Chapter 7

• To define the needs of analysis

 Example:
• The technician used qualitative analysis to determine
that the solution contained Cu2+ and Cl- ions.
 Definition :
• The determination of how much of a given component
is present in a sample.

 Example :
• The technician used quantitative analysis to find that
the ore contained 42.88% silver by mass.
Qualitative Analysis tells 'what' is in a
sample, while Quantitative Analysis
is used to tell 'how much' is in a
sample.
  This analysis shows important for:
• Purchasing raw material
• Development of new products
• Evaluation of the product produced.
Analysis
Hierarchy
 Impurities must be removed during processing
to prevent an adverse reaction or an
undesirable appearance.
 Any trading of goods have specific limit.
 Presence in the oils or fats during processing,
condensation, broken coils, and etc
 Continued present induced hydrolysis, FFA
increase & off flavors
 Methods:
1. Hot plate method
 10 grams-15 grams heated in beaker with gentle agitation on
hot plate until foaming stops and incipient smoking begins.
 The loss in weight between beginning and ending sample
represent the moisture
2. Air oven method:
 the similar method as above only the difference at heating
medium using oven
 More accurate and reliable
3. Vacuum oven method:
 also similar with 2 method above only done in vacuum below
100 mmHg operating pressure or above 25-30º C H 2O boiling
point.
4. Karl Fisher method:
 Using visual titration method (vt) or electrometric titration (et)
method. Color change from yellow to brown( vt). And yellow
to dark solution more practical and precise (et)
5. Skillet (frying pan) moisture:
 Qualitative method. Popping, spitting or reaction indicates
presence of moisture.(assignment)
 Foreign material in incoming crude edible oil
during processing must be removed to produce
an acceptable finished product.
 Methods:
1. Insoluble impurities:
o Dissolved in 50 ml of kerosene, vacuum filter through Gooch crucible
and wash either used petroleum ether or kerosene, dried and get final
weight.
2. Filterable impurities( standard disc method):
o using 500 grams of heated sample 70 C to 90 C and filtered through
vacuum funnel using Whatmann No2 filter paper. Make comparison
between standard and current filtrate.
3. Turbidimeter impurities:
o amount of undissolved impurities in oil can be determined. Sample
heated 70º ± 1.0 ºC and detain at least 5- 10 minutes to avoid bubble.
Data can be determined in ppm. Can’t used for meat fats and products
containing emulsifiers because above the spec.
 During processing or transportation, metals can
be encountered
 Reduce efficiency of the process or cause
deterioration of the quality
 Most element such as copper, iron, calcium,
magnesium, sodium lead, zinc and nickel.
 Using AAS or ICPMS recently. Previously is
chemical titration.
 Non Fatty Impurities
(Trace Metals Analysis)
 Caustic refining introduce NaOH in oil to react
with FFA and produce soap.
 Traces of remaining soap (unwanted substance)
after treatment are necessary to avoid
deterioration/poison of hydrogenation catalysts &
oxidative stability.
 2 AOCS (American Oil Chemists’ Society)
methods:
• Conductivity method
• Titration method
 Data used to predict consistency final product
such as formulation, freeze point and etc
 Melting and solidification are the common lab
test performed.
 Melting point analysis defined as a point of temp when
material changes from solid to liquid.
 Natural fats do not have a true melting points.
 Pure components have sharp and accurate melting point
 Fats and oils have complex mixtures of compounds
gone trough softening process removing hardness and
metals before become liquid.
 Melting procedure was complicated and crystals can
exist in several polymorphic modification
 The different crystal forms are often stable enough to
exhibit distinctive melting point. Infect the definition
of melting range and melting interval can be used.
 Only with ridge(and specific definition of fat treatment
& test procedure can be determined a melting point.
 Methods:
 Capillary melting point: A capillary tube(Ø 1 mm) filled
10mm with melted fat. The end is sealed and tempered
almost 16 hours at 4º C
 Softening point: open capillary tube point similar with above
only tube is not seal. The endpoint should be the physical
movement of the fat column under standard hydrostatic
pressure.
 Slipping Point: similar with softening method except sample
put in metal tube with heated at rate 0.5º C/minute while
immersed in brine solution 600 ml. End point when
temperature of fat rises from the cylinder
 Methods:
• Wiley melting point: using rotating solidified disc in
suspended water –alcohol bath & slowly heated while
being stirred with rotating thermometer. The end point
occurs when the fat disc become completely spherical.
• Mettler Droping Point: utilize Mettler instrument.
 Proportion of solid and liquid fat in margarine,
spread or specialty product at given
temperature has an important relation with
product performance at that particular
temperature. For example margarine at room
temperature
 This proportion can’t be determined from
single point melting analysis but through
calculation of oils & fats contents in a fat
different temperature
 This method uses: calorimetric, dilatometric
or Nuclear Magnetic Resonance (NMR).
 Usual temperature uses in analysis are:
• 10.0º C, 21.1º C, 26.7º C, 37.8º C and 40º C
 SFI or Solid fat index or dilatometric method
determination at different temperature covering
the range over which a fat passes from solid to
liquid. Can be plotted in the graph:
 Information from graph:
• Plastic range; Fats and oils products generally have the best
consistency for mixing & working within solid content
range from15 to 25% which usually identified as the plastic
range.
• Melting point; The dilatometric melting point is the
temperature at which the solids curve meets the liquid line,
that is the lowest temperature at which the solid contents is
zero. The melting point is obtained by extrapolating the
solids curve to zero either graphically or mathematically.
 The graph will show:
• Flat Solids Curve; Flatter solids slopes generally have a
greater plastic range because the solids remain within
the plastic range for a wider temperature range
• Steep solid curve; Sharp melting properties usually
accompanied by a high oxidative stability and
characterized by a steep solids slope. Eg: frying oil,
cookie filler, nondairy application. These products
require sharp melting profile and good flavor stability.
 Three methods to test Solid Liquid Content:
• Solid Fat Index
• Solid Fat Content
• Differential Scanning Calorimetry Fat Solids Content.
 It is an empirical measure of the solid fat
content.
 Calculated at various temperatures at the
specific volume utilizing a dilatometric scale
measured in units of milliliters times 1000.
 Arbitrary approach and lot of assumption
 Quantity of solid glycerides in a fat by
measuring the pulse NMR signal of the liquid
fat.
 Hydrogen atom in solid doesn’t give signal but
hydrogen atom in liquid does.
 SFI & NMR analysis may be correlated but no
identical result provided.
• SFI-empirical measure;
• NMR- direct measure
 Using heat of fusion(heat of melting): specific
enthalpy difference between the solid and
liquid forms of species at T & P
 Partial area under melting curve considered as
measurement(temperature)
 It is a point which a balance is achieve between heat
generated and heat lost which vary to the rate of
crystallization and degree of supercooling in the liquid.
 Methods of testing:
• Titer
• Quick titer
• Congeal point
• Cloud point
• Cold test
 Consistency is generally assumed to be a
combination of those effects that tend to give
the impression of resistance.
 Plasticity relates to the capacity of the product
to be molded.
 The factor most directly influencing the
consistency of a fat is the proportion of the
material in the solid phase.
 A fat become firmer as the solids content
increases.
 The smaller the crystals, the firmer the fat.
 Critical performance factors of fats and oils are
related to consistency and plasticity.
 The quality of butter, margarine and spread
depends upon the consistency of the fat portion
and its ability to spread on bread.
 A wide plastic range and a smooth consistency are
mandatory for roll in shortenings and margarines
used for thin layer lamination at refrigerator
temperatures
 Plasticity also important for the workability
and creaming properties required for
shortenings used in the preparation of icings
and aerated batters.
 Two measures are used:
• Consistency ratings
• Penetrations
 Important because :
• Fatty acid contents
• Pattern of glyceride distribution elaborated by plants
and animals
• Physical character
• End use performance
 Involved with:
• Chemical
• Instrument analysis
 Saponification value is number of miligramms of
potassium hydroxide required to
saponify(hydrolyze) 1g of fat and related to the
molecular mass of the fat.
 Measure alkali reactive group in fats or oils & can
be used to predict type of glycerides
 Glycerides contains shorter fatty acids that have
higher saponification value than longer chain fatty
acid to.
 Screening tools for types of oils and fats
 Systematic name Trivial name Shorthand Molecular wt. Melting point (°C)
designation
butanoic butyric 4:0 88.1 -7.9
pentanoic valeric 5:0    
hexanoic caproic 6:0 116.1 -3.4
octanoic caprylic 8:0 144.2 16.7
nonanoic pelargonic 9:0 158.2  
decanoic capric 10:0 172.3 31.6
dodecanoic lauric 12:0 200.3 44.2
tetradecanoic myristic 14:0 228.4 53.9
hexadecanoic palmitic 16:0 256.4 63.1
heptadecanoic margaric (daturic) 17:0 270.4 61.3
octadecanoic stearic 18:0 284.4 69.6
eicosanoic arachidic 20:0 412.5 75.3
docosanoic behenic 22:0 340.5 79.9
tetracosanoic lignoceric 24:0 368.6 84.2
hexacosanoic cerotic 26:0 396.7  
heptacosanoic carboceric 27:0 410.7  
octacosanoic montanic 28:0 424.8  
triacontanoic melissic 30:0 452.9  
dotriacontanoic lacceroic 32:0 481  
 No. of No.of Melting
Systematic Name Common Name Double Bonds Carbon Point C
Atoms
9-Decenoic Caproleic 1 10 -
9-Dodecenoic Lauroleic 1 12 -
9-Tetradecenoic Myristoleic 1 14 18.5
9-Hexadecenoic Palmitoleic 1 16 -
9-Octadecenoic Oleic 1 18 16.3
9-Octadecenoic* Elaidic 1 18 43.7
11-Octadecenoic* Vaccenic 1 18 44
9,12-Octadecadienoic Linoleic 2 18 -6.5
9,12,15-Octadecatrienoic Linolenic 3 18 -12.8

9-Eicosenoic Gadoleic 1 20 -
5,8,11,14- Arachidonic 4 20 -49.5
Eicosatetraenoic
5,8,11,14,17- - 5 20 -
Eicosapentaenoic
13-Docosenoic Erucic 1 22 33.4
4,7,10,13,16, - 6 22 -
19-Docosahexaenoic
 Iodine value is denote % by weight of iodine
bound by 100 g of fat & approximate to measure
degree of unsaturated.
 Usual method used Wijs reagent & potassium
iodide to convert to equal iodine and titrate with
thiosulfate reagent and starch indicator until blue
color appear.
 The rate of addition of iodine to double bonds
depends on their distance from the carboxyl group
Conjugated double bonds Non- conjugated double
bonds
 Replace most conventional method by using
GLC
 Advantages:
• permits identification of source oils that cannot be
identified by the classical methods
• Ability to identify the source oil proportions in a
blended product
• Can be made rapidly
 GLC/GC detector: Flame Ionization Detector
 Carrier gas: helium and nitrogen]
 Detection for:
• Saturated fatty acid
• Monounsaturated fatty acid
• Poly unsaturated fatty acid
 Refractive Index is used to Measure changes in unsaturated oil
or when oil is hydrogenated.
 The index of refraction is the degree of deflection of a beam of
light that occurs when it passes from the one transparent
medium to another
 Measurement usually at 25 ºC. For high melting fats required
40 to 25 ºC depending upon the melting point.
 RI ↓ temperature ↑ and ↑ the carbon chain length with double
bonds.
 Oil and Fat RI
Palm Oil 1.453-1.456
Palm Kernel Oil 1.453-1.456
Coconut Oil 1.448-1.450
Olive oil 1.467-1.471
Soybean Oil 1.470-1.478
Corn Oil 1.474-1.476
Sesame Oil 1.473-1.476
 Determination of monoglycerides & free
glycerin in fats
 Based on quantitative oxidation with periodic
acid (α-monoglycerides)
 Replace with latest analytical instrument such
as TLC, GLC or HPLC
 This method applicable for others emulsifiers
such as acetylated monoglycderides and
Propylene glycol ester
 Normally use to delay decomposition processes that results in
offensive flavor
 Several phenolic compound that inhibit oxidation of fats by
interrupt free radical mechanism of oxidation.
 Mostly are synthetic anti oxidants such as propyl gallate(PG),
butylated hydroxyanisole(BHA), butylated
hydrotoulene(BHT), tertiary butylhydroquinone(TBHQ)
 FDA allows only 200ppm as max. level in food.
 Qualitative or quantitative measurement.
 Natural antioxidant that stop oxidative rancidity. Act as
free radical chain breaking antioxidants.
 Tocopherol decrease during processing especially
during deodorization. (more volatile)
 Calorimeter, paper chromatography, TLC, column
chromatography, GLC, GLCMS, HPLC
 Sensory evaluation
• Taste assessment is the ultimate method of grading
finished oil quality.
• To determine oil flavor, 5 to 10 mililiters of oil is taken
into mouth, thoroughly swished throughout the mouth
with air drawn over the top and expectorated into a
waste cup.
• A panel of experienced tasters rates the flavor of the oil
according to an established intensity scale.
 Peroxide value
• Oxidation of lipids major cause of deterioration
• Miliequivalents of active oxygen per 1000g of fat
which oxidized potassium iodide to iodine. It also can
be in milimoles per kilogram.
• It shows good correlation with organoleptic flavor
score
• High PV usually shows poor flavor ratings and vice
versa.
 Anisidine value
• Measure amount of α and β unsaturated aldehydes
present in the oil.
• Based on fact that presence of acetic acid, p-anisidine
react with the aldehydic compounds in oil,producing
yellowish color
• 1000 times the absoprtion of a 1%sample solution in a
1-cm cell after reaction with anisidine.
 Color and appearance are important due to
• the cost of processing
• quality of the finished product
• what the products look like to the end user
 The color is due to the presence of carotenoid
pigments or chlorophyll pigments
 Changes in appearance of finished products are
perceived as indicating poor quality product
 Methods:
• Lovibond
• Spectrophotometric Color Method
• Wesson color method