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Chem 33 Notes

Earl St Sauver


Logistics and Housekeeping

There’s some sort of schedule change. I don’t really know, I came in a touch late, but there
appears to be a sched. change.
There’s a review session the night before the test. Homework is likely due a week from
today on the 13th.
HW will be posted today.
There’s a call for climate justice... Tommorrow at 10/7/2010 there’s a lecture/presentaiton
on the reasearcht hat they did over the summer.

The Boltzman Distribution

ni Ei −Ej
= e− kt (1)

This distribution is the beginning of statisitcal mechanics, and intutiviely makes sense given
that there’s a finite amount of energy for any set of a molecules. While on a macro scale, the
energy is about RT but in the boltzman equation for individual molecules it’s aproximately
kT . kT is aproximately the energy of collisions, and so if they’re both at a lower state the
chance that the energy in the lower electron state will make the jump is low.

Contribution to U
• Translation

• Rotation

These notes come with no warranty of being correct, logical, or complete, particularly in regard to
spelling. If you can’t handle an occasional chmestry in these notes, put it down now. If you send corrections
to, I may or may not fix it... eventually

• Vibration

These are all WITHIN molecules.

There’s also electronic contributions, but they’re effectively zeroed out. We also can’t
get an answer for classical mechanics for electrons because it totally breaks down.
Then there’s also intermoleculer interactions which are V(R) that are dominant in the
gas phase. IN liquid and solid phase there are higher order interactions, with molecules
working together in groups of 3 or 4 or 5, but we’re going to ignore that for now. Let
n = deg. of freedom
U= Un
= ( modes)(#given terms in erengry expression per mode)(Contribution per quadratic term)
= Utrans + Urotation + Uvib

In classical mechanics we get.

Utrans = ntrans · 1 ·
kt 2kt
Urot = nrot · 1 · = for linear
2 2
= for nonlinear

Uvib = nvib · 2 ·
= (3N − 5)
(3N − 6) Ue l ≈ 0

3RT 2 2
Ucl,m = Na vUmolecule = + RT + (3N − 5) RT + Uinteraction m
2 2 2
= (6N − 5) + Uinteraction, m for linear
= (6N − 6) + Uinteraction, m for nonlinear

and this classical model clearly doesn’t actually agree with science, so we have to get rid of
this dealio.

The graphics here only represnet one mode, and each mode has a diff type of spacing and
so each mode will have a different type of modes.
SUmarizing the QM result

trans Uqm = Uc l
rotational Uqm ≈ Uc l
vibrational Uqm =0

Then plugging these suckers in we get

Uqm,m ≈ RT + RT + small terms for vol, contraction, linear
3 3
≈ RT + RT nonlinear
2 2

the rotations in hydrogen are apparently almost the same as low frequenecy vibrations.

Derivation of second law
From 1851 Kelvin, no (CYCLIC) process is possible what the sole result the absorption
of heat from a resovoir and its complete conversion with work. You can do an isothermal
expansion, but eventually the piston falls out.
From 1854 Clausman, It is imposible to have a cyclic process which does nothing but
transfer heat from low temperature