THERMAL ANALYSIS

PRESENTED BY: MD MERAJ ANJUM M.PHARM 1ST YEAR BBAU,LUCKNOW

Thermal analysis is a group of techniques in which the variation of physical Property of a substance is measured as a function of temperature Various techniques of thermal analysis:
Technique Thermogravimetric Analysis abbreviation TGA Property Mass difference applications Sample purity Decomposition Dehydration Oxidation Phase changes Dehydration Decomposition Reactions Heat capacity Phase changes Reactions Calorimetry
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Differential Thermal Analysis

DTA

Temperature difference

Differential Scanning Calorimetry

DSC

Energy difference

. a technique in which the mass of a substance is measured as a function of temperature, while the substance is subjected to a controlled temperature programme.
Controlled temperature programme can mean: heating and/or cooling at a linear rate (by far commonest) combinations of heating, cooling and isothermal stages other, more modern approaches, in which the temperature profile is modified according to the behaviour of the sample.

GAS IN

WEIGHT

BALANCE CONTROLLER

GAS-TIGHT ENCLOSURE
SAMPLE

HEATER SAMPLE TEMP.

POWER

FURNACE TEMP.

TEMPERATURE PROGRAMMER

Balance: automatic recording balance (i)Null type balance (ii) Deflection balance Furnace: heating device It Should produce linear heating over the whole working temperature range Sample holder: different types (i) Shallow pans (ii) Deep crucibles (iii)Loosely covered crucibles (iv) Retort cups Unit for temperature measurement and control (Programmer) Recorder: automatic recording unit for the mass and temperature changes
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(1) In the study of polymer It provides information about the decomposition mechanism in the polymer. Decomposition pattern is characteristic for each kind of polymers so useful for identification purpose.

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Useful for testing of purity of sample E.g. an unusual weight loss below 100 0C in TG curve of calcium oxalate is due to impurity in the sample 3. Study of organic compound: By making use of DTA, TG and using derivatography a large no of the compound have been studied.

E.g. in the study of decomposition of malonic acid the phase transition occurred in the region of 70 0C with melting at about 140 0C followed by decomposition above 150 0C.

This is a comparison method

Analytical method for recording the difference in temperature (T) b/w a substance and an inert reference material as a function of temperature or time Any transformation change in specific heat or an enthaply of transition can be detected by DTA

T VS Temp.

Sharp Endothermic changes in crystallanity or fusion Broad endotherms - dehydration reaction Physical changes usually result in endothermic curves Chemical reactions are exothermic

The key features of a differential thermal analysis kit are as follows 1. Sample holder comprising thermocouples, sample containers and a ceramic or metallic block. 2. Furnace. 3. Temperature programmer. 4. Recording system.

Differential Thermal Analysis

advantages: instruments can be used at very high temperatures instruments are highly sensitive characteristic temperatures determined disadvantages: uncertainty of heats of fusion, transition, or reaction estimations is 20-50% transition or reaction can be accurately
DTA

Quantitative identification and purity assessment of materials are accomplished by comparing the DTA curve of sample to that of a reference curve Impurities may be detected by depression of the M.P

Differential Scanning Calorimetry (DSC)

.

Definitions
A calorimeter measures the heat into or out of a sample. A differential calorimeter measures the heat of a sample relative to a reference. A differential scanning calorimeter does all of the above and heats the sample with a linear temperature ramp. Endothermic heat flows into the sample. Exothermic heat flows out of the sample.

DSC: The Technique

Differential Scanning Calorimetry (DSC) measures the temperatures and heat flows associated with transitions in materials as a function of time and temperature in a controlled atmosphere. These measurements provide quantitative and qualitative information about physical and chemical changes that involve endothermic or exothermic processes, or changes in heat capacity .

DSC Thermogram

Heat Flow -> exothermic

Crystallisation

Cross-Linking (Cure)

Oxidation

Glass Transition

Melting

Temperature
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Sample

Reference

T1 Pt thermopile Low mass 1 gram N2 flow heater Pt thermopile heater

T2

DW
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Differential Scanning Calorimetry

DSC differs fundamentally from DTA in that the sample and reference are both maintained at the temperature predetermined by the program.
during a thermal event in the sample, the system will transfer heat to or from the sample pan to maintain the same temperature in reference and sample pans two basic types of DSC instruments: power compensation and heat-flux

power compensation DSC

. .

heat flux DSC

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There are two types

1. Power compensated DSC 2. Heat flux DSC

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Power Compensation DSC

individual heaters controller

DP

sample holder

sample pan

reference pan

Al or Pt pans
sensors
inert gas vacuum thermocouple inert gas vacuum

DT = 0

Pt resistance thermocouples separate sensors and heaters for the sample and reference furnace separate blocks for sample and reference cells temperature controller differential thermal power is supplied to the heaters to maintain the temperature of the sample and reference at the program value
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Heat Flux DSC

heating coil

sample holder sample and reference are connected by a low-resistance heat flow path Al or Pt pans placed on constantan disc sensors
sample pan reference pan

constantan chromel/alumel wires

inert gas vacuum

thermocouples

chromel wafer

chromel-constantan area thermocouples (differential heat flow) chromel-alumel thermocouples (sample temperature)
furnace one block for both sample and reference cells temperature controller the temperature difference between the sample and reference is converted to differential thermal power, dDq/dt, which is supplied to the heaters to maintain the temperature of the sample and reference at the program value.GH . 22

Thermogram

dH/dt, mJ/s

exo Glass transition

melting
crystallization endo

Temperature, K
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To estimate degree of crystallization that has occurred at particular temperature at 124 0C min are required to develop max. crystallinity. To characterize the crystallization behavior at a series of temperature. To test the purity of drug samples. Pure data with relative uncertainties of 10 %.
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