Part VII – July 1969 - Papers - Thermodynamic Activity Measurements Using Atomic Absorption: Copper-Zinc

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.