Professional Documents
Culture Documents
Abstract-All available
c~hemicnl and therrnodymmic
information
is utilized
to construct
a diagram
showing the st,abilitj- relationships
of the known vanadium
compounds
in aqutous equilibrium
in tcrrrls of
osidati;n
pot,rntial
and pH.
The disparity
between
the ohserved
precipitation
conditions
wnd t how
c~alculnted from the pnblishcd
free enrrgirs of tho oxides is used to cstirnate the frcr: encrg)- of h>-drat,ion of
the hydrated
forms found in nature.
The well-established
vanadium
mineral
species (not including
rilicates)
are assigned
regions of stability
on the equilibrium
diagram
on the basis of chrmicnl
conTtitution.
crystal structnre
and obsorvetl
petrologic
associations.
It is found that a completolv
wlflwnristent
;rlt,rrution
sequence
appears on the mineral diagram,
showing t,he changes that occw in t hr
vnnadirml
arcs undr~ weathering
conditions.
Montroseite,
TO(OH), is evidentI)- the prim:w>- nlinwal
sources of vnnadiunl.
Two distinct
branches
appear in the alteration
sequence:
one is confined to acid
<.onditions
charact,eristic
of zones of primary
vanadium
oxide concentrwt.ion
in the sandstone
in the
presenrr
of pyrite;
an d t,he other occurs in more basic conditions
where calcite is common.
The equilibrilmr diagram
is 11wr1 to draw tentative
conclusions
regarding
thp conditions
~mder which the original
~~~ontrowit~~ uxs d,l~o,:it~d in thr wntlstonrs,
pwsnmably
throngh
the action of nlinrralizing
sohltions.
* Publication
aut,horized
by the Director,
U.S. Geological
Survc~,.
t Present addrrss:
Department
of Geology. Harvard
University-,
Cambridge.
131
Mnssac!lusetts.
17.$.;\.
GARRELS
Ihr equilibrium
+ 2H,O -
V20,(s)
+ 4H
constant8
-RT
111 K
-1.36-i
log h
Thus the solubility of vanadium falls Do lop2 moles/l. at pH 3.5, and the vertical line
on the E,,-pH diagram may serve as a boundary between the vanadyl solut,ion and
t#he 172O,1solid stability fields. The equilibrium oxidation potential with respect, to
t,he HZ/H+ couple: E,, between oxidized and reduced species can also be estimat,ed
from free energy changes according to:
E,
zzz
EJ -
0a05g1B
log I\:
n
made by GARRELS
(1953), and the results subsequently correlated with the uranium
oxide system and the Colorado Plateau ores (GRRRELS,
1955). It is non-possible to
expand GARRELS'
preliminary diagram to include many more vanadiumbearing
species. Fig. 1 shows the key relations among the various ions in solution and stable
solids in the vanadium-water system. Shaded areas are fields of stability of solids.
and are defined as areas in which the solubility of the solid is less than apl)roxirnately
0.01 mole/l. of the major vanadium species in equilibrium.
Unshaded areas are
fields in which the predominant dissolved vanadium species exceeds 0.01 molt/l., and
;lie labclled with thesespecies.
Boundaries betweendissolved speciessre drawn where
1.0
0.8
0.6
>
cvo+2
vonadvl
Cl.4
-0
o-2
2
aJ
z
0
-VAL
?j -0.2
cl
0
x -0,4
0
-0.6
\::.
-0.8
?,.I.
.i
. .
:>:.
.>:;;
_ :.
::
. .
456789
10
I1
12
13
l-4
pH units
the molar concentration ratio of the two major ions is unity, The only solids COW
sidered are those resulting from interaction of vanadium and water. A diagram
very similar to the theoretical one portrayed would be achieved by controlling pH
with HClO, and NaOH, and oxidation potential with H,O,. None of these reagents
would yield solids involving Na+ or C!lO,--they
would be essentia,lly inert diluents.
and would serve chiefly to maintain electrical neutrality.
The dashed lines on the diagram indicate the range of stability of water and
hence by inference the general limits of a natural system. Above the upper dashed
line water is in equilibrium with more than 1 atm of oxygen:
below the lower
dashed line with more than 1 atm of hydrogen.
4n independent study of the vanadium-water
syst,em has recently bee11reported
by ~LTOMBE,
~OUBOV
and POT'RBATX
(1956). netailed information is available in
134
i1.2
1.0
0.8
0.6
I
YC
0.4
0.2
-0.8
-1-21
i
I
0123456789
1
lo
1
11
!
12
/
1s
!
:1
PH
Fig. 2. Tbc diagram of Fig. 1 rnodifkl
awording
to the rstimat~ed free crtergks
oftho osidea.
The dotted boundary
indicates
the estirnat~cd region of stability
itr, V(J(OH).
of hydmtiw
of montmxc~-
falls below about Ct.01 mole/l.) and those predict,etl by Fig, 1. These discrepancies
a.re utilized in a lat)er section to est,imate the energies of hydration of IT,O,. I,(),
and f;,05.
On t,he basis of these est3imat,es, t,he eq~~ilibri~l~~l diagram has been
rtlodj~e~~ and redrawn in Fig. 1. Presumably.
since all of the mineral vanadium
oxides (except the met,astable paramontroseite)
are hydrat,ed. the diagram of Pip. 2
will hare significant bearing on the natural system.
Perhaps the most satisfact,ory scheme in developing t,he interrelat,ions
of the
diagram is to discuss them sequentially in terms of the various valences of vanadium.
to work from the top of t-he diagram to t.he bottzom. considering first t.he behaviortr
GARRELS
vanadiurrb
111water solutions in equilibrium with air at room temperatures. only solids itlId
dissolved species containing quinquevalent vanadium are quantitatively iml)ortatltj.
I JlIaYc
DELT~MBE ct al.(c)
State(a)
(1
a,
0
~ 34,7
(r
--60.6
lo!)
-~ 143(d)
-1X9
-~ 271
--31x
334
a(i
aq
aq
(1
cr
54.2
~ 60.1
109.0
142.6
~ 189~0
-,71.0
318.0
~ 344.0
-:342~0
112.8
ac1
s
CP
aq
aq
aq
a9
~221.8
---665,3(g)
-1867(h)
.-1863(h)
1856(k)
(I
3.
60.1
lO)~O
142.(i
1 ,Y!),O
il.0
~318.0
:I44~0
34-.0
:! I ?w((~)
112.x
13,6(f)
----1.x
665.3
1X75.(j)
- lS70~3(j)
1Xt?x(,j)
Notes:
Vanadium forms a pervanadyl cation VO,+ only at low pH; the isoelectric poinb is
between pH 1 and 2, above which the vanadium is converted to comples anions.
At this point, the solubility of vanadium falls to a minimum, as is evidenced by the
stability field of the solid hydrated V,O,. At higher pH values a variety of anions
occurs; in general they range from deeply coloured, highly polymerized species at
lower pH values to colourless, less condensed ions at high pH values.
The most direct information concerning the fields of stability of vanadates irl
l%mnod~nsmic
equiliblia
solutions is provided by the diffusion rate studies of JANDER and JAHR (1933).
According to their technique, vanadium in a solution at a specified pH is allowed to
diffuse upward into a vanadium-free solution of equal ionic strength and pH for a
period of days. after which time the solution is separated and analysed by layers.
Several sharp breaks were found in their diffusion rate+pH curve: which is redrawn
from their data in Fig. 3(b). They also attempted to approximahe values of the
molecular weight#s of the diffusing ions by assuming that t,he molecular weight is
proportional t,o the inverse square of the diffusion rate? but this assumpt(ion is sub,jrct, to gross errors. The most careful titration experiments have been made by
er-
I
I
,
I
,
majYl
I
I
I
yrt1
,
I
I
I
I
Pyro
4
Hydrogen
10n concentration,
10
12
pH
diffusion experiments
of JATDER md LHR
(1933).
I)vCRlW (1951), and his final titrat#ion curve (pH vs. added HClO,) is shown redrawn
in Fig. :3(a). It is very similar to a curve determined by J.~KDER and JAHR (1%X3).
DVCRET
also attempted to determine the formula of the reacting vanadate ions by
careful interpret,ation of the shapes of t,he curves. Such an interpretation is very
uncertain. and his conclusion t,hat the largest va,nadate ion produced is H,V20,p
(corresponding to the orange polyvanadate) is not support8ed by any other evidence
that has been accumulated for this system.
(rystallographic
data on the vanadate system are meagre.
BAKER
(lSY5)
has described a series of very soluble crystalline orthovanadates
which are isomorphous with the corresponding phosphates and arsenates thus indicating the
existence of the \T0,-3 ion in solution. A series of compounds has been shown by
crystallographic
study to be salts of the ion V100z8-6: which corresponds to the
orange polyvanadate
ion (Ev_4ss
et al.:
1955). but, it,s structure is st,ill unknown.
137
H,I:,,0,8--
7 4H.r s
[H,I-,,0,,-4]
\,I),4&O(s)
-+ (3 -
n)R,O
liV,O,~n.H,O(s)
+ (3 -
tz)H.,O
+ 2H * t+ 2V0,~
-; 6H,O
t,he phosphates and arsenates, the acidified ions are inhererAy unstable and immediately split out water t(hrough condensation
reactions.
Only the acidified polyand
H,V,,O,,-*
persist
as
predominant
species in solution,
ranadate ions HV,0028-5
but even these may actually be metastable.
Below pH 5.5. polyvanadate solutions
on heatring or long sbanding precipitate insoluble products such as K,T,O,, and
(atV,C),,.9H,O (hewettite) (MARVIS. unpublished data). The tendency of ranadates
t,o form high molecular weight complexes in acid solutions is very similar Lo that of
t,he molybdates a#nd tungsDates. These form isopoly ions in solutions of pH 3 to (i
such as Mo,O,,-.
Mo,O,,-* and H,0W,,046 P20. The structures of-these complexes
are known? but no relation has been found between the structure of the polyvanadate ion and the polymolybdate
and polytungstate compounds.
Iaboratory
investigations of compounds of this type are hampered by the sluggishness with
which the condensation and decomposition reactions occur in solution. Sometimes.
many hours are required for a freshly prepared solmion of a poly-ion to reach a
st,able condition.
I~CRET
(1951) gives acid-base titration curves for quadrivalerlt I-anadium.
At low pH the ion in the blue solution is ranadyl, TO+?-. which behaves like a
simple metallic caCon. It hydrolyses to form TO(OH)+ according t)o the reactiolr
(ROSSOTTT
and ~~~~~~~~~~~19%):
results in precipitation
IO(OH)+
of the hydroxide:
H,O m+ \O(OH),(s)
+ H
At, a VO(OH)+ content of 0.01 molar. the precipit*ation pH calculated from tjhr free
energy of formation (as illustrated earlier) of the anhydrous oxide is 3.5 (Fig. 1,
Table 1). This difference in precipitation pH may be a,scribed to the hydratiorl free
energy of \,O,:
\T201(s) T -Hz0 + VO(OH)2(~)
AF
7 1. I kcal
less;
1VO(OH),(s)
+ T,0,mm2+ :IH,O + H
Trivaht
vanadi~sm
+ 3H,O -
dV(OH),(s)
Thus, V,O, is more stable than V(OH),, and is analogous in this respect, to Be,O,
and B$O,.
The apparent, difficulty in obtaining artificially the anhydrous oxide,
or perhaps a compound such as &O(OH),
or VO(OH), is not, surprising in view of
The free energy of montroseite.
t,he fairly small free energy change on hydration.
VO(OH), is unknown, but its prevalence in the Colorado Plateau sandst,ones, and
the absence of V,O,, suggests that it is the most stable llydrated phaSse at t,he
temperat,ure of formation.
At present. we can only assume that t,he energy of
formation of montroseite from V,O, is quite smaJ1. without predicting whether
at the lower tenl~erat~~res it is positive or negative. An est,imat,ed stabilit~7 field for
VO(OH) is indicated by the dotted lines in Fig. 2, and is used in int,erpret,ing the
mineral system in Fig. 4, described in later sections.
The hydroxide shows no amphoteric behaviour in Dhe pH range up to 14.
Trivalent vanadium ions and conlpounds are notably unstable with respect to the
atmosphere;
even tjhe natural oxide montroseite alters at an appreciable rate in
t,he laborator?.
Bivalent vanadium
therefore, as GARRELS
vi3
_+_ e-
where E* is the standard electrode potential, F is the Faraday, and 7~ the number of
electrons involved.
Thus E" is obtained from bF". and E,!is obtained from:
The further condition is imposed that (W3) and (Viz) (activities) are equal.
As can be determined from the equation, or from Fig. I? the boundary between
these two species is simply BP, and extends parallel to t#he pH axis.
140
H&J +
To
zH~- f
of including
No,7i9,dnI.ipsb~tl(*CC,7b
solids
\4Iere two solids containing vanadium in different valence states are juxtaposed,
tile boundary is determined by equations such as that, relating V,O, and V,O,,:
V,O,(s)
E,, = ISo +
O*O59
F log (H-1)
01':
E,,
h'o
--
pH
0.059
Several cases occur involving a solid containing vanadium in one valence and
solution containing dissolved vanadium in a species of higher or lower valence. For
example. Vz03 dissolves to form V,0,-2 as the oxidation potential is increased in
alkaline solut,ion. The equation is:
%Vz03(s) + 3H,O ---zV,0,-2
0.059
E,( = EO + 4
log [V,0,-2]
+ 6H-+ i- 4e-
; x 0.059 pH
The specific position of the line thus is fixed by knowledge of E, pH, and the
stipulaGon that [V,0,-2] is 0.01 molar.
Considerable uncertainty attends the boundaries drawn between VzO, and the
vanadates.
As shown on Fig. 1. mixed oxides containing both quadrivalent and
quinquevalent vanadium occur in this position. The possibility presents itself that
these mixed oxides may be regarded as vanadyl vanadates, but the few structures
of these compounds that have been published indicate that they have no saltlike
data are available
character (e.g. NaV,O,,, WADSLEY. 1955). No thermodynamic
for them, but there is no evidence to indicate that their appearance will appreciably
shift the precipitation boundary from that shown.
Effect of temperatuw
The effect of temperature on the field boundaries shown in Fig. 1 cannot be
calculated with assurance in the absence of data on heat capacities of the species
involved.
However, the temperature coefficient at, 25C can be found and used to
141
H. 7'.
EVANS,Jr.nnd K. Al.U.ums~s
determine the trend and probable change of boundaries over a limited temperature
change. Changes in boundaries can be calculated in terms of aE/aT or aA.FIaT:
~aE = _ ~_~
;?, Ax=
aT
iTAP
._ --1*)
aT
In general, a temperat,ure change of a few t,ens of degrees would apl)ear t,o have
litt,le effect on the general fields of stabilitp.
For example% for the reactsion:
V20, + H,O ---f V20, f
using entropy
entropy is :
2H-
+ 2e-
the c~hal~g(~ill
98 = -~ 15.65 cal/mole/(
whence
aE
aT
15.65
~~
2 x 23,060
= 0~00031 T'olt/Y(
decomposition boundary between pH 4 and pH 10. As has been noted earlier, this
region probably expands slightly upward and to the left at higher temperatures.
Mont.roseite is formed in this region.
~~~~~~~n~~ose~~~:V,O, or VO, (EVAKS
and MROSE, 1955). This mineral is derived
by solid state oxidation from montroseitc; it is probably metastable and ha,s no place
on the ayueous equilibrium diagram. Nevertheless. it is important in the weat,hering
process. because it, provides a path for t,he breakdown of the chemically resistant
montroseite. It proba8blp always forms a11intermediate first step in the weatheriuy
of mont,roseit~e.
-0.4
2-
VALENT
3
tlydrogcnim
5
concentration,
-L-I
7
6
pH
units
~~o~~/,~~~~~:
31,0,-4H,O
or V,O,(OH),
(STERY rt al.. 195i).
This species is
cotnmon replacing montroseite in partially oxidized ores. Its mode of occurrence
indicates that it results from solid state aheration of montroseite (or paramontroseite) under conditions in which vanadium is not dissolved.
D&to&~:
V,0,*2H,O
or VO(OH), (THOXPSON et al., 1957). This species is a
hydrated yuadrivalent
phase, occurring as crystalline crusts lining cavities. Ih
evidently forms from solution in ground waters carrying vanadium not yet, oxidized
ltqond the (l~~adri~~alent,state.
Nimplotite:
Ca0+2V,0,*5Hz0
(THOMPSON et al., 195X). Though its formula
may be written CaV,O,*5H,O,
simplotite is green in colour and does not represeub
fixation of the soluble brown-red vanadite ion. Its structure appears to be a complex
sheet related to that of autunite, and as yet has no synthetic analogue.
lb is
commonly associated with dut,tonit#e but appears to indicate a relatively alkalilie
environment.
Corvusite: CaO.xV,O,.yV,O,.nH,O.
This mineral has distinct physical prol)elties but has not been defined chemically within the above general formula. The
valence apparently can vary without appreciable alteration of the stru&ure so that)
it may be either inherently non-stoichiometric or an intimate mixture of two or more
closely related phases. The ratio x : y is usually about 1 : 5 or 1 : 6. It is associated
with acid environments and evidently hovers near the top of the V,O, field.
Nelanovanadite:
2Ca0.2V,O,*3V,O,.nH,O.
Although
this species also hs
not been clearly defined chemically, it is entirely distinct from corvusite.
It is
found in alkaline environments and appears to be associated with the metavauadate
field, while corvusite is associated with the polyvanadate
field.
Zawqjoife:
V,0,.3H,O
or VO,(OH).H,O
(WEEKS et al.. 1955). Navajoit)e Iias
not been synthesized, but it apparently corresponds to the hydrated V,O, field. Tt)
has a crystal structure closely related to that of corvusite and hewettite.
Hewettite:
Ca0*3V,0,*9Hz0
or CaV,0,,.9Hz0.
Hewettite
is an insoluble
product of the more acid side of the polyvanadate field, forming below pH 5.5. Its
structure consists of a sheet arrangement closely similar to that of navajoite and
corvusite.
This mineral has formerly been incorrectly
Pascoite : 3Ca0*5V,O,*16H,O.
described as 2Ca0*3V,O,*llH,O
(PALACHE et al.. 1951. p. 1055) but actually is a
soluble salt of the orange polyvanadate complex? Ca,V,,O,,~l6H,O
(EVANS e.t al..
1955).
K,Mg,V,,0,,*16H20
(WEEKS et al., 1953). also is a soluble polyHummerite:
vanadate.
Rossife: Ca(VO&.4H,O.
Rossite is a metavanadate. and is easily synthesized
from neutral solutions.
is the dehydration product of rossite.
&!eta?-ossite : Ca(V0,),.2H,O
Carnotite: Kz(U0,)zV,0,.3H,0.
The least soluble vanadium complex (except
possibly montroseite and the silicates) is carnotite and its analogues. It decomposes
below pH 2.2 but is stable at the expense of all other quinquevalent
vanadium
The crystal structure does not contain ort,hominerals at higher pH values.
vanadate groups as proposed by SUNDBERGand SILL&X (1949), but has been found
by recent work (BARTON and APPLEMAN. 1957; APPLEMAN and EVANS, 1958) to
have structural and chemical properties of a metavanadate.
The structure conbains
V,O,-6 groups with vanadium in five-fold co-ordination (as in KVO,.H,O).
Tyuyamunite:
Ca(UO,),V,O,~SHsO
is the calcium chemical analog of carnot,ite.
Rauvitc:
xUO,.yV,O,.zH,O.
In acid solutions deficient in metal cations,
rauvite is formed as an insoluble colloidal product of variable composition wit11y
usually somewhat greater than Z. It is believed to have a structural relationship to
the sheet structure of carnotite. and may be a precursor to t,he formation of carnotite
in very acid environments.
144
Thermodynamic
equilibriaof vanadiumin aqueoussystems
VANADIUM MINERAL PARAGENESIS UNDER WEATHERING
A typical partially oxidized ore body in the central Colorado Plateau region
consists of bluish-black vanadium oxide disseminated through the sandstone in
bands. Locally, sometimes in conjunction with woody debris, the vanadium oxide
ore is concentrated into pods or blue-black eyes.
In the centre of these pods, in
fresh openings, jet-black montroseite is often still preserved.
Outward from these
cores the vanadium mineral assemblage changes continuously to a more oxidized
state. This change in state of oxidation is accompanied by characteristic colour
changes. Generally speaking, the trivalent and trivalent-quadrivalent
minerals are
black, the quadrivalent-quinquevalent
minerals are dark blue, green or brown, and
the fully oxidized minerals are lighter brown, yellow or red-orange.
Sometimes
these three zones are separated by sharp boundaries.
Pyrite is usually present,
creating locally rather strongly acid conditions under weathering.
Good examples
of these relations can be seen at the Bitter Creek Mine and the J. J. Mine in
Montrose County, Colorado, and the Monument No. 2 Mine in the Monument
Valley district of Arizona.
More rarely, the environment of oxidation is slightly alkaline, in regions where
pyrite is absent and calcite is abundant. The most notable example of this situation
is the Peanut Mine in Bull Canyon, Montrose County, Colorado.
In this case, a
wholly different series of minerals is found in the oxidation sequence.
Petrologic and paragenetic studies almost always indicate that the primary
vanadium minerals are silicates and the oxide, montroseite.
It is very likely that
all of the other vanadium minerals in the sandstones, including carnotite, were
derived from montroseite.
Vanadium bound in silicates apparently is not released
by weathering and therefore these minerals, although important commercially, are
incidental to the present discussion.
The first stage in the oxidation of montroseite under any conditions is the
The conversion is brought about by a solid state
formation of paramontroseite.
reaction in the presence of oxygen either in the air or in groundwater as explained
by EVANS and MROSE (1955).
Reaction is very rapid, and fresh montroseite
specimens alter quickly in the open air. EVANS and MROSE have concluded t,hat
paramontroseite
itself is metastable, owing its existence purely to the crystal
structural control of the original montroseite.
In the presence of water, paramontroseite is quickly decomposed and new hydrated oxides of quadrivalent, and
quinquevalent
vanadium are formed.
This process gives rise to an interesting
sequence in which one anhydrous variety of V,O, (paramontroseite)
is apparently
less stable than various hydrated hydroxides (e.g. duttonite, V,O,.2H,O),
which
in turn are thermodynamically
less stable than the normal anhydrous oxide having
a distorted rutile structure. No trace of the stable anhydrous oxide has yet been
found in nature;
therefore, the rate of conversion of the hydrated oxides is
apparently neglible, even in terms of earth processes.
If further oxidation is retarded (especially if the ore is kept submerged below the
water table where the supply of oxygen is limited), two other quadrivalent minerals
may form in place of the paramontroseite-doloresite
or duttonite.
Doloresite is
observed as a paramorphic replacement of the paramontroseite,
with remnants of
the latter usually remaining (STERN et al., 1957). Duttonite forms as drusy crystals
145
IO-(20
pp.)
Thermodynamic
equilibriaof vanadiumin aqueoussystems
stability range is indicated by the shaded boundary in Fig. 4, and all other vanadium
minerals in this range become metastable with respect to the uranium complex.
The ready formation of carnotite from acid solutions has been a puzzle in view of
the crystal structure determination
of SUNDBERG and SILLI!% (1949), which
indicated that the vanadium is bound in it as orthovanadate
groups (V04-3),
because in such solutions the orthovanadate
concentration
is exceedingly small
(less than lo-l2 moles/l. at pH 6). New studies (APPLEMAN and EVANS, 1958) have
shown that the proposed structure is incorrect, and that vanadium is in five-fold
co-ordination in the carnotite structure in V,0,-6 groups. Also, it is found (BARTON
and APPLEMAN, 1957) that carnotite behaves chemically like a metavanadate,
so
that its association with neutral or slightly acid environment,s is fully explained.
When the environment is strongly acid, rauvite may be formed.
The role of
this unusual mineral in the paragenetic sequence is uncertain, but it may have an
intermediate position between the formation of the polyvanadate
complex and
carnotite under very acid conditions.
The structure of rauvite cannot be directly
determined since it is characteristically non-crystalline, at least in three dimensions:
but it is felt that it probably consists of a random stacking of a sheet type of
structure, which is related in some way to the sheet structure of carnotite.
In concluding this survey of the weathering paragenesis of vanadium minerals.
it may be said that all field or microscopic observations of petrology and mineral
associations studied, without any significant exceptions, support the weathering
scheme derived herein from the thermodynamic
properties of vanadium.
INIPLICATIONSOF THE EQUILIBRIUM. DIAGRAM
ON THE PROBLEM OF ORE DEPOSITION
While the paragenesis of the vanadium and uranium minerals under weathering
conditions on the Colorado Plateau now seems fairly well defined, the manner of
deposition of the primary montreseite-uraninite-coffinite
ore is still an unsolved
problem.
Accepting the current hypothesis that the ores were brought in by
mineralizing solutions at 55-110C
(COLEMAN, 1957), it appears probable from
the thermodynamic considerations that they could not have been carried in solution
in the reduced state in which they were deposited.
Trivalent vanadium is too
insoluble for transport except at pH values considerably below those expected for
such solutions; a similar situation holds for quadrivalent uranium. Consequently,
the vanadium and uranium must have been carried in more oxidized state, and
deposited under the action of reducing agents, such as divalent sulphur or the wood
debris commonly enclosed in the sandstone.
On the other hand the El, could not
have been sufficiently high, to permit all vanadium to be in the quinquevalent state.
as the small solubility of carnotite would prevent transport.
Therefore the best
estimate is that vanadium was carried as the quadrivalent VgOg-2, which, so far as
is known, does not interact with sexivalent uranium. These tionsiderations suggest,
referring to Fig. 2, that the mineralizing solutions had a pH of about 9 and an
oxidation potential of about -0.1 volt. Even if the transport and deposit of vanadium
and uranium can be accounted for under the conditions, the presence of pyrite or
marcasite, which petrologically
appears to be contemporary
with montroseite,
147
poses a problem because of the presumably low solubility of iron in this thermodynamic range.
The only certain conclusion that can be made now is that the problem of ore
deposition on the Colorado Plateau will be solved at least partly through the further
study and refinement of the thermodynamic
equilibriLlm properties, especially in
the region suggested above.
SUMM_4EY
of carnotite.
10,765.
RAKER H. (1885) The orthovanadat,es of sodium and their analogs. J. Chem. Sot. 47, 353-361.
BARTO?; P. B., JR. and APPLEMAN D. E. (1957) Cryst~al chemistry of carnotite. Ao?vcznceain S&ear
Engineerirzg, Vol. II: Proceedings of the Second Nuclear Engineering
and Science Congress.
Ihiludelphin (Edited by DUNNING J. R. and PRENTICE B. R.), Pt. 2, pp. 294-299. Porgamon
Press, New York.
CHRIST C. L., CLARK J. R. and EVANS H. T., Jtt. (1954) The crystal structure of potassium
metavanadate
monohydrate,
KVO,.H,O.
Acta Cry&. Camb. 7, 801-807.
COLE;MAXR. G. (1957) Mineralogical evidence on the temperature of formation of the Colorado
Plateau uranium deposits. &~n. Geot. 52, 1-4.
DELTOMBE E., DE ZOUBOV I\. and POURBAIX M. (1956) Comport.ement
electrochimique
du
vanadium. Diagramme dhquilibre tension-pH du syst&me V-H,0 a 25C. Rappwt tschurigue Aio.
29 Centre Belgo dEtude de la Corrosion, Bruxeiles.
DUCRET L. P. (1951) Contribution a 16tude des ions des valence quatre et einq da vanadium.
Ann. Chim. 6, 705-776.
EVANS H. T., JR. and MROSE MY, E. (1955) A crystal chemical study of montroseite and paramontroseite.
Amer. Min. 40, 861-875.
EVANS H. T., JR., MROSE M. E. and MARVIN R. (1955) Constitution of the natural antI artificial
decavanadates.
Amer. Min. 40, 314-315 (Abstract).
148
Thermodynamic
FISCHER
of the Uraran
mineral belt.
Bull. 988-A.
GARRELS R. M. (1953) Some thermodynamic
relations among the vanadium oxides, and their
relation to the oxidation state of the uranium ores of the Colorado Plateaus.
Amer. Min. 38,
1251-1265.
G~RELS
R. 31. (1955) Some thermodynamic
relations among the uranium oxides and their
relation to the oxidation sbates of the uranium ores of the Colorado Plateaus.
Amer. Min.
40, 1004-1021.
GKUNER J. W., GARDINER L. and HWTH D. K., JR. (1953) Annucd report for July 1, 1952 to Narch
31, 1953. U.S. Atomic Energy Comm. RME-3044,
Tech. Inf. Service, Oak Ridge, Tenn.
HESS F. L. (1933) Uranium, vanadium, radium, gold, silver, and molybdenum
sedimentary
deposits.
Ore Deposits of the Western States, Lindgren
Memorial
lolume,
pp. 450--481.
Amer. Inst. of Mining and Metallurgical Engineers, New York.
JANDER G. and JAHR K. F. (1933) Aufbau und Abban Hfihermolekularer
anorganischer Verund Vanadansalzo.
%.
bindungen in Liisung an Beispiel der 1anadinsLure, Polyl-anadate
Anorg. Chem. 212, l-20.
KRUMBEIN W. C. and CARRELS R. RI. (1952) Origin and classification of chemical sediments in
terms of pH and oxidation-reduction
potentials.
J. Geol. 60, l-33.
LATI~IER TV. M. (1952) Oxidation Potentials (2nd Ed.). Prentice-Hall,
New York.
MCKELVEY V. E., EVERHART D. L. and GARRELS R. M. (1955) Origin of uranium deposits. Ecocon.
Geol., Fzftieth Anniversary
Tohme Pt. I, pp. 464-533.
PALACHE C., BERMAN H. and FRONDEL C. (1951) Danas System of Mineralogy
(7th Ed.) Vol. 11.
Wiley, New York.
POUBBAIX 34. J. N. (1949) Thermodynamics
of Dilute Aqueous Solutions.
Arnold, London.
ROSSOTTI F. J. C. and ROSSOTTI H. (1955) Studies on the hydrolysis of metal ions. XII:
The
hydrolysis of vanadium (IV) ion. Acta Chem. &and. 9, 1177-1192.
ROSSOTTI F. J. C. and ROSSOTTI H. (1956) Eq wlb
1 rlum studies of polyanions. I: Isopolyvanadat,es
in acidic media. Acta Chem. Stand. 10, 957-954.
STERN T. I\-., STIEFF L. R., EVAXS H. T., JR. and SHERWOOD A. M. (1957) Doloresite. a new
vanadium oxido mineral from the Colorado Plateau.
Amer. ,Win. 42, 587-593.
STIEFF L. It., STERN T. W. and SHERWOOD A. M. (1956) Cofl?nite, a uranous si1icat.e with hydroxyl
subst,itution: A new mineral. Amer. Min. 41, 675-688.
SUNDBERC I. and SILL&N L. G. (1949) On t,he crystal structure of KUO,VO,
(synthetic anhydrous
carnotite).
Ark. Kern,,, 1, 337-351.
SYNE:EK V. and HANIC~ F. (1954) The crystal structure of ammonium metavanadate.
Ehlys.
J.
4, 12&130.
THOMPSON M. E., ROACH C. H. and MEYROWITZ R. (1957) Duttonite,
a new quadrivalent
vanadium oxide from the Peanut mine, Montrose County, Colorado.
Amer. Min. 43, 455-460.
THOMPSON M. E., ROACH C. H. and MEYROWITZ R. (1958) Simplotite,
a new quadrivalent
vanadium mineral from the Colorado Plateau.
Amer. &fin. 43, 16-24.
WADSLEY A. D. (1955) The crystal structure of Na,_,V,OI,.
Acta Cryst. Camb. 8, 695-701.
WEEKS A. D., CISNEY E. and SHERWOOD A. M. (1953) Montroseite, a new vanadium oxide from
the Colorado Plateaus.
Amer. Min. 38, 1235-1241.
LVEEKS A. D. and THOMPSON M. E. (1954) Identification
and occurrence of uranium and
vanadium minerals from the Colorado Plateaus.
Ti.S. Geol. Survey Bull. 1009-B, 13-62.
~VEEKS A. D., TIIOMPSON M. E. and SHERWOOD A. M. (1955) Navajoite,
a new vanadium oxide
from Arizona.
Amer. Min. 40, 207-215.
149