Heat Mass Transfer

DOI 10.1007/s00231-006-0209-4

ORIGINAL

Experimental data of solubility at different temperatures: a

simple technique
J. M. P. Q. Delgado

Received: 16 May 2006 / Accepted: 3 November 2006

Springer-Verlag 2006

Abstract This article describes a simple and inex- DT transverse (radial) dispersion coefficient
pensive experimental technique, easy to set-up in a (m2/s)
laboratory, for the measurement of solute solubilities K permeability in Darcy’s law (m3s/kg)
in liquids (or gases). Experimental values of solubility k average mass transfer coefficient (m/s)
were determined for the dissolution of benzoic acid in L length of test column (m)
water, at 293–338 K, of 2-naphthol in water, at n number of soluble spheres (–)
293–373 K, and of salicylic acid in water, at 293–343 K. p pressure (kg/ms2)
The experimental results obtained are in good agree- Pe¢ peclet number based on diameter of active
ment with the theoretical values of solubilities sphere (= u0 d1 /D¢m) (–)
presented in literature. Empirical correlations are Q, Q1 volumetric flowrate (m3/s)
presented for the prediction of solubility over the en- r spherical radial coordinate (m)
tire range of temperatures studied, and they are shown s standard deviations (kg/m3)
to give the solubility value with very good accuracy. SL surface area per unit length (m)
T temperature (K)
u interstitial velocity (vector) (m/s)
List of symbols u0 absolute value of interstitial velocity far from
a radius of the active sphere (m) the active sphere (m/s)
A area of a soluble sphere (m2) ur, uh components of fluid interstitial velocity (m/s)
c solute concentration (kg/m3)
c0 bulk concentration of solute (kg/m3)
c* saturation concentration of solute (kg/m3) Greek letters
cout concentration in the outlet stream (kg/m3) e bed voidage (–)
d diameter of inert particles (m) / potential function (m2/s)
d1 diameter of active sphere (m) h spherical angular coordinate (rad)
D diameter of test column (m) x cylindrical radial coordinate (distance to the axis)
DL longitudinal dispersion coefficient (m2/s) (m)
D¢m effective molecular diffusion coefficient w stream function (m3/s)
(m2 /s)

J. M. P. Q. Delgado (&) 1 Introduction

Departamento de Engenharia Quı̀mica,
Faculdade de Engenharia da Universidade do Porto,
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal Solubility is perhaps the most fundamental of all che-
e-mail: jdelgado@fe.up.pt mical phenomena. The significance of what dissolves

123
 Heat Mass Transfer


what, to what extent, at what temperature and pressure, c  c0 kSL
and the effects of other species, was recognized at a very ¼ 1  exp  L : ð2Þ
c
 c0 Q
early stage. In more recent times the importance of
solubility phenomena has been acknowledged In order to guarantee that the outlet stream is
throughout science. For example, in the environment, saturated, it is important to observe the approximate
solubility phenomena influence the weathering of rocks, criterion (c – c0)/(c* – c0) > 0.999 (error less that
the creation of soils, the composition of natural water 0.1%). The number of soluble spheres presented in a
bodies and the behaviour and fate of many chemicals. packed bed is given by,
The characteristic ability of water to behave as a
polar solvent changes when water is subjected to high Vcolumn 3 ð1  eÞD2 L
n¼ ¼ ð3Þ
temperatures and pressures. As water becomes hotter, Vparticle 2 d31
its molecules seem much more likely to interact with
nonpolar molecules. For example, at 300C (and high and the general validity of the above theory holds,
pressure) water has dissolving properties very similar provided that the approximate criterion
to acetone, a common organic solvent.
Also, solid–liquid and solid–gas mass transfer 6ð1  eÞkL
[6:908: ð4Þ
investigations with Newtonian or non-Newtonian fluids u0 ed1
are frequently made by following the rate of dissolu-
tion of a low solubility solute. In all researches, accu- If the criterion of Eq. (4) is to be satisfied, it is
rate solubility data are required. important to know the value of the average mass
On mass transfer investigations in porous media, as transfer coefficient, k, so as to be able to estimate the
in studies of dispersion coefficients and solute trans- interstitial velocity of liquid, u0.
port, the most common solutes used are benzoic acid,
2-naphthol, naphthalene, salicylic acid and succinic 2.1 Mass transfer around a buried soluble sphere
acid with water or air (see [13]). In these experiments,
knowledge of accurate solubility data at different For the propose of analysis, let as consider the situation
temperatures is very important, i.e., for low solubility of a slightly soluble sphere of diameter d1 ( = 2a)
solutes. buried in a bed of inert particles of diameter d (with d
The experiment proposed is simple and inexpensive, > d1), packed uniformly (void fraction e) around the
and it provides an accurate method for the measure- spheres. The packed bed is assumed to be ‘‘infinite’’ in
ment of solubilities of solid solutes in liquids and gases. extent and a uniform interstitial velocity of liquid, u0, is
imposed, at a large distance from the spheres.
In order to obtain the flow field in the vicinity of the
2 Theory buried sphere, Darcy’s law, u = – K grad p, is coupled
with the continuity equation, div u = 0, and Laplace’s
Consider a vertical column of length L, containing a equation, 2 / = 0, is obtained for the flow potential
packed bed of soluble spherical particles of diameter / = Kp.
d1. If liquid flow is steady, with a uniform volumetric In terms of spherical coordinates (r, h), the potential
flowrate Q, if the concentration of solute in the liquid and stream functions are, respectively (see [2]),
fed to the bed is c0 and the solubility of the solid par-  
ticle is c*, a mass transfer boundary layer will develop. 1 a3
/ ¼ u0 1 þ r cos h ð5Þ
In the analysis of results of experiments of dissolu- 2 r
tion of soluble spherical particles in liquid flow, the 
u0 a3 
equation for dissolution rate is given by, w¼ 1 r2 sin2 h ð6Þ
2 r
@c
Q ¼ kSL ðc
 c0 Þ ð1Þ and the velocity components are
@x
where SL is the active surface area per unit length and  a3 
@/
k is the average mass transfer coefficient. Given ur ¼ ¼ u0 cos h 1  ð7Þ
@r r
constant flowrate, uniformly distributed particles and
 
isothermal conditions, Eq. (1) is integrated between 1 @/ 1 a3
the inlet and outlet conditions of the bed, x = 0 to L uh ¼ ¼ u0 sin h 1 þ : ð8Þ
r @h 2 r
and c = c0 to c. The following equation results,

123
Heat Mass Transfer

Making use of the potential and stream lines, it is (0.496 mm average particle diameter) through which
possible to perform a material balance on the solute water was steadily forced down, at temperatures in the
in a differential element of a ‘‘stream tube’’ to obtain range 293–373 K.
(see [1]) A stainless steel tube (21 mm i.d. and 200 mm long)
was used to hold the bed of soluble solid spheres in an



@c @ @c @ 2 @c
upright position while a metered stream of distilled
¼ DL þ DT x ð9Þ water was fed to the top of the column, as sketched in
@/ @/ @/ @w @w
Fig. 1. Near the bottom of the stainless steel column, a
where x is the distance to the flow axis, and DL and DT perforated plate, covered with fine wire mesh, was used
are the longitudinal and transverse dispersion coeffi- to support the bed.
cients, respectively. The distilled water was initially deaerated, under
The boundary conditions to be observed in the vacuum, to avoid liberation of gas bubbles in the rig, at
integration of Eq. (9) are: (1) the solute concentration high temperature. The test column was immersed in a
is equal to the background concentration, c0, far away silicone oil bath kept at the desired operating tem-
from the sphere; (2) the solute concentration is equal perature by means of a thermosetting bath head (not
to the equilibrium concentration, c = c*, on the surface represented in the figure). The copper tubing feeding
of the sphere and (3) the concentration field is sym- the distilled water to the column at a constant metered
metric about the flow axis. rate was partly immersed in a pre-heater and it had a
For very low fluid velocities, dispersion is the direct significant length immersed in the same thermosetting
result of molecular diffusion, with DT = DL = D¢m, and bath as the test column; the copper tubing leaving the
the numerical solution presented by Carvalho et al. [1] test column was immersed in a chillier to cool the
applies. Those authors suggest that their results are outlet stream before reaching the UV analyser.
well approximated (with an error of less than 1%) by The water flowrate was then adjusted to the re-
quired value, Q, and the concentration of solute in the
 1=2
D0m 4 0 2=3 4 0
outlet stream was continuously monitored by means of
k¼e 4 þ ðPe Þ þ ðPe Þ ð10Þ a UV/VIS Spectrophotometer (set at 274 nm, for 2-
d1 5 p
naphtol, at 226 nm, for benzoic acid and 292 nm, for
where Pe¢ = u0 d1/D¢m is the Peclet number for the salicylic acid).
soluble sphere. The solubility of the solutes studied in water was
Now, by substituting the average mass transfer calculated from the steady state average concentration
coefficient, given by Eq. (10), into Eq. (4), the fol- of solute, cout, in the outlet stream (refrigerated to
lowing expression is obtained for the approximate room temperature), as c* = (1 + Q1 /Q )cout, where Q
validity criterion of theory developed above: and Q1 were the measured volumetric flowrates.
!
The spheres of solutes studied were prepared from
2
1 p p d1 p.a. grade material, which was molten and then poured
1þ 0þ [ ð11Þ into moulds made of silicone rubber. Wherever any
Pe0 Pe 5ðPe0 Þ1=3 ð1  eÞL
slight imperfections showed on the surface of the
Finally, with Eq. (11) we could predict the volumetric spheres, they were easily removed by rubbing with fine
flowrates that guarantee saturation in the outlet sand paper. Using callipers three measurements were
stream, Q = Pe¢p D2 e D¢m/(4d1). However, an made of the diameter of each sphere along three per-
important aspect to consider is the dependence of Q on pendicular directions.
the effective molecular diffusion coefficient, D¢m.
Fortunately, values of D¢m increase with temperature, 4 Results and discussion
and the value of D¢m, at room temperature or lower, is
a good estimate. The reproducibility of the experiments was tested by
independently repeating the measurement of solubility
under identical operating conditions, and in the vast
3 Experimental setup majority of cases the results of repeated measurements
of solubility did not differ by more than 8%.
Experiments were performed on the dissolution of Each experimental run gives a value of c* if the
spheres of benzoic acid, 2-naphthol and salicylic acid condition represented by Eq. (11) is observed. This
(6.0 mm of internal diameter), buried in beds of sand requirement meant that extremely low velocities of

123
 Heat Mass Transfer

Fig. 1 Sketch of
experimental set-up

liquid had to be observed in the experiments equations were programmed using Microcal Origin
(approximately 0.15 mm/s). software (version 7.0). For benzoic acid in water we
Experiments were performed with spheres 6 mm in propose the following equation (R = 0.990 and
diameter, buried in sand with an average grain size of p < 0.0001),
0.496 mm. As the experiments were carried out with
pressurized and deaerated water, it was possible to Table 1 Experimental solubilities at different temperatures and
their sample standard deviations (s)
work at temperatures of up 373 K. The value e = 0.40
was taken from references in the literature (see [11]). System T (K) c*exp (kg/m3) s (kg/mm3)
Table 1 summarizes the experimental solubilities
Benzoic acid–water 293.15 2.86 0.15
obtained, as well as the corresponding sample standard 303.15 4.14 0.22
deviations (s). The experimental solubility values ob- 313.15 5.94 0.14
tained for the three solutes in water are plotted as a 323.15 8.42 0.06
333.15 11.87 0.08
function of temperature in Figs. 2, 3 and 4.
338.15 13.76 0.14
The values of c* obtained for 2-naphthol in water are 2-Naphthol–water 293.15 0.61 0.03
in good agreement with the values of Moyle and Tyner 303.15 0.93 0.07
[8], McCune and Wilhelm [7] and Seidell [10], and 313.15 1.32 0.16
323.15 2.01 0.14
those for benzoic acid in water are in good agreement
333.15 3.01 0.10
with the values proposed by Ghosh et al. [5], Sahay 343.15 4.32 0.02
et al. [9] and others. For salicylic acid, only a few 353.15 6.45 0.14
previous values [4, 10] were found and they are shown 363.15 9.05 0.11
368.15 11.22 0.19
in Fig. 4. This highlights the usefulness of the present
Salicylic acid–water 293.15 1.50 0.08
work. 303.15 2.40 0.12
The results presented in Figs. 2, 3 and 4 suggest that 313.15 3.80 0.10
our data are consistent and accurate; they were taken 323.15 5.80 0.09
333.15 8.70 0.13
as reference data to help identify mathematical
343.15 13.00 0.08
expressions for the prediction of c*. The regression

123
Heat Mass Transfer

14 16
This work This work ln( c*) = −12 .2365 + 0.0432 × T (K)
Ghosh et al. (1991) 14 Eisenberg et al. (1955)
12 Sahay et al. (1981) Seidell (1941)
Kumar et al. (1978)
Dunker (1964) 12
10 Steele and Geankoplis (1959)
Eisenberg et al. (1955) 10
c * (kg/m )

c* (kg/m )
3
3

8 Seidell (1941)
8
6
6

4 4

2 2
ln( c*) = −9.0971 + 0.0346 × T (K)
0
0 270 280 290 300 310 320 330 340 350
270 280 290 300 310 320 330 340
T (K)
T (K)
Fig. 4 Solubility of salicylic acid in distilled water at different
Fig. 2 Solubility of benzoic acid in distilled water at different temperatures
temperatures

lnðc
Þ ¼ 9:0971 þ 0:0346  TðKÞ ð12Þ

and the data shown in Fig. 2 are within 5% of this line.
For 2-naphthol in water we propose the following
equation (R = 0.995 and p < 0.0001),
lnðc
Þ ¼ 12:0355 þ 0:0394  TðKÞ
and the data shown in Fig. 3 are within 7% of this line.
Finally, for salicylic acid in water we propose the
following equation (R = 0.998 and p < 0.0001), with
an error lesser that 5% (see Fig. 4),
lnðc
Þ ¼ 12:2365 þ 0:0432  TðKÞ
The agreement between our results and other pub-
lished data suggests that the proposed method is
accurate. However, it is important to remember that,
for higher solubility solutes, natural convection near
the surface of the dissolving solids may become sig-
nificant, thus invalidating the method.
5 Conclusions
The main conclusion from this work is that the
experimental technique described for measuring the
solubilities of a solute in a liquid, at different temper-
ð13Þ atures, is perfectly suitable and easy to use. The results
show that it is possible to obtain good results for sol-
ubility values, using simple procedures.
The experimental values obtained for c* of 2-naph-
tol in water, benzoic acid in water and salicylic acid in
water, over a range of temperatures above ambient,
are in good agreement with the values given in the
ð14Þ
literature.
Acknowledgments The author wishes to thank Fundação para
a Ciência e a Tecnologia for the Grant N SFRH/BPD/11639/
2002.
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Heat Mass Transfer
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