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The Kinetic Theory, Part 1

Maxwell derived the velocity distribution of gas particles using assumptions of equal likelihood of particle velocities in different directions and conservation of particle number during collisions. Boltzmann provided a more rigorous kinetic theory derivation using the assumption that initial velocities of colliding particles are independent. He defined a "H-function" of the velocity distribution and showed it always decreases due to collisions, reaching a minimum for Maxwell's velocity distribution. The H-function is proportional to thermodynamic entropy, establishing a statistical mechanical foundation for the second law of thermodynamics.

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40 views

The Kinetic Theory, Part 1

Maxwell derived the velocity distribution of gas particles using assumptions of equal likelihood of particle velocities in different directions and conservation of particle number during collisions. Boltzmann provided a more rigorous kinetic theory derivation using the assumption that initial velocities of colliding particles are independent. He defined a "H-function" of the velocity distribution and showed it always decreases due to collisions, reaching a minimum for Maxwell's velocity distribution. The H-function is proportional to thermodynamic entropy, establishing a statistical mechanical foundation for the second law of thermodynamics.

Uploaded by

AlbertJnBaptiste
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© © All Rights Reserved
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12. The Kinetic Theory, Part 1.

1. Early Kinetic Theory


18th-19th Century Caloric theories of heat:
Pressure of a gas due to repulsive force of caloric particles.
Temperature is a measure of amount of caloric present.
1830s-50s. Wave theory of heat:
Heat is a vibrational motion of the ether.
1840s:
Joule's mechanical equivalent of heat and advocacy of the dynamical theory.
Early dynamical ("kinetic") theories of heat.
A gas is made up of many particles.
Motion of particles is responsible for pressure and heat.
- Bernoulli (1738):

[pressure] [velocity]2

- Herepath (1820):

[temperature] [velocity]

- Waterston (1843): [temperture] [velocity]2


Common assumption: All particles move at same velocity.

2. Maxwell
1860. Maxwell's Velocity Distribution

"Illustrations of the dynamical theory of gases"

Velocites of gas particles should vary due to collisions.


"To find the average number of particles whose velocities lie between given limits,
after a great number of collisions among a great number of equal particles."

Let: N = total # of particles.


Nf(v)dv = average # of particles with velocity between v and v + dv.
Assume:
(i) Velocities are distributed identically in x-, y-, and z-directions.
So: f(v) = g(vx)g(vy)g(vz), for some function g.
(ii) All directions of impact are equally likely.
So: f(v) depends only on v = |v|.

Ng(vx)dvx = ave #
particles with velocity
between vx and vx + dvx

This entails:

1
#(v 2 /! 2 )
e
= probability for velocity to be v.
3 3/2
!"
2
2
4
v 2e #(v /! ) = probability for velocity to be v.
(2) 4v2f(v) =
!3 "
(1) f(v) =

(3) [mean squared velocity] = v2 = (3/2).


Uffink, J. (2007) "Compendium of the Foundations of Classical Statistical Physics", in J. Butterfield & J. Earman (eds.) Philosophy of Physics, Elsevier, pp. 923-1074.

Check:
(1) Note: (i) and (ii) entail g(vx) = Ce
And: N =

"

!"

Ng(vx )dvx =

"

!"

NCe

!(vx2 /" 2 )

!(vx2 /$ 2 )

for constants C, .

dvx = NC $ % . So C =

$ %

$ 1 #(vx2 /! 2 ) ' $ 1 #(vy2 /! 2 ) ' $ 1 #(vz2 /! 2 ) '


1
#(v 2 /! 2 )
e
e
e
=
e
So: f(v) = &
)&
)&
) ! 3" 3/2
%! "
( %! "
( %! "
(
(2) [probability for velocity to be v]
= [probability for velocity to be v] [# of v-values]
= 4v2f(v)

surface area of
sphere with radius v

(3) v2 = [weighted sum of all possible values of v2]

=
=

"

"

[ probability for velocity to be v ] ! [v 2 ] ! dv


v

$
= (3/2)$ .
0

4
3

2 &(v 2 /$ 2 )

ve

dv

Key concept: f(v)dv is probability for velocity to lie in range (v, v + dv).
Which is just the relative number of particles with a velocity in that range.
Recall: Assumption (i): Velocities are distributed identically in x-, y-, and zdirections; so f(v) takes general form f(v) = g(vx)g(vy)g(vz).
"As this assumption may appear precarious,
I shall now determine the form of the
function in a different manner." (1866)

New derivation will appeal to collisions between gas particles.


Instead of assuming orthogonal components of a single gas particle are
independent, now just assume that initial velocities of colliding gas particles
are independent ("Stozahlansatz").
"Collision number assumption":
Term coined later by Ehrenfest
& Ehrenfest (1912)

1866. Second Derivation of Velocity Distribution

"On the Dynamical Theory of Gases"

Consider: Collisions with initial velocities v1, v2 and final velocities v'1, v'2.
Let P1 be at rest (r = 0, = 0, z = 0), and P2 traveling in z-direction
towards particle 1 (r = const., = const., z(t) = z0 + |v2 - v1|t).
z

Assumption (Stozahlansatz):
N(v1, v2) = [# of collisions during dt in which (v1, v2) (v'1, v'2)]
= N2f(v1)f(v2)dv1dv2dtdV
Nf(v2)dv2 = [# particles with velocity in (v2, v2+dv2)].

v2

Nf(v1)dv1 = [# particles with velocity in (v1, v1+dv1)].

initial velocities

dV = rdrddz = |v2 - v1|rdrddt = volume swept out by P2.

So:

N(v1, v2) = N2f(v1)f(v2)|v2 - v1|dv1dv2rdrddt.

And: N(v'1, v'2) = N2f(v'1)f(v'2)|v2 - v1|dv1dv2rdrddt.

Time-reversal invariance
where |v'2 - v'1| = |v2 - v1|
and dv'1dv'2 = dv1dv2.

Now: f(v) is stationary iff N(v1, v2) = N(v'1, v'2) iff f(v1)f(v2) = f(v'1)f(v'2).
And: This entails f(v) = Ce

!(v 2 /" 2 )

(1860 result).

Uffink, J. (2007) "Compendium of the Foundations of Classical Statistical Physics", in J. Butterfield & J. Earman (eds.) Philosophy of Physics, Elsevier, pp. 923-1074.

Maxwell's Uniqueness Argument


f(v1)f(v2) = f(v'1)f(v'2) means that the transition (v1, v2) (v'1, v'2) is equally
probable as the transition (v'1, v'2) (v1, v2).
Suppose not: Suppose (v1, v2) (v'1, v'2) is more probable than (v'1, v'2) (v1, v2).
To remain stationary, there would have to be a closed transition cycle:
(v1, v2) (v'1, v'2) (v''1, v''2) ... (v1, v2).
But:
"...it is impossible to assign a reason why the
successive velocities of a molecule should be arranged
in this cycle rather than in the reverse order."
So:

(v1, v2) (v'1, v'2) (v''1, v''2) ... (v1, v2).


must be equally probable as
(v1, v2) (v'1, v'2) (v''1, v''2) ... (v1, v2).

But:

This just means that (v1, v2) (v'1, v'2) is equally probable as
(v'1, v'2) (v1, v2).

3. Boltzmann
1872. Boltzmann's H-Theorem

Ludwig Boltzmann
(1844-1906)

"Further Studies on the Thermal Equilibrium of Gas Molecules"

"If one wants... to build up an exact theory... it is before all necessary to determine the probabilities of the various states that one
and the same molecule assumes in the course of a very long time,
and that occur simultaneously for different molecules. That is, one
must calculate how the number of those molecules whose states lie
between certain limits relates to the total number of molecules." .

Let: f(v1, t)dv1 = [# particles with velocities in (v1, v1+dv1) at time t].
Task: Determine how f(v1, t) changes between t and t + dt.
Note: f(v1, t + dt)dv1 = [# particles with velocities in (v1, v1+dv1) at time t + dt]
= f (v1, t)dv1 + [changes]

= f (v1,t)dv1 +
So:

!f (v1,t)
!t

[changes ]
dtdv1

!f (v1,t)
!t

dtdv1 + ...

Taylor expansion
of f(v1, t + dt)dv1.

Uffink, J. (2007) "Compendium of the Foundations of Classical Statistical Physics", in J. Butterfield & J. Earman (eds.) Philosophy of Physics, Elsevier, pp. 923-1074.
Janssen, M. (preprint) "Dogs, Fleas, and Tree Trunks: The Ehrenfests Marking the Territory of Boltzmann's H-Theorem".

Two types of [changes]:


(i) Collisions during dt in which particles with initial velocities in (v1, v1+dv1) end
up with velocities outside (v1, v1+dv1). Subtract from f(v1, t)dv1.
(ii) Collisions during dt in which particles with initial velocities outside (v1, v1+dv1)
end up with velocities inside (v1, v1+dv1). Add to f(v1, t)dv1.
Assumption (Stozahlansatz):
(a) [type (i)] = N 2dv1dt ! r dr ! d" ! d v2 f (v1,t)f (v2,t) | v2 # v1|
(b) [type (ii)] = [time-reverse of (i)] = N 2dv1dt ! r dr ! d" ! d v2 f (v'1,t)f (v'2,t) | v2 # v1|

So: [changes] = N 2dv1dt ! r dr ! d" ! d v2 f (v'1,t)f (v'2,t) # f (v1,t)f (v2,t) | v2 # v1|


Thus (Boltzmann Equation):
!f (v1,t)
!t

= N 2 " r dr " d# " d v2 f (v'1,t)f (v'2,t) $ f (v1,t)f (v2,t) | v2 $ v1|

Now: f(v1, t)/t has a minimum when f(v'1, t)f(v'2, t) = f(v1, t)f(v2, t).
And: This entails f(v) = Ce !(v

/" 2 )

(Maxwell's result).

Boltzmann's Uniqueness Argument:


Define "H-function":
Then:

H[f (v,t)] = ! d vf (v,t)ln f (v,t)

f (v1,t)f (v2,t)
dH
= " d v1 d v1... f (v'1,t)f (v'2,t) ! f (v1,t)f (v2,t) ln
dt
f (v'1,t)f (v'2,t)

Note: Integrand has form (x - y)ln[y/x].


And: This is always less than or equal to zero!
x > y (x - y) is pos, ln[y/x] is neg.
x < y (x - y) is neg, ln[y/x] is pos.
x = y (x - y) = ln[y/x] = 0.

dH
! 0.
dt
And: The Maxwell distribution is the unique distribution for which dH/dt = 0.
So:

Now: What is H?

"It has thus been rigorously proved that whatever may have been the initial
distribution of kinetic energy, in the course of time it must necessarily
approach the form found by Maxwell... This [proof] actually gains much in
significance because of its applicability to the theory of multi-atomic gas
molecules. There too, one can prove for a certain quantity [H] that, because
of the molecular motion, this quantity can only decrease or in the limiting
case remain constant. Thus, one may prove that because of the atomic
movement in systems consisting of arbitrarily many material points, there
always exists a quantity which, due to these atomic movements, cannot
increase, and this quantity agrees, up to a constant factor, exactly with the
value that I found [in an earlier paper] for the well-known integral dQ/T."
"This provides an analytical proof of the Second Law in a way completely different from those attempted so far. Up till now, one has attempted
to proof that dQ/T = 0 for a reversible cyclic process, which however
does not prove that for an irreversible cyclic process, which is the only
one that occurs in nature, it is always negative; the reversible process
being merely an idealization, which can be approached more or less but
never perfectly. Here, however, we immediately reach the result that
dQ/T is in general negative and zero only in a limit case..."

H is proportional to -S, where S is the thermodynamic entropy!


Call -H the "Boltzmann entropy" SB.

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