PTT 259

OLEOCHEMICAL PROCESS
AND PRODUCTS

OIL AND FAT

ANALYSIS
NOR MUNIRAH ROHAIZAD
Oil and Fat Analysis

To ensure the
quality control
in the process

WHY
To ensure
To determine
products
the cause of
function and
product failures
design
Oil and Fat Analysis

Non fatty Refining and Performance

impurities bleaching testing

Melting,
Color and
solidification
appearance
and consistency

Flavor,
Composition
randicity and
analysis
stability
 NON FATTY IMPURITIES
Non fatty
impurities

Impurities Soap Moisture Trace metal

analysis analysis analysis analysis

Insoluble Filterable Turbidimeter

Hot
Vacuum
plate Air
oven
oven Karl
Fisher
Moisture analysis
1) Hot plate method
 useful for a rapid preliminary screening.
 applicable to all the ordinary oils and fats. It
also applicable to solvent extracted oils and
fats, which may contain residues from solvents
with fairly high boiling points.
 Procedures:
 10 g sample heated in beaker with gentle
agitation on hot plate until smoking begins
 Moisture and volatile matter = The loss in
weight between the beginning and the ending
sample
Moisture analysis
2) Air oven method
 accurate, more reliable than hot plate
 applicable to all the ordinary oils and fats
which have a relatively low moisture
content (below one percent), but not to
drying or semi-drying oils or oils of the
coconut oil group.
 time consuming
Moisture analysis
2) Air oven method
 Procedures:
 approximately 5 grams of a representative
sample is weighed into a dried, tared moisture
dish and dried in the oven for 30 minutes at
101°C (± 1°C).
 This
procedure is repeated until a constant
weight is determined
 Theloss in weight is calculated as the moisture
and volatile matter
Moisture analysis

3) Vacuum oven method

 vacuum method no to exceed 100 mm of

Hg at temperature 20 – 25 deg above b.p
of water at the operating pressure until
constant weight is obtained in successive
1h drying periods.
Moisture analysis
4) Karl Fischer method
 It is based on the Bunsen reaction
between iodine and sulphur dioxide in
an aqueous medium
Moisture analysis
4) Karl Fischer method

The amount of
iodine consumed is
equivalent to the
amount of water
present in the
sample.
Impurities analysis

 Foreign material in incoming crude edible oils

must be removed to produce an acceptable
finished product

 Methods to remove impurities:

 insoluble impurities
 filterable impurities
 turbidimeter impurities
Impurities analysis

1) Insoluble impurities
• Dirt, seed fragments and etc
insoluble in kerosene or
petroleum ether
• Utilizes the residue from the
moisture and volatile matter
determination
• After wash with warm
kerosene, the crucible is dried
and weighed
Impurities analysis
2) Filterable impurities

 During processing, undissolved impurities

might be present such as salt which
formed after the reaction
 Methods: filter a standard quantity (500
g) of heated (70 – 90 deg.) oil sample with
vacuum suction funnel through Whatman
No. 2 filter disc.
Impurities analysis
3) Turbidimeter impurities

 Amount of undissolved impurities in oil

can be determined using this method
 method: sample will be poured into
prescribed sample bottle to eliminate
air bubbles. Then the sample will be
heated to 70oC and allowed to stand at
5 – 10 mins in controlled temp. oven
Impurities analysis
3) Turbidimeter impurities cont.
 The turbidimeter readings can be
converted to ppm of impurities
using a calibration curve
 Not suitable for meat fats and
products containing emulsifiers –
contain impurities that cannot be
effectively measured by this
method
Trace Metals Analysis
 Metals in oils and fats can reduce the
efficiency of the process and cause the
deterioration of the product quality

 Most prevalent metals found: copper, iron,

calcium, magnesium, sodium, lead, zinc, and
nickel

 Can be traced by analysis using AAS (Atomic

Absorption Spectroscopy) & ICP (Inductive
Coupled Plasma)
 Soap analysis
 In caustic refining, NaOH is added into the oil to
react with free fatty acid and produce soaps

 Traces of soap in oil after refining and bleaching

could poison hydrogenation catalyst. It also can
shorten the frying life of shortening.

 2 methods available for determining soaps:

- Conductivity procedure (Cc 15-60)
- Titration procedure (Cc 17-79)
MELTING, SOLIDIFICATION AND
CONSISTENCY
 Most frequently and routinely analysis
performed

 Helps with quality control and product

development – good indications of the mouth
feel, overall general behaviour at cool, ambient
and elevated temperature
Melting point analysis

 Natural fats do not have true

melting points

 Melting range or melting interval

is most appropriate terms

 Several melting point procedures

have been standardized by AOCS
 Melting point analysis
1) Capillary melting point
 Similar with procedure used to
determine the melting point of
pure organic compound
 Capillary tube is filled with
melted sample and tempered at
4-10°C. Then, it is heated until
the fat become clear.
Melting point analysis
2) Wiley melting point:
 A fat disk is solidified and chilled in a metal
form for two hours or more.
 The disk is then suspended in an alcohol–
water bath and slowly heated while being
stirred with a rotating thermometer.
 The Wiley melting point occurs when the fat
disk becomes completely spherical.
Melting point analysis
3) Dripping point
 Method: 17 drops of melted fats will be
put in the sample cup and put in a
freezer for 15 mins
 Cold solidified sample warm in a furnace
until it becomes fluid enough to flow
 When the sample flow, it trips a
photoelectric circuit that records the
temperature on digital read out.
 Melting point analysis
 Advantages:
 had become a standard in most
fats and oil laboratory
 fast, reliable result
 good correlation with Wiley
result
 ability
to analyse products with
low melting points
 Solidification Analysis
 Solidification of mixed fatty acids: point where a
balance is attained between the heat generated
and heat lost, which will vary according to rate of
crystallization.

 Types of evaluation:
Solidification
Analysis

Titer test Cloud point Cold test

Solidification Analysis

1) Titer test:
 measure the solidification point of fatty
acid
 For edible oils and fats, commonly
specified for low iodine values hard fat
refers to as titer stocks
 For inedible fats, used for soap making or
as a raw material for fatty acid
manufacture
Solidification Analysis
2) Cold test:
 the ability of an oil to resist
crystallization by determining the time
(in hours) required for the oil to become
cloudy at 0°C (32°F).
 Method: dry filtered oil is placed in a
sealed 4-ounce bottle and submerge into
an ice bath.
If the oil remains clear for 5.5 h, the oil
pass the cold test.
 Solidification Analysis
3) Cloud point:

 is obtained by stirring a sample of fat while

it is being cooled until the oil has clouded
enough to block a light beam of known
intensity.
Consistency Analysis
 Consistency: impression of resistance in terms
of plasticity

 It depends on the portion of solid phase and

crystal size.

 Fat become firmer as the solid content

increases and crystal size reduced

 Butter and margarine depends upon the

consistency of fat portion and its ability to
spread on bread
Consistency Analysis

o Consistency rating

 pressing a finger into the product/

squeeze the product in the hand

 Still applicable and effective

 required an experienced evaluator

 Consistency Analysis
o Penetration
 Widely used method to measure the
consistency of plasticized shortening
or margarine
 measure the depth to which the cone
penetrates into the surface of the
shortening or margarine after
allowing the cone to settle into the
product
 The samples are evaluated to
determine the relative softness at low
temperature and firmness at high
temperature.
 Products with a wide plastic range are
workable at both high and low
temperatures
 COMPOSITION ANALYSIS
 Usually done by using wet chemical analysis (classical
method)
Saponification
value

Antioxidant Iodine
analysis value

Composition
analysis

Tocopherol refractive
analysis index
 Saponification value
 Measure the alkali-reactive groups in fats and
oils

 Useful in predicting type of glycerides – it is a

measure of the average Molecular Weight (or
chain length) of all the fatty acids

 Glyceride with short-chain fatty acid have

higher saponification values than long-chain
fatty acid
 Saponification value
Saponification - hydrolysis of ester under
alkaline condition.

Example: vegetable oils and animal fats has

same range of saponification value: 180 -
200
Composition analysis
 Iodine value
 Measure degree of unsaturation in
oil.
 It is inversely related to titre.
 Hard fats with a high percentage of
saturation will have low iodine
values and a high titre
Composition analysis
 Refractive index
 a basic value that relates to molecular
weight, fatty acid, chain length, degree of
unsaturation, and degree of conjugation
 used as a rapid control for the
determination of the product endpoint for
hydrogenation reactions.
 A refractometer with temperature control
at 25 deg. is used
 A refractive index decrease with no. of
double bonds present in fatty acids
 Composition analysis
 Triglyceride structure
 HPLC procedures used to determine
relative amounts of glycerides present in a
fat
O
O
H2 C O C R
H2 C OH HO C R O
O
HC OH + HC O C R + 3 H2O
HO C R O
H2 C OH O
HO C R H2 C O C R

Glycerol 3 Fatty Acids

Antioxidant analysis

 Antioxidants are widely used in fats and oils

products to delay decomposition processes
that result in offensive flavors.

 To measure the amount of synthetic

antioxidant (butylated hydroxyanisole (BHA),
butylated hydroxytoluene (BHT) used in fat
and oil products.

 Use GC or HPLC for quantitative analysis

which require less than an hour to provide
accurate and reproducible results.
Tocopherol analysis
 Vegetable oils contain tocopherols, which
are natural antioxidants that retard
oxidative rancidity.
 high proportions of the tocopherols
provide optimum oxidation stability.
 The instrumentation and procedures
evaluated have involved calorimeters,
paper chromatography (PC), column
chromatography (CC), GLC, GLC/mass
spectrometry (GLC/MS), and HPLC
separation techniques
FLAVOR, RANCIDITY AND STABILITY

 Customer use organoleptic evaluations to

judge the quality of fat and oil

 Organoleptic:
 evaluation of oil products has long been
recognized as the most sensitive method
of assessing quality, but it is also
recognized that these evaluations
generally lack precision and
reproducibility
Flavor analysis
Sensory evaluations
 most common method of grading
finished oil quality

 Experienced taster/ flavorist rate the

flavor of the oil according to
established intensity scale.

 time consuming, expensive

Flavor analysis

Sensory evaluations
 Rancidity analysis
 The sharp pungent odours mixed with stale and
musty odours (unpleasant smell)

 The major cause of rancidification of oil and

fats are:
1) Oxidation
2) Hydrolysis

 Factors that contribute to the rancifidication

and formation of off-flavor are temperature,
light, moisture, metals and oxygen.
Rancidity
 Hydrolytic Rancidity.
Hydrolytic rancidity results in the formation of free
fatty acids and soaps (salts of free fatty acids) and is
caused by either the reaction of lipid and water in
the presence of a catalyst or by the action of lipase
enzymes.

 Oxidative Rancidity.
Oxidative rancidity results from more complex lipid
oxidation processes which involve free radical
reactions.
 Rancidity

 Analysis to measure:
a) Peroxide value
b) Anisidine value
c) Free fatty acid and acid value
Rancidity
1) Peroxide Value

• measures the concentration of substances

that oxidize potassium iodide to iodine.

• PV of 1.0 or less indicates freshness;

1 to 5 PV, low oxidation;
5 to 10 PV, moderate oxidation;
>10 PV, high oxidation;
>20 PV, poor flavor.
 Rancidity
• Oxidation of lipids is a major cause of
their deterioration.

• Hydroperoxides formed by the reaction

between oxygen and the unsaturated fatty
acids are the primary products of this
reaction.

• Hydroperoxides have no flavor or odour

but break down rapidly to form
aldehydes, which have a strong,
disagreeable flavour and odour
Rancidity
 Rancidity

2) Anisidine value
• The anisidine value measures the amount of
α and β unsaturated aldehyde present in the
oil.
• The method is based on presence of acetic
acid, p-anisidine reacts with aldehydic
compound in an oil, producing yellowish
reaction products.
• The color intensity depends on the amount
of aldehydic compound present.
Rancidity
3) Acid Value
• The flavors resulting from FFA developed
depend on composition of fat thus,
rancidity analysis can be measure by FFA
• Number of mgs of KOH required to
neutralize the Free Fatty Acids in 1 g of
fat.

ml of KOH x N x 56
AV = = mg of KOH
Weight of Sample
Stability analysis
 Stability of a fat or oil generally accepted as the
storage life of the product until rancidity become
apparent
 Most fats and oil products are tested for flavor
stability as a part of quality control program to
ensure customer specification limits are satisfied
 Types of method to evaluate stability
o Active Oxygen Method
o Oil stability index
o Schaal oven test
COLOR AND APPEARANCE
Color and appearance relate to the cost of
processing and quality of finished product

Some crude oil can have unexpectedly high

pigmentation cause by field damage,
improper storage, faulty handling during
crushing and extraction

During processing, product appearances may

be an indicator of a problem
Color analysis
1) Wesson color method
2) Lovibond (British Standard)
3) Spectrophotometric color method for oil
4) Automatic Tintometers
5) FAC (Fatty Acid Committee) method
6) Gardner color
7) Chlorophyll
8) Coloring agents determination
REFINING AND BLEACHING
 Purposes of refining and bleaching analysis:
As a basis for settlement of crude contracts
under the trading rules of the various oil
trading associations
As a yardstick for the efficiency of the
refining and bleaching operations
As indicator for caustic and bleaching
earths types and levels for processing
Most crude vegetable oils are traded on the
basis of refining loss or neutral oil, refined or
bleached color, and flavor.
REFINING AND BLEACHING
 Refining loss
 The loss of free fatty acids, oil and
impurities when the sample is treated
with alkali solutions under specific
conditions of the test
 The refining loss is calculated by
subtracting the refined oil sample
weight from the original crude oil
sample weight
REFINING AND BLEACHING

 Neutral oil and loss

 Extracts the oil or fatty materials on a
column of activated alumina by ether-
methanol.
 The mixture extracted consists
primarily of triglyceride and
unsaponifible material.
REFINING AND BLEACHING
 Bleaching analysis
 Technique involves the addition of a
bleaching earth or carbon or both to
refined oil, heating it to 120 oC and
hold at that temperature for 5 min
while agitating at 250 rpm
 Then the earth removed by filtration
filtration and the oil color is
determined
PERFORMANCE TESTING
Performance testing is essential for the
development of new product especially
for fat and oils products designed for a
specific food product, formulation or
process
Most performance testing was design for
bakery products, baking, frying, candy,
coating, formulated foods, nondairy
product, shortening and margarines
Most common performance evaluations
are:
 Creaming volume
 Pound cake test
 Icing volume
 White layer cakes
 Crème filling test
 Cake mix evaluation
 Puff pastry testing
 Restaurant deep-fat frying evaluation
 Ice cream bar coating evaluation