A 11 Id 2 IMbMlE

Ross. A.bertfUlS2 14641 2

QCIOO .U573 V8^^Wi97fl + -v - i ^ NSRDS-NBS 65

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The National Bureau of Standards was reorganized, effective April 9, 1978.
National Bureau of Stanza:" JUN 19 1979

Rate Constants for Reactions of Inorganic Radicals

in Aqueous Solution

Alberta B. Ross and Pedatsur Neta

Radiation Chemistry Data Center

Radiation Laboratory

University of Notre Dame

Notre Dame, IN 46556

f j * L. ' A Wf ctu\ i UAreUiuu U' A: ’M 7

‘ c/b

U.S. DEPARTMENT OF COMMERCE, Juanita M.Kreps, Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued June 1979
Library of Congress Cataloging in Publication Data

Ross, Alberta B

Rate constants for reactions of inorganic radicals in aqueous solution. (Nat. stand, ref. data ser. ; NSRDS-NBS 65) "National Standard Reference Data System.”

Supt. of Docs, no.: 03.48:65

1. Chemical reaction, Rate of--Tables. 2. Radicals (Chemistry)--Tables.

I. Neta, Pedatsur, joint author. II. Title. III. Series: United States. National Bureau of Standards. National standard reference data series ; NSRDS-NBS 65. QC100.U573 no. 65 [QD502] 602’.ls [541’.394] 79-607030

NSRDS-NBS 65

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 65, 62 pages (June 1979)

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Foreword

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III
Preface

This report is one of a series of data publications on radiation chemistry; the aim of the series

is to compile, evaluate, and present the numerical results on processes occurring in systems which

have been subjected to ionizing radiation. Various kinds of data are important in radiation chemistry. The quantities which were measured first were the observed radiation yields or G values (molecules formed or destroyed per 100 eV). Various indirect methods based on G values have been used to determine yields of transient species and relative rates of reactions. The spectral properties (optical,

electron spin resonance) of transients have provided a direct method for their identification, and rates of the very fast reactions of transients which occur in irradiated systems have been measured directly

by spectroscopic methods. Conductivity and luminescence methods have also provided a means of

measuring properties of transients and their kinetics. Some reactions which occur in irradiated systems

have also been studied by other methods, such as photochemistry, electric discharge, ultrasonics, chemical initiation, electron impact, etc. The emphasis in these publications is on the data of radiation

chemistry, but where other pertinent data exist, they are included.

The data of radiation chemistry are voluminous; thousands of systems have been investigated.

As a result there are certain collections, e.g. rate constants of particular types of reactions or certain

properties of transients, for which tabulations of the data are considered essential, but for which

critical assessment of each value is impossible. On the other hand, certain systems and properties

have been studied so extensively that critical examination of these data is desirable and timely.

Authors of this series of data publications have been asked to evaluate the extent to which the data can be critically assessed, to describe their criteria for evaluation, and to designate preferred values

whenever possible.

IV
Contents

Page Introduction 1 Table 1. C03“ reactions. (1.1-1.100) 5

Table 2. S04

~ reactions. (2.1-2.116) 14

Table 3. S02

~, S03

~, S2 03“, S2 02~, S05" and Se03" reactions. (3.1-3.16) 23

Table 4. N03, N03

2

“, N02 , N2 04, N203 , NO,2- reactions. (4.1-4.25) 25

Table 5. P04

2- reactions. (5.1-5.73) 28

Table 6. Cl2

“ reactions. (6.1-6.100) 33

Table 7. Br2“ reactions. (7.1-7.66) 38

Table 8. I

2” reactions. (8.1-8.30) 42

Table 9. (SCN)2

" reactions. (9.1-9.41) 44

Formula Index 46

References 49

V

Rate Constants for Reactions of Inorganic

Radicals in Aqueous Solution

Alberta B. Ross and Pedatsur Neta

Radiation Chemistry Data Center, Radiation Laboratory*,

University of Notre Dame, Notre Dame, IN 46556

Rate constants have been compiled for reactions of various transient inorganic radicals produced by radiolysis or

photolysis in aqueous solution. Data are included for the carbonate radical, sulfate radical, phosphate radical, nitrate radical and other nitrogen-, sulfur- and selenium-containing radicals, and the halide and pseudohalide radicals Cl2

~, Br2

~,

I 2' and (SCN)2

~. The radicals react with other inorganic ions, as well as aliphatic, aromatic and heterocyclic compounds.

Keywords: Aqueous solution; carbonate radical; chemical kinetics; halogen radical anions; nitrate radical; oxyanion

radicals; phosphate radical; photolysis; radiolysis; rates; selenium radicals; sulfate radical; thiocyanate radical anion. Introduction

The radiolysis of water produces short-lived intermediates, hydrated electrons, hydrogen atoms and hydroxyl

radicals, which react rapidly with solutes in the water to form other short-lived reaction intermediates (73-0030,

75-0001, 75-0002, 77-001 1)

1

. This compilation includes reaction rates for short-lived species derived from a number of inorganic ions, including carbonate, sulfate, sulfite, phosphate, nitrate, thiocyanate, and the halide ions

by radiolysis or photolysis. The radicals react by oxidizing a wide variety of solutes in aqueous media, most

commonly by electron transfer, but also by hydrogen abstraction, addition, substitution, and disproportionation.

Methods

Carbonate radical. The C03

" radical is produced by oxidation of carbonate or bicarbonate ions with OH or S04

'

radicals,

C032- -f OH — C03- + OHCO32- + S04

' - C03- + S04

2'

by photoionization of carbonate

C03

2 + hv — C03 + eaq

or by photolysis of certain carbonato-metal complexes, e.g.

Co(NH3) 4C03 + + hv -* C03

- + Co2+ + 4 NH3

The C03

~ radical has a broad optical absorption with \max 600 nm and €max 1880 M~ ] cm'

1 (66-0001). The

protonation

CO3- + H

+ CO3H

was suggested to have pKa 9.6 (73-7109), but it does not result in shifts in the optical (73-7109) or ESR spectra

(75-5244).

•The Radiation Laboratory is operated under Contract EY-76-C-02-0038 with the Department of Energy. The Radiation Chemistry Data Onter is supported jointly In the National Bureau of Standards. Office of Standard Reference Data and the Department Energy. This is Radiation laboratory Document No. NDRI/-1933.

Literature references are cited following the tables.

1
The majority of the rate constants for reactions of C03

" or C03 H were determined by following the decay of these

radicals through their optical absorption. The carbonate radical can oxidize certain aromatic and heterocyclic

compounds and inorganic ions, probably by direct electron transfer. It can also abstract hydrogen from aliphatic

compounds, but this reaction is generally slow. Intermediate or stable products from C03' reactions were identified

in only a limited number of cases and the mechanisms are mostly speculative.

Sulfate radical. The S04

~ radical is produced from peroxodisulfate ions by reaction with eaq ~

S2 08

2- + eaq - — S04

' + S04

2".

Reaction with various other radicals and metal ions can also yield S04

~. The other most commonly used method for production of this radical is photolysis of S2 08

2'

S208

2- + hv —* 2 S04

-

Oxidation of sulfate ions to yield S04

" radicals can be also carried out photolytically or radiolytically, but those processes are relatively inefficient and were not used frequently for obtaining rate constants. The S04

‘ radical has an optical absorption at \max 450 nm and €max 1100 M~] cm' 1 (66-0019, 69-0158). This

radical may protonate in strongly acidic solutions (67-7274) but no pA^a value has been determined. The rate constants for reactions of S04

~ were determined in most cases by following the decay of the 450 nm absorption. In some cases, the kinetics of formation of the product radicals was monitored.

This radical is a strong oxidant which can react with many organic and inorganic compounds by direct electron

transfer oxidation. The reaction with benzene and most aromatic and heterocyclic compounds involves this mechanism. However, addition to aliphatic double bonds and abstraction from saturated compounds were also shown

to take place. The products and mechanism of reaction of this radical were studied in some detail, many of which

are summarized under the corresponding reactions in table 2. Phosphate radical. The P04

2 " radical and its protonated forms are produced from peroxodiphosphate or phosphate

ions by the same methods as described for S04

~. The acid-base forms and their optical absorption properties can be

summarized as follows (78-1075):

h2 po4 hpo4

-

*0 o^

to 1

P^a 5.7 8.9

^max 520 510 530 nm

^max 1850 1550 2150 M~x cm' 1

The rate constants for reactions of these radicals were determined in most cases by following the decay of their broad absorption in the 500-540 nm region. These radicals can abstract hydrogen from saturated organic

compounds, add to olefins, and oxidize many aromatic compounds. H2 P04

is somewhat similar to S04

" in its reactivity, but HP04

- and P04

2 " are less reactive, both in H abstraction reactions and in electron transfer oxidations.

Other sulfur-, nitrogen- and selenium radicals. Various radicals have been produced from sulfite, selenite, nitrite, nitrate, and related anions, by one-electron oxidation or reduction, carried out either radiolytically or photolytically.

Some of the details for the production and observation of these radicals are given in tables 3 and 4. Representative

examples are:

SO,2

" + OH — S03- + OHN02

- + OH — N02 + OH"

N03" + eaq ' — N032'

S206

2- + hv -+ 2 S03“

S203

2 -T hv — S203 + eaq

2
Only a few rate constants have been reported for these various radicals, most of them are for the radical-radical

reaction. The reactions of these radicals with organic and inorganic compounds were studied in only a very limited

number of cases so that the rates and mechanisms are largely unknown.

Halide and pseudohalide radicals. Radicals of the type X2” can be produced from halides and some pseudohalides.

Tables 6-9 list the rates for Cl2

~, Br2“, I2

“ and (SCN)2

“, respectively. The radicals are produced by oxidation of the

halide ion followed by the complex formation. Oxidation of X" can be achieved in most cases by reaction with OH

X- + OH -> X + OH'

although complex and acid-base equilibria are involved, which cause the Cl' reaction to be efficient only in acid

solution (73-1039). Oxidation of Cl' in neutral and alkaline solutions can be carried out by S04

“ (e.g. 75-5244).

S04

' + Cl' -* S04

2" + Cl

Photolysis of halides can also result in their oxidation.

The X2

“ radicals are formed in the equilibrium

X + X' X2

-

which is shifted predominantly to the right {K s 105 M~] ) (65-0383, 68-0375, 73-1039). Their reaction kinetics are conveniently studied by observing their intense absorptions near 340 for Cl2

', 360 for Br2

“, 380 for I2

' and 480

for (SCN)2

“, all of the radicals having e of the order of 104 M~] cm'1

. The reactivities of the X2

" radicals generally decrease in this order: Cl2

', Br2

', (SCN)2', I 2

'. Cl2' can abstract hydrogen from aliphatic compounds but the equivalent reactions of the other X2

' radicals are barely detectible in the

pulse experiments. The reaction of Cl2' with some unsaturated compounds produces Cl adducts, and presumably the

other X2

“ radicals may react in a similar fashion, although little information is available on them. The main reaction

of the X2

' radicals is the one-electron oxidation, which takes place with many aromatic and heterocyclic compounds

and with certain inorganic ions. However, X2“ radicals are weaker oxidants than S04

“ and H2 P04

. The latter can

oxidize benzene and most of its derivatives, while X2“ can only oxidize phenols, anilines, and anisoles.

Arrangement of the Tables

Entries in each table have been numbered in order to provide for the assembly of an index. Within the tables reactions of the transient with the same or other transient species are listed first. Next are reactions of inorganic

solutes which have been ordered alphabetically by main element; the organic reactants follow in alphabetical order

by name. The reaction is given whenever evidence for the nature of the products is available; otherwise, only the

reactants are given in column 2. Rate Constants {k): Most of the second order rate constants are derived from pseudo-first order rates for the decay of

the transient or the build-up of a product. The error limits given are those reported in the original papers; lacking

such a statement the uncertainty in the rate constant should be assumed to be ±25%. Second order rates for reaction of two radicals have usually been derived from measurements of 2k/e; the value of € used to calculate 2k

has been listed in the Comments column. Possibilities for error in the determination of € increase the error limits for 2k, which should be assumed to be ±50%, lacking a specific error statement. In some cases the rates are designated (rel.) and have been calculated with reference to the rate of a competing

reaction, given in the Comments column. Ratios of rates are listed for a few reactions in the form k/kx in which kx is the rate of reaction of the transient with competing solute, X.

Ionic Strength (I): The ionic strength has been quoted from the original paper or calculated from the given solute concentrations, if that information was available. When the reported rate constants were corrected for ionic strength

the designation —>-0 is used.

3
Comments: The source of the transient and method of measurement are included in this column, along with other

information on product identification, or related values for equilibrium constants, pA, or isotope effects. Temperature is assumed to be room temperature unless otherwise specified.

References : The references are designated by the serial number of the paper assigned by the Radiation Chemistry

Data Center; the first two digits of the number represent the year in which the work was published.

Abbreviations and Symbols

A frequency factor ident. identification abs. absorption K equilibrium constant

alk. alkaline kf specific rate of the forward reaction

bipy 2,2'-bipyridine K specific rate of the reverse reaction

BuOH butanol L ligand

calcd. calculated M mol dm" 5

c.k. competition kinetics meas. measured

concn. concentration MeOH methanol

contg. containing obs. observed

cor. corrected <t> quantum yield detd. determined p.b.k. product-buildup kinetics

dien diethylenetriamine phot. photolysis

d.k. decay kinetics polymn. polymerization

e-r. electron radiolysis p.r. pulse radiolysis

€ extinction coefficient (molar absorptivity) 2-PrOH 2-propanol

activation energy rel. relative esr electron spin resonance RNO 7V,7V-dimethyl-/?-nitrosoaniline

estd. estimated A51 activation entropy

f.phot. flash photolysis satd. saturated

formn. formation soln. solution

G radiation yield (molecules per 100 eV) T temperature

AG° free energy *0.5 half-life y-r. gamma radiolysis therm. thermal

g!y glycinato unpub. unpublished

MR activation enthalpy

4
TABLE 1. Rates of reaction of CO, in aqueous solution*

No. Reaction k(Af' s'

1 ) PH I Method Comment Ref.

1.1 CO, -|- CO, — 2k = 1 .2, x 10

7 8.4- -+0 p.r. D.k. at 600 nm in N2 0- 66-0139

C02 + C04

2" 13.5 satd. soln.; e = 1860

See 78-1506 for mechanism AT

1 cm"

1 ; kiilt< s 5 x 10

at pH 13-13.5 2k = 4 x 10

7 7-9 0.1 f.phot. D.k. at 600 nm in airsatd. Co(NH,)4CO t + soln.; £ = 1830 AT

1 cm"1 .

73-7109

2k = 1.9 x 10

7 10.2 - p.r. D.k. at 600 nm in N20- 73-7109

2k = 2.9 x 10

7 12.7 satd. soln.; £ = 1830

M~' cm'

1 ; 0.1 K2 CO,. 2k = 6.9 x 10

7 11.8 - p.r. D.k. in 0.1 M Na2C03

soln.; See above. 73-7109

1.2 CO, -4- O9 — 1.5 x 10" 11.6 0.3 p.r. D.k. of CO3

" at 600 nm 66-0001

CO3

-(- Oj or 02

" at 260 nm in 02-

(or —* CO,

2" satd. soln.; €(260 nm)

See 70-0247)

(4 ± 1) x 10

8 - 11.8 0.6 f.phot.

for 02" = 1220 JT 1 cm

" 1 assuming €(600 nm) for CO3

" = 1800 AT' cm"'. D.k. at 260 nm (02

"), € = 1850 AT' cm"' and 600 nm (CO,") in 02-satd.

soln., € = 1860 AT 1 cm"

1 ; product (CO,

2"?) has £(260 nm) = 410 AT

1 cm"

1 .

70-0247

7.5 x 10

B 8-13 - f.phot. D.k. at 600 nm in air- 72-7335,

< 5 x 10

s

satd. soln. contg. NaHCO, and 2,6-anthraquinonesulfonate.

72-7464

1 . 2a C03’ 4- Br~ -11 - p.r. No reaction. 78-1506

1.3 CO3 -f- BrO — (4.3 ± 0.4) x 10

7 13 0.4 p.r. D.k. 68-0153

CO,

2

" + BrO

1.4 CO^ -f" Br02 — ( 1.1 ± 0. 1 ) x 10

8 13 0.4 p.r. D.k. 68-0153

CO,

2

’ + Br02

Co(U) ions 1.5 C03

- + Coaq2+

(4.4 ± 0.4) x 10

6 7.0 0.03 f.phot. D.k. at 600 nm in 73-7109

2.8 x 10

°

6.9 x 10

8

6.5 0.04 f.phot. Co(NH3)4C03

+

soln. D.k. at 600 nm in Co(NH,)4C03

+

soln. 78-1501

CO," + CoL(H20)22+1.5a 4.7 0.04 f.phot. D.k. at 600 nm in Co(NH3)4CO,+

soln. 78-1501

L = 5,7,7, 12,1 4,1 4-hexamethyl-1 ,4,8, 1 1 -tetraazacyclotetradeca- 1 ,4,8, 1 1 -tetraene

1.5b CO," + CoL(H20)22+

7.3 x 10

8 4.7 0.04 f.phot. D.k. at 600 nm in Co(NH3) 4CO f +

soln. 78-1501

L = 5,7^, 12, 14, 14-hexamethyl- 1 ,4,8, 1 l-tetraazacyclotetradeca-4,1 1-diene

Co(III) complexes

1.6 CO," + Co(NH3)4C03+ < 10° 7.0 0.03 f.phot. D.k. at 600 nm in Co(NHj)4C03

+

soln. 73-7109

1.7 C03 + (1.4 ± 0.1) x 10

7 7.0 0.03 f.phot. D.k. at 600 nm in 73-7109

Co(NH,)4(OH2)23+ Co(NH,)4C03

+

soln. 1.7a CO," + Co(NH,)63+

CO," + Cofen),

3

< 5 x 10

4 6.5 0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO t +

soln. 78-1501

1.7b < 1 x 10

5 6.5 0.04 f.phot. D.k. at 600 nm in Co(NH3) 4C03

+

soln. 78-1501

1.7c CO," + Co(NH3)50P03H +

CO," + CofNH,).,a

2+ < 4 x 10

s 6.5 0.04 f.phot. D.k. at 600 nm in Co(NH ! ),CO i +

soln. 78-1501

1.7d 2.0 x 10° 6.5 0.04 f.phot. D.k. at 600 nm in Co(NH3)4C0 , +

soln. 78-1501

5
Table 1. Rates of reaction of CO", in aqueous solution

11 —Continued

No. Reaction k(\r' s"

1 ) PH

1.7e CO," + Co(NH,)s Br

2+

5.7 x 10

6 6.5

1.7f CO," + Co(NH,)s OSO, +

1.5 x 10

6 6.5

l-7g CO," + Co(NH,)sO,C(;,H52+ 7 x 10

s 6.5

1.7h CO," + Co(NH,)502 CCH;, 2+

1.1 x 10

6 6.5

1.7i CO," + Co(NH,)s N022+

1.0 x 10

8 6.5

1 7j CO," + Co(NH,)s0S02 +1.1 x 10

ft 6.5

1.8 CO," + (2.9 ± 0.3) x 10

h 7.0 Co(NH,)s(OH2)3+

1.7 x

10'‘ >7.6 ~ 3 x 10

4 <5.6

1.8a CO," + Cr(NH,)5Cl2+ < 1 x 10

s 6.5

1.8b CO," + Cr(NHJsOH2 ,+ 7 x 10

5 >6.3

4 x 10

s <4.3

1.8c co:) - + Cu.,“ ~ 10

4 4.5

1.9 CO," + FeiCN),

4- -+ 2.7 x 10

8 11.6 CO,

2

" + Fe(CN)(;v

1.9a CO, -f H202 8 x 10

s 8-9

CO, + H02 5.6 x 10

7 13-14

1.10 CO," + I" — (1.3 ± 0.3) x 10

8 ~11

CO,

2' + I 1.10a CO," + lr(NH JSC12+ 2.4 x 10

7 6.5

1.10b CO," + Mn„2+

1.5 x 10

7 6.0

1.10c CO," + N02

" — 4.0 x 10

5 ~11

CO,

2

' + no2 l.lOd CO," -I- no2 — 1.0 x 10

9 ~11

C02 + NO,"

l.lOe CO," + Ni„,2+ < 10

4 5.8

1.11 CO," + cis-Pt"(gly)2 (4.4 ± 0.8) x 10

9 8.5

1.12 CO," + (3.4 ± 0.6) x 10

9 8.5

troni-Pt"(gly)2 1.12a CO," + Rh(NH,),Cl

2 + < 10

4 6.5

1.12b CO, + Rh(NHJ,OH21+

1 x 10

s >6.9 < 5 x 10

4 <4.9

I Method Comment Ref.

0.04 f.phot. D.k. at 600 nm in Co(NH,),CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO,

+

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4C0, +

soln. 78-1501

0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 73-7109

0.04 f.phot. D.k. at 600 nm in Co(NH,)4C0, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln.; pKa for complex = 6.6.

78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4C0, +

soln.; p/Ta for complex = 5.3.

78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

p.r. D.k. at 600 nm as well

as p.b.k. at 420 nm for ferricyanide ion in soln. contg. 0.072 M Na2CO,,

1.22 x 10"4 M ferrocyanide,

0.03% oxygen and 0.1 atm. N20; at pH 13 k ss

(3. 5-4.0) x 10

8

.

66-0139

3 f.phot. D.k. at 600 nm in N2 -satd.

soln.; pH-dependent (9-13). 70-0247 — 0 p.r. D.k. at 600 nm. 78-1506

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501 — 0 p.r. D.k. at 600 nm. 78-1506

- p.r. Est. from opt. and

condy. d.k. 78-1506

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.05 p.r. D.k. in 0.05 M NaHCO,. 77-1053

0.05 p.r. D.k. in 0.05 M NaHCO ,. 77-1053

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4C0,+

soln. 78-1501

0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln.; pKt for complex = 5.9.

78-1501

6
Table 1. Rates of reaction of C04 in aqueous solution

3—Continued

No. Reaction k(Af' s'

1 ) pH I Method Comment Ref.

1.13 car + Ru(bipy)(

2 ^

(4.0 ± 0.4) x 10

H ~ 0.02 p.r. D.k. of the Ru complex in N2 0-satd. soln. contg. 0.005 M each of HCO.,' and CO , 2

'.

77-1093

1.13a cor + Ru(NH,)f;,+ 6.0 x 10

f' 6.5 0.04 f.phot. D.k. at 600 nm in Co(NH,)4CO:; +

soln. 78-1501

1.13b CO.r + Ru(NH;i)5a

2+

7.7 x 10

6 6.5 0.04 f.phot. D.k. at 600 nm in Co(NH,)4C0,+

soln. 78-1501

1.13c CO," + Ru(NH,)-OH2

* +

1.4 x 10

9

1.8 x 10

8

>5.2

<3.2

0.04

0.04

f.phot.

f.phot.

D.k. at 600 nm in Co(NH,)4C0., +

soln. D.k. at 600 nm in Co(NH,)4CO,+

soln.; pKa for complex = 4.2.

78-1501

78-1501

1.13d cor + SCN"

CO,

2' + SCN

(8 ± 1.5) x 10" ~11 p.r. D.k. at 600 nm. 78-1506

1.13e co.r + so/- -

co,~ d

- so..

1.0 x 10' ~11 - 0 p.r. D.k. at 600 nm. 78-1506

1.13f co;r + so3

- ->

C02 -l- S04 *- 5.0 x 10

8 9.6 p.r. D.k. at 260 nm; also condy. study

78-1506

1.14 co3

- + uo/+ ~ 1.5 x 10" “ 0.16 f.phot. D.k. at 580 nm; results somewhat irreproducible.

76-7279

1.14a CO,' + Zn,/+ < io

4 4.7 0.04 f.phot. D.k. at 600 nm in Co(NH,)4C0,+

soln. 78-1501

1.15 Acetanilide 3.2 x 10" 7.0 0.06 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 75-7313

1.16 Acetate ion 6 x 10

2 12.1-

12.7

f.phot. D.k. at 600 nm in airsatd. soln. contg. 0.05 M Na2S208, 0.5 M Na.,CO ,; CO from reaction of S04

- + CO.,

2'.

72-7383

1.17 Acetone 1.6 x 10

2 12.1-

12.7

f.phot. D.k. at 600 nm in airsatd. soln. contg. 0.05 M Na2 S208, 0.5 M Na2 CO:j ; CO ," from reaction of S04

- + CO/".

72-7383

1.18 Acetonitrile 3.2 x 10

3 12.1-

12.7

f.phot. D.k. at 600 nm in airsatd. soln. contg. 0.05 M Na2S208

, 0.5 M Na2CO ,; CO ,’ from reaction of S04

‘ + CO/".

72-7383

1.19 Acetophenone 1.0 x 10'

(3 ± 1) x 10

s

~ 12.5 f.phot.

p.r.

D.k. at 550 nm in deoxygenated soln. contg. 0.3 M Na2 CO ,. D.k. at 600 nm; CO,'

also reacts with acetophenone-OH adduct, k = (1.5 ± 0.5) x 10’\

71-7574

78-1506

1.20 A-Acetylcysteine (1.8 ± 0.4) x 10

8 12.0 0.003 f.phot. D.k. at 600 nm; rate pH

dependent; value from

graph; CO,' generated from Co(NH ,)4CO,

+

.

75-7110

1.21 TV-Acetylglycine < 10" 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C0,

+

soln. 73-7352

1.22 7V-Acetylglycylglycine < 10

4 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO," soln. 73-7352

1.23 A-Acetyltrvptophan (4.2 ± 0.4) x 10

8

(6.2 ± 1.5) x 10

8 7

11.8

0.1

0.1

f.phot.

f.phot.

D.k. at 600 nm in Co(NH,)4CO,

+

soln. 73-7109

1.24 Alanine < 10* 7.0 0.06 f.phot. D.k. at 600 nm in Co(NH,)4CO," soln. 73-7352

7
Table 1. Rates of reaction of CO", in aqueous solution*—Continued

No. Reaction *(.W" s'') pH

1.25 Aniline 5.4 x 10" 7.0

1.25a Anisole

6.0 x 10"

2.8 x 10

s -

1.26 Anthrasemiquinone-1-

sulfonate radical ion •C0:| - + AQ —

CO,

2

' + AQ

4.6 x 10

9 -

1.27 Anthrasemiquinone-2-

sulfonate radical ion

2.2 x 10" -

1.28 Anthrasemiquinone2,6-disulfonate(5.4 ± 0.6) x 10" 2 x 10

9 7.5 8.0

radical ion 1.2 x 10

9 6.5

1.4 x 10

9 8-13

1.29 Anthrasemiquinone2, 7-disulfonate

1.9 x 10

9 -

radical ion 1.30 Arginine (9 ± 0.9) x 10

4 7.0

1.31 Ascorbate ion CO,' + AH' —*(1.1 ± 0.1) x 10

9 11

•A' + CO,

2' + H

+ 1.32 Aspartate ion V

r-H o 7.0

1.33 Benzene 3 x 10’ 7.0

< 5 x 10

4 11.7

1.34 Benzophenone 1.5 x 10

f‘ -

1.35 y?-Bromophenoxide ion 1.8 x 10" 12.2

fert-Butanol See 2--Methyl-2-propanol.

1.36 Carbon tetrachloride _ 12.0-

13.5

1.37 Chloroacetate ion < 2.0 x 10* 12.1-

12.7

1.38 /j-Chlorophenoxide ion 1.9 x 10

K 12.2

1.39 a-Chymotrypsin 1.0 x 10° 11.3

(1.2 ± 0.1) x 10

9 7-11

I Method Comment Ref.

0.06 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 75-7313

- p.r. D.k. at 600 nm. 78-1506

p.r. D.k. at 600 nm; CO,"

also reacts with anisole- OH adduct, ls3x 10

’

78-1506

f.phot. D.k. at 600 nm in airsatd. soln. contg. 0.05 M Na2 S20H and 0.5 M Na2CO,; CO, from reaction of S04 + CO ,"

; semiquinone

formed from CO,

2

" +

triplet AQ.

72-7383

- f.phot. See 1.26. 72-7383

- f.phot. D.k. in Na2CO, soln. 69-7297

f.phot. D.k. in 02-free carbonate soln. 73-7569

- f.phot. D.k. in NaHCO, soln. 72-7335

f.phot. D.k. in air-satd. 0.05 M NaHCO., soln. 72-7464

f.phot. See 1.26. 72-7383

0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO,

+ soln. 73-7352

p.r. D.k. at 600 nm in N20-satd. 0.5 M

carbonate soln.

73-3006

0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO: , +

soln. 73-7352

0.06 f.phot. D.k. at 600 nm in Co(NH ,)4CO, +

soln; uncertainty 50-100%.

75-7313

p.r. Benzene (1.4 x 10"' M)

had no effect on decay of CO,'; CO; ," reacts with benzene-OH adduct, k = 2 x 10

9

78-1506

— f.phot. D.k. at 550 nm in 02-free carbonate soln. 71-7574

0.3 p.r. D.k. at 570 nm in N2 0-satd. carbonate soln. 77-1098

- p.r. Decay of CO ,' faster in CC14 than in N20 soln. 66-0139

1.65 f.phot. D.k. at 600 nm in airsatd. S2 0„

2

" soln.; CO ,' generated by S04

" +

CO , 2' -+ S04

2

' + CO,'.

72-7383

0.3 p.r. D.k. at 570 nm in N20-

satd. carbonate soln. 77-1098

0.12 p.r. D.k. in N20-satd. soln.; mol wt. 20,000; concn.

effect.

74-1096

0.03 f.phot. D.k. at 600 nm; mol. wt. 25,000; HCO, or CO,'

generated from Co(NH ,)4CO , +

; k independent of pH.

73-7352,

75-7110

8
TABLE 1. Rates of reaction of COJj in aqueous solution

3—Continued

No. Reaction k(AT

l s"1 ) pH I Method Comment Ref.

1.40 Cysteine (2.7 ± 0.3) x 10

H 11.2+

0.3

0.3 p.r. D.k. in N20-satd. soln. 72-0036

(4.6 + 0.5) x 10 7.0 0.03 f.phot. D.k. at 600 nm; HCO, 73-7352,

3.5 x 10

8 9-10 0.003 f.phot. or CO," generated from 75-7110

2.5 x 10

B 12 0.003 f.phot. Co(NH,)4C0,+

. 1.41 Cysteine methyl ~ 1 x 10' 4-10 0.003 f.phot. D.k. at 600 nm; value from 75-7110

ester graph; HCO , or CO,"

generated from Co(NH,)4CO,+

. 1.42 Cystine dimethyl (7.2 ± 0.7) x 10

f> 7.0 0.03 f.phot. D.k. at 600 nm in 73-7352

ester Co(NH,)4CO, +

soln. 1.43 Diethyl disulfide 4.5 x 10‘ ~8 - p.r. D.k. at 600 nm in N20- 76-1143

6.6 x 10' ~11 satd. soln.; 0. 1-1.0 M HCO," or CO,

2". 1.44 jY^Y-Dimethylaniline 1.8 x 10

9

(1.4 ± 0.2) x 10

9

7.0 0.06 f.phot. D.k. at 600 nm in Co(NH,)4C0, +

soln. 75-7313

p.r. D.k. at 600 nm, as well

as condy.

78-1506

1.45 Dimethyl disulfide 1.0 x 10

8 ~8 - p.r. D.k. at 600 nm in N.,0- 76-1143

8.0 x 10

7 ~11 satd. soln.; 0. 1-1.0 M HCO," or CO,

2

". 1.46 3,3'-Dithiobis(pro- (1.3 ± 0.1) x 10

7 6.8 0.1 f.phot. D.k. at 600 nm; CO,H 73-7109

pionate ion) (3.0 ± 0.3) x 10' 11.5 and CO," generated from Co(NH,)4C0,+

. (1.0 ± 0.1) x 10

7 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C0,+

soln. 73-7352

1.3 x 10

7 7-12 0.003 f.phot. D.k. at 600 nm; CO,H

and CO," generated from Co(NH,)4C0, +

; value from

graph.

75-7110

1.47 Dithiothreitol (4.1 ± 0.4) x 10

8 11 0.3 p.r. D.k. at 600 nm in N2 0- 73-1020

(threo-2,3-Dihydroxy-1,4—dithiobutane)

satd. carbonate soln.

1.48 Duroquinone < io

f> 12 p.r. No reaction; previously

reported (76-7587)

k = 2 x 10

4 suggested to be for different reaction.

78-1506

1.49 Ethanol 1.5-1. 7 x 10

4 12.5 - f.phot. D.k. in soln. contg. 0.3 M 71-7574

CO ." + CH,CH2 OH ( +OH1 — Na2CO, and 2 x 10"4 M

CO,

2

" + CH,CHOH + H20 acetophenone or benzophenone.

1.5 x 10

4 12.5 f.phot. D.k. at 600 nm in airsatd. soln. contg. 0.05 M Na.,S2 0„ and 0.5 M

Na2CO ,; CO,"

generated from S04

" +

CO,

2" — S04

2

" + CO,".

72-7383

1.50 Ethoxybenzene 4.1 x 10

s 7.0 0.06 f.phot. D.k. at 600 nm in Co(NH,)4CO,+

soln. 75-7313

1.50a Ethylenediaminetetra- 1.1 x 10

6 - - 0 p.r. D.k. at 600 nm. 78-1506

acetate ion 1.51 Formate ion (1.1 ± 0.1) x 10

s 6.4 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO,

4 soln. 73-7109

1.6 x 10

s - -+0 p.r. D.k. at 600 nm. 78-1506

1.52 Glucose (7 ± 0.7) x 10

4 7.0 0.03 f.phot. D.k. at 600 nm in 73-7352

Co(NH,)4CO, +soln. 1.53 Glutathione (5.3 ± 0.5) x 10

6 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C0, +

soln. 73-7352

1.54 Glutathione (1.3 ± 0.1) x 10° 7.0 0.03 f.phot. D.k. at 600 nm in 73-7352

disulfide Co(NH,)4CO,^ soln. 9
Table 1. Rates of reaction of CO, in aqueous solution

J —Continued

No. Reaction k(M~' s'

1 ) PH I Method Comment Ref.

1.55 Glycine < 10* 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 73-7352

1.56 Glycylglycine (2 ± 0.2) x 10

4 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C0, 4 soln. 73-7352

1.57 Glycylglycylglycine (4 ± 0.4) x 10

4 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH ,)4CO, 4 soln. 73-7352

1.58 Glycylglycyltrypto- (7 ± 0.7) x 10

8 7.0 0.003 f.phot. D.k. at 600 nm in 74-7296

phan Co(NH ,)4CO, +

soln; k is pH

dependent, k — 4 x 10 8

at pH 10. 1.59 Glycylhistidine (4.3 ± 0.4) x

10'“ 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO, 4 soln. 73-7352

1.60 Glycyltryptophan (7.2 ± 0.7) x 10

8 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH: ,)4CO,

+

soln. 73-7352

X

00 +1 © 5c X O 7 0.003 f.phot. D.k. at 600 nm in 74-7296

Co(NH ,)4C0: , +

; k is pH

dependent, k = 4.5 x 10

8 at pH 10. 1.61 Glycyltyrosine (3.0 ± 0.3) x 10

7 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C03 +

soln. 73-7352

1.62 Histidine (7 ± 0.7) x 10

6

1 1 .2 ± 0.3 p.r. D.k. in N,0-satd. 72-0036

0.3 soln. (5.6 ± 0.6) x 10° 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO,

+

soln. 73-7352

8.5 x 10" 10 0.003 f.phot. D.k. at 600 nm; k is pH dependent; k ~ 1 x 10 ’ at pH 5 (values from graph); CO ,

- generated from Co(NH,)4CO;t +

.

75-7110

1.63 /?-Hydroxy benzoate 7.9 x 10' 12.2 0.3 p.r. D.k. at 570 nm in 77-1098

ion N20-satd. carbonate soln. 1.64 Imidazole (5.5 ± 0.6) x 10

1 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH.,)4CO., +

soln. 73-7352

1.65 Indole 3.2 x 10

8 7.0, 0.1 f.phot. D.k. at 600 nm; CO ,H 73-7109

12.0 or CO ,

- generated from Co(NH ,),CO,

1 . 4.1 x 10

8

(4.1 ± 0.4) x 10

8

5-13 0.003 f.phot. D.k. at 600 nm; CO,H

or CO , generated from Co(NH ,)4CO, +

; value from graph.

74-7296

1.66 Indole-3-propionate 7.0 0.1 f.phot. D.k. at 600 nm; CO,H 73-7109

ion (6.8 ± 1.7) x 10

8 12.0 0.1 and CO ,

- generated from Co(NH ,)4CO;, +

. 4.2 x 10

8 7-11 0.003 f.phot. D.k. at 600 nm; CO,H

and CO ,

- generated from Co(NH ,),CO , +

; at

pi = 0.1 k increases with pH; values from graph.

74-7296

Isopropanol See 2-Propanol.

1.67 Lysozyme (5.5 ± 0.6) x 10

8 7.0- 0.03 f.phot. D.k. at 600 nm; CO,H 73-7352

12 and CO, generated from Co(NH ,)4CO , +

. 75-7110

1.68 3-Mercaptopropionate (2.4 ± 0.6) x 10

8 12.0 0.003 f.phot. D.k. at 600 nm; CO,H 75-7110

ion and CO,

- generated from Co(NH ,)4C0, +

; k is dependent on pH, k ~ 3 x

10' at pH 7, values from

graph.

10
Table 1. Rates of reaction of C03 in aqueous solution’—Continued

No. Reaction k(M~' s'

1 ) pH i Method Comment Ref.

1.69 Methanol 5 x 10

s 12.5 — f.phot. D.k. at 600 nm in air- 72-7383

satd. soln. contg. 0.5 M Na2CO,; CO ," generated from S04

" + CO,

2" —*• S04

2' + CO,". < 2.6 x Iff’ 6.4 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C0, +

soln. 73-7109

1.70 Methionine (1.2 ± 0.1) x 10

8 1 1.2 ± 0.3 p.r. D.k. in N20-satd. 72-0036

0.3 soln. (3.6 ± 0.4) x 10' 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH;,)4C0;, +

soln. 73-7352

(4.8 ± 0.5) x 10

7

5.2 x 10

8

11.0 0.003 f.phot. D.k. at 600 nm; CO,"

generated from Co(NH,)4C0,+

; slight pH effect.

75-7110

1.71 /7-Methoxyphenoxide 12.2 0.3 p.r. D.k. at 570 nm in N2 0- 77-1098

ion satd. carbonate soln. 1.71a Methyl radical (3 ± 1) x 10

9 - - p.r. D.k. at 600 nm in 78-1506

CO." + CH , -* CH,0C02

' Na2CO,-CH ,Cl soln. 1.71b TV-Methylaniline 1.8 x 10

9 - - p.r. D.k. at 600 nm. 78-1506

1.72 5-Methylcysteine (2.5 ± 0.2) x 10'

(5 ± 0.5) x 10

7

7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C0:, +

soln. 73-7352

11.0 0.003 f.phot. D.k. at 600 nm; CO ," generated from Co(NH ,)4C0 , +

; slight pH effect.

75-7110

1.73 />-Methylphenoxide 4.8 x 10

8 12.2 0.3 p.r. D.k. at 570 nm in N20- 77-1098

ion satd. carbonate soln. 1.74 2-Methyl-2-propanol < 1.6 x 10

2 6.4 0.03 f.phot. D.k. at 600 nm in 73-7109

(/ert-Butanol) Co(NH;,)4CO, +soln. 1.75 jV-Methyltryptophan (4.3 ± 0.4) x 10

8 7-11 0.003 f.phot. D.k. at 600 nm; CO ,H and CO," generated from Co(NH ,)4CO , +

.

74-7296

1.76 Nitromet'nane (1 ± 0.1) x 10

6 7 0.003 f.phot. D.k. at 600 nm in Co(NH ,)4C0,^ soln. 75-7110

1.77 aci-Nitromethane (1.5 ± 0.4) x 10

7 12 0.003 f.phot. D.k. at 600 nm; CO," 75-7110

anion generated from CO," + CH2 =N02

' Co(NH3)4CO, +

; product

'C^COCHzNOa' obs. by esr (72-5050).

1.78 />-Nitrophenoxide ion 4.8 x 10

7 12.2 0.3 p.r. D.k. at 570 nm in N.,0-

satd. carbonate soln. 77-1098

1.79 Norpseudopelle- (1.1 ± 0.1) x

10‘’ Ti 0.015 p.r. D.k. at 600 nm in N.,0- 71-0061

tierine-TV-oxyl satd. carbonate soln. (9-Azabicyclo[3,3,l]nonan3-one-9-oxyl)

1.80 Penicillamine 2 x 10' 4 0.003 f.phot. D.k. at 600 nm; CO,H 75-7110

(3-Mercaptovaline) 2.4 x 10

H 10 or CO;," generated from

1.2 x 10

H 12 Co(NH ,) 4CO, +

; values from graph. 1.81 Phenol (2.2 ± 0.2) x 10' 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO,

+

soln. 73-7352

4.9 x 10" 7.0 0.06 f.phot. D.k. at 600 nm in 75-7313

Co(NH ,) 4C0, tsoln.; k

increases with pH

to 5 x 10 at pH 12. 1.82 Phenoxide ion 2.4 x 10

B 12.2 0.3 p.r. D.k. at 570 nm in N20-

satd. carbonate soln. 77-1098

3.3 x 10

8

1 £k - p.r. D.k. at 600 nm. 78-1506

11
TABLE 1. Rates of reaction of C04 in aqueous solution”—Continued

No. Reaction k(AT' s'

1 ) PH

1.83 Phenylalanine < 1 x lO" 1 1 .2 ±

0.3

(5 ± 0.5) x 10

4 7.0

1.84 Phenylalanylglycine (4.0 ± 0.4) x 10

:> 7.0

1.85 1-Propanol 1.9 x 10

4 12.1-

12.7

1.86 2-Propanol

CO,' + (CH,)2CHOH —

HCO,’ + (CH,),COH

3.9 x 10

4 12.1-

12.7

< 4 x 10* 6.4

1.87 Ribonuclease A

5 x 10

4

(5.0 ± 0.5) x 10

7

1.4 x 10

8 7.0 11.0

1.88 2,2,6,6-Tetramethyl-4—oxo-1-

piperidinyloxyl

(TAN)

(4.8 ± 0.5) x 10

H

4.6 x 10

H 10-11

1.89 Thymine

* V o 7.0

1.90 Toluene 4.3 x 10

4 7.0

1.91 Trichloroacetate ion < 1.5 x 10

2 12.1-

12.7

1.92 Trypsin (6.8 ± 0.7) x 10

8 7.0

1.93 Tryptamine (1.25 ± 0.1) x 10" 8

1.94 Tryptophan (4.4 ± 0.4) x 10

8 1 1 .2 ±

0.3

4.3 x 10

8 12

1.95 Tryptophan methyl

ester

(9.5 ± 1) x 10

8 7

1.96 Tryptophanamide (1.3 ± 0.1) x 10" 7

I Method Comment Ref.

0.3 p.r. D.k. in N20-satd.

soln. 72-0036

0.03 f.phot. D.k. at 600 nm in Co(NH,)4C<V soln. 73-7352

0.03 f.phot. D.k: at 600 nm in Co(NH,).,CO,

+

soln. 73-7352

f.phot. D.k. at 600 nm in airsatd. soln. contg. 0.05 M Na2S20H and 0.5 M

Na2 CO,; CO ,’ generated from S04

’ + CO ,".

72-7383

f.phot. D.k. at 600 nm in airsatd. soln. contg. 0.05 M Na2S2 0H and 0.5 M

Na2CO,; CO,’ generated from SO," + CO , 2

’.

72-7383

0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO,

+

soln. 73-7109

- p.r. D.k. at 600 nm. 78-1506

0.03 f.phot. D.k. at 600 nm; CO,H 73-7352,

0.03 f.phot. or CO," generated from Co(NH ,)4CO , +

; k is pH

dependent; value from

graph; mol. wt. 13,700.

75-7110

0.015 p.r. D.k. at 600 nm in N2 0-

satd. carbonate soln. 71-0061

p.r. D.k. at 600 nm in airsatd. soln. 71-0618

0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 73-7352

0.06 f.phot. D.k. at 600 nm in Co(NH,)4CO,

+

soln. 75-7313

f.phot. D.k. in air-satd. soln. contg. 0.5 M Na2CO, and

0.05 M Na2S,08; CO ,' generated from S04

’ +

CO,

2’.

72-7383

0.03 f.phot. D.k. at 600 nm in Co(NH,).,CO,

+

; mol. wt. 23,800.

73-7352

0.003 f.phot. D.k. at 600 nm in Co(NH ,)4CO;, +

; k is pH

dependent, k ss 9 x 10

8

at pH 12; values from

graph.

74-7296

0.3 p.r. D.k. in N20-satd. soln. 72-0036

0.003 f.phot. D.k. at 600 nm; CO,H

or CO,’ generated from Co(NH,)4CO,+

; k is pH

dependent, k a 6.2 x 10

8

at pH 9 and 7 x 10

8 at pH 7; values from graph.

74-7296

73-7352

0.003 f.phot. D.k. at 600 nm in Co(NH,),CO;,

4 soln.; k pH-dependent.

74-7296

0.003 f.phot. D.k. at 600 nm in Co(NH ,)4CO, 4 soln.; k pH-dependent.

74-7296

12
Table 1. Rates of reaction of C03 in aqueous solution

3 —Continued

No. Reaction k(Af' s’

1 ) pH I Method Comment Ref.

1.97 Tryptophanylglycine (7 ± 0.7) x 10

H

(2.9 ± 0.3) x 10

8

6 0.003 f.phot. D.k. at 600 nm in Co(NH t )4C03 +

soln.; k pH-dependent.

74-7296

1.98 Tyrosine 1 1 .2 ±

0.3

0.3 p.r. D.k. in N2 0-satd. soln. 72-0036

(4.5 ± 0.4) x 10'

(1.4 ± 0.1) x 10

8

7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4C0 t +

soln. 73-7352

11 0.03 f.phot. D.k. at 600 nm; CO,’

generated from Co(NH,)4C03 +

; k pH

dependent.

75-7110

1.99 Uracil < 10

4 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO, +

soln. 73-7352

1.100 Urea < 10' 7.0 0.03 f.phot. D.k. at 600 nm in Co(NH,)4CO,+

soln. 73-7352

T'he transient is represented in the anionic form; pKa has been reported to be 9.6.

13
Table 2. Rates of reactions of SO/ in aqueous solution

No. Reaction k(Af' s"

1 ) pH I Method Comment Ref.

2.1 S04 4 S04 — 2k = 1.0 x lO” 5.5 0.06 f.phot. D.k. at 455 nm in 67-7012

s2oH

2- aerated sulfate soln.; recalcd. for €4

- 5 =

1100 AT 1 cm"

1 . 2k = (8.8 ± 0.8) x 10

H 0.1 1 f.phot. D.k. at 455 nm in 67-7058

(7.5 ± 0.25) x 10

H 1.0 0.13 aerated S2 0/~ soln.; (9.5 ± 1) x 10

H 4.8 0.03 recalcd. for =

1100 AT

1 cm"

1

. 2k = (1.6 ± 0.3) x

10‘' - 1 M f.phot. D.k. in aerated 2.5 x 67-7274

h2so4 10

1 M ceric sulfate; recalcd. for =

1100 AT

1 cm

1 . 2k = 3.6 x

10“' ~

’ 4 M p.r. D.k.; used €4S0 == 1000 73-1030

h2 so4 AT

1 cm'1 (66-0019).

2.2 S04

" 4- As02

" —* X o X O

cc 7-8 - phot. C.k. with fumarate ion 73-5403

S04 -f -As02 (rel.) in S20/" soln.; effect of solute on fumarate-SO/ adduct obs. by esr; rel. to

k(SO/ + OH") = 7.3 x 10

7

. 2.3 S04

" 4 Br" — (3.5 ± 0.4) x 10° 7 0.03 p.r. D.k. at 450 nm in air- 75-1069

S04

2

' 4 Br satd. S20„ " soln. contg. 0.05 M fert-BuOH.

1.6 x 10

<; 7-8 - phot. C.k. with fumarate ion in 73-5403

(rel.) S20K

2

" soln.; effect of

solute on fumarate-S04 adduct obs. by esr; rel. to k(SO/ + OH") = 7.3 x 10

7

. 2.4 S04

" 4 HCO," — (9.1 ± 0.4) x 10

6 7. 5-8.

5

0.03 f.phot. D.k. at 330 nm (SO/) as 67-7058

S04

2

" 4 CO,' 4 H

+

9.3 x 10

6 7-8 phot.

well as p.b.k. at 600 nm

(CO/) in aerated

10’ 2 M S20/~ soln. C.k. with fumarate in 73-5403

(rel.) S2 0H

2 " soln.; effect of

solute on fumarate-SO/

adduct obs. by esr; rel. to *(SO/ + OH") = 7.3 x 10

7

. 2.5 S04

‘ 4 CN' 8.0 x 10

7 7-8 - phot. C.k. with fumarate in 73-5403

(rel.) S2 0H soln.; effect of

solute on fumarate-SO/

adduct obs. by esr; rel. to k(SO/ + OH") = 7.3 x 10

7

. 2.6 SO/ 4- OCN" 5.0 x 10

H 7-8 - phot. C.k. with fumarate in 73-5403

(rel.) S20/’ soln.; effect of

solute on fumarate-SO/

adduct obs. by esr; rel. to k(SO/ 4 OH") = 7.3 x 10

7

. 2.7 SO/ + SCN" ^ (5.2 ± 0.5) x

10'' 7 0.03 p.r. D.k. at 450 nm in air- 75-1069

S04

2

' 4 SCN satd. S2 0/" soln. contg. 0.05 M tert-BuOH.

14
Table 2. Rates of reactions of S04 in aqueous solution—Continued

No. Reaction k(M

~

' s ') pH

2.8 S04 + Cem

(1.43 ± 0.3) x 10

H - SO/’ + Ce"

1.3 x 10

H

(rel.)

2.9 so4

" + cr — 1.9 X 10

8 7-8 S04

2- + Cl (rel.)

3.1 x 10

8 6.8

1.3 x 10

8

2.10 S04" + Cr

2+ > 10

1' 1.0 2.11 S04

" + Fe

2+ — 9.9 x 10

8 - SO/' + Fe' +

8.5 x 10

8 2.12 S04_ + NH2OH 8.2 2.13 S04

" + nh’oh +

1.5 x 10

7 4.1 2.14 S04

- + n2h4 8.1 x 10

8 9.5 2.15 S04

" + N2 Hs +

2.1 x 10

8 4

2.16 S04

- + N;1- 7.4 x 10

8 7-8

S04

2

- + -N;i (rel.)

~3x 10" 7

2.17 S04

" + N02

" 8.8 x 10

8 7 so4

2

- + no2 2.18 S04

- + NO’ 1.4 x 10

6 9

(rel.)

2.1 x

10'’ 7-8

(rel.)

2.19 S04

" + OH' — 4.6 x 10 >11

SO/- + OH

(6.5 ± 1.0) x 10

7 alk.

(8.3 ± 0.8) x 10

7 >11

(rel.)

7.3 x 10'

1 Method Comment Ref.

1 M

H2 SO4

f.phot. D.k. at 455 nm; Ce'" produced from ceric

sulfate.

67-7274

4 M

h2 so4

y-r. Air-satd. soln. contains Ce'\ Ce"' and formic

acid; ratios calcd. from assumed mechanism:

*(S04

‘ + Ce'")/*(S04- +

HCOOH) s 160; A(S04

- + Ce m

)/^(S04

- +

2-PrOH) = 1.6; rel. to £(SO t + 2-PrOH) = 8 x 10

7

.

72-0094

phot. C.k. with fumarate ion in S20K"" soln.; effect of

solute on fumarate-S04 adduct obs. by esr; rel. to k(SO/ + OH ) = 7.3 x 10

7

.

73-5403

p.r. D.k. at 480 nm; soln. contains S20H

-", terr-BuOH

and phosphate buffer.

75-5244

p.r. P.b.k. (Of) in 0.002 M

S20H-; k = 4.1 x 10

8 in 2 M S04

" soln.

76-1141

- therm. Estimated. 68-9084

1 p.r. D.k. at 450 nm. 66-0019

_ p.r. _ 78-1075 - p.r. - 78-1075

- p.r. - 78-1075

- p.r. - 78-1075

phot. C.k. with fumarate in S20H

~~ soln.; effect of

solute on fumarate-S04

"

adduct obs. by esr; rel. to Jfc(S04

" + OH") = 7.3 x 10

7

.

73-5403

- p.r. - 78-1075

- p.r. - 78-1075

~ phot. C.k. with RNO in airsatd. S.Oj,-- soln.; rel. to k(S04

- + EtOH) = 6.2

x 10

7

.

70-7234

phot. C.k. with fumarate in S2 0K

" soln.; effect of

solute on fumarate-S04 adduct obs. by esr; rel. to Ar(S04

- + OH ) = 7.3 x 10

7

.

73-5403

- p.r. D.k. at 460 nm; soln. contains S20„- . 69-0158

- p.r. D.k. cs. OH" concn. in 0,-free S,0H— soln. 72-7008

0.06-

0.08

p.r. C.k. with tyrosine; effect of pH on formn. of tyrosine

transient at 410 nm; rel. to Ar(SO 4 " + tyr) = 3.2 x 10

J at pH 7.

75-1069

— p.r. D.k. at 450 nm; soln. contains S2 0H

‘- and tert-BuOH. 75-5244

15
Table 2. Rates of reactions of S04 in aqueous solution—Continued

No. Reaction k(Af' s'

1 ) PH

2.20 so; 4 h2 o — 10 -104s'

1 _ hso; 4 OH < 3 x 10 ' s'

1 7

2.21 so; + h2 o2 1.2 x 10

7 7

2.22 so; 4 h2 po; — 3.6 x 10

K 7-8

so;* + h

+ 4 hpo; (rel.)

2.23 so; + hpo;' -*

1.8 x 10

H

4.3 x 10

7 77-8

SO;- + H

4 + PO 2' (rel.)

6.2 X 10

7 8.3 2.24 so; 4 H ,po ; 1.6 X 10

7 4

2.25 so; 4 h2 po; < 7 X 10

4 7

2.26 so; 4 hpo42' (1.2 ± 0.3) x

10*' 9

2.27 so4 4 so; — > 5.3 x 10

H - so4

2

' 4 so;

2.6 x 10

K 7-f

(rel.)

2.28 S04

' 4 HSO-" — < 10

s hso4

" + so;

2.29 so; 4- SiO,

2' — 2 X 10

7 so4

2' 4 Sio;

2.30 so; 4 Tl

+ (1.70 ± 0.2) x 10"

2.31 Acetanilide 3.6 x 10* 7 so; + QHNHCOCH, —

so;' 4 Cf ,H- + NHCOCH,

2.32 Acetate ion 5.0 x 10

(

' 6.8 SO; 4 CH,COO' -> SO;' CH , 4 CO, (1) so; + ch ,coo‘

HSO; + CH2COO" (2)

8.7 X

10'’ 7-8

(rel.)

2.33

Acetic acid (8.8 ± 0.2) x 10

*

2.34 Acetophenone 3.1 x 10

H 7 SO; 4 C(,H-COCH, —

so;' 4 C„H-

+ COCH,

2.35 />-Acetylbenzoate ion 2.0 x 10* 7 SO; 4 CH: ,COC,.H ,COO' —* SO;* 4 CH,COC„H4 + COOI Method Comment Ref. _ therm. Estimated. 68-9084

p.r. Extrapolated from d. le- es. OH' concn. (see 2.19). 72-7008

- p.r. - 78-1075

phot. C.k. with fumarate ion in S2 0; soln.; effect of

solute on fumarate-S04

"

adduct obs. by esr; rel. to A(SO; 4 OH') = 7.3 x 10

7

.

73-5403

- p.r. - 78-1075

phot. C.k. with fumarate ion in S2 0K

" soln.; effect of

solute on fumarate-S04

"

adduct obs. by esr; rel. to *(S04

' 4 OH') = 7.3 x 10

7

.

73-5403

^ * p.r. - 78-1075 - p.r. - 78-1075 - p.r. - 78-1075 - p.r. - 78-1075

p.r. Rate with HSO; higher

by at least a factor of

2.5.

72-7008

phot. C.k. with fumarate ion in S_>0H

" soln.; effect of

solute on fumarate-S04 adduct obs. by esr; rel. to £(SO; 4 OH") = 7.3 x 10

7

.

73-5403

- p.r. D.k. at 450 nm. 77-1047

- f. phot. - 70-7262

1 M

h2so4

f.phot. D.k. at 455 nm; soln. contains ceric sulfate- h2so4

.

67-7274

p.r. D.k. at 450 nm; soln. contains 0.01-0.05 M

SO 2"

77-1001

p.r. D.k. at 450 nm; soln. contains S20H

"", <ert-BuOH, and phosphate

buffer; predominantly (1); C02 yield meas. by y-r. (78-1505).

75-5244

phot. C.k. with fumarate ion in S20H

“" soln.; effect of

solute on fumarate-S04 adduct obs. by esr; rel. to k(SO.,' 4 OH") = 7.3 x

10’; product ident. by esr.

73-5403

1 M

h2 so4

p.r. D.k. at 455 nm; soln. contains ceric sulfate- h2so4

.

67-7274

0.03 p.r. D.k. at 450 nm in ~ 10 " M S2 0H

“ soln. 77-1001

0.03 p.r. D.k. at 450 nm in ~ 10 “ M S2 0; soln. 77-1001

16
No. Reaction ifAT's' 1

) pH I Method Comment Ref.

2.36 Acrylamide sor -i- ch2 = CHcoNHa

1.6 x 10 s 7.3 - p.r. - 77-1503

2.37 Acrylate ion sor + CHz = CHCOO"

1.1 x 10 8 6.5 p.r. - 77-1503

2.38 Acrylonitrile 1.7 x 10 8 ~7 - p.r. Soln. contains S208*~; 69-0158

SO4 _ + CH2 = CHCN( + H2 0)— product obs. by

CHzOHCHCN + hso4 _ absorption spectrum.

8.1 x 10 7 7.4 - p.r. - 77-1503

2.39 Alanine S04 ' + CHaCHNHa* COO'(1.0 ± 0.1) x 10 7 7 0.03 p.r. D.k. 75-1069

2.40 Allyl alcohol SO4 ' -1- CH2 = CHCHzOH

1.5 x 10 9 6.8 p.r. — 77-1503

2.41 Allyl cyanide

S04 ' + CH2 = CHCHzCN

1.1 x 10 9 7 — p.r. - 77-1503

2.42 Anisole (4.9 ± 0.5) x 10 9 - - p.r. P.b.k.; product ident. 75-1171

S04 ' -1- C6 H5 OCH3— by esr. •CsH5

+ OCH3 -1- S04 2

"

2.43 Benzamide 1.9 x 10 8 7 0.03 p.r. D.k. at 450 nm in 77-1001

S04 ' + GHsCONHz^ -lO^A/SjOg 2-

soln. S04 2- + -G;H5

+ CONHz

2.44 Benzene 8.0 x 10 8 ~7 - p.r. Soln. contains S208 2-

; 69-0158

S04 CeH6—* final product ident. by

•QHe+ + S04 ^ absorption spectrum.

•Cb H6 +(+ H2 OW 6.7 x 10 8 9 - phot. C.k. with RNO in air- 70-7234

.CsHsOH + H

+

(rel.) satd. S2 O8 soln.; rel. to £(S04 ~ + Et0H) =

6.2 X 10 7 ~3 x 10 9 7 0.03 p.r. D.k. at 450 nm in S2 O8 2” 77-1001

soln. contg. 0.1 M

tert-BuOH; also p.b.k. at 315 nm (76-1187).

l,3>5-Benzenetricarboxylate ion See Trimesate ion. 1,2,4,5-Benzenetetracarboxylate ion See Pyromellitate ion.

Benzoate ion S04 ' + GsHsCOO'-hS04 2- + Celt^COO'

GsH5 + C00' ( + H2 O)—

HOQsHsCOO' + H

+

(l) CeHTCOCT-^

•GsHs + COz(2)

1.2 x 10 9 7 0.03 p.r. D.k. at 450 nm in ~ 10~ 2 M S2 O8 2"

soln.; CO2 yield in y-r.

suggests reaction (2) contributes 56% (78-1505).

Absorption of OH adduct

in p.r. suggests

reaction (1) contributes 20% (78-1504).

77-1001

Benzonitrile SO4 ' -1- (GHsCN-^

S04 2” -1- -CeHs+CN

1.2 x 10 8 7 0.03 p.r. D.k. at 450 nm in -lO'M/SzOs 2" soln. 77-1001

Benzyl methyl ether SO4 - + (GH5 CH2 OCH3

k/fa-PrOH = IB 1.8 therm. T = 75°C; c.k. in S2 Os ^-alcohol soln.; obs. C6 H5 CHO yield.

74-9006

o-Bromobenzoate ion SO4 - + BrCeHiCOO'—> S04 2-

-(- BrCeH4 + COO“

BrGH4+ C00' ( + H2 0)-^

•OQH4COO' + 2 H

+

-f Br' (1) BrC6H4 + COO" ( + H2 OH

BrC6H4 (OH)COO'+H+

(2)

8.7 X 10 8 7 0.03 p.r. D.k at 450 nm in ~ 10-2 Af S2 O8 2- soln.; Br” and CO2 yields meas. on y-r. indicate reaction (1) contributes ~ 16% and reaction (3) -10% (78-1505).

77-1001

BrQjH^ COO'-*

•CeHiBr+COsO)

17
Able 2. Rates of reactions of S04 in aqueous solution—Continued

No. Reaction k(\T' s ') pH

2.49 />-Bromobenzoate ion 1.0 x 10* 7

2.50

/erf-Butanol See 2-Methyl-2-propanol.

/>-Chlorobenzoate ion 3.6 x 10

K 7

2.51 Crotonic acid 7.7 x 10

H 4.8

2.52

Crotononitrile See Ally 1 cyanide

/>-Cyanobenzoate ion 3.3 x 10 4.8

2.53 Cycloheptanol ^^2-l’rOH ~ 2-4 1.8

2.54 Cyclohexene

X X O ~ 7

2.55

SO, + C( ,H|„ ( + H20) —

C() H loOH + HS04

-

Diethyl disulfide 2.6 x 10

H ~ 4.5

2.56

S04

* + RSSR -+

SO,

2

' + (RSSR) + 1,2-Dimethoxy- (5.0 ± 0.5) x 10

9

2.57

benzene SO,' + DMB —

SO,

2

* + (DMB)"

1,3-Dimethoxy- (7.0 ± 0.7) x 10

9

2.58

benzene SO,' + DMB —

SO,

2

' + (DMB) +

1 ,4— Dimethoxy- (7.2 ± 0.7) x 10

9

2.59

benzene so; + DMB —*• S04

2

' + (DMB) + 2,3-Dimethoxy- 8.5 x 10

9 > 3

2.60

benzoate ion 2,4— Dimethoxy- 3.8 x 10

9 > 3

2.61

benzoate ion 3,4-Dimethoxy- 4.5 x 10

9 > 3

2.62

benzoate ion 2,6-Dimethoxy- 2.5 x 10

9 > 3

2.63

benzoate ion 3,5-Dimethoxy- 4.4 x 10

9 > 3

2.64

benzoate ion Dimethyl disulfide 3.8 x 10* ~ 4.5 so; + RSSR —

SO,

2' + (RSSR)-

+

I Method Comment Ref.

0.03 p.r. D.k. at 450 nm in ~ 10 ' M S2(V" soln.; Br' and C02 yields meas. on y-r. indicate — 30% debromination and ~ 40% decarboxylation;

see reactions under o-bromobenzoate (78-1505).

77-1001

0.03 p.r. D.k. at 450 nm in ~ 10'2 M S2 0H

2

' soln.; C02 yield meas. on y-r.

indicates — 40%

decarboxylation (78-1505).

77-1001

p.r. 77-1503

0.03 p.r. D.k. at 450 nm in ~ 10'2 M S20H

2

- soln.; C02 yield meas. on y-r.

indicates ~ 30%

decarboxylation (78-1505).

77-1001

therm. T = 75°C; c.k. in S-jO/'-alcohol soln.; obs. ketone formn.; for l-</-cycloheptanol ratio =

1.5.

74-9006

p.r. Soln. contains S20/';

product obs. by

absorption spectrum.

69-0158

0.3 p.r. D.k. at 300 nm in Arsatd. 0.1 M S20H

2

' soln. 76-1143

0.003 p.r. P.b.k.; product ident. by esr and absorption

spectra.

75-1171

0.003 p.r. P.b.k.; product ident. by esr and absorption

spectra.

75-1171

0.003 p.r. P.b.k.; product ident. by esr and absorption

spectra.

75-1171

0.03 p.r. P.b.k. in Ar-satd. S20H

2

' soln. 77-1006

0.03 p.r. P.b.k. in Ar-satd. S20H

' soln. 77-1006

0.03 p.r. P.b.k. in Ar-satd. S20H

' soln. 77-1006

0.03 p.r. P.b.k. in Ar-satd. S^h" soln. 77-1006

0.03 p.r. P.b.k. in Ar-satd. S2 0H

'" soln. 77-1006

0.3 p.r. D.k. at 300 nm in Ar-satd.

0.1 M S20/ soln. 76-1143

18
Table 2. Rates of reactions of S04

' in aqueous solution —Continued

No. Reaction k(Af' s'

1 ) pH I Method Comment Ref.

2.64a Dioxane S04 + C4Hk02 —

hso4

- + C4H-02

1.6 x 10

7 7-8 0.003 p.r. C.k.; rel. to £(S04

‘ + TMB) = 2.4 x

10^; obs. buildup of TMB+

(see 2.108); V*.> = 1.7.

78-1076

2.65 Ethanol S04

" + CH ,CH2OH -

3 x 10

7 1 p.r. D.k. at 450 nm; HS04 soln. 66-0019

HS04

' + CH ( CHOH (7.7 ±

(6.2 ±

2.2) x 10

7

1.4) x 10

7 4.8

1.0

0.03

1

f.phot. D.k. in aerated 10 " M K2S2 Oh soln. 67-7058

(3.4 ± 0.3) x 10

7

1.6 x 10

7 7-8

1 M

h2so4 0.003

f.phot.

p.r.

D.k. at 455 nm in ceric sulfate-H2S04 soln.

C.k., rel. to *(S04

‘ + TMB) = 2.4 x 10

J

; obs. buildup of TMB +

(see 2.108); k^/k^ = 2.4.

67-7274

78-1076

2.66 1 -(p-Ethy1- k / k2_ phenyl)ethanol

-I’rOH = 26 1.8 therm. T — 75°C; c.k. in S208

2

alcohol soln.; obs. ketone

formation.

74-9006

2.67 Formate ion (1.7 ±: 0.2) x 10

8 7 0.03 p.r. D.k.; S2 082

' soln. 75-1069

S04

" + HCOO' -> S04

2

- + C02

' 2.7 x 10

8 7-8 phot. C.k. with fumarate ion in s2 08

2' soln.; effect of

solute on fumarate-S04

'

adduct obs. by esr; rel. to k( S04

" OH ) = 7.3 x io7

.

73-5403

2.68 Formic acid (1.35 ± 0.2) x 10

6

1 M

h2 so4

f.phot. D.k. at 455 nm in ceric sulfate-H2S04 soln. 67-7274

2.69 Fumarate ion S04

~ + 'OOCCH =CHCOO" —

-00CCHCH(0S0 3 ")C00-(1)

S04

' + OOCCH = CHCOO

S04

2

' + "OOCCH =CH- + C02

1.6 x 10

7

(2)

7 p.r. D.k. at 450 nm; kjk2 ~ 1 from C(C02) by ”y-r. (78-1505); adduct obs. by

esr (75-5244).

77-1106

2.70 Glycine (9 ± 0.9) x 10

6 7 - p.r. D.k. in S2 08

‘" soln. 75-1069

2.71 Histidine ~ 2.5 x

10‘; 7 0.03 p.r. D.k. in S2 08

2' soln. 75-1069

2.72 Homophthalate ion (1.1 ±

S04

' + ArCH2COO” -> S04

2'

-I- ArCH2 + C02

0.2) x 10

9 7 p.r. D.k. at 450 nm as well

as p.b.k. at 328 nm

(ArCH2

-) in S208

2

' soln.; C02 yield meas. by y-r. (78-1505) and absorption

of ArCH2 radical by p.r. (78-1504) indicate predominant decarboxylation from side chain.

76-1187

2.73 /j-Hydroxybenzoate ion S04

' + H0C6H4C00' -> S04

2' + -0QH4C00‘ + h

+

2.5 x 10

9 7 p.r. D.k. in S2 08

2 soln. 77-1001

2.74 Lysozyme 1.8 x 10

1 " 7 0.03 p.r. D.k. in S2 08

" -tert-BuOH

soln. 75-1069

2.75 Malonate ion so4

- + OOCCH2 COO' —

S04

2

" + OOCCH2 + C02

5.5 x 10

6 7 p.r. D.k. at 450 nm; radical obs. by esr; C02 yield meas. by y-r. (78-1505).

77-1106

2.76 Methacrylic acid 1.1 x 10

9

7 x 10

8 2.9

6.9

p.r.

p.r.

— 77-1503

2.77 Methacrylonitrile 3.8 x 10

8 7 p.r. - 77-1503

19
Tari t 2 Rates of reactions of SO/ in aqueous solution—Cont in ued

No. Reaction k(M~' s'

1 ) pH I Method Comment Ref.

2.78 Methanol 2 x 10 _ 1 p.r. D.k. at 450 nm. 66-0019

SO/ -|- CH,OH — (2.5 ± 0.4) x 10

7 HSO/ -I- CH.OH (2.5 ± 0.6) x 10

7 4.8

1.0

0.03 f.phot. D.k. in aerated 10 " M

K2S208 soin. 67-7058

( 1.1 ± 0. 2) x 10

7 - 1 M

h2 so4

f.phot. D.k. at 455 nm in ceric sulfate-H ,S04 soln. 67-7274

7.6 x 10“

(re!.) 9 phot. C.k. with RNO in airsatd. S2 0/ soln.; rel. to *(SO/ + EtOH) = 6.2 x 10

7

.

70-7234

1.3 x 10‘

(rel.) 7-8 phot. C.k. with fumarate in S20/ soln.; effect of

solute on fumarate-SO/

adduct obs. by esr; rel. to *(SO/ + OH ) = 7.3 x 10

7

.

73-5403

( 1.1 ± 0. 1 ) x 10

7 7 0.03 p.r. D.k. in S20H " soln. 75-1069

3.2 x 10“ 7-8 0.003 p.r. C.k.; rel. to /t(SO/ + TMB) = 2.4 x 10 *; obs. buildup of TMB +

(see 2.108);

kH /ku = 2.7.

78-1076

2.79 Methionine 1.1 x 10

J Methoxybenzene See Anisole 7 0.03 p.r. D.k. in S20/ soln. 75-1069

2.80 2-Methoxybenzoate ion 7.0 x 10

’ > 3 0.03 p.r. P.b.k. in Ar-satd. S20/' soln. 77-1006

2.81 3-Methoxybenzoate ion 7.6 x 10* > 3 0.03 p.r. P.b.k. in Ar-satd. S2 0/' soln. 77-1006

2.82 4—Methoxybenzoate ion 3.5 x 10^ SO/ 4 CH ,0C„H4C00' —

S04

2

" 4 CH t 0C„H/C00‘

7 p.r. P.b.k. at 560 nm

(cation radical) in S20H soln.

77-1001

7.6 x 10

9 > 3 0.03 p.r. P.b.k. in Ar-satd. S2 0„" soln. 77-1006

2.83 l-Methoxy-2-methyl- ^/^2-Pr<)H = 14

1 -phenylpropane

SO; + C*,H,CH(OCH,)CH(CH ( )2

1.8 therm. T = 75°C; c.k. in S20K

2"- alcohol soln.; obs. benzaldehyde and isopropyl

phenyl ketone formn.

74-9006

2.84 Methyl methacrylate 1.0 x 10* SO/ 4 CH_. = C(CH t )COOCH

,

7.3 p.r. - 77-1503

2.85 2-Methyl-2-propanol (9.1 ± 1.0) x 10

’ - - p.r. D.k. in S2 0/~ soln. 72-7008

SO/ 4 (CH/3COH — A/A2_PlOH = 0.05 HS04 4 CH^QCH^OH

1.8 therm. T = 75° C; c.k. in S2 0H

2 '-alcohol soln.; obs. acetone formn.

74-9006

( 8.0 rt 0. 8) x 10

5 7 0.03 p.r. D.k. in S20K

2

' soln. 75-1069

4.0 x'10’ 7-8 0.003 p.r. C.k.; rel. to k (SO/ + TMB) = 2.4 x 10 *; obs. buildup of TMB + (see 2.108).

78-1076

2.86 />-Nitroso-/V/V- 2.3 x 10

’

dimethylaniline (rel.) SO/ 4 NOCfl H4N(CH5)2

7 phot. Air-satd. S20/ soln.;

rel. to k(S04

’ 4 EtOH) =

6.2 x 10

7

.

70-7234

2.87 3-Pentanol ^/^2-PrnH = 1-3 SO/ + (C,H,)2CHOH

1.8 therm. T — 75°C; c.k. in S20/ -alcohol soln.; obs. ketone formn.

74-9006

2.88 l-Phenyl-3-butanol ^/^2-pr<>H = 25

SO/ + C(> HsCH2CH2CHOHCH3

1.8 therm. T = 75°C; c.k. in S20„“ -alcohol soln.; obs. ketone and

acetaldehyde formn.

74-9006

20
Table 2. Rates of reactions of S04

~ in aqueous solution—Continued

No. Reaction k(\f

1 s') pH

2.89 1-Phenylethanol so; + C6 HsCHOHCH,

^/^2-l’rOH — 22 1.8

2.90 1 -Phenyl-2-propanol

SO; + Cf) H-CH,CHOHCH

^^2-VrOH = ^

i

1.8

2.91 2-Phenyl-2-propanol

so; + Cf,H-COH(CH ( ) 2

^^2-l’rOH ~ 8.4 1.8

2.92 1-Propanol 4.8 X 10~

(rel.) 9

5.8 x 10

7 7-8

2.93 2-Propanol (8.5 ± 3.0) x 10

7 4.4

(9.1 ± 2.8) x 10

7 1.0

(4.6 ± 0.2) x 10

: -

8.5 x 10

7 9

(rel.)

4.0 x 10

7 7-8

8.0 x 10

7 7

3.2 x 10

7 7-8

2.94 Propionate ion so; + ch s ch2coo -> S04

2

’ + CH,CH2 + C02

4.6 x 10* 7

2.95 Pyridine (2.2 ±

' SO+

- + c5h5n

0.2) x 10

K 7

2.96 Pyridinium ion (2.0 ±

SO+

" + CS H-NH

0.4) x 10

7 3.9

2.97 Pyromellitate ion (1.7 ±

(1,2,4,5-Benzenetetracarboxylate ion)

0.2) x 10

7 9

2.98 Ribonuclease 1.2 x 10

10 7

2.99 Serine so; + hoctj

2chnh/coo2.3 x 10

7 7

2.100 Succinate ion so; + oocch2ch,cooSO/- + OOCC.H2CH2 + co2

7.1 x 10° 7

I Method Comment Ref.

- therm. T = 75°C; c.k. in S2 0/ -alcohol soln.: ohs. ketone formn.

74-9006

therm. T = 75°C; c.k. in S20K

2 —alcohol soln.; obs. acetaldehyde formn.

74-9006

therm. T = 75°C; c.k. in S20/ -alcohol soln.; obs. ketone formn.

74-9006

phot. C.k. with RNO in airsatd. S20/“ soln.;

rel. to £(SO; + EtOH) =

6.2 x 10

7

.

70-7234

phot. C.k. with fumarate in S2 08- soln.; effect of

solute on fumarate-S04

"

adduct obs. by esr; rel. to £(S(V + OH ) = 7.3 x io7

.

73-5403

f.phot. D.k. in aerated 10

2 M

K2S208 soln. 67-7058

1 M

h2 so4

f.phot. D.k. at 455 nm in ceric sulfate-H2 S04 soln. 67-7274

phot. C.k. with RNO in airsatd. S2 08

- soln.; rel. to Ar(SO; + EtOH) = 6.2 x 10

:

.

70-7234

phot. C.k. with fumarate in S2 08

-" soln.; effect of

solute on fumarate-SO;

adduct obs. by esr; rel. to &(S04 + OH ) = 7.3 x io

7

.

73-5403

0.03 p.r. D.k. at 450 nm: S208

2 - ferr-BuOH soln. 75-1069

0.003 p.r. C.k.: rel. to A(SO.; + TMB) = 2.4 x 10 •, obs. buildup of TMB +

(see 2.108); Ah

/A|, = 2.7.

78-1076

“ p.r. D.k. at 450 nm; C02 yield obs. by y-r. (78-1505).

77-1106

- p.r. D.k. at 450 nm; S2 08

"

soln. 76-1187

, p.r. D.k. at 450 nm; S20„-

soln. 76-1187

p.r. D.k. at 450 nm; S208

2

soln. 76-1187

0.03 p.r. D.k. at 450 nm; S20/ —

fer/-BuOH soln. 75-1069

0.03 p.r. D.k. at 450 nm; S208

" - /ert-BuOH soln. 75-1069

- p.r. D.k. at 450 nm; C02 yield obs. by y-r. (78-1505).

77-1106

21
Table 2. Rates of reactions of S04 in aqueous solution—Continued

No. Reaction s’

1 ) pH I Method Comment Ref.

2.101 Terephthalate ion 1.7 x 10* SO/ + C,,H4(COO')2 -* S04

2

' + QH.COO' + CO_. (1) S04

‘ + C,,H ,(COO')2( + OH ) S04

2

’ + HOC,,H 4(COO ), (2)

9 p.r. D.k. at 450 nm; ~ 60% (1) and ~ 40% (2) based on C02 yields by “y-r. (78-1505).

77-1001

2.101a Tetrahydrofuran 1.0 x 10* S04

’ + C4 HhO

HSO/ + C.H-0

7-8 0.003 p.r. C.k.; rel. to A(SO/ + TMB) = 2.4 x 10 obs. buildup of TMB* (see 2.108); A h

/A|, = 2.0.

78-1076

2.102 o-Toluate ion 1.4 x 10* SO/ + CH t C, H 4 COO’ —

HSO/ + CH,C„H ( COO"

7 p.r. D.k. at 450 nm; product

ident. by abs. spectrum

by p.r. (78-1504); C02 yield by y-r. < 10% (78-1505).

77-1001

2.103 m-Toluate ion 2.0 x 10* 7 p.r. D.k. at 450 nm.; abs. spectrum by p.r. indicates predominant formation

of OH adducts (78-1504).

77-1001

2.104 p-Toluate ion 1.8 x 10 SO/ + CH ,C(> H4COO’ —

S04

2’ -f CH,C,H4 + C02 (1) so/ + ch,c( ,h4coo’

S042

’ + CH2 C,,H 4COO' (2) SO/ + CH t C,H4C00’ ( + OH*)^

S04

2

’ + CH ,Cf ,H4(OH)COO’ (3)

7 p.r. D.k. at 450 nm; ~ 30% (1), 30% (2) and 40% (3) based on C02 yields by y-r. (78-1505) and abs. spectra by p.r. (78-1504).

77-1001

2.105 Trimesate ion (8.3 ± 0.8) x 10‘ (1,3,5-Benzenetricarboxylate ion)

9 p.r. D.k. at 450 nm. 76-1187

2.106 1,2,3-Trimethoxy- ~ (6 to 8) x 10

’

benzene

0.003 p.r. P.b.k.; product ident. by optical absorption and esr spectra.

75-1171

2.107 1,2,4-Trimethoxy- (7.8 ± 0.8) x 10

H benzene

0.003 p.r. P.b.k.; product ident. by optical absorption and esr spectra (see 2.108).

75-1171

2.108 1,3,5-Trimethoxy- (1.8 ± 0.2) x 10

benzene (TMB)

SO/ + TMB —

0.003 p.r. P.b.k.; product ident. by optical absorption and esr spectra.75-1171

S04

2

’ + (TMB)-* (2.4 ± 0.5) x10'; 7-8 0.003 p.r. P.b.k. at 580 nm. 78-1076

2.109 2,3.4-Trimethoxy- 2.5 x 10

’

benzoate ion > 3 0.03 p.r. P.b.k. in Ar-satd. S2 0/’ soln. 77-1006

2.110 3,4,5-Trimethoxy- 5.0 x 10

’

benzoate ion > 3 0.03 p.r. P.b.k. in Ar-satd. S2 0/ soln. 77-1006

2.111 2,4,5—Trimethoxy— 4.4 x 10* benzoate ion > 3 0.03 p.r. P.b.k. in Ar-satd. S2 08

2

’ soln. 77-1006

2.112 2,4,6-Trimethoxv- 2.6 x 10* benzoate ion > 3 0.03 p.r. P.b.k. in Ar-satd. S2 0H

2

’ soln. 77-1006

2.113 Trimethylanilinium 1.5 x 10*

ion SO/ + C,H,N(CH,)/ —

S04

2' + -C.H./ N(CH ,)/

7 p.r. D.k. at 450 nm; S20/’

soln. 77-1001

2.114 Tryptophan ~ 2.3 x 10 7 0.03 p.r. D.k. at 450 nm; S2 0/ -

<ert-Bu()H soln. 75-1069

2.115 Tyrosine 3.2 x 10* SO/ -f ArOH —

7 0.03 p.r. D.k. at 450 nm; S20,,

2’- tert-BuOH soln. 75-1069

SO/’ + ArOH" (3.0 ± 0.2) x

10*' ArOH* ArO- + H

+ 6.8 p.r. D.k. at 450 nm as well as p.b.k. at 407 nm

(aryloxy radical).

76-1112

2.116 Vinyl acetate 1., x 10* SO/ + Ac0CHCH2

( + H20)-^

AcOCHCH2 OH + HS04

’ ~ 7 p.r. Soln. contains S2 0H product obs. by absorption spectrum.

69-0158

>.

.

.

22
Table 3. Rates of reaction of S02

", S03

~, S203

~, S202

", S03", Se02" and SeO, in aqueous solution

No. Reaction k(M~' s"

1 ) pH I Method Comment Ref.

3.1 2S02

~ — S204

2" 2k = (1.0 ± 0.1) x 10

10 ~4 -vO f.phot. D.k. at 370 nm, as well

as p.b.k. at 330 nm in 0.06 M HS03 soln,; assumed €(330 nm) = 5700

AT' cm"

1 ; 2k < 1.3 x 10"’

72-7008

based on 2A7e(370) s

2.5 x 10

7

. 2k = (1.3 ± 0.4) x 10

9 acid p.r. D.k. at 360 nm (e = 600

M~' cm"

1 ) as well as

p.b.k. at 320 nm in S02 + HSO, soln.

74-1033

2k = (2.2 ± 0.3) x 10

9 3.1 ~1 p.r. P.b.k. at 320 nm in 10 M HS03 /S02 soln. contg.

1 M HCOO'/HCOOH; e(320) s

8500 MT

1 cm"

1 .

75-1118

3.2 2SO j" S03 + SO 0.03 f.phot. D.k. at 270-290 nm in 68-7072

2S03‘ —* S2 06

2"

0.03 f.phot.

N2 or air-satd. SO .'”

soln.; 2k! € = 1.3 to 1.9 x 10°. D.k. at 275 nm in air- 68-7281

free 0.1 4/Na2S200 soln.; 2k/e = (3.5 ± 2.0) x 10

6

. 2k = 1.9 x 10

9 11.8 0.03 e-r. Obs. steady-state S03

" 72-5049

(rel.) concn. by esr in N2 0-

satd. SO t "’ soln.; rel. to 2*(-CH2 C02

" + -CH2C02 1 =

1.0 x 10

9

. 2k = (1.1 ± 0.2) x 10

9 3.7- ^0 f.phot. D.k. at 255-320 nm in 72-7008

9.8 S03

2"/HS03" soln.; 2k/

e

= 8.3 x 10" - 3.6 x

10*’; same in S2 0( ,'~ soln. 2k = 8.5 x 10

8 5.4, -^0 p.r. D.k. in S032'/HS03

" soln. 72-7008

10.2 2k = 5.4 x 10

R - phot. C.k. in soln. contg. 73-5022

(rel.) 1.6 x 10"3 M S03

2

', 0.68 M acetone and 10" M Na4B,07

; rel. to 2k =

1.4 x 10

; for secondorder decay of (CH JXOH.

2k == (1.4 ± 0.2) x 10

9 10 p.r. D.k. at 255 nm (€ = 74-1033

2k = (0.85 ± 0.2) x 10° 5 1200 ± 50 M~' cm"

1 ) in S0,/HS03" soln., k =

1.4 x 10^ by pulse conductivity at pH 9.5;

sulfate is formed by

hydrolysis of S03; rel. amounts of sulfate and

dithionate formed depend

on pH.

3.3 S03 + N20 — (3.5 ± 1.0) x 10

7 13 1 p.r. D.k. at 260 nm in N20- 71-0461

S03 —(— O —

N

2 satd. soln. contg. 0.002 M SO ( "

; best fit with /HO" + SO:t2

") = 2:5 x 10

8 and e(260 nm) for SO," =

1300 M~' cm"'. 3.4 S03 + 02 — S05 < 10

9

** - f.phot. Estd. 72-7008

3.5 S03

" + ch3ch2oh < 2 x 10

3 — 0.1 f.phot. D.k. at 270 nm in N2-

satd. 0.1 M S20,,~ soln. 72-7008

3.6 S03" + (CH;3)2 CHOH < 10

3 - 0.1 f.phot. D.k. in N2-satd. 0.1 M

S20( ," soln. 72-7008

23
Table 3. Rates of reaction of S02 , SO, , S20, , S202 , SO- , Se02 and SeO, in aqueous solution —Continued

No. Reaction k(Af' s"') pH 1 Method Comment Ref.

3.7 S20," + SjO," 2k = (7.1 ± 1.8) x

10'' 7 0.003 f.phot. D.k. at 380 nm in N2-

satd. S20,

2

’ soln.; 2k/e = 4.1 x 10

f

’; same

68-7072

8 x 10

H

at pH 10.9; addn. of

ethanol, carbonate ion

or ally! alcohol did not

affect the decay rate. 3.8 s2o," + s,o,

2" — 4.5, <0.002 p.r. P.b.k. at 370 nm or d.k. 73-1027

SAV

9.6 at 320 nm in S2 0,

2"

soln.; k = 1.8 x 10* at

I = 0.1. 3.9 S2 0, -f- S2 02 2k/e a 5 x 10

4 7, 0.003 f.phot. D.k. at 270 nm in S2 0,

2 " 68-7072

2k a 4 x 10

K

10.9 soln.; addn. of 02 , methanol, ethanol or

allyl alcohol did not affect the decay rate. 3.10 SO," + SO," 1 p.r. D.k. in N2 0-satd. HSO,"

soln.; €(265 nm) > 560

M~' cm’

1 ; not simple

order.

72-7008

3.11 SO," + ch,ch2oh <

10’ 9 - f.phot. D.k. in air-contg. S2Of) 2

" soln. 72-7008

3.12 2 Se02

" - Se2 04

2' 2k/e = 8.8 x 10" 6.2 - p.r. D.k. in soln. of Se02 77-1173

2k/e = 9.2 x 10" 4.5- contg. 2-methyl-2-propanol;

7.5 Amax = 330 nm; 6max = 1450

M

~ 1 cm’

1 . 3.13 2 SeO," —* Se2 Of,2’ 2k/e = 4.0 x 10

s 9-11 - p.r. D.k. in soln. of Se02 77-1173

or —* SeO, + SeO,

2 ’ contg. N20; \mix = 430 nm;

€max = 1350 AT' cm’

1 . 3.14 2 HSeO, —* products 2k/e = 7.5 x 10

s 5-6 p.r. D.k. in soln. of Se02 contg. N2 0; \mJX = 430 nm;

€max = 600 Af' cm"

1 .

77-1173

3.15 2 H2SeO,

+ — products 2k/e = 2.1 x 10

f* 1 p.r. D.k. in soln. of Se02 contg. HC104; \max = 430

nm; € = 930 AT

1 cm’1 .

77-1173

3.16 SeO," + tryptophan (3.4 ± 0.4) x

10'j 7.4 0.006 p.r. D.k. in N20-satd. SeO,

2 ’ soln. 76-1151

24
Table 4. Rates of reaction of NO,, N02

, N204, NO, , N20,, N02 in aqueous solution

No. Reaction k(AT s ) pH I Method Comment Ref.

4.1 NO., — (7.59 ± 0.21) x 10

3 s'

1

first order decay

acid - p.r. D.k. at 635 nm in 0.1—4 M HNO,.

67-0002

9.5 x 10

2 s'1 acid “ f.phot. D.k. in 0.1-6 M HNO,

contg. K,Ce(NO;,)f> . 67-7274

9.7 x 10 ’ s' 1 2.8 p.r. D.k. at 670 nm in 4 M

NaNO,; k varies with

dose, concn. and pH,

k ~ 3 x 10

4 s’

1 at pH 7.

69-0417

8 x 10

3 s’

1 acid p.r. D.k. at 600 nm in 0.2-15 M HNO,; 1st and 2nd order rates detd. by graphical method; dependent on dose and

concn.

74-1140

(1.6 ± 0.2) x 10" s'

1 nat p.r. D.k. at 635 nm in 5.0 and

7.35 M NaNO, soln.; discrepancy in k values

attributed to dose rate

effects.

76-1171

4.2 NO, + NO, N206 2k = 8.4 x 10

8 acid p.r. D.k. at 670 nm in 1-4.0 M

NaNO,, > 0.12 M HNO, soln.; 2k/c = 2.8 x 10

6

.

69-0417

2k = (0.79 ± 0.04) x 10° acid f.phot. D.k. at 635 nm in 3.5-15 M HNO, and 10'3 M

(NH^CefNO^; €(635

nm) = 250 ± 90 AT 1 cm'

1 .

70-7728

2k = 3.7 x 10

8 acid p.r. D.k. at 600 nm in 0.2-15 M HNO,; €(600 nm) = 285 AT

1 cm’

1 ; 2At/€ = 1.3 x 10

6 (±20%).

74-1140

4.3 NO, + Ce

1 " (1.70 ± 0.04) x 10

6 Ce

lv + NO,'

acid f.phot. D.k. at 635 nm in 6 M

HNO, contg. 10'3 M

(NH4)2 Ce(N0,)6; Ea =

1.0 ± 0.2 kcal mol’

1

(4.2 ± 0.8 kj mol'

1 ) based on 6 runs at 50°C;

k in 1-15 M HNO, varied from 0.64 to 4.1 x 10

6

indicating presence of

several Ce'" complexes.

64-7009

70-7727

(3.70 ± 0.1) x 10

s nat f.phot. D.k. at 600 nm in 0.1 M

K2Ce(NO,)h contg. Ce(NOJ,.

67-7274

(1.3 ± 0.3) x 10

6 acid p.r. D.k. at 600 nm in 2 M

HNO, contg. 10'2 M Ce"

1 ; cor. for NO, + NO,.

74-1140

4.4 NO, + Cl' 1.0 x 10

8 - -

' p.r. P.b.k. at 345 nm (C^l

in 2 M NO,’ soln. 76-1141

4.5 NO, + Fe

2+

(8.0 ± 1.6) x 10

6 acid p.r. D.k. at 600 nm in 2 M

HNO, contg. 10'3 M Fe

2+

; cor. for NO, + NO,.

74-1140

4.6 NO, + N02

' 1.2 x 10° 7 - p.r. D.k. 69-0417

4.7 NO, + Tl +

(3.46 ± 0.1) x 10' g

' f.phot. D.k. at 600 nm. 67-7274

4.8 Acetic acid (4.6 ± 0.4) x 10

4 NO, + CH,COOH

f.phot. D.k. at 600 nm. 67-7274

4.9 2,6-Disulfoanthra- 1.0 x 10

quinone radical ion (A ) NO, + A' —* NO,' + A

8.0 f.phot. D.k. 73-7569

4.10 Ethanol (3.9 ± 0.4) x 10

( ’ 2 f.phot. D.k. at 600 nm. 67-7274

NO, + CH ,CH2OH (2.2 ± 0.4) x 10" acid “ p.r. D.k. at 600 nm in 5 M

HNO,; cor. for NO, + NO,.

74-1140

25
Table 4. Rates of reaction of NO,, N02 , N204

, NO.,

2

-, N2 0:„ NO,'' in aqueous solution—Continued

No. Reaction k(\T' s'

1 ) pH I Method Comment Ref.

4.11 Ethylene glycol NO, + CH,OHCH,OH(1.6 ± 0.3) x 10" acid - p.r. D.k. at 600 nm in 5 M

HNO,; cor. for NO, + NO.,. 74-1140

4.12 Formic acid NO, + HCOOH(2.06 ± 0.1) x 10

s “ - f.phot. D.k. at 600 nm. 67-7274

4.13 Glycerol (1.8 ± 0.4) x

10*’ NO, + CH,OHCHOHCH,OH

acid — p.r. D.k. at 600 nm in 5 M

HNO,; cor. for NO, + NO.,. 74-1140

4.14 Methanol NO, + CH,OH

(1.0 ± 0.1) x 10"

(1.2 ± 0.2) x 10" acid

f.phot.

p.r.

D.k. at 600 nm.

D.k. at 600 nm in 5 M

HNO,; cor. for NO, + NO,.

67-7274

74-1140

4.15 2-Propanol (3.6 ± 0.2) x 10" - - f.phot. D.k. at 600 nm. 67-7274

NO, + (CH,)2CHOH (2.3 ± 0.5) x 10" acid p.r. D.k. at 600 nm in 5 M

HNO,; cor. for NO , + NO ,. 74-1140

4.16 N02

-I- N02 - 2k =

N204

(7.6 ± 2.7) x 10'

2k = 3 x 10

7 7 -

f.phot.

p.r.

C. k. with ferrocyanide

ion in NO," soln.; obs.

effect of intensity on

buildup of ferricyanide

at 420 nm; assumed

€^,,2 == 10 and *(N02 + Fe(CN/-) =

4.3 x 10". D. k. at 400 nm in NaNO, (>0.5 M) soln.; 2k/e = 1.44 x 10

s

; assumed £4(K) = 208

M

~

' cm '.

68-

7024

69-

0417

2k = (9.0 ± 2.0) x 10

H p.r. D.k. at 400 nm in N02

’

soln. saturated with N2 0; K = 1.53 x 10"5 M

for N204 ^ 2N02.

69-0439

2k = (9.2 ± 3.0) x 10

R p.r. D.k. at 410 nm in N02 soln. saturated with N,0.

76-1171

4.17 N02 + FeiCN)^ —

NO/ + Fe(CN),*"

(4.3 ± 1.0) x 10" 7 - f.phot. P.b.k. at 420 nm in NO,

soln. 68-7024

4.18 N02 + NO N203 1.1 x 10" 7 p.r. D.k. at 400 nm in NO-N2 0 soln.; kr = 8.0 x 10 s .

70-0228

4.19 N20,(+H2 0)-* (1.0 ± 0.1) x 10 * s"

1 7 - p.r. - 69-0439

N02

" + N03

" + (6.0 2H + ± 1.0) x 10

4 s"1 “ p.r. D.k. at 350 nm. 76-1171

4.20 NO,2

" + H20 —

N02 + 20H'

1.0 x 10*

1.3 x 10*

1.6 x 10*

alk.

-

p.r.

p.r.

p.r.

D.k. at 290 nm; also condy. change; 400 nm

absorption obs. (N02); pA" = 7.8, 4.8 for (H

+ +)

NO,2

' ^ HNO,' (+ H

+

) ^

H2 NO,.

Conductivity change in NO," soln. contg. 0.2 M

MeOH.

D.k. at 260 nm.

70-0151

70-0254

76-1171

4.21 HNO,- — NO, + OH' - - - p.r. *0.5 = ^M'S. 70-0151

4.22 NO,2

" + 02 —

NO.,' + 02

‘ 2 x 10

H

(rel.)

12 y-r. Evaluated £/*(NO,2

- + H,0) = 2 x

1 O

’ from dependence of C(N02 ") on [02 J; assume /HNO,

2

' + H20) = 1 x 10*.

67-0032

4.23 NO,2

' + H2 P04

" —

HNO,- + HPO/*

5 x 10

8 7 — p.r. D.k. at 290 nm. 70-0151

26
Table 4. Rates of reaction of N03, N02, N204, NO,", N203, N02

" in aqueous solution—Continued

No. Reaction k(M~' s

-

') pH I Method Comment Ref.

4.24 N20:, (

H

20) —

5.3 x 10

2 s_l 5 - p.r. D.k. at 260 nm as well 70-0228

2N02

" + 2H +

1.0 x 10

3

as condy. change in N02'-N0-N2 0 soln.; tf(N203 NO + N02) =

7.3 x 10~5 M.

(See also 70-7264).

4.25 N02

2

' + h2 o -* 9.0 - p.r. D.k. at 270 nm; soln. 69-0439

NO + 20H" contains 0.25 M tert-BuOH;

(7.7 ± 1.7) x 10

2

pK = 7.7, 5.7 for (H

+ +)

no/-^hno2-(+ H

+

) —

h2 no2. (See also 70-7264). - p.r. D.k. at 270 nm. 76-1181

27
Table 5. Rates of reaction of P04 in aqueous solution

No. Reaction k(Af' s'

1 ) PH

5.1 H2 P04 + H2 P04 — 2islx 10" 3.5, H4P208 4.1

2k == (2.5 ± 0.5) x 10

H 3.8

5.2 HPO/ + HPO/ — 2k = 4.7 x 10

H 6.6- r,p2o8

2- 8.2

2k a 1.4 x 10

8 —9

5.3 P04

2

' + P04

2' — 2k a 1 x lO

9 11.2- PO 4" 11.7

2k = (1.0 ± 0.2) x 10

8 ~ 12

5.4 HPO/ + Br" — 6.5 x 10

6 9

HP04

2

' + Br

5.5 H2 P04 + Br' 8 x 10

8 4

5.6 HPO/ + cr < 10

4 7

5.7 h2 po4 + cr -* 2.2 x 10° 4

HPO/ + Cl 5.8 po4

2 + r — 3 x 10

8 12 P04v + I 5.9 HPO/ + N2 H4 4.9 x 10

8 9.4

5.10 HPO/ + N2 H5 +

1.4 x 10

8 7

5.11 h2 po4 + N2 H5 +

1.9 x 10

8 4

5.12 HPO/ + N/ 1.1 x 10

8 7

5.13 HPO/ + NH,OH 4.9 x 10

8 9

5.14 H2 P0 4 + NH,OH^ 1.2 x 10

7 4

5.15 HPO/ + NO/ — 1.4 x 10

7 7 HP04

2'

-(- no2 5.16 P042

' + OH' — (2.0 ± 0.2) x 10

r' >12

P04v + OH

5 x 10

s >12

5.17 HPO/ -f H,02 -* (2.7 ± 1.0) x 10

7 9.0 HP04

2

' + 2H" + 0/

5.18 H2 PO, + H2 02 (5.5 ± 1.0) x 10

7 4.5

I Method Comment Ref. ~1 p.r. D.k. at 500 nm in 1 M

H2 P04

" contg. N2 0; 2k/1. = 2.5 x 10"; e s

400 AT' cm'

1 .

70-0302

p.r. D.k. at 500 nm in 1-3 M

phosphate satd. with N20;

interpreted from 2k/e =

(11 ± 1) x 10* cm s’

1 and

€ = 230 AT' cm'

1 .

73-1050

~3 p.r. D.k. at 500 nm in 1 M

HP04

2

’ contg. N20;

2At/€ = 5.5 x 10

f

’ - 6.1 x 10

s

; £ a 800 AT 1 cm

1 .

70-0302

-^0 p.r. D.k. at 500 nm in N20-

satd. 0.3 M phosphate;

interpreted from 2k/t at 3-7 x 10

3 cm s

' and

£ = 720 AT 1 cm'

1 .

73-1050

~~6 p.r. D.k. at 500 nm in 1 At P04

4' contg. N20; 2k/e = 1.9 x 10

s - 2.4 x 10

s

; € = 4800 Af' cm'

1

.

70-0302

-^0 p.r. D.k. at 500 nm in N20-

satd. 0.3 AI phosphate;

interpreted from 2k/t sst 10

4 cm s'

1 and

£ = 2700 AT' cm'

1 .

73-1050

~0.2 p.r. D.k. at 520 nm in 0.02 Af

Li4P2 08 soln. 78-1075

-0.06 p.r. D.k. at 520 nm in 0.02 Af

Li4 P2 0B soln. 78-1075

-0.12 p.r. D.k. at 520 nm in 0.02 Af

Li4P2 08 soln. 78-1075

-0.06 p.r. D.k. at 520 nm in 0.02 Af

Li4 P2 08 soln. 78-1075

-0.2 p.r. D.k. at 520 nm in 0.02 Af

Li4 P2 08 soln. 78-1075

-0.2 p.r. D.k. at 520 nm in 0.02 AI

Li4 P2 08 soln. 78-1075

-0.12 p.r. D.k. at 520 nm in 0.02 Af

Li4P20g soln. 78-1075

-0.06 p.r. D.k. at 520 nm in 0.02 Af

Li4P208 soln. 78-1075

-0.12 p.r. D.k. at 520 nm in 0.02 Af

Li4P208 soln. 78-1075

-0.2 p.r. D.k. at 520 nm in 0.02 Af

Li4 P2 08 soln. 78-1075

-0.06 p.r. D.k. at 520 nm in 0.02 Af

Li4P2 08 soln. 78-1075

-0.12 p.r. D.k. at 520 nm in 0.02 Af

Li4 P208 soln. 78-1075

-1 p.r. D.k. at 500 nm in 0.3 Af HPO/" soln.; first order decay rate 9.15 x 10

4 at pH 12.65.

73-1050

-0.2 p.r. D.k. at 520 nm in 0.02 AI

Li4 P20H soln. 78-1075

0.1 f.phot. D.k. at 500 nm in 0.03 AI Na2 HP04 soln. 70-0326

0.1 f.phot. D.k. at 500 nm in 0.1 Af NaH2 P04 soln. 70-0326

28
Table 5. Rates of reaction of PO2' in aqueous solution — Continued

No. Reaction k(\T' s"’) pH I Method Comment Ref.

5.19 P04

2

' + HPO , 2' 5.5 x 10

s 12 —0.2 p.r. D.k. at 520 nm in 0.02 M 78-1075

P043

' + H" + P032' Li4P208 soln. 5.20 HPO+

‘ + HPO,2' 5.9 x 10" 9 -0.2 p.r. D.k. at 520 nm in 0.02 M

Li4 P208 soln. 78-1075

5.21 H2 P04 + H2 PO,' 4 x 10' 4 -0.06 p.r. D.k. at 520 nm in 0.02 M

Ii4P2 08 soln. 78-1075

5.22 P04

2

' + h2 po2

- 7.9 x 10' 12 -0.2 p.r. D.k. at 520 nm in 0.02 M 78-1075

P04

3' + H

T + HP02

' Li4P208 soln. 5.23 HP04

‘ + H2 P02

' 5.9 x 10 7 -0.12 p.r. D.k. at 520 nm in 0.02 M

Li4P20B soln. 78-1075

5.24 h2 po4 + H,P02‘

HP04

' + HPO-2- -

3.9 x 10

8

< 10s

4 -0.06 p.r. D.k. at 520 nm in 0.02 M

Li4P208 soln. 78-1075

5.25 - - p.r. D.k. at 520 nm. 77-1047

H2 P04

' + P05

2'

5.26 P04

2

' 4- S03

2' — 4.1 x 10' 12 -0.2 p.r. D.k. at 520 nm in 0.02 M 78-1075

P04

‘- + SO,' Li4P208 soln. 5.27 HP04

- + S032' 2.7 x 10

7 9 -0.2 p.r. D.k. at 520 nm in 0.02 M

Li4P2 08 soln. 78-1075

5.28 H2P04 + HS03

‘ 2.7 x 10

8 4 -0.06 p.r. D.k. at 520 nm in 0.02 M

Li4P208 soln. 78-1075

5.29 HP04

- + s2032' 1.0 x 10

8

1.9 x 10

8

7 -0.12 p.r. D.k. at 520 nm in 0.02 M

Li4P208 soln. 78-1075

5.30 HP04

- + S2 052' 7 -0.12 p.r. D.k. at 520 nm in 0.02 M

Li4P2 08 soln. 78-1075

5.31 Acetate ion 8.5 x 10

4 7.1 -0.12 p.r. D.k. at 520 nm in Li4P208 77-1106

HP04

' + CH3COO' -> soln. H2 PO,' + CH2COO‘

5.32 Acetic acid 3.4 x 10

s 3.6 -0.06 p.r. D.k. at 520 nm in Li4P.,08 77-1106

H2 P04 + CH3COOH soln.; k x /h2 s 0.5 detd. H3 P04 + CH2COOH (1) from C02 yields by y-r. H2 P04 + CH3COOH (78-1505).

H3 P04 + C02 + CH3 (2) 5.33 Acetone 3.3 x 10

5 3.2- -0.06 p.r. D.k. at 520 nm in Li4P2 08 77-1106

h,po4 + ch3 coch , 4.6 soln. H3 P04 + CH2COCH3 5.34 Acrylamide < 10

6 7.4 -0.12 p.r. D.k. at 520 nm in 0.02 M

Li4P208 soln. 77-1503

2.2 x 10

8 4 -0.06 p.r. D.k. at 520 nm in 0.02 M

Li4P2 08 soln. 77-1503

5.35 Acrylic acid 6.2 x 10

6 7.5 -0.12 p.r. D.k. at 520 nm in 0.02 M 77-1503

HPO,' + CH2 = CHCOO'-+ Li4 P208 soln.; product

-HO3 POCH2 CHOO- radical obs. by esr (77-5209).

H2 P04 + CH2 =CHCOOH 1.6 x 10

8 4 -0.06 p.r. D.k. at 520 nm in 0.02 M 77-1503

H203 P0CH2CHC00H Li4P2 08 soln. 5.36 Acrylonitrile 4.4 x 10

7 7.3 -0.12 p.r. D.k. at 520 nm in 0.02 M

Li4P2 08 soln. 77-1503

6 x 10

7 3.8 -0.06 p.r. D.k. at 520 nm in 0.02 M

Li4P208 soln. 77-1503

5.37 Alanine 1.6 x 10‘ 12 -0.2 p.r. D.k. at 520 nm in Li4P2 08 77-1106

P04

2

' + CH3CH(NH2)C00'

2.1 x 10

8 soln. 5.38 Ailyl alcohol 7 -0.12 p.r. D.k. at 520 nm in 0.02 M 77-1503

1.4 x 10

9 4 -0.06 p.r.

Li4P2 08 soln. D.k. at 520 nm in 0.02 M

Li4P2 08 soln. 77-1503

5.39 Allyl cyanide 3.4 x 10

7 7.2 -0.12 p.r. D.k. at 520 nm in 0.02 M

Li4P208 soln. 77-1503

8.8 x 10

8 4 -0.06 p.r. D.k. at 520 nm in 0.02 M

Li4 P2 08 soln. 77-1503

29
*

TaBLK 5. Rates of reaction of P0~ in aqueous solution — Continued

No. Reaction k(AT' s'

1 ) pH 1 Method Comment Ref.

5.40 />-Aminobenzoic acid H,P04 + NH2C() H,COOH

1.5 x

10'’ 3.3 -0.06 p.r. D.k. at 520 nm in Li4P20H soln. 77-1106

5.41 Benzoate ion HP04

'

-1- C,,H-COO' <

10' 7.1 -0.12 p.r. D.k. at 520 nm in Li4P20H soln. 77-1106

5.42 Benzoic acid 2.4 x 10

H H2 P04 + C„HsCOOH —

'(C„H-,COOH)

+ + H2 PO/

(QH-.COOH)* — QHS + C02 + H

+

(1)

(C, H-COOH) f + H20 HOC„H,COOH (2)

3.2 -0.06 p.r. D.k. at 520 nm in Li 4 P20H soln.; kf/k., ss 1 detd. from C02 yield by y-r. (78-1505).

77-1106

5.43 />-Chlorobenzoate ion H.PO. + ClC„H4 COO'

4.8 x 10 5.0 -0.06 p.r. D.k. at 520 nm in Li4 P20H soln. 77-1106

5.44 />-Chlorobenzoic acid H2 PO ; + C1C,H4C00H

1.0 x 10

t

’ 3.3 -0.06 p.r. D.k. at 520 nm in Li4 P20H soln. 77-1106

5.45 Crotonate ion HP04

' 4- CH ,CH = CHCOO'

3.5 x 10" 7.4 -0.12 p.r. - 77-1503

5.46 Crotonic acid H,P04 + CH ,CH =CHCOOH

4.5 x 10

H 4 -0.06 p.r. - 77-1503

5.47 p-Cya nobenzoate ion H2 PO v + CNC„H4C00'

1.0 x 10' 4.6 -0.06 p.r. D.k. at 520 nm in Li4 P20K soln. 77-1106

5.47a /7-Cvanophenoxide ion 1.9 x 10

H 11.2 -0.2 p.r. D.k. at 520 nm in Li4 P2 0H soln. 77-1503

5.48 Deoxyribose (7.5 ±

HPO/ + C-H.,0- —

H2 P0,- + C5HaOs

1.2) x 10

7 9.0 f.phot. D.k. at 500 nm in 0.03 M

hpo4

2-. 70-0326

5.49

5.50

Dihydrouracil < (2.9 ± 0.6) x 10'

Ethanol

9.0 f.phot. D.k. at 500 nm in 0.03 M

hpo4

2\

70-0326

po/' + CH,CH2 0H

HPO/' + ch',choh

1.9 x 10' 12.0 -0.2 p.r. D.k. at 520 nm in Li4P20K soln. 77-1106

HPO/ + CH4CH2OH -> (4.0 ±

H2 P04

' + CHjCHOH

0.6) x 10'

2.0 x 10

7

9.0

7 -0.12

f.phot.

p.r.

D.k. at 500 nm in 0.03 M

HP04

2'. D.k. at 520 nm in Li4 P2 Oa soln.

70-0326

77-1106

5.51

H2 P04 + CH jCH .OH ^

HjP04 + CH,CHOH

Formate ion

7.7 x 10' 4 -0.06 p.r. D.k. at 520 nm in Li 4 P20H soln. 77-1106

P04

2

' + HCOO' -> HP04

2’ + COO"

2.2 x 10' 12 -0.2 p.r. D.k. at 520 nm in Li 4P2Oa soln. 77-1106

HP04

‘ + HCOO' (2.9 ±

H2 P04

' + COO'

0.7) x 10

7

2.5 x 10

7

9.0

7 -0.12

f.phot.

p.r.

D.k. at 500 nm in 0.03 M

HP04 soln. D.k. at 520 nm in Li4P2 0K soln.

70-0326

77-1106

H2 P04 + HCOO' —

H,PO, + COO'

1.5 x 10

8 4.5 -0.06 p.r. D.k. at 520 nm in Li 4 P2 0H soln. 77-1106

5.52

5.53

Fumaric acid H ,P0j + HOOCCH = CHCOOH

HOOCCHCH(COOH)OPO,H,

i)-Glucose

1.5 x 10

7 3.2-

4.6 -0.06 p.r. D.k. at 520 nm in Li4 P2 0H soln.; product radical obs. by esr (77-5209).

77-1106

HPO/ + C, H l20„ ^ (8.0 ± 0.2) x 10' H2 P04

' + C( H n Or,

9.0 — f.phot. D.k. at 500 nm in 0.03 M

HPO/' soln. 70-0326

5.54

H2 P04 + C,H l20(> -^ (1.1 ±

H ,P04 Hh C,H n O( , Glycine

0.3) x 10

8 4.5 f.phot. D.k. at 500 nm in 0.1 M

H2 P04

’ soln. 70-0326

PO,

2

' + NH2 CH,COO —

HPO,2

* + NH2CHCOO'

2.6 x 10 12 -0.2 p.r. D.k. at 520 nm in Li,P2Oa soln. 77-1106

H2 PO t + NH t + CH2COO’ ^

H,PO ; + NH/CHCOO'

<

10’ 4.5 -0.06 p.r. D.k. at 520 nm in LUP2 O8 soln. 77-1106

30
Table 5. Rates of reaction of P04 in aqueous solution — Continued

No. Reaction k(M~' s' ) pH

5.55 /?-Hydroxybenzoate ion 1.7 x 10

8 7.2 HP04

' + OHC(,H4COO' —

h2 po4

~ + ocf,H4cocr po/ + 0HC() H4C00' — 5 x 10

7 11.4

5.56 HP04

' + 0QH4C00'

/>-Hydroxybenzoic acid 1.3 x 10

9 3.3

5.57 H2 P04 + 0HCf> H4C00H

Maleic acid 3.1 x 10

7 3.2-

5.58

H2 P04 + HOOCCH = CHCOOH-».

HOOCCHCH(COOH)OPO ( H2 Malonic acid 1.8 x 10

s

4.6

3.2-

5.59

H2P04 + CH2 (COOH)2 —

H,P04 + CH(COOH), (1) H2P04 + CH2(COOH)2 H ( P04 + CH2 COOH + C02 (2) Methacrylate ion 2.3 x 10

7

4.6

7.3

5.60 HP04

“ + CH2 = C(CH3 )COO'

Methacrylic acid 7.3 x 10

8 4

5.61 H2 P04 + CH2 = C(CH,)COOH

Methacrylonitrile

HP04

' + CH2 = C(CH,)CN 2.8 x 10

7 7.4 H2 P04 + CH2 =C(CH,)CN 3.9 x 10

8 3.9 5.62 Methanol P04

2

' + CH,OH — 1.0 x 10

7 12 HPO+2

' + CH2 OH

hpo4

~ + ch4 oh 1.0 x 10

7 7 H2 P04

' + CH2OH

H2 P04 + CH,OH 4.1 x 10

7 4

5.62a H:i P04 + CH2 OH

/7-Methoxyphenoxide ion 8.2 x 10

8 11.3

5.63 Methyl methacrylate

HP04

‘ + CH2 = C(CHs )COOCH f 3.9 x 10

7 7.3 H2 P04 + CH2 = C(CH ,)COOCH

,

6.2 x 10

8 4

5.64 2-Methyl-2-propanol

P042- + (CH4).,COH 4.2 x 10

s 12 HP04

2 " + CH2C(CH,)2OH

HPO/ + (CH j),COH 4.5 x 10

5 7 H2 P04

’ + CH2 C(CH,)2OH

H.P04 + (CH:i ).,COH ^ 3.9 x 10° 4

5.64a H.P04 + CH2 C(CH3)2OHPhenoxide ion 5.9 x 10

8 11.6

5.65 2-Propanol

P04

2

' + (CH3 )2CHOH -> 1.8 x 10

7 12 HP04

2' + (CH:j)2COH

HP04

‘ + (CH,)2CHOH (4.0 ± 1.0) x 9.0 H2 P04

- + (CH3)2COH

H2P04 + (CH:j ) 2CHOH (1.6

10

7

2.5 x 10

7 ± 0.3) x

7

4.5 H f P04 + (CH:})2COH 10

8

1.4 x 10

8 4

I Method Comment Ref.

-0.12 p.r. D.k. at 520 nm in Li4P2 08 soln. 77-1106

-0.2 p.r. D.k. at 520 nm in Li4P20H soln. 77-1503

-0.06 p.r. D.k. at 520 nm in Li4P208 soln. 77-1106

-0.06 p.r. D.k. at 520 nm in Li4P208 soln. Product radical obs. by esr (77-5209).

77-1106

-0.06 p.r. D.k. at 520 nm in Li4P208 soln. Product radical obs. by esr (77-5209);

k l /k2 ^ 1 detd. from C02 yield by y-r. (78-1505).

77-1106

-0.12 p.r. - 77-1503

-0.06 p.r. - 77-1503

-0.12 p.r. 77-1503

-0.06 p.r. - 77-1503

-0.2 p.r. D.k. at 520 nm in Li4P2 08 soln. 77-1106

-0.12 p.r. D.k. at 520 nm in Li4P208 soln. 77-1106

-0.06 p.r. D.k. at 520 nm in Li4P208 soln. 77-1106

-0.2 p.r. D.k. at 520 nm in Li4P208 soln. 77-1503

-0.12 p.r. _ 77-1503

-0.06 p.r. - 77-1503

-0.2 p.r. D.k. at 520 nm in Li4P2 08 soln. 77-1106

-0.12 p.r. D.k. at 520 nm in Li4P208 soln. 77-1106

-0.06 p.r. D.k. at 520 nm in Li4P2 08 soln. 77-1106

-0.2 p.r. D.k. at 520 nm in Li4P208 soln. 77-1503

-0.2 p.r. D.k. at 520 nm in Li4P2 08 soln. 77-1106

- f.phot. D.k. at 500 nm in 0.03 M

HP04

2' soln. 70-0326

-0.12 p.r. D.k. at 520 nm in Li4 P208 soln. 77-1106

- f.phot. D.k. at 500 nm in 0.1 M

H2 P04

' soln. 70-0326

-0.06 p.r. D.k. at 520 nm in Li4 P208 soln. 77-1106

31
Table 5. Rates of reaction of P04

~ in aqueous solution — Continued

No. Reaction k(M

~ 1 s'

1 ) pH I Method Comment Ref.

5.66 Propionic acid 4.2 x 10° 3.2- -0.06 p.r. D.k. at 520 nm in Li4 P20K 77-1106

H2 P04 + CH,CH2 COOH — 4.6 soln.; kf/k.2 ss 4 detd. from H,P04 + CH.CHCOOH (1) C02 yield by y-r. (78-1505).

H2 P04 + CH t CH2COOH —

H3 P04 + CH3CH2 + C02 (2) 5.67 Ribose (9.0 ± 2.0) x 10

7 9.0 - f.phot. D.k. at 500 nm in 0.03 M 70-0326

HPO/ + C5 H iuOs — HP04

2' soln. H2 P04

' + CsH()Os 5.68 Succinic acid 1.6 x 10

h 3.2- -0.06 p.r. D.k. at 520 nm in Li4 P20H 77-1106

H2 P04 + (CH2 COOH)2 — 4.6 soln. H3 P04 + HOOCCH2CHCOOH

5.69 Terephthalate ion 3.5 x 10' 5.2 -0.06 p.r. D.k. at 520 nm in Li4 P2 0K 77-1106

H2 P04 + HOOCQH4COO' soln. 5.70 Terephthalic acid — 6 x 10' 3.4 -0.06 p.r. D.k. at 520 nm in Li4 P2 0H 77-1106

H2 P04 + HOOCCf) H4COOH soln. 5.71 Thymine (9.6 ± 1.0) x 10

7 9.0 -0.2 f.phot. D.k. at 500 nm in 0.03 M 70-0326

HPO.,

2' soln. 5.72 Toluic acid 5.4 x 10

8 3.3 -0.06 p.r. D.k. at 520 nm in Li4P208 77-1106

H2 P04 + CH3C(,H4COOH soln. 5.73 Uracil (9.7 ± 2.0) x 10

7 9.0 - f.phot. D.k. at 500 nm in 0.03 M 70-0326

HP04

2 soln. (6.0 ± 2.0) x 10

8 4.5 - f.phot. D.k. at 500 nm in 0.1 M 70-0326

H2 P04

’ soln.

32
Table 6. Rates of reaction of Cl2 in aqueous solution

No. Reaction k(M~' s'

1 ) PH I Method Comment Ref.

6.1 Cl2

' + Cl2' - 2k = (1.4 ± 0.2) x 10

10 1.1, 0.5 f.phot. D.k. in NaCl-HC104 soln.; 67-7171

ci,' + cr

2k = (1.4 ± 0.3) x

10"’

6 assumed e(350 nm) = 1.25 x 10*M~' cm'

1 . 3.1 p.r. D.k. in N20-satd. Cl

soln. assuming €(360 nm) =

lO

4 ^1 cm'

1 ; independent

of pH 0.9 - 3.2.

68-0313

2k = (1.2 ± 0.3) x 10

10 1.9 0.1 p.r. D.k. 72-3107

2k = 5.2 x 10

9 1 0.2 f.phot. D.k. in FeCl

2+

soln. (10'3 M Fe

:1+

, 0.1 M H

+

, 73-7159

2k = (1.8 ± 0.5) x

10‘°

0.1 M Cl'); €(366 nm) =

1.0 x 10* AT 1 cm'

1 . ~1 p.r. D.k. in NaCl or HC1 soln. assuming € = 1.25 x 10

4 AT 1 cm'

1 .

74-1087

2k = (4 to 14) x 10

9 <10 p.r. D.k. in LiCl soln.; values from graph; k increased

as concn. decreased.

74-1149

2k = (2.7 ± 0.5) x 10

9

2k = (1.3 ± 0.5) x 10

10

7.0 <14 p.r. D.k. in 1.5-14 Af LiCl

soln. at 340 nm;

calcd. from

obs. 2k/

e

= (5 to 8) x 10

s

.

75-1154

“ p.r. D.k. in Cl' soln.; €(340

nm) = (1.24 ± 0.08) x 10

4 76-1048

2k = 1.7 x 10

10 AT' cm'

1 . 7 0.2 p.r. D.k. in CF soln.; €(340

nm) = 1.25 x lO

4 ^1 cm'

1 ; 77-1097

obs. change in [Cl2'] with

dose. 6.1a ci2

‘ — ci + cr kf = (1.1 ± 0.4) x 2 0.02 p.r. Abs. at 340 nm depends 73-1039

10

s s'

1 on [Cl']; kr = 2.1 x 10 M s . 6.2 Cl2' + 02

' -> < 2 x 10

9 - - p.r. D.k. in 02-satd. 1.3 and 74-1149

2cr + o2 5 M LiCl soln. compared

with deaerated soln. 6.2a Cl2

" + ho2 -> (4.5 ± 0.5) x 10

9 0AM 0.5 p.r. Calcd. from effect of 77-1170

2Cr + H

+ + 02 h2 so4 Cl~ on G(Fe’

+

) in airsatd. Fe'

+

soln. 6.3 Cl2' + SCN' - (2.9 ± 0.3) x 10

9 2.6 - p.r. D.k. in N2 0-satd. 6 x 10” 1 69-0565

2Cr + SCN M Cl' soln.; addn. of

0.1 M NaC104 gave k =

3.7 x 10

4

; product is (SCN)2' detd. by

absorption spectrum; a:(ciscn' + scn' cr +

(SCN)2') = 3.0 x 10

4

. 6.4 Cl2

' + Ce',+ — (0.8 or 4.0) x 10

4 1 - 1 - y-r. Calcd. from G(Ce, +

) in 75-0440

Ce

4+ + 2Cf Ce

4+

soln. contg. 10 M

LiCl assuming &(C12 +

Cl 2

') = 2 x 10

9

. 6.5 Cl2

' + OCIO (1.0 ± 0.1) x 10" 5 -

' f.phot. D.k. in C102-C1" soln. 73-7043

33
Table 6. Rates of reaction of Cl2 in aqueous solution —Continued

No. Reaction k(nr' s"') pH I Method Comment Ref.

6.6 Cl," + Co(ll) CoCi2+ + cr

(1.4 ± 0.2) X 10

6 ~1 0.3 f.phot. D.k. in Cl soln.

(0.1 M Cl", 0.005 M

73-7316

Cl2 , 0.1 A/H +

) contg.

0.1 -0.5 M Co(Il); A//' = 29 ± 4 kj mol"

1 and A51 = -31 ± 10 J K"

1 mol"

1

detd. at 13.5 to 41.5°C.;

inner sphere substitution

reaction. 6.7 Cl2

" + CoL2+ — (1.0 ± 0.4) x lO'

1 1 1.1 f.phot. D.k. 72-7506

Co

1 " L = 5,7, 7, 12, 14,14-hexamethyl-l,4,8,1 l-tetraazacyclotetradeca-4,1 1-diene

6.8 + Cr..,2+ -

[Cr(OH,).Cl]2+ + Cl" Cl/ + Cr..,2+ -

[Cr(OH2)J

,+ + 2C1"

Cl2

" + Cu

2 +

(2.4 ± 0.3) x 10°

(2.4 ± 0.3) x 10

9

< 1.5 x 10

8

1 0.2 p.r. D.k. in deaerated Cl"

soln.; A6'° = -263 kj mol"

1 ; reaction 50% inner sphere and 50% outer sphere.

74-1104

6.9 - - p.r. - 75-1188

6.10 Cl2

" + CuL2+ — Cu'" 6.5 x 10

H 2 0.02 p.r. D.k. 78-1503

L = 5,7,7.12,14,14—hexamethyl-l,4,8,ll-tetraazacyclotetradecane

6.11 Cl2

" + CuL2+ — Cu

1 " 3.2 x 10

8 2 0.02 p.r. D.k. 78-1503

L = 5,7,7,12,14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,ll -diene

6.12 Cl2

" + Fe

2+ -> (3.8 ± 0.3) x 10

7 2.1 0.04 p.r. D.k. 68-0313

FeCl

2 + + Cl" (1) (1.4 ± 0.2) x 10

: 1 0.1 p.r. D.k. in soln. contg. 0.01 73-1039

Cl2

" + Fe., 2+ -* M NaCl and 0.1 M

Fe

,+ + 2C1" (2) perchloric acid. = (4.0 ± 0.6) x

10'’ 1 0.2 f.phot. D.k. in FeCl

2+

soln. (10*3 M Fe

3+

, 0.1 M H

+

, 73-7159

k2 = (1.0 ± 0.2) x 10

7 0.1 M Cl") in pres, of Fe"

+

; AT/’ for the inner sphere reaction (1) =

31.5 ± 4 kj mol'

1 and AS' = -21 ± 15 J K"

1 mol"

1 ; A//1 for the outer sphere reaction (2) =

22.7 ± 4 kj mol"

1 and AS1 = -42 ± 15 J K"

1 mol'

1 . 6.13 a; + Mn.,,24 — 8 x 10

f> 1 0.25 f.phot. D.k. in Cl," soln. (0.1 73-7317 Mn"

1 + 2C1" M Cl", 0.005 M Cl2 , 0.1 M H

+

) contg. 0.001-0.02 M Mn2+

; Ea = 34 ± 4 kj mol"

1 (16 to 40°C);

reaction is inner sphere

electron transfer

controlled; A//1 = 32 ± 4

kj mol'

1 , AS1 = -4 ± 6

J K"

1 mol'

1 . 6.14 a; + n2 h, + 8.0 x 10

6 1 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093

1.4 x 10

7 6.8 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

contg. S2 0K

2

". 6.15 a2

" + nh2oh 9.3 x 10

6 6.7 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093 < 10

s contg. S20K

2". 6.16 ci; + nh ( oh" 1 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093

6.17 a2

" + n; 1.2 x 10

y 7 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093

contg. S20H

2’.

34
Table 6. Rates of reaction of Cl2 in aqueous solution—Continued

No. Reaction k(Af' s"

1 ) pH I Method Comment Ref.

6.18 cir + no2

CL, + NiL2+ — Ni'"

2.5 x 10

8 7 ~1 p.r. D.k. in 1 M Cl" soln. contg. S,08

"-. 78-1093

6.19 2.0 x 10

9 2 -0.02 p.r. D.k. in 0.005 - 0.01 M 78-1502

L = 5,7.7, 12, 14,14—hexamethyl- 1.4,8, 11 -tetraazacyclotetradecane Cl soln.

6.20 Cl2

_ + NiL2+ -> Ni"

1 9.6 x 10

9 2 -0.02 p.r. D.k. in 0.005 - 0.01 M 78-1502

L = 5,7,7,12,14,14—hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4, 11 -diene CT soln.

6.21 Cl2

_ + NiL2+ -> Ni"

1 8.7 x 10

9 2 -0.02 p.r. D.k. in 0.005 - 0.01 M

Cl" soln. 78-1502

L = 5,7,7,12,14,14—hexamethvl-1,4,8,1 l-tetraazacyclotetradeca-l,4,8,ll-tetraene

6.22 a2

~ + oh- 7.3 x 10

6 10-13 - p.r. Unpub. data from R.W.

Fessenden. 78-1093

6.23 Cl2

‘ + h2 o2 1.4 x 10" 1 -1 p.r. D.k. in 1 M CT soln. 78-1093

6.24 Cl2

* + PtCl/- (1.1 ± 0.2) x 10

9 - - p.r. D.k. in 0.5 M HC1; 75-1188

Pt(iii)

(1.60 ± 0.10) x 10

9 ~1 p.r.

transient with c(260

nm) == 13000 Af ] cm"

1 was formed.

D.k. in 0.1 M HC1 soln.; 76-1055

1.0 M NaCl soln. gave

k = (1.25 ± 0.3) x 10

9

. 6.25 a2~ + PtL,

2+

(8.9 ± 1.9) x 10

9

•X- - p.r. D.k. in 0.5 M HC1; 75-1188

Pt(iii) transient with 6(280 L = ethylenediamine nm) = 15900 M~ 1 cm"

1 was formed. 6.26 Q,

- + PtLCl" -» (6.4 ± 0.4) x 10

9 - - p.r. D.k. in 0.5 M HC1; 75-1188

Pt(III) transient with 6(280 L = diethvlenetriamine nm) = 17000 AT ' cm"' was formed. 6.27 Cl-T + PtLCl + -> (4.2 ± 0.4) x 10

8 - - p.r. D.k. in 0.5 M HQ; 75-1188

Pt(III) transient with e(290 L = tetraethvldiethylenetriamine nm) = 7240 AT

1 cm"' was formed. 6.28 or + S03

2- 3.3 x 10' 7 -1 p.r. D.k. in 1 M Cl soln. 78-1093

contg. S208

2 -. 6.28a Cl2' + Ti(III) - 4 x 10

8 ~i p.r. D.k. at 380 nm in 0.02 M

HC1 contg. formic acid. 73-1057

6.29 Cl2

‘ + T1(I) -> Tl(II) 5 x 10

9 - 1 p.r. P.b.k. at 260 nm in 0.99 M HC1 soln. 74-1038

6.30 Cl,' + V

2+ -> (1.95 ± 0.2) x 109 i 0.2 p.r. D.k. in deaerated CT 74-1104

2cr + v

3+

soln.; AG° = -241 kj mol '; outer sphere

diffusion control. 6.31 Acetanilide - 2.0 x 10

7 7 -1 p.r. D.k. in 1 M Cl" soln. 78-1093

Cl," + Cf,H4NHC0CH3 contg. S2 08

2

". 6.32 Acetic acid < 10

4

1 -1 p.r. D.k. in 1 M Cl" soln. 78-1093

6.33 Acetone 1.4 x 10

3 1 -1 p.r. D.k. in 1 M Cl soln. 78-1093

6.34 Acriflavin - 4 x 10

9 - 1 p.r. D.k. at 450 nm (dye) in N2 0-satd. 1 M KC1 soln. 70-0241

6.35 Acrylate ion 1.9 x 10

7 7 -1 p.r. D.k. in 1 M Cl" soln. 78-1093

Cl2

" + CH2 =CHCOO" contg. S208

2". 6.36 Acrylic acid

ci,- + ch2 =chcooh

5.4 x

10'' 1 -1 p.r. D.k. in 1 M Cl soln. 78-1093

6.37 Acrylonitrile 2.2 x 10

ft 7 -1 p.r. D.k. in 1 M Cl soln. 78-1093

Cl2

" + ch2 =chcn contg. S2 08

2". 6.38 Adenine < 5 x

10"’ 2.7 - p.r. D.k. in 0.1 M NaCl soln. 68-0313

6.39 Alanine 1.3 x 10" 1 -1 p.r. D.k. in 1 M Cl" soln. 78-1093

35
Table 6 Rates of reaction of Cl2 in aqueous solution—Continued

No. Reaction k(AT' s’

1 ) PH 1 Method Comment Ref.

6.40 Allyl alcohol 5.9 x 10

H 1,7 ~1 p.r. D.k. in 1 M Cl' soln.; 78-1093

or + ch2 =chch2 oh at pH 7 Cl2 was

generated by SO, from SO 2'

6.41 />-Aminobenzoate ion 1.1 x 10" 7 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

contg. S2 0/~.

6.42 />-Aminobenzoic acid 2.2 x 10‘ 1 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

6.43 Anilinium ion 1.2 x 10

7 1 ~1 p.r. D.k. in 1 M Cl' soln. 78-1093

Cl2

' + QH-NH,+ 6.44 Anthrasemiquinone- 6.5 x 10

K 8.0 - . f.phot. D.k. 73-7569

2,6-disulfonate radical ion Cl2

~ + A' -> A + 2C1' 6.45 Ascorbic acid 6.8 x 10

8 2 - p.r. - 72-0266

Cl2

" + AH2 - (6.0 1.0) x 10

8 2 - p.r. D.k. in N2 0-satd. 0.5 M 73-3006

•AH + H

+ + 2C1* Cl" soln. 6.46 Benzenesulfonate ion < 1 x 10

1 7 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

contg. S20„'". 6.47 Benzoate ion 2 x 10" 7 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

contg. S20/’.

6.48 Benzonitrile < 1 x 10’ 1,7 ~1 p.r. D.k. in 1 M Cl" soln.; at 78-1093

} pH 7 Cl2

’ was generated

by S04

’ from S2 0H

2

". 6.49 p-Bromobenzoate ion 7 x 10" 7 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093

contg. SoOH

2". 6.50 />-Chlorobenzoate ion 3 x 10" 7 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

contg. S20H'\ 6.51 5-Chlorouracil 1.0 x 10

7 2.0 - p.r. D.k. in 0.01 M NaCl soln. 72-3107

6.52 /j-Cyanobenzoate ion 5 x 10" 7 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093

6.53 />-Cyanophenol 4.0 x 10

7 1 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093

6.54 Cysteine (8.5 ±

SC o 00 X © 1.8 4 p.r. D.k. in 0.1 M Cl soln. 72-0036

6.55 Cytidine 4 x 10 2.0 - p.r. D.k. in 0.01 M NaCl soln. 72-3107

6.56 Cytosine (9.1 ± 0.7) x 10

7 2.7 - p.r. D.k. in 0.1 M NaCl soln. 68-0313

1.0 x 10' 2.0 - p.r. D.k. in 0.01 M NaCl soln. 72-3107

6.57 Deoxyadenylic acid < 5 x 10" 2.7 - p.r. D.k. in 0.1 M NaCl soln. 68-0313

6.58 Deoxycytidylic acid < 5 x 10" 2.7 - p.r. D.k. in 0.1 M NaCl soln. 68-0313

6.59 Deoxvguanylic acid (1.2 ± 0.1) x 10

8 2.7 - p.r. D.k. in 0.1 M NaCl soln. 68-0313

6.60 Dithiothreitol (3.0 ± 0.3) x 10* 2 - p.r. D.k. 73-1020

6.61 Dodecyl sodium sulfate 3.9 x 10" 2.0 - p.r. D.k. in 0.5 M NaCl soln. 72-3107

6.62 Ethanol 4.5 x 10* 1 ~i p.r. D.k. in l M Cl soln. 78-1093

Cl2

" + CH3 CH2 OH

6.63 Formate ion 1.9 x 10" 7 ~i p.r. D.k. in 1 M Cl’ soln. 78-1093

Cl/ + HC02

‘ contg. S2 0H

2 ". 6.64 Formic acid 1.0 x 10" 3.7 ~i p.r. D.k. in 1 M Cl’ soln. 78-1093

Cl2

' + HCOOH contg. S2 0H

2 ". 3 x 10’ 3 ~i p.r. D.k. in 1 M Cl soln. 78-1093

6.7 x 10

s 1 ~i p.r. D.k. in 1 M Cl soln. 78-1093

6.65 F umarate ion 4 x 10" 7 ~i p.r. D.k. in 1 M Cl soln. 78-1093

Cl,' + 'OOCCH = CHCOO' — contg. S2 0H

2

"; adduct cr + "OOCCHCHC1COO" radical obs. by esr (75-5244).

Cl2

‘ + OOCCH = CHCOOH 2.4 x 10" 3.7 -i p.r. D.k. in 1 M Cl" soln. 78-1093

contg. S2 0H

2

". 6.66 F umaric acid ~2x 10'’ 1 ~i p.r. D.k. in 1 M Cl soln. 78-1093

Cl2

" + HOOCCH = CHCOOH

6.67 Glutamic acid 2.3 x 10

s 1 ~i p.r. D.k. in 1 M Cl soln. 78-1093

6.68 Glycine ~ 5 x 10" 9.8 ~i p.r. D.k. in 1 M Cl" soln.; 78-1093

<104

1 at pH 9 8 Cl 2 generated

by SO, from S20„

2 ’. 6.69 Guanine (8.1 -± 0.6) x 10

7 2.3 - p.r. D.k. in 0. 1 M NaCl soln. 68-0313

36
TABLE 6. Rates of reaction of Cl, in aqueous solution—Continued

No. Reaction k(AT

] s'1 ) pH I Method Comment Ref.

6.70 Hexadecyltrimethyl- 1.2 x 10

7 2.0 p.r. D.k. in 0.01 M HC1 soln. 72-3107

ammonium chloride

Hexadienedioate ion See Muconate ion. Hexadienoate ion See Sorbate ion.

6.71 Hexenedioate ion 1.6 x 10

8 7 ~1 p.r. D.k. in 0.1 M C\~ soln. 78-1093

or + oocch2 ch=chch,coo’ contg. S20H

2'. 6.72 Histidine (1.4 ± 0.1) x 10

7 1.8 - . p.r. D.k. in 0.1 M Cl' soln. 72-0036

6.73 Hydroquinone 1.4 x 10

9 1 ~1 p.r. D.k. in 0.1 M Cl' soln. 78-1093

Cl2

- + 0HQH40H — 1.5 x 10

9 9.5 ~1 p.r. D.k. in 0.1 M CT soln. 78-1093

2Cr + 2H+ + •OC6H40’ contg. S208

2

’. 6.74 /7-Hydroxybenzoate ion 2.8 x 10

8 7 ~1 p.r. D.k. in 0.1 M Cl’ soln. 78-1093

Cl2’ + 0HC6H4C00’ -> contg. S2 08

2

’; product

2Cr + H

+ + 0C(1H4C00’ radical obs. by esr. 6.75 p-Hydroxybenzoic acid 1.3 x 10

8 3.1 ~1 p.r. D.k. in 0.1 M Cl’ soln. 78-1093

Cl,' + 0HC6H4C00H contg. S,0R

2’. 1.1 x 10

8 1 ~1 p.r. D.k. in 0.1 M Cl' soln. 78-1093

6.76 Maleate ion 3 x 10

6 6.5 ~1 p.r. D.k. in 0.1 M Cl soln. 78-1093

contg. S208

2’. 6.77 Methanol 3.5 x 10

J 1 ~1 p.r. D.k. in 1 M CT soln. 78-1093

6.78 Methionine (7 ± 0.7) x 10

6 1.8 - p.r. D.k. in 0.1 M CT soln. 72-0036

6.79 /?-Methoxybenzoate ion 2.0 x 10

8 7 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

Cl2' + CH ( OC() H4COO' -> contg. S2 08

2

’; product

2C1' 4- CHs 0

+ C6H4C00' radical identified by

optical p.r. 6.80 />-Methoxyphenol 1.1 x 10

9 1 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

6.81 2-Methyl-2-propanol ~ 7 x 10

2 1 ~1 p.r. D.k. in 1 M Cl" soln. 78-1093

6.82 Muconate ion 2.1 x 10

8 7 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

contg. S208

2’. 6.83 Phenol 2.5 x 10

8 1 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

6.84 ^-Phenoxybenzoate ion 1.5 x 10

8 7 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

contg. S208

2’. 6.85 Phenylalanine (6 ± 0.6) x 10

6 1.8 - p.r. D.k. in 0.1 M CT soln. 72-0036

6.86 Polyoxyethylene(15)nonyl 2.1 x 10

8 2.0 - • p.r. D.k. in 0.01 M NaCl soln. 72-3107

phenol

6.87 2-Propanol 1.2 x 10

s 1 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

(1-9 ± 0.3) x 10" IpIwnI - p.r. D.k. in 0.5 M HC1. 75-1188

6.88 Propionic acid 2.2 x 10* 1 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

6.89 Salicylic acid 1.1 x 10

8 1 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

6.90 Serine 1.2 x 10" 1 p.r. D.k. in 1 M Cl soln. 78-1093

6.91 Sorbate ion 6.8 x 10

8 7 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

contg. S208

2

’. 6.92 Succinic acid ~ 8 x 102 1 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

6.93 Terephthalate ion 6 x 10° 7 ~1 p.r. D.k. in 1 M Cl’ soln. 78-1093

contg. S208

2’. 6.94 Tetramethylpiperidone 1.4 x 10° 2 1 p.r. D.k. at 350 nm. 71-0618

TV—oxyl (TAN)

6.95 Thymidylic acid (4.4 ± 0.3) x 10' 2.7 p.r. D.k. in 0.1 M NaCl soln. 68-0313

6.96 Thymine (1.2 ± 0.1) x 10

8 2.7 - p.r. D.k. in 0.1 M NaCl soln. 68-0313

7.0 x 10' 2.0 - p.r. D.k. in 0.01 M NaCl soln. 72-3107

6.97 />-Toluate ion 5 x 10° 7 ~1 p.r. D.k. in 1 M Cl soln. 78-1093

contg. S208

2

’. • 6.98 Tryptophan (2.6 ± 0.3) x 10

9 1.8 - p.r. D.k. in 0.1 M Cl' soln. 72-0036

6.99 Tyrosine (2.7 ± 0.3) x 10

8 1.8 - p.r. D.k. in 0.1 M Cl’ soln. 72-0036

6.100 Uracil (4.1 ± 0.3) x 10' 2.7 - p.r. D.k. in 0.1 M NaCl soln. 68-0313

3.5 x 10

7 2.0 - p.r. D.k. in 0.01 M NaCl soln. 72-3107

3.7 x 10

7 6 - p.r. - 75-5244

37
TablF 7. Rates of reaction of Br_, in aqueous solution

No. Reaction k(M~ s' ) pH I Method Comment Ref.

7.1 Br, + Br,' —*• k = 1.8 x 10*

Br," + Br

2 0.03 p.r. D.k. in aerated 10 * M

Br' - 10‘;* M Br.,; k/e =

2.2 x 10’ cm s’

1 ; e(360

nm) = 8200 AT

1 cm'

1 .

65-0382

k = (1.8 ± 0.3) x 10” 7 0.01 p.r. D.k. in N,0-satd. 10'“ M Br ; £(360 nm) =

9600 ± 800 AT

1 cm '.

65-0383

2k = (3.3 ± 1.0) x 10” 7 <0.01 p.r. D.k. in 10'4 - 10'2 M

Br soln.; £(365 nm) =

7800 ± 2000 AT

1 cm'

1 .

66-0425

2k = (3.7 ± 0.6) x 10” 6 0.02 f.phot. D.k. in 0.02 M Br' or HgBr2 - HgBr4

“’ soln.; €(360 nm) = (7.8 ± 0.2) x 10* AT 1 cm'

1 .

67-7171

k = 2.8 x 10” 12 0.02 p.r. D.k. in N2 0-satd. 10

“ M Br' soln.; £(360 nm) =

8200 AT 1 cm'

1 .

68-0153

2k = 5.3 x 10” 1 0.2 f.phot. D.k. in FeBr“

1 soln. (10' ' M Fe

<+

, 0.1 A/ H

+

, 0.1 M Br ); £(366 nm) =

7.8 x 10* AT' cm'

1 .

73-7159

1.6 x 10” f.phot. Calcd. from assumed mechanism for d.k. at 350 nm in Br soln. 10

’

to 10' 1 M.

75-7346

2k = (3.1 ± 0.9) x 10” p.r. D.k. in Br soln.; €(360 nm) = (8.56 ±

0.24) x

10'* AT

1 cm'

1 .

76-1048

2.4 x 10” 0.02 p.r. D.k. in N20-satd. Br

soln.; €(360 nm) =

9600 AT

1 cm'

1 ; rates

in micellar systems also

detd.

76-1058

7.1a Br2" — Br + Br' k, = (2.5 ± 1) x 10

4 s'

1 2 p.r. Calcd. from dependence

of [Br2 ] on ( Br’]; kr =

(5.4 ± 3) x 10” and Kr' =

(2.2 ± 1) x 10

:> AT'.

65-0383

kf = (7 ± 2) x 10

s

s'

1 ~2 0.12 f.phot. Calcd. from buildup of Br2

" in Br -Br2 soln.;

k, = (1.1 ± 0.1) x

10'°.

75-7222

7.2 Br2 + Br — Br,' 1.37 x 10” ~7 f.phot. Calcd. from assumed mechanism for d.k. at 350 nm in Br soln. 10'5 to 10’ 1 M.

75-7346

7.3 Br2

' 4- H — H

+

4- 2Br" (7 ± 1) x 10” 2 - p.r. - 70-7726

7.4 Br2

' 4- H02 — (1.6 ± 0.5) x 10” Br2 4- H02

’ 2 — p.r. D.k. in air-satd. 0.1 M Br’ soln. 65-0383

7.5 Br2

' 4- BrO' — (8.0 ± 0.7) x 10

7 BrO + 2Br'

— 0.02 p.r. D.k. in Br - BrO' soln. 68-0153

7.6 Br2

" + Br02 — (8.0 ± 0.8) x 10

7 BrO 4- BrO' + Br' - 1 p.r. D.k. in Br - Br02 soln. 68-0153

7.7 Br2 4- BrO, no reaction — — p.r. D.k. of Br2

' unaffected by BrO,’. 68-0153

7.8

* Br2

* + C102 (1.2 ± 0.1) x 10” - - f.phot. D.k. in Br - C102 soln. 73-7043

7.9 Br2

' 4- Co

+ —» (1.0 ± 0.3) x 10

10 Co

2+

4- 2Br' — - f.phot. D.k. in Br' soln. contg. Co

2 +

; e1(| " + Co

2 T Co +

. 70-7726

7.10 Br2

' 4- Co

2 ' - - f.phot. No reaction. 70-7726

73-7316

7.11 Br2

‘ 4- CoL

2+

(1.4 ± 0.1) x 10” 1 0.2 f.phot. D.k. in Br' soln. 72-7506

Co"

1 2.0 x 10” 9.2 0.1 L = 5,7,7,12,14,14—hexamethyl-1,4,8,1 l-tetraazacyclotetradeca-4,1 1-diene

p.r. D.k. in N2 0-satd. Br'

soln. 76-1203

38
TABLE 7. Rates of reaction of Br2 in aqueous solution—Continued

No. Reaction £(AT' s') pH I Method Comment Ref.

7.12 Br2

- + Crai| 2+ — (1.9 ± 0.2) x 10" 1 0.2 p.r. D.k. in deaerated Br" 74-1104

[Cr(OH2)sBr]2+ + Br

- soln.; AG° = -213 kj

mol"'; inner sphere

diffusion controlled mechanism.

7.13 Br2

- + CuL2+ -> Cu"

1 2 x 107 6 0.02 p.r. D.k. 78-1503 L = 5,7,7,12,14,14—hexamethyl-l,4,8,ll-tetraazacyclotetradecane

7.14 Br2

- + CuL2+ — Cu'" 1 x 10

7 6 0.02 p.r. D.k. 78-1503

L = 5, 7,7,12, 14,14-hexamethyl-l,4,8,1 l-tetraazacyclotetradeca-4,1 1-diene

7.15 Br2

" + Fe,,

2 * - (3.6 ± 0.4) x 10

6 1 0.2 f.phot. D.k. at 366 nm (Br,~) or 73-7159

Br

- + FeBr

2+

p.b.k. at 405 nm (FeBr

2+

); AH' = 25.2 ±2kJ mol"

1 ; AS' = -42 ± 12 J k"' mol"

1 ; inner sphere substitution controlled mechanism.

7.16 Br.,

- + ferricenium 3 x 10

tt - - p.r. - 74-1182

ion — ferrocene 7.17 Br2

-+- H202 —

< io

( 7 - p.r. D.k. in N20-satd. 1 M 78-1093

H

+ + 2BV + H02 NaBr soln. 7.18 Br2

- + Mn2+ -> 6.3 x 10

6 1 0.25 f.phot. D.k. in Br;,

- soln. (0.1 73-7317

2Br

- + Mn<+ M Br

-

, 5 x 10

-s M Br2 and 0.1 il/H + );£a =

36 ± 4 kj mol

-1

; AH* --- 33.6 ± 4 kj mol

-1

; AS1 =

-3 ± 6 J K

-1 mol

-

'; inner sphere electron

transfer. 7.19 Br2

- + NiL2+

Ni'" 3.4 x 10" 2 p.r. D.k. in 0.005 - 0.01 M 78-1502

L = 5,7,7,12, 14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradecane Br

-

soln.

7.20 Br2

- + NiL2+

Ni"' 9.8 x 10

9 2 p.r. D.k. in 0.005 - 0.01 M 78-1502 L = 5,7,7, 12, 14, 14—hexamethyl-1 ,4,8, 1 1 -tetraazacyclotetradeca-4, 1 1-diene Br

-

soln.

7.21 Br2

- + NiL2+ — Ni

1 " 9.5 x 10

9 2 - p.r. D.k. in 0.005 - 0.01 M

Br

-

soln. 78-1502

L = 5,7,7,12,14,14—hexamethyl-1,4,8,1 l-tetraazacyclotetradeca-l,4,8,ll-tetraene

7.22 Br2

" + PtCl+

2- — (2.8 ± 0.2) x 10

K 1 ^0 p.r. D.k. in N,0-satd. 0.1 76-1055

Pt(III)—or 0.01 M Br soln. contg.

Br2

- + Ru(bipy);j

2 "

PtCl4

2-

; Pt(III)—

(€.,,„ nm = 8.4 x 10

4 AT

1 cm

-1

) may be PtBrn Cl4_n

-

. 7.23 (3.1 ± 0.5) x 10

9 1 M - f.phot. D.k. in 10 * M Br soln. 73-7066

[Ru(bipy) s ,+ Br'] + Br

- h2 so4 7.24 Br2

- + SCN

- 1.9 x 10

9 - - p.r. D.k. in N20-satd. 5 x 69-0180

2Br" + SCN or — 10 ' M Br

- soln. contg. Br" + BrSCN" 10

-r> - 2 x 10 ‘ M SCN

-

as well as p.b.k. at 500 nm (SCN)2

-

; ^(BrSCN

- + SCN- — Br- +

(SCN)2

-

) = 1.1 x 10

2

. 7.25 Br2

" + Tl +

1 0.01 f.phot. no reaction 74-7625

7.26 Br2

" + U02 + -> 0.33 x 10 ‘ s'

1 1.7 - f.phot. D.k. in Br

- - U(VI) 76-7279

2Br* + U022+

soln.; react, probably

reoxid. of U(V) to U(VI). 7.27 Br2

* + V

2+ — (1.48 ± 0.2) x 10

9 1 0.2 p.r. D.k. in Br

- soln.; AG° = 74-1104

2Br” + V'

t+ -191 kj mol

-

'; outer sphere diffusion control. 39
TABLE 7. Rates of reaction of Br2 in aqueous solution —Continued

No. Reaction k(\r' s’

1 ) pH I Method Comment Ref.

7.28 Acriflavin (3.7 ± 0.6) x 10" - - p.r. D.k. of Br2

’ in N,0-satd.

10

1 M Br” soln. as well

as dye bleaching at 450 nm.

70-0241

7.29 Alcohol dehydrogenase 2.6 x 10" 7 - p.r. D.k. in 0.05 M Br" soln.; 74-1125

(yeast) k — 1.0 x 10 * for horse

liver enzyme (78-3007). 7.30 Ascorbic acid (1.1 ± 0.4) x 10

H 2 - p.r. PA = 4.17, 11.57. 72-0266

Br2

" + AH_, — (1.1 ± 0.4) x 10" 7 •AH + H

+ + 2Br" (8.7 ± 0.9) x 10K 7.2 0.5 p.r. D.k. in N20-satd. Br’ 73-3006

soln. 7.31 />-Bromophenoxide ion 2.75 x 10

H 12.5 - p.r. - 74—3052

7.32 Carboxypeptidase A (1 to 2.5) x 10" 8-11 - p.r. D.k. in 0.05 M Br" soln. 73-1060

7.33 />-Chlorophenoxide ion 1.73 x 10

H 12.5 - p.r. - 74-3052

7.34 a-Chymotrypsin 1.6 x 10" 6.7 p.r. D.k. in N2 0-satd. 0.04 M Br"; mol. wt. = 20,000.

74-1096

7.34a Concanavalin A 7 x 10" 7.1 — p.r. P.b.k. at 530 nm in N2 0-

satd. 10"2 M KBr soln. 78-3005

7.35 /?-Cyanophenoxide ion 1.8 x 10

H 12.5 - p.r. - 74-3052

7.36 Cysteamine 3 x 10

K - - p.r. - 74-1168

7.37 Cysteine (1.8 ± 0.2) x 10

H 6.6 0.1 p.r. D.k. in N2 0-satd. Br"

soln.; k increases with pH.

72-0036

7.38 Cytochrome C (ferro) Br2

"

-I- Fe

+ cytC—

1.5 x 10" 7 p.r. — 77-3091

2Br" + Fe*cytC

1.8 x 10" 7.39 Diethyl disulfide 4-5 0.02 p.r. D.k. in N2 0-satd. Br’ 76-1143

Br2

’ 4- RSSR — soln., as well as p.b.k. 2Br" + RSSR-+

at 430 nm (RSSR- +

). 7.39a Diethyl sulfide ~2x 10" 3.9 0.2 p.r. D.k. at 360 nm in N2 0- 77-1164

Br2' + (C2 H-)2S — satd. KBr soln. (C2 H-,)2SBr- 4- Br" < 1 x 10* 7.40 3,5-Diiodotyrosine 6 - p.r. D.k. in N2 0-satd. 0.04 M 73-1067 ~ 1.3 x 10" 8 Br’ soln.; values from

graph. 7.41 Dimethyl disulfide 2.2 x 10" 4-5 0.02 p.r. D.k. in N20-satd. Br"

soln., as well as p.b.k.

at 430 nm (RSSR* +

).

76-1143

7.42 m-Fluorotyrosine < 1 x 10

H 6 - p.r. D.k. in N20-satd. 0.04 M 73-1067 ~ 1.2 x 10" 11 Br" soln.; values from

graph. 7.43 Formate ion < Iff* 7 p.r. D.k. in N20-satd. 1 M

Br" soln. 78-1093

7.44 d-Guanylic acid 4 x 10

7 - - p.r. - 74-1168,

Br2

" + GMP 2 x 10

H 12 74-1181

2Br" 4- GMP- + 7.45 Histidine (1.5 ± 0.2) x 10' 7.6 0.1 p.r. D.k. in N2 0-satd. Br"

soln. 72-0036

7.46 Hydroquinone 1 x 10* - - p.r. - 74-1168

7.47 />-Hydroxybenzoate ion 2.28 x 10* 12.5 - p.r. - 74-3052

7.48 Lactate dehydro- (5.5 ± 0.5) x 10" 7.2 0.005 p.r. D.k. in N20-satd. Br" 77-1132

genase soln. 7.49 Methionine (1.1 ± 0.1) x 10' 7.3 0.1 p.r. D.k. in N2 0-satd. Br"

soln.; k increases with pH.

72-0036

7.50 /j-Methylphenoxide ion 3.74 x 10* 12.5 - p.r. - 74-3052

7.51 Nicotinamide-adenine 9.0 x 10* - - p.r. P.b.k. at — 400 nm in 71-0158

dinucleotide, reduced

Br,‘ + NADH —

N20-satd. 0.1 M Br" soln.

2Br" + H

+ + NAD7.52 Papain 1.05 x 10" 7 - p.r. D.k. in 0.05 M Br’ soln.; 74-1026

2.30 x 10" 11.5 activated enzyme used.

40
TABLE 7. Rates of reaction of Br2 in aqueous solution—Continued

No. Reaction k(M~' s'

1 ) pH I Method Comment Ref.

7.53 Phenol 6 x 10" 6 _ p.r. 74-3003

7.54 Phenoxide ion 5 x 10

8 2.88 x 10

8 10

12.5 - p.r.

p.r.

- 74-3003

74-3052

7.55 Phenylalanine < 1 x 10

6 7.0 0.1 p.r. D.k. in N20-satd. Br"

soln. 72-0036

7.56 Promethazine 4 x 10

9 - r

4 p.r. - 74-1168

7.57 Pyrene (triplet state) Rr2

- +

3 Py —

2Br~ + Py

+

1 x 10

9 p.r. D.k. at 414 nm (*Py) or 360 nm (Br2

~) or p.b.k.

at 448 nm (Py +

) in 0.02 M

Br" contg. 10"2 M

hexadecyltrimethyl

ammonium bromide; triplet state formed by f.phot.

76-1181

7.58 Ribonuclease 4.6 x 10

9 4.5 - p.r. D.k. in 10

2 M Br" soln. 72-0037

7.59 Subtilisin

(serine protease)

1 x 10

9 7 p.r. D.k. in N20-satd. 0.04 M

Br" soln.; k increases with pH in alk. soln.

73-1147,

74-1119

7.60 Superoxide dismutase (0.44 ± 0.03) x 10

9 <10 — p.r. Bovine enzyme; k =

(1.18 ± 0.04) x 10

9 for 73-1148,

74-3081

human enzyme; k

decreases at higher pH.

7.61 Tetramethylpiperidone 1.6 x 10

9 5-6 - p.r. D.k. at 380 nm. 71-0618

yV-oxyl (TAN)

7.62 Thymine < 1 x 10

7 - - p.r. - 74-1168

2 x 10

8 12

7.63 Trypsin (2.55 ± 0.3) x 10

9 7.0- - p.r. D.k. in N20-satd. 0.04 73-1067

8.0 3/BU.

(5.30 ± 0.5) x 10

9 11.5 7.64 Tryptophan (7.7 ± 0.8) x 10

8 7.0 0.1 p.r. D.k. in N20-satd. Br" 72-0036

soln. 7.65 Tyrosine (2.0 ± 0.2) x 10

7 7.5 0.1 p.r. D.k. in N2 0-satd. Br" 72-0036

Br2

" + HOC6H4CH2 CHNH2COOH -* soln.; k increases with pH.

2Br~ + H

+ + < 1 x 10' 6 - p.r. D.k. in N20-satd. 0.04 73-1067

•OC6H4CH2CHNH2 COOH ~ 1.4 x 10

9 12 M Br" soln.; values from

graph. 5 x 10

8 12 - p.r. - 74-1168

7.66 Uracil < 1 x 10' - p.r. - 74-1168

2 x 10

8 12

41
Table 8. Rates of reaction of I 2 in aqueous solution

No. Reaction k(Af' s'

1 ) pH I Method Comment Ref.

8.1 I2

~ + I 2

' — 2k = (7.7 ± 1.5) x

10'' 1.4- _ f.phot. D.k. at 404.7 nm in 57-7007

V + I 6 3 x 10"5 to 10' ' M Y

soln.; €(404.7 nm) =

11,700 AT' cm'

1 . 2k = (1.17 ± 0.2) x 10'" 6.0 - f.phot. D.k. at 385 nm in 67-7171

(8.7 ± 0.5) x 10" 1.1 N20-satd. 10'* M Y

(6.7 ± 0.6) x 10" 6.5 soln., or Hgl j2

" soln. (10"4 M Hgl 2 +

10"2 M I ); €(385 nm) =

1.4 x 10

4 AT' cm '.

2Jc = (9.0 ± 2.0) x 10" alk. p.r. Computer analysis of

abs. at 335 and 390 nm

in N20-satd. 1" soln.; €(390 nm) = 15,600 cm'

1 ; €(335 nm) =

8200 M~' cm"

1 .

76-1105

8.2 1/ — I + T k, = 6 x 10

4 s'1 p.r. tT' = 1.13 x 10

s Af';

k r = 7.6 x 10" AT' s

' 1

detd. by effect of

[I ] on [I/].

68-0375

k( = 1.7 x 10

f> s"‘

k, = (9 ± 1) x 10

s s'1

f.phot. D.k. at 385 nm in Hgl 2-F soln. 74-7224

- - f.phot. Detd. in I soln. 74-7554

8.3 I 2

~ + Co

2+ - - f.phot. no reaction 73-7316

8.4 I 2

' + CoL

2+ — (7.2 ± 0.8) x 10" 2 0.03 f.phot. D.k.; 1 2

~ from ion 72-7506

CoLI2 + pair Co(NH ,)((

' +

, I'. L = 5,7,7,12,14,14—hexamethyl-1,4,8,1 l-tetraazacyclotetradeca-4,1

1

-diene

8.5 V + Co(NH:t)s

I 2+

( + H

+

) — ~ 2.5 x 10

4 _ - f.phot. Estd. from intensity 72-7506

1," + Co

2+

4- 5NH4 + dependence of 9>(Co ). 8.6 W + Cr„,2+ — (1.5 ± 0.2) x 10" 1 0.2 p.r. D.k.; AG° = -138 kj 74-1104

(Cr(OH2),I]2+ + r mol '; inner sphere

diffusion control. 8.7 I 2

* -f Fe^2+ 3.6 x 10" - - - AG° = -22 kj mol '; 74-1104

Fel

2+

4- I- unpub. work cited; inner sphere

substitution. 8.8 I 2

‘ 4- 10" — (5.0 ± 0.6) x 10

7 13.6 - f.phot. D.k. in (1-3) x 10 M 70-0018

10 4- 2F IO" and I soln. 8.9 I 2

' + IOH-> (1.8 ± 0.8) x 10"’ alk - p.r. Computer anal, of abs. at 76-1105

I,' + OH' 335 nm and 390 nm in N2 0-

satd. I" soln. 8.10 I 2

‘

-»- V

2+ ^ (1.43 ± 0.2) x 10

8 1 0.2 p.r. D.k.; AG° = -116 kj 74-1104

21" + V

4+ mol'

1 ; outer sphere. 8.11 Acriflavin < 2 x 10

H p.r. Decay of I 2

" only

slightly increased in presence of dye.

70-0241

8.12 Alcohol dehydrogenase — 1.2 x 10* - - p.r. Est. from d.k. in 73-1065

(yeast) N20-satd. F soln.

42
Tablf 8. Rates of reaction of I 2 in aqueous solution—Continued

No. Reaction k(Af' s'

1 ) pH I Method Comment Ref.

8.13 Aldolase

(rabbit muscle) ~ 3 x 10" - p.r. Est. from d.k. in N2 0-satd. L soln. 73-1065

8.14 Ascorbate ion (1.4 ± 0.3) x 10

8 7 - p.r. - 72-0266

8.15 Ascorbic acid 5 x 10" 2 - p.r. - 72-0266

8.16 />-Bromophenoxide ion 5.0 x 10

7 12.5 - p.r. At pH 7 k sb 5 x 10". 74-3052

8.17 //-Chlorophenoxide ion 5.8 x 10' 12.5 - p.r. 74-3052

8.18 Cysteine (1.1 ± 0.1) x 10

8 6.8 0.1 p.r. D.k. in N2 0-satd. I” soln.; k increases with pH.

72-0036

8.19 Dithiothreitol (1.9 ± 0.2) x 10

7 7 - p.r. D.k. 73-1020

8.20 Histidine < 1 x 10" 7.0 0.1 p.r. D.k. in N2 0-satd. I” soln. 72-0036

8.21 Lactate dehydrogenase

(4.3 ± 0.5) x 10

<J 7.2 0.005 p.r. D.k. at N20-satd. I~ soln. 77-1132

8.22 Methionine < 1 x 10" 7.0 0.1 p.r. D.k. at N20-satd. I” soln. 72-0036

8.23 /?-Methylphenoxide ion 9.8 x 10

7 12.5 - p.r. - 74-3052

8.24 Nicotinamide-adenine

dinucleotide, reduced

I2" + NADH -*

21” + NAD- + H

+

~ 5 x 10' 0.1 p.r. D.k. at 370 nm in N2 0-satd. I” soln. 71-0158

8.25 Phenoxide ion 5.7 x 10

7 12.5 - p.r. - 74-3052

8.26 Phenylalanine < 1 x 10* 7.0 0.1 p.r. D.k. in N20-satd. I” soln. 72-0036

8.27 Tetramethylpiperidone

A’-oxyl (TAN)

1.7 x 10

y 5-6 - p.r. D.k. at 390 nm; final product may be I.,”. 71-0618

8.28 Trypsin (1 to 6) x 10

8 11-12 p.r. D.k. in N2 0-satd. 0.04 M I” soln.; values from

graph.

73-1067

8.29 Tryptophan < 1 x 10

6 7.0 0.1 p.r. D.k. in N2 0-satd. I” soln.; k increases with pH.

72-0036

8.30 Tyrosine < 1 x 10" 7.0 0.1 p.r. D.k. in N20-satd. I” soln. 72-0036

43
TaBLF. 9. Rates of reaction of (SCN)2 in aqueous solution

No. Reaction k(Af' s'') pH

9.1 2(SCN)/ —

(SCN), + 2SCN'

2k = 2.9 x 10" 7

2k s 3 x 10* -

2k = (2.4 ± 0.4) x 10

9 ~5.7

2k = (2.5 ± 0.2) x

10'' -

9.1a (SCN)2-^

SCN + SCN'

k( = 3.4 x 10* s'

1 -

kf s 3 x 10* s’

1 1,6

9.2 (scn)2

- + r —

ISCN' + SCN'

1.6 x 10

9 -

9.3 (SCN)2

" + NiL2+ -*

Nim

(1.0 ± 0.4) x 10

9 2

L = 5,7,7,12,14,14—hexamethyl-l,4,8,ll-tetraazacyclotetradecane

9.4 (SCN)2

" + U02 + —

2SCN" + U022+

(1.46 ± 0.34) x 10

9 1.0

9.5 Alcohol dehydrogenase

(yeast)

9.6 x 10

8 7

9.6 Aldolase < 5 x 10' 7

9.7 D-Amino acid oxidase 6.6 x 10

8 -

9.8 Ascorbic acid (SCN)2

‘ + AH2 -*•

(1.0 ± 0.5) x 10

7 1.8

H

+ + 2SCN' + -AH < 1.0 x 10

7 -

(SCN)2 + AH' —

H

+

4- 2SCN' + A-'

(6.0 ± 1) x 10

8

(4.8 ± 0.8) x 10

8

7

6.7

9.9 />-Bromophenoxide ion OJ © X

'o

X 12.5 9.10 Carboxypeptidase A (4 to 12) x 10

B 8-11

9.11 p-Chlorophenoxide ion 3.40 x 10

8 12.5 9.12 a-Chymotrypsin 9 x 10

8 6.7

9.13 />-Cyanophenoxide ion 6.3 x 10

7 12.5 9.14 Cvsteamine 8 x 10

7 -

9.15 Cysteine (5 ± 0.5) x 10

7 6.6

9.16 3,4—Dihydroxyphenylalanine 3 x 10

7 -

9.17 Dithiothreitol (2.1 ± 0.2) x 10

7 7

I Method Comment Ref.

0.01 p.r. D.k. in presence or absence of 02

; £(500

nm) = 7100 M cm"

1 .

65-0386

-+0 p.r. Second order decay in N20-satd. CNS' soln.; value from graph; £ =

7600 AT

1 cm'

1 .

68-0375

0 p.r. D.k. in 02 -satd. soln. of < 0.5 M CNS'; £ not

given.

72-0475

0.005 p.r. Addn. of Cl increases k to 3.3 x 1 O' at 5 M LiCl. 75-1119

p.r. = 2 x 10

s M. k, =

7.0 x 10

9 AT' s'

1 detd. by effect of [SCN J on

[(SCN)2

-].

68-0375

f.phot. First-order decay in N2 or N2 0-satd. 2.5 x 10

’

to 2 x 10~ + M CNS' soln.; second order in presence

of 02 with 2k/

e

= 2.0 x 10

f

’.

68-7072

0.005 p.r. D.k. in N2 0-satd. CNS'

soln. 70-0164

-0.02 p.r. D.k. in 0.005-0.01 M SCN~

soln. 78-1502

- f.phot. D.k. in CNS' - U(VI) soln.; reaction probably reoxid. of U(V) to U(VI); assume

[(SCN)2

'1 = (U02 +

J.

76-7279

p.r. D.k.; k = 5.6 x 10

8 in horse liver enzyme (78-3007).

74-1125

0.1 p.r. D.k. in SCN~ soln.; value from graph; k increases with pH.75-3058

p.r. D.k. in N20-satd. 0.05 M

SCN soln.; mol. wt. 50,000.

77-1198

- p.r. P.b.k. at 380 nm in 0.1 M SCN" soln. 72-0266

- p.r. D.k. in N20-satd. 10' 2 M

SCN" soln. 73-3006

0.1 p.r. D.k. in SCN’ soln., as

well as p.b.k. at 360 nm. 72-0266

0.01 p.r. D.k. in N2 0-satd. 10

2 M

SCN" soln. 73-3006

- p.r. - 74-3052 - p.r. D.k.; values from graph. 73-1060 - p.r. - 74-3052

0.04 p.r. D.k. in N20-satd. SCN"

soln. 74-1096

- p.r. - 74-3052 - p.r. - 74-1168

0.1 p.r. D.k. in N20-satd. SCN’

soln.; k increases with pH.

72-0036

- p.r. - 74-1168

0.1 p.r. D.k. in SCN' soln. 73-1020

44
Table 9. Rates of reaction of (SCN)2 in aqueous solution—Continued

No. Reaction k(Af' s'') pH I Method Comment Ref.

9.18 Formate ion < 2 x 10

3 7 ~1 p.r. D.k. in N20-satd. 1 M 78-1093 SCN' soln. 9.19 Histidine < 1 x 10“ 7.0 0.1 p.r. D.k. in N2 0-satd. SCN" 72-0036

soln. 9.20 Hydroquinone 6 x 10

7 - - p.r. - 74-1168

9.21 /j-Hydroxybenzoate ion 2.65 x 10

H 12.5 - p.r. - 74-3052

9.22 Lactate dehydrogenase 1.5 x 10° 7.2 0.005 p.r. D.k. in N20-satd. SCN" 77-1132

soln. 9.23 Lysozyme 6.6 x 10

8

• 1 0.1 p.r. D.k. in N20-satd. SCN" 69-3039,

soln. 70-0967

9.24 Methionine (2 ± 0.2) x 10“ 7.0 0.1 p.r. D.k. in N2 0-satd. SCN" 72-0036

soln.; k increases with pH.

9.25 /?-Methylphenoxide ion 5.52 x 10

8 12.5 - p.r. At pH 7 k s 10

7

. 74-3052

9.26 Nicotinamide-adenine 4.7 x 10

8

1

0.1 p.r. D.k. in N2 0-satd. SCN' 71-0158

dinucleotide, reduced soln. (SCN)2

‘ + NADH -

2SCN' + NADH+

9.27 /i-Nitrophenoxide ion 3.9 x 10' 12.5 - p.r. - 74-3052

9.28 Papain 9.5 x 10° 7 - p.r. D.k.; activated enzyme 74-1026

1.75 x 10“ 11.5 used. 9.29 Phenol < 1 x 10

7 - - p.r. - 74-1168

9.30 Phenoxide ion 3 x 10

8 12 - p.r. - 74-1168

3.42 x 10

8 12.5 - p.r. - 74-3052

9.31 Phenylalanine < 1 x 10“ 7.0 0.1 p.r. D.k. in N20-satd. SCN' 72-0036

soln. 9.32 Promethazine 2 x 10“ - - p.r. - 74-1168

9.33 Ribonuclease 3.4 x 10' 7 0.05 p.r. D.k. in N2 0-satd. SCN" 72-0037

soln.; k increases at pH > 9.5. 9.34 Serum albumin 1 x 10

; (bovine) 6.0 0.01 p.r. D.k. in SCN" soln.; also 76-1185

5 x 10

8 (human) 6.5 detd. reactivity with

alkyl sulfate complexes. 9.35 Subtilisin 1 x 10

8 7 - p.r. D.k. in N.,0-satd. 0.04 M 73-1147,

(serine protease) SCN" soln.; k increases 74-1119

with pH in alk. soln. 9.36 Tetramethyl- 1.1 x 10“ 2 0.1 p.r. D.k. in 0.1 MCNS' soln. 71-0618

piperidone-iV-oxyl (TAN) 1.0 x 10

’ 5-6

1.1 x 10 12

9.37 Thymine < 1 x 10“ 6 - p.r. - 74-1168

3 x 10

7 12

9.38 Trypsin (5.1 ± 0.5) x 10

8 7-8 0.04 p.r. D.k. in N20-satd. SCN" 73-1067

(3.06 ± 0.3) x 10“ 11.5 soln. 9.39 Trypsinogen (2.6 ± 0.3) x 10

8 7-8 - p.r. - 73-1067

(3.6 ± 0.4) x 10“ 12.1 9.40 Tryptophan 3 x 10

8 7 - p.r. - 69-3039

(SCN)2" + TrpH -* (2.7 ± 0.3) x 10

8 7.0 0.1 p.r. D.k. in N20~satd. SCN" 72-0036

2SCN" + Trp- + H

+

soln.; k increases with pH.

(pA of TrpH" = 4.3, 4.6 x 10

8 11.2 - p.r. - 73-1147

ref. 76-1151)

9.41 Tyrosine (5 ± 0.5) x 10“ 7.0 0.1 p.r. D.k. in N.,0-satd. SCN" 72-0036

soln.; k increases with pH.

3.2 x 10

8 11.2 B p.r. - 73-1147

45
.
Formula Index

As02

" Arsenite ion, 2.2 Br Bromine atom, 7.2 Br~ Bromide ion, 1.2a, 2.3, 54—5.5

BrCoH|-N52+ Bromopentaamminecobalt(III) ion, 1.7e BrO Hvpobromite ion, 1.3, 7.5 Br02

' Bromite ion, 1.4, 7.6 BrO,' Bromate ion, 7.7 Br2

’ Bromine molecule anion, table 7 CC14 Carbon tetrachloride, 1.36 CCoH,2 N4 0,

+ Carbonatopentaamminecobalt(III) ion, 1.6 CH02

' Formate ion, 1.51, 2.67, 5.51, 6.63, 7.43, 9.18 CHO . Bicarbonate ion, 2.4 CH,N02’ aci-Nitromethane, 1.77 CH20., Formic acid, 2.68, 4.12, 6.64 CH,N02 Nitromethane, 1.76 CH4N20 Urea. 1.100 CH40 Methanol, 1.69, 2.78, 4.14, 5.62, 6.77 CN Cyanide ion, 2.5 CNO~ Cyanate ion, 2.6 CNS’ Thiocyanate ion, 1.13d, 2.7, 6.3, 7.24 CO , Carbonate radical ion, table 1 C2C1,0., Trichloroacetate ion, 1.91 C2 H2C102

~ Chloroacetate ion, 1.37 C2 H,N Acetonitrile, 1.18

C.,H ( 02 Acetate ion, 1.16, 2.32, 5.31 C2H402 Acetic acid, 2.33, 4.8, 5.32, 6.32 C2 Hs N02 Glycine, 1.55, 2.70, 5.54, 6.68 C2 H(i O Ethanol, 1.49, 2.65, 3.5, 3.11, 4.10, 5.50, 6.62 C2 H,,02 Ethyleneglycol, 4.11 C2 Hfl S., Dimethyl disulfide, 1.45, 2.64, 7.41

C.,H7 NS Cysteamine, 7.36, 9.14 C,H I8CoN-02

' + Acetatopentaamminecobalt(III) ion, 1.7h C2 N2S2' Bisthiocyanate radical ion, table 9 C3 H2 04

2~ Malonate ion, 2.75 C,H;{ N Acrylonitrile, 2.38, 5.36, 6.37 Ct H;i O., Acrylate ion, 2.37, 6.35 C,H4N2 Imidazole, 1.64 C,H402 Acrylic acid, 5.35, 6.36 C,H404 Malonic acid, 5.58 CjH-NO Acrylamide, 2.36, 5.34 C( H-02 Propionate ion, 2.94 C t H-02S~ 3-Mercaptopropionate ion, 1.68 CjHfi O Acetone, 1.17, 5.33, 6.33; Allyl alcohol, 2.40,

5.38, 6.40 C,Hf) 02 Propionic acid, 5.66, 6.88 C,H7 N02 Alanine, 1.24, 2.39, 5.37, 6.39

C.,H: N02S Cysteine, 1.40, 6.54, 7.37, 8.18, 9.15 C;( H7NO( Serine, 2.99, 6.90 C t H80 1-Propanol, 1.85, 2.92; 2-Propanol, 1.86, 2.93,

3.6, 4.15, 5.65, 6.87 ChH803 Glycerol, 4.13 C4H,04

2' Fumarate ion, 2.69, 6.65; Maleate ion, 6.76 C4H s C1N202 5-Chlorouracil, 6.51 C4H4N202 Uracil, 1.99, 5.73, 6.100, 7.66 C4H404 Fumaric acid, 5.52, 6.66; Maleic acid, 5.57 C4H404

2

' Succinate ion, 2.100 C.H-N Allyl cyanide, 2.41, 5.39; Methacrylonitrile, 2.77, 5.61 C4H-N ,0 Cytosine, 6.56 CjH-02

’ Crotonate ion, 5.45; Methacrylate ion, 5.59 C4H9N04

~ Aspartate ion, 1.32 C4Hfi N202 Dihydrouracil, 5.49

C4Hr> 02 Crotonic acid, 2.51, 5.46; Methacrylic acid, 2.76,

5.60; Vinyl acetate, 2.116 C4H604 Succinic acid, 5.68, 6.92 C4H7 NO, A

r-Acetylglycine, 1.21 C4HkN2 0, Glycylglycine, 1.56 C4H8N2 04Pt cw-Bis(glycinato)platinum(II), 1.11;

fra/w-Bis(glycinato)platinum(II), 1.12 C4H80 Tetrahydrofuran, 2.101a C4H802 Dioxane, 2.64a C4H9N02S Cysteine methyl ester (Methyl 2-amino-3-

mercaptopropionate), 1.41; 5-Methylcysteine, 1.72 C4H1() 0 2-Methyl-2-propanol (tert-Butanol), 1.74, 2.85,

5.64, 6.81 C4H hi02S2 Dithiothreitol (tAreo-2,3-Dihydroxy-l,4—

dithiobutane), 1.47, 6.60, 8.19, 9.17 C4HioS2 Diethyl disulfide, 1.43, 2.55, 7.39 C4H| 2 N4Pt

2+ Bisethylenediamineplatinum(II) ion, 6.25 C4H l;j ClN,Pt

+

Chlorodiethylenetriamineplatinum(II) ion, 6.26 C5H5N Pyridine, 2.95 CSHSNS Adenine, 6.38 C5H-N-0 Guanine, 6.69 C5Hf) N

+ Pyridinium ion, 2.96 C-Hf) N2 02 Thymine, 1.89, 5.71, 6.96, 7.62, 9.37 C-H802 Methyl methacrylate, 2.84, 5.63 C5 HyNO;) S A-Acetylcysteine, 1.20 CsH9N04 Glutamic acid, 6.67 C5H9Os Deoxyribose, 5.48 C5Hl0O2 Ribose, 5.67 C5Hn N02 S Methionine, 1.70, 2.79, 6.78, 7.49, 8.22, 9.24; Penicillamine (2-amino-3-methyl-3-thiobutyric acid), 1.80 C5H 120 3-Pentanol, 2.87

Cf.FeNf,

4- Hexacyanoferrate(II) ion, 1.9, 4.17 C6H4BrO’ /?-Bromophenoxide ion, 1.35, 7.31, 8.16, 9.9 C6H4C10’ /?-Chlorophenoxide ion, 1.38, 7.33, 8.17, 9.11 Cf^NO^’/j-Nitrophenoxide ion, 1.78, 9.27 Cf) H404

2

' Muconate ion (2,4—Hexadienedioate ion), 6.82 Cf) H50~ Phenoxide ion, 1.82, 5.64a, 7.54, 8.25, 9.30

Cf.H^O jS' Benzenesulfonate ion, 6.46 Cf) Hf) Benzene, 1.33, 2.44 C() H() 0 Phenol, 1.81, 6.83, 7.53, 9.29 Cfl Hfl 02 Hydroquinone, 6.73, 7.46, 9.20

Hexenedioate ion, 6.71 C9H7 N Aniline, 1.25 C() H7 02

’ Sorbate ion (2,4-Hexadienoate ion), 6.91 C6H7 06

~ Ascorbate ion, 1.31, 7.30, 8.14, 9.8 C6H8 N

+ Anilinium ion, 6.43 Cf) H804

S.,

2' 3,3'-Dithiobis(propionate ion), 1.46 C9H8Ofl Ascorbic acid, 6.45, 7.30, 8.15, 9.8 C6H9N2 04 A-Acetylglycylglvcine, 1.22 Cf) HvN402 Histidine, 1.62, 2.71, 6.72, 7.45, 8.20, 9.19 C6H m> Cvclohexene, 2.54 C0Hn N304 Glycylglycylglycine, 1.57 Cfl H l206 Glucose, 1.52, 5.53 Cf) H 14N402 Arginine, 1.30 Cf,H24CoNf>3 ^ Trisethylenediaminecobalt(IlI) ion, 1.7b C7 H4Br02

’ o-Bromobenzoate ion, 2.48; />-Bromobenzoate ion, 2.49, 6.49 C-H4C102' p-Chlorobenzoate ion, 2.50, 5.43, 6.50 C7 H tNO" /j-Cyanophenoxide ion, 5.47a, 7.35, 9.13 C-H-C102 ^-Chlorobenzoic acid, 5.44 47
QH-N Benzonitrile, 2.46, 6.48 C-H-NO />-Cyanophenol, 6.53

CjHjjO," Benzoate ion, 2.45, 5.41, 6.47 C7 H-0, />-Hydroxybenzoate ion, 1.63, 2.73, 5.55, 6.74,

7.47, 9.21 C-H, N02 />-Aminobenzoate ion, 6.41 C: H„02 Benzoic acid, 5.42 C: H,,O t ^-Hydroxybenzoic acid, 6.75; Salicylic acid, 6.89 C7 H7 NO Benzamide, 2.43 C7 H7 NO, />-Aminobenzoic acid, 5.40, 6.42 C7 H 7 0' /?-Methylphenoxide ion, 1.73, 5.62a, 7.50, 8.23, 9.25 C7 H7 02

’ />-Methoxyphenoxide ion, 1.71 C-H8 Toluene, 1.90 C7 HbO Anisole, 1.25a, 2.42; />-Methylphenol, 6.80

C-H.jN A^-Methylaniline, 1.71b C7 H l40 Cycloheptanol, 2.53 C7 H20CoNsO22+ Benzoatopentaamminecobalt(lll) ion, 1.7g

C8 H 4 NO," /J-Cyanobenzoate ion, 2.52, 5.47, 6.52 QH404

' Terephthalate ion, 2.101, 5.69, 6.93 Ca H(> 04 Terephthalic acid, 5.70 Ch H: N Indole, 1.65 C8 H7 02 o-Toluate ion, 2.102; /n-Toluate ion, 2.103;

/>-Toluate ion, 2.104, 6.97

0,11-0," 2-Methoxybenzoate ion, 2.80; 3-Methoxybenzoate

ion, 2.81; 4-Methoxybenzoate ion, 2.82, 6.79 C„HhO Acetophenone, 1.19, 2.34 C„H802 Toluic acid, 5.72 QH.jNO Acetanilide, 1.15, 2.31, 6.31

/)-Nitroso-AvY-dimethylani)ine, 2.86 OjHl.O Benzyl methyl ether, 2.47; Ethoxybenzene, 1.50; 1-Phenylethanol, 2.89 C^H |,,02 1,2-Dimethoxybenzene, 2.56; 1,3-Dimethoxybenzene,

2.57; 1,4-Dimethoxybenzene, 2.58 QHnN jV,A-Dimethylaniline, 1.44 QH | 2 N02 Norpseudopelletierine-A-oxyl

(9-Azabicydo[3,3,l]nonan-3-one-9-oxyl), 1.79 C^H^^O, Glycylhistidine, 1.59 G,H,04

" 2,3-Dimethoxybenzoate ion, 2.59;

2.4-

Dimethoxvbenzoate ion, 2.60; 3,4-Dimethoxybenzoate ion, 2.61; 2,6-Dimethoxybenzoate ion, 2.62;

3.5-

Dirnethoxybenzoate ion, 2.63 G,H,Ofl

* Tnmesate ion, 2.105 G,H60j2" Homophthalate ion, 2.72 G,Ht O," />-Acetylbenzoate ion, 2.35

GjH.jIjNO, 3,5-Diiodotyrosine, 7.40 G,H h) FNO, m-Fluorotyrosine, 7.42 G,H m N02 Phenylalanine, 1.83, 6.85, 7.55, 8.26, 9.31 G,H n NO, Tyrosine, 1.98, 2.115, 6.99, 7.65, 8.30, 9.41 G,H n N04 3,4-Dihydroxyphenylalanine, 9.16 G H i20 1-Pheny 1-2-propanol, 2.90; 2-Phenvl-2-propanol,

2.91 G,H l20, 1,2,3-Trimethoxybenzene, 2.106;

1.2.4-

Tnmethoxybenzene, 2.107;

1.3.5-

Tnmethoxybenzene, 2.108 G,H l3 N.O- Cytidine. 6.55 G,H I4 N Trimethylaniiinium ion, 2.113 G,H I4 N,Ot P Deoxycytidylic acid, 6.58 G,H |() N02 2,2,6,6-TetramethyI-4-oxo-l-piperidinyloxyl

(TAN), 1.88, 6.94, 7.61, 8.27, 9.36 C)nH2Ol

. L

" Pyromellitate ion, 2.97 ClnH|„Fe + Ferricinium ion, 7.16

Cl( )H,,Os " 3.4.5-2,3,4—Trimethoxybenzoate ion, 2.109; 2.4.5-Trimethoxybenzoate ion, 2.110; Trimethoxybenzoate ion, 2.111;

2.4.

6-

Trimethoxybenzoate ion, 2.112

C|„H, 2 N2 Tryptamine, 1.93 C|„H i 2 N208

’ Ethylenediaminetetraacetate ion, 1.50a C|„H l2 02 Duroquinone, 1.48 C|„H, 4N50(i P Deoxyadenylic acid, 6.57 Cl(l H l4 N-07 P Deoxyguanylic acid, 6.59 C I(i H I 4N508 P Guanylic acid, 7.44 C 10H I40 l-(p-Ethylphenyl)ethanol, 2.66; l-Phenyl-3-

butanol, 2.88 C|„H l6N2OyP Thymidylic acid, 6.95

C| 0H i 7 N,06S Glutathione, 1.53 Cm H I() N02 Indole-3-propionate ion. 1.66 C,,H l2 N202 Tryptophan, 1.94, 2.114, 3.16, 6.98, 7.64, 8.29, 9.40 CnHuN.O Tryptophanamide, 1.96 Cn

H| 4 N2 0, Phenyialanylglycine, 1.84

C, ,H, 4N2 04 Glycyltyrosine, 1.61 Cn

H|,,0 l-Methoxy-2-methyl-l-phenylpropane, 2.83 CI2 H l4N2 02 A^-Methyltryptophan, 1.75; Tryptophan methyl

ester (Methyl 2-amino-3-indolylpropionate), 1.95

C, 2 H25 Na04S Dodecyl sodium sulfate, 6.61

C| 2 H2 ,,ClN,Pt

+ Chlorotetraethyldiethylenetriamineplati- num(II) ion, 6.27

C| ( H40, /?-Phenoxybenzoate ion, 6.84

C| 3 HioO Benzophenone, 1.34 C) t H l4N2 0, AGAcetyltryptophan, 1.23

C|.,H l5N;,0, Glycyltryptophan, 1.60; Tryptophanylglycine,

1.97 C14 H() 08S2

' Anthrasemiquinone-2,6-disulfonate radical

ion, 1.28, 4.9, 6.44; Anthrasemiquinone-2,7-

disulfonate radical ion, 1.29 Cl4 H7 05S" Anthrasemiquinone-l-sulfonate radical ion, 1.26; Anthrasemiquinone-2-sulfonate radical ion, 1.27 C14 H 14CIN;, Acriflavin, 6.34, 7.28, 8.11 C|-H l8 N4 0. Glycylglycyltryptophan, 1.58 CUl H l(l Pyrene (triplet state), 7.57 Ck

,H28CoN42+

5,7,7, 12, 14, 14-Hexamethyl-l,4,8, 11-

tetraazacyclotetradeca-l,4,8,ll-tetraene cobalt(II)

ion, 1.5a C1(,H 28 N4Ni

2+

5,7,7, 12, 14, 14-Hexamethyl-l,4,8, 11-

tetraazacyclotetradeca-1,4,8,1 l-tetraenenickel(II)

ion, 6.21, 7.21 C l(l H;)2 CoN42+

5, 7, 7, 12, 14, 14-Hexamethyl-l,4,8, 11-

tetraazacyclotetradeca-4,1 l-dienecobalt(II) ion, 1.5b, 6.7, 7.11, 8.4 Clf,H t2 CuN42+

5,7,7, 12, 14, 14-Hexamethyl-l ,4,8,1 1-

tetraazacyclotetradeca-4,1 l-dienecopper(II) ion, 6.11 C„,H;)2 N4Ni

2+

5,7,7,12, 14. 1 4-Hexamethyl-l,4,8,l 1 -

tetraazacyclotetradeca-4,1 l-dienenickel(Il) ion, 6.20. 7.20

C| 6HViCuN42+5,7,7,12, 14,14-Hexamethyl-l,4,8,lltetraazacyclotetradecanecopper(II) ion, 6.10 CK(H 8lN4Ni

2+

5,7, 7, 12, 14, 14-Hexamethyl-l,4,8, 1 1-

tetraazacyclotetradecanenickel(H) ion, 6.19, 7.19, 9.3 CI7 H20N2S Promethazine, 7.56, 9.32

48
C| H H| f) N,0+S2 Cystine dimethyl ester (Dimethyl

3,3'-dithiobis(2-aminopropionate)), 1 .42

C| 9H42C1N Hexadecyltrimethylammonium chloride, 6.70 C20H32 N() Ol2 S2 Glutathione disulfide, 1.54 C2 |H2() N7 O, 0P2 Nicotinamide-adenine dinucleotide, reduced,

7.51, 8.24, 9.26 CwH24N6Ru2+ Tris(2,2'-bipyridine)ruthenium(II) ion, 1.13, 7.23 Ce

+ Cerium(III) ion, 2.8, 4.3, 6.4

Cl’ Chloride ion, 2.9, 4.4, 5.6-5.

C1CoH| 5 N52+ Chloropentaamminecobalt(III) ion, 1.7d ClCrH|-N s2+ Chloropentaamminechromium(III) ion, 1.8a ClH| 5 IrN5 2+ Chloropentaammineiridium(III) ion, 1,10a

ClH )5N5Rh2+ Chloropentaamminerhodium(III) ion, 1.12a C1H, 5N-Ru

2+ Chloropentaammineruthenium(III) ion, 1.13b C102 Chlorine dioxide, 6.5, 7.8

Cl2

" Chlorine molecule anion, table 6

Cl4Pt

2’ Tetrachloroplatinate(II) ion, 6.24, 7.22 Co

+

Cobalt(I) ion, 7.9 Co

2+

Cobalt(II) ion, 1.5, 6.6, 7.10, 8.3 CoH, 5INr) 2+ Iodopentaamminecobalt(III) ion, 8.5 CoH 15N50,S+

Sulfitopentaamminecobalt(III) ion, 1.7j CoH,-N504S

+ Sulfatopentaamminecobalt(III) ion, 1.7f CoH )5N(i 022+ Nitritopentaamminecobalt(III) ion, 1.7i CoH 16N402

* + Diaquotetraamminecobalt(III) ion, 1.7 CoH, () N504P

+ Phosphatopentaamminecobalt(III) ion, 1.7c CoH,„Nf> 1+ Hexaamminecobalt(III) ion, 1.7a Cr

2+ Chromium(II) ion, 2.10, 6.8, 7.12, 8.6 CrH| 7 N50

,+ Aquopentaamminechromium(III) ion, 1.8b Cu

2+

1.8c, 6.9 Fe

2+

Iron(II) ion, 2.11, 4.5, 6.12, 7.15, 8.7 H Hydrogen atom, 7.3 HIO" 8.9 HNO f

4.21 HO" Hydroxide ion, 2.19, 5.16, 6.22 H02 Hydroperoxy radical, 6.2, 7.4 H03P

2~ 2.23, 5.19-5.20 H03S~ Hydrogen sulfite ion, 5.28 HO,Se 3.14 H04P" Phosphate radical ion, table 5 H04P

2" 2.26 HO-P2" 5.25 HOsS" Hydrogen peroxysulfate ion, 2.28 H20 Water, 2.20, 4.19, 4.20, 4.24, 4.25 H202 Hydrogen peroxide, 1.9a, 2.21, 5.17-5.18, 6.23, 7.17 H202 P Hypophosphite ion, 2.22, 5.22-5.24 H2 03 P~ Phosphite ion, 2.24, 5.21

H203Se 3.15 H2 04P Phosphate radical, table 5 H204P Phosphate ion, 2.25, 4.23 H ( NO Hydroxylamine, 2.12, 5.13, 6.15 H4N0 Hydroxylammonium ion, 2.13, 5.14, 6.16 H4N2 Hydrazine, 2.14, 5.09 H5 N2 t Hydrazinium ion, 2.15, 5.10-5.11, 6.14 H^N^Rh' Aquopentaamminerhodium(III) ion, 1.12b H, 7 N-ORu + Aquopentaammineruthenium(III) ion, 1.13c H, 8 N(> Ru ~ Hexaammineruthenium(IlI) ion, 1.13a

1 Iodide ion, 1.10, 5.8, 9.2 IO" Hypoiodite ion, 8.8

I

2

" Iodine molecule anion, table 8 Mn2+

1.10b, 6.13, 7.18 NO Nitric oxide, 4.18 N02 Nitrogen dioxide, l.lOd; table 4 N02

" Nitrite ion, 1.10c, 2.17, 4.6, 5.15, 6.18 N02

2“ Nitrite radical anion, 4.25 N03 Nitrate radical, table 4 N03

" Nitrate ion, 2.18 N03

" Nitrate radical anion, table 4 N2 0 Nitrous oxide, 3.3 N2 03 Dinitrogen trioxide, 4.24 N2 04 Dinitrogen tetroxide, table 4 N3

~ Azide ion, 2.16, 5.12, 6.17 Ni

2+

Nickel(II) ion, 1.10c 02 Oxygen, 3.4, 4.22 02

‘ Superoxide ion, 1.2, 6.2 02S" Hyposulfite radical ion, table 3 02Se" 3.12 02 S2

" Thiosulfite radical ion, table 3 02 U

+ Uranyl(IV) ion, 7.26, 9.4 02 U

2+ Uranyl(VI) ion, 1.14 03 S~ Sulfite radical ion, 1.13f; table 3 03S

2

" Sulfite ion, 1.13e, 2.27. 5.26-5.27, 6.28 03S2" Thiosulfate radical ion, table 3 03S2

" Thiosulfate ion, 3.8, 5.29 03Se" 3.13 03 Si"~ Silicate ion, 2.29 04P

2" Phosphate radical ion, table 5 04S" Sulfate radical ion, table 2 05S" Peroxysulfate radical ion, table 3 05S2 Peroxythiosulfate ion, 5.30

Ti(III) Titanium(III) ion, 6.28a

TI +

Thallium(I) ion, 2.30, 4.7, 6.29, 7.25 V"

+ Vanadium(II) ion, 6.30, 7.27, 8.10 Zn

2H Zinc(II) ion, 1.14a

49

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oxidation of vanadium(II) and chromium(II) by di-iodide, dibromide, and dichloride ions generated by pulse radiolysis,

J. Chem. Soc. Dalton Trans. (11): 1142-8 (1974). 74—1119 Bisby, R.H.; Cundall, R.B.; Adams, G.E.; Redpath, J.L., Selective free radical reactions with proteins and enzymes. The inactivation of subtilsin Carlsberg and subtilsin Novo, J. Chem. Soc., Faraday Trans. 1 70(12): 2210-8 (1974). 74—1125 Badiello, R.; Tamba, M.; Quintiliani, M., Primary and

secondary radicals in the radiation-induced inactivation of

yeast alcoholdehydrogenase, Int. J. Radiat. Biol. 26(4): 311-9

(1974). 74—1140 Pikaev, A.K.; Sibirskaya, G.K.; Shirshov, E.M.; Glazunov,

P.Ya.; Spitsyn, V.I., Pulsed radiolysis of concentrated aqueous solutions of nitric acid, Dokl. Phys. Chem. (Engl.

Transl.) 215(1-3): 328-31 (1974), transl. from Dokl. Akad. Nauk SSSR 215(3): 645-8 (1974). 74—1149 Zhestkova, T.P.; Pikaev, A.K., Destruction rate of Cl2

”

anion-radicals during pulse radiolysis of concentrated aqueous lithium chloride solutions. Bull. Acad. Sci. USSR,

Div. Chem. Sci. (Engl. Transl.) 23(4): 877-8 (1974), transl. from Izv. Akad. Nauk SSSR, Ser. Khim. (4): 913-4 (1974). 74-1168 Willson, R.L., Electron-transfer reactions studied by pulse

radiolysis, Biochem. Soc. Trans. 2(5): 1082-4 (1974). 74-1181 Willson, R.L.; Wardman, P.; Asmus, K.D., Interaction of dGMP radical with cysteamine and promethazine as possible model of DNA repair. Nature (London) 252(5481): 323-4

(1974). 74—1182 Teitelbaum, Z.; Meyerstein, D., Kinetics of reaction of ferricenium ion with some free radicals in aqueous solution. A pulse radiolytic study, Proc. Int. Conf. Coord. Chem., 16th, Dublin, Ireland, Aug. 19-24, 1974, R56, 2p. (Chem. Abs.

85: 191822g).

74—3003 Simic, M.; Powers, E.L.; Centilli, M.; Cross, M., Radiation

sensitization of bacterial spores and phage T7 by NaBr, Int.

J. Radiat. Biol. 25(1): 43-50 (1974). 74—3052 Kemsley, K.; Moore, J.S.; Phillips, G.O.; Sosnowski, A., Reaction of radical probes with substituted phenols as models

for the investigation of tyrosine in aldolase and chemically modified aldolase, Acta Vitaminol. Enzymol. 28: 263-7

(1974). 74—3081 Roberts, P.B.; Fielden, E.M.; Rotilio, G.; Calabrese, L.; Bannister, J.V.; Bannister, W.H., Superoxide dismutase

inactivation by radiation-induced radicals: Evidence for histidine residues in the active site, Radiat. Res. 60(3): 441-

52 (1974). 53
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75-0440

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75-1171

75-1188

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75-7110

Former de Violet, P.; Bonneau, R.; Logan, S.R., Laser flash photolytic study of mercury(Il) iodide in aqueous solution, J. Phys. Chem. 78(17): 1698-701 (1974). Chen, S.; Hoffman, M.Z., Reactivity of the carbonate radical

in aqueous solution. Tryptophan and its derivatives, J. Phys.

Chem. 78(21): 2099-102 (1974).

Barkatt, A.; Ottolenghi, M., Laser flash photolysis of aqueous triiodide solutions. Mol. Photochem. 6(3): 253-61

(1974).

Falcinella, B.; Felgate, P.D.; Laurence, G.S., Aqueous

chemistry of thallium(ll). Part I. Kinetics of reaction of

thallium(II) with cobalt(ll) and iron(lll) ions and oxidation

reduction potentials of thallium(II), J. Chem. Soc. Dalton

Trans. 1367-73 (1974). Snook, M.E.; Hamilton, G.A., Oxidation and fragmentation

of some phenyl-substituted alcohols and ethers by

peroxydisulfate and Fenton's reagent, J. Am. Chem. Soc.

96(3): 860-9 (1974). Anbar, M.; Farhataziz; Ross, A.B., Selected specific rates of

reactions of transients from water in aqueous solution. II. Hydrogen atom, NSRDS-NBS 51, 1975, 56p.

Ross, A.B., Selected specific rates of reactions of transients from water in aqueous solution. I. Hydrated electron. Supplemental data, NSRDS-NBS 43-Supp., 1975, 43p.

Vladimirova, M.V.; Milovanova, A.S., Radiation-chemical

oxidation of Ce’^ and reduction of Ce

4+

in the a and y

radiolysis of LiCl solutions. High Energy Chem. (Engl.

Transl.) 9(4): 309-11 (1975), transl. from Khim. Vys. Energ.

9(4): 357-60 (1975). Redpath, J.L.; Willson, R.L., Chain reactions and

radiosensitization: Model enzyme studies, Int. J. Radiat. Biol. 27(4): 389-98 (1975). Eriksen, T.E., Pulse radiolytic investigation of the S02

- radical ion, Radiochem.-Radioanal. Lett. 22(1): 33-40

(1975). Zhestkova, T.P.; Pikaev, A.K., Pulse radiolysis of concentrated aqueous solutions of lithium chloride. High

Energy Chem. (Engl. Transl.) 9(2): 138-42 (1975), transl. from Khim. Vys. Energ. 9(2): 165-70 (1975). Woods, R.J.; Lesigne, B.; Gilles, L.; Ferradini, C.; Pucheault, J., Pulse radiolysis of aqueous lithium chloride

solutions, J. Phys. Chem. 79(24): 2700-4 (1975).

O'Neill, P.; Steenken, S.; Schulte-Frohlinde, D., Formation

of radical cations of methoxylated benzenes by reaction with OH radicals, Tl"~, Ag~

+

, and S04

*~ in aqueous solution. An

optical and conductometric pulse radiolysis and in situ radiolysis electron spin resonance study, J. Phys. Chem.

79(25): 2773-9 (1975).

Storer, D.K.; Waltz, W.L.; Brodovitch, J.C.; Eager, R.L., A

pulse radiolysis study of some platinum(II) and platinum(IV)

complex ions in aqueous solutions. The formation and

characterization of platinum(I) and platinum(III) transients,

Int. J. Radiat. Phys. Chem. 7(6): 693-704 (1975).

Felicioli, R.; Montagnoli, G.; Monti, S.; Moore, J.S.; Phillips, G.O.; Sosnowski, A., Radiation inactivation of rabbit muscle aldolase, Int. J. Radiat. Biol. 27(6): 525-32 (1975). Chawla, O.P.; Fessenden, R.W., Electron spin resonance and pulse radiolysis studies of some reactions of S04

*’, J. Phys. Chem. 79(24): 2693-700 (1975). Chen, S.; Hoffman, M.Z., Effect of pH on the reactivity of

the carbonate radical in aqueous solution, Radiat. Res. 62(1): 18-27 (1975).

75-7222 Treinin, A.; Hayon, E., Charge transfer spectra of halogen atoms in water. Correlation of the electronic transition energies of iodine, bromine, chlorine, hydroxyl, and hydrogen

radicals with their electron affinities, J. Am. Chem. Soc.

97(7): 1716-21 (1975). 75-7313 Chen, S.; Hoffman, M.Z.; Parsons, G.H.Jr., Reactivity of the carbonate radical toward aromatic compounds in aqueous

solution, J. Phys. Chem. 79(18): 1911-2 (1975).

75-

7346 Wong, D.; Di Bartolo, B., Evolution of the dihalide ion Br2

~

in aqueous solutions, J. Photochem. 4(4): 249-68 (1975).

76-

1048 Broszkiewicz, R.K., On the effect of Br~ on formation of Cl2

~

in the pulse radiolysis of the aqueous chloride solutions. Bull. Acad. Pol. Sci., Ser. Sci. Chim., 24(2): 123-31 (1976). 76-1055 Broszkiewicz, R.K.; Grodkowski, J., Pulse radiolysis studies on aqueous systems PtCl4'~-Cr and PtCl4

2 -Br", Int. J. Radiat. Phys. Chem. 8(3): 359-65 (1976). 76-1058 Frank, A.J.; Graetzel, M.; Kozak, J.J., On the reduction of dimensionality in radical decay kinetics induced by micellar systems, J. Am. Chem. Soc. 98(11): 3317-21 (1976). 76-1105 Buechler, Hch.; Buehler, R.E., The radical ion complex

IOH": spectrum and reactions studied by pulse radiolysis of aqueous iodide solutions, Chem. Phys. 16(1): 9-18 (1976). 76-1112 Bansal, K.M.; Fessenden, R.W., Pulse raaioiysis studies ot the oxidation of phenols by *S04

" and Br2~ in aqueous

solutions, Radiat. Res. 67(1): 1-8 (1976). 76-1141 Kim, K.-J.; Hamill, W.H., Direct and indirect effects in pulse irradiated concentrated aqueous solutions of chloride and sulfate ions, J. Phys. Chem. 80(21): 2320-5 (1976). 76-1143 Bonifacic, M.; Asmus, K.-D., Free radical oxidation of organic disulfides, J. Phys. Chem. 80(21): 2426-30 (1976). 76-1151 Posener, M.L.; Adams, G.E.; Wardman, P.; Cundall, R.B., Mechanism of tryptophan oxidation by some inorganic

radical-anions: A pulse radiolysis study, J. Chem. Soc., Faraday Trans. 1 72(10): 2231-9 (1976). 76-1171 Broszkiewicz, R.K., The pulse radiolysis study of NaN02 and NaNO, solutions. Bull. Acad. Pol. Sci., Ser. Sci. Chim.

24(3): 221-9 (1976). 76-1181 Frank, A.J.; Graetzel, M.; Henglein, A.; Janata, E., Kinetics

of the heterogeneous electron transfer reaction of triplet pyrene in micelles to Br2

~ radicals in aqueous solution, Int. J. Chem. Kinet. 8(6): 817-24 (1976). 76-1185 Eadsforth, C.V.; Power, D.M.; Thomas, E.W.; Davies, J.V., Investigation of the interaction of alkyl sulphates with serum

albumin using the thiocyanate radical ion -(SCN)2 , Int. J. Radiat. Biol. Relat. Stud. Phys., Chem. Med. 30(5): 449-57

(1976). 76-1187 Zemel, H., Electron spin resonance and pulse radiolysis studies of the mechanism and kinetics of S04

* reactions with aromatic compounds in aqueous solution, Ph.D., Thesis, Carnegie-Mellon Univ., Pittsburgh, PA, Aug. 5, 1976, 158p.

76-1203 Tait, A.M.; Hoffman, M.Z.; Hayon, E., The reaction of radiation-generated free radicals with cobalt(II) and

cobalt(III) complexes containing macrocyclic ligands, Int. J. Radiat. Phys. Chem. 8(6): 691-6 (1976). 76-7279 Burrows, H.D.; Pedrosa de Jesus, J.D., A flash photolytic

study of the photo-oxidation of some inorganic anions by the uranyl ion, J. Photochem. 5(3/4): 265-75 (1976). 76-7587 Scheerer, R.; Graetzel, M., Photo-induced oxydation of carbonate ions by duroquinone, a pathway of oxygen

evolution from water by visible light, Ber. Bunsenges. Phys.

Chem. 80(10): 979-82 (1976).

54
77-0011 Farhataziz; Ross, A.B., Selected specific rates of reactions of

transients from water in aqueous solution. III. Hydroxyl

radical and perhydroxyl radical and their radical ions, NSRDS-NBS 59, 1977, 113p. 77-1001 Neta, P.; Madhavan, V.; Zemel, H.; Fessenden, R.W., Rate

constants and mechanism of reaction of S04

-~ with aromatic compounds, J. Am. Chem. Soc. 99(1): 163-4 (1977). 77-1006 Steenken, S.; O'Neill, P.; Schulte-Frohlinde, D., Formation

of radical zwitterions from methoxylated benzoic acids. 1 . One electron oxidation by Tl” +

, Ag'

+

, and S04

~, J. Phys. Chem. 81(1): 26-30 (1977). 77-1047 Maruthamuthu, P.; Neta, P., Radiolytic chain decomposition

of peroxomonophosphoric and peroxomonosulfuric acids, J. Phys. Chem. 81(10): 937-40 (1977). 77-1053 Waltz, W.L.; Brodovitch, J.C.; Kundu, K.P., A pulse

radiolysis study of the reactions of platinum(II) glycine

complexes in aqueous media, Radiat. Phys. Chem. 10(2): 77-

87 (1977). 77-1093 Meisel, D.; Matheson, M.S.; Mulac, W.A.; Rabani, J., Transients in the flash photolysis of aqueous solutions of

tris(2,2-bipyridine) ruthenium(II) ion, J. Phys. Chem. 81(15): 1449-55 (1977). 77-1097 Zansokhova, A.A.; Kabakchi, S.A.; Pikaev, A.K., Mechanism of Cl2

" formation in the pulse radiolysis of neutral aqueous solutions of alkali metal chlorides. High Energy Chem. (Engl. Transl.) 11(1): 50-4 (1977), transl. from Khim.

Vys. Energ. 11(1): 67-71 (1977). 77-1098 Moore, J.S.; Phillips, G.O.; Sosnowski, A., Reaction of the carbonate radical anion with substituted phenols, Int. J. Radiat. Biol. Relat. Stud. Phys., Chem. Med. 31(6): 603-5

(1977). 77-1106 Maruthamuthu, P.; Neta, P., Reactions of phosphate radicals with organic compounds, J. Phys. Chem. 81(17): 1622-5

(1977). 77-1132 Buchanan, J.D.; Armstrong, D.A.; Greenstock, C.L.; Ruddock, G.W., Pulse radiolysis of lactate dehydrogenase,

Int. J. Radiat. Biol. Relat. Stud. Phys., Chem. Med. 32(3): 247-57 (1977). 77-1164 Asmus, K.-D.; Bahnemann, D.; Bonifacic, M.; Gillis, H.A., Free radical oxidation of organic sulphur compounds in aqueous solution, Faraday Discuss. Chem. Soc. 63: 213-25

(1977). 77-1170 Gilbert, C.W.; Ingalls, R.B.; Swallow, A.J., Pulse irradiation of aqueous solutions containing ferrous and chloride ions: reaction between Cl2

" and H02 , Radiat. Phys. Chem. 10(4): 221-5 (1977). 77-1173 Tamba, M.; Badiello, R., Selenium dioxide free radicals: a study by pulse radiolysis, Radiat. Phys. Chem. 10(4): 283-8

(1977).

77-1198 Anderson, R.F.; Patel, K.B.; Adams, G.E., Critical residues

in D-amino acid oxidase. A pulse-radiolysis and inactivation study, Int. J. Radiat. Biol. Relat. Stud. Phys., Chem. Med.

32(6): 523-31 (1977). 77-1503 Maruthamuthu, P.; Neta, P., unpubl. data. 77-3091 Seki, H.; Imamura, M.; Illian, X.A.; Ilian, Y.; Stein, G., Oxidation and reduction of cytochrome C with Br2

", 02~, and C02

“ studied by pulse radiolysis, J. Radiat. Res. 18(1): 6

(1977).

77-

5209 Maruthamuthu, P.; Taniguchi, H., An in situ photolysiselectron spin resonance study of some reactions of phosphate

radicals, J. Phys. Chem. 81(20): 1944-8 (1977).

78-

1075 Maruthamuthu, P.; Neta, P., Phosphate radicals. Spectra, acid-base equilibria, and reactions with inorganic

compounds, J. Phys. Chem. 82(6): 710-3 (1978). 78-1076 Eibenberger, H.; Steenken, S.; O'Neill, P.; SchulteFrohlinde, D., Pulse radiolysis and electron spin resonance

studies concerning the reaction of S04

-~ with alcohols and

ethers in aqueous solution, J. Phys. Chem. 82(6): 749-50

(1978). 78-1093 Hasegawa, K.; Neta, P., Rate constants and mechanisms of

reaction of Cl2” radicals, J. Phys. Chem. 82(8): 854-7 (1978). 78-3005 Davies, J.V.; Moore, J.S.; Mudher, S., Implication of protein aromatic amino acids in concanavalin A-carbohydrate

interactions, Int. J. Radiat. Biol. Relat. Stud. Phys., Chem.

Med. 33(1): 11-9 (1978). 78-3007 Tamba, M.; Pini, L.; Badiello, R., Radiation chemical

evidence for differences in the amino-acid composition of yeast and horse-liver alcohol dehydrogenases, Int. J. Radiat.

Biol. Relat. Stud. Phys. Chem. Med. 33(1): 95-101 (1978). 78-1501 Cope, V.W.; Hoffman, M.Z.; Chen, S., Reactivity of the carbonate radical toward metal complexes in aqueous

solution, J. Phys. Chem., 82(25): 2665-9 (1978). 78-1502 Maruthamuthu, P.; Patterson, L.K.; Ferraudi, G., Redox

reactions of free radicals with Ni(II) complexes. A pulse

radiolytic study, Inorg. Chem., 11(5): 225-7 (1978). 78-1503 Patterson, L.K., to be publ. 78-1504 Zemel, H.; Fessenden, R.W., The mechanism of reaction of S04 “ with some derivatives of benzoic acid, J. Phys. Chem.

82(25): 2670-6 (1978). 78-1505 Madhavan, V.; Levanon, H.; Neta, P., Decarboxylation by

SO4 -

radicals, Radiat. Res. 76(1): 15-22 (1978). 78-1506 Lilie, J.; Henglein, A.; Hanrahan, R.J., Reactions of the carbonate radical anion with organic and inorganic solutes in aqueous solution. Abstracts of the American Chemical Soc. Meeting, Miami Beach FL, 11-15 Sep 1978, and Radiat. Phys. Chem., 17(11): 3157-63 (1978).

55
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1. PUBLICATION OR REPORT NO. NSRDS-NBS 65

4. TITLE AND SUBTITLE

Rate Constants for Reactions of Inorganic Radicals

in Aqueous Solution

7. AUTHOR(S)

Alberta B. Ross and Pedatsur Neta

5. Publication Date June 1979

Organization Code

8. Performing Organ. Report No.

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NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

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Library of Congress Catalog Card Number: 79-607030

Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 200-word or leas factual summary of moat ai ghi ficant information. It document includes a significant bibliography or

literature survey, mention it here.) Rate constants have been compiled for reactions of various transient

inorganic radicals produced by radiolysis or photolysis in aqueous

solution. Data are included for the carbonate radical, sulfate radical

phosphate radical, nitrate radical and other nitrogen-, sulfur- and

s e 1 en ium- c on t a in ing radicals, and the halide and pseudohalide radicals

Cl, Br and (SCN) The radicals react with other inorganic

ions, as well as aliphatic, aromatic and heterocyclic compounds.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name;

separated by semicolons) Aqueous solution; carbonate radical; chemical kinetics; halogen

radical anions; nitrate radical; oxyanion radicals; phosphate radical; photolysis;

radiolysis; rates; selenium radicals; sulfate radical; thiocyanate radical anion.

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Liquified Natural Gas. A literature survey issued quarterly.

Annual subscription: $20.00.

Superconducting Devices and Materials. A literature survey

issued quarterly. Annual subscription: $30.00. Send subscription orders and remittances for the preceding bibliographic

services to National Bureau of Standards, Cryogenic Data

Center (275.02) Boulder, Colorado 80302.
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