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Spring 2008
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5.62 Lecture #9: CALCULATION OF MACROSCOPIC
qtrans
The macroscopic thermodynamic properties are written in terms of Q. Q is
related to the single-molecule partition function q, which is the sum over the molecular
energy levels or states. Atoms and molecules have different kinds of states or energy
levels. Each type of state makes its contribution, through q, to the macroscopic property
under consideration.
3/2
⎛ 2πmkT ⎞
=⎜
⎝ h 2 ⎟⎠
q trans V
N
1 ⎡
⎛ 2πmkT
⎞ ⎤
3/2
q Ntrans
Q trans = = ⎢⎜⎝ ⎟ ⎥
V
N! N!
⎣
h 2 ⎠ ⎦
⎡
⎛ 2πmkT ⎞3/2 ⎤
lnQtrans = – ln N ! + N ln ⎢⎜ ⎟ V
⎥
⎣⎝ h 2 ⎠
⎦
3
⎛ 2πmk ⎞ 3
= −N ln N + N + N ln ⎜ 2 ⎟ +
N lnT + N lnV
2
⎝ h ⎠
2
Calculate the translational contribution to the average energy (one of the contributions to
U, internal energy)
⎛ ∂ ln Q trans ⎞
E = kT2 ⎜ ⎟
⎝
∂T
⎠
N,V
⎛ ∂ ln Q trans ⎞ 3N
⎜ ⎟ =
⎝
∂T
⎠
N,V 2 T
⎛ 3 N⎞ 3 3
E = kT2 ⎜ ⎟ = NkT = nRT
⎝ 2 T⎠ 2 2
5.62 Spring 2008 Lecture 9, Page 2
⎛ ∂U ⎞
CV ≡ ⎜ ⎟
⎝ ∂T ⎠N ,V
⎛ ∂E ⎞ ∂ ⎡3 ⎤
CVtrans = ⎜ trans ⎟ = ⎢ NkT ⎥
⎝ ∂T ⎠N ,V ∂T ⎣ 2 ⎦
3 3
= Nk = nR
2 2
Recall from 5.60 that CV for an ideal monatomic gas was often observed to be
3
CV = CV / n = R
2
There are no other important places other than translation for an ideal monatomic gas to
put internal energy.
⎛ ∂A
⎞ ⎛ ∂lnQ ⎞
p = −
⎜ ⎟ = kT ⎜ ⎟ (recall dA = –pdV – SdT + µdN)
⎝
∂V
⎠N,T ⎝ ∂V ⎠N,T
because A = –kT ln Q
32
⎛ 1
⎞ ⎛ 2πmkT ⎞
= N ln V + ln + N ln ⎜
⎝ h 2 ⎟⎠
ln Q trans (only the first term
⎝
N!
⎠
is V dependent)
⎛ ∂ ln Q trans ⎞ N
⎜⎝ ⎟⎠ =
∂V N,T V
So
p = NkT/V
pV = NkT = nRT
IDEAL GAS LAW
S = k ln Q + E /T
⎡ (2πk)3/2 ⎤ 3 3
ln Q trans = N ln ⎢ 3 ⎥ + 2 N ln m + 2 N ln T + N ln V − ln N!
⎣ h ⎦
⎧⎪ ⎡ (2πk)3/2 ⎤
3 3
⎛ V ⎞⎫⎪
So ln Q trans = N ⎨
ln ⎢ ⎥ +1+
ln m +
ln T + ln ⎜ ⎟⎬
⎪⎩
⎣
h 3 ⎦
2
2
⎝ N ⎠⎪⎭
V kT V
Now = ∴ln = ln k + ln T − ln p
N p N
⎡ ⎡ (2π)3/2 k 5 2 ⎤
3 5
⎤
So ln Q trans = N ⎢ln ⎢ ⎥ + 1+
ln m +
ln T − ln ⎥
p
⎣
⎣
h3 ⎦
2
2
⎦
E
S = k ln Q + = k ln Q + ( 3 / 2 ) Nk
⎡ ⎡ (2π)3/2 k 5/2 ⎤
5 3 5 ⎤
S = Nk ⎢ln ⎢ 3 ⎥ + + ln m + ln T − ln p ⎥
⎣ ⎣ h ⎦
2 2 2 ⎦
S 5 3 5
= ln T + ln m − ln p + + ln (constants)
Nk 2 2 2
S 5 3
= ln T + ln m − ln p −1.164871
Nk 2 2
5 3
S Nk = ln T + ln m − ln p − 1.15170 [p] = bar
2 2
SACKUR-TETRODE EQUATION
1911-13
e −ε(L,M,N )/kT h 2 ⎛ L2 M 2 N 2 ⎞
Pi = PL,M,N = where ε(L, M, N) = ⎜ + + 2⎟
q trans 8m ⎝ a 2 b 2 c ⎠
quantum = ε x (L) + ε y (M) + ε z (N)
state
The lowest possible energy is for
L=M=N=1
probability of molecule in
numbers # L, M, N
Because the allowed energies of a molecule are so closely spaced, the discrete P(ε) can be
approximated by a continuous P(ε) dε. If P(ε) is treated as continuous, then PL,M,N must
also be treated continuous because these distributions must map onto each other. The
problem is more easily solved for 1 dimension at a time. Consider the x-dimension only
because
1 2 12 12
⎛ 2πmkTa 2 ⎞ ⎛ 2πmkTb 2 ⎞ ⎛ 2πmkTc 2 ⎞
q trans = qx qy qz = ⎜ ⎟⎠ ⎜⎝ ⎟⎠ ⎜⎝ ⎟⎠
⎝ h2 h2 h2
Now P(εx) and P(L) are two continuous distribution functions which must map onto each
other. In essence, they represent the same distribution but the variable has changed.
Problem is to relate P(L) to P(εx). This can be done by
dL
Calculate so that P(εx) can be calculated
dε x
1/2
L2 h 2 ⎛ 8ma 2 ε x ⎞
εx = or L = ⎜
8ma 2 ⎝ h 2 ⎟⎠
1/2 1/2
dL d ⎛ 8ma 2 ε x ⎞ ⎛ 2ma 2 ⎞
so = ⎜ ⎟ =⎜ 2 ⎟ −1/2
εx
dε x dε x ⎝ h 2 ⎠ ⎝ h ⎠
so P ( ε x ) = P(L) = ⎜⎝ h 2 ⎟⎠ εx
−1/2
dε x qx
⎛ 2ma 2 ⎞
1/2
e−εx /kT −1/2
1/2 ⎜ 2 ⎟
= εx
⎛ 2πmkTa 2 ⎞ ⎝ h ⎠
⎜ ⎟
⎝ h2 ⎠
P ( ε x ) = ( πkT)
−1/2
ε −1/2
x e −εx kT
(
Check normalization require ∫0 P ( ε x ) dε x = 1)
∞
⎛ 1 ⎞
1/2
P (εx ) dεx = ⎜ ⎟ ε−x1/2 e−εx kT
dεx
⎝ πkT ⎠
⎛ 1 ⎞
1/2
π1/2
∫ P(εx )dεx = ⎜ ⎟
⎝ πkT ⎠
= 1
(1 / kT)1/2
correctly normalized.
Therefore:
BOLTZMANN KINETIC
P ( ε x ) = ( πkT)
−1/2
ε −1/2
x e −εx kT ENERGY DISTRIBUTION
FUNCTION IN 1D
We know f(x) but we want to take the information contained in f(x) and re-express it in
terms of a different variable, y.
f(x)dx ≡ g(y)dy
dy
dy = dx
dx
dy dy
f (x)dx = g(y) dx thus f (x) = g [ y(x)]
dx dx
and
dx
g(y) = f [x(y)]
dy
g[y(x)] means: evaluate the function g(y) at the value of y determined by the value of the
function y(x) evaluated at x.
∂r ∂s ∂t
… …
∂x ∂x ∂x
∂r ∂s ∂t
… …
∂ ( r, s,t,…) ∂y ∂y ∂y
=
∂ ( x, y, z,…) ∂r ∂s ∂t
… …
∂z ∂z ∂z
. . . … …
. . . … …
Example: x, y, z, ↔ r, θ, φ
x = r sin θ cos φ
y = r sin θ sin φ
z = r cos θ
3 x 3 determinant
∂x ∂y ∂z
∂r ∂r ∂r sθcφ sθsφ cφ
∂x ∂y ∂z
dxdydz = drdθdφ = rcθcφ rcθsφ −rsθ drdθdφ
∂θ ∂θ ∂θ
−rsθsφ rsθcφ 0
∂x ∂y ∂z
∂φ ∂φ ∂φ
q = ∑ e−εi kT
i
and that the fractional population of the i-th level in one molecule is
fi = e−εi kT
q
ni = Nfi .
The population ratio for levels i and j
fi ni
= = e ( i j)
− ε −ε kT
fj nj
For T > 0.
For T → 0K f j fi
But if f j > fi (as occurs in a laser gain medium) that would imply T < 0.
There is no possibility of equilibrium with T < 0K, but one often uses a population ratio
as a thermometer. Thus a “steady state” (but not equilibrium) situation is often described
by a negative absolute temperature. Note that, if you started with a steady state sample at
“T < 0K”, and then turned off the source of energy input that sustains the nonequilibrium
steady state, that “T” (defined by a population ratio) would become increasingly negative,
pass through –∞ directly to +∞, and then decrease to the equilibrium T of the
surroundings.