Chapter 12

EDTA Titrations
 Overview

12-1 Metal-Chelate Complexes

12-2 EDTA
12-3 EDTA Titration Curves
12-4 Do It with a Spreadsheet
12-5 Auxiliary Complexing Agents
12-6 Metal Ion Indicators
12-7 EDTA Titration Techniques
 12-2: EDTA

Ethylenediaminetetraacetic acid (EDTA) is a

compound that forms strong 1:1 complexes
with most metal ions.
Used in industrial processes and products
such as detergents, cleaning agents, and
food additives that prevent metal-catalyzed
oxidation of food.
Metal-EDTA complexes find their way into the
environment because they can pass through
wastewater treatment plants unscathed.
 12-1: Metal-Chelate Complexes
Metal ions are Lewis acids that accept electron pairs
from electron-donating ligands (Lewis bases).
Monodentate ligands bind to a metal ion through only
one atom (e.g., CN- through the C atom).

A ligand that attaches to a metal ion through more than

one ligand atom is said to be multidentate, or a chelating
agent.
 12-1: Metal-Chelate Complexes
Ethylenediamine is a simple chelating
agent, which is bidentate.

Chelate effect the ability of multidentate

ligands to form more stable metal
complexes than those formed by similar
monodentate ligands.
 12-1: Metal-Chelate Complexes
The reaction of with two molecules of
ethylenediamine is more favorable than its reaction
with four molecules of methylamine, a
monodentate ligand:
 12-1: Metal-Chelate Complexes

Adenosine triphosphate (ATP) is an important

tetradentate ligand, which binds divalent metal
ions (Mg2+, Mn2+, Co2+, and Ni2+) through four of
their six coordination positions. The fifth and sixth
positions are occupied by water molecules.
12-1: Analytically Useful Chelating
Agents
 12-2: EDTA
A titration based on complex formation is called
a complexometric titration.
EDTA is the most widely used chelator in
analytical chemistry.
By direct titration or through an indirect series of
reactions, virtually every element of the periodic
table can be measured with EDTA.
 12-2: EDTA: Acid-Base Properties
EDTA is a hexaprotic system, designated H6Y2+.

The first four pK values apply to carboxyl protons; the

last two are for the ammonium protons.
The neutral acid is tetraprotic, with the formula H4Y,
which can be dried at 140oC for 2 h and used as a
primary standard.
 12-2: EDTA: Acid-Base Properties
The fraction of EDTA in each of its protonated forms
is plotted in the figure:
 12-2: EDTA: Acid-Base Properties
We can define a for each species as the fraction of
EDTA in that form. For example, aY4- is defined as:

where [EDTA] is the total concentration of all free (not

complexed to metals) EDTA species in the solution.
Therefore, aY4- is given by:
12-1: Example: What Does aY4-
Mean?
 12-2: EDTA Complexes
The equilibrium constant for the reaction of a metal
with a ligand is called the formation constant, Kf, or
the stability constant:

Kf for EDTA is defined in terms of the species Y4-

reacting with the metal ion.
 12-2: EDTA Complexes

The table shows that formation constants for most

EDTA complexes are large and tend to be larger or
more positively charged cations.
 12-2: Conditional Formation Constant
Most EDTA is not Y4- below pH 10.37. The species
HY3- and H2Y2-, and so on, predominate at lower pH.
If the pH is fixed by a buffer, then aY4- is a constant
that can be combined with Kf:

This is called the conditional formation constant and it

describes the formation of MYn-4 at any particular pH.
12-2: Conditional Formation Constant
 12-3: EDTA Titration Curves
We can calculate the n+
concentration of free M
during its titration with
EDTA:

If K f' is large, we can

consider the reaction to
be complete at each
point in the titration.
The titration curve is a
plot of pM versus the
volume of EDTA added
and has three natural
regions.
 12-3: EDTA Titration Curves
Region 1: Before the Equivalence Point
The concentration of free metal is equal to the
concentration of excess, unreacted Mn+.

Region 2: At the Equivalence Point

[Mn+] = [EDTA]

Region 3: After the Equivalence Point

The concentration of free EDTA can be equated to
the concentration of excess EDTA added after the
equivalence point.
 12-3: Titration Calculations
Consider the reaction of 50.0 mL of 0.040 0 M Ca2+
(buffered to pH 10.00) with 0.080 0 M EDTA.

Region 1: Before the Equivalence Point

After the addition of 5.0 mL of EDTA
 12-3 Titration Calculations
Region 2: At the Equivalence Point
Virtually all the metal is in the form CaY2-. [CaY2-] is
equal to the original [Ca2+] with a correction for
dilution.

The concentration of free Ca2+ is small and unknown.

12-3 Titration Calculations
 12-3 Titration Calculations
Region 3: After the Equivalence Point
Virtually all of the metal is in the form CaY2-, and
there is excess, unreacted EDTA.
After the addition of 26.0 mL of EDTA, there is 1.0
mL of excess EDTA.
 12-3 Titration Calculations

The concentration of
Ca2+ is governed by:
 12-4: Do It with a Spreadsheet
Consider the titration of metal ion M (initial
concentration = CM, volume VM) with a solution of
ligand L (concentration = CL, volume added = VL) to
form a 1:1 complex:

The mass balances for metal and ligand are:

 12-4: Do It with a Spreadsheet
Substituting Kf[M][L] from Equation 12-8 for [ML] in the
mass balance:

Now substitute the expression for [L] from Equation 12-10

back into Equation 12-9, then solve for the fraction of
titration, .
 12-4: Do It with a Spreadsheet

The equation for titrating L with M:

 12-5 Auxiliary Complexing Agents
For many metals to be titrated
in alkaline solutions with
EDTA, we use an auxiliary
complexing agent to prevent
metal hydroxide precipitation.
Reagents are ligands such as
ammonia, tartarate, citrate, or
triethanolamine
They must bind strongly
enough to prevent metal
hydroxide from precipitating,
but weakly enough to give up
the metal when EDTA is
added.
 12-5: Metal-Ligand Equilibria
Consider a metal ion that forms two complexes
with the auxiliary complexing ligand L:

b are the cumulative formation constants.

The fraction of metal ion in the uncomplexed state,

M, is:

Where Mtot is the total concentration of all forms of

M (M, ML, and ML2).
 12-5: Metal-Ligand Equilibria
The mass balance is: Mtot = [M] + [ML] + [ML2]

Equations 12-13 and 12-14 allow us to say

[ML] = b1[M][L] and [ML2] = b2[M][L]2

Therefore,
Mtot = [M] + b1[M][L] + b2[M][L]2
= [M]{1 + b1[L] + b2[L]2}

Substituting into Equation 12-15:

12-5: Metal-Ligand Equilibria
12-5: EDTA Titration in the Presence of
Ammonia
Consider the titration of Zn2+ by EDTA in the
presence of NH3.

We now need a new conditional formation

constant to account for the fact that only some of
the EDTA is in the form Y4- and only some of the
zinc not bound to EDTA is in the form Zn2+:
12-5: EDTA Titration in the Presence of
Ammonia
12-5: EDTA Titration in the Presence of
Ammonia
12-5: EDTA Titration in the Presence of
Ammonia
 12-6: Metal Ion Indicators
End-point detection methods:
1. Metal ion indicators (most common)
2. Mercury electrode
3. Ion-selective electrode
4. Glass (pH) electrode

Metal ion indicators are compounds that change

color when they bind to a metal ion must bind
metal less strongly than does EDTA.
Example: the reaction of Mg2+ with EDTA at pH 10
with Calmagite indicator.
12-6: Metal Ion Indicators
12-6: Metal Ion Indicators
 12-7: EDTA Titration Techniques
1. Direct titration: Analyte is titrated with standard
EDTA. Analyte is buffered to a pH where K f' for
the metal-EDTA complex is large and the color of
the free indicator is different than that of the
metal-indicator complex.

2. Back titration: A known excess of EDTA is

added to the analyte. Excess EDTA is then
titrated with a standard solution of a second metal
ion.
12-7: EDTA Titration Techniques
 12-7: EDTA Titration Techniques
3. Displacement Titration: Use when the analyte,
such as Hg2+, does not have a satisfactory indicator.
Hg2+ is treated with excess Mg(EDTA)2- to displace
Mg2+, which is titrated with standard EDTA.

There is also no suitable indicator for Ag+, however

Ag+ will displace Ni2+ from tetracyanonickelate(II) ion:
2Ag+ + Ni(CN)42- 2Ag(CN)2- + Ni2+

The Ni2+ liberated can be titrated with EDTA to

determine the amount of Ag+ added.
 12-7: EDTA Titration Techniques
4. Indirect Titration: Anions that precipitate with certain metal ions
can be analyzed with EDTA using an indirect titration.

Example: Sulfate can be analyzed by precipitation with excess Ba2+

at pH 1.
BaSO4 (s) is washed then boiled with excess standard EDTA at
pH 10 to bring Ba2+ back into solution as Ba(EDTA)2-.
Excess EDTA is back-titrated with Mg2+.

5. Masking: A masking agent is a reagent that protects a component

of the analyte from reaction with EDTA.

Example: Al3+ in a mixture of Mg2+ and Al3+ can be measured by

masking the Ag+ with F-, leaving only the Mg2+ to react with EDTA.