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5.3 Complexometric Titration

 Titration with EDTA

 EDTA titration curve

 End point detection methods

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 Titrations based on complex formation are called

complexometric titrations

5.3.1 Titration with EDTA

EDTA => Ethylenediaminetetraacetic acid

 EDTA molecule has 6 binding sites for bonding a metal ion.

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Acidic Properties of EDTA

Let H4Y represent the EDTA molecule:

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Figure 5.5: Fraction () of EDTA species as a function of pH.
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Complexes of EDTA and Metal Ions

EDTA is often used as the disodium salt (Na2H2Y).

it reacts with many metal ions to form a complex:

Carrying out the rxn in a basic buffer solution

removes the as it is formed.

 This moves the position of the equilibrium to the right & favors

formation of the complex (Le Châtelier's Principle).

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Q. What is the role of buffer solution in complexometric

titrations of EDTA?

Answer: The buffer adjusts the pH to ensure that the

rxn goes to completion.

 Also, for EDTA,

 Thus, if the solution is buffered to about pH 10.3, most of the

EDTA will exist as ions.

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 Above pH 10.3, most metal ions react quantitatively with

EDTA.

 The reagent (EDTA) combines with metal ions in a 1:1 ratio

regardless of the charge on the cation.

For example:
[ 𝐀𝐠𝐘 ¿¿𝟑−]
𝑲 𝒇= ¿
¿¿¿
[ 𝐀𝐥𝐘 ¿¿ −]
𝑲 𝒇= ¿
¿ ¿¿
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Generally, for metal ion Mn+

Here, [Y4-] is pH-dependent.

𝑲 𝒇 =¿ ¿ ¿
The pH dependence of Y4-:
Define: 4 =

=> [Y4−] =4

where, CT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]

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 Substituting [Y4−] =4 in Kf expression:

= Kf ⟹ = 𝛼 4 Kf

= K f′

Where K = 𝛼 4 Kf is the conditional formation constant.

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To compute free metal ion concentrations:

✈ Use the conditional formation constants, Kf

4 values have been tabulated vs. pH

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5.3.2 EDTA Titration Curve

 Complexometric titration curves are usually a plot of

pM = –log [Mn+] as a function of the titrant volume.

A titration curve for the rxn of Mn+ & EDTA can be plotted as

pM vs. volume of EDTA added as titrant.

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Example:

Construct the titration curve of pCa vs. volume of EDTA

for 50.0 mL of 0.0050M Ca2+ being titrated with 0.010M

EDTA in a solution buffered to a constant pH of 10.0

Given: At pH 10.0, Kf = 5.0 x 1010 & = 0.35

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Solution:

Conditional Formation Constant, K for pH = 10.0

K= (4)(Kf) = (0.35)(5.0 x 1010) = 1.75 x 1010

a) pCa value before any EDTA is added

[Ca2+] = 0.0050M

pCa = -log [Ca2+] = -log (0.0050) = 2.30

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b) pCa values before the equivalence point (10.0mL)

The expected titration reaction is

Ca2+ + Y4- CaY2-

Excess Limited

pCa is calculated from the excess Ca2+

Excess mmol Ca2+ = mmol Ca2+ – mmol of added Y4-

Then, [Ca2+] =
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When 10.0 mL of EDTA solution is added:

mmol Ca2+ soln = 50.0 mL x 0.0050 mmol/mL = 0.250 mmol

mmol Y4- added = 10.0 mL x 0.010 mmol/mL = 0.10 mmol

Excess mmol Ca2+ = mmol Ca2+ present – mmol Y4- added

= 0.250 mmol – 0.10 mmol
= 0.150 mmol
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Then, [Ca2+] = 2.50 x 10-3 M

and

pCa = -log (2.50 x 10-3) = 2.60

Note: Before eq. pt. pCa is calculated in the same way as the

above calculation. Avoid confusion!

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c) pCa value at the equivalence point

At equivalence point: mmol Ca2+ = mmol Y4-

MCa2+ x VCa2+ = MY4- x VY4-

VY4- = = = 25.0 mL

Ca2+ + Y4- CaY2-

at equim. 0.0 mmol 0.0 mmol 0.25 mmol

[CaY2-] = = 0.00333 M
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Note: Here, the dissociation of the CaY2- should be considered

CaY2- Ca2+ + Y4- (where, Kd = )

Initial (M): 0.00333 0.0 0.0

Change (M): - x +x +x

Equil.(M): 0.00333 – x x x

Kd = = 5.71 x 10-11
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𝟏 Kd = = 5.71 x 10-11
𝐊 𝐝= =¿ ¿ ¿
𝐊𝐟
Assuming 0.00333 – x
= 5.71 x 10-11

x = = 4.3 x 10-7

[Ca2+] = x = 4.3 x 10-7 M

and
pCa = -log (4.3 x 10-7) = 6.36
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d) pCa value after equivalence point (>25.0mL of EDTA)

Ca2+ + Y4- CaY2-

Limited Excess

☞ Excess mmol Y4- = mmol Y4-added – mmol Ca2+ present

[Y4-] =

☞ mmol CaY2-formed = mmol Ca2+ reacted

[CaY2-] =
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Now calculate pCa when 30.0 mL of EDTA soln is added:

mmol Ca2+ = 50.0 mL x 0.0050 mmol/mL = 0.250 mmol

mmol Y4-added = = 0.30 mmol

Excess mmol Y4- = 0.30 mmol – 0.250 mmol = 0.05 mmol

[Y4-] =
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= = 0.003125 M

K= =

=
= 1.09 x 10-8 M
✈ pCa = -log (1.09 x 10-8 ) = 7.96

Note: After equivalence point pCa is calculated in the same

way as the above calculation. Avoid confusion!

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Table 5.5:

Data for the titration of 50.0 mL of 0.0050 M Ca2+ with

0.010 M EDTA solution at pH 10.0.

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Vol. EDTA, mL [Ca2+] [CaY2-] CT (M) pCa

0.00 0.0050 2.30

5.00 3.64 x 10-3 2.44
10.00 2.50 x 10-3 2.60
15.00 1.54 x 10-3 2.81
20.00 7.14 x 10-4 3.15
24.00 1.35 x 10-4 3.87
25.00 4.36 x 10-7 0.003333 4.36 x 10-7 6.36 (Eq. pt)
26.00 1.43 x 10-9 0.003289 0.000132 8.85
30.00 2.86 x 10-10 0.003125 0.00025 9.54
35.00 1.43 x 10-10 0.002941 0.001176 9.85
40.00 9.52 x 10-11 0.002778 0.001667 10.02
45.00 7.14 x 10-11 0.002632 0.002105 10.15
50.00 5.71 x 10-11 0.002500 0.002500 10.24
55.00 4.76 x 10-11 0.002381 0.002857 10.32
60.00 4.08 x 10-11 0.002273 0.003182 10.39
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Fi
(0
cu
Figure 5.6: EDTA (0.010 M) titration curve for of
pH
2+
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5.3.3 End Point Detection Method

 Complexometric titration uses the formation of a colored

complex to indicate the endpoint.

Metal ion-Indicator:

is formed when a compound that changes color (indicator)

binds to a metal ion.

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For instance, titration of Mg2+ by EDTA

Eriochrome Black T(EBT) is the common indicator for EDTA

titrations.

Indicator rxn:

Mg2+(Colorless)+ EBT (Blue) MgEBT (Wine red)

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✈ For an EDTA titration, the indicator must bind the metal ion less

strongly than EDTA

☞ Needs to release metal ion to EDTA

MgEBT + EDTA MgEDTA + EBT

(Wine red) (Colorless) (Colorless) (Blue)