Exam Molecular Thermodynamics (CH 3141) 06-11-2013

Write your name and student number on each paper sheet that you hand i n !
Write the answers to problems 1 to 3 and to 4 on separate sheets, as they w i l l be coiTected
by different people.
Symbols that are not defined here have the same meaning as i n the lectures and/or
Sandler's book and/or the formulary. Define symbols that y o u use, that were not defined
in Sandler's book or i n the lectures, or that may be ambiguous!
W i t h this exam you may use the 'FoiTnulary Molecular Thermodynamics'.
W i t h each question: read carefully,
Success!

and think before y o u start scribbling!!!

Say o f the statements below i f they are true or false. Give a brief explanation (no
explanation means no points)!

a) For a one-component system. -

b) To specify a microstate requires a small number o f variables, to specify a macrostate

requires a large number o f variables.
c) A l l systems w i t h i n a canonical ensemble are in the same macrostate.
d) The probability that a system i n a Grandcanonical ensemble has N molecules is

e) A canonical ensemble contains many micro-canonical ensembles.

f) I n a system w i t h pairwise additive interactions, changes i n fi-ee energy w i t h respect to
an arbitrary order parameter are given by
()A

47iNp\g(r,AX(rydr

g) Monte Carlo simulations can be used directly to compute the thermal conductivity o f a
fluid.
h) I n Monte Carlo simulations, ensemble averages should only be updated after accepted
trial moves.
i) The Debye length increases w i t h increasing electrolyte concentration,
j ) The total charge o f the double layer around an i o n is zero.

Composition

In a temperature vs. composition phase diagram, the so-called binodal curve ( =

coexistence curve) provides the compositions o f coexisting phases. Compositions i n between the binodal pomts at a certain temperature are not thermodynamically stable.
Systems w i t h such an overall composition w i l l phase separate into two coexisting phases.
In the case o f polymer solutions these two phases w i l l be a solvent-rich phase w i t h a
relatively low polymer concentration, and a polymer-rich phase w i t h a relatively low
solvent concentration.
a) What is larger (according to the Flory-Huggins theory and in reality), the volume
fraction o f polymer i n the solvent-rich phase or the volume fraction o f solvent in the
polymer-rich phase?
(NB. The above illustration is not f o r a polymer solution, so you caimot deduce the
answer from the figure.)
b) Explain this by considering the transfer o f a polymer molecule f r o m a phase that
mostly consists o f the same polymer to a phase that mostly consists o f solvent, and the
transfer o f a solvent molecule f r o m a phase that mostly consists o f solvent to a phase that
mostly consists o f polymer.
c) Give the expression for the Helmholtz energy o f m i x i n g according to the FloryHuggins theory.
d) Derive f r o m the expression f o r the Helmholtz energy an expression for the chemical
potential o f polymer as a ftinction o f the volume fraction o f polymer.
e) Indicate how at a given temperature (in the Flory-Huggins theoiy this is at a given
value o f the Flory-Huggins parameter) the composition o f coexisting phases can be
calculated f r o m the expressions o f the chemical potentials.
(you do not have to perform the calculation).

f ) The spinodal cui-ve (see figure) separates compositions that are thermodynamically
metastable from those that are thermodynamically unstable. Metastable compositions are
those between the binodal and the spinodal curves, unstable compositions are those
between the two branches o f the spinodal.
The spinodal is where d^^jdij)^^ = 0 . Derive an expression f o r the spinodal according to
the Flory-Huggins theory. Write the result i n terms o f

as a function o f (f) .

Keto-enol tautomei ism o f acetone.

keto

enol

Acetone is an example o f a molecule that can exist i n two forms: the 'keto tautomer' and
the 'enol tautomer' (the keto f o r m is most abundant). These two forms are in a dynamic
equilibrium i n which they are interconveited all the time. Obviously, the internal singlemolecule partition flinctions are different f o r the two forms. Call the internal partition
fiinction o f the keto f o r m q. , and o f the enol f o r m q. , .
a) Give an expression f o r the internal partition function q.^^ o f acetone i n terms o f q.^^^^
and

?i,,,.

We consider a dilute vapour o f acetone, which may be considered as an ideal gas.

b) Give the equilibrium constant

f o r the tautomerisation reaction in terms o f g.^^

and

q.^^^^. Y o u may use the general expression as given i n the 'Formulary'.

p
c) Give the expression, i n terms o f q,^^^ ^ and q.^^^ ^, f o r the equilibrium constant Kp=
where P^ and P^ are the partial pressiu'es o f the enol and the keto tautomers.
N o w consider the system as an ideal-gas mixture o f A^^, 'keto mlecules' and

'enol

molecules'.
d) Write down the expression f o r the canonical partition function o f the mixture.
e) Deduce f r o m this expression f o r the partition fimction the expression f o r the Helmholtz
energy o f the mixture.
f ) Explain i n words, how the equilibrium values o f A^^, and A^^ can be deduced f r o m this
expression f o r the Helmholtz energy.
(You do not yet have to do the derivation)
g) Peiform the derivation described under (f), and demonstrate that the result is consistent
w i t h what was found under (b).

N B . write tlie answer to problem 4 on a separate sheet!

4
Consider a system of W hard spheres inside a volume V at temperature T.
(a) Show that the configurational integral at low densities can be expressed as
Z{N, V,T)^V(Vc ) ( F - 2c)...(F - (TV - l ) c ) in which c is a constant.
(b) What is the physical meaning of the constant c ? Explain in 10 words maximum.
(c) Which approximations are made in (a]? Explain why these approximations are only
valid at low densities. Briefly explain your answer.
(d) Explain that c=4ua^/3

in which a is the diameter of a hard sphere.

(e) Show that at low densities, lnZ(N,V,T)

^ NinV
IV

pV
[ f ] Use the equation of (e] to derive an equation for the compressibility Z = in
NkJ
terms of the number density p=N/V

(g) The second virial coefficient for a system with pair interactions equals
B = 27r][\ - exp[-^(/..(/-)])/-V/0

in which uij is the pair interaction potential. Show that the expression derived in (f)
is in agreement with the value of B of this system.