J. K. S.
Wan
Queen's University
Kingston, Ontario, Canada
Forty years ago Sidgwick (1) recognized
that the first row elements such as nitrogen are rigor-
ously restricted to an octet of valence electrons and thus
assigned a “maximum covalency” of four to the first-
row elements. Apparently, this is a consequence of
the electronic configurations of these first-row atoms,
which can accommodate a maximum of eight electrons
in their 2s and 2p orbitals. The well-known stable
ammonium cation, NH4+, probably owes its stability
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to the valence shell octet. While it is generally ac-
cepted that ammonium compounds are similar in
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properties to those of alkali compounds, the question
as to whether ammonium can exist in a neutral state as
a radical or a metal has been a controversial subject in
chemistry for many years.
Some Theoretical Considerations
Two interesting theoretical approaches have been
made in recent years in order to give some insight into
the existence of NH4. The first approach was given by
Bernstein (0) who related the stability of NH4 to the
question as to whether saturated molecules such as
NH3 in the gas phase have an affinity for a hydrogen
atom, since hydrogen bond formation between NH3 and
ROH in gas phase has been detected by infrared spec-
troscopy. With the simple thermochemical cycle con-
structed below, Bernstein (2) obtained the relation
D(X—H) + D(XH—A) =
D(H—A) + D(X—HA) (!)
X + H + A
D(X-H) D(H-A)
XH + X + HA
D(XH-A) D(HA—X)
XHA
.where A = saturated molecule, NH3, HX hydrogen
donor molecule, and D bond dissociation energy.
= that reaction of NH3 with H2, which was formed in the
Since D(XH—A) equals AH/, the enthalpy of hydro-
—
gen bond formation, one readily obtains the bond dis-
sociation energy of the HA radical in the form of
H(H—A) D(X—H)
=
D(X—HA) -
AH/ -
By treating XH and X-—HA as diatoms so that an ap-
proximation of D(X—H) and DiX—HA) may be ob-
tained from a Morse function, Bernstein (2) made an
estimate that NHd in the gas phase could he stable by
about 7 to 33 kcal/mole. In a more recent and modi-
fied treatment (3) the same author estimated the stabil-
ity to be less than 10 kcal/mole.
In the other approach, Bishop (0) carried out a
quantum mechanical calculation in which the neutral
NH4 was described by a wave function composed of
Slater orbitals centered on the nucleus of the nitrogen
40 / Journal of Chemical Education
Is There a Neutral Ammonium Radical?
atom. The wave functions were of the same type as
those used in a similar calculation for methane (5) ex-
cept that the extra electron was placed in a 3s obital.
The result of the calculation suggested that NH4 is
stable by approximately 4.4 kcal/mole and its ionization
potential is about 3.94 ev. Although the calculated
ionization energy seems to be slightly lower than the
value of 4.2 ev, which could be calculated from a Bom-
Haber cycle of ammonium halide crystals, nevertheless,
Bishop’s work is probably more reliable than a previous
calculation by Horvath (6), who, using a set of less satis-
factory wavefunctions, predicted NH4 to be unstable.
If one accepts the arguments proposed by Bernstein
(2) and Bishop (/) that NH4 is a stable molecule, the
next formidable task is to find direct experimental sup-
port.
Some Experimental Approaches
The task of producing a neutral NH4 molecule for
experimental study is by no means an easy one. Bernal
and Massey (7) claimed that the reaction
2NH, + H3 — 2NH4 (3)
does not occur at low pressures and their calculations
show that at 0°K, a transition should occur from a mix-
ture of crystalline NH3 and H2 to metallic NH4 at a pres-
sure between 60,000 and 140,000 atmospheres. Such
conditions of temperature and pressure would challenge
and defy the effort by any experimentalist of the pres-
ent day.
However, Melton and co-workers (8, 9) seemed to
have found an easier experimental approach and ob-
tained some promising results in their study of decom-
position of NH3 on a platinum wire at temperatures
ranging from 75 to 1300°C. Using a mass spec-
trometer, they observed a transient ion, NH4+-, evolved
= from the hot surface of the catalyst. They suggested
decomposition, led to formation of some species of em-
pirical composition NH4 which was then ionized by the
hot platinum surface to give NH4+. A similar experi-
ment of catalytic decomposition of H20 also leads to
(2)
observation and conclusion of the presence of H30 (10).
In a separate investigation, Martin (11) studied the
room temperature emission of transient ions from NH3
and HsO evolving from a palladium surface. In the
case of NH3, Martin obtained a complex emission
spectrum ranging from NH4+ to N+ ions. His result
suggested complete atom scrambling and redistribution
of the NH3 molecules on the catalyst surface. In the
case of H20, he found H40+ to be the major transient
ion instead of the expected H30+. The apparent dif-
ference of Martin’s and Melton’s results could be partly
due to the use of a different catalyst.
 Although the evidence of NH4 from these studies is
not direct, it argues strongly in favor of the existence
of NIL.. Perhaps similar experiments can be carried
out in an epr cavity with NH3 flowing through a platinum
catalyst and the radical NH4 could be detected on the
catalyst surface before it is ionized and desorbed.
Historically two other major types of attempt have
been made to search for experimental evidence of NH4.
The first involved investigations of the reaction of a H
atom with NHS and the second group studied the neu-
tralization of NH4+ by an electron.
Reaction of H Atoms with NH3
Reactions of the type
H + A HA
have led to the production and detection of many in-
organic free radicals. Some interesting examples are
given below:
H + NO -+ HNO (5)
H + 02-^H02
H + CO — HCO
H + HCN
— H2CN
Reaction (5) was observed by Robinson (12) at low
temperatures and reaction (6) was observed by Foner
and Hudson by mass spectrometry (13). Both an in-
frared study (14) and an esr investigation (15) have
been made to support the occurrence of reaction (7) at
low temperatures. Reaction (8) was also detected by
esr (15).
It is perhaps worth noting that the above reactions
(6) to (S) all involve a hydrogen atom adding to mole-
cules containing multiple bonds. The similar addition
of a hydrogen atom to saturated molecules such as
H + NHS — NH4
is presumably much more difficult to detect directly.
Nevertheless, Farkas and co-workers (16) have pro-
posed the existence of NH4 as meta-stable intermedi-
ate in the mechanism of homogeneous and hetereo-
geneous exchange reaction of NH3 with deuterium:
D + NH3 NH3D -* NHjD + II
Kemball (17) has also studied the exchange reaction be-
tween NHS and D2 on a platinum surface and found the
initial exchange product to be always NH2D. This
suggested that NH3D is a possible intermediate.
In a study of the decomposition of NC13 in the gas
phase, Apin (18) found a clearly defined upper limit of
the decomposition above which NCU does not decom-
pose, while below the limit self-ignition occurs. He
then proposed the reaction
Ci + NCU + M —
NCU + M
as a determining step for the upper limit and suggested
that NCU is a stable radical which apparently does not
react in the volume and is lost at the wall.
In some more recent studies, the transition state the-
ory has been applied and worked out in detail for the
following reactions:
H + HC1 — HiCl
H + CU -* HCU
Both H2C1 and IIC12 were-treated as transition states
with linear structure and their vibrational frequencies
were calculated from kinetic analyses (19, 20). While
such examples suggest reaction (9) can be treated so as
to produce NH4 in a transition state, direct experi-
mental detection of NH4 was lacking up to that time.
Flash photolysis experiments involving reaction of XH3
with hydrogen failed to produce NH4 (3). Art esr
study (21) of Ii atoms, generated by microwave dis-
charge, reacting with NH3 in a flow system in which
products were trapped at 77°K, revealed only the pres-
ence of NH2, possibly formed by the reaction
H + NH3 Hs + NH2 (14)
From bond energy considerations, reaction (14) is ex-
(4) pected to be unfavorable. However, since the H atoms
were generated by discharge, they might be in excited
states.
The failure of observing NH4 in previous experiments
with H atoms and NH3 may simply be due to the fact
that NH4 has a low stability and a very short life time.
(6) Such difficulties seemed to have been resolved by Mel-
(7) ton (22) who has constructed a mass spectrometer with
three separate compartments in series. Each compart-
(8)
ment was equipped with a separate ion source and could
thus ionize reaction products produced in a preceeding
compartment for mass identification. With such a
modified apparatus, reactions can be followed in time
starting about 10-14 second after irradiation up to the
time for the formation of final stable products. Melton
(22) applied this technique to study the radiolysis of
NH3. In addition to the primary free radicals pro-
duced by the dissociation of NH3, he observed also
secondary transient neutral species including NH4.
Reaction (9) was then postulated as the mechanism
leading to the formation of NH4. In the analysis of
the mass spectrum, the relative abundance per 100 ev
(9)
electron of NH4 was found to be very small, in the order
of 0.1 as compared to the abundance of H atoms taken
as 100. Furthermore, Melton (22) stated that the rel-
ative abundance of NH4 was difficult to determine ac-
curately due to possible contribution from H20. This
apparently sets the value of 0.1 to be the upper limit
and suggests either reaction (9) is very inefficient or the
(10)
average life time of NH4 is exceedingly short.
Investigations of Ammonium Amalgam
The existence of ammonium amalgam has been pro-
posed since the mid-nineteenth century but the exact
nature of the amalgam remains controversial.
Shortly after Moissan (23) stated that ammonium
amalgam contains no NH4 but is an ammoniacal mer-
cury hydrogen compound, Smith (24) attempted to
establish the fact that a neutral ammonium configura-
(11) tion, NH4, can exist as an amalgam. This was followed
by the measurements of the lowering of the freezing
point of mercury in ammonium amalgam by Rich and
Travers (25) and their result suggested the presence of a
metallic solute, NH4, which was stable at least around
the freezing point of mercury. Subsequently, McCoy
and co-workers (26) isolated tetramethylammonium
amalgam at low temperatures and in ethanolic medium
(12) and claimed that tetramethylammonium ion can also
(13) form a neutral species. Their result was supported by
Volume 45, Number 1, January 1968 / 41
the experiments of Schulback (27), who studied the
electrolysis of the tetraalkylammonium iodides in liquid
ammonia.
Johnston and Ubbelohde (28) investigated the condi-
tions under which amalgam formation took place by the
electrolysis of ammonium sulfate with a mercury
cathode. They found definite evidence of amalgam
formation at room temperature and pH higher than 4.
They proposed the following discharge mechanism of
NH4 + ions at the mercury cathode:
NHU + e~ -*
'/alb + NIL,
—* Nil, -f- xHg —Amalgam
It appears that by using sufficiently high current densi-
ties, reaction (16) can be made faster than reaction (15)
even at room temperature, thus building up increasing
concentration of ammonium in the mercury.
The tentative view on the ammonium amalgam as
summed up by Johnston and Ubbelohde (28) is that NH4
dissolves in mercury and gives up one s-electron to the
conduction band. While the molecule NH4 dissolved
in mercury may compactly be referred to as “am-
monium,” it should be stressed that the evidence for
its existence is indirect. Perhaps it would be worth-
while to repeat some of the amalgam experiments in the
cavity of an esr spectrometer.
In a more recent polarographic study of quaternary
ammonium compounds, Southworth and co-workers
(29) reaffirmed the postulated existence of neutral
ammonium. They stated that in electrolytic reduction
of simple aliphatic quaternaries, the quaternary am-
monium ion acquires an electron to form a neutral en-
tity, which subsequently either reacts with water to
form hydrogen and quaternary hydroxide, or breaks
down into a tertiary amine and a hydrocarbon. It is
reasonable to assume that in liquid systems the life
time of the neutral ammonium will be too short for di-
rect detection. However, if the neutral ammonium
radical can be generated and trapped in a solid lattice,
it might have a life time long enough for spectroscopic
study.
Irradiation of Solid Ammonium Compounds
It is well known that irradiation of ionic solids may
lead to the ejection of electrons which, in some cases,
can be trapped in solids (30). There are various mech-
anisms in which an electron may be trapped in the
crystal lattice; it can be trapped in an anion vacancy
as an F center, or it can be stabilized as one of the many
known electron-excess color centers such as AT center, R
center etc. (31). Among the most studied solids are the
alkali halides, for example, irradiation of LiF crystals
at a high dose rate produces unpaired electrons, elec-
tron-deficient centers, as well as metallic Li (32).
The trapping of electrons as F centers and other
electron-excess paramagnetic centers is well established
in alkali halide crystals. However, to the best of the
author’s knowledge, F centers or other electron-excess
centers have not been reported in any of the radiation-
damaged ammonium compounds. In fact, though
there have been numerous published reports on irradi-
ated ammonium compounds, few have accounted for
the fate of the ejected electrons. Pick (S3) and Ruch-
ardt (34) irradiated NH4Br by X-ray at temperatures
42 / Journal of Chemical Education
below —
50° C and observed an optical absorption band
at 3.25 ev. The band was found to have its position
and width independent of temperature, and was as-
cribed by these authors as due to the ionization of the
neutral NH4 radical, which is presumably formed in the
following reactions:
Br" * Br -†- e~ (17)
e~ + NH4+—>- NH4(trapping of electron) (18)
NH4 -(- /ii. —>-
NH4+ + e"(ionization) (19)
(15)
(16) A similar observation was also reported by Kamiyoshi
(35), who studied the irradiation of XLI4I and found an
absorption band at 3.3 ev. If the interpretation of the
above experiments was true, then a similar esr study
should reveal the presence of NH4 radical. In a recent
study combining both optical and esr methods, Ivanzig
and co-workers (36) established the nature of this ab-
sorption band at 3.3 ev as due to a Vk center, which is a
halogen molecule ion, X2~.
In another study of irradiated glycine crystals, part
of the resulting esr spectra was interpreted as due to
the presence of an NH4 radical (37). This was later
disproved by ATorton (38), who, using 1JC isotope sub-
stitution, found that the correct interpretation is CH-
NH3+(C02)-.
In the crystalline state, Ag+ doped substitutionally
for K+ in KC1 crystals has been shown to react with
electrons to form a neutral Ag atom (39). The same
process was also found to occur in irradiated frozen
silver nitrate and silver sulfate solutions (40). Thus,
by analogy, if KC1 crystals are doped with the NH4 +
ion, would irradiation produce the corresponding NH4
radical for observation? We will attempt to show the
difference between the KCLAg and the KCLXH, sys-
tems from a pure thermodynamic point of view. In the
KCLAg system, the process in the solid state
AgCl(s) + CU(s) =
Ag(s) + Cl,-(s) f20)
is approximately 36 kcal exothermic; whereas the
similar process in the KC1:NH4 system
NH4C1(s) + Cl-(s) =
NH4(s) + Ch-(s) (21)
„ is about 30 kcal endothermic. However, it is quite
clear that such a simple thermodynamic consideration
cannot govern whether the reaction may or may not
occur. Perhaps it is then worthwhile to study such
systems as the KC1:NH4 and also systems involving
frozen NH4+ salt solutions.
In a recent study of irradiated KAsFe crystals, Wan
and Bernstein (41) found the existence of isolated K
atoms in the crystals. An analogous study of irradiated
NH4AsFfi is now in progress in the author’s laboratories
in the hope that it may lead to formation and isolation
of the NH4 radical in the crystals.
Finally, it should be mentioned that trapping of an
electron by a saturated molecule and its subsequent
stabilization is, by all means, not impossible. In
crystal state, the existence of molecule-ions such as F2~,
Cl2“, and Br2~ have been established by esr and optical
methods (31). CI2~ was also observed in sulfuric acid
glasses at 77°K (42). In addition, detailed theoretical
studies of the stability of these halogen molecule-ions
have been carried out (43).
Conclusion
Some experimental evidence, both direct and in-
direct, has been obtained to support the existence of a
neutral ammonium radical, although unequivocal proof
and detailed studies of its structure and reactivity are
still lacking.
Acknowledgment
The author wishes to thank Drs. H. J. Bernstein and
J. R. Morton for stimulating discussions. Financial
support by the Research Corporation, New York, and
the National Research Council of Canada is gratefully
acknowledged.
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Volume 45, Number 1, January 1968 j 43