Accepted Manuscript

The effect of high intensity ultrasound (HIU) on the kinetics of crystallization

of sucrose: Elimination of latent period

Kaman Singh, Satya Prakash Gupta, Ashok Kumar, Ajay Kumar

PII: S1350-4177(18)30251-7
DOI: https://doi.org/10.1016/j.ultsonch.2018.05.030
Reference: ULTSON 4188

To appear in: Ultrasonics Sonochemistry

Received Date: 15 February 2018

Revised Date: 22 May 2018
Accepted Date: 23 May 2018

Please cite this article as: K. Singh, S.P. Gupta, A. Kumar, A. Kumar, The effect of high intensity ultrasound (HIU)
on the kinetics of crystallization of sucrose: Elimination of latent period, Ultrasonics Sonochemistry (2018), doi:
https://doi.org/10.1016/j.ultsonch.2018.05.030

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 The effect of high intensity ultrasound (HIU) on the kinetics of crystallization of sucrose:
Elimination of latent period#

Kaman Singh, Satya Prakash Gupta, Ashok Kumar, Ajay Kumar

Ultrasonic Laboratory, Department of Chemistry, Babasaheb Bhimrao Ambedkar University

Lucknow-226025

E-mail –drkamansingh@yahoomail.com

ABSTRACT: The application of a technique to eliminate the latent period during crystallization
of sucrose by high intensity ultrasound (HIU) was investigated in this paper. Employing HIU (20
kHz, 750W) to crystallization of sucrose, latent period was eliminated and it was found to obey
first order kinetics (K ~10-5 sec-1) in the temperature range of 30-50°C. Employing Arrhenius
equation, the average energy of activation (Ea) estimated as 5.0 kcal mol-1. Traditional
knowledge indicates that crystallization is sufficiently spontaneous; however, the magnitude of
“K” and other thermodynamic quantities of the process indicate that crystallization is actually a
slow process. Generally, chemical reactions which posses low rate constants, need the high
energy of activation. On the contrary, the energy of activation is appreciably less. The energy of
activation with a rate constant of the order of 10-5 sec-1 could be predicted of the order of 20 kcal
mol-1 at 27 °C. The low energy of activation for crystallization of sucrose is of interest. A very
interesting elucidation can be had from neutron diffraction data and transport property of the
sucrose which is discussed in details in this paper.

Keywords: Sonocrystallization, Latent period, Sucrose, Kinetics, Activation energy.

# a part of this manuscript has been presented at Asia-Oceania Sonochemical Society

Conference (AOSS-3) held on 14-16th September 2017 in Chennai (India)
 1. Introduction

Crystallization of sucrose is a vital step during sugar processing on which the economy of
sugar industry depends significantly. Therefore, fundamental and applied works on various
aspects of crystallization of sucrose have been the subject of many research projects in the past
[1-5]. A review of the literature [1-5] reveals that the kinetic data were complex and Arrhenius or
Eyring’s equations were not applicable as such as long as the latent period resists. The
occurrence of latent period in case of crystallization of sucrose was first studied by VanHook et
al [1]. The kinetic of the process was followed in a relative way means of change in
concentration supersaturate syrup in which the crystal seeds are uniformly suspended. Although
any property dependent on concentration may be used for this purpose the refractive index is
most direct and most convenient. Theoretically we expect that if deposition of sucrose molecule
on crystal seed occurs from the beginning of the process, the refractometer reading would
decrease but it has been noticed that the refratometer did not indicate any decrease in
concentration in the initial interval of time (Fig.1) which is referred as latent period in the
crystallization of sucrose. The latent period refers to a decrease of the rate of crystallization in
the initial intervals of time leading to incomplete exhaustion of sucrose from the mother liquor.
The latent period in the crystallization process presents a serious drawback especially in sugar
industry where the rate of crystallization is undoubtedly hampered due to its presence which may
ultimately affect the economy of the industry.

Fig.1. Plot illustrating latent period during crystallization of sucrose (Reprinted with permission
from Ref. [4]. Copyright 2013 Elsevier).
 The studies on the occurrence of the latent period and mechanism during the
crystallization of the sucrose have attracted the attention of a number of workers. VanHook et al
[2-4] investigated the influence of seed/source ratio on the occurrence of latent period and kinetic
studies initiated by them have been thoroughly investigated by Ramaiah et. al [5].

In the earlier studies, it has been reported that the occurrence of latent period / induction
period during crystallization of sucrose was eliminated employing either sucrose solution of the
different supersaturation index or seed crystals of the size less than 0.28mm. VanHook et al [1]
investigated the influence of seed /sucrose ratio on the occurrence of latent period and found that
at very low seed sucrose ratio, the latent period becomes more pronounced and extended. Their
study clearly established that as the supersaturation increased from 1.0 to 1.03 the length of
induction period decreased from 45 to 11 min. Ramaiah et al [5] studied the effect of grain size
and found that for the same seed sucrose ratio the crystal with dimension <0.3mm gave no
induction period when used as seed. However, the present work provides new insights on
control/ removal of occurrence of latent period / induction period during crystallization of
sucrose using HIU. The existing process of elimination of latent period is tedious from a
practical point of view, however, elimination of latent period employing HIU is simple to operate
and gives reproducible results.The deliberate addition of seed in conventional process at the
correct time during the ongoing process is also comburesome whereas, application of HIU could
be extended to online process and does not need additional manpower for seeding. The entire
equipment system can run for a long time without any care because of its high automation and its
operation is also easy.

The industrial application of ultrasound on scale control in the sugar industry further
gives us the confidence to apply power ultrasound for the elimination of induction period /latent
period during crystallization. Hu et al [6] applied the ultrasonic technique for scale control in the
sugar industry and their results indicated that not only the viscosity of sugar solution was
reduced, but also the heat transfer coefficient and evaporation intensity of the evaporation system
were improved by 42.4% and 15.2% respectively, and the scale was removed remarkably with
no significant effects on white sugar quality. In addition, chemical detergent was not necessary,
so no chemical contamination existed and labour intensity was reduced in this technique.
Furthermore, the ultrasonic equipment is easy to operate and has good performance in terms of
high continuity and automisation.

Literature survey revealed that the most important effect of ultrasound on crystallization
is the induction of nucleation and growth of crystal [7]. A review article by Ruecroft et al [7] on
the application of power ultrasound to crystallization of organic molecules constitutes a
comprehensive review for ultrasonic chemists’. In this review they have also reviewed the
developments in scale-up methods and available equipment.

Power ultrasound has been used in crystallization to induce nucleation in many organic
reactions. The potential of ultrasonic energy in assisting the cooling crystallization of dextrose
monohydrate was investigated by Devarakonda and others [8] and they reported that ultrasonic
energy can be used to induce nucleation and increase the overall mass rate of crystal growth.
They also reported that employing ultrasound product with the desired crystal size could be
produced.
Narducci and Jones [9] compared results of conventionally seeded crystallization
experiments for adipic acid (20−40 wt % of solute) with unseeded experiments. When adipic
acid was initially crystallized under insonation, unseeded experiments produced crystals with
irregular habit and varying size distributions whereas, a short ultrasonic burst applied at the
beginning of the cooling crystallization offers comparable advantages compared to conventional
seeding, in terms of size distribution and a regular crystal shape. The use of a short ultrasonic
burst produced product with regular hexagonal particle shapes, with reduced elongation than
after conventional seeding. By increasing the power of ultrasound more regular crystal habits and
narrowed particle size distributions could be achieved.

Li et al [10] investigated the effect of power ultrasound (PUS) in controlling the

supersaturation, induction period, nucleation and crystal growth during crystallization of 7-
amino-3-desacetoxy cephalosporanic acid. Their experimental results show that insonation leads
to the reduction of both the induction period and metastable zone width of the crystallization so
that the process of crystallization can be more efficiently controlled than without insonation.
Agglomeration is also greatly reduced. The crystal size and size distribution can also be tailored
by adjusting the sonication parameters.
 The effect of ultrasound on induction time and metastable zone width of primary
nucleation of a potassium sulphate solution in a batch reactor was investigated by Lyczko et al
[11]. They reported that induction time and metastable zone width significantly reduced by
ultrasound. It has been shown that ultrasound can influence the heterogeneous primary
nucleation of potassium sulphate and it seems to decrease the activation energy so they can
decrease the critical radius. Ultrasound can induce nucleation which could be extended to
industrial crystallisation processes. Moreover, ultrasound could allow deliberate seeding to be
avoided and thus avoiding the introduction of foreign particles into the solution.

High-Intensity Ultrasound (HIU) or power ultrasound is shown to affect induction period

in crystallization. This is shown for several systems including sucrose, lactose, and lipid systems
[12-15]. Published reports [12] revealed that ultrasound irradiation (20 kHz, 100 W) is an
efficient tool for controlling polymorphic crystallization of tripalmitoylglycerol and and cocoa
butter. The effect of sonication has been examined in terms of rate of nucleation and
polymorphic control. It was found that sonication accelerated the rate of nucleation in both the
cases as measured by induction time for the occurrence of crystals and by the number of crystals
nucleated.

Chow et al [13-14] reported the primary and secondary nucleation of ice during the
sonocrystallisation of ice for solutions in the concentration range of 0–45 wt.% sucrose.
Employing sonication at 20 kHz, clear evidence of the stimulation of primary nucleation was
noted, by increasing the temperature at which nucleation takes place. Application of alternating
pressures at a frequency of 67 kHz to the sample whose heating and cooling is controlled and
monitored carefully provides confirmation of the fragmentation of ice dendrites growing in a
sucrose solution to produce new ice crystals (secondary nucleation).
Various parameters such as sonication time, pH and initial lactose concentration of
reconstituted lactose solution for anti-solvent acetone based lactose recovery using
sonocrystallization have been studied by Patel et al [15]. Sonocrystallization offers spontaneous
supersaturation resulting in early nucleation, great ability in rapid and uniform blending of the
anti-solvent resulting in rapid lactose recovery from sonicated samples as compared to non
sonicated samples. Furtheremore, the lactose recovery was found to be directly proportional to
the acetone concentration. The recovery of lactose is found to be in the range of 80 – 92 %
within 4 min of sonication, whereas the commercial effluent treatment techniques are time
consuming and not effective enough. Sonocrystallization using acetone as an anti-solvent could
be a novel process for the rapid recovery of lactose from the whey, which is to be explored with
real waste water from dairy industry [15].
The above literature clearly illustrates that power ultrasound has been used in crystallization
to induce nucleation (primary and secondary) and reduction of the latent period in many
reactions, however, there is a dearth of such application in crystallization of sucrose although
few reports are available for primary and secondary nucleation of ice during the
sonocrystallisation of ice for solutions in the concentration range of 0–45 wt.% sucrose and there
is no such work directly on the effect of ultrasound effect on induction period/latent period in the
crystallization of sucrose. Furthermore, elimination of latent period employing HIU is simple to
operate and gives reproducible results.The deliberate addition of seed in conventional process at
the correct time during the ongoing process is also comburesome whereas, application of HIU
could be extended to industrial crystallization. Moreover, ultrasound could allow deliberate
seeding to be avoided and thus avoiding the introduction of foreign particles into the solution.

2. Material and methods

2.1. Materials

Extra pure Sucrose of purity 99.9% was purchased from Merck Specialties Pvt. Ltd.
Mumbai (India).

2.2. Apparatus

The ultrasonicator (Sonics vibra-cell VCX750, USA) high intensity liquid processor was
used for sonication. The ultrasonicator used in the present study was an amplifier power
(automated). It is a “high intensity ultrasonic probe (horn type-step Horn ½ Solid, Part No.630-
0219) with diameter of the tip was 1/2" (13mm). Its microtips and probes are fabricated from
titanium alloy (Ti-6Al-4V) and are autoclavable. The length of probe was 139 mm and
amplitude was 114 microns”. The vacuum oven of Vaiometra Model, Associated Scientific
Technologies, Delhi (India), was used in the test study. Abbemat digital refractometer, 300
Model Anton Paar, Ashland (United States), was used for measuring refractive index with an
accuracy of ±0.00001. The double walled crystallizer (Fig. 2) employed in these studies was
similar to the one used usually in commercial sugar factories with all the required conditions for
the kinetic studies, crystallizer was designed and fabricated. In crystallizer the temperature can
be maintained constant by circulating water from thermostat in the outer jacket of the
crystallizer. It is provided within opening O to draw the analytical liquid from time to time
without disturbing the solution. An outlet is also provided in the lowest point of the basal to drain
out the washings. A stirrer S is provided (bush bearing) B which can be rotated by means of
pulley P actuated with reducing gear. The volume of the crystallizer used was 250 mL.

Fig.2. Crystallizer (A stirrer S is provided (bush bearing) B which can be rotated by means of
pulley P actuated with reducing gear)

2.3. Experimental setup (Methods)

Sucrose was dried at 60°C in a vacuum oven for about five hours. The sucrose content of
the samples was 99.97% with undetectable ash. The syrup was prepared by a usual method with
water of pH 7.0. The calculated quantity of sucrose to give desired supersaturation at the
experimental temperature T was weighed and dissolved in water at a higher temperature (800C)
and cooled slowly to the experimental temperature T. The supersaturation (S) was calculated
according to the following formula.

………………… (i)

Syrups of known supersaturation were prepared and transferred carefully into the
crystallizer where it was allowed to attain the constant temperature for about half an hour. The
crystallizer (Fig. 2) employed in these studies was similar to the one used usually in commercial
sugar factories with all the required conditions for the kinetic studies.

In an experiment syrup of sucrose with supersaturation (S = 1.08) was prepared and added to
the crystallizer. When the system attained a constant temperature, an aliquot was withdrawn by a
small drop pipette and the refractive was recorded initially. A weighed amount of seed crystal (5
g/100g of the solution) was added to it and the stirring was started simultaneously with time. At
different intervals of time the syrup was withdrawn with dropper plugged with washed glass
wool and its refractive index was recorded.

In another experiment, two sets of sucrose solutions with supersaturation indices (S = 1.13)
were prepared and added to the crystallizer. A solution was irradiated with ultrasonic waves (20
kHz, 750 W) as a function of time with help of ultrasonicator and another was followed without
treatment. The sucrose samples sonicated for different intervals of time were withdrawn with
dropper plugged with washed glass wool and their refractive indices were recorded. This
practice of sonication of the samples and subsequent measurement of its refractive index was
followed until 80min. In the absence of ultrasound too at different intervals of time the syrup
was withdrawn and its refractive index was recorded. In all these experiments the temperature
was maintained at 35 ±0.05°C and the refractive index with an accuracy of ± 0.0001 was noted.
Results

Crystallization of sucrose was investigated at supersaturation index (S = 1.08) and a typical

set of kinetic data observed are given in Fig. 3. It is observed from the data in Fig. 3 that during
crystallization of sucrose the so called latent/induction period is invariably present at the
beginning of the process. These observations are consistent with reported literature [1-5]. It is
evident that the rate of deposition is slow as compared to that occurring at the latter stages of
crystallization process. It is of interest to note that the refractive index which is a measure of the
sucrose content in the liquid phase, decreased progressively with time suggesting the occurrence
of crystallization. Further, the refractive index attained a minimum value with time (see Fig. 3)
which corresponded to supersaturation equal to 1.08 which points out that under the
experimental conditions.
In another experiment, two sets of sucrose solutions with supersaturation indices (S = 1.13) were
taken. A solution was irradiated with ultrasonic waves (20 kHz, 750 W) as a function of time
with help of ultrasonicator and another was followed without treatment. It is observed from the
curve (Fig.4) that in the absence of ultrasound, the latent period invariably present at the initial
interval of time (approx. 30 min) whereas latent period completely eliminated employing HIU.
The duration of the latent period can be calculated by extrapolation of the curve. This is also
obtained by finding out the time up to which the first order of kinetic was not applicable. The
dotted line in Fig. 3 and bold lines (black) in Fig. 4 refer to the expected plot (extrapolated)
whereas, the smooth lines refers to the observed plots (curved shape) which illustrates the
duration of the latent period.

Fig.3. Graph showing latent period during crystallization of sucrose (S = 1.08). (error bars
indicate standard deviations) dotted lines show extrapolation
 Fig.4. Graph illustrating sonicated and unsonicated ways of crystallization of sucrose (S= 1.13)
The HIU power was 750 W at 20 kHz with duration 5 min at each interval (error bars indicate
standard deviations)

During crystallization, sucrose molecule does not undergo any chemical change. The
sucrose molecule in solution differs from that on the crystal in respect of certain physical and
thermodynamical properties. The studies on the kinetics of the reaction enable one to understand
the order of the reaction, specific reaction rate, energy of activation and thermodynamic
properties associated with the process. Kinetic studies of a process refer simply the investigation
on the amount of substance undergone change at different intervals of time. Thus, crystallization
of sucrose can be represented as

Sucrose (in solution) Sucrose (in solid phase) ………….…..… (ii)

The reaction (i) refers to the deposition of sucrose molecules from the solution phase on the
crystal surface. The system is obviously a heterogeneous one involving two phases; sucrose
solution and solid crystal.

A sucrose solution of known concentration or supersaturation is maintained at a constant

temperature either stirred at a desired number of revolutions per min. or kept stationary. The loss
in sucrose content in the solution on account of the deposition of sucrose molecules due to
crystallization process at different intervals of time‘t’ is noted by a refractometer. Refractive
index is a linear function of sucrose concentration if the initial concentration of sucrose is
represented by ‘a’, refractometer reading recorded at varied time ‘t’, give the concentration of
sucrose existing in the solution phase at time ‘t’, viz (a-x) where x is the concentration of sucrose
underwent change at ‘t’, from law of mass action, we get.

dx/dt = K (a-x)n …………..……(iii)

where n and K are the order and rate constant of the reaction, respectively.

Following the kinetics of sucrose solutions by this method, the loss of sucrose molecules from
the solution phase occurs according to the following equation.

. …………….. (iv)

From obtained data, at different sonication time, the rate constant was computed and such
representative data are shown in Table 1.

It is of interest to note that the values of “K” obtained from employing the first order kinetic
equation and given in the last two columns of Table 1 (with sonication) are fairly constant in the
initial stage of the process. Thus, “Kav” was of the order of 0.361 min. -1) x10-3 upto 40 min. Later
“K” decreased appreciably with time suggesting the inapplicability of the first order equation at
later intervals of time, i.e. in the proximity of equilibrium. This is in accord with the suggestion
made earlier [1-5] that the kinetic consideration for crystallization process can be envisaged only
much before the attainment of the equilibrium process of crystallization and dissolution. On the
other hand (without sonication) the values of “K” obtained from employing the first order
equation and given in the last columns of Table 1 are in random order (different value of
kinetics for different intervals of time) because of occurrence of the latent period in the initial
stage of crystallization. However, values of “K” are of same order (approximately) in the latter
stages in both the case (with sonication and without sonication) as non-occurrence of the latent
period.
 Table 1

Data Showing the Values of Refractive Indices and Rate Constant of Sonocrystalization
of Sucrose

a=1.38907 (initial concentration of sucrose syrup)

-1 -1
S.No Sonication time (min.) (a-x) K (min. ) x10-3 (With K (min. ) x10-3 (Without
sonication) sonication)

1 0 1.38907

2 10 1.38412 0.357 0.086

3 20 1.37899 0.364 0.224

4 30 1.37408 0.361 0.338

5 40 1.36906 0.362 0.363

6 50 1.36786 0.307 0.339

7 60 1.36665 0.271 0.282

8 70 1.3665 0.232 0.232

9 80 1.3665 0.203 0.202

10 90 1.3665 0.180 -

Data are shown in Table 1 clearly illustrate that during sonocrystallizaton, the validity of
the application of first order kinetics was observed in the initial phase of the reaction. Such
characteristics are of diffusion controlled reactions. In such reactions, the experimentally
measured rate is not the rate of interaction between the molecules but is, instead, the rate of
diffusion.

Studies on the kinetics of crystallization of sucrose in the temperature range of 30-600C

enabled us to obtain thermodynamic data (Table 2). Applying Arrhenius equation to these data
activation energy was found as 5.0 kcal mol-1 (Fig. 5).

The following equation due to Eyring representing the velocity constant (K) in terms of
fundamental thermodynamic quantities is of interest for the consideration of its application to
data of sonocrystallization of sucrose.

K = (kBT/h) exp. (∆S0)/R exp. -(∆H0/RT) ……………………….(V)

Where kB is the Boltzmann's constant; T is the absolute temperature; h, the Planck’s

constant; R, the gas constants, ∆S the change in entropy and ∆H is the change in the heat content
of the system.

Table 2 gives the values of thermodynamic quantities of crystallization of sucrose

evaluated from the Eyring’s equation. It is of interest to see that of these quantities, the entropy
change is negative in nature and suggests the loss of a degree of freedom during the
sonocrystallization process.

Fig.5. Arrhenius plot for sonocrystallization of sucrose

 Table 2

Thermodynamic Parameters of Sonocrystallization of Sucrose

Temp. (K) K (x10-5 sec-1) ∆G (kcal mol-1) ∆H (kcal mol-1) ∆S (cal K-1 mol-1)

308 0.5846 7.375 4.472 -9.427

318 0.7599 7.449 4.452 -9.424

328 0.9821 7.516 4.432 -9.402

3. Discussion

The magnitude of the velocity constant K ≃ 10-5 sec-1 is surprisingly of a low order as the
crystallization process is thought to be very fast. For reactions with K ≃ 10-5 sec-1, the energy of
activation could be predicted to be of the order of 20.0 kcal mol-1. The low value of energy of
activation (5.0 kcal mol-1) recorded for sonocrystallization of sucrose is of significance and
throws light on the mechanism of this process. In the process of sonocrystallization, sucrose
molecules do not undergo any change. The process is purely a physical reaction. The data,
however, suggest that some energy, in the form of activation energy is required by sugar
molecule in the solution phase before it is deposited on the crystal surface. This energy seems to
be involved in the following two processes.

(i) As in adsorption process, the sugar molecule has to acquire a certain amount of energy to
overcome the surface barrier before it is deposited into the crystal lattice.
(ii) The sucrose molecule in solution phase remains solvated with water molecules attached
by loose bonds to its many polar OH groups, A part of activation energy may,
therefore, be taken as the energy required to pull the loosely bound solvent molecules
apart, to give isolated, unsolvated sucrose molecules as only such molecules can only
be crystallized.
 The process I or/ and II involve low energies and hence the low order of activation energy
(5.0 kcal mol-1) for crystallization of sucrose. The positive values of ∆G and ∆H further indicate
the slow nature of the sonocrystallization process in accordance with low magnitude of velocity
constant K ≃ 10-5 sec-1.

The low energy of activation for sonocrystallization of sucrose is of interest. A very

interesting elucidation can be had from well established [16-18] neutron diffraction data and
transport property of the sucrose. The sucrose crystal is monoclinic (a = 10.65Å, b=8.70Å, c=8.0
Å, β= 1050 44’). The form in which the sucrose molecule exists in its crystal network is indicated
in Figure 4. It is of interest to note that two bonds indicated in Figure 4 by dotted lines between
H’6 and O5 and H’1 and O2 in glucose and fructose units are due to intermolecular hydrogen
bonding. The formation of these two hydrogen bonds in addition to the ether linkage (through O1
see Fig. 5) between glucose and fructose units renders it to simulate the formation of a triple
bond.

The presence of hydrogen bond network further supports the fact that solid phase
conductance in sucrose [19-20] and its allied crystalline products attribute to the protons of the
hydrogen bond network in sucrose

Fig.6. Sucrose molecule in solid phase (dotted lines show hydrogen bonding H’1 and H’6 of
fructose unit near to O2 and O5 of glucose unit)
 The solvated sucrose molecules cannot be set into the crystal lattices. For this purpose,
these are de-solvated by breaking the hydrogen bonds with which the water molecules are
attached to it and it is done at the expense of some energy by molecular collisions (activation
energy, etc.) All the pure, simple and de-solvated molecules are not suited for crystallization.
Only those molecules in which the rotation of glucose and fructose units around the ether linkage
hydrogen atoms H’1 and H’6 of fructose unit near to O2 and O5 of glucose unit such that the
hydrogen bonds referred to above can be formed. In solution state, the glucose and fructose units
rotate independently around O1 whereas, in the crystalline state, the formation of the above
hydrogen bonds restricts the rotational movements, consequently; reduces entropy, as actually
observed in the present work.

4. Conclusion

The present study concludes that occurrence of latent period (20-25 min) during
crystallization of sucrose can be eliminated by high intensity ultrasound (20 kHz, 750W). This
aspect of the present investigation is very important from the practical point of view and it can be
applied to initiate and control crystallization on an industrial scale and moreover, intentional
seeding which is common in industrial crystallization processes could be avoided if the operation
is carried out under the influence of ultrasound. Furthermore, it is a non-chemical device and
easy to operate as well. As long as latent period persists, observed data are not amenable to
follow first order kinetics. However, crystallization of sucrose under the influence of power
ultrasound was found to obey first order kinetics in the temperature range of 30-50°C. The
magnitude of the velocity constant K ≃ 10-5sec-1 is surprisingly of a low order as the
crystallization process is thought to be very fast. For reactions with K ≃ 10-5 sec-1, the energy of
activation could be predicted to be of the order of 20.0 kcal mol-1. The low value of energy of
activation (5.0 kcal mol-1) recorded for sonocrystallization of sucrose is of significance and
throws light on the mechanism of the process. In solution state, the glucose and fructose units
rotate independently around ether linkage whereas, in the crystalline state, the formation of the
hydrogen bonds restricts the rotational movements, consequently; it reduces entropy.
Acknowledgments

The authors are thankful to Sugar Factory management for giving us the opportunity to
work on industrial level sonocrystallization. The financial support to (SPG) from UGC is
gratefully acknowledged.

References

[1] A. Van Hook, Kinetics of sucrose crystallization: pure sucrose solutions, Ind. Eng. Chem.
36 (1944) 1042-1047.

[2] A.Van Hook, Kinetics of sucrose crystallization, Ind. Eng. Chem. 37 (1935) 782-785.

[3] A. Van Hook, Kinetics of sucrose crystallization - sucrose - non-sucrose solutions, Ind. Eng.
Chem. 38 (1946) 50-53.

[4] A.Van Hook, in: Honig, P. Principles of Sugar Technology; Revised edn. Vol. 2, Elsevier,
2013, pp. 152-153.

[5] N.A. Ramaiah, S.K.Sanyal, Studies on the kinetics of crystallization of sucrose: Effect of
grain size on the induction period, Proc. Sug. Tech. Asso. Ind. 1961, 29 p.65

[6] A. Hu, J. Zheng, T. Qiu, Industrial experiments for the application of ultrasound on scale
control in the Chinese sugar industry, Ultrasonics Sonochemistry,13 (2006) 329–333.

[7] G. Ruecroft, D. Hipkiss, T. Ly. N. Maxted, P.W. Cains, Sonocrystallization:  The use of
ultrasound for improved industrial crystallization, Org. Pro. Res. Dev. 9 (2005) 923-932.

[8] S. Devarakonda, J. M. B. Evans, A. S. Myerson, Impact of ultrasonic energy on the

crystallization of dextrose monohydrate, Cryst. Growth Des., 3 (2003) 741-746.

[9] O. Narducci, A. G. Jones, Seeding in Situ the Cooling Crystallization of Adipic Acid using
Ultrasound, Cryst. Growth Des., 12 (2012) 1727−1735.

[10] H. Li, H. Li, Z. Guo, Y. Liu, The application of power ultrasound to reaction crystallization,
Ultrasonics Sonochemistry.13 (2006) 359–363.
[11] N. Lyczko, F. Espitalier, O. Louisnard, J. Schwartzentruber, Effect of ultrasound on the
induction time and the metastable zone widths of potassium sulphate, Chem. Eng. J., 86 (2002)
233–241

[12] K. Higaki, S. Ueno,T. Koyano, K. Sato, Effects of ultrasonic irradiation on crystallization

behavior of tripalmitoylglycerol and cocoa butter, 78 (2001) 513–518.

[13] R. Chow, R. Blindt, R..Chivers, M. Povey, The sonocrystallisation of ice in sucrose

solutions: primary and secondary nucleation, Ultrasonics. 41 (2003) 595–604.

[14] R. Chow, R. Blindt, R. Chivers, M. Povey, A study on the primary and secondary nucleation
of ice by power ultrasound, Ultrasonics. 43 (2005) 227–230.

[15] S. R. Patel and Z. V. P Murthy, Ultrasound assisted crystallization for the recovery of
lactose in an anti-solvent acetone, Cryst. Res. Technol. 44 (2009) 889 – 896.

[16] G.M. Brown, H.A. Levy, Sucrose: Precise determination of crystal and molecular structure
by neutron diffraction.Science. 141 (1963) 921-923.

[17] G.M. Brown, H.A. Levy, Further refinement of the structure of sucrose based on neutron-
diffraction data. Acta Cryst. B29 (1973) 790-797.

[18] C.A. Beevers, W. Cochran, Sweet crystallography – the crystal structure of sucrose,

Proc. Royal. Soc. A. A90 (1947) 790.

[19] K. Singh, M. Prasad, Solid state conductance in sucrose and its allied crystalline products,
Ind. Chem. Soc. 82 (2005), 437-440.

[20] M.M. Szostk, K. Piela, K. H. Natkaniec, I. Natkaniec, E. Bidzinska, Optical nonlinearity

and electric conductivity origin study on sucrose crystal by using IR, Raman, INS, NMR, and
EPR spectroscopies, Carb. Res. 395 (2014) 29-37.
Highlights

• The application of a technique to eliminate the latent period during crystallization

of sucrose by high intensity ultrasound (20 kHz, 750W) was investigated
• Sonocrystallization of sucrose was found to obey first order kinetics (K ~10-5 s-1)
in the initial part of reaction process. Such characteristics are of diffusion
controlled reactions.in the temperature range of 30-50°C.
• Employing Arrhenius equation, the average energy of activation (Ea) was
estimated as 3.5 kcal/mole. However, energy of activation with rate constant of
the order of 10-5 sec-1 could be predicted of the order of 20 kcal/mole at 27 °C.
• Traditional knowledge indicates that crystallization is sufficiently spontaneous;
however, the magnitude of “K” and other thermodynamic quantities of the
process indicate that crystallization is actually a slow process.
• In solution state, the glucose and fructose units of sucrose rotate independently
around O1 whereas in the crystalline state, the formation of the hydrogen bonds
restricts the rotational movements, consequently; entropy decreases.