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

• Precision
Accuracy and Precision
Significant figures
 Types of Analytical Chemistry
• Qualitative Analysis

• Quantitative Analysis

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1. Qualitative Chemistry

• What is in the sample?

• 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 :
III. Based on the nature of methods
B. Instrumental method
– more accurate
– based on specific physical or chemical
properties of the analyte
– Examples:
III. Based on the nature of methods
C. Miscellaneous or special method
– Involves the crude drugs and other natural
products
– Examples:
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
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

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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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