Analytical

Chemistry:
Introduction
 Course Syllabus
• Course Title: Analytical Chemistry
• Course Units: 5 units (3 units lecture, 2 units
laboratory)
• Course Objectives: At the end of the course, the
students should be able to explain how the
composition of a sample is determined, plan and
interpret experimental work in both qualitative and
quantitative chemistry and can discuss the application
of the two analytical techniques.

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Course Outline

• Analytical Measurements
• Solutions
• Chemical Equilibrium
• Gravimetry
• Titrimetry
• Acids, Bases and Salts
• Acid-Base Titration
• Acid and Bases in Non-Aqueous Solvents

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Course Outline
• Complex Ions
• Oxidation Reduction Equilibrium
• Oxidation Reduction Titration
• Precipitation Equilibria and Titration
• Potentiometry
• Electrolysis
• Spectrophotometry
• Spectroscopy
• Chromatography

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Analytical Chemistry

• Branch of science that deals with the separation, identification and

determination of the components in a sample

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Analytical Chemistry

• Analytical chemistry is particularly concerned with the questions of

"what chemicals are present, what are their characteristics and in
what quantities are they present?"

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Analytical Chemistry

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Accuracy and precision

• Accuracy - pertains to agreement of an experimental

results with true value

• Precision - is the measure of reproducibility of data

within a series of results.
•
Accuracy and Precision
Significant figures
Types of Analytical Chemistry

• Qualitative Analysis - is a method of analytical chemistry

which seeks to find elemental composition of inorganic
compounds and the functional group of organic
compounds.

• Quantitative Analysis- in analytical chemistry, the

measurements of quantities of substances produced in
reactions rather than simply noting the nature of the
reactions

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 1. Qualitative Chemistry

• What is in the sample?

• Identification
• Composition determination
• Ascertainment of impurities- ascertainment means to discover
through experimentation or examination
 2. Quantitative chemistry
• How much is in the sample?

determination of the proportion of components in a substance (we

measure the substances- quantity)
Classification of Analysis

I. Based on sample size

II. Based on the extent of determination
III. Based on nature of methods
IV. Based on materials used
 I. Based on sample size

• Ultramicroanalysis < 1 mg
• Microanalysis 1 mg – 10 mg
• Semi-microanalysis 10 mg – 100 mg
• Macroanalysis 100 mg – 1 g
II. Based on the extent of determination

• Proximate analysis
total amount of a class or a group of active plant principles in a
given sample.

• Ultimate analysis
Amount of a specific constituent or a single chemical species
present in the sample
III. Based on the nature of methods

A. Classical method
B. Instrumental method
C. Miscellaneous or special method
III. Based on the nature of methods

A. Classical method
• also known as general/ chemical/ wet/
stoichiometric method
• example : titrimetric analysis; gravimetric analysis
III. Based on the nature of methods

B. Instrumental method
• more accurate
• based on specific physical or chemical
properties of the analyte
• Examples: Spectrometry; polarimetry;
chromatography
III. Based on the nature of methods

C. Miscellaneous or special method

• Involves the crude drugs and other natural
products
• Examples: Acid value; Ash content; Water
content
•
IV. Based on materials used

• Chemical = titrimetric method

• Physical = instruments and special apparata
• Biological = use of microorganism and animals and parts thereof
Types of Quantitative Analysis

A. Volumetric Analysis
B. Gravimetric Analysis
C. Special Methods
D. Physico-Chemical Methods
Types of Quantitative Analysis

A. Volumetric Analysis
analysis involving the measurement of volume of a
solution of known concentration required to react with the desired
constituent.
 Types of Quantitative Analysis
Divisions of volumetric analysis:
I. Neutralization
II. Precipitation
III. Compleximetry
IV. Oxidation-reduction
permanganate
ceric sulfate
iodometry
iodimetry
bromine
potassium iodate
diazotization assay with nitrite

Neutralization- chemical reaction where a base and acid react to form a salt.
Precipitation- supernatant and precipitate (a process in which a solid is separated from a
suspension or solution)
Compleximetry - a form of volumetric analysis in which the formation of a colored
complex is used to indicate the end point of a titration
Types of Quantitative Analysis

B. Gravimetric Analysis
Analysis involving the accurate measurement
of weight of substance being determined which
may be isolated in pure form or converted to
another substance of known composition by
making it react quantitatively with another
substance usually a precipitant.
 Types of Quantitative Analysis
C. Special Methods
analysis which require a distinct type of technique
such as analysis of crude drugs, assay of fats and fixed
oils, assay of volatile oils and assay of alkaloids.
Types of Quantitative Analysis

D. Physico-Chemical Methods
Analysis based on some specific physical or
chemical property or properties of the
substance being analyzed with the use of
instruments such as: spectrophotometer,
chromatograph units, polarographer, polarimeter,
flourometer.
Specialized Analytical Methods and Equipment

• Distillation -determination of alcohol, protein components, volatile

component, alkaloids
• Microscopy – physical characterization
• Polarimeter – rotatory power
• Refractometer – purity of substance
• Dessicator – moisture content
Specialized Analytical Methods and Equipment

• Oven – moisture content

• Moisture Balance – moisture content
• Chromatography – identity and quantity of component
• Spectroscopy – identity and purity
• Polarography – quality and quantity of components
• Biological tests – determination of amounts required to produce the
desired, definite effect
Qualitative Inorganic Analysis

• Detecting Cations
• According to their properties, cations are usually classified into five groups.
• Each group has a common reagent which can be used to separate them from
the solution. The separation must be done in the sequence specified,
otherwise, some ions of 1st group can also react with 2nd group reagent, so
that the solution must not have any ions left from previous groups to obtain
meaningful results.

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Activity

•Create a schematic diagram

on the separation of cations
and anions using the
qualitative analysis.

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1st analytical group of cations

• 1st analytical group of cations consists of ions that form insoluble

chlorides.
• As such, the group reagent to separate them is hydrochloric acid,
usually used at a concentration of 1–2 M. Concentrated HCl must not
be used, because it forms a soluble complex ion ([PbCl4]2-) with Pb2+.
Consequently the Pb2+ ion would go undetected.

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1st analytical group of cations

• The most important cations in 1st group are Ag+, Hg22+, and Pb2+. The
chlorides of these elements cannot be distinguished from each other
by their colour - they are all white solid compounds.
• PbCl2 is soluble in hot water, and can therefore be differentiated
easily.

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1st analytical group of cations

• Ammonia is used as a reagent to distinguish between the other two.

While AgCl dissolves in ammonia (due to the formation of the
complex ion [Ag(NH3)2]+), Hg2Cl2 gives a black precipitate consisting of
a mixture of chloro-mercuric amide and elemental mercury.
Furthermore, AgCl is reduced to silver under light, which gives
samples a violet colour.

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1st analytical group of cations

• PbCl2 is far more soluble than the chlorides of the other two
ions, especially in hot water.
• Therefore, HCl in concentrations which completely
precipitate Hg22+ and Ag+, may not be sufficient to do the
same to Pb2+.
• Higher concentrations of Cl- cannot be used for the
aforementioned reasons.
• Thus, a filtrate obtained after first group analysis of Pb2+
contains an appreciable concentration of this cation, enough
to give the test of the second group, viz. formation of an
insoluble sulfide.
• For this reason, Pb2+ is usually also included in the 2nd
analytical group.
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2nd analytical group of cations

• The 2nd analytical group of cations consists of ions that forms acid-
insoluble sulfides.
• Cations in the 2nd group include: Cd2+, Bi3+, Cu2+, As3+, As5+, Sb3+, Sb5+,
Sn2+, Sn4+ and Hg2+.
• Pb2+ is usually also included here in addition to the first group.

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2nd analytical group of cations

• The reagent can be any substance that gives S2- ions

in such solutions; most commonly used are H2S (at
0.2-0.3 M), CH3CSNH2 (Thioacetamide/ATK)(at 0.3-
0.6 M).
• The test with the sulfide ion must be conducted in
the presence of dilute HCl.
• Its purpose is to keep the sulfide ion concentration
at a required minimum, so as to allow the
precipitation of 2nd group cations alone.

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2nd analytical group of cations

• If dilute acid is not used, the early precipitation of 4th group cations
(if present in solution) may occur, thus leading to misleading results.
• Acids beside HCl are rarely used. Sulfuric acid may lead to the
precipitation of the 4th group cations, while nitric acid directly reacts
with the sulfide ion (reagent), forming colloidal sulfur.

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2nd analytical group of cations

• The precipitates of these cations are almost indistinguishable, except

for CdS which is yellow.
• All the precipitates, except for HgS, are soluble in dilute mineral
acids. HgS is soluble only in aqua regia, which can be used to
separate it from the rest.

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2nd analytical group of cations

• The action of ammonia is also useful in differentiating the cations.

• CuS dissolves in ammonia forming an intense blue solution, while CdS
dissolves forming a colourless solution.
• The sulfides of As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ are soluble in yellow
ammonium sulfide, where they form polysulfide complexes.

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3rd analytical group of cations

• 3rd analytical group of cations includes ions that form sulfides which
are insoluble in basic solution.
• The reagents are similar to these of the 2nd group, but separation is
conducted at pH of 8–9. Occasionally, a buffer solution is used to
ensure this pH.
• Cations in the 3rd group are, among others: Zn2+, Ni2+, Co2+, Mn2+,
Fe2+, Fe3+, Al3+, and Cr3+.

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 4th analytical group of cations
• Ions in 4th analytical group of cations form carbonates that are insoluble
in water.
• The reagent usually used is (NH4)2CO3 (at around 0.2 M), the pH should be
neutral or slightly basic.
• Caution should be taken to properly separate all lower analytical groups
beforehand, as many of cations in previous groups also form insoluble
carbonates.

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4th analytical group of cations

• Most important ions in the 4th group: Ba2+, Ca2+, and Sr2+. After
separation, the easiest way to distinguish these ions is by testing
flame colour: barium gives a yellow-green flame, calcium orange-red
and strontium deep red.

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5th analytical group of cations

• Cations which are left after carefully separating previous groups are
considered to be in the fifth analytical group.
• The most important ones are Mg2+, Li+, Na+, K+ and NH4+.

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Qualitative Inorganic Analysis

• Detecting Anions
• Halides are precipitated by silver nitrate; they can be further identified by
color.
• Sulfates can be precipitated by barium chloride.
• Nitrates can be reduced to ammonia.

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1st analytical group of anions

• The 1st group of anions consist of CO32-, HCO3-, CH3COO-, S2-, SO32-,
S2O32- and NO2-.
• The group reagent for Group 1 anion is HCL(dil) or H2SO4.

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Modern techniques

• Qualitative inorganic analysis is now used only as a pedagogical tool.

• Modern techniques such as atomic absorption spectroscopy and ICP-
MS (Inductively coupled plasma mass spectrometry) are able to
quickly detect the presence and concentrations of elements using a
very small amount of sample.

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Study smart.
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