CHAPTER - II

CHEMISTRY OF HETEROPOLYACIDS AND SAIjTS AND

THEIR STRUCTURES

25
lister and Yoshino have described the preparation and
properties of the interesting compound HagUgCoClOgJg.lCHgO -which
apparently contain periodate coordinated to Co(III). Starting
from the above compound, Hyman and Plane104 prepared a dark green

polynuclear complex having the composition H3 Co4l303gH24 Similar

105
compounds have also been prepared by direct method and formulated
as H,3w
Co„IJ50„H
4 3 24 12 .3HgO. Since this latter compound and the one
prepared by Hyman and Plane, have not been fully characterised,
so we have taken up this work.

Considering the above cobalt periodato compound belongs

to heteropolyacids, a brief review of heteropolyacids is necessary.

The weak osy-acids formed by the amphoteric elements of

Groups ¥ and VI of the Periodic Table have the pronounced ability
to condense forming molecular species having several molecules of
simple acid anhydrides. Such acids are known as "Polyacids". Mien
the polyacid contains only one type of acid anhydride, it is an
isopolyacid, but i$ more than one kind of acid anhydride is present
a heteropoly acid results.
 45

The free acids and most salts of the heteropoly anions are
extremely soluble in water and in various oxygenated organic sol­
vents, Mien crystallised from water, the heteropolyacids and salts
are always obtained in highly hydrated condition. They are decom­
posed by strong base:

34 0H“ + P 2^18° 6 2 = 18 Mo042“ + 2 H'P042“ + 16 HgO

16-
18 OH" + Fe2Wl2°42 = 12 W042" + Fe203.nH20 + 9 HgO

Many heteropolyacids are stable without depolymerization in quite

strongly acid solutions! they are often themselves strong acids.
In general, heteropolymolybdates and tungstates of small cations
including those of some heavy metals, are water soluble, but with
larger cations insolubility is frequently found.

The table lists the principle types of het eropolymolybdat es,

many of which have exact or similar heteropolytungstate analogs :

(shown in table 8).

 46

Table 8

T
Ratio of 0 Principal types of Heteropolymolybdates
h et ero 0_____ ________ ___________
atoms to 0 Principal het ero atom f
Mo atoms $ occurring Anion formulas
0
11 12 SeriesjLJ P7, As7, Si17, (8-n)-
Xll+ M°1S040
Ge17, SnI7<?),
Ti(IV), Zr(I?),
Hf1^, B(III)
n(12-n)-
Series B: Ge17, ThI7,SnI7(?) X Mo12°42

is 11 Pv, As7, Ge17 Ynt,n n -t(12p-n)-

X ^°11°39
(possibly dimeric)
is 10 P7, As7, Pt17 Xn +Mo io°xT(2X"60“ri)'

1j 9 Mn17, Ni17 X "^°9032 (10-n)-

1! 6 Co111, I711, Te7^, Al111, ' rn-i- „ 1(12-n)-

Crin, Fe111, Rh111, Hi, X Mo6°24
Cu, Mn.

P7, As7 (l6-2n)-

2 S 18 X2 Mo18°62

2:17 Y As*
P*, X2n+ Mo17°X 7(2x-l02-2n)
j

lm: 6ma Hi11, Co11, Mn11, Cu11, m( 2x-36-n)-

xK+ «°6°x ]
Se17, P111, As111, P7 m

a for the tungstate analog of the Co compound, it has been

found m = 2.
 47

This preferential tendency of the hetero atom to combine with 6

or 2 x6 molecules of the other acid anhydride Bed Miolati, Copaux
and Rosenheim107 to represent the poly-acid anion as a coordination
complex based on an extension of the general concepts introduced by
Werner. It was suggested that the acid anhydride molecules are
coordinated to the hetero atom which serves as the centre of a
coordination complex, the het eropolyanion. For each non-metallic
element (X), a parent acid was regarded as resulting from suffi­
cient hydration of the anhydride to give six oxygens coordinated
to the central atom i.e. a material of formula H 12-n XO, , n being
the oxidation state of X. Heteropclyacids then result from partial
or complete substitution of these oxygens by equivalent simple
groups such as Mo04 , W04 or 703 or hypothetical doubled groups
such as MOgO^2", WgO^2" or 7g0g2" or by coordination of the anhydride
molecules Mo0„,
3, WD
*«w3, or ^g*W2 tiiese oxygens, in this fashion,
limiting series of 6- and 12- acids were derived as indicated in
the table, a fixed coordination number of six being implied for
all central atoms.
 48 -

Het eropolyacids according to Miolati and Rosenheim

--------- p-----------5------
CentralS Oxidation 0 Parent 5 Limiting jj Known
atom, 0 state, n 0 acid S Heteropoly S compounds
X S 0 S acids 3
0 S

B +3 He BO/ H B<Mo2°7>6
9L

Si +4 H, SiO, H8[si(W207)6 H4Si¥120.

8_ "6

P +5 Hr7LP06i H, p(w2o7)6 h3pw12o

Te •*6 H, TeO, >] H Te(Mo04)6

I 47 h5[I06J I(Mo04)6

That all of these compounds are highly hydrated suggests

strongly that a portion of the hydrogen regarded as acidic is

2-
actually present as water. Furthermore, groups such as Mo207
2-*
and ’Wg°7 are entirely hypothetical and have no independent

existence.

1 Oft
As an alternative, Pfeiffer suggested that complexes

of high coordination number can he more easily built' around a 'central

polyatojnic'.ion. Thus "WD3 or Mo03 molecules are coordinated around

the X06 ion giving rise to Hl2_n[ X06(Mo03)6] , the 6-het eropoly-

molybdic acid, and to H12-n X0g(Mo03 ^12] , the 12-heteropolymolybdic

 49 -

109
acid. This view has been developed further by Pauling ahd
Keggin110 based on their X-ray investigations of crystal structures

of such compounds. Pauling's conclusion is that since sufficient

space is available around Mo(VI) or W(VT) for the formation of an
octahedral species, these acids are made up of twelve MoOg or DX)g
octahedra linked to each other by the mutual sharing of three corners,
with the three unshared corners accommodating hydrogen ions to give
a stable neutral unit as R12°18^0H^36 Cohere R = Mo or W). The
tetrahedral ion is accommodated at the centre of this
structural pattern (Fig.5). This predicts a basicity of 8-n for the
acid, and further that no such acid molecule containing less than
eighteen molecules of water would be stable; this latter prediction
is, however, contrary to the existence of several anhydrous acids
of this type, H 8-n .XMo12°40 (where X = P, Si, Ti),

osygen in ROg
octahedra (shared
corners)

= XO tetrahedra.

(Structure of the 12-heteropolyacids as proposed by Pauling.)

Keggin^"*', however, suggested the existence of a central X04 tetra­

hedron surrounded by twelve MoOg or octahedra in four groups

of three octahedra, where each 0 -acom at the corner of the
 50

tetrahedron is shared with the three octahedra, each of -which

again shares an edge (i.e. two 0-atoms) with each of its two
neighbours (Fig.6(a)). The four or W30l3 groups thus formed
are linked together by sharing edges (Fig. 6(b)), such that each
ROg belonging to a group has two O-atoms in common with a ROg
belonging to each of the two groups closest to it, giving rise
i(8-n)-
to the anion XR|2_ qj . The packing together of such aggregate
ions in the crystal leaves large empty spaces -which can accommodate
several water molecules, thus permitting the existence of high
hydrates, e,g. H, PW12°40 ,29HgO which readily loses water down to
H P¥12°40 .SEgO® In the salts the space occupied by three of
these water molecules is taken up by three cations, -which accounts
for the preferential formation of salts such as KgH S 3H0120 rath er
112
than the one involving replacement of all the acidic hydrogens
It will be hoted that all of the hetero species occurring in this
series A, of 12-heteropoly anions are small enough to make a co­
ordination number of four toward oxygen appropriate.

This Keggin model has been strongly supported by the X-ray

crystallographic analysis of several 12-heteropolyacids and their
salts [R = Mo(YI), X = P(V), As(Y), Ti(IV), Zr(IV); X = W(YI),
X = B(III), Ge(IY), P(Y), As(V), Si(IV)]. However, data on the

composition of materials in solution do not agree. Nor is ohere

an adequate explanation for the structures of the 6-acids.
 (a)

Fux-6 truciure of the 12,-heiero poly acs'dsj

KecjCjm model J
 51

In the 12 hetero acids of type B, the hetero species are

larger than those in the ones of type A, and it might he expected
that their structures -would he such as to have the hetero atoms
in central octahedra of oxygen atoms. Their structures are not
known, hut the do decat ung state structure has a central octahedron.

113
The same general principles have been applied to the
case of the 6-heteropolyacids. The anion ™6°84 (12-n)- •where
R = Mo(VI) or ¥(VI)j-will have six ROg octahedra arranged in a

hexagonal annuls where each such octahedra shares an edge (i.e.

two O -atoms) with each of the neighbouring octahedra'*'14. The
12-
central cavity of the resulting R^.0
6 24 unit can ;Just accommodate
rn +
an octahedron where the remaining cation X may he accommodated
to have a six-fold coordination (Fig.7). The XOg octahedra plays
the same part here as that of the X04 tetrahedron in Keggin‘s

representation of the 12-heteropolyacids mentioned above. In

conformity with this the central atoms of the 6-heteropolyacids

are those which exhibit a coordination number of six Te(VI),
I(VII), Ga(III), Al(III), Gr(III), Fe(III), Co(III), Ni(II) etc.l.
lnfi
This structure has been experimentally substantiated by Evans u

from an X-ray crystallographic analysis of the molybdotellurates.

Crystals of this compound contain octahedral Te(QH)g molecules,
(almost regular with Te - OH, 1.91A0). There is some distortion

from the idealized arrangement (Fig.8) due to the different Mo-0

tit
and Te - 0 bond lengths. The heteroplv ion in Na^HgCr Moq024,8H20
Fig. 7 Structure of the
6-heteropoly-acids
(Anderson model).
 52

115
has the same structure (Cr- 0, 1.975A°)

The structure of paramolybdat e ion, Mo7°24 , formally regarded

as 6-molybdomolybdat e ion, has been shorn to be
MoMo6°24
similar to that of the 1:6 heteropolymolybdates 116 {Fig. 9)

The H^Og11 ^°io^38^" i°n !

A model of this ion, studied in (NH4)g H4CogMo-y-j03g .7HgO

is readily made from a chain of four edge-sharing octahedra by
adding eight more octahedra, four in front and four behind,as shown
in Fig. lo. Alternatively, the ion may be constructed from two
planar CoMog units (similar to TeMogQ24®“ ion) from which one Mo

is removed, and one unit is rotated relative to the other so that

the Co atom of one unit occupies the position of a Mo atom in the
117
other. The four H-atoms were not located'
 OTe, ®Mo, O0
FIG. The TeMo60^i ion
in (NH4)6(TeMo6 024) • 7H20,

ra.
Fig. 9 Structure of paramotybdate an/onjMojO^JJ 6
-
 53

The structures of the heteropoly ions belonging to the

-1 o
1:9 series are also known •

Ce(IV) and Th(IV) as hetero atom also form 12-het eropoly-

acids. Owing to the larger size of these hetero atoms it might
be expected that the arrangement of the ROg octahedra will be such
in these cases so as to have an octahedral cavity of six O-atoms
where the hetero atom may sit to satisfy its coordination number
of six. The actual structure awaits a complete X-ray crystallo­
graphic analysis.

The 12-molybdocerate (IV) anion, CeMo12042 , has long

119
been known . Ripan and Todorut reported 8-tungstocerate-(III)
and -(IV) anions'1'20 ‘**22 -fchich they formulated CeWg0285~ and
4_ 123
CeWgOgg . Peacock and Weakley described the above 8-tungsto­
cerat es as 10-tungstocerates. They have also discussed much about
III 1
the preparation and structure of the salts of the anions Ln %q°35
(In = La, Ce, Pr, Nd, Sm, Ho, Sr, Yb and Y) and ceIVW100 3 56“.