314 Concise Coordination Chemistry

N
H

H
N

(a) Structure of phorphine ligand

CH,
H,C CH

CH, *HC CH,

N

H,C CH,CH,CO,

H,C CH,CH,CO,
(b) Heme group

(OH) herme

C-0

Fe globin
heme
N -0

HN
heme
CH,CHCO
NH,
(c) Haemoglobin sub-unit
Fig. 14.I
 Biological Coordination Compounds 315
14.1.2 Structural Features of Haemoglobin
Each haemoglobin molecule consists of four sub-units, each unit being a folded
chain. Asub-unit consists of a protein unit, (globular protejn, called globin), a
heme group anda histidine unit (F1g. 14.1c).
2. The heme unit is a chelate of iron with porphine
3. Its molecular weight is abour oS,000.
ligand.
4. The four polypeptide chains of haemoglobin are wound in
sucha manner as to
make the molecule spherical.
5. The iron in haemoglobin is in the Fe(II) state; it is
coordinated to the four
nitrogern atoms in the porphine group.Two more ligands, a histidine unit and a
water molecule are also coordinated to Fe(II), The histidine ligand is the link
between the heme group and the protein unit. The water molecule is denoted
by a circle in the figure, because, the exact geometry of the
bonding betweern
H,0 and Fe(II) is not certain. fo C1)rcd co Lor
6. The complex is octahedral. The porphyrin ring is
conjugated and planar The
"Charge transfer between stable and low-lying orbitals on the ring and iron is
the origin for the red colour of the complex. The water ligand in
can be readily replaced by molecular oxygen to form the red-colouredhaemoglobin
Oxyhaemoglobin; this is present in the arterial blood. The water-coordinated
complex is called deoxyhaemoglobin; it is blue, the colour çharacteristic of
the venous blood. As each sub-unit can bind one
O2,. cach haemoglobin
molecule can bind up to four O, molecules.
7. In oxyhaemoglobin, the Fe() is in the low-spin state and is diamagnetic; but in
.deoxyhaemoglobin, the Fe(I) is in the high-spin state and is paramagnetic. The
size of Fe(II) is increased by about 30 per cent, when it changes from the
diamagnetic toparamagnetic state. This increase in size distorts the bonds around
Fe and also the shape of the complex. In oxyhaemoglobin, the Fe(I) is of the
right size to get into the hole at the centre of the porphyrin ring; but in
deoxyhaemoglobin, because of its enlargerment, it is above the plane of the ring.
The O, molecule is bonded to the heme group as shown in Fig.14.2.

O
-N N
Fe
-NI N
N (imidazole)
A portion of oxygenated
haemoglobin
Fig. 14.2 Thebonding of the oxygen molecule with the
heme unit of haemoglobin
The arteries carTY blood to the muscles in various parts
of the body, where oxygen
transferred to a myoglobin molecule and
IS required. In the muscles, the oxygen is glucose. When haemoglobin loses
stored, untilit is required to produce energy from
to iron. Then, the protein part of it
1ts O2, a water molecule is again coordinated
 Concise Coordination Chemistry

CONH,
CH, CONH,
NH,OC CH,
H,C
N
HC CONH,
Co*

.CH;
NH,OC
CH,
H,C
H,C CONH,

H,C
OC N
H,C
HÌ
NH
CHCH,

CH,OH
cobalamin
(a) The structure of
HO OH

H H
H H

H,C

NH,
-N

(6) The ligand 5'deoryadenosyl group

Fig. 14.8
 contribution to syntheuc

14.5 VITAMIN B12 (CYANOCOBALAMIN)

liver. It is
Vitamin B12is a cobalt complex (Fig. 14.8). It isa coenzyme and occurs in extract in
liver
tightly bound to several enzymes in the body. It was isolated from
1948. In 1965, Dorothy Hodgkin (Nobel Laureate) determined its structure
crystallographically.
The following are,the important structural features of this vitamin:
The cobalt in it exists as Co(III).
2. Cobalt is located at the centre of a macrocyclic ring called corrin ring; this ring
resembles the porphine ring. However, this ring is not conjugated like the
porphyrin ring.
3. Jaaddition, acomplex organic portion consisting of a sugar, a phosphate group
and aD organic base are bonded in the molecule.
 Biological Coordination Compounds 327

4. Co(III)is octahedrally bonded by four N atoms of the corrin group, the organic
base and the sixth ligand X. Vitamin Bj, is cyanocobalamin, Xbeing CN.
Normally, X is H,0.
5. Cobalamin refers to the structure without the ligand X.
X= CN : cyanocobalamin
X= H,0 : aquacobalamin
X=CH3 : methylcobalamin
X= 5'-deoxyadenosyl : coenzyme B12·
Vitamin B12 is cyanocobalamin.
Theexact role of vitantnBhthe cellprocesses is not clear; however, it can
only in concert with a number of enzymes. The B1,coenzymes function in concert
with a number of enzymes to effect several biological reactions. One such reaction is
dehydration of diols by dioldehydrases assisted by a B12 coenzyme.
RCHOHCH,OH ’ RCH,CHO + H,0 (R= CH3 or H)
It is of criticalimportance in the metabolisms of carbohydrates, fats and proteins.
Inhumans, deficiency of vitamin B,2 causes pernicious anaemia. Methylcobalamin
(X=CH3)is responsible for the environmental conversion of Hg() to toxic CHHg
through methane-producing bacteria. Similarly, it can transfer methyl groups to TI(),
P(II) and Au().
 t
Douorpoci" aleu dwlor

6
100°c

(m4
Calo
420c

b60°

Tang(
 11
THERMOGRAVIMETRIC ANALYSIS

1.1 INTRODUCTION
property of the system is measured as a function
In thernmometric methods of analysis some are listed below :
temperature. Most frequently used thermometric methods
ofthe
Table 11.1. Thermoanalytical Methods
Property measured Apparatus
Designation
Thermobalance
Thermogravimetric analysis | Change in weight
(0 (TGA) Thermobalance
Derivative thermogravi Rate, of change of weight
2. metric analysis (DTGA)no nc ds
Differential thermal Heat evolved or DTA apparatus
aoi3. analysis (DTA) absorbed (01)
Heat evolved or Differential
Calorimetric DTA DC
4. absorbed teot flow Calorimeter
Titration calorimeter.
Thermometric titrations Change of temperature
660°C 5.
Thermal methods of chemical analysis include such techniques as thermogravimetricanalysis
thermometric titrations (TT). In addition another
i(TGA), diferential thermal analysis (DTA) and involves the measurements of weight
thermoanalytical method evolved recently (P. L. Waters, 1960) heating. Thistechnique has been
a sample during
loss due to the escape of all volatile matters from Thermogravimetric analysis involves the
fractional thermogravimetric analysis (FTGA).
+NOO isalled it is being heated at a predetermined rate In
weighing of thesubstance under investigation whiledifference in temperature between the sample
DTA, changes in heat content as a function of the solution
an inert reference compound, is measured. In thermometric titrations changes in
jand titrant.
|temperature are measured and plotted against the volume ofsubstance is recorded as a function
a
Thus, in thermal methods, the thermal behaviour of
considered as thermal spectra, usually
fof temperature and/or time and the recorded curves may be
techniques because their applications do not
jcalled thermograms. TGA and DTA are valuable
With the development of sophisticated,
usually impose any restriçtion on the systems being studied. there
|rugged andsensitive automatic recording thermobalances, is an increasing tendency now to
materials such as
use TGA as the first stage in a multi-instrument approach for the analysis of
and
oil shells, polymers, moon rocks and catalysts. The increasing awareness in the arca of TGA
DTA is evidenced in the increasing nuraber of reserch papers published every year incorporating
the thermal behaviour of wide variety of materials. This has, in a way, necesstiated the publication
OT two new journats from 1970 in the field of thermal analysis-Journal of Thermal Analysis and
Thermo Chimica Acta, and inclusion of appropriate headings to various aspects of TGA and DTA
in Chemical Abstract.
91
 1.2 WHAT IS THERMOGRAVIMETRIC ANALYSIS
The trchnique of thermogravimetric analysis involves the weighing of the substance Thermogravimnetrio An
investigations while it is being heated at a predetermined and preferably. linear rate
There arc, in fact, three types of thermogravimetry: () static or Almost all the th
quasistatic TGA, and (i) dynamic thermogravimetry. isothermal gravimetry, ype of to the end ofIna
instruments.
attached
() Isothermal or static thernogravimnetry has been known since long in which
weight is recorded as a function of time at aconstant temperature. he sam was used in that
case.
() In quasistatic TGAthe sample is heated to constant weight at the sample attached to
each step in a
increasing temperatures. serie; hehind(Ya waveHeating
in a li
(iii) In dynamnic thermogravimetry the sample is heated at a uniform rate, but
the results are subject to errors due to the effect of
changing air unfortuna.: isvarious forms
that the depend
convection, the measurement of temperature, heating rate, and heat
are often overlooked. It is, therefore, apparently suitable for the of buoyancy
reactipn,
whi
fheating
10°-500°C per hr.,)r
approximate quantitative thermal behaviour of a system and
determination of precise constants. Studies in dynamic determination
transformer. Other ec
cannot be used for as close to the furna
11.3
recently in 1923 with the advent of automatic recording
INSTRUMENTATION
thermogravimetry
TGAinstruments
the nichrome windir
began on one commercial ins
In thermogravimetric analysis the programmes for seri
determination of against
reproducible and recognisable stoichiometry is produced is temperatureby which a materialAbeating
at a reference
ratee
thermobalance. There are several types of thermobalances tacilitated the use of the so-cal
availabie conmercially, but the basiaffcultTheto size of
instrumental requirements in TGA are a precision balance, contro
atmosphere control devices. heating device, temperature oland are suitable t
One of the
-Furnace temperature. As
Controller produced during
achy
mportant proble
s 4-5°C per mi
i) TH
Furnace X-Y Recorder
Hepending on t
Vacuum Sample Cup þf sample cups
Shallow
to allow the ga
in the study o
Gas Deep c
Covere
Balance Control
NU) Retop
he weight c
Balance the reaction
Fig. 11.1. A schematic modern ither in the
Weight Measurement : Thermobalance. thermogravimetric analyser. tary out th
Weighing mechanism in TGA may bihply cov
modification of a single or double pan balance, an electronically
balance or a simple spring balance depending upon the self-balancing device, a torsamosphere
the laboratory, a precision torsion balance
may be
requirement. For the preliminary wo oxide, hy
The balance Should have the easily adopted for use as a thermoblancgsually
(a) It following
should be simple to operate, characteristics: bf thermal
(6) It should have an egulate tb
(c) It should be able toadjustable
respond
range of weight change, \I.4, DE
(d) lt rapidly to changes in weight and
should be rugged, accurate, very sensitive and Se
mechanically stable.
eriolves
vatiwtt
 ThermogravimetriàAnalyßn d
used are either the null point or h
thermobalances that have been obstructe
the substance UDa Almost all the
commercil instruments a beam of light
modern
ear rate.
finstruments. In some
spring has been used in
quartz spring balance.Photoelectric
galvanome
attached,to the end of a quartz use torque motor-a
Dpes

-mal gravimetry. commercial thermobalances of

case. Several pair split phos
usedin that needle to somé null-point. Null is detected by a
in which the.S d sample attached to
was the
light beam. control have o
the
/behind a wave in a Measurement. The furnace design and
re. Heating and Temperature sophistication of the instrument The maiti requiremmen
h step in a series on the degree of a linéar heating programme
arious forns depending be smooth so that it/can maintain either programme is a varia
that the heating rate simplest temperature
e, but un fortunatei is
(i0°-500°C per hr.) or a fixed temperature. The thermometers situated
conventional thermocounles or resistance
air buoyancy a transformer. Other equipments use windings are commonly used.
t of reaction, whi winding as possible. Platinum, and tungstern Pt-Rh, up to 1450°C) at leat
e determination close to the turmace pursuit a maximum temperature of1100°C; a
a be nichrome windings 1600°C. In one of the most common
mot be used for
instrument is capable of reaching about is compared electronically
commercial the furnace
vimetry began jone signal from a thermocouple in heating modes
struments. orogrammes for serious work, the can be programmed to correspond to a variety of
which
inst a reference potential
quickly and it is
materia) and heating rates. very important. Small furnace cools very
nich a The size of the furnace is
also
Although large furnaces maintain isothermal temperature
se of the so-calls temperature very late.
control linear heating rate. attain the required
jally, but the basaifficult to maintain linear heating rate, but they measuremnent of sarmple
temperature oandare suitable tomost important and also difficult problems in TGA is the products
One of the
below, the self-heating during oxidation, the gaseous
remperature. As has been discussedreaction of the sample with the atmosphere are some heating of the
broduced during heating and the measurement. The usual rate of
which introduce error in temperature
important problems Work
is 4-5°C per
minute.
shapes of sample cups have been used for TGA
Cups. Several four basic designs
1f ) The Sample system being investigated. Generally there are
Hepending on the nature of the cup.
cups-shallow pan, deep crucible, covered cup and retort during heating and it is necessary
bf sample products are produced
Shallowpans-are used when volati<e wide application
escape. These pans have found a
diffuse to the surface tÍ
to allow the gases to behaviour of polymers. area studies.
in the study of the thermalused in industrial scale calcinations or surface self-generated atmosphere.
Deep crucibles are the studies have to be carried out in
Covered cups are used where point studies. because
useful in boiling in TGA
yU RetOt Cups are
Control. Atmosphere control is extremely importantsample heating, or
1 \ o Atmosphere gaseous products formed during
sample is due to the atmosphere can be achieved
in the
fhe weight changesample atTOSphere./The control of necessary to
with the balance kinetic studies where it is affected by
fhe reaction of a the balance. In certain kinds of
usually
#Pither in the sample or in generated atmo_phere, the regulation is of maintaining the
in a sample way
loose fitting lid. Another nitrogen, argon, carbon
Ey out the experiment container with
covering the sample balance_with an inert gas, such as very low density helium
TGA may bgpimply the whole and
device, a torsimosphere is by flushing Because of the low thermalconductivity decompositions and the study
hydrogen or helium. of polymer
líminary worloxide, preferred as an inert atmosphere for thecompounds In all serious works it is necessary to
study
thermobafanceusually of several other
classes of
nemal behaviour
fegulate the gas pressure. (DTGA)
THERMOGRAVIMETRIC ANALYSIS
DERIVATIVE electronic circuits to record the
with
commereial thermobalances are provided thermogravimetric arnalysis in
derivative at
Several
As i
thermogravimetry, the specimen as it is being heated
ble. Yative automatically. the rate ofchange of weight of the
olves themeasurement of
94
Chenical Analy.
of
uniform slow rate. In
order to appreciatethe usefulness derivative thermogravimetric
analy
a obtained in the pyrolysis of a mixture containing calcium carbonate
curves
let us examine (see Fig. 11.2). It is evident from the figure that the plateau inthe
magnèsiumcarbonate. quite clear, but the shoulder at about 870°C is not very clear. However
(of TGA)at
700°C is
the shoulder has been clearly resolved into a peak. It com
thermogra
thermogram obtained in DTGA,derivative curve.
the without
not have been pin-pointed
logs
weight
erce

DTG

MgCOt.
caMg[co),1 0 TGA

MgO+
CâMgcUy20
MgO+3o
CaCO, 40
Mg.50
Cao 400 600 800
Temperature °C
1000

MgCO..
Relation between TGA and DTG curves for the pyrolysis of CaC0, and
Fi. 11.2,
AFFECTING TGA
11.5 FACTORS obvious sources of errors, such as sensitivity of the balance, ennors
:
In addition to the system, etc., the following factors may af
difficulties inherent in a chemical
weighing, unusual
results.
the accuracy of TGA Buoyancy and Convection
1 Effect of Changing Air themobalance is to support the inert sample from
beld
The most favoured arrangement for Under this condition.the inert sample
maysh
cylindrical, capped tube furnace.
in the centre of a correction has, therefore, to be applied to the recorded wei
mg;
an apparent weight gain up to 10 weight gain are :decreased air buoyancy, increased convectid
change. The causes for the apparent
heat on balance mechanjsm. The magnitude of the apparent weight gain may
and the effect of for the acti
considerably by proper venting but for careful work correction h¡s to be used
reduced
samples.
Measurement of Temperature
2
practice in TGA is to measure the temperature in the furnace near the sample;t
The usual those determined by the more common proce
temperatures so determined are usually higher than difference ispartly due to themal lag
temperature directly. Thecause of this
of measuring the detectable change in weight. The results of vario
partly due to the finite time required to cause a
the drying of bulky precipitates, it wou
workers suggest thiat when thermobalance is used to study
be well to use slow rates of heating.
3 Effect of Atmosphere
thermobalance in ambient air, the atmosphere n
When a sample is dried or decomposed in gaseous decomposition products or
the sample is continuously modified due to the addition of Even smallchanges in compositio
loss of th¢ part of original gas by reaction with the sample. flush the thermobalan
this atrmosphere can affect the thermogram. It is therefore necessary to pössible.
continuously with inert gas in order to maintain as constant an atmosphere 2s a

4 Effect of Heat of Reaction

and furn
The heat of reaction will affect the difference between sample temperaturedepending,
temperature, causing the sample temperature to lag or lead the furnace temperarure
whether the reaçtion
of temperature lag is isto'increase
endthemicthe furnace
or exothermi When and
termperature the the
reàction is endothermle,
differential temperature w
C
 Thermogravimetricc Analysis 95
additive. But when the reaction is exothermic this effect will tend to compensate each other.
Effect of Heating Rate
Heating rate has been found to affect the thermoeram annreciably. The effect of
heating Ta
isimportant if the thermogram is to be used for kinetic analysis. Fig. 11.3 illustrates the effect of
heating rate on the thermogram of calcium oxalate monohydrate. The pleateau from the room
temperature to 100°C corresponds to monohydrate. The loss of CO commences at 413°C and that
of CO, at 685°C. It is apparent from Fig. 11.3. that the three loss of CO and
reactions-dehydration,
inss of CO,- at lawer heating rates have lower onset and decomposition ternperatures.
CacyoH,0249 CaGo +94o6 )
mg
50 100

Start
120
Ca Ihr
¤t 150°C /hr corrected for
differences in scale and
bapparent weight gain
aco b
330 380
220
413 Ca Co
270 575
685
485
800

830 900

Fig. .3. Effect of heating rate on the thermogram of CaC,o,.H,0.

Similarly, on heatingNiSO, 7H,0 at 2.5°C/min. only one platuex in the TG curve corre
sponding to NiSO, H,0 is obrained, but if it is heated at the rate of o.6eC/min. the curve breaks
corresponding to Niao,.6H,0, NiSQ.SH,0, NisO.4H,0, NiSO,3H,Q NiSO,2H}O and
NiSO,.H,0 are obtained.
6 Sample Characteristics
(a) Weight of the Sample. A larg sample affects. the T.G. curve and the curye deviates
from liFearity as the temperature rises. Hence, small samples are preferred. If 20 mg of the
CuSO,.5H,0is used, no platuëx córresponding to CuSO,.3H,0 is obtained, but. if only 0.5 mg of
the sample is used, this plateau can be obseryed.
(6) Particle SizeParticle size also affects the TG curve. Smaller particles decompose at
lower temperature while larger size particles of the sample take longer time and decompose at higher
temperature.
(c) Compactness of the Sample. Compact samples decompose at higher temperature th¡n
thà loose samples.
(a) Previous History of the Sample. The source and method of preparation of the sample
also have been found to affect TG curve. For example precipitated Mg(OH), decomposes at a
different termperature than the naturally occurring Mg(O),
11.6 APPLICATIOÞNS OF TGA. sybhe oting
Petermination of Optimum Drying Temperature Range
hermogravimetric analysis is being widely used in qualitative and quantitative analyses and
thermal stability studies etc.!Much of the work in thermogravimtry has been done to establish
optimum temperature ranges for the conditioning of precipitates for conventional gravimetric
analysis. Some thermogravimetric curves are shown in Fig. l1.4. Curve A shows the thesmogram
of calcium oxalate. It is normally precipitated as the monohydrate from hot solution. The curve
eRhibits several platuex corresponding respectively to monohydrate from room temperature to
00°C, anhydrous calcium oxalate from 226° to 398°C, calcium c¡rbonate from 460° to 635°C and
alcium oxide from above 840°C. The calcium carbonate is an excellent weighing form if heated
 96
to 500 ± 25°C. Curve B of
Fig. I1.4
Chemi
magnesium oxalate which represents the alysi Thermogravime

13426 478
398
635
CaC,O4
reveals
160°C: the anhydrous compound
and the oxide is stable from 480o
that dihydrate is
exists
to
thermogram
stable
between 220° and up Temp"C
1000°C.
f 600r

838 1025 is best made as the oxide at a

Weig hing, 400 5004
152t
226
397

478
M,C,0,
gó0
The curve C of Fig. 11.4
chromate. The initial drop in weight
temperature
represents the
above 480°C. therefor
T.G. Curve of silv A00
Weight Ag,CrO, just about 92°C the weight
becomes indicates the excess
812°C after which oxygen is lost. constant and remainswater, 3004
92
The so an
52 256 Hg,CrO,
chromate can, therefore, be represented
ZAg,CrO4 ’
as decompositionof
silve 100
200

94ßl Silver chromate is thus A8Cr,O4+ 2Ag + 20,.

155 671
Quinolinium to 800°C. Hence in stabBe'over atemperature
gravimetric ratge of about 9o
405 Phosph0 analysis of
475500 Molybdate Offsilver chromate can be dried anywhere inchromium.,the
Temperature C laboratory manuals direct to
weigh the
preci
this region, and, inpitfaa
The initial drop in weight in curve Dprecipitate exactly at 135p Fig. ~Weigh
a 1000 800 600

of Fig. 11.4 11.6 Rer

Fig. 11.4. Examples of Curve excess water. It is obvious fromthis
is stable over the range curve that mercurousrepresents
chroma
th (A) LiCIO4
emploved for weighing. At 256°C it commences to 52-256°C, so that this form observed weig
constant at about 671°C. decompose Cr,0, and the weight becoma ioy tico
into would b wt. loSs by an

Thus, while TGA provides the

possibility of determining the drying temperature rangesd LICIO,3H,o
precipitate for laboratory gravimetric work, 10423 g; obse
of the preipitation often have a profound this should always be borne in mind that the conditio 0.717 g; by ar
to empBoy a slow heating rate.
effect on the pyrolysis curve. It should
always be preferred (C) Mixture c
2 Analysis of Mixtures (21.3 wt.%) ar
An inspection of Fig. 11.4, curves A and B will wt. 0.9985 g:
reveal a significant difference in behaviad 0.533g. and b
between the oxalates of calcium and magnesium as
It will be noted that magnesium oxalate represented by their decomposition reaction determined
CaC,0, -’ CaCO, + CO found byt
CaCO, -’ CaO + CO, 3
AKir
MgC,0, ’ MgO + CO + CO,
does not pass through the carbonate stage. This difference in their reaction ar
thermal
simultaneous determination by TGA. They can be determined in a mixture behaviour permits the order of
by igniting at tw (Weignt, e
temperatures : at 500°C at which CaCO, andMgO are stabi automatica
473° 100 while at 900°C both metals exist as simple oxides. The weighcaon K
AgNog Img of a mixed precipitate at these two temperatures will perm (1
calculation of both the calcium and magnesium contents oft (2
608 (3
2 original sample.
Cu(NO),\151 The TGA of Cu-Ag alloy is based on the relative st There arE(4
bilities of their nitrates.C. Duval has simultaneously dete
278° mined the Cu and Ag content in the alloy by TGA. TGA curng thedeterminc
dynar
3 Mixture In Fig. 11.5, indicate that AgNO, is stable up to 473°C ats time durE
400° which it loses NO, and O, and the weight becoms cons based on
above 608°C when it is converted into metallic Ag CuP
700 nitrate, on the other hand, decomposes into CuO in two sr where K
Cuo being stable above700°C. Thus the weights of the ms gas cons
permit the analysis of the Cu-Ag aly
Fig. 11.5. TGA analysis of a binary Precipitate at 400 will curve A of Fig. 11.6 reveals the by
A

Cu-AG alloy. An inspection of decomposition patert

curve for
anhydrous LiCIO,. The
 -lysi Thermogravimetric Analysis
ermogram f 600f sharp and ensues at about 470°C. The
stable up t!
g° and 400 Temp'C
500
for the reaction theoretical weight
ng, therefoni LiCio, ’ LiCl+ 20,
B0°C. a00 4
for a 1.0114 gram sample of LiCiO, is 0.608
somewhat higher experimental weight gram.
loss of0.625 gram The
urve of silv 300
A be due to two factors : may
ess waier, an!
() possible loss of sample by
mains so up t
tion of silv! 200 vigorous decomposition reactions; and carry-off during the
(inthe occurrence of another
100 such asS decomposition reaction.
eof about 90 4LiCIO, ’2 Li,0 t 2CI, +7O,
The alkalinity of the decomposition residues obtained
the precipitat. 1000 800 600 400 200 100 200
attests to the presence of Li,0.
n, and, in faci +Weightloss mg Gain
An interesting extension of TGA to rapid quantiative
ctly at 135° Fig. 11.6Representative TGA Cuve or
semi-quantitative analytical work is illustrated by the
represents th (A) LiCIO, s'ample wt. 1.0114 g, determination of water in LiCIO,.3H,0 and LiCIO,.H,0 as
rous chroma! observed weight losses byTGA, 0.625g represented in curve B
rm would hi wt. loss by analytical balance 0.623g. to lose water at about 80°C(Fig. 11.6). The sample commenced
and
eight becoma (B) LiClO,.H,0 (28.3 wt.%) + about 350°C to yield anhydrous attained constant weight at
molten LiClO,. The latter
LICIO,.3H,O (71.7 wt.%). Sample wt started
thure ranges L0423 g; observedtotal wt. loss; by TGA LiCI The decomposing rapidly at about 470° togive substantially
TGA Curve B gives values of 26.6 weight % water
the condition 0.717g; by analytical balance 0.742 g.
and 73.4 weight% LiCIO4. (as against 28.3 wt.%) water and
ws be preferred (C) Mixture of LICIO,(51.4 w.o), water 71.7 wt. % LiCIO, determined by a gravimetric method)
(21.3 wt.%) and LiCI(24.6 wt.%). Sample
wt. 0.9985 g; observed wt. loss by TGA Curve Cof Fig. 11% represents the TGA run on 0.9985
0.533g. and by analytical balance 0.533g. gram Sample of gross composition 54.1 wt. % LiCIO,, 21.3
ein behaviou wt.% H,0,and 24.6 wt. % LiCl. On the basis of weight losses
tion reaction determined from this mixture during the dehydration and decomposition steps, the composition
found by she TGA was 56.3 wt. % LiCIO,, 19.5 wt.% of H,0 and 24.2 wt. % LiCI.
3 Kinetic Studies
VfGA, DTAand other thermoanalytical methods can be used to study kinetics of a chemical
reaction and to detefmine, basic kinetic constants such as the rate constant, K,activätion energy,
rpermits the E,order of reaction; *, andfrequency factor, 4: In these methods achange in some physical property
gniting at twd (weight, enthalpy, length or volume) as a function of temperature is measured continuously and
study
4eO are stabl automatically. The following types of reactions involving change in weight may be used to
kinetics :
es.The weigh reaction (1) A (solid phase) ’ B (solid phase) + C (gas phase)
res will perm
contents ofth (2) A (solid or liquid phase) ’ B (gas phase)
(3) A (solid phase) + B (gas phase)’ C (solid phase)
che relative st (4) A (solid phase) + B (solid phase) ’ C(solid phase) + D (gas phase)
approaches for kinetic studies : isothermal or static method: which inolves the
aneously dete There are two the degree of tr¡nsformation at constant temperature as afunctiop of time and
determination of
GA. TGAcurv of
which involves the determination of degree of transformation as a functionare
to473°C aftd the dynamic method by TGA
of the above reactions
lime during alinear increase of temperature. Kinectic studies
-comes cons based on the Arrhenius equation
llic Ag. Cup K= Ae-E/RT (11.1)
is the energy of activation, R is the
uO in tWo S where K is thesráte of reaction. A is the frequency factor, E
htsofthe mix gas constant and T is the temperature.
first order reactions. The weight loss yis given
he Cu-Ag allo A. Broido (1969) has developed a method for
reveals the T by
sition pattert