Infrared Spectra of Gaseous and Solid Hydrazoic Acid and DeuteroHydrazoic Acid:

The Thermodynamic Properties of HN3

David A. Dows and George C. Pimentel

Citation: The Journal of Chemical Physics 23, 1258 (1955); doi: 10.1063/1.1742253
View online: http://dx.doi.org/10.1063/1.1742253
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 1258 RICHARD F. WALLIS

in the main body of the paper while for A=O it consti-
tutes a generalization to two effective nuclear charges
of the Wang wave function lO for which the best value of
the dissociation energy is 3.76 ev when Z= 1.166.
When the parameter A is varied to minimize the energy,
the calculation constitutes a generalization of that due
10 S. C. Wang, Phys. Rev. 31, 579 (1928).
to Weinbaumll who obtained a dissociation energy of
4.00 ev when Z= 1.193 and A=0.256. The results of the
present calculations are given in Table II. It may be
seen that both the Wang and the Weinbaum calcula-
tions are improved by about 0.1 ev by the use of two
effective nuclear charges.
II S. Weinbaum, ]. Chern. Phys. 1, 593 (1933).

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 23. NUMBER 7 JULY, 1955

Infrared Spectra of Gaseous and Solid Hydrazoic Acid and Deutero-Hydrazoic Acid:
The Thermodynamic Properties of HN 3
DAVID A. Dows* AND GEORGE C. PIMENTEL
Department of Chemistry and Chemical Engineering, University of California, Berkeley, California
(Received October 11, 1954)

Infrared studies of HN3 and DN3 in the gas and solid phases and of HN3 in CCI, solutions are presented.
The two low-frequency skeletal bending modes are identified, permitting calculation of the thermodynamic
properties of hydrazoic acid. Hydrogen bonding of HN3 and DN3 in the solid state is indicated by frequency
shifts of the NH and ND stretching motions (216 and 151 cm- I , respectively). No evidence of hydrogen
bonding was observed in solutions of HN3 in CCI, at concentrations up to 0.3 M. An irreversible phase
transition is observed on warming solid hydrazoic acid above about 120°K.

T RE infrared spectrum of gaseous hydrazoic acid

has been given by Daviesl and by Eyster and
Gillette. 2 These authors are in general agreement except
on the spectral features observed in the region below
800 cm-l • There is question as to the spectral locations
of the two fundamental vibrations expected below
800 cm-l , the skeletal bending motions. In the studies
reported here, the structure observed in the region 600-
750 cm-l is well enough resolved to aid in the selection
of these fundamentals.
An infrared study of the hydrogen bonding of RN 3
and DN3 in solution has been made by Buswell, Mc-
Millan, Rodebush, and Wall. 3 No evidence of hydrogen
bonding between two RN 3 molecules was detected
although it was concluded that there is a strong inter-
action between RN3 and ether or water. The spectrum
of solid hydrazoic acid is interesting in comparison
with these results.
The structure of hydrazoic acid is known from the
analysis by Eyster4 of the spectrum of the second over-
tone of the N - R stretching frequency and it is con-
firmed by the microwave study of Amble and Dailey.5
The three nitrogen atoms of RN 3 are colinear and the
hydrogen atom is attached at one end with an angle of
112° between the NR bond and the N 3 skeleton. Thus
the molecule has symmetry C. with five type A' vibra-
* Present address: Department of Chemistry, Cornell Uni-
versity, Ithaca, New York.
1M. M. Davies, Trans. Faraday Soc. 35, 1184 (1939).
2 E. H. Eyster and R. H. Gillette, J. Chern. Phys. 8, 369 (1940).
3 Buswell, McMillan, Rodebush, and Wall, J. Am. Chern. Soc.
61, 2809 (1939).
, E. H. Eyster, ]. Chern. Phys. 8, 135 (1940).
6 E. Amble and B. P. Dailey, J. Chern. Phys. 18, 1422 (1950).
tions (in-plane) and one type A" vibration (out-of-
plane). All vibrations are both infrared- and Raman-
active. If the molecule is treated as a symmetric top
(which it closely approaches) the A" fundamental is
expected to be a pure perpendicular band, while the A'
fundamentals are expected to be hybrids consisting of
superimposed parallel and perpendicular bands. The
parallel components should have the appearance of a
parallel band of a linear molecule, the Q-branch being
quite weak. With the structure given by Amble and
Dailey and assuming the moments of inertia do not
change as a function of vibrational state, the separations
of the P- and R-branch maxima are calculated to be
26 cm-l for both RN3 and DN 3, while the Q-branches of
the perpendicular bands should be 36 and 22 cm- l
apart for RN3 and DNa, respectively.
EXPERIMENTAL
Rydrazoic acid was prepared by adding a large
excess of stearic acid to sodium azide and heating to
about 90°C under vacuum, allowing the RNa to distill
out of the reaction mixture as it formed. Explosion
shielding was provided. The pressure of hydrazoic acid
was maintained below 50 mm during the preparation
and the gas came in contact with glass, mercury, and
Apiezon N stopcock grease. The infrared spectrum of
the gas showed no evidence of impurities or decomposi-
tion over a storage period exceeding one month at room
temperature.
Deutero-hydrazoic acid was prepared in the same
manner using monodeutero-stearic acid. This material
was prepared from sodium stearate, dried nrst at 130°C

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 INFRARED SPECTRA OF HNa AND DNa, GAS AND SOLID 1259

kBr prllm

3300 3100 2400 2200 2000 1300 1100 900 700 500

~Ol+-----------------~ __~__------__~--~~,-~------------~~----~~-L--------------~

3300 3100 2400 2200 2000 1300 1100 900 700 500
WAVE NUMBERS IN eM"

FIG. 1. Infrared spectra of HNs gas and DNa gas (pressure given in rnrn of Hg).

for 24 hours and then at room temperature in a vacuum
desiccator over P 20 5 for 48 hours. In a dry box, P 20 S
was added to 99.5 percent D 20, the dried sodium
stearate was added to this solution of deuterated phos-
phoric acid, and the mixture was warmed until the
deuterated stearic acid melted. The mixture was cooled,
filtered, and the deuterated stearic acid was placed in
in a vacuum desiccator over P 20 5. The sample probably
contained some unreacted sodium stearate.
The DNa prepared from the deuterated acid contained
about 15 percent RNa, presumably because the P 20 5
was not completely dry, and about 10 percent D 20.
The gases were condensed at 77°K and warmed to
- 20°C to transfer the DNa to another bulb; this pro-
cedure was repeated until the infrared spectrum gave
no more evidence of D 20. The RNa interfered in the
spectral studies because of the overlap of the absorption
of RNa at 1150 cm- l with the weaker absorption of
DNa near 1180 cm-l .
The spectra were obtained with a Perkin-Elmer
Model 21 spectrophotometer (NaCI and CaF 2 prisms)
and a Perkin-Elmer Model 12-C spectrometer (LiF
and KBr prisms). The spectral slit widths are shown
on the spectra. Frequency accuracy ranges from about
3 cm- l at 500 cm-l to about 5 cm-l at 3300 cm-l . For
the gas spectra, lO-cm cells with KBr windows were
used. In obtaining the solid spectra, gas was sprayed
0
onto a salt window cooled to about 80 K with liquid
nitrogen. The low-temperature cell is similar to that
described by Wagner and Rornig 6 with a glass spray-on
tube added to facilitate transfer of the sample onto
the cold salt window. The temperature was measured
6 E. L. Wagner and D. F. Hornig,]. Chern. Phys. 18,296 (1950).
during every spectral study using a copper-constantan
thermocouple embedded in the salt window. Both NaCI
and AgCl windows were used, with no differences in
the spectra.
SPECTRA
The spectra of gaseous RNa and DNa are shown in
Fig. 1. The structure of the RNa band at 2150 cm-l
observed with the lithium fluoride prism agreed closely
with that given by Davies.! The spectrum of DNa was
examined in this same region, using both LiF and CaF 2
prisms, and no resolution differences were observed.
Above 900 cm-l the spectrum of RNa is in agreement
with that given by previous investigators except that
a weak doublet was observed at 950 cm- l (with a spacing
appropriate to the calculated P-R spacing of RNa)
and no absorption was detected at 1381 cm-t, a band
listed by Eyster and Gillette 2 but not by Davies. l
The absorptions near 522 cm-l for RNa and 498 cm-l
for DNa have the doublet appearance appropriate to
parallel bands; hence these features are assigned to the
in-plane bending motion, VO' Assignment of the RNa
band at 522 cm- l to a difference frequency, as is done
by Eyster and Gillette,2 is implausible since the cor-
responding sum frequency is not observed.
Figure 2 shows the structure near 700 cm-l under
optimum spectral conditions using a NaCI prism. For
both RN3 and DNa the structure is indicative of a
perpendicular band and hence is assigned to the A 1/
vibration, the out-of-plane bending, V6. The choice of
the band centers, at 672 cm- l for RN 3 and 638 cm- l for
DN 3, is discussed later.
When RNa was condensed on a salt window cooled
to 80 o K, a solid material, phase I, was obtained having

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 1260 D. A. DOWS AND G. C. PIMENTEL

100~------------------------------------------~

-
'Ci
~

c:::
.9
VI
VI

"e .I
~
.1
QJ
JQ..
.I
Q,
VI
c:::
0
eI.
t
~

I-- HN3 p=150mm

50
eso 800 750 700 650 600
Wavenumber in em-I
100

-
~
c:::
.9
VI
.~
E
VI
c:::
•1
Os ~• .I .I
OJ O. {. ~. f
0 v.
~
I--
DN3 p=200mm
50
850 800 750 700 650 600
Wavenutnber in em-I
FIG. 2. Infrared spectra near 700 cm-1 of HNa gas and DNa gas: Q-branch assignments.

the spectrum shown by a dotted line in Fig. 3(a). When ing to about 170 0 K where RNa began distilling off the
the solid was allowed to warm slowly, an abrupt window.
transition occurred at about 120 0 K to give a solid, The spectrum of solid DNa was obtained using a
phase II, having the spectrum shown by a solid line in sample containing about 25 percent RNa. The solid

.,
Fig. 3a. No further changes in the spectrum of phase II exhibited a transition from a low-temperature phase I
occurred on cooling the solid slowly to 80 0 K or on warm- [dotted line, Fig. 3 (b)] to another phase II [solid line,

1"C/,¥ · Fig. 3(b)] as did RNa, but the transition temperature

(., l!.:/v
was not measured. The large amount of RNa prevented

\./"-'t.
_ .... I
o ".!
'
accurate determination of the shape of the absorptions
of DNa near 2160 and 1230 em-I.
The frequencies observed in the spectra of RNa
and DNa in the gas state and in the solid phase II are
~ " listed in Table I with proposed assignments. The fre-

(b) ~".s . quencies observed for the solids in phase I are given
in Table II. Table III lists those sharp features ob-
DN 3 (s)
-II
····1
served near 700 cm- I in the spectra of gaseous RNa
.1000 100
and DNa which are interpreted to be associated with
Q-branches of the sub-bands of a perpendicular band.
FIG. 3(a). Infrared spectra of phases I and II of solid HNa The average spacings observed are 34.5 and 16.0 cm- I
(BOOK). 3(b). Infrared spectra of phases I and II of solid DNa
(BOOK). for RNa and DN 3 , respectively.

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 INFRARED SPECTRA OF HNa AND DNa, GAS AND SOLID 1261

DISCUSSION TABLE II. Infrared spectra of HNa and DNa: solid phase I.

Spectra of the Gas Phases HN,(sI) DN,(sI) Assignment

In attempting to interpret the detailed structure of 3090 2308 VI

the absorptions near 700 cm-t, it is possible to ac- 2412 2va

2379
count for the qualitative difference in appearance of the 2380 V2+V7
HN3 and DN3 spectra. The calculated separations of 2349 2V4
2162 2155 P2
the P- and R-branch maxima, 26 cm-I , indicates that 1299 1230 Pa
the P- and R-branches of neighboring sub-bands will 1180 977 P4
overlap and reinforce each other for HN 3 where the
average Q-branch spacing is 34.5 cm-I . The P- and R-
branch maxima will be separated by about 26 cm- I for A II class indicates that the ratio 1'6(HN3)/ 1'6(DN 3) is
DN3 also, but the observed Q-branch spacing, 16.0 cm-I , 1.06. Among the possible band centers mentioned above,
is too small to permit the reinforcement observed for the pair 672 cm-I (HN3) and 638 cm-I (DNa) are in the
HN 3• ratio of 1.05. This ratio is quite reasonable if an-
The spacings between Q-branches permit calculation harmonicity is considered. The next best selection, the
of values of I a/ if hydrazoic is assumed to be a sym- pair 637 cm-I (HN 3) and 622 cm- I (DN 3), are in the
metrical top, if Coriolis interaction is neglected, and ratio 1.02 and seem less likely. Still, in calculating
if the large moment of inertia of the hypothetical sym- thermodynamic properties of HN 3, it seems wise to
metrical top is assumed to be the arithmetic mean of attach an uncertainty of 35 cm-I to the assignment of
1'6=672 cm-I •
TABLE I. Infrared spectra of RNa and DNa: Three lines, located at 643.0, 714.5, and 790.0 cm-t,
gas phase and solid phase II. are observed in the spectrum of HN3 but do not have
obvious assignments.
HN,(g) HN,(sIl) DN,(g) DN,(sIl) Assignment
The proposed assignments in Table II present some
3336 m 3120 vs 2480m 2329 s VI interesting points. The HN 3 band at 950 cm-t, not
3250 W 3305w V2+V4
2358 m 2442 m 2va
observed by earlier workers, has been tentatively
2435 w 2380w V2+V7 assigned as the difference frequency, 1'2- 1'4. This
2402m 2402w 2170w 2202w va+v4 assignment is strengthened by the appearance of the
2304s 2298w 2V4
2140 vs 2169 vs 2141 vs 2165 vs V2
corresponding sum, 1'2+1'4, at 3250 cm-t, but the dis-
1274m 1280m 1183 m 1229 m Va crepancy between the calculated and observed difference
1150 vs 1182 vs 955 s 958 s V4
frequency is larger than expected for a difference
950 vw P2-P4
672 w 638w V6 frequency.
522 w 498w v. The combination 21'4 is observed in the spectra of
(266) (?) (215) (?) V7
gaseous and solid HN 3 while 21'3 is observed in the
spectra of DN 3 • Furthermore, the relative intensities
of 1'3 and 1'4 differ in the spectra of gaseous HN3 and
the largest moments of inertia of hydrazoic acid, DN 3 and in the transition from gas to solid, 1'4 shifts
h'=!(h+Ic) (the prime denotes the upper vibra- more than 1'3 for HNa while the reverse is true for DN 3.
tional state). This calculation gives 1.6 and 3.7.10-40 g All of these observations show a change of character
cm2 for la' of HN3 and DN 3, respectively. From the of these two vibrations upon deuterium substitution,
known structure of HN 3, the values of I a are calculated the vibration 1'3 taking on more of the character of the
to be 1.54 and 2.51.10-40 g cm2 for HN3 and DN J ,
respectively. The discrepancy between I a and I a/ seems TABLE III. Q-branch frequencies near 700 em-I: HNa and DNa.
too large to attribute wholly to a change in the moment
of inertia of DN 3 (but not HN 3) in its excited vibrational Branch HN,(g) t.v DN,(g) t.v
state. RQ. (?) 864.0 726.0
The band center of a perpendicular band is expected 37.5 17.5
to lie between the two most intense Q-branches. The RQ4 826.5 708.5
32.5 15.0
rather obvious maximum in absorption of the band of RQa 794.0 693.5
DN 3 indicates the band center is at 622, 638, or 654 33.5 16.0
RQ2 760.5 677.5
cm-I • These figures were obtained by extrapolation of 35.0 15.0
the resolved Q-branch frequencies (see Table II) to the RQI 725.5 662.5
maximum in absorption as observed with the KBr 36.5 16.5
RQo 689.0 646.0
prism. The spectrum of HN 3 has no clear maximum of 34.5
absorption but three possible band center positions PQI 654.5
34.5
halfway between Q-branches are 637, 672, and 708 PQ2 620.0
cm-I . The Teller-Redlich product rule applied to the

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 1262 D. A. DOWS AND G. C. PIMENTEL

hydrogen bending motion. The combination Va+V4 is not Bands were observed in the spectra of the solutions at
affected by this change and is observed in the spectra frequencies 3320, 3250, 2394, 2298, and 2140 em-I, in
of both HN a and DNa. close agreement with the gas phase frequencies. Within
experimental uncertainty, the optical density of each
Thermodynamic Properties of HN a of these bands varied directly with the concentration
of HN 3. The intensity of the NH stretching band
The rather definite assignment of the low-frequency
relative to other bands was approximately the same as
vibrations, V5 and V6, provides a basis for the calcula-
in the gas phase. The spectral studies of CC1 4 solutions
tion of the thermodynamic properties of hydrazoic acid
of HN3 corroborate the conclusion of Buswell et al. that
in the perfect gas state. Table IV gives the values of
Cpo, (HO-HoO)/T, (FO-Foo/T), and So at various HN 3 does not form hydrogen bonded polymers in
solution.
temperatures. These calculations are based on the
Examination of the shifts of the NH and ND stretch-
molecular parameters given by Amble and Dailey 5
ing frequencies in the solid state (216 and 151 em-I)
with the product of the moments of inertia equal to
reveals normal behavior of deuterium relative to hydro-
6963.10-120 ga cm 6 • The uncertainty of these values is
gen. The band attributed by Buswell et al.a to the
probably determined by the uncertainty of ±35 cm-I
hydrogen bonded ND stretching motion (observed in
in the assignment of V6.
this investigation at 2202 cm-I in the solid phase) is also
present in the spectrum of gaseous DN3 (at 2170 em-I)
Hydrogen Bonding
and can be assigned as a combination, V3+V4. Thus no
The principal differences between the spectra of evidence was found which corroborates the abnormal
gaseous and solid hydrazoic acid are of the type ob- hydrogen bonding properties of DN 3 proposed by
served when hydrogen bonding occurs. The bands Buswell et al. 3
associated with NH and ND stretching motions shift The shift of the NH stretching frequency with hy-
to lower frequencies and are intensified relative to drogen bonding may be compared to the corresponding
other bands. The bands assigned as the fundamentals shift for o-valerolactam, for which TsuboF reported a
V2, Va, and V4 all shift to higher frequencies. For V3 shift of 210 cm-I and a hydrogen bonding energy of
and V4, which involve hydrogen bending motion, the 5.1 kcal per bond in CC1 4 solution. It is likely that the
upward shift also indicates hydrogen bonding. similar frequency shifts of HN a and o-valerolactam are
This evidence for hydrogen bonding in the solids indicative of similar hydrogen bond energies. Hence
of both HN3 and DN3 contrasts with the results of the absence of polymerization of HN 3 in solution is
Buswell et al} concerning hydrogen bonding of hy- probably associated with entropy terms opposing for-
drazoic acid in solution. To clarify the situation, a por- mation of open dimers or polymers from an extended
tion of their studies of HN 3 in CC1 4 was repeated. molecule like HN 3. Cyclic dimers probably do not form
Solutions with HN 3 concentrations 0.32,0.093, and 0.027 because of unfavorable bonding angles.
M were studied in the spectral region 3500-2000 em-I. More detailed study of the spectra of solid HN 3 and
The 0.32 M solution was prepared by condensing DN3 reveals no evidence of splitting of bands, even in
together known amounts of HN 3 and CC1 4 in vacuum the hydrogen stretching regions where the intermolec-
and warming to room temperature. The other solutions ular interactions are strong because of hydrogen
were prepared by dilution of the 0.32 M solution. bonding. Two of the possible explanations of the
absence of splitting of the NH or ND stretching motions
TABLE IV. Thermodynamic properties of hydrazoic are that the unit cell contains only one molecule or
acid, cal/deg mole.
that there are several molecules per unit cell and the
TOK Cpo (HO-HoO)/T -(FO-HoO)/T so factor group selection rules provide only one infrared-
active hydrogen stretching mode.
273.16 10.095 8.577 47.606 56.179
298.16 10.443 8.721 48.366 57.083
All the combinations observed in the gas phase
spectra are also observed in the solid spectra. In addi-
100 8.023 7.959 39.428 47.384 tion solid HNa and DN3 each show a band for which
200 9.072 8.212 44.997 53.204
300 10.464 8.730 48.417 57.139 there is no counterpart in the gas phase spectrum,
400 11.740 9.326 51.008 60.330 either 2402 or 2435 cm-I for HN 3 (one of these is
500 12.805 9.922 53.153 63.071 associated with the combination, V3+V4) and 2380
600 13.709 10.482 55.014 65.493
700 14.462 10.997 56.667 67.660 cm-I for DNa. It is possible that these new bands may
800 15.102 11.472 58.164 69.631 be due to combinations between V2 and lattice torsional
900 15.651 11.907 59.540 71.443
1000 16.122 12.305 60.817 73.117 motions of hydrazoic acid about the axis of smallest
1100 16.529 12.670 62.007 74.673 moment of inertia. These torsional motions, called V7,
1200 16.879 13.008 63.120 76.124
1300 17.189 13.312 64.174 77.482 are tentatively assigned at 266 or 233 cm- I for HN a and
1400 17.454 13.602 65.173 78.771 215 cm-I for DN 3.
1500 17.681 13.868 66.123 79.987
7 M. Tsuboi, Bull. Chern. Soc. Japan 22, 215 (1949).

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 IN F R ARE D S P ECT RA 0 F H N 3 AND D N 3, GAS AND SOL I D 1263

The spectra of the solid phases I and II differ in
several ways. For both HN 3 and DN 3, several bands
are distinctly sharper in phase II and the frequencies of
)11, )13, and )14 suggest stronger hydrogen bonding in
phase I than in phase II. The band assigned to )12+)17
is present in the spectrum of DN 3 (sI) but was not ob-
served in the spectrum of HN 3 (sI).
Mador and Williams 8 have recently mentioned a
transition in solid hydrazoic acid occurring at 148°K.
The low-temperature phase is a clear colorless glass
and the transition produces a polycrystalline material.
No obvious change of this sort was noted in the present
work and the light scattering by the solid was small
and about the same for both phases I and II. In view of
the discrepancy between the observed transition tem-
peratures (148°K8 and about 1200K), it does not seem
likely that the glassy low-temperature phase observed
by Mador and Williams is identical to phase I.
The observation that phase I cannot be obtained
81. L. Mador and M. C. Williams, J. Chern. Phys. 22, 1627
(1954).
by cooling phase II below the transition point could be
due to supercooling of phase II, and phase I may be a
stable crystal modification. On the other hand, the
broadness of the bands suggests a certain amount of
disorder in phase I, and this phase may have a glassy
structure (as indicated by Mador and Williams 8) or it
may be an unstable disordered crystalline arrangement
(due to fast growth) which becomes ordered on warm-
ing. A transition from a glass to a crystal usually can be
identified by a marked increase in scattering, which was
not observed. Hence the last proposal, an unstable,
partially disordered crystal, seems to be the most likely
explanation of solid phase I. It is interesting to notice
that similar transitions have been reported by Malherbe
and Bernstein9 and by Nightingale and Wagner.1°
Ammonium azide also shows a transition with the
temperature behavior described in the foregoingY
-
9 F. E. Malherbe and H. J. Bernstein, J. Chern. Phys. 19, 1607
(1951).
10 R. E. Nightingale and E. L. Wagner, J. Chern. Phys. 22, 203
(1954).
11 Dows, Whittle, and Pimentel (to be published).

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 23. NUMBER 7 JULY. 1955

Ion Pair Yields in the X-Ray Decomposition of Hydrogen Bromide

in Rare Gas Atmospheres*
EDWARD G. ZUBLER,t WILLIAM H. HAMILL, AND RUSSELL R. WILLIAMS, JR.
Department of Chemistry, University of Notre Dame, Notre Dame, Indiana
(Received September 23, 1954)

The rate of x-ray induced decomposition of hydrogen bromide has been measured both in the pure gas
and in rare gas atmospheres. The rate of ion pair formation under identical irradiation has been determined
from the saturation ionization currents in rare gases and ion pair yields for decomposition of hydrogen
bromide have been computed. Average yields were A-HBr, 4.7; Kr-HBr, 4.0; Xe-HBr, 4.7; HBr, 4.6;
HBr-Xe, 5.2; where the first substance named is the major component. A mechanism for decomposition by
ion formation accounts for a yield of 4.0. Values above this are attributed to dissociative excitation without
ionization.

INTRODUCTION the following steps:

HBr ~HBr++e (1)
T HE ion pair yield, MIN, for decomposition and
synthesis of hydrogen bromide by alpha-particle
bombardment has been computed previouslyl.2 from
e +HBr ~ H+Br- (2)
Br-+HBr+~ H+2Br (3)
estimates of the ionization produced by a known
amount of radon added to the systems. Based on the H +HBr ~ H 2+Br (4)
measurements of Lind and Livingston,2 a theory and
mechanism for these reactions were developed by 2Br+M (5)
Eyring, Hirschfelder, and Taylor. 3 For decomposition which can account for an ion pair yield of 4.0. If dis-
of pure hydrogen bromide, that mechanism contains sociative excitation of hydrogen bromide occurs, the
* From the Ph.D. dissertation of E. G. Zubler. Presented at number of molecules decomposed per ion pair formed
the 125th American Chemical Society meeting, Kansas City, may be greater than 4.0 by 2.0 molecules per
Missouri, March 23-April 1, 1954. dissociation.
t Present address: General Electric Company, Nela Park,
Cleveland, Ohio. In this work we have estimated the number of ion
1 R. Gillerot, Bull. soc. chim. Belges 39, 509 (1930). pairs by saturation ionization current measurements.
2 S. Lind and R. Livingston, J. Am. Chern. Soc. 58, 612 (1936).
3 Eyring, Hirschfelder, and Taylor, J. Chern. Phys. 4, 570
This is difficult or impossible in mixtures containing
(1936). hydrogen bromide, and therefore, we have had to base

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