Section 8

Complex-Formation Titrations

Complex-Formation Titrations General Principles

Most metal ions form coordination compounds with electron-pair donors (ligands)
Mn+ + qLm- MLqn-mq Kf = [MLqn-mq]/[Mn+][Lm-]q

The number of covalent bonds formed is called the coordination number (e.g. 2,4,6) e.g., Cu2+ has coordination number of 4 Cu2+ + 4 NH3 Cu(NH3)42+ Cu2+ + 4 Cl- Cu(Cl)42-

Complex-Formation Titrations General Principles

Typical Inorganic Complex-Formation Titrations
Analyte
Hg(NO3)2 AgNO3 NiSO4 KCN

Titrant

Remarks

Br-, Cl-, SCN-, Products are neutral mercury(II) CN-, thiourea complexes; various indicators used CNProduct is Ag(CN)2-; indicator is I-; titrate to first turbidity of AgI CNProduct is Ni(CN)42-; indicator is AgI; titrate to first tubidity of AgI Cu2+, Hg2+, Ni2+ Products are Cu(CN)42-, Hg(CN)42-, Ni(CN)42-; various indicators used

Complex-Formation Titrations General Principles

The most useful complex-formation reactions for titrimetry involve chelate formation A 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)

Complex-Formation Titrations General Principles

Chelate Formation Titrations Ligands are classified regarding the number of donor groups available: e.g., NH3 = unidentate (one donor group) Glycine = bidentate (two donor groups) (also, there are tridentate, tetradentate, pentadentate, and hexadentate chelating agents) Multidentate ligands (especially with 4 and 6 donors) are preferred for titrimetry.
react more completely with metal ion usually react in a single step provide sharper end-points

Complex-Formation Titrations General Principles

Aminopolycarboxylic acid ligands
The most useful reagents for complexometric titrations are aminopolycarboxylic acids
(tertiary amines with carboxylic acid groups)

e.g., ethylenediaminetetraacetic acid (EDTA)

EDTA is a hexadentate ligand EDTA forms stable chelates with most metal ions

Complex-Formation Titrations Solution Chemistry of EDTA(H4Y)

EDTA has four acid dissociation steps pKa1= 1.99, pKa2= 2.67, pKa3= 6,16, pKa4= 10.26 5 forms of EDTA, (H4Y, H3Y-, H2Y2-, HY3-, Y4-) EDTA combines with all metal ions in 1:1 ratio Ag+ + Y4- AgY3Fe2+ + Y4- FeY2Al3+ + Y4- AlYKMY = [MYn-4]/[Mn+][Y4-]

Complex-Formation Titrations
Formation Constants for EDTA Complexes

Cation
Ag+ Ca2+

KMY

Log KMY Cation

KMY

Log KMY

2.1 x 107

7.32 8.69

Cu2+ Zn2+ Cd2+

6.3 x 1018 3.2 x 1016 2.9 x 1016

18.80 16.50 16.46

Mg2+ 4.9 x 108

5.0 x 1010 10.70

Sr2+
Ba2+ Fe2+ Co2+

4.3 x 108
5.8 x 107

8.63
7.76

Hg2+
Pb2+ Al3+ Fe3+ V3+

6.3 x 1021
1.1 x 1018 1.3 x 1016 1.3 x 1025 7.9 x 1025

21.80
18.04 16.13 25.1 25.9

Mn2+ 6.2 x 1013 13.79 2.1 x 1014 14.33 2.0 x 1016 16.31

Ni2+

4.2 x 1018 18.62

Th4+

1.6 x 1023

23.2

Complex-Formation Titrations Equilibrium Calculations with EDTA

For Mn+ + Y4- MYn-4 KMY = [MYn-4]/[Mn+][[Y4-] Need to know [Y4-], which is pH-dependent pH dependence of Y4-:

Define: a4 = [Y4-]/CT
CT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y] Conditional Formation Constant, KMY
[MYn-4]/[Mn+][[a4CT] = KMY

KMY = a4 KMY = [MYn-4]/[Mn+][[CT]

Complex-Formation Titrations Equilibrium Calculations with EDTA

Computing free metal ion concentrations: Use conditional formation constants, KMY a4 values depend on pH Thus, KMY are valid for specified pH only a4 values have been tabulated vs pH
a4 = (K1K2K3K4) / ([H+]4 + K1[H+]3 + K1K2[H+]2 + K1K2K3[H+] + K1K2K3K4)

Y4- complexes with metal ions, and so the complexation equilibria are very pH dependent. Only the strongest complexes form in acid solution, e.g., HgY2-; CaY2- forms in alkaline solution.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Fig. 9.1. Fraction of EDTA species as a function of pH.

Kf = conditional formation constant = Kfa4.

It is used at a fixed pH for equilibrium calculations (but varies with pH since a4 does).

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Fig. 9.2. Effect of pH on Kf values for EDTA chelates.

Complex-Formation Titrations Equilibrium Calculations with EDTA

Example: Add excess EDTA to Ni2+ solution at pH 3.0. 50.0 mL 0.0500M EDTA added to 50.0 mL 0.030M Ni2+ Assume very little Ni2+ is uncomplexed: C(NiY ) = [NiY2-] = 50.0 mL x 0.030M/100.0mL = 0.015M C(EDTA) = ((50.0 x 0.050) (50.0 x 0.030))/100.0 = 0.010 M KMY = a4KMY = [NiY2-]/[Ni2+][0.010] =0.015/[Ni2+][0.010] KMY = 4.2 x 1018; a4 = 2.5 x 10-11 @ pH = 3.0 [Ni2+] = 1.4 x 10-8M
2-

Complex-Formation Titrations Metal-EDTA Titration Curves

Titration curve is: pM vs EDTA volume

Conditional Formation Constant, KMY for specific pH e.g., 50.0mL 0.020M Ca2+ with 0.050M EDTA, pH 10.0 at pH 10.0, K(CaY ) = (a4)(KCaY) = (0.35)(5.0 x 1010) = 1.75 x 1010 (a) pCa values before the equivalence point (10.0mL) Ca2+ + Y4- CaY2assume: [CaY2-] = added EDTA dissociated chelate [Ca2+] = unreacted Ca2+ + dissociated chelate Dissociated chelate = CT << [Ca2+], [CaY2-] [Ca2+] =((50.0 x 0.020) (10.0 x 0.050))/(60.0) = 0.0083M pCa = 2.08 at 10.0mL EDTA
2-

Complex-Formation Titrations Metal-EDTA Titration Curves

Titration curve is: pM vs EDTA volume
Conditional Formation Constant, KMY for specific pH e.g., 50.0mL 0.020M Ca2+ with 0.050M EDTA, pH 10.0 at pH 10.0, K(CaY ) = (a4)(KCaY) = (0.35)(5.0 x 1010) = 1.75 x 1010
2-

(b) pCa value at the equivalence point (20.0mL)

assume: [CaY2-] = added EDTA dissociated chelate [Ca2+] = dissociated chelate = CT << [CaY2-]

[CaY2-] = ((20.0mL x 0.050M)/(70.0mL))-CT 0.0142M K(CaY ) = [CaY2-] / [Ca2+] [CT] = (0.0142)/[Ca2+]2 [Ca2+] = ((0.0142)/(1.75 x 1010))1/2 = 9.0 x 10-7M; pCa = 6.05 at 20.0mL EDTA
2-

Note: assumption (CT << [CaY2-]) is OK

Complex-Formation Titrations Metal-EDTA Titration Curves

Titration curve is: pM vs EDTA volume
Conditional Formation Constant, KMY for specific pH e.g., 50.0mL 0.020M Ca2+ with 0.050M EDTA, pH 10.0 at pH 10.0, K(CaY ) = (a4)(KCaY) = (0.35)(5.0 x 1010) = 1.75 x 1010
2-

(c) pCa value after the equivalence point (25.0mL)

assume: [CaY2-] = stoichiometric amount [Ca2+] CT = [excess EDTA] + [Ca2+] [excess EDTA]

CT = ((25.0 x 0.050)-(50.0 x 0.020))/(75.0) = 0.0033M [CaY2-] = ((50.0mL x 0.020M)/(75.0mL))-[Ca2+] 0.0133M K(CaY ) = [CaY2-] / [Ca2+] [CT]; [Ca2+] = (0.0133)/(0.0033)(K(CaY )) [Ca2+] = 2.30 x 10-10 pCa = 9.64 at 25.0mL EDTA
22-

Note: assumption ([Ca2+]<<CT << [CaY2-]) is OK

As the pH increases, the equilibrium shifts to the right.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Fig. 9.3. Titration curves for 100 mL 0.1 M Ca2+ versus 0.1 M Na2EDTA at pH 7 and 10.

The points represent the pH at which the conditional formation constant, Kf', for each metal is 106, needed for a sharp end point.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Fig. 9.4. Minimum pH for effective titrations of various metal ions with EDTA.