Determination of thermodynamic functions from scanning calorimetry data. II. For the system that includes self-dissociation / association process

The basic relations between the molar fractions and the scanning calorimetry data for the system that includes self-dissociation/association process such as are presented, where m_i is the stoichiometric coefficient of the ith state A_i. The relations are described for each state j as where f_j(T) is the molar fraction function of state j and ΔH_j(T) is the difference enthalpy function of the system referred to the state j, which can be obtained by scanning calorimetry; R is the gas constant; and T is the absolute temperature. By these relations, scanning calorimetry data can be deconvoluted in order to determine the thermodynamic functions by means of single and double deconvolution. The concentration dependence of the data is analyzed by a method presented in this paper. The nonlinear least squares fitting method for the determination of the functions is discussed. For an example of the application of this method to the actual scanning calorimetry data, thermodynamic data of multistate thermal transition of Vibrio parahaemolyticus hemolysin are analyzed.