Chem 338

Homework Set #4 solutions September 25, 2001

From Atkins: 4.2, 4.4, 4.6, 4.12, 4.18, 4.19, 4.22

4.2) Suppose you put a cube of ice of mass 100 g into glass of water at just above 0ºC.
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) ?
o +33 kJ
a) ∆S sys = = +0.12 kJ K -1
273
o −33 kJ
b) ∆S surr = = −0.12 kJ K -1
273

4.4) Calculate the change in entropy of 100 g of ice at 0ºC as it is melted, heated to
100ºC, 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.
∆S1o ∆S2o ∆S 3o
100 g H2 O(s) 0°C H2 O(l) 0°C H2 O(l) 100°C H2 O(g) 100°C
1 mol
amount of ice: n = 100 g × = 5.5509 mol
18.015 g

q n∆H ofus (5.5509)(6.01)

∆S1o = rev = = = 0.12213 kJ / K
T T 273.15
Tf 373.15
∆S2o = nC p,m ln = (5.5509)(0.07529) ln = 0.13038 kJ / K
Ti 273.15
o
o n∆H vap (5.5509)( 40.7)
∆S 3 = = = 0.60544 kJ / K
T 373.15
o
∆S total = ∆S1o + ∆S2o + ∆S 3o = 0.858 kJ / K = 860 J / K
Total heat input into the system:
q = ∆H o = n∆H ofus + nC p,m ∆T + n∆H vap
o

= 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)

100ºC liquid to gas phase change

Temp
warming of liquid from 0ºC to 100ºC

0ºC 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 Time

Entropy vs. time

860

liquid to gas phase

change

∆S (J)

warming of liquid from 0ºC to

100ºC (varies as ln T)

ice to liquid phase

0 change

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:
pV (1.00)(15.0)
n= = = 0.7312 mol
RT (0.0820578)(250)
For the isothermal expansion/compression of a perfect gas:
Vf
∆S o = nR ln
Vi
Solving for Vf:
∆S
V f = Vi e nR

For an entropy change of –10.0 J/K :

−10.0
V f = (15.0)e (0.7312)(8.31451)

= 2.90 L

4.12) Calculate the change in entropy when 100 g of water at 80ºC is poured into 100 g
of water at 10ºC 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 = 45ºC.
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 (45°C) since nh = nc
 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
1 mol
In each case, the amount of water is: n = 100 g × = 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)

In each case, ∆S ro is given by ∑ ν p S m

o o
− ∑ ν r Sm
prod reac

∆S ro = 2(159.8) − [2(250.3) + (205.138)] = −386.1 J K -1 mol-1

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

∆S ro = 2(107.1) + (223.07) − [2(96.2) + (152.23)] = 92.6 J K -1 mol-1

(c) Hg(l) + Cl2(g) → HgCl2(s)

∆S ro = (146.0) − [( 76.02) + (223.07)] = −153.1 J K -1 mol-1

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

∆S ro = ( −112.1) + ( 33.150) − [( 41.63) + ( −99.6)] = −21.0 J K -1 mol-1

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

∆S ro = 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 Kirchhoff’s 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) 2H2 O(g)

∆S 1 ∆S 2
∆S 3
o
∆S273
2H2 (g) + O2 (g) 2H2 O(g)

Where,
273 273
∆S1 = nC lin
p,m ln = 2( 27 R) ln
283 283
273 273
∆S2 = nC lin
p,m ln = ( 27 R) ln
283 283
− lin 283 283
∆S 3 = nC non
p,m ln = 2( 4 R) ln
273 273
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
where, ∆ r C p = ∑ ν p C pprod reac
,m − ∑ ν r C p,m (as in Kirchhoff’s law)
prod reac
 ∆ r C p = 2( 4 R) − 2( 27 R) − ( 27 R) = −2.5 R = −20.786 J K -1 mol-1

o o 283
∆S283 − ∆S273 = ( −20.786) ln = −0.75 J K -1 mol-1
273

(b) CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

For this reaction,

∆ r C p = C lin non − lin

p + 2C p [
− C non
p
− lin
+ 2C lin
p ]
( )
= R 27 + 8 − 4 − 7 = 12 R

o o 283
∆S283 − ∆S273 = ( 12 R) ln = +0.15 J K -1 mol-1
273

4.22) The change in Gibbs energy that accompanies the oxidation of C6H12O6(s) to
carbon dioxide and water vapour at 25ºC 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)

∆Gro 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
# moles of glucose = 6376.5 × 3
= 2.25 × 10 −3 mol
2828 × 10 J
180.16 g
2.25 × 10 −3 mol × = 0.41 g of glucose
mol