06/05/2013

Introduction to Analytical
Chemistry
Complexometry

Complexometry:: an overview
Complexometry

kompleks

Atom pusat

Ligan

Bilangan Koordinasi

Unidentat

Khelat

Tetapan kestabilan

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Classical analysis
Quantitative Classical Chemical Analysis

Gravimetry Titrations

Acid-base Precipitation Complexometric Redox

Titrations involving iodine (I2)

Permanganimetric Dichromatometric

Iodimetry

Iodometry

Iodometric titration of copper

Chelating Agents in Analytical Chemistry

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Ethylene diamine tetra acetic acid (EDTA)

EDTA forms 1:1 complexes with metal ions by with 6 ligands: 4 O &
2N. EDTA is the most used chelating agent in analytical chemistry,
e.g. water hardness.

Acid/Base Properties of EDTA

EDTA is a hexaprotic system (H6Y2+) with
4 carboxylic acids and 2 ammoniums:
pK1 = 0.0
O OH
O pK 2 = 1.5
+ pK 3 = 2.0
O NH
NH
+
OH pK 4 = 2.66
pK 5 = 6.16
OH
O OH pK 6 = 10.24

We usually express the equilibrium for the

formation of complex ion in terms of the Y4-
form (all six protons dissociated). You should
not take this to mean that only the Y4- form
reacts

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Fraction of EDTA in Y4- Form

Similar to acids and bases, we can
define fractional compositions, ,
defined as the fraction of free EDTA in
a particular form.
Free means uncomplexed EDTA
So, for Y4-: [Y 4- ]
Y =4
[H Y ]+ [H Y ]+ [H Y] + [H Y ]+ [H Y ]+ [HY ]+ [Y ]
6
2+
5
+
4 3
-
2
2- 3- 4-

=
[Y ]4-

[EDTA]

EDTA Complexes
The equilibrium constant for a reaction
of metal with EDTA is called the
formation constant, Kf, or the
stability constant:
M n+ + Y 4 MY n 4 Kf =
[MY ] n4

[M ][Y ]
n+ 4

Again, Kf could have been defined for

any form of EDTA, it should not be
understood that only the Y4- reacts to
form complex ion.

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pH Dependence of Y4-

Formation Constants for M-EDTA Complexes

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Some Metals Form 7 or 8

Coordinate Complexes
The rings formed in the
M-EDTA complex can
become strained. If the
oxygen atoms pull back
toward the nitrogen
atoms, the strain is
relieved. This opens up
the metal to other
ligands. Water
molecules frequently
occupy these sites.

Conditional Formation Constant

We saw from the fraction plot that most of the
EDTA is not in the form of Y4- below a pH ~10.

We can derive a more useful equilibrium
equation by rearranging the fraction
relationship: [Y 4- ] 4-
Y = 4
[EDTA ]
[ ] = [EDTA]
Y Y 4

Kf =
[MY ] = [MY ]
n4 n4

[M ][Y ] [M ] [EDTA]
n+ 4 n+
Y 4-

If we fix the pH of the titration with a buffer,

then Y4- is a constant that can be combined with
Kf

K f' = Y 4- K f =
[MY ]n4
M n+ + EDTA MY n 4 K f' = Y 4 K f
[M ][EDTA]
n+

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Example

Calculate the concentration of free Ca2+ in
a solution of 0.10 M CaY2- at pH 10 and pH
6. Kf for
2+
CaY2- is 4.9x10
2
10
'
Ca + EDTA CaY K f = Y 4 K f
at pH = 10.00, K = Y 4 K f = (0.36)(4.9 1010 ) = 1.8 1010
'
f

at pH = 6.00, K f' = Y 4 K f = (2.3 105 )(4.9 1010 ) = 1.1106

Ca 2+ + EDTA CaY 2
Conci 0 0 0.1
Concf x x 0.1 - x

At low pH, the metal-complex is less stable

K f' =
[CaY ] = 0.1 x
2
[ ]
x = Ca 2+ = 2.4 106 M @pH = 10
[Ca ][EDTA] x
2+ 2
= 3.0 10-4 M @pH = 6

Calcium/EDTA Titration Curve

For calcium, the end point
becomes hard to detect
below ~pH=8. The
formation constant is too
small below this point. This
can be used to separate
metals. At pH=4, Ca does
not perform significant
complexaion with EDTA.
However, Fe can still form
the complex, so it can be
titrated without interference
from Ca.

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Generic Titration Curve

Like a strong acid/strong base
titration, there are three points
on the titration curve of a metal
with EDTA: before, at, and after
the equivalence point.

Well consider a titration where

we have 50.0 mL of 0.040 M
Ca2+ (buffered at pH=10) with
0.080 M EDTA.
Ve=25.0 mL
K f' = (0.36)(4.9 1010 ) = 1.8 1010

Before the Equivalence Point

Whats pCa2+ when we have added 5.0 mL

of EDTA?

[Ca ] = 25.0
2+ - 5.0 50.0
(0.040) = 0.0291 M
25.0
55.0

Fraction Initial Dilution

Remaining Concentration Factor

pCa 2+ = log(0.0291) = 1.54

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At the Equivalence Point

Whats pCa2+ when we have added 25.0
mL of EDTA?
At the equivalence point almost all the metal is
in the form CaY2-
50.0
[ ]
CaY 2- = (0.040) = 0.0267 M
75.0
Initial Dilution
Concentration Factor
Free Calcium is small and can be found w/
algebra ' [CaY 2 ] 0.0267 x
Kf = = 1.8 1010
Ca 2+ + EDTA CaY2
[Ca ][EDTA] =
2+
x2
x = 1.2 10 6 M
Conci 0 0 0.0267
Concf x x 0.0267 - x pCa 2+ = log(1.2 106 ) = 5.91

After the Equivalence Point

Whats pCa2+ when we have added 26.0
mL of EDTA?
We have 1.0 mL excess EDTA

[EDTA] = (0.080) 1.0 3

= 1.05 10 M
76.0
Initial Dilution
Concentration Factor

[CaY ] = (0.040) 50.0

2-
= 2.63 10
2
M
76.0
Initial Dilution
Concentration Factor

K f' =
[CaY ] = 2.6310
2 2
= 1.8 1010 Ca 2 + = 1.4 10 9 M
[Ca ][EDTA] [Ca ](1.05 10
2+ 2+ 3
)
pCa 2+ = 8.86

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Auxiliary Complexing Agents

In aqueous solution, metal-hydroxide
complexes or precipitates can form,
especially at alkaline pH

We often have to use an auxiliary
complexing agent
This is a ligand that binds strongly enough to the
metal to prevent hydroxide precipitation, but weak
enough to be displaced by EDTA

Ammonia is a common auxiliary complex for

transition metals like zinc

Metal Ion Indicators

To detect the end point of EDTA titrations, we
usually use a metal ion indicator or an ion-selective
electrode

Metal ion indicators change color when the metal ion

is bound to EDTA:

Eriochrome black T is an organic ion

MgEbT + EDTA MgEDTA + EbT
(Red) (Clear) (Clear) (Blue)

The indicator must bind less strongly than EDTA

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Metal Ion Indicator Compounds

EDTA Titration Techniques

Direct titration: analyte is titrated with
standard EDTA with solution buffered at
a pH where Kf is large

Back titration: known excess of EDTA is

added to analyte. Excess EDTA is
titrated with 2nd metal ion.

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EDTA Titration Techniques (2)

Displacement titration: For metals
without a good indicator ion, the analyte
can be treated with excess Mg(EDTA)2-.
The analyte displaces Mg, and than Mg
can be titrated with standard EDTA

Indirect titration: Anions can be

analyzed by precipitation with excess
metal ion and then titration of the metal
in the dissolved precipitate with EDTA.

Example Titration

25.0 mL of an unknown Ni2+ solution was
treated with 25.00 mL of 0.05283 M
Na2EDTA. The pH of the solution was
buffered to 5.5 and than back-titrated
with 17.61 mL of 0.02299 M Zn2+. What
was the unknown Ni2+ M?

Zn 2+ + Y 4- ZnY 2-
mol EDTA = (25.00 mL)(0.05283 M) = 1.32 mmol EDTA
mol Zn 2+ = (17.61 mL)(0.02299 M) = 0.4049 mmol Zn 2+
Ni 2+ + Y 4- NiY 2-
mol Ni 2+ = 1.321 mmol EDTA - 0.4049 mmol Zn 2+ = 0.916 mmol
M Ni 2+ = (0.916 mmol)/(25.00 mL) = 0.0366 M

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Redox

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Oxidation - A process by which a substance (reductant)

gives up electrons to another substance (oxidizing agent).
The reductant is oxidized.

Reduction - A process by which a substance (oxidant)

accept electrons from another substance (reducing
agent).

In a chemical reaction, the total number of electrons

are conserved; so also are the number of charges.
Thus, it is convenient to assign fictitious charges to
the atoms in a molecule and call them oxidation
numbers. Oxidation numbers are chosen so that (a)
conservation laws are obeyed, and (b) in ionic
compounds the sum of oxidation numbers on the
atoms coincides with the charge on the ion.

Rules for Assigning Oxidation Numbers:

1. The oxidation numbers of the atoms in a

neutral molecule must add up to zero,
and those in an ion must add up to the
charge on the ion.
2. Alkali metal atoms have oxidation
number +1, alkaline earth atoms +2, in
their compounds.
3. Fluorine always has oxidation number -1
in its compounds. The other halogens
have oxidation number -1 in their
compounds except those with oxygen
and with other halogens, where they can
have positive oxidation number.

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Oxidation Numbers (cont.):

4. Hydrogen is assigned oxidation number +1 in its
compounds except in metal hydrides such as LiH,
where convention (2) takes precedence and hydrogen
has oxidation number -1.

5. Oxygen is assigned oxidation number -2 in

compounds. There are two exceptions: in compounds
with fluorine, convention 3 takes precedence, and in
compounds that contain O - O bonds, conventions 2
and 4 take precedence. Thus the oxidation number
of oxygen in OF2 is +2: in peroxides (such as H2O2
and Na2O2) it is -1. In superoxides (such as KO2)
oxygen's oxidation number is -1/2.

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Problem 12-5: Redox Titration- I

Volume (L) of KMnO4 Solution Problem: Calcium Oxalate was
precipitated from 1.00 mL blood by
a) the addition of Sodium Oxalate so
M (mol/L)
the Ca2+ conc. in the blood could
be determined. This precipitate was
Moles of KMnO4
dissolved in a sulfuric acid solution,
Molar ratio which then required 2.05 mL of
b)
in redox rxn. 4.88 x 10-4 M KMnO4 to reach the
endpoint via the rxn. of Fig. 4.14.
Moles of CaC2O4 a) Calculate the moles of Ca2+.
b) Calculate the Ca2+ conc. in blood.
c) Chemical Formulas Plan: a) Calculate the moles of
Ca2+ in the H2SO4 solution (and
blood sample).
Moles of Ca+2
b) Convert the Ca2+ conc.into units
of mg Ca2+/ 100 mL blood.

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Problem 12-5: Redox Titration - Calculation - II

Equation:
2 KMnO4 (aq) + 5 CaC2O4 (aq) + 8 H2SO4 (aq)
2 MnSO4 (aq) + K2SO4 (aq) + 5 CaSO4 (aq) + 10 CO2 (g) + 8 H2O(l)

a) Moles of KMnO4

b) Moles of CaC2O4

c) Moles of Ca+2

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