ADVANCED ANALYTICAL INSTRUMENTATION

THERMOGRAVIMETRY

Introduction:
Instrumental gravimetric analysis techniques are those in which a physical property of a
substance or its reaction products is measured as a function of temperature. Usually, the substance
is subjected to a controlled temperature program. This method find widespread use for both quality
control and research applications on polymers, pharmaceutical preparations, clays, minerals, metals,
and alloys.
Thermogravimetric Analysis (TGA):
1. Principle:
In a thermogravimetric analysis (TGA) the mass of a sample in a controlled atmosphere is
recorded continuously as a function of temperature or time as the temperature of the sample is
increased. A plot of mass or mass percentage as a function of time is called a thermogram.
2. Instrumentation:
Commercial instruments for TGA consist of (1) a sensitive microbalance, called a
thermobalance; (2) a furnace; (3) a purge-gas system for providing an inert, or sometimes reactive,
atmosphere; and (4) a computer system for instrument control.
2.1 Thermobalance:
A number of different thermo-balance designs available commercially are capable of providing
quantitative information about samples ranging in mass from less than 1 mg to 100 g. Many of the
balances can detect changes in mass as small as 0.1 g. Although the sample holder must be housed
in the furnace, the rest of the balance must be thermally isolated from the furnace. The Figure 1 is a
schematic diagram of one thermo-balance design.

Figure 1: Schematic of thermogravimetric analyser.

In the figure 1, A is beam balance, B is sample cup and holder, C is a counter weight, D is a
lamp and photodiodes, E is magnetic coil and F is a permanent magnet. G, H and I are computer
data acquisition, data processing and control systems respectively. J is a printer and display unit. A
THE UNIVERSITY OF DODOMA, COURSE CODE: CH 613 1
INSTRUCTOR: DR VEGI MAHESWARA RAO
 ADVANCED ANALYTICAL INSTRUMENTATION

change in sample mass causes a deflection of the beam, which interposes a light shutter between a
lamp and one of two photodiodes. The resulting imbalance in the photodiode current is amplified
and fed into coil E, which is situated between the poles of a permanent magnet F. The magnetic
field generated by the current in the coil restores the beam to its original position. The amplified
photodiode current is monitored and transformed into mass or mass-loss information by the data-
processing system. In most cases mass versus temperature data can either be plotted in real time or
stored for further manipulation or display at a later time.
2.2 The Furnace:
Furnaces for TGA typically cover the range from ambient temperature to 10000C, although
some can be used for temperatures up to 1600°C. Heating rates can often be selected from 0.1°C
/min to 100°C/min. Some units can heat as rapidly as 200°C/min. Insulation and cooling of the
exterior of the furnace is required to avoid heat transfer to the balance. Nitrogen or argon is usually
used to purge the furnace and prevent oxidation of the sample. For some analyses, it is desirable to
switch purge gases as the analysis proceeds.
2.3 Calibration:
The temperature axis is usually calibrated by using a material of known Curie point or
sometimes a melting point standard. The Curie point is the temperature at which a ferromagnetic
material becomes paramagnetic. The ferromagnetic material is suspended in a magnetic field
oriented such that a vertical component of magnetic force acts on the sample. The magnetic force
acts as an equivalent magnetic mass on the TGA balance beam to indicate an apparent sample mass.
When the sample is heated through its Curie point, the magnetic mass is lost, and the balance
indicates an apparent loss in mass. Temperature accuracy is better than 1OC with most furnaces, and
temperature precision is typically ±0.1°C. Furnaces are usually cooled by forced air. Most furnaces
can be cooled from 10000C to 50°C in less than 20 minutes.
2.4 Sample holders:
Samples are typically contained in sample pans made of platinum, aluminum, or alumina.
Platinum is most often used because of its inertness and ease of cleaning. The volumes of sample
pans range from 40 L to more than 500 L. Autosamplers are available as attachments for most
TGA systems. With the majority of these units, all aspects are automated under software control.
The sample-pan taring, loading, and weighing; the furnace heating and cooling; and the pan
unloading are totally automatic.
The temperature recorded in a thermogram is ideally the actual temperature of the sample.
This temperature can, in principle, be obtained by immersing a small thermocouple directly in the
sample. Such a procedure is seldom followed, however, because of possible catalytic decomposition
of samples, potential contamination of samples, and weighing errors resulting from the

THE UNIVERSITY OF DODOMA, COURSE CODE: CH 613 2

INSTRUCTOR: DR VEGI MAHESWARA RAO
 ADVANCED ANALYTICAL INSTRUMENTATION

thermocouple leads. Because of these problems, recorded temperatures are generally measured with
a small thermocouple located as close as possible to the sample container.
3. TGA/MS and TGA/FTIR:
TGA is used to determine the loss in mass at particular temperatures, but TGA cannot
identify the species responsible. To obtain this type of information, the output of a
thermogravimetric analyzer is often connected to a Fourier transform infrared (FTIR) or a mass
spectrometer (MS). Several instrument companies offer devices to interface the TGA unit to a
spectrometer.
4. High-Resolution TGA:
In high-resolution TGA, the sample heating rate fluctuates so that the sample is heated more
rapidly during periods of constant mass than during periods when mass changes occur. This allows
higher resolution to be obtained during the interesting periods and reduces the time of inactivity.
5. Applications:
Because TGA monitors the mass of the analyte with temperature, the information provided
is quantitative, but limited to decomposition and oxidation reactions and to such physical processes
as vaporization, sublimation, and desorption. Among the most important applications of TGA are
compositional analysis and decomposition profiles of multicomponent systems.
In polymer studies, thermograms provide information about decomposition mechanisms for
various polymeric preparations. In addition, the decomposition patterns are characteristic for each
kind of polymer and can sometimes be used for identification purposes (Figure 2).

In this diagram

PVC = polyvinylchloride;

PMMA= polymethylmethacrylate;

LDPE = low-density polyethylene;

PTFE= polytetrafluoroethylene;

PI = aromatic polypyromelitimide.

Figure 2: The decomposition patterns for five polymers obtained by thermogravimetry.

In the Figure 3 there is a recorded thermogram obtained by increasing the temperature of

pure CaC2O4.H20 at a rate of 5°C/min. The clearly defined horizontal regions correspond to

THE UNIVERSITY OF DODOMA, COURSE CODE: CH 613 3

INSTRUCTOR: DR VEGI MAHESWARA RAO
 ADVANCED ANALYTICAL INSTRUMENTATION

temperature ranges in which the indicated calcium compounds are stable. This figure illustrates the
use of TGA in defining the thermal conditions needed to produce a pure species.

Figure 3: Thermogram of calcium oxalate monohydrate.

Advantages of Thermobalances over other balances:
i. It can sense very small mass changes in the order of 10-6 g.
ii. It requires only small sample weights.
iii. By this balance, one can maintain fast heating rates with good resolution.
iv. There is no influence of surrounding environmental factors such as temperature, pressure and
humidity….on the experimental results.
v. The thermobalance can also be useful for isothermal studies.
vi. In this thermobalance, one can hold the furnace at 10000C without any balance drift.

THE UNIVERSITY OF DODOMA, COURSE CODE: CH 613 4

INSTRUCTOR: DR VEGI MAHESWARA RAO