CHM 342 Surface

1
CHM 342 (2-46) Surface Chemistry

(. )
Surface Tension
Surface tension holds water droplets on the
leaves of the Japanese Root Iris.
How can an insect in the above
picture walk on the water?
( )
2
(. )
Floating a tack on water.
The tack doesnt really float on the
water, because it is more dense that the
water and should sink to the bottom
The reason that it doesnt sink is because
of the surface tension of the water
What is density?

What is surface tension?
3
(. )
A tack on the surface of a glass of water.
Poking the surface of the
water with a toothpick is
not sufficient to disturb
the surface tension
4
(. )
If you dip the toothpick in a soap solution before you poke the water then
the soak will disrupt the surface tension.
5
(. )
The origin of surface tension.
6
(. ) Work required for the Formation of Surface
Separation of liquid
requires work
against cohesion
forces

Surface tension ( or o) - increase in free energy as a result of
formation of 1 unit (m
2
,cm
2
) of surface

Formation of surface of square AO results in increase in the free
energy AG:
) ! ! positive! (always 0 ;
A
G
T p,
>
|
.
|
\
|
c
c
=
0 A G
A
> =
7
(. )
YOUNG-LAPLACE EQUATION
Equation of Capillarity
Pressure inside a drop or bubble is always greater than in
the continuous phase.
The balance between surface tension and external forces
(e.g. gravity) dictate the shape of drops and bubbles.
R
1

R
2

|
|
.
|
\
|
+ =
2 1
R
1
R
1
P
- Interfacial Tension
P - Pressure
R - Radius
8
(. )
Surface Tension is a Force!
Force: mg [N, Newton]
Force: 2L
units: [N/m]
L
Soap film
Surface tension is a vector, i.e. has direction
9
(. )
Measurement of
Surface Tension
External force
Surface tension
x
f
T

Force
Ring tearing
x
Ring tearing technique
nce} circumfere {ring 2
factor) on (correcti f
=
10
(. )
SURFACE TENSION MEASUREMENT
-- du Nouy ring --
t + = ) R 2 ( 2 wt wt
ring total
wt
total
= total weight , wt
ring
= ring weight
R = ring radius , = surface tension
Still commonly used but values may be as
much as 25% in error.
Adamson, Physical
Chemistry
of Surfaces, 2nd Ed
p. 22 (1976)
11
(. ) SURFACE TENSION MEASUREMENT
-- Wilhelmy Plate --
2l
b) (wt wt
cos()
plate total

=
= surface tension
u = contact angle
wt
total
= total weight
wt
plate
= plate weight
b = buoyancy force
l = length of plate
Normal platinum is used to have q 0 and plate just touches
liquid so buoyancy is small
12
(. )
SURFACE TENSION MEASUREMENT
-- Drop Weight Method --
W = 2tr
W = weight of droplet
r = radius of droplet
= surface tension
Ref. Adamson, Physical Chemistry of Surfaces, 2nd Ed , p. 19 (1976)
9
See: http://www.erc.ufl.edu/education/courses/intephen1/_files/lecture1.ppt
13
(. )
Drop on a Solid Surface
Youngs equation relates interfacial tensions and contact angle
u
o
LV

o
SV

Solid, S
Liquid, L
Vapor, V
o
SL

u o o o cos
LV SL SV
+ =
Contact angle, u
(reflects the degree of wetting)
14
(. )
Wetting Phenomena
u
u
u
u > 90
o

u = 90
o
u < 90
o

u = 0
o
u =180
o

Absolute wetting
No wetting
15
(. )
Wettability of Powders
Solid
u
Liquid
Vapor
o
LV

o
SV

o
SL

u o o o cos
LV SL SV
+ =
16
(. )
Micelles are not really
dissolved in water, they
are suspended.
These sort of
suspensions are called
colloids.
Colloids : Particles of
one substance dispersed
throughout another.
Colloids can be detected
by the scattering of light
that is passed through the
sample, this is called the
Thyndall Effect.
Colloids
The Tyndall effect is evident as a beam of
light passes through a colloidal dispersion
of water droplets in the atmosphere.
17
(. )
Types of Colloidal Dispersions
18
(. )
All soaps are detergents;
all detergents are
surfactants.
( )

Surfactants
Surfactants are molecules that preferentially adsorb at an
interface, i.e. solid/liquid (froth flotation), liquid/gas (foams),
liquid/liquid (emulsions).
Significantly alter interfacial free energy (work needed to
create or expand interface/unit area).
Surface free energy of interface minimized by reducing
interfacial area.
19
(. )
If enough soap is added to water the molecules
arrange themselves into a structure called a micelle
Hydrophilic ( lyophobic,
water-loving) head
containing a charged
functional group
Hydrophobic ( lyophilic,
water-fearing ) tail
containing a
hydrocarbon chain
Soap Molecules
20
(. )
Amphiphilic Surfactants
Amphiphilic surfactants contain a non-polar portion
(tail) and a polar portion (head).
S
O
-
Na
+
O
O
S
O
O
O
O O
O
+
Na
-
O
Aerosol OT
Sodium dodecylsulfate (SDS)
21
(. )
Classification of Surfactants
Anionic

Cationic

Zwitterionic

Nonionic
N
+
Br
-
S
O
-
Na
+
O
O
Cetylpyridinium bromide
O
O
P
O
O
O
OCH
2
CH
2
N(CH
3
)
3
+
O
-
Dipalmitoylphosphatidylcholine (lecithin)
O
O
O
O
OH
Polyoxyethylene(4) lauryl ether (Brij 30)
Soap
22
(. )
Molecular Architecture
Aerosol OT
23
(. )
4 nm
Unimers (monomers)
Normal micelles
spherical
cylindrical
Bilayer lamella
Reverse micelles
Inverted hexagonal phase
Surfactant aggregates
24
(. )
If concentration is sufficiently high, surfactants can form aggregates
in aqueous solution micelles.
Typically spheroidal particles of 2.5-6 nm diameter.
McBain
Lamellar
Micelle
Hydrocarbon
Layer
Water
Layer
Water
Layer
Hartley
Spherical
Micelle
+
+
+
+
+
+
+
+
-
-
- -
-
-
-
-
-
-
-
-
-
-
-
-
Micelles
25
(. )
0
2
4
6
8
10
12
14
0 1
Surfactant concentration
CMC

Critical Micelle Concentration
CMC
Below CMC only unimers are
present
Above CMC there are micelles in
equilibrium with unimers
Onset of micellization observed by sudden change in
measured properties of solution at characteristic surfactant
concentration
critical micelle concentration (CMC).
26
(. )
Onset of micellization observed by sudden change in measured
properties of solution at characteristic surfactant concentration
critical micelle concentration (CMC).
Critical Micelle Concentration
( From: Klimpel, Intro to ChemicalsUsed in Particle Systems, p. 29, 1997,
Fig 20 )
27
(. )
Solution Properties & CMC
0
2
4
6
8
10
12
14
0 1
CMC
C
o
n
c
.

unimers
micelles
0
2
4
6
8
10
12
14
0 1
CMC
Osmotic pressure
t
0
2
4
6
8
10
12
14
0 1
(Surfactant concentration)
1/2

CMC
Molar conductivity
1/R
0
2
4
6
8
10
12
14
0 1
CMC
I
sc

Light scattering
28
(. )
--Driving Force--
Lyophobic (solvent-fearing) groups can perturb solvent structure and
increase free energy of system. Surfactant will concentrate at the
solvent-gas interface to lower AG
o
.
AG
o
can also be decreased by aggregation into micelles such that
lyophobic groups are directed into interior of structure and lyophilic
solvent-loving) groups face solvent.
Decrease in AG
o
for removal of lyophobic groups from solvent contact
by micellization may be opposed by:
(i) loss in entropy &
(ii) electrostatic repulsion for charged headgroups
Micellization is therefore a balance between various forces
AIR
WATER
Micellization Thermodynamics
29
(. )
Micellization Thermodynamics
m
.
[SURF]
[SURF]
m

K
mic

m
mic
m
mic
mic
] [ ] SURF [ cmc
c c
K = =
) 100 30 ( ln ln
m
ln
m
ln
m m
mic
o
mic
= ~ + = =
A
= A m cmc RT cmc RT
c RT
K
RT G
G
o
o
Nonionic surfactant
m - number of aggregation
above cmc: [SURF] ~ cmc
mic mic
m m ] [ c c cmc c
o
~ + =
T
cmc
RT cmc R S
T
cmc
RT H
cmc RT G
d
ln d
ln
d
ln d
ln
2 o
mic
2 o
mic
o
mic
= A
~ A
~ A
30
(. )
--Temperature and Pressure--
For ionic surfactants there exists a critical temperature above which
solubility rapidly increases (equals CMC) and micelles form
Krafft point or Krafft temperature (T
K
),
Below T
K
solubility is low and no micelles are present.
(Klimpel, Intro to Chemicals Used in Particle Systems, p. 30, 1997, Fig 22)
Micelles
31
(. )
surfactant
crystals
T
K

Temperature
Surfactants much less effective below Krafft point, e.g. detergents.

For non-ionic surfactants, increase in temperature may result in
clear solution turning cloudy due to phase separation. This critical
temperature is the cloud point.

Cloud point transition is generally less sharp than that of Krafft
point.
Micelles
--Temperature and Pressure--
32
(. )
Krafft Point, CMT and Cloud Point (~ temp.)
(I) Krafft Point
Cloud
point
(II) CMT and Cloud Point
1
c
T
Micelles +
solution
Solution
CMC
CMT
Phase
Separation
1
T
krafft

CMC
c
T
Micelles +
solution
Solution
Crystals +
solution
Liquid
crystals
I. Above the Kraft point, the solubility is sharply increase due to the formation of micelles.
II. Some surfactants (e.g. polyoxyethylene (POE)-based) dehydrate and phase separate
upon temperature elevation (cloud pint).
III. In Pluronic block copolymer, the micelles form as a result of the dehydration of
polyoxypropylene segments (critical micelle temperature or CMT).
33
(. )
Soap: How does soap clean?
34
(. )
soap decreases surface tension of water, making it a better wetting agent.
soap converts greasy and oily dirt into micelles that become dispersed in
water.
soap keeps the greasy micelles in suspension and prevents them from
redepositing until they can be washed away. (repulsion of the charges)
Soap: How does soap clean?
35
(. )
Acid-catalyzed and base-catalyzed hydrolysis.
Through the breakdown of esters by a hydrolysis process.
This bond is broken
How are soap produced?
36
(. )
The saponification of a triglyceride.
Soaps are not produced from simple esters such as methyl acetate
but from more complex esters
animal fat
How are soap produced?
37
(. )
What are all of these
chemicals ?
What do they do ?
What is in a box
of detergent ?
38
(. )
What is in a box of detergent ?
39
(. )
40
(. )
Solubilization
Spontaneous transfer of a compound insoluble in the bulk solvent into
the solution inside the surfactant micelles.
polar compound
Reverse micelles
non-polar compound
Normal micelles
amphiphilic compound
0
2
4
6
8
10
12
14
0 1
CMC
S
o
l
u
b
i
l
i
t
y

Solubility of a poorly soluble
compound increases as a
result of solubilization in the
micelles.
41
(. )
HLB and Use of Surfactants
Amphiphilic surfactants are characterized by the hydrophilic-
lipophilic balance (HLB): a relative ratio of polar and non-polar
groups in the surfactant.
HLB number, ranging from 0-40, can be assigned to a surfactant,
based on emulsification data. Semi-empirical only.
Strongly hydrophilic surfactant, HLB 40
Strongly lyophilic surfactant, HLB 1
oil
water
C
oil

C
water

C
6
H
13
COO
-
C
8
H
17
COO
-
C
10
H
21
COO
-

HLB decreases
42
(. )
HLB ca. 1 to 3.5: Antifoams
HLB ca. 3.5 to 8: Water-in-Oil Emulsifiers
HLB ca. 7 to 9: Wetting and spreading agents
HLB ca. 8 to 16: Oil-in-Water Emulsifiers
HLB ca. 13 to 16: Detergents
HLB ca. 15 to 40: Solubilizers
HLB and Use of Surfactants
Strongly hydrophilic
Strongly Lipophilic
Question:
Why antifoaming or water-in-oil emulsifiers use low-HLB
surfactants & why detergents use hi-HLB surfactants?
43
(. )
HLB needed for emulsification of the oil phase
* Calculate the required HLB for the oil phase of the following o/w emulsion: cetyl
alcohol 15 g., white wax 1g. Lanolin 2 g, emulsifier (q.s.), glycerin 5 g. water
100 g.
HLB (from reference) Fraction
Cetyl alcohol 15 x 15/18 = 12.5
White wax 12 x 1/18 = 0.7
Lanolin 10 x 2/18 = 1.1
Total required HLB = 14.3
Surfactant blends are commonly used to obtain desired emulsifying
properties.
If there are several oil ingredients the required HLB is calculated as a
sum of their respective required HLB multiplied by the fraction of each.
* What is the HLB of the mixture of 40 % Span 60 (HLB = 4.7) and 60 % Tween 60
(HLB = 14.9)?
HLB of mixture: 4.7 x 0.4 + 14.9 x 0.6 = 10.8
* In what proportion should Span 80 (HLB = 4.3) and Tween 80 (HLB = 15.0) be
mixed to obtain required HLB of 12.0?
4.3
.
(1-x) + 15
.
x = 12 x = 0.72 ( 72 % Tween 80 and 28 % Span 80)

CHM 342 Surface

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CHM 342 (2-46) Surface Chemistry

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