Chapter-9 Complexmetric

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 (f.wt. 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.
Direct titration
(f.wt. Zn = 65.39 g/mol, O=16.00 g/mol)

Back titration
(f.wt. Cr(C6H4NO2)3= 418 g/mol)

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? (f.wt. Hg= 200.59 g/mol)
Examples for other complexometric
Titrations
(f.wt. KCN= 65.1 g/mol)

HOMEWORK
14 18
Prof. Dr. Ibrahim Badr

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Chapter 9

❑9.2 Chelates, EDTA

❑9.4 Indicators, types of EDTA titrations

Prof. Dr. Ibrahim Badr

 This type of titrations is based on the formation of a

 Ligand is an anion or molecule that forms a coordinate

 Coordination number is the number of covalent bonds

Q Is a chelating ligand a monodentate or multidentate?

 EDTA is the most widely used chelating agent in complexmetric or

 H3Y- ↔ H+ + H2Y2- Ka2 = 2.2×10-3

 H2Y2- ↔ H+ + HY3- Ka3 = 6.9×10-7

 HY3- ↔ H+ + Y4- Ka4 = 5.5×10-11

•Change in the pH affects K’f

•Most metal ion titrations require basic

 Erichrome black T (EBT)

Kf M-EBT < Kf M-EDTA

 End point reaction

M1 + EDTA (excess) = M1-EDTA + EDTA (unreacred)

EDTA (unreacrted) + M2 = M2-EDTA

Al(OH)3 + EDTA = Al(EDTA) + EDTA excess

EDTA excess + Zn2+ = Zn-EDTA

 This method could be used if there is no suitable indicator for

 For this to happens the formation constant of

 Hg2+ + MgEDTA HgEDTA + Mg2+

 Water is said to be hard if it contains Mg2+ and Ca2+ salts.

1. Hard water precipitate soap

Ca2+ + 2RSO3- Ca(RSO3)2

2. When water is heated, Ca and Mg salts precipitate and

 Ca++, Mg++ < > EDTA

 Water hardness is expressed

 If water contains (Ca++ +

a) Calculate the molarity of Cu(II) solution.

(f.wt. Zn = 65.39 g/mol, O=16.00 g/mol)

(f.wt. Cr(C6H4NO2)3= 418 g/mol)

(f.wt. KCN= 65.1 g/mol)

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