ACH150X Complexation Reactions and Titrations 2020

CHAPTER
Complexation Reactions And Titrations

ANALYTICAL CHEMISTRY
Llewellyn C. Anthony
anthonyl@cput.ac.za
17
Complexation Reactions And
Titrations
Complexation Reactions And Titrations anthonyl@cput.ac.za
Objectives
• Define/describe: Coordination compounds; Ligand; Coordination number;

Multidentate ligands
• Explain why multidentate ligands are preferred to monodentate ligands in
complex formation titrations
• Draw the structure of EDTA and explain why it is such a versatile reagent
• List indicators for EDTA titrations and its applications
• Discuss the types of EDTA titrations
• Explain how the scope of EDTA titrations can be improved
• Explain how water hardness can be determined
• Calculations from titrimetric data
§ Complexation Reaction
Introduction
One of the first uses of these reactions was for titrating cations
Complexes are coloured or absorb ultraviolet radiation (excitation of valence
electron) – basis for spectrophotometric determinations
Some complexes are sparingly-soluble and can be used in gravimetric
analyses or for precipitation titrations
Complexes are also used to extract cations from one solvent into another
and to dissolve insoluble precipitates
§ Complexation Reaction
Introduction
The most useful complex-forming reagents are organic compounds

containing several electron-donor groups that form multiple covalent bonds
with metal ions
Inorganic complexing agents are also used to control solubility and to form
coloured species or precipitates
Formed when metal ions react with electron pair donors
§ The Formation of Complexes

Definitions
Complex: species comprising a metal + ligand

Ligand: have at least one pair of unshared electrons available for bond
formation (electron pair donor), e.g. H2O, NH3, Cl, Br, I…
An ion or a molecule that forms a covalent bond with a cation or neutral
metal atom by donating a pair of electrons, which are then shared by two

Definitions
A specific metal ion can normally form bonds with ligands to a maximum of
2, 4 or 6
Gives an indication of the maximum number of bonds that can be formed by
the metal
Coordination number: the number of covalent bonds that a cation tends to
form with electron donors, e.g. [Cu(NH3)4]2+, [CuCl4]2, [Cr(NH3)6]3+
Complexiometric method: titrimetric methods based on complex formation

Definitions
Chelate: when a metal ion coordinates with two or more donor groups of a
single ligand to form a five- or six-member heterocyclic ring
This formation of a cyclic structure with a metal atom is known as chelation
The cyclic structure is known as the chelate, and the ligand is called a
chelating agent

Types Of Ligands
Unidentate: a ligand that has a single donor group, e.g. NH3

Bidentate: a ligand that has two groups available for covalent bonding, e.g.
Cu2+ complex with glycine where the Cu2+ is bonded to both O and N
Tridentate, tetradentate, …
O O
O
C O O C
2 H 2N + 2 H+
Cu2+ + Cu
OH
H2C N N CH2
glycine H H

Types Of Ligands: Multidentate (Chelate)
Binds to metal ions through more than one ligand atom [EDTA is
hexadentate (binds through two N and four O atoms)]

Types Of Ligands: Multidentate (Chelate)
It is hexaprotic in the form H6Y2+
HO2CH2C CH2CO2H
+ +
HNCH2CH2NH
HO2CH2C CH2CO2H
Macrocycles: metal ions and cyclic organic compounds
The organic compounds contain nine or more atoms in the cycle and include
at least three heteroatoms, usually O, N, S
The ions of alkali metals cam form complexes with crown ether and
cryptand
D. J. Cram, C. J. Pedersen and J.M. Lehn – Nobel Prize in Chemistry (1987)
crown ether cryptand metal ion encased in cryptand metallacrown

§ Complex Formation Titrations
Metal-ions can complex with ligands

Metal-ion solutions can be titrated with chelating agents in order to
establish the concentration of metal ions in solution
Advantage of chelation as compared to ordinary complex formation is that
chelation is essentially a single step process whereas complex formation
involves formation of intermediate species
§ Chelation
M + L 
 ML
ML + L 
 ML2
ML2 + L 
 ML3
. . .
. . .
. . .
MLn 1 + L 
 MLn
§ Why Chelation Is Preferred

Examples
(a). The reaction between a metal (M) (coordination number 4) and a

tetradentate ligand (D)
M + D 
 MD
K f = [MD]
[M][D]
where K f = formation constant


Examples
(b). The reaction between a metal (M) (coordination number 4) and a

bidentate ligand (B) occurs in two steps
[MB2 ]
M + 2B 
 MB2 2 =
[M][B] 2
 2 = equilibrium constant
for overall process
M + B 
 MB K 1 = [MB]
[M][B]
[MB2 ]
MB + B 
 MB2 K2 =
[MB][B]

Examples
(c). The reaction between a metal (M) (coordination number 4) and a

monodentate ligand (A) occurs in four steps
M + 4A 
 MA4  4 = [MA4 ]4
[M][A]
 4 = equilibrium constant
for overall process
§ Complexation Equilibria
Figure 17-1
Titration curves for complexiometric
titrations
Titration of 60.0 mL of a solution that is
0.020 M in metal M with (A) a 0.020 M
solution of the tetradentate ligand D to give
MD as the product; (B) a 0.040 M solution of
the bidentate ligand B to give MB2; and (C) a
0.080 M solution of the unidentate ligand A
to give MA4
The overall formation constant for each
product is 1020
§ Conclusion From Curves
Clear superiority of multidentate ligand that reacts in 1:1 ratio with metal
ion
Large change in pM at equivalence point
Makes endpoint detection easier
Multidentate ligands thus preferred in titrations, because reactions are
more complete, i.e. formation constants are larger
§ Aminocarboxylic Acid Titrations
EthyleneDiamineTetraAcetic acid [EDTA] is a weak acid and contains four

carboxyl groups, i.e. H4Y EDTA
HO2CH2C CH2CO2H
+ +
HNCH2CH2NH
HO2CH2C CH2CO2H
The EDTA molecule has six potential sites (in green) for bonding to a metal
ion
§ EDTA
Properties of EDTA
(1) Acid/Base
The fully protonated form is hexaprotic, H6Y2+
The electrically neutral form is tetraprotic, H4Y
The form commonly used in EDTA titrations is the disodium salt, Na2H2Y
Because EDTA is polyprotic, the forms that exist in solution depend on pH

§ EDTA Titrations
Acidic Properties of EDTA
H 4Y 
 H + + H 3Y  K 1 = 1.02×10 2
H 3Y  
 H + + H 2Y 2 K 2 = 2.14×10 3
H 2Y 2 
 H + + HY 3 K 3 = 6.92×107
HY 3 
 H + + HY 4 K 4 = 5.50×10 11
§ EDTA Titrations
EDTA has six pKa values, with the first four apply to carboxyl protons
(CO2H), while the next two apply to ammonium protons (NH+)
pKa1 = 0.0 (CO2H) pKa2 = 1.5 (CO2H)
pKa3 = 2.00 (CO2H) pKa4 = 2.69 (CO2H)
pKa5 = 6.13 (NH+) pKa6 = 10.37 (NH+)

§ EDTA Titrations
 
O2CH2C CH2CO2H O2CH2C CH2CO2H
+ + + +
HNCH2CH2NH H 4Y HNCH2CH2NH H 3Y 
  
HO2CH2C CH2CO2 O2CH2C CH2CO2
   
O2CH2C CH2CO2 O2CH2C CH2CO2
+ + + +
HNCH2CH2NH H 2Y 2 
NCH2CH2NH HY 3
   
O2CH2C CH2CO2 O2CH2C CH2CO2

O2CH2C CH2CO2
 Structure of H4Y and its dissociation products

Note that the fully protonated species H4Y exists as the

NCH2CH3N Y4
double zwitterion with the amine nitrogens and two of the
 
carboxylic acid groups protonated
O2CH2C CH2CO2
The first two protons dissociate from the carboxyl groups,
while the last two come from the amine groups
§ EDTA Titrations
EDTA is useful because:

It is readily available as a primary standard (usually the disodium
salt)
It forms 1:1 metal-ligand complex
Large formation constants with many metal ions
It forms stable, water-soluble metal complexes
§ Complexes of EDTA and Metal Ions
The reagent combines with metal ions in a 1:1 ratio regardless of the charge
on the cation
Ag+ + Y 4 
 AgY 3
Al 3+ + Y 4 
 AlY 
M n+ + Y 4 
 MY (n 4)+
K MY = [MY (n 4)+ ]

[M n+ ][Y 4 ]
§ EDTA
Properties of EDTA
(2) Ability to form metal-EDTA complexes
Formation constant (stability constant), Kf = the equilibrium constant for the

reaction of a metal ion (Mn+) with a ligand
For EDTA, Kf is usually written in terms of Y4
By convention, Kf will be expressed in terms of Y4
Note that Y4 is not the only form of EDTA that complexes with Mn+
§ EDTA
Properties of EDTA
Metal-EDTA complex is unstable at very low pH

H+ competes with metal ion for EDTA
Metal-EDTA complex is unstable at very high pH
OH competes with EDTA for metal ion
Unreactive hydroxide complexes may form
Metal hydroxide may precipitate
§ EDTA
Use of Auxiliary Complexing Agent (ACA)
Prevents metal ion from precipitating in the hydroxide form

Forms weak complex with metal ion
Displaced by EDTA during titration
Examples
Ascorbate, citrate, tartrate, ammonia, and triethanolamine
§ EDTA
Use of Auxiliary Complexing Agent (ACA) – Examples
Titration of Ca2+ and Mg2+ at pH 10

Ascorbic acid (ascorbate) as ACA
Titration of Pb2+ at pH 10
Tartaric acid (tartrate) as ACA
§ EDTA
EDTA Titration Techniques
EDTA Titration Techniques are useful for the determination of [metal]

Direct titration
Titrate with EDTA
Buffered to an appropriate pH
Colour distinct indicator
Auxiliary complexing agent
§ EDTA
EDTA Titration Techniques
Back titration necessary under three conditions

If analyte blocks the indicator
If analyte precipitates in the absence of EDTA
Example
(Al3+-EDTA) at pH 7, indicator Calmagite) back titration with Zn2+
If analyte reacts too slowly with EDTA

Excess EDTA, & titrate with metal ion
§ EDTA
EDTA Titration Techniques: Indirect Titration
Used to analyze anions that precipitate metal ions

CO32, CrO42, S2, SO42
Anion is precipitated with excess metal ion
Precipitate is filtered and washed
Excess metal ion in filtrate is titrated with EDTA
Example
SO42 + Ba2+  BaSO4(s) at pH 1
Filter BaSO4(s) and boil with excess EDTA at pH 10

Ba(EDTA)2 and excess EDTA is back titration with Mg2+
§ EDTA
Water Hardness
Total concentration of alkaline earth ions in water

Concentration of Ca2+ and Mg2+ are usually much greater than the rest
Hardness is [Ca2+] + [Mg2+]
Often expressed as milligrams of CaCO3 per liter (ppm)
If [Ca2+] + [Mg2+] = 1.00 mM = 1.00 mmol/L
~100 mg CaCO3 = 1.00 mmol CaCO3
Implies hardness is 100 mg CaCO3 per liter (100 ppm)

§ EDTA
Measuring Water Hardness
Treat water with ascorbic acid to reduce Fe3+ to Fe2+

Treat water with CN to mask Fe2+, Cu+, and other metal ions
Titrate with EDTA in ammonia buffer at pH 10
Determine [Ca2+] + [Mg2+]
OR
Titrate with EDTA at pH 13 without ammonia
Mg(OH)2 precipitates at pH 13 and is not accessible to EDTA
[Ca2+] is determined separately in this case
§ EDTA
Titration of Ca2+ and Mg2+ with EDTA

Add small amount of Calmagite indicator to solution
Red Mg-In/Ca-In complex is formed
Titrate with EDTA until colour changes to blue
§ EDTA
Titration of Ca2+ and Mg2+ with EDTA
Mg2+/Ca2+ in solution is used up as EDTA is added
Just before equivalence point the last EDTA displaces indicator from Mg-In
Unbound In is blue and indicates end point
Mg-In + EDTA → Mg-EDTA + In

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CHAPTER

Complexation Reactions And Titrations

• Define/describe: Coordination compounds; Ligand; Coordination number;

The most useful complex-forming reagents are organic compounds

§ The Formation of Complexes

Complex: species comprising a metal + ligand

§ The Formation of Complexes

§ The Formation of Complexes

§ The Formation of Complexes

Unidentate: a ligand that has a single donor group, e.g. NH3

§ The Formation of Complexes

§ The Formation of Complexes

It is hexaprotic in the form H6Y2+

§ The Formation of Complexes

Macrocycles: metal ions and cyclic organic compounds

§ The Formation of Complexes

crown ether cryptand metal ion encased in cryptand metallacrown

§ Complex Formation Titrations

Metal-ions can complex with ligands

§ Why Chelation Is Preferred

(a). The reaction between a metal (M) (coordination number 4) and a

where K f = formation constant

§ Why Chelation Is Preferred

(b). The reaction between a metal (M) (coordination number 4) and a

§ Why Chelation Is Preferred

(c). The reaction between a metal (M) (coordination number 4) and a

§ Conclusion From Curves

§ Aminocarboxylic Acid Titrations

EthyleneDiamineTetraAcetic acid [EDTA] is a weak acid and contains four

The electrically neutral form is tetraprotic, H4Y

Because EDTA is polyprotic, the forms that exist in solution depend on pH

(CO2H), while the next two apply to ammonium protons (NH+)

pKa1 = 0.0 (CO2H) pKa2 = 1.5 (CO2H)

pKa3 = 2.00 (CO2H) pKa4 = 2.69 (CO2H)

pKa5 = 6.13 (NH+) pKa6 = 10.37 (NH+)

EDTA is useful because:

§ Complexes of EDTA and Metal Ions

K MY = [MY (n 4)+ ]

Formation constant (stability constant), Kf = the equilibrium constant for the

For EDTA, Kf is usually written in terms of Y4

By convention, Kf will be expressed in terms of Y4

Metal-EDTA complex is unstable at very low pH

Prevents metal ion from precipitating in the hydroxide form

Titration of Ca2+ and Mg2+ at pH 10

EDTA Titration Techniques are useful for the determination of [metal]

Back titration necessary under three conditions

If analyte reacts too slowly with EDTA

Used to analyze anions that precipitate metal ions

Filter BaSO4(s) and boil with excess EDTA at pH 10

Total concentration of alkaline earth ions in water

Implies hardness is 100 mg CaCO3 per liter (100 ppm)

Treat water with ascorbic acid to reduce Fe3+ to Fe2+

Titration of Ca2+ and Mg2+ with EDTA

Titration of Ca2+ and Mg2+ with EDTA

Mg2+/Ca2+ in solution is used up as EDTA is added

Unbound In is blue and indicates end point

Mg-In + EDTA → Mg-EDTA + In

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