In the Laboratory

Kinetics of the Osmotic Hydration of Chickpeas

Gabriel Pinto*
Departamento de Ingeniería Química Industrial y del Medio Ambiente, E.T.S.I. Industriales,
Universidad Politécnica de Madrid, 28006 Madrid, Spain; *[email protected]

Ali Esin
Department of Food Engineering, Middle East Technical University, Ankara 06531, Turkey

It is widely accepted that presenting real-life examples periment is to perform it with a biology or physics instruc-
and activities in the classroom increases students’ enthusiasm tor, as an interdisciplinary activity. Measurement, graphing
to learn and understand the principles in chemistry (1–3) of data, and modeling are all combined in this experience.
and science (4–7) in general. This article is a continuation
of a program intended to help chemistry instructors make Theory
connections between students’ everyday experiences and
chemical principles taught in the classroom (8–14). A Mass transfer is the molecular scale movement of a sub-
straightforward experience introducing students to several stance through a medium under a concentration gradient in
concepts, found in university-level freshmen and sophomore the direction of decreasing concentration. The rate of the
chemistry, physics, calculus, and biology classes, allows the transfer depends on the degree of departure of the system
quantitative explanation of a process familiar to students: the from equilibrium and ends when equilibrium is attained. For
swelling of chickpeas in water. example, when a wet piece of cloth is placed in a stream of
Chickpea (Cicer arietinum) is a widely-used plant of the air, at the surface of the cloth, molecules of water vaporize
leguminous family. Most students know that chickpeas (and and diffuse through into the main portion of the air stream,
other legumes or fruits, such as dried plums) swell in water. where they are carried away and the cloth dries. The process
As water enters the chickpea, the concentrated solution within ends when equilibrium is attained between the concentra-
the chickpea is diluted. Conversely, a cucumber shrinks into tion of water vapor in the air and the concentration of water
a pickle in brine because water leaves the comparatively di- vapor at the surface of the cloth.
lute solution within the cucumber. The study of water Diffusion is the net movement of molecules from a re-
absorption by dried legumes is pertinent because this is a step gion of greater concentration to a region of lesser concentra-
in their industrial preparation (15, 16) and could serve as an tion in search of equilibrium. Across a membrane, water
example to make students aware of questions arising in the moves in two directions, not only one direction. At equilib-
food industry. rium, the net result is a decrease of concentration in the more
As noted by Konak (17), skins around fruit and veg- concentrated region and an increase in the concentration of
etables act as osmotic membranes. An adequate explanation the less concentrated region. We call this process osmosis
of osmosis can be found in most chemistry textbooks (18), when diffusion takes place across a membrane. Thus osmo-
where important and varied practical applications of this phe- sis is the movement of water across a semipermeable mem-
nomenon, such as desalination of saltwater by reverse osmo- brane from an area of higher concentration of water to an
sis, are cited. Unfortunately, in chemistry courses osmosis is area of lower concentration of water. Owing to the complex
usually reduced to the calculation of the osmotic pressure of morphology of plant tissues, mass transfer in osmotic hydra-
hypothetical solutions. A simple demonstration model of os- tion or rehydration of cellular plant foods, such as fruits and
mosis was discussed by Morse (19) in this Journal. vegetables, involves several physical effects of transport mecha-
In a general chemistry course, this experiment could nism, such as osmosis, diffusion, hydrodynamic mechanism
serve as an introduction to the concepts of osmosis, mass penetration, and others (20).
transfer, and diffusion. The simplicity of the procedure lies Under isothermal conditions, the kinetics of moisture
in the fact that only mass measurements are taken over time, absorption by foods, such as cereal grains or legumes, can be
so hydration is directly observed and monitored. In this ex- modeled by the Peleg equation. Peleg (21) first introduced
periment students measure the rate at which water is absorbed the model to describe moisture absorption by milk powder
by dried chickpeas. Measurements are made at several tem- and rice. This model may be represented by the following
peratures, using water and salt solutions. By calculating the equation,
initial hydration rate at different temperatures, an Arrhenius- t
type activation energy can be estimated. M (t ) = M 0 + (1)
The proposed experiment is inherently safe and inex- k 1 + k2t
pensive to do. It can be done in the laboratory or, at least
partially, as a take-home project in a kitchen, given the fact where M(t) and M0 are the moisture content of the solid
that the materials needed, such as a balance, are easy to ob- (w兾w) at times t > 0 and t = 0, respectively, and k1 and k2 are
tain or frequently found at home. Although an analytical bal- rate constants. According to this model, the equilibrium mois-
ance was used in the laboratory, students performing the ture, ME, is asymptotically attained; that is, when t → ∞:
experiment at home would not need a balance that weighs 1
to as many decimal points. Another possibility for this ex- ME = M0 + (2)
k2

532 Journal of Chemical Education • Vol. 81 No. 4 April 2004 • www.JCE.DivCHED.org

 In the Laboratory

Similarly, the instantaneous absorption rate, dM(t)兾dt, is

given by,

d M (t ) k1
= 2 (3)
dt (k1 + k2 t )

and the initial rate, that is, the rate at t = 0, is given by 1兾k1.
A general feature of mathematical relations such as eq 1 is
that they can be transformed to a linear relationship in the 0.0 h 1.5 h 3.0 h 4.5 h
form:
t Figure 1. Appearance of five chickpeas after different times of soak-
= k1 + k2 t (4) ing in distilled water at 20 ºC. Coins of one dime (United States),
M (t ) − M 0 2 cents (European Union), and 10 kopecs (Russia) were included
for comparison.
In this experiment, as a result of the negligible initial equi-
librium moisture content of the chickpeas at room condi-
tions, we assume M0 = 0 and eqs 1–4 may be simplified.
This model, as pointed out by Peleg (21), is an empiri- chemically, and physically unstable at temperatures of 40 and
cal model that was not derived from any set of physical laws 50 ⬚C, as a result of fermentation, as showed by the forma-
or diffusion theories. But in our case, if experimental data fit tion of foam.
acceptably with it, the equation is very useful for the calcu-
lation of initial absorption rate, in accordance to eq 3. Some Hazards
important relations mathematically analogous to the Peleg
equation are the Langmuir-type absorption isotherm and the There are no significant hazards associated with this ex-
Michaelis–Menten kinetic expressions. Water absorption has periment. Nevertheless the students should be advised not
also been described in the literature by models assuming that to eat fermented chickpeas (after a long soaking in hot wa-
the process is controlled by mass transfer or by assuming that ter).
the water diffusion inside the food is the rate-controlling step.
Results and Discussion
Experimental Procedure
The swelling of chickpeas when soaked in water is illus-
Chickpeas were purchased at a local market in León, trated in Figure 1. In accordance with experimental weight
Spain; however, other legumes would be adequate. In fact, data, the adsorbed water at the surface of the chickpea that
the described experiment could be used to compare the cannot be wiped off is negligible in comparison with the ab-
absorption patterns of different chickpeas cultivations and sorbed water, being less than 0.5% of the chickpea’s weight
other legumes such as beans or lentils. in each case. The repetition of the experiment showed a good
A sample of 20 chickpeas was studied in each experi- reproducibility of measurements. Typical results in the varia-
mental series. Chickpeas were selected in terms of weight tion of the mass of chickpeas during soaking as a function of
(∼0.7 g), size (10.6 ± 0.2 mm of diameter), and aspect (ho- time show characteristic asymptotic curves, as observed in
mogeneity). Samples selected for each run were weighed on Figures 2 and 3. Figure 2 illustrates the variation of moisture
an electronic balance (± 0.0001 g) and immersed in a beaker
containing 200 mL of distilled water or aqueous solutions
of NaCl up to 3.0 M, at 20 ± 1 ⬚C (room temperature). At
selected intervals, samples were quickly removed with a spoon,
gently wiped with clean paper towel, and weighed. Clean tow- 0.9
els must be used for each weighing to avoid contamination
with salt or water. The moisture uptake (MU) was calculated
as follows,
0.6
MU(t )

(mass CP)t − (mass CP) 0

MU(t ) ⬅ (5)
(mass CP) 0 50 °C
0.3 40 °C
where CP stands for chickpeas. 30 °C
20 °C
The experiment was repeated with new samples of chick- 5 °C
peas at temperatures of 5, 30, 40, and 50 ⬚C. For these tem-
0.0
peratures, the beaker was immersed in a thermostatic bath 0 100 200
set at the predefined constant temperatures. The precision Time / min
on temperature measurements was ± 1 ⬚C.
There are not data for times longer than 270 min (4.5 Figure 2. Graph of the moisture uptake for chickpeas immersed in
hours). At longer times the chickpeas became biologically, distilled water at different temperatures.

www.JCE.DivCHED.org • Vol. 81 No. 4 April 2004 • Journal of Chemical Education 533

 In the Laboratory

-4.0

0.6

ln[IHR / (10ⴚ3 minⴚ1)]

-4.4
MU(t )

0.3
-4.8
0.0 M
0.5 M
1.0 M
3.0 M -5.2
0.0
0 100 200 3.2 3.4 3.6

Time / min 1 ⴚ3 ⴚ1
/ (10 K )
T
Figure 3. Graph of the moisture uptake for chickpeas immersed in Figure 4. Graph of natural logarithm of the initial hydration rate
differing concentrations of aqueous solutions of NaCl; T = 20 ºC. (IHR) as a function of reciprocal temperature.

uptake with the immersion time during osmotic hydration where T is the absolute temperature. The correlation coeffi-
over a range of temperatures. Figure 3 shows the variation of cient of ᎑0.9970 is obtained.
moisture uptake with immersion time with varying NaCl From the slope of this plot, ᎑Ea兾R, the apparent energy
concentrations of the immersion solution. of activation, Ea, was calculated as 19.5 ± 0.9 kJ兾mol. This
The values of the parameters of the Peleg model, the value agrees well with the literature value of 17 kJ兾mol for
equilibrium moisture uptake (ME ), taken as 1兾k2, and the the activation energy of fluidity of water (22), which mea-
initial rate of hydration, taken as 1兾k1, for the different sures the temperature dependence of the viscosity of water.
samples are listed in Table 1. As expected, the hydration rate The fluidity of water is relevant to its molecular mobility in
increases with temperature, owing primarily to the combined pores and slits, such as in the process studied in this experi-
effect of increasing diffusivity and decreasing viscosity. Ac- ment. As pointed out by several authors (23, 24), when a
cording to an Arrhenius-type behavior the semilog plot in rate is controlled by chemical reaction and thus related to
Figure 4 predicts the temperature dependence of the initial classical collision theory, the Ea is generally higher than that
hydration rate (IHR) as, expected for a diffusion-controlled process, which generally
exhibits Ea of only a few kilojoules per mole. Thus, as ex-
d MU(t ) pected, the studied process appears to be a diffusion-con-
IHR ⬅ trolled process and Ea is associated with the energy barriers,
dt 0
such as softening of the cell walls, that must be overcome for
(6)
water to flow and diffuse into the chickpeas. This result gives
(− 2.35 ± 0.11)103 K insight into the mechanism of the process. Generally the mass
= (24.8 ± 7.0 min −1) exp
TK transfer coefficient increases with temperature.

Table 1. Water Absorption Parameters, Equilibrium Moistures Uptake, ME, and Initial Hydration Rates
Calculated from Experimental Data

Initial Hydration
T/ºC [NaCl]/(mol L᎑1) k1/min k2 ME
Rate/(10᎑3 min᎑1)

5 0.0 190 ± 7 1.05 ± 0.05 0.95 ± 0.05 5.3 ± 0.2

20 0.0 130 ± 5 1.02 ± 0.03 0.98 ± 0.03 7.7 ± 0.3
30 0.0 94 ± 3 0.93 ± 0.02 1.08 ± 0.02 10.6 ± 0.3
40 0.0 76 ± 2 0.83 ± 0.02 1.20 ± 0.03 13.2 ± 0.3
50 0.0 58 ± 1 0.79 ± 0.01 1.27 ± 0.02 17.2 ± 0.3
20 0.5 131 ± 4 1.66 ± 0.04 0.60 ± 0.02 7.6 ± 0.2
20 1.0 145 ± 6 1.97 ± 0.05 0.51 ± 0.01 6.9 ± 0.3
20 3.0 164 ± 6 2.13 ± 0.05 0.47 ± 0.01 6.1 ± 0.2

534 Journal of Chemical Education • Vol. 81 No. 4 April 2004 • www.JCE.DivCHED.org

 In the Laboratory

Further Discussion: Uniqueness of a Model

The Arrhenius equation was originally developed for 8

simple chemical reactions where the energy of activation has

IHR / (10ⴚ3 minⴚ1)

a precise meaning. From the reported data it can be deduced
that the logarithm of the initial hydration rate, IHR, when
7
plotted versus the absolute temperature reciprocal, yields a
straight line in the temperature range considered. But the re-
ported experimental data can be fitted by a variety of alter-
native mathematical models, for example, 6

ln(IHR) = −12.55 + 0.0263T (7)

5
0 1 2 3
with a correlation coefficient of 0.9999, or
NaCl Concentration / (mol Lⴚ1)
IHR ⫽ 5.0 ⫻ 10⫺3 ⫹ 2.27 ⫻ 10⫺5 (T ⫺ 273)1.61 (8) Figure. 5. Graph of the natural logarithm of the initial hydration
rate (IHR) as a function of NaCl concentration of the immersion
with a correlation coefficient of 0.9999. A discussion of a solution.
model’s uniqueness and the need to establish the meaning of
experimental parameters by independent assays will be of
great educational value to the students. The variation of ini-
tial hydration rate with the NaCl concentration in the im-
mersion solutions is shown in Figure 5. Results are in
accordance with the expectation that the increased salt con- curring in the chickpeas, or with other assays that could moni-
centration in the immersion liquid results in the decrease of tor the structural changes in the starch and protein molecules,
hydration kinetics. The process of diffusion, which students given the fact that transitions from a glassy solid state to the
know from physics, can be used as a platform to introduce rubbery liquid state is also appreciated in the process (26).
the concept of mass transfer and also the basic equation for This experiment could also be performed for other legumes
transfer processes: such as lentils or beans and with other salt solutions such as
NaHCO3. It is known that with dried vegetables, especially
driving force beans, peas, and chickpeas, a pinch of sodium bicarbonate
Transfer rate per unitt area = (9) added to the soaking water improves the cooking abilities of
resistance
these legumes. Use of soft water, preferably distilled, for soak-
ing is also recommended as calcium and magnesium ions in-
In our case, according to eq 9, which is only a first-order crease the firmness.
law, the initial moisture uptake rate (dM(t)兾dt)0 can be de-
scribed by the expression,
Summary

d M (t ) This simple kinetics experience assists in teaching the

= SKtr ∆C (10) concepts of osmotic flow, mass transfer, diffusion, kinetics
dt 0 of hydration, modeling, and estimation of activation energy.
The experiment can be safely, inexpensively, and easily per-
where S is the surface area for mass transfer, Ktr denotes the formed. It will enable the students to generate and interpret
mass transfer coefficient, and ∆C is the difference between quantitative experimental data while investigating a familiar
concentration of salts in the chickpeas and in the immersion physical phenomenon with practical implications. The ex-
liquid. The work by Machado et al. (25) is recommended for periment performs the role of introducing first-year students
further reading on different mathematical models to describe to an interdisciplinary phenomenon.
the kinetics of moisture uptake of foods during soaking pro- In a broader sense, this experiment could be used to in-
cesses. troduce students to the importance of the water cellular flow
It should be stressed that a successful curve fitting is not in living organisms. The importance of this area was acknowl-
a confirmation of a hypothesis. The true test is to use the edged with the award of the 2003 Nobel Prize in Chemistry
model to estimate the moisture gain after 6, 12, or 24 hours to Peter Agre and Roderick MacKinnon, who have made fun-
of immersion and then compare the estimates with the val- damental discoveries of how water and ions move through
ues actually recorded. membranes (27). Agre discovered and characterized the first
water channel protein and MacKinnon elucidated the struc-
Further Studies tural and mechanistic basis for ion channel functions. Water
channels are crucial for life and are found in all organisms
It would be interesting to complement the absorption from bacteria to humans (28). In plants, they are critical for
data by size (radius) and hardness measurements and micro- water absorption in the root and for maintaining the water
scopic analysis in order to follow the structural changes oc- balance through the plant.

www.JCE.DivCHED.org • Vol. 81 No. 4 April 2004 • Journal of Chemical Education 535

 In the Laboratory

Acknowledgments 14. Pinto, G. Educ. Chem. 2003, 40, 11.

15. Singh, U. Qual. Plant Foods Human Nutr. 1985, 35, 339.
The authors would like to gratefully recognize the fi-
16. Afacan, N. Determination of the Important Parameters for
nancial support provided by the Fundación Española para la
High Quality White Roasted-Chickpea Production. M.Sc.
Ciencia y la Tecnología (Spanish Foundation for Science and
Thesis, Middle East Technical University of Ankara, Turkey,
Technology) under the project “Teaching/Learning of Chem-
2000.
istry and Everyday Life” (Grant No. 17502/57-1F). We would
17. Konak, A. R. Chem. Eng. Educ. 1997, 31, 40.
also like to thank the reviewers and editors for useful and
18. For an example, see Fine, L. W.; Beall, H.; Stuehr, J. Chemistry
thought-provoking suggestions.
for Scientists and Engineers, Preliminary Ed.; Saunders College
Publishing: Philadelphia, PA, 2000.
Literature Cited
19. Morse, J. G. J. Chem. Educ. 1999, 76, 64.
1. Roesky, H. W.; Möckel, K. Chemistry Curiosities; VCH: 20. Barat, J. M. E.; Chiralt, A.; Fito, P. J. Food Sci. 1998, 63, 836.
Weinheim, Germany, 1996. 21. Peleg, M. J. Food Sci. 1988, 53, 1216.
2. Jones, M. B.; Miller, C. R. J. Chem. Educ. 2001, 78, 484. 22. Metz, C. R. Shaum’s Outline Series, Theory and Practice of Physi-
3. Beauchamp, G. J. Chem. Educ. 2001, 78, 523. cal Chemistry; McGraw-Hill: New York, 1976.
4. Essays in Physical Chemistry; Lippincott, W. T., Ed.; American 23. Rydberg, J.; Musikas, C.; Choppin, G. R. Principles and Prac-
Chemical Society: Washington, DC, 1988. tices of Solvent Extraction; Marcel Dekker: New York, 1992.
5. Van Wie, B. J.; Poshusta, J. C.; Greenlee, R. D.; Brereton, R. 24. Paz, I.; Pinto, G. Spectrosc. Letters 2002, 35, 357.
A. Chem. Eng. Educ. 1994, 28, 188. 25. Machado, M. F.; Oliveira, F. A. R.; Gekas, V.; Singh, R. P.
6. Steidle, C.; Myers, K. J. Chem. Eng. Educ. 1999, 33, 46. Int. J. Food Tech. 1998, 33, 225.
7. Fraser, D. M. Chem. Eng. Educ. 1999, 33, 190. 26. Blanshard, J. M. V.; Lillford, P. J. The Glassy State in Foods;
8. Zubizarreta, J. I.; Pinto, G. Chem. Eng. Educ. 1995, 29, 96. Nottingham University Press: Loughborough, United King-
9. Pinto, G. J. Chem. Educ. 1998, 75, 725. dom, 1993.
10. Pinto, G. Educ. Chem. 2000, 37, 71. 27. Nobel e-Museum: Nobel Prize in Chemistry 2003. http://
11. Pinto, G. Educ. Chem. 2001, 38, 150. www.nobel.se/chemistry/laureates/2003 (accessed Feb 2003).
12. Pinto, G. Anales de la Real Sociedad Española de Química 2003, 28. Agre, P.; King, L. S.; Yasui, M.; Guggino, W. B.; Ottersen,
99 (1), 44. O. P.; Fujiyoshi, Y.; Engel, A.; Nielsen, S. J. Physiol. 2002,
13. Pinto, G.; Rohrig, B. J. Chem. Educ. 2003, 80, 41. 542, 3.

536 Journal of Chemical Education • Vol. 81 No. 4 April 2004 • www.JCE.DivCHED.org