Journal Title
Title of Journal: Monatsh Chem
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Abbravation: Monatshefte für Chemie - Chemical Monthly
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Publisher
Springer Vienna
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Authors: Justyna Nyk Bogusław Onderka
Publish Date: 2012/08/25
Volume: 143, Issue: 9, Pages: 1219-1224
Abstract
The activity coefficient of oxygen f textO0 in liquid Ag and binary Ag–Te dilute alloys were determined between 1285 and 1485 K by coulometric titration using the electrochemical cell Ir O in liquid metal or alloy yttria stabilized zirconia air Pt The experimental and evaluation procedures described in the literature were adopted The oxygen activity coefficient was determined in pure liquid silver to be ln f textO0 = 17602 mathordleft/ vphantom 17602 T right kernnulldelimiterspace T + 06315 Next the oxygen activity coefficient in dilute Ag–Te–O alloys for variable X Te content from 001 to 006 was measured From the obtained results Wagner’s interaction parameter varepsilon textOtextTe as a function of temperature was derived in the form varepsilon textOtextTe left pm 032 right = 18483 mathordleft/ vphantom 18483 T right kernnulldelimiterspace T + 7668 The electrochemical coulometric titration method seems to be very useful to study the thermodynamics of oxygen interaction in liquid silver and its alloysThe byproduct of the electrolytic refining of copper ie “anode slime” 1 is a valuable source of silver gold platinum group metals selenium and tellurium The processing of slime usually involves many steps with the common goal of removing Cu Se Te etc and leaving pure Ag Au and Ptgroup metals as raw silver—socalled doré metal So the anode slime containing precious metals is dried and then charged into a rotary Kaldo furnace in which it is melted converted and firerefined 2 The product of this process is the doré metal from which anodes are casted for elimination of remaining impurities in an electrorefining process Pure silver cathodes contain 9999 AgTellurium in silver slimes is a harmful impurity element because of limited volatilization during converter blow contrary to selenium and bismuth and it tends to accumulate in the metal phase As a result of the low stability of oxides it cannot be oxidized easily during the Kaldo process in a rotary furnaceSuch conventional processing by smelting of slimes in converters with the addition of fluxes and oxidizing agents and with the injection of oxygen into the molten bath reduces the amount of Cu Se and Te The refining step of the liquid alloy by oxidation is very efficient for selenium whereas oxidation of tellurium does not take place until the Se/Te mass ratio decreases to 055 3 4 Thus the knowledge of oxygen interaction in Ag–Te–O liquid alloys is a key in the Ag purification process but no previous information is available on the tellurium–oxygen interactions in molten silver Additionally oxygen and other dissolved gases in the liquid alloy can have a great effect on the chemical mechanical and electronic properties of materials Thus the knowledge of oxygen activity in the wide composition and temperature range of liquid multicomponent alloys can help one to design and optimize the conditions for the preparations of new innovative materialsThe modified coulometric titration method is suitable for the determination of oxygen concentration and activity in liquid metals eg Ag 5 or Te 6 7 As silver oxide is unstable at elevated temperatures 8 9 it seems to be the only method for the measurement of the activity of oxygen in unsaturated liquid Agbased alloys An additional problem is connected with the high tellurium partial pressure at elevated temperatures in the range of dilute liquid solutions of Te in silver 10The activity coefficient of oxygen in liquid silver has been determined several times 5 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Some results were obtained by use of modified titration technique 5 15 16 25 which is especially suitable for the determination of low oxygen concentrations and activities in liquid metallic alloys Published solubility and activity data of oxygen in liquid silver were recently reviewed by Assal et al 9 in their study on the thermodynamic properties of the Ag–O system
Keywords:
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