THERMO GRAVIMETRIC

ANALYSIS

Submitted by : Javed Iqbal

Roll no : F19 5023
Class : MSC chemistry (A)
Submitted to : Dr. Abdul Hamid
Subject : Physical Chemistry
 Contents

 Thermal analysis
 Types of thermal analysis
 Principle of thermal analysis
 Recording of results
 Information obtain from TG curve
 Instrumentation
 Factors affecting
 Applications
Thermo gravimetric Analysis or
thermal gravimetric Analysis(TGA)
 Thermo gravimetric Analysis is a method of
thermal analysis in which the mas of sample
is measured over time as the temp. changes .
 This measurement provides information about
physical phenomena such as phase
transitions, absorption, adsorption and
desorption as well as chemical phenomena
including chemisorption, thermal
decomposition and solid gas reaction(e.g
oxidation or reduction)
TGA of calcium oxalate
monohydrate
 The successive plateau corresponds to
the formation of anhydrous salt calcium
carbonate and calcium oxide
 Cc2 o4.H2o------->cac2o4+ H2o
 Cac2o4--------> caco3 + co
 Caco3----------> Cao + co2
 The thermo gram indicate that the
loss of water begins at 100*C and loss of
CO at 400*C and CO2 at 680*C
 Types of
Thermogravimetry
Three types

1. Iso thermogravimetry in this technique the sample weight

is recorded as a function of time at constant temperature
2. Quasistatic thermogravimetry in this technique the
sample is heated to constant weight at each of the series of
increasing temperature
3. Dynamic thermogravimetry in this technique a sample is
heated in an environment whose temperature is changing in
predetermine manner generally at linear rate
Thermo gravimetric
Analysis(TGA)
Principle
 In thermo gravimetric analysis the sample is heated in
given environment (air, N2 and AR etc.) at controlled
rate.
 The change in the weight of the substance is recorded
as a function of temperature or time.
 The temp. is increase at a constant rate for a known
initial weight of the substance and the changes in
weight are recorded as function of temp. at different
time interval.
 This plot of weight changes against temp. is called
thermo gravimetric curve or thermo gram
 Description

it is a tecnhnique which is studied under thermal

analysis and is empolyed for detection of such type
of material which undergo mass change when
subjected to thermal events decomposition ,oxidation,
reduction etc.

For this reason it is very significant to optimize those

conditions on which the change of mass of sample
depend throughout the experiment.
 Recording of results

1. The instrument used for thermogravimetry is

programed precision balance for rise in temp
known as thermo balance
2. Result are displayed by a plot amass change vs
temp or time are known as TG curve.
3. TG curves are normally plotted with the mass
change in percentage on the y axis and temp or
time on the x axis.
 Recording of results

There are two temp in the reaction

 Ti (procedural decomposition temp)
representing the lowest temp at which the on
set of a mass change is seen
 Tf (final temp) representing lowest temp at
which the process has been completed
respectively.
 The reaction temp and interval depend on the
experimental condition therefore they donot
have any fixed value.
Information obtained from TG
curves
Plateau: a plateau is that part of the TG curves where
the mass is essentially constant or there is no change
in mass
Procedural decomposition temp :
The initial temp is that temp at which the cumulative
mass change reaches a magnitude that the thermo
balance can detect
Information obtained from TG
curves

Final temperature:
1. Final temperature is that temp ( in celcius or
kelvin) at which the cumulative mass change
reaches a maximum
Reaction interval :
2. The reaction temp is the temp difference between
Tf and Ti.
Information obtained from TG curves

It can be concluded that thermogravimetry is

concerned with the change in weight of material as its
temp changes.
First this determine the temp at which the material
losses weight this loss indicated decomposition or
evaporation of sample
Second the temp at which no weight loss that takes
place is revealed which indicate stability of the
material. These temp ranges are physical properties
of chemical compound and can be used for there
identification.
 Instrumentations
There are different instruments are used in this process
Microbalance:
It is the most important component of thermo balance.
A microbalance is used to record a change in mass of sample .
FEATURES:
It should accurately and reproducibly record the change in mass of
sample in wide range of atmospheric change in temp mass using
a recorder
It should provide electronic signals to record the change in mass.
The electronic signals should provide rapid response to change in
mass.
It should be stable at high ranges mechanically and electrically
 Instrumentations
Modern microbalance have ability to be not affected
by vibration .
Its operation should be user friendly.
After sample has been placed on microbalance it is
for 10-15 minute to stabilize.
Types of balance:
 Deflection type instrument
 Null type instrument
 Instrumentations
Deflection balance:
Following types :
Beam type
1. helical type
2. Cantilevered beam
3. torsion wire
Null point balance:
It consist of sensor which detect the deviation from the
null point and restore the balance to its null point and
restore the balance to its null point by means of
restoring force.
 Instrumentations
Sample holder or Crucible:
 The sample to be studied is placed in sample
holder or crucible it is attached to weighing arm of
microbalance.
 There are different varieties of crucible used some
different shapes and size while some different
material used.
 They are made from platinum, aluminum ,quartz or
alumina and some other material like graphite
,stainless steel and glass etc .
 Instrumentations
Crucible should have temp at least 100k greater than
temp range of experiment and must transfer heat
uniformly to sample therefore the shape thermal
conductivity and thermal mass of crucible are
important its depend on weight and nature of sample
and temperature range .
There are different types of crucible:
1- Shallow pans
2- Deep crucible
3- Loosely covered crucibe
4- Retort cups
 Instrumentations
Furnace:
Furnace should be designed in such a way that it
produces linear heating range.
It should have a hot zone which can hold sample and
crucible and its temp correspond to temp of furnace.
There are different combination of microbalance and
furnace available the furnace heating coil should be
wound in such a way that there is no magnetic
interaction b\w coil and sample or there can cause
apparent mass change.
 Instrumentations
Coil used are made of different material with variant
temp changes.
 Nichrome wire or Ribbon for T<1300k
 Platinum for T>1300K
 Platinum 10% rhodium alloy for T< 1800k

The size of furnace is important a high mass furnace

may have high range of temp and obtain uniform hot
zone but require more time to achieve the desire
temp comparatively a low mass furnace may heat
quickly but its very difficult to control rise in temp and
maintain hot zone .
 Temperature measurement

It is done with the help of thermocouple.

The position of thermocouple is important it can be
adjusted in following ways
1- Thermocouple is placed near the sample and has
no contact with sample container this arrangement is
no preferred in low pressure .
2- The sample is kept inside the sample holder but
not in contact with it .It responds to small temp
change only.
3- Thermocouple is placed either in contact with
sample or with sample container.
 Recorder

The recorder mainly two types :

1- Time base potentiometer strip chart recorder.
2- X-Y recorder .
In some instrument light beam galvanometer
photographic paper recorders or one recorder with
two or more pens are also used .
In the X-Y recorder we get curve having plot of weight
directly against temperatures.
Block diagram of TGA
Example: TGA Curve for AgNO3
The horizontal portion of the curve indicates that there
is no change in weight(AB&CD) and the portion BC
indicates that there is weight change.
The weight of the substance remains constant up to a
temperature of 473*C indicating
that Ag NO3 is thermally stable up to
A temp. 473*C.
At this temp. its starts losing its weight and
this indicates that the decomposition
starts
at this temp. it decomposes to NO2, O2 and Ag
Factors affecting the TG
curve
Two types:
(1) Instrumental factor
(2) Sample characteristics
Instrumental factor :
Furnace heating rate: the temp. at which the compound
decomposed depends upon the heating. When the heating rate
is high, the decomposition temp is also high. A heating rate of
3.5 C per minute is usually recommended for reliable and
reproducible TGA.
Furnace atmosphere : the atmosphere inside the furnace
surrounding the sample has a profound effect on decomposition
temp of the sample .A pure N2 gas from cylinder passed
through the furnace which provide an insert atmosphere.
Factors affecting the TG
curve
Sample characteristics :
1. Weight of the sample:
a small weight of the
sample is recommended using a small weight
eliminates the existence of temperature gradient
through out the sample.
2. Particles size of the sample :
The particles
size of the sample should be small. The use of large
particles or crystals may result in apparent very
Rapid weight loss during heating
 Applications of TGA
1. From TGA we can determine the purity and thermal
stability of both primary and secondary standards.
2. Determination of the composition of the complex mixture
and decomposition of mixture
3. For studying the sublimation behavior of various
substances .
4. TGA is use to study the kinetics of the reaction rate
constant
5. Used in the study of catalyst: the change in chemical
states of the catalyst may be studied by TGA techniques .
6. Zinc chromates is used as a catalyst in the synthesis of
methanol .