COMPLEXOMETRIC TITRATIONS METAL-

METAL-CHELATE COMPLEXES
Chapter 13 Coordination complexes:
metal compounds formed by Lewis acid-base interactions.
Metal ion = Lewis acid electron pair acceptor
Ligand = Lewis base electron pair donor

Monodentate ligands bind through one donor atom only

Polydentate ligands (or chelating agents) bind through more than
one donor atom per ligand

Examples of
polydentate
ligands:

Chelate effect:
EDTA = ETHYLENEDIAMINETETRAACETATIC ACID
Multidentate ligands form more stable complexes than the
equivalent number of monodentate ligands.
due to larger decrease in entropy when monodentate ligands
react
(Recall: Driving force for reactions large ve H and large +ve S)
Forms strong 1:1 complexes with
most metal ions. (Not with Group
1A metals Na, K, Li)

Large formation constants.

Coordinates to the metal through

both N-atoms and O-atoms.

Forms stable water soluble

complexes.

EDTA is a hexaprotic acid. Fraction of EDTA in the form Y4-

HO2CH2C CH2CO2H Highlighted, acidic protons
lost upon metal complexation. EDTA H6Y2+ + H5Y+ + H4Y + H3Y- + H2Y2- + HY3- + Y4-
HNCH2CH2NH
[EDTA] Total concentration of all free uncomplexed EDTA
HO2CH2C CH2CO2H H6Y2+ H5Y+ + H+ species in solution

pK1 = 0.0
H6Y2+ Fraction of EDTA present in the form Y4-:
pK2 = 1.5
Carboxyl [Y 4 ]
Neutral species = H4Y protons 4 =
pK3 = 2.0 Y [H6 Y 2+ ] + [H5 Y + ] + [H4 Y ] + [H3 Y ] + [H2 Y 2 ] + [HY 3 ] + [ Y 4 ]

pK4 = 2.66 [Y 4 ]
4 =
Recall: pK = -log K Y [EDTA ]
pK5 = 6.6
large pK small K Ammonium
protons The value of Y4- is pH dependent!
i.e. loose carboxylic pK6 = 10.24
protons first. Lower pH higher [H+] less EDTA in the form Y4-
HY3- Y4- + H+

1
 Fractional Composition Diagram for EDTA

At this range Y4-

predominates, thus
titrations are routinely
done in buffered solutions
near or above pH 10.

Formation Constant or Stability Constant

Equilibrium constant for the reaction of a metal ion with EDTA is

defined as:
[MY n 4 ]
Mn+ + Y4- MYn-4 Kf =
[Mn + ][ Y 4 ]

NOTE: this does not imply that only Y4- reacts with Mn+.

Only some of the EDTA is present in the form Y4-. How much?

[Y 4 ]
4 = [ Y 4 ] = [EDTA ]
Y [EDTA ] Y 4

where [EDTA] = total concentration of all

EDTA species not bound to a metal ion

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

Conditional / Effective Formation Constant Effective titration:

Reaction must go to completion
[MYn 4 ] Large Kf or Kf' in this case
Kf = Since 4 is pH dependent, so is Kf'
[Mn+ ] [EDTA ] Y
Y4
Metals with higher Kf values can be titrated at lower pH
Fix the pH using buffers is constant.
Y4
Effect of pH on EDTA Titration of Ca 2+
Conditional formation constant (Kf'):

[MYn 4 ]
K f = 4 K f =
Y [Mn+ ][EDTA ] Less distinct
end point
Allows us to consider EDTA complex formation as if the
uncomplexed EDTA is in one form.

Mn+ + EDTA MYn-4 K f = 4 K f

Y

at a fixed pH, find 4 and evaluate Kf'

Y

2
 EDTA Titration Curves Example

Consider the titration of 25.0 mL of 0.020 M MnSO4 with 0.010 M

Region 1 before equivalence EDTA in a solution buffered at pH 8.00.
Excess Mn+ left after each Calculate pMn2+ at the following volumes of added
addition of EDTA. EDTA and sketch the titration curve:
unreacted Mn+. 0.0 mL 50.0 mL
20.0 mL 50.1 mL
40.0 mL 55.0 mL
Region 2 - at equivalence 49.0 mL 60.0 mL
nM = nEDTA or [Mn+] = [EDTA] 49.9 mL
Slight dissociation of MYn-4:
MYn-4 Mn+ + EDTA
At equivalence: Remember: EDTA titrations
n1 = n2 have a 1:1 stoichiometry.
Region 3 - after equivalence
Excess EDTA. c1v1 = c2v2
Virtually all metal in MYn-4
form. (0.020 M)(25.0 mL) = (0.010 M)v2
v2 = 50.0 mL

20.0 mL EDTA before equivalence

Mn2+ + EDTA MnY2-
10-4 mol
nMn = cMnvMn = (0.020 M)(0.0250 L) = 5.0
K f = 4 K f = (5.6 10 3 )(7.41 1013 ) = 4.2 1011 10-4 mol
nEDTA = cEDTAvEDTA = (0.010 M)(0.0200 L) = 2.0
Y

nMn unreacted = (5.0

10-4)-(2.0
10-4) = 3.0
10-4 mol
log Kf = 13.87
Kf = 7.41
1013 nMn unreacted 10-4 mol
3.0
[Mn] unreacted = = = 0.067 M
Kf is large reaction goes to completion vT 0.0450 L

pMn2+ = -log[Mn2+] = 2.18

0.0 mL EDTA:
Also check:
0.020 M Mn2+:
vEDTA / mL pMn2+
pMn2+ = -log[Mn2+] = -log(0.020) = 1.70 0.0 1.70
20.0 2.18
40.0 2.81
49.0 3.87
49.9 4.87

50.0 mL EDTA at equivalence

55.0 mL EDTA after equivalence
nMn = nEDTA or [Mn2+] = [EDTA] Virtually all metal in the form MnY2-
assume negligible dissociation. All Mn2+ in the MnY2- form and there is excess EDTA.
10-4 mol
nMn = cMnvMn = (0.020 M)(0.0250 L) = 5.0
nMn 10-4 mol
5.0 10-4 mol
nMn = cMnvMn = (0.020 M)(0.0250 L) = 5.0
[MnY2-] = = = 0.0067 M
vT 0.0750 L 10-4 mol
nEDTA = cEDTAvEDTA = (0.010 M)(0.0550 L) = 5.50
HOWEVER some dissociation does occur!
Mn2+ + EDTA MnY2- We know Kf for the
forward rxn use it nEDTA excess = (5.50
10-4)-(5.0
10-4) = 5.0
10-5 mol
Initial conc. 0 0 0.0067
+x +x -x nEDTA excess 10-5 mol
5.0
[EDTA] excess = = 10-4 M
= 6.25
Final conc. x x 0.0067 - x vT 0.0800 L

[MnY 2 ] 0.0067 x Kf' large assume nMn 10-4 mol

5.0
= K 'f = 4.2x1011 0.0067-x 0.0067 [MnY2-] = = 10-3 M
= 6.25
[Mn2 + ][EDTA ] x2 vT 0.0800 L
x= [Mn2+] = 1.26 x 107 M
pMn2+ = -log[Mn2+] = 6.9

3
 10-4 M
[EDTA] excess = 6.25 Mn2+-EDTA Titration:
[MnY2-] = 10-3
6.25 M
12

Mn2+ + EDTA MnY2- 10

8
Initial conc. 0 10-4
6.25 10-3
6.25

pMn2+
+x +x -x 6
4
Final conc. x 10-4+x)
(6.25 10-3-x)
(6.25
2
3 0
[MnY 2
] (6.25 10 x)
= K 'f = 4.2x1011 0 10 20 30 40 50 60 70
[Mn2 + ][EDTA ] x(6.25 x10 4 + x )
Volume EDTA / mL
(6.25 10 3 )
4.2x1011
x(6.25 x10 4 ) vEDTA / mL pMn2+ vEDTA / mL pMn2+
0.0 1.70 50.0 6.90
Also check: x = [Mn2+] = 2.4 x 1011 M 20.0 2.18 50.1 8.92
vEDTA / mL pMn2+ 40.0 2.81 55.0 10.62
50.1 8.92 pMn2+ = -log[Mn2+] = 10.6 49.0 3.87 60.0 10.93
55.0 10.62 49.9 4.87
60.0 10.93

EDTA Titration Curves Buffered at pH 10 Auxiliary Complexing Agents

Can introduce a ligand that binds strongly to the metal ion, thus
Greater Kf' greater change at
preventing hydroxide precipitation at high pH.
equivalence

Auxiliary ligand binds more weakly to the metal ion than EDTA.
K f = 4 K f pH dependent
Y
NH3 normally used:
4 decreases as pH NH3 fixes pH and complexes metal species.
Y
decreases
end point more distinct at Tartrate, citrate or triethanolamine have also been used.
higher pH

Ensure no metal hydroxide

precipitation at high pH

Recall: Metal Ligand Equilibria

Ki = stepwise formation constant
i = overall or cumulative formation constant
[ML ] [ML 2 ]
M+L ML 1 = K1 = M + 2L ML2 2 =
[ML ] [M][L ] [M][L ]2
M+L ML 1 = [ML ] = 1[M][L ]
[M][L ]
[ML 2 ]
[ML 2 ] ML + L ML2 K2 =
M + 2L ML2 2 = [ML2 ] = 2 [M][L ] 2 [M][L ]2
[M][L ]2
[ML ] [ML 2 ] [ML 2 ]
Fraction of free or uncomplexed metal ion, M: 2 = K 1K 2 K 1K 2 = = = 2
[M][L ] [ML ][L ] [M][L ]2
[ M] cM = total concentration of all forms of M
M = cM = [M] + [ML] + [ML2] Mass balance expression
cM
In general:
cM = [M] + 1[M][L] + 2[M ][L]2
cM = [M](1 + 1[L] + 2[L]2) n = K1K2Kn

[M] 1
M = M =
[M](1 + 1[L ] + 2 [L ]2 ) 1 + 1[L ] + 2 [L ]2

4
 EDTA Titrations with Auxiliary Complexing Agents
Example

New conditional formation constant if say NH3 is added to the Consider the titration of 50.0 mL of 0.00100 M Zn2+ with 0.00100 M
solution. EDTA at pH 10 in the presence of 0.10 M NH3. (This is the
Consider: concentration of NH3. There is also NH4+ in the solution.)
only some EDTA in the form Y4-
some metal ion is bonded to NH3 Find pZn2+ after addition of 20.0, 50.0 and 60.0 mL of EDTA.

Kf =
Note: We always assume that EDTA is a much stronger complexing
Kf agent than NH3.
Mn+ Y 4
i.e. Kf for EDTA > Kf for NH3
1
where Mn+ =
1 + 1[L ] + 2 [L ]2 + ... + p [L ]p

At equivalence:
Zn2+ forms the following complexes with NH3: c1v1 = c2v2
Zn(NH3)2+, Zn(NH3)22+, Zn(NH3)32+ and Zn(NH3)42+ (0.00100 M)(50.0 mL) = (0.00100 M)v2
v2 = 50.0 mL
1
=
Zn2 + 2
1 + 1[NH3 ] + 2 [NH3 ] + 3 [NH3 ] + 4 [NH3 ] 3 4
20.0 mL EDTA before equivalence
10-5 mol
nZn = cZnvZn = (0.00100 M)(0.0500 L) = 5.00
1 = 1.51 x 102, 2 = 2.69 x 104, 3 = 5.50 x 106, and 4 = 5.01 x 108
10-5 mol
nEDTA = cEDTAvEDTA = (0.00100 M)(0.0200 L) = 2.00
[NH3] = 0.10 M

Very little free Zn2+ in the presence of nZn unreacted = (5.00

10-5)-(2.00
10-5) = 3.00
10-5 mol
2 + = 1.8x10 5
Zn 0.10 M NH3 most Zn2+ complexed by NH3
nZn unreacted 10-5 mol
3.00
CZn unreacted = = = 4.29 10-4 M
vT 0.0700 L
At pH 10 = 0.36
Y4 BUT not all Zn2+ is free, most complexed with NH3
Kf = K [ Zn2+ ] =
Zn2 + Y 4 f C = (1.8 10-5)(4.29 10-4) = 7.7 10-9 M
Zn2 + Zn2 +
= (1.8 x10-5) (0.36) (1016.50) = 2.05 1011 pZn2+ = -log[Zn2+] = 8.1

50.0 mL EDTA at equivalence

60.0 mL EDTA after equivalence
nZn = nEDTA or [Zn2+] = [EDTA]

10-5 mol
nZn = cZnvZn = (0.00100 M)(0.0500 L) = 5.0 Most Zn2+ in the ZnY2- form.
nZn 5.00 10-5 mol
[ZnY2-] = = = 5.00 10-4 M 10-5 mol
nZn = cZnvZn = (0.00100 M)(0.0500 L) = 5.00
vT 0.1000 L
10-5 mol
nEDTA = cEDTAvEDTA = (0.00100 M)(0.0600 L) = 6.00
Some dissociation occurs:
Zn2+ + EDTA ZnY2-
Final conc. x x 5.00 10-4 - x
nEDTA excess = (6.00
10-5)-(5.00
10-5) = 1.00
10-5 mol
[ ZnY 2 ] 5.00 10 4
x
= Kf = 2.05 x1011 nEDTA excess 10-5 mol
1.00
C Zn [EDTA ] x2 [EDTA] excess = = 10-5 M
= 9.09
vT 0.1100 L
x = CZn = 4.94 x 108 M
nZn 10-5 mol
5. 0
[Zn2+] = ZnCZn = (1.8 x10-5)(4.94 10-8) [ZnY2-] = = 10-4 M
= 4.55
vT 0.1100 L
= 8.9 10-13 M
pZn2+ = -log[Zn2+] = 12.1

5
 10-5 M
[EDTA] excess = 9.09 EDTA Titration Curves at Different Concentrations of
10-4 M
[ZnY2-] = 4.55 Auxillary Complexing Reagent (NH3)

Zn2+ + EDTA ZnY2-

Final conc. x 10-5+x)
(9.09 10-4-x)
(4.55

In the presence of excess EDTA, no more interaction between Zn2+

and NH3

K f = 4 K f = (0.36)(3.16 1016 ) = 1.14 1016

Y

[ ZnY 2 ] (4.55 10 4 x )
= K 'f = 1.14 1016
[ Zn2 + ][EDTA ] x(9.09x10 5 + x )

x = [Zn2+] = 4.4 x 1016 M

pZn2+ = -log[Zn2+] = 15.4 Higher [NH3] smaller pM change near the equivalence point
DONT make [NH3] too high

Metal Ion Indicators

Metal ion indicator changes colour when it binds to a metal ion.

It must bind less strongly than EDTA does!
i.e. Kf (Metal-In) < Kf (Metal-EDTA)

E.g.:
MgIn + EDTA MgEDTA + In
(red) (colourless) (colourless) (Blue)

Other ways to detect the end point:

mercury electrode
ion-selective electrode
pH electrode

EDTA Titration Techniques

1. Direct Titration
2. Back Titration
3. Displacement Titration
4. Indirect Titration
5. Masking