16/07/2026
Thermal reaction hazards are nearly always assumed to initiate at temperatures above ambient; indeed, calorimeters for measuring the hazard onset temperature don’t even exist.
For example, the method for calibrating such devices begins at temperatures above room temperature, assuming that lower temperatures are of no interest.
In order to test chemical stability below room temperature, it is necessary to cool the calorimeter internals – this will be the new ambient temperature, and chemical stability can be tested above that. With this temperature stable, the heat-loss (or, in this case, heat gain) calibration can be performed, allowing chemical testing to begin below ambient temperature.
In Figure 1 (main image), the heat-wait-search test starts from a low temperature (-20 °C). At every 5 °C, the sample temperature is held constant to determine whether an exotherm can be detected (wait/search period). However, unlike standard calorimeters, the sample temperature (red) is higher than the calorimeter temperature (green). The period of constant temperature (the search period) is when the “onset” temperature of the exotherm is identified and corresponds to when the exotherm is generating enough heat to be detectable - in this case, it occurs at 20 °C.
Once the exotherm has been detected, the chemical reaction can be allowed to proceed and tracked (adiabatically) as the temperature gradually increases toward completion.
At a sample temperature of around 179 °C, the reactants are consumed, and the temperature flattens. In this test, another red line represents the sample pressure, which clearly increases as the exotherm accelerates.
Extending the working temperature range of an adiabatic calorimeter below ambient is not often needed but is crucial when the process runs at low temperature.
In Figure 2 (main image), the exotherm was observed to start at 20 °C, which would not be possible in a standard calorimeter, where the minimum detectable temperature is around 30 °C or higher.
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