Topic 7-Aw Prediction

Dr Ted Labuza University of Minnesota Department of Food Science and Nutrition St Paul MN 55108 voice 612-624-9701 fax 651-483-3302
tplabuza@tc.umn.edu
Topic 7 FScN 4342 Water Activity Prediction
Dr Ted P. Labuza
Department of Food Science and Nutrition University of Minnesota St Paul 55108 USA 612-624-9701 fax 625-5272 tplabuza@umn.edu
tplabuza 2008 Slide # 1
Water Activity Prediction by Raoults Law
tplabuza 2008
Slide # 2
1. Raoults law
! Assumes
water activity lowering due to solutes (range 0.95 to 1) ! Colligative effect based on # of particles ! All solutes dissolved in all water ! No between solute interaction ! Dilute solution ? How dilute
Page #
Dr Ted Labuza University of Minnesota Department of Food Science and Nutrition St Paul MN 55108 voice 612-624-9701 fax 651-483-3302 tplabuza@tc.umn.edu
aw = !
n H2 O = ! X H2 O nH 2 O + nso lute
X H2 O = mole fraction water water X s = mole fraction solute = 1 " X H2 O
! = effective activity coefficient

Raoults Law Example 1

What is aw if you add 20 g propylene glycol to 100 g meat at 50% moisture content (wb)? Boundary conditions: 100 g meat with 50 g wate+ 50 g solids Assume initial aw = 1 before addition of solute Assume meat solids no effect Assume all solute dissolved Assume ideal ie ! =1 Ideal Calculation: Moles glycol =20/76= 0.263 Moles water = 50/18 = 2.778 Xwater = [ 2.778/(2.778 + 0.263) ] =0.9136 =aw= 0.914 Xsolute = 1-0.9136=0.0864
position on real solute isotherm accounts for ! ! 1

Propylene glycol isotherm
800 700 600 500 400 300 200 100 0.85 0.90 0.95 1.00
y = - 2.4286e+5 + 8.4204e+5x - 9.7383e+5x^2 + 3.7593e+5x^3 1.000 R^2 =
Example 1 Solution #2
water activity
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Example 1 Solution #2
position on real solute isotherm
800 700 600 500 400 300 200 100 0.85 0.90 0.95 1.00
y = - 2.4286e+5 + 8.4204e+5x - 9.7383e+5x^2 + 3.7593e+5x^3 1.000 R^2 =
water activity
tplabuza 2008
20 g glycol to 50 g water gives 50/20 = 2.5 g water/g glycol or 250 g water / 100 g glycol Use polynomial regression aw = 0.906 thus less than ideal which gave 0.914 From this ! = 0.906/0.914 = 0.991
Slide # 7
questions
How good is assumption ? Can we estimate activity coefficient from base principals? Van Laar equation
a = ! X water = ! [1 " X solute ] ln a = ln ! + ln [1 " X solute ] at low X s ln(1-X s ) =X s ln ! H 2O = K # $Xs % & Van Larr equation thus ln a = K # $Xs % & + ln [ X water ]
2 ln a =K# $Xs % & Xs 2 2
To determine make solutions at different levels of Xs Plot ln [a/Xw ] vs Xs 2

Single Solute correction for non-ideality

Van Laar equation from heat of mixing (Hildebrandt and Scott)
ln! = Ks X 2s
! = activity coefficient Ks = solute constant Xs = solute mole fraction
ln a/Xw slope = K s
Xs
aw = X H2O eKs Xs
tplabuza 2008
ln ! = ln
aw 2 = Ks X s Xw
Slide # 9
Page #
Compound PEG 600 PEG 400 Peg 200 lactose lysine lactulose sucrose ornithine NaCl [2 - 26%] citric acid DE 32.8 DE 42 DE 55 DE 64 DE 83 DE 91 K -56.0 2 -26.6 0.8 -6.1 0.3 -10.2 -9.3 0.3 -8.0 0.3 -6.47 0.06 -6.4 0.4 -6.26 -6.17 0.49 -5.97 -5.31 -5.18 -4.57 -3.78 -2.99
Slide # 10
tplabuza 2008
Compound
tartaric acid -4.68 + 0.5 maltose -4.54 + 0.02 proline -3.9 + 0.1 a-ABA -2.57 + 0.37 alanine -2.52 + 0.37 glucose/fructose-2.25 + 0.02 malic acid -1.82 + 0.13 sorbitol -1.65 + 0.14 lactic acid -1.59 + 0.2 xylose -1.54 + 0.02 glycerol -1.16 + 0.01 propylene glycol-1.0 mannitol -0.91 + 0.27 NaCl [0 to 2%] +17.91 KCl [below 2%] +10.81 alanine +2.59 + 0.37 urea +2.02 lactic acid +1.59 + 0.2 glycine +0.87 + 0.11
tplabuza 2008
Increases activity
Slide # 11
substance water propylene glycol glycerol ethanol NaCl KCl sucrose lactose fructose glucose citric acid
MW in Daltons = 18.016 = 76 = 92.1 = 46.1 = 58.45 = 74.55 = 342.3 = 342.3 = 180.2 = 180.2 = 192.12
tplabuza 2008
Slide # 12
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Norrish 1 solute Example 1
What is aw if you add 20 g propylene glycol to 100 g meat of 50% moisture content? Boundary conditions 100 g meat with 50 g water 50 g solids Assume initial aw = 1 before addition Assume meat solids no effect Assume all solute dissolved Assume non-ideal ie ! <1 Moles glycol =20/76= 0.263 Moles water = 50/18 = 2.773 Xwater = [ 2.778/(2.778 + 0.263) ] =0.9136 Xsolute = 1-0.9136=0.0864 K = -1 so ! = exp (-1 x 0.0.08642)= 0.9926 vs 0.991 obs aw = 0.9926 x 0.9136 = 0.907
Slide # 13
tplabuza 2008
comparison
! Raoults
law ! Graphical ! Van Lar-Norrish

! Measured
0.914 0.906 0.907
errror 0.003
tplabuza 2008
Slide # 14
What if add 20 g PEG 600?

Moles PEG =20/600= 0.03 Moles water = 50/18 = 2.778 Xwater = [ 2.778/(2.778 + 0.03) ] =0.989 =aw Xsolute = 1-0.989=0.011 K = -56 so ! = exp (-56 x 0.0.0112)= 0.993 aw = 0.993 x 0.989 = 0.982
tplabuza 2008
Slide # 15
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Example 2
How much PG is needed to reach an aw of 0.85 ?
tplabuza 2008
Slide # 16

nwater = 50/18 = 2.778 moles
Example 2 Solution 1
aw = !
nwater nwater + nsolute 2.778 2.778 + nsolute
= 0.85 =
nsolute = 0.490 moles = 37.26 grams
tplabuza 2008
Slide # 17

From isotherm at aw =0.85 m= 147.5 g water/100 g PG
800 700 600 500 400 300
y = - 2.4286e+5 + 8.4204e+5x - 9.7383e+5x^2 + 3.7593e+5x^3 1.000 R^2 =
Example 2 solution 2
147.5 50 = 100 x x = 33.9 g PG

tplabuza 2008
200 100 0.85 0.90 0.95 1.00
water activity
Slide # 18
Page #
How much NaCl is needed to reach same aw of 0.85 ?
Conc. (% w/w) 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 19.0 19.5
tplabuza 2008
Example 3
aw 0.906 0.902 0.897 0.892 0.888 0.883 0.878 0.873 0.867 0.862 0.857 0.851 0.845
From Table ~ 19% salt w/w Thus 19/81 = x/50
X= 11.7 grams
Slide # 19
Example 4
tplabuza 2008
Slide # 20
Do by iteration
! ln
aw = ln Xw + Ks (1 - Xw)2 ! Assume value for Xw ! Calculate aw ! repeat and make plot aw vs Xw
tplabuza 2008
Slide # 21
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Example calculation
! 50 ! eg
g water -> 2.778 moles water @ 10 g PG n2 = 10/76 = 0.132

2.778 = 0.9546 2.778+0.132 Xs = 1- X w = 0.045 Xw = ln a w = - 0.0464 - 1 [0.045]2 = - 0.0485 a w = 0.9527 @ 10g PG in 50 g water
tplabuza 2008
Slide # 22
Example calculation g PG aw = 0.953 ! 20 g PG aw = 0.907 ! 30 g PG aw = 0.862 ! 40 g PG aw = 0.820

! 10
Example solution propylene glycol 50 40 30 20 10 0
0.9
1.0
water activity
tplabuza 2008
at aw = 0.85 ----> amount needed is 32.5 g PG vs 33.9 grams from isotherm and 37.3 g from Raoults Law
Slide # 23
g glycol added
Water Activity Prediction by Norrish Equation
tplabuza 2008
Slide # 24
Page #
Multiple solute solution
lnaw = ln X H2O +
! K [X ]
i i i= 1 n
! [X ]
i i =1
[1 " X ]
H2 O
Xi = mole fraction of ingredient in all water + all solute = nsi/ (nH 2O + Nsolute ) Ki = Van Laar constant for solute
tplabuza 2008
Slide # 25
Complex Food System Piglet Liquid Diet

Component Composition grams Canola Oil 40 Demineralized whey solids 10 (50% lactose, 50% protein) Gum Arabic 1.0 HFCS-solids 10 Potassium chloride 0.8 Sodium chloride 0.2 Glycerol 4.0 Propylene Glycol 8.0 Citric acid 2 Water 24
tplabuza 2008
aw Food Calc 2.0

Slide # 26
aw Food Calc 2.0
Sum solute moles = 0.2575 Moles water = 1.332 Example X glycerol = 0.0434/(1.332 +0.2575) = 0.0273
tplabuza 2008
Slide # 27
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tplabuza 2008
Slide # 28
3. Grover Equation
! aw
= 1.04 - 0.1 Es + 0.0045 (Es)2
!E o Es = ' # i # " mi
$ & & %
Ei = Grover value for component i mi = g H2 O/g solids of component i limit Es < 10 Chorleywood-Camden Computer program Based on lowering relative to sucrose in baked goods
Grover constants
Compound water and fat 28 DE 42 DE gums starch 60 DE lactose sucrose glucose, fructose protein egg white glycerol < 20% glycerol >20% sorbitol acids propylene glycol ethanol Salts
tplabuza 2008
Ei 0.0 0.7 0.8 0.8 0.8 1.0 1.0 1.0 1.3 1.3 1.4 2.0 4.0 2.0 2.5 4.0 8.0 9.0
Slide # 30
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10
Example 1
What is aw if you add 20 g propylene glycol to 100 g meat of 50% moisture content? Boundary conditions 100 g meat with 50 g water 50 g solids Assume initial aw = 1 before addition Assume meat solids no effect Assume all solute dissolved Moles glycol =20/76= 0.263 Moles water = 50/18 = 2.778
tplabuza 2008
Slide # 31
initial meat water activity component moisture protein starch fat grams 50 15 1 34 mi 3.333 50.0 1.47 Ei 1.3 0.8 0 Ei/mi 0.390 0.016 0.00
Example 1
"(Ei/mi)= Es = 0.406 mi = grams water total per gram component get Ei values from Table aw = 1.04 - 0.1 Es + 0.0045 (Es )2 initial aw = 1.04 - 0.1x0.406 + 0.0045 (0.406)2 = 1.0014
20 g PG added to meat component moisture protein starch fat PG grams 50 15 1 34 20 mi 0.0 3.333 50.0 1.47 2.5 Ei 1.3 0.8 0 4 Ei/mi 0.390 0.016 0.00 1.6
Example 1
"Ei/mi= Es = 2.006 aw = 1.04 - 0.1 Es + 0.0045 (Es )2 aw = 1.04 - 0.1 x 2.006 + 0.0045 (2.006)2 =0.857
tplabuza 2008
Slide # 33
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11
comparison
Raoult's Norrish Isotherm Grover 0.914 0.907 0.906 0.857
tplabuza 2008
Slide # 34
Piglet Diet
aw Food Calc 2.0 Es= Sum (Ei/mi)=3.302 aw = 1.04 - 0.1 Es + 0.0045 (Es )2 aw = 1.04 - 0.1 x 3.302 + 0.0045 (3.302)2 =0.759
4. Money and Born

1 aw = 1 + 0. 27N
N = moles humectant/100 g H2O Thus 20 g water in meat @ 50% water So 40 g in 100 g water N=40/76=0.526 aw = 0.876
Comparison Raoult's Norrish Isotherm Money & Born Grover
tplabuza 2008
0.914 0.907 0.906 0.876 0.857

Slide # 36
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12
Piglet diet
aw = 1/[1 +0.27 N]
aw Food Calc 2.0

tplabuza 2008
Sum N = 1.073 aw = 0.775

Slide # 37
5. Ross Equation
! ! !
Assumes no interaction of solutes All water available to all ingredients Gibbs Duhem relationship applies
G = 1N1 + 2 N2 dG = 1dN1 + N1d 1 + 2dN2 + N2 d2 for the addition or subtraction of N 1 or N 2 ! dG $ ! dG $ dG = # # dN & & dN1 + # # dN & & dN2 = 1dN1 + 2 dN2 " 1% " 2% thus: N1d1 + N2 d 2 = 0 d = RTd ln a substitute in and divide both sides by RT / N
total
X 1d ln a1 + X 2 d ln a2 = 0 if multiple solutes then and X 1 represents water: (X + (X + ln aw = ' . * 2 -d ln a2 ' . * 3 -d ln a3 * * ) X1 , ) X1 , aw = aw

tplabuza 2008
( ) (a )
0 2
w 3
Note for starches, proteins, gums etc the individual isotherm is used to get the ingredient aw
Slide # 38
Ross equation
aw = ! a H i for example aw = a H1 a H2 aH i
where a Hi = activity of solution of component i assuming all of each ingredient is dissolved in all the water or interacts with all the water For Example 1 20 g PG added to 100 g meat aw = 0.906 For example 2 assume initial meat at 0.99 from measured
af = a i a H1 a i = 0.99 af = 0.85 thus aH1 = 0.85 / 0.99 = 0.859

From isotherm mi = 155 g water / 100 g glycol or 32.3 g per 50 g water
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13
Comparison of methods
Comparison of all methods Raoult's Norrish Isotherm Ross Money & Born Grover 37.3 32.5 33.9 32.3 24.8 21.2
tplabuza 2008
Slide # 40
Combined program aw 3.0
tplabuza 2008
Slide # 41
Piglet Diet Summary

Grover Money & Born Ross with Norrish Norrish 0.759 0.775 0.813 0.816
tplabuza 2008
Slide # 42
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Dr Ted Labuza University of Minnesota Department of Food Science and Nutrition St Paul MN 55108 voice 612-624-9701 fax 651-483-3302

Water Activity Prediction by Raoults Law

X H2 O = mole fraction water water X s = mole fraction solute = 1 " X H2 O

! = effective activity coefficient

Raoults Law Example 1

position on real solute isotherm accounts for ! ! 1

To determine make solutions at different levels of Xs Plot ln [a/Xw ] vs Xs 2

Single Solute correction for non-ideality

law ! Graphical ! Van Lar-Norrish

0.914 0.906 0.907

What if add 20 g PEG 600?

How much PG is needed to reach an aw of 0.85 ?

How much PG is needed to reach an aw of 0.85 ?

nwater nwater + nsolute 2.778 2.778 + nsolute

nsolute = 0.490 moles = 37.26 grams

How much PG is needed to reach an aw of 0.85 ?

147.5 50 = 100 x x = 33.9 g PG

200 100 0.85 0.90 0.95 1.00

From Table ~ 19% salt w/w Thus 19/81 = x/50

How much PG is needed to reach an aw of 0.85 ?

aw = ln Xw + Ks (1 - Xw)2 ! Assume value for Xw ! Calculate aw ! repeat and make plot aw vs Xw

g water -> 2.778 moles water @ 10 g PG n2 = 10/76 = 0.132

Example calculation g PG aw = 0.953 ! 20 g PG aw = 0.907 ! 30 g PG aw = 0.862 ! 40 g PG aw = 0.820

Water Activity Prediction by Norrish Equation

Complex Food System Piglet Liquid Diet

aw Food Calc 2.0

aw Food Calc 2.0

= 1.04 - 0.1 Es + 0.0045 (Es)2

4. Money and Born

0.914 0.907 0.906 0.876 0.857

aw Food Calc 2.0

Sum N = 1.073 aw = 0.775

X 1d ln a1 + X 2 d ln a2 = 0 if multiple solutes then and X 1 represents water: (X + (X + ln aw = ' . * 2 -d ln a2 ' . * 3 -d ln a3 * * ) X1 , ) X1 , aw = aw

af = a i a H1 a i = 0.99 af = 0.85 thus aH1 = 0.85 / 0.99 = 0.859

Combined program aw 3.0

Piglet Diet Summary

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