Chapter 2

Reagents and Physico-Chemical Methods

n this chapter an outline of the materials, procedures and

various physico-chemical methods employed are presented.

2.1

Reagents
The metal salts used for the synthesis of the complexes were

BDH grade samples. The dicarboxylic acids used for the preparation
of the parent 4-coordinated and 6-coordinated systems like succinic
acid (H2suc), malonic acid (H2mal), oxalic acid (H2ox) and terephthalic
acid (H2tpa) were either BDH or Merck make and used as such. The
Lewis-bases

used

for

the

present

study

like

pyridine

(py),

ethylenediamine (en), 1,3-propylenediamine (pn), 2,2'-bipyridine (bipy)

and 1,10- phenanthroline (phen) were either BDH, fluka or E.Merck
samples. The solvents employed for the present study were of BDH
make and purified by standard procedures.(1) All the reagents and
indicators used were prepared by standard procedure.

2.2
2.2.1

Preparative Details
Metal Dicarboxylates
Metal dicarboxylates were generally prepared by reacting the

respective metal carbonate with a hot aqueous solution of the

relevant dicarboxylic acid taken slightly in excess than required for
1:1 stoichiometry without adjusting pH. The reaction mixture was
boiled on a steam bath for about 1h. The complex was separated
and washed repeatedly with hot water followed by methanol.

Chapter 2

52

2.3

Elemental Analysis
All

the

metal

dicarboxylates

and

their

adducts were

characterised by elemental analysis. Various metal ions were

estimated by standard procedures.(2) Representative procedures
employed are given below for each metal ion.
2.3.1 Estimation of Nickel
Weighed quantity (0.1g) of the complex was digested with
con.H2SO4 followed by con.HNO3 to oxidise and decompose the
organic matters. The clear solution so obtained was evaporated to
dryness and the residue was extracted with distilled water. It was
then diluted to 50 ml and 25 mg of murexide indicator was added
followed by 5 ml of 1M NH4Cl solution. Ammonia solution was then
added to it till pH was raised to 7 as indicated by the yellow colour of
the solution. It was then titrated against standard EDTA solution.
Near the end point, 5 ml of con.NH3 was added till the pH was 10
and the titration continued until the colour changed to violet.(2)
2.3.2 Estimation of Cobalt
About 0.1g of the complex was digested with con.H2SO4
followed by con. HNO3 as before. A few drops of perchloric acid was
also added to the resulting solution. The clear solution obtained
was evaporated to dryness and the residue was then extracted with
50 ml of distilled water. Hexamine buffer was added to the resulting
solution till pH was 6. It was then titrated against standard EDTA
solution using xylenol orange indicator till the colour changes from
red to yellow.(2)

Reagents and Physico-Chemical Methods

53

2.3.3 Estimation of Copper

Weighed quantity (0.1g) of the complex was digested using
con.H2SO4 and HClO4. The resulting clear solution was evaporated
to dryness and the residue was then extracted with distilled water
into an iodine flask. The Cu+2 solution thus obtained was brought
to a pH of 4-5.5 by adding ammonia solution followed by acetic
acid. The estimation of copper was done by iodometric titration
using standard sodium thiosulphate solution and starch as
indicator.(2)
2.3.4 Estimation of Carbon, Hydrogen and Nitrogen
The conformation of the composition of all the adducts and
metal dicarboxylates was done by estimating carbon, hydrogen and
nitrogen by employing Heraeus CHN rapid analyzer.

2.4

Spectral Methods

2.4.1 IR spectra
IR

spectra

were

recorded

using

Shimadzu

IR-470

Spectrophotometer operating in the range 4000-400 cm-1. The

samples were prepared either in the nujol mull form or as KBr
pellet.
2.4.2 Electronic spectra
A ShimadzuUV-160A Spectrophotometer operating in the
spectral range 1100-200 nm was used for electronic spectral
studies. It has a accuracy of 2 nm. The spectra were recorded
for the insoluble solid samples by making them as pasty mass by
grinding with nujol and then spreading the paste uniformly on a

Chapter 2

54

transparent glass or a Whatman filter paper strip. The reference

used was either a clean transparent glass or a Whatman filter
paper strip wetted with nujol. For the soluble samples the spectra
were recorded by dissolving them in CH3OH, water or CHCl3. The
cuvettes used were of quartz make with path-length of either 1 cm
or 0.5 cm.
2.4.3 EPR Spectra
The X-band EPR spectra of the Cu(II) complexes
recorded employing a Varian E-112 EPR

were

spectrophotometer

operating at 9.1 GHZ with a microwave power of 5 mW. The field set
is around 3000 G and the scan range used were either 2000 or
500 G. The spectra were obtained either at room temperature (for
insoluble solid samples) or at liquid nitrogen temperature of 770K
(for soluble samples). More often a methanol-toluene mixture was
used as solvent to facilitate better glass formation at low
temperature. DPPH or tetracyanoethylene (TCNE) radicals were
used as g marker.
The fundamental principles of EPR are essentially the same
as those of NMR. Practical difference arises from the fact that the
magnetic moment of an electron is substantially larger than that of
proton. The energy of resonance absorption is
E = h = gH

. (2.1)

where denotes the frequency of the radiation used, h is Plancks

constant, g is the spectroscopic splitting factor, is the Bohr
magneton and H is the magnetic field.

Reagents and Physico-Chemical Methods

55

The various spin-Hamiltonian for the interaction of an electron

with the magnetic field can be given by the equation
= gHz

. (2.2)

where g for a free electron has the value 2.0023, is Bohr

magneton, eh/2mec with a value of 9.27310-21 erg gauss-1, z is
the spin operator and H is the applied field strength. The spectra of
powder samples result from the superimposition of all the
orientations of single paramagnetic centers and has a shape
influenced by the anisotropic part of the Hamiltonian. The nuclear
spin of copper (I = 3/2) splits both the parallel and perpendicular
lines into four hyperfine lines. The energy absorbed during a
resonance transition h can be expressed as

h = gH + Am1

. (2.3)

For copper, the nuclear spin quantum number m1 takes

values 3/2 and 1/2
We have analysed the EPR spectra of Cu complexes mostly by
assuming axial symmetry for which the relevant spin Hamiltonian is

= gIIHzSz + g(HySy + HxSx) + AIIM SzIzM+ AM (SyIyM + SxIyM) + AIIN

H
SzIzN + AN (SyIyN + SxIxN)

. (2.4).

where z-axis is the symmetry axis of the molecule and S and I terms
are components of the electron and nuclear spins in the specified
directions. In equation (2.4), the first two terms are Zeeman for
electron, third and fourth terms are the components due to the

Chapter 2

56

nuclear (metal) hyperfine interaction and fifth and sixth terms are
contribution from the superhyperfine interaction of the ligand (N)
and the unpaired electron.
In a rigid medium each molecule has an orientation with
respect to the magnetic field and the tensor g and the hyperfine
coupling constant A can be written as

g = g ||2 cos 2 + g 2 sin 2

A=

H || =

(A g
2
||

2
||

cos2 + A g sin 2
2

. (2.5)

.(2.6)

hv
hv
and H =
g ||
g

. (2.7)

The hyperfine splitting arises because of the electron spin

interacting with its own nucleus, and further to that the superhyperfine splitting due to the electron spin interacting with the nuclear
spin of the neighbouring atom (s). The parallel and perpendicular
components arise because of the anisotropy of the field felt at the
free electron because of the overall structure of the molecule and
also the orientation of the molecule with respect the external
magnetic field applied.
A can also be calculated from the equation

A=

g ||2 + A||2
g ||2 A||2 + g 2 A2

(3)

.(2.8)

Reagents and Physico-Chemical Methods

57

The average of g, ie., gav can be calculated from the equation

gav = ( 2 3 ) g + ( 1 3 ) g ||

.(2.9)

It can be seen that for tetragonally compressed copper(II)

complexes g > g where g = 2 and for tetragonally elongated copper(II)
complexes g > g > 2. In a square planar copper(II) complexes if the
unpaired electron resides in the dx2-y2 orbital, g>g>2 while g >g= 2
when the unpaired electron is in the dz2 orbital.
The g is a parameter indicative of covalency. For a covalent
complex g < 2.3 and for an ionic environment g = 2.3 or more.
For a square planar copper(II) complex, the g value is expressed as
.

2k
and g = 2.002
E xz

g = 2.002

8 k 2
E xy

(2.10)

where k is the orbital reduction factor, is the spin orbit coupling

constant, Exz is the energy of 2B1g 2Eg transition and Exy is the
B

energy of 2B1g 2B2g. Combining the above two expressions

B

G=

g 2.002
g 2.002

4 k 2 E xz
k 2 E xy

(2.11)

The value of G indicates the strength of the ligand, whether

strong or weak. If G < 4.0 the ligand forming copper (II) complex is
regarded as a strong field ligand. In the case of Cu(II) complexes the
2 is related to A , g
inplane covalency parameter Cu

and g

according to Kivelson and Neiman equation.(4)

Chapter 2

58

2 = (A /0.036) + (g 2.002) + 3/7 (g - 2.002) + 0.04 ..(2.12)

Cu

2 is in between 0.5 to 0.80 and for

For covalent bonding, Cu
2
ionic it approaches 1. Cu
is inversely related to the covalency of

the Cu-N bond. That means for a compound which has low value
2 , the covalency of the Cu-N bond is high or the ionic
for Cu

character will be less. In the case of bonding, the ionic character

increases as the nitrogen donor increases.

2.5

Coordination Chemistry of Copper(II)

Copper(II) forms complexes with coordination numbers four,

five and six, the latter being predominant. A significant number of

7 and 8 coordinate geometries also occur. Unlike other first row
transition metal ions, the copper(II) complexes are characterised by
a variety of distortions.(5,6) Majority of 6-coordinate copper(II)
complexes involve an elongated tetragonal or rhombic octahedral
structure, with a few involving a compressed tetragonal structure
caused by Jahn-Teller effect. The tetrahedral geometry of Cu(II) ion
always involves a significant compression along the S4 symmetry
axis. Only the square planar geometry is regular for Cu(II) ion, but
even there it involves a slight tetrahedral distortion. Copper(II) ions
with five coordination rarely possess a regular square pyramidal
geometry; it generally undergoes both an elongation and a trigonal
in-plane distortion,(6) or less frequently, a tetrahedral distortion (J.T
effect). The trigonal bipyramidal geometry of Cu(II) may be regular,
but is frequently distorted slightly towards a square pyramidal
stereochemistry.

Reagents and Physico-Chemical Methods

59

Generally, Cu(II) complexes are blue or green due to d-d

electronic transitions causing absorption in the 600-900 nm
regions. If there is a strong charge transfer band spreading to the
visible region the complex appears red or brown. Since copper (II)
ion is subjected to Jahn-Teller distortion and a regular octahedral
complex is not formed, the formal Eg and T2g terms get splitted. The
spectra do not usually correspond to the simple

2E

2T
2g

excitation(7) but rather to one based on altered multiple states as

shown in Fig. 2.1.

Eg

B2g
2
A1 g

T2 g

D
2

Free ion

Eg

Octahedral

Fig. 2.1 Splitting of 2Eg and

B1 g

Tetragonally distorted

T2g states in Cu(II) in various fields

Tetragonal copper(II) complexes are expected to show the

transition

2B
1g
B

2A1g, 2B1g 2B2g and 2B1g 2Eg but bands due to

B

these transitions usually overlap to give often one broad absorption

band.(8,9)
Four-coordinate Cu(II)

complexes are common, but the

strict tetrahedral or square planar stereochemistries are rare.

Intermediate stereochemistry of approximate D2d symmetry is more
usual and four transitions between the d-orbitals may be
observed.(10,11) The spectra of such complexes often show two or

Chapter 2

60

three

less

resolved

bands

below

about

20,000

cm-1.

The

polarisation properties of these bands have been studied in some

detail in certain cases assisting in the assignments of the
transitions involved.(7,12)

2.6

Coordination Chemistry of Cobalt(II)

The most common states of cobalt are +2 and +3. A few Co(IV)

and Co(V) compounds also exist(13) such as golden yellow Cs2CoF6,

red brown Ba2CoO4 and blue black K3CoO4. Most simple salts exist in
the Co(II) oxidation state and crystallise from aqueous solution as
CoX2.6H2O or CoX2.4H2O. Most Co(II) salts in aqueous solution
readily dissociate to give the [Co(H2O)6]2+ ion which is pale pink. The
existence of trication [Co(H2O)6]3+ is possible in very strong acids,
which is blue in colour and is rapidly reduced by water to
[Co(H2O)6],2+ liberating oxygen.
Co(II) complexes adopt two major stereochemistries, six
coordinate distorted octahedral and tetrahedral. Although a few low
spin square planar systems are known cobalt phthalocyanines,
cobalt(salen)-type Schiff bases as well as some five-coordinated
systems such as [Co(CN)5]3- are square pyramidal with one unpaired
electron; and [CoBr(N(C2H4NMe2)3)]+ is trigonal bipyramidal with three
unpaired electrons. Octahedral and tetrahedral stereochemistries are
often found in equilibrium and in aqueous solution even [Co(H2O)6]2+
has a small amount of [Co(H2O)4]2+ present.
The d7 electronic configuration is the most favoured to form the
tetrahedral as opposed to the octahedral stereochemistry. Ligand
polarizability as well as ligand size are important factors, with the
more polarizable ligands (eg. I, P, As, aromatic N donors) favouring

Reagents and Physico-Chemical Methods

61

tetrahedral structures. Most O and N (amine) donors, however, favour

octahedral coordination. Octahedral Co(II) complexes are pink to
violet in colour (absorption ~500 nm), whereas tetrahedral complexes
are more intensely blue (~600 nm). The colour of octahedral Co(II) is
dominated by 4T1g(F) 4T1g(P) transition (3), with the two lower
energy transitions (to 4T2g (F) and 4A2g(F) levels), occurring in the near
IR and visible regions of the spectrum respectively.(14) A simplified
Orgel diagram for octahedral and tetrahedral cobalt(II) is shown in Fig
2.2 In octahedral systems the 4A2g level is usually close to the 4T1g(P)
level and the transition to these two levels are close together. Since
the 4A2g state is derived from t 32g e g4 and 4T1g(F) ground state is derived
from t 52g e g2 configuration, 4T1g(F) 4A2g(F) transition is essentially a
two electron process. Hence it is weaker by about a factor of 10-2
than the other transitions. There is one more spin allowed transition
in octahedral complexes which is the transition 4T1g(F) 4T2g(F).

T1(P)

T1g(P)

P
4

A2g (F)

T1(F)

T2 (F)

4
4

T2g (F)

F
4

T1g(F)

A2 (F)
t

Fig 2.2 Orgel diagram for tetrahedral and octahedral Co(II)

Chapter 2

62

The T ground term results in temperature-dependent orbital

contributions to the magnetic moment, with values (4.8-5.2 BM)
falling off appreciably with decreasing temperature. Tetrahedral
Co(II) is dominated by the broad and intense 3 transition
4A (F)
2

4T1(P) with the lower energy 1 and 2 transitions occurring

in the near IR region

(to 4T2(F) at 3000-5000 cm-1, to 4T1(F) at

5000-8000 cm-1). The spin only moment of 3.87 BM for the

tetrahedral ligand field is modified by mixing the lower energy 4T2(F)
level into the ground 4A2

term via spin-orbit coupling, and this

results is greater than spin only magnetic moments (15-25%)

depending on the ligand; the moment is temperature independent
in this case.

2.7

Coordination Chemistry of Nickel(II)

Nickel compounds have been found to occur with the metal

in oxidation states varying from -1 to 4.(15) However, comparatively

very few compounds correspond to the lowest (-1) and to the higher
(+3, +4) oxidation states. Ni(-1) has been claimed to be formed only
in a few organometallic compounds.(16)
The reported Ni(0) complexes are all diamagnetic which show
the ligands stabilise the 1S (3d10) configuration relative to the other
ones.(17) Ni (+1) complexes are also comparatively rare similar to
Ni(-1) and are paramagnetic (d9 configuration, eff = 1.72-2.4 BM).
The
coordination

overwhelming
numbers

of

majority
four,

of

five

Ni(II)
or

six.

complexes

have

Complexes

with

coordination numbers of 3,7 and 8 are still quite rare. In almost all its
six-coordinated complexes of nickel(II) has a pseudo octahedral
stereochemistry with a spin triplet as ground state (high spin

Reagents and Physico-Chemical Methods

63

configuration). The magnetic moments of octahedral Ni(II) usually lie

between 2.9 and 3.3 BM and the temperature dependence of the
magnetic susceptibilities follow Curie-Weiss law.
Five-coordination is also now quite common in Ni(II)
complexes and many polydentate ligands such as polyamines,
salicylaldimine polyarsines and polyphosphines have been designed
with the purpose of favouring this stereochemistry.(18,19)
However,

five-coordinate

complexes

with

monodentate

ligands [Ni(CN)5]3- and [Ni(OAsMe)5]2+ are also known. The five

coordinate Ni(II) complexes have structure

which are generally

near to one of the two limiting geometries, namely the square

pyramid and trigonal bipyramid. The electronic ground state of
Ni(II) in five coordinated complexes can neither be a spin singlet or
a spin triplet. Spin singlet corresponds to low spin configuration
while spin triplet to high spin configuration.
The majority of 4-coordinated nickel(II) complexes are square
planar and invariably diamagnetic, whereas pseudo tetrahedral
complexes which are always paramagnetic are relatively rare. It is
in general found that ligands with weaker donor strengths favour a
pseudo tetrahedral structure, whereas ligands with higher donor
strengths tend to produce square planar structure. It must also be
borne in mind that ligands which contains bulky substituents on
the donor atoms may prevent a planar structure due to steric
hindrance, and a distorted tetrahedral structure may become
preferred.(20) Nickel(II) in tetrahedral geometry

has an orbitally

degenerate ground state and the magnetic moments are expected to

be substantially higher than those of six-coordinate complexes

Chapter 2

64

because of large orbital contribution. The magnetic moments are

usually found to be in the range 3.3-4 BM at room temperature.
Strong Ni-ligand interactions stabilise planar configuration
in 4-coordinated Ni(II) complexes. Planar complexes of Ni(II) are
often yellow owing to an absorption around 500 nm. The majority
of square planar complexes are formed by interacting either
chelating ligands or tetradentate macrocyclic ligands with Ni(II).
Porphyrins and phthalocyanines also stabilise square planar and
octahedral Ni2+ complexes.

Fig.2.3

d-orbital splitting patterns and electron occupation for Ni2+ in

tetrahedral, octahedral, tetragonally distorted and square planar
geometries.

Another common feature of square planar Ni(II) complexes is

their ability to coordinate extra ligands in solution to set up
equilibria between four, five and six-coordinated complexes. Thus
diamagnetic square planar complexes can be transformed in
coordinating solvents or in the presence of extra ligands to

Reagents and Physico-Chemical Methods

65

paramagnetic octahedral Ni(II) species. The electronic spectral

features of nickel have been thoroughly reviewed.(19-21) Tetrahedral
complexes are usually highly coloured due to their expected d-d
transition from 3T1(F) state to 3T2(F) (1), to 3A2 (F) (2) and to 3T1(P)
(3), respectively. But the observed spectra tend to be complicated
by spin-orbit coupling effects.
Three d-d transitions resulting in
3A (F)
2g

3A (F)
2g

3T (F)
2g

(1),

3T1g(F) (2) and 3A2g(F) 3T1g(P) (3), would be observed for

Ni(II) in an octahedral field. The simplified Orgel diagram for

tetrahedral and octahedral Ni(II) is shown in Fig 2.4. Ni(II) square
planar complexes have a single band in the range 18000-25000 cm-1
due to transition for 1B1g 1A1g.(21)
B

Fig. 2.4

The simplified Orgel diagram for Ni (II) in tetrahedral and octahedral

ligand fields

Chapter 2

66

2.8

Thermal Analysis
Thermal methods of analysis have become an important tool

in the study of solid state reactions, phase equilibria, measurement

of specific heat etc. The study of the reactions involving solids has
three aspects, viz., phenomenological, thermodynamic and kinetic.
The

phenomenological

study

is

mostly

concerned

with

the

quantitative and semiquantitative observations occurring during

the reactions. The thermodynamic aspect is static in nature. It is
related to the initial, final and equilibrium states of the system and
the driving force behind the transformations. The kinetic approach
is mainly concerned with the rate of transformations of the
reactants into the products and the mechanism of transformations.
The present investigation involves mainly the study of the influence
of procedural factors on kinetic parameters obtained from nonisothermal kinetic analyses using TG and DTG data.
2.8.1 Thermogravimetry (TG)
The present thermal experiments were carried out using
Seiko thermal analyser in an atmosphere of dry nitrogen, from
room temperature to about 8000C.

The kinetic parameters were

calculated by using a computer programme.

Thermogravimetry is defined as a technique whereby the
change in mass of a substance is recorded as a function of time or
temperature, as it is heated or cooled in a suitable environment at
a

controlled

rate.

Mainly

two

methods

are

employed

in

thermogravimetry: (1) isothermal or static thermogravimetry, where

the sample mass is recorded as a function of time at constant
temperature and (2) non-isothermal or dynamic thermogravimetry,

Reagents and Physico-Chemical Methods

67

where the sample is heated in an environment whose temperature

is changing in a linear rate.
In derivative thermogravimetry (DTG) the derivative of mass
change with respect to time is recorded as a function of time or
temperature. The derivative curve may be obtained either from the
TG curve by manual differentiation methods or by electronic
differentiation of the TG signals. The area under the DTG peak at
any temperature gives the rate of mass change at that temperature.
The DTG curve allows the ready determination of the temperature
at which the rate of mass change is maximum (Ts) and the initial
temperature (Ti) at which cumulative mass change begins and the
final temperature (Tf) at which the cumulative mass change reaches
a maximum corresponding to complete reaction.
2.8.2

Differential Thermal Analysis (DTA)

DTA is a thermal technique in which the temperature of a

sample is compared with the temperature of a thermally inert

material and the temperature difference is recorded as a function of
the sample or furnace temperature, as the sample is heated or cooled
at a uniform rate. The temperature changes in the sample are due to
endothermic

or

exothermic

reactions

that

occur

during

the

temperature programme and the corresponding deviation from the

reference temperature is studied. This difference in temperature
between the sample and the reference, i.e., T= Tsample-Tref is recorded
as a function of temperature.

Chapter 2

68

In non-isothermal method, the following aspects are studied.

a) Phenomenological Aspects: This study is used to find the initial
temperature (Ti), the final temperature (Tf) and the temperature of
maximum mass loss (Ts) from DTG peaks. The TG plateau gives
the percentage mass loss during each stage of decomposition. The
DTA curve identifies the exothermic or endothermic nature of the
different changes undergone by the sample.
b)

Kinetic Aspects: One of the most important applications of

thermogravimetry involves the study of reaction kinetics and
mechanism of solid state thermal decomposition reactions. The
reaction rate of a solid thermal decomposition can be expressed
by the general equation(22)

d
E
= A. exp
. f ( )
dt
RT

. (2.13)

where, A = pre-exponential factor, t = time, and = fractional

decomposition. E= activation energy. The f () = depend on the
mechanism of the reaction.

W0 W
W0 Wt

(2.14)

where, W0, W and Wt are initial, actual and final sample weights
respectively.

Reagents and Physico-Chemical Methods

69

When the temperature of the sample is increased at a constant rate of

=

dT
, we can write
dt

d A
-E
=
exp
f ( )
dT
RT

(2.15)

or as

d
A
-E
=
exp
dT
f ( )
RT

. (2.16)

On integration

g () =
0

d
A
=
f ( )

T
0

exp RT dT

.(2.17)

where g () is the integrated form of f ()

or, ln g () =

E
AR
+ ln
RT
E

.(2.18)

Plotting the LHS of equation 2.18 against 1/T should give a

straight line with a slope of -E/R irrespective of g() values
employed. The kinetic parameters can be calculated from the same
linear plot. The value of E and A can also be evaluated from the
slope and intercept respectively. The entropy of activation (S)
could be calculated from the equation.

k .Ts
S
exp

R
h

A=
where

.(2.19)

k = Boltzmann constant, h = Plancks constant

S = entropy of activation.

Chapter 2

70

c) Mechanism of reaction from non- isothermal TG: Deduction of

the mechanism or reaction from non-isothermal methods has
been discussed by Sestak and Berggren.(23) Kinetic parameters
are evaluated from non-isothermal TG curves by the application
of Arrhenius equation. The usual non-mechanistic kinetic
equations are extension of those used in homogenous kinetics,
where it is assumed that f () = (1-)1-n and mechanistic and
kinetic studies are based on the assumption that the form of
g() depends on the reaction mechanism. A series of f() forms
are proposed and the mechanism is obtained from the one that
gives the best representation of the experimental data.
Four non-mechanistic methods are usually used for the
calculation of kinetic parameters from the TG curve. The forms of
these equations used are given below, where the term g() has been
introduced for convenience and defined as.

g() =

1 (1 )1 n
1 n

1. Coats-Redfern equation

. (2.20)
(22)

AR
2 RT E
g ( )
(1
) = ln
2
E RT
T
E

In

2. Mac Callum-Tanner equation

. (2.21)

(24)

3
AE
0.435 [0.499 + 0.217 E ]10
0.485
E
...(2.22)

T
R

log10 g() = log10

Reagents and Physico-Chemical Methods

3. Horowitz Metzger equation

ART

71

(25)

Ea

s
In g () = In
+
E RTs ETs

4. MKN equation

... (2.23)

(26)

AE
g ( )
+ 3.7721 - 1.9215 ln E - 0.12039
= ln
1.9215
T

ln

E

T

...(2.24)

where = fraction of decomposition, n = order parameter,

T = temperature in Kelvin, A = pre-exponential parameter,
= heating rate in 0C min-1, E = activation energy, R = gas constant,
Ts = DTG peak

temperature, = (T-Ts), M = mass loss in TG

experiment, a = area of DSC curve at time t and after the completion

of the reaction.
The kinetic parameters can be calculated from the linear plot
of the LHS of the kinetic equation against 1/T for equation 2.21,
2.22 and 2.24 and against for equation 2.23. The value of E and
A are calculated from the slope and intercept respectively.
The Coats-Redfern equation (eqn.2.21) was used for solving
the exponential integral in the present study because it is one of
the

best

approaches

recommended

by

several

authors.(27-29)

Satava(30) listed nine probable reaction mechanisms from the

Coats-Redfern equation which are given in Table. 2.1.

Chapter 2

72

Table 2.1 Mechanism based equations

Eqn.
No

Form of g ()

Rate Controlling process

One- dimensional diffusion

+ (1-) In (1-)

Two- dimensional diffusion

[1-(1-)1/3]2

Three-dimensional diffusion, spherical

symmetry, Jander equation.

(1

-In (1-)

Random nucleation, one nucleus on each

particle, Mampel equation

[-In (1-)]1/2

Random nucleation, Avrami equation I

[-In (1-)]1/3

Random nucleation, Avrami equation II

1- (1-)1/2

Phase boundary reaction, cylindrical

symmetry

1-(1-)1/3

Phase boundary reaction, spherical

symmetry

2.9

2
3

) (1 )2 / 3

Three dimensional diffusion, spherical

symmetry, Ginstling- Brounshetin equation

Magnetic Susceptibility Measurements

Magnetic moment of all the complexes were measured at

room temperature (282)0C using Gouy balance with mercury(II)

tetrathiocyanatocobaltate(II) as calibrant. Magnetochemistry is
used to investigate the magnetic properties of transition metal
complexes. Magnetic moment can provide information about the
oxidation state of the metal ion, electronic structure and symmetry
properties of the complexes. This also would give a clear idea about

Reagents and Physico-Chemical Methods

73

the number of unpaired electrons in the central metal atoms or ion

in the complex.
In first row transition metals, the spin only magnetic
moment can be calculated using the equation
(s,o) = [ 4S (S+1)]1/2

..(2.25)

The magnetic susceptibilities of the complexes were measured

at room temperature using a Gouy magnetic balance. The Gouy tube
was standardised(31) using mercury(II) tetrathiocyanatocobaltate(II).
Diamagnetic corrections for the rest of the molecules were
computed from Pascals constants.(32,33) Gram susceptibility was
calculated using the formula.
g =

+ E
W

.. (2.26)

where = air displacement constant, = Gouy tube constant

E = change in weight in mg, W = weight of the sample in gram
The effective magnetic moments, eff, were calculated from
corrected molar magnetic susceptibility, m*.
m = g mol. wt

(2.27)

m* = m + D
where, D is the diamagnetic correction
eff = 2.84 m* T BM

. (2.28)

Chapter 2

74

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