;Q+ 4tkc New England Association of Chem
M a d e l i n e P. G o o d s t e i n
Central Connecticut State College
New Britain, Connecticut 06050
Interpretation of Oxidation-Reduction
The oxidation-reduction (or redox) con-
cept is currently in widespread use in chemistry (1) as
an organizing structure for chemical knowledge; (2)
as a guide to the prediction of reactions, and (3) as a
mathematical device to enable the balancing of certain
complex reactions. Despite characterization of the
concept as arbitrary and arithmetical, the oxidation-
reduction concept has been found too useful to abandon.
Since World War 11,new theoretical ideas and usages
have developed in reaction mechanisms, complex ion
formation, and electronegativity which are of signifi-
cance to the redox concept. I n the light of these de-
velopments, it has become feasible to reexamine redox
usage for governing principles. According to a study
made by Yalman which appeared in 19.59 ( I ) , electro-
negativity was employed in the definition of oxidation
state in half of the introductory college texts examined.
Electronegativity is a construct calculated from experi-
mentally-determined parameters; the recent emergence
of its use in the calculation of oxidation states suggests
a physical principle as a basis for the redox classifica-
tion. The following discussion is devoted to the de-
velopment of this idea.
The Oxidation N u m b e r
The Oxidation Number ond Eledronegotivity
The key elements to current utilization of the redox
concept lie within the definition of the oxidation num-
ber. (The terms oxidation number and oxidation state
am nsed interchaneeablv.) A set of rules has been
1 It can be seen that current practice in bhe calculation of oxida-
tion states of stable free radical molecules such ss NO and NO2
treats two electrons as bonded by the less electronegative atom
to the more electronegative atom giving the latter a complete
electron octet.
Several different conventions are currently in use for designat-
ing oxidation numbers. I n t h i ~paper, positive oxidation states
are indicated by a Roman numeral in parentheses following the
atom (Stock convention), When the sign is negative, a minos
sign follows t,he numeral within the parentheses; when the sign
is positive, it has been chosen to make its inclusion optional.
The same convention is adopted for oxidation numbers not in
formulas.
There may appear t o be a. discont,inuity in the calculation of
oxidation numbers in that electrons shared by atoms of equal
electronegativity count 8s zero in the calculation of oxidation
numbers, but as soon as the sharing is the least unequal the oxida-
tion number of each atom changes. However, it is noted that
finite changes to, from, or through the condition of equal elec-
tron-sharing ordinarily take place only by redox mechanisms
(see litter) and only with abrupt changes in orbital electron
densities.
452 / Journal of Chemiml Education
chers
developed for the calculation of oxidation states; these
rules are generally consistent among the various intro-
ductory texts. Application of the rules enables rapid
identification of the more electronegative atom in a
bonded pair of atoms. When this relative order of
electronegativities is established, the oxidation number
of an atom may readily be calculated.
The zero reference state is assigned to any atom which
is bonded only to atoms of equal electronegativity or is
non-bonded. Accordingly, an atom in the elemental
state or in the atomic ground state configuration has a
zero oxidation number. The oxidation number of a
given atom increases by one unit for each electron
entered by the given atom into a bond with a more
electronegative atom, and decreases by one unit for each
electron bonded to thegiven atom by an atom of lesser
electronegativity.' For example, a hydrogen atom in
the elemental state or the monatomic ground state con-
figuration has an oxidation number of zero. The oxida-
tion number of hydrogen when bonded to a more elec-
tronegative atom is (I+).? When bonded to an atom
of lesser electronegativity such as lithium, hydrogen is
assigned the oxidation state of (I-).
When the atoms linked to a given atom are all more
electronegative than the given atom, the oxidation num-
ber is positive; it is negative when all of the linked atoms
are less electronegative. When a given atom in a mol-
ecule, such as the carbon atom in an alcohol or aldehyde
group, is bound to a more electronegative atom in one
bond but to a less electronegative atom in another, the
oxidation number may be less meaningful in that it gives
only a net count of electrons linked to atoms of differing
electronegativities. For example, the terminal carbon
H
I
atom in -C-C=O is more electronegative than the
linked H atom, equal in electronegativity to the linked
C atom, and less electronegative than the linked oxygen
in two bonds. The sum of the count at each bond may
be shown as 2(I+) + (I-)+ (0) = (I+),3 the oxida-
tion state of the carbon atom.
The oxidation number of a given atom equals the sum of
the electrons linked by the given atom to atoms of higher
electronegativity, less the sum of the electrons linked to the
given atom by atoms of lesser electronegativity.
Change in Oxidation Number
Consistent with the electronegativity criterion, the
oxidation number of an atom changes as a result of any
changes in the relative order of electronegativity with
linked atoms. Since every increase in oxidation num-
ber during an oxidation-reduction reaction is accom-
panied by a decrease in oxidation number eleswhere
among the reactants, it follows that every alteration in
order of electronegativity affecting the bonding of one
atom in a reaction is accompanied by a change in order
of electronegativity in the opposite direction a t a bond
of another atom.
Three variations in order of electronegativity are
possible, i.e., those in which an atom is bonded to an
atom of (1) greater electronegativity; (2) equal electro-
negativity, and (3) lesser electronegativity. A shift
in either direction between any of these categories alters
the oxidation state of the atom.
I n order to include in tile above definition the redox
changes which affect non-bonding electrons, such as in
the oxidation of R3P: to Ral': 0, the following considera-
tion is convenient. An atom which possesses a lone
pair of electrons, such as the P atom in RJ':, may be
regarded as linking the lone pair of electrons to an atom
of zero eleetronegativity. Thus, the phosphorous
atom in R3P: is the "more electronegative" atom link-
ing the lone pair of electrons to an atom of lesser (zero)
electronegativity. This approach permits the above
definition to be extended to cover all changes in oxida-
tion st,ate and makes it easier to recognize the physical
changes underlying the treatment being developed.
The approach by which an atom is regarded as at,tach-
ing its non-bondi~igelect,rons to an at,om of zero electro-
negativity is not novel; Gillespie (2) applied this treat-
ment to a non-bonding pair.
Electron Density Models of Oxidation State Changes
The changes in the order of electronegativities which
take place in an oxidat,ion or reduction may conveniently
be pictured by the use of molecular orbital representa-
tions.
Figures l a and l b illustrate, respectively, equal and
unequal sharing of an electron pair.
In Figure 2a, changes in relative orders of electro-
negativities are pictured in which the letters A, B, and
Figure I. Boundary surfocc. of m.lecu1.r 0rbitdr: 0, homonucleo. dio-
tomic molecules; b, diatomic molecules, B mwe eledronegotive than A.
C represent atoms whose electronegativities increase
from A to B to C.
Figure 2b illustrates a case in which redox does not
take place even though a shift in electron density occurs.
If the molecule AB, for example, were to represent
hydrogen chloride, the molecule could dissociate to
form H + and C1-. Since the relative order of electro-
negativities would remain unchanged, this would not
be a redox reaction. For the same reason, displacement
of B, as pictured, by the more electronegative atom C
is not considered to be an oxidation-reduction reaction.
For atom A to have undergone a change in oxidation
state, the bond between atoms A and B would have had
to rupture and, in the new bond formed by atom A, the
electron density would have had to shift so that it was
either equally shared or was greater near atom A.
Comparison of Lewis Acid-Bose ond
Oxidation-Reduction Reocfions
I t is expedient to compare the redox concept as
presented wit,h the Lewis acid-base concept. The redox
concept distinguishes between those Lewis acid-base
reactions which are redox reactions and those which are
not. I n non-redox Lewis acid-base reactions, an atom,
A, may be initially bound by a paired-electron link
to an atom of lesser elect,ronegativity. When this
bond is broken, atom A bonds to another atom whose
electronegativity is also less than t,hat of A. In redox
chemist,ry, however, A would bond t,o an atom of
greater elect,roriegativit,y t h i ~ nthat of A.
Some Relevant Aspacts of the Electronegativity Concept
Although the electronegativity concept has been
freely used in t,he foregoing, mention must be made of
considerations pertinent to its use. The definition of
and the establishment of values for electronegativity
have beeo much debated in the literature. Current,
aspect,s of t,he matter have been reviewed by l'ritchard
and Slcinner (3) and by Ferreira (4). The most widely
accepted definitions are those of Mulliken ( 5 ) , and
Pauling (6). New ideas on electronegativity have
Figure 2. Boundary rvrfocer of molecular orbitals, relative order of
>
magnitudes of electronegativitier, C B >A: o, redox changes of atom 8:
b, redor chmger do not occur in these rhifh of electmn density.
Volume 47, Number 6, June 1970 / 453
 been proposed recently by Iczkowski and Margrave (7),
Hinze, Whitehead, and Jaff6 (8),and by Klopman (9),
among others. A number of methods for the deter-
mination of electronegativity values have been de-
veloped among which may be mentioned those of Paul-
ing (lo), of Rfulliken (5), of Sanderson (11), and of
Allred and Rochow (12). Discussion of the above is
beyond the scope of this paper. With respect to the
topic as applied herein, the following comments are
made.
Ferreira has noted that the meaning of electronega-
tivity seems to be intuitively understood by chemists
(4) Still, the construction of a precise definition has
been fraught with problems. Theoretically, an atom
develops an electron-attracting power as a result of the
effective nuclear charge outside of the atomic kernel
acting upon the outermost shell of electrons. This
effect is complicated by the partial screening effects of
valence electrons upon each other.
Electronegativity was defined by Pauling as the
power of a neutral atom in a molecule to attract elec-
trons to itself (6). Ferreira has pointed out that, be-
cause molecules are not just simple additive combina-
tions of atoms, electronegativity cannot, in principle,
be called an atomic parameter. However, the valence-
bond theory and the LCAO-molecular orbital theory
"preserve" the atoms in the molecules. By accepting
this idea of a "preserved" atom, it becomes possible to
use knowledge of atomic electronegativity for the
understanding of chemical phenomena (4).
As of now, the Rlulliken definition appears to be the
most widely accepted theoretical definition of atomic
electronegativity. Mulliken defined electronegativity
as one-half the sum of the ionization potential and
electron affinity of an atom (5). As a result of new
experimental procedures, it is now possible to reliably
determine ionization potentials and many electron
affinities (IS). Numerical values of electronegativity
obtained by the Pauling thermochemical methods are
roughly proportional to the Mnllikenvalues although the
validity of the Pauling procedure has been questioned
(4). Because thermochemical data are relatively easy
to obtuin and because agreement exists with other
methods of establishing elect,ronegativity values, the
Pauling electronegativity scales are much used.
Iczkowski and Margrave (7) have recently proposed
that electronegativity may be treated as the property
of an orbital in an atom, and may be defined as
where x is electronegativity, E is the energy of an orbital
and n the number of electrons in the orbital. The
Mulliken definition becomes a special case of the Iczkow-
ski-Wlargrave definition, where the change - i n n is one
electron-(8).
It might seem that bond polarity would be a more
convenient term to use in the redox treatment than
electronegativity. This urould be the case if bond
polarities could be directly equated with bond dipole
moments. However, asymmetric distribution of elec-
tron density within a molecular orbital as a result of
differences in electronegativity is not the only deter-
minant of a bond dipole moment. Mulliken has pointed
out that even a purely covalent bond may have a large
454 / Journal of Chemical Educofion
dipole moment (14). The bond moment may be
present due solely to differences in atomic size so that
the centers of positive and negative charge do not co-
incide. I n the case of the hydrogen fluoride molecule,
a bond moment exists not only because of the difference
in electronegativities but also because the small hydro-
gen atom is almost embedded in the larger electron
cloud of the fluorine atom. I t can be postulated that
there are bondings where the direction of the bond di-
pole is opposite to that of the order of electronegativi-
ties, as was proposed by Coulson for the tetravalent
carbon-to-hydrogen bond (15).
Oxidofion State Change and Complex Formation
The recent development of theories of complex forma-
tion apparently is in accord with the above interpreta-
tion. Complex formations are, by themselves, not
regarded as oxidation-reduction reactions by chemists;
they do not involve changes in oxidation state (i.e., the
electrons in the complex linkage are initially non-bond-
ing electrons within the orbitals of the more electro-
negative atom). This corresponds to the view of
complex formation as essentially involving overlapping
of orbitals without transfers in electron density between
ligand and central atom. Pauling has claimed that the
electronegativities of atoms and the non-cornplexed ions
which they form are practically equal. This suggests
that the change in energy per change of charge in the
orbital of an atom is fairly constant., a t least until the
electron shell is filled or stripped. The modification of
t,he electronic structure of the cent,ral ion which occurs
in complex formation may alter the electron screening
within the valence shell of the ccntral ion which, in turn,
may alter the central ion's electron-attracting power.
Since this change in electron attracting power is not the
result of an increase or decrease in electron density
from an outside source but is due instead to the distribu-
tion of the atom's own electron density, it must be
considered a change in its atomic electronegativity.
The change in electronegativity with change in oxida-
tion state may then alter the relative stability of the
different oxidation states of the element. As in all other
redox reactions, electronegativity difference is not the
only factor involved in the reaction energetics. While
it might be desirable to determine the electronegativity
of the central atoms of complexes, in practice the oxida-
tion potential is an even more useful parameter.
Clarriflcotion of Reactions Involving
Oxidation State Changes
The rules given in introductory chemistry texts en-
able relatively unequivocal determinations of oxidation
numbers, whether the rules are considered to be
arbitrary or whether they are interpreted in terms of the
physical meaning of the electronegativity principle as
developed above (within the limitations imposed by
electronegativity values precise to, a t best, two signifi-
cant figures). However, the situation is much less clear
when it comes to the classification of reactions in which
changes of oxidation state occur. I t might seem that
any reaction where oxidation state changes occur
would be classed as a redox reaction, but this is not so.
An oxidation-reduction reaction is defined by most
introductory texts as any reaction in which a change of
oxidation state occurs. However, advanced texts and
journals may differ from this by the grouping of certain
reactions which embody changes of oxidation state
together with non-redox reactions; any mention of
change in oxidation state is omitted. Although the non-
redox treatment accorded such reactions is fairly uni-
form, deviations from the prevalent practices may be
found. More puzzling is the fact that some reactions in
which oxidation state changes occur have been specifi-
cally identified as non-oxidative (18).
No explanations of the above deviations from redox
treatment were found in the literature, nor was any
statement given on governing criteria. Apparently,
textbook and journal writ,ers have intuitively under-
stood the basis for the classification of these reactions
without regard t o their changes in oxidation state.
The next section of this paper will present a classi-
fication scheme based on the rather complicated prac-
tice prevailing in the literature for reactions in which
changes in oxidation state occur. Offered with this will
be a rationale hypothesized as underlying the present
redox classification treatment. I t is noted that, in the
same sense that any classification system in necessarily
of an arbitrary nature, SO also is any system which classi-
fies redox reactions.
The scheme to be prescntcd is based on the idea that
a reaction in which given atoms undergo oxidation stat,c
changes is not considered to be an oxidat,ion-reduction
reaction unless the difference in relative electronega-
tivities is a factor in causing the reaction t o occur.
Furthermore, the degree to which the reaction tends to
be treated as a redox reaction in advanced texts and in
journals depends t o a considerable extent, on the degree
t o which the electronegativity difference between the
atoms undergoing oxidation state change is a factor in
causing the change in oxidation number. The greater
the electronegativit,y difference and, correspondingly,
the more significant its effect on the reaction, the
more likely it is t,hat the reaction dl be treated as a
redox reaction.
Accordingly, three categories of reactions embody-
ing oxidation state changes were set up; they were
named, for convenience herein, (I) the stronger oxida-
tions, (2) the very weak oxidations, and (3) the pseudo-
redox react,ions. The stronger oxidations are those in
which the electronegativity difference between atoms
undergoing oxidation state changes is a significant
factor in causing them to undergo the changes in
oxidation state. The very weak oxidations are those
correspondingly in which the electronegativity differ-
ence between atoms undergoing a change in oxidation
state is a very minor factor in causing the reactions t o
take place. The pseudo-redox reactions comprise
the reactions in which the electronegativity difference
between atoms undergoing a change in oxidation state
is not a factor in causing the reaction to occur. The line
of demarcation between the stronger and the very weak
oxidations is not sharply delineated.
The three categories will be discussed next in greater
detail.
The Pseudo-Redox Reaction
The criterion for this category is as stated above.
Typical of the reactions in this category are organic
elimination reactions, photoexcitations, radiolyses, and
the solution of halogens in water.
I n both the organic elimination and the halogen solu-
tions, the atoms undergoing change in oxidation state
are atoms of the same element initially bonded to each
other. One atom is then reduced, the other oxidized.
For example, in the elimination of carbon dioxide from
a p k e t o acid
n n
C' is reduced while C v is oxidized. Likewise, when
chlorine dissolves in water, the bond between the chlo-
rine atoms undergoes scission; one chlorine atom forms
C1- with an oxidation state of (I-) while the other
combines to form OCI- where it has a n oxidation state
of (I+). I t is evident that the difference in relative
electronegativities of the atoms undergoing oxida t'~ o n
and reduction is not a causative factor of reaction. I n
the p k e t o acid elimination, bond scission is the result
of a n inductive effect transmitted from the strongly
electronegative carbonyl carbon. The bond scission
which occurs when the halogens dissolve in water is the
result of the strong polarizing effect of the medium.
The practice of excluding radiolyses and photo-
excitations from the redox category is a170 in accord with
the idea that the relative atomic electronegativity
differencebet.ween the atoms undergoing oxidation state
change is not a factor in causing the oxidations and
reductions t o occur. Radiolyses result from the pene-
tration of particles initially external to the medium
while photoexcitations in which changes of oxidation
state occur require strong steric or electron-delocalizing
effects. An example of a photo-excitation in ~vhich
changes of oxidation state occur is
Here, the clectron is pulled out of the bond away from
the more electronegative atom.
I n the pseudo-redox reaction, the changes in oxida-
tion state are due to factors other than the atomic
electronegativity differences of the "preserved" atoms
in molecules.
Definition of an Oxidation-Reduction Readion
I t is proposed that an oxidation-reduction reaction
be defined as a reaction in which a change i n the relative
order of atomic electronegatiuities takes place between a
given atom and the atoms lo zohich it i s bonded prior and
subsequent to reaction; concurrently, an opposite chanqe
i n order of electronegatiuities takes place elsewhere among
the ~eactants. The difference i n relative electronegativities
of the atoms undergoing oxidation state change is a factor
i n causing the changes to occur.
Stronger and Very Weak Oxidofions
Many kinds of reactions in which changes of oxida-
tion state take place are treated as redox reactions in
texts and periodicals. Among these are (1) inorganic
reactions in which net transfer of electrons occur; (2)
electrochemical reactions; (3) free radical autoxida-
tions; (4) free radical reactions in which transfers of
electrons take place (as with metallic complexes or
semi-quinones); (5) many organic reactions of which a
partial listing would include all of those reactions in
which carbon progresses through the oxidation stages
Volume 47, Number 6, June 1970 / 455
from t.he aII<ancs to the carboxylic acids and then to
carbon dioxide, reactions in which peroxy compounds
undergo oxidation or reduction, oxidations by per-
mangan:rt,e, dichromate, cerium (IV), cobalt (III), and
ot,her inorganic oxidants, and reactions where hydride
transfers takc place.
In free radical and organic chemistry, there are, how-
cvcr, other rcact,ions where changes in oxidation state
occur but ~ d ~ i careh rarely, if ever, described as redox
react,ions. Among t,lieseare the free radical hydrogena-
tion of olefins, the balogenat,ions of double bonds (both
hetcrolytic and homolytic), and electrophilic aromatic
snhstitutions. Note that the atoms undergoing oxida-
ti011 differ in relative electronegativities from those
undergoing reductiorl in these reactions, unlike the
pseudo-rcdox elimination or halogen solution reactions
previously described. I<'or example, when a double
hond is chlorinated, both elemental chlorine atoms are
rcduccd while both carbon at,oms are oxidized. The
addition of hydrogen chloride to an olefin bond is the
pseudo-rcdox react~ionmost akin to the chlorination;
one carbon atom is oxidized, the linked carbon atom
is reduced, and no change in oxidat,iou state takes place
for the H and C1 atoms.
A hypothesis is tentatively offered to account for the
difference in treatment between these "very weak"
oxidat,ions and the "stronger" ones which were cited as
receiving general acceptance as redox reactions. While
a detailed analysis is beyond the scope of this paper, it is
hoped that a brief discussion will indicate the support-
ing rationale.
When the very weak oxidations are scrutinized as a
group, it appears that, in each case, the relative elec-
tronegativity is only a minor factor in causing these
reactions to occur. Other, more dominant, factors are
significant to the reaction energetics. Moreover, it
also appears that the mechanisms by which these re-
actions take place closely resemble certain non-redox
mechanisms, alt,hough differing always to a t least some
slight extent. I n the st,ronger oxidations, on the other
hand, relative electronegativity differences play a more
important role and, correspondingly, they tend to
proceed by mechanisms which often distinctly differ
from those of non-redox mechanisms.
I n the case of the halogenation of double bonds, a
major factor promoting t,he heterolytic reactions is the
polarizable a electron pair. These oxidative addition8
require a step in which the elemental halogen is polar-
ized to form the cyclic halonium ion. In contrast, non-
oxidat,iveolefin additions, such as additions of HBr and
H,O, result from the interact,ion of the already polar
molecule and the r electron system.
In homolytic halogenations and hydrogenations, the
high reactivit,y of the free radicals is the most significant
factor in the mechanism. Energetics favor hetero-
combinat,ions over homocombinations, since the more
ionic bonds tend to have greater bond energies (10).
Except for highly electronegative atoms such as oxy-
gen this effect is probably completely overshadowed by
t,he high free radical reactivity.
The electrophilic aromatic ~ubstitut~ions all require
the formation of the "unusual" cations, such as Br+ or
NO2+. Thc reactions are facilitated by the latter and
by the conjugated aromatic hond system. Since the
L'nnusnal" cation regains the major share of the electron
456 / Journol of Chemicol Education
pair in the bond, these reactions are oxidation-reduc-
tions. However, because one of the p orbitals of the
strongly electron-attracting "unusual" cation con-
jugates with the parallel r orbital of the aromatic ring,
the oxidation is milder than would be expected on the
basis of electronegativity differences alone.
All of the heterolytic mechanisms of the very weak
oxidations exhibit some "unusual" configuration in an
intermediate step and, as~ociatedwith it, the redox
electron-pair shift discussed above. There appears to
be no special merit in treatment of the very weak oxida-
tions as redox reactions although, in each case, the fact
that changes in oxidation state occur lends an addi-
tional perspective from which to view the reactions.
The stronger oxidations-i.e., those reactions where
the relative electronegativity differences of the atoms
undergoing changes in oxidation state are significant
factors in causing the changes to o c c u r ~ f t e npossess
reaction mechanisms unique to the class of oxidation-
reduction. The uniqueness tends to diminish as the
significance of the electronegativity factor likewise
decreases. To illustrate, electrochemical reactions and
inorganic reactions where transfers of electrons take
place are clearly unique to redox chemistry. Among
the more distinctive organic reaction mechanisms are
those of the group typified by the chromic acid oxida-
tion of alcohols; they involve ester-type intermediates
and concerted electron movements in several bonds.
The formation of the hydride species through simul-
taneous bond-making and bond-breaking, as in the
bromine oxidation of alcohols, or through concerted
electron movements in a conjugated ring structure as in
the reduction of nicotinamide adenine dinucleotide, also
has characteristics unique to redox chemistry. At the
other extreme, autoxidations greatly resemble non-redox
free radical reactions and appear to differ only in that
they involve the diradical oxygen; most other free
radical redox reactions are simply treated as very weak
oxidations. The demarcation between the stronger
and the very weak oxidations is not sharp.
An important factor underlying the significance of
the redox class probably lies in the relatively distinctive
processes by which many of the stronger redox reactions
occur.
The classification of the reactions which embody
changes of oxidation state as given above has been
offered not in justification of the present practices but
rather as recognition and interpretation thereof. A
need for assessment of the treatment now given in the
literature, however it is interpreted, is implied.
Since those redox reactions where electronegativity
differences are of very minor significance are grouped
with similar non-redox reactions, the rough electro-
negativity values presently in use are probably about as
reliable as need be for the semi-quantitative purposes of
redox classification.
Summary
An interpretation of the oxidation number system
based upon the electronegativity principle has been
presented. As proposed, the definitions of oxidation
state and of change in oxidation state permit physical
interpretations which, in turn, allow removal of the
adjective "arbitrary" now frequently found in descrip-
tions of the oxidation number. A'Ioreover, acceptance
of the treatment permits both of the major classes of ers College, Columbia University. Appreciation is ex-
chemical reaction, the acid-base reaction-already pressed to the Editors of the NEACT Report and the
so firmly established-and the reaction in which changes JOURNAL OF CHEMICAL EDUCATIONfor their unfailing
of oxidation state take place, to rest upon experimental courtesy and helpful criticism.
criteria and physical interpretations.
The system of classification of the reactions in which
Lilemture Cited
changes of oxidation state take place was examined as
applied in the literature. I t was found that the pre- YA=mN. R. G.. J. CHEM. EDYO., 36. 215 (19591.
~ . J.. J. Cnew. Eonc.. 40,295 (1903).
G n z e s ~ rR.
dominant practices have not been uniformly adopted P B I T C ~ RHI .) ,0.. A N D SIINNEB.H. A,. Chem. Re"., 55, 745 (1955).
nor have the underlying criteria been made explicit. Fesnr;ln*. R.. Adaon. Chcm. Phya.. 13. 55 (1967).
M u ~ ~ ~ rR. e 8..
s . J . Chcm. Phvs.. 2. 782 (1934); 16, 497 (1949).
Three groupings of reactions embodying oxidation state P A U L L L.,
N ~"The
, Nature of t h e Chemical Bond." (3rd d.1, Cornell
Univmdty Preae. Ithaoa. New York. 1960, p. 95.
changes were proposed in this paper as corresponding to Icmowsnl, R. P.. A N D MasonAvr, J. L., J . Am. Chcm. Soe., 83,3547
the present complex practices, the pseudo-redox re- (19611.
actions, the very weak oxidations, and the stronger (8) Hmee, J.. WHITEHEAD. M. A,, A N D Jmst. H. H.. J . Am. Chem. SDC..
oxidations. The groups were segregated according to (9) KLOPYAN,G.. J. Am. Chem. Soe., 86, 1463, 4550 (1964): 81, 3300
(1965); J . Chrm. Phya.. 43, 8124 (1965).
the approximate degree of electronegativity difference IlOI ~ , L.. he N a t l m ni t h e Chemical Bond." (2nd 4.)
, ~PAULINO. ~ ~ .
Cornell
between the atoms undergoing oxidation state changes. University Press. Itheoa. New ~.rk<9;2, chap. 2.
It was suggested that an important factor in the signifi- . . SANDERBOX.
111) R. T.. "Chemical Periodioitv."
.. Reinhold Publiahina.Corn..
. .
New ~ o r k 1960,
, p. 31-4.
cance of the redox class probably lies in the relatively (12) ALLRDD. A. L.. AND ROCROW, E. G., J . Inor&?,N d . Cham.. 5, 269
~-"*-,.
110SRj
distinctive processes by which many of the stronger (13) Vmnsnsrev. V. I.. et 81, "Bond Energies. Ionizstion Potentiela and
Electron Affinities:' Translated by Soripta Teohnioa Ltd.. St.
redox reactions occur. Martin's Presa. New York. 1966.
(14) Mumrnerr. R. 8.. J . Chem. Phvs.. 3. 573 (1935).
Acknowledgment (15) Cou~aow.C. A,. "Valence." (2nd d.). Oxford University Presa, London,
1961,p.219.
(10) For example, see STEWART. R., "Oxidation Meohanisma: Applications
The author acknowledges with thanks the kind en- to Orgsnic Chemistry,'' W. A. Renjamin. Ino., New York, 1964,
couragement of Professor 0. Roger Anderson of Teach- p. 27.

Volume 47, Number 6, June 1970 / 457