20120201

Wrap up Blankschtein & Puvvada

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Continue with student presentations
Micellization Thermodynamics
(continued) Review of seminal paper
Puvvada and Blankschtein Molecular-
thermodynamic approach to predict
micellization, phase behavior and phase
separation of micellar solutions. I. Application
to nonionic surfactants J. Chem. Phys. 1990,
92, 6, 3710.
continuing
Finish discussion of the model
Computational scheme
Discuss P&Bs evaluation of the thermo.
properties
Model predictions and comparison with
experiments
Equilibrium state of micellar system
fully specified by the time averaged:
Minor radius of the micellar core, l
c

Number of surfactant molecules in the
micelle, n
The geometrical shape of the micelle, Sh
Time averaged variables are used since micelles fluctuate.
Computational strategy
For each of the 3 micelle shapes
Spheres
Cylinders
Disks / bilayers (turned out not to be favored in case
examined by P & B)
The free energy of micellization, g
mic
, is computed
and minimized with respect to l
c

An interpolation scheme is used to account for
finite n for cylinders or disks
Model contains 3 molecular
parameters which must be specified:
n
c
a known property of the hydrocarbon chains
evaluated from experimental results based on
11 carbon chain hydrocarbons
a
h
estimated from the volume of the head
group and its end to end length

Determining n
For spheres a zero growth model is used
For cylinders and disks an interpolation is
made between the infinite n idealized case
and the equivalent spherical micelle,
( ) ( ) ( ) ( ) | | cyl g sph g
n
n
cyl g n g
mic mic
sph
mic mic
* *
*
*

|
|
.
|

\
|
+ =
g
w/hc
, contribution of moving the
hydrocarbon tail from water to the
hydrocarbon core, is the largest
contributor to g
mic

As a
h
increases, the steric contribution ,g
st
,
increases with the increase being larger for
cylinders than for spheres.

>>> larger head groups favor spherical
over cylindrical micelles
The hydrocarbon tail anchoring
contribution increases with
increasing n
c
; is larger for
spheres than for cylinders
Hydrocarbon/water interface
creation term depends
mostly on the shape and
varies little beyond that.
Optimum l
c
is somewhat larger for
spherical rather than cylindrical
micelles
Evaluation of Thermodynamic
Properties
Free energy expressions
Apply multiple chemical equilibrium
principle
Yields micellar size distribution
Find critical micelle concentration
Defined by break in the monomer mole fraction
versus total surfactant concentration curve
Free energy expressions
( )
( )
molecule water a and molecule
surfactant a of volume e between th ratio the is
parameter n interactio the is ,
surfactant fraction volume the is
mers - in surfactant fraction mol the is
(total) surfactant fraction mol the is
where
2
1
1 ln
2
0
I
I
|
.
|

\
|
+
(

+ + =

P T C
m X
X
C
X X X kT
m
m
m w w
|
|

Free energy expressions, cont.
( )
( ) { } 1 1
2
1

1 1 ln
2
0

|
.
|

\
|
+
(

|
.
|

\
|
+ + + =

|

nC
X X n X kT
m
m n n n
Micelle size distribution
( )
( )
)
`

=
=
kT
n ng
X X
n
mic
n
n
n
exp
gives that requiring
1
1

Critical Micelle Concentration
Found from break in monomer mol fraction
versus total surfactant mol fraction curve
Result is the same for each shape
( ) ( )
)
`

~
kT
Sh g
X
mic
CMC
1
exp
*
Comparison with experimental
data
CMC
As a function of EO count in headgroup for C
m
E
n

nonionic surfactants
As a function of T for C
m
E
n
nonionic surfactants
As a function of n
c
for alkyl glucosides
Critical parameters (T
c
and X
c
) for C
m
E
n
nonionic
surfactants
Osmotic compressibility for C
12
E
8
Project guidance
Literature review of general area of interest
Status/progress report due 2/15
Draft due 2/22 (substantially complete)
Assessment of the state of the art in your specific area of interest
Status/progress report due 2/29
Draft due 3/7 (substantially complete)
Identification of research/development needs and/or opportunities
Status/progress report due 3/21
Draft due 3/28 (substantially complete)
Ideas for meeting one (or some closely related) of the
needs/opportunities
Status / progress report due 4/4
Draft due 4/11 (substantially complete)
Final project report
With all four of the above major parts
Due 4/25