INTRODUCTION TO

ANALYTICAL CHEMISTRY
CHM 202

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 Module 1: Review of
fundametal concepts
Chemical analysis
Sampling techniques

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Analytical chemistry
• Analytical Chemistry: Measurement Science with a set of powerful tools
and methods useful in all fields of science and medicine.

• It gives both Qualitative and Quantitative information in an analysis.

• Qualitative analysis: chemical identity of elements or compounds in a

sample while Quantitative analysis indicates the amount of each
substance in a sample.

• Analytes are components of a sample that are to be determined.

Role of analytical chemistry
• Applications: Sciences, industry, and medicine.
• Examples:
• Determination of concentrations of oxygen, CO2 in blood samples to
diagnose or treat illnesses.

• Effectiveness of smog – control devices is accessed by measuring

amount of hydrocarbons, nitrogen oxides and CO present in
automobile exhaust gases.

• Mechanisms of chemical reactions are elucidated through reaction rate

studies.
Quantitative analytical methods
• Results of a typical quantitative analysis can be computed from two
measurements:

• Mass or volume of sample

• Some quantity that is proportional to the amount of analyte in the

sample e.g. mass, volume, light intensity, electrical charge etc.

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Classification of analytical methods
• Gravimetric (mass of analyte or some compound related to it are
determined ).
• Volumetric (volume of solution containing enough reagent to react
completely with the analyte is measured)
• Electroanalytical (measurement of electrical properties like current,
potential, resistance and quantity of electrical charge)
• Spectroscopic: measurement of the interaction of electromagnetic
radiation and analyte atoms or molecules or production of such
radiation by analytes.
• Miscellaneous methods: Mass spectrometry, radioactivity, sample
thermal conductivity, optical activity etc.

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Classification of analytical methods contd.

• Classical methods: Gravimetric and volumetric

• Instrumental methods: Electroanalytical and spectrophotometry

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Classification of analytical methods contd.
• Classification can be made according to size of sample or level of
constituents.

Sample Size Mass (g)

Macro 0.1
Semimicro 0.01-0.1
Micro 0.0001-0.01
Ultramicro <0.0001

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Classification of analtical methods contd.

Types of constituents concentration

Major 1-100 % (Gravimetric and
Volumetric)
Minor 0.01-1%
Trace 100 ppm-1ppb
Ultratrace <1 ppb

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Chemical analysis
• Chemical analysis:the study of the chemical composition and
structure of substances.
• STEPS IN A CHEMICAL ANALYSIS
• SELECT A METHOD

• OBTAIN A REPRESENTATIVE SAMPLE

• PREPARE A LABORATORY SAMPLE

• DISSOLVE THE SAMPLE

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Steps in chemical analysis contd.
• ELIMINATE INTERFERENCE

• MEASURE PROPERTY OF THE ANALYTE

• CALCULATE RESULT

• ESTIMATE THE RELIABILITY OF RESULT

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Method selection

• Choice of method depends on experience and intuition.

• Level of accuracy required. High reliability requires a large investment
on time.

• Selected method represents a compromise between accuracy required,

time and money available for analysis.

• Number of samples to be analysed: If samples are large, there is need

to invest time on assembling and calibration of equipment and
preparation of standard solutions.

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Sample
• Sample is the material of interest.

• Generally, a small fraction of the material of interest is used in a

chemical analysis.

• The composition of this fraction must reflect as closely as possible the

average composition of the bulk of material under investigation.

• SAMPLING describes the operation involved in procuring a

reasonable amount of material that is representative of the whole
sample.
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Sampling
• Sampling - the most difficult step in analytical procedure,`why?
• Trying to obtain a laboratory sample from a large whole.
• Non homogeneity of sample with regard to size/composition
particularly in large quantity.
• A number of steps must be taken to ensure that the laboratory sample
is a representative of the whole sample.
• The end product of the sampling step is usually an amount of
homogenous material weighing a few grams or at most few hundred
grams.
• **The reliability of an analysis cannot exceed that of sampling step, a
painstaking analysis with poor sampling is a wasted effort**.
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Sampling contd.
• Steps involved in sampling bulk material
• Identification of the population from which the sample is to be
obtained.
• Collection of a gross sample (thoroughly representative of the
population being sampled)
• Reduction of the gross sample to a few hundred grams of homogenous
laboratory sample (suitable for analysis)
• Examples of sample population: A carton of bottles containing
paracetamol
• Soil from a mechanic workshop
• A field of rice
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Sampling contd.
• To sample bulky and heterogeneous materials,
• A gross sample is taken by random picking of materials.

• Crushing of gross sample into smaller particle size, some of these are
taken and the rest discarded.

• Sampling of solutions of homogeneous samples are easier because any

portion would give a representative sample.

• Professional bodies have specified procedures for sampling different

materials.
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Sampling cond.
• For biological samples, conditions under which samples are collected
(fasting or after meals) and preservatives (e.g. anticoagulants added to blood
samples to prevent clotting) may affect a particular analysis.
• The components of blood are plasma (serum and fibrinogen) and cellular
elements (erythrocytes (red), leucocytes (white) and platelets). Cells are
separated from the plasma by centrifuging whole blood
• Blood samples can be analysed as whole blood, or separated as plasma or
serum. For physiological conditions, plasma or serum are used for analysis.
• To obtain plasma, anticogulant (e.g. heparin or a citrate salt) is added to the
blood sample to prevent clotting. Plasma contains fibrinogen (soluble
protein)and it is light pink in colour.
• Serum:The straw -coloured fluid obtained when blood is left to clot
(fibrinogen is converted to fibrin-insoluble protein through a series of
chemical reactions involving calcium ion) .
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Sample drying
• Drying is necessary to get anhydrous sample or remove adsorbed
moisture but retain chemically combined water.
• Drying is carried out in an oven or desiccators. Analysis can also be
carried out in received form.

• Most chemical analyses are performed on replicate samples, the masses

or volumes would have been determined by careful measurements with
an analytical balance or a volumetric device.

• Quality of results is improved by replication while giving a measure of

reliability.
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• Replicate samples or replicates
• These are portions of a material of approximately same size that are
carried through an analytical procedure at the same time and same way.

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Dissolution of sample
• Properties of solvent for dissolution
• Solvent used in the dissolution of a sample should completely dissolve
it in a short time as possible.
• Chosen solvent must not interfere with subsequent test of analysis e.g.
water, organic solvents and conc. acids. Water is used in dissolving a
number of inorganic salts and some organic compounds.
• When materials to be analysed are not soluble in common solvents, e.g.
high molecular mass polymers, animal tissues, silicate minerals etc, the
materials are converted into soluble forms.
• A property that is proportional to concentration can be measured once
the analyte is made soluble.

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Destruction of organic materials
• Animal and plant tissues, biological fluids and organic compounds are
decomposed by wet and dry digestion.

• Wet digestion:oxidation of the organic constituents of a sample with

oxidising reagents such as nitric acid, sulphuric acid, perchloric acid or
combination of them. Others include hydrogen peroxide, aqueous
bromine.
• Acids oxidise organic matter to CO2, H2O and other volatile products
which are released while salts or acids of the inorganic constituents are
left.

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Decomposition of sample contd.

• Dry digestion/ashing:Decomposition occurs by heating sample at a

high temperature (400 - 600oC) in a muffle furnace.

• Atmospheric oxygen burns off the organic matter, leaving an organic

residue.
• Oxidising aids may also be used to enhance ashing efficiency, .e.g.
MgSO4.

• Residue is leached with 1-2 mL conc HCl and transfered to a flask for
further treatment.
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Elimination of Interferences
• Interferences or interferent are species other than the analyte that affect
final result. They interfere with measurements and must be eliminated.

• Interferents may cause error in an analysis by enhancing or reducing

the quantity being measured.

• Different techniques – separation methods are used (Filteration,

precipitation, centrifugation etc. A technique is said to be specific if it
works for only one analyte and selective it works for few.

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Measurement
• The matrix or sample matrix is all the components in the sample
containing an analyte.

• The property, x (physical or chemical) being measured must vary in a

known and reproducible way with the concentration of analyte.

• Measurement of property is directly proportional to the concentration

i.e. CA α x; CA = kx where k is proportionality constant, A is the
analyte.

• The process of determining k is called CALIBRATION.

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Calculation and evaluation of results
• Calculation of results
• Analyte concentrations are computed with modern calculators and
computers.
• The computations are based on raw experimental data from
measurement, characteristics of measuring instruments and the
stoichiometry of the reaction.

• Evaluation of results: This involves estimating the reliability of results.

For the data to be valuable, some measure of uncertainties associated
with the computed results must be provided.

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Volumetric analysis
• Volumetric analysis is one of the most accurate and useful analytical
techniques for millimole amounts of analyte. It involves volume
measurement.
• General Principle
• Titration: A quantitative analysis, in which the amount of analyte is
determined from the quantity of a standard reagent consumed by it.
• Standard solution is a solution of known concentration.
• Titrimetric method is convenient, rapid and accurate. The accuracy is
limited by the degree of accuracy of the concentration of standard
solution.
Titration
• Titration is carried out by adding a reagent (solution) of known
concentration (titrant) from a burette into a known volume of the
analyte (test) solution in a flask until reaction is judged to be complete.
• The volume of the titrant required to just react completely with the
analyte is measured.
• The solution being titrated (analyte) is called TITRAND while the
solution employed in titrating is known as TITRANT.
• The amount of analyte in the sample solution can be determined from
the knowledge of the concentration of the standard solution and the
balanced equation of reaction between the analyte and the reagent is
known.

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Requirements of a reaction for titrimetric
analysis
• Reaction must be rapid or occur instantaneously i.e. X and Y must
react to form a product in the very shortest time.

• It must be stoichiometric. A well defined reaction between analyte and

titrant must be known. e.g. HCl + KOH → KCl + H2O

• There should be a marked change in some property of the solution

when reaction is complete. e.g. change in colour, electrical or physical
property e.g. pH.

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Requirements of a reaction for titrimetric
analysis
• Reaction must be specific and no side reactions.
• The end point of reaction should coincide with the equivalence point
or not too far from it.
• End point: The point at which the reaction is observed to be complete.
• The equivalence point: a point at which equivalent amount of titrant is
added to a test solution.

• Reaction should be quantitative i.e. equilibrium of reaction should be

far to the right so that a sufficiently sharp change will occur at the end
point to obtain the desired accuracy.

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Standard Solutions
• Standard solutions: These are solutions of known concentrations.
• The concentration of a standard solution can be established directly or
indirectly by:
• dissolving a known weighed quantity of a pure reagent and diluting it
to a known volume.
• titrating a solution containing a weighed quantity of a pure substance
with a reagent solution.
• A highly purified chemical compound known as primary standard is
essential for the preparation of standard solution to serve as reference
material.
• The process of determining the concentration of a standard solution
using a primary (1o) standard is called STANDARDIZATION.
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Characteristics of a primary standard
• Must have a high analytical purity (100% pure); (0.01-0.02% impurity is
tolerable).
• Readily available at modest cost.

• Must not contain hydrated water (to avoid changes in composition with
variations in humidity).

• Reasonably soluble in titration medium.

• Be stable to drying temperature and at room temperature.

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Characteristics of a primary standard contd.
• Have a high molar mass to minimize error in weighing.

• Reaction with other reagents must be stoichiometric

• Few substances meet these requirements, therefore, secondary (2o)

standards are used. These are less pure than primary standards and the
% purity must be established.

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Examples of standards for various types of
titration
• Acid / Base Titration
• (i) Acidimetric standard: Anhydrous Na2CO3, Borax(Na2B4O7.10H2O)
• (ii) Alkalimetric standard: Potassium phthalate KH(C8H4O4), Benzoic
acid, Oxalic acid (H2C2O4.2H2O).

• Precipitation titration: AgNO3, KBr

• Complexometric: EDTA(Na2), AgNO3

• Redox: K2Cr2O7, KIO3, I2

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End point determination
• Indicator: This is a compound with a physical property e.g. colour,
temp. etc that changes suddenly near the equivalence point. This
sudden change is due to the disappearance of the analyte or the
appearance of titrant at the equivalence point.

• Equivalence(eq) point: This is the point at which the quantity of

titrant added is the exact amount necessary for the reaction
stoichiometry with the titrand (analyte).
• **In titration, the eq. point cannot be determined experimentally, its
position is only estimated by observing some physical change related to
the condition of equivalence**

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End point determination contd.
• End point: This is noted by a sudden change in the physical or
chemical property of the solution.
• Instruments can be used to detect end points. E.g. colorimeters,
turbidimeters, temperature monitors, voltmeters, conductivity meters
etc.
• Difference between the end point and equivalence point is called
titration error (i.e. Et =Vep – Veq).
• Et = Titration error
• Vep= volume at end point
• Veq = volume at equivalence point

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Titrimetric methods
• Acid – Base: Many inorganic and organic compounds are acids and
bases. Acid and base are titrated with a standard solution of a strong
base or acid.

• End point can be monitored by an indicator following a colour change

with an indicator or change in pH with a pH meter.

• Weaker acids and bases can also be titrated. Organic acids and bases
are titrated in non aqueous solvent.
• Types : strong acid/strong base, strong acid/weak base, weak
base/strong acid and weak acid/weak base
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Titrimetric methods contd.
• Precipitation/Argenometric: Titrant forms an insoluble product with
the analyte e.g. Cl- + Ag+ → AgCl (white precipitate)
• change in (i) colour of indicator or (ii) Potential of solution can be
monitored for end point detection.

• Redox: Titration of an oxidizing agent with a reducing agent. End

point detection by indicators or electrometric.

• Complexometric: Titrant (complexing agent) forms a water soluble

complex with the analyte (metal ion).

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Review of Molarity Calculation
• Mole: A mole is the amount of substance containing the number of
particles as the number of carbon atoms in exactly 12 g of carbon -12
• The number of particles in 1 mole of a substance is the Avogadro’s
number.
• Avogadro’s constant = Number of particles /number of moles
• No of particles = no of moles
• Avogadro’s constant
• Avogadro’s constant = 6.023 x 1023
• Q1. Calculate the no. of moles in a sample with particle no 1.52 x 1022
• Moles = No of particles/Avogadro’s constsnt
• Moles = 1.52 x 1022 = 0.0252
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Review of molarity calculation contd.
• Q2. Determine the number of particles in 4.25 g of calcium(Ca)
• [Ca = 40]
• Solution: 1 mole of Ca = relative molecular mass of calcium =
Avogadro’s number of particles
• 1 mole of Ca = 40 g/Mol = 6.023 x 1023
• 40 g mole of Ca = 6.023 x1023 particles

• 1 g mole = 1 x 6.023 x1023 = 1.506 x 1022 particles

• 40
• 4.25 g mole = 1.506 x 1022 x 4.25 = 6.399 x 1022 particles
• 39
Review of molarity calculation contd.
• One mole is the molar mass of a substance expressed in grams
• Example: Calculate the number of grams in one mole of CuSO4.5H2O
• [Cu=64, S =32, O=16, H=1]
• Molar mass = 64 + 32 + (16 x 4) + 5(1 x 2) +16) = 64+32+64 +5(18) = 250
g/Mol
• One mole of CuSO4.5H2O = 250 g
• 0.5000 mole = 250 x 0.5 = 125 g
• 3 moles = 250 x 3 = 750 g
• Mole = mass (g) ; Mass = Mole x Molar mass
• Molar mass g/Mol (i)
Review of molarity calculation contd.
• Molar mass represents atomic or molecular weight of a substance.
• Atomic mass of sodium atom = 23
• Molecular mass of sodium chloride (NaCl) [Na =23, Cl = 35.5]
• = 23 + 35.5 = 58.5
• Moles NaCl = mass (g)
• 58.5 g/Mol
• Molecular mass of CuSO4.5H2O [Cu=64, S =32, O=16, H=1]
• = 64 + 32 + (16 x 4) + 5(1 x 2) +16) = 64+32+64 +5(18) = 250 g/Mol
• Moles CuSO4.5H2O = mass (g)
• 250 g/Mol
Review of molarity calculation contd.
• Moles of Na+ in NaCl = mass (g)
• 23 g/Mol
• Moles of Cl- in NaCl = mass (g)
• 35.5 g/Mol
• Moles of Cu2+ in CuSO4.5H2O [Cu = 64]
• = mass (g)
• 64 g/Mol
• Moles of K+ in K2SO4 = mass (g)
• [ K = 39] (39 x 2) g/Mol
• (there are 2 moles of K+ in K2SO4 hence the atomic mass is multiplied
by 2
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Practice Questions
• Q1. List the different classes of analytical chemistry
• Q2. Highlight the requirements of (i) titration reaction (ii) primary
standard.
• Q3. Digestion methods include------------- and -------------------
• Q4. What is the difference between end point and equivalence point?
• Q5. What are the steps involved in chemical analysis?
• Q6. What is the difference between plasma and serum?
• Q7.In analytical chemistry, -------- and ---------------information can be
obtained in an analysis.
• Q8. What class is a sample with costituents level of 0.01-1%?

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Practice Questions contd.

• Q1. Calculate the number of particles in 0.0315 moles of a sample .

• (Av. constant = 6.023 x 1023).

• Q2. Determine the number of particles in 4.65 g of iron metal (Fe =

56).

• Q3. Determine the no of moles (i) in 2.326 g of Na2SO4

• (ii) Na+ in the same mass of Na2SO4
• (Na =23, S=32, O= 16).
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