Chapter: IV

Results and Discussion on Electronic Absorption Spectra,

powdered XRD and Thermoanalytical studies of metal
complexes
Section A
Electronic Absorption Spectral Study of Complexes:
Cu(II) complexes:
The Cu (II) complexes display three absorption bands at
10548-10593(υ1), 16420-16528(υ2) and 24271-24449(υ3) cm-1 which
are assigned to 2B1g-2A1g, 2B1g-2B2g and 2B1g-2Eg transitions. The
Position of these bands and their assignments suggest distorted
octahedral geometry. The electronic absorption spectra of Cu(II)
complexes and their positions are shown in figure 4.1-4.2and the data
is represented in table 4.1.
Mounika et. al[1] reported electronic spectra of Cu(II) complex
displayed three prominent bands at 16558, 24096 and 38461 cm-1 due
to 2Eg-2T2g, symmetry forbidden ligand-metal charge transfer and
ligand bands. On the basis of electronic spectra, a distorted octahedral
geometry around Cu (II) is suggested.
Table 4.1: Electronic Absorption Spectral data of Cu(II)
complexes.
Sr. No. Complex Absorption maxima cm-1 (nm)
υ1 υ2 υ3
1 Cu-L1 944 (10593) 605(16528) 409(24449)
2 Cu-L2 945(10582) 607(16474) 411(24330)
3 Cu-L3 948(10548) 609(16420) 410(24390)
4 Cu-L4 946(10570) 607(16474) 409(24449)
5 Cu-L5 945(10582) 606(16501) 411(24330)
6 Cu-L6 948(10548) 608(16447) 412(24271)

133
Figure 4.1: Electronic absorption spectrum of Cu-L1

Figure 4.2: Electronic absorption spectrum of Cu-L5

134
Ni(II) Complexes:

The electronic spectra of the Ni(II) complexes, showed d-d

bands in the region 24449-24937(υ3), 16528-16611(υ2) and 12970-
13280(υ1) cm-1. These are assigned to the spin allowed transitions
3
A2g(F)-3T2g(F), 3
A2g(F)-3T1g(F) and 3
A2g(F)-3T1g(P) respectively,
consistent with their well-defined octahedral configuration. The
electronic absorption spectra of Ni(II) complexes and their band
positions are shown in figure 4.3-4.4and the data are represented in
table 4.2.

Sumathi et. al[2] reported electronic spectra of Ni(II) complex

showed bands at 10582, 14471 and 25038 cm-1 due to 3A2g-3T2g(F),
3
A2g-3T1g(F) and 3A2g-3T1g(P) transitions respectively. This indicated
that the complex of Ni(II) is six-coordinate and having octahedral
geometry.

Table 4.2: Electronic Absorption Spectral data of Ni(II)

complexes.

Sr. No. Complex Absorption maxima cm-1 (cm)

υ1 υ2 υ3
1 Ni-L1 753(13280) 603(16583) 406(24630)
2 Ni-L2 755(13245) 602(16611) 409(24449)
3 Ni-L3 770(12987) 605(16528) 401(24937)
4 Ni-L4 765(13071) 602(16611) 401(24937)
5 Ni-L5 770(12987) 604(16556) 409(24449)
6 Ni-L6 771(12970) 603(16583) 407(24570)

135
Figure 4.3: Electronic absorption spectrum of Ni-L2

Figure 4.4: Electronic absorption spectrum of Ni-L6

136
Co(II) Complexes:

The electronic spectrum of Co(II) complexes exhibited three

bands in the region of 10141-10810(υ1), 16920-17985(υ2) and 19646-
20449(υ3) cm-1 which are tentatively assigned to 4T1g-4T2g(F), 4T1g-
4
A2g(F) and 4T1g-4T1g(p) transitions respectively which indicates the
presence of Co(II) complexes and their band positions are shown in
figure 4.5-4.6and the data is represented in table 4.3.

Devendra et. al[3] reported the electronic spectra of Co(II)

complex which displayed three bands at 13450, 15815 and 19676
cm-1 corresponding to transitions from 4T1g(F)-4T2g(F), 4T1g-4A2g and
4
T1g(F)-4T1g(p) respectively. These transitions suggested the
octahedral geometry for Co(II) complex.

Table 4.3: Electronic Absorption Spectral data of Co(II)

complexes.

Sr. No. Complex Absorption maxima cm-1 (cm)

υ1 υ2 υ3

1 Co-L1 926(10799) 556(17985) 493(20283)

2 Co-L2 925(10810) 587(17035) 509(19646)

3 Co-L3 964(10373) 581(17211) 489(20449)

4 Co-L4 940(10638) 591(16920) 493(20283)

5 Co-L5 980(10204) 559(17889) 505(19801)

6 Co-L6 986(10141) 562(17793) 490(20408)

137
Figure 4.5:. Electronic absorption spectrum of Co-L2

Figure 4.6: Electronic absorption spectrum of Co-L3

138
Cr(II) Complexes:

The Cr(III) complexes showed electronic bands at 16778-

16891 (υ1), 23529-23923 (υ2) and 34843-35087 (υ3) cm-1, these can
be assigned to 4A2g-4T2g(F), 4A2g-4T1g(F) and 4A2g-4T1g(p) transitions
respectively, thus suggesting octahedral structure. The electronic
absorption spectra of Cr(III) complexes and their band positions are
shown in figure 4.7-4.8and the data are represented in table 4.4. Jain
et. al[4] reported same observations for Cr(III) complexes 4.4.

Table 4.4 : Electronic Absorption spectral data of Cr(III)

complexes.

Sr. No. Complex Absorption maxima cm-1 (cm)

υ1 υ2 υ3

1 Cr-L1 592(16891) 418(23923) 285(35087)

2 Cr-L2 593(16863) 421(23752) 286(34965)

3 Cr-L3 596(16778) 425(23529) 287(34843)

4 Cr-L4 593(16863) 418(23923) 285(35087)

5 Cr-L5 594(16835) 424(23584) 285(35087)

6 Cr-L6 595(16806) 425(23529) 286(34965)

139
Figure 4.7: Electronic absorption spectrum of Cr-L2

Figure 4.8: Electronic absorption spectrum of Cr-L4

140
Fe(III) Complexes:
In case of iron complexes the d-d bands are generally spin-
forbidden and obscured by strong charge transfer bands[5]. In present
case the iron complexes show strong charge transfer band around
25000cm-1. The electronic absorption spectra of iron complexes and
their band positions are shown in figure 4.9-4.10 and the data is
represented in table 4.5
Table 4.5: Electronic Absorption Spectral data of Fe(III)
complexes:
Sr. No. Complex Absorption maxima cm-1 (cm)
υ1 υ2 υ3
1 Fe-L1 536(18656) 445(22471) 381(26246)
2 Fe-L2 543(18416) 445(22471) 388(25773)
3 Fe-L3 545(18348) 450(22222) 392(25510)
4 Fe-L4 537(18621) 447(22371) 391(25575)
5 Fe-L5 542(18450) 451(22172) 381(26246)
6 Fe-L6 547(18281) 452(22123) 390(25641)
The spectra showed three bands in range 18281-18656(υ1),
22123-22471(υ2) and 25510-26246(υ3) cm-1 which may be assigned
to high spin octahedral complexes. Thus the transitions are 6A1g-
6 6
T1(D), A1g-4T1 and A1g-4T2g respectively corresponding to
octahedral geometry.
The last d-d band assigned to transition 6A1g-4T2g in the present
case may be associated with the charge transfer bands travelling into
visible region of spectra.
Hossain et. al[6] reported the electronic spectra of Fe(III).
Fe(III) complexes gave four bands at the range 18500-18725, 21000-
21185, 24325-24750 and 25770-25640 cm-1 corresponding to
6
transitions A1g-4T1g(G), 6
A1g-4T2g(G), 6
A1g-4Eg(G), 6
A1g-4A1g(G)
respectively. These spectra indicated the octahedral stereochemistry
of Fe(III) complexes.

141
Figure 4.9: Electronic absorption spectrum of Fe-L2

Figure 4.10: Electronic absorption spectrum of Fe-L4

142
 Section B

Power X-ray diffraction studies of metal complexes:

X-ray diffraction is a powerful method to understand the

structure of the compound[7]. X-ray method can determine the
structure and symmetry properties of complexes. It gives information
of inter atomic distance, bond angles and electronic arrangement in a
complex.

It is possible to observe the molecules indirectly by using x-ray

radiation of very small wavelength of the order of 10-8 cm and
involves the studies of crystalline solids by the phenomenon of X-ray
diffraction. When the beam of monochromatic X-ray strikes the plane
of atoms in the crystal, an interference phenomenon is observed.
Bragg’s equation[8] gives the relation between interplanar distance
and the diffraction angle.
nλ=2dsinθ
Where,
n=order of reflection.
λ=Wavelength of X-rays.
d=interplaner distance
θ=angle of incident.
Constructive interference of the radiation from successive
planes occurs when the path difference is an integral multiple number
(n) of wavelength. This is Bragg’s law. All crystals of a substance
possess the same elements of symmetry. Bragg pictured the
diffraction effect or a reflection of X-rays from the lattice planes of
the crystal. The atoms in the plane are being responsible for scattering
of the X-rays to an extent dependent upon the number of its

143
electrons. This made a new and significant tool available to the
crystallographers and as result, an extensive amount of work on single
crystal was carried out to reveal the internal structure of the
compound and is a convenient and practical means for qualitative
identification of crystalline compounds. Now a days, single crystal
and powder methods are well established and powerful techniques to
understand the structure of solids.
The procedure in analyzing the powder diffractogram of an
unknown sample is consisting of measuring the intensities of the
peaks, the diffraction angle θ or 2θ. Once θ is determined, it is used
for calculating the inter planer spacing d of reflection planes from the
values of λ of X-rays used, and then the dimensions of unit cell are
determined. Powder diffraction technique is very important method
for identification of unknown compound and applicable to all
crystalline substances.

Scanning of Powder Diffraction and Indexing of the Data:

The X-ray powder diffraction of representative metal
complexes was scanned on Philips 50-90 PW-3710 diffractometer
attached to a computer along with graphical assembly and Cu-K
radiation source connected with the tube Cu-Ni-40 Kv/40 Ma
producing 1.543 Å wavelength radiations was used with scanning rate
2◦/min. Each test sample of 10mg was spread in the form of a film
and spectra were scanned in the range of 10-900.
The data obtained was deduced using computer program
powder-X. The preliminary data in the form of 2θ and intensity ratio
were fed to the computer and corresponding h, k, l values were
assigned to each peak. The programme calculates the lattice
parameters a, b, c (Å) and α, β,γ (degree) along with standard
144
deviation in each. The crystal volume is also obtained from the unit
cell data.
The densities of each of the complexes were determined using
specific gravity bottle by principle of Archimedes[9]. The density is
related to the formula factor as follows:
ρ=ZM / VNA
Where, Z=Number of formula units in the cell.
M=Mass of hydroden atom in amu.
V=Crystal volume.
NA=Avogadro’s number.
The calculated densities were correlated with the
experimentally obtained densities. The observed densities were used
to fix the value of Z to the nearest whole number. By using literature
values for definite crystal system, probable space group was assigned
to each of the complexes[10].
Once the dimension of the unit cell, the density and the
chemical composition of crystals are known, the number of atoms per
unit cell can be established. From the space group, number of atoms
in equivalent position contained by the unit cell can be deduced. In
this way unit cell represents the lattice structure of a crystal.

Results and discussion:

X-ray diffraction studies of some of the representative metal

complexes has been done and discussed in brief as follows:

Cu(II) complexes:

The Cu(II) complex of ligand L2, L3, L5, L6 were selected for
X-ray powder diffraction studies. The X-ray diffraction spectra of the
complex are shown in figure 4.11-4.14. The unit cell data, crystal

145
lattice parameters and the data obtained after indexing the powder
pattern are presented in table 4.6-4.9. The standard deviation was
within the permissible range. The diffractogram of complex L2 has 10
reflections between 10-850 with maximum reflection at 2θ=14.3710
corresponding to the value of d=6.15832A0. The crystallographic data
of the complex fits perfectly in monoclinic system with 4 molecules
per unit cell. Complex of Cu(II) with quinic acid was synthesized by
Behrens[11]. The structural studies reported that the crystal had
monoclinic system with 4 molecules per unit cell. The crystal data
obtained was: a=21.5123, b=6.1960, c=7.7592, α=γ=900, β=99 and
V=1018.3 Å3.

Table 4.6: Induced X-ray Diffraction Data of Complex Cu-L2:

Peak 2θ(obs.) 2θ(calc.) d(obs) d(calc.) Miller Indices of Intensity

No. planes

h K l
1 14.371 14.359 6.15832 6.16350 -1 1 1 16000
2 17.523 17.509 5.05692 5.06115 -1 0 2 5000

3 21.334 21.343 4.16150 4.15981 0 2 0 4000

4 23.606 23.607 3.76580 3.76564 -3 1 1 2000

5 26.175 26.169 3.40182 3.40254 -2 2 0 6000

6 28.116 28.111 3.17119 3.17179 2 0 2 5000

7 32.254 32.254 2.77321 2.77321 0 3 0 5000

8 39.699 39.703 2.26857 2.26836 3 3 0 3000

9 46.724 46.725 1.94257 1.94250 -4 0 5 1000

10 47.746 47.745 1.90335 1.90338 0 4 2 570

146
Unit cell data and crystal lattice parameter of complex Cu-L2

parameter Data Parameter Data

a(Å) 12.69125 Volume (A◦) 1069.6
b(Å) 8.31963 Density (obs.) 6.15832
c(Å) 10.13021 Density (calc.) 6.16350
α(degree) 90 Z 4
β (degree) 111.24 Space group P2/m
γ(degree) 90 Crystal system Monoclinic
lattice

Figure 4.11: X-ray diffractogram of Cu-L2

The diffractogram of complex Cu-L3 has 12 reflections

between 10-90◦ with maximum reflection at 2θ=25.030corresponding
to the value of d=3.55471. The crystallographic data for Cu-L3 are
summarized in table below 4.7.

147
Table 4.7: Induced X-ray Diffraction Data of Complex Cu-L3:

Peak 2θ(obs.) 2θ(cal) d(obs) d(calc.)

Miller Intensity
No. indices of
Planes
h k l
1 12.326 12.342 7.17512 7.16588 0 0 1 450
2 17.900 17.680 4.95135 5.01249 -1 1 0 1000
3 18.900 18.867 4.69150 4.69979 -4 0 1 700
4 20.888 21.020 4.24945 4.22296 -5 0 0 350
5 25.030 24.830 3.55471 3.58294 0 0 2 1400
6 27.450 27.267 3.24667 3.26804 5 1 0 1300
7 29.904 29.841 2.98556 2.99174 -7 0 1 400
8 35.306 35.062 2.54017 2.55728 6 1 1 200
9 36.385 36.575 2.46723 2.45487 -6 1 2 280
10 40.675 40.960 2.21636 2.20163 5 2 0 250
11 44.757 44.714 2.02326 2.02511 -4 2 2 220
12 47.802 47.982 1.90124 1.89453 -6 2 2 150

Unit cell data and crystal lattice parameter of complex Cu-L3

parameter Data Parameter Data

a(Å) 21.51 Volume (A◦) 810.2
b(Å) 5.16 Density (obs.) 3.55471
c(Å) 7.3 Density (calc.) 3.58294
Α(degree) 90 Z 4
β (degree) 101 Space group P2/m
γ(degree) 90 Crystal system Monoclinic lattice

148
 Figure 4.12: X-ray diffractogram of Cu-L3

The diffractogram of complex Cu-L5 has 11 reflections

between 10-85◦ with maximum reflection at 2θ=25.683
corresponding to the value of d= 3.46577 . The crystallographic
data for Cu-L5 are summarized in table 4.8.
Table 4.8: Induced X-ray Diffraction Data of Complex Cu-L5:
Peak 2θ(obs.) 2θ(cal) d(obs) d(calc.) Miller Intensity
No. indices of
planes
h k l
1 17.229 16.375 5.14262 5.40890 0 0 1 300
2 21.490 20.845 4.13164 4.25807 -1 1 0 1200
3 25.683 26.622 3.46577 3.34573 -1 1 1 1300
4 27.370 26.622 3.25591 3.34573 -1 1 1 1350
5 32.495 33.097 2.75317 2.70445 0 0 2 300
6 35.894 36.520 2.49988 2.45840 -2 1 0 270
7 36.883 36.520 2.43504 2.45840 -2 1 0 240
8 40.021 40.263 2.25109 2.23807 -1 2 1 250
9 41.592 42.422 2.16959 2.12904 0 2 0 230
10 45.008 45.763 2.01254 1.98109 -2 0 1 220
11 51.128 50.585 1.78510 1.80297 0 0 3 100

149
Unit cell data and crystal lattice parameter of complex Cu-L5

parameter Data Parameter Data

a(Å) 4.9168 Volume (A◦) 130.75
b(Å) 4.9168 Density (obs.) 3.46577
c(Å) 5.4089 Density (calc.) 3.34573
α(degree) 90 Z 4
β (degree) 90 Space group P2/m
γ(degree) 120 Crystal system monoclinic

Figure 4.13: X-ray diffractogram of Cu-L5

The diffractogram of complex Cu-L6 has 12 reflections

between 10-85◦ with maximum reflection at 2θ=27.442
corresponding to the value of d=3.24756 . The crystallographic data
for Cu-L6 are summarized in table 4.9.

150
Table 4.9: Induced X-ray Diffraction Data of Complex Cu-L6:

Peak 2θ(obs.) 2θ(cal) d(obs) d(calc.) Miller Intensity

No. indices of
planes
h k l
1 11.465 11.174 7.71160 7.91229 1 1 0 550
2 12.256 12.547 7.21614 7.04906 -3 0 0 390
3 14.114 13.324 6.26988 6.63991 2 1 0 580
4 17.832 18.618 4.97012 4.76206 -4 0 1 1000
5 19.884 19.739 4.46161 4.49398 -4 1 0 350
6 23.922 23.861 3.71687 3.72626 0 0 2 1100
7 27.442 27.356 3.24756 3.25753 -6 1 0 1250
8 31.487 31.524 2.83892 2.83567 -7 1 1 250
9 36.201 36.128 2.47938 2.48417 0 0 3 280
10 40.541 40.578 2.22341 2.22146 -7 2 2 210
11 49.108 49.113 1.85368 1.85352 -2 4 2 120
12 51.506 51.395 1.77288 1.77642 -11 2 1 100

Unit cell data and crystal lattice parameter of complex Cu-L6

parameter Data Parameter Data

a(Å) 21.543 Volume (A◦) 1395.4
b(Å) 8.532 Density (obs.) 3.24756
c(Å) 7.592 Density (calc.) 3.25753
α(degree) 90 Z 4
β (degree) 101 Space group P2/m
γ(degree) 90 Crystal system monoclinic

151
 Figure 4.14: X-ray diffractogram of Cu-L6

Ni (II) Complex:

The Ni(II) complex of ligand L2 and L6 was selected for X-ray

powder diffraction studies. The X-ray diffraction spectra of the
complex is shown in figure 4.15-4.16 The unit cell data, crystal lattice
parameters and the data obtained after indexing the powder pattern is
presented in table 4.10-4.11. The standard deviation observed was
within the permissible range. Some novel Schiff base metal
complexes of Ni(II) derived from 2[5-bromo-2-
hydroxybenzylidene)amino]pyridine-3-ol(BSAP) and [5-chloro-2-[(2-
hydroxynaphthylidene)amino]-phenyl-methanone(HNAC) were
synthesized by Jain[4]. The structural studies reported that the crystal
has orthorhombic system with 11 molecules per unit cell. The crystal
data obtained was a=12.67352Å b=23.790Å c=16.6256Å ,
V=5012.79Å.

The diffractogram of complex Ni-L2 has 10 reflections between

10-850 with maximum reflection at 2θ=20.423 corresponding to the

152
value of d=4.34511. The crystallographic data for Ni-L2 are
summarized in table 4.10
Table 4.10: Induced X-ray Diffraction Data of Complex Ni-L2:
Peak 2θ(Expt.) 2θ(obs) d(obs) d(calc.) Miller Intensity
No. indices of
planes
h k l
1 9.515 9.276 9.28711 9.52600 0 1 0 900
2 11.554 11.511 7.65260 7.68100 2 0 0 600
3 15.786 15.748 5.60940 5.62300 0 0 1 790
4 19.563 19.550 4.53413 4.53715 2 0 1 1200
5 20.423 19.667 4.34511 4.51032 3 1 0 1500
6 21.781 21.678 4.07716 4.09626 2 1 1 1000
7 25.315 25.293 3.51540 3.51833 3 1 1 1050
8 27.717 28.079 3.21597 3.17533 0 3 0 600
9 29.255 29.040 3.05024 3.07240 5 0 0 400
10 39.053 38.973 2.30461 2.30916 2 2 2 200

Unit cell data and crystal lattice parameter of complex Ni-L2

parameter Data Parameter Data
a(Å) 15.362 Volume (A◦) 822.86
b(Å) 9.526 Density (obs.) 4.34511
c(Å) 5.623 Density (calc.) 4.51032
α(degree) 90 Z 11
β (degree) 90 Space group P21/n
γ(degree) 90 Crystal system Orthorhombic
lattice

153
 Figure 4.15: X-ray diffractogram of Ni-L2

The diffractogram of complex Ni-L6 has 10 reflections between

10-850 with maximum reflection at 2θ=18.027 corresponding to the
value of d=4.91680. The crystallographic data for Ni-L6 are
summarized in table below 4.11
Table 4.11: Induced X-ray Diffraction Data of Complex Ni-L6:
Peak 2θ(Expt.) 2θ(obs) d(obs) d(calc.) Miller Intensity
No. indices
of planes
h k l
1 16.375 16.411 5.40890 5.40167 0 0 1 700
2 18.020 18.112 4.91680 4.91265 0 1 0 190
3 18.027 18.034 4.91680 4.91333 1 0 0 1810
4 24.447 24.123 3.63827 3.63828 0 1 1 840
5 30.542 30.526 2.92464 2.92330 1 1 1 600
6 33.097 33.019 2.70445 2.70446 0 0 2 320
7 41.013 41.112 2.19886 2.19635 1 2 0 150
8 50.104 50.106 1.81913 1.81654 0 2 2 130
9 54.137 54.140 1.69275 1.69270 1 0 3 90
10 62.060 62.060 1.49432 1.49435 1 3 1 60

154
Unit cell data and crystal lattice parameter of complex Ni-L6
parameter Data Parameter Data
a(Å) 4.9168 Volume (A◦) 130.75
b(Å) 4.9168 Density (obs.) 4.91680
c(Å) 5.4089 Density (calc.) 4.91333
α(degree) 90 Z 11
β (degree) 90 Space group P21/n
γ(degree) 90 Crystal system Orthorombic

Figure 4.16: X-ray diffractogram of Ni-L6

Co (II) Complexes:
Co(II) complexes of ligand L3 and L6 were selected for X-ray
powder diffraction studies. The X-ray diffraction spectra of the
complexes are shown in figure 4.17-4.18. The unit cell data, crystal
lattice parameters and the data obtained after indexing the powder
pattern is presented in table 4.12-4.13. The standard deviation was
within the permissible range. The solid complexes of Co(II) were
prepared from N-benzilidene-2-hydroxybenzohydrazine by
Shelke[12]. The structural studies reported that the crystal has
monoclinic system. The diffractogram of Co(II) complex showed

155
reflections with maxima at 2θ (30.49) corresponding to d value
2.9292 and values of lattice constants were a=8.34 Å, b=3.16 Å,
c=6.75 Å, α=γ=90◦≠β and unit volume, V=165.39. Complex of Co
(II) with (RS)-4-(7-chloro-4-quinolyl amino) pentyldiethylamine
diphosphate was synthesized by Deshmukh[13]. The structural
studies reported that the crystal had monoclinic system with
8molecules per unit cell. The crystal data obtained was a=21.7266 Å,
b=23.251 Å, c=27.5645 Å α=γ=90◦, β=89.8
The diffractogram of complex Co-L3 has 12 reflections
between 10-850 with maximum reflection at 2θ=23.579
corresponding to the value of d= 3.77015. The crystallographic data
for Co-L3 are summarized in table 4.12.
Table 4.12: Induced X-ray Diffraction Data of Complex Co-L3:
Peak 2θ(obs.) 2θ(cal) d(obs) d(calc.) Miller Intensity
No. indices of
planes
h k l
1 11.576 11.570 7.63794 7.64223 0 0 1 32
2 20.749 20.774 4.27751 4.27235 -2 0 0 38
3 23.579 23.569 3.77015 3.77163 -1 0 2 58
4 24.949 24.940 3.56609 3.56732 0 1 2 20
5 29.356 29.321 3.04006 3.04361 0 3 1 26
6 34.832 34.816 2.57359 2.57472 -2 3 1 27
7 42.268 42.274 2.13647 2.13618 -4 0 0 32
8 54.111 53.978 1.69351 1.69736 1 4 3 25
9 57.702 57.729 1.59636 1.59568 -4 3 3 38
10 68.096 68.098 1.37582 1.37578 -4 0 5 26
11 76.203 76.193 1.24835 1.24849 2 7 2 48
12 78.039 78.019 1.22350 1.22377 -2 7 3 44

156
Unit cell data and crystal lattice parameter of complex Co-L3

parameter Data Parameter Data

a(Å) 8.710298 Volume (A◦) 675.46
b(Å) 9.954352 Density (obs.) 3.77015
c(Å) 7.790333 Density (calc.) 3.77163
α(degree) 90 Z 1
β (degree) 101.19 Space group P2/m
γ(degree) 90 Crystal system monoclinic

Figure 4.17: X-ray diffractogram of Co-L3

The diffractogram of complex Co-L6 has 12 reflections

between 10-850 with maximum reflection at 2θ=18.378
corresponding to the value of d=4.82363. The crystallographic data
for Co-L6 are summarized in table 4.13.

157
Table 4.13: Induced X-ray Diffraction Data of Complex Co-L6:

Peak 2θ(obs.) 2θ(cal) d(obs) d(calc.) Miller Intensity

No. indices of
planes
h k l
1 6.812 6.812 12.96519 12.96476 0 0 1 200
2 12.292 12.304 7.19490 7.18788 -2 0 0 110
3 13.621 13.649 6.49560 6.48238 0 0 2 1000
4 18.378 18.347 4.82363 4.83180 -1 1 0 2400
5 20.514 20.535 4.32589 4.32159 0 0 3 510
6 25.680 25.660 3.46617 3.46892 -3 1 1 1000
7 26.662 26.648 3.34071 3.34248 -4 0 2 1990
8 29.648 29.641 3.01075 3.01145 3 0 3 100
9 31.952 31.931 2.79866 2.80053 -4 1 2 200
10 36.852 36.824 2.43707 2.43885 -5 1 2 400
11 46.225 46.246 1.96236 1.96151 -7 0 3 150
12 47.399 47.397 1.91647 1.91653 -6 1 4 120

Unit cell data and crystal lattice parameter of complex Co-L6

parameter Data Parameter Data

a(Å) 14.51140 Volume (A◦) 974.29
b(Å) 5.130262 Density (obs.) 4.82363
c(Å) 13.08709 Density (calc.) 4.83180
α(degree) 90 Z 1
β (degree) 97.84 Space group P2/m
γ(degree) 90 Crystal system monoclinic

158
 Figure 4.18: X-ray diffractogram of Co-L6

Cr (III) Complexes:

The Cr (III) complex of ligand L6 and were selected for X-ray

powder diffraction studies. The X-ray diffraction spectra of the
complex is shown in figure 4.19. The unit cell data, crystal lattice
parameters and the data obtained after indexing the powder pattern
are presented in table 4.14. XRD studies of Cr (III) complex with
benzyloxybenzadehyde-4-phenyl-3-thiosemicarbazone were carried
out by Prathima[14]. The structural studies reported that the crystal
has triclinic system with 8 molecules per unit cell . The crystal data
obtained was a=8.3109Å, b=4.2692Å, c=3.5313Å, α=99.0850,
β=94.560, ν=102.140 and cell volume=120.1A◦.

The diffractogram of complex Cr-L6 has 10 reflections between

10-85◦ with maximum reflection at 2θ=22.487 corresponding to the
value of d=3.95069. The crystallographic data for Cr-L6 are
summarized in table 4.14.

159
 Table 4.14: Induced X-ray Diffraction Data of Complex Cr-L6:

Peak 2θ(Expt.) 2θ(obs) d(obs) d(calc.) Miller Intensity

No. indices of
planes
h k l
1 14.296 14.185 6.19041 6.23871 1 0 1 28
2 22.487 22.934 3.95069 3.87471 0 1 1 82
3 25.562 25.545 3.48197 3.48420 1 0 2 23
4 28.516 28.593 3.12760 3.11935 2 0 2 48
5 30.817 30.826 2.89914 2.89835 3 -1 1 22
6 34.410 34.301 2.60421 2.61225 -3 -1 2 20
7 42.360 42.404 2.13204 2.12990 1 -2 1 26
8 46.725 46.733 1.94252 1.94221 3 2 1 19
9 47.988 47.985 1.89430 1.89440 -4 -2 1 21
10 52835 52714 1.73138 1.73506 -6 -1 3 20

Unit cell data and crystal lattice parameter of complex Cr-L6

parameter Data Parameter Data

a(Å) 14.533 Volume (A◦) 498.13
b(Å) 4.5321 Density (obs.) 3.95069
c(Å) 7.563 Density (calc.) 3.87471
α(degree) 90 Z 8
β (degree) 99 Space group P2/c
γ(degree) 90 Crystal system Triclinic

160
 Figure 4.19: X-ray diffractogram of Cr-L6

Fe (III) Complex:

The Fe (III) complexes of ligand L2 was selected for X-ray

powder diffraction studies. The X-ray diffraction spectra of the
complexes is shown in figure 4.20. The unit cell data, crystal lattice
parameters and the data obtained after indexing the powder pattern is
presented in table 4.15. The standard deviation observed was within
the permissible range.

A series of mononuclear iron (III) complexes of substituted-

salicylaldimine based ligands were prepared by Chi-Hueng[15]. They
were characterized by X-ray crystal structure analysis. The complexes
were found to crystallize in monoclinic system having 4 molecules
per unit cell with probable space group P21/n and P21/c respectively.

Single crystal of Iron (III) complex of diethyldithiocarbamate

and 1,2-bis(diphenyl phosphino) ethane were synthesized by
Tanmay[16]. The structural studies reported that the crystal has
monoclinic system with 4 molecules per unit cell having probable
161
space group P21/n. The crystal data obtained was a=19.0170Å,
b=11.7288Å, c=20.1715Å α=γ=90◦, β=101.27◦ and V=4412.4 Å3.

Complex of Fe(III) with an asymmetric tetradentate Sciff base

ligand derived from dehydroacetic acid, 4-methyl-o-
phenylenediamine and salicylic aldehyde were synthesized by
Munde[17]. The structural studies reported that the crystal has
monoclinic system with 2 molecules per unit cell. The crystal data
obtained was : a=7.0696 Å, b=14.8954 Å, c=5.3504 Å, α=γ=90◦ and
V=830.4539 Å3.

The diffractogram of complex Fe-L2 has 10reflections between

10-85◦ with maximum reflection at 2θ=21.783 corresponding to the
value of d=4.07672. The crystallographic data for Fe-L2 are
summarized in table 4.15.

Table 4.15: Induced X-ray Diffraction Data of Complex Fe-L2:

Peak 2θ(Expt.) 2θ(obs) d(obs) d(calc.) Miller Intensity

No. indices of
planes
h k l
1 20.390 19.811 4.35198 4.47794 1 0 1 18
2 21.783 21.911 4.07672 4.05320 2 0 1 40
3 24.089 23.717 3.69139 3.74851 -3 0 0 24
4 27.358 27.332 3.25737 3.26037 -3 1 1 26
5 30.268 30.119 2.95046 2.96476 1 1 2 28
6 40.115 40.083 2.24599 2.24772 -2 1 3 38
7 41.346 41.451 2.18196 2.17667 -5 1 1 30
8 48.021 48.000 1.89305 1.89384 -3 3 2 31
9 56.524 56.583 1.62681 1.62525 4 1 3 25
10 60.171 59.950 1.53663 1.54177 6 0 2 36

162
Unit cell data and crystal lattice parameter of complex Fe-L2

parameter Data Parameter Data

a(Å) 11.456 Volume (A◦) 628.58

b(Å) 7.562 Density (obs.) 4.07672

c(Å) 7.256 Density (calc.) 4.05320

α(degree) 90 Z 2

β (degree) 101 Space group P2/m

γ(degree) 90 Crystal system Monoclinic

lattice

Figure 4.20: X-ray diffractogram of Fe-L2

163
 Section-C

Thermal Studies of Metal complexes:-

The majority of compounds including metal complexes possess

physical and chemical changes when subjected to heat. Under defined
experimental conditions, these changes are characteristic of the
substance examined and can be used for its quantitative and
qualitative analysis. The techniques in which changes in properties of
substance are measured as a function of temperature, in controlled
temperature program are known as thermo-analytical techniques.
These methods are based upon the measurement of dynamic
relationship between the temperature and some properties of
substance such as mass, heat of reaction or volume.

When the sample to be analyzed is heated, various

physicochemical changes like thermal decomposition, oxidation,
dipole moment, electrical potential, magnetic susceptibility, crystal
structure, electrical conductivity, water evaporation, sublimation takes
place with a consequent change in the weight of the sample. Thermal
decomposition studies of the substance are very useful in predicting
the thermal stability of the substance. Chemical changes in the
substance can be studied with the help of thermogravimetric analysis
(TGA) and differential thermal analysis (DTA) and therefore thermal
properties are among the important properties of substances.

Thermogravimetric Analysis (TGA):

Thermogravimetry is a process in which the change in the

weight of a substance when heated at a controlled rate is recorded as a
function of temperature and or time, a substance is decomposed in the
presence of heat, which causes bonds of the molecules to break. A
164
plot of sample weight change as a function of temperature provides
both qualitative and quantitative information of sample. It directly
records the loss in weight as a function of temperature for transitions
that involve dehydration or decomposition. Thermogravimetric curves
are characteristic of a given compound or a material, due to the
unique sequence of physical transition and chemical reactions that
occur over definite temperature ranges. Changes in weight are the
result of breaking or formation of various bonds and evolution of
volatile or heavier reaction products[18]. Kinetic studies of thermal
decomposition reactions of a substance are of great importance in
calculating various parameters like energy of activation (Ea), free
energy change (∆G), order of reaction (n), pre-exponential factor (z)
and entropy of activation (∆S), which directly govern the factors of
thermal stability of any substance.The course and character of the TG
curves are influenced by several experimental factors such as rate of
heating, atmosphere of the furnace, geometry of the furnace and
sample holder, particle size, heat of reaction and compactness of the
sample.

In view of possibilities offered by such methods in the

investigation of both physical phenomena (melting point,
sublimation, adsorption, change in crystallographic properties etc.)
and chemical phenomena (dehydration, decomposition, oxidation –
reduction etc.), methods of thermal analysis have found application in
almost all the natural sciences.

165
Differential Thermal Analysis (DTA) :

It may be stated that a single thermal property is not sufficient

to characterize a chemical reaction or system, but that as many
thermal methods as possible be employed.

Differential thermal analysis (DTA) is a thermal technique in

which the heat effects, associated with physical or chemical changes
are recorded as a function of temperature or time as the substance is
heated at a uniform rate. Heat or enthalpy changes, either exothermic
or endothermic are caused by phase transitions. Generally phase
transitions, dehydration reactions and some decomposition reactions
produce endothermic effect, whereas crystallization, oxidation and
some decomposition reaction produce exothermic effects. The heat
effects occurring during these chemical and physical changes are
measured by differential thermal analysis. Each substance will give a
DTA curve whose number, size, shape and position of various
endothermic and exothermic features serve as a means of qualitative
information of the sample. The endotherms or exotherms can be used
to calculate the heat of reaction or heat of phase transition. The area
(A) of DTA peak is given by following equation:

A = ± G m ∆H/K
where,
G = sample geometry
m = sample mass
K = constant
∆H (enthalpy change) = - ve → exothermic
+ve → endothermic

166
 DTA is used to study the thermal stability of large number of
metal complexes and organic ligands.

The thermogravimetric studies of metal complexes find

extensive applications in determining the purity, metal-ligand bond
strength and melting points[19]. The simultaneous use of TG and
DTA for the study of metal complexes provides the useful
information. The TG is most useful when it compliments DTA. The
similarity in the values of thermodynamic and kinetic parameters
indicates the basic steps involved in the thermal degradation of
chelates are same[20]. The simultaneous use of TGA and DTA plays
an important role in the study of thermal behaviour of the inorganic
substances.

Thermal properties are important in kinetic studies of thermal

decomposition and energy of activation (Ea). TG and DTA studies for
some selected metal complexes were performed in static air on
laboratory fabricated instruments. The use of TG and DTA was made
in the present study of metal complexes with a view to understand
stoichiometry, thermal stability, the presence and nature of water
molecules. The water in inorganic compounds are classified as lattice
water and coordinated water. There is however no definite border line
between the two. According to Freeman and Carroll[21], the water
gets eliminated below 150°C can be considered as lattice water and
above 150°C as water gets coordinated to metal ion[22].

In the present study the simultaneous thermogravimetric and

differential thermal analysis of representative metal complexes were
performed on Perkin Elmer, in an air over a temperature range of 0° C
to 1000°C. The heating rate was 10°K min-1and flow rate of air 10

167
ml/min. The reference substance used was α-Al2O3 in platinum
crucible and samples weighed in the range 4 to 7 mg. Considering
percentage loss in weight the thermal decomposition behavior of Fe
(III), Co (II), Ni (II), and Cu (II) complexes of some selected β-
diketones are discussed on the basis of their TG-DTA curves as
follows.

Cu (II) complex:

The simultaneous TG/DTA analysis of a representative metal

complex of Cu (II) was studied from ambient temperature to 1000◦C
in nitrogen atmosphere using α-Al2O3 as reference. The thermogram
curve of Cu(II) complex shows weight loss 8.11% (cal. 8.20) in the
temperature range 190-2150C and sharp endotherm at 1950C which
clearly indicate a removal of two coordinated water molecules[23].

The anhydrous complex first showed decomposition from 265-

5700C with a 20.16% (cal. 20.50) mass loss and a broad exothermic
peak with 3900C in the DTA which may be attributed to the removal
of the non-coordinated part of the ligand. The second step of the
decomposition from 580-8650C with a mass loss of 55.10% (cal.
51.79) corresponded to the decomposition of the coordinated part of
the ligand. A broad endotherm in DTA was observed for this. The
mass of final residue corresponds to stable CuO, 17.95% (17.10)
which is in agreement with earlier workers[24].

Prasad et. al[25] reported thermogram of Cu(II) complexes

with clomiphene citrate. The TGA and DTA curves showed three
decomposition steps for all complexes. In the three step
decomposition, first degradation step occurs at the temperature range
128-2450C correspond to loss of two coordinated water molecules.

168
The major weight loss occur in second thermal decomposition step at
the temperature range 195-4160C. The third thermal decomposition
step occurs in the temperature range 305-6400C corresponding to the
loss of coordinated inorganic ligands. The final residue of the
decomposition at above 6400C corresponds to metal (II) oxide.

Figure 4.21: TG, DTA Curve of complex Cu-L2

Ni (II) complex:

The thermogram of the Ni(II) complex showed a mass loss of

7.17% (cal. 8.10) in the temperature range 150-1850C and
endothermic DTA peak in the region 1830C indicating the loss of two
coordinated water molecule. The anhydrous complex first showed
decomposition from 3700C to 4500C with a 21.15% (cal. 22.85)
mass loss and a broad exothermic peak with 3550C in the DTA which
may be attributed to the removal of the non-coordinated part of the
ligand. The second step of the decomposition from 475-8650C with a
mass loss of 55.05% (cal. 55.95) correspond to the decomposition of
the coordinated part of the ligand[26]. A broad endothermic peak in

169
the DTA was observed for this step. The mass of the final residue
NiO, 18.25%(cal. 18.65) which is in agreement with earlier workers.

Mapari et al.[27] reported thermogram of mixed ligand

complexes of N-(2-hydroxy-1-naphthylidene)-2,6-diisopropylaniline
and N-(2-hydroxybenzylidene)-2,3-dimethylaniline with Ni(II) ions.
The Ni(II) complexes lost their weight in the temperature range 125-
2600C corresponding to two coordinated water molecules with an
endothermic peak in DTA curve. After the total loss of water, the
organic moiety decomposed on further increament of temperature.
The complete decomposition of ligands occurred at a 450-6500C and
the observed residue corresponds to the respective oxide.

Figure 4.22: TG, DTA Curve of complex Ni-L3

Co(II) complex:

The thermogram of the Co(II) complex showed a mass loss of

7.90% (cal. 8.15)in the temperature range 180-2250C and
endothermic DTA peak in the region 1900C indicate the loss of two
coordinated water molecules[28]. The anhydrous complex first
showed decomposition from 245-5300C with a 22.11%(cal.22.29)
170
mass loss and a broad exothermic peak with 2650C in the DTA which
may be attributed to the removal of the non-coordinated part of the
ligand. The second step of the decomposition from 545-8800C, with a
mass loss of 49.15% (49.80) correspond to the decomposition of the
coordinated part of the ligand[29]. A broad endothermic peak in the
DTA was observed for this step. The mass of the final residue CoO,
13.30% (cal. 14.10) which is in agreement with earlier workers[30].
Verma et. al[31] reported thermogram of the Co(II) complex of β-
diketone.

The TGA curves of all the complexes almost indicate

continuous weight loss till a stable metal oxide was formed. Weight
loss of 5.15%-6.25% between 1580C-1950C has been observed which
indicated the presence of two molecules of water of coordination. On
further increasing the temperature, no weight loss takes place
probably which was attributed to the formation of stable metal oxide.

Figure 4.23: TG, DTA Curve of complex Co-L5

171
Fe(III) complexes:

The simultaneous TG/DT analysis of a representative metal

complex of Fe(III) was studied from ambient temperature to 1000◦C
in nitrogen atmosphere using α-Al2O3 as reference. The thermogram
curve of Fe(III) complex shows weight loss 7.10%(cal.7.97) in the
temperature range 170-1950C and sharp endotherm at 1900C clearly
indicate removal of two coordinated water molecules. The anhydrous
complex exhibited a single step decomposition from 2150C to 8400C
with 70% mass loss and a broad endothermic peak in the DTA. The
Fe2O3 is obtained as the end product[32].

Figure 4.24: TG, DTA Curve of complex Fe-L6

Thermal Decomposition and Kinetic Parameters of Metal

Complexes:

Kinetics of thermal decomposition reaction is useful for

industrial and analytical importance. In the present study the thermal
decomposition of Cu(II), Ni(II), Co(II) and Fe(III) complexes has

172
been carried out at uniform heating rate of 10◦C/minute and TG-DTA
curves have been reported. The kinetics and thermodynamic
parameters for their decomposition have been evaluated.

Thermal decomposition kinetics were studied by using

analytical data. Since various methods have been proposed for kinetic
analysis[33], some of the prominenet methods were selected from
those reported in literature. Horowitz-Metzer (HM) approximation
method[34] gives reasonably good results as compared to other
methods which is seen to be more accurate but time consuming.

Horowitz-Metzer approximation method:

Log[1-(1-α)1-n/(1-n)]=[logZRTs2/Eβ]-[Ea/2.303RTs]+[Eaθ/2.303RTs2]

The equation used for calculating entropy change (∆S) and free
energy change (∆G) are

∆S=2.303R logZh/kTs and ∆G=Ea-(∆S Ts/1000R)

Where,

Α=Fraction decomposed n=Order of reaction

T=Absolute temperature Z=Frequency factor

Ea=Energy of activation θ=T-Ts

Ts=Temperature at half weight loss β=Rate of heating

10◦C/min

R=Molar gas constant h=Planck’s constant

k= Boltzmann constant

173
 Using the computer Microsoft Excel Programme the linear
plots of the left hand side of above equation versus 1/T and again
θ=T-Ts were drawn by the method of least square for different values
of ‘n’ order of reaction ranging from 0 to 3 in increment of 0.01 and
the corresponding correlation coefficients were evaluated. The
highest value of correlation coefficient gave the correct value of ‘n’
from the slope and intercept, Ea and Z or A values, values of ∆s and
∆G were determined. The calculated values of the activation energy
of the complexes were relatively low, indicating the autocatalytic
effect of the metal ion on the thermal decomposition of the
complexes. The complexes have high negative entropy which indicate
that the decomposition reactions proceed with a lower rate than the
normal ones[35]. The negative values of entropies also indicates that
the activated complexes have more rigid structure than the reactants
or intermediates. The more ordered nature may be due to the
polarization of bonds in the activated state, which might occur
through charge transfer electronic transitions.

Table 4.16 : Thermodynamic and Kinetic Parameters

Complex Step n Ea KJ Mol-1 Zs-1 ∆JK-1 mol-1 ∆GKJmol-1 Corelation

coefficient
(r)
Cu First 1.9 57.17 3.8x103 -155.2 50.12 o.9912
complex
Second 1.6 43.16 5.1X103 -198.5 60.14 o.9914
Ni First 1.2 121.93 7.7X109 -56.7 98.3 0.9897
Complx
Second 1.8 56.29 51.3X1014 -203.36 86.45 0.9914
Co First 1.7 40.15 1.93 -244.67 55.12 0.9875
Complex
Second 1.0 19.33 6.85 -263.25 41.79 0.9815
Fe First 1.9 59.98 7.4 -139.7 57.48 0.9876
Complex
Second 1.4 49.12 5.7 -203.15 61.13 0.9919
Third 0.5 25.55 7.9 -254.14 78.27 0.9915

174
Results and Discussion:
The Horowitz-Metzer method has been used to calculate the
thermal parameters ∆G, ∆S, Ea and Z for non-isothermal
decomposition of Cu, Ni, Co, Fe complexes. Generally, with
decreasing value of ∆E, the value of Z increases, and higher values of
activation energy suggest higher stability[36]. Higher values of Ea
and lower values Z suggest that the transition state is in a highly
ordered state compared to the individual reactants and the reaction
was slower than normal[37]. The organic moiety decomposed further
with increasing temperature. Although the decomposed fragments of
the ligands could not be approximated owing to continuous weight
loss, the complete decomposition occured at approximately at 640-
6500C. At the end of the final step, stable metal oxides were formed
corresponding to Fe2O3, CoO, NiO and CuO.
A small variation in the stability observed from the energy of
activation may be attributed to some intermolecular interactions
occurring therein. The negative values of the apparent entropy of
activation (∆S) indicate that the activated complexes have more
ordered or more rigid structure than the reactants or intermediates as
the reactions are slower than normal[38]. Entropy of activation
followed no definite trend. The values of the kinetic parameters
follow nearby same pattern for each complex. This similarity
indicates that the basic steps involved in the thermal degradation of
the complexes were the same.
The thermal stability of the complexes showed variation due to
some inter molecular interaction occurring in them, besides this there
were several other experimental factors[39]. The values of
thermodynamic and kinetic parameters, Ea and Z of the complexes
determined are comparable with the values found for other related
compounds by earlier workers[40-42].

175
References:
[1] K. Mounika, B. Anupama, J. Pragathi, C. Gyanakumari, J of
Scientific Research 2(3), 513-524, (2010).

[2] S. Sumathi, C. Anitha, P. Tharmaraj, C. D. Sheela,

International J of Inorganic Chemistry, Article ID 154326,
8 pages, (2011).

[3] Devendra Kumar, Rabeena Akhtar, Shivani Singh, J of

Chemical and pharmaceutical Research, 4(@): 1301-1307,
(2012).

[4] R. Jain and A. Mishra, J. Serb. Chem. Soc., 77, 1-27(2012).

[5] Lever ABP, “Inorg. Electronic Spectrosc opy” 2nd Edn.,

Elservier, New York, 456, (1984).

[6] Md. Belyat Hossain, M. A. Yousuf, M. Rafiqul Islam, Md.

Ahedul Akbor, Bangladesh Pharmaceutical Journal, 15(2),
(2012), 177.

[7] J. Bassett., R. C. Denney., G. H. Jeffery., J. Mendham.,

“Vogel’s Text book of Quantitative Inorganic Analysis”,
ELBS Longman, England (1985), 849-868.

[8] R. K. Agrawal., S. C. Rastogi., Thermo Chem. Acta 63,

(1983), 363.

[9] F.H. Urena, Moreno-M. N. aretro., Trans. Met. Chem. 20,

(1995), 262.

[10] P. S. Mane, S. D. Salunke, S. G. Shirodhakar J. Indian

Chem. Soc., 79, 7,(2002), 611-613.

[11] Norah Barba-Behrens, Farfan Salazar-Garcia, Transition

Metal Chemistry, 15, (1994), 575.

176
[12] V. A. Shelke, T. K. Chondhekar, Bull. Chem. Soc. Ethio,
(2011), 25(30), 381.

[13] J. H. Deshmukh, M. N. deshpande, J. Chem. Pharm. Res,

(2011), 3(3), 706.

[14] B. Prathima, Y. Sabba Rao, A. Varada Reddy, International

J Pharmacy and pharmaceutical Sciences, 4, (2012), 3.

[15] Chi-Hueng, Jian-Wei Lu, Ho-Hsiang Wei, Masuo Takeda,

Inorganic Chimica Acta, 360, (2007), 2944.

[16] Tanmay K. Jana, D. P. Kumar, r. Pradhan, S. Dinda, Inorg.

Chemica Acta, 10, (2009).

[17] A. S. Munde, T. K. Chondhekar, J. Serb. Chem. Soc, 75(3),

(2010), 349.

[18] C. Kittle, “Introduction to Solid State Physics,” 5th Edn,

Willey Estern Ltd. New Delhi, (1994)

[19] W. W. Wendladt, “Thermal Methods of Analysis,” Heyden

Philadelphia, (1977)

[20] M. I. Pope, M. D. Jude, “ Differential Thermal Analysis,”

Hyden Philadelphia, (1977)

[21] Freema and Carroll, J. Physical Chem, 62, (1958), 391

[22] A. S. Aswar, J. Indian Chemical Soc, 75, (1998), 395

[23] J. Sestak, V. Satava, W. W.. Wendland, Therm. Chem. Acta,

7, (1973), 333.

[24] J. T. Makodi, A. S. Aswar, J. Indian Chem Soc, 80(1),

(2003), 44.

[25] K. S. Prasad, L. S. Kumar, H. d. Revanasiddappa, Chemical

Sciences Journal, 28, (2011).

177
[26] Vogel, AI A. Text book of Qualitative Inorg. Analysis, 3rd
Edn, Longmans: London, (1975).

[27] Astmaram Mapari, Kiran Mangonkar, International J Chem

Tech Research, 3, 2, (2011), 636.

[28] Norah Barba-Behrens, Farfan Salazar-Garcia, Transition

Metal chemistry, 15, (1994), 575.

[29] V. A. Shelke, T. K. Chondhekar, Bull. Chem. Soc. Ethio,

(2011), 25(30), 381

[30] A. A. Pawanoji, B. H. Mehta, Asian Journal of Chem. 21, 9,

(2009), 6869.

[31] P. N. Verma, Javed Sheikh, Harjit Juneja, African Journal of

Basic & Applied Sciences, 3(2), (2011), 35.

[32] N. H. Gaur, Rashmi Sharma, R. S. Shindhu, J. Indian Chem.

Soc,78(1), (2001), 26.

[33] H. Horowitz, G. Metzer, Anal. Chem, 35, (1963), 1464.

[34] K. Aroma, Indian J Chem, 74, (1997), 589.

[35] K. Arora, Indian J. Chem,74, (1997), 589.

[36] E. I. Huseniny, M. Diefallah, Thermo. Chem Acta, 11,

(1992).

[37] A. S. Aswar, V. V. Dhande, V. B. Badweik, Russ J Inorganic

Chem, 52, (2007), 8, 1200.

[38] P. K. Sharma, A. K. Sen, S. N. Dubey, Indian J of Chem, 33,

(1994),1031.

[39] P. Chourasia, K. K. Suresh, A. P. Mishra, Proc. Indian Acad.

Sci (Chem Sci), 105, (1993), 173.

178
[40] A. S. Aswar, J. T. Makode, J Indian Chem Soc, 80, (2003),
44

[41] V. V. Dhande, V. B. Badweik, A. S. Aswar, Russ. J Inorg

Chem, 52, (2008), 8, 1204.

[42] P. P. Mandlik, A. S. Aswar, Polish J Chem, 77, (2003), 129.

179