Contributions to the Data on Theoretical Metallurgy: [Part] 7. The Thermodynamic Properties of Sulphur and its Inorganic Compounds Page: 96
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96 DATA ON THEORETICAL METALLURGY.--VII
for the formation of PbSO4.2PbO from the elements. These figures
apparently are the only suitable values obtainable. Calculations
made from the data of Schenck and Albers (139) and Schenck and
Borkenstein (140) for the reaction PbSO4.2PbO+2PbS= 5Pb (l)
+ 3SO2 give AH298.1= --309,390 and AF298.1= -275,600. These values
are given no consideration, as they correspond to a positive heat and
free energy of reaction for PbSO4+2PbO= PbSO4.2PbO at 298.1,
which appears unreasonable.
The formation of PbSO4-2PbO from the elements involves
AC,= - 6.32 + 13.79 X 10- T+ 5.631X 105 T-2 (495)
Allow and I are obtained from AH 298.1 --332,390 and AF298.1=
--291,680 and the following relationships are derived.
3Pb + S(rh) + 302= PbSO4.2PbO;
AH= - 329,230- 6.32 T+ 6.90 X 10-3 T2 - 5.631 X 105T-1, (496)
AF= -329,230+ 14.55 Tlog T - 6.90 X 10-3T2--2.816 X 10, T-1 +95.19 T, (497)
AH298.1 = - 332,390; AF298s. = - 291,680.
PbSO4.3PbO.-The reaction 13 (PbSO4.2PbO) +PbS= 10 (PbSO4.
3PbO)4S02 was studied by Schenck and Albers (139). For this
reaction also
A C,= 20.13- 47.13X 10-3 T- 8.180X 105 -2 (498)
and 2= -R In K+46.36 log T--23.56X 10-3T-4.090X 105T-2 (499)
are employed. The 2-calculations are summarized in table 67.
TABLE 67.-13 (PbSO4.2PbO) + PbS =1 O(PbSO4.3PbO) +4S02
T Pso, -Rin K 46.361og T -23.56X10-3T -4.090X105T 2 192,600 1
1,043 7. 76X10-2 20. 31 139.93 -24.57 -0. 38 135. 29 184. 66 -49.37
1,063 1. 36X10-1 15. 86 140. 31 -25. 04 -. 36 130. 77 181. 1.9 -50. 42
1, 073 1. 68X10-1 14. 18 140. 50 -25. 28 -. 36 129.04 179. 50 -50. 46
1, 033 2. 05X10-1 12. 59 140. 68 -25. 52 -. 35 127. 40 177. 84 -50. 44
1,088 2.25X10-' 11.85 140.78 -25.63 -. 35 126.65 177.02 -50. 37
1,052 1.07X10-1 17. 76 140.10 -24. 79 -. 37 132. 70 183.08 -50.38
1,063 1. 30X10-1 16. 22 140.31 -25. 04 -.36 131. 13 181. 19 -50.06
1,058 1.51X10-1 15.02 140. 22 -24. 93 -. 36 129. 95 183.04 -52. 09
1,043 8. 42X10-2 19. 67 139. 93 -24. 57 -. 38 134. 65 184. 66 -50.01
1, 052 1. 04X10-1 17. 99 140. 10 -24. 79 -. 37 132. 93 183. 08 -50. 15
1, 063 1. 34X10-1 15. 97 140. 31 -25. 04 -. 36 130. 88 181. 19 -50. 31
1, 083 1. 99X10-1 12. 83 140. 68 -25. 52 -. 35 127. 64 177. 84 -50. 20
1,073 1. 70X10-1 14. 08 140. 50 -25. 28 -. 36 128.94 179. 50 -50. 56
1,083 2. 00X10-1 12. 79 140. 68 -25. 52 -. 35 127. 60 177.84 -50. 24
1,073 1. 64X10-1 14. 37 140. 50 -25. 28 -. 36 129. 23 179. 50 -50. 27
1,083 1. 97X10-1 12. 91 140. 68 -25. 52 -. 35 127. 72 177. 84 -50.12
Mean_. -50.34
A plot of I against 1/T gives a line the slope of which is AHo= 192,-
600. The individual I-values based on this slope and the X's are
shown in the last column. Their mean, 1= -50.34, is adopted and
the resulting heat and free-energy equations follow:
13(PbSO4.2PbO) + PbS= 10(PbSO4.3PbO) + 4802;
AH= 192,600+20.13 T- 23.56X 10-3T2-+ 180X 105T-1, (500)
AF= 192,600- 46.36 T log T+ 23.56 X 10-a32+4.090 X 105 T--50.34 T, (501)
AH298.1 = 199,250; AF0298.1= 146,860.
The heat and free energy of formation of PbSO,.3PbO are obtain-
able from the results just computed and the values presented for the
other reactants and products. Thus, AH298.3= -386,120 and aFo298.
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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/m1/98/: accessed April 19, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.