IC 6454 Revision of the Free Energy of Formation of Sulphur Dioxide

The recent determination by Eckman and Rossini of the heat of formation of sulphur dioxide appears to be of much greater accuracy than any previous measurement . The value obtained by them , 70,940 cal . , is in good agreement with that of Thomsen ( 71,080 ) , but differs by about 1,700 calories from Berthelot's result ( 69,260 ) , and by 1,940 calories from the provisional figure ( 69,000 ) adopted by Lewis and Randall in their studies of the free energies of the sulphur compounds . This large discrepancy suggested the desirability of a recalculation of the free energy of sulphur dioxide . In addition it is now possiblt to fix the specific heat of S₂ gas with greater certainty than at the time of the original calculations . These two changes are incorporated in the recalculations described below , and directly affect the values of AH , and the Ar terms in the free energy equation . In the determination of the integration constant of the latter equation , the free energies and specific heats of water vapor and the oxides of carbon are required as auxiliary data . In this work these are based , with certain exceptions , upon the equations previously deduced , which differ appreciably from the corresponding equations of Lewis and Randall . 56 · The principal equilibria employed below , and the plan of calculation , remain the same as in the calculations of Lewis and Randall . Before beginning this revision a search of the literature was made , extending to August , 1930 , for studies of additional equilibria . Only one reaction was found that gives promise of increased accuracy . This is the equilibrium of sulphur dioxide with copper , cuprous oxide , and cuprous sulphide . In this case , however , certain of the subsidiary data are lacking , and until they become available , the existing studies of the equilibrium in this system can not be successfully utilized . The changes in the numerical data mentioned above , especially in the thermochemical constants , are therefore solely responsible for the rather significant differences of the revised from the original values of the free energy .