Complexometric Reactions

& Titrations
 Is a type of titration based on complex formation
between the analyte and titrant.

 Complexometric titrations are useful for determination

of a mixture of different metal ions in solution.

 Complexes are compounds formed from combination

of metal ions with ligands (complexing agents, electron
donating species). A metal will thus accept electrons
from a ligand where coordination bonds are formed.
 Many complexes are sparingly soluble and can
be used in gravimetric analysis or for
precipitation reactions.

 Complexometry are also used for extracting

cations from solvents.
 Formation of Complexes
 Coordination complexes are neutral compounds or
ionic compound.

 Most metal ions react with electron pair donor to

form coordination compounds or complexes.
 The donor species (Ligands) must have at least one
pair of unshared electrons for bond formation H 2O,
NH3, .......etc.
 When the ligand is an organic compound having
two or more sites (EDTA) for coordinating metal
ions, the ligand is called a chelating agent and the
formed complex is a chelate.
 In aqueous solution, most metal ions exist as
aqueous complexes [Cu(H2O)6]2+
 The number of bonds that a metal ion form with e-

donors is its coordination number.

 Typical coordination numbers are 2,4,6. As an

example, Ag, Cu, Co.......2,4,6, respectively.

 The complexes can be positive, neutral, or negative.

[Cu(NH3)4]2+, [Cu(NH2CH2COO)2], [CuCl4]2-

Note that:
 When neutral ligands coordinate with metal ion,

charge of the formed complex will be same as the

charge of metal ion.
 Formation of coordination complexes is similar to
Lewis acid-base reactions.
 A ligand that has a single donor group is called
Unidentate
-
OH, CN-, F-, Cl-, Br-, NH3, H2O
Whereas a ligand that has two groups available for
bonding a cation is known as Bidentate
1,2-diaminoethane
There are other ligands such as, tridentate,
tetradentate, pentadentate, hexadentate.
EDTA (ethylenediaminetetraacetic acid)
 Also, some functional groups forms
complexes
- Amines

- Sulfonic acids

- Carbonyl group

- Halides

- Carboxy group

In some cases, a ligand can displace another

ligand in order to form more stable complex
 Example
 Dissolving copper sulfate in water. In this case, Cu
Dissolving copper sulfate in water. In this case, Cu
ions form complex with H2O molecules.
[Cu(H2O)4]2+
If you add ammonia slowly, the following reaction
occurs
[Cu(H2O)4]2+ + NH3 [Cu(NH3)(H2O)3]2+

[Cu(NH3)(H2O)3]2+ + NH3 [Cu(NH3)2(H2O)2]2+

And so forth……….
Each of these reactions has equilibrium constant ( Keq)
 The net reaction can be written as
Cu2+ + 4NH3 [Cu(NH3)4] 2+

In the case of complexes, we can write an equilibrium

constant which known as formation constant K f.
Keq= [Cu(NH3)4]2+/[Cu2+][NH3]4 = Kf
ExampleAg+ + NH [Ag(NH )]+
3 3

Kf =[Ag(NH3)]+/[Ag+][NH3] = 2.5 x 103

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

Kf =[Ag(NH3)2]+/[Ag(NH3)]+[NH3] = 1.0 x 104

 The overall reaction is the sum of the two steps
and the overall formation constant is the product
of the stepwise
+ +
Ag + 2NH3 [Ag(NH3)2]
Kf = [Ag(NH3)2]+/[Ag+][NH3]2 =2.5 x 107

The formation constant is also called the stability

constant, Ks.
 The equilibrium constant for dissociation of the complex
is called instability constant (Ki) or dissociation constant
(Kd).

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

Keq = [Ag+][NH3]2/ [Ag(NH3)2]+ = Kd = 1/ Kf

 Kf = 1/ Ki
The value of Kf indicates stability of the complex
 Complexation Equilibria
Complexation reactions involve a metal ion M
reacting with a ligand L to form a complex
ML.
M + L = ML
Complexation reactions occur in a stepwise
fashion
ML + L = ML2
ML2 + L = ML3
MLn-1 + L = MLn
Each of these reactions has formation constant.
 Metal ions and ligands
 Cu, Co, Ni, Zn, Cd, and Hg (II) form stable
complexes with N ligands (NH3 and
triethylenetetraamine (trien))

 Al, Pb, and Bi are better complexed with ligands

containing O atoms.

 Chelating agents with both O and N (EDTA as an

example) forms stable complexes with different
metals.
 EDTA (polyaminocarboxylic
acid)
 EDTA is widely used as a complexometric titrant for
metals.

It is a hexadentate ligand, as it has six sites for binding a
metal ion
4 carboxyl groups and 2 amino groups
It is also the most widely used chelating agent in titrations.
 Chelating agent is an organic compound that has two or

more groups capable of complexing with a metal ion. The

complex formed is called a chelate.
chelating agent = ligand
 Titration with a chelating agent is called a chelometric

titration.
 EDTA Equilibria
 EDTA = H4Y (tetraprotic acid)
H4Y have four Ka values corresponding to the stepwise
dissociation of the four protons.
H4Y = H + + H 3Y- Ka1= 1.0 x 102-
H3Y- = H+ + H2Y2- Ka2= 2.2 x 103-
Ka3= 6.9 x 107-
Ka4= 5.5 x 1011-
Because H4Y has a very low solubility in water, the
disodium salt Na2H2Y.2H2O is usually used.
 Complexes of EDTA and metal
ions
Solutions of EDTA are important as titrants
because it combines with metal ions in a 1:1 ratio
EDTA
Mn+
1:1 complex
Regardless of the charge on the cation
Example
Ag+ + Y4- = AgY3-
Al3+ + Y4- = AlY-
 EDTA is a remarkable reagent because:
- It forms chelates with all cations EXCEPT
alkali metals.
- Most of these chelates are stable for titrations.
- The great stability results from the six
complexing sites within the molecule as shown
in the following structure
 Equilibrium Calculations
involving EDTA
 EDTA titrations are always performed in solutions
that are buffered to a known pH to:
- Avoid interferences by other cations
OR
- To ensure satisfactory indicator behavior.
 Calculating [Mn+] in a buffered solution containing

EDTA when the pH is known.

 Conditional Formation Constant
 Consider the following equation
Mn+ + Y4- = MY(n-4)+
Kf = [MY(n-4)+] / [Mn+][Y4-]............ (1)
4 = [Y4-] / CT
CT = [Y4-] + [HY3-] + [H2Y2-] + H3Y-] + [H4Y]
Substitute 4CT for [Y4-] from equation (1) in the Kf
expression
Kf = [MY(n-4)+] / [Mn+]4CT
By combining 4 and Kf, we get the C.F.C (Kf)
Kf 4= Kf= [MY(n-4)+] / [Mn+]CT
Where K  is a constant only at the pH for which  is applicable.
 Example
 Calculate the concentration of Ni2+ in a solution that
was prepared by mixing 45.0 mL of 0.040 M Ni 2+
with 55.0 mL of 0.050 M EDTA. The mixture was
buffered to a pH of 3.0. Kf =1.05 x 108
Solution
CNiY2- = 45.0 x 0.040 / 100= X M
CEDTA= (55.0 x 0.050) – (45.0 x 0.040) / 100= Y M
Kf = X / [Ni2+] Y
[Ni2+] = X / Y (1.05 x 108)= Z M
Titration curves for 50 mL of 0.0050
M Ca2+ & Mg2+ with EDTA @ pH
10.0
Kf = 1.75 x 1010

Kf = 1.72 x 108

Transition range for

the EBT ind.
 Effect of pH on the titration of
0.010 M Ca2+ with 0.010 M EDTA
Titration curves for 50 mL of
0.010 M solns of different metal
ions @ pH 6.0
Minimum pH needed for
titration of different cations with
EDTA
 Indicators for EDTA Titrations
 Several organic compounds are used as indicators
for metal ions in EDTA titration.
 Eriochrome Black T (E.B.T).

MIn- + HY3- = HIn2- + MY2-

Red Blue
 The metal-indicator complex must be less stable
than that of metal-EDTA complex or the EDTA will
not displace it from the metal.
 Solutions of E.B.T must be freshly prepared, as it is
unstable in solution.
EBT Indicator
 Calmagite

Calmagite is another indicator used for

complexometric titration. Calmagite has a similar
structure to E.B.T.
Calmagite Indicator
 Titrations Methods Employing
EDTA OR
Applications of Chelometric
Titrations
- Direct Titration - Back Titration - Displacement Titration

Direct Titration
 Many metals can be determined by titration with standard

EDTA solutions using metallochromic indicators.

 An NH – NH Cl buffer (pH= 9 - 10) is used for metals
3 4
which form complexes with ammonia.

This method can be performed by direct titration with

EDTA using metal ion indicators.
 In this method, Mn+ solution should be adjusted to
the suitable pH + Ind.; titrate with EDTA up to the
eq.p. (color of the ind. will be changed). This
method can be used for determination of Al, Ba, Bi,
Cd, Ca, Ce, Cu, Hg, Mg, Fe, Ni, Zn, Pb, Zr, Sc, Sr,
……..etc
 Back Titration
 This method is useful for determination of metal ions that is
difficult to determine by direct titration; it is used when:

- The reaction between the metal ion and EDTA is slow OR

- A satisfactory ind. is unavailable.

* In this method, a measured excess of EDTA soln. is added to

the analyte soln. (to prevent precipitate formation) ; the exces
EDTA is back titrated with a standard Mg or Zn ion solution
in the presence of E.B.T or Calmagite up to the end point.
 This method is also useful for cations such as Cr (III) and

Co (III) that react slowly with EDTA.

 Displacement Titration
 In this method, an excess of a solution containing the Mg or
Zn complex of EDTA is added to the analyte solution. The
analyte will displace Mg or Zn ion (the analyte complex is
more stable than that of Mg or Zn). The liberated Mg 2+ or
Zn2+ is then titrated with a standard EDTA soln.

MgY2- + M2+ MY2- + Mg2+

 Displacement methods are useful where no satisfactory

indicator is available for the metal ion being determined.
 Advantages of EDTA as a
Complexing Agent
 EDTA has six coordination sites and therefore can form
up to six coordination bonds.
 Form stable complexes with most cations at different pH
values.
 Combines with metal ions in a 1:1 mole ratio, regardless
of the charge on the cation.
 Its disodium salt is water soluble and can be obtained in a
high purity, therefore can be used as a primary standard
material.
 Has a high molecular weight, thus the error in weighing is
very small or negligible.
 Titration Curve
 Draw a curve for the titration of 38 mL of a solution
of 0.010 M Ca2+ with 0.010 M EDTA. Calculate pCa
after addition of 0.00, 15, 30, 37, 38, 39, 48 and 59
mL of EDTA. K`f= 1.8 x 1010
 Titration Curve
 Preequivalence
[M]= Original V. of M x[M] – Added V. of L x [L]

 At the Eq. point

Total V
Eq. V. of L x [L]

Total V
[M]=
 Postequivalence
Postequivalence K `f
Eq. V. of L
(Added V. of L – Eq. V. of L)

[M]=
K `f
 Masking and Demasking Agents
 Zn, Mg, and Pb can be determined in a single
sample by performing 3 titrations

2 titrations with EDTA 1 titration with Mg2+

- Treat the sample with an excess of NaCN. NaCN masks
Zn2+ & prevent it from reacting with EDTA.
Zn2+ + 4CN- = Zn(CN)42-
 EDTA Mg2+ soln. EDTA

CH2SHCHSHCH2OH

Y4- Zn2+
Pb2+ & Mg2+

2- + 4-
PbY + 2R(SH)2 Pb(RS)2 + 2H + Y

Zn(CN)4- + 4HCHO + 4H2O Zn2+ + 4HOCH2CN + 4-OH

 Titration of CN- by using AgNO3
Cyanometric titrations
 It is a type of titration that involving a ligand and a
metal ion.
+ -
Ag + CN [Ag(CN)2]-
This complex is very stable
The end point of this titration can be recognized by
appearance of turbidity due to the precipitation of
silver cyanide:
+ -
Ag + [Ag(CN)2] 2 AgCN
OR Ag+ + [Ag(CN)2]- Ag[Ag(CN)2]
 This method for determination of CN- is called Liebig’s
method.
 Turbidity of the solution appears after [CN -] has dropped to
a low conc. However, in practical, the equivalence point can
be recognized only by formation of precipitate.
 The end point occurs early during the titration and that is
why NH3 is added, which resulting in [Ag(NH3)2]+
formation.
 The problem in using this method is that the silver cyanide
precipitate is slow to redissolve and it is time consuming.
 In 1983, Deniges has modified this method by using I - as
the indicator. Precipitated AgI is less soluble than silver
cyanide and thus precipitates in place of the latter at the end
point. [Ag(NH ) ]+ + I- AgI + 2NH
3 2 3