Water

Activity
Prediction
GUSTAVO V. BARBOSA-CÁNOVAS
Washington State University
Pullman, Washington , USA
 Water Activity
9Water activity is a critical factor that determines
shelf life, influence how fast organisms will grow
in a product, and may be the most important
factor in controlling spoilage.
9By measuring water activity, it is possible to:
ƒ predict which microorganisms will and will not be
potential sources of spoilage.
ƒ have an insight on the activity of enzymes and vitamins
in foods that can have a major impact their color, taste,
and aroma.
 Water Activity: Concept
The water activity scale extends from 0 (bone dry) to
1.0 (pure water)

Water Activity = aw = ρ/ρo

where ρ = water vapor pressure inside the food

ρo = vapor pressure of pure water under the
same conditions of temperature, etc.

Relative humidity = ρ/ρo

Each solute will affect the aw uniquely
WATER ACTIVITY - STABILITY DIAGRAM
Water activity (Aw) of food products
Food Product Aw
Fruits &Vegetables 0.97-1.00
Meats 0.95-1.00
Cheese 0.68-1.00
Jams & Jellies 0.75-0.94
Honey 0.54-0.75
Noodles 0.50
Dried Milk 0.20
Crackers 0.10
 Some devices used to measure water
activity in semimoist foods
LUFF Aw-Wet Messer Fiber-dimensional hygrometer
(Germany)
NOVASINA Thermoconstanter Electrical conductivity of immobilized
(Switzerland) salt solutions

VAISALA Humicap (Finland) Electrical capacitance of polymer thin

film

DECAGON Aqualab (U.S.A.) Dew point by the chilled mirror

OTTAWA aw-Meter (Canada)
NAGY aw-Kryometer (Germany)
technique
Thermometric device suited to establish
compliance or non-compliance of test
samples with a standard
Cryoscopic measurements; initial
freezing point
Procedure for calculation of
Aw in semimoist foods
Prediction of Water Activity
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Has been limited to aqueous

solutions of electrolyte and
non electrolyte solutes
 Raoult’s Law
y i P = xi Pi 0

Where
¾ P is the system pressure
¾ Pi0 is the saturation vapor pressure of the pure solvent
¾ yi and xi are the mole fraction of a particular component
in the vapor and liquid phases respectively
The application of Raoult’s Law to food systems is not
practical because of solvent-solute interactions.
 Raoult’s Law
„ Assumes water activity lowering due to
solute (range 0.95 to 1.0)
„ All solute dissolved in all water
„ No between solute interaction

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Prediction of Water Activity
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Water activity can be estimated by

different theoretical and empirical models
considering the types of solutes in the
solution:
¾Electrolytes
¾Nonelectrolytes
¾Mixtures
Prediction of Water Activity
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Non-electrolytes solutions
¾Money and Born Equation
¾Grover Equation
¾Norrish Equation
¾Teng and Lenzi
Prediction of Water Activity
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1.0
aw =
(1.0 + 0.27n )
where n is the number of moles of sugar per 100 g of water.

9This empirical equation is use for calculating Aw of sugar

confections, such as jams, fondant creams and boiled sweets.
 Prediction of Water Activity
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a w = 1.04 − 0.1isici + 0.0045i (sici ) 2

where
¾ Ci is the concentration of component i
¾ Si is the sucrose equivalent for different ingredients
such as lactose (1.0), invert sugar (1.3), 45DE corn
syrup (0.8), and gelatin (1.3).
The Grover model is an empirical approach to estimated Aw
in candy formulations.
 Prediction of Water Activity
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log (aw/xw) = -ki(1-xw )2

xw = mole fraction of water

ki = Norrish constant for ingredient i

9 Norrish equation takes into account a nonideal thermodynamic

approach to determine the Aw of binary mixtures.
9 Norrish Equation - accounts for water binding properties of the
solute and is more useful for large concentrations of solute.
 Example
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„ The water activity of a glucose-water solution (2.44:1

wt/wt) can be estimated by means of the Norrish equation.
The mole fractions are: X1 = 0.804 and X2 = 0.196. The
Norrish constant for glucose.is 2.25. Substituting for the
values in the Norrish equation results in an estimated
water activity of 0.74.

log (aw/xw) = -ki(1-xw )2

 Example
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„ The experimental water activity of this mixture is

reported as 0.78 (Teng and Seow, 1981).

„ The use of Raoult’s law gives a water activity

estimate of 0.80.
Prediction of Water Activity
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a w = 1 + ∑ i Ai m i For i=1 to k

Where Ai is the polynomial coefficient, m is the

solute molality, and k is the degree of the
polynomial
Prediction of Water Activity
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Electrolytes solutions

¾Pitzer Equation
¾Bromley Equation
Prediction of Water Activity
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a w = exp( −0.01802φΣi M i )
Where φ is the
osmotic coefficient,
zm and zx are the
charges of m and x
ions, vm and vx are
the respective
number of ions, M
is the solution
molality. B(0),
B(1), Bmx and C are
the Pitzer
coefficients.
 Example
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 Example
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9An electrolyte 1:1 type is in solution(e.g., a solution

of NaCl, 2.31 molal at 25°C).
9The Pitzer's Bmx(0), Bmx(l), and Cmx parameters for
NaCl are 0.0765, 0.2664, and 0.00127, respectively.
The following can be defined for the ions: zNa = 1,
zCl = 1, νNa = 1, and νCl = 1.
9The osmotic coefficient is evaluated from equation:
Φ=-1000 lnas/(Ms∑νrmr)
 Example
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mNa=2.31 mCl=2.31 I=2.31 zNazCl  =1.0
F = -0.211 BNaCl = 0.089 Φ = 1.001
Water activity is evaluated from Equation:

a w = exp( −0.01802φΣi M i )

aw = exp(-0.01802 x 1.001 X (2.31 + 2.31 a, = 0.92

The experimental water activity of this mixture is 0.92 (Teng
and Seow, 1981).
Prediction of Water Activity
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Where φ is the
osmotic
coefficient, zm
and zx are the
charges of m
and x ions, vm
and vx are the
respective number of ions. M
is the solution molality, I is
a w = exp( −0.01802φΣi M i ) the ionic strength. B, Bm, Bx,
δm, δx are the Bromley
coefficients.
 Example
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The Bromley B parameter is equal to 0.0574 for the

NaCl. The ionic strength I=2.31 and the charge product
zNazCl  =1.0.
•Substituting these values gives in the equations
presented above:
T1 = -0.0615 T2 = -0.0226 a = 1.5
The osmotic coefficient (Φ ) and the water activity are:
Φ = 1.0062 aw = 0.919
 Prediction of Water Activity
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Multicomponents Mixtures
¾Ross Equation
¾Ferro-Fontán-Benmergui-Chirife
Equation
¾Ferro-Chirife-Boquet Equation
¾Lang-Steinberg Equation
¾Pitzer-Kim Equation
Procedure for calculation of
Aw in semimoist foods
Prediction of Water Activity
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0
aw = Πi (aw )i
aw0=water activity of each component in the binary mixture
 Prediction of Water Activity
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Ii
a w = Π i ( a wi ( I )) I

I i = 0 .5 vi m i Z m Z x

awi(I)= water activity of a binary solution of I at the same total ionic strength (I)
of the multicomponent solution. Ii is the ionic strength of component i in the
mixture, vi is the total of ions of the solute i in solution, mi is the molality of the
solute, and zm and zx are the charges of m and x ions.
 Prediction of Water Activity
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(aw)m = X1exp(−Km X2 )
2

−1
n  Mt   n  Cs 
K m = ∑ K s C s  
 M t =  ∑  

s=1  Ms   s = 1  M s  

X1 and X2 are the molar fractions of the solvent and solutes, Ks is the Norrish K
value for each solute in the mixture, Cs is the weight ratio of each solute to the
total of solids in the mixture, and Ms is the molecular weight of each component
 Example
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A solution of glucose (5.96% wt/wt) and sucrose

(46.01%wt/wt) has a measured water activity of
0.926 (Teng and Seow,198l). The K values of
glucose and sucrose are 2.25 and 6.47,
respectively. The Km and Mt values are evaluated
from equations mentioned above.
Km = 5.65 Mt = 310.82
Then, the predicted water activity using Ferro-
Chirife-Boquet equation is 0.923.
Prediction of Water Activity
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Log(1 − a ) = ( MW − ∑ ai wi ) / ∑ bi wi
w
Where ai and bi are the Smith equation constants for each component i in
the mixture. M is the moisture content of the mixture, W is the total dry
material of the mixture, wi is the dry material of each component i in the
mixture.

9The model may predict water activities over the

range 0.30 to 0.95 of a multicomponent mixture
 Example
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A mixture of starch (0.79 g/g of total sample) and

sucrose (0.09 g/g of total sample) has a moisture
con- tent of 0.219 g of water/g of solids at an aw of
0.90. The Smith constants for each component are
(Lang and Stein- berg, 1981):
Starch: ai = 0.0989 bi = -0. 1485
Sucrose: ai = -0.5944 bi = 1.2573
 Example
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Rearranging the data in terms of the Lang and
Steinberg model:
M=0.29gofwater/g of solid W=0.89g of solids
(ai wi)starch= 0.08 g of water (ai wi)sucrose = -0.06 g of water
(biwi)starch=-0.12g of water (biwi)sucrose=0.13g of water

Replacing the above values in Lang-Steinberg equation

and taking the log10 to base 10:

aw = 0.90
Prediction of Water Activity
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{
φ − 1 = (∑ mi )−1 IF'−F ) +∑ i ∑ j mim j (λij + Iλ'ij ) + 2∑ i ∑ j ∑ k mim jmk µijk }
F = dF / dI
F = − 0 . 392 I 0 . 5 /( 1 + 1 . 2 I 0 . 5 ) λ ' ij = d λ ij / dI

Where m is the molality of a particular ion (i,j,or k). λij is the second
virial coefficient, µijk is the third virial coefficient, and I is the ionic
strength.
 Example
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An aqueous solution of NaCl (9.29% wt/wt) and LiCl (1.57%
wt/wt) has an experimental water activity of 0.9312 (Tsong and
Seow, 1981). Pitzer and Kim equation can be expressed as

where Bij, F and I are

evaluated by
 Example
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I = 2.198 F = -0.2087 BNaCL = 0.0902 BLiCl = 0.1652

CNaCl = 0.00127 CLiCl = 0.0036 ∑ mi = 4.408 ∑ mz = 4.408

¾The predicted values for the osmotic coefficient and water

activity are the following:
Φ = 1.0811 aw= 0.92
Prediction of Water Activity
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∑ i ai si wi
aw =
∑ i si wi

Where ai is the initial water activity of component i used in the mixture, si

is the sorption isotherm slope of component i at the mixture temperature,
and wi is the dry weight of component i.
 Prediction of Water Activity
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Based on the concept proposed by Salwin and Slawson, and
the linear relationship of Favetto and Chirife (1985).

awM =1− ∑ Kimi

i
Where awM= water activity in equilibrium state o final of a
complex mixture, k = constant of Faveto and Chirife equation at
25°C[kg w/g mol], m = molality and i= number of solutes in a
complex mixture.
Prediction of Water Activity
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ÂVega-Mercado H., Romanach B.,

Barbosa-Cánovas G.V. et al, Developed
an Interactive Computer Program to
accurately predict the Aw of
multicomponent systems containing
fiber, proteins and fats
 Prediction of Water Activity
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ÂProgram Capabilities
ƒ Predict Aw of model food systems by several well
accepted equations (Bromley, Pitzer, Norrish,
Ferro-Cherife-Boquet, Ross, Ferro Benmergui-
Cherife)

ƒ Establish similarity levels between foods of

known aw and composition to new products
where composition is available
 Prediction of Water Activity
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ÂProgram Capabilities
ƒ Calculate deviation factors based on
previously established similarity levels,
where the presence of fibers, fats and
proteins is taken into account

ƒ Programmed in MS-DOS QBASIC 1.0,

available from the authors
Prediction of Water Activity
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ÂThe accuracy of the predicted aw is affected
when the algorithm is applied to food systems
which contain fats and proteins.
ÂFood products containing fats and proteins
show a deviation factor of 1.07, on average,
after one iteration.
ÂThe discrepancy in aw values, awpred and awrep,
can be explained in terms of water bound on
proteins or associated with fatty mesomorphic
structures.
Procedure for calculation of
Aw in semimoist foods
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Thank you!!