This document discusses thermodynamics concepts including entropy, free energy, and equilibrium. It provides examples of using thermodynamic data like equilibrium constants measured at different temperatures, standard enthalpy and entropy values, and vapor pressure to calculate standard thermodynamic quantities for chemical reactions. It also shows how the temperature dependence of equilibrium constants can be used to determine whether reactions are exothermic or endothermic.
This document discusses thermodynamics concepts including entropy, free energy, and equilibrium. It provides examples of using thermodynamic data like equilibrium constants measured at different temperatures, standard enthalpy and entropy values, and vapor pressure to calculate standard thermodynamic quantities for chemical reactions. It also shows how the temperature dependence of equilibrium constants can be used to determine whether reactions are exothermic or endothermic.
This document discusses thermodynamics concepts including entropy, free energy, and equilibrium. It provides examples of using thermodynamic data like equilibrium constants measured at different temperatures, standard enthalpy and entropy values, and vapor pressure to calculate standard thermodynamic quantities for chemical reactions. It also shows how the temperature dependence of equilibrium constants can be used to determine whether reactions are exothermic or endothermic.
This document discusses thermodynamics concepts including entropy, free energy, and equilibrium. It provides examples of using thermodynamic data like equilibrium constants measured at different temperatures, standard enthalpy and entropy values, and vapor pressure to calculate standard thermodynamic quantities for chemical reactions. It also shows how the temperature dependence of equilibrium constants can be used to determine whether reactions are exothermic or endothermic.
Tutorial 3 - Thermodynamics (Entropy, Free Energy and Equilibrium)
1. The equilibrium constant Kb for dissociation of aqueous ammonia is 1.710 × 10-5 at 20°C and 1.892 × 10-5 at 50°C. What are the values of ΔH° and ΔS° for the reaction?
NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq)
2. Consider the Haber synthesis of gaseous NH3 (ΔH°f = -46.1 kJ/mol; ΔG°f = -16.5 kJ/mol):
N2 (g) + 3 H2 (g) 2 NH3 (g)
(a) Use only these data to calculate ΔH° and ΔS° for the reaction at 25°C. (b) Account for the sign of ΔS°. (c) Is the reaction spontaneous under standard-state conditions at 25°C? Explain. (d) What are the equilibrium constants Kp and Kc for the reaction at 350 K? Assume that ΔH° and ΔS° are independent of temperature.
3. The temperature dependence of the equilibrium constant is given by the equation
° ° −∆ 1 ∆ ln = +
where ΔH° and ΔS° are assumed to be independent of temperature.
(a) Derive this equation from equations in the notes. (b) Explain how this equation can be used to determine experimental values of ΔH° and ΔS° from values of K at several different temperatures. (c) Use this equation to predict the sign of ΔH° for a reaction whose equilibrium constant increases with increasing temperature. Is the reaction endothermic or exothermic? Is your prediction in accord with Le Chatelier’s principle?
4. The normal boiling point of bromine is 58.8°C, and the standard entropies of the liquid and vapor are S°[Br2(l)] = 152.2 J/(K•mol); S°[Br2(g)] = 245.4 J/(K•mol). At what temperature does bromine have a vapor pressure of 227 mm Hg?
5. The molar solubility of lead iodide is 1.45 × 10-3 M at 20°C and 6.85 × 10-3 M at 80°C. What are the values of ΔH° and ΔS° for dissolution of PbI2?
PbI2 (s) Pb2+ (aq) + 2 I- (aq)
Assume that ΔH° and ΔS° are independent of temperature.
6. Use the data in Appendix B to calculate the equilibrium constant K for the following reaction at 80°C:
2 Br- (aq) + Cl2 (g) Br2 (l) + 2 Cl- (aq)
Assume that ΔH° and ΔS° are independent of temperature.
7. Use the data from Appendix B to determine the normal boiling point of carbon disulfide (CS2).
8. A humidity sensor consists of a cardboard square that is colored blue in dry weather and red in humid weather. The color change is due to the reaction:
CoCl2 + 6 H2O (g) ⇌ [Co(H2O)6]Cl2 (s)
For this reaction at 25°C, ΔH° = -325 kJ/mol and ΔS° = -899 J/(K•mol). Assuming that ΔH° and ΔS° are independent of temperature, what is the vapor pressure of water (in mm Hg) at equilibrium for the above reaction at 35°C on a hot summer day?
9. The following reaction, sometimes used in the lab to generate small quantities of oxygen gas, has ΔG° = -224.4 kJ/mol at 25°C:
2 KClO3 (s) 2 KCl (s) + 3 O2 (g)
Use the following additional data at 25°C to calculate the standard molar entropy S° of O2 at 25°C: ΔH°f(KClO3) = -397.7 kJ/mol, ΔH°f(KCl) = -436.5 kJ/mol, S°(KClO3) = 143.1 J/(K•mol), S°(KCl) = 82.6 J/(K•mol).
