CHEM 301 LECTURE

Unit 10. COMPLEXOMETRIC TITRATION

I. Complex Ion Formation

one of the factors that affect solubility of compounds in water
increases solubility
example: formation of the silver-ammonia complex
Ag+ + 2NH3 Ag(NH3)2+ Kf = 1.5 x 107 formation constant (always >1)

Example:
1. Calculate the molar solubility of AgCl (Ksp =1.6 x 10-10 ) in 1.0 M NH3.

Solution:
The reactions involved are the solubility equilibrium of AgCl and the formation of the silver-ammonia complex:

AgCl Ag+ + Cl- Ksp = 1.6 x 10-10

+
Ag + 2NH3 Ag(NH3)2+ Kf = 1.5 x 107
AgCl + 2NH3 Ag(NH3 )2+ + Cl- K = 2.4 x 10-3

-3 + -
K = 2.4 x 10 = [Ag(NH3 )2 ][Cl ] = (s)(s)
[NH3]2 (1-2s)2

s = 0.049 s = 0.045 M
(1-2s)

II. Coordination Compounds

consist of a complex ion and a counter ion

complex ion
a charged species in which a central metal ion is bonded to molecules or ions called ligands
type of bond: Lewis acid-base (metal - acid; ligand - base)

+ +2
examples: complex ions: Ag(NH3)2 Cu(NH3)4
Fe(CN)6-4 HgI4-2

coordination compound:
a. with complex cation: [Co(NH3)6]Cl3
b. with complex anion: Fe4[Fe(CN)6]3
c. cation and anion are complexes: [Co(H2O)6][Co(CN)6]
d. with more than 1 kind of ligand: Ca[Cu(OH)3(Br)(NH3 )2]

coordination number: number of atoms bonded to the central atom

donor atom: atom in the ligand that is directly bonded to the central atom

1 of 5
CHEM 301 LECTURE

types of ligands:
- - -
monodentate: H2O, NH3, OH , Cl , Br
bidentate: C2O4-2
polydentate: EDTA - hexadentate (6 donor atoms capable of bonding with a metal ion)

Example: consider the complex: [Cd(C2O4)2(NH3)2]-1

what is the oxidation number of Cd? +3
how many type of ligands are present? 2
what is the coordination number around Cd? 6
what is the donor atom of NH3? N
-2
what is the donor atom of C2O4 ? O

III. Formula Writing

1. The formula of a complex should be enclosed in square brackets [ ], charged or not.
2. The symbol of the metal is written first, followed by anionic ligands, and finally by neutral ligands.

examples: [Ag(NH3)2]+ [Fe(CN)6]-4 [Co(CN)4(NH3)2]+2

some common ligands:

ligand ligand name
H2O aquo or aqua
NH3 ammine
Cl- chloro
OH- hydroxo
-2
O oxo
CO3-2 carbonato
C2O4-2 oxalato
CN- cyanato or cyano
SCN- thiocyanato
NO2- nitrito
NO3- nitro
EDTA ethylene diamine tetraacetic acid

2 of 5
CHEM 301 LECTURE

IV. Nomenclature of Coordination Compounds

Consider the compound with an anionic complex: Ca[Cu(OH)3(Br)(NH3 )2]

1. The cation is named before the anion. calcium __________

2. Within a complex, the ligands are named first, in alphabetical order, the metal ion last:

calcium __ammine__bromo__hydroxo_________

3. The number of ligands of the same kind in a complex is indicated by Greek prefixes di-, tri-, tetra-…
Note: prefixes are not regarded in alphabetical arrangement.

calcium diamminebromotrihydroxo_________

4. If the complex is an anion, end in –ate.

calcium diamminebromotrihydroxocuprate

5. The oxidation number of the transition metal is indicated by Roman numerals.

calcium diamminebromotrihydroxocuprate(II)

Note: (a) it is not necessary to indicate the oxidation number of calcium since it is a
representative element.
(b) the name of the complex is a single word.

more examples:

compound/ion systematic name

[Ag(NH3)2]+ diamminesilver(I)

[Co(NH3)6]Cl3 hexamminecobalt(III) chloride

Fe4[Fe(CN)6]3 iron(III) hexacyanoferrate(II)

[Co(H2O)6][Co(CN)6] hexaaquocobalt(III) hexacyanocobaltate(III)

Na4[Mn(CN)4(SCN)2] sodium tetracyanodithiocyanatomanganate(II)

3 of 5
CHEM 301 LECTURE

V. Complexometric Titration

basis: formation of stable complex ion between a metal (M) ion and a complexing agent (ligand, L)

M + L M-L
metal ion chelon chelate

chelon: polydentate ligand that form stable, water-soluble 1:1 complex with a metal ion
chelate: cyclic complex ion formed by the cation and the ligand

chelometric titration: the amount of chelon added is measured

titrant: ethylenediaminetetraacetic acid (EDTA, H4Y)

used in preparation: disodium EDTA, Na2H2Y

NaOH: to increase solubility of Na2H2Y O -2

buffered to pH 10: to obtain full anionic form, Y-4 O C

O CH2
C CH2
O O N
O
-*
*- CH2
CH2 C O Ca
O C CH2
* * N CH2
O
N CH2 CH2 N CH2
C
-* *- CH2
O C CH2 CH2 C O O O C

O O O
* six donor atoms
CaY-2

indicators:
SO3-
SO3-
O2N

OH OH
- N
eriochrome black T (EBT, H2In ) N calmagite
N N
OH
OH
CH 3

Hardness of water: - due to minerals that dissolve in water

+2 +2
- Ca and Mg form precipitate with soap
- other ions: iron, aluminum, manganese, zinc
- the hardness of water is measured as ppm CaCO 3

4 of 5
CHEM 301 LECTURE

Example:
In the analysis of a hard water sample, a 50.0 mL sample was titrated with a 0.1473 M EDTA solution to reach the
end point. If the titration required 38.50 mL of EDTA, calculate the hardness of the water sample as ppm CaCO 3
(100.1 g/mol).

at equivalence point: mol CaCO3 = mol EDTA x (1 CaCO3/ 1EDTA)

= (M x V)EDTA x (1/1)

ppm (mg/L) CaCO3 = mol CaCO3 x MM x 1000(mg/g) / L sample

Answer: 11,400 ppm

VI. EDTA Titration

Reactions involved:
• initial reaction in flask: Ca2+ + HIn2- CaIn- + H+ CaIn- is wine red in color
• titration reactions: Ca2+ + H2Y2- CaY2- + H+ EDTA binds with Ca2+
CaIn- + MgY2- CaY2- + MgIn- formation of CaY2- more preferred
than MgY2-
• indicator reaction: MgIn- + H2Y2- MgY2- + H2In- formation of MgY2- more preferred
-
than wine red MgIn ; clear blue
HIn2- is produced
Kf: CaY2- > MgY2- > CaIn- > MgIn-

at equivalence point:
moles EDTA = moles Ca2+
moles EDTA = moles CaCO 3
(M x V)EDTA = grams CaCO3/MM

VII. EDTA Titer

an alternative unit of concentration for EDTA other than molarity

titer: mg CaCO3 equivalent 1 mL of EDTA

EDTA titer = mg CaCO 3/mL EDTA

5 of 5