A Method for the Determination of Diffusion Coefficients of Food
Components in Low- and Intermediate Moisture Systems
W. NAESENS, G. BRESSELEERS,
ABSTRACT
A simple set-up to measure translational diffusion of components in
low moisture systems is described. The tracer technique was tested
on the diffusion of t4C-labeled tripalmitin and palmitic acid in a
model system containing paraffin oil, microcrystalline cellulose and
gum arabic. Different methods to evaluate the apparent diffusion
coefficients from the experimental diffusion curve were compared.
Good results were obtained using a curve-fitting procedure based on
the sum of least squares.The technique appears to be suitable for
measuring diffusion coefficients up to .10e9 cm2/sec. The proce-
dure offers the possibility to quantify the mobility of chemical
components in dried foodstuffs in order to elucidate the mechan-
isms and kinetics of reactions occurring during storage.
INTRODUCTION
THE RELATIVE MOBILITY of chemical substances is one
of the determining factors in chemical and enzymatic reac-
tions. The displacement of reactants and reaction-products
is important, not only in liquid and gaseousmedia but also
in dry systems. With respect to dried foods, a relation be-
tween reactant mobility and chemical reaction has often
been put forward (Labuza et al., 1970; Seow, 1975; Duck-
worth et al., 1976). The diffusion of individual food com-
ponents in dried systems has been suggested as one of the
major factors restricting enzymic activity (Brockmann and
Acker, 1978; Potthast, 1978).
Accurate knowledge of diffusion coefficients is a pre-
requisite for a better understanding of the loosely used
term “mobility” in order to approach the above mentioned
subject from a more quantitative viewpoint. Duckworth
(1962) has shown a relation between moisture content and
diffusion of labeled glucose in dried potato and carrot tis-
sues by means of autoradiography. In a companion study
(Duckworth and Smith, 1963), various counting techniques
have been used to measure the extent of diffusion of simple
soluble constituents in both plant and animal products, but
all the data obtained were qualitative. Later, Duckworth
and co-workers have done extensive studies on the mobility
of various low molecular weight proton-containing solutes
in finely-devided samples of various colloidal test materials
at different moisture levels using wide-line NMR (Duck-
worth and Kelly, 1973; Seow, 1975; Duckworth et al.,
1976).
Mobihty of components in dehydrated systems has
also been of interest in the study of volatile retention in
freeze-dried foods. Selective diffusion and microregion
entrapment have been proposed as the basic underlaying
mechanisms (Flink, 1975; Omatete and King, 1978). The
microregion entrapment theory of Flink and Karel (1972)
is more a qualitative description of mobility whereas the
selective diffusion theory of Thijssen and Rulkens (1968)
is a quantitative diffusion-based analysis. They derived
diffusion coefficients for water and volatiles at different
water concentrations from sorption- and desorption mea-
All authors are wifh the Laboratory of Food Preservation, Catholic
University of Leuven, de Croylaan 42, 3030 Heverlee, Belgium.
1446-JOURNAL OF FOOD SCIENCE-Volume 46 (1981)
and P. TOBBACK
surements (Menting et al., 1970). Unfortunately, their
techniques cannot be suitably used for nonvolatiles. In
the same context, Chandrasekaran and King (1972) have
described a diffusion technique which is only applicable
to aqueous solutions.
Quantitative diffusion in foods or related systems has
been predominantly measured in homogeneous liquids or
liquefied heterogeneous media such as solutions or gels
(Brown and Chitumbo, 1975; Busk and Labuza, 1979;
Stahl and Loncin, 1979; and many others). When presented
in dry systems, diffusion is mostly a matter of sorption or
desorption of water or volatiles. The experimental set-up
for diffusion measurements as described in these studies
generally does not allow an adaption for measuring diffu-
sion of nonvolatile components in dehydrated systems.
This is also true for the extensive diffusion research carried
out in the field of adsorption, synthetic polymers and
heterogeneous catalysis. A useful method however has been
described by Moore and Ferry (1962) for the quantitative
determination of diffusion of 14C-labeled penetrants
through polymer solutions. A thin layer of radioactive
penetrant or a disk of polymer containing the radioactive
penetrant was joined to a nonradioactive disk and the
diffusion was followed by measuring the activity at the ini-
tially inert surface by means of a Geiger tube.
While diffusion phenomena play an important role in
relative dry systems and should be taken into consideration
whenever quantitative analysis of the reactions occuring
in such systems are made, methods for accurately determin-
ing diffusion coefficients seem to be lacking. In this study,
a tracer method is proposed which allows the determination
of the apparent translational diffusion in partially dried
systems. Before handling the practical aspects of the set-
up, some attention must be paid to the basic principles of
diffusion.
Basicdiffusiontheory
The one-dimensional solution of Fick’s second law for
an extended source of infinite extent with initial condi-
tions
c = c, x<o for t = 0 (1)
c=o x>o >
and for a constant diffusion coefficient is given by Crank
(1956):
X
c (x,t) =F 1 - erf (2)
2 (Dt)r 12>
where C(x,t) is the concentration of the diffusing substance
at distance x and time t, D is the diffusion coefficient, Co
is the initial concentration and erf is the well-known
error function of which elaborate tables are.available. The
diffusion coefficient can be estimated at any point of the
experimental diffusion profile by means of Eq(2).
A relative simple method to estimate the diffusion coef-
ficient is stated by Jost (1957). The equation of the tangent
at the inflection point of the sigmoid c_urveis given by
CO CO
C=-2(nDt)r/2X+?-

The intercept with the x-axis (xc) is thus given by
x0 = (rrDt)’ /2 (4)
from which D can readily be calculated.
A more general solution, which is also valid for concen-
tration-dependent diffusion coefficients, is given by Crank
(1956):
1 dx Cl x dC
Dc=co = - --2t dC o (5)
I model system without diffusant was weighed and brought rapidly
and
CO
xdC=O (6)
0 tem, so that it was perfectly flat and orthogonal to the length-axis
with Cr any value of C between 0 and Co. The procedure
is to plot the concentration-distance curve for a known
time, to locate plane x=0 by use of Eq (6), and then to
evaluate D at various concentrations C, from Eq (5). The
latter results from the tangent of the diffusion curve at
C=C, (dC/dx) and from the area under the curve from C=O
to C=Cr (JxdC). A method of improving the accuracy of
the calculations near the extremes of the concentration
range is given by HalI (1953).
EXPERIMENTAL
Preparation of the diffusion model system
Tripalmitin or palmitic acid was chosen as diffusants in a medi-
um containing 20 times more liquid araffin oil in which it is
completely miscible at 50°C. 45 mg 1%C-labeled (~1 PCi) tripal-
mitin and 900 mg paraffin oil were dissolved in 2 ml chloroform and
emulsified with 20 ml of a 5% (w/v) aqueous solution of gum arabic
(Merck 4282) with an Ultra-Turrax Mixer Emulsifier (Janke and
Kunkel K.G., Type TP 18/10, Staufen, W. Germany) for 2 min at
maximum speed. The emulsion was then well mixed with 15g
microcrystalline cellulose (Avicel, Merck 2230) and 60 ml bidis-
tilled water by means of the Ultra-Turrax for 3 min at maximum
speed. When palmitic acid was used instead of tripalmitin, 60 ml
0.2M Tris-HCl pH 8.0 was used instead of 60 ml water. Similar
suspensionswere prepared in the absenceof the diffusants.
The suspensions were poured into plastic petri-dishes to a
depth of about 3 mm, quickly frozen with liquid air and freeze-
dried at a pressure of less than 0.1 Torr in such a way that the
maximum temperature never exceeded 25’C (Secfroid, Lyolab C
3023, Lausanne, Suisse). The freeze-dried suspensions were then
stored at 5O’C above standard saturated salt solutions (Greenspan,
1977) for about 7 days. MgCl, (a, = 0.31) and NaCl (a, = 0.74)
Fig. 1 -Perspective view of a diffusion cylinder and plunger. The arrow
and L. for the labeled layer of the system.
MEASUREMENT OF DIFFUSION IN DRY SYSTEMS.. .
were chosen. After equilibration, the water activity (aw,) of the
samples was measured with a calibrated electrical hygrometer (Nova
Sina Ag, SMT-B, Zurich, Suisse) at the same temperature.
Diffusion set-up
The diffusion experiments were performed in thick glass-wall
cylinders of 1.2 cm inner diameter and about 7 cm length. Each
cylinder was graduated at 1 m m accuracy (Fig. 1). A glass plunger
fitted precisely in the cylinder. Approximately 0.75-lg of the
into the cylinder which was stoppered at one end. The dry mixture
was compressed so that lg of system was distributed over exactly
2 cm. Attention was paid to the upper face of the compressedsys-
of the cylinder because this plane was considered later as the initial
(x=0)-plane. An equal amount of the diffusant-containing model
system was deposited on the first layer in the same manner and the
cylinder was stoppered at the other end. The cylinder was stored
at the desired condition of relative humidity at 50°C.
Concentrationdistance curve
After a certain time, the diffusion system was analyzed in order
to obtain the concentration-distance curve. The stoppers at both
ends were removed and the plunger was gently placed in the glass
cylinder on the side of the diffusant-containing model system. The
plunger was moved forward by a screw action so that the model
system was gradually forced out of the cylinder. Slices of about
0.2-0.3 m m thickness were scraped off with a razor blade and
the powder of each slice was collected in a pre-weighed 20 ml
plastic scintillation vial. The weight of the powder was determined
and the activity was measured with a liquid scintillation counter
(Beckmann, LS 9000) using 1 ml water and 7 ml Hydroluma (Lu-
mat, 1077) as scintillation medium. No correction for quenching
was found to be necessary and the background was substracted.
The activity of the last slices expelled from the system, expressed
as cpm/g, was set equal to Co and the relative concentration of the
diffusant in the preceding slices was calculated as C/Co. The dif-
fusion distance could be easily calculated from the weights of the
successiveslices and the compression factor.
RESULTS& DISCUSSION
THE MODEL SYSTEM presented here stands for a typical
example of a powdered, heterogeneous and porous sub-
stance. In such systems, it is convenient to define D as an
overall or apparent diffusion coefficient (Stahl and Loncin,
1979). As shown in Figure 2, the tripalinitin system gives a
symmetric profile. This suggests that the displacement of
indicates the initial (x=0)-plane; N. L. stands for the nonlabeled layer
Volume 46 (1981)-JOURNAL OF FOOD SCIENCE- 1447
 tripalmitin is only due to Brownian motion. Little is known mental curve in order to obtain a reproducible value.
about the physical state of the oil in the model system. Solutions using Eq (2) are also quite acceptable. The value
Probably the emulsion is reconstituted upon rehydration of D becomes also more accurate if several experimental
as described by Lladser and Arancibia (1972) and by Gejl- points are used. Curve fitting based on the method of the
Hansen and Flink (1978). We have also found by scanning least squares can be usefully applied for this purpose.
electron microscopy that at least part of the oil is present According to this method, a number of diffusion coeffi-
as oil globules. An asymmetric and much less developed cients in the range of the expected value of D are selected.
diffusion profile is obtained with the palmitic acid system The best fit diffusion coefficient minimizes the sum (S) of
(Fig. 2). This was even true in the absence of the Tris-HCl the squared deviations between the experimental concentra-
buffer. It is well-known that diffusion of ,ionic compounds tions (C,) and the calculated concentrations (C,) at the
is complicated by interactions with the matrix (Duckworth different locations:
and Smith, 1963; Karel, 1976). The Ca++ present in the s = c (C, - Cc)2
model system may be one of the interacting factors. The (7)
diffusion coefficient of palmitic acid cannot be calculated The C,‘s are calculated from Eq (4) and the plane corres-
from the simple equations as given above and is not further ponding to x=0 can be determined by Eq (6). The proce-
discussed. dure can be implemented on a computer which, if neces-
The tripalmitin system in Figure 2 shows that our sary, also plots the diffusion curve. A reliable diffusion
diffusion technique yields a fairly good experimental coefficient is rather easily obtained in this way. Even with
curve. Similar symmetric curves were obtained after 90 this method, small differences between the D values of
days and at a,=0.33. Apparent diffusion coefficients from similar diffusion experiments may still exist. This is illus-
the experimental curves were calculated using the de- trated in Table 1 where the diffusion coefficients at two
scribed methods (Table 1). Eq (4) offers very rapidly a diffusion times are compared. The differences seem to
good estimate of D. Eq (4) can also be easily applied to get diminish as the diffusion profile becomes more developed.
an idea of the required diffusion time when D is approxi- Moore and Ferry (1962) reported a precision of D within
mately known. The method using Eq (5) and (6) was found about 5% in their diffusion methods. When diffusion was
to be rather inaccurate and time consuming. It was neces- slow, their precision was largely dependent on the accuracy
sary to calculate D at more than one point of the experi- with which the thickness of the disks, varying between as
little as 0.15 and 0.4 cm, was known. Also in our set-up,
the deviations of the experimental compression factor from
the theoretical value of 2 cm/g may represent a source of
error. However, it must be stressed that adding the second
layer in the diffusion set-up did not cause the initial layer
to compress.
The diffusion of tripalmitin is low compared with the
diffusion coefficients for nonionic solutes and ions in lique-
fied food related systems which range from lop5 to 5 x
lop8 cm2sec-1 (Karel, 1976; Busk and Labuza, 1979).
On the other hand, it is well known that diffusion coeffi-
cients are strongly dependent on water concentration. A
possible decrease over seven orders of magnitude from very
high moisture to nearly dry material has been reported
(Bomben et al., 1973). Few diffusion data in the low mois-
ture range are available. Fish (1958) accurately measured
the diffusion coefficient of water by adsorption and desorp-
tion in starch gel and scalded potato at moisture contents
as low as 0.8% (dry basis). The diffusion coefficient was
found to decrease very markedly with decreasing moisture
content, especially below 30% moisture: 3.6 x 1O-8
cm2sec-l at 14.1%, 1.5 x 10-9cm2sec-1 at 6.3%, and
DISTANCE x (cm)
1.05 x lo-i0cm2sec-’ at 0.8% for starch gel. Menting et
al. (1970) measured the diffusion of water and aceton in
Fig. 2-Diffusion curves after 45 days of tripalmitin l - l and pal-
malto-dextrin at moisture contents above 10% (wet basis)
mitic acid o - o in the model system containing paraffin oil, micro-
crystalline cellulose, and gum arabic at an a, of 0.71 and 50°C. A
at 21.5’C. The D of aceton was 1.5 x lo-l1 cm2sec-l
Tris-HCI buffer pH 8.0 was used in the preparation of the palmitic at 10.2% (awZO.6) and 3.0 x 10-9cm2sec-1 at 20.1%
acid system. (awr0.85). Diffusion coefficients of water were one to
two orders of magnitude higher but followed the same
pattern. The authors also showed that there is an inverse
Table I-Tripalmitin diffusion coefficients at 5@C in the model linear relationship between log D and the molecular diam-
system at two water activities as calculated by three different eter of the diffusant in this moisture range. Compared to
methods these results, the diffusion of the large molecule tripalmitin
(Table 1) in our model system at a,=0.33 (4.5% H20 on
D x 10’ (crn%~-~) dry basis) and aw=0.71 (7.5% H,O) is remarkably high,
Time Least even when corrected for the difference in diffusion tem-
ha (days) Eq (4) Eq (5) and (6jb squares perature. Activation energy for diffusion is below 10 kcal/
mol (Fish, 1958; Menting et al., 1970; Stahl and Loncin,
0.33 45 4.2 4.2 4.0 1979), SO one can easily calculate that the diffusion coeffi-
90 4.7 4.5 4.4 cient of aceton in the malto-dextrin system at 10.2% water
0.71 45 7.4 7.8 7.6 should not exceed 5.5 x lo-“cm2sec-’ at 5O’C. The
90 7.4 7.8 7.7 relative low extent of binding between tripalmitin and the
a As measured by means of the Sina hygrometer
carbohydrate may be responsible for the higher tripalmitin
b Mean value mobility. Moreover, the negligible solubility of tripalmitin

1448-JOURNAL OF FOOD SCIENCE-Volume 46 (1987)

 MEASUREMENT OF DIFFUSION IN DRY SYSTEMS. ..

in water makes it reasonable that it is not molecularly Brown, W. and Chitumbo. K. 1975. Solute diffusion in hydrated
transported like water-soluble diffusants. It is probable polymer networks. Part 1. Cellulose gels. J. Chem. Sot. (Faraday
Trans. I) 71: 1.
that the diffusion of tripalmitin is poorly dependent on Busk. G.C. Jr. and Labuza, T.P. 1979. A dye diffusion technique to
the water in the system. On the contrary it is likely that evaluate gel properties.
Chandrasekaran.
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SK. and King, C.J. 1972. Multicomponent diffu-
its mobility is highly influenced by the paraffin oil present sion and vapor-liquid equilibria of dilute organic components in
in the model system in which it is completely miscible at aqueous sugar solutions. A.1.Ch.E. J. 18: 513.
Crank, J. 1956. “The Mathematics of Diffusion,” Oxford University
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other than water might play a role in the process of mobili- Duckworth. R.B. 1962. Diffusion of solutes in dehydrated vege-
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This view is also supported by the relative small difference The aqueous environment for chemical change in intermediate
moisture foods. In “Intermediate Moisture Foods,” Ed. Davies,
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Flink. J. 1975. The retention of volatile components durine. freeze
is already sufficient to determine a reliable value of D. This drying: a structurally based mechanism. Id “Freeze Drying and
means that it is possible to measure diffusion coefficients Advanced Food Technology, ” Ed. Goldblith, S.A.. Rey. L.. and
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this range it may be easier to use a direct scanning-method Hall. L.D. 1953. An analytical method of calcuiating variable dif-
which is less time consuming and nondestructive. fusion coefficients.
Jest. W. 1957. “Diffusion
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The measurement of the translational diffusion of com- tung,” Verlag von D. Steinkopff, Darmstadt. W. Germany.
ponents in this way is more quantitative than the above- Karel, M. 1975. Physico-chemical modification of the state of
water in foods. A speculative survey. In “Water Relations of
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L.C., Hoogstad, B.. and Thijssen, H.A.C. 1970. Diffusion
of water and organic volatiles in carbohydrate-water
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curve-fitting procedure based on the sum of least squares cetane in polyisobutylene-cetane mixtures and in three meth-
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food components in systems at low- and intermediate mois- Omatete, 0.0. and King; C.J. 1978. Volatiles retention during re-
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Aroma recovery and retention in concentration and drying of This work was supported by the Fund for Joint Basic Research of
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tische Reaktionen. Lebensmittel-Technol. ll(4): 2.

Volume 46 (1981)-JOURNAL OF FOOD SCIENCE- 1449