Shakhov
CHEMICAL
THERMODYNAMICS
IN NONFERROUS
METALLURGY
(Khimicheskaya termodinamika v tsvemoi metallurgii)
Vol. HI
A Reference Book
Metallurgizdat
Gosudarstvennoe Nauchno-Teldmicheskoe
Copyright _ 1965
Israel Program for Scientific Translations Ltd.
IPST Cat. No. 1394
$6.00
IX/18
TABLE OF CONTENTS
Page
PREFACE ............................................ ix
111
i.
Page
iv
Page
vi
EXPLANATORY
LISTOFABBREVIATIONS
OFU.S.S.R. INSTITUTIONS
AND JOURNALS APPEARING IN THIS TEXT
vii
PREFACE
Inthe periodbetweenthepublicationof the secondandthird volumesof
thepresentwork, theXXII Congressof the CommunistPartyof the Soviet
Unionadopteda newprogramcontainingdirectivesfor developing andad-
vancingtheproductionof light, nonferrousandrare metals.
Thepublicationof this referencebook, whichdealswith bothproduc-
tion technology andproperties of thesemetals, shouldbe of assistance
in this task.
Thethird volumeof the presentmanualcontainsdataonthe thermo-
dynamicpropertiesof tungsten,molybdenum, titanium,zirconium,niobium,
andtantalum.
Thechaptersontungsten,molybdenum, titanium, andzirconiumwere
preparedby A.L. Lomov,andthoseonniobiumandtantalumby V.I.
Lavrent'ev.
Critical commentsonthebookandsuggestions concerningits contentsor
pr_esentation of the datashouldbe sentto thepublishinghouse. Theywill be
takeninto considerationin subsequent editionsof this manual.
ix
Chapter 1
TABLE 1
Density of tungsten
For ed Drawn
TABLE 3
3200 /
14,600 1960 Waidner, Burgess
3o8o f
14,600 2900 1910 W artenberg
2974 "l
14,500 1911 Forsythe
3027 /
Worthing /24/ compared his data with the data of the authors shown in
Table 3, with the exception of those of Waidner and Burgess,and calculated
the melting point of tungsten for the radiation constants Cs 14350 and 14300.
The results of these calculations are shown in Table 4.
TABLE 4
Radiation constant C,
Author
14,350 14,300
Luckey /25/ found the following values of melting points for tungsten in
a nitrogen atmosphere under various pressures. He melted tungsten elec-
trodes in an electric arc.
TABLE 5
TABLE 6
Mackay 1331
Kubaschewski and Evans ]27/ consider the boiling point of tungsten to
and Sinke /29 ] the boiling point of tungsten is 6203 ° and 5800°K, respectively,
TABLE 7
Langmuir / 3 5[ found the following values for the vapor pressures of tungsten.
The vapor pressure was calculated from the rate of evaporation in vacuo,
Langmuir, working with Jones and Mackay /33], later corrected his
own data /35/ and also converted the pressures from mmHg to bars.
TABLE 8
Langmuir derived the following equation for the vapor pressure of tung-
sten:
Temperat_e, °C .... 3990 4337 4507 4690 4886 5007 5168 5403 5666 5927
Kubaschewski and Evans /27/ suggested the following equation for the
variation of the vapor pressure of tungsten with temperature, valid from
2000 to 3500 °. 42000
* log P (mm Hg)= -- _ --0.146 log T-
The data of Stull /29/ are the most reliable, since they were compiled
by this author from numerous data obtained by other workers. We recom-
mend the Kubaschewski-Evans equation /27/ for the calculation of the vapor
pressure of solid tungsten.
TABLE 9
Average specific
Temperature Year Author Reference
heat capacity
range, "C
eal/deg-g
TABLE 10
TABLE 11
True specific
Temperature
heat capacity Year Author Reference
"C OK cal/deg.g
The average and true atomic heat capacities of tungsten are presented
TABLE 12
Average atomic
TABLE 13
Tree atomic
°C °K % %
0 -- 6.78 -- 1926 l
450 -- 7.25 -- 1926 Magnus, Danz /46/
900 -- 7.72 -- 1926
300 -- 6.150 --
500 -- 6.325 --
700 -- 6.500 --
1600 -- 7.240 --
Kelley /50/ proposed the following heat capacity values for solid tungsten
at low temperatures.
Atomic heat capacity, Cp cal/g-at, deg (0.02) 0. 21 1.47 3.90 5.00 5.51 5.97
tungsten as an ideal monatomic gas from 288 to 3000°K (Stull and Sinke /29/).
TABLE 14
According to Rossini et al. /51/, the molar heat capacities of solid and
liquid tungsten are 5.97 and 5.0903 cal/mole, deg., respectively. These
values are very close to the molar heat capacity values of Stull and Sinke
The following equations were derived for the specific and atomic heat ca-
Jaeger and Rosenbohm /49/ propose the following equations for the spe-
cific and atomic heat capacities of tungsten for temperatures of 0°C and
above.
cp =0.03199 + 0.04848 • 10-4/-- 0.1174 • 10-°#,
Kelley /54/ recommends using the following equation for the calculation
more accurate results than the equations of Magnus and Holzmann /53/ and
Langmuir, and Mackay ]33] on tbe heat of fusion of tungsten, which were
other hand, show very good agreement; Stull and ,_inke /29/ propose the
proposed by Stull and Sinke /29/ (8420 cal]g-atom) as the most reliable.
TABLE 15
Table 16 shows the most reliable values for the heat of vaporization of
TABLE 16
25
5929 199638
176018 } 1935 KeUey 1341
Langmuir /30/ derived the following equation for the variation of the
tungsten, Kelley /34/ derived the following equation for the change of heat
capacity of tungsten as a function of temperature:
TABLE 17
Rossini et al. /51/ give the following value: AF°ga= 191.6 kcal/g, atom.
* [Referred to in the Russian original as "Isobaric potential", represented by the symbol "Z" .]
10
Table18gives log P and the free energy of sublimation of solid tungsten
from 298 to 3000°K /29/.
TABLE 18
at Q. L
.I I I t
TABLE 19
o o o o
r. *K HO -- HOgs r. .I( Hr -- H 29S r. "K Hr--Hns
cal/g- atom cal/g, atom cal/g, atom
* According to Lange /45/, one bar denotes an accuracy of up to _0.7 cal/g, atom, whereas two bars denote
a higher accuracy.
11
The enthalpies of solid tungsten from 288 to 2000°K are calculated ac-
cording to the following equation:
TABLE 20
Enthalpy Enthalpy
0 0 0 0
HF --//298 HT -- H298
12
TABLE 21
Year Autho_
Solid mns_um
Gaseous Illn_e/l
40.7
I 1, 0 I To,
m. 1 /62/
TABLE 22
cal/g-atom deg
Solid mnssten
Gaseous ningsten
41.5,52
41-56"0-01 [ 1952
19_0 I Rossini
Kelley et al I /51/
/501
TABLE 23
Entropies of umgsten
13
It is more commonly referred to as "the free energy function". These
values are given for tungsten in Table 25. The free energy function values
in the second column refer to solid tungsten, those in the third column to
ideal monoatomic gaseous tungsten.
TABLE 24
s T ST sT
TABLE 25
;_r--n_gs Fr-n_gs
T. oK T. eK T. eK
2. OXIDES OF TUNGSTEN
At present, the following oxides of tungsten are known: WO_, WOs, in-
termediate oxides WO2.72 (WlBO_) or 13 WO 3 • 5 WO 2 and WO2.9(W20OsB } or
18 wch. 2 wov
These data of Vasil'eva, Gerasimov, and Simanov /63/ are in good
agreement with those of Glemser and Sauer /64/, who found the following
compounds in the W--O system.
14
WO s- WO2.gS , _ phase,
WO2.n--W02.88, _ phase,
WO2.Ts-- WO2.sS, 7 phase,
WO_.o3--WOz, 6 phase.
3w_ (s)--*
w (s)+ 2wo3 (g).
The authors used this equation for calculation of the standard thermodynam-
ic data of WO z. The accuracy of this equation is _3%. It was derived by
using the value of Cen s for WO._, according to Venturini /72/, the values for
C_ for solid bodies at their transition temperatures, and the average equa-
tions for the oxides UO_/73/, VO 2/27/, and Th02/27/, whose values ofCpm s
are close to that of WO 2.
15
b
compound was calculated by Blackburn et al. /74/, who measured the vapor
/75/, is S_9 B = 17.1± 1.0e.u. Gerasimov et al. /76/ calculated the entropy
$9°98 = 15.0± 1.5 e.u. for WO2, using the entropies of tungsten (S_98), accord-
ing to Clusius and Zosine /77/, and of 02, according to Kelley /78/. Griffis
/79/ gives the value S_9 B = 19.7+ 1 e.u. Kubaschewski and Evans /27/ con-
sider the value S2°0a = 15± 2.5 e.u. to be the most reliable for WO 2. This
absolute entropy value for WO 2 and also the value S_gB = 15,0+ 1.5 e.u.
of formation of WO2(s ) are given in Table 26. It can be seen from this table
that the results, particularly those obtained in the last few years, are in
good agreement.
TABLE 26
Heat of formation--
Method Year Author Reference
AH298 kcal/mole
TABLE 2'/
Heat of formation
16
Alterthum and Koreff /68/ calculated the heat of formation of gaseous
WO 2 for the reaction W(s) + O 2 = WO2 (g). This calculation, taking into
account also the heat of vaporization of WO_, gives 82.6 kcal/mole as the
result.
Entropy of formation of WO z. Brewer /71/ considers the value
AS° e = -41.0 cal/mole- degrees as the most reliable for the entropy of for-
mation of WO 2 (s).
Gerasimov and co-workers /76/ calculated the entropy of formation of
solid WO_ from emf data. Their value, AS_ = -41.7 • 1.5 e.u., is in good
agreement with that of Brewer /71/.
Free energy of formation of WO_. Brewer /71/ considers the
value bF°l = -122 kcal/mole for the free energy of formation of solid WO_
as the most reliable. The corresponding value of Gerasimov et al. /76/,
obtained by emf measurements ( AF°_, = -124.0 _ 2 kcal/mole), is very close
to that of Brewer /71/.
Kubaschewski and Evans give /27/ the following temperature variation
for the free energy for the equation W (s)+ 02 (g) = WO_ (s)
17
Temperature of sublimation of WO3. The temperature of the "
beginning of sublimation was determined by W6hler and Baltz /69/. Accord-
ing to these authors, this temperature is between 800 and 900 ° . The tem-
perature of the beginning of sublimation was more accurately determined
by Meerson /70/, i.e., 850 ° . Jaeger and Germs /89/ showed that at 1200 °
35% of WO s sublimes within ten minutes. According to Rossini /51/, the
sublimation temperature of WO 3 is 1102 ° at a pressure of 0.0058 mm Hg.
Vapor pressure of WO 3.
Temperature, °K ......... 933 1026 1175 1253 1353 1460 1508 1630" 2000**
Vapor pressure, mm Hg .... 0.0193 0.206 3.23 9.09 41.1 144.0 294.0 760 760
Average specific heat capacities, cal/g • deg ...... 0.0442 0.0678 0.0783
TABLE 28
Temperature. °K
Cdet, Ccale,
Molar Heat Capacity, cal/degree • mole... (0.06) (0.82) (3.15) 7.76 11.91 15.11 19.50
Kubaschewski and Evans /27/ consider the accuracy of this formula for
the above range to be 6%.
• Extrapolated.
• * Calculated by Born/90/.
18
In their calculations of the thermodynamic parameters of _-WO_ Gera-
sirnov and co-workers used the following equation /95/:
which was derived by Sawada /92/. This expression may also be used for
the calculation of AH°,, A_,, and AS °0s of tungsten trioxide.
Rossini and co-workers /51/ give the value Cp = 19.48 cal/mole.degree
for the molar heat capacity of tungsten.
Heat of vaporization of WO s. The beat of vaporization of WO s
at 1 arm., as given by. Born /90/, is 49 kcal/mole. This value, as calcu-
lated by Alterthum 117/ according to Trouton's rule, is 40.64kcal/mole.
Heat of sublimation of WO s. The heat of sublimation of WO a is
approximately 122.0 and 109.0 kcal/mole at 25 ° and at the melting point
(1473 °) /5/, resvectively. According to Vyeno ]93], L_ubi = ll2.6kcal/mole
at 1368.1°K.
Rossini /51/ gives the following value for the heat of sublimation of WOs:
Lmbl = 112 kcal/mole at 1102 ° and 0.0058 mm Hg.
Ent_ropy of sublimation of WO s. The entropy of sublimation of
WO s is ASmbl = 81 cal/deg-mole at 1102 ° and 0.0058 mm Hg. According to
Vyeno /93/, _mbl = 58.4 cal/degree.mole at 1368.1°K.
Free energy of sublimation of WO s. According to Vyeno/93/o
the free energyofsublimationofWOs is &F_8 = 95.2 kcal/mole. At 1368.1°K,
AF=b_ 32.7 kcal/mole.
Energy of dissociation of WO s. The energy of dissociation of
gaseous WO s into atoms at 0_K is Do = 465 + 7 kcal/mole /71/.
Entropy of WO s. Vasil,eva, Gerasimov, and Simanov /94/, /95/
calculated the values for the standard entropies of a- and _-WO s to be _ =
20.0 e.u. and S_ = 17.6 e.u., respectively. These data are in good agree-
ment with the values found by other authors. Thus, Seltz et al. ]103] de-
termined the standard entropy at 250C as S098 = 19.9 e.u. Rossini and co-
workers /51/ and also Kubaschewski and Evans /27/ obtained the same
value for the standard entropy of WO s. The latter authors consider the
value 19.9 e.u. to be accurate within + 0.2 e. u.
Heat of formation of WO s. Table 29 gives experimental data of
various authors for the heat of formation of WO s from simple compounds.
Table 30 gives the most reliable values for the heat of formation of WO a
from simple compounds.
In the opinion of Gerasimov and Vasilleva /102/ the most reliable value
for the heat of formation of WO s is A?/_a = -200.2 kcal/mole.
We recommend this value for thermodynamic calculations.
The heat of formation of WO$ from simpler compounds is given with a
fair degree of accuracy by the following equation:
19
TABLE 29
Heat of formation of WO 3
Heat of formation,
A 1"i998 Method Year Author Reference
kcal/mole
Heterogeneous equitibrium
193 ± 1 1958 Grt ffis 1751
H 2- W-- WO 2- H20 for WO2.90
TABLE 30
Heat of formation
Year Author Reference
4/'/298, kcal/mole
2O
TABLE 31
Entropy of formation of WO 3
gasil'eva, Gerarimov
61.6" 1960 /94/
and S hnanov
TABLE 32
* B-W03.
,,,,a_W03.
Kubaschewski and Evans /27/ give the following equation for the tem-
perature variation of
3. SULFIDES OF TUNGSTEN
21
Temperature of decomposition of WS 2. Picon /105/heated
WS 2 to 1100 ° in vacuo and did not observe any changes in the composition
of this compound. At 1200 °, however, approximately a 60% loss in the
sulfur content was observed. A complete decomposition of WS_ was ob-
served at 2000 °.
Vapor pressure of WS 2. No data are available.
Heat capacity of WS_. No data are available.
Entropy of WS 2. Rossini /51/ gives the following values for the ab-
solute entropy of WS2: S°29a--23 cal/mole • degree. According to Kubaschew
ski and Evans /27/, the absolute entropy value S%s for WS1.95-2.00 is
22.4 ± 3.0 cal/mole- degree.
Heat of formation of WS 2. Table 33 shows tentative values for
the heat of formation of WS 2 from its elements,
TABLE 33
Heat formation'of WS 2
Heat of formation
Author P_fel:ence
--AH098 kcal/mole Year
Kubaschewski and Evans /27/ gave the same equation and showed that
its accuracy is +8 cal.
4. HALIDES OF TUNGSTEN
1394
22
Boiling point of WF 6. Barber and Cady 11081 determined the boil-
ing point from the pressure-temperature curve for liquid WF 6 to be 17.06
0.05 °. This value is somewhat lower than that reported by Ruff and Ascher
(17.5 =) 11381.
Kelley /34/ gives the boiling point of WF e as 290.4°K, Kubaschewski and
Evans /27/, as 17_C.
Table 34
Vapor presmre of WF 6
928.580 67942.9
log P (ram Hg) = 6.88699
T T=
Vapor pressure, aun ..... 0.0001 n001 0.01 0.1 0.25 0.5 1.00
Stull /28/ quotes Ruff and Aseher /138/ and Kelley /34/ and gives values
for the vapor pressure for WFs, which differ only slightly from those of
Kelley /34/.
Temperature, *C..... -71.4 -56.5 -49.2 -41.5 -33.0 -27.5 -20.3 -10.0 +1.2 17.3
Barber and Cady /108/ claim that the data of Ruff and Ascher /138/ for
the vapor pressures of solid WF 6 obey, fairly accurately, the following equa-
tions:
23
Heat of transition of WF 6. Barber and Cady ]108] calculated a
value of 1600 ± 300 cal]mole from a plot of logP as a function of T, based
on their own experimental results. The same authors calculated the tem-
perature of transition of WF 6 from the data of Ruff and Ascher ]138] for
logP_ f(T) and found the value Ltrans = 2290 cal/mole. Although the last
value is of the order of 1600 cal/mole, it is probably too high.
Rossini ]51 ] considers as the most reliable the value for the heat of
transition of WFs, as reported by Barber and Cady (1600 cal]mole) /108/.
Entropy of transition of WF 6. Rossini ]51/ gives the entropy
of transition of solid WF 6 as 6.0 cal]deg, mole.
Heat of fusion of WF 8. The heat of fusion of solid WFs was deter-
mined by Barber and Cady ]108]. They calculated this value from the
slope of the line logP = _(_)as 500±100 cal/mole. The same authors
]108] used the data of Ruff and Ascher ]138] and the same method to cal-
culate the heat of fusion of WF 6 as 510 cal]mole,
From vapor pressure data of WF 6 a value of 1800 cal was calculated
for the heat of fusion of WF 8 ]109]. Kubaschewski and Evans ]27/ Calcu-
lated from this result an approximate value of 500 cal/mole for the [molar]
heat of fusion of WF 6. Rossini ]51] also gives the value of 500 cal/mole.
Entropy of fusion of WF 6. The entropy of WF 6 is 1.8 cal]mole.
degree ]51].
Heat capacity change of WF 6 during vaporization. The
heat capacity change of WF e during vaporization is
In the derivation of this equation Kelley ]34/ utilized the data of Ruff
and Ascher ]138] on the vapor pressure of WF 6.
Entropy of vaporization of WF 6. According to Kelley ]34/,
the entropy of vaporization is AS 290.4 = 21.9 cal]degree, mole.
Free energy change of vaporization of WF 6. The free
energy change of vaporization of WF 6 is AF°gs = -166 cal/mole. &Fas a
function of T is expressed by the following equation ]34]:
* [ProbablyAF_ is meant.]
24
The free energy change of sublimation of WF s. The free
energy change of sublimation of WF s is calculated by the equation /24/:
and A/_ = 129 _ 4 kcal, and AS = 145 ± 4 e.u. for reaction (2).
and WCI= (s) + 2WCI s (g) = 3WC14 (g) from 450 to 600".
The heats of these two reactions are 66 _ 4 kcal and 50 ± 4 kcal [per
mole], respectively.
The entropy of the first reaction is _= 90± 4 e.u. and is AS= 60± 4
e.u. for the second reaction. These data were reported by S_chukarev and
co-workers /I 11/.
Heat of formation of WC14. Rosslniet al./51/ give this value as
AH_= -71 kcal/mole.
• [ProbablyAF_ismeanL]
25
Tungsten pentachloride WC15 (M = 361.205)
Melting point of WC15. Roscoe /113/ gives the melting point for
WC15 as 248 °. Shchukarev and Novikov ]112/ obtained the value of 230± 10 °
various authors.
TABLE 35
Both Kubaschewski and Evans /27 ] and Rossini et al. /51/ consider
TABLE 36
* The results are reported in the order in which they were obtained.
26
the boiling point (286°). Kubaschewski and Evans /27/ give an approximate
value of 12.5 kcal/mole at a boiling point of 270 °.
Entropy of vaporization of WCI s. ASvap=28.3± 10e. u, /112/.
Heat of sublimation of WCI s. According to Shchukarevand Novi-
kov /112/, the heat of sublimation of WCI s is 16.7 ± 0.5 kcal.
In another work, Shchukarev and co-workers /111/ found the value 18.5±
0.5 kcal for the sublimation process WC1 s (s) -- WC1s(g ) in the temperature
range 150 to 253 °.
Entropy of sublimation of WCI s. The entropy of sublimation of
WCI s has been given as AS= 30.3 e.u./112/ or AS= 33.1 ± 0.7 e.u. /111/.
Heat of disproportionation of WCI s. Shchukarevandco-work-
ers /111/ found optical-tensometric methods that gaseous tungsten penta-
chloride disproportionates with formation of gaseous tungsten tetrachloride
and tungsten hexachloride.
The disproportionation of tungsten pentacb_loride, according to the equa-
tion 2WC1 s (g) = WC1 s (g) + WC14 (g) in the range 300 to 500 °, is accompanied
by a heat effect AH°98 = 6 kcal /111/.
Entropy of disproportionation of WC1 s. Shchukarevand co-
workers /112/ determined the entropy for the disproportionation equation
2WCls(g ) = WCls(g ) + WCl4(g ) to be _m = 5 e.u.
Heat of formation of WCI s. The heat of formation of WCls AH_ =
-84 kcal/mole /51/.
Shchukarev and Novikov /112/ found by experiment that the vapor pres-
sure of WCI s increases from 43ram Hg at 215 ° to 752mmHg at 341 ° (Table
38).
27
TABLE 37
TABLE 38
38 mm Hg at 226.9 °
233 mm Hg at 284.0 °
760mmHg at 336.5 °
The vapor pressure of a- and _-WCls in the solid state is given by the'
following equations:
and
logP(mmHg) = -3840T "1+ 9.26. (from 500 to 557°K).
28
Shchukarev and Novikov /112/ determined the heat of _raporization of
liquid WCI 6 as 12.6 _ 0.5 kcal.
Rossini /511 gives this value at 336.5 ° as Lvap = 14.9 kca1/mole.
Entropy of vaporization of WCI 6. According to Shchukarevand
Novikov /112/, the entropy of vaporization of WCI s is 20.4 ± 1.0 e.u. This
value was determined from experimental values of vapor pressures. Ros-
sini 151/ considers the best value for the entropy of vaporization of Liquid
WCI s at the temperature 336.5 ° to be 24.4 cal/mole - degree.
Heat of sublimation of WC1 s. _chukarev and Novikov /112/
calculated this value from vapor pressure data for WCls(s ) as Lmbl = 14.6_
0.5 kcal/mole.
Vernon /120/ gives the heat of sublimation of WCIs, calculated from the
vapor pressure of this compound, as 23.8 kcal. Shchukarev and Novlkov
/119/ investigated the process of sublimation by a gravimetric method in
the range 156 to 383 ° and gave the value 13.7 kcal. This value seems to
be the most reliable.
For solid a-WC]_ Kubaschewski and Evans /27/ give the value Lmbl =
17.5 _: 1.5 kcal/mole, at a temperature of 226.9 ° and a pressure of 38 mmHg.
Rossini and co-workers /51 / give the value L=b! = 21.0 kcal/mole [for the
same modification under the same conditions]. According to these authors
the heat of sublimation for _-WC1 s at 284 ° and 233mm HE is 17.4kcal/mole.
Entropy of sublimation of WCI_. The entropy of sublimation of
solid WCls_ as calculated by _chukarev and Novikov, is 24.2 ± 1,0 e.u. This
value was calculated from vapor pressure results. In another lrtudy /119/,
Shchukarev and Novikov used a gravimetric _nethod for the study of the sub-
limation of WC] s and determined the entropy of this compound as 22.5 e.u.
According to Rossini /51/, the sublimation ofa-WCl s is accompanied by
an entropy change, ASmbl, of 42.0 cal/mole, degree at 226,9". The corre-
sponding entropy change for _-WC16 is 31.2 cal/mole" degree at 284 °.
Heat of dissociation of. WC1 e. The heat of dissoclation of WC_
from 1087 to 1727 ° is 9000 cal/mole. The values of the lmartial pressure
of CI_ and the equilibrium constants K - _" for the dissociation of this
Pw¢_
compound are given in Table 39 /120/.
TABLE 39
D_oci_ion of WCI6
(P_ial pressure of CI 2 and equillb_ium r._m_,_mt)
29
i
Tungsten bromides
WBr 2 ................ 19
WBr 4 ................ 35
WBr5 ................ 42
WBr 6 ................ 44
Tungsten iodides
AH_S,
kcal/mole
WI 2 ................. -1
WI4 ................. 0
WI5 ................. +27
5. CARBIDES OF TUNGSTEN
Density of W2C. Becker /121/ calculated from X-ray data the density
of this compound at room temperature and obtained the value 17.15 g/cm 3.
Molar volume of W2C. According to Becker /121/, the molar vol-
ume of W2C is 22.1 cmS/mole.
Hardness of W2C. WzC is harder than corundum (it scratches co-
rundum).
Temperature of transition of W2C. Tungsten carbide W2C is
converted from the a- to the fl-modification at 2300 -- 2400 °.
Melting point of WzC. Table 40 shows the melting point of W2C
according to various workers.
TABLE 40
3O
Tungsten monocarbide WC (Af = 195.931)
TABLE41
Heat of fmmatica of WC
Heat of fm:ma_en
Tear Autho_ Reference
--&H0 kcal/mole
aF r = --9100 + 0.47".
The temperature range of this equation is 298 to 20O0°K, and its accuracy
is not less than + 3 kcal.
The heterogeneous equilibria (WO s + Ha) and (WO s + CO) were studied
by W6hler andGiinther /129/, VanLiempt/80/, Relnders and Vervloet /130/,
31
Shibata, W6hler, and Kunst /81, 131/, and others. The main object of
these studies was the determination of the equilibrium and the investigation
of phase change on the reduction isotherms of WO s. The equilibrium con-
stants, Kp, however, were not determined by sufficiently accurate methods
and the authors ]129, 80, 130, 81, 131/ did not take into account the varia-
tion of the heat capacity of WO s with temperature. As a result, the values
obtained for/(p show differences which may be as high as 40%.
Moreover, the authors did not identify by X-ray methods either the initial
reactant WOs, or the intermediate oxides WO2.90 and WO2.Tz , formed as a
result of reduction of WO s. This is one of the causes of the wide discrepan-
cies of the data.
Thus, Shibata /81/, when studying the equilibrium of tungsten oxides
with a mixture of CO 2 + CO, erroneously assumed the reaction equation as
2WO s + CO _ W205 + CO 2 and calculated the thermodynamic parameters for
W20 s. Later investigations did not confirm the existence of this compound.
W6hler and Gtinther /129/, Shibata /81/, Reinders and Vervloet /130/,
and other authors observed in the study of the reaction (WO$ + H2) three
stages of reduction:
2) W,O5
3) 1 WO,
+ H,
+ H,
= 2WO=
= 1 W+ +H20,
HzO, IA)
2 2
2) 1 W,O.
3) 1 WOs +
+ H2 =
H2 =
± WO2 +
3
12 W + HiD.
H20,
I (B)
Schenk and Dingman /144/ studied the reduction equation (WC_ + CO) and
attributed the formula WsO 8 to the intermediate oxide.
Funaki and Acada /145/ observed seven stages of reduction of tungsten
trioxide:
The equilibrium constant obtained by WShler and Gtinther /129/ and the
variation of log Kp with temperature are presented in Table 42.
32
TABLE 42
850
logKps = --_-- + 1.059;
These equations differ only slightly from those obtained by W6hler and
Gfinther in their earlier work /129/. The experiments were performed
very carefully. The flaws in this method were apparently those inherent
in the static method; also, no X-ray studies of WO s or its reduction prod-
ucts were conducted.
Chaudron /146/ studied the reaction (WO s + I{2) at lower temperatures
(_400 °) than W6hler et al. /129, 131/. Chaudron /146/, like W5hler and
G/inther /129/, observed three stages of reduction of WO s. On the basis
of the data of Chaudron/146/, VanLiempt /143/ derived the following equa-
tions for each reduction stage:
2468
logKp,= - _ + 3.15;
loggps=_ + 0.845.
111._...._1
T
33
J
t
For the sake of comparison, Table 43 shows the values for the three
These values were determined from the linear equation of log Kp as a func-
tion of I which VanLiempt [143/ derived from the data of Chaudron / 146],
T
and also from those calculated from the equations of W6hler and Giinther
TABLE 43
Temperature_ "K
Author Reference
Stage 973110731117311273*
Kp
W6hler, Shibata,
11311
Kunst
WShler 9 Shibata,
1.53 1.85 2.16 2.46 /131/
Kunst
It can be seen from this table that the results of W/_hler, Shibata, and
Kunst /131/ and those of W6hler and Gfinther /129/ show good agreement
tion six lower oxides of tungsten were found, namely:W4Ou, W20 s, W409,
WO2, W203, and WO. These authors /145/ obtained two reduction isotherms
of tungsten trioxide at 870 and 700 °. Table 44 shows the equilibrium con-
with hydrogen at 700 °. For comparison, this table also contains the equi-
librium constants of W6hler /129, 131/ (reaction scheme A), and those of
Smithells /142/ (reaction scheme B). In addition, the table also shows the
equations for log Kp = [ (_--) for the reduction reaction (WO a + H2) as deter-
obtained by Funaki and Acada ]145] for one stage (particularly the second),
sometimes show discrepancies greater than 35%. For this reason the equa-
34
somewhat inaccurate. Despite, therefore, their very interesting method
of investigation, the values obtained by these authors for the equilibrium
constants cannot be used for calculation of the thermodynamic functions
of the oxides of tungsten.
TABLE 44
6.06
6.58 1933
5.75 Kp,=6.115 _p, = 6. ! 15 logKp = - _ + 2.765
6.39
3.55
2.67 798.5
2.50 Kh=3.49 logK_----- -- -7--¥ 1.398
2.33
g_=2.73
.£ 2.45
2.30 ogX =-
596
l 29.8
K_,=2.26
Ks,,== 2.33-
! 17.2
WOt 2.19
ogXp= - -7- +0m4
1.29 1810
0.456
0.,914
Kp -----0.667 LogX_=- -r- + ! ._s
2383
0.379
WO 0.370 Kp=0.37o ff_=O .579 gh=0.519
2352
Kp -----0.3_
35
The equilibria a- and _-WO 3 + H 2 /76, 94, 95, 132/
For the four stages of reduction of _-WO s by hydrogen the mean values
of the equilibrium constant Kp were obtained. These values are given in
Table 45.
TABLE 45
I Stage II Stage
961 2.60
965 2.78
1023 4.91
1064 7.64
1) logKpl = 379'2.0
r b 4,8268,
z_.s + 1.684,
2) logKp.==-
2219.0
4) log Kplv =ffi T {- 1.5809.
The mean experimental error range for the first two equations is ±3%,
for the third ±1.5%, and for the fourth _1%.
36
Equilibrium of the reaction (J3-WO 3 + H2), 630 to 791 °
4soe.s _. 5.10866,
2) logK_l = r
3) log Kpm --
9o4.m
r
I-o.9o60,
r_s t-1.650.
4) log gpl v = T
The mean error of the first two equations is within 2%, while that of the
second two is within 0.6%.
The authors combined the reactions of the four stages of reduction and
obtained equations for the equilibrium constants and for the free energy for
complete reduction according to the equation:
=- WO= -{-3H= _.W -{-31"I=O
(v)
I+ If+ Ill+ IV -- V:
5654
V. logKpv .... + 4.56
T
hence,
Al_r.v = 25,870 - 20.89T.
TABLE 46
a- WO 3+ H 2 _- WO 3+ H2
37
Vasil'eva, Gerasimov, and Simanov /94, 95/ used the data of Chipman
/133/ for the formation of water vapor to calculate the free energy of for-
mation &F of a- and fl- WO s from their elements.
l
H, + ¥ O. = H,O. (VI)
VI. o
AFr.vl- _ -59,251 + 0.871T lnT-0.0475T 2 + _40,800 + 6,8085T.
T
3 = "-WOa;
W +-_-0,
3 0 (vii)
w+-]- , = p-wo,
Vll.aF_..vu= 3AF_-.vl--AF_.v •
1
The values of AFt° for the reaction (V1) H_ + _-02 = I-_O and (VII) W+ _ 02 =
a-W02, at the temperatures of the experiment, are given in Table 47, and
3
for the reaction (VII) W + -_ 02 = fl-W02 in Table 48.
TABLE 47 TABLE 48
Free energy of formation of 3H20 and a-WO 3 Free energy of formation of/3-WO 3
In the calculation of the free energy of fl-W02 the following forms of the
Cp- r(T)reactions were used:
0.90. I{_
forO_ Cp == 7.52 + 0.81-10 -s T- _ /134/;
Using the method of Temkin and Shvartsman /135/, which obviates the
necessity of calculations, the integration constant J and AH in the equation
AF_=[(T), Vasil'eva, Gerasimov, and Simanov /94, 95/ calculated thermo-
dynamic parameters for the formation of a- and fl-WO 3 from their elements
3 3
according to the equations W + _- O 2 = a-WO s and W +-_-O_ = fl-W02, under
standard conditions :
38
w + _0, = p.wo_
3
For the reaction W + _ (3= = a-WE)t, the variation of AF_ with T is given
by the equation
VIII. AFt= -203,000 + 61.6T- (- 0.574Me+
TABLE 49
Free energy
-aFT, kcal]mot¢
873 1`51.0
923 148.0
1023 142.6
1073 139.8
39
The values for AF_ of Table 49 do not differ from those of Table 47 by
more than 0.5% and the values of Table 50 agree with those of Table 48
within 0.3%.
Thus, the equilibrium constants of the reduction of tungsten oxides by
hydrogen permit calculation of the thermodynamic functions of the forma-
tion of WO 3 from its elements.
However, since the high values of equilibrium constants cannot be mea-
sured with sufficient accuracy, and since that accuracy depends on the values
calculated for water vapor, the thermodynamic functions of the formation
of tungsten oxides from their elements must be independently determined.
For the reaction
!w
9 + Tt O= = _-wo2
which is valid for experimental data in the temperature range 943 to 1230°K.
The values for AFr°.l , calculated according to this equation over the tem-
perature range 973 to 1273°K, and also those for AFrO' i, calculated by Vasil,-
eva, Gerasimov, and Simanov /132/ from equilibrium data for reaction (13
for the same temperatures, are shown in Table 51.
For the reaction
10o WO 1 10o
T =-{-"_-0= == -_ W0=.72 (I13
This equation governs data from 900 to 1173°K. The values of AFt. u,
calculated from this equation in the range 923 to 1173°K, and the values of
AFr. nfor reaction (II), calculated by Vasil'eva, Gerasimov, and Simanov
]132] from equilibrium data, are shown in Table 52.
TABLE 52
Combination of the solutions of equations (I) and (II) results in the equation
4O
Gerasimov et al./76/ used the heat capacities of O z and W, given by
Britske et al./136/, in his calculation of the standard thermodynamic pa-
rameters. The heat capacity of WO 2 was calculated by the expression
C,p = 17.83 + 1.89.10-ST-3.342 • 10s] `-2 with an accuracy of +3%.
Using these values for the reaction W + O z = WO z Gerasimov et al./761
obtained the equation
where Mo, MI, and Mt are the coefficients of the Temkin-Shvartaman equa-
tion /135/.
Hence,,
A/Fzm = -136.6 _ 2 kcal/mole;
in Table 53.
data for reaction 2 WOa + H_ 2 W. + I_O are reported
TABLE 53
am
41
I
The heat capacity change ACp for the reaction WO2 + 2H2-* W + 2H20
in the range 500 to 1000 ° was calculated from the literature for the heat
capacities of H2, H20 ]27/, W /139], and from Cp = 14.0 cal/deg.mole for
wo2:
ACp= 6.98 -k 4.32" 10-ST - 0.08" 10ST -2.
Using the methods of Z-functions and least squares, the following equa-
tions were obtained from the equilibrium data of Table 53 and fromACp.
From these equations the values AH%s = 19.4 ± 0.2 kcal/mole and AFt%e =
13.9 ± 0.2 kcal/mole were calculated.
From the above values for AF%s and AH_ e /27/ the heat contents and
the free energy for the reaction W + O2 = WO 2 were also calculated and the
following values obtained: AH%e = -135.0 ± 0.3 kcal/mole and AF%a =
-123.1 ± 0.3 kcal/mole. The heat of formation of WO 2 was also obtained
by direct combustion in a bomb calorimeter. The same method also served
for the determination of the heat of combustion of WOs, WO2.72 , and WO2.90.
The heat of formation of WO s as determined by calorimetric measurements
/59] is given below:
--_r/*n|,
kcal/mole
l_.S
W + -_ O,-_ WOs .............
I_.5
I_.I
_.0
WOs -I- ?Os-_ WO= ............. 61.4
_.8
_.3
15.0
W02.7= + --_--0= _ WOa ......... 16.2
17.1
15.8
4.7
0. I0 6.9
WOg.00 ÷ _ Ot _ WO_ ......... 6.2
6.4
These data were used for the calculation of the heats of formation of tung-
sten oxides. The corresponding AH%s,s are shown in Table 54.
The individual standard entropies of W and O 2 ]140/ were utilized to
calculate the standard entropy of WO2, 8_9 s = 17.1 ± 1.0 e.u.
Griffis /79/ also gives the thermodynamic parameters obtained from an
exhaustive study of the heterogeneous equilibrium (WO s + H2) by the static
equilibrium method in an improved apparatus. Griffis noted /79/ that his
earlier measurements /75/ were not sufficiently accurate, since he did not
take into account the effect of thermal diffusion. The data in ]75]* are
more accurate and were used to calculate the standard heats of formation
and entropies of the solid oxides WO2, WO2._, WO2.90 , and WO s.
:-i;-r-obab-l;-/79/ is imcnded.]
42
TABLE 54
wc_.9o 193, I
All data were obtained by alternative reduction and oxidation and are
summarized in Tables 55 -- 58.
TABLE 5,5
Tempera- PH.O
Kp-- PEI_ Tempera-
PHt ture, "C rare, *C
TABLE 56
-M_nPH
Variation of the equilibrium constant _-----_ with temperature
-- ¢°"
Ht
for the system WO2.90-- H 2- WO2.72-- H20
The changes in the heat capacity ACp for the equilibrium reactions were
calculated from the values of Cp for 1_, 1-120, WO s /27/, W /78/, and for
WO_, according to Kopp's rule.
43
TABLE 57
PH,O . .
Variation of the equilibrium constant Kp--_ wltn temperature
• }l s
I I
TABLE 58
°H,._PH
W s -, WO,,
+ -_-O.
A/'/_e , : -- 202.8 J¢- 1.4 kcal/g- atom,
44
1O0
18 WO N• so + Ha --*-_--WO= 79 + HgO" (H)
W+ _ Oz -. WO2.,,,
A/ff2o . ------ 193.1 + 1.4 kcal/g- atom.
leo
?2 WO 2 79 + H= -'* --_--W09 + H20" (Ill)
o.o_.1o_ 28.67".
AF_ = 6110 + 3.35T lnT-- 0,89 X 10-_F2 4 T
-wo, + H. -- t--w
2 + HiD, (IV)
45
It shouldbenotedthatthedataof Griffis /76/ are in good agreement
with those of Vasil_eva, Gerasimov, and Simanov /95/, and the data of the
Soviet authors are reported as being exceptionally accurate.
Morozova and Getskina ]82/ ignited WO2.67 together with benzoic acid
in a high-precision vacuum calorimeter and found its heat of combustion
as AHocoPmb. = 24.8 ± 0.2 kcal/g_formula. This value was used to calculate
the heat of formation of WO2.67 , which is -175.5:1= 0.2 kcal/g, formula.
The heat content and free energy for this reaction, calculated by the
above equations, are, respectively:
46
Chapter 2
Isotope content, _ ..... 15.84 9.04 15.72 16.53 9.46 23.70 9.63
Demarquay /13/ gives the following equations for the temperature de-
pendence of a :
in the range 20 to 1300 °
at = 4.65. lO s + 0.9.10-'t,
47
Edwards and co-workers /14/ determined the thermal expansion of
molybdenum in the temperature range 1100 to 2500°K and derived the fol-
lowing equation
TABLE 60
TABLE 61
We consider 2890°K as the best value for the melting point of molybdenum.
48
TABLE 63
TABLE 64
TABLE 6,5
1400 1.29-10 "15 1.13 • 10"10 38O0 _50" 10"2 5.10" 108
* Boiling point
49
4
The vapor pressure of molybdenum from 1200 to 2500°K was also deter-
mined by Zwikker /29/ and his results are shown in Table 66.
TABLE 66
Tempera- Rate of vaporiza- Vapor pressure, Tempera- Rate of vaporiza- Vapor pressure,
ture, "K tion, g/cm3.sec, mm Hg Ulre_ *K tion, g/cm3-see, mm Hg
Langmuir and Mackay /24/ give the following equations for the rate of
vaporization and the vapor pressure as functions of temperature:
37,040
- + 9.67,
T
5O
o
Kelley /27/ gives the following values for the vapor pressures of liquid
molybdenum:
Stull /20/.
TABLE 67
_75 I 4237 60
1
Figure 1 shows graphically the function log P= f -_ for liquid molybdenum
plotted according to the values of Kelley /27/ and Stu11 /20/. It can be seen
from this figure that the points of Stu11 /20/ fit a straight line better than
those of KeLley /27/. Therefore, we consider the data of Stu11 /20/, which
logpiJ
,.0\ _._ o
iJi
Data of $tull
u[
Z5
X Data of Kelley
2.O
_0 015 O_ 02_ O_ O_ _,
0-'3
I
-&t5
-£0
\l
-£$
51
Heat capacity, heat capacity change during vaporization
authors.
TABLE 68
TABLE 69
52
4
TABLE 69 (continued)
1700 8. 00 9.36
1800 8.18 9.53
swt_ su_ /2z/ s_u, stake /2a/
1900 8.35 27_ 9.70
TABLE 70
53
b
TABLE 71
Cp(g) = 4.97
TABLE 72
1394 54
e
TABLE 73
process.
TABLE 74
_'ubl [
r. oK /_ubl -log Jfp
cal/g • at. -log Kp r..x i cal/g. _t_
55
The variation of the free energy of sublimation of molybdenum with tem-
perature can be expressed by the following equation:
_F:ubl = 155,960-1.66TlogT+
TABLE 75
TABLE 76
56
o
TABLE 77
TABLE 78
T. eX
,..K #-st,,
cal/deg • g-atom ca.U'deg, g-atom
Free energy function. Stull and Sinke /23/ give entropies and
F'--/_s
free energy functions q)#==-- T for solid and gaseous molybdenum
in the temperature range 298 to 3000°K. These values are presented in
Table 79.
TABLE 79
g
cal/de g- g- atom cal/de g- g. atom cal/deg.g.atom cal/deg.g, atom
57
TABLE 79 (continued)
* The two last values refer to the entropy and free energy function of liquid
molybdenum.
8. MOLYBDENUM OXIDES
58
Energy of dissociation of MoO z. Blackburn and co-workers
report /48/that the energy of dissociation, D o, of gaseous MoO= into gas-
eous atomic molybdemtm and oxygen is 284.6 kcaJ/mole at 0=K.
Entropy of MoOr. King /49/ determined the hea_ capacity of MoO=
in the range 51 to 298°K and from his results calculated the standard en-
tropy of this compound, i.e., 8_= 11.06 ± 0.05 cal/deg- mole. According
to Tonosaki /50/° the standard entropy of MoO 2 i8 19.3 cal/deg.mole.
Kubaschewski and Evans /22/ give the standard entropy of MoO= as S_s =
13.6 ± 2.0 cal/deg- mole. The great discrepancies in the values of the ab-
solute entropy of MoO= are evidently due to the difficttlty of determining
the heat capacity of this compound, which'is unstable on heating.
Heat of formation of Moo=. Tonosaki /50/ found the heat of for-
mation AHem of solid MoO 2 to be -131.692 kcal/mole. The heat of forma-
tion of MoO 2 as determined by various authors has the following values:
We consider Mah,s value, AHseu= -140.8 kcal/mole /53/, the most re-
liable.
Entropy of formation of MOO=. Tonosaki /50/ determined the
entropy of formation of MoO= as AS_m = -36.5 cal/deg- mole. Brewer /44/
gives the value ASseu = -36.6 cal/deg- mole.
Free energy of formation of MoO=. The value ofthefree en-
ergy of formation of MOO=, according to /44/, is &F_ ffi -120 kcal/mole
and, according to /50/, AF_m = -120.816 kcal/mole.
The variation of the free energy of formation of Moo= with temperature
according to the reaction Mo (s) + 02 = MoO 2 (s) is expressed by the follow-
ing equation AFt= 140,100 + 4.6TlogT-55.8 T cal, which is valid in the tem-
perature range 298 to 1300°K. The accuracy of the equation is +6 kcal/22/.
59
TABLE 80
Density of MoO 3
21 4.692
-78 4.726 1934 H_ilsm_m, Biltz /55/
-195 4.754
TABLE 81
TABLE 82
1 2 i a 4 $ I 6
6O
o
Temperature. "K .... 973" 1007 1058 1087 1124 II6S 1190 1128 1287 I_ 1424
Ueno /61 / studied the vapor pressure of MoO$ in the range 635 to 675 °,
using a Knudsen effusion cell, and derived the following equation for the
variation of the vapor pressure of solid MoO s with temperature:
Kubaschewski and Evans /22/ quote Ueno's equation /61/ for the vapor
pressure of solid MoOs, but consider the following equation more reliable:
This equation is valid from 298 ° to the melting point. For liquid molybdenum
the same authors give the equation
was derived from vapor pressure curves presented below /62/. These
curves were obtained by measurement of the boiling point of MoO s at fixed
pressures.
61
Temperature, "C Pressure, mm Hg
905 53
960 100
1015 200
1057 300
1100 450
1155" 650
Figure 2 shows the graph of the function log P f 1 for gaseous MoO s.
T
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(a
According to
o Stull
,gO
_'_ X _ x Kelley
4-Kubasehewski and E'_
•_ "%x
N • Zelikman and Gorov
2.0
x\. 'N,qk
_5
¢0
_0
a9 zg_ \_ .o
-a$
\ \
X\_ x
-t.O N k
"4
-£f
+t
Heat capacity, eal/mole .... (0.06) (0.08) (3.16) 7.31 11.04 13.79 17.57
* Extrapolation.
62
From the results of Seltz and co-workers 1641. Kelley 1631 derived the
following equation, valid from 298 to 1068°K, for the variation of the molar
heat capacity of solid molybdenum trioxide:
c r = _3.6 + m.5.10-sr.
Smith and co-workers ]65/ note that the results of Seltz /64/for the
TABLE 83
r, "K cp r. "K cp r, -K cp
cal/mole .deg cal/mole -deg cal/moic -deg
63
TABLE 84
Data on the molar heat capacity of liquid MoO s are given by Cosgrove
and Snyder /60/.
Heat of fusion of MoO s. The first measurements of the heat of
fusion of MoO s were presented by Hoermann /69/ and Groschuff /70/. Kel-
ley /71/ gives the average of these data, i.e., Lfus = 2500 cal. This value,
however, is very low. Cosgrove and Snyder /60/ found by experiment that
the heat of fusion Lfus of MoO s is 12,540 cal/mole. Kubaschewski and Evans
/22/ consider the value 12.55 ± 0.40 kcal/mole to be the most reliable.
Heat of vaporization of .MoO s. The heat of vaporization of MoO s,
according to /62/, is 35.1 kcal/mole.
At its boiling point (1280°), the heat of vaporization LvapOf molybdenum
trioxide is 42.7 5= 4.0 kcal/mole /22/.
Heat of sublimation of MoO s. The experiments 0fUeno /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 MoO s. According to Ueno /61/,
ASsubl = 46.5 cal/mole, deg at 928.1°K. Rossini et al. /21/ give ASsubl =
67 cal/mole, deg at 700 ° .
Free energy of sublimation of MoO s. According to Ueno/61/,
AFsubl = 20.5 kcal/mole at 928.1°K. If the heat and entropy values of sub-
limation of Rossini et al. /21/ are used, the free energy of sublimation at
973°K is AFsubl = 65 --0.067 " 973 = 65 --65.191 = --0.2 kcal/mole.
Heat of dissociation of (MoOs)q. For the dissociation of
(MoOs)s-_ 3 MoO s AH= 220.9 kcal/mole /48/.
Entropy of dissociation of MoOs*. Blackburn andco-workers
/48/ give the energy of dissociation of gaseous MoO s into atomic molyb-
denum and oxygen as D o = 410.3 kcal/mole at 0°K. According to Brewer
]44], the energy of dissociation of gaseous MoO 3 into atoms is 445.0 +
5 kcal/mole at 0°K.
Heat content of MoO s. According to Cosgrove and Snyder /60/,
the heat content of solid molybdenum trioxide is given by the equation:
64
and that of liquid molybdenum trioxide is given by:
TABLE80
En_opy of solidMoO3/651
r.'K r.qg
cal/mot¢ •deg
TABLE 86
T. "K 0 B 1". *g @,
r
65
Heat of formation of MoO s. The heat of formation of MoO s from .
its elements is given in Table 87.
TABLE 87
Heat of formation
Method of determination Year Author Reference
- A H_9 8
kcal/mole
Direct determination at
166.14
constant volume / 1903 Delepine /72/
167.0
Direct determination at !
constant pressure
Calculated from the re-
181.5 action 3Na=O2 nu Mo = 1910 Mixter /73/
NazMoO 4 + 2Na_,O
The most reliable values for the heat of formation of MoO s are the fol-
lowing: AH°98 = -180.3 _: 1.5 kcal/mole /44/, AH°gs= -178.2+l.5kcal/mole
/22/, AH°_8= -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 MoO s. The entropy of formation AS°98
of MOO3, according to Brewer /44/, is -61.5 cal/deg, mole. Smith and co-
workers [65/ give the value AS°gs = -61.75 e.u.
Free energy of formation of MoO s. According to Brewer /44/,
the free energy of formation AF°98 of MoO s is -162 kcal/mole. According
to Smith et al. /65[, AF°98 =-161.92 kcal/mole.
Kubaschewski and Evans /22/ give the following equation of the free en-
9. SULFIDES OF MOLYBDENUM
66
ArtificiaLly prepared molybdenum disulfide (fl-MoSa) has a rhombohedric
structuore. The parameters of the crystal lattice are a = 3.17 A and c =
18.38 A.
The structure of fl-MoS= was first investigated by Bell and Herfert /77/.
The authors assumed that it corresponded to the CdCI 2 structure. Later,
however, /78/, it was shown that the structure of fl-MoS_ is described by
the spatial group R_m m C_. Zelikman and co-workers /79/ studied the
structure of MoR a 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-MoS 2 (molybdenite) and fl-MoS 2. fl-MoS=
does not occur in nature.
D e n s it y o f MoS z. The density of MoS z is given in Table 88.
TABLE 88
Demity of MoO 3
14 4.80 Crystalline
1901 Guichard /80/
14 4.88 Amo[ph0_s
67
o
.n which the equilibrium constant/(ps for the reduction of MoS_ with hy-
drogen is determined:
PH
From the experimental values of/(p =- _ and from the equilibrium
constant Kp,= P_," Ps_ for the dissociationn,ofr, hydrogen sulfide 2H_S =
2H= + $2, the authors calculated the vapor pressure of sulfur Ps, = K_31 for
reaction MoS= _ Mo + S_; Kp(3) = P(s,) = Kp2, " Kp(_), or log Ps, = 2 log K PO) +
log K_2 r
The mean experimental values of Kpct) , the known values of Kp(_) and the
calculated values of log Ps_ are presented in Table 89.
TABLE 89
TABLE 90
Kelley /90/ interpolated the data of Andersen /89/ and gave the follow-
ing values for the heat capacity:
C1_ cal/deg, mole ..... (0.02) (0.33) (1.85) 5.72 9.79 12.57 15.19 15.17"
68
Kelley /91/ used the data of Regnault /92/ to obtain the following equation
for the variation of the molar heat capacity of solid MoS_ with temperature:
Smith and co-workers /65/ determined the heat content of solid molyb-
denum disulfide calorimetrically /660 67/ at low temperatures and from
these results calculated the heat capacity. The calculated values are pre-
sented in Table 91.
TABI_ 91
Cp, cat/mole- deg. ....... 0.28 0.63 1.12 1.74 2.46 3.24 4.07 4.97
Temperature, *K ............ 20 30 40 50 60 70 80 90
Entropy S_, cal/mole- deg ..... 0.140 0.315 0.560 0.870 1.25 1.69 2.17 2.71
69
i
Rossini and co-workers /21/ give the heat of formation of MoS 2 (s) as
-55,500 cal]mole.
Entropy of formation of MoS 2. Makolkin /95] determined the
entropy of formation of MoS 2 experimentally and found AS_9 s = -6.608
cal/deg_mole. In his reference book Kelley /93/ gives AS°g8 = -7.0
cal]mole • deg.
TABLE 92
o o
• w HT --H0
Functlonsoand _ in cal/mole, deg. for solid MoS 2 /65/
T
H T -- H; H r -- H 0
T, eK 0 # T, eK 0 •
The equation for the variation of the free energy of formation of MoS_
with temperature according to the equation Mo (s) + 2S(rh) = MoS 2 (s) was
derived by Kelley ]93/ from the experimental results of Parravano and
Malquori /94/ and from data on the heat capacity of MoS2:
Makolkin /95] determined the emf of the galvanic cell Pt(He)KCI'_0.01 N)[[
KCI(0.01N) ]H2S/MoS2, and obtained the value AF°9$ = -53,960 cal]mole.
Rossini et al. /21/ give the value AFs°gs = -53.8 kcal/mole.
The equation for the free energy of formation of MoS 2 from molybdenum
and gaseous sulfur can be obtained from Kelley,s equation (I) above, by al-
lowing for the free energy change for the sublimation of sulfur:
2S (rh) _ $2 (g).
7o
e
Richardson and Jeffes /97/ give the following equation for the free en-
ergy of formation of molybdenum disulfide from its elements Mo (s) + SS =
MoSs (s) from 1073 to 1373°K:
TABLE 93
Temper_ure, "K
71
Heat of formation of Mo2S3. McCabe /98/ gives the heat of for-
mationof MoaSs as AH_98 = -102.0± 7.0 kcal/mole.
Free energy of formation of Mo2Ss. The free energy of for-
mation of Mo_Sa for the reaction 2Mo (s) + 1 1/2 $2 (s) = Mo2Ss (s) is given by
Vapor pressure, arm... 0.0001 0.001 0.01 0.1 0.25 0.5 1.00
Values for the vapor pressure of MoF6 interpolated by Stull /20/ are
given below.
Temperature, *C .... -65.6 -49.0 -4.08 -32.0 -22.1 -16.2 -8.0 +4.1 17.2 36
1310
logP= - _ + 7.12 (Tmelt-Tbo/_
72
B
5210
log P(mmHg) = - _ + 13.1.
73
Heat of sublimation of MoCls. Kubaschewski
andEvans/22/
give the heat of sublimation of MoC15 at its melting point as Lsubl = 23.5 ±
3.0 kcal/mole.
Entropy of MoC15. According to Brewer et al./103/, the standard
entropy of MoCls is given by 8_9 s = 65.0 + 5.0 cal/mole • degree.
Heat of formation of MoCls. Gmelin/104/ gives the heat of for-
5
mation of MoCls according to reaction Mo (s) + _- C12 = MoCls (s) as AH,°gs =
90.8 kcal/mole. Brewer and co-workers /103/ and Rossini and co-workers
/21/ give the value AH,°98 = -90.8 ± 2.5 kcal/mole.
MoCl4 ......... 79
MoC13 ......... 65
MoC12 ......... 44
MoBr 5 ......... 51
MoBr 4 ......... 45
MoBr 3 ......... 41
MoBr 2 ......... 29
MoI 5 ......... 18
MoI 4 ......... 18
MoI 3 ......... 15
MoI 2 ......... 12
74
• 11. CARBIDES OF MOLYBDENUM
75
Theaccuracy of this equation is +3%. The equation is based on the data
of Sato /113/ for the heat content of MozN,
Heat content of MozN. Usingthe dataofSato /113], Kelley /40/
determined the heat contents of Mo_N from 400 to 8000K with a mean ac-
curacy of±3%. His values are quoted below:
Heat content !/7 _ H;98 eal/mole .... 1610 3360 5280 7290 9370
Entropy S T -- _298 cal/mole- deg .......... 4.64 8.54 12.03 15.13 17.19
Tonosaki /115/ also calculated the heat and the free energy [of forma-
tion] for this reaction. He gave AHt°98 = 7973cal and AF°08 = 5909 cal.
76
The data of Chaudron /114/ and Tonosaki /115/ are believed to be in-
sufficiently accurate.
TABLE 94
They found the following values of the equilibrium constant: IKp _ffi--'_--_!
77
ACp = -- 12.95 -t- 3-75-10-3T -- 0.503"10 sT-2, (I)
The standard entropy of the reaction, A,.q_9s = 27.5 cal/mole • degree, was
calculated from the following data: S°98 = 6.8 for molybdenum, S_9 s = 49.15
for H2S, S_9 a = 15.1 for MoS2, and S°ga = 31.33 cal/mole-degree forH2. Sub-
stituting in equation* (!II) AS_°98 = 27.5 cal/mole • degree and T = 298°K gives
-112.8 cal/mole, degree for AH0. Since AH0 varies with temperature, an
average value of 50,200 cal/mole was calculated for the range 1078 to
1373°K. Substituting this value for AH0 and the value /= -l12.88cal/mole
degree in equations (II) and (IV) for reaction MoS2 + 2H2 _-Mo + 2H2S, the
following equations are obtained:
hence
AH_ga= 46,670 cal/mole and AFt9 s = 38,460 cal/mole.
/_H, for two temperatures: 973 and 1123°K. At 973 °, /(p = 3.55, at
Pcn4
1123 °, Kp = 18.5. The values AH0 = 21.500 cal/mole and I= -7.29 cal/mole
degree were also calculated by these authors. The heat and free energy
of this reaction are given by
hence
78
q
The actual process proceeds in stages and the equation mentioned above
is ordy for the overadl reaction. It has been investigated by G1emser and
Lutz /118/, who gave its heat of reaction as _f/_ = -266.24 kcad.
79
Chapter 3
TABLE 95
Isotopes of titanium
46 7.90
47 7.75
48 73.45 47.91
49 5.51
50 5.34
8O
Q
TABLE M
TABLE 97
Eppelshe/mer,
900 i 5" 3.3132 Ill/
Penman
room temper-
3.283 ± 0.003* Lev/ngez /12/
aulre
Adem'te_ Pe_g-
as above 3.29" 113/
not, l_ymer
81
s
82
a suspended titanium wire which was a part of a heated loop. The tem-
perature at which the wire melted was determined by means of an optical
pyrometer. The most reliable values are apparently those of SchSfield
/48/ and Oriani and Jones /47/.
TABLE 98
From 883
emf measurements 1951 Womer 129/
to 887
Edwards, Johnston
884 i 3.5 Thermal analysis 1953 /31/
Ditmat_
TABLE 99
[w_inr of tlranh,rn
IV[elting
83
Vapor pressure and boiling point
TABLE lO0
A. D. McQnillan, M.K.
35O0 1958
McQuillan /23/
Luchinskii /17/ gives a value above 3450 °, Stull and Sinke /33/ give
3550 °. It seems that the last value is the most reliable and should be used
TABLE 101
* The values in the first column were obtained by measuring the resistance of a titanium wire,
those of the second column by calculating the decrease in weight of this wire.
24.275
log P= 7.782 0.00023T.
T
84
i
the vapor pressure of titanium from 1587 to 1764_K. Their results are
TABLE 102
P,ate of valxx-
No. of Effective sUr- Vapor pwssare,
Time, sec izaZion
sample face, cm 2 arm.108
g. cm-2 sec-1.10 8
Vickery /54/ determined the constants A and B for liquid and solid ti-
B
tanium in the simplified vapor pressure equation: log P (ram Hg) =d -- --_.
These constants are A = 3.810, B = 2472, and A = 3.350, B ffi 1525 for solid
From experimental data Blocher and Campbell /18/ derived the follow-
ing empirical equations for the variation in the vapor pressure of solid and
point (2000 + 10"K), Van Arkel /55/ obtained a vapor pressure of 1.2- 10 -2
Table 103.
85
TABLE 103
cal/g-atom'deg
capacity,
cal/g- deg
cal/g-atom, deg
Kelley /56/ determined the specific heat capacity of titanium in the range
Johnson ] 57/, using high purity titanium samples, repeated Kelley's ex-
periment /56/ and found the following atomic heat capacities at 15.4 to
TABLE 104
100 3.434
Jaeger et al, ]58/ give the following values for the atomic heat capacity
The average specific and atomic heat capacities of titanium are pre-
sented in Table 105.
Table 106 contains the heat capacities of solid, liquid, and gaseous ti-
tanium, as given by Stull and Sinke ]33/.
Rossini and co-workers /32/ give heat capacities of 6.010 and 5.8385
cal/g, atom. degree for solid and gaseous titanium, respectively.
Kelley /61/ derived the following equation for the atomic heat capacity:
1394
86
TABLE 10,5
t,'c cp cp Year
cal/deg, g cat/g- atom- deg
0--100 0.1462
0-- 187.5 0.1503
_Hunter 1141
0-- 254 0.1516 -- 1910
0-- 333 0.1563
-253-- 196 0.0205 -- 1913 Dew_ 1601
0 0.1442
50 0.1458
-- 1941
100 0.1497 Luchimkii /17/
2O0
3O0
0.1578
0.1660
I
TABLE 106
r OK Cp T, IK c, r. '_ cp0 .
The same author /62/ gives the following values for the atomic heat
capacity of titanium:
fora-Ti (from 298 to 1150°K):
Jaeger et al./63/ derived the following equations for the specific (I) and
atomic (H) heat capacity of titanium
87
In a later work ]64], these authors give the following equation for the
variation in atomic heat capacity with absolute temperature:
Blocher and Campbell /18/ calculated the heat of sublimation Lsubl of ti-
tanium at the given temperatures from the following equations:
where
T T
T Is ='T-
o 0
:ubl :bl
r, "x \T/g \----{_}s
* The values of the first column were obtained from resistance measurements , those
of the second from loss in weight.
** The heat of sublimation Lsubl was calculated from the equation of Carpenter and
Reavell /66/.
88
From their data on the vapor pressure of titanium (Table 102) Edwards
and co-workers /31/ calculated the heat of sublimation Lmbl from 1587 to
1764_K. Their results are presented in Table 108.
Rossini and co-workers /32/ consider only one value for the heat of sub-
limation to be reliable, i.e., Lmbl = ll2kcal/mole at 298_. Stull and
Sinke /33/ give Lmbl = 106.5 kcal/g-atom at 1812 ° and 0.036mmHg.
TABLE 108
--R_-p
T. o_
cal/g, atom. de I
89
for a-Ti (accuracy 3%, 298 to 115001<)
TABLE 109
Kothen and Johnston / 57/ determined the heat content of titanium from
15 to 298.16_K. Their results are presented in Table 110.
TABLE ii0
100 133.70
The heat content of titanium can be calculated from 200 to 817 ° from
the following equation derived by Jaeger et al. / 58/.
--0.271055.10-6t s -{-0.151877-10-°t 4.
Table 111 shows the heat content of solid, liquid, and gaseous titanium,
according to Stull and Sinke /33/. The second column of this table con-
tains the heat content of solid, liquid, and gaseous titanium, the third col-
umn that of gaseous titanium, considered as an ideal monoatomic gas.
Entropy of titanium. Kothen and Johnston /57/ determined the
entropy of titanium from 15 to 298*K. Their results are presented in
Table 112.
90
TABLE 111
7, *It
HI"--/_398 Hr _/_11 m r. qc NT--//elm HT -_n8
_a_$- _om cat/8 . atom cal/_- atom cal/_, atom
298 0 0 1700 11290 7370
300 !1 il 1800 12131) _9_
4OO e_9 577 1900 1297O 8494
500 1280 1119
coo 196o 16411 2100 18SeO
7oo 2168 19100 1027'3
am) 3355 25OO 19900 IIMM
9oo 4om) 3194
IOOO 48_o 37O4 25OO 91500 12175
1100 4214 26OO
1200 729O 4726 27OO 25101) 13514
IS00 8070 5241 28OO 239OO 142O6
1400 24700 14912
1500 6289 3OOO 25500 1.5633
1600 104711 6825
TABLE 112
r. *K T, oK r. qc
jcallg, at.deg cal/g-at-deg cal/g-at.deg
TABLE 113
5_11
_ Year Author Reference
Kelley /71/ calculated the entropy of solid titanium from its heat capac-
ity and found ,Segs = 7.24 + 0.05 eal/g-atom- degree.
Kubasehewski and Evans /65/, referring to Kelley's work, give Sos --
7.2 + 0.4 eal/g-atom, degree. Rossini and co-workers /32/ consider the
most reliable value to be 7.24 eal/g, atom-degree.
91
The entropy of gaseous titanium was calculated by Bacher and Goudsmit •
/72/ as S°gs = 43.07 + 0.1 cal/g, atom-degree. Kelley /71/ and Rossini
et al./32/ give S_9 s = 43.08 + 0.01 cal/g, atom • degree and S_°gs = 43.069
cal/g" atom • degree, respectively.
Kelley /71/ quotes the data of Jaeger et al./64/ on entropies from 400
to 1500°K (Table 114).
TABLE 114
Table 115 contains entropies of solid, liquid, and gaseous titanium, ac-
cording to Stull and Sinke /33/. The second column presents entropies of
liquid, solid, and gaseous titanium, the third column the entropy of titani-
um, considered as ideal monoatomic gas.
TABLE 115
Entropy Entropy
T, oK ¢, T, eK $;
cal/deg, g. at.I cal/deg,
$; g. at. cal/deg'g.at. cal/deg, g. at.
92
table contains values for the (I_ of titanium considered as an ideal mono-
atomic gas (Stull and Sinke /33/).
TABLE 116
@"for O,tamum/5"//
T, "K ro'caVg.at.deg
ir, *K 4Wcal/g-avde i T,*E O'cal/g-at.deg
1 O6 0.626
TABLE 117
F._K r T, *K
cal/g.at.deB
cal/g.at.deg
The following oxides of titanium are known: TIC), TiaO4, TilOs, TisOs,
TiO_ and Ti%.
93
face-centereod cubic lattice of the NaC1 type. The unit cell parameter of
TiO is 4.24 A. /75/. According to Ehrlich /73/, the crystal lattice param-
eter of stoichiometric TiO is 4.165 /_. Grove et al. ]82/ studied the solid
phase of TiC) by X- ray methods and came to the conclusion that there are
no substantial changes in structure up to the melting point.
Density of TiO. Br_ikken /76/ andDawihl andSchrbter /77/ give
the density of TiO as 5.53 g/cm s and 4.93 g]cm s, respectively.
a_ transition temperature in Tit:). Naylor reports /78/
that the a _- _ temperature transition in TiO (more correctly TiO0.7- I._.Q
takes place at 1264¢K. According to Kubaschewski and Hopkins /79/, the
transition temperature is 990 °. Kubaschewski and Evans /65] consider
the most reliable value to be 991 ° . The same value is given by Rossini
et al. /32/.
Melting point of TiO. Pirani andAlterthum ]80/ determined the
melting point of TiO as 1750 °. Bumps, Kessler, and Hansen ]81/ (1952)
found that the solid phase of TiO is subject to a peritectic reaction and de-
composes at 2010°K to give a-titanium and a liquid phase. Kubaschewski
and Evans /65] give the melting point of TiO as 2020°K.
Vapor pressure of TIC). Groveetal./82/ studied the vapor pres-
sure of TiC) by the Knudsen effusion method. The results of these experi-
ments obey the following equation for the vapor pressure of TiO:
According to Gilles and Wheatley /83/, the total pressure of the gaseous
phase in equilibrium with the [solid phase of] TiO is 10 -3 atm at 2275+ 50°K,
and 1 atm at 2970+ 100°K.
Heat capacity of TiO. The molar heat capacities of solidTiO at
low temperatures are given below according to Kelley /62/.
Molar heat capacity cal/deg.mole ..... (0.00)* (0.09)* 0.65 3.05 5.47 7.34 9.55
Kelley /62/, using the data of Naylor /78/, has calculated the following
equations for the molar heat capacity of titanium monoxide:
fora-TiO (accuracy 1.5%, 298 to 1264°K)
_"'Extrapo-lat e d.
94
Heat of sublimation of TiO. According to Gilles and Wheatley
/83/, the heat of sublimation of solid TiO is given by LOb I = 135+ 1 kcal/mole
at 298°K. Grove and co-workers /82/ give 134.6 kcal/mole. Using a mass-
spectrometric technique, Berkowitz et al./84/ obtained L_b I = 139kca1/mole
at 298°K for the sublimatinn process TiO (s) _ TiO (g).
Energy of dissociation of TiO. The energy of dissociation of
titanium monoxide into the atoms according to the reaction TiO (g) =
Ti (g) + O at 0°K was calculated by extrapolation and is 160 + ? * kcal/mole,
according to Gilles and Wheatley/83/.
Heat content of TiO. The data of Naylor/78/ on the heat content
of TiC) are presented in Table 118. These data were found by KeUey /62/
to conform to the following equation:
for TiC)(a) (accuracy I_, 298 to 1264_K)
TABLE 118
TABI_ 119
T.-K "1
s,-sm ,.'X #--ffi ,.*X
95
Kelley /71/ used the data of Shomate ]85/ on the heat capacity of titani-
um monoxide at low temperatures to calculate the entropy of solid TiO.
He obtained the following results: Sg_ = 0.25 (extrapolated), S 0298 __ S 052 =
8.06 (experimental), and S_g s = 8.31 ± 0.04 cal/degree.mole.
Kelley /71/ used data on molar constants /86/ and spectroscopic re-
sults /87/ to calculate the entropy of gaseous titanium monoxide. He
obtained $2°98= 55.80 + 0.10 cal/mole • degree for TiO (g). Kubaschewski
and Evans /65/ quote the data of Shomate /85/ on the entropy of solid TiO
and consider 8.3 + 0.1 cal/mole • degree to be the most reliable value; the
same value is given by Rossini et al. /32].
Heat of formation of TIC). Humphrey /88/ found that the heat
of formation of TiC)(g) at 0 ° is given by AH ° = -123.9 kcal/mole. Brewer
]74/, with reference toHumphrey/88/, gives AH°gs= 123.9+0.3kcal/mole.
Kubaschewski and Evans /65/ give AH°gs= -135.0± 10.0 kcal/mole.
The heat of formation of gaseous TiO is given as AH_gs= 43 kcal/mole.
The same value is given by Rossini and co-workers ]32].
Entropy of formation of TiO. For the entropy of formation of
solid TiO, Brewer /74/ gives AS_9 s = -22.8 cal/mole- degree.
Free energy of formation of TiO. The free energy of the for-
mation of TiO was determined by Humphrey /88/ as -116.92 kcal/mole at
0 °. Brewer ]74/ gives AF_s = -117.1 kcal/mole.
For the free energy of formation of solid TiO, Kubaschewski /89/ gives
the following equation:
96
found that Ti1Os decomposes into TiO (g) + TiOl (g}. The heat change ac-
companying this decomposition is given by A//_ = 296.0 kcal/mole. From
the data of these authors the following equation was derived:
Mott /51/ determined the boiling point of Ti2Os as 3300_K. Brewer /74/
states that at 3300 i 300"K the total pressure of the gaseous products of
TidDs in equilibrium with the solid phase is 1 arm.
Heat capacity of TilO s. Data on the heat capacity of solid Ti_
at low temperatures are given by Kelley/71/.
Molar heat capacitT_ cal/mole- (leg ....... (0.01)* (0.17)* 1.26 6.30 12.30 17.26 24.27
Rossini and co-workers /32/ give the Cp for Tiz(_ as 23.27 cal/mole'deg.
at 2980K.
Heat of transition of TizO s. Naylor/78/ determined the heat of
transition of Ti_ and found Luam = 215 cal/mole at 473_K, Kubaschewski
and Evans / 65/, referring to the work of Naylor / 78/, and also Rossini and co-
workers /32/, give Luam = 0.22 ± 0.05 kcal/mole.
Entropy of transition of Ti_)3. According toNaylor /78/, the
entropy of the a _ _ transition is given by AS = 0.450 cal/mole • degree at
473_. Rossini /32/ and co-workers give/L_uans = 0.46 at 473°K.
Heat content of TizOs. The heat content of Ti_)s, according to
Naylor /78/, is given in Table 120. According to Kelley /71/, these values
_it the following equations:
for TizO3 (a) (accuracy 2%, 298 to 473°K)
TABLE 120
T. °K /IF--/#*H8 r. oK
Mr--_ m J r. -x
t
400 2610 8OO 15830 1400 I 3eseo
473 (,.) 488S 9OO 1927O 1500 4O56O
5100 i000 22740 leO0 i 44180
o<P> 59_5 1100 1700 47890
9140 1200 29e00 1800 51490
1244O JmO 3,3m0
" £ztxapolate_
97
Entropy of Ti203. The data of Naylor /78/ from 400 to 1800_K
are presented in Table 121.
TAI3LE 121
From the heat capacity data of Shomate /85/ for solid Ti203, from 53
to 297"K, the author obtained 809 s = 18.18 + 0.09 cal/mole • degree (the sum
of the entropies S_= 0.50 (extrapolated) and 8_98 --S_$= 18.33cal/mole"
degree (experimental)). Kubaschewski and Evans ]65], referring to the
work of Shomate /85/, give S_°gs = 16.83 + 0.2 cal/mole, degree. The same
value is also given by Rossini and co-workers ]32].
Heat of formation of Ti203. According toNasu /92/, the heat of
3
formation of Ti202 for the reaction 2Ti + _ 02 = Ti2Os -388.070 kcal/mole.
98
Temperature, "K ................. 10 25 50 100 l&0 200 298.16
Molar heat capacity, cal/mole- dog ..... (0.02)" (0.34)* 2.43 11.00 20.10 27.35 37.00
c, = .47 +
and for TisO5 _) (accuracy 1%, 450 to 1400_K)
TABLE 122
The entropy of TisO5 from 400 and 1400°K, according to Naylor /78/,
is given in Table 123.
TABLE 123
0 0 0 0 0 0
1", "K Sr -- S_8 T, "K ST -- $2_8 T, oK Sr -- S21NI
From the heat capacity data of Shomate /85/ Kelley calculated the en-
tropy of TisO 5 as S_= 30.9 ± 0.2 ca.I/mole- degree. He obtained this
* Extrapolated.
99
valueby additionof the followingentropies:$52 = 0.97 cal/mole • degree
(extrapolated result) and S°98 --3°2 = 29.95 cal/mole, degree (experimental).
Kubaschewski and Evans /65/, referring to the work of Shomate /85/,
give S_°gs = 30.9 + 0.3 cal/mole • degree. Rossini and co-workers /32/give
S_0 s = 30.92 cal/mole • degree.
Heat of formation of Ti30 s. Humphrey/88/ measured the heat
of formation of Ti30 s at 0 ° and found AH ° = - 586.9 kcal/mole. Brewer
/74/, referring to the work of Humphrey /88], gives AH098 =-587.0+ 0.5
kcal/mole, Rossini and co-workers/32/ give AH°gs = - 584 kcal/mole.
Entropy of formation of Ti30 s. Brewer /74/ gives AS°o8 =
-63.5 cal/mole • degree.
Free energy of formation of Ti30 s. According toHumphrey
/88/, free energy of formation of Ti305 is given by AFt98 = -553.1 kca]]mole.
Brewer /74/ gives hF°98 = -553.0 kcal/mole, Rossini et al./32/ give
AF _gS = - 550 kcal/mole.
TABLE 124
Density of TiO 2
100
Transition temperature of TiO2. The transition temperature
potassium titanate and KC1, heatedinan atmosphere of gaseous HC1 and air,
produces anatase at 700 to 800 °, brookite at 800 to 1040 °, and rutile above
1040 °. Junker /104/ showed that futile is converted into brookite at about
1300 °.
TABLE 125
18.80"
19.8-- 20.5t
* Anatase
** Rmile
Brookite
TABLE 126
The most reliable values for the melting point of TiO2 rutile are 1860 °
chewski and Evans /65/. Brewer /74/ gives 3200± 300°K. At this tem-
of TiO2 is 1 atm.
101
Dissociation temperature of TiC) 2. The dissociation tempera- •
ture of TiO2 was investigated by Born /110/. He showed that TiO2 dissoci-
ates into oxygen and titanium, both at 2000 ° and 1 atm and 3000 ° and 10-3atm.
Junker /104/ showed that dissociation of TiO2 occurs at 2230 ° with for-
mation of lower oxides.
Vapor pressure of TiO2. The following equation for the sublima-
tion pressure of TiO2 is based on the experimental work of Grove etal./82/:
Heat capacity of futile, cal/mole'deg...(0.02)* (0.22)* 1.45 4.43 7.57 10.05 13.16
Temperature, °K ................. 10 25 50 100 150 200 298.16
Heat capacity of anatase, cal/mole.deg..(0.01)* (0.18)* 1.17 4.59 7.62 10.00 13.22
Kelley /62/ gives the following equations for the heat capacities of the
two allotropes:
for futile (298 to 1800°K)
These equations were derived from the data of Naylor /78]. Kubaschew-
ski and Evans /65/, referring to the work of /78/, give the following two
equations:
for futile (298 to 1800°K)
Kelley /61/ gives the following equation for molar heat capacity of TiO_
from 298 to 1300_K:
Rossini et al./32/ give CP298 = 13.16 and CP298 = 13.22 cal/mole • degree
for futile and anatase, respectively.
Heat of transition of TiO2. Rossini and co-workers /32/ give
the heat of the a_] transition in anatase as Ltrans = 0.3 kcal/mole at 642 °.
• Extrapolated.
102
Entropy of transition of TiO=. The entropy of transition ofatm-
tase at 642 ° is given by AStran s = 0.3 cal/mole, degree 1321.
Heat of fusion of TiO_. From a study of the TiOz--AI=Os system,
Bunting 1108/ calculated a heat of fusion of 11,400 callmole.
This value however is not accurate. Kubaschewski and Evans /65/
give Lfus = 15.5 ± 2.5 kcal/mole.
Heat of sublimation of TiOt. Grove et al. 1621 studied the vapor-
ization of TiO2 by the Knudsen effusion method and found Lmbl = 138.9
kcal/mole at 0 ° for TiOt (S)-* TiO= (g).
Lmbl = 146.0 kcal/mole at 298°K was obtained by Berkowitz et al. 1841,
using mass- spectrometric methods.
Heat content of TiO#. Data of Naylor / 78/ on the heat content of
rutile and anatase are presented in Tables 127 and 128.
TABLE 127
TABLE 128
The data of Tables 127 and 128 obey the following equations:
for futile (accuracy 1_, 400 to 1800°K)
103
1
give S°98 = 12.05= 0.05 for rutile and Sggs = 11.935= 0.1 cal/mole • degree for
anatase. Rossini and co-workers /32/ give the same values. Kelley/ll3/
TABLE 129
TABLE 130
TABLE 131
Heat of formation
_A/./*9
_ S Method Year Author Reference
218.'1 ± 0.3 Combustion of titanium with paraffin 1931 Roth, Becket /117/
oil
220.7 ± 0.I -- 1931 Sieverts, Gotta 11181
104
is given by AS_m = -22.8 cal/mole •degree. Kubaschewski and Hopkins
note however that this value is not accurate. According to Kelley/113/,
the entropy of formation of TiO= is given by _S_8 = -43.7 cal/mole-degree.
Free energy of formation of TiO 2. According to thedataof
Humphrey /88/, the free energy of formation of TiO_ is given by AP =
-212.3 kcal/mole at 0 °. Brewer /74/ gives bP_ = -212.4kcal/mole.
Kubaschewski /89/ derived the following equation:
TABLE 132
105
H e a t c o nt e nt o f TiS_. Data on the molar heat content of titanium
disulfide above 298°K, according to Todd and Coughlin /127/, are present-
ed in Table 133.
TABLE 133
The data of Todd and Coughlin /127/ conform to the following equations:
for TiS_ (a) (accuracy I%, 298 to 420°K)
Entropy of TiS2. From the heat capacity data of Todd /128/ for
solid TiS2, Kelley /I13/ calculated its entropy from 53* to 298_. He then
obtained 8_9 a = 18.73 cal/mole • degree by adding SOt = 1.38 (extrapolated
result) and S_gs--S_I = 17.35 cal/mole, degree (experimental).
Todd and Coughlin /127/ determined the entropy of TiS2 from 298 to
1100_. Their results are presented in Table 134.
TABLE 134
* [Probably 51 is imended.]
106
o
TABLE 135
t, _ "_P P. P, P.
Fluorides of titanium
There are three titanitun fluorides: TiF2, TiFs, and TiF4. Only ther-
modynamic data for the last two compounds are given below. Unfortunately,
almost no data for TiF2 are available. Rossini and co-workers /32/ give
107
Titanium tetrafluoride TiF4 (M = 123.9)
CHLORIDES OF TITANIUM
The following chlorides of titanium are known: TIC1, TIC12, TiCls, and
TIC14. The heat of formation of gaseous TiC1 is given as AH°s =+122
kcal/mole ]32].
108
wasstudiedabove950_Kby SkinnerandRuehrwein/133/. The partial
pressures of TiCls, TiClz, and TIC14, and the sum of these pressures are
presented in Table 136.
TABLE 136
Tc_.al
Tcmpezamr_
"K
presmi¢, _'ncl, _'TJCl, A'uct,
Pexprl
97/ 16.$ S 8 IS
100e 36.$ !1 18 SO
I041 66.7 S M m
1071 41 86 112
at 850 °, the same authors found /(lisp= 49.5 kcal/mole and ,q,S,,.p: 32.2
cal/mole • degree. Disproportionation of TiC]_ at this temperature may
also proceed according to the equation 3TIC1| (s) = 2TiCIs (g) + TI (s). In
this case, the heat and entropy of disporportionation of TIC12 are given by
/-di,p = 87.2 kcal/mole and _disp= 30.7 cal/mole.degree, respectively.
According to Funaki and Uch-umura /132/, the free energy of dispro-
portionation of TiC12 is
AFt= 39.0- 10s-29.5Tcal.
Heat content of solid and gaseous TIC12, The O' fuaC_on fm TiCI 2 La
109
Entropy of TIC12. The entropy of TiCl_ is given by Soge= 24.7
cal/mole • degree and S_9 s = 65.9 e.u. for solid and gaseous titanium di-
solid TiC12 is given by S_gs = 26.2 ± 2.1 cal/degree .mole. For the en-
tropy of solid TIC12, Kubaschewski and Evans /65/ give S_96 = 29.0 +
TABLE 139
Solid TiCI 2
123.3 + 0.7
1956 Clifton, Macwood /134/
123.7 ± 1.0 /
118.7" 1955 Skinner, Ruehrwein /133/
118.3 1955 Skinner, Ruehrwein /133/
120.1 1956 Krive et al. /136/
120.6 1956 Altman et al. /137/
121.0 ± 1.1 1957 Hartmann, Rinck /138/
Gaseous TiC12
69.1" 1
1955 Skinner, Ruehrwein /133/
69.5
* At 0".
For the heat of formation of solid TiCI2, Rossini et 8/./32/ give &H_9 s =
- 114 kcal/mole.
type crystal lattice with the following parameters: a = 6.82 A and a = 53°20
/65/.
Sublimation and disproportionation pressure of TiC/3.
Clifton and Macwood /134/, using the effusion method, derived the follow-
110
and from 593 to 821_K
6987
log P(mm Hg) T + 8.407.
TABLE 140
7000
logP(mmHg) =-_ + 10.5.
111
Farber and Darnell /139/ found experimentally that the heat of sublima- ° ,
tion of TiC1 s is 42 kcal/mole at 298°K and 39 kcal/mole at 688_K.
Entropy of sublimation of TiC1 s. According toCliftonand
Macwood / 134/, the entropy of sublimation of TiC1 s is given by AS s°ubl =
41.6 cal/mole-degree at 298°K. Farber andDarnell /139/ quote 37.e.u.
and 31 e.u. at 298 and 688°K, respectively.
Free energy of sublimation of TiCls. For the free energy
of sublimation of TiCls at 298°K, Clifton and Macwood /134/ give AFt98 =
29.6 + 1.0 kcal/mole. The variation of the free energy with temperature
/134/ is given by the following equation:
112
Q
Heat content of TiCls. The heat content of solid and gaseous ti-
tanium TiC13 is given in Table 141 /133/.
@*, cal/mole-deg.
"r-_, c_/mole
r, "K T. eK
TiCl3(s) TiCI3 (g)
TiCI 3 (s) TiCI3 (g)
TABLE 143
Refv.lv_
-A/t 0 , kcal/mole
Heat of formauon, I Year I Autho_
298
S oli d TiCI 3
161.1 }
1954 Schafer et al. /1401
161.6
170.0i )
1955 Skinner, Rnehrwein 1133/
17fL1" 0.8
Liquid TiCI 3
Gaseous TLCI 3
127.'ff 11331
128.0
130.2 i 1.4 11341
1956 [ Clifton, Macwo0d
128.7 1956 I Altman et al. 11371
• At O'K.
113
Entropy of TiC13. According toAltman et ai./137/, the entropies
of solid and gaseous TiC13 are given by S2°0a = 34.4 cal/mole- degree and
S_°ga = 74.9 cal/mole •degree, respectively., For solid TiCls, Kubaschewski
and Evans /65/ give S_98 = 39.0 + 4.0 cal/mole • degree.
Free energy function of TiC13. Skinner and Ruehrwein /133/
give the following values for the _' function of solid and gaseous TiCI 3 from
298 to 1500°K (Table 142).
Heat of formation of TiC13. The heat of formation of solid,
liquid, and gaseous TiCls is given in Table 143.
d¢ = 1.767-0.00162t/142/
TABLE 144
114
TABLE 145
Boiling point,
Year Authc_ Reference
"C P, mm Hg
t,'C p t,*C P
TABLE 147
290 0.01
According to Arii, the vapor pressure of TIC14 from 20 to 135 °/154, 155/,
is given by the equation:
1947.6
log P(mmHg) = 7.64433
7
For the vapor pressure of TiC14 from 293 to 408°K, Kelley /56/ derived
the following equation:
115
2.0775.10 s
log P(mmHg) = 8.0015-
T
Temperature t "C ......... -13.9 +9.4 21.3 34.2 48.4 58.0 71.0 90.5 112.7 136.0
TABLE 148
T. eK % r..x % r..K cp
* These values are for liquid TIC14, the others for solid TiC14.
Table 149 shows the heat capacities of liquid and gaseous TIC14 above
room temperature.
TABLE 149
Accuracy I
of deter- Temperature
Heat capacity Cp cal/mole, deg mination, range, °K Author
I Reference
Liquid
Gaseous
Cp=24.61+ 1.54.10-3T - 1.94X 1057" "2 1.5 298-- 575 Herman; Spencer /158/; /159/
116
For the heat capacity of liquid and gaseous TIC14 at 298_K, Rossini and
co-workers/32/give Cp= 22.88 and C_ = 37.5cal/mole-degree, respectively.
Heat of fusion of TIC]4. The specific heat of fusion of TiC]4, ac-
cording to different authors, is presented in Table 150.
TABLE 150
Specific
heatoffusion
ofTiC14 a_25"
Biltz and Meinecke / 1461 studied the system TiC]4--CI'2 and obtained a
heat of fusion of TIC14 of 2120 cal/mole.
Nasu /161, 162/ studied the systems TIC14- CC14, TiC14- SbCl4,
TIC14 -- SiCl4. and TiCLs -- SnC]4. Calculations based on studies of the first
three systems led to heat of fusion values of 2340, 2170, and 2420 cal/mole,
respectively, while the fourth system led to a much higher value, i.e..
3110 cal/mole. The average of these four values is 2260 cal/mole, which
is only slightly different from the value of 2230 cal/mole, obtained by Lati-
mer /145J. Kelley considers the average of the last two quoted values, i.e.,
2240 cal/mole, to be the true heat of fusion of TIC14.
The system TIC14--SO2 was investigated by Bond and Stephans /1831.
These authors obtained for the heat of fusion of TIC14 the higher value
2720 cal/mole.
Kubaschewski and Evans /65/ consider Latimer's value /1451 (Lfm = 2.S±
0.1 kcal/mole) to be the most reliable. Rossini and co-workers /321 give
the value adopted by Kelley, i.e., 2.24 kcal/mole.
Entropy of fusion of TIC14. Rossini and co- workers 1321 give
ASfu s = 9.0 cal/mole" degree at 250°K.
Heat capacity change during vaporization of TiCI 4. The
heat capacity change during vaporization of TiCI4 from 293 to 408"K is given
by AC_= -11.5 cal/mole •degree /1561.
Heat of vaporization of TIC14. According to Arii /lf_/, the
heat of vaporization of TiCI4 is 8960 cal/mole at 25" and 8620 callmole at
136 ° .
Kelley 1156/, referring to the results of Arii/154, 155/, gives 9622
and 8346 cal/mole at 298 and 409"K, respectively. Kubaschewski and Evans
/65/ consider the values adopted by Kelley/156/, i.e., Lvjp = 9.6 ± 0. 9-
kcal/mole at 25 ° and Lvap= 8.4 + 0.2 kcal[mole at the boiling point of TiC]_
to be the most reliable.
According to Schiller and Zeppernik /153/,. the heat of vaporization of
TIC14 is 8.65 kcal/mole at 136.5". Rossini et al./32/ give 8.4kcal/mole
at 135.8 ='.
The heat of vaporization of TIC14 from 293 to 408"K obeys the following
equation ] 156/:
Lvap = 13,050-ll.5Tcal/mole.
117
Entropy of vaporization of TIC14. According toSch_fer and
TABLE 151
The data of Herman /1 58/ fit the following equation (accuracy of 0.5%,
298 to 2000°K):
Skinner and Ruehrwein /133/ later obtained the heat content of solid and
gaseous TIC/4 values quoted in Table 152.
TABLE 152
H T -- H 0O,cal/mole
T, OK
TiCI 4 (1) TiCl 4 (g)
500 -- 1o,ooo
I000 -- 22,800
1500 -- 35,600
1394
118
TiC14 at this temperature S ° = 124 cal/mole" degree. The same authors
11681 calculated the entropy of gaseous TIC14 from spectroscopic data and
obtained S ° = 117 cal/mole- degree at ll00aK.
For the entropy of liquid TiCI4, Kubaschewski and Evans 1651 and Ros-
sini and co-workers 1321 give S*_ = 60.0+ 0.6cal/mole.degree and S'_=
60.4 cal/mole- degree, respectively.
Kubaschewski and Evans 1651 give S_ = 84.4 ± 0.1 cal/mole- degree for
the entropy of gaseous TIC14. Rossini and co-workers 1321 also consider
this to be the most reliable value.
TABLE 153
Entropy$098,
cal]mole, deg
Liquid TIC14
59.51
calculatedfromh_a*cap_i_ d_=ofTIC14 I _2 I_ /145/
/lc_/
60.3 + 1.5 Calculated from vapor pressure and enUopy data I 1933 [Iost_
for gaseousTiC14 ................... j 1950 / vl/
l I Kelley
Gaseous TiCI4
/ls5!
84.3i 1.0
11661
84.4 As above .......................... [ ] P&amasivan
81.5
TABLE 155
5OO -- 76.8
1000 -- 92.0
1500 -- 102.6
119
The _)' function for TIC/4. The {D' functions for gaseous and liquid
TIC14, calculated by Skinner and Ruehrwein ]133], are shown in Table 155.
Heat of formation I
Solid TiCI 4
196.4"
I 1955 I Skinner, Ruehrwein I /133/
Liquid TiCI 4
Gaseous TiC14
182.6
1955 Skinner, Ruehrwein /133/
183,0
11681
182.9
181.6 } 1955
1956
Farber,
Altman
Darnell
et al. 11371
" At 0*K,
For liquid TIC14, Bichowsky and Rossini /171] give AH_9 a = 181.4
For the heat of formation of gaseous TIC14, the same authors/65] give
Ti (s) + 2C12 = TIC12 (1), and of gaseous TIC14, according to the reaction
120
BROMIDES
OFTITANIUM
We present here thermodynamic data on TiBr2, TiBrs, and TiBr 4. For
the first two compounds, Rossini and co-workers/32/ give the following
heats of formation: TiBr2, A/_2 u = 95 kcal/mole; TiBr$, AH*zm = -132
kcal/mole.
Hall and co-workers /174/ studied the vapor pressure of TiBr4 and de-
rived the following equation:
Ceki /176/ gives the following equations for the variation of the vapor
pres
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