Chapter one

Introduction
 Definition
• Analytical chemistry is a branch of chemistry that focuses on the
identification, quantification, and characterization of chemical
substances.
• It involves developing, applying, and studying analytical methods
and techniques to obtain information about the composition and
properties of matter.
• The process of determining the type and amount of matter is called
Chemical analysis.
• Qualitative Analysis: provides information about the identity of an
atomic, molecular or biomolecular species.
• Quantitative Analysis: provides numerical information as to the
relative amounts of species.
• Structural analysis is the determination of the spatial arrangement of
atoms in an element or molecule or the identification of
characteristic groups of atoms (functional groups).
• An element, species or compound that is the subject of analysis is
known as an analyte.
• The remainder of the material or sample of which the analyte(s)
form(s) a part is known as the matrix.
• Analytical chemistry is all about Chemical Analysis.
 Roles of analytical chemistry
Analytical chemistry is applied throughout industry, medicine, and
all the sciences
Analytical chemistry plays a crucial role in various fields, including:
 Environmental Monitoring: Analyzing air, water, and soil samples
to assess pollution levels.
 Food Safety: Ensuring the quality and safety of food products
through chemical analysis.
 Pharmaceutical Industry: Developing and controlling the quality
of drugs and medicines.
 Clinical Chemistry: Diagnosing diseases and monitoring patient
health through blood and urine analysis.
 Forensic Science: Identifying and analyzing evidence in criminal
investigations.
Overall, Analytical Chemistry play central role in all other sciences.
The Vocabulary of Analytical Chemistry
1. Technique is any chemical or physical principle that we can
use to study an analyte.
2. Method is the application of a technique for a specific analyte
in a specific matrix.
3. Procedure is a set of written directions that tell us how to apply
a method to a particular sample, including information on how
to collect the sample, how to handle interferents, and how to
validate results.
4. Protocol is a set of stringent guidelines that specify a procedure
that an analyst must follow if an agency is to accept the results.
 Classification of Analytical Methods
Classical, wet chemical methods and modern instrumental methods
make up analytical chemistry.
In classical qualitative analysis, one or more chemical reagents are
added to the analyte. The identity of the analyte can be determined by
studying chemical reactions and their components. The added
reagents are selected to react selectively with one or a single class of
chemical compounds to produce a distinct reaction product.
In certain cases, the reaction product is a precipitate, a gas, or a
colored substance. Take, for example, copper(II), which reacts with
ammonia to form a deep blue copper-ammonia complex. Similarly,
dissolved lead(II) reacts with chromate-containing solutions to
produce yellow lead chromate. The same method can be used to
qualitatively test negative ions (anions) and positive ions (cations). A
common example is a reaction between carbonates and strong acids,
which results in the formation of carbon dioxide gas bubbles
For Quantitative Analysis: Gravimetric and volumetric analysis are
two types of traditional quantitative analysis. Both approaches rely on
lengthy chemical reactions involving the analyte and additional
reagents.
Gravimetric Analysis: A precipitate is formed when an excess of
added reagent reacts with the analyte. The filtrate is measured after it
has been washed, dried, and weighed. The concentration or quantity of
the assayed material in the analyte is calculated using its mass.
Volumetric Analysis: titrimetric analysis is another name for
volumetric analysis. From a buret, the reagent (the titrant) is
progressively or stepwise applied to the analyte. The secret to good
titrimetric analysis is to consider the titration's equivalence point (the
point at which the quantities of the two reacting species are
equivalent).
Instrumental Methods of Analysis: classified based on the property of
the analyte to be tested.
1. Spectroscopy is a technique for determining how molecules deal
with electromagnetic radiation.
2. Electroanalytical method: The potential (volts) and/or current
(amps) in an electrochemical cell containing the analyte are
measured.
3. Separation methods (chromatography, electrophoresis, and
field flow fractionation): are used to make content mixtures less
complicated.
 General Steps in Chemical Analysis

The analytical process often begins with a question that is not phrased
in terms of a chemical analysis. The question could be “Is this water
safe to drink?” or “Does emission testing of automobiles reduce air
pollution?” A scientist translates such questions into the need for
particular measurements. An analytical chemist then chooses or
invents a procedure to carry out those measurements. When the
analysis is complete, the analyst must translate the results into terms
that can be understood by others—preferably by the general public.
We can now summarize general steps in the analytical process:
Step 1 - Formulating the question: Translate general questions into
specific questions to be answered through chemical measurements.
Step 2 - Selecting analytical Procedure: Search the chemical literature
to find appropriate procedures or,
if necessary, devise new procedures to make the required measurements.
Step 3 – Sampling: Sampling is the process of selecting representative
material to analyze. If you begin with a poorly chosen sample or if the
sample changes between the time it is collected and the time it is
analyzed, the results are meaningless. “Garbage in, garbage out!”
Step 4 - Sample preparation: Sample preparation is the process of
converting a representative sample into a form suitable for chemical
analysis, which usually means dissolving the sample. Samples with a low
concentration of analyte may need to be concentrated prior to analysis. It
may be necessary to remove or mask species that interfere with the
chemical analysis.
Step 5 – Analysis: Measure the concentration of analyte in several identical aliquots
(portions). The purpose of replicate measurements (repeated measurements) is to
assess the variability (uncertainty) in the analysis and to guard against a gross error
in the analysis of a single aliquot. The uncertainty of a measurement is as important
as the measurement itself, because it tells us how reliable the measurement is. If
necessary, use different analytical methods on similar samples to make sure that all
methods give the same result and that the choice of analytical method is not biasing
the result. You may also wish to construct and analyze several different bulk
samples to see what variations arise from your sampling procedure.
Step 6 - Reporting and interpretation: Deliver a clearly written, complete report
of your results, highlighting any limitations that you attach to them. Your report
might be written to be read only by a specialist (such as your instructor) or it might
be written for a general audience (perhaps your mother). Be sure the report is
appropriate for its intended audience.
Step 7 - Drawing conclusions: Once a report is written, the analyst might not be
involved in what is done with the information, such as modifying the raw material
supply for a factory or creating new laws to regulate food additives. The more
clearly a report is written, the less likely it is to be misinterpreted by those who use
it.
Although there likely are as many descriptions of the analytical approach as
there are analytical chemistry, it is convenient to define it as the five-step
process as shown below
Methods of expressing the concentration of a solution

Quantitatively, the concentration of a solution describes the quantity of

a solute that is contained in a particular quantity of that solution.
Knowing the concentration of solutes is important in controlling the
stoichiometry of reactants for reactions that occur in solution, and are
critical for many aspects of our lives, from measuring the correct dose
of medicine to detecting chemical pollutants like lead and arsenic.

common ways of expressing solution concentration

Molarity is the number of moles of solute present in exactly 1 L

of solution.
 “Parts-per” concentration
One common method of expressing the concentration is based on the
quantity of solute in a fixed quantity of solution. The “quantities”
referred to here can be expressed in weight, in volume, or both (the
weight of solute in a given volume of solution.) In order to
distinguish among these posibilities, the abbreviations (w/w), (v/v)
and (w/v) are used. For example, a solution containing 5 g of NaCl
and 95 g of H2O is a 5% solution of NaCl.
Example: Find the percent (w/w) concentration of a solution
containing 4.5 g of sucrose in 90 mL of water.
Solution: 90 mL of water has a mass of 90 g, so the concentration
will be
.
x100% = 4.8% (w/w) sucrose
.
Percent means “parts per 100”; we can also use parts per thousand (ppt) for
expressing concentrations in grams of solute per kilogram of solution. For more
dilute solutions, parts per million (ppm) and parts per billion (109; ppb) are used.
Weight/volume and volume/volume basis
It is sometimes convenient to base concentration on a fixed volume,
either of the solution itself, or of the solvent alone. In most instances,
a “5% by volume” solution of a solid will mean 5 g of the solute
dissolved in 100 ml of the solvent.
Example: The minimum oxygen concentration needed to support
most fish is around 5 ppm (w/v). How many moles of O2 per liter of
water does this correspond to?
Solution: 5 ppm (w/v) means 5 grams of oxygen in one million mL
(1000 L) of water, or 5 mg per liter. This is equivalent to
.
= 1.6 × 10−4 mol
. /

If the solute is itself a liquid, volume/volume measure usually refers

to the volume of solute contained in a fixed volume of solution.
 Molarity: mole/volume basis
Molarity is the number of moles of solute present in exactly 1 L
of solution.

Example: How would you make 120 mL of a 0.10 M solution of

potassium hydroxide in water?
Solution: The amount of KOH required is (0.120 L) × (0.10 molL−1) =
0.012 mol. The molar mass of KOH is 56.1 g, so the weight of KOH
required is .012 mol × 56.1 gmol−1 = 0.67 g. We would dissolve this
weight of KOH in a volume of water that is less than 120 mL, and then
add sufficient water to bring the total volume up to 120 mL.
Example: Calculate the molarity of a 60% (w/w) solution of ethanol
(C2H5OH) in water whose density is 0.8937 g mL−1.
Solution: One liter of this solution has a mass of 893.7 g, of which
(0.60×893.7 g) = 536.2 g consists of ethanol. The molecular weight of
C2H5OH is 46.0, so the number of moles of ethanol present in one litre
(that is, the molarity) will be
.
= 11.6 mol/L
. /

Although molar concentration is widely employed, it suffers from one

serious defect: since volumes are temperature-dependent (substances
expand on heating), so are molarities; a 0.100 M solution at 0 ◦C will
have another concentration at 50 ◦C. For this reason, molarity is not
the preferred concentration measure in applications where physical
properties of solutions and the effect of temperature on these
properties is of importance.
Mole fraction: mole/mole basis
This is the most fundamental of all methods of concentration
measure, since it makes no assumptions at all about volumes. The
mole fraction of substance i in a mixture is defined as
𝑋=∑

𝑖𝑛 which 𝑛 is the number of moles of substance i, and the

summation is over all substances in the solution. Mole fractions run
from zero (substance not present) to unity (the pure substance).
Example: What fraction of the molecules in a 60% (w/w) solution of ethanol in
water consist of H2O?
Solution: From the previous example, we know that one liter of this solution
contains 536.2 g (11.6 mol) of C2H5OH. The number of moles of H2O is
(893.7−536.2) g÷18.0 g mol−1 = 19.9 mol. The mole fraction of water is thus
.
= 0.63
. .
 Molality: mole/weight basis
A molal solution contains one mole of solute per 1 kg of solvent.
Molality is a hybrid concentration unit, retaining the convenience of
mole measure for the solute, but expressing it in relation to a
temperature-independent mass rather than a volume. Molality, like
mole fraction, is used in applications dealing with certain physical
properties of solutions.
Example: Calculate the molality of a 60% (w/w) solution of ethanol
in water.
Solution: From the above problems, we know that one liter of this
solution contains 11.6 mol of ethanol in (893.7 − 536.2) = 3 57.5 g of
water. The molality of ethanol in the solution is therefore (11.6 mol)
÷ (0.3575 kg) = 32.4 mol kg−1
.
 Ion Concentrations in Solution
When ionic compounds dissolve in a solution, they break apart into
their ionic state. Cations and anions associate with the polar water
molecules. For example, ammonium dichromate (NH4)2Cr2O7 is a
strong electrolyte that dissociates in aqueous solution to give hydrated
NH4+ and Cr2O72− ions. If we consider this solution mathematically, we
can see that for every ammonium dichromate molecule that dissolves,
there will be three resulting ions that form (the two NH4+ ions and the
one Cr2O72− ion). This can also be thought of on a larger molar scale.
When 1 mole of (NH4)2Cr2O7 is dissolved, it results in 3 moles of ions
(1 mol of Cr2O72− anions and 2 mol of NH4+ cations) within the
solution.
To discuss the relationship between the concentration of a solution and
the resulting number of ions, the term equivalents is used. One
equivalent is defined as the amount of an ionic compound that
provides 1 mole of electrical charge (+ or -). It is calculated by
dividing the molarity of the solution by the total charge created in the
solution.
When we carry out a chemical reaction using a solution of a salt such
as ammonium dichromate, we need to know the concentration of each
ion present in the solution. If a solution contains 1.43 M (NH4)2Cr2O7 ,
then the concentration of Cr2O72− must also be 1.43 M because there is
one Cr2O72− ion per formula unit. However, there are two NH4+ ions
per formula unit, so the concentration of NH4+ ions is 2 × 1.43 M =
2.86 M. Because each formula unit of (NH4)2Cr2O7 produces three ions
when dissolved in water (2 NH4+ + 1 Cr2O72− ), the total concentration
of ions in the solution is 3 × 1.43 M = 4.29 M. The equivalent value of
(NH4)2Cr2O7 can then be calculated by dividing 1.43 M by 4.29 M,
yielding 0.333 equivalents. Thus, for (NH4)2Cr2O7 , dissolving 0.333
moles of the compound will yield 1 mole of ions in the solution.
 Preparation of Solution
to prepare standard solution, it is possible to start
with solid or liquid samples.
Preparation of Molar Solutions
If solute is a pure solid (or liquid) that will be
weighed,
grams to weigh = VL x M x [Link]
If solute is already dissolved, but the solution is
to be diluted,

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If concentration given in percentage and specific density
of the solute given, to calculate molarity,

Preparation of Normal Solutions

If solute is a pure solid (or liquid) that will be weighed,
grams to weigh = VL x M x EWsol
If solute is already dissolved, but the solution is to be diluted,

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