The application of thermogravimetry analysis (TGA) caused a real revolution in the early

1950s. Today, thermogravimetry (TG) resolves many analytical problems in inorganic

chemistry, organic chemistry, ceramics, metallurgy, pigment development, mineralogy and
geochemistry. Application of thermogravimetry is limited to events with detectable mass
changes. Otherwise, other techniques, such as differential thermal analysis (DTA) or
differential scanning calorimetry (DSC), must be used. The main thermal events recorded by
TG are summarized in table 1

Sublimation A (solid) → A (gas)

Vaporization A (liquid) → A (gas)
Adsorption A (solid) + B (gas) → A (solid) (Bgas-ads)
Absorption A (solid) + B (gas) → A (solid) (Bgas-abs)
Desorption A (solid) (Bgas-ads) → A (solid) + B (gas)
A (solid) (Bgas-abs) → A (solid) + B (gas)
Oxidation A (solid) + B (gas) → C (solid)
Pyrolisis A (solid) → B (solid) + Gases
Volatilization A (solid) + B (gas) → Gases
Heterogeneous catalysis A (solid) + (Gases)1 → A (solid) + (Gases)2
Table 1 shows the thermal event registered by Thermogravimetry Analysis (TGA).

Other than that, there is some type of the reaction that have been observed by scientists
or researcher nowdays in Thermogravimetry Analysis (TGA). For example,

1. Loss of constituent water molecules such as dehydrations may be either single or

multi-stage and may involve the loss of the elements of water. Example from hydroxyl
groupings (-OH).

2. Decomposition reactions, which may be either of a disproportionation or of a

degradation type. In Brill (1905) research probably on his first publication in the field of
thermogravimetry, presented the data of this degradation type. He studied about the
decomposition of magnesium, calcium and barium carbonates;

MIICO3 MIIO + CO2

 3. Degradation reactions specifically involving the atmosphere such as oxidative
degradation. An example is provided by the oxidation in air of trispropylenediamine
chromium (III) chloride;

2[Cr(pn)3]Cl3 Cr2O3 + volatiles

4. Loss of constituent volatile ligands from inorganic complexes. An example is provided

by the loss of ethylenediamine from trisethylenediamine chromium (III) chloride;

[Cr(en)3]Cl3 [Cr(en)2Cl2]Cl + en

The function of differential thermal analysis (DTA) is to measures the difference of

temperature between a sample and a reference (ΔT) versus temperature. Furthermore, for
differential scanning calorimetry (DSC) function is to records the differences of heat quantity
between a sample and a reference versus temperature. Both of the techniques was applied
by a programmed heating rate. DSC gives a value for the amount of absorbed or evolved
energy in a particular transition and therefore also provides a direct calorimetric measurement.

Applications of DTA and DSC to a samples are:

• Determination of enthalpy in phase changes
• Determination of phase diagrams
• Determination of enthalpy in chemical reaction
• Kinetic analysis
• Identification and characterization

The Thermogravimetric analysis (TGA) is used to monitors the mass of the analyte with
temperature, the information provided is quantitative, but limited to decomposition and
oxidation reaction 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 system. Beside the application of TGA also can be determine by
other purpose which are,

i. Determination of the solvation state of a compound. Thermogravimetry can be used

as a rapid method to determine the solvation state of a compound.

ii. Uses of thermogravimetry to facilitate interpretation of differential scanning calorimetry

thermograms. Thermogravimetry is a powerful adjunct to DSC studies, and are
routinely obtained during evaluations of the thermal behavior of a drug substance or
excipient component of a formulation. Since TG analysis is restricted to studies
 involving either a gain or a loss in sample mass (such as desolvation decomposition
reactions), it can be used to clearly distinguish thermal events not involving loss of
mass (such as phase transitions).

iii. Estimating the isothermal lifetime of pharmaceutical coatings using thermogravimetric

decomposition kinetics. Determining the decomposition rate and expected thermal
lifetime of formulation components at the elevated temperatures of formulation
processes is essential for avoiding thermal decomposition of the formulation
components during processing. Such processes include melt-extrusion casting, spray-
congealing, and hot-melt fluid-bed coating or enrobing of drug substances.
Thermorgravimetric Analysis instruments has developed automated
thermogravimetric analysis and related kinetic programs that enable a rapid
determination of decomposition rates to be made.

The thermal decomposition is dependent on the nature of both anion and cation there has
been little attempt to relate thermal decomposition data to modern theories. There are some
of the example of research about the anion derived from the element according to its group.

1. Anions derived from elements of group 3.

For example, some borates of lithium and sodium have been studied. The
decomposition of some calcium aluminate hydrates and calcium carbo-aluminate been
investigated, that of the former under constant water vapour pressure.

2. Anions derived from elements of group 4.

i. Carbonates is the one of the compound that have been research by one of the
scientist called Freeman where he studied about the kinetics of the
decomposition of calcium carbonate, comparing results obtained with results
from isothermal studies. Lanthanum carbonate has been investigated as a
suitable weighing form for lanthanum, other lanthanon carbonates have been
studied .The effect of crucible design on the decomposition characteristics of
lead carbonate has been studied. Other recent studies on carbonates include
ammonium scandium carbonate and certain cobalt complex carbonates.
Thermogravimetric studies of solid-state reactions between cerium oxide,
neodymium oxide or samarium oxide with either sodium carbonate or sodium
 sulphate and of the strontium carbonate, zirconium oxide and barium carbonate
and zirconium oxide systems have been made. There were scientist have
studied about the systems of sodium carbonate, silica and calcium carbonate
and silica by both thermogravimetric and differential thermal analysis and
discussed their behaviour in relation to glass manufacture.

ii. Formates, acetates, oxalates and other oxycarbon anions such as copper,
formate and aluminium acetate have recently been investigated. However,
oxalates have received a great deal of attention, for example those of copper,
beryllium, magnesium, calcium, zinc, cadmium, lead, manganese, cobalt,
nickel, scandium, yttrium, lanthanum, lanthanon, thorium and
uranium ,complex cobalt oxalates, oxalato-niobates and other complex
oxalates. The additivity of the decomposition curves of a mixture of oxalates
has been demonstrated, and the thermal decomposition pattern of oxalates in
different atmospheres has received attention. Other compounds of oxycarbon
anions that have been studied include potassium hydrogen phthalate, caesium
propionate, butyrate, and isovalerate and lanthanum and cerium palmitate,
laurate and stearate.

iii. Silicates also one of the compound that have been investigated about the
dehydration behaviour of several silicates and silicate minerals. The use of
thermogravimetry combined with infrared studies has been suggested to permit
a distinction to be made between constitutional and adsorbed water. The effect
of alkaline-earth chlorides on the dehydration of silica Xerogel has been studied.

iv. Thermogravimetry has been used also to determine the conditions under which
calcium orthoplumbatelv is formed

3. Anions derived from elements of group 5.

i. Nitrogen, the reaction between boron oxide and sodamide to yield boron
nitride and the oxidation of aluminium nitride have been studied
thermogravimetrically. The thermogravimetric behaviour of cerium
praseodymium, neodymium, samarium, thorium, plutonium and nickel nitrates
has been investigated. Lead azide also has been studied.
 ii. Phosphorus, the resistance to oxidation of some transition metal phosphides
has been described. Phosphates of ammonium, sodium, beryllium, strontium,
aluminium, antimony, chromium and iron and some halophosphates have
been studied. The decomposition of disodium dihydrogen pyrophosphate and
the reactions between magnesium pyrophosphate and strontium oxide or
magnesium hydroxide have been reported. Gerrard, Mooney and Rothenbury
(1962) have used thermogravimetry in their investigation of polymers formed
from chloroborazoles and phosphorus esters.

iii. Other Anion such as Arsenic acid and arsenates of chromium, cobalt and
nickel have been investigated thermogravimetrically. Ammonium
metavanadate, some niobates and tantalates and some oxalato-niobates
have also been studied.

4. Anions derived from element of group 6.

i. Oxides, peroxides and related compounds, the thermal dehydration of copper,

beryllium, magnesium, iron and nickel hydroxides has been also investigated
thermogravimetrically. The thermogravimetric studies of oxides may be sub-
divided into two main sections:

(a) Dehydration reactions of hydrated oxides and subsequent

disproportionation reactions

(b) Solid-state reactions, which may be either solid - solid reactions involving
loss of volati1e or solid - gas reactions involving loss or gain in weight, have
also been reported.

ii. Sulphides, sulphates and other anions of sulphur, the oxidation and thermal
decomposition of copper , zinc, cadmium, mercury, germanium, tin, lead and
various nickel sulphides has been described and there have been two studies
on pyrite. Sulphates of the metals listed below have been studied such as
copper, beryllium magnesium, calcium, mercury, indium, tin, lead, nickel,
uranium, lanthanum and other lanthanon as well as several double and
complex sulphates. Solid - solid and solid – gas reactions involving sulphates
have also been reported.
5. Anions derived from other elements of group 6.

The selenides of arsenic, rhenium and mercury have been shown to sublime at definite
temperatures. The decomposition of magnesium selenates has been compared to the
corresponding sulphates. The thermal decomposition of neodymium and basic yttrium
chromate has been studied also, as well as some isopolychromates of potassium.
Tungstic acid, ammonium paratungstate, several 12-heteropoly tungstates ammonium
and quinolinium molybdophosphate have been investigated thermogravimetrically.

6. Anions derived from elements of group 7.

Thermogravimetric studies of mono-amine dichloro zinc and basic aluminium chlorides

have been made. A study of the application of high temperature thermogravimetry of
chlorides and sulphates to soil analysis has been reported. The thermal decomposition
of the following compounds involving oxyanions has been reported which are sodium
barium bromate and chlorate and copper iodate, together with the perchlorates of
potassium, magnesium, calcium and barium. Binary systems of potassium perchlorate
with either alkaline or alkaline-earth metal nitrates, and the course of the reaction
between potassium chlorate and manganese dioxide have been followed by using
thermogravimetric techniques.

7. Anions derived from elements of group 8.

Alkali metal, copper, magnesium and alkaline-earth ferrocyanides have been

examined by Seifer. Work on ammonium chloroplatinate and bromoplatinic acid has
also been reported.

8. Complex inorganic compounds.

Complex compounds of cobalt, chromium, nickel and platinum in which the ligand
groups are wholly or partly either ammonia, ethylenediamine, propylenediamine or
pyridine have been widely studied. The 8-hydroxyquinolines of many bivalent metal
uranium and plutonium have been studied. Bivalent metal anthranilates, substituted
anthranilates of lanthanum and and other related chelate complexes have all been
studied thermogravimetrically.
 Although most thermal analysis methods can deal with samples as solids, semi-solids
or liquids, a review of the current literature would suggest that the broad term, solid-state
characterization, could apply to a majority of the applications in pharmaceutical research.
Common applications include the characterization of the physicochemical properties of
crystalline solids and the detection and identification of polymorphic forms. With the increased
utilization of solid dispersions and other polymeric dosage forms, thermal analytical
techniques have been called upon more frequently to aid researchers with their development
and characterization. Thermal analytical techniques are also used to study the effects of
lyophilization and to develop optimal lyophilization formulations and cycles. Several
techniques are also used to study kinetics in the solid-state, including decomposition,
accelerated stability and the effects of aging on various formulations.
Other than that, industry also use the application of TGA to analysis on their product.
For example,
i. Polymer.

The thermoplastic polymer is common in packaging and household items. For the
analysis of plastic raw materials, DSC can be used to analyze the effect of additives (including
stabilizers and colour) and optimization the materials and manufacturing processes plasticity.
For example, studies of oxidation induction time (OIT) by DSC of thermoplastics can be
determined (usually a polyolefin) which antioxidant polymer stabilizer additive amount.
Polymer composition analysis is the advantage of TGA, which separates the filler, the
polymeric, resin and other additives. TGA can also test the thermal stability, and an additive
effect and influence, such as flame retardants.

ii. Metal

Metal manufacturing (cast iron, grey iron, ductile iron, compacted graphite iron, 3000
series aluminium alloys, copper alloys, silver, and complex steels) is one of the applications
of thermal analysis. Liquid metal samples were removed from the furance and put into the cup
with thermocouple temperature sensor embedded. The temperature is then monitored and
recorded phase change diagram (liquidus, eutectic, and solidus). The phase change diagram,
the chemical composition of metal castings or its crystal structure also can be calculated

iii. Food

Most changes are related to food temperature, mainly in the production, transportation,
storage, preparation, consumption process. For example, low-temperature sterilization
pasteurization, sterilization, evaporation, cooking, freezing, cooling, and other processes
cause changes in physical and chemical properties of food ingredients, and the impact of the
final product, such as taste, appearance, texture and stability. It will thus enhance certain
chemical reactions, such as hydrolysis, oxidation or reduction reactions may also cause
physical changes in the food, such as evaporation, melting, crystallization, polymerization or
gelation. More accurate understanding of the effects of temperature on the properties of the
food make food manufacturers improve production technology and product quality. In principle,
most of the analysis may be applied in the food industry and to monitor food quality. Thermal
Analysis Applications usually relatively small, mainly when used to measure temperature
changes in the physical properties of foods (TG / DTG, DTA, DSC).

iv. Printed Circuit Boards (PCB)

Power consumption is an important issue in today's PCB design. Power dissipation

causes a temperature difference, heat dissipation problems caused by the wafer. In addition
to reliability problems, excess heat will affect the performance and safety of the equipment.
An integrated circuit operating temperature should be kept below the limit makes circuit
damaged. Thermal analysis equipment and therefore the printed circuit board industry can
use.

In thermogravimetric analysis, the change in weight in relation to a change in

temperature in a controlled environment is measured. Heat is used in TGA to force reactions
and physical changes in materials and a schematic diagram of a TG apparatus is given in
diagram 1. The thermogravimetric analysis instrument usually consists of a high-precision
balance and sample pan. The pan holds the sample material and is located in a furnace or
oven that is heated or cooled during the experiment. A thermocouple is used to accurately
control and measure the temperature within the oven. The mass of the sample is constantly
monitored during the analysis. An inert or reactive gas may be used to purge and control the
environment. The analysis is performed by gradually raising the temperature and plotting the
substances weight against temperature.

Diagram 1 shows the Schematic diagram of apparatus for the measurement of

thermogravimetry.