2013/2014 1

46
Complexometric Titration
47
Complexometric Titration
Determinations of metals

Titrate metal ions with titrant which
is a complexing agent
EDTA very useful complexing agent
EDTA titration for determination of
water hardness (how much Ca and
Mg?)
48 49
Complexes
M = Central metal
atom
L = Ligand
X = counter ion
Central metal atom
must have ability to accept 1 @ more pairs of
e
-
in available d orbital typically a metal ion.
50
Ligand
Anion, cation @ neutral sp. with ability to donate
e
-
pair to form a coordinate covalent bond.








M
z+
L :

L :

L :

L :

ligand
Covalent
bond
Central metal atom
Eg: H
2
O, NH
3
, Cl
-
,
Br
-
, EDTA
Cont
51
2013/2014 2
52
coordinate covalent bond

53
Counter ion
Required if complex is charged.
The number of covalent bonds formed is called
the coordination number.
Eg : Cu
2+
has coordination number of 4
i. Cu
2+
+ 4 NH
3
Cu(NH
3
)
4
2+
ii. Cu
2+
+ 4 Cl
-
Cu(Cl)
4
2-






Cl

Cu

Cl
Cl

Cl

2-
Cont
54
Chelate is formed when a metal ion coordinates
with two of more donor groups of a single ligand
(forming a 5- or 6- membered heterocyclic ring)

Chelating agent: ligand having more than one
electron donating group

The most widely used chelating agent in
titration is (EDTA)

The titration are called : complexometric,
chilometric or EDTA titration.


Cont
55
EDTA
EDTA is a hexadentate ligand.
EDTA forms stable chelates with most metal ions.
6 binding sites
4 H on carboxylic acid groups
2 lone pairs of electrons on amine group
Forms strong 1:1 complexes with most
metal ions.

Metal-EDTA complex becomes less
stable at + pH.

Regardless of the coordination number
of the central spesies, the molecule
will adapt to the number needed.

56 57
2013/2014 3
58
Species present in a solution of
EDTA
N CH
2
CH
2
N

-
OOCCH
2


H
+
CH
2
C

OO
-
H
+
CH
2
C

OOH
-
OOCCH
2
H
3
Y
-
N CH
2
CH
2
N

-
OOCCH
2


H
+
CH
2
C

OO
-
H
+
CH
2
C

OO
-
-
OOCCH
2
H
2
Y
2-
N CH
2
CH
2
N

-
OOCCH
2


H
+
CH
2
C

OO
-
H
+
CH
2
C

OOH
HOOCCH
2
H
4
Y

59
CH
2
C

OO
-
N CH
2
CH
2
N

-
OOCCH
2


CH
2
C

OO
- -
OOCCH
2
Y
4-
N CH
2
CH
2
N

-
OOCCH
2


CH
2
C

OO
-
H
+
CH
2
C

OO
-
-
OOCCH
2
HY
3-
pH EDTA will
influence
distribution of
H
4
Y, H
3
Y
-
,
H
2
Y
2-
, Y
4-
.
Cont
60
5 species EDTA as a function of pH
The alpha value for a
species is given by
a
species
=[species]/C
T

o
0
= [H
4
Y]/C
T
o
1
= [H
3
Y
-
]/C
T
o
2
= [H
2
Y
2-
]/C
T
o
3
= [HY
3-
]/C
T
o
4
= [Y
4-
]/C
T

C
T
= [Y
4-
] + [HY
3-
] + [H
2
Y
-2
] + [H
3
Y
-
] + [H
4
Y] 61
Metal Chelate Complexes
Formation Constant (K
f
)
The equilibrium constant for the reaction
between a metal ion (M
+n
) & a chelating agent
is known as a formation constant or stability
constant.
Chelate effect: Multidentate chelating agents
form stronger complexes (K
f
) with metal ions than
monodentate ligands.
Monodentate ligand: a chelating agent with only
one pair of free electrons
Multidentate ligand: a chelating agent with
more than one free electron pair.
62
Monodentate ligands rarely used as titrants
Sharp end point generally difficult to achieve.
Stepwise formation constants are frequently
close together, not very large, single
stoichiometric complex cannot be observed)

Multidentate ligands (tetradentate &
hexadentate) are preferred for titrimetry :
react more completely with metal ion
provide sharper end-points
usually react in a single step (form a 1:1
complex)
Cont
63
M = metal ion M, that has a
coordination no. of 4

If A = tetradentate ligand
Curve A : M + A MA (1step)

If B = bidentate ligand
Curve B : M + B MB (2step)
MB + B MB
2


If C = monodentate ligand
Curve C : M + C MC (4step)
MC + C MC
2

MC
2
+ B MC
3
MC
3
+ C MC
4
Cont
2013/2014 4
64
EDTA Equilibria
EDTA has 4 acid dissociation steps:
Y
3-
] [H
] [Y ] [H
10 5.5 K Y H HY
Y
-2
] [H
] [HY ] [H
10 6.9 K HY H Y H
Y
-
] [H
] Y [H ] [H
10 2.2 K Y H H Y H
Y] [H
] Y [H ] [H
10 1.0 K Y H H Y H
4
11 -
a4
4 3
2
3
7 -
a3
3 2
2
3
2
2 3 -
a2
2
2 3
4
3 2 -
a1 3 4
+
+
+
+
+
+
+
+
= = +
= = +
= = +
= = +
65
Complex-Formation Titrations
Solution Chemistry of EDTA(H
4
Y)
Combine with metal ions in a ration 1:1
regardless of the charge on the cation.
Eg: Ag
+
+ Y
-4
AgY
3-
In general;



We usually express the equilibrium for the
formation of complex ion in terms of the Y
4-

form (all 6 protons dissociated).
| |
| || |
+

+
= +
4
4
f
4 4
Y M
MY
MY Y M
n
n
n n
K
66
Can calculate [M
n+
] at a given pH
Define: o
4
= [Y
4-
]/C
T
(o
4
values depend on pH)

C
T
= The concentration of uncomplexed
EDTA
= [Y
4-
] + [HY
3-
] + [H
2
Y
2-
] + [H
3
Y
-
] + [H
4
Y]
Substitute [Y
4-
] into K
f
equation


C
T
[Y
4-
] x
= o
4
=
[MY
n-4

]
K
f
[Y
4-
] [M
n+

]
=
[MY
n-4

]
K
f
[M
n+

] C
T
x o
4
Cont
67
If we fix the pH of the titration with a buffer,
then o
Y
4- is a constant that can be combined
with K
f









We can use K
f
to calculate the equilibrium
concentrations of the different species at a specific pH
only.
K
f
value holds for a specified pH only when o
4
is used.
| |
| |
C
T
M
MY
4
f
Y
f
- 4
+

= =
n
n
'
K K
o
Conditional Formation
Constant
Cont
68
Calculation of o
4
for EDTA
a4 a3 a2 a1 a3 a2 a1
2
a2 a1
3
a1
4
a4 a3 a2 a1
4

K K K K ] [H K K K ] [H K K ] [H K ] [H
K K K K
o
+ + + +
=
+ + + +
Calculate o
4
in EDTA solution at pH=10.2

Ans: 0.47
69
pH Dependence of
Y
4-

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70
Detection of the End Point:
Indicators
The most common technique used to detect end
point in EDTA titration metal ion indicator
A metal ion indicator is a compound whose colour
changes when it binds to a metal ion.
For an indicator to be useful, it must bind metal less
strongly than EDTA does.
Eg : Eriochrome black T (EBT), Xylenol Orange
Eg: Titration of Mg
2+
with EDTA using EBT as
indicator
MgEBT + EDTA MgEDTA + EBT
(red) (colorless) (colorless) (blue)
71
For metal ions that do not have a
satisfactory indicator, a displacement
titration may be feasible.
The analyte is treated with excess Mg(EDTA)
2-

to displace Mg
2+
, which is then titrated with
standard EDTA.

M
n+
+ MgY
2-
MY
n-4
+ Mg
2+

** The formation constant of MY
n-4
must be
greater than Mg(EDTA)
2-
for reaction to work.
Cont
72
A Masking agent is a reagent that protects
some components of the analyte from
reaction with EDTA.
Eg : Al
3+
react with F
-
to form a very stable
complex AlF
6
3-
. The Mg
2+
in a mixture of
Mg
2+
and Al
3+
can be titrated by first
masking the Al
3+
with F-, leaving only
Mg
2+
to react with EDTA.
Cont
73
EDTA Titration Curves
The titration of a metal ion
with EDTA is similar to the
titration of a strong acid
(M
+
) with a weak base
(EDTA).


74
Exercise
Titration of 50.0 ml 0.100 M Ca
2+
with 0.100 M
EDTA standard solution.

Ca
2+
+ Y
4-
CaY
2-
K
f
= 5.0 x 10
10

Ca
2+
solution is buffered at pH 10.

a) 0.00 mL EDTA (Ans: 1.0)
b) 25 mL EDTA (Ans: 1.48)
c) 50 mL EDTA (Ans: 5.78)
d) 75 mL EDTA (Ans: 9.95)
e) 100 mL EDTA (Ans:10.26)
Precipitation titration
75
2013/2014 6
76
Precipitation titration

77

78 79
Precipitation Equilibria
Precipitation reactions are process in which
soluble reactants yield an insoluble solid product
that falls out of solution.
Most precipitations take place when certain
cations and anions combined to produce an
insoluble ionic solid called a precipitate.
The equilibrium constant expression for the
solution of a solid
AgCl(s) Ag
+
(aq) + Cl
-
(aq)
K
eq
=

K
sp
= [Ag
+
] [Cl
-
] = Solubility Product
[Ba
2+
] = 7.5 x 10
-3
M in saturated BaF
2
.
Calculate K
sp
.
Solution :
BaF
2
(s) Ba
2+
(aq) + 2F
-
(aq)
x 2x
7.5 x 10
-3
2(7.5 x 10
-3
)
K
sp
= [Ba
2+
] [2F
-
]
2
K
sp
= (7.5 x 10
-3
) (15.0 x 10
-3
)
2
= 1.6 x 10
-6
Example
81
The concentration of solute in a
SATURATED solution is the same
whether the solution fills a beaker or a
swimming pool, so long as there is
solid in equilibrium with it. BUT much
more solid will dissolve in the
swimming pool !!!!
ALERT !!
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82
Molar Solubility
Equilibrium between solid compound and
ions in a saturated solution.
Molar solubility, s
number of moles of a substance (the
solute) that can be dissolved per liter of
solution before the solution becomes
saturated.
Eg: BaSO
4
(p) Ba
2+
(aq) + SO
4
2-
(aq)
At , s M s M
K
sp
= [Ba
2+
] [SO
4
2-
] = s
2

Determine the molar solubility of CaCO
3
if the K
sp
is
3.8 x 10
-9
at 25 C.
Solution:
CaCO
3
(s) Ca
2+
(aq) + CO
3
2-
(aq)



K
sp
= 3.8 x 10
-9

Thus, s
2
= 3.8 x 10
-9

s = 6.2 x 10
-5
M = [Ca
2+
] = [CO
3
2-
]
[ ]
0
0 0
A + s + s
[ ]
equilibrium
+ s + s
Example
84
Precipitation Titration
Basis for ppt titration: ppt rxn must
be rapid
Complete
Exist an indicator for detection of end-point
Frequently used reagent:
AgNO
3
For the determination of halides, SCN
-
,CN
-
, a
few divalent anions & mercaptans

M
+
+ X
-
MX (s)
(titrant) (analyte)

85
Detection of the End Point:
The end point can be detected by :

Potentiometric method using electrode

Indicator method

Light scattering method, either with
turbidimetry or nephelometry
86
Indicator method
i. Mohr titration ~ formation of a colored
precipitate at the end point.

ii. Volhard titration ~ formation of a soluble,
colored complex at the end point.

iii. Fajans titration ~ adsorption of a colored
indicator on the precipitate at the end point.

87
Mohr Titration
Developed for the determination of Cl
-
&
Br
-
& CN
-
Uses AgNO
3
as titrant and Na
2
CrO
4
as
indicator
Titration reaction:
Ag
+
+ Cl
-

AgCl (s) K
sp
= 1 x 10
-10

white (ppt)

Indicator reaction:
2Ag
+
+ CrO
4
2-
Ag
2
CrO
4
(s)
excess yellow red (ppt)
2013/2014 8
88
The AgCl end point is indicated by the
first appearance of red Ag
2
CrO
4
.
Blank determination with sample
without Cl
-
is required to eliminate
titration error and obtain equivalent
point instead of end point.
Cont
89
Volhard Titration
For the determination of Ag
+
, Cl
-
, Br
-
, I
-
,
SCN
-
in acid medium.
Add known excess Ag
+
to halide solution,
followed by back titration of the excess
with thiocyanate.
Fe
3+
used as indicator end point marked
by appearance of red Fe(SCN)
2+
(water
soluble)


90 91
Analyte reaction:
X
-
+ Ag
+
(excess) AgX (s)
white (ppt)
Back Titration reaction:
Ag
+
+

SCN AgSCN(s)
white (ppt)

Indicator reaction:
Fe
3+
+ SCN Fe(SCN)
2+
red (ppt)
Cont
92 93
2013/2014 9

94

95
96 97
Fajans Tiration
Adsorption indicator is used.
Adsorption indicator is an organic
compound that tends to be adsorbed onto
the surface of the solid in a precipitate
titration.
When Ag
+
is added to Cl
-
, there will be
excess Cl
-
ions in solution that selectively
adsorbed on the AgCl surface ~ crystal
surface with ve charge.
98
After equivalent point, excess Ag
+

adsorbed on precipitate surface ~ +ve
charge.

Cont
Anionic dye indicator
(dichlorofluorescein) is added and
attracted to +ve charged precipitate
(small particle preferred).
The change of indicator colour after this
interaction signals the end point
(greenish-yellow turns pink).

99
Cont
2013/2014 10
100
Exercise
Calculate pCl for the titration of 100.0mL of 0.1000 M
Cl
-
with 0.1000 M AgNO
3
for the addition of :


a) 0 mL titrant

b) 20 mL titrant
c) 99 mL titrant
d) 99.5 mL titrant
e) 100.00 mL titrant
f) 100.50 mL titrant
g) 110.00 mL titrant