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## 5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008 Lecture #29 page 1

## Apply statistical mechanics to develop microscopic models for problems you’ve

treated so far with macroscopic thermodynamics

Separated atoms
0

Products Reactants

## Product & reactant

E energy levels

−εr = -D0,r
−εp = -D0,p

Chemical equilibria
Gas phase: Calculate Kp from microscopic properties

aA + bB F cC + dD

Q = (qtrans
N
N ! ) qint
N

## lnQ = N ln (qtrans qint ) − ln N ! = N ln (qtrans qint ) − N ln N + N = N ln (qtrans qint N ) + N

G = −kT lnQ + NkT = −NkT ln (qtrans qint N ) = −NkT ln (q N )

For molecules in the gas phase, internal degrees of freedom are rotations and
vibrations and electronic states.
5.60 Spring 2008 Lecture #29 page 2

## qint = qrot qvib qelec

qelec = e D 0 kT
Dissociation energy D0 from ground electronic level
Usually no other electronic levels matter

1
qvib = ∑ e −nε 0 kT
= 1 + e −ε 0 kT
+ e −2ε 0 kT
+ e −3ε 0 kT
+" =
n 1 − e −ε 0 kT

Note we’ve set the zero of vibrational energy as the lowest vibrational level.

The zero-point vibrational energy has been included in qelec by using the

dissociation energy rather than the bottom of the electronic potential energy.

## qvib ≈ 1 - Need to calculate it, but it’s not large

We have not treated qrot. Levels are NOT evenly spaced: εrot = J(J + 1)ε0,rot

## We’ve seen that qtrans ≈ 1030, qtrans/N ≈ 106.

For multiple species in chemical equilibrium, need to use Ni for each species and
use partial pressure values in pV term.

## Gi = −Ni kT ln (qi Ni ) = −ni RT ln (qi Ni )

Gi = −RT ln (qi Ni ) = Gi ° + RT ln ( pi p ° )
⎛ qi Ni kT ⎞ ⎛ qi kT ⎞
Gi ° = −RT ln ⎜ ⎟ = −RT ln ⎜ ⎟
⎝ Ni p °V ⎠ ⎝ p °V ⎠

## Example: simple reaction at 300 K: A-B + C-D → A-C + B-D

Assume all molecules have high vibrational frequencies ⇒ qvib ≈ 1 for all species
Translational & rotation: high-T limits
Assume similar rotational energies (depends on moments of inertia)
⇒ qtrans & qrot contributions are all equal
5.60 Spring 2008 Lecture #29 page 3

⎛q q ⎞
ΔGi ° = −RT ln ⎜ AC BD ⎟ = −RT ln K p
⎝ qAB qCD ⎠
qAC qBD e D AC 0, kT
e D BD0, kT
= e(
D0,AC +D0,BD −D0,AB −D0,CD ) kT
Kp = =
qAB qCD e D AB 0, kT D CD
e 0, kT

## Only dissociation energies matter since the other degrees of freedom

contribute equally.

## e.g. isomerization in an organic molecular crystal

NA molecules of A, NB molecules of B, NA + NB = N

## No translation or rotation, no change in pV ⇒ all the change is in the electronic

and vibrational energy

If vibrational frequencies are the same, then only the difference in dissociation
energies is needed.

Q= ∑ i
e −Ei kT = ∑
Ei

Ω ( Ei ) e −Ei kT
microstates energies

## Recall the entropy due to mixing of two species

N
N! N
N! N N

Q= ∑
Ei
Ω ( Ei ) e −Ei kT = ∑
NA = 0 NA !NB !
e ( NADA +NBDB ) kT
= ∑
NA = 0 NA !NB !
e( A ) e( B )
D kT A D kT B

energies
N
N!
∑N qANA qBNB = ( qA + qB ) = qAN (1 + s )
N
where s = qB qA = e (
N DB −DA ) kT
= = e ΔD0 kT

NA = 0 A !NB !

The binomial theorem gives a simple closed form for the sum.

## It’s convenient here to redefine the zero of energy as –DA so qA = 1 and

N
Q = (1 + s ) = 1 + a1s + a2s2 + a3s3 + " + aN sN

## The ground state of the system has all A molecules

5.60 Spring 2008 Lecture #29 page 4

## System energy is E(NB) = NBΔD0.

Probability that the system has this energy is

p ( NA ) = aNA sNA Q

## The average number of B molecules is

N
a1s + 2a2s2 + 3a3s3 + " + NaN sN s ⎛ ∂Q ⎞ ⎛ ∂ ln Q ⎞
NB = ∑ NBp ( NB ) = = ⎜ ⎟=
NB Q Q ⎝ ∂s ⎠ ⎝⎜ ∂ ln s ⎠⎟

and E = U = NB ΔD0

## If vibrational energies differ then qvib also needs to be included.

In general, low vibrational frequency favors a species since the levels are closely

## spaced, so there are many low-energy states of that species.

For chemical reactions involving covalent bonds, the bond energies dominate

over entropy. But the treatment we’ve given could also be used for much more

## subtle changes like rotation of CO molecules in a CO crystal.

Note that this treatment assumes no interactions between different unit cells.

## Solid-solid phase equilibria

Phase transitions between different crystalline phases may be easier to treat
then chemical reactions, because there is just one state at any temperature:
the crystal in phase α or the crystal in phase β.

## Problem set problem

Einstein model for crystalline phases α and β, frequencies να , νβ
Binding energy per atom: −εα, −εβ

Phase α Phase β
0

−εβ
−εα

## energy, so no need to account for this separately.

You can predict the phase transition temperature based on a simple first

principles model.

Phase transition only occurs if the crystal with stronger binding energy, e.g. α

## phase, also has higher vibrational frequency.

Note that this treatment assumes complete cooperativity: the crystal is either

all one or all the other phase. This gives rise to an abrupt T-dependence of the

equilibrium.

## Example: helix-coil transition in biopolymers. Interactions make few long

segments of helix or coil more stable than many short segments. (Similar for

## Extra example (using QM result for qtrans)

Can also calculate solid-gas phase equilibria, i.e. vapor pressure over the crystal.

## Assume monatomic ideal gas – only translational partition function.

N
⎡⎛ 2πmkT ⎞3 2 ⎤ ⎛ ∂Ag ⎞
Q =q g N
trans N! = ⎢⎜ ⎟ V⎥ N! A = −kTln Q
g g
μ =⎜g

⎣⎢⎝ h
2
⎠ ⎦⎥ ⎝ ∂N ⎠T,V
32
⎛ 2πmkT ⎞
ln Q = Nln ⎜
g
⎟ V − Nln N + N
⎝ h
2

32 32
⎛ ∂ln Q g ⎞ ⎛ 2πmkT ⎞ ⎛ 2πmkT ⎞ V
⎜ ⎟ = ln ⎜ ⎟ V − ln N − 1 + 1 = ln ⎜ ⎟
⎝ h ⎝ h N
2 2
⎝ ∂N ⎠T,V ⎠ ⎠
32
⎛ 2πmkT ⎞ kT
μ g = −kTln ⎜ ⎟ (ideal gas)
⎝ h p
2

## Condition for phase equilibrium: μs = μg

32 52
⎛ kT ⎞ ⎛ 2πm ⎞ (kT )
μ = −ε − 3kT ln ⎜
s g
⎟ = μ = −kT ln ⎜ 2 ⎟
⎝ hνE ⎠ ⎝ h ⎠ p
3 32
⎛ 2πm ⎞
32
(kT )5 2 ⎛ hνE ⎞ (2πm ) ν3E
ε = kT ln ⎜ 2 ⎟ ⎜ kT ⎟ = kT ln
(kT ) p
12
⎝ h ⎠ p ⎝ ⎠
32
(2πm ) ν3E
p=
(kT ) e ε kT
12

gives vapor pressure p(T) over the crystal! Strong binding energy or low T give
low pressure as expected. Low vibrational frequency also gives low p, since this
allows higher entropy in the crystal.
So you can calculate the p-T phase diagram that you described before in
macroscopic terms only.