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JOMO KENYATTA UNIVERSITY OF AGRICULTURE

AND TECHNOLOGY
DEPARTMENT OF FOOD SCIENCE AND TECHNOLOGY
COURSE OUTLINE- MAY – AUG 2018
AFS 2211: FUNDAMENTALS OF FOOD CHEMISTRY
LECTURER: MAMICHA KIRAGU
CONTACTS: mamichakiragu@gmail.com +254-714-635-248

PART 1 1
COURSE OBJECTIVES
Course Purpose
To make the students acquire knowledge of the chemical components of food, their
functions, reactions and interactions during handling, processing and storage

Learning Objectives
At the end of the course, the student will be able to:
■ Describe the chemistry of the various types of chemical components of foods
■ Explain the changes of the chemical components during processing and storage
■ Discuss the influence of these chemical constituents on quality and acceptability of
foods.

PART 1 2
COURSE DESCRIPTION
■ Introduction to food chemistry.
■ Chemical components of food.
■ Structures and properties of:
– Water
– Carbohydrates
– Proteins
– Lipids
– Vitamins and minerals in plants and animals.
■ Functional properties of food components during processing and preservation and
storage of foods.
■ Structure and stability of food components during processing and storage.
– Protein denaturation.
– Browning reactions.
– Lipid auto oxidation.
■ Food additives and their toxicity.
■ Enzymes in food processing.

PART 1 3
INTRODUCTION TO FOOD CHEMISTRY

■ Chemical substances found in the largest amounts in food:


– Water
■ found inside cells in plants and animals
– Carbohydrates
– Fats
– Protein

PART 1 4
Structure and properties of water
Composed of 2 Hydrogen
atoms and 1 oxygen atom
covalently bonded (H2O)
Electrons stay with Oxygen
more which leads to
polarity
Polarity = molecule has a
positive (H) end and a
negative end (O)
Polarity gives water unique
properties
Hydrogen Bonding

= Negative (Oxygen) pole of a water


molecule is attracted to the positive
(Hydrogen) pole of another water
molecule
■ It is a weak attraction but does give
water some cool properties
■ Molecules that are not polar will not
experience hydrogen bonding
Some unique properties of water
1)High Boiling Point = 100oC (212oF)
2)Solid form is less dense than liquid form (ice floats in liquid water)
3) Cohesion = water molecules wanting to stay together, keeps water in puddles
instead of widespread droplets or molecules
4) Adhesion = water molecules wanting to stay connected to other polar
surfaces (glass)
5) Capillary action = water rising on its own up through a thin column
■ Combination of adhesion attracting water molecules to the side of the
column and cohesion pulling more water up into the column
■ Glass tubes and plant roots are good examples
Water can be part of mixtures

Mixture = a combination of pure substances occupying the same space


(physically mixed but not chemically bonded)
Ex. Air is a mixture of gases (oxygen, carbon dioxide, nitrogen, etc…)
Water can dissolve other substances into it to create a solution
Water is the solvent
The dissolved substance is the solute
Salt water is a good example
Suspensions = a solid settles in a liquid, does not dissolve
Sand in water

Blood is a combination of a solution and a suspension


It contains cells (not dissolved) and other dissolved substances like sugar
Polarity of Substances

■ “Like dissolves like”


■ Polar liquids dissolve other polar liquids
■ Polar liquids will not mix with non-polar substances (i.e. – oil & water don’t
mix)
■ Substances that repel water = hydrophobic
■ Substances attracted to water = hydrophilic
pH

pH describes the concentration of H+ ions in a solution (acidity)


Water has a fairly neutral pH because not many of its molecules lose a hydrogen ion
Some solutions have an abundance of H+ ions and are called acids
Some solutions have a lack of H+ ions (or abundance of OH-) and are called bases
pH Scale
Scale extends from 1 to 14
1-6 = acid (acidic)
8-14 = base (basic or alkaline)
7 = neutral
Buffers = weak acids or bases that can be used to balance out strong changes in pH
Our bodies use buffer chemicals to maintain a balanced pH
Litmus paper
Red = acidic, blue = basic

pH paper
Different colors correspond to a specific pH

Cabbage juice – similar reaction as pH paper


WATER ACTIVITY

Water activity is the effective mole fraction of water, defined as aw = γwxw = P/P0 a where
γw is the activity coefficient of water, xw is the mole fraction g of water in the aqueous
fraction, P is the partial pressure of water above the material and P0 is the partial
pressure of pure water at the same temperature
❑ Water activity can be defined as the ratio of the vapor pressure of water in the
system to the vapor pressure of pure water at the same temperature.
❑ It can also be expressed as the equilibrium relative humidity (ERH) of the air
surrounding the food at the same temperature.
❑ Water activity is an important property in food systems. Most chemical reactions
and microbiological activity are controlled directly by the water activity.
❑ In food science, it is very useful as a measure of the potential reactivity of water
molecules with solutes.

Partial pressure of water above the solution normalized to the partial pressure above pure water.
aw=p/po~%ERH
PART 1 11
PREDICTION OF WATER ACTIVITY
❑ Raoult’s law is the basic equation for determination of water activity
of ideal solutions. According to Raoult’s law, water activity is equal to
the mole fraction of water in the solution:

where Xw is the mass fraction and M is the molecular weight. The


subscript w is for water and s for solute
❑ Raoult’s law is not valid for macromolecular solute due to the very low
molecular weight ratio of water and solute. If the solute ionizes in
solution Raoult’s law can be written as:

where ψ is the degree of ionization.


WATER ACTIVITY OF SOME COMMON FOODSTUFFS

The typical water activity of some foodstuffs

Type of product Water Activity (aw)

Fresh meat and fish .99

Bread .95

Aged cheddar .85

Jams and jellies .8

Plum pudding .8

Dried fruit .6

Cookies .3

Milk powder .2

Instant coffee .2

PART 1 13
MOISTURE SORPTION ISOTHERM

■ Highly product
specific (physical and
chemical structure)
■ Highly temperature
dependent
■ Show
sorption/desorption
hysteresis
■ Affect both
physical/chemical
reactivity of the food
and the dynamics of
water transport

PART 1 14
MOISTURE SORPTION ISOTHERM

❑ Sorption isotherms of
food materials are
generally in sigmoid
shape (type II). The
effects of Raoult’s law,
capillary effects, and
surface–water
interactions are important
in sorption curves and
they are additive.

PART 1 15
MOISTURE SORPTION ISOTHERM

❑ Type I isotherm is observed in pure crystalline sugar. It shows very little moisture gain
up to a water activity of 0.7 to 0.8 since the only effect of water is hydrogen bonding
to the –OH groups present on the surface of the crystal
❑ Thus, surface effect is important, which means grinding the sugar to smaller
particles will increase the moisture content at low water activity values. As the water
activity is increased, water begins to penetrate into the crystal, causing dissociation
of sugar–sugar interactions and a solution is obtained. At this stage, the effect of
Raoult’s law is important.
❑ The type III isotherm is observed in the case of anticaking agents. In these types of
materials, binding energy is so large that water activity is depressed while water is
absorbed. When all the binding sites are filled, the increase in moisture content
causes water activity to increase drastically.

PART 1 16
MOISTURE SORPTION ISOTHERM

Zone 3: Bulk water


Zone 2: Loosely
bound water
Zone 1: Tightly bound
water.

PART 1 17
TEMPERATURE DEPENDENCY

PART 1 18
TEMPERATURE DEPENDENCY

EFFECTS OF TEMPERATURE ON WATER ACTIVITY


❑ The temperature dependence of water activity can be described by
the Clasius-Clapeyron equation if the isosteric heat and water
activity values at one temperature are known

where qst is net isosteric heat of sorption or excess heat of sorption, and
aw1 and aw2 are the water activities at temperatures T1 and T2.
TEMPERATURE DEPENDENCY

PART 1 20
SORPTION AND DESORPTION

SORPTION ISOTHERM
❑ A moisture sorption isotherm describes the relationship between
water activity and the equilibrium moisture content of food
products at constant temperature. It is also called the equilibrium
moisture content curve.
❑ Desiccators can be used for preparation of sorption isotherms. In
the desiccator method, saturated salt solutions, sulfuric acid or
glycerol solutions are put into the bottom of desiccators .
SORPTION AND DESORPTION

❑ Although the desiccator method is very commonly used for water activity determination
and preparation of sorption isotherms, there are some errors arising from this method.

❑ The error comes from the disturbance of equilibrium caused by opening the desiccators,
taking the sample, and closing it again.

❑ These disturbances cause adsorption of water from the surrounding air by samples with
low water activities and desorption of water from samples having high water activities.

❑ If desorption occurs, the results are not affected significantly since desorption occurs
slowly. However, if adsorption occurs, water activity is affected significantly since
adsorption is a fast process.
SORPTION AND DESORPTION

❑ Equilibrium moisture content (X*) is the moisture content of a substance at equilibrium


with a given partial pressure of the vapor. It is used to describe the final moisture content
that will be reached during drying.

❑ Free moisture content is the moisture content in a substance in excess of equilibrium


moisture content (X − X*). Free moisture can be removed by drying under the given
percent relative humidity.

❑ The moisture content data can be given in a dry or wet basis. Moisture content is in a dry
basis if it is expressed as the ratio of the amount of moisture in the food to the amount of
dry solid (kg of moisture/kg of dry solid). If the moisture content of a sample is described
as the ratio of the amount of water in the food to the total amount of wet solid (kg of
moisture/kg of wet solid), it is in a wet basis.

❑ Moisture content is usually given in a wet basis to describe the composition of the food
material. It is more common to use moisture content in a dry basis to describe moisture
changes during drying.
SORPTION AND DESORPTION

❑ The SI is useful to determine the shelf life and to assess the background of operations
such as drying, conditioning, mixing, packaging, and storage.

❑ SI also gives information about the specific interaction between water and the product

❑ The two principal techniques used for the adjustment of water activity are the integral
and differential methods.

❑ Integral method, several samples are prepared and each is placed under a
controlled relative humidity environment simultaneously, moisture contents of the
samples are measured after constant weight is attained.

❑ Differential method, a single sample is placed under successively increasing or


decreasing relative humidity environments. Moisture content is measured after each
equilibration. The differential method has the advantage of using only a single
sample. As a result, the error coming from the sample variation is eliminated.
SORPTION AND DESORPTION

PART 1 25
SORPTION AND DESORPTION

■ Hysteresis
❑ Sorption isotherms can be generated from an adsorption process or a desorption
process
❑ The difference between these curves is defined as hysteresis (see figure below).

❑ Hysteresis is observed in most hygroscopic foods. In the figure, in region A, water is


tightly bound. In region B, the water is less tightly held and usually present in small
capillaries, and in region C, water is free or loosely held in large capillaries.
❑ Desorption isotherms usually give higher moisture content than adsorption
isotherms.
PART 1 26
FREEZING OF WATER
Freezing:
• In ice structure, a water molecule may bind four others -
hexagonal structure- hollow structure- high specific volume
• Melting- breaking some H- bonds resulting to more compact
packing in liquid
• The phase diagram of water indicates 3 phases with
equilibrium lines; TC (melting), TA Vapor and TB
(sublimation)
• Possible to supercool water but on introducing an ice
crystal- supercooling ceases and temp rises to 0C
• Slow freezing results to larger crystals and vice versa
• Large crystals are usually located in extracellular spaces
• Small crystals- both intra and extracellular
• Crystal growth occur readily at temperatures close to the
freezing point
• When food freezes, it changes in volume dependent on its
water content
• Freezing may cause changes in food that may be
unacceptable
• Changes include: Destabilization of emulsions, flocculation
of proteins, increase in toughness of fresh/ meat, loss of
textured integrity and increase in drip loss in meat
• Carbohydrate presence can influence ice formation

PART 1 27
FREEZING- CRYSTAL GROWTH AND NUCLEATION
• Crystal growth is contrast to nucleation
• Occurs readily at temps close to FP
• More important to initial crystallization than
progress it
• Solutes will greatly decrease ice crustal growth

• Ice crystal size at the completion of freezing is


related to the number of nuclei
• In liquid system, nuclei can be added= seeding
• Slow removal of heat results in a continuous ice
phase
• With high super cooling, nucleation increases as
crystal growth decreases
• Crystals have a tendency to enlarge during storage
• Recrystallization is evident when temperatures
fluctuate widely
• When water in food freezes, solute concentration
in unfrozen liquid increases accompanied by
changes in pH, viscosity, osmotic pressure, vapor
pressure and other properties

PART 1 28
GLASS TRANSITION
• In aqueous systems containing some polymers,
decrease in temp may lead to formation of glass
• Glass= amorphous solid material as opposed to
crystalline
• An undercooled liquid with high viscosity
• Achieved by high cooling rate
• Disordered liquid state is immobilized into a
disordered glassy solid
• When water containing foods are cooled below the
freezing point of water, ice may be formed and
remaining water is high in dissolved solubles
• When Tg is reached, remaining water is transformed
to glass
• Ice formation during freezing may destabilize
sensitive products- rupturing cells, breaking
emulsions
• Presence of glass forming substances may prevent
this= cryoprotection, done using cryoprotectants
• Rapidly removing water from foods leads to
formation of a glass
• Water present in foods may act as a plasticizer=
increase plasticity and flexibility
• Increasing water content decreases tg

PART 1 29
aw AND REACTION RATES

Moisture content (d.w.b.)

log (RATE)
Microbial growth

aw
aw AND REACTION RATES ..CONTD

■ Moisture content and aw


affect both chemical and
microbial spoilage
■ Dried foods= mc of 5-15%
(lower parts of the moisture
SI), intermediate foods = mc
20-40% (aw over 0.5 and
capillary water)
■ Aw can be reduced by drying
or adding solutes sa sugar or
salt.
■ Below a aw of 0.9, no
bacterial growth, usually mold
inhibited between 0.88 and
0.8 aw
■ Most enzymes inactive below
aw of 0.85, lipases may be
active even at 0.1 aw
EXAMPLE- POTATO CRISP OXIDATION

PART 1 32
GAB MODEL

PART 1 33
EFFECT OF aw ON TEXTURE

PART 1 34
AW EFFECT ON POWDER PROPERTIES

PART 1 35
Aw AND PACKAGING

■ Packaging can do much to


retain optimal conditions of
foods for long storage life
■ SI play an important role in
selection of packaging
materials
■ Hygroscopic products have a
steep SI- need moisture proof
packaging- eg instant coffee
■ For foods whose ERH is above
that of the external climatic
conditions, packaging serves to
prevent moisture loss eg
processed cheese and baked
goods
■ Mixed products packed
together reach a mean ERH but
not a mean MC
■ Stability in dehydrated foods is
impaired when packaged
together

PART 1 36
WATER BINDING IN MEAT

• Water binding capacity of meat caused by muscle proteins-


myofibrils
• 34 % of the muscle protein water soluble
• Main portion is structural
• Monolayer water in meat localized at hydrophilic groups
including; carboxyl, amino, hydroxyl and sulphydryl groups. Also
at nondissociable carboxyl and imino groups of peptide bonds
• Binding of water strongly influenced by pH
• Multilayer water in meat is immobilized between networks of
membranes and filaments of the structural proteins, cross-
linkages and electrostatic attractions of peptide chains
• Changes in water binding capacity in meat during processing,
aging and storage relate to free water
• Shrinkage of structure would thus decrease WHC
• Freezing of meat leads to a decrease in WHC in the isoelectric
pH range of muscle
• Heating and freezing will also affect the WHC of meat muscle
• Addition of certain salts such as phosphates may greatly affect
WHC
• Water retention in food systems is important when there is need
for it to act as a plasticizer

PART 1 37
aw IS A CONSIDERATION FOR GMPs

• Aw is one of the criteria for


establishing GMP regulations and
classification of foods
• Controlled foods have pH greater than
4.6 and aw greater than 0.85 ( low
acid foods)
• When packed in hermetically sealed
containers, processing to commercial
sterility is a must
• Intermediate foods, aw 0.9 to 0.6-
achieve stability by combination of aw
and other factors sa pH, heat,
preservatives and ERH

PART 1 38
Exercise 1
NaCl, sucrose or the NaCl-sucrose solutions are commonly used for osmotic
dehydration of potatoes.

(a) Estimate the water activity of 20% sucrose solution.

(b) Estimate the water activity of 20% NaCl solution

(c) Estimate the water activity of solution containing 10% NaCl and 10%
sucrose.

(d) Which solution do you think will be more efficient for osmotic dehydration
of potatoes having water activity of 0.942?

Data:
Molecular weight of water: 18 kg/kg-mole
Molecular weight of NaCl: 58.44 kg/kg-mole
Molecular weight of sucrose: 342 kg/kg-mole
NaCl ionizes and its maximum degree of ionization, ψ: 2.
END OF CHAPTER ON WATER

PART 1 40

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