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Thermodynamics

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1) Gaskell #11.6 (i) Define the problem We consider the dissociation reaction of nitrogen at 3000 K and determine the partial pressure of atomic nitrogen gas at a total pressure of 1 atm and the total pressure of the gas at a partial pressure of N2 of 90 % of the total pressure. (ii) Plan a solution The key to the solution is the standard Gibbs free energy of the dissociation reaction and the relation to the equilibrium constant: N2 = 2N

p2 0 G = RT ln K p = RT ln N p N2

The total pressure is given as the sum of the partial pressures of the atomic and the diatomic nitrogen. (iii) Execute the solution 1. G0 (3000K) = 945,000-114.9*3000 J = 600,300 J For a total pressure of 1 atm the partial pressure of N2 is 1 pN and hence:

p2 600,300 = R * 3000 * ln N 1 pN , therefore pN = 5.9*10-6 atm

0.12 -9 600,300 = R * 3000 * ln P , thus P = 3.2*10 atn 0.9

2) Gaskell #11.7 (i) Define a solution We calculate first the total pressure at which the equilibrium mol fraction of N2 is equal to 0.2 when ammonia gas is heated up to a temperature of 300C. Next we determine the standard enthalpy and entropy changes for the dissociation reaction of ammonia gas. (ii) Plan a solution The reaction is: 2NH3(g) = N2(g) + 3 H2(g)

The stoichiometry of the reaction tells us that per unit of N2 in equilibrium three times that unit must exist as H2 gas. If the mol fraction of N2 in equilibrium is 0.2 the mol fraction of H2 is therefore 0.6 and the mol fraction of NH3 is then 1 0.2 0.6 = 0.2. From the textbook appendix A-1 we know that

G 0 = 87,030 25.8T ln T 31.7T

p3 p N2 G 0 = RT ln K p = RT ln H 2 2 p NH3 and Daltons Law we can

solve the problem. To obtain the standard entropy of the reaction we use the thermodynamic relation

G = S and once we have the entropy and Gibbs free energy we T

obtain the enthalpy from G = H TS. (iii) Execute the solution At 300C or 573K we have: G 0 = 87,030 25.8 573 ln 573 31.7 573 = 25,021.8 J Therefore lnKp = 5.25 and Kp = 191. From XN2 = 0.2, XH2 = 0.6, and XNH3 = 0.2 it follows that pN2 = 0.2P, pH2 = 0.6P, and pNH3 = 0.2P and thus

191 = 0.6 3 0.2 2 P = 1.08P 2 and thus P = 13.3 atm. 2 0.2

G 0 = S 0 (T) = 25.8(1 + ln T ) + 31.7 and hence T H 0 (T ) = G 0 + TS 0 = 25,021 + 221.4T . At 300C the standard entropy of the

dissociation reaction is thus -221.4 J/K and the standard enthalpy is -101,814 J.

3) Determine the maximum temperature to which molybdenum can be heated without formation of the oxide MoO2 in an atmosphere of 69 percent hydrogen and 31 percent by volume of steam (G0 = -585,760- 19.2*TlnT + 233.7*T)

4) The equilibrium constant K for the hydrogenation of pyridine (used for pharmaceuticals, herbicides, pesticides, food flavorings, dyes, adhesives, paints, etc) to piperidine (used for pharmaceuticals, for the production of vulcanization accelerator, etc) in the temperature range between 140C and 260C is: lnK = -46.699 + 24320/T. Calculate Hm0, Sm0, cp m0at 200C.

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