0960–3085/04/$30.00+0.

00
# 2004 Institution of Chemical Engineers
www.ingentaselect.com=titles=09603085.htm Trans IChemE, Part C, March 2004
Food and Bioproducts Processing, 82(C1): 60–72

MODELLING DIFFUSION OF MOISTURE DURING

STOVING OF STARCH-MOLDED CONFECTIONS
M. B. SUDHARSAN1, G. R. ZIEGLER2,* and J. L. DUDA3
1
Nestlé Product Technology Centre, Orbe, Switzerland
2
Department of Food Science, Penn State University, University Park, USA
3
Department of Chemical Engineering, Penn State University, University Park, USA

S
tarch molding is a widely used shape forming technique in the confectionery industry.
Candy is deposited into cavities imprinted in dry granular starch contained in a shallow
tray. For products that cannot be deposited at their final moisture content, a drying or
stoving stage follows deposition, and largely determines the productivity of the process. In the
present work a finite difference model was developed that quantitatively predicted the moisture
diffusion from a single candy piece into the starch bed or air at a given temperature (50
C).
The model suggested that a ‘skin’ or region of of low moisture content (3–4% wet basis) and
diffusivity (1013 m2 s1) was formed near the surface of the candy at normal operating
conditions of the drying room that then slowed the drying process, and that the spacing
between the candies does not affect the drying rate at typical print densities. The model
adequately predicted experimental results from model systems and in production. Controlling
the relative humidity of the drying air, the initial moisture content in the starch bed, and the
temperature of the drying chamber may avoid skin formation, improve drying rate and
minimize the drying energy required.

Keywords: confectionery; diffusion; drying; mathematical modelling; starch-molding; stoving.

INTRODUCTION
Confectionery items such as jellybean centers, candy corn,
marshmallows, starch gums, caramels, nougat, gummies and
cream centers may be manufactured using starch molding
techniques. Hot candy liquor is deposited into cavities
imprinted in dry granular starch contained in a shallow
tray, and the finished candy piece is sieved from the molding
starch after setting. A variety of shapes can be produced on
the same equipment by simply changing the print board.
Because of its versatility, starch molding is one of the most
widely used shape-forming techniques for non-chocolate
confectionery and confectionery centers.
For products that cannot be deposited at their final moisture
content, a drying or stoving stage follows deposition. The trays
are held in a drying atmosphere at 50–60
C, and 10–40%
relative humidity until the candies reach the desired moisture
content. The drying time varies from 24 to 72 h depending on
the type of candy, and is the rate-limiting step in the molding
process. Drying is an energy-intensive process, and manufac-
turers are interested in optimization to achieve maximum
production capacity with minimal energy consumption.
*Correspondence to: Professor G.R. Ziegler, 116A Borland Lab, Department
of Food Science, Penn State University, University Park, PA 16802, USA.
E-mail: grz1@psu.edu
Once the candies are sieved out, the starch is dried and
recycled back to the mogul for reuse. The process of
recycling the molding starch is called starch conditioning,
which is also energy-intensive. The typical amount of
energy needed to reduce the moisture content of one
kilogram of starch by 1% is 64 kJ (27.5 BTU lb1; Collins,
1989). The required ratio of molding starch per unit mass of
candy deposited is a key factor in minimizing the starch
conditioning energy. Tray size is standardized to facilitate
mechanical handling by the mogul, but it is uncertain
whether tray depth has ever been optimized in relation to
drying efficiency.
The relative rates of drying through the surface exposed
to air vis-à-vis that in contact with the molding starch has
not been clearly explained in the literature. Brock (1950)
determined that the final moisture content in trays of
molding starch was established by the relative humidity
(RH) of the drying air, but that the drying rate was
influenced by temperature alone. Grover (1947) studied
moisture permeation rates through confectionery jelly and
concluded that the rate of drying was independent of RH
below 60%. While drying temperatures are common in the
literature, much less attention is given to other environ-
mental conditions such as RH or air velocity, suggesting
atmospheric conditions have little effect on the process
(Kintz, 1996). Motion of the air has no effect except as it
influences the RH by carrying moisture away from the

60
 DIFFUSION IN STARCH MOLDING
Figure 1. Transport mechanism of moisture during stoving of starch jellies.
starch and out of the conditioned area (Brock, 1950). These
observations lead to the conclusion that for most starch-
molded products drying is diffusion controlled.
It is common to find a dry ‘skin’ on the surface of
products manufactured using starch molding, formed from
a region of low moisture content near the surface. This skin
is beneficial to products with a soft center since it prevents
pieces from sticking together and resists mechanical stresses
during handling. Seager (1991) intuitively explained the
formation of this moisture gradient by stating that the
moisture transfer inside the candy cannot replace loss of
moisture on the surface. The presence of a skin could
severely limit the drying rate since moisture diffusivity is
concentration dependent. Initially, moisture must move
rapidly from the outer surface of the product to encourage
‘skinning’, which aids in shape definition (Best, 1990).
However, if too rapid, moisture removal at the surface can
result in ‘case hardening’ that can actually slow moisture
transfer overall. Moisture trapped in this way may cause
‘sweating’ during storage. Ziegler et al. (2003) observed
skin formation in a model starch molding system using
magnetic resonance imaging, and determined that drying
was effectively diffusion-controlled after the first 30
minutes. Ziegler et al. also concluded that drying via the
candy–molding starch interface was more effective than that
through the candy–air interface.
The possible transport mechanism for moisture migration
during the actual drying process has been outlined in
Figure 1 (Ziegler and Sudharsan, 2000). The objective of
the present work was to develop a model that would
quantitatively predict the moisture diffusion from a single
candy piece into the starch bed or air at a given temperature
(50
C).
MODEL FOR MOISTURE MIGRATION
DURING STOVING
The rate-limiting mechanism for moisture transfer
(convection or internal diffusion limited mass transfer)
was determined by evaluation of the Biot number (Bi) at
the candy–air and starch–air interface. In the case of a flat
plate, Bi is given by equation (1).
Km L
Bi ¼
D isotherms.
Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
61
The average mass transfer coefficient, Km, was calculated
using the correlation between Sherwood number (Kml=Dg),
Reynolds number (lrV=m) and Schmidt number (m=rDg) for
an external laminar flow along a flat plate given by equation
(2) (Cussler, 1996):

1=2 !1=3
Km l rlV m
¼ 0:323 (2)
Dg m rDg
The velocity of air in the drying room is approximately
0.05 m s1 (Kintz, 1996), and this value has been used for
further calculations. The length (l) of candy pieces was
taken to be 5 cm and thickness (L) to be 0.5 cm. The
diffusion coefficient of moisture in candies is not well
reported. Yamamoto et al. (1997) has reported values of
the diffusivity of moisture in sucrose at 30
C, a major
ingredient in the candy, of the order of 1011–
1014 m2 s1. Vagenas and Karathanos (1992) have reported
diffusivities in gelatinized starch, another ingredient in
candy, in the order of 1010–1011 m2 s1. Vagenas and
Karathanos (1991) have estimated the effective diffusivity in
granular Hylon 7 to be between 1–2  109 m2 s1 in the
temperature range 40–60
C at a porosity of 0.5. A conser-
vative value of 5  109 m2 s1 was taken as the diffusion
coefficient of moisture for the Biot number analysis, giving
a Bi value of the order 103, suggesting that internal diffusion
in the candy and starch phases would probably be the rate
limiting mechanism for moisture transfer.
The variety of shapes of real candy pieces is complex,
making modelling difficult. To circumvent this problem, the
shape of the candy pieces have been taken to be a hemi-
sphere (Figure 2), not an unreasonable shape. The shape of
the starch bed has been taken to be a hollow hemisphere,
with the candy residing in the center (Figure 2). All the
assumptions involved in developing the model have been
listed below:
(i) no change in densities of the candy or the starch bed;
(ii) no shrinkage or expansion occurs in the candy or
starch bed during the drying process;
(iii) uniform moisture content in the starch bed and
candy at the beginning of the process;
(iv) heat transfer in the system is much faster when
compared to mass transfer and the system is consid-
ered isothermal;
(v) diffusion coefficient in the candy was a function of
moisture content in the candy (Yamamoto et al.,
1997; Vagenas and Karathanos, 1992);
(vi) diffusion coefficient in the starch bed was a constant
within the typical operating moisture range (between
6 and 12%);
(vii) the diffusion process in the system is assumed to be
Fickian;
(viii) the air–candy and air–starch surfaces immediately
reach equilibrium determined by the external relative
humidity;
(ix) the candy–starch interface immediately came
to its equilibrium value as determined by the
(1)
62 SUDHARSAN et al.

Figure 2. Finite difference grid used in the starch–candy system.

Moisture Diffusion in the Candy Phase about the center axis. Thus the ‘j’ term in equation (3) is
neglected giving equation (4):
The unsteady-state diffusion equation in spherical coor-
dinates, neglecting the convective terms is presented as
equation (3) (Bird et al., 1994):

@X 1 @ 2 @X 1 @

 ¼ 2 r D(X ) þ
@X 1 @ 2 @X 1 @ @t r @r @r r sin (y) @y
¼ 2 r D(X ) þ

@t r @r @r r sin (y) @y D(X ) sin (y) @X

  (4)
D(X ) sin (y) @X 1 @ r @y
 þ
r @y r sin (y) @f t¼0 X ¼ Xo 0  r  Rcandy y ¼ all (5)


D(X ) @X t ¼ all X ¼ Xequ 0  r  Rcandy y¼0 (6)
 0  r  Rcandy , t  0 (3)
r sin (y) @f
t ¼ all X ¼ Xequ r ¼ 0 y ¼ all (7)
Since the moisture content in the candy and starch bed is @X p
t ¼ all ¼ 0 0  r  Rcandy y ¼ (8)
uniform at the beginning of the process, there is symmetry @y 2

Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
 DIFFUSION IN STARCH MOLDING 63

The fourth boundary condition is the flux condition at the the Taylor series was used to account for the steep gradients
starch-candy interface. This is dealt with separately. Figure 2 that might arise at the interface.
summarizes the boundary conditions. Differencing equations (4) and (9) resulted in tri-diagonal
matrixes with fringes (Sudharsan, 2001). In the case of the
candy phase the set of simultaneous equations obtained
Moisture Diffusion in the Starch Phase were non-linear and in the starch phase equations were
The process of moisture migration in the starch bed was linear. The Gauss–Seidel iterative technique was used to
by porous diffusion with adsorption of moisture on the solve the matrix (Press et al., 1992). The generalized
surface of the starch particles. Previous work on the diffu- algorithm to solve the starch–candy system completely is
sion of moisture in granular starch suggested that the explained in Figure 3. The concentration values at the
effective diffusivity at 50
C might be constant (Vagenas starch–candy interface were always solved before going
and Karathanos, 1991) in the operating moisture range of 6– onto the next time step and were checked for change,
12% (wet basis). The unsteady-state diffusion equation in because the flux condition solved initially was solved
spherical coordinates neglecting the convective term and the using the values at the previous time step and was not
‘j’ term is presented as equation (9) (Bird et al., 1994): truly the implicit solution at the interface.

 A 50  50 grid (50 nodes radial direction and 50 nodes in
@Y 1 @ 2 @Y 1 @ the ‘y’ direction) was overlaid on the candy and starch
¼ 2 r Ds þ
@t r @r @r r sin (y) @y


Ds sin (y) @Y
 (9)
r @y
t¼0 Y ¼ Yo Rcandy  r  Rstarch y ¼ all (10)
t ¼ all Y ¼ Yequ Rcandy  r  Rstarch y¼0 (11)
@Y p
t ¼ all ¼ 0 Rcandy  r  Rstarch y¼ (12)
@y 2
@Y
t ¼ all ¼ 0 r ¼ Rstarch y ¼ all (13)
@r
The fourth boundary condition is the flux condition at the
starch–candy interface and is explained below.
At the starch–candy interface, any moisture that leaves
the candy enters the starch bed, and the water activity of the
starch is equal to the water activity of the candy at this
interface.
astarch
w (Y jt¼t
r¼Rcandy ,y¼y ) ¼ aw
candy
(X jt¼t
r¼Rcandy ,y¼y ) (14)
t¼t t¼t
@Y  @X 
rstarch Ds  ¼ rcandy D(X ) 
@r r¼Rcandy ,y¼y @r r¼Rcandy ,y¼y
(15)

Solving the System of Diffusion Equations

To predict the moisture profiles in the starch-candy
system, it was necessary to solve unsteady-state diffusion
equations in the candy phase [equation (4)] and the starch
phase [equation (9)] simultaneously with the appropriate
boundary conditions. The Crank–Nicholson finite difference
scheme was used to solve the diffusion equations implicitly
with the grid shown in Figure 2.
To solve for the concentration profile at the starch-candy
interface, the flux condition [equation (15)] was solved
simultaneously with the water activity relation [equation
(14)] at the interface (Sudharsan, 2001). From equation (14)
a relation between the equilibrium moisture content in the
candy and the equilibrium moisture content in the starch
was derived. This relation was then back substituted into
equation (15) (Sudharsan, 2001). This converted equation
(15) into an equation with one variable, which was solved
using the bisection method (Press et al., 1992). While finite Figure 3. Generalized algorithm to solve the starch–candy system
differencing equation (15) a second-order approximation of implicitly.

Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
64 SUDHARSAN et al.
phases respectively, and the solution was obtained for 0.1 s
time steps. The choice of time step as 0.1 s seemed appro-
priate as the implicit solution obtained using Dt ¼ 0.01 s was
not significantly different, while that obtained using Dt ¼ 1 s
was different. A 100  100 grid in the candy and starch
phases respectively took approximately 2 weeks to solve for
30 h of drying time on a 700 MHz desktop computer. The
implicit solution obtained using a 100  100 grid was not
significantly different from that obtained using a 50  50
grid.
The mass average concentration of the candy was then
obtained by integrating the concentration profile radially and
later in the ‘y’ direction according to equation (16).
H Company Inc., Bohemia, NY, USA) using methanol (Karl
V X dv
Xavg ¼ (16)
(2=3)pR3candy
To integrate, Simpson’s 3 rule was used (Press et al., 1992).
Press et al. have commented that using a one-dimensional
integral technique to evaluate a multidimensional integral
would yield a solution of low accuracy. As a first step to
evaluate the integral the above technique was used.
The integral solution obtained was checked by solving for
a simple case, the volume of a hemisphere (23 pR3candy ). The
predicted volume of the hemisphere was 8.9% less than the
true value while using 50  50 grid (50 nodes in radial
direction and 50 nodes in ‘y’ direction) and was 4.9% less
than the true value while using a 100  100 grid and was
1.59% less than the actual while using a 300  300 grid.
Reducing the grid size further improved the integral solution
but it was impractical to solve the system of diffusion
equation for such a refined grid. As a first approximation,
the 50  50 grid was chosen and a 9% numerical error in
the integral solution was expected. This then was the source
of error observed in Figure 11 (i.e., an initial moisture
content lower than the given initial conditions). However,
this approach still allows us to compare one case to another.
A ‘C’ program was written to solve the above unsteady-state
diffusion equation for a given set of initial and boundary
conditions in the candy phase and evaluate the mass average
concentration. The code was developed on a Linux work-
station with 128 MB RAM and an Intel 700 MHz PIII proces-
sor. The GNU ‘C’ compiler from Free Software Foundation
(Boston, MA, USA) was used to compile the source code.
The experimental parameters needed to model the starch–
candy system were the adsorption isotherm of starch,
desorption isotherm of candy, diffusion coefficient of
water in the starch bed and the diffusion coefficient of
water in the candy as a function of moisture content.
MATERIALS AND METHODS
Adsorption Isotherm of Starch at 50
C
Molding starch (unmodified cornstarch) was obtained from
National Starch and Chemical Company (Bridgewater, NJ,
USA). Cornstarch (2–4 g) was vacuum dried and placed in
aluminum weighing dishes (44 mm i.d.  12 mm deep) on
wire mesh supports inside sealed Mason canning jars (473 ml).
The jars were filled to a depth of about 1 cm with saturated salt
solution, and kept in an environmental chamber (Environ cab,
Lab-Line Inc., IL, USA) at 50  1
C. Different salt solutions
were chosen so that the samples were equilibrated over a broad
range of relative humidity. Greenspan (1977) has tabulated
Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
values of relative humidity of various saturated salt solutions
for a broad range of temperature. The starch samples took 2–4
days to equilibrate at a given relative humidity. The moisture
content in the samples was then determined using nuclear
magnetic resonance (NMR) (Minispec-MQ20, Bruker,
Canada) as described below.
Determination of Moisture Content
in Starch using NMR
The free induction decay signal intensity per unit mass of
starch was calibrated against moisture content determined
by potentiometric Karl Fischer titration (Koehler Instrument
Fischer grade, anhydrous, Fischer Scientific, Pittsburgh, PA,
USA) as the solvent to extract moisture from the starch
(Troutman, 1999). The GAB equation [equation (17)] was
used to fit the data:
Wm CKaw
M¼ (17)
(1  Kaw )(1  Kaw þ CKaw )
where C and K are fitted parameters.
The GAB equation (Van den Berg, 1984) gave a good fit
(r2 value ¼ 0.9892, average error ¼ 1.4%) to the data
(Figure 4). The values of the GAB parameters obtained
using ‘Solver’ (Microsoft Excel, Microsoft Corp., Redman,
WA, USA) were Wm ¼ 0.087, K ¼ 0.574 , C ¼ 31.8.
Desorption Isotherm of Candy at 50
C
Commercial gummy bears were frozen and cut into small
chips. Typical formulae used in manufacturing gummy bears
is 40% sucrose, 41.36% corn syrup 42 D.E., 6.32% gelatin,
1.04% citric acid and 11.28% water (Warnecke, 1991). Care
was taken not to contaminate the product; the work area and
accessories used were cleaned with ethyl alcohol and
potassium sorbate, an anti-molding agent. The shredded
product (0.25–0.5 g) was placed in aluminum weighing
dishes (44 mm i.d.  12 mm deep) over pure water in a
desiccator. Once the product picked up moisture more
than twice its weight, it was taken out and equilibrated
over saturated salt solutions in Mason jars as described
above. The dishes were weighed periodically after 2 days to
check if the sample had reached a constant weight. Samples
kept at a water activity of 0.45 and above equilibrated within
14 days. For samples kept at water activities below 0.45, a
clear sign of equilibration was not observed; a loss of
approximately 103 g (0.2%) was observed for every 2
days. Although the samples did not equilibrate completely,
the percentage loss of moisture suggested that the samples
were near equilibrium. Methanol was used as a solvent for
moisture extraction. The solvent was titrated against Karl
Fischer reagent and the amount of moisture in the product
was back calculated using the dilution factor and amount of
moisture present in the solvent (Troutman, 1999). The GAB
equation gave a good fit to these data (r2 value ¼ 0.9942,
average error ¼ 5.35%). Values of the GAB equation para-
meters obtained were Wm ¼ 0.041, K ¼ 1.13, C ¼ 31.3. The
isotherm obtained (Figure 5) is comparable to the J-type
isotherm obtained by Troutman (1999) for starch jelly
centers at 20
C, and to the isotherm reported by Van den
Berg and Bruin (1981) for crystalline sucrose at 40
C.
 DIFFUSION IN STARCH MOLDING 65

Figure 4. Adsorption isotherm for cornstarch at 50
C.

Estimation of Diffusion Coefficient of

Moisture in the Starch Bed at 50
C
A tray filled with saturated salt solution (sodium chloride,
RH 74.4%), a small fan and a balance (Mettler PE-360) Figure 6. Experimental setup to determine sorption curves for starch and candy.
were placed inside a Plexiglas box (0.4  0.2  0.2 m) as
shown in Figure 6. The whole box was kept in an environ-
mental chamber at 50
C. A circular Plexiglas dish with an The experimental drying curve was fitted to the one-
inner depth of 1 cm and an inner diameter of 7.68 cm dimensional, unsteady-state diffusion equation [equation
(weight ¼ 67.09 g) was custom made, filled with vacuum (18)] with constant diffusivity and a flux condition at the
oven-dried starch, and placed on the balance. The Mettler starch–air interface:
PE-360 type balance was chosen since it was sensitive @Y @2 Y
enough (0.001 g) to record the change in weight of the ¼ Ds 2 (18)
starch yet not sensitive to other vibrations in the environ- @t @z
mental chamber. The weight of the drying dish was recorded Y ¼ Yo z ¼ all t¼0 (19)
periodically until equilibrium was attained, after approxi-
mately 39 h. It was observed that the relative humidity in the @Y
rstarch Ds ¼ Kg [astarch
w (Y jt¼t starch
z¼1 )  aw (Yequ )]
box did not reach its equilibrium value immediately. This @z
suggested that the fan speed was not fast enough and that z ¼ 1 cm t ¼ all (20)
there was a significant film resistance for mass transfer. @Y
From Figure 7 a small bend in the sorption curve can be ¼ 0 z ¼ 0 t ¼ all (21)
seen during the start of the experiment that can be attributed @z
to the film resistance in the air phase. The bulk density of An implicit finite difference scheme was used to solve the
the starch bed was 700.2 kg m3. Cracks and a 1 mm (10%) diffusion equation (Press et al., 1992). A ‘C’ program was
increase in the bed depth were observed in the starch bed written to do the fitting (Sudharsan, 2001). The solution
during adsorption. This increase in the depth was neglected obtained was checked against the solution obtained by
during estimation of the diffusivity. Crank (1975) for a linear isotherm. One-hundred nodes

Figure 5. Desorption isotherm for candy at 50
C. Figure 7. Experimental and fitted sorption curves for starch at 50
C.

Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
66 SUDHARSAN et al.
were used to discretize the length of the starch bed with
Dt ¼ 0.1 s. To solve for the flux condition at the starch–air
interface, the relationship between the equilibrium RH and
the moisture content of starch was needed. This was
obtained from the GAB isotherm of molding starch. The
bisection method was used to solve the flux condition and
the technique was similar to that used in solving the flux
condition at the candy–starch interface. Once the concentra-
tion profile in the slab was estimated as a function of time,
the profile was integrated using Bode’s five-point rule (Press
et al., 1992) to estimate the mass of the sample at a given
time t. The dimensionless mass, M*, was then calculated
using equation (22).
Mt  Mo
M ¼ (22)
Mequ  Mo
There was good fit between the experimental and
predicted adsorption curves (Figure 7; r2 ¼ 0.998, average
error ¼ 0.66%). The estimated effective diffusivity in the
starch bed was 4.1  109 m2 s1 and the mass transfer
coefficient in the system, Km, was 4.5  104 kg m2 s1.
Vagenas and Karathanos (1991) have estimated the effective
diffusivity in granular Hylon 7 to be between 1  109 and
2  109 m2 s1 in the temperature range 40–60
C at a
porosity of 0.5.
The apparent diffusivity of moisture in the porous starch
bed obtained using the experiment above was checked using
the procedure outlined below. Let the adsorption isotherm of
starch be linear and given by equation (23).
Cstarch ¼ ACair (23)
The apparent diffusivity of the system could be obtained
from the equation (24) (Weisz, 1995). Weisz (1995) has also
commented that in the case of non-linear isotherms the value
of diffusivity derived might not change by more than a
factor of 1.6:
Dapparent ¼ Dg =A (24)
In the present case the diffusivity of water vapor at 50
C
in air (Dg ¼ 2.47  105 m2 s1) was estimated (Wilke and
Lee, 1955) and it was divided by the slope (A ¼ 2615) of the
starch isotherm at Y ¼ 6% (typical moisture content at the
start of the drying process). The value of Dapparent thus
estimated was 9.5  109 m2 s1. The estimated value does
not account for the tortuosity, usually between 1.5 and 2
(Weisz, 1995), or the porosity of the system (e 0.48), both
of which would decrease the estimated diffusivity value
even further, but not by orders of magnitude.
Diffusion Coefficient as Function of Moisture
Content in the Candy at 50
C
The experimental setup to obtain the drying curve of the
candy is similar to that of the starch (Figure 6), except that
magnesium chloride (aw ¼ 0.305) was used as the salt
solution and the depth of the drying dish used was 1 mm.
The inner radius of the custom made drying dish was
7.67 cm (weight ¼ 97.15 g). Frozen starch jelly slurry was
obtained from Harmony Foods Inc. (Santa Cruz, CA, USA).
The composition of the starch jelly was comparable to the
example formulation given by Warnecke (1991). The slurry
was reheated so that it was fluid enough to be deposited in
Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
the drying dish. The drying dish was placed on the balance
and the weight of the dish was noted periodically until a
constant weight was reached.
The candy drying experiment was stopped after 4 days
even though complete equilibration of the sample was not
obtained. The initial thickness of the sample in the drying
dish was 1 mm. At the completion of the experiment, the
thickness of sample at the center of the dish was observed to
be 0.5 mm and at the sides it was 0.95 mm, a uniform gradient
was not observed. To account for this shrinkage, the average
thickness of the sample was taken to be 0.75 mm. Also, the
bend seen in the drying curve of starch was less apparent in
the drying curve of candy (Figure 8) because the RH of the
ambient air was between 30 and 40% at the time of closing the
Plexiglas box and the salt solution did not take long to bring
the relative humidity to 30.5%.
The unsteady-state diffusion equation with variable diffu-
sivity [equation (25)] was solved using implicit finite
differencing technique (Press et al., 1992). The exponential
function in equation (26) was used to describe the concen-
tration dependence of the diffusion coefficient of moisture in
the candy. A ‘C’ code was developed to solve equation (25).
One-hundred nodes were used to discretize the radius of the
candy with Dt ¼ 0.1 s. Once the concentration profile in the
slab was estimated as a function of time, the profile was
integrated using Bode’s five-point rule (Press et al., 1992) to
estimate the mass of the candy at a given time t. The values
of Do(1.7  1010 m2 s1) and Ao (0.23) were optimized by
trial and error to give the best fit for the experimental drying
curve (Figure 8) (r2 ¼ 0.9973, average error ¼ 1.35%).
 
@X @ @X
¼ D(X ) (25)
@t @z @z


A
D(X ) ¼ Do exp  o (26)
X
X ¼ Xo z ¼ all t ¼ 0 (27)
X ¼ Xequ z ¼ 1 mm t ¼ all (28)
@X
¼ 0 z ¼ 0 t ¼ all (29)
@z
The experiment was repeated using a salt solution of
sodium bromide of aw ¼ 0.51 (Greenspan, 1977). This was
done to check the ability of the diffusion model proposed
Figure 8. Experimental and fitted sorption curves for candy at 50
C.
 DIFFUSION IN STARCH MOLDING
Figure 9. Diffusion coefficient for moisture as a function of moisture
content of candy at 50
C.
[equation (26)] to interpolate. The experimental drying
curve was compared with the predicted drying curve
(Do ¼ 1.7  1010 m2 s1 and Ao ¼ 0.23). There was good
agreement between the predicted and the experimental curve
(r2 ¼ 0.9829, average error ¼ 5.85%).
The diffusivity of moisture in starch jellies, as a function
of moisture content is not well reported in literature.
Yamamoto et al. (1997) have estimated diffusivity in
sucrose, a bulk ingredient in the candy, as a function of
moisture content at 30
C using a power law model (Figure 9).
They have reported effective diffusivity values between
1015 and 1011 m2 s1 in a moisture content range of
0.02–0.4 (wet basis). These values of the effective diffusivity
are significantly lower than the present work (Figure 9).
In addition to the compositional differences, this could be
attributed to the lower temperature (30
C) at which they
carried out their experimental work. Using the isotherm of
the candy a relationship between the water activity and the
diffusion coefficient of the candy was obtained (Figure 10).
RESULTS AND ANALYSES
The experimentally obtained adsorption isotherm of the
starch, desorption isotherm of the candy, the effective diffu-
sion coefficient in the starch bed and the effective diffusion
coefficient in the candy as function of moisture content, were
used in the model to solve for the concentration profile in the
starch–candy system. It was observed that the solution was
most sensitive to the order of magnitude of the diffusion
coefficients, i.e., if the prediction of the diffusion coefficients
in the above experiments were off by an order of magnitude,
then the concentration profile obtained would have been very
different. The isotherms mostly influenced the equilibrium
values at the interfaces.
The effect of the initial moisture content of the starch bed,
the relative humidity of the drying air, and the spacing
between the pieces, on the drying process was investigated;
the starch–candy system was solved implicitly for five
different cases (Table 1). The mass average concentration
of moisture in the candy as a function of drying time for the
five different cases is shown in Figure 11.
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67
Figure 10. Diffusion coefficient for moisture as a function of water activity
for candy at 50
C.
Case 1: Typical Operating Conditions
This case is representative of the typical commercial
operating conditions at which drying is done. The initial
moisture content in the candy was 25% but the predicted
mass average concentration was 22.1% (Figure 11), this error
was due to the numerical error while evaluating the multi-
dimensional integral as explained earlier. At time t ¼ 0.1 s
(Figure 12) a skin of very low moisture concentration
(approximately 3.8% wet basis) was formed around the
candy. The effective diffusivity at this concentration was
5  1013 m2 s1. The effective diffusivity at the center of the
candy was in the order of 1011 m2 s1. The diffusivity in the
starch bed was in the order of 109 m2 s1, about 100 times
faster than that in center of the candy. From this it was evident
that the moisture in the bulk of the candy was not able to
replace the quick loss of moisture at the surface of the candy,
conforming with the intuitive explanation given by Seager
(1991). The skin formed not only limited the moisture
escaping into the starch bed but also into the air above.
There was no significant accumulation of moisture in the
starch bed even after 30 h of drying (Figure 13). This
suggested that the starch played an important role in
absorbing moisture from the candy. This is contrary to the
conclusion made by Kintz (1996); she had concluded that
starch played no role in the drying of the candies. At t ¼ 30 h
it could be seen that the moisture content in the center of the
candy was still between 20 and 22% (wet basis) and
surrounded by skin of low moisture content. This might
explain, why the centers of Swedish fish (a low-moisture
product similar to wine gums) are soft yet the outer surface
is hard enough to withstand any mechanical stresses. Also,
the candies do not stick together when the skin is very dry.
Stickiness is an important quality criterion for manufactures
who wish to avoid lumping of candies within a package.
At the end of 30 h of drying, it could be seen that the skin
formed at the starch–candy interface was thicker than that
formed at the starch–air interface. The surface area of the
candy exposed to the starch bed was 2pR2candy and that exposed
to the air is only pR2candy (half that exposed to starch). Therefore
the amount of moisture removed into the starch bed was much
more than that removed into the air. This was more evident
from a plot of the concentration profile in the candy, as shown
in Figure 14 for y ¼ p=2 and time t ¼ 30 h.
68 SUDHARSAN et al.
Table 1. Operating conditions of different drying cases studied.
Initial moisture in Initial moisture in
the starch (wet basis) the candy (wet basis)
Case 1 6% 25%
Case 2 10% 25%
Case 3 6% 25%
Case 4 6% 25%
Case 5 6% 25%
Case 2: Higher Initial Moisture in the Starch Bed
The effect of increasing the initial moisture content of the
starch bed to 10% while keeping other operating conditions
the same as in case 1 was modeled. It can be observed that
the center moisture in the candy had dropped by the same
3–4% (Figure 15) as observed in case 1 after 30 h of drying,
but that the moisture content in the skin was around 10–13%
(w.b.) or about four times higher than in Case 1. At a
moisture content of 8–13% (w.b.) the candy is very sticky
(by observation). The moisture content at the candy–air
interface was still around 3.6% due to the low relative
humidity of the air (10%). From Figure 11 it can be seen
that the mass average concentration of the candy was much
higher for case 2 than case 1, which could be attributed to
the lower concentration gradient, i.e. driving force, at the
starch–candy interface, again pointing to the importance of
moisture transport to the molding starch. Here a quasi-
steady state is reached in the starch bed. If the starch used
is not conditioned properly, it is possible that the initial
moisture content in the starch bed is around 10%. In such
cases it is common to see sticky products.
Case 3: Higher Relative Humidity of Air
This case was chose to study the effect of the RH of
the drying air on the process. The RH of air was taken to be
Figure 11. Mass average concentration of moisture in candy as a function of drying time.
Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
Air relative Diameter of Thickness of the
humidity (%) candy piece (cm) starch bed (cm)
10 2 1
10 2 1
30 2 1
10 2 1.5
10 2 0.5
30%, with the other operating conditions as in case 1.
The initial moisture content in the starch bed was 6% and
the equilibrium moisture content at 30% RH was 8.4%,
therefore it could be clearly seen that starch absorbs moisture
from the external air. A similar situation can be seen in the
manufacturing plant when the starch is exposed to uncondi-
tioned air (  40% RH). In Figure 16 it can be seen that the
moisture content at the starch–candy interface rises from
3.6% in case 1 to 9%. The mass average concentration is
approximately the same as observed in case 1.
Case 4: Greater Spacing Between the Candies
The effect of increasing the space between candy pieces on
the drying process was studied by increasing the depth of the
starch bed to 1.5 cm. The mass average concentration profile
obtained was very similar to profiles in case 1 (Figure 11). It
was predicted that increasing the depth of the starch bed by
0.5 cm would not therefore improve the drying rate.
Case 5: Lesser Spacing Between the Candies
The effect of decreasing the space between candy pieces
on the drying process was modeled by decreasing the depth
of the starch bed to 0.5 cm. The mass average concentration
profile obtained was similar to the profiles in cases 1 and 4,
suggesting that decreasing or increasing the spacing, at least
 DIFFUSION IN STARCH MOLDING
in the range 1–3 cm edge-to-edge, might not affect the
drying during typical drying conditions, perhaps because
of the larger diffusivity in starch (at least 100) when
compared with the diffusivity in candy. This does not
mean that spacing between the candies could be reduced
completely, because making a good impression in the starch
requires certain structural integrity and continuity with the
air phase must be maintained.
DISCUSSION AND CONCLUSIONS
Stoving of starch jellies is necessary to remove excess
moisture from the candy. During stoving at typical operating
conditions the moisture migration in the starch–candy–air
system was via three different routes.
(i) direct migration of moisture from the candy into the
starch bed;
(ii) direct migration of moisture from the candy into
the air;
(iii) migration of the moisture from the starch bed into
the air, depending on the relative humidity of air.
At typical operating conditions, starch plays an important
role in taking up moisture from the candy and giving it up to
the air. The effect of intial moisture content in the candy and
the thickness of the candy piece in this diffusion-limited
drying process is more obvious, while the effect of initial
moisture content in the starch bed, relative humidity and
thickness of the starch bed are less intuitive and have been
explained below. The effect of temperature on the drying
process has not been modeled in this study. At higher
temperature the diffusion coefficients in the candy would
increase and may improve drying. In general, the conclu-
sions drawn from these modelling exercises confirm
observations made in model systems (Ziegler et al., 2003)
and during tests we undertook in a commercial manufactur-
ing plant.
Initial Moisture Content in the Starch Bed
At typical operating conditions, a skin of low moisture
content and diffusivity was formed at the candy–starch
Figure 14. Moisture concentration profile in starch–candy system at
y ¼ p=2 and time t ¼ 30 h (case 1).
Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
69
interface. This skin limited the moisture migration from
the candy into the starch bed. We hypothesized that moisture
diffusivity could be improved by initiating the drying
process with higher moisture content in the starch bed, but
perhaps not as high as case 2, limiting skin formation at the
expense of a lower moisture gradient at the starch–candy
interface. For example, let equation (30) determine the flux
at the starch–candy surface.
@X
Moisture flux ¼ rcandy D(X ) (30)
@r
Now by increasing the initial moisture content in the starch,
the concentration gradient (@X =@r) decreases but the diffu-
sivity (D) improves. Therefore for some moisture content
the flux is maximized. This is an excellent optimization
problem, and has been left for future work. It might also be
possible that the typical operating conditions used by
manufactures are already optimal.
Thickness of the Starch Bed
The thickness of the starch bed did not affect the drying at
typical operating conditions. This does not mean that the
thickness could be reduced indefinitely since getting a good
shape definition on the starch might become a key factor.
Typical tray heights vary from 46 to 56 mm with starch
depths typically from 23 to 33 mm (Pyrz, 1994). Since the
thickness of the starch bed did not affect the drying rate at
typical operating conditions it would be possible to reduce
the depth of the trays. Any reduction in the depth of the tray
would reflect as saving in the energy required to condition
the starch, i.e. the amount of starch used per kg of candy
deposition could be reduced. Reduction in the depth would
also mean more trays could be stacked in the drying room.
Any capacity increase should also be augmented by increas-
ing the amount of drying air used to avoid a higher RH of air
in the stoving room.
Relative Humidity of Air
Air is the final sink for all the excess moisture in the
candy. The relative humidity of the air indirectly controlled
the concentration gradient at the starch–candy interface,
since the starch bed picked up or lost moisture as dictated
by the relative humidity of the air. Starting the drying
process at a higher relative humidity and decreasing this
parameter during the process might help in enhancing
diffusion during the initial stage of the process and
decreasing the humidity during the later stages might
give the mechanical stress needed for handling the candies.
The way in which the relative humidity should be
decreased as a function of time is also an excellent control
problem.
NOMENCLATURE
aw water activity
acandy
w water activity in the candy for given moisture content
astarch
w water activity in the starch bed for given moisture content
A sorption constant
Ao exponential constant
Bi Biot number
C adsorption constants relating the energies of interaction
between the first and further adsorbed molecules at indivi-
70 SUDHARSAN et al.

Figure 12. Moisture concentration profile in starch–candy system at time t ¼ 0.1 s (case 1; candy section displaced upwards to aid in visualization).

Figure 13. Moisture concentration profile in starch–candy system at time t ¼ 30 h (case 1; candy section displaced upwards to aid in visualization).

Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
 DIFFUSION IN STARCH MOLDING 71

Figure 15. Moisture concentration profile in starch–candy system at time t ¼ 30 h (case 2; candy section displaced upwards to aid in visualization).

Figure 16. Moisture concentration profile in starch–candy system at time t ¼ 30 h (case 3; candy section displaced upwards to aid in visualization).

Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72
72 SUDHARSAN et al.

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ACKNOWLEDGMENTS
The authors express their gratitude to General Mills Inc. for financial
support, and to Harmony Foods Inc. for supplying samples and allowing us
to verify models in a production setting.
The manuscript was received 30 June 2003 and accepted for publication
after revision 30 January 2004.

Trans IChemE, Part C, Food and Bioproducts Processing, 2004, 82(C1): 60–72