TABLE 4. Cobalt(I) reactions — Continued

No.

Reaction k/dm? mol 6“?

I

wc

pH

Method

‘Comments

Ref.

4.12

4.13

als
4.15

4.16
417

4.18

4.19

420

Co* + Os (et or af) (6.0 + 0.6) x 10°

Cot + OH (et) ca.8 x 10°

Cot + Phat <10
Cot + SOs > (2.8 + 0.5) x 10°
Cot + SO.” + SOF”

Cot + Zn** <10"
Cot + allyl alcohol —> ca. 10
(Co-allyl aleohol)*

Co* + 9,10-anthra~
quinone — Co?* + (9,10-
anthraquinone)-

(1.05 + 0.1) x 10°

Co* + benzophenone —> 2.5 x 10°
Co** + (benzophenone)-

Cot + 1,4-benzoquinone —> 4.0 x 10°
Co** + (1,4-benzo-
quinone)

(6.1 + 0.5) x 10°

(7.35 £ 0.7) x 10°

0.019

25+2

2542

RT
2542

RT
2542

ca, 22

RT

RT

2542

14

nat

nat

nat
nat

10

7.0

47

10

pr

rr
Pr

pr

Pr

Absorption of pro-
duets similar to

that of Ox” but
decay slower (see
ref. 76-1072).
Product transfers

an electron to
1,4-benzoquinone
(cce ref. 76-1134).
Evidence possibly
indicates product

to be CoOs*.
Estimated from de-
cay of Co* in ab-
sence of OH scav—
cengers, taking in—

to account the

major competing
reaction Co* + Cot.

Formation of SO.~
inferred from the
absorption produc
ed on pulse radio—
lysis of solutions

of Co + S:0.7.
Product charac
terised by its
absorption spec—
trum.

Measured by the
rate of formation

of the semiquinone
in the presence of
ca. 1 mol dmTM* 2—
methyl-2-propanol.
Measured by the
rate of formation

of the kétyl radi—
cal in the presence
of ca. 1 mol dm-*
2-methyl-2-propanol.
‘Measured by the
rate of formation

of the semiquinone
in the presence of
ca. 1 mol dmTM*
2-methyl-2-propanol.
Measured in the
presence of 1 mol
din? 2-methyl-2—
propanol.

Measured in the
presence of ca. 1
mol dm-* 2-methyl-
2-propancl.

Buxt..76-1072

Buxt.75-1027

Raxe..66-0848,
Bust..76-1072

Baxe..66-0848
Buxt..76-1072

Rao.73-1104

Rao.75-1032

Rao.75-1032

‘Sell.76-1134

Rao.73-1104


‘Taste 10, Indium({l) reactions

No. Reaction

A/dm mol? s~* * I

wc

pH

Method

Comments

Ref.

nig

10.1 In* + In** (et or af)

10.2 In** + OH (et)

10.3 In** + N20

2k = ca, 12x 07

10° (Liaioy

2k = (1.6 + 0.2)
x10

2k = (4.9 + 0.7) -
x 10°

< 10 -

0.0075

RT

25

25

3.6

3.6

nat

Pr

pr

Reinterpreted from
data in ref. 76-1087.
Measured in the pre~
sence of 1 mol/dm?*
2-methyl-2-propanol
taking €aso = 7006
dm? mol* emTM,
Measured from the
initial decay of

In** in the absence
of OH scavengers.
Estimated from the
values of G(Ns)
measured in the
‘y-radiolysis of

In** + N,O solutions.

Tayl.69-0971

RM. Sellers,
unpub, data

R.M. Sellers,
unpub. data

Sell72-0844

“If the data source gives no errors none are shown here but they should be assumed to be at least 25% (or =+50% for 2k).

TABLE 11. Iridium({l) reactions

No. Reaction

k/dm? mol" 5 * I

wc

pH

Method

Comments

Ref.

IP (from xq + IrCle?”)
Wl +I dis)

2k = (3.3 + 0.4)
x 10°

0.0018

RT

pr

Bros73-1066

If the data source gives no errors none are shown here but they should be assumed to be at least ++25% (or +50% for 2k).

TaBLE 12. Manganese(I) reactions

No. Reaction

k/dm? mol” s~ I

uc

pH

Method

Comments

Ref.

Mn ng

121 Mn* + Curt (et?)

12.2

Mant + 10.7 (ot?)

12.3 Mat + NOs” (et?)

fra = 1.6 + 0.2 2.0

(MnS0,)

fra — 1401 2.0

(MnSO.)

see entries 12.1 and 12.2.

RT

RT

5-8

5-8

Measured by competi—
tion kinetics using
NOs” as competitor

in the presence of

0.5 mol dm~* MnSO..
Rate constant relative
to Mn* + NOs").
‘Measured by competi-
tion kinetics using
NOs” as competitor

in the presence of

0.5 mol dm~$ MnSO,.
Rate constant relative
to Mn* + NOs").

Fiti70-0117

Fis70-0117

"If the data source gives no errors none are shown here but they should be assumed to be at least -+25% (or -+50% for 2k).

35


Hg
Mies + Het — eet

Mee + HeOH —-
get On

Hee + HeOrD. —-
Met 20H

Hew
Hes? + Hes? Cee?)

Hed
Hate (and hydrolysed forms)
Hee Sgn

Bg + Hg? Hee + Hee

Mgt + Het He)

HgOH + Heo
Hes0 + 20
or Hess

He! + Het

(5.0 & 0.5) x 10"

2k — 04+ 02)
perc

2k 0 + 0.5)

2k G2 + 0.5)

2k = 0 + 1.0)

2k a4 + 04

<0.017

0

<0.017

<on

Rr

Rr

a.

a7

sas

10.2

Measured from the
PH dependence of
Hee

Measured from the
PH dependence of

Fuji..73-1080

Fus75-1044

Fuji..73-1080

Fara.72-0290

Fujs75-1044

Pika 75-1218



Tapes 14, Nickel() and sickelGM) reactions — Continued

Now Reaction fama maakt a = 7 ee pe Method Ret
Vasa “E Getbpy et (oO (2.7 = 0.8) x10" -0.016~ Rr 70 Pr Pate 76
olo28
14.55 NEL* + Fe@py* (od 44 00)~10" 0016 RT 70
14.56 NIL + BLO* @O G4 027% 20% 0.06- ar <125 0 pe
os
aa.s7 + HPO. @D < 10+ 2.01— Rr 5.50 pe - raie..70-
14.58 NIL + NO Gt or O20, (3.9% 0.4) x 107 a Rr 70 Pe Reaction possibly rate. 76-
fe NUT) complex.

nat Fo am)

14.60 Lt Rea @s-404x10° 0016 RT 70 pr
oo olo2s

461 NLT 4 RuGVE).NO=* 40.7) ~107 0.016 RT 70 pe raie76-
eo o.o28

14.62 NiL* + acetic acid @220n~100 cos, Rr 285 Pe rait76.
co o.08

ses 8 4 0.5)x10" 0.004 er 70. pr Pase.76-

14.64 NiL* + 1,4-bemno (8-4 0.5)% 10" 0.004 Rr 70 pe rain 70
uinone (oo

14.65 NIL* + 3-bensoyl— 2.5 0.8)x 10" 0,004 Rr 70 pe Taie76-
‘pyridine (oo

14.65 NIL* + flucrencein 2-4 03)x10° 0.008 Rr 70 Pr rene
oo

14.07 NEL* + methyl iodide (4.6 -£0.5)x10" 0.02 Rr o2 Pr rai 76

Kot or Sn2)



TABLE 3. Cd(1) reactions — Continued

No. Reaction ‘k/dm? mol" 57! * I wc pH Method Comments Ref.
3.18 Cat + Co(NHs)OH** 9.0 + 1.3) x 10" 0.08 RT Tl pr - Meye.69-0428
(et)
3.19 Cd* + Co(NHs)sNs** (1.41 + 0.2) 0.08 RT 5-6 pr - Meye.69-0428
(e) x10
3.20 Cd* + Co(NH)sNCS* (1.32 + 0.2) 0.08 = «RT 5-6 pr - Meye.69-0428
(et) x10
3.21 Cat + Co(NHssOOCCHS** (9.0 + 1.3) x 10" 008 = =RT 5-6 pr - Meye.69-0428
(et)
3.22 Cat + Crt <i = RT nat pr - Baxe..66-0848
3.23 Cat + CrO* (et) (9.8 + 1.0) x 10° 0.02" 252 nat a - Buxt..76-1072
3.24 Cat + CraOr*" (et) (1.6 + 0.2) x 10% 0.02" 2542 nat Pr - Bust..76-1072
3.25 Cat + Cut (et) (1.2 + 0.2) x 10° 0.08 RT nat pr - Meye.68-0855
(1 + 0.2) x 10° 0.04 = RT 5-8 Y — Measured by compe- Fiti70-0117
tition kinetics
using NOs” as com—
petitor and taking
Ca* + NO,-) =
3.5 x 10* dm?
mol"? $4,
3.26 Cd* + Hs0.—> (1.55 + 0.2) x 10° - RT nat pr - Meye.68-0855,
Ca** 4+ OF + OFT (2.2 + 0.2) x 10% - 25 nat pr - Buxt..76-1072
2.8 x 10° - RT nat pr Buxt..67-0062
Ey =92 +08 - 1-30 nat pr - Buxt..76-1072
KJ mol"
Products identified
in y-radiolysis
studies (see Buxt..
73-0039).
3.27 Cd* + HsO* <10° = 0.08 RT - pr - Meye.68-0855
3.28 Cat + 105” (et) (2.3 + 0.3) x 10° 0.08 = «RT nat pr - Meye.68-0855
(2.1 + 0.2) x 10° 0.04 «RT 5-8 7 Measured by compe- Fiti70-0117
tition kinetics
using NOs” as com—
petitor and taking,
Cat + NOs-) =
3.5 x 10" dm*
mol 5“,
3.29 Cat + MnO¥ (et) (78 + 0.8) x 10° - — ea22 10 pr Measured by the Rao.73-1104
rate of depletion
of the MnO.” ab
sorption in the
presence of ca. 1
mol dm-* 2-methyl-
2-propanol.
1.3 x 10% ca. 20 nat pr Measured by the Daxe..65-0305
0.004 rate of depletion
of the MnO.
absorption.
3.20 Cat + Nit <1 - RT at pr - Baxe..66-0848
3.31 Cat + NOs" (et) 2.0 + 0.3) x 10° 0.08 == RT nat pr - Meye.68-0855
E,=12541.7 0.08 3-90 nat pr - Meye.70-1228
KJ molTM*
3.32  Ca* + NOs” (et) (5 + 0.5) x 10" 0.08 RT nat pr - Meye.68-0855,


75-1092

75-1128

75-1130

75-1153

78-1171

75-1188

75-1203

75-1215,

75-1218

‘75-7093

76-1001

76-1003

electron transfer to TI** and Ag** in aqueous solution. A pulse
radiolysis and in situ radiolysis EPR study, ANGEW. CHEM.
INT. ED. ENGL. 14(6): 430-1 (1975)

Meyerstein, D., Kinetics of complexation of copper(I) ions with
maleate and fumarate in aqueous solutions. A pulse radiolytic
study, INORG. CHEM. 14(7): 1716-7 (1975).

ie, J Simic, M.G; Endicott, J.F., Chemical behavior of
thodium(II)-ammine complexes generated by the pulse
radiolytic one-electron reduction of rhodium(IIl) ammines,
INORG. CHEM. 149): 2129-33 (1975).

O'Neill, P.; Schulte-Froblinde, D., Evidence for formation of a
(T10H)* complex, J. CHEM. SOC., CHEM. COMMUN. (10):
387-8 (1975).

Barkatt, A., Rabani, J., Kinetics of spur reactions of electrons in
ethylene glycol-water glassy ice. A pulse radiolytic study, J.
PHYS. CHEM. 79(24): 2592-7 (1975).

O'Neill, P.; Steenken, S.; Schulte-Frohlinde, D., Formation of
radical cations of methoxylated benzenes by reaction with OH
radicals, T**, Ag**, and SO.” 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, RL, A
pulse radiolysis study of some platinum(II) and platinum(IV)
complex ions in aqueous solutions. The formation and
characterization of platinum(l) and platinum({II) transients,
INT. J. RADIAT. PHYS. CHEM. 7(6): 693-704 (1975).

Fujita, $.5 Horii, H.; Mori, T.; Taniguchi, S., Pulse radiolysis of
Hg(CN)s in aqueous solutions, BULL. CHEM. SOC. JPN.
48(11): 3067-72 (1975).

Ten, Y.A.; Czapski, G.; Ardon, M., The formation of CrO,?* in
the reaction of Crt + Oz in aqueous acid solutions, ISR. J.
CHEM. 13(1): 15-21 (1975).

Pikaev, A.K.; Sibirskaya, G.K.; Spitsyn, V.I., Pulsed radiolysis
of aqueous solutions of compounds of divalent mercury, DOKL.
PHYS. CHEM. (ENGL. TRANSL.) 224(1-3): 994-7 (1975).
‘Translated from DOKL. AKAD. NAUK SSSR 224(3): 638-41
1975).

Falcinella, B.; Felgate, P.D.; Laurence, G.S., Aqueous chemistry
of thallium({I) with manganese({I), iron(II), and cobalt(I) ions, J.
CHEM. SOC., DALTON TRANS. (1): 1-9 (1975).

Tait, A.M; Hoffman, M.Z.; Hayon, E., The reactivity of
cobalt(I) complexes containing unsaturated macrocyclic ligands
in aqueous solution, J. AMER. CHEM. SOC. 98(1): 86-93
(1976).

Baxendale, J.H.; Garner, C.D; Senior, R.G.; Sharpe, P., The
reduction of molybdenum(II) trifluoroacetate by pulse radiolysis
in methanol, J. AMER. CHEM. SOC. 98(2): 637-8 (1976).

76-1016

76-1039

76-1042

76-1055

16-1072

76-1087

76-1093

76-1134

76-1186

10121

77-1027

77-1500

Faraggi, M.s Loopold, J.C., Puleo radiolysis studies of cloctron—
transfer reaction in molecules of biological interest. II. The
reduction of Cu(I1)-peptide complexes, RADIAT. RES. 65(2):
238-49 (1976).

Tait, A.M.; Hoffman, M.Z.; Hayon, E., Reactivity of nickel(l)
and copper) complex containing 14-membered macrocyclic
ligands in aqueous solution, INORG. CHEM. 15(4): 934-9
1976).

Jungbluth, H.; Beyrich, J.; Asmus, K.-D., Reduction of
mercuric halides and pseudohalides in aqueous solution.
Formation and some physicochemical properties of HgCl, HgBr,
Hgl, HgSCN, and HgCN radical molecules, J. PHYS. CHEM.
£80(10): 1049-53 (1976).

Broszkiewicz, R.K.; Grodkowski, J., Pulse radiolysis studies on
aqueous systems PtCl?"-Cl- and PtCl’--Br-, INT. J.
RADIAT. PHYS. CHEM.8(3): 359-65 (1976).
Buxton, G.V.; Sellers, R.M.; McCracken, D.R., Pulse radiolysis
study of monovalent cadmium, cobalt, nickel and zinc in
aqueous solution. Part 2. Reactions of the monovalent ions, J.
(CHEM. SOC., FARADAY TRANS. 1 72(6): 1464-76 (1976).
Fujita, S.; Horii, H.; Mori, T's Taniguchi, S., Pulse radiolysis of
HgBra in aqueous solutions, BULL. CHEM. SOC. JPN. 49(5):
1250-3 (1976).
Brodovitch, J.C Storer, D.K Waltz, W.L; Eager, RL, A
pulse radiolysis and flash photolysis study of the formation and
characterization of platinum(III) amine complex ions, INT. J.
RADIAT. PHYS. CHEM. 8(4): 465-75 (1976).
Sellers, R.M.; Simic, M.G., Pulse radiolysis study of the
reactions of some reduced metal ions with molecular oxygen in
aqueous solution, J. AMER. CHEM. SOC. 98(20): 6145-50
(1976).
Buxton, G.V; Green, J.C; Sellers, R.M., Oxidation of
copper(l)-olefin complexes in aqueous solution by oxygen and
hydrogen peroxide, J. CHEM. SOC., DALTON TRANS. (21):
2160-5 (1976).
Buxton, G.V.; Sellers, R.M., The radiation chemistry of metal
ions in aqueous solution, COORD. CHEM. REV. 22(3): 195-
(274 (1977).
Simic, M.G.; Hoffman, M.Z.; Brezniak, N,V; Kinetics of
ligand-to-metal intramolecular electron transfer in cobalt(III)-
ammine complexes containing a coordinated radical, J. AMER.
CHEM. SOC. 99(7): 2166-72 (1977).
Buxton, G.V.; Green, J.C., Reactions of some simple a- and
B-hydroxyalkyl radicals with Cu** and Cu* ions in aqueous
solution, J. CHEM. SOC., FARADAY TRANS. 1 74: 697-714
ase).

U.S, GOVERN? PRINTING OFFICE

1978253601


‘Tamu 18. Rhodium({) reactions
Ne Reaction Aides mol? ae = 7 we pe Ret
RMNEs).A* and related complexes

aw RANE yO 3.5 x10" - er 40 7s,
TMNT DAHAOF tN

16.20 RANE) HLO" 4 HO —~ 400+ = Rr a0 m.73
ROVE aOTAOD NES

16.5 RAVE + Os Bel x 108 - Rr 40 1ak..78

184 RRO + 2k — oa. 1.2 x10" - RT a0 wan7e
FEMME) (aie?)

es oa Lax 108 - er a0 1n..7

50


‘TamLE 17. Platinum() and platinum(ID reactions — Continued

Ro

Reaction Zea) 7 we a Mothoa ‘Comments Wer
Tas Se 77 OB a ca os Pr Measured in the
os
1719 PET 4 Cum eo (3.2 © 0.7) x 10" ma oo os pr
17.2000 PEM 4 Fem (oo (2.5 © 0.4) = 10" 5. oa. os pr
pereny Bs
PEM from Exon da” + OF
ze. esl eee 25 + 0.2) 10" - RT 4.0-7.0 Pr
2.4" 0.8) x 10" - RT 7.09.6 Pr
17.22 wey 4 On (a.2" = 0.5) x 10% - Rr 7.0-9.6 we Brod..76
Cee HO

728 py a (4.2 + 0.9) x10" = Rr 4.0-7.0 pr

r
72a cen G.s + 0.4) x 10" = RT 29.85 ” Brod...7¢

ery canine a

(a3 © 2.8) x10" - RT 40-01 Eph. Brod...7¢

17-250 (PEM 4 Cu < 10+ Rr 63-06 pr -
1726 weme y (2.5% 0.2) = 10° Rr 6.36.6 Pe =

EeCNa— Goo.
az27 0 eam < 10° = RT 6.36.6 pr -
2728 Gem (6.6 1B) x 10" = Rr 2aaas Pro Gflentry 17.25

em or pA. = 08 = 0.2
pee eee wee = KY 2a Pr Reaction may be Brod.7¢
17.300 em 4 cm (11 + 0.09) x 10° = Rr 345.1 pe Brod...7¢

emi
27.320 ey Com 2.7% 1.0) x 10" - nr 2a pr

coer)
1732 Em 1h (8.7 ste 1.0) x 107 - Rr aa er Brod-7¢

Pun (ain?)



TABLE 20. Samarium(II) reactions — Continued

No. Reaction ‘k/dm® mol“ 5° * I we pH Method Comments Ref.
20.22 Sm** + Os (af or et) 3.9 x 10° 0.015 RT nat Pa - Fara.72-0065
(4.2 + 0.5) x 10° 0375 «RT 3-6 Pr - Pika..73-1084
20.23 Sm** + OH (et) 6x10 - RT nat pr - Fara.72-0065
(6.2 + 0.8) x 10° 0.375 RT 3-6 pr - Pika..73-1084
20.24 © Sm** + Ru(NH,)Br* 1.5.x 10° 0.06 RT 6 Pr - Fara.73-0107
(et)
20.25 © Sm** + Ru(NHs)sCi* 15x10 0.06 RT 6 pr - Fara.73-0107
(et)
4.3 x 10° 1.0 RT 6 pr - Fora.73-0107
(NaClO.)
6.5 x 10° 1.0 RT 6 Pr - Fara.73-0107
(NaCl)
20.26 © Sm** + Ru(NH,)sH.0** 65x10" 03 RT 2 - Fara.73-0107
(eo)
18x 10" 1.0 RT 2 - Fara.73-0107
(NaCl)
1.3 x 10° 1.0 RT 2 - Fara.73-0107
(Nac)
20.27 Sm** + Ru(NHs)sI?* ca. 10% 0.06 RT 6 - Fara.73-0107
(et)
20.28 Sm** + Ru(NH,)OH** 4.010" 0.06 RT 6 Pr - Fara.73-0107
(et)
2.2.x 10° 10 RT 6 pr - Fara.73-0107
(NaCl0,)
6.0 x 10° 1.0 RT 6 Pr - Fara.73-0107
(NaCl)
20.29 Sm** + Ru(NHa)e** 25x10" 0.06 RT 6 pr - Fara.73-0107
(e) 2.0 x 10° 1.0 RT 6 pr - Fara.73-0107
(NaClO,)
8.0 x 10° 1.0 RT 6 pr - Fara.73-0107
(NaCl)
20.30 Sm** + Yb** (et) 3.0 x 10° 0.015 RT nat pr - Fara.72-0065

“If the data source gives no errors none are shown here but they should be assumed to be at least +25% (or +50% for 2k).


TABLE 21. Thallium(0) and (II) reactions — Continued

No. Reaction ‘k/dm? mol 5-1 * I wc pH Method Comments Ref.

21.29 TI + CHsCOHCHs (04423)x10° 0 - 23+2 043  y Estimated from the Bure.70-0336
(et or af ‘y-ray induced chain

reaction in TIT +

2-propanol solutions,

taking A(T! + TP)

= 5.5 x 10* dm? mol"?
4 (gee entry 21.25).

21.30 TF* + anisole —> 6.0+05)x108  - 22 4 pr Radical cation pro- O'Ne..75-1171
Tit + (anisole)* duct characterised

by its absorption and
esr spectra.

21.31 TH + 1,2-dimeth- (6.0 +0.6)x108 - 22 4 pr Radical cation pro- O'Ne..75-1171
oxybenzene —> TI + duct characterised O'Ne..75-1086

(1,2~dimethoxybenzene)* by ite absorption
and esr spectra,

21.22 — TIOH* + 1,2-dimethoxy— 12% 10° - RT >47 pr Radical cation pro— O'Ne..75-1086

benzene — Tit + OH- + duct characterised
(1,2-dimethoxybenzene)* by its absorption
and esr spectra.

21.33 TH+ + 1,3-dimethoxy- (8.0 + 0.8) x 108 2+2 4 pr Radical cation pro— O'Ne..75-1171
benzene > TI* + (1,3- duct characterised
dimethoxybenzene)* by its absorption

and esr spectra.

21.34 ‘TH + 1,4-dimethoxy- (6.5 + 0.7) x 10° 2W+t2 4 pr Radical cation pro- O'Ne..75-1086
benzene —> TI* + duct characterised O'Ne..75-1171
(1,4-dimethoxybenzene)* by its absorption

and esr spectra,

21.35 TIOH* + 1,4-dimethoxy 4.5 x 10% RT >47 pr _ Radical cation pro- O'Ne..75-1086

benzene > TIt + OH- + duct characterised
(1,4-dimethoxybenzene)* by its absorption
and esr spectra,

21.36 TIOH* + menaquinone slow RT 68 pr - Rao.73-1047

21.37 TH*+1,2,3-trimethoxy- @2+03)x108 2+2 4 pr Radical cation pro- O'Ne..75-1171
benzene > TI + (1,2,3- duct characterised
trimethoxybenzene)* by its absorption and

esr spectra.

2138 TF* + 1,2,4-trimeth— (6.8 + 0.7) x 10° 22 4 pr Radical cation pro- O'Ne..75-1171
oxybenzene —> TI* + duct characterised
(1,2,4-trimethoxybenzene)* by its absorption

and cor epectra. .

21.39 © TH* + 1,3,5-trimeth~ (7.0 + 0.7) x 10° 22 4 pr Radical cation pro- O'Ne..75-1171
oxybenzene — TI* + duct characterised
(1,3,5—trimethoxybenzene)* by its absorption

and cor spectra.

58


‘TABLE 17. Platiqum() and platinum(I) reactions

Now Reaction = 7 we pH Method Comments Ret
Pe Reactions
De from PCL + exe
aa Pee NIO (ot or O ad < 4x10 - Rr nae pr -
172 PE + OL Grorad = 2 > 107 = Rr nae Pr =
17300 pet pa eS “Km ae OS) 0.003 Rr an Pe whether
Es Pet fate constants
‘k= GAS 0.15) 0.013 Rr Pr Measured in the Ghoa.6s
x ae Presence of 0-1 mol
Sms Rel.
aa (8 + 0.25) = 107 er nat pe
ws G's $ 018) = 10" = Rr mae Pr
= dicthyleneeriamine).
16 ‘Be ao 20) 2 om nat Pr
PE from PLLGI” + HL = diethylenetriamine).
ae eC aaney 2A — GB 0.5) - ca: 23 pr - Stor 75
x 10° 2s
Pe from Pian yat* + oa
x10" 2s _
PA Yrom Phonya* +
azo bet Pet (aie) 2k @e £08) - ca 23 pr = Stor 75—
PE from PiLGI* + H UL = tetracthyidieehylenetriamine).
azo | Pee Pe aie?) Se G8 a OO) - on 23 Pr -
= 10% @
ava @ + Dx 10° 6 = ca os Pr Stor..75—
fhechaniem)
1722 PEM + Cameo (5 © 0.2) x 10 os - 8 pr Stor...75—
icy 25



TABLE 4. Cobalt(I) reactions — Continued

Reaction k/dm? mol-*

. I °C pH Method Comments

Ref.

447

4.48

4.50

451

4.52

4.53

CoL* + Ru(NH,)sNO** (et) 3.9x10" 0.016- RT 92 pr Measured in the
0.028 presence of 1 mol
dm“? 2-methyl-2—
propanol.

CoL* + acetic acid > 7.5 x10" 0.01- RT 48 pr Measured in the
CoLH* + CHsCOOTM 0.05 presence of 1 mol

dm“ 2-methyl-2-
propanol. See ref.
for evidence for
proton transfer
mechanism.

CoL* + 9,10-anthraquinone 44x 10° 0.004 RT 92 pr Measured in the
-2-sulphonate —> CoL** + presence of 1 mol
(9,10-anthraquinone-2- dmTM* 2-methyl-2~
sulphonate) propanol. Semi—

quinone product
characterised by
its absorption.

CoL* + 3-benzoylpyridine 4.6 x 10 0.004 RT 92 pr Measured in the
(et +?) presence of 1 mol

dm”* 2-methyl-2~
propanol. Only
50% electron trans—
fer to the 3-
benzoylpyridine.
Other reaction
pathway(s) not
characterised.

CoL* + fluorenone —> 43x 10° 0.004 RT 92 pr Measured in the
CoL** + (fluorenone) presence of 1 mol

dm”* 2-methyl-2-
propanol. Ketyl
radical product
characterised by
its absorption.

CoL* + menaquinone —> 4.6 x 10° 0.004 RT 9.2 pr Measured in the
CoL#* + (menaquinone)~ presence of 1 mol

dmTM* 2-methyl-2-
propanol. Semi~
quinone product,
characterised by
its absorption.

CoL* + methyl iodide (et) 4.7.x 10° 0.015 RT 92 pr Noevidence for

substitution (Sx2)
reaction pathway.

CoL* (L = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) o

3

CoL* + Co(bpy)s** (et) 8.5 x 107 0.016- RT 65 pr Measured in the
0.028 presence of 1 mol
dm“* 2-methyl-2—
propanol.

18

‘Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

‘Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001


TABLE 13. Molybdenum reactions

No. Reaction A/dm? molTM* s“ * I °c

pH = Method

Comments

Ref.

[Mox0CCFs).]" (from Mox(O2CCFs). + es in methanol)
13.1 [Mos(0:CCF)4J” + ‘R= (4.5 + 1.0) - RT
[Mox(02CCFs).- x 10°
(dis?) 'K = (25 +10) - RT
x10"

13.2 [Mox(OsCCF3).J (9 +03)x10° = RT
+ 0s (af?)

Measured from decay
of Mo(1 1/2) species
in methanol. Two decay
processes observed,
one of which believed

reaction. Rate con-
stant (unclear whether
or 2k) calculated
taking €reo = 2600
dm* mol" em".

Note that if the
slower process does
not involve the

Mo(1 1/2) species,
the valne of €, and
hence k, is incorrect.
Measured in
Methanol.

Starting mater—

ial [Mox(O.CCFs)4]
not regenerated,

0 reaction does

not involve

electron transfer.

Baxe...76-1003

Baxe...76-1003

“If the data source gives no errors none are shown here but they should be assumed to be at least 25% (or 50% for 2k).

36


72-0381

72-0460

72-0461

72-0844,

72-1088

73-0038

73-0039

73-0043

73-0107

73-0121

73-0122

73-1047

73-1053

‘18-1057

73-1066

73-1080

73-1084

aqueous solutions, INT. J. RADIAT. PITYS. CHEM. 4(3): 353-
8 (1972).

Baxendale, J.H.; Fiti, M., Transient species in the reactions of
some pyridyl complex ions with hydrated electrons, J. CHEM.
SOC. DALTON TRANS. (18): 1995-8 (1972).

Lati, J.; Meyerstein, D., Trivalent nickel. 1. A pulse radiolytic
study of the formation and decomposition of the ammoniacal
complex in aqueous solution, INORG. CHEM. 11(10): 2393-7
972).

Lati, J.; Meyerstein, D., Trivalent nickel. II. A pulse radiolytic
study of the formation and decomposition of the
ethylenediamine and glycine complexes in aqueous solution,
INORG. CHEM. 11(10}: 2397-401 (1972).

Sellers, R.M., Ph.D. Thesis, Univ. of Leeds, 1972.

Wright, R.C.; Laurence, G.S., Production of platinum(III) by
flash photolysis of PtClet”, J. CHEM. SOC., CHEM. COMMUN.
(3): 132-8 (1972)

Jayson, G.G.; Parsons, B.J.; Swallow, AJ., Oxidation of ferrous
ions by perhydroxyl radicals, J. CHEM. SOC, FARADAY
TRANS. 1 69(1): 236-42 (1973).

Buxton, G.V.; Dainton, F.; McCracken, D.R., Radiation
chemical study of the reaction of Nit, Cot and Ca* with NO.
Evidence of the formation of a hyperoxidised state by oxygen
atom transfer, J. CHEM. SOC, FARADAY TRANS. 1 69(1):
243-54 (1973).

Nazhat, N.B.; Asmus, K.-D., Reduction of mercuric chloride by
hydrated electrons and reducing radicals in aqueous solutions.
Formation and reactions of HgCl, J. PHYS. CHEM. 77(5): 614
20 (1973).
Faraggi, M.; Feder, A., Electron-transfer reactions of cobalt(III)
and ruthenium(II) ammines with europium({I), ytterbium(II),
and samarium(II) in aqueous solutions, INORG. CHEM. 12(1):
236-41 (1973).

Robinson, E.A.; Schulte-Froblinde, D., Pulse radiolysis of 1,4~
dicyanobenzene in aqueous solutions in the presence and
absence of thallium(l) ions, J. CHEM. SOC. FARADAY
TRANS. 1 69(4): 707-18 (1973).

Jayson, G.G.; Parsons, B.J.; Swallow, A.J., Appearance of
sulphatoferric complexes in the oxidation of ferrous sulphate
solutions. A study by pulse radiolysis, J. CHEM. SOC.
FARADAY TRANS. 1 69(6): 1079-89 (1973).

Rao, P.S.; Hayon, E., One-electron redox reactions of free
radicals in solution. Rate of electron transfer processes of
quinones, BIOCHIM. BIOPHYS. ACTA 292: 516-33 (1973).
Farhataziz; Mibalcea, 1; Sharp, LJ.; Hentz, RR. Pulse
radiolysis of liquids at high pressures. IV. Hydrogen-atom
reactions in aqueous 0.1M HClO, solutions, J. CHEM. PHYS.
59(5): 2309-15 (1973).

Ellis, J Green, M.; Sykes, A.G.; Buxton, G.V.; Sellers, R.M.,
Pulse radiolysis of titanium({II) and other metal(II1) ions in the
presence of formic acid, J. CHEM. SOC., DALTON TRANS.
(16): 1724-8 (1973).

Broszkiewicz, R.K., Pulse radiolysis studies on complexes of
iridium, J. CHEM. SOC, DALTON TRANS. (17): 1799-802
973).

Fujita, S.; Horii, H. Taniguchi, S., Pulse radiolysis of mercuric
ion in aqueous solutions, J. PHYS. CHEM. 77(24): 2868-71
(1973).

Pikaev, A.K.; Sibirskaya, G.K.; Spitsyn, V.L, Study of divalent
samarium, europium, thulium, ytterbium, and of tetravelent
praseodymium ions by pulse radiolysis in aqueous solution,
DOKL. PHYS. CHEM. (ENGL. TRANSL) 209(4-6): 339-42

73-1104

74-1017

74-1037

74-1038

74-1040

74-1072

74-1104

74-1142

74-1146

74-7265

75-1027

75-1032

75-1044

75-1049

75-1064

75-1077

75-1086

67

(1973), Transl. from DOKL. AKAD. NAUK SSSR 209(5):
1154-7 (1973).

Rao, P.S.; Hayon, E., Rate constants of electron transfer
processes in solution: Dependence on the redox potential of the
acceptor, NATURE(LONDON) 243: 344-6 (1973).

Schwarz, H.A.; Comstock, D.; Yandel, J.K.; Dodson, R.W., A
pulse radiolysis study of thallium(Il) in aqueous perchloric acid
solutions, J. PHYS. CHEM. 78(5): 488-93 (1974).

Kelm, M, Lilie, J.; Henglein, A.; Janata, E., Pulse radiolytic
study of Ni*. Nickel-carbon bond formation, J. PHYS. CHEM.
78(9): 882-7 (1974).

Dodson, R.W.; Schwarz, H.A., Pulse radiolysis studies of
chloride complexes of thallium({l). Absorption spectra and
stability constants of TICI*, TICla, and TICls, J. PHYS. CHEM.
78(9): 892-9 (1974).

Harel, Y; Meyerstein, D., On the mechanism of reduction of
porphyrins. A pulse radiolytic study, J. AMER. CHEM. SOC.
96(9): 2720-7 (1974).

Mulazzani, Q.G.; Ward, M.D; Semerano, G3 Smmi, SS;
Giordani, P., Gamma and pulse radiolysis of
tetracyanonickelate(II) anion in aqueous solution, INT. J.
RADIAT. PHYS. CHEM. 6(3): 187-201 (1974).

Laurence, G.S; Thornton, A.T., Kinetics of oxidation of
transition-metal ions by halogen radical anions. Part. IV. The
oxidation of vanadium(I]) and chromium(II) by diiodide,
dibromide, and dichloride ions generated by pulse radiolysis, J.
CHEM. SOC., DALTON TRANS. (11): 1142-8 (1974).

Cohen, H.; Meyerstein, D., Ultraviolet-visible spectrum, and
kinetics of formation and decomposition, of penta-
aquahydridochromium(IIl) and chromium(II) in aqueous
perchlorate solutions: A pulse-radiolysis study, J. CHEM. SOC.,
DALTON TRANS. (23): 2559-64 (1974).

Cohen, H.; Meyerstein, D., Chromium-carbon bonds in aqueous
solutions. A pulse radiolytic study, INORG. CHEM. 13(10):
2434-43 (1974),

Falcinella, B.; Felgate, P.D.; Laurence, G.S., Aqueous chemistry
of thallium(II). Part I. Kinetics of reaction of thallium({I) with
cobalt(II) and iron(II) ions and oxidation-reduction potentials of
thallium(I1), J. CHEM. SOC., DALTON TRANS. 1367-73
1974).

Buxton, G.V.; Sellers, R.M., Pulse radiolysis study of
monovalent cadmium, cobalt, nickel and zinc in aqueous
solution. Pt. 1. Formation and decay of the monovalent ions, J.
CHEM. SOC., FARADAY TRANS. I 71(3): 558-68 (1975).
Rao, P.S; Hayon, E., One electron oxidation of odd-valent
metal ions in solution, J. PHYS. CHEM. 79(9): 865-8 (1975).
Fujita, S.; Horii, H.; Mori, T.; Taniguchi, S., Pulse radiolysis of
mercuric oxide in neutral aqueous solutions, J. PHYS. CHEM.
79(10): 960-4 (1975).

Armor, J.N.; Hoffman, M.Z., Reactivity of coordinated nitrosyls.
IV. One-electron reduction of ruthenium nitrosylpentaammine
(8+) ion in aqueous solution, INORG. CHEM. 14(2): 444-6
(1975).

Kelm, M5  Henglein, A., Pulse radiolytic investigation
of the reduction of cadmium(II) ions, J. CHEM. SOC.,
FARADAY TRANS. 1 71(5): 1132-42 (1975).

Armor, J.N Furman, R.; Hoffman, M.Z., Reactivity of
coordinated nitrosyls. V. Generation and characterization of a
ruthenium({I) alkylnitroso complex, J. AMER. CHEM. SOC.
97(7): 1737-42 (1975).

O'Neill, P.; Steenken, S.; Schulte-Froblinde, D., Formation of
radical cations from 1,2- and 1,4-dimethoxybenzene by



Contents

Introduction.
Arrangement of the tables
List of abbreviations.
Table 1. — Silver(0) and (II) reactions.
Table 2. Gold(0) and (II) reactions.
Table 3. Cadmium(I) reactions..
Table 4.  Cobalt(I) reactions..............
Table 5. Chromium(]), (II) and (V) reaction:
Table 6.  Copper(I) and (III) reactions
Table 7. Europium(II) reactions
Table 8. — Iron(II) reactions .....
Table 9. Mercury(0) and (I) reactions
Table 10. Indium(II) reactions.
Table 11. _Iridium(II) reactions
Table 12. Manganese(I) reactions
Table 13. Molybdenum(II) reactions
Table 14. Nickel(I) reactions
Table 15. —_ Lead(I) reactions...
Table 16. Praesodymium(IV) reaction:
Table 17. _ Platinum(I) and (III) reactions
Table 18. | Rhodium(II) reactions........
Table 19.  Ruthenium(1), (II), (III) and (IV) reaction:
Table 20. | Samarium(II) reactions
Table 21. —_ Thallium(0) and (II) reactions
Table 22. Thulium/(II) reactions..
Table 23. —-Ytterbium(II) reactions
Table 24. — Zinc(I) reactions.
Table 25. —_ Intramolecular electron transfer reactions for
some metal complexes
References.



Tamir 7. Europium(D reactions

aaction 7am mar 7 Tp Mammon Comments om
Buk Gnclades only thoss Fata constants mcasured hry pales Fedialyl).
xe, poe For x nat - - Fare.72-0005
Slax
Eur + CodvHecie sore See 2s ° pe - Fere.73-0107
costs arxoneie 28 Ed é be = Pare:va_o107
Bacio
Gaross1 £6 2s . pe - 90107
ew
Burt + Goovstayecne* < 20 Sos” as ° pr Fere.72-0107
bare GoRnue @erosz10e cos 3s é ar : Farai7suo107
ety Gsee3rin Le ae s a Parara_o1o?
Gacioo
eatonnie 05 2s « - Pare.79-0107
. Gacy
(tiny -
pur CocnnsapeNet <20 cos as ° = - Fare.79-0107
Burr} GoQyMoiNGss+ =% oes 3s ‘ Be = Forza_o1e7
men Ga = 18. a rr =
Slox -
katt 4 10." < 108 = Rr nat e - Fern.72-0065
Butt ob Maou (oo enn1o Se Rr nat pe - Fare.72-0065
Eur + Nw oO o2nio oe Rr nat Pe -
ett 4 NO < 10 oon Rr nat - -
rut + Os <0 oe er pe -
Ear + OM wD exe °° Rr nat Pr Measured from
a
(a © 0.2) x 10° - Rr 2 ee - Pitce..78—1004
a Rr ae ee = Sonies oreo
Rae RACH eRe on “Su oe Be Fs ba z ven 7acono7
G5 & 0.2) x 10" 2s « pe - Fare.79-0107
< 2x10 2s 2 pe - Fare.73-0107
eo. ST Tio cd & He = Far{za-ote7
ea Losi 25 s Es = panra_o1o?
(@.0 + 0.6) x 10" 2s . pe - Pare.73-0107
8 $83 5 to 3s s Ee = Breira_otoy

hone are shown here but they should be

29


TABLE 4. Cobalt{I) reactions — Cvutinued

No. Reaction ‘k/dm* mol* 57? * I wc pH Method Comments Ref.
421 Cot + menaquinone—> (4.0 + 0.4) x 10" - RT 7.8 pr Measured by the Rao.73-1047
Co®* + (menaquinone)~ rate of formation Rao.75-1032.
of the semiquinone
in the presence of
ca. 1 mol dmTM*
2-methyl-2-propanol.
(4.1 + 0.1) x 10° -  ca,22 70 pr Measured in the Rao.73-1104

presence of ca, 1
mol dmTM* 2-methyl-

2-propanol.
422 Cot + 1,4 (683 + 0.7) x 10° - a.22 078 pr Measured by the Rao.73-1104
naphthoquinone-2- rate of formation
sulphonate > Cot + of the semiquinone
(1,4-naphthoquinone-2— in the presence of
sulphonate)” ca, 1 mol dmTM*
‘2-methyl-2-propanol.
‘423 Cot + riboflavin > (2.55 + 0.3) x 10° - 2.2270 pr Measured by the Rao.73-1104
Co** + (riboflavin)” rate of formation
of the reduced
riboflavin in the

presence of ca. 1
mol dm"* 2-methyl-

2-propanol.
ColD) complexes
CofCNatTM (from ColCNs*
+ tea)
4.24 — Co(CN)st” + Ha0—> (1+ 0.x - 20 oa. 18 pr Measured in the Vene.71-0097
Co(CN)sH- + OHTM 108s presence of ca.
0.1 mol dm"? Hs.
Proton transfer
mechanism implied
from isotope ef-
fect (compare
entry 4.25).
425 Co(CN)st” + DO > (19 + 0.2)x - 20 © oa. 13 pr Measured in D,0 in Vene.71-0097
Co(CN)sD*- + OD 10's the presence of
ca. 0.1 mol dm-*

CoL* (L = 5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca~4,14~diene)

4.26 CoL* + Hs0 > 20 0.001 RT 9-10 Measured in the Tait..76-1001
CoLH** + OH- presence of 1 mol
dm“* 2-methyl-2-
propanol. See ref.
for evidence for

4.27 CoL* | HOt > 1.2 x 10° 0.015, RT 3.54.2 pr Measured in the Tait..76-1001
CoLH?* + Hs0 presence of 1 mol
dm“? 2-methyl-2~
propanol. See ref.
for evidence for
proton transfer
mechanism.

15


TaBLE 5. Chromium(I), chromium({I) and chromium(V) reactions — Continued

No.

Reaction

k/dm* mol"? 6°? *

I

wc

pH

Method

Comments

Ref.

5.9

5.10

5.11

5.12

5.13

5.14

5.15

Gt + Os

Cet* 4 .CONHs >
CrCONH**

r+ + .CHOH
(CrCH,OH**

Crt + CO >
crC02*

Cr* + .CHaCHO >
CrCHsCHO** or
‘CrCHsCH(OH),"*

Cr** + .CH:COOH >

CrCHsCOOH**

Cr+ + .CHOH.COOH >
(CrCHOH.COOH?*

(1.6 + 0.2) x 10°

(1.6 + 0.2) x 10*

(1.9 + 0.3) x 10°

(6.5 + 0.7) x 10*

1.6x 10°

(1.1 + 0.1) x 10°

3.5 x 10°

25x 10°

14x 10°

2542

RT

2542

2242

2242

2542

2242

2242

21

26-43

1-3

34

14

pr

pr

pr

pr

pr

pr

Measured from the
rate of formation

of CrO,** in the
presence of 0.5

mol dm* 2-methyl-
2-propanol. Produet
characterised by its
absorption spectrum
and by conductivity
measurements.
Measured from the
rate of formation

of Cr02**,

Measured by com-
petition with 1,4~
benzoquinone taking
Cet* + CHO) =
3.2 x 10° dm* mol"!

Measured by the
rate of formation

of the product in

the presence of 1
mol dm"* formamide.
Product characterised
by its absorption
spectrum and decay
kinetics.

Measured by the rate
of formation of the
product. Product
characterised hy its
absorption spectrum
and decay kinetics.
Measured by rate

of formation of the
product in the pre~
sence of 1 mol dm~*
formic acid. Product
characterised by its
spectrum and decay
kinetics.

Measured by the rate
of formation of the
product, which may
be in the form of

an acetal.

Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics,

Sell.76-1134

Ilan..75-1215

Sell.76-1134

Cohe.74-1146

Cohe.74-1146

Elli....73-1057

Cohe.74-1146

Cohe.74-1146

Cohe.74~1146


TABLE 4. Cobalt(l) reactions — Continued

Reaction

‘k/dm® mol" 6? * I wc pH

Method

Comments

Ref.

4.37

4.38

4.39

4.40

441

442

4.43

444

445,

CoL* + Fe(bpy)s** (et)

CoL* + Hs0 >
CoLH** + OH-

CoL* + Hs0* >
CoLH* + 1:0

CoL* + HPOS”
CoLH** + POS

CoL* + HaPOe >
CoLH* + HPO?

CoL* + NHa* >
CoLH* + NHs

CoL* + N20 (et)

CoOL + Oa CoLO:*

CoL* + Ru(NHs)e** (et)

2.3 x10" ca. RT 9.2
0.02

48 0.001 RT) 9-10

3.1x10° 0.015 RT 35-42

1.0 x 10° 0.06- RT 10.0
0.3

98x10" 0.005- RT 55
0.01

6.8 x 10° 0.015- RT 7.0
01

3.9.x 10" 0.01 RT 9.2

LTx10 0.02 RT 92

4.0 x 10° 0.016- RT 9.2
0.028

17

pr

pr

pr

r

Measured in the
presence of 1 mol
dmTM* 2-methyl-2-
propanol.
Measured in the
presence of 1 mol
dm“* 2-methyl-2-
propanol. See ref.
for evidence for
proton transfer
mechanism,
Measured in the
presence of 1 mol
dmTM* 2-methyl-2-
propanol. See ref.
for evidence for
proton transfer
mechanism.
Measured in the
presence of 1 mol
dm”? 2-methyl-2-
propanol. See ref.
for evidence for
proton transfer
mechanism.
Measured in the
presence of 1 mol
dm”? 2-methyl-2-
propanol. See ref.
for evidence for
proton transfer
mechanism.
Measured in the
presence of 1 mol
dm“* 2-methyl-2~
propanol. See ref.
for evidence for
proton transfer
mechanism.
Reaction possibly
involves two elec
tron oxidation to
Co(II) complex.
Measured in the
presence of 1 mol
dm”? 2-methyl-2-
propanol. Reaction
does not involve
formation of CoL?*,
assumed therefore
to involve the
coordination of

the Ox.

Measured in the
presence of 1 mol
dm”? 2-methyl-2-
propanol.

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001


TALE @. Tron(ID and iron(II radical complex reactions

No. Reaction ame mao = 7 we pr Momoa Comments =
aa RE pe Gee Onn Oa 133s oat pr Ba product charac
820 KeHOe Fert + HO. 8 © 0.) x 10" to 208 on ope
Be cardio. bey
Sas
a 88 + 081s
83 FeHOwt 4 Fert Ks & 2ame 1.0 20 0.1 pr Meanured from the 5
Womourer® mort (acio.y os Direc of tes
exer the eben
Koa team Lo 2s on pe FowouresTM
mort Gici0.7 os
narod
Km asia LO 20 oa »
mot Grci0.7 ey
Secess
mos Gc10. bey
Maes,
4 FeHOw + SOu- = K— 90% 20am PO geen 0. pe Menmured from
Saro.s0- mort Garci0., bey pranpes ere
orang Shrine ateorpeion
Se renosrer
85 reHoret @s2onx10 10 20 pr Fumacvesed a
Toe Hos + ree a dato. product,
Snare
anette
Be Ferret + 50 a ee Pr Measured from the
PorrO.resoe* Gac10./ on oe
Nrao oe
oi rtnosees
az 2110.50. —- FeSO." + ea. 104 6+ — eer oa pr FeSO Sharacter—
Sone bey
epectram.
os oa. 108 6-2 — seen one
esOarer HOS 3 Sharecterieed by

30


TasLe 3. Ca(_) reactions — Continued

No. Reaction K/dm? mol" st*# °C pH Method Comments Ref.
Caigly)
3.66 Ca(gly) + BrOs” (et) (6.1 £ 1.2)x10" 021 RT 105 pr - Meye.70-1228
3.67 Calgly) + 105" (et) (18 + 0.4) x10 0.21 RT 105 opr - Meye.70-1228
3.68 Ca(gly) + NOs” (et) @5 + 1.7)x10 0.21 RT 1105p - Meye.70-1228
3.69 Cafgly) + NOs” (et) 24 + 0.5) x10 0.21 RT 1105p - Meye.70-1228
CANTA
3.70 CANTA* + BrOs” (et) (1.02 + 0.2) x 107 0.10 RT 107 pr - Meye.70-1228
3.7L CANTA®” + CANTA? E Vease = (12 0.10 RT 10.7. —pr_—_Unclear whether & Meye.70-1228
(et or af) 0.4) x 10 or 2k.
cms"
K=@+4x 0.10 RT = -10.7._—pr_—_Unclear whether & Meye.70-1228
10° or 2k.
3.72 CANTA?TM + 105" (et) (6.1 + 1.2)x 10° 0.10 RT 107) opr - Meye.70-1228
3.73 CANTA* + NOs” (et) (4.2 + 08)x 10" 0.10 RT 107 pr - Meye.70-1228
3.74 CANTA*” + NOs” (et) (45 + 0.9)x 107 0.10 RT 10.7 pr - Meye.70-1228
Ca{D-radical complexes .
3.15 CACHSCHOH* + Hs0 > 257 s* - RT nat pr Products inferred Kelm..75-1004
Ca#* + CH.CHAOH + OHTM from conductivity
measurements.
3.76 CACHsCOHCHs* + Ha0 161s - RT nat pr Products inferred Kelm..75-1064
Ga! + CHCHOHCHs + OH from conductivity
measurements.
3.77 Cds** + -CHa(CHs),COH ca. 1x10" - RT nat pr __Isobutene detected Kelm..75-1064
Cat + Ca?* + (CHs)sC=CH: + OHTM as product.

If the data source gives no errors none are shown here but they should be assumed to be at least -+25% (or +50% for 2k).

12


‘TABLE 21. Thallium(0) and (II) reactions — Continued

No. Reaction ‘/dm? mol" s* * I wc pH Method Comments Ref.
2113 Th* + 1,4-dicyano— 2.7 x 10° - RT pr Organic product Robi.73-0121
benzene —> 271" + characterised by
(1,4-dicyanobenzene)” its absorption
spectrum.
TE (Rate constants from pulse radiolysis and flash photolysis experiments only).
Tig and TIOH*
2114 THY + Cot = hy = 62 + 0.5) x 10" 0.75 25 0.6 fiph. Evidence for Fale..74-7625
TI* + Co* products and equili—
brium from conven—
tional kinetic studies.
2115 TH + Cot (@5405)x10* 0.55 222 03 kph. Evidence for Fale..75~7093
THY + Cort products from
conventional kinetic
studies.
21.16 TH + Fett (2.42 + 0.1) x 10° 030 14.7 = 0.6._~—fiph. Evidence for pro~ Fale..75~-7093
Tit + Fe ducts from conven—
tional kinetic
studies.
(2.50 + 0.1) x 10° 030 «18.306 ~—siph. Fale..75-7093
(2.53 + 0.1) x 10° 030° 207 «06 =~ Eph, Fale..75~7093
(2.60 * 0.1) x 10° 0300 248 0.6 Eph. Fale..75-7093
(2.70 + 0.1) x 10* 0.30 © 29.006 =~ ph. Fale..75~7093
(2.73 + 0.1) x 10° 0.30 © 38.9 «06 iph. Fale..75~7093
(2.81 + 0.1) x 10 0.30 26.0 0.6 fph. Fale..75~7093
2.91 + 0.1) x 10° 0.30 © 396 = 06 siph. Fale..75~7093
E,=48+2ks mol 0.30 14-40 06 — Eph. Fale..75~7093
©7£07)x10° 1 23 0 Pr Schw...74-1017
(ACIO,)
2117 TPt + Fett = (1 + 0.15) x 10 030 © 25 0.6 ph, Evidence for pro~ Fale..74-7625
TH + Fert ducts and equilibrium
from conventional
kinetic studies.
21.18 Ti+ + HO, > 2.5 + 1)x 10° - RT 1 pr Estimated from ini~ Cere..66-0097
Tit + Ht +02 tial decay of TI”
in aerated solutions.
2119 Ti+ + HOS pK = 46 +02 var 21 27 pr Evidence for O'Ne.75-1130
TIOH* + Ht ky = 3.5% 108 8 var 21 2-7 pr rium from optical and
ky = (14 + 0.5) x 10 var 21 27 pr conductivity measurements.
21.20 THY + H.0.—> 2.8 + 08) x10" - RT 1 pr Evidence for pro- Cere..66-0097
Tt + HOs + Ht ducts from HaOs and
Ha yields in y—irradi~
ated TH solutions.
(sce ref. 71-0036).
2121 Tt + Mutt .9+02)x10 0.75 «= 223 0.3 ~— Eph. _Evidence for pro~ Fale..75-7093
Tit + Mn** ducts from conven—
tional kinetic
studies ete. (eee
ref. 75-7093).
2122 TH+ Os > 2x10 - RT 52 y Rate constant and Fara..71-0036
TH + Oa products deduced
from HaOs and Ha
yields in y—irradi—
ated TH solutions.
No account taken
of hydrolysis of
TiF* (cee entry 21.19).
2123 TH + Te see entry 21.6
21.24 TH! + Tht see entry 21.12


Reaction:

Rate Constant:

Tonic Strength:
C1)

Temperature:
pH:
Method:

Chemical Symbols:

List of Abbreviations

dis

et

int et
Oat
pt

et - is

2k

PEABS

var
RT
nat
comp.
f.ph.

pr
bpy

en

sly
EDTA
NAD+
NTA
PNDA

adduct formation

dismutation (disproportionation)

electron transfer

intramolecular electron transfer

oxygen atom transfer

proton transfer

inner sphere electron transfer

uncertain

rate constant for second order reaction

extinction coefficient at wavelength A

activation energy (units kJ mol?)

equilibrium constant

acid dissociation constant (= -logioK)

rate constant for forward reaction of
equilibrium

rate constant for reverse reaction of
equilibrium

value uncertain

extrapolated to zero ionic strength

calculated taking into account the
formation of ion pairs

various

room temperature

natural pH of the solution

competition kinetics

flash photolysis

‘y-radiolysis

pulse radiolysis

bipyridy!

ethylenediamine

glycine

ethylenediamine tetraacetate

nicotinamide adenine dinucleotide

nitrilotriacetate

p-nitroso-N,N-dimethylaniline

ligand (specified in table).


TABLE 6. Copper(l) and copper(IIl) reactions — Continued

No. Reaction k/dm* mol* s* * I we pH Method Comments Ref.
631 CuL* + 9,10-anthra~ (l1+01)x10° 0.008 «= RT) 7.0 pr Measured in the Tait..76-1039
quinone-2-sulphon— presence of 1 mol
ate (et) dm”? 2-methyl-2-
propanol.
6.32 CuL* + 1,4-benzo- (2.6 + 0.3) x 10° 0.004 RT 7.0 pr Measured in the Tait..76-1039
quinone (et) presence of 1 mol
dm“? 2-methyl-2-
propanol.
6.33 CuL* + 3-benzoyl- no reaction 0.004 «RT 70 pr - Teit..76-1039
pyridine observed
6.34 Cult + eosin Y no reaction 0.006 «RT 7.0 ia - Tait..76-1039
observed
6.35 — CuL* + fluorescein no reaction 0.004 «=« RT 7.0 pr - Tait..76-1039
observed
6.36 CuL* + methyl iodide (.1+0.3)x10* 0.01 RT (92 pr Measured in the Tait..76-1039
(et or Sy2) presence of 1 mol
dm ° 2-methyl-2—
propanol.
Cult) Reactions
Cu(E) aquo ion (Cu(OH)s, Cu(OH)s* and CuO)?
6.37 CuOH?' = Cu(OH)s! + pK = 24+ 0.2 var 25 0.6 pr _ Degree of hydro- Sell72-0844
Ht lysis deduced from
conductivity experi-
ments (see ref.
70-0512).
Note: pK of this value
is also in keeping
with the data of
Baxendale et af (ref.
65-0394) and of
Meyerstein (ref. 71-
0174) taking into
account equilibrium
, 6.39.
pK =3.05+0.05 var RT 9.27 pr - Baxe..65-0394
638 © Ci(OH)s* = hy = (4.2 1.4) var RT = 3.50 pr_—Estimated from decay Baxe..65-0394.
CuOH* + OH x 10s of Cull in the pre—
and K = 13x sence of Br”, CHOH,
107¢ dm* mol HaOzete. Values of
k= 28410) var RT 3.65 pr _—fy taken to be same
x10¢s as MCu* + OH).
and K = 9.0x
10°* dm* mol*
6.39 Cu(OH).* = pk >6 var 25 0-6 pr - Sell72-0844
Cy(OH)s + H”
6.40  Cu(OH)at + Cut (et) (18 +0.6)x10" 0.00325 48 pr Estimated from decay Sell72-0844
of Cu! in deaerated
solutions.
(1.6 £0.5)x10* 0.00825 6 pr Possibly some contri— Sell72~0844
bution from Cu(OH)s +
Cut,
(B6+12)x10° 0.002» «RT ont pr Possibly some con- Meye71-0174
tribution from
Cu(OH)s + Cu*.
641 Cu(OH)s* + Cu(gly)* @1405)x10" 0.008 «= RT 5.5 ra - Meye71-0775

(et?)

27


Tawie 24. Zine() reactions — Continued

No. Reaction k/dm? mol" s#* uC pH Method Comments Ref.
24.29 Zn* + H.O* <l0e 0.08 =—RT - pr
24.30 Zn* + 10s” (et) (86+05)x10° 0.08 RT nat pr
(L7 + 0.3)x10% 0.4 RT 5-8 Y
(ZnS0,)
2.1 x 10° dm? mol"
$7 (eee entry 24.33).
24.31 Zn* + Nit (et) <5x10 008 = RT nat pr - Meye.68-0855,
Sxl = RT nat Pr - Baxe..66-0848
24.32 Zn* + NOs" (et) @22+0.3)x10° 0.08 = RT nat, Pr - Meye.68-0855
24,33 © Zn* + NOs" (et) @14£0.3)x10° 0.08 = RT pr - Meye.68-0855
24.34 © Zn* + NO <13 x100 0 RT nat Pr - Meye.68-0855
Zn0* + Na 8.7 + 0.4) x10" - 2542 nat pr Products charac Bust..76-1072
35.5 + 14K) - 1-30 nat pr __terised by their
mol-* absorption spectrum
(see ref. 76-1072)
and in y-radiolysis,
experiments (see
ref. 73-0039).
2435 Zn* + O— (2.4 + 0.4) x 10° - RT nat pr - Meye.68-0855,
Zn** + O37 3.3 x 10° - RT nat Pr - Baxe.,66-0848
Products charac—
verised by their
absorption spectrum
(cee ref. 76-1072)
and reactivity with
1,4-benzoquinone (see
ref. 76-1134).
24.36 Zn* + OH (et) S.7x10e = RT nat pr No correction made Baxe..66-0848
for competing reac
on Zn* + Zn*.
ca. 8 x 10° - 2542 nat pr Estimated from Buxt.75-1027
decay of Zn* in
the absence of OH
scavengers taking
into account compet-
ing reactions such
as Zn* + Zn*, Zn* +
H202, OH + OH etc.
24.37 Zn* + Pb** (et) 400x108 0 - RT nat Pp - Baxe..66-0848
2438 — Zn* + Rubpyh* (et) 25x10 = RT nat Pr - Baxe.72-0381
24.39 Zn* + Ru(NHs)e** (et) 2.2+0.3)x10° 0.08 RT nat Pr - Navo.70-1229
24.40 Zn* + Si0eTM > (1.3 0.1)x10" 0,02" 252 nat Pa - Buxt..76-1072
Zn** + SO.” + SOF
24.41 © Zn* + Znt 2k< 8x1 0.4 = 2542 nat pr Estimated from rate Buxt.75-1027
of decay of Zn* in
the presence of 2~
methyl-2—propanol,
Major competing reac—
tion is Zn* +
-CHsC(CHs):0H.
2442 — Zn* + allyl alcohol > ca. 108 - 2542 nat pr Product characterized Buxt..76-1072
(Zn - allyl alcohol)* by its absorp-
tion spectrum.

63


‘TABLE 25. Intramolecular electron transfer

reactions for some metal complexes*

No. Reaction kis 7 °C pH ~— Method = Comments Ref.
Electron adducts
25.1 (NHs)sCoTM(p-OOCC.H.NOs)” > 2.6 x 10° - RT 7.0 pr - Simi..77-1027
(NH)sCo"(p-OOCCAHANOs)
25.2 (NHs)sCoTM(m-OOCCsH.NOs)” —> 15 x10" - RT 7.0 - Simi..77-1027
(NHs)sCoTM(m-OOCCsH.NOs)
28.3 (NHs)sCoTM(o-OOCCsH,NO2)” —> 4.0 x 10" - RT 7.0 - Simi..77-1027
(NH,)sCoTMo-OOCC.H.NO:)
25.4 (NHs)sCoTM(o-OOCC.H.NOsH) —> 9.5 x 10* - RT 08 pr - Simi..77-1027
(NH,)xCoTMo-OOCCH.NO,) + Ht
25.5 (NHs)sCoTM[2,4-OOCCH«(NOshI- 3.5 x 10* - RT 7.0 - Simi..77-1027
=> (NHs)sCoTM[2,4-OOCCsH.(NOs)a]
25.6 (NHs)sCoTM3,5-OOCCsH«(NOs)3)” 13x10 - RT 7.0 - Simi..77-1027
—> (NH )sCoTM[3,5-OOCC.H,(NO2)s]
25.7 CuTM(gluthathioneTM) —> 8.6 + 0.3) - RT u pr Fara.76-1016
CuYgluthathione) x10
in range 1:2 to
1:5 and of (CaTM]
in the range
(2-10) x 10* mol
dm",
25.8 CuMgly)a(gly-) (1.7 + 0.3) - RT 9 pr Rate constant Fara.76-1016
Catgly)s x10¢ independent of
[Cu"}: [gly]
ratio in range
1:6 to 1:15 and
of [Cu] in the
range (1-10) x
107* mol dm*.
Hydroxyl radical adducts
25.9 (NHs)sCoTMOOCC.HOH —> <1e - RT 6.0 pr - Cohe.71-0282
(NH,)sCo"OOCCH.OH + H*
Hydrogen atom adducts
25.10 (NHs)sCoTMOOCC.HsH < 10 - RT 1 pr - Cohe.71-0282

(NHs)sCo"OOCCsH.H + H*

“Intramolecular electron transfer reactions of metallo-proteins and related systems not included...

°N.B. First order rate constants.


62-0164

64-0133

65-0385

65-0393

65-0394

65-0799

66-0848

67-0019

67-0062

68-0169

68-0302

68-0431

68-0435

68-0855

69-0144

69-0428

69-0971

References

Radiolysis of compounds of the noble metals in
aqueous solution. I. Action of gamma rays on the chlorides of
Pil and Pt in acid solution, RADIATION RES. 17(3): 274-85
(1962).

Asmus, K.-D; Henglein, A; Ebert, M5 Keene, J.P.
Pulsradiolytische Untersuchung schneller Reaktionen von
hydratisierten Elektronen, freien Radikalen und Ionen mit
Tetranitromethan in waessriger Loesung, BER. BUNSENGES.
PHYS. CHEM. 68: 657-63 (1964).

Baxendale, JH; Keene, J.P. Stott, D.A., Determination of
some fast reaction rates using the pulsed radiolysis of
permanganate solutions, Pulse Radiolysis, Ebert, M.; Keene,
J.P. Swallow, AJ; Baxendale, J.H. (eds), Acad. Press, N.Y.,
1965, p. 107-15.
Baxendale, J.H.; Fielden, E.
Ag* solutions, Ibid., p. 207-16.

Baxendale, J.H.; Fielden, E.M.; Keene, J.P., Formation of CuTM
in the radiolysis of Cu** solutions, Ibid., p. 217-20.

Cordon, S., Ibid., p 285.

Cercek, B.; Ebert, M.; Swallow, AJ., Novel valence states of
thallium as studied by pulse radiolysis, J. CHEM. SOC. PT. A
(5): 612-5 (1966).

Baxondale, J.H.; Keone, J.P.s Stott, D.A., Reactions and relative
potentials of some metal ions in unstable valence states, CHEM.
COMMUN. 715-16 (1966).

Konstantatos, J.; Katakis, D., The radiolysis of concentrated
neutral sodium perchlorate aqueous solutions, J. PHYS. CHEM.
71(4): 979-83 (1967).

Buxton, G.V.; Dainton, F.S; Thielens, G., Kinetics of reactions
of the hydrated electron, CHEM. COMMUN (4): 201 (1967).
Dainton, F.S; Wiseall, B., Reactions of nitrosodimethylaniline
with free radicals, TRANS. FARADAY SOC. 64(3): 694-705
(1968).

Adams, G.E.; Broszkiewic, R.B; Michael, B.D., Pulse
radiolysis studies on stable and transient complexes of
platinum, TRANS. FARADAY SOC. 64(5): 1256-64 (1968).
Ghosh-Mazumdar, A.S.; Hart, E.J., A pulse radiolysis study of
bivalent and zerovalent gold in aqueous solutions, ADVAN.
CHEM. SER. 81: 193-209 (1968).

Pukies, J.; Roebke, W.; Henglein, A., Pulsradioytische Unter-
suchung einiger Elementarprozesse der Silberreduktion, BER.
BUNSENGES. PHYS. CHEM. 72(7): 842-7 (1968).

Pukies, J.; Roebke, W., Pulsradioytische Untersuchung der
Reduktion des Ag*-Ions in ammoniakalischer Loesung, BER.
BUNSENGES. PHYS. CHEM. 72(9/10): 1101-5 (1968).
Meyerstein, D.; Mulac, W.A., Reductions by monovalent zinc,
cadmium, and nickel cations, J. PITYS. CHEM. 72(3); 784-8
(1968).

Ghosh-Mazumdar, A.S; Hart, EJ., Electron pulse radiolysis of
aqueous tetrachloro and tetracyano complexes of Pt, INT. J.
RADIAT. PHYS. CHEM. 1; 165-76 (1969).

Meyerstein, D.; Mulac, W.A., Reduction of cobalt(III) complexes
by monovalent zinc, cadmium, and nickel ions in aqueous
solutions, J. PHYS. CHEM. 73(4): 1091-5 (1969).

Jayson, G.G.; Keene, J.P.; Stirling, D.A; Swallow, AJ., Pulse—
radiolysis study of some unstable complexes of iron, TRANS.
FARADAY SOC. 65(561): 2453-64 (1969).

Taylor, R.S.; Sykes, A.G., Preparation, spectrum, and stability
of indium(1) in aqueous solution, J. CHEM. SOC. PT. A 2419-
23 (1969).

‘eene, J.P., Pulse radiolysis of

66

70-0117

70-0178

70-0336

70-0512

70-0580

70-1228

70-1229

70-7309

10-7726

71-0036

71-0097

71-0174

71-0234

71-0282

71-0775,

72-0065

72-0066

72-0290

Fit, M., La cinetique de competition dans V'etude des
rmediaires instables. I. Les ions Cot, Mn*, Zn*, Cd* et
Nit, REV. ROUM. CHIM. 15(1): 77-85 (1970).

Baxendale, J.H.; Rodgers, M.A.J.; Ward, M.D., Radiolysis of
aqueous solutions of ruthenium (II) hexa-ammine and
chloropenta-ammine, J. CHEM. SOC. PT. A (8): 1246-50
1970).

Burchill, C. G.G., Radiation-induced oxidation of
alcohols by TI(III) in acid aqueous solution, CAN. J. CHEM.
48(16): 2466-73 (1970).

Barker, G.C; Fowles, P., Pulse radiolytic induced transient
electrical conductance in liquid solutions. Part 3. Radiolysis of
aqueous solutions of some inorganic systems, TRANS.
FARADAY SOC. 66(7): 1661-9 (1970).

Baxendale, J.H.; Koulkes-Pujo, A.-M., Une etude par radiolyse
pulse sur l'espece transitoire Au Il, J. CHIM. PHYS. 67(9):
1602-7 (1970).

Meyerstein, D.; Mulac, W.A., The effect of ligands on the
chemical properties of monovalent cadmium ions, INORC.
CHEM. 9(7): 1762-6 (1970).

Navon, G.; Meyerstein, D., The reduction of ruthenium(II)
hexsammine by hydrogen atoms and monovalent zinc,
cadmium, and nickel ion in aqueous solutions, J. PHYS.
CHEM. 74(23): 4067-70 (1970).

Burchill, C.E.; Wolodarsky, W.H., The photochemistry of
aqueous solutions of TI(IIl) perchlorate, CAN. J. CHEM.
48(19): 2955-9 (1970).

Thornton, A.T.; Laurence, G.S., The rates of oxidation of Fe*,
Mn**, and Cot by Bra” radical ions, CHEM. COMMUN. 443-4
1970).

Faraggi, M.; Zehavi, D.; Anbar, M., Effect of thallous ions on
the yields of hydrogen and hydrogen peroxide in radiolyzed
aqueous solutions, TRANS. FARADAY SOC. 67: 2057~
ag71).

Venerable, G.D.I; Halpern, J., Pulse radiolysis of aqueous
solutions of pentacyanocobaltate({I). The detection and
characterization of pentacyanocobaltate(|), J. AMER. CHEM.
SOC. 93(9): 2176-9 (1971).

Meyerstein, D., Trivalent copper. I. A pulse radiolytic study of
the chemical properties of the aquo complex, INORG. CHEM.
10(3): 638-41 (1971).
Baxendale, J.H.; Mulazzani, Q.
reduction of Ru(NHs)sN2** by y-
J. INORG. NUCL. CHEM. 33(
Cohen, H.; Meyerstein, D., Oxidation of benzoatopentaammine-
cobalt(III) by hydroxy! radicals, J. AMER. CHEM. SOC. 93(17):
4179-83 (1971)

Meyerstein, D., Trivalent copper. II. A pulse radiolytic study of
the formation and decomposition of amino complexes, INORG.
CHEM. 10(10): 2244-0 (1971).

Faraggi, Mj Tendler, ¥., Pulse radiolysis in lanthanide ayucvus
solutions. 1. Formation spectrum and chemical properties of
divalent europium, ytterbium, and samarium ions, J. CHEM.
PHYS. 56(7): 3287-93 (1972).

Faraggi, M.; Feder, A., Pulse radiolysis studies in lanthanide
aqueous solutions. II. Formation, spectrum and some chemical
properties of praseodymium(IV) in aqueous solution. J. CHEM.
PHYS. 56(7): 3294-7 (1972).

Faraggi, M.; Amozig, A., Pulse radiolysis of metallic ions in
aqueous solutions. I. Pulse radiolysis in Hg** and Hg.** ions in

A study of the oxidation and



‘Taste 6. Copper(l) and copper(II) reactions

No.

Reaction

k/dm?* molTM sTM* *

I wc

pH

Method

Comments Ref.

61

62

6.3

65

66

67

68

69

6.10

Cut
Cu* + Cu(OH)s* (et)

Cut + MnO." (et)

Cut + NsO

Cu* + -CH,O1 =
CuCH,0H*

Cut + (CHs)COH >
CuCOH(CHS).*

CuCOH(CHs):*4. Ht >
Cut + products

Cu* + -CH,CH:OH >
CHs=CHs + OH” + Cu?*

Cut + -CHs(CH,),COH —
‘CuCH.(CHs)COH*

Cut + acrylamide =
Cu-aerylamide*

Cu* + benzoquinone

(L.8 + 0.6) x 10°
(1.6 + 0.5) x 10°

(8.6 + 1.2) x 10°
5x10

(6.4 + 0.6) x 10°

yea. 10%

Ay ca. 10° sTM*

ca. 6 x 10°

32x10"

1.9 x 10%

2.6 x 10°

K=(@1+0.1)x
10* dm? mol*

hy = 2x 10°

Ay = 1.1.x 10% 8?

< 10°

0.003 25,
0.003 25
0.002 «RT

0.08

0.004 = 25

- 25+2

24

48

6

nat

nat

nat

45

45

345

45

45,

25
25

49

pr

pr

pr

pr

pr

See comments under Sell72-0844
entry 6.37.
See comments under Sell72~0844
entry 6.37.

- Meye71-0174
Measured by the Baxe..65-0385
rate of depletion
of the MnO.” ab-
sorption. Depen-
dence of & on {Cu?*]
detected.
Measured by the Sell72-0844
rate of depletion
of the MnO,” ab-
sorption.
Estimated from Ng Sell72-0844

+ N20 solutions.
Idemtity of product Buxt.77-1500
inferred from its

absorption spectrum.

Rate constants esti Buxt.77-1500
mated from rate of

growth and decay of

‘CuCH,OH*.

Identity of product Buxt.77-1500
inferred from its

absorption spectrum.

Estimated from de~ Buxt.77-1500
pendence of decay of

absorption attri—

buted to CuOH(CH,)a*

on [H*] (see entry 6.5).

Estimated from yields Buxt.77-1500
of Cu! in y-radiolysis

of Cutt + CaH solutions.

Products inferred from

data for entry 6.8.

Product inferred Buxt.77-1500
from its absorp—

tion spectrum. Esti~

mated from yields of

Cut in the Y-radio—

lysis of Cu®* + 2-

methyl-2—propanol +

aH, solutions. Final

product is CHa=C(CHs)s.

Measured from the Buxt..76-1186
effect of [acryl-

amide] on the yield

and rate of formation

of Cu-acrylamide*.

Estimated from the Sell.76-1134

non-formation of

benzosemiquinone in

the pulse radiolysis

of Cu?* + benzoquinone

solutions.



Compilation of Rate Constants for the
Reactions of Metal Ions in Unusual

Valency States*

George V. Buxton and Robin M. Sellers**

Gookridge Radiation Research Centre, Cookridge Hospital,
Leeds L$16 6QB, Great Britain.

Kinetic data have been compiled for reactions of uncommon oxidation states of metals which are
produced by radiolysis of aqueous solutions of metal ions. Most of the reaction rates are for transient species,
and the rates were determined by pulse radiolysis; some data were obtained by flash photolysis and gamma
radiolysis. Metal ions from Groups IB, IIB, IIIA, IVA, VIB, VIIB, VIIIB, and the lanthanides are included
in the compilation.

Key words: Aqueous solution; chemical kinetics; complex ions; electron transfer; metal ions; radiation
chemistry; rates; transients...

Introduction

The discovery of the hydrated electron as a major product of the radiolysis of water and the development of
pulse radiolysis have together resulted in the accumulation, during the last ten years, of a considerable amount of
information on the chemistry of unusual valency states of metal ions in aqueous solution, which has been reviewed
recently (G. V. Buxton and R. M. Sellers, 77-0121).1 For the most part attention has been focussed on hyper
reduced states produced in reaction (1), which affords a simple, and often unique, method of their formation.
Reactions of hydroxy! radicals and hydrogen’ atoms, and of simple radicals derived from them, with metal ions have
been less commonly studied.

iq + Mt > M@-ot a
2M@-D+ _, Met 4 Mie-2)+ (2)
M@-D+ 4 S$ + products (2)

This compilation lists the rate constants for reactions of these metal ions in unusual valency states. In the
majority of cases the species are unstable, generally decaying by dismutation (2), or reaction with the solvent or a
solute (3). This instability has been the principal criterion on which the decision to include data in this tabulation
has been based. However, because the bulk of information on these metal ions has been obtained by pulse radiolysis
methods, we have also included some rate constants for the reactions of stable metal ions such as Cu*, Cr?* and
Eu** measured by these methods. In these examples, indicated in the tables, much other data not recorded here has
been obtained by other techniques.

‘This is data review prepared for, and in cooperation with, pthe Radiation Chemistry Data Center of the Redistion Laboratory, University of Notre Dame, Indiana 46556, The
Laboratory is operated under contract with the Department of Energy. The work of the Center is supported in part by the National Bureau of Standards, Office of Standard Reference Data.
**Present addres: Central Electricity Generating Board, Berkeley Nuclear L Berkeley, G ire GL13 9PB, Great Britain,

‘Literature references are given at the end of this paper.




TABLE 4. Cobalt(I) reactions

No. Reaction k/dm? mol" 6? * I we pH Method Comments Ref.
Coreg
41 Cot + Bra” (et) (1.0 + 0.3) x 10 - RT nat fph. — Competing reac ‘Thor.70-7726
tions Bra” + Bra
and Co* + Co* not
considered.
42 Cot + BrOs” (et) (48£0.5)x10 0.019" = 2542 nat pr - Buxt..76-1072
(1 + 1.1) x 10° +0 25+2 nat pr - Bust..76-1072
43 Cot + Catt <10 - RT nat pr - Baxe..66-0848
44 Cot + Cot (et or af 2k < 4x 10° 0.019" 252 nat. pr Estimated at 370 Bust.75-1027
nm taking ésr0 =
2080 dm? mol“
em,
45 Cot + Cut (et) (41 0.4)x10" 0.019" 2542 nat pro - Buxt..76-1072
(2.06 + 0.36) x 10% 0.04 RT 5-8 Measured by compe- Fiti70-0117
tition kinetics
‘using NOs” a8 com-
petitor and taking
HCo* + NOs”) = 18x
10° dm* molTM $7
46 Cot + HiOs—> (1.6 + 0.2) x 10° - 25 nat pr - Bust..76-1072
Cot + OH + OHTM 19x 10° - RT nat pr - Bust..67-0062
Ey = 13.0410 - 1-30 nat pr - Bust..76-1072
WJ mol Products identified
in y-radiolysis,
studies (see ref.
73-0039).
47 Cot + 10s" (et) (4.3 + 0.4) x 10° 0.019% 2542 nat pr - Buxt..76-1072
(4.9 + 0.8) x 10° 0.04 RT 5-8 Y Measured by compe~ Fiti70-0117
tition kinetics
using NOs~ a8 com-
petitor and taking
(Cot + NOs) =
1.8 x 10° dm*
mol~* 5-3.
48 Cot + Mn0x (et) 1.06 x 10% ca. 20 nat pr Measured by the Baxe..65-0385
0.004 rate of depletion
of the MnO." ab-
sorption.
49 Co* + NaO —> CoO* + Ne 7x 10° - RT nat y Estimated from Ns Buxt..67-0062,
yields in the y—
radiolysis of CoTM*
+ Na0 solutions.
(1.0 + 0.1) x 10° - 2542 nat pr - Buxt..76-1072
Products inferred
from ‘y-ray induced
chain reaction in
the system Co®* +
HCO.” + Nj0. (see
ref. 73-0039).
4.10 Cot + NOs” (et) (18 + 0.2) x 10° 0.019 2542 nat pr - Bust..76-1072
4.11 Cot + Nit* <1 - RT mat pr - Baxe..66-0848

13


Equilibrium constants are quoted under the ‘Rate Constants’ heading, and are prefixed by “K —” followed by
the appropriate units. If the individual rate constants for the forward and reverse processes are known these are
shown as “k;” and “k,” respectively. Activation energies are prefaced by “E, =” and are given in units of kJ
mol”.

Ionic Strength (J): Ionic strengths have either been taken directly from the original work, or calculated from
the conditions given. In the few instances where the formation of ion pairs has been taken into account the values
are followed by an asterisk. If insufficient information is given to enable the ionic strength to be calculated the
column has been left blank. The ionic strength of rate constants extrapolated to zero ionic strength is given as “—>
0”. Unfortunately in a number of studies little or no attempt has been made to maintain the ionic strength constant.
The practice of many reaction kineticists of adding a high concentration of inert electrolyte, such as NaClO,, has not
been widely adopted by radiation chemists, no doubt because of possible complications due to direct radiolysis of the
electrolyte (cf. J. Konstantatos and D. Katakis, 67-0019). There is no reason however why an ionic strength of say
0.1 or 0.5 mol dmTM$ should not become standard for pulse radiolytic measurements. It is to be hoped that more
consideration will be given to this problem in future studies.

Temperature: Where temperatures are quoted in the original work these have been given. In the absence of
any information temperatures are given as room temperature (RT). The temperature ranges over which activation
parameters have been measured are given as appropriate. Since many of the rate constants quoted in these tables are
near the diffusion controlled limit and have therefore small activation energies, little uncertainty is engendered by
an imprecise knowledge of the temperature. For example a change in temperature of 5° from 25° changes k by 11%
for an activation energy of 16 kJ mol.

Comments: Information and comments relevant to the reactions and rate constants are given in this column as
outlined above. No attempt has been made to give a complete description of the conditions employed in the
measurement of the rate constants quoted, but where the concentration of one or more of the solutes exceeds 0.1
mol dm this has been noted.

References: The references are listed following the tables in order of the serial number of the paper in the
files of the Radiation Chemistry Data Centre at the University of Notre Dame. The first two digits of this number
represent the year in which the work was published. The references in the tables also give the first four letters of
the first author's name and a dot for each additional author up to a maximum of four dots.


TABLE 4. Cobalt(1) reactions — Continued

No.

Reaction

A/dm? molTM s~* *

I

wc

pH

Method

Comments

Ref.

454

4.55

4.56

4.57

4.58

4.59

4.60

CoL* + Cr(bpyls** (et)

CoL* + Hs0* >

CoLH?* + HiO

CoL* + Os > CoLO.*

CoL* + acetic acid >
CoLH** + CHsCOO-

CoL* + 9,10-anthraquinone—
2,6-sulphonate — CoL?*
+ (9,10-anthraquinone-
2,6-sulphonate)”

CoL#* + (indigosulphonate)TM

CoL* + riboflavin >
CoL?* + (riboflavin)

1.6 x 10"

1.6 x 10*

11x10

6.2 x 10*

3.8 x 10°

4.9 x 10°

1.0 x 10°

0.016-
0.028

0.06-
0.6

0.02

0.01-
0.05

0.004

0.004

0.004

RT

RT

RT

RT

RT

RT

RT

65

0.25-
1.25

65

48

65

65

65

Pr

Pr

Pr

pr

pr

Measured in the
presence of 1 mol
dm“? 2-methyl-2—
propanol.

Measured in the
presence of 2 mol
dm”? 2-propanol.
See ref. for evi~
dence for proton
transfer mechanism,
Measured in the
presence of 1 mol
dm”? 2-methyl-2-
propanol. Reaction
does not involve
formation of Col*,
assumed therefore
to involve the
coordination of Os.
Measured in the
presence of 2 mol
dm“ 2-propanol.
See ref. for evi-
dence for proton
transfer mechanism.
Measured in the
presence of 1 mol
dm“* 2-methyl-2—
propanol. Semi~
quinone product
characterised by

its absorption.
Measured in the
presence of 1 mol
dm”* 2-methyl-2—
propanol. Radical
anion product char—
acterised by its
absorption.
Measured in the
presence of 1 mol
dm 2-methyl-2—
propanol. Radical
anion product char-
acterised by its
absorption.

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

‘Tait..76-1001

Tait..76-1001

‘Tait..76-1001

“If the data source gives no errors none are shown here but they should be assumed to be at least +25% (or 50% for 2k).

19


Compilation of Rate Constants
for the Reactions of Metal lons
in Unusual Valency States

George V. Buxton and Robin M. Sellers

Cookridge Radiation Research Centre,
Cookridge Hospital,

Leeds LS16 6QB,

Great Britain

U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps, Secretary
Dr. Sidney Harman, Under Secretary
Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued June 1978


TAwLE 14, Nickel) and nickel(II) reactions — Continued

Ne. Reaction ‘kam? mol oe 7 we Pt

3479 ~(NIL* +} RetNHDe* GO @s HOsx10 oo1e- RF 70

aae0 | NLT @.5-0.4)x107 O.016- RT 70 Tait..76-
RudNH)eNO (oo 0.028

14.81 NIL* + acetic acta 9 0.2)210° 0.0155 RT aes
ms) 0.06

aaes (5.0 £0.5)x 10" 0.004 70

14.83 NiL* + 1.4-benzoquinone — (B.8 =H 0.4) x10% 0.004 er 70 waite
eo

aga NEL* + 3_bensoylpyri— (7.5 © 0.8) x10" 0.004. Rr 70 Tait 76
dine (od

14.85  NiL* + cosin ¥ ed (2.7 0.3) x10" 0.004. Rr 70

14.86 NiL* + Auorescein (oo (3.54 0.5) x 10" 0.004 Rr 70 Taie.76-

14.87 NiL* + methyl todide G8 £01)~x10" 0.01 Rr on waie76,
(et oF 5n2)

aass NidHsou® Ho - Rr nat Kelm...74

14.89 NiCH.OH + HAsO. (ot?) Rr at

14:00 NICO. + H.O = RT mat

2401 | NiGH,ONT + HO Rr nat
Ne GOH + On

14.92 NIGHOH* 4 140. 2) - RT

14.98 © NiGOH(GH.)." + BLO = Rr

1a0a = Re

14.96 = Rr



TABLE 1. Silver(0) and Silver(II) reactions — Continued

No. Reaction kam molt st* wc pH Method Comments Ref.

113 Agi + 1,2-dimethoxy- (6.0 + 0.6) x 10" - 2042 — nat(?) pr Product charac~ O'Ne..75-1171
benzene + Ag* + terised by absorp— .
(1,2-dimethoxybenzene)* tion spectrum and

esr.

1.14 Agt* + 1,3-dimethoxy- (6.3 + 0.6) x 10" - 202 —nat(?) product charac— O'Ne..75-1171
benzene —> Ag* ++ terised by absorption
(1,3-dimethoxybenzene)* spectrum and esr.

115 Agi + 1,4-dimethory- (4.6 + 0.5) x 10" - 202 —nat(?)—pr_-——Product character— O'Ne..75-1171
benzene — Ag* + ised by absorption
(1,4-dimethoxybenzene)* spectrum and esr.

1.16 Agt* + 1,2,3-trimeth— 2.5 + 0.3) x 10? - 202 — nat(?) pr Product character— O'Ne..75-1171
oxybenzene —> Ag* + ised by absorption
(1,2,3-trimethoxy— spectrum and esr.
benzene)*

LAT Ag + 1,2,4tri- (2.0 + 0.7) x10" - 2042 — nat(?) pr Product character O'Ne..75-1171
‘methoxybenzene —> ised by absorption
Agt + (1,2,4-trimeth— spectrum and esr.
oxybenzene)*

118 Ag + 1,3,5-tri- 6.6 + 0.6) x 10" - 20+2 nat(?) —ppr_—_—Product character— O'Ne..75-1171
‘methoxybenzene —> ised by absorption
Ag* + (1,3,5-trimeth— spectrum and esr.
oxybenzene)*

"If the data source gives no errors none are shown here but they should be assumed to be at least -+25% (or +50% for 2k).

TABLE 2. Gold(0) and Gold(II) reactions
No. Reaction kfm? molt st* wc pH Method Comments Ref.
Au(0) from Au(CNa" + xm
21 Aue + Au? —> Aus? B2+09)x10° 0.001 RT u pr Product assumed. Chos.68-0302
@9+0.7)x10 O01 RT oB pr Solutions contain— Chos.68~-0302
ed 9.8 x 107? mol
dm“? Ha.

22 Au? + Fe(CN)et" (et?) 5.5 x 10° - RT - pr - Chos.68-0302

2.3 Au? + N20 (et or O at) 5.5 x 10* - RT Pe - Ghos.68-0302

24 Au? + Os (et or af) 3.6 x 10° - RT - pr - Chos.68-0302

Au(O) from Au(CN)s- + H
25 Au? + Au®—> Aus? (6.0 + 1.0)x 10" 0.015, RT 2 fa - Chos.68-0302
Aull) from Au(CN)s- + OH
260 Aull + Ault (2.4 + 0.6) x 10° 0.01 RT 2 Solutions contain— Chos.68~0302
(dis o aff ed 0.1 mol dm“ HCl.
(48 + 1.2)x10° 0.01 RT 47 pr Solutions contain— Ghos.68-0302
ed 0.01 mol dmTM* KCl.
Au({f) from AuCle- + H

27° Aull + Aull, (14+ 0.3)x10° 0.01 20 2 pr Nature of products Baxe.70-0580
Aut + Aut ~see ref. 70-0580.

@640.7)x10° 0.011 20 2 pr Solutions contain— Baxe.70-0580
ed 10° mol dm“* CI.

(1.24 0.1)x10° 0.131 20 2 pr Solutions contain— Baxe.70-0580
ed 10-* mol dm“
Cv + 0.12 mol dmTM* NaClO..

2.7 £0.6)x10* 0.02 20 2 pt Solutions contain~ Baxe.70-0580
ed 107? mol dmTM* CI.

25+ 0.2)x107 0.11 20 2 pr Solutions contain~ Baxe.70-0580

ed 10~! mol dm“* CI".

“If the data source gives no errors none are shown here but they should be assumed to be at least +25% (or -+50% for 2h).

6


TABLE 1. Silver(0) and Silver(II) reactions

No. Reaction K/dm? molt s** ws pH Method Comments Ref.
Ag{0) - aquo ions and
complexes
LL Ag? + Agt — Agst 5.9.x 10 - RT pr Product charac— Puki..68-0431
terised by ab—
sorption spec—
trum and charge.
(6.5 + 0.3) x 10° - 2 © «10 pr -
(6.2 + 0.3) x 10" - 29 1.0 pr Measured at pree—
sure of 6.72 kbar.
12 Agst + Agt > 38x10 = +0 RT pr Products charac
Agt* + Ag.? terised by ab—
sorption spectrum.
13 Age? + Agt—> Ags* cal RTO + pr Product charac— Puki..68-0431
terised by absorp-
tion spectrum.
14 AgsP/Agst + MnO." (et) 12x10" = 0.008 RT pr Measured by the Boxe..65-0385
rate of depletion
of the MnO.” ab—
sorption,
15 Ags* 1 Ox (ct or af) 3.8 x 10% - RT - pr Product uncertain, Baxe..65-0393
but transfers an
electron to
1,4-benzoquinone
(cee Sell.76-1134).
1.6 Ags* + 1,4-benzo- (1.5 + 0.3) x 10° - 2542 58 pr Measured by the Sell. 76-1134
quinone —> Ags?*(?) + rate of formation
(1,4-benzoquinone) of the semiquinone
in the presence of
1 mol dm~*
2-methyl-2-propanol.
1.7 Agst + menaquinone —> slow - - 10 pr Only 24% electron Rao.73-1047
Ags**(?) + (menaquinone)~ transfer, which may
be due to side
reactions. Solutions
contained
1 mol dmTM*
2-methyl-2~propanol.
Ag(O) - ammine complexes
1.8 Ag? + Ag(NHs).* >
‘Age(NH.),* 5.2x 10° - RT - pr _Ag® generated from Puki.68-0435
aq + Ag(NHs)s* —
might be same as
product of ea, ++
‘Ag. Product con-
tains unknown num-
ber of ammine
ligands.
19 Agd(NHs)at + AgdNHs),*—> 2k = 2.6x10% =~ RTO + pr Product uncertain; Puki.68-0435
‘Aga(NHs)a2* ? gives ultimately
Ags’,
1.10 Aga(NHs)a* + Ag(NHs)s* > 10 RT pr Measured from rate Puki.68-0435
‘Aga(NH),2* ? of formation of
product, nature of
which is uncertain.
AgKIl) - aquo complex
1.1L Agtt + Agtt—>
Ag* + Ag* 1.5 x10" - RT - pr Puki..68-0431
1.12 Ag** + anisole > (8.8 + 0.4) x 10” - 2042 — nat(?) pr Product charac— O'Ne..75-1171
Agt + anisole* terised by absorp-

tion spectrum and esr.


‘Taste 21. Thallium(O) and (11) reactions

Reaction

kfdent molt s* wc pt

‘Method

‘Comments

Ref.

a1.

212

214

215

216

aL?

218

219

21.10

211
2112

19)

Ta

TH + HiOs—>
‘TY + OH + OH”

TY + HO.
TI + HOM

Twa
Tt +07
Te + Or
TY + 07

Tres

‘Tht

T+ 7h
w+ Tt

TH (2) + 1,4-benzo~

Sxl - RT 01,52

<i RT mat
13x10" = RT 01,52

@.0 + 02)x 10" ~ RT nat

L4xle = RE 52

K 223x104 - RT 65
ke> toe RT 65

45 + yx 10 - RT at

28x10  - ca. 25 1.0

quinone —> TI” + (Lt-ben20—

Gainone)
nm
Tht + HiOs—>

amit + OH 4 OHM

Tht + NO
(0 ator et)

Tht + Or
‘2TI* + Os"

Tat = TP + TY
Tat +18
amt

(+ 2)x10 - RT nat

(4 + 02)x10" . 25 vat

0.0+02)x10°  ~ RT nat
12x10 RT 0.15.2

see entry 21.5

(444 09)x10 +0 RT nat
G5 1x1 0.0006 = RT at

(5 tY21e 0.015 RT nat

55

23

pr

Re

Rate constant and
products deduced
from HyOn and Ha
yields in y-irradi~
ated TY solutions.
Rate constant and
products deduoed
from H;0s and Ha
yields in y-irradi-
‘ted TY solutions,

Rate constant and
‘products deduced
from Ha0s and Hs
yields in y-irradi—
ated TH solutions.
Measured from the
effect of (11*J on

the absorption due

to Th".

Products deduced
from HiOs and He
yields in y-irradi~
‘we TY solutions,

No account taken of
the hydrolysis of T#*
(see entry 21.19).

No account taken of
‘competing reaction
Th? + TH (eee entry
21.12).

Semiquinone product
identified by its
absorption spectrum,

Products deduced
from HO» and Hs
yields in y-irradi~
ated T solutions.
-y-radiolysis studies
indicate that Ns is
‘one of the products
of this reaction.

Rate constant and
products deduced
from HsOs and Hs
yields in y-irradi-
ated TP solutions.

Products deduced
‘from HaQ, and He
yields in y-irradi-
‘ted TE solutions.

[No account taken of
the bydrolysis of
TI* (eee entry
21.19.

Fara..71-0036

Fara..71-0036
Fara..71~0036

Fara..71-0036

Fara..71-0036

Cere..66-0097

Fara..71-0036

Rao.75-1032

Para..71-0036

Sell72-0844

Fara..71-0036
Fara..71-0036

Para..71-0036


TAMLE 14. Nickel) and nickel({U) reactions — Continued

Ne. Reaction K/dem® molt at = 7 we pH Method Ror
Waal Nit + OS 2 x 10% = Br nat PF
New on
14.32 0 Nit + O.—- NiO. (1.4 & 0.2) x 10% - Rr pr Meye-658
‘ES A = Rr Pe me Oe
with 1.4—bensoqui—
fone Get. 76-1134).
dass Nit + Peet < 107 - Rr pe - Baxe65-
asa Nit} Rane (oo (2.0 © 0.6) = 10" o.08 Rr Pe
1ass 0 Nit 4} SO GS = 0:2) x 10" 0049 as se 2 r
NEY SO + SO.
a.360 0 NEY 4+ Zest < 107 - er nae pe Baxe.0o-
ais? Nit 4 -CH,ON —- 2m 10" = ner nat Pr elm 7a
tage Nit - Nico. 6.6 = 10% Rr nat pr Kelm..74
14.39 0 Nit 4 CaO 2an10°  4x10-5 RT nat Pr Kel. 74
NiGHOn”
14.400 Nit 4 CHACOMCH. —~ 1a x 10% RT nat pr Kolm... 74-
MGOMCHO
° Nit 4 OHM fF CH= CCH.
34.420 NST + “GH, NICHT aex10e 4510-8 RT nae pr

(CGiH. — cyclopentyl radical)

3B


No.

Tawi 6. Copper(l) and copper(III) reactions — Continued

Reaction A/dm mol” s“* * I °c pH

Method

Comments

Ref.

6.18

6.19

6.20

6.21

6.22

6.23

6.24

6.25,

6.26

6.27

6.28

6.29

6.30

CuL* + Cofen)s** < 10 0.016- «RT 10
0.028

CuL* + Co(NHs)e** <10 0.016- RT 7.0
0.028

CuL* + CoL'(OH)* < 10 0.016- RT 70
0.028

(’ = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,7,10-tetraene).
CuLt + Cr(bpy)s** (et) @.7404)x10! 0.016 RT 7.0
0.028

CuL* + Fe(bpy)s** < 10° 0.016- RT 7.0
0.028

CuL* + Hs0* (pt) (5.0 + 0.5) x 108 0.06- RT = <125
03

CuL* + HaPO” < 10 0.01- RT 5.50,
0.1
CuL* + N20 (et or O at) (1.7 + 0.2) x 10® - RT 78

Cult + O1—> 2.6 + 0.3) x10" - RT 70
CuLO2*

CuL* + Ru(NHs)* (7.2 + 0.7) x 10* 0.016- RT 1.0
(et) 0.028

CuL* + Ru(NHs)sNO*+ <10 0.016- = RT 70
0.028

CuL* + ‘acetic acid < 10 0.015- RT 4.85
0.06

CuL* + 9,10-anthra— (4.3 £0.4)x 10 0.004 = RT 1.0
quinone-2,6—disul-
phonate (et)

26

pr

pr

pr

pr

pr

pr

pr

pr

Pr

Measured in the
presence of 1

mol dmTM* 2-methyl~
2-propanol.
Measured in the
presence of 1

mol dm“* 2-methyl~
2-propanol.
Measured in the
presence of 1

mol dm“* 2-methyl-
2-propanol.

Measured in the
presence of 1

mol dm“* 2-methyl-
2-propanol.
Estimated in the
presence of 1

mol dm”* 2-methyl-
2-propanol.
Reaction may
involve proton
transfer to the

metal centre to

give a hydrido
complex.

Measured in the
presence of 1

mol dm“* 2-methyl-
2-propanol.
Reaction possibly
involves two electron
oxidation to Cu(III)
complex.

Product does not
transfer an elec
tron to 1,4-benzo-
quinone, and identi-
fied therefore as Oa
adduct.

Measured in the
presence of 1 mol
dm? 2-methyl-2-
propanol.

Estimated in the
presence of 1 mol
dm“* 2-methyl-2—
propanol.

Estimated in the
presence of 1 mol
dm”? 2-methyl-2—
propanol.

Measured in the
presence of 1 mol
dm”? 2-methyl-2—
propanol.

Tait..76-1039

Tait..76-1039

Tait..76-1039

Tait..76-1039

Tait..76-1039

‘Tait..76-1039

Tait..76-1039

Tait..76-1039

Tait..76-1039

Tait..76-1039

Tait..76-1039

Tait..76-1039


Tame 14. Nickel) and nickel(IID reactions — Continued

Most 4 HT = K — 2000 + 1200 M-» 0.04 25-42
NiOnHe (Ge. PK = 8.2
o3)
iow —— > 2800 = - 252
MUD complexes
NBC Nad @ x10" - Rr
NEm(NEn + NINE ae Sas % 10" = RE

Rate constants for the decay of NiTMendn and Ni“gly)a are given
‘Those rate eomsants Lunnot be attributed to any specific rewction

pe

Sen.76-1194

Sel-7o-1134

in source giver no errors none are shown here but they should be



Taste 6. Copper(l) and

copper(II) reactions — Continued

No. Reaction ‘dm? mol“ 57 * 7 wc pH Method Comments Ref.
6.11 Cut + ethylene = K=(222+01) - 2542 4 Measured from he Bust..76-1186
Cu-ethylene* x 10° dm* mol“ effect of admitting
ethylene to solu-
tions of Cu-acrylamidet
(cee entry 6.9).
6.12 Cut + fumaric acid = fy = (L7 + 0.4) - 2242 3.65 pr_—- Measured from the Meye75-1092
Cu-fumaric acid* x10 rate of formation
ky = (2.4 + 0.4) - 2242 = 3.65 pr _—of the product in
x 108s the presence of 1
K = (11 + 2.0) mol dm“* methanol.
x 10° dm? molTM*
K = (0.0 + 2.0) - 2242 3.65 pr_~—- Measured from the Meye75-1092
x 10* dm* mol"? effect of (fumaric
acid] on the yield
of Cu-fumaric acid*
— in the presence
of 1 mol dmTM* meth-
anol.
613 Cut + iso-butene = K=(7+0.1) - B+2 4 Measured from the Buxt..76-1186
Cu-iso-butene* x 10¢ dm? mol? effect of admitting
iso-butene to solu-
tions of Cu-acrylamide*.
6.14 Cut + maleic acid = ky = (2.0 + 0.4) - 2242 3.65 pr _—- Measured from the Meye75-1092
Cu-maleic acid* x10 rate of formation
ky = (1.8 + 0.4) - 2242 3.65 pr_of the product in
x 105s the presence of 1
K = (11 + 0.3) mol dmTM* methanol.
x 10¢ dm? mol,
K=(13 + 02) - 2242 3.65 —pr_— Measured from the Meye75-1092
x 10¢ dm? mol? effect of [maleic
acid] on the yield
of Cu—maleie. acid*
in the presence of
1 M methanol.
6.15 Cut + tetranitro- (4.2 + 0.4) x 10* - Rr - pr Measured from the Asmn...64-0133
methane —> Cu?* + rate of formation
NOs + C(NO2)s~ of the nitroform
anion.
(4.7 + 0.5) x 10° - 28+2 4.9 pr Measured from the Sell.76-1134
rate of formation
of the nitroform
anion,
Cull) Co
Cul* (L = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca~4,1-diene)
6.16 CuL* + Co(bpy)s** (12+01)x107 0.016 RT = 7.0 pr Measured in the Tait..76-1039
(et) 0.028 presence of 1
mol dm~* 2-methyl-
2-propanol.
6.17 CuL* + CoL'(OHXOH)* <10 0.016- RT 7.0 pr Measured in the Tait..76-1039
0.028 presence of 1
mol dm~* 2~methyl—
2-propanol.

(L’ = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11~diene).

25


TABLE 24. Zine([) reactions

No. Reaction k/dm? mol“! s#* wc pH Method Comments Ref.
Inv
24.1 Zn* + BrOs (et) (2.1£03)x10° 0.08 RT nat pr : - Meye.68-0855
24.2 Zn* + Ca** (et?) <1x10" 0.08 RT nat pr The reason for the Meye.68-0855
8.3 x 10° - RT nat pr discrepancy between Baxe..66-0848
these two values is
not clear.
24.3 Zn* + Cl0s" <3x10* 0.08 RT nat pr - Meye.68-0855
244° Zn* + Cot <3x10° 0.08 RT nat pr - Meye.68-0855
24.5 — Zn* + Co(bpy)s** (et) 2.6 x 10° - RT nat Pr - Baxe..72-0381
24.6 — Zn* + Cofen)s** (et) 2.5 £0.4)x10* 0.08 RT 5-6 pr - Meye.69-0428
24.7 Zn* + cis-Cofen)sCh* (1.91 0.3) x 10° 0.08 RT 5-6 pr - Meye.69-0428
(et)
24.8 © Zn* + trans— 2.340.3)x10° 0.08 RT 5-6 pr - Meye.69-0428
Cofen)sCla* (et)
24.9 Zn* + Cofen)sCOs* (47£0.7)x10 0.08 RT 5-6 - Meye.69-0428
(et)
24.10 Zn* + cis-Colen)sFs* 64+ 08)x108 0.08 RT 56 - Meye.60-0498
(et)
24.11 Zn* + Co(en)sFH:0%* (4.7£0.7)x10" 0.08 RT 5-6 pr - Meye.69-0428
(et)
24.12 Zn*+ cis-Colen)NHCP* (1.47 0.2)x 10° 0.08, RT 56 pr - Meye.60-0428
(et)
24.13 Zn* + cis 2.7 +0.7)x10° 0.08 RT 5-6 pr - Meye.69-0428
Co(en):NHsNOz** (et)
24.14  Zn* + Co(NH,)e* (Ra + 1.2) x 108 0.08 RT 5-6 pr - Meye.69_0248,
(et)
24.15 Zn* + Co(NHs)sBr* (2.6 + 0.4) x 10° 0.08 RT 4.0 pr - Meye.69-0428
(et)
24.16 Zn* + Co(NHs)sCP* 2.24 0.3)x10° 0.08 RT 5-6 pr - Meye.69-0428
(et)
24.17 Zn* + Co(NHs)sCN** (1.30 + 0.2) x 10° 0.08 RT 56 - Meye.69-0428
(et)
24.18 Zn* + Co(NHs)sF** @2+12)x10° 0.08 RT 5-6 - Meye.69-0428
(et)
24.19 Zn* + Co(NHs)sfumar- (124 0.3)x10° 0.08 RT 5-6 - Meye.69-0428
ate* (et)
2420 Zn* + Co(NHs)sH20*t (1.56 + 0.2) x 10® 0.08 RT 4.0 pr - Meye.69-0428
(et)
24.21 Zn* + Co(NHs)OH** (1.10 + 0.2) x 10° 0.08 RT 66 pr - Meye.69-0428
(eo)
24.22 Zn* + Co(NHs)sNs** (1.49 + 0.2) x 10° 0.08 RT 5-6 Pp - Meye.69-0428
(et)
24.23 © Zn* + Co(NH)sNCS** (1.65 + 0.2) x 10° 0.08 RT 5-6 pr - Meye.69-0428
(et)
24.24 Zn* + Co(NH,)sOOCCH,?* (5.0 + 0.8) x 10* 0.08 RT 5-6 pr - Meye.69-0428
(et)
24.25 0 Zn* + Cet <10" - RT nat pr - Baxe..66-0848
24.26 Zn* + Cr0r* (et) (1.6 + 0.2) x 10% 0.020 252 nat pr - Buxt..76-1072
24.27 Za* + Cut* (ot) (2.5 + 0.4) x 108 0.08 RT nat pr - Meye.68-0855,
0.54 2.0)x10° 04 RT 5-8 7 Measured by compe- Fiti70-0117
(2nS0,) ion wit
Rate constant cal~
culated taking
KZn* + NOs”) = 2.1
x 10° dm* mol” s“*
(cee entry 24.33).
24.28 © Zn* + HaOs > (1.80 + 0.3) x 10° - RT nat ra - Meye.68-0855
Zn** + OH + OH- (2.3 + 0.2) x 10° - 25+2 nat pr Products inferred Buxt..76-1072
from ‘y-radiolysis
experiments (see
ref. 73-0039).
E, = 105 + 1.0 - - nat pr - Bust..76-1072

kJ mol“
62


Arrangement of the Tables

The tables are listed in alphabetical order of the chemical symbols of the metals involved. Within each table
the arrangement is by oxidation state, starting with the lowest, and is further subdivided according to the
complexing ligands in the order aquo ions (and hydrolysed forms), inorganic ligands in alphabetical order of the first
letter of the chemical symbol of the principal element of that ligand (e.g. N for ammonia), and organic ligands in
alphabetical order of their written names. For each individual transient species the reactants are in the order:
inorganic species, organic radicals, both in alphabetical order of their chemical symbols, followed by organic
compounds in alphabetical order of their written names.

Table 25 is somewhat different, and lists the rate constants for some intramolecular electron transfer
reactions. ‘I'he reactions are subdivided according to the method of production of the transient species. Note that all
the rate constants in this table are first order, and have therefore units of s~1. Reactions of metallo-proteins and
related compounds are not dealt with in this compilation.

The data given for each reaction are the measured rate constant, and a brief description of the experimental
conditions etc. as outlined below. Literature data published to approximately mid-1976 are covered.

Reaction: Three main methods have been used to measure the rate constants reported here:

(i) by monitoring the rate of removal of the absorption of the
metal species at some convenient wavelength
by monitoring the rate of formation of some product
by competition kinetics.
Methods (j) and (iii) have the disadvantage that they do not involve characterisation of the products of the reaction,
and in many instances in the literature no additional experiments have been performed to overcome this. Often the
reaction type has been assumed. Particular attention has been given to this problem in this compilation. Where there
is no experimental information on the products given in the original work or elsewhere, only the left hand side of
the equation is given, followed in brackets by the possible type of reaction as originally suggested, or as seems
appropriate. If experimental evidence is given, the products are quoted, and the nature of the evidence indicated in
the column headed ‘Comments’.

In some cases the reactive intermediates themselves have not been fully characterised, and in such instances
brief details of the method and conditions of formation are given.

Rate Constants: Most of the rate constants listed were measured under conditions where the reaction obeyed
first order kinetics and no knowledge of absolute concentrations of the transient species is required. Error limits on
the rate constants are those quoted in the original work. In the great majority of cases their magnitude is + 10 -
15% of the rate constant value, which is typical of the precision of the mean of pseudo first order rate constants
measured by pulse methods. If the data source gives no errors none are shown here, but they should be assumed to
be at least + 25% to allow for the possibility that the rate constant is derived from a single measurement.

Second order rate constants are prefaced by “2k =” or “2k/€, =” as appropriate. In cases where it is not
clear whether the value refers to 2k or k this is noted in the ‘Comments’ column. The measured quantity is 2k/é.
and is subject to the same limitations given above for pseudo first order rate constants. Calculation of 2k requires a
knowledge of €, and where this quantity is quoted in the original work it is given under ‘Comments’. In many
instances, however, the values of €, used to calculate 2k have not been clearly stated.

Evaluation of €, requires a knowledge of the concentration of transient species present which, in radiation
chemical systems, means that the dose per pulse and the G value? of the species must be known. In our experience
these quantities are each likely to be uncertain by -+ 10%, so that the error in 2k may be as much as three times as
large as the error in 2k/€. Therefore, in the absence of any quoted errors, the error in 2k should be assumed to be
+ 50%.

°C in the number of molecules ofa species produced per 100 eV of absorbed energy.


TABLE 4. Cobalt(l) reactions — Continued

No. Reaction A/dm? mol s~* * I °C pH Method Comments

Ref.

428 Colt + HPO” > 3.0.x 10" 0.005 RT 55 pr Measured in the
CoLH* + HPO? 0.01 presence of 1 mol
dm”? 2-methyl-2—
propanol. See ref.
for evidence for
proton transfer
mechanism.

4.29 CoL* + N,0 (et) 9.0 x 10° 0.01 RT 9.2 pr Reaction possibly
involves two elec-
tron oxidation to
Co(tI1) complex.

430 CoL* + Os CoLO,* 9.0 x 10° 0.02 RT 9.2 pr Measured in the
presence of 1 mol
dm"? 2-methyl-2-
propanol. Reaction
does not involve
the formation of
CoL**, assumed
therefore to in—
volve the coordin—
ation of the Os.

ry

NHN.
CoL* (L = 5,7,7,12,14,14-heramethyl-1,4,8,11-tetraazacyclotetradeca~4,11-diene). C )
NHN

PN

4.31 CoL* + Co(bpy)s** (et) 12x 10° ca. RT 9.2 pr Measured in the
0.02 presence of 1 mol
dm”* 2-methyl-
propanol.
4.32 CoL* + Colen)s** (et) 7.9 x10* ca, RT 9.2 pr Measured in the
0.02 presence of 1 mol
dm"* 2-methyl-2~
propanol.
4.33 CoL* + Co(NHs)e** (et) 7.5 x 10# ca. RT 9.2 pr Measured in the
0.02 presence of 1 mol
dm * 2—methyl-2—
propanol.
4.34 CoL* + CoL?* (et) 4.0 x 10° ca. RT 92 pr Measured in the
0.02 presence of 1 mol
dm Z-methy!-2—
propanol.
4.35  CoL* + CoL’* (et) 6.7 x 10° ca. RT 9.2 pr Measured in the
0.02 presence of 1 mol
dm“* 2-methyl-2-
propanol.

(L’ = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,2,8,10-tetraene)
4.36 CoL* + Cr(bpy)s** (et) 12x 10° ca. RT 92 pr Measured in the
0.02 presence of 1 mol
dm“* 2-methyl-2~
propanol.

16

Tait..76-1001

Tait..76-1001

Tait..76-1001.

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001

Tait..76-1001


TABLE 20. Samarium({I) reactions

No. Reaction ‘k/dm? mol"* 5“! * Tr wc pH Method Comments Ref.
Smt sg
20.1 Sm** + BrOs (et) 71x 108 0.015 = RT nat pr - Fara.72-0065
(7.0 + 0.5)x 10° 0.0375 «RT 6 pr - Pika..73-1084
20.2 Sm** + Co(en)s** < 1x10 0.06- = - RT 6 pr - Fara.73-0107
1.0
20.3 Smt + Co(NHs)Br* 3.5.x 107 0.06 RT 6 pr - Fara.73-0107
(ep)
1.6 x 10° 1.0 RT 6 pr - Fara.73-0107
(NaClO,)
2.5.x 108 1.0 RT 6 pr - Fara.73-0107
(NaCl)
20.4 Sm + Co(NHa)sCl** 3.8.x 10" 0.06 RT 6 pr - Fara.73-0107
(et)
1.7 x 10° 1.0 RT 6 pr - Fara.73-0107
(NaCl)
2.3 x 10" 10 RT 6 pr - Fara.73-0107
(NaCl)
20.5 © Sm** + Co(NHs)sCN7* <3.0x10* 0.06 RT 6 pr - Fara.73-0107
20.6 © Sm** + Co(NH,)F** 2.5 x 10" 0.06 RT 6 pr - Fara.73-0107
(et) 11x10" 1.0 RT 6 pr - Fara.73-0107
(NaClO,)
1.8 x 10° 10 RT 6 Pr - Fara.73-0107
(NaCl)
20.7 ‘Sm** + Co(NHs)sH:0** 6.0 x 10° 0.3 RT - pr - Fara.73-0107
(et) 8.8 x 10 1.0 RT - Pr - Fara.73-0107
(NaClO,)
2.6 x10" 1.0 RT - a - Fara.73-0107
(NaCl)
20.8 — Sm** + Co(NHs)el** (et) 5.8 x 10" 0.06 RT 6 pr - Fara.73-0107
20.9 Sm + Co(NHs)sNs** (et) 78x10" 0.06 RT 6 Pr - Fara.73-0107
2.5 x10" 0.5 RT 6 pr - Fara.73-0107
(NaClo.)
20.10 Sm** + Co(NHs)sNCS** < 10x 10° 0.06 RT 6 Pr - Fara.73-0107
< 10x 10° 05 RT 6 pr - Fara.73-0107
(NaCl0,)
20.11 Sm** + Co(NH).e* < 10x 10% 0.06 RT 6 pr - Fara.73-0107
(et)
5.0 x 10° 10 RT 6 pr - Fara.73-0107
(NaCl)
20.12 Sm** + Co(NH.)OH#* 15x 107 03 RT - pr - Fara.72-0107
(et)
5.0 x 10" 10 RT - pr - Fara.73-0107
(NaClO,)
5.0 x 10" 1.0 RT - a - Fara.72-0107
(NaCl)
20.13 Sm** + CrOe (et) (4.0 + 0.5) x 10° 0.375 RT 6 pr - Pika..73-1084
20.14 Sm + Cur* (et) 8.3 x 10" 0.015 = RT nat pr - Fara.72-0065
20.15  Sm** + H.Os (et) 3.5 x 107 0.015 RT nat pr - ‘Fara.72-0065
(6.7 + 0.3) x 10" 0.375 = RT 6 pr - Pika..73-1084
20.16 Sm** + Eu®* (et) 15 x 10° 0.015 = RT nat pr - Fara.72-0065
20.17 — Sm**+ 10s" (et) 49x10" 0.015 = RT nat pr - Fara.72-0065
20.18 Sm** + MnO." (ed) (4.7 + 0.5) x 10° 0.375 RT 6 Pr - Pika..73-1084
6.5 x 10° 0.015 = RT nat pr - Fara.72-0065
20.19  Sm** + NOs" (et) 11x10 +0. RT nat pr - Fara.72-0065
(1.3 + 0.2) x 10° 0.375 = RT 6 pr - Pika..73-1084
20.20 Smit 4°NO4” (et) (15 + 0.2) x 108 0375 RT 6 rt - Pika..73-1084,
2.0 x 10° 0.015 «RT nat pr - Fara.72-0065
20.21 Sm** + Na (et?) 2.0 x 10 0.015 = RT nat pr - Fara.72-0065

58


TABLE 23. Yiterbium(II) reactions

No. Reaction k/dm? molTM* 5~* * I wc pH Method Comments Ref.
Yo3d (Rate constants from pulse radiolysis studies only).
23.1 Yb* + BrOs- < 10 0015 RT nat pr - Fara.72-0065
23.2 © Yb* + Cofen)s’* <5x10 006-10 RT 6 ra - Fara.73-0107
23.3 Yb** + Co(NHs)sBr'* (et) 3.0 x10 0.06 = «RT 6 pr - Fara.73-0107
14x10 1.0 RT 6 pr - Fara.73-0107
(Nacio,)
25x10" 1.0 RT 6 ra - Fara.73-0107
(NaCl)
23.4 Yb** + Co(NHs)sCl* (et) 43x 10° 006 «RT 6 i - Fera.73-0107
19x10" 10 RT 6 Pr - Fara.73-0107
(NaCl0.)
2.3.x 10" 1.0 RT 6 Pr - Fara.73-0107
(NaCl)
23.5 Ybt* + Co(NHs)sCN** (et) 3.0 x10 0.06 «RT 6 ra - Fara.73-0107
23.6 Yb** + Co(NHs)sF** (et) 11x10" 0.06 = «RT 6 Pr - Fora.73-0107
6.0 x10" 1.0 RT 6 pr - Fara.73-0107
(NaClO,)
1.0 x 10° 1.0 RT 6 ra - Fara.73-0107
(NaCl)
23.7 Yb** + Co(NHs)sHa0"* 2.2.x 10° 03 RT 2 pr - Fara.73-0107
(ep)
6.4.x 10° 10 Rr 2 p - Fara.73-0107
(NaClO,)
23.8 Ybt* + Co(NHs}sNs** (et) 16x10" 006 = RT 6 - Fora.73-0107
2.6 x 107 05 RT 6 pr - Fara.73-0107
(NaClO.)
23.9 Yb** + Co(NHs)sNCS** < 50x10 05 RT 6 pr - Fara.73-0107
(Neco)
23.10 Yb?* + Co(NHs)e* < 5.0.x 10¢ 006 RT 6 Pr - Fara.73-0107
23.11 Yb** + Co(NHs)sOH?* (et) 7.7 x 108 03 RT 5.5 pr - Fara.73-0107
19x10" 10 RT 55 pr - Fara.73-0107
(NaclO,)
2.9 x10" 10 RT 55 pr - Fara.73-0107
(NaCl)
23.12 Yb** + Cut* (et) 12x10" 0.015 RT nat ia - Fara.72-0065
23.13 Yb** + Hy0s (et) 9.1.x 108 0.015 RT nat Pr - Fora.72-0065
23.14 Yb** + 10s" (et) 2.1.x 10¢ 0.015 (RT nat Pr - Fara.72-0065
23.15 Yb** + MnO.” (et) 8.3 x10" 0.015 RT nat Pp - Fara.72-0065
23.16 Yb** + NOs" (et) 47x10" 0.015 RT nat pr - Fara.72-0065
23.17 Yb** + NOs" (et) 3.6 x 10° 0015 RT nat pr - Fara.72-0065
23.18 — Yb#* + Na0 (et?) ca. 10 0.015 RT nat oa - Fara.72-0065
23.19 Yb + Os (et or af (6.3 + 1)x10" 0375 «RT 2 pr - Piks..73-1084
6.5 x10" 0.015 RT nat fa -
23.20 Yb** + OH (et) 3x10 0.015. RTs, pr -
@2+03)x10" 0375 RT. 2 PF - Pil
23.21 Yb** + Ru(NHs)sBe* 3.3.x 10" 006 «RT 6 pr - Fara 73-0107
(et)
23.22 Yb** + Ru(NH,)sCi* (et) 15x10? 0.06 «RT 6 Pe - Fara.73-0107
1.8 x 10" 1.0 RT 6 pr - Fara.73-0107
(NaCl0,)
2.8 x 108 1.0 RT 6 pr - Fara.73-0107
(Nec)


Tamir 9. Mercury(0) and mercury() reactions — Continued
A/ame molt = we PEE Method Ror
7 = 10° Rr = Pr Jung-76-1042,
2k = G4 + 0.5) Rr - Pr Fuji.-75-12038
Gulnted taking: exon
SNS8OO dent molTM om!
2k 1.210% Rr - we = Jung--76-1042
ween 1 on Perey bes = am ew tenee ohare Sng se ese
HgcNt or Oa feriald by tee
HgCN + OFF (on Bl x 10° Rr - pe
HgCN 4+ -cHLOH 4.0 = 10° RT - pe
HgCN 4. CHCHOH (ort 2.9 x 10° Rr - pr
HecN?)
MIgCN + (CH.).CHOH —~ 2.4.x 10° Rr = 7 Faji.75-1208
er + CN" + CH.GOGH. + Ht
MeCN + -CHC(CH).OH 1.6 x 10° nr - Pe 75-1203
taf)
BIgCN + 1,4 benzo 3.5 x 10° nr - pr Jung.-76-1042
Guinone —~ HigeN +
ea ensoquinoney
Het
Hel + Het —- Hest. 2k — 5.0.x 10" RT = pe Jung..76-1042

33



‘Tamie 9. Mercury(0) and

meroury() reactions — Continued

Ne. Reaction Rams molt a= we PH Mathod Ret
oan Hal + Os HgtO. > 10" Rr = Pr Jung..76
os2 > 10" Rr - Pr 76
933 1.4 x 10° Rr - pr Jung.-76
eas > 10" RT - Pr 76
o.26 > 10 RT - pr Jung-76
oss 1.0 x 10" Rr - pe Jung..76

TL HigsCN* + On +
Gia honzequimone)

THE the data source gives no error none are shown here but they should be assumed to be

iat least 25% (or +5096 for 2h).


TamLE 17. PlatinumcD

Ss Elame mals 7 PH Method Ret.
Sone W — G9 & 1.9) 10" = Rr 20 a Brod..76-1098
ting cance
SSO amt mol
Unclear whether
Wr CHeCOHCH. or
6.8 1-0) = - ca - Pro Measured in the Stor-75-1188
3s
PEE from erans—PkendaCla* +H
Pee pe (aia) Be 0.8 1.0) ~ - a 2 Pr Stor.75-2188
PE from trams Phen Cla + CHO
Pe pen Cate) Be = (04 + 0.88) - - pr
- co Pe Stor.75-1188
eM from Pudien) CLt + OH
wun (2.8 + 0.8) = 10" - Rr nat a Brod...76-1098
eu
Pe from PLLCE* + Cla UL — tetranthyldtathylenetriamine)
pen Ga Gs 0.4) = 10" 2 =~ o3 pe
Pen, pen 2k = ca. 8x 10" - - 03 pr
PEM from PLLCI* 4 OH  —~ tetraethyldiethylenesriamine).
cong ean 18 OSs = o- nat pr - Bred...76-1093

cea source gives ho errors none are shown here but they should be assumed to be at least sb 25% (or 250% for 24).

ao


TapLe 5.

Chromium(), chromium({) and chromium(V) reactions — Continued

No.

Reaction

k/dm? molTM? s~* * I

ee

pH

Method

Comments

Ref.

5.16

5.17

5.18

5.19

5.20

5.21

5.22

5.23

5.24

a* + CHsCHOH —
(CrCH(CHs)OH**

Cr+ + .CHOHCH.OH >
CrCHsCHO** or
CrCH.CH(OH),**

Crt* + -CH(COOH): >
(CrCH(COOH).**

Cr+ + CHsCHCOOH +
(CrCH(CHs)COOH?*

Gr** + CHsC(OH)COOH
CrCOH(CH,)COOH?*

79x10" -

1.5 x 10° -

60x10" -

L1x 10 -

9.2x10" -

Cr+ +.CH,N(CH;)CHO— (1.1 + 0.1) x 10° -

(CrCHaN(CHs)CHO**

Cett + (CHs):COH
CrCOH(CH;).**

Get +R CR
-R = radical from dioxane
(H abstraction)

Cr* + -CHsC(CHs),0H —
(CrCHC(CHs).0H?*

5.1x 10" -

1.0 x 10° -

1.0 x 10° -

2242

2242

2242

2242

2242

2242

22

o-1

3.04.5

0-1

pr

pr

pr

pr

pr

Pr

pr

pr

Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
product. Product is
identical to that
formed in the reaction
Cr+ + CH:CHO (see
entry 5.13).
Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
produet. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
product in the pre~
sence of 1 mol dmTM*
CHsN(CH,)CHO. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
Measured by the rate
of formation of the
product. Product
characterised by its
absorption spectrum.
amd decay kinetics.

Cohe.74-1146

Cohe.74-1146

Cohe.74-1146

Cohe.74-1146

Cohe.74-1146

Cohe.74-1146

Cohe.74-1146

Cohe.74-1146

Cohe.74-1146


Tami 19. Rutheniam(). (iD. GID and (Vv) reactions — Continued

Ne Reaction Fame mmo oe 7 we pe Method

‘Rut’ (The precise nature of these complexes is uncertain: all were formed by OH oxidation of the
198 0 Rue? Bs = 10% ‘Sx 20 20 mee ve
TaN ETa)at (ate)

19.9 RuvHy.cr*

ax10— 20 nat Pr

corresponding Ru" complex).
‘Unclear whether Baxe..70-

Baxe..70-

acuation and Bydro~
Syme emai

TIF the data source gives no errors none are shown here but they should be assumed te be at

52

last 25% (or 50% for 2h).


TapLe 23. Ytterbium(I) reactions — Continued

No. Reaction k/dmn* mol? 5“ * I wc pH Method Comments Ref.
23.23 Yb** + Ru(NHs)sH.0** 1.0.x 10" 0.3 RT 2 Pr - Fara.73-0107
(et) 2.9.x 10" 10 RT 2 Pr - Fara.73-0107
(Naclo,)
3.2 x 10* 10 RT 2 pr - Fara.73-0107
(NaCl)
23.24 Yb** + Ru(NH,)sI** (et) ca, 10° 0.06 «RT 6 pr - Fara.73-0107
23.25 -Yb** + Ru(NHs)e** (et) 5.0.x 10° 0.06 RT 6 pr - Fara.73-0107
4.5 x10" 1.0 RT 6 - Fara.73-0107
(Nelo)
3.0 x 10* 1.0 RT 6 pr - Fara.73-0107
(NaCl)
23.26 Ybtt + Ru(NH,)OH#* 13x10" 006 =RT 6 pr - Fara.73-0107
(c) 2.3.x 10" 03 RT 6 pr - Fara.73-0107
5.0 x10" 1.0 RT 6 pr - Fara.73-0107
(NaCloy
14x10 1.0 RT 6 pr - Fara.73-0107
(oc

“If the data source gives no errors none are shown here but they should be assumed to be at least -+25% (or +50% for 2 k).

61


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 chem:
istry. The quantities which were measured first were the observed radiation yields or G values (mole-
cules 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, chem-
ical 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


TADLE 14. Nickel) and nickel) reactions — Continued

coo Braet ma eG oo
Mitt thm Br. tb ta hacamathyttsts0)Inistrsaracyclontradeon tt Item) S
NL + Colborne” GQssonsie ome mr 70 ope
ca oe
wat @onomxie oo mr 70 we mate re2080
Eaxteomocoron co 3288

Cr = 5.7,7,12,14,14 hexamothyl-1.4,8,11_totrannmcyclotetrads
Na

> + Coleman? GO aa 0.1) = 40" O.o1e~ pr
01028,

NIL* + Cotter (eo 9 + 0.2)=10° 0.016 RT 70 ve ‘Tait..76-1089

NILY + CoLOED.* (oo (.6-£0.4)x107 0016 RT. 70 pe Tait.76-1089
olo28

! = 2.5,9,10-totramethyl-1,4,8,11_tetransacyclotetradecn—1,3,8,10-tetraene).

Nie Cree Ga Eon lO Oole Re 7.0 be Vate_76-1029

NIL + Fetpy)et? (oo @2402)%10° oor RT 70 Pr Tais..76-1039

NILt + HPO” @O (4-2 0.2)x10" 001-010 RT 5.50 pe ‘Tait..76-1029

NILt 4 NAO (ot oF 8 + 0.2) = 107 - Rr 70 pr ‘Taie-76-1039

Oa
NIL + On — G.7 + 0.2) x 10° - Rr 70 pe ‘Taie..76-1039

aL


TABLE 14. Nickel) and nickel) reactions — Continued

Reaction K/dme molt a= 7 wre PH Method ‘Comments Ret
Niall! aleoholTM " - ~ ~
Nit +} 1,4 benzo 2.3 + 0.5) = 10" = 2s 60 Pr Measured by the Sen.7e-1194

quinone —~ Nee
Ga penscquinone)—

Nit 4, menaquinone —- 2a x 10° - <a. 25 z0
Nis yn Gmomacuinon (2.5: 0.3) x 10" = RE To
Nit + totranitre— (2.4 0.2) = 10" - 252 59
2k = 05 + 0.2) oa 20%2 -
x 10" (HCOwNa)
8.1 1.0) = 10" on 20 + 2 -
= (HCO.Na)
ME (= 5.5.7.12,12,14 hexamethyt-1,4,8,1 1 ~tetraanacyclotetradecane).
NIL* + Cothpy)t* @s £0210 coi RT 70
Nt G4 01x10" o01e RT 70
(CoLXOH.KOED** (oo 0.028

(Le = 5.7,7,12,14,14_nexamothyl-1.4,8,11_tetraasacyclotetradeca—4,11—diene).

NIL* +" Gofemat* Gd GA Oa) 210" 0.016 RE 7.0
NIL + Co(NHaa (oo G2 +02"10° 016 RT 70
+ 4 CoLKOEDs* (oo (7 £02107 0.016- ar 10

oloze

39

pe

ve

Sbeception spectrum.

presence of
Bopropenct. ~

Measured in the

Rao.75-1032
Rao7a_10a7

Patt. 7e1089


TaBLE 24. Zino(f) reactions — Continued

No.

Reaction A/dm? molTM s~* * I wc

pH

Method

Comments

Ref.

24.43

24.44,

24,45

24.46

24,47

Zn* + benzophonone —> 2.5 x 10° - RT
Zn** + (benzophenone)

Zn* + 1,4-benzo— 8.0 + 0.6) 10° - 252
quinone > Zn** +

(1,4-benzoquinone)

4.8 x 10° - RT

Zn* + menaquinone > (8.8 + 0.4) x 10° - RT
‘Zn* + (menaquinone)-

Zn! Complezes

ZnL* (from ZnL** + CHsCO~CHs), L = hematoporphyrin (ix)
(no reference made to number of protons involved with complex).

ZnL* + ZnL* +
(ZaL).**

(2.1 + 0.4) x 10* Ol RT

(ZaL).** > P W+2s% O01 RT

P — dihydroporphyrin <016 st Ol RT
product

10

5.7

7.0

cal

13

13

pr

pr

pr

Measured in the
presence of ca.

1 mol dmTM? 2~
methyl-2-propanol.
Ketyl radical pro-
duct characterised
by its absorption
spectrum,

Measured in the
presence of 1 mol
dmTM* 2-methyl-2-
propanol. Semi—
quinone product
characterised by

its absorption
spectrum.
Measured in the
presence of ca.

1 mol dm“? 2—
methyl-2-propanol.
Measured in the
presence of ca.

1 mol dm“? 2-methyl~
2-propanol. Semi~
quinone product
characterised by

its absorption
spectrum.

Unclear whether &
or 2k, Measured
in the presence of

1 mol dm“? 2~pro-
panol. Dimerisstion
‘mechanism implied
from subsequent
reactions (see entry
24.47) and
comparison with the
products of reduction
of ZnL** in aprotic
solvents,

Reaction suggested
to involve internal
rearrangement.
Reaction presumed
to involve splitting
of dimer.

Rao.75-1032

Sell.76-1134

Rao.75-1032

Rao.73-1047,
Rao.75-1032

Hare.74-1040

Hare.74-1040

Hare.74-1040

“If the data source gives no errors none are shown here but they should be assumed to be at least +25% (or +50% for 2h).

64


TABLE 3. Cd({) reactions — Continued

No. Reaction k/dm? mol s** uC pH

Method

Comments Ref.

3.33 Cd* + NsO — CdO* + Na <2x10° - RT nat
1x10* - RT nat
5 + 0.4) x 10° - 25 nat
E, = 5.6 + 1.3 - 1-30 nat
KJ mol"

3.34 Cd* + Os (et or af) (2.4 + 0.4) x 10° - RT nat
3.3.x 10° - RT nat
(3.6 + 0.4) x 10° - 2542 nat

3.35 Cd* + OH — Cd?* + OH ca. 8 x 10° - 25 nat

1.8 x 10° - RT nat

2x 10% - RT nat

BEES

pr

pr

pr

pr

- Meye.68-0855
- Buxt..67-0062

Solutions contain~ Bust..76-1072

ed 0.1 mol dm“*

methanol.

Products inferred

from ‘y-ray indue~

ed chain reaction

in the system

Ca** + HCO." + NiO.

G(N;) measured in

the system Cd** +

N,0. (see ref.

73-0039).
- Meye.68-0855
- Baxe..66-0848

Absorption spec— Buxt..76-1072

trum of products

similar to that of

02"; but decay

slower (see ref.

76-1072). Pro~

duct transfers an

electron to

p-benzoquinone

(o0e ref. 76-1134),

Evidence possibly

indicates product

to be CdOs*.

Estimated from de— Bust.75-1027

cay of Cd* in ab—

sence of OH sca~

vengers taking in~

to account the

major competing

reaction Cd* + Cat.

Experimentally de- Baxe..66-0848

termined rate con-

stant for the decay

of Ca* in the ab-

sence of OH scaven—

gers. Not correct-

ed for Cd* + Cd*

or other competing

reactions.

Estimated from Kelm..75-1064

computer analysis

of the decay of

the optical absorp—

tion and conduc~

tivity of Ca* in

the absence of OH

scavengers, taking

Cd* + Cd* and

Ca* + Hae as the

competing reac—

tions. Products

identified from

conductivity

changes.



TapLE 19. Ruthenium. (ID, GID and (IV) reactions
Reaction Kame mols a 7 we pr Method ‘Comments Ref

RawverdaNe

Raveena + 2k = 2.7 210° 20-42 nat ve Baxe.71-0234
a(NEta)oNe* (ie)

Reqvey.cr + 1.0 —~ a7 Ht O4et 20 pe

Ra(NH)eHeO" + 10x10 3x10 20 nat Pr Baxe..70-0178
RecNcit =
RA(NHOLCD + RuCNEL) EO"

Ru(NHysNO** + O- 7.6 x 10° Rr = pe Armo.75-1049

RUNHNOTM 1 HECCE 5.7 x 10% - RT 1.0-10.3 pr Armo..75-1077
“Ra(NH.)2NO. CHAC(CH2).08TM

Ra(NHyeNO* + 3x10" = RT nat Pr Armo..75-1077
OaCaC(CH)sOH
Gt oro

Re(NE aaNet? + HO 250 -t 20e* - oe 2 nat pr Baxe.71-0284
Ra(NEL)OHe* OS Ne

Ss.



TABLE 21. Thallium(0) and (II) reactions — Continued

No. Reaction ‘k/dm* mol"! 8“? *

I wee pH Method

‘Comments Ref.

21.25 TH + TI* (dis) 2k = (8.8 + 0.6) x 10*

2k = (5.2 + 0.5) x10
2k = (5.5 + 0.5) x 10*
2k 1.2 + 0.9) x 10%
3 & 0.1) x 10°

2k = (1.2 + 0.1) x 10°

2k = (1.3 + 0.1) x 10°
Ey = 7.9 £15k) mol

2k/esre = (6.1 + 0.6)
x 10¢ ems"

2kl exe = (1.3 + 0.2)
x 10% cms"

2126 © TIOH* + TIOH*

is)

2k = (4.6 + 1.6) x 10°

2k = 5x 10°

21.27 TH* + -CH,OH
(et or af)

(1.2 + 0.3) x 10

21.28 T* + CHsC HOH
(et or af)

(L5 + 0.4) x 10

1 23 0 pr
(HC10,)

0.25 25 1
025 25 06
0.50 25 0.6
1.0 25 0.6
1.0 25 0.3
1.0 25 0
- 1545 =

fph.
fph,
£ph.
fph.
fph,
£ph.
fph.

1 w2+2 0
(HCIO.)

fph.

1 +2 0
(HC10,)

ca. 0 RT 65, pr

- 23+2 0.43 Y

57

Measured from decay
of TI* monitored

at 280 om. Value

of €neo used to cal—
culate rate constant
not given, but is ca,
3200 dm? molTM* em“.
Measured from decay
of TH* monitored

at 270 nm. Rate
constant calculated
taking €zre = 5500
dm? mol” cm”. This
value was obtained by
interpolation from the
measured spectrum of
‘Ti and the value of
a0 = 5400 dm? mol-*
cm” measured by Cercek
et al (ref. 66-0097).
Note however that this
latter value was mea—
sured in solutions at
pH ca, 6.5 and refers
therefore to TIOH*
(see entry 21.19).
Measured in the pre-
sence of 5 x 10TM* mol dmTM*
‘TTM and 1 x 10-*

mol dm”? TH.
Measured in the pre~
sence of 5 x 10°

mol dm“* TY and 5
x10" mol dm 2-
propanol.

Measured from decay
of TIOH* monitored

at 260 om. Rate
constant calculated
taking és = 5400
dm? mol” emTM*.
Extinction coeffi-

cient used to caleu—

late rate constant

not given.

Estimated from the
‘y-ray induced chain
reaction in TIT +
methanol solutions,
taking (TI + TI)

= 5.5 x 10* dm* mol*
871 (Gee entry 21.25).
Estimated from the
‘y-ray induced chain
reaction in TH! +
ethanol solutions,
taking AT! + TH)

= 5.5 x 10° dm® mol
87 (see entry 21.25).

Schw...74-1017

Fale..74-7625

Bure.70-7309

Bure.70-7309

Cerc..66-0097

‘O'Ne.75-1130

Bure.70-0336

Bure.70-0336


TABLE 3. Cd(I) reactions — Continued

No. Reaction ‘k/dm? mol* o7* * I wC pH Method Comments Ref.
3.51 Ca* + 2-hydroxy- (8.57 + 0.4) x 10" - e022 7.0 pr Measured by the Rao.73-1104
1,4-naphthoquinone > rate of formation
Cat + (2-hydroxy-1,4- of the semiquinone
naphthoquinone)- in the presence of
ca. 1 mol dm=*
2-methyl-2-propanol.
3.52 Cd* + menaquinone—> (4.6 + 0.5) x 10° - RT 7.0 pr Measured by the Rao.73-1047,
Ca** + (menaquinone)” rate of formation Rao.75-1032
of the semiquinone
in the presence of
ca. 1 mol dm“
2-methyl-2~propanol.
(4.68 + 0.5) x 10° -  a.22 70 pr Measured in the Rao.73-1104
presence of ca. 1
mol dmTM* 2-methyl~
2-propanol.
3.53 Cd* + NAD > (2.9 + 0,3) x 10° -  ca,22 7.0 pr Measured by the Rao.73-1104
Ca* + NAD- rate of formation
of NAD- in the
presence of ca. 1
‘mol dm“* 2-methyl~
2-propanol.
354 Cat + 14 (7.35 + 0.7) x 10° -  a.22 70 pr Measured by the Rao.73-1104
naphthoquinone-2— rate of formation
sulphonate of the semiquinone
ca + (4 in the presence of
naphthoquinone-2~ ca. 1 mol dmTM*
sulphonate) ‘2-methyl-2-propanol.
3.55 Cat + PNDA (et) 14x10" - RT nat pr - Dain.68-0066
3.56 Cd* + riboflavin > (6.10 + 0.5) x 10° - 22-10 pr Measured by the Rao.73-1104
Cat + (riboflavin) rate of formation
of the reduced
riboflavin in the
presence of ca. 1
mol dmTM* 2-methyl-
2-propanol.
Calf) complexes
CaEDTA
3.57 CAEDTA*TM + BrOs" (et) (6.9 + 1.8)x 10° 0.16 RT 113 pr - Meye.70-1228
Ex=46412 0.16 390 113 pr - Meye.70-1228
KJ mol"
3.58 CdEDTA* + CaEDTA K'less0 = (58 0.16 RT 11.3 pr Unclear whether & Meye.70-1228
(et or af) 1.5) x 10° or 2k.
cms?
‘B= (442) 0.16 RT 113 pr _—_Unclear whether & Meye.70-1228
x10" or 2k.
3.59 CaEDTA + 10s" (et) 2.7 + 0.6) x 10° 0.16 RT 11300 opr - Meye.70-1228
3.60 CAEDTA*” + NOs“ (et) (8.2 + 0.6) x 10* 0.16 RT ns Pr - Meye.70-1228
E=84412 0.16 3-90 113 pr - Meye.70-1228
KS mol
3.61 CaEDTA” + NOs“ (et) (1.66 + 0.3) x 10" 0.16 RT 11300 opr - Meye.70-1228
Ca{en),* (n unknown)
3.62 Cafen)a* + BrOs" (et) —(1.28 + 0.3) x 10* 0.64 RT 14 opr - Meye.70-1228
3.63 Cafen)a* + 10s” (et) (2.5 + 0.5) x 10° 0.64 RT 114 opr - Meye.70-1228
3.64 Calen)a* + NOs” (et) (1-12 + 0.2) x 10° 0.64 RT M4 opr - Meye.70-1228
3.65 Cdlen)a* + NOs (et) (4.5 + 0.9) x 10* 0.64 RT 14 pr - Meye.70-1228

ll


Foreword

The National Standard Reference Data System provides access to the quantitative data of phys-
ical science, critically evaluated and compiled for convenience and readily accessible through a
variety of distribution channels. The System was established in 1963 by action of the President’s
Office of Science and Technology and the Federal Council for Science and Technology, and
responsibility to administer it was assigned to the National Bureau of Standards.

NSRDS receives advice and planning assistance from a Review Committee of the National
Research Council of the National Academy of Sciences-National Academy of Engineering. A num-
ber of Advisory Panels, each concerned with a single technical area, meet regularly to examine
major portions of the program, assign relative priorities, and identify specific key problems in
need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels
which make detailed studies of users’ needs, the present state of knowledge, and existing data re-
sources as a basis for recommending one or more data compilation activities. This assembly of
advisory services contributes greatly to the guidance of NSRDS activities.

The System now includes a complex of data centers and other activities in academic insti-
tutions and other laboratories. Components of the NSRDS produce compilations of critically
evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computa-
tions of useful functions derived from standard reference data. The centers and projects also
establish criteria for evaluation and compilation of data and recommend improvements in ex-
perimental techniques, They are normally associated with research in the relevant field.

The technical scope of NSRDS is indicated by the categories of projects active or being
planned: nuclear properties, atomic and molecular properties, solid state properties, thermody-
namic and transport properties, chemical kinetics, and colloid and surface properties.

Reliable data on the properties of matter and materials are a major foundation of scientific
and technical progress. Such important activities as basic scientific research, industrial quality con-
trol, development of new materials for building and other technologies, measuring and correcting
environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility
to support American science, industry, and commerce is vitally fulfilled.

. .

Ernest AMBLER, Director

seny


TABLE 9. Mercury(0) and mercury() reactions — Continued

New Reaction ‘e/ame molt a 7c pe Method ‘Commonts
oe ig et Bk — oa LS Re 11.0 7 =
ae @or 14) KOM RT aa i -
Pats Panes at immermediane pH’
9.9 Het + Os (or or ad a0 + 0.0) 10" - ees 7 -
= Rr 4112 Pe =
acon RT aa re =
understanding of why thie should be, and we suggest. therefore, that the reaction mechanisms written above should be viewed
Sith caution. Note also that the spectral data for Hg" obtained by Farage! and Amozig Gef. 720200) and by Fujita ef al. (ref
75-1060) do noe correnpond
Tar and rotated spoctes
9100 Hebe ho tigBr — Mgebee 2k 8x10 Rr - ee Jung76
2k = 0 + 0.27 ar - Pr
oan HgBr + 0. — HgDroe Dor er - pr
212 HgBr 4 1,4 benzo > 10" RT 555 pr Jung-76
‘quinone —~ Heirs +
Gia bonzoquinone)=
“methane —- Hebe + ~ ~ _ une
GODS + NO.
8.14 HgBrO. + 1,4-benzo— 7x10" Rr - pe Jung-76
‘quinone —- HigBe
Oe Ga tense
quinone)
Bgct
9.315) Hecl + Bec 2k — 0 + 0.5) ar - pe Nash.
TygaCle = 10"
246° HeCl + 0. HecIo. (2.0 -£ 0.8) = 10" er - pr Nezh.7
one 3.0 x 10" ee ~ pr Jung-76
3.9 + 0.4) 10" ase2 sa Pe Suntre®
(2.5 © 0.3) = 10" Rr 555 ee Nash.?

a2



Taste 5. Chromium(]). chromium({1) and chromium(V) reactions

No. Reaction ‘/dm* molTM 97 * I wc pH Method Comments Ref.
CD) Reactions
Crea
51 Crt + HAO <5x 10st - 22+2 30-43 pr_Estimated from first Cohe.74-1142
order, dose dependent
decay of Cr*. Major
competing reactions
thought to be Crt +
HaOs. Ha detected as
product (6 = 2.9 at
pH 3.4).
Cr (from H + Cet)
52 CrH** + HO <1ist - ee 0-2 pr - Cohe.74-1142
5.3 CrH*t + HOt > (1.8 + 0.2) x 10¢ var 2220-2 pr G(Ha) = 3.8 at pH Cohe.74-1142
C+ + Ha + HO 0-2.
CH{UD) reactions (includes only those measured by radiolytic methods).
Cat
54 Cet + Bro (1.9 + 0.2) x 10° 02 223 1 pr __ Reaction occurs by Laur.74-1104
GrBr* + Bro inner sphere dif—
fusion controlled
mechanism.
C(CxBst+) — 2.4 in
‘y-radiolysis experi
ments,
55 Gt + > (2.4 + 0.3) x 10° 02 2243 1 pr Reaction occurs by Laur.74-1104
CrCP* + CI) or parallel mechanisms
ce + 2CI() involving inner
sphere (path a) and
outer sphere (b) dif
fusion control with
approximately equal
probability. G(CrCi**)
= 14 in y-radiolysis
experiments.
56 Ct + La (1.5 +.0.2) x 10° 02 2243 1 pr Reaction occurs by Laur.74-1104
Crt +r inner sphere dif—
fusion controlled
‘mechanism. Crl?*
characterised by
flash photolysis
and y-radiolysis
experiments. G(CrI**)
= 0.85 at 0°C.
5.7 Cett + MnO" (et) 37x10  €a.0.01 20 nat pt Measured by the Baxe..65-0385
rate of depletion
of the MnO«~ ab-
sorption,
58 Cet + NAO <1 - 25 nat y Estimated from Sell72-0844
the values of

20

‘G(Na) measured in
the y-radiolysis of

Cr+ + NaO solutions.


Library of Congress Cataloging in Publication Data

Buxton, George V
Compilation of rate constants for the reactions of metal ions in
unusual valency states.

(Nat. stand. ref. data ser., Nat. Bur. of Stand. ; NSRDS-NBS 62)

Supt. of Docs. no.: C 13.48:62

1, Chemical reaction, Rate of—Tables, etc. 2, Metal ions—Tables,
I, Sellers, Robin M., joint author. II. Title. III. Series: United States.
National Bureau of Standards. National standard reference data series
; NSRDS-NBS 62.
QC100.U573 no. 62 [QD502] 602°.1s [546’.3]

78-816

NSRDS-NBS 62

Nat, Stand, Ref. Data Ser., Nat. Bur. Stand. (U.S.), 62, 78 pages (June 1978)
CODEN: NSRDAP

©1978 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE
WASHINGTON: 1978

‘For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.
Stock No. 003-003-01882-1 Price $2.40
(Add 25 percent additional for other than U.S. mailing).

- 20402


TaMLE 15. Load() reactions

No. A/dm molto 7 7G pH

asa < 107 = Rr nat

152 = 10° = Rr Bae

isa Bom 10" = Rr met

15.5 Pht 4 ON GH 7.7 = 108 - Rr nes

as.6 < 107 = Rr nat

is? 1 20.8) 10" = ase 6S

15.5 Pht 4 monaquinone —- (3.7 = 0.4) x 10" - Rr 72 Pe Reo.7
Peet (monaquinone)~ Rao?

TIE the data source gives no errors none are ahown here but they should be ansumed te be at


TABLE 6. Copper(I) and copper([II) reactions — Continued

No. Reaction k/dm? mol 5-1 * I uC pH Method ‘Comments Ref.
642 Cu(OH):* + Cu(OH)* 2% = (46406 0002 RT 6 pr Estimated from the Meye71~0174
(ef) x10" decay of CuTM in
N,0 saturated solu—
tions.
2k < 5x10? 0.004 25 6 pr Possibly some contri- Sell72-0844
bution from Cu(OH).*
+ Cu(OH)s and Cu(OH)s
+ Cu(OH)s.
6.43 Cu(OH)s* + ca.3x10 ca. RT 52 pr Estimated from decay Meye71-0174
‘CuNOs* (et) 0,002 of Cu" in presence
of NOs”.
6.44 — Cu(OH)s* + mena- 2.0 + 0.2) x 10° - RT 9.0, pr 40% of CulTM claimed Rao.73-1047
quinone (?) 10.6 to react by elec—
tron transfer. CuTM
formed by OH +
Cu(Cl0y)s.
- - RT 8.0 pr 20.3% electron trans— Rao.73-1047
fer. Cull formed by
OH + CuSO.
- 10.6 pr 39% electron transfer. Rao.73-1047
CuTM formed by OH +
CuSO.
Cu(H1) Complexes. (The precise nature of these complexes is uncertain: all were formed by OH oxidation of the corresponding Cu”
complex).
6.45 CuTM(NHs), + 2k = (3.00.5) <0.008 = RT. la pr - Meye71-0775
CuTM(NHs)q (af?) x10"
6.46  CuTMa-alanine)s (8.0 + 2.4)x10"  <0.002.—s«RT 63 - Meye71-0775
(int et?) st
6.47 CulTM(8-alanine), (7.0 +2.1)x10° — <0.002 «RT 58 - Meye71-0775
(int et?) ot
6.48 CuTM(a-amino-n- 6.0 +15)x10* <0.002.—-RT 6.1 pr - Meye71-0775
butyric acids (int et?) o
649 CulTM\B—amino-n— (45 +1.3)x10*  <0.002,—s-RT 6.0 pr - Meye71-0775
butyric acid)s (int et?) st
6.50 CulTMy-amino-n— (12+04)x10°  <0.002 RT 48 pr - Meye71-0775
butyric acids (int et?) 4
651 Cu®a-amino~ (.540.5)x10°  <0.002 RT 62 pr - Meye71-0775
iso-butyric acid)s st
(int et?) 2.5 +08)x10 <0.002 RT 13 pr - Meye71-0775
ra
6.52 CuTM(en)y (int et?) <3st 0.002 RT 58 pr - Meye71-0775
120 s* 0.002 «RT 116 opr - Meye71-0775
653 Caen), + 5 x 108 0.002 «RT 58 pr - Meye71-0775
CuTen), (af?) 2k = 39x10" 0.002 «RT u6 opr - Meye71-0775
6.54 CuM(gly)e (int (6.0 + 2.0) x 10% <0.002 RT 61 pr - Meye71-0775
et?) st
2.2+0.7)x10! <0.002 RT 15 pr - Meye71-0775

“If the data source gives no errors none are shown here but they should be assumed to be at least 25% (or 50% for 2k).
“The form of Cul reacting reinterpreted from original references according to equilibria 6.37 and 6.39.

28


TamLe 14. Nickel@) and nickel) reactions

Eames molt a 7 wre PH Mathod ‘Comments Ree.
< 84x 10" 0.08 Rr nae pr = Maoys.68_0855
“2 tor Rr nae pe = Bane 66-0848
<5 x10" 08 Rr Ste Pe = Maye. 09-0428
(6.9 0.9) = 10" S08 Br rs Pe = Meye.do—0428
(@.3 & 2.1) x10" 0.08 er 56 pr Meye.69-0428
<5x10 0.08 er so er - Meye-
Serio os. Rr 6 Pr Meye-69—0428
too (O08. Rr 56 Pr Moye.69-0423,
(a7 ons 10" oles Rr s6 Pe Meye.69-0428
(2.8 0.8) x 10" 0.08 Rr 56 pr Meye.69-0428
(2.05 = 0.2) = 10" 0.08 RT 4.0 pr -
(is == 10) = 10" Sos Rr Bs = =
(G12 =e O18) = 10" oe Rr Bo Pr
SSrio- 0a 20 Pr =
G3 © 0.3) = 10" os Re Te Br =
Gia T's) = 10" oloe Rr ve Be =
GA = Ve) = to O08 BT Ts po =
< 5x10" 0.08 RT so a -
< 10" — ar “ pe -
< 2.4% 107 e108 Rr mae Pe =
Bio. (2.2 = Od x 10" cae 2s nat pe =
Net OH + OFT GS = 0:8 = oe = ee ee
‘ack x TO" = ar nae Be

fied i y—radiot
Join atuction Gow
Toe 7320035).

Nit + HOt < 10" 0.08 er nae pe
NE + 10.” oo 2.2 © 0.8) = 10" O08. Rr nat pe =
Ne} Mnos Co 7-5 = 10° olo0s RT nae Pr Measured by the
NES Nt slow (< 10") eT nat pr Kelm..74-1087
Nit + NO. (oo @.5 + 0.2) = 10" 0.08 nr nat pe Meye-68-0855
Ne} Now = Cra = 10+ 0.08 Rr nat Pe Meye.68—0855
Ni Nao 61a = Loe a RE nae Pe Maye.68-0855,
NOT Ne
ea 4 02) a 10" erent ee Buxt.-76-1072
- RT nae pr Buxt.67-0062
= i830 nae Pe Bunu.e7-0062,

Neo a
37 Gee ref. 73-0039).


Taste 5. Chromium(I), chromium(I]) and chromium(V) reactions — Continued

No. Reaction /dma? mol"? ~* * I wc pH Method Comments Ref.
5.25 Cr + CHsCHOCHCHs > 34x10" - 2@+2 0-1 pr Measured by the rate Cohe.74-1146
(CrCH(CHs)OCH.CH:** of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
5.26 Crt + CHsC(CHs):COOH 11x10" - x21 pr Measured by the rate Cohe.74-1146
CrCHsC(CH,),COOH** of formation of the
product. Product
characterised by its
absorption spectrum
and decay kinetics.
5.27 Cr¥* + anthraquinone- (2.8: 0.3) x 10° -  a22 70 pr Measured by the rate Rao.75~1032
2,6-disulphonate —> of formation of the
Cr+ + (anthraquinone— semiquinone in the
2,6-disulphonate)~ presence of ca. 1
mol dm~* 2-methyl-2~
propanol.
5.28 Cr + 1,4-benzo- (8.2 + 0.3) x 10" - te 3.4 pr Measured by the rate Sell.76-1134
quinone — Cr** + of formation of the
(1,4-benzoquinone)- semiquinone in the
presence of 0.5 mol
dmTM* 2-methyl-2-
propanol.
(8.5 + 0.4) x 10° ~  ca22 70 pr Measured by the rate Rao.75-1032
of formation of the
semiquinone in the
presence of ca. 1 mol
dm* 2-methyl-2—
propanol.
5.29 Crt* + tetra (1.2 + 0.2) x 10° - +234 pr Measured by the rate Sell.76-1134
nitromethane —> of formation of the
Crs* + NOs + C(NOs)s~ nitroform anion in
the presence of 1
mol dm7* 2-methyl-2~
propanol.
CAV) (from CrO2- + ex)
5.30 CY + Cr (dis or af) 2k/ eso = (7 3) 0,003 25 nat pr - Sell72-0844

x 108 cm s“*

“If the data source gives no errors none are shown here but they should be assumed to be at least +25% (or +50% for 2h).

23


TABLE 3. Cd(I) reactions

No. Reaction k/dm?® mol" s** 7 wc pH Method Comments Ref.
Chey
3.1 Cd* + BrOs” (et) (1.25 + 0.2) x 10° 0.08 == «RT nat, pr - Meye.68-0855
Ey=134417K 0.08 3-90 nat fa - Meye.70-1228
mol
3.2 © Cat + Cat Ca 2k = ca, 1.2 x 10° 04 2542 nat pr Measured at 300 nm Buxt.75-1027
taking €s00 = 8080
dm* mol”? cm",
Rate constant es—
timated from studies
of Ca* decay in pre-
sence of several
different OH scav—
engers.
2k = 3.0.x 10° 0.002 RT nat pr Measured at 300 nm Kelm..75-1064
taking €s00 = 16500
din* mol”* em“, Rate
constant estimated
from computer analy—
sis of Cd* decay.
Competing reactions
taken to be Cd* +
H,Os and Cd* +
R. (R = CH,COHCH,
CHsCHOH, CHO). Pro-
duct identified
from effect of ionic
strength on its
decay.
2k= 50x10" 0.004 «= RT nat, pr Measured at 313 nm Bark.75-1153
taking €s01 = 14000
dm? mol"? cm“.
Rate constant in
dependent of OH
scavenger used.
3.3 Cat + Colen)s** (et) (1.6 + 0.2) x 10° 008 = RT 5-6 Pr - Meye.69-0428
3.4 Cat + cis-Cofen)sCle* (2.3 + 0.3) x 10° 0.08 RT 56 pr - Meye.69-0428
(et)
35 Ca* + trans—Cofen)sCla* (2.6 + 0.4) x 10° 0.08 RT 5-6 pr - Meye.69-0428
(et)
3.6 Cd* + Cofen)COs* (et) (6.7 + 1.0) x 10 008 = RT 56 vr - Meye.69-0428
3.7 Cat + cis-ColensFa* (6.0 + 0.9) x 10" 008 = =RT 5-6 pr - Meye.69-0428
(et)
3.8 Cd*+Cofen)sFH.0** (et) (4.1 + 0.6) x 10* 008 = =RT 5-6 pr - Meye.69-0428
3.9 Cd* + cis-Co(en)sNHsCP* (1.75 + 0.26) 0.08 RT 5-6 pr - Meye.69-0428
(e) x10
3.10 Cd*-+cis-CofensNHNO#* = (2.8+0.7)x10° 0.08 RT 5-6 Pr - Meye.69-0428
(et)
3.11 Cat + Co(NHs)e** (et) (1.72 0.3) 008 = RT 56 pr - ‘Meye.69-0428
x10
3.12 Cd*-+Co(NHs)sBr** (et) (25 + 0.4) x 10° 008 = RT 4.0 pr - Meye.69-0428
3.13 Cd*+ Co(NHs)sCl* (et) (2.2 + 0.3) x 10° 008 = RT 5-6 Pa - Meye.69-0428
3.14 Ca*+ Co(NHasCN** (et) (9.1 + 1.4) x 10 008 RT 5-6 pr - Meye.69-0428
3.15 Cd* + Co(NHs)sF** (et) (6.4 + 0.8) x 10° 0.08 RT 56 pr - Meye.69-0428
3.16 Ca*-+ Co(NHs)sfumarate* (8.3 + 2.1) x 10" 008 = RT 5-6 pr Products of the Meye.69-0428
(et or af?) reaction have re-
atively large ab-
sorption.
3.17 Cd* + Co(NH)sH.07* (6.2 + 0.9) x 10* 0.08 RT 4.0 pr - Meye.69-0428,
(et)


‘TaBLE 21. Thallium(0) and (II) reactions — Continued

No. Reaction k/dm* mol“ “+ * I wc pH Method Comments Ref.
TE" chloro~complexes
2140 TH+ + cr = Tic K=(2+07) 1 23 0 pr Measured from ef Dods.74-1038
x10'dm* mol"? (HCO) fect of (CI] on ab~
sorption spectrum
of TH,
fy = 9x 10° 1 23 0 pr Measured from rate Dods.74-1038
(aco) of attainment of
equilibrium.
by = 14x 1055 1 23 0 Pa
(HCIO,)
2141 Tit + cr K=(19+04) 1 23 0 pr Measured from ef— Dods.74-1038
TICs x10 dm* mol" = (HCO) fect of [CI"] on
absorption spectrum.
of TH,
2142 Tih +cr= K=134+3dm* 1 23 0 pr Measured from ef— Dods.74-1038
TIC mol"? (ico) feet of [CI] on
absorption spectrum
of TH,
21.43 TH + TI" (dis) 2k = 5.38 x 10° 1 23 0 pre [cr] = 1x10 Dods.74-1038
mol dm->
2k = 5.58 x 10° 1 23 0 pre (CL = 9.71079 Dods.74-1038
mol dm"
2k = 4.74 x 10° 1 23 0 pr (Cl"] = 0.1 mol Dods.74-1038
m3
2k = 3.70 x 10° 1 23 0 pr (CI'] = 0.98 mol Dods.74-1038
dm*
Plus data at intermediate chloride concentrations.
"If the data source gives no errors none are shown here but they should be assumed to be at least ++ 25% (or ++ 50% for 2k).
TaBLE 22. Thulium(II) reactions
No. Reaction k/dm* mol? sTM* * I re pH Method Comments Ref.
Tmay
22.1 Tm** + OH (et) (7+ 1)x10° - RT 3.6 fa - Piks..73-1084

"If the data source gives no errors none are shown here but they should be assumed to be at least 25% (or +50% for 2k).

59


(ot or 29 (2.2 © 0.4) x 10" 078
(rrKSO261
Pe 4 M02 GF at 7) @ + Dx 10" 0.78
(PreSODe1
Prev 4 HS0.- 2.0 + 0.3) = 10" a
tor Hao
4 NOs (erry @ + px107 0.75
[PeSO0e1
Rev Pee 2k — 1.6 + 0.8) <
(ece comments) = tom

ar

Rr
RT
Rr

pe

Measured from effect
of pH on absorption
oe Praw).

Fara. 72-0066

Fara.72—0066

Fara.72-0066

“data source gives no errore mone are shown here but they should be

sumed to be at least 25% (or 50% for 24).


Tamie 17. Platinum() and platinum(I1) reactions — Continued

Ram? mol 7 we PE Method "Comment Ref
2k — oa. 2x10" os = o8 Pr Rate constant in Stor 7S-4n8e
aicy 2s for the decay of
the second transient

(ery ie entry

7-11. “Meamured in

PEM from PCat + he

Pen Pen Geo (2.8 0.3) x 10" 2x 107+ - = From dependence of Wrig-72-7088

Per 4 PHM (aia 2k = (4.6 + 0.4) x on 58 eph. Wrig.72—7088
18 x Lon - Rr nat pe Adam..68-0169
2.0 = 108 a - Rr nat Pr Ghon.69-0144
2.0 = 108 a+ - Rr nae Pr Adam..68-0169
Bhd Pelee + omg
Gee. 68-0169).
PES from Petondat® + Cle
Cee CES as + ons - oa. os pr Decay approxi Stor..75-1188

Mot diene Bea.

a7


‘TABLE 3. C(I) reactions — Continued

No. Reaction, k/dm* mol"* 5“ * I sc pH Method ‘Comments Ref.
3.36 Cat + Pb** (et) 75x10? - RT nat pr - Baxe..66-0848
3.37 Cat + Ru(NHs)e** (et) (2.2 + 0.3) x 10° 0.08 RT nat pr - Nav..70-1229
3.38 Cat + SiO?” > (2.4 + 0.2) x 10° 0.02* 252 nat pr Product identifi Bust..76-1072
Catt + SO. + SOe- cation: SO." ob-
served to form at
same rate as Cd*
decayed.
3.39 Cd* + Zn** <0 - RT nat pr - Baxe..66-0848
3.40 Cd* + -CH,OH — CdCH,OH* 2x10 - RT nat pr Product inferred Kelm..75-1064
from conductivity
measurements.
341 Cat + CHsCHOH > <2x10 - RT nat pr - Bark.75-1153
CaCHsCHOH* (1.3 £ 0.7) x 10° - RT nat pr Product inferred Kelm..75-1064
from conductivity
measurements.
3.42, Cd* + -CHOHCH.OH < 2x10 - RT nat pr - Bark.75-1153
3.43 Cd* + CHsCOHCHs > < 2x10 - RT nat pr - Bark.75-1153
CaCHsCOHCHs*
(24 + 1.2)x 10° - RT nat pr Product inferred Kelm..75-1064
from conductivity
measurements.
3.44 Cd* + -CHOHCHOHCH.OH <2x10 - RT nat pr - Bark.75-1153
3.45 Ca* + -CHx(CHs),COH — ca. 1 x 10° - RT nat pr _Isobutene detected Kelm..75-1064
Ca¥ + (CHs)sC=CHs + OH- as product.
< 2x10 - RT nat pr - Bark.75-1153
3.46 © Cd* + ~(CHsCH.0),(CHCH:0)- < 2x10 - RT nat pr Radical from Bark.75-1153
polyethylene glycol
(mw 104) + OH.
3.47 Cd* + allyl alcohol < 5x10" - %5+2 nat pr - Buxt..76-1072
3.48 Cd* + 9,10-anthra— (1.03 + 0.1) x 10° - ca22 7.0 pr Measured by the Rao.73-1104
quinone —> Ca?* + rate of formation
(9,10-anthraquinone)- of the semiquinone
in the presence of
ca. 1 mol dmTM*
2-methyl-2-propanol.
3.49 Cd* + benzophenone > 1.0 x 10° - RT 70 pr Measured by the Rao.75-1032
Ca** + (benzophenone)~ rate of formation
of the ketyl radi—
cal in the presence
of ca. 1 mol dmTM*
2-methyl-2-propanol.
3.50 Cd*+ 1,4-benzoquinone—> (4.1 + 0.8) x 10° - +2 5.4 pr Measured by the Sell.76-1134
Ca#* + (1,4-benzoquinone)~ rate of formation
of the semiquinone
in the presence of
1 mol dm“*
2-methyl-2-propanol.
44x10° - RT 70 pr Measured in the Rao.75-1032
presence of ca. 1
mol dm”* 2-methyl-
‘2-propanol.
(7.7 + 0.8) x 10° - ca.22 = 7.0 pr Measured in the Rao.73-1104
presence of ca. 1
mol dmTM* 2-methyl-
2-propanol.

10