31

Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

CRYSTALLIZATION KINETICS OF AMMONIUM

PERCHLORATE IN AN AGITATED VESSEL
Dr. Nahidh W. Kaseer
Lecturer
Chem. Eng. Dept
University of Technology

Dr. Rafi J. Yaqob

Lecturer
Chem. Eng. Dept
University of Tikrit

Ahmmad Khaled
Assistant Lecturer

ABSTRACT
Overall crystal growth kinetics

growth rate on each variables of concern

for ammonium perchlorate in laboratory

(temperature, seed size, and stirrer

scale batch agitated vessel crystallizer

speed) .

have

5.80 0.19 0.79

1.38
RG 22.438 10 4 exp
.N .L .C
8.314T

been

determined

from

batch

experiments performed in an integral

mode.

The

effects

of

temperature

between 30-60C, seed size 0.07, 0.120

and 0.275 mm and stirrer speed 160,
340, and 480 rpm, on the kinetics of
crystal growth were investigated. Two
different

methods,

viz.

polynomial

fitting and initial derivative were used to

predict

the

kinetics

expression.

In

general both methods gave comparable

results for growth kinetics estimation.
The order of growth process is not more
than two. The activation energy for
crystal growth of ammonium perchlorate
was determined and found to be equal to
5.8 kJ/ mole.
Finally, the influence of the
affecting parameters on the crystal
growth rate gives general expression that
had an obvious dependence of the

The

general

expression
saturation

overall

had
is

growth

shown
the

that

most

rate
super

significant

variable. While the positive dependence

of the stirrer speed demonstrates the
importance of the diffusional step in the
growth

rate

model.

Moreover,

the

positive dependence of the seed size

demonstrate the importance of the
surface integration step in the growth
rate model. All the studied variables tend
to

suggest

that

characteristics
perchlorate

the

growth

of

from

rate

ammonium

aqueous

solution

commenced in a batch crystallizer are

diffusion kinetic controlled process.
KEYWORDS:
Ammonium

Crystallization,

perchlorate

crystal

growth kinetics, seeded solutions

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Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

NOMENCLATURES

Mass deposit per unit mass of

Rate of cooling ,C/min

free solvent ,kg/kg

Concentration ,kg/kg

RG

Overall growth rate,kg/m2.s

C*

Saturation concentration,kg/kg

Temperature ,C

kn

Rate constant of nucleation,kg/s

Tmax Maximum allowable

Seed size,m

Stirrer speed,rpm

undercooling temperature,C

super saturation of a system may be

INTRODUCTION
Crystallization is one of the basic

achieved by cooling, evaporation, or as a

processes in the final treatment of the

result of chemical reaction. In other

products in the chemical industry. Kinetic

words, the crystallization and nucleation

data on crystallization process are of

phenomena

basic importance for the design of

concentration exceeds solute solubility

industrial

(William, 1994). Formation of crystalline

crystallization

equipment.

occur

masses

crystallizer and the crystal size of the

nucleation

product,

even-

Nevertheless, due to the complexity of

increasing attention is being rapid in the

each one of these different stages, and in

literature to the kinetics of crystallization

order to perform studies which establish

(Nyvlt, 1989) .

clear conclusions about crystal growth, it

consequently

The crystallization process consists of

and

conjection

solute

These data determine the size of the

and

implies

where

crystal

between
growth.

is of great importance to control the

two stages. The first called (nucleation)

system

at

maximum

which is the formation of the solid phase,

nonexpected phenomena, i.e. primary or

whereas the second, entitled growth, is

secondary

the build-up of layer of solute on nucleus

growth experiments (Grases, 1993).

nucleation

and

during

avoid

crystal

(Ullman, 1988). Super saturation is the

The present study is mainly directed to

driving force for both stages of the

study the kinetics of crystal growth and

process. The degree of the supers

nucleation for ammonium perchlorate

aturation or deviation from equilibrium of

and state the expression rates

saturated condition is the main factor

nucleation and for crystal growth in

controlling the deposition process. The

accordance with the previous mentioned

for

33

Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

forms. Although, the process has a great

The solution had been introduced in a

complexity and distinction between the

flask supplied with an enclosure to

two mechanism that conducted through

minimize evaporation of water. The

crystal formation would take a great deal

enclosure was supplied with a calibrated

of attention. The crystal growth kinetic

thermocouple. Later on, the solution was

will be studied at temperature range,

heated to (10C) higher than the prescribe

agitation speed and range of seed size at

temperature to ensure complete solvating

constant degree of super saturation .

of the stock. Afterwards, the solution was

cooled incrementally at constant rate till
the desired temperature was reached.

EXPERIMENTAL SECTION
The.

determination.

super

This was accomplished by adjusting the

saturation curves and consequently the

flow rate of the coolant medium (water).

metastable limits was commenced in a

At first sight of nucleus formation, the

100 ml Erlenmeyer flask fitted with a

temperature of the solution was recorded.

magnetic stirrer, and a digital temperature

The difference between the saturation and

reader

nucleus formation temperature represents

calibrated thermocouple. A schematic

the maximum allowable undercooling

diagram of the apparatus had been

difference (Tmax) that corresponds to

illustrated in Fig. (1). The flask was

the

immersed

maximum

which

in

of.

incorporated

water

with

bath.

The

particular

cooling

allowable

rate.

This

undercooling

temperature of the cooling medium

difference may be interpreted latter to

(water) was carefully controlled via two

determine the maximum super saturation

needle valves suited at the inlet and exit

allowance before nucleation occurs (i.e,

ports to alter the flow rate of the inlet and

the

outlet streams from the bath. 100 W lamp

subsequently, to estimate the nucleation

was used for good observation to

rate expression.

illuminate the sample under test. 100 ml

of

saturated

solution

of

metastable

zone

width)

and

The widths of the metastable zone

prescribed

between temperature range (30-60C) and

concentration had been prepared of pure

various cooling rates range between (0.5-

Ammonium perchlorate (99.95% pure) .

2C/min) was determined. Similarly in a

same manner the nucleation in the

34

Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

presence of the crystalline material (i.e.

operated in a batch wise sequence over a

seeds) was determined. The solution was

range of variables; temperature range

seeded with (0.8 gm) of crystal (0.275

(30-60C), stirring speed (160, 340, and

mm). Afterwards the solution was cooled

480 rpm) and seed size (275 m, 118 m,

down

70 m).

to

its

working

saturation

temperature.
Growth kinetics determination was
evaluated

from

MATHEMATICAL TREATMENT

isothermal

It has been frequently suggested by

desupersaturation curve. The process take

Nyvlt (1971) and Mullin (1984) that

place in a batch crystallizer shown in Fig.

nucleation rate in bulk system is most

(2). The crystallizer is constructed from

conveniently correlated by an expression

glass vessel of 16 cm internal diameter

of the form :-

and of 2 Liter capacity. To prevent

evaporation from the aqueous solution,

Rn = Kn Cn ... (1)

which might cause an appreciable error,

Where (Kn) is the mass nucleation rate

the vessel was supplied with an enclosure

coefficient and (n) is the order of the

made

digital

process with respect to super saturation

(C). The nucleation rate may also be

regulatory stirrer and cooling coil had

expressed in term of the rate at which

been incooperated with the vessel to

super saturation is created by cooling:

from

Perspex.

thermometer with a thermocouple,

commence the determination of the super

saturation

curves.

propeller mixer 6

stainless

cm

steel

diameter is

Rn = qb .. (2)
Where b

incorporated with a motor to provide

agitation.

dT
, and (q) is the mass
dt

deposited per unit mass of free solvent

To maintain the solution at the

present in a solution, which is cooled by

desired temperature, the vessel had

(1C). However, (q) is a function of

placed inside a water bath incorporated

concentration and of crystallizing species.

with inlet and outlet port streams in

Mathematically, this can be expressed in

addition the water bath was manufactured

this way:

with a thermostat. The crystallizer was

35

Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

*

dC
. (3)
q
dt

metastable limits become more narrowed

when the solution was super saturated

Where C is the solution concentration

(seeded) (i.e. between 1.2 and 2.65C)

expressed as mass of anhydrous salt per

than the unseeded solution that ranged

unit

Maximum

between (2.0 and 3.80C). This was

allowable super saturation (Cmax), may

contributed to the existence of the seeds

be

that work as an initiators (as a catalyst)

mass

of

expressed

solvent.

interm

of

maximum

allowable undercooling (Tmax):

for nucleus formation.

d C
Tmax (4)
Cmax
dT
Hence Eq. (1) can be rewritten to give:

d C

dT

b kn d C Tmax (5 )

dT

Or

2) Nucleation kinetics of ammomium

pechlorate :Typical

relationships

maximum

allowable

between

the

undercooling

temperature and the rate of cooling

d C

log b (n 1) log
dT

LogKn nLogT

increased, the degree of super saturation

for nucleation was increased that in

(6)

return increased the rate of nucleation.

Which indicate that the dependence of

Eventually, the lesser degree of rate of

(log b) on (Log Tmax) is linear and the

cooling affected the rate of nucleation in

slope of the line gives the order of the

a way that leads to greater median size of

nucleation process (n). The experimental

crystals.

data for the ammonium perchlorate

3)

solution over the temperature range

events it was intended to investigate the

between 30 and 60 C are analyzed using

growth kinetic of ammonium pechlorate

least squares method in accordance with

crystals from aqueous solution in a

Eq. (6).

laboratory batch cooling crystallizer.

max

Crystal growth kinetics :- in this

Isothermal desupersaturation curves

RESULTS AND DISCUSSION

are constructed from the experimental

1)

data

Metastable Zones : from Figs 3

& 4, it was noted that the width of the

taking

into

consideration

the

36

Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

influence of temperature , stirrer speed

General expression of crystal growth

and seed size.

rate:

The

experimentally

desupersaturation

To formulate the most general rate model

were

to account the effect of the variables

manipulated

(temperature, stirrer speed and seed size),

polynomial

equation suggested by Nyvlt (1971) and

curves

subsequently
mathematically

determined

(i.e,

the

fitting and the initial derivative) to

Mullihn (1984):-

determine expressions of crystal growth

rate and also to formulate

Rn = Kn Cn

general

expression of the crystalline growth rate,

Can be modified to :

which takes into account, the effects of

the three variables (i.e, temperature,

E d g
RG aLc exp
N C .. (7)
RT

stirrer speed, and seed size). A fourth

The values of the growth rate model in

order polynomial fitting by the least

Eq. (7) were estimated by implementing

squares technique and initial derivative

Rosenbrock

techniques

superior

optimization method to the data of eight

evaluation in comparison to the second

experiments. The graphical presentation

order

(Initial

of the growth rate correlation between the

typical

observed and predicted growth rates is

which

polynomial

derivative

gave

technique

method).

desupersaturation

curves

and

its

shown in

and

Quasi-

Newton

Fig. 13. The last Fig. of

polynomial fittings are shown in Figs. 7,

constants are shown in the following Eq.

8, 9. It was found that

5.80 0.19 0.79 1.38 (8)

RG 0.00224 exp
N L C
8.314T

polynomial
polynomials

and
give

the

the fourth
second-order

good

fit

for

experimental .
All

results of growth rate data as a

function of super saturation are depicted

in Figs. 10, 11, 12.

CONCLUSIONS
1)

In determining the metastable

limits, it was observed that the metastable

limits for ammonium perchlorate have
relatively narrow limits, e.g. between 2.0
to 3.6 C for the unseeded solution and
between 1.2 to 2.65 C for the seeded
solution.

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Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

2)

Increasing the rate of cooling, the

diffusional step in the growth rate model.

metastable limits become more broading

Moreover, the positive dependence of the

for both seeded and unseeded solution.

seed size demonstrates the importance of

Accordingly, higher rate of cooling gave

the surface integration step in the growth

higher

and

rate model. Eventually, all the studied

consequently smallest median size of the

variables tend to suggest that the growth

produced crystals.

rate

3)

perchlorate

rate

of

nucleation

the temperature dependence of the

characteristics
from

of

ammonium

aqueous

solution

nucleation expression, (Kn) was found

commenced in a batch crystallizer are

more

diffusion kinetic controlled process.

sensitive

to

the

temperature

variations in unseeded solution than in

REFERENCES

seeded solution.

1-Grases F. Studies on Lead oxalate

4)

The values of nucleation parameters

crystalline growth J.. Colloids and

show lower numeric value in seeded

Interface science, vol. 155, P. 265 (1993).

solution than in unseeded solution, which

2-Mullin J. W., Compression between

means faster and lower rate for the

indirect

seeded

Methods

solution

than

the

unseeded

and
for

direct
the

contact

coding

crystallization

of

solution.

potassium sulfate Chem. Eng. Res. Des.,

5)

Vol. 62, P.297, Sep. 1984.

The affecting parameters on the

ammonium

3-Nyvlt J. , Industrial crystallization

pechlorate from aqueous solution (e.g.

from solutions Butterworths, London ,

temperature, seed size, and stirrer speed),

1971.

fourth order polynomial fitting gave

4-Nyvlt

superior evaluations in comparison to the

crystallization 10th Ed. Elesevier Press.,

second

New York (1989).

crystal

growth

order

rate

of

polynomial

technique

J.

and

Zaceks,

Industrial

(initial derivative method).

5-Ullman Encyclopidia of Industrial

6)

chemistry : Crystal growth , 5th Ed.,

The general overall growth rate

expression show that super saturation is

V.A. 8, P.173, (1988).

the most significant variable. While the

6-William. P. M., Optimize Batch

positive dependence of the stirrer speed

Crystallization Chem.

demonstrates the importance of the

Eng. Progress, P.73, Sep. (1994).

38

Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

Fig. (1) Apparatus for the determination of the

metastable limits and the kinetics of nucleation

Fig. (3) Metastable limits at different rate

of cooling (unseeded solution)

Fig. (2) Layout of the apparatus

Fig. (4) Metastable limits at different rate

of cooling (seeded solution)

Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41)

Fig. (5) Effect of cooling rate, b, on the

maximum allowable undercooling
temperature, Tmax for unseeded solution
(saturation temperature 30 C

Fig. (7) Desupersaturation curve of

ammonium perchlorate at 40 C, 160 rpm and
0.275 mm seed size (experiment 2)

39

Fig. (6) Effect of cooling rate, b, on the

maximum allowable undercooling
temperature, Tmax for seeded solution
(saturation temperature 30 C

Fig. (8) Desupersaturation curve of

ammonium perchlorate at 40 C, 480 rpm and
0.275 mm seed size (experiment 6)

40

)Tikrit Journal of Eng. Sciences/Vol.16/No.1/March 2009, (31-41

.
60-30

0.275, 0.12, 0.070

480, 340, 160 .

.
.

5.8

/.

5.80 0.19 0.79 1.38

RG 0.00224 exp
N L C
8.314T

.
.
() .