Paper: Fundamentals of Analytical Chemistry

Module 33
Thermoanalytical methods- II

Thermal analysis includes a number of important techniques which have in common the

characterization of materials by describing their properties, or changes in their properties, as a

function of temperature and time. According to Wendlandt, four thermal methods are most

important:

1. Differential thermal analysis (DTA)

2. Differential scanning calorimetry (DSC)

3. Thermogravimetric Methods (TGA)

4. Derivative Thermogravimetry (DTG)

In this module, Thermogravimetric Methods (TGA) and Derivative Thermogravimetry

(DTG) have been described.

Thermogravimetric Methods (TGA)

A. Introduction

Thermogravimetry is defined as “a technique whereby the weight of a substance, in an

environment heated or cooled at a controlled rate, is recorded as a function of time or

temperature”. A plot of mass as a function of temperature (a thermogram) provides

both qualitative and quantitative information.

Thermogravimetry is of three types:

(i) Isothermal or static thermogravimetry

Here, the sample weight is recorded as a function of time at constant temperature.

 (ii) Quasistatic thermogravimetry

Here, heating of sample is done to constant weight at each of a series of increasing

temperature.

(iii) Dynamic thermogravimetry

Here, heating of the sample is done in an environment whose temperature changes in

a predetermined manner, usually at a linear rate.

B. Instrumentation

Instrument used for thermogravimetry consists of a precision balance (thermobalance)

in which changes in temperature occur at a linear rate. Representation of the results is

done by a plot of weight change versus temperature or time. This plot is known as

thermogravimetric curve (TG curve). Weight should be plotted on ordinate and

temperature (T) or time (t) should be plotted on the abscissa (Fig.1).

Fig 1. Thermogravimetric Curve

 The principle of thermogravimetry is based on the simple fact that the sample is

weighed continuously as it is being heated to elevated temperatures. In the market

both manual as well as automatic recording balances are available but for practical

reasons, the latter type is preferred. However, manual recording is still used for long

term isothermal measurements (for example, with helix type thermobalance).

Different components of a thermobalance (Fig.2) are (i) recording balance (ii) furnace

(iii) furnace temperature programmer and (iv) recorder. The specific details of each

component depend on the particular application that is required of the instrument.

Fig 2. Thermobalance

Basic units of a thermobalance are:

1. Balance

Balance is the most important component of a thermobalance. A good balance must

possess following characteristics:

(i) Accuracy, reproducibility, capacity and sensitivity of a thermobalance should

be similar to an analytical balance.

(ii) Sufficient range of automatic weight adjustment should be present.

(iii) Mechanical and electronic stability of a thermobalance should be high.

(iv) Thermobalance should respond to weight changes rapidly.

(v) It should not get affected by vibration.

(vi) It should be easy to operate.

Recording balances are mainly of two types: (i) deflection-type instrument and (ii)

null-type instrument (Fig 3).

Fig 3. Deflection balances: (a) Beam type (b) Helical or spring type (c) Cantilever

type (d) Torsion type

(i) Deflection Balances: There are of following types:

(a) Beam type: In these type of balances, conversion of beam deflection takes place

about fulcrum into a suitable weight change which can be easily identified.

(b) Helical type: An elongation or contraction of the spring with weight change

occurs in these type of balances. Transducers are used for suitable recording of

changes in length of spring.

(c) Cantilevered beam: Here, one end of the beam is fixed while the other end where

sample is placed undergoes deflections.

(d) Torsion wire: In these balances, a taut wire attached to the beam acts as a

fulcrum. The taut wire is firmly fixed at ends such that deflection of beam is

proportional to changes in weight and torsional characteristics of taut wire. Instead

of a wire a ribbon made of metal can also be used.

(ii) Null –Point balances

These type of balances are gaining much popularity in recent times in analysis of

compounds. In null-point balances, a sensor is present which is useful in detection of

the deviation of the beam from its null position. If deviation occurs then, a restoring

force (electrical or mechanical weight loading) is applied to the beam for restoration

of its null position from the horizontal or vertical norm (Fig 4). The force applied to

restore the beam is proportional to change in weight and this restoring force is

recorded directly.

Fig 4. Null Type Balances

2. Sample holder for placing sample

Sample holder’s geometry, size and material play a crucial role in determining the

shape of a thermogravimetric curve. Sample holder’s size and shape is governed by

the nature of the sample, weight of the sample and the maximum temperature range to
be used. Alumina, stainless steel, platinum, graphite, glass, quartz, etc. are used to

make sample holders. There are following types of sample holders used to place

samples in the furnace:

(i) Shallow pans: Shallow pans are usually employed in cases where it is necessary

to eliminate diffusion as rate controlling step. As volatile material is produced

throughout the sample mass, it should diffuse to the surface instantaneously to

escape and be registered as a weight loss. In some cases, like polymers, side

reactions may occur. In such cases, the sample is arranged in a thin layer so that

volatile fragment is free to escape.

(ii) Deep crucibles: Deep crucibles are used for samples where partial equilibrium or

side reaction is wanted. These type of crucibles are employed to study calcinations

at industrial scale. Deep crucibles are also employed in surface area

measurements.

(iii) Loosely covered crucibles: These type of crucible is usually employed in self-

generated atmosphere studies.

(iv) Retort cups: Retort cups resemble alchemist’s retort. These type of cups prove to

be very useful in determinations involving boiling points. The retort is helpful in

providing the single plate of reflux necessary for a simple boiling point study.

3. Furnace used in thermogravimetry

The furnace and control system should be designed to produce a linear heating

rate over the whole working temperature range of furnace. The choice of furnace

heating element and the type of furnace depend upon temperature being studied.

For 1100°C, the material of furnace is nichrome wire or ribbon. If a wire is being

used, it should be wound coiled so as to accommodate differential thermal

expansion of various components.

For temperature between 1100 and 1500°C, one should use platinum or any alloy

of platinum and rhodium. By using platinum – rhodium alloy having rhodium

content of 40%, one can use the furnace up to 1750°C. For temperature above

1750°C, tungsten or molybdenum may be employed in a reducing atmosphere.

The size of furnace is an important factor. It becomes easier to obtain a larger

uniform hot zone in the high mass furnace. With the small mass furnace, it

becomes difficult. The position of furnace relative to the balance is important.

With some balances like quartz fibre spring balance, the furnace is below the

weighing system but with beam balance, several choices are possible (Fig 5).

Fig 5: Position of furnace with respect to balance

4. Measurement of temperature

This measurement can be carried out in a number of ways. Thermocouple is the

most common method used for temperature measurement. For measurement of

temperature of about 1100°C, chromal or alumel thermocouple constructed from

alloys of platinum and rhodium are used. For very high temperatures, tungsten or

rhodium thermocouples are generally used (Fig 6).

 Fig 6: Position of a thermocouple in a thermobalance

5. Recorder

The recording systems are mainly of two types:

(a) Time-base potentiometric strip chart recorder, and

(b) X-Y recorders

6. Thermobalance in thermogravimetric analysis

A good thermobalance should possess the following characteristics:

(i) The thermobalance should possess the capability to record continuously the

changes in weight of a sample as a function of temperature or time.

(ii) Furnace of thermobalance should have a wide range of temperature.

(iii) Recording of temperature should be done to an accuracy of about ± 1%.

(iv) The temperature which is recorded ideally is the temperature of the sample.

(v) Recording of loss in weight of the sample should be done to an accuracy of

about ±1%.

(vi) A linear heating rate should be used.

(vii) The sensitivity of balance should be proportionate to the size of the samples

being used.

(viii) There should not be any chemical attack of volatile products on the apparatus.
 (ix) The crucibles should be located within hot zone.

(x) The balance has to be protected from the furnace due to its very high

temperature.

(C) Factors which affect TG curves

If study of a system is done by various thermobalances, then the shape of the

thermogravimetric curve obtained with different thermobalances will vary from

instrument to instrument. Thus, it is difficult to make meaningful comparisons

between TG data obtained on different thermobalances in different laboratories. The

difference in the shapes of TG curves may be attributed to different factors; leading to

errors. The factors affecting the thermogravimetric curves can be divided into two

main groups:

a. Instrumental effects and

b. Sample characteristics

C. Thermogravimetry applications

1. Automatic thermogravimetric analysis

(A) Automatic gravimetric analysis for a single component system

(B) Automatic gravimetric analysis for a binary mixture

2. Evaluating precipitates obtained by gravimetry

By using thermogravimetric procedures one can easily determine the correct drying

temperatures of various precipitates obtained in gravimetric methods. For example:

 i. Usually, for determination of lithium triple periodate is used. However, Duval in his

study found out that it is not suitable for gravimetric analysis as the

thermogravimetric curve of triple periodate showed that there occurs a constant

decrease in weight from 40°C to 947°C and concluded that, there is no drying

temperature for this precipitate.

ii. Duval rejected the salicylaldoxime method for determination of zinc as he was unable

to find any constant weight plateaus because he employed a fast heating rate. The

workers confirmed that 135°C is the minimum drying temperature. Later Kettaach

proved that a temperature of about 150°C is sufficient for drying of the complex,

regardless of the moisture content.

3. Evaluating suitable standards

Duval carried out a number of experiments on thermogravimetry to find suitable

standards in analytical chemistry. Duval combined his TG studies with IR absorption

spectrophotometric studies order to arrive these conclusions. He confirmed that the

following substances cannot be used for preparing standard solution:

Magnesium ammonium chloride, ammonium bicarbonate and ammonium fluoride.

He observed that following compounds are most suitable for preparing standard

solutions:

Lithium sulphate monohydrate, Sodium dichromate dehydrate, Sodium

cobaltinitrate, Hydrazinium chloride, Hydrazinium sulphate, Ascorbic acid and

methylglucamine.

Duval advised that not to heat the compounds above the temperature given in the

following table.
 Substances Temperature °C

EDTA 109

Urea 165

NaF 850

Ni(NO3)2 .6 H2O 50

KHCO3 125

NiSO4 .7H2O 100

4. Testing purity of samples

As an analytical tool, the thermobalance can be used in determining the purity of

various substances.

5. Determining Curie point

If a ferromagnetic material is kept on a thermobalance with the pole of the magnet

above the sample, the TG balance will show the weight which will be less than the

actual weight. Ferromagnetic materials lose their magnetism on heating at exactly

reproducible temperature on curie points. A range of metals or alloy with curie points

between 150°C and 1000 °C is available. In the TG curve, the temperature at which

the thermogram shows an increase in weight is the curie temperature of this

substance.

6. Organic substances

Many organic substances have been successfully studied by DTA and TG methods.

7. Oxide mixture

Thermogravimery has been successfully employed to study the reaction between

various oxides. For example, the system CuO-Cu2O-Cr2O3 was studied by this

technique.
8. Building materials

One of the interesting examples is cement where study of a ternary compound in the

system CaO- Al2O3-SO3 is done.

Derivative Thermogravimetry (DTG)

Introduction

In thermogravimetric analysis, mass of a sample (m), is continuously recorded as a

function of temperature (T) or time (t), i.e.,

m= f (T or t)

The quantitative measurement of the change in mass is done by determining the

distance, on the curve mass axis, between the two points of interest or between two

horizontal mass levels.

In derivative thermogravimetry, derivative of the mass change with respect to time is

recorded as a function of temperature or time.

dm = f ( T or t)

dt

The curve which an analyst obtains is the first derivative of the mass change curve.

Instead of the stepwise curve a series of peaks are obtained. And the areas under the

peaks are proportional to the total mass- change of the sample. A derivative and a

mass loss curve is shown in the following figure.

 Fig 7: A TG and DTG mass loss curve

The derivative curve may be obtained either from thermogravimetric curve by manual

differentiation methods or by electronic differentiation of the TG signal. Accessory

equipment is available for most thermobalances so that the derivative curve can be

recorded, without any difficulty, along with the thermogravimetric curve. It should be

noted that the DTG and TG curves are obtained under similar experimental

conditions.

Figure 7 shows a thermogram of nylon and its DTG curve. There is a minimum in the

DTG curve at the point of inflection of the thermogravimetric curve. This makes

identification simpler. Consequently, DTG is a valuable method of data presentation

for qualitative analysis.

 I. Multiple choice questions

1. In static thermogravimetry, the weight of the sample is recorded as a function of

time

a. at a constant temperature

b. at constant pressure

c. both a and b

d. None of these

2. Technique which is used to measure mass loss of material as a function of

temperature is

a. DTA

b. DSC

c. TGA

d. None of these

3. Plot of mass change versus temperature (T) is known as

a. DTA curve

b. TG curve

c. DSC curve

d. Both a and b

4. Which three parameters are measured by TGA technique

a. Mass change, Temperature, Temperature change

b. Mass change, pressure change, heat capacity

c. Temperature difference, heat capacity, electrical change

d. None of these

Answers:
 1. a. At a constant temperature

2. c. TGA

3. b. TG curve

4. a. Mass change, Temperature, Temperature change

II. Fill in the blanks:

1. In TGA technique, temperature measurement is commonly done by using _______

2. Furnace temperature range in TGA method is _______

3. Chromal –alumel thermocouple are often used for temperature up to ________

4. In derivative thermogravimetry, graph is plotted between __________

5. In the market both _________ as well as automatic recording balances are available
but for practical reasons, the latter type is preferred.

Answers:

1. Thermocouples
2. -150°C to 2000°C
3. 1100°C
4. dm/dt
5. manual
III. Match the following:

1. Temperature for EDTA A. 165°C

2. Temperature for Urea B. 109°C

3. Tungsten or molybdenum furnace temperature C. 1100°C

 4. Temperature of nichrome wire D. 1750°C

Answers:

1. B

2. A

3. D

4. C

IV. Which statement is true or false?

1. A plot of mass as a function of temperature (a thermogram) cannot provide qualitative

and quantitative information. (False)

2. The DTG curve may be obtained either from thermogravimetric curve by manual
differentiation methods or by electronic differentiation of the TG signal. (True)

3. In isothermal thermogravimetry technique, the sample is heated to constant weight at

each of a series of increasing temperature. (False)

4. In quasistatic thermogravimetry, the sample is heated in an environment whose

temperature is changing in a predetermined manner, generally at a linear rate. (False)

5. Instrument used for thermogravimetry consists of a precision balance (thermobalance)

in which changes in temperature occur at a linear rate. (True)

6. In null-point balances, a sensor is present which is useful in detection of the deviation

of the beam from its null position. (True)

V. Do you know?

1. Thermogravimetry is defined as “a technique whereby the weight of a substance, in an

environment heated or cooled at a controlled rate, is recorded as a function of time or

temperature”.

2. In derivative thermogravimetry, the derivative of the mass change with respect to

time, i.e. dm/dt, is recorded as a function of temperature or time.

3. The factors affecting the thermogravimetric curves can be divided into two main

groups: Instrumental effects and sample characteristics.

4. The principle of thermogravimetry is based on the simple fact that the sample is

weighed continuously as it is being heated to elevated temperatures.

5. Accessory equipment is available for most thermobalances so that the DTG curve can

be easily recorded along with the TG curve.

VI. Interesting facts:

1. Jesse Russell, Ronald Cohn wrote a book on thermogravimetric analysis.

2. A wide temperature ranges of furnaces are used in thermogravimetric analysis.

3. In the market both manual as well as automatic recording balances are available but for

practical reasons.

4. Different types of balances also used in thermogravimetric analysis according to the mass of

the sample.

5. In dynamic thermogravimetry, heating of the sample is done in an environment

whose temperature changes in a predetermined manner, usually at a linear rate.

 6. In torsion wire balances, a taut wire attached to the beam acts as a fulcrum. The taut wire is

firmly fixed at ends such that deflection of beam is proportional to changes in weight and

torsional characteristics of taut wire.

VII. Points to remember:

1. Wendlandt found four thermal methods for thermal analysis.

2. In TGA technique, thermobalance is widely used.

3. Different types of furnaces and balances are used, according to the sample

measurement.

4. DTG is a valuable method of data presentation for qualitative analysis.

5. Thermal analysis includes a number of important techniques which have in

common the characterization of materials by describing their properties, or

changes in their properties, as a function of temperature and time.

6. Recording balances are mainly of two types: (i) deflection-type instrument and

(ii) null-type instrument.

 References

1. DA Skoog, FJ Holler and SR Crouch, Principles of instrumental analysis, sixth

edition.

2. http://pubs.rsc.org//content/articlelanding/2013/ta/c3ta13543h/unauth#!divAbstra

ct

3. http://lalithvarun.blogspot.in/2013/02/what-is-thermogravimetric-analysis.html

4. http://slideplayer.com/slide/9234657/

5. https://www.slideshare.net/adnanhanifhanif/thermogravematric-analysis

6. https://www.researchgate.net/publication/257616820_Copper_removal_from_aq

ueous_solution_using_biochar_Effect_of_chemical_activation