RI 3262 Progress Reports – Metallurgical Division 9. Thermodynamic Data on Metallurgically Important Compounds of Lead and the Antimony-Group Metals and their Applications

"INTRODUCTION The use of thermodynamic calculations to answer practical problems in metallurgy, especially those that are relatively difficult to test experimentally, is rapidly becoming a conventional method of procedure. Nevertheless, these methods cannot he applied effectively until the fundamental thermodynamic constants used for them have become available either by direct experiment or by recalculation of data already existing in more or less undigested form.In an attempt to collect such data far the compounds of lead and the antimony group the incentive has been to make a preliminary survey that will disclose the gaps or questionable phases of available information and to collect data that may be used to answer certain rather practical problems presented by operating metallurgists.This report comprises three sections; the first gives the basis of selection of the constants which may now be given or estimated, and the later sections discuss the application of the figures obtained to two of the more interesting problems.The reader will discover that many of the quantities involve critical study of a number of more or less discordant observations. Although certain data could be rejected on the basis of thermodynamic comparisons, it must not be overlooked that many of the figures are the results of rational estimates rather than exact experiment. The use of thermodynamic methods to control and partly authenticate such estimates is one of its most valuable characteristics for the practising metallurgist or chemist, who cannot check by direct experiment each property of the materials which he converts to usable form.Nevertheless, while it is definitely possible in certain instances that the final figure selected for the heat or free energy of a process or substance may be in error by as much as a few hundred to a few thousand calories per formula weight, questionable figures are usually revealed by the thermodynamic calculations made. When quantities of such degree of accuracy are, and they often must be, used for estimating an unknown reaction, the result often gives no more than the order of magnitude of the desired quantities. Yet even in these extreme cases the answer is far more reliable and valuable than an unordered guess or a conclusion based on incorrect data."