CHM4400

Advanced Analytical Chemistry

Particle Size Analysis

Bo Zheng
bozheng@cuhk.edu.hk
Science Center Rm. 165
 Introduction

The ideal instrument for particle size analysis would provide a complete
distribution of the characteristic dimension of the particle.

Particle size analysis usually involves: (1) electrical properties; (2) transport
properties; (3) optical properties.

The instruments using these properties for particle size analysis generate
complex data at a high rate, and proper data analysis is critical in most
occasions.

In the current lecture, techniques such as microscope imaging, image

analysis, and sieving, are not considered, although these techniques can
also perform particle size analysis.
 Electrical Properties: Coulter Effect

The increase in resistance:

If a nonconducting particle
suspended in a conducting
medium is placed within a
small aperture, an increase in
the resistance across the
orifice, relative to that of the
medium alone is produced.
DR = (8rfd/3pD4) [1 + 4/5 (d/D)2 + 24/35 (d/D)4 + …]
rf is the resistivity of the conducting medium.
With suitable external circuitry, the resistance pulse
DR results in a voltage pulse iDR for a particle of
diameter d, where i is the current across the aperture.
 Coulter Counter Setup

MLK
N

The voltage pulses are counted and scaled using a multichannel analyzer in
Coulter counter
Coulter Counter Measurement Result

Pulse height histogram for T4

viruses with resistivity equivalent
diameters. N is the number of
pulses with indicated height.

In this example, the resistive pulse

technique is extended to particles
sizes well below 1 mm diameter and
is used for measurements on
viruses and other biological particles.
 Hydrodynamic Chromatography

SEC HDC

If a suspension of particles is injected into a

flowing carrier fluid (mobile phase) and then
passed through a column packed with stationary,
solid spheres, the larger particles elute from the
column before the smaller particles. The reason
is that larger particles experience a larger mean Typical HDC calibration
velocity in the packed column, because their size chromatogram using 2340 Å and
excludes them from the slower carrier fluid 1090 Å latex spheres.
velocity zones near the surface of the packing.
 Light Scattering

As particle size increases from smaller than 1/20 times to larger than l,
scattering from different portions of a single particles is out of phase, causing
interference and reduced intensity.
For large particles, rays emitted in a backward direction observed at point D
can destructively interfere because of the path difference between SXD and
SYD.
 Light Scattering

(d<0.05l)

(0.05l<d<l)
(d>l)

scattering angle

Raleigh scattering: When particle size is small (d<0.05l), the scattered

light shifts toward the side and rear and finally spreads in all directions.
The strong wavelength dependence of Rayleigh scattering (Is  1/l4) gives
us the blue sky.
 Mie Scattering
90o scattering

incident light
forward scattering

90o scattering

For particle sizes larger than a wavelength, Mie scattering predominates.

Mie scattering had an angular distribution of scattered light in which most

scattering is in the forward direction. Thus, light detection in a plane
intersecting the forward scattered light contains information of particle size.

The water droplets that make up the cloud are much larger than the
molecules of the air. The Mie scattering is responsible for the white
appearance of clouds.
 Fraunhofer Diffraction
For particles having a diameter much larger than l, there is little effect of
refractive index. A special case of Mie scattering theory, Fraunhofer
diffraction, is invoked.

For a single particle, the intensity distribution, I(x), of the Fraunhofer

diffraction pattern is given by the Airy equation:
I = I0(2J1(x)/x)2
where I0 is the intensity at the center of the pattern and J1 is the 1st-order
spherical primary Bessel function.

x = 2prs/lf; r is particle radius; s is radial distance, f is the lens focal length.

Airy function

x
 Particle Size Analysis

The Airy patterns for particles of radii r, 2r,

and 0.5r. Cumulative undersize distribution
N
g(N) = S K(N,di)f(di)Dd
i=1
g(N): The output of the Nth detector
K(N,di): detector response coefficient
di: the ith diameter
Dd: particle size interval
a = 2pr/l
f(di): size distribution
 Dynamic Light Scattering
When monochromatic, coherent light beam is incident on a dilute solution of
macromolecules such as proteins or suspension of colloidal particles and the
solvent refractive index is different from that of the solute (proteins or
microspheres), the incident light is scattered by each illuminated
molecule/particle in all directions. The scattered light waves from different
macromolecules or particles mutually interfere or combine, at a distant fast
photomultiplier tube (PMT) and produce a scattered intensity s(t’) that is not
uniform on the scattering or detection plane.

laser

PMT
 Dynamic Light Scattering
If all the particles are stationary, the scattered light intensity at each direction would be
a constant (independent of time). However in reality all the particles are undergoing
constant Brownian motions, causing fluctuations of the scattered intensity.
Dynamic light scattering measures the intensity fluctuations. When incident light is
scattered by a moving macromolecule or particle, the detected frequency of the
scattered light will be slightly higher or lower than that of the original incident light
owing to Doppler Effect, depending on whether the particle moves towards or away
from the detector. Thus, the frequency distribution of the scattered light is slightly
broader than that of the incident light.
This frequency broadening is so small (~10 5-107 Hz) in comparison to the light
frequency (~1015 Hz) that it is very difficult to detect in the frequency domain, but it can
be recorded in the time domain via a time autocorrelation function. At time t’, the
scattered light intensity is s(t’) and at a very small time later (t’+t), the diffusing
particles will have new positions and the intensity at the PMT will have a value s(t’+t)
which correlates with s(t’), the closer the measurement is to time zero, the more
similar s(t’+t) is to s(t’) since the particles have not had much time to move. As time
goes on there is no more similarity between the starting state and the current state;
the measured intensities do no correlate anymore to the beginning one.
 Dynamic Light Scattering

The output of photodetector S(w) is

proportional to E2, E is the electric
field vector
E = E1sinw1t + E2sinw2t

S(w) = A{E12sin2w1t + E22sin2w2t +

E1E2[cos(w1-w2)t – cos(w2+w1)t]}

Autocorrelation function:

C(t) = DS(t’) DS(t’+t)

where DS(t’) is the deviation from

t = DTq2
the mean at time t’, DS(t’) = S(t’) – S.
The bar means an average over all
times t’.
 Autocorrelation Function

The autocorrelation function is an exponential decay, with a time constant t.

t = DTq2

q is the modulus of the scattering vector: q = 4pnsin(q/2)/l

where n is the refractive index and q is the scattering angle.

DT is the translational diffusion coefficient.

For spherical particles, we have Stokes-Einstein equation to calculate the

hydrodynamic particle diameter dh:

dh = kBT/3phDT

where kB is Boltzmann’s constant, T is temperature, and h is viscosity.

 Dynamic Light Scattering

A cuvette sample cell is usually used and temperature

is well controlled by a liquid jacket. The refractive
index of the liquid is matched to the suspending
medium.
Solvents must be carefully filtered to remove dust
particles.
The upper concentration limit is determined by
multiple scattering phenomena, where light scattered
from one particle is rescattered by another.
Usually 90o detection angle is used. Photomultiplier
tube is the most common detector.