Complexometric Titrations The complexes form when;

Most metal ions form very stable complexes (Kf>>1) readily 1. The central atom (metal) accepts an electron pair(s) from
with reagents having electron donor groups (ligands). The one or more ligands.
number of coordinate bonds formed with ligands equals the 2. The ligand possesses at least one electron pair to donate.
coordination number of metal ion in that complex. 3. Bonding (coordinate covalent bonding) occurs between the
metal ion and the ligand.
Uni-dentate:
A number of common anionic and molecular ligands that can
Cu2+ + 4 :NH3 = Cu(NH3)42+ form complexes are:
Cu(H2O)62+ + 4 :NH3 = Cu(NH3)4(H2O)22+ Kf Anionic ligands include halides, SCN1-, CN1-, OH1-, RCOO1-,
S2-, C2O42- (oxalate), etc.
A multi-step process, as many molecules are bonded
sequentially. Formation constant values differ and
Molecular ligands include water, ammonia, RNH2 (amines)
decreases with the increasing number ‘steps’ of formation.
C5H5N (pyridine) H2NCH2CH2NH2 (ethylenediamine), etc.

Chelate Effect:
Complexes where M+n forms more than one bond per
ligand (multidentate) are termed chelates, e.g. bidentate Kf, chelate >> Kf,monodentate
ligand (glycine) forms a "chelate ring.“
Driving force of chelation: Entropy effect - entropy gain (more
As titrants for measuring metal ions, multidentate ligands disordered product side) is higher for reactions involving
are preferred (less number of ‘steps’ to form the complex), multidentate ligands, chelates, compared to those with
larger Kf values, giving sharper end/equivalence points. monodentate ligands.

Cd(H2O)62  4(CH3 )2 NH  Cd(H2O)2 ((CH3 )2 NH)42  4H2O

O NH2 O 1 4 1 4
H2N O Cu NH2
2+ K f  3  106
OH
Cd(H2O)62  2en  Cd(H2O)2 (en)22  4H2O
glycine H 2N O
1 2 1 4
K f  2  1010
partial structure en = H2NCH2CH2NH2

EDTA, H4Y, (tetraacetate ion, Y-4) is a widely used chelating

(hexadentate) ligand. One step process, i.e. no intermediate
species.

O O
OH
N OH
HO N
HO
O O

Hexadentate EDTA generate the titration curves with

sharp end points.

1
 Cd(H2O)62  4(CH3 )2 NH  Cd(H2O)2 ((CH3 )2 NH)42  4H2O
1 4 1 4
K f  3  106
Cd(H2O)62  2en  Cd(H2O)2 (en)22  4H2O
1 2 1 4
K f  2  1010

6
2 2
Cd(H2O)  EDTA  CdEDTA  H2O
6

1 1 1 6
K f >1016
Y4-

EDTA dissociation constants: weak acidity.

H4Y + H2O = H3Y- + H+ K1 = 1.02 x 10-2

H3Y1- + H2O = H2Y2- + H+ K2 = 2.14 x 10-3
Small K H2Y2- + H2O = HY3- + H1+ K3 = 6.92 x 10-7
4 steps HY3- + H2O = Y4- + H1+ K4 = 5.50 x 10-11

Further, it is insoluble. At pH~7, [Y-4] - insignificant.

At pH >10; [Y-4] - significant, dominates.

Y-4 = EDTA-4
Large K
1 step

Fractional Composition

?!

2
 Generic reaction:
H 4Y  M  n  MY  n  4  4 H 
[ MY  n 4 ][ H  ]4
K 'f  Effective K'f = f(pH)
[ H 4Y ][ M  n ] Conditional equilibrium
constant.

Small [H+], large pH of medium; leads to large Kf’.

The formation constant of EDTA complexes are
pH dependent.

At buffer pH > 10, EDTA exists mostly in the Y-4 form.

(At lower pH, Y-4 combines with H+ ions, thus at low pH, Y-4
is in competition for H+ and metal ions.)

The affinity of different metal ions to Y-4 is vastly different.

Therefore for each ion there is a minimum pH needed for Minimum pH required
the formation of an analytically satisfactory complexation. for quantification
i.e. K sufficiently large.
The minimum pH required to override the competition of
Y-4 to protons and seek a given metal ion M+n can be
determined.

Functional/effective K'f =f(pH)

Functional/effective K'f =f(pH)
H 4Y  M  n  MY  n 4  4 H 

Low [H+]
Ca+2

High [H+]

@ pH=6

3
 Functional/effective K'f =f(pH)

@ pH=6

Mg(II) and Ca(II) K'f ; 6.16108 , 4.81010 at pH = 10.

Minimum pH required
Titrated separately, Mg(II) and Ca(II) can be quantitated. for quantification
Difference in K values does not permit analysis for each ion i.e. K sufficiently large.
separately when in a mixture in one titration procedure.
(because of the non-appearance of two sigmoids, one after
another)

Total hardness (Ca(II) + Mg(II)) determination, feasible however.

The optimum pH for Ca(II) analysis is 10, but pH as low as 8

gives acceptable titration curves because of large K'f.

Color Indicators for EDTA titrations:

At high pH (=10, basic) some M+n ions precipitate as
hydroxides, and in such cases direct titration is not possible. Metal ion complexometric indicator – a weaker chelating agent
than EDTA. e,.g. Eriochrome Black T.
Ex. Zn(II); Strategy - before buffering the solution add (H2In-, type; may be used as an acid - base indicator, too)
ammonia to form Zn(NH3)4+2 complex ion,
and titrate vs EDTA. Kzn-EDTA-2 > Kzn(NH3)4+2. Eriochrome Black T

However, this modification drastically changes the pZn value, SO3-Na SO3-Na

shortening the pZn change at the end point, less sharper O2N O2N

end point.
OH + M+ O M+
N OH N O
If Kf value is sufficiently large, affinity of Y-4 for M+n is N N
significant, then even at pH=6 yields acceptable titration
curves (Fe(III)).
Color 1
Before end point

4
 SO3-Na
SO3-Na O 2N
O2N
O-
O M+ + EDTA MEDTA +
N O-
N O N
N

Color 1 Color 2
Just after end point

Which ion gives a sharper end point? Mg+2

Types of EDTA titrations: Direct titration:

unknown M+n + indicator (or ISE for M+n)

 + buffer; titrate with std. EDTA

titrate (1 mol M+n = 1 mol EDTA)

Back titration:
Sharpening of end point of Ca+2 vs EDTA:
used when,
a. unknown Ca+2+indicator+trace of Mg+2 a. suitable metal ion indicator not available.
 + buffer; titrate with std. EDTA b. M+n and EDTA reaction is slow.
determine end point. V mL c. M+n forms ppt. at titration conditions.
b. Indicator + trace of Mg+2 (blank titration) unknown M+n + known excess vol. std. EDTA
 +water +buffer; titrate with std. EDTA
determine end point. V' mL  + buffer; titrate unreacted EDTA vs std. Mg+2 or std. Zn+2
Volume for Ca(II) = (V-V') mL find end point  unreacted EDTA.
possible because KMg(II)-EDTA < KCa(II)-EDTA Calculate EDTA consumed in the reaction vs M+n.

requirement: [MgEDTA]-2 or [ZnEDTA]-2 less stable

Than the [MEDTA]+n complex.

5
 Displacement reaction (use of an auxilliary agent MgY-2 or ZnY-2:

Prepare MgY-2 (or ZnY-2) solution (pH=10)

Add exc. of MgY-2 to a measured vol. of unknown M+n solution.
(KMg-Y<KM-Y)

MgY-2 + M+n = MY+n-2 + Mg+2

releases Mg+2 QUANTITATIVELY (1:1)

titrate “freed” Mg+2 produced vs std. EDTA.

( 1mol M+n = 1mol Mg+2)

requirement: [MgEDTA]-2 or [ZnEDTA]-2 less stable

than [MEDTA]+n complex.

Scope: Selectivity toward different metals is achieved

by pH control.
Minimum pH required
for quantification
Masking agents may be used to 'remove' interfering ions
from the reaction sphere via formation of stable complexes
with auxiliary ligand.

Minimum pH required
for quantification