Complexometric Titration
You are an analyst at a company for water purification, and you need to estimate
the water hardness (Ca2+& Mg2+).
Plan and design the chemical analysis approach to perform this task.
Complex (Coordination Compound)
Compound results from the combination of metal ion as (acceptor) with donor
molecules (ligand) through coordinated bonds (donor→ acceptor)
Examples: Metal ion + Ligand→ Coordination compound (complex)
(Lewis acid) + (Lewis base)
Mn+ + L= (L M)
Complex Ion = Transition Metal Cation Surrounded by Ligands
Ligand = Molecule or Ions of Nonbonding Electron Pairs
Bonding is Called “Coordination”
Complexometry
A volumetric titration involves the formation of soluble complex between metal
ion (as acceptor) and ligand (as donor) to form coordination bonds.
The metal ion is known as Central metal atom.
The anion or neutral molecule is known as Ligand (L)
Nature of The Acceptor Atom (Metal Ion)
The metallic ion (atom) has stable electronic configuration It forms additional
completed shells by accepting electron pairs from donor atoms.
Coordination Number:
•The no. of coordinate bonds formed to a metal ion by their ligands.
•The number of electron pairs that metal ion share or accept.
Coordination Number: Zn(OH)
•It could be 2, 4, 6, depending on the metal ion and its oxidation number.
•Independent on the nature of donor atom.
Nature of The Donor Atom
In aqueous solution, donors are nonmetallic elements N, O, and S
Type of complexing agents (ligands)
This classification is according to the no. of sites attached to the metal ion
[Link] (Monodentate) Ligand or "Simple Ligand" The ligand attached to
metal at one site e.g. H2O, NH3 , CN - , Cl - , I - , Br - (i.e. forming one coordinate
bond, or capable of donating one unshared pair of electrons)
2. Bidentate Ligand - The ligand attached to metal at two sites.
[Link] Ligands - The Ligand attached to metal at 3 sites
[Link] Ligands -The Ligand attached to metal at 4 sites
[Link] Ligands (Chelating Agent) Substance with multiple sites available
for coordination bonding with metal ions. Such bonding typically results in the
formation of five or six membered rings.
Chelation
Chelate: A complex formed between the ligand containing two or more donor
atoms and a metal, forming ring structure (heterocyclic rings or chelate rings).
Chelating agents: organic molecules containing two or more donor groups that
combine with metal to form a complex of ring structure.
Titration With Multidentate Complexes (Chelating Agents)
Chelating agent: Ethylene diamine tetra acetic acid (EDTA) possess enough donor
atoms to fill the whole coordination sphere of metal ions in one step.
The three-dimensional structure of the 1:1 metal-EDTA chelate with Mn2+ .
Advantages of EDTA or H4Y
[Link] forms very stable and soluble stoichiometric, 1:1 complexes with many metal
ions.
[Link] offers some selectivity against specific metal ions by controlling the pH at
which titration is performed.
[Link] disodium salt of EDTA (Na2H2Y. 2H2O) is an acceptable primary standard
and commercially available.
[Link] the metal complexes are soluble, coprecipitation errors are absent.
[Link] end point could be easily achieved using metal ion indicators.
Factors Affecting the Stability of Metal-EDTA Chelate
[Link] of the solution
2. Nature of the metal ion Factors Affecting the Stability of Metal-EDTA
Chelate
•Complexes of divalent cations: only stable in basic medium
•Chelates of trivalent cations: stable in acidic media (pH 1-2).
•Chelates of tetravalent cations: stable at pH values less than 1.
Types of EDTA titration
a. Direct titration – solution containing the metal cation is buffered to the
desired pH and titrated directly with EDTA using auxiliary complexing agent
such as citrate, tartrate or triethanolamine to avoid precipitation of the metal
as hydroxide
b. Back titration – in the absence of metal indicator, the solution is treated
with excess EDTA, buffered to the desired pH and the excess is determined
using standard solution of either sulfates or chlorides of zinc or magnesium
c. Replacement titration – applied for cations that do not react with the metal
indicator like Ca+2; in the determination of Ca+2 , small amount of magnesium
chloride is added to EDTA where Ca+2 initially displaces Mg+2 in the EDTA
complex and displaced Mg+2 combines with EBT producing a red complex;
when all the calcium is titrated, the liberated Mg+2 is released, combines with
EDTA and the endpoint is observed with the formation of blue un complexed
indicator.
Detection of End Point: use Metal Ion Indicators
• Organic dyes with acid-base properties that undergoes a color change upon
proton transfer to/from the dye molecule.
• In addition, the dye molecules contains a chelating group that is joined to the
conjugated system responsible to for the color.
•The success of an EDTA titration depends on the precise determination of
the end point.
•These indicators responds to a change in pM and thereby convert the break
in pM into the color changes.
•The most common procedures uses the metal ion indictors.
Characteristics of Metal Ion Indicators
[Link] colored chelates (complexes) and exhibit a different color in the free
form than in the complex form.
[Link] reaction between metal and indicator must be reversible.
3. The metal-indicator complex should be less stable than the metal-EDTA
complex.
4. The color reaction should be specific or at least selective.
5. Changes its color according to the pH of the medium. [Link] colored
chelates (complexes) and exhibit a different color in the free form than in the
complex form.
Examples of Metal Ion Indicators
1. Eriochrome black T (EBT) - It can be represented by H2In .The color of
indicator change with the change of pH.
EBT contains 2 replaceable phenolic hydrogen.
Titration methods involving complexes
Determination of cyanide – Liebig method
• The titration is carried by the dropwise addition of AgNO3 in a solution of a
cyanide forming a soluble cyanide complex of silver:
• The endpoint of the titration is the formation of a permanent faint turbidity:
•Determination of nickel
An ammoniacal solution of nickel is treated with a measured excess of standard
cyanide solution:
• The excess cyanide is determined according to the Liebig method
