Infrared Spectra-Structure Correlation Study
of Vanadium-Oxygen Compounds
LEO D. FREDERICKSON, Jr.
Spectran laboratories, Inc., Denver, Colo.
DONALD M. HAUSEN
Union Carbide Nuclear Co., Grand lunction, Colo.
Plnfrared absorption bands charac-
teristic of vanadium-oxygen vibra-
tional modes in various compound
classes-e.g, deca-, hexa-, meta-,
pyro-, and orthovanadates, vanadyl
salts and oxides-have been as-
sembled in the form of a spectra-
structure correlation chart. Hexavana-
dates, decavanadates, and vanadyl
compounds show good correlation be-
tween spectra and structure of their
classes. The metavanadate classifica-
tion appears identifiable on the basis
of the presence of more strong bands,
and each pattern is suitably distinctive
to permit qualitative identification.
Ortho- and pyrovanadates appear to
b e identifiable as a class or group, b y
virtue of lower frequency absorption
band groups. Spectral data and in-
terpretations are summarized in the
paper.
A SALOGUUS TO phosphorus in its
higher valence states, vanadium
forms covalent linkages with oxygen,
and this, together with its relatively
light atomic weight, provides for the
appearance, and therefore study, of the
vanadium-oxygen fundamental vibra-
tions in the rock-salt region of the
infrared spectrum.
Compounds containing vanadium and
oxygen in combination comprise a
variety of chemical classifications, pri- used was Harshaw Chemical Co. in-
marily as a result of the conditions of
acidity during their formation. Ortho-
vanadates (XaV04)are formed a t rela-
tively high pH, pyrovanadate salts
(X4Vz07) a t intermediate alkalinity,
mctavanadates (xVo3) at or near neu-
tral p H values, while complex poly-
vanadates (X2V6016, XfiV10028) are the
result under acidic conditions. Of the
four known oxides of vanadium, V Z O ~ as of physical descriptions and properties
and Vz04 contain covalent oxygens in
their structures; other oxides, V203
and VO, display poorly defined spectra
t h a t may not indicate V-0 covalency.
Other classes include vanadyl com-
pounds with a single, covalent oxygen
linked to vanadium, and the vanadium
ores including the minerals vanadinite,
hummerite, metahewettite, pascoite,
corvusite, carnotite, and tyuyamunite.
While the majority of vanadium com-
pound;; exist as crystalline solids, somc resolution for the instruments used.
of the analogs of phosphorus, notably
vanadium oxytrichloride and vanadium
818 0 ANALYTICAL CHEMISTRY
oxytribromide, are liquids under normal
conditions.
The economic importance of vana-
dium in our technology and the complex
conventional chemistlry of the element
have prompted this investigation of the
infrared absorption spectra of a variety
of vanadium-oxygen compounds, for
the purposes of establishing the feasi-
bility of qualitative analysis for pure
compounds, commercial products, and
minerals, and determination of spectra-
structure correlations for the vanadiuni-
oxygen vibrational frequencies.
EXPERIMENTAL
The infrared spectra reported in this
study were recorded on two Perkin-
Elmer Model 21 spectrophotometers,
both equipped with sodium chloride
optics. Samples were examined in the
solid state both as potassium bromide
pellets and as mulls in mineral oil; in
the liquid state, in conventional sand-
wich-type demountable cells. Solids
were mortar-ground for preliminary
particle-size reduction, followed by
further grinding to suitable infrared
particle size in a mechanical vibrator-
mixer. Mulls were prepared in the
usual manner, with final grinding and
mulling done between infrared windows
in the mull medium. Concentration of
samples in matrix potassium bromide for
pellets was 1% by weight or less. KBr
frared-quality powder.
Vanadium compounds examined were
obtained from various commercial and
private sources and were of the highest
purities obtainable; usually C.P. salts
were examined. No special purification
of materials was attempted, although
every effort was made to select the
purest ones, and to establish the iden-
tity of compounds through careful check
given in the literature, as well as
examination of infrared spectra with
respect to detection of obvious impuri-
ties, etc. Certain of the compounds
were prepared for examination in the
laboratories of the investigators when
they could not be readily obtained from
other sources. Identity of vanadate
compounds was necessarily confirmed in
most instances by comparison with x-ray
diffraction pattern data.
Spectra were recorded in the range
5000 to 650 cm.-1, at medium to low
Some of the spectral presentations do
not include all of this range, as no in-
formation of importance in the work
was to be found therein.
FUNDAMENTAL VANADIUM-OXYGEN
VIBRATIONS
I n an attempt to correlate observed
infrared absorption spectra with chemi-
cal structure, a vanadium-oxygen com-
pound (or compounds) was sought, pos-
sessing simple structure and free from
extraneous potential interactions and
distortions which might be expected to
be present in the more elaborate struc-
tures to be included in the study. Such
a compound was available in the phos-
phorus analog, vanadium oxytrichlo-
ride, a tetrahedral structure with Csv
symmetry. This compound is a liquid,
thus providing the desired freedom from
crystal lattice forces and interactions,
to permit more nearly normal location
of fundamental vanadium-oxygen vibra-
tional frequencies to appear in its spec-
trum. Examination of the spectrum
of this molecule, as shown in Spectrum
1, shows the presence of a single strong
absorption band located at 1035 cm.-*,
assigned as the V I fundamental by
Miller and Cousins (6), and identified as
arising from the V-0 stretching motion
in the molecule.
Another simple compound, although
solid, was found in vanadium pentoxide,
shown in Spectrum 2. Here, the V-0
stretching mode is observed as a strong
band located a t 1020 cm.-’, or very
nearly the same location for this V-0
mode in VOCl,. These two spectra
tend to locate the “normal” position for
this stretching vibration between oxygen
and vanadium.
Another broad band is present in the
spectrum of vanadium pentoxide, cen-
tering a t 825 cm.-I The V Z O struc-~
ture has been described ( 2 ) as a double
chain of distorted, trigonal bipyramids,
joined a t the corners to form layers, the
latter held together by lattice or residual
forces.
The V205structure consists of VO
bondings of variable bond lengths, some
of which vibrate at lower frequencies
than others. The 1020 cm.-l band has
been assigned to a VO bond which is
considerably shorter than other bonds
in the structure; the 825 cm.-* band
very probably arises from the stretching
modes of the longer VO bonds.
Further support for these assignments
C(JII1CSfrom Siebert's work ( 7 ) on the
tctr:thedral ion in aqueous solu-
tion whose assignmeni,s are as follows:
y1 Y2 0 v4
Si0 345 825 480
nhere v1 arid v3 ale the syinrnetric and
assymmetric stretching modes, respec-
tively, for a lower frequency bond.
.I slight long wavelmgth shift of both
Y-0 bands is apparent, in spectrum 3
for potassium fluorov:madate.
VANADIUM COMPOUNDS AND INFRARED
SPECTF!A
Metavanadates. A nuinLcr of
metavanadates were obtained from
several sources for exunination during
t h e course of this invwtigation. Stud-
ies by Evans et (11. (9,4 ) have deniori-
strated t h a t the crystal structure of both
the hydrated and anhydrous potassium
inetavanadate is of the chain type, of
composition (VOa).-)L, cross-linked on
trigonal pyramid edges with other
chains, and vanadium esisting in five-
fold coordination wii h oxygen in the
crystal lattice. Examination of eight
infrared spectra for meta-salts, (Spectra
4-10), shows wide variation in individual
patterns for changes in the substituted
cation. In these eptxtra, several ab-
sorptions appear which are apparently
t,he result, of V-0 st'retching modes for
c m l i of several, different osygen atoms
according to the part'icular location or
arrangement within tlhe lattice. A t
lower frequency, a broad and general
absorption occurs wliich is similar to
the V20h pattern. ?'his is apparently
caused by lower frequency VO bondings.
1100 1050 lo00 950
I I I I
-
S -
vs
vs
- S
4 I
10
Figure 1 .
Cation Exchange in KBr-Pellet
Spectra. Observation of t h e spectra
in 4 t o 7 shows t h e meta-salts t o be
recorded both as K B r pellet spectra
a n d as mulls, with considerable dif-
ferences between them. These differ-
ences were first noted as a probable
interaction or cation exchange be-
tween t h e meta-salts a n d t h e matrix
potassium bromide, incurred during
t h e process of grinding, mixing, and
pressing of t h e pellet for infrared
examination.
To prove this theory, several individ-
ual salts were examined by x-ray dif-
fraction technique before and after
pelleting in KBr. The x-ray evidence
thus obtained indicated that the crys-
tallinity was destroyed under conditions
imposed by pelleting, for vanadate salts
showing large spectral differences be-
tween pellet and mull techniques. Fur-
ther, i t was observed that pota,'si u in
nietavanadate, when subjected to iden-
tical pelleting condit'ions, produced in-
frared spectra identical to those pro-
duced by mulling in mineral oil; x-ray
diff ractinn examination after pelleting
also showed this salt unchanged as a
result of the conditions of pelleting. I n
summary, sodiurn and ammonium meta-
vanadates appear to have been partially
metathesized after prlletizing, resulting
in amorplwus, solid solutions of t h e
vanadates in the KDr.
Discrepancies in infrared spect,ra of
certain metavanadate salts in KBr
media are attributed to cation exchange,
involving the K + ions of the potassium
bromide, and the cation of the meta-
salt involved. Minor matrix effects
FREQUENCY. CM-l
900 850
H E X A V A N A D A T E S ( V - 0 STRETCHINO) ( T W O
DECAVANADATES (V-0 S T R E T C H I N G ) ( O N E S T R O N O BAND)
VANADYL SALTS (V-0 S T R C T C U I N O ) (ONE STRON5 B A N D )
11
I
12
WAVrLEN5TU. MICRONS
Infrared absorption-structure correlation chart, V - 0 vibrations
have also been obseived in spectra for
vanadates of multivalent elements,
such as calcium and magnesium in
KBr pellet form.
K B r pellet spectra are, in most in-
stances, reproducible even though they
do not correspond to mull spectra, and
also may be suitably distinctive for ube
in qualitative identification. The ex-
tent to which variation in concentration
of meta-salt in matrix KBr mill affect
the resulting pattern in infrared spectra
has not been explored to any extent,
since most epectra require minimum
concentrations of sample.
Hexavanadates. T h e spectra in
Nos. 11 t o 17 illustrate t h e absorption
patterns for six compounds in t h e
simple polyvanadate rlass. Absorp-
tions in the V-0 stretching frequency
region are relatively strong in inten-
sity, and occur a t two rather constant
' locations, one near 1000 cm.-l, and the
other near 960 em.-'. Structural stud-
ies of Block ( 1 ) and of Wadsley (8) on
hexavanadates show that, for these sub-
stances, vanadium may coordinate n i t h
either five or six oxygens, existing in the
form of zig-zag chains of VO6 octahedra,
joined at corners to form roriugated
sheets or layered structures. Vanadium
exists in the final, assumed structure in
the form of V308anions, interleaved
with cations. Observation of these
spectra for various substituted cations
shows this structure to be little affected
by atomic mass or cationic radii differ-
ences. These spectra show the presence
of a strong VO band of loner frequency,
located near i50 cm.-', although there
is minor variation in its location from
8(IO 750 700
METAVANADATES ('4-0 STRETCHING)
(SEVERAL STRONG BANDS)
ORTHWVANADATES
( V - 0 STRETCHING)
( S E V E R A L STRONG
BANDS)
P Y R O V A N A D A T E S (V-0 STRETCHING)
( S E V E R A L S T R O N G BANDS)
STRONG B A N D S )
1
13 14
VOL. 35, NO. 7,JUNE 1 9 6 3 819
 1, Vanadium oxytrichloride, VOCI,

2. Vanadium pentoxide, Vz06

3. Potassium fiuorcvanadate

4. Sodium metavanadate, N a V 0 3
(In Nuiol)

5. Sodium metavanadate, N a V O a
(In KBrl
40

PO

0
7 e 10 It 12 13 14 15
WAVLLLNOTH ( M I C R O W S )

820 ANALYTICAL CHEMISTRY

 FREQUENCY (CM')
1400 1200 1 0 0 0 950 900 8XJ 800 750 700 650

80

60
6. Ammonium metavanadate, NHdV03
(In Nuiol)
40

P I ! ! P ! I ! ! ! , . ! ! ! ! ! ! : 1

80

60

7. Ammonium metavanadate, NH4V03

(In KBr)
40

20

8. Potassium metavanadate, KVOa

9. Calcium metavanadate, Ca(VOa)n

10. Mercury metavanadate, Hg(VO&

VOL. 35, NO. 7, JUNE 1963 821

 FREOUENCY (CM )
1403 1200 1000 950 900 8x1 800 750 700 650

1 1. Sodium hexavanadate, Na2V6O17*3H20

12. Potassium hexavanadate, K2VeOI7.3H20

1 3. Ammonium hexavanadate, (NH4),VS017.-

3 HzO

14. Barium hexavanadate, BaV6o17.3HzO

15. Calcium hexavanadate, CaV,jO17.3H20

7 I1
10 12 13 14 15
w&vE:LENarn (MICRONE)

822 ANALYTICAL CHEMISTRY

 16. Magnesium hexavanadate,
MgV6017*3Hz0

17. Metahewettite, CaV6017.3HzO

18. Pascoite, C a ~ V I U O 1~5. H z 0

19. Hummerite, KzMgzVloOa. 16HzO

20. Amine decavanadate

VOL. 35, NO. 7,JUNE 1963 823

 FREQUENCI (CM')
looa
960 300 em .oo 750 too .eo

2 1. Sodium ammonium decavanadate,

Nar(NH&VIoOn. 1 6Hz0

22. Sodium pyrovanadate, Na4V207qnH20

23. Calcium pyrovanadate, CaZVz01.2HzO

24. Strontium pyrovanadate, SrZV20i .nHzO

2 5 . Zinc pyrovanadate, Zn2VZOi.nH20

8 9 IO I1 LE 1. 14
WAVILLLNOTCI CMICROW.)

824 ANALYTICAL CHEMISTRY

 26. Sodium orthovanadate, NaaV04

2 7. Magnesium orthovanadate,

2 9 . Vanadinite, PbS(VO&CI

30. Vanadium tetroxide, VzOI

7 8 9 IO I1 I2 13 14 ia
WAVELENOTH <MICRONS>

VOL. 35, NO. 7,JUNE 1963 825

 FREQUENCY C M )
1400 1200 1000 950 900 850 Iyx) 7- 700 .eo
100

60

3 1. Vanadium trioxide, V20,

40

20

100

K,

32. Vanadyl chloride, VOCll

40

20

0
100

!-
0
Y "
0
z 33, Vanadyl sulfate, VOSO4
f 40

i
z
4 ao
L
k

0
100

mo

.o
34. Ammonium vanadyl tartrate
40

20

0
lo0

35. Vanadyl oxalate

40

so

0
7 . s IO I1 I2
WAVE L KNOT U tM I C R O W )
1s 14

826 0 ANALYTICAL CHEMISTRY

compound t o compound. Part of this
absorption is probably (due to the pres-
ence of water.
Wadsley’s work (8) also indicates
that there is one short T‘O bond at each
vanadium atom with the remaining VO
bonds being appreciably longer and
more variable. The 1-0 stretching
modes in the hexavanadate spectra are
therefore observed to o x u r in two dis-
tinct regions, 950 to 1000 cm.-l and
720 to 760 em.-‘
Decavanadates. T h e spectra of
several representatives of this classifi-
cation are presented in Spectra 18-21.
Previous a t t e m p t s t o elucidate t h e
structure of these compounds b y x-ray
diffraction technique83 have been
largely unsuccessful; however, t h e
presence of strong infrared bands in the
975 em.-’ region, attributable to V-0
stretching motions, indkates some simi-
larity to hexavanadate spectra-structure
correlations and suggeats a sheet- or
layer-type configuration for these salts.
Generally, only one strong band pre-
dominates in this region for decavana-
dates, in contrast to two such bands
associated with the previously described
hexa-salts. This significant difference
\)errnits the differentiation between the
two classes by means of infrared spectra.
Other absorptions of lower frequency
in the spectra of the decavanadates
appear to correlate with structure, but
their assignment is not as obvious as is
the apparent V-0 stretzhing mode near
960 em.-’ It is apparent that the spec-
tra of individual members of this class
are not suitably distinctive for use in
qualitative analysis, b u t may only be
identified as members 01’ the class.
Ortho- and Pyrovanrtdates. A lim-
ited number of representatives of these
classes were available for study, a n d
their spectra are presented i n Spectra
22-29. Included are vanadinite, a
supposed lead-orthovartadate salt, a n d
volborthite, a syntheti,: copper-ortho-
vanadate. Generally, the spectra show
absorptions occurring a t frequencies
lower than is the case for other classes
studied, and while qual.itative identifi-
cation of individuals appears a possi-
bility, no unique correlation or classify-
ing information appears for the spectra
as a group. The VO bonds in these
compounds are of the longer type, com-
pared to the other classes which contain
both long and short type VO bonds.
Oxides. I n addition to the primary
stable oxide VzOs, the tetravalent vana-
dium occurring i n VzC4 is shown to
possess an infrared srlectrum, as in
Spectrum 30. The barisis appearing in
this spectrum are not a s intense as in
the primary oxide, althcugh location of
the principal absorptior s indicates the
likely covalent nature of the bonding.
A poor infrared spectrum has been ob-
served for the oxide V203, showing a
broad, weak absorption between 1000
and 900 cin.-l I t s spectrum has been
included in Spectrum No. 31, although
it shows no definite structure or evidence
of covalence between vanadium and
oxygen in this form.
Vanadyl Salts. A number of com-
pounds were studied which contain
vanadium in t h e vanadyl configura-
tion (VO-X) wherein a single oxygen
atom exists in covalence with vana-
dium. These spectra are shown in
Spectra Nos. 32-35. An extremely
strong absorption band is noted in
these spectra, located near 1000 em.-’,
and arising from the V-0 stretching
motion. Such structures contain no
polymeric arrangement or multiplicity
of vanadium atoms that might distort
fundamental frequencies, and these
compounds show nearly “normal” loca-
tion for the V-0 stretching fundamen-
tal. The strength and characteristic
location of this absorption in these
compounds nearly assures the ‘dentifica-
tion of this form of vanadium-oxygen
bond.
Vanadium Minerals. Among the
naturally occurring sources of vanadium,
the minerals hummerite (K&i.g2Vlo-
0%. 16H20), metahewettite (CaV80n.3-
HzO), and pascoite (CasV10028. 15Hz0)
have been established as containing
vanadium in the polyvanadate class of
structures (9). This has been confirmed
by the infrared spectra, which exhibit
the strong V-0 stretching bands in the
950-cm.-l region, analogous to the poly-
vanadate spectra shown in Spectra Nos.
11-21. The classification of hummerite
as a decavanadate is shown to be correct,
with exact correspondence of spectral
features of this class near 960, 845, 800,
and 750 cm.-l However, pascoite,
whose structure has been indicated (6) to
be of the hexa-class, possesses spectral
features indicating that i t should be
classified with the decavanadates. Meta-
hewettite, assumed to possess the hexa-
vanadate structure, shows confirming
evidence of this in its spectral pattern,
with absorption bands located near 1000,
960, and 740 cm.-’
SPECTRA-STRUCTURE CORRELATIONS
Infrared absorption bands character-
istic of V-0 vibrational modes in the
various compound classes studied have
been assembled in the form of a spectra-
structure correlation chart in Figure l .
Hexavanadates, decavanadates, and
vanadyl compounds show very good
correlation between spectra and struc-
ture of their classes. The metavana-
date classification appears to be identifi-
able on the basis of the presence of more
strong bands, and each pattern is suit-
ably distinctive to permit qualitative
identifications. Ortho- and pyrovana-
dates appear to be identifiable as a class
or group, b y virtue of lower frequency
absorption band groups, with individual
mcmbers identifiable also. Other mis-
cellaneous compounds have been in-
cluded in the correlation.
DISCUSSION
Other minerals containing vanadium,
such as corvusite, carnotite, and tyuya-
munite were examined by infrared;
however, their spectra are not included
in this paper since there was reason to
doubt the purity of the samples available
for study. Other minerals accompany
these substances in nature, and the
samples examined showed evidence for
such contamination, with accompanying
distortion in their infrared spectra.
Matrix effects produced in the in-
frared spectra of certain of the com-
pounds when examined in potassium
bromide pellet medium have been ob-
served by a number of workers, with
many types of compounds, and are
believed to be generally recognized by
spectroscopists as a potential hazard,
particularly in structural analysis work.
It is the authors’ conclusion that
mineralogical examination b y infrared
spectrometry might be performed most
reliably using mull technique in the
light of the experiences with KBr pellets
during this work.
ACKNOWLEDGMENTS
The authors are indebted to the fol-
lowing: William P. Schoder, UCNC,
Grand Junction, Colo., for synthesis of
many pure vanadium compounds; John
Lane, UCNC, Grand Junction, Colo.,
for background information on vana-
dium chemistry and assistance in prepa-
ration of samples for examination; Tom
Nillensifer, T h e Shattuck Chemical Co.,
Denver, Colo., H. R. Grady, Vanadium
Corp. of America, Cambridge, Ohio,
and Richard P. Fischer, U.S.G.S., Den-
ver, Colo., for their kindness in supply-
ing samples; and to William Riggle,
UCNC, Grand Junction, Colo., for
drafting of figures.
LITERATURE CITED
(1) Block, S., Ph.D. thesis, Johns Hopkins
University, Baltimore, RId., 1954.
(2) Bystrom, A., Wilhelmi, K. A,, Rrct-
zen, D., Acta Chem. Scand. 4, 1119
(1950).
(3) Christ, C. L., Clark, J. R., Evans,
H. T., Jr., Acta Cryst. 7, 801 (1954).
(4) Evans, H. T., Jr., Block, S., Bid!.
Geol. SOC.Am. 64, 1419 (1953).
( 5 ) Miller, F. -4.)Cousins, L R., J . Chetn.
Phys. 26, 329 (1957).
(6) Palache, C., Berman, H., Frondel, C.,
“Dana’s System of Mineralogy,” 7th
ed.. 3. 10.55 (1951).
( 7 ) Siebert, Hans,‘ Z. Anorg. Allgem.
Chem. 274, 24-33 (1953).
(8) Wadsley, A. D., Acta Cryst. 8 , 695
(1955).
(9) Weeks, A. U., Thompson, M. E.,
U.S. Geol. Surv. Bull. 1009-D (1934).
RECEIVED for review September 13, 1962.
A4cceptedApril 4, 1963. Presented in part
at the XVIIIth Intl. Congress of Pure and
Applied Chemistry, Montreal, Canada.
August 1961, and a t the Fourth Annual
Rocky Mountain Spectroscopy Confer-
ence, August 1961.
VOL. 35, NO. 7, JUNE 1963 827