ME 581 Homework Four Fall 12

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Prof. W. H. Warnes Office: Dearborn Hall 303E Phone and Voice Mail: (541) 737-7016 FAX (541) 737-2600 matsci.oregonstate.edu DUE Thursday, November 29, 2012
This page last updated December 9, 2012 email: warnesw@engr.orst.edu

1) The ternary phase diagram for the silver-cadmium-copper system is shown below in an isothermal slice at 600 [C]. Use the diagram to answer the following questions about the ternary: a) What are the phases that are represented in the ternary system at this temperature? b) Which of the three elements has the lowest melting temperature, and how can you tell from the phase diagram? c) Locate the composition 70%Cd - 20%Ag - 10%Cu on the phase diagram. What phase or phases are present in equilibrium? d) Locate the composition 10%Cd - 60%Ag - 30%Cu on the phase diagram. What phase or phases are present in equilibrium? e) Estimate the compositions and mass fractions of the phases in equilibrium for part (d) above. f) How many three phase equilibrium regions are shown at this temperature? Identify them by naming the phases in equilibrium for each region.

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2) I need to produce some H2 gas by dissociating ammonia using the reaction NH3 (g) = 1/2 N2 (g) + 3/2 H2 (g). Assuming that I start with pure ammonia gas at 1 [atm] pressure and keep the total pressure constant, a) at what temperature does the equilibrium composition contain 50% ammonia gas? b) at what temperature has 95% of the ammonia gas dissociated at equilibrium? 3) When a mixture of PCl5 and PCl3 is allowed to come to equilibrium at 500 [K] with a total pressure of 1 [atm] it is found that the partial pressure of Cl2 gas in the furnace is 0.1 [atm]. What was the original ratio of PCl5 to PCl3 in the starting mixture (which initially had no Cl2 gas)? Data for the PCl5 (g) = Cl2 (g) + PCl3 (g) can be found in the appendix. 4) I would like to understand the process of reducing ZnO solid to pure Zn in order to better control the oxidation process of forming ZnO. The proposal is to use carbon monoxide (CO) gas as the reducing agent. The reaction

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will be done at a high temperature (1500 [K]), above the boiling point of Zn so that the pure Zn will be in the vapor phase. The likely reaction for this process is: ZnO (s) + CO (g) = Zn (g) + CO2 (g) a) The standard free energy of reaction can be written as combination of several of the reactions in the appendix of Gaskell. Write them out and develop an equation for the standard free energy of reaction as a function of temperature for this reduction process. b) Calculate the partial pressure of Zn vapor in the gas mixture at equilibrium at T = 1500 [K]. Assume a total pressure of 1 [atm]. 5) Determine the maximum pressure of O2 gas in which a Si wafer may be heated at a temperature of 1273 [K] without oxidizing to form SiO2. 6) Data for the free energy of formation of NiO from both liquid and solid Ni are given in the appendix to Gaskell. Using ONLY this information (you don't need to look up anything else) calculate the melting temperature of Ni, the latent heat of melting and the entropy of melting of Ni.

SOLUTIONS

1a) What are the phases that are represented... Don't get confused between the number of components and the number of phases. There are three components, since it's a ternary; Ag, Cd, and Cu. There are more than three phases visible on this isothermal section of the diagram. The phases are: L, liquid (Cu), solid solution (Ag), solid solution BETA, a Ag-Cd solid solution with some Cu dissolved in it, and GAMMA, a different Ag-Cd solid solution with less Cu dissolved in it. On the modified ternary diagram below I colored each of the FIVE single phase regions in LIGHT BLUE. 1b) Which of the three elements has the lowest melting temperature... By looking at the pure component apex it is possible to determine whether the component is in the liquid or solid state. At the Cd apex, the phase is liquid, and at the Cu and Ag apices the components are solid phases. Therefore, 600 [C] is above the melting temperature of Cd and below the melting temperatures of Ag and Cu. Thus, Cd must have the lowest melting temperature of the three. 1c) Locate the composition 70%Cd - 20%Ag - 10%Cu on the phase diagram. What phase or phases are present in equilibrium? I have marked the position of this composition on the diagram as an ORANGE dot (labeled "(c)"), which is clearly in the single-phase LIQUID region.

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1d) Locate the composition 10%Cd - 60%Ag - 30%Cu on the phase diagram. What phase or phases are present in equilibrium? I have marked the position of this composition on the diagram as a GREEN dot (labeled "(d)"), which is in the two-phase region containing the solid solution phases of (Cu) and (Ag). 1e) Estimate the compositions and mass fractions of the phases in equilibrium for part (d) above. To do this calculation, we need a tie-line that passes through the overall composition of the system (at point (d)) and intersects the solubility lines for the two phases of (Cu) and (Ag). I have sketched this as the DASHED GREEN LINE in the figure. Since we don't know precisely where this tie-line goes, we have to estimate it by remembering that each of the compositions along the solubility line for the (Cu) phase on the left (along the edge of the light blue colored region) matches to one composition along the solubility line for the (Ag) phase on the right. A figure showing all of the tie lines would look like a fan of lines more densely positioned at the (Cu) end than along the (Ag) end. To use the tie line, we need to determine the length of the two sides of the "lever arms", which means finding the composition of the phases at the ends of the tie line. I estimate the composition of the (Cu) solid phase to be 1%Cd-3%Ag-96%Cu, and the composition of the (Ag) solid phase to be 14%Cd-83%Ag-3%Cu. The mass fractions are found from the lever rule which is basically the conservation law for the components. We can therefore use any of the components in the lever rule to find the mass fractions.

The small differences in the three calculations are due to the round-off errors in reading the compositions off the diagram. You could also have done this by measuring with a ruler the lengths of the lever arms. 1f) How many three phase equilibrium regions are shown at this temperature... In the figure below I have marked each of the three-phase regions with a different color. There are three different three-phase regions: RED region: LIQUID, GAMMA and BETA. GREEN region: LIQUID, BETA, and (Cu). YELLOW region: BETA, (Ag), and (Cu).

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2a) at what temperature does the equilibrium composition contain 50% ammonia gas? Start with the conservation relation from the reaction stochiometry equation:

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We'll use this to give us the partial pressures of the gases at equilibrium:

We also know the free energy of the reaction, based on the appendix in the back of Gaskell (NOTE: we have to reverse the reaction in the appendix to match our dissociation problem, and divide by two to match the stochiometry of the reaction):

Setting the two equations for the equilibrium constant equal to each other gives the following generalized equilibrium relation:

For this part of the problem, we are asked to find the temperature which yields 50% of the gas mixture AT EQUILIBRIUM to be methane gas From the expression for the partial pressure of methane we derived above, we have:

Plugging x = 0.333 into the general equation above gives us an equation to solve for the equilibrium temperature, T:

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Using an equation solver, I found T = 401.8 [K] = 128.8 [C]. 2b) at what temperature has 95% of the ammonia gas dissociated at equilibrium? This is the same approach as the first part of the problem, with the only difference being how much of the ammonia has DISSOCIATED. In this case, for 95% dissociation, the x = .95:

Again, the solver gives me T = 565.63 [K] = 292.6 [C].

3) ...what was the original ratio of PCl5 to PCl3 in the starting mixture... This problem is very much like problem 2 except we are working backward. We know the equilibrium conditions, but we don't know the initial conditions. I'll go through the problem with the same steps as problem 2.

where A is the ratio of PCl5 to PCl3 in the starting mixture that we are solving for. We'll use this reaction stochiometry information to give us the partial pressures of the gases at equilibrium:

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ME 581 Homework Four Fall 12

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We also know the free energy of the reaction, based on the appendix in the back of Gaskell (NOTE: we again have to reverse the reaction in the appendix to match our dissociation problem):

From the problem statement, we know the final partial pressure of the chlorine gas, which we can use to find x, and then A:

This is the final answer: we need a ratio of 0.371moles of PCl5 for each mole of PCl3 in the starting mixture.

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4a) The standard free energy of reaction can be written as combination of... Looking up the reactions in the back of Gaskell to build up the reaction we are interested in I find the following:

4b) Calculate the partial pressure of Zn vapor in the gas mixture at equilibrium at T = 1500 [K]. Assume a total pressure of 1 [atm]. Plug and chug. Remember that the assumption of zero compressibility of the condensed phase means it doesn't show up in the equilibrium constant equation.

Now we need to look at the reaction stochiometry to track the changes in the partial pressures on reaction. We can see that the amount of Zn vapor that forms is equal to the amount of CO2 vapor, so the partial pressures are always equal: pZn = pCO2. We also know, from the problem statement, that the total gas pressure is 1 [atm], so that Ptot = 1 [atm] = pZn + pCO + pCO2 = pCO + 2pZn. Putting these together, we have two equations in two unknowns, pZn and pCO.

5) ...maximum pressure of O2 gas in which a Si wafer may be heated at a temperature of 1273 [K] without

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oxidizing to form SiO2. I intended you to use the Ellingham diagram in the book for this one. You may, of course, do the full calculation but it takes a bit longer. Here's my graphical solution using Figure 12.13. Find the SiO2 reaction on the diagram (I marked this in GREEN), and mark the temperature of interest (which I marked with a RED dot). Now draw a line from the DELTA-G = 0 point through the reaction/temperature point to find the oxygen partial pressure in equilibrium (this line is shown as the BLUE dashed line). Where this line intersects with the oxygen partial pressure scale gives the answer (BLUE circle). It looks like about pO2 = 10-30 [atm]. Partial pressures lower than this will preferentially form the un-oxidised Si, and pressures larger than this will favor the SiO2.

6) ...calculate the melting temperature of Ni, the latent heat of melting and the entropy of melting of Ni.

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ME 581 Homework Four Fall 12

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The Gaskell data for these two reactions is shown below:

The melting temperature will be the temperature at which these two equations give the same DELTA-G:

That's pretty close to the handbook value I have of 1726 [K]. Reversing the liquid reaction and adding it to the solid reaction gives the melting reaction for Ni:

End of File.

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