Thermal dynamics of bomb calorimeters.

Abstract

The thermal dynamics of bomb calorimeters are modeled using a lumped heat transfer analysis in which heat is released in a pressure vessel/bomb immersed in a stirred water bath that is surrounded by a static air space bounded by an insulated (static) jacket, a constant/controlled temperature jacket (isoperibol), or a changing temperature (adiabatic) jacket. The temperature history of the water bath for each of these boundary conditions (methods) is well described by the two-term solution for the calorimeter response to a heat impulse (combustion), allowing the heat transfer coefficients and thermal capacities of the bomb and water bath to be determined parametrically. The validated heat transfer model provides an expression for direct calculation of the heat released in an arbitrary process inside a bomb calorimeter using the temperature history of the water bath for each of the boundary conditions (methods). This result makes possible the direct calculation of the heat of combustion of a sample in an isoperibol calorimeter from the recorded temperature history without the need for semi-empirical temperature corrections to account for non-adiabatic behavior. Another useful result is that the maximum temperature rise of the water bath in the static jacket method is proportional to the total heat generated, and the empirical proportionality constant, which is determined by calibration, accounts for all of the heat losses and thermal lags of the calorimeter.