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Entropy
James Chou
BCMP201 Spring 2008
An interesting observation
Random distribution of
kinetic energy through
random collisions
#v x2
f (v x ) =
exp 2
2
2"
2!"
1
! 2 = average of (v x " v x )
!=
-Vx
Vx
v x2 =
0
2
kB T
m
-Vx
Vx
P ( X = 1) + P ( X = 2) + ...+ P ( X = 6) = 1
Without additional information about the die, the most unbiased distribution is such that all
outcomes are equally probable.
P ( X = 1) = P ( X = 2) = ... = P ( X = 6) = 1 6
H = !" pi ln pi
i=1
H = !" pi ln pi = ln6 .
i=1
log e x = ln x, e = 2.73
ln( AB) = ln A + ln B ,
ln( A / B) = ln A ! ln B ,
d
1
ln( x ) =
dx
x
N!
!=
( Np1 )!( Np2 )!...( Np6 )!
Using Stirlings approximation for very large N, ln N!! N ln N " N , ln# becomes
6
i=1
i=1
i=1
i=1
ln ! = "N # pi ln pi = NH
i =1
# of possible outcomes
Statistical Entropy
H = Const ! ln"
S = const ! ln" ,
What is temperature?
Not in Equilibrium
Equilibrium
E2
E1
E = E1 + E 2 = const.
dE1 = !dE 2
dS
dS
dS dE 2 dS1 dS2
= 1+ 2
=
!
=0
dE1 dE1 dE 2 dE1 dE1 dE 2
At equilibrium,
dS1 dS2
=
dE1 dE2
It is more convenient to measure T in degrees Kelvin (K). The conversion factor between
energy and degree is the Boltzmanns constant, kB = 1.38 X 10-23 J / K. Hence we redefine
S and T by incorporating the conversion factor.
S = kB ln!
and
T " T / kB .
Lower T
3e
2e
e
Higher T
3e
2e
e
! 5! $
S1 = kB ln#
&
" 2!2!%
! 5! $
S2 = kB ln#
&
" 3!2!%
!E !S = e ( k B ln 3)
! 5! $
S1 = kB ln#
&
" 2!2!%
! 5! $
S2 = kB ln#
&
" 3!2!%
!E !S = 3e ( k B ln 3)
Same change in entropy, but more energy is given away by the system initially with higher
T. Hence temperature is a measure of the tendency of an object to spontaneously give up
energy to its surroundings.
Can we derive the equation of state of a gas (PV = nRT) from the
concept of entropy?
! = !v " !r
!v = # of velocity states
!r = # of position states
One particle
N particles
Since v " E 1 2 ,
S = kB ln! =
3kB N
ln E + Const.
2
S = kB ln! =
3kB N
ln E + Const.
2
1 dS 3k B N
=
=
T dE
2E
n = # of moles,
"
3
3
E = k B NT = k B ( nN 0 )T
2
2
N0 = 6.02 x 1023 mol-1
3
E = nRT .
2
E=
3
kB T .
2
F=
!px 2mv x
=
= mv x2 L .
!t 2L v x
F = " mv x2 i L = Nm v x2 L .
i=1
v x2 + v y2 + v z2
1
2
2
2
2
Since P = F L = Nm v x V and E = N m v = N m v x ,
2
2
2
E.
3
3
E
=
nRT , we obtain PV = nRT .
Finally, since
2
we obtain PV =
In the joint system, the probability of the molecule of interest in a particular state,
E a , is
# SB ( E B ) &
p( E a ) = !B ( E B ) " P0 = exp%
( " P0 .
$ kB '
SB ( E B ) = k B ln(!B ( E B ))
! S (E )$
p( E a ) = exp# B B & ' P0
" kB %
S( E B )
Ea
E tot = E B + E a ! E B
EB
E tot
We can use the first-order Taylors expansion to approximate SB ( E B ) because E B is very near E tot .
SB ( E B ) ! SB ( E tot ) "
dSB ( E tot )
1
E a = SB ( E tot ) "
Ea
dE B
kB T
Hence we obtain
" S ( E ) % " (E %
" (E %
p( E a ) = P0 ! exp$ B tot ' exp$ a ' = A ! exp$ a '
# k B & # kB T &
# kB T &
IMPORTANT: The probability distribution of the molecule of interest in equilibrium with its surrounding
depends only on the temperature of the surrounding.
Random distribution of
kinetic energy through
random collisions
" 1 2%
! mv
" !E %
$ 2
'
P = A exp $
=
A
exp
$ kT '
# k BT '&
$# B
'&
"
%
$ !v 2 '
= A exp $
'
k
T
"
%
B
$ 2$
'
# # m '& &
#v x2
f (v x ) =
exp 2
2
2"
2!"
1
!=
v x2 =
kB T
m
k
A !!" B
Transition
state
" !E a %
' , where E a is the
RT &
proportional to exp$#
Ea
" !E a %
k = Aexp$
'
# RT &
!E
A
Arrhenius equation
k
Catalyzed by either mutation
or binding of PrPSc
PrPC
PrPSc
Ea
!E
S = kB ln!
T = ( dE dS ) N,V
# "E &
p( E a ) = A ! exp% a (
$ kB T '