Complexometric titrations
Titrimetric methods based on complex formation, sometimes called
complexometric methods, have been used for more than a century.
A chelate is produced when a metal ion coordinates with two or more donor
groups of a single ligand to form a five - or six-member heterocyclic ring.
A ligand that has a single donor group, such as ammonia, is called unidentate
(single - toothed), whereas one such as glycine, which has two groups
available for covalent bonding, is called bidentate. Tridentate, tetradentate,
pentadentate, and hexadentate chelating agents are also known.
Titrimetric methods based on complex formation, sometimes called
complexometric methods, have been used for more than a century.
A chelate is produced when a metal ion coordinates with two or more
donor groups of a single ligand to form a five - or six-member
heterocyclic ring.
A ligand that has a single donor group, such as ammonia, is called
unidentate (single - toothed), whereas one such as glycine, which has
two groups available for covalent bonding, is called bidentate.
Tridentate, tetradentate, pentadentate, and hexadentate chelating
agents are also known.
Amonocarboxylic acid titration:
Tertiary amines that also contain carboxylic acid groups form remarkably stable
chelates with many metal ions.
Ethylenediaminetetraacetic Acid (EDTA):
Ethylenediaminetetraacetic acid-also called (ethylenedinitrilo) tetraacetic acid
which is commonly shortened to EDTA, is the most widely used
complexometric titrant. EDTA
Complexes of EDTA and Metal Ions:
EDTA is a remarkable reagent not only because it forms chelates with all
cations except alkali metals but also because most of these chelates are
sufficiently stable for titrations. Solutions of EDTA are particularly valuable
as titrants because the reagent combines with metal ions in a 1:1 ratio
regardless of the charge on the cation. For example, the silver and aluminum
complexes are formed by the reactions:
Calculation of the Cation Concentration in EDTA Solutions:
In an EDTA titration, we are interested in finding the cation concentration as a
function of f the amount if titrant (EDTA) added. Prior to the equivalence
point, the canon is in excess, and its concentration can be found from the
reaction stoichiometry. At the equivalence point and in the postequivalence-
point region, however, the conditional formation constant of the complex must
be used to calculate the cation concentration. Example below demonstrates
how the cation concentration can be calculated in a solution of an EDTA
complex. Example illustrates this calculation when excess EDTA is present.
Factors that are important in determining the magnitude of
break in titration curve at end point.
1. The stability of complex formed: The greater the stability constant for
complex formed, larger the charge in free metal concentration (pM) at
equivalent point and more clear would be the end point.
2. The number of steps involved in complex formation: Fewer the number
of steps required in the formation of complex, greater would be the break in
titration curve at equivalent point and clear would be the end point.
3. Effect of pH: During a complexometric titration, the pH must be constant
by use of a buffer solution. Control of pH is important since the H+ ion plays
an important role in chelation. Most ligands are basic and bind to H+ ions
throughout a wide range of pH. Some of these H+ ions are frequently displaced
from the ligands (chelating agents) by the metal during chelate formation.
Equation below shows complexation between metal ion and H+ ion for ligand:
M2+ + H2-EDTA2- M-EDTA2- + 2H+
Thus, stability of metal complex is pH dependent. Lower the pH of the
solution, lesser would be the stability of complex (because more H+ ions are
available to compete with the metal ions for ligand). Only metals that form
very stable complexes can be titrated in acidic solution, and metals forming
weak complexes can only be effectively titrated in alkaline solution.
Table-1: Indicators used in complexometric titrations
•
Structures of some pM indicators
Indicators for EDTA Titrations:
In general, these indicators are organic dyes that form colored chelates with
metal ions in a pM range that is characteristic of the particular cation and dye.
The complexes are
often intensely colored and are discernible to the eye at concentrations in the
range of 10-6 to 10-7 M.
Eriochrome Black T is a typical metal ion indicator that is used in the titration
of several common cations. The structural formula of Eriochrome Black T is
shown in Figure. Its behavior as a weak acid is described by the equations:
EDTA is a very unselective reagent because it complexes with numerous
doubly, triply and quadruply charged cations. When a solution containing two
cations which complex with EDTA is titrated without the addition of a
complex-forming indicator, and if a titration error of 0.1% is permissible, then
the ratio of the stability constants of the EDTA complexes of the two metals M
and N must be such that KM/KN ≥ 106 if N is not to interfere with the titration
of M.
EDTA has the widest general application in analyese because of the
following important properties
1. Weak acide , contains 4 acid
2. N atom has unshared pair of electron this means the EDTA molecule has
six potential sides for bonding and considering hexadentate ligand
3. The solubility of free acid is limited , but disodium salt (Na2H2Y)is
soluble in water
4. Form stable complexes with metal ion
5. The end point is readily detected
6. It is reacted with many meatel ions (except the alkali metals and make
complexes with 1:1 ratio
7. Many indicators can be used in thes reactions
8. It has low price
9. It is dissociated in four steps
Titration Methods Employing EDTA:
Direct Titration:
Many of the metals in the periodic table can be determined by titration with
standard EDTA solutions. Some methods are based on indicators that respond
to the analyte itself, while others are based on an added metal ion.
Back-titration Methods:
Back-titration is useful for the determination of cations that form stable EDTA
complexes and for which a satisfactory indicator is not available. A measured
excess of standard EDTA solution is added to the analyte solution. After the
reaction is judged complete, the excess EDTA is back-titrated with a standard
magnesium or zinc ion solution to an Eriochrome Black T.
• Displacement Methods:
• In displacement titrations, an unmeasured excess of a solution containing
the magnesium or zinc complex of EDTA is introduced into the analyte
solution. If the analyte forms a more stable complex than that of
magnesium or zinc, the following displacement reaction occurs:
• where M2+ represents the analyte cation. The liberated Mg2+ or, in some
cases Zn2+, is then titrated with a standard EDTA solution.
The Determination of Water Hardness:
The determination of hardness is a useful analytical test that provides a measure of
the quality of water for household and industrial uses. The test is important to
industry.
because hard water, on being heated, precipitates calcium carbonate, which clogs
boilers and pipes.
Water hardness is ordinarily determined by an EDTA titration after the sample has
been buffered to pH 10. Magnesium, which forms the least stable EDTA complex
of all of the common multivalent cations in typical water samples, is not titrated
until enough reagent has been added to complex all of the other cations in the
sample. Therefore, a magnesium ion indicator, such as Calmagite or Eriochrome
The Determination of Water Hardness:
The determination of hardness is a useful analytical test that provides a measure of
the quality of water for household and industrial uses. The test is important to
industry.
because hard water, on being heated, precipitates calcium carbonate, which clogs
boilers and pipes.
Water hardness is ordinarily determined by an EDTA titration after the sample has
been buffered to pH 10. Magnesium, which forms the least stable EDTA complex
of all of the common multivalent cations in typical water samples, is not titrated
until enough reagent has been added to complex all of the other cations in the
sample. Therefore, a magnesium ion indicator, such as Calmagite or Eriochrome
• Complex metric titration curves
Acomplexometric titration is the one in which the reaction between the
analyate and titrate involves the formation of a complex.
In case of complexometric determination of metals ions we compute pM the
negative log of the free metal ion concentration present in the solution at
different stages of the titration .the plot is similar to one obtained in acid –base
titration
