models to estimate potential ground-
water contamination from chemicals in land disposal sites, hydrolysis rate constants
were determined under carefully controlled conditions. Rate constants are reported.
for 54 compounds: n-(aminothioxomethyl) acetamide, acetonitrile, 2-acetylaminofluor-
ine, auramine., azaserine, chlorambucil, chordane, chlornaphazine, beta-chlornaphtha-
lene, 2-choloro-l,3-butadiene, l-(0-chlorophenyl) thiourea, 3-chloropropanenitrile,
cyclophosphamide, ODD (p,p' isomer), daunomycin, dial late, dichloroethyl ether,
1,2-dichloropropane, 0,0-diethyl-O-pyranzinyl phosphorothioate, diisopropylfluoro
phosphate^ dimethoate, 2,4-dithiobiuret, ethyl methanesulfonate, ethylene thiourea,
ethylene-bj_s--(dithiocarbamic acid), 2-fluoroacetamide, hexachlorobenzene, hexachloro-
ethane, hexae.thyl tetraphosphate, isodrin, lasiocarpine, lindane, malonitrile,
melphalan, methomy1, methyl methacr-ylate, N-methyl-N-nitro-N-nitroso-guanidine,
2-methylazi.ridine, methylthiouraciI, alpha-naphthaylthiourea, N-nitroso-N-ethylurea,
n-nitroso-n-methylurethane', octamethylpyrophosphoramide, di-n-octylphthalate,
phorate, 1,3-propane sultone, safrole, tetraethyl pyrophosphate, thioacetamide, .
thiram,' toxaphene, 0,0,0-triethyl-ester phosphorothioic acid, 0,0,S-triethy1ester
phosphorodithioic acid, and tris(.2,3-dibromopropyl)phosphate.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
I). IDUNTIFIERS'OPE'! ENDED TERMS
U.S. fr.vi-cntrenta!
RG£;on ill Informatior
CsnlQr (SPM52J
841 C;:as'.r,ut Straot
[>:.,:->,,'^.;_'<;« DA \Cj\
. ri!"''-.CB!Ci*i3. rii AS1*
C. COS AT I I n-M'Ciloup
Resource)
N STATEMENT
19. SECURITY CLASS /This H,-ptnll
UNCLASSIFIED
RELEASE TO'PUBLIC.
21. NO. Or- hAGES
V 163:
z;. PRICE
EPA Form 2220-1 (9-73)
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EPA/600/3-87/019
August 1987
MEASUREMENT OF HYDROLYSIS RAT':' CONSTANTS' '
FOR EVALUATION OF HAZARDOUS WASTE LAND DISPOSAL:
Volume 2. Data on 54 Chemicals
by
J. 'Jackson Ellington, Frank E. Stancil, Jr.,
Uilliam D. Payne^, and Cheryl Trusty*?
Measurements Branch
Environmental Research Laboratory
Athens, GA 30613
1 Technology Applications, Inc.
Environmental Research Laboratory
Athens, GA 30613
^University of Georgia
Athens, GA 30602
EflVIRONMENTAL RESEARCH .LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
. ATHENS;. .GEORGIA 30613
-.' ; ' HE^'OOUCEDBY
. . . . . . ' US. DEPARTMENT OF COMMERCE
I ' NATIONAL lECI-iN'CAL
[ ' . IfJFOHMATIGNfO-.ViCE
' ' ' . ' SPRINGFIELD.VA.rz-61-
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.. ABSTRACT
To provide input data for a mathematical model to estimate potential
groundwater contamination from chemicals in land disposal sites, hydrolysis
rate constants were determined for 31 regulated chemicals under carefully
controlled conditions. Hydrolysis rates were measured under sterile conditions
at precisely controlled temperatures and at three pH levels (3,7, and 11).
Conditions were adjusted to provide sufficiently precise rate constants to meet
modeling requirements determined through model sensitivity tests. In addition
to close monitori;:g of temperature and pH, precautions were taken to minimize
impact of adventitious processes. Chemical concentrations as a function of
incubation time were measured by gas chromatography, liquid chromatography, or
ion exchange chromatography. Identities and purities of the chemicals were
determined by mass spoctrometry supplemented, in some cases, by infrared spec-
trometry. .
Four chemicals (PL-trans-4-chlorosti1bene oxide, benzyl chloride,
2,4-dichlorophenoxyacetic acid methyl ester, and lindane) were used as standard
reference compounds (SRCs) to ensure reproducibility and control of two parameters,
temperature and pH, that affect hydrolysis rates of chemicals in an aqueous
environment. The acetate and lindane were used as SRCs in the pH ranges of 8 to 9.5
and 9.5 to 11, respectively. Benzyl chloride and the stilbene oxide were used in
conjunction with neutral and acidic hydrolysis rate determinations, respectively.
Determinations of the hydrolysis rates of the SRCs were repeated at varying
temperatures and pH's over a 15-month period. During the study, the rates for
the SRCs were determined on four gas chromatographs and three liquid chromatographs
by four chemists. For these determinations the greatest variability from the
mean at the 95% confidence limit was ±12% for the acetate. The mean
and uncertainty at the 95" confidence level was: stilbene oxide (17.0 ±2.0 M-l
niin-1), benzyl chloride [ (7.2 ± 0.5) X 10"4 mirr1], acetate (699 ± 77 M"1 min'1), anc
lindane (3.3 ± 0.1 M'1 mirr1)'.
Hydrolysis rate constants are reported for the following 54 compounds:
n-(aminothioxomethyl) acetamide, acetom'trile, 2-acetylaminofluorine,
auramine, azaserine, chlorainbucil, chlordane, chlornaphazine,
beta-chlornaphthalene, 2-chloro-l,3-butadiene, l-(0-chlorophenyl)
thiourea, 3-chloropropanenitrile, cyclophosphamide, DDD (p,p'
isomer), daunoinycin, diallate, dichloroethyl ether, 1,2-dichloropro-
pane, 0,0-diethyl-O-pyranzinyl phosphorothioate, diisopropylfluoro
phosphate, dimethoate, 2,4-dithiobiuret, ethyl methanesulfonate,
ethylene thiourea, ethyiene-fcn_s_-(dithiocarbamic acid), 2-fTuoroaceta-
rnide, hexachlorobenzene, hexachloroethane, hexaethyl tetraphosphate,
isodrin, 1asiocarpine, 1indane, maloncnitrile, melphalan, methomyl,
methyl methacrylate, N-methyl-'i-nitro-M-nitroso-guanidine, 2-methyl-
aziridine, methylthio-'raci1, alpha-nephthay1thiourea, N-Nitroso-N-
e'chylurea, n-Nitroso-n-methylurethane, octamethylpyrophosphoramide,
di-n-octylphthalate, phorate, 1,3-propane sultone, safrole, tetra-
ethyl pyrophosphate, thi.oacetamide, thiram, toxaphene, o,o,o-tri-
ethyl-ester phosphorothioic Acid, 0,0,5-triethylester phosphorodi-
thioic acid, tris(2,3-dibromopropyl)phosphate.
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f
r
DISCLAIMER
. The information in this document has been funded wholly or in part 'by
.the United States Environmental Protection Agency.. It "has been subject to
the Agency's peer and administrative review, and .it has been approved for
publication as an EPA document. Mention of trade names or commercial products
does not constitute endorsement or recommendation for use by the U.S. Environ-
mental; Protect ion Agency. . .
11
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.
. FOREWORD .
As environmental controls become more expensive and penalties for judg-
ment errors.become more severe, environmental management requires more precise-
assessment tools based on greater knowledge of relevant phenomena. As a part
of tin's Laboratory's research on occurrence, movement, transformation, impact,
and control of chemical contaminants, the Measurements Branch determines the
occurrence of unsuspected organic pollutants in the aquatic environment and
develops and applies techniques to measure physical, chemical, and microbial
transformation and etjuilibrium constants for use in assessment models and for
development of property reactivity correlations.
In implementinq the land banning provision of the 1984 Hazardous and
Solid Wasvc- Amendments to PL 98-616 (RCRA), a mathematical model, was developed
to estimate notential groundwater contamination from chemicals in land disposal
sites. Applujtion of the model requires as input th^ hydrolysis rate constant(s)
for the chemical of concern. This report documents the laboratory measurement
of hydrolysis rate constants for 31 compounds regulated under Rf.RA. Approximately
four thousand chemical analyses were required on 35 different organic compound1;
(including standard reference compounds) to perform the rate constant measure-
ments. Experimental conditions were selected and carefully controlled to
provide sufficiently precise, rate constants to meet the requirements resulting
from model sensitivity tests.
Rosemarie C. Russo, Ph.D.
Director
Environmental Research Laboratory
. Athens, Georgia
ri i
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All compounds except 2-chloro-l, 3-butadiene, ethylene thiourea,
hexachlorobenzene, hexachloroethane, and safrole were hydrolyzed to
some extent under the varying conditions of pH and temperature employed.
Half-lives of hydrolyzable compounds ranged from 'a few minutes to centuries
at pll 7 and'25°C.
This report covers a period from August 1986 to May 1987, and work was
completed as of May 1987.
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:... . ACKNOWLEDGMENTS
i ' '._:'
! . This work, was conducted at the Athens Environmental Research Laboratory
| through the combined efforts of. EPA, Technology Applications, Inc. (TAI), and
University, of Georgia (UGA) personnel. The technical assistance 'of Miss Sarah
Patrnan fUGA; is grateful ly acknowledged. Mr. Alfred Thruston and Dr. Tii.-othy
Collette generated the chemical spectral data (Appendices A and B) needed to
. .-verify identity and estimate purity. The assistance of Mr. Heinz Kollig in
1iterature searches for hydrolysis data and methods of analysis and review of
this report is grateful ly akno.v! edged. The assistance of Dr. Lee Wolfe throughout
. the project and including review of this report is also gratefully acknowledged.
Discussions with Mr. William Donaldson were always fruitful and are so acknowledged.
.Mrs. Kari.n Blankenship's effort in typing the draft and subsequent revisions was
exefnpl ary.
VI
L.
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r
CONTENTS . :
' Page
forewor
Abstrac
List of
Acknowl
1
2
3
4
5
d ...-...
». ' . '
Tables and Illustrations ....;.. :.
edgments . . . . . v . . . . '..
. -Introduction . . . .
1.1 Purpose . . . .
1.2 Background . . .
1.3 References for Section 1 .
. Hydrolysis Kinetics .
2.1 Hydrolysis Mechanism
2.2 Rate Laws . .
2.3 Contributing Factors to Hydrolysis Rates . . . .
2,3.1 Temperature
2.3.2 pH, Buffer Catalysis
2.3.3 Ionic Strength
2.3.4 Sterility
2.3.5 Sorption
2.4 References for Section 2
Laboratory Determinations
3.1 Standard Reference Compounds (SRC) .......
3.1.1 Acid SRC
3.1.2 Neutral SRC
3.1.3 Base SRC
3.2 Rate Studies-OSU Chemicals
. Experimental .....
4.1 Chemicals and Solvents ....
4.1.1 Source ; .
4.1.2 Identity and Purity . . .
4.1.3 Solvents .......
4.2 pH Measurements
4.3 Buffers
4.4 Temperature Control . .
4.5 Sterile Water . . . .
4.6 Methocin of Ana'ysis
Data Analysis and Presentation .
5.1 Data Compilati'on Methods . .
5.2 Standard Reference Compound Data ........
5.3 Summary Sheets for OSW Chemicals ........
5.3.1 N-(Aminothiox,omethyl )-acetamide.. . .. . '.'
5.3.2 Acetonitrile . . .».-..
5.3.3 2-Acetyl aminofluorine '. . ....
5.3.4 Auratnine -.'..'
5.3.5 Azaserine. . .' . . . . . . ... . . ...
5.3.6 ' Chl'orambucil .....'....
5.3.7 Chlordane .....'...
5.3.8 Chlornaphazi ne . . . .
5. 3. .9 Beta-Chlornaphthalene. . . . . . . ; . .
5.3.10 2-Chloro-l,3-butadiene ..........
5.3.11 l-(0-Chlorophenyl)thiourea .......
.... i i i
.... iv
.... vii
.... viii
.... 1
.... 1
.... 3
.... 7
.... 7
.... 7
.... 8
..... 8
.... 8
.... 8
..... 9
.... 9
.... 9
.... 9
.... 10
.... 10
.... 10
. . . . 10
.... 10
.... 10
.... 16
.... 16
.... 16
.-...- 16
.... 16
.... 16
. . . . 16
.... 16
. . . . 17
.... 17
. . . . 18
18-
. . . . 18
. . . . 18
. . . . 28
.... 30
. . . . .33
35
. . . .. 36
. . . . -38
. . . -.- 39
. ... . 42
, . '. . 43'
. . . . 45
. . . . '46
VI 1
I
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5.3.12
5.3.13
5.3.14
5.3.15
5.3.16
5.3.17
5.3.18
5.3.19
5.3.20
5.3.21
5.3.22
5.3.23
5.3.24
5.3.25
5.3.26
5.3.27
5.3.28
5.3.29
5.3.30
5.3.31
5.3.32
5.3.33
5.3.34
5.3.35
5.3.36
5.3.37
5.3.33
5.3-39
5.3.40
5.3.41
5.3.42
5.3.43
5.3.44
5.3.45
5.3.46
5.3.47
5.3.48
5,3.49
5.3.50
5.3.51
5.3.52
5.3.53
5.3.54
3-Chloropropaiienitrile .
Cyc lophosphamide
ODD (p,p' isomer). . . '.-.. .
Daunomycin
Diallatc
Dichloroethyl ether. ....
1 ,2-Dichloroprcpane,
0 ,0-Oi ethyl -0-pyranzinyl phosphorothioate. ...
Diisopropyl fluorophosphate
Dimethoate . .
2,4-Dithiobiuret .
Ethyl methanesulfonate
Ethylene thiourea.
Ethyl ene-bis-(dithiocarbann'c Acid) .
2-Fluoroacetamide. . ........
Hexachlorobenzene
Hexachloro.ethane
Hexaethyl tetraphosphate .....
Isodrin ,
Lasiocarpine
Lindane
Mai ononit rile
Melphalan
Methomyl
Methyl methacrylate .
N-Methyl -N-ni tro-M-nitroso-quanidine
2-Methylaziridine .
Methyl thiouraci 1 .
Alpha-Naphthyl thicurea .
N-Kitroso-N-ethyl'jrea
N-Nitroso-N-inethylurethane ...........
Octamethyl pyrophosphoramide
Di-n-Octylphthalate
Phorate
1,3-Propane sulcone. . . . . . . .
Safrole ........'......
Tetraethyl pyrophosphate .'.
Thioacstamide . .
Ihiram ......
Toxaphene.
0,0,0-Triethylester phosphorothioic acid ....
O.O.S-Triethylester phosporodithioi.c acid. . . .
. Tri s(.2,3-Dibroinopropyl )-phosphate. .......
48
51
52
54
56
60
61
63
65
66
67
69
70
71
73
75
75
77
78
79
81
83
85
86
87
88
89
90
93
95
96
97
98
99
100
101
102
103
105
107
109
110
111
113
147
VI 1 .
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.. LISTS OF TABLES AND .ILLUSTRATIONS
Tables .
i . '...
i ' .
1 Illustrations
1.
?.
?
4.
5.'
6.
Chemicals frotn OSW "Second Third" list
Hydrolysis Data for DL-trans-4-Chlorostilbene Oxide ......
Hydrolysis Data for Benzyl Chloride .
. Hydrolysis L^ata for Methyl -2, 4-Dichlorophenox.y Acetate .....
Hydrolysis Data for Lindane ....'..
Hydrolysis Rate Constants and Half-Lives at 259C .......
5
}?
13
14
'5
?3
1. .Hydrolysis of DL-_tra_ns_-4-Chlorosti Ibene Oxide at 28°C, .
. pll 3.1 j 19
.2. ' Hydrolysis of Benzyl Chloride at 52.9°C, pH 7 . . . 20
3. Hydrolysis of Methyl-2,4-D^chlorophenoxy Acetate at 23°C,
... pH 9.06 21
4. Dependence of Benzyl Chloride Hydrolysis on Temperature .... 22
.IX
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... SECTION 1
' . ' . ''' - . . ' INTRODUCTION .'.'.;' '.
.1.1 Purpose . .
In inplementihg the .1984 Hazardous and Solid Waste Amendments to the
Resource Conservation and Recovery Act (RCRA), EPA's Office of Solid Waste
(OSW) will apply a decision rule based on a mathematical model to chemicals
under consideration that considers horizontal underground mover ent of a
chemical based on advection, dispersion, sorpticn, and chemical hydrolysis.
Application of the model requires as input the second-order or first-crder .
. hydrolysis rate constants for chemicals containing hydrolyzable functional
groups. A total of 362 compounds, divided into three groups, are to be
regulated initially. This report provides first- and second-order .hydrolysis
rate constants for those organic compounds in the second group for which
satisfactory values were not developed, in an earlier evaluation process and
describes the laboratory experiments conducted to measure hydrolysis rate
constants (1).
1.2 Background -
The Hazardous and Solid1 Waste Amendment?, of 1984 to PL 98-616 (RCRA)
stipulate that land disposal of "hazardous wastes" is prohibited unless the EPA
Administrator determines that prohibition of 'some wastes is not required to
protect hu-Tan health and the environment because those particular wastes are
not likely to r-?ach unacceptable levels in groundwater as a result of land
disposal. The 'amendments define hazardous waste as any of 362 specific compounds
(either part of or inclusive or Appendix VI11 compounds). In compiling this
list, major considerations wert toxicity of the material and quantity of waste
material generated annually. ' .
To provide a practical tool for determining which listed hazardous
.materials -.ay be disposed of by land disposal and under what conditions, the
! use of a relatively simple model was suggested that would estimate potential
| '; 'ouridw'a'ter contamination for each listed chemical. The model considers hori-
| zontal movement based on advection,-dispersion, sorption, and tran's format ion.
,;'.' . Hydrolysis is the only transformation process specifically considered. Although
>. other transfonnation processes, such as microbial degradation and chemical
« . . reduction, -.ay take place, they are not presently included in-the model. The
:' . model ;2SStries no unsaturated ZODL- for groundvVJter and assumes saturated ground-
water "zones" ranying from 3 meters to 560 meters in .depth, the mean depth of
I \ those considered is 78.6 meters. 'Organic carbon contents used in the model
, will range.from 1' to Q.1%. The point at which the groundwater must meet
standards may vary but was orign-al ly set'at 150 meters -horizontal ly from the
' point of ftnroduction. ' " ... '
; ' For each cbenical considered, the maximum alIqwable concentration for the
'j . receiving g'roundwater, 15Q moters "downstream," is entered into the model,
i . which asstnes envi rorwental characteristics for selected subterraniari systems.
). . The concentration cf leachate leaving the disposal si.te is computed for various
; conditions of rainfall, soil type, pil, etc. A computed leachate concentration
i that would cause unacceptable groundwater conditions is selected by OSW as the
t - . . ' ..
i -: ".'". .''. : . . r . ,' -.'-.
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maximum al lowa.ble concentration in leachates. A chemical nay be disposed of by
land only if freatnenL brings the leachate concentration down to the level
'selected -that, woul d ,;ot cau.se grot/ndwater to exceed the acceptable concentration.
The. model, inn"approach appl ies to landfills, surface impoundments, waste pilei,
and.land treatment operations. Land treatment operations may be addressed in a
different manner to allow for reduction in concentrations resulting from the
l.and -treatment process. -. '
... It-is. necessary to acquire octaiiol./water partition coefficients and
hydrolysis rate constants, for' each of tne 352.chemicals except for solvents
("fast track" in the list), .vhich will be treated as non-degrading, non-sorbing
constituents and chemicals already banned by the State, of- California (listed as
"California"). These two groups comprise 21 and 44 chemicals, respectively.
The remainder of the 362 ch.micals were separated into 3 groups by OSW: SI in
the "first third," 12! in the "second third," and 95 in the "third third."
Rate constant :and partition Coefficient data are required for these three groups.
by 7/36, -5/87, and 4/83, respectively. Partition .coefficient data are reported
in a companion document and have "orrespondinn delivery dates.
Hydrolysis of the organic compounds OP the OSW list of chemicals was
addressed by- d working group cf four experts assembled at the Environmental
Research Laboratory, Athens, G'«, on April 25 and 26, 1985. The experts were
chosen for their extensive t'uv.-ret ic,jl and experimental knowledge and experience
in the area of chenical reactivity of organic compounds in water. The work
group consisted of Cr. N. Lee X'olfo, U.S. Cnvi ro amenta! Protection Agency,
Athens,'.GA; Dr. Rob.rrt Taft, University of California, 'Irvine, CA; Dr. Clifford
Piunton, University of California, Santa Barbara, CA; and Or. William Mabey,
Kennedy/v'encks engineers, San KranciscO; CA.
The panel addressed only the organic compounds on the list of 362 chemicals
provided by Gi>W. Ihe inorganics included on the list were not addressed. The
inorganics will be examined .by another group and reported under a separate .
task. .For the organoinetalIic compounds on the list, the panel did not attempt
to estimate data, but did provide experimental rate data where available.
The evaluative procedure the panel followed was to divide the compounds
into three categories: those that had no hydrolyzt:ble functional groups, those
that would hydrolyze witn half-lives gr.jdtcr than a year, and those that would
hydro1y«:e with half-lives of less than a year. Hydrolys.is rate data were-provided
for some of the chemicals on the list. Ihe present and previous report was
.concerned with developing hydro'ysis rate data for the remainder.
. Of'the 31 compounds-in the "first thi r.j," .54. are either inorganic, contain
no hydroly-rable .functional group, contain a hydrolyzable functional group that
was judged by exports to be non-labile, or have acceptable literature values
for-hydro-lysis fvp'oru"! by Wolfe- (1). Acceptable first Or second-order hydrolysis
rate censtants for the r,?-nai-ninq 27 compounds- in the "first third"'is described
'in ""oasurfment of hydrolysis Rate Constants for evaluation of Hazardous Waste
Land Disposal, KPA/6f!n/3-36/0-13. ' . . ' .. '
Fisiv prestjnt report covers the 121 "second third"" chemicals. Of the !21
compounds,'0.7 rt'ere. f:l. ir.inatei! for the reasons cited above. Acceptable-first or...
Sec-ond-or;'(.'r-hydrolysis rate, constants for the remain-ing 54 compounds is .-
described-.in the text of this:.report. ' "'
'.''-. . ' - ' ..- 2 . ' ' . .
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r
Table 1 lists the chemical name and Chemical Abstract Number of "the 54
."second third" compounds'. The CAS number was used as the definitive chemica-1
descriptor when there was any ambiguity in re.latiny the name 'of the chemical to'
the structure of the compound. The expert panel did not have time to conduct
" an extensive search of the Iiterature because of the number of compounds and
short time period. Before beginning laboratory measurements, we, therefore,
conducted a three-pronged search of 'the.1iterature. The literature was searched
for methods of chemical analysis, laboratory generated hydrolysis values, as
we'll as protocols to follow.in laboratory generation of hydrolysis data. The
literature searches were conducted either-manually or electronically through
use of DIALOG, a database management system that yields access to over 200 databases.
Compounds with acceptable rate data extracted from the literature are noted in
Table 6, the summary table for rate data on the 54 compounds.
Suggested screening protocols and detailed test protocols for hydrolysis
of che-.nicals in water were., reported by Mabey £t aj_. (2). Suffet et £K (3)
suggested refinements to the above hydrolysis protocols. Neither source docu-
mented detailed laboratory methods to apply the suggested protocols; however,
the suggested protocols were based.on .present knowledge of the theory and
experimental aspects of hydrolysis and, therefore, provided a good foundation
to initiate the laboratory determination of hydrolysis rate constants for the
05W chemicals. The methods used for generation of the reported data evolved
after consideration of the two documents, discussions with Dr. Lee Wolfe,
j. Atnens EKL, and our experience with the "first third" measurements.
i The concept of standard reference compounds (SRC) evolved from discussions.
' . with Dr. Wolfe, Mr. Will ion T. Donaldson, and Mr. Heinz Kcllig all of Athens
j ERL. Standard reference compounds are compounds that are used a.s quality
1 assurance standards and as references in inter-laboratory generation of -hydrolysis
I . data. Repetition of rate constant measurement for these compounds over the course
I of thn two reporting periods has established baseline information for evaluating
experimental techniques and for all aspects of quality assurance. Four compounds
were selected, one each for acid and neutral hydrolysis, and two for basic .
.! .hydrolysis (Section 3.1). . . . ; "
Each standard reference compound is also amenable to analysis by both
gas chromatography and liquid chromatography. Reproduction of the hydrolysis
constants of the SKCs at the established concentrations, plls, and temperatures
insured that the experimental conditions for each set of compounds were acceptable
anJ the rate constants-for the OSW compounds could be determined wi.th required '. '
precision and accuracy. Tab I (.'5'. 2 through 5 .(Section 5.5.2) contain SRC rate
cons-tdnt data generated during laboratory detecni nati-ons of-rate constants of
the OSW compounds.- A range of .pseudo-first-order .hydrolysis rates for all ' ' .
S?.Cs'jnd second-order rate constants .for the acidic and basic reference'compound
'./ere established from these determinations. . . ' '
1.3 References for Section i - -
. .'.'.. Wolfe, '!. Lee:. "Screening of Hydrolytic-Reactivity of OSW Chemical's,"
submitted to Office of Solid Waste and 'Emergency Response, U.S.'EPA, Washington,
."' ~'C. May- 1935.' . ' '' ' . - - ' .
-------
.2. Mill., T., W. R. Ma bey, 0. C. Boniberger, T. W. Chou, D. G. Hendry,
and J. H. Smith. 1982. Laboratory Protocols for Evaluating the Fate of Organic
Chemicals in Air and Water. U.S. Environmental Protection Agency, Athens, GA.
EPA/600/3-82/022.
3. Suffet, I. H., C.-.W. Carter, and G. T. Coyle. 1981. Test Protocols
for the Environmental Fate.'ar.d "ovenent of Toxicants: Proceedings of a Symposium
of the Association of Official-Analytical Chemists (AOAC), October 21, 1980,
j Washington, DC, Edited by G. Zweig and M. Beroza, Pub!ished January 1981 by the
! -. . . AOAC. - . . .
-------
TABLE 1. Chemicals From OSW "Second Third List
CAS Number
Chemical
591-08-2
75-05-8
53-96-3
492-^90-8
115-02-6
305-03-3
57-74-9
494-03-1 .
91-58-7
126-99-8
5344-82-1
542-76-7
50-18-0
7.2-54-8 .
20830-81-3
2303-16-4
111-44-4.
78-87-5
297-97-2
5b-91-4.
60-51-5.
541-53-7
62-50-5
96-45-7
111-54-6
n-(Aminothioxomethyl.)-acetamide
Acetonitrile ' .
2-Acetylaminofluorine
Auramine
Azaserine
Chlorambucil .
Chlordane .
Chlornaphazine /
Beta-Chlornaphthalene
2-Ch1oro-l,3-butadiene
l-(0-Chlorophenyljthiourea
3-Chloropropanenitrile
Cyclophosphamide
ODD (p.p1 iso,ner) .
Daunomycin
Dial late ' .; '..''
Dichloroethyl ether
1,2-Dichloropropane : '
0,0,-Diethyl -0-pyr'anzinyl phosphorothioate
Diisopropyl fluoi-ophosphate
Dimethoate . : .
?,4-Dithiobiuret
Ethyl methanesulfonate
Ethylene thiourea
Ethylene-b^s-(dithiocarbamic acid)
-------
r
(TABLE 1. Cent.)
640-19-7
:" : 118-74-1
' . 67-72-1 , ..
' 757-58-4 ;
465-73-6
303-34.-4
58-89-9 ' .
109-77-3
148-32-3
16752-77-5
80-62-6
70-25-7
75-55-8
56-04-2
86-33-4;
759-73-9
615-53-2
152-16-9
117-84-0
298-02-2
1120-71-4.
94-59-7
107-49-3
., ' 62-55-5
' .137-26-8
8001-35-2
126-68-1 '
" 2524-0.9-6
. 126-72-7
2-Fluoroacetamide
Hexachlorobenzene
Hexachloroethane
Hexaethyl tetraphosphate
Isodrin
Lasiocarpine
Lindane
Malanonitril e
Melphalan .
Methomyl
Methyl methacrylate
H-Methyl-N-nitro-N-nitrosoguanidine
2-Methyl aziridi.-c: :
Methylthiouraci1
Alpha-Naphthaylthiourea
N-Nitroso-N-ethylurea
N-Nitroso-N-mcthylurethane
Octamethylpyrophosphorainide
. Di-n.-Octylphthalate
Phorate
1,3-Propane sulfone .
Safrole . .
Tetraethyi pyropht>sphate
Thioac'et amide
Tlriram . '...'
Toxap'nene .
0,0,5-Triethylester phosphorothioic acid
0,0,S-Triethylester phosphorodithipic
Tris(2,3-Dibroinopropyl) phosphate
-------
I . . (-X):
SECTION 2
HYDROLYSIS KINETICS
2.1 Hydrolysis Mechanism . . . '
Hydrolysis of organic compounds refers to reactio.i of the compound with
water in which bonds are broken and new bonds with HO- and H- are formed. A
common example is the reaction of an alkyl hali-de with the loss of halide ion
RX + HOH .- ROH + HX (or H+, X~)
j The rate of the reaction may be promoted by the hydronium ion (H+, or HjO+)
i . or the hydroxyl ion (OH"). The former is referred to as specific acid catalyis
! and the latter as specific base catalysis. These two processes together with
! the neutral water reaction were the only mechanisms considered in this study.
1 This allowed direct measurement of the HjC* or OH" concentration through, accurate
determination of solution pH.
Some chemicals show a pH dependent elimination reaction:
H X
H+ or
- C - C --> C = C + HX
OH- . . .
In this study only the disappearance of substrate was monitored wi-th no attempts
to identify mechanisms. .
2.2 Rate Laws
If all processes referred to in Section 2.1 are included where the rate of
hydrolysis is given by tne equation,
.' d[C] '. - - . .":'
- ---- -- kh[C] = kA[H+][C] + kB[OH-][C] + kN'[H20][C] : (2.1) .
dt '
where [C] is the concentration of reactant and kn is the pseudo-'i rst-oroier rate
constant at a specific pH and temperature, k,\ and kp, are second-: rder rate
constants and kjj1 the pseudu-t'irst-order rate constant for the acid, base and
neutral promoted processes, respectively. The water concentration is essen-
tially not depleted .by the reaction and much greater than [C], thus ktj'Q^O] is
a constant (kv). .
Equation 2.1 assures each individual rate process is first order in
substrate, thus k|, can be Jefined as: . .
. kh-=-kA[H+] + kB[0!r] + kN .-. (2.2)
-------
Using the autoprotolysis equilibrium expression . ;
.- ' . (2.3)
equation 2.2 may be rewritten as
' . -
+ kr- : ' (2.4)
' '
Equation. 2.4. shows. the dependence of k^ on [H*] and on the relative values of.lu,
kB>- and kN. ' . .' ...
As a good approximation, the second-order rc'cc constants for acid hydrolysis
and .for base hydrolysis can be calculated by dividing, the pseudo-first order
rate constant obtained at the appropriate pH by *he hydronium ion or hydroxyl
ion concentration, respectively. The half-life of a chemical at a given pH and
temperature can be calculated from equation 2.5, where kn is the observed rate.
' . ' 0.693
... t1/2 = - . (2.5)
Data evaluation methods and calculations are discussed in more detail in Section
5.1. '...:' .
Excellent discussions of the hydrolysis rate laws are provided by Mabey and Mill
(1,2). ' . .
2.3 .Contributing Factors to Hydrolysis Rates
. 2.3.1 Temperature . '..''.
Water and oil baths that precisely held temperature were used when
experimentally determining rates of hydrolysis (Section 4.4). This removed the
.contribution of temperature as a variable during the actual experiments.
, '. 2.3.2 pH, B-jffcr Catalysis ' . ' .
i . . . N3S calibration standards were used to calibrate the pH meter
j before measurements. The pll was usually neasured at the temperature of analysis.
I In regions where only kr\ contributes to hydrolysis, K^ ;vi 11 decrease by a factor
f . of 10 for each unit increase in pH. Similarly .-,'here only kg contributes to
I . hydrolysis, K|, will increase by a factor of 1C) for each unit increase in pH.
i ' kft. is for the pH-independent hydrolysis rate moasureTient. Buffers (0^005-M)
wtre used to. control pH and avoid buffer catalysis (3). '"..
| .' 2..3.-3 Ionic Strength. ' . ' "
I6n;ic strengch, depending on the chemical < can lead either to hydrolysis
acceleration 'or retardation. For this reason, concentrations of buffer solutions
': ; '.'.' .' -8 . . ' . "' .." :
-------
r
v/ere set as low as possible, ..yet high enough to maintain constant pi! over the
course of the hydrolysis'determination. The compound concentration was corres-
pondingly set low, usually 10''^ M or less. '
2.3.4 Sterility ; .. " ". .
Sterile conditions vvsre maintained for all studies to prevent
microbial degradation of the chemicals (Section 4.5). . . .
2.3..B Scrption' '!'.''.
Chemicals analyzed by gas chromatography were' extracted from the
aqueous layer and glass surfaces with iso-octane. Samples analyzed by liquid
chroma tography were checked for sorption by emptying the sample container,
rinsing the container with acetcnitrile, and analyzing the acetonitrile in the
sane manner as the sample. . .
2.4 References.for Section 2
I. Ma bey, W. and T. Mill. 1978. Critical Review of Hydrolysis of
Organic Compounds in Water .Under Environmental Conditions. J. Phys. Chem. Ref.
Data. 7(2).: 383-415.
2. Mill, T., W. R. Mdbey, D. C. Bomberger, T. W. Chow, D. G. Hendry,
and J. H. Smith. 1982. Laboratory Protocols for Evaluating the Fate of Organic
Chenicals in Air and Water. U.S. Environmental Protection Agency, Athens, GA.
EPA/600/3-82/022. . ' "
3. Perdue, E. M. and fl. L. Wolfe. 1933. Prediction of Buffer Catalysis
in field and Laboratory Studies of Pollutant Hydrolysis Reactions. "Environ.
Sci. Techno!. 17, 635-642. ' . ' .
-------
[.' . . . SECTION 3 ' ' .
I ' . . . ... LABORATORY DETERMINATIONS . . -
f. -
| ' 3.1 Standard Reference Compounds (SRC)
Four compounds were used as standard reference compounds, one each for
| acid and neutral, and two for base hydrolysis. The SRC hydrolysis rate constants
[ were determined before analysis of samples and interspersed with laboratory
; determination of hydrolysis rates of the compounds in Table 1. Pertinent
i information as to concentration, pH, temperature, and instrument for analysis
| is tabulated in Tables 2 through 5. The rate values for all four SRCs are in
good agreement with literature or calculated values.
3.1.1 Acid SRC . . .
DL-trans-4^Chlorostilbene oxide was selected as the SRC for acid
hydrolysis studies. Operating conditions and calculated rates are in Table 2.
The chlorine was essential for analysis by the electron capture detector.
I
I 3.1.2 Neutral SRC .
| Benzyl chloride was selected as the SRC for neutral hydrolysis
f conditions, since the rate is known to be independent of pH below 13. Also,
> the degradation rate at room temperature is fast enough to allow easy sampling.
Table 3 tabulates analytical parameters. Of particular interest is the last
j column of K^ values extrapolated from three elevated temperatures.
I. - ' ' '
I 3.1.3 Base SRC
[ .&. Methyl-2,4-dichlorophenoxy acetate (2,4-D methyl ester) served as
f the base SRC in the pH range 8 - 9.5. Table 4 contains rate values and corre-
I' spending analytical parameters. Data are reported as calculated from analytical
f . runs.
b. Lindane, not as sensitive to hydroxide ion catalysis, served as
the SRC in the pH range 9.5 to 11. Data are reported in Table 5.
3.2 Rate Studies-OSW Chemicals . .
A general description of laboratory operations will be given in the
remainder of this section. A typical hydrolysis experiment consisted of pre-
paring a spiking solution of the compound of interest, preparing buffer solutions,
transferring spiked buffer r.o individual "rate point tubes" (_5-ml Teflon
lined, screw cap, or sealed ampules), then monitoring degradation by sacrificing
individual tubes and determining percentage of the substrate remaining.
10
i
L
-------
r
Spikinn «--;urions ,v,c< . ;>-a,u,re(j by dissolving the substrate in acetonitrile,
meth-snol-, cr wate-. The concentration was such that 0.1 ml diluted to 100 ml
with buffer gave a,.suDjlr't-;- concentral *(,.. -»»*. wa$ IxlO'^M or was 50% of the
water solubility or less* .' ~
Initial hydrolysis runs ivere performed at pH 3, 7, and 11. Buffprs were
prepared at. these pils then ireasured at the temperature of the hydrolysis run.
Each run-consisted of five or six tubes. Immediate analysis of one tube estab-
lished the 100% response pea'< (T0). Analysis'Of a second tube within 3 to 6
hours gave a good estimate of sampling frequency for the"remaining tubes.
The initial, hydrolysis runs were.used to set pH and temperature condi-
tions for subsequent rate determinations. The rate determinations were normally
performed in triplicate; however, some compounds required more replicates
and some less.
-------
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Kwurce*
-------
. __ ---.-"'= 'i' Hydrolysis Data Foru;_ ^-v^./j-chlorostilbene Oxide
I __---- " . .
t- - "' ' :: -i_. !
Temp, j MeLhod of X103 K,a K2b. . K?(;.r1 .min'1)
Date pH (°C) Analysis (m.in~i) (M-l mtn~l)
11-1-85
.. 11-6-85
11-6-85
11-6-85
11-6-85
11-6-85
31-15-86
11-15-86
11-15-86
11-15-86
li- 15-86
3-11-86
3-11-86
3-11-86
3-11-86
5-14-86
8-13-86
8-13-86
8-15-86 .
11-18-86
11-18-86
11-19-86
11-19-86
11-19-86
11-19-86
11-19-86
11-19-86
12-31-&6
12-31-86
.1-9-87
1-9-87 '
3.13
3.10
3.10 '
3.07
3.07
3.63 .
3.01
3.01
3.59
3.59
.3.01
3.06
3.06
3.06
3.06
2: 99
2.95
2.95
3.03
2.39
2.89
3.05
. 3.05
3.05
3-. 02
3.02
3.02
3.10
2.96
3.12
3.13
28.0
23.0
28.0-
28-0 .
23.0
38.2
28.0
28.0
33.2
33.2
23.0
28.0
23.0
23.0
23.0
23.0
25.3
25.3
24-. 3
25.0
25.0
25.0
25.0
23.0
25.0
2E.O
25.0
25.0
25.0
23.0
23.0
LC
LC ' '
LC
LC
GC.
GC
LC
LC
LC
LC
LC
LC
. GC
LC
: GC
LC
LC
LC
LC
LC
LC
LC
LC
LC
LC
LC
LC
LC '
LC
LC
LC .
17.4
. 14.4
14.9
14.3
14.6
17.0
20.8
23.7
23.5
24.5
21.1
16.9
14.3
.16.9
14.4
12.9
19.4
24.2
11.1
.29.5
35.8
24.4
22.8
22.8
17.4
16.1
19.0
16.9
18.5
.15.5
10.1
23.5
18.2
18.8
16.8
17.1
72.3
21.3
24.2
91.4
95.3
21.6
19.4
16.4
19.4
16. 5
12.6
17.3
21.6
11.9
22.9
27.3
27.4
25.6
25.6
18.2
16.8
19.9
21.2
16.9
.20.4
13.6
15.3
11- 8
12.2
10.9
11.1
11.5
13.8
15.7
14.6
15.2
14.0
12.6
10.6
12.6
10.7
16.8
16.6
20.6-
13.1
22.9
27.8
27.4 .
25.6
25.6
18.2
16.8
19.9
21.2
16.9
27.4
18.3
17.0 ± 5.4°
| . a. Pseudo.-first-order rate constant from the slope line when. In "X "remaining
i - . ' . ' .'...
j -. . . .versus time was plotted. Standard deviation of slope was <10% in. each case. '
f b. Second-order rate constant.
r . '
t . - ..'
! c. Extrapolation to 25°C using activation energy of 25.6 kcal/mole.
d. Mean and standard deviation of 31 determinations. '
12
-------
Table 3. Hydrolysis Data For Benzyl Chloride
Date
11-26-35
11-26-85
11-26-85
11-26-85
11-27-35
11-27-85
11-27-85
11-27-85
11-29-85
11-29-85
12-2-85
12-2-35
5-21-86
5-21-86
7-2-86
8-19-35
8-22-86
8-22-86
8-22-86
11-19-86
11-19-86
11-21-86
11-21-35
11-21-86
1-9-37
1-9-87
1-27-37
1-27-87
pH
7.00
7.00
7.00
7.00
7.00.
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00
7.00'
7.00
7.00
7.00
7.00
7.00
.7.00
Temp. Method of .
(°C) Analysis XlO^K^inin"13)
52.9
52.9
52.9
52.9
23.0
28.0 .
28.0
28.0
45.0
45.0 .
36.4
36.4
53.4
53.4
53.5
45.0
42.7
46.0
45.0
45.0
45.0
45.0
45.0
45.0
45.0
45.0 '
49.0
49.0
LC
LC
LC
LC
LC
LC
1C
LC
GC
LC
GC
LC
GC
GC
GC
GC
GC
GC
.GC
GC
GC
GC
GC
GC
GC
. GC
GC
GC
203.5
191.0 '
211.3
216.0
10.4
12.2
11.1
9.8
:72.7
72.2
31.9
33.9
140.2
136.5
154.3 '
65.8
70.0
67.0
55.0
63.9
60.6
69.0
69.0
78.0
66.9
. 69.4
98.9
98.6
X104 Mining)
(Extrapolatedb)
8.8 .
8.3
9.2
9.4
7.2
3.5
7.7 .
6.8
7.3
7.2
8.3
8.8
5.8
5.6
6.3 .
6.6
9.0
6.0
5.5
6.4
6.0
6.9
6.9
7.8
6.7
6.9
6.4
6.4
7.2 ± l.lc
a. First-order rate from the slope of the line when ln% remaining versus
time was plotted. Standard deviation of the slope was -CIO,, in each .
case. . ...
b. Extrapolated to 25°C using activation energy of 22.5 ± 1.4.kcal/niole.
c. Mean and standard deviation of 26 determinations.
13
-------
Table 4. Hydrolysis Data For 2,4-DME
Date
10-7-85
10-7-85 '
10-8-85
10-8-85
10-9-85 .
10-5- Rr.
10-11-85
10-11-85
10-11-85
10-11-85
3-6-86
3-6-86
3-6-86
3-6-86
5-12-86
5-12-86
5-13-86
.5-13-86
7-2-86
7-3-86
8-14-S6
8-14-86
8-14-86
12-31-86
12-31-86
1-9-87
1-9-87
.PH :.
9.06
9.06.
9.65
9.65
7.11
7.11
9.14
9.14-
8.00
8.00
8.87
8.87
9.10
9.10
9.38
9.45
9.38
9.45
8.75
8.72
8.81
8.81.
8.81
8.74
8.54
3.55
8.55
Temp.
(°C)
28.0
28.0
28.0
28.0
70.3
70.3
28.0
28.0
48.5
48.5
25.0
25.0
25.0
25.0
. 25.0
25.0
25.0
25.0
31.0
31.0
23.0
23.0
23.0
45.0
45.0
'45.3
45.3
Method of
Analysis
LC.
GC
LC
.GC.
LC
GC
LC
GC
LC
GC
LC
GC
LC
GC
LC
LC
GC
GC
LC
LC
LC
LC
LC
' GC
GC
GC
GC
X104 K,a
(mi'n-1;
80. 7b
70.4
262.0
278.0 .
114.0
100.0
118.0
103.0.
103.0
86.0
57.1
41.8
95.0
79.0
230.0
249.0
224.0
224.0
91.2
79.2
29.9
33.0
36.0
340.0
350.0
412.0
415.0
K?
(M-l min-1)
560C
489
467
. 495
5451
. 4775
681.. :
593
2079
1731
770
563
754
627
958
883
933
794 .
1038
966
541
596
650
1547
2520
2847
2867
MM'1 i.nrT1}
(ExtrapolatecP)
481'
420
401
426
729
638
58^
509
6C2
567
769
563
754
627
958
883
933
794
768
715
599
.661
721
593
966 .
1077
1084
699 ± 190°
a. Extrapolation to 25°C using activation energy of 9.0 (±0.4) kcal/mole.
b. .Pseudo-first-order rate constant from slope of the line when ln% remaining
versus time was plotted. Standard deviation of slope was <10% in each case.
c. Second-order rate constant, variation of Kw and hydroxide ion concentration
with changing temperature included in calculation.
d. Mearrand.standard deviation of 27 determinations.
14
-------
Table 5. Hydrolysis Data For Lindane
Date
9-2-86
9-3-86
9-3-86
9-3-86 .
9-4-85 .
11-19-86
11-19-85
11-19-86
12-31-86
12-31-86
1-8-86
1-8-86
PH
10.98
10.98
11.60
11.29
11.08
10.37
10.37
10.37
10.45
10.31
10.71
10.71
Temp.
46.0
46.0
22.8
37.0
46.0
45.0
45.0
45.0
45.0
45.0
45.3
45.3
Method of
Analysis
GC
GC
GC
GC
GC
GC
GC
GC
GC
GC
GC
GC
X103 K,a
(min ]
71.5
78.0
9.9
40.2
83.4
14.8
14.6
14.5
20.0
18.4
36.0
33.1
^(M'l min'l)
17.6°
19.2
2.9
8.7
16.3
15.8
15.6
15.4
7.7
22.5
17.2
15.8
MM'1 min'M
(Extrapolated")
3.29
3.59
3.5P-
3.24
3.05
3.19
3.15
3.11
3.57
.4.54
3.39
3.12
3.3 ± 0.2d
a. Pseudo-first-order rate constant from slope of the line when In % remaining versus
time was plotted. Standard deviation of slope was <10% in each case.
b. Extrapolation tc 25°C using activation energy of 15.1 (±0.5) kcal/mole.
c. Second-order rate constant, variation of Kw and hydroxide ion concentration with
changing temperature included in calculation..
d. Mean and standard deviation of 12 detenninations.
t
-------
SECTION' 4
:XPI:K [MENTAL
4.1 Chemicals .and Solvents' . '' . .
4.1.1 Source . ' ' ' '
The LPA repositories at Research Triangle Park, NC, and Las Vegas,
''V, were the first choice for chemicals on which hydrolysis rates were measured.
Comnercial chenical companies were the second sources. The supplier of each
chemical is listed on the data sheets in the Section 5.3.
4.1.2 Identity 'and Purity -.
Stated purities are listed on the data sheets. The chemicals were
analyzed by mass spectroraetry for confirmation of the stated identity. The
generated mass spectral data are in Appendix A. FT-IR was used to characterize
three of the "second third" compounds. {Appendix 8).
4.1.3 Solvents . ' .
Solvents were "distilled in glass," Burdick and Jackson solvents
either gas chromatograph or KPLC grade, as required by the method of analysis.
4.,? pM Measurement
An Orion Research EA920 pH meter equipped with an Orion Research A310300
Ross combination oloctroJe was used for all pH measurements, national Bureau
of Standards (NRS) reference standards were usoJ to calibrate and.check the pH
i^oter. The pil meter had a stated accuracy of fQ.02 units. The temperature
compensation probe.was used for all measurements. The pi) was measured at the
temperature of the hydrolysis rate measurement and adjusted with base or acid
to ootain the
-------
4.4 Temperature Control .
Forma Scientific refrigerated and heated baths (Model 2095) were used for
temperatures in the range of'2 to 70°C (i0.02°C).. A Lauda C-20 oil bath with a
stated control accuracy of ±0.01°C and a fine control range of ±0.2°C was used
for temperatures above 68CC. Temperatures were measured with American Society
for Testing and Materials (-ASTM) thermometers, calibrated by NBS procedures
and N3S certified masters'. The .thermometers were calibrated in 0.1°C increments.
4.5 Sterile Water
Water used in the experiments was unchlorinated ground v/ater that was
first processed through a high capacity reverse osmosis unit and a deionizer
unit. This "house" deionized water was further purified by passage through a
Rarnstead Nanopure II deionizer, 4-Module unit with Pretreatment, High Capacity,
and Z-Ultrapure cartridges. Water obtained from this unit had a resistance of
greater than 16 meg ohms. This double deionized water was autoclaved for 30
min/liter and allowed to cool'before use. The sterile water was stored in a
sterile-cotton-plugged container until used. All hydrolysis runs were conducted
in screw cap tubes. Data from smear plate counts on agar indicated growth as
being less than 1 colony per milliliter through 9 days at 25°C and pH of 5, 7,
and 9. Sterility checks on the water were performed intermittently.
Buffer solutions were checked for bacterial growth. Buffer solutions,
prepared as described above, were transferred at room temperature to screw cap
test tubes. One-half were flame transferred, the other half without flaming.
A sanple (1 ml) from each tube was plated daily, for nine concurrent days on
TGF. agar. After.a 48-hour incubation, no growth was found. This confirmed
sterility. Control checks during hydrolysis runs showed no growth.
4.6 Methods of Analysis
Details of the methods of chemical analysis are listed on the data sheet
for each compound. Generally gas chromatography was the first method of choice
for four reasons: . .
1) sensitivity and specificity of detectors :
2) .solvent extraction stopped hydrolysis and allowed multiple
injection-s over extended periods of time
3) solvent extraction also lessened problems caused by compound
sorpticn-to glass .
4) direct aqueous injection of water soluble compounds that were
not amenable to other methods of analysis .
High performance liquid chromatography (HPLC) was used extensively; ion .
chroinatography and the diode array UV-detector were used in the analysis of
sodiuor.fluoroacetate and thiourea, respectively. Hydrogen cyanide released by
the decomposition of 2-methyllactonitrile was monitored by EPA Method 335.
Linearity, of detector response in the concentration range of analysis for
each chemical was established to ensure reliable concentration versus tir.ie plots.
.' ' - : 17 ' -.'.'''''
L
-------
. ' .-.;...'. SECTION'S
'. '' ' '. . . DATA ANALYSIS AND PRESENTATION
-.'.'.
5.1 ' Data Compilation Methods
Raw data'consisted of time of sampling and percentage substrate remaining.
The measured concentration at time zero was considered 100* and was the reference
point for the remaining points. The data were processed :on a Lotus 1-2-3/IBM
PC-XT'using a data entry/linear regression program. The raw and calculated
data were entered.in a notebook. Graphs were made by using persona! computers
to plot In (% remaining) vs. time and to calculate statistical values.
.- Values obtained from the linear regression program include the slope
(pseiido-f irst-ordei- rate constant), Y-intercept, variance, SD of Y-intercept,
SO of slope, and the correlation coefficient (r-). . .
5.2 Standard Reference Compound Data
.All the laboratory data on the SRCs are summarized in Tables 2, 3, 4, and 5.
Figures 1, 2, .and 3 are representative graphical presentations of hydrolysis .
data for three SRCs. Figure 4 is an Arrhenius plot for hydrolysis of benzyl
chloride at four temperatures. See 5.3.32 for lindane data and illustrative figure.
An energy of activation of 22.5 ± 1.4 Kcal/inole for benzyl chloride was calculated
from the cata associated with Figure 4. An error of 10% in the slope was
assumed. Arrhenius plots for the other SRCs yielded the following energies of
activation: . CSO (25.6 kcal/mole); 2,4-DME (9.0 ± 0.4 kcal/mole).and lindane
(15.1. t .0.5 kcal/mole). The change in the hydrolysis rate constants for benzyl
chloride and the methyl ester of 2,4-D after March 1986 illustrates how susceptible
rate determinations are to slight changes in the controlled parameters. No
plausible explanation has been found for either the increased 2 4-D.rate or the
decreased benzyl chloride rate.
5.3 Summary. Sheets for CSW Chemicals . .
A summary sheet was prepared for each chemical. The summary sheet, contains .
information pertinent to the analysis of each chemical, and includes source,
purity, and analytical method. Also included on the sheet is information on
pH, temperature, pseudo-first-order and second-order rate constants, half-lives,'
and correlation coefficients (r?). Sample identity was confirmed by mass spec-
trometry and infrared spectrometry as reported -in the Appendices. Where a litera-
ture/reference for the hydrolysis of a compound was obtained, the summary sheet
contains the second-order rate constant if applicable and first-order rate
constants at 25°C. For several of the compounds, lab data were generated in
this study to fill in gaps in the literature. . . ' .
Data from all the summary sheets were used to derive the values in T.a.b.l e
6. These values are the calculated rate constants at 25°C. The.rate constants
were assumed, to vary a factor of 10 for each 20°C change in temperature (Ref.
L, Section 1). This corresponds to an activation energy of about 20 kcal/mole.
when applicable extrapolated values (25°C) were obtained using activation
parameters. A temperature, correction was applied to all calculations invplv.ing
Kw or. [O'H'J. When statistical tests of the data indicated the hydrolysis was
' ' ' ' 13 ' '-.'.' " .
-------
v ...'**??'^^"jssw^^-wT^raeST'C^^
T1/2
R2.
'= 1.74.x. 10~2 min""1
= 39.8 min.
= 0.999
c
"c
'o
c
Q)
10
10
o
' 0
_T r r , _T_
50 . ... 100 150
Time (min)
200
Figure 1. Hydrolysis of DL-trans-4-Chlorostilbene
Oxide at 28°C,. pH 3.13
19
-------
K
T
1
1/2
2
10
0
2.04 x 10~2 min'
34. min.
0.994
Time (min)
100
125
Figure 2. Hydrolysis of Benzyl Chloride at 52.9°C,
pH 7.0
20
L
-------
T1/2
R2
8.07 x 10~3 min"1
85 min.
0.994
D)
C
«*
C
*o
(
0)
1.0 M
L
0
Figure 3.
_J,J,I
50 100 150
Time (min)
200
Hydrolysis of Methyl~2,4~Dich!orophenox^
Acetate at 28°C, pH 9.0
21
-------
^^^
4.0-
2.0-
1.0
3.0
3.1 .3.2
100G/T (°K)
3.3
Figure 4. Dependence of Benzyl Chloride
Hydroly.-Js on Temperature
-------
TABLE G. HYDROLYSIS. RATE CONSTANTS AND HALF-LIVES AT 25°C
LABORATORY DETERMINED RATE DATA
ro
CAS. Number
. 591-08-2
75-05-8 .
.53-96-3
492-80-8
115-02-6
305-03-3
57-74-9
494-03-1
91-58-7
126-99-8
53.44-82-1
542-76-7
50-18-0
72-54-8
Compound
n-(/CTinothioxo:nethyl )-
acet amide
Acetonitri lea
2-Acetyl ami ncflucrine
Aurainined
' -Azaserine
Chlorainbucil.a
Chlordane (cis-isomer)
Chloronaphazine3
Beta-Chlornaphthalene
2-Chloro-l,3-butadienea
l-(0-Chl orophenyl )thiourea
3-Chl oropropaneni t ri 1 e
Cyclophosphamide3
DDD.(p,p' isomer)
Rate Constants
ACID Neutral Base
M-l hr-1 . hr-1 M-l hr-1.
(1.7 t 0.2) X 10-5 i.5Q ±0.09
5.8 X 10-3 :
2.3 X 10-6 ' 6 X 10-3
5.5 ' 3.9 X 10-4
328 ± 20 . (2.6 ± 0.4) X 1Q-4 6.8 ±0.7
0.4'
.4.3 X 10-3
3.2 X 10-3
(9.5 ± 2.8) X 10-6
. Polymerizes in absence of inhibitors (no hydrolysis)
(9.8 ± 3.0) X 10-7 0.14 ± 0.03
(1.3 ± 0.1) X 10-4 12>071 ± 1,960
7.1 X 10-4
(2.8 ± 0.9) X 1Q-6' .5.2
Calculated
Half-Life .
at pH 7
4.6 yr
. ->150,000 yr'' . '
34. yr
74 d
9-9 d.
1.7 hr
M97.000 yr . ' .. ''[
i
216 hr .1
i
8.3 yr
.81 yr. . :
22 d ' :
41 d i
28 yr
-------
Table 6. cont. .. . . . . . .. ; . ' '
..-' . LABORATORY DETERMINED RATE DATA ' ' ' . '- ' .' . .
'CAS Number
20330-81-3
.2303-16-4 '
111-44-4.' -
7R-87-5
297-97-2
Compound
. Uaunomycin
Di all ate
Dichloroethyl ether3
1 ,2-Dichloropropane
0,0-Di ethyl -0-pyranzinyl
.Rate Constants
ACJD Neutral-
M-l hr-1 hr-1
(9.7 ± 0..5) X 10.-5
(1.2 t 0.7) X lO"5
3.2 X ID"2
(5.0 ± 0.2) X 10-6
(1.0 ± 0.06) X 10-3
Base
-M-l hr-1.
10
0.9 i 0.4
4.3 X I'O-4
7.3 ± 0.7 ..
Calculated- . .. .'".
Ha If -Life . ]
' at pH 7
298 d.
6.6 yr ;
22 hr
'
15.8 yr'. . i
29 d ;
55-91-4
60-51-5
541-53-7
62-50-0
96-45-7
111-54-6
640-19-7
118-74-1
67-72-1
phosphorothioate
Dlisopropyl fluorophosphate3 3.8
Diniethoate3
2,4-Dithiobiuret
Ethyl methanesul fonatea
Ethylene thiourea .
Ethylene-Bis-(Dithio-
carbamic Acid) [as in. '
di sodium salt, .Habam]
2-Fluproacetarnid ;
7.2 X 10-3
1.7 X.10-4
(7.1 ± 1.3) X 10-3
1.5 X lO-2
28 9.6 hr
756 ' 118.hr
98 hr
' ' ''. . 46 hr
Zero hydrolysis observed after 90 days at 90°C and pH (3, 7, 9.)
848. 0.01 . . 69.hr
Kexachlorcsthane
^3.3 ± 0.3) X 10-5 2.4 yr
Zero hydrolysis observed after 13 days at 85°C.and pH (3, 7, 11)
Zero hydrolysis observed after 11 days at 85°C and pH (3, 7, 11)
-------
F
Table 6. cent.
LABORATORY DETERMINED RATE DATA
Rate Constants
CAS' Number Compound
ACID
M-l hr
757-58-4 Hexaethyl tetraphosphc.tta
465-73-6 Isodrin
303-34-4 la's i oca rpine
58-89-9 . Lindane -
109-77-3. Ma-lononitrile
148-82-3 Melphalana
16752-77-5 . Methomyla .
80-62-6 Methyl..methacryl ate
70-25-7 )l-Methyl-M-nitro-N-nitroso-
guanidine3
75-55-8 2-Methylaziridinea
56-84-2 Methyl th'iouracil
86-88-4 Alpha-Naphthaylthiourea
759-73-9 N-Nitrosp-N-ethylureaa
615-53-2 . f.'-fJi t roso-M-niethyl urethane3
4.9
Neutral
hr-1
Base
"1 hr'1
9.3 X lO-2 '
1.7 X lO-6 ..
(4.9 ± 0.1) X 10-5 9.3 ± o.i
(1.2 ± 0.2) X ID'4 198 ± 6
(1.35 ± 0.42-). X 10-3 806 ± 45
0.15
8.9 X ID'5 210
200 ± 47
2.7 X ID'2 9.5 X
4.0 X lO-3 8.0 X lO-3
(9.7 ± 2.7) X ID'6 .
(8.0 ± 2.4) X lO'5 9.9 X 10'2
63 0.19 . 5.3 X 106
9.5 2.9 X 10-2 2.9 X 103
Caicu1 ated
Half-Life
at p.H 7
7.5 hr
46 yr.
1.6 yr
206 d
20.2 d
4.6 hr
262 d
3.9 yr
19 hr
37 hr
8.2. yr
361 d
0.96 hr
24 hr
-------
.Table 6. cent.
LABORATORY DETERMINED RATE DATA
CAS Number
152-16-9
117-84-0
.298-02-2
1120-71-4 -
94-59-7
107-49-3 .
62-55-5
137-26-8 :
8001-35-2
126-68-1
ACID :
Compound . M~l hr~l
Octamethylpyrophosphoramide3 0.23 ± 0
Di-n-0ctylphthalatea
Phorate9
1,3-Propane sultone3
. Safrole Zero hydrolysis
Tetreethyl pyrophosphate3
Thioacetamide3 . (6.0 ± 0.06) X
Th iram ' . .
Toxaphene
0,0,0-Tri ethyl ester
Rate Constants
Neutral Base
hr'1 M'1 hr"1
.03 .IX 10-11
7.4
7.2.X ID'3 ;
8.2 X ID'2
observed after 26 days at 85°C and pH
9.3 X 10-2
ID'2 (8.6 ± 1.1) X 10-5 1.4 ± O.C9
5.0 X ID"3 4,153 ± 00
(8.0 ± 2.2) X ID'6 3.2 ± 2.2
(2.0 ± 0.2) X lO'5
Calculated
Half-Life
. at -pH 7
3,400 yr
107 yr
96 hr .
8.5 hr
(3, 7, 11)
7.5 hr
336 d
5.3 d
10 yr
3.9 yr
phosphorothioic Acid
2524-09-6 0,0,S-Triethylester >(2.0 ± '0.2) X 10'5 .. <3.9.yr
phosporodithioic Acid
126-72-7 Tris.(2,3-Dibromopropyl)- (1.0 ± 1.1.) X 10'5 78 : 4.4 yr
phosphate . .
a. Values were extracted from the references in Section 5 for the particular chemical. The neutral hydrolysis
rate for thioacetamide was determined at Athens-ERL. .
-------
pj=" S '
independent of pll, hydrolysis values from the extremes of pH (acid and/or base) .
were included when calculating the neutral hydrolysis rates reported in Table 6.
Confidence limits were calculated from the mean and standard deviation values
and are the values reported in Table 6.
, Constraints of time, personnel, bath space, and availability of instruments
.of analysis dictated that rate determinations be confined to shorter periods of
time (note the half-lives and temperatures in summary sheets). 'Ideally, decrease
in compound concentration was monitored through three half-lives (<12% remaining);
as- seen in the summary sheets, some compounds decreased <10% during the period
of analysis while others decreased to zero concentration.
. . An illustrative plot-on semi-log paper of % Remaining vs. Time is included
w.ith applicable data sheets. Included on the sheet are the pseudo-first-order
rate constants, half-life, and r?. .
27
-------
5.3.1 . N-(Aminot_h1bxpmethy1_)-acet_ain1_d_e
:CAS 'No. 591^:08^ .' ...'.'
HYDROLYSIS. AND ANALYSIS DATA
Hydrolysis Data: .. . .
pH . Temp.'°C k^hr'1) k^M^hr"1) t1/2(d) r2
3.28
3.23
3.28
7.16
7.16
9.64a
10.543
85
85
85
85 -
85
25
25
. 5.6xlO-3
-<. 5x10-3
4.5x10-3
0.51
. 0.52
0.26
0.90
5.2 '
6.4
6,4
0.06
0.06
.1.59 0.11
.1.41 0.03
.968
.979
.974
.996.
.999.
Congdon,- W. I. and J. T. Edward. 1974. The Alkaline Hydrolysis
of M-Acylthioureas. Can. J. Chem. 52, 697-701. .
Comments: The hydrolysis rate constant of fi-acetylthiourea levels
off at.higher concentrations of hydroxide ion. A 22,000-fold
increase in hydroxide ion concentration caused only a 170-fold
increase in the pseudo first-order rate constant. .Presumably
hydrolysis of N-acetylthiourea involves reaction of the
un-ionized molecule (dominant at lower pH) with hydroxide ion. :
Water Solubility: .
Source: Aldrich -.-.'.
Listed Purity: 99" Identity-Purity cbmfinned, by.spectral analysis.
Analysis Concentration: 2 ppn ...
Analytical Procedure: N-(A.iii nothioxomethy] )-acetamidewas
analyzed, by 20-rnicrol iter injections onto a.Resolvex Cig column.
.Instrumentation: GC HPLC X ' . .
Detector: UV at 276 n;r, '. '; ' '
. Gclumn: Resolvex C^, 10 micron, 25 cm' ' - ;
Mobil'; Phase: acetonitrile: water (50:50)
28
1
-------
5.3.1 N-(Arninofhioxomethyi)
Acetamide
K! =5.1 x 10~1 hr~1
T1/2 = 1.4 hr
R2 = 0.999
a>
c
[c
*D
E
a>
0.0 1.0 2.0 3.0 4.0 5.0 6.0
10
10
Figure 5.3.1
Time (hr)
Hydrolysis of N-(Aminothioxomethyl]
-Acetamide at 85°C, pH 7.16
29
-------
5.3.2..: Ace torn tri le : .
CA5 ?:o. 7^05^ ...-. . -
HYHHOLYSIS AND ANALYSIS DATA
.Hji.'ro lysis Data: . - ,
pH '-:
3.2f>
6.
9.
9.
10.
10.
10.
10.
10.
99
95
95
93
42
42
13
13
Ten p.
85.
85.
S5.
. 85.
23.
65.
66.
85.
85.
CC
0
0
5
5
0
0
0
5
5
h'o measurable
No measurable
No ;noisurasl
a
' No measurable
o
0
0
0
No measurabl
.0012
.0009 . . .
.0032.
.0052
e
0
2
hydrolysis
hydrolysis
hydrolysis
hydrolysis
hydrolysis
.3C*
.30*
t't/z
over
over
in
in
i n
24.
32.
3.
5.
1
1
1
1
2
5
5
r*'
31 days.
31 days.
.5
.5
7.
d
d
d
d
hours. .
hours.
5 hours.
-- - - '
0.919
0.975
* average of two runs .- .
Go:nc;onts: Hydrolysis of alky! niVriies is a known acid or base
catalysed process. A second-order basic hydrolysis rate constant
was doti?nninod at 66°C and H5°C. Tno calculated energy of
activation (27.7 Kcdl/molo) was in good agreement with .the value
of 23.7 Kcal/niole reported by Gueison (1). The extrapolated second-
order alkaline hydrolysis rate constant (1 x !0"^'-'"'nr*l) is in good
agreement with the value measured at 25°C by Peskoff and Meyer .
'(5.67 x lO-^l-^hr-l) (2). ' ' .
1.. Gueison, A. G. and V. A. Linetskii. 1969. Alkaline Hydrolysis of
Nitrilcs. ' Khim. Pron. (Moscow). j4_5(4)., 2:54-205, '
2. Peskoff fl. and J. Meyer. 1-913. Zur Kenntnis der folgereaktionen. Ill
Die Hydrolyse von Saureamiden und N'itrile. Z. Phys. Chem., ;32, 129-163.
.'..'ater Solubility: -Miscible- .
Source: Aldrich . .. . ' :
Listed Purity: 99.95, con-finned by spectral -analysis
Analysis Concentration: 10.?, pp.. ' - .-
Analytical Procedure: '.Experiments.'wore conducted in 10.0 ml
glass sealed ampules to prevent thfi .evaporation' of'the compound.
n-: G" _X_ HPLC..__ ' - ". .'
'-. - - " 30' ' " - . ..'.'
-------
Detector: FID
Column: DBWAX, 1.0 micron.film, 30m x 0.53mm ID
.Temperature -Program: 30°C isothermal
31
-------
5.3.2 Acetoniirile
- 10
~1 '1
T1/2
R2
1.25 x 10~ hr
5.5 days
0.974
OV
C
V
"o
E
G)
0
1 Oy-p~T -] . [ 1 [i 1 T 1 rp
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0
Time (days)
Figure 5.3.2
Hydrolysis of Acetonitrile at 85.5°C
pH iO.13 -..'.;
32
L.
-------
5.3.3 2-Acetylaminofluorene
L
. No. '53-96-3- .
ro lysis
pll
2.97
2.97
2.49
2.49
7.34
9.80
9.80
10.25
10.25
10.39
10.39
10.-39
HYD
Data: .
Temp.°C
85.5'
85.5
85.6
85.6
.85.5
85.5
85.5
85.5
85.5
85.6
85.6
85.6
ROLVSIS AND
kjfhr-1)
0.0019
0.0024
0.0059
0.0073
0.0007 .
0.0024
0.0023
0.0040
0.0042
0.0152
0.0151
0.0516
ANALYSIS DATA
k2(M~1hr"1)
1.77
2.24
2.13
2.26
i.ie
.1.13
0.70
0.73
1.93
1.91
1.97
t1/2(hr.)
365
239
100
95
990
289
301
173
165
45
46
44
?
0.907
0.932
0.999
0.999
0.863
0.933
0.932
0.988
0.981
0.999
0.999
0.999
! Comments: Acetanilides are very stable in aqueous solution.
I They undergo specific acid and base catalysis with maximum
stability in the pH range of 5 to 7.
Water Solubility: 10.13 * .52 mg/1 at 26.3 ± 0.7°C
. Source: Aldrich , .
Identity-purity confirmed by spectral analysis.
" ' Analysis Concentration: 0.3 -- 1.5 mg/L .
I- . .Analytical Procedure: 0.005M buffered water inj'ected directly
| onto a 20 niicroliter injection loop.
j : ' . Instrumentation: GC __ HPL'C 'x
i ' . . ' ' '"'' ''''
}. '' Detector: Kratos Spectroflow 757 .. '
i ' . . . '
i . ' '
i . Column: 'ODS Ultrasphere, 4..6 mm ID x 1'5 cm, 5 micron
Mobile Phase: .Methanol :water (70:30) . .'
33
-------
5.3.3 2 Acetylominofluorene
K
, = 6.9 x 10~3 hr"1
/2 ~ 4.2 days
R
2
= 0.999
i
D)
C
'c
~*
a
E
10
0.0
1.00.0 200.0
Time (hr)
r
300.0
Figure 5.3.3
Hydrolysis of 2-Acetylaminofluoren
at 85.6°C, pH 2.49
34
L.
-------
5.3.4 __
CAS No. 49^j30-8 ' '
-... '.' HYDROLYSIS AND ANALYSIS DATA
Literature Data: :
'. Aurami.rie is a weak base that forms salts with hydrochloric, sulfuric, and
other acid's.' Auramine decomposes at temperatures .above'. 70°C. Del ben et al.
(1) reported a second-order acid rate constant of 5.5 M-l hr-1. Holmes and Darling
(2) reported the hydrolysis of.auramine in neutral solution. The calculated
activation energy and hydrolysis rate at 25°C was 23.SOO t 700 .cals/mole and
0.00038 hr-1 respectively (log A = 14.02 ± 0.51). In alkaline solutions (3) the
free imine functional group undergoes a slow reaction with water to yield a
carbinol. .Equilibrium is reached after a few days at room temperature and is
characterized- by an equi 1 ibriuin constant pK = 9.8.
1. . D.ulben, P., S. Paoletti and V. Crescenzi. 1976. On the Fa.ding of Auramir^
0 in the Presence of Ueak Polyacids in Water. Eur. Polynu J. , _12, 813-Pi5.
2. Holmes., W. C. and J. F. Darling. 1924. The Hydrolysis of Ajramine. J. Am.
' Chem. Soc. 45, 2343-23'^.
3. Goldacre, R. J. and J. W. Phillips. 1949. The lonization of Triphenylmethane
Dyes. J. Cheni. Soc., pp. 1724-1/32. '
35
-------
5.3.5 Azaserine
; NO.
irolys
pH
3.20
3.20
3.20
3.17
7.00
7.00
. 7.00
7.47
7.47
7.47
10.37
10.37
10.37
8.87
8.87
8.87
115-02-6
is Data:
Teup.
45
45
45
23
65
65
65
84
84
84
66
66
66
35
85
. 85
HYDROLYSIS. AMD
°C k (hr)
i . 53:
1.53
1.61
0.18
0.0145 .
0.0137
0.0188
0.15
0.17
0.17
1.88
1.73
2.24
0.925
0.826
0.780
ANALYSIS D
k2(M-lhr-
2504
2425 .
2552
266
. 608
560
725
3950
3540
3340
tl/2
[
i -> on vie i co ocn/t g.43 hr 0.994
.0.43 hr 0.993
0.43 hr 0.916
3.84 hr 0.988
i
' -' 1.99 d 0.952
2.11 d 0.928
1.53 d 0.821
4.56 hr 0.997
4.32 hr 0.997
4.32 hr 0.999
t
1 0.36 hr 0.998
0.41 hr 0.988
0.31 hr 0.999
0.75 hr 0.922
| 8.87 85 0.826 3540 O.S4 hr
'[ 8.87 . 85 0.780 3340 0.89 hr 0.993
Comments: Energy of activation and log A for the acid catalyzed hydrolysis is:-
19,064 ± 1,683 cals/mole and 16.5 ± 0.14 respectively. The hydroxide catalyzed
hydrolysis yielded an activation er.er.gy of 22,150 cals/mole and log A = 17.08 ±
0.94.
Water Solubility: > 1.0 g/L
Source: Sigma . .
Listed Purity: None stated
! ' Analysis Concentration: 7 my/L ' . .
Analytical Procedure: Azaserine was analyzed by direct injection of 20 ml
of solution into Zorbax NHj column for each sample. . ' .
Instrumentation: GC HPLC X . ' '
Detector: UV at 252 nm' .' .:-':..:
Column: Zorbax Nib (25 cm) or tnicro-Bundapak C^g (30 cm) ' '
Mobile Phase: Methanol : 0.05 M flal-^PO,} (50:50.)' ' . . . .;
. ' '. 36 '. . ' - :'''
L.
-------
r
CD
C
a
E
0)
Ql
5.3.5. Azaserine
Kj = 2.2 hr~1
tj/2.^ 0.3 hr
R2 '='0.999
101-
10
0
0.0
0.2 0.4 0.6
Time (hr)
0.8
Figure 5.3.5
Hydrolysis of Azaserine at 66°C,
pH .10.37
37
-------
5.3.6 Chlorambucil
' ; '.CAS.Wo.; 305-03-3' . - ' '-..''.'
i '"-'' ' ' ' '
[ . - ..\. ; ' ' HYDROLYSIS AND ANALYSIS DATA
i '':.'.
! Literature Data: .
..Chlorambucil is one of a series of nitrogen mustards tested as anticancer
". drugs (5.3..0, 5.3.13, and 5.3.34). Hopwood and Stock (1) reported a neutral
hyiJroiysis rate constant jf.0.38 hr-1 at 25°C (half-life l.S.hr).
1. Hopwood, W.J. and J. A. Stock. 1971/1972.. The F.ffect of Macromolecules
upon-the Rates of Hydrolysis of Aromatic Nitrogen Mustard Derivatives.
Chan. Biol. Interactions. 4, 31-39.
38
-------
5.3.7 Chlordane...
CAS No. 57-74-9 . ;
. . , HYDROLYSIS AMD ANALYSIS DATA
Hydrolysis Data: cis-Chlordane^
'i. '
I
I
!
t
V"
I.
. PH.
10.18
10.18
10.18
10.85
.Iemp.°Cv
84.0
84.0
84.0
65.0
k^'hr'1)
0.36
. 0.34
0.32
0.04
k2(M'1hr-1)
78.8
74.4
70.0
4.7
t1/2(d)
0.03
0.08
0.08
0.70
r2
0.986
0.989
0.977
0.995
1. 57-74-9 is CAS Mo. for technical chlordane
2. Zero degradation was observed for trans-chlordane during five days
at pHs of 3, 7, and 11 and at 85°C. The only degradation observed
with £j_s_-chlordane is reported above.
Comments: The two major components of technical chlordane are the cis and
trans isomers. The data above are consistent with the structures of the isomers.
cis-Chlordane (CAS No. 5103-74-2) is more susceptible to hydroxide catalyzed
delTydrohalogenation because the 1-exo, 2-exo orientation of the chlorine atoms
| facilitates the E? elimination of HC1. The trans isomer (CAS No. 5103-71-9)
has.1-exo, 2-endo orientation of the chlorine atoms and thus does not undergo
E2 elimination. Calculated activation energy for alkaline hydrolysis of cis-
chlordane is Ea = 34,966 ± 1,800 cals/mole, log A = 23.3 ± 0.10. . ; .
Water Solubility: 56 ppb
Source: RTF
Listed Purity: . . .
Analysis Concentration: 5 ppb in H20 : . .
Analytical Procedure: Extract 10 ml buffer with 1 ml 50 ppb Endosulfan II in
. ' isooctane. Add 2 ml isooctane and shoot.
Extraction Solvent: isooctane
. . .Instrumentation: GC X HPLC . ' '
3.9
-------
Detector: ECD
Column: CV-1, 2.65 M,'0.53mm'ID, .5m long
Temperature Program: 190°C.isothermal
Mobile Phase: H/A
Internal Standard: Endosalfan - II, 17 ppb
-10
-------
I
5.3.7 aChlordane
~2 "1
T1 /2
R2
- 4.1 x 10~z hr
= 0.7 days
= 0,995
lU^T
d> -
£
f V
Q)
a: -
^ _
m°
JN.
0.0
i ' : i r
1.0 2.0
Time (days)
3.0
Figure 5.3.7 Hydrolysis .of a-Chlordane at 65°C,
pH 10.85 ;..;
'-'.. '.. 41 '
-------
5.3.8 ': Chlornaphazine
CAS No. 494-03-1
HYDROLYSIS AND ANALYSIS OATA
Literature .Data: ".-.'
Chlornaphazi ne, .a nitrogen mustard, undergoes netural hydrolysis with a
half-life of 216 hours (1). . ' . ' .
1. Ghielmetti, G. 1950. Caratteristiche Di Una Azotoiprite Aromatica La'
Bi s(2-chloroeti 1 )-s-flafti lamina. Farmaco Ed. Sci. 5, 275-280.
-------
r
5.3.9 Beta-Chlornaphthalgne
CAS No. 91-58-7
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: '
pH
3.04
3.14
' ' ' 3.19
2.93
2.93
7.10
7.14
7.30
7.30
7.0C
7.06
. 9.65
9.58
9.75
. 9.75
9.51
Temp. °C
85.5
85.5
85.5
85.8
85.8
85. 5
85.8
85.5
85.5
85.5
85.5.
86.0
85.5
85.5
85.5
85.6
X103k1(hr1)
4.23
1.51
1.10
2.72
2.46
4.44'
3.28
1.25
2.03
1.23
1.25
6.60
2.84
3.46
1.81
3.50
ko(M hr~l) ti/ofhr)
163.0
459.0
630.0
255.0
281.0
156.0
211.0
554.0
341.0
563.0
554.0
105.0
244.0
200.0
382.0
198.0
r2
0.977
0.959
0.880
0.989
0.964
0.978
0.873
0.971
0.928
0. 729
0.660
0.661
0.985
0.974
0.978
0.822
Comments: Data for all pHs were combined and used to calculate the neutral
hydrolysis rate constant.
Source: RTP lot No. 0130
Listed Purity: 99£ .
Analysis Concentration: 1.6 ppm
Analytical Procedure: Extract 10 ml of aqueous sample with 3.0 ml. isooctane.
Dilute extract. 1:1 with internal standard solution (2,4-D methyl ester 200 ppb).
Extraction Solvent: Isooctane .
Instrumentation: GC X HPLC . . . . ...
Detector: ECD. . . . .
Column: DB-1 30m, .32mm.ID ' . . .
Temperature Program: 170° Isothermal. - . ...
Internal Standard: 2,4-D Methyl ester at 100 ppb
- ''".'' .: 43 - :'-..'-'';'..'
L
-------
5.3.9 B Chloronapthalene
K
= M.2 x
Ti /o ^ 23 days
/ *~
R2 .-0.9706.
o>
c
'c
a
E
a
:,\
.10--
10U-
0.0 .100.0. . 200.0 300.0
'. Time (hr).
1-00.0
Figure 5.3:9 Hydrolysis of B-Ch!oronapthalene
. . at' '35.5°r, pH 7.30 '
44
-------
f ' ' ' ' -
* -
f . ' . 5.3.10 2-Chloro-l,3-butadiene
i ' -'..
CAS No.
HYDROLYSIS AND ANALYSIS DATA
i Literature Data: . " .
i ' ..-.' .
' Chloroprene-(2-Chloro-l,3-butadiene) polymerizes spontaneously at room
temperature and forms cylic diniers on prolonged standing in the presence
of polymerization, inhibitors (1). Chloroprene is stable to hydrolysis. On
refluxihg with concentrated alcoholic sodium hydroxide, alcoholic silver
nitrate, or pyridine, only traces of chlorine aro split off (2).
1. Bauchuritz, P.S. 1964. Chloroprene. In: Kirk, R. E. and Othmer, D. F.,
eds., Encyclopedia of Chemical Technology, 2nd ed. , Vol. 5, New York, John
Wiley and Sons, pp..215-231. .
2. Carothers, VI. H., I. Williams, A. H. Collins and J. E. Kirby. 1931.
Acetylene Polymers and their Derivatives II. A Mew Synthetic Rubber:
Chloroprene and its Polymers. J. Am. Chem. Soc. 53, 4203-4225.
L
-------
.5.3.11 l-(.Q-ehloropheny1 )fhiourea
> No.
Irolysi
pH
3.24
3.24
' 3.24
7.16
7.16
7.15
7.09
7.09
9.57
9.57
9.57
5344-82-1..
s Data:
;. . Tomp.°C
85 . .
- 85
85
85
85 .
85
65
65
85
.35
. 85
HYDROLYSIS
X103k1(hr.-1)
0.010
0.011
0.011 .
0.015
0.019
0.019
0.0007
0.0013
0.044
0.048
0.041
AND ANALYSIS
k2(M-1hr'1)
41.1
44.8
38.3
t1/2(hr) r2
2.9 0.914
2.7 0.994
3.24 85 0.011 . .2.7 0.969
I ' . ''.; . ' ... - . "
1.9 0.996
1.5 0.967
.1.6 0.912
40.1 0.956
22.7 0.860
0.7 0.986
0,6 0.977
0.7 0.988
Comments: .Calculated energy of activation and log A for hydrolysis at pll 7 was
34,482 ±7.295 cals/mole ami 19.29 ± 3.05, respectively. Extrapolation to 25°C
was based on Ea = 34,482 calr,/mole. .
Source: Aldrich
Listed.Purity: 98% Identity-purity confirmed by spectral analysis.
| Analysis Concentration: 2 ppm
Analytical Procedure: Direct injection onto HPLC column, high pH samples
were neutralized before analysis.
Instrumentation: GC HPLC _X_ '
Detector: UV at 264 nm
'Column': -Nova Pak C^ .
Mobile.Phase: Acetonitrile:Water (50:50)
46
-------
O)
c
*c.
*o
E
0)
o:
K1
T-1
R2
10
10°-}-
0.0
l-(o-Chlorophenyl)
thiourea
4.4 x 10~2 hr'
= :0.986
20.0
40.0
Time, (hr)
60.0
figure 5.3.1 1
Hydrolysis of 1 -(p-Chlorophenyl)
ihiourea at 85°C, pH 9.57
47
L.
-------
r
5.3.12 3-Chloropropanenitrile
CA-i.No. 542-76-7
.HYDROLYSIS AMD ANALYSIS DATA
Hydrolysis Data:
pH . Temp.°C k^hr'1) k2(M'ihr-1)
3.22
3.22
.? 22
3.15
3.1:
6.92
6.92
6.92
6.92
7.19
7.01
7.01
7.04
7.04
9.S2
10.49
10.49
8.56
8.56
9.11
9.11.
85.5
85.5
85.5
85.1 '
85.1
45.4
45.4
. 45.4
45.4
8.5.5
65.6
65.6
65.0
65.0
85.5
45.4
45.4
25.5
25.5
25.5
25.5
0.0029
0.0025'
0.0036
0.0026
0.0036 '
0.0344
0.0278
0.0274
0.0249.
None lett
0.422
0.401
0.443
0.463
None 1 eft
None left
None left
0.0491
0.0407'
0.1774
0.1509
at first
at 0 t ine
at O.time
at 0 time
13004
10779
13241
11263
9.8 d
8.2 d
8.1 d
11.1 d
.8.0 d
20.1 hr
24.9 hr
25.3 hr
27.8 hr
time point.
1.7 hr
1.7 hr
1.6 hr
1.5 hr
point.
point.
point.
14.1 hr
17.0 hr
3.9 hr
4.6 hr
0.995
0.987
0.975
0.968
0.974
0.995
0.999
0.994
0.999
0.982
0.993
0.967
0.993
0.941
0.989
0.984
0.978
Water Solubility: 45000 mg/L at 25°C .
Source: Aldrich
! Listed Purity: 98" Identity-purity confirmed by spectral analyt,nn ID
:.. .-.- ." ' ' ;. 43 - ':
L
-------
. Temperature Program: 90°C to 160°C at 40°C/min hold fjr 6 min at 160°C.
.Internal Standard: MalononitrHe at 10.4 ppm
49.
-------
*?'
5.5.12 3Chroropropanenitrile
R
2
/= 6.7 x 10'
- 1.7 hr
- 0.993
hr
~1
CD
^C
*C
*O
E
Q)'
0.0
1.0 2,0 3.0 4.0
.. Time (hr)
5.0.
Figure 5.3.12 Hydrolysis of 3-Chloropropanenitrile
; , ' :at 22.8°C, pH 7.01
''"'. . "' 50 ; " . . '"''.
-------
r : -.5.3.13 Cyclophosphamlde .' .. . . ' . '. .
| CAS N'o. 50-1S-0 ..'-''.-.
t '
; ' HYDROLYSIS AND. ANALYSIS DATA
{ '"'..
f Literature Data: .
> The hydrolysis of cyclophosphanride is independent of pH in the pH 3-10
[ region. Kensler (1) reported a neutral hydrolysis rate constant of 7.14 X 10"4
|. hr-1 and activation energy of 25,000 cals/mole. The half-life at pH 7 and 25°C is
! 40 days. . .
t
^ . . -
f . - -
1. Kensler, T. T., R. J. Behn^ and D. Brooke. 1979. High-Performance Liquid
Chromatographic Analysis of Cyclophosphamide. J. Pharm. Sci. 68, 172-174.
1
*
L,.
51
-------
5.3.. 14 DDO (p,p* isomer)
CAS flo. 72-54-8 , , .
'. . . . HYDROLYSIS AND ANALYSIS DATA
Hydrolysis .Data:
: . . pH Temp.:°C X103k1(hr-1) k^r^hr'1) t1/2(d)
3:21
3.21
'... 3.21
. 7.22 .
7.22
; ' 7.22
\. ' ' .
9.67
: 9.67
9.67 .
10.26
; . 10.26
i
'85
35 .
85
85
85
85
85
85
85.
65
.65
.1.0 .
0.9
0.5
4.9
5.4
4.6
731
867
622
29!
305
495
579
420
127
133
28.8
31.9
60.0
. 5.9
5.3
6.3
0.04
0.03
0.05
0.10
0.09
0.800
0.842
0.886
0.997
0.999
0.994
0.985
0.999
0.974
0.975
0.994
Comments: The calculated energy of activation for basic . .
hydrolysis, is Ea = 16,143 ± 2,051 cals/mole, log A = 12.5 ± 0.7.
Water Solubility: .
Source: RTP
Listed .Purity: 99%
Analysis Concentration: 4.o.pg/L Confirmed by spectral analysis.
Analytical Procedure: Extract 10 ml buffer witii 2 ml (7 iig/L)
Endosulfan I in isooctane. Final analysis concentration was
24 ^g/L ODD and 7.2 pg/L Endosulfan I.
Extraction Solvent:. Isooctane
Instrumentation: GC X
"''' .-'.-'
Detector: ECD
' ; '.''.. ' ' '
Column: OV-1, 2.61i micrcn film, 5m x O.C3mm ID
'''' '
Temperature Program: 200°C isothermal
.Internal Standard: Endosulfan I
52
L-.
-------
5.3.14 ODD
T
,/2.
R-
2 _
U)
^c
*c
'o
£
10l
= 4.9 x 10~3 hr"1
= 5.9 days
0.997
0.0 50.0 100.0 150.0 200.0 250.0.300.0
';".... ". Time (hr) . . .. .
Figure 5.3.14 Hydrolysis of ODD at 85°C, pH 7.22
'' .53 '''''
L
-------
j. 5.3.15 baunomycin
CAS No. 20830-81-3
HYDROLYSIS AMD ANALYSIS DATA
Hydrolysis Data:
1 IT O
pH Temp.°C ki(hr ) ko(M hr"1) tj/p(d) rc
3.21
3.21
. 3.21
7.09
7.09
t 7.09
9.13
9.18
; 9.18
9.70
9.70
9.70
'(' Comments:
hydrolysis
85
85
85
85
85
85
85
85
85
65
65
65
0.039
0.038
0.040
0.027
0.027-..
0.029
1.63
1.42
1.60
0.45
0.37
0.29
The calculated energy
is: E, = 2
0,455 ± 3,6
3420
2990
3350
710
600
460
of activation
71 cals/mole a.
0.73
0.76
0.72
1.C7
1.05
1.01
0.02
0.02
0.02
0.06
0.08
0.10
for base
id the loq
0.953
0.955
0.944
0.994
0.990
0.997
0.936
0.988
0.979
0.927
0.963
0.938
cataly
A = 1
Water Solubility: Daunomycin hydrochloride is readily soluble
in water.
Source: Fluka
Listed Purity: Not stated
Analysis Concentration: 3.6 mg/L
Analytical Procedure: Daunomycin was analyzed by direct
injection of 20 microliters of each sample.
Instrumentation: GC HPLC X
Detector: UV at 532 nm.
Column: . f!ova-Pak C^g, 15 .cm
Mobile Phase: acetoriitri le:water (50:50) with .005 M Pic B 8
54
-------
IT*" '
5.3.15 Daunomycin
1/2
R2
.= 1.4 hr~1
= 0.5 hr
= 0.988
O)
c
*c
*o
E
Q)
CtL
101
10
o
0.0
0.2 0.4 0.6
Time (hr)
0.8
1.0
Figure 5.3.15 Hydrolysis of Daunomycin at 85°(
pH 9.18 :
55
-------
r
'5.3.16A :Cis-Oiallate , .
CAS No. 2303^-16-4* .. .: . . .
HYDROLYSIS ADD ANALYSIS DATA
Hydrolysis Data: ' . ' .
pH ' Temp.°C k^hr'T1) l^f-rV'1) t1/2(d) r2
' 7.20 0.927
5.80 0.933
0.21 0.900
0.24 0.993
i
' 5.80 0.996
I 6.98 . 65.1 0.015 . 1.90 0.960
0.23 0.961
0.56 0,810
2.30 0.932
0.73 0.383
0.83 0.919
0.38 0.977
5.3.
CAS
3.07 65.0
3.09 65.1
3.12 35.0 .
3.02 85. o
7.'08 65.3
6.98 . 65.1
7.04 85.0
7.09 85.0
9.87 65.0
9.61 35.0
9.61 35.0
9.65 85.0
16B Trans-Dial!
No. 2303-16-4*
0.004
0.005
0.140
0.113
' 0..005
0.015
0.101
0.052
0.012
0.039
0.033
0.033
ate
. . HYDROLYSIS AND. ANALYSIS DATA
Hydrolysis Data:
PH
3.07
3.09
3.02 '
3.12
7.08
6.98'
7.04
7.09
9.61
9.61
9.65
Temp.°G
65.0 '
65.1 .
34.3
85.0
65.3
65.1
35.0
' 85.0
85.0
85.0
35.5
k^hr"1)
0.004
0.006
0.115
0.139 '
O.OC5 '
0..015
o.ior
0.055
. 0.299 '
. 0.-302
0.456
k^M^hr"1) t1/2(d)
' 7.90
4.80
' ' 0.25
, 0.21 .
.. 5.8'Q
'.-1.90
0.28
. 0.53
233 0.09
235 '0.09
.-318 .0.06'
r'
.0.934
0.927
0.997
0.893
0.938
0.974
. 0.960
0.741
0.888
0.919
' 0.913
*Mixture' of £is arid _t^rd_n_s isonecs
: ". ' ' . ' 56
-------
Comments: Smith and Fitzpatrick (1) reported the complete breakdown of diallate
at 75°C in 12N sulfuric acid and IN sodium hydroxide. Dial late contains
approximately equal amounts of the cis and t ra ns i comers. Under the much milder
conditions employed in our hydrolysis studios, the hydrolysis mechanism anc rate
under acidic and neutral conditions were essential ly the same. Hydrolysis of
the trans isomer was catalyzed by hydroxide ion while the cis isomer hyd-olysis
was retarded by a factor "of three.
1. Smith, A. E. and Anne Fitzpatrick. 1970. ..The Loss of Five Thiolcarbanate
Herbicides in fionsterile Soils. J. Agr. Food Chem. _18, 720-722.
Water Solubility: 14 mg/L"1 at 25°C
Source: EPA '..'
Listed Purity: 100^ Identity-purity confirmed by spectral analysis. .
Analysis Concpntration: 5CO ii
Analytical Procedure: Extract buffered diallate solution with 1 ml internal
standard solution (1.9 mg/L. Zinophos in acetonitrile). Dilute 1:5 with isouctane.
Extraction Solvent: Isooctane
Instrumentation: GC X HPLC __
Detector: NPD
Column: 15m, 0.53mm ID, DB-5, 1 micron film
Temperature Program: 140° - 180°C at 5°/min, hold lOmin at 180°C.
Mobile Phase: N/A
Internal Standard: 1.9 ppn Zinophos in acetonitrile.
57
-------
pr-
5.3.T6A cis-Diallate
K1
T1/2
R2
5.6 x 10~3 hr'1
5.2 days
0.934
icr-ra
c
*c
1
Q>
10'-
10
o
0.0
D
50.0 ". 100.0.
Time (hr)
. 150.0
Figure 5:3.1 6A
Hydrolysis of cis-Diallate at 65°C
. pK 3.09
-------
5.3.16B trans Diallate
O)
c
*c
'a
£
0)
ex
Kv = 5.6 x 10"*5 hr"
Ti/2 = 5.1 days
R2 = 0.927
10
o
0.0
50.0 100.0
Time (hr)
150.0
Figure 5.3.16B
Hydrolysis of trans-Diallate at 65°C,
pH 3.09
59
-------
F"
i
L
5.3.17 . Pich 1 oroethy 1 et'he r
CAS Ho'., -yi 1-44-4 . -
'. .. ', .... HYDROLYSIS AND. ANALYSIS DATA
Liter-ature Data:
-Van Duuren ct al. (1) measured a netural hydrolysis rate of 0.032 hr~l
.ancf half-lffe of 21. hours at 25°C.
1.. Van Duuren, 1^. L. , C. Katz, B. M. Goldschmidt, K, Frenkel and A. Sirak.
1972. Carcinogenicity of Halo-ethers. II Structure-Activity Relationships of
Analogs of B-isVchlproiaethyl )ether. J. fiat. Cancer Inst. 4^, 1431-1439.
60
-------
5.3.18. 1,2-Dichlorbpropane .
CAS -No. _78187I5 '
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp;°C .X103k.1(hr-1} ' k.^M'^r'1) t1/2(d)
3.19
3.21
3.21
7.20
7.15
7.15
9.60
9.60
9.60
9.96
9.96
85
35
35
35
85
85
85
85
85
66
66
'1.39-'
1.72
1.46 .
1.47
1.69
. 1.22
2.99
3.16
2.73
U.26
0.27
. 2.60
2.75
.2.37
0.24
.0.24
21
17
20
20
17
24
10
9
11
111
107
0.913
O.S44
0.970
0.973
0.953
0.986
0.977
0.971
0.936
0.785
0.831
Comments: The.calcul ateu energy >f activation for basic hydrolysis is 30,
cals/mole. The extrapolated basic K, at 25°C is 4.3 x 10'^ M'1 hr'1.
Water Solubility: . . .
Source: Al drich . ' . :
Listed Purity: 99" Identity-purity confirmed by spectral analysis.
Analysis Concentration: 0.31 ppm .
Analylical Procedure: Extract 10 ml buffer with 1 ml 102 ng/L
1,3-dibromopropane in isooctane. Dilute 1:1 with isooctane and
analyze. Final concentration was 1.5 ppm 1,2-dichloropropane and
51 ug/L 1,3-dibromopropane. : ' .
.Extraction .Sol vent: Isooctane . '
Instrumentation: GC 'X HPLC ' . .
Detector: , ECD '. ' . '
'Column:. DB-5, 5 micron f i 1 m," 1 rvn x 0.53mm . ' ....
Temperature Program: 75°C for 2 :nin to.250°C for 1 min at
12°C/min. ' - . ' . . ', . . /
Internal Standard: .1,3-dibroiiiopropane .. ' : . . ' . '
.-..'' ' 61 '.'' ' .
700
ttj^V-a i.i -A -iJ^.*,..,- . ..
-------
5.3.18 1,2-Dichloropropane
T
1/2
R2
= 1.2 x 10~3 hr~1
= 24 days
= 0.986
CO
£
| 10'-
0.0
50.0 100.0 150.0
Time (hr)
200.0
Figure 5.3.18
Hydrolysis of 1,2Dichloropropane
at 85°C, pH 7.15
62
L.
-------
L
5..3.19 .0.0-Diethy1-0-pyraz1ny1 phosphoro thioate
CAS. No. . 297-97-2
.HYDROLYSIS AND ANALYSIS DATA . ' ..
Hydrolysis
' P.". ;.'
" \'3.12-
3,12
.3.12
7.22
7.15
7.15
7.15
10.00
10.00
10; 00'
10.00 .
Data:
, Temp.°C
''85
85
,85
85
'85
.85
85
65
65
65
65
Mhr'1)
' '0.18 '
0-16
0.16
: 0.19
0.16
0.17
0.17
' 0.42 '
0,41
0.38
0.37
.k-,(M-1hr~1-) v1/2(d)
0.16
0.18
0.18
0.16
0.16
0.17,
0.17
335 0.07
. 323 0.07
.304 0.07
261 0.08
r2
0.978
0..97S
0.987
0.992
0.997
0.994
0.998
0.985
0.998
0.972
0..974
Water Solubility:
Source: RTP
Listed Purity: 98.7% identity-purity confirmed by spectral analysis.
Analysis Concentration: 95
Analytical Procedure: Extract 10 ml buffer with 3 ml of 0.52 ppm Disulforon in
iso-octane
.
Extraction Solvent: Isooctane
Instrumentation: GC X '
' ' '
Detector: NPD . . ' . '
Column:- 30m.OV-l, l.Orn fil-n, 0.32mm ID . . ': ''-'.
Temperature' Program: 160°C for 3 min then 10°C per mi n to 2?0°C hold at
22n°rf'or. 10 min. , .
' ' . ' ..'''.'' '
Internal Standard: Disulfoton . .
-------
a>
c
*c
'a
£
. Q
a:
KO
C\
5,3.19 0,0-Diethyl-O-pyrazinyl
phosphorothioate
K1 - 4.1 x 10"' hr"
T1/2 ='1.7 hr
R2 '.=' 0.998
0,0
.1
1.0
2.0
ime (hr)
3.0
4.0
Figure 5.3,1 9 Hydrolysis ;jf. 0,0-Diethyl~0-p.yraziny
phosphorothiodte at 65°C, pH 10.00
64
-------
r
5.3.20 Dilsopropyl fluorophosphate
CAS Ho. 55-91-4
HYDROLYSIS AND ANALYSIS DATA
Literature Data:
Kilpatrick and kilpatrick (1) have reported the acid, neutral, and base
hydrolysis rate constants as 3.8 M'1 hH, 7.2 X 10'3 hr-* and 27.6 M'1 hr'1,
respectively at 25°C.
1. Kilpatrick, M. and M. L. Kilpatrick. 1949. The Hydrolysis of Diisoprcpyl
Fluophosphate. J. Phys. Colloid. Cliem. 53, 13/1-1384.
55
-------
i
^f-r .
5.3.21 Dimethoate
CASTIo, .60-51-5
''. ' . HYDROLYSIS AMD ANALYSIS DATA
f Literature Data:
..The rate constant for neutral hydrolysis at 25°C is 1.72 X 10"4 hr-1 with
an alkaline second-order rate constant of 7F,5 M~l hr-1. The reported rate and
half-life were extracted from Grimmer et. al. (1) who measured the rates of
hydrolysis of several phosphate esters at 25°C and 40°C and from pH 2 to 10.
1. Grimmer, F., W. Dedek and E. Leibnitz. 1968. I. Mitt. Hydrolysegeschwindigkeit
Und Mechanismus. Z. Naturforschg. 1958. B23(l), 10-17 ;
66
-------
'5..3.22 2,4-Ditniobuiret : . .
CAS Mo. 54J_-53-7 .: - . - .
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: - . ;
pH Temp.°C ' k^nr'1) k'2(M-1hr'1) t1/2(hr) r2
3.07
3.03
3.03
7.12
7.12
.7.04
7.04
9.60
9.60
9.99
85
85
65
85
85
65
65
85
85
65
0.52
C.55
0.08
1.13
1.33
0.26 .
0.26
1.12'.
0.84
0.24
1.2
. 1.4
8.7
0.7
0.5
2.6
2.6
0.7
0.7
2.9
0.999
0.841
0.990
0.922
0.944
0.976
0.943
0.887
0.996
0.861
Comments: Rate data at pH 7 and 9 were used to calculate a neutral ensrgy of
activation and log A (Ea = 17,814 ± 3561 cals/mole, log A = 10.92 ± 1.51).
[ Hydrolysis was retarded at lower pH. .
[ Water Solubil ity: '-..-
[. Source: Pfaltz and Bauer .
| Listed Purity: identity-purity confirmed by spectral analysis.
f .Analysis Concentration: 7 mg/L in H20/buffer
I . Analytical Procedure: Direct injection - 20 ml onto LC
Instrumentation: GC __. HPLC _X_ .
Detector: UV - 280 run .
Column': Ultrasphere ODS, 5 micron,-4.6miii X 25cni ' -
' "' 'Mobile Phase: Acetonitril,?: 0.05 M., ri3H2P04 (5:95)' '.''.
67
-------
5.3.22 2,4-Dithiobiuret
'Kj = 1.3 hr"1
T1/2 = °-5 hr
R2 - 0.944
O)
c
*c
*o
E
CD
10'-
D
D
0.0 0.2 0.4 0.6 0.8
Time (hr)
1.0
Figure 5:3.22 Hydrolysis of 2,4-Dithiobiure-
at 85°C, pH 7.12
68
t-
L'
-------
5.3.23 Ethyl methanesulfonate
CAS'No.' 62-50-0
HYDROLYSIS AND ANALYSIS D/JA
Literature Data:
Barnard and Robertson (1) reported an activation energy of 21,120 cals/mole
and neutral hydrolysis ratu1 constant of 0.015 hr~*'at 25"C.
1. Barnard, P. W. C. and R. E. Robertson. 1961. The Hydrolysis of a Series of
Straight-Chain Alkyl Methanesulphonic Esters in1 Water. Can. J. Chem. 3^9,
881-888- .
69
-------
r
L..
5.3.24 . Ethylene thiourea : . '
.CAS No.' . 96-45-7 - ' ./. - .
. HYDROLYSIS AND.. ANALYSIS DATA
Literature Data:- .... ' .-.
Ethylene thiourea'(£TU) is very stable towar'd hydrolysis. No changes in
concentration were observed in buffered aqueous solutions (pH 5, 7, and 9) held
at 90°C for 3 months (1). ETU is a decomposition product of the dithiocarbamates
such as Maneb and Nabam.
1. Cruickshank, P. A. and H..C. Jarrow. 1973. Ethylenethiourea Degradation.
. J. Agr. Food Chem. 21_. 333-335. . .
70.
-------
r*
5.3.25 . Ethylene-Bis-(Dithiocarbaiiiic Acid)*
CAS No. 11-54-5 ...
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: , .
pH Temp.°C k^hr'1) k2(M-1hr'1) t1/2(d)
0.005 . 0.992
0.004 0.999
0.02 0.938
.0.20 0.988
0.20 0.954
1 . 7.12 4?,5 0.044" 0.66 0.958
0.54 : 0.886
0.08 0.973
0.06 0.954
0.13 0.978
0.14 0.955
*The free acid is unstable; chemical analyzed was the -lisodium salt (Nabam).
Comments: Metal salts of- ethylene-bj_s-dithiocarbamic acids can follow
at least two routas of decomposition. Route 1, favored by boiling dilute
acid, yields transient formation of the free acid with immediate decomposition
to two moles of carbon disulfide and 1 mole ethylenediarnine. Route 2 is a
slower reaction favored by-cooler dilute acid. Route 2 yields 1 mole of
ethylenethiourea, 1 mole of carbon disulfide and 1 mole of hydrolgen sulfide
1. Clarke, D. B., H. Baum, E. L. Stanley and W. F Hester. 1951. Determination
of Dithiocarbamates, 2.3 1842-1850.
Water Soluoil.ity: > 1.0 g/L
Source: RTP .
Analysis Concentration: 10 mg/L '
Analytical Procedure: Read on IJV spectrofhotoneter - maxima at. 286-30 nm
Instrumentation: Diode Array !JV ': . . '
3.15
3.03
2.96
7.07
7.07
7.12
7.12
9.95
10.13
10.55
10.55
45.5
45.5 '
29.0
66.0
66.0
4?, 5
45.5
66.0
66.0
45.5
45.5
5.45
7.66
1.48
0.142
0.145.
0.044"
0.054
0.353
0.507
0.224
0.211
. 7694
8214
1351
71
L.
-------
5.3,25 Ethyl en e-bis(dithiocarbarmc
acid), sodium salt
K1 '-.= 7.7 hr~1 .. .
T1/2 '= .09 hr';.' . '
R2 = 0.999
O>
c
*c
'o
E
Q)
0.0
Figure 5.3.25
0.5
Hydrolysis of Ethylene-bis(dithiocarbar
acid),, sodium salt at 45.5°C, pH 3.03
72
-------
r
X t
5.3.26 2-F1uoroacetamide . .
CAS Ho.'.640-19-7-
' .. HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:.
pH
3.02
3.02
. 7.23
7.23
7.04
7.04
9.66
I 9.66
9.66
9.75
10.41
| 10.41
10.41
Temp.°C
85.5
85.5 '
85.5
85.5 .
85.5
85.5
85.5
85.5
85.5
85.5
69.2
69.2
69.2
Mhr )
0.011
0.011 .
0.011-
0.012
0.009
0.009
0.802
0.661
0.863
0.946 '
1.51
1..54
1.59
k2(M-1hr-i)
545
449
587
523
. 382
339
402
t1/2(hr)
63.0
63.0
63.0
58.0
77.0
77.0
0.9
1.0
0.8
0.7
0.5
0.5
0.4
rd
0.998
0.997
0.998
0.999
0.997
0.998
0.999
0.999
0.985
0. 985
0.997
0.998
0.997
Comments: The calculated alkaline activation energy is 4,436 ± 3,333 cals/mole,
and the log A is 5.43 ± 1.88. The pH 3 and pH7 data were used to calculate the
hydrolysis rate and half-life at pH 7 and 25°C.
Water Solubility: "Freely" Merck iio. 4051 Ninth ed.
Source:. Aldrich .
f Listed Purity: 98% Identity-purity confirmed by spectral analysis.
[ Analysis Concentration: 6 ppm . : '
> - - .
' Analytical Procedure: Direct aqueous injections;
Instrumentation: GC X HPLC . .'.-
t . --. _
i Detector: FID at 200°C . -
. . Column: DSWAX, 30m x 0.53mi,n ID . ' '..--.
Temperature Program: -95°C to 150°C for 1.2 min at 15°C:per niin1 - '
73
-------
5.3.26 2 r luoroaeatcmide
T1/2
R2
= 1.2 x 10~2 hr~1
= 2.4 days
= 0.999
c.
'c
"o
E
Q)
o:
10
I ' i ' i 7 I
0.0 50.0 100.0 150.0 200.0 250.0
ime (hr)
Figure 5.3.26 Hydrolysis of 2 -Fluoroacetamid*
at 85.5°C, pH 7.23
-------
r
5.3.27 Hexachlorqberizene
CAS No. 118-74-1 ' . .
HYDROLYSIS AND'ANALYSIS DATA
Hydrolysi s Data:
pH Temp.°C ..-.'
. 3.13 85 '' ' - .
3,13 85 .'... . .
. 3.13 '.85 .... . .
7.20 35 No detectable disappearance within experimental error
7.20 85 after 13 days at 85°C.
7-20 .85 . - -
9.27 85
9.27 .85 . . . '
9.27 8?
Water Solubility:
Source:. RTP .
Listed Purity: 93 - 99% Identity-purity confirmed by spectral analysis.
Analysis Concentration: 5 'ug/L in.buffered water ;
Analytical Procedure: Extract 10 ml buffer wi.th 2 ml of 25C u9/L
2,4-D methyl ester in isooctane. Inject isooctane layer v/ith a . .
frnal concentration of 25 pg/L hexachlorobenzene and 250 uy/L 2,4-D
methyl ester as the internal standard.
.Extraction Solvent: Isooctane . .
Instrumentation: G.C X HPLC ' '.
Detector: ECD
Column: D13-5, i.O micron film, 15m x 0.53mm ID . . '
Temperature Program: 180°C isothennal '
Internal Standard: 250 ug/L 2,4-D methyl, ester ' .
75
"Wm
-------
r
5.3.28 Hexachloroethane
CAS No. 67-72-1 " '.
. ' HYDROLYSIS ,-HD ANALYSIS DATA- '
Hydrolysi s Data: .
pH Temp.°C . ' .
3.10 85
3.16 85 ' . . .
3.16 80
7.16 85 Ho detectable disappearance within experimental.
7.18 85 error after 11 days.
7.18 85
9.36 85 . '
9.65 85
9.65 85
Water Solubility:
Source: KTP , .
Listed Purity: 98% Identity-purity confirmed by spectral analysis.
Analysis Concentration: 0.6 mg/L
Analytical Procedure: Extract 10 ml buffer with 2 ml of 7.77 mg/L
solution of 1,2,4-tnchlorobenzene in isooctane. Dilute 1:600
witn isooctane for a final GC analysis concentration of 5 pg/L. ..
Extraction Solvent: Isooctane
Instrumentation: GC X HPLC .
Detector: ECD
Column: OV-1, 5m x 0.53 mm, 2.65 micron. . .
Temperature Program: 80°C for
-------
r
5.3.29 Hexaethyl tetraphcsphate . "
CAS.No. 757-5S-4' .
..''.. . .;'' ' KYDROLYS1S AND ANALYSIS DATA
Literature Data:
The stability of hexaethyl tetraphosphate to hydrolysis is the same as
tetraethyl pyrcphosphate: k,= 0.093 hr'1 and half-life 7.5 hr at ^5°C and pH 7
(1). - -. '
1. Coates, H. 1949. The Chemistry of Phosphorus Insecticides. Am. Appl. Biol,
36, 155-159. ' '.'
77
L-: ' ....-.:
-------
5.3.30 - Isodrin . .
CAS No. 465-73-6 . . '.'."'.'
HrUROLYSLS AND AMALY.SIS DATA
Hydrolysis..Data: '
pH Temp.°G X103k.1(hr"1) ''kgt'M'W'1) tr?\d) r2 .
>55
43 0.690
>55
58 0.667
32 0.531.
3.47
3.47
3.47
7.32
7.32
9.73
9.73
9.73
84
84
84
84
84
'84
84
84
<.5
0.6
. <.5
0.5
0.9
. <.5
X.5
<.5
>55
>55
. . >55
Comments: Half-life was calculated from estimated 10%
disappearance after nine days.
| Uater Solubility:
Source: Aldrich
1 .Listed Purity: 98% Identity-purity confirmed by spectral analysis.
.i . '
J Analysis Concentration: 5 ;ig/L
!
i .. Analytical Procedure: Isodrin concentrarions were 5 ppb in.
I buffered water during kinetic measurements. Extrac.ion of a 10-ml
i . . '. " sample with 2 ml of isooctane that contained endosulfan I (28
! ppb) and dilution of the extract with 2-ml isooctane gave a GC
> ' analysis concentration of 12.5 yg/L
*t Extraction Solvent: Isooctane .
; ' ' Instrumentation: GC _*_ - HPLC ... .
Detector: ECD . ' . .
.Column:. .OV-1, 2.65 micron film, '5m x 0.53>-ni ID'
Temperature Program: 190°C isothermal .
Internal Standard: Endosulfan I .-..'".
73
-------
r
5.3.31 Lasiocarpine .
CAS-No. 302_-34LI4 ''.'. ' . .
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH. Temp.°C ki(hr~') k9(K"^hr~^)
J 1 \J
3.16
r i r;
J . i U
7.08
7.08
7.08
9.50
9.50
9.50
9.85
9.85 ,
O J .
85
85
85
35
85
. 85
85
85
65
65
\m\J\J\J\J
0.0006 '
o nnnfi
U.. VJU.\_ U
0.015
0.014
0.014
1.10
1.22
1.16
.1.25-
C.25
1099
1225
1167
281
291
/ *t O U
>48.0
\AQ ft
/^O . u
1.9
2.0
2.0
0.03
0.02
0.02
0.12
0.12
_
0.96*
0.99J
0.991
0.990
0.997
0.988
0.992
0.997
Comments: The calculated energy of activation for the base
catalyzed hydrolysis is Ea '= 16,866 ± 846 cals/mole with
log A 13.4 ± .0.10. . '
Water Solubility:
Source: RTP
Listed Purity: 62% Identity-purity confirmed by spectral analysis.
Analysis Concentration: 4 pp-7;
Analytical Procedure: Lasiocarpine was analyzed by direct
injection of 20 microliters of each sample onto the column.
Instrumentation: GC HPLC _X__
Detector: UV at 230 nm ' .
Column: Nova Pak C^g . .
Mobile Phaser acetonitri lerwa.ter (50:50) with .005 M Pic R 8
79
"hU^j r- -^ U
-------
5.3.31 Lasiocarpine
K,- .= 1.4 x 10~2 hr~1
Tj/2 2 days
R2 .= 0.991
a>
c
a
E
0)
a:
0.0
20.0 40.0 60.0
Time (hr)
80.0
Figure 5.3.31 Hydrolysis of Lasiocarpine at 85°C
pH 7..03 .".;
80 .
-------
5.3.32 Lindane
GAS No. 58-89-9
Hydrolysis Data:
pH
HYDROLYSIS AND "ANALYSIS DATA
-1.
Tei7ip..°C .XlO-'Mhr"1) k.2
-1/2
2.96
2.99
2.99
2.99'
> i j
j i /
3.17
3.17
6.85
7.24
7.24
7.24
10.98
10.98
11.08
11.29
1.1.60
. 65.5 '
84.4
84.4
84.4
cc c; .
f j j J
65.5
65.5 .
65.5
65.5
65.5
65.5
46.0
. 46.0
4C-0
37.0
23.0
0.4
i.4
1.0
0.7
( 1
\ . i
0.1
0.3
6.5
12.0
12.2
11.9
4290
4680
5000
2410
595
1056
1152
978
552
174
.' 65 d
, . 20 d
29 d
43 d
>7fln H
/ \J\J \J -J
240 d
107 d
- 4.4 d
2.4 d
2.4 d
2.4 d
0.16 h
0.15 h
0.14 h
0.03 h
1.15 h
0.251
0.894
0.651
0.320
0/517
0.377
0.996
0.999
0.997
0.999
0.999
0,997
0.994
0.999
0.930
Comments: The calculated energy of activation for bast? catalyzed'
hydrolysis is: Ea = 15,100 + 500 cals/iiiolo, log A - 13.09 + 0.13.
Water Solubility: 6-12 mg/L . ' . .
Source: RTp ' . . . . .
Listed Purity: 95" Identity-purity confirmed by spectral analysis.
Analysis Concent rat: ion: 200-jjg/L .' . '
Analytical Procedure: Extract 10 ml buffer with 2 ml'of 5.2 mg/L
2,4-D nethyl ester in isooctane. Dilute 1:100 with i:ooctane for
.a final analysis concentration of 20 ug/l. lindar.e. and 100 i.g/L I.S.
Extraction Solvent: Isoocta.ne '/ . '
I'nstrunentation: GC _X_ ' .IIPLC ' __ '
Dotector: ECD . . ' . . '. :
.Coiumn: OV-1, 2.65-microri film,-5m x 0.53mm
Temperature-Progra;;!.: 160°C isothermal'
Internal Standard: 2,4-D methyl ester ' .. '
. ' 81 " ' . '.-:
e^*»-,
-------
r
5.3.32 Lindane
T1/2
R2
= 2.4 hr"1
= 0.3 hr
= 0.999
D)
'£
'c
"a
E-
Q)
1 ol-
0.0
0.2 0.4 0.6
Time (hr)
0.8
figure 5.3.32 Hydrolysis of Lindane at 37°G
pH 11.29
82
6EU-rJA..I
-------
err-
5.3.33 Malononitrile
CAS No. 109-77-3
''. .' HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
':P'H:
3.24
3.31
3.31
7.09
7-.21'
7.21
7.21
7.14'
8.85
' 8.97
8.97
8.97 '
Temp.°C
85o5
85.6
85.6
85. 5
:85.5
85.5
.85.5
85. 6
27.0
27.5
27.5
27.5
1 0 k i ( h r ) k 9 ( r-. hr ) ^i/ov^r) ^
5.0 .
1.6
0.8
288.0
510.0
456.0
588.0
288.0
8.8
11. .4
11.8
13.0
139
433 .
866
2.4
1.4
. 1.5
I.Z.-
2.4
1067 78.8
1010 60.8
1046 58.7
1152 53.3
0.923
0.911
0.810
0.982
0.994
0.990
0.935
0.998
0.933
0.992
0.986
0.987
Comments:. Extrapolated alkaline second-order rate constant to 25°C was
806 ± 4.5 Ir1 hr"1 (assumed Ea = 20, cals/nole).
Water Solubility: 13 g/100 ml 1300 mg/L
Source: Aldrich
Listed Purity: 99% .
Analysis Concentration: 25 mg/L
Analytical Procedure: Basic runs were neutralized with 8 drops of 0.5 M
Instrumentation: GC_X_ HPLC ' '
Detector: FID
Column:. DBWax 30m .53mm ID 1.0 micron film ''.
Temperature Program: 95°C then 40°C/min to 160°C'
.Internal Standara: 3-chloropropanem'trile . .
83
-------
r
5.3.33 Malononltrile
T1/2
R2
=-5.1 x 1CT1 hr~1
= 1.4 hr
-0.995
Q>
C
o
E
Q)
CtL
°-° 1'0' .2.0- 3.0 .4.0. 5.0 -eiO-
Time (hr) ;
Figure 5.3.33 Hydrolysis .of Malononitrile at 23.S°C
. pH 7.13
-------
Internal Standard: 2,4-0 methyl ester
5.3.34 Melphalan .
CAS No. 148-82-3 .' .
HYDROLYSIS AND ANALYSIS DATA
Literature Data:
Melphalan is a nitroyen mustard used in cancer chemotherapy. Melphalan
hydrolysis is not acid or base catalyzed. The neutral hydrolysis rate at 25°C
is: k = 0.145 hr"1 and half-lifa of 4.8 hours (1).
1. Flora, K. P., S. L. Smith and J.C. Cradock. 1.979. Application af a Simple
High-Performance Liquid Chnnoatographic Method for the Determination of'Melphalan
in the Presence of its Hydrolysis Products. J. Chromatogr. 177, 91-97.
85
-------
5.3.35 Kethomyl
CAS f.'o. 16752-77-5
HYDKOI.YSIS AND ANALYSIS DATA
Literature Data:
Chapman and Cole (1) reported the pH-disappearance rate profile at 25PC
for methomyl at p.Ms 4.5, 6, 7, and 8 in sterile phosphate .buffers. Ho catalysis
.by acid was observed. A neutral rate constant (8.9 X 10~5 hr~l) and an
alkaline second-order constant (210 M~l hr-1) was calculated. The second-order
constant was in good agreement with Lemley and Zliong (258 H~l hrl, 25°C, 79.2
M-l h-I at 15°C).
1. 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.
2. Lemley, A. T., W. Z. Zhong, G. E. Janauer and R. Rossi. 1984. Chapter 15
in Treatment and Disposal of Pesticide Wastes, R. F. Kruger and J. N. Seiber
Eds., ACS Symposium Series, Washington, D.C. pp. 245- 259.
86
-------
.5.3.36 Methyl methacrylate
CAS No. ' 80- 62^6'
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: -
, - '..pH ': '.'.-Teinp.'C 103k1(:hr-1)
t1/2(hr)
3.17
.3.17
7.07
7.11
7.11
7.11
9.33
9.86
10.00'
10.06
11.13
11.13
11.13
85.0
.. 85.0.'
. 25.0.
85.0
. 85.1
85.1
85.5
66.0
66.2
66.5
25.0
25.0
25.0
Mo neasureable hydrolysi
No measureable hydrolysi
No measureable hydrolysi
0.1860 '
0.0078
0.0187
Complete hydrolysis, 15
1.84 ' 1940
4.60 3480
4.04 2620
0.31 . 230
0.26 190
0.24 180
s, 53 hr
s, 53.hr
s, 72 hr
3.7
88.4
37.1
mi n
0.37
0.15
.0.17
2.23
2.66
2.88
0.804
0.789
0.977
0.993
0.999
.0.990
0.995
0.981
0.977
Comments: The hydrolysis at pH 7 can be attributed to hydroxide catalysis.
The second-order .aIkaline hydrolysis rate constant at 25°C (200 + 47 M-l hr-1,
a= 0.05) is in good agreement with Shrama and Shrama (1) [171 M ^ hr~*].
Water Solubility:. "Sparingly" JARC Vol 19(1979}
Source: .Aldrich
Lasted Purity: 99% Identity-purity confirmed by spectral analysis.
Analysis Concentration: 10.5 ppm
Analytical Procedure: Prepared fresh stock prior to each run in autoclaved
H£0. Added to buffer for an initial analysis concentration of 1Q.5 ppm direct
aqueous injection.
Instrumentation: GC X HPLC __ '
Detector:. FID . .
Column: DBWax 30m, 0.53mm ID . . . .
87
-------
5.3.37 . N-Methyl-rN-Nitro-N-Nitroso'guanidine
CAS' No. 70-25-7. . . .' . '.'.' .
' HYDROLYSIS ANO ANALYSIS DATA
Literature Data: ... .
Hydrolysis is catalyzed by hydroni.uci ion-below--pH 3 (k,c..jd - 4.9 M'^hr"*,
25°C). It has a second-order alkaline hydrolysis rate constant of approximately
9.5 X 10;* M-l hr-1 at 25°C (1). The observed half-life at pH 7. and 3/°C was 5
hours. The above yields a neutral rate of 0.027 hr-1- at 25°C.
1.' McCalla, D. R., A. Reuvers. and R. Kitai. 1963. Inactivation of-Biologically
Active ll-Methyl'-fl-Nitro-M-Nitro'so Compounds i:i Aqueous Solution: L'f'fect of
Various Conditions of pH and II lumniation. Canad. J. Biochem. 48,, .C.07-B11.
' 83
-------
5.3.38 2-Methylaziridine
CAS No. 75-55-8
HYDROLYSIS AND ANALYSIS DATA
Literature Data: . .
Water is sufficiently acidic to proyide a very low concentration of
2-methylaziridinium ion (approx. 2 X 10~°) (1). Tne iminium ion has a pKa
of 9.61 and the free imine has a pK& of 5.38 (1). The rate constant for a ring
opening in aqueDus solutions was (7.0 ±" 0.2) X 10-3 m-jn-l at 65°C. The derived
rate and half-1'fe at 25°C are 0.008. hr"1 and 87 hr, respectively. Addition of
acids accelerates production of the aminoalcohols and/or polymerization. Bunnett
et
4.
2t al. (2) reported data that yields an acidic second-order rate constant of
1.0 X 1U-3 M-l hr-1.
1. Biust, G. J., and H. J. Lucas. 1957. Basicity Constants and Rates of
Hydration of Some Imines. J. Am. Chem. Soc. 79, 6157-6160.
2. Bunnett, J. F., R. L. McDonald And F. P. Olsen. 1974. Kinetics of Hydrolysis
of Aziridines in Moderately. Concentrated Mineral Acids. J. Am. Chem. Soc.
96, 1855-1861.
89
-------
5.5.39 Methylthiouracil
GAS. No'. 56-04-2
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH' .
3.41
.3.41
3.41
3.02
5.72
5.72
5.72
7.17
7.35
7.35
7.35-
9.05
9.65
9.65
9.65
Temp.°C
. 85-'
85
' 35 .
66
85 -'
85 ..
. 85 .
66
'85
'85
85
66 .
85
85
85
LO-^k^hr-1) k^M-^hr1) t1/2(hr)
Mo hydrolysis after 8 days
1.07
0.69
0.54
7.6
91.5
95.5
. 75.4
. 13.7.
27.3
37.4
34. S
27.0 d.
42.0 d
54.0 d
3.8 d
0.3 d
0.3 d
0.4 d
2.1 d .
1.1 d
0.8 d
0.8 d
0.898
0.647
0.915
0.847
0.848
0.932
0.991
0.847
0.990
0.837
0.896
Comments: At pH 7.35 and 85°C the hydrolysis, rate is three times greater than
the rate at pH .9.65 and 85°C (pH was measured, at 85°C). S-Methyl-3-thiouracil
has two ionizable protons and hence two pKs. Thus the ionization can be written
as: .
Pk2
H2A
7.73
A2-
where a value of 7.33 (1) has been reported for pKi. The value ot pK? would be
>11.. The resistance to acid hydrolysis and the greater rate of hydrolysis at
pH 7.35 is strong evidence that the morioion (HA~) is the degraded species.
Hydrolysis is most likely mediated by attack of a molecule of water on the
9.0.
-------
rnonpanion. As the pH 15 increased, the equilibrium is shifted more to the
dianion and the rate of hydrolysis correspondingly decreases. Thus the rate at
pH 7.35 and 8.5°C-was extrapolated to pH 7 and 25°C.using the calculated.
Ea = 32,649 cals/mole. . . .
.1.. Garret, E. R. , and D. 0. Weber. 1970. Metal Complexes of Thipuracils I:
Stability.Constants by Potentiometric.Titration Studies and Structures of
Complexes., J. Pharnu Sci. J59, 1333-1398.
Water Solubility: 0.48 g/L .
Source: Aldrich
Listed Purity: 99% Identity-purity was confirmed by spectral analysis
Analysis Concentration: 1.1 ppm in buffared 1^0
Analytical Procedure: 20 ml direct injection on LC
Instrumentation: GC . HPLC _X_
Detector: UV - 230 nm
Column: Waters Nova-Pak C\Q ( 4 M, 4.6mm X 15cm)
Mobile Phase: '0.05.M NaHoPO/pMethanol (90:10) '
91
-------
5.3.39 Methylthiouracil
T1/2
R2
= 1.4 x 10~- hr
= 2.1 days
= 0.937
O)
c
a
E
Q)
10
o
0.0
D
20.0 40.0 60.0
Time (hr)
80.0
Figure 5.3.39
Hydrolysis of Methylthiouracil at 66°C,
pH 9.05
92
-------
5-3.40 '.Alpha-riaphthylthiourea
CAS No:/86-88-4 .
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis. Data:
.. ' pH' '.: Temp.°C
]/2
(d)
3.26':
3.26 .
3.26
7.17
7.17
7.17
9.80
9.80
9.80
--85
. 85' . '
85
' 85 '
85
85:
85
85
85
0.009
0.010
0.011
0.019
Q.025
0.024
0.046
0.049
0.056
.3.1
2.8
2.6.
. 1.5
1.2
1.2
25.0 0.6
27.0 0.6
31.0 0.5
0.995
0.964
0.972
0.915
0.988
0.985
0.944
0.981
0.964
Water So-1 ability:
Source: RTP
Listed Purity: 93.9% Identity-purity, confi rnied by spectral
analyst s. .
Analysis Concentration: 2 mg/L
Analytical.Procedure: Alpha-Naphthaylthiourea was analyzed by
direct injection of 20 microl-i ters buffered solution onto the
Resolvex Cjg column for each sample.
Instrumentation: GC HPLC X
Detector: UV at 222 nm
Column: Resolyex Cjg, 10 micron, 4.6 x 25cm
.Mobile Phase: acetonitrile:water.(50:50)
93
-------
5.3.40 Alp h'g No p h th y I th ? o u re a
Ki - 2.5 x 10~2 hr"1
Tj/2 ~ ' - days
R2 =' 0.988
>- o
Ci\
0.0
20.0 ' 40.0
Time (hr)
60.0
Figure 5.3.40 Hydrolysis of Alpha-Naphthyl
.. . thiourea at 85°G, pH 7.17
94
-------
.5.3.41. N-Nitroso-N-Ethylurea
CAS No. 759-73-9 . .'
HYDROLYSIS AND ANALYSIS DATA
Literature Data:
Druckrey et al. (1) reported stability data at 20°C and at pH values
from 4 to 9. Values of second-order and neutral rate constants were extrapolated
to 25°C. A half-life of 0.8 hours was calculated at 25°C and pH 7. This value
was in good agreement with that of Garrett et al. (2).
1. Druckrey, H., R. Preussmann, S. Ivankcvie and D. Schmahl. 1967. Orgontrope
Carcinogene Wirkungen bei 65 Verschiedenen N-Nitroso-Verbindungen an BD-
Ratten. Z. Krebforsch. 69, 103-201.
2. Garrett, E. R., S. Goto and J. F. Stubbins. 1965. Kinetics of Solvolyses of
Various N-Alkyl-N-Nitrosoureas in Neutral and Alkaline Solutions. J. Pharm.
Sci. 54, 119-123.
95
-------
5.3.42 N-.Nitroso-'l-HethyTurethane .
CAS Ho.' 615-53-2 . ..'''. . '
".' : ' HYDROLYSIS AND ANALYSIS DATA . '. '
li.lerature Oata:: Rate Data calcluated from Me Call a et a'l. (!). McCall'a reported
rate d^ta in one pH unit increments from pH 2 through pH 9 at 37°C.
1. McCalla, D. R.,. A. Reuvers and R. Kitai. 1968. Inactivation of Biologically
Active .N-Methyl-N-!litroso Compounds in Aqueous Solution: Effects of Various
. .Conditions of pH and Illumination. Canad. J. -Biocheni. 46, 307-811.
-------
5-3.43 Octanethyl pyrophosphoratrn'de
CAS No. 152-15-9 ...
. - . . . HYDROLYSIS AMD ANALYSIS DATA . ..
Literature Data: .....
Heath and Cascipieri (1) measured the hydrolysis rates of some dimothylamides
of phosphoric acids in.acids, alkalies, and water. Octamethylpyrophosphoramide
in water at pK. 7 was held at 100°C for one week. No'hydrolysis was observed
within experinental error. The second-order dcid and alkali,ie rate constants
were 0.23 ±. 0.03 M-l hr-1 and 1 X. 10-H M-l hr-1 respectively. The half-life at pH
7 and 25°C based on the acid contribution would be 3,400 years.
1. Heath, p.. P., and P. Casapieri. 1950. Hydrolysis of Dimethyl amides of
. Pnosphoric Acids. Trans. Faraday Soc. 47, 1093-1101.
97
-------
5.3.44 ," Di-n-OGty1j)hthal;ate.- ' .
CAS No;.. . 117-S4-0 , . . .
. ' ' . . . HYDROLYSIS A.'iD ANALYSIS DAFA ; .
Literature Data: Wolfe '!) et al. 'oported j second-order alkaline 'hydrolysis
rate constant of 12.9 M-I nr-i at 30°C. Hydrolysis at neutral pH would be. ,
doni.n..»-ed-by the alkaline contri-but ion thu-s the calculated second-order rate at
25PC was used'to tletemine the ha 1 f-l.ife at pH ,7 and 25°C.: . ' . '.
1. -rt'olfe, N. L. , Q. F. Pari's, W. C. Ste.en
-------
5.3.-55 £ji?j:a_t_e . . . . ' '
CAS: f;0. 2g3-02-2 ; ' '.
' ' . HYDi-lOl.YSIS AM ANALYSTS DATA ' '
Literature Data: . . . .
'Charrian- and Cole.(I.) deter nod at 25°C the pH-disappearance 'rate profiles
for 24'insecticides inuiuding.phorate; The determinations covered'4 or 5 pH
values over the range 4.5. to 8. in sterile phosphate buffers. The neutral rate
constant for phorate was O.OQ/2 iir-1 with a corresponding 96 hr half-life at 25°C.'
Acid or ba ;e cacalysis was not observed in the above pH range.
i. Ghapnan, R. A.,and C. M. Cole. 1932. Observations on the Influence of Water
and Soil pil on the Persistence of Insecticides. J. Environ. Sci. Health.
' -817(5), 487-504.. - . ' '
'99
-------
5.3.46 1.3-Propane Sultone .
CAS No. 1120-71-4
. 'HYDROLYSIS AND ANALYSIS DATA
Literature Data:
From the data of Bordwell et al. (1) a neutral hydrolysis rate constant of
0.082 hr-1 and half-life of 8.5 hr were calculated. The energy of activation was
20,400 cals/mole.
1. Bordwell, F. G., C. E. Osborne and R. D. Chapman. 19S9. The Hydrolysis
of .Soltones. J. Am. Chem. Soc. 81, 2698-2705. . .
100
-------
5.3.47 .Safrole
CAS Mo,; .94-59-7
. HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
: .pH Te;Tip.°C
15'..
22
27
27
3.27
12
29
29
29
29
9.81
9.77
9.60
9.60
9.60
66.5
85.5
.85.1-
85.1
'85.1
65.9
85.2
85.id
85.2
85.2
65.6
85.5
85.3
85.3
85.3
No detectable hydrolysis over 9 days
No detectable hydrolysis over 14 days
No detectable hydrolysis over 26 days
flo detectable hydrolysis over 26 .days
Mo detectable hydrolysis over 26 days
Mo detectable hydrolysis over 14 days
No detectable hydrolysis over 14 days
No detectable hydrolysis over 21 days
No detectable hydrolysis over 21 days
No detectable hydrolysis over 26 days
No detectable hydrolysis over 14 days
No detectable hydrolysis over 9 days
No detectable hydrolysis over 26.days
No detectable hydrolysis over 26 days
No detectable hydrolysis over 26 days
Water Solubility: Insoluble
Source: .Aldrich
Listed Purity: 97% Identity-purity confirmed by spectral analysis.
Analysis Concentration: 2.4 mg/L
Analytical Procedure: Safrole was analyzed by direct injections
into a 20 microliter injection loop of each sample.
Instrumentation: . GC '_ HPLC X
Detector: Kratos Spectrqflow.757 UV at 290 nm
Column:- ODS Ultrasphere 4.6mm x 15cm, 5 micron '
Mobile. Phase: rnethanol :water (6.5:35)
101
-------
5.3.4S Tetraethyl pyrophosphate' '.....-
-CAS No. lOZ^il-l '''-.' ' ."'
hVDROLYSI.5 AND ANALYSTS DATA-
-Literature Data: .'..'' . -
Tetraethyl pyrophosphate hydrolysis is a first-order reaction with a value
of the rate constant of '0.093 hr-l-at 25°C and an activation energy of
10.7 Kcal/inole (1). The hydroxide catalyzed hydrolysis was too fast to
measure. . .
1. Ketelaar, J. A. A. and A. H. Bloksma. 1948. The Rate of Hydrolysis and
Composition of Tetraethyl. pyrophosphate. ftecueil. 67, 665-676.
-------
5.3.49 Thioacetamide
CAS No.'. 62-55-5
HYDROLYSIS AND ANALYSIS DATA
Hydrolysi s Data: . ...
pH Temp.°C k^hr"1)' k2(M*1hr'1) t1/2(d) r2
7.18 85 , 0.025 . 1.2 0.923
7.18 85 Q.026 1.1 0.647
7.13 85 0..020 0.9 0.925
Comments: Peters and De Ranter (1) reported -
-------
5.3.49 Thioacetamide
p ,/ i n. 2 | ..-1
. O y\ I VJ 111
T.1/2- ~ 1-6 days
R2 - 0.930
D)
4C
*C
*O
E
a)
101
1.0
,0
0.0
20.0 40.0 60.0
Time (hr)
80.0
Figure 5.3.49
Hydrolysis of Thioacetamide at 850C,
pH 7.05 : ;
104
-------
5.3.50 Thlram . ' ' ': ''...
CAS No. 137-26-8 ''.'
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
PH
3.22
3.29
6.95
6.97
6.97
10.49
10.79
10.79
Teinp.°C
85
85
65
65
65
24 ' '
24
24
Mh.r-1}
0;06 .
0.06
0.27
0.26
0.29
1.83. . '
2.33
2.26
t. .
. .2.3x105
2.2:
-------
5,3.50 Thirarn
Kr =1.8 x hr
-1
T1/2
R2
CD
£
*C
'o
£
-------
.5.3.51 Toxapherie
CAS No. 8001-35-2 . '
"'' HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: .
; pH ... Te;Tip.°C X103k1(hf-1) k2(M'1hr1) t1/2(d)
3.24 '
. 3.25
3.25
7.20 .
7.20
,7.20
. .9.63
9.35
9.35
: -85 .
85
' 85 ..'
85 .
' 85.
35
85
85
85
3.0
2.0-
1.8
5.6
4.1 -.
4.7
2.0
10.5
.15.2
9.8
. 14.4-
.15.9
5.2
7.0
6.2
0.7 1.6
3.7 2.7
5.2 1.9
0.980
0.804
0.920
0. 956
0.5C2.
0.894
0.974
0.603
0.965
Comments: Toxaphene is difficult to quantitate because it is a
mixture.of more than 670 compounds, primarily polychlorinated
bornanes-(CigHi5_nCln). The chlorine content is 67-69 percent.
by weight. . Quantitation was based on decreasing response to '
electron capture detection for an envelope of GC eluted
compounds. The hydrolysis values at pH 3 were used as the true
neutral contribution to hy-'rolysis.
Water Solubility: 4 mg/L
Source: ' RTP . .
Listed. Purity: lOOf, technical toxaphene, 68% chlorine. Identity-
purity was confirmed by spectral analysis.
Analysis. Concentration: 500 pg/L in buffered water
Analytical Procedure: Extract 10 ml buffer with 2 ml isooctane,-
.dilute 1:25. Final analysis concentration was 100
Extraction Sol vent: Isooctane
Instrumentation: GC X IIPLC
Detector: ECD .
Column: -'OV-1, 2.65 micron film, 5m x.0.53mm ID
temperature Program: 210°C isothermal
107
-------
5.3.51 Toxqphene
T
R
1/2
2 _
= 5.6 x 10~3 hr~1
= 5.2 days
0.956
0)
I 10'H
o
10
. 0.0
50.0
100.0
Time (hr)
TSO'.O
Figure 5.'3.51
Hydrolysis of Toxqphene at 85°C,
. : pH 7.20
108
-------
5.3.52 0.0,0-Triethyl ester phosphorothioic acid
CAS No.. 126-68-1
HYDROLYSIS AMD ANALYSIS DATA
Hydrolysis Data; .
pH Temp.°C X103k1(hr1) kjtM'V'1) t1/2(hr) r2
3.09 35.3 18.2 . 38.0 .864
3.23 85.5 16.C 43.2 .982
. 3.23 85.5 15.8 . 43.8 .992
3.23 85.5 13.3 52.0 .997
7.10 85.0 10.6 . . 64.9 .996
7.10 85.0 13.1 52.5 .980
7.10 85.0 .14.2 . 48.6 .992
9.82 85.0 14.3 48.4 .962
9.56 85.0. 13.3 51.8 .876
9.56 85.3 14.2 . . 48.7 .951
9.56 85.3 13.5 51.2 .990
Comments: The hydrolysis of the ester is a neutral process (same rate at all
pH levels). An activation energy of 23,000 cals/mole was used to extrapolate
the rate to 25°C. . .
Water Solubility: 100 ppm
.Source: Chemical Services
Listed Purity: None listed. Identity-purity confirmed by spectral analysis.
Analysis Concentration: .46 ppm
Analytical Procedure: Extract 5 ml buffered solution with 2.5 ml isooctane. Dilute
1:1 with internal standard solution (800 ppb TEP in isooctane).
Instrumentation: GC X HPLC
Detector: IIPD . . '
Column: D85 15m, 0.53mm ID
Temperature Program: 100°C Isothermal
109
-------
.5.3.53 ' 0,0,S-Triethyl ester phosphorodithioic acid
CAS. No. 2524-09-6 .'''.
.--.: . . HYDROLYSIS AND ANALYSIS DATA . .
Literature Data: A standard for this compound could not be obtained. However'
the half'-i ife would be less .than compound 5.3.52 (the S-ethyl.is a better
Teaying.group'than Q-ethyl).
110
-------
3.13
3.20.
3.20
7.09
7.09
7.13
8.83
8.83
9.67
9.67
85
85
85
: 85
85
85
85
85
66
66
0.00177
0.00249
0.00435
0.0923
0.1004
0.1125
2.9507.
3.4572
2.1379
2.1258
13855
16234
3492
3472
5.3.54 Tr j s(2,3-di bromopropy)-phosphate
CAS No. 126-72-7
HYDROLYSIS AND ANALYS.IS DATA .
Hydrolysis Data:. ...
: pH Temp.°C k^hr^1) k^M^hr1} _ t1/2 r2
16.3 d .671
11.6 d .718
6.6 d .943.
7.5 hr .997
6.9 hr .994
6.2 hr .951
0.23 hr .935
0.20 hr .999
. 0.32 hr .993
0.33 hr .999
Comments: The calculated activation energy and log A for the secondrorder
hydrolysis are 18, 576 ± 1,002 cals/mole.and'15.52 ± 0.03 respectively.
Hydrolysis at pll 3 was used to calculate the neutral contributici to overall
hydrolysis. Hydrolysis of phosphate esters is mediate^ by the neutral .water
molecule and hydroxide ion. .
Water Solubility: 4 ppm '..'.
Source:' EPA/RT? or FDA ...
Listed Purity: 99£ Identity-purity confirmed by spectral analysis
Analysis Concentration: 116.ppb . .
Analytical Procedure: Extract 10 ml buffer containing tris with 2 ml'i.sdoctane.
Add' 3 ml isoocta'-.e and inject 1 ml onto GC. ' . : .
Extraction Solvent: Isooctane ' ' .
Instru:!ientatibn: GC_X_ HPLC ___ . . : :
Detector: 'EC .
Column: 10n, SE-54 thin film (approximately 0.1 micron) . -' .
Temperature. Program: 205°C for 0.5 ^iin then 8°C/min to 230°C. .
Ill
-------
5.3.54 Tris (2;5--D?brorr.opropyl)
phosphate
V O 1 U ,-~ 1
r\ ^ < /... 1 n r
T1/2 = 0.3 hr
R- -.= 0.993
1 0^5}
c
b
E
o
a:
10H
10
o
i 1 ' | 'I I ' 1 r y ~T -|
0.0 0.2 0.4 0.6 0.8 1.0 1,2
Time (hr) ;;
Figure 5.3.54 Hydrolysis of Trir (2,3-Dibromo.propyl)
phosphate at 66°C, pH 9.6
-------
' ... . APP.'ItiDIX A . ' :.
' ' - - ' MASS S?ECTROMETR1C ANALYSIS - ...
Objective: 'The objective of this MS work .'./as to check the identity of the
fol-lowTruj chemical s: N-(ami not hioxomethyl-)acet amide, l-(o-chlorophenyl )thiourea,
3-chl orooropanenitrile, ,0,0-diethyl -Opyrazinyl phosphorothioate, 2,4-dithiobiuret,
2-fluoroacetamide, isodri n, alpha-napthyl thicurea , .octamethylpyrophosphoramide,
toxaphene, acetonitrile, 2-acetyi aini'nofluorene, cis-chlordane, trans-chlordane,
1,2-dichloropropane, drallate, p,p'-DDD, di-n.-octylphthalate, hexachlorobenzene,
lindane, hexachloroethane.* 1 asiocarpine, malononitrile, methylthiouracil,
thioacetanrde, thiram, methyl methacrylate, azaserine, chlorambucil, heptachlor,
and kepone. These chemicals are used.as standards for determining the "second-third"
hydrolysis rate constants. The mass spectrum of ea:h standard was determined
by either GC/MS or probe/MS. ! ' . ' .
Apparatus and conditions: Analyses were carried out with a Finnigan
Model 4500 gas chronatograph - mass spectrometer interfaced to the Finnigan
Incos Data Systen. The moss spectral matching program used the "1984 EPA/fllH
Incos Compatible Library Containing 42,197 Mass Spectra" obtained from W. L.
Budde.of EMSL-Cinn (EPA/NIH Library). The 1983 version of the bound'"EPA/NIH
.Mass Spectral Database" and the 1933 version of the "Eight Peak Index of
Mass Spectra" were also used as references.
The GC column was a DB-5 fused capillary 3Cm X 0.25mm; for most chemicals,
the temperature program was 3 min at 45°C, 45-280°C at 10°/min.' Acetonitrile,
because of its volatility, was injected directly on the column at room temperature.
Lasiocarpine, azaserine, thiram, N-(aminothioxomethyl )acetamide, l-(0-chlorophenyl.)-
thiourea,' 2,4-di thiobiuret, and 2-fluoroace.tamide .could not be analyzed by GC; they
were analyzed from a direct probe at 75-200°C.
RESULTS . '
Standard Reference Compounds ' .
M- (Am i no t li i ox ome t hy 1) a c e t am i d e: The .probe ma-ss spectrum was an excellent
match to the standard spectrum of H-(aminothioxomethyl)acetamide in the
EPA/NIH Library. . . . -.' ' . ' ' '
l-(o-Ch1urophenvl)thiourca: The probe mass spectrum was not in any .
available database. The fragmentation pattern, however, shows 'charjcteristics
expected for i-(0-chl orophenyl )thiourea. . There-is a promine-nt molecular ...
ion at m/z 186 with a chlorine isomer pattern indicating one chlorine. '
The base .peak, at m/z 151 represents a chlorine loss; the ion at m/z- 127 '
represents a chlorophenyl-Ni'2 group. . '.
3-Chloropropanenitrile: 'The GC mass spectrum was ah excellent match .to
Fne standard spectrum of 3-chl oropropaneiii trile in the EPA/NIH Library. . ' .
.113
-------
0,0-Diethyl-0-pyrazinyl phosphorothioate: The GC mass spectrum was an
excellent match to the standard spectrum of 0,0-diethyl-0-pyrazinyl
phosphorothioate in the EPA/NIH Library. .
2,4-Dithiobiuret: The probe mass spectrum was not in any available
database. The fragmentation pattern shows characteristics expected of
2,4-dithiobiuret. There is a/prominent molecular ion at m/z 135 with an
3.8% m/z 137 ion indicating 2 sulfur groups. A large m/z CO ion represents
a -CSNH2 group.
2-F1uoroacetamide: The probe mass spectrum was not. in any available
database. The fragmentation pattern, however, shows characteristics
expected of 2-fluoroactamide. There is a prominent molecular ion at m/z
77. The m/z 60 ion represents a loss of -OH.
Isodrin: The GC mass spectrum was an excellent match to the standard spectrum
of isodrin in the EPA/NIH Library. .
alpha-Naphthylthiourea: The compound decomposes on a GC column to 2-isothiocyanato
naphthalene!There is an excellent match to the standard spectrum of 2-isothiocyanato
naphthalene in the EPA/NIH Library.
Octamethylpyrophosphoramide: The GC mass spectrum .'as an excellent match to
the standard speccrum of octamethylpyrophosphoramide in the EPA/NIH Library.
Toxaphene: Toxaphene is a mixture of many compounds produced by the
chlorination of camphene. Toxaphene gives a characteristic smear when
analyzed bv GC and is best identified by this profile. The mass spectra is
not revealing, only showing a highly chlorinated family of compounds.
The GC-MS ion chromatogram of.this toxaphene standard matches the toxaphene
profile in "Analysis and GC-MS Characterization of.Toxaphene in Fish and
Water" by David L. Stall ings, EPA-600/3-76-076, August, 1976.
Acetonitrile: The GC mass spectrum was an excellent match to the standard
spectrum of acetonitrile in the EPA/NIH Library.
2-Acetylaminofluorene: The GC mass spectrum was an excellent match to the
standard spectrum of 2-acetyl aminofl uorene in the EPA/NIH Library.
cis-Chlordane: The GC mass spectrum was a good match to the standard spectrum
of chlordane in the EPA/NIH Library. The mass spectra of the cis and tran-
isomers of chlordane are very similar and cannot be distinguished from each other.
The GC retention times of the two compounds are.quite different, however.
trans-chlordanc: The GC mass spectrum was a good match to the standard
.spectrum of chfordane in the EPA/NIH Library. The mass spectra of .the cis
and trans isomers of chlordane are very similar and cannot be distinguished
from each other. . .
114
-------
1,2-Dichloroprppa-ne: The GC mass spectrum was a good match to the standard
spectrum of 1,2-dichlbropropane in the EPA/NIH Library.
Dial late:' The gas chrciTiatograph separates diallate's ci_s and trans isomers
:into two" separute peaks. . The fiC mass spectrum of each" was a good match to the
standard spectrum of diallate in the EPA/NIH Library. The mas'S spectra of
the tw isomers are very similar and cannot be distinguishes .rrom each other.
p,p'-:DDD.: The GC mass spectrum was a good .match to the standard spectrum of
.p,p-'-DDO in'the EPA/NIH Library.
Di-n-Octylpnthalate; The GC mass spectrum was a good match to the standard
spectrum of di.-n-octylphttv.late in the EPA/N'H Library.
Hexachlorobenzene: . The GC mass spectrum was an excellent match to the standard
spectrum of hexachlorobenzene in the EPA/NIH Library.
Lindane: The GC mass spectrum was a good match to the standard spectrum of
lindane in the EPA/NIH Library.
Hexachloroethane: The GC mass spectrum was an excellent match to the standard
spectrum.of hex^chloroethane in the EPA/NIH Library.
Lasiocarpine: .The probe mass spectrum was a good match to'the standard
spectrum of lasiocarpine in the EPA/NIH Library.
Malononitrlle: The GC mass spectrum was a good match to the standard spectrum
of maTonbnitrile in the -EPfl/fjIH Library. . .
Methylthiouraci1: The GC mass spectrum was not in any available database.
The fragmentation pattern, however, shows characterstics expected for
methylthiouracil. There is a prominent molecular ion at m/z 142. There is
a large m/z.63 ion representing a loss of -HMCSNH.
Thioacetamide: The GC mass spectrum was a good match to the .standard spectrum .
of thioacetamide in the EPA/NIH Library.
Thiram: The probe mass spectrum was a good match to the standard spectrum
of thiranr in the EPA/NIH Library; " .
Methyl Methacrylate: ' The GC mass spectrum was a good match to the standard :..
sp'ectrum of liietiT>i~"methacry'! ate in the EPA/IUH Library.
Azaserino: The probe mass spectrum v;a3 .net. in any available database.
The fragmentation pattern, however, shows character!sties expected for azaserin;
The highly reactive UN group apparently protonates giving a protonated .
molecular ion at m/z 174. There is a char-acteri stic acid loss -COOU (plus a
protonated ion) at m/z 123; ions at m/z 69, and 74 represents -COCHNN and '-.'-.
-HCNH2COOH, respectively. . . .
Chlorambucil '. The probe mass spectrum was not in any available database.
The fragmentation pattern, however, shows characteristics expected for
chlor.ambuci 1.. There is a prominent molecular ion at m/z 303, with a chlorine
isomer pattern .indicating two.chlorines. The base peak at m/z 254, represents
a -CH2C1 loss. .-..''
' ' '
-------
Heptachlor: The GC mass spectrum ;vas a good inatch to the standard spectrum
of-hi-ptaelTlof-in the EPA/M1H Library. . . . '
Kcpono: The GC.inass spectru-n-was a good match to the standard spectrum of
fTepone in the EPA/filM Library. . .
1.V6
-------
riM^-;. iPtX TPUM
OS--!?.-:?? 9:36:00 + 3:28
.-.HNR.l-:: 1 -HCETYL- ; -THIOUREH LOTttPI-1C1540:r; J J
COMO-;. : El-PROLE
DATn: flTHI
CrtL!: C51
48
N--AcetaMide
H
H2N-C-N~C-CH3
' ^ ii it
so
co
-r~^-rt -,-.j- -
i.
-------
I'o :>". ::; t >. ii:oo ZIQS
-'(.'!> LL: 1-' i-CHLOr-Of'Hl-'M'.'L ' - Z'-TH ! O'JFCH
CM: II".....: ti-PPuUf: .
OMTM:' Ch-TnIO It! J
Cnl. I: " :.'f. u-.:
l-
-------
".HNfl h
>:> r.irr,..
+ l:.":f>
:OPnHEIH TP. Il.E
Di'lTMt i.'K'III'l B
C..LI: c:<"!; BS.
3 -Ch 1 or gpr op a.n e n i tr.i 1 e
N=C-C-C CI
61
.CO I i 53
1-1 |..-|-,"}-.-l-^-r-^-r.-1-'"r-'-r-«-Tf-i.-
r-o . ' ;-o
91
-------
MH-JS SPECTPUM DnTAl DPP MTO
D2--u5--Sr 1S:»3:OO * O:52 CftLI: CFEB41 »::
SAMPLE: O.O-DIETHYL-CK 2-PYRAZIHYL> F'HOSPHC-OTHIOftTE LOT It 39 .'3-2
CC'HDS.: El
10O.O -i
r-.-
c
so. o -
4
65
7
1,1
U.
,1
ft,..
'
9
t
L
.LLjL
3
J
o , o-D i e thy 1 -o-pyraz i ny I
107
\1~JL
phospliopothioate
H A2^5"
/G~Nx \
^ *C-0-P=S
s / 1
142
1
ill
i:
II, 1,
3
1
|
I
*
,,134 I
lltLv OJJ
Jl
l-n;
t TT.
'f9 'f7 -'a" 21-5 1
i TJI. ..... I. i, i i. J:
100
200
-------
i . -t -O IT H I OB IURET ' LOT »D544 1 0
Ot'.Tft: DTBUF »3'i
'I ML I: CJ1.JM S3
'l.C'O.Vi/
2,-4-Di thiobiuret'
H
H2N-C-N-C-NHP
ii it 2
S S
!
4e
ll
SJ 1
L-U-t-.^X_r-, L
I , ,-r.i_l.^
^ft -' ' v-
!
1
1.
1
.' ' S3 '.-. . .
64
72
li 1,
11 ' ' 1 ' ' 1
i\
jJL^J.
T'O . '
t. ''.
'01'.
. ' 1
S5
u^_..,.L_(:iLJ.^.. [LCJIL,^^,,,
i"1 :»' l.'m ,!.-,
133
'-.I :^,-.^^l
-------
MIC:- \'-t'.>~. rp'.in
OV : '":'' I-J :.':'"'< *."0:
>-i;,% C:. f L:j'>v,rr rMMIOE:
CMMI: .-.: ci -F-F-MBE
OH T H : f-'l '"» ir--
tMLi: >:Sir i
2-F1 uoi^ o AC e t an i tie
H
HJM-OC-F
2 " ',
0 H
M-2
70
i *-
ro
-------
I'MSS SPECTRUM
yi'-"04 :3r ^:57:'^Lt -i 7'lt3Z
SAMPLE: I300PIH 3 TO 25(3 !'
Cut IDS.: El
GC rEMP: 233 DEO. C
Of-lTAi ISOOP HI."
2-4 O
280
3':
-------
TH: lli.r- 9 J 0:{l
alpha-Nap thy 1 thiom^oa
H S
N-C-NH,
2-Xsothiocyanato naphthalene
101
114
l-'l
i rsn
-------
IOC.;;' -i
50.0 -
HuS'J. i.PECTPUH
d^-'uS-St* 1-1:10:00 * 18: 12
SMl-lPLE: OCfMnETHY PYROPHOSr-HC'RftM IOE U01KOOI030
CC I'EMP: JOO DFC. . C .
' ' . . 135
3.1
DHTH: Of-P KlO'ji
CHL1: CFEE-i;: MS
153
.M-2 ' "
Octane
MA .0 0 ,CH,
CH
-/
CH
-------
Mti .; f i.r iruM
O" I'l 4.' !tlOJ:"'i ». 2i
^..flS-l h i ..LCTGIIITPILE LC
C""O '..I t I 'Ci".
'mlE-l'O
I 0'3. O -i
Acetoni tr i le
N=C-CH
39
M--2 28
I
30
33
4;
-------
! t" Tf.l-K
..* ' 10: ''': " * . >; JS
' : / MI *." T it . .f I / MJ.II i t.u if.'[ 'nf i.i.i ! Ft .-''.. ,*
I
i-
(
2-Acetylaninofluorenc
tf-9
NI-C-CH3
.-Jli-,-
140
-------
r
. O -i
50.0 -
237
MM'.V; iTPEC rPUn
tC-'iH-ar lM:4f.:»HO * ZT::3;
SuMPI. F.l HLPHt. OILORADHlIt: LOTMP.SOl STO
c01 IDS. i ei
G''. TEMP: -J-n DEC;. C
!;!l.Uili lUlJil
272
233
II llTlU
99
II
283
OfiTM: MCHLOP: Bli-5.':
t'Ml. I: CFEfc'3 «S .
cis-Chlordane
IS*
143
111
240
260
300
320
ISO
160
I
230
-------
50. O -
MM':/; SPECTRUM.
CO OJ'37 11:31:00 » 22:13
. 5'-r-'.PLE: -I^MMMH
,Cr.:lO-i. i El
GC tCMF: ; j-a
CnLI: CrrCM. '1*3 '.**
trans-Ch1ordane
Ci '
cr
v V',111
iC3
i
Jill,
t
,!,:^.jj
'i ;ao . 3\'0
o?'.*
r^,...-r,.^J.I..I.l....
M,
UiU ,1.
".''.<*'
1 *
» _ . t t 1
III
i
.iijl
!
Jl
1
jr
t . » ,
i-
|; ,Iilii, '-
» i ., ,i, »|. »..|(
:: ill
."ii --! Ji
,i ,11! I,! i,jl|'
};, ; ;!,'i: i |i|i|i . i|ii:j!l-!
-------
It" LO ! «0-H-'.;'ii:L
DxTi-'i: lit. Vf ftp »-l '.''.
'l-.LII Ch't.fM Hi
1 00.. 0 --,
49
_^..LLJ
Til
2-D i ch 1 OP opp op.an'e
H H
Gl
I 'S3 c,-
-I*-- T-t-T-f ,P/ .
3-;-
-------
HWiS SPECTRUM
o;- tfK'gr 11! 13:00 + 17: 4O
SAMPLE: OlftLLttTE LOTKV002
CO! ID-;.: F.I
GC TEMP: 135 DEG. C"
D&Tli: DIflLL Ulu
CHL1: CFEB-ll ttj
100.0-,
so. a -H
46
S6
kU
129
109
I-.9.?. .H
ua
109
Diallate
(CH^-CV .9 :' y ci ci
H
H
2S-;
152
150
200
250
-------
MM-;; sptc itijn ' '
Oj-T'4-sr 12:S4:OO * 23:47
SHf-IPLEi P,F"'-DC.IO LOTmiSC'3 STO
Cut ID--:.: El
fcC-TCMP: ^" DEO'. C'
63
101
til
H
CI-C-CJ
rt
137
1S1
1 93
DnTftl 'ODD »1427
CrtLI: CFEE4 t, 3
-------
oo
CO
_
;- M';. ::r 10: I"J:'Xi 2T:44
.I'lf-I.C:' 01 -II-MI T-.'L F--MTHMI.HTE LOTtlt'lG4 -_.1U
. Jllir.. : LI
GO ICt-li : JO-' CiL'j. C
' EHHHllCEG 'S fSS -ill
93
50-
pHl'M! L'OF' HI'.-''-!
LMt. I: r.FKU-U It i
Di~n-Octylph thai ate
0
150
i-00
,--, --- .- r
250
273
-------
100.0 -i
HH-f.S SPECTRUM
<->::. 04-*.- 1-4:17:00
SAMPLE: HK
COMDS. : El
GC TEI'IF': liT DEC. ..C
LOTHEC14L
SO
O3
107
118
Jl,
too
D«T«: HEXCB .t»107i
Cm. I: CFEB4 t»3
15O
Hexachlorobenzene
Ci Cl
Cl Cl
177
1'KO
200
Llr
-------
UlfLiil
5fi
M.iSS SPECTF'Uri
i:C-.'O-i-87 lJ:-4::>Xt + 18:33
'-M.IIPLE: LltlOxtlf-" t.OTItK-^nO
(.rjUD-i. : El ' .
'JC TEtiP: 203 DUG. C
1C'9
- '- I"
a
121
U,
135
y
[JMlli: LIMLi S! 1 1 1 '
-HLIl CKtE:4 Hi
ll .33 -»= '
1-411i*, . t-f-f ,
Lindane
1 /^\ 1
H Cl
-------
MfLE: HE::M'"HL.OPi"CTHMtC LCi TBEf.Ol
,tl( r.-.. : I: 1
IL'Nf': 10:' nt.0. C
OMTM: HEXF.T
C'MLIl CFEB4
OJ
01
->
'
.,, ,., , *r. ,,
9
-»
8.
*""i4 *V*i
3
_'
i|
i
'
1 .'- '
H exach 1 or o ethane
Cl
"1
Cl
CI-C-C-CI '.
II
Cl Cl
Jj.
1
1.
t\
-t
If
.L.
;
11
, 1
. I no
roo
-------
DnTM: LuSfO 1*1 13
' . 5
J
5
_
t-U
3
b
t,-,J4-
CSJ
0"; t£-37 15:37:00 * 1:53 CuLI: Cil*I ft 3
'_"M'-lPLE; LM2IOLHPPIME LOT«EW-0£f0930-01
CONDS. : R I -PROBE
..''-
1
5
00 1
!v2o,i|iiL^J
j
100 1
20 ' .
- '''. '
i :>- ' " ,'
i
:-o
'
j '
I
' . ' '
.
1-11
1
',
Lasiocai^pine
H
CH
CH5
H,C-C-OH
3 I
0=C-C~CHCH3
X
COO CH2
335
r
2*0
260
zee
700
3-41)
-------
.;' .1II I i:: M. ,L Or li .f i! r PI LE ' ' L'011
;.'.' Iti'lP: ' .-0 DF."i7
. '.'HL! : C SI? »'
Malononi tri le
N=C-C-CEN
M--2
V 5S
I I
} ' ' *^"r -^-t~-«"r= t-y----r-.r--^-r-
-
-------
lOO.Q -i
M.fiS SPEC t>UM
ii't'13-yr t.!':41.Ot> ».-
tii? i PI IP: ci-t ot:i:.. c
!L LOT»MM IJSII'?
: MRTMU "1
C i)L I : -Ci'l 3 « S
142 ..
JO.O -
Me chylthipuraci1
s
II
-------
. ?
MM , ' I'! ' Tt-Mt1 ..
'..r::.l: I M Ij.i.i:'. !. I !' I 111! l.nl t'.i'l"'. I'M
1.1 III. I ..111
rs I!.! II-: -j'^ C.-l.f,. >;
I
Thioacetanide
5
fi.
n.-z
-1--'- -r-'r--
-------
i'
I
^
I-
:
I
C'.< I'." -^r I":O~:IUA * i:l-)
5«P!HLK: TMIPdd ' L UTBPO'il. JUL 1O
GC TEUP: 49 DEC.. C
>3#
(iMlxi THlf-'nft 111 ;:!
<: -HL 11 c :: i ? »?
s s .
N-C-S-S- C-N (CH3)2
47
L
' "54'
..I I
105
100
1 T'H
j-
K'.v'i
16-t
-------
i
MH'r-S SF-ECTRiJII
I'J':- 10.-ST 1-1: IT; OC1 » 2: 15
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COMO-... ; ;:|
iiC TtMfi '3C DEC. C
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I
OATH: MEME it 155
CfiLIi C317 IIJ.
Methyl Methacrylate
0
II
n3C~~0 C C CHj
.CH2
160
-------
-C.
OJ
M.6
MnSi SPECTRUM .
'
. SAMPLE: rtHHSi-IPIHt
. COtIDS. ; E I-f-'Pij&E
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C.ML.Ii C ii
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^ NH2
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l^'O " 140
-------
IflO.O -,
63
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Chlorafibuci 1
(CI-CH2CH2)2 N -A- CH2CH2CH2CO OH
110
ISO
j?.jff..._,t
194
Hi , 2<3f.
~\U-W~< M-i,
230
-'5
200
250
-------
MnSS SPECTRUM
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NMr'S SPEC'I RUM - .
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-------
. APPENDIX'S
FT-1?. ANALYSIS
The identities of three of the "second third" compounds (.methyl
.nethacrylate [MM], 0,0,0-triethylester phosphorothioic acid [OP], an'd
'tn"s(2,3-dibromopropyl jrphosphate [Tris]) -wj're confirmed by their infrared
spectra. A Digilab FTS-20C Fourier transform infrared instrument with a
glowbar source and a HCT detector we re'.'used for this purpose. 'In each
case., spectra were obtained as a thin-flip; Between KBr disks. Figures Bl
and B2 are the spectra of-HM and OP, respectively. In both cases, .the
spectra :natch very well with standard icforence spectra to give acceptable
confirmation of MM and OP. . Additionally, Figure B3, which is a spectrum
of Tris, matches well vith the standard reference spectrum. There was
some concern as to whether'T'ris could possibly be the tris(l,3-dibromo-2-
propyl )phosphate isomer, for which no standard reference spectrum could be
located. This possibility was essentially eliminated by recording the
spectra of 2,3-dibromo-l-propanol. (Figure B4) and 1,3-dibromo-2-propanol
(Figure 85).- Since the C-H bands (at. 3000 and 1500 cm"-1) of the two
alcohols are. quite different, and the C-H bands of Tris closely match
those of 2,3-dibromo-l-propanol, the structure of Tris .was confirmed.
117 -
-------
4iia i?£i3ixLde~ib
Figure Bl. Infrared Spectra of Methyl Methacrylate
-------
o. o. o-m IE rnYLPMosfhc^o mIDA re
Figure B2. Infrared Spectra of O..0,0-Triethylester Phosphorothioic Acid
-------
p
"£
i
M
in
34£:a 32C3 3ZZQ 2d::i3 2S2J 2*23 221-3 2^2d Icfea ife MC3 T& ifc"
ETA rais
Figure 83.. Infrared Spectra of Tris(2,3-Dibromopropy1 )Phosphate
-------
3u23 3620 3^
2-Ji!3 2223 2223
HAVENL'HEERS
1 ,3-OIcRC,MQ-2-PRCPAJ-;CL
Figure B5. Infrared Spectra of l,3-Dibromo-2-Propanol
eea
-------
DISILAB rrs-iMX
w
en
"V
u
o
2
<
e
V*
.,
'':ft
2.3-D JEflQ-.Q-1 -I'RC^AJ -CL
Figure B4. Infrared Spectra of 2,3-Dibromo-l-Propanol
.eea
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