CHEM 3411, Fall 2010

Solution Set 7

In this solution set, an underline is used to show the last significant digit of numbers. For instance in

x = 2.51693

the 2,5,1, and 6 are all significant. Digits to the right of the underlined digit, the 9 & 3 in the example, are not
significant and would be rounded off at the end of calculations. Carrying these extra digits for intermediate values in
calculations reduces rounding errors and ensures we get the same answer regardless of the order of arithmetic steps.
Numbers without underlines (including final answers) are shown with the proper number of sig figs.

1 Exercise 20.3b pg 777

Given
Consider a sample of CO2 gas (M = 44.010 × 10−3 kg/ mol) at temperature T = 300 K.

In terms of given variables, this is written:

M = 44.010 × 10−3 kg/ mol

T = 300 K

Find
Calculate the fraction of molecules in this gas sample that have speeds in the range vi = 200 m s−1 to vf = 250 m s−1 .

Strategy

For this exercise we’ll begin with the Maxwell distribution of speeds (Equation 20.4 pg 748)

( ) 32
M
v 2 e−M v
2
/2RT
f (v) = 4π
2πRT

Using this speed distribution we can determine the fraction of molecules within a range of speeds p by integrating
this range over the distribution.
∫ vf
p= f (v)dv
vi

Since we’re dealing with a rather narrow range of velocities we can simplify tbe integral by assuming f (v) is roughly
constant over this range of velocities. This allows us to pull f (v) out of the integral and therefore not have to deal
with the complicated integrand. Further, this is how you’d be expected to approach such a similarly complex integral
on an exam.

∫ vf
p= f (v)dv
vi
∫ vf
≈ f (v̄) dv
vi
≈ f (v̄) (vf − vi )

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CHEM 3411, Fall 2010
Solution Set 7

vf −vi
where v̄ is the mean velocity v̄ = 2 .
Substituting in our given values and constants gives.

vf − vi
v̄ =
2
250 m s−1 − 200 m s−1
=
2
= 225 m s−1

p ≈ f (v̄) (vf − vi )
( ) 32
M
v̄ 2 e−M v̄ /2RT
2
≈ 4π
2πRT
( )3
44.010 × 10−3 kg mol−1 2 ( )2 −3 −1 −1 2 −1
≈ 4π −1 225 m s−1 e−44.010×10 kg mol (225 m s ) /(2×8.3145 J K mol 300 K)
2π8.3145 J K mol 300 K
≈ 0.095765

This can be compared to the exact solution where the original integral is integrated to give the following expression
for the fraction of gas molecules.
[ √ ]vf
1 π ( √ ) v −αv2 
p= erf v α − e 
4 α3 2α vi

M
where α = 2RT .
Evaluating this exact expression gives p = 0.0.095438 which is very close the approximate value we found.

Solution

p ≈ 0.0958

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CHEM 3411, Fall 2010
Solution Set 7

2 Exercise 20.9 pg 777

Given
A solid surface with dimensions l = 3.5 mm by w = 4.0 cm is exposed to helium gas (M = 4.0026 g mol−1 ) at a
pressure P = 111 Pa and temperature T = 1500 K for t = 10 s.

In terms of given variables, this is written:

l = 3.5 mm = 3.5 × 10−3 m

w = 4.0 cm = 4.0 × 10−2 m

M = 4.0026 × 10−3 kg mol−1

P = 111 Pa

T = 1500 K

t = 10 s

Find
How many collisions do the helium atoms make with this surface during this t = 10 s exposure.

Strategy
To determine the total number of collisions we’ll begin with the collision flux Zw which tells us the number of
collisions per an area per a second. Therefore the total number of collisions n with a surface of area A during t
seconds is given by

n = Zw At

The area of the surface we’re interested in is simply given as the product of dimensions.

A=l×w

Further, our textbook gives us the following expression for collision flux Zw (Equation 20.14 on page 753)

p
Zw = √
2πmkT
For this expression we can find the mass of each molecule m from the molar mass M by

M
m=
NA
where NA is Avagadros constant.

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CHEM 3411, Fall 2010
Solution Set 7

Putting these pieces together gives us an expression for the number of collisions n.

n = Zw At
plwt
=√
2π NMA kT

Substituting in the given values and constants gives.

plwt
n= √
2π NMA kT
111 Pa × 3.5 × 10−3 m × 4.0 × 10−2 m × 10 s
=√
−3 kg mol−1
2π 4.0026×10
6.022×1023 mol−1
1.38065 × 10−23 J K−1 × 1500 K
= 5.284 × 1021

Solution

n = 5.284 × 1021

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CHEM 3411, Fall 2010
Solution Set 7

3 Exercise 20.12 pg 777

Given
A manometer was connected to a bulb containing nitrogen (MN2 = 28.0134 g mol−1 ) under slight pressure. The gas
was allowed to escape through a small pinhole, and the time for the manometer reading to drop from li = 65.1 cm
to lf = 42.1 cm was 18.5 s When the experiment was repeated using a fluorocarbon gas, the same fall took place in
82.3 s.

In terms of given variables, this is written:

MN2 = 28.0134 g mol−1

li = 65.1 cm

lf = 42.1 cm

tN2 = 18.5 s

tFlc = 82.3 s

Find
Calculate the molar mass of the fluorocarbon MFlc .

Strategy
In solving this exercise we’ll begin by recognizing that the same change in the manometer reading for each experiment
implies that the same number of molecules (either nitrogen or the fluorocarbon) effused out of the bulb in each
experiment. This is stated as

nN2 = nFlc

Where nN2 and nFlc are the number of nitrogen and fluorocarbon carbon molecules respectively that effused out of
the bulb in the respective experiments.
We know that the number of molecules ni (for any molecule type i) that effuse through a surface is given by the
product of rate of effusion Zw,i A0 and the duration of the experiment ti .

ni = Zw,i A0 ti

The rate of effusion Zw,i A0 (the product of collision flux and effusion area) is given by Equation 20.16 on page 754
of our text book.

pA0 NA
Zw,i A0 = √
2πMi RT

This gives us the following expression for the number of molecules of each type i that effuse during each of the
respective experiments.

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CHEM 3411, Fall 2010
Solution Set 7

ni = Zw,i A0 ti
pA0 NA ti
=√
2πMi RT

As we started by recognizing that nN2 = nFlc for the number of molecules that effuse in each experiment, we can
substitute this expression for each ni (where i is either N2 or Flc).

nN2 = nFlc
pA N t pA N t
√ 0 A N2 = √ 0 A Flc
2πMN2 RT 2πMFlc RT
t t
√ N2 = √ Flc
MN2 MFlc

(where the last equation is simplified by removing terms common to each side).
We can solve this equation for the unknown mass of the fluorocarbon MFlc and substitute in the given values.

( )2
tFlc
MFlc = MN2
t N2
( )2
82.3
s
= 28.0134 g mol−1
18.5
s
= 554.40 g mol−1

Solution

MFlc = 554 g mol−1

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CHEM 3411, Fall 2010
Solution Set 7

4 Exercise 20.14b pg 777

Given
There is a temperature gradient of dT
dz = 3.5 K m−1 in a sample of hydrogen gas (M = 2.016 × 10−3 kg mol−1 ) with
a mean temperature of T = 260 K.

In terms of given variables, this is written:

dT
= 3.5 K m−1
dz

M = 2.016 × 10−3 kg mol−1

T = 260 K

Find
What is the flux of energy J arising from this temperature gradient?

Strategy
We can start with the equation of energy flux J in terms of the coefficient of thermal conductivity (Equation 20.20
pg 756)

dT
J = −κ
dz
dT
As we know the temperature gradient dz in our sample, we just need to figure out the coefficient of thermal
conductivity κ for this sample to calculate J. As the sample is at a non-standard temperature of T = 260 K we can’t
just use the tabulated thermal conductivity for hydrogen gas from our textbook as this value is for T = 273 K.
Instead, we’ll assume this hydrogen gas sample is a perfect gas and use kinetic theory to determine the gases transport
properties. Our textbook gives us the following expression for the thermal conductivity of a perfect gas (given in
Table 20.3 and dervied from Equation 20.23 on page 757).

c̄CV,m
κ= √
3 2σNA
We now determine the variables in this expression for κ. The mean speed c̄ is found from the Maxwell distribution
to be (Equation 20.7 pg 750)

( )1/2
8RT
c̄ =
πM
( )
8 × 8.3145 J K mol−1 × 260 K
=
π × 2.016 × 10−3 kg mol−1
= 1652 m s−1

Next we’ll determine the molar constant volume heat capacity CV,m of this sample of gas, and this too is temperature
dependent. As you’ll recall, the temperature dependence of the constant pressure molar heat capacity Cp,m is given
by an expression of the form

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CHEM 3411, Fall 2010
Solution Set 7

Cp,m = a + bT + c/T 2

Using values from Table 2.2 of our textbook we find Cp,m for hydrogen at T = 260 K.

Cp,m = a + bT + c/T 2
J [ ]
27.28 + 3.26 × 10−3
K−1 × 260
2
=   
K + 0.50 × 105
K2 / (260 K)
K mol
J
= 27.91
K mol

We can relate Cp,m to CV,m by the simple relationship

CV,m = Cp,m − R
= 27.91 J K mol−1 − 8.3145 J K mol−1
= 19.59 J K mol−1

Lastly, the collision cross-section σ for hydrogen gas is found from Table 20.1 to be σ = 0.27 × 10−18 m−2 .
With these values we can now calculate κ.

c̄CV,m
κ= √
3 2σNA
1652 m s−1 × 19.59 J K mol−1
= √
3 2 × 0.27 × 10−18 m−2 × 6.022 × 1023 mol−1
J
= 0.04691
Kms

As we’ve found the coefficient of thermal conductivity for our hydrogen gas sample, we can now determine the energy
flux of the temperature gradient.

dT
J = −κ
dz
J
= −0.04691 × 3.5 K m−1
Kms
J
= −0.1642 2
m s

Solution

J
J = −0.16
m2 s

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CHEM 3411, Fall 2010
Solution Set 7

5 Exercise 20.24 pg 778

Given
The mobility of a Li+ ion in aqueous solution is u = 4.01 × 10−8 m2 s−1 V at T = 25◦ C. The potential difference
between two electrodes placed in the solution l = 1.00 cm apart is ∆Φ = 12.0 V.

In terms of given variables, this is written:

u = 4.01 × 10−8 m2 s−1 V

l = 1.00 cm

∆Φ = 12.0 V

Find
What is the drift speed s of the Li+ ion?

Strategy

The drift speed of an ion s can be related to ionic mobility u by the definition of ionic mobility (Equation 20.34 pg
761).

s = uE

where E is the magnitude of the electric field. For the two electrodes with potential difference ∆Φ separted by a
distance l, the electric field magnitude E is given by (Equation 20.30 pg 760).

∆Φ
E=
l
Combining these expressions and substituting in the given values yields the ion drift spped s.

∆Φ
s=u
l
12.0 V
= 4.01 × 10−8 m2 s−1 V
1.00 × 10−2 m
= 4.812 m s−1

Solution

4.8 m s−1

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CHEM 3411, Fall 2010
Solution Set 7

6 Exercise 20.31 pg 778

Given
At T = 25◦ C Glycine in water is found to have a diffusion constant of D = 1.055 × 10−9 m2 s−1 and the viscosity of
water is found to be η = 1.00 cP.

In terms of given variables, this is written:

T = 26◦ C = 298 K

D = 1.055 × 10−9 m2 s−1

η = 1.00 cP = 1.00 × 10−3 kg m−1 s−1

Find
Estimate the effective radius a of a glycine molecule.

Strategy
The diffusion constant of molecule D can be related to its effective radius a by the Stokes-Einstein equation.

kT
D=
6πηa

We can simply rearrange for a as we know the remaining variables.

kT
a=
6πηD
1.38065 × 10−23 J K−1 × 298 K
=
6π1.00 × 10−3 kg m−1 s−1 × 1.055 × 10−9 m2 s−1
= 2.0689 × 10−10 m
= 2.0689Å

Solution

a = 2.07Å

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