THE REDOX THERMODYNAMICS FOR DIOXYGEN SPECIES (02, 02-', HOO', HOOH,

AND HOO-) AND MONOOXYGEN SPECIES (0, 0-', 'OH, AND -OH) IN WATER AND
APROTIC SOLVENTS

Donald T. Sawyer

Department of Chemistry
Texas A&M University
College Station, Texas 77843, U.S.A.

Biological systems activate dioxygen (02) by reduction via elec-

tron transfer and H-atom transfer to give intermediates that may be
further activated by transition metals in proteins and metabolic co-
factors. The reaction thermodynamics for these processes are influ-
enced by the solution matrix and its acidity. Thus, the redox ther-
modynamics of 02 are directly dependent upon proton activity,

(1 )

which in turn depends upon the reaction matrix. Table 1 summarizes

the pKa' values for a series of Br0nsted acids in several aprotic
solvents and water. 1 In acetonitrile the activity values for pKa'
range from -8.8 for (H30)CI04 to 30.4 for H20. This means that the
formal potential (Eo,) for reaction 1 in acetonitrile (MeCN) is +1.75
V vs. NHE in the presence of 1M(H30)Cl04 and -0.56 V in the presence
of 1M (BU4N)OH.
Another limiting factor with respect to chemical-energy flux for
oxidative metabolism and respiration is the solubility of 02. Be-
cause of its non-polar character dioxygen is much more soluble in or-
ganic solvents than in H20 (Table 2) .2
The reduction potentials for 02 and various intermediate species
in H20 at pH 0, 7, and 14 are summarized in Figure 1;3-5 similar data
for 02 in MeCN at pH -8.8, 10.0, and 30.4 are presented in Figure
2.2,6,7

M. G. Simic et al. (eds.), Oxygen Radicals in Biology and Medicine

© Plenum Press, New York 1988 11
Table 1. Effective pKa,' Values for Br~nsted Acids in Aprotic Solvents
and water 1

Solvent [0.5M (Et4N)CI04]

Br~nsted Acid MeCN DMF Me2SO pyr H2O

(H30 )CI04 -8.8 0.7 2.6 4.6 0.0

MePhS03H -3.8
(PyrH)CI04 1.8 3.1 4.4 5.7 4.9
2,4-(N02)2PhOH 4.3 4.5 4.9 5.5
(NH4)CI04 5.9 9.6 11.7 7.3 8.7
(Et 3NH)CI 10.0 9.9 12.7 7.6 10.1
PhC(O)OH 7.9 11.5 13.6 11.6 3.2
2-Pyr-C(0)OH 8.6
PhOH 16.0 19.4 20.8 20.1 9.2
12-EtOPhOH 19.3 21.5 23.8 21.8 9.6
H2O 30.4 34.7 36.7 30.5 14.8

MeCN, acetonitrile; DMF, dimethylformamide; Pyr, pyridine

Table 2. Solubilities Qf 02 (1 atm) in Various Solvents 2

Solvent [02]1 atm, roM

H2O 1.0
Me2SO 2.1
DMF 4.8
pyr 4.9
MeCN 8.1
Hydrocarbons -10
Fluorocarbons -25

The reduction manifolds for 02 (Figures 1 and 2) indicate that

the limiting step (in terms of reduction potential) is the first
electron transfer to 02, and that an electron source adequate for the
reduction of 02 will produce all of the other reduced forms of dioxy-
gen (02-·, H02·, H202, H02-, ·OH) via reduction, hydrolysis, and dis-
proportionation steps (Scheme 1) .8,9 Thus, the most direct means to
activate 02 is the addition of an electron (or hydrogen atom), which
results in significant fluxes of several reactive oxygen species.

12
 +1.66
I - -- -. -- +1.13

0, -0.05(.0.12) H~' +1.44 H,o, .0.80 H,O+ .0Il +2.72 2H!0

I +0.695 (+0.78) II +1.763 II pH 0 (lM H+)
+0.73 (+0.79) I
+1.229 (+ 1.27)

+1.20

rI +0.64 I
0:2 -0.33(-0.16) ~; +0.89 H~2 +0.38 H2 0 + .OH +2.31 2 H 20
-I +0.281 (+0.36) II + 1.349 II pH 7
+0.31 (+0.37) I
+0.815 (+0.86)

+0.65
ir------- --- -- +0.09
I I
-0.33(-0.16) +0.20 -0.03 _ _ +1.77
o ~. H02- HO +·0 40W
r -0"'" (.0.02) II .0.867 II pH 14 (lM OW)
-0.03 (+0.01) I
+0.401 (+0.44)

Figure 1. Standard reduction potentials for dioxygen species in water

[02 at 1 atmj (formal potentials for 02 at unit activity).

Col
~
+2.17 V vs. NHE
,- +1.64 I
I I
+0.64 HO. +1.96 H ° +1.32 H ° .OH +3.24 2H °
02 2 22 2+ 2
pH-8.8
I +1.30 II +2.28 I~ [1 M(H3 0)004]
+1.31 I
____ +1.79____ __

+1.06
I +0.53 -- I
II I
02 -0.47 H 20. +0.85 H 20 2 +0.21 H20 + .OH +2.13 2H 2 0
pH 10.0
[1:1(Et3NH)Cl/Et 3 N]
I' ~.19 II +1.17 II
+0.20 I
+0.68

-0.50
-1.04
r-I I
02 -0.63 02: "-1.27 H02- .... -1.02 HO-+ .0- ...... +0.80 40H-
pH 30.4
[lM(Bu4N)OH]
~.~ II II
-0.90
I' ~.11I
-0.53

"(02-. -1.51 .. H2 0 2) ....(H2 0 2 -0.90 ~ -OH +"OH ) ...... ( "OH +0.92 .. -OH)

Figure 2. Formal reduction potentials for dioxygen species in

acetonitrile (02 at unit activity).
REACTIVITY OF 02-' AND H02'
The dominant characteristic of 02-' in any medium is its ability
to act as a strong Br0nsted base via formation of H02·,10,11 which
reacts with allylic hydrogens, itself, or a second 02-' (Scheme 1).

1,4-CHD r 1l2
1,3-CHD' + H20 2
1,3-CHD + 1/2 PhH

k,10 2 M- 1 s- 1

HA
i H 2 0 2 + A-

H0 2- + 02

I H 20 2
~ 02-' + H2 0 + 'OH

Scheme 1 (Me2S0)

Within water, superoxide ion is rapidly converted to dioxygen and

peroxide

K, 2.5x10 B M (2)

Such a proton-driven disproportionation process means that 02-' can

deprotonate acids much weaker than water (up to p Ka=23) .12
The data of Figures 1 and 2 indicate that 02-' is a moderate
one-electron reducing agent [cytochrome c(Fe III ) is reduced in
H20 13 ,14 and iron(III) porphyrins in dimethylformamide].

LlE, +0.7 V (3)

Superoxide ion reacts with proton sources to form H02', which

disproportionates via a second 02-' or itself (Scheme 1). However,
with limiting fluxes of protons to control the rate of H02' formation
from 02-', the rate of decay of H02' is enhanced by reaction with the
allylic hydrogens of excess 1,4-cyclohexadiene (1,4-CHD) ,15 Because
H02' disproportionation is a second-order process, low concentrations
favor hydrogen-atom abstraction from 1,4-CHD. This is especially so
for Me2S0, in which the rate of disproportionation for H02' is the
slowest (PhCl>MeCN>H20>DMF>Me2S0).

15
REDOX THERMODYNAMICS FOR ATOMIC OXYGEN
The electron-transfer potentials for the reduction of ground-
state atomic oxygen in water and in acetonitrile are summarized in
Tables 3 and 4. 3 ,4,15 In addition, selected values for the reduction
of the zero-valent oxygen in 03, HOI03, and HOCI are included. 3 Be-
cause the valence (charge number) of oxygen in water is zero, these
reduction processes represent the facilitated reduction of protons
via stabilization of the product H-atoms through strong covalent-bond
formation with atomic oxygen. Thus, the standard-state reduction of
protons,

EO, O.OOV vs. NHE (4)

is shifted to a much more favored process in the presence of atomic

oxygen

(5)

Likewise, the electron-transfer reduction of H20 [with zero-

valent (neutral charge) hydrogen and oxygen), which must overcome the
stabilization of the strong O-H bonds, results in a -1 charge for
oxygen rather than proton reduction

EO, -0.82V vs. NHE (6)

In contrast, an equivalent charge-density change for the neutral

oxygen in ·OH is strongly favored?

(7)

and reduction of the combination of the zero-charge oxygen of water

with -I-charge 0-· yields two -I-charge hydroxide ions 4

(8)

Although the chlorine atom is among the strongest one-electron

oxidants known 4

EO, +2.41V (9)

when it is stabilized by the covalent bond of the C12 molecule and of

the ClO- ion its propensity to change valence is reduced 3 ,4

EO, +O.63v (10)

EO, +1.36V (11)

16
 (12)
EO, +0. 89V (13)

Thus, C12 can transfer an electron from an -OH because of the stab-
ilization of 'OH via bond formation with an H' from another -OH and
of the resulting 0-' via bond formation with a Cl· [~EO, +0.47V (Eq.
(11) - Eq. (13)) 1

(14)

NUCLEOPHILIC ATTACK VIA SINGLE-ELECTRON TRANSFER

The facile nucleophilic displacement of chloride ion from alkyl
chlorine compounds (all O-charge atoms) by -OH (-l-charge 0) to give
an alcohol (with all neutral-charge atoms) is a charge-transfer pro-
cess via electron transfer from the -OH to the chlorine atom of
RCl 1 6,17

n-BuCl + -OH ~ n-BuOH + Cl- (15)

Likewise the nucleophilic addition of -OH (-l-charge 0) to C02 gives

bicarbonate ion with the charge of the oxygen of the C-OH group
changed to zero via electron transfer (and charge transfer) to a
neutral carbonyl oxygen

oII
O=C=O + -OH ~ HO-C-O- (16)

The dissolution of Na20(s) (-2-charge 0) in water occurs via a charge

transfer (and electron transfer) from 0 2 - to the neutral oxygen of
H20 to give -OH (-l-charge 0)

(17)

The data of Figures 1 and 2 and of Tables 3 and 4 provide per-

suasive evidence that the electron-transfer and atom-transfer chem-
istry for dioxygen species and monoxygen species is strongly depen-
dent upon proton activity, anion solvation, and relative X-OO and Y-O
covalent bond energies. Hence, the solvation energy of -OH is 22.5
kcal less in acetonitrile than in water, which causes the 'OH/-OH
redox potential to be +0.92V vs NHE in MeCN instead of +1.89V vs NHE
in H20.

17
Table 3. Redox Potentials for Atomic Oxygen Species in Aqueous Media

EO, V vs. NHE

pH 0;
O(g) + 2H+ + 2e- -+ H20 +2.42
O(g) + H+ + e- -+ ·OH +2.12
·OH + H+ + e- -+ H20 +2.72
03 (g) + 2H+ + 2e- -+ +2.07
03 + e- -+ 03-· +0.95
HOOH + 2H+ + 2e- -+ 2H20 +1.76
HOI03 + H+ + 2e- -+ I03- + H20 +1. 6
HOCI + 2H+ + 2e- -+ HCl + H20 +1. 49
pH 7:
O(g) + 2H+ + 2e- -+ H20 +2.01
O(g) + H+ + e- -+ ·OH +1. 71
·OH + H+ + e- -+ H20 +2.31
03(g) + 2H+ + 2e- -+ 02(g) + H20 +1. 66
03(g) + e -+ 03-· +0.95
HOOH + 2H+ + 2e- -+ 2H20 +1.35
I04- + 2H+ + 2e- -+ I03- + H20 +1.2
pH 14:
O(g) + H20 + 2e- -+ 2 -OH +1. 60
O{g) + H20 + e -+ ·OH + -OH +1.31
O{g) + e -+ 0-· +1. 43
·OH + e -+ -OH +1. 89
HOH + e -+ H· + -OH -2.93
0-· + H20 + e- -+ 2 -OH +1.77
03(g) + H20 + 2e- -+ 02(g) + 2 -OH +1. 25
03 (g) + e -+ 03-· +0.95
-+ 02(g) + 2 -OH +1.55
HOO- + H20 + 2e- -+ 3 -OH +0.87
I04- + H20 + 2e- -+ I03- + 2 -OH +0.8
CIO- + H20 + 2e- -+ Cl- + 2 -OH +0.89
CIO- + e- -+ Cl- + 0-· +0.02

18
Table 4. Redox Potentials for Atomic Oxygen Species in MeCN [H+ - 1M
(H30)CI04; -OH = 1M (BU4N)OH(MeOH)]

EO, V vs. NHE

Acid, pH(-8.8):
O(g) + H+ + e ~ 'OH +2.64
'OH + H+ + e ~ H2O +3.24
O(g) + 2H+ + 2e- ~ H2 O +2.94
03(g) + 2H+ + 2e- ~ 02 (g) + H2O +2.59
HOOH + 2H+ + 2e- ~ 2H20 +2.28
HOCI + 2H+ + 2e- ~ HCI + H2O +2.0
Base, pH 30.4:
O(g) + H20 + e +0.34
+0.80
'OH + e +0.92
HOH + e -3.90
o (g) + H20 + 2e- ~ 2 -OH +0.63
03 + H20 + 2e- ~ 02 + 2 -OH +0.28
ClO- + H20 + 2e- ~ CI- + 2 -OH -0.08
HOO- + H20 + 2e- ~ 3 -OH -0.10

ACKNOWLEDGMENTS
This work was supported by the National Science Foundation under
grant No. CHE-8516247.

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20