Dr Ted Labuza University of Minnesota Department of Food Science and Nutrition St Paul MN 55108 voice 612-624-9701 fax 651-483-3302
[email protected]
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 [email protected]
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Water Activity Prediction by Raoults Law
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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
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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 [email protected]
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
tplabuza 2008 Slide # 4
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
tplabuza 2008 Slide # 5
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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Dr Ted Labuza University of Minnesota Department of Food Science and Nutrition St Paul MN 55108 voice 612-624-9701 fax 651-483-3302 [email protected]
Example 1 Solution #2
position on real solute isotherm
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 =
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
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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
tplabuza 2008 Slide # 8
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
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ln ! = ln
aw 2 = Ks X s Xw
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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 [email protected]
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
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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
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Increases activity
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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
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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 [email protected]
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
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comparison
! Raoults
law ! Graphical ! Van Lar-Norrish
! Measured
0.914 0.906 0.907
errror 0.003
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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
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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 [email protected]
Example 2
How much PG is needed to reach an aw of 0.85 ?
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How much PG is needed to reach an aw of 0.85 ?
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
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How much PG is needed to reach an aw of 0.85 ?
From isotherm at aw =0.85 m= 147.5 g water/100 g PG
Propylene glycol isotherm
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
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200 100 0.85 0.90 0.95 1.00
water activity
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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 [email protected]
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
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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
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Example 4
How much PG is needed to reach an aw of 0.85 ?
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Do by iteration
! ln
aw = ln Xw + Ks (1 - Xw)2 ! Assume value for Xw ! Calculate aw ! repeat and make plot aw vs Xw
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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 [email protected]
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
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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
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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 [email protected]
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
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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
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aw Food Calc 2.0
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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
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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 [email protected]
tplabuza 2008
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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
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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
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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
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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 [email protected]
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
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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
tplabuza 2008 Slide # 32
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
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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 [email protected]
comparison
Raoult's Norrish Isotherm Grover 0.914 0.907 0.906 0.857
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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
tplabuza 2008 Slide # 35
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
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0.914 0.907 0.906 0.876 0.857
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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 [email protected]
Piglet diet
aw = 1/[1 +0.27 N]
aw Food Calc 2.0
tplabuza 2008
Sum N = 1.073 aw = 0.775
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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
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( ) (a )
0 2
w 3
Note for starches, proteins, gums etc the individual isotherm is used to get the ingredient aw
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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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Dr Ted Labuza University of Minnesota Department of Food Science and Nutrition St Paul MN 55108 voice 612-624-9701 fax 651-483-3302 [email protected]
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
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Combined program aw 3.0
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Piglet Diet Summary
Grover Money & Born Ross with Norrish Norrish 0.759 0.775 0.813 0.816
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