Steps in doing analysis:

1. Deciding on an analytical method

2. Collecting and preparing bulk sample
3. Preparing the laboratory sample
4. Defining the samples to be analyze (replicate
samples)
5. Preparing solutions of the sample
6. Elimination of interferences
7. Calibration, measurement and calculating results
8. Evaluating results and estimating reliability
Classification of analysis
1. Macro - more than 0.1 g of sample is available
2. Semi -micro- 10-100 mg of sample is available
3. Micro - 1-10 mg of sample is available
4. Ultra-micro – samples are in the order of
micrograms
Divisions of quantitative analysis
a. Volumetric methods – the quantity of desired constituent is
computed based on the volume of reagent needed for
reaction with sample.
b. Gravimetric methods – the quantity of desired constituent is
computed based on the weight of precipitate obtained from
sample.
c. Colorimetric methods – the unknown is converted into a
colored compound and the intensity of the color is compared
with standard.
d. Other physico-chemical methods such as turbidity,
nephelometry, polarimetry, refractometry.
e. Gas-Volumetric methods
Volumetric methods
1.Chemical indicator methods – completion of the reaction is indicated by the change
in color of the indicator used.

2.Electrometric methods - completion of the reaction is indicated by the electrical

means.

a) Potentiometric methods
– changes of potential of a cell of which the solution being titrated is a component part.
b) Coductometric method
– changes in conductivity of the solution being titrated.
c) Amperometric method
– changes of amperage of an electric current passing through a solution during
titration.
d) Coulometric method
– quantity of unknown is established for ampere-time measurements of an
electrolytic cell where the solution to be titrated is added.
Gravimetric methods
1.Chemical precipitation methods
a)Analysis of sulfates by precipitation as BaSO4
• SO42-(aq) + BaCl2 + HCI BaSO4 (s)
b) Analysis of iron content
• Fe3+ + OH- Fe(OH)3 Fe2O3
2. Electrolytic deposition method
• Analysis of Cu– pass electric current through a solution
of Cu2+ to deposit Cu metal.
Gas-Volumetric methods
1. Absorption methods – amount of desired constituents is
computed based on the change in volume of the gaseous
sample after selective absorption of the component.
Pass through KOH
Mixture of CO2 + O2 O2

Change in volume = volume of CO2 absorbed

2. Combustion method – based on change in volume brought

about by burning a mixture of gasses.
Sampling and Sampling Preparation
1. The sample is collected in the manner consistent with
the goal of the analysis.

2. The sample should be handled so to prevent its

contamination or alteration.

3. The sample is brought into the laboratory and prepared

for the technique chosen.
Sampling Plan
A good sampling plan must be able to guarantee that the information needed to meet
the objectives of the measurements being made is obtained. The design of such a
plan must take into consideration of the following:
1. Objectives
a. What do you want to know?
b. What do you need this information?
c. What happens to the results?
d. What actions will follow?
2. Analytes and Methods
A sampling plan should identify what analytes (constituents of)
the material are to be determined. The preferred method to be
used is that one has been standardized and whose accuracy
and precision can be verified.
3. Sampling Locations and Increments
It is important to identify the parts of a material and the
corresponding portions that will make up the sample.
4. Others (legal and safety aspects).
Different Approaches to sampling
1. Random Sampling
– refers to sampling without bias. Increments are taken in such a way that any portion of the
bulk of the material has the same probability of being included when a sample is taken.

2. Systematic Sampling
– one of the most commonly employed sampling techniques; incremental samples are taken at
preset intervals.

3. Stratified Sampling
– an extension of systematic sampling where each batch is further divided into groups (strata).

4. Sequential Sampling
– samples are taken at preset but random intervals to check for compliances to a specific
parameter; also reduces the number and amount of samples taken.
5. Sampling for food surveillance studies

6. Environmental Sampling
– deals with determining changes in analyte concentration over a specific time period or
location: could be monitoring study or simply a report of an average value.
Preparation of a Laboratory Sample
The gross sample is systematically mixed and reduce to
obtain the laboratory sample. If the mixing is done by
hand, the following methods can be used.
1. Long-pile and Alternate- Shovel Method
2. Coning
3. Tabling
4. Riffling
Liquids Reagents for Dissolving or Decomposing Samples
• Hydrochloric Acid
– the concentrated form of the acid (12 M) is an excellent solvent for metal oxides and
metals that are more easily oxidized than hydrogen.
• Nitric Acid
– hot concentrated nitric acid (~15 M) is able to dissolve all common metals except for
aluminum and chromium (due to surface oxide formation).
• Sulfuric Acid
– hot concentrated sulfuric acid (~18 M) is able to effectively decompose and dissolve
many samples due to a high boiling point of 340 0C.This mixtures dehydrates and
decomposes samples containing organic compounds.
• Perchloric Acid
– hot concentrated perchloric acid (~9 M) is considered a potent oxidizing agent and is
able to attack alloys and stainless steels that are resistant to other mineral acids.
• Oxidizing Mixtures
– rapid dissolution can be achieved by using a mixture of acids or by adding an
oxidizing agent to a mineral acid e. g. aqua regia ( 3 parts concentrated HCI and 1 part
concentrated HNO3)
• Hydrofluoric Acid
– this acid is primarily used in the decomposition of silicates and minerals where silica
is not to be determined. It’s also occasionally added to other acids to act on difficult to
dissolve steels
Types of errors in experimental measurements

1. Random or indeterminate errors – errors which do not affect each

determination in the same manner. These are due to inherent
limitations of the equipment, to limitations of observation and to lack
of care in making the measurement. These errors can be reduced by
performing experiments replicate.

Examples: variation in judgement of end points, variation in

temperature, mistakes in observation of balance rest points.

2. Systematic or determinate errors- errors that affect each individual

result of replicate determinations in the same manner.

Examples: instrument errors – weights that are incorrect in mass,

balance arms of unequal lengths.
Methodic errors - coprecipitation of impurities, slight
solubility of precipitates and occurrence of side reactions.
Common weighing errors:

1.Inaccuracies in the values of the weights. This can be eliminated by

calibration.
2.Moisture – condensation water vapor on dry samples or precipitates may cause
a weight gain so it is standard practice to weight all samples in a covered bottle.
3.Temperature – object to be weight should be at room temperature. If object
weight are still warm, weights are too light because convection currents set up in
the balance tend to push the left pan up and retard the swings of the balance.
4.Electrification – glass vessels acquire a charge of static electricity when they
are wiped with a dry cloth. This may cause the swings of the balance to change
in an allowed to stand until most of the surface moisture is evaporated.
5.Buoyancy – can be corrected by applying the equation below:
 
Wv = weight in a vacuum
Wa = weight in air
d0 = density of object
dw = density of weights (approx. 8)
dair = density of air (0.0012 g/mL) at ave. T ,P humidity
• Blank analysis – an analysis of a material containing
all the constituents of he given sample except the
desired constituent. The numerical result obtained in the
blank is used to correct the value obtained in the
unknown.

• Control analysis – an analysis of a material

containing all the constituents of the given sample
except that the material used is of known composition.
Methods used to describe the accuracy of the
measurements:

1. Absolute error = True Value – Experimental Value

2. % Relative Error = True value – Expt’l value x 100

True value
Methods used to describe the precision of
the measurements:

1. Range: highest value – lowest value

2. Average deviation (d)
3. Standard deviation (s)
4. Student’s t - to correct for uncertainties due to small
population; to take into the fact that x is not the same
as u.
Criteria for rejection of outlier:
• 4d rule
1. Compute the mean and average deviation of the “good”
results.
2. Find the deviation of the suspected result (outlier) from
the mean of the “good” ones.
3. Find the deviation of the suspected result from the mean
of the “good” ones is at least 4 times the average
deviation of the “good” results then the outlier is rejected.
• Q test
1. Calculate the range of the results
2. Find the difference between the suspected results
and its nearest neighbor.
3. Divide the result in NO. 2 by the range in No. 1 to
obtain Q.
4. If Qcomputed > Qtable then the result can be discarded.