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CHAPTER 7 THERMODYNAMICS: THE SECOND AND THIRD LAWS

7.1

(a) rate of entropy generation =

∆Ssurr q = − rev time time ⋅ T rate of heat generation =− T −1 −(100. J ⋅ s ) = = 0.341 J ⋅ K −1 ⋅ s −1 293 K

(b) ∆Sday = (0.341 J ⋅ K −1 ⋅ s −1 ) (60 sec ⋅ min −1 ) (60 min ⋅ hr −1 ) (24 hr ⋅ day −1 )
= 29.5 kJ ⋅ K −1 ⋅ day −1
−∆H , if T is larger, ∆S is smaller. T

(c) Less, because in the equation ∆S =

7.3

(a) ∆S = (b) ∆S =

qrev 65 J = = 0.22 J ⋅ K −1 T 298 K
65 J = 0.17 J ⋅ K −1 373 K

(c) The entropy change is smaller at higher temperatures, because the matter is already more chaotic. The same amount of heat has a greater effect on entropy changes when transferred at lower temperatures.
dq . At constant pressure, we can T

7.5

(a) The relationship to use is dS = substitute
dq = n C P dT : dS = n C p dT T

SM-172

Upon integration, this gives ∆S = n Cp ln

T2 . The answer is calculated by T1

simply plugging in the known quantities. Remember that for an ideal monatomic gas
CP =
5 2

R: 431.0 K = 6.80 J ⋅ K −1 310.8 K

−1 −1 ∆S = (1.00 mol) ( 5 2 × 8.314 J ⋅ K ⋅ mol ) ln

(b) A similar analysis using CV gives ∆S = n CV ln monatomic ideal gas is 3 2 R:
−1 ∆S = (1.00 mol) ( 3 ⋅ mol−1 ) ln 2 × 8.314 J ⋅ K

T2 , where CV for a T1

431.0 K = 4.08 J ⋅ K −1 310.8 K

7.7

Because the process is isothermal and reversible, the relationship dS = can be used. Because the process is isothermal, ∆U = 0 and hence
q = − w, where w = − PdV . Making this substitution, we obtain

dq T

P dV nRT nR dV = dV = T TV V V ∴ ∆S = nR ln 2 V1 dS = Substituting the known quantities, we obtain
∆S = (5.25 mol) (8.314 J ⋅ K −1 ⋅ mol−1 ) ln = 14.8 J ⋅ K −1

34.058 L 24.252 L

7.9

The change in entropy for each block (block 1 and block 2) are:

∆S1 =

q1 q and ∆S2 = 2 energy is transferred, then the change in entropy T1 T2 q1 q + 2 T1 T2

for the system is:

∆S sys = ∆S1 + ∆S2 =

SM-173

11 (a) ∆S ° = 50.5 kJ ⋅ mol−1 −1 q ∆H 46.00 mol × ( − 6. are for 298 K.or TB = ∆H vap ∆S vap .If 1 J of energy is transferred from block 2 to block 1 q1 = +1 J.9 K. The data in the Appendix. For ethanal(l) ⎯⎯ → ethanal(g).30) kJ ⋅ mol−1 = 26.01 kJ ⋅ mol−1 ) = = = −22.0 J ⋅ K −1 T T 273.2 K 7. using the enthalpy and entropy differences between the gas and liquid forms at 298 K. ∆S sys must be positive and.1 J ⋅ K −1 ⋅ mol−1 TB = 26. calculation of ∆H °vap or ∆S °vap . SM-174 . q2 = −1 J. give a good approximation of these quantities but the values are not exact. Thus. but the boiling point of ethanal is not 298 K.19 kJ ⋅ mol−1 − ( −192. however. K 90.13 (a) The boiling point of a liquid may be obtained from the relationship ∆S vap = ∆H vap TB .07 g ⋅ mol (b) ∆S = = = = +134 J ⋅ K −1 T T 351. and ∆S sys = 1 1 − T1 T2 For the transfer of heat from block 2 to block 1 to be spontaneous. This relationship should be rigorously true if we have the actual enthalpy and entropy of vaporization. therefore.8°C or 293. (c) These numbers are in very good agreement.0 g × 43. T2 would have to be greater than T1 .5 K 7.11×103 J ⋅ mol−1 = 290. q ∆H ° 1.2 J ⋅ K −1 ⋅ mol−1 = 90.1 J ⋅ K −1 ⋅ mol−1 (b) The boiling point of ethanal is 20. (d) Differences arise partly because the enthalpy and entropy of vaporization are slightly different from the values calculated at 298 K. the data in the appendix give ∆H vap ≅ −166.3 J ⋅ K −1 ⋅ mol−1 − 160.11 kJ ⋅ mol−1 ∆S vap ≅ 250.

which is in reasonably close agreement. such disorder is not possible. Because all the groups attached to boron are identical. Using this information and the relationship TB = ∆H °vap ∆S ° vap 21.51 × 103 J ⋅ mol−1 = = 253 K. 85 J ⋅ K −1 ⋅ mol−1 (b) The experimental boiling point of dimethyl ether is 248 K.17 (a) The value can be estimated from ∆H °vap = T ∆S °vap ∆H °vap = (353 K) (85 J ⋅ mol−1 ⋅ K −1 ) = +30. kJ ⋅ mol−1 (b) ∆S °surr = − ∆H °system ∆Ssurr T ⎛ ⎞ ⎛ 30 kJ ⋅ mol−1 ⎞ 10 g −1 = −⎜ ⎟ = −11 J ⋅ K −1 ⎟ ⎜ ⎝ 78. 7.11 g ⋅ mol ⎠ ⎝ 353 K ⎠ 7. 7.21 There are six orientations of an SO 2 F2 molecule as shown below: O S F F S O F O O O F F S O O F O S F F F O S F O F S O F O SM-175 .7. given the nature of the approximation.15 (a) Trouton’s rule indicates that the entropy of vaporization for a number of organic liquids is approximately 85 J ⋅ K −1 ⋅ mol −1 . COF2 and BF3 are both trigonal planar molecules. but it would be possible for the molecule to be disordered with the fluorine and oxygen atoms occupying the same locations.19 COF2 .

the carbon is more rigidly held in place and will have less entropy.00 atm. because it has greater complexity.02 × 10 = (1.0 mol of Ar(g) at 2. (b) When we consider the two structures.The Boltzmann expression for one mole of SO 2 F2 molecules having six possible orientations is S = k ln66. bromine is a liquid and iodine is a solid. Because water is a molecular substance held together in the solid phase by weak hydrogen bonds. because it will occupy a larger volume than 1. it is clear that pentene will have more flexibility in its framework than cyclopentane. because Br is more massive and contains more elementary particles than F in HF. If the two substances had the same state (i.00 atm. because the compounds are in different states. C(s) < H 2 O(s) < H 2 O(l) < H 2 O(g) 7. However. (d) 1. being a molecule rather than a single atom.23 (a) HBr. which we will take to be the standard state from graphite. and in C(s). 7. The main question concerns where to place C(s) in this order. (c) I 2 (l) because molecules in liquids are more randomly oriented than molecules in solids.38 × 10 −23 J ⋅ K −1 )ln66.e. and that will essentially become a question of whether C(s) should have more or less entropy than H 2 O(s) .9 J ⋅ K −1 23 23 7. (b) NH3 .02 × 10 S = 14. both were gases or both liquids) we would expect iodine to have the higher entropy due to its larger mass and consequently larger number of fundamental particles.27 (a) In the standard state.0 mol Ar(g) at 1.. we would expect the liquid to have a higher entropy than the solid. because we would automatically expect C(s) to have less entropy than any liquid. which will be SM-176 .25 It is easy to order H 2 O in its various phases because entropy will increase when going from a solid to a liquid to a gas.

68 J ⋅ K −1 ⋅ mol−1 + 1 ⋅ mol−1 )] 2 (205. (c) Ethene (or ethylene) is a gas and polyethylene is a solid.5. Also. Therefore. (b) CO(g) + 1 → CO 2 (g) 2 O 2 (g) ⎯⎯ ∆S °r = 213.74 J ⋅ K −1 ⋅ mol−1 −1 −1 − [197.91 J ⋅ K −1 ⋅ mol−1 − [130.29 (a) Entropy should decrease because the number of moles of gas is less on the product side of the reaction. (b) Entropy should increase because the dissolution of the solid copper phosphate will increase the randomness of the copper and phosphate ions. for the same mass. and that the entropy change for the reaction in which a compound is formed from the elements is also not 0. whereas polyethylene will be made up of fewer but larger molecules.31 ∆SA > ∆SC > ∆SB.33 (a) H 2 (g) + 1 → H 2 O(l) 2 O 2 (g) ⎯⎯ ∆S °f = ∑ S °products − ∑ S °reactants −1 = 69. The change in entropy in container C is greater than that of container B because of the disorder due to the vibrational motion of the molecules in container C.14 J ⋅ K = −163.14 J ⋅ K ⋅ mol )] = − 86. 7. 7. 7. so we automatically expect ethene to have a higher entropy. The change in entropy for container A is greater than that for container B or C due to the greater number of particles. a sample of ethene will be composed of many small molecules. we predict pentene to have a higher entropy.comparatively rigid. Note that the absolute entropies of the elements are not 0. (c) Entropy should decrease as the total number of moles decreases.50 J ⋅ K −1 ⋅ mol−1 SM-177 .67 J ⋅ K −1 ⋅ mol−1 + 1 2 (205.34 J ⋅ K −1 ⋅ mol−1 The entropy change is negative because the number of moles of gas has decreased by 1.

1 J ⋅ K −1 ⋅ mol−1 )] = − 36.m = a + bT + c T 2 then dS = ∆S = ∫ T2 T1 a + bT + c T 2 dT T T2 T1 T2 ⎛ a c ⎞ c = ∫ ⎜ +b + 3 ⎟dT = a ln(T ) + bT − 2 T1 2T T ⎠ ⎝T ⎛T = a ln ⎜ 2 ⎝ T1 ⎞ 1 ⎞ c⎛ 1 ⎟ + b(T2 − T1 ) − ⎜ 2 − 2 ⎟ 2 ⎝ T2 T1 ⎠ ⎠ ∆S for heating graphite from 200 K to 500 K is ⎛ 500 K ⎞ -2 -1 = (16. 7. (c) CaCO3 (s) ⎯⎯ → CaO(s) + CO 2 (g) ∆S °r = 39. but the four moles of solid products are more ordered than the four moles of solid reactants.0 J ⋅ K −1 ⋅ mol−1 ) + 82.9 J ⋅ K −1 ⋅ mol−1 ] = + 160.m dqrev Cp.54 × 105 J ⋅ K ⋅ mol-1 ) ⎛ 1 1 − ⎜ 2 2 ⎟ 2 (200 K) ⎠ ⎝ (500 K) -1 -1 = 7.00477 J ⋅ K ⋅ mol ) ⎝ 200 K ⎠ × (500 K − 200 K) ⎞ (−8. = T1 T T T if Cp.The entropy change is negative because the number of moles of gas has decreased by 0.86 J ⋅ K -1 ⋅ mol-1 ) ln ⎜ ⎟ + ( 0.8 J ⋅ K −1 ⋅ mol−1 It is not immediately obvious. → 3 KClO4 (s) + KCl(s) (d) 4 KClO 3 (s) ⎯⎯ ∆S °r = 3(151. therefore. ∆S = ∫ dT .35 T2 C p.m ⋅ dT and.59 J ⋅ K −1 ⋅ mol−1 − [4(143.6 J ⋅ K −1 ⋅ mol−1 The entropy change is positive because the number of moles of gas has increased by 1.91 J ⋅ K ⋅ mol − If we assume a constant heat capacity at the mean temperature of 350 K: SM-178 .5.75 J ⋅ K −1 ⋅ mol−1 + 213.74 J ⋅ K −1 ⋅ mol−1 − [+92.

m ln ⎜ 2 ⎟ = ( 33. 7.22 J ⋅ K ⋅ mol ⎝ 348 K ⎠ ⎠ Step 2. Carrying out the phase change at this temperature.3 J ⋅ K ⋅ mol ) ln ⎜ ⎟ = 5. Step 3.m ln ⎜ 2 ⎝ T1 ⎞ ⎛ 373 K ⎞ -1 -1 -1 -1 ⎟ = ( 75.86 J ⋅ K -1 ⋅ mol-1 ) + ( 0.33 J ⋅ K ⋅ mol ⎝ 373 K ⎠ ⎝ T1 ⎠ Therefore.9 J ⋅ K -1 ⋅ mol-1 7.37 The entropy of vaporization of water at 75o may be carried out through a series of three reversible steps. The sum of the ∆S’s for these three steps will be equivalent to vaporizing water at 75o in one irreversible step. Namely.6 J ⋅ K -1 ⋅ mol-1 ) ln ⎜ ⎟ = 10. the entropy of vaporization of H2O at 100oC is given to be 109. heating the reactants to 100oC: ⎛T ∆S1 = C p.C p. the amount of energy which flows from one to the other must first be calculated: SM-179 .6 J ⋅ K ⋅ mol T1 ⎝ 200 K ⎠ Not integrating the heat capacity leads to roughly a 34% error in ∆S.6 J ⋅ K -1 ⋅ mol-1 ) ln ⎜ ⎟ = −2.39 To calculate the change in entropy for the hot and cold water.0 J ⋅ K -1 ⋅ mol-1 .6 J ⋅ K ⋅ mol and ∆S = C p.m ln T2 ⎛ 500 K ⎞ -1 -1 = (11. the molar enthalpy of vaporization of H2O at 75o C is: ∆S v.54 × 105 J ⋅ K ⋅ mol-1 ⎞ −⎜ ⎟ (500 K) 2 ⎝ ⎠ -1 -1 = 11. cooling the products to 75oC: ⎛T ⎞ ⎛ 348 K ⎞ -1 -1 ∆S3 = C p.m = (16. reversibly heating the reactants to 100oC. Step 1.00477 J ⋅ K -2 ⋅ mol-1 ) ( 350 K ) ⎛ −8.m = ∆S1 + ∆S 2 + ∆S3 = 111. and finally cooling the products back to 75oC.

00 mol × 8.1 J ⋅ K -1 Therefore.78 mol + 3.m ln ⎜ 2 ⎝ T1 = +11.3 J ⋅ K ⋅ mol ) ln ⎜ ⎟ ⎝ 293 K ⎠ ⎠ ⎞ ⎛ 310. -1 18.m ln ⎜ 2 ⎝ T1 = −11. and the total ∆S for the entire system: ⎛T ∆Sc = nc ⋅ C p.015 g ⋅ mol 18. and Ti .1 K ⎞ -1 -1 ⎟ = (2. Solving for T f we find: Tf = (n c ⋅ Ti .h ) nc + nh The moles of hot and cold water are: 50 g 65 g nc = = 2.2 × 103 J ⋅ mol−1 = −73 J ⋅ K −1 111.41 (a) The change in entropy will be given by ∆Ssurr = −∆H system T ∆H system T = = −1.1 K With Tf.7 K ∆Ssystem = SM-180 .78 mol and nh = = 3.9 J ⋅ K -1 ⎛T ∆S h = nh ⋅ C p.c .m (H 2 O) ⋅ (T f − Ti .78 mol) ( 75. and nh are the moles of cold and hot water. respectively.h ) where nc . Dividing both sides by C p. ∆S tot is: ∆S tot = ∆Sc + ∆S h = +0.3 J ⋅ K ⋅ mol ) ln ⎜ ⎟ ⎝ 323 K ⎠ ⎠ 7.q (H 2 O)cold = −q (H 2 O) hot = nc ⋅ C p. therefore: Tf = ( 2.m (H 2 O) ⋅ (T f − Ti . we can calculate ∆S for the hot and cold water. respectively.15 K) 2.c ) = nh ⋅ (T f − Ti .00 mol × 8.61 mol. h are the temperatures of the cold and hot water.7 K 1. and Ti .61 mol = 310.h ).78 mol ⋅ 293.m (H 2 O) we obtain: nc ⋅ (T f − Ti .c ) = nh ⋅ C p.61 mol ⋅ 323.c ) + (nh ⋅ Ti .015 g ⋅ mol-1 and T f is.1 K ⎞ -1 -1 ⎟ = (3.61 mol) ( 75.2 × 103 J ⋅ mol−1 = + 73 J ⋅ K −1 111.15 K ) + (3.8 J ⋅ K -1 ⎞ ⎛ 310.

312 mol) (8.43 (a) The total entropy change is given by ∆S tot = ∆Ssurr + ∆S . which is obtained by use of the ideal gas law: (4. SM-181 . so ∆Ssurr = −∆S = −3.00 mol × 4.6) so w = 0.84 J ⋅ K −1 .7 K (c) ∆Ssurr = −∆H system T = + 29. No work is done in free expansion (see Section 6.00 mol × − 4. + 3. it is clear that if ∆H r is large compared to ∆Sr .7 K = −(1.60 × 103 J ⋅ mol−1 = = − 29. (b) For the irreversible process.84 J ⋅ K −1 .00 mol × − 4. ∆S for an isothermal.67 L) = n(0.95 atm) (1.314 J ⋅ K −1 ⋅ mol−1 ) ln = +3.0 J ⋅ K −1 158. The total change in entropy is therefore ∆S tot = +3. ∆S tot = 0. Because ∆U = 0. it follows that q = 0.0 J ⋅ K −1 158.0 J ⋅ K −1 ∆Ssystem = ∆H system T = 1.84 J ⋅ K −1 .7 K ∆H system 1. reversible process is calculated from ∆S = qrev − wrev V = = nR ln 2 . 7.60 × 103 J ⋅ mol−1 = + 29.60 × 103 J ⋅ mol−1 ) 158. 7.312 mol. then the reaction will generally be spontaneous.84 J ⋅ K −1 .(b) ∆Ssurr = ∆S system = −∆H system T T = −1. no heat is transferred into the surroundings.7 K 7.45 Exothermic reactions tend to be spontaneous because the result is an increase in the entropy of the surroundings. To do the calculation we need the value of T T V1 n. and their entropy is unchanged: ∆Ssurr = 0. Because the 1. Using the mathematical relationship ∆Gr = ∆H r − T ∆Sr .67 L process is reversible. n = 0. Therefore.0 J ⋅ K −1 158.60 × 103 J ⋅ mol−1 = − 29.00 mol × 4.33 L ∆S = (0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 ) (323 K). ∆S is the same.

87 J ⋅ K −1 ⋅ mol−1 ] = − 149.7 J ⋅ K −1 ⋅ mol−1 ∆G°r = − 1111.47 (a) ∆H °r = 3(−824.1kJ ⋅ mol−1 (c) ∆H °r = 9.09 kJ ⋅ mol−1 − [− 1219.4 kJ ⋅ mol −1 )] = −195.2 kJ ⋅ mol−1 or ∆G°r = ∆H °r − T ∆S °r = 11.83 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = − 4.14 J ⋅ K ⋅ mol )] = −133.40 J ⋅ K −1 ⋅ mol−1 ) − [2(146.8 kJ ⋅ mol−1 ∆Gr may also be calculated from ∆H °r and ∆S °r (the numbers calculated differ slightly from the two methods due to rounding differences): ∆G°r = ∆H °r − T ∆S °r = − 235.16 kJ ⋅ mol−1 − [2(33.17 J ⋅ K −1 ⋅ mol−1 ∆G°r = 3(−742.17 J ⋅ K −1 ⋅ mol−1 )/(100 J ⋅ kJ −1 ) = −196.06 J ⋅ K −1 ⋅ mol−1 )] = −175.4 J ⋅ K −1 ⋅ mol−1 ) −1 −1 +1 2 (205.18 kJ ⋅ mol−1 )] = −57.5 kJ ⋅ mol−1 ∆S °r = − 80.8 kJ ⋅ mol−1 − (298 K) (−133.83 J ⋅ K −1 ⋅ mol−1 ∆G°r = 97.1 kJ ⋅ mol−1 (b) ∆H °r = − 1208.89 kJ ⋅ mol−1 − [2(51.3 kJ ⋅ mol−1 ] = + 56.31 kJ ⋅ mol−1 )] = − 4.2 kJ ⋅ mol−1 − (298 K) ( −175.6 kJ ⋅ mol−1 ] = 11.7 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = 56.29 J ⋅ K −1 ⋅ mol−1 − [2(240.8 kJ ⋅ mol−1 ∆S °r = 3(87.2 kJ ⋅ mol−1 ) − [2(−1015.2 kJ ⋅ mol−1 ) − [2(−1118.7.80 kJ ⋅ mol−1 SM-182 .8 J ⋅ K −1 ⋅ mol−1 − [68.20 kJ ⋅ mol−1 ∆S °r = 304.15 kJ ⋅ mol−1 − [− 1167.4 kJ ⋅ mol−1 )] = − 235.5 kJ ⋅ mol−1 − (298 K) (−149.73 kJ ⋅ mol−1 or ∆G°r = ∆H °r − T ∆S °r = −57.

49 (a) 1 2 N 2 (g) + 3 2 H 2 (g) ⎯⎯ → NH 3 (g) ∆H °r = ∆H °f (NH 3 ) = − 46. (c) C(s). g) − [ S °m (H 2 . g) = − 241.82 kJ ⋅ mol−1 ∆S °r = S °m (H 2 O. g)] −1 −1 = 188.7.740 J ⋅ K −1 ⋅ mol−1 + 1 2 (205.36 J ⋅ K −1 ⋅ mol−1 ∆G°r = −110.58 kJ ⋅ mol−1 S °m (H 2 O.61 J ⋅ K ⋅ mol ) −1 −1 +3 2 (130.83 J ⋅ K −1 ⋅ mol−1 − [130.68 J ⋅ K ⋅ mol )] = −99.42 J ⋅ K −1 ⋅ mol−1 ∆G°r = − 241.49 kJ ⋅ mol−1 S °m (NH 3 ) = 192.36 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = −137. g) = 188. g) − [ S °m (C.2 kJ ⋅ mol−1 S °m (CO.45 J ⋅ K −1 ⋅ mol−1 ∆S °f (NH 3 ) is negative because several gas molecules combine to form 1 NH3 molecule.68 J ⋅ K −1 ⋅ mol−1 + 1 2 (205.42 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = − 228.11 kJ ⋅ mol−1 3 ∆S °r = S °m (NH 3 . g) = 197.11 kJ ⋅ mol−1 − (298 K) ( −99.67 J ⋅ K −1 ⋅ mol−1 − [5.67 J ⋅ K −1 ⋅ mol−1 SM-183 .83 J ⋅ K −1 ⋅ mol −1 ∆S °f (H 2 O. g) = −110.14 J ⋅ K ⋅ mol )] = +89.53 kJ ⋅ mol−1 − (298 K) (89. g)] −1 −1 = 197. g)] −1 −1 = 192.45 J ⋅ K −1 ⋅ mol−1 − [ 1 2 (191. g) + 1 2 S °m (O 2 .82 kJ ⋅ mol−1 − (298 K) ( − 44. graphite + 1 → CO(g) 2 O 2 (g) ⎯⎯ ∆H °r = ∆H °f (CO.14 J ⋅ K ⋅ mol )] = − 44.53 kJ ⋅ mol−1 ∆S °r = S °m (CO. g) + 2 S ° m (H 2 . (b) H 2 (g) + 1 → H 2 O(g) 2 O 2 (g) ⎯⎯ ∆H °r = ∆H °f (H 2 O. g) − [ 1 2 S °m (N 2 . s) + 1 2 S ° m (O 2 . g) is a negative number because there is a reduction in the number of gas molecules in the reaction when S °m is positive.38 J ⋅ K −1 ⋅ mol−1 ∆G°r = − 46.38 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = −16.

g) − [ 1 2 S ° m (N 2 . (b) ∆G°r = ∆G°f (CaO. (d) 1 2 N 2 (g) + O 2 (g) ⎯⎯ → NO 2 (g) ∆H °r = ∆H °f (NO 2 ) = +33.61 J ⋅ K ⋅ mol ) + 205. the important point to gain is that the S °m value of a compound is not the same as the ∆S °f for the formation of that compound.19 kJ ⋅ mol−1 )] = −141. g) − ∆G°f (CaCO3 . s) + ∆G°f (CO 2 .89 J ⋅ K −1 ⋅ mol−1 ∆G°r = 33.06 J ⋅ K −1 ⋅ mol−1 − [ 1 2 (191. For all of these.51 Use the relationship ∆G°r = ∑ ∆G°f (products) − ∑ ∆G°r (reactants) : (a) ∆G°r = 2∆G°f (SO3 .03 kJ ⋅ mol−1 ) + (− 394.18 kJ ⋅ mol−1 − (298 K) ( −60. g)] = 2(− 371. g) − [2∆G°f (SO 2 . g) is somewhat negative due to the reduction in the number of gas molecules during the reaction.89 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = +51.41 kJ ⋅ mol−1 The reaction is not spontaneous.14 J ⋅ K ⋅ mol ] = −60.The S °m (CO. SM-184 . g) is larger than ∆S °f (CO. g) because in the formation reaction the number of moles of gas is reduced. ∆S °f is often negative because one is bringing together a number of elements to form that compound. g)] −1 −1 −1 −1 = 240. g) + S ° m (O 2 . g) = 240.8 kJ ⋅ mol−1 ) = + 130. s) = (− 604.18 kJ ⋅ mol−1 ∆S °r = S °m (NO 2 . 7.74 kJ ⋅ mol−1 The reaction is spontaneous.36 kJ ⋅ mol−1 ) − (− 1128.06 kJ ⋅ mol−1 ) − [2(− 300.06 J ⋅ K −1 ⋅ mol −1 The ∆S °f (NO 2 .33 kJ ⋅ mol−1 S °m (NO 2 .

55 To understand what happens to ∆G°r as temperature is raised. s) + 1 2 S °m (N 2 .78 J ⋅ K −1 ⋅ mol−1 − [5. +124.19 kJ ⋅ mol−1 .07 J ⋅ K ⋅ mol )] = − 234.740 J ⋅ K −1 ⋅ mol−1 −1 −1 −1 −1 1 +1 2 (191. l)] = 16(−394.0 kJ ⋅ mol−1 . s) + 5 2 S °m (Cl2 . Those compounds with a positive free energy of formation are unstable with respect to the elements. (c) NO(g). +86.36 kJ ⋅ mol−1 ) + 18(− 237. g) + 18∆G°f (H 2 O.4 kJ ⋅ mol−1 )] = −10 590.2 J ⋅ K −1 ⋅ mol−1 The compound is less stable at higher temperatures. Therefore. −305. From this it is clear that the free energy of the reaction becomes less favorable (more positive) as temperature increases. 7. we need only to find out whether the standard entropy of formation of the compound is a negative number.61 J ⋅ K ⋅ mol ) + 2 (130. we use the relationship ∆G°r = ∆H °r − T ∆S °r . g) + 1 2 S °m (H 2 . 7. 1 (b) C(s). This is calculated for each compound as follows: (a) P(s) + 5 → PCl5 (g) 2 Cl 2 (g) ⎯⎯ ∆S °r = S °m (PCl5 . graphite + 1 → HCN(g) 2 N 2 (g) + 2 H 2 (g) ⎯⎯ ∆S °r = S °m (HCN. Thus (a) and (d) are thermodynamically stable.68 J ⋅ K ⋅ mol )] = +34.09 J ⋅ K −1 ⋅ mol−1 + 5 2 (223. (d) SO 2 (g). only if ∆S °r is a negative number. g)] −1 −1 = 364. (b) HCN(g).7 kJ ⋅ mol−1 .9 kJ ⋅ mol−1 The reaction is spontaneous.(c) ∆G°r = 16∆G°f (CO 2 . −300.55 kJ ⋅ mol−1 . l) − [2∆G°f (C8 H18 .6 J ⋅ K −1 ⋅ mol−1 − [41.53 The standard free energies of formation of the compounds are: (a) PCl5 (g).13 kJ ⋅ mol−1 ) − [2(6. SM-185 . g) − [ S °m (P. g) − [ S °m (C.90 J ⋅ K −1 ⋅ mol−1 HCN(g) is more stable at higher T. g)] = 201.

8 J ⋅ K −1 ⋅ mol −1 )/1000 J ⋅ kJ −1 ) = −233. l) = 2(69.8 J ⋅ K −1 ⋅ mol −1 7.56 kJ ⋅ mol−1 ∆G°r can also be calculated from ∆S °r and ∆H °r using the relationship: ∆G°r = ∆H °r − T ∆S °r = −196.22 J ⋅ K −1 ⋅ mol−1 − [31. g)] = 248.1 k J ⋅ mol−1 − (298 K) (+125. g) − 2 S °m (H 2 O 2 .6 J ⋅ K −1 ⋅ mol−1 ) = + 125.91 J ⋅ K −1 ⋅ mol−1 ) + 205. g) − [ S °(S.35 kJ ⋅ mol−1 ) = − 233.10 kJ ⋅ mol−1 ∆G °r = 2∆G °f (H 2 O. g)] −1 −1 = 210.76 J ⋅ K −1 ⋅ mol−1 − [ 1 2 (191. l) = 2( − 285.6 kJ ⋅ mol−1 (b) 2 F2 (g) + 2 H 2 O(l) ⎯⎯ → 4 HF (aq) + O 2 (g) SM-186 . (d) S(s) + O 2 (g) ⎯⎯ → SO 2 (g) ∆S °r = S °(SO 2 . l) = 2( − 237.28 J ⋅ K −1 ⋅ mol−1 SO 2 (g) is more stable as T increases. g) + 2 S ° m (O 2 .14 J ⋅ K −1 ⋅ mol−1 ] = +11.83 kJ ⋅ mol−1 ) − 2( − 187.13 kJ ⋅ mol−1 ) − 2( − 120. s) + S °(O 2 .61 J ⋅ K ⋅ mol ) −1 −1 +1 2 (205. g) − [ 1 2 S °m (N 2 .14 J ⋅ K −1 ⋅ mol−1 − 2(109.57 ∆H °r = 2∆H °f (H 2 O. l) + S °m (O 2 . l) − 2∆G °f (H 2 O 2 .78 kJ ⋅ mol−1 ) = − 196.38 J ⋅ K −1 ⋅ mol−1 NO(g) is more stable as T increases.(c) 1 2 N 2 (g) + 1 2 O 2 (g) ⎯⎯ → NO(g) 1 ∆S °r = S °m (NO.80 J ⋅ K −1 ⋅ mol−1 + 205.14 J ⋅ K ⋅ mol )] = +12. l) − 2∆H °f (H 2 O 2 . (a) 2 H 2 O 2 (l) ⎯⎯ → 2 H 2 O(l) + O 2 (g) ∆S °r = 2 S °m (H 2 O.

14 J ⋅ K −1 ⋅ mol−1 ) − [2(202. l)] = 4 ( − 88.6 J ⋅ K −1 ⋅ mol−1 ∆H °r = 4∆H °f (HF.68 J ⋅ K −1 ⋅ mol−1 )/1000 J ⋅ kJ −1 ) = −98. l) − [∆H °f (B2 O3 .12 J ⋅ K −1 ⋅ mol−1 ) + 3(69.66 kJ ⋅ mol−1 − (298 K) (14. aq) − [2∆H °f (H 2 O.78 J. aq) − [2 × ∆G °f (H 2 O.8 kJ ⋅ mol−1 ) + 6( − 271. ∆H °r = 2∆H °f (BF3 .1 kJ ⋅ mol−1 ∆S °r = 2S °m (BF3 .08 kJ ⋅ mol−1 ) − [2( − 285. l) − [ S °m (B2 O3 .91 J ⋅ K −1 ⋅ mol−1 )] = +14.83 kJ ⋅ mol−1 ) − [( −1272.g) + 2 S °m (H 2 O.42 kJ ⋅ mol−1 SM-187 . l)] = 4 ( − 296.68 J ⋅ K −1 ⋅ mol−1 ∆G°r = − 232.78 J ⋅ K −1 ⋅ mol−1 )] = −378.83 kJ ⋅ mol−1 )] = −748.1 kJ ⋅ mol−1 )] = − 232. g) + 3S °m (H 2 O. g) − [2 S °m (F2 .6 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = −753. aq) + S °m (O 2 .59 In order to find ∆G°r at a temperature other than 298 K. s) + 6∆H °f (HF.K −1 ⋅ mol−1 ) + 2(69.0 kJ ⋅ mol−1 ) + 3( − 285.91 J ⋅ K −1 ⋅ mol−1 ) − [53.7 J ⋅ K −1 ⋅ mol−1 ) + 205. we must first calculate ∆H °r and ∆S °r and then use the relationship ∆G°r = ∆H °r + T ∆S °r to calculate ∆G°r . g) + 3∆H °f (H 2 O.97 J ⋅ K −1 ⋅ mol−1 + 6(173.1 J ⋅ K −1 ⋅ mol−1 − (353 K) ( − 378.13 kJ ⋅ mol−1 )] = −713. g)] = 2( − 1137.01 kJ ⋅ mol−1 7. g)] = 2(254.02 kJ ⋅ mol−1 ∆G°r can also be calculated from ∆S °r and ∆H °r using the relationship: ∆G°r = ∆H °r − T ∆S °r = −748.66 kJ ⋅ mol−1 ∆G °r = 4 × ∆G°f (HF.∆S °r = 4 S °m (HF.82 kJ ⋅ mol−1 ) − [2( − 237. l)] = 4( −330. S) + 6 S °m (HF.

377 J ⋅ K −1 ⋅ mol −1 − 5. the reaction will be Because ∆H °r is negative and = − 283.8 J ⋅ K −1 ⋅ mol−1 ∆G°r = − 256. g) − [ S °m (CaC2 .96 J ⋅ K −1 ⋅ mol−1 + 2(56.(a) In order to determine the range over which the reaction will be spontaneous. aq) + ∆H ° (C H . aq)] = 59. we consider the relative signs of ∆H °r and ∆S °r and their effect on ∆G°r . where the term T ∆S °r will be less than ∆H °r .082 kJ ⋅ mol−1 SM-188 .9 K.740 J ⋅ K −1 ⋅ mol−1 = − 3. Because ∆H °r is negative and ∆S °r is also negative.363 J ⋅ K −1 ∆G°r = + 1.2 kJ ⋅ mol−1 − (353 K) ( + 77. s) + 2S °m (HCl. graphite) = + 2. To find the temperature of the cutoff.8 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) ∆S °r is positive.94 J ⋅ K −1 ⋅ mol−1 − [69.9 K The reaction should be spontaneous below 612. aq)] = (− 877. aq) + S °m (C 2 H 2 . diamond) = + 1.3 kJ ⋅ mol−1 ∆S °r = S °m (CaCl2 .8 kJ ⋅ mol−1 ) + 2( − 167. For this reaction.68 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) T = 612.5 J ⋅ K −1 ⋅ mol−1 )] = + 77. s) r f 2 f 2 2 f 2 + 2∆H °f (HCl.73 kJ ⋅ mol−1 − [( −59.895 kJ ⋅ mol−1 − (353 K) ( − 3. diamond) − S °m (C (s).1 kJ ⋅ mol−1 − (T ) (−378. we calculate the temperature at which ∆G°r = 0.7 kJ ⋅ mol−1 spontaneous at all temperatures.1 kJ ⋅ mol−1 ) + 226.895 kJ ⋅ mol −1 ∆S °r = S °m (C (s). (b) ∆H ° = ∆H ° (CaCl . g) − [∆H ° (CaC .16 kJ ⋅ mol−1 )] = − 256.8 J ⋅ K −1 ⋅ mol−1 + 200. that temperature is ∆G°r = 0 = − 232. (c) ∆H °r = ∆H °f (C (s).363 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) = + 3. we expect the reaction to be spontaneous at low temperatures.

15 kJ ⋅ mol−1 ) − (− 228.Because ∆H °r is positive and ∆S °r is negative. Comparing the Boltzmann entropy calculations for the cis and trans forms: cis: SM-189 . so the standard molar entropies should be more similar.57 kJ ⋅ mol−1 ) = +86.63 (a) 1-propanol (C3 H8 O) and 2-propanone (C3 H 6 O) have similar numbers of electrons so that we would expect the molar entropies to be similar. This is observed.8 kJ ⋅ mol−1 ) − ( -32. Note: This calculation is for atmospheric pressure.65 For the cis compound there will be 12 different orientations: For the trans compound there will only be 3 different orientations.6 kJ ⋅ mol−1 Positive ∆G°r indicates a nonspontaneous reaction. Reaction A is spontaneous but reaction B is not spontaneous 7. we might expect the liquid phase to be more ordered than for 2-propanone.82 kJ ⋅ mol−1 ) − (− 228. hydrogen bonding will not be important because the molecules are too far apart. Diamond can be produced from graphite at elevated pressures and high temperatures. Because 1-propanol exhibits hydrogen bonding. The standard molar entropy for 2-propanone is 200 J ⋅ K −1 ⋅ mol−1 while that of 1-propanol is 193 J ⋅ K −1 ⋅ mol−1 . (b) In the gas phase. the reaction will be nonspontaneous at all temperatures. 7. 7.61 Assuming standard state conditions. ∆Gro for C2H4(g) + H2O(g) → CH3CH2OH(l) is: ∆G°r = ( −174.8 kJ ⋅ mol−1 ) − ( 68. however. ∆Gro for C2H6(g) + H2O(g) → CH3CH2OH(l) + H2(g) is: ∆G°r = ( − 174.57 kJ ⋅ mol−1 ) = −14.4 kJ ⋅ mol −1 Negative ∆G°r indicates a spontaneous reaction.

50 J ⋅ K −1 600 K 2290 J = 9.02 × 10 = (1.02 × 10 S = 9. s) − [4∆G°f (Fe3 O 4 . and melting point is given by ∆S °fus = ∆H °fus .79 ⋅ K −1 234 K For Pb : ∆S °fus = For Hg : ∆S °fus = For Na: ∆S °fus 2640 J = 7.38 × 10−23 J ⋅ K −1 ) ln 36. enthalpy of fusion.6 kJ ⋅ mol−1 Because ∆G°r is negative. s)] ∆G°r = 6(−742. The relationship between entropy of fusion.69 This is best answered by considering the reaction that interconverts the two compounds 4 Fe3 O 4 (s) + O 2 (g) ⎯⎯ → 6 Fe 2 O3 (s) We calculate ∆G°r using data from Appendix 2A: ∆G°r = 6∆G°f (Fe2 O3 . the process is spontaneous at 25°C.67 According to Trouton’s rule.12 J ⋅ K −1 371 K These numbers are reasonably close but clearly much smaller than the value associated with Trouton’s rule.13 J ⋅ K −1 23 23 23 23 The cis form should have the higher residual entropy. Fe2 O3 is thermodynamically more stable. the entropy of vaporization of an organic liquid is a constant of approximately 85 J ⋅ mol−1 ⋅ K −1 . Therefore.4 kJ ⋅ mol−1 )] = − 391.02 × 10 S = 20.6 J ⋅ K −1 trans: S = k ln 36. SM-190 . 7.38 × 10−23 J ⋅ K −1 ) ln 126. Tfus 5100 J = 8. 7.S = k ln 126.2 kJ ⋅ mol−1 ) − [4(− 1015.02 × 10 = (1.

the entropy change of the surroundings must be a negative number ∆H °system ⎛ ⎜ ∆S °surr = − T ⎝ ⎞ ⎟ . the entropy change of the surroundings is primarily a result of the dispersal of thermal motion.4 kJ ⋅ mol−1 − ( − 166. For (b). (e) The driving force for the dissolution is the dispersal of matter. (d) Because the surroundings participate in the solution process only as a source of heat. diamond SM-191 .5 kJ ⋅ mol −1 This process is predicted to be nonspontaneous. ∆G °r = − 100. the change in enthalpy does not favor the dissolution process.7. we know it is spontaneous). (c) Locational disorder is dominant.9 kJ ⋅ mol−1 This process is predicted to be nonspontaneous. 7.9 kJ ⋅ mol−1 ) = + 66. the entropy change of the system must be positive. (c) The presence of added sulfur or iron should not affect these answers.4 kJ ⋅ mol−1 ) = + 33.71 We can calculate the free energy changes associated with the conversions: (a) 2 FeS(s) ⎯⎯ → Fe(s) + FeS2 (s) (b) FeS2 (s) ⎯⎯ → S(s) + FeS(s) For (a). graphite ⎯⎯ → C(s).75 The values are calculated simply from the Hess’s law relationship that the sums of the various energy quantities for the products minus the similar sum for the reactants will give the overall change in the state function desired: C(s). Because spontaneous processes are accompanied ⎠ by an increase in entropy. 7.9 kJ ⋅ mol−1 − 2 ( −100. ∆G °r = − 166.73 (a) Because the enthalpy change for dissolution is positive. resulting in an overall positive ∆S . (b) In order for the process to be spontaneous (because it occurs readily.

) The standard free energy change for this reaction is positive as follows. diamond) = + 2. the trend is expected—the three delocalized bonds in C(s) graphite are actually slightly more exothermic than the four C—C single bonds in diamond.77 The entries all correspond to aqueous ions. graphite) = 2. (Notice that if one considered the C— C bonds in graphite to be localized. diamond) = +1. the carbon atom is bonded to four other carbon atoms by single C—C bonds (approximately by 348 KJ ⋅ mol−1 ). the opposite prediction would have been made. Even though these approximations overestimate the effect of delocalization on the C—C bond strength in graphite. Given the actual numbers. In graphite.740 J ⋅ K −1 ⋅ mol−1 = −3.377 J ⋅ K −1 ⋅ mol−1 − 5.900 kJ ⋅ mol−1 Notice that the values used for the entropy calculation are absolute entropies. using the values of 518 kJ ⋅ mol−1 of delocalized C—C bonds. making the standard enthalpy change a positive number. as given in Table 6. The fact that they are negative is due to the reference point that has been established. is not 0. from a positive standard enthalpy change and a negative standard entropy change for the reaction.363 J ⋅ K −1 ⋅ mol−1 ∆G° = ∆G°f (C(s).895 kJ ⋅ mol−1 ∆S ° = ∆S °m (C(s).∆H ° = ∆H °f (C(s). all the carbon atom are bonded to four other carbon atoms in a very rigid lattice. 7. In diamond. It is not surprising that the change in entropy upon going from graphite to diamond would decrease. Because ions cannot SM-192 . the change is clearly small however. the carbon atom is bonded to three other carbon atoms with delocalized bonds (we can approximate this very roughly.7). because we would expect graphite to have a higher molar entropy than diamond. whereas in diamond. diamond) − ∆S °m (C(s). Similarly. not ∆S ° values and that the S °m value for C(s). one can compare the bond formation and breaking that accompanies a change from graphite to diamond. graphite. Graphite has a delocalized structure similar to that of benzene.

01 kJ ⋅ mol−1 − T (118. we need to know ∆H ° and ∆S ° for the process: H 2 O(l) ⎯⎯ → H 2 O(g) ∆H °r = ∆H °f (H 2 O. This definition is then used to calculate the standard entropies for the other ions. l) = 188. a reference point that defines S °m (H + .50 g ∆Gr = ( −273.82 kJ ⋅ mol−1 ) − [ − 285.91 J ⋅ K −1 ⋅ mol−1 ] = 118.57 kJ − 0.79 1 2 O 2 (g) → H 2 O(l) and 0.015 g ⋅ mol ⎠ Therefore.35 kJ − 6.9 kJ − ( −6.T∆S. The fact that they are negative will arise in part because the solvated ion M(H 2 O) x n + will be more ordered than the isolated ion and solvent molecules (M n + + x H 2 O).01 kJ ⋅ mol−1 ∆S °r = S °m (H 2 O. therefore. l) = ( − 241.58 kJ -1 ⎟ ⎝ 18.83 J ⋅ K −1 ⋅ mol −1 − [69. g) − S °m (H 2 O.92 J ⋅ K −1 ⋅ mol−1 ∆G°r = ∆H °r − T ∆S °r = 44.81 (a) In order to calculate the free energy at different temperatures. aq) = 0 has been established.50 g of H 2 (g) consumed: ⎛ ⎞ 0. g) − ∆H °f (H 2 O.92 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) T(K) ∆G°r (kJ) 298 373 423 8. ∆G = ∆H .29 kJ SM-193 .actually be separated and measured independently.83 kJ ⋅ mol−1 ] = 44.58 kJ ) 298 K = 216 J ⋅ K -1 7.25 kJ ⋅ mol-1 ) ⎜ = −6. ∆S r = −70. ∆H r − ∆Gr T Given the reaction H 2 (g) + ∆S r = 7.

97 kJ ⋅ mol−1 ) C 6 H12 (l) + 3 C 2 H 2 (g) ⎯⎯ → C 6 H 6 (l) + 3 C 2 H 6 (g) ∆G °r = − 205. because this is the normal boiling point of water.83 The dehydrogenation of cyclohexane to benzene follows the following equation: C6 H12 (l) ⎯⎯ → C6 H 6 (l) + 3 H 2 (g) We can confirm that this process is nonspontaneous by calculating the ∆G°r for the process.The reaction goes from being nonspontaneous near room temperature to being spontaneous above 100°C. l) − ∆G°f (C6 H12 .6 kJ ⋅ mol−1 The reaction of ethane with hydrogen can be examined similarly: C2 H 2 (g) + H 2 (g) ⎯⎯ → C 2 H 6 (g) ∆G°r = ∆G°f (C2 H 6 . g) − ∆G°f (C2 H12 . using data in Appendix 2A: ∆G°r = ∆G°f (C6 H 6 . 7.82 kJ ⋅ mol−1 ) − 68.7 kJ ⋅ mol−1 = +97. l) = 124.15 kJ ⋅ mol −1 = −100.13 kJ ⋅ mol−1 SM-194 . (b) The value at 100°C should be exactly 0.6 kJ ⋅ mol−1 ∆G°r = 3( − 100. (c) The discrepancy arises because the enthalpy and entropy values calculated from the tables are not rigorously constant with temperature. Better values would be obtained using the actual enthalpy and entropy of vaporization measured at the boiling point.97 kJ ⋅ mol−1 We can now combine these two reactions so that C2 H 2 (g) accepts the hydrogen that is formed in the dehydrogenation reaction: C6 H12 (l) ⎯⎯ → C6 H 6 (l) + 3 H 2 (g) + 3[C2 H 2 (g) + H 2 (g) ⎯⎯ → C2 H 6 (g)] ∆G°r = + 97. g) = ( − 32.3 kJ ⋅ mol−1 − 26.

79 kJ ⋅ mol−1 = −9. and ∆S ° are as follows: ∆G °r = ∆G°f (2) − ∆G°f (1) = 62. 7. Essentially.We can see that by combining these two reactions.91 kJ ⋅ mol−1 ∆G°r = ∆H °r − T ∆S °r −7.90 kJ ⋅ mol−1 ) − (−6.33 J ⋅ K −1 ⋅ mol−1 ∆G°r = ∆G°f (3) − ∆G°f (1) = 58.86 kJ ⋅ mol−1 = −7.86 kJ ⋅ mol−1 = − 2.99 kJ ⋅ mol−1 ) = −9.18 kJ ⋅ mol−1 ∆G°r = ∆H °r − T ∆S °r − 2.99 kJ ⋅ mol−1 ) = − 4.89 kJ ⋅ mol−1 ∆H °r = ∆H °f (2) − ∆H °f (1) = (−11. ∆H °.91 kJ ⋅ mol−1 − (298 K) (∆S °r )/(1000 J ⋅ kJ −1 ) ∆S °r = −7.17 kJ ⋅ mol−1 ) − (− 6.79 kJ ⋅ mol−1 ∆H °f = ∆H °f (3) − ∆H °f (1) = (−16.85 (a) H3C H C C CH3 H H3C H H C C CH3 H3C H3C H C C H cis-2-Butene trans-2-butene 2-Methylpropene (b) For the three reactions. the overall process becomes spontaneous.11 J ⋅ K −1 ⋅ mol−1 SM-195 .97 kJ ⋅ mol−1 − 65.89 kJ ⋅ mol−1 = − 4.07 kJ ⋅ mol−1 − 65. we are using the energy of the favorable reaction to drive the nonfavorable process.18 kJ ⋅ mol−1 − (298 K) (∆S °r )/(1000 J ⋅ kJ −1 ) ∆S °r = − 4. the calculation of ∆G °.

21 kJ ⋅ mol−1 ∆S °r = S °m (H 2 . g) + S °(CO 2 . We need to calculate ∆H °r and ∆S °r for each process.74 J ⋅ K −1 ⋅ mol−1 − [128.73 kJ ⋅ mol−1 − (298 K) (∆S °r )/(1000 J ⋅ kJ −1 ) ∆S °r = − 2.07 kJ ⋅ mol−1 − 62.73 kJ ⋅ mol−1 ∆G°r = ∆H °r − T ∆S °r − 4.90 kJ ⋅ mol−1 ) − (− 11. we can examine those values to place the three compounds in order of their relative absolute entropies. The ordering is S °m (1) > S °m (2) > S °m (3).97 kJ ⋅ mol−1 = − 4.95 J ⋅ K −1 ⋅ mol−1 ] = + 215. l) = (−393. g) − [ S °m (HCOOH.72 kJ ⋅ mol−1 ) = +31.87 ∆H °r = ∆H °f (CO2 .90 kJ ⋅ mol−1 ∆H °r = ∆H °f (3) − ∆H °f (2) = (−16.8 K (b) CH 3 COOH(l) ⎯⎯ → CH 4 (g) + CO 2 (g) SM-196 .47 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) T = 144. (a) HCOOH(l) ⎯⎯ → H 2 (g) + CO 2 (g) 7. g) − ∆H °f (HCOOH. (c) Because ∆S ° is also equal to the difference in the S °m values for the compounds.47 J ⋅ K −1 ⋅ mol−1 The reaction will become spontaneous above the temperature at which ∆G ° r = 0 : 0 = 31.∆G°r = ∆G°f (3) − ∆G°f (2) = 58.17 kJ ⋅ mol−1 ) = −5.51 kJ ⋅ mol−1 ) − (− 424. l)] = 130.68 J ⋅ K −1 ⋅ mol−1 + 213.78 J ⋅ K −1 ⋅ mol−1 The most stable of the three compounds is 2-methylpropene.90 kJ ⋅ mol−1 = −5.21 kJ ⋅ mol−1 − T (215.

A consideration of the parameters shows that this is driven by the entropy increase in the production of the gas.81 kJ ⋅ mol−1 ) + (−393.4 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) T = 185. g) + S °(CO 2 .6 kJ ⋅ mol−1 ∆S °r = S °m (C6 H 6 .5 kJ ⋅ mol−1 ) = +16.∆H °r = ∆H °f (CH 4 . l) + ∆H °f (CO 2 .74 J ⋅ K −1 ⋅ mol−1 − (167.2 J ⋅ K −1 ⋅ mol−1 The reaction will become spontaneous above the temperature at which ∆G ° r = 0 : 0 = 16. g) − ∆H °f (CH3 COOH. l) = (−74.4 J ⋅ K −1 ⋅ mol−1 The reaction will become spontaneous above the temperature at which ∆G ° r = 0 : 0 = 40.18 kJ ⋅ mol−1 ∆S °r = S °m (CH 4 .2 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) T = 67.51 kJ ⋅ mol−1 ) − [−385.36 K (c) C 6 H 5 COOH(s) ⎯⎯ → C6 H 6 (l) + CO 2 (g) ∆H °r = ∆H °f (C6 H 6 .0 kJ ⋅ mol−1 + (− 393.18 kJ ⋅ mol−1 − T (240. s)] = + 49.74 J ⋅ K −1 ⋅ mol−1 − [159.26 J ⋅ K −1 ⋅ mol−1 + 213.51 kJ ⋅ mol−1 ) − (− 484. SM-197 .3 J ⋅ K −1 ⋅ mol−1 + 213.0 K It is clear from these calculations that all of these carboxylic acids are thermodynamically unstable with respect to decomposition to produce CO 2 (g). s)] = +173. g) − [ S °m (CH 3 COOH. because the enthalpy of the reaction in all cases is endothermic. g) − [∆H °f (C6 H 5 COOH. l) + S °(CO 2 .1 kJ ⋅ mol−1 ] = + 40. g) − [ S °m (C6 H 5 COOH.6 J ⋅ K −1 ⋅ mol−1 ) = + 219. g) + ∆H °f (CO2 . l)] = 186.58 kJ ⋅ mol−1 − T (219.8 J ⋅ K −1 ⋅ mol−1 ] = + 240.