Fundamentals of Water

Activity and Moisture

Sorption Isotherms

Wendy Ortman

Decagon Devices
Outline
 Water Activity
 Definition and theory
 Measurement methods
 Moisture Content
 Definition
 Measurement methods
 Moisture Sorption Isotherms
 Applications for water activity and
isotherms
Water Activity Definition
 Water activity is derived from
fundamental principles of
thermodynamics and physical
chemistry.
 Standard State (Pure Water) is defined
 System must be in equilibrium
 Temperature must be defined
Water Activity Definition
Correct Definition: Water Activity is a measure of the energy status of
the water in a system.

Old Definition: Water activity is the amount of “free” or “available”

water in a product as opposed to “bound” water.

aw = f/fo = p/po
Vapor pressure of water above sample @ °C
aw = ——————————————————
Vapor pressure of pure water @ same °C

aw = ERH (%) /100

Water Activity Definition
aw = p/po

1. Equilibrium
2. Constant T & P
WaterMoleculeDemostration.wmv
Water Activity Instrumentation

water vapor
Sample
(humidity)

Water Activity is measured by equilibrating

a product with the vapor phase and
measuring the relative humidity of the vapor
phase.
Electrical Properties Sensors
 Advantages
 Accuracy = ±0.01aw
 Relatively insensitive to
volatiles
 Measures entire aw range

 Disadvantages
 Needs calibration
(secondary method)
 Need temperature control
or compensation of sensor
 Some sensor hysteresis
Chilled Mirror Dew Point
 Advantages
 Primary method of measuring
vapor pressure (not
calibrated)
Fan
 Highest accuracy ±0.003aw Optical Sensor
 Rapid measurement <5 Mirror
minutes Infrared Sensor

 Measures entire aw range

(0.03 – 1.0aw)
 High reliability
Sample
 Disadvantages
 Need clean mirror
 Readings affected by alcohol
and propylene glycol
Dewpoint and Volatiles
 Interference: Propylene Propanol

Glycol, Ethanol, Propanol,

 No Interference: Glycerin
Ethanol

 All problematic volatiles

are small, volatile, and
have both polar and non- Propylene Glycol

polar carbons
 The interference likely due Glycerin

to surfactancy
Getting the Most Out of Your
Instrument
Accurate Measurements
 Calibration / Verification Standards
 Saturated Salt Slurries
 Unsaturated Salt Solutions
 Temperature
 Sample Preparation
 Need representative sample
 If slicing / grinding – be consistent
 Prevent moisture exchange with environment
Standards
Unsaturated Salt Solutions
 Unsaturated salt solutions make excellent
standards.
 Solutions are relatively unaffected by
temperature over a wide range.
 Any aw level can be computed.
Temperature Effect
 Water activity changes with temperature thus:
 it is necessary to control temperature
 compensate for temperature difference between sample
and sensor
 wait for thermal equilibrium

 Research purposes for temperature control:

 temperature vs. aw studies
 accelerated shelf-life studies
 isotherm generation
 lab to lab sample comparison
 Compliance with government or internal regulations for
specific products
 Eliminate extreme ambient temperature fluctuations
Sample Preparation
 Range of test material is immense
(raw ingredients to finished products)
 Need representative sample
 If slicing / grinding – be consistent
 Test immediately
Moisture Content
Moisture Content Defined
 Quantitative measure of amount of water
 Empirical measurement with no standard
 Primary Method: Loss on Drying
Wet Weight - Dry Weight
x100
Dry Weight (db) or Wet Weight (wb)
 Primary Method: Titration
3Z  ROH  I 2  H 2O  3ZH   ROSO3  2 I 
Moisture Content Challenges
 Without a standard, cannot measure
accuracy
 Is water the only thing that volatizes?
 Many different methods
 Many sources of variation
 Reporting Basis
Why Measure Moisture
Content
 Water activity vs. moisture content
 Purity
 Labeling
 Nutrition
 Point of sale
Moisture Content Measurment
 Direct Methods  Indirect Methods
 Dessication by Water  Electrical
Transfer Measurements
 Distillation  Infrared, Halogen,
 Oven Drying Microwave Drying
 TrueDry  Dewpoint
 Calcium Carbide or  NMR Spectroscopy
Hydride  NIR Spectroscopy
 Karl Fischer Titration  Microwave
Spectroscopy
Water activity vs. Moisture content
 Moisture Content
 Quantitative amount of water in a sample on a wet or
dry basis.
 An extensive property that depends on the amount of
material.

 Water Activity
 A measure of the energy status of the water in a
system (Qualitative).
 A intensive property that does not depend on the
amount of material.
Applications for Water Activity
and Moisture Content
 Water Activity Can Help You:  Moisture Content Can Help
 Control microbial growth You:
 Adjust texture at a given water
 Control chemical reaction activity
rates
 Control chemical reactivity and
 Conduct shelf life testing rates
 Predict effects of temperature  Determine ingredient
abuse concentrations
 Formulate profitable products  Determine nutritional content
 Achieve optimal texture
 Control moisture migration
 Model dry ingredient mixing
 Avoid caking and clumping
 Predict packaging needs
 Characterize products
Microbial Growth
 Scott (1953 & 1957) showed that
microorganisms have a limiting
water activity level below which they
will not grow.

 Water activity, not water content,

determines the lower limit of
available water for microbial growth.
Scott,W.J. 1953. Water relations of Staphylococcus aureus at 30ºC. Aust. J. Biol. Sci. 6:549-564.
Scott,W.J. 1957. Water relations of food spoilage microorganisms. Adv Food Res 7:83-127.
Microbial Growth
 Growth Limit
 Every microorganism has a water activity level
below which it cannot grow.

aw limit Microorganisms
0.91 Gram Negative Bacteria
0.86 Gram Positive Bacteria
0.88 Yeast (practical limit)
0.80 Production of mycotoxins
0.70 Molds (practical limit)
0.62 Osmophilic yeast
0.61 Xerophilic molds
0.60 Absolute limit for all growth
Microbial Failures
The consequence of a microbiological failure, as it
relates to product recalls, can be very costly.

 Recalls can cost millions of dollars in

product losses and operational delays
 Sales may suffer as a result from:
 loss of consumer confidence
 consumers relating the recall to other
products
 Company reputation damage.

Figure 1 from http://www.humaneresearch.org/

Prevent Mold with aw
 Chemical/Biochemical Stability
In general, reaction rate
increases as water activity
increases from the
monolayer value. Common
reactions related to Loss of

chemical stability: Crispness

Powder
Maillard Browning Caking

Lipid Oxidation Collapse

Hydrolysis
Nutrient Degradation
Enzymatic Reactions
Enzymatic Stability
Chemical/Biochemical Stability
 Maillard reactions are a
complex series of
reactions involving
 free amines (amino acid)
 carbonyl groups (reducing
sugars)

 Maximum loss of amino nitrogen

occurs at 0.60-0.70 aw
Chemical/Biochemical Stability
Lipid Oxidation

 A minimum reaction rate at

a water activity of about
~0.3 aw

 Rate increase from

0-0.3aw and 0.4-0.8aw
Increased Shelf Life = More $$$

Storage Water Activity

Conditions
(5 weeks) 0.113 0.30 0.5289 0.6886 0.9358
Color 1 3 4.5 6 10
Smell 10 4 1 1 10
Color Tan 1 10 Red
Smell Peppery 1 10 Rancid
Physical Stability
 Physical Properties
 Texture, Hardness, Compaction
 Coating Integrity
 Moisture migration
 Powder Flow Properties
 Caking and Clumping of powders
Textural Properties
 Hard or crisp products
 low water activity
 break when physically
stressed
 are crisp and crunchy
12.00
 soften when exposed to aw Completely Dissolved
10.00

Moisture Content (w.b.)
8.00 Dissolution Begins

 Soft products 6.00

 intermediate to high aw 4.00
Surface begins to be sticky

 bend when stressed

and color becomes cloudy

2.00
 are moist, juicy, tender,
0.00
and chewy. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

 harden when exposed to  Lifesaver as is Water Activity 0.29 a Water Activity

w

aw
What Does Water Activity Have to Do
with Texture For Taffy?
1600

1400

1200
Too
1000

Soft
Hardness (g)

800
Too Hard Good
600
and
400 Sticky
200

0
0.43 0.53 0.57 0.65
Water Activity

As is Water Activity 0.58 aw

Moisture Migration
 Moisture migration can
lead to:
 texture changes
 microbial growth
 degradation reactions
Component A
 organoleptic changes

 Examples of Multi-domain Component B

systems
 Cream filled cake
Component A
 Candy with coating
 Filled chocolates
 Ice cream with inclusions
Solutions to Moisture
Migration
 Solutions to limit moisture
migration
 make components to same
water activity
 lower aw of high aw component
 raise aw of low aw component
 retard diffusion process within
component (viscosity)
 edible barrier
 separate packaging
Controlling Water Activity
 Dehydrate Product  Additives
 Edible films and coatings  Ingredients involved in water
 Keep water from migrating binding
between the different  Humectants:
components in a composite  salt – (NaCl)
samples.  sugars – (glucose, fructose,
 They are located on the sucrose, syrups)
surface or as thin layers  glycols – (glycerol, PEG,
between several parts propylene glycol)
within the product.  amino acids – (glycine,
alanine)
 polymers – (starch, gums)
 acids – (citric acid, lactic acid)
 Anticaking agents
Controlling Water Activity
 Additives
 Limitations on aw lowering
 Solubility
 Molecular weight
 Organoleptic
 Crystallization in storage
 Reactivity – Browning reaction
 Toxicity
Process Control of Water
Activity
 Formulate with aw in mind to achieve optimal
stability
 aw measurement confirms shelf life, quality, and
safety testing data on-line
 aw is a more effective production specification
 Control belt speed, oven temperature
 Archive information for inspections, customer
complaints
Process Control of Water
Activity

Packaging
QA/QC
and Shelf Life
• Optimize for • Raw Ingredient
Chemical and • Predictive Modeling Inspection
Physical Stability • Packaging • Feedback Control • Quality and
• Humectants Requirements Consistency
• Shelf Life Testing • Safety
Product
Manufacturing
Formulation
Problems with Moisture Specs
9
8
Moisture Content (% d.b.)

7
6
5

4
3
2 Product
Could Mold
1 Product Safe
0
0 0.2 0.4 0.6 0.8 1
Water Activity
Maximize Profits with Water
 Example: Pet Food Manufacturer

Did product formulation studies and had a critical water

activity limit of 0.65 for product.

Production and QC were performing moisture content

analysis.
 never had a micro problem or shelf life concerns
 checked water activity of product (aw = 0.43)

Now use water activity measurements

 pet food is sold on a weight basis
 now able to sell more product and continue to maintain a safe
and stable product
Maximize Profits!!!
Example: if you .....
• have a production rate of 20,000 lbs/hr
• operate 16 hrs/day, 22 days/mo.
• sell your product for $0.40 per pound
• currently dry to a targeted moisture of 8% (0.50aw).
• raise to a 0.65aw (10% moisture content)
You would be producing over an additional 1,689,600
lbs/yr
and an additional $675,840 per year of revenue for
the same amount of raw material, man hours, wear &
tear, and less in utilities.
JUST FOR SELLING WATER!!
Moisture Sorption Isotherms
The relationship between water activity
and equilibrium moisture content of a
sample at a specified temperature is
called the moisture sorption isotherm.
Moisture Sorption Isotherm
Icing Creme Filling Cake
Wood Pulp Granola Bar Milk Powder
Each product has its 50

own unique moisture 45

sorption isotherm – due 40

Moisture Content (% d.b.)

35
to different interactions 30
(colligative, capillary, 25

and surface effects) 20

between the water and 15

the solid components at 10

5
different moisture 0
contents. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Water Activity
Temperature
Temperature must
be specified and
held constant.
The effect of
temperature on the
moisture sorption
isotherm follows
the Clausius-
Clapeyron
equation.
Desorption isotherms of potato slices at various temperatures.
From Gorling, P. (1958) in Fundamental Aspects of the
Dehydrationof Foodstuffs. Society of Chemical Industry,
London, pp 42-53.
Full Isotherm
25
Moisture Content (% d.b.)

20
Desorption
15

10
Adsorption
5

0
0 0.2 0.4 0.6 0.8 1
Water Activity

*Data is for Starch

Method 1: Desiccator Isotherm
Method
 Determine equilibrium moisture contents
at several water activities.
 Place product (dried or hydrated) into
controlled humidity chambers at constant
temperature
 Need six to nine different aw levels (5 min)
 Temperature control
 Measure the weight gain or loss with time
until equilibrium.
 One to Three weeks for equilibrium
Desiccator Isotherm Method

 Very slow
 Very laborious
 Lots of Space
 Few data points
 Usually only working
isotherm
Method 2: Dynamic Vapor
Sorption (DVS)
 Cycling of water activity is
automatic Temp: 25.0 °C

 Gravimetrically
DVS Change In Mass (ref) Plot Meth: polymer film.sao
MRef: 2.28063

dm - dry Target RH

determines when weight 4

3.5
100

90

change has slowed to an 3

80

acceptable level 2.5

70

Change In Mass (%) - Ref

 Facilitates evaluation of
60

Target RH (%)
2

50
1.5

sorption kinetics 1
40

 Still relies on equilibration

30

0.5
20

to set water activity levels 0

250

-0.5
350 450 550 650 750 850
10

0
Time/mins
DVS - The Sorption Solution © Surface Measurement Systems Ltd UK 1996-2007
Highlights of Static Isotherms
+ Decrease equilibration time, no mold growth
+ Sample not exposure to room Temp and %RH conditions
+ Can select any %RH between 3 and 95%
+ Decreased manual labor
+ Can be used to investigate kinetics of water sorption

- Still time consuming (usually only one sample can be run at a time)
- Limited data resolution
- Difficult to capture real-time sorption events, such as Tg and
hydrate formation and loss
DVS Isotherms Comparison

* Data is from Shelly Schmidt

Method 3: Dynamic Isotherms
 Dynamic Dewpoint Dry Air Wet Air
Isotherm
 Controls neither the water
content nor the water Fan
activity Optical Sensor

 Water activity is determined Mirror

Infrared Sensor
using a standard chilled-
mirror dewpoint sensor
 Weight tracked by magnetic
force balance
 Isotherm data in approx. 24- Sample

48 hrs
Precision Balance
Highlights of Dynamic Isotherms

+ Equilibration to known water activity not

necessary, making them very fast.
+ Incredibly high data resolution
+ Can be used to investigate sorption changes due
to matrix transitions
+ Provides a more real world sorption picture

- Does not provide kinetics of sorption

- Can result in non-equilibrium conditions and larger
hysteresis
Comparing Isotherm Methods
DVS Dessicator DVS2 PEC

25

20
Moisture Content (% d.b.)

15

10

0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
Water Activity
Comparing Isotherm Methods
DVS Dessicator DVS2 PEC DDI Method

25

20
Moisture Content (% d.b.)

15

10

0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
Water Activity
AquaLab Vapor Sorption Analyzer
Dynamic and Static in One Instrument
 Dynamic and static methods can be
analyzed on 1 sample

 Dynamic isotherms for matrix

transitions

 Static isotherms for kinetic research

 Run a sample initially with Dynamic

isotherm to determine regions of
interest

 Investigate the time dependency in the

regions of interest using a Static
isotherm
DVS and DDI Isotherm of One Sample

* Data is for Microcrystalline Cellulose at 25C

Dynamic Isotherms and Glass Transition

Large number of
water binding sites
become available

Caking, Clumping,
Crystallization, Loss
Limited Water of Texture
Binding Sites

RHc Critical Water Activity

Amorphous Metastable State

*Spray Dried Milk Powder

Savitsky/Golay 2nd Derivative
Dissolution Onset at
0.2 Glass Transition at 0.731
0.437
0.1

0
0 0.2 0.4 0.6 0.8 1
-0.1

-0.2

-0.3 Crystallization Onset

at 0.548
-0.4

-0.5
*Data is for Spray Dried Milk Powder
 DDI Method for Phase Transitions
High
Rubbery State

Tg

Constant T
Scan aw

Low Glassy State Critical %MC or aw

Low %Moisture Content or aw High

Additional Glass Transitions
Milk Powder Malto 16.5 Infant Formula Drink Mix Fiber Powder

25

20
Moisture Content (d.b.)

15

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Water Activity
Dynamic Isotherm Only
DDI Method

20
Moisture Content (% d.b.)

18
No Crystallization or Kinetics
16
14
12
10
8
6
4 Glass Transition Inflection Point
2
0
0 0.2 0.4 0.6 0.8 1
Water Activity

* Data is for Spray Dried Milk Powder at 25C

Static Isotherm Only
Kinetics of Sorption and Diffusion
10.00% 10.00% 0.8000

9.00% Crystallization 9.00%

0.7000
8.00% 8.00%
0.6000
% Moisture Content

% Moisture Content
7.00% 7.00%

Water Activity
0.5000
6.00% 6.00%

5.00% 5.00% 0.4000

4.00% 4.00%
0.3000
3.00% 3.00%
No inflection point visible 0.2000
2.00% to indicate glass transition 2.00%
0.1000
1.00% 1.00%

0.00% 0.00% 0.0000

0.0000 0.2000 0.4000 0.6000 0.8000 0.0 2000.0 4000.0 6000.0
Water Activity Time (min)

* Data is for Spray Dried Milk Powder at 25C

Glass Transition and Crystallization
Measurement
Static Isotherm Dynamic Isotherm
25

20
% Moisture Content

15 Crystallization

10

5
Glass Transition Inflection Point

0
0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000 1.0000
Water Activity

* Data is for Spray Dried Milk Powder at 25C

Applications for Isotherms
Dynamic Isotherms Static Isotherms
 Identify glass transition  Kinetics of moisture
and deliquescence points sorption
 Identify critical aw values  Crystallization
 Prevent powder caking  Equilibrium moisture
 Determine hygroscopicity content values
 Temperature abuse
 Predict packaging needs
Determine Crystallization

Milk Powder at 25C

Determine Glass Transition
Drinking Chocolate Powder at 15C, 25C & 40C (100ml)
12  15C (100ml)  25C (100ml)  40C (100ml)

10
Moisture Content (% w.b.)

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Water Activity
Determining Deliquescence
Point

Deliquescence
Point

*Sucrose
Determine Relative Hygroscopisity
 Hygroscopisity is defined
as the equilibrium moisture
content (EMC) at a given
aw. A higher EMC or
steeper isotherm slope,
indicates a more
hygroscopic material.
 At low aw, Croscarmellose
is most hygroscopic
 At aw > than 0.70, Sorbitol
and Sucrose experience
phase changes and
become hygroscopic
 Mannitol is non-
hygroscopic over the entire
water activity range
Powder Flow and Caking
 Caking is water
activity, time and
temperature
dependent process.
 Free flowing powder
is transformed into
lumps and eventually
an agglomerated
solid.
 Problem is ubiquitous
in the food and
pharmaceutical
industries.
Powder Flow and Caking
 Solutions: To maintain the flow properties and
prevent caking of powders
 Establish a Critical Water Activity
 Treatment of the powders below critical water activity
 packaging in high moisture barrier packages
 storage at low temperatures
 in package desiccation
 agglomeration
 addition of anticaking agents
 Prevent Product Loss
0.5
60

50 0.4
Moisture Content (% w.b.)

40 0.3

2nd Derivative
30 0.2

20 0.1

10 0
0 0.2 0.4 0.6 0.8

0
-0.1
0 0.2 0.4 0.6 0.8 1
Water Activity Water Activity

Dry Soup Mix at 25°C

 Impact of Critical aw

Before critical aw After critical aw

Product Formulation
Moisture sorption
isotherms of cellulose
model systems
containing various
amounts of glycerol at
37°C.

Labuza, T. P., Heidelbaugh, N. D., Silver, M., and Karel, M. (1971). Oxidation at intermediate
moisture contents. Journal of American Oil Chemists Society. 48:86-90.
Product Formulation
 All 3 components have
same water activity
 3 components have
very different moisture
contents
 Each component has a
unique texture
 Icing serves as a
moisture barrier for the
cake
Modeling Temperature Abuse
Temperature abuse could lead to spoilage during storage

Granola Bar Isotherm at 3 different Temperatures

 Water activity is
35
temperature 30

Moisture Content (% d.b.)

dependent 25

20

15
 Most products have 10 15c

a lower water activity 5

25c
40c

value at lower 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
temperature. Water Activity
Isotherms at Different Temperatures
15c 20c 25c 30c 35c 40c

25
Moisture Content (% d.b.)

20

15

10

0
0 0.2 0.4 0.6 0.8 1
Water Activity

*Data is for Spray Dried Milk Powder

Tracking Changes in Package
 Package permeability can be Evaporation

determined using changes in H20

water activity H20
 Moisture sorption isotherm
P/Lo H20
slope needed to adjust for
non-steady state P/Lo aw in

 Once package permeability is P/Lo

known, it can be used to
predict shelf life in a package aw out

 Models are also available to

determine package needs to
achieve a specific shelf life Fick’s 1st Law
 WVTR must be converted to
PApsat
P/Lo (permeance) to use in
models
Q  awout  awin 
Lo
 Package Performance
 = slope of the isotherm (g/g)
awo = initial water activity

Shelf life prediction of packaging awc = critical water activity

pa = atmospheric pressure (kPa)

 ha  a wc  M = total mass of product inside the

t shelf   ln  package (g)

 ha  a wo  es = saturation water vapor pressure at

package temperature (kPa)
A = package surface area (m2)
Time Constant
gv = package conductance (g m-2 s-1)

 pa M ha= Humidity of air,

 WVTR = Water Vapor Transmission Rate

es Ag v t = Time in package,
= Time constant
Package Performance Example
Example: A milk powder producer wants to know more information
about his packaging material, especially under abuse conditions.

14

12
Moisture Content (% wb)

10

8
y = 2.59x + 2.89
6 2
R = 0.97
4

2
Critical aw = 0.43
0
0 0.2 0.4 0.6 0.8
Water Activity
 Package Calculations
Water Activity and Shelf Life Prediction

 ha  awc   0.60  0.43 

tshelf   ln    133.6 ln    136.7 days
 ha  awo   0.60  0.10 

Required Package WVTR for 1 year Shelf Life

k M 0.026  272
   0.282 g m -2 day -1kPa  WVTR of 0.54
x es A 3  0.023  338.3

Common Resealable Plastic Package WVTR = 5.0 g m-2 days-1

Use Isotherms and aw to
Increase Shelf Life
60

50
Moisture Content (% w.b.)

40

30

20

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Water Activity
Water Activity, Texture, Packaging
Before After

 Shelf life of less than  Shelf life increased to

30 days over 6 months
 Limited market  3 stores to over 60
 Undesirable texture stores carrying
changes product
 Risk of mold growth  Increased confidence
in safety and quality

Increased Profit and Growth with a Better and Safer

Product
Who Uses Water Activity and
Isotherms and for What?
Companies Uses
Ingredient mixing, powder flow,
Kraft
product formulation
Ingredient mixing, product
General Mills
formulation, deliquescence
Excipient stability, glass transition,
Glaxo-Smith Kline
moisture migration, API stability
Ingredient mixing, product
Quaker
formulation, deliquescence
Powder flow, caking, chemical
Meade Johnson
stability, glass transition
Powder flow, caking, chemical
Nestle Pet Care
stability, glass transition,
Conclusion
 Complete moisture analysis is a relatively
simple but powerful way to control product
safety and quality.

 Water Activity, Moisture Content, and Moisture

sorption isotherms can easily be measured with
instrumentation

 Complete moisture analysis relates to:

 Microbial Growth
 Chemical / Biochemical Stability
 Shelf Life
 Product Formulation
 Physical Properties
Thank you
Decagon Devices, Inc.
2365 NE Hopkins Court
Pullman, Washington 99163
Phone: (509) 332-2756 / (800) 755-2751
Fax: (509) 332-5158
Email: [email protected]
Web: www.aqualab.com