processes by use of a simple model of atoms and molecules in the

gas phase. The probabilities of molecular speeds and the values of

average speeds depend on the molecular mass and temperature for
noninteracting gas molecules. The frequency of collisions and the transport
properties (viscosity, diffusion, and heat conduction) for gases of rigid spheri
cal
molecules can be calculated. However, the behavior of real gases is more
complicated, again because of intermolecular interactions.
The prediction of rates of chemical reactions is much more difficult, so
we will first consider the experimental aspects of gas reactions and the use of
this information to obtain mechanisms of reactions. Then we turn to chemical
dynamics to learn about the role of the transition state and to photochemistry t
o
learn about the various processes that can occur after a molecule has absorbed a
photon.
The last chapter in this part of the book deals with the kinetics of reactions
in the liquid state. The study of viscosity, diffusion, and electrical transport
of
ions provides information that is useful in understanding the rates of reactions
in liquids. Relaxation methods are useful for studying very fast reactions in
the liquid phase, and the theory of diffusion-controlled reactions yields an
upper limit for the rate constants of bimolecular reactions. This will help us t
o
better understand the acid base catalysis, enzyme catalysis, and the rates of
electrochemical reactions.
Kinetics
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17.1
17.2
17.3
17.4
17.5
17.6
17.7
17.8
17.9
17.10
17
ProbabilityDensity forMolecular Speeds ofGasMolecules
Velocity Distribution in One Direction
Maxwell Distribution of Speeds
Types of Average Speeds
Pressure of an Ideal Gas
Collisions with a Surface and Effusion
Collisions of Hard-SphereMolecules
Effects ofMolecular Interactions on Collisions
Special Topic: Transport Phenomena in Gases
Special Topic: Calculation of Transport Coefficients
17.1 PROBABILITY DENSITY FOR MOLECULAR
SPEEDS OF GAS MOLECULES
The kinetic theory of gases is concerned with the properties of idealized models
of molecules. We will calculate the distribution of molecular speeds, the pressu
re
of an ideal gas, and the rate of collision with a surface assuming point molecul
es.
Then we will calculate the rates of molecular collisions and the mean free path
assuming that the molecules are tiny hard spheres. These calculations will help
us
interpret the rates of chemical reactions. This simple model can also be used to
calculate rates of mixing of gases by diffusion, the rate of conduction of heat,

and
viscosity.
In beginning our consideration of elementary kinetic theory, we will assume that
molecules are represented by points in space that move in straight lines. In oth
er
words, the molecules are assumed not to have volume or cross-sectional area, and
they are assumed to move in straight lines because they do not interact with eac
h
other except in collisions.
Kinetic Theory of Gases
vx
vz
ivx
vy
kvx
kvz
ivx + jvy
jvy
v = ivx + jvy + kvz
r
i j k
r i j k
r
i j k
x y z
x y z .
.
x t
.
f , ,
f , ,
f , , .
x y z
x
x y z
x y z
x x x y y y z
z z x y z x y z x y z
x y z
x y z x y z
x y z
614
  
  

   
 


2 2 21/2
Velocity vector of a particle in velocity space. The length of the vector
that represents the speed and direction of a particle can be calculated from the
components
, , and by use of the Pythagorean theorem, given in equation 17.3.
v
v v v
velocity vector
speed
probability
density

Chapter 17 Kinetic Theory of Gases

v
v
v
v
  
  
v v v
v
v v v
v v
v
v v v v
v v v v v v v
v v v v v v v v v v v
v v v
v v v v v v
Figure 17.1
Earlier we used the position vector to specify the position of a particle in
three-dimensional space in terms of the unit vectors , , and in the direction of
the , , and axes:
(17 1)
Taking the derivative of with respect to time yields the for that
particle:
(17 2)
where d /d . Since the velocity of a gas molecule is represented by a vector,
the velocity has a magnitude and a direction. The velocity vector for a molecule
can be plotted in velocity space as shown in Fig. 17.1. The component velocities
,
, , and , of a molecule have signs, but we are often more interested in the
magnitude of the velocity vector than its direction. The magnitude of the
velocity vector is referred to as the of the particle. As shown by Fig. 17.1,
the speed can be calculated from the components of the velocity vector by using
the Pythagorean theorem:
( ) (17 3)
This quantity is also referred to as the absolute value of the velocity vector.
At a given instant, the velocity vectors for molecules in a gas can be represent
ed
by points at the ends of the vectors, as shown in Fig. 17.2. To describe the
distribution of velocities in three dimensions, we represent the probability of
finding
a molecule with a velocity in the range to d , to d , and to
d by ( ) d d d , where d d d is the infinitesimal volume
in velocity space. This element of volume is illustrated in Fig. 17.3. Thus the
( ) is the probability per unit volume at a point in velocity
space. The probability for all of velocity space is unity:
( ) d d d 1 (17 4)
3 2 1
1
2
3
1
2
3
1 2 3
vy
dvz
dvx

dvy
vz
Volume
element
v
f .
f , , f
f , , f f f f .
x f f
x
m x
m
f
f .
x y z
x x x y y y z z z
x y z x y z
x x x
x
x x
x
x
x x
m kT
x
615


  
 


2
2
v /2
Points representing the heads of velocity vectors for the molecules in a plane.
Note that very few molecules have very high speeds, that is, large absolute valu
es of the
velocity vector, and that the distribution is isotropic, that is, the same in ea
ch direction.
(See Computer Problem 17.G.)
The volume element in
velocity space is infinitesimal in size,
and it has the density of points at the
end of a specific velocity vector .
17.2 Velocity Distribution in One Direction
17.2 VELOCITY DISTRIBUTION IN ONE DIRECTION
v
v v
v
v
v
x



v v v
v v v v v v v v v
v v v v v v

v v v
v
v v
v
v
v v
v
Figure 17.2
Figure 17.3
Alternatively, this equation can be written
( ) d 1 (17 5)
where is the velocity vector.
The probability density ( ) ( ) is called a joint probability density
because three things have to occur: The component velocities must be in the
range to d , to d , and to d . In the case of a gas, the three
velocity components are independent. Therefore, the probability density for the
velocity vector is the product of the probability densities in the three directi
ons:
( ) ( ) ( ) ( ) ( ) (176)
The probability density in the direction is represented by ( ), and ( ) d
is the probability that a molecule has a velocity in the direction between and
d .
The energy of a molecule of mass moving in the direction with velocity is
/2, and so the Boltzmann distribution (equation 16.2) indicates that the probabi
lity
density ( ) that a molecule has velocity is given by
( ) const e (17 7)
2.00 10 6
2.50 10 6
1.50 10 6
1.00 10 6
0.50 10 6
vx /m s 1
f(vx)/103s m 1
500 0 500 1000
f .
m kT
m
f .
kT
x
x
f .
f
f
m kT
x x x
m kT
x
x
x x x x
x x
x
616
n
x ax dx
a a a a a a
x ax dx
a a a
 


 
n
n
2
2
1/2 1/2 1/2
2
3 2 5 3
0
1/2 1/2 1/2
2
3 5
/2
1/2
1/2
/2
v
v
Definite Integrals Occurring in the Kinetic Theory of Gases
Integral 0 1 2 3 4 5
1 1 1