MSE 3001: Applied Thermodynamics Homework Set #7 Solutions

1) You want to use a zirconia boat (see picture below) to evaporate materials in a vacuum furnace. Thermal evaporation is a common processing approach for the synthesis of thin films or nanocrystalline powders. If the processing temperature is 2000 K and your vacuum is 133*10-5 Pa does the zirconia boat decompose under these conditions? Data: ZrO2 (s) = Zr (s) + O2 (g); G0 = 1,087,589 + 18.12T*lnT -247.36*T Joule

(i) Define a solution: We want to find out if a Zirconia boat decomposes into elemental solid zirconium and oxygen gas at 2000 K and a vacuum of 133*10-5 Pa. (ii) Plan a solution: From the given vacuum data we can determine the oxygen partial pressure in the atmosphere and compare this value with the equilibrium oxygen partial pressure for the decomposition reaction. If the equilibrium partial oxygen pressure at 2000 K is higher than the oxygen partial pressure in the atmosphere then the boat will indeed decompose because the system tries to reach equilibrium and thus has to produce more oxygen gas. If the equilibrium partial oxygen pressure is less than the oxygen partial pressure in the vacuum the oxide, i.e., the zirconia boat is stable. (iii) Execute the solution: Since the vacuum pressure is 133*10-5 Pa the oxygen partial pressure is 0.21*133*105 Pa = 28*10-5 Pa. The value of G0 at 2000 K is 868,326 J. With
G0 = RT ln(pO 2 )

The value for the partial oxygen pressure is obtained as 2.1*10-23 atm or 2.1*10-18 Pa. The equilibrium oxygen partial pressure is considerably less than the oxygen partial pressure in the vacuum atmosphere and therefore the boat will NOT decompose. (iv) Evaluate the solution:

Zirconia boats are frequently used for thin film deposition in ultrahigh vacuum equipment and at high temperatures. It is not surprising that the zirconia boat is stable, otherwise it would not be used for these applications. 2) A gas mixture of the following composition by volume: CO: 30%, CO2: 10%, H2: 10%, N2: 50% Is fed into a furnace at 1200 K. Calculate the equilibrium composition of the gas mixture, assuming the total pressure in the furnace to be 1 atm. Use the following data: C (s) + O2 (g) = CO (g); G0 = -111,713 -87.86*T Joule C (s) + O2 (g) = CO2 (g); G0 = -394,133 -0.84*T Joule H2 (g) + O2 (g) = H2O (g); G0 = -246,438 + 54.39*T Joule Assume that all gases behave ideally. (i) Define a solution A mixture of CO, CO2, H2, and N2 gases is equilibrated at 1200K and we calculate the equilibrium composition. (ii) Plan a solution First, we have to come up with the reaction itself. The nitrogen gas is inert and does not participate in the reaction. It does, however, exert pressure and has to be taken into account when calculating partial pressures. Since the volume fraction is 50 % for the nitrogen gas the volume fraction and hence the partial pressure remains constant throughout the reaction toward equilibrium. We thus know from the outset that the partial pressure of N2 is 0.5 atm at a total pressure of 1 atm. We therefore furthermore know that the sum of the partial pressures of the remaining gases has to be 0.5 atm. Relative to a total pressure of 1 atm the sum of the molar fractions of the gases other than N2 has to be 0.5. The hydrogen gas will reduce the CO2 to form more CO and H2O vapor. The reaction is thus: CO2(g) + H2(g) = H2O(g) + CO(g) (1) (I) (II) (III)

We did not include N2 in the reaction since it does not participate. We could add N2 on both sides, but this would be a very uncommon practice. From the initial composition of the gas we can see that water vapor does not exist initially. The CO2 gas must therefore react with the H2 gas to form some H2O gas and along the process will develop some CO gas in addition to the existing CO gas. For calculations we need the standard Gibbs free energy of the reaction. We have to see how we can use the three equations that are given in the problem statement to come

up with our equation (1). We can generate (1) from (II) (I) (III). This means that we obtain the standard Gibbs free energy for reaction (1) from
0 0 0 G 0 (1) = G ( II) G ( I) G ( III) = 35,982 + 32.63T

(iii) Execute the solution G0(1) (1200K) = 3174 J, and thus Kp = 0.727. CO2 Initial 1 During 1-x H2 1 1-x H2O 0 x CO 3 3+x

During the reaction the total number of units of gases is thus 5. Note that the problem statement defines the composition in terms of percentages. If we start with a total of 10 mol of gas mixture then 5 mol are N2 gas, 1 mol CO2, 1 mol H2, and 3 mol CO gas. The molar fractions during the reaction are thus: CO2: (1-x)/5 CO: (3+x)/5 H2O: x/5 H2: (1-x)/5 For reaction (1) the equilibrium constant is obtained as
p p x (3 + x ) K p = CO H 2O = = 0.727 and hence x = 0.161. p CO 2 p H 2 (1 x ) 2

The molar fractions for the mixture of CO, CO2, H2, and H2O in equilibrium are thus: CO2: (1-x)/5 = 0.1678 CO: (3+x)/5 = 0.6322 H2O: x/5 = 0.0323 H2: (1-x)/5 = 0.1678 Since the total pressure of the mixture of CO, CO2, H2, and H2O must be 0.5 atm we obtain the partial pressure of the gases:

pCO2 = 0.1678*0.5 atm = 0.084 atm pCO = 0.6322*0.5 atm = 0.316 atm pH2O = 0.0323*0.5 atm = 0.016 atm pH2 = 0.1678*0.5 atm = 0.084 atm The composition of the gas mixture in equilibrium at 1200 K is then: 1.6 vol% H2O(g) 8.4 vol% CO2(g) 8.4 vol% H2(g) 31.6 vol% CO(g) 50 vol% N2(g) (iv) Evaluate the solution The first test is the summation of the equilibrium partial pressures or mol fractions and they indeed add up to 0.5 atm. Since the gas mixture initially contained 30 % CO and additional CO has to be formed if the reaction proceeds according to (1) we would expect the equilibrium volume fraction of partial pressure of CO to be higher than 0.3 atm or 30 vol%, but probably not my much. Our result shows that indeed the partial pressure increased only by 0.016 atm.