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Module 2.

2
Applications of Coordination Complexes

Now -a- days chelate compounds are utilized in a number of fields. A few of
them are given here.The applications of coordination compounds are of
great importance. These compounds are widely present in the mineral
,plant and animal worlds. They play many important functions in the area of
analytical chemistry, metallurgy, biological functioning, industry and in
medicine.

I. Applications in qualitative analysis:


a) Separation of AgCl from Hg 2Cl2:
In the I group silver ions precipitate as a white prrecipitate of AgCl, it is
soluble in ammonia due to the formation of [Ag(NH 3)2]Cl.
On the other hand, white ppt of Hg 2Cl2 turns black on treatment with
ammonia.
b) Separation of Cu & Cd ions :
Cadmium ion is separated from a mixture of copper and cadmium ions by
adding KCN solution. Copper ion forms a stable complex with KCN in the
solution. Cadmium complex is unstable: it decomposes to give Cd +2 ions.
These ions give yellow precipitate with H 2S.
c) Test for Fe+2 (Ferrous ion) & Fe+3 (Ferric ion):
Ferrous salt solution gives a deep blue coloured precipitate with potassium
ferri cyanide. This test indicates the presence of ferrous ion.
Ferric salt solution gives deep blue coloured precipitate with potassium
ferro cyanide. This test indicates the presence of ferric ion.
d) Test for K+ and 4+ ion:
Potassium salt solution gives yellow precipitate with sodium cobalti nitrite.
This test indicates the presence of potassium ion.
3K+ + Na3 [Co(NO2)6] K3 [Co(NO2)6]
Yellow precipitate
Nesslers reagent is used for identification of ammonium ion. It gives
reddish brown precipitate.

e) Test for nickel ions:


Nickel salts react with dimethyl glyoxime in presence of ammonium
hydroxide to give a red precipitate of nickel dimethyl glyoximate.

f) The complex Ferroin is used as indicator in some redox titrations.


[Fe(phenanthroline)3]3+
II) Applications in quantitative analysis:
a) Estimation of several cations like Mg 2+, Zn2+, Cu2+, Ni2+ using EDTA as
titrant in the presence of suitable indicator.
Ex: Erio chrome black T
b) Dimethyl glyoxime is used for estimation of nickel. 8-Hydroxy quinolene
is used for estimation of zinc.
c) The hardness of water is estimated by simple titration against EDTA
solution. EDTA forms stable complexes with the metal ions present in the
hard water. i.e., Ca+2 and Mg+2 ions. Since stability constants of calcium
and magnesium complexes of EDTA are different, the selective estimation
of these ions is possible.
III. In photography:
Developed film is fixed by washing it with a dilute solution of sodium
thiosulphate.
AgBr(s) + 2Na2S2O3 (aq) Na3[Ag(S2O3)2](aq) + NaBr(aq)
IV. Electroplating:
Many coordination complexes are used as electrolytes for electroplating.
These complexes deliver the metal ions in controlled manner. For example,
for silver plating the complex K[Ag(CN) 2] is used.
V. Extraction of metals:
Silver and gold are extracted from their respective ores by treatment with
sodium cyanide solution. This also involves complex formation.
Ag+(aq) + 2NaCN(aq) Na[Ag(CN)2](aq) + Na+
Au+(aq) + 2NaCN(aq) Na[Au(CN)2](aq) + Na+

VI. Biological uses:


a) The complex of calcium with EDTA is used to treat lead poisoning.
Inside the body calcium in the complex is replaced by lead. The more
stable Pb-EDTA complex is eliminated in urine.
b) The platinum complex cis [Pt(NH3)2Cl2] known as cisplatin is used as
an anti-tumor agent in the treatment of cancer.
c) Many natural compounds occur as co-ordination complexes.
For example, Haemoglobin [a complex of Fe 2+]
Chlorophyll [a complex of Mg 2+]
Vitamin B12 [a complex of Co2+]
and Carboxypeptidase A [a complex of Zn +2]
VII. Plant growth:
The standard treatment for this problem is supplying Fe(III) EDTA
complex. This complex is soluble in water and readily enters the roots of
trees, where it is eventually converted into a useful form.

VIII. Applications of coordination complexes in analytical chemistry


Broadly classified under the following heads:
1). Use of insoluble inner metallic complexes in gravimetric analysis.
Ex: a) Estimation of Ni(II) as red coloured bis (dimethyl glyoximato)
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nickel(II).
b) tris (8-hydroxy quinolinato) Al(III). As yellow coloured solid.
c) Light green coloured bis (quinaldinato) copper(II) or as dull green
coloured bis (salicylaldoximato) copper(II).
2). Solvent extraction and separation of a metal ion through complexation.
Iron(III) and Al(III) form first order complexes with 8-hydroxy quinoline(L).
FeL3 and AlL3. FeL3 is formed at pH 2-10, and is soluble in chloroform.
AlL3 is formed at a higher pH. And is not readily soluble in CHCl 3.
Therefore they can be separated by addition of 8-hydroxy quinoline and
extracting with CHCl3.
3). Spectrophotometric estimation of trace amounts of metal ions. Several
transition metal ions form complexes with intense colours. They can be
determined by measuring the optical density of the complex at optimum
wave length.
Ex: Fe(II) ion forms dark red complexes with dipyridine or o-phenanthroline,
at
pH 2-9; max = 515 m.
Fe(III) ion forms a complex [Fe(SCN)6]-3 in 0.05-0.5M HNO3; max =
480m

Use of organic sequestering agents in the removal of interference in


gravimetric estimations:
An organic ligand may react with more than one metal ion to form
sparingly soluble precipitates. In such cases direct estimation of a particular
metal ion in the presence of interfering ions is not feasible. A strong
sequestering agent like EDTA is of immense value. It is effective in making
the interfering radicals ineffective. By this makes the organic ligand a
specific reagent for a selected ion.
Ex: Ag+; Cu+2; Ni+2; Co+2; Cd+2 etc are precipitated with an organic ligand,
Benzimidazole, in ammoniacal medium. But in the presence of EDTA, only
Ag+ precipitates quantitatively with benzamidazole, while all other metal
ions form highly stable and soluble EDTA-complexes.
Some more applications of chelate compounds:

Now -a- days chelate compounds are utilized in a number of fields. A few of
them are given here.

i. In medicine:
Heavy metals like lead; mercury iron; copper; nickel; and chromium
are toxic. They form complexes hindering the normal metabolism.
They are eliminated by a suitable chelating agent.

Example:

Dermatitis caused by Cr and Ni is treated with EDTA cream.

Pb and Cu poisoning is treated with Ca EDTA complex. Pb and Cu


form chelates with EDTA and are eliminated.

ii. In softening of hard water:

To prevent scales formation in boilers, calgon (chemical name is


sodium hexa metaphosphate) is added. Then Ca+2 and Mg+2 ions,
that are responsible for hardness of water, are eliminated as complex
compounds.

Ca+2 + [Na4 (PO3)6]2 Ca[Na4 (PO3)6] or [Ca2 (PO3)6]2

iii. Solvent extraction and separation of metal ions through


complexation, can be achieved in the case of metal ions like Iron (III)
and aluminium (III) ions. They form first order complexes with 8-
hydroxyquinoline,(L). 8 Hydroxy quinoline is a very good chelating
agent for the separation and estimation of the two ions. FeL 3 is
formed at pH 2 to 10; and is soluble in chloroform.

AlL3 is formed at higher pH and is not readily soluble in CHCl 3

Therefore they can be separated by addition of 8-Hydroxyquinoline


and extracting with CHCl3 .
iv. In the presence of EDTA, beryllium may be precipitated with
ammonia in the presence of several metal ions like Al +3; Bi+3; Cr+3;
Co+3; Cu+2; K+3; Pb+2 etc.
v. Spectrophotometic estimation of trace amounts of metal ions:
Several transition metal ions form complexes with intense colours.
They can be determined by measuring the optical density of the
complex at optimum wavelength.

m.

Fe(III) ion forms a complex [Fe(SCN) 6 ]-3 in 0.05 0.5M HNO3; max =
480m

vi. Use of insoluble inner metallic complexes in gravimetric analysis:


a) Estimation of Ni(II) as a red coloured bis(dimethylglyoximato)
nickel(II).
b) Tris (8-hydroxy quinolinato)Al(III) as yellow coloured ssolsid.
c) Light green coloured bis(quinaldinato)copper(II) or as dull green
coloured bis(salicylaldoximato) copper(II).

Structure of EDTA:
Detection and the Determination of the Composition of a Complex:-
Today the coordination chemists are fortunate that they can detect and
determine the structure of complexes. Some of the methods are simpler
which are given briefly in the following paras.
Detection of the complexes:- The formation of the complex may be
indicated by several properties of the system. By careful consideration of
one or more of these properties the formation of a complex compound can
be contended.
1. By the change in solubility of the reaction products:
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The solubility of a compound may be either increasing or decreasing


due to the formation of a complex compound. For example AgCN is a
sparingly soluble salt. But when KCN solution is added, it readily
dissolves due to the formation of a complex compound. The reaction
is
AgCN + KCN K[Ag(CN)2]
Potassium argento cyanide
soluble compound
Similarly AgCl dissolves readily in NH4OH solution due to the
formation of a complex, ion [Ag(NH3)2]+
Nickel salts are soluble in water. It is precipitated by the addition of
dimethyl glyoxime. The complex is less soluble than either of the
component materials in it i.e., Ni +2 salt or dimethyl glyoxime.
2. Change of Colour: Sometimes the colour of a chemical changes
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drastically due to complex formation. The following examples serve to


explain it.
Ex 1: CuSO4 is a pale blue coloured salt. It dissolves in water
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easily. To the pale blue solution, when ammonia solution is


added, a dark blue coloured solution is formed due to complex
formation.
Cu+2 + 4NH3 [Cu(NH3)4]+2
Pale blue in Dark blue coloured
solution compound in solution

Ex 2: FeCl3 is straw yellow in colour. On addition of potassium


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thiocyanate solution, a blood-red coloured complex is formed.


Fe+3 + 6SCN [Fe (SCN)6]3
Straw yellow Colourless Blood red colour
colour

These transition metal complexes involve the transition of electrons


from lower energy d-orbital to higher energy d-orbitals .i.e., eg t2g or
t2g eg orbitals. These transitions develop typical colours. The
absorption falls in the visible region of the electromagnetic radiations.

3. pH method: Generally the ligands are either weak acids or weak


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bases. When these ligands are added to a central metal ion, a


complex is formed with the resulting change in the [H +] in the solution.
This might be due to complex formation but not necessarily due to
complex formation.
When boric acid reacts with glycols, H+ ions are produced therefore
the pH of the solution drops.
4. Conductivity measurements: This method is more useful to determine
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the charge on a complex ion, provided the complex is sufficiently


stable. Decrease or increase in the molar conductivity of a solution, in
which the complex is formed, is generally observed. This may be due
to the disappearance or generation of ions possessing higher
conductivity.
For example, copper ions combine with glycinate ions to form the
non-electrolyte bis(glycinato) Cu(II) molecule. Hence the conductivity
decreases.

Another example can also be considered. AgCl is an insoluble


substance. Hence it has a low molar conductivity. NH 3 solution also is
a weak electrolyte in water. When these two unite the conductivity of
the solution increases due to the generation of conducting ions.
AgCl + 2NH3 [Ag(NH3)2]+ + Cl
The measurement of conductivity of a complex also provides
information about the composition of the complex. For example the
conductivity of the uni-univalent complex, [Co(NO2)2(NH3)4]Cl,
indicates that the two NO2 groups are in the coordination sphere.
And the non-electrolytic behaviour of the complex [Pt(NH 3)2Cl2]
indicates that two chloride ions are present in the coordination sphere
and are bound to platinum.

5. Magnetic susceptibility: A measurement of the magnetic susceptibility


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sometimes indicates the formation of a complex. This method also is


used to infer the valence of the metal ion, nature of the bonding and
the geometry of the coordination compound. For example, bis
(dimethyl glyoximato) nickel(II) is diamagnetic indicating a four
coordinated square planar structure. And [NiCl 4]2 is paramagnetic
and has a tetrahedral structure.
UDetermination of the composition of a complex: U

There are several techniques, such as dipole moments


measurements; infra-red spectra; nuclear magnetic resonance;
electron spin resonance etc which may furnish highly valuable
information on the structure of the complex. Here only Jobs method
(Method of continuous variation) is described. This method is
employed for the determination of the formula of a complex.
UPrinciple: This method uses a measureable, additive property of the
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system. The selected additive property should be such that various


species formed by the metal and the ligand in the system have
different values. Optical density is one such common property. Jobs
method is mainly employed in such solutions that contain only one
stable complex.
Consider the solutions of a central metal ion(M) and a ligand(L). The
concentrations of these solutions are known. Generally equimolar
solutions are prepared. A series of solutions is prepared by mixing
the metal ion and the ligand. The two solutions are mixed in
complementary quantities so that the combined volume of the two
solutions remains constant in each of the series of mixtures. (Ex: 1 cc
metal + 1 cc ligand: 2c.c + 8c.c . 9cc metal ion + 1cc ligand. Total
volume = 10 cc).
The concentration of each of the solutions in the series is C
moles/litre. Then for each solution we have
CL + CM = C ------------ (1)
The mole fraction of the ligand in the series changes as C L/CM
changes.
Each of these solutions is diluted with known but fixed quantity of the
solvent, and homogenised. The pH of each of the solutions in the
series is adjusted to an optimum value by adding drops of a strong
acid (HNO3) or an alkali (KOH). Similarly the optimum wave length of
light (max) is selected such that the optical density at the pH and for
the max is maximum for the complex and not for the metal ion or the
ligand. Then the optical density of the solutions prepared is measured
by means of a spectrophotometer. A graph is plotted between the
P A curve
mole fraction of the ligand and the optical density. XL = of the type
shown in the figure given below is obtained. Tangents
are drawn on the two legs of the
Optical density

curve. The point of intersection of the


two tangents gives the number of
ligands bound per metal ion .i.e.
Molefraction of the ligand, XL
coordination number, n, of the metal

XL = ------------ (2)

To get the number of ligands bound per metal ion, the following
manipulations are carried out.
Divide equation (1) by C

+ + = 1 ------------- (3)


But = from equation (2)


+ =1 = 1 -------------- (4)

Then, equation (2) divided by equation (4) gives




= = -------------- (5)
(1 )


But = ;


= --------------- (6)
(1 )

From the value of n, the formation of the complex can be written as


MLn. If XL = 0.5, n = 1 ; complex is ML.
If XL = 0.66; n = 2; the complex formed is ML 2

Limitations of Jobs method:-


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i) The method of continuous variation applies to solutions more


sensitively only if one complex form is present under the experimental
conditions. Sometimes a metal may give more than one stable
complex with the same ligand.
ii) There should not be any volume change on mixing the metal ion
and the ligand solutions.
Assignment questions:
1. What are the main features of (i)coordination number and
(ii)stereochemistry of complex compounds?
2. Write a note on chelate compounds.
3. How are chelate compounds useful to the scientist?