Complexometric Titration

SMK Negeri 13 Bandung

Complexometric Titration
Reaction result is complex substance
Common standard solution : EDTA
(Ethylene Diamine Tetra acetic Acid )

What is complex substance?
A substance formed by covalent
coordination bond;

A bonding formed by pair electrons
sharing, while the source of pair
electrons is only one atom/group.
The covalent coordinate in a
complex substance
Between the center atom (metal ion)
and the ligand (ion/atom/group that
give the pair electrons).

Center atom give the orbital.
Ligand give the pair electrons.

Complex stability
If M
n+
+ L
x-
[ML]
n-x

While [ML]
n-x
is complex substance
then
[ML]
K = ----------- is K
stab

[M] [L]

K
stab
= stability constant
The more stable the substance will
has bigger K
stab

The complex is difficult to
dissociated to be its ions
(Compare with weak acid or
base)
EDTA
(Ethylene Diamine Tetra acetic Acid)
Ligand that have 6 pairs of electron.
Other name : trilon B, complexon III,
sequestrene, versene dan chelaton 3.
Release 2 H
+
from 2 carboxylic.
Most available in disodium salt form.
Wrote as H
2
Y
=

EDTA concentration always
termed in Molar, because
EDTA has 6 electrons pair
which could be used in
covalent coordinate bond
one-by-one.
EDTA reacts with any
metal with mole ratio 1 :
1.

REACTIONS
M
2+
+ H
2
Y
=
MY
=
+ 2H
+

M
3+
+ H
2
Y
=
MY
-
+ 2H
+

M
4+
+ H
2
Y
=
MY + 2H
+
M
5+
+ H
2
Y
=
MY
+
+ 2H
+

M
n+
+ H
2
Y
=
MY
(n-4)
+
2H
+



pH influence to metal-EDTA
complex stability
Every reaction of metal ion with EDTA
resulted H
+

As Le Chatelier, if [H
+
] increased,
the equilibrium goes to the left (ions)
means
At low pH or high [H
+
] , the stability
of metal-EDTA is decreased.
Some of K
stab
of metal-EDTA
2+ Ions 3
+
Ions
Mg 8.7 Al 16.3
Ca 10.7 Fe 25.1
Sr 8.6 Y 18.2
Ba 7.8 Cr 24.0
Mn 13.8 Ce 15.9
Fe 14.3 La 15.7
Co 16.3 Lu 20.0
Ni 18.6 Se 23.1
The Equivalence Point Detection
Instrumental : spectrophotometric,
amperometric, conductimetric or
potentiometric
Conventional : Using indicator
Indicator available: metal ion
indicator (metalochromic indicator)
This indicator is sensitive to very low
concentration of metal ion (pM)
Metal ion Indicator
Ligand in the form of organic ion
which its free ion colour differ from
its complex.
Could also function as indicator pH.
Its Colour change depend on the pH (
owning typical pH job).
Complex metal-indicator own the K
stab

expressed by K
in
.

Criterion of Choosing Indicator
For Choosing the metal ion indicator,
we have to know:
1. pH work indicator.
2. pH titration ( barbed with the
nature of metal ion and metal
complex stability EDTA.
Metal stability EDTA must > Metal
Indicator
Some of metal ion indicators.
EBT (Eriochrome Black
T)/Solochrome Black T/WDFA
Murexid
Xylenol Orange
Pyrocathecol Violet
Bromopyrogalol Red
Variamin Blue B
EBT (Eriochrome Black T)
Solochrome Black T / WDFA
At pH < 5.5 red (H
2
D
-
).
At pH 7 -11 blue (HD
=
).
At pH > 11.5 yellowish-orange (D
3-
).
At pH 7-11 reacting with the metal
ion. M
++
+ HD=
(blue)
MD
-

(red)
+ H
+


Preparation of EBT Solution.
0.2 gram EBT dissolved in 15 ml three
ethanol amine and 5 ml alcohol
absolute.
This solution is stable for a few
months.
0.4 gram EBT dissolved in 100 ml
methanol, stable at least 1 month.
1 gram of EBT attenuated with 200 -
500 gram of KCL or NaCl or K
2
So
4
or
Na
2
So
4
. Most stable during carried
through to run dry in bottle call a
meeting to order.
Murexide
Until pH 9 reddish violet (H
4
D
-
)
pH 9 -11 Violet (H
3
D
=
)
Above pH 11 blue-violet or blue (H
2
D
3-
)
At pH base
Ni-murexide, Co-murexide yellow
Cu-murexide orange
Ca-murexide red
Preparation of murexide Solution.
0.5 g of the powdered dyestuff in
water, shaking thoroughly, and
allowing the undissolved portion to
settle. This solution can only be used
on making of. Everyday the old
supernatant liquid is decanted and
the residue treated with water as
before, to provide a fresh solution of
the indicator.
1 g murexide attenuated with 500
gram pure NaCl, most stable.

Xylenol Orange
The indicator at acid pH (1 5) is
coloured lemon yellow.
XO Metal at acid pH is intensely red.
Titration is generally conducted at pH
1-3, titration at pH 5 conditioned by
hexamine.
0.5 % XO solution in water, most
stable.
Types of Complexometric
Titrations
1. Direct Titration.
The solution containing the metal ion
to be determined is buffered to the
desired pH (e.g. to pH = 10 with NH:-
aq. NH,) and titrated directly with the
standard EDTA solution. It may be
necessary to prevent precipitation of
the hydroxide of the metal (or a basic
salt) by the addition of some auxiliary
complexion agent, such as tartrate or
citrate or triethanolamine.
2. Back Titration.
Metal ion reacted by excessive EDTA,
then at certain pH, the excess of EDTA
titrated with the standard metal ion
solution such as Mgso
4
or Znso
4
.
At equivalence point obtained mmol of
the rest of EDTA = mmol metal std, so
that countable.
mmol metal ion = mmol (EDTA metal
std).
Why these Types of titrations are selected.
1. Metal ion precipitated at pH
titration.
2. Its Complex forming is too slow.
3. There are not appropriate metal ion
indicators ( complex stability of metal
indicators are ineligible).
End Point determined with the
sensitive metal ion indicator to metal
standard.
3. Substitution Titration.
Metal ion titrated by EDTA with the
other metal ion attendance as an aid
of determination of the end point (
For example, determination of Ca
2+
with aid of Mg
2+).
The titration is conducted if:
1. Metal ion does not react ( or its
reaction dissatisfactory) with
indicator, or
2. Complexion of metal EDTA more
stable than other.
Examples:
Stability of Ca EDTA>Mg
EDTA
Stability of Ca EBT>Ca EDTA
Hence titration Ca by EBT
have to entangle the Mg, so
that the end point can be
reached.
4. Alkalimetric Titration.
When metal ion reacted by
EDTA will be formed by a
number of ion H
+
. This ion H
+

titrated by NaoH solution
uses acid-base indicator.
Its condition, metal ion
solution have to really
neutral before is reacted by
EDTA.