Complexometric Analytical Techniques

Many metal ions form slightly dissociated complex ions. This is possible because most metal
ions can accept unshared pairs of electrons from an anion or molecule to form coordinate
covalent bonds. The product resulting from this reaction is called complex ion.

Many cations will form complexes in solution with a variety of substances that have a pair of
unshared electrons (e.g. on N, O, S atoms in the molecule) capable of satisfying the coordination
number of the metal. The metal ion acts as a Lewis acid (electron pair acceptor) and the
complexing agent is a Lewis base (electron pair donor) The molecule or ion that containing the
donor atom is called the ligand.

Ag+(aq) + 2 H2O(l) Ag(H2O)2+(aq)

In this condition Ag+(aq) tend to be good Lewis acids. It bonds to the water H 2O molecules to
form a hydrated ion. Water is the Lewis base, donating electron pairs to form coordinate
covalent bonds. The number of molecules of the complexing agent will depend on the
coordination number of the metal and on the number of complexing groups on the ligand
molecule. However, if a ligand is added to a solution that forms a stronger bond than the current
ligand (e.g NH3), it will replace the current ligand

Ag(H2O)2+(aq) + 2 NH3(aq) Ag(NH3)2+(aq) + 2 H2O(l)

generally H2O is not included, since its complex ion is always present in aqueous solution

Ag+(aq) + 2 NH3(aq) Ag(NH3)2+(aq)

But simple complexing agents such as ammonia are rarely used as titrating agents because a
sharp end point corresponding to a stoichiometric complex is generally difficult to achieve. This
is true since the stepwise formation constants are frequently close together and not very large,
and a single stoichiometric complex cannot be observed.

Certain ligands that have two or more complexing groups on the molecule, however, do form
well-defined complexes and can be used as titrating agents. This is true because a single
coordinate bond monodentate may form weak bond with metal ion. Thus, a polydentate
multidentate ligand commonly an organic agent which has two or more groups capable of
complexing with a metal ion. This are called a chelating agents.
EDTA (EthylenediamineTetraacetic Acid)

One such reagent that is widely used is ethylenediaminetetraacetic acid (EDTA). The complex
which is formed in this manner is called a chelate. Titration with such a chelating agent is called
a chelometric titration which is a particular type of complexometric titration.

There are six complexing groups in EDTA. We represent EDTA by the symbol H 4Y, which
recognizes the fact that it is a tetraprotic acid. The four hydrogens in the formula refer to the four
acidic hydrogens on the four carboxyl groups. It is the unprotonated ligand Y4- that is responsible
for the formation of complexes with metal ions.

A pair of unshared electrons capable of complexing with a metal ion is located on each of the
two nitrogen atoms and each of the four carboxyl groups. Thus there are six complexing groups
in EDTA. We represent EDTA by the symbol H 4Y, which recognizes the fact that it is a
tetraprotic acid. The four hydrogens in the formula refer to the four acidic hydrogens on the four
carboxyl groups.

It is the unprotonated ligand Y4- that is responsible for the formation of complexes with metal
ions (Mn+)

Mn+ + Y4- <===> MYn-4

Thus, in the determination of Ca by the use of a complexometric titration of the type that is
described above. The titration is performed by adding a standard solution of EDTA to the sample
containing the Ca. The reaction that takes place is the following:

Ca2+ + Y4- <===> CaY2-

Before the equivalence point, the Ca2+ concentration is nearly equal to the amount of unchelated
(unreacted) calcium since the dissociation of the chelate is slight. At the equivalence point and
beyond, pCa is determined from the dissociation of the chelate at the given pH. The equivalence
point is detected through the use of an indicator which is itself a chelating agent. The specific
indicator used is Eriochrome Black T. It contains three ionizable protons and we will represent it
by the formula H3In. In neutral or somewhat basic solutions, it is a doubly dissociated ion, HIn 2-,
which is blue in color. Eriochrome Black T cannot be used as an indicator for the titration of
calcium with EDTA, since it forms too weak a complex with calcium to give a sharp end point.
Therefore, a solution containing the magnesium complex of EDTA, MgY 2-, is introduced into the
titration mixture. Since Ca2+ forms a more stable complex with EDTA than magnesium, the
following reaction occurs:

MgY2- + Ca2+ <===> CaY2- + Mg2+

The magnesium that is released in this manner then reacts with the doubly ionized ion of the
Eriochrome Black T. The complex that is formed between magnesium and that ion is red, hence
at the start of the Ca titration the solution is red. This reaction can be written as follows:
Mg2+ + HIn2-<===> MgIn- + H+
(blue) <===> (red)
The solution is then titrated with a standard solution of EDTA. At the beginning of the titration,
the EDTA reacts with the remaining calcium ion that has not been complexed. After all the
calcium has reacted the next portion of EDTA reacts with the magnesium complex which was
formed earlier. The added EDTA competes favorably with the red magnesium-indicator complex
(MgIn-), to give MgY2- and HIn2-and thereby giving a blue color at the end point.

MgIn- + H+ + Y4- <===> MgY2- + HIn2-

(red) <===> (blue)
pH Limitation of EDTA
In order to get a complete titration, EDTA requires a certain minimum pH for the titration of
each metal ion Note that the metal EDTA complex becomes less stable as pH decreases.

Effects of pH on the composition of an

EDTA solution

End Point becomes less distinct as pH is lowered, limiting the utility of EDTA as a titrant. One
general trend you should see is that as pH gets lower so does the Kf (Formation constant). As a
general rule of thumb we use 10 as a cutoff. Thus Kf must be >=10 for an EDTA titration to
work. Thus pH required when titrating using EDTA is 10. An ammonium buffer is used to
maintain the condition at pH 10.

Addition of EDTA

Determination of the Concentration of Metal ion at Equivalence point

Just as other titrimetric method, the concentration of the concentration of the metal is computed
in the same manner.

moles EDTA = moles analyte

MEDTA x VEDTA = M M+ x V M+

Then Thus
M M+ = MEDTA x VEDTA ppm = M M+ x ( MM M+) x 1000
V M+

In the case of determination of Ca in a solution it is express as ppm CaCO3.

Chemical Masking

Chemical masking is a method use to decrease the concentration of a free metal ion to a level
where a particular interfering reaction will occur. This method is applicable when analyzing a
metal ion in the presence of another metal ion. In this condition, the interfering metal ion is
masked with another agent. Masking agent binds tightly to a metal ion that it will not titrate with
EDTA. These can be used to prevent other ions from interfering in a given titration

Example in the analysis is Cu2+ where Fe 3+ may interfere in the analysis using I2 titration. F - is
introduced to mask Fe 3+ :
Fe 3+ + 6 F - FeF63+

FeF63+ + I2 N.R. Fe is already been masked the Cu2+ thereby

Preventing interference to the reaction of Cu2+ with I2.

Cyanide ion can also be used to mask certain metals in the titration of Ca2+ or Mg2+ with EDTA.
For instance CN- (cyanide) will form strong complexs with Zn2+, Hg2+ Co2+,Cu+, Ag+, Ni2+
Pd2+ Pt2+ Fe2+ and Fe3+, but not Mg2+,Ca2+, Mn2+ or Pb2+ so you can titrate any into in the
second set in the presence of an ion from the first set by adding CN- to the solution (Note CN- is
extremely toxic -dont do this at home) CN- is especially nice because you can demask it with
formaldehyde.

The analytical study in a sample containing Mg and Ca in a brine sample containing only salts of
these two ions. Maybe accomplished by a titration method using the chelating agent, EDTA First,
the titration is conducted under conditions where both ions react with the EDTA, and the end
point is detected after both are titrated. Then, one of the ions (Mg) is precipitated as Mg(OH) 2 by
increasing the pH. A subsequent titration of the solution determines only the remaining Ca ion,
which remains soluble. The Mg content can be determined by difference.

The purpose of this experiment is four-fold:

 improve proficiency with quantitative titrimetric determinations.

introduce complex-formation titrations for determinations of metal ions

using a widely applicable chelating agent, EDTA.
provide an example of determining each of two analytes in a mixture,
implementing a physical separation of analytes by selective precipitation

The analytical study conducted here involves the determination of both the
"total hardness" and the relative concentrations Ca in a brine sample
containing only salts of this ion. This is accomplished by a titration method
using the chelating agent, EDTA (ethylenediamine tetraacetic acid). First, the
titration is conducted under conditions where the ion react with the EDTA, and
the end point is detected after both are titrated. Then, precipitated as
Ca(OH)2 by increasing the pH. A subsequent titration of the solution
determines only the remaining Ca ion, which remains soluble.

(1) The acidification and boiling step is to remove carbonates, which if

present, will precipitate CaCO3 when the solution is made basic. The
precipitate obscures the end point.

(2) As the end point is approached, the color goes from purple to blue. When
you think it is blue, read the buret, then add another drop of titrant; if there is a
perceptible color change, again read buret and add another drop. Continue
until a drop of titrant gives no color change, then record the preceding buret
reading. If CaCO3 or Mg(OH)2 is present, the purple color returns; add more
titrant until the blue color persists for at least one minute.

(3) Trace amounts of many metals, such as Cu or Cd, react with the indicator
and interfere seriously with the end point. If these metals are present, they
can be masked with a few drops of 0.1M KCN

(4) It is necessary to keep the pH at about 10 for two reasons: (a) all reactions
between metal ions and EDTA are pH dependent, and for divalent ions,
solutions must be kept basic (and buffered) for the reaction to go to
completion; (b) the eriochrome black T indicator requires a pH of 8 to 10 for
the desired color change.