Mass transfer of gas

and solute through

packaging materials
Jung H, Han and Martin C. Scan Ion

introduction 12
General theory 14
Diffusivity 15
Solubility/partitioning 15
Overall mass transfer of gases and solutes 18
Summary 20
References 22

Introduction
There are many applications in the area of food packaging that use mass transfer phe-
nomena. Examples include selecting a packaging material to predict and extend product
shelf life, and to control the in-package atmosphere for protection and preservation of
food products. Permeation, absorption and diffusion are typical mass transfer phe-
nomena occurring in food packaging systems (Figure 2.1). Permeation is the ability
of permeants to penetrate and pass right through an entire material in response to a
difference in partial pressure - the gas and water vapor transmission rates of pack-
aging materials give a good indication of permeation. This property of the packaging
material may also be referred to as the "permeance" (ASTM, 1993; Segall and
Scanlon, 1996). To convert the permeance (which is evidently dependent on the thick-
ness of the film) into an intensive property, the permeance is multiplied by the film
thickness to derive the permeability (P) of the film. Thus the mass transfer coefficient
for permeation is permeability (P). The mass transfer of a solutefi*oma solution through
a (polymeric) material is also a useful way to determine mass transfer coefficients
experimentally, because it requires simple permeation apparatus (i.e. a permeation
cell) consisting of the high and low concentration solution chambers divided by the
test film material. The concentration increase of the substance in the low concentration
chamber is measured to determine the permeance. Durrheim et al (1980) showed the

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 Mass transfer o f gas and solute through packaging materials 13

Permeation • • • Permeability (P)

Solubility (S) and

Absorption
partition coefficient (K)

Diffusion Diffusivity (D)

Figure 2.1 Mass transfer phenomena and their characteristic coefficients.

relationship between the chain length of various alkanols and their permeability
through mouse skin and human epidermal tissue. It was found that the permeability
increased exponentially with increasing length of the carbon chain, up to eight carbons.
Diffusion is the movement of a diflfusant in a medium caused by a concentration dif-
ference acting as a driving force. Diffusivity (D) is a measure of how well the compound
diffuses in the medium. Schwartzberg and Chao (1982) reported the diffusivities of dif-
ferent kinds of food components in food systems. Rico-Pena and Torres (1991) meas-
ured the diffusivity of potassium sorbate through a methylcellulose-palmitic acid film
under various conditions of water activity and pH. The diffusivity of potassium sorbate
through the ediblefilmincreased with decreasing pH and with increasing water activity.
Absorption and its counterpart desorption measure the affinity of a given substance
for two media with which it comes into contact. Flavor scalping of d-limonene, an orange
flavor component, into the sealing layer of aflexiblepackaging material for orange juice
is a good example of absorption in packaging. The d-limonene has a much higher affin-
ity for the plastic layer than for the juice, in which it should preferably reside. The
affinity of a substance for a material can be expressed using the solubility (S) or parti-
tion (K) coefficient. A microbial stability model for intermediate moisture foods has been
suggested based on the concentration distribution of sorbate in edible polysaccharide
films (Torres et aL, 1985; Torres, 1987). The intermediate moisture foods were also
coated with a zein protein-containing sorbate. The microbial stability factor was the sor-
bate concentration during storage, and the higher concentration of the residual sorbate
was assumed to maintain the higher microbial stability of the intermediate moisture food.
The permeability, solubility, and diffusivity have characteristic values for a migrating
component through a particular medium. These parameters are therefore essential in
simulating the mass transfer profile. This chapter reviews mass transfer phenomena
and defines the diffusivity, permeability, solubility, and partition coefficient of trans-
ferring molecules. Gases and solutes are considered separately.
1 4 Innovations in Food Packaging

General theory
The mass transfer rates of molecules through a package material or through a mem-
brane are often described as irreversible processes (Miller, 1960). A generalized ther-
modynamic driving force is required to elicit movement of the molecules, which, for
the movement of gases and solutes, is the gradient in the chemical potential of the
migrating species (dMj/dx). For most packaging and membrane applications the area
through which transfer occurs is large compared to the thickness, so that one-
dimensional flow (or flux) is considered. The linear coefficient linking the flux (per
unit cross-section) to the driving force (Miller, 1960) can be considered as a resistance
of the package or membrane material to the passage of the given species:
Flux = (Material resistance) ^ (Driving force) (2.1)

With the appropriate substitutions and assumptions, the gradient in chemical potential
is related to the concentration gradient of the migrating species. Figure 2.2 shows an
example of mass transfer through a packaging material. The permeation of a molecule
is its movement from the region where its concentration is Ci to the region where the
concentration is lower at Q. The absorption phenomenon explains the transferfi*omcon-
centration Ci to Csu the diffusion phenomenon expresses the movement of molecules
from concentration Qj to Qo- Desorption explains the change in concentration

^S1

c
CD
O
c
o
O

^ Cso CQ

•
Distance

Figure 2.2 Concentration profile during mass transfer. Q and Q are the gas concentrations in the
environment and inside the package respectively, while C51 and C50 are the concentrations o f gas at the
outer surface o f the packaging material and inside o f the packaging material respectively.
 Mass transfer of gas and solute through packaging materials 15

between Qo ^^d Q . To evaluate how fast either solutes or gases move in response to
the thermodynamic driving force, the factors making up the material resistance are
examined separately.

Diffusivity
Events occurring within the material are examined first where diffusion is the domi-
nant factor. Diffusion obeys Pick's law (Crank, 1975), and Pick's first law can be
expressed as:

dC_
J<i=-D— (2.2)
dx
where J^, D, C and x are the flux per unit cross-section, the diffusivity, the concentra-
tion of the diffusant, and the distance across which the diflfusant has to travel, respec-
tively. Pick's second law can be used to analyze unsteady state diffusion with time t:
dC ^ d^C
^ = - ^ ^ (2.3)

Crank (1975) introduced various solutions for equation (2.3) with different geome-
tries of the material (e.g. infinite slabs, spheres etc.) and various initial boundary con-
ditions. Analytical solutions of equation (2.3) for the case of heat transfer problems
were also presented by Carslaw and Jaeger (1959). After integrating equation (2.2) for
the case where the concentrations Qi and Qo remain constant (and provided that D is
a constant), thefluxof the diflfusant in the steady state is given by equation (2.4):

F/«x,J, = - ^ = Z ) ( ^ L ^ (2.4)

where Q is the amount of diffused moving substance (mol or kg), A is the cross-sectional
diffusing area, and L is the thickness of the package or membrane. The diffusivity D
has units of m^5' ' and the flux has units of mol m -2 5*- 1 01' kgm~-^s

J,-L L [kg][m]
D ~ or -—- = {m? (2.5)
AC A-t •AC " [m^][s][kg ' m~^] [s]

Solubility/partitioning

Henry's law and solubility

Before gas can diffuse through the packaging material firom C^i to Qo it must first dis-
solve into the material. The sorption of a gas component into a packaging material
16 Innovations in Food Packaging

generally has a linear relationship to the partial pressure of the gas as shown in
Henry's law under conditions where the gas concentration is lower than its saturation
concentration or maximum solubility:

P = ^^. (2.6)

where/7 andX^ are the partial pressure of the gas in the atmosphere and the molar frac-
tion of gas in the packaging material respectively, and a is the Henry's law constant in
Pa (Moore, 1972). If the permeable gas molecule has an affinity to the packaging
material matrix, or is immobilized in the microvoids of the matrix polymer at a rela-
tively low pressure, the sorption behavior follows a logarithmic non-linear relation-
ship, which is expressed as a Langmuir-type sorption (Robertson, 1993). Equation
(2.7) shows the linear relationship between the concentration at the surface of
the packaging material and the partial pressure of the gas for the example shown in
Figure 2.2:

C = H-^ P\ (2.7)

where pi is the partial pressure of the gas on the high concentration (Ci) side. This
relationship is compatible with equation (2.6) when dealing with dilute solutions, as
in permeation situations, so that Q i oc JQ. The constant H~^ can be expressed in the
form of equation (2.8):

^.1. n n V
s [mo/][m3^J
^ STP
Px
P\
V
^material ''Pi
P\ ^STP
^ STP ^material
material ' P\
-» 1 ^ STP
^STP Has^\-<ateriaA^P^^
i-^gas^^^material^i-^^^
material
(2.8)

where n is the number of moles of gas that dissolve in the packaging material, and
^material is the volume of the packaging material into which the gas dissolves. VSTP is
the volume occupied by 1 mole of the gas under standard temperature and pressure
(iTP) conditions (0°C and 1 ato). This has a value of 22 414 X IQ-^nPmor^ for an
ideal gas, and thus can be taken as a constant. The solubility S of the gas in equation
(2.8) can be expressed as in equation (2.9):

S = ""' ^^^^ (2.9)

V • D
material ^l

where S is the solubility in mol m\as mol'^ ^material P^~^ which is equivalent to
Pa~^, which shows the volume ratio of the absorbed component in a material under
standard gas conditions (Geankoplis, 1993). The solubility is a constant which is inde-
pendent of the absorbed concentration at a given temperature (Robertson, 1993).
From equations (2.8) and (2.9), the concentrations of gas at the edges of the packaging
material can be expressed as:

Csi = i r ^ ^ d C,o = -TT^ (2.10)

'^STP ^ STP
 Mass transfer of gas and solute through packaging materials 17

Convective mass transfer

The driving force for the mass transfer of solute molecules in a medium or material is
solely the concentration difference between two positions. The concentration differ-
ence at the boundary film layer between the solution and the material is therefore per-
tinent for describing the driving force for partition of the solute between the solution
and the packaging material. In this case, the convective mass transfer coefficient A^
may need to be considered, since this coefficient is dependent on solution agitation
and the absorption affinity of the solute for the solution and for the material. Figure 2.3
represents the mass transfer of a solute across a membrane or a packaging material.
The convective mass transfer coefficient, h^, with dimensions of velocity (ms~^), is
the parameter which expresses the resistance to transfer of mass at the surface of the
material. The parameter is also referred to as the surface mass transfer coefficient. The
flux on the solution side of the boundary film layer is given by:
^H - Ki AC = h^, (q - c/) (2.11)
As shown in Figure 2.3, there may be more than just resistance to mass transfer on the
solution side. On the package or membrane side at the interface, a fiirther resistance
to mass transfer may exist:
Jr, = h AC = h (C\ - C,) (2.12)
h ms ms ^ si sl^

The absorption affinity of the migrating solute across the interface itself can be expressed
using the partition coefficient K, which is the concentration ratio for the solute between

Convective Diffusional
mass transfer mass transfer

^ ^
^
C^

"^ 4 C

C s o - ^

OQ •

•hH^
d L

Figure 2.3 Mass transfer o f a solute through a membrane.

18 Innovations in Food Packaging

the two different phases (solution and packaging material). At the interface, the partition
coefficient of the solute between the solution and the material is:

^ = ^ a n d C : , =KCi (2.13)

Similar expressions prevail for desorption. After the solute molecule has been
absorbed into the material layer, the next transfer phenomenon that follows is diffu-
sion, which can be represented by Pick's laws (equations (2.2) and (2.3)).

Overall mass transfer of gases and solutes

Gaseous difFusivity and permeability
Since the driving force for gas penetration through a packaging material is the differ-
ence in gas concentrations or partial pressures between the two sides of the packaging
material, the gas flux Jg of both permeation and diffusion can use the partial pressure
term instead of the concentration gradient. In the mass transfer situation of Figure 2.2,
the concentration can be substituted for the partial pressure/? and the solubility S from
equations (2.4) and (2.10):

Flux^^ J = D' ^si - ^so

-^ ^ ^= D
n . • ^'^i~^ Po^
^-^ -= p.
P ' — Pi~Po
^ n \A\
V 'L V
STP ^ ^ STP

where J^ is the flux, and/^i and/7o ^^^ the partial pressures of the gas on the left- and
right-hand sides of Figure 2.2 respectively (Ci and Q sides). The partial pressure/>i
would generally be a constant at ambient conditions. However,/^o is dependent on the
diflrusion of the gas inside the food material or on its reactivity with food components.
Fast diffusion would displace the absorbed gas into the inside of the food within the
package and generate a larger A/? across the package material. Alternatively, in a mod-
ified atmosphere package, where the left-hand side represents the inside of the package,
Ci may vary according to the respiratory activities of the food in the package.
From equation (2.14), the permeability, the diffusivity, and the solubility of a gas
have the relationship shown in equation (2.15):
P = DS (2.15)

Therefore, the SI units of P, D and S are m^s~^ Pa~^, m^s~^ and Pa~^, respectively.
Alternatively, equation (2.14) can be rearranged using the flux definition in equation
(2.4) to retain all relevant dimensions:

P = Q^as-^STP-L ^2.16)
"^material * ^ ' (^1 PQ)

SO that P has units of m|^^ ^thickness ^arla ^~^ Pa~^, compatible with units found in
many packaging texts for permeability: cubic centimeters (or ml) of gas (under STP
 Mass transfer of gas and solute through packaging materials 19

or other defined conditions) multiplied by package thickness in ml (= 0.001 inch) per

100 square inches per 24 hours per atmosphere (ASTM, 1993).

Solute mass transfer coefFicient and overall permeability

For solutes, the overall mass transfer coefficient U includes the resistances to mass
transfer at the surfaces and solute diffusivity through the membrane. The total resist-
ance {R^ is the sum of all the resistances to mass transfer:

R, = — = R , + R.rf • = — + — + — (2.17)
t Tj surface diffusion h D h
ma md
where A^^ and hy^^ ^re the convective mass transfer coefficients associated with
absorption and desorption respectively. In the case of a multilayerfilm,the diffusional
resistance will be the sum of the resistances of each layer. Assuming afilmofn layers
without any interfacial resistance, the diffusional resistance is:

^.^..„=^ = ^ +^ +- +|- (2.18)

where Lj and Dj are overall thickness and overall diffusivity respectively, and L„ and
Dn are the thickness and the diffusivity of the «th layer. Vojdani and Torres (1989a)
used equation (2.18) in estimating the overall diffusivity of potassium sorbate through
methylcellulose and hydroxypropyl methylcellulose multilayer films. In their synop-
sis of permeability in multilayer materials, Cooksey et al. (1999) recommended using
a similar equation for calculating overall permeability from permeability data of indi-
vidual layers.
The resistance to absorption of the solute into the package, and its desorption on the
low concentration side (Figure 2.3), depends on the properties of the solvents, pack-
age, and solutes, and it also depends on the degree of agitation of the solvents on both
sides of the package material. In the case where resistances are small, such as when
agitation ensues on the solution side, and diffusion in the interface region is identical
to that through the membrane material as a whole, then C[ ~ C^ and C^i ~ Qi, so that
only the partition coefficient affects the rate of mass transfer across the interface.
The flux of the overall mass transfer, Jj, is the product of the overall mass transfer
coefficient, C/, and the concentration difference driving mass transfer, which is:
JT = UAC = UiC, - C,) (2.19)
Equation (2.19) shows the overall mass transfer from the high concentration (Ci) side
to the low concentration (Q) side through a packaging material. In such a mass trans-
fer phenomenon, the totalfluxJ j is the same as thefluxesat the interfaces, J^, and the
flux of the diffusional mass transfer, J^. Therefore, the total flux Jj^ and the overall
mass transfer coefficient U are analogous to the flux of permeation and the perme-
ation coefficient (the permeability P), respectively, in the transfer of gas through a
package given above, but in this case the driving force is a concentration difference
rather than a difference in partial pressure.
20 Innovations in Food Packaging

•^r = ha =Ja= JM = U{C, - C,) = h^^ ( q - C^,)

D'(C,-C ^) (2.20)

From equations (2.13) and (2.20), where surface resistance is dominated by the parti-
tion coefficient, the diffusion flux J^ can be written by substituting Q i with K C^ and
assuming that the partition coefficient is identical for desorption and absorption. The
convective mass transfer and the surface mass transfer coefficient /z^ are not as diffi-
cult to work with experimentally when the dimensionless partition coefficient K is
introduced, as shown in equation (2.21):

Washitake et al (1980) measured the permeability of betamethasone and salicylic acid

through eggshell membrane using equation (2.21). Smith and Haigh (1992) and Diez-
Sales et al. (1991) designed diffusion cells for drug penetrations and validated their
permeation phenomena with equation (2.21). Durrheim et al. (1980) introduced the
partition coefficient to determine the permeability of a drug through mouse skin and
human epidermal tissue. They converted the flux of equation (2.21) to a finite volume
model. The permeability was determined by equation (2.22).
y . dC/
p = -^— = ^ ^ (2.22)
A AC A AC
where Fis the finite volume of a drug-accepting chamber, A is the area through which
mass transfer takes place, and the flux J in this case was pertinent for their cell - i.e.
it was not expressed on a per unit area basis.
Torres and his group (Torres et al., 1985; Torres, 1987) used the partition coeffi-
cient K and equation (2.21) to estimate the transfer rates of a preservative into a maize
zein coating applied to intermediate moisture foods. However, since the late 1980s the
partition coefficient has been ignored and the definition of diffiisivity D in nP's'^ has
been used as a permeability constant P for sorbate in polysaccharide edible films
(Vojdani and Torres, 1989a, 1989b, 1990; Rico-Pena and Torres, 1991). Therefore, the
considerations of equation (2.21) are based on unhindered equilibration between the
concentration in the film and the concentration in the bulk solution (Torres et al.,
1985). Keshary and Chien (1984) also used equation (2.21), with the assumption that
the partition coefficient K = 1, for a nitroglycerine patch.

The definitions of permeation, diffusion and absorption have been reviewed with sep-
arate considerations for gas and solute penetration. Permeation is the mass transfer
phenomenon that occurs when a molecule passes through a material or membrane from
an area of high concentration to an area of low concentration. Diffusion is the movement
 Mass transfer o f gas and solute t h r o u g h packaging materials 21

Table 2.1 Summaty of mass transfer through packaging material

Gas transmission Solute permeation

Flux7 Mass transfer coefficient Flux J Mass transfer coefficient

Ap ^las ' ^ P AC Permeability P

Permeation P Permeability P(w ^s-'Pa-')
VsTP-L m^ • s • Pa

AC
Diffusion Diffusivity Q D Diffusivity Q
L s

Absorption •^ ./ . Solubility S {Pa'^) h^AC Surface mass transfer coefficient h

'^laterial ' ^^

of molecules within a material caused by a concentration difference. Absorption is the

surface sorption of the molecules from the surroundings to the material. The mass
transfer coefficients of permeation, diffiision, and absorption are the permeability (P),
the diffusivity (D), and the solubility (5) in the case of a gas, or the partition coeffi-
cient (K) for a solute, respectively. Table 2.1 summarizes the definitions and the units
of the coefficients.
The units and definition of the diffiisivity of a molecule are identical regardless of
whether the diflfiisant is a gas or a solute. The diffusivity defines the transfer rate of an
amount of the diffiisant across a known distance in the material. In both gas and solute
diffusion, the diffusion has a driving force of the difference in concentration of the
molecule within the material.
The permeation of gas and solute molecules has the same physical phenomenon of
penetration as a permeant through a material. However, gas and solute permeation
usually have their flux defined differently. Henry's law is applied to relate the surface
concentration of a gas component with the partial pressure in the atmosphere in which
the packaging material is in contact. On the other hand, solute permeants do not
follow Henry's law. The permeability of a solute is directly related to the overall mass
transfer coefficient, which includes the surface mass transfer coefficient (Z^^) and the
diffusional resistance (L/D). Often, the surface mass transfer coefficient is dictated by
the partition of the solute between solvent and membrane. The partition coefficient
(K) relates the concentration of solute at the surface (Q) with the concentration of the
solute in the solution.
Most permeable substances that affect the quality of food products are gases such as
oxygen, carbon dioxide, noble gases, nitrogen and water vapor. These gases affect ranci-
dity, ripening, and hydration/dehydration of a food product, and generally determine the
length of a product's shelf hfe. Therefore, the oxygen transmission rate OTR {OP Ap/L,
where OP is oxygen permeability) and water vapor transmission rate WVTR {WVP
[Ap/L, where WVP is water vapor permeability) are commonly used for quantifying the
performance of packaging materials in industry. Because OTR and WVTR are common
practical examples for the passage of a substance (oxygen and water vapor) through a
material (the package), solute permeation has not been considered as extensively as
22 Innovations in Food Packaging

gas permeation. However, in the case of drug delivery and active packaging systems
solute permeation is theoretically important in order to explain active ingredient transfer,
and its experimental determination is reasonably straightforward. This warrants study-
ing all the factors that affect how fast solutes will permeate through given materials.

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