CHEM151 PHYSICAL CHEMISTRY

PROBLEM SET NO. 1 Gases

1. Give the basic assumptions/postulates of the kinetic
assumptions/postulates always true? (Source: Timberlake)

molecular

theory.

Are

these

In relation to gases, there are five assumptions made by the kinetic molecular theory:
1. A gas consists of small particles (atoms or molecules) that move randomly with high velocities
2. The attractive forces between particles of a gas are usually very small
3. The actual volume occupied by gas molecules is extremely small compared with the volume that
the gas occupies
4. Gas particles are in constant motion, moving rapidly in straight paths
5. The average kinetic energy of gas molecules is proportional to the Kelvin temperature
As with other scientific postulates, these are always dependent on the state of the system. Though
the five assumptions may hold true in general, assumptions 1 and 2 tend to fail in circumstances of
higher pressure. High pressures mean lower volume, and so there is restricted motion and the
attractive forces tend to increase as the particles get close together.
2. Oxygen is pumped into a tank to supply breathing air for scuba diving, until the gas pressure
reaches 5.04 atm. Helium is then pumped in until the total pressure is 20 atm. The gases mix
completely. What is the partial pressure of each gas in the tank?
Given:

PO2 = 5.04 atm (partial pressure of oxygen)

PT = 20 atm (total pressure of tank)
PHe = ?

According to Daltons Law, the total pressure of a gas mixture is the sum of the partial pressures of
the gases in the mixture. So in this case, PT = PO2 + PHe. PO2 and PT are already given, so solving for
PHe:
PHe = PT PO2
PHe = 20 atm 5.04 atm
PHe = 14.96 atm
So the partial pressures of each gas are 5.04 atm for O2 and 14.96 atm for He
3. Freon-12 is used as a refrigerant in central home or air conditioners. The rate of effusion of
Freon-12 to Freon-11 (molar mass = 137.4 g/mol) is 1.07:1. The formula of Freon-12 is one of the
following: CF4, CF3Cl, CF2Cl2, CFCl3, or CCl4. Which formula is correct for Freon-12?
Since the problem deals with the rate of effusion of the gas, it utilizes Grahams law of diffusion. The
rate of effusion of a gas has the same form as Grahams law of diffusion, save for the fraction on the
left side of the equation.
Given:

t2 = 1.07 (effusion rate for Freon-11)

t1 = 1 (effusion rate for Freon-12)
M2 = 137.4 g/mol (molecular mass of Freon-11)
M1 = ? (molecular mass of Freon-12)

Substituting given values into the effusion form of Grahams law:

t2
=
t1
1.07
=
1

M2
(Graham' s law of diffusion - adapted for effusion)
M1
137.4 g/mol
M1

Squaring both sides to remove square root

2
137.4 g/mol
1.07

=
M1
1

137.4 g/mol
1.1449 =
M1
137.4 g/mol
M1 =
1.1449
M 1 = 120.01 g/mol

Having a calculated molecular mass for Freon-12, correlating with the molecular masses of the
available formulas and determining the correct one accordingly:
Using C = 12.011, F = 18.998 and Cl = 35.45:
CF4 = 88.003 g/mol
CF3Cl = 104.455 g/mol
CF2Cl2 = 120.907 g/mol
CFCl3 = 137.359 g/mol
CCl4 = 153.811 g/mol
Since the calculated M1 lies closest to CF2Cl2, it can be considered as the correct formula for Freon-12.
4. Consider two (2) gases, A and B, each in a 1.0L container with both gases at the same
temperature and pressure. The mass of gas A in the container is 0.25 g and the mass of gas B in
the container is 0.51 g.
a. Which gas sample has the most molecules present?
b. Which gas sample has the largest average kinetic energy?
c. Which gas has the highest velocity?
d. How can pressure in the two containers be equal to each other since the larger gas B
molecules collide with the container walls more forcefully?
a. Considering that temperature, pressure and volume are constant, it is safe to assume that the
number of moles is also constant. This means that both containers have equal number of
molecules present for that particular gas.
b. Seeing that kinetic energy is related to the temperature of the system (which in this case is
kept constant), the average kinetic energy will be the same for both samples.
c. Since gas sample A is lighter, this means that the gas particles are smaller. By this token, the gas
particles are moving faster and so gas A has the highest velocity.
d. All things considered, this can be looked at in a matter of how the gas particles in each container
collide with the walls. True, one might think that the heavier gas molecules of gas B yield higher
pressure because they hit the walls with more force, but in reality the pressures are equal. This is
because of the fact that since the molecules of gas A are smaller, they have a higher velocity than
the gas B molecules. So instead of colliding with the container walls more forcefully like gas B, gas
A collides with the walls more frequently.

5. Helium is collected over water at 25C and 1.00 atm total pressure. What total volume of gas
must be collected to obtain 0.492 g of helium? (At 25C the vapor pressure of water is 23.8 torr)
Given:

PT = 1.00 atm or 760 torr

PH2O = 23.8 torr
T = 25C or 298K
mHe = 0.492 g

(total pressure)
(vapor pressure of water)
(temperature)
(mass of helium obtained)

In order to solve for the volume of collected gas, first the pressure of helium in the system should be
solved for. In a system such as this, helium isnt the contributor to the total pressure of the system,
because water vapor does so as well. PT and PH2O are given so solving for PHe
PT = PHe + PH2O
PHe = PT - PH2O
PHe = 760 torr 23.8 torr
PHe = 736.2 torr
Considering ideality, the ideal gas equation can be modified to calculate for the volume necessary.
PV = nRT
The number of moles (n) can be rewritten as:
number of moles (n) =

mass of compound
m
=
molecular mass of compound

Plugging this in place of n in the ideal gas equation:

m
RT

Solving for V :

PV =

mRT
P
Plugging in all given values :
V=

(0.492 g)(0.0821
V=
(736.2 torr .

L.atm
)(298K)
K.mol

1 atm
)(4.003 g/mol)
760 torr

V = 3. 1 L

The volume of helium gas to be collected to get a mass of 0.492 g is 3.1 L

6. Natural gas in a mixture of hydrocarbons, primarily methane (CH4) and ethane (C2H6). A typical
mixture might have Xmethane = 0.923 and Xethane = 0.077. What are the partial pressures of the two
gases in the 14.00 L container of natural gas at 21C and 1.48 atm? Assuming complete
combustion of both gases in the natural gas sample, what is the total mass of water formed?
This problem primarily utilizes Daltons Law of Partial Pressures. X represents what is known as the
mole fraction, or an expression of the ratio of the number of moles of one component to the number
of moles of all components present (courtesy of Raymond Chang).

Given:

Xmethane = 0.923
Xethane = 0.077
PT = 1.48 atm
T = 21C or 294 K
V = 14.0 L

(mole fraction of methane)

(mole fraction of ethane)
(total pressure)
(system temperature)
(system volume)

Required formula:
Pi = XiPT

where:

Pi = partial pressure of component i

Xi = mole fraction of component i
PT = total pressure

Pmethane = Xmethane . PT
Pmethane = 0.923 x 1.48 atm
Pmethane = 1.37 atm
Pethane = Xethane . PT
Pethane = 0.077 x 1.48 atm
Pethane = 0.11 atm
The partial pressures of both methane and ethane in the container are 1.37 atm and 0.11 atm
respectively. Now calculating for the total number of moles of gas in the container using the ideal gas
equation.
PV = nRT
PV
RT
Substituting given values :

n=

(1.48 atm)(14.0 L)
L.atm
(0.0821
)(294K)
K.mol
n = 0.858 moles

n=

Using the mole fraction equation to find the number of moles of each gas :

Required formula:
Xi = ni / nT
or ni = XinT

where:

ni = number of moles of component i

Xi = mole fraction of component i
nT = total number of moles in system

nmethane = 0.923 x 0.858 moles

nmethane = 0.791 mol CH4
nmethane = 0.077 x 0.858 moles
nmethane = 0.066 mol C2H6
Treating the two combustion processes separately and determining how many moles of water each
gas component forms through stoichiometry:
Methane
0.791 mol CH 4 x

CH4 + 2O2

CO2 + 2H2O

2 mol H 2 O
= 1.582 mol H 2 O
1 mol CH 4

Ethane
0.066 mol C 2H6 x

2C2H6 + 7O2

4CO2 + 6H2O

6 mol H2 O
= 0.198 mol H2 O
2 mol C 2H6

Therefore total number of moles of H2O formed is 1.582 mol + 0.198 mol = 1.78 mol H2O
Converting from moles to mass of water formed:
mass H 2 O = 1.78 mol H 2 O x

18.02 gl H 2 O
= 32.1 g H 2 O
1 mol H 2 O

7. A compound contains only nitrogen and hydrogen and is 87.4% nitrogen by mass. A gaseous
sample of the compound has a density of 0.977 g/L at 710 torr and 373K. What is the molecular
formula of the compound?
For the sake of simplicity, assume that there is a 100 g sample of the compound. Since it is 87.4%
nitrogen, then by gram virtue the 100 g sample is essentially 87.4 g of nitrogen and the rest is
hydrogen, which is 12.6 g. Looking for an empirical ratio between the two using simple proportioning:
1 mol N
= 6.24 mol N
14.01 g N
1 mol H
12.6 g H x
= 11.7 mol H
1.08 g H
87.4 g N x

Since nitrogen exists in the largest amount, using it as a reference for the ratio:
6.24 mol
=1
6.24 mol
11.7 mol
Ratio of H =
=2
6.24 mol

Ratio of N =

Given the ratio the empirical formula of the compound is NH2. Calculating for the molecular formula
of the compound using the given information:
Required formula (modified ideal gas equation to calculate for densities, etc.):
d = PM / RT
or M = dRT/P

Where:

d = density of the gas

R = gas constant
T = Kelvin temperature
P = system pressure
M = molecular weight

Substituting values into the equation to find for molecular weight:

g
L.atm
(0.977 )(0.0821
)(373K)
L
mol.K
M=
1 atm
710 torr x
760 torr
M = 32.03 g/mol

Since the molecular weight is simply just the empirical weight doubled, then the molecular formula is
simply double that of the empirical formula. The compound can be assumed to be N2H4.

8. Balloons now are used to remove huge trees from their cutting place on the mountain slopes to
conventional transportation. Calculate the volume of a balloon needed if it is desired to have a
lifting force of 1000 kg when the temperature is 290K at 0.940 atm. The balloon is filled with
helium. Assume that the air is 80 mol % N2 and 20 mol % O2. Assume that the entire assembly is
weightless.
The first step is to calculate for the molecular weight of air. According to the question, the air is 80
mol % N2 and 20 mol % O2. By principle, there will be 28 g/mol of nitrogen and 32 g/mol of oxygen in
the air (based on their diatomic nature). Taking 80% and 20% of these respectively, we 22.4 g/mol of
nitrogen and 6.4 g/mol of oxygen, and totaling both we get the molecular weight of air, which is 28.8
g/mol.
Using the form of the ideal gas equation that contains density and solving for the density of the air
and the helium that will be added:
dair =

PM
RT

Pa
)(28.8 g/mol)
atm
dair =
J
1000 g
(8.3145
)(290K)(
)
K.mol
1 kg
kg
dair = 1.138 3
m
(to check that units cancel out, Pa is N/m 2 , and J is N.m)
(0.940 atm)(101,3 25

Pa
)(4.003 g/mol)
atm
=
J
1000 g
(8.3145
)(290K)(
)
K.mol
1 kg
kg
= 0.158 3
m
(0.940 atm)(101,3 25

dhelium

dhelium

The lifting force is essentially the product of the volume of the balloon multiplied by the difference in
the densities of the interacting gases, which is air and helium. In equation form:
Vballoon(dair dhelium) = 1000kg
Rearranging and solving for Vballoon:
Vballoon =
Vballoon =

1000 kg
d air - dhelium
1000 kg
(1.138 - 0.158)

Vballoon = 1021 m

Big balloon, shit.

kg
m3

9. The gravitational constant g decreases by 0.010 m s-2 km-1 of altitude.

a. Modify the barometric equation to take this variation into account. Assume that the
temperature remains constant.
b. Calculate the pressure of nitrogen at an altitude of 100 km assuming that sea-level pressure is
exactly 1 atm and that the temperature of 298.15 K is constant.
PART A
This problem requires the use of the barometric equation, which in its differential form is shown
below (formula obtained from somewhere in Levine nakalimutan ko kung saan katamad na hanapin):
dP
Mg
=
dh
P
RT

Owing to the fact that there is a decrease of g by 0.010 m/s2 for every kilometer, then for every
second the change in the gravitational acceleration is:
0.010

s 2 = 10 5 s -2 h
1000 m

The h is the height travelled, and has to be considered. Given that this is the change to the original
value for gravitational acceleration, then in this scenario it expression for g would be as follows:
g = 9.807 m/s2 10-5 s-2 h
This can be substituted into the original barometric equation, which will now become:
dP
M
=
(9.807 m/s 2 - 10 -5 s -2 h) dh
P
RT

PART B
In order to calculate for the pressure of nitrogen at a particular height, the barometric equation
shown above should be integrated accordingly using simple calculus:
M

P dP = RT 9.807 s
P
ln P 0

dh 10 5 s 2 h dh

h
M
m
10 5 s 2 h 2
9
.
807
h
=

RT
2
s2 0

P
M
m
6 2 2
ln =
9.807 2 h 5x10 s h
P
RT
s

0
Substituting in the provided values :
g
28.0

5
6 2
5
2
mol
=
9.807 2 (10 m) 5x10 s (10 m)

J
s

(8.314
)(298.15 K)
K.mol
P
ln = 10.51
P0
Taking both sides to the base e :

P
ln
P0

P
ln e = e 10.51
P0
P
= e 10.51 = 2.73 x 10 -5
P0
Since original pressure is 1atm, then the pressure of nitrogen at 100 km is 2.73 x 10 -5 atm

10. Suppose that on another planet where the atmosphere is ammonia that the pressure on the
surface, at h = 0, is 400 torr at 250 K. Calculate the pressure of ammonia at a height of 8000 m.
The planet has the same g value has the earth.
This question uses the exact same principle as the previous one, working on the differential form of
the barometric equation, and then integrating it to calculate for the pressure of ammonia at that
particular height.
dP
Mg
=
dh
P
RT
1
Mg
dP =
dh
P
RT

ln P 0 =

Mgh
RT 0

P
Mgh
ln =
RT
P0
Taking both sides to the base e :
P
ln e
P0

Mgh

= e RT

Mgh

P
= e RT
P0

Solving for P to find the pressure of ammonia at a height of 8000 m. Make sure to first convert the molecular
weight of ammonia into kilograms so that the units cancel out correctly (the J in the denominator). Plugging in
all necessary information as obtained from the problem.
P = P0 e

(0.017)(9.807)(8000)
(8.314)( 250)

P = (400 torr) . e

(0.017)( 9.807)(8000)
(8.314)(250)

P = (400 torr) . e 0.642

P = 210.5 torr