Chemistry 520 - Problem Set 3

Due Wednesday January 27, 1999 by 5 P.M.

1. Chang, Problem 4.13 (page 4.48)

Initially: P = 14:0 atm, T = 298 K, n = 1:00 mol, making V = nRT=P = 1:75 L.
(a) After the expansion, P = 1:00 atm, n = 1:00 mol, V = 23:5 L making T =
PV=nR = 286 K
(b) w = ,Pex
V = 1:00 atm  (23:5 , 1:75) L = ,21:75 L atm = ,2204 J.
q = ms
T = 17:03 g  0:0258 J g,1 C,1  (286 , 298)C = ,5:27 J.

U = q + w = ,2209 J.
2. Chang, Problem 4.16 (page 4.48)
Since the process is exothermic (heat is released) q < 0.
Since the number of moles of gas is increasing, the process does work (w < 0)
Since q and w are both negative,
U < 0
Finally,
H =
U +
(nRT ) where n is the number of moles of gas. Because the
second term is on the order of 1 kJ, the magnitude of the rst is much larger and

H < 0.
3. Chang, Problem 4.65 (page 4.55) [Note, the external pressure should be 200 atm.]
Initially, n = 2 mol, T = 298 K and Pi = 1:00 atm. Therefore, Vi = nRT=Pi = 48:90
L
After the compression, n = 1 mol, T = 298 K [isothermal expansion means that
T = const:] and Pf = 200 atm. Therefore, Vf = nRT=Pf = 0:2444 L
For the irreversible process,
w = Pex
V = ,200 atm  (0:1222 , 24:45) L = 9932 L atm = 986 kJ:
Because the process is isothermal,
H =
U = 0
Therefore, q = ,w = ,986 kJ.
For the reversible
process,


w = ,nRT ln Vf =Vi = ,2 mol  8:314 J mol,1K,1  298 K ln(0:2444=48:45) = 26:3
kJ
As in the irreversible case,
H =
U = 0 and q = ,w = ,26:3 kJ.
4. Calculate the work (in joules) done on the system for each of the following examples.
Be sure to specify the sign of the work. To help in identication of the system, I have
written the system in italics.
(a) A box of groceries weighing 10 kg is carried up three ights of stairs (10 m
altogether).
w = F 
z = 10 kg  9:8 m s,2  10 m = 980 J.
1

(b) The volume of an ideal gas changes from 1 L to 3 L at an initial temperature of

25C and a constant external pressure of 1 atm.
w = ,Pex
V = ,1 atm  (3 , 1) L = ,2 L atm = ,203 J.
(c) The volume of an ideal gas changes from 1 L to 3 L at an initial temperature of
25C and a constant external pressure of 10,6 atm.
w = ,Pex
V = ,10,6 atm  (3 , 1) L = ,2  10,6 L atm = ,2:03  10,4 J.
(d) The volume of an ideal gas changes from 1 L to 3 L at a constant temperature
of 25C and the expansion is performed reversibly for an amount of gas that
corresponds to an initial pressure of 1 atm.
n = PiVi=RT = 1 atm  1 L=0:08206 L atm mol,1 K,1  298 K = 0:0409 mol.
w = ,nRT ln(Vf =Vi) = 0:0409 mol8:314 J mol,1 K,1 298 K ln(3=1) = ,111 J
5. Calculate the heat (in joules) absorbed by the system for each of the following examples. Be sure to specify the sign of the heat.
(a) 100 g of liquid water is heated from 0C to 100C at 1 atm.
q = 100 g  4:184 J C,1 g,1  100 C = 41:8 kJ.
(b) 100 g of liquid water is frozen to ice at 0C and 1 atm.
q = 100 g  ,333:4 J g,1 = ,33:3 kJ.
(c) 100 g of liquid water is evaporated to steam at 100C and 1 atm.
q = 100 g  2257 J g,1 = 226 kJ.
6. In the following problem, you will need the following information, the heat of combustion (metabolization) of sucrose is -5644 kJ/mol and its molecular formula is
C12 H22 O11. A Table containing a variety of physical constants for water was handed
out in class.
(a) A hiker, caught in a rainstorm might absorb 1 liter of water in her clothing. If it
is windy so that this amount of water is evaporated quickly at 20C, how much
heat would be required for this process?
q = 1 L  998:2 g L,1  2447 J g,1 = 2443 kJ
(b) If all this heat were removed from the hiker (no signicant heat was generated
by metabolism in this time), what drop in body temperature would the hiker
experience? The clothed hiker weighs 60 kg and you can approximate the heat
capacity of the hiker and clothes as equal to that of water. (The conclusion from
this calculation is to stay out of the wind if you get your clothes wet).

q = ms
T
2:443  10 J = 60  103 g  4:184 J C,1 g,1 
T

T = 9:73 C
6

(1)
(2)
(3)

(c) How many grams of sucrose would the hiker have to metabolize (quickly) to
replace the heat of evaporating 1 liter of water, so that her temperature would
not change?
One mol of sucrose releases 5644 kJ of heat. Therefore, to receive 2443 kJ, one
would need to ingest 2443/5644 = 0.433 mol of sucrose.
Since the molecular weight of sucrose (based on the formula given in the problem)
is 342.2 g/mol, one would need to ingest 148 g of sucrose in order to maintain a
constant temperature.
7. Some of the thermodynamic equations or relations we have discussed are true in
general. Others are true only under restricted conditions, such as constant volume
or for an ideal gas. For each of the following equations, state what are the minimum
conditions sucient to make them true in the framework of chemical thermodynamics:
(a)
U = q + w
Always true!
(b) q =
H
True only for processes performed at constant pressure
(c)
H =
U +
(nRT )
True only for ideal gases.

2 
(d) P + nV 2a (V , nb) = nRT
Never true, but provides a good approximation of the equation of state of real
gases at relatively low pressures.
(e) w = ,Pex
V
When the only work is P-V; and the expansion is performed against a constant
external pressure.