13th January; Lecture about how to estimate

diffusivities

� ktridiC �
1,. - 6- ��·(ft
�� i @avh'c.&t .
M�
{J)
<
� e5T.
z > ds
fY\ � Mass � faAlic&. ( m J
-=
\Jx � .� � ch.- vvi C L(t) 8nJ_ �e_�

� = .· � (4� MA-i->S � GvtS� ( ( .3� xibz 3 Jjo k- )

- · 1 °'
�e �Gvwp-C�) .
. Rwi- ' Iv\ £llvt - �� V�'

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. rn . (i)
� � Al bM$i,I. 1-1\-v ::: G �/�OD cr-y'Male_ <coif
� � . (ow Cm/�ec;
. �-fks 1 a��n'cf&_ �WL<HK
\/ ;i,-
· 2 m� ¼ 0, 35�5
Page 1 of 22
w
So doeslf1\1 \
that make s. �
any sense??
 The reason that makes no sense is that there are other molecules in the
system that would collide with each other thus making the path a
molecule takes chaotic. hence molecules meander in a "random walk like
manner"; see next page.

Page 2 of 22
 path way of a
single molecule in
a mixture.

_i_

Page 3 of 22
Will now present an historical prospective of various attempts to predict Diffusivities from physical
properties of a systtem; the first is a simple probability approach to molecular movement and the
second is a hydrodynamic approach.

Page 4 of 22
 st� o{ k�CW\ Moh� U1'ctPft 1 ���ihl
- � �ix: t. � . ' . --- . { S:eo?'--wv,
G · S-
b I e.;,15 l
� \ CJ I j 1 (/ 1
-J-fi -t'fi f Jb
� ,_,ecl--
� . V
Mt'cwt 0&L¼ll.ecl ctt&plaeoi,.._� , " ,
x tl\r-eJ-i�
<._ Y/-) :: ;}_ i ,7t {i)
D �·c1eJ .. ·
[%J
=c �

· < x ;> /2-t

Assumes a particle has a

=
'-
,, D
50:50 chance of "hopping" to
left or right along a line a
distance δ in a fixed time
period.

�& � �leu, l-D �s � � �, c&:��

<.f
> ::- d-D,t CtM..JI Z � > = Jilt. 2-

W'f. b d-1.t:�10J Ai- S 't Sf&/\ .

,_ \l-00

Fet. The�
Il= + + r., "2..
viM�,VfJA:L- Sl{£>fEH
-r- X2 e,(L

'- > � Co D t]
l (J
A.l,_

� { <( r
IH,rL'1 � Ei��lf fvt Lklt'�
�olE:
I
)<.
DOES tJoT

elJ
Page 5 of 22 \- l l,l Dt'S,a,,te,E" �
�cui.,E.. S�=l:E. �
� �--
__ -
___-�/
-,' -4.
Now move to the Hydrodynamic Approach; which treats a solute molecule moving in a solvent
with a force balance.

Page 6 of 22
 '

N01+ G� 01Zfd & o,rf"',;s1�

Teusk.e � SeC/� {/;. \ 1 - & . re,
Hy <l ID d y rta /.-1 i c Apy,e-a&l .
5-fok:es ·- E 1 sT8 t' bQuw-hun

JJ [ LI�t] ::::
AJ 5
z_
kB'z= T
/ �
!3oLTWAJ k_
COt-.JS�
[. 3f X/D-
23
J/ K

Note: these diffusivities are still "mutual" diffusivities

and are also considered translational diffusivities

Page 7 of 22
 If the solute molecule is NOT a sphere then the DRAG on the molecule is affected
by its shape

Translational Drag Coefficients (f) for Stokes-Einstein Equations

Sphere: f = (6 rr µB Ra)

Prolate Ellipsoid:

a
P = a/b>1
(ora>b)
b

Oblate Ellipsoid

P = a/b < 1

Thin Circular Disc f = 16 µBa

Radius a

C
Cylinder
Radius a
Length L () f = 4rrµsl / [ /ne(L/a) + 0.193]

Page 8 of 22
 Wha i:S � dUJoAO"lc<L
"'"' �,� +b1Y1 is � q
·Jr '
C;

2.ft>3 C,1-1
+�1n,s ,actei <' Ji�'
��&,.- ftiMJe-w, -LJzztt dfvteipf 61' �kv}\ ;4. t1.
see Page 3
�/
Note this "image assumesV\\�the solute �
o
molecule does not rotate about an axis
before it collides with another molecule. If 0� 00 � S'i-<4�) i'1�s !

r
everything were a sphere, the rotation
would not have much affect on the "drag"
VJ.,----
V /
J

on the particle, but if the solute were a

cucumber then the drag would be
significantly affect depending on how the
\; . -- .

molecule were rotating.

This rotational affect is called "rotational

diffusion"

UU-U(s fY\C(,r < l I

�o� Di��

Page 9 of 22
using a probability approach similar to tranlational randome jumps in a '

���J�ii­
\{2,f\1\9bL,�
{'1el1"' SQ� &,,t� \i�
straight line; assume a molecule can have a 50:50 chance to "rotate" in
a positive or negative angle

( . z ¢ {V\)� � f\ �
'-
<. 'I-..
7- (_n.) > -= (\ � z.

wktr� 0 :: &}.b� � tu.d.._

�dL�1
\V

Y\ � �\ - tl\, � .

ji • < ¢ tt:) I � 'J fJr-t-

� tA t- 1- D @)

s-D
.

ttll

Page 10 of 22
 analogous hydrodynamic approach

Translational Diffusivity
Rotational Diffusivity

I L

L _ �:- '-;_/t: 19
t) � �- I -)

C · 9{r

,-.· +?
\l

Page 11 of 22
Rotational Drag Coefficients

Disc

Ellipsoid fr= (16 n µs a b2 } / 3

I
3
Ellipsoid fr= (8n a /3} / [ /ne(2a/b} - ½]

Page 12 of 22
"IM\Uct' � ���c� \c&� D� � 7
() s l� � D-r
�

a 'l M�a_ck .i (\O'lJ,aAJ):> �

C \� l\t�uJ!Ai MA

·0]1-
A

Page 13 of 22
 Since the hydrodynamic approach in the late 1930s, there has been a plethora of
correlations derived trying to predict diffusivities based on incrporating ever increasing
number of physical properties of the system; here are a few such correlations for liquid and
gases systems

Page 14 of 22
Page 15 of 22
Page 16 of 22
Page 17 of 22
 Now onto another significant effect on diffusivities known as transport in
"restricted spaces", which leads to the concept of an "effective diffusivity".

So, Diffusivity, mass diffusivity or diffusion coefficient is a proportionality

constant between the molar flux due to molecular diffusion and the gradient in
the concentration of the species (or the driving force for diffusion). The
diffusivity is generally described for a given pair of species and pairwise for a
multi-species system. The assumption here is that both the solute and solvent
molecules have the freedom to translate and rotate between collisions.

However in a number of cases, the solvent and solute are moving within a
"restricted" space (e.g., proteins in an PAGE electrophoreous gel, proteins
moving through a HPLC packed column, drug molecules diffusion through
polymer capsules). As a consequence of this confinement, the solute:solvent
molecules also collide with the solid restrictions, thus affecting their freedom to
move.

There are numerous ways to corrected for this restriction through an "effective
diffusivity".

Page 18 of 22
 Di�'o"n .� �'olo("(t;f � �� .
0'
{l,t,i
.
Mt
I t�(
t �'{ .

!liii¼ -+ fl\� t ufbf bu I ·. � 1 l :VJ-tr� I

.
� �I 11,1�J-v-� •

'/hie) ® m/f t,,t,,;/5

iwr , ,
;j
� � .
�. IIW-t--f•� d» _rndJ;- �
- 'St}. lO-r-tf{;f-

Page 19 of 22
Page 20 of 22
 /Y\�s ]� � Dbstr� [-f+cds
11
f

'Jtl¾ � ,ii -ft&__ " P ore rn & /I

LI�� Y-

•
, � �

>-�
L ;
1
V

- �;':.,.<WcuJ)
� o/
(ft.�) f � \Jwiltt. - \/e�t.
\f��

Page 21 of 22
be Cl/4v'ZVL{ � ecr t
s+o � �
;te,sl\l' i d-£J (; fa:,(Q__, . .

�&,to dj f\lVM C,
lI

?_ '

3 t� � � j-

Wnfils ( J 0'l1j' J; &f-w:;

Lf. K e? �
�
�s �?�)
Note: there are a
number of models
that correct for
transport in a
restricted space
BUT I have only
discussed here the
easiest one,
obstruction.

"

Page 22 of 22