Chemistry 231 Tutorial Session # 7

G. Marangoni Date: Friday, November 26, 2010.

The following questions will be answered on the tutorial session. 1. When 2.00 mol of a gas at 330 K and 3.55 bar is subjected to an isothermal compression, its entropy decreases by 25.0 J/K. Calculate the final pressure and the Gibbs energy change for the transformation. 2. Calculate the equilibrium constant for the reaction CO(g) + H2 (g) H2CO (g) given that for the production of liquid formaldehyde from CO and H2, the standard Gibbs energy of reaction is 28.95 kJ/mole and the vapour pressure of formaldehyde is 1500 Torr at 298.2 K. 3. For the reaction PCl5 (g) PCl3 (g) + Cl2 (g), the equilibrium constant for the reaction is 0.285 at 485 K and 4.96 at 556 K. Estimate the standard enthalpy change for the reaction and calculate the standard Gibbs energy change at 575 K. Clearly state any assumptions. 4. The equilibrium constant for the reaction N2 (g) + 3 H2 (g) 2 NH3 (g) is 0.1744 at 500 K. Calculate a) The standard Gibbs energy change for the process. b) If the reaction mixture contains 0.10 mole of H2(g), 0.15 mole of N2(g), and 1.5 moles of NH3(g), calculate the nonstandard reaction Gibbs energy for the process. c) Calculate the G when 0.10 mole of the NH3 reacts to give additional N2 and H2. 5. A sample containing 35.0 g of Ar is enclosed in a container of volume 0.165 L at 390 K. Calculate P using the ideal gas and the van der Waals equation of state. Based on your results, does the attractive or repulsive contribution to the interaction potential dominate under these conditions?

Please answer the following questions. Answers will be posted on the website.
6. The equilibrium pressure of H2 above a mixture of UH3 (s) and U (s) is 1.04 Torr at 298 K. Calculate the standard Gibbs formation energy of UH3 (s). 7. Calculate the van der Waals parameters of methane from the values of the critical constants. 8. For the equilibrium N2O4 (g) 2 NO2 (g), the equilibrium constant at 298 K is 0.148. a) Calculate the rG at 298 K.

b) Given that the system initially contains 0.300 mole of N2O4 and 0.500 mole of NO2, calculate the composition of the system when equilibrium is attained at 2.00 bar pressure. 9. For the above system, the standard enthalpy change for the reaction is 57.20 kJ/mole. Calculate the equilibrium constant for the reaction at 500 K assuming a) the rH is constant over the temperature range of interest; b) using the heat capacity change for the reaction to calculating the dependence of the rH with temperature. 10. A sealed container was charged with 0.300 mole of H2 (g) 0.400 mole of I2 (g) and 0.200 mole of HI (g) at 870 K and 1.00 bar pressure. Given that the equilibrium constant for the reaction is 870 for the reaction H2 (g) + I2 (g) 2 HI (g), calculate the composition of the system at equilibrium.

Answers
1. Note that we will treat this as an isothermal expansion of an ideal gas.

2. Note that we have the standard Gibbs energy for the production of liquid formaldehyde from CO (g) and H2 (g).

We want the standard Gibbs energy change for the reaction

The difference between the reactions is the Gibbs energy change for the vapourization of formaldehyde. for which the Gibbs energy change can be written

3.

First calculate the molar volume of the gas.

Because PvdW < Pideal gas, the attractive part of the interaction appears to dominate using the van der Waals equation of state. 4. Use the integrated vant Hoff equation hence we must assume that the standard reaction enthalpy does not change between 485 and 556K.

5. a)

b)

c) For the advancement of 0.100 mole of NH3 towards equilibrium N2 (g) + 3 H2 (g) 2 NH3 (g) Initial advancement () final 0.15 mol +0.05 mol 0.20 mol 0.10 mol +0.15 mol 0.25 mol 1.50 mol -0.10 mol 1.40 mol

The difference in the Gibbs energy upon advancing the reaction by 0.10 mol of NH3 =39.34 kJ/mol 51.89 kJ/mol = -12.50 kJ/mol 6. For the equilibrium reaction

Note that in the above reaction

7. Critical constants are found in Table 7.2 Appendix A, page 550 of the Thermodynamics book (the short version); Table 7.2 Appendix B, page 1010 of the Physical Chemistry book (the full text).

8.

For the equilibrium N2O4 (g) 2 NO2 (g)

a) b) For the advancement of the reaction towards equilibrium N2O4 (g) 2 NO2 (g)

So we know the reaction has to proceed in the reverse direction to establish equilibrium. Initial advancement () final 0.300 mol + mol 0.300 + mol 0.500 mol -2 0.500 - 2 mol

At equilibrium, total moles = 0.800 - The system must move towards reactants to reach equilibrium

Solving for using the quadratic equation, we obtain X(1) = 0.324 mol X(2) = 0.176 mol We can ignore X(1) since that would yield a negative number of moles of NO2 at equilibrium. Hence, at equilibrium

9. a)

For the equilibrium N2O4 (g) 2 NO2 (g)

b) Note The heat capacity change for the reaction is obtained from the back of the text. rCpo = 2 Cpo(NO2(g)) - Cpo (N2O4(g)) = 2 x 37.20 J/K mol 77.28 J/K mol = -2.88 J/K mol

Using the heat capacity change for the reaction gives

Separating variables and integrating both sides of the equation gives

For T = 500 K

Note not a huge difference between the both answers when we neglect the heat capacity change and its influence on the reaction enthalpy. 10. H2 (g) + I2 (g) 2 HI (g)

So we know the reaction has to proceed in the forward direction to establish equilibrium. Data Table H2 (g) I2 (g) HI (g) Initial 0.300 mol 0.400 mol 0.200 mol advancement () -eq mol -eq mol +2eq mol Equilibrium (0.300 - eq) mol (0.500 - 2eq) mol (0.200 + 2eq) mol At equilibrium, total moles = 0.900 mol The system must move towards products to reach equilibrium

Solving for eq using the quadratic equation, we obtain eq (1) = 0.293 mol eq (2) = 0.411 mol We can ignore eq (2) since that would yield a negative number of moles of H2 and I2 at equilibrium. Hence, at equilibrium