MT SEMESTER

ANALYTICAL CHEMISTRY
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PRELIMINARY REVIEWER
21 02
3. all zeros to the left of an implied decimal
point and to the right of a non-zero digits
Analytical Chemistry: are significant
Introduction 4. also, when they follow a unit, bar or
scientific notation
Analytical Chemistry 5. all zeros to the right of a decimal point and
 Branch of science that deals with the to the right of a non-zero digit are significant
separation, identification and determination
Types of Analytical Chemistry
of the components in a sample.
 Analytical chemistry is particularly 1. Qualitative Analysis
concerned with the questions of "what  Describing. Asks “what particular
chemicals are present, what are their sample”
characteristics and in what quantities are 2. Quantitative Analysis
they present?"  Deals with numbers. Asks “how
many drops..”
Accuracy and precision  Do not forget to write the unit of
measurement.
Accuracy- near to each other and near to the true
1. Qualitative Chemistry
value.
 What is in the sample?
2. Quantitative chemistry
 How much is in the sample?

Classification of Analysis
I. Based on sample size
II. Based on the extent of determination
Precision- near to each other, but not near to the III. Based on nature of methods
true value. IV. Based on materials used

I.Based on sample size

 Ultramicroanalysis - < 1 mg
 Microanalysis - 1 mg – 10 mg
 Semi-microanalysis- 10 mg – 100 mg
Significant figures  Macroanalysis - 100 mg – 1 g
1. all non-zero are significant
II.Based on the extent of determination
2. all zeros to the Left of the expressed
decimal point and to the right of a non-zero  Proximate analysis
digit are not significant  Total amount of a class or a group of
active plant principles in a given
sample.

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 IV. Oxidation-reduction
 Ultimate analysis
 Permanganate
 Amount of a specific constituent or a
 ceric sulfate
single chemical species present in
 iodometry
the sample
 iodimetry
III.Based on the nature of methods  bromine
 potassium iodate
A. Classical method
 diazotization assay with nitrite
 also known as general/ chemical/
wet/ stoichiometric method B. Gravimetric Analysis
B. Instrumental method
 Analysis involving the accurate
 based on specific physical or
measurement of weight of substance being
chemical properties of the analyte
determined which may be isolated in pure
 uses a device to do its work and yield
form or converted to another substance of
results
known composition by making it react
C. Miscellaneous or special method
quantitatively with another substance
 Involves the crude drugs and other
usually a precipitant.
natural products
 Used on molecular level. C. Special Methods
IV.Based on materials used  analysis which require a distinct type of
technique such as analysis of crude drugs,
 Chemical = titrimetric method
assay of fats and fixed oils, assay of volatile
 Physical = instruments and special apparata
oils and assay of alkaloids.
 Biological =use of microorganism and
animals and parts thereof. D. Physico-Chemical Methods
Types of Quantitative Analysis  Analysis based on some specific physical or
chemical property or properties of the
A. Volumetric Analysis
substance being analyzed with the use of
B. Gravimetric Analysis
instruments such as: spectrophotometer,
C. Special Methods
chromatograph units, polarographer,
D. Physico-Chemical Methods
polarimeter, flourometer.

A. Volumetric Analysis Specialized Analytical Methods and Equipment

 Distillation -determination of alcohol,
 analysis involving the measurement of
protein components, volatile component,
volume of a solution of known concentration
alkaloids
required to react with the desired
 Microscopy – physical characterization
constituent
 Polarimeter – rotatory power
 Divisions of volumetric analysis:  Refractometer – purity of substance
 Dessicator – moisture content
I. Neutralization
 Oven – moisture content
II. Precipitation  Moisture Balance – moisture content
III. Compleximetry

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  Chromatography – identity and quantity of • PbCl2 is soluble in hot water, and can
component therefore be differentiated easily.
 Spectroscopy – identity and purity
• Ammonia is used as a reagent to distinguish
 Polarography – quality and quantity of
between the other two. While AgCl dissolves
components
in ammonia (due to the formation of the
 Biological tests – determination of amounts
complex ion [Ag(NH3)2]+), Hg2Cl2 gives a black
required to produce the desired, definite
precipitate consisting of a mixture of chloro-
effect
mercuric amide and elemental mercury.
Furthermore, AgCl is reduced to silver under
Qualitative Inorganic Analysis
light, which gives samples a violet colour.
• Detecting Cations
• PbCl2 is far more soluble than the chlorides
– According to their properties, of the other two ions, especially in hot
cations are usually classified into water.
five groups.
• Therefore, HCl in concentrations which
– Each group has a common reagent completely precipitate Hg22+ and Ag+, may
which can be used to separate not be sufficient to do the same to Pb2+.
them from the solution. The
separation must be done in the • Higher concentrations of Cl- cannot be used
sequence specified, otherwise, for the aforementioned reasons.
some ions of 1st group can also
• Thus, a filtrate obtained after first group
react with 2nd group reagent, so
analysis of Pb2+ contains an appreciable
that the solution must not have any
concentration of this cation, enough to give
ions left from previous groups to
the test of the second group, viz. formation
obtain meaningful results.
of an insoluble sulfide.
1st analytical group of cations
• For this reason, Pb2+ is usually also included
• 1st analytical group of cations consists of in the 2nd analytical group.
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 2nd analytical group of cations
must not be used, because it forms a soluble
• The 2nd analytical group of cations consists
complex ion ([PbCl4]2-) with Pb2+.
of ions that forms acid-insoluble sulfides.
Consequently the Pb2+ ion would go
undetected. • Cations in the 2nd group include: Cd2+, Bi3+,
Cu2+, As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ and
• The most important cations in 1st group are
Hg2+.
Ag+, Hg22+, and Pb2+. The chlorides of these
elements cannot be distinguished from each • Pb2+ is usually also included here in addition
other by their colour - they are all white solid to the first group.
compounds.
• The reagent can be any substance that gives
S2- ions in such solutions; most commonly

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 used are H2S (at 0.2-0.3 M), CH3CSNH2 • The reagents are similar to these of the 2nd
(Thioacetamide/ATK)(at 0.3-0.6 M). group, but separation is conducted at pH of
8–9. Occasionally, a buffer solution is used to
• The test with the sulfide ion must be
ensure this pH.
conducted in the presence of dilute HCl.
• Cations in the 3rd group are, among others:
• Its purpose is to keep the sulfide ion
Zn2+, Ni2+, Co2+, Mn2+, Fe2+, Fe3+, Al3+, and Cr3+.
concentration at a required minimum, so as
to allow the precipitation of 2nd group
cations alone.
4th analytical group of cations
• If dilute acid is not used, the early
• Ions in 4th analytical group of cations form
precipitation of 4th group cations (if present
carbonates that are insoluble in water.
in solution) may occur, thus leading to
misleading results. • The reagent usually used is (NH4)2CO3 (at
around 0.2 M), the pH should be neutral or
• Acids beside HCl are rarely used. Sulfuric acid
slightly basic.
may lead to the precipitation of the 4th
group cations, while nitric acid directly • Caution should be taken to properly
reacts with the sulfide ion (reagent), forming separate all lower analytical groups
colloidal sulfur. beforehand, as many of cations in previous
groups also form insoluble carbonates.
• The precipitates of these cations are almost
indistinguishable, except for CdS which is • Most important ions in the 4th group: Ba2+,
yellow. Ca2+, and Sr2+. After separation, the easiest
way to distinguish these ions is by testing
• All the precipitates, except for HgS, are
flame colour: barium gives a yellow-green
soluble in dilute mineral acids. HgS is soluble
flame, calcium orange-red and strontium
only in aqua regia, which can be used to
deep red.
separate it from the rest.

• The action of ammonia is also useful in

differentiating the cations. 5th analytical group of cations
• CuS dissolves in ammonia forming an intense • Cations which are left after carefully
blue solution, while CdS dissolves forming a separating previous groups are considered
colourless solution. to be in the fifth analytical group.
• The sulfides of As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ • The most important ones are Mg2+, Li+, Na+,
are soluble in yellow ammonium sulfide, K+ and NH4+.
where they form polysulfide complexes.
Qualitative Inorganic Analysis
• Detecting Anions
3rd analytical group of cations
– Halides are precipitated by silver
• 3rd analytical group of cations includes ions nitrate; they can be further
that form sulfides which are insoluble in
identified by color.
basic solution.

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 – Sulfates can be precipitated by
barium chloride.
– Nitrates can be reduced to
ammonia.
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.

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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