1.

8-Hydroxyquinoline
2. Diphenylthiocarbazone
3. Tenoyltrifluoroacetoine
◢ Complexed Formation Titration - Depend on the 4. Ammonium pyrrolidine
combination of ions other than the hydronium and 5. Acetyleacetone
hydroxyl ions to form a soluble, slightly dissociated ions 6. Dibenzo-18-crown-6
or compound as in the titrations of metal ions with an
organic complexion agents such as
Ethylenediaminetetraacetic acid (EDTA)
◢ Complex-formation reagents are widely used in
analytical chemistry. One of the first uses of these
reagents was for titrating cations, the major topic of this
chapter. In addition, many complexes are colored or
absorb ultraviolet radiation; the formation of these
complexes is often the basis for spectrophotometric
determinations. ◢ Ethylenediaminetetraacetic acid [also called
(ethylenedinitrilo)tetraacetic acid], EDTA, a hexadem
which is commonly shortened to EDTA, is the most widely
used complexometric most important a titrant. Fully
◢ Most metal ions react with electron-pair donors to form
protonated EDTA has the structure
coordination compounds or complexes. The donor
species, or ligand, must have at least one pair of unshared
electrons available for bond formation. Water, ammonia,
and halide ions are common inorganic ligands. In fact,
◢ The EDTA molecule has six potential sites for bonding a
most metal ions in aqueous solution actually exist as aquo
metal ion: the four car- boxyl groups and the two amino
complexes. Copper(II), for example, is readily complexed
groups, each of the latter with an unshared pair of
in aqueous solution by water molecules to form species
electrons. Thus, EDTA is a hexadentate ligand.
such as 𝐶𝑢(𝐻2 𝑂)2+ 4 .
◢ EDTA, a hexadentate ligand, is among the metric most
important and widely used reagents in titrimetry.
◢ A ligand is an ion or a molecule that forms a covalent
◢ The various EDTA species are often abbreviated H₄Y,
bond with a cation or a neutral metal atom by donating a
H₃Y¯, H₂Y²¯, HY³¯, and Y⁴¯.
pair of electrons that are then shared by the two.

◢ 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-membered heterocyclic ring.
◢ A ligand that has a single donor group, is called
unidentate, 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.
◢ Many different organic complexing agents have become
important in analytical chemistry because of their
inherent sensitivity and potential selectivity in react- ing
with metal ions. Such reagents are particularly useful in
precipitating metals and in extracting metals from one
solvent to another. The most useful organic reagents
form chelate complexes with metal ions.
◢ 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.
◢ EDTA is a remarkable reagent not only because it forms
chelates with all cations but also because most of these
chelates are sufficiently stable for titrations. This great
stability undoubtedly results from the several complexing
sites within the molecule that give rise to a cagelike
structure in which the cation is effectively surrounded
and isolated from solvent molecules. One of the common
structures for metal/EDTA complexes is shown in Figure
10-6.

Forming Soluble Complexes for Extractions and Other Uses

Many organic reagents are useful in converting metal ions
into forms that can be readily extracted from water into an
immiscible organic phase. Extractions are widely used to
separate metals of interest from potential interfering ions and
for achieving a concentrating effect by extracting into a phase
of smaller volume. Extractions are applicable to much smaller
amounts of metals than precipitations, and they avoid
problems associated with coprecipitation.

◢ Eriochrome Black T is a typical metal-ion indicator used
in the titration of several common cations. The structural
formula of Eriochrome Black T is shown in Figure 10-14.
Its behavior as a weak acid is described by the equations
◢ Note that the acids and their conjugate bases have
different colors. Thus, Eriochrome Black T behaves as an
acid/base indicator as well as a metal-ion indicator.
◢ The metal complexes of Eriochrome Black T are generally
red
◢ The metal complexes of Eriochrome Black T are generally
red, as is H2In¯. Thus, for metal-ion detection, it is
necessary to adjust the pH to 7 or above so that the blue
form of the species, HIn²¯, predominates in the absence
of a metal ion. Until the equivalence point in a titration,
the indicator complexes the excess metal ion so that the
solution is red. With the first slight excess of EDTA, the
solution turns blue as a consequence of the reaction
◢ A properly selected acid-base indicator can be used to
visually indicate the approximate pH of the sample. The
indicator is usually some weak acid or base dye that
changes colors at a definite pH values.
◢ The weak acid formed HIn2 will have one color and the
weak acid negative ion will have a different color
◢ With the first slight excess of EDTA, the solution turns
blue as a consequence of the reaction
◢ Eriochrome Black T can be used in the determination of
total calcium plus magnesium (total hardness) because
both metals have similar formation constants with EDTA
and are titrated together.
◢ A limitation of Eriochrome Black T is that its solutions
decompose slowly with standing. It is claimed that
solutions of Calmagite, an indicator that for all practical
purposes is identical in behavior to Eriochrome Black T.
do not suffer this disadvantage. Many other metal
indicators have been developed for EDTA titrations. In
contrast to Eriochrome Black T, some of these indicators
can be used in strongly acidic media (material)
Several different types of titration can methods can be used
with EDTA as described below
✦ Direct Titration – Direct titration procedures with a
metal-ion indicator that responds to the analyte are the
easiest and most convenient methods to use. Methods
that use an added metal ion are also widely employed.
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, whereas others are based on an added
metal ion.
✦ Potentiometric Methods – Potential measurements can
be used for end-point detection in the EDTA titration of
those metal ions for which specific ion electrodes are
available.
In addition, a mercury electrode can be made sensitive to
EDTA ion and it is used in titrations with these reagents.
✦ Spectrophotometric Methods – Measurement of
UV/visible absorption can also be used to determine the
end points of titrations. In these cases, an instrument
responds to the color change in the titration rather than
relying on a visual determination of the end point.
✦ Back-Titration Methods – Back-titrations are useful for
the determination of cations that form stable EDTA
complexes and for which a satisfactory indicator is not
available; the determination of thallium is an extreme
example.
Back-titrations procedures are used when no suitable
indicator is available, when the reaction between analyte
and EDTA is slow, or when the analyte forms precipitates
at the pH required for its titration.
✦ 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. Displacement titrations are used
when no indicator for an analyte is available.
◢ 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 the common multivalent cations in typical water
samples, does not form a stable EDTA complex until
enough EDTA has been added to complex all the other
cations in the sample. Therefore, a magnesium ion
indicator, such as Calmagite or Eriochrome Black T, can
serve as indicator in water-hardness titrations. Often, a
small concentration of the magnesium-EDTA chelate is
incorporated in the buffer or in the titrant to ensure the
presence of sufficient magnesium ions for satisfactory
indicator action.
◢ Hard water contains calcium, magnesium, and other heavy
metal ions that form precipitates with soap except
detergent.
◢ Precipitation titrimetric is based on reactions that yield
ionic compounds of limited solubility. The slow rate of
formation of precipitates however limits the number of
precipitating agents that can be used in titrations to a
handful.
◢ The most widely used and important precipitating
reagent is the Silver Nitrate; it can be used for the
 determination of halogens, halogen-like anions,
mercaptans, fatty acids, and divalent inorganic anions.
Titrations with Silver Nitrate are sometimes called as
Argentometric Titration
Some chemical indicators are described with specific methods
later in this section.
◢ Three types of end points are encountered in titrations
with silver nitrate:
i. chemical
ii. potentiometric
iii. amperometric
Potentiometric end points are obtained by measuring the
potential between a silver electrode and a reference
electrode whose potential is constant and independent of the
added reagent.
To obtain an amperometric end point, the current generated
between a pair of silver microelectrodes in the solution of the
analyte is measured and plotted as a function of reagent
volume.
The end point produced by a chemical indicator usually
consists of a color change or, occasionally, the appearance or
disappearance of turbidity in the solution being titrated. The
requirements for an indicator for a precipitation titration are
analogous to those for an indicator for a neutralization
titration:
(1) The color change should occur over a limited range in the
p-function of the reagent or the analyte, and
(2) The color change should take place within the steep
portion of the titration curve for the analyte.
◢ The Mohr method was first described in 1865 by K. F.
Mohr, a German pharmaceutical chemist who did much
pioneering work in the development of titrimetry. Because
Cr (VI) is a carcinogen, the Mohr method is no longer in
common use.
◢ Sodium chromate can serve as an indicator for the
argentometric determination of chloride, bromide, and
cyanide ions by reacting with silver ion to form a brick-
red silver chromate (Ag₂CrO4) precipitate in the
equivalence-point region. The reactions involved in the
determination of chloride and bromide (X) are:
The solubility of silver chromate is several times greater than
that of silver chloride or silver bromide. For the titration of
chloride and bromide, it should be possible to select a
chromate ion concentration such that the Ag2CrO4 appears at
a silver ion concentration corresponding to the equivalence
point of the titration.
✦ High chromate ion needed imparts such an intense
yellow color to the solution that it obscures the red color
of the silver chromate.
✦ Lower concentrations of chromate ion are generally used,
and, as a consequence, excess silver nitrate is required
before precipitation begins.
✦ An additional excess of the reagent must also be added to
produce enough silver chromate to be seen. These two
factors create a positive systematic error in the Mohr
method that becomes significant in magnitude at reagent
concentrations lower than about 0.1 M. A good way to
correct for this error is to standardize the silver nitrate
solution against primary-standard-grade sodium chloride
using the same conditions that are to be used in the
analysis. This technique not only compensates for the
over- consumption of reagent but also for the acuity of the
analyst in detecting the appearance of the color.
✦ The Mohr titration must be carried out at a pH of 7 to 10
because chromate ion is the conjugate base of the weak
chromic acid. Consequently, in acidic solutions, where the
pH is less than 7, the chromate ion concentration is too
low to produce the precipitate at the equivalence point.
Normally, a suitable pH is achieved by saturating the
analyte solution with sodium hydrogen carbonate.
◢ An adsorption indicator is an organic compound that
tends to be adsorbed onto the surface of the solid in a
precipitation titration. Ideally, the adsorption (or
desorption) occurs near the equivalence point and results
not only in a color change but also in a transfer of color
from the solution to the solid (or the reverse).
✦ Fluorescein is a typical adsorption indicator useful for the
titration of chloride ion with silver nitrate. In aqueous
solution, fluorescein partially dissociates into hydronium
ions and negatively charged fluoresceinate ions that are
yellow-green. The fluoresceinate ion forms an intensely
red silver salt. Whenever this dye is used as an indicator,
however, its concentration is never large enough to
precipitate as silver fluoresceinate.
✦ In the early stages of the titration of chloride ion with
silver nitrate, the colloidal silver chloride particles are
negatively charged because of adsorption of excess
chloride ions. The dye anions are repelled from this
surface by electrostatic repulsion and impart a yellow-
green color to the solution.
✦ Beyond the equivalence point, however, the silver
chloride particles strongly adsorb silver ions and thereby
acquire a positive charge.
✦ Fluoresceinate anions are now attracted into the
counter-ion layer that surrounds each colloidal silver
chloride particle.
✦ The net result is the appearance of the red color of silver
fluoresceinate in the surface layer of the solution
surrounding the solid.
✦ It is important to emphasize that the color change is an
adsorption (and not a precipitation) process because the
solubility product of the silver fluoresceinate is never
exceeded. The adsorption is reversible.
✦ Titrations involving adsorption indicators are rapid,
accurate, and reliable. Their application, however, is
limited to the relatively few precipitation reactions in
which a colloidal precipitate is formed rapidly.

◢ In the Volhard method, silver ions are titrated with a

standard solution of thiocyanate ion:

Iron(III) serves as the indicator. The solution turns red

with the first slight excess of thiocyanate ion:

The titration must be carried out in acidic solution to prevent

precipitation of iron(III) as the hydrated oxide.

The indicator concentration is not critical in the Volhard

titration. In fact, calculations demonstrate that a titration
error of one part in a thousand or less is possible if the iron(III)
concentration is held between 0.002 and 1.6 M. In practice, it
is found that an indicator concentration greater than 0.2 M
imparts sufficient color to the solution to make detection of
the thiocyanate complex difficult because of the yellow color
of Fe3+. Therefore, lower concentrations (usually about 0.01
M) of iron(III) are preferred.

The most important application of the Volhard method is for

the indirect determination of halide ions. A measured excess
of standard silver nitrate solution is added to the sample, and
the excess silver ion is determined by back-titration with a
standard thiocyanate solution.

The strong acid environment required for the Volhard

procedure represents a distinct advantage over other
titrimetric methods of halide analysis because such ions as
carbonate, oxalate, and arsenate (which form slightly soluble
silver salts in neutral media but not in acidic media) do not
interfere.

Silver chloride is more soluble than silver thiocyanate. As a

consequence, in chloride determinations by the Volhard
method, the reaction occurs to a significant extent near the
end of the back-titration of the excess silver ion. This reaction
causes the end point to fade and results in an
overconsumption of thiocyanate ion, which in turn leads to
low values for the chloride analysis. This error can be
circumvented by filtering the silver chloride before
undertaking the back-titration. Filtration is not required in the
determination of other halides because they all form silver
salts that are less soluble than silver thiocyanate.