[

CHM 132
ANALYTICAL CHEMISTRY 2

Complexometric Titration
Introduction to Complex Formation
[
LEARNING OBJECTIVES
 Define complex formation and identify its
applications
 Analyze the steps involved in complexation
equilibria
 Calculate the alpha values of metal complexes
[
COORDINATION COMPOUNDS
+3 +2

Complex/Coordination Compounds
- Product of the reaction of metal
ions with electron-pair donors
called ligands
Coordinate covalent bond or dative bond
[COORDINATION COMPOUNDS
Metals can combine with complexing agents (LIGANDS)
through Lewis acid–base type bonding. The metal has an
empty orbital, the agent has a lone pair of electrons.
[
LIGANDS

Some common ligand groups

water ammonia halides

carbonyls hydroxides mercaptans

 in aqueous systems, ligands are typically anionic

or polar neutral species
[
LIGANDS

Classification of ligands according to dentate

number

Unidentate
single donor group - ammonia

Bidentate
two donor groups - glycine

Multidentate
variable number based on need - EDTA
[
COORDINATION NUMBER

 number of covalent bonds that the metal tends

to form with the ligand

 typical values are 2,4, and 6

 complexes formed due to coordination may be

(+) charged, (-) charged, or neutral
[
COORDINATION NUMBER

Copper(II) with a coordination number of 4

Cu(NH3)42+

Cu(NH2CH2COO)2

CuCl42-
[
MONODENTATE LIGANDS

 possess only one accessible donor group

Example
Water, H2O – most metal ions exist as aquo
complexes in water

Ag(H2O)2+ Cu(H2O)42+ Fe(H2O)63+

 charge and coordination number are NOT related

[
MONODENTATE LIGANDS

Common monodentate ligands

Neutral Anionic
H2O OH-
NH3 CN-
RNH2 S2-
RCOO-
SCN-
[
BIDENTATE LIGANDS

 form two bonds with metal ion

Example
Ethylene diamine (en) – NH2CH2CH2NH2
[
BIDENTATE LIGANDS

Common bidentate ligands

 8-hydroxyquinoline
[
BIDENTATE LIGANDS

Common bidentate ligands

 Dimethylgyloxime - DMG
[
BIDENTATE LIGANDS

Common bidentate ligands

 1,10-phenanthroline
[
CHELATE

 complex formed when metal ion coordinates

with two or more donor groups of a single
ligand to form a 5- or 6-membered ring

O C O O C O
Cu
H2 C NH NH CH
2
[
CHELATE

 chelating agent – refers to the multidentate

ligand

 chelon – refers to the multidentate ligand that

forms stoichiometric, stable, 1:1
soluble complex
Mn+

18
 EDTA
- -
O
O
C O
O
C
N
N
- -
C
O
O C
O
O

 a polyaminocarboxylate ligand

 a polydentate ligand (hexa- or sexidentate)

 most widely used chelator

 one of the most versatile chelons

 common sequestrant and antioxidant added to foods, body
19
care and household products.
20
21
[ Why Am I Eating EDTA?
• EDTA is a ligand that can attach to metals in more
than one site….
• it acts as a preservative as it ties up critical
metals that bacteria need.
Some Ligands Can Bond to a Metal Ion in More
Than One Place…Chelating Agents
• There will be fewer actual complexes formed, so the
calculations will be less intricate. It is handy if the ratio of
metal to ligand could be 1:1.
Some Ligands Can Bond to a Metal Ion in More
Than One Place…Chelating Agents

a polydentate ligand (hexa- or sexidentate)

Mn+
 Chelon

Ethylenediamine tetraacetic acid (EDTA)

 most widely used complexometric titrant

 forms 1:1 complexes with most metals

 forms stable, water soluble complexes

 high formation constant

 EDTA

 the disodium salt is often used since it is more

soluble

 has 6 donor groups

 Complexation Reactions
 widely used in analytical chemistry
Gravimetry

DIMETHYLGLYOXIME
 Complexation Reactions

Titrimetric Methods
Metal-EDTA
 Complexation Reactions
Spectrophotometry Metal-dithiocarbamate
 Metallobiomolecules
• one third of all proteins contain at least one
metal ion as essential prosthetic group
Vitamin
B12

http://www.scientificpsychic.com/health/vitamins.html
 SOLUBLE COMPLEX FORMATION

+
metal ion ligand complex
chelon* chelate*
chelator coordination compound
chelating agent
complexing agent
sequestering agent

ligand could be: ion or neutral molecule

organic or inorganic

e- pair acceptor: e- pair donor:

32
LEWIS ACID LEWIS BASE
 Formation of [Ag(NH3)2]+

(1) Ag+ + NH3 Ag(NH3)+

Kf1 = 2.1 x 103

(2) Ag(NH3)+ + NH3 Ag(NH3)2+

Kf2 = 8.2 x 103

Ag+ + 2NH3 Ag(NH3)2+

[Ag(NH3)2+]
Kf = [Ag+] [NH3]2

= 1.7 x 107 33
COMPLEXATION EQUILIBRIUM

34
FORMATION CONSTANT

35
  values for metal complexes

MBE: CAg+ = [Ag+] + [Ag(NH3)+] + [Ag(NH3)2+]

[Ag+] [Ag+]
0 = Ag+ =
[Ag+] +CAg+
[Ag(NH3)+] + [Ag(NH3)2+]

+]
[Ag(NH3)+[Ag(NH
] 3 )
1 =  = [Ag+] + [Ag(NH )+] + [Ag(NH ) +]
𝑨𝒈𝑵𝑯𝟑
+ CAg+ 3 3 2

+
[Ag(NH3)[Ag(NH +
2 ] 3) 2 ]
2 = 𝜶𝑨𝒈 𝑵𝑯𝟑 𝟐+ =
[Ag+] +C[Ag(NH
Ag+ 3 ) +] + [Ag(NH ) +]
3 2

36
  values for metal complexes
[Ag(NH3)+] = [Ag(NH3)2+] =
[Ag(NH3)+] [Ag(NH3)2+]
Kf1 = Kf2 =
[Ag+] [NH3] [Ag(NH3)+] [NH3]

[Ag(NH3)+] = Kf1 [Ag+] [NH3] [Ag(NH3)2+] = Kf2 [Ag(NH3)+] [NH3]

= Kf2 Kf1 [Ag+] [NH3]2
[Ag(NH3)+]
1 = AgNH3+=
[Ag+] + [Ag(NH3)+] + [Ag(NH3)2+]

Kf1 [Ag+] [NH3]

=
[Ag+] + Kf1 [Ag+] [NH3] + Kf2 Kf1 [Ag+] [NH3]2
Kf1 [NH3] β1 [NH3]
= =
1 + Kf1 [NH3] + Kf1 Kf2 [NH3]2 1 + β1 [NH3] + β2 [NH
39 ]2
3
  values for metal complexes

M =

ML =

ML =

40
 EDTA complexes

[MYn-4]
Kf =
[Mn+] [Y4-]

41
42
43
Fractional composition of EDTA

Y4-

44
Effect of pH on the composition of EDTA

Expressing 4 in terms of Ka and [H+]:

45
Effect of pH on the composition of EDTA

46
 Effect
Conditional
of pH on the
formation
composition
constant
of EDTA

Note that, at a given pH, 4, the fraction of total EDTA in the
unprotonated form, Y4-, is constant.

where K’MY is a constant only at the pH for which 4 is applicable.

47
Calculation of [Y4-]

48
 Calculation of [Mn+]

Mn+ Mn+

free; unbound; bound;

uncomplexed; complexed;
dissociated undissociated
49
 Mn+ Y4- MYn-4
initial
equilibrium

[MYn-4]
Kf =
[Mn+] [Y4-]

bound; complexed;
undissociated

free; unbound; uncomplexed;

dissociated
50
51
52
 Calculation of [Mn+]

+
[NiY2-]
Kf =
[Ni2+] [Y4-]
[NiY2-] pH = 3.00
Kf =
[Ni2+] 4[EDTA] 4 = 2.1 x 10-11

Kf 4 = Kf’ = 2.1 x 10-11 (antilog 18.4)

= 5.275 x 107 53
 Calculation of [Mn+]

+
[CaY2-]
Kf =
[Ca2+] [Y4-]
[CaY2-] pH = 6.00
Kf =
[Ca2+] 4[EDTA] 4 = 1.8 x 10-5

Kf 4 = Kf’ = 1.8 x 10-5 (antilog 10.65)

= 8.040 x 105 54
 Calculation of [Mn+]

+
Kf 4 = Kf’ = 8.040 x 105

[CaY2-] 0.10 ‒ x
8.040 x 105 = =
[Ca2+] [Y4-] x2

Ca2+ Y4- CaY2-

initial 0 0 0.10
equilibrium x x 0.10 ‒ x
pH = 6.00
x = [Ca2+] = 3.52 x 10-4 M 4 = 1.8 x 10-5
55
 Calculation of [Mn+]

Ni2+ Y4- NiY2-

initial 1.5 mmol 2.5 mmol 0
equilibrium x 1.0 mmol 1.5 mmol
[NiY2-] 0.015 M0.015 M
= 2+] =2+
Kf [Ni 4-
=
[Ni ] 0.010
[Y ] M (5.275 107) M
[Ni2+]x0.010
= 2.84 x 10 -8 M
K  = K ’ = 5.275 x 107
f 4 f 56
EDTA Titration Curves

57
 EDTA Titration Curves
Before Titration

0.00500 M pCa = 2.30

Before EP

3.6364 × 10-3 M pCa = 2.44

58
 EDTA Titration Curves
At EP

1.75 × 1010

3.3333 × 10-3 M

4.3644 × 10-7 M pCa = 6.36 59

 EDTA Titration Curves
After EP
1.75 × 1010

3.2895 × 10-3 M

1.3158 × 10-4 M

1.4286 × 10-9 M pCa = 8.85

60
 +
Titration of 50.00 mL of 0.00500 M Ca2+ with 0.0100 M EDTA at pH 10.00

after EP

at EP

before EP
before Titration

61
EDTA Titration Curves

64
EDTA Titration with
EDTA
auxiliary
Titration
complexing agents

+
+ 4
+ +4

65
EDTA Titration with auxiliary complexing agents

+ 4

+ +4

66
EDTA Titration with auxiliary complexing agents

67
EDTA Titration with auxiliary complexing agents

68
69
70
71
72
 EDTA
HInTitration
2‒

HIn2‒
I. STANDARDIZATION of EDTA
H2In‒
1° standard
reaction
condition
indicator
N
O2

-
S
O
H2In- ↔ HIn2- ↔ In3-
3

N
N
pH: 2-6 7-11 12-14
O
H
O
H
73
I.STANDARDIZATION of EDTA
 before titration (addition of indicator to analyte):

Mn+ + HIn2- MInn-3 + H+

metal ion indicator metal-indicator
complex

 during titration (addition of EDTA):

Mn+ + H2Y2- MYn-4 + 2H+

metal-EDTA
metal ion EDTA
complex

 since: KMY >> KMIn

 at equivalence point:

MInn-3 + H2Y2- MYn-4 + HIn2-

74
Metal ion indicators

75
EDTA Titration Techniques

76
EDTA Titration Techniques

77
 𝒈
Zn: 65.41 Τ𝒎𝒐𝒍

+ +

78
Applications of EDTA Titration

79
Applications of EDTA Titration

80
Applications of EDTA Titration

81
Applications of EDTA Titration

+
82
 0.01205 mol 100.09 g 1000 mg
𝐭𝐨𝐭𝐚𝐥 𝐡𝐚𝐫𝐝𝐧𝐞𝐬𝐬 = 0.02365 L
L 1 mol CaCO3 1g

= 𝟓𝟕𝟎. 𝟓 𝐩𝐩𝐦 𝐂𝐚𝐂𝐎𝟑

g mg
0.01453 L 0.01205 molൗL 100.09 ൗmol 1000 ൗg
𝐩𝐩𝐦 =
0.05000 L

=
g mg
1.09896x10−4 mol 84.32 ൗmol 1000 ൗg
𝐩𝐩𝐦 =
0.05000 L
=
MM, 𝒈Τ𝒎𝒐𝒍 moles ppm, 𝒎𝒈Τ𝑳
total -- 2.85 𝑥 10−4 570.5
CaCO3 100.09 1.75 𝑥 10−4 350.5
MgCO3 84.32 1.10 𝑥 10−4 185.3 83
 EDTA Titration Curves

 Some metals forms precipitate when the pH is raised

to the level required for their successful titration with
EDTA.
 Thus, buffering is needed. Usually, the buffer used is
NH3-NH4Cl. This will make the concentration of Y4-
constant and also it will prevent the metals from
precipitating as hydroxides.
 NH3 will complex with the metal and keep the metal in
solution
 NH3 is an auxiliary complexing agent/ligand.

Account for αM
84
 EDTA Titration Curves

 The ligand can form complexes with different metals.

Sometimes, one metal interfere with the
determination of the other metal.

 MASKING AGENT – an auxiliary ligand that

preferentially forms highly stable complexes with
the potentially interfering ion.

 The interfering ion is masked, i.e., it will not react with

the titrant because it is already chelated by the
masking agent.
85
 0.01133 mol 81.41 g 250 mL
0.03837 L
L mol 1.056 g
= x 100
50.00 mL

0.0002647 mol Fe3+ 1 mol Fe2 O3 159.7 g 250 mL

0.00230 L L 2 mol Fe3+ mol 1.056 g
= x 100
50.00 mL

MM, 𝒈Τ𝒎𝒐𝒍 %
ZnO 81.41 83.79
Fe2O3 159.7 0.23
87