Complex Formation Titrations: Dr. Cherrie Pascual Institute of Chemistry UP Diliman

Complex Formation
Titrations
Dr. Cherrie Pascual
Institute of Chemistry
UP Diliman
IMPORTANT DISCLAIMER: THE MATERIALS HERE ARE
SOLELY FOR THE PURPOSE OF INSTRUCTION FOR CHEM
28 CLASSES OF DR. PASCUAL AT IC-UPD AND NOT
INTENDED TO BE REPRODUCED/COPIED FOR ANY
OTHER PURPOSE.
COMPLEX FORMATION TITRATIONS
∙ complexometric titrations
∙ coordination cpds. or complexes – formed by rxn. of
metal ion w/ ligands
∙ Lewis acid-base rxn.
metal ion or central atom (Lewis acid) – e- pair acceptor
ligands – e- pair donor (Lewis base)
chelate – complex produced when metal ion
coordinates w/ 2 or more donor grps. of a single ligand to
form a heterocyclic ring
EDTA
EDTA – hexadentate ligand; 6 donor atoms (2 N & 4 O)

EDTA w/ 4 acidic Hs; w/ 4 Kas
5 various EDTA species in an aq. soln:
H4Y, H3Y-, H2Y2-, HY3 & Y4-
distribution of EDTA species – a fn. of pH
pH 0-2, H4Y predominates
pH 10-14, Y4- predominates
Metal-EDTA Complex: 1:1 regardless of charge of cation
Mn+ + Y4- MY(n-4)+
Ag+ + Y4- AgY3-

Mg2+ + Y4- MgY2-
Al3+ + Y4- AlY-
CT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]
Total molar conc. of uncomplexed EDTA
α-values – give mole fractions of any particular form
Plot α values vs. pH (next curve)

Mn+ + Y4- MY(n-4)+
but [Y4-] = α4CT

conditional or effective formation const.
(pH-dependent Keq; apply at a single pH only)
used to calc. equil concn. of metal ion and
complex at any pt. in titrn. curve
EDTA Titration
EDTA Titration Curves: plot pM vs. VEDTA

Example: Derive a curve for titration of 50.00 ml 0.00500 M Ca2+
w/ 0.0100 M EDTA in soln. buffered to const. pH of 10.0
Ca2+ + Y4- CaY-
= 0.35 × 5.0 × 1010 = 1.75 × 1010

a) Initial pCa (VEDTA = 0.00 ml)
[Ca2+] = 0.00500 M
pCa = 2.30
b) Pre-equiv. pt. (e.g. VEDTA = 10.00 ml)
50.00 × 0.00500 − (10.00 × 0.0100)

[Ca ]=
60.00
= 2.50 × 10-3 M
pCa = 2.60
c) Equiv. pt. – no x’s Ca2+ nor EDTA
VEDTA = 25.00 ml
50.00 × 0.00500
[CaY ]= = 3.33 × 10 M
75.00
[Ca ]=C
CaY
1.75 × 10 =
[Ca ]C
3.33 × 10
[Ca ] = = 4.96 × 10 M
1.75 × 10
pCa = 6.36
d) Post-equiv. pt. (w/ x’s EDTA)
e.g. VEDTA = 35.00 ml
= 1.18 × 10-3 M
[Ca2+] = 1.42 × 10-10 M

pCa = 9.85
Ca2+ w/ larger ΔpM at eq. pt. reg. than Mg2+
due to more complete rxn. bet. Ca2+ & EDTA (see
next curve)
Effect of pH on titration of Ca2+ w/ EDTA:

pH K` CaY the higher the pH
8
8 2.6 × 10 the larger K` CaY
10 1.8 × 10 10 the more feasible
12 4.9 × 10 10 the titration
• Cations w/ larger Kf provide good endpts. even
in acidic soln. (see last curve)
• Fe3+ & In3+ - can be titrated even at strongly

acidic pH (pH = 2)
• Cu2+, Zn2+, Al3+ & Fe2+ - in moderately acidic pH

Auxillary complexing agent
Auxillary complexing agent – sometimes added to keep metal ion in
soln. at pH required for titration.
e.g. Zn2+ titrn. in NH3-NH4Cl buffer
∙ NH3 prevents ↓ of Zn(OH)2 by forming NH3 complexes w/ Zn2+
Titration rxn:
Zn(NH3)42+ + HY3- → ZnY2- + 3 NH3 + NH4+
∙ auxillary complexing agent – decreases sharpness of endpts.; must be

kept at min.
Indicators for EDTA Titrations
Metallochromic indicators – colored organic cpds. (dyes)
that form colored chelates w/ metal ions; chelates of diff.
color fr. free indicator
 widely used: Eriochrome Black T (EBT)

H2In- (red) + H2O HIn2- (blue) + H3O+
HIn2- (blue) + H2O In3- (orange) + H3O+
at pH > 7, blue HIn2- predominates if no metal ion
Endpt. rxn: MIn- (red) + HY3- HIn2- (blue) + MY2-

Kf metal-indic ≤ 1/10 Kf metal –EDTA complex otherwise
premature endpt. observed
Titration Methods Employing EDTA
1)Direct Titrations
2)Back-Titration Methods
3)Displacement Methods
Determination of H2O hardness: a measure of H2O quality;

by EDTA titration
Hardness – refers to total concn. of alkaline earth ions in H2O

[Ca2+] & [Mg2+] > concn. of other alkaline earth ions
Hardness ≡ [Ca2+] + [Mg2+]
Commonly expressed as mg CaCO3/li

soft H2O: Hardness < 60 mg CaCO3/li
Liebig Titration
Liebig Titration of CN- w/ AgNO3
(titrn. involving unidentate ligand)
Ag+ + 2 CN- Ag(CN)2- Kf ≈ 1021
Endpt. – appearance of turbidity due to pptn. of
AgCN
Ag+ + Ag(CN)2- Ag[Ag(CN)2] or 2 AgCN
(x’s Ag+)
# mmol Ag+ = ½ # mmol CN-
Sample Problems
1. Given: Titration of 50.00 ml of 0.0100 M Sr2+ with 0.0200 M EDTA in
a solution buffered to pH 11.0. Calculate pSr values after addition
of a) 0.00 ml, b) 10.00 ml, c) 25.00 ml and d) 30.00 ml of titrant.
Kf of Sr-EDTA complex = 4.3 × 108, at pH 11.0: α4 = 8.5 × 10-1
2. How many grams of NaCN are present in a solution that is titrated
just to a permanent turbidity with 26.05 ml AgNO3 solution
containing 8.125 g AgNO3/L?
3. a) An average of 42.35 ml of EDTA is required to titrate
50.00 ml of standard 0.7682 g MgCO3/L. Calculate the M of
EDTA.
b) Titration of a 25.00 ml sample of mineral water at pH 10
required 18.81 ml of the EDTA solution in (a). A 50.00 ml
aliquot of the mineral water sample was rendered strongly
alkaline to precipitate Mg as Mg(OH)2. Titration with a Ca-
specific indicator required 31.54 ml of EDTA solution.
Calculate ppm CaCO3 and ppm MgCO3 in the sample.
4. How many milliliters of 0.1000 M AgNO3 are required to
titrate to a faint turbidity a solution containing 10.00 mmol
KCN?

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Complex Formation

EDTA – hexadentate ligand; 6 donor atoms (2 N & 4 O)

Ag+ + Y4- AgY3-

Plot α values vs. pH (next curve)

but [Y4-] = α4CT

EDTA Titration Curves: plot pM vs. VEDTA

Ca2+ + Y4- CaY-

= 0.35 × 5.0 × 1010 = 1.75 × 1010

50.00 × 0.00500 − (10.00 × 0.0100)

c) Equiv. pt. – no x’s Ca2+ nor EDTA

[Ca2+] = 1.42 × 10-10 M

Effect of pH on titration of Ca2+ w/ EDTA:

• Fe3+ & In3+ - can be titrated even at strongly

• Cu2+, Zn2+, Al3+ & Fe2+ - in moderately acidic pH

∙ NH3 prevents ↓ of Zn(OH)2 by forming NH3 complexes w/ Zn2+

Zn(NH3)42+ + HY3- → ZnY2- + 3 NH3 + NH4+

∙ auxillary complexing agent – decreases sharpness of endpts.; must be

 widely used: Eriochrome Black T (EBT)

Endpt. rxn: MIn- (red) + HY3- HIn2- (blue) + MY2-

Determination of H2O hardness: a measure of H2O quality;

Hardness – refers to total concn. of alkaline earth ions in H2O

Commonly expressed as mg CaCO3/li

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