CHAPTER 4

OXIDATION-REDUCTION REACTIONS

IN THE same way as we have looked at transfer and exchange reactions of ionic
and molecular species in preceding chapters, here we shall look at transfer and
exchange reactions of electrons.
DEFINITION. A substance which gains one (or several) electrons is called an
oxidizing agent; conversely, a substance liable to lose an electron is a reducing
agent. An oxidation-reduction couple is defined by
oxidizing agent + ne ^ reducing agent.
The reaction involving gain of an electron is a reduction; the converse reac-
tion is an oxidation.

ELECTRON TRANSFER REACTIONS IN NON-POLAR MEDIA

Consider a reducing agent A and an oxidizing agent capable of exchanging

an electron. The electron transfer reaction is:
+ -
A + B^AB
By accepting an electron the oxidizing agent B becomes the anion B~, and
the reducing agent becomes the cation A + by loss of an electron. A + andB"
remain associated (ion pair) due to the weak dissociating power of the solvent
0 < about 15).
Examples. 1. Hydrocarbons R such as naphthalene can be reduced in ether
by alkali metals:
+
Na + R ^ Na R
2. Alkali metals also reduce, in non-polar solvents, nitric oxide NO, oxygen
0 2 , hydrogen, metals, etc.:
K + NO^KNO
K + 02^K02
Li + iH 2 ^ Li H
K + Pb ^ K Pb

127
128 CHEMICAL REACTIONS IN SOLVENTS AND MELTS

3. Nitric oxide NO can reduce copper halides:

NO + CuX 2 ^ NO CuX 2

All these reactions are characterized by equilibrium constants, which can be

represented on scales pA or pB, as for complexes.
Note. It is difficult to distinguish between association reactions of A and B by formation of
a complex or by electron transfer without bringing in considerations of the structure and the
nature of the bond. Association by electron transfer is only a limiting case and actual reac-
tions usually occur without complete transfer and without the compound formed being a true
ion pair. It is therefore more logical to talk about complexes in these cases.

ACTION OF THE SOLVENT. The solvent itself can sometimes play the part of an
oxidizing agent and accept an electron in the presence of a reducing agent; e.g.
ammonia and the aliphatic amines:

NH 3 + Na ^ Na N H 3

RNH 2 + Na ^ Na RNH 2

NaNH 3 , NaRNH 2 are almost undissociated (see further "solvation of the

electron").

ELECTRON EXCHANGE REACTIONS IN POLAR MEDIA

In media sufficiently polar to make the ion pairs practically totally dissociated,
oxidation-reduction reactions are electron exchange reactions between a reduc-
ing agent of a system 1 and an oxidizing agent of a system 2:

Red t ^ Oxj + e
Ox 2 + e ^ Red 2
Ox 2 + Red x ^ Red 2 + Ox!
e.g.
Fe2+^Fe3+ + e
Ce 4 + + e^Ce3 +

Ce 4 + + F e 2 + ^ C e 3 + + Fe 3 +
Ce 4 + is reduced by Fe 2 + .
More generally,
Red x ^ Ox t + «i£
Ox 2 + n2e ^ Red 2
«iOx 2 + « 2 Red x ^ « 1 Red 2 + n2Oxt
PREDICTION OF REACTIONS. SCALE OF POTENTIAL. 1. In water the free solvated
electron does not exist for any length of time.
 OXIDATION-REDUCTION REACTIONS 129
Oxidation-reduction power is characterized by an oxidation-reduction po-
tential E, defined by Nernst's formula:
Ox + ne ^ Red
^ „ RT t [Ox]
E = E0 + loge
L J
thus at 20°
£ = E0 + log-
[Red]
E0 is the standard potential, characteristic of the system considered and analo-
gous to the equilibrium constant. It is defined by reference to an arbitrary origin
which is, in water, the potential of the standard hydrogen electrode (platinum
electrode, pH = 0 and solution saturated with hydrogen at a pressure of
1 atmosphere).
A scale of potential is drawn, shown in Fig. 58, on which the values of E0
(scale in volts) are placed. Each couple appears on the scale at the correspond-
ing value of E0. The strongest oxidizing agents (electron acceptors) appear at
the top left; the strongest reducing agents (electron donors) at the bottom right.
The scale has then the most reducing species at the bottom and the most
oxidizing at the top.
By means of this scale we can qualitatively predict that an oxidizing agent
is liable to react with all reducing agents of a system situated lower on the scale
(lower standard potential), and inversely.
Also the equilibrium constant of the reaction can be predicted, e.g.:
flOxj + ne^aRcd1, E1
b Red 2 ^ b Ox 2 + ne, E2
a Ox± + b Red 2 ^ a Red x + b Ox 2
K= lRediHOx2]>. lQgK= Et-E2
[OxJ 0 [Red2]» 0-058 A
This is, to a close approximation, the distance between the two oxidation-
reduction couples on the scale of potential.
2. In another solvent which does not solvate the electron, we can work in the
same way as in water. A scale of potentials is drawn on which the standard
potentials of different oxidizing-reducing agents in the given solvent are placed.
This scale has an arbitrary origin, which can be the potential of a standard
hydrogen electrode in the solvent considered (platinum electrode, solution with
[H + ] = 1 and saturated with hydrogen at a pressure of one atmosphere).

Limitations of the Scale of Potential by the Oxidation or Reduction of the Solvent.

1. Consider aqueous solutions. The water can be reduced:
2 H 2 0 + 2e^ H 2 t + 2HO", E0 = -0-81 V
5 CRS
130 CHEMICAL REACTIONS IN SOLVENTS A N D MELTS

The strongest reducing agents, e.g. the alkali metals and various other metals,
cannot exist in water as they reduce it with evolution of hydrogen and hydroxide
formation. Water thus limits the possibilities of reduction of the weakest oxid-
izing agents (Fig. 58).
E (volts)
A

Water is o x i d i z e d — ■ »
Ce*+- -Ce3

Cl 9 -Cl-

Br2 t 10V
9
Fe 3"Mk&i
Fe(CN)|- - Fe(CN)^
Clj2 + - ^Cu I
Sn'V- -Sn2+t
H+-
Pb2+- -PbT

Cd2+- I
Zn2+- -Cd 1

-10 V
-Zn]

Water is reduced — * -
ii
li
II
JL -2 0 V
n
II
II
II
II
il
« I
Na+—M—Na *
K + - * - K 1 -30 V
Li+—»-Li T.

FIG. 58. Scale of standard potentials in water.

In acidic surroundings this limit occurs for still weaker reducing agents be-
cause the solvated proton is more easily reduced than the proton of the water
molecule:
2H + + 2e ^ H2T, E0 = 0-00 V
2HA + 2e^ H2 + 2A", E0 = -0-05SpKA

On the other hand, water can be oxidized:

2H 2 0 - 4e ^ 0 2 t + 4H + , E0 = 1-23 V
 OXIDATION-REDUCTION REACTIONS 131

and the strongest oxidizing agents cannot exist in aqueous solution. Thus per-
manganate oxidizes (slowly) water in an acidic environment with formation of
oxygen. Water thus limits the possibility of oxidation of the weakest reducing
agents (Fig. 58).
In alkaline media this limitation occurs for less strong oxidizing agents, the
ions O H " being more easily oxidized than water:
4HCT - 4e ^ 0 2 | + 2 H 2 0 , E0 = 0-42 V
equally
2 H 2 0 + 4B - 4e ^ 0 2 t + 4HB + , E0 = 1-23 V - 0-058 pKA.
The region of potential in which oxidation-reduction reactions can occur in
water is thus theoretically 1-23 V. But as the oxidation and reduction of water
are slow, a greater region can be used in practice, about 2 V (34 units of pK).
2. In the majority of other solvents, limits are imposed in the same way by
reduction and oxidation of solvent, and these define a region of useful potential.
Thus in all acidic solvents it is the reduction of the proton of the solvent mole-
cule which limits the reducing agent side:
In acetic acid:
2HO Ac + 2e ^ H 2 t + 2AcO~
In alcohols:
2 R O H + 2 e ^ H 2 T + 2RO"
In ammonia we have
2NH 3 + 2e ^ H 2 | + 2NHJ
For other solvents there are various reduction reactions which are limiting;
e.g.
InSOCl 2 :
2S0C1 2 + 4e^ SI + S 0 2 | + 4C1"
InN204:
N 2 0 4 -I- e ^ N O T + NOJ
InNaClmelt:
N a + + e ^ Na
I n N a N 0 3 nielt:
NOj + 2 e ^ N O j + O2"
Similarly there are various limiting oxidation reactions:
InH2S04:
2H 2 S0 4 - 4e ^ H 2 S 2 0 8 + 2H+
InNH3:
8NH 3 - 6 e ^ N 2 T + 6NKU"
InNaClmelt:
2C1- - 2 e ^ C l 2 T
In N a N 0 3 melt:
2NO3 - 2e ^ 2 N 0 2 t + 0 2 t
132 CHEMICAL REACTIONS IN SOLVENTS AND MELTS

The more difficult its own oxidation the easier it is, using a solvent, to go to
more oxidizing conditions, e.g. we go to a more oxidizing medium in alkali
fluoride melts than in bromides or chlorides. Similarly, the more difficult its
reduction the easier it is, using a solvent, to go to more reducing conditions;
thus for solvents where reduction occurs at a proton (acidic solvents), the more
strongly acidic they are, the more easily they are reduced: H 2 S 0 4 more easily
than HO Ac, which is reduced before water, which is reduced before ammonia.
Figure 61 shows, very roughly, the fiields of utilizable potential in various
solvents.
Note. A number of oxidation-reduction reactions are slow, sometimes even extremely slow.
This is often especially the case in reactions with the solvent. The standard potentials then
only give rough predictions. It follows that limitations by the solvent can generally only be
determined to an order of magnitude.
ELECTRON SOLVATION In certain solvents, ammonia, aliphatic amines, metal
salt melts, the electron can exist free, solvated by solvent molecules. For ex-
ample :
In ammonia:
N H 3 + e ^ e9 NH 3 or NH3"
InNaClmelt:
Na + + e ^ e9 Na +
or:
2Na + + e ^ Na, Na + or NaJ

In these solvents, then, the concentration (and the activity) of the electron
can be defined, and the oxidation-reduction couples characterized by an equi-
librium constant:
Ox+ ^ Red, *=[0X][C]"
[Red]
RT
By analogy with potential, one can use E0 = 2-3 — F pK. The value of the
constants EQ can be placed on a scale of potential, origin corresponding to
[e] = 1 (Fig. 59). The strongest reducing agents, like "Red 3 " on the figure, com-
pletely yield their electron to the solvent; for example:
InNH3:

Na + NH 3 "-* N a N H 3 ^ Na + + NH3~
InRNH2:
+ -
Li + RNH 2 -> Li RNH 2 ^ Li + + RNH 2
In CaCl 2 melt:
Li + Ca 2 + -> Li + + Ca + (or e, Ca 2 + )

Predictions by means of this scale are made in the same way as with scales
of potential whose origin is arbitrary.
The scale thus defined is limited for oxidizing agents by solvent oxidation.
 OXIDATION-REDUCTION REACTIONS
E

Limitation by oxidation
of solvent

Ox, Red9

OxA Red1

Ox3 Red 3

FIG. 59. Scale of potentials in a solvent which solvates the electron.

COMPARISON OF SCALES OF POTENTIAL IN VARIOUS SOLVENTS

It is interesting, in comparing the properties of different solvents, to relate

their different scales of potentials, each determined in a given solvent. It is
sufficient for this to relate the origins, arbitrary or real, of these scales. Several
methods have been proposed:2,5
1. Determination, by calculation, of the standard potential presented by a
system, chosen afterwards as reference, in two distinct solvents (one of them
usually water). For example, for the system Rb + /Rb, the difference in solvation
energies of the Rb + ion can be calculated in each of two solvents, using Born's
equation1,2'5
2. The standard potentials of the H + /H 2 f system can be related, using the
solvation of hydrogen (solubility measurements), taking into account the
differences in H + solvation of different solvents, i.e. their basic power, as has
been shown elsewhere (see Chapter 2).
3. Measurement of electrode potentials. When two identical electrodes, e.g.
silver, are dipped into two Ag+ ion solutions in two different solvents (one
generally being water), a potential difference is set up between the two elec-
trodes, and this is the sum of the potential differences at the junction of the
two solutions (determined by calculation) and of

AE = — log,C- ^ i = 0-058 log - ^ + i (at 20°)

F * [Ag+] s *[Ag ls
[Ag+]e and [Ag+]s being the activities of theAg + ion in water and in the sol-
vent S.
Whence
AE = 0-058 log P,
134 CHEMICAL REACTIONS IN SOLVENTS AND MELTS

PAg+ being the partition coefficient of Ag + between water and the solvent S,
which can be determined by other means.
The standard potential of the Ag + /Ag system can then be deduced in each
solvent, compared to that in water.
Notes, (i) Conversely, these potentiometric determinations constitute a method of deter-
mining the partition coefficients of different ions.
(ii) If the definition of activity coefficients of solvation (with respect to water) is used (see
Chapter 2, p. 69), the standard potentials of all systems are the same as those in water, and
the scale of potential in water is more or less valid in every solvent.
4. REDOX SCALE (coloured oxidation-reduction indicators). Compounds
whose oxidized and reduced forms have different colours can be used as indi-
cators of potential. By analogy with the Hammett H function for acids and
bases, a function JR has been proposed, 3,4,5 defined with the aid of groups of
indicators by
0-058i? = (£ 0 )H 2 O + 0-058 log - ^ 2 L (at 20°)
Qted
The function 0-058i£ plays a part analogous to potential and the scale 0-058i£
coincides with the scale of potential in water.

TABLE 11. STANDARD POTENTIALS IN WATER OF SOME COLOURED OXIDATION-REDUCTION

INDICATORS5

Charge type Reducing form | E 0 (V)

I/I + Dicyclopentadienyl-Fe(II) (ferrocene) 0-40

Dicyclopentadienyl-Co(II) (cobaltocene) -0-92
Triethylene tetramine-disalicylidine-Fe(II) -0-26
Triethylene tetramine-disalicylidine-Co(II) -0-46
Triethylene tetramine-dipyrrolidine-Fe(II) -005
Di(2-methyl-pyridinaminosalicylidine-Fe(II) -0-20
I-/I Tri(<;-phenanthroline-6-sulphonate)-Fe(II) 1-22
Tri(3,4-dimethyl-o-phenanthroline-6-sulphonate-Fe(II) 1-08
Tri(o-phenanthroline-6-sulphonate)-Os(II) 0-96
Tri(3,4-dimethyl-o-phenanthroline-6-sulphonate-Os(II) 0-85
I2+/I3+ Tri(o-phenanthroline)-Fe(II) (ferroin) 1-13
Tri(3,4-dimethyl-o-phenanthroline)-Fe(II) 0-93
Tri(3,4,7,8-tetramethyl-o-phenanthroline)-Fe(II) 0-90
Tri(aa'-dipyridyl)-Fe(II) 110
Tri(o-phenanthroline)-Os(II) 0-88
Tri(3,4-dimethyl-o-phenanthroline)-Os(IT) 0-71
Tri(3,4,7,8-tetramethyl-o-phenanthroline)-Os(lI) 0-65
Tri(<m'-dipyridyl)-Os(II) 0-88

The following symbols have been proposed: R0 (couples I + / I , R+ (couples

I / I + ) R (couples I/I").
2+

Table 11 gives a list of some oxidation-reduction indicators, with standard

potential values in water (the standard potentials in some other solvents—
 OXIDATION-REDUCTION REACTIONS 135

< <
z o
< o < z
o
> 5 x I-
LU
DC
O
CO Q
>
O O X
< o
E (Volts)
i

Hg Hgf
+
Ag Ag Ag
Hg Hg;
Ag

H 2+ H+
(a)-
Cu Cu2+Cu4- Cu

Cu
H2.+ H+
Pb-
H+ Ho+H+
H+
Pb4Pb; Cu4 Hg+ Ag4
Pb Pb
Pb- Cd"
Tl TI+ Cd H+
Cd - f C d 2+TI4- Tl-
Cd +
Cd-
Zn4 Pb4 Cu
Zn + Pb
n 2+Zn4-
Cui

H 2 -LH+
H
Cd-i 2+H+

Cd4
Zn

Zn

Ca-
Na Na+ Na +
Ca Ca2+ Na4- Caj- Na- Ca4
Ca4- Rb
K | K + Rb. K I Na4
Rb Na T Rb_L K 4
Rb+Rb+ K" Rb"
Li T L i + Li- K Rb 4 K
Li
Rbi~
Li- Li 4
Li4

FIG. 60. Comparison of scales of standard potentials in various solvents 5 : (a) ferro-
cene, (b) cobaltocene (see also Fig. 104).
136 CHEMICAL REACTIONS IN SOLVENTS AND MELTS

acetonitrile, formamide and methanol - are given under the corresponding

solvents).
It is supposed that the standard potential of indicators of the same group do
not vary from one solvent to another or vary from the same, known value. Using
these coloured substances a scale which can be used experimentally in every
solvent can thus be set up, allowing the comparison of standard potential values
of different systems in various solvents.

<

I
o _ o
o z
< <
w
'V///

22
'M
m 'M
'M

W,
W,
m

Z77,

vz Z77, w,
FIG. 61. Approximate ranges of potential for some solvents.

Figure 60 represents the scales of potential in some solvents, placed appro-

priately according to the first method (reference system Rb + /Rb). The variation
of standard potentials of two indicators are given in (a) and (b). 5
Here, the regions of potential which can be used in different solvents can be
placed appropriately, showing which solvents allow strong oxidizing agents and
which strong reducing agents (Fig. 61).

REFERENCES

1. W.A.PLESKOV, UspekhiKhim. 16, 254 (1947).

2. H.STREHLOW, Z. Elektrochem. 56, 827 (1952).
3. H . M . K O E P P , Dissertation, Gottingen, 1955.
4. H.WENDT, Diplomarbeit, Gottingen, 1958.
5. H . M . K O E P P , H.WENDT and H.STREHLOW, Z. Elektrochem. 64, 483 (1960).
 OXIDATION-REDUCTION REACTIONS 137

OXIDATION-REDUCTION AND ACIDITY.

OXIDATION-REDUCTION AND COMPLEXES

There are numerous reactions involving the simultaneous exchange of an

electron and another species, ion or molecule.
1. IN NON-POLAR MEDIA, oxidation-reduction reactions are often accompanied
by the exchange of an anion in the opposite direction to the electron exchange;
for example:

Fe(N0 3 ) 2 + Ce(N0 3 ) 4 ^ Fe(N0 3 ) 3 + Ce(N03)3

(exchange of an electron and a nitrate ion)

Pb(CH3C02)4 + SbCl3 ^ Pb(CH3C02)2 + SbCl3(CH3C02)2

(exchange of two electrons, and two acetate ions)

These exchanges are imposed by the electrical neutrality of the compounds
in non-polar media.
These reactions, involving oxidation-reduction and complexes, can be pre-
dicted using scales analogous to the scales of exchange of any two ions (see

Exchanges AcO~/e

Pb(OAc) 4 i Pb(OAc) 2
Co(OAc) 3 Co(OAc) 2

Ce(0Ac) 4 J-Ce(0Ac) 3

Fe(OAc) 1 Fe(OAc>

SbCI 3 (0Ac)2|SbCl3

TiCU

V0(0Ac)3|V0(0Ac)2
Cr(0Ac)3-[ Cr(OAc) 2

FIG. 62. Prediction of oxidation-reduction reactions in non-polar media. Scale of

acetate ion/electron exchanges in acetic acid.

Chapter 3 "Complexes"). For example, Fig. 62 shows an approximate scale

for electron/acetate ion exchange, allowing the prediction of oxidation-reduction
reactions between acetate complexes: all reducing agents (on the right of the
scale) can react with an oxidizing agent (on the left) situated above.
5a CRS
138 CHEMICAL REACTIONS IN SOLVENTS AND MELTS

In certain reactions, there may also be exchange of an electron and a cation

in the same direction, for example, the reduction of a hydrocarbon by a hy-
dride:
R + LiH ^ RLi + £H2

2. IN POLAR MEDIA, the arguments which can be used about the influence of
acidity, or the formation of complexes, on oxidation-reduction reactions are
completely analogous to those used for reactions in water.
It is often useful to represent this influence by diagrams giving the apparent
standard potential of a system as a function of pH or of pX (X being any spe-
cies involved in the reaction).f

t For these arguments, consult G. Chariot, Les Reactions en solution et Vanalyse qualitative,
Masson, 1957, and Les Methodes de la chimie analytique, Masson, 1961.