Accumulation of Solutes at Interfaces

36

Does an isotherm describe an

equilibrium or kinetic relationship
between Γ2 and C2 (Q9)?

A.  Equilibrium
B.  Kinetics

37

1
 Equilibrium
G = Gibbs Function/ Gibbs Free Energy
dG = Vdp - SdT + ∑iµidni

So at equilibrium, dG would be (Q10):

A.  Positive
B.  Negative
C.  Zero
38

Given the Gibbs adsorption isotherm applies at the

air-water interface 1 dσ
Γ2 = − C2
RT dC2

and assuming surface tension decreases with

increasing concentration of chemical 2 (that is, dσ/
dC2 < 0), would you expect an excess or depletion of
chemical 2 at the air-water interface (Q11)?

A.  Excess
B.  Depletion

39

2
 Time for a movie!

Hydrophobic effect
§  Nonpolar molecules in water à increase in order in
water molecules à rejection of nonpolar molecules
and aggregation
§  Amphipilic molecules (surface-active molecules or
surfactants)
–  air water interface
–  critical micelle concentration à pollutant removal
(transport and filtration)
–  Phospholipids: cell / membranes barrier to water
transport

41

3
 Driving force for self-assembly/association/aggregation of
non polar molecules
The hydrophobic effect
Hydrophobic molecules aggregate to
reduce the area exposed to water

WATER – Hydrogen bond

Applications of SAAs

textiles, cosmetics, pharmacy, paint and food,

cleaning/detergents (40%)

Surfactants are compounds that lower the surface tension

4
 Surface Active Agents

Dirt

•  Small amphiphilic organic compounds: hydrophobic tails and hydrophilic head

groups → water insoluble component and a water soluble component
•  Hydrophilic “loves” water → polar residues
•  Hydrophobic “hates” water → non-polar residues, e.g. HC
•  Surfactants diffuse in water and adsorb at interfaces
•  Properties at the interface are modified

Surface active agents

Air-water interface Air-oil interface Oil-water interface
air air oil

water
water oil

Strong adsorption, Little adsorption, Strong adsorption,

substantial lowering little lowering of substantial lowering
of surface tension surface tension of interfacial tension

Gibbs-Isotherm
dγ dγ a=activity
Γi = − ~− c=concentration
RTd ln ai RTd ln ci

5
 Surface active agents
As the surface becomes crowded with surfactant more
molecules will arrange into “micelles” (later more). At some
critical concentration (CMC) the surface becomes “saturated”
with surfactant and any further surfactant addition remains in
solution.

Low concentration Higher concentration C>Cmc

Adsorption
Adsorption is the accumulation of
atoms or molecules at interfaces,
for example, at the surface of solids
Examples - Water decontamination:
1) Activated Carbon
2) Ion-exchangers

Surface energy and adsorption

47

6
 Adsorption Isotherm
Langmuir BET Freundlich

48

Langmuir Isotherm
Gas or solute
molecules

S
Adsorption
Sites

Figure 4.5: Adsorption of molecules on an ideal surface

49

7
 Assumptions of the Langmuir
Isotherm
§  Chemisorption in a limited number of identical sites
(monolayer)
§  In the liquid or gas phase the molecules behave like
an ideal gas or solute (i.e. obeys the ideal gas law
and Henry’s law)
§  There are no interactions (or uniform interactions)
between adsorbed molecules
V/Vm
Langmuir isotherm (red) and
BET isotherm (green)

1
50
P/P0

Assumption for Langmuir isotherm

A.  Formation of a monolayer (no multilayers)
B.  All adsorption sites are the same
C.  No lateral interactions between adsorbate
molecules
bCe
q = Q0
1 + bCe
q = the number of moles ( or mass ) of adsorbate adsorbed per unit mass of adsorbent
Q 0 = the number of moles ( or mass ) of adsorbate adsorbed per unit mass of adsorbent
at complete surface coverage
b = Langmuir coefficient
Ce = concentration of adsorbate
1 1 1
= +
qe Q 0bCe Q 0 51

8
 Langmuir BET Freundlich

In liquid/gas In gas

52

BET
300
250 N2 adsorption used to
determine surface
200 area and micro/
mesoporosity
Vad

150
100 2975
50
0
0 0.35 0.5 1
P/Ps 53