THERMAL ANALYSIS

Measurement of changes in physical

properties of a substance as a function of
T, whilst substance is subjected to a
controlled temperature program.
Generalized instrument:
Temperature programmer
↓
Sample in furnace with controlled
atmosphere
↓ x axis ↓ y axis
temperature property

Output: Plot of the property (y axis) versus T.

http://www.thermalcal.com
What properties are measured? See:
http://www.ngb.netzsch.com/methods.htm
We will only consider a few thermal analysis
techniques:
Property Technique Abbreviation
Mass Thermogravimetry TG
Derivative thermogravimetry DTG
Temp Differential thermal analysis DTA
Rate of heat flow
Differential scanning calorimetry
DSC
Evolution of gas
Evolved Gas Detection EGD
Analysis of evolved gas
Evolved Gas Analysis EGA
Take a look at thermal analysis instruments
http://www..co.uk/
Types of thermal event
phase transition
adsorption, desorption
melting (fusion)
sublimation
thermal decomposition
radiolytic decomposition
glass transition
oxidation/ combustion
heterogeneous catalysis
double decomposition
addition
desolvation
 Thermogravimetry (TG)

Measurements of changes in sample mass with

temperature are made using a thermobalance. This
is a combination of a suitable electronic
microbalance with a furnace and associated
temperature programmer. The balance should be in
an enclosed system so that the atmosphere can be
controlled.
Y axis is %mass loss; X axis is temp (or time,
since usually a linear heating rate).

Optimum conditions
i) few mg sample
ii) thin layer of sample
iii) open sample container
iv) inert gas flow
v) slow heating rate
Instrument calibration
The sample temperature often lags behind
the furnace temperature, especially for a
vacuum, fast gas flow or high heating rate.
We therefore need an independent check, or
calibration, of the sample temperatiure.
In the Curie point calibration method a
ferromagnetic material replaces the sample
in the furnace. A magnet is placed
underneath the furnace. At the Curie point,
the substance loses its ferromagnetism so
that a sudden change in the apparent mass
of the sample is registered.
Using mixtures, a multi-point temperature
calibration can be performed.
e.g. Curie points (in oC) of alumel 163; Ni
354; perkalloy 596; Fe 780; Hisat 1000.
Typical TG curves

1. no change
2. desorption/drying
(rerun)
3. single stage
decomposition

4. multi-stage
decomposition
5. as 4, but no
intermediates or
heating rate too
fast
6. atmospheric
reaction
7. as 6, but
product
decomposes at
higher
temperature
Derivative thermogravimetry (DTG)
plots change in mass with temperature, dm/dt,
and resolves changes more clearly.
Some applications of TG
Accurate definition of conditions for drying
analytical precipitates
Thermal stability range of materials - drugs.
Conditions of polymer degradation, metal
oxidation.
Fingerprint minerals, e.g. identify polymers
TG of various polymers
Some applications of TG (cont.)

A thermogram of a compound which is either

MgO, MgCO3 or MgC2O4, shows a mass loss
of 45.5 mg from a total of 87.5 mg used for
analysis. What compound is it?

Determine reaction kinetics.

Take a look at
thermogravimetric analysis being
used to follow dehydration
kinetics of a crystal
http://www.dsc-tga-dma-lab.com/TGA.htm
thermogravimetry http://
www.looksmart.com/r?page=/search/frames/index.html&isp
=US&name=&bcolor=ffcc00&key=thermogravimetry&url
=http%3a//www.bbk.ac.uk/Departments/Chemistry/staff/mo.html&pskip=&
nskip=10&se=0,0,0,153&index=3
Some technical literature concerning a TG
instrument
1 Baffles; 2 Reactive gas capillary; 3
Fused silica jacket; 4 Gas outlet stopcock;
5 Sample temperature sensor; 6 Furnace
heater; 7 Furnace temperature sensor; 8
Electrical connections; 9 Vacuum and
purge gas tubing; 10 Thermostated
balance chamber; 11 Parallel guided
ultramicro balance; 12 Furnace motor to
open sample chamber; 13 Cooling;
14(15) Protective (reactive) gas inlet; 16
Vacuum

14
15

16
Differential thermal analysis, DTA
Difference in temperature, ∆ T, between
a sample and a reference material is
measured when they are subjected to a
controlled temperature program (usually
T increases linearly with time).
<10 mg of sample (s) and inert reference
(r) are contained in Al pans each with
thermocouple, held in heating block,
with thermocouple.

There is a constant temperature difference

∆ T between s and r since they have different
heat capacities. But when the sample
undergoes an endo (exo) thermic change ∆ T
becomes different.
Typical results from DTA
Analysis of a polymer shows several features
due to physical and chemical changes,
including:
glass transition: glassy, amorphous polymer
becomes flexible, ∆ H = 0, but change in Cp.
Often Tg ~ 2/3 Tm.
crystallization of amorphous polymer into
microcrystals is exothermic.
oxidation peak would be absent in N2
atmosphere
DTA of polymer
 Some uses of DTA
1. To construct phase diagrams and study
phase transitions.
2. To find ∆ H
Peak areas depend upon sample mass, m,
enthalpy change ∆ H of the process, and
geometric and conductivity factors such as
heating rate φ and particle size (included in
a constant k for a certain substance)..

peak area ∝ ∆ H × m
(cm2) (Jg-1 ) ( g)
usually the sample peak area is compared
with a standard undergoing an enthalpy
change at a similar T (since the calibration
constant depends on T), under the same
conditions,
e.g. indium MPt 156.4 oC; ∆ Hfusion = 28.5 J g-1

Example of DTA experiment to find ∆ H

The relative molecular mass (Ms) of a sample

is 64.3, and of a reference (Mr) is 98.4. The
enthalpy change of fusion of the reference
(∆ Hm[r]) is 6.83 kJ mol-1 , and it melts at
nearly the same temperature as the sample. 10
mg samples of the sample and reference give,
under the same conditions, peak areas 60.0
cm2 (for s) and 45 cm2 (for r).
Find the latent heat of fusion of the sample,
(∆ Hm[s])
 3. To fingerprint substances

↑ a
endo ↑
∆T

b
temp →
DTA of (a) butter and (b) margarine

4. To determine M.Pt., B.Pt., decomposition

temperatures of organic compounds
DTA of
benzoic acid
A ambient
pressure;
B 200 lb in-2
pressure
what are the
two peaks?
Differential scanning calorimetry DSC
DSC is a thermal analysis method where differences
in heat flow into a substance and a reference are
measured as a function of sample temperature, while
both are subjected to a controlled temperature
program.
The basic difference between DTA and DSC
DSC- calorimetric method, energy differences
measured.
DTA- temperature differences measured.
The applications of both techniques are similar, but
DSC is now more popular. DTA is used for higher
temperature and qualitative applications. DSC is used
for calorimetric determinations, sample purity
determinations and kinetics.
Look at the video: on DSC and DTA in the library,
QD79.T38.T44 (1994)

http://www.thermalcal.com/
Two major types of DSC instruments are
available
Heat flux device – more popular; more
stable baseline and more durable cell.
Difference in heat flow into s and r is
measured with (linear) change in sample
temperature.
Power compensation device – better
resolution; faster heating and cooling rates.
s and r heated by separate heaters to keep
same temperature, as T is changed
linearly.
Newer Tzero technology DSCs eliminate
assumptions used in one-term equation
concerning heat flow, where sample heat
flow q = -∆ T/R .
 Power compensated DSC
crimped Al pans (<500 o C)
s and r are isothermal

Instrument has 2 small, independent furnaces, one

for s and one for r, embedded in a large
temperature-controlled heat sink . The s and r
holders have Pt resistance thermometers for T
measurements.
One control circuit, the average temperature
control unit, provides the x axis: average
temperature of s and r as a function of time.
The second control unit, differential temperature
circuit, provides a signal proportional to the
difference in power input (mW) to the 2 furnaces.
Heat flux DSC
An electrically heated constantan (60% Cu, 40%
Ni) thermoelectric disc enables the heat to flow into
s and r, which are in small Al pans in a raised
platform. The differential heat flow to s and r is
monitored by the difference in output at the two
chromel/constantan area thermocouples.
Temperature of s is obtained from the
chromel/alumel junction under the s disc.
Heat Capacity Measurement Using DSC
Baseline change h occurs for substances with
different Cp, or for same substance after
phase change.
h ∝ Cp where Cp is thermal capacity (= mass in g
× specific heat capacity in J g-1o C-1 );
h = B φ Cp
B = calibration factor, found by using standard
e.g. sapphire; m is sample mass g; φ is heating
rate oC s-1 ; unit of y axis (h) is J s-1 .
To measure Cp for a substance, obtain DSC
results for:
empty pans in both holders,
sample in one pan and reference in other pan.
s, r in crimped Al pans (T<500 oC)
standard in one pan and reference in other.
Other uses of DSC are shown in the video:
such as
kinetics of curing araldite;
determination of polymer oxidation
temperatures as a guide to stability;
determination of phase diagrams of liquid
crystals;
determination of thermal conductivity;
determination of purity of pharmaceutical
products, e.g. phenacetin below
 The sample atmosphere is
important in determining the
reaction that takes place.

DTA record of CaC2O4.H2O in

the presence of O2 ; the rate of
heating was 8 oC min-1 .

endo in N2

exo in air

endo
↓

temperature oC
Multiple techniques in Thermal Analysis
Most thermal analysis instruments are modular
and can measure several properties. The
instrument types are:
a) Simultaneous: 2 or more techniques applied at the
same time.
b) Coupled: 2 techniques with an interface.
c) Combined: 2 instruments use different samples.
d) Complementary: a separate method complements the
thermal analysis results.
An example of a) is a TG-DTG-DTA instrument
Evolved gas detection (EGD)
when interfaced with a TG instrument, can
distinguish when a gas is evolved.
Evolved gas analysis (EGA)
identifies what is the gas evolved?
e.g. using a jet separator interface to a ms; or
using intermittent gc sampling coupled to DSC.
Below are TG-DTA-MS curves for
decomposition of hydrated Co(C4H4O6).2.5H2O
in Ar, with heating rate 2.5 o C min-1
Useful books:
Principles of Instrumental Analysis
Skoog; Holler; Nieman, Saunders
5th Ed. (1998) Chapter 31.
Instrumental Analysis
G.D. Christian and J.E. O’Reilly
Allyn and Bacon (1986) Chapter 17.
Introduction to Thermal Analysis
M. E. Brown Chapman and Hall
QD79.T38 B76 (1988)
Thermal Methods.
J. W. Dodd, K. H. Tonga
ACOL, Wiley 1987
CRC Critical Reviews in Analytical
Chemistry: Modern Methods of Thermal
Analysis. T. Miesel.
November 1981 p. 267.