Mathematical Model for Water Diffusion During Brining of

Hard and Semi-hard Cheese

JULIO A. LUNA and MdNlCA S. CHAVEZ

ABSTRACT tally. Due to this, theseauthorsalso suggested a relationbe-

The integral method, which is an approximate analytic method, was
used to obtain the theoretical profile of moisture changes during brin-
ing of cheese. A mass layer was defined in the model where all water
variations take place. The model was applied at different times to
semi-hard cheese brining and compared with experimental data. A
moisture pseudo diffusion coefficient was obtained from experimental
data as part of the proposed model. Agreement was good, which
demonstratedthe applicability of the model.
Key Words: Cheese, brining, mathematical model, water diffusion
INTRODUCTION
DURING BRINING, salt is absorbedfrom sodiumchloride
solutioninto cheese,andsimultaneously wateris lost, resulting
in a cheesevolumereductionbecauselesssalt is absorbedthan
moistureis lost. Brining involvesheatand masstransferfur-
thermore,both processes influencethe final quality of cheese.
Governingequationsof the systemare coupledby the water
contentvariablein the liquid phaseof the porousmediumbut,
throughLuna and Bressan(1985)analysisbasedon the char-
acteristicof the process,heatandmasstransferduringbrining
can be treatedseparately.However, in most of the brining
cheeseanalysiswaterlosshasbeenneglected,so specificstud-
ies on it havenot yet beenreported.
Thus, the objectiveof our work was to designa mathemat-
ical modelto describemoisturechangesduringhardandsemi-
hard cheesebrining. To achievethis, the transferequation,
subjectto proposedboundaryconditions,was solvedby the
IntegralMethod.The methodbasiswasto definea masslayer,
whereall water variationoccurredso a masslayer thickness
was obtained.First, the proposeddifferential equationwas
integratedover the masslayer to removethe spacevariable.
Then, a polynomialprofile was chosento havemoisturecon-
centrationdistributionover the layerandfitted usingproposed
boundaryconditions. The polynomial, thus obtained, de-
pendedon time only. Then, it was introducedinto the mass
integralequationand, after performingthe indicatedopera-
tions, an ordinarydifferentialequationin terms of the mass
layerwas obtained.Solutionof the lastequation,togetherwith
the profile previouslyobtained,gavethe moistureconcentra-
tion profile over the masslayer.
The outwardmigrationof wateris relatedto the penetration
of saltinto thecheese.In fact, it canbe describedasan impeded
mutualdiffusionprocess.Differentfactorsaffectthis phenom-
enon(Geurtset al., 1974).Theseauthorsproposeda cheese
matrix structuremode1which providedsalt concentration pro-
file, a pseudodiffusioncoefficient,andmoisturechangeanaly-
sis duringthe saltingprocess.At brining,while moisturecontent
increasesgradually,salt contentdecreases in the sameway,
from the edgeof the cheeseinward. Moisturecontentaway
from the rind approaches initial moisturecontentasymptoti-
tweensaltandmoisturetransportin orderto obtaininformation
aboutwaterbehaviorduringsalting.This relationshiphaddif-
ficultiesand lack of clarity in mathematical
waterloss studies
(Guineeand Fox, 1983).
To completeour mathematicalmodelfor brining cheesea
pseudodiffusion coefficientwas definedfor a specific posi-
tion. This pseudocoefficientwas usedto producea moisture
profile. It wasprovidedby differentapproximate methods:one
coefficientwas obtainedfrom a graph in normal scale, the
otherfrom probabilitygraphpaper.Thevaluesobtainedthrough
eachmethodwere similar. Finally, the validity of the model
wasverifiedusingexperimental datafrom Geurts’et al. (1974)
andGuineeandFox (1983),and our own data.
THEORY
The systemunderstudy is a cheeseconsideredas a rigid
semi-infinitemediumimmersedin an infinite sodiumchloride
solutionas describedin Fig. 1. Initially, the moistureconcen-
trationin thecheeseis constant,thenit changesduringbrining.
We assumedthattherewasno chemicalreactionandtherewas
no convectivemasstransferin the system;thus we can treat
the processas a one-dimensional isothermaldiffusion. During
brining thereis no changein moistureand sodiumchloride
concentration at the cheesesurface.The diffusion coefficient
is thena functionof the waterandsodiumchlorideconcentra-
tion insidethe cheese.
The mathematical formulationof this problemis:
ac a
D$ ; x > 0; t > 0 (1)
at=ax ( 1
whereD is the water diffusioncoefficientin the cheese.
Equation(1) is subjectedto the boundaryconditions:
c = c, atx=O,t>O (2)
c = co atxrO,t=O (3)
1
Brining medium

The authors are with lnstituto de Desarrollo Tecnoldgico para

la lndustria Qu/inica (INTEC)- Consejo National de lnvestiga-
ciones Cientificas y Tknicas (CONICET), Univ. Nat. del Litoral. -I
Giiemes 3450, C. C. No. 91,3000-Santa Fe, Reptiblica Argentina.
Fig. 1 -System under study.

Volume 57, No. 1, 1992-JOURNAL OF FOOD SCIENCE-55

DIFFUSION OF WATER IN CHEESE. . .

Cheese When this profile is introducedinto the massintegralequa-

tion, an ordinary differential equationfor s(t) is obtained:
di3
12 D, = 6 dt t>o

subjectto
Flow of
NoCl
39
s=o t=O (12)
I
I
%
I X
The solution of Eq. (11) with (12) gives:

Knowing s(t) the moisture concentrationprofile is deter-

Fig. 2-Schematic view of the moisture profile inside the cheese,
and the mass layer.
Using the Integral Method in the problem defined by Eq.
(1) to (3) involves integratingEq. (1) over a penetrationdis-
tanceS(t), which is a function of time, called the masslayer,
indicatedin Fig. 2. The masslayer is definedas the distance
beyondwhich thereare no changesin the moistureconcentra-
tion.
Equation(1) is integratedin relationwith the spacevariable
from the position x = 0 to x = 6(t) to obtain:
(4)
The rule of differentiationin the integralis usedin the right-
hand side of Eq. (4); using integral limits basedon:
mined accordingto Eq. (10).
D, is a pseudodiffusion coefficientdefinedin x = 0 where
D(C,, C,,,) = D, = constant.D, was obtainedusing two
different graphicmethod.
MATERIALS & METHODS
EXPERIMENTAL GOUDA cheeseswere provided by a local factory.
They were cylindrical (135 mm high, 200 mm diameter, 1 kg in
weight)with aninitialmoistureof 45%.Thebrinesolutioncontained
20.50% sodium chloride and 1.5% calcium chloride; pH 5.5, tem-
perature 12.6”C.
To avoid simultaneous salt diffusion from different directions, the
cheeses were waxed on the side and on one flat surface so that only
one unwaxed surface was in contact with the brine solution. Ten
cheeses were brined and taken out of the brine in pairs for moisture
analysis after 0, 2, 4, 6, and 8 days of salting. A 20 mm diameter
cylinder was cut from the cheese center, and from this cylinder 50
mm high slices were cut moving from the unwaxed surface. The slices
were analyzed in duplicate for moisture using a CEM microwave
oven.

from which
RESULTS & DISCUSSION
THE MASS LAYER thickness,6, must be previously deter-
mined to apply Eq. (10) to any proposedcase.We obtainedit
is obtained. using two different graphic methods.The first one selectsS
where, from moistureconcentrationvs. penetrateddistancegraph, in
w commonscale,as the distanceat which the following relation
e = I x-o CM dx is satisfied:

Equation(6) is calledthe massintegralequationin the pres- (C-G)

ent problem. Its solution is chosenas a polynomialprofile for
the moistureconcentrationdistributionover the masslayer:
C(x,t) = a, + a,x + a& + a4x3 (8)
The first threecoefficientsin the polynomialare determined
by using the boundaryconditionsgiven by Eq. (5), and the
fourth coefficient is obtainedfrom using equation(1) at x =
6, where the moistureconcentrationequalsC$
(9)
Application of Eq. (5) and (9) to Eq. (8) yields the moisture
concentrationprofile in the form:
C(x.t) = c, + (Co - C,) ;x - ; x2 + $x3 (10)
( 1
so:
a,=C,; a2=i (CO-CJ; a3=$ (CO-C,); ad=+ (Co-C,)
-= 0 gg
(Co-cd) -
(14)
HereC, andC, aresurfaceandinitial moistureconcentration
equaled30.36% and 45.08%, respectively;and 0.99 was cho-
sendueto the estimationof the maximumrelativeerror, which
was 0.75%, so a relative error of 1% was suitable.
From the samegraphicmethodusingvisual appreciation,6
was also selected.Mass layer indicateswhere C approaches
Co asymptotically,which meansthat the curve slopeis null in
that range. This importantassumptionwas implicitly used in
the visual appreciation.
Table 1 shows6 values using Eq. (14), &, and visual ap-
preciation,S2. Both a1 and a2 were used in linear regression
to obtain D,r and D,, accordingto (13). A correlationcoeffi-
cient helpedus to selectthe most suitableD, value. For visual
appreciationR2 equals0.97 and for Eq. (14) 0.89 so, Ds2 =
9.56x lo-11m2/secwas taken.
The secondgraphicmethodproposedby Geurtset al. (1974)
providedD, using probability graph paper.Theseauthorsap-
proximatedsalt penetrationbehaviorduring brining to an error
function which allowed the use of probability paper. Water

56-JOURNAL OF FOOD SCIENCE-Volume 57, No. 1, 1992

 Table 1 -Mass layer thickness obtained from Eq. (14), &, and visual ap- Table 3-Percent deviation between experimental and theoretical mois-
preciation, & ture concentration during brining process
Period of Experimental Experimental VE according to % Deviation* % Deviation’
brining (days) 6, h-d a2 Imm) (brining days) using D,? using DSJ
2 20 20 2 3.04 2.55
4 2.32 2.67
: 31 30
33 6 2.65 3.54
8 39 40 a 2.88 3.59
a With respect to VT, which was obtained from Eq (13) and (10).

Table 2-Theoretical mass layers at surface moisture concentration 30.36%

and initial concentration 45.08% Table *-Percent deviation between experimental and theoretical mois-
Theoretical Theoretical ture concentration during brining process
Period of
brining (days) S2 (mm) S3 b-m) VE according to: % Deviation’
2 19.91 22.59 Fig.1 -Geurts et al. (1974) 1.64
4 28.16 31.59 Fig.lO-Geurts et al. (1974) 1.14
6 34.46 39.12 Guinee and Fox (1983) 4.05
8 39.82 45.18 0 With respect to VT, which is obtained from Eq (13) and (10).

_ 09999 ,

OS

82
OS
8:
02
0t F 2 days of brining
Experimental data
b
0011 1 I 1 I 1 I l 8 days of brining
0 2 4 6 6 I) 12
-model prediction
x/K ~mm/doyV2)
I I I I I
25’ ’
Fig. 3-Moisture concentration from experimental data plotted I 9 18 27 36 45
on probability paper. Distance .fiom cheese surface (mm)
Fig. 4-Experimental and Theoretical valuesof moisture con-
centration during two and eight days of brining.
behavioris analogousto salt penetrationbut oppositeso, we
proposedthe following relationfor waterloss:
(Co- C)
-= Percentdeviationvaluesshowgoodagreement betweenthe
(15)
(Co-Cs) modelproposedand experimentaldatain both cases.
with z = 2 (Dt)rnandresultingK = 1 to satisfythe condition: To extendits applicability,experimentaldatafrom Geurts
et al. (1974)and Guineeand Fox (1983)were analyzed.We
x = 0. -= G-C) , appliedour modeland, finally, comparedresultsobtainedby
’ (G-G) percentdeviationvalues.
In the work by Geurtset al. (1974)Goudacheesewas used
Equation(15)wasplottedon probabilitypaperfor eachtime andsodiumchlorideandmoisturedistributionsweremeasured
of brining (2, 4, 6, 8 days).Our experimentaldatacould be after8.1 daysof brining(pH 5.64,T = 12.6”C,C, = 30.52%,
approximated to a straightline, D, is obtainedfrom the tangent G = 43.83%)and8 daysof brining (pH 4.79, T = 12.8”C,
of it, which provedthat D, was constantfor the samecheese C, = 31.00, Co = 41.13%).Thesehad beenplottedin Fig.
at everybrining time as is shownin Fig. 3. From Fig. 3 it 1 and Fig. 10 of that paper,respectively.We measuredmass
wasfeasibleto getthepseudodiffusioncoefficient,D, amounts layerusingthe visual methodfrom thesefigures:6 equaled5
to 1.23x 10-10cm2/sec. This methodapproaches waterbehav- cm and 4.5 cm, respectively.Data thus obtainedwere intro-
ior to Eq. (15) and thenwaterconcentration datato a normal ducedinto Eq. (10) andtheoreticalprofileswere obtained.
distributionthat is the straightline obtainedin Fig. 3. In the sameway, 6 = 5.75 cm was foundfrom the dataof
Theoreticala2and8, shownin Table2 werecalculatedfrom GuineeandFox (1983)Fig. 3 on experimental moistureprofile
Eq.(13)usingDs2andD, values.Theoreticalmasslayerthick- after 9 daysof brining of Roman0cheese(T = 20”, C, =
nesswasintroducedin Eq. (10)to obtain,finally, a theoretical 30.50%,C,, = 46.29%).Then Eq.(lO) was appliedto these
waterdistributionprofile. Figure4 showsthe goodagreement experimentaldata. Percentdeviationvaluesin Table 4 show
betweenthe theoreticalprofilesand the experimental onesfor good fitting of the proposedmodel to experimentaldata in
2 and8 daysof brining.It alsoshowsthat the proposedmodel hardcheeseduringbrining; thus,the modelvalidity was dem-
is valid only insidethe masslayerfor eachbrining time. onstrated.
Table3 showspercentdeviationvalues(Helderman,1974)
for the theoreticaland experimentaldata,basedon Eq. (17).
CONCLUSION
THE PROPOSEDtheoreticalmodel permittedeasyand ac-
curateestimationof water diffusion during brining in semi-
% deviation= hardcheeses.It was importantto havethe correctvaluesof
J D, or valuesof the masslayer 6(t), becausemoistureconcen-

Volume 57, No. 1, 1992-JOURNAL OF FOOD SCIENCE-57

DIFFUSION OF WATER IN CHEESE. . .
nation profiles dependedstronglyon thosefactors.The prob-
ability graph papermethodwas nearly as good as the others
and so were its results,but it was mathematicallymore com-
plicatedthan the others.The equationsfor the water loss pro-
vided here, togetherwith other studies of sodium chloride
diffusion in cheese,provide an important tool for analyzing
changesin propertiesduring cheeseripening.
NOMENCLATURE
Polynomialcoefficient
t Moisture concentrationin the cheese
Moistureconcentrationin the cheesesurface
2 Moisture concentrationinside the cheesebefore
brining begins.
D Diffusion coefficientof water in the system
Diffusion coefficient at x = 0
? Pointsconsidered
Time (minutes)
:E Experimentalvalue
MICROFILTRATION OF SKIM MILK. . .From page 48
A comparisonof the relative volume of control skim milk
micelles(Fig. 2) with that of micellescomprisingthe permeate
and retentatefractions (Fig. 3 and 4) reflects the expected
volume differencesbetweenpermeateand retentatefractions.
A more effective size separationwas obtainedwith the 100
nm membrane(Fig. 3) with relatively small numbersof mi-
celles larger than 100 nm presentin contrastto permeateob-
tained using the 200 nm membrane(Fig. 4). Both retentate
fractionsstill containedlarge numbersof micelleswith diam-
eters less than 100 nm indicating that microfiltration would
needto be extendedpast the 4:l concentrationlevel, together
with possibleuse of diafiltration, to effect a greaterremoval
of smallermicellesfrom the retentatefractions. However,the
possibility of rearrangements in the size of micelles in reten-
tatesor permeatesshould also be considered(McGannet al.,
1980) since the skim milk systemis in dynamic equilibrium,
dependentupon a variety of environmentalfactors.
Micellar caseincomposition
Resultsof the densitometricanalysisof the micellar casein
componentcompositionof the permeateandretentatefractions
are given in Table 4. The Q- and rc-caseincontentswere
comparablein all of the fractions, however, the qZ-casein
contentwas significantly higher and the p-caseinsignificantly
lower in both permeates.The lower p-caseincontent in the
permeatefractions (smaller micelles)was in agreementwith
the report of Donnelly et al. (1984). However, the magnitude
of this differencebetweenlarge and small micelleswas much
greaterin our study. Since the permeatefractions only rep-
resentan enrichmentof smaller micelles, comparisonof our
58-JOURNAL OF FOOD SCIENCE-Volume 57, No, 1, 1992
VT Theoreticalvalue
X Spatialcoordinate(mm)
6 Mass layer
8 Integral along the masslayer
Subscripts
0 Initial state
S At the cheesesurface
REFERENCES
Geurts, T.J., Walstra, P., and Mulder, M. 1974. Transport of salt and water
during salting of cheese. 1. Analysts of the process involved. Neth. Mik
l+iry J. 28: 102.
GmmneemTzoand Fox, P.F. 1983. Sodium Chloride and moisture changes
e cheese durmg salbn . J. Davy Research. 50: 511.
Helderman, D.?T . 1974. Predicting the rc?a.tronships between unfrozen water
fraction and temperature during food freezmg using freezing point
depression. Trans. ASAE 17: 83.
Luna, J.A. and Bressan, J.A. 1985. Heat transfer during brining of Cuar-
tirolo Argentmo cheese. J. Food Sci. 61: 858.
MS received l/23/91; revised 6/29/91; accepted 7/15/91.
compositionaldatawith thosefor narrowlydefinedmicelle size
fractionsof Donnelly et al. (1984) is necessarilylimited.
REFERENCES
Davies, D.T. and Law, A.J.R. 1983. Variation in protein composition of
bovine casein micelles and serum casein in relation to mice&r size and
milh temperature. J. Dairy Res. 60: 67.
Donnelly, W.J., McNeill, G.P., Buchheim, W., and McGann, T.C.A. 1984.
A comprehensive study of the relationship between size.and protein com-
l;o$on 111natural bovme casem mrcelles. Blochrm. Brophys. Acta 789:
Ekstrand! B., Larsson-Raznihiewicz, M., Brannang, E., and Swensson, C.
1981. Srze distribution of casein micelles related to coagulating proper-
g; ~lco5~parrson between drfferent breeds of cattle. Swedrsh J. Agric.
McG&m,‘T.d.A., Kearney, R.D., and Donnelly W.J. 1979. Developments
on column chromatography for the separati&r and characterization of
casein micelles. J. Dairy Res. 46: 307.
McGann, T.C.A, Donnell ., W.J., Kearney, R.D., and Buchheim, W. 1980.
Comption and size $ strrbutron
. . of bovine cesein micelles. Biochim.
Biop ys. Acta 630: 261.
Miller, G.L. and Burton, AL. 1959. Spectrophotometric determination of
aldoses by an iodometric procedure. Anal. Chem. 31: 1790.
Rose, D. and Colvin, J.R. 1966. Appearance and size of micelles from bo-
vine milk. J. Dairy Sci. 49: 1091.
Yoshikawa,. M.? Taheuchi, M., Sasaki, R., and Chiba, H. 1982. Chemical
charactermatron of bovine casein micelles fractionated by size on CP-lO/
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MS received 2/ll/Sl; revised 7/20/91; accepted 8/11/91.
Mention of brand or firm names does not constitute an endorsement by
the U.S. Department of Agriculture over others of a similar nature not
mentioned.
Wethank Mr. T. Dobson for technicalassistancewith electron microscopyand Mr.
P. Smith for su~vlvinaoasteurizedskim mik