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Autumn 2012 CHEM452B Bruce H.

Robinson
322 Gould Hall HW 10(A)

Homework 10A KEY (there will not be a 10B)


Q1A) Let c be the speed of sound in air. The square of the speed of sound, c 2 , equals the change in the pressure
(P) of the gas with respect to the change in the density ( ) of the gas, at constant entropy (sound travels
adiabatically) You might check out the Wikipedia on Speed of Sound.

1A) Re-express the above words into an equation (that then will need to be solved to determine the actual speed
P
of sound). c 2
U

1B) To simplify the analysis of the equation of 1A: Evaluate the derivative that relates the density to the molar
volume. (You will need this to simplify the expression of A);
MW C MW
V
dV 2
M W 2 V
d MW
1C) . From this expression, and the cyclic rule, relate the speed of sound to the molecular weight and the
temperature assuming an ideal diatomic gas. Using the above two expressions, relate c 2 to the derivative
S S
P dV P
dV V P V
2 V P
c n
2
n
S d V S d S nM W S

P V P V
S T
CP P
2 T P V P 2
c
2 V V
nM W S T nM W C V

V T

T V P V
I .G . 2 CP P RT CP CP I .G. 7
c2 V
nM W C V MW C CV 5
V V

1D) At room temperature, 25C , what is the speed of sound for an average air atom weighing 29 g/mole.
Compare your answer to the actual speed of sound. Assume air behaves as an ideal gas.
7 RT 7 RT 345 m
c
5 M W 5 M W sec
This answer is extremely close to the experimental speed of sound.

1E) what is the mean square velocity of the gas under the same conditions as D)? Why is the root-means-square
velocity different from the speed of sound?
1
2m v
2
23 RT

3 RT 506 m
1

vrms v 2
M W
2

sec
The speed of sound is a unidirectional propagation which does arise from the mobility of the gas molecules. It
seems to make sense that the velocity of directed information would be slower than the random motion of the
molecules. But realize, the molecular motion is what causes sound to propagate in a medium at all.
Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)
Q2) Show that the reversible work W=-PdV cannot be an equation of state. Use the Universal Equation of state
to show this is not possible.

First use the fact that V is a state function to relate beta and kappa:
2 ln V 2 ln V

PT T P


P T T P
Now, using that use the Euler test on the work:
PdV PV dT PV dP
dw
2w 2w

PT T P
PV PV

P T T P
PV PV
PV PV
P T P T T P T P
PV PV

P T T P
V V
V P P
P T T P
1 V V 1 V V
V P P
V T P P T V P T T P
V 0

Q3) For a simple A to B transition (which can include a chemical reaction), it is instructive to realize all needed
quantities follow from the chemical potential. Primarily we are thinking of a transition such as ice to water but it
applies to a change between any two states. The general expressions are given:
B A Using dG Expression d SdT VdP
Let us assume that the chemical potential has a simple dependence on the pressure and temperature:
T 2 P2 [This dependence is not necessarily true for any system, it is made up to show how the
chemical potential is used to derive the phase transition -- or the equilibrium status of a chemical reaction.]

3A) The first item is: Find the relation of T and P when the two phases are in equilibrium.
0 T 2 P 2

P T

3B) Show that you can get H and S both from the chemical potential. Give explicit equations for
H and S this this particular cases of
Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)

S 2 T and V 2 P
T P P T

T 2 P 2

H T 2 T T 2 T
T P
2 2
T T
P P

3C) Part B) gave H and S , from the chemical potential. Now show that H T S equals the original .
T S 2T 2 H T 2 P 2
H T S T 2 P 2

3D) Show, for equilibrium (or coexistence) H T S (Notice this is only true at equilibrium, not all the time,
but it is consistent with the original result in A).
T S 2 T 2 H T 2 P 2
2

H T S T P T
2 2 2
T 0

3E) Derive from the chemical potential an expression for: V



V 2 P
P T

3F) Using the general form of the chemical potential, develop the Clausius Clapeyron Equation
0 d SdT VdP
dP S

dT V
dT H
dP
T V

3G) Solve the general Clausius-Clapeyron equation for the specific from of the enthalpy, H , you found in C)
and obtain a relation between P and T. [It is not supposed to look like anything else you have seen.]
H T 2 P 2 2 T 2
dT H dT 2 T 2 dT T
dP
T V T 2 P P

PdP TdT


PdP TdT
P 2 Po2 T 2 To2
Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)
3H) Show that the result of P as a function of T is the same as you found in 3A), but now you went through the
differential forms and the expression for the enthalpy.

From 2A got that 0 now we get the analogous answer that 0 0 d .

4A) Breathalyzer tests are based on Henrys law. A sample of breath taken from a driver has a partial pressure
of ethanol which is 1.0 106 atm. What is the percentage by weight of ethanol in the breath? Assume ethanol
forms a Henrys Law solution in the saliva and that ethanol in the breath is in equilibrium with ethanol in the
saliva. Assume the Henrys Law constant for ethanol is 1.0 103 atm. The vapor pressure of pure ethanol is
much higher than water. Ethanol boils at 78.4C, and at 25C has a vapor pressure of 59.2 mmHg or torr.
PEtOH EtOH K H EtOH H 2O
1.0 106 EtOH 1.0 103
EtOH 1.0 103
We now have the mole fraction but need the weight fraction. Assume in water of 18g/mole, ethanol is 46
g/mole. In an arbitrary volume, V, the mass fraction of ethanol is:
m m n 46
f et et et 2.56 EtOH 2.56 103 0.26%
msol mwater nwater 18
Is the person drunk? In the breath finding 0.1 mg EtOH in 1 liter of air (breath) converts to 0.021 g EtOH in a
deciliter of blood (this 0.021% of alcohol). The legal max limit is 0.08% in the blood.
The density of water is 1 gram/cc or 1 kg/liter or 100 grams in one deciliter. Using the above mass fraction
then there is 0.26 grams of ethanol in the persons blood which is indeed way over the limit 26/8 = 3 times legal
max.

Q5) Imagine an ideal solution in equilibrium with its vapor. Let the mole fraction of component i in solution =
xi. Let the mole fraction of component i in vapor = yi. The partial pressures of the gaseous components are Pi =
yi P where P is the total pressure and Pi = P and yi = 1.One way of writing Raoults Law is Pi = xi
P, where xi = 1. (Reading Section 8.3 in the text will be useful for answering these questions) The point of
the exercise is simply to understand something about bubble points, dew points, and boiling points of mixtures.

a. For a binary mixture of two components (1 and 2), find an equation for P using only P1*, P2*, and x1.
This is the bubble point line. If the pressure on a binary solution is reduced from a high value, once the
pressure crosses the bubble point, bubbles of vapor will form in solution. Think of a bottle of Coke or
beer. The contents are under pressure. When you open the bottle, the pressure drops and bubbles form
in solution.
Pi xi Pi* yi P
P Pi xi Pi * x1P1* 1 x1 P2* P2* x1 P1* P2*
i i

x1 P1*
b. Find an equation for y1 using only P1*, P2*, and x1.
Answer : y1

P2 P1 P2 x1
* * *

Pi xi Pi yi P
*

x1 P1* x1 P1*
y1 *
P P2 x1 P1* P2*
Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)
c. Rearrange the equation from part (b) to find an equation for x1 using only P1*, P2*, and y1.

x1 P1* y1 P2* x1 P1* P2* y1 P2* y1 x1 P1* P2*

x1 P1* y1 x1 P1* P2* y1 P2*


y1 P2*
x1
P1* y1 P2* P1*
P1* P2*
d. Use the information above to verify that: P
P1 P2 P1 y1
* * *

y1 P2*
x1
P1* y1 P2* P1*
y1 P2* P1*
x1 P1* y1 P
P1* y1 P2* P1*
x1 P1* P2* P1*
* P
y1 P1 y1 P2* P1*
This equation relates the total pressure to the mole fraction of component 1 in the vapor phase. This is
the equation for the dew point line. At low pressures the system is in a vapor. When the pressure is
raised to when it crosses the dew point line, condensation causes droplets of liquid to form.
e. The same definitions above can be used to understand how solutions boil. Given that a toluene-benzene
solution boils at 100C at 1.00 atm, and that P1* = 0.742 atm and P2* = 1.800 atm, find:
i. the mole fraction x1 of toluene in the solution (Answer: x1 = 0.76)
Pi xi Pi * yi P
P P2* x1 P1* P2*
1 1.80 x1 0.742 1.80

x1
1 1.8 0.756
0.742 1.80
ii. the mole fraction y1 of toluene in the vapor (Answer: y1 = 0.56)
x P* 0.756 0.742
y1 1 1 0.56
P 1.0

Q6) Benzene (Bnz) and Acetone (Ace) form an ideal solution at 300K (i.e. the mixture obeys Rauolt's law). and
*
PAce 250.Torr and PBnz
*
100.Torr .[You should sketch a pressure v. composition diagram. It might help in
grading.]
A) The pressure is reduced on the liquid (mixture) until the first vapor forms and the vapor at this point is 75%
benzene, yBnz 0.75 . What is the total pressure on the vapor at this point?
The best way to work this on an exam is go in a different order. The direct expression is rather awkward and takes a
while to develop, but as we have it above,
P2* P1* 100 250
P 117.65torr

P1 y1 P2 P1
* * *
100 0.75 250 100
B) What is the mole fraction of the acetone in the liquid?
Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)
Pi xi Pi* yi P
y2 P 0.25 117.
x2 0.117
P2* 250
C) If the pressure is reduced further, when the last trace of liquid disappears what is the mole fraction of acetone in
the vapor? y2 0.117 , relative composition does not change but we move from a liquid to a vapor (or gas).

D) If the pressure is reduced further, at what pressure does the last trace of liquid disappear? Qualitatively we will
be very close (but above) 100 torr. Given y2 0.117 , we can directly compute the total pressure.
Pi xi Pi * yi P
yi P .117 .878
1 xi P
250 100
*
i i Pi
1
P 108.
.117 .878

250 100

E) What is the mole fraction of acetone in the last trace of liquid?


Pi xi Pi * yi P
x2 P2* y2 P 0.117 108
y2 P 0.117 108
x2 0.05
P2* 250
It is almost pure benzene at this point. Just as the vapor is enriched by the more volatile component, now the
liquid is enriched by the less volatile component (the benzene).

Additional practice question for the final exam:

EQ1) Osmotic Pressure


The Columbia river drains into the Pacific Ocean at a rate of 7,500 m3 of water/sec. The river is fresh water,
and the ocean is salt water, which is about 1 M in ions total (not worrying about which kind, but basically
NaCl).
A) If there were a semi-permeable membrane that let water through but not salt, how great would the osmotic
pressure be between the ocean and the river?
csolute RT 1 0.082 298 25 Atm

B) One atmosphere of osmotic pressure will raise water 32 feet or 10 meters. Using the osmotic pressure how
high would the ocean rise compared to the fresh water?
h 10 25 250 meters
C) This membrane then could act like a dam with the height given by part B). How much energy would be
captured by a turbine run by the water falling over a barrier such as this? [Hint: Compute the potential energy
difference for the water from the top to the bottom of a height generated by the osmotic pressure.] The mass of
water is 1 kg/liter or 103 kg/m3.
PE mgh 103 9.8 250 J 3 2.4 MJ 3
m m
D) [Following what you did in part C).] What is the potential energy output (in Joules) for one cubic meter of
water to fall 200 meters? PE mgh 103 9.8 200 J 3 1.9 2 MJ 3
m m
Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)

E) A typical power plant generates 600 MW or 600 106 J sec . Given that the Columbia drains 7,500 m3 sec
of water how many power plants could be replaced by a 200 meter high dam at the mouth of the Columbia?
[The US uses about 5000 such plants for the entire US electrical need.]
3
PE 2 MJ 3 7.5 103 m 15 103 MJ
m sec sec
15 103 MJ
PE sec 25 power plants
600 MJ
sec/ power plant

EQ2) Water boils at 100C at one atmosphere, the heat of vaporization is H vap 40 kJ mole .
[Explain what approximations you use to determine your results?] Water is 55M, or 0.018 mole
.
A) What is the partial pressure of the water above a 2.0 M NaCl solution of water at 100C?

The chemical potentials of the water is lowered, so the gas must do the same (at 100C).
P
g g o RT ln g
Po
o RT ln
Po Po Pg Pg 4.0
1 salt 1 1 0.073
Po Po 55
Po Pg
0.073
Po
P 0.927 Atm

At 100C, expect water to be nearly boiling, but now salt is added and this reduces the partial pressure by
making the liquid more stable.

B) At what temperature will the solution from part A) boil?

Use the C.C. equation and notice that the pressure is .927 at 100C and want to find T where P=1Atm
P H T
ln 2
P1 RT1 T2
1 40 T
ln
0.927 8.3 0.373 T2
T
0.006
T2
T2 102.2C
Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)
EQ3) Benzene and Toluene form an ideal solution at 300K (i.e. the mixture obeys Rauolt's law).
*
Ptoluene 30.0Torr and PBenzene
*
90.0Torr . The liquid is composed of 3 moles of toluene and 2 moles of
benzene. [You may want to sketch a pressure vs. composition diagram.] B=benzene, A=toluene
a) At what pressure does the first vapor form?

P Pi xi Pi* .4 90 .6 30 1.2 .6 30 54torr


Pure liquid is .4 mole fraction Benzene, and .6 Toluene.

b) What is the composition of the first trace of vapor formed?

Pi xi Pi * yi P
xi Pi* .4 90
yi 0.67 torr Benzene
P 54
c) If the pressure is reduced further, at what pressure does the last trace of liquid disappear?

yBenzene 0.4
yi .4 .6
1 xi P P
90 30
*
Pi
1
P 41.0 torr
.4 .6

90 30
d) What is the composition of the last trace of liquid?

Pi xi Pi * yi P
yi P 0.4 41
xi 0.18 torr Benzene
Pi * 90
This set of questions is very similar to the one above with Acetone and Benzene. Now the benzene is the
more volatile component.

EQ4) The partial pressure of ethanol and water as a function of the mole fraction, at 25C, are given.

EtOH PEtOH torr PH2O torr


Autumn 2012 CHEM452B Bruce H. Robinson
322 Gould Hall HW 10(A)

Using this data determine Henrys constant for ethanol in water and water in ethanol.

As developed in class the Henrys constant is found in the limit as the mole fraction of ethanol goes to zero for
the Henrys law constant of ethanol, where the water is taken to satisfy Raoults law (in this limit, as the
solvent).
PEtOH PH 2O P EtOH K EtOH torr 1 EtOH PH*2O torr
PEtOH PH 2O 1 EtOH PH*2O
K EtOH
EtOH
EtOH 0.02 .05 0.08 1.0
K H = 214.2800 200.7800 187.9050 179.4800
lim K H =223torr=0.3Atm
0