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Differential Thermal Analysis

What is Differential Thermal Analysis? 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. Both sample and reference material must be heated under carefully controlled conditions. If the sample undergoes a physical change or a chemical reaction, its temperature will change while the temperature of the reference material remains the same. That is because physical changes in a material such as phase changes and chemical reactions usually involve changes in enthalpy, the heat content of the material. 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. Instrumentation

Instrumentation and working The sample is loaded into a crucible, which is then inserted into the sample well (marked S). A reference sample is made by placing a similar quantity of inert material (such as Al2O3) in a second crucible. This crucible is inserted in the reference well, marked R. The dimensions of the two crucibles and of the cell

wells are as nearly identical as possible; furthermore, the weights of the sample and the reference should be virtually equal. The sample and reference should be matched thermally and arranged symmetrically with the furnace so that they are both heated or cooled in an identical manner. The metal block surrounding the wells acts as a heat sink. The temperature of the heat sink is slowly increased using an internal heater. The sink in turn simultaneously heats the sample and reference material. A pair of matched thermocouples is used. One pair is in contact with the sample or the sample container; the other pair is in contact with the reference. The output of the differential thermocouple, Ts - Tr or T, is amplified and sent to the data acquisition system. This allows the difference in temperature between the sample and the reference to be recorded as a function of either the sample temperature, the reference temperature or time. If there is no difference in temperature, no signal is generated, even though the actual temperatures of the sample and reference are both increasing. Operating temperatures for DTA instruments are generally room temperature to about 1600 OC; some DTA equipments are capable of operating from -150 OC to 2400 OC. To reach the very low sub-ambient temperatures, a liquid nitrogen cooling accessory is needed. Some low temperatures (but, not -150 OC) may be reached with electrical cooling devices or with forced air-cooling. When a physical change takes place in the sample, heat is absorbed or generated. For example, when a metal carbonate decomposes, CO2 is evolved. This is an endothermic reaction; heat is absorbed and the sample temperature decreases. The sample is now at a lower temperature than the reference. The temperature difference between the sample and reference generates a net signal, which is recorded. Modern DTA instruments have the ability to change atmospheres from inert to reactive gases, as is done in TGA. As is the case with TGA, the appearance of the DTA thermal curve depends on the particle size of the sample, sample packing, the heating rate, flow characteristics inside the furnace, and other factors. Thermal matching between the sample and the reference is often improved by diluting the sample with the inert reference, keeping the total masses in each crucible as close to each other as possible. Sample crucibles are generally metallic (Al, Pt) or ceramic (silica) and may or may not have a lid. Many metal pans with lids have the lid crimped on using a special tool. Best results are obtained when the area of contact between the sample and the pan or crucible is maximized. Samples are generally in the 110 mg range for analytical applications.

DTA thermogram of a polymer

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 Applications 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 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 cm2 (for s) and 45 cm2 (for r). Find the latent heat of fusion of the sample, (Hm[s]) 3. To fingerprint substances

4. To determine M.Pt., B.Pt., decomposition temperatures of organic compounds .

5. To characterize inorganic materials

The peak at 113C corresponds to a solid-phase change from the rhombic to the monoclinic form, while the peak at 124C corresponds to the melting point of the element. Liquid sulphur is known to exist in at least three forms, and the peak at 179C apparently involves a transition among these. The peak at 446C corresponds to the boiling point of sulphur. 6. To quantitatively analyze polymer mixtures

This is a thermogram of a physical mixture of seven commercial polymers. Each peak corresponds to the characteristic melting point of one of the components. Poly tetrafluoroethylene (PTFE) has an additional low temperature peak, which arises from a crystalline transition. Clearly, differential thermal methods can be useful for qualitative analysis of polymer mixtures.

7. To characterize polymers

0 Schematic DTA thermal curves for the totally amorphous polymer structure and the semi-crystalline polymer structure. Both show Tg ; only the semi-crystalline polymer has a crystallization exotherm. Effect of atmosphere on DTA thermogram

The two minima indicate that the sample becomes cooler than the reference material as a consequence of the heat absorbed by two endothermic processes; equations for these decomposition reactions are shown below the minima. The single maximum indicates that the reaction to give calcium carbonate and carbon dioxide is exothermic. When the differential thermogram is obtained in an inert atmosphere, all three reactions are endothermic, and the maximum is replaced by a minimum; here, the reaction product from the decomposition of calcium oxalate is carbon monoxide rather than carbon dioxide.

References D. A. Skoog, F. J. Holler, and T. A. Nieman, Principles of instrumental analysis, 5/e, Harcourt Publishers, 2001. J. W. Robinson, E. M. S. Frame, and G. M. Frame II, Undergraduate Instrumental Analysis, 6/e, Marcel Dekker, 2005. P. Gabbott, Ed., Principles and Applications of Thermal Analysis, Blackwell, 2008.