INTERPRETATION OF TGA

DATA & SOURCES OF

ERRORS IN TGA
 OUTLINE

TGA Curves
Types of TGA Curves
Interpretation of TGA Data
Sources of Errors in TGA
Elimination of Errors
 TGA CURVES

 Data from thermogravimetric analysis is often shown by a

graph representing mass as a function of temperature for
dynamic TGA.
 Results are displayed by a plot of mass change versus
temperature or time and are known as Thermogravimetric
curves or TG curves.
 TYPES OF TGA CURVE

1) TG curves are classified according to their shapes into seven

types.
 TYPES OF TGA CURVE

Type A- this curves shows no mass

change over the entire range of
temperature. It can be concluded
that the decomposition temperature
for sample is greater than the
temperature range of instrument.
Type B- this curves shows that
there is large mass loss followed by
mass plateau and is formed when
evaporation of volatile product(s)
during drying, desorption or
polymerization takes place. If a non-
interacting atmosphere is present in
the chamber, type B curve will
change into type A curve.
 TYPES OF TGA CURVE

Type C- this curve shows

the single-stage
decomposition
temperatures (Ti and Tf).
Type D- this curve shows
the multi-stage
decomposition processes
where reaction is resolved.
Type E- this curve shows the
multi-stage decomposition
reaction where reaction is
not resolved.
 TYPES OF TGA CURVE

Type F- this curve shows the

increase in mass in the
presence of an interacting
atmosphere e.g. surface
oxidation reactions.
Type G- this curve shows
multiple reactions one after
the other e.g. surface
oxidation reaction followed
by decomposition of reaction
product(s).
 INTERPRETATION OF TGA DATA

Plateau:
A plateau is that part of the TG curve (Point A) where
the mass is essentially constant or there is no change
in mass .
 Procedural Decomposition Temperature:
The initial temperature, Ti, (Point B) is that temperature (in
Celsius or Kelvin) at which the cumulative-mass change reaches
a magnitude that the thermobalance can detect.
 Final Temperature:
The final temperature, Tf, (Point C), is that temperature (in
Celsius or Kelvin) at which the cumulative mass change reaches
a maximum.
 INTERPRETATION OF TGA DATA

Formalized TG Curve
 INTERPRETATION OF TGA DATA

 Reaction Interval:
The reaction interval is the temperature difference between
Tf and Ti.
 Isobaric Mass-change Determination:
A technique in which the equilibrium mass of a substance at
constant partial pressure of the volatile product(s), is measured
as a function of temperature while the substance is subjected
to a controlled temperature program. The record is the isobaric
mass-change curve; the mass is plotted on Y-axis and
temperature on X-axis increasing from left to right.
 INTERPRETATION OF TGA DATA

 Evolved Gas Detection (EGD):

A technique in which the evolution of gas from a substance
is detected as a function of temperature while the substance is
subjected to a controlled temperature program.
 Evolved Gas Analysis (EGA):
A technique in which the nature and/or amount of volatile
product(s) released by a substance are/is measured as a
function of temperature while the substance is subjected to a
controlled temperature program. The method of analysis should
always be clearly stated.
 INTERPRETATION OF TGA DATA

Information from TG Curve:

The plot of weight/mass against temperature or time
produced by a thermogravimeter is called Thermogram.
The following features of TG curve should be noted
1) Plateau: a region of no mass change indicates the thermal
stability of the sample/substance. Thermal stability is the
ability of a substance to maintain its properties as nearly
unchanged as possible on heat. This information about
thermal stability is significant for engineers as they then
know the temperature ranges of in which substances like
alloy, building materials, polymers, etc. can be used.
 INTERPRETATION OF TGA DATA

2) Weight/Mass Loss: heating a sample to given temperature

causes it to lose weight/mass. Mass/weight loss is
informative to inorganic chemist who can then determine the
composition of substance/sample and understand the
reaction involved in decomposition.
3) Procedural Decomposition Temperature: by looking at
thermogram, one can determine the procedural
decomposition temperature (Ti) indicating the decomposition
or evaporation of sample/substance
4) Composition: weight/mass lost by heating helps determine
the composition of substance/sample, also allows analytical
chemists to identify unknown compound or determine the
amount/percentage/weight of a compound in mixture of
different compounds.
INTERPRETATION OF TGA DATA
INTERPRETATION OF TGA DATA
 SOURCES OF ERRORS IN TGA

 Accuracy involves both trueness and precision.

 Trueness is the closeness of agreement between the mean
value and a true value.
 Precision is the closeness of agreement between individual
values.
 Trueness and precision are a measure of the systematic and
random errors of measurement, respectively.
 There are a number of sources of error in TGA, and they could
lead to inaccuracies within the recorded temperature and
mass data.
 A few of the errors might be corrected through placing the
thermo balance at proper place and handling it along with
great care.
 SOURCES OF ERRORS IN TGA

 The important causes of errors in measurement are

instrumental influences, environmental influences, sampling
and sample preparation, experimental parameters,
shortcomings of the operator, evaluation methodology, and
time-dependent factors.
 The accuracy of analytical methods can be enhanced by
having a broad understanding of the measurement procedures
and method development in a competent manner.
 SOURCES OF ERRORS IN TGA

A. Buoyance effect:
 If a thermally inert crucible is heated while empty there is
common an apparent weight modifies as temperature
increases.
 This is because of effect of change within buoyancy of the gas
in the sample environment along with the temperature,
increase convection and probable effect of heat from the
furnace in the balance itself. Present, in most modern
thermobalances, this effect is negligible.
 Therefore, if essential, a blank run along with empty crucible
could be performed over the appropriate temperature range.
 The resultant record could be used as a correction curve for
subsequent experiment performed in the similar condition.
 SOURCES OF ERRORS IN TGA

B. Condensation on balance suspension:

 Condensation of the sample will also affect the mass of the
sample and as a result the shape of TG curve .
 This could be prevented through managing a dynamic
atmosphere around the sample within the furnace so in which
the entire condensable product might be driven through the
flowing gases.
C. Random fluctuation of balance mechanism
D. Reaction among sample and container
E. Convection effect from furnace
F. Turbulence effect from gas flow
G. Induction effect from furnace
 SOURCES OF ERRORS IN TGA

How previous mentioned errors can be eliminated?

Error C(Random fluctuation of balance mechanism) could be

prevented through proper placing of balance within the
laboratory and error E (Convection effect from furnace) could be
prevented through sensible choice of sample container. Last
three errors E,F,G (Convection effect from furnace, Turbulence
effect from gas flow, Induction effect from furnace) have to be
considered in the design of the furnace, the balance and its
suspension system.
 SOURCES OF ERRORS IN TGA

Elimination of Errors:
 Through avoiding excessive heating rate and proper gas flow
rate some of above mentioned errors might be avoided.
1) In the light of above elaborates it is essential to calibrate
thermobalance before to use.
2) Calibration of thermobalance for the measurement of mass.
3) It could be completed through adding known mass of the
sample container and noting the reading of the chart.
4) Temperature calibration: ferromagnetic standards are used
for these reasons. In a magnetic field there substances
showed detectable mass changes. The ferromagnetic
standards are quite appropriate for the temperature range
from 242 to 771° C.
 SOURCES OF ERRORS IN TGA

Other Important Sources of Errors

Several factors contribute to systematic and random
measurement errors in analytical procedures.
The significant ones are listed below:
1) Instrumental influences
2) Sampling and sample preparation
3) Environmental influences
4) Experimental parameters & Evaluation methodology
5) Time-dependent factors
6) Shortcomings of the operator
7) Gross errors
 SOURCES OF ERRORS IN TGA

1) Instrumental Influences:
A common cause for systematic errors in TGA measurement is
improper adjustment of the instrument used for the measurement.
2) Sample Preparation:
Sample selection and preparation in TGA is a major step in
analytical measurements. Measurement errors can occur if the
following factors are overlooked:
 Changes in the sample due to stress
 Change in the material properties over time, during storage or
transport
 Instability of the sample
 Inaccurate sample weighing
 Inaccurate determination of the sample geometry
 SOURCES OF ERRORS IN TGA

3) Environmental Influences:
The measuring system should be insensitive to influences of
its environment. In TGA, the key factors affecting the
measurement signal are given below:
 Pressure
 Temperature
 Vibrations
 Contamination
4) Method Parameters and Evaluation:
Conditions, such as sample mass, sample geometry, heating
and cooling rate, atmosphere, temperature range, crucible,
force, pressure, displacement and frequency, sampling and
sample preparation and storage, in which a measurement is
carried out must be monitored for each measurement.
 SOURCES OF ERRORS IN TGA

5) Time-Dependent Factors:
Time is another key factor that affects measurement errors in a
systematic way. For example, a sensor’s sensitivity can change over
time.
6) Shortcomings of the Operator:
Individual abilities, practical skills, experience and theoretical
knowledge of the operator also influence systematic and random
errors of measurement.
7) Gross Errors:
Gross errors are mainly comprising the following:
 Wrongly transcribed results and measurement data
 Signs and rounding
 Errors in calculations
 Programming errors in computer programs
 Incorrect weighing or determination of sample geometry
 Mistaken identity of sample material or wrong reagent concentrations
 SOURCES OF ERRORS IN TGA

Detection and Elimination of Measurement Errors

Systematic errors of measurement can be detected using
comparative measurements. The three major comparative
measurements are listed below:
 Deliberate change of the experimental parameters
 Use of a fundamentally different measuring method
 Inter laboratory studies (Round Robin studies)