TURBIDIMETRY IN PARTICLE SIZE ANALYSIS 1

Turbidimetry in Particle Size 8 On-line Particle Size Determination

Using Turbidimetry 26
Analysis 9 Other Considerations 27
9.1 Choice of the Methods 27
Theodora Kourti 9.2 Corroboration of Results 28
Department of Chemical Engineering, McMaster 10 Conclusion 28
University, Hamilton, Ontario, Canada L8S 4L7 Abbreviations and Acronyms 29
Related Articles 29
References 29
1 Introduction 2
2 Theoretical Background 5
2.1 Turbidity and Particle Size 5 The size of particles in a suspension can be estimated
2.2 The Scattering Coefficient 6 by measuring the turbidity of the suspension. Turbidity
2.3 Turbidity and Moments of the measures the attenuation of a beam of light traveling
Particle Size Distribution 7 through the suspension caused by the scattering and
3 Particle Size Determination in Mono- absorption of light by the particles. The amount of
disperse Suspensions 7 scattering and absorption depends on the size of the
3.1 Specific Turbidity 8 particles and their concentration in the suspension. Most of
3.2 Turbidity Ratio 8 the reported applications in the literature use turbidimetry
4 Particle Size Distribution Determination for the estimation of the particle size distribution (PSD) or
in Polydisperse Suspensions 9 an average size for particles with diameters ranging from
4.1 Specific Turbidity 9 0.035 to 50 µm. Turbidimetric techniques are low cost,
4.2 Turbidity Ratio 11 experimentally simple, fast, nondestructive and require
4.3 The Wavelength Exponent no calibration. They are robust methods with very good
Technique 12 reproducibility and can be used either off- or on-line, in a
4.4 Resolution of a Conflict in the laboratory or a plant environment. They have been used for
Literature 13 particle or droplet size determination in a variety of diverse
4.5 Solving for the Particle Size systems such as latex particles, silver bromide sols and
Distribution 13 cow’s milk. Most of the time common ultraviolet/visible
(UV/VIS) spectrophotometers are utilized for the turbidity
5 Estimation of Average Diameters 16
measurements. Certain modifications may be necessary on
5.1 Turbidity-average Diameters 17
these instruments depending on the size of the particles.
5.2 Volume – Surface-average Diameters 17
The turbidity of the suspension is measured and the size
5.3 Weight-average Diameters 18
of the particles or the PSD is estimated utilizing light
5.4 Other Applications of Turbidimetry 18
scattering theory. For spherical isotropic homogeneous
6 Procedural Details 19 particles and absence of multiple scattering this theory
6.1 Instrumentation and Forward is well established. The extension to nonspherical and
Scattering 19 inhomogeneous particles is a field of active research
6.2 Refractive Indices of the Particles yielding numerous publications.
and the Medium 20 A controversy existed in the literature regarding the
6.3 The Choice of the Wavelengths 22 capability of turbidimetry to provide the full PSD but
6.4 Preparation of Samples 22 has now been resolved. For polydisperse suspensions,
6.5 Particle Volume Fraction for Spe- for certain combinations of particle sizes and optical
cific Turbidity 23 properties, the method cannot provide the full PSD,
7 Effect of Errors on the Estimated but only an average of the PSD. This limitation is
Particle Size and Particle Size simply a result of the light scattering patterns and it is
Distribution 23 expected theoretically. In some cases it can be overcome
7.1 Error in Measurements 23 by simply altering the optical properties of the suspension
7.2 Error in the Value of the Refrac- (i.e. choosing the proper wavelengths for the turbidity
tive Index Ratio, m 23 measurements or a medium with a different refractive
7.3 Error in the Assumed Distributional index to suspend the particles). To make the best use of
Form 24 the method and interpret the results in a meaningful way

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This article is © 2006 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2006 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1517
2 PARTICLE SIZE ANALYSIS
one should be aware of this limitation and work with
it. When this is done, excellent results can be achieved.
The advantages of the method and a good knowledge
of its capabilities make it a very robust choice for many
applications. The numerous reports from the successful
application of the method are a testimony to this.
1 INTRODUCTION
Turbidimetry refers to a group of techniques that utilize
either turbidity measurements at different wavelengths,
or a combination of measurements of turbidity and
of the particle volume fraction, to estimate the size
of particles in suspensions. Turbidity measures the
attenuation of a beam of light when it passes through
a suspension of particles. Using light scattering theory
this attenuation can be theoretically related to the size
and concentration of particles in the suspension if the
optical properties (refractive indices of particles and
medium) are known. For spherical particles and absence
of multiple scattering this theory is well established.
Extensions to nonspherical particles have been reported.
Simple UV/VIS spectrophotometers can be modified
(and in some cases used as bought) for the turbidity
measurements. Wavelengths in the near-infrared (NIR)
range can also be utilized. Particle sizes from the
lower submicrometer range to many micrometers can
be measured with the proper choice of wavelength for the
turbidity measurements. Applications of turbidimetry for
particle size determination have been reported mainly for
particles with diameters between 0.035 and 50 µm. The
simplicity of this fast, noninvasive method, its low cost,
good reproducibility and the wide range of particle sizes
that it covers have made it very attractive for particle
size determination. Mainly owing to its simplicity, the
method is robust and suitable for industrial production
environments as an on-line particle size determination
method.
The first attempts to use turbidimetry for particle size
determination started in the 1950s. At the time work-
ers tried to use approximation theories.1/ or tabulate
turbidity functions.2,3/ mainly owing to a lack of power-
ful computing machines. Ever since, there has been an
abundance of reports on the use of turbidimetric tech-
niques for the determination of particle size in a variety
of systems, such as silver bromide sols in water,.4 – 6/
polystyrene latexes,.7,8/ poly(vinyl acetate) latexes,.9 – 15/
homogenized milk and oil-in-water emulsions,.16 – 18/ cou-
pler dispersions.19/ and minerals..20/ A wide range of
wavelengths in the UV/VIS region have been utilized for
the turbidity measurements but also work in the NIR
region has been reported..6,16,17,19/ The determination of
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DOI: 10.1002/9780470027318.a1517
particle size using on-line turbidimetry has also attracted a
lot of attention..6,9 – 11,15,21 – 24/ Some of the work reported
in the literature for particle size determination in poly-
disperse systems (full PSD or an average diameter) for
different materials is given in Table 1.
A controversy in the literature.11,12,31/ regarding the
capability of turbidimetry to provide the full PSD has
been resolved by a theoretical analysis and experimental
verification reported in Kourti et al..15,32/ The results can
be summarized as follows.
The capability of turbidimetric techniques to provide an
average particle size or the PSD of a suspension and their
sensitivity to experimental error cannot be generalized
across refractive indices and particle size ranges. It
depends on the optical properties of the suspension and
the size of the particles relative to the wavelength and
conclusions cannot be extrapolated from one optical
regime and particle size to another and from one
technique to another. For monodisperse suspensions the
particle size can always be estimated using turbidimetry,
provided that two turbidity measurements at widely
separated wavelengths together with a measurement of
the particle volume fraction in the suspension is used. This
is irrespective of the optical properties of the suspension
(refractive indices of particles and medium, wavelength
of light) and the size of the particles. In some simpler
cases only two turbidity measurements or measurement
of one turbidity and the volume fraction are sufficient.
For polydisperse suspensions, turbidity measurements
at sufficient wavelengths (the number depends on the
detail of the PSD one wishes to resolve) together with a
measure of the particle volume fraction are required for
the determination of the full PSD. However, for certain
combinations of particle sizes and optical properties,
the method cannot provide the full PSD, but only
an average of the PSD. This limitation is simply a
result of the light scattering patterns and it is expected
theoretically. More specifically, it stems from the fact
that for some combinations of optical properties and
particle size, a light scattering function (the wavelength
exponent) changes very slowly with the relative size of
the particles to the wavelength. When this happens, in
the presence of experimental noise, estimation of the full
PSD is not possible. In some cases this limitation can
be overcome by simply altering the optical properties of
the suspension (i.e. choosing proper wavelengths for the
turbidity measurements or a medium different than water
to suspend the particles). Therefore, to make the best use
of the method and interpret the results in a meaningful
way, one should be aware of the regimes where this
limitation occurs.
Because of the behavior of the wavelength exponent,
turbidimetric techniques that utilize the measurement of
the particle volume fraction (which is a measurement of
 Table 1 Examples of applications of turbidimetry in particle sizinga

System m Particle size, Wavelengths Turbidimetric Assumed PSDb Commentsb Other methodsb
D (µm) (nm) method
Minerals.20/ : TiO2 1.9 0.1 < D < 10 436, 546, Specific Log-normal on weight Estimated PSD Centrifugal
Al(OH)3 1.86 650, 800 turbidity basis agrees very well sedimentation
Al2 O3 1.33 with measured
SiO2 1.163 PSD from
centrifugal
sedimentation

DOI: 10.1002/9780470027318.a1517
TiO2 pigments..25/ – Mean crystal 190 – 1100 44 turbidities No shape assumed. Study involves TEM
Oval-shaped crystals. sizes: and volume Estimate 26 heights of empirical modeling
Estimate crystal 0.086 – 0.237 fraction histogram in the range with latent

This article is © 2006 John Wiley & Sons, Ltd.

size-area equivalent 0.012 – 0.6375 nm variables – PLS
diameter
Stable silver bromide sols 1.7 D < 0.25 (1) 436, 546 Specific (1) Apparent diameters Important EM
in water.5/ (2) 450, 800 turbidity (2) Log-normal discussions on
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS

(ZOLD) apparent
diameters. See
section 5
Ostwald ripening process: 1.7 D < 0.8 2.22 µm Specific Apparent diameter (Dt ) On-line monitoring EM
silver bromide grains.6/ turbidity of grain growth.

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See section 8
Variety of materials.26/ – Weight average: 900 Specific Assumed g PSD with Some particles too Sieve
PVC, 138 turbidity known spread. large. Only D32 Coulter counter
sand, 116, 196 Reported average size expected to be
protein, 20 – 30 correct.
KCl 92 – 284

Polystyrene latexes.7/ 1.2 0.65 < D < 1.3 440 – 610 basis: Turbidity ratio Positively skewed with For polystyrene see EM
546 maximum also Haseler..19/

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polydispersity 1.5 See sections 4.2
and 7.3
Polystyrene.8/ 1.2 Synthesized 300 – 800 Turbidities No assumption on shape Solve directly for the
bimodal and only heights of the PSD
trimodal PSDs
Styrene – butadiene 1.16, 1.14 0.04 < D < 0.14 300 – 600 Specific (1) Apparent Dt Only Dt correct SEM
rubber and acryloni- (101 points) turbidity (2) Log-normal DLS
trile – butadiene (3) No shape
rubber.27/ assumption
Copolymer latexes: 1.17, 1.15 D < 0.4 350 – 1000 Specific Apparent diameters See section 5.1 EM
poly(butadiene – turbidity
styrene).28/
Photographic 1.166, 1.21 0.05 < D < 1.0 400 – 800 Specific Log-normal on weight Conclude that EM
dye-forming coupler turbidity and basis (verified by EM) success of method
dispersions.29/ wavelength depends on values
exponent of a
3

(continued overleaf )
 4
Table 1 (continued)
System m Particle size, Wavelengths Turbidimetric Assumed PSDb Commentsb Other methodsb
D (µm) (nm) method
Ektacolor coupler 1.15 D < 1.0 400, 700 Specific Log-normal See sections 4.1, 4.2, –
dispersions.19/ – droplet 400, 2.22 turbidity 5.2 and 7.3
size distribution
Cis-polyisoprene 1.136 0.6 < D < 1.1 650, 800, Specific Log-normal on weight Broad PSDs.15/ See Coulter counter
Latexes.58/ 950, 1100 turbidity basis also section 9.2 EM

DOI: 10.1002/9780470027318.a1517
Copolymer latexes: – 12 < DN < 50 400 – 600 Specific Apparent diameter See section 5.2. Some EM
divinyl – benzene/ turbidity (D32 ) coincidental

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styrene.66/ observations are
discussed by
Kubota et al..68/
Latexes.68/ – 2 < D < 40 400, 700 Specific Apparent diameter See section 5.2 EM
turbidity (D32 )
Octacosane 1.15 D < 3.0 436, 546 Turbidity 1. Log-normal Approach has serious EM
suspensions.48/ ratio and 2. One parameter limitations..50/ See
wavelength PSD, positively section 4.3.
exponent skewed
Poly(vinyl acetate).16/ 1.1 0.1 < D < 1.0 320 – 720 Turbidity ratio Positively skewed See sections 4.2 and EM

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4.4
Poly(vinyl acetate) 1.1 1. Dw : 0.20 300, 600 Specific Log-normal See sections 4.4 and Disc centri-
latex.11,12/ 2. Dt : 0.11 turbidity 8.0 fugation
Angular light
scattering
Poly(vinyl acetate).15,44/ 1.095 0.035 < D < 0.4 400 – 600 Specific Log-normal (Dap D Dw ) Experimental & HDC
turbidity theoretical analysis DLS
demonstrates the

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limitations of
turbidimetry in
some (m, a)
regions
Poly(vinyl acetate).23,24/ 1.095 D < 0.4 400 Specific Apparent diameter, Dw First successful DLS
turbidity on-line application
Poly(vinyl acetate) 1.1 D < 0.4 350 – 700 Method of Moments of PSD See section 4.5 HDC
latex.10/ moments
Paraffin oil in (water C 1.1, 1.05 0.1 < D < 10.0 300 – 1700 Specific (1) Log-normal See also other Coulter counter
glycerol/ C milk.16/ 0.1 < D < turbidity (2) An upper limit work.17,30/ for
40.0 function similar systems.
(3) Exponential type Successful
application
a The systems have been ordered based on the optical properties of the suspension (value of m).
b Abbreviations (other than those already defined in the text): PLS, partial least squares; TEM, transmission electron microscopy; ZOLD, zeroth-order logarithmic distribution; EM,
electron microscopy; SEM, scanning electron microscopy; DLS, dynamic light scattering; HDC, hydrodynamic chromatography.
PARTICLE SIZE ANALYSIS
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
the particle size and number independent of the scattering
properties) provide reliable estimates for the particle size
(the PSD or an average diameter) in a wider range of
sizes and optical properties than techniques that utilize
turbidity measurements only.
In this article, a brief overview of light scattering
theory is first presented followed by a description of
the turbidimetric techniques that are most commonly
used for particle size determination. For each technique
we include its theoretical background, comments on its
advantages and limitations and references to its successful
applications in the literature. We also include discussions
regarding the regions of particle sizes and optical
properties where the technique may present difficulties
in providing reliable estimates of the particle size or
the PSD. We then present cases where turbidimetry was
used to provide estimates of the average diameters of
the PSD and discuss the advantages and pitfalls of such
uses. We follow with details on the procedure such as
choice of wavelengths, calculation of refractive index
and instrumentation. The sensitivity of the turbidimetric
methods to experimental error is extensively discussed.
Applications on the use of the method for on-line
particle size measurements follow. We conclude with
a discussion on how users should proceed with choosing
the appropriate method for their application and with
comparing results from other particle sizing techniques.
Throughout the article several applications reported in
the literature are critically discussed in order to point
out some approaches with serious limitations and some
coincidental observations that may result in misleading
conclusions. In this way the readers can judge if the
approaches reported in the literature are suitable for
their use.
2 THEORETICAL BACKGROUND
2.1 Turbidity and Particle Size
Turbidity, tl0 (cm 1 ), gives a measure of the attenuation
of the intensity of a beam of light traversing through a
suspension of particles (Equation 1):
 
1 I0
tl0 D ln .1/
l I
where I0 and I represent intensities of the incident and
transmitted beams, respectively, and l is the length of
the optical path (i.e. cell length, cm). The value of the
turbidity changes with the wavelength of the incident light
beam, l0 . I is measured at 180° to I0 .
The attenuation of the intensity of light traversing
through a particle suspension is due to scattering of
light by the particles and in some cases (depending
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DOI: 10.1002/9780470027318.a1517
5
on the wavelength) absorption of light by the particles
and/or the medium. The amount of light scattered and
absorbed by the particles depends on their size, their
concentration in the suspension, the size of the particles
relative to the wavelength of the incident beam and
the refractive indices of the particles and the medium.
Therefore, theoretically, turbidity can be related to the
particle size. For a monodisperse suspension (particles of
equal diameter, D) of spherical, isotropic particles, in the
absence of multiple scattering (Equation 2):
pD2
tl0 D N Kext .2/
4
where N is the number of particles per cm3 and Kext is
the extinction coefficient at wavelength l0 . Kext is equal
to the sum of the absorption Kabs and the scattering Kscat
coefficients. The extinction coefficient can be calculated
from the rigorous Mie theory and the equations for
this calculation can be found in several sources..3,33 – 36/
In the work presented in this article we assume no
absorption (Kext  Kscat ) and this is the case for most
of the work reported in the literature. In most of the
reported applications workers have chosen to avoid
wavelengths where the medium or the particles absorb,
for practical reasons, explained in section 6.3. However,
should readers decide to work with absorbing particles,
they should use Kext for Equations (3), (4), (12), (13),
(15) and (18). The validity of the discussions in this article
does not change with the nonabsorption assumption.
For a monodisperse suspension of spherical, nonab-
sorbing, isotropic particles, in the absence of multiple
scattering (Equation 3):
 
pD2 pD2 D np
tl0 D NRscat D N Kscat D N K , .3/
4 4 lm nm
where Rscat , the scattering cross-section, is the total energy
scattered by one sphere when the incident light is of
unit intensity and either plane polarized or unpolarized.
The scattering coefficient, Kscat , or K.D/lm , np /nm /, is
dimensionless and it is an involved function of two
parameters, a and m. a D p.D/lm / is defined as the
relative size of the particle diameter to the wavelength
of the light in the medium (lm ) and m D np /nm is the
ratio of the refractive index of the particles to the
refractive index of the medium. lm D l0 /nm , where l0
is the wavelength of the incident beam in vacuo. Both
np and nm are evaluated at l0 . The estimation of the
refractive indices for homogeneous and inhomogeneous
particles is discussed in section 6.2. In cases where the
particles absorb, the refractive index has both real and
imaginary parts.
For a polydisperse suspension of spherical nonab-
sorbing, isotropic particles, in the absence of multiple
6 PARTICLE SIZE ANALYSIS

scattering turbidity is given by Equation (4): here in some detail. The scattering coefficient is defined
Z 1   as the ratio of the scattering to the geometrical cross-
pD2 D np section. The scattering coefficient exhibits an oscillatory
tl 0 D N K , f .D/ d.D/ .4/
0 4 lm nm dependence on a, with a series of successive minima and
where f .D/ is the normalized PSD. maxima (Figure 1). The first maximum occurs at lower
In general, because Kscat is an involved nonlinear a values the larger is the value of m; the numerical
function of a (i.e. D/lm ), it is possible from turbidity value of Kscat at the first maximum is larger the larger
measurements at a sufficient number of wavelengths is m. At large values of a, m has virtually no effect
(or a combination of turbidity measurements and other on Kscat , in agreement with the theory of diffraction
properties of the particle suspension) to estimate the for objects very large compared with the wavelength
size of the particles in a monodisperse suspension or used, and Kscat approaches the value of 2. Values of
the PSD in a polydisperse suspension. However, it has Kscat for various large a values are shown in Table 2.
been shown.32/ that for certain combinations of (m, a) Note that for m D 1.2 and 200 < a < 220 the value of
values the estimation of the particle size or the PSD the oscillating Kscat can be found between 2.12 and 1.99,
of the suspension may present difficulties with some whereas for 2500 < a < 2700, Kscat oscillates between
turbidimetric techniques. Being aware of these (m, a) 2.016 and 2.006. When plotted against a, the scattering
regimes will help the user choose the proper turbidimetric coefficient also exhibits secondary fluctuations (ripples)
technique and proper wavelengths to work with in order that become increasingly irregular for higher values of m.
to obtain the most reliable estimate of particle size of a Another parameter which is often used in light scattering
suspension. is r D 2ajm 1j; r is the phase shift suffered by a wave
passing through the center of a sphere..37/ When Kscat is
plotted against r, the r position of the extremes (minima
2.2 The Scattering Coefficient and maxima) of the main oscillation is independent of
Certain features in the behavior of the scattering the value of m..33,34/ Recall that this discussion is for
coefficient are important in explaining the capability of spherical, isotropic spheres. Scattering for nonspherical
turbidimetric techniques to provide the particle size or particles is an area of active research.38/ and publications
the PSD of a suspension. These features will be discussed are available..39 – 41/
As mentioned earlier, in the general case the scattering
4.0 coefficient can be calculated from the rigorous Mie
m =1.2 theory..3,33 – 36/ In certain (m, a) regimes the equations for
3.5 Kscat can be approximated with simple expressions which
m =1.1 give Kscat within 1% accuracy from its true value..37/
3.0
These expressions are discussed here because they help
2.5 in elucidating some of the problems encountered by
researchers when converting turbidity measurements to
2.0 particle size.
Kscat

1.5 1. When the suspended particles are very small com-

1.0 pared with the wavelength both outside (a − 1) and
inside (jmaj − 1), the particle,.34,37,42/ the Rayleigh
0.5 scattering theory gives Equation (5):

0.0    2
0 20 40 60 80 100 D np 8 m2 1
K , D a4 .5/
α = πD/λm lm nm 3 m2 C 2

Figure 1 Scattering coefficient, Kscat , plotted against a for 2. For particles very large compared with the wave-
m D 1.1 and 1.2. length, the scattering coefficient approaches a

Table 2 Range of values (maximum – minimum) observed for the oscillating Kscat in different ranges of a values for m D 1.1 and 1.2

m 20 < a < 40 80 < a < 100 140 < a < 160 200 < a < 220 800 < a < 1000 1500 < a < 1700 2500 < a < 2700
1.1 3.45 – 1.64 2.39 – 1.88 2.24 – 1.99 2.175 – 1.98 2.051 – 1.998 2.03 – 2.002 2.0195 – 2.002
1.2 2.7 – 1.7 2.26 – 1.94 2.16 – 1.98 2.12 – 1.99 2.0365 – 2.0065 2.023 – 2.006 2.016 – 2.006

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DOI: 10.1002/9780470027318.a1517
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS 7

constant value independent of m.3,33,34,37/ (Equa- 6.0 4

tion 6):
  5.5
D np
K , D2 .6/
lm nm

Exponent z
5.0 3

Exponent y
Walstra.37/ has reported that this is true for r D 4.5
2ajm 1j > 300 and a > 2000. Table 2 gives the
range of Kscat values for different a values and m D 1.1 m =1.05
4.0 2
and 1.2. Note that for m D 1.2 and a values between m =1.1
200 and 220 the values of the oscillating Kscat can be 3.5
found between 2.12 and 1.99. Assuming a constant m =1.15
m =1.25 m =1.2
value of 2.0 may introduce a maximum of 6% error in 3.0 1
0 2 4 6 8 10 12
Kscat in this range. For very large values of a, assuming
Kscat D 2.0 gives Kscat within 1% accuracy from the α = πD/λm
true value.
Figure 2 Exponents y and z for m D 1.05, 1.1, 1.15, 1.2 and 1.25.
Equations (5) and (6) are the two extremes of a
general expression where for monodisperse suspensions where both k and y are functions of D. When the particle
of nonabsorbing spheres, the dependence of the scattering sizes in the suspension are such that k and y do not change
coefficient on the diameter at a given wavelength is significantly with D, then (Equation 10):
approximated by Equation (7):.4,5/ Z 1
   z tl0 D Nk Dy f .D/ d.D/ D Nk Jy .10/
D np D
K , Dk 0
D k0c az .7/ 0
lm nm lm where k and y are constants. In these cases, turbidity is
where k0 and k0c are proportionality constants. Note proportional to the yth moment, Jy , of the PSD. The value
that z D 4 in the Rayleigh regime and z D 0 for large of y (i.e. the order of the moment) changes with a and m
particles (compare Equation 7 with Equations 5 and 6, (Figure 2). For a < 0.5, y approaches the limiting value
respectively). When plotting Kscat against the wavelength of 6 (z D 4, Rayleigh regime) and therefore turbidity is
for constant D, we have Kscat D k00 l0 z , and therefore z proportional to the sixth moment of the PSD. For values
has been termed ‘‘the wavelength exponent’’..43/ When of m between 1.1 and 1.2, and for a < 1.6, the value of y is
plotting Kscat against a at constant lm , we can write almost independent of the value of m. Kourti et al..15,32,44/
Equation (8): discussed that for small values of m (m D 1.05, 1.1, 1.15)
the value of y is approximately 4.0 (4.2  y  3.8) for a
ln.Kscat / D z ln a C ln k0c .8/ very wide range of a values (for m D 1.05, 3 < a < 14; for
m D 1.15, 3 < a < 6). For suspensions with PSDs in the
The value of z can be obtained for any a at any m value above (m, a) regions, turbidity would be approximately
from the slope of ln Kscat vs ln a. proportional to the fourth moment of the PSD. Finally,
for very large particles, y D 2 and turbidity is proportional
to the second moment of the PSD.
2.3 Turbidity and Moments of the Particle Size
Distribution

In regimes where Kscat can be approximated by Equa- 3 PARTICLE SIZE DETERMINATION IN

tion (7), the turbidity of a monodisperse suspension at a
given wavelength l0 can be written as t D NkDy , where
y D z C 2 and k is a constant. Several authors.5,43/ have
tabulated values of y or z for several pairs of (m, a) values
(in the notation of Heller et al.,.43/ z  n). Values of y
and z are plotted in Figure 2 for several m values and
a  12.0. From Equations (4) and (7), for a polydisperse
system, at a given l0 , we can write Equation (9):
Z 1
tl 0 D N k.D/Dy.D/ f .D/ d.D/ .9/
0
MONODISPERSE SUSPENSIONS
The turbidity of a suspension of spherical particles
as given in Equation (3) is a function of both the
number concentration of particles (N) and the particle
diameter (D). The estimation of these two unknowns
requires sufficient measurements of turbidity at different
wavelengths or measurements of turbidity and another
property that is also related to particle concentration
and diameter. Two approaches have been used in the
literature:.33/ the turbidity at a given wavelength is divided

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DOI: 10.1002/9780470027318.a1517
8 PARTICLE SIZE ANALYSIS

either by the particle volume fraction or by the turbidity
value at another wavelength, such that the unknown
number of particles is eliminated, and the new quantity
is related to particle size only. Once the particle size is
determined, substitution into Equation (3) will give N.
3.1 Specific Turbidity
The volume fraction of the spherical particles in a
monodisperse suspension is given by Equation (11):
pD3
fDN
6
The particle volume fraction can be measured (see
section 6.5) using gravimetric analysis or densito-
metry..21,23,45/ The specific turbidity, defined as the ratio
of the turbidity of the suspension to the volume fraction
of the suspended particles, is independent of the particle
number concentration (Equation 12):
 
D np
tl 0 3 K ,
lm nm
D .12/
f 2 D
Specific turbidity is plotted against diameter in Figure 3
for two different types of particles suspended in water:
poly(vinyl acetate) with m ³ 1.1 and polystyrene with
m ³ 1.2. The particle diameter D can be calculated
from one turbidity measurement and the particle volume
fraction when the optical properties of the suspension
are known and the expected particle size range is known.
For example, if it is known that we have submicrometer
particles then one specific turbidity measurement for
poly(vinyl acetate) at 600 or 400 nm would give the
8 poly(vinyl acetate) particles suspended in water. The
Specific turbidity × 10−4 (cm−1)
particle diameter. Note that owing to the oscillatory
behavior of the specific turbidity, more diameters may
correspond to one specific turbidity value. For example,
for polystyrene a specific turbidity reading of 15 000 cm 1
at 400 nm in the range shown in Figure 3 corresponds to six
different diameters (0.15, 1.7075, 1.855, 1.865, 1.9225 and
2.56 µm; four due to the main oscillating pattern of Kscat
and two due to a secondary rippling effect). Therefore,
if the size range is not a priori known, measurements at
two (preferably widely spaced) wavelengths are required
to extend the applicability of the method to a wide
.11/ range of particle sizes..15/ Once the particle size has
been estimated, the concentration of the particles in
the suspension (N) can be calculated from Equation (3).
Note that in the Rayleigh regime, where Kscat is given
by Equation (5), the specific turbidity at given lm is
directly proportional to the volume of the particles
(t/f / D3 ), and that for very large particles (Kscat D 2.0) it
is proportional to the inverse of the diameter (t/f D 3/D).
3.2 Turbidity Ratio
The ratio of two turbidity readings taken at two
wavelengths is a quantity independent of the particle
number concentration (Equation 13):
 
D np
tl01 K ,
lm nm l
D   01 .13/
tl02 D np
K lm , nm
l02
Subscripts l01 and l02 denote that the quantities t, np ,
nm and lm are evaluated at these wavelengths; l01 ,
l02 are the wavelengths in vacuo. Figure 4(a) shows
the turbidity ratio (at 400/600 nm) for polystyrene and

particle diameter could be estimated from one turbidity

7 ratio (two turbidity measurements) if the ratio was a
PS-400 nm
monotonic function of particle size or a. However, this is
6
not the case, as can be seen in Figure 4(a). An indentation
5 exists in the turbidity ratio vs a curve, at the lower a
PS-600 nm
regime, owing to the first inflection point of the Kscat
4 vs a curve (in polydisperse suspensions, this indentation
vanishes). Also, for larger particles, the turbidity ratio
3 PVAc-400 nm vs a curve exhibits an oscillatory behavior. Therefore,
2
PVAc-600 nm unless the size range is a priori known, a reading at a third
wavelength (two turbidity ratios) is advised, to define
1 uniquely the particle size. Again once the particle size is
estimated the number of particles can be calculated from
0 Equation (3).
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
An example where only one turbidity ratio is
Diameter (µm)
not sufficient to determine the particle size was
Figure 3 Specific turbidity plotted against particle diameter for reported by Kourti..15/ The turbidity ratio measure-
monodisperse poly(vinyl acetate) and polystyrene latexes at 400 ment at l01 D 400 nm and l02 D 500 nm for a 60 : 40
and 600 nm. poly(styrene – butadiene) latex was repeated several times

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TURBIDIMETRY IN PARTICLE SIZE ANALYSIS 9
7 and t500 /t600 ) plotted against diameter for monodis-
perse polystyrene suspensions. The diameters are in
6 a range around the first indentation in the turbidity
ratio – diameter curve. Note that suspensions with two
τ400 nm/τ600 nm

5
very different particle sizes (0.2 and 0.25 µm) will give the
4
same turbidity ratio at two different wavelengths (1.72
for t500 /t600 and 3.54 for t400 /t600 ). In fact, for this exam-
3 ple, with an experimental error as small as 2.0% in the
turbidity ratios, any solution between 0.2 and 0.25 µm is
PVAc possible. It would be preferable if the three wavelengths
2
PS
at which the measurements were taken were more widely
1 separated.
The turbidity ratio method practically gives no informa-
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 tion on the particle size for (i) very large particles, where
for all the wavelengths used the scattering coefficient is
(a) Diameter (µm)
constant (substitution of Kscat D 2 in Equation 13 gives a
4.0
turbidity ratio equal to unity), and (ii) very small particles,
where for all the wavelengths used the Rayleigh Equa-
τ400 / τ600 tion (5) applies and turbidity ratio becomes independent
3.5 of the particle size.
Turbidity ratio

3.0
4 PARTICLE SIZE DISTRIBUTION
DETERMINATION IN POLYDISPERSE
2.5 SUSPENSIONS

2.0 Specific turbidity and turbidity ratio measurements can

τ500 / τ600
1.5
0.10 0.15 0.20 0.25
(b) Diameter (µm)
Figure 4 (a) Turbidity ratio at 400/600 nm plotted against
particle diameter for polystyrene with m ³ 1.2 and poly(vinyl
acetate) with m ³ 1.1 latexes. (b) Turbidity ratios for polysty-
rene, m ³ 1.2. Note that owing to the oscillation in the curves,
particle suspensions with two different diameters (0.2 and
0.25 µm) give the same turbidity ratio values at two different
wavelengths.
(for four different dilutions of the same sample). Each
time, two estimates (two solutions) of particle size were
obtained. In one of the solutions the estimates of the
diameter were between 209 and 228 nm and in the other
between 157 and 165 nm. Results from other methods had
shown that the true diameter range was around 200 nm
[specific turbidity (208 – 221 nm), HDC (228 nm) and DLS
(194 nm)] and therefore the first solution could be picked
as the correct one.
Caution should be exercised when diameters are in
a range around the first indentation in the turbidity
ratio– diameter curve when using the turbidity ratio
method. Figure 4(b) shows turbidity ratios (t400 /t600
also be used to estimate the PSD in polydisperse suspen-
sions. Numerical approaches that can be used to solve
for the PSD from turbidity and specific turbidity mea-
0.30
surements are discussed in detail in section 4.5. However,
the estimation of the full PSD is not always possible with
turbidimetry..15,32/ Some turbidimetric techniques are not
theoretically expected to provide the full PSD of a suspen-
sion if, because of its optical properties (refractive indices
of medium and particles) and the sizes of the particles, the
(m, a) values of the suspension are within certain ranges.
In such cases the specific turbidity technique will provide
an estimate of an average diameter while techniques sim-
ilar to the turbidity ratio provide no information on the
particle size. The (m, a) regimes where the estimation
of the full PSD is practically possible are discussed for
each one of the turbidimetric methods presented in this
section.
4.1 Specific Turbidity
Examples of successful applications of the method for
particle and droplet size distribution determination can
be found in Meehan and Beattie,.5/ Walstra.16/ and Yang
and Hogg..20/ For a polydisperse suspension of spherical
particles, the volume fraction is (Equation 14):
Z 1
pD3 p
fDN f .D/ d.D/ D N J3 .14/
0 6 6

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10
where J3 is the third moment of the PSD. The specific
turbidity is given by Equation (15a):
Z 1  
n tl 0
D2 K lDm , nmp f .D/ d.D/
tl 0 3 0
D Z 1 .15a/
f 2 3 0
D f .D/ d.D/
0
Alternatively, the specific turbidity of a suspension can
be written as Equation (15b):
Z 1
tl0 t
D .D, l0 /F.D/ d.D/ .15b/
f 0 f assumed shape of the PSD or using a regulariza-
where t/f.D, l0 / is the specific turbidity corresponding
to particles with diameter D and wavelength l0 and F.D/
is the normalized PSD on a weight basis.
For a suspension of spheres, when the optical properties
of the suspension are known, a minimum of P specific
turbidity measurements are required for the estimation
of a P parameter PSD from Equation (15a) or (15b),
as discussed in the next section. For example, if we
assume that the PSD is known to be log-normal described
by the mean diameter and the variance, we need at
least two specific turbidity measurements. If the form of
the PSD is not assumed and we attempt to recover the
frequency distribution at P given diameters (i.e. P discrete
points), then at least P specific turbidity measurements
are required.
In the presence of experimental error, the estimation of
the full PSD from Equation (15a) or (15b) is impossible
if all the turbidities (i.e. at all the wavelengths required
for the estimation) are approximately proportional to the
same moment of the PSD, Jy . Given that f is always
proportional to the third moment J3 of the PSD, in these
cases specific turbidity becomes proportional to Jy /J3 ,
that is proportional to the (y 3)rd power of the Dy3
average diameter..32/ Kourti et al..32/ showed that when
this happens for all of the P wavelengths used, many
alternative solutions (PSDs) correspond to the same
specific turbidity measurements and it is impossible to
isolate the true solution unless there is some a priori
knowledge. However, all these alternative solutions have
their Dy3 average diameters numerically very close to
each other. In that case it was suggested that only this
average diameter Dy3 can be correctly estimated from
specific turbidities.15,32/ in this range of wavelengths.
The (m, a) regimes where the full PSD is practically
impossible to estimate for nonabsorbing particles are as
follows:
1. For any m value and very small a (Rayleigh regime).
If for all the wavelengths used for the turbidity
measurements we are in the Rayleigh regime, then
substitution of Equation (5) in Equation (15a) gives
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PARTICLE SIZE ANALYSIS
Equation (16):
Z 1
D6 f .D/ d.D/
J6
D kl0 Z0 1 D kl0 D kl0 D3t .16/
f J3
D3 f .D/ d.D/
where Dt (or D63 ) is the turbidity-average diam-
eter and kl0 D 4p4 lm4 [.m2 1//.m2 C 2/]2 and the
subscript l0 denotes that t, lm and m are evalu-
ated at l0 . Llosent et al..27/ tried to estimate the
full PSD in the Rayleigh regime using either an
tion method (discussed later) to solve at discrete
points for the PSD. Their results confirmed the
suggestions of Kourti et al..32/ that only the turbidity-
average diameter can be correctly estimated in these
regimes.
2. For any m value and very large diameters (where
Kscat ³ 2), we have Equation (17):
Z 1
D2 f .D/ d.D/
tl 0 J2 3
D 3Z 1
0
D3 D .17/
f 3 J 3 D 32
D f .D/ d.D/
0
D32 , the volume – surface average, is also sometimes
referred to as the Sauter mean diameter.
3. (m, a) regimes where the exponent y is close to
4.0. In an extensive study with theoretical analy-
sis and experimental validation, Kourti et al..15,32/
showed that for suspensions with PSDs in (m, a)
regimes where the exponent y is very close to 4.0
(3.8 < y < 4.2), specific turbidities result in apparent
diameters numerically very close to the weight aver-
age (Dw or D43 ) of the true PSD. The regions of (m, a)
values where this happens can be read from a y vs a
plot, such as that in Figure 2. From such a plot we can
see that y ³ 4, for m D 1.05 at 3.0 < a < 14 and for
m D 1.15 at 3.0 < a < 6.0. If the whole distribution
covers a values in this regime for all the wavelengths
used for the turbidity measurements, then within
experimental error many alternative solutions are
possible and only the weight-average of the distri-
bution can be correctly estimated. This is true for
any type of distribution (multimodal or unimodal
continuous distribution, or simply the mixture of
two populations). Table 3 gives an illustration of the
effect of small measurement errors on the estimation
of the PSD in these regimes, for m D 1.1. In case A,
the true distribution is log-normal (see Equation 21)
with Dg D 175 nm and s D 0.2 and weight-average
diameter Dw D 201 nm. The turbidities for such a
suspension were theoretically calculated at three
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS 11

Table 3 Illustration of effect of small random measurement errors on the estimated PSD for m D 1.1a

Case True PSD Different random Estimated PSD

error for each test
Dg (nm) s DN (nm) DW (nm) Dg (nm) s DN (nm) DW (nm)
A 175 0.2 178 201 A1 116 0.39 125 199
A2 198 0.08 198 202
B 455 0.2 464 523 B1 520 0.002 520 520
B2 336 0.362 359 533
a Two cases with different true PSDs are examined: (A) Dg D 175, s D 0.2 and (B) Dg D 455, s D 0.2. A maximum error of š1.2% was introduced
randomly in the specific turbidities at several wavelengths. Then the PSD was re-estimated. For each case two different random errors were tried,
and two very different PSDs were obtained, both far from the true solution, but with Dw close to the true solution.

wavelengths. An error of less than 1.0% was then
introduced in the three turbidity values and the
parameters of the PSD were re-estimated (case A1).
Note that the estimated Dw D 199 is within 1% of the
value of the true weight average of the PSD whereas
Dg and s are significantly different. A different
random error less than 1% was introduced in the three
turbidities for case A2. Again, only the weight aver-
age of the estimated distribution Dw D 202 is within
0.5% of the true value and the other parameters are
significantly different from the true distribution but
also from case A1. Similar results were obtained for
case B. For different random errors of š1.2% on the
turbidity values, cases B1 and B2 were obtained with
weight averages within 2% of the true value but with
all the other parameters significantly different from
the true distribution.
Reports in the literature confirm that the PSD cannot be
estimated with specific turbidity in some cases. Haseler.19/
working with Ektacolor suspensions (m D 1.15) reported
that experimental errors in specific turbidities (measured
at 400 and 700 nm) would lead to large errors in the
calculated distribution. These results were observed
because of the small (m, a) values with which he was
working. Based on the above discussion, only Dw could
be correctly estimated in those (m, a) regimes. Walstra,.16/
trying to estimate the globule size distribution in cow’s
milk (m D 1.1) from specific turbidity measurements,
reported that for very fine emulsions (D32 < 200 nm) with
rather high polydispersity the reliability of the method
decreases and showed that a set of experimental data
could be fitted to many different types of distributions
with the same Dw .
The observations of Kourti et al..15,32/ revealed a very
useful property of the specific turbidity: the weight-
average diameter of suspensions can be correctly esti-
mated even though the determination of the PSD is
impossible. This property of specific turbidity can be uti-
lized for practical purposes where a fast estimate of the
weight-average diameter is required and is sufficient to
monitor the progress of a process. Gossen.23,24,46/ utilized
this information and used specific turbidity to monitor
the progress of polymerization reactions with on-line
measurements. The a range where specific turbidity mea-
surements give Dw may be extended further when the
distribution is log-normal. For example, for suspensions
with m D 1.1 and log-normal distributions of submicrom-
eter particles, it has been observed that the mean value
of the apparent diameters, estimated from specific tur-
bidities at 400 and 600 nm, is within 5% the true weight
average diameter of the PSD..15,32/ Monitoring these two
apparent diameters gives information on the weight aver-
age of the PSD.
It should be noted that in all the regimes where the
estimation of the full PSD is impossible, specific turbidity
gives good estimates of meaningful average diameters.
Compared with other turbidimetric techniques, where
information only from turbidity measurements is used,
the specific turbidity has the advantage that an additional
measurement is used, the solids volume fraction, which
is always proportional to the third moment of the PSD.
Therefore, whenever turbidities at two or more wave-
lengths are proportional to the yth moment of the distri-
bution, although the estimation of the true PSD is impossi-
ble, a meaningful average of the PSD, the Dy3 average, can
always be obtained from specific turbidity measurements.
4.2 Turbidity Ratio
The ratio of two turbidity readings taken at different
wavelengths for a polydisperse suspension is given by
Equation (18):
Z 1  
n
D2 K lDm , nmp f .D/ d.D/
tl01 l01
D Z0 1   .18/
tl02 n
D2 K lDm , nmp f .D/ d.D/
0 l02
Again, subscripts l01 and l02 denote that the quantities
t, np , nm and lm are evaluated at the corresponding
wavelengths; l01 , l02 are wavelengths in vacuo. For a
PSD described by P parameters, a minimum of (P C 1)
turbidity measurements at different wavelengths (one of

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12
which is chosen as reference) are required, in principle,
for the estimation of these parameters. The method gives
no information on the particle size in the following cases,
for nonabsorbing particles:
1. For any value of m and very large particles where
Kscat D 2, the turbidity ratio equals 1.0.
2. For any value of m and very small particles, where
the Rayleigh Equation (5) applies, the turbidity ratio
equals a constant value, independent of the particle
size.
3. When, for all the wavelengths used, turbidities are
approximately proportional to the same moment
of the PSD. This case is observed for very small
m values (m ³ 1.15, 1.1, 1.05) and for a very wide
range of a values below the first Kscat maximum,
where the exponent y changes very slowly with a.
This in turn means that even for broad distributions
with sizes falling in these a regimes, turbidities at
widely separated wavelengths will be proportional to
approximately the same moment of the PSD, and
their ratio will be almost independent of the particle
size. Kourti et al..15,32/ showed that for m D 1.1
and submicrometer particles, the estimation of the
true PSD from turbidity measurements at 350 and
700 nm (with reference l0 D 546 nm) is impossible for
measurement errors as small as 0.5%. One example is
reported in which the effect of error on the estimated
PSD is studied for a turbidity ratio error as small
as š0.35% in the above three wavelengths. The
PSD was re-estimated for different errors (less than
š0.35%) each time. Several very different log-normal
distributions were obtained; for example, one of the
estimated PSDs had a geometric mean Dg D 500 nm
and standard deviation s D 0.15, Dw D 541 nm and
polydispersity 1.05, while another had Dg D 285 nm,
s D 0.4, Dw D 499 nm and polydispersity 1.6.
The turbidity ratio method should therefore be avoided
for the estimation of the PSD for systems of very small or
very large particles and for systems with small m values
(m < 1.15) and a values below approximately 10 (for a
short wavelength of 400 nm and water medium, these a
values cover all the submicrometer size range). In these
regimes the method is so sensitive to experimental error
that it offers practically no information on the size of the
suspended particles (i.e. neither the PSD nor an average
can be estimated).
Owing to the behavior of the turbidity ratio in the
ranges of (m, a) values described above, controversial
reports on the capabilities of the turbidity ratio to
provide the full PSD have appeared in the literature.
Wallach and Heller.7/ obtained estimates very close to the
true distribution for polystyrene suspensions (m D 1.2)
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PARTICLE SIZE ANALYSIS
with particle diameters between 650 nm and 1.3 µm from
turbidity measurements at l01 D 440 nm, l02 D 610 nm
and l03 D 546 nm. The values of m and a in their system
were such as to allow for successful PSD determination.
However, when Haseler.19/ tried the turbidity ratio
method for a system with smaller m and a values (m D
1.15, l0 in the range 400 – 700 nm and submicrometer
particles), he reported that within experimental error a
large number of different distributions gave the same
turbidity spectra. Similarly, Maxim et al..31/ reported that
the ‘‘turbidity ratio leads to multivalued solutions and
unless prior estimates of the answer by some other
method are available there are no criteria for choosing
between alternative solutions’’. They were working with
small m values (m D 1.1), submicrometer particles and
wavelengths of 320 – 720 nm with a reference wavelength
of 546 nm, that is an (m, a) area where Kourti.15/ showed
that even a 0.5% error in the turbidity ratio measurements
means that the PSD estimation is practically impossible.
The results of both Haseler and Maxim et al. were
expected based on the (m, a) values of their systems.
It is clear from the above examples that one cannot
generalize conclusions on the capability of turbidimetric
techniques to provide the PSD across (m, a) values.
4.2.1 Methods Similar to Turbidity Ratio
Alternatively to Equation (18), some authors.47,48/ use
the ratio given in Equation (19):
.tl/f/l01
.19/
.tl/f/l02
Notice that, numerically, f is eliminated from Equa-
tion (19), hence there is no reason to measure it. Other
authors use the DQ (dispersion-quotient) method (Equa-
tion 20):.33/
tl01 l202
DQ D .20/
tl02 l201
Both of the above approaches have the same limitations
as the turbidity ratio method for the estimation of the
PSD.
4.3 The Wavelength Exponent Technique
In this approach, the particle size can be estimated only
from turbidity measurements as in the turbidity ratio
technique (i.e. the particle volume fraction does not need
to be known). The change of the turbidity of a suspension
with the wavelength is recorded and related to the size
of the suspended particles. The technique is described in
detail in Bateman et al.,.49/ Heller et al..43/ and Kourti..15/
It has been shown.15,50/ that the turbidity ratio and
the wavelength exponent are theoretically equivalent
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
methods for the determination of the parameters of
the PSD. The functions used in the formulations of the
two techniques to convert the turbidity measurements to
PSDs can be derived from each other, and in case of
no measurement error the use of either method gives
identical results. Consequently, in the (m, a) regions
where the estimation of the particle size in a suspension
is not possible using the turbidity ratio method, the
wavelength exponent method also fails. It should also be
noted that although the two methods are theoretically
equivalent for the determination of the PSD, the
formulation of the turbidity ratio method is less complex
than that of the wavelength exponent. Consequently,
the turbidity ratio method requires less computation to
calculate the PSD and the error propagation is smaller.
Melik and Fogler.48/ suggested an approach in which a
combination of the wavelength exponent and the turbidity
ratio method is used and claimed that with this approach
the two parameters of the PSD can be estimated from only
two turbidity measurements. However, since these are not
two different methods but are theoretically equivalent, at
least three turbidity measurements are required for the
determination of a two-parameter PSD using either of
the methods or their combination. Otherwise (i.e. using
two turbidity measurements only), an infinite number
of solutions will be obtained. The claims of Melik and
Fogler.48/ were shown.50/ to be unfounded.
4.4 Resolution of a Conflict in the Literature
The analysis presented by Kourti et al..15,32/ which
showed that the capability of a turbidimetric technique
to provide the PSD is strongly related to the (m, a)
values of the suspension helped to resolve a controversy
that existed in the literature. This conflict, on whether
the true PSD of a suspension can be estimated from
turbidimetric techniques, arose between Maxim et al..31/
and Zollars..11,12/ As discussed earlier, Maxim et al. used
the turbidity ratio method to estimate the full PSD
in commercial suspensions, with m D 1.1 and particles
with diameters smaller than 1.0 µm. A high correlation
between the parameters of the distribution was observed.
The authors stated that a valid estimate of the true
distribution is impossible in the presence of experimental
error. According to the analysis presented by Kourti
et al..32/ these observations are justified (and were
expected) for the (m, a) values of the suspension and the
turbidity ratio method. Zollars used a simulation study
with no experimental error to re-estimate the parameters
of log-normal PSDs from theoretically calculated specific
turbidities. Of course, the parameters were correctly re-
estimated. The author stated that ‘‘turbidimetry does
not exhibit multiple solutions as reported by other
investigators’’. His observations.11,12/ are also justified
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13
for a specific turbidity method and re-estimation of
the parameters with no experimental error. Both the
workers were correct for the types of cases they were
studying. However, their findings cannot be extrapolated
over turbidimetric methods and (m, a) regimes. This
extrapolation caused the controversy.
4.5 Solving for the Particle Size Distribution
Equations (15a) and (18) give the value of the specific
turbidity or turbidity ratio, respectively, at given wave-
lengths if the PSD, f .D/, is known. The inverse problem
is to determine the PSD given the turbidity or the specific
turbidity measurements at several wavelengths, l0i . If a
continuous set of measurements of tl0 vs l0 was avail-
able, one could theoretically deconvolute these equations
to yield f .D/. However, in practice, one usually has tur-
bidity measurements at a finite number of wavelengths,
so we have to reconstruct f .D/ from only a number of dis-
crete values of tl0i . This is a typical problem in science..51/
We routinely measure ‘‘enough points’’ and then ‘‘draw a
curve through them’’. In doing so for this problem, we are
making some assumptions either about the underlying
function f .D/ or about the nature of Kscat , or both.
Two approaches have been taken in the literature
to solve for f .D/. When a small number of turbidity
measurements are available, a type of distribution that
can be described by a few parameters is assumed for
f .D/ (i.e. Gaussian, log-normal, etc.) and we solve for
these parameters. When many turbidity measurements
are available it is possible in some cases to solve for fj
[the discretized f .D/] at a number of selected diameters,
Dj . In general, the second approach requires many more
turbidity measurements than the first.
4.5.1 Approximate the Particle Size Distribution
with a Known Distributional Form
When a small number of turbidity measurements are
available, a convenient approach is to approximate f .D/
with a distributional form that can be described by a
few parameters. This form is then substituted into Equa-
tion (15a) or (18) and its parameters are estimated from
the turbidity measurements using non-linear parameter
estimation procedures such as the Levenberg – Marquardt
algorithm..52/ The assumed distributional form is one
that is known to describe similar systems (e.g. for latex
particles the log-normal distribution described by two
parameters is frequently used).
Extensive reviews on the distributional forms that
have been used to describe the PSD in various sus-
pensions can be found in several sources..15,33,53/ Some
workers.1/ calculated turbidity for a Gaussian distri-
bution of spheres. However, most naturally occurring
14 PARTICLE SIZE ANALYSIS

populations are skewed and not symmetrical. The log- since the contribution of tails of very large particles to the
arithmic normal distribution.11,15,20,33/ has been used to theoretically calculated specific turbidity is eliminated.
described such populations. In this distribution ln D is Note that if Equation (22) can be directly used, then
normally distributed. The normalized PSD, f .D/ is given the polydispersity of a suspension with a log-normal
by Equation (21): distribution is given by Dw /DN D exp.3s2 / and the
  particle volume fraction is given by Equation (26):
1 .ln D ln Dg /2
f .D/ D p exp .21/
sD 2p 2s2 f D ND3g exp.4.5s2 / .26/

where ln Dg is the mean of ln D and Dg is both the median
and the geometric mean diameter; s is the standard
deviation of ln D and it is called the geometric mean
standard deviation. For small values of s (s < 0.14)
the frequency curve can be closely approximated by a
normal distribution..33/ The nth moment of the log-normal
distribution is given by Equation (22):.54/
 
n .ns/2
Jn D E.D / D exp n.ln Dg / C .22/
2
The number- (DN ), volume – surface- (D32 ), weight- (Dw )
and turbidity- (Dt ) average diameters can therefore be
calculated as (Equation 23):.15/
 1/3
J1 J3 J4 J6
DN D ; D32 D ; Dw D ; Dt D .23/
J0 J2 J3 J3
The calculation of the moments of the estimated PSD
from Equation (22) are correct only if the integration is
done from Dmin D 0 to Dmax D 1 or, in practice, if the
upper limit of the PSD, D0max , is such that when using
f .D/ from Equation (21), we have Equation (24):
Z D0max
f .D/ d.D/ D 1.0 .24/
0
Sometimes it may be known a priori (either from
another method such as EM, DLS or particle chromatog-
raphy, or by filtering of the suspension) that particle
sizes smaller than Dmin and/or larger than Dmax do not
exist. In these cases if we wish to estimate a log-normal
envelope we can do so. In the parameter estimation all
the integrations should be done between Dmin and Dmax .
A log-normal envelope, characterized by Dg and s, can
be estimated; however, the PSD should be normalized
before each iteration in the parameter estimation. Fur-
thermore, the calculation of the various moments should
be done using the explicit equation for the moments
(Equation 25):
Z Dmax
Jn D Dn f .D/ dD .25/
Dmin
and not Equation (22). The log-normal distribution
estimated with previous knowledge of Dmin and Dmax is
expected to be a more accurate estimate of the true PSD,
Some workers.4,5/ had named as log-normal the
distribution with the frequency function in Equation (27):
f 0 .D/ D Df .D/ .27/
The two distribution functions are related by Equa-
tion (28):.55 – 57/
f .D/ dD D f 0 .D/ d ln D .28/
Therefore, if f 0 .D/ is used, then Equation (4) should be
integrated with respect to ln D.29/ and not with respect to
D. This distribution described by f 0 .D/, has been called a
ZOLD.
When applying Equation (15b), f .D/ should be
expressed on a weight basis. A log-normal distribution on
a weight basis can be used..20,29,58/ If the number distri-
bution is log-normal, then the weight distribution is also
log-normal with the same geometric standard deviation s
(Equation 29):.54,59/
 
1 .ln D ln Dwm /2
F.D/ D p exp .29/
sD 2p 2s2
where F.D/ is the corresponding weight distribution for
f .D/ of Equation (21). Dwm is both the median and the
geometric mean diameter on a weight basis. Dwm and Dg
are related by Equation (30):
Dwm D Dg exp.3s2 / .30/
Heller et al..7,47,53/ used another type of distribution
that can be described by two parameters. However, the
maximum polydispersity for that distribution is DW /DN D
1.5..15/ Therefore, even though the distributional form
can describe positively skewed distributions, it cannot
successfully describe highly polydisperse systems.
4.5.2 No Assumptions on Shape of Particle Size
Distribution
If no distributional form is assumed for f .D/, then an
alternative is to solve for f .D/ at a finite number of
points..8,60 – 64/ In this approach, in the space of diameters
from Dmin to Dmax we define P points (i.e. P diameters Dj ,
j D 1 : P) and we try to estimate fj at the corresponding
diameter Dj . The number of P points must be less than

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DOI: 10.1002/9780470027318.a1517
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS 15

or equal to the number of specific turbidity or turbidity (Equation 38):

ratio measurements made.
Note that if the integrand of Equation (4) is discretized X
P 1
q.fO / D b2 .fO12 C fO22 / C .2fOj fOj 1 fOjC1 /2 .38/
at P 1 intervals, then turbidity at a given wavelength l0i
jD2
can be approximated by Equation (31):
with b × 1. The solution now is:
X
jDPDDmax
tl0i ³ fj gij .31/ f D .0T 0 C xH/ 1 0T t∗ .39/
jD1DDmin
where (Equation 40):
where fj ³ Nf .Dj / D Nj is the discretized PSD and gij
depend on the kernel and the quadrature equation 1 C b2 2 1 0 0 0 0 ...
used..27,61/ gij is evaluated at given Dj from the Mie 2 5 4 1 0 0 0 ...
theory. Note that for the simple case that the suspension 1 4 6 4 1 0 0 ...
is a mixture of P monodisperse suspensions with diam- HD 0 1 4 6 4 0 1 ...
eters D1 , D2 , . . . , DP , with relative number of particles ... ... ... ... ... ...
... ...
N1 , N2 . . . , NP , we have Equations (32) and (33): 0 0 0 0 1 2 4 5
0 0 0 0 0 1 C b21 2
p 2 .40/
gij D D K.l0i , Dj / .32/
4 j Note that in this method one has to choose the location
X
P of Dmin and Dmax and the number of intervals but also the
Nj D N .33/ value of x. The choice of these parameters was discussed
jD1 in detail by Eliçabe and Garcia-Rubio..61,62/
This technique was tested with simulations.61,62/ for
When turbidity is calculated for L wavelengths then
the estimation of unimodal and bimodal PSDs of
Equation (31) can be written as Equation (34): varying breadth and mean diameter. Satisfactory results
were reported.61/ for broad distributions with particle
t ³ 0f .34/
diameters in the micrometer range (distributions with
where t D [tl01 , tl02 , . . . , tl0L ]T , 0 D fgij g, f D [f1 , f2 , . . . , Dmax D 1.45 or 2.25 µm). For m D 1.2 the results were
fP ]T and T denotes transpose. not satisfactory for distributions covering sizes from 50 to
In the inverse problem, we have to estimate f from 325 nm, that is, a regime where a large number of latex
turbidity measurements t∗ (Equation 35): particle diameters are expected to be found.
More attempts to resolve the PSD with no assumptions
t∗ D 0f C e .35/ were reported later by other workers..63,64/ Finally, an
empirical method that relates turbidity measurements to
where e is the vector of errors (measurement errors particle size using latent variable methods has also been
plus errors due to discretization of the true distribution). reported..25/
Solving Equation (35) is a linear algebra problem..65/ The Gulari et al..8,60/ tried to estimate PSDs in polystyrene
least-squares solution is Equation (36): suspensions (m ³ 1.2), from a large number of turbidity
measurements at the wavelength range between 300 and
fls D .0T 0/ 1 0T t∗ .36/ 800 nm. In each case, the unknown PSD was assumed
to be the sum of 20 equally spaced delta functions
However, because the rank of 0 is incomplete, small (gij from Equation 32). The height (mass fraction) and
errors in t∗ result in large errors in the estimated position of each diameter was optimized using a non-
parameters. For this reason, regularization methods.65/ linear least-squares minimization procedure. During the
should be used. A penalty function is introduced to the analysis, the insignificant parameters are zeroed and the
original least-squares problem (Equation 37): parameter matrix collapses until convergence is reached.
The suspensions tested in that study were synthesized by
minfj0f̂ t∗ j2 C xq.f̂ /g .37/
f̂
mixing two or three monodisperse latexes, with particle
diameters approximately 1 µm separated from each other.
where x is a nonnegative parameter and j j indicates the The distributions were resolved on a weight basis. In each
modulus. q.f̂ / could be the sum of squares, or the first or distribution the weight fraction of the small particles
second differences, of the estimates. Eliçabe and Garcia- was significant. Users should be careful when using this
Rubio.61,62/ added another term to the sum of squares of approach (i) when a very small weight fraction of the
the second differences in order to force f1 and fp to zero small particles is present (see discussion on bimodal

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16
distributions, section 7.3) and (ii) for suspensions with
(m, a) values where y does not change significantly with
a. Readers should also keep in mind that the resolution
of the method depends on the location of the assumed
delta functions (number and width of D intervals) and
of course on the number of measurements (observations)
available.
In general, the estimation of f .D/ at a finite number
of points is expected to give satisfactory results only
for certain suspensions (i.e. corresponding to certain
m and a values). The results will be questionable in
(m, a) regimes where y does not change significantly
with a. Kourti and MacGregor.44/ emphasized that more
sophisticated deconvolution methods cannot overcome
the limitations that turbidity ratio and specific turbidity
have for particles in the (m, a) regimes where turbidity is
simply proportional to a moment of the PSD. Several
years later, Llosent et al..27/ confirmed this by trying
several deconvolution approaches to estimate the PSD
in the Rayleigh regime; only turbidity-average diameters
could be correctly estimated and not the PSD.
4.5.3 The Method of Moments
This method was presented.9,10/ as an alternative tech-
nique to solving for the PSD, but has some limitations for
the particular application it was used. In this approach the
term K.D/lm , np /nm /pD2 /4 in Equation (4) is approxi-
mated with a polynomial (Equation 41):
  X P
D np pD2
K , ³ Cil Di
lm nm 4 iD0
Turbidity can thus be expressed as a sum of P moments
of the unknown PSD. Using P turbidity ratios (P C 1
turbidity measurements) one can estimate the P moments
(J0 of the normalized distribution is unity). The PSD is
then represented analytically using a set of its moments,
by modifying a gamma distribution which serves as a basis.
The method was applied for particle size determination in
poly(vinyl acetate) latexes..9,10/ First, the Cil coefficients
at each wavelength were estimated from Equation (41)
by calculating the value of Kscat pD2 /4 exactly from the
Mie theory for a set of 20 diameters (between 0.04 and
0.8 µm) and setting the value of P equal to 6. Six Cil
were estimated for each wavelength. The procedure was
repeated for seven wavelengths (350 – 800 nm).
As discussed in a critical review,.15/ the expansion of the
scattering coefficient to a power series of a (or for constant
lm , to a power series of D) is an approximation applicable
for small a and ma values. In these cases the coefficients of
ai (or Di ) are known functions of the optical constants.37/
(i.e. no estimation of Cil is necessary). The a values
corresponding to the diameters and wavelengths reported
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DOI: 10.1002/9780470027318.a1517
PARTICLE SIZE ANALYSIS
in the particular application.9,10/ were very large (a as
large as 9.5). For larger m and a values the approximating
equations for the calculation of Kscat include more
involved functions.37/ of a [or r D 2a.m 1/] than the
simple power series expansion attempted in the method
of moments. As discussed earlier, the term Kscat D2 can
be set proportional to Dy for larger values of a, and the
value of y changes as a function of the particle size. For
poly(vinyl acetate) latexes in particular, and for a very
wide range of a values, the value of y is very close to
4.0. For most of the diameters used for the calculation
of the above term in that study.9,10/ at each wavelength,
the a values were such that y was close to 4.0. It is clear
that a reasonable value from the parameter estimation
is expected only for C4l , since all the other coefficients
are practically equal to zero. From the results reported
by Kiparissides,.9/ only C4l seems to have a consistent
value for all the wavelengths; the estimated values of
all the other coefficients change, both in sign and value,
randomly..15/ It should be clear that with meaningless
estimates of the Cil coefficients the correct estimation of
the moments of the PSD is impossible.
5 ESTIMATION OF AVERAGE DIAMETERS
Several workers have tried to use turbidimetry to estimate
only an average of the PSD of a polydisperse system. To
do this they treat the system as monodisperse. That is,
for specific turbidity, instead of using Equation (15a) they
.41/ use Equation (12) and estimate a single, average diameter
which is termed an ‘‘apparent diameter’’ (Equation 42):
tl0 3 K.aav , m/
D .42/
f 2 Dav
where aav D pDav /lm . Dav is the apparent diameter that
always corresponds to the Dy3 average of the PSD.
The concept of the ‘‘apparent’’ diameter was intro-
duced and theoretically explained in very careful work
by Meehan and Beattie..4,5/ They commented that the
apparent diameter obtained by treating a polydisperse
system as monodisperse corresponds to an average of
the unknown PSD. They also concluded that different
kinds of averages are yielded by different light scattering
methods, and that the kind of average obtained by a light
scattering method depends on the value of m of the sus-
pension, the type of the PSD and the actual size of the
particles in the suspension. Their comments have been
corroborated by numerous reports.3,4,7,15,16,29,66/ where it
is either discussed and/or shown experimentally that the
type of average obtained from the apparent diameter
depends on the turbidimetric technique used and the m
and a values of the suspension.
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
It has been suggested.7/ that the ratio of the apparent
diameters estimated at two wavelengths can provide
a rough idea of the polydispersity of the system.
However, this is not always true. It has already been
shown that, sometimes, especially for small m values
(m ³ 1.1), the apparent diameters corresponding to very
broad distributions or to bimodal distributions do not
change significantly with the wavelength, leaving the
impression that the system is monodisperse. Note that for
monodisperse systems, the apparent diameters obtained
from two different turbidimetric methods (i.e. specific
turbidity, turbidity ratio) should be numerically very close
to each other (i.e. equal, within experimental error).
Specific turbidity has been the only turbidimetric
method used in the literature for the determination
of averages of the PSD. This is because, as already
discussed, it is the only turbidimetric method that can
provide estimates of meaningful averages of the PSD
(Dy3 averages) at some well-defined (m, a) regimes.
The following averages may be obtained from specific
turbidity: (i) the turbidity-average for very small particles
(a < 0.5) and any value of m, (ii) the volume – surface
average for very large particles and any m value and
(iii) weight-average for a combination of (m, a) values
and m < 1.2 which can be identified very easily for the
system under investigation. In this section we discuss
the use of specific turbidity for the estimation of
meaningful average diameters. A critical discussion of
several applications reported in the literature is presented,
so that the readers can identify with situations closer to
their needs.
5.1 Turbidity-average Diameters
These averages can be obtained from specific turbidity
measurements, for suspensions with any value of m,
provided that all the particles in the suspension are small
compared with the wavelength at which the turbidity
measurements are taken (Rayleigh regime).
A practical application, where the growth of sil-
ver bromide grains is monitored on-line by following
turbidity-average diameters, was reported by Haseler
and Parkin.6/ for an Ostwald ripening process. They were
careful to choose long wavelengths [infrared (IR) regime,
2.22 µm] so that the Rayleigh scattering theory could be
applied even for the largest particles in their system..15/
Note that in the Rayleigh regime, if two particle
suspensions have the same value of m, the ratio of their
specific turbidities measured at the same wavelength (see
Equation 16) gives the ratio of their turbidity-average
diameters, independent of the value of m (Equation 43):
 
t1 /f1 Dt1 3
D .43/
t2 /f2 Dt2
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17
This characteristic can be exploited to provide a fast
and inexpensive tool to monitor particle growth in a
suspension where the value of m is not accurately known.
By simply measuring specific turbidity (turbidity and
solids fraction) at each time interval, the relative increase
in the turbidity-average diameter as a function of time
can be recorded. From a measurement of the diameter or
the PSD with another technique (which is independent
of m) at the end of the process, we can back-calculate the
turbidity-average diameter at each instant in time.
A report.28/ that a correct turbidity-average can be
obtained for a values as large as 4.74 from specific
turbidity measurements should be treated with caution.
These observations were rather coincidental with the
polydispersities of the systems investigated, as explained
in detail elsewhere..15/ In the same work.28/ the term
‘‘weight’’ average was used for what in fact is the
‘‘turbidity’’ average, as can be deduced from the definition
in the original publication,.67/ where EM results for the
latex samples used in the later study.28/ were presented.
5.2 Volume – Surface-average Diameters
Volume – surface-average diameters have been estimated
in the literature from specific turbidity measurements
of suspended particles that were very large compared
with the wavelength (Kscat ³ 2). It should be noted that,
although the value of the oscillating Kscat stays very close
to 2.0 for large a values, the error by assuming it to be
equal to 2.0 is small only for very large a values (i.e.
the error is within 3% for a > 800 and within 1% for
a > 2000) (see Table 2). For a values around 200 – 260,
where some of the cases reported in the literature are, the
error of assuming Kscat D 2.0, depending on the spread of
the distribution, could be as large as 6% for m D 1.2 and
9% for m D 1.1 (at these a values Kscat still depends on m).
Therefore, depending on the range of a values covered by
the true distribution, the estimated D32 average diameter
could be within 10% error of the true value.
Bagchi and Vold.66/ showed experimentally that for
very large particles, the specific turbidity varied linearly
with the inverse of the volume – surface-average diameter
(1/D32 ). However, a linearity observed with respect to the
inverse of other averages was coincidental and attributed
to the fact that the degrees of polydispersity of the latexes
investigated were very similar..15/ Kubota et al..68/ dis-
cussed this coincidental linearity and presented more
experimental results from suspensions of various poly-
dispersities, verifying that only the specific turbidity vs
(1/D32 ) curves are linear, as was theoretically expected.
Kourti.15/ showed that a claim by Dobbins.69/ and
Dobbins and Jizmagian.70/ that the volume – surface-
average diameter can be obtained from one specific
turbidity measurement in any particle size regime cannot
18
be supported. Their observations, that ‘‘the specific
turbidity is primarily dependent on the D32 diameter and
only weakly dependent on the type of the distribution’’,
were shown to be coincidental with the types of
distributions that they used for their investigation. These
distributions had also their weight averages close to each
other and all of them included particle sizes in the same
range. Similar claims by Haseler.19/ were also discussed
in Kourti..15/ It was shown that in the examples reported
by Haseler,.19/ the estimated D32 was close to the true
value because the location of the whole distribution was
correctly estimated, and not because specific turbidity is
always expected to give a correct D32 as claimed..69,70/
It has been suggested.71/ that the specific turbidity of a
polydisperse system can be expressed as Equation (44):
tl 0 3 K.aav , m/
D .44/
f 2 D32
where (Equation 45):
Z 1 Z eter selected this way in the polydisperse systems he stud-
1
K.aav , m/ D2 f .D/ d.D/ D D2 K.aav , m/f .D/ d.D/
0 0
.45/
where aav corresponds to an average diameter Dav . It was
suggested that the two parameters aav and D32 can be used
to interpret turbidity data over a wavelength range. The
D32 diameter will correspond to the true PSD whereas aav
will correspond to the average diameter ‘‘seen’’ by the
measurements ‘‘averaged over the wavelength range’’.
However, by definition, the only correct form for the
calculation of an average diameter from specific turbidity
measurements is that of Equation (42). Equation (44) is
valid only for very large diameters, where K.aav , m/ D 2,
independent of particle size. In any other case if we
try to estimate the two parameters (aav and D32 ) in
Equation (44), ‘‘over a range of wavelengths’’, these
estimates will be highly correlated. Their numerical
values will depend on the wavelength range used and
the D32 estimate will not, in general, correspond to the
volume – surface-average of the true PSD.
5.3 Weight-average Diameters
For suspensions with small values of m (usually m < 1.15)
and particle sizes corresponding to certain a values
(i.e. for m D 1.05, 3 < a < 14; for m D 1.15, 3 < a < 6),
the apparent diameters obtained from specific turbidity
measurements are numerically close to the weight-
average diameter, Dw . This average is essentially the only
correct estimate of the particle size that can be obtained
for polydisperse systems in these (m, a) regimes. If users
know the value of m of their suspensions they can devise
simple ways to obtain this average. For example, it has
been observed.15/ that the mean value of the apparent
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DOI: 10.1002/9780470027318.a1517
PARTICLE SIZE ANALYSIS
diameters from specific turbidities at 600 and 400 nm,
obtained for a variety of polydisperse poly(vinyl acetate)
latexes (m ³ 1.1) with different distributions (unimodal,
multimodal) in the submicrometer regime, is numerically
very close to the true weight average of the distribution.
That means that for m D 1.1 the weight average from
submicrometer particle suspensions can be estimated very
simply, from two specific turbidity measurements at 400
and 600 nm. Similar heuristic rules could be derived for
other suspensions with small m values.
Cheesman,.72/ for example, suggested a technique in
which the specific turbidity is measured at several wave-
lengths and the apparent diameter (Dav ) is estimated
for each wavelength. Then the corresponding aav values
are calculated (aav D pDav /lm ) at each wavelength. The
apparent diameter that gives aav near the a value of the
first point of inflection of the Kscat vs a curve is chosen to be
the weight-average diameter (for m D 1.1, this a value was
chosen 2.7 and for m D 1.2, it was 2.2). The apparent diam-
ied was within 4% of the true weight-average diameter.
The observations of Cheesman can be explained
theoretically. At the a value at the inflection point (see
peaks of the first ripple of the y vs a curve in Figure 2)
the value of y, for almost any value of m, is close to 4.5. If
the weight-average diameter corresponds to this a value,
then the a values for the individual particle diameters of
the distribution are located around it and the value of y
varies between 4 and 4.5. Hence in this technique, the
wavelength is chosen such that the entire distribution is
brought to an a regime where y is close to 4.0 and the
apparent diameter is the weight-average diameter.
As has been pointed out,.44/ the fact that the weight-
average diameter of suspensions can be correctly esti-
mated even though the PSD determination is impossible
is a very useful property of the specific turbidity. It
was suggested.44/ that this property could be utilized
for practical applications, in situations where following
an average diameter is sufficient to monitor the progress
of a process. An example would be on-line particle size
measurements to monitor the progress of polymerization
reactions. Gossen.23,46/ and Gossen and MacGregor.24/
used this suggestion and applied specific turbidity on-
line to monitor weight-average diameters of poly(vinyl
acetate) particles during latex production. The results
reported.23,24,46,73/ show good agreement between the
weight-average diameters obtained by turbidimetry and
those obtained by on-line DLS.
5.4 Other Applications of Turbidimetry
The dependence of turbidity on particle size can also be
exploited in other ways than its conventional use in par-
ticle size determination. Kourti.15/ suggested that simple
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
turbidity measurements at one wavelength can be used
to monitor polymerization processes in order to detect
the onset of several events, as for example the begin-
ning of the reaction in latex systems (i.e. the end of
induction period) or the onset of agglomeration. By fol-
lowing turbidity measurements at one wavelength during
the emulsion polymerization of vinyl acetate in a con-
tinuous laboratory-scale reactor, Kiparissides et al..9,10/
could detect whether the reactor was operating under
steady-state conditions or under oscillations. Turbidity
measurements at 400 nm were used by Kourti.15/ to fol-
low qualitatively the effect of several variables on particle
size during vinyl acetate emulsion polymerizations. Tur-
bidity measurements at one or more wavelengths (and
reduced to the same degree of dilution) can also be used
for routine operations to monitor the progress of the
reaction and detect any deviations from a known desir-
able path. Finally, Crawely et al..74/ discussed the use of
turbidity measurements at several wavelengths in studies
of crystallization, agglomeration and attrition.
6 PROCEDURAL DETAILS
6.1 Instrumentation and Forward Scattering
The turbidity of a suspension can be measured very
easily in a laboratory or a plant environment. Very often
spectrophotometers in the UV/VIS range are utilized for
this purpose. A dilute suspension is inserted in the cell of
the spectrophotometer. We have (Equation 46):
 
A 1 100
tl0 D 2.303 D ln .46/
l l T
where A is the absorbance reading, T is the percent
transmittance at wavelength l0 and l is the optical path
(i.e. width of cell). There are also reported applications
where turbidity measurements at longer wavelengths,
in NIR regime,.6,16,17,19,26/ were used for particle size
determination. Sometimes, certain modifications may
be necessary.19/ in the instruments used to measure
turbidity so that forward scattering is rejected and
theoretical calculations of turbidity can be legitimately
compared with the measured values. This is because
for the determination of particle size from turbidity
measurements, it is assumed that the detector measures
the attenuation of the beam of the source light. However,
all the spectrophotometers measure the attenuated light
from the source plus a certain amount of light scattered at
small angles. Forward scattering will add error to the value
of the true turbidity. Reports in the literature.34/ mention
that the larger the particles the greater is the possible
discrepancy between the true and the measured (or
apparent) turbidity, but for small particles and particles
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DOI: 10.1002/9780470027318.a1517
19
comparable to the wavelength the difference between the
true and apparent turbidity should be minute. Bohren
and Huffman.75/ suggested that although conventional
spectrophotometers are not usually designed to reject
scattered light at small angles, such instruments may be
adequate for scattering measurements if the particles
are not too large. For monodisperse polystyrene latexes
(m D 1.2) with diameters of 109, 312 and 1050 nm and
turbidity measurements at wavelengths between 300 and
600 nm, they used a conventional spectrophotometer,
suggesting that the forward scattering should not be
significant. Walstra.76/ suggested that sometimes errors
attributed to forward scattering.18/ were in fact due to
extremely high optical densities that the investigators had
included in their results.
The brief analysis that follows illustrates the conse-
quences of the error added to the value of the true
turbidity due to forward scattering. The effect that an
error in the measured turbidity value has on the estimated
particle size depends on the turbidimetric technique used
and the (m, a) values of the system and it cannot be
generalized. The turbidity ratio utilizes two turbidity
measurements at different wavelengths, therefore the
error due to forward scattering is introduced twice in
this method, but only once in the specific turbidity. In
Figure 5 we plot.15/ as a function of a, for two different m
values, the percentage error in the estimated diameter in
monodisperse suspensions for a 3% error in the measured
specific turbidity. Note that the effect changes with the
(m, a) combination. For m D 1.2 and a values near the
specific turbidity maximum (which for m D 1.2 occurs at
a D 7.33), the error becomes very large. However, for a
14
12
Error in diameter (%)
10
8
m =1.2
6
4
2 m =1.1
0 1 2 3 4 5 6 7
α = πD/λm
Figure 5 Percentage error in the estimated particle diameter of
monodisperse suspensions plotted as a function of a for m D 1.1
and 1.2 when there is a 3% error in the specific turbidity
measurements.
20
values less than 4.0 the error in the diameter is the same
for m D 1.1 and 1.2, and it is approximately 4.0%. For
water medium (nm ³ 1.33), a value of a D 4 corresponds
to D/l0 ³ 1 (a D 4 D pDnm /l0 ), which means that for
particles smaller and comparable to the wavelength the
error is small. Therefore, if the error due to forward
scattering introduces a 3 – 4% error in specific turbidity,
then for particles comparable to l0 the effect on particle
size should not be significant, and this would explain the
observations reported by various workers. A final note on
Figure 5: it demonstrates that a 3% error in the specific
turbidity measurements may cause a very large error in
the estimated size for a values near the peaks or the
valleys of the Kscat vs a curve. This is due to the light
scattering behavior and has nothing to do with the source
of the error (i.e. this 3% could be due to either a wrong
solids fraction measurement or to forward scattering, and
would have the same effect on the estimated size).
Errors in turbidity measurements due to forward
scattering are discussed in a number of references,
where suggestions are given for the modification of
the spectrophotometers..6,18,20,30,49,76 – 78/ Also, several
empirical approaches have been suggested to account for
the difference between true and apparent turbidity..20,66/
For example, a correction factor (R) can be estimated.20/
for several suspensions with known particle diameters; R
is equal to the ratio of the measured to the theoretically
expected turbidity. This factor can then be used for
unknown suspensions, but with (m, a) values in the same
range for which it was estimated. In another approach,
a calibration was used.66/ to relate apparent specific
turbidity with the true particle size for large latex particles
where forward scattering is significant.
Users can assess the accuracy of the turbidity mea-
surements of their spectrophotometers by comparing the
experimental values with theoretically calculated values
for monodisperse suspensions with known diameters, cov-
ering the range of (m, a) values that they plan to analyze.
Before proceeding to any modifications one should judge
whether the accuracy is satisfactory for the purpose of the
study to be carried out using the turbidimetric results. For
example, if the purpose of the study is to use the method as
a reproducible and inexpensive way to monitor particle
size during a reaction, then the accuracy of the spec-
trophotometer with no modifications may be satisfactory,
and similarly if the objective is to detect the qualitative
effect of various parameters (emulsifier, impurities) on
the particle size of the latex. For other applications that
require more accurate determinations of larger particles,
one may consider modifications of the spectrophotometer
and the use of a correction equation.76/ that accounts for
the angle of acceptance of the detector for the calculation
of the scattering coefficient. Kourti.15/ used two spec-
trophotometers without modifications for diameters up to
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PARTICLE SIZE ANALYSIS
400 nm and suspensions with m D 1.1 and 1.2: a Hewlett-
Packard Model 8450A at wavelengths of 350 – 700 nm
and a bandwidth of 2 nm and a Bausch and Lomb (now
Spectronic Instruments) Spectronic 20 at wavelengths of
380 – 580 nm and a bandwidth of 20 nm. The accuracy of
the method was tested by estimating the size of monodis-
perse suspensions with known diameters and also by
comparing the size estimated by turbidimetry with that
measured by EM and DLS. For numerous unknown sam-
ples, the diameters estimated by turbidimetry were in
very good agreement with those measured by DLS and
EM. Forward scattering did not introduce any problems.
Gossen and MacGregor.24/ used for on-line measure-
ments in a pilot-plant environment a Bausch and Lomb
single-beam Spectronic 20 equipped with a cylindrical
Pyrex flow-through cell with a 1 cm pathlength, without
any modifications for forward scattering. The incident
beam had a bandwidth of 20 nm and the wavelength was
400 nm. Weight-average diameters up to 200 nm obtained
during latex production were in very good agreement with
weight-average diameters obtained by on-line DLS,.73/
and a change in Dw of the order of 10 nm was detectable.
The accuracy of the results was considered satisfactory
for their objective to monitor changes in the particle size
due to process disturbances.
6.2 Refractive Indices of the Particles and the Medium
Turbidity is a very strong function of the optical properties
of the particle suspension, that is, the ratio of the refractive
index of the particles to that of the medium, m, and the
refractive index of the medium, nm . The latter is used for
the calculation of lm and consequently the calculation of
a. For the correct determination of the particle size the
values of these properties must be accurately known. The
values of the refractive indices for different materials can
be found in relevant handbooks..79/ Refractive indices
can also be directly measured, or estimated using a
combination of techniques as described below.
Llosent et al..27/ used a Bellingham Abbé 60 refrac-
tometer to measure the refractive index of latex particles,
np , required to calculate m for their work. The refractive
index of the polymer film was measured at several wave-
lengths. They then used the measured values to estimate
the constants for a Cauchy.80/ equation that expresses np
as a function of the wavelength l0i (Equation 47):
B C
np .l0i / D A C 2
C 4 .47/
l0i l0i
This equation was subsequently used to calculate np at
other wavelengths.
If the value of the refractive index of the medium nm
is known but np and therefore m are not known, it may
be possible to estimate m directly using a combination of
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
techniques. Kourti.15/ suggested that, since turbidimetry
is very sensitive to the value of m, it is probably the best
method to ‘‘estimate’’ the values of m as a function of
wavelength for a specific suspension. Suppose we wish to
estimate the value of m for suspensions of polybutadiene
particles in water. Using a monodisperse suspension of
polybutadiene particles in water with known diameters
(estimated by EM or DLS), the scattering coefficient and
therefore m can be calculated from the specific turbidity
measurements at one wavelength (provided nm is known).
By measuring specific turbidities at more wavelengths one
can estimate the dependence of m on wavelength. The
advantage of this approach is that the value of m for
a particular suspension is measured in the environment
in which it will be used. This may be more meaningful
than, say, using a latex film to measure the refractive
index of particles and dividing by the refractive index of
medium. Once m has been measured it can be used for
suspensions of the same material (i.e. polybutadiene in
this example), but of course for any particle sizes or PSD.
DLS is an excellent method for this purpose because
the particle sizes can be measured in suspension and
for monodisperse particles DLS is independent of the
refractive index. Another method to determine optical
constants would be angular light scattering.
Sometimes the medium may not be a clear substance
but may have additives. In latex samples, for example,
emulsifier may be added to the water medium, or
monomer may be dissolved in it if the samples are
withdrawn at low monomer conversions. In these cases
the refractive index of clear water cannot be used. The
refractive index of the medium for a given concentration
of water-soluble monomer (or other substance present
in it) can be read directly from a calibration curve
of refractive index as a function of the concentration
of monomer in water. Such calibration curves can be
easily constructed from refractive index – concentration
increments obtained from differential refractometers. In
high dilutions the effect of monomer on the refractive
index of the medium is usually negligible.
6.2.1 Inhomogeneous Particles/Latex Particle
Applications
Sometimes the particles in the suspension may not
be homogeneous. Examples from latex systems are
carboxylated particles that swell in water, particles
swollen with monomer in latex samples withdrawn at
low conversions and particles produced by core and
shell polymerizations. There are several issues related to
determining the optical properties of such particles and
research is active on light scattering by inhomogeneous
particles..81 – 83/
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21
For monomer swollen particles, or particles produced
by core and shell polymerizations, one approach is to
calculate the value of m by treating the particles as coated
spheres. For coated spheres the refractive index ratio can
be calculated as m D m1 v1 C m2 v2 , where m1 is the ratio
of the refractive index of the core to the medium and
v1 is the volume fraction of the core; m2 and v2 are the
corresponding values for the coating. (v1 C v2 D 1.0). This
approximation is not very accurate for thin coatings. In
the above approach, for monomer swollen polymers, the
volume fractions of the monomer and polymer are treated
as core and coating respectively. It should be emphasized
that this is an approximation, and the true morphology
of monomer swollen particles may be different than a
core and coating approximation. Bohren and Hoffman.75/
also presented an algorithm to calculate the scattering
functions of coated spheres (consisted of homogeneous
core and homogeneous coating of uniform thickness) and
they discuss the limitations of this algorithm, in general,
for anisotropic spheres. For very accurate calculations,
these approximations to estimating the value of m for
core and shell particles must be checked experimentally.
This can be done as mentioned earlier by using another
method (i.e. DLS) to estimate the particle size and then
using turbidimetry to estimate the value of m for particles
with known polymer composition. The above calculations
should be performed on monodisperse suspensions. A
calibration curve could then be constructed to give the
value of m as a function of the polymer composition in
the particle. If DLS is used to verify the particle size of
monomer swollen particles, the same degree of dilution
must be used to make sure that the same particle size is
measured (because monomer is dissolved in water and
extracted from the particle with high dilutions).
For monomer swollen particles and carboxylated
particles that swell in water, both the density and the
refractive index depend on the degree of swelling and
appropriate corrections should be made. In monomer
swollen particles, the amount of monomer associated
with the particles (and therefore the refractive index of
the particles and the medium) depends on the conversion,
the solubility of monomer and the degree of dilution of
the original sample.
Latex produced by multicomponent polymerization is
also a case where the calculation of the refractive index of
the particles may present difficulties. The refractive index
depends on the polymer composition and may change
during the reaction due to composition drift. Therefore,
calibration may be needed to relate the refractive index
of the particles to their composition (by taking into
account the conversion of the monomers at the time of
sampling). When monitoring particle growth with on-line
turbidimetry during multicomponent polymerizations,
on-line gas chromatography can be utilized to provide
22
information on the composition of the particles. The
refractive index can then be calculated from the particle
composition utilizing some type of calibration. On-line
densitometry combined with on-line gas chromatography
can provide information on the particle volume fraction,
f. More details on this topic can be found in Kourti..15/
6.3 The Choice of the Wavelengths
As discussed earlier, the successful determination of the
PSD or of an average particle size of a suspension
depends on the m and a values of the suspension and
the turbidimetric technique used. The refractive index of
the medium and therefore the value of m of a suspension
can be altered by adding other substances to the medium
[e.g. glycerol.5,16/ ] provided that these substances do not
affect the particle size. The range of a values covered
by the PSD can also be manipulated by changing the
wavelengths at which the turbidity measurements are
taken. As a general rule, wavelengths widely separated
from each other should be used when the estimation
of the full PSD is required. In this way the range of a
values covered by the PSD changes significantly from one
wavelength to another (the y exponent changes) and the
probability of the turbidity being proportional to the same
moment of the PSD at both wavelengths is reduced. It
should be noted, however, that when wavelengths widely
separated from each other are used, the value of m at each
wavelength must be accurately known; using a constant
m may result in false estimates..15/ If only one value for
m, estimated at, say, l00 , is available and must be kept
constant for all the wavelengths, then wavelengths on
either side of l00 (i.e. both shorter and longer) and as close
to l00 as possible must be used.
To keep wavelengths widely separated, several workers
chose one wavelength in the UV/VIS range and one in
the IR region. The first (1.7 µm).16,17/ and the second
(2.22 µm).19/ IR transmission windows for water have
been the choices for long wavelengths. Most workers
Turbidity (cm−1)
have avoided wavelengths below 400 nm where some
particles may absorb light and wavelengths where the
medium absorbs light.
Eliçabe and Garcia-Rubio.62/ used wavelengths in
regimes where particles absorb to resolve the PSD for
a computer-simulated polystyrene latex example, where
clear water was assumed to be the medium. The resolution
of the PSD was improved. However, in practical situations
for latex particle size analysis, it is preferable to avoid
working at short wavelengths where absorption occurs
(e.g. the styrene ring absorbs at 269.5 nm). In latex
samples withdrawn at low monomer conversions, residual
monomer which absorbs light at certain short wavelengths
may be present in the particles and extracted owing to
dilution in the medium. As a consequence, if particle size
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DOI: 10.1002/9780470027318.a1517
PARTICLE SIZE ANALYSIS
determination is attempted at these short wavelengths
without accounting for the distribution of the absorbing
monomer between the medium and the particles, the
results may be questionable. However, calculating the
monomer distribution is tedious and requires a knowledge
of conversion, partition coefficient of the monomer
between the water and the polymer phase and the degree
of dilution. It is clear that using short wavelengths is
not practical if the objective is to follow particle growth
during the reaction.
6.4 Preparation of Samples
In particle size determination by light scattering methods,
it is usually assumed that the scattering by an array
of particles is incoherent (the particles are randomly
positioned in space to avoid mutual polarization) so
that the scattering functions corresponding to an isolated
particle may be used, and also that there is no significant
multiple scattering. These conditions are practically
met.33/ when turbidity measurements are taken with
sufficiently dilute suspensions. In practice this is achieved
by diluting the suspension and working at a concentration
range where the turbidity, at the shortest wavelength to
be used, varies linearly with the particle concentration.
Figure 6 shows how turbidity changes with concentration.
The shorter the wavelength, the lower is the concentration
of suspended solids required to avoid multiple scattering.
The fact that the sample needs to be diluted may
have an effect on the particle size in certain cases. For
example, in latex samples withdrawn at low conversion,
polymer particles swollen with monomer may change size
by changing the degree of dilution, and this should be
taken into account. Also, for latex particles stabilized
3.0
2.5 460 nm
2.0
360 nm
500 nm
1.5
1.0
560 nm
0.5
0.0
0 1 2 3 4 5 6
Solids concentration (mg mL−1)
Figure 6 Turbidity plotted against solids concentration in the
sample: linearity check.
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
by ionic or nonionic emulsifiers or other groups, the
user must be careful to dilute the sample without risking
destabilization. Some emulsifier (the same as the one used
in the latex production) must be added to the diluting
medium to prevent destabilization. Samples prepared in
this way remained stable for a long time;.15/ turbidity
measurements taken 3 years after the samples were
prepared showed no difference within experimental error
with measurements taken for those samples when they
were freshly prepared. Kourti.15/ discussed in detail other
considerations for latex particle size determination, for
both off-line and on-line applications.
6.5 Particle Volume Fraction for Specific Turbidity
Particle volume fraction is measured by gravimetric
analysis. The weight of the dry solids per cubic centimeter
(c, g cm 3 ) is measured and converted to volume fraction
using the density of the particles (r, g cm 3 ); f D c/r.
Particle volume fraction is usually measured on undiluted
samples. The particle volume fraction corresponding to
the diluted sample on which the turbidity measurement
is taken is calculated by taking into account the degree of
dilution. Therefore, the degree of dilution must be known
very accurately. Particle volume fraction for on-line
applications can be measured by densitometry..21,23,24/
7 EFFECT OF ERRORS ON THE ESTIMATED
PARTICLE SIZE AND PARTICLE SIZE
DISTRIBUTION
The determination of the particle size or PSD of a
suspension using turbidimetry involves measurements
and assumptions. Errors in the measurements and
uncertainty in the assumptions will have a minor or a
major effect on the estimated size. The sources of errors
can be grouped as follows:
ž Experimental errors in measurements: these involve
random measurement errors and errors due to for-
ward scattering (bias) in the turbidity measurements.
For specific turbidity methods there are also errors in
the calculation of the solids volume fraction due to
dilution, error in gravimetric analysis and uncertainty
in the value of density of the particles.
ž Uncertainty in the m values and the dependence
of the m on the wavelength: m is required for the
theoretical calculation of the scattering functions.
ž For polydisperse samples, error in the assumptions
related to the PSD: either the form of the PSD has
to be assumed or the number of discrete points, their
range and the value of the smoothing parameters.
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23
The sensitivity of the estimated particle size to such
errors has been investigated by several workers. The
results are briefly summarized in the following sections.
7.1 Error in Measurements
The effect of measurement errors on the estimated
particle size depends on the technique used (specific
turbidity or turbidity ratio) and on the (m, a) values of
the system and cannot be generalized, as illustrated in the
following. Kourti.15/ reported an average error of 0.4% in
the repeatability of transmittance readings. Such an error
is translated to an average 2% error in specific turbidity.
For the (m, a) values used, with m D 1.1 and a < 3.5
this error would translate to a maximum error of 2% in
the particle diameter for monodisperse suspensions. If a
different technique, say turbidity ratio, was used for the
same (m, a) regime, then from a small bias of C0.5%
on the transmittance readings at both wavelengths (the
same bias would be the case due to forward scattering)
the error in the particle size for monodisperse particles
can be 2 – 3%. For the same size regime, if instead of the
bias the error was random (š0.5%), then the error in the
particle size can be as large as 9%. Because the effects
of turbidity measurements on particle size cannot be
generalized over (m, a) values, a good practice for users
would be to construct a curve such as that in Figure 5
for the m value of the suspensions with which they plan
to work. The effect of a certain percent error in specific
turbidity (or turbidity ratio) on the estimated particle
diameter can be calculated with simulations for a wide a
range. Then, by changing the value of a used (by changing
the wavelength), they can move the system to a regime
where measurement errors would not affect the particle
size significantly.
The effect of measurement errors on the estimated
PSD in polydisperse systems was the subject of a detailed
study.15,32/ and it has been shown to depend on the
technique used (specific turbidity or turbidity ratio) and
on the (m, a) values of the suspension. As discussed in
section 4, the estimation of full PSD is impossible within
experimental error in some (m, a) regimes. However, in
these regimes, if specific turbidity is used, an average
diameter can be correctly estimated and the effect of
measurement error on this average diameter is not large.
In regimes where only the weight-average diameter can be
estimated, for a random error of š3% in specific turbidity
at three wavelengths, the maximum error was for a weight
average 5%. As a comparison the maximum error for the
number average in these regimes was 40%..15/
7.2 Error in the Value of the Refractive Index Ratio, m
Kourti.15/ studied the effect that errors in the value of
m have on the estimated PSD. It was concluded that
24
turbidimetry is sensitive to such errors but the magnitude
of the effect on the estimated PSD depends on the
(m, a) values of the suspension. In certain (m, a) regimes,
the effect that the error in m has on the estimated
parameters of the PSD is comparable to the effect of
turbidity measurement errors, whereas in others it is
much higher. In regimes where the y exponent does not
change significantly with the particle size, the errors in the
value of m had a larger effect on the estimated size than
turbidity measurement errors. Therefore, observations
reported in the literature on the magnitude of this
effect cannot be generalized for any (m, a) values. For
example, the observation of Wallach and Heller.7/ that
‘‘the error of the disregard of the dispersion of m is
less that experimental error’’ was simply a coincidence
of the (m, a) values of the system with which they were
working. Whenever there is uncertainty in the value
of m of the suspension to be analyzed, a sensitivity
analysis should accompany the results, to indicate the
degree of confidence. Alternatively, the results should be
corroborated with another method.
Sometimes, the dependence of the refractive index of
the medium, nm on the wavelength is known, but only one
measurement for the refractive index of the particles, np ,
at one wavelength l00 is available. If this is the case, it is
recommended that a constant m (calculated at l00 ) is used
at all the wavelengths, and not a variable m calculated
with constant np and wavelength-dependent nm . For
water medium, a wavelength-dependent nm decreases
with longer wavelengths and using constant np will force
m to increase with longer wavelengths (when it is expected
to decrease); this in turn means significant errors when
analyzing real data since the estimated particle size moves
in the opposite direction to the true value. Finally, when
a constant value of m is used, the error is smaller if the
turbidity measurements are taken at wavelengths both
shorter and longer and as close as possible to the one at
which m was measured.
In all cases, however, if the wavelength-dependent nm
is known, it should be used to calculate the value of lm
and therefore a for the scattering coefficient calculation.
7.3 Error in the Assumed Distributional Form
The main criticism in the literature about approaches
that attempt to recover the PSD by assuming a type of
the distribution (i.e. log-normal, Gaussian, etc.) is that
the assumed distribution may be very different from
the true one. When a distributional form is assumed, a
constraint (i.e. the shape of the distribution) is forced
upon the solution. The expected result is a PSD with the
assumed shape that will envelope the true distribution;
the details of the true PSD are not expected to be
resolved. The estimation of the location of the main
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DOI: 10.1002/9780470027318.a1517
PARTICLE SIZE ANALYSIS
body of the distribution is therefore the most satisfactory
result expected in this case.
The error introduced in the estimated PSD when
the assumed distributional form is different from the
true one has been studied either experimentally or with
simulated cases by several workers. Wallach and Heller.7/
tried to estimate the PSD of three suspensions with
positively skewed, negatively skewed and symmetrical
distributions, using the turbidity ratio method and
assuming a distributional form which can describe only
positively skewed distributions. In the cases of negatively
skewed and symmetrical PSDs, the estimates of the
parameters chosen to describe the distribution had a
significant error; however, Kourti.15/ reported that a
careful examination of those results showed that the
estimated PSD enveloped (i.e. recovered correctly)
the main body of the true distribution. This behavior
was expected since the polydispersities of the three
synthesized distributions and of the assumed distribution
were very small; no distributions with very long tails to
small or large particles were studied.
In an extensive simulation study, Kourti.15/ investigated
the error introduced in the estimated PSD when the shape
is assumed to be log-normal. Specific turbidities were
calculated (at 400, 500 and 600 nm) for several polystyrene
suspensions of submicrometer particles with several types
of continuous distributions: positively skewed, negatively
skewed, symmetrical, bimodals with broad peaks and
overlapping tails. The polydispersities were from 1.04
to 1.9. Then, from these calculated specific turbidities
and assuming a log-normal form, the PSD of the
suspension was re-estimated. The following conclusions
were drawn that are valid for the estimation of the PSD
(using the specific turbidity method) of suspensions of
submicrometer particles, excluding the Rayleigh regime
where only Dt can be estimated and the (m, a) regimes
where specific turbidity can only give Dw :
ž When the true distribution is continuous with no long
tails to either small or large particles, the estimated
distribution with a log-normal assumption will cover
the main body of the true PSD when plotted on a
number basis.
ž On a weight basis the main body of the true
distribution will be covered by the estimated log-
normal distribution, in all cases, even when the true
PSD has long tails.
ž The weight-average diameter of the distribution
estimated with a log-normal assumption is very close
to the true weight average of the suspension, even
in cases that the true distribution is significantly
different from a log-normal shape. For the cases
studied the weight-average diameter of the PSD
estimated when assuming a log-normal form (on a
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
number or weight basis) was, in general, within 1.0%
of the weight average of the true PSD.
These conclusions are corroborated by experimental
results reported by Haseler.19/ for submicrometer
polystyrene suspensions. They also agree with the obser-
vations of Yang and Hogg..20/ These authors also studied
experimentally the error on the estimated PSD when
the shape of the true distribution is different from the
assumed log-normal form. The estimated distribution
was compared with the true one on a weight basis; the
distributions studied were broad, covering particle sizes
from 0.1 to 10.0 µm. They found that ‘‘the estimated dis-
tribution conformed closely to the central portion of the
true distribution (on a weight basis) and was not strongly
biased towards either of the tails’’.
It should be noted that when using Equation (31) to
estimate fj for diameter Dj .j D 1, 2, . . . , P/, instead of
assuming a form for the PSD, there are also assumptions
involved. These include the choice of the parameter in
the regularization algorithm and the number of points
to which the PSD will be discretized and the location
of the Dj s. The number of points depends on the
available number of turbidity measurements at different
wavelengths. For a study on the effect that the number
of discrete points at which fj is estimated has on the
estimated PSD, readers are referred to Eliçabe and
Garcia-Rubio..62/ In that study the true distributions were
all simulated continuous distributions.
There is also the question of whether there is an advan-
tage in proceeding with collecting more wavelengths and
trying to estimate the distribution using Equation (31). In
the case of continuous unimodal distributions, the reso-
lutions of the two techniques under experimental error
seem to be comparable; an assumption of a log-normal
shape that will provide the main body of the true PSD and
the true Dw may be sufficient for most routine applications
in the submicrometer and lower micrometer region.
7.3.1 The Resolution of Bimodal Distributions
Regularization methods have the potential to recover the
PSD without assuming any shape, if the true distribution
is a bimodal one with two broad peaks, such as that
shown by the histogram in Figure 7. Eliçabe and Garcia-
Rubio.62/ resolved such a simulated distribution where the
particle diameters covered a very wide range from 50 to
2550 nm; in that study wavelengths in the absorption range
were included for the turbidity measurements. For such
bimodal distributions, the regularization methods have
the capability (provided that there are enough turbidity
measurements) to uncover the true shape whereas the
log-normal assumption will always produce an envelope
around the main body, as shown in Figure 7. Distribution I
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DOI: 10.1002/9780470027318.a1517
25
I
f (D )
II
D0 D0 + 0.2 D0 + 0.4 D0 + 0.6 D0 + 0.8
Diameter (µm)
Figure 7 Bimodal distribution as resolved by a log-normal
assumption. Case I: the estimated log-normal distribution
(continuous line) and the true distribution (histogram) are
located between 0 and 0.8 µm (D0 D 0.0). Case II: the estimated
log-normal distribution (dashed line) and the true distribution
(histogram) are located between 0.4 and 1.2 µm (D0 D 0.4).
in Figure 7 shows the distribution (on number basis)
estimated with a log-normal assumption for polystyrene
suspensions (m ³ 1.2) where the true distribution (shown
by the histogram) was in the size range between 0.0 and
0.8 µm (D0 D 0.0). Distribution II is the log-normal PSD
estimated when the size range for the true distribution
was between 4.0 and 1.2 µm (D0 D 0.4). Note that
although the two histogram distributions have the same
breadth (0.8 µm), in case II the distribution has a smaller
polydispersity (since the average size is larger). Note that
in case I the estimated log-normal distribution tends to
envelope only the larger particles of the true distribution,
whereas in case II it uncovers the correct range but of
course cannot resolve the bimodal shape.
When dealing with bimodal distributions one should
keep in mind that the contribution of small particles to
the value of the specific turbidity could be totally obscured
by the contribution of the large ones, depending on their
a values (relative to the a value location where the peak
of Kscat occurs). As an example, assume a polystyrene
suspension (m ³ 1.2) with a bimodal distribution which
consists of two monodisperse populations with D1 D
0.6 µm and D2 D 0.1 µm, and where the number of
small particles is 10 times the number of the large ones
(N2 /N1 D 10). The contribution of the small particles to
the total specific turbidity at 400 nm is only 0.46%. Hence
the presence of small particles will cause less disturbance
than the experimental error even though there are
10 times more small than large particles. In such a case
it is not expected that the regularization methods will
produce the correct solution within experimental error.
26
Wallach and Heller.7/ suggested using combinations
of two distributions with the same form to describe
distributions that are negatively skewed, or bimodals.
A combination of two-parameter distributions (say two
log-normal distributions) requires the estimation of five
parameters (D1g , D2g , s1 , s2 , N2 /N1 ). At least five specific
turbidity measurements at wavelengths far from each
other are required for this estimation if the particles
are in the submicrometer range. These parameters are
expected to be very highly correlated and therefore the
solution to be sensitive to experimental error. A good
solution may be obtained in cases where the contribution
of the distribution of the smaller particles to the overall
specific turbidity is large; otherwise the large particles will
always obscure the small particles.
Readers should keep in mind that in general, bimodal
distributions (except those where the distance between
the modal diameters of the two populations is large
compared with the breadth of the two populations) are
very difficult to resolve with most particle sizing meth-
ods. Using EM, for example, a large number of particles
must be counted, sometimes at different magnifications
in order to resolve the distributions successfully. DLS will
usually result in distributions weighted towards larger
particles. For bimodals where the distance of the two
modal diameters is large compared with the breadth of
the distributions, one can usually determine very success-
fully the particle sizes involved in the two populations (by
EM and sometimes by DLS), but it is difficult to estimate
the relative number of particles in the two populations. In
such cases, if the diameters involved are known very accu-
rately from EM (D1 , D2 , . . . , Dn ), then using a sufficient
number of turbidity measurements one could estimate the
relative number of particles (f1 , f2 , . . . , fn ) (from Equa-
tions 31 and 39). Again, in order to obtain reasonable
estimates, the small particles should weigh significantly
and the distribution must be in an (m, a) regime where
specific turbidity measurements do not simply result in
the same apparent diameters (otherwise all combinations
resulting in the same average are possible solutions).
8 ON-LINE PARTICLE SIZE
DETERMINATION USING
TURBIDIMETRY
As early as 1973, Hamielec and Wright.84/ suggested
using turbidimetry for on-line latex particle size determi-
nation. The configuration of a sampling device for on-line
measurements of the PSD of poly(vinyl acetate) latexes
using turbidimetry was suggested from that laboratory
in 1976..85/ On-line turbidity measurements in fully auto-
mated systems have been reported for poly(vinyl acetate)
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PARTICLE SIZE ANALYSIS
latexes by Kiparissides et al..9,10/ and Zollars.11/ but no
quantitative results from on-line particle size determi-
nation were reported by these workers. Haseler and
Parkin.6/ used on-line turbidity measurements to moni-
tor the growth of silver bromide in a ripening process.
The ripening suspension was circulated continuously in
an undiluted state through a thin cell.
In all of the applications mentioned above only
turbidity was measured on-line. An experimental set-
up to combine on-line determination of the particle
volume fraction with on-line turbidity measurements,
required for on-line specific turbidity measurements, was
first suggested by Pollock..86/ However, no results were
reported on particle sizing, probably because he faced
some problems with that set-up. A simulation for on-line
latex PSD determination in continuous latex reactors was
presented by Bradolin and Garcia-Rubio..22/
Raphael and Rohani.26/ described a device that could
be used on-line to measure the mean particle size
in continuous precipitators or crystallizers. The solids
concentration for this set-up is assumed to be known
and no measurements on the particle volume fraction are
taken on-line. This device was not tested on-line, however,
for continuous production; the measurements reported
were from spot samples. These samples were diluted in a
vessel from which the diluted sample is pumped through
the device and turbidity measurements are taken.
A serious disadvantage of some of the set-ups suggested
for on-line latex particle size determination.9,10,11,22,86/
is that they require a continuous flow of diluted latex
through the spectrophotometer. For specific turbidity
measurements this means that a known amount of latex
is continuously mixed with a known amount of diluent.
Both the latex and diluent have to be pumped at constant
flow rates. This in turn requires that a very small amount
of latex be pumped at the exit of the reactor, at flow
rates as low as 10 mL min 1 , for long periods of time.
A peristaltic pump tried by Gossen.21/ for this set-up
failed owing to coagulation of the latex due to high
shear and chemical attack of the tube by the monomer.
Other types of pumps tried in the same laboratory also
failed..23/ Another problem with continuous dilution
of the latex is that an enormous amount of waste
(very dilute latex) is created that requires treatment
before disposal. This would cause problems in large-scale
operations. The set-up suggested earlier from the same
laboratory.85/ utilizes discrete sampling, but it has serious
disadvantages..23/
A system suggested by Gossen.23,24/ measures both
solids fraction and turbidity on-line, utilizes discrete
sampling, is mechanically simple, has a short cycle time
and high accuracy and it is set up such that thorough
cleaning of the sampling element is performed after each
sample. This sampling device was used for the on-line
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS
application of specific turbidity to monitor particle growth
during poly(vinyl acetate) production in continuous pilot-
plant reactors. Samples were taken at discrete intervals
of 5 min. Results were reported for a period of 10 h.
The weight-average diameters estimated by turbidimetry
showed excellent agreement with results from on-line
DLS..73/ These results, obtained by Gossen, represent
the first published successful effort.24,46,73/ to combine
on-line turbidity and density measurements and to
monitor, on-line, weight-average diameters during latex
production in pilot-scale reactors, in a fully automated
manner. Details on the set-up and an error propagation
analysis study can be found in Gossen..23,24/
9 OTHER CONSIDERATIONS
9.1 Choice of the Methods
It is a well-established perception in particle size analysis
that there is no method which can be successfully
utilized for every application. The effectiveness of each
particle sizing method depends on the special needs
applicable to each case. The selection of the method is a
compromise between accuracy, cost, speed of analysis and
robustness of the instrument in the plant or the laboratory
environment. This section gives some examples that might
help users decide if turbidimetry is suitable for their
applications.
There are cases where an accurate estimate of the
full PSD is required. In such cases the time required
for analysis and the cost of the method are not usually
an issue. Examples of such cases are the evaluation of
a new process and the PSD of the new product, the
study of the effects of various parameters on particle
size in a set of designed experiments and the detailed
study of a nucleation process where the PSD reflects the
mechanisms that take place. For such cases more time
and effort are usually spent than for routine particle size
analysis and more than one particle sizing methods and/or
alternative approaches to the same method are used. EM
will provide measurements of the sizes involved in the
distribution, and will give an indication of the type of the
distribution (i.e. detect the presence of two populations,
etc.). However, resolving the full f .D/ with EM is a
tedious task because a very large number of particles need
to be photographed and counted from representative
parts of the sample. Specific turbidity can be used to
obtain a correct estimate of the weight-average diameter
of submicrometer particles if the (m, a) regimes do not
allow for the full PSD determination. If the (m, a) values
allow for the full PSD determination, then regularization
methods, where no fixed shape of the distribution is
assumed, should be tried first. If these methods show that
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DOI: 10.1002/9780470027318.a1517
27
the shape is smooth and the log-normal assumption is
sufficient, then this assumption can be used for subsequent
routine analysis. DLS could also be used to corroborate
the results for submicrometer particles. Alternatively,
sedimentation field fractionation.87 – 89/ could be used;
this method would be especially useful in cases where
EM cannot be used either because the particles change
size when they are measured dry or they need special
treatment for EM measurements.
Sometimes only routine-type checks are needed and
an average of the PSD or the log-normal assumption
that will provide the main body of the distribution
may be sufficient. Turbidimetry could be used as a fast,
inexpensive technique for such applications.
In some cases only qualitative information is required,
for example when studying qualitatively the effect of
certain process parameters on the particle size. In such
cases almost any technique can be utilized provided that
the same quantity is followed and that this quantity
is sensitive to small changes in the particle size. For
example, specific turbidity can be used to follow a
weight-average diameter or DLS to follow the intensity-
average diameter. It is important that the same method
be used to follow the same average throughout the
study because, as discussed in the next section, different
methods are theoretically directly related (and therefore
are more sensitive) to different averages of the PSD.
Other applications where the dependence of turbidity
on particle size can be qualitatively exploited is to
use turbidimetry as a detection system (as discussed
in section 5.4) to detect the onset of agglomeration or
reactor oscillations in latex production.
When the product is suspected to contain two pop-
ulations of particles with different sizes (e.g. large and
small particles due to a secondary nucleation), the small
particle population will be clearly detected by EM or
chromatographic (i.e. size separation) techniques. Size
separation techniques are very powerful in detecting
small-particle populations. If the contribution of the
small particles to the overall turbidity is significant
then the bimodal distribution can be resolved by tur-
bidimetry using regularization algorithms (i.e. solving
for PSD without assuming a fixed shape). Otherwise,
specific turbidity will only provide the weight-average
diameter for a bimodal suspension of submicrometer
particles.
When choosing a method for on-line measurements,
one must consider several factors: the type of process
(batch or continuous), the purpose of the measurement
(is it routine analysis where we are satisfied with an
average size, or do we need accurate PSD determination),
the required sampling frequency and analysis time of
the method, the cost relative to the expected accuracy
and the reliability and robustness of the method in the
28
plant environment. Turbidimetric methods utilize the
fastest measurements (light is used as a probe). As a
comparison, fractionation (separation) techniques cannot
provide any estimate of the particle size or the PSD until
the fractionation is completed.
It is clear that users must consider several factors before
choosing the technique or a combination of techniques
that are most suitable for their needs. This requires a
good knowledge of the process, the product and the
capabilities and limitations of the technique. Finally,
quoting Groves,.90/ ‘‘the validity of the data need have no
direct relation to the cost of instrumentation’’.
9.2 Corroboration of Results
When another particle sizing method is used to corrobo-
rate results from turbidimetry, this second method must
be chosen carefully. In general, when comparing results
on the full PSD from different methods, the size range
to which each of the methods is applicable, their res-
olution, the effects of errors on the estimated size and
any assumptions introduced in each technique should be
considered. This holds even when comparing results from
two different turbidimetric techniques (i.e. turbidity ratio
and specific turbidity). Erroneous conclusions may be
obtained, as illustrated with the following examples.
The size range to which each of methods is applica-
ble should be considered. Wales.58/ used particle size
measurements from a Coulter Counter instrument to cor-
roborate results from turbidimetry. Some discrepancies
were observed between the two methods. From a detailed
discussion.15/ of his work it became clear that in particle
size regions where both Coulter Counter and turbidime-
try are capable of providing a valid estimate of the PSD
the two methods compared favorably. The discrepancies
observed for suspensions with PSDs in the lower sub-
micrometer range were not due to forward scattering as
originally claimed..58/ Rather, they were due to the fact
that the Coulter Counter instrument could not detect
very small particles (in the lower submicrometer region)
and specific turbidity for the (m, a) values of those sus-
pensions could only provide a correct Dw and not the full
PSD. Discrepancies between turbidimetry and Coulter
Counter results were also observed by Walstra..16/ The
Coulter Counter instrument should not be used to cor-
roborate results from other techniques when dealing with
distributions of small particle sizes (i.e. lower submicrom-
eter particles) or PSD with tails of small particles.
Any assumptions involved in the methods should be
considered. Some average diameters obtained by various
techniques can be directly derived from the underly-
ing theory whereas others depend on the validity of
certain assumptions. Only quantities estimated directly
from theory should be compared. For example, DLS
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DOI: 10.1002/9780470027318.a1517
PARTICLE SIZE ANALYSIS
measures an ‘‘average diameter’’ that corresponds to
the mean diffusion coefficient of the suspension. With
the assumption that the distribution of the diffusion
coefficients is Gaussian, a PSD and its corresponding
weight-average diameter can be calculated. However,
although the estimated mean diffusion coefficient is cor-
rect, this weight-average diameter is not always equal
to the true weight average of the suspension. In con-
trast, the weight average measured by turbidimetry is
numerically close to the true weight average for most
submicrometer suspensions. In another example, some
DLS instruments utilize the Rayleigh – Gans approxima-
tion to convert distributions from an intensity basis to
a weight basis. This approximation is not valid for very
large particles and may cause serious errors in the calcu-
lation of the PSD on a weight basis for broad distributions
or widely spaced bimodal distributions, even if the distri-
bution estimated on an intensity basis is correct.
10 CONCLUSION
Turbidimetric particle sizing methods are experimentally
simple, robust and have very good reproducibility and
potential for on-line applications. They have been applied
for the estimation of the PSD or an average size to a
variety of particle suspensions (Table 1) with diameters
ranging from 0.035 to 50 µm.
Specific turbidity can be used for reliable estimates of
the average particle size and of the PSD of a suspension
for a wider range of particle sizes than the turbidity ratio
or the wavelength exponent techniques. This is because
specific turbidity involves two independent measurements
of the particle size via two different properties of
the suspension (turbidity and solids volume fraction),
whereas the other turbidimetric techniques are based on
turbidity measurements only. Therefore, if the volume
fraction of particles in the suspension can be measured,
specific turbidity should be the turbidimetric technique
of choice. The turbidity ratio or the wavelength exponent
method should be used only if the particle volume fraction
is unknown.
Because of the light scattering behavior, turbidimetric
methods are not theoretically expected to provide infor-
mation on the full PSD in many situations. In order to
decide the type of information about the particle size
(average size or full PSD) that can be extracted from any
turbidimetric method, one must consider both the value of
the refractive index ratio (m) of the suspension and the a
values covered by the distribution. The same PSD that can
be successfully estimated for one system may be impossi-
ble to estimate for another system with a different m value.
There are a few critical combinations of (m, a) values
in turbidimetric analysis for nonabsorbing particles:
TURBIDIMETRY IN PARTICLE SIZE ANALYSIS 29

ž suspensions of submicron particles and values of m Size Distributions ž Ultrasonic Measurements in Particle
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PARTICLE SIZE ANALYSIS
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