2nd Semester 2020-2021

Complex-Formation Titrations
= uses complex-forming reagents for titrating cations. These
reagents are organic compounds that contain several electron-
donor groups that form multiple covalent bonds with metal ions.

Complex-Forming Reactions
• Most metal ions react with electron-pair donors to form
coordination compounds or complexes.
• The donor species or ligand must have at least one pair or
unshared electrons available for bond formation.
• The number of covalent bonds that a cation tends to form with
electron donors is its coordination number typical values for
coordination number are two, four, and six.
• The species formed as a result of coordination can be
electrically positive, neutral, or negative.
Complexometric methods
= titrimetric methods based on complex formation; based upon a
particular class of coordination compounds called chelates.
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.
Ligands ca be
◦ Unidentate = 1 donor group
◦ Bidentate = 2 donor groups
◦ Tridentate, tetradentate, pentadentate, hexadentate
Advantages of multidentate over unidentate ligands
◦ they generally react more completely with cations and
provide sharper end points
◦ they ordinarily react with metal ions in a single step
process wherea unidentate ligands usually involves two
or more in termediate species.
Titrations with Aminocarboxylic Acids
Tertiary amines that contains carboxylic acid groups
form stable chelates with many metal ions.
a. Ethylenediaminetetraacetic acid (EDTA)
= most widely used complexometric titrant
= has six potential sites for bonding a metal ion; the
four carboxyl groups and two amino groups.
= a hexadentate ligand.

b. Equilibrium Calculations Involving EDTA and EDTA

Titration Curves
A titration curve for the reaction of a cation Mn+ with
EDTA consist of a plot of pM versus reagent volume
EDTA

Ex. Cu-EDTA complex

c. Indicators for EDTA Titrations
= generally these are organic dyes that form
colored chelates with metal ions in a pM range
that is characteristic of a particular cation and
dye.

Erichrome Black T
= typically a metal-ion indicator used in titration
of several common cations but behaves as an
acid /bae indicator. It forms red complexes with
more than two dozen metal ions. But only a few
are appropriate for end point detection.
 D.A. Skoog, D.M. West, F.J. Holler, and S.R.
Crouch, Fundamentals of Analytical Chemistry,
9th ed., Thomson Learning Asia, Singapore, 2014.
 Supplemental Notes
 Web references