MACROMOLECULES

characterized

: molar mass
geometrical size and shape

* natural
- polysaccharides
- polypeptides
- nucleic acid

* synthetic
- polymers:
nylon
polystyrene

macromolecules have special questions and problems

= determination of their size, shapes, and lengths

= large deviation from ideality of their solution

http://physics.ucsc.edu/~sacarter/polymers.shtml

LEVELS OF STRUCTURE

PRIMARY, SECONDARY, TERTIARY, QUATERNARY

Size and shape

= X-ray diffraction

Limitations:
-single crystal
-crosslinking
-mixture of molecules
-natural shape

http://pubs.usgs.gov/of/2001/of01-041/htmldocs/xrpd.htm

Franklin and
Gosling

http://www.learner.org/courses/essential/physicalsci
/session5/closer1.html

DNA

http://en.wikipedia.org/wiki/Rosalind_Franklin

 Mean Molecular Mass

monodisperse : single definite molar mass
polydisperse : mixture of molecules with
various chain lengths and molar
mass

various techniques of measuring molar masses

= resulting in different types of mean values

* by osmotic pressure measurements (osmometry )

= number-average molar mass, Mn

* by viscosity measurements -

= viscosity-average molar mass, MV

* by light-scattering experiments
= weight-average molar mass, MW
* by sedimentation experiments -

= Z-average molar mass, MZ

1
M n Ni Mi
N i

mi NiMi/NA

1
M w mi Mi
m i
Mw

iNi M
iNi Mi

2
i

Mz

iNi M
iNi Mi2
3
i

VISCOMETER

(intrinsic viscosity)

Assumption:
-slow moving liquid where t>100s
-monodisperse macromolecule
http://en.wikipedia.org/wiki/Viscometer

Polydisperse

Osmosis
-movement of molecules through a semipermeable
membrane

The osmotic pressure, , is the pressure that must

be applied to stop the influx of solvent.

11

Osmosis
Examples:
(a) Transport of fluids through living cell
membranes ,
(b) Basis of osmometry, determination of
molecular mass by measurement of osmotic
pressure.

12

 Osmometry
= vant Hoff equation
- an ideal solution - non-ideal solution
= [P]RT
= [P]RT(1 + B[P] + . . . . .)
? how do we relate the equation to molar mass ?
[P] = related to mass concentration c
Mn
if
= number-average molar mass of P
then,
RT B

1 c ......
c M
n
where
M=n rgh

 RT B

1 c ......
c Mn Mn

Coefficient B , osmotic virial coefficient

= arises largely from the effect of excluded
volume relationship
B = NAuP

uP , excluded volume

uP = 8u
from a plot of (h/c) against c :

RT B
slope
x
g M n M n

RT
y - intercept
g M n

 RT B

1 c ......
c Mn Mn

RT B
slope
x
g M n M n
from the slope, B is obtained B = NAuP
uP
approximate volume of a molecule
approximate radius

 thermodynamically,

= excluded volume
excess entropy
= attraction and repulsion
excess enthalpy
for most solute-solvent system

= Flory theta temperature, q

(the critical miscibility temperature in the limit of infinite molecular weight)

= q solution

Osmometry
h

Semipermeable membrane: stops polymers, passes solvent.

17

Osmosis
Eventually the pressure difference between the
arms stops osmosis.

18

19

However A is now increased by greater pressure p

*A ( p) A ( x A , p )
account for the presence of solute
A ( x A , p ) *A ( p ) RT ln x A
take the effect of pressure into account
p

*A ( p ) *A ( p) Vm dp
p

where Vmis the molar volu me of pure solvent A

combining equations, we have
p

- RT ln x A

V dp
m

Dilute solutions : ln x A replaced by ln(1 - x A ) - xB and Vm is constant

RTxB Vm

RTxB Vm
nB
When the solute is dilute, xB . Because nAVm = V,
nA
total volume of the solvent, the equation simplifies to

p = [M ]RT

Vant Hoff
Eq.

nB
where [M ] =
is the molar concentration of the solute
V

21

The Virial form of the Vant Hoff

Equation
Osmotic pressure is easily measured, and is quite large.
Osmometry can be applied for the determination of
molecular weights of large molecules (proteins, synthetic
polymers), which dissolve to produce less than ideal
solutions. The Vant Hoff equation can be rewritten in the
virial form:

= [B] RT {1 + B [B] + ...}

where B is the empirically determined osmotic virial

coefficient

22

Consider poly (vinyl chloride) PVC, in cyclohexanone

at 298 K
Pressures are expressed in terms of heights of solution,
=0.980 g cm-3 in balance with the osmotic pressure
c (g L-1)
h (cm)

1.00
0.28

2.00
0.71

4.00
2.01

7.00 9.00
5.10 8.00

Use = [B] RT {1 + B [B] + } with [B] = c/M, where c

is the mass concentration and M is the molar mass. The
osmotic pressure is related to the hydrostatic pressure by
= gh, where g = 9.81 m s-2. Then:
23

h
RT

c rgM

Bc RT RTB
c

1

2
M rgM rgM

Plot h/ c vs. c to find M, expecting a straight line with intercept

RT/ gM at c = 0.
Data set:
c(g L-1)
1.00 2.00 4.00 7.00 9.00
h/c(cm g-1 L) 0.28 0.36 0.53 0.729 0.889

24

The data give an

intercept of 0.21.

25

The data give an intercept of 0.21 cm g-1 L, which is equal to

RT/ gM
Thus:

RT
1
M

rg 0.21 cmg -1 L

8.314 JK

-1

-1

mol (298 K )
1

-3
-2
(980 kgm ) (9.81ms ) 2.110 -3 m 4 kg -1

1.2 10 kgmol
2

-1

where we have used 1 kg m2 s-2=1J

26

 Vapour-phase Osmometry

= molar mass too low for membrane osmometry

- two (2) thermistors (temperature probe)

- chamber is saturated with solvent

* the difference in temperature is measured
for a series of concentrations
* calibration use of samples of known molar
mass

VAPOR OSMOMETRY

http://willson.cm.utexas.edu/Teaching/Chem367L392N/Files/Vapor%20Pressure%20Osmometry.pdf

http://willson.cm.utexas.edu/Teaching/Chem367L392N/Files/Vapor%20Pressure%20Osmometry.pdf

http://panza.uchicago.edu/Phys.261/materials/Osmometer/

http://willson.cm.utexas.edu/Teaching/Chem367L392N/Files/Vapor%20Pressure%20Osmometry.pdf

 Polyelectolytes and Dialysis

Macromolecules are polyelectrolytes

polymers: - string of acid groups
- string of basic groups
- both acids and bases
= on ionization polyanions or polycations
= mixed cation-anion character
polyampholyte

 problems:
(1) variable number of cations per single
macromolecules
(2) presence of salt affects osmotic pressure
= high concentration of added salt
= molar mass can be obtained unambiguously

 Donnan Equilibrium

= physiological systems

Consider a system of the following components:

a. an aqueous solution of an electrolyte
this solution = internal solution

b. another aqueous solution of an electrolyte

this solution = external solution
c. a semi-permeable membrane
* in this system:
the diffusible ions will move across the membrane
equilibrium

Donnan equilibrium
The equilibrium characterized by an unequal distribution of
diffusible ions between two ionic solutions (one or both of the
solutions may be gelled) separated by a membrane which is
impermeable to at least one of the ionic species present, e.g.
because they are too large to pass through the pores of the
membrane. The membrane may be replaced by other kinds of
restraint, such as gelation, the field of gravity, etc., which prevent
some ionic components from moving from one phase to the other,
but allow other components to do so.

 Donnan Equilibrium

in this system:
the diffusible ions will move across the membrane
equilibrium
the Donnan principle :

that at equilibrium the products of the

concentrations of the pairs of diffusible ions going
to make up any possible electrolyte will be equal
on the two sides of the membrane

 Three different processes :

Donnan equilibrium

Case I: electrolytes in the internal and external

solutions have a common ion
Case II: electrolytes in the internal and external
solutions have no common ion
Case III: external liquid does not have any solute,
just pure water

 In the study of these systems, the following are the

restrictions:
only monovalent ions are present

volumes of the internal and external

solutions are the same (equal volumes)
no volume change in either solutions

Case I : electrolytes in the internal and external

solutions have a common ion
consider initial conditions:

Na+
C1

PC1

internal solution

Na+ ClC2 C2
external solution

at equilibrium:
internal (NaCl) = external (NaCl)

@ at equilibrium:
internal (NaCl) = external (NaCl)
or
RT ln ai(Na+)ai(Cl-) = RT ln ae(Na+)ae(Cl-)

[Na+]i[Cl-]i = [Na+]e[Cl-]e
requirement for Donnan equilibrium

 from conditions of electrical neutrality:

[Na+]i = [Cl-]i + x[P-] and [Na+]e = [Cl-]e

difference in concentration of ions across the

membrane:
[Na ]i - [Na ]e

xP [Na ]i
xP [Na ]i

[Na ]i [Na ]e 2[Cl- ] x[P ]

[
]
[
]i
xP
xP
Cl
Cl
i

[Cl ]i - [Cl ]e [Cl ]i [Cl ]e 2[Cl- ]

where:

[Cl- ] 21 ( [Cl- ]i [Cl- ]e )

 recall: vant Hoff equation = RT [solute]

RTP Na i Cl- i - Na e Cl- e

= RT [P]{1 + B [P]}
where:
2

x Cl e
B
- 2
4Cl 2xP Cl-
thus,
* when salt concentration is so high
[Cl-]i and [Cl-]e >> [P]
then,
B[P] << 1
and = RT[P]

 effect of salt added

= extent to which ions are bound to the macromolecules

equations show:

* cations will predominate the anions in the compartment

containing the polyelectrolyte (polyanion)
equilibrium distribution of ions in two compartments
connected/separated by a semi-permeable membrane
in one which contains a polyelectrolyte
= Donnan equilibrium

 SEDIMENTATION
= heavy particles settle down the bottom of a
column of solution
rate of sedimentation depends on:
(a) strength of the field
(b) masses and shape of the particles
at equilibrium:

= particles are dispersed over a range of height

= spread of heights depends
masses of the molecules

 sedimentation - normally very slow

= may be made fast by using a centrifugal
use of ultracentrifuge
solute moves outwards as sedimentation
proceeds
the rate can be monitored
refractive index of the sample

 rate of sedimentation
* consider a solute of mass, m and with an effective mass
meff = bm with b = 1 - rus
(vs = (V/mB)T -partial specific volume

* if r is the distance of solute particles from the axis of

rotation (rotor spinning at an angular velocity of w)
centrifugal force of magnitude = meffrw2
* acceleration outwards experiences friction
force = f s - (friction coefficient)(speed)
* particles adopt a drift speed
a steady speed through the medium

 at drift speed
centrifugal force = frictional force
meff r w2 = f s
2
2
thus,
meff r bmr
s

speed
f
f

s
S 2
r

let S = the sedimentation

constant ,
2
bmr
S
then,
2
fr
Mn
m

since,
S bMn
NA
then,
fNA

? what is f, the frictional coefficient or constant?

* for a spherical particle of radius = a
in a solvent of viscosity = h
= for solute molecules that are not small compared to
the solvent molecules
f is given by the Stokes relation
f = 6ah
* for spherical molecules

S bmrw2 b Mn
6ahNA
frw

* for non-spherical molecules

= appropriate values for f are given in table

 when dealing with macromolecules :

= measurements : series of concentrations
extrapolated to zero concentration
from S, to get M know the radius, a
n
= requirement can be avoided by using the
Stokes-Einstein relation
kT

D
* D, diffusion coefficient
= a measure of the rate at which molecules
spread down a concentration gradient
it follows,

SRT
Mn
bD

SRT
Sedimentation Equilibria
Mn
bD
* difficulty in using sedimentation rates to measure
molar masses lies
- inaccuracies inherent in the determination of
the diffusion coefficients

allow system to come to equilibrium

= D is no longer relevant
* the weight-average molar mass can be determined
from the ratio of the concentrations of the
macromolecules at two different radii

- the number of solute molecules with any given

potential energy, E, is proportional to e-E kT

= ratio of concentrations at different height

can be used to determine their masses
- due to motion, the kinetic energy of a molecule of mass,
meff, arising from its circulation around the axis of the
centrifuge is
E = meff r2 w2 = b m r2 w2
therefore,
- the ratio of the concentrations
at radii, r1 and r2, is

-E1

c1 N1 e kT -b m ( r - r ) 2kT
e
-E
c 2 N2 e kT
2

2
2

2
1

so that,

2RT
c

ln
MW
(r - r ) c
2

= gives the weight-average molar mass

Sedimentation/Ultracentrifugation

http://biophy.uchicago.edu/ultracentrifugation.php

Sedimentation velocity is an
analytical ultracentrifugation
(AUC) method that measures the
rate at which molecules move in
response to centrifugal force
generated in a centrifuge. This
sedimentation rate provides
information about both the
molecular mass and the shape of
molecules. In some cases this
technique can also measure
diffusion coefficients and
molecular mass.
http://www.ap-lab.com/sedimentation_velocity.htm

SCANNING ABSORPTION OPTICS

Plot of LnA vs r2 (radial distance from the center of the
Rotor)
Anglular velocity

Partial specific volume

http://www.nottingham.ac.uk/ncmh/harding_pdfs/Paper116.PDF

http://biophy.uchicago.edu/ultracentrifugation.php
http://www.nottingham.ac.uk/ncmh/harding_pdfs/Paper116.PDF

* troublesome to have several types of average

= different values gives additional information
about
the range of molar masses in the
sample
= example:
proteins same averages
synthetic polymers different averages

 Mean Molar Mass

heterogeneity index or polydispersity index
Mw
= ratio
Mn
* various averages of protein molar masses are expected to
be the same
* a synthetic polymer normally spans a range of molar
masses and the different average yield different
values
= typical synthetic materials have index 4
* the term monodisperse is conveniently applied to
synthetic polymers in which this index is less than 1.1

 macromolecules = strongly non-ideal solutions

* being so large they displace a large quantity of

solvent instead of replacing individual solvent
molecules with negligible disturbance
* its great bulk makes it unable to move freely through
the solution
*significant contribution to the Gibbs energy from the
enthalpy of solution

 Colligative Properties
= classical methods for molar mass
* for macromolecules = the number of molecules in solution may be
very small though the mass of the
solute may be appreciable
= only osmometry is sufficiently sensitive

 Electrophoresis
= motion of macromolecules in response to an
electric field
electrophoretic mobility
= result of a constant drift speed, s, when the driving
ezE equals the viscous retarding force, fs

= mobilities of macromolecules depend on their net

charge, size (molar masses) and their shape
= valuable tool in the separation of biopolymers
from complex mixtures, fractionation of
biological cells

force

 Gel electrophoresis
= migration takes place through a cross-linked
polyacrylamide gel
= to separate a sample according to the molar
masses of its components
however, shape and net charge will also determine the
drift speed
example:
proteins with the same size but different net charge
travel along the slab at different speeds

 Gel electrophoresis
- to avoid this problem and to effect a separation by
molar mass
controlled denaturation of the proteins
(sodium dodecyl sulfate, an anionic detergent denatures
proteins into rods by forming a complex )
* most proteins bind a constant amount of ion, thus the
net charge per protein is well regulated
* under this conditions, different proteins in a mixture
may be separated according to size only
* molar mass is estimated by comparing its mobility in its
rod-like complexes form with a standard sample of
known molar mass

 Isoelectric point
in aqueous medium, naturally occurring
macromolecules acquire a charge
proteins and other biopolymers is that their overall
charge depends on the pH of the medium
* in general,
- in acidic media protons attach to basic groups
the
net charge is positive
- in basic media protons are lost
the
net charge is negative
at the isoelectric point, pH at which net charge of bp is zero
- thus, the drift speed of a biopolymer depends on the
pH of the medium
s = 0 at the isoelectric point

 Isoelectric focusing
(separation based on isolectric pt.)
= an electrophoresis method that is based on the
change of drift speed with pH
* consider : mixture of distinct proteins dispersed in a
medium with a pH gradient along the direction of an
applied electric field
each protein in that mixture will stop moving at a
position in the gradient where the pH is equal to the
isoelectric point
the protein mixture can be separated into its
components

 Capillary electrophoresis
drift speed (traditional electrophoresis methods)
=
rather low
several hours are often necessary to effect good
separation of complex mixture

solution: increasing the drift speed

to increase the electric field strength
= limitation: very large electric fields can heat the
large surfaces of an electrophoresis
apparatus unevenly
nonuniform distribution of electrophoretic
mobilities and poor separation

 Capillary electrophoresis
Solution:
= the sample is dispersed in a medium and held in a
thin glass or plastic tube (diameters, 20 - 100 m)
= small size of the apparatus makes it easy to
dissipate heat when large electric fields are
applied
excellent separations may be effected in minutes
rather than hours
each polymer fraction emerging from the capillary
can be characterized further by other
techniques

 Size-exclusion chromatography (SEC)or

gel permeation chromatography (GPC)

= fast and relatively inexpensive technique for molar

mass determinations of polymers
= a solution of the polymer sample is filtered through a
column
- small molecules permeate thru the porous structure
of the gel
require a long elution time
- larger molecules are not captured, pass through
rapidly
- the average molar mass of a macromolecule
determined by observing its elution time in a
column calibrated against standard samples

 Size-exclusion chromatography (SEC) or

gel permeation chromatography (GPC)

= range of molar masses can be altered

by selecting columns made from polymers with
different degrees of cross-linking and different
materials :
- polystyrene
gels : nonpolar systems
- porous glass gels : more polar systems
- polyacrylamide gels : for proteins
= limitation : elution time also depends on the shape of
the polymer
thus, direct comparison of calibration standards and
unknown samples
= can lead to errors

 Size-exclusion chromatography (SEC) or

gel permeation chromatography (GPC)
- problem is common in SEC of proteins: two proteins
with similar molar masses may have distinct shapes
different elution times on the same column
- SEC does give reasonably accurate molar mass values
for a large number of proteins
when elution is performed under pressure
moreover, only a few milligrams of material are
needed for reliable measurements

 Viscosity
- presence of macromolecular solute
increases the viscosity of a solution
- effect is larger at lower concentrations

- at low concentrations,
h = h* ( 1 + [h]c + )
where, [h] is the intrinsic viscosity

- 1
*
h lim

c 0
c

 Measurement - several ways

Ostwald viscosimeter
- time taken for the solution to flow through a
capillary is measured and compared with
standard sample

t
x
* t * *
Rotating Drum viscosimeter
- rotating concentric cylinders and the torque
on the inner cylinder is monitored while
the
other cylinder is rotate

 there are many complications in the interpretation of

viscosity measurements
most work are base on empirical observations
molar masses are usually based on comparisons with
standards nearly non-dispersed samples
some regularities can be observed, like
- for q solutions of macromolecules it has been
found to fit the Mark-Kuhn-HouwinkSakurada equation:
K MaV

 complications in viscosity measurements

= some fluids are non-newtonian

= viscosity changes with rate of flow
presence of rod-like molecules
- oriented by the flow
- slide past each other more freely
-stresses due to flow may break up
molecules

 Light Scattering
= electromagnetic radiation falls on an object
radiate
if the medium is perfectly homogeneous
= all the secondary waves interfere destructively
except the original propagation direction
if the medium is inhomogeneous
= radiation is scattered into other directions

 Light Scattering
Scattering by particles with diameters much
smaller than the wavelength of the incident
radiation
= Rayleigh scattering
Characteristics of Rayleigh scattering
intensity of scattered radiation depends on 1/l4
shorter wavelength radiation is scattered more
intensely than longer wavelength

 Characteristics of Rayleigh scattering

intensity depends on the scattering angle, q

- proportional to 1 + cos2q
= light is unpolarized
- proportional to cos2q
= light is polarized
intensity depends on the strength of the interaction
the light with the molecule
interaction is large = polarizability is large

of

mathematically,
- scattering intensity, I, at the angle q

I AIo M W g[P]
= 1 + cos2q
(for unpolarized light)
= cos2q
(for polarized light)
= incident intensity
= molar concentration of the solute
= weight-average molar mass
MW
A = constant

where, g
g
Io
[P]

* ideal ignores the complications due to the

interaction between solute particles

* actual experimental data plotted

extrapolated to zero
Turbidity (t)
- a solute scatters light away from the forward direction
transmitted intensity is reduced
- intensity of the forward direction
- tl
given
e a Beer-Lambert Law type
I Ioby

 for macromolecules of moderate size

- turbidity is related to the mass concentration,
c, by the equation,
Hc 1
1 2Bc .....

t MW

dn
where, H dc , n = refractive index
Hc
plotting t against c
* y-intercept = weight-average molar mass

 Large-particles scattering

= wavelength of the incident radiation comparable

to the size of the scattering particles
- scattering may occur at different sites
- interference between different rays is important

*as a result,
- the scattering intensity is distorted

I
P observed
IRayleigh
= a measure of the distortion is the ratio,

other factors to consider

if the molecule is regarded as composed of a number of

atoms i at distances Ri from a convenient point
= interference occurs between the radiation
scattered by each pair
scattering from all the particles is then calculated
= by allowing for contributions from all possible
orientations of each pair of atoms in each
molecule

 if there are N atoms in the macromolecule and if all are

assumed to have the same scattering power, then,

sinsRij

2
sRij
N i j

where

4 1
s sin

 Small-particle scattering

- molecule is much smaller than the wavelength of

the incident radiation like sRij << 1
then, the deviation from Rayleigh scattering
is proportional to the square of the
radius of gyration, Rg of the molecule

P - 1 Rg2

Rg = radius of a thin hollow spherical shell of the same

mass and moment of inertia thus same rotational
characteristics as the molecule
2

1 2
Rij R g
N ij

since sRij << 1 = use expansion

sin x = x - (1/6)x3 + ..
sin(sRij) = sRij - (1/6)(sRij)3 + ..

it follows,

2
1
2

s
P 2 1 sRij ..... 1 - 2 Rij2 .....
6

6 N ij
N i j

* the sum over the square of the separations gives the

radius of gyration of the molecule

1 2 2
P 1- s Rg
3
showing that
P - 1 R g2

 deviation from Rayleigh scattering is determined by Rg

analysis of the scattering intensity should give the

value of Rg for the molecule in solution

* Rg - can be used to interpret the size of the molecule ,

like,
1/2
3

R
g R
solid sphere particle of radius R :
5
1
Rg
2 3
long thin rod of length l :

Light Scattering

http://www.nbtc.cornell.edu/facilities/downloads/Zetasizer%20chapter%2015.pdf

http://www.nbtc.cornell.edu/facilities/downloads/Zetasizer%20chapter%2015.pdf

http://www.nbtc.cornell.edu/facilities/downloads/Zetasizer%20chapter%2015.pdf

 Mass Spectrometry
= among the most accurate techniques for determination of
molar masses
= consists of ionizing the sample in the gas phase
measure : mass-to-charge number ratio (m/z) of all
ions
= macromolecules - a challenge - difficult to produce
gaseous ions of large species without fragmentation
- two new techniques :
matrix-assisted laser desorption/ionization (MALDI)
electrospray ionization

 Mass Spectrometry
= commonly used is the MALDI-TOF mass spectrometry
the macromolecule is first imbedded in a solid matrix
organic material and inorganic salts
sample is then irradiated with a pulsed laser(nitrogen
laser)
the laser energy ejects electronically excited matrix
ions, cations, and neutral macromolecules
=
creating a dense gas plume above the sample
surface
the macromolecule is ionized by collisions and
complexation with small cations, like H+, Na+, & Ag+

 Mass Spectrometry
- in the TOF spectrometer, the ions are accelerated over a
short distance d by an electrical field of strength, E
and then travel through a drift region of length l
- the time, t, required for an ion of mass m, and charge
number z, to reach the detector at the end of the drift region
is
1/ 2
m where e = fundamental charge
t l

2zeEd
* because d,l, and E are fixed for a given experiment, the
time of flight t, of the ion is a direct measure of its m/z
ratio, which is given by
2
m
t
2eEd
z
l

Determine the number-average

and the weight-average molar
masses for a sample of poly(vinyl
chloride) from the following data:

The amounts in each interval are as

follows:

 COLLOIDS
true solution - - - - - - - - - - - - - - - suspension

sugar or salt

soil in water
in water

( individual molecules or ions)

(large molecules or
aggregates)

colloidal suspension

between extremes
no distinct line of separation between them

 COLLOIDS
* colloidal dispersion
= suspension of finely divided particles in a
continuous medium
particles = the dispersed phase or colloid
medium = the dispersing medium
* dispersing medium may be solid, liquid, or gas just
as the disperse phase

 COLLOIDS

* lower limit of microscopic visibility :

about 2 x 10-7 m (0.2 m or 200 nm)
= upper limit of the size of colloidal particles
* lower limit of the size of colloidal particles:
5 x 10-9 m (5 nm)

 COLLOIDS
* essential properties :
due to the fact that the ratio of surface area to
volume
= very large

* true solution : one phase

colloidal dispersion : two phases
= as each particle has a definite surface of
separation between it and the medium
which the particles are dispersed

in

* types of dispersions are tabulated showing the general

name and common examples
Dispersing
medium
Gas

Liquid

Solid

Dispersed phase
Gas

Liquid

Solid

Aerosol

Foam
(whipped cream)

(mist, fog, clouds)

Emulsion
(milk, mayonnaise)

Aerosol
(smoke)
Sol
(Au in water)

Solid Foam

Gel

Gel

(pumice, Styrofoam)

(jelly)

(ruby glass, gold in

glass)

 COLLOIDS
Lyophobic and Lyophilic Sols

= lyophobic sols
- dispersed phase: low affinity for the medium
- hydrophobic sols if the medium is water
= lyophilic sols
- strong affinity between the disperse phase and
the dispersion medium

 COLLOIDS
preparation:
- substances maybe known as :
= intrinsic colloids - readily form sols in contact with
a suitable dispersion medium
= extrinsic colloids - do not form colloidal
dispersions readily

 COLLOIDS
- method : two classes

(1) condensation
= initially in true solution
= chemical reactions are used to produce the sol
ex. sols of various oxides have been prepared by
hydrolysis of salts

 COLLOIDS
- method : two classes
(2) Dispersion
= originally in massive form is disintegrated into
particles of colloidal dimensions
(a) peptization
(b) physical dispersion methods
(c) electrical disintegration

 COLLOIDS
Light Scattering
= optically clear medium path of light cannot be
detected (particle size not larger than
about 10-9 m in diameter)
= with colloidal particles, some of the light is scattered
the path of light through the medium is made
visible due to scattering
known as Tyndall effect

 COLLOIDS

Electrical Properties
= application of an electric potential across two electrodes
placed in a sol
migration of colloidal particles in an electric field
is called electrophoresis

 COLLOIDS
Gels
= under certain conditions, lyophilic sol maybe
coagulated and produces a semi-rigid jellylike mass
product is known as gel

* two types:
- elastic gels : food products, jellies, jams, and
cornstarch puddings
- nonelastic gels : silicic acid or commonly known as
silica gel

 COLLOIDS
= main difference: behavior on dehydration
elastic gel forms an elastic solid = original sol
can be regenerated by the addition of water
non-elastic gel leads to a glass or powder

= another distinction: ability to take up solvent

elastic gel: swells, like gelatin in water
= process - imbibition
non-eleastic gel: do not swell
= rigid wall - volume of the gel does not
change with solvent

 COLLOIDS
Emulsions
= droplets of one liquid dispersed in another liquid

= generally unstable unless

= stabilizer:
emulsifying agent
or stabilizing agent

 COLLOIDS
Emulsions
= soaps and detergents :effective emulsifying agents for oilwater emulsions
HC chains become attached to the oil and the
polar groups to the water
* micelle : refers to particles that are stabilized by
emulsifying agents
emulsifying agents reduce the interfacial tension
between the two phases

 COLLOIDS
Structure and stability
= colloids are thermodynamically unstable
but kinetically nonlabile
the change in Gibbs energy, dG, when the surface
area of the sample changes by d at constant T & P
is dG = d, where is the interfacial tension, it
follows the dG <0 if d <0
= colloidal particles attract each other over large
distances, so there is a long-range force that tends to
condense them into a single blob

 COLLOIDS
Structure and stability
reasons:
= the energy of attraction between two individual atoms i
and j, varies with their separation as 1/(Rij)6

= the sum of all these pairwise interactions, however,

decreases only as approximately 1/R2 where R is
the separation of the centers of the particles
= the sum has a much longer range than the 1/R6
dependence characteristic of individual particles
and small molecules

 COLLOIDS
Structure and stability
* factors opposing the long range dispersion attraction
for example:
= a protective film at the surface of the colloid particles
stabilizes the interface and cannot be penetrated
- thus, the surface atoms of a platinum sol in water
react chemically and are turned into Pt(OH)3H3,
and
this layer encases the particle like a shell
= a fat can be emulsified by a soap because the long HC
tails penetrate the oil droplet but the carboxylate head
groups surround the surface, form H-bonds with
water, and give rise of negative charge

 COLLOIDS
Electrical double layer
kinetic nonlability of colloids
existence of an electric charge on the surfaces

= due to this charge, ions of opposite charge tend to

cluster nearby ionic atmosphere
distinguish two regions of charge

- 1st, fairly immobile layer of ions that adhere tightly to the

surface of the colloidal particle
- - 2nd, the charged unit attracts an oppositely charged
atmosphere of mobile ions

 COLLOIDS
Electrical double layer
- 1st, fairly immobile layer of ions that adhere tightly to the
surface of the colloidal particle
the radius of the sphere (rigid layer) is called the
radius of shear
= factor
determining the mobility of the particles

the electric potential relative to its value in the bulk

medium
= called the zeta potential, , or the
electrokinetic potential

 COLLOIDS
Electrical double layer
- 2nd, the charged unit attracts an oppositely charged
atmosphere of mobile ions
the inner shell of charge and the outer ionic
atmosphere is called the electrical double layer

 COLLOIDS
Electrical double layer
* DLVO theory : theory of the stability of lyophobic
dispersions (B. Derjaguin & L. Landau and E. Verwey and
J.T.G. Overbeek)
= assumes : balance between the repulsive interaction
between the charges of the electric double layers on
neighboring particles and the attractive interactions
arising from van der Waals interactions between the
molecules in the particles
= the potential energy arising from the repulsion of
double layers on particles

-s
Aa
e rD
Vrepulsion
R
2

where A is a constant, is the zeta potential,1 R is

the separation of centres, s is the separation of
the surfaces of the two particles (s = R 2a for
spherical particles of radius a), and rD is the
thickness of the double layer.
-valid for thick double layers
If thin:

1/ 2

RT
rD
2 q
2rF Ib

B
Vattraction s

b = 1 mol kg1

 COLLOIDS
Electrical double layer

* at high ionic strengths: the ionic atmosphere is dense

the potential shows a secondary minimum at large
separations
* flocculation : aggregation of the particles arising from the
stabilizing effect of this secondary minimum
flocculated material can often be redispersed by
agitation because the well is so shallow
* coagulation: the irreversible aggregation of distinct
particles into large particles
- occurs when R is so small (primary minimum)
van der Waals forces are dominant

 COLLOIDS
electrical double layer
ionic strength is increased by the addition of ions,
particularly those of high charge type
= such ions act as flocculating agents
basis: Schulze-Hardy rule
that hydrophobic colloids are flocculated most
efficiently by ions of opposite charge type and high
charge number

 COLLOIDS
electrical double layer
Schulze-Hardy rule
- Al3+ ions are very effective
used to induce the congealing of blood
- when river water with colloidal clay flows to the sea
the salt water induces flocculation and
coagulation
= a major cause of silting in estuaries
- metal oxide sols tend to be positively charged
whereas sulfur and the noble metals tend to be
negatively charged

 COLLOIDS
electrical double layer
primary role of the electric double layer :
to confer kinetic non-lability
= particles coalesce only if
collision is sufficiently energetic to disrupt the layers
of ions and solvating molecules, or
- thermal motion has stirred away the surface
accumulation of charge
= disruption may occur at high temperatures
- sols precipitate when they are heated

 COLLOIDS
electrical double layer
protective role of the double layer
= the reason why
- it is important not to remove all the ions
when a colloid is being purified by dialysis,
and
- proteins coagulate most readily at their
isoelectric point

MICELLES

Micelle Formation
-CRITICAL MICELLE
CONCENTRATION (CMC)

-Krafft temperature.
-ionic surfactants cluster of 100
-non-ionic surfactants-cluster of
1000

Spherical liposome

Lamellar micelles/ membrane formation

FLUID MOSAIC MODEL

LIPID RAFT MODEL

SURFACE FILMS
Monolayers
Langmuir-Blodgett Films monolayer on a solid support

Surface film balance

surface pressure: Surface pressure is the

difference between the surface tension of the pure
solvent and the solution: = * .

Collapse pressures

THERMODYNAMICS OF SURFACE FILMS

SURFACE GIBBS ENERGY

nJ() = nJ {nJ() + nJ()}

Surface excess

Gibbs Isotherm

For dilute solutions

SAMS for nanofabrication

http://www.attension.com/critical-micelle-concentration

http://chemweb.calpoly.edu/jhagen/CMC_Surface_Tens.pdf

SURFACE TENSION AND

CONTACT ANGLE

Interfacial tension ij
-force/unit length (mN/m or J/m2)
-arises from the imbalance of
forces
-on molecules at the interface
(i.e. gas-liquid)
-caused by the attraction between the
molecules of the liquid by various

intermolecular forces

wiiir/wiii//5/5/rllrh

The work needed to change the surface area, , of

a sample by an infinitesimal amount d is
proportional to d, and we write

PULL METHODS

WILHELMY PLATE METHOD

htt://wwwulu/h/C446/Exrit/x1

DUNOUY RING METHOD

htt://wwwulu/h/C446/Exrit/x1

htt://wwwulu/h/C446/Exrit/x1

Freud et.al. JACS, ,52,1772,1930

=F/Lcosq

CAPILLARY RISE METHOD

P = r g h =2/R = (2 cos )/r
= rh rg/2cos

= r (h +r/3 )rg/2cos
R
x
h

http://www.udel.edu/pchem/C446/Experiments/exp1.pdf

If water at 25C rises through 7.36 cm in a capillary of

radius 0.20 mm, its surface tension at that temperature is

Curved surfaces
YOUNG-LAPLACE EQUATION

Area of the element:

A = r1r2

Surface move outward

by r:
Wp=pr1r2 r

Area after expansion:

A= (r1 + r)(r2 + r)

Increase in Area:
dA= (r1 + r2) r

W= (r1 + r2) r =Wp=pr1r2 r

(1/r1 + 1/r2) = p -Young-Laplace Equation

The Laplace equation shows that the

difference in pressure decreases to zero
as the radius of curvature becomes
infinite (when the surface is flat). Small
cavities have small radii of curvature, so
the pressure difference across their
surface is quite large.

DROP METHOD

Young equation
(homogeneous, smooth, rigid solids)
LV

Vapor

SV

Liquid
SL

Solid

LV

Strain field

SV

Horizontal balance of forces:

Young equation
SV = SL + LV cos

Liquid

dA

SL

dGS = (dGS)SV + (dGS)SL + (dGS)LV

dGS = dA (SL - SV) + dA LV cos ()
At equilibrium:
dGS /dA = 0
SV - SL = LV cos

If SV - SL > LV cos then cos = 1!

We now see that the liquid wets

(spreads over) the surface,
corresponding to 0 < c < 90,when 1
< wad/lg < 2. The liquid does not wet the
surface,corresponding to 90 < c <
180, when 0 < wad/lg < 1. For
mercury in contact with glass, c =
140, which corresponds to wad/lg =
0.23, indicating a relatively low work of
adhesion of the mercury to glass on
account of the strong cohesive forces
within mercury.

Wettability
Contact angle:
0
180
cos 1

Spreading Complete wett. Partial wetting

90o
0

SL= SV

-1

Negligible wett.

Non-wett.

For wetting to occur, the surface energy of the solid should be greater
than the liquid:
1) hard solids - covalent, ionic, metalic => high energy surfaces SV 500 to 5000 ergs/cm2
2) weak molecular crystals - vdW, H bonds => low energy surfaces V 50 ergs/cm2

Thank you!
Jose S. Solis, Ph.D.
Imee Su Martinez, Ph. D.
Institute of Chemistry
University of the Philippines - Diliman