Mass Spectrometric Investigation of the Sublimation of Molybdenum Dioxide

R. P. Burns, G. DeMaria, J. Drowart, and R. T. Grimley

Citation: The Journal of Chemical Physics 32, 1363 (1960); doi: 10.1063/1.1730922
View online: http://dx.doi.org/10.1063/1.1730922
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THE JOURNAL OF CHEMICAL PHYSICS

VOLUME 32, NUMBER 5

MAY, 1960

Mass Spectrometric Investigation of the Sublimation of Molybdenum Dioxide*

R. P.

BURNS, G. DEMARIA,t

J.

DROWART,t AND

R. T.

GRIMLEY

Department of Physics, University of Chicago, Chicago, Illinois

(Received November 30, 1959)

A mass spectrometric investigation of the vapor in thermodynamic equilibrium with powdered molybdenum dioxide has shown the vapor phase to consist, in decreasing order of importance, of the species MoOa,
(MoOa)" Mo0 2 , and (MoO,),. The heats, entropies, and free energies of reaction have been determined for
the reactions (T= 16000 K):
!x Mo0 2 (s) ...... (MoO,)z(g)+!x Mo(s)

where x= 1,2,3

Mo0 2 (s) ...... Mo0 2 (g)

t:.H T= 134.4 7 kcal/mole

2MoO,(g) ...... (MoO,).(g)

t:.H T= -1l0.28 kcal/mole

3MoO,(g) ...... (MoO,),(g)

t:.H T= -222.813 kcal/mole

For the case x= 1, 2, 3 the t:.H T'S are 121.83, 133.47, and 142.613 kcal/mole, respectively. Entropies
of the gaseous molecules MoO" (MoO,)" (MoO,)" and Mo0 2 at T= 1600 0 K are 96.6, 151.0, 201.2, and
85.5 eu, respectively. In addition, the atomization energies (t:.HoO) for the reaction
MoOz(g) ...... Mo(g)+xO(g)

were calculated to be 277.47 and 419.71O kcal/mole for x=2 and 3, respectively.

INTRODUCTION

HE only previously reported study of the vaporization of M002(S) is that of Blackburn, Hoch, and
Johnston,l who have examined the system employing
the Knudsen effusion technique. The conclusion of the
previous work is that the vaporization takes place
mainly by disproportionation of M002(S) to MoOa(g)
and Mo(s) with the side reaction Mo02(s)--tMo02 (g)
accounting for the remainder of the gaseous species.
The present mass spectrometric investigation was
undertaken in order to determine the importance of
polymers in the vapor over Mo02(s) .

EXPERIMENTAL TECHNIQUE

The general characteristics of the experimental

technique have been described previously.2 In the
present work a molybdenum outer cell was used in
conjunction with a Morganite recrystallized alumina
liner.a An alumina lid was used which had an effusion
hole 1 mm in diameter. In order to maintain a more
uniform thermal distribution in the cell, a molybdenum
cover having a 3-mm hole was used over the alumina
lid. Temperatures were read from a blackbody hole in
the base of the molybdenum cell, using a Leeds and
Northrup optical pyrometer which was calibrated

* Supported in part by the Office of Ordnance Research, U. S.

Army, and in part by the National Science Foundation.
t On leave of absence from Instituto di Chimica Fisica, Universita degli Studi, Rome, Italy.
t On leave of absence from Laboratoire de Chemie Physique
Moleculaire, Universite Libre de Bruxelles, Brussels, Belgium.
1 P. E. Blackburn, M. Hoch, and H. L. Johnston, J. Phys.
Chern. 62, 769 (1958).
2 M. G. Inghram and J. Drowart, "Mass spectroscopy applied
to high temperature chemistry," appearing in International
Symposium on High Temperature Chemistry at Asilomar, California (Stanford Research Institute, Palo Alto, California, 1959).
'Morganite Incorporated, Long Island City, New York.

against a National Bureau of Standards calibrated

lamp.4
Two samples of Mo02 powder were used in this work.
The first experiments were conducted with a sample5
whose x-ray pattern indicated mainly Mo02 with a
possible trace of MoOa impurity, while later experiments were conducted with a high-purity sample
(98.56% M002).6
EXPERIMENTAL RESULTS

As the temperature of the Knudsen cell assembly

was increased to about 850 o K, the ion (MoOa)a+
corresponding to the molecule (MoOa)a was observed.
Since MoOa(s) vaporizes as (MoOa)a(g) in this temperature range,7 the peak was attributed to small
quantities of MoOa impurity.
Sample A was found to contain less MoOa impurity
than sample B used in earlier work. However, in both
cases, the sample was heated in the 800-900 o K range
until no further trimer could be detected.
The temperature was then increased and the instrument sensitivity obtained by means of a quantitative
vaporization of a weighed amount of silver.2 After the
calibration, the temperature was again increased until
the vapor species from M002(S) were observed.
The temperature range 1500-1780 oK was examined
and the most important species found to be MoOa+,
(MoOah+, Mo02+, and (MoOa)a+. In addition, small
peaks of M020 5+, M020 4+, and Moa0 8+ were found.
4 National Bureau of Standards Ribbon Filament Lamp Test
No. G-18631a (1956).
Sample B, prepared by Dr. Joan Berkowitz, Arthur D. Little
Company, Cambridge, Massachusetts.
6 Sample A, Shattuck Chemical Company, Denver, Colorado.
7 J. Berkowitz, M. G. Inghram, and W. Chupka, J. Chern. Phys.
26, 842 (1957).

1363
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1364

BURNS,

DEMARIA,

DROWART,

AND

GRIMLEY

TABLE 1. Partial pressures of MoOs (g) in equilibrium with Mo02 (s).

Expt.

TOK

P(atm)

Expt.

TOK

P(atm)

Expt.

rK

P(atm)

A18
A17
A16
B14
A15
B6
B5
A14
A2
Al
B13
A13

1481
1512
1540
1566
1575
1596
1598
1605
1608
1610
1632
1636

1.4X10-s
3.1XlO-s
6.2XlO-s
1. 4X lO-7
1. 6X lO-7
3.3XlO-7
2.8XlO-7
3.6XI0-7
4.0XlO-7
3.5XlO-7
6.5XlO-7
7.5XIo-7

B12
A4
A3
A12
All
B2
Bl
B3
B4
A10
A5
A6

1640
1647
1652
1657
1675
1679
1681
1683
1687
1696
1702
1709

7.7X10-7
9.5XlO-7
1. OX 10-s
1.1X10-s
2.0XI0-6
2.3XI0-s
2.8XlO-6
2.6XI0-s
2.9XlO-6
2.9XlO-6
3.0XI0-s
3.0XlO-s

B15
A9
B7
B9
A7
A8
A20
Bll
B16
BlO

1716
1720
1721
1728
1732
1735
1747
1765
1773
1777

4.1XlO-6
4.4XlO-6
5.1XlO-6
5.8X10-6
5.4XlO-6
5.9XI0-6
7.9XI0-6
1. OX lO-5
1.1XlO-5
1. 4X lO-5

No AlxOy species were observed, nor was any reaction

between Mo02(s) or Mo(s) and A120 s apparent.
Approximate appearance potentials were determined
using the linear extrapolation method, using mercury
as the standard for the energy scale. The corrected appearance potentials were MoOs+, 12.00.6 ev;
(MoOs) 2+, 12.10.6 ev; (MoOs)s+, 12.01.0 ev,
and Mo02+, 9.40.6 ev. Ionization efficiency curves
indicated that MoOs+, (MoOsh+, and (MoOs)s+ were
all produced by direct ionization of the corresponding
neutral molecule. In the case of Mo02+, however, a
break in the ionization curve (13.5-14 ev) was noted
which indicated that at 17 ev slightly less than half

o 1.1003
o (1.1003)2

" 1.102

(Mo03 !,

FIG. 1. Partial pressures (atm) of the vapor species over

Mo0 2 solid as a function of l/TX lO4 deg K-l.

the Mo02+ peak was the result of ionization of the

Mo02 molecule. Of the possible parent molecules,
energetic considerations indicate that MoOs is the most
likely source of that part of the Mo02+ peak which is a
fragment, since the electron energy required for fragmentation in the case of the dimer and trimer is well in
excess of bombardment energies employed (17 ev).
Thus, the intensity of the MoOs+ ion was increased by
approximately 6% to correct for fragmentation loss.
Examination of the ionization efficiency curve of
M020.+ revealed thresholds at approximately 10 and
14.5 ev, whereas for MosOs+ a similar double threshold
was found with values of 12.2 and 14.5 ev. In both
cases the higher valued threshold resulted from the
onset of a fragmentation process whereas the lower
threshold appeared to result from a simple ionization
process of the parent M020. and MosOs molecules.
Approximate pressures were calculated to be M020.,
1.0XW-7 atm and MosOs, 1.2X1Q-s atm at 1774K.
The presence of a parent M020 4 molecule must be considered doubtful, but the upper limit of possible M020 4
at 1774K was found to be 2.4X1Q-7 atm.
After repeated cyclings of the sample to higher temperatures (ca. 1775K), it was noted that the partial
pressures of the vapor species began to decrease with
time. This effect was attributed to a molybdenum
metal coating on the sample surface which caused a
diffusion-limited vaporization process. In this study all
data were taken before the onset of the reduced activity.
It is interesting to note that data obtained from the
98.56% pure sample (A) and the slightly less pure
sample (B) agree well within the error of the pressure
calibrations. (See Table I and Fig. 1).
The relative ionization cross sections used were
Ag=34.8, Mo02=59.1, MoOs=62.4, (MoOsh=124.8,
and (MoOs)s = 187 .2.s Pressures were calculated by
using the above cross sections together with corrections
for multiplier efficiency and molecular effects.2 Partial
pressure (atm) data for the vapor species over solid
Mo02 are presented in Tables I and II and in Fig. 1.
The capital letters in the first column of Tables I and II
s J. w. Otvos and D. P. Stevenson, J. Am. Chern. Soc. 78, 546
(1956).

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1365

SUBLIMATION OF MOLYBDENUM DIOXIDE

TABLE II. Partial pressure of species in equilibrium with M002 (s).

Expt.

roK

MoO.
(atm)

(MoOah
(atm)

MOO2
(atm)

TABLE IV. Summary of experimentally determined reaction

enthalpies, entropies, and free energies.

(MoOa)a
(atm)

B14
B6
B5
A19
B13
A3
All
B2
B3
B4
AlO
A5
A6
B15
B7
B8
B9
A7
A20
B16
BlO

1566
1596
1598
1627
1632
1652
1675
1679
1683
1687
1696
1702
1709
1716
1721
1725
1728
1732
1747
1773
1777

1. 4X lO-7 2.9X10-s
3.3X10-7 6.5XlO-s
2.8XlO-7
1. 3X 10-7
6.5XlO-7 1. 4X 10-7
1.0X10-il 2.3XI0-7
2.0X10-il 5.7X10-7
2.3X10-il 5.8XlO-7
2.6X10-il
2. 9X 10-il 7.5XI0-7
2.9X10-il 9.4XI0-7
3.0XlO-iI 8.7XlO-7
3.0XI0-il
4.1X10-il 1. 3X 10-i1
5.1XlO-iI
1.4XI0-il
5.8XI0-il
5.4X10-il 1. 6X 10-il
7.9X10-il
1.1XlO-5
1. 4X lO-5 3.7X10-il

I1ST

kcal/mole

eu

1. 3/2Mo02(s)-->MoO a(g)+
!Mo(s)
2. 3Mo02(s)-->(MoOah(g)+
Mo(s)
3. Mo02(s)-->Mo02(g)
4. 9/2Mo02(s)--> (M003la(g) +
3/2Mo(s)
5. 2MoOa(g)-->(MoOah(g)
6. 3Mo03(g)--> (MoOala (g)

121.83

46.4

47.6

133.47

50.6

52.4

134.47
142.613

48.4
50.6

56.9
61.6

-llO.28 -42.1
-222.813 -88.6

-42.8
-81.1

Reaction

4.9X1Q-9
1.5XlO-s
4.1X10-s 6.9X1Q-9
6.9X10-s
1. 6X 10-7
1.6X10-7 3.8XlO-s
2.1X10-7
5.6XI0-8
2.7X10-7 7.1XI0-s
3.6X10-7
1.1XI0-7
3.7X10-7 1.4XI0-7
5.2XlO-7 1.9X10-7
9.2XlO-7
1. OX10-i1 3.1X10-7

refer to the sample of Mo02 used, while the numbers

refer to the order in which the data points were taken.
DISCUSSION

The present work confirms the estimate of Kelley9

and the findings of Blackburn et al. l regarding the
importance of the disproportionation reaction in the
vaporization of M002(S). On the other hand, it is found
that Mo02(g) is of considerably less importance than
concluded by Blackburn et al. and also that the
(MOOa)2(g) molecule is of more importance than their
estimate.
Equations for logP vs liT are given in Table III
and are the result of least squares fits of the data in
Tables I and II. The reaction energies t:.H T, t:.ST, and
t:. F T( T = 1600 OK) calculated from the experimental
data are given in Table IV. t:.Ho = 123.9 kcal/mole for
reaction I, Table IV, is to be compared with t:.Ho =
133.6 kcal/mole given by Blackburn, et aU Also
t:.Hoo=137.4 kcal/mole for reaction 3 is to be compared with t:.Hoo=129.8 kcal/mole, and t:.HT=228.8
kcal/mole for reaction 6 to t:.Hoo=220.9 kcal/mole
obtained by the same authors.
The slight discrepancies in some of the reaction
enthalpies can be attributed to a combination of one or

more of the following causes. Blackburn et al. underestimated the contribution of (MoOah(g) and overestimated the contribution of Mo02(g) to the total
pressure. These authors determined the relative
amounts of the gaseous species indirectly by two
quantitative vaporizations assuming that MoOa(g)
and Mo02(g) were the main vapor species and reported the vapor to consist of 22 wt % Mo02(g) in one
experiment and 36 wt % Mo02(g) in the other. Since the
results of quantitative vaporizations are extremely
sensitive to the amount of impurity, we prefer to
determine the composition of the gas phase mass
spectrometrically. Furthermore, S298 for Mo02(s)
used by Blackburn et al. has been determined by
King lO to be substantially lower than the previously
reported value. As was mentioned before, the present
work indicated that when measurements were attempted above '" 1800 o K, a gradual reduction in
activity occurred. Since Blackburn et al. investigated
the temperature range 1800-2000 oK, an additional
possibility exists that these authors encountered some
reduction in activity at the temperatures of their
measurements.
The entropies of the gaseous oxides at 16()()OK are
given in Table V. The values in the first row are calculated from the experimental data, S298Mo02(S) =11.06
eu lO and ST- S298Mo02(S) =37.1 eu which was estimated by an extension to high temperatures of the
method of Latimerll in which the entropy of Mo(s)
was combined with an average contribution of 0-TABLE V. Entropies of gaseous molybdenum oxides T=1600oK.
ST

TABLE III. Log P vs l/T for the vapor species in equilibrium

with Mo02(s).
log P MoOa (.) =-2.661X104 /T+10.130

= -2. 915X10 4/T+l1. 067

log

P(MoO')2(')

log

P(MoO,).(.) =

This work
Chandrasekharaiah
and Brewer"
DeMaria et al. b

ST

ST

ST

(MoO,)
eu

(MOO')2
eu

(MOO')3
eu

(Mo0 2)
eu

96.6

151.0

201.2

85.5
85.5

96.3

87.4

-3. ll7X 104/T+11. 067

log PMo02 (.) =-2.936X104/T+lO.574

" Footnote 13.

b Footnote 14.
10

I1F To
kcal/mole

I1HT

T=1600oK

No.

K. K. Kelley, Climax Molybdenum Bulletin Cdb-2 (1954).

11

E. G. King, J. Am. Chern. Soc. 80,1799 (1958).

W. M. Latimer, J. Am. Chern. Soc. 73, 1480 (1951).

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1366

BURNS,

DEMARIA,

DROWART,

obtained from other XO z type compounds lz (X =Ti,

Zr, Mn, Si, Th, or U). The data in the second and
third rows are calculated from free energy and enthalpy
functions with the data of Chandrasekharaiah and
Brewerl3 and DeMaria et al. l4 The agreement is seen to
be quite good for M003(g) and MoOz(g). The value
S1600(Mo03)3(g) =201.2 eu is to be compared to
S9oo(MoOa)a(g) = 193.1 eu given by Berkowitz et al.7
By combining the heat of formation of M002 l5.l6
with the experimental data and calculated data mentioned in the foregoing the atomization energies !J.Ho
for the reactions MoOz(g)~Mo(g)+20(g) and
MoOa(g)~Mo(g) +30(g) are calculated to be 277.4
12 K. K. Kelley, U. S. Bureau of Mines Bulletin 476 (1949).
13 M. S. Chandrasekharaiah and L. Brewer, UCRL-8736
(University of California, Berkeley, California).
14 G. DeMaria, R. Burns, ]. Drowart, and M. G. Inghram,
]. Chern. Phys. 32, 1373 (1960), this issue.
16 B. A. Staskiewicz, ]. R. Tucker, and P. E. Snyder, ]. Am.
Chern. Soc. 77, 2987 (1955).
16 A. D. Mah, ]. Phys. Chern. 61, 1572 (1957).

AND

GRIMLEY

7 kcal 419.710 kcal/mole, respectively. These values

are to be compared to the values 262 and 411 kcal/mole
given by DeMaria et aI.l 4 to the values 285 and 410
kcal/mole of Blackburn et al.,! and to the values
295 and 426 kcal/mole derived from the data of
Blackburn et al. using the free energy functions mentioned previously.la.l4 Dissociation energies for the
molecules M020 5 and MOaOg are not given since accurate free energy functions for these molecules are
lacking.
ACKNOWLEDGMENTS

The authors wish to acknowledge the kindness of the

S. W. Shattuck Company, of the Climax Molybdenum
Company, and of Dr. Joan Berkowitz, Arthur D. Little
Company, for providing the samples used in this work.
The help of Miss Anne Plettinger in providing x-ray
data is appreciated.
Particular thanks are given to Dr. Mark G. Inghram
for his suggestions and interest in this work.

THE JOURNAL OF CHEMICAL PHYSICS

VOLUME 32, NUMBER 5

MAY, 1960

Thermodynamic Study of A1 20 3 Using a Mass Spectrometer*

]. DROWART,t

G.

DEMARIA,t

R. P.

BURNS, AND M.

G.

INGHRAM

Department of Physics, The University of Chicago, Chicago, Illinois

(Received November 5, 1959)

The evaporation of alumina under nearly neutral conditions in tungsten and molybdenum Knudsen cells
has been investigated by mass spectrometric methods. The atomization energies of the gaseous molecules
are DoO(AIO) = 1155 kcal/mole; D oO(AJ,0)=2457 kcal/mole; DoO(AJ,02)=3657 kcal/mole.

INTRODUCTION

conditions. Ackermann and Thorn,4.6 however, comN a study of the vaporization of alumina under pared the weight loss of alumina-loaded tungsten effureducing conditions (AbOa-Si) Grube, Schneider, sion cells with the amount of alumina evaporated near
Esch, and Fledl concluded that AI20 is the major 2600K. They concluded that the ratio of tungsten to
aluminum-containing species in the vapor. From a alumina weight losses might be accounted for by recomparative vapor pressure study (in tungsten Knud- duction of alumina by tungsten and the vaporization
sen cells) of the aluminum-oxygen system under re- of one or more gaseous aluminum oxides and one or
ducing (Ab03-AI) and under nearly neutral conditions more gaseous tungsten oxides. A similar view has been
6
(AI20 a) Brewer and Searcy2 concluded that under re- held by von Wartenberg. On the other hand, Medve7
ducing conditions Al and AbO are the principal vapor dev has calculated that the molecule AbOa is of major
species while under neutral conditions AIO and atomic importance in the vapor of aluminum oxide under neuoxygen are the principal vapor components. Cochran3 tral conditions.
Amass spectrometric analysis8 0f the vapor in thermoconfirmed the predominance of AbO under reducing
dynamic equilibrium with AI-AI203 showed the pre* Supported in part by the Office of Ordnance Research, U.S. dominant gaseous species to be Al and AI20 and gave

Army, and in part by the National Science Foundation.

t On leave of absence from Laboratoire de Chimie Physique
Moleculaire, Universite Libre de Bruxelles, Brussels, Belgium.
t On leave of absence from Istituto di Chimica Fisica, Universita degli Studi, Rome, Italy.
1 G. Grube, A. Schneider, U. Esch, and M. Fled, Z. anorg.
Chern. 260, 120 (1949).
2 L. Brewer and A. W. Searcy, ]. Am. Chern. Soc. 73, 5308
(1951).
3 C. N. Cochran, ]. Am. Chern. Soc. 77, 2190 (1955).

4 R. ]. Ackermann and R. ]. Thorn, ]. Am. Chern. Soc. 78,

4169 (1956).
6 R. ]. Ackermann and R. ]. Thorn, Proceedings of the 16th
International Congress of Pure and Applied Chemistry (Paris,
1957), p. 667.
6 H. vonWartenberg, Z. anorg. u. allgem. Chern. 269, 76 (1952)
7 V. A. Medvedev, Zhur. fiz. Khim. 32, 1690 (1958).
8 R. F. Porter, P. Schissel, and M. G. Inghram, ]. Chern. Phys.
23, 399 (1955).

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