Food Hydrocolloids 15 (2001) 4346

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Relationships between water activity and viscosity of solutions

J. Mazurkiewicz a, P. Tomasik b,*, J. Zapotny a
a

Department of Physics, Mickiewicz Ave., 21, 31 120 Cracow, Poland

Department of Chemistry, University of Agriculture, Mickiewicz Ave., 21, 31 120 Cracow, Poland
Received 1 June 2000; received in revised form 10 August 2000; accepted 6 September 2000

Abstract
Water activity, aw, in solutions of NaCl, glycerol, d-glucose, sucrose, and urea was correlated against viscosity, h of these solutions.
Relationship is non-linear, which follows the h paw2 1 qaw 1 r equation. Generally, these relationships provide control over the water
activity of solutions at a required viscosity and, vice versa control over viscosity at a given water activity. q 2001 Elsevier Science Ltd. All
rights reserved.
Keywords: Non-linear relationships; Viscosity control; Water availability

1. Introduction
Water is one of the most essential component of foodstuffs. Its amount therein determines several foodstuffs
properties such, for example, as sensory properties, texture,
stability on storage due to, for instance, enzymatic and nonenzymatic decomposition (Rockland & Beuchat 1987;
Rockland & Stewart 1981), rheology (Sikora, Mazurkiewicz, Tomasik, & Pielichowski, 1999), and phase transfers,
for instance, crystallisation. Amount of water is also a
crucial parameter in foodstuff manufacture and transport.
However, knowledge of the amount of water is expressed
either in moles or molar concentration as expressing as a
molar fraction might be insufcient for controlling the properties of foodstuffs and processing taking place therein.
Because of hydration and other intermolecular interactions
in the presence of water, not all water molecules present in
the foodstuff will be available for the role they were anticipated to play. Such circumstances are usually encountered
in concentrated, (non-ideal solutions) aqueous solutions and
blends. This phenomenon has been explained in the beginning of the twentieth century. It found a practical involvement in form of so-called activity. This term may be
understood as a correction factor to the concentration
expressed in molality, and molar fraction. Depending on
the method used in the determination of the concentration
these correction factors are known as molal and rational
activities, respectively. Obviously, water activity in solu* Corresponding author. Tel.: 148-12-633-88-26; fax: 148-12-633-62-45.
E-mail address: rrtomasi@cyf-kr.edu.pl (P. Tomasik).

tions depends on the molecular structure of solute and its

dissociation (Apelblat & Korin, 1998; Libus, 1996; Pierotti,
Deal, & Derr, 1959; Rudakov & Sergyevskii, 1997; Wang,
Liu, Fan, & Lu, 1994). In multiphase systems a number of
phases is essential (Chou, Sridhar, & Pal, 1998).
In spite of the the appreciation enjoyed for over a century
and the practical application of water activity, such an
approach in food chemistry and technology evokes considerable interest on the level of determination of water activity
coefcients. Among others Chen (1989) reported an abundant collection of water activity coefcients for various
solutes in a wide range of solution concentrations. Recently
(Hills, Manning, & Ridge, 1996), for heterogeneous porous
systems a new theory of water activity was proposed.
Observed activity was calculated as the volume average of
a local, spatially varying activity of water, independently it
resided in the system as bulk, surface, and/or structural
water. This approach might be useful in studying the
water behaviour in foodstuffs.
Rheological behaviour is another important and readily
available property of solutions and suspensions. It is
commonly used for describing foodstuff properties and quality. Although viscosity has a strong link to the technological
value of solutions and suspensions, and their sensory quality
there are also links to solvation (Mazurkiewicz & Tomasik,
1982), and shape (Batko, Mazurkiewicz, & Tomasik, 1988) of
solutes, state of hydration of ions (Mazurkiewicz, NowotnyRozansa, & Tomasik, 1988) and interpretation of solute
solute interactions in solutions; a method helpful in predicting
the texture of foodstuffs (Mazurkiewicz, Zaleska, & Zapotny,
1993; Mazurkiewicz, Rebilas, & Tomasik, 2000).

0268-005X/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0268-005 X(00)00 048-5

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J. Mazurkiewicz et al. / Food Hydrocolloids 15 (2001) 4346

Table 1
Water activity (aw) and viscosity (h [cP]) of aqueous solutions of selected solutes
Molality (g mol/kg)

Urea

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0

Glycerol

NaCl

Sucrose

d-Glucose

aw

Aw

Aw

aw

0.998
0.996
0.995
0.993
0.991
0.989
0.988
0.986
0.984
0.983
0.980
0.976
0.972
0.970
0.967
0.959
0.952
0.945
0.938
0.931
0.925
0.918
0.912
0.905
0.899
0.893
0.887
0.881
0.875
0.869
0.863

0.900
0.902
0.904
0.906
0.909
0.911
0.914
0.917
0.919
0.923
0.929
0.936
0.944
0.952
0.960
0.984
1.012
1.042
1.076
1.114
1.155
1.199
1.246
1.297
1.351
1.408
1.469
1.533
1.601
1.672
1.746

0.998
0.996
0.995
0.993
0.991
0.989
0.987
0.986
0.984
0.982
0.978
0.975
0.971
0.967
0.964
0.955
0.946
0.937
0.928
0.919
0.910
0.901

0.899
0.907
0.930
0.954
0.977
1.001
1.027
1.055
1.084
1.100
1.146
1.212
1.283
1.320
1.400
1.543
1.765
2.023
2.342
2.742
3.244
3.946

0.997
0.993
0.990
0.987
0.984
0.980
0.977
0.974
0.970
0.967
0.960
0.953
0.946
0.939
0.932
0.913
0.893
0.873
0.852
0.830

0.899
0.908
0.916
0.924
0.932
0.940
0.948
0.957
0.967
0.977
1.002
1.034
1.073
1.123
1.184
1.397
1.721
2.180
2.801
3.611

0.998
0.996
0.994
0.993
0.991
0.989
0.987
0.985
0.983
0.981
0.976
0.972
0.968
0.963

0.89
0.97
1.11
1.29
1.47
1.66
1.86
2.07
2.31
2.60
3.49
5.09
7.90
12.53

In this paper correlation between water activity in

aqueous solutions of NaCl, d-glucose, sucrose, glycerol,
and urea and viscosity of these solutions are studied.

2. Materials and methods

2.1. Materials
NaCl, glycerol, urea, d-glucose, and sucrose, all of analytical grade, were purchased from Sigma Poland. Water was
re-distilled.
Table 2
Parameters of Eq. (1) (c0 0:999)
Solute

Urea
Glycerol
d-Glucose
Sucrose
NaCl

0.0003
0.0001
2 0.00005
2 0.0009
2 0.0015

2 0.0163
2 0.0187
2 0.0195
2 0.0198
2 0.0310

aw

0.982

1.58

0.963

2.65

0.943

6.71

0.923

16.47

0.903

34.64

0.883

63.94

0.863
0.853

107.08
134.69

2.2. Viscometric measurements

The viscometric measurements were carried out with the
Zimm rotary viscometer (Zimm & Crothers, 1962) modied
in our laboratory (Mazurkiewicz & Tomasik, 1996).
Measurements were carried out at 25 ^ 0:058C: Concentrations of particular solutions are reported in Table 1 Particular runs were continued until subsequent readings reached
constant value. Water activity coefcients were taken from
the research article by Chen (1989). These data are derived
for solutions at 258C.
3. Results and discussion
Relationships between water activity, aw, in solutions of
dissociating solutes known since the middle of this century,
was proved in numerous studies, and was recently looked
upon in terms of statistical mechanics (Ally & Braunstein,
1998). This study pointed that such relationships are valid
for nonelectrolytes such as solutes also. They are nonlinear
in concentration, c, of the solute as shown by Eq. (1). Parameters of this equation for particular solutes are given in
Table 2.

J. Mazurkiewicz et al. / Food Hydrocolloids 15 (2001) 4346

45

Table 3
Parameters of Eqs. (2) and (3)
Solute

Urea
Glycerol
d-Glucose
Sucrose
NaCl
a
b

Eq. (3) a

Eq. (2)
p

R2

44.68
629.88
11455
12592
146.88

2 89.31
2 1229.40
2 21999
2 24980
2 284.44

45.53
600.88
10561
12390
138.62

1.000
0.974
0.996
0.988
0.976

R 2b

2 17.34
2 27.37
2 28.49
2 110.42
2 15.41

13.78
25.88
29.23
108.79
13.65

0.97
0.99
0.99
0.99
0.99

h0 0:89:
The correlation coefcient. Number of experimental points in particular series is available from Table 1.

aw xc2 1 yc 1 c0

where c is expressed in g/kg and c0 is the activity coefcient

for pure water.
One may see that deviation from linearity [x-term in Eq.
(1)] is the most pronounced for the series of aqueous solutions of NaCl. Deviations from linearity in the case of
organic, non-dissociating solutes under study are almost negligible. Decrease in both terms x and y in Eq. (1) follows the
order of NaCl . sucrose . d-glucose . glycerol . urea.
Intuitively this order corresponds with the number of sites of
solute molecules open for interaction with water though not
necessarily via the hydrogen bond formation. In the case of
dissociating NaCl the number of water molecules involved in
hydration of ions should be taken into account. Such relationships linking rational water activity with the hydration number
of saccharides was shown by Rudakov and Sergyevskii
(1997).
Clearly, there is a non-linear relationship between the
water activity, aw, in solutions of the same solutes and viscosity, h , of these solutions. Eq. (2) of the same character as
Eq. (1) is followed.

h pa2w 1 qaw 1 r

Unlikely as in Eq. (1) where x and y decreased parallely, q

coefcient in Eq. (2) increases as p coefcient decreases. Eq.
(2) can be presented in an alternative exponential form [Eq.
(3)] with the constant h 0 being the viscosity of pure water at
258C.

h h0 1 expt 1 uaw

Parameters of both equations are given in Table 3.

The p and u reect the deviation of h vs aw function from
the linearity. The p-value for solution of NaCl is low. It
means that with an increase in concentration of the solution
the number of water molecules engaged in the hydration of
ions and solventsolute interactions did not increase significantly. It might be assumed that as the concentration of
NaCl increased, ions originally separated by an hydration
coat in the diluted solution formed contact ion pairs with
reduced number of molecules involved in the formation of
hydration coat. Low p-value for urea can be rationalised in a
similar way. Urea is known (Szejtli, 1986) for its ability to

associate into cages being the hosts in channel complexes.

Such an association employs polar groups open for hydration in diluted solutions. Thus, the association increasing
with concentration of solution liberated water molecules
engaged in hydration of urea molecules in diluted solution.
Relatively low p-value for glycerol suggests that in concentrated aqueous solution its molecules might be strongly
associated and in a consequence there is a weak hydration
of such associates. Extremely high p-value for sucrose
might be interpreted as strong hydration of sucrose associates. Indeed, Robinson and Stokes (1963) reported very
strong hydration of sucrose. A similar approach may be
applied for rationalisation of results of the measurements
by Na, Arnold, and Myerson (1995) who estimated water
activity in supersaturated aqueous solutions of two a-amino
acids of zwitterion structure and two dioic acids.
4. Conclusion
The viscositywater activity relationships provide
control over the water activity of solutions at a required
viscosity and, vice versa control over viscosity at a given
water activity.
References
Ally, M. R., & Braunstein (1998). Journal of Chemical Thermodynamics,
30, 4958.
Apelblat, A., & Korin, E. (1998). Journal of Chemical Thermodynamics,
30, 12631269.
Batko, A., Mazurkiewicz, J., & Tomasik, P. (1988). QSAR, 7, 245248.
Chen, C. S. J. (1989). Food Science, 45, 13181321.
Chou, K. -C., Sridhar, S., & Pal, U. B. (1998). Calphad, 21, 483495.
Hills, B. P., Manning, Ch. E., & Ridge, Y. (1996). Journal of Chemical
Society, Faraday Transactions, 92, 979983.
Libus, Z. (1996). Zeitschrift fuer Physikalische Chemie, 196, 165176.
Mazurkiewicz, J., Nowotny-Rozansa, M., & Tomasik, P. (1988). Chemica
Scripta, 28, 375379.
Mazurkiewicz, J., Rebilas, K., & Tomasik, P. (2000). Zeitschrift fuer
Lebensmitteln Untersuchung und Forschung, in press.
Mazurkiewicz, J., & Tomasik, P. (1982). Monatshefte fuer Chemie, 113,
12531262.
Mazurkiewicz, J., & Tomasik, P. (1996). Bulletin of the Chemical Society of
Belgium, 105, 173180.

46

J. Mazurkiewicz et al. / Food Hydrocolloids 15 (2001) 4346

Mazurkiewicz, J., Zaleska, H., & Zapotny, J. (1993). Starch/Die Staerke,

45, 175177.
Na, H. -S., Arnold, S., & Myerson, A. S. (1995). Journal of Crystal Growth,
149, 229235.
Pierotti, G. J., Deal, C. H., & Derr, E. L. (1959). Industrial Engineering and
Chemistry, 51, 95102.
Robinson, R., & Stokes, R. (1963). Electrolyte solutions (Russian translation), Moscow: Izdat. Mir (646pp.).
Rockland, L. B., & Beuchat, L. R. (1987). Water activity: theory and
applications to food, New York: Marcel Dekker.
Rockland, L. B., & Stewart, G. F. (1981). Water activity: inuences on food
quality, New York: Academic Press.

Rudakov, A. M., & Sergyevskii, V. V. (1997). Zhurnal Fizicheskoi Khimii,

71, 14201424.
Szejtli, J. (1986). Cyclodextrin inclusion complexes, Budapest: Akademiai
Kiado (chap. 2).
Sikora, M., Mazurkiewicz, J., Tomasik, P., & Pielichowski, K. (1999).
International Journal of Food Science and Technology, 34, 377
383.
Wang, J., Liu, W., Fan, J., & Lu (1994). Journal of Chemical Society,
Faraday Transactions, 90, 32813285.
Zimm, B., & Crothers, D. (1962). Proceedings of the National Academy of
Science USA, 48, 905910.