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BASIC ANALYTICAL
CHEMISTRY
CHAPTER OUTLINE
4.1
4.2
4.3
Treatment
analysis
of
samples
prior
to
chemical
Standards
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.
Chapter 4
Classification of Sampling
1. Base on method used for sampling
Sample Weight (mg)
Meso
>100
>100
Semi-micro
10 100
50 - 100
Micro
1 10
< 50
Ultra-micro
<1
>1%
Minor
0.1 1 %
Trace
< 0.1 %
Ultratrace
Chapter 4
Sampling
Deciding how to obtain a sample for analysis
depend on,
1.
2.
3.
Obtaining a representative
sample is the first step of
an analysis.
The gross sample is several small
portions of the sample. Sample
taken at random an assumed to
be as representative.
Sampling Solids
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2008
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Chapter 4
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12
How it is done?
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Chapter 4
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Sampling Liquids
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Sampling Liquids
Sampling techniques will depend on the types
of liquid.
1.
2.
3.
Biological fluids
A special
sampling
bottle or bag
is used to
collect liquid
samples.
Chapter 4
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Sampling Gases
1. 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.
2. 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.
Examples
Rotary vane pump with open flows to 32 L/min,
locking flow valve, 10 feet tubing, and silencer for
quieter operations. Suitable for use with asbestos
cassettes, VersaTrap cassettes, and bioaerosol
impactors
Chapter 4
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Sampling Gases
Tend to be homogeneous.
Large volume of samples is required
because of their low density.
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.
Chapter 4
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Sample Storage
There is a time gap between when the
sample is taken and the actual analysis is
being carried out.
Therefore the sample should not be
adulterated by foreign matter or there is a
lost of analyte during storage.
During the storage of samples certain side
reactions can occur. This will change the
properties of the samples that will be
analysed.
Therefore, the sample, once collected must
be handled and stored in a manner so as to
protect it from contamination or alteration.
Chapter 4
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Sample Storage
2SO2
O2
2SO3
Chapter 4
20
Sample Storage
For liquids samples, make sure that it is kept
in bottles with stoppers.
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.
Chapter 4
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8.
Chapter 4
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3.
Chapter 4
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Chapter 4
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Desiccator
Chapter 4
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Weighing bottles.
Chapter 4
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Weighing dish.
Chapter 4
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Volumetric flask.
Chapter 4
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Typical pipets
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Measuring pipettes.
Chapter 4
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Chapter 4
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Single-channel and
multichannel digital
displacement pipets
and microwell
plates.
Chapter 4
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Typical burette.
Chapter 4
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Meniscus illuminator.
Chapter 4
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Chapter 4
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Wash bottles:
(a) polyethylene, squeeze type; (b) glass, blow type.
Chapter 4
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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.
Chapter 4
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Chapter 4
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Sources of error:
i.
ii.
iii.
iv.
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Samples Dissolution
Sample dissolution is digestion or mineralization the
analyte into solution and to get rid of the interfering
organic substances in the samples.
Chapter 4
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A. Method Dissolving
Inorganic Materials
1.
2.
45
Chapter 4
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B. Method Dissolving
Organics Materials
1.
Wet Digestion
A method for decomposition of an organic
material, such as resins or fibers into an ash
by treatment with a boiling oxidizing acid or
mixture of acid.
The acids oxidize organic matter to carbon
dioxide, water and other volatile products
which are driven off leaving behind the salts
or acids of the inorganic constituents.
Chapter 4
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B. Method Dissolving
Organics Materials
2. Dry Ashing
Example
Hydrochloric acid, nitric acid or aqua regia (3:1)
dissolve many inorganic substances.
HF acid decompose silicates.
Perchloric acid is used to break up organic
complexes.
Chapter 4
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TOTAL DISSOLUTION
Process whereby the entire sample
dissolve in a solvent
PARTIAL DISSOLUTION
Process whereby only the analyte
dissolve in a solvent
Chapter 4
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Usually use
the
combination of
acid
Performed in
kjedahl flask
Boiled of the
acids, white
fumes evolve
Eg, sulphuric
acid and nitric
acid
Chapter 4
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1. Wet Digestion
Priciple of wet digestion (wet ashing)
Usually use combination of acids to achieve a
complete dissolution.
A small amount (5 mL) of H2SO4 is used with
larger volumes of HNO3 (20 to 30 mL).
Usually performed in a Kjeldahl flask.
HNO3 destroys the bulk of organic matter,
but it does not get strong enough to destroy
the last traces.
.
Chapter 4
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cont
52
Performed at high
temperature
Process of dry
ashing
(dry method)
Atmospheric O2
serves as oxidant
Chapter 4
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Example:
lead is volatilized at temperature more than 500c,
especially if chlorine if present (blood and urine
samples). The crucible are preferred for lead for
minimal retention losses. If an oxidizing material
(Mg (NO3)2 is added to sample, the ashing
efficiency is enhanced.
Chapter 4
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2. Dry Ashing
Chapter 4
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2. Dry Ashing
Performed by weighed sample in crucible,
heated in muffle furnace then the residue is
dissolve in suitable acid (1-2 mL of hot
concentrated or 6 M HCl).
Typical ashing temperatures are 450-550C.
Magnesium nitrate is commonly used as an
ashing aid.
Charring the sample prior to muffling is
preferred. Charring is accomplished using an
open flame.
Further reading page 55 (G.D Christian).
Chapter 4
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2. Dry Ashing
Care must be taken to ensure that non of
the volatile elements (Hg, Arsenic) from
escaping during ashing.
Dry ashing often used to remove organic
substances from interfering with the
analyte.
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ADVANTAGES
AND
DISADVANTAGES
WET DIGESTION
DRY ASHING
Chapter 4
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WET DIGESTION
ADVANTAGES
Superior in term of
rapidity
Freedom from loss by
retention
Low level of
temperature maintained
DISADVANTAGE
Introduction of
impurities from the
reagent necessary
for the reaction
Chapter 4
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DRY ASHING
ADVANTAGES
DISADVANTAGE
60
Other Technique
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
microwave digestion vessel with a mixture
of appropriate acids.
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Other Technique
Microwave
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.
62
Other Technique
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.
Chapter 4
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Chapter 4
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Chapter 4
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Eliminating Interferences
Interferences are substances that prevent
direct measurement of the analyte and must
be removed.
ANALYTES - are
May included separation steps:
components of a
precipitation
sample that are to
chromatography
be determined.
distillation
dialysis
extraction into an immiscible solvent
Chapter 4
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Standard Solution
Definition
Standard solutions are solution whose
concentrations are known to a high degree
of accuracy.
Characteristics:
i) Maintain its concentration over a long
period of time (months or years) after
preparation. This eliminates the need for
restandardization.
ii) Must be able to undergo rapidly,
stoichiometric, and complete reaction with
the analyte.
Chapter 4
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Standardization
1
volume (L)titrant
b (mol titrant)
a (mol primary std)
Chapter 4
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Standard Solution
Standard Solution
How to prepare 1L 0.77M of NaCl?
Commercial Standard
1. Technical or commercial grade. Not use in
analytical work, but cleaning solution.
Standard Solution
A standard solution can be prepared in
either of two ways:
1.
Chapter 4
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Primary Standard
Definition
A compound of highest purity and it is used to determine,
directly or indirectly, the concentration of the standard
solution for a titration.
Ideal primary standards for volumetric titration should have the
following characteristics:
i.
ii.
iii.
iv.
v.
vi.
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Primary Standard
The number of primary standards available is very limited for example
oxalic acid (H2C2O4.2H2O), sodium carbonate (Na2CO3), calcium
carbonate (CaCO3), sodium chloride and arsenic trioxide.
Others:
1) potassium hydrogen phthalate
2) potassium dihydrogen phosphate
3) potassium hydrogen tartarate,
4) Sodium carbonate
5) Sodium oxalate
6) Benzoic acid
7) Potassium dichromate
Chapter 4
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Secondary Standard
A less pure substance whose composition is
reliably known.
The purity or the concentration of a
secondary standard must be established by
careful stoichiometric analysis, usually
against a primary standard.
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Stock Solution
78
Dilution
Dilution
M1V1 = M2V2
Chapter 4
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