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) (c) H2S(g) 1 1 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 (a) 1 mol of CO2 (s) (b) 1 mol of KBr(s) (c) seawater in winter at 2C (d) 3 mol O2 gas (e) perfume vapors diffusing through a room B 1 mol of CO2(g) 1 mol of KBr (aq) seawater in summer at 23C 2 mol of O3 gas Dew forming Notes: CO2= carbon dioxide KBr = Potassium bromide (O2=oxygen, O3=ozone)

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) b) 2C4H10 (g) + 13O2 (g) 4CO2 (g) + 5H2O(g) c) N2 (g) + O2 (g) 2NO(g)

H 105.5kJ H 2527kJ H 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 0 + ? 0 + + S + ? 0 ? + ? G ? + ? ? + Result/comment ? Spontaneous ? ? ? ? ? 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 nonspontaneous at 25C. Comment on the temperature range they might be spontaneous. H (kJ) (a) The decomposition of hydrogen peroxide (oksijenli su) 2H2O2 (liquid) 2H2O(liquid) +O2 (gas) (b) The formation of ozone from oxygen 3O2 (gas) 2O3 (gas) (c) 2N2O + O2 (gas) 4NO(gas) (d) Formation of table salt 2Na(solid) + Cl2 (gas) 2NaCl(solid) S (J/K) G (kJ) ? Spontaneous?

-196 286 197.1 -822.2

125 -137 198.2 -181.7 Answer:

(a) (b) (c) (d)

G (kJ) ? -233.25 326.8 137.9 768.1

Spontaneous? Yes No No Spontaneous at higher temperature when T> 994K Yes 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 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

Sign of S

Sign of G

Spontaneous?

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 A(g) + 2B(l) 2C(g) 3D2 (l) 2D3 (l) 2E (g) + F (g) 3G (l) J (l) J (s) Sign of H Negative Negative Positive Negative Sign of S Sign of G cannot decide + cannot decide Spontaneous? yes cannot decide no

16. A thermodynamic system is taken from an initial 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. (1 J=1 Pa1m3) (Exam Archive)

40 30

P (Pa)

20 10 0 0

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: AB 22.83 J/K; BC 8.6J/K CA -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) (b) CO2 (g) H2 (g) CO(g) H2O(g) (c) NH4CO2NH2 (s) 2NH3 (g) CO2 (g)

H 87.9kJ H 41.2kJ 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 IIIB) or (AIIIIVVVIVIIVIIIB). 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

Pressure (kPa)

8 6 4 2 0 0

B VI IV V

VIII

VII

I
2 4

A
6

III
8
3

10

12

14

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 -2C was dropped into a lake at 35C. The ice irreversibly absorbed heat, becoming 1g of water at 35C. 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 -2C into 1g water at 35C 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 (Kg) Water, Cp 4.2 J (Kg) Water, fusionH 334 J g
Sirreversible

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

ice, -2 degrees ice, 0 degrees w ater, 0 degrees w ater, 35 degrees

Sreversible Sreversible

Sreversible

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 1000C. When re-equilibrated at 1000C, 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 1000C 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.

S
Sirr
Srev2

f
Srev3

i
water

Srev1

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)

vapor

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 : NoWe 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