ENVE 206

Physico-chemical Principles of
Env. Eng
CHAPTER 3
Liquid-Liquid (L-L) & Liquid-Gas (L-G)
Interfaces –Part 4
2020 – 2021 Spring
Filiz B. Dilek
 Micelle Formation- Critical Micelle Concentration (cmc):

Micelle formation can be represented by a reaction


nS  mM 
 S M 
n m 
 z

where n: degree of aggregation; S- : surfactant HC tail; M+: polar head; z: net charge of the micelle, z=n-m

The equilibrium constant for the reaction:

a mic
K n m a: activity
aS  aM
The well-known thermodynamic result can be applied:
G 0   RT ln K
G 0   RT ln a mic  n ln a S  m ln a m 
Dividing both sides by n expresses this free energy change per mole of surfactant, ∆𝐺°𝑚𝑖𝑐 (= ∆𝐺°/n)

At the cmc,
am  a S  aCMC
So;

G 0 1 m 
  RT  ln a mic  ln aCMC  ln aCMC 
n n n 

Proper arrangements and assumptions (since n is large, 1/n ln amic can be neglected as
compared to others) will lead:

 m
G 0
mic  RT 1    ln aCMC
 n
cmc occur in dilute solutions, so activity (a) may be replaced by the concentration (c) of
surfactant at the cmc.
Note: If m is set as «0» for ionic micelles, contribution of surfactant alone (without including the
contribution of ionic part) will be determined.
Example: Calculate the standard free energy change per mole of non-ionic surfactant
if the c.m.c is 8*10-4 mole/dm3. Aggregation number is 10 and temperature is 25°C.

Solution:
 m
G 0
mic  RT 1    ln aCMC Non-ionic surfactant, so m=0
 n

= 8.314 N.m/(°K.mole)*298 °K (1+0/n) ln (8*10-4 mole/dm3 / 55.5 mole/dm3)

= -27618 N.m/mole = -27618 J/mole= -27.6 kJ/mole

Note: Molar conc. of water: 55.5 mole/dm3

Activity= mole fraction * activity coef (=1)
Mole fraction= Csolute/Cwater = Csolute / 55.5 mole/dm3
Also, in a way, the unit within ln function will be eliminated.
 Spreading
Adhesion and cohesion
The work of adhesion between two immiscible liquids is equal
to the work required to separate unit area of the liquid-liquid
interface and form two separate liquid-air interfaces (Work of
adhesion (a) and of cohesion (b), and is given by the Dupre
equation 𝑾𝒄 = 𝟐𝜸𝑨
Spreading of one liquid on another
When a drop of an insoluble oil is placed on a clean
water surface, it may behave in one of three ways:

1. Remain as a lens, (non-spreading).

2. Spread as a thin film until it is uniformly

distributed over the surface as a 'duplex' film. (A
duplex film is a film which is thick enough for the
two interfaces - i.e. liquid-film and film-air - to be
independent and possess characteristic surface
tensions)

3. Spread as a monolayer, leaving excess oil as

lenses in equilibrium.
 If the area occupied by the oil drop is increased by dA, the change in the surface free energy:
dG = (γO/A + γO/W − γW/A ) dA

If this quantity is negative, the spreading will take place sponteneously. Then,
initial spreading coefficient (S) for the case of oil on water):
S = γW/A − (γO/A + γO/W )
The condition for initial spreading is that S be positive or zero.

Also, considering work of adhesion & cohesion equations,

𝑾𝒄 = 𝟐𝜸𝑩
S can be written as:
𝒐𝒓 𝑾𝒂 (𝑶/𝑾 = 𝜸𝑾/𝑨 + 𝜸𝑶/𝑨 − 𝜸𝑶/𝑾 𝒐𝒓 𝑾𝒄 (𝒐𝒊𝒍) = 𝟐𝜸𝑶/𝑨
 𝑾𝒂 (𝑶/𝑾) − 𝑾𝒄 (𝒐𝒊𝒍) = 𝜸𝑾/𝑨 + 𝜸𝑶/𝑨 − 𝜸𝑶/𝑾 − 𝟐𝜸𝑶/𝑨

𝑾𝒂 (𝑶/𝑾) − 𝑾𝒄 𝒐𝒊𝒍 = 𝜸𝑾/𝑨 − 𝜸𝑶/𝑨 + 𝜸𝑶/𝑾

S= 𝑾𝒂 (𝑶/𝑾) − 𝑾𝒄 𝑺
𝒐𝒊𝒍

If 𝑾𝒂 (𝑶/𝑾 > 𝑾𝒄 𝒐𝒊𝒍 , the oil-water interaction is sufficiently strong to promote the
wetting of water by oil (Positive S)

Conversely, no wetting occurs if 𝑾𝒂 (𝑶/𝑾 < 𝑾𝒄 𝒐𝒊𝒍 since the work req’d to
overcome the attraction b/w oil molecules is not compansated by the attraction b/w
oil and water (Negative S no spreading)
Factors affecting the Spreading Coefficient