An investigation of the effects of acid solutions of vanadium in column chromatography
by Theodore Van Vorous
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemistry
Montana State University
© Copyright by Theodore Van Vorous (1954)
Abstract:
During an investigation of the possibility of using column chromatographic methods for the analysis of.
Vanadium minerals it was found that the concentration of acid in the test solution determined to a great
extent the distance Vanadium will migrate in certain absorbents. The purpose of this thesis is to show
the effect of this phenomenon with various absorbents, solvents, and concentrations of acid.
Since the analysis of Vanadium minerals necessarily involves to a great extent the Geochemistry of that
element, a brief outline of the Geochemistry of Vanadium has also been included in the introduction. M IlfVSSTXGftTIOH OF THE SEFSGTS OF ACID SOLUTIOES
OF VAHftDIUM IH GOLtEH CHRGMftTOGRftHiY
by
THEODORS VftH VORQUS
A THESIS
Submitted to the Graduate Faculty
in
partial fulfillment of the requirements
for the degree of
.Master of Science in Chemistry
at
Montana State College'
Approved?
Head, Major Department
Bozeman, Montana
August, 1954
V 3
2
TABLE OF CONTENTS
Cjiapter
Pare
I, ABSTRACT . . ..............................
3
II, IHTROiyiCTION ..............................
4
III. APPARATUS
...............
9
IV. EXPERIMENTAL P R O C E D U R E S ...................
15
V. GENERAL CONSIDERATIONOF THE D A T A .........
19
VI. DATA . . . ................................
20
VII,
. . . . . . . . .
DISCUSSION.................................
VIII. SUMMARY
. ................................
IX. LITERATURE..........
X. ACKNOWLEDGEMENT................
68
72
73
76
1 ’ iAng
3 -
ABSTRACT
Since thes analysis of Vanadiimi minerals necessarily involves to a
great extent the Geochemistry of that element^ a brief outline, of the
Geochemistry of Vanadium has also been included in the introduction„
4
lit
IieROWCTTOW
Since this study Is net only concerned' with the effect
of acid concentration on the Mgration of Vanaditm? tnt is
also somewhat a study of tb*. separation of vanadium from ether
ionsj,. it Is Important to know what ions occur with vanadium*
FOr that reason* a brief summary of the geooh&mioal character*
lstlcs of vanadium Is included in this introduction*
Part A$
. .
GeochemiBtry of Vanadium
The wide distribution of vanadium throughout the earth’s
crust has been clearly established* not only In ores and coals
but in clays* limestones# sandstones and igneous rocks*
Vana­
dium occurs in appreciable amounts in the more basic igneous
and met amorphic rocks* up to .08# or more of vanadium tri oxide*
but seems to be absent or nearly so from the highly siliceous
rocks*.
Some of the igneous and met amorphic rocks Can carry up
to »15# of vanadium trioxide in ferric aluminoua silicates*
especially in a biotit® separated from a pyroxene gneiss*
In
general, the. search fop vanadium should be limited to rooks
containing less than 60# silica*
In the upper lithosphere vanadium Ie oxyphil® / a behavior
dictated by the fact that it has three stable oxidation states*
3. * © *#
tri-3 quadri- * quinquivalent vanadium*
Because of its
poor uion in the periodic table,# vanadium resembles phosphorous
and titanium in its manner of occurrence but differs from them
in several respects*
It does net occur in the early pentlandite
B
asgemfolages o r the late magmatic sulfides4
On the other hand#
vanadium does "become enrl&hed la titahiferotis Irdn ores due to
the.repl&oement of titanium*
It-also concentrates.ih basic
rocks* but has no connection with the phosphorous content in
that.respect*
-
: "
-
In igneous rooks vanadium usually does not form independent, minerals, but instead is. concealed' in the structure- of
other minerals*-
An exception- xb Ardennito, a complex manganese—-
almninum^arsonicWahadimn,' silicate Iti which the vanadium oc-Cufs
a$
-
-.'
.. -
Because Of the similar loule radii of vanadium In Its three oxidation states and ferric Iron, aluminum and quadric
valent titanium, vanadium has*a great many replacement poSsihiIiitxes*
Quxnguxvalent vanadium also'easily replaces phosphorous
in Apatite*
.
.
.
*
Feldspars are nearly devoid of vanadium, but the pyrox- enes5aamphxbole, and the mxcas are normally carriers of vanadium*
In this respect one mxoa, roScoeIit o .Can be considered to Tbe
a vehadlum mineral because much o f the aluminum in i ts structure
has been replaced by vanadium^
..
..
'
.-
Vanadium minerals, of secondary origin, .are more Common
because they become-more highly concentrated*
1
Because of the
higher redox potentials they Occur as vanadates*
She minerals
might be considered to be mineralogioai curiosities because the
conditions that form them are- seldom met*
The vanadium in these-
6’
minerals' normally comes, from enriched ground waters and ther­
mal waters■* The chief metals found with these vanadates are
calcium.,, manganese, (ferric) iron, uranium, lead, copper,
zinc and hi smith.
They may form simple vanadates such as
puoherlte (bismuth vanadate) and steigerite (aluminum Vanadate)
or complex vanadates, such as deseloizite (a leadrcopper-zinc
vanadate) and earnotite (potassium uranyl vanadate)^
Vanadium, is found in the biosphere in a number of plants
and small sea. animals as well as in crude oil.*. In Persian
crude oil, vanadium can occur as high as S »
8
in any event,
it constitutes a poison for cracking catylists. .
.
.
.
In the Geochemical cycle of vanadium several important
things are to be noted*
Solution and migration takes place at
relatively high fddox potentials and in the quinqui-valent state
it has a tendency to form anion complexes*
When vanadium is
mobilized it moves with the ground water until heavy metals such
as copper, zinc, or lead are met and then vanadates will form*.
This is especially true in the presence of doIomitic and calcitic limestones which'give the water and appropriate pH for
precipitation*
Vanadium will also precipitate in the presence
of sulfide ion, a condition often met in crude oil,
When a study was made of the effects of organic material
on the concentration of vanadium in clays and shales.it was
shown that as the organic material percentage went up so did
the vanadium percentage •„ This is true, in general-for. all
7
sedimentary material containing organic material.
'
Tlies© generalities I hay© mentioned are the more import
tant-characteristics of the GeocheMStry of vanadium*
They
should serve at least as a partial guide to understanding the
mode of occurrence of vanadium*,
■
fart BI .
•Considerations of the Thesis
• ,
Up to the present time no publications have been men*
tioned in Chemical Abstracts concerning the effect of.acid
ooncehtratlon on the migration of vanadium lops .in column
chromatography#
In addition*;, very few references were found
concerning the use of .column•chromatography for the separation
and determination ■of vanadiums,
-Of the references available*
the most comprehensive,was written by Th Ashisawa (B-Il).■ This
study'covered various solvents * absorbents* and color develop*
m g agents that ■were tried in, order to develop Inorganic
analysis methods for water samples* minerals*, and various rocks
found in Japan.
Since there was a general lack ',of information Concerning
appropriate solvents* absorbents and, holer developing agents
for Inorganic, column chromatography*...a ,,brief study had to be 1
made of" these subjects .as. they apply to vanadium analysis,*
After usable combinations of the above-named factors were found,*
experimentation could proceed*
During this experimentation* it
was observed- that in a hydrated’calcium silicate (Sllene. B.F.)
absorbent as well as in, other ,similar absorbents there was a
8
definite tendency for the migration distance of vanadium to
be affected by the a d d concentration "of the test solution.
A series of tests was set up to further investigate this
fact..
Columns were 'set up in which several possible factors
Such as vanadium* acid*, and other ion concentrations were
varied* one at a time *
The effect of varying these factors
is the basis for this Thesis.
r
9
HI,
APP AlUTUS
A*
,Apparatus Sstms fog Vacuum System
®ae original equipment used by the author is illus­
trated in Figure I*,
It consisted of a column made of various
diameters, of soft glass, tubing pulled out at the bottom to
-c constrict ,it and ,enlarged at the.top- to allow easy application
of test solutions»
The diameter of glass tubing was varied in
Slsa from 6mm to lorn (O4D,) to find a suitable size to use*
The bottom of the tube was packed with a small wad of glass
wool to prevent the absorbent from being pulled out by the
vacuum*. This column was placed in a .Cork of suitable.size to
fit a 500ml suction flask of the conventional type, and con*
nested to a water suction pump*
A test tube of suitable length
was placed below the- tip of the column inside the flask to col**
Ieet the solvent coming through the column*
It was found that this type of Setup had the dla*
advantage of packing the absorbent too tightly and also drying
out at the bottom*-.
B*
Original Setup for Gravity ,Feed System
.
To overcome the disadvantages of the suction system*
a gravity fed column was tried*
The- apparatus consisted of a
separatory funnel suspended about four feet above the column
and connected to it with rubber ,tubing* . Th* columns ware made
of 8am (0,D,) glass tubing about 300m long* and,pulled out at
the bottom*
The columns were filled with the absorbent in the
10
fo&m of & Blurry to about one half of their lengthy and the
solution to be tested was applied at the top,
Ihe columns
-were then connected to the rubber tubing and a pinch clamp
opened to allow the solvent to flow*
Although this system worked well* it had the dis­
advantage of allotting only one sample to be run at.a time
unless a number of such setups were used,
0*
Apparatus Betuo for a Multiple Oolumn System
Tb# multiple.column setup (Fig, 5 ) was essentially
the same as the original gravity system except that calcium
chloride drying tubes were used in place of a separatory tube*
The multi-outlet tube was made in such a .way that a source of
air or nitrogen pressure could be applied* thus obtaining
gravity and gas pressure at the same time on the columns*
it
was found later that the system flowed sufficiently fast with
no gas pressure applied^ Sg this part of the apparatus'was removed*
Ihis system allowed twelve columnszto be. run at
once With two six multi-outlet tubes,. ,This greatly increased
the speed of the method and also its Versatility*
It too had
a bad point in that the rubber, tubing was attacked by the
solvents being used*
This was remedied ,by uging glass tubing
Vifith surgical rubber joints as shown in Fig* 4,
11
Figure I
12
Simple Gravity Feed System
— Separatory Funnel
— Solvent
Rubber Tubing
-Test Solution
•Absorbent
8mm Soft Glass
Column
Figure 2
—
Glass Wool
—
Collection Beaker
13
Multiple Column Gravity Feed System
Multiple Outlet Tube
-Kubber Tubing
-Calcium Chloride
Drying Tube
Solvent
"Tube Clamp
8 mm (O.D.) Column
"Test Solution
Column Stand
'Absorbent
"Glass Wool
"Collection Test Tube
Figure 3
14
Modified Column Assembly
- Rubber Tubing
■ Glass Tubing
One Hole Rubber Cork
Calcium Chloride
Drying Tube
Gum Rubber Tubing
8 mm Glass Tubing
Gum Rubber Tubing
-- Clamp
Tubing
Glass Wool
Figure 4
15
IV,
■EXPERIMENTAL PROCEDURES
I’ll© .following conditions and proc-edures were
followed for all of the experimentation except where devlations are specifically noted*
These.conditions are not" listed
In any particular order,
I*
Except in the early experimentation, the absorbent
being used #as washed and then poured into the columns aa a
thick slurry.
This was done with a partial vacuum applied to
the bottom of the column to Insure an even flow and no bubble
(
formation,
3,
The absorbents used were as follows t
a.
Aluminum Oxide— -Baker Reagent Urade (ignited)
thru #100 mesh,
b*
Hydrated Calcium Silicate (Silene E*F*)--0olumbl&
Southern Corp,.--thru #100 mesh,
c <. lr.lca3.ca.um Phosphate--Salinkrodt Reagent Grade-ground to pass #100 mesh,
d*
Bone Aahw-unknown analysis for impurities-*
unknown producer,
e>
Diatomaceous Earth— Tech. Grade
f*
Fullers Earth—
&.
Magnesium Carbonate— Baker C.p,
h,
Calcium. Oarbonate--Baker C*P*
O i- The eluting solvents used were as follows:
a.
Methyl Alcohol - Water (Isl)
16
b»
EthgrI Alcohol'.-?■ Water ■(Isl)
c-. n-Propyl Alcohol ^ Water (Iil)'
d,
ISO-^Propyl - Alophdl (Isl)
e+
n^Batyl Alcohol
W&tdr (1*1)
'
Oarbop Tetrachloride
Se
Ethyl Acetate • . .
h.
Benzene
1»
n-Butyl Alcohol - IS Hydrochloric Aeid (Isl)
3»
nf,Butyl Alcohol -■ IB Bitric Acid - OMne. (10)
The colorsdeveloping agents used were as follows s
6*
a.
Hydrogen Sulfide passed through the column
"b»
8-Bydroxyquiziolin© at the correct pH
Ci
Ammonium Polysulfido. ■
di.
Ultra-violet light (uranium)
e*
Sodium Thipoyanate
»1B spin*
ft.
Ammonium Hydroxl.de
BH '
go
Phosphobungstie Acid
SSbe solutions containing Vanadium were made up from
the following reagents $
6.
a*
Spdlum ortho-vanadate--
b.
Sodium meta-vanadate--
c.
Ammonium meta-vanadate—
d*
Vanadium TrioMde
Since the absorbents containing carbonates and active
Terms of silica evolved gas .In acidic solutions* the solutions
17
were kept below & BBT sold condition during the experimentation*
7*
In generalf. the solutions containing Vanadium were
made up to contain IOgQ micro grama v/ml and diluted to the
desired concentration*
8*
Since,Vanadium will develop a distinct color in
absorbents containing active sill.catesno color developing
solutions, were needed with these absorbents:f
9^.
It was. found that when absorbents were used,, the
Vanadium solutions could be diluted to a Concentration of 5
micro grams v/al and still give a distinctly visible colored
line*
'
10*
Unless otherwise noted* the. columns were, rub for
sixteen (18) hourS%
l
Ihis time was chosen for convenience and
because very little movement occurred after a longer period of
time*
11*-
When the columns were filled, a line was drawn on
each column,at a predetermined height so that equal amounts of
absorbent could be adden*
As a check on the consistency of
packing, the amount of solvent flow from each column was
measured*
Also, each batch of solvent was cheeked with 0m
Hydroxyqninolino to see that all of the Vanadium, had been re*
talned,
18*
A check was made of the. ions that might Interfere
with the experiment*
Solutions..of phosphate, chlorate, sulfate
and several other ions were, added to the absorbent slurry to
V
IS
see wbat effect the# had on the migration dlstance @f the
Vanaoliw Ions*
15<. fhe eoid Sonoentration, was varied between *01 #
ana .2 H in, the second, section of the experimentation,^
Below
the^O]:..# acid concentration no measurable movement was noted
in a hydrated calcium silicate (811ene,B*P».) absorbent*
•
■
'
:•
'
,
19
Tt
GENERAL CONSIDERATION: OP TRE DATA
In Part I of the data, consideration is. 'given to findu­
ing an appropriate solvent’ and absorbent for" Vanadium,
solvents that were tried are IlAted In Table I,
The
Since some
work has been done by other authors on the problem of finding
a suitable absorbent for Vanadium, this problem will he
covered In/descriptive form*
Part II of the data deals first with the effects of
varying the concentration of Vanadium in the solution being
tested*
The acidity of the solution varied at the same time
that the: Vanadium concentration varied*
Next the acidity
alone was varied between aero and I N acid, conditions*
Lastly
the acidity was varied with a constant amount of interfering
anion added to the absorbent*'
/
80
VI,
DATA
Fayt If
■
;
In Table I* data eoncepriing the use of a number of
solverus Is listed*
Although this table shews 'the effects of
these solvents on the migration of vanadium, it does not show
other Important factors we must know In order to pick a suit­
able solvent*;
Por example* it does not show that n-Butanol
and water move so slowly that the bottoms of the columns dry
out and
crack*■
Others, such as methanol and water, move so
fast in hydrated calcium silicate that they do not give a good
separation of vanadium from the other Iona that occur with it.*
Another factor that had to be considered was that solvents that
are acidic In nature could not be used easily because they
caused excessive channeling In the absorbents
employed.
that the author
It was found that n^Propanol and water was the best
all-around solvent that could be found.
For that reason, it
was used almost exclusively In Part II of the experimentation^
Aluminum Oxide was. the first absorbent to be used*.
It had to be ignited and then r©-ground to pass #100 mesh
before it was suitable as a column material*
It was found
that this absorbent did not give very good separations and
dried out easily* causing channeling*/ ■
Bone ash was a good absorbent for vanadium as well 1
as other ions, excluding uranium.
It did, however* have &
very slow solvent flow rate which caused the columns to dry
4
21
out 'easily,-*.
a?he carbonate absorbents -were Ineffectual beOause-•
of the gag evolved when the acidic test solutions were applied.
Bydrated. calcium silicate and %%atomaceou@ Earth
had the properties of very good absorbents for vanadium.
They
^dljMiot dry out or channel except at high acid concentrations,
gave good separations, of vanadium from other ions such as
copper* lead*, bismuth and cadmium*
tain uranium at all,
They did not* however*
This fact* of course*. has the advantage
of completely separating vanadium from uranium in carnotlte
ore* -as an example*
Because of the distinct advantages of hydrated cal- ■
eium silicate and Diatomaoeous Earth over the ether absorbents
tried* they were used exclusively- in the experimentation of
Part IZ*..
A literature search revealed, that the best color
developing reagent for vanadium was B-Bydroxyquinoline (ezine)*
This reagent was used' to develop color for vanadium whenever
this was necessary.
It was not. needed.In'Byarated calcium
silicate or Dlatomaceous ESrth because vanadium developed a
distinct color without the addition of a Separate reagent*
Ihe following lists are the key to -the- numbers used
to Indicate the different solvents and vanadium containing, com:
‘
pounds used in the experimentation^'
MtMM«••*>*M «M■»»
Solution
I*
0* Amima&lusB mt&*9a#aaat»
Bodltm a*tbo*v@a&<3*#
Solvemt
4* VmmatUBk trloM#
I&at#
I* %^thW3#l~*Wat@r (1;3L)
&,
Metbeisol*.-! #
Aold (1*1)
B-s.
Ethanol— Water (1:1)
4* Bthenol^i B m W e Aold (1*%)
n*BuWidi^l B %dmohlorlo Aold (1*1)
6*
Vf
% Bltrlo Aold— i# o%lme
n^Butanol— B a W y (1*1)
8, n#Pr@oaw^#i B mtrlo Aoid (1*1)
'
9* h-?ropanoi— Water (1:1)
10* l9o*Pr@p8nol**i B Bltrio Aold (Itl)
11» leo^Promnol^-Wator (1*1)
18* Oerbom Setreohlorlde
- 15* Ethyl Acetate
14* Bontom
Ohlorofor#
,.
-
'
Table I
iii,I. 'll;.l.il..l'-''.I.,.MiJJ......... .
'
II
I
I
II
I
ill
I
i l l
'
I
I I
i
.Q-Js* %
I
.68.
?.?
55
,5
a
- S : 66
' I OO
H
; " I 55
.13 :TS ]
M
6@
SC :v .
tf
n ' 55
/
I' .3 !
M
H
2B: n ,■
■
-
.>5 '
»
Sf
: 1,0
:
»:
-*5
U
55
*5
9*0
n
-
66
1*0 '
6,5
is
]:
It
If ; 55
»5 -
6,*5
•
ii
I
n
6
66
1,0
5*0 ,
it
•I
-it
if
55
st5
5,0
H
I
It
-2P. IS.
4:5 - ■MO,
n
it
:IE. ■n :
''lB n ■
.3
.
IO^
9*0
W
n
- ■ ,6.
i*e
29 .n
:SB
1*0
Il
'
16
66
;": :
■
. ^
Hydrated Calcium
Silicate
:2
IB
■
i , :
Vg :
''&
.w.B
. .. I
--CordBieiiiiSiI All of tiie above soIverrhs developed, colop in tbe
coluBiii Wxtlipufc lib© addition of colon developing; agentsi Tit©
color was a dark grey in each case except for solvent number
6s which gave a reddish-brown due to- the oxime»
mH-lV-lihnt-|-hfTriTll~lll--,-n^r^Ii^iTrr»^>-.'T>|1'»l.i-Ct«l»V»rTl|«;
3 I
:|1K|
Hydrated Oaletnm '
Silieate
25
Oowgeints I All of t&ug above solvents developed color $ n the
eolums, without Pheraddition of color developing agents i ':fEie
color was grey for $13 and $14 and a yellowish^grey for $15.
86
Figure I
Table H
Micrograms of Vanadium Added from Stock Solution
Solvent:
Absorbent:
Times
Distance of Vanadium Migration (Cm's)
HA**
'
^r-
i ■.
I
I
#
'
jt i'
I
'583 % Bisbornaeeotis E arth
Sf
;59B Ir
50B
H
313
W
If
n
3@B M
It
H
It
35B
M I
383 V'
37B
,in
86
1*0
8*8
59
>9
;• 2,5
'•
ft ■
16
I
I
' n
d.8
2,0 I
n
46'
J
1*8
I
Il
40
*6
- 1*6 ,I
If
ti : 53
' IS ; 26
-,5
I '1^ |
Il
' W
' t! : 20
. »8
,■
ft
: '13 - ; B- : 6 *6 ;
.41
ft
;■ fr : &*&
If
• It ;
*9
I
ft
»9
I
n
-; *# I
it
. ol
If
: :*4 -
.
383. ft
Uu
ft
If
?t I
5&B If
9.
it
V
If
:a4B
i in
If
; '
3SB ft
0
,
'
It
,OS ;
ft
O •
;
."
Gommentfis:
M s o line of v a m d l w migration in this
series varied from a dark green a t 'the highest concentration
to a yellow at a concentration of 6.6 micro grams/ml <,
Mlcrograias of Vanadium Added from Stock Solution
Diatomaceous Earth
-Bydrated Calcim Silicate
Solvent* n.Propanol / Water
Absorbent: Diatomaceous Earth
Time*
16 Hours
Distance of Vanadium Migration
(Cm1S)
I
30
Diatomaceous Earth With
2# BgBOa
BlOj "
>501 *
B70f "
O^rmnahty $ The ■baa© line .of.vanadium migration In this
eeriaa was a yellow^greon at the highast honoentnation Ao^n
to a liarl to d i s t m g m sh yellow at the lowast concentration
Microcrams of Vanadium Added from Stock Solution
--- Diatomaceoua Earth/Phosphate Soln
- - — Diatomaceous Earth / Water
- - - Hydrated Calcium Silicate
t Water
Solvent* n-Propanol / Water
Absorbentj Diatomaceous Earth
I N Phosphate Soln.
Times
16 Hours
Distance of Vanadium Migration (Cm1S)
; :■
4
69
Eydeated Calatum sill
•cate v/l'tJa■a constant
IQOppm ? added
74 I *
I 96
Ln. I ■
Oommeate* The.bea*. lip# of vanadium-migration la this series
tlon*
The uranium *&s .found la the wash solution bebaus* it
Mlcrograms of Vanadium Added from Stock Solution
Solvent: n-Propanol / Water
Absorbent: Hydrated Calcium Silicate
vfith a constant 100 ppm of
uranium added
Time:
16 Hours
Distance of Vanadium Migration (Cm's)
54
T&bla VI
©ommen-bss. In this series a distinct change in color took place
as the Concentration went up*, The aeries la grey to pale
green to dark green with a gr'&y ring above the green,' At the
hrgnsst concentration the absorbent.channeled a great deal*
making the meaanrementa vaty from what they .Wonld be expected
1OO
.
,
"s
200
175
150
125
Figure I
Table VI
100
75
50
Mlcrograma of Vanadim Added from Stock Solution
Distance of Vanadim Iiigration (Cm's)
10.0
9 .0
8 .0
7 .0
6 ,0
5 .0
4 ,0
3 .0
2 .0
1.0
'36'.
with
Ge&aim B H e a t e
Phosphate Sola
' 175
Comments: The .colon change in this series was from a dark
grey at the lowest concentration to a deep yellow with a ■
green line below it at the highest concentration#:
Micrograms of Vanadim Added from Stock Solution
Absorbent / Phosphate Soln
Absorbent / Water
Solvent* n-Propanol / Water
Absorbent* Hydrated Calcim Silicate
and I N Phosphate Solution
16 Hours
Distance of Vanadim Migration (Cm1S)
#8
M B p Bi
L m # *1
% & 6 W m # @ w # 3NH#Bb
*
I lB ;1&*8 I *88 T
Ia
08
I
##
*4$ | Sgg
I m Ii A,j
I *90 I 8%3
09*8 ; i*se 1 ,4*8 I . *
I 9*0
I
OommeD&e* m # oai&e ^ m m g e la t&&&. ae*&** #*# fee# @ **%&,
&% *8&. ia#»at aoaasaBmtiaa. # ; % d##&.g#@&a at .tba b w # « t
FSr***: I i m t#r the 'aal'd <%w&nte&tlo& *a%&*a
enaan&llng*
O
175
150
100
Figure I
Table VIII
325
75
50
Micrograms of Vanadim Added from Stock Solution
Solvent! n-Propanol / Water
Absorbent: Diatomaceous Eartii
Timei
16 Hours
Distance of Vanadium Migration (Cm's)
40
A
8 23^
cWt'ed OalGdxiM Silicate
1501 »»
I 178
■11: 10
Oommentsi Ho color developed in the above tests until
color as the concentration went up
41
Table X
I
I
I
&
I
g^ S
I
8
I
to
{125 B.0
Matomaceous Earth
;1B4B "
M
12EB *
tt
1286 *
n
187B
128B"
is.
S II!
I
If
os S
si
I III I«
9
10
ft
so
as
ir
30
1,15
H
it
40
»15
it
it
tt
SO
^lS
tt.
«
it
60
»15
tt
125B "
ft
n
80
f!5
ft
150 B fl
t!
ft
100
»1S
■tt
tt
tt
IBS
*15
ff
it
ISO
ilS
tt
tt
175
»15
it
H
200
*%5
ft
11[ 10
»10
M
'tt
Itt I $0
I *io
•• it
ft
I it
,10
i;
'
'
%#tra
fl5
16
■
ESBlB n
M
'tt
“*sr
50
" * m.
mlCL
Comments? ITo color -developed In the above tests until
S^Bydroscyquinoline.was passed through the columns 9 With
.this- reagent an. Indistinct- reddish- color- aopeared that1was
parclally covered b y .the color of the absorbent* '
I-,
4,S .. .Table. XI . .
a
W
3 5;Hydrated Galoiiim B i M Os to
10
*
20
"
100
-VB
I
LSll
Gomentss Ho color developed in the above teats nntll.
S-Hydro.^cyquinoline was. passed through the columns*
45 ^
I & I,
SfiT1E
ill
ISSH *
100
.800
LSlf «
L94H %
Qomments g Ho color developed In the above -tests mfcil
S-=Hydro^iiTilnollne was added to the cesiums*
44
-I«H S3<H '
;• I Fr! O .
d *r)'e
.8.8;
l # "
04 I ■"'$
0 &#m&Dte;
The
Oolw had to be developed with 8 *Eydro3 yq#laollMa
movement Ws'- '1mm#"''
.............. ., ,
U.
I g#
S > «? I BH
IBS I Sydmted SaleSUm Silicate
^n,, M
_ ,_
^^
tivr^u
-xAi©' OrXny a
tae base of %be vaaad&um migration was & yellow^graen in
eaea Gage* All of the vanadima seemed to be held at the
top of the.column in the neutral eolation*
Figure I
Test Solution Normality
47
^ ' j©i
S *! ■’
i Ii
hiVi.
■p -Il
D5.atoitiac®Qus Earth
04 S
158B !f
08 I
»1
1613 ”
165B n
166B %
Goraraeuts? Acl d added In each ease was HMO3 „ The line at
the.base of the v anadiunt-ml gnat ion was a dark yellow?,green
in eaeh case*,
Centimeters of Vanadlm I-Ilgratlon
.16
14
Test Solution Normality
i R.j
#
-
j#)
'
&8$p
W e W *
I # I-#@5
* , I .'$-#&.tb, I Br ^ W s p W t e JSttSacij 'i ''&5#B **'
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*&
'I
60# *
6&@ #
-1
f s6 .
$64
the haa@ of. the. vahaaiwm migration, mas. a yellow^green in
each cas@\ All of the vanadium seemed to he held at the •
of the columns In the 'neutral solution op at least 11 did
not migrate more than jL crn, . . . . .
50
SM # %
:fI>§
I I «5
Silicate
.with I B % $ Q 4
•
ilGGB ^
L67D
'a
,* ( i
.?!,
51
I
t
j# I
0# %
wi th I # #010 . Sola
'1606 %
161# "
$164#
$165# %
r
52
■
'
d
m
Galelum Silicate
176} »
LSI! *
1841"
■
^7.
^".VIA Vtit1CSV^ -UiB J-JtBB BU
cba base of the vanadium migration was a yellow^green with
a Oi5Igixt yellow ■lixi© Imm wide above It in each, case ^
.10
.20
.30
.40
.50
.60
.70
Normality of Vana d i m Solution
^SO
.90
1.0
S4
%ble XX
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was a pale, yellow color In a line about 5mm wide* The
.
color wag Very distinct even though a pale color. .
.:
Figure I
Table XX
... Absorbent / Phosphate Solution
- - -Absorbent / Water (Reference)
.10
.20
.30
.40
.50
J60
.70
Normality of Vanadium Solution
.8 0
.90
1 .0
Table
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was a g r e e n line with a dark yellow above it.*.
:
if
,
: 3 02
H
^wi__ '
.. — Absorbent / Sulfate Solution
- - Wibsorbent / Water (Reference)
o
TE5
720
3o
745
35
35
775
Normality of Vanadium Solution
35
35
CT
58
Figure I
Table XXII
...Absorbent / Chlorate Solution
- - -Absorbent / Water (Reference)
Ol
_____________________________________________________
.ID
.20
.30
.40
.50
.60
.70
Normality of Vanadim Solution
.80
.90
1.0
60
Table ZXIIl
Slafcomiaceous Sa^th
doraments t Acid added in each case was HHO3 6: . The line at
the base of the vanadium migration was a dark fellow^graeh
in each case,
IIIH 0IcI1
BlL
*10
.20
.30
»40
.50
.60
.70
Normlity of Vanadium Solution
.80
.90
1.0
62
— -— -Absorbent / Phosphate Solution
- - -Absorbent / Water (Reference)
Normality of Vanadium Solution
O
64
-
a*
3
1OB- I f m a ^ o r r i a c e c m s E a r t h w i t h #
5
i 'ji B ;;!
9
,II H PotaBBiuia Sulfate
I solution si&ds.d.
I' 1*3
I
0 4 . 6 rt
2$a81
"
6offiraontss. The H u e at the base of th©.vanadium migration
T5i£> Cl
O
n
Wix
-f-pva^S vt-VO
yI 5 HA ^
- ^ ' '4- Ia
x-t _
t
dr
Figure I
Table XXV
I
5
I
----Absorbent / Stilfate Solution
- - -Absorbent / Water (Reference)
o
oo
Tso
730~~
7u o ~~
Tso
TSo
Tto
Normality of Vanadium Solution
Iso
I90
Ho
66
Table XXVI
gil
4
:I I m g w
I#
IM
D I Biatomace-oue Earth with}. 9.} 255
i.
I H F o t a s s i w Ohio rats-. I
^
so Ihtl o% added
B ffI
•
,!
‘
I
I | ^
I t! I n
I
, *&&
'
I «15
1*25
1*4 -:
i*5 :
ItG
l+?5
805D
Oomments
The color at the base 'of the vanadium migration
was a deep yellow band about 5 mm wide in each case*,
—
-----Absorbent / Chlorate Solution
- - -Absorbent / Water (Reference)
.10
.20
.30
.40
.50
.60
.70
Normality of Vanadim Solution
.80
.90
1.0
68
VIZ*
DISC058I0&
The following,a-dissuasion of Part TI only4
It; is to b© noted first that only two absorb©nts #or@
us&d in Part IT*
Tbs reason for this la that the aridity
effect was not noted to such an e&treme in any of the other
absorbents tried'by the author*.
In Tables IT*. H I and IV the algration of vanadium
at any concentration. Sooms to- correlate well with, the acidity
of the eolation it is in*.
The change from a light to a
darker color correlates, with the vanadium concentration*
allene S*.?,. seemed to ,allow a longer migration distance than
Diatomaceoua Barth at equal concentrations of vanadium*
Addition of -ohosphdto- ions seemed to slew tho vanadium ©yon
.
more* but not In a linear manner*
Tbena la a dla&lact break
point at which the phosphate ions slow down the vanadium to a
greater extent*
.
In Table V the addition of a constant amount, of uran*
Ium-ions lengthened the distance of migration, -a constant
x-
amount*
Tbld was due to the acidity of the uranium solution*
It is to be noted here that none of .the uranium was retained
by this absorbent*
:
In Tables IX, X, XI end XIl a migration was observed
to occur la neutral or slightly alkaline solution., but it was
a constant value*
Tbia means, that the migration distance la
definitely correlated.with acidity in these absorbents*.
$9
fable XliI illustrated that two forma o f va n a d iu m in
vergr lots? acid concentration migrate only a very short distanee*
The fact that each migrated equal OlatanaeB led the
author to use only one .form In the experiments to follow.
Tables XIV through XXVl and the accompanying graphs
•show the effects of accurately .controlled acid concentrations
on the migration bf vanadium^
They, also serve to show the -
effect of interfering anions to a more accurate degree^
#@te
^
here that the phosphate lone had a depressing effect on vanadium
migration while the sulfate and chlorate ions had a raising
effect which was 'somewhat linear in nature *
With'these generalities in mind* obtained from the
various tables, we •can elaborate further on the data,#
Tm
most evident fact we can sea In the data is.that the'migration
dletanca of vanadium does depend to a great extant, on the
acidity of the'Solution being, tested^. In fact* .over the range
of sero to '3.. S acidic .conditions.#..the distance of movement is
a linear expression of acidity^ ,Abdwra this 5 .& acid condition
the effect .Is one of .leveling off*' Evidently, the effect oaa.
,be explained in. the following manner'*., .The,.active ,,silica forms.,
in the absorbents.used, had a .,greater tendency to absorb the
hydrogen ions, than ,the ,.vanadium ions with which they .came in
contact* As the hydrogen ions ware used. In the .process, of: .
moving down ,the columns there is a.greater chance, for the
vanadium to be absorbed*
.This phenomenon •la.alco shown by the
YO
fact*, not gentibB&d previouslythat the band of vanadium'
nolqr development sddeaa slightly as the aoldlty goea up^,
In low agldlo. ooudltlous the hydrogen Iona are absorbed move
vapidly giving the vanadium ions less opportunity,to be .
absorbed*
As, the aoldlty goes up the time required for
absorption goes dp at a rate dependent on the speed of sol­
vent flow and various other factors *
This means that with
a change In. time in a localised area vanadium has a greater
chance of absorption and. may be absorbed in a wider band,*
This of course infers an unequal spread of hydrogen ions' in
the columns,
Since this acidity effect depends on using the
hydrogen" ions before the vanadium ions, can be absorbed, it
would necessarily- mean that the migration distance of two
unequal concentrations of vanadium at equal a d d concentrations
should be approximately the same*
This was found to.be. the-
case*
When foreign anions are added to the absorbent} the
distance of vanadium migration, changes to .an observable degree *
In the- ease of phosphate Ionsi,: the distance is shortened*
This
means that the phosphate ions can absorb the hydrogen' ions and.
keep them, immobile so that the vanadium ions can be absorbed
sooner*
It also means that the areas between the absorbent
-particles that were formerly filled by water molecules are nowfilled by a combination of water molecules and reactive phos«
phate -ions*
The combination of these two absorbent ions would
S
shorten the migration dSstanoe*
With foarelgp sulfate and ohlorate anions added to the
absorbent the migration distance Is lengthened*
Ihle means
that these lone are tending to out down the absorbing power
of the silieate Ions*
The change in migration distance should
be variable with the amount of these foreign anions that ar*
added to the absorbent*
vizi*
s m w w
I* GWtga of ag&d&ty over
range of 8@ro to & B
ooad&tlona oatieea a Ilaoap raise In the migration dlatanoe of
vanadium*
S*
Above 3 # aeld oondltlone, th@ distance of a&gra*
tlon tend# to level off*
8*
With a eoaatant aoldity and oonatont vanadlom oo%*»
eentratlon* the distance of vanadium migration Ie dereadent
to a large degree an the foreign anion# present^
4*
If the foreign aaloaa preae&t have & ta&dg&sy to
Goaplea: with or absorb vanadium, the migration dlstanoe will
be shortened.
If, on the other hand* the foreign anions d@*
proas th@ absorbing power of the absorbent, the migration
diBt&noe will be lengthened*
8,
With no foreign anions present, acidity oonatant*
and vanadium oonaentratlon constant, the migration distance of
vanadium depends on the rate of solvent flow* type of absorbent,
degroo of naoklng and other mlaoellanaeus faotora*
6*
%&th the particular absorbents used by the author,
nwProranol and Water (Itl) was found to be the beet solvent*
It gavo the beet separation of vanadium from other ions that
occur with vanadium*
7*
To develop color for vanadium, oxlno in absolute
Rthanol Is the bast reagent available*
73
1%. - . LI%RATB&B
M
,
GeoohemietrF of Vaaadlum
,
i1«■
Glsrlt©s (1984) Data of GeoohemistrFa
Government Printing Office - Dept, of Interior,
Bulletin #'770* pp.. Sl5 SSSr 698-723
■
Kalervo.Rankama and Th. G# Sahama, (1950)
Geochemistry, Bniv- of Chicago Press*
P P . 594-603
38
Analea Asoq ,., of Argentina. Volw -SOj pg4 36
Bdl♦. Instw G e q l < Minero esuana, vol. 60*.
Bp* 3-9
5*
Chem,. Mews1,, vol. 66 (1892), pg, 211
6»
Compt. Bend*., vol.
7*
ComPt. Bend* ,, vol. 117
(1893), p-g* 546
8«
Compt. Kenci-,, vol. 128
(1899)> pg^. 532
9*
Compt, Bend.,, vol. 130
(1901)s pg, 91
10*
Compt. Bend,,., vol* 134
(1904), pg, ISOS
49 (1859),
pg,„ SOI
11». ' Boon. Oeoli, VOl* 42 (1947)* pg* 634-6.
IS,
J, Am, Qhem,; Soc,., vol. .21, pg. 706
13*
I . Chem. Soc., vol* 7 7 , pg, 1094 ■
^4 '
TraaeA Roy*. 890. Edinburg, vol, 6 1 , pt* 11*
p g , .553
15*
.
U.S.G.S. Bulletin,, #167, pp. 4,9* 73
•>** These references' are the best available general sources of
information concerning the Geochemistry of Vanadium
74
16,
17.
BullatlR* #518*
IIO
W o n of 8o+Afr&oawDGmt. of
@*ol*
Suevey Bulletia, #39, eg# 117
B*
OhromatoKraohlo Separation of Vaaadlum
I*
Lederer and Lederer (1958), ChromatoRrerby.
ELdevlor Pr#&8
0*
IBoOmie and Pollard (1088)* OhrpioetoaraKblo
Matbede of Inorganlo Analyale
3«
0, 0# Smith (1988), Inoraanie Ohromatoaraphy
#* Van Boatrand Preea* pn» 84«56* 93*180
' 4.
AB&3a_gb@g&fvol* 21
Gf
vol* Ba
G*
Anal* Obem##val, GS
?+
(1049), PB. 70.V&
(1988), PT, 64
(1083), pg, 840
VOl, @1 (1950), Pg* B91
8*
B&oobem* I.* vol* SI (1050), pg* 688
9*
$ W 1 , Son*.O M m « prance* (1948), rr, ?86*?86
10*
jl. Am# 0bem*_ .8oo*, vol, 74 (1958), pg;* 8333
11*
Bpr te # Balneol * Lab# Aknvom Dnlv.. vol# 8
(1981), pp* 1*48
IB*
B*
^
u
a
r
t
(London), vol, 7* pp# 807*383
General Befarenoea for Vanadlim
1#
^hralm* (1946) Inor^anlo Ohesdatry
4th Edition, rp# 304, 470, 404* 888, 700
Interaeieneo Puhliahera
?5
2k
Hillebrand9 Lmdells, Bright, and- Hoffman
(1955)s Applied Inorganjo Aaalygig. Snd
Bdition9 Ghapt. SS9 Iohn Wiley & Sons., Ino*
3»
Th., Moeller, (1952), Inorganic ■Ghemlstry.
Ghapt,.. SO9 John Wlley & Sons9 Inc,'
4*
A. F. Wells,- (1045), Structural Inorganie '
Ghem-Istry,, pg-, 421, Clarendon Press (Oxford)
\
YG
X*
ACKNOWLEDGEMENT
Th© author Wishes to acknowledge the, valuable assis­
tance given throughout this investigation by D r Hay Ioodriffe
He also wishes to thank the.other members of the staff of the
Chemistry and Geology,Departments at Montana■State'College
for their interest and help.In this.investigation+
I
II-1 S O S
M ONTA NA S TA TE U N IV ER SITY L IB R A R IE S
2
7 6 2 100 20 8 2 4
CD
Il I Illlllli IIII Illl
lw78
VJTSi
cop*2
11*809
Vorcus, Theodore
investigation of the eiie^E
of acid solutions of vanadium
NAME
JUL2
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