Complex-Formation Titrations

based upon reactions that yield complex ions or

coordination compounds
a A + b T --In c Product
Polyvalent

Ligand

Complex Ion / Coordination Compound

Cation

or Complexing Agent

remarkable growth in their analytical application is

based upon a particular class of coordination
compound called chelates
widely used for titrating cations

Complex-Formation Titrations

Uses of Coordination Compounds

1.

Formation of Colored Substances

can be used to indicate the presence of a specific

metal ion and/or determine its concentration in the
sample

2. Chemical Masking

masking agent decreases the concentration of a free

metal ion to a level where a particular interfering
reaction will not occur

3. Titration of Metal Ions

Ligand
donor
species
must have at
least one pair
of
unshared
electrons
available for
bond
formation

A.Nature
1. Inorganic
2. Organic
H2O, NH3, Cl1EDTA, NTA
B. Number of Electron Pair Donors
1. Unidentate
2. Polydentate or
Multidentate
H2O, NH3, Cl1EDTA, NTA

Complex-Formation Titrations

Coordination Number number of covalent

bonds that a cation tends to form with electron
donors
e.g. two, four, six

Chelate - produced when a metal ion coordinates

with two (or more) donor groups of a single ligand
to form a five or six- membered heterocyclic ring
Cu 2+ + 2 GLYCINE

Titrants : Complexing Agents

polydentate /
multidentate

generally react
more completely
with cations and
thus provide
sharper end points

ordinarily react
with metal ions in a
single-step process

NTA

Nitrilotriacetic acid
second most
common
complexing agent
used for titrimetry

tetradentate
ligand

Titrants : Complexing Agents

EDTA Ethylenediaminetetraacetic acid

free acid, H4Y and the dihydrate of the sodium
salt, Na2H2Y . 2 H2O, are the commercially
available in reagent quality
forms very stable, 1:1complexes with most metal
ions
its dilute solutions are very stable
it is sensitive to pH of the solution, thus it is
somewhat selective in its reactivity with different
metal ions
hexadentate ligand

Indicators
1. Xylenol

weak complexing
agents

exhibit different
colors in their
complexed and
uncomplexed form

Orange

one of the few

indicators that can be
used in acidic
solutions

Indicators
2. Eriochrome

Black T

oldest and most

widely used
complexation
indicator
used exclusively in
the pH range 7 to 11

oxidized slowly by
dissolved oxygen,
ascorbic acid is
sometimes added to
retard this reaction or
solid EBT is added
directly to the sample
prior to titration

Indicators
3.

Calmagite
structure is very
similar to EBT
more stable than
EBT in aqueous
solution

4.

Arsenazo I

excellent indicator for

EDTA titrations of the
rare earths

unlike EBT and

Calmagite, not
blocked by small
amounts of copper or
iron (III) during
calcium and
magnesium titrations

Analytes

virtually every
metal cation
with the
exception of
the alkali
metal ions

determinations
of analyte or
mixture of
analytes involve
one or a
combination of
the titration
methods

Applications
1.

Direct Titration Method

Determination of Water Hardness

expressed in terms of the concentration of calcium

carbonate that is equivalent to the total
concentration of all the multivalent cations in the
sample
hard water precipitates calcium carbonate upon
being heated, which then clog boilers and pipes
calculated as ppm CaCO3

Applications
2. Back-Titration Method

cations that cannot be titrated directly but form very

stable EDTA complexes are good candidates for
back-titration

3. Indirect / Replacement Titration Method

unavailability of a suitable indicator may also be

overcome by replacing the analyte with an
acceptable substitute

Exercise 14
An antacid tablet weighing 15.476-g was dissolved in
acid and diluted to 500.0-mL.
A 25.00-mL aliquot of the solution was made
sufficiently basic to precipitate the Al as Al(OH)3. The
remaining Mg required 16.49-mL of 1.043 x 10 -2 M
EDTA for titration.
A second 25.00-mL aliquot was withdrawn from the
500-mL flask and treated with 50.00-mL of the EDTA.
This solution was made basic and the excess EDTA
back titrated with 11.73-mL of 5.594 x 10 -3 M MgCl2.
Calculate the percentage of both Mg and Al in the
sample.
Molar Masses: Al = 26.98 Mg = 24.31

Exercise 14
An antacid tablet weighing 15.476-g was dissolved in
acid and diluted to 500.0-mL.
A 10.00-mL aliquot of the solution was made
sufficiently basic to precipitate the Al as Al(OH)3. The
remaining Mg required 6.596-mL of 1.043 x 10 -2 M
EDTA for titration.
A second 25.00-mL aliquot was withdrawn from the
500-mL flask and treated with 50.00-mL of the EDTA.
This solution was made basic and the excess EDTA
back titrated with 11.73-mL of 5.594 x 10 -3 M MgCl2.
Calculate the percentage of both Mg and Al in the
sample.
Molar Masses: Al = 26.98 Mg = 24.31

Exercise 14
A 0.4085-g sample containing lead, magnesium and zinc
was dissolved and treated with cyanide to complex and
mask the zinc:
Zn 2+ + 4 CN 1- Zn(CN)4 2-

Titration of the lead and magnesium required 42.22-mL

of 0.02064-M EDTA. The lead was next mask with BAL
(2,3-dimercaptopropanol), and the released EDTA was
titrated with 19.35-mL of a 0.007657-M magnesium
solution. Finally, formaldehyde was introduced to
demask the zinc:
Zn(CN)4 2- + 4 HCHO + 4 H2O Zn 2+ + 4 HOCH2CN + 4 OH 1-

which was titrated with 28.63-mL of 0.02064-M EDTA.

Calculate the percentages of the three metals in the
sample.
Molar Masses: Zn = 65.37 Pb = 207.2 Mg = 24.31