Theory of complexometrie analysis

Introduction

ACOmplexing agent is any clectron-donating ion or moleuea

or
called a ligand,wvhich, by its abilitv to fom oneeor more ovalen
bonds withthe metal ion, produces a complex which has
properties fromthose of the free metal iion. )Thus,the metal IN
precipitated from the complex by the usual metal ion Prcipuants
th
decomposition potential of the complex at the droppins
also, is usually nmore negative
thann that of the free metal
[Link]
ion can existin different valency States,the redox
Bonding in complexes
The bonds are either ordinary covalent bonds which both the metal and
in
the ligand contribute one electron each, or co-ordinate bonds in which
both electrons are contributed by the ligand. Thus, the hexacyanoferrate
204 Precipiation and complexomeiric methode
to consist of
three
considered
ion may be ordinary
bonds (Fig. 8.1la),although in the covalent
threeco-ordinate which have complex
bonds (Fig. [Link]) been shown the
identical hybrid to
a regular octahedron (Fig8
towards the apices
of [Link]). ,be
diteceh

CN
CN CN CN
CN CN
TFe

CN|
Fe

CN CN CN
Fe
CN CN CN4

CN
Hy brid bonds

(a) (b)
(c)

Fig. 8.1 The hexacyaoferrate iron(III) ion

The negative charge on the complex ion is equal to thetotal

the negative groups minus the valency of the metal ion. numberof
When
groups only are involved, the charge on the complex neutral
is
positive
annd is
to the valency of the metal ion, e.g. (Cu(NH}) ]2+ equal

Werner's co-ordination nunber and electronic structureof

complex ions
Werner (1891) first noticed that for each atom there is an gheer
maximum number of small groups which can be accommodated arond it

This number, which is called Werner's co-ordinationnumber, depends

purely upon steric factors and is in no way related to the valency of the ion
Thus, although the valency shell of the elements of the third period i
theoretically capable of expanding up to 18 clectrons, and that te
fourth to 32 electrons, there is, in practice, a limit to the number smal of

groups which can be accommodated owing to limitations of space around

the ion. In the second period,the maximum number is 4 and in the third
period it is 6; with certain elements such as tungsten and molybdenum is
it
8. For example, in the [BF]- ion,the octet is completed and the maximum
co-ordination number is reached, but in the [AÍF]- ion the outer shell
Contains 12 electrons and cannot expand to the maximum number of 18
electrons since the maximum co-ordinationnumber has been reached.
Within the limits imposed by Werner's co-ordinationnumber, there isa
tendency forthe metal to attain. or approach inert gas structure, and this is
probably the driving force forcomplex [Link] examplesin Tae
8.1illustrate this point.
itapial
Complexometricanalysis 205

configuration of metal ions and complex ions

8.1 Electronic
Table Electronic configuration
Electronic
Complex ion of complex ion
configuration
ion
Metal [Co(NH)e]" 2,8, 18,8
2. 8, 14

8, 17 |Cu(NH)? 2, 8, 17, 8
2,
Cu(CN) 2,8, 18,8
2, 8, 18 18 2, 8, 18, 32, 18, 8
2, 8, 18, 32, |Hg(CNS),}'
2, 8, 18, 8
2, 8, 14
IFelCN 2,8, 17, 8
Fe 8, 13
2,
ed

agents
Chelating
involving simpleligands, that is, thoseforming only one bond
Complexes as co-ordination [Link] having more than one
described
àre are called
group chelatíng agents (from a Greek word
electron-donating since they combine with metal ions in a manner
claw),
meaning crab's claw to form cyclic structures. Thus, 1,2-
of a

(ethylenediamine) behaves like two ammonia

reminiscent molecules
diaminoethane and cobalt ions:
andforms chelates with copper

en

en

en = ethylenediamine (H,NCH,CH,NH)
the cobalt ion
The copperionis common to two five-membered rings and
to three five-membered rings. The latter has no plane of symmetry and,
thus, exists in two optically active forms. There is no fundamental
difference between co-ordination and chelate compounds except that in
rings are the
the latter, ring size influences stability. Five- or six-membered

most stable and are readily formed, although both larger and smaller rings
may also be formed.
contain groups with
Many organic compounds will chelate metals if they
and OH), or
an easily replaceable proton(-COOH, phenolic
enolic

heutral groups offering a lone pair

of electrons (NH,, CO and alcoholic
the
OH), and the structures of the molecules are such as to permit
of rings which can be
Tormation of stable rings. The greater the number
Tormed, the more stablethe chelate is likely tobe. Most rings formed in
cnelates involve thehighest valency state of a metal
since these are more
Stable than those involvinglowervalency states.
The solubility metal chelates in water depends upon the presence of
of

as COOH, SO,H,NH, and OH. When both

groups such acidic
yarophilic
and basic over a wide range
ELOups are present,the complex will be soluble
 206 Precipiation and complexomnetricmethods

of pH. When hydrophilic groups are absent, the

chelating agent andthe metal chelate will be low, but
solubilitieso
of
they will
organic solvents. The term sequestering agent is both
the
chelating agents which form water-soluble generally
complexes with

,
valent metal [Link], althoughthe metals remain
insolution. appled
give normal ioni
reactions(Ethylencdiaminetetra:acctic acid theyfal
sequestering agent, whereas dimethyglyoximg and
chelating agents,forming insoluble complexes.)
salicylaldoxime

HOOCCH;
CH,-COOH
N-CH,-CH,-N
HOOC-CH;
CH-COOH
Ethylenediamine tetra-acetic acid

CH,-ÇNOH CH=NOH
CH-C=NOH OH
Dimethylglyoxime Salicylaldoxime

As a agent,ethylenediaminetetra-acetic
sequestering acid reacts
with most
polyvalent metalto form water-soluble complexes which
ions
cannot be
extracted from aqueous solutions with organic solvents,)
Dimethyllyoxime
and salicylaldoxime form complexes which are insoluble in water, but

soluble in organicsolvents;for example, nickel dimethylglyoxime hek

sufficiently low solubility in water to be used as a basis for gravimetrio
assay.

Nature and stability ofmetal complexes of

ethylenediaminetetra-acetic acid

Ethylenediaminetetra-acetic acid forms complexes with most cations in a

1:1 ratio, irrespective of the valency of the ion:

M2* + [H,X]? + 2H+

[MX]2-
M?* + [H,X]2 [MX]- +2H
M* +[H,X|? [MX]+ 2H+
where Ma metal and [H,X2-is the anion of the disodium salt (disodiun
is

edetate) which is most frequently used. The structures of these compee

with di, tri- and tetravalent metals contain three, four and five nis
respectively:
 KOAika

Complexometric analysis 207

O0C CH, O0C CH,

O0CCH.

Efect of p H on complex formation

Edetic acid ionises in =
four stages (pK1 =2.0, pK, 2.67, pk;= 6.16 and
DK, =10.26) and, since the actual complexing species is Y,
complexes
will form more efficiently and be more stable in alkaline solution. If,
however, the solubility product of the metal hydroxide is low, it may be
precipitated if the hydroxyl ion concentration is increased too much. On
the other hand, at lower pH valueswhen the concentration of Y4- is lower,
the stability constant of the complexes will not be so high. Complexes of
most divalent metals are stable in ammoniacal solution. Those of the
alkaline earth metals,such as copper, lead and nickel, are stable down to
pH 3 and hence can be titrated selectively in the presence of alkaline earth
metals. Trivalent metal complexes are usually still more firmly bound and
stable in strongly acid solutions; for example, the cobalt(III) edetate
complex is stable in concentrated hydrochloric acid. Although most
complexes are stable over a fair range of pH, solutions are usually buffered
ata pH at which the complex is stable and at which the colour change of
the indicator is most distinct.

Colour of complexes
Ihere is always a change in the absorption spectrum when complexes are
formed and this formsthe basis of many colorimetric assays.

Stability ofcomplexes
Ihe general equation for the formation of a 1:1 chelate complex, MX, is
M +X MX
Where M is the metal ion and X the chelating ion
 Log
208 Precipitation and complexometric methods 6toble

[MX]
.. Stability constant (K) =
[M][X]
where ]represents activities.
Increase in temperature causes a slioht
increase in the ionisation of the complex and a slight
lowering of K Th
presence of eletrolytes having no ion in common with
the complex
decreases K, whilst the presence of ethanol increases K, probably due t
the suppression of ionization. Table 8.2 gives
values of thelogarithms of
stability constants of edetate complexes of metals of
pharmaceutical
interest.

Table 8.2 Stability constants of edetate complexes

Cation Log K Cation

Log K
Ba?+ 7.8 Co2+ 15.5
8.7 Co34
Mg2+ 26.0
Ca? 10.6 A13+ 15.5
Cr2+ 13.0 Zn2+ 16.5
Cr3+ 24.0 Pb2+ 17.0
Mn2+ 13.5 Ni2+ 18.0
Fe2+ 14.3 Cu2+ 18.0
Fe3+ 25.1 Hg2+ 21.0

Log
pM (--)

(Oenton

Equivalent of Sodium Edetate

Fig. 8.2 Change of p[M] during complex formation with disodium edetate

Titration ofmetal ions using disodium edetate

0.2%)the
Since edetic acid is only sparingly soluble in water (about
disodium
When
disodium salt is usually used (solubility about 10%).
Pou
End point detection in complexometricanalysis 209

solutionrun into a solution of a metal ion buffered

is
edetate to promote
complex formation, the rate of change of concentrationof metal
efficient
slow at first, but increasesvery rapidly as the amount of disodium
ion is
added approaches one equivalent, inthesame way as hydrogen ion
edetate
changes during the titration of a strong acid with a
concentration 8.2 strong
Fig. shows a plot of log (M"*) and pM{log
base. 1/|M"*] or,
against equivalents of disodium edetate
-log(Mm1)) added.

End point detection in complexometric titration using pM

indicators
The end point of complexometric titrations is shown by means_of pM
indicators. The concept of pM arises follows:
as
If K is the stability constant,

K= [MX]
[M][X]
then

[M) = [MX]
[X]K
or
[MX]
log [M]=log logK
[X]
and
[X]
pM = log pK
[MX]
Therefore, if a solution is made such that X]=(MX],pM= -pK (or
pM= pK, where K= dissociation constant). This means that, in a
solution containing equal activities of metal complex and free chelating
agent, theconcentration of metal ions will remain roughly constant and
will be buffered in the same way as are hydrogen ions in a buffer. Since, pH
however,chelating agents are also bases, equilibrium in a metal-buffer
solution is often greatly affected by a change in pH. In general,for
chelating agents of the amino acid type (e.g. edetic acid and ammoniat
riacetic acid), it may be said that when (X] =MX], pM increases with pH
until about pH
10, when it attains a constant value. This pH is, therefore,
usually chosen for carrying out titrations of metals with chelating agents in
buffered soution.

The pM indicator is a dye which is capable of acting as a chelating agent

to give a dye-metalcomplex. The latter is different in colour from dye the
1tself and also has a lower stability constant than the chelate-metal
complex. The colour of the solution,therefore, remains that of the dye
complex until the end point,when an equivalent amount of sodium edetate
has been added. As soon as there is the slightest excess of edatate, the
etal-dye complex decomposes to produce free dye; this is accomplished
by a change in
colour.
fnd Pon
Ihe colours of dyes and of the metal complexes vary with pH. This fact