ADSORPTION OF COBALT, BARIUM, AND ZINC FROM VERY DILUTE SOLUTIONS

148 Pages·4.509 MB·English

by  KVAMME, ORVILLE JAMES

ADSORPTION OF COBALT, BARIUM, AND ZINC
FROM VERY DILUTE SOLUTIONS
Dissertation
Presented in Partial Fulfillment of the Requirements
for the Degree Doctor of Philosophy in the
Graduate School of The Ohio State
University
By
ORVILLE JAMES KVAMME, B.S., M.S.
The Ohio State University
1952
Approved by:
C7fj
i
Adviser
dviser
Table of Contents
Page
I, Introduction................................. 1
II. Literature Survey........................... 4
A. Properties of Radiocolloids.......... 4
1. Dialysis........................... 4
2. Electrophoresis and Filtration... 5
3. Hadioautography.................... 8
4. Sedimentation and Centrifugation. 9
B. Target Separations by Filtration 12
C. Properties of the Filter Paper....... 16
D. Radiocolloids Interpreted in Terms
of the Diffuse Double Layer Theory... 30
III. Experimental Procedure..................... 36
A. Target Chemistry....................... 36
B. Experimental Technique................ 42
IV. Experimental Results and Discussion....... 48
A. Adsorption of Divalent Cobalt,
Barium, and Zinc on Filter Paper,.... 48
1. Dependence on......... pH.......... 48
a. Cobalt......................... 48
b„ Barium......................... 64
c. Zinc. ...... 72
2. Dependence on Concentration.... 80
3. Dependence on Ammonium Chloride
Concentration...................... 87
£29772
-ii-
Eflgft
4. Dependence on Manganous and Cup-
ric Chloride Concentration......... 96
5. Dependence on Ammonium Sulfate
Goncentra tion....................... 104
B. Nature of the FilterP aper Adsorption.. 109
1. Effect of Washing the Adsorbed
Cohalt and Zinc..................... 109
2. Titration of theF ilter Paper 116
3. Adsorption of Zinc at a Water-
Hexane Interface.................... 119
C. Adsorption of Cesium on FilterP aper... 122
V. Summary.................... 126
VI. Conclusions................................... 134
VII, Bibliography............ 137
VIII. Autobiography................................ 140
-iii-
Tables
Page
I. Effect of pH on Cobalt Adsorption after
Three-Day Standing....................•>.... 49
II. Effect cf pH on Cobalt Adsorption by
Paper and Glass with Filtration Within
Ten Minutes after Titration............... 52
III. Adsorption of Cobalt by Successive
Filters after Three-Day Standing....... 55
56
57
IV, Effect of pH on the Adsorption of Barium
in Concentrations less than 1 x 10-8
g. atoms/30 ml.................. 66
V. Effect of pH on Barium Adsoprtion
(Stable Barium Added)...................... 68
VI, Effect of pH on Adsorption of Zinc........ 73
74
VII. Effect of Concentration of Cobalt on
its Adsorption....................... 81
VIII. Effect of Concentration of Zinc on its
Adsorption........... 84
IX. Effect of Ammonium Chloride Concentra­
tion on Cobalt Adsorption............. 88
X. Effect of Ammonium Chloride Concentra­
tion on Zinc Adsorption....,.............. 94
XI. Effect of Manganous Chloride Concentra­
tion on Cobalt Adsorption................. 97
XII. Effect of Cupric Chloride Concentra­
tion on Zinc Adsorption......... 101
XIII. Effect of Ammonium Sulfate Concentra­
tion on Zinc Adsorption......... 105
XIV. Effect of Washing the Adsorbed Cobalt 110
XV. Effect of Washing the Adsorbed Zinc....... 112
£agft
XVI. Effect of Washing the Adsorbed Zinc
with Solutions of Various Acidities 114-
XVII. Adsorption of Zinc by a Water-Hexane
Interface......... 120
XVIII. Effect of pH on Adsorption of Cesium 123
- V -
Figures
P^ge
1. Effect of pH on Adsorption of Cobalt
by Paper...................... 51
2. Effect of pH on Cobalt Adsorption by
Glass and Paper............................. 59
3. Effect of pH on Adsorption of Cobalt
by SuccessiveF ilters............ 60
A. Effect of pH on Adsorption of Cobalt
by Glass..................................... 62
5. Effect of pH on Adsorption of Barium
by Paper.... ................................ 67
6. Effect of pH on Adsorption of Barium
by Paper, Stable Barium Added............. 70
7. Effect of pH on Adsorption of Zinc
by Paper..................................... 75
8. Effect of Ammonia Concentration on
Adsorption of Zinc.''..,......... 78
9. Effect of Ammonia Concentration on
Adsorption of Cobalt........................ 79
10. Effect of Cobalt Concentration on Ad­
sorption of Cobalt by Paper................ 82
11. Effect of Zinc Concentration on Ad­
sorption of Zinc by Paper.................. 85
12. Effect of Ammonium Chloride Concentra­
tion on Adsorption of Cobalt by Paper 90
13. Effect of Ammonium Chloride on Cobalt
Adsorption................... 92
1/+. Effect of Ammonium Chloride Concentration
on Adsorption of Zinc by Paper............ 95
15. Effect of Manganous Chloride Concentra­
tion on Adsorption of Cobalt............... 98
-vi-
Page
16. Effect of Cupric Chloride Concentra­
tion on Adsorption of Zinc................. 102
17. Effect of Ammonium Sulfate Concentra­
tion on Adsorption of Zinc....... ......... 106
18. Titration Curves for the FilterP aper 117
-vii-
ACKNOWLEDGMBNT
The author wishes to take this opportunity to
express his appreciation to Professors M. H, Kurba­
tov and J. D. Kurbatov for their excellent instruction
and advice in the accomplishment of this work. Besides
problems of a technical nature that arose in the course
of this study, their consideration of the personal
problems of the author was particularly appreciated.
To the United States Air Force, the author ex­
presses his sincere gratitude for making this work
possible.
INTRODUCTION
It has been known for almost forty years that
certain heavy elements, such as radioactive isotopes
of lead, bismuth, and polonium, can be filtered at
concentrations much below that of so-called “saturated
solutions" of their oxides. As these solutions often
exhibit properties which are more like colloids than
true solutes, they have become known as "radiocolloids".
More recently it has been shown that the elements,
yttrium, zirconium, and lanthanum, exhibit the same
property, when the concentration of their respective
compounds are much lower than theirs olubilities. In
the above examples of radiocolloids, each element had an
oxidation state of three or more.
This tendency of some radioactive isotopes to be
adsorbed on filter paper has been utilized in separa­
tions of activated target materials, the value of which
lies in its speed and simplicity of operation. However,
as yet, there is no satisfactory explanation for this
phenomenon of filter paper retention. Also, very little
is known concerning the factors which influence target
separations by filtration.
This work has been conducted, with the following
objectives in mind:
(l) To determine whether elements in the plus
-2-
two oxidation state are removed from very
dilute solutions by filter paper.
(2) To determine the factors that influence
filter paper retention, for the following
general purposes:
(a) To increase the scope and efficiency
of target separations by filtration.
(b) To attempt to provide a satisfactory
explanation for the phenomenon of fil­
ter paper retention.
(c) To provide a comparative study of ad­
sorption of cobalt, barium, and zinc
—6
in concentrations lower than 1 x 10~
mole per liter.
For this study of some divalent cations, radioactive
cobalt, barium, and zinc were utilized as tracers, since
the experimental conditions of this work were such that
the concentrations of the solute were too small to be
measured by other quantitative methods. All activity
measurements were made on a Geiger counter.
The effect of the following parameters upon filter
paper retention were studied: The effect of pH, of
concentration of several divalent cations, of ammonium
chloride concentration, of ammonium sulfate concentra­
tion, and of washing the filter paper.
In order to determine more of the nature of the
filter paper retention, the following studies were