Critical Review of Hydrolysis of Organic Compounds in Water
`Under Environmental Conditions
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`W.MIIbny undT.Mill
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`Stanford Research ."rt5I'itttte, Merlin Paris. California 94025
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`This review examines the rate constants for hytlrolysis in water of I2 clauses Oforgatiic compounds with the
`IJb3et:ti\'e of using these data to estimate the preslstertcc of these compounds in freshwater aquatic systctlls. Fri-
`rnary data were obtained by literature review through most of l9T5 and some of 1976. These data. which include
`values for acid. base, and water promoted rate constants (75,,
`it... wk] and Iernperature coefficients are presented
`in IS tables in section 4. Estimated rate constants for nydrolysia under environmental conditions are presented
`in 13 tables in section 5. inciuding rate coltstanls at 298 K and pll T for acid,hasc, and water promoted reactions
`togethvt with \-aim.-st for the estimated rate constant [in] and the half-life {t,__.}].
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`Key words: Acid; base; environmental conditions: freshwater systems; hydrolysis: organic compounds; rate con-
`SIEIIIS.
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`lntrottuction .
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`1.1. Background .
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`L2. Content of This Review .
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`l 3 Error Anaiycitt
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`1.4. Literature Review .
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`1,5. Format .
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`[.6 Acknowledgments .
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`References for Section I
`2. Physical and Chemical Properties of Freshwater
`Aquatic Systems .
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`2.]. Cliulatilcl i:sIit::u uf U.S. PEI.’-‘.\lI\'|‘£l1l‘I Stu-mitts
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`4.7. Acyluting and Alliylilliltg Age-tits
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`References for Section 4.7 .
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`5 Rated nf l~l_\.'rirnlysis'. Estimates of l.ifctin1t'.s
`Under Environmental Conditions .
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`5.]. Alkyl. Allyl, and Bcnzyl llalidcs and
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`5,2. Epuxides .
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`5.3. Esters .
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`5.4. Alnitics .
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`5.5. Calbutliattrs .
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`an:lRivc1's .
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`3. Hydrolysis Kinetics .
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`3.2. Effect of pH .
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`3.3, Effect ofTemperaturt: .
`3.4. Effects of ionic Strength and Buffers .
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`390
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`4. Rates of Hydrolysis: Literature Review .
`4-. l. Alkyl, Ally}, and Benzyl Halides and
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`Polyhaloalkanes .
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`References for Section 4.1 .
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`© I9'i'8 by the U.S. Secretary of Cmnmorcc on behalf of ill!‘ United States.
`This copyright
`is assigned lo the .'\n1cric:in lnslilute of Physics and the
`Amoriccn Chemical Society.
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`5.6. Phusphorit: and Pltosphunit: .-"will Esters .
`5.7. Acyluting and Alltylutittg Agents and
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`1-‘IGIJRE l. pH Dept.-ndcritrtr ofk, for hytlrolysis by
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`0041-zsstmatzi t4-o:u3sIu.sn
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`383
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`1.91-up. ctmn. Roi. Data. vol. 7. No. 1. tin
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`NOVARTIS EXHIBlT 2042
`Noven v. Novartis and LTS Lohmann
`IPR2014-00550
`Page 1 of 33
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`334
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`W. MABEY AND 1'. Mill.
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`5.l. Organic halides .
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`I.
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`introduction
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`1.1. Background
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`During 1975, 293 billion pounds of about 3,000 different
`organic compounds were manufactured in the United States,
`exclusive of petroleum products ill.‘ Each year about 5,000
`new compounds are synthesized, and 200 to 300 of them
`come into commercial use
`Many millions of pounds of
`synthetic organic compounds are deliberately introduced into
`the environment for weed and pest control. and many mil-
`‘rutts of pounds of other chemicals are introduced into the
`environmental through dispersive uses.
`The effects on the biosphere ofthese often persi.<-.tcnt.oflen
`biologically active synthetic chemicals are only now becom-
`ing fully apparent: fish kills, species extinction or encrvation,
`and perhaps as many as several hundred thousand human
`cancers per year have been associated with the increasing
`production and dispersion of synthetic chemicals [3]. in an
`effort to avert further, and perhaps tragic. biological conse-
`quences of a continuing and unrestricted discharge of chem-
`ical: to [he air_ water‘ and enil_ Ii'\F gaunt-nmrnt l"tf‘.gRI‘I
`.‘t(J|TIl".
`years ago to regulate the manufacture and use of selected
`compounds. such as DDT, which had been shown to be ex-
`ceptionally hazardous to the biological environment. The
`Toxic Substances Control Act of 1976 is one further step
`toward regulating the introduction of hazardous chemicals
`into the environment.
`
`Fortunately. the environment has the capacity to cleanse
`itself of many kinds of chemicals through a variety of chem-
`ical and biological processes. lltn understanding of this proc-
`ess. espccially how rapidly the environment can degrade a
`specific chemical structure to a simpler and potentially less
`harmful chemical, is a key to the rational use of natural rev
`sourccs with minimal abuse. The ability to predict the proba-
`ble fate of specific compounds in the environment is also es-
`sential for screening the thousands of chemicals that may be
`considered for applications leading to their ultimate intro-
`duction into water. soil.or air.
`The objective of this review is to provide one kind of pre-
`dictor of environmental
`fate—hydt-olysis of organic com-
`pounds in freshwater systems—based on the best available
`ltinetic data for hydrolysis in water.
`
`' Figures in buckets indicate lilerllurc references at
`subsection.
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`the end of each section or
`
`1. Phys. t.‘.1lcm. lot. I:In1u.Vo|. T. No. 2, 1978
`
`There are at least two reasons why hydrolysis may be a sig-
`nificant chemical process in the environment. First, many
`l-tydrolyaable chemicals, including pesticides and plasticizers.
`eventually find their way into groundwater, streams, and
`rivers through leaching and runoff. Second. rates of hydroly-
`sis in aquatic systems are independent of commonly used but
`rapidly changeable indicators of the degradative capacity of
`aquatic systems. such as sunlight, microbial popttlalinnsy and
`oxygen supply; rates do depend on pH.
`temperature. and
`concentration of chcn1ical—praperties that may change only
`slowly and seasonally.
`In undertaking a review of this kind, which claims to pre-
`dict rates of hydrolysis in aquatic (freshwater}systems on the
`basis of laboratory data. we are aware of the belief that such
`estimates are of little value because the rates ofhydrolysis ob-
`tained in laboratory studies do not reflect the complexity
`found in the environment. This concern, although under-
`standable, is not well founded. There are several examples
`where rates of hydrolysis have been measured in both pure
`and natural waters and which showed good agreement be-
`tween the two kinds of measurements for a variety of chem-
`ical structures [9,.'),o] providing that both pH and tempera-
`ture were measured.
`
`Another objection raised occasionally concerns the validity
`of the extrapolation of data for hydrolyscs measured in the
`laboratory at concentrations of chemicals that often exceed
`0.01 M to environmental conditions where typical concentra-
`tions of trace organics rarely exceed 10“ M. The apparent
`implication ofthis concern is that at high dilution other com-
`plications may arise but in fact it is axiomatic that rate proc-
`esses found to be simple at high concentrations remain so at
`luw Cotlccsltratiotta; rrtot-cover, with only one exception, the
`rate laws for hydrolysis reviewed here show a simple first-
`order dependence on the chemical. Thus the actual half-life
`of the chemical
`is
`independent of its concentration and
`depends only on easily and accurately measurable param-
`eterslike pH and temperature.
`For these reasons we believe that in most cases extrapola-
`tion from laboratory to field site is relatively uncomplicated
`and that estimates of persistence summarized in section 5
`provide valuable information on the upper limit for persis-
`tencc of hydrolyzahle dissolved organic compounds. From
`these estimates it should be possible to also assess possible
`effects of intervention by other environmental processes.
`Thus, if field measurements of the half-lives (persistence) of
`
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`
`HYDROLYSIS OF ORGANIC COMPOUNDS
`
`385
`
`specific chemicals depart significantly [by factors of 5 or
`more) from those predicted in section 5 after [airing into ac-
`count differences in pH and temperature. then some other
`process such as hiodegradalion. or photolysis or insolubiliza—
`tion may have changed the measured half-life. These esti-
`mates apply only to chemicals dissolved in water;
`in most
`cases any suspended or oil solubliacd chemicals will hydrol-
`yse much more slowly than predicted.
`only recently has tltctc been muuit inter est in Incaautittg U1
`estimating the rates of hydrolysis of organic compounds
`under environmental conditions which include very dilute
`solute concentrations in pure or natural waters in the pH
`region '1 to B at or below 293 K. In the absence of much
`environmentaliy-"intended" data,
`this review has drawn
`upon a large amount of hydrolysis data from studies con-
`cerned with kinetics and mechanism. Some ol these data were
`
`obtained from experiments in mixed solvcnts,or at high teln-
`peraturcs {to 393 K} or extreme pH values. and often lack
`tlata nn lt_-mlinralllrfl Li|_'[H_'l'I(iEfl|Z‘lZ‘.
`In some cases data are given for compounds which are not
`of environrnemal concern; however these data do describf‘
`the range of rate constants for the class of compounds and
`make it possible to estimate the rate constant(s} tor and per-
`sistence toward hydrolysis of organic compounds not
`in-
`cluded in this review.
`
`We hope this review will stimulate more and better studies
`of liydrolysis of synthetic chemicals in water under carefuily
`defined conditions, both in the laboratory and in the field, to
`.=uppl<-mt-nt the data presented here and further valirlate the
`concept
`that careful
`lalmratory studies on individual proc-
`esses can accurately predict the fair: and persistence of client-
`icals in the environment.
`
`1.2. Content of This llovlow
`
`This review provides information on kinetics of hydrolysis
`in water of 13 classes or organic structures, with sufficient
`detail within each class to enable the reader to find either the
`spccific cornpound or one close enough to estimate reliably
`the rate i:onstant(s) for hydrolysis. The classes of compounds
`rei.-(owed arc:
`(1) Organic halides
`(a) Alliylhalides
`{ll} Allyl halides
`(c) Benayl halides
`(d) Polyhalomethanes
`(2) Epoxides
`{3} Esters
`(a) Aliphatic acids
`OJ) Aromatic acids
`(4) Amide-s
`(5) Carbarnates
`{6} Phosphorus ester:
`(3) Phosphonates
`fl») Phosphates and thiophosphates
`(c) Phosphonohalidates
`(7) Acylating and alkylating agents and pesticides
`Kinetic data are presented in two sections. Section 4,
`"Hydrolysis Rate Data," summarizes primary kinetic data on
`
`hydrolysis ofthese compounds in water or [in a four cases) in
`mixed solvenunscctiott 5. "Estimated Hydrolysis Rates under
`Environmental Conditions," uses data from section 4 to
`estimate rate constants and lialf—lives for these same com-
`pounds at 298 K, pH T, and zero ionic strength. conditions
`typical ofa great majority of freshwater systems (section 2.1}.
`The classes of compounds reviewed here cover a significant
`fraction of the hydrolyzable structures found in organic
`molcculca. Many of the individual compounds listed in this
`review are used in quantity in industrial or agricultural ap-
`plications; others are unique to laboratory studies. Most of
`them have been subject to study in water solvent under condi-
`tions that require few assumptions and relatively short extra-
`polations to environmental conditions.
`5e\'eral classes of hydrolyzable compounds have not been
`included in this review because some are hydrolytically inert
`under ordinary conditions and are best considered as refrac-
`tory toward water {nitriles, vinyl, and aromatic chlorides are
`twamplt-9),
`rmrl ritiiprc are liyrlrnlytirally unstable hut have
`not been cxztrrlined in arty quantitatively useful way.
`
`L3. Error Analysis
`
`Because many tliffcrent kinds of experimental pgocedurcs
`are used to measure hydrolysis reactions, no one error analy-
`sis procedure is applicable to all sets of data. Rate constants
`for hydrolysis of most compounds appear to he of high preci-
`sion, often with less than 2% standard deviation. Different
`investigators have reproduced individual rate constants to
`within iS0%. Some sets of experimental data are reported
`with error limits that involve ajudgrnental factor in selection
`of data. These error limits maybe considered equal to twice
`the standard deviation.
`Most experimental rncasurcments of E or M!’ are made
`over tcniperature spans of 40-80 K and usually around 345
`K. Bensotns "rule" [I] indicates that with a random error of
`2% in rate constant Ir, activation energy E may be deter-
`mined with an accuracy of about 5%; however. with a random
`error of 10% in lr, E is only accurate to 100% or a factor of 2.
`Put another way,
`if E is known only with an accuracy of
`1.10%, It is known only with an accuracy of :Et(l%.
`Values for It. estimated in section 5 at 293 K are probably
`not more accurate than a factor of2(1l00%)0t'lcss accurate
`than a factor of 5 (:250°z’o] owing to uncertainties in pH,
`temperature coefficients, and. in some cases, solvent effects.
`
`1.4. Litorntoro Source:
`
`A thorough search of the current literature through 1975
`was made using Chemical Abstracts. Data were searched
`under the major subject headings for specific compounds.
`
`1.5. Format
`
`The review is divided into five sections; to assist the user.
`references are renumbered as appropriate within each sec-
`tion. Althoutzh every effort has been made to use a consistent
`format throughout, some differences among tables are un-
`avoidable owing to differences in the ltinds of compounds
`and the reliability of data available for various compounds.
`
`1. Phys. Chem. Ital. Data. Vol. 1', No. 2. I9?!
`
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`
`336
`
`W. MABEY AND T. MIl.l.
`
`Section 4 reports primary kinetic data in the form of rate
`constants for acid (3:4). neutral UK”), and base catalyzed (kg)
`hydrolysis reactions, together with available temperature co-
`efficients. Data are summarized in 13 tables. Section 5 uses
`
`data from section 4 to estimate in at 298 K and pH 7 for se-
`iected compounds in i3 tables.
`In each table, compounds are grouped by class, such il$
`alkyl halides. epoxides, and esters. and are listed in order of
`increasing complexity. Line formulas are used in most cases
`to avoid ambiguities of nomenclature.
`Rate constants is are expressed in units of s" or M“s".
`where M=rnol - dm"’. Very large and very small values of it are
`listed in two ways; "at uulumrt lrcadirrg 10'
`-fl require: that every
`listing in that column be multiplied by 10" to retrieve it: a
`column listing of S[-ll] means 5>¢l0"‘. Throughout this re—
`view. we have used the S1 unit of joules for energy and en-
`tropy: conversion of joules to calories requires division by
`4.134. Units for A are the same as for in: units for AS'' are
`.l/rnol: units for Eand Mi‘ are ltlfrrrol. To simplify presenta-
`tion Hf data in the tahles, we-. have fixed the value of R at
`0.CIl9l4 ldlmol K. which ittclutlcs a conversion factor of
`2.303 for base 10 log units.
`
`1.6. Acknowledgments
`
`This review was prepared under Contract No. 5455905 with
`the Office of Standard Reference Data. National Bureau of
`Standards. We thank Dr. L. Cevantrnan for his advice. ell-
`patiettet-., M5. Kathleert
`t:oura|.;e11rt:rit.
`lrnrl currsiderable
`Williams typed the many versions of this Inanttscrint with
`persistence and skill.
`
`Rufnroncos to r Section I
`
`[1] U3. Tariff Cornmission Report for IW4.
`12} Estimate provided by Chemical Fazonorntcs Department. SRI.
`[3] Higginson. .l.. Proceedings 8th Canadian Cancer Conference. Honey
`Harbour, Pergamon Press. New York, 1963. p. -10.
`I4] Zcpp. H. G.. Wolfe. ."i. I... Cc-1'rlon.J. .I\.. and Baughrnan. C. L.. Environ.
`Sci.Tcch.9. ll-14ll9T5].
`I5] Hebe)‘. W. Barazr.
`.-\.. Lan. 3., Riclrardson. H.. Henriry. D. C., and
`Mill. T.. M:-alt. 172 Meeting Amer, Chem. Soc.. San Francisco. (3..
`Aug. 1976. PESTOGI.
`[0] Wolfe. N. L.. Zepp. B. 6., Baughman, G. L.. ‘.Firn:t|t:r. fl. (2.. and Gor-
`don..l. A.. Chemical and Photochemical Transformation of Selected
`Pesticides in Aquatic Systems, EPA soor3.7s—o6r, September I9'r'Ii.
`[7] Benson. 3. W.. The Foundations of C.'remI':r:t Kim-tr'c:. 5t:Graw—Hil|
`Bunk Cn., New York {I960}.
`
`2. Physical and Chemical Properties of
`Freshwater Aquatic Systems
`
`The freshwater systems of North America's streams, rivers,
`lakes. and groundwater comprise several hundred thousand
`square miles of area draining 7 million square miles of
`diverse environmental regions. Since one objective of this
`review is to provide reliable estimates of lifetimes for organic
`compounds in freshwater aquatic systems. some review of the
`range of physical and chemical properties of freshwater is
`rir~s:ir:al-n|e._
`
`J. Phys. Cllorn. Rd. Data. Vol. ‘I. No. 2,1979
`
`2. I . Characteristics of U.S. Freshwater Streams
`and Rivers
`
`Detailed information on most freshwater systems in the
`United States. including temperature range. pH. and mineral
`content. is available from the United States Ceologieai Sur-
`vey it]. These data have been summarized for 111 streams
`and rivers in the United States that account for over 95% of
`the water volume; table 2.] summarizes mean concentration
`values for 11 inorganic constituents found in natural waters
`at pH 7.5 and 287 K.
`‘t‘.-able. 2.1 Analysis for U.1i.
`
`rivers and streams
`
`(nu-"In \JJll'rI_¢'€:
`in mryrt-‘.i_ _
`_'.
`-
`_
`___
`I
`_]
`—
`__
`_.
`
`,\;..+ ['15 Ii 13.?" I new; i mi‘
`I
`in
`[No
`?.?l 1.4 .-
`t
`t,__'..
`9 L23 J2 le_.n_s i_1_:_:_r___i__3i:_
`pit 7..-, Tt;'r|:p1?l'at.t:rf.’ RSTK
`
`
`
`is
`
`The following values represent average conditions in most
`freshwater systems in nonwinler months: temperature 293 K,
`pH 7.0. and ionic strength 0.00.
`Review of the hydrolysis literature for organic chemicals
`sliowe that many rule constants have been evaluated at 293 K
`or higher; only a few data have been Obtained at lower tern-
`pcratures. Although higher than either the mean or
`the
`average temperature of the rivers and streams. we have
`chosen 298 K as the environmental reference temperature for
`this review in order to use as much primary kinetic data as
`possible for estimates of persistence without temperature ex-
`trztpolattons.
`Estimates of persistence {half-lives] summarized in Section
`5, will he 50 percent longer at 293 K and 130 percent longer
`at 23? K. based on an average energy of activatiort
`for
`hydrolysis of 65 kl/rrrol.
`
`Roforonco for Section 2
`
`[I] Quality of Surface Writer.» of the United States. Parts 2~1ti. U.S. Geo-
`logical Survey Water Supply Papers 2U‘92—209'9. 19?? -73.
`
`3. Hydrolysis Kinetics
`
`3.1. Rate Laws
`
`Hydrolysis refers to reaction of a compound in water with
`net exchange of some group X with OH at
`the reaction
`center:
`
`HX+H;0"ROH+HX.
`
`The detailed mechanism may involve a protunated or anionic
`intermediate or a carbonium ion, or any cornhittation ofthese
`intermediates. But whatever the mechanism. the rate law for
`hydrolysis ofsubstrutc RX usually can be put in the form
`
`-—_._‘fllfl_=lr..[RX]=l:5[0H‘][RX]-!~k,.[H*]ERX]
`d.
`
`I
`
`1
`
`(
`
`+k.v'[H,0][RX].
`
`where kg, it‘. and lcN' are the second-order rate constants for
`acid and base catalyzed and neutral processes, respectively.
`
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`
`HYDI'tOLY8lS OF ORGANIC COMPOUNDS
`
`3'31’
`
`In water lr,..'[H;0] is a constant (kg). The pseudovfirst-order
`rate constant)!» is the observed or estimated rate constant
`for hydrolysis at constant pH. Equation (1) assumes that the
`individual rate processes for the acid. base. and neutral
`hydrolyses are each first order in substrate. With only a few
`exceptions, this is the case, and
`
`rh=rh[0H‘]+Ir,.[H‘]+Ir,¢.
`
`[2]
`
`From the autoprotolysis water equilibrium, eq (3), cq [2]
`may be rewritten as eq [4].
`
`[H*l[0H‘l=K.
`
`t.= l"K' +k,. H°}+t..
`[H-3
`[
`
`3.2. Effect of pH
`
`(3)
`
`(4)
`
`From eq (4) it is evident how pH affects the overall rate: at
`high or low pH (high OH‘ or H‘) one of the first two terms is
`usually dominant, while at pH 7 the last term can often be
`most important. Hot-vever. the detailed relationship ofpli and
`late dcpcmls uu the specific values of in L4, and 145,-. At any
`fixed pH, the overall rate process is pseudo first order, and
`the half-life of the substrate is independent of its concentra-
`tron:
`
`t.,=0.693X.lr..
`
`(5)
`
`Equation (4) is conveniently expressed graphically as three
`equations~ont- each for. the acid, base, and neutral hydrol-
`ysis reactions—in which log lr. is plotted against pH. The
`curves obtained are especially useful for estimating the effect
`of acid or base on the rate of hydrolysis. Figure l depicts a
`typical log in. vs pH plot for compounds which undergo acid,
`
`water, and base promoted hydrolysis. It is obvious from eq (4)
`that
`the upper curve in figure 1
`is a composite of three
`straight lines—(a) log lr.=log (ksK..)'l'PH; {bi log K.-log kg.
`and (c) log lr..=log 3:4-pH—\vith slopes + I, 0. and -1. respec-
`tively. The lower curve results when l:,¢=0.
`Most log in vs pH curves are found to have one or two in-
`tcrcepts corresponding to pH values where two kinds of rate
`processes contribute equally to the overall process. Thus in
`figure l the intercept Luv corresponds to a value of pH where
`f:,¢[H‘]=.lr,q; similarly.
`IN, corresponds to k.[OH']=rl:,...
`In
`cases where 1:4, R... or kfifl, only one intercept is observed.
`Values of pH corresponding to I may be calculated readily
`from the values of l:,., 1:... and leg:
`
`l.m=—l0g
`
`1.-»= -log (k,K_/k_..)
`
`(7)
`
`l_4,="[l0g(.h5K,,/rE,1}]2’2.
`
`Lase of intercepts in tabulating data on rates of hydrolysis as a
`function of pH greatly simplifies the taslc of estimating the
`effect of pH on the rate constant k. for a specific compound.
`For example, I5‘; for alkyl halides lie above pH 1!. Obviously,
`the basecatalyzed process for hydrolysis of allryl halides is
`never of concern in estimating persistence in aquatic systems.
`Values of 14», in. and Lu are tabulated for specific com-
`pounds in section 5.
`
`3. 3. Hint at Temperature
`
`Section 5 reports estimated ha|f—lives at 293 K based on
`rate data listed in section 4 at several different temperatures
`and with temperature coefficients for the rate constants.
`
`.095“R.‘.1E
`
`H‘-'-"RE 1. PH dependence of}. for hydrolysis by ar:iLl.\-rater. and base promoted processes.
`
`|>a<—..
`
`J.Phys.Chom.ltot.Do1a,\o‘ol.1,No.2.HTS
`
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`

`
`388
`
`W. MAIEY AND T. Mill.
`
`dict: they can lead either to rate acceleration or retardation.
`depending on the substrate. the specific salts, and their con-
`centration. Salt effects of this ltind are associated with
`
`changes in activity coefficients of ionic or polar species or
`transition states with significant charge separation; no bond
`making or breaking is involved in such interactions.
`Table 3.1 which lists some effects of different non-nucleo-
`
`The effect of temperature on the rate constant for a spe-
`cific hydrolysis process can be expressed in several ways, all
`ofwhich are variants of the general relation
`
`log [tr/s"}=—A/T+B log r+c.
`
`-:9)
`
`There is no uniform practice for expressing values ofA. B, or
`C; different investigators have used different versions of eq
`(9}. usually in more familiar Arrhenius or absolute rate theory
`format
`
`log {Ir/s")=log A-E/RT Arrhenius (10)
`
`(1 1}
`log (lc/s")=log [lrT,../lt}—Nf'/RT+ A3.”/R Absolute
`Rate Theory
`
`Equation [9lcar1 also he used to describe more accurately the
`effect of temperature on the rate constant and activation
`parameters by inclusion of 2 heat capacity contribution in the
`constants B and C. When the heat capacity term. AC1,
`is
`known or can be estimated, AH‘ and J55‘ are then calculable
`at a specific temperature, T3, from MI: and 155". or .EtH'r_and
`$3‘:
`
`AH;,=.iH:+sc;,r. or w;,=a1r*..—s c,,(r,-T.)
`
`AS‘§J=AS§+2.303 arr, (log T.)
`
`or A3r_=A5y_+2.303 dC,|og (T;/T1)
`
`A few authors have expressed rate parameters for a reac-
`tion in the mixed terms of E and 115". Although such a prac-
`rice is not immediately useful within the individual Arrhenius
`or absolute rate theory treatments, the rationale appears to
`he that AS’and E are more easily conceptualized for diagnosis
`of the reaction mechanism.
`
`Recasting of data to fit a uniform temperature dependent
`relationship might assist
`in mechanistic interpretations;
`however, the probable loss of precision for some data argues
`against such a practice. Therefore this review uses the origi-
`nal
`temperature dependence relationships developed for
`each compound to extrapolate rate constants to the chosen
`environmental temperature of 293 K.
`Each table of data in section 4 lists the appropriate tem-
`perature coefficients together with values of coefficients in
`ap|.JIU|.Irinlt' units. For a few compounds where no tempera-
`ture coefficients were determined and the reported data are
`not at 293 K. we have extrapolated to 298 K using a stated
`tcmperattirn coefficient. based nn 9 similar roar-tinn with
`known temperature dependence relationships. In :1 very few
`examples where data are reported within 15 K of 298 K, we
`have used the data without further correction.
`
`3.4. Ionic Strength and Butler Effects on Hydrolysis
`
`The Ionic strength of most natural freshwater is quite low,
`usually much less than 0.0‘: M in total cation and anion con.
`centrations (see table 2.1). This is
`fortunate since ionic
`strength effects on hydrolysis reactions are difficult to P”.
`
`I.Phy:.Chom. |t|f.DoIa,Vo|. 7,N-9.1, I931
`
`philic salts on the hydrolysis of several kinds of compounds.
`shows that in most cases rather massive amounts of these
`salts cause only 30-40% changes in rate constant. Concentra-
`tions necessary to effect these rate changes are found only in
`ocean or brackish waters or in highly buffered laboratory ex-
`perirnents.
`Table 3.1.
`Compound
`_
`l
`
`Salt. cltccts in h-,-drolztsiv reactions.
`Silltl . H
`
`3<..'k”" Refer:-nccf
`1.-fr-'4
`
`u
`
`3
`
`I
`
`I
`l
`I
`
`
`Solverlt. T.I'K
`-
`-I 1.13:. o.:os5 } aorioi .'t(-C{-Ol"II'.‘:I.-I:‘|'t'¢:.-
`1'.-Bulr
`323
`g
`|
`1.
`0.1.0!-I “Cl,
`.193
`08 i
`‘Y-But)-rolnetono. NGCI. 0.51
`
`0 as
`|l.Vt.:C1U-,. c.r.o o.1oi-t new... 293
`i
`1 35
`Litil. 2.00
`0.1591 ttc1o.. 293
`iCu.oo,t;r
`
`
`1.00‘
`.v.«c1o_, 2.00 0.1534 1-t:;to.. 298
`i
`":39 i____f __
`i
`i‘_*‘_°_1_:.9-_‘°°_ 1"'_‘“1”‘.-‘flit
`.3”?
`i‘?! Q°"i‘E__
`akfkfl is the ratio of HILEE with Us} and without Us") salt.
`
`JV
`Il
`I
`"I
`
`l l
`
`.
`
`Another effect of nucleophilic added salts is to accelerate
`the rate of hydrolysis by a general acid or general base pro-
`moted proccro {where H‘ or 0H" promoted reactions arc spe-
`cific acid or base processes}. Some anions can effect dis-
`placement of leaving groups more rapidly than water (kg) and
`in doing so catalyze hydrolysis via the sequence
`
`R-X-t-A‘ -v RA+X',
`RA+H,0—+ ROH+H:t.
`(HA-1-X :1 A‘-t-HX;_
`
`The use of nucleophilic anions such as phosphate or acetate
`at ll} M to 001 M to buffer hydrolysis reactions it: a common
`and useful practice. Unfortunately. the general acid or base
`catalyzed term lro[A‘] added to eq {2)to give
`
`Ilfat:-tlin[Ol‘l_]'+f€A[ll‘]+h_v+f€r:[A'l.
`
`can often be as large as the specific acid or base terms be-
`cause both [if] and [0H‘] are relatively low in the buffered
`1:51" 3.2.
`.’iutl<'t‘,‘.‘t1t!.'it)'rc:t'II=\:[:.
`(n! for dlnaalnronrnr rtarttun; ['-].
`
`|:-.n;-
`a s
`I
`;.-ts.
`01
`I
`mi
`3 a
`not‘
`3 s
`-o .-'
`.
`
`
`
`I
`
`.1 -=.-.i,-..-mt...
`tn, uturr n -.-.
`truth‘ .".,r1 .
`r. ms.-.:t
`“Emu u..- _\'».'.nr.-Scott
`fir:-v---Ju-n c:-nsut.-It Klt'.{'I: \'a:5r'.
`rxc.-t r...'5 to 1.5-. s In HcBr
`t.-. [.00 (5).
`la. 0112 I.
`l.
`rt
`1'-I»-r no ’Pf.A\'I[dI.
`.alf u...s...t= .'...
`.....t...
`.1.|.l
`.....r-.
`it-.-.,-nrtx-2'.-.-.
`
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`
`HYDROLYSIS OF ORGANIC COMPOUNDS
`
`389
`
`region rrorn pH 5 to 9. A5 a result, the value of It. may in-
`crease significantly. Table 3.2 lists