Lecture 1 Notes: Dilute Limits
These are properties of solutions in the dilute limit, where there is a
solvent A and a solute B where nA> nB.
mix
These properties are a direct result of A
pure
(l,T,p) A
(l,T,p)
Use two measures of concentration:
a.
Mole F
Lecture 3 Notes: Entropy Probabilities
The partition functions play a central role in statistical mechanics
All the thermodynamic functions can be calculated from them!
Start with average system energy U = <E>
Substitute 1/kT
pE 1
i
Q
i
U E
i
i
Ee
E
i
i
Lecture 6 Notes: Zero Order Reactions
aA + bB cC + dD
Rate of Reaction:
Rate
1 dB 1 dC 1 dD
1 d A
a dt
b dt
c dt
d dt
Experimentally Ratek
Where
Cii
N
i1
k = rate constant
Ci = Concentration of Reactant i
i = Order of reaction with respect to
reactant i
Lecture 2 Notes: Statistical Mechanics
Properties of
Individual
Atoms/Molecules
H E
Macroscopic
Thermodynamic
Properties
Statistical
Mechanics
G H TS
RT ln K p
0
0
0
Goal of Statistical Mechanics: to describe macroscopic,
thermodynamicproperties in terms
Lecture 5 Notes: Applied Methods
Apply statistical mechanics to develop microscopic models for problems youve
treated so far with macroscopic thermodynamics
Separated atoms
0
Products
Reactants
Product & reactant
E
energy levels
r = -D0,r
p = -D0,p
Chemic
Lecture 9 Notes: Chain Reactions
IV) Chain Reactions
Where a product from a step in the mechanism is a
reactant for a previous step (i.e. the reaction feeds itself).
a) Stationary or stable chain reactions.
The concentration of reactive intermediates
is c
Lecture 10 Notes: Molecular Structure
Arrhenius Law
kAe
where
Ea /RT
Ea Activation Energy
A Pre-Exponential Factor
k(T)
lnk(T)
k=A
Slope=-Ea/R
T
Typically:
T
Ea ~ 50-300 kJ/mole
12
15
A (unimolecular) ~ 10 10
(bimoledular) ~ 10
11
-1
sec
liter/(mole sec)
Lecture 7 Notes: Reaction Intermediates
Mechanisms: A series of elementary steps that make up
areaction.
e.g. for A + B + 2C D + E
Mechanism could be:
A+BF
F+CG+D
G+CE
Elementary
Single Step
Reactions
F and G are reaction intermediates
Molecularity: The n
Lecture 8 Notes: Reversible Reactions
III)
Reversible Reactions
B
k1
A
If 1
st
K
B
k-1
order,
eq
eq
Aeq
Rforward = Rf = k1[A]
Rbackward = Rb = k-1[B]
At Equilibrium, Rf = Rb
k1[A]eq = k-1[B]eq
k1
Keq
k
1
st
a) 1
order reversible reactions
A
B
k1
d[A]
k
Lecture 4 Notes: Double-Stranded
Polymers
Starting with QM energy levels for molecular translation, rotation, & vibration,
solve for q and Q, & all the thermodynamics, for these degrees of freedom. The
results are the fundamentals of molecular statistical