Академический Документы
Профессиональный Документы
Культура Документы
Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to IP: 144.32.128.70 On: Wed, 29
Jun 2016 23:18:53
MAY, 1960
BURNS, G. DEMARIA,t
J.
DROWART,t AND
R. T.
GRIMLEY
where x= 1,2,3
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
1363
Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to IP: 144.32.128.70 On: Wed, 29
Jun 2016 23:18:53
1364
BURNS,
DEMARIA,
DROWART,
AND
GRIMLEY
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
o 1.1003
o (1.1003)2
" 1.102
(Mo03 !,
Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to IP: 144.32.128.70 On: Wed, 29
Jun 2016 23:18:53
1365
Expt.
roK
MoO.
(atm)
(MoOah
(atm)
MOO2
(atm)
(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
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
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
I1F To
kcal/mole
I1HT
T=1600oK
No.
11
Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to IP: 144.32.128.70 On: Wed, 29
Jun 2016 23:18:53
1366
BURNS,
DEMARIA,
DROWART,
AND
GRIMLEY
MAY, 1960
G.
DEMARIA,t
R. P.
BURNS, AND M.
G.
INGHRAM
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
Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to IP: 144.32.128.70 On: Wed, 29
Jun 2016 23:18:53