Extractive Metallurgy Division - Heats of Solution in Liquid Tin of the Group III Elements Aluminum, Gallium, Indium, and Thallium

The partial molar heats of solution at infinite dilution in tin of aluminum at 300° and 350°C and of gallium, indium, and thallium at 240°, 300°, and 350°C have been measured by tin solution calori-metry. Aluminum, gallium, and thallium are endo-thermic on solution; indium is exothermic. Any temperature dependence of the heats of solution lies within the experimental scatter. Over the dilute ranges investigated, only aluminum has a measurable change in its heat of solution with composition. HEATS of solution of one element in another reflect the interaction between them. The investigation of partial molar heats of solution in dilute alloys is of particular interest as the properties of the solvent are altered to only a limited extent by the presence of the solute and also as the interaction between solute atoms is small. When the heats of solution of a related series of elements in a solvent are known, a systematic comparison may be made. In the investigation reported here, the partial molar heats of solution of the Group III elements aluminum, gallium, indium, and thallium in dilute solution in tin were measured. This work follows an investigation of the heats of solution in tin of the Group IB elements.' EXPERIMENTAL PROCEDURES Materials. Samples of gallium, indium, and thallium were obtained from Johnson, Mathey and Co., Ltd. Indium and thallium were supplied as wire, 1.6 mm in diam; gallium was in the form of irregular pieces. The supplier reported the following minimum purities: gallium—99.95 pct; indium—99.99 pct; thallium—99.99 pct. The aluminum, obtained from Alcoa Research Laboratories, was reported to be 99.995 pct pure. The tin was supplied by Baker and Co., Inc.; the reported analysis indicated a tin content of at least 99.96 pct with lead as principal impurity. Calorimeter. this description will cover only the essential features of the calorimeter with special attention to modifications made since an earlier description was published.' A Dewar flask containing the tin bath was held in a constant-temperature bath of a near-eutectic mixture of lithium, sodium, and potassium nitrates. This bath, which was stirred vigorously, was heated by a primary resistance winding in the container wall and by a secondary winding immersed in the salt. The voltage supplied to both windings was stabilized. The temperature of the salt bath was controlled by means of a platinum resistance thermometer in one arm of a Wheatstone bridge. The light from a mirror galvanometer in the bridge circuit fell on a photocell which controlled the current in a saturable reactor in series with the secondary winding. In this manner, the temperature of the salt bath was controlled to ±0.003°C and that of the tin bath to at least ±0.002°C. Each of these temperatures was measured by two iron-constantan thermocouples in series, coiled in a helix to minimize heat loss and immersed in the salt and tin baths in protective sheaths. The temperature of the laboratory was kept constant to ± 1°C during a run. Specimens were dropped into the tin bath from an addition arm held at O°C which was part of the cal-orimetric system. The system was evacuated to about 0.02 1 to minimize oxidation and to reduce transfer of heat. The bath was stirred by a glass stirrer introduced through a double Wilson seal. The samples were scraped clean before weighing, which was carried out as rapidly as possible. Each sample was immediately placed in the evacuated addition arm to minimize contamination. These precautions were especially necessary with aluminum. After the runs with gallium and thallium at all temperatures and with indium at 240° and 350°C (Series I) were completed and before the runs with indium at 300°C and aluminum at 300° and 350°C (Series 11) were begun the following changes were made. The shape of the Dewar flask was changed so as to result in a lower surface to volume ratio of the bath and at the same time the amount of tin was reduced from 500 to 400 g. The paddle type stirrer was replaced by a helical screw and the rate of stirring was increased to about 150 to 200 rpm.