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For the gaseous equilibrium represented below, it is observed that greater amounts of PCl3 and Cl2 are produced

as the temperature is increased. PCl5(g) <===> PCl3(g) + Cl2(g) a) What is the sign of DS for the reaction? Explain. b) What change, if any, will occur in DG for the reaction as the temperature is increased. Explain your reasoning in terms of thermodynamic principles. c) If He gas is added to the original reaction mixture at constant volume and temperature, what will happen to the partial pressure of Cl2? Explain. d) If the volume of the original reaction is decreased at constant temperature to half the original volume, what will happen to the number of moles of Cl2 in the reaction vessel? Explain. ----------------------------------------(a) DS is positive (or "+", or ">0") 1 point Moles products > moles reactants 1 point Note; all species are gaseous, so (g) need not be indicated. To earn credit, number of particles (moles) must be discussed. No explanation point earned for just nothing that disorder increases, or that PCl5 is decomposing or dissociating. (b) DG will decrease (or become more negative, or become smaller). 1 point DG = DH - TDS and since DS is positive, TDS is positive ( > 0). Thus increasing T will result in a larger term being subtracted from DH, or, DG = -RT ln K and K is going up in value since T is increasing.) Note: full credit earned for part (b) if: DS < 0 in part (a) which leads to DG is increasing because TDS is added to DH, or, DS = 0 in part (a) which leads to no change in DG (c) no change (one point) PHe is not part of the a) reaction (He is not involved) or, b) law of mass action or, c) reaction quotient or, d) equilibrium constant expression; one point hence altering PHe has no effect on the position at equilibrium (d) moles of Cl2 will decrease (one point) The decrease in volume leads to an increase in pressure (concentration), therefore the reaction shifts to the left because:

(one point for any of the following) Q > Ksp (Q > Kc, or, the rate of the reverse reaction increase more than the rate of the forward reaction, or, the reaction shifts toward the lesser moles of gas. Note: "LeChatelier's principle" alone is not sufficient to earn the explanation point. If response suggests that the number of moles of Cl2 is halved because the system is "cut" in half, only one point is earned.

2 H2S(g) + SO2(g) <===> 3 S(s) + 2 H2O(g) At 298 K, the standard enthalpy change, DH, for the reaction represented above is -145 kilojoules. (a) Predict the sign of the standard entropy change, DS, for the reaction. Explain the basis for your prediction. (b) At 298 K, the forward reaction (i.e., toward the right) is spontaneous. What change, if any, would occur in the value of DG for this reaction as the temperature is increased? Explain your reasoning using thermodynamic principles. (c) What change, if any, would occur in the value of the equilibrium constant, Keq, for the situation described in (b)? Explain your reasoning. (d) The absolute temperature at which the forward reaction becomes nonspontaneous can be predicted. Write the equation that is used to make the prediction. Why does this equation predict only an approximate value for the temperature? --------------------------------------Note: for parts (a), (b), and (c), just writing an equation is not sufficient for the 'explanation" point. To earn credit, the student must connect the equation to the issue to be explained. a) two points Statement that [delta]S is negative 3 moles of gas ---> 2 moles of gas plus solid (3 moles ---> 2 moles earns no points), OR 2 gases ---> one gas + solid OR use of [delta]G = [delta]H - T[delta]S with [delta]G = 0

b) two points [delta]G is less negative, goes to 0, goes positive, gets larger Explanation using [delta]G = [delta]H - T[delta]S

c) two points Keq decreases (exponent goes more negative) as T increases

OR Keq goes from > 1, to 1, to < 1, as T increases Correct explanation using the equation [delta]G = - RT ln K (or ln(k1 / k2) = ([delta]H / R) (1/T2 - 1/T1) OR higher T favors the reverse reaction (Le Chtelier) because the forward reaction is exothermic. Note: if answer for (a) is that [delta]S is positive, then statement that Keq will decrease or increase depending on the relative magnitudes of T and [delta]G change earns two points.

d) two points Since [delta]G = 0 at this point, the equation is T= [delta]H / [delta]S ([delta]G = [delta]H - T [delta]SS is NOT sufficient without [delta]G = 0.) Prediction is not exact since [delta]H and/or [delta]S vary with T.

2 C4H10(g) + 13 O2(g) ------> 8 CO2(g) + 10 H2O(l) The reaction represented above is spontaneous at 25 C. Assume that all reactants and products are in their standard states. (a) Predict the sign of DS for the reaction and justify your prediction. (b) What is the sign of DG for the reaction? How would the sign and magnitude of DG be affected by an increase in temperature to 50 C? Explain your answer. (c) What must be the sign of DH for the reaction at 25C? How does the total bond energy of the reactants compare to that of the products? (d) When the reactants are placed together in a container, no change is observed even though the reaction is known to be spontaneous. Explain this observation. ---------------------------average = 4.5 a) one point [delta]S < 0 The number of moles of gaseous products is less than the number of moles of gaseous reactant OR a liquid is formed from gaseous reactants.

b) one point [delta]G < 0 [delta]G becomes less negative as the temperature is increased since [delta]S < 0 and [delta]G = [delta]H T[delta]S. The term - T[delta]S adds a positive number to [delta]H.

c) one point [delta]H < 0 The bond energy of the reactants is less than the bond energy of the products.

d) one point The reaction has a high activation energy OR is kinetically slow, OR a specific neuton of the needs for a catalyst or spark.

Cl2(g) + 3 F2(g) ---> 2 ClF3(g) ClF3 can be prepared by the reaction represented by the equation above. For ClF3 the standard enthalpy of formation, DHf, is - 163.2 kilojoules/mole and the standard free energy of formation, DGf, is - 123.0 kilojoules/mole. (a) Calculate the value of the equilibrium constant for the reaction at 298 K. (b) Calculate the standard entropy change, DS, for the reaction at 298 K. (c) If ClF3 were produced as a liquid rather than as a gas, how would the sign and magnitude of DS for the reaction be affected? Explain. (d) at 298 K the absolute entropies of Cl2(g) and ClF3(g) are 222.96 joules per mole-Kelvin and 281.50 joules per mole-Kelvin, respectively. (i) Account for the larger entropy of ClF3(g) relative to that of Cl2(g). (ii) Calculate the value of the absolute entropy of F2(g) at 298 K. -----------------------------average = 3.5 (Only 30 scores of nine; kids did not see stoichiometry in (b), had problems on which gas constant to use, and a hard time in (c) in relating a more negative value.) a) two points [delta]G = - RT ln K; rearranging gives ln K = [delta]G - RT ln K = - 123,000 J ((8.31 J/mol K) (298 K)) = 49.7 K = 3.72 x 1021

b) two points [delta]G = [delta]H - T[delta]S - 246,000 J = - 326,400 J - (298) (x) x = - 270 J / K

c) two points [delta]S is a larger negative number ClF3 (liquid) is more ordered (less disordered) than ClF3 (gas) This was my answer before I saw the standard given above: A liquid is more ordered than a gas. There would be a greater entropy change in gas + gas ---> liquid than in gas + gas ---> gas. Therefore, sign is the same, but absolute magnitude is greater.

d) three points i) ClF3 is a more complex molecule (i.e. more atoms) with more vibrational and rotational degrees of freedom than Cl2 ii) Cl2 + 3 F2 ---> 2 ClF3; use Hess's Law [sigma]Srxn = [sigma]S products - [sigma]S reactants - 270 = [2 (281.50)] - [222.96 + 3x] x = 203 J mol1 K1

BCl3(g) + NH3(g) <---> Cl3BNH3(s) The reaction represented above is a reversible reaction. (a) Predict the sign of the entropy change, DS, as the reaction proceeds to the right. Explain your prediction. (b) If the reaction spontaneously proceeds to the right, predict the sign of the enthalpy change, DH. Explain your prediction. (c) The direction in which the reaction spontaneously proceeds changes as the temperature is increased above a specific temperature. Explain. (d) What is the value of the equilibrium constant at the temperature referred to in (c); that is, the specific temperature at which the direction of the spontaneous reaction changes? Explain. --------------------------------------a) two points DS will be negative. The system becomes more ordered as two gases form a solid.

b) two points DH must be negative. For the reaction to be spontaneous, DG must be negative, so DH must be more negative than -TDS is positive.

c) two points As T increases, -TDS increases. Since DS is negative, the positive -TDS term will eventually exceed DH (which is negative), making DG positive. (In the absence of this, DG = DH - TDS and general discussion of the effect of T and DS gets 1 point.)

d) two points The equilibrium constant is 1. The system is at equilibrium at this temperature with an equal tendancy to go in either direction. OR DG = 0 at equilibrium so K = 1 in DG = -RT ln K (In the absence of these, DG = -RT ln K gets 1 point).

The above concludes the AP scoring standards published in 1991. The following is simply alternate ways of answering which the AP readers may or may not have given full credit to. a) The amount of entropy goes down, DS is negative. b) DG = DH - TDS. If DS is negative, then DH must also be negative to get a negative DG. c) Let us say DG is positive when DH is positive and DS is positive. As T goes up - TDS becomes more negative until it makes DG (which equals DH - TDS) become negative. d) At the temperature when the direction changes, the rate forward = the rate reverse. Since K = kf / kr, this equals 1.