Topic 3

Sampling and evaluation of

experimental data

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 Chemical Analysis
Types of analysis :
1. Measurements of physical and chemical
properties.
2. Qualitative analysis
3. Quantitative analysis
4. Diagnostic analysis
Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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QUALITATIVE or QUANTITATIVE
analysis
QUALITATIVE
Analysis conducted to identify what are the
constituents present in the sample (identification of the
sample component)

QUANTITATIVE
Analysis to determine how much of each
constituent present in the sample.
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 Qualitative analysis is what.
Quantitative analysis is how much.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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 STEPS INVOLVED IN AN ANALYSIS
1) Identifying problems: 5) Propose solution:
Type of info needed Conduct external
(quality, quantity, evaluation
characterization,
fundamentals)
4) Analyse data :
Statistical, verify results,
interpret results
2) Design of
experimental procedure
:Design criteria (cost
accuracy), identify 3) Conduct experiment:
interferents, select Gather data
method, sampling

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 SAMPLING AND EVALUATION OF
EXPERIMENTAL DATA
Population - The group of things, items or units under
investigation
Sample - Obtained by collecting information only
about some members of a "population
Sampling Act of collecting sample to produce
meaningful information.

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 What is the purpose of sampling?
The purpose of SAMPLING is to obtain a
REPRESENTATIVE SAMPLES of the whole
sample that can be taken to the laboratory for
chemical analysis and the results obtain will be
ACCURATE.

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In a chemical analysis :
A chemical analysis is usually performed on only small
portion of the material collected to be characterized.
If the amount of material is very small and it is not needed
for further use, then the entire samples may be used for
analysis.
WHAT ARE THE MATERIALS THAT CAN BE
SAMPLED?????????

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 Sampling-water sampling

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 Water pollution

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 Soil erosion

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 Soil sampling

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 Sampling

Air Sampling Solid Sampling

Liquid Sampling

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 Air Sampling
Grab sampling
An actual sample of air is taken in a flask, bottle, bag or other
suitable container. Done over a period of few seconds or up To
1-2 minutes.

ANALYSIS

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 Air Sampling

Continuous or integrated sampling

Gases or vapours are removed from the air

over a measured time-period and concentrated
by passage through a solid or liquid sorbent.

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 EXAMPLE
A sample is collected by opening a tube,
connecting it to a sample pump, and pulling
air through the tube with the pump.
Airborne chemicals are trapped onto the
surface of the sorbent.
The tube is then sealed with push-on caps, and
sent to a laboratory for analysis.
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 Liquid sampling
Liquid sample tend to be homogeneous and are
more easier to sample.
Liquids mix by diffusion only very slowly and
must be shaken to obtain a homogeneous mixture.
If water sample is taken from the river, then the water
samples is collected at the SURFACE, MIDDLE and at
the BOTTOM of the river bed.

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If the liquid is in a large container, then the
liquid should be stirred first before the samples
are taken at the top, middle and at the bottom of
the container.

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 Solid sampling
Inhomogeneity of the solid sample, variation in
sample size and variation within the particle size make
sampling of solids more difficult then other material.
The easiest but usually the most unreliable way to
sample a solid material is by the grab sample, which is
one sample taken at random and assume to be
representative.

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Solid samples usually need further treatment.
Example if ores are being sampled, first crush the
ore to a smaller size and then sieve and use the
QUARTERING TECHNIQUE to get the right
sample size to the laboratory.
Solid samples may need drying.

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 QUARTERING TECHNIQUE

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 Purpose of drying solid samples :
To ensure that the exact weight is obtained
during the QUANTITATIVE chemical analysis.

How it is done :
Solid samples dried in oven at 105 110oC for
1- 2 hours. Plant and tissue samples dried by
heating

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Problems associated with drying of samples :
1. Samples might decompose at high temperature
2. Some samples are sensitive to heat, therefore
drying can be carried out in a desiccators

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 Sample storage
Samples storage pupose:

There is a time gap between when the sample is taken and

the actual analysis is being carried out.

For liquids samples, make sure that it is kept in bottles

with stoppers.

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Acidic liquid samples can be stored in glass container
whereas basic liquid samples in plastic container.

Solid samples is easier to keep and have less chance to

be adulterated by foreign matters.

Sometimes it can also get absorbed or adsorbed to the

wall of the container.

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What are the problems encounter during
storage of samples?
The sample can be adulterated / contaminated by foreign matter .
There is a lost of analyte during storage.
Decomposition of sample.
Side reactions can occur. Example in the air pollution studies the
content of SO2 in air is not stable due to the following reaction
2SO2 + O2 2SO3
To avoid the above reaction the sample is cooled to 4oC
The sample should not react with the wall of the container or get
adulterated.
During storage of samples eg liquid samples, sometimes there is a
lost of analyte if it is volatile .[so the container should be closed
tightly]

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 Replicate Samples
Most chemical analyses are performed on replicate
samples whose weights or volumes have been
determined by careful measurements with an
analytical balance or with a precise volumetric device.
Obtaining replicate data on samples improves the
quality of the results and provides a measure of their
reliability.

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 Tecniques to analyse samples
using solution
Most analyses are performed on solution of the sample.
Ideally, the solvent should dissolve the entire sample
rapidly

using solid
ashing

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Ashing in analytical chemistry is defined as the
heating of a substance to leave only
noncombustible ash, which is analyzed for it's
elemental composition

WET ASHING, DRY ASHING,

MICROWAVE, FUSIONS.

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 Advantages of Ashing
The ability to decompose large sample sizes.
Little or no reagents is required.
The technique is relatively safe.
The ability to prepare samples containing volatile
combustion elements such as sulfur, fluorine and chlorine
(the Schniger oxygen flask combustion technique is very
popular in this case).
The technique lends itself to mass production.

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 Disadvantages of Ashing
Losses due to retention to the ashing container.
Losses due to volatilization.
Contamination from the ashing container.
Contamination from the muffle furnace.
Physical loss of 'low density' ashes when the muffle door is
opened (air currents).
Difficulty in dissolving certain metal oxides.
Formation of toxic gases in poorly ventilated areas. (Note
that all charring should take place in a hood and the muffle
furnace must have a hood canopy for proper ventilation).

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 Wet ashing
To treat solid sample by acid digestion, producing clear
solution with no loss of the element to be determine.
Strong mineral acids are good solvents for many
inorganics.
Hydrochloric acid, nitric acid or aqua regia (3:1
HCl:HNO3) dissolve many inorganic substances.
HF acid decompose silicates.
Perchloric acid is used to break up organic complexes.

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 Dry ashing (gravimetric)

Performed by weighed sample in crucible, heated in

muffle furnace then the residue is dissolve in suitable acid.
Typical ashing temperatures are 450 to 550 C.
Magnesium nitrate is commonly used as an ashing aid.
Charring the sample prior to muffling is preferred.
Charring is accomplished using an open flame.

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Care must be taken to ensure that non of the
volatile elements (Hg, Arsenic, Pb) from escaping
during ashing.
Dry ashing often used to remove organic substances
from interfering with the analyte.

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 MICROWAVE

In some cases the dissolution of sample can be done

by using microwave oven to accelerate the
dissolution process (at microwaves T=100 250oC).
The sample is sealed in specially designed micromave
digestion vessel with a mixture of appropriate acids.

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Microwave ovens can be used for rapid and efficient
drying and acid decomposition of samples.
Advantages of microwave digestions include
reduction in times from hours to minutes and low
blank levels due to reduced amounts of reagents
required.

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 FUSION
A weighed sample is mixed with a flux (sodium
peroxide) in a metal (zirconium) or graphite crucible. The
mixture is heated over a flame, or in furnace and the
resulting fused material is leached with either water or
appropriate acid (dilute mineral acid) or alkali.
These techniques are required for sample types that are
inorganic in nature and unreactive toward acid
decomposition

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 Fusions for Trace Analysts
Fusions are considered to be more of a 'last resort' by
trace analysts because:
They are expensive and often not available (high purity
fluxes).
They yield high solids solutions that can salt out in the
nebulizer.
Large dilutions of the sample are a necessity.

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 They often require expensive equipment.
Spectral interferences from the flux and/or crucible
construction material must be considered.
Contamination of the sample with the crucible
construction element and impurities must be
considered
7. They are labor intensive.

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