Contributions to the Data on Theoretical Metallurgy: [Part] 7. The Thermodynamic Properties of Sulphur and its Inorganic Compounds Page: 85
ii, 154 p. : tables ; 24 cm.View a full description of this report.
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THERMODYNAMIC PROPERTIES OF SULPHUR
TABLE 60.--2(CuOCuS04= 4CuO+ S02+02
T K -R In K 39.17 log T -16.78X10-T -4.490X10T -2 15400
1, 013 2. 01X10-s 21. 49 117. 73 -17. 00 -0. 44 121. 78 152.02 (-30. 24)
1, 033 5. 51X10-5 19. 48 118. 06 -17. 33 -. 42 119. 79 149. 08 -29. 29
1,053 2. 64X10-4 16. 37 118.39 -17. 67 -. 40 116.69 146. 25 -29.56
1,073 9. 69X10-4 13. 79 118. 71 -18. 00 -. 39 114. 11 143. 652 -29. 41
1, 083 1.95X10-3 12. 40 118. 87 -18.17 -. 38 112.72 142. 20 -29. 48
1,093 3. 50X10-' 11. 24 119. 02 -18. 34 -. 38 111. 54 140.90 -29 36
Mean -29.42
In this case the I against 1/T plot yields AH0o=154,000. The average
I, omitting the first value, is 1= -29.42. The heat and free-energy
relationships follow.
2(CuO.CuSO4) =4CuO+2S02+ 02;
AH- 154,000 -17.01 T- 16.78X 10-3T2+ 8.979X 10'T-1, (458)
AF- 154,000+39.17 T log T + 16.78X 10-3T2+4.490X 105T---29.42 T, (459)
H8.1= 160,590; AFo0es.1= 119,330.
Combination of equations (456), (457), (458), and (459) and the
heat and free energy of formation of CuO gives AH298.1= -188,000
and AF298.1= -161,330 for the formation of CuSO4 from the ele-
ments. These values are in good agreement with those obtained from
the reactions involving Cu20 and also agree qualitatively with the
other available figures.
A few other equilibria involving CuSO4 have been studied. Reinders
and Goudriaan (134) and Schenck and Hempelmann (143) have con-
sidered the reaction Cu2S+2CuSO4=2Cu20 +3S02. These data,
however, do not add anything quantitative to the situation so far as
CuSO4 is concerned. The same is true of the 3CuS+CuSO4=
2Cu2S+2SO2 reaction studied by Reinders and Goudriaan (184).
Both these reactions have been discussed by Randall, Nielsen, and
West (130). Discussion of Schenck and Hempelmann's data for the
reaction 3Cu+CuSO4=2Cu20+SO2 will be postponed until after the
heat and free energy of formation equations for CuSO4 have been
derived.
For the present, adoption of the results of Ishikawa and Murooka
(50), which are about the mean of the available figures, appears to be
the most reasonable procedure. Their figures correspond to an
entropy of formation of AS298.1= -88.4, which in turn yields S298.1=
25.3 for CuSO4. The entropy of CuSO4 has not been determined more
directly, but this figure appears entirely reasonable in comparison
with those for other sulphates (70). For the formation of CuSO4 from
the elements,
AC,= -7.66+ 13.68X 10-3T-3.754X 105T-2. (460)
On evaluating AH0 and I from Ishikawa and Murooka's values of
AH298.1 and AF298.1, the following results are obtained:
Cu + S (rh) + 202= CuSO2;
AH= -183,880-7.66 T + 6.84 X 10-3T2+3.754X 105T-, (461)
AFo = - 183,880+17.64 Tlog T -6.84X10-'T2+ 1.877X 1056T-1+43.26 T, (462)
AH298.1= -184,300; AF19s.i1= -157,950.
It may be shown now that Schenck and Hemp elmann's (143) data
for the 3Cu+CuSO,=2Cu20,+SO2 reaction are min agreement, within85
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Kelley, K. K. Contributions to the Data on Theoretical Metallurgy: [Part] 7. The Thermodynamic Properties of Sulphur and its Inorganic Compounds, report, 1937; Washington D.C.. (https://digital.library.unt.edu/ark:/67531/metadc66396/m1/87/: accessed April 25, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.