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The set contains study problems and exam questions from the previous semesters
on Second Law of Thermodynamics, spontaneity, entropy, enthalpy and Gibbs
energy. The gas constant (R) = 8.314 J mol-1 K-1 = 0.082 atm L mol-1 K-1
10. Indicate whether the entropy of the system would increase or decrease in each of
the following reactions. Explain why (Exam Archive)
(a) P4 (s) 5O2 (g) P4 O10 (s)
(b) C6H12O6 (s) 6O2 (g) 6CO2 (g) 6H2 O(g)
1 1
(c) H2S(g) O2 (g) S8 (s) H2O(g)
2 8
Answer: a) decrease b) increase c) decrease
11. Choose the member with the higher entropy in each of the following pairs and
justify your choice:
A B Notes:
(a) 1 mol of CO2 (s) 1 mol of CO2(g) CO2= carbon dioxide
(b) 1 mol of KBr(s) 1 mol of KBr (aq) KBr = Potassium bromide
(c) seawater in winter at 2°C seawater in summer at 23°C
(d) 3 mol O2 gas 2 mol of O3 gas (O2=oxygen, O3=ozone)
(e) perfume vapors diffusing Dew forming
through a room
Answer: (a) B (b) B (c) B (d) A (e) A
12. For each of the following reactions, indicate whether the reaction is spontaneous
or not and at what temperatures. Explain (Exam Archive
a) 2H2O(g) + O2 (g) 2H2O2 (g) ΔH 105.5kJ
b) 2C4H10 (g) + 13O2 (g) 4CO2 (g) + 5H2O(g) ΔH 2527kJ
c) N2 (g) + O2 (g) 2NO(g) ΔH 180.6kJ
Answer: a) non spontaneous at all T b) spontaneous at low T c) cannot decide
13. Complete the missing parts (?) in the following table:
H S G Result/comment
– + – ?
0 ? – Spontaneous
+ – ? ?
? 0 – ?
0 ? + ?
– – ? ?
+ + ? ?
+ ? + Nonspontaneous at all temp
14. Given below their H and S values, calculate the Gibbs energy change for the
reaction; also determine whether the following reactions are spontaneous or non-
spontaneous at 25°C. Comment on the temperature range they might be
spontaneous.
H (kJ) S (J/K) G (kJ) Spontaneous?
?
(a) The decomposition of hydrogen
peroxide (oksijenli su) -196 125
2H2O2 (liquid) 2H2O(liquid) +O2 (gas)
(b) The formation of ozone from oxygen
3O2 (gas) 2O3 (gas) 286 -137
Answer:
G (kJ) ? Spontaneous?
(a) -233.25 Yes
(b) 326.8 No
No
(c) 137.9
Spontaneous at higher temperature when T> 994K
Yes
(d) 768.1
But non-spontaneous when T> 4525 K
15. (Exam Archive)
a) For each of the following reactions taking place at constant temperature and
pressure, fill in all the blanks as best as you can. Indicate the sign of the enthalpy
change, entropy change, and Gibbs energy change as positive / negative / cannot
decide. Finally, fill in if the reaction is spontaneous or non-spontaneous as yes / no
/ cannot decide. For all your cannot decide responses explain why in the space
provided below.
10
0
0 1 2 3 V (m3)
17. For each of the following reactions, indicate whether the reaction is spontaneous
or not and at what temperatures. If it is not possible to decide from the information
given, explain why. (Exam Archive)
(a) PCl3 (g) Cl2 (g) PCl5 (g) H 87.9kJ
(b) CO2 (g) H2 (g) CO(g) H2O(g) H 41.2kJ
(c) NH4CO2NH2 (s) 2NH3 (g) CO2 (g) H 159.2kJ
Answer: a) spontaneous at low T b) cannot decide c) spontaneous at high T
18. Consider the following reaction of
A2B molecule being decomposed into A
(white) and AB molecules (white-gray):
A2B (gas) AB(gas)+A(gas).
a) What are the signs (+, −, or 0) of H, S, and G for this reaction at room
temperature? Explain
b) How can you make this reaction spontaneous?
Answer: a) G +, S +, H + b) by increasing temperature
Answer: G -, S -, H -
20. In a process in a factory, there are two ways of reaching from state A to state B,
as shown in the graph: (A →I→II→B) or (A→III→IV→V→VI→VII→VIII→B). The
properties of this gas may be well described by the ideal gas law, PV = NRT. The
heat capacity at constant volume, Cv is 3R/2. You are given one mole of the gas.
(Exam Archive)
10
II B VIII
8
Pressure (kPa)
VI
6
VII
IV
4
V
2
I A III
0
0 2 4 6 8 10 12 14
3
Volume (m )
ln 1.007 0.00735
ln 1128
. 012060
.
ln 2 0.69300
ln 2150
. 0.76546
ln 4 1.38629
ln 35 3.55500
22. You equilibrated ice and water under standard conditions. You injected a 1 ml
sample of that water into a giant oven fixed at 1000˚C. When re-equilibrated at
1000˚C, this sample of H2O existed as a vapor. Clearly, the Sf position of H2O was
reached by proceeding along an irreversible pathway (i.e., water vaporizing at nearly
1000˚C and one atmosphere describes a non-equilibrium condition).
Entropy changes of irreversible processes cannot be calculated directly. Instead, you
will attempt to calculate the entropy change of this sample by imagining a series of
equilibrium processes, which would bring you from the initial state, Si, to the same
final state, Sf. In your analysis, all pathways chosen should describe reversible
scenarios. Eventually, the entropy changes of these reversible processes can be
summed to yield the overall entropy change.
Using short notes, please describe three
reversible processes to be considered. We are
not asking for math or equations. Rather, how
would you manipulate the H2O along each of
the pathways? Each pathway, i.e., Srev1, Srev2
and Srev3, should define an independent
process of change. Please use words such as
“system”, “surrounding”, “dq”, “transfer”,
“infinitesimally slowly”, etc. (Exam Archive)
23. If A → B + 10C, could you claim with absolute certainty that S > 0? (Hint: State
all factors which can influence S in proceeding from initial state to final state) (Exam
Archive)
Answer : No-
We have a S term relating to changes of numbers – a system with more numbers
has more disorder
- We have a S term relating to mixtures and mixing – with everything else equal, a
system comprised of different participants has more disorder than a system
comprised of identical participants.
- We have a S term relating to phase transformations – identical participants
comprising the system posses different degrees of disorder, depending on their
phase. Solid crystalline forms are the most ordered whereas gaseous phases are the
most disordered.
- We have a S term relating to temperature changes – as thermal excitation
increases, the intrinsic motions of the system participants increase: greater modes,
greater mean fluctuations, and greater frequency of motions. As a result, disorder
increases with temperature.
- We have a S term relating to volume changes – with everything else equal, a
system comprised of x participants has more disorder when the volume space of the
system increases.
24. For each of the following processes, state whether each of q, w, U, and S is
positive, negative, or zero.
a) An ideal gas expands adiabatically into vacuum
b) Ice melts to liquid water at OC and 1 atm
c) Water is cooled from 50C to 20 C at constant pressure of 1 atm
d) Two ideal gases each initially at the same T and P are mixed at constant T and
P.
e) An ideal gas expands reversibly and isothermally
Answer: a) q=0, w=0, U=0, S is + b) q, w, U, and S are all positive c) q is -, w is
+, U is -, S is – d) q is +, w is -, U=0,S is + e) w is -, q is +, U=0, S is +