TABLE 79 (continued) T.

oK

cal/de g' go atom

S:

caVdegogoatom

S~

.;
c al/deg-g-atorn

cal/de g- goatom

.;

800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 2600 2700 2800
2900

3000

12.85 13.62 14.32 14.96 15.57 16.14 16.68 17.21 17.71 18.19 18.65 19.10 19.53 19.95 20.36 20.75 21.14 21.52 21.89 22.25 22.61 26.46· 26.80-

48.37 48.92 49.47 49.95 SO.38 SO.78 51.15 51.49 51.81 52.12 52.40 52.68 52.94 53.19 53.43 53.67 53.90 54.12 54.34 54.56

54.n
54.99 55.20

8.98 9.46 9.91 10.34 10.75 11.14 11.51 11.88 12.23 12.57 12.89 13.21 13.51 13.81 14.11 14.37 14.65 19.92 15.18 15.43 15.69 17.16· 17.4~
function

45.26 45.63 45.99 46.33 46.65 46.96 47.24 47.51 47.77 48.02 48.25 48.48 48.70 48.91 49.10 49.30 49.49 49.67 49.84 SO.OI SO.18 SO.34 SO.SO
of liquid

The two last values molybdenum,

refer to the entropy

and free energy

8.

MOLYBDENUM OXIDES

The following oxides of molybdenum exist: MoOs- a-oxide; Mo02.S89 or M<>g026-/3'-oxide; Mo02.S75 or MOs02s-/3-oxide; MOO:!.75or M040u-'Y-oxide and Mo02-o-oxide. These data are taken from Magneli, as quoted by Hegedus and co-workers./43/.

Molybdenum

dioxide MoO:! (M

127.95)

Cry s tal s t r u c t u reo f Mo02• Molybdenum dioxide has a di.stor-ted rutile structure (Brewer /44/). The lattice parameters are a = 5.61 A, b = 4.84 C = 5.53 and a = 119.6° (Magneli /45/). Mol a r vol u mea n d den sit Y 0 f lVIo02• The molar volume of MoO:! is 20 cms /mole (Biltz /46/).

A,

A,

According to Stefanovics /47/, the density of Mo02 is 6.342 g/cm3 at 14°. Temperature of disproportionation of MoO:!. According to Brewer /44/, solid molybdenum dioxide disproportionates into solid molybdenum and gaseous oxygen at 2250 ± 50 K and at a pressure of 1 atm. Vapor pressure of Mo02. Blackburn and co-workers /48/ measured the vapor pressure of molybdenum oxides by the Knudsen effusion method. They found that some of the solid Mo02 sublimes without decomposition, while the greater part dtsproportionates into gaseous MoOs and solid molybdenum. Heat of disproportionation of Mo02• According to Blackburn et al , /48/, disproportionation of solid Mo02 into gaseous MoOs and solid molybdenum is accompanied by the heat change IlHg = 133.6 kcal/mole of Mo03•
0

58

Energy of dissociation of Mo~. Blackburn and co-workers report 1481 that the energy of dissociation. D:, of gaseous MoOI into gaseous atomic molybdenum and oxygen is 284.6 kcal/mole at O"K. Entropy of MoO.. King 1491 determined the heat capacity of MoO. in the range 51 to 298°Kand from his results calculated the standard entropy of this compound, i. e., = 11.06 ± 0.05 cal/deg' mole. According to Tonosaki 150/, the standard entropy of MOOz 19.3 cal/deg. mole. is Kubaschewski and Evans 1221 give the standard entropy of MoO. as = 13.6 ± 2.0 cal/deg· mole. The great discrepancies in the values of the absolute entropy of MOOzare evidently due to the difficulty of determining the heat capacity of this compound, which"is unstable on heating. Heat of formation of MoOz. Tonosaki 1501 found the heat of formation AH:" of solid M~ to be -131.692 kca1/mole. The heat of formation of MO<l.z determined by various authors has the following values: as

S:,.

S:..

&H~,.= -140.9 kcal/mole (Stasliewicz et al./51/);

AH:', =
AH~

-142.8 kcal/mole (Mixter /52/);

&H:', = -140.8 kcal/mole (Mah

153/);

&H~n = -131.0 ± 2 kcal/mole (Brewer 144/) = -139.5 ± 3.0 kcal/mole (Kubaschewski, Evans 122/); = -130 kcal/mole (Rossini et ale 121/).

AH:"

We consider Mahra value, MIN= -140.8 kca1/mole 153/, the most reliable. Entropy of formation of MoOz. Tonosaki /501 determined the entropy of formation of Mo<>zs AS", = -36.5 cal/deg· mole. Brewer 14:4:/ a gives the value AS:N = -36.6 cal Jdeg : mole. F r e e en erg y 0 f for mat ion 0 f MOO,. The value of the free energy of formation of Moo,. according to /44/, is AF:" '" -120 kcal/mole and, according to 150/, M;" = -120.816 kcal/mole. The variation of the free energy of formation of MO<>z with temperature according to the reaction Mo(s) + 0, = MO<>z is expressed by the follow(s) ing equation &Fr= 140,100 + 4.6TlogT-55.8 T cal. which is valid in the temperature range 298 to 1300 K. The accuracy of the equation is ±6 kcal/22/.
0

Molybdenumtrioxide Mo~ (M = 143.95) Crystal structure of MoOs. Structure type 00.. Spaqal group D~ Lattice parameters of the orthorhombic structure: a = 3.9 A, b = 13.8 A; c = 3.7 A/53, 54/. Molar volume and density of MoOs. According to Hiilsmann and Biltz 155/, the molar volume of MoC>:, 30.69 at 21 is 30.47 at -78°; and 30.29cms/mole at -195°. The density values of MoC>:, presented in Table 80. are Mel tin gpo i n t 0 f MoC>:,.The melting point of molybdenum trioxide is presented in Table 81 according to various authors. Stull/20/, Brewer /44/. and KubaschewskiandEvans/22/. consider 795° the best value for the melting point of Mo~.
0 ;

59

TABLE 80 Density of Mo03 Temperature, DensiV glcm Year Author Reference

°c
26 19.5 21 -78 -195

4.696 4.500 4.692 4.726 4.754

1915 1915

Muller Wedekind, Horst

/9/ /56/ /55/

1934

Hiilsrnann, Biltz

TABLE 81 Melting point of Mo03 Melting point, DC 791 795 795 795.2 Year 1908 1921 1931 1953 Author Groschuff Jaeger, Feiser Cosgrove, Snyder Germs Reference /57/ /58/ /59/ /60/

BOiling p o i n t of MoOs. The boiling point of MoOs. as determined by Feiser /59/, is 1155 Kelley /27/ gives the value 1424°K, Kubaschewski and Evans /22/ 1553°K. Brewer /44/ 1530 ± 50 K at a pressure of 1 atm. and Rossini et al. /21/1428°K. Va p 0 r pre s sur e 0 f MoOs. The vapor pressure of MoOswas determined by Feiser /59/. It was calculated on the assumption that losses in weight during vaporization of MoOsin a current of gas are proportional to the vapor pressure. The results of the investigation are given in columns 2 and 5 of Table 82. Columns 3 and 6 of the same table give the vapor pressure of MoOsas calculated by Ramsay- Young's rule for temperatures exceeding the melting point of MoOs.
0 • 0

TABLE 82 Vapor pressure of Mo03 Temperature, oK

I

Vapor pressure, mm Hg
II

Temperature, oK

Vapor pressure, mm Hg
Ii

•
1123 1173 1223 1273 1323 1373 1428

•
17.9 38.6 146.0 261.2 443.9 760.0

873

898 923 973 993 1023 1073

883

0.000 0.009 0.018 0.050 0.300 0.600 1.750 10.100

7.7

23.4 53.9 105.1 179.8 288.3 476.2 760.0

77.2

60

•
The discrepancy between the data of columns 2 and 5, 3 and 6 of Table 82 may be due, according to Feiser, to the possibility of polymerization of MoOsmolecules. Kelley /27/ used the data of columns 3 and 6 of Table 82 to derive the following equation for the variation of the vapor pressure of solid MoO, with temper-atur-e: 15 110 logP(atm) = --' -+ 1.46IogT-1.32·10-sT+ 9.071

and over liquid MoO. logP(atm) =_11,820 -7.041ogT+ 30.494.

According to Kelley'S /27/ equations. MoO. has the following values of vapor pressure.
Temperature,
Vapor pressure,

• K .••••••••••••• mm Hg ••.••.••••

934 0.076

999
0.76

1074(5) 7.6

120'7(1) 76

1283 190

1350 380

1424 760

Stull /20/ compared the experimental results of various authors and gave the following values for the vapor pressure of solid and liquid MoOs:
Temperature,
Vapor pressure.

• K ••••

9'13-

100'1 1

1058

1087 10

1124 20

1165

1190 60

1128 100

128'1 200

1355

1424 '160

mm Hg 0.3

40

400

Ueno /61/ studied the vapor pressure of MoOsin the range 635 to 675°, using a Knudsen effusion cell, and derived the followingequation for the variation of the vapor pressure of solid MoOawith temperature: logP(mm Hg)

_13,902.7 + 13.033.

Kubaschewski and Evans /22/ quote Uenovs equation /61/ for the vapor pressure of solid MoOs, but consider the following equation more reliable: logP(mmHg) = 16 150
'T

-5.53Iog T+ 32.08.

This equation is valid from 298° to the melting point. Forliquidmolybdenum the same authors give the equation log P (nun Hg} = -14,110· T-l_7.08 logT+ 34.54. valid from the melting point to the boiling point. Zelikman and co-workers /62/ measured the vapor pressure of MoOs by the effusion method and also by observing the boiling point at given pressures. By comparing the results of both methods, they concluded that MoO. polymerizes in the gaseous phase and found that from 950 to 1000 the composition of gaseous MoOscorresponds to (MoOsh Or MOso.. The equation 7685 log P(mmHg) = --+ 8.26
0

was derived from vapor pressure curves presented below /62/. These curves were obtained by measurement of the boiling point of MoOsat fixed pressures. *
Data of Rossini et a1./21/.

61

Temperature,
905 960 1015 1057 1100 1155·

•C

Pressure, mm Hg
53 100 200 300 450 650

Blackburn and co-workers /48/ measured the vapor pressure with a Knudsen effusion cell and confirmed the fact that MoOsvaporizes as (Mo~)s. Figure 2 shows the graph of the function log P f _!_ for gaseous Mo~.
It was plotted from the data of Stull /20/,

Kelley /27/. Kubaschewski and Evans /22/, and Zelikman et al, /62/. Whereas the points of Stull /20/, Kelley /27/, and Zelikman et al./62/ fit well into the plotted curve, those of Kubaschewski and Evans /22/ are located outside the curve. The high accuracy of the comparatively recent results of Zelikman et al. /62/ (1956) is indicated by the fact that they show good agreement with those of Stull /20/ and Kelley /27/. The best values for thermodynamic calculations are therefore considered to be those of Stull /20/. Kelley /27/. and Zelikman and co-workers /62/.
logp( mrn.Hg) J.D

, "'r'\,.

es
2.0 U '"0

['A.-

o Stull

According to

r, I'., "c
1'.

x Kelley + Kubaschewski and Evans • Zelikman and Gorovit

I'.
OSJ 0.7 0.7J

~
1'+

.\
~

o.S
0.0 0.8
Q.4;

0.9 jIlYS"

-tu
-1.0

KO ~

.-/11
~

tfU

~~
+_I

-LS
FIGURE 2. Vapor pressure of Mo03'

He at cap a cit y 0 f MoD,. The heat capacity of solid Mo~ at low temperatures shows the following variation with temperature:
Temperature, Heat capacity, OK • . . • • . .. cal/mole ..•.
10 (0.06) 25 (0.08) 50 (3.16) 100 7.31 150 11.04 200 13.79 289.1 17.57

• Extrapolation.

62

From the results of Seltz and co-workers /64/. Kelley /63/ derived the following equation. valid from 298 to 1068°K. for the variation of the molar heat capacity of solid molybdenum trioxide:

Cp-13.6+ 13.5.1(,'7'.
Smith and co-workers /65/ note that the results of Seltz /64/ for the heat capacity of MoOsat temperatures below zero degree centigrade are not accurate enough to verify the function Cp ..., 1(1'2) in the range 0 to 60°K. For this reason. Smith and co-workers /65/ made a new investigation of the heat capacities of Mo~ at low temperatures. The authors /65/ obtained their data by using the low-temperature calorimeter described in /66. 67/. The general accuracy of the determination of Cp was approximately 0.2% at temperatures higher than 50"K. and possibly 0.5% at 200K.
TABLE 83

Experimental data

OIl

I
!M.Ol 98.19 102.18 106.02 109.73 113.31 116.79 121.10 126.20 131.10 135.85 140.49 145.03 149.46 153.79 158.04 162.22 167.21 172.98 178.65 176.10 181.69 187.18 192.58 197.89 203.13 208.28 213.38 218.34

cal/mole .deg

cp

the heat capacity of solid Mo03/63/

T·lC

cal/mole . deg

cp

II
T -It

cal/mole- deg

cp

7.017 7.388 7.754 8.088 8.401 8.698 8.970 9.312 9.716 10.085 10.447 10.762 11.076 11.368 11.640 11.918 12.165 12.449 12.785 13.083 12.964 13.264 13.541 13.826 14.076 14.308 14.571 14.778 15.007

223.30 228.21 233.06 237.86 242.62 241.71 246.45 251.10 260.27 264.79 269.28 213.74 278.15 2M.Sf 286.89 291.20 299.76 58.72 63.10 67.02 73.97 71.12 80.11
295 ••

15.224 15.391 15.583 15.788 15.967 15.948 16.120 16.295 16.458 16.611 16.676 16.951 17.275 17.384 17.544 17.104 17.832 17.9'20 3.173 3.524 3.995 4.390 4.754 5.074 5.397 S.?03 6.069

88.54 92.96 97.17 101.19 19.16 24.65 24.47 29.89 31.86 35.64 40.69 44.48 47.72 54.53 59.43

6.527 6.945 7.299 7.675 0.387 0.578 0.735 0.949 1.066 1.301 1.730 2.100 2.425 2.707 3.097

255.70

17.mt

SO.&6

3.606

SS.25 70.62

18.27 20.86 23.68 30.02 36.99 41.58 45.24 48.36 51.12

0.316 0.516 O.SS) 0.890 1.418 2.188 2 •• 2.759 3.143

1.827

SS.02

&U3

Experimental data on Cp per mole of MoO, are presented in Table 83. They were obtaitled in the same order as given in Table 83. The gaps inbetween the series of numbers separate data obtained in the further series of experiments. Values of the heat capacities of solid MoOsin the range from 10 to 3000K at intervals of 10° are presented in Table 84. According to Orr /68/ the heat capacity of solid molybdenum trioxide fits the following equation in the temperature range 298 to 1808°K: Cp = 20.07 + 5.80 ·10-3r-3.68· 10-5r2• The accuracy of this equation is 2"10.

63

TABLE 84

T.

OJ(

Heat capacities of Mo03 cal/m~re. deg

IT.

oJ(

cal/m~fe. deg

IT ..

J(

cal/m~fe. deg

10 20 30 40 50 60 70 80 90 100 110

0.39 0.90 1.67 2.65 3.66 4.69 5.68 6.66 7,56 8.42

200

120 130 140 150 160 170 180 190

210 220

9.23 10.00 10.73 11.40 12.02 12.61 13.17 13.69 14.18 14.64 15.07

290 300

230 240 250 260 270 273.15 280 298.1S

15.48 15.87 16.25 16.61 16.96 17.07 17.30 17.65 17.93 17.98

Data on the molar heat capacity of liquid MoOs are given by Cosgrove and Snyder /60/. He at 0 f fu s ion 0 f MoOs. The first measurements of the heat of fusion of MoOs were presented by Hoermann /69/ and Groschuff /70/. Kelley /71/ gives the average of these data, I. e., l-tc« = 2500 cal. This value, however, is very low. Cosgrove and Snyder /60/ found by experiment that the heat of fusion Lfus of MoOs is 12,540 cal/mole. Kubaschewski and Evans /22/ consider the value 12.55 ± 0.40 kcal/mole to be the most reliable. He at of vap 0 r i z a ti 0 n 0 f .MoOs. The heat of vaporization of MoOs, according to /62/, is 35.1 kcal/mole. At its boiling point (1280°), the heat of vaporization Lvap of molybdenum trioxide is 42.7 ± 4.0 kcal/mole /22/. Heat of sublimation of MoOs. The experiments of Ueno /61/ showed that at 928.1°K, Lsubl= 63.7 kcal/mole and at 298.1°K Lsubl= 49.8 kcal/mole. Kubaschewski and Evans /22/ give the values 70.6±5.0kcal/mole and 62.2 ± 3.0 kcal/mole at 25° and at the melting point (795°), respectively. Rossini and co-workers /21/ give Lsubl = 65 kcal/mole at 700°. Entropy of sublimation of MoOs. According to Ueno /61/, ~Ssubl= 46.5 cal/mole·deg at 928.1°K. Rossini et al , /21/ give ASsub1= 67 cal/mole· deg at 700°. Free energy of sublimation of MoOs. According to Ueno/61/, ~Fsubl = 20.5 kcal/mole at 928.1°K. If the heat and entropy values of sublimation of Rossini et al , /21/ are used, the free energy of SUblimation at 973°K is ~Fsubl = 65 -0.067·973 = 65 -65.191 = -0.2 kcal/mole. Heat of dissociation of (MoOsh. For the dissociation of (MoOsh-3MoOs ~H= 220.9 kcal/mole /48/. Entropy of dissociation of MoOs*. Blackburn and co-workers /48/ give the energy of dissociation of gaseous MoOs into atomic molybdenum and oxygen as = 410.3 kcal/mole at OOK. According to Brewer /44/, the energy of dissociation of gaseous MoOs into atoms is 445.0 ± 5 kcal/mole at O°K. He at con ten t 0 f MoOs. According to Cosgrove and Snyder /60/, the heat content of solid molybdenum trioxide is given by the equation:

Dg

[Energy of dissociation may be meant.]

64

and that of liquid molybdenum trioxide is given by: Hr-Hm-l.25151.1o'-2.19714.1o'T

+ 1.47790.Ur-'T'

- 2.33333·lcrra.

Entropy of MoO,. From the data of Seltz /64/ on the heat capacity of MoO, from 70 to 299-1{,Kelley /37/ calculated the following values for the entropy of Moo,: S'o = 2.97 (this value was obtained by exptrapolation). S;..-Sf. = 15.71 (this value was obtained by direct measurements), and So = 18.7 ± 0.3 cal/mole' deg. ~ssini and co-workers /21/ give the entropy of Moo, as = 18.58 cal/mole . deg. Smith et al./65/ calculated the entropy of solid MoO, at low temperatures; these data are presented in Table 85 /65/.

S:..

TABLE

ss

Entropy of solid Mo03 /65/

T.-It eal/mole' deg

r.-It

cal/mole· deg

s;-

10 m 30 to

eo
90 100 110
70 80

50

0.048 0.197 0.4S0 0.811

1m 130 150 160 110 180 190 JOG 210 2JO

l.2.
1.857

ItO

2.499 3.189 3.916 4._ 5.427

I._ 10.000
12.178

6.195 6._ 7.733 8._

11._
10.737

ttO
270

T••

cal/mole· deg

.r-

_, 273.15 _,
190 _.IS 100

14._ 14.111 11.114 11.111 16._ 17._ 17.476 18.0ID

12.. 1 11.171

.... ...

Fr e e e ne rgy

fun ction
(I)' -

value of the functions

~-~
O

of MoOs. Smith et ale /65/ calculated the

•-+ and T for T 7' Their results are presented in Table 86.
TABLE B6

~-~ S;

~-<

solid MoO, at low temperatures.

Variation of.'and

H T-

II!
'

'I.-I(

••
0.025 0.073 0.153 0.271 0.416 0.608 0.832 1.083 1.358 1.652

H~-~
r 0.023 0.124 0.297 0.540 0.870 1.249 1.667 2.106 2.558 3.013 3.467

T••

.'

eal/mole' deg

H;-~
T

30 40

10 20

60 70 90

SO
80

100 110

1.960

220

160 170 1110 HID 200 210

ItO ISO

120 130

2.281 2.612 2.!IED 3.2M 3.643 3.995 4.350 4.705

3.914

5.062 5.418 5.773

5.203 5.610 6.005 6.387 6.758 7.116 7.463 7.791

4.353 4.783

6._ 6.831 7.180 2&0 7._ 27D 273.15 7.635 7.870 280 8.212 290 298.15 8._ 300 8.561

230 240

T••

••
6.127

'''';<
I..
8.12& 8." 8.7. 1.011 9.41S 10.011 10.144

I._ I._

65

Heat of formation of Mo~. its elements is given in Table 87.

The heat of formation

of Mo~

from.

TABLE 87 Heat of formation Heat of formation

-A

of Mo03

Hg88

Method of determination

Year

Author

Reference

kcal/mole Direct determination constant volume at at

166.14

167.0

Direct determination
constant pressure

}
=

1903

Delepine

/72/

Calculated 181.5 action

from the re-

3Na.O. Mo Na.MoO. 2Na2O

1910

Mixter

/73/

175.6

Direct determination Direct determination re-

1924

Moose,

Parr

/74/

180.4 ± 0.6

calculated

for 19° at con-

1934

Neumann, Kunz

Kroger,

/75/

stant pressure 178.0

1955

Stasliewicz

et a1.

/51/

The most reliable values for the heat of formation of Mo~ are the following: ~H~98 = -180.3 ± 1.5 kcal/mole /44/, ~H~98 = -178.2± 1.5kcal/mole /22/, ~H~98 = -178.1 kcal/mole /53/. The reader can consider the value -178.1 kcal/mole as the most accurate for the purpose of calculation. Entropy of formation of MoOs. The entropy of formation l!.S~98 of Mo~, according to Brewer /44/, is -61.5 cal/deg· mole. Smith and coworkers /65/ give the value l!.S~98 = -61. 75 e. u. Free energy of formation of Mo~. According to Brewer /44/, the free energy of formation ~Fg98 of MoOg is -162 kcal/mole. According to Smith et al. /65/, ~F~98 = -161.92 kcal/mole. Kubaschewski and Evans /22/ give the following equation of the free energy of formation of MoOg: l!.F~ = 38,700-19.5T from 298 to 1300°K. The accuracy of this equation is ± 3 kcal.,

9.

SULFIDES

OF MOLYBDENUM Mo~ (M = 160.082)

Molybdenum disulfide

Cry s t a I s t r u c t u reo f MoSz. It has been established recently that MoS2 exists in two modifications: natural Mo~ (mineral molybdenite) and artificially prepared molybdenum disulfide. Natural MoS:! (a-M0S:!) has a hexagonal structure of type C}. Its spatiaJ group isD:". Parameters of the crystal lattice are a = 3.15 A, C = 12.30 A /76/ .

66

Artificially prepared molybdenum disulfide (~-MoSz)has a rhombohedric struc~re. The parameters of the crystal lattice are a = 3.17 A and c =
18.38 A.

The structure of I3-Mo~ Was first investigated by Bell and Herfert /77 /. The authors assum.ed that it corresponded to the Cd~ structure. Later. however. /78/. it was shown that the structure of I3-MoSais described by the spatial group R_ - C~. Zelikman and co-workers /79/ studied the structure of MOSz samples. synthesized by means of five different methods. It was found that all samples had a layer-like structure. which. however. differed somewhat from both. a-Mo~ (molybdenite) and I3-MoSa. J3-MoSz does not occur in nature. Dens ity of Mo~. The density of MoSzis given in Table 88.
TABLE 88

Density of Mo03 Temperature,

·c
14 14

Density,.,

g1cm3
4.80 4.88 5.05

State Crystallin .. Amorphous Molybdenite

Year

Author

Reference

1901 1925

Guichard Hassel

/80/

/81/

Heat of sublimation and decomposition of MoSz. Molybdenum. disulfide is the most stable of the molybden sulfides (MoSz, MO:!Ss, MoSs). Guichard /82/. Picon /83/. Montoro /84/, Joly /85/ showed that the behavior of MoSadepends on the conditions under which it is heated. Guichard /82/ observed that molybdenite heated for a short time in an electric arc furnace dissociated with formation of M~Ss. On heating for longer periods of time molybdenite dissociates completely into metallic molybdenum. [and sulfur]. M~Ss is formed when MoS:!s heated in a crucible in i the presence of air. Picon /83/ noted appreciable dissociation of MoSzin vacuo at 1100 to 1300°. Montoro /84/ and Guichard /86/ report that MoSa dissociates in vacuo at 1100 without-formation of intermediate Mo.zSs. When MoSsis heated in a carbon crucible at 1200°, dissociation of molybdenum disulfide proceeds to completion with the formation of metallic molybdenum. within two hours. Zelikman and Krein report in a later work /87/ that at atmospheric pressure MoSzdissociates appreciably only at temperatures exceeding 1300°; the probable dissociation product is M~Ss. Melting point of MoSz. Zelikman and Belyaevskaya /88/ found that molybdenum. disulfide (molybdenite) melts at 1650 to 1700° with simultaneous decomposition. Under these conditions the rate of dissociation of MoSzis very high and a lower sulfide (apparently MO:!Ss) for-n.ed as the is intermediate product. Dissociation pressure of MoSa. Thermaldissociationofmolybdenum. disulfide at 800 to 1100° was studied by Zelikman and Krein /87/. They used an adaption of the dynamic method, described by Vol'skii /19/,
0

67

.n which the equilibrium constant/(p. for the reduction of MoS2 with hydrogen is determined:

M~
pI . P H. S, ~oS

+ 2Ha +!: Mo + 2H:$.

PH.

PHoS From the experimental values of /(p - -constant /(P.=

and from the equilibrium

for the dissociation of hydrogen sulfide 2~S =

2Hz+ S:!. the authors calculated the vapor pressure of sulfur P So = /(P(S) for reaction MoSz;= Mo + Sz; /(P(S) .... p(s.) = K: •. Kp(2)' or log P s. = 2 log l( P(I) + log /(PCI)' The mean experimental values of Kp(I)' the known values of /(P(2) and the calculated values of log Ps. are presented in Table 89.
TABLE 89 Dissociation pressure of MoS2

Temperature.

°c

_
Xso(2)

VHoS
VH• 2l0gK

P(l)

-logK

P(I)

-logPs.

1000
1100

900

810

0.0027 0.0083 0.0120 0.0319

5.137 ".162 3.842 2.992

3.65 2.90 2.25

1.75

8.7IfT 7.062 6.092 ".742

He at cap a city 0 f MoSz. Andersen /89/ determined the true molar heat capacity of MoS:!(natural molybdenite) at constant pressure. The mineral contained 0.31% FeSz and 0.58% Si~ as impurities. These were allowed for in the calorimetric determinations. The results are shown in Table 90.
TABLE 90 Heat capacity of MoS2 Heat capacity Heat capacity call deg • mole 10.51 11.18 13.28 14.14 14.88 15.08

Temperature.

OK

cal/deg vrnote
2.291 2.601 3.264 3.944 5.164 1.368 9.318

Temperature.

OK

56.1 60.1 10.5 80.6 100.2 118.1 143.5

161.3 189.5 220.4 249.5 219.1 292.1

Kelley /90/ interpolated the data of Andersen /89/ and gave the following values for the heat capacity:
Temperature.

OK

• • • ••
•.•.•

10 (0.02)

25 (0.33)

50 (1.85)

100 5.12

150 9.19

200 12.51

298.1 15.19

298 15.11'

Cpt

cal/deg.mole

• According to Rossini and co-workers

/21/.

68

Kelley /91/ used the data of Regnault /92/ to obtain the following equation for the variation of the molar heat capacity of solid Mo~ with temper-atureCp= 19.7+ 3.15·10-IIT(at273-729°K).

Smith and co-workers /65/ determined the heat content of solid molybdenum disulfide calorimetrically /66, 67/ at low temperatures and from these results calculated the heat capacity. The calculated values are presented in Table 91.
TABLE Hul: capacity 91 cal/mole· deg of solid MoS2 according to Smith /65/,

Cp

T.·.
43.71 48.58 Sl.43 55.32 51.66 59.44 64.56

Cp

C,

25.37 19.69
23.55

'n.Sl 30.88 34.18 38.63

0'.500 0.179 0.375 0.S33 0.659 0.823 1.042

1.317 1.645 1.880 2.101 2.279 2.409 2.817

74.58

69.01
86.68 91.99

80.96

101.54

96.94

3.161 3•• 4 ••• 4." 5.1a &.1&1 &,.

The rounded-off values of Cp for MoSzat temperatures given below:

Temperature,"K ••••••.• deg •••••••. 20 0.28 30 0.63 40 1.12 50 1.74 60 2.46 70 3.24

of 20 to 900K are
80 4.07 90 4.97

Cpo

cal/mole·

Entropy of Mo~. From the heat-capacity data of Andersen 189/. Kelley /37/ calculated the entropy as J = 1.04 (extrapolated). -8:",.. 14.00 (measured) and = 15.0 ± 0.2 cal/mole' deg. Rossini and coworkers /21/ give the value S~a = 15.1 e. u, Smith and co-workers /85/ calculated the entropy of solid Mo~ from their data on the heat capacity of Mo~ from 20 to 90 K and obtained the following results:

S;,.

S:.

S:..
90 2.71

Temperature, • Entropy

'K

•..

• • . • • • • •. deg ••••.

20 0.140

30 0.315

40

50

60 1.25

70 1.69

80 2.17

S~,

cal/rnole·

0.560 0.870

Free

energy

function
T

of MoSa. Table 92 contains the values of calculated by Smith et aI. /65/, according ==-

the functions GI' and of HT-a:, to equation

.. =T

F;-H;

~-ifo
T

+s;..
-

H eat 0 f for mat ion 0 f Mo~. The heat of formation of molybdenum disulfide was calculated from the fOllowingequation:

An;

= - 57640 + 6.85T 5.60.IO-arJ -

0.503 .10'1· •

and is lJf~. = -56,270 cal/mole. The foregoing equation was derived by Kelley /93/ on the basis of results obtained by Parravano and Malquori /94/. Makolkin /95/ determined the heat of formation of MoSzas All:'. = 55,930 cal/mole by studies of the 'electromotive force of galvanic cells. In another study. using analogous methods of measurement for the reaction Mo(s) + 2S(rh) = MOSz (5), Makolkin /96/ obtained the value faH~ = -55,910 cal/mole. 69

Rossini and co-workers /21/ give the heat of formation of Mo~ (s) as -55,500 cal/mole. Entropy of formation of Mo~. Makolkin /95/ determined the entropy of formation of Mo~ experimentally and found t.S~9a = -6.608 cal Zdeg- mole. In his reference book Kelley /93/ gives t.S~98 = -7.0 cal Zmole : deg.
TABLE 92 HO -Ho T 0 in cat/mole T

Functions.'and

. deg. for solid MoS2 /65/

T.°l(

.'
0.055 0.110 0.19 0.29

HT-H~ T

20 30
40 50

0.085 0.205 0.37 0.58

T. 01(

.'
0·.42 0.57 0.74 0.93

HT-H~ T

60

80 90

70

0.83 1.12 1.43 1.78

Free energy of formation of Mo~. From their results on the pressure of dissociation of Mo~, Zelikman and Krein /87/ calculated the free energy of formation of this compound at various temperatures. The calculated results are given below:
Temperature, Free energy

·c
-A

800 cat/mole ...•..•..• 43140

900 37730

1000 35480

1100 29800

F;"

The equation for the variation of the free energy of formation of Mo~ with temperature according to the equation Mo (s) + 2S(rh) = Mo~ (s) was derived by Kelley /93/ from the experimental results of Parravano and Malquori /94/ and from data on the heat capacity of Mo~:
AF;=

-57,640-15.78TlogT+

5.60·10-3T2(I)

0.252· 1OST-l+ 49.24T.

Makolkin /95/ determined the emf of the galvanic cell Pt(~)KCl<0.01 N)II KCl(O.Ol N) /~S/Mo~, and obtained the value AF~98 = -53,960 cal/mole. Rossini et al, /21/ give the value t.F~98 = -53.8 kcal/mole. The equation for the free energy of formation of Mo~ from molybdenum and gaseous sulfur can be obtained from Kelley's equation (I) above, by allowing for the free energy change for the sublimation of sulfur: 2S (rh) =S2 (g). The free energy of formation of this reaction is:
AF~

31,360-1.36T

logT+ 5.8' 10-3T2-38.62T.

(II)

Subtracting equation (II) from (I) gives Mo (s) + ~ (g)

AF~= -89,000-14.42T

= Mo~ (s),
(III)

log.T-0.2· 10-3T2 + 87.86 T.

70

Richardson and J effes /97/ give the followingequation for the free energy of formation of molybdenum disulfide from its elements Mo (s) + ~ :: MoSz(s) from 1073 to 1373"K:
AF~

-52,560 + 10.2T cal/mole.

Richardson and J effes /97/ estimate the accuracy of this equation as ±10%. We consider that the equation of Kelley 193/ for .AF; of M~ is the best.

Molybdenum trisulfide MoSs (At = 192.148) Vapor pressure of MoSs. Parravano and Malquori 194/ studied the reaction 2MoSs:: 2M~ + ~ (g) from 628 to 691"K. The authors calculated partial pressures from equations for the reactions Sa(g) :: 4Sz(g) and S6(g) = 3Sz(g) and the results of these calculations are shown in Table 93.
TABLE 93

Dissociation pressw:e of MoS3 /94/ Temperature, "K

Toral Ptot. pressure atm. Vapor pressure sulfur PS2 6.86'10-4 3.37'10-3 1.20'10-2 of

628 663 691

5.26'10-3 3. 79'10-2 2.35'10-1

En t r 0 p y 0 f MoSs. The entropy of solid MoSswas calculated by Kelley /37/ from 6S for the reaction of formation of MoSs. Its value is given by s:', ::15.9 ± 1.0 kcal/mole· deg. He at of forma tion of MoSs. Using the results of Parravano and Malquori /941 and data for the reaction MC' 35(rh) = MoSs, Kelley 1931 + calculated the following approximate equation for the heat of formation of MoSsAH;= -60,440-3.5T. The heat of formation from this equation is given by A1f:":: -61,480 cal/mole. Rossini et al./211 give the heat of formation of MoSsfrom its elements as AH:', = -61,200 cal/mole. Entropy of formation of MoSs. According to Kelley 193/, the entropy change for the reaction Mo + 3S (rh) = MoSs(s) is given by = -13.8 cal/mole· deg. Free energy of formation of MoSs. Kelley /931 derived the approximate equation AFJ = -60,440 + 8.1 T 10gT-9. 78 T for reaction Mo + 3S(rh) = MoSs. It leads to A.F:" = - 57,380 call mole.

.AS:'

MOlybdenumsesquisulfide M~Ss (M = 288.098)

S:'.

Entropy of M~Ss. According to McCabe 198/, of MazSsis 28.0 ± 2.0 cal/mole. deg.

the standard entropy

71