Paul A.

Giguere
Universit6 Laval
Quebec GIK 7P4
I
The Great Fallacy of the H+ Ion
Canada
and the True Nature of H30+
The term hydrogen ion and the symbol H+ are still cur-
rently used to designate the entity characteristic of acids
(BrQnsted's definition), especially in aqueous systems. Yet,
that formulation has been a perennial source of confusion, not
only in teaching, but also in interpreting experimental results.
Even among modern chemistry textbooks one finds an in-
credible diversity, if not discrepancy on this most fundamental
question. Most authors do acknowledge a more complex
species than the over-simple H+. They call it variously hy-
drated proton (protonated water would he more logical!),
proton hydrate, "wet" proton, oxonium ion, and more ap-
propriately, hydronium ion'. As for the formula, beside the
right one, H30+, authors use any of the following: H+.,,
H+(HzO),, H+(H20)4. (H8. 3Hz0)+, HgOqt, etc. In a recent
"comprehensive" monograph ( 2) Hs0+ is barely mentioned
as such! But there is no longer any excuse for such uncertainty.
We now have sufficient data, experimental and theoretical,
t o get a clear picture as I intend to show hereafter.
Historical Background
The question originated with the theory of electrolytic
dissociation (Arrhenius, 1887). Since all common acids contain
hydrogen, which they give up readily, it was logical t o identify
them with the H+ ion, the counterpart of the OH- ion in bases.
The invention of t he pH scale (SQrensen, 1909) established
definitely that practice. However, when physicists began
probing the structure of the atom, it was soon realized that H+
is no ordinary ion. In fact, strictly speaking, it is not an ion
according t o the definition that an ion is "an atom, or group
of atoms that carries a positive or negative electric charge" ( I ) .
The symbol H+ represents, not an atom, hut a subatomic
particle, the proton.
The proton is unique in chemistry by virtue of its atomic
mass and electronic size. Because of the latter it exerts an
intense electric field on its surrounding. Therefore, it cannot
remain free under ordinary conditions. In the case of aqueous
acids it must he combined with the solvent, and H30t is the
simplest possible entity. Now, the concept of H30+ got a bad
start when it was first mentioned, a t the turn of the century,
in a paper dealing with organic compounds of. . . quadrivalent
oxygen (3). The formula OHsOH and the name oxonium hy-
droxide were suggested for it by analogy with ammonium
hydroxide, NHqOH. Soon afterwards, physical chemists rec-
ognized various indirect evidence for H:iO+ in aqueous acids:
for instance from acid catalysis (Goldschmidt and Udby,
1907), cryoscopy (Hantzsch, 19081, molecular volume (Fajans,
19211, and refractivity (Fajans and Joos, 1924) (Cf. Bell (4)
for a review). Following the discovery of X-ray diffraction by
crystals, Volmer (5) showed that the solid monohydrate of
perchloric acid (M.Pt. + 50C) is isomorphous with ammo-
nium perchlorate. From this he concluded rightly that it is an
ionic compound, HsO+C104-, not a molecular hydrate,
HCIOcH20, as it is still often considered. Definite identifi-
cation of H30+ ions finally came with the discovery of nmr.
In 1951 two independent groups (6) showed that in the crys-
talline hydrates of strong mineral acids the three protons are
equivalent. Shortly after, the fundamental vibrations of H30+
ions were identified in frozen acid solutions (7).
Still, from all that evidence one could not infer the nature
of the ion in aqueous acids. Indeed, due t o the much greater
mobility of liquids the association ofa proton with a given H20
molecule could well be too short-lived to vield a distinct
chemical entity. That seemed all the more likely as a number
of early attempts t o detect the vibrations of HnO+ had failed.
But, as explained below, these early studies, mostly by Raman
spectroscopy, were doomed to failure. Infrared spectra turned
out t o he much more revealing as we reported some twenty
years ago (8). Our assignment of the fundamental hands of
HsO+ in aqueous aciddwas disputed by some (9,10) hut later
on definitely confirmed (11,12). Finally, an elaborate X-ray
and neutron diffraction study of hydrochloric acid (13) has
given Hs0+ the consecration of direct experimental proof. Yet,
in spite of all this evidence, it is a safe bet that all the
"doubting Thomases" will not he convinced.
The Thermodynamics Viewpoint
I t is in the realm of thermodynamics that the H+ ion con-
cept seems particularly fallacious, and even absurd. As early
as 1919 Fajans (14) estimated the proton affinity of the H20
molecule a t 182 kcallmole, a remarkably accurate value for
the time. From that he derived the orenosterous fieure 10-130
. . "
for the concentration of free protons in water. In a more pic-
turesque vein Sidgwick (15) wrote that "in loT0 universes filled
with a 1 N acid solution there would he only one unsolvated
hydrogen ion!" Therefore, the equation
Hz0 = H+ +OH- (1)
still currently used to describe the ionic dissociation of water
is purely fictitious. Even in t he gas phase this process is
physically impossible. Because of the high ionization potential
of the hydrogen atom it would require an enormous energy:
387 kcal mole-', to he exact. And even if that much energy
were provided, complete atomization would take place in-
stead
H20-2H+O (2)
since it requires only 221 kcal mole-'. Formally speaking, the
ionization of water is a bimolecular orocess. which should he
written as such
2H20 = HsO+, OH- (3)
The conventional excuse for the H+ formalism is that it stands
for H 0'. But experience shows it is not always so. Take, for
instance, the uhlrs of thermodvnumic functions for hvdratim
of ions (16). I t is customary to head the list of ions with the
' The present state ul ronfuiiun is wrll rxl*ml,lifird I,). rulr .{ 14 of
the NwntncIature of Inr,ryanic ('hem~stry of the IL!1'.4CI 1 1 ,.
"The ion HgO', uhleh is i n fact the monr.h\dn,ted un, tun, 1s to hr
known as the oxonium ion when it is believed have tdis constitution,
as for example in HzO+CIOc, oxonium perchlarate. The widely used
term hydronium should be kept for the cases where it is wished to
denote an indefinite degree of hydration of the proton, as, for example
in aqueous solution. If, however, the hydration is of no particular
importance to the matter under consideration, the simpler term hy-
drogen ion may be used." (Italics mine.)
And for good measure there is a footnote.
"The committees concur in oxonium for the ion H-Of. but see little
dration."
All this notwithstanding, hydronium sees preferable to oxonium
which applies to all compounds of trivalent oxygen.
/'
Volume 56, Number 9. September 1979 1 571
objectionable H+. I n the case of partial molal volumes, the
accepted value, VH+" = -5.4 cm3 mole-I a t 25", refers ob-
viously t o t he H30+ ion, not t o the bare proton. However,
when it comes to the enthalpy of hydration, this time the given
value, AH = -270 kcal mol-', refers not to the HaO+ ion, hut
t u H7; which explains why it is more than twice as large as for
the other monovalent ions. Actually, that quantity is the sum
ot'two quite different terms. Pirrt i i the enthalpy of the gas-
phase reaction
H2 0 + H+ - H30+ AH0 = 166 kcal mole-'
(4)
also known as the proton affinity of HzO. It has been measured
accurately, in particular by mass spectrometer (17). (Cf. (18)
for a review). Clearlv. it does not belona in the above tables
. .
since reaction (4) is not a hydration. In hydration processes
the Hz0 molecule retains essentially its structure. What we
have here, instead, is a true chemical reaction, with formation
of a stronz covalent bond. Incidentally, the O-H bonds in the
free ~ ~ 0 : ion, 130 kcal mole-', are even stronger than those
in H~ 0 , 1 1 0 kcal mole-'. The other term, namely the enthalpy
of hydration of the gaseous H30t, is not known so accurately.
Values ranging from -70 t o -125 kcal mole-' have been re-
ported for it (16). This wide uncertainty may stem from t he
present dichotomy. At any rate, the accepted value, -103 kcal
mole-', seems reasonable by comparison with -106 and -101
kcal mole-I, respectively, for the isochore Na+ and OH- ions.
In retrospect, the confusion between H+ and H30+ appears
as a remnant of the traditional lack of concern of thermody-
namicists for things structural.
The Real H30t
The above mentioned nmr studies (6) not only established
t he H20+ ion as an entitv hut also vielded some structural ~ - ~ - - -
" - ~ ~
information; i.e. the nonhonded H-H distance (Fig. 1). Be-
cause the O-H distance was not measurable by t hat tech-
nique it was not possible to decide between a flat triangle and
a shallow pyramidal structure. The latter, more probable by
analogy with the isoelectronic NH3 (19), was later confirmed
by neutron diffraction (20). In fact, the O-H bonds have the
same length as in ice, and apex angles fall generally between
110" and 115". This means a rather flat pyramid, 0.25 t o 0.3
A high. Likewise, the dynamics of H30+ have been studied in
various crystalline compounds, mostly by infrared (21). In-
deed, because of the ionic charge on the hydrogen atoms, the
HqOf ion is stronelv nolar. Therefore, its vibrations (even the
.. . .
parallvl ones) art: t w weak tu bc, detected ensdy I I V the Hamnn
effect. This accounts rm thr ahwe mentioned failure of mrly
studies. In liquid acids the overwhelming absorption of water
makes more difficult the observation of the HaO+ bands;
particularly the two O-H stretching (Fig. 2). Still, the weak
maximum around 2900 cm-' clearly belongs to the ion. Its low
frequency (compared to 3100 cm-I in watrr, is i nd~r nt i w of
\.cry strong hydrogen hmding. The tu,o bending modw I.,.
the symmrtric, rentt!nvl aruund 1200 cm-1, and u.1 .it I X0
Figure 1. Structure ol,the average H30t ion in various crystals.
572 1 Journal of Chemical Education
Frequency (cm-')
Figure 2. Infrared absorption spectra of thin films of the four hydrohalic acids.
(Concentrations in mole per cent). Reproduced from ( 12).
cm-' are much more obvious. The former, located in a "win-
dow" of the water absorption, can be detected even in a 1 M
solution: that is with some fifty water molecules per hydro-
nium ion. Interestingly, the same lower limit holds for the 3610
cm-I Raman hand of the OH- ion in alkaline solutions
(22).
Finally, diffraction methods have provided direct confir-
mation of H30+ ions in liquid acids. Liquids always give rather
diffuse diffraction patterns from which structural information
is not easily extracted. Nevertheless, much progress has been
achieved by using these data to test theoretical models. In the
case of water this had led to accurate interatomic distances
(23). A similar extensive investigation (13), using both X-ray
and neutrons, has enabled measurement of the O-H (or
rather O-D) bond length of the ion in concentrated hydro-
chloric acid, 1.02 A. More important, perhaps, is the O-H-0
distance, 2.52 A (Fig. 3), significantly shorter than that in
water, 2.83 A (23). From these data a model, was proposed
(Fig. 4), in which H30+ is coordinated to four water molecules;
three of them linked by strdng H-bonds, the fourth, by much
weaker cbarge-dipole forces. In short, the geometry of the
H:%0+ ion, whether in crystals or in liquid acids, is now known
with same accuracy as that of H20 in liquid water, ice, or the
hydrates.
The Average Lifetime ol H30+
Obviously, an important property of the HaO+ ion in
aqueous acids is its average lifetime T. I t has been the object
of much speculation and calculation. A first estimate of 0.24
psec (lo-" sec) was calculated a priori by Conway, Bockris
and Linton (24) from their elaborate measurements of proton
conductance. A higher value, by about one order of magnitude,
was derived by Eigen (25) from his dielectric relaxation data.
The exact value, however, was found by means of nmr through
various methods. Meiboom (26) first used the 170-induced
proton relaxation to measure the rate of the acid-catalyzed
proton exchange reaction in water and very dilute acids:
More accurate measurements (27) have yielded a rate con-
stant k, = 7.9 X lo9 1 mole-' sec-' at 25C. The half-life of
that bimolecular reaction,
1
to5 = - =
1
= 2.2 psec
k.c
7.9 X lo9 X 55.35
(6)
is, therefore, the average lifetime of H30+, T.
Now, a most significant corollary to these measurements,
which has been generally ignored, was the determination of
the rate of the base-catalyzed proton transfer,
HzO + OH- SOH- + H20 (7)
I t turns out that this reaction is about half as fast as its acid
counterpart; namely k b = 4.5 X lo9 1 mole-' sec-'; hence tos
= 4.0 psec! It is an ironic observation that the OH-ion in water
has an average lifetime barely double that of HaO+, yet its
reality has never been questioned. Incidentally, this ratio of
0
.- 1' 0
-I 0
r c l 160
HCi 8.20 H20
-I
HCi 399 H20
- I
Figure 3. Correlation functions from Xqay diffraction paitern of hydrochloric acid
~oiutions, reproduced from Triaio and Narten (13).
u
Figure 4. Model illustrating the average coordination of H30i ions in dilute
aqueous acids, redrawn from ( 13).
1:2 was already known from the excess mobility of these two
ions, as pointed out by Conway et al. (24). Short as these
lifetimes may be, they are sufficient for both ions to vibrate
as discrete chemical entities. For instance, the lowest fre-
quency in the spectrum of HaO+, 1200 cm-', requires a min-
imum lifetime of only 0.03 psec. The corresponding figures for
the other vibrations are listed in Table 1. Obviously, as the
concentration of the acid increases, so does the average life-
time of the HaO+ ions, while that of the Hz0 molecule de-
creases. The numbers in Table 2 are based on Eieen's an-
-
proximate relationship between lifetime and concentration
(28). It is not often realized that because of the fast uroton
exchange, the average lifetime of a given Hz0 molecule in
water is less than one millisec. at ordinary temperature.
The Mechani sm of Proton Transfer
Proton transfer reactions are among the fastest and most
common reactions. They are important not only in solution
chemistry, but also in the gas phase and in biological systems
(for instance in carrying electric charges within proteins as
zwitterions). In condensed phases, proton transfer obviously
takes olace t hr ou~b hvdroaen bonds. The latter. then. mav
- . - . .
be regarded as a preliminary stage. On the basis df their con-
ductivitv measurements Conwav. Bockris and Linton (24)
concludkd that the rate-determining step could not be a
classical proton migration, nor quantum mechanical tun-
nelling, hut rather rotation of the water molecules that accept
the proton. Intuitively, we can picture as follows the most
favorable situation: (a) the three O-H-0 nuclei are co-linear,
(b) the 0-0 distance is at a minimum, and (c) the 0-H
stretching is maximum. Since the actual transfer occurs via
stretching of the O-H bond, its period is roughly the same
(Table 11, about 10 fsec (1 femtosec = sec). Note that
this takes only 0.2% of the average lifetime of H30+.
The hvdroeen bond distance. 0-0. is a most imuortant
-
parameter, of course. Originally, it was assumed that the po-
tential curve for oroton transfer was of the double-well tvue.
Given the experimental distance of 2.52 A, and an O-H boid
leneth of 1.02 A (13). this leaves less than 0.5 A for a uotential
hairier. I n fact, quantum mwhanicnl ralnrlntions 13i1 shuu,ed
that in that case the "wress urnton" wi ~ ~ l d t w trar111tv1 inn
single asymmetric potential well. However, the abobe 0-0
distance is an equilibrium distance. One must also take into
account the thermal vibrations of atoms. In liquid water and
ice the root-mean-square amplitudes of H and 0 atom vi-
brations are of the order of 0.2 A (30). Interestingly enough,
Newton (29) has found by ab initio calculations that for an
Table 1. Approximate Values of the Vibrational Frequencies,
Periods, and Number of Vibrations (N) ot the H,0+ Ion in Water
and Dilute Acids.
O-H stretch. 3000 0.01 200
HOH bend. (asym.) 1700 0.02 100
HOH bend. (sym.) 1200 0.03 75
Libration 800 0.04 50
Translation 300 0.1 20
Table 2. Average Lifetime T of a Given H,O Molecule in
Aqueous Acids and Bases at 25%
pH ras 7.. rm
TS hall-llfe dueto add-catalyzed proton transler.
vb. half-life due to base-catalyzed proton transfer.
Volume 56. Number 9, September 1979 1 573
0-0 distance of 2.37 A or less the notential curve of the nro-
ton is of the single, symmetric-well type. This is reasonable
considerine the short distance involved. Therefore, it seems
that tunnelling plays no significant rdle hericontrary
to current belief.
This, then, raises the question of why the protons spend
most of their time covalently bonded in H30+ ions? The an-
swer must be that proton transfer in aqueous solutions is a
concerted process involving reorganization of the hydrogen
bond pattern around the "excess or defect proton." Indeed,
the short lifetime of HsO+ (and OH-) is comparahle to the
lifetime of the hydrogen bond (31). This model, which relates
proton transfer with thermal agitation, can account for the
anomalies of proton conductance; in particular the large de-
crease in the heat of activation with temperature, from 2.5 kcal
mole-' at room temperature down to one tenth that value near
400K (32).
What about H.04+?
The H904+ formulation often used in textbooks was first
postulated in 1954 on the basis of such indirect evidence as
s~eci f i c heat and entronv (33). Since then it has received
.- .
sipport from various sources, both experimental and theo-
retical (10). Eigen (281, with whom it has become identified,
looked upon it as the hydration complex of H30+ (primary
hydration shell); that is, essentially, as in the abovemodel (Fig.
4). Nevertheless, the Hg04+ formulation is misleading because
it does not distinauish between the covalent O-H bonds of
H30+ and the hy&ogen bonds to the three water molecules.
Furthermore, i t suggests that the ionic charge is evenly dis-
tributed over the whole complex. Chemical intuition tells us,
on the contrary, that it must rest mostly on the central H30+
ion. Actually, Newton and Ehrenson (29) have calculated that
in the free H904+ species, only 7% of the positive charge is
transferred to each of the three water molecules. In other
words, the various building blocks in this complex largely
retain their identities. A better formulation would be H30f
:iH20. But even this is not always correct; as, for instance, in
very concentrated acids where there is insufficient water for
complete hydration of the H3Of ions. At any rate, there is no
need to specify the extent of hydration in this particular in-
stance. Here again the OH- ion provides a valid term of
comnarison. Because of its neeative charee it is a strona hv-
.. .
drugen Iwnd ucreptor. 111fact, there is conrlusiee widt!nre,
tanh from mass snertrumetrv (18) and ob inirio calculations
(29), that the 0<- . 3~z0 complex is particularly stable, with
hydrogen bonds nearly as strong as those in H30t.3Hz0. But
we never formulate the aqueous OH- ion as H70r-. Why,
then, write Hg04+ in lieu of H30+?
What about H502+?
The H502+ ion, variously called proton dihydrate or dia-
quohydrogen ion, was suggested first by Huggins (34) to ac-
count for the abnormal mobility of the proton in water. He
pictured it as a strong, symmetric hydrogen bond linking two
water molecules (HzO.H.OHz)+. So far, however, HsOzt ions
have been observed onlv in the solid state (20. 21 1. Their
characteristic is a very ihort 0-0 distance (2.41-2.45 A).
Otherwise, their aeometrv varies considerably from one
wmpo~~nrl tcr theo;her depending on th(.irsurro&dinc in the
cr\fstal lattice. This is true, in particular, of the luration of the
excess proton, which ranges from a centrosymmetric HsOz+
to the hydrate H30f.He0 (35). Clearly, the HsOzt ion is an
uncommon species which requires stabilization by the crystal
field.
In spite of this, the concept of "H50zf grouping" in aqueous
acids (and conversely, H302- in bases) is still advocated by
Zundel and coworkers (10,36). Its main feature is said to he
"an easily polarizable hydrogen bond;" in other terms, the
nroton fluctuatine verv r a~i dl v between two water molecules
which retain t hzr idkntiiy, ior between two OH- ions in
HaOz-). But this is contrary to experimental evidence, hoth
from spectroscopic and diffraction data. The three water
molecules in the H30+.3Hz0 complex must he equivalent on
the average, except during the fast proton transfer. And this,
in the final analysis, is what these "Hs02+ and H30z-
groupings" refer to; namely the activated complex, or tran-
sition state of the proton transfer reaction. Like all activated
complexes they dissociate at the first vibration. As a conse-
quence, the 0--H stretching band of the proton donor is
broadened considerably towards low frequencies. In fact, this
so-called "continuum'~occurs also in no;-aqueous acid solu-
tions, e.g. CH30H (l o), and in the H-X hands of super-
saturated hvdrohalic acids (37). In short. there are nodistinct
H5O2+ ions or groups in aqueous acids
The Strange Case of Hydrofluoric Acid
-
A typical example of the errors engendered by the HC ion
fallacy is the current theory of hydrofluoric acid. Chemistry
textbboks tell us that hydrogen fluoride in dilute aqueous
solution is a weak acid, like formic and acetic acids. This is a
most surprising observation considering that the other three
hydrogen halides are very strong acids. The "accepted" value
of the pK, based on electrochemical measurements, is 3.2 for
HF, compared with -7.4 for HCI, -9.5 for HBr, and -10 for
HI (38). Now. what could be the reason for such an enormous
. .
difference-more than 101O-between the dissociation con-
stants of HF and HCI? That riddle has long challenged the
imaginations of chemists. Back in 1912 Pick (39) put forward
an hvpothesis which has endured ever since. Essentially he
pos&iated that the dissociaiion is a two-step process:
HF-?IH++F- (8)
HF + F- 2 HF2- (9)
The first equilibrium, kl, which must be rewritten thus,
H20 + HF + HaO+ + F-
(10)
would lie far to the left (the dissociation amounting to only
2% in dilute solution), and the second one, kz, slightly to the
right.
But, that hypothesis raises some serious objections. First,
chemical intuition tells us that the H-F bond, which is nearly
50% ionic in character (40), cannot remain undissociated in
a strong ionizing solvent like water. More concretely, Pick's
hypothesis cannot account for certain properties of hy-
droflnoric acid. For instance, contrary to ordinary weak acids,
HF in water seems to become more and more dissociated with
increasing concentration. So much so that in the pure state
it is near& as strong as sulfuric acid, judging from the Ham-
mett acidity function (41 ). Likewise, the vapor pressure and
boiline noint curves of the H9O-HF hinarv svstem ~r ovi de
-. " "
clear evidence against Pick's model. Hydrofluoric acid, like
the other three hydrohalic acids, shows strong negative de-
viations from Raoult's law leading to a maximum boiling az-
eotrope (Fig. 5). This can only mean that the solute is largely
ionized over that concentration range. Otherwise, undisso-
ciated HF would lower the boiling point of water.
The Key to the Riddle
The apparent contradiction between the electrochemical,
and the other nhvsio-chemical nro~erties of hvdrofluoric acid
has been resoivld thanks to infrared spectrbscopy (42). As
may be gathered from Figure 2 the absorption spectra of the
four hydrohalic acids show great ressemblance. The major
difference in the case of HF is a large shift of the strong vr
band to about 1830 cm-I. Such a large shift (100 cm-I) is
uncommon for an OH bending mode. I t is indicative of an
exceptionally strong H-bond. ~ogically, it must he related to
the electrolytic anomalies mentioned above. A suitable model
to that effect is the strongly hydrogen-honded ion pair, or
proton transfer complex,
.. . H---H+.. .F-
574 / Journal of Chemical Education
waipnt x HF Wcigh1.l. HCi
Fi gur e 5. Boiling-point curves 01 the binary systems H20-HF and
H20-HCI.
Ion pairs of hydronium chloride and bromide had been de-
tected previously in liquid sulfur dioxide (43). Normally, one
would not expect them in measurable concentration in
aqueous solutions. However, the case of hydrofluoric acid is
unique in that the F- ion is the strongest proton acceptor
known, as shown by the remarkable stability of the HF2- ion.
This, coupled with the strong proton donor nature of &0+,
explains the great strength of these ion pairs.
Therefore, the dissociation process should be represented
as follows:
H20 + HF - ( H3 0 t . . . F-) + H30+ + F- (11)
Judging from the freezing-point lowering (41) only about
15 oer cent of the ion oairs are dissociated at infinite dilution.
As the concentration of HF increases, the F- ions gradually
reolace the H,O moleculee which stabiliee the ion pairs. This,
cdupled with ihe incipient formation of HF2- ions, increases
the number of charged species, and the apparent strength of
the acid. Thus we see that, contrary to the heavier hydrogen
halides, HF behaves as a weak acid in aqueous solutions be-
cause the F- ion is a hetter proton acceptor than H20.
CohcluSIOnS
The present review may be summarized as follows:
(1) The hydronium ion H30+ is just as real as its counter-
part, the hydroxide ion OH-.
(2) In water and aqueous solutions both ions are equally
short-lived due to rapid proton transfer. Their average lifetime
at 25OC are respectively 2.2 and 4.0 psec, as measured by
nmr.
(3) The existence of discrete H30+ ions, first detected hy
infrared spectroscopy, has recently been confirmed directly
hy X-ray and neutron diffraction in hydrochloric acid.
(4) In aqueous acids the H30+ ion is strongly H-bonded to
three Hz0 molecules, with 0-0 distances (2.52 A) much
shorter than in pure water (2.83 A).
(5) Proton transfer between H30+ and water (or water and
OH-) is a concerted process accompanied by rearrangement
of the H-bond network. It takes less than 1 per cent of the
average lifetime of the H30+ ion.
(6) Contrary to current theory HF is mostly ionized in
water like the other three hydrogen halides. I t behaves as a
weak acid because of the limited dissociation of the strongly
H-bonded ion pairs, H30+-F-, the predominant species in
dilute solutions.
(7) The erroneous H+ ion formulation, and names such as
"proton hydrate" should he abandoned to avoid confusion.
Likewise, there is no need, in gerneral, to indicate the extent
of hydration of the hydronium ion as in H30+.3H20. The term
hydrogen ion is here tostay, of course, like other time-honored
misnomers in Science.
Literature Cited
(1) Weas% R. C., (Editor). '"Handbaok ofchemistry and Physic.," 55th ed. The Chemical
Ruhber Co. Cleveland, Ohio. 1975. pp. Bd5. F-98.
(2) Franks, F., (Edilnrl. "Water. A Comprehensive Tieatire." Val. 3, "Aqueous Solutions
oiSimple Electrolytes.'' Plenum P~e r s , NPW Ymk, 1973.
(3) Collie, J. N. , andTickle, T. , J . Chrm. Soe, 75.710 118991.
(4) BeI1.R. P.;'TheProtonin Chemistry,'(2nd ed. Cur n~i l University Pross,NewYork,
1973.
I51 Volmer,M.,Ann. Chem., 440,200i19241.
(6) (a) Richards, R. E., and Smith. J . A. S., Trans. Farodoy Soc, 47, 1261 (19511. lhl
Kakiuchi, Y., Shomo. H.. Komatsu, H.. and Kigmhi. J.. J. Chem. Phya.. 19. 1069
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