Complexation Titration

Forming Complexes
Most metals ions react with electron-pair
donors to form coordination compounds or
complexes.
The donor species (ligand) must have at
least one pair of unshared electrons
available for bond formation.
Cu(H
2
O)
4
2+
, Cu(NH
3
)
4
2+
, Cu(NH
2
CH
2
COO)
2


CuCl
4
2-

Ligands
A ligands is a neutral molecule or ion having a
lone pair that can be used to form a bond to a
metal ion.
Chelating agents: unidentate, bidentate,
tridentate, tetradentate, pentadentate,
hexadentate


Gramicidin A antibiotic ion channel
Nonactin forms a complex with the K + ion; the
coordination occurs through the 8 O atoms.
Chelation in Biochemistry
Chelating ligands can form
complex ions with metals
through multiple ligands.
This is important in many
areas, especially
biochemistry.
Box 13-1 Chelation Therapy & Thalassemia
A successful drug for iron excretion
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 in 1987
Crown Ether Complex of Potassium

Potassium permanganate is dissolved in
benzene by addition of 18-crown-6.
Coordination Compounds
colored & paramagnetic (often)
consists of a complex ion
(1) Coordination compounds are neutral
species in which a small number of
molecules or ions surround a central
metal atom or ion.
ex.
[Co(NH
3
)
5
Cl]Cl
2
complex ion : [Co(NH
3
)
5
Cl]
2+

Coordination Compounds
coordinate covalent bond

Complex ion = metal cation + ligands
e acceptor e donor
center (one) surrounding ( > 2 )
transion metal
Lewis acid Lewis base

[ Co(NH
3
)
5
Cl ]Cl
2

H
2
O , NH
3
, :Cl

..
..
.. ..
..
ionic force
counter ions
central metal ligands
complex ion
20.3 Coordination Compounds
(2) Coordination number :
The # of donor atoms surrounding the central
metal
The most common : 4
or
6
(3) Ligands :
A neutral molecule or ion having a line pair that
can be used to from a bond to a metal ion.
monodentate : H
2
O , NH
3

bidentate : en , ox
polydentate : EDTA
Chelating agents
13-1 Metal-Chelate Complexes
EDTA forms strong 1:1 complexes with most metal ions
As a metal-binding agent
Useful chelating agents

13-2 EDTA
(ethylenediaminetetraacetic acid, a hexadentate)
(1) The most widely used chelating agent in titration
(2) Forms strong 1:1 complexes regardless of the charge on
the cation
Acidic Properties of EDTA
C C N N
CH
2
-COOH
CH
2
-COOH
HOOC-H
2
C
HOOC-H
2
C
H H
H H
C C N N
CH
2
-COOH
CH
2
-COO
-
-
OOC-H
2
C
HOOC-H
2
C
H H
H H
H
+ +
H
H
4
Y
C C N N
CH
2
-COOH
CH
2
-COO
-
-
OOC-H
2
C
-
OOC-H
2
C
H H
H H
H
+ +
H
C C N N
CH
2
-COO
-
CH
2
-COO
-
-
OOC-H
2
C
-
OOC-H
2
C
H H
H H
H
+ +
H
H
3
Y
-

K
1
=1.0210
-2





H
2
Y
-2

K
2
=2.1410
-3

C C N N
CH
2
-COO
-
CH
2
-COO
-
-
OOC-H
2
C
-
OOC-H
2
C
H H
H H
H
+
C C N N
CH
2
-COO
-
CH
2
-COO
-
-
OOC-H
2
C
-
OOC-H
2
C
H H
H H
HY
-3

K
3
=6.9210
-7





Y
-4

K
4
=5.510
-11

The Nature of EDTA Complexes
with Metal Ions
The reagent combines with metal ions in a 1:1 ratio
regardless of the charge on the cation.


M
+n
+Y
-4
MY
+(n-4)
] ][ [
] [
4
) 4 (
+
+
=
Y M
MY
K
n
n
MY
(1) Multidentate chelating agents form stronger
complexes (K
f
) with metal ions than bidentate
or monodentate ligands.
(2) Neutral EDTA is a tetrabasic acid
(3) Metal-EDTA complex is unstable at both low pH
& high pH.
At low pH
H
+
& M
n+
At high pH
OH
-
& EDTA
For EDTA
] [Y ] [M
] [MY
K MY Y M
4
4
f
4 4
+

+
= +
n
n
n n
Pb
2+
as example:
At pH 10, tartrate is present
to prevent Pb(OH)
2
Pb-tartrate complex must be
less stable than Pb-EDTA
(4) Auxiliary complexing agents:
prevent metal ions from
precipitating.
13-3 Metal Ion Indicators
Metal ion indicator: a compound whose color changes when
it binds to a metal ion.




For an useful indicator, it must bind metal less strongly than
EDTA does. the indicator must release its metal to EDTA
Example: MgIn + EDTA MgEDTA + In
Indicator is pH dependent.
If metal block the indicator, use back titration.
NH
3
NH
3
[H
3
N:Cu:NH
3
]
2+
Cu
2+
+ 4:NH
3
pale bule
deep bule
:
:
Demonstration 13-1 Metal Ion Indicator
Color Changes
P.294
COLOR PLATE 8
Titration of Mg
2+
by EDTA, Using Eriochrome Black T Indicator
(a) Before (left), near (center), and after (right) equivalence point.
(b) Same titration with methyl red added as inert dye to alter
colors.
Demonstration 13-1 Metal Ion Indicator Color Changes
Indicator for EDTA Titrations
Ertichrome Black T
H
2
O+H
2
In
-
HIn
-2
+H
3
O
+
H
2
O+HIn
-2
In
-3
+H
3
O
+
O
2
N
SO
3
-
OH
N
N
OH
K
1
=510
-7

K
2
=2.810
-12
red blue
blue orange
MIn
-
+HY
-3
HIn
-2
+MY
-2
red blue
At the end point:
MgIn + EDTA MgEDTA + In
-
(red) (colourless) (colourless) (Blue)
Before Titration:
Mg
2+
+ In
-
MgIn
(colourless) (blue) (red)
During Titration: Before the end point
Mg
2+
+ EDTA MgEDTA
(free Mg
2+
ions) (Solution red due to MgIn complex)
Compounds changing colour when binding
to metal ion.
K
f
for Metal-In
-
< K
f
for Metal-EDTA.
Requirements for Indicator
Metal-indicator complex must be less stable
than the metal-EDTA complex.
Binding between metal and indicator must not
be too weak. It has to avoid EDTA replacing at
the beginning of the titration.
In general, the metal-indicator complex should
be 10 to 100 times less stable than the metal-
titrant complex.

Eriochrome Black T is blue, but turns red in the presence of metals
13-4 EDTA Titration Techniques
are useful for the determination of [metal]

Direct titration
Titrate with EDTA
Buffered to an appropriate pH
Color distinct indicator
Auxiliary complexing agent

Back titration
Excess EDTA, & titrate with metal ion
For analyte
ppt in the absence of EDTA :
Ex: (Al
3+
-EDTA) at pH 7, indicator Calmagite) back
titration with Zn
2+

react slowly with EDTA
block the indicator
Displacement titration
No satisfactory indicator
Ex1: Hg
2+
+ MgY
2-
HgY
2-
+ Mg
2+
K
f
HgY
2-
>

MgY
2-

Ex2: 2Ag
+
+ Ni(CN)
4
2-
2Ag(CN)
2
+ Ni
2+
, Ni
2+
is titrated with EDTA

Indirect titration
Determine [Anion] that precipitate metal ions: CO
3
2-
, CrO
4
2-
S
2-
SO
4
2-

Ex: SO
4
2-
+ Ba
2+
BaSO
4
(s) at pH 1
filter BaSO
4
(s) and boil with excess EDTA at pH 10
Ba(EDTA)
2-
and excess EDTA is back titration with Mg
2+


Masking
Masking prevents one element from interfering in the analysis of
another element.
Ex: Al
3+
+ Mg
2+
+ F
-
AlF
6
3+
+ Mg
2+
then only Mg
2+
can be react with
EDTA masking Al
3+
with F
-

Masking agent: CN
- ,
F
-
(using with pH control to avoid HCN & HF)

In general, the metal-indicator complex should
be 10 to 100 times less stable than the metal-
titrant complex

Expt:
The formation constants of the EDTA complexes
of Ca
2+
and Mg
2+
are too close to differentiate
between them in an EDTA titration, so they will
titrate together. Ca
2+
can actually be titrated in the
presence of Mg
2+
by raising the pH to 12 with
strong alkali; Mg(OH)
2
precipitates and does not
titrate.

Equilibrium Calculations
Involving EDTA
EDTA titrations are always performed in
solutions that are buffered to a known pH to
avoid interferences by other cations or to
ensure satisfactory indicator behavior.
Conditional Formation Constant
. applicable is for which pH at the only constant a is K
] [
] [
] [
] [
] ][ [
] [
] [ ] [ ] [ ] [ ] [
] [ ] [ ] [ ] [
4
'
MY
) 4 (
4
'
4
) 4 (
4
) 4 (
4 3
2
2
3 4
4 3 2 1 3 2 1
2
2 1
3
1
4
4 3 2 1
4
T
n
n
MY MY
T
n
n
MY
n
n
MY
T
C M
MY
K K
C M
MY
K
Y M
MY
K
Y H Y H Y H HY Y C
K K K K H K K K H K K H K H
K K K K
+
+
+
+
+
+

+ + + +
= =
= =
+ + + + =
+ + + +
=
o
o
o
D
H K K K
D
H K K
D
H K
D
H
K K K K H K K K H K K H K H D
] [
] [
] [
] [
] [ ] [ ] [ ] [
3 2 1
3
2
2 1
2
3
1
1
4
0
4 3 2 1 3 2 1
2
2 1
3
1
4
+
+
+
+
+ + + +
=
=
=
=
+ + + + =
o
o
o
o
13-5 The pH-dependent Metal-EDTA
Equilibrium
Since the anion Y
4-
is the ligand species in complex
formation, the complexation equilibria are affected
markedly by the pH
Fraction Composition of EDTA Solutions
.....
K K K
] [H
K K
] [H
K
] [H
1

1
] [Y
[EDTA]
K K K K K K ] [H K K K K K ] [H K K K K ] [H K K K ] [H K K ] [H K ] [H
K K K K K K

] [EDTA Y
[EDTA]
] [Y

] [Y ] [HY ] Y [H ] Y [H Y] [H ] Y [H ] Y [H
] [Y

6 5 4
3
6 5
2
6
Y
4
6 5 4 3 2 1 5 4 3 2 1
2
4 3 2 1
3
3 2 1
4
2 1
5
1
6
6 5 4 3 2 1
Y
Y
4
4
Y
4 3 2
2 3 4 5
2
6
4
Y
4
4
4 4
4
+ + + + = =
+ + + + + +
=
= =
+ + + + + +
=
+ + +

+ + + + + +

+ +

15D-3 Equilibrium: pH dependent M-Y

Y H 4
4
a4 a3 a2 a1 a3 a2 a1
2
a2 a1
3
a1
4
a4 a3 a2 a1
4
a4 a3 a2 a1
4
a4 a3 a2
3
a4 a3
2
a4 4
4
Y H
4
4
C Y
K K K K ] [H K K K ] [H K K ] [H K ] [H
K K K K

K K K K
] [H
K K K
] [H
K K
] [H
K
] [H
1

1
] [Y
C
=
+ + + +
=
+ + + + = =

+ + + +
+ + + +

Species EDTA as a function of pH

Fig. 9.1. Fraction of EDTA species as a function of pH.
Y
4-
complexes with metal ions, and so the complexation equilibria are very pH dependent.
Only the strongest complexes form in acid solution, e.g., HgY
2-
; CaY
2-
forms in alkaline solution.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Calculation of the Cation
Concentration in EDTA Solutions
Calculate o
4

Calculate conditional formation constants K

Ni
+2
+Y
-4
NiY
-2
18
4
) 4 (
10 2 . 4
] ][ [
] [
= =
+
+
Y Ni
NiY
K
n
n
MY
0.015M-x x x
Calculate equilibrium [Ni
+2
] at pH=3 and pH=8
pH o
4
pH o
4
2
3.710
-14

8
5.410
-3
3
2.510
-11

9
5.210
-2
4
3.610
-9

10
3.510
-1
5
3.510
-7
11
8.510
-1
6
2.210
-5
12
9.810
-1

7
4.810
-4
Value for o4 for EDTA at selected pH value
) ( 10 1 . 8 ] [Ni 10 27 . 2
015 . 0
10 27 . 2 10 2 . 4 10 4 . 5 K 8 pH
) ( 10 2 . 1 ] [Ni 10 05 . 1
015 . 0
10 05 . 1 10 2 . 4 10 5 . 2 K 3 pH
K K
C Y] [H ] Y [H ] Y [H ] [HY ] [Y ] [Ni
10 2 16
2
16 18 3 '
NiY
5 2 8
2
8 18 11 '
NiY
NiY 4
'
NiY
T 4 3
2
2
3 4 2
M x
x
x
M x
x
x
+

+
= = =

= = =
= = =

= = =
=
= + + + + =
Conditional Formation Constant

Most of the EDTA is not Y
4-
below
pH=pK
6
=10.37. The species HY
3-
, H
2
Y
2-
, and so
on, predominate at lower pH.
It is convenient to express the fraction of free
EDTA in the form Y
4-




P.300
The number K
t
f
=
Y
4-
,K
f
is called the conditional formation
constant or the effective formation constant.

P.300

(1) We can use K
f
to calculate the equilibrium concentrations
of the different species at a given pH.
(2) K
f
: HgY
-2
PbY
-2
CaY
-2
K
f
pHK
f

pH
pH9.0 K
f

EDTA(pH9.0)
Complex-Formation Titrations
Formation Constants for EDTA Complexes


Cation K
MY
Log K
MY
Cation K
MY
Log K
MY
Ag
+
2.1 x 10
7
7.32 Cu
2+
6.3 x 10
18
18.80
Mg
2+
4.9 x 10
8
8.69 Zn
2+
3.2 x 10
16
16.50
Ca
2+
5.0 x 10
10
10.70 Cd
2+
2.9 x 10
16
16.46
Sr
2+
4.3 x 10
8
8.63 Hg
2+
6.3 x 10
21
21.80
Ba
2+
5.8 x 10
7
7.76 Pb
2+
1.1 x 10
18
18.04
Mn
2+
6.2 x 10
13
13.79 Al
3+
1.3 x 10
16
16.13
Fe
2+
2.1 x 10
14
14.33 Fe
3+
1.3 x 10
25
25.1
Co
2+
2.0 x 10
16
16.31 V
3+
7.9 x 10
25
25.9
Ni
2+
4.2 x 10
18
18.62 Th
4+
1.6 x 10
23
23.2
Fig. 9.2. Effect of pH on K
f
values for EDTA chelates.
K
f

= conditional formation constant = K

f
o
4
.
It is used at a fixed pH for equilibrium calculations (but varies with pH since o
4
does).
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Fig. 9.3. Titration curves for 100 mL 0.1 M Ca
2+
versus 0.1 M Na
2
EDTA at pH 7 and 10.
As the pH increases, the equilibrium shifts to the right.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Example at p. 277
pH affects the titration of Ca
2+
with EDTA
K
,
f
is smaller at lower pH.

470
Figure 17-7
Influence of pH on the
titration of 0.0100 M
Ca
2+
with 0.0100 M
EDTA. Note that the
end point becomes less
sharp as the pH
decreases because the
complex formation
reaction is less
complete under these
circumstances.
471
Figure 17-8
Titration curves for 50.0 mL of 0.0100 M solutions of
various cations at pH 6.0.
Fig. 9.4. Minimum pH for effective titrations
of various metal ions with EDTA.
The points represent the pH at which the conditional formation
constant, K
f
', for each metal is 10
6
, needed for a sharp end point.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

472
Figure 17-10
Influence of ammonia
concentration on the end
point for the titration of 50.0
mL of 0.00500 M Zn
2+
.
Solutions are buffered to pH
9.00. The shaded region
shows the transition range
for Eriochrome Black T.
Note that ammonia
decreases the change in
pZn in the equivalence-
point region.
The Effect of Other Complexing
Agents on EDTA Titration Curves
Formation constants are the equilibrium
constants for complex ion formation one
ligand at a time.
The overall or cumulative formation of the complex ion at
any given step in this process is denoted as beta, .
For step 2: the cumulative equation is the sum of
equations 1 and 2 in the formation process.
12.5 Auxiliary Complexing Agents
Metal-ligand Equilibria; Fractions of metal ion in
solution: General formula to find fraction of metal ion
in solution with all of its complexed ions:
Problem: Ammonia complexes of zinc: Zn
2+
and NH
3

form four complexes. If the concentration of free,
unprotonated NH
3
is 0.10 M, find the fraction of zinc in
the form Zn
2+
.
Problem: Find the fraction of thallium present when
thallium complexes with 0.20 M CN

. Thallium forms
four complexes with cyanide ion: log K
1
= 13.21, log K
2

= 13.29, log K
3
= 8.67, log K
4
= 7.44.
13-6 EDTA Titration Curves
The end point break depends upon
1) [M
n+
]
2) [L
1
]
3) [pH] selectivity
4) K
f

The smaller K
f
, the more alkaline the solution must
be to obtain a k
f
of 10
6
.

12-3 EDTA Titration Curves
The titration curve is a graph of pM
versus the volume of added EDTA.

The right side figure illustrates for
reaction of 50.0 mL of 0.050 0 M
M
n+
with 0.050 0 M EDTA,
assuming K
f

= 1.15 10
16
,
where the concentration of free
M
n+
decreases as the titration
proceeds.

There are three regions in an
EDTA titration curve:
(a) Before the equivalence point.
(b) At the equivalence point.
(c) After the equivalence point.
EDTA Titration Curve
Region 1
Excess M
n+
left after each addition
of EDTA. Conc. of free metal
equal to conc. of unreacted M
n+
.
Region 2
Equivalence point:[M
n+
] = [EDTA]
Some free M
n+
generated by
MY
n-4
M
n+
+ EDTA
Region 3
Excess EDTA. Virtually all metal
in MY
n-4
form.

Since at equivalence point,
there is exactly as much
EDTA as metal in the
solution, we can treat the
solution as if it had been
made by dissolving pure
MY
n4
. Some free M
n+
is
generated by the slight
dissociation of MY
n4
:




The Ca
2+
end point is more
distinct than the Sr
2+
end
point because the
conditional formation
constant, for CaY
2
is greater
than that of SrY
2

470
Figure 17-6
EDTA titration curves for
50.0 mL of 0.00500 M
Ca
2+
(K
CaY
=1.7510
10
) and
Mg
2+
(K
MgY
=1.7210
8
) at pH
10.0. Note that because of the
larger formation constant, the
reaction of calcium ion with
EDTA is more complete, and a
larger change occurs in the
equivalence-point region. The
shaded areas show the
transition range for the
indicator Eriochrome Black T.
The titration rxn:
M
n+
+ EDTA MY
n-4


K
f
= o
4
K
f


Three regions:
(1) Before equivalence
point : excess M
n+

(2) At equivalence point
[M
n+
]= [EDTA]
(3) After equivalence point :
excess EDTA

Example at p.302
Titration of Ca
+2
and Mg
+2
The K of EDTA of Ca
+2
and Mg
+2
are too
close to differentiate between them in an
EDTA titration.
Generally, they will titrate together.
This titration is used to determine total
hardness of water.

Titration of Ca
+2
EB-T cannot be used to indicate the direct
titration of Ca
+2
in the absence of Mg
+2
with
EDTA.
The indicator forms too weak a complex with
Ca
+2
to give a sharp end point.

Example: calculate the pZn of solutions
prepared by adding 20.0, 25.0, and 30.0 mL of
0.0100M EDTA to 50.0 mL of 0.00500M Zn
2+
.
Assume that both the Zn
2+
and EDTA solutions
are 0.100M in NH
3
and 0.175M NH
4
Cl to provide
a constant pH of 9.0
pH9.0(NH
3
+NH
4
Cl)0.0100M
EDTA50.00mL 0.00500M Zn
2+
pZn
EDTA(a) 20.0 mL (b)25.0 mL (c) 30.0 mL
K
ZnY
:pHNH
3

K"
ZnY
= o
M
o
4
K
ZnY
=
[ZnY
2-
]
C
T
C
M
476
Figure 17-11
Structure and
molecular model of
Eriochrome Black
T. The compound
contains a sulfonic
acid group that
completely
dissociates in
water and two
phenolic groups
that only partially
dissociate.
478
Figure 17-12
Structural formula
and molecular
model of
Calmagite. Note the
similarity to
Eriochrome Black T
(see Figure 17-11).
Example 17-5
Determine the transition ranges for Eriochrome
Black T in titrations of Mg
2+
and Ca
2+
at pH 10.0,
given that (a) the second acid dissociation
constant for the indicator is


(b) The formation constant for MgIn
-
is

(c) Ca
2+
K
f
= 2.5x10
5
H
2
O + HIn
2
-
In
3-
+ H
3
O
+
K
2
= 2.8 x 10
-12
Mg
2+
+ In
3-
MgIn
-
K
f
= 1.0 x 10
7
pH10.0EBTCa
2+
Mg
2+
EBT
Resolution
A small measured amount of Mg
+2
is added to
the Ca
+2
solution.
Ca
+2
gives more stable K than Mg
+2
.
A correction is made for the amount of EDTA
used for titration of the Mg
+2
.

At the end point:
MgIn + EDTA MgEDTA + In
-
(red) (colourless) (colourless) (Blue)
Before Titration:
Ca
+2
+EDTA+Mg
2+
+In
-
MgIn+CaEDTA

During Titration: Before the end point
Ca
2+
+ EDTA CaEDTA

K
f
for Mg
+2
-EDTA < K
f
for Ca
+2
-EDTA.
EDTA titration calculations
Problem 12-7: Consider the titration of 25.0 mL of 0.0200
M MnSO
4
with 0.0100 M EDTA in a solution buffered to
pH 8.00. Calculate pMn
2+
at the following volumes of
added EDTA and sketch the titration curve: (a) 0 ml, (b)
20.0 ml, (c) 40.0 ml, (d) 49.0 ml, (e) 49.9 ml, (f) 50.0 ml,
(g) 50.1 ml, (h) 55.0 ml, (i) 60.0 ml.

Solution: from Table 12.2, we get log(K
f
) = 13.89. At pH
= 8.00, (Y
4-
) = 4.2 x10
-3
.
The above calculation will be carried out based on
whether the titration is before or after the equivalence
point. Here Ve*0.0100 M = 25.0*0.0200 M; Ve = 50.0 ml
(a) to (e) are before the equivalence point and will follow the same
calculation equation:
[Mn
2+
] * (0.025 + V) = 0.025 *0.02 0.01*V


(f) this is the equivalence point
K
f
= 4.2 x10
-3
x 10
13.89
= [MnY
2-
]/([Mn
2+
][EDTA])
= (0.02*0.025/0.075)/ ([Mn
2+
])
2

[Mn
2+
] =8.179 x10
-7
.
pMn
2+
=

Calculations (g) to (i) are beyond the equivalence point, where
[EDTA] can be obtained from the following
[EDTA]*(0.025 + V) = 0.01*V 0.02*0.025
then K
f
= 4.2 x10
-3
x 10
13.89
= [MnY
2-
]/([Mn
2+
][EDTA])
A beaker containing 50.0 mL of 0.300 M Ca
2+
at pH 9 is titrated
with 0.150 M EDTA.
The pCa at the equivalence point is:
(a) 4.97.
(b) 5.13.
(c) 5.84.
For Ca
2+
K
f
= 10
10.65
; = 0.041 at pH = 9
2
' 9
2
1.8 10
f
CaY
K
Ca EDTA

+
(

= =
(

2
2
2
9 9
0.1
1.8 10 1.8 10
CaY
Ca

+
(

( = =


2 6
7.45 10 Ca
+
( =

pCa= 5.13
At the equivalent point, all Ca
2+
ions have formed complex
and free Ca
2+
come from the dissociation of complex:
CaY
2-
Ca2
+
+ EDTA

50 " Mg
2+
0.050M " EDTA
0.050M . pH 10.0 .
Mg
2+
?
K=2.02 x 10
8
EDTA ,
Mg
2+
. : Y
4-
- Mg
2+
1:1 MgY
2-
.
[MgY
2-
] ~

50.0ml x 0.05M

100ml

= 0.025M

Mg
2+
+ Y
4-
MgY
2-
K =

[MgY
2-
]

[Mg
2+
]

[Y
4-
]

= 2.02 x 10
8
0.025M

[Mg
2+
]

= 2.02 x 10
8
[Mg
2+
]

[Mg
2+
] = 1.1 x 10
-5
M

O
CH
3
OH
+
HN
CO
2
-
CO
2
-
CH
3
NH
+
-
O
2
C
-
O
2
C
SO
3
-
Xylenol Orange

M-In + EDTA M-EDTA + In

'





'

M-In + EDTA M-EDTA + In









OH
-
O
3
S
O
2
N
N N
OH
Eriochrome black T
pK
1
=6.3
pK
1
=11.6

EDTA 0.01M
Zn-EDTA
n(EDTA)=n(Zn
2+
)
Erio T

EDTA 0.01M
Zn
2+
, 20ml
Buffer pH=10
Erio T-Zn
Zn
2+
EDTA
Zn
2+
+ EDTA Zn-EDTA
Ca
2+
EDTA
Ca
2+
+ EDTA Ca-EDTA
(x mole) Ca
2+
+ (y mole) EDTA-Mg
(y mole) Ca-EDTA + (y mole) Mg
2+
+ (x-y mole) Ca
2+
x mole > y mole
K(EDTA-Mg) = 4.9 x 10
8
K(EDTA-Ca) = 5.0 x 10
10
EDTA

(y mole) Ca-EDTA + (y mole) Mg-EDTA + (x-y mole) Ca-EDTA

mole EDTA= C x V = (y mole) + (x-y mole) = x mole

1:1
Mg:EDTA
Mg
2+
EDTA
EDTA

Mg
2+
Mg-EDTA

EDTA 0.01M
Ca-EDTA, Mg-EDTA
n(EDTA)=n(Ca
2+
)
Erio T

EDTA 0.01M
Ca
2+
, 20ml
~1ml Mg-EDTA
Buffer pH=10
Erio T-Ca
Ca
2+
EDTA
Ca
2+
+ Mg-EDTA +EDTA Ca-EDTA+ Ca-EDTA + Mg-EDTA
First
2nd
3rd