Chem 338 Homework Set #4 solutions From Atkins: 4.2, 4.4, 4.6, 4.12, 4.18, 4.19, 4.

22 September 25, 2001

4.2) Suppose you put a cube of ice of mass 100 g into glass of water at just above 0C. When the ice melts, about 33 kJ of energy is absorbed from the surroundings as heat. What is the change in entropy of (a) the sample (the ice), (b) the surroundings (the glass of water) ? +33 kJ o a) S sys = = +0.12 kJ K -1 273 33 kJ o = = 0.12 kJ K -1 b) S surr 273 4.4) Calculate the change in entropy of 100 g of ice at 0C as it is melted, heated to 100C, and then vaporized at that temperature. Suppose that the changes are brought about by a heater that supplies heat at a constant rate, and sketch a graph showing (a) the change in temperature of the system, (b) then enthalpy of the system, (c) the entropy of the system as a function of time. 100 g H2 O(s) 0C amount of ice:
o S1 o S2 o S 3

H2 O(l) 0C

H2 O(l) 100C

H2 O(g) 100C

n = 100 g

1 mol = 5.5509 mol 18.015 g

nH o q fus (5.5509)(6.01) o S1 = rev = = = 0.12213 kJ / K 273.15 T T

o S2 = nC p,m ln

Tf Ti

= (5.5509)(0.07529) ln

373.15 = 0.13038 kJ / K 273.15

o o nH vap (5.5509)( 40.7) S 3 = = = 0.60544 kJ / K T 373.15 o o o o = S1 + S2 + S 3 = 0.858 kJ / K = 860 J / K S total

Total heat input into the system:

o q = H o = nH o fus + nC p,m T + nH vap

= 33.361 + 41.793 + 225.92 = 301 kJ For a constant rate of heat input into the system:

Temperature vs. time (as in the last homework set)

100C

liquid to gas phase change

Temp
warming of liquid from 0C to 100C

0C

ice to liquid phase change

Time

Enthalpy vs. time (note: q = H and q is being delivered at a constant rate) 301

H (J)

0 0 Time

Entropy vs. time

860

liquid to gas phase change

S (J)
warming of liquid from 0C to 100C (varies as ln T) ice to liquid phase change

0 0

Time

4.6) A sample of carbon dioxide that initially occupies 15.0 L at 250 K and 1.00 atm is compressed isothermally. Into what volume must the gas be compresed to reduce its entropy by 10.00 J K-1 ? First calculate the number of moles of gas: n= pV (1.00)(15.0) = = 0.7312 mol RT (0.0820578)(250)

For the isothermal expansion/compression of a perfect gas: S o = nR ln Solving for Vf: V f = Vi e

S nR

Vf Vi

For an entropy change of 10.0 J/K : V f = (15.0)e = 2.90 L 4.12) Calculate the change in entropy when 100 g of water at 80C is poured into 100 g of water at 10C in an insulated vessel given that Cp,m = 75.5 J K-1 mol-1. We first need to find the final temperature. Since the amounts of hot and cold water are the same, the final temp is just the average of the initial temperatures: (80 + 10)/2 = 45C. More rigorously, this is obtained by noting that the heat lost by the hot water is exactly equal to the heat gained by the cold water since the container is insulated: qlost by hot water = qgained by cold water nh C p,m (T f 353) = nc C p,m (T f 283) and thus, T f = 318 K (45C) since nh = nc
10.0 (0.7312)(8.31451)

Since entropy is a state function we can break down this process into two steps, the cooling of the hot water and the heating of the cold water: S = S hot + Scold 318 318 = nh C p,m ln + nc C p,m ln 353 283 In each case, the amount of water is: n = 100 g 1 mol = 5.5509 mol 18.015 g

S = (5.5509)( 75.5)[ 0.1044 + 0.1166] = 5.11 J / K 4.18) Calculate the standard reaction entropy at 298 K of (a) 2CH3CHO(g) + O2(g) 2CH3COOH(l)
o o o In each case, S r is given by p S m r Sm prod reac o S r = 2(159.8) [2(250.3) + (205.138)] = 386.1 J K -1 mol-1

(b) 2AgCl(s) + Br2(l) 2AgBr(s) + Cl2(g)

o S r = 2(107.1) + (223.07) [2(96.2) + (152.23)] = 92.6 J K -1 mol-1

(c) Hg(l) + Cl2(g) HgCl2(s)

o S r = (146.0) [( 76.02) + (223.07)] = 153.1 J K -1 mol-1

(d) Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

o S r = ( 112.1) + ( 33.150) [( 41.63) + ( 99.6)] = 21.0 J K -1 mol-1

(e) C12H22O11(s) + 12O2(g) 12CO2(g) + 11H2O(l)

o S r = 12(213.74 ) + 11(69.91) [( 360.2) + 12(205.138)] = 512.0 J K -1 mol-1

4.19) The constant-pressure molar heat capacities of linear gaseous molecules are approximately 7/2 R and those of nonlinear gaseous molecules are approximately 4R. Estimate the change in standard reaction entropy of the following two reactions when the temperature is increased by 10 K from 273 K at constant pressure. (a) 2H2(g) + O2(g) 2H2O(g) This problem is analogous to the derivation of Kirchhoffs law for the determination of the temperature dependence of the enthalpy. Using this first reaction as an example, here is the path that we should consider:
o S283

2H2 (g) + O2 (g)

S 1 S 2

2H2 O(g)
S 3

2H2 (g) + O2 (g) Where, S1 = nC lin p,m ln S2 = nC lin p,m ln

o S273

2H2 O(g)

273 7 R) ln 273 = 2( 2 283 283 273 7 R) ln 273 = (2 283 283 283 283 = 2( 4 R) ln 273 273

lin S 3 = nC non ln p,m

o o S283 = S1 + S2 + S273 + S 3 o o or, S283 S273 = S1 + S2 + S 3

But we can write the sum of the three entropy terms as: 283 S1 + S2 + S 3 = r C p ln 273
prod reac where, r C p = p C p ,m r C p,m (as in Kirchhoffs law) prod reac

7 R) ( 7 R) = 2.5 R = 20.786 J K -1 mol-1 r C p = 2 ( 4 R) 2 ( 2 2 o o S283 S273 = ( 20.786) ln

283 = 0.75 J K -1 mol-1 273

(b) CH4(g) + 2O2(g) CO2(g) + 2H2O(g) For this reaction,

non lin lin r C p = C lin C non + 2C lin p + 2C p p p 7 +847 = 1R =R 2 2

283 o o S283 R S273 = (1 ) ln = +0.15 J K -1 mol-1 2 273

4.22) The change in Gibbs energy that accompanies the oxidation of C6H12O6(s) to carbon dioxide and water vapour at 25C is 2828 kJ/mol. How much glucose does a person of mass 65 kg need to consume to climb through 10 m? C6H12O6(s) + 9O2(g) 6CO2(g) + 6H2O(g)
o Gr yields the maximum non-expansion work (like climbing),

work = mgh, for 65 kg through 10 m : work = (65)(9.81)(10) = 6376.5 J 1 mol glucose 2828 10 J
3

# moles of glucose = 6376.5 2.25 10 3 mol

= 2.25 10 3 mol

180.16 g = 0.41 g of glucose mol