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11/14/2013

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Gases
2009, Prentice-Hall, Inc.
Lecture 1003
KMT
Grahams Law
Deviations from Ideality
John Bookstaver
St. Charles Community College
Cottleville, MO
Chemistry, The Central Science, 11th edition
Theodore L. Brown; H. Eugene LeMay, Jr.;
and Bruce E. Bursten
Gases
Kinetic-Molecular Theory
Relationship between temperature
of a Gas and Its Average Kinetic
Energy
2009, Prentice-Hall, Inc.
11/14/2013
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Gases
2009, Prentice-Hall, Inc.
Kinetic-Molecular Theory
This is a model that
aids in our
understanding of what
happens to gas
particles as
environmental
conditions change.
Gases
2009, Prentice-Hall, Inc.
Main Tenets of Kinetic-
Molecular Theory
Gases consist of large numbers of
molecules that are in continuous,
random motion.
11/14/2013
3
Gases
2009, Prentice-Hall, Inc.
Main Tenets of Kinetic-
Molecular Theory
The combined volume of all the
molecules of the gas is negligible
relative to the total volume in which the
gas is contained.
Gases
2009, Prentice-Hall, Inc.
Main Tenets of Kinetic-
Molecular Theory
Attractive and
repulsive forces
between gas
molecules are
negligible.

11/14/2013
4
Gases
2009, Prentice-Hall, Inc.
Main Tenets of Kinetic-
Molecular Theory
Energy can be
transferred between
molecules during
collisions, but the
average kinetic energy
of the molecules does
not change with time, as
long as the temperature
of the gas remains
constant.
Gases
2009, Prentice-Hall, Inc.
Main Tenets of Kinetic-
Molecular Theory
The average kinetic
energy of the
molecules is
proportional to the
absolute
temperature.
11/14/2013
5
Gases
Molecular Effusion and
Diffusion
Grahams Law
2009, Prentice-Hall, Inc.
Gases
2009, Prentice-Hall, Inc.
Effusion
Effusion is the
escape of gas
molecules
through a tiny
hole into an
evacuated
space.
11/14/2013
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Gases
2009, Prentice-Hall, Inc.
Effusion
The difference in the
rates of effusion for
helium and nitrogen,
for example,
explains a helium
balloon would
deflate faster.
Gases
2009, Prentice-Hall, Inc.
Diffusion
Diffusion is the
spread of one
substance
throughout a space
or throughout a
second substance.
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Gases
where
MM n m
MM
m
n
nRT
2
3
m
2
1
KE
2
= =
= v =
Gases
thus
then
2
1
2
MM
RT 3
nRT
2
3
MM n
2
1
|
.
|

\
|
= v
= v
RMS speed
11/14/2013
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Gases
Gases
2
1
B
2
1
A
B
A
MM
RT 3
MM
RT 3
v
v
|
|
.
|

\
|
|
|
.
|

\
|
=
substituting:
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Gases
simplifying
A
B
B
A
MM
MM
v
v
=
Grahams Law
Gases
Real Gases: Deviations from
Ideal Behavior
van der Waals Equation
2009, Prentice-Hall, Inc.
11/14/2013
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Gases
2009, Prentice-Hall, Inc.
Real Gases
In the real world, the
behavior of gases
only conforms to the
ideal-gas equation
at relatively high
temperature and low
pressure.
Gases
2009, Prentice-Hall, Inc.
Real Gases
Even the same gas
will show wildly
different behavior
under high pressure
at different
temperatures.
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Gases
2009, Prentice-Hall, Inc.
Deviations from Ideal Behavior
The assumptions made in the kinetic-molecular
model (negligible volume of gas molecules
themselves, no attractive forces between gas
molecules, etc.) break down at high pressure
and/or low temperature.
Gases
2009, Prentice-Hall, Inc.
Corrections for Nonideal
Behavior
The ideal-gas equation can be adjusted
to take these deviations from ideal
behavior into account.
The corrected ideal-gas equation is
known as the van der Waals equation.
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12
Gases
2009, Prentice-Hall, Inc.
The van der Waals Equation
) (V nb) = nRT
n
2
a
V
2

(P +

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