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# Problem Set - 3 MM 651 Thermodynamics of Materials 1.

An empirical equation for the excess Gibbs energy of liquid Ag[1]-Cu[2] alloy is Gex = - R (2100 + 0.511 T) x1 x2. Derive the equations for Hex, Sex, 1, 2 and compute 1 and 2 at 1550 K and x2 = 0.5 2. The activity coefficient of Zn in liquid Zn Cd alloy at 700 K is given by ln zn = 0.875 X2cd 0.30 X3cd Derive the expression for ln cd on composition and calculate the Gibbs free energy of mixing for Xcd = 0.4 at 700 K. 3. CaO and MgO form solid solutions with limited solubility. Assuming that the solutes obey Henrys law with CaO = 12.88 and MgO = 6.23, calculate the solubility of CaO in MgO and MgO in CaO. 4. Melts in the system Pb-Sn exhibit regular solution behaviour. At 473 C, apb = 0.055 in a liquid solution of Xpb = 0.1. Calculate the value of the aoL and find the activity of Sn in a liquid solution of Xsn = 0.5 at 500 C. 5. The Gibbs free energy of mixing of a solid solution is given by Gmix = 10,600 X1 X2 + RT [X1 ln X1 + X2 ln X2] Calculate the critical temperature Tc for phase separation. Calculate the spinoidal and the phase boundary at 0.7 Tc. 6. Ge-Si forms an isomorphous system with complete solid and liquid solutions. The melting points of Ge and Si are 1200 oC and 1680 oC respectively. At 1475 oC, the liquidus and solidus compositions are respectively, XSi = 0.32 and XSi = 0.665. Assuming the both the solid and liquid solutions are ideal solutions, estimate the values of heat of fusion of Ge and Si. 7. A (TmA= 1400 K) and B (TmB=1000 K) form a eutectic and their Heats of Fusion are 3200 and 2500 cals/mol respectively. At 1200 K, solubility of B in solid A, XBS = 0.05 and in liquid XBL = 0.40. At 600 K, the solubility of A in solid B is 0.07 and of B in solid A is 0.03. Find the activity coefficient of A and B at 600 K and of B in solid A at 1200 K. Assume the liquid to be an ideal solution. 8. The excess gibbs free energy for the Fe-Ni liquid solution is given by the expression

Gex = (-4100 + 0.8 T) x1 x2 J/mol. Calculate the values for Hex, Sex and compute 1 and 2 at 1800 K and x2 = 0.5 9. Two elements A and B (or 1 and 2) form complete solutions in both the solid [] and liquid [L] phases. Two calculate the phase diagram, it is necessary to compare the Gibbs free energy of mixing of both the solutions. Assume that both the solutions are regular solutions. Formulate the equations for Gibbs free energy of mixing of both the solutions assuming that the reference state is {L,L}