: To study more precisely than before the spontaneous heating properties of thermally unstable substances, it was tried to make such a new adiabatic apparatus that the operation is easy and the accurate data can be obtained with good reproducibility and a wide applicability can be expected, applying a more completer adiabatic control technique than those of most apparatus in the past. Thus, the purpose of this note is to place on record the constructional and procedural details and the experimental performances of this apparatus.
Main features of this apparatus are as follows.
1) Adoption of the PID-SCR temperature control technique. Some instruments were also used together with this technique to realize the control as complete as possible, such as a pre-amplifier to amplify the ΔT value, a zero suppression circuit to compensate the stray thermal e.m.f. of the differential thermocouple (Fig.2), a cold junction based on the thermoelectric effect, a voltage shock absorber, some noise filters, etc. Ultimately, the adiabatic control of ±0.2 μV(±0.005 °C) could be achieved at the initial slow heating stages of the sample.
2) Attempt to control adiabatically between the sample and the atmosphere. In other words, the establishment of the true physical adiabatic condition around the sample was intended, rather than the apparent stability of the ΔT base line as observed in such cases that the control is made between solid and solid or between solid and liquid.
3) Adoption of air bath. This is for the control to be able to follow easily even at the rapid Heating stages of the sample.
To check the sensitivity of this apparatus, the effect of the rate of heat evolution on the rise rate of sample temperature was measured by evolving Joule heat of 150 to 800 μW in the cell at 60 °C. As the result, 55 μW was found as the lowest limit of the sensitivity of this apparatus (Fig.5).
H.J. Pasman also made an adiabatic vessel under the similar conception as ours, using a Dewar as the cell10). He reported he had succeeded in detecting a heat production of 10 mW / kg by using a large sample amount of 1 kg or so. However, the mentioned experiment was actually carried out under such a condition as brings about a heating rate more than 100 mW/kg. In the present case it is probably owing to the strict PID-SCR control that the sensitivity comparable to that of the large scale test could be obtained, in spite of the sample amount less than 1 g and the cell of only a tentative design. Therefore, it will be easy to get a more improved sensitivity on this apparatus, should a new cell structure be devised and should a larger amount of sample be used.
Pure linolic acid/absorbent cotton mixture, in the form of uniformly scattered fiber assembly in the cell, was used throughout this study as a model of spontaneously heating stacks. The cotton acts as the substrate and was practically inactive to oxygen under the conditions of this study. Oxygen of 1 atm was used as the atmosphere. The standard experimental conditions are as follows : the sample amount, linolic acid, 50 μl, absorbent cotton, 50 mg ; the flow rate of oxygen, 2.3 ml/min ; the range of the pre-amplifier, ±50 μV ; the initial ambient temperature, 60 °C.
Main experimental results are as follows.
1) The reproducibility of the heating curve is very well. For example, the scatter was within ±1 min for a temperature rise of 8 °C during 70 min at 70 °C (Fig.7).
2) The spontaneous heating process is, in the same way as experienced in the usual reaction; affected sensitively by factors such as the temperature ; the surface area, the loading density or the extent of pre-oxidation of the sample ; the coexistent substances ; as well as the range of adiabatic control.
3) An excellent linear relationship was found to hold between In ΔT and 1/T, assuming the reaction to be of the zero-order at the initial stages, where T is the initial ambient temperature and Δt is the time taken to produce a given temperature rise of 100 μV (2.5 °C) from the initial temperature (Fig.9, Eq.4).
4) Under the condition that the linolic acid/cotton ratio is kept constant, the rise rate of the sample temperature decreases gradually at successively lower loading densities of the sample (Fig.11). This fact means that, as the sample happens to be the fiber assembly, the thermocouple for the sample does not indicate the temperature of the assembly itself but shows that of the space in the cell which contains the distributed linolic acid/cotton mixture. In other words, the observed heating curve does not reflect the progressive state of oxidation reaction of the sample itself, but only tells of the accumulation process of heat of reaction evolved within the time, during which the sample has been exposed to oxygen. Thus, the initial minute temperature rise after a given elapsed time is proportional to the sample amount (Table 1), and the time taken to produce a given temperature rise of 50 μV (1.25 °C) is inversely proportional to the sample amount (Fig.12), assuming the zero-order reaction to take place at the initial stages, other conditions being equal.
This apparatus showed to be very useful for studying the spontaneous heating behavior of a wide range of substances and the effects of temperature, coexistent substances and atmosphere on it, with relatively small sample amounts and with easy procedures. However, the modification of the design may naturally be made as desired, to suit special requirements and to get a more improved sensitivity.
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