CHAPTER-3

SUMMARY
 SUMMARY

The main objective of the present investigation is to establish some new, simple, highly
accurate, selective and sensitive methods for the trace determination of titanium and
zirconium to increase their usefulness in routine analysis. The occurrence of titanium
and zirconium in very low concentration in natural samples of wide variety, their
enrichment in the byproduct of many industrial processes and their increasing
applications, demands better methods of detection and determination based on sensitive
and specific reactions of the metal ions. The results have been presented of eight
systems in this thesis involving spectrophotometric methods of determination of
titanium and zirconium and are summarized below in Table.115. The thesis consists of
following eight methods for determination of titanium and zirconium.

The methods (2.1-2.4) include the reaction of titanium with various reagents namely:

2.1 3-hydroxy-2-(3'-methyl-2'-thienyl)-4-oxo-4H-1benzopyran

2.2 6-chloro-3-hydroxy-2-(4'-methoxy phenyl)-4-oxo-4H-1-benzopyran

2.3 6-chloro-3-hydroxy-2-(2'-furyl)-4-oxo-4H-1-benzopyran

2.4 2-hydroxy acetophenone-4-methyl benzoylhydrazone

The methods (2.5-2.8) include the reaction of zirconium with various reagents namely:

2.5 6-chloro-3-hydroxy-2-(2'-hydroxyphenyl)-4-oxo-4H-1-benzopyran

2.6 6-chloro-3-hydroxy-2-phenyl-4-oxo-4H-1-benzopyran

2.7 6-chloro-3-hydroxy-2(2'-thienyl)-4-oxo-4H-1-benzopyran

2.8 6-chloro-2-(2'-furyl)-3-hydroxy-7-methyl-4-oxo-4H-1-benzopyran

In the first method, a yellow colored complex is formed between titanium and 3-
hydroxy-2- (3'-methyl-2'-thienyl)-4-oxo-4H-1-benzopyran in basic medium While the
second one makes use of 6-chloro-3-hydroxy-2-(4'-methoxy phenyl)-4-oxo-4H-1-
benzopyran as a complexing agent for titanium in basic medium. In third method,
spectrophotometric determination of titanium is effected using 6-chloro-3-hydroxy-2-
(2'-furyl)-4-oxo-4H-1-benzopyran for the complexation of the metal ion in acetic acid
solution containing sodium sulphite. The fourth deals with a method employing 2-
hydroxy acetophenone-4-methyl benzoyl hydrazone as a complexing agent for
titanium. In the fifth system, a simple and sensitive spectrophotometric method for
trace determination of zirconium has been worked out by effecting complexation of 6-
chloro-3-hydroxy-2(2'-hydroxyphenyl)-4H-chromone-4-one in propanol-H2O medium.
In the sixth system, a simple and sensitive spectrophotometric method for trace
determination of zirconium has been worked out by effecting complexation of 6-
chloro-3-hydroxy-2-phenyl-4H-chromone-4-one in ethanol-H2O medium. The seventh
system is based on formation of complex between zirconium and 6-chloro-3-hydroxy-
2(2'-thienyl)-4-oxo-4H-1-benzopyran in propanol-H2O medium. The eighth system
furnishes details of a spectrophotometric methods for the trace determination of
zirconium using 6-chloro-3-hydroxy-2(2'-furyl)-7-methyl-4-oxo-4H-1-benzopyran in
propanol-H2O medium.

All these methods summarized below in Table.115, are free from the
interferences of large number of metal ions. Sandell’s sensitivity, standard deviation
and stoichiometry of the complex formed have been determined in each case. Further,
the analysis of a variety of samples including reverberatory flue dust and water samples
has been carried out satisfactorily to a greater extent. The applicability of the method is
tested by analyzing satisfactorily a wide variety of samples with good reproducibility.
All the methods are rapid, simple and employ easily available and relatively
inexpensive chemicals and solvents.
Method in Aqueous conditions i) max (nm) i) Molar absorptivity Non-interfering metal ions
thesis ii) Beer’s law range (L mol-1 cm-1)
(µg/mL) ii) Sandell’s Senstivity
iii) Extractant/ (µg Zr cm-2)
Solvent medium
2.1 Ti(IV).0.10 M NaHCO3, 1.0 mL of 0.05% 3- i) 437 i) 3.614×104 Na(I), K(I), Cr(VI), Se(IV),
hydroxy-2-(3'-methyl-2-(3'-methyl-2'- ii) 0.0-2.5µg Ti/mL ii) 0.00132 Ba(II), Mn(II), Bi(III), Ca(II),
thienyl)-4-oxo-4H-1-benzopyran (in alcohol), iii) Dichloromethane Be(II), Sb(II), Tl(I), Rh(III),
in 10 mL aqueous volume Sr(II), Pb(II), Mo(VI), V(V),
Re(VII), Ce(IV), Th(IV), U(VI),
Ag(I), Cu(II), W(VI), Nb(V)

2.2 Ti(IV).0.06 M NaHCO3, 2.0 mL of 0.05% 6- i) 431 i) 2.75×104 Na(I), K(I), Se(IV), Cr(VI),
chloro-3-hydroxy-2-(4'-methoxyphenyl)-4- ii) 0.0-2.5µg Ti/mL ii) 0.00174 Re(VII), Sr(II), Tl(I), Sb(III),
oxo-4H-1-benzopyran (in alcohol), in 10 mL iii) Chloroform Co(III), Hg(II), Zn(II), Ba(II),
aqueous volume V(V), Cd(II), Ag(I), Ca(II),
U(VI), Rh(III), Mo(VI), Ta(V),
Bi(II), As(III), Be(II), Cu(II),
Ce(IV), W(VI)

2.3 Ti(IV), 0.05 M CH3COOH, 2.0 mL of 5% i) 432 i) 1.659×104 Dy(III), Nd(III), Gd(III),
Na2SO3, 2.0 mL of 0.05% 6-chloro-3- ii) 0.0-2.5µg Ti/mL ii) 0.00289 Ce(IV), Y(III), Mn(II), Sr(III),
hydroxy-2-(2'-furyl)-4-oxo-4H-1-benzopyran iii) Dichloromethane Tl(I), Cd(II), Sm(III), Re(VII),
(in alcohol), in 10 mL aqueous volume Se(IV), Hg(II), Mg(II), Sb(III),
Ca(II), Be(II), Bi(II), V(V),
Ag(I), As(III), Hg(I), Eu(III),
Rh(III), Ba(II), Cu(II)
Method in Aqueous conditions i) max (nm) i) Molar absorptivity Non-interfering metal ions
thesis ii) Beer’s law range (L mol-1 cm-1)
(µg/mL) ii) Sandell’s Senstivity
iii) Extractant/ (µg Zr cm-2)
Solvent medium
2.4 Ti(iv) Ti(IV), 1.0 mL of 0.1% 2-hydroxy i) 371 i) 2.570×104 Na(I), K(I), Co(II), Cd(II),
acetophenone-4-methyl benzoyl hydrazone ii) 0.0-6.0µg Ti/mL ii) 0.00186 Mg(II), Dy(III), Sm(III), Cr(VI),
(in acetone), in 10 mL aqueous volume iii) Carbon tetra Se(IV), Hg(II), Nd(III), Sr(II),
chloride Re(VII), Ca(II), Ag(I), La(III),
Gd(III), Y(III), Tl(I), Ba(II),
Mn(II), Pr(III), Ho(III), Au(III),
Eu(II), Zn(II), Ce(IV), Ni(II),
Th(IV), Bi(II), Os(VIII), Pt(IV),
Hg(I), Sb(III), W(VI)

2.5 Zr(IV), 1.5 mL of 0.05% 6-chloro-3-hydroxy- i) 400 i) 1.780×104 Ca(II), Mg(II), Hg(II), Ba(II),
2-(2'-hydroxyphenyl)-4-oxo-4H-1benzopyran ii) 0.0-6.0 µg Zr/mL ii) 0.00512 Hg(I), Pr(III), Gd(III), Nd(III),
(in alcohol), in 10 mL aqueous volume iii) Propanol-H2O Ho(III), Be(II), Cd(II), Mn(II),
La(III), Sm(III), Y(III), Eu(III),
Dy(III), Tl(I), Sr(II), Re(VII),
Co(III), Ni(II), As(III), Rh(III),
Cu(II), Pt(IV) Al(III), U(VI)
2.6 Zr(IV),1.0 mL of 0.05% 6-chloro-3-hydroxy- i) 413 (i) 2.543×104 Mg(II), Be(II), Ca(II), Cd(II),
2-(phenyl)-4-oxo-4H-1-benzopyran (in ii) 0.0-4.0µg Zr/mL (ii) 0.00359 La(III), Sm(III), Pr(III), Nd(III),
alcohol), in 10 mL aqueous volume iii) Ethanol-H2O Hg(II), Mn(II), Dy(III), Hg(I),
Ho(III), Y(III), Eu(III), Ba(II),
Gd(III), Sr(II), Se(IV), Tl(I),
Co(III), Ni(II), Re(VII), Al(III),
Pt(IV), U(VI), Sb(III), As(III),
Rh(III), Nb(V), Cu(II)
Method in Aqueous conditions i) max (nm) i) Molar absorptivity Non-interfering metal ions
thesis ii) Beer’s law range (L mol-1 cm-1)
(µg/mL) ii) Sandell’s Senstivity
iii) Extractant/ (µg Zr cm-2)
Solvent medium

2.7 Zr(IV), 1.0 mL of 0.05% 6-chloro-3-hydroxy-
2-(2'-thienyl)-4-oxo-4H-1-benzopyran(in
alcohol), in 10 mL aqueous volume
i) 426 i) 1.58×104 Be(II), Ca(II), Cd(II), La(III),
ii) 0.0-5.0µg Zr/mL ii) 0.00578 Sm(III), Pr(III), Gd(III), Nd(III),
iii) Propanol- H2O Hg(II) Ba(II), Mg(II), Hg(I),
Ho(III), Mn(II), Y(III), Eu(III),
Dy(III), Tl(I), Re(VII), Co(III),
Ni(II), Sb(III), As(III), Al(III),
Pt(IV), Rh(III), Sr(II), Se(IV),
U(VI), Cu(II)

2.8 Zr(IV),1.5 mL of 0.05% 6-chloro-2-(2'-furyl)-
3-hydroxy-7-methyl-4-oxo-4H-1-benzopyran
(in alcohol), in 10 mL aqueous volume
i) 416 i) 2.19×104 La(III), Sm(III), Nd(III), Pr(III),
ii) 0.0-5.0µg Zr/mL ii) 0.00347 Be(II), Cd(II), Hg(II), Mg(II),
iii) Propanol- H2O Eu(III), Ca(II), Gd(III), Hg(I),
Ba(II), Ho(III), Y(III), Dy(III),
Mn(II),Co(III), Pt(IV), Tl(I),
Re(VII), Ni(II), Al(III), As(III),
Sr(II), Sb(III), Rh(III), Se(IV),
U(VI), Cu(II)