J. Chem.

Thermodynamics 74 (2014) 263268

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Diffusion of sodium alginate in aqueous solutions at T = 298.15 K

Ana C.F. Ribeiro a,, Ins Fabela b, Abilio J.F.N. Sobral a, Luis M.P. Verissimo a, Marisa C.F. Barros a,b,
M. Melia Rodrigo b, Miguel A. Esteso b,
a
b

Department of Chemistry, University of Coimbra, 3004 535 Coimbra, Portugal

U.D. Qumica Fsica, Facultad de Farmacia, Universidad de Alcal, 28871 Alcal de Henares, Madrid, Spain

a r t i c l e

i n f o

Article history:
Received 20 January 2014
Received in revised form 19 February 2014
Accepted 20 February 2014
Available online 28 February 2014
Keywords:
Mutual diffusion coefcient
Sodium alginate
Polyelectrolyte solutions
Viscosity
Density

a b s t r a c t
Taylor dispersion technique was used for measuring mutual diffusion coefcients of sodium alginate
aqueous solutions at T = 298.15 K, by using as carrier stream solution both pure water and solutions of
this polyelectrolyte at a slightly different concentration. The limiting values found at innitesimal ionic
strength, D0, were determined by extrapolating to c ? 0. These studies were complemented by molecular
mechanics calculations. From the experimental data, it was possible to estimate both the limiting conductivity and the tracer diffusion coefcient values for the alginate anion, and the hydrodynamic radius
of the sodium alginate (NaC6H7O6), as well as to discuss the inuence of the kinetic, thermodynamic and
viscosity factors on the diffusion of sodium alginate in aqueous solutions at nite concentrations. Thus,
the aim of our innovative research is to contribute to a better understanding of the structure and the thermodynamic behavior of these polymeric systems in solution and supplying the scientic and technological communities with data on these important parameters in solution transport processes.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
It is well known that in recent decades there has been a marked
increase on the interest to understand the physicochemical properties of the polysaccharides in aqueous solutions, which play a fundamental role in human nutrition. The importance of this subject
lies in their several applications, e.g., in food industry [1], as gelling
or thickening agents, serving their complexes with proteins as
important materials in a variety of food delivery applications due
to they improve the ingredient performance and shelf-life stability
in many food systems. They are also important components in formulations for pharmaceutical, medical and biomedical applications [2], and, also they have been used in many other industrial
applications, such as in packaging, coating or protective lms for
the shipping and in controlled delivery of drugs [3], as well as
biosorbent of heavy metals from wastewater [4].
Among carbohydrates, we have been particularly interested in
sodium alginate, an electro-active bio-polymer extracted from
the cell walls of brown algae (1) (gure 1) [5]. This carbohydrate

Corresponding authors. Tel.: +351 239 854460; fax: +351 239 827703
(A.C.F. Ribeiro). Tel.: +34 91 885 48 61; fax: +34 91 885 47 63 (M.A. Esteso).
E-mail addresses: anacfrib@ci.uc.pt (A.C.F. Ribeiro), fabela_cbr@hotmail.com
(I. Fabela), asobral@ci.uc.pt (A.J.F.N. Sobral), luisve@gmail.com (L.M.P. Verissimo),
marisa.barros@gmail.com (M.C.F. Barros), mmelia.rodrigo@uah.es (M.M. Rodrigo),
miguel.esteso@uah.es (M.A. Esteso).
http://dx.doi.org/10.1016/j.jct.2014.02.014
0021-9614/ 2014 Elsevier Ltd. All rights reserved.

is a linear polysaccharide (NaC6H7O6)n of (14) linked a-L-guluronate (G) and b-D-mannuronate (M) residues arranged in a nonregular, block wise pattern along the linear chain.
However, the physical properties and behavior of these chemical systems are poorly known, even though this is a prerequisite to
obtain an adequate understanding. In fact, there are in the literature a few studies on the transport of alginate in aqueous media
(e.g., [69]). Our research group has already measured some mutual diffusion coefcients of sodium alginate in dilute aqueous
solutions by using a conductimetric technique [10].
Having in mind, that it is very common in the scientic literature to nd misunderstandings concerning the meaning of the
parameter diffusion coefcient, it is necessary to distinguish
these two processes of transport: self-diffusion DT (intradiffusion,
tracer diffusion, single ion diffusion, ionic diffusion) and mutual
diffusion D (interdiffusion, concentration diffusion, salt diffusion)
[11]). Many techniques are used to study diffusion in aqueous solutions. Methods such as NMR, polarographic, and capillary-tube
techniques with radioactive isotopes measure self-diffusion coefcients (intradiffusion coefcients). However, for bulk ion transport the appropriate parameter is the mutual diffusion
coefcient, D. Relationships derived between intradiffusion and
mutual diffusion coefcients, DT and D, have had limited success
and consequently mutual diffusion coefcients are much needed.
We have been particularly interested in the characterization of
mutual diffusion of sodium alginate in aqueous dilute solutions at

264

A.C.F. Ribeiro et al. / J. Chem. Thermodynamics 74 (2014) 263268

A) with an IEEE interface. Binary diffusion coefcients were evaluated by tting the dispersion equation

Vt V 0 V 1 t V max t R =t1=2 exp12Dt  t R 2 =r 2 t;

FIGURE 1. Sodium alginate general structure [5].

T = 298.15 K. In this work, we propose to extend our studies of

some transport properties using different techniques, already
started with some concentrations of alginate to other concentrations [10], and complement them with viscosities and densities
measurements, and molecular mechanics calculations.
From diffusion coefcient at innitesimal concentration, the
limiting ionic conductivity, the tracer diffusion coefcient and the
hydrodynamic radius of the unit of sodium alginate (NaC6H7O6)
are computed. Moreover, for nite concentrations, the inuence
of kinetic, thermodynamic and viscosity on the behavior diffusion
of alginate in aqueous solutions is also discussed.
Our main goal is to reach a better understanding of the structure of these electrolyte solutions, the behavior of the alginate
ion in solution as well as to supply the scientic and technological
communities with data on these important parameters in solution
transport processes and, consequently, to give a useful tool for the
structural interpretation of these systems.
2. Experimental
2.1. Materials
Sodium alginate was used as received (table 1). Milli-Q water
(from A10 Millipore) was used as solvent.
For the diffusion measurements, solutions were freshly prepared in calibrated volumetric asks (uncertainty concerning their
compositions within 0.1 %). For viscosity and density measurements, they were prepared by direct weighing both the solute
and the solvent in a Mettler AE 240 analytic balance with a precision of 0.0001 g (uncertainty in their composition within 0.02 %).
The pH for the fresh solutions was measured as equal to
(5.080 0.030) by using a PHM 240 Radiometer pH meter with an
Ingold U457-K7pH conjugated electrode and u(pH) = 0.02.

to the detector voltages. The additional tting parameters were the

mean sample retention time tR, peak height Vmax, baseline voltage
V0, and baseline slope V1.
The concentrations of the injected solutions (c Dc) and the
carrier solutions (c) differed by 0.150 g  L1 or less. Solutions of
different composition were injected into each carrier solution to
conrm that the measured diffusion coefcients were independent
of the initial concentration difference and therefore represented
the differential value of D at the carrier-stream composition.
2.2.2. Viscosity measurements
Viscosity measurements were performed with an Ubbelohde
viscometer, calibrated from water, immersed into a water-thermostat bath which temperature was controlled within 0.02 K by
using a digital thermometer. The arithmetic mean value of four
ow times for each solution was taken to calculate such viscosity
values. The measurement of the efux time was carried out with
a stopwatch with a resolution of 0.01 s. The uncertainty of these
values was less than 1%.
2.2.3. Density measurements
The densities of sodium alginate aqueous solutions at
T = 298.15 K were determined by using an Anton Paar DMA
5000 M densimeter. This equipment has a precision of
1  106 g  cm3 and an accuracy of 5  106 g  cm3 in ranges
of (090) C and (01.0) MPa. The uncertainty of the results
obtained is estimated to be less than 0.001%.
2.2.4. Molecular mechanics studies
Energy minimization was obtained in Hyperchem 8 (Hypercube, Inc. USA) using the molecular mechanics geometry optimization MM+ force eld, under a conjugated gradient (PolackRibiere)
with a nal RMS gradient of 0.42 kJ  mol1, in vacuum. The calculations were performed in a HP-Z620 workstation under Windows
7.
3. Results and discussion

2.2. Methods
2.2.1. Diffusion measurements
The Taylor dispersion method for measuring diffusion coefcients is based on the dispersion of a very small amount of solution
(0.063 cm3) injected into a laminar carrier stream of pure solvent
or solution of slightly different composition owing through a long
capillary tube of (3.2799 0.0001) 103 cm in length (e.g., [1219]
and a radius of (0.05570 0.00003) cm.
The ow rate was 0.23 cm3  min1 (by using a Gilson model
Miniplus 3 peristaltic pump) with a retention time of about
8  103 s by using a 6-port Teon injection valve (Rheodyne, model
5020). The dispersion tube and the injection valve were kept at
T = (298.15 K 0.01 K) in an air thermostat.
Dispersion of the injected samples was monitored using a differential refractometer (Waters model 2410) at the outlet of the
dispersion tube. Detector voltages, V(t), were measured at accurately timed 5 s intervals with a digital voltmeter (Agilent 34401

TABLE 1
Sample description.
Chemical name

Lot

Source

Mass fraction purity

Sodium alginate

4114

JMG Santos, Lda, Portugal

0.98

3.1. Tracer diffusion coefcient of the alginate anion and mutual

diffusion coefcient of sodium alginate at innitesimal concentration
Table 2 gives the experimental values for the mutual diffusion
coefcient when the carrier stream is pure water, at different
concentrations, as well as the value at innitesimal ionic
strength, D0, estimated by extrapolating to c ? 0. This value,
D0 = 0.773  109 m2  s1, is in good agreement with that
(D0 = 0.778  109 m2  s1) obtained as an adjustable parameter
from the application of the polynomial equation in c to our
experimental data previously reported from the conductimetric
technique [10].
By using the Nernst-Hartley equation [11,20]

D0



R T jZ c j jZ a j k0c k0a
;
jZ c Z a j
k0c k0a
F2

where D0 value is the mutual diffusion coefcient for the sodium

alginate at innitesimal ionic strength (table 2), R is the gas
constant in J  K1  mol1, T is the absolute temperature, F is the
Faraday constant, Zc and Za, and k0c and k0a (in S  m2  mol1) represent the algebraic valences and the equivalent conductance at innitesimal concentration of Na+ and alginate ions, respectively, and
taking the limiting ionic conductivity of sodium ion as equal to

265

A.C.F. Ribeiro et al. / J. Chem. Thermodynamics 74 (2014) 263268

TABLE 2
Mutual diffusion coefcients D, of sodium alginate aqueous solutions at different
concentrations and the respective standard deviations, SD, obtained from the Taylor
technique by using pure water as carrier stream, at T = 298.15 K and at atmospheric
pressure.
c/(g  L1)
0.0010
0.0030
0.0050
0.0075
0.0100

TABLE 3
Mutual diffusion coefcients, D, of sodium alginate in aqueous solutions at different
concentrations, c, and the respective standard deviations, SD, obtained either by the
conductimetric or by the Taylor techniques (by using carrier stream solutions of
different concentrations) at T = 298.15 K and at atmospheric pressure.

(D SD)/(109 m2  s1)a

0.754 0.020
0.718 0.018
0.670 0.018
0.635 0.018
0.580 0.018
D0 = 0.773  109 m2  s1b

0.0010
0.0030c
0.0050b
0.0075c
0.0100b
0.1000b
0.3000b
0.5000b

D is the mean diffusion coefcient value from 46 experiments and SD is the

standard deviation of that mean, for sodium alginate supplied by JMG Santos, Lda,
Portugal (Lote 4114). u(c) = 0.0001 g  L1, u(D) = 0.02  109 m2 s1; u(T) = 0.01 K.
b
Extrapolated value obtained from the D least-squares for the total number of
injections, where D/(109 m2  s1) = 0.773  19.126c (R2 = 0.995).

50.10  104 S  m2  mol1 [20], we estimated k0a , being equal to

20.45  104 S  m2  mol1.
From this value, and assuming that the limiting tracer diffusion
coefcients of this alginate ion D0T , can be estimated through the
Nernst equation (equation (3)),

D0 Z a F 2
k0a T
;
RT

limiting tracer diffusion coefcient value, D0T 0:544  109 m2s1,

was obtained for the alginate ion.
Support for our D0T value comes from the estimation of the same
parameter obtained by Aoki et al. [9], but determined by the use of
time-evolution of diffusing dye. In fact, their value
(D0T 0:5  109 m2s1) is very close to ours and, according to
these authors, it was quite independent of the viscosity and very
close to the D values usually found for organic molecules in water.
Our calculation shows that the mutual diffusion coefcient of
the sodium alginate at innitesimal ionic strength is signicantly
larger (1.4 times) than that the corresponding tracer diffusion coefcient for the alginate anion, what characterizes the electrostatic
dragging effect of the sodium ions on the alginate ions.
3.2. Inuence of the kinetic and the thermodynamic factors on the
behavior diffusion of alginate in aqueous solutions at nite
concentrations
Table 3 gives the average values of the mutual diffusion coefcient, D, (that is, by using nite concentrations of the carrier stream
solutions) determined by both the Taylor and the conductimetric
techniques. As usual, good reproducibility was observed, within
3% (e.g., [12]). From the values in table 3, we have obtained a limiting value of D0/(109 m2  s1) = (0.780 0.002), which in in very
good accordance (<1%) with that obtained in the case of the use of
pure water as carrier stream solution.
The interpretation of the diffusion behavior of this aqueous system (sodium alginate) can be done on the basis of the Onsager
Fuoss model (equation (4)), suggesting that D is a product of both
a kinetic, FM (or molar mobility coefcient of a diffusing substance)
and a thermodynamic factors, FT (FT = col/oc), where l represents
the chemical potential of the solute. Thus, two different effects
can control the diffusion process: the ionic mobility and the gradient of the Gibbs free energy,

DOF F M  F T ;

where

FM M



jZ c j jZ a j R T
D0 D1 ;
jZ c Z a j
c

(D SD)/(109 m2  s1)a

c/(g  L1)

0.782 0.008
0.781 0.006
0.780 0.007
0.775 0.008
0.772 0.007
0.752 0.001
0.710 0.003
0.663 0.003

D is the mean diffusion coefcient value from 46 experiments and SD is the

standard deviation of that mean, for sodium alginate supplied by JMG Santos, Lda,
Portugal (Lote 4114).
b
D values obtained from the conductimetric technique [10].
c
D values obtained from the Taylor technique (this work). u(D) = 0.02  109
m2  s1; u(T) = 0.01 K.

and

FT

1c


@ ln y
;
@c

being c the concentration in mol  m3, y the mean molar activity

coefcient of the solute, the other symbols having their usual meaning, and M, in mol2  s  m3  kg1, is given by

k0c k0a

N 2A e20

ma jza jk0c mc jzc jk0a

!
c DM 0 ;

where the rst-order electrophoretic term, is given by

2

DM 0 

c
jza jk0c  jzc jk0a
NA jz jm k0 jz jm k0 2
c c a
a a c

mc ma
k
;
mc ma 6p g0 1 ka

where g0 is the viscosity of water in Pa  s, NA is the Avogadros constant, e0 is the proton charge in coulombs, mc and ma are the stoichiometric coefcients, k is the reciprocal average radius of ionic
atmosphere, in m1 (see e.g., [21]), a is the mean distance of closest
approach of ions in m, (we used a = 5.0  1010 m) and the other
symbols have their usual meaning.
From our measurements of diffusion coefcients, D, and considering equation (4), we have estimated the thermodynamic factor
values for the interval of concentrations where, in general, these
equations are valid (i.e., c 6 0.01 g  L1, table 4).
The values for D1, shown in table 4, are very small and, consequently, FM is almost constant for the concentration range studied.
In fact, these values of D1 for the studied interval of concentrations
and for different molecular mass of alginate [3,8] only contribute a
0.1 %, approximately, to the decreasing of D0.
The decrease of the diffusion coefcients, D, and also of the gradient of the free energy with concentration, FT, (fourth column in
table 4) leads us to conclude that this behavior observed for the sodium alginate in aqueous solutions at T = 298.15 K appears to be
affected by the presence of aggregated species (this fact is conrmed by molecular mechanic calculations), which have a lower
mobility than the alginate monomers due to their size. Considering
our experimental conditions (i.e., dilute solutions) and assuming
that parameters such as viscosity, dielectric constant and hydration, (factors not taken into account by this model) do not change
with concentration, we can conclude that the variation in D is
mainly due to the variation of FT (attributed to the non-ideality
in thermodynamic behavior) and, in a lesser amount, to the electrophoretic effect in the mobility factor, FM (table 4).

266

A.C.F. Ribeiro et al. / J. Chem. Thermodynamics 74 (2014) 263268

TABLE 4
Mobility factor, FM, and thermodynamic factor, FT, of sodium alginate calculated from our experimental D values and from equations (4)(8) at T = 298.15 K and at atmospheric
pressure.

a
b
c
d

c/(g  L1)

D1/109 m2  s1a

FM/109 m2  s1b

FT/109 m2  s1c

F0 T/109 m2  s1d

0.0000
0.0010
0.0030
0.0050
0.0075
0.0100

0.000
7.7  104
8.5  104
9.3  104
1.0  103
1.08  103

0.773
0.773
0.773
0.773
0.773
0.773

1.000
1.012
1.010
1.009
1.000
0.999

1.000
1.028
1.036
1.044
1.047
1.058

D1 represents the electrophoretic correction for the molecular mass of the alginate M = 375 kDa [3]. This parameter is estimated by using equations (5), (7), and (8).
FM = (D0 + D1), where D0 is the diffusion coefcient at innitesimal concentration.
FT = Dexp/FM.
F0 T = Dexp gr/FM, being gr the relative viscosity (equation (9)) of this work [11,20].

3.3. Inuence of the viscosity factor on the behavior diffusion of

alginate in aqueous solutions at nite concentrations

TABLE 5
Density, d, and viscosity, g, data for sodium alginate aqueous solutions at T = 298.15 K
and at atmospheric pressure.

The diffusion of this polyelectrolyte in aqueous solutions may

also depend on the viscosity change in the solution (negligible in
dilute solution, but becoming important when the concentration
increases) and, consequently, the estimated values of FT in the
absence of this viscosity-effect (table 4) may show large deviations
from the real values. Thus, on the basis of Gordons (possessive
genitive) equation [11,20].

0.00100
0.00500c
0.01396
0.10667
0.26713
0.50730
1.01678
4.98590
7.49026
9.98762

g0
;
g

DG DOF

c/(g  L1)

d/(g  cm3)

(106 Sd)a

g/(103 Pa  s)

103 Sgb

0.997060
0.997100
0.997106
0.997144
0.997220
0.997340
0.997681
0.999809
1.001365
1.002704

1.2
1.3
1.4
1.3
1.4
2.1
1.2
2.2
2.0
2.9

0.903
0.921
0.914
1.337
2.034
2.706
4.037
13.74
37.54
70.14

0.9
1.0
0.8
0.7
0.9
0.8
0.9
0.5
0.7
0.7

where g0 and g represent the viscosity of water and the solution,

respectively, and DOF is the diffusion coefcient obtained by the
OnsagerFuoss equation (equations (4)(8)), we have estimated a
new FT values (last column in table 4) as equal to:

F 0T


FT

3.4. Hydrodynamic radius of the unit of sodium alginate (NaC6H7O6)

g
:
g0
F 0T

Sd stands for the standard deviation of the density measurements.

Sg stands for the standard deviation of the viscosity measurements.
u(c) = 0.0001 g  L1; u(g) = 5  104 mPa  s; u(T) = 0.01 K.
c
Interpolated values.
b

10

These
values are, obviously, higher than those of FT calculated from equation (6) becoming the discrepancies more signicant when the concentration increases. This fact of increasing of
the thermodynamic factor makes the contribution of the FM factor
to be even smaller when the concentration of sodium alginate
becomes higher.
Despite of this treatment so far has been phenomenological,
and therefore, the dependence of D and FT on factors such as the
nature of the ion and different types of interactions cannot be theoretically understood, we may interpret that behavior on the basis
of interactions water/sodium alginate. This hypothesis is supported by molecular mechanics calculations. In fact, assuming
the possibility that some water molecules are tightly bound to certain ions, they cannot be effective in dissolving further ions added.
Therefore, as the concentration of alginate increases, the amount of
effective water decreases, and the activity coefcient increases.
The hydration of these ions reduces the amount of free solvent
from the present for a given stoichiometric concentration, then
the effective concentration increases and the activity coefcient
must also increase. In our case, this increasing is not compensated
for the decreasing due to interactions sodium cation-alginate anion, and of course it is not unreasonable that the activity coefcient
and, consequently, the thermodynamic factor should rise above the
unity.
The experimental viscosity values of sodium alginate aqueous
solutions used to calculate the F 0T factor, for the concentration
range here studied, are collected in table 5 together with the density values for the same concentrations. These data were linearly
tted by using a least-squares regression method to obtain their
dependence with concentration.

As is well-known, the StokesEinstein equation (equation (11))

[11] can be used to extract the size of solute molecules treated as
Brownian particles immersed in a continuum uid, provided that
the solute particle is at innitesimal concentration and it is large
compared to the solvent molecules. Equation (11) (where kB is
the Boltzmann constant) establishes a link between the hydrodynamic radius of an equivalent spherical particle, Rh, and its selfdiffusion coefcient at innitesimal concentration, D0T , also known
as the tracer diffusion coefcient:

D0T

kB T
:
6 p g 0 Rh

11

Thus, the Stokes radius of the alginate anion estimated from this
equation, which assumes that the particles are perfectly spherical
and are solely subject to solvent friction (table 6) is equal to
0.451 nm, under innitesimal ionic strength conditions, which is
close to the value estimated for the radius of a monomeric unit
of alginate, obtained by molecular mechanic simulations

TABLE 6
Hydrodynamic radius, Rh, of sodium alginate at solutions of the different concentrations, c, and different viscosities, g, at T = 298.15 K and at atmospheric pressure.
c/(g  L1)

1016 (Dg/T) /(m  s1  kg  K1)

Rh/nm

0.00100
0.00300
0.00500
0.00750
0.01000
0.10000
0.20000
0.30000

23.72
23.88
24.14
24.23
24.41
31.85
44.84
51.09

0.309
0.307
0.304
0.302
0.300
0.230
0.163
0.143

A.C.F. Ribeiro et al. / J. Chem. Thermodynamics 74 (2014) 263268

267

FIGURE 2. (a) 5 Units system of sodium alginate, after MM+. (b) 5 Units system of alginic acid, after MM+.

FIGURE 3. (a) Isopotential 3D map for 5 units of sodium alginate (positive (lighter) and negative (dark) zones). (b) Isopotential 3D map for 5 units of alginic acid.

(i.e., 0.490 nm, see section 3.5) from the volume of this bare ion.
These differences may be justied if we consider the limitations of
Stokes relation. Although this relationship is only approximated
(arising from the acceptance that both the solute kinetic species
and the solvent are not structured, together with the assumption
that viscosity is the only responsible of the diffusivity reduction),
it can be used to estimate the radius of the moving species, since alginate ions are large enough when compared with water molecules.
By taking into account the Stokes equation (equation (11)) and
replacing the water viscosity by the viscosity of the solutions, the
values of the effective hydrodynamic radius Rh of alginate are estimated as a function of the concentration of the solute and collected
in table 6. The signicant differences between each one and the
innitesimal value for the effective hydrodynamic radii Rh (approximately 30%) come again to support the importance that the viscosity effect has on the properties of the alginate solutions.
However, as it can be observed, for c 6 0.01 g  L1 the maximum
variation observed in these Rh values, is around 3%. Furthermore,
this table 6 gives the (Dg/T) values, whose variation observed for
c 6 0.01 g  L1 is relatively small (less than 4%), and be close to
the imprecision of the diffusion measurements (<3%).
3.5. Molecular mechanics analysis
After MM+ geometry optimization, by energy minimization in
vacuum, we observed that the 5 monomers system model of
sodium alginate adopts a curved/helical conformation, probably
due to the joining effect of the sodium cations that move along
the structure in order to be coordinated by more than one carboxylate group, as can be shown in gure 2.
Just for comparison, the alginic acid at pH 7 (our pH value
obtained for c = 0.01 g  L1), under the same geometry optimization process, adopts a linear conformation as can be also seen in
gure 2. That point out to a determinant effect of the sodium cations on the conformation of the polymer, but this is just a trivial
observation since the results show that the alginic acid coordinates
and folds around cations quite easily.
The isopotential 3D map for the sodium alginate shows more
important differences between it and the parent alginic acid (gure
3). In fact, the 5 unit model of sodium alginate shows a strong

negative potential that has just small positive islands in the periphery, due to the sodium cations. This fragment of polymer is just a
model of the real polymer and caution need to be taken in comparing it to the laboratory experiments, but its behavior is adequate to
a polyelectrolyte with a negative backbone surrounded by sodium
cations, as can be seen in gure 3. This kind of structure usually
presents strong ion/polymer interaction and also strong water/
polymer interactions.
4. Conclusions
By using the Taylor technique, it was possible to determine
experimental mutual diffusion coefcient values, D, for aqueous
solutions of sodium alginate at T = 298.15 K, at different concentrations of the solute, in two different ways: by using both pure water
and the same aqueous solution at slightly different concentrations
as the carrier stream solution. The limiting values found at innitesimal ionic strength, D0, from both set of data were coincident
(differences less than 1%). This study was complemented with
molecular mechanics calculations.
Regarding the results obtained for the diffusion coefcient, possible electrostatic interactions have to be present (sodium cation/
alginate anion and water/sodium alginate), resulting in a decrease
in the diffusion coefcient values when the solute concentration
increases. As an estimating purpose to study the behavior of the
diffusion coefcients of electrolytes in aqueous solutions, and spite
of their limitations, the OnsagerFuoss theory is a useful tool to
analyze the structure of these systems. From it, we can conclude
that the variation in D is mainly due to the variation of the thermodynamic factor, FT (attributed to the non-ideal behavior), and, to a
lesser extent, to the electrophoretic effect in the mobility factor, FM.
Viscosity values for these sodium alginate aqueous solutions
were also measured to consider the inuence of this parameter
on the D values. Such an inuence of the viscosity factor was put
in evidence especially when the solute concentration becomes relatively high.
All this information, together with some other computed
parameters for the alginate anion, that is, the limiting ionic conductivity and the tracer diffusion coefcient value, DT, besides
the hydrodynamic radii of the sodium alginate, permit us to

268

A.C.F. Ribeiro et al. / J. Chem. Thermodynamics 74 (2014) 263268

provide the usefulness of the transport data to model the diffusion

for in vivo applications.
Acknowledgments
Financial support from FCT (FEDER)-PTDC/AAC-CLI/098308/
2008 and PTDC/AAC-CLI/118092/2010 is gratefully acknowledged.
MCFB is grateful for the SFRH/BD/72305/2010 grant. One of the
author (A.C.F.R.) is grateful for the Sabbatical Leave Grant (BSAB)
from Fundao para a Cincia e Tecnologia. M.M.R. is grateful to
the University of Alcal for the nancial assistance (Mobility
Grants for Researchers).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jct.2014.02.014.
References
[1]
[2]
[3]
[4]
[5]

D. Gmez-Diaz, J.M. Navaza, J. Food Eng. 56 (2003) 387392.

I.L. Shih, Mini Rev. Med. Chem. 10 (2010) 13451355.
A.M.F. Lima, V. Soldi, R. Borsali, J. Braz. Chem. Soc. 20 (2009) 17051714.
A. Karagunduz, D. Unal, Adsorption 12 (2006) 175184.
T. Andersen, B.L. Strand, K. Formo, E. Alsberg, B. Christensen, Carbohydr. Chem.
37 (2012) 227258.

[6] H.H. Paradies, D. Wagner, R.W. Fischer, Ber. Bunsenges. Phys. Chem. 100 (1996)
12991307.
[7] A. Straatmann, A.W. Borchard, Eur. Biophys. J. 32 (2003) 412417.
[8] D. Zhong, X. Huang, H. Yang, R. Cheng, Carbohydr. Polym. 81 (2010) 948952.
[9] K. Aoki, B. Wang, J. Chen, T. Nishiumi, Electrochim. Acta 83 (2012) 348353.
[10] A.C.F. Ribeiro, A.J.F.N. Sobral, S.M.N. Simes, M.C.F. Barros, V.M.M. Lobo,
A.M.T.D.P.V. Cabral, F.J.B. Veiga, C.I.A.V. Santos, M.A. Esteso, Food Chem. 125
(2011) 12131218.
[11] H.J.V. Tyrrell, K.R. Harris, Diffusion in Liquids: A Theoretical and Experimental
Study, Butterworths, London, 1984.
[12] M.C.F. Barros, A.C.F. Ribeiro, A.J.M. Valente, V.M.M. Lobo, A.M.T.D.P. Cabral,
F.J.B. Veiga, C. Teijeiro, M.A. Esteso, Int. J. Pharm. 447 (2013) 293297.
[13] J. Barthel, H.J. Gores, C.M. Lohr, J.J. Seidl, J. Solution Chem. 25 (1996) 921935.
[14] R. Callendar, D.G. Leaist, J. Solution Chem. 35 (2006) 353379.
[15] A.C.F. Ribeiro, C.I.A.V. Santos, V.M.M. Lobo, A.M.T.D.P.V. Cabral, F.J.B. Veiga,
M.A. Esteso, J. Chem. Thermodyn. 41 (2009) 13241328.
[16] A.C.F. Ribeiro, C.I.A.V. Santos, V.M.M. Lobo, M.A. Esteso, J. Chem. Eng. Data 55
(2010) 26102612.
[17] A.C.F. Ribeiro, C.I.A.V. Santos, A.J.M. Valente, O.S. Ascenso, V.M.M. Lobo, H.D.
Burrows, A.M.T.D.P.V. Cabral, F.J.B. Veiga, C. Teijeiro, M.A. Esteso, J. Chem. Eng.
Data 53 (2008) 755759.
[18] A.C.F. Ribeiro, C.I.A.V. Santos, V.M.M. Lobo, A.M.T.D.P.V. Cabral, F.J.B. Veiga,
M.A. Esteso, J. Chem. Eng. Data 54 (2009) 115117.
[19] A.C.F. Ribeiro, S.M.N. Simes, V.M.M. Lobo, A.J.M. Valente, M.A. Esteso, Food
Chem. 118 (2010) 847850.
[20] R.A. Robinson, R.H. Stokes, Electrolyte Solutions, second ed., Butterworths,
London, 1959.
[21] H.S. Harned, B.B. Owen, The Physical Chemistry of Electrolytic Solutions, third
ed., Reinhold Pub. Corp., New York, 1964.

JCT 14-42