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The Analytical Process

1) Selecting a method
2) Sampling
3) Preparing the laboratory sample
4) Defining replicate samples
5) Preparing of solutions of samples
6) Eliminating interferences
7) Measurement of analyte concentration
8) Calculations
9) Determining reliability of data
Selecting the method

Method used must be fit for the purpose


> Ex. databank of trends, quality assurance, goods assessment,
forensics
Source of methods:
1. In-house method
2. Methods published in open scientific lit
3. Methods supplied by trade organizations
4. Methods in books published by professional organizations (Ex.
Royal Academy of Chemistry)
5. Methods from standards organizations (Ex. US-EPA)
6. Methods from statutory organizations
Factors to consider in choosing a method:
1. Limit of detection
Important for trace analysis
Should ideally be at least 1/10th of the concentration to be
measured
Ex. legal limit of Pb in tap water is 50 ppb, therefore
analytical limit of detection should be 5 ppb
2. Accuracy
Very often NOT important in trace analysis
3. Precision
4. Speed to minimize effort and cost
5. Equipment required
6. Sample size
Especially in clinical chemistry and forensics
Ex. blood samples
Linked to limit of detection
7. Cost
8. Safety
9. Specificity degree of discrimination between analyte and other
substances present or extracted from the matrix

Making your choice: Will the method selected be adequate for the
decision you have to take when the result is available?

Sampling

Process of selecting a portion of material, in some manner, to represent or


provide information about a larger body of material
Types of samples
1. Representative sample sample that is typical of parent material for
the characteristic under inspection
must take into account the state of the parent material:
a) homogeneous Ex. vegetable oil at 40oC, filtered aqueous
solution
b) heterogeneous Ex. palm oil at 15oC, muesli breakfast cereal
c) static system composition of material is permanent wrt
position in space and stable in time
Ex. sample of oil in a drum, warehouse stock of food
d) dynamic conditions parent material is changing with time;
removal of portion at any instant represents only a snapshot
of that moment in time and in that particular location
Ex. estuarine or riverine water
2. Selective sample sample deliberately chosen by using a sampling
plan that screens out materials with certain characteristics and/or
selects only material with other relevant characteristics; directed or
focused sampling
Ex. suspected contamination of sample due to rat feces
3. Random sample sample selected by a random process to eliminate
questions of bias in selection and/or to provide a basis for statistical
interpretation of measurement data
Types:
a) simple random sampling any sample has an equal chance
of selection
Ex. raffle draw
b) stratified random sampling lot is subdivided/stratified and
a simple random sample is selected from each stratum Ex.
regional raffle draws
c) systematic sampling first sample is selected at random
then the subsequent samples are taken according to a
previously arranged interval (every 5th, 10th, etc.)
Ex. take every 50th bottle in a production line for quality
control analysis
4. Composite sample consists of 2 or more portions of material
(collected at the same time) selected so as to represent the material
being investigated
ratio of components taken to make up composite can be in
terms of bulk, time or flow

components of the composite sample are taken in proportion to


the amount of the material they represent Ex. food samples
may be bulked together in proportion to the amount normally
consumed
Preparing the laboratory sample
Crushing and grinding of lab samples

required to decrease the particle size of solid samples


tend to alter composition of sample, hence particle size should be
reduced no more than is required for homogeneity and ready attack
by reagents
factors that can cause appreciable changes in samples composition
as a result of grinding:
heat can generate loss of volatile components
increase in surface area increases susceptibility to reaction
with atmosphere Ex. Fe content of rx can decrease by as much
as 40% during grinding
water content altered substantially during grinding
differences in hardness of the component softer components
ground to fine particles more easily and be lost as dust
intermittent screening often increases efficiency of grinding
tools employed:
large samples with large lumps: jaw crushers, disk puverizers
medium-size samples and particles: ball mills useful device for
grinding of solids that are not too hard
small materials: mortars
> Plattner diamond mortar used for crushing hard, brittle
materials

Mixing Solid Lab Samples

essential to ensure a random distribution of the components in the


analytical samples
common method: rolling sample on a sheet of glazed paper
others: rotating sample for some time in a ball mill or a twin-shell Vblender
Note: long standing, finely ground homogeneous materials may
segregate on the basis of particle size and density

Types of Moisture in Samples


Essential water part of the chemical identity of the sample; present in
stoichiometric amounts
o Water of crystallization/hydration
Ex. BaCl2 2H2O

o Water of constitution
present as H and OH groups which combine to give
H2O
takes higher T to expel from samples
Ex. C6H12O6 6C + 6H2O
Non-essential water superficially held water or water bound to the
sample physically and removed at a much lower T range (100-120oC)
o Adsorbed water retained on surface of solid
o Sorbed water condensed water in interstices of capillaries of
colloidal solids
o Occluded water liquid water entrapped in microscopic pockets
spaced irregularly throughout solid crystals

Common Practices
1) remove moisture from samples prior to weighing or to bring water content
to some reproducible level
2) determine water content at the time samples are weighed for analysis so
that results can be corrected to a dry basis
Example: A food sample analyzed as received, is found to contain 14.57%
protein and 10.4% water. Calculate % protein on a dry basis.
Example: 1.000 gram of soil as received, gave a moisture content of 14.0%.
The oven-dried sample, completely moisture-free, showed 18.00% K. Find
the % K in the sample as received.
Methods of Moisture Determination
1) Application of Heat
a. Drying done to make sample anhydrous or to remove adsorbed
moisture but retain chemically combined water
i. Air-drying
ii. Oven-drying
1. conventional oven
2. vacuum oven 50-100 mm Hg
3. microwave oven
iii. Dessicator
iv. IR lamps
Disadvantages of drying:

Procedure not specific for water

Large (+) systematic errors in samples that yield volatile


decomposition products upon heating

Time-consuming
b. Freeze-drying or lyophilization

For biological materials and unstable natural products


Water from frozen sample is evaporated in a high vacuum
system, T kept below 0oC
Nearly dry sample further dried at high T in order to attain a
minimum weight in the shortest possible time

c. Distillation with a high boiling liquid immiscible with water


Total vapor pressure above a binary system of immiscible
liquids = sum of vapor pressure of the 2 liquids
Two liquids boil and distill over a lower T than they would if they
were not in a mixture
Common carrier liquids: toluene, o-xylene, m-xylene, p-xylene
2) Chemical Methods: Karl Fischer Titration
KF Reagent:
o Solution A: pyridine, methanol, SO2 + sample
o Solution B: I2 in methanol (titrant)
Reactions:
C5H5NI2+C5H5NSO2+C3H5N+H2O2C5H5NHI+C5H5NSO3
C5H5NSO3 + CH3OH C5H5N(H)SO4CH3
important because C5H5NSO3 is also capable of consuming water
C5H5NSO3+ H2O C5H5NHSO4H
undesirable because not specific for water; prevented by excess CH 3OH
Endpoint:
o yellow light reddish brown color of excess I2
o may also be determined using electrometric methods
Interferences: compounds that react with one of the
components of the reagent to produce water
o carbonyl compounds (RCHO)
o metal oxides react with HI
o oxidizing or reducing substances that reoxidizes iodide
produced or reduces I2 in the reagent
Preparing of solutions of samples: Decomposing and Dissolving the
Sample
Sources of error:

Incomplete dissolution of analytes ideal sample treatment


should dissolve sample completely
Losses of analyte by volatilization
Introduction of analyte as a solvent contaminant
Introduction of contaminants from reaction of the solvent with
the vessel walls

Decomposing Samples by Inorganic Acids in Open Vessels


Most common reageant: mineral acids

Hydrochloric acid excellent for inorganic samples but finds


limited application for decomposing organic materials;
widespread use for dissolving many metal oxides and metals
more easily oxidized than hydrogen

Nitric acid strong oxidant that dissolves all common metals


except Al and Cr; alone or in combination with other acids and
oxidizing agents, widely used for decomposing organic samples
(wet ashing)

Sulfuric acid many materials are decomposed and dissolved


by hot, concentrated sulfuric acid; effectiveness due to its high
boiling point

Perchloric acid attacks a number of iron alloys and stainless


steel that are intractable to other mineral acids; problem:
explosive when hot, concentrated perchloric acid comes in
contact with organic materials or easily oxidized inorganic
substances

Oxidizing mixtures
Aqua regia 3:1 mixture of HCl:HNO3
Br2 or H2O2 hasten oxidation of organic materials
HNO3 + HClO4 useful also for organics
Hydrofluoric acid primary use is for decomposition of silicate
rocks and minerals in the determination of species other than
silica

Microwave Decompositions

May be carried out in open or closed vessels, but the latter is


preferred since higher temperatures are realized because of the
higher pressures.
Evaporative losses are also avoided. Less reagents required,
less risk of interferences due to contamination.
Loss of volatile components of sample avoided.
Easy to automate. Main advantage: speed
Vessels for moderate-pressure digestions
High-pressure microwave vessels designed to operate
at 80 atm or 10 times the pressure that can be tolerated
by moderate-pressure vessels
Microwave ovens designed to heat simultaneously 12
of the moderate-pressure vessels
Microwave furnaces for performing fusions and for dry
ashing samples containing large amounts of organic
materials; temperatures of 1000oC reached in 2 minutes!

Elimination of Interferences
Interference arises whenever a species in the sample matrix either
produces a signal that is indistinguishable from that of the analyte or,
alternatively, attenuates the analyte signal
2 Methods:
1) use of a masking agent immobilizes or chemically binds the
interfering species in a form in which it no longer contributes to or
attenuates the signal from the analyte
> Ex. use of F- to prevent Fe3+ from interfering in the iodometric
determination of Cu2+
2) Converting either the analyte or the interferences into a separate
phase that can be separated mechanically
> Most common method: chromatography
> Others: precipitation, extraction, ion-exchange, distillation

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