Contributions to the Data on Theoretical Metallurgy: [Part] 11. Entropies of Inorganic Substances: Revision (1948) of Data and Methods of Calculation Page: 52
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52 CONTRIBUTIONS TO DATA ON THEORETICAL METALLURGY
From spectroscopic data, Giauque and Wiebe compute Ss98.16=
49.4, in agreement with their third-law value. Murphy (367) more
recently has calculated the entropy from molecular-constant data,
I~4.30X 10-40 and w= 2,270. Their result, which has been corrected
for differences in natural constants, is S298.16=49.33 +0.05. This
value is adopted.
Blagg and Murphy (44) computed the entropy of DI (g) from molec-
ular-constant data corresponding to I=8.4X 10-40 and w= 1,620.
Evidently some mistake was made, as they obtain an impossibly
low value in comparison with that for HI (g). Repetition of the
calculation yields S298.1-= 50.69 0.05, which is higher than the value
for HI (g) by the anticipated amount.
Azide.-Eyster and Gillette (157) have computed the entropy of
HN3 (g) from the moments of inertia, 1,=70.75X 10-40, 12=69.38X
10-40, and 13=1.376X10-40, and the vibration frequencies, 658, 739,
1,152, 1,269, 2,140, and 3,336 cm.-' Repetition of the calculation
leads to St+r,298.16= 56.06, S,298.16=0.70, and S98.16= 56.8 0.3.
Cyanide.-The heat capacity of HCN was measured by Giauque
and Ruehrwein (185) (140-3000). Their calculations, which have
been checked, are S5.0o=0.13 (extrapolation), S159.8-S5.0= 16.77
(crystals, less abnormal heat absorption near 170.370), AS170.37=
3.8/170.37= 0.02 (abnormal heat absorption), AS259 .=- 2,009/259.86 =
7.73 (fusion), S9.80-S59.86= 2.36 (liquid), AS298.80= 6,027/298.80=
20.17 (vaporization at 1 atm. pressure), AS298.80=0.03 (correction to
ideal gas state), and AS298.80=0.73 (correction for polymerization).
The sum is S29s.80=47.94 for HCN (g). The value for 298.160 is 0.02
less, or S298.16=47.920.2. It also is evident that Sls.so0=27.01 for
HCN (1), which corresponds to S2~98,.= 26.970.10. The values
for HCN (1) apply to the equilibrium mixture of polymers.
From molecular-constant values, 1=18.72 X 10-40, 1= 2,089 (1),
w2=712 (2), and wo3=3,313 (1), which were reported by Bartunek and
Barker (38) and used by Giauque and Ruehrwein (185), there are
computed Str, 298.16=47.615, S, 298s.18=0.586, and S98.,6= 48.200.10
for HCN (g). This value from molecular-constant data is adopted.
Giauque and Ruehrwein obtained S98.1=48.23; Badger and Woo (34)
obtained S398.2=48.23; and Gordon (198) obtained Ss9.16=48.29.
From molecular-constant values given by Bartunek and Barker
(38) and Crawford and Brinkley (113), I=22.92 X 10-40, w = 1,906 (1),
2= 569 (2), and o= 2,630 (1), there are obtained S+7,298. 648.126,
SV, 298.16= 1.010, and S2098.6=49.14-0.10 for DCN (g).
The National Bureau of Standards tables (370) list S98.16= 30.8
for HCN (aq).
Cyanic Acid.-The value, S2098.1-=43.6, for HCNO (aq.) is given in
the National Bureau of Standards tables (370).
Sulfide.-Heat-capacity measurements of H2S at low temperatures
were made by Clusius and Frank (95, 97,162) (110-2090) and Giauque
and Blue (175) (160-2130). The calculations of the latter investi-
gators are repeated here. They find S16.o=0.26 (extrapolation),
8003.52-I .0=7.65 (crystals III), ASo03.52= 368.0/103.52=3.55 (tran-
sition), S126.0- S.52= 2.48 (crystals II), S127.0 o S26.0= 121.3/126.22=
0.96 (transition), Ss87 .61- S12.o= 5.32 (crystals I), ASI7.61= 568.1/187.61
=3.03 (fusion), S212.7~- S87.1=2.05 (liquid), AS212 .77=4,463/212.77
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Kelley, K. K. Contributions to the Data on Theoretical Metallurgy: [Part] 11. Entropies of Inorganic Substances: Revision (1948) of Data and Methods of Calculation, report, 1950; Washington D.C.. (https://digital.library.unt.edu/ark:/67531/metadc12637/m1/56/: accessed April 24, 2019), University of North Texas Libraries, Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.