Use the observations about each chemical reaction in the table below to decide the sign (positive or negative) of the reaction enthalpy AH and reaction entropy AS. Note: if you have not been given enough information to decide a sign, select the "unknown" option. reaction observations cd (pick one) positive negative ΔΗ is ✓ unknown A This reaction is spontaneous only below 23. °C. AS is unknown ΔΗ is B This reaction is endothermic and proceeds slower at temperatures below 133. °C. positive AS is negative C This reaction is spontaneous except below 95. °C but proceeds at a faster rate above ΔΗ is negative 155. °C. AS is positive ☑

The reaction shown below is involved in the refining of iron. (The table that follows provides all of the thermodynamic data you should need for this problem.) 2Fe2O3(s)+3C(s,graphite)4Fe(s)+3CO2(g) (a) Find H for the reaction. (b) S for the reaction above is 557.98 J/K. Find S° for Fe2O3(s). (c) Calculate G for the reaction at the standard temperature of 298 K. (There are two ways that you could do this.) (d) At what temperatures would this reaction be spontaneous? Compound Hf (kJ mol-1) S° (kJ mol-1) Gf (J mol-1 K-1) Fe2O3(s) -824.2 ? -742.2 C(s, graphite) 0 5.740 0 Fe(s) 0 27.3 0 CO2(g) -393.5 213.6 -394.4.83

Define the following: a. spontaneous process b. entropy c. positional probability d. system e. surroundings f. universe

Methane can be produced from CO and H2.The process might be done in two steps, as shown below, with each step carried out in a separate reaction vessel within the production plant. Reaction 1 CO(g)+2H2(g)CH3OH(l) S = -532 J/K Reaction 2 CH3OH(l)CH4(g)+12O2(g) S= +162 J/K NOTE: You should be able to work this problem without using any additional tabulated data. (a) Calculate H for reaction 1. (b) Calculate Gf for CO(g). (c) Calculate S° for O2(g). (d) At what temperatures is reaction 1 spontaneous? (e) Suggest a reason why these two steps would need to be carried out separately. Substance Hf (kJ mol-1) Gf (kJ mol-1) S (J mol-1 K-1) CO(s) -110.5 197.674 CH3OH( l ) -238.7 -166.4 126.8 CH4(g) -74.8 186.2

10.51 The combustion of acetylene was used in welder's torches for many years because it produces a very hot flame: C2H2(g)+52O2(g)2CO2(g)+H2O(g) H= -1255.5 kJ (a) Use data in Appendix E to calculate S for this reaction, (b) Calculate G and show that the reaction is spontaneous at 25°C. (c) Ls there any temperature range in which this reaction is not spontaneous? (d) Do you think you could use Equation 10.4 to calculate such a temperature range reliably? Explain your answer.

For the reaction C2H2(g)+4F2(g)2CF4(g)+H2(g) S is equal to 358 J/K. Use this value and data from Appendix 4 to calculate the value of S for CF4(g).

On the basis of your experience, predict which of the following reactions are spontaneous. (a) CO2(s)CO2(g) at 25°C (b) NaCl(s)NaCl(l) at 25°C (c) 2NaCl(s)2Na(s)+Cl2(g) (d) CO2(g)C(s)+O2(g)

Nickel metal reacts with carbon monoxide to form tetra-carbonyl nickel, Ni(CO)4: Ni(s)+4CO(g)Ni(CO)4(g) This reaction is exploited in the Mond process in order to separate pure nickel from other metals. The reaction above separates nickel from impurities by dissolving it into the gas phase. Conditions are then changed so that the reaction runs in the opposite direction to recover the purified metal. (a) Predict the sign of S for the reaction as written above. (b) Use tabulated thermodynamic data to calculate H, S , and G for the reaction. (c) Find the range of temperatures at which this reaction is spontaneous in the forward direction.

Determine whether each of the following statements is true or false. (a) An exothermic reaction is spontaneous. (b) When G° is positive, the reaction cannot occur under any conditions. (c) S° is positive for a reaction in which there is an increase in the number of moles. d) If H° and S° are both negative, G° will be negative.

Limestone is predominantly CaCO3, which can undergo the reaction CaCO3(s)CaO(s)+CO2(g). We know from experience that this reaction is not spontaneous, yet S for the reaction is positive. How can the second law of thermodynamics explain that this reaction is not spontaneous?