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Adsorption Isotherms of Citric Acid Acting as a Growth-

Suppressor onto the (100) and (111) Faces of Sodium Chloride
Crystals in Supersaturated Aqueous Solution
By Shigeko Sasaki*, Noriaki Kubota, and Norihito Doki

DOI: 10.1002/ceat.200500353

The growth-starting supercooling DTG, a degree of supercooling at which a crystal starts to grow when the solution is continu-
ously cooled, was measured in supersaturated aqueous solutions in the presence of citric acid as an impurity1). It was mea-
sured both for the (100) and (111) faces of sodium chloride crystals. From the measured data of DTG, the Langmuir constants
of the (100) and (111) faces were determined at pH = 4.5 to be 6.16 ± 0.88 L/mol and 12.5 ± 2.0 L/mol, respectively. This DTG
method is a convenient method for the determination of adsorption isotherms of an impurity onto specific crystallographic
faces of a crystal.

1 Introduction
It is well known that impurities in solutions can have dra-
matic suppression effects on crystal growth [1–4]. An active
impurity for growth suppression is believed to adsorb be-
forehand on a specific surface of a crystal. However, little is
known about the adsorption of active impurities in aqueous
solution on specific crystallographic surfaces of crystals due
to experimental difficulties. The ordinary adsorption experi-
ment, in which impurity species are made to adsorb on the
surface of small particles suspended in solutions, can not be
applied to adsorption measurements on a specific crystal sur-
face because an impurity species can not be adsorbed exclu-
sively on the particular surface of the crystalline particles
suspended in the impurity doped solution. A direct in situ
detection of impurity species adsorbed on the specific sur-
face of a crystal in aqueous solution is also difficult.
In previous studies, we measured the growth-starting
supercooling DTG, a degree of supercooling at which a crys-
tal starts to grow when the solution is cooled continuously,
for the (100) face of a KDP (potassium dihydrogen phos-
phate) crystal in aqueous solution in the presence of an
Al(III) impurity [5], and the (100) face of a sodium chloride
crystal in aqueous solution in the presence of a Pb(II) impu-
rity. The measured values of DTG were analyzed theoreti-
cally using a model [5, 6], and the Langmuir constants were
deduced for the adsorption of the impurities Al(III) and
Pb(II), respectively, for the (100) faces of KDP and sodium
chloride crystals. In this study, we measured the growth-
starting supercooling DTG for the (100) and (111) faces of a
sodium chloride crystal, respectively, on which a growth-sup-
pressor – citric acid – had been adsorbed beforehand. From
the measured data of DTG, the Langmuir constants for ad-
– the solution was kept at 34.3 °C (TA), a temperature of
[*] S. Sasaki (author to whom correspondence should be addressed,
shigeko@iwate-u.ac.jp), N. Kubota, N. Doki, Department of Chemical
Engineering, Iwate University, Ueda 4–3–5, Morioka 020–8551, Japan.
1) List of symbols at the end of the paper.
sorption of citric acid were determined both for the (100)
and (111) faces of sodium chloride crystals.
2 Experimental
Two types of sodium chloride crystals of different shapes
were used as seed crystals for the measurement of the
growth-starting supercooling DTG. These crystals were pre-
pared as follows: The cubic crystals, which have only (100)
faces, were crystallized from a pure aqueous solution by
natural cooling. On the other hand, sodium chloride crystals
having (111) faces were crystallized from a solution contain-
ing citric acid by natural cooling. The pH of the solution was
adjusted to 4.5 by adding solid sodium hydroxide. The crys-
tals having the (111) faces were cured by growing them at a
supercooling of 2 °C in a pure sodium chloride solution at
room temperature for 6 h in order to remove citric acid
which might remain on the crystal surface.
An experimental apparatus for the DTG measurement is
shown in Fig. 1, in which a seed crystal (1), glued to a stain-
less steel wire, was placed in sodium chloride solution in a
glass cell (2) of working volume of 40 mL. The temperature
of the solution was controlled by a thermo-regulator (3).
The specific crystallographic face of a seed crystal was set at
an angle perpendicular to the axis of a CCD microscope (5).
It was observed through the CCD microscope on a monitor
screen (7). The solution was agitated gently using a magnetic
stirrer (9) throughout the experiment. The temperature was
measured with a thermometer (10) inserted into the solution
in the cell. The solution saturated at 35 °C was used for the
measurement of the growth-starting supercooling. The pH
of the solution was adjusted to 4.5.
The experimental procedure, which was basically the same
as in previous papers [5, 6], is briefly summarized. Initially,
0.7 °C lower than the saturated temperature 35 °C, for a peri-
od of tA, as shown in Fig. 2, during which the crystal did not
grow and citric acid was made to adsorb on the crystal sur-

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 Full Paper

Table 1. Adsorption conditions.

Ts [°C] TA [°C] DTA [°C] tA [h]

Series 1 35.0 34.3 0.7 2–24

Series 2 and 3 35.0 34.3 0.7 22

3 Theory

The face growth rate G of a crystal in the presence of an

impurity is given by the following equation if the equilibrium
adsorption of impurities is assumed [7]:
G
ˆ1 aheq …for aheq ≤ 1† (1)
G0
and, for aheq > 1, G/G0 = 0, where G0 is the face growth rate
Figure 1. Experimental apparatus: (1) seed crystal; (2) glass cell; (3) thermo-
in the corresponding pure system, and heq is the equilibrium
regulator; (4) cooler; (5) microscope; (6) CCD camera unit; (7) monitor coverage of active sites for impurity adsorption. The param-
screen; (8) video recorder; (9) magnetic stirrer; (10) thermometer. eter a, the impurity effectiveness factor, is related to the crit-
ical radius of a two-dimensional circular nucleus of the crys-
36
tal and defined, in the case of sodium chloride [6], as:
∆TA=0.7ºC
35 T ca
Temperature [ºC]

adsorption time, tA S
aˆr (2)
T kTrL
34 A
∆TG
cooling where c is the edge free energy per unit length of a step on
33 the surface of a crystal, a is the surface area of crystal per
growth-starting point Ο growth unit, k is the Boltzmann constant, T and r are the
32
temperature and the relative supersaturation of the solution,
31 respectively, L is the average spacing between active sites
0 5 10 15 20 25 30 where impurities are to be adsorbed, and r = (T + To)/T,
Time [hour]
which is nearly constant if T does not change significantly
Figure 2. Temperature profile.
and To is not a large negative value. To is a constant
when the solubility C is approximated by the linear rela-
tion C = b(T + To). The sodium chloride-water system is
face. Following this adsorption period, the solution was
considered in the present study, where T ∼ 303–308 K,
cooled continuously at a constant rate of 0.3 °C/min until the
To = 9 · 102 K, and r ∼ 4.
specific crystallographic face of the seed crystal started to
In the case that the supersaturation is changed by altering
grow. The start of growth was detected visually on the
the solution temperature T, as in this study, the supersatura-
monitor screen. The growth-starting temperature TG was
tion can be related to the supercooling DT (i.e., Ts–T) as:
recorded and the growth-starting supercooling DTG (i.e.,
TS–TG) was calculated. The temperature was measured with DT
rˆ (3)
a thermometer inserted into the solution in the cell. Three T ‡ To
series of experiments were conducted (see Tab. 1). For the
Therefore, the impurity effectiveness factor becomes, by
first series, DTG of the (100) face was measured for the solu-
inserting Eq. (3) into Eq. (2):
tion with an impurity concentration 0.4 mol/L, using a cubic
seed crystal. Adsorption time tA was varied between 2–24 h ca
aˆr (4)
to determine the time needed for DTG to reach a constant kDTL
equilibrium value, which corresponds to an equilibrium ad-
From Eqs. (1) and (4), the face growth rate G can be writ-
sorption. For the second series of experiments, the equilibri-
ten as a function of supercooling DT as:
um growth-starting supercooling DTGeq was measured for
the (100) face. For the third series of experiments, equilibri-
G ˆ G0 …DT † 1 …DT DTc † …for DT ≥ DTc † (5)
um growth-starting supercooling DTGeq was measured for
the (111) face. Both the second and the third series of ex-
where DTc is a critical supercooling, which corresponds to
periments were performed as a function of impurity concen-
(1–aheq) = 0 and below which G = 0. It is written by:
tration for a fixed adsorption time of tA = 22 h. The impurity
concentration was varied between 0.05–0.5 mol/L. ca
DTc ˆ r h (6)
kL eq

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Eq. (6) can be related to impurity concentration c if the iment, where Pb(II) ion was selected as an impurity for the
Langmuir adsorption isotherm heq = Kc/(1 + Kc) is assumed (100) face of sodium chloride crystal.
to apply for the equilibrium coverage of active sites, as: Fig. 5 shows the adsorption isotherms obtained, which
were drawn using the Langmuir constants obtained. Thus,
ca Kc
DTc ˆ r (7) the measurement of DTG can be used conveniently for the
kL 1 ‡ Kc
determination of adsorption isotherms of a specific face of a
where K is the Langmuir constant. For the case of r = 1, crystal. The DTG method may be the only way which can be
Eq. (7) reduces to: applied to the measurement of an impurity adsorption iso-
therm onto a specific crystallographic face in aqueous solu-
ca Kc
DTc ˆ (8) tion.
kL 1 ‡ Kc
which was derived in previous papers [5]. The critical super-

Growth-starting supercooling, ∆TG [ºC]

5
cooling DTc should be equal to the above-mentioned
growth-starting supercooling DTGeq, which will be obtained
4
for equilibrium adsorption.
3
T = 34.3 [ºC]
4 Results and Discussion A
2
∆T = 0.7 [ºC]
A
4.1 The Effect of Adsorption Time tA on DTG c = 0.4 [mol/l]
1
pH=4.5
The results of the first series of experiments are shown in
0
Fig. 3, where the value of DTG is plotted as a function of ad- 0 5 10 15 20 25
sorption time tA. The value of DTG, increases as the adsorp- Adsorption time [hour]
tion time is increased, and reaches a constant level after Figure 3. Effect of adsorption time on the growth-starting supercooling.
about 15 h. Therefore, we concluded that the adsorption of
[ºC]

citric acid was complete, reaching a final equilibrium state at 6

Geq

tA > 15 h for the (100) face. The equilibrium growth-starting

Equilibrium growth-starting supercooling, ∆ T

supercooling DTGeq was measured, both for the (100) and 5 Eq (7)
(111) faces, for a fixed adsorption time of tA = 22 h (i.e.,
4
> 15 h), as mentioned above in the experimental section.
3
pH=4.5
4.2 Equilibrium Growth-Starting Supercooling as a Function 2
of Impurity Concentration (100) face
1 (111) face
The value of equilibrium DTGeq obtained for the adsorp- 0
tion supercooling of DTA = 0.7 °C at tA = 22 h is plotted in 0 0.1 0.2 0.3 0.4 0.5 0.6
Fig. 4 as a function of citric acid concentration c. The solid Citric acid concentration,c [mol/L]
lines in Fig. 4 are the best fit of Eq. (7) to the obtained data Figure 4. The equilibrium growth-starting supercooling DTGeq as a function of
with a non-linear least squares method. As seen in Fig. 4, citric acid concentration in solution.
the values of DTGeq for the (100) and the (111) faces in-
crease as the citric acid concentration is increased. The value 1

of DTGeq for the (111) face is 0.7–0.8 °C larger than that of

Surface coverage, θeq[-]

0.8
the (100) face. By the fitting of Eq. (7) to the obtained data,
the Langmuir constants of the (100) and the (111) faces were
0.6
determined to be 6.16 ± 0.88 L/mol and 12.5 ± 2.0 L/mol, re-
spectively. Unfortunately, the soundness of the Langmuir
0.4 pH=4.5
constants determined by the measurement of DTGeq can not
be confirmed by comparing them with literature or other ex- (111) face
0.2 (100) face
perimental values because no data are available. But we be-
lieve that these values are acceptable, because the soundness
0
of this method itself has already been confirmed by Kubota 0 0.1 0.2 0.3 0.4 0.5
et al. [6]. Kubota et al. [6] showed the validity of this method Citric acid concentration, c [mol/L]
by comparing the Langmuir constant determined by this Figure 5. Adsorption isotherms of citric acid onto the (100) and (111) faces of
method with that obtained by the ordinary adsorption exper- a sodium chloride crystal.

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5 Conclusions Ts [K] saturated temperature of a solution

T0 [K] constant in C = b (T + T0)/T,
The growth-starting supercooling DTG was measured for DTA [K] adsorption supercooling, at which
the (100) and (111) faces of a sodium chloride crystal in the impurities are made to adsorb
presence of a crystal growth suppressor (citric acid), and the DTG [K] growth-starting supercooling a
following conclusions were drawn: temperature, supercooling at which
– The Langmuir constant of the (100) face was determined a crystal starts to grow on cooling
to be 6.16 ± 0.88 L/mol and that of the (111) face was de- DTGeq [K] equilibrium growth-starting
termined to be 12.5 ± 2.0 L/mol. supercooling or DTG when the
– Citric acid adsorbed onto the (111) face of a sodium chlo- solution is cooled after an
ride crystal more than the (100) face. equilibrium adsorption is attained
– The measurement of DTG can be a convenient method for
the determination of adsorption isotherms of a specific
face of a crystal. Greek symbolss
Received: November 9, 2005
a [–] impurity effectiveness factor
defined by Eq. (2) (see also Eq. (4))
Symbols used b [g/100g–H2O K] temperature coefficient of solubility
c [J/m] edge free energy per unit length of a
a [m2] size of growth unit or the surface step
area of a crystal per growth unit heq [–] equilibrium coverage of active sites
c [mol/L] impurity concentration by adsorbed impurities
C [g/100 g H2O] solution concentration or solubility r [–] relative supersaturation – (Cs–C)/C
G [m/s] face growth rate of a crystal in the
presence of impurity
G0 [m/s] face growth rate of a crystal in pure References
solution
k [J/K] Boltzmann constant [1] J. W. Mullin, Crystallization 4th ed., Butterworth-Heinemann, Oxford
K [L/mol] Langmuir constant 2001, p. 254.
[2] P. A. Meenam, S. R. Anderson, D. L. Klug, in Handbook of Industrial
L [m] average distance between the active Crystallization (Ed: A. S. Myerson), Butterworth-Heinemann, Boston
sites on the step 2002, p. 67.
[3] K. Sangwal, Prog. Cryst. Growth Charact. 1998, 36, 163.
r [–] (T + T0)/T [4] J. Nyvlt, J. Ulrich, Admixtures in Crystallization, VCH, Weinheim 1995.
tA [h] adsorption time [5] N. Kubota et al., Cryst. Growth Des. 2004, 4, 533.
T [K] temperature [6] N. Kubota, S. Sasaki, N. Doki, M. Yokota, Cryst. Growth Des. 2005, 4,
509.
TA [K] adsorption temperature [7] N. Kubota, J. W. Mullin, J. Crystal Growth 1995, 84, 509.
TG [K] growth-starting temperature, at
which a crystal starts to grow on
cooling

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