[COXTRIBUTION FROM THE JOHN HARRISON LABORATORY O F CHEMISTRY, No. 59.1
T H E ELECTROLYTIC METHOD APPLIED TO URANIUM. Br LILYGAVIT KOLLOCK A N D EDGAR F. SMITH. Received July 5. 1901.
T
HE purpose of the present communication is to call attentim
to the conditions under which uranium can be q u a n ~ t a tively determined in the electrolytic way in solutions of the acetate, the sulphate, and the nitrate, and also to record several separations of uranium by the same means from other metals. I t is not necessary to comment further upon the form in which the uranium is precipitated or upon the way in which the deposit is subsequently treated in order to weigh it, as those points have received sufficient attention elsewhere.’ ELECTROLYSIS O F URANIUM 8
ACETATE. .e
$
.-E:
e= 2. $s Db
0.0986 0.0986 0.1972 0.1972 0.1972 0.2952 0.2952 0.2298 0.2298 0.2298
I 2
3 4
5 6
7 8 9 IO
0.2
125 125
0.2
125
0.2
I25
0.2
125 125 125 125 125
0.2
0.2 0.1
0.1 0.2
0.1 1 2 5
0.0988 0.0989 0.1968 0.1970 0.0966 0.2946 0.2948 0.2297 0.2299 0.2299
zl?
WbK
+ 0.0002
+
0.0003
- 0,0004
-0.oo02
-0.0006 - 0.0006 -0.0004 -0.OooI
+ 0.0001
+
O.oo0I
It was hoped that possibly iron might be separated from uranium in the acetate solution. Direct experiment demonstrated the opposite. T h e basic iron salt invariably separated when the temperature of the solution rose to 50’ C. Further, the presence of iron in the solution apparently retarded the precipitation of the uranium, as none of the hydroxide of the latter separated with a current of 0.18 ampere and 8 volts. On adding chrome alum to the uranium acetate solution containing 2 cc. of free acetic acid and increasing the voltage to 2 0 , there occurred no 1
A m . Chem.J.. I , 329; This Journal, 2 0 , 279; and Smith’s “Electrochemical Analyeis,”
p. 94.
608
L I L Y GATIT Ii0LLOCI.I .\XI) E D G A R I . ShIITIi.
deposition of uranic hydroxide : the chromic oxide hand was converted into chromic acid.
011
t h e other
THE ELEcTnoLrsxs O F UKAXI'I. SITRATE SoLvnoss. Ur,Or Temperpresent Dilutioii. ature. ingrams. cc. 'C. 0.1222
125
7j
0.1222
12j
6j
Volt-
Current
age.
h-.D,l,,7=-0.0;j A N.D.,,, -=0.04 A
4.6 2.25
Time. Hours.
Ur,,O, found i u prams.
5 7
Quantitative results were also obtained by the electrolysis of the sulphate. The neutral salt solution was diluted to 1 2 5 cc. and heated to 7 jo C., when a current of from 0 . 0 2 to 0.04 ampere for IO: sq. cni. of cathode surface and 2 . 2 5 volts was passed. ELECTROLYSIS OF ~ K . C W L SULPHATE. .-
+
% C 16
%t%
;'
A E
3
-;
: Y
9.5
z$
$9
0.1320
125
0.1320
Izj
75 75
0.1393 0.1393
I2j
7j
125
70
-
.-.
-
'j
K.D.lo7-=:o.oz .I K.D.,,; -= 0 . 0 2 X N.D.,,; := 0.04 X N.D.l,!j ~- 0.038 A
i .
.-
.
z
-.-6:
0.1320
2
54
0.1322
----0.0002
2.25
j
0.139j
- - 0.0002
2.2j
7
0.1392
L
c:
1
,
2;
.:c
,
-,:
"-
I-
L Z
: '.L
7
3F:
k'
.... --0.0001
T H E S E P A R A T I O N O F U R A S I U 3 I F R O M B4XIUi14, CALCIYJI, M A G S E -
S I U M , A N D ZINC.
I n the paper by Smith' to which reference ha5 already been made, he calls attention to the separation of uranium in the electrolytic way from the alkali metals and from barium. Actual results are given. It seemed desirable to amplify the suggestion ; hence the presentation of the results given below. I t may be said here, that in attempting to separate nickel and cobalt no satisfaction could be obtained, SO that eventually that particular line of experiment was abandoned. During the precipitation of the urano-uranic hydrate the dish should be well covered so that a5 little evaporation as possible occurs. I t wa5 observed that in case of evaporation there was danger of other salts separating upon the exposed metal and on refilling with water the uranium precipitate was apt to enclose the same and thus carry with it a slight impurity. This precaution is especially necessary in the separation from zinc. 1
Loc
(If
ELECTROLYTIC METHOD APPLIED
609
TO URANIUM
SEPARATION O F URANIUM FROM BARIUM (ACETATES).
I
0.1116 0.11
05
125
70
2
0.1116
0.11
0.5 125
3
0.1116
0.11
0.2
65 70
125
2 sf 0.1119 fo.0003 N.D.,,,=o.ozA N.D.,,,=0.04 A 8 51 0.1117 +o.O0OI N.D.,,,=o.r A 4.5 4 0.1117 +o.omI
SEPARATION OF URANIUM FROM CALCIUM (ACETATES).
I
z
0.11160.1
0.2 0.1116 0.1 0.2
3 0.1116
0.1
4 0,1116
0.1 0 . 2
0.2
70 N.D.,,,=o.o25A A 125 70 N.D.,,,=o.04 A 125 70 N.D.,,,=o.05 125 70 ~ , D . , , j = o . 0 2 5 A
125
2.5
6 ; 0.1113 54 0 . 1 1 1 4
2.25
:4
2.0
46 0.1115
2.25
-0.0~03
-0.oo02
-0.0003
0.1113
-O.OOOI
SEPARATION OF URANIUMFROM MAGNESIUM(ACETATES).
125
I
0.1116
0.1
0.1
2
0.1102
0.1
0.1 125
3
0.1120
0.1
0.1
125
70 N . I ) . , , , = o . o ~ ~ A 2 . 2 5 6 0.1115 -O.OOOI 70 N.D.,,,=o.oj A 2 . 2 5 5$0.1104 $o.oooz 4 0.1119 -O.OOOI A 4.0 75 N.D.,,,=o.15
SEPSRATION O F URANIL'M FROM ZINC ( A4CETATES).
I
0.1120 0.1 0.1
125
2
0.1102
0.2 0.2
125
3 4 5 6
0.1102
0.1 0.1
125
0.1102
0.1 0.2
125
70 70 70 75
O.IIOZ
0.15o.z
125
75
O.IIOZ
0.2 0.2
125 175
....
N.D.,,,Lo.ozI A 2.25 6 0.1120 N.D.,Oj=~.o17 A 2.25 6 0.1099 -0.0003 N.D.,,,=o.oz A 2.2 6 0.1100 --oo.oo02 4.4 4j0.1103 +O.OOOI N.D.,,,-00.025A Tu'.D.,,,=o.o~ A 2.2 6 0.1105 Jr0.0003 N.D.,,,=o.oz A 2 . 2 5 6 0.1099 -0.0003
C'NIVERSITY O F PENNSTLVANIA.
