Faculty of science

Complexometric Titrations
3rd Year Students, General- Science
Course Code: 317 Chem.

Lecture# 7
Date: March 29, 2020
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Classification of Quantitative Analysis

Quantitative
analysis

Volumetric Gravimetric

Acid base Oxidation Precipitation

Complexometric
Titration Reduction Titration

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 Analytical Problem
You are an analyst at a company for water
purification, and you need to estimate the water
hardness (Ca2+ & Mg2+ amount).

Your job: Plan and design the chemical analysis

approach to perform this task.

Type of hardness limit

Soft water 60-120 mg/L
Hard water 120–180 mg/L
very hard ˃ 180 mg/L
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 Complex (Coordination Compound)
Compound results from the combination of metal ion as
(acceptor) with donor molecules (ligand) through coordinated
bonds (donor→ acceptor)

Metal ion + Ligand→ Coordination compound (complex)

(Lewis acid) (Lewis base) +

Mn+ + L= (L M) H3N Ag NH3

Examples: [Ag(NH3)2]+ +
NH3
[Fe(SCN)6]3- Ag
NH3
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 Complex Ion = Transition Metal Cation Surrounded by Ligands
Ligand = Molecule or Ions of Nonbonding Electron Pairs

Bonding is Called “Coordination”

For the complex Co3+ is the electron acceptor and shares a

[Co(NH3)6]3+ pair of electrons with each of N-atom in NH3

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 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)

Coordination bond

Cu 2  4 NH 3  [Cu ( NH 3 ) 4 ]2 NH3


Ligand NH3  Cu  NH3

NH3
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 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.
•It could be 2, 4, 6, depending on the metal ion and its oxidation
number.
•Independent on the nature of donor atom.

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Zn(OH ) 2
4
Fe(NH 3 )6  
3+

7
Nature of The Donor Atom
In aqueous solution, donors are nonmetallic elements
N, O, and S.
Ion Coordination Typical complex
number
Ag + 2 Ag(NH3) 2+
Cu2+ 4 Cu(NH3)4 2+
Zn 2+ 4 Cd(NH3)4 2+
Hg 2+ 4 Hg(NH3)4 2+
Co2+ 6 Co(NH3)6 2+
Ni2+ 6 Ni(NH3)6 2+
Fe3+ 6 Fe(CN)6 3-
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 Type of complexing agents (ligands)
This classification is according to the no. of sites attached
to the metal ion
1. Unidentate (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)

H3N Ag NH3

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2. Bidentate Ligand

The ligand attached to metal at two sites.

NH2 NH2 H2N

H2C H2C CH2
2 + Cu2+ Cu
H2C H2C CH2
NH2 NH2 H2N

Ethylene diamine Copper amine complex

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3. Tridentate Ligands

The Ligand attached to metal at 3 sites

Diethylene triamine

4. Tetradentate Ligands
The Ligand attached to metal at 4 sites

Triethylene tetramine

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5. Multidenate 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.

Ethylene Diamine Tetra acetic Acid

EDTA has six sites for

complex formation.
The electron pairs on the two
nitrogen atoms and the four
electron-rich carboxyl groups.
EDTA
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 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.

Examples: H2 2+
Ethylene diamine H2C-NH2 H2C-N NH2 -CH2
EDTA Cu2+ + 2 Cu
H2C-NH2 H2C-N NH2 -CH2
H2

Chelate effect Cu(II) ethylenediamine chelate

Enhancing the stability of multidentate complexes than unidentate

complexes.
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Titration With Multidentate Complexers (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.

EDTA

The three-dimensional structure of the 1:1 metal-EDTA

chelate 2+.
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Advantages of EDTA or H4Y
1.It forms very stable and soluble stoichiometric, 1:1 complexes
with many metal ions.

2.It offers some selectivity against specific metal ions by

controlling the pH at which titration is performed.

3.The disodium salt of EDTA (Na2H2Y. 2H2O) is an acceptable

primary standard and commercially available.

4.Since the metal complexes are soluble, coprecipitation errors

are absent.

5.The end point could be easily achieved using metal ion

indicators.
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Factors Affecting the Stability of Metal-EDTA Chelate

1. pH of the solution

M 2  H 2Y 2  MY 2  2 H  pH  5
M 2
 HY 2
 MY 2
H  pH  8
M n   Y 4  MY 2 pH  12

2. Nature of the metal ion

•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.

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For better comparison of chelates, stability constants are used

Stability constants for some metal-EDTA chelates

Metal ion Log Kstab
Mg 2+ 6.7
n 4 ( n4)
Ca 2+ 10.7 M Y  MY
Sr2+ 18.7
Ba2+ 7.9 ( MY ( n 4) )
K stab  n 4
Mn2+ 13.8 ( M )(Y )
Fe 2+ 25.1
Zn 2+ 16.5
Co2+ 16.3
Cu2+ 18.8
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 Titration curves
For derivation of the titration curve, consider the titration of 50.0 mL
of 0.1 M solution of Mg2+ (buffered at pH 10) with 0.1 M EDTA
solution.

We calculate the concentration of Mg2+ (as pMg= -log(Mg) and

plotted versus the volume added from ETDA

1) pMg before the addition of EDTA

Mg2+ = 0.1 M , so, pMg=-log (0.1)=1.0 pMg

Volume EDTA (ml)

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2) pMg after adding 10.0 mL EDTA, we will calculate the
remaining unchelated Mg solution in the whole solution (60 ml)

MVMg 2  MVEDTA
(50 * 0.1)  (10 * 0.1)
M Mg 2 unreacted   0.067M
50  10
PMg   log(0.067)  ....

3) pMg after adding 25.0 mL EDTA, we will calculate the

remaining unchelated Mg solution in the whole solution (75 ml)

(50 * 0.1)  (25 * 0.1)

M Mg 2 unreacted   0.067M
50  25
PMg   log(0.067)  ....
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 4) pMg at the equivalence point
At this Point, 50 mL of EDTA have been added to completely react
with Mg solution

We will use the stability constant to calculate the pMg

2 4 2 ( MgY 2 )
Y  MgY   8
Mg K stab
( Mg 2 )(Y 4 )
5.0 x10

a a 0.05-a

Concentration of MgY2- is calculated as follows

(50 * 0.1)
M Mg 2   0.05M
50  50
(50 * 0.1)
M MgY 2   0.05  a
50  50
(0.05  a )
Substitute at equation Kstab K stab   5.0 x108

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 (0.05  a )
Substitute at equation Kstab K stab   5.0 x108

a2

a, is neglected because it is very small relative to 0.05

So, (0.05)
 5.0 x108
a  ( Mg 2 )  1.0 x10 5 , PMg  5.0
a2

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5) pMg, beyond the equivalence point:

By adding 60 mL of the 0.1 M EDTA

(50 * 0.1)
M MgY 2  a
50  60

Neglect the term a

and then substitute (MgY2-) of 5/110 M in K stab equation
(60 x0.1)  (50 x0.1)
There will be an excess from EDTA Y 4   1 / 110
(50  60)
(5 / 110)
 5.0 x108
(1 / 110)(a )

a  1x10 8 M And pMg=8.0

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The titration curve is plotted by using the previous data

Volume added (ml )EDTA pMg

0
5
10
25
50
51
55
60

Please complete this table and plot the titration curve!!!

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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.

•These indicators responds to a change in pM and thereby

convert the break in pM into the color changes.

•The success of an EDTA titration depends on the precise

determination of the end point.

•The most common procedures uses the metal ion indictors.

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 Characteristics of Metal Ion Indicators
1.Form colored chelates (complexes) and exhibit a different
color in the free form than in the complex form.

2.The reaction between metal and indicator must be

reversible.

3. The metal-indicator complex should be less stable than the

metal-EDTA complex.
Metal-indictor +EDTA Metal-EDTA+ free indicator

4. The color reaction should be specific or at least selective.

5. Changes its color according to the pH of the medium.

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 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. + Metal ion

EBT contains 2 replaceable phenolic hydrogen.

Pink
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 EBT is a tribasic acid at pH 10, exists as blue HIn2-
2 3
H 3 In  HIn  In
Red Blue Orange
pH below 7 pH 7-11 pH above 11

The blue form of the indicator reacts with metal ions, to

give a wine red chelate

2 2  
Mg  HIn  MgIn  H
pH10

Analyte Free indicator Metal –indicator

colorless Blue complex
Wine red

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By the titration with EDTA, it initially chelates the free Mg2+ ion,
then displaces the chelated Mg from the indicator.

 3
MgIn  HY  MgY 2  HIn 2
pH 10

Metal –ind. Titrant Metal–EDTA Free indicator

complex EDTA complex Blue
Wine red colorless colorless

EBT is used for the determination of

Mg 2+, Zn 2+, Cd 2+, pb 2+ , Hg 2+ & Mn 2+ salt at pH 7 – 11
using ammonia buffer (pH = 10)

EBT cannot be used for the determination of

Cu 2+, Fe 3+, Al 3+, Co 2+ and Ni 2+
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 2. Murexide
Ammonium salt of purpuric acid
and its anion has the following
structure

 OH  2 OH 
H 4 Ind 
 H 3 Ind  H 2 Ind 3

Reddish violet Violet Blue
pH < 9 9-11 > 11

•Murexide is used for the direct titration of calcium at pH=12, the

end point changes from red to blue violet.
•At pH=12, Mg-murexide is less stable than the Ca-complex, so Ca2+
ion can be titrated in the presence of Mg at this pH.
•Murexide gives yellow chelates with Cu, Co, Ni metals ions.
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It is used for the determination of
Ca 2+, Co 2+, Ni 2+, & Cu2+ salts at pH 9-11

Ca 2+ + H3In2-  Ca H2In- + H+
Ca H2In- + H2Y2-+ OH -  CaY 2- + H3In2-+ H2O
Pink Violet

Metal Color of complex Color of indicator

Ca 2+ Pink violet
Cu 2+ Orange Violet
Co 2+ Yellow violet
Ni 2+ yellow violet

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Common Metal Ion Indicators

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Complexometric Titrations: Types
1. Direct titration
The solution of the metal ion to be determined is buffered to
the desired pH( e.g. to pH=10 with NH4+, NH4OH) and titrated
directly with the standard EDTA solution.
The end point is determined by the change in color of a metal
indicator that responds to changes in pM.

Mg 2  EBT  Mg  EBT EDTA

pH 10
 Mg  EDTA  EBT
Blue Wine red Colorless Blue

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Requirements for Direct EDTA Titrations
1.M-EDTA complex must be more stable than M-Ind.
complex in buffered medium.

2. The compound to be determined is water soluble.

3.The reaction between EDTA and metal must be rapid. If

not, it must be catalyzed.

4. Mn+ should not be precipitated at the pH of titration. If Mn+ is

precipitated as MOH, auxiliary reagent must be added to
prevent pptn. of M n+.

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Examples

1- pb2+ ion forms precipitate of pb(OH)2 at the pH 10.

So, tartaric acid (auxiliary reagent) is added to convert

pb(OH)2 to soluble lead tartarate complex.

2-Sometimes buffer acts as auxiliary reagent

During titration of Cu2+ salt in alkaline medium, Cu(OH)2 is ppt.

and the reaction with EDTA becomes slow.

So, by using ammonia instead of alkali hydroxides, the soluble

[Cu(NH3)4]2+ is formed which is less stable than Cu-EDTA and
hence the reaction forward rapidly.
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Direct Determination of Water Hardness
•Water hardness is due to the presence of Ca2+ & Mg2+ salts.
•EDTA forms complex with Ca2+ & Mg2+
•Ca-EDTA complex is more stable than Mg-EDTA complex.
•At pH 12 EDTA forms complex with Ca2+ only.

Total Ca2+ & Mg2+

•Total Ca2+ and Mg2+ determined by titration with EDTA at pH 10
using ammonia buffer and EBT as indicator

Upon titration with EDTA, Ca2+ will be chelated first, then Mg2+.

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For Ca2+ only

Direct titration with EDTA at pH 12 using 8% NaOH and Murexide.

Mg2+ is precipitated as Mg(OH)2 leaving Ca2+ to be titrated with
EDTA

For Mg2+ Total – Ca2+ = Mg2+

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2. Back Titration
This procedure involves:

1. Addition of known excess of standard EDTA solution to the

sample
2. The medium is buffered.

3.Titrate excess EDTA with standard metal ion solution such as

Mg2+ or Zn2+
pH  acidic
M n   excessEDTA   M  EDTA  unreacted  EDTA

The color change at the end point:

From free ind. colour  to M-Ind. complex
(opposite that direct titration)
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 Why do we use Back Titration?

1.Detection of some insoluble substances such as BaSO4,

Ca(C2O4)2, PbSO4, Mg3(PO4)2, which soluble in hot EDTA.

2. When the reaction between Mn+ & EDTA is slow (incomplete)

e.g. Fe3+, Al3+, Cr3+, Th4+.

3. The precipitation of metal at the pH suitable for titration e.g.

Al(OH)3.

4. The suitable indicators are not available

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Example #1: Determination of Aluminium salts
•Sample of Al3+ is heated with known excess of standard
EDTA at pH 7-8.
•The solution is then adjusted to pH=10 using ammonia buffer.

•The residual EDTA is titrated against standardZn2+ using EBT

indicator.
•The color change from blue to wine red.

pH 7-8
Al3+ + H2Y2-  AlY- + 2 H+
Boil
pH 10
Zn2+ + H2Y2-  ZnY2- +2 H+
Zn2+ + H Ind2-  Zn-Ind-+ H+
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 Example #2: Determination of Mn salts

Mn can not be directly titrated with EDTA in alkaline solution

due to the precipitation of the Mn(OH)2.

1.An excess of EDTA is added to an acidic solution of the Mn salt.

2. Ammonia buffer is used to adjust the pH to 10.

3. The excess EDTA (unreacted) after chelation is titrated with

standard Zn2+ solution.

pH  acidic
Mn 2  excessEDTA   Mn  EDTA  unreacted  EDTA

unreacted  EDTA  Std .Metal 

pH 10

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3. Replacement or substitution titration
1.Used for metal ions that does not react (or react
unsatisfactorily) with a metal indicator.

2. When metal ions form unstable EDTA complexes.

The metal ion Mn+ to be determined is treated with Mg-EDTA

complex.
n n 2
M  Mg  EDTA  M  EDTA  Mg

The amount of Mg ion librated is equivalent to the cation present

and can be titrated with standard solution of EDTA and a suitable
metal indicator.

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 4. Alkalimetric Titration
• When a solution of disodium EDTA, Na2H2Y is added to a
solution containing metallic ions

• Complexes are formed with the liberation of two equivalents

of hydrogen ion:

• Therefore, the hydrogen ions liberated can be titrated with a

standard solution of sodium hydroxide using an acid-base
indicator.

M n   H 2Y 2  ( MY ) ( n 4)   2 H 
2H+ + 2NaOH →
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 Analysis of Metal Ion Mixtures
EDTA is a very unselective reagent because it complexes
di, tri, and tetra- valent cations.

To increase the selectivity of EDTA, some procedures

could be followed:
•Control of pH of the medium
•Adjustment of oxidation number of metal ion
•Using masking and demasking agent

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 Control of pH of the medium
1.First group: Trivalent & tetravalent cations (Bi3+ , Fe3+ , Th4+) and Hg2+
titrated (form stable complex) at pH 1-3 using conc. HNO3.

2.Second group: Divalent metals (Co2+ , Ni2+ , Cu2+ , Zn2+ , pb2+ and Cd2+)
titrated (form stable complex) at pH 4-6 using acetate buffer.

3.Third group: Alkaline earth metal (Ba2+ , Sr2+ , Ca2+) and Mg2+ titrated
(form stable complex) at pH=10 using ammonia buffer or 8% NaOH.
• At pH 1-3, metal ion from first group could be titrated without
interference of the second and third groups.

• At pH 4-6, Mn+ of the second group without interference of the third group.

Analysis a mixture of Bi3+ & pb2+

1. First titrate Bi3+ at pH = 2 using xylenol orange as indicator.

2. Then increased pH to 5 by adding hexamine and titrating pb2+.
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 Adjustment of Oxidation Number of Metal Ion
This procedure remove the interferences between metal ions of the
same group of pH.
Examples
1. Ascorbic acid is reducing agent used in:
•Removal of interference of Fe3+ in first group (pH 1-3) →
reduced to Fe2+
•Removal of interference of Hg2+ in first group (pH 1-3) →
reduced to Hgo (ppt.)
•Removal of interference of Cu2+ in second group (pH 4-6)
→ reduced to Cu+.
alkaline
2. Oxidation of Cr3+  to CrO42-
H2O2
3. Fe2+ , Hgo, Cu+, CrO42- do not react with EDTA
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Masking and Demasking Agents

Masking agents: A reagent added to prevent reaction

of some metal ion with EDTA (block metal ions)

These reagents form complexes with interfering ions

which are more stable than complexes formed with
indicator & EDTA.

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 Masking and demasking agents
(A) Cyanide (KCN)
Used as a masking agent for Ag+, Cu2+, Cd2+, Co2+, Ni2+, Zn2+.
M+ + 4 CN -  [M(CN)4]2-
(B)- Triethanolamine:
Used as a masking agent for Fe3+ , Al3+ and Sn2+
(C) Fluoride (NH4F):
Used as a masking agent for Fe3+ and Al3+ to give hexafluoro
complex [FeF6]3- and [AlF6]3-
(D)- Iodide (KI):
Used as a masking agent for Hg2+ to give tetraiodo complex (HgI4)
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 Demasking Agent
Reagents that release of a metal ion from a masking agent

Example
The masking by CN– can be removed by
(mixture of formaldehyde – acetic acid)
- on addition of demasking agent to [Zn(CN)4]2-, Zn is
liberated and titrated.
[ Zn(CN ) 4 ]2  4 H   HCHO  Zn 2  4 HO  CH 2  CN

[ Zn(CN ) 4 ]2  4CH 3COOH  4 HCHO  Zn 2  4 HO  CH 2  CN  4CH 3COO 

(less stable) (more stable) Cyanohydrin
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 OH

M CN 
nm
m  mH 2 CO  mH   mH2C Mn+

Metal-Cyanide Formaldehyde CN
Complex

Oxidation with H2O2 releases Cu2+ from Cu+-Thiourea complex.

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 Reference
Daniel Harris,(2007), “Quantitative Chemical Analysis” 7th
Edition, New York.

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