Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
~; * *, *
,~* **,
by
(1951)
DOCTOR OF SCIENCE
at the
June, 1954
Signature of Author __
Department of etalrgy, Yebruay 8, 1954
Certified by
/ ,Thesis Supervisor
i-f
Room 14-0551
77 Massachusetts Avenue
Cambridge, MA 02139
M ITLibraries
Document Services
Ph: 617.253.5668 Fax: 617.253.1690
Email: docs@mit.edu
http://libraries.mit.eduldocs
DISCLAIMER OF QUALITY
Due to the condition of the original material, there are unavoidable
flaws in this reproduction. We have made every effort possible to
provide you with the best copy available. If you are dissatisfied with
this product and find it unusable, please contact Document Services as
soon as possible.
Thank you.
Abstract
by
sulfide join.
John Chipman
Professor of Metallurgy
iv.
TABLE OF CONTENTS
Chapter Page
Number Number
Title Page i
Abstract ii
Table of Contents iv
List of Illustrations vii
List of Tables x
Acknowledgments xi
I. INTRODUCTION
I-1. General
11-4. Furnace 34
11-5. Furnace Tube Assembly 37
11-8. Materials 45
v.
Chapter Page
Number Number
PRELDIINARY EXPERIMCEITS 48
III-l. Development of Two-Phase Melt Sampling 48
Technique.
IV-l. General 73
IV-2. One Phase Melts 74
V. EXPERIIENTAL RESULTS 77
V-I. General 77
Chapter Page
Number Number
APPENDIX
A. Detailed Account of Gas Analysis Procedure 128
LIST OF ILLUSTRATIONS
Figure Page
Number Title Number
Figure Page
Number Title Numter
22. Furnace 36.
23. Furnace Tube Assembly 38.
24. Detail of Gas-Tight Tube Fittings 41.
25. Electrical Heating and Control Diagram 43.
26. Two Phase Sampling Aid 50.
27. Miscibility Gap Cu-S System 52.
28. Quenched Specimen. Copper Melted in Iron
Crucible 1250 0 C Hydrogen Atmosphere. 55.
29. Quenched Specimen. Immiscible Liquids in Iron
Crucible 1250 0C. Hydrogen Atmosphere. 56.
30. Quenched Specimen of Immiscible Liquids in Iron
Crucible 1250 0 C. Hydrogen Atmosphere. 57.
Figure
Number Title Page
Number
LIST OF TABLES
Table Page
Number Title .Number
ACKNOWLEDGMENTS
difficulty;
numerous instances;
I-1 General
ones.
In the field of extractive metallurgy considerable
improvement.
of the, constituents.
Cu
Figure 1
Location of Commercial Matte Compositions in
the Ternary Cu-Fe-S
System (Reuleau-)
4
Table 1
Source Percentage
Cu S Fe Fe 3 0 4 Zn Pb Bi As Ag Ai
IN
5
locates commercial matte compositions on the ternary diagram
Figure 2
Liquidus Surface Cu-Fe-S System (Reuleaux3)
7
tamination.
the ternary system. From these sections the author has drawn
Fe 10 20 30 -40 50 60 70 80 90 S
FeS 1 -08 %S--
Figure 14 6
Isothermal Section Cu-Fe-S System 1150C (Schlegel & Schuller6)
Cu
10 90
Cu2 S
20 80
I 250*C
m,+yFi
70
40 60
.\. 1 +m 2 +yFe
/ 50 50\
0
60
\40
7 30
80 20
90,
10
yFe
Fe
10 20 30 ,-W40 50 60 70 80 S
90
FeS,. 0 8 %S--
Figure 5
Isothermal Section Cu-Fe-S System (Schlegel & Schuller6)
Cu
I 90
Cu2S 1350 0 C
2 k8 O
3 'O
60
50/ 50
40
m, + y7F
70, 30
mI + m 2 + y
81 20
2/
Fe 10 20 30 /- 40 50 60 70 80 90 S
FeSL 0
8
Figure 6
Isothermal Section Cu-Fe-S System (Schlegel & Schuller 6 )
Figure 7 is an isothermal section of the system at 90000
and indicates readily the primary solid precipitates re-
that the join Cu2 S-FeSl.08 passes through the ternary eutetic
point whereas the join Cu 2 S-FeS does not. This is also true
compositions.
14
1400 - 1-
Cul FeS30O
S, -
1100 S *Cu4 FeS3 0 8
U
0 jS.Cu I
Cu4 FeS
0 800 -1-
Ge Cu1.FeS ,o+FeS
4
Ge
500!Cg~S
CuF S
Kupfer in %
I 0 40 | 20'
200 L A -. ,A- J -- - -
Cu2 S 20 40 60 80 FeSy,0 .
Fe,,8 -in %
of Cu-Fe-S System
6
(Schlegel and Schuller )
15
8
a ----- Fe -S -Cu Cu/S:::::1.3
6 -
S5 -
4 10
Figure 9
Effect of Cu Addition on S Activity in Fe
15500C
(Rosenqvist and Cox 8 )
Since the ternary system copper-iron-sulfur is bounded
1800
1600
E.
1400 ........
'Fe 10 20 30 40 50 60 70 80 90 Cu
Weight Percentage Copper
+C - 1500
1300
Hz
8 1500
750- ~
E +a
2 25 3 35 4 ' 5 5
Cu 05 1 1.5
Weight Percentage Iron
Figure 10
Cu-Fe Binary System
(Daniloff )
18
Figure 11
Cu-S Binary System
(Rhines 16)
Oc Atomic Percentage Sulfur
20 30 40 50
1600
15 ' 20 25 30 35 40 45 50
Weight Percentage Sulfur
Figure 12
Fe-S Binary System
(Chipman 2 5 )
19
0F e /C
00
0.6
: I
04
~ /
02
/ 2 04 0.6 08
Copper (mole fraction)
Figure 13
Activity Composition Diagram
Cu-Fe System
16000C
(Chipman9 )
20
I..
| | ,/ ss I| | |. |3
6'__8 .Chipmon u.Tall a 4"175eumgredm~et ~ ?0
~-0 e reenebv sse be!,#75" Z10
5 190
180
3-0 170
z -# - -0- - -1'0
1- 150
4? OW o6t 08 10 1;Z If r.6' M0 ZZ Z# Zo
Sulphur( wt. %) 130
12'0
- 110g
30 4F
-.000L0l
1?0 -- 4 oOniEAl
L-.P- t t" --
IV~ 9 6' 8 10 1? 1# 1 10 6O0 ? 9 06 08 3t 3? 3f 36 380
Sulphur (wt. %)
Figure 14
Sulfur Activity in the Fe-S Binary System
(Mauer, Hammer, Mobius 10)
0320 0325 0330 0.335 0.340 0.345 0350 0355
MOL FRACTION SULPHUR
4.,
4
0.355
good. Rosenqvist
15 has
studied the following two reactions:
This study of the second reaction was done only at one temper-
previously believed.
Schuhmann and Moles has determined the equilibrium
6 -
1350 /
5 -/1350
MISCIBILITY GAP
0 - -II
0
0 0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2
% S BY WEIGHT
Figure 17
Sulfur Activity in Cu-S System
24
0.5
3
0.4
H2 S/ 2 103
H20/H2
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1.0 1.2.
WT. PCT S. IN CU.
Figure 18
(Rosenqvist1 5 )
They arbitrarily choose the activities of both copper and
present at equilibrium.
states that the system has only one degree of freedom. Con-
the condensed phase and the sulfur pressure before the in-
point out at this time that the work was carried out in the
ternary system.
II. Description of Equipment and Materials Used
the composition of the gas mixture before and after the gas
gas inlet
gas
outlet
,24/40 joint
10/30 joint'
inlet
outlet
deail of
bubbler
dtail \
manomet-er
air into the main gas stream. Needle valves were provided
11-4 Furnace
3 4 .5 inches
ANALYSIS. APPARATUS
36
. -zj- - - :, LEGEND
A tEo r g/e' *LOBAR
HEAT ELEMENTS
SB. W. K-30 USILATING
BRICK
C TRANSITE TOP
0 TRANSITE COVERS OVER
$LOBAR ENDS
C E HOLE FOR FURNACE TUBE
F RAVOTUBE FOR TEMPER-
ATURE CONTROL
6 I/16" THICK ALUMINUM-
D
-PAINTED SHEET IRON
BOTTOM AND SIDES.
-
A
Fig. 22 -- Ftrnace
37
deep and was insulated with Babcock and Wilcox K-30 type
painted sheet iron on the sides and bottom with a 3/8 inch
exit
thermocouple
leads
cooling water in ..., water out
Band W K-30
:!/
globar heating
rods gas exit tube
gas bubbler- 3 alumina
tube
radiation shields
thermocouple
tube
.alunina spacer
zirconium furnace
silicate tube
alumina crucible
about one quarter of an inch below it, was the gas exit tube.
protection tubes. They and the gas exit tube supported three
alumina radiation shields spaced approximately one-quarter
fitting between the ceramic tube and the brass head. The
protection sleeves terminated prior to passing through the
Figure 24. Above the head the gas bnbbling tube was con-
CERAMIC TUBE
HOLES
BRASS HOLLOW
SCREW
BRASS WATER-COOLED
- HEAD
NEOPRENE
(7 0-RING
required.
mental campaign.
43
110 V
220V 110 V
7
6
Fig. 2 5--Electrical
Heating and Control Diagram
6 Furnace
7 Rayotube: Leeds and Northrup Co. 22.4 MV at 1650*C,
lens to object distance 24 inches minimum.
44
II-'8. Materials
sulfur.
than 99.9 per cent pure. The sulfur used was U.S.P. pre-
.0009 .010
Sn .0003 .010
As .001 . 001
Ni .0015
.00009
TL .0002
0' .035
Table 3
S .008 CO .007
47
analyzing 99.95% iron, .04% oxygen, and .005 carbon was also
used.
The cuprous sulfide used in this investigation was
prepared by Moles 22 and involved reacting copper with molten
sulfur. This material contained 78.42% copper and 20.55%
sulfur. The main impurity was expected to be oxygen but
this would be removed readily by the hydrogen atmosphere
used in the experimental runs.
Iron sulfide was prepared by a method previously used
23
by Krivsky and Inder. Iron powder was intimately mixed
with 10% excess sulfur and reacted in an alumina crucible
by heating gently with a Bunsen flame. Approximately 30 grams
could be made in each batch without excessive evolution of
heat. The crucible was covered with a watch glass while
the charge was cooling. Several such batches were con-
solidated and charged into a large crucible in a closed
furnace tube assembly. The charge was then melted under
hydrogen and held at 130000 for approximately one hour while
bubbling hydrogen through it. The product of this process
analyzed 64.7% Fe, 34.4% S and .06% R 203 . A modification
of this process in which nitrogen was bubbled through the
melt instead of hydrogen yielded a product analyzing 63.3% Fe,
melt surface. The tube was then lowered very slowly while
fell sharply when the end of the sampling tube became im-
mersed in the top liquid; the tube was held in this position
several days. Sampling was done once daily and then the
50
30o
(.j
51
p X SMITH, D'4
a SCHUHMANN a MOLES"
+ JENSEN12
7
o SMITH, C.S 2
V SUDO0 3
0 ROSENQVIST' 5
0 THIS INVESTIGATION
1300 I
0I
wI
IRHINES' 6 RHINES1 6
H0
0X1
-w 0
1200 - o
I
-XI
01 0
11006
0 2 4 6 8 10 12 14 16 18 20
WEIGHT % S--
Figure 27
Miscibility Gap Cu-S System
53
Table 4
Weight Percent
Time T emBerature Silicon
(Hrs.) 0 Metal Phase Matt e Phase
0 1239 -03 13
24 1257 .03 02
48 1126 .03. 09
#K
58
one gas and (b) jolding.the iother ga.* Later in this section
how well one gas could be held in the system while the
a:
wm20
16
12
4-x
01-
0 2 4 6 8 10 12 14
% H2 S
Figure 31
Gas Analysis Error Versus Percent H 2 S
60
range was enhanced by cutting off part of the gas and com-
in the normal way with the left leg of the manometer set at
61
the 77.50 centimeter mark. The gas was then cut off and
compressed as described for Case II of Appendix A.
Table 5
A B
Test Compression Test Compression
Ratio Ratio
1. 15.582 1. 15.414
2. 15.547 2. 15.436
3. 15.541 3. 15. 427
4. 15.542 4. 15.546
5. 15.586 5. 15.565
6. 15. 433
7. 15.538
MODIFICATION A
MODIFICATION B
LIQUID
X7. NITROGEN TO VACUUM PUMP
a I TRAP
STOPCOCK 5
MODIFICATION C
Table' 6
(Modification B)
3 2.829 3.045
4 2.902
66
methods of- sampling for the furnace inlet and exit gases.
Table 7
Table 8
-Batch Flush
1. 14.916 14.847
2. 14.981 15.106
3. 15.057 14.962
1. 0.363 0.367
2. 0.369 0.362
3. 0.361 0.368
1. 0.308 0.294
2. 0.294 0.292
3. 0.298 0.303
4. 0.302 0.305
5. 0.301 0.300
6. 0.299 0.296
69
Table 9
Reproducibility of Gas Analysis
Method at Different Compositions
(f H2 S)
sulfide than the exit gas was then bubbled through the system
and the exit gas re-analyzed. Usually the two exit gas
was then altered to the exit gas value and allowed to bubble
for a prolonged period (at least eight hours and usually over-
established.
A similar procedure was adopted for the equilibrium
Table 10
0 0.254
24.5 0.371
27.0 0.294
gas mixture was approached from the high and low side as
bubbled through the melt until the exit gas became of the
in this region (see Results), and the inlet gas had only
Table 11
0 0.00.
19 0.00 2.42
20 2.63
23 2.63 2.24
24 2.41
30 2*41
31 2.22 2.25
43 2.22
7
together with that of the gas flow train and other auxiliary
the bath was molten the remainder of the desired charge was
74
was bubbled through the melt. The entire furnace tube was
and all exit gases from the furnace tube left by way of the
gas exit tube. The search for equilibrium was then started
experiments.
IV-2. OQn-Phase Melts
samples were taken. One sample was kept for reference while
over 600 gas analyses were made during the course of these
analyses.
head and passed out the gas exit tube. Due to the very low
V-l. General
-- Experimental Results
(Analyses by Weight %)
Experimental Results
(Analyses by Weight %)
*For 2 and 3 phases data first line refers to high sulfur liquid, second line to low sulfur liquid.
0
Table 13
Experimental Results*
(Analyses on a Molar Basis)
1 2 1150 3.01 1.066 .1830 .6883 1.917 .5503 .0945 .3552 .1717 .6457
1.518 -0419 -0384 1.598 .9499 .0262 .0240 .0276 .0253
2 2 1251 4.11 1.072 .1782 .6848 1.935 .5540 .0921 .3540 .1662 .6388
1.507 .0471 .0502 1.604 .9395 .0294 .0313 .0313 .0333
3 2 1351 5.53 1.068 .1844 .6808 1.933 .5525 .0954 .3522 .1727 .6375
1.504 .0543 .0443 1.603 .9382 .0339 .0276 .0361 .0245
4 2 1351 5.74 1.105 .1484 .6705 1.924 .5743 .0771 .3485 .13~43 .6068
1.516 .0415 .0418 1.599 .9481 .0261 .0261 .0274 .0276
5 2 1256 4.45 1.096 .1538 .6783 1.928 .5685 .0798 .3518 .1403 .6189
1.521 .0380 .0380 1.597 .9524 .0238 .0238 .0250 .0250
6 2 1154 3.40 1.123 .1307 .66/j 1.919 .5852 .0681 .3465 .1164 .5921
1.529 .0270 .0424 1.598 .9568 .0169 .0265 .0177 .0277
7 1 1349 5.60 1.121 .1289 .6717 1.922 .5832 .0671 .3495 .1150 .5992
8 1 1263 4.54 1.122 .1280 .6727 1.923 .5835 .0666 .3498 .1141 .5996
9 1 1148 3.27 1.123 .1284 .6705 1.922 .5842 .0668 .3489 .1143 .5971
10 1 1155 47.7 1.083 .1508 .7092 1.943 .5574 .0776 .3650 .1392 .6548
11 1 1247 46.2 1.091 .1470 .6986 1.937 .5632 .0759 .3607 .1347 .6403
12 1 1349 41.2 1.090 .1577 .6839 1.932 .5642 .0816 .3540 .1447 .6274
13 1 1353 75.1 1.089 .1479 .7023 1.939 .5616 .0763 .3622 .1358 .6455
14 1 1353 76.9 1.082 .1549 .7045 1.941 .5574 .0798 .3630 .1432 .6511
15 1 1354 13.6 1.097 .1529 .6786 1.929 .5687 .0793 .3518 .1394 .6186
16 1 1357 7.30 1.098 .1570 .6702 1.925 ..5704 .0816 .3482 .1430 .6104
Table 13 (Continued)
Experimental Results
'(Analys6s on a Molar Basis)
Experimental Results
(Analyses on a Moldr Basis)
33 1 1148 325.5 .4939 .6768 .9611 2.132 .2317 .3175 .4508 1.370 1-946
34 1 1151 155.55 .4975 .6800 .9484 2.126 .2340 .3199 .4461 1.367 1.906.
35 1 1148 71.6 .4986 .6847 .9381 2.121 .2351 .3228 .4423 1.373 1.881
36 1 1148 26.7 .5060 .6901 .9141 2.110 .2398- .3271 .4332 1.364 1.807
37 1 1148 16.6 .5063 .6940 .9066 2.107 .2403 .3294 .4303 1.371 1.791
38 3 1150 2.71 .9677 .2797 .7138 1.961 .4935 .1426 .3640 .4235 .7376
1.484 .0820 .0359 1.602 .9263 .0512 .0241 .0526 .0242
39 3 1285 3.79 .9281 .3377 .6914 1.957 .4742 .1726 .3533 .3639 7450
1.181 .3653 .1419 1.688 .6996 .2164 .0841 .3093 .1202
40 ,I1 1350 6.0 .8296 .4548 .6827 1.967 .4218 .2312 .3471 .5482 . 8299
41 3 1353 4.44 .7912 .5316 .6253 1.948 .4062 .2729 .3210 .6719 .7903
.6629 .9198 .2030 1.786 .3712 .5150 .1137 1.388 .3062
42 1 1354 923 1.095 .1248 .7313 1.951 .5613 .0640 .3747 .1140 .6679
43 1 1253 1336 1.090 .1268 .7375 1.954 .5578 .0649 .3774 .1163 .6766
44 1 1153 2000 1.090 .1261 .7388 1.955 .5575 .0645 .3779 .1157 .6778
45 2 1351 4.23 .8642 .4131 .6867 1.964 .4400 .2104 .3496 .4780 .7946
1.214 .3305 .1372 1.682 .7218 .1965 .0816 .2722 .1130
46 2 1357 4.20 .8503 .4376 .6714 1.959 .4340 .2234 .3427 .5146 .7896
1.031 .5021 .2018 1.735 .5942 .2894 .1163 .4870 .1957
47 1 1361 40.0 .5022 .6988 .9963 2.107 .2383 .3317 .4301 1.391 1.805
48 1 1158 12.0 .5025 .7035 .8944 2.100 .2393 .3350 .4259 1.400 1.780
*For 2 and 3 phase data first line refers to high sulfur liquid, second line to low sulfur liquid.
84
Table 12
2.18
2.221-
0 LOG P2 0.394
PH2S/ PH 2 T
2.26[-
2.30
Cu 2 S(4) + H2 (9)
2 Cu (1) + H2 S(9)
(SCHUHMANN AND MOLE S)
2.32
a. x
0 2.38
2.42
L OG PH2 S/H 2 - -O
2.46
THIS INVESTIGATION:
3 PHASE EQUILIBRIUM
2.00 LIQUID METAL-LIQUID MATTE
SOLID GAMMA IRON
2.54
x
2. ~ .
58 I i I I I I i I I I I i 1 ' 1
6.0 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 7.0 7.1 7.2 7.3
10 4 /T
Figure 33
Log PH2,/P Versus Temperature. 3 Phase Data.
86
8 100
6 %80
6-
METAL PHASE
%S 60
- 4-0
% Fe
2 -
x
+20 10 4
00
Figure 34+
Composition of Iron-Saturated Metal Phase of
Miscibility Gap Versus Temperature.
87
24 100
MATTE PHASE 80
%CU 60z
w x
0
020
aD
20 0
6.0 6.2 6.4 6.6 6.8 7.0 7.2
T
Figure 35
Composition of Iron-Saturated Matte Phase of Miscibility
Gap Versus Temperature
88
I
U2S
21 80
1150*C
m+ yF
30OA
mI + m2 +
k 41 0 .a.
*c,
50/ m2
6 0
7 20
8 20
Fe
10 20 30 , 40 50 60 70 80 90
FeS 1 -0 8 %S -
Figure 36
Isothermal Section Cu-Fe-S System. Miscibility Gap Including Iron Solubility According to this
Investigation. Numbers in Parentheses Equal
PH2/PH
Cu
I 90
\(4.90)
Cu2 S
20 -480
3 70 1250*C
4
+ m2 +yFe
A~
0
0\0
5 0 cC,
60 40
m2
80 20
9 10
yFe
Fe
10 20 30 /' 4 0 50 60 70 80 90
FeS1D8
% S--
Figua re 37
Isothermal Section Cu-Fe-S System Miscibility Gap Data Including Iron Solubility Limit from this
Investigation. Numbers in Parentheses Equal PH S H
Cu
FeV
Fe 10 20 30 /40 50 60 70 80 90 S
Fe Sj.og
Figure 38
Isothermal Section Cu-Fe-S System Miscibility Gap Including Iron Solubility Limit from this Investigation.
Numbers in Parentheses Equal P /P(
H2 S H 2
92
tions at/ = 0.141 were carried out only at 13500 C and are
1350 0 C
0.4
0.81-
,8 = 0.141
N
x~
a- I .2
cn
zm SCHUHM ANN THI S
AND MOLES INVESTIGATION
0 I.6
2.0--
MISCIBILITY GAP
2.4F-
2 8
. K -
Figure 39
Log PH S/PH Versus a 1350 %
94
0.40
Q60
0.80
1.00
1.20
61
0.
a. 1.40
0
0
I 1.60
1.80
2oo
2.20
2.40 "-
1.70 1.74 1.78 1.82 1.86 1.90 1.94 1.98
a =NS/NCu
Figure 40
data were plotted and the best line drawn through the
0.4
- a =1.93
0.8
n. 1.89
0 1.2 1.85
1.6 --
~~ '1.77
2.0 -
I I I I I 1 1
6.0 6.4 6.8 7.2
104y
-3400 17,500
-3800 18,500
-4200 19,500 w
a.a
- 0
0 c
-4600 20,500 2
0
II
-5000 21,500
-5400 22,500
-5800 23,500
1.75 1.77 1.79 1.81 1.83 1.85 1.87 1.89 1.91 1.93 1.95
a=NS/NCu
Figure 42
Partial Molar Heat of Transfer of Sulfur from H2S Gas to Matte.
98
2.20
2.00-
-. 25
-.50
-. 75
1350*C LOGP 2$ 1.OC
1.80 -- 2 .5
51
1.7!
2.0
1.60
CuzS-FeS /
u 1.40 -
z
1.20-
-2.1
-2.2
1.00 / /MELT + y Fe 6
-Z.3 (SCHLEGEL a SCHULLER
0.80-
0 .4 01 I I I I I I I I I I I I I
0 0.20 0.40 0.60 0.80 1.00 1.20 1.40
:N Fe/NCu
Figure 43
Iso-Sulfur Activity Lines Cu-Fe-S System. One Phase Region
99S
Cu2 S
21
I 350*C
30/ MISCIBILITY 70
GAP
6 60
/
50 2
0i
0
6 40
7 25 30
8 MELT + 20
yFe
90 10
*, /
Fe
50 60 70 80 90 S
%S-
Figure 44
Iso-sulfur Activity Lines in Cu-Fe-S System (-1.25 Line Extrapolated to Data of Mauer, Hammer,
and Mobius10 in Fe-S System) (Weight 5 Diagram)
.01
VI. Derived Results
2.22
0-
a.
N
(D
0
IJ 2.30
2.38
= NFe/NCu
Figure 45
Versus Composition of Matte Phase of Miscibility Gap 1350 0C.
PH2 S/ H2
a'= N'/Nou' (METAL PHASE)
0.08 0.16 0.24 0.32
2.18 0
2.22
2.26
0
1-3:
(I)
O 2.30
0
2.34
2.38
2.42
0 0.4 0.8 1.2 1.6
the same scale in Figure 47. From this figure the values
to 0.95 when the solid gamma iron phase was present; this
therefore neglected.
for iron and copper is the same with the iron activity
C,,
2.26
a-
0
2.30-
2.34
2.38
0 .16 .32 .48 .64 .80 .96 1.12 1.28 1.44 1.60
S OR S
Figure 47
Log PH2S H2 Versus Iron-Copper Ratio. Miscibility Gap. 13500
106
2.05
1.95
1.85 _ XXx
1.75 -
1.65
1.55
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
O'
/3OR
Figure 48
Copper Activity in Miscibility Gap, 135000,
1.0
0.9
0.8
0.7
0.6
0
Fe
0.5
0.4 -
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
$ OR 0'
Figure 49
Iron Activity in the Miscibility Gap 135000
108
reaction
the relationship
dlog a~u 2 S =2 d log aCu + 0log 'H2S
follows:
0 C
111
1.00
X\
x
0.84
x
0.68
0.52
xtx
0.36
0.20
0 0.2 0.4 0.6
S= NFe/NCu
Figure 50
Activity of Cu2 S Along High Sulfur Boundary of Miscibility Gap 135000
II~
0.4 NFe/NCu
/x '7
X/ /
/ /
x
0.8
5x
CY
x 1.2 /
/X
/X
/ /
X
CM
x
/ / /
1.6
/ / /
2.0
/ / /
2.4
2.6 I I I I I I I I I
0.75 0.85 0.95 I .05 1.15 1.25
a =Ns/Ncu
Figure 51
tion of the copper and iron activity occurs over a very small
1.6 -
a0u
0 0.20\ 0.40 0.50 0.6 X .66
0.8
xx
xx
'X X \X k,
0.0
0.40 0.56 0.72 0.88 1.04 1.20
a Ns/Ncu
Figure 52
Cu Activity as a Function of OL. 135 0 0 c.
1.0 1 '7
I I I
0.9
B NFe/Ncu
0.8 -
-'
0.7 -
-I
-I
0.6 k
OFe ...
0.5
- MS "BLIN
0.4 |-
0.3
0.2 0.20
0.1
0
0.68 0.84 1.00 1.16
a = NS/NCu
Figure 53
0.5
log allu. -5
-.50
log PHi2S/?Ht
matte and solid gamma iron. When they are, the present
reference states.
119
2 PO22
range.
range of composition.
0.7 and extending into the one phase region from the two
phase boundary limit appears to be scientifically a very
solution.
124,
X. BIBLIOGRAPHY
pp. 873-884.
10. Mauer, E., Hammer, G., and Mobius, H.; Das Gleich-
235.
12. Jensen, E., Avh. norske Vidensk Akad., Oslo, 1, No. 6, 1947
Metals, 1948.
17. Elliot, J. F., and Chipman, J.; J. Amer. Chem. Soc. 73,
1951, p. 2683.
18. Darken, L. S.; J. Amer. Chem. Soc. 72, 1950, p. 2909.
Mines, 1937.
M.I.T., 1950.
1948.
25. Chipman, J.; Metals Handbook; Amer. Soc. Metals; 1948;
p. 1196, 1215.
p. 325.
Company.
Reference: Figure 21
were read. Six such tests gave an average value for this
~ 16.2 x
I
x
o x
w 16.0
a.
0
C)
z
w
a 15.8
C
-a-
15.6
equilibrium:
readily solved.