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Notes Solutions Chapter 05 Large
Notes Solutions Chapter 05 Large
Notes Solutions Chapter 05 Large
= =
2.08 atm
EP101: Gas Law
Calculate the pressure (in atm) in a container filled with 5.038 kg of
xenon at a temperature of 18.8
o
C, whose volume is 87.5 L.
Strategy:
(1)Convert all information into the units required, and
(2)substitute into the ideal gas equation.
T = 18.8
o
C + 273.15 K = 292.0 K
Xe
5038 g Xe
n = 38.37 mol Xe
131.3 g Xe / mol
=
38.37 mol 0.0821 L atm 292.0 K
87.5 L
nRT
P
V
= = = 10.5 atm
EP102: Sodium Azide Decomposition - I
Sodium azide (NaN
3
) is used in air bags in automobiles. Write
a balanced chemical equation for the decomposition of
NaN
3
into N
2
(g) and Na(s). Calculate the volume in liters of
nitrogen gas generated at 21.0
o
C and 823 mm Hg by the
decomposition of 60.0 g of NaN
3
.
Strategy:
(1) Write balanced equation.
(2) Use stoichiometric coefficients to calculate moles of N
2
.
(3)Convert given parameters into appropriate units.
(4) Calculate V using the ideal gas law.
(1) 2 NaN
3
(s) 2 Na (s) + 3 N
2
(g)
mol NaN
3
= 60.0 g NaN
3
/ 65.02 g NaN
3
/ mol =
= 0.9228 mol NaN
3
mol N
2
= 0.9228 mol NaN
3
x 3 mol N
2
/2 mol NaN
3
= 1.38 mol N
2
T = 273.15 +21.0 = 294.2 K
P = 823 mm x 1 atm/760. mm = 1.08 atm
-1 -1
1.38 mol0.08206 L atm mol K 294.2 K
1.08 atm
nRT
V
P
= = = 30.8 L
EP102a: Calculate the density of ammonia gas
(NH
3
) in grams per liter at 752 mm Hg and
55.0
o
C.
Strategy:
(1) Assume one mole and calculate V for given
conditions.
(2) Use density = mass/volume to calculate density.
P = 752 mm Hg x (1 atm/ 760 mm Hg) =0.989 atm
T = 55.0
o
C + 273.15 = 328.2 K
-1 -1
1 mol0.08206 L atm mol K 328.2 K
0.989 atm
nRT
V
P
= =
= 27.2 L
17.03 g
27.2 L
mass
density
V
= = =
-1
0.626 g L
Calculation of Molar Mass
n = =
P x V
R x T
Mass
Molar Mass
Molar Mass = M =
Mass x R x T
P x V
m
RT
nRT mRT
M
V
P P MP
mRT RT
M
VP P
= = =
= =
EP103: A volatile liquid is placed in 590.0 ml flask and allowed to
boil until only vapor fills the flask at a temperature of 100.0
o
C and
736 mm Hg pressure. If the masses of the empty and gas filled flask were
148.375g and 149.457 g respectively, what is the molar mass of
the liquid?
Strategy:
Use the gas law to calculate the molar mass of the liquid.
Pressure = 736 mm Hg x 1atm/760 mm Hg = 0.968 atm
Mass of gas = 149.457g - 148.375g = 1.082 g
-1 -1
1.082 g 0.08206 L atm mol K 373K
0.968 atm 0.5900 L
mRT
M
PV
= =
=
-1
58.0 g mol
Gas Mixtures
Gas behavior depends on the number,
not the identity, of gas molecules.
The ideal gas equation applies to each
gas individually and to the mixture as
a whole.
All molecules in a sample of an ideal
gas behave exactly the same way.
Daltons Law of Partial Pressures - I
In a mixture of gases, each gas contributes to the
total pressure: the pressure it would exert if the gas
were present in the container by itself.
To obtain a total pressure, add all of the partial
pressures: P
total
= P
1
+P
2
+P
3
+P
N
Pressure exerted by an ideal gas mixture is determined
by the total number of moles:
P=(n
total
RT)/V
n
total
= sum of the amounts of each gas pressure
the partial pressure is the pressure of gas if it was present
by itself.
P
1
= (n
1
RT)/V P
2
= (n
2
RT)/V P
3
= (n
3
RT)/V
the total pressure is the sum of the partial pressures.
P= (n
1
RT)/V + (n
2
RT)/V + (n
3
RT)/V
= (n
1
+n
2
+ n
3
)(RT/V) =(n
total
RT)/V
Partial pressures in terms of mol fractions
1 1
1 1
1 2 3
P n
= P = x P
P n + n + n
EP104: Daltons Law of Partial Pressures
A 2.00 L flask contains 3.00 g of CO
2
and 0.100 g
of helium at a temperature of 17.0
o
C.
What are the partial pressures of each gas, and
the total pressure?
T = 17.0
o
C + 273.15 = 290.2 K
n
CO2
= 3.00 g CO
2
/ (44.01 g CO
2
/ mol CO
2
)
= 0.0682 mol CO
2
2
2
-1 -1
0.0682 mol 0.08206 L atm mol K 290.2 K
2.00 L
CO
CO
n RT
P
P
= =
= 0.812 atm
n
He
= 0.100 g He / (4.003 g He / mol He)
= 0.0250 mol He
P
Total
= P
CO2
+ P
He
= 0.812 atm + 0.298 atm
P
Total
= 1.110 atm
-1 -1
0.0250 mol 0.08206 L atm mol K 290.2 K
2.00 L
He
He
n RT
P
P
= =
= 0.297 atm
EP105: Daltons Law using mole fractions
A mixture of gases contains 4.46 mol Ne, 0.740
mol Ar and 2.15 mol Xe. What are the partial
pressures of the gases if the total pressure is
2.00 atm ?
Strategy:
(1) Calculate mol fraction each gas
(2) Partial pressure = mol fraction x total P
Total # moles = 4.46 + 0.74 + 2.15 = 7.35 mol
X
Ne
= 4.46 mol / 7.35 mol = 0.607
P
Ne
= X
Ne
P
Total
= 0.607 ( 2.00 atm) = 1.21 atm
X
Ar
= 0.740 mol / 7.35 mol = 0.101
P
Ar
= X
Ar
P
Total
= 0.101 (2.00 atm) = 0.202 atm
X
Xe
= 2.15 mol / 7.35 mol = 0.293
P
Xe
= X
Xe
P
Total
= 0.293 (2.00 atm) = 0.586 atm
Whats Behind the Ideal Gas Law?
A purely empirical law - solely the
consequence of experimental
observations
Explains the behavior of gases over a
limited range of conditions.
A macroscopic explanation. Says
nothing about the microscopic behavior
of the atoms or molecules that make up
the gas.
The Kinetic Theory of Gases
Starts with a set of assumptions about the
microscopic behavior of matter at the atomic level.
Supposes that the constituent particles (molecules)
of the gas obey the laws of classical physics.
Accounts for the random behavior of the particles
with statistics, thereby establishing a new branch
of physics - statistical mechanics.
Offers an explanation of the macroscopic behavior
of gases.
Predicts experimental phenomena that ideal gas
law cant predict. (Maxwell-Boltzmann Speed
Distribution)
The Four Postulates of the Kinetic Theory
A pure gas consists of a large number of
identical molecules separated by distances
that are great compared with their size.
The gas molecules are constantly moving in
random directions with a distribution of
speeds.
The molecules exert no forces on one
another between collisions, so between
collisions they move in straight lines with
constant velocities.
The collisions of molecules with the walls of
the container are elastic; no energy is lost
during a collision. Collisions with the wall of
the container are the cause of pressure.
An ideal gas
molecule in a cube
of sides L.
Cartesian Coordinate System for the Gas Particle
Cartesian Components of a
Particles Velocity
n. informatio l directiona
no conveys and quantity scalar a is that Note
axes. Cartesian
principal three the along velocity the of components
are and , and particle the of speed the is Where
2 2 2 2
u
u u u u
u u u u
z y x
z y x
+ + =
Consider the force exerted
on the wall by the
component of velocity
along the x axis.
Calculation of the Force Exerted on a
Container by Collision of a Single Particle
( )
( )
2
2
2 2
2
2
length of box
speed
2
2 and similarly for and
,
2
2 2 2
x x
x
x x
x x y z
y
x z
tot
mu
u
F ma m
t t
mu mu
L
t
u
u mu
F mu F F
L L
Thus
mu
mu mu m
F u
L L L L
= = =
=
= =
= =
= + + =
Calculation of the Pressure in Terms of
Microscopic Properties of the Gas Particles
2
,
2
Since the number of particles in a givengas sample can be expressed
average over
as , where is the number of moles and is Avogadro's
square of speed of all particles
!
num
tot one particle
A A
m
F u
L
nN n N
=
2
2 2
2 3
2
ber,
2
2 /
6 3
1
2
2
3
tot A
Tot
A A
Tot
A
m
F nN u
L
F mu L mu
P nN nN
Area L L
nN mu
P
V
=
= = = =
= =
2
A
mu
nN
3V
n Kinetic Energy/mole
2
3 V
The Kinetic Theory Relates the
Average Kinetic Energy of the
Particles to Temperature
from ideal gas law
Note that is independent of molecular mass
2
or
3
3
2
!
avg
avg
nKE
P
V
RT
PV
KE
n
=
= =
avg
avg
3
KE = RT
2
KE
Root Mean Square Speed and
Temperature
2
2
1 3
2 2
A
rms
N mu RT
u u
=
=
3RT
M
where R is the gas constant (8.314 J /mol K), T is the
temperature in kelvin, and Mis the molar mass expressed in
kg/mol (to make the speed come out in units of m/s).
2
,
2
independent of !
tot one particle
m
F u
L
m
=
Not all molecules have the same speed.
But what is the distribution of speeds in a
large number of molecules? The kinetic
theory predicts the distribution function
for the molecular speeds.
Molecular Speed Distribution
The Mathematical Description of the
Maxwell-Boltzmann Speed Distribution
2
2 2
-23
( ) 4
2
where: peed in , mass of particle in kg
Boltzman's constant = 1.38066 10 J /K,
and temperature in K
B
mu k T
B
B A
m
f u u e
k T
u s m s m
k R N
T
=
= =
= =
=
f(u)du is the fraction of molecules that have
speeds between u and u + u.
The distribution of
molecular speeds for N
2
at three temperatures
Features of the Speed Distribution
The most probable speed is at the peak of
the curve.
The most probable speed increases as the
temperature increases.
The distribution broadens as the
temperature increases.
Relationship between molar mass and
molecular speed at fixed T
The Speed Distribution Depends on
Molecular Mass
The most probable speed increases as the
molecular mass decreases.
The distribution broadens as the molecular
mass decreases.
Calculation of Molecular Speeds
and Kinetic Energies at 300.0 K
Molecule H
2
CH
4
CO
2
Molecular
Mass (g/mol)
2.016 16.04 44.01
Kinetic Energy
(J /molecule)
6.213 x 10
- 21
6.213 x 10
- 21
6.213 x 10
- 21
Speed
(m/s)
1,926 683.8 412.4
2
2
1 3
2 2
A
rms
N mu RT
u u
=
=
3RT
M
Various Ways to
designate
the average
Speed.
Molecular Mass and Molecular Speeds
Molecule H
2
CH
4
CO
2
Molecular
Mass (g/mol)
Kinetic Energy
(J /molecule)
rmsspeed
(m/s)
2.016 16.04 44.01
6.213 x 10
- 21
6.213 x 10
- 21
6.213 x 10
- 21
1,926 683.8 412.4
Larger
Same Kinetic Energy
Slower
The Three Measures of the Speed of a
Typical Particle
3
2
8
rms
mp
avg
RT
u
M
RT
u
M
RT
u u
M
=
=
= =
EP106: Calculate the Kinetic Energy of a
Hydrogen Molecule traveling at 1.57 x 10
3
m/sec.
Strategy: (1) calculate mass of molecule. (2) Use KE=1/2mu
2
Mass = 2.016 g/mol x 10
-3
kg/g
6.022 x 10
23
molecules / mol
= 3.348 x 10
- 27
kg / H
2
molecule
KE = 1/2 mu
2
= 1/2 (3.348 x 10
- 27
kg/ molecule)
x ( 1.57 x 10
3
m/sec)
2
KE = 4.13 x 10
- 21
kg m
2
/ sec
2
molecule
KE = 4.13 x 10
- 21
J / molecule
The Process of Effusion
Effusion
Effusion is the process whereby a gas escapes from its
container through a tiny hole into an evacuated space.
According to the kinetic theory a lighter gas effuses faster
because the most probable speed of its molecules is higher.
Therefore more molecules escape through the tiny hole in unit
time.
This is made quantitative in Graham's Law of effusion: The rate
of effusion of a gas is inversely proportional to the square root
of its molar mass.
1
Rateof effusion speed
M
Effusion Calculation
2
mass of He 4.003
1.409
mass of H 2.016
= =
EP107: Calculate the ratio of the effusion rates of helium
and hydrogen through a small hole.
Strategy:
(1)The effusion rate is inversely proportional to square root of
molecular mass.
(2) find the ratio of the molecular masses and take the square
root.
(3)The inverse of the ratio of the square roots is the effusion rate
ratio.
2
effusion rate He 1
0.7097
effusion rate H 1.409
= =
Path of one
particle in
diffusing
through the
gas.
Diffusion
The movement of one gas through another by
thermal random motion.
Diffusion is a very slow process in air
because the mean free path is very short (for
N
2
at STP it is 6.6x10
-8
m). Given the nitrogen
molecules high velocity, the collision
frequency is also very high
(7.7x10
9
collisions/s).
Diffusion also follows Graham's law:
M
1
diffusion of Rate
Diffusion of a
gas particle
through a
space filled
with other
particles
Relative Diffusion Rates of NH
3
and HCl
Relative Diffusion Rate of NH
3
compared to HCl in
the reaction
NH
3
(g) + HCl(g) = NH
4
Cl(s)
HCl = 36.46 g/mol NH
3
= 17.03 g/mol
Rate
NH3
= Rate
HCl
x ( 36.46 / 17.03 )
1/ 2
Rate
NH3
= 1.463 Rate
HCl
Gaseous Diffusion Separation of
Uranium 235 / 238
235
UF
6
vs
238
UF
6
Separation Factor = S =
after Two runs S = 1.0086
after approximately 2000 runs
235
UF
6
is > 99% Purity !
Y - 12 Plant at Oak Ridge National Lab
(238.05 + (6 x 19))
0.5
(235.04 + (6 x 19))
0.5
The ideal gas law is accurate over only a range
of conditions
The effect of intermolecular attractions on measured gas
pressure.
The effect of
molecular
volume on
measured gas
volume.
The van der Waals equation of state is valid over a
wider range of conditions than the ideal gas law:
( ) nRT nb V
V
a n
P =
+
2
2
Where P is the measured pressure, V is the
container volume, n is the number of moles of gas
and T is the temperature. a and b are the van der
Waals constants, specific for each gas.
EP109: van der Waals Calculation of a Real gas
Problem: A tank of 20.00 liters contains chlorine gas at a temperature
of 20.00
0
C at a pressure of 2.000 atm. The tank is pressurized to a new
volume of 1.000 L and a temperature of 150.00
0
C. Calculate the final
pressure using the ideal gas equation, and the Van der Waals equation.
-1 -1
2.000atm20.00L
1.663 mol
0.8206 L atm mol K 273.15 K
PV
n
RT
= = =
-1 -1
1.663 mol 0.08206 L atm mol K 423.15 K
57.75 atm
1.000L
ideal
nRT
P
V
= = =
( )
( )
2
2
-1 -1
-1
2
2 -2
2
1.663 mol 0.8206 L atm mol K 423.15 K
1.000L 1.663 mol 0.0562 mol L
1.663 mol 6.49atm L mol
63.7 19.9
1.00
45.8 a
0 L
tm
vdW
nRT n a
P
V nb V
=
= =
57.75 atm
ideal
P =
If attractive interactions dominate
ideal vdW
P P >
EP110: Gas Law Stoichiometry
Problem: A 2.79 L container of ammonia gas for which P= 0.776 atm
and T=18.7
o
C is connected to a 1.16 L container of HCl gas for which
P= 0.932 atmand T= 18.7
o
C. What mass of solid ammonium chloride
will be formed? What gas is left in the combined volume, and what
is its pressure?
Strategy:
1) Calculate the moles of each reactant and determine limiting reactant.
2) Calculate the mass of product from balanced equation
3) Determine which reactant is left and its pressure
Solution:
Balanced equation: NH
3
(g) + HCl (g) NH
4
Cl (s)
T
NH3
= 18.7
o
C + 273.15 = 291.9 K
3
-1 -1
0.776 atm 2.79 L
0.0903 mol
0.08206 L atm mol K 291.9 K
NH
PV
n
RT
= = =
-1 -1
0.932 atm 1.16 L
0.0451 mol
0.08206 L atm mol K 291.9 K
HCl
PV
n
RT
= = =
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