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
 A.Nature

Ligand 1. Inorganic 2. Organic

H2O, NH3, Cl1- EDTA, NTA
donor
species
B. Number of Electron Pair Donors
must have at
least one pair 1. Unidentate 2. Polydentate or
of Multidentate
unshared H2O, NH3, Cl1- EDTA, NTA
electrons
available for
bond
formation
 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 NTA
generally react Nitrilotriacetic acid
more completely second most
with cations and common
thus provide complexing agent
sharper end points used for titrimetry
ordinarily react tetradentate
with metal ions in a ligand
single-step process
 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 Orange

weak complexing
one of the few
agents
indicators that can be
used in acidic
exhibit different
solutions
colors in their
complexed and
uncomplexed form
 Indicators

2. Eriochrome Black T
oldest and most
widely used oxidized slowly by
complexation dissolved oxygen,
indicator ascorbic acid is
sometimes added to
used exclusively in retard this reaction or
the pH range 7 to 11 solid EBT is added
directly to the sample
prior to titration
 Indicators

3. Calmagite 4. Arsenazo I
excellent indicator for
EDTA titrations of the
structure is very
rare earths
similar to EBT
unlike EBT and
Calmagite, not
more stable than blocked by small
EBT in aqueous amounts of copper or
solution iron (III) during
calcium and
magnesium titrations
 Analytes

virtually every determinations

metal cation of analyte or
with the mixture of
analytes involve
exception of
one or a
the alkali
combination of
metal ions 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