Journal of Crystal Growth 252 (2003) 343–349

Experimental determination of the metastable zone width of

borax decahydrate by ultrasonic velocity measurement
. uz*,
H. Gurb . .
B. Ozdemir
Department of Chemical Engineering, Istanbul Technical University, Maslak 80626, Istanbul, Turkey

Received 17 September 2002; accepted 17 December 2002

Communicated by T. Hibya

Abstract

The metastable zone width of borax decahydrate (disodium tetraborate decahydrate), represented by the maximum
undercooling DTmax ; both in pure and impure aqueous solutions were determined according to polythermal method by
using the ultrasonic technique. It is found that the metastable zone width of borax decahydrate in pure solutions
determined by ultrasonic method fulfills well the linear relation between logDTmax and logð  dT=dtÞ: However, the
sensitivity of the method using the ultrasonic technique increases with increasing saturation temperature, probably due
to the increase of temperature dependence of solubility with increasing saturation temperature. A comparison of the
nucleation temperatures from ultrasonic measurements and from visual determination shows that both detection
techniques give almost the same results for borax decahydrate. The results obtained from ultrasonic measurements
show, that the presence of Ca2+ as impurity has only a small effect on the metastable zone width of borax decahydrate
as long as the impurity concentrations is in the range of 25200 ppm. Similar to the effect of Ca2+, Mg2+ also has a
small effect on the metastable zone width of borax up to the impurity concentration of 100 ppm. However, the presence
of 200 ppm Mg2+ results in a reasonable increase of the metastable zone width.
r 2003 Elsevier Science B.V. All rights reserved.

PACS: 81.10.A

Keywords: A1. Metastable zone width; A1. Ultrasonic velocity measurement; A1. Impurities; B1. Borax decahydrate

1. Introduction at about 801C, then the resultant strong liquor is

Borax, which is one of the most important
chemicals for the borate industry, is present as
tincal ore in large tonnages in the deposits of
Kirka/Turkey. In the production of refined borax,
the upgraded tincal ore is crushed to about
o2.5 cm, dissolved in hot recycled borax liquor
*Corresponding author.
. uz).
E-mail address: gurbuzh@itu.edu.tr (H. Gurb .
fed to a vacuum crystallizer after clarification [1].
Crystallization is an important step in the process
sequence. In order to produce crystals with a
specified purity and crystal size distribution at
minimum cost, it is necessary to operate the
crystallizer at the optimum supersaturation within
the metastable zone.
The metastable zone width is an experimentally
measurable quantity and it depends mainly on the
temperature, concentration, cooling rate, presence

0022-0248/03/$ - see front matter r 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-0248(02)02519-8
344 . uz,
H. Gurb .
. B. Ozdemir / Journal of Crystal Growth 252 (2003) 343–349
of impurities and mechanical effects. A knowledge
of the metastable zone width for any set of
conditions is very important for the tailoring of
the crystallization process.
The experimental determination of the meta-
stable zone width is mainly carried out by the
polythermal method, in which the onset of
nucleation can be detected visually or instrumen-
tally [2–10]. Experimental values of the metastable
zone width for a given system depend very strongly
on the method of determination [5,9]. Ultrasonic
velocity through a solution is one of the concen-
tration dependent properties and it can be used to
detect the onset of nucleation. The techniques
based on the measurement of ultrasonic velocity in
solutions have already been used to determine the
metastable zone width [7,9,10], supersaturation [6],
and crystallization kinetics of various chemicals
[11,12].
In the present work, metastable zone width of
borax decahydrate (disodium tetraborate decahy-
drate) both in pure and impure aqueous solutions
were determined according to the polythermal
method by using the ultrasonic technique. This
technique is explained in detail by Omar and
Ulrich [7,10,11]. It mainly consists of subjecting
the solution to consecutive cooling and heating
with constant cooling/heating rate and measuring
the temperature and ultrasonic velocity in the
solution.
2. Experimental procedure
All experiments were carried out with 0.5 l of
solution in a jacketed, well-sealed glass crystallizer.
Temperature control of the crystallizer was ac-
complished by a programmable thermostatic bath
with a cryostat facility. Measurements of ultra-
sonic velocity and temperature were made using a
LiquiSonics 30 immersion probe. The accuracy of
this system for ultrasonic velocity and temperature
is 70.01 m/s and 0.01 K, respectively. Details
about the experimental set-up are given in Refs.
[6,7,10].
Aqueous borax solutions saturated at 293, 303,
and 313 K were prepared by dissolving analytically
pure, commercially available borax decahydrate
(manufactured by Merck KgaA) in distilled water.
The metastable zone widths of these solutions were
determined as a function of cooling rate in the
range of 1025 K/h. The solutions were continu-
ously stirred at a constant rate using a magnetic
stirrer. To ensure complete dissolution, solutions
were kept at a temperature of 10 K above the
saturation temperature for 30 min before each run.
In the case of impure solutions, the effects of Ca2+
and Mg2+ ions on the metastable zone width of
borax solutions saturated at 303 K were examined
by using the same procedure. Ca2+ and Mg2+ ions
were introduced to the solutions as analytically
pure CaCl2 and MgCl2 compounds, respectively.
The impurity concentration was changed in the
range of 25–200 ppm.
3. Experimental results and discussion
3.1. Metastable zone width of borax decahydrate in
pure solutions
According to the polythermal method using the
ultrasonic technique, both the nucleation point
(onset of nucleation) and the saturation point can
be determined from the change of ultrasonic
velocity during the consecutive cooling and heat-
ing steps [7,10].
In Fig. 1 the course of the ultrasonic velocity
during the cooling/heating cycle is given for borax
solution saturated at 303 K as a representative
example. As can be seen from Fig. 1, the ultrasonic
velocity of unsaturated borax solution (1) de-
creases linearly, while the solution is cooled at a
constant rate of 18 K/h. After the temperature
corresponding to the saturation temperature, Ts ;
the ultrasonic velocity of supersaturated solutions
continues to decrease linearly by further cooling.
The solid phase is not formed until the tempera-
ture of the onset of nucleation, Tp : When
nucleation takes place, the ultrasonic velocity
decreases sharply and the slope of the line changes.
During the heating step of the cycle, the crystals
formed dissolve and the ultrasonic velocity in-
creases due to both the increase of the temperature
and the concentration of the liquid phase of
suspension. After all crystals are dissolved, the
 . uz,
H. Gurb .
. B. Ozdemir / Journal of Crystal Growth 252 (2003) 343–349 345

1580 Table 1
Experimental values of saturation and nucleation points of
1570
1
borax decahydrate in pure solutions
Ultrasonic Velocity, m/s

1560
TsðlitÞ dT=dt TsðusÞ TsðvisÞ TpðusÞ TpðvisÞ
1550 2
Cooling (K) (K/h) (K) (K) (K) (K)
1540
3 293 14 295.34 295.69 285.02 285.59
1530 18 295.25 295.05 283.08 283.50
Heating
1520 22 294.97 295.98 283.21 284.20
25 294.86 296.10 281.63 282.50
1510
4 TP:Nucleation Point TS:Saturation Point
1500 303 14 303.84 304.20 294.98 295.05
290 292 294 296 298 300 302 304 306 308 310 312 314 18 304.15 304.08 294.47 294.56
Temperature, K 22 304.12 304.48 294.08 294.76
Fig. 1. The course of ultrasonic velocity in pure borax solution 25 303.92 304.40 293.76 294.05
during the cooling/heating cycle (TsðlitÞ ¼ 303 K,
dT=dt ¼ 18 K/h). 313 13 314.34 314.69 306.75 307.15
18 314.85 314.56 306.39 306.90
21 314.94 315.08 305.87 306.44
value of ultrasonic velocity reaches the value of the 25 314.60 314.80 305.38 305.96
saturated solution (2). Therefore, the temperature
corresponding to the intersection of cooling and
heating curves can be taken as the saturation
point. Since the ultrasonic velocity is a function of dC 
DCmax ¼ DTmax ; ð3Þ
the solution density and the adiabatic compressi- dT
bility, the shapes of the plots of ultrasonic velocity  
dC  dT m
against temperature depend on the solute-solvent  ¼ kN DCmax : ð4Þ
dT dt
system [11].
In order to compare the ultrasonic technique By assuming that the mass nucleation rate is
with the conventional visual detection, the tem- equal to the rate of supersaturation at least at the
peratures corresponding to the onset of nucleation beginning of nucleation (Eq. (4)), the relationship
(Tp ) and the saturation (Ts ) were detected both by between the cooling rate (dT=dt) and maximum
ultrasonic velocity measurement and by visual undercooling is given by
observation in pure borax solutions and the results  
1m dC log kN
are given in Table 1. log DTmax ¼ log 
m dT m
The metastable zone width is expressed as a  
maximum undercooling DTmax ; which is given by 1 dT
þ log  ; ð5Þ
m dt
DTmax ¼ Ts  Tp : ð1Þ
where m and kN are the order of nucleation and
The relation of maximum supersaturation to the rate constant of nucleation, respectively [2,5].
maximum undercooling can be expressed by According to Eq. (5) the dependency of
Z Ts    log DTmax on log(dT=dt) can be described by a
dC first-order equation. Since the slope of the straight
DCmax ¼ dT: ð2Þ
Tp dT line given by this equation is the inverse of the
apparent nucleation order of a given system, the
Since the maximum undercooling is generally lines have to be exactly parallel for various
not very large, the temperature dependence of saturation concentrations. However, some devia-
dC  =dT can be assumed constant over the tion from parallelism has been shown for a variety
temperature range examined. Thus, the maximum of inorganic aqueous solutions. Since the deviation
supersaturation can be given by the following from parallelism reflects the errors depending on
equation: the measurement method, a modified linear
346 . uz,
H. Gurb .
. B. Ozdemir / Journal of Crystal Growth 252 (2003) 343–349

regression method has been used to correct the
straight line [2].
Fig. 2 shows the experimental results from the
ultrasonic velocity measurements for borax solu-
tions saturated at about 293, 303, and 313 K. In
Table 2, the equations for straight lines obtained
by both linear regression and modified linear
regression of experimental data are given. As can
be seen from Table 2, the metastable zone widths
evaluated by the ultrasonic method fulfill well the
linear relationship between log DTmax and logð 
dT=dtÞ: However, the straight lines obtained by
linear regression are not exactly parallel due to the
measurement errors. Therefore, the equations were
corrected by using the modified linear regression
method and the corrected straight lines were
shown in Fig. 2. The apparent nucleation order
of borax decahydrate calculated from the cor-
rected straight lines is 3.37, which is in well
agreement with the result given in literature [2].
The correlation between the experimental and
corrected values of log DTmax are 0.90, 0.97, and
0.98 for borax solutions saturated at about 293,
303, and 313 K, respectively. For the solution
saturated at 293 K, the deviation of experimental
results from linearity is greater than those for
other solutions saturated at 303 and 313 K. A
possible explanation for the greater deviation from
linearity in the case of saturated solutions at 293 K
may be found by comparing the changes of
ultrasonic velocity during the onset of nucleation
for solutions saturated at different temperatures.
In Fig. 3 the change of ultrasonic velocity
during the cooling/heating steps as a function of
temperature was compared for solutions saturated
at 293, 303, and 313 K. As can be seen from the
plots in Fig. 3, the ultrasonic velocity changes
more sharply during the onset of nucleation when
the saturation temperature increases. The reason
for this is probably the increase of the temperature
dependence of the solubility of borax decahydrate
(dCs =dT) with increasing saturation temperature.
Its value is 1.2, 1.7, and 2/(100 g sol. K) for
solutions saturated at 293 K, 303 K, and 313 K,

1.20
1600
1.15
1580
Ultrasonic Velocity, m/s

1.10
1560
1.05
log ∆Tmax

1.00 1540

0.95 1520
Exp. Val.(Ts:293 K)
0.90 Exp. Val.(Ts:303 K) 1500
Exp. Val.(Ts:313 K)
Cor. Val.(Ts:293 K)
0.85 Cor. Val.(Ts:303 K) 1480
Cor. Val.(Ts:313 K) Ts:293K Ts:303K Ts:313K
0.80 1460
1.00 1.10 1.20 1.30 1.40 1.50 1.60 270 280 290 300 310 320 330
log (-dT/dt) Temperature, K
Fig. 2. Graphs of log DTmax versus log(dT=dt) from ultra- Fig. 3. Comparison of the course of ultrasonic velocity during
sonic velocity measurements. cooling and heating cycle for different saturation temperatures
(dT=dt ¼ 25 K/h).

Table 2
Equations of the straight lines obtained by both linear regression and modified linear regression of experimental results

TsðlitÞ (K) Equation of straight line (by linear regression of exp. Corrected equation of straight line (by modified linear
results) regression of exp. results)

293 log DTmaxð293 KÞ ¼ 0:3510 log ð  dT=dtÞ þ 0:6235 log DTmaxð293 KÞ ¼ 0:2299 logð  dT=dtÞ þ 0:6933
303 log DTmaxð303 KÞ ¼ 0:2299 log ð  dT=dtÞ þ 0:6914 log DTmaxð303 KÞ ¼ 0:2299 logð  dT=dtÞ þ 0:6054
313 log DTmaxð313 KÞ ¼ 0:3069 log ð  dT=dtÞ þ 0:5427 log DTmaxð313 KÞ ¼ 0:2299 logð  dT=dtÞ þ 0:5558
 . uz,
H. Gurb .
. B. Ozdemir / Journal of Crystal Growth 252 (2003) 343–349
respectively. The higher the saturation tempera-
ture, the greater the change of concentration is for
the equal temperature change during the nuclea-
tion. Thus, in borax solutions saturated at higher
temperatures nucleation temperature can be de-
termined more sensitively by using the ultrasonic
velocity measurements.
It is known that the experimental values of the
temperature corresponding to the onset of nuclea-
tion depend very strongly on the detection
method. Since the crystals have to grow to a
certain detectable size, the minimum detectable
nucleus size is very important especially in
methods depending on the detection of nucleus
formation. While the crystals become visible in the
size range 5–10 mm, the minimum detection size by
Coulter Counter is 12 mm [5]. On the other hand
in using the detection techniques based on a
concentration depending property of the solution,
the sensitivity of the method changes with the
concentration dependence of the measured prop-
erty. For example, the concentration dependence
of density and ultrasonic velocity for fluoranthene
in trichloroethylene is 6.05  102 kg/(m3 K) and
8.38  102 m/(s K), respectively. Thus the meta-
stable zone widths of fluoranthene in trichlor-
oethylene determined by ultrasonic velocity
measurement are narrower than those determined
by density measurements [9].
In Fig. 4 the nucleation temperatures obtained
by the ultrasonic detection technique and by visual
observation are compared.
It can be seen that almost the same results were
obtained for borax decahydrate by the two
methods examined. Thus, the size of nuclei
detected by ultrasonic technique could be the same
with the size of nuclei detected visually. However,
ultrasonic technique may give better results than
visual detection for compounds with a high
temperature dependence of solubility.
3.2. Metastable zone width of borax decahydrate in
the presence of impurities
The addition of impurities can increase or
decrease the width of metastable zone. Tincal ore
contains minor amounts of gypsum, calcite,
dolomite and clay minerals as gangue minerals
347
310
Nucleation Temperature, K
305
300 Us-293 K
Vis-293 K
295 Us-303 K
290
Vis-303 K
Us-313 K
Vis-313 K
285
280
12 14 16 18 20 22 24 26 28 30
Cooling Rate, K/h
Fig. 4. Comparison of the nucleation temperatures obtained by
ultrasonic velocity measurements and by the visual method.
and some borate minerals such as inderite
(Mg2B5O11  15H2O), inderborite (CaMg-
B5O11  11H2O), kurnakovite (Mg2B5O11  15H2O)
[1]. During the dissolution of the upgraded ore,
Ca2+ and Mg2+ ions from these minerals pass to
the saturated borax liquor [13].
Therefore, in the present study the effects of
Ca2+ and Mg2+ on the metastable zone width of
borax decahydrate were also investigated by using
ultrasonic velocity measurements. In all experi-
ments in the presence of impurities, the saturation
temperature and the cooling/heating rate were
kept constant as 303 K and 18 K/h, respectively. In
Fig. 5 the change of ultrasonic velocity during the
cooling/heating steps as a function of temperature
is given for borax solutions containing Mg2+ of 0,
25, 50, 100 and 200 ppm. For borax solutions
containing Ca2+ of 0, 25, 50, 100 and 200 ppm, the
change in the course of the ultrasonic velocity as a
function of impurity concentration is negligible
(figure is not presented). In Table 3, the metastable
zone width of borax decahydrate is given as
maximum undercooling for varying impurity
concentrations.
It is known that polyvalent metal cations with a
strong ability to form coordination complexes
usually broaden the metastable zone. On the other
hand the effect of any impurity on the width of
metastable zone depends on both the impurity/
compound combination and the concentration of
impurity [2,5]. The results given in Table 3 show
that Ca2+ has only a small effect on the metastable
348 . uz,
H. Gurb .
. B. Ozdemir / Journal of Crystal Growth 252 (2003) 343–349

1570 solutions saturated at 293, 303, and 313 K. The

1560 determination of the metastable zone width by
means of the polythermal method was done using
Ultrasonic Velocity, m/s

1550
1540 the ultrasonic velocity measurement as a detection
1530 technique for the onset of nucleation. The results
1520 pure
show that the dependencies of log DTmax ; on
25 ppm Mg logð  dT=dtÞ fulfill well the linear relation for
1510 50 ppm Mg the borax solutions saturated at 303 and 313 K.
1500 100 ppm Mg
200 ppm Mg
The plot of log DTmax ; versus log(dT=dt) shows a
1490 higher deviation from linearity for the borax
1480 solution saturated at 293 K, probably because of
282 286 290 294 298 302 306 310
the lower temperature dependence of solubility in
Temperature, K
comparison to the solutions saturated at 303 and
Fig. 5. The course of ultrasonic velocity in borax solution 313 K. It could be concluded that the sensitivity of
during the cooling/heating cycle in the presence of the impurity the method using ultrasonic velocity measure-
Mg2+ (TsðlitÞ ¼ 303 K, dT=dt ¼ 18 K/h).
ments increases with the temperature dependence
of solubility.
Table 3 The nucleation temperatures were compared
Effect of Ca2+and Mg2+ impurities on the metastable zone
with the results obtained from the visual determi-
width of borax decahydrate (TsðlitÞ ¼ 303 K; dT=dt ¼ 18 K=h)
nations. Since the method using ultrasonic techni-
Impurity Impurity concentration Maximum undercooling que is easy and gives almost the same results with
(ppm) (DTmax ; K) the method using visual detection of nuclei
— — 9.68 formation, it can be used to determine the
metastable zone width of borax decahydrate for
Ca2+ 25 9.78 every set of conditions. Moreover, especially for
50 9.99
the compounds with high temperature dependence
100 10.37
200 10.69 of solubility this method will probably give better
results than visual detection.
Mg2+ 25 9.32 The effects of Ca2+, Mg2+ impurities on the
50 9.77 metastable zone width of borax decahydrate were
100 9.95
examined by the ultrasonic method in borax
200 17.21
solutions saturated at 303 K. It is found that
Ca2+ has only a small effect up to a concentration
of 200 ppm, whereas Mg2+ retards the nucleation
and broadens the metastable zone of borax
zone width of borax for the examined impurity decahydrate strongly when its concentration ex-
concentrations. Very similar to the effect of Ca2+, ceeds 200 ppm.
Mg2+ also has a small effect on the metastable It is concluded that, the polythermal method
zone width of borax up to the impurity concentra- using ultrasonic velocity measurement for the
tion of 100 ppm. However, the presence of detection of nucleation point can be used
200 ppm Mg2+ results in a reasonable increase of successfully in the determination of the metastable
the metastable zone width. zone width of borax decahydrate both in pure
and impure solutions. The sensitivity of the
method for any compound having a high
4. Conclusions temperature dependence of solubility could be
higher than other methods using detection
The metastable zone width of borax decahy- techniques such as density measurement, visual
drate was determined experimentally in aqueous detection, etc.
 . uz,
H. Gurb .
. B. Ozdemir / Journal of Crystal Growth 252 (2003) 343–349 349

Acknowledgements [4] P.M. Ushasree, R. Muralidharan, R. Javayel, P. Ramasa-

The authors gratefully acknowledge financial
support from the Volkswagen Foundation.
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