Food Chemistry

Lecture 3
 3. Chemical methods
Karl Fischer Reagent Titration
The need for dehydrated foods stimulated the search for more rapid and accurate methods
for determining moisture. The Karl Fischer reagent has proved to be quite adaptable for this
purpose.
 The Karl Fischer method for moisture determination is based on the reaction
which involves the reduction of iodine by sulphur dioxide in the presence of
water.

 2 H2O + SO2 + I2 ------------- H2SO4 + 2 HI

 As shown by the above reaction for each mole of water one mole of iodine is
required.
 Methanol is used to dissolve iodine and pyridine is used to dissolve sulphur
dioxide.
 Numerous variations have been proposed for the preparation of the Fischer
reagent.
 The sample in which water is to be determined is dispersed in an appropriate
solvent (i.e. methanol, mixture of methanol-sulphur dioxide-pyridine etc.).
 The solution is then titrated with a solution of iodine in methanol.
 The excess of iodine that cannot react with water is in free form.
 Adding to the system a few drops of methylene blue gives a green end point.
 Contd.
• Interfering substances are ascorbic acid (oxidation),
aldehydes, ketones (release water), mercaptans,
diacylperoxide, thioacids and hydrazines – fading end point.
• The determination of moisture is carried out in a non
aqueous system.
• Fluids are delivered but with an automatic pipet or syringe.
• Viscous fluids or pastes are generally homogenized with a
solvent.
• Solids are either homogenized with solvent or titrated as
suspensions.
• Granular products must be pulverized.
 Advantages

• It is a method of choice for determination of water in many low moisture

foods such as dried fruits and vegetables, candies, chocolate, roasted
coffee, oils and fats.
• Superiority of the method was demonstrated in determining moisture in
sugar rich foods (honey) or foods rich both in reducing sugars and proteins.
• The procedure has been applied also to foods with intermediate moisture
foods (bakery doughs, baked products, fat rich cake mixes) and to foods
with high levels of volatile oils.
• The Karl Fischer reagent has proved to be quite adaptable for moisture
determination by chemical method.
 Disadvantages

• The main difficulty in using the Karl Fischer method

arises from the lack of complete water extraction.
• Formaldehyde is found to be a more rapid and
versatile extractant of water from foods than
methanol.
• Modification of the extraction procedure is
exemplified by a method for the water
determination in dairy products, where in xylene or
carbon tetrachloride is employed in mixed solvent
systems with alcohol.
 4. Physical Methods

1) Infrared determination – based on measuring the absorption at wavelengths

characteristic of the molecular vibration in water. The most useful wavelengths are 3.0 & 6.1 μm.

2) Gas chromatographic method: based on extracting the moisture with an organic solvent and
determining water in the extract by gas chromatography.

3) Electric method
The moisture determination in dielectric-type meters is based on the fact that the dielectric
constant of water (80.37 at 20◦C) is higher than that of most solvents. The dielectric constant is
measured as an index of capacitance. As an example, the dielectric method is used widely for
cereal grains. Its use is based on the fact that water has a dielectric constant of 80.37, whereas
starches and proteins found in cereals have dielectric constants of 10. By determining this properly
on samples in standard metal condensers, dial readings may be obtained and the percentage of
moisture determined from a previously constructed standard curve for a particular cereal grain.
 4) Densitometric/Hydrometry method

Hydrometry is the science of measuring specific gravity or

density, which can be done using several different
principles and instruments.
While hydrometry is considered archaic in some
analytical circles, it is still widely used and, with proper
technique, is highly accurate.
Specific gravity measurements with various types of
hydrometers or with a pycnometer are commonly used
for routine testing of moisture (or solids) content of
numerous food products.
These include beverages, salt brines, and sugar solutions.
Specific gravity measurements are best applied to the
analysis of solutions consisting of only one solute in a
medium of water.
 5) Refractometric method

Moisture in liquid sugar products and condensed milks can be

determined using a Baumé hydrometer (solids), a Brix hydrometer
(sugar content), gravimetric means, or a refractometer. If it is
performed correctly and no crystalline solids are evident, the
refractometer procedure is rapid and surprisingly accurate (AOAC
Method 9.32.14C, for solids in syrups). The refractometer has been
valuable in determining the soluble solids in fruits and fruit
products (AOAC Method 932.12; 976.20; 983.17).
Some refractometers are designed only to provide results as
refractive indices, others, particularly hand-held, quick-to-use
units, are equipped with scales calibrated to read the percentage
of solids, percentage of sugars, and the like, depending on the
products for which they are intended.
Tables are provided with the instruments to convert values and
adjust for temperature differences. Refractometers are used not
just on the laboratory bench or as hand-held units. Refractometers
can be installed in a liquid processing line to monitor the ˚Brix of
products such as carbonated soft drinks, dissolved solids in orange
juice, and the percentage of solids in milk.
 6) Polarimetric method

Polarimetry is a non-destructive method used to

measure the concentration and purity of a substance
in a solution based on its rotation of the plane
polarised light. Polarimetry can be used only for
optically active substances.
A substance is said to be optically active if it rotates
the plane polarised light, either left or right. Optical
activity of a substance depends on its chirality. A chiral
substance is one that cannot be superposed on its
mirror image. The presence of a chiral centre in the
structure of a substance makes it chiral.
 A common example for a chiral centre is acarbon atom
with four different groups attached to it. A chiral
substance and its non superposable mirror image are
known as enantiomers. The enantiomers are identical
in almost all properties expect a few including their
optical activity.They rotate light by exactly the same
amount but in the opposite direction.