Steps in a Quantitative Chemical Analysis

1. Selecting a method of analysis

2. Sampling
3. Moisture Determination
4. Dissolving the sample
5. Eliminating interferences
6. Calibration and measurement
7. Calculation of results and evaluation of their
reliability
1. Selecting a method of analysis
Purpose of Analysis
a. Preparation of a databank of figures to establish
trends
b. Acceptance/rejection of a chemical/product
before use in a manufacturing operation
c. Assessment of the value of a consignment of
goods before payment
d. Prosecution of a company for selling a product not
up to the stated specification
e. Criminal charges of a person found to be in
possession of drugs.
1. Selecting a method of analysis

Sources of Methods
a. In-house methods developed by one laboratory for
their own special needs
b. Methods published in the open scientific
literature, e.g. The Analyst
c. Methods supplied by trade organizations
d. Methods in books published by professional
organizations, e.g. Association of Official Analytical
Chemists (USA)
e. Methods from standards organizations, e.g. ISO
f. Methods from statutory publications
1. Selecting a method of analysis

Factors to consider in choosing a method

a. Limit of detection (LOD)
b. Accuracy
c. Precision
d. Speed
e. Equipment required
f. Sample size
g. Cost
h. Safety
i. Specificity
2. Sampling

the process by which a portion of material is reduced

in size to an amount of homogeneous material that
can be conveniently handled in the laboratory and
whose composition is representative of the
population; varies according to the physical state and
size of the bulk sample.
needs a statistical approach to get a very small
fraction of a material to represent it for purposes of
laboratory analysis.
the most difficult step in the entire analytical process
and the step that limits the accuracy of the analysis
Types of Samples
a. Representative: typical of the parent material for
the characteristic under inspection
b. Selective: uses a sampling plan that screens out
materials with certain characteristics and/or selects
only material with other relevant characteristics
c. Random: selected by random process to eliminate
problems of bias in selection and/or to provide a
basis for statistical interpretation of measurement
data
d. Composite: consists of two or more portions of
material (collected at the same time) selected so as
to represent the material being investigated.
Types of sampling: differ with different samples

a. Solids
Particulates
Metals and Alloys
b. Liquids
c. Gases
d. Atmospheric samples
3. Moisture in Samples
Types of Water
a. Essential Water: forms an integral part of the molecular or
crystalline structure of a compound in its solid state.
Water of crystallization in a stable solid hydrate, e.g.
BaCl2.2H2O
Water of constitution found in compounds that yield
stoichiometric amounts of water when heated or
otherwise decomposed e.g. Ca(OH)2 (s) CaO(s) + H2O(g)
b. Nonessential Water: retained by the solid as a consequence
of physical forces
Adsorbed water resides on the surface of the material
Sorbed water is contained within the interstices of the
molecular structure of a colloidal compound
Occluded water is trapped in random microscopic pockets
of solids, particularly minerals and rocks (removed by
decrepitation)
Moisture determination in solids

The sample is weighed before and after drying the

sample.
This step is done so that the composition of the
sample does not depend on the relative humidity
and temperature at the time of analysis.
 Test yourself: moisture determination
1.000 g of soil, as-received, gave a moisture content of 14.00 %.
The oven-dried sample, completely moisture-free, showed 18.00
% K. Find % K in the sample as-received.

Sample
As-recd Dry
% H2O 14.00 % 0%
%K ? 18.00 %
% NVM 86.00 % 100.00 %

% K as -rec'd % K dry
% NVMas -rec'd % NVMdry
% K dry 18.00
% K as -rec'd % NVMas -rec'd 86.00 15.48
% NVMdry 100.00
Methods for determining moisture
Direct methods
a. Methods that require application of heat
Oven-drying
Distillation
b. Freeze drying or lyophilization
c. Chemical Methods
Karl Fischer Titration
Calcium Carbide Method
Cobalt Chloride Paper (blue when dry, pink when moist)

Indirect methods: those which measure physical property of the

sample that is linearly related to its water content, e.g.,
absorbance, refractive index, electrical conductivity, specific
gravity
4. Dissolving the sample: trial and error method
using solvents of progressively increasing reactivity
a. distilled water at room temperature
b. hot distilled water
c. dilute non-oxidizing acid (e.g. HCl)
d. dilute oxidizing acid (e.g., HNO3, H2SO4, HClO4)
e. concentrated non-oxidizing acid
f. concentrated oxidizing acid
g. acid mixture (e.g., aqua regia = 3 HCl:1 HNO3)
h. HF: primarily used for decomposition of silicate
rocks and minerals in the determination of species
other than silica
i. use of flux
Basic Fluxes: alkali metal carbonates, hydroxides,
peroxides and borates
Acidic Fluxes: pyrosulfates, acid fluorides, boric oxide
5. Eliminating interferences

a. Interferences are species other than the analyte

that affect the final measurement.
b. A scheme must be devised to isolate the analyte
from interferences before the final
measurement is made.
Separation by precipitation
Separation by extraction
Separation by ion-exchange
Separation of inorganic species by distillation
6. Calibration and measurement
All analytical results depend on a final measurement of
a physical property of the analyte, which varies in a
known and reproducible way with the concentration of
the analyte.
7. Calibration of results and evaluation of their
reliability

Results are calculated and their reliability

estimated.
The experimenter must provide some measure of
the uncertainties associated with computed
results if the data are to have any value.