Struct Chem
DOI 10.1007/s11224-015-0647-z
ORIGINAL RESEARCH
Which halogen is the strongest oxidant? A study with systematics
and surprises
Maja Ponikvar-Svet1 • Diana N. Zeiger2 • Joel F. Liebman2
Received: 9 July 2015 / Accepted: 17 July 2015
 Springer Science+Business Media New York 2015
Abstract Although it is generally accepted that fluorine
is the strongest oxidant among the halogens and so among
all of the elements, it has not been explained in the liter-
ature why this is the case. In this paper, we ask whether this
‘‘common knowledge’’ is indeed true; we also explore
various means of determining the oxidation strength of the
halogens by considering the energetics of binary halides,
hypohalites and dihalogens. In addition, we use Latimer
diagrams to evaluate the redox chemistry of these com-
pounds. Ultimately, we find that the conventional wisdom
holds and that our investigations have provided a clear
understanding of why fluorine is, indeed, the strongest
oxidant among the halogens.
Keywords Fluorine  Halogen  Oxidant  Latimer
diagram  Enthalpy of formation  Redox potential
This paper is dedicated to Magdolna (Magdi) Hargittai on the
occasion of her 70th birthday.
& Maja Ponikvar-Svet
maja.ponikvar-svet@ijs.si
& Diana N. Zeiger
dzeige1@umbc.edu
& Joel F. Liebman
jliebman@umbc.edu
1
Department of Inorganic Chemistry and Technology, Jožef
Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
2
Department of Chemistry and Biochemistry, University of
Maryland, Baltimore County, Baltimore, MD 21250, USA
Introduction
The title of the current paper asks the simple question,
‘‘Which halogen is the strongest oxidant?’’ Upon remem-
bering that the category ‘‘halogen’’ includes fluorine,
chlorine, bromine, iodine and astatine, there is an imme-
diate and simple answer: fluorine. The grade of F would
plausibly be given to the beginning student of chemistry
who does not provide this answer. However, why is fluo-
rine the strongest oxidant? What evidence is there for this
assertion? An attempt to answer this question is offered in
the present paper by looking closer at the formation of
halogen-containing compounds and by investigating both
some experimental and some theoretical variables.
Definition of oxidation process and related
reactions
In inorganic chemistry, the term oxidation usually
describes a process in which electrons are removed from
a molecule or atom. This criterion is clearly sufficient for
discussion of the oxidation properties of halogens with the
emphasis on fluorine; however, for the sake of com-
pleteness, let us also provide the official, more sophisti-
cated and precise, definition of oxidation as given by the
International Union of Pure and Applied Chemistry
(IUPAC) [1]:
1. The complete, net removal of one or more electrons
from a molecular entity (also called ‘‘deelectronation’’).
2. An increase in the oxidation number of any atom
within any substrate.
3. Gain of oxygen and/or loss of hydrogen of an organic
substrate.
123

All oxidations meet criteria 1 and 2, and many meet
criterion 3, but this is not always easy to demonstrate.
Formation of binary compounds
Fluorine forms a binary compound with most elements
(i.e., all elements except for He, Ne and Ar, as well as those
elements with the highest of atomic numbers that have too
short a half-life and/or too low abundance to perform the
necessary synthetic chemistry). Additionally, the resulting
binary fluoride has the same, and even not uncommonly a
higher, oxidation state, than the formally related binary
chloride, bromide and iodide, and (presumably) astatide.
For example, the alkali metal halides are generally
assumed to have 1:1 M/X stoichiometry for all species
(e.g., Refs. [2, 3]); the apparent exceptions such as LiF2
[4], NaCl3 [5], CsBr3 [6] and KI3 [7] contain polyatomic
anions. Higher polyhalides, such as Cs2I8 [8], will also not
be discussed in the current paper (we acknowledge now
that there are predictions of higher valence cesium fluo-
rides [9] formed under high-pressure conditions). There are
also nearly 20 molecular hexafluorides (16 of which are
well-defined species), but only four hexachlorides and one
hexabromide [10], and we note neither hexaiodides nor
hexaastatides. Most of these hexahalides are metal, or ‘‘at
least’’ metalloid, derivatives—sulfur and xenon being the
sole nonmetals to form such species; indeed, these last two
hexahalides are both hexafluorides.
Let us now consider the nonmetals sulfur, chlorine,
iodine and xenon. They readily form stable and conve-
niently isolated hexafluorides, pentafluorides, heptafluo-
rides and hexafluorides, respectively, with central atom
oxidation states VI, V, VII and VI, respectively. Xenon
octafluoride with oxidation state VIII is a source of con-
tention as to its isolability under any set of experimental
conditions [11–13]. With chlorine, sulfur forms only the
dichloride and the thermally labile tetrachloride [14];
chlorine forms the monochloride [dare we use the name, or
even the descriptor chlorine(I) chloride for Cl2]; iodine
forms the trichloride with an early suggestion of the pen-
tachloride [15]; finally, xenon forms the fragile tetrachlo-
ride [16, 17]. With bromine, sulfur forms the dibromide,
and chlorine and bromine form the monobromide [again,
dare we refer to BrCl as chlorine(I) bromide or even use the
formula ClBr]. There is evidence for ClBr3 [18], but the
suggested structure is Cl–Br(Br)–Br, and so it is better
understood as a bromine(III)-mixed halide than as chlorine
tribromide. Iodine tribromide [19] and xenon dibromide
[20] have also been proposed. With iodine, sulfur forms
S2I2 [21] and has also been suggested to form another
binary species, SI2, recognized as a possible product in a
classical synthesis and cryogenic matrix reaction [22, 23].
123
Struct Chem
Chlorine forms ClI, and iodine forms I2, but we wonder
whether these species qualify as monoiodides. We know of
no classical chemistry for any astatine counterparts; asta-
tine is an artificial element with a half-life of 7.5 h and is
too radioactive for many plausible studies to have been
performed. AtCl, AtBr and AtI have been observed using
mass spectrometry [24] and thermochromatography [25].
AtF and other astatine fluorides remain uncharacterized in
the experimental primary chemical literature [26] (this is
mainly due to astatine radioactive decay and short lifetime,
perhaps also because these last species are too involatile to
have been observed by the employed techniques).
Thus, we deduce that fluorine encourages high oxidation
states more than do the other halogens and so is the most
oxidizing of all of them. Perhaps, we should not be sur-
prised by this conclusion. After all, the electronegativity of
fluorine is so high—is it not the highest of all of the ele-
ments? The electronegativity of the halogens drops pre-
cipitously going down the periodic table,
F  Cl [ Br [ I. No reference need be given for this
truism from elementary chemistry courses. Now, it is found
that the electronegativity of fluorine is the second highest
of all of the elements; so what element is first? This is
unequivocally neon, while helium and fluorine are roughly
the same using Allen’s contemporary definition [27, 28].
Electronegativity cannot suffice as an explanation in that
neon and helium are definitively nonoxidizing, if not
chemically inert. Furthermore, the highest oxidation state
for most elements as found in neutral binary compounds is
with oxygen. While this special value is very commonly
shared with those of fluorine, notable exceptions include
ðVÞ
nitrogen, chlorine, manganese and xenon, such as N2 O5
ðVIIÞ ðVIIÞ
versus NðIIIÞ F3 ; Cl2 O7 versus ClðVÞ F5 ; Mn2 O7 versus
MnðIVÞ F4 ; and XeðVIIIÞ O4 versus XeðVIÞ F6 . The corre-
sponding high-valence binary fluorides do not exist. Should
we allow the consideration of binary ionic species? While
N(V) is found in both [NO3]- and [NF4]?salts, and Cl(VII) is
found in [ClO4]- and [ClF6]? salts, Xe(VIII) is found in
Xe(VIII)O4; however, its existence remains unknown, or at
best debatable, in both binary ionic and neutral fluorides.
The record for the experimentally observed highest oxi-
dation state is IX, found in admittedly gaseous [IrO4]?
[29]; this oxidation state has yet to be found in any salt and
is unmatched by any iridium fluoride. It may be argued that
there is too much steric hindrance for [Xe(VIII)F7]? for this
species to exist, for example as a product from the plau-
sible reaction of [KrF]? and XeF6 [30]. However, the
isoelectronic IF7 has long been known, and [XeF7]- with
an additional lone pair is a viable anion and has been
spectroscopically characterized as its Cs? and NF4? salts
[31]. Relatedly, Xe(VIII)F8 remains unformed from the
decomposition of the aforementioned [NF4]?[Xe(VI)F7]-,
Struct Chem
while [Xe(VI)F8]2- is well established in salts wherein
NF4? is among accompanying cations. (We also note that
[I(VII)F8]-, an ion isoelectronic to XeF8
ðVIIIÞ
, forms stable
salts [32]).
Enthalpies of formation of binary halides
The same conclusion that fluorine is the most oxidizing of
the halogens may be drawn by looking at the enthalpies of
formation of related binary halides. Consider the binary
halides of carbon, CF4, CCl4, CBr4 and CI4 (all from Ref.
[33], save the last from Ref. [34]); of boron BF3, BCl3, BBr3
and BI3 (all from Ref. [35]); of sodium halides, NaF, NaCl,
NaBr, NaI (all from Ref. [35]); and those of the other alkali
metals (all from Ref. [35]). The same order is found for the
gas phase phosphorus(III) halides [35], where the data for
PI3 were derived as the sum of the enthalpies of formation
[35] and of sublimation [36]. The enthalpies of formation
become less negative or equivalently, more positive, and the
species become less thermodynamically stable, in the order
fluoride \ chloride \ bromide \ iodide. This is consistent
with the electron transfer to halogen, and hence the ionicity
and electrostatic stability being the greatest for fluoride, and
then for chloride, bromide and iodide, decreasing in that
order. These statements are all consistent and sensible, but
… The same order of enthalpies of formation is experi-
mentally found for OF2 [35] \ OCl2 [37] \ OBr2 [38], and
in addition, from the analysis of high-level quantum
chemical calculations that are accurate to approximately
10 kJ mol-1 [39] for both species: OBr2 * OI2. Most
assuredly, the oxygen in OF2 is expected to have positive
oxygen and negative fluorine, while the other oxygen
halides likewise have negative oxygen and positive halo-
gen. We may ask how, then, can we compare oxygen
difluoride to the other oxygen dihalides?
Electron affinities and comparison of dihalogens
At this point, we turn to a discussion of the electron
affinities of the halogens as part of the understanding of the
electron-attracting power of these elements. After all, is it
not the halogen’s electron affinity, the exothermicity of the
gas phase reaction
XðgÞ þ e ! X
ðgÞ ; ð1Þ
the simplest, most unambiguous measure of the electron
attraction, the oxidizing power of an element? Let us take
the electron affinity values of F, Cl, Br, I from exquisitely
precise studies [40–43]. Doing so recovers the expected
order of oxidizing power Cl [ Br [ I, but then, it is seen
that F \ Cl. While fluorine has thus been spoken of as
perhaps anomalous [44–46], and an approximately
110 kJ mol-1 ‘‘correction’’ factor has been suggested
therein for fluorine with eight valence electrons in any
environment, these data are experimentally incontrovert-
ible. There is an approximately 55 kJ mol-1 spread
between the electron affinities of all four elements. We
now cite a set of earlier measurements [47] for the electron
affinities of F, Cl, Br, I. These values are less precise than
those noted above, but are more than accurate enough to
confirm the order F \ Cl [ Br [ I. This study additionally
allowed for distinguishing the energies of the two processes
2
P3=2 XðgÞ þ e ! X ð2Þ
ðgÞ
2
P1=2 XðgÞ þ e ! X
ðgÞ ; ð3Þ
where it is acknowledged that few discussions of atomic
halogens distinguish between the two spin–orbit states. If
one considers the 2P3/2–2P1/2 spin–orbit averaged value for
the two atomic states, the order I \ F \ Br \ Cl is found,
where the total spread is reduced to approximately
30 kJ mol-1, and I and F are found to differ by only
10 kJ mol-1. Do we wish to conclude that fluorine and
iodine have essentially equal oxidizing power?
With what other species can comparisons be made?
What other species educate us as to the oxidizing power of
the halogens? Let us remain, however, temporarily, in the
gas phase. The first comparison is made with the diatomic
halogens, F2, Cl2, Br2, I2. That is, we consider the ener-
getics of the related reactions
X2ðgÞ þ e ! ½X2 
ðgÞ : ð4Þ
From any of three references [48–50] with alternative
methods of determining the corresponding electron affini-
ties for all four of these species, we find the following order
of electron affinities: F2  Cl2 * Br2 \ I2, with a total
spread of nearly 100 kJ mol-1. That the electron affinity
value for the fluorine-containing species is greater than
those for the corresponding compounds with chlorine and
the other halogens is sensible and satisfying. However, it is
perhaps disconcerting that the molecular electron affinities
are smaller than those of the corresponding atomic quan-
tities until it is realized that it is an antibonding, and hence
relatively destabilizing, molecular orbital in which the
‘‘new’’ electron goes. Indeed, it may well be surprising that
the diverse [X2]- are bound at all.
Diatomic halogens and aqueous halides
We now turn to the simplest of all of the redox couples that
connecting the diatomic halogens to the aqueous halide
ions. To return us to more fundamental thermochemical
123

quantities, we consider the separate standard enthalpies,
Gibbs energies and temperature ‘‘corrected’’ entropies of
formation, i.e., DfH, DfG and TDfS where T = 298.15 K.
Here we consider the process
X2 þ 2e ! 2X : ð5Þ
The exothermicity and exoergicity decline significantly
in the classical order F  Cl [ Br [ I whether the dia-
tomic halogen is taken in the proper standard phase (F2, gas;
Cl2, gas; Br2, liquid; I2, solid), all in gaseous or all in
aqueous solution themselves. It may be surprising to the
reader that the choice of phase is quite unimportant. Using
the data in Wagman [35] for what follows here, we confirm
that the enthalpy and entropy are in opposition to each
other. Gaseous dihalogens possess higher entropy than
those in the aqueous phase, and so more entropy is lost upon
reduction of the ‘‘lighter species’’ gaseous F2 and Cl2 than
of the ‘‘heavier’’ species, liquid Br2 and solid I2, to form
aqueous halide ion. However, gaseous halogens have more
positive enthalpy than do their condensed-phase counter-
parts: to the defined 0.0 kJ mol-1 of the standard state are
added the enthalpies of vaporization and sublimation of
liquid Br2 and solid I2, respectively. We know that the
enthalpy and entropy must roughly cancel for the unsol-
vated elements because the free energies of vaporization
and sublimation necessarily must equal 0.0 kJ mol-1 at the
phase change temperature, and these temperatures are quite
close to the 298.15 K that defines the thermodynamic
standard state. The exothermicity associated with the for-
mation of the aqueous halide ions, or equivalently with the
negative of their enthalpies of formation, declines steeply in
the order F  Cl [ Br [ I; the reader may recall that the
four values were not that different for the gaseous species. It
is not surprising that anion solvation energies decrease in
the order F  Cl [ Br [ I as befits ever-increasing atomic
size, decreasing localized size/charge ratio and decreasing
ion-water hydrogen bond energies. Measurements of the
halide–water hydrogen bond/complexation enthalpies for
one halide ion with 1, 2, 3,…, n water molecules in the gas
phase were reported (see the pioneering studies [51, 52]).
This solvation corresponds to ‘‘freezing’’ or localizing
the solvating waters around the anion. Solvation entropies
significantly increase in the order F \ Cl \ Br \ I. Indeed,
the absolute entropy of aqueous F- is negative. Numeri-
cally, the value is –13.8 J mol-1 K-1, while that of aque-
ous Cl-, Br- and I- are positive (56.5, 82.4 and
111.3 J mol-1 K-1, respectively) and their neutral, iso-
electronic, noble gas counterparts (Ne, Ar, Kr, Xe) are
approximately equal, clustered around 62 ± 4 J mol-1 -
K-1. We noted previously that fluorine has an anomalously
low electron affinity, and it apparently also has an
anomalously negative entropy of solvation. It appears that
it is the solvation energy order that generates the
123
Struct Chem
decreasing, well-known, conventional, oxidizing power
order F  Cl [ Br [ I.
Latimer diagrams
The redox chemistry associated with both [OX]- and HOX
(as well as with other halogen oxygen-containing species)
may be put into context by the use of reduction potential
diagrams originally given by Latimer [53]. The diagrams
show the standard reduction potentials connecting the
various oxidation states of a given element including the
skip potentials. They make it possible to deal with complex
systems; the table of redox potentials is organized by the
voltage of the process, rather than by the chemical species
involved, and so the table does not provide a qualitative
understanding of the redox system. Changes in free energy
(dependent on concentration, temperature, the presence of
other non-inert reagents and pH) affect redox potentials. In
practice, pH changes are the most important factor in
aqueous chemistry that influence redox potentials because
large numbers of H? (or, to be more precise and correct,
[H3O]?) and OH- ions are usually involved in redox half-
reactions. For this reason, it has become conventional to
construct Latimer diagrams for the two extremes, at
pH = 0 and pH = 14 (or more precisely, 13.996). Poten-
tial diagrams in acid and alkaline solution constructed by
using the standard electrode potentials as reported by
Bratsch [54] are presented in Figs. 1 and 2.
The Latimer diagrams clearly illustrate that fluorine has
the highest oxidizing potential not only among halogen
elements but also among all the elements of the periodic
table. Is this surprising because fluorine is not the most
electronegative element? Actually, it is not, because, unlike
electronegativity, oxidizing potential is a measured vari-
able. The potentials for astatine are estimated values only
and for this reason will be omitted from the following
discussion. The given redox potentials illustrate the higher
oxidizing potentials of halogens and their anions in acid
than in alkaline solution. The only exception to this is the
ClO3-/ClO2 couple with a negative (reducing properties)
potential. In fact, ClO2 (as OClO, not its isomer ClOO) is
the only isolable halogen-containing compound with
halogen in the (IV) oxidation state. When relating [XO]-
and HXO to X2 in acid media, a decrease in redox poten-
tials from Cl to I is observed. In alkaline media, the
potential of the BrO-/Br2 couple is, however, the highest:
the order is Br [ Cl [ I  At. It is interesting to note that
the redox potentials for [XO]-/X- couples are given [54]
for alkaline media only and follow the expected order of
Cl [ Br [ I; in acid media, we must use the data for the
conjugate acids and the HXO/X- couples. A look at higher
oxidation states shows that the potentials of XO3-/XO-
Struct Chem
Fig. 1 Standard potentials for
systems involving halogens and
their anions in acid solution at
pH = 0.000 (E in V).
Estimated values are given in
parentheses
couples are given for acid media only, and again, the
potential of the BrO-/Br2 couple is the highest; the order is
Br [ Cl [ I. Figure 1 clearly illustrates the diversity of
redox reactions proceeding in aqueous media. It is there-
fore not surprising that redox titrations involving mostly
bromine and iodine and their anions in acid solutions are
advantageously used in classical analytical chemistry [55,
56]. The reader will note that we ignore here any system-
atic discussion of redox potentials involving heptavalent
halogen because the derived oxoanions are not the same for
all three halogens. Cl(VII) and Br(VII) are unequivocally
tetracoordinate unprotonated ions, while I(VII) includes
both tetra and (hydrated) hexacoordinate ions of diverse
degrees of protonation. Nonetheless, we note that there is
no ambiguity in the assertion that Br [ Cl for the [XO4]-/
[XO3]- couples.
Oxygen monohalides and hypohalites
Let us now turn to a discussion of compounds containing
both oxygen and halogens. Before proceeding, we note that
hypohalite ions have been written in the literature both as
[OX]- and as [XO]-. The former, written with the ‘‘O’’
first, is reminiscent of the well-known hydroxide and
acetate ions, [OH]- and [OAc]-, respectively. The latter is
more consistent with other oxohalogen anions such as
chlorite, chlorate and perchlorate [ClO2]-, [ClO3]- and
[ClO4]-. Rather than deciding between using [OX]- or
[XO]-, we will use both interchangeably. Relatedly,
hypohalous acids have been written as HOX, reflecting the
oxygen–hydrogen bond, and as HXO, such as chlorous,
chloric and perchloric acids as well as most other oxyacids
such as sulfuric and nitric acids, H2SO4 and HNO3. As in
the case of [OX]- and [XO]- also for hypohalous acids,
HOX and HXO will be used interchangeably.
Consider now the oxygen monohalides, OX, in which
there is a half-filled antibonding molecular orbital in which
the ‘‘new’’ electron goes. That is, we consider the ener-
getics of the related reactions
OXðgÞ þ e ! ½OX ð6Þ
ðgÞ
The measured [57] electron affinity order here is
F * Cl \ Br * I, and the total spread is but 10 kJ mol-1.
Do we wish to conclude that the oxidizing power of all four
halogens is numerically nearly the same? Or do we con-
clude that the oxidizing power of iodine is higher than that
of fluorine?
We recognize [OX]- as the long-known, trivially named
hypohalite ions, all recognized in salts and aqueous solu-
tions alike except for the case of X = F, for which neither
salts nor solutions are known to the experimental chemist
(LiOF has been seen in a cryogenic matrix [58]); see Ref.
[59, 60] for theoretical discussion of such compounds).
These species are the conjugate bases of the hypohalous
acids, HOX, and indeed the anions and these acids have
been studied separately, except for the case of X=F, for
which ‘‘the pK of HOF is probably [7’’ [61]. We find that
123

Fig. 2 Standard potentials for
systems involving halogens and
their anions in alkaline solution
at pH = 13.996 (E in V).
Estimated values are given in
parentheses
the reduction potentials for the [OX]- ions (X=Cl, Br, I) in
alkaline media are all rather close, as are the corresponding
reduction potentials of HOX (X=Cl, Br, I) in acid media.
[OCl]- is a common oxidant and is found in many
household bleach products. However, this choice of species
does not reflect its power as an oxidant; rather, consider-
ations of ease, safety and economics presumably dictate
this choice of species.
Hypofluorous acid, HFO and hypofluorite ion,
[FO]2
We now shift our attention to the comparison of hypoflu-
orous acid, HFO, and hypofluorite ion, [FO]-, with the
corresponding species containing the other halogens. More
properly, we need only compare HFO and [FO]- with
HClO and [ClO]- because we earlier compared the related
123
Struct Chem
Cl, Br and I species. Whether from high-level quantum
chemical calculations [62–64] or from experimental ref-
erences cited therein, the enthalpy of formation of gaseous
HFO is slightly more negative than that of gaseous HClO
(although the individual values vary from reference to
reference, the value for HFO is found in each source to be
roughly 10 kJ mol-1 more negative than that for HClO).
Equivalently, as the enthalpies of formation of gaseous F2
and Cl2 are 0.0 kJ mol-1 by definition, the gas phase
reaction
HFOðgÞ þ 1=2Cl2ðgÞ ! HClOðgÞ þ 1=2F2ðgÞ ð7Þ
is endothermic by the aforementioned *10 kJ mol-1.
Given the range of literature values for the enthalpies of
formation of HFO and HClO, we believe that it is safe to
say that the reaction is roughly thermoneutral if not
endothermic. If we assign a positive oxidation state to the
halogen atoms in both HFO and HClO, we would conclude
Struct Chem
that F(I) is comparably if not less oxidizing than Cl(I). Of
course, the reader may protest and assert that hypofluorous
acid does not have positive fluorine, and an immediate
conclusion may be that any comparison between HFO and
HClO is inconsistent and hence invalid. We accept the
inconsistency but still proceed.
Turning now to aqueous media, consider now the
reaction
HFOðaqÞ þ 1=2 Cl2ðgÞ ! HClOðaqÞ þ 1=2 F2ðgÞ ð8Þ
We recall that the enthalpy of solvation is the difference
between the enthalpy of formation of a gaseous species and
that of its infinitely dilute aqueous solution. The enthalpy
of solvation of HFO is not known from experiment. Can we
derive this quantity from the archival [35] value for HClO,
or can we at least extrapolate the enthalpy of solvation of
HFO through calculating the difference between the
enthalpy of formation of HFO and HClO? It is plausible
that the difference between the enthalpies of solvation of
ClOH and FOH is approximately the same difference as
that between ClCH2COOH and FCH2COOH (more pre-
cisely, the enthalpies of solvation of substituted acetic
acids, XCH2COOH [65], have been successfully approxi-
mated [66] by calculating the sum of the solvation
enthalpies of XCH3 and HCOOH. The HCOOH cancels
out; thus, we are saying that the difference between ClOH
and FOH is comparable to that of the difference between
ClCH3 and FCH3. Alternatively, we are saying that the
contribution of the component CH2CO is roughly the same
for both acetic acids). The difference between the enthal-
pies of solvation of FCH2COOH and ClCH2COOH is small
[65, 67], and so, the difference between the enthalpies of
solvation of HFO and HClO is, presumably, also small.
Therefore, the difference between the enthalpies of for-
mation of aqueous HFO and HClO is small. We therefore
conclude that the reaction of interest is roughly ther-
moneutral and that F(I) and Cl(I) are comparably oxidizing.
In the previous paragraph, we derived that the enthalpy of
formation of aqueous HFO and HClO are nearly the same.
So, too, are the enthalpies of formation of gas phase [FO]-
and [ClO]- [62], with the latter being somewhat more stable.
From this information, we deduce that the reaction
½FO 1 
ðgÞ þ =2Cl2 ðgÞ ! ½ClOðgÞ þ =2F2ðgÞ
1 ð9Þ
is roughly thermoneutral. If we now assume that the dif-
ference between the hydration enthalpies of [ClO]- and
[FO]- is approximately the same as that between
[ClCH2COO]- and [FCH2COO]-, we deduce that the
reaction
½FO 1 
ðaqÞ þ =2 Cl2ðgÞ ! ½ClOðaqÞ þ =2 F2ðgÞ
1 ð10Þ
is roughly thermoneutral as well. F(I) and Cl(I) are com-
parably oxidizing. Again, then, why is it normally assumed
that HFO and [FO]- are much more powerful oxidants than
their chlorine-containing counterparts? HFO needs ‘‘tam-
ing’’ [68] and [FO]- salts cannot even be isolated, whereas
the chlorine-containing species are household products.
There is a simple answer: elemental fluorine and elemental
chlorine are not the products of any experimentally realized
redox reaction of interest. Rather, the products are aqueous
F- and Cl-, or their protonated equivalents HF and HCl,
and we have already shown that F2 is a vastly superior
oxidant to Cl2. The energetics of the total redox reactions
of hypohalite and hypohalous acids to halide ion vastly
favor F(I) over Cl(I).
Closing remarks
We conclude that fluorine is the most powerful oxidant
among the halogens. However, the reasons and the sup-
porting data are often obscure, if not contradictory. We
provide the necessary reconciliation here, accompanied by
clarification.
Given Magdi Hargittai’s numerous writings on the sci-
ence-humanities interface, we opt to close our paper with
the words of the poet Eliot [69], who wrote in ‘‘The Little
Gidding.’’
We shall not cease from exploration
And the end of all our exploring
Will be to arrive where we started
And know the place for the first time.
Acknowledgments One of the authors (MPS) gratefully acknowl-
edges the Slovenian Research Agency (ARRS Grant P1-0045, Inor-
ganic Chemistry and Technology) for financial support.
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