CHL721 Adv Chem Engg Thermodynamics

HW #8

Due date: 27th April, 2015 (in lecture)

(* all equation numbers below are w.r.t Ch-2 of Barret &

Hansen)
Q1: Thermodynamics of micelle formation
a. Assuming ideal gas statistics, derive the entropic
contribution to surface free energy in eq. 2.101
b. Starting with eq. 2.106, show that chemical potential
can be expressed in form given in eq. 2.107.

Q2: Spherical Micelles

Each sodium dodecyl sulfate surfactant (SDS) molecule in a
spherical micelle can be visualized as a cone of fixed volume

and variable head-group area a s . In the micellar form,

the internal interaction free energy per molecule can the
be written as
s
2
( a sas )
as
=

where, * signifies values corresponding to the minimum of

free energy.
a. Show that aggregation number for a spherical
micelle of radius R can be written as
=4 R2 /a s=36 2 /a3s .

b. Now use a Taylor series expansion up to 2 nd order in

aggregation number to express internal free energy as
+C ( )
=

, where C is a constant. Also find C in

terms of known parameters ( s , , a s ).

c. Now starting at eq. 2.108 and using the result derived

in part (b) above, derive an expression for distribution

of surfactant mole fraction x / about = .

Determine the corresponding standard deviation.
d. Determine numerical value of standard deviation and
make a plot of x versus given following data for
2

SDS: s=20 mJ m , a s=0.60 nm , =60 ,

=10 mM
.
x