 Crystal size distribution (CSD) is measured with a series of

standard screens.
 The size of a crystal is taken to be the average of the screen
openings of successive sizes that just pass and just retain the
crystal.
 The cumulative wt % either greater or less than a specified
screen opening is recorded.
 Typical size distribution data on the following figure are
plotted in two cumulative modes, greater than or less than,
and as differential polygons or histograms.
Cumulative wt % retained or passed, against sieve aperture
CONDITIONS OF PRECIPITATION

 evaporation of the solvent

 changing to a temperature at which the solubility is
lower
 chemical reaction between separately soluble gases
or liquids
 induced by additives (salting out)
SUPERSATURATION
GROWTH RATES
NUCLEATION
Nucleation rates are measured by counting the numbers
of crystals formed over periods of time.
The nucleation rate depends on the extent of
supersaturation

B  k1 c b (2)

Values of the exponent b have been found to range from

2 to 9, but have not been correlated to be of quantitative
value for prediction.
 CRYSTAL GROWTH

The growth rates of crystals depend on their instantaneous

surface and the linear velocity of solution past the surface
as well as the extent of supersaturation, and are thus
represented by the equation

G  k2 c g (3)

Values of the exponent (g) have been found of the order

of 1.5, but again no correlation of direct use to the design
of crystallizers has been achieved.
In laboratory and commercial crystallizations, large crystals
of more or less uniform size are desirable.
This condition is favored by operating at relatively low
extents of supersaturation.
The optimum extent of supersaturation is strictly a matter for
direct experimentation in each case.
As a rough guide, the data for allowable subcooling and
corresponding supersaturation of the Table 1 may serve.
Since the recommended values are one-half the maxima
shown, it appears that most crystallizations under
commercial conditions should operate with less than about
2C subcooling or the corresponding supersaturation.
 Table 1. Maximum Allowable Supercooling T (C) and
Corresponding Supersaturation C (g/100 g water) at 25C
Growth rates of crystals also must be measured in the
laboratory or pilot plant, although the suitable condition
may be expressed simply as a residence time.
Table 2 gives some growth rate data at several
temperatures and several extents of supersaturation for
each substance.
In most instances the recommended supersaturation
measured as the ratio of operating to saturation
concentrations is less than 1.1.
It may be noted that at a typical rate of increase of
diameter of 10–7 m/sec, the units used in this table, the
time required for an increase of 1mm is 2.8 hr.
 Table 2.
Mean Overall Growth Rates of Crystals (m/sec) at Each Face
Batch crystallizers often are seeded with small crystals of a
known range of sizes.
The resulting CSD for a given overall weight gain can be
estimated by an approximate relation known as the McCabe
Delta-L Law, which states that each original crystal grows by
the same amount L:
1. All crystals have the same shape.
2. They grow invariantly, i.e. the growth rate is
independent of crystal size.
3. Supersaturation is constant throughout the crystallizer.
4. No nucleation occurs.
5. No size classification occurs in the crystallizer
6. The relative velocity between crystals and liquor
remains constant.
The relation between the relative masses of the original and
final size distributions is given in terms of the incremental L
by
 wi  L0 i  L
3
R (4)
 wi L30 i

When R is specified, L is found by trial, and then the size

distribution is evaluated
EXAMPLE

Seed crystals with this size distribution are charged to a

batch crystallizer
L0, length (mm) 0.251 0.178 0.127 0.089 0.064
w (wt fraction) 0.09 0.26 0.45 0.16 0.04

On the basis of the McCabe L law, find:

a. The length increment that will result in a 20-fold increase
in mass of the crystals.
b. The mass growth corresponding to the maximum crystal
length of 1.0 mm.
SOLUTION
a. When L is the increment in crystal length, the mass ratio is

 wi  L0 i  L  wi  L0 i  L
3 3
R   20
 wi L0 i 3
0.003935

By trial, the value of L = 0.2804 mm

0.003935

b. When Lmax = 1  L = 1 – 0.251 = 0.749

 wi  L0 i  L  wi  L0 i  L
3 3
R   181.79
 wi L0 i 3
0.003935
All continuous crystallizers are operated with some degree of
mixing, supplied by internal agitators or by pumparound 
MSMPR (mixed suspension mixed product removal).
By analogy with the terminology of chemical reactors it could
be called CSTC (continuous stirred tank crystallizer).
Several such tanks in series would be called a CSTC battery.
A large number of tanks in series would approach plug flow,
but the crystal size distribution still would not be uniform if
nucleation continued along the length of the crystallizer.
 (a) The single stage CSTC.
(b) Multistage battery with overall residence time
1 k
t   Vci
Q 1
THE POPULATION BALANCE
The crystal population density, n (number of crystals per unit
size per unit volume of system) is defined as:
N dN
lim  n (5)
L0 L dL

Where N is the number of crystals in the size range L per

unit volume.
The value of n depends on the value of L at which the
interval dL is taken, i.e. n is a function of L.
The number of crystals in the size range L1 to L2 is thus given
by: L 2

N   n dL (6)
L1
Application of the population balance is most easily
demonstrated with reference to the case of the continuously
operated MSMPR crystallizer assuming:
1. Steady-state operation.
2. No crystals in the feed stream.
3. all crystals of the same shape, characterized by a chosen
linear dimansion L.
4. No break-down of crystals by attrition.
5. Crystal growth rate dependent of crystal size.
A continuous MSMPR crystallizer
A population balance (input = output) in a system of volume
V for a time interval t and size range L = L2 – L1 is

n1G1V t  n2 G2V t  Qn L t (7)

where Q : volumetric feed and discharge rate

G : crystal growth rate (dL/dt)
n : average population density

As L  0
d nG  Qn (8)

dL V
Defining the liquor and crystal mean residence time  = V/Q
and assuming the growth is independent of size (L Law),
i.e. dG/dL 0, then:
dn n
 (9)
dL G
Upon integration:
 L 
n  n0 exp    n0 exp x  (10)
 G 
where x is the ratio of crystal size of a crystal that has grown
for a period to the residence time .
dn
n  lim
0

L0 dL

is the concentration of crystals of zero length which are the

nuclei; it also is called the zero size population density.
Equation (10) is the fundamental relationship between crystal
size L and population density n characterizing the CSD.
The quantity n0 is the population density of nuclei (zero-sized
crystals).
A plot of log n vs. L should give a straight line with intercept
at L = 0 equals to ln n0 and a slope – 1/G.
Therefore, if the residence time  is known, the crystal growth
rate, G, can be calculated.
The number nucleation rate, B, can be expressed as a function
of the supersaturation, c:

dN
B  k1 c b (2)
dt L 0

The crystal growth rate G can be expressed in a similar

manner:
dL
G  k 2 c g (3)
dt L0

dL dL dL
as  .
dt L0 dL L0 dt
The nucleation rate may be expressed in terms of the growth
rate by
B  n0 G (11)

or B  k3 G i (12)

where i  b g (13)
consequently n0  k4 G i 1 (14)

So a plot of log n0 vs. log G should give a straight line of slope

i -1 or a plot of log B vs. log G should give a line of slope i.
Thus the kinetic order of nucleation, b, may be evaluated if
the kinetic order of growth, g, is known.
Population plots characterizing the CSD and the nucleation and the
growth kinetics for a continuous MSMPR crystallizer
The nucleation rate is
dn  dL dn 
B  lim  lim 
0
  Gn0 (15)
L0 dt L0  dt dL 

The number of crystals per unit volume is

 
 L
nc   n dL   n exp    dL  n0G
0
(16)
0 0  Gt 

The total mass of crystals per unit volume is

 
 L 
mc   mn dL    c L n exp    dL  6 c n G 
3 0 0 4
(17)
0 0  G 

where  is the volumetric shape factor

c the crystal density
Accordingly, the number of crystals per unit mass is
nc 1

mc 6 c G 3 (18)

The mass of crystals per unit volume with length less than L or
with dimensionless residence time less than x is
L x
m L   mn dL   c G  n 0  x 3 e  x dx
4
(19)
0 0

The value of the integral is

x
3 x  x  x 2 x 3 
xe dx  6 1  e  1  x    
0   2 6 
This expression has a maximum value at x = 3 and the
corresponding length LD is called the predominant length
(modal size)
LD
x 3 LD  3G
Gt
The cumulative mass distribution is
mL  x 2
x 3

m  x

 1  e 1  x    (20)
mc  2 6 

and the differential mass distribution is

dm x 3 e  x
 (21)
dx 6

which has a maximum value of 0.224 at x = 3.

The median size of the mass distribution is defined as the
size of the crystal of which 50% by mass of the product
from an MSMPR crystallizer is larger or smaller than the
size.

mL x  x2 x3 
m   1  e  1  x     50%
mc  2 6 

It is obtained by trial that x = 3.672

LM  3.672 G
1.0
0.9 m
0.8
0.7
0.6
median
0.5
0.4
0.3 modal d m
0.2 dx
0.1
0.0
0 1 2 3 4 5 6 7 8 9 10
x
CSD may be conveniently classified by the median size (LM)
and the coefficient of variation (CV).
The CV, which quantifies the size spread, is a statistical
property related to the standard deviation of a Gaussian
distribution and is normally expressed as a percentage by:

 L84%  L16% 
CV  100   (22)
 L50% 

The higher the CV the broader the spread, CV = 0 denoting a

mono-sized distribution.
The nucleation rate must generate one nucleus for every
crystal present in the product. In terms of M’, the total mass
rate of production of crystals

M' M' 1.5 M '

B 
0
  (23)
nc mc 6av  c Gt  av  c L3pr
3
EXAMPLE
Analysis of Size Distribution Data Obtained in a CSTC
Differential distribution data obtained from a continuous
stirred tank crystallizer are tabulated
w L (mm)
0.02 0.340
The volumetric shape factor is av =
0.05 0.430
0.06 0.490 0.866, the density is 1.5 g/mL, and the
0.08 0.580 mean residence time was 2.0 hr.
0.10 0.700
Find growth rate G and the nucleation
0.13 0.820
0.13 1.010 rate B0.
0.13 1.160
0.10 1.400
0.09 1.650
0.04 1.980
0.03 2.370
SOLUTION
The number of crystals per unit mass smaller than size L is
1 wi
L
N  3 (a)
av  0 Li

It is also related to the CSTC material balance by

dN  L 
 n  n exp 
0
 (b)
dL  G 

Integration of eq. (b) is

 L  0   L 
L
N   n exp   dL  G n 1  exp    (c)
0

0  G    G 
The number of crystals per unit mass smaller than size L is
calculated using eq. (a):

wi Li N
0.02 0.34 0.3917
0.05 0.43 0.8759
0.06 0.49 1.2685
0.08 0.58 1.5841
0.10 0.70 1.8085
0.13 0.82 1.9900
0.13 1.01 2.0872
0.13 1.16 2.1513
0.10 1.40 2.1793
0.09 1.65 2.1948
0.04 1.98 2.1987
0.03 2.37 2.2005
The relation of N and L is represented by eq. (c):

  Li  
N i  G n 1  exp  
0

  G 

According to eq. (c), there are two unknowns, i.e. G and n0.
We have a set of data of Ni and Li (see previous table). Thus
both unknowns can be determined by regression:
G = 0.3515 mm/hr
n0 = 3.4528 nuclei/mm4 = 3.4528  1012 nuclei/m4
Accordingly:
B0 = G n0 = 1.2137  109 nuclei/m4 hr
EXAMPLE
Crystallization in an MSMPR with Specified Predominant
Crystal Size
Crystals of citric acid monohydrate are to made in an
MSMPR at 30C with predominant size LD = 0.833mm (20
mesh). The density is 1.54 g/mL, the shape factor av = 1 and
the solubility is 39.0 wt %. A supersaturation ratio C/C0 =
1.05 is to be used. Take the growth rate, G = v , to be the
value given in Table 2.
For a mass production rate of 15 kg/hr of crystals, M’ = 15,
find the nucleation rate and draw the differential mass
distribution of the crystal.
SOLUTION
G  dL dt  4  108 m s  0.144 mm hr

The predominant size is related to other quantities by

LD  0.833  3 G
  0.833 30.144  1.93 hr

The cumulative and differential mass distributions are

represented by eqs. (16) and (17), respectively.

L L
x   3.60 L
G 0.1441.93
 0.16

0.14

0.12
Differential distribution

0.10

0.08

0.06

0.04

0.02

0.00
0 0.5 1 1.5 2 2.5 3 3.5
Length, mm
The population equation for an MSMPR crystallizer oparated
at steady state with crystal growth rate independent of size,
is written in eq. (8):
d nG  n
 (8)
dL G

For batch crystallizer operated at unsteady state, the simple

population balance relationship must be modified to:

d nG  n (26)

dL t
PROGRAMMED (CONTROLLED) COOLING
If natural cooling is employed, e.g. by passing coolant
through the jacket or coils at a steady rate and constant inlet
temperature, the temperature in the vessel will fall
exponentially as shown in the following figure.
Supersaturation increase very quickly in the early stages and
peaks when nucleation occurs after exceeding the
metastable limit.
This sequence of events leads to an uncontrolled
performance and results in small crystals with a wide CSD.
Natural, controlled (constant nucleation) and size-optimal
cooling modes in a batch crystallizer. (a) temperature
profile. (b) supersaturation profile