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Final Exam
2011/1/14
Constants
R = 8.314 J / mol K
= 0.0821 L atm / K mol
= 8.314 L kPa / K mol
In case that you need thermodyanmics data to solve the problems, please find four
tables, including Table1, Table2-1, Table2-2 and Table 3
1.
2.
3.
A sample consisting of 2.0 mol CO2 occupies a fixed volume of 15.0 L at 300 K.
When it is supplied with 2.35 kJ of energy as heat its temperature increases to 341
K. Assume that CO2 is described by the van der Waals equation of state, and
2
-2
-1
calculate w, U and H. a = 3.640 L atmmol , b = 0.04267 Lmol . You may
treat CO2 as an ideal gas to solve this problem, but only get 2 points on the
calculation of H. (2% for w , 3% for U , 4% for van der Waals solution of H, 2%
for ideal gas solution of H, 9% total)
4.
The bond enthalpy in NO is 632 kJmol-1 and that of each nitric N-O bond in NO2 is
469 kJmol-1. (a) Draw Lewis structures of NO and NO2 and show the bond order of
each compounds. The mean bond enthalpies given in the table below. (b) Using
Lewis structures, estimate the bond enthalpy of NO2 and (c) explain the reason of
the difference between actual bond enthalpy and estimated enthalpy (3% each, 9%
total)
Table 1
5.
6.
Using the standard enthalpy of formation of the following values, calculate the
standard reaction enthalpy for each of the following reactions. (2% each, 6% total)
(a) 3NO2(g) + H2O(l) 3HNO3(aq) + NO(g).
(b) B2O3(s) + 3CaF2(s) 2BF3(g) + 3CaO(s).
(c) H2S(aq) + 2KOH(aq) K2S(aq) + 2H2O(l).
7.
8.
Troutons rule states that the standard entropy of vaporization is ~ 85 J K-1 mol-1 for
most substances. Based on this rule, estimate the standard enthalpy of vaporization
of liquid bromine, which boils at 59 C. (4%)
9.
Consider the super-cool water to form ice at -10 C , the molar entropy change of
the system can be estimated as
Using the principle of 2nd law to quantitatively explain why this process is
spontaneous! Assuming that the heat capacitances are independent of temperature.
(5%)
10. Explain (a) why are almost all combustion reactions are spontaneous? (2%) (b) how
an endothermic reaction can be spontaneous? (2%) (c) how to assist an originally
non-spontaneous endothermic reaction becoming spontaneous? (2 %)
11. A scientist proposed the following two reactions to produce ethanol, a liquid fuel:
C2H4(g) + H2O(g) CH3CH2OH(l)
(A)
C2H6(g) + H2O(g) CH3CH2OH(l) + H2(g)
(B)
Reaction B is preferred if spontaneous, because C2H6(g) is a cheaper starting material
than C2H4(g). (a) Assume standard-state conditions and determine whether the
above reactions are spontaneous. (5%) (b) Assuming that H and S are
independent of temperature, estimate at what temperature ranges the above
reactions would become spontaneous. (5%)
12. You wish to construct a fuel cell to do electrical work for you based on the oxidation
of a hydrocarbon fuel. To understand how it works, you will (a) derive the relation
between Gibbs free energy and the maximum non-expansion work at constant T
and P (5%), (b) calculate the maximum non-expansion work available through the
combustion of one mole octane fuel (C8H18, in liquid phase) at the standard-state
conditions (5%) and (c) estimate the minimum heat that must be released to the
environment which cannot be transferred to do the electrical work. (5%)
Table 3
Solutions:
1. Ans.
(a) From ideal gas law, T = PV/nR.
T1 = P1V1/nR = 1 x22.4/1x0.0821 ([atm][L]/[mol][atmLK-1mol-1]) = 273 K
T2 = P1V2/nR = 1 x44.8/1x0.0821 ([atm][L]/[mol][atmLK-1mol-1]) = 546 K
T3 = T1 = 273 K (cycle 31 is isothermal. Thus, T3 = T1)
(three correct: 2, one wrong:1, two&three wrong:0)
(b) Cycle 12: w12 = -PV = -P1(V2-V1) = -1 x 22.4 = 22.4 atmL = -2.27 kJ
U12 = 3nRT/2 = 3P1(V2-V1)/2 = +3.40 kJ (T21 = T2-T1 = P1(V2-V1)/nR)
q12 = U12 - w12 = +5.67 kJ
Another way to calculate Cycle 12 is also correct
q12 = 5nRT/2 = +5.67 kJ
U12 = 3nRT/2 = 3P1(V2-V1)/2 = +3.40 kJ
w12 = U12 - q12 = -2.27 kJ
Cycle 23: w23 = -PV =0, U23 = 3nRT/2 = -3P1(V2-V1)/2 = -3.40 kJ
(T32 = T3-T2 = -P1(V2-V1)/nR), q23 = U23 = -3.40 kJ
Cycle 31:
w31 nRT1
V1
V3
V
dV
nRT1 ln 3 PV
1 1 ln 2 1.57kJ
V
V1
3. Ans.
Sample is in the fixed volume, i.e. under constant-volume condition.
V = 0, thus, w = 0.
2.35 kJ of heat was supplied, thus q = +2.35 kJ.
FromU = q + w, H = U + PV, van der Waals equation (P+an2/V2)(V-nb)=nRT,
For initial state: (P1+an2/V2)(V-nb)=nRT1.
For final state: (P2+an2/V2)(V-nb)=nRT2.
Differential between final and initial state,
(P2- P1)(V-nb)=nr(T2 - T1) and P = nRT/(V-nb).
nRV T2 T1
2 0.082115 (341 300)
H U V P q V P q
2.35
V nb
15 2 0.04267
= 2.35 [kJ] +(2x0.0821x15x41)/(15-2x0.04267) [atm] x 1.10x102 [Jatm-1 L-1]
= +3.03 kJ
Thus, w = 0, U = +2.35 kJ, and H = +3.03 kJ.
(2% for w , 3% for U ,
4% for van der Waals solution of H, 2% for ideal gas solution of H)
4. Ans.
(a) The Lewis structure for NO and NO2 show that the bond order in NO is a double bond
and that in NO2 is 1.5 on average. (2%, if both Lewis structure is correct, then 1 point. If
both bond order is correct, then 1 point)
(b) Bond enthalpy of NO at 632 kJmol-1 is close to N=O value listed in table, whereas the
N-O bond enthalpy in NO2 is of 469 kJmol-1 is slightly greater than the average of a N-O
single and N=O double bond;
(630 kJ + 210 kJ) = 420 kJ.
The extra stability is due to resonance stabilization. (5%)
(c) The bond energies are the same for the two bonds, because the bonds are equivalent
due to resonance. (2%)
5. Ans.
Reaction enthalpy is obtained from H = U + ngasRT.
Thus, H = U + ngasRT = 8.0 + 2x8.314x583 =17.7 kJ. (6%)
7. Ans:
For this irreversible process, we may construct two (reversible) steps first, (1) and (2),
and then to calculate their individual entropy changes. We then sum them up to obtain
the total entropy change of the system.
(1) Compression from P1 to P2 at constant temperature (T1):
(must be a reversible process)
(5%)
(2) Heating from T1 to T2 at constant pressure (P2):
(can be either reversible or irreversible)
8. Ans: (4%)
9. Ans: (5%)
Therefore,
It is a spontaneous process!
10.Ans:
The criterion for spontaneous process is G = H - TS < 0 at constant T and P.
(a) For most combustion reactions, H < 0, and H overwhelms the contribution of
the TS term for the G being always negative.
(b) For endothermic reactions, H > 0, the only way for G < 0 is TS > H, so S
must be positive to overcome the positive contribution of H.
(c) Following (b), increasing T for TS > H is a way to assist the original
non-spontaneous reaction to be spontaneous.
10
12. Ans:
(a) Starting from G H - TS
G = H - TS
(at constant T and P)
= U + PV - TS
(U H + PV)
= q + w + PV - TS (U = q + w)
= TS + (-PV + we,max) + PV - TS
(for reversible process, q = TS and w = -PV + we,max )
= we,max (5%)
Meaning that the maximum non-expansion work is equal to the Gibbs free
energy for a reversible process.
(b) C8H18(l) + 25/2 O2(g) 8 CO2(g) + 9 H2O(l)
we,max = Gr0 = [9(-237.13) + 8(-394.36)] [(+6.4) + 0] = -5295.5 kJ mol-1
or | we,max | = 5295.5 kJ mol-1
(5%)
(c) Hc0 = -5471 kJ mol-1, the minimum heat that must be released to the
environment (cannot be used to do the electric work) is
qTS =Hc0 - Gr0 = -5471 + 5296 = -175 kJ mol-1
or | q | = 175 kJ mol-1
(5%)
11