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Entropy and Probability

This document discusses entropy and probability from a statistical perspective. It defines entropy as a measure of disorder in a system, with higher entropy states having higher probability. The document uses examples of gas particles in containers to illustrate microstates (precise descriptions of particles) and macrostates (general descriptions). It shows that as the number of particles increases, the number of possible microstates and macrostates increases. The fundamental assumption of statistical mechanics is that all microstates are equally probable. Finally, it derives the Boltzmann equation relating entropy S to the natural log of the number of microstates W.

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Fer Moncada
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210 views

Entropy and Probability

This document discusses entropy and probability from a statistical perspective. It defines entropy as a measure of disorder in a system, with higher entropy states having higher probability. The document uses examples of gas particles in containers to illustrate microstates (precise descriptions of particles) and macrostates (general descriptions). It shows that as the number of particles increases, the number of possible microstates and macrostates increases. The fundamental assumption of statistical mechanics is that all microstates are equally probable. Finally, it derives the Boltzmann equation relating entropy S to the natural log of the number of microstates W.

Uploaded by

Fer Moncada
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Entropy and Probability

(A statistical view)
Entropy ~ a measure of the disorder of a
system.
A state of high order = low probability
A state of low order = high probability
In an irreversible process, the
universe moves from a state of low
probability to a state of higher
probability.
We will illustrate the concepts by
considering the free expansion of a gas
from volume Vi to volume Vf.
The gas always expands to fill the
available space. It never spontaneously
compresses itself back into the original
volume.

First, two definitions:


Microstate: a description of a system that
specifies the properties (position
and/or momentum, etc.) of each
individual particle.
Macrostate: a more generalized
description of the system; it can be in
terms of macroscopic quantities, such
as P and V, or it can be in terms of the
number of particles whose properties
fall within a given range.
In general, each macrostate contains a
large number of microstates.
An example: Imagine a gas consisting of
just 2 molecules. We want to consider
whether the molecules are in the left or
right half of the container.

R
1

There are 3 macrostates: both molecules


on the left, both on the right, and one
on each side.
There are 4 microstates:
LL, RR, LR, RL.
How about 3 molecules? Now we have:
LLL, (LLR, LRL, RLL), (LRR, RLR, RRL), RRR
(all L) (2 L, 1 R)

(2 R, 1 L)

(all R)

i.e. 8 microstates, 4 macrostates


How about 4 molecules? Now there are
16 microstates and 5 macrostates
(all L) (3L, 1R) (2L, 2R) (1L, 3R) (all R)
1

4
6
4
number of microstates

In general:

N
1
2

W
2
4

M
2
3

4 1

16

1 5 10 10 5 1

32

1 6 15 20 15 6 1

64

1 7 21 35 35 21 7 1

128

1 8 28 56 70 56 28 8 1

256

1 1
1 2 1
1
1

3
4

3
6

2N N+1
This table was generated using the formula
for # of permutations for picking n items
from N total:
WN,n =

N!
N! (N-n)!

multiplicity

i.e. W6,2 =

6!
2! 4!

= 15

Fundamental Assumption of Statistical


Mechanics: All microstates are equally
probable.
Thus, we can calculate the likelihood of
finding a given arrangement of molecules
in the container.
E.g. for 10 molecules:

Conclusion: Events such as the


spontaneous compression of a gas (or
spontaneous conduction of heat from a
cold body to a hot body) are not
impossible, but they are so improbable
that they never occur.

We can relate the # of microstates W of


a system to its entropy S by considering
the probability of a gas to spontaneously
compress itself into a smaller volume.
If the original volume is Vi, then the
probability of finding N molecules in a
smaller volume Vf is
Probability = Wf/Wi = (Vf/Vi)N

ln(Wf/Wi) = N ln(Vf/Vi) = n NA ln(Vf/Vi)

We have seen for a free expansion that


DS = n R ln(Vf/Vi) ,
so
DS = (R/NA) ln(Wf/Wi) = k ln(Wf/Wi)
or
Sf - Si = k ln(Wf) - k ln(Wi)

Thus, we arrive at an equation, first


deduced by Ludwig Boltzmann, relating the
entropy of a system to the number of
microstates:
S = k ln(W)
He was so pleased with this relation that
he asked for it to be engraved on his
tombstone.

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