Calorimetry

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Author: Michael Smetana

Objective

                The object of this experiment is to demonstrate knowledge of the Calorimeter and its function while discussing the endothermic and exothermic reaction of a material.

Materials Used

                The materials used were two samples of very small but approximately identical size of PET Ceramic, and Al₂O₃, one Calorimeter, computer running windows 2000, computer program called Q-Series.

Background

                Differential Scanning Calorimetry

                Differential scanning calorimetry or DSC is a thermo-analytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference are measured as a function of temperature. Both the sample and reference are maintained at nearly the same temperature throughout the experiment. Generally, the temperature program for a DSC analysis is designed such that the sample holder temperature increases linearly as a function of time. The reference sample should have a well-defined heat capacity over the range of temperatures to be scanned. The basic principle underlying this technique is that, when the sample undergoes a physical transformation such as phase transitions, more (or less) heat will need to flow to it than the reference to maintain both at the same temperature. Whether more or less heat must flow to the sample depends on whether the process is exothermic or endothermic. For example, as a solid sample melts to a liquid it will require more heat flowing to the sample to increase its temperature at the same rate as the reference. This is due to the absorption of heat by the sample as it undergoes the endothermic phase transition from solid to liquid. Likewise, as the sample undergoes exothermic processes (such as crystallization) less heat is required to raise the sample temperature. By observing the difference in heat flow between the sample and reference, differential scanning calorimeters are able to measure the amount of heat absorbed or released during such transitions. DSC may also be used to observe more subtle phase changes, such as glass transitions. DSC is widely used in industrial settings as a quality control instrument due to its applicability in evaluating sample purity and for studying polymer curing.

Application of DSC

Differential scanning calorimetry can be used to measure a number of characteristic properties of a sample. Using this technique it is possible to observe fusion and crystallization events as well as glass transition temperatures. DSC can also be used to study oxidation, as well as other chemical reactions. 

Glass transitions may occur as the temperature of an amorphous solid is increased. These transitions appear as a step in the baseline of the recorded DSC signal. This is due to the sample undergoing a change in heat capacity; no formal phase change occurs.

As the temperature increases, an amorphous solid will become less viscous. At some point the molecules may obtain enough freedom of motion to spontaneously arrange themselves into a crystalline form. This is known as the crystallization temperature (Tc). This transition from amorphous solid to crystalline solid is an exothermic process, and results in a peak in the DSC signal. As the temperature increases the sample eventually reaches its melting temperature (Tm). The melting process results in an endothermic peak in the DSC curve. The ability to determine transition temperatures and enthalpies makes DSC an invaluable tool in producing phase diagrams for various chemical systems.

DSC may also be used in the study of liquid crystals. As matter transitions between solid and liquid it often goes through a third state, which displays properties of both phases. This anisotropic liquid is known as a liquid crystalline or mesomorphous state. Using DSC, it is possible to observe the small energy changes that occur as matter transitions from a solid to a liquid crystal and from a liquid crystal to an isotropic liquid.

Using differential scanning calorimetry to study the oxidative stability of samples generally requires an airtight sample chamber. Usually, such tests are done isothermally (at constant temperature) by changing the atmosphere of the sample. First, the sample is brought to the desired test temperature under an inert atmosphere, usually nitrogen. Then, oxygen is added to the system. Any oxidation that occurs is observed as a deviation in the baseline. Such analyses can be used to determine the stability and optimum storage conditions for a compound.

DSC is widely used in the pharmaceutical and polymer industries. For the polymer chemist, DSC is a handy tool for studying curing processes, which allows the fine tuning of polymer properties. The cross-linking of polymer molecules that occurs in the curing process is exothermic, resulting in a positive peak in the DSC curve that usually appears soon after the glass transition.

In the pharmaceutical industry it is necessary to have well-characterized drug compounds in order to define processing parameters. For instance, if it is necessary to deliver a drug in the amorphous form, it is desirable to process the drug at temperatures below those at which crystallization can occur.

In food science research, DSC is used in conjunction with other thermal analytical techniques to determine water dynamics. Changes in water distribution may be correlated with changes in texture. Similar to material science studies, the effects of curing on confectionery products can also be analyzed.

DSC curves may also be used to evaluate drug and polymer purities. This is possible because the temperature range over which a mixture of compounds melts is dependent on their relative amounts. This effect is due to a phenomenon known as freezing point depression, which occurs when a foreign solute is added to a solution. (Freezing point depression is what allows salt to de-ice sidewalks and antifreeze to keep your car running in the winter.) Consequently, less pure compounds will exhibit a broadened melting peak that begins at lower temperature than a pure compound.

In last few years this technology has been involved in metallic material study. The characterization of this kind of material with DSC is not easy yet because of the low quantity of literature about it. It is known that it is possible to use DSC to find solidus and liquidus temperature of a metal alloy, but the widest application is, by now, the study of precipitations, Guiner Preston zones, phase transitions, dislocations movement, grain growth etc.[i]

                Heat Capacity

                Heat Capacity is the amount of heat required to raise the temperature of a unit mass of a substance through 1 degree Celsius.

                Calorimetry

                Calorimetry is the science of measuring the heat of chemical reactions or physical changes. Calorimetry involves the use of a calorimeter.

    Calorimeter

                A calorimeter is a thermally insulated container where the sample is heated up and the amount of heat given out by the material is measured.

                Endothermic

                Endothermic, also known as endergonic, refers to a transformation in which a system receives heat from the surroundings.  This can be seen on a Graph as the lower peak line.

                Exothermic

                Exothermic refers to a transformation in which a system releases energy (heat) to the surroundings.

Procedure

                The first step in this experiment is to select a material that is to be examined.  In this case of this experiment the sample is a ceramic "PET", and the open calibration sample is Al₂O₃.  Initially the calorimeter should be opened and TARED to zero.  Next the two samples should be placed in the sample beds of the machine.  Then the machine is to be closed.

                The next step after adding the materials and closing the calorimeter up is to run the Q-Series program.  First Set the mode to "standard", Test to "Ramp", sample to "copper", Start 50^oc, continue to 600^oc at 20^oc per minute.

The Argon Gas should be turned on to 10kpaG, and then select type "Aluminum", Press "Start". The next stage in this experiment is to wait for the calorimeter to stop, but since this is just a demonstration, none of these steps were actually done.

After the Calorimeter has completed in cycle, the data will appear on the screen.  This data is then to be saved to a text file and transferred to flash drives for calculations.

Results

The Endothermic Reaction takes place at 250^oc with -6.43833 mW, while the Exothermic Reaction takes place at 138.2^oc with a total of 2.058794 mW.

Discussion

                Notice that the amount of heat flow is almost always generally lower then the zero mark, and the endothermic reaction is the only place on the graph where the amount of Heat Flow is greater then Zero.  This is because there is a point in each material where the Cubic Structure changes inside.  This is the transition temperatures.  This happens because it takes more energy to create this transformation causing the material to absorb more heat.

                On the other hand the material sees an exothermic reaction at a higher temperature. This is where it has to release all the built up stress that was induced due to the heating process.  Since certain crystal structures can only handle so much dislocation prior to deformation, the material must eject the built up heat and transform to another structure.   

Conclusion

                It seems that this type of material can withstand a great amount of heat before breaking down and reverting to an Energy explosion of the exothermic reaction.  This seems to be typical of most ceramics as they generally act as great thermo conductors.  While a metal would probably exhibit changes more rapidly as it doesn't tent to withhold heat.

                In this experiment I learned that there is a difference between measuring the calorie and measuring the calorimetry of an object.  I learned how import some of these tests are in order to determine the possible application of the specific specimen.