Professional Documents
Culture Documents
http://ocw.mit.edu
Spring 2008
For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.
Hypothesis
TOPICS COVERED
This is a course in building microscopic models for macroscopic
phenomena. Most of first half involves idealized systems, where inter
particle interactions can be ignored and where individual particles are
adequately described by simple energy level formulas (from Quantum
Mechanics 5.61 or Classical Mechanics). The second half deals with nonideality, interacting atoms, as in solids and, in gas phase collisions and
chemical reactions.
I.
II.
Lecture 1, Page 2
Solid-State Chemistry
models for solids
prediction of macroscopic properties from microscopic interactions
III.
Kinetics Models
Kinetic Theory of Gases (Boltzmann)
bulk properties obtained from averages over speed
distributions
less powerful than stat. mech., but simpler to apply in everday
circumstances
transport properties relaxation to equilibrium
IV.
Lecture 1, Page 3
Non-Lecture
Review of Thermodyamics
First Law:
dU = dq + dw
dU = 0
dn
i
(Tsurr, pext)
H = U + pV
H(S, p, {ni})
dH = TdS + Vdp +
dn
i
A = U TS
A(T, V, {ni})
dA =SdT pdV + idn i
i
G = H TS = A + pV
G(T, p, {ni})
dG =SdT + Vdp + idn i
i
T =
=
S
V,{ni } S
p,{ni }
U
A
p =
=
V S,{ni }
V T,{ni }
Lecture 1, Page 4
V =
=
p S,{ni }
p
T,{ni }
A
G
S =
=
T V,{ni }
T p,{ni
}
U
H
A
G
i =
=
=
=
n i S,V,{n j =ni } n i S,p,{n j ni } n i T,V,{n j ni } n i T,p,{n j ni }
2 U
2 U
p
T
SV
{ni }
VS
{ni }
V,{ni }
V
S,{ni }
2 G
2 G
V
=
i
=
= Vi
2 G
2 G
=
i
= Si .
V =
p
T
G
H = G T
T p
G
G
U = G T p
T p
p T
G
A = G p
p T
Lecture 1, Page 5
2 G
Cp = T 2
T p
Condition for
Equilibrium
N, p, T
G minimized
N, V, T
A minimized
N, p, S
H minimized
N, V, S
U minimized
N, U, V or N, H,p
S maximized
(2nd Law)
closed, isolated
system
(N, E, V) S(N, E, V)
Q(N, T, V) A(N, T, V)
Lecture 1, Page 6
Lets begin!
Macroscopic: U, H, A, G, S, , p, V, T, CV, Cp
N 1023 particles
pV = RT
F=CP+2
# components
# phases
There are only a few things about a bulk system that we can (or need to)
measure!
Classical Mechanics:
px, py, pz, x, y, z for each particle ( p 3N , q 3N )
Quantum Mechanics:
quantum state (nx, ny, nz) for each particle.
Classical Mechanics:
Quantum Mechanics:
Lecture 1, Page 7
Suppose we had all this information, every time there is a collision, we need
to do a complicated calculation.
Cartoon description
Classical Phase Space
q 3N (
t 0 + t ) , p 3N (
t 0 + t )
p 3N
q 3N ( t 0 ) , p 3N ( t 0 )
q 3N
( )
3N quantum numbers
Lecture 1, Page 8
* idealizations (initially)
* amazing properties of average over very large numbers of degrees of
freedom
* combinatorics
* average and most probable behaviors
Formalism: How do we describe the state of a system consisting of man
particles: an assembly?
Each quantum state of an assembly consisting of N non-interacting particles
is described by 3N quantum numbers.
state
n1x
n1y
1
1
2
1
E = i
1
2
i=1
nx ,ny ,nz
h2
2
2
2
=
n
+
n
+
n
y
z
2 x
8mL
Since the and states have different sets of occupation numbers they are in principle
distinguishable, but they do have the same E. Degenerate state.
Degeneracy (E,N) number of (in principle) distinguishable assemblies with
the same total E and N
But collisions cause the quantum state to change rapidly and unpredictably with time.
What do we do?
Make the ERGODIC HYPOTHESIS
Replace time average over microscopic description by ensemble average
ENSEMBLE collection of an enormous number of replicas of the assembly. In a sense
this includes all microscopic states that the time evolving state would pass through after
an infinite amount of time. WE CAN DO THIS!