Chapter 9
Complexometric Titrations
OUTLINE:
❑9.1 Complexes, ligands
❑9.2 Chelates, EDTA
❑9.4 Indicators, types of EDTA titrations
Prof. Dr. Ibrahim Badr
9.1 Complexes and Ligands
(a quick review of basics)
This type of titrations is based on the formation of a
complex between analyte and reagent
What is a complex?
Metal ion Ligand
+ -
Lewis acid .. Lewis base
“electron acceptor” “electron donor”
Examples
Ag+ 2C N [NC-Ag+-CN]-1
Ligand is an anion or molecule that forms a coordinate
bond by donating a pair of electrons.
Coordination number is the number of covalent bonds
around metal ion
C.N. for Ag+ = 2
Ligands
Mondentate Polydentate
Bind through one atom Bind through more
:NH3 H2O: Cl- than one atom
“chelate”
Bidentate
Tridentate
Tetra, hexa….
Q Is a chelating ligand a monodentate or multidentate?
9.2 Chelates
Ethylenediamine tetraacetic acid EDTA, [Y4-]
EDTA is the most widely used chelating agent in complexmetric or
chelometric titrations.
Most elements in periodic table can be analyzed by EDTA.
EDTA is hexadentate ligand
Forms 1:1 metal to ligand stoichiometry regardless of the metal ion
charge
The chelon effect: Multidente ligands from more stable complexes with
larger formation constat (Kf)compared with mono or bidetnate.
EDTA Equilibria
H4Y ↔ H+ + H3Y- Ka1 = 1.0×10-2
H3Y- ↔ H+ + H2Y2- Ka2 = 2.2×10-3
H2Y2- ↔ H+ + HY3- Ka3 = 6.9×10-7
HY3- ↔ H+ + Y4- Ka4 = 5.5×10-11
Formation Constant and Effect of pH of Equilibria
The reaction between metal (Ca) and EDTA (Y4−) can be written
as:
Ca2+ + H4 Y ⇔ CaY 2− + 4H+
[𝐶𝑎𝑌 2− ] . [𝐻 + ]4
𝐾𝑓 =
[𝐶𝑎2+ ] . [𝐻4 𝑌]
Thus increasing the pH (decreasing the hydrogen ion
concentration) increases 𝑡ℎ𝑒 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝐾𝑓 and shifts the
above equilibria to the right, which is formation of more 𝑐𝑜𝑚𝑝𝑙𝑒𝑥
(𝑚𝑎𝑘𝑒𝑠 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑙𝑒𝑥 𝑚𝑜𝑟𝑒 𝑠𝑡𝑎𝑏𝑙𝑒).
Effect of pH of Kf’
•Change in the pH affects K’f
•Most metal ion titrations require basic
medium to form stable enough chelates.
9.4 Indicators, types of EDTA titrations
Erichrome black T (EBT)
OH
OH
O3S N N
M-EBT EBT
(Red) (Blue)
End point is detected in EDTA titrations
Before E.P.
Mg2+ + EDTA MgEDTA
At E.P.
EBT
MgEBT
(red) + EDTA MgEDTA + (Blue)
At the end point the color of the indicator changes from red to
blue. For this change to occur:
Kf M-EBT < Kf M-EDTA
Types of EDTA
Direct EDTA
Titration reaction
Mg + EDTA MgEDTA
End point reaction
MgEBT + EDTA MgEDTA + EBT
M
Back titrations
What if (M + EDTA) reaction is slow? Or there is no
suitable indicator.
Back titration is the solution.
M1 + EDTA (excess) = M1-EDTA + EDTA (unreacred)
EDTA (unreacrted) + M2 = M2-EDTA
Example
Al3+ + OH- = Al(OH)3
Al(OH)3 + EDTA = Al(EDTA) + EDTA excess
EDTA excess + Zn2+ = Zn-EDTA
Displacement titration
This method could be used if there is no suitable indicator for
M1-EDTA reaction
M1 + MgEDTA M1-EDTA + Mg2+
Mg2+ + EDTA MgEDTA
For this to happens the formation constant of
M1 EDTA > Mg EDTA
EXAMPLE
Hg2+ + MgEDTA HgEDTA + Mg2+
Mg2+ + EDTA MgEDTA
Water Hardness
Water is said to be hard if it contains Mg2+ and Ca2+ salts.
What are the problems associated with hard water?
1. Hard water precipitate soap
Ca2+ + 2RSO3- Ca(RSO3)2
2. When water is heated, Ca and Mg salts precipitate and
clogs boilers and pipes.
Water Hardness
Ca++, Mg++ < > EDTA
VEDTA Ca++ + Mg2+
Water hardness is expressed
in (mg CaCO3/L)
If water contains (Ca++ +
Mg++) = 1 1mg/L
Hardness of water = 1 mg /L
CaCO3
Examples for EDTA Titrations
Direct titration
A Cu(II) was analyzed using EDTA. 10 mL of Cu(II) required 20.00 mL of 0.0500 M
EDTA ([Link]. for copper = 63.39 g/mol)
a) Calculate the molarity of Cu(II) solution.
b) Calculate the concentration of Cu(II) in w/v%.
c) This method is classified as (back-titration - direct titration - indirect titration).Select the
suitable answer.
d) Mention the name of a suitable indicator for this titration.
Examples for EDTA Titrations
Direct titration
([Link]. Zn = 65.39 g/mol, O=16.00 g/mol)
Examples for EDTA Titrations
Back titration
([Link]. Cr(C6H4NO2)3= 418 g/mol)
Examples for EDTA Titrations
Replacement titrations
A 1.5 g antiseptic drug (merbromin C20H8Br2HgNa2O6)
containing Hg(II) digested and treated with excess
MgEDTA. The liberated Mg was titrated with 0.001 M EDTA
and required 2.4 mL to reach endpoint. What is the % of Hg
in the sample? ([Link]. Hg= 200.59 g/mol)
Examples for other complexometric
Titrations
([Link]. KCN= 65.1 g/mol)
HOMEWORK
14 18
Prof. Dr. Ibrahim Badr
