POLYACIDS.

The weak acid formed from the amphoteric metals of groups v & vi
especially W, V, Mo as central atom are known as poly acids. They
are mainly of 2 types.
1) The anions of weak acid derived from metals such as Mo, V, W
has the property of condensing reversibly as the ph is lowered to
give a series of anions from what are termed as iso poly acids.

2) If the condensation takes place in presence of certain other non-

metals such as P, Si , it is then known as hetero poly acids and the
product is termed as hetero poly anions.
.The poly anions are primarly built of MO6 octahedra , but they are
prepared by starting with the tetrahedral [MO4]2- , link with each
other by sharing an edge or a vertex. The basic building unit is 6
oxygen atoms surrounding each metal atom , with metal ions
occupying octahedral holes.

Edge sharing octahedra

.Poly acids of Mo, W, V are very difficult to study because the
extent of hydration and protonation of various species in
solution is not known.

.The first step in poly acid formation as the PH is lowered must

be to increase the coordination no. From 4 to 6 by adding
water molecules.

.Hetero poly anions are formed if a molybdate or tungstate

solution is acidified in the presence of P, Si, or other ions.

.Many different technique have been empolyed in the study of

poly acid like light scattering, cryoscopy, spectrophotometry
etc.
 Eg : addition of one chromate radical to H2CrO4 give corresponding
isopoly acid H2Cr2O7. The chromate ion is stable only at high PH, as pH
is lowered protonation & dimerisation occurs.

CrO42- + H+ (OH)CrO3- + H+ (OH)2CrO2

2 (OH)2CrO2 Cr2O72- + H2O + H+

General Formula
[XO4]2- + H+ [XO3(OH)]-n+1

2 [ XO3(OH)]-n+1 [O3X O XO3]-2n+2 + H2O

It involves the formation of oxo-bridge by elimination of water molecules of
weak acid
Iso poly acids may be defined in another way also in which these
acids are formed from a single acid by the elimination of water
molecules of the same acid.
-H2O
.2 H2CrO4 H2Cr2O7
-2H20
.3 H2CrO4 H2Cr3O10

.4 H2CrO4 -3H2O
H2Cr4O13

The important isopoly acids are isopolymolybdates,

isopolytungstates & isopolyvanadates.
ISOPOLY ACIDS OF VANADIUM
When V2O5 is dissolved in strong alkaline solution tetrahedral vanadate
[VO4]3- is formed. It is acidified to add protons and polymerise to form
very large no. of isopoly acids of V.
PH 12 PH 10 PH 9
[VO4]3- [VO3.OH]2- [V2O6.OH]3-
colourless
PH 2.2
[V3O9]3- PH 7 [V5O14 ]3- PH 6.5 V2O5.(H2O)n
orange red
PH < 1
[V10O28 ]6- [VO2]+
Pale yellow
Isopoly vanadate
 ISOPOLY ACIDS OF MOLYBENUM
When the trioxide of Mo (MoO3) is dissolved in aq. alkali, the
resulting solution contain Td [MoO4]2-. When this molybdate
solution is acidified it get condensed and gives an extensive range
of polymolybdates.

[MoO4]2- PH 6 [Mo7O24]6- PH 1.5 -3

[Mo8O26]4-
Normal molybdate Para molybdate Octa molybdate

PH < 1

MoO3.2H20
Hydrated oxide
ISOPOLY ACIDS OF TUNGSTEN
The oxide of tungsten WO3 is strongly acidic and dissolve in aq. NaOH
forming Td tungstate ion [WO4]2-. When this tungstate solution is
acidified it condenses and gives an extensive range of poly tungstates .

PH 6 -7
[WO4]2- [HW6O21]5- [W12O41]10-
Normal tungstate fast Para tungstate A Slow Para tungstate B
PH 3.3

[H3W6O21]3- [W12O40]6-
Pseudometa tungstate Metatungstate
PH < 1 (weeks/months)

WO3.2H2O
HETERO POLY ACIDS / ANIONS

Hetero poly anions are formed if a molybdate or tungstate soution is

acidified with phosphate or silicate or other non metal ions.

Eg: [HPO4]2- + 12 [MoO4] + 24 H+ [PMo12O4O]3- + 12 H2O

.The 2nd anion or atoms in the hetero poly anion is situated in the
cavities formed by MO6 Oh ( M = Mo , W ).

.The ratio of heteroatom like P, Si, B etc to central metal atoms like
Mo, W is usually 1:12 , 1:9 , 1:6 , 2:18.
 HETEROPOLY ACID is a class of acid made up of a particular
combination of hydrogen and with oxygen certain metals and non-
metals. This type of acid is a common re-usable
acid catalyst in chemical reactions.

To qualify as a hetero polyacid, the compound must contain:

1)a metal such as tungsten, molybdenum or vanadium, termed the

addenda atom;

2)an element generally from the p-block of the periodic table, such
as silicon, phosphorus or arsenic, termed the hetero atom;
acidic hydrogen atoms.
.Due to the possibilities of there being different combinations of
addenda atoms and different types of hetero atoms there are a lot
of hetero polyacids. Two of the better known groups of these are
based on the Keggin, HnXM12O40, and Dawson, HnX2M18O62 .

1) 1:12 tetrahedra (Keggins structure)

These occur with small hetero atoms such as P, As, Si, Ge
which yield Td oxyanions.
Eg: (NH3)4[PMo12O62]

2) 2:18 tetrahedra (Dawson structure)

If solutions of 1:12 are allowed to stand 2:18 ions are generally
Formed.
Eg: [P2Mo18O62]6-
Two of the least discussed hetero poly anions are in the
ratio ;

3) 1:6 octahedral
These are formed with large no. of hetero atoms which coordinate
to 6 edge sharing MO6 octahedra.
Eg: [TeMo6OO24]6-

4) 1:9 octahedral
These are formed by encapsulating hetero atoms coordinated
to 9 edge sharing MO6.
Eg: [MnMo9O32]6-
 Applications

. Commercially used as dyes.

. Keggin & Dawson compound can be used as pigments.
.Hetero poly anions can be used in quantitative & qualitative
analytical techniques.
.They also used as catalyst in analytical chemistry.
.The intense blue colour of these anions can be used as
sensitive test for reducing agents.