Paper: Fundamentals of Analytical Chemistry

Module 32
Thermoanalytical methods -I

Introduction

When matter is heated it undergoes certain physical and chemical changes. These changes

which are physical or chemical in nature occur at widely varying temperatures. For example,

changes such as melting or boiling which are physical in nature may take place over a wide

temperature range, and the temperature range is governed by the material involved in the

analysis. Changes which are chemical in nature, such as decomposition, may also occur at

varying temperatures.

The changes either physical or chemical in nature which take place when a sample undergoes

heating, are characteristic of a substance under examination. By measurement of the

temperature at which such reactions take place and the heat involved in the reaction, the

substances present in the material can be easily characterized. The majority of known

inorganic compounds have been so characterized. If heating of an unknown sample is done

than the physical and chemical changes taking place in the reaction help us to provide the

information regarding the identity of the material under investigation. These changes which

take place during the reaction give an indication of the temperature at which the material

under examination stops to be stable under normal conditions. This information is very useful

to industrial chemists, such as those who make varnishes and paints, since it allows them to

predict the service lifetime of such compounds. In recent times, thermogravimetric methods

of analysis have become very popular in analytical chemistry. The term thermal analysis

incorporates those methods in which determination or recording of system’s physical

parameters is done as a function of temperature.

 The various techniques of thermal analysis are summarised in table 1

S.No. Technique Abbreviations Instrument used Parameter Graph obtained

measured

1. Thermogravimetry TG Thermobalance Mass Mass vs. Temperature

or Time
2. Derivative DTG Thermobalance dm/dt dm/dt vs.
Thermogravimetry Temperature

3. Differential Thermal DTA DTA apparatus ∆T ∆T vs. Temperature

Analysis

4. Differential Scanning DSC Calorimeter dH. dt dH. dt vs.

Calorimetry Temperature

5. Thermometric - Calorimeter Temperature Temperature vs.

Titrimetry Titrant volume

6. Dynamic Reflectance DRS Spectrophotometer Reflectance %Reflectance and

Spectroscopy Temperature
7. Evolved Gas Detection EGD Thermal Thermal T.C. vs. Temperature
Conductivity Cell Conductivity
8. Thermomechanical TMA Dilatometer Volume of Volume or Length vs.
Analysis (Dilatometry) Length Temperature
9. Electrical Conductivity EC Electrometer or Current (I) I or R vs.
Bridget or Resistance
(R) Temperature

10. Emanation Thermal ETA ETA apparatus Radioactivity E vs. Temperature

Analysis (E)

Thermal changes are generally studied by recording changes taking place while the

temperature is varied which results in a thermal analysis curve or thermogram. It is important

to mention here that single thermal analysis method does not provide complete information of

a system. However, additional information may be provided by other thermal methods if

required.

According to Wendlandt, four thermal methods are most important which will be considered,
 A. Differential thermal analysis (DTA)

B. Differential scanning calorimetry (DSC)

C. Thermogravimetric Methods (TGA)

D. Derivative Thermogravimetry (DTG)

A. Differential Thermal Analysis

I. Introduction

Differential thermal analysis (DTA) in comparison to thermogravimetry is, in fact far more

versatile and provides data which is more fundamental in nature. Differential thermal analysis

is a very simple technique where the difference in temperature between a material and a

reference substance against temperature (or time) is recorded as the two samples are allowed

to undergo identical temperature regimes in a controlled environment. Therefore, a

differential thermogram is a plot that consists of temperature difference between a sample

and reference (differential temperature, ∆T). This difference in temperature is plotted as a

function of time (t), temperature of sample (Ts), temperature of reference (Tr) or temperature

of furnace (Tf). A typical DTA curve is shown in following figure (Fig 1) which consists of

two types of peaks; an exothermic peak and an endothermic peak. A peak’s shape and size

may provide valuable information about the nature of material under investigation.

Fig 1: An ideal DTA curve

Generally, sharp endothermic peaks give ideas of changes in crystallinity or fusion processes

whereas board endotherms signify dehydration reactions. Generally, in many cases, changes

in physical parameters give rise to curves which are endothermic in nature whereas chemical

reactions (particularly those of an oxidative nature) give rise to exothermic peaks.

The temperature difference in the test substance (∆T) is due to the difference in energy

between the products and the reactants of a reaction or between the two phases of a material.

This difference in the energy is manifested as enthalpic changes which are either exothermic

or endothermic in nature.

The DTA curve of a sample would be parallel to either time or temperature axis till any

physical and chemical change of state takes place in the material under investigation. The

detection of every physical or chemical change can be done easily with DTA.

II. Factors affecting DTA curve

The DTA curve is affected by a larger number of factors than the TG curve. The special

influences on DTA curves will be considered. The various factors which may affect a DTA

curve are as follows.

i. Factors related to environment

ii. Factors related to the instrument

iii. Sample factors

i. Factors related to environment

a. Sensitivity of DTA technique towards the gaseous environment around the sample is

very high in comparison to TG.

 b. Two types of gaseous atmospheres are employed in differential thermal analysis: (i)

static gaseous atmosphere and (ii) dynamic gaseous atmosphere.

c. Reproduction of a static gaseous atmosphere is very difficult as the concentration of

atmosphere which surrounds the sample changes chemically because of the evolution

of various gases. Convection currents are responsible for physical changes during the

analysis. Therefore, the studies done in the presence of a static gaseous environment

are not precise.

d. Dynamic gaseous atmosphere is widely used as the results obtained are reliable and

reproducible. The gases, either reactive or inert in nature, produced during the

analysis are swept past the sample in a controlled manner.

ii. Factors related to the instrument

a. Sample holder: The geometry and the material used in the fabrication of the

sample holder affects resolution, shape and size of peaks obtained in differential

thermal analysis. Materials whose thermal conductivity is very high are used in the

construction of sample holders (e.g. metals).

b. Differential temperature sensing devices: Generally, heats of transitions are

much less as compared to the heats of reactions. If the wires which are being used

in temperature sensing devices are much thick, then distortion of the heights of

various peaks may be encountered. If a wire which is thin is used in these devices

then, a very less amount of distortion in peak heights is observed.

 c. Characteristics of the furnace: The type of winding used in the furnace has a

very profound effect on the curves obtained by differential thermal analysis. A

change is observed in the base line if the winding which is used in the furnace is

non-uniform. This type of effect is generally seen in hand –wound furnaces.

d. Temperature programmer controller: There is requirement of temperature

controlling during differential thermal analysis as a constant heating rate is

necessary to obtain satisfactory results.

e. Thermal Regime: Rate of heating employed in the differential thermal analysis

has a great effect on DTA curves. If higher heating rates are used then sharper

peaks with greater intensity are obtained. Generally, heating rates of about 10 to

20° per minute are used.

f. Recorder: Curves obtained by differential thermal analysis are affected by the

type, chart- speed, span and pen- response of a recorder.

iii) Sample Characteristics

a) Physical

Heat capacity remains constant with progress of the reaction. But this is changing with the

progress of the reaction. The effect of particle size is related to the effects of density of

packing and overall thermal conductivity of material being used as the sample. In general,

following interferences are drawn from the variation in size of the particle:

 Size of the particle alters peak area.

 Size of the particle has a great influence on the peak temperature.

 Size of the particle also alters completion temperature.

 b) Chemical

Peaks obtained in differential thermal analysis are greatly affected by chemical reactivity of

sample, sample holder, material from which thermocouple is made, ambient gaseous

environment and added diluents.

III. Instrumentation used in DTA

Many different types of instruments are available for DTA studies. DTA apparatus is shown

in fig 2. The various components are as follows:

(a) Furnace: This device is used for heating sample.

(b) Sample holder: This is used to contain the sample as well as reference material.

(c) DC Amplifier: Generally, a low-level DC amplifier is employed.

(d) Differential temperature detector: The function of this detector is to measure

differential temperature.

(e) Furnace temperature programmer: The main function of this is to increase the

temperature of the furnace at a steady rate.

(f) Recorder: This is to record the DTA curve.

(g) Control equipment: Its function is to maintain a suitable atmosphere in the furnace

and sample holder.

Fig 2: A schematic diagram of a typical DTA apparatus

 IV. Applications of differential thermal analysis

Some applications of DTA which are of interest to chemists are:

A. Physical chemistry: Some main applications are as follows:

(a) Heat of reaction

(b) Specific heat

(c) Thermal diffusivity

B. Analytical Chemistry: The various applications are as follows:

(a) Qualitative analysis – Curves obtained by differential thermal analysis for two

compounds are not identical. Therefore, this technique can serve as a finger print for

different materials.

(b) Identification of products – Products which are formed when a compound reacts

with another compound, can be easily identified by the curves obtained by means of

differential thermal analysis.

(c) Melting Points – As melting point can be easily determined by DTA, it means that

this technique can be used as a direct check of the purity of the compound.

(d) Quantitative Analysis – Areas of DTA peaks are proportional to total heat of

reaction and hence to sample weight. Thus, the amount of a sample can be easily

calculated with the help of standard curves of peak area vs. weight. Example (Fig 3

and 4).
 Fig 3: Schematic DTA curve of a typical polymer

Fig 4: DTA curve for seven component polymer mixture showing endothermic peaks
associated with melting

C. Inorganic Chemistry

 Differential thermal analysis has been employed for studying thermal stability of

different inorganic substances and complexes.

 DTA curves are more helpful in the identification of intermediate compounds.

  Oxalates, carbonates, oxides and metal amine complexes can be easily determined by

differential thermal analysis.

 DTA has been used to study the oxides of uranium and plutonium.

D. Organic Chemistry

 Differential thermal analysis has been widely used in identification of substances,

determination of purity of different compounds and quantitative analysis including the

determination of kinetic parameters of organic chemicals, oils, polymers, explosives,

fats and pharmaceuticals.

B. Differential Scanning Calorimetry (DSC)

I. Introduction

It is a thermal method whereby the energy necessary to establish a zero-temperature

difference between a substance and a reference material is recorded as a function of

temperature or time when both are heated or cooled at a predetermined rate. Recording of

DSC curves is done by chart abscissa which indicates the transition temperature. The area of

the peak, obtained by DSC technique, corresponds to the total energy which is transferred to

or from the sample. Comparison of the DSC technique with DTA is given in table 2.

Table 2: Comparison of DSC with DTA

Feature DSC DTA

Sample size 2- 10 mg 50-20 mg

Sensitivity of heat of A few joule/mol 0.5kJ/mole

transition
 Cycles of heating and Possibility of programmed Usually programmed heating
cooling heating and cooling

Second order phase Can be seen with sample Not seen

transition size of 200 mg

Specific heat measurement Accurate Inaccurate

II. Instrumentation for DSC

A block diagram of the instrument used in differential scanning calorimetry is shown in Fig

5. The DSC instrument is capable of working on the temperature control of two similar

sample holders in the sample holder assembly. The left half consists of a circuit for

controlling differential temperature while the right half consists of a circuit to control average

temperature. The circuit used to control the average temperature is an electrical signal which

is proportional to the temperature of the sample and reference holders and is generated

through programmer.

Sample: By using differential scanning calorimetry, analysis of liquids and solids in powder,

crystal or granule form can be done easily.

Reference substance: An inert substance like alumina is usually employed as the reference

material.

Environment: Usually, measurements in differential scanning calorimetry are done in gas

environment. Generally, for flowing gas a rate of about 20-30mL/min is recommended.

A schematic DSC curve and DSC apparatus are shown in Fig 6 and 7.
 Fig 5. Block diagram for DSC instrument

III. Factors affecting DSC curves:

1. Size of sample: Sample size of about 0.5 to 10 mg is generally sufficient for DSC.

Use of small samples help in faster scanning and provide peaks with better shape and

good resolution. Samples with small size tend to have better contact with gaseous

environment. However, if large samples are used then, smaller heats of transitions

may be measured with high precision. In principle, like, DTA, DSC involves the

heating of the sample and an inert reference in parallel.

 Fig 6. Schematic DSC curve

Fig 7. DSC Apparatus

IV. Applications of DSC

 Differential scanning calorimetry can be used for all applications of conventional

differential thermal analysis. Most important feature of DSC is the small size of the

sample required for an analysis.

 Some other applications of DSC in different fields are,

 Melting point

 Crystallization time and temperature

 Heat of melting and crystallization

 Oxidative stability

 Thermal stability
 I. Multiple choice questions:

1. In DTA technique which parameter is measured

a. dH/dT
b. dm/dT
c. ∆T
d. Temperature

2. Which type of instrument is used in DSC technique

a. Thermobalance
b. Calorimeter
c. Spectrophotometer
d. Thermal conductivity cell

3. Which factor does not affect DTA curves

a. Human error factor
b. Environment factor
c. Instrument factor
d. Sample factor

4. DTA curves for two compounds are

a. Not identical
b. Identical
c. Depends upon nature of substance
d. None of these

Answers:

1. c. ∆T
2. b. calorimeter
3. a. human error factor

4. a. not identical
 II. Fill in the blanks:

1. _____ is a very simple technique where the difference in temperature between a

material and a reference substance against temperature (or time) is recorded as the

two samples are allowed to undergo identical temperature regimes in a controlled

environment.

2. Thermal changes are generally studied by recording changes taking place while

______ is varied which results in a thermal analysis curve or thermogram.

3. Sensitivity of DTA technique towards the gaseous environment around the sample

is very ___ in comparison to TG.

4. The size of the sample used in DSC technique is about ______

Answers:

1. Differential thermal analysis

2. the temperature

3. high

4. 2- 10 mg

III. Match the following:

1. Specific heat measurement in DSC A. Not accurate

2. Sensitivity of measurement of B. Zero temperature

heat of transition in DTA

3. DSC C. 0.5 KJ/mol

4. Specific heat measurement in DTA D. Accurate

Answers:

1. D

2. C

3. B

4. A

IV. Which statement is true or false?

1. DSC is a technique in which the difference in the amount of heat required to increase the

temperature of a sample and reference is measured as a function of temperature. (True)

2. DTA measurements are carried out in gas environment. (False)

3. DTA has been used to study the oxides of uranium and plutonium. (True)

4. DTA technique can be used for the measurement of heat capacity. (False)

V. Do you know?

1. Thermal analysis comprises a group of techniques in which a physical property of a

substance is measured as a function of temperature, while the substance is subjected to

a controlled temperature programme

2. In today's market most manufacturers no longer make true DTA systems.

3. The area under a DTA peak is the enthalpy change and is not affected by the heat

capacity of the sample.

4. A DTA curve can be used as a finger print for identification purposes.

5. When matter is heated it undergoes certain physical and chemical changes. These

changes which are physical or chemical in nature occur at widely varying

temperatures.

VI. Interesting facts:

 1. In recent times, thermogravimetric methods of analysis have become very

popular in analytical chemistry.

2. The term thermal analysis incorporates those methods in which determination or

recording of system’s physical parameters is done as a function of temperature.

3. The DTA curve of a sample would be parallel to either time or temperature axis

till any physical and chemical change of state takes place in the material under

investigation.

4. The detection of every physical or chemical change can be done easily with

DTA.

5. Differential scanning calorimetry can be used for all applications of conventional

differential thermal analysis.

6. Most important feature of DSC is the small size of the sample required for an

analysis.

VII. Points to remember:

1. The sharp endothermic peaks give ideas of changes in crystallinity or

fusion processes.

2. Two types of gaseous atmospheres are employed in differential thermal

analysis: (i) static gaseous atmosphere and (ii) dynamic gaseous

atmosphere.

3. Curves obtained by differential thermal analysis are affected by the type,

chart- speed, span and pen- response of a recorder.

4. Dynamic gaseous atmosphere is widely used as the results obtained are

reliable and reproducible. The gases, either reactive or inert in nature,

 produced during the analysis are swept past the sample in a controlled

manner.

5. If heating of an unknown sample is done than the physical and chemical

changes taking place in the reaction help us to provide the information

regarding the identity of the material under investigation.

VIII. References

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

edition.

2. http://sv.rkriz.net/classes/MSE2094_NoteBook/96ClassProj/experimental/dydyn

am/dynamic.html

3. http://www.pharmachitchat.com/drug-excipient-compatability-studies-using-

thermal-methods/

4. http://www.hitachihightech.com/global/products/science/tech/ana/thermal/descri

ptions/dsc.html

5. https://www.researchgate.net/figure/229816356_fig12_Figure-6-Schematic-

DSC-curves-showing-different-transitions-and-reactions-of-a-polymer

6. https://www.researchgate.net/figure/234081548_fig2_Fig-2-a-Scheme-of-the-

DSC-apparatus-b-Scheme-of-the-DSC-sample-cell