CHAPTER 18- Practice Exercise A.
Kweyete
PAHLAVAN_
Entropy, Free Energy, and Equilibrium
Problem #1. Which one of the following substances in each pair would have the largest
entropy?
(a) H2O(s) at 25oC , 1 atm and H2O(l) at 25oC, 1 atm
(b) SO2(g) at STP and SO3(g) at STP
(c) H2O(l) at 25oC and H2O(l) at 100oC
(d) Ne(g) at 25oC,1 atm and He(g) at 25oC, 1 atm
(e) NH3(g) at 298 K,1 atm and NH3(g) at 25oC, 2 atm
Problem #2. For each of the following reactions determine if the entropy change (∆So)
increased or decreased
and entropy value (∆So) is positive or negative.
(a) 2H2 (g) + O2 (g) 2H2O (g) decreased, negative
(b) 2Hg (l) + O2 (g) 2Hg (s) undetermined
(c) N2 (g) + 3H2 (g) 2NH3 (g) decreased, negative
(d) 2HF (aq) 2F-(aq) + 2H+(aq) increased, positive
(e) 2C (s) + O2 (g) 2CO (g) increased, positive
(g) decomposition of carbonated water. increased, positive
Problem #3. Calculate the entropy change (So) for the following reaction at 25oC;
2SO2 (g) + O2 (g) 2SO3 (g)
Given the following standard entropy values at 25oC:
SO2 (g), 248.5 J/K.mol; O2 (g), 205.0 J/K.mol; SO3 (g) , 256.2 J/K.mol.
So = [ (2 x 256.2)] – [(2 x 248.5) + (205)] = 512.4 – 702 = -189.6 J/K
Problem #4. S is -198.2 J/K for reaction: N2(g) + 3H2(g) 2NH3(g)
at 25oC. Given So(N2) =191.5 J/K.mol and So(H2) = 130.58 J/K.mol at 25oC, what
is the value of So(NH3)?
-198.2 = [2 So(NH3) ] - [(3 x 130.58) + (191.5)]
2 So(NH3) = -198.2 + 583.24 = 385.04
So(NH3) = 192.52 J/K-mol
Problem #5. Calculate Go for the following reaction at 25oC.
4NO (g) + 6H2O (g) 5O2 (g) + 4NH3 (g given the following Gof values;
NO(g), 86.71 KJ/mol ;H2O(g) , -228.61 KJ/mol
O2(g), 0.0 KJ/mol ; NH3(g), -16.66 KJ/mol
Go = [ (4 x -16.66)] – [(4 x 86.71) + (6 x -228.61)]
1
= [-66.64] – [346.84 – 1371.66]
= [-66.64 + 1024.82] = 958.18 KJ
Problem #6 (a) Consider the reaction for oxidation of glucose: C6H12O6 (s) + 6O2 (g) 6CO2 (g)
+ 6H2O (l) using standard values table, calculate So and Ho.
So = [ (6 x 213.6) + (6 x 69.9) ] – [(6 x 205) + (212.1)]
= [ 1281.6 + 419.4] – [ 1230 + 212.1 ] = 259 J/K
Ho = [ (6 x -393.5) + (6 x -285.8) ] – [(6 x 0) + (-1274.5)]
= [ -2361 – 1714.8 ] – [ -1274.5 ]
= -2801.3 KJ
(b) Calculate the free energy for reaction: CaCO3 (s) CaO (s) + CO2 (g) at 25oC.
Go = [ (-604.5 – 394.5) ] - [ -1128.8)] = 129.8 KJ
Problem #7. Consider the following reaction at 25oC. C (s) + H2O (g) CO (g) + H2 (g)
Given H = 131.4 KJ , S = 135 J/K , G = 91.2 KJ, calculate the temperature which the
o o o
reaction performed.
T = (131.4 – 91.2 ) / (0.135) = 297.78 K
Problem #8. Calculate G at 298 K for the following reaction if reaction mixture consists of 2.0
atm of SO2(g) , 2.0 atm O2(g) , and 2.0 atm of SO3(g).
2SO2 (g) + O2 (g) 2SO3 (g) , Go298= -140.4 KJ
Kp = (2)2 = 0.5
(2)2(2)
∆G = ∆G° + RTlnQ
= -140.4 + (8.314)(298)(-0.693)(10-3) = -142.11 KJ
Problem #9. Calculate the equilibrium constant for the following reaction at 25oC.
2H2(g) + O2(g) 2H2O(l)
Given the following standard free-energy: H2O(l) , Gof = -237.2 KJ/mol at 25oC.
∆G° = -RTlnK
-237200 J = -(8.314)(298)lnK
lnK = 95.739
K = e95.739 = 3.79 x 1041 .
Problem #10. Given the following data at 25oC:
substance So(J/mol.K) Hof(KJ/mol)
NO2(g) 240.45 33.8
N2O4(g) 304.33 9.66
2
(a) Calculate the value of Go for the following reaction at 25oC: 2NO2 (g)
N2O4 (g)
∆H° = 9.66 – 2(33.8) = -57.94 kJ = -57940 J
∆S° = 304.33 – 2(240.5) = -176.67 J
∆G° = -57940 – (298)(-176.67) = -5292.3 J = -5.292 kJ
(b) Is the formation of N2O4 (g) a spontaneous process at 25oC and standard-state
conditions?
Yes
(c) What is the value of the equilibrium constant for this reaction?
∆G° = -RTlnK
-5292.3 J = -(8.314)(298)lnK
lnK = 2.136
K = e2.136 = 8.466
Problem #11. Go equals +20.00 KJ for the reaction below at 298 K and 1atm of pressure;
CuS (s) + H2 (g) Cu (s) + H2S (g)
(a) Calculate the equilibrium constant for the reaction.
∆G° = -RTlnK
20000 J = -(8.314)(298)lnK
lnK = -8.07
K = e-8.07 = 3.13 x 10-4 .
(b) At 298 K, does the equilibrium lie largely in the direction reactants or
products?
Lies in direction of reactants
Problem #12. Consider the reaction 4CuO (s) 2Cu2O (s) + O2 (g), at 298 K, given the following;
substnace Hof (KJ/mol) Gof(KJ/mol)
CuO(s) -157.3 -129.7
Cu2O(s) -168.6 -146.0
(a) Calculate So for the reaction
∆G° = 2(-146) – 4(-129.7) = 226.8 kJ = 226800 J
∆H° = 2(-168.6) – 4(-157.3) = 292 kJ = 292000 J
∆S° = (292000 – 226800)/ 298 = 218.8 J
(b) Is this reaction feasible for preparation of Cu2O(s) at standard state conditions?
NO
(c) If the reaction is not feasible, how could it be made to occur?
Increase the temperature beyond 298 K
