STEPS IN A QUANTITATIVE ANALYSIS

Define the Problem

Select a Method
Select a method
Sample Preparation Sampling
Eliminate
Interferences
Calculate the Results
and Report Writing
Perform the
Measurement
DEFINITION OF THE PROBLEM
To determine the best method of analysis
the analyst should ask the following questions.
SELECT A METHOD
Factors to consider include:
Accuracy
Detection limit
Time
Cost/number of analyses
Complexity of sample - selectivity
Equipment
Technical expertise
LIST OF JOURNALS
Analytical Chimica Acta
Analytical Abstracts
Journal of Analytical Chemistry
Analytical Communications
Analyst
Journal of the Association of Official Analytical
Chemists
Journal of Chromatography
Journal of Chromatographic Science
Talanta
Trends in Analytical Chemistry
LIST OF BOOKS
SELECTING AN ANALYTICAL METHOD
Performance Characteristics
Criteria used to compare which of several
instrumental methods would be the best for a
particular analysis.
e.g. Limit of Detection.
Figures of Merit
Quantitative (numerical) measures of
performance characteristics.
e.g. LOD of Pb (AAS) = 15 ppb
LOD COMPARISON
(g/L) / ppb
VALIDATION OF ANALYTICAL METHOD
(METHOD VALIDATION)
Analysis of Standard Samples (SRM)
Analysis by Other Methods
Standard Addition to the Sample
VALIDATION OF ANALYTICAL
METHOD
Analysis of Standard Samples
- A sample whose analyte concentration is
known.
- The standard reference material (SRM)
can be obtained from The National Institute
Of Standard and Technology (NIST).
- The analyte concentration in the SRM
has been certified by the institute.
- Compare the data obtained from the
method with the certified value.
Analysis by Other Methods
- The result of the analytical method can be
evaluated by comparison with data obtained
from a different method.
Standard Addition to the Sample
- The known amount of the analyte is added
to the sample and then analyzed by the
proposed method. The effectiveness of the
method can be established by evaluating
the recovery of the added quantity.
- The standard addition method will reveal
errors arising from the way the sample was
treated or from the presence of the other
compounds in the matrix.
SAMPLING
Sampling is the process to get a
representative and homogeneous sample.
Representative means that content of
analytical sample reflects content of bulk
sample.
Homogeneous means that the analytical
sample has the same content throughout.
OBTAIN A SAMPLE DEPEND ON
The size of the bulk to be sampled.
The physical state of the fraction to be
analyzed (solid, liquid, gas)
The chemistry of the material to be assayed.
(Nothing can be done that would destroy or
alter the identity or quantity of the analyte)
SAMPLING BULK MATERIALS
Identify the population from which the sample
is to be obtained.
Collect a gross sample that is truly
representative of the population being
sampled.
Reduce the gross sample to a laboratory
sample that is suitable for analysis.
SAMPLING METHODS
Methods of sampling are given in standard reference
books.
ASTM (American Society for Testing and Material)
APHA (American Public Health Association)
AOAC (Association of Official Analytical Chemists
International)
Homogeneous samples present no problem, a simple
grab sample approach taken at random and
assumed to be representative.
Several samples have to be taken if parent sample is
heterogeneous.
SAMPLING SOLID
Inhomogeneity of the material, make sampling of
solids more difficult.
The easiest way to sample a material is grab
sample, the sample taken at random and assumed
to be representative.
For reliable results, it is best to take 1/50 to 1/100 of
the total bulk. The larger the particle size, the
larger the gross sample should be.
The gross sample must be reduced in size to obtain
a laboratory sample.
EXAMPLES
Stockpile of cereals: take increment from surface and
interior.
Compact solids (metals and alloys): obtained by
random drilling or by sawing across the metal at
random intervals and collecting the `sawdust as the
sample.
Obtaining a random sample from a bulky material
(ore, grain, coal) can be achieved while the material
in motion (conveyor belt). Periodically transfer
portion into a sample container.
SAMPLING SOLID
CONE AND QUARTER
SAMPLING LIQUIDS
Liquid samples are homogeneous and are
much easier to sample.
The gross sample can be relatively small.
If liquid samples are not homogeneous, and
have only small quantity, they can be
shaken and sampled immediately.
Sampling techniques will depend on the
types of liquid.
EXAMPLES
Large volume of liquids (impossible to mix)
- Sampled after transfer (during discharge)
- If in a pipe, sampled after passing through a pump
or at different points in pipe system.
Large stationary liquids (lakes, rivers)
- Sampled at different depths using a sample thief
- Sample thief is a bottle that can be opened and
filled at any desired location in the solution.
Biological fluids
- The timing of sampling is very important
e. g. before meal or after meal.
SAMPLING GASES
Tend to be homogeneous.
Large volume of samples is required because
of their low density.
Examples:
- Air analysis: Use a `Hi-Vol sampler that is
containing filters to collect particulates.
- Liquid displacement method: The sample must
has little solubility in the liquid and does not react
with the liquid
- Breath sample: The subject could blow into
evacuated bag.
SAMPLING GASES
Air Samplung Pump
Dust Sampler
Air Sampling Filters
Hi-Vol Hi-Vol
SAMPLE STORAGE AND
PRESERVATION
Samples are preserved to prevent from:
Decomposition of biological samples through the
action of bacteria. Refrigerated after collection until
the time of analysis.
Precipitation of metals from water samples. Acidified
(10% HNO
3
) immediately upon collection.
Loss of water from hygroscopic material.
Loss of volatile analytes from water samples.
SAMPLE PREPARATION
Sample preparation or sample treatment is a step in
chemical analysis where the sample is brought into
the correct size form for analysis.
Sample preparation:
Most laborious
Time-consuming
Error-prone steps
Distribution of Time Analysts Spend on
Sample Analysis
GENERAL PRINCIPLES FOR SAMPLE
PREPARATION
PREPARING A LAB SAMPLE
Converting the sample to a useful form:
Solids are usually ground to a suitable particulate
size to get a homogeneous sample.
Dry the samples to get rid of absorption water.
(Drying at 110 to 120C for 1 hour and cooled in
dessicator before weighing).
Solid samples must be dissolved in solution.
DEFINING REPLICATE SAMPLES
Replicate samples are always performed
unless the quantity of the analyte, expense
or other factors prohibit.
Replicate samples are portion of a material of
approximately the same size that is carried
through an analytical procedure at the same
time and the same way.
PREPARING SOLUTION
Most analyses are performed on solutions.
A solvent is chosen that dissolves the whole sample
without decomposing the analyte.
Digestion should be performed in Teflon or quartz
containers to reduce contamination.
Several sources of error are encountered in the
sample dissolution step:
- Incomplete dissolution of the analyte.
- Losses of analyte by the volatilization.
- Introduction of analyte as a solvent contamination.
- Contamination from the reaction of the solvent with
vessel walls.
DECOMPOSITION AND DISSOLUTION
Simple Dissolution
Acid Treatment/Wet Digestion
Fusion Techniques
Organic Solid
Dry Ashing
Wet Digestion
Inorganic Solid
SIMPLE DISSOLUTION
Dissolution by water.
WET DIGESTION
Dissolution in various strong mineral acids.
HCl Carbonates, phosphates, oxides
H
2
SO
4
Organic material at 300C
HNO
3
Any metals not dissolve by HCl
HClO
4
Steel
HF Silica
Aqua Regia (HCl:HNO
3
, 3:1) Not stable
HNO
3
:HCl:HF (5:15:3) Alloys
GRADE OF ACIDS
Very High Purity Chemicals
- ARISTAR
TM
(BDH), Ultra-Pure (NBS)
Analytical Reagents
- Certified AR
TM
(Fisher) and Puriss
TM
(Fluka)
Chemically Pure (CP)
- CP
TM
(Sigma), GPR
TM
(BDH)
Practical Grade
- Purified
TM
(Sigma), LR
TM
(BDH)
Commercial or Technical Grade
WET DIGESTION
MICROWAVE DECOMPOSITION
FUSION TECHNIQUES
Contamination by flux material
High salt content
High temparature, loss of analyte through
evaporation
Sample container may react with flux material
DISADVANTAGES OF FUSION
TECHNIQUES
DESTRUCTION OF ORGANIC MATERIAL
FOR INORGANIC ANALYSIS
For organic materials (animal and plant tissue,
biological fluid ) containing inorganic analytes such
as trace metals, the organic matrix is destroyed via :
Dry Ashing
Involves slow combustion at 400-700C , which
leaves behind the inorganic residue which is soluble
in dilute acid.
Wet Digestion
Heat organic with oxidising acids (HNO
3
/H
2
SO
4

mixture), inorganic residue left behind.
ELIMINATING INTERFERENCES
Interferences are substances that prevent
direct measurement of the analyte and must
be removed.
Techniques
- Separation
- Standard Addition
MEASUREMENT
The analytical measurement is often the simplest stage
of the analytical process.
All reagents used must be of high purity (reagent grade).
For trace analysis a blank measurement must be
performed.
Analytical measurements are divided into two types:
classical (gravimetric, volumetric) and instrumental.
The physical or chemical property proportional to the
analyte concentration is measured.
Suitable standards must be measured to determine the
relationship between analyte quantity and the physical/
chemical property being measured (i.e., calibration).
Classical Methods (Gravimetric, Volumetric)
Accurate and precise to approx. 0.1% but require large
amount of analyte (mmol, mg).
Instrumental Methods (Spectroscopy,
Chromatography)
More selective and sensitive than classical methods but
less precise.
Accurate to ! 1%
Measure of physical/chemical property of an analyte
related to concentration.
Rapid/may be automated/may be used for determination
of multiple analytes at a time.
CALCULATING RESULTS
Determine the concentration of the analyte in the
sample solution.
Use results to calculate the amount of analyte in the
original (bulk) sample.
Evaluation of results
Requires appropriate use of statistics
Must be reasonable, reliable and related to the
problem as originally stated
Careful thought should be given to data presentation,
so that it is readily digested and conclusions are
clearly demonstrated.
REPORT
Report results with limitation/accuracy
information.
A professional chemist/charted chemist
should verify the report.
Test Report an example
Professional Chemist