[19531 Addison and Lewis.

1869

384. The Liquid Dinitrogen Tetroxide Solvent System. Part X I I P

Factors related to the Mechanism of Metul-Dinitrogen Tetroxide
Reactions ; the Dipolar Nature of Dinitrogen Tetroxide in the Liquid
State.
By C . C . ADDISONand J. LEWIS.
The paper considers factors having a direct bearing on the reaction
mechanisms which occur in metal-liquid dinitrogen tetroxide reactions.
The following two factors concern the ion-pair mechanism : (a) Apparently
discordant evidence on the dipole moments of the N204and NO, molecules
has been correlated. Recalculations based on published data show that all
experimental results may be interpreted satisfactorily if i t is assumed that
pNIOIis zero, and that pNOlvanes with temperature, although no simple
explanation of this unique variation in pNo2is available. (b) A mechanism
for the formation of [NO+]I30,-] ion-pairs in the liquid is postulated which
involves initial heterolytic dissociation into PO,+] PO,-], followed im-
mediately by the oxidative transfer of an oxygen atom. The following
factors support the mechanism involving direct metal-tetroxide reactions :
(c) The products of reaction of sodium and zinc with gaseous N,O,-NO,
mixtures a t temperatures below 150" have been shown to be identical with
those obtained from the liquid tetroxide. ( d ) Conditions are defined under
which sodium nitrite is stable in contact with gaseous N,04-N02 mixtures.

INprevious papers in this series (e.g., Part VIII, J., 1951, 2833; Part IX, J., 1951, 2838)
kinetic measurements of the reaction between metallic zinc and liquid dinitrogen tetroxide
have been interpreted on the basis of two mechanisms of reaction : the-first, operative a t
low temperatures, involves an electron-transfer reaction between the zinc and ion-pairs
of the form [NO+][N03-], and the second, which predominates above 14", involves fission
of the N-N bond of the tetroxide on impact at the metal surface, followed by reaction
between the metal and nitrogen dioxide. The metal oxide produced is then assumed to
react directly with dinitrogen tetroxide to give the metal nitrate. Since reactions
involving other metals (notably uranium) may be interpreted on the same mechanisms,
it is necessary to consider the evidence upon which these reaction mechanisms are based.
There are five factors of importance to which reference has not been made previously.
They concern (a) the dipole moments of the N,O, and NO, molecules, (b) the mode of
formation of [NO+][N03-] ion-pairs, (c) the reaction of metals with gaseous dinitrogen
tetroxide, (6)the stability of nitrites in the gaseous tetroxide, and (e) the reaction of metal
oxides with liquid and gaseous dinitrogen tetroxide. The first four factors are discussed
in this paper, and the fifth in the following paper.
(a) Dipole Moments of N204. and NO, Molecules.-The existence of ion-pairs
[N0+][N03-] in small concentration in liquid dinitrogen tetroxide was postulated in
Part IV (J., 1951, 1294) on the assumption that the N,04 molecule in the liquid state has a
zero dipole moment. However, since various authors give conflicting interpretations of
their experimental data, it is necessary to assess the evidence in support of this zero value.
The first determination of the dipole moment of nitrogen dioxide was made by Ghosh
and Mohanti (2. Physik, 1929, 30, 531) who found pN0, = 0-62 D for the gas. These
calculations are of limited accuracy, since they were based on Nernst-bridge measurements
of the dielectric constant E by Badeker (2. Physikal. Chem., 1901, 36, 316). A later
determination by Zahn (2.Physik, 1933,34,461) gave the values NO, = 0.39 D and ~ N , o= ,
0.55 D ; this work was criticised on grounds of interpretation by Williams, Schwingle, and
Winnings (J. A M . Chem. SOC.,1934, 56, 1427; 1936, 58,200) who deduced a zero value
for ~ N ~ o ,and
, a value of NO, which varied with temperature. Zahn (2.PFcysik, 1935, 36,
461) later agreed with this interpretation. However, independent measurements by
* Part XII, J., 1952, 1399.
 1870 Addison and Lewis: The Liquid
Schulz (ibid., 1038, 109, 517) led to the values NO, = 0-32 D and p~,o, = 0.42 D ; Schulz
implied that the criticism of Zahn's interpretation by Williams et al. was incorrect. The
assumption of a zero dipole for the N204molecule therefore necessitates a temperature-
variable dipole moment for the NO, molecule, whereas if NO, is assumed to be constant, a
finite value for ~ N , o ,results which is greater than that of pN0,.
Zahn and Schulz assume that the contribution of N,04 and NO, molecules to the total
electrical polarisation is determined by the relative amounts present (f,andf,, respectively).
Hence,
p = fl(A 1 + BlP-1 + f & 4 2 + B2P-I
where A , and A , are the optical constants given by

where I\i is L4vogadro's number and CL is the polarisability of the molecule. Assuming
B, and B, to be constant ( B = 4xiVp2/9k, where k is Boltzmann's constant), these
authors determined values for ~ N , o , and pNo,, but did not obtain sufficient data to enable
a value for the dipole moment of each molecule to be calculated at any one temperature.
If p ~ o varies
, with temperature, then Debye's equation cannot be applied. In order to
compare the two sets of experimental data, the results of Williams et al. at two temDeratures
have been substituted in {he above equation, and the values of ~.N,o,and p ~ o ,areLgiven in
Table 1.
TABLE1.
(a) T, = 298' K, T2 = 318" K . ( b ) T, = 298" K, T2= 343" K .
p ~ ~ o ,............... 0.283 0.332 0.284 0.287 0-238 0.283 0.361 0.389 0.267 0.457
t(h'ot ............... 0.423 0.422 0.410 0.415 0-457 0.387 0.387 0-373 0.395 0.359
(c) T, = 318'K, T2 = 343" K . ( d ) T, = 298" K, T,= 368' K.
px,o, ............... 0.469 0.348 0-360 0.321 0.392 0.333 0.391 0.306 0.393 0.471
t ( ~ o * ............... 0.352 0.389 0.370 0.387 0.386 0.341 0.341 0.342 0.337 0.339

The greater spread of results in the case of p ~ , o , no doubt arises from the smaller
concentration of N,04 molecules a t the higher temperature, leading to greater errors in its
evaluation. The means of the results in Table 1 are compared in Table 2 with Schulz's

TABLE2.
(a) (b) (4 (dl
Schulz's results ..........................................
{ Calc. 0.416 0.416 0.415 0.411
from data of Williams ef al. ..................
pNtO4
0-28 0-38 0-39 0.39
mot { Schulz's results .......................................... 0.321 0.320 0.320 0-321
Calc. from data of Williams e t al. .................. 0-42 0.38 0.38 0.34

results (Zoc. cit.). If it is assumed that p~,o, = 0, Schulz's data may be recalculated t o
give p ~ o ,a t a series of temperatures (see Figure). Schulz applied an arbitrary correction
of 5% for the contribution of atom polarisation, but this correction has been excluded from
the results shown in the Figure. In view of the agreement shown, it is clear that the
different conclusions of the above authors arise solely from differences in interpretation.
The values for the dielectric constant and refractive index of liquid dinitrogen tetroxide
have been substituted into Onsager's equation ( J . Amer. Chem. SOC.,1936, 58, 1486), viz.,

In comparison with the above values, this equation gives p = 0.51 D for dinitrogen
tetroxide in the liquid state. In view of the limited applicability of this equation in media
of low dielectric constant, the value obtained is reasonably close to that determined by
Schulz. If the dipolar character of liquid dinitrogen tetroxide arises from a finite dipole
in the tetroxide molecule, the agreement between the two independent p~,o, values would
provide evidence that the N,O, structure is the same in the gas as in the liquid state.
However, this assumption is not justified (seebelow), and the above agreement is fortuitous.
[19531 Dinitrogen Tetroxide Solvent System. Part X I I I . 1871
None of the results discussed above leads to a definite conclusion regarding the value
for ~ N , o , , but appropriate evidence is available from the measurements of e made by
Williams et aZ. (Zoc. cit.) on gaseous N0,-N20, mixtures, at a single temperature, in which
the NO,/N,O, ratio was varied by change in pressure. Since no temperature change is
involved, all dipole moments are constant, and the Debye equation may be applied directly
to the experimental results. When this is done, a zero dipole moment for the N20,
molecule is obtained.
This conclusion involves a temperature-variable dipole for the NO, molecule. Williams
et al. (Zoc. cit.) have shown that this variation is larger than can be accounted for on the
assumption that the molecule possesses two moments corresponding to two vibrational
states. From ultra-violet absorption measurements, H a m s and King (J. Chem. Phys.,
1940, 8, 775) considered the possibility of nitrogen dioxide's possessing two low-lying
electronic states of approximately the same energy. We have examined the variation in
p ~ o ,from this point of view. When one activated state only is considered, we have

Since the observed moment p decreases with increasing temperature, the moment p1
in the excited state must be less than the moment in the ground state. On the

40" 60" 80" 100" 120" 740"

Temperature

assumption that the statistical weight factor K is unity, the difference between the values
of p / b at 300" K and 400" K has been calculated for a range of values of pl/po and hv/kT
(Table 3).
TABLE3.
300' K 400" K
P 1/PO hv/kT PIP; hvlkT PIP0 h/P0)300 - b'/P0)400
0.5 { 3-3
1.0
0.33
0.99 11
0.9304
0.8892
2.5
0-75
0.25
0.9809
0.9164
0.8838
0.0102
0.0140
0.0054

0.1 { 3-3
1.0
0-33
0.9839
0.8708
0.7897
2.5
0.75
0-25
0.9651
0.8433
0-7784
0.0188
0.0274
0.01 13

0.0 { 3-3
1.0
0-33
0-9820
0-8851
0.7624
2.5
0-75
0-25
0.9614
0-8241
0.7497
0.0206
0.0310
0.0230

The value of p, is not known. However,

PO = (P300 - P400) / [ ( p / k l ) 3 0 3 - (P/PO)4001
and from the Figure, p3,,,, - psoois approximately 0.3 D ; the maximum value of the
denominator (col. 6, Table 3) then gives a value of about 10 D for p,. In order that the
calculated value of po should be in a range of possible values, a degeneracy of the molecule
in the activated state has been considered. Maximum variation in dipole moment with
temperature occurs when hv = kT (Van Vleck, Phys. Reviews, 1927, 29, 729; 30, 31) and
also as pl/po approaches zero. The statistical weight K being assigned values of 1, 2, 3,
and 4 (and on the assumption that pL1/po= 0 and hv = kT at 300" K), the differences
1872 Addison and Lewis: The Liquid
between the two values of p/po are 0.031, 0-042, 0-046, and 0.048, respectively. Variation
of K within reasonable limits does not therefore bring about the necessary decrease in b,
and it is not possible to explain the temperature variation in p ~ o ,by assuming one excited
state ; the assumption of three electronic levels involves too many unknown parameters
to permit corresponding calculations to be made. However, the considerable amount of
evidence for the symmetrical structure of the N204molecule in the solid and in the gaseous
state supports the assumption of a zero value for pN,o, (and thus a temperature-variable
NO,) in the liquid state also.
(b) Mode of Formation of [NO+][NO3-] Ion-$airs.-Of the various possible ion-pairs,
the [NO+][NO,-] pair has been postulated, since almost all the chemical reactions of the
N204 molecule are in accord with this formulation. In the absence of any plausible
mechanism involving either intermolecular or intramolecular rearrangements of the N,O,
molecules themselves, atom transfer may be considered to occur subsequent to the initial
homolytic (i) or heterolytic (ii) dissociation of N20, molecules : (i) N204 + NO, +NO,,
+
(ii) N204 + NO2+ NO,, and the mode whch predominates is determined by the
dielectric constant of the medium (Waters, J., 1942, 153).
(i) Homolytic dissociation. If atom transfer follows this mode, it must result from
impact between NO, molecules, a type of reaction which occurs also in the equilibrium
2BrF3 BrF,+ + BrF4- (Banks, Emel&, and Woolf, J., 1949, 2861). A molecule
having the structure proposed by Longuet-Higgins (Nntzcre, 1944, 153, 408) could serve as
an intermediate, thus

Since no dipolar constituent is present in the gaseous state (see below), an intermediate
compound of this structure is more likely than the unsymmetrical molecule ON*O*N02
considered by See1 (2. artorg. Chem., 1952, 269, 103). The existence of an intermediate
compound having a different structure from the parent molecules has a direct analogy in
dinitrogen trioxide (Addison, Lewis, and Thompson, J., 1951, 2838). This interpretation
however is incomplete, since it does not provide any reason why these particular ions
should be formed.
(ii) Heteroljtic dissociation. The extent of ionic dissociation of N20, broadly follows
the E ranges suggested by Waters (Zoc. cit.). Thus, in pure dinitrogen tetroxide (E = 2-42),
ionic dissociation occurs to the extent of only about 0.1% ; the rate of reaction with metals
is decreased by the dilution factor only on dilution of the tetroxide with liquids (e.g.,
benzene) of similar low dielectric constant. In glacial acetic acid (e = 7.1) containing
sodium acetate, ionic dissociation is increased sufficiently to enable the presence of ions to
be detected by electrolysis (Angus, Jones, and Philips, Nature, 1949, 164, 433). The
addition of diethylnitrosamine (e = 42.5) increases the electrical conductivity of liquid
dinitrogen tetroxide by a factor of lo8 (Part VI, J., 1951, 1303). In solution in pure nitric
acid, dinitrogen tetroxide is completely dissociated into ions (Goulden and Miller, J., 1950,
2620), and in sulphuric acid (e = 110; Brand, James, and Rutherford, J . Chem. Phys.,
1952,20,530) ionisation is again complete (Gillespie, Graham, Hughes, Ingold, and Peeling,
J., 1950, 2504).
Such dissociation reactions involve a simple change from equal to unequal sharing of
the bonding electrons, so the first stage in the heterolytic dissociation of dinitrogen tetroxide
gives rise to NO2+ and NO2- ions. Detailed studies in each of the above liquid systems
have identified the ions present as NO+ and NO3-; the reaction NO2+ NO2-+ +
NO+ + NO,- must therefore follow immediately the primary heterolytic dissociation, and
be irreversible. The high oxidising power of the nitronium ion, and its close proximity
t o the nitrite ion in the [N0,+][N02;] ion-pair would render the two groups incompatible.
Oxygen-atom transfer is then an oxidative process which is consistent with the chemical
properties of the ions concerned. Since it is the initial heterolytic dissociation, and not
the oxidative process, which is influenced by e of the medium, the ultimate ionic products
of dissociation are independent of medium.
[19531 Dinitrogen Tetroxide Solvent System. Part X I I I . 1873
The equilibria existing in dinitrogen tetroxide may then be represented by the following
scheme :

I *
O=N\+,o\,N-0- 'I
I NO'+NO,-
0 T
All the equilibria shown occur in the liquid state; only those to the left of the vertical
broken line occur in the gaseous state. The complete absence of nitrite ion as a
reaction product indicates that the oxidation of NO2- by NO2+ takes place before either
ion is able t o react independently with other reactants introduced into the system.
Reactions with ethylenic linkages can be explained on the basis of the polar nature of the
nitrogen in the tetroxide (Levy and Scaife, J., 1946, 1093) without assuming the existence
of discrete NO2+ and NO2- ions (Ingold, Nature, Zoc. cit.); it is significant that dinitro-
compounds are formed in gaseous reactions also, when no ion-pairs exist. The possibility
that nitronium and nitrite ions are produced on impact is not supported elsewhere in the
chemistry of dinitrogen tetroxide.
(c) Reaction of Metals with Gaseous Dinitrogen Tefroxide.-In their study of gaseous
N,04-NO, mixtures, Williams et aZ. (Zoc. cit.) determined the value of p ~ o for
, a range of
pressures and a t a single temperature. The values of pN0, and ~ N , o , were constant and
independent of pressure, indicating that only these two components are present in the
gaseous phase. The concentration of a third ionic component would vary with pressure,
and its presence would lead to variations in pN0, and ~ N , o , . The same conclusion follows
independently from a consideration of the low dielectric constant in the gaseous state.
If a second mechanism, involving N,04 and NO, molecules only, operates in the liquid
state, then reaction with gaseous mixtures (which contain no ion-pairs) should follow the
same mechanism t o give the same reaction products as with the liquid. When sodium is
burnt in the gas (Holt and Sims, J., 1894,65,432; Dulong, Ann. Chim. Phys., 1816,2,317)
a mixture of sodium nitrite and sodium nitrate is produced. At the temperature of
burning sodium the gaseous phase contains oxygen and nitric oxide, and reaction with the
latter gives rise to nitrite (following paper). At 300", metallic zinc is converted into zinc
oxide by nitrogen dioxide (Sabatier and Senderens, Compt. rend., 1892, 115, 236). The
reaction of metallic sodium and zinc with gaseous N204-NO, mixtures has therefore been
studied at temperatures below 140" (at which temperature dissociation of NO, becomes
appreciable).
(i) The gas mixture was passed, a t 60-80" and at atmospheric pressure, over metallic
sodium. During about 15 min. the metal acquired a thin coating of white solid; after
this, the coating was sufficiently cohesive t o prevent further reaction. The coating was
scraped from the metal, and its X-ray powder photograph was found to be identical with
that of pure sodium nitrate.
(ii) The gas mixture was passed, a t 120-140", over a block of pure zinc. The metal
developed a crust of white solid, which did not inhibit the reaction. Spectrophotometric
analysis of the product showed the absence of nitrite, and chemical analysis confirmed that
the product was pure zinc nitrate. A similar reaction, carried out at 60-80", gave a yellow
viscous liquid identical with a mixture of zinc nitrate and the compound Zn(N0,),,2Nq0,
(Part VII, J., 1951, 2829). When this product was heated at loo", dinitrogen tetroxlde
was evolved and pure zinc nitrate remained. At the temperature (300")used by Sabatier
and Senderens (Zoc. cit.) anhydrous zinc nitrate decomposes rapidly to zinc oxide (Part VII,
loc. cit.).
Since the products of reaction in the gaseous and in the liquid state are identical, it is
permissible to consider a mechanism of reaction in the liquid state which does not involve
ion-pairs.
1874 Addison and Lewis: The Liquid
(d) Stability of Nitrites in Gaseous Dinitrogen Tetroxide.-The close analogy drawn
above between reactions in the liquid state, and in the gaseous state below 140°, is only
justified if nitrites are also stable in contact with gaseous N,O,-NO, mixtures over a
corresponding temperature range. Oswald (Ann. Chirn., 1914,1,44) found that oxidation
occurred at I O O O , and also took place very slowly a t room temperature. This reaction has
been re-examined ; the experimental conditions and results are given below :
Expt. No. ................................. 1 2 3 4 5 6 7
Temp. ....................................... 40" 70" 85" 100" 100" 122" 200°
Reaction period (hours) ............... 6 6 40 7 7 43 3
% conversion into nitrate ............ 0.0 0.0 0.85 0.5 0.0 5-4 49-5
The nitrate content of the product was determined by ultra-violet spectrographic analysis
(J., 1952, 338). At the lower temperatures the oxidation of nitrite is negligible over long
periods, although on prolonged contact (Expt. 3) slight oxidation does occur. At
temperatures above the dissociation temperature of nitrogen dioxide (Expt. 7) oxidation is
considerable; reactions of this type are considered in detail in the following paper. The
dissociation temperature of the NO, molecule is normally quoted as 140°, but Expt. 6
implies that slight dissociation occurs below this temperature.
The authors are indebted to Dr. S. C. Wallwork for the X-ray crystallographic analysis, and
to Dr. H. C. Bolton for valuable discussion.
THE UNIVERSITY,
NOTTINGHAM. [Received, December Stit, 1952.1