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NS102 Study Problems Set 4

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

1. Predict whether each of the following processes involves an increase or decrease


in entropy or whether the outcome is uncertain
(a) The decomposition of ammonium nitrate
2NH4NO3 (solid)  2N2 (gas) + 4H2O (gas) + O2 (gas)
(b) The conversion of SO2 to SO3
2SO2 (gas) + O2 (gas)  2SO3 (gas)
(c) The extraction of sucrose from sugar juice
C12H22O11 (aqueous)  C12H22O11(solid)
(d) The “water gas shift” reaction (involved in the gasification of coal)
CO(gas) + H2O(gas)  CO2 (gas) +H2(gas)
Answer: (a) increase; (b) decrease; (c) decrease; (d) uncertain
2. Under what temperature conditions would you expect the following reactions to
occur spontaneously?
(a) 2NH4NO3 (solid)  2 N2 (gas) + 4H2O(gas) H=  236.0 kJ
(b) I2 (gas)  2I(gas) H= +151.0 kJ
Answer: (a) spontaneous at all temperatures
(b) at low temperatures: non-spontaneous; at high temperatures: spontaneous
3. For each of the following reactions, indicate whether S for the reaction should be
positive or negative. If it is not possible to determine the sign of S from the
information given, indicate why.
a) CaO(solid) +H2O (liquid)  Ca(OH)2 (solid)
b) 2HgO(solid)  2Hg(liquid) + O2 (gas)
c) 2NaCl(l)  2Na(l) + Cl2 (g)
d) Fe2O3 (s) + 3 CO (g)  2Fe (s) + 3CO2 (g)
Answer: (a) negative; (b) positive; (c) positive; (d) uncertain
4. 1 mol of hydrogen gas is contained in the left-hand
side of the isolated container. The right hand side is
evacuated (Equal volumes of V for left and right). When
the valve is opened, hydrogen gas streams into the right
side.
a) What is the change in internal energy of the system?
b) What is the final entropy change?
c) Does the temperature of the gas change?
Answer: a) U=0 b) Entropy increases with a value of S=5.76 J/K) c) Temperature
is constant (isothermal process)
5. Suppose your roommate is tidying up your messy room at the dorm after a big
poker party. Since more order is created by your roommate, does this represent a
violation of the second law of thermodynamics? Why?
Answer: No, there is no violation of 2nd Law
6. What is the entropy decrease in 1 mole of helium gas, which is cooled at 1atm
from room temperature 298 K to a final temperature 4 K? (Cp of helium=21 J/mole.K)
Answer: S = - 90.5 J/K
7. Indicate if the entropy of the system would increase, decrease or stay the same in
the reaction A (g) + 3B (g) → 4C (l). Why? (Exam Archive)
Answer: Decrease
8. Which of the following thermodynamic quantities are state functions? (Exam
Archive)
Q( ) W( ) U( ) H( ) S( )
Answer: Q (NO) W (NO), U (YES), H (YES), S (YES)
9. Indicate whether the entropy of the system would increase or decrease in each of
the following reactions. Explain why. (Exam Archive)
(a) CCl4 (l)  CCl4 (g)
(b) C3H8 (g) + 5O2 (g)  CO2 (g) + 4H2O(l)
(c) N2 (g) + 3H2 (g)  2NH3 (g)
(d) 2KClO3 (s)  2KCl(s) + 3O2 (g)
Answer: a) increase b) decrease c) decrease d) increase

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

(c) 2N2O + O2 (gas)  4NO(gas) 197.1 198.2


(d) Formation of table salt
2Na(solid) + Cl2 (gas)  2NaCl(solid) -822.2 -181.7

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.

Reaction Sign of H Sign of S Sign of G Spontaneous?


A(g) + 2B(l) → 2C(g) Negative   
3D2 (l) → 2D3 (l) Negative   
2E (g) + F (g) → 3G (l) Positive   
J (l) → J (s)
g: gas; l: liquid; s: solid
b) Can you make a reaction that is non-spontaneous at high temperature by
decreasing its temperature? Show/explain why or why not.
Answer: a)
Reaction Sign of H Sign of S Sign of G Spontaneous?
A(g) + 2B(l) → 2C(g) Negative  – yes
3D2 (l) → 2D3 (l) Negative – cannot decide cannot decide
2E (g) + F (g) → 3G (l) Positive  + no
J (l) → J (s) Negative – cannot decide

16. A thermodynamic system is taken from an initial C


40
state A to another B and back again to A, via state C,
as shown by the path A-B-C-A in the PV diagram. 30
P (Pa)

(1 J=1 Pa∙1m3) (Exam Archive) 20 A B

10

0
0 1 2 3 V (m3)

c) Calculate the entropy change along each part of the path.


(Parts a) and b) of this question is Question 12 in Problem Set 2)
Answer: AB 22.83 J/K; BC 8.6J/K CA -31.43 J/K

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).

This reaction is non-spontaneous at


room temperature.
(Exam Archive)

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

19. Consider the following spontaneous


reaction of A2 molecules (white) and B2
molecules (gray): 2A2  B2  2A2B .
What are the signs (+, -, or 0) of H, S,
and G for this reaction? Explain
(Exam archive)

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 )

e) What is the amount of entropy change in each pathway?


f) If you find a direct method of going directly from A to B without any intermediate
steps, which of the following quantities will change? Q, W, U, S, H. You do not
need to do any calculations here.
(Parts a) - d) of this question is Question 18 in Problem Set 2)
Answer: e) 17.3 J/K f) Q and W
21. (Exam Archive)
a) 1g of ice at -2˚C was dropped into a lake at 35˚C. The ice irreversibly absorbed
heat, becoming 1g of water at 35˚C. Please calculate the entropy change of “the
system” (1g H2O).
b) If the lake is “the surroundings”, please calculate the entropy change of the lake.
c) Is the transformation of 1g ice at -2˚C into 1g water at 35˚C thermodynamically
spontaneous? Please justify your answer by calculating the entropy change of the
Universe
Hint: S of the irreversible process can be re-defined as a sum of three reversible
processes:

Ice, Cp  2.1 J (K×g)


Water, Cp  4.2 J (K×g)
Water, Δ fusionH  334 J g

ln 1.007  0.00735
ln 1128
.  012060
.
ln 2  0.69300
ln 2150
.  0.76546
ln 4  1.38629
ln 35  3.55500

Answer: Ssys = (0.0154 + 1.2228 + 0.5064) = 1.7446 J/K

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 +

25. A non-spontaneous reaction may be driven by coupling it to a reaction that is


spontaneous.
The formation of an amino acid in our body requires 14.2 kJ/mol of energy input. The
change in Gibbs energy for the conversion of ATP molecules into ADP molecules
corresponds to G= ‒31 kJ/mol under the conditions prevailing in a typical cell.
(a) Is the formation of the amino acid spontaneous?
(b) Can ATP ADP conversion drive the amino acid formation reaction?
(c) How many moles of amino acid are synthesized by the conversion of 1 mole of
ATP molecule?
Answer: (a) no (b) yes (c) 2.2 moles