Scribd
Upload
8 views

Statistical interpretation of Entropy

Statistical interpretation of entropy

Uploaded by

Testimony Felix
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPS, PDF, TXT or read online on Scribd
8 views

Statistical interpretation of Entropy

Statistical interpretation of entropy

Uploaded by

Testimony Felix
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPS, PDF, TXT or read online on Scribd
You are on page 1/ 6

Statistical Interpretation of Entropy

Statistical mechanics bridges between

phenomenological thermodynamics underlying microscopic behavior

-Statistical mechanics requires a separate lecture (see textbook part II)


but

abstract nature of entropy asks for an intuitive picture for state function S

Here: heuristic approach to statistical interpretation of entropy by

Ludwig Boltzman
Consider a gas in a box from an atomistic point of view
atoms (or molecules) are moving in a disordered manner within the box
having collisions with the walls

V1 V2
V2
Probability to find a particular atom in V2 reads p(1) p 
V1
Let's pick two atom: 2
 V2 
Probability to find both of them at the same time in V2 reads p(2) p p  
 V1 
N
V 
Probability to find all N atom at the same time in V2 reads p(N) pN  2 
 V1 
Let W1 be the “thermodynamic
probability” to find system in the
homogeneously occupied
state (more precisely:
# of possible microstates)

Thermodynamic probability to
find system in a state with
all atoms in V2 reads:
N
 V2 
W2  W1  or
 V1 
N
W1  V1 
 
W 2  V2 

Note: W1>>W2 for N large V1 V2


Entropy S quantifies the thermodynamic probability W of a particular state

S function(W )

We know: S extensive S A B S A  SB

SA + SB = SA+B

Thermodynamic probability WA+B to find combined system A+B in a state where


subsystem A is in a state of thermodynamic probability WA
and
subsystem B is in a state of thermodynamic probability WB reads WA B  WA WB

Which function does the job f(WA B ) f(WA WB ) f(WA )  f(WB )

so that S(WA B ) S(WA )  S(WB )


S C ln W

Check: S A B C ln WA B = C ln WA WB C ln WA  C ln WB

S A  SB

Let’s determine C

We know entropy change with volume changeV0Vf for an ideal gas


in an adiabatically isolated box

Vf
S nRln (see lecture)
V0

Wf
Now we apply S C ln Wf  C ln W0 C ln N
W0  Vf 
N S C ln  
Wf  Vf  V
 0
with  
W0  V0 
Vf V Vf
S N C ln n NA C ln f comparison with S nRln
V0 V0 V0
R k BNA
C  k B
NA NA

S k B ln W
W: # of possible microstates

Principle of increase of entropy

Adiabatically insulated system


approaches state of maximum
probability.

You might also like