UNIT- 1

INTRODUCTION
1.1. What is Analytical Chemistry?
Analytical chemistry is a measurement science consisting of a set of powerful
ideas and methods that are useful in all fields of science and medicine.
It is “the science of inventing and applying the concepts, principles, and
strategies for measuring the characteristics of chemical systems and species.”
It deals with methods for determining the chemical composition of samples.
Analytical chemists typically operate at the extreme edges of analysis,
extending and improving the ability of all chemists to make meaningful
measurements on:
❖ smaller samples,
❖ More complex samples,
❖ species present at lower concentrations
❖ Within shorter time scales.
The techniques of this science are used to identify the substances which may be
present in a material and determine the exact amounts of the identified
substances
❖ It is concerned with the chemical characterization of matter and the answer to
two important questions:
✓ Qualitative (“what is it?“)
✓ Quantitative (“how much is it ?“)
Qualitative: provides information about the identity of an atomic, molecular or
biomolecular species
➢ Establishes the chemical identity of the species in the sample.
Quantitative: provides numerical information as to the relative amounts of
species.
Determines the relative amounts of the analyte, in numerical terms
 1.2. Roles of analytical chemistry
❑ Analytical chemistry plays an important role in nearly all aspects of
chemistry, for example agricultural, clinical, environmental and
pharmaceutical chemistry
❑ Analytical chemistry is applied throughout industry, medicine, and all
sciences.
❑ Analytical chemists work to improve the reliability of existing techniques to
meet the demands of for better chemical measurements which arise
constantly in our society
1.3. Classification of analytical chemistry
Gravimetric Methods: Determine the mass of the analyte or some
compound chemically related to it.
Volumetric Methods: The volume of a solution containing sufficient reagent to
react completely with the analyte is measured.
Spectroscopic Methods: Based on measurement of the interaction between
electromagnetic radiation and analyte
Chromatographic Methods: Separation techniques and quantification is based
on polarity.
Electro analytical Methods: Involve the measurement of electrical properties
such as voltage, current, resistance and quantity of electrical charge.
1.4. Methods of chemical analysis
Chemical analysis: determination of the physical properties or chemical
composition of samples of matter.
❖ A large body of systematic procedures intended for these purposes
❖ It is divided into two categories depending on the manner in which the
assays are performed.
i. Classical analysis: also termed as wet chemical analysis, consists of those
analytical techniques that use no mechanical or electronic instruments other
than a balance.
❑ The method usually relies on chemical reactions between the analyte and a
reagent that is added to the analyte.
ii. Instrumental analysis: involves the use of an instrument, other than a
balance, to perform the analysis.
➢ In some cases, the instrument is used to characterize a chemical reaction
between the analyte and an added reagent; in others, it is used to measure a
property of the analyte.
➢ Both classical and instrumental quantitative analyses can be divided into
gravimetric and volumetric analyses.
a. Gravimetric analysis: relies on a critical mass measurement
b. Volumetric analysis: relies on a critical volume measurement.
Eg. In titration usually a liquid solution of a chemical reagent (a titrant) of
known concentration is placed in a burette.
o The titrant is added gradually, in a procedure termed a titration, to the
analyte until the chemical reaction is completed.
o The added titrant volume that is just sufficient to react with all of the analyte
is the equivalence point and can be used to calculate the amount or
concentration of the analyte
➢ Instrumental analysis is subdivided into categories on the basis of the type
of instrumentation employed.
Separation Techniques
✓ Gas chromatography
✓ High performance liquid chromatography
✓ Ion chromatography
✓ Super critical fluid chromatography
✓ Capillary electrophoresis
✓ Planar chromatography
Spectroscopic techniques
✓ Infrared spectrometry (IR) ✓ Inductively coupled plasma MS
✓ Raman spectrometry ✓ Atomic fluorescence spectrometry
✓ Nuclear magnetic resonance ✓ Ultraviolet/visible spectrometry
✓ Atomic absorption spectrometry (UV) etc.
✓ Inductively coupled plasma
atomic emission spectrometry
Mass Spectrometry ✓ HPLC MS
✓ Electron ionization MS Electrochemical techniques
✓ Chemical ionization MS ✓ Amperometric technique
✓ High resolution MS ✓ Voltammetric techniques
✓ Gas chromatography MS ✓ Potentiometric techniques
✓ Fast atom bombardment MS ✓ Conductiometric techniques
1.5. Steps in quantitative chemical analysis
 1. Choosing a Method:
The first step is the selection of a method.
Factors need to be considered in the selection process are:
➢ Accuracy required
➢ Cost of analysis (total investment)
➢ Number of sample to be analyzed
➢ Time required for analysis
➢ Skill required
➢ Complexity of the sample
➢ Number of components in the sample
2. Acquiring the Sample:
➢ Sampling is the process of collecting a small mass of a material whose
composition accurately represents the bulk of the material from which it
was taken.
➢ To produce meaningful information, an analysis must be performed on a
representative sample.
➢ For large heterogeneous sample, great effort is required to get a
representative sample.
➢ Sometime proper sampling is the most difficult step in an analysis and the
source of greatest error.
The final result of an analysis will never be any more reliable than the reliability
of the sampling.
3. Processing the sample: The third step in an analysis is to process the
sample.
➢ Sometimes no sample processing is required prior to the measurement step
such as pH of water sample can be measured directly.
➢ Under most circumstances, sample need to be processed in a variety of
different ways.
i. Preparing a Laboratory Sample
➢ A solid Laboratory sample is ground to decrease particle size, mixed to
ensure homogeneity, and stored for various lengths of time before analysis
begins
ii. Defining Replicate Samples
➢ Replication improves the quality of the results and provide a measure of
reliability.
iii. Preparing Solutions: Physical and Chemical Changes
➢ Performed on solutions of the solutions of the sample made with a suitable
solvent.
4. Eliminating Interferences:
➢ Need to eliminate substances from the sample that may interfere with the
measurement step.
➢ Few chemical or physical properties of importance in chemical analysis
are unique to a single chemical species.
➢ Species other than the analyte that affect the final measurement are
called interferences.
5. Calibration and Measurement:
➢ Analytical results depend on a final measurement of a physical or
chemical property (X).
➢ Ideally, the measurement of the property is directly proportional to the
concentration (CA).
▪ CA = kX
Where, k is proportionality constant.
➢ The process of determining k is an important step in most analyses.
This step is called a calibration.
6. Calculating Results: Analyte concentrations from experimental data need to
be calculated.
➢ These computations are based on the raw experimental data collected in
the measurement steps, the characteristics of the measurement
instruments and the stoichiometry of the analytical reaction.
7. Evaluating Results by Estimating Their Reliability:
➢ Analytical results are incomplete without an estimate of their reliability.
➢ Some measure of the uncertainties associated with computed results need
to be provided.
Systematic Analysis of Ions
1.1. Systematic Classification of Cat Ions and Anions into Analytical Groups
In systematic analysis ions are separated form complex mixtures in to groups,
advantage being taken of the sample reaction of the ion within a group with reagent
called the group reagent.
1.1.1. Classification of Cat ions
❖ Cat ions are positively charged ions. According to their properties, cations are
usually classified into six analytical groups. Such as group I, II, III, IV, V and VI
❖ Each group has a common reagent which can be used to separate them from the
solution. To obtain meaningful results, the separation must be done in the
sequence specified below. Cationic analysis is based on the solubility products of
the ions.
❖ As the cation gains its optimum concentration needed for precipitation it
precipitates and hence allowing us to detect it.
Requirements of a substance as a group reagent
1. It must precipitate cat ions completely ( or practically)
2. The resulting precipitate must dissolve in acids so that analysis can be continued.
3. The excess reagent added must not interfere with detection of the ions left in the
solution.
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 below. Otherwise, for example
some ions of the 1st group can also react with 2nd group reagent, so that the solution must
not have any ion left from previous groups to obtain meaningful results.
Table1.2. Classification of Cat ions
Group Cat ions Group
number Reagent Properties of Compound
I + 2+
Ag , Pb , Hg2 +2
3F HCl ✓ Chlorides are insoluble in H2O and
dilute acids
II 2+ 2+ 2+
Ca , Sr , Ba , Pb 2+
3F H2SO4 ✓ Sulfates are insoluble in H2O and
dilute acids
III 3+ 2+ 2+
Al , Zn , Sn , Sn 4+
3F NaOH ✓ Hydroxides are insoluble in excess
(excess) NaOH
IV 3+ 3+ 2+ 3+
Bi , Cr , Fe , Fe , mg , 6F NH32+
✓ Hydroxides are insoluble in excess
Mn2+ NaOH and NH3
V 2+ 2+ 2+
Cd , Co , Cu , Hg , Ni 2+ 2+
6F NH3 ✓ -Hydroxides are insoluble in excess
(Excess) NaOH but soluble in NH3
VI + +
K , Na , NH4 +
No Group ✓ Chlorides, sulfates and hydroxides
reagent are soluble in water.
1st Analytical Group of Cations
❖ 1st analytical group of cations consists of ions that are colourless in aqueous
solutions and 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. 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.
❖ 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.
❖ AgCl is reduced to Ag under light, which gives samples a violet colour.
❖ PbCl2 is far more soluble than the chlorides of the other two ions, especially in hot
water. Therefore, HCl in concentrations which completely precipitate Hg2+2 and
Ag+ may no be sufficient to do the same to Pb2+.
❖ Higher concentrations of Cl− cannot be used for the before mentioned reasons. 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.
❖ This group can be determined by adding the salt in water and then adding dilute
hydrochloric acid. A white precipitate is formed, to which ammonium
hydroxide is then added. If the precipitate is insoluble, then Pb2+ is present; if the
precipitate is soluble, then Ag+ is present, and if the white precipitate turns
black, then Hg2+2 is present.
Pb2+ + 2 KI → PbI2 + 2 K+
Pb2+ + K2CrO4 → PbCrO4 + 2 K+
Confirmation test for Silver:
Ag+ + KI → AgI + K+
2Ag+ + K2CrO4 → Ag2CrO4 + 2 K+
Confirmation test for dimeric mercury ion:
Hg2+2 + 2 KI → Hg2I2 + 2 K+
2 Hg2+2 + 2 NaOH → 2 Hg2O + 2 Na+ + H2O
2nd Analytical Group of Cat ions
❖ All of them are colourless in aquoes solutions. These ions form sulfates,
carbonates and a number of other salts with various anions which are slightly
soluble in water.
❖ Chlorides of group II cations are water soluble. Pb2+ partially precipitated with 1st
group as PbCl2 and the residue is precipitated as PbSO4 with 2nd group.
❖
To separate Pb2+ ions from Ca2+, Sr2+, and Ba2+ sulfates, PbSO4 are soluble in
alkaline solution on heating. PbSO4 + 4OH- → [Pb(OH)4]2- + SO42-
❖ To dissolve the sulfates of Ca2+, Sr2+, and Ba2+ they must 1st be converted into the
corresponding carbonates by the action of Na2CO3.
❖ Ba2+ is identified by the formation of BaCrO4 ppt when K2CrO4 is added to the
solution.
❖ Sr2+ ion with CrO42- ion is also gives a yellow ppt of SrCrO4, which differs from
BaCrO4 only by being soluble in acetic acid (CH3COOH).
Confirmation test:
✓ The most important ions in the 2nd group are Ba2+, Ca2+, and Sr2+.
✓ After separation, the easiest way to distinguish between these ions is by testing flame
colour:
• Ba2+ gives a yellow-green flame,
• Ca2+ gives orange-red, and
• Sr2+ , deep red.
3rd Analytical Group of Cations.
❖ The cations of this group differ from those of group I and II by forming water
soluble chlorides and sulfates.
❖ Oxides and hydroxides of Al3+, Zn2+ and Sn2+ are amphoteric in nature and
hydrated oxide of Sn4+ is acidic.
❖ The cations from group III are easily detected in the solution (Zn) and in the ppt
(Sn and Al) after dissolution using confirmatory test.
❖ The group is determined by making a solution of the salt in water and
adding ammonium chloride and ammonium hydroxide.
❖ Ammonium chloride is added to ensure low concentration of hydroxide ions.
✓ The formation of a gelatinous white precipitate indicates Al3+.
✓ Hydrogen sulphide is passed through the supernatent liquid. If a white
precipitate forms, Zinc is present.
Sn + H2S → SnS (brown) + 2H+
2+

Sn4+ + 2H2S →SnS2 (yellow) + 4H+

4th Analytical Group of Cations
❖ The fourth group of cations include Bi2+, Fe2+, Fe3+, Cr3+ , Mg2+ and Mn2+ form
water soluble chlorides and sulfates. These cations do not form complex ammines
and hydroxo complexes they can be precipitated from their solutions as
corresponding hydroxides by the action of aqueous NH3.
❖ But the precipitation of Mn(OH)2 in the presence of ammonium salts is always
incomplete. To achieve complete precipitation Mn2+ is oxidized into Mn4+, which
is precipitated as MnO(OH)2.
Confirmation test for bismuth:
Bi3+ + 3 KI (in excess) → BiI3 + 3 K+
BiI3 + KI → K[BiI4]
Bi3+ + H2O (in excess) → BiO+ + 2 H+
With NaOH, KOH or NH3, Bi3+ gives white precipitate of Bi(OH)3
❖ The group is determined by making a solution of the salt in water and
adding ammonium chloride and ammonium hydroxide. Ammonium chloride is
added to ensure low concentration of hydroxide ions.
✓ The formation of a reddish brown precipitate indicates Fe3+;
✓ a green precipitate indicates Cr3+ or Fe2+.
✓ These last two are distinguished by adding sodium hydroxide in excess to
the green precipitate.
✓ If the precipitate dissolves, Fe2+ is indicated; otherwise, Cr3+ is present.
❖ Manganese salts are faint pink or colourless. The precipitate, washed in water is
reacted with extremely dilute hydrochloric acid. This precipitates nickel salts, if
any. The supernatent liquid is filtered and reacted with excess of Sodium
Hydroxide. This precipitates any Manganese salts.
❖ Mg2+ ions are distinguished by flame color and gives bright white flame.
5th Analytical Group of Cations
❖ The 5th group of cations include: Cd2+, Co2+, Cu2+, Hg2+ and Ni2+. All these ions
produce water soluble chlorides and sulfates.
❖ Their hydroxides and oxides are insoluble in alkalis, but readily soluble in aqueous
NH3 solutions to from the ammine complexes.
❖ If H2S is added to the solution containing Cd, yellow ppt is formed (CdS).
❖ All the precipitates, except for HgS, are soluble in dilute nitric acid. HgS is
soluble only in aqua regia, which can be used to separate it from the rest.
❖ The action of ammonia is also useful in differentiating the cations.
✓ CuS dissolves in ammonia forming an intense blue solution, whereas
✓ CdS dissolves forming a colourless solution.
Confirmation test for copper:
2 Cu2+ + K4[Fe(CN)6] + CH3COOH → Cu2[Fe(CN)6] + 4 K+ (reddish brown or
black precipitate )
Cu2+ + 2 NaOH → Cu(OH)2 + 2 Na+ ( Blue ppt)
Cu(OH)2 → CuO + H2O (endothermic)
Confirmation test for mercury:
Hg2+ + 2 KI (in excess) → HgI2 + 2 K+
HgI2 + 2 KI → K2[HgI4] (red precipitate dissolves)
2 Hg2+ + SnCl2 → 2 Hg + SnCl4 (white precipitate turns gray)
❖ Nikel and Cobalt with NaOH or KOH, give
✓ greenish ppt of Ni(OH)2 and
✓ pink ppt of Co(OH)2 respectively.
th
6 Analytical Group of Cations
❖ Most of the salts formed by these ions are readily soluble in water. Group VI
Cations are not
precipitated by the group reagents for the other groups and remain in the solution
when cations of other groups are separated as in soluble or slightly soluble salts or
hydroxides.
❖ They are detected in systematic analysis left after carefully separating previous
groups.
Confirmation test
❖ NH4+ gives a reddish-brown colored precipitate with Nessler's reagent is known
as potassium tetraiodomercurate(II), (K2HgI4).
NH4+ + 2[HgI4]2− + 4OH− → HgO·Hg(NH2)I ↓ + 7I− + 3H2O
❖ The rest of the ions are distinguished by flame colour:
✓ Li+ gives a red flame,
✓ Na+ gives bright yellow (even in trace amounts),
✓ K+ gives violet flame colour.
1.1.2. Classification of Anions
❖ The anions are separated into five groups and their classification is based on the
different solubility’s of Ca, Ba, Cd and Ag salts in water.
Table1.3. Classification of Anions
Group Anions Group Reagent Properties of compounds
number
I SO32-, CO32-, PO43-, C2O42-, F-. 2F Ca(AC)2 ✓ Ca salts are water insoluble but are soluble in
HAC,exceptCaC2O4 and CaF2
II SO42-, CrO42- 1F Ba(AC)2 ✓ Ba salts are water insoluble, chromate is soluble
and sulfate is insoluble in HAC.
III S2-,CN- 1F Cd(AC)2 ✓ Cd salts are water insoluble
IV Cl-, Br-, I- , SCN- Sat.AgAC(0.1F) ✓ Ag salts are insoluble in water and dil.HNO3.
V ClO3-, NO3-, NO2- No group reagent ✓ Ca, Ba, Cd and Ag salts are water soluble.
1st Analytical Group of Anions
❖ The 1st group of anions consists of SO32-, CO32-, PO43-, C2O42-, F-. The reagents
for Group 1 anions are dilute hydrochloric acid (HCl) or dilute sulfuric acid
(H2SO4).
❖ Sulfites produce SO2 gas, which smells of burning sulfur, when treated with dilute
acid. They turn acidified K2Cr2O7 from orange to green.
❖ Carbonates give a brisk effervescence with dilute H2SO4 due to the release of CO2,
a colorless gas which turns limewater milky due to formation of CaCO3
❖ The milkiness disappears on passing the lime water through an excess of the gas,
due to formation of Ca(HCO3)2.
❖ Carbon Monoxide in the mixture will burn with a blue flame to produce carbon
dioxide. The two gases are confirmed in this way, confirming the presence of the
oxalate ion.
❖ Acetates give the vinegar-like smell of CH3COOH when treated with dilute
H2SO4.
❖ A blood red colouration is produced upon addition of yellow FeCl3, due to
formation of iron(III) acetate.
❖ Sulfides give the rotten egg smell of H2S when treated with dilute H2SO4.
❖ A small amount of the sample is acidified with Concentrated Nitric Acid to which
a little ammonium molybdate is added.
❖ The presence of Phosphate Ions is indicated by the formation of a bright yellow
precipitate layer.
❖ Upon treatment with concentrated sulphuric acid, oxalates yield colourless
CO2 and CO gases.
❖ These gases burn with a bluish flame and turn lime water milky, Oxalates also
decolourise KMnO4 and give a white precipitate with CaCl2.
❖ When we add concentrated sulphuric acid to fluoride ions, they are protonated to
give hydrogen fluoride. This is because hydrogen fluoride is a weak acid, its anion
F- can be protonated back to the gas. F- + H2SO4 -> HF + HSO4-
❖ When we hold a glass rod at the mouth of the test tube, a white waxy deposit is
obtained on the glass rod. This is because of the reaction of HF with Silica. (Glass
rod - is of course nearly all silica!). HF(g) + SiO2(s) -> SiF4(g) + H20(l)
nd
2 Analytical Group of Anions
❖ The 2nd groups of anions consist of SO42-, CrO42-, BO3−3.
❖ SO42- react neither with concentrated nor diluted H2SO4. Sulfates give a white
precipitate with BaCl2 which is insoluble in any acid or base.
❖ Borates give a green flame characteristic of ethyl borate when ignited with
concentrated H2SO4 and ethanol....
3rd Analytical Group of Anions
❖ The 3rd groups of anions consist of S2- , S2O32-and CN-.
❖ The presence of sulfide is confirmed by adding lead(II) acetate paper, which turns
black due to the formation of PbS.
❖ Sulfides also turn solutions of red sodium nitroprusside purple.
❖ Thiosulfates produce SO2 gas when treated with dilute acid. In addition, they form
a cloudy precipitate of sulfur.
❖ When ferric ions are added to a solution of cyanide ions, no specific change in
color is observed. However, if we add the ferric ions to the solution after adding
thiosulphate or S22-, we get a blood red coloration of ferric thiocyanate.
✓ Ferric thiocyanate is Fe(SCN)3.
✓ Actually, this is a characteristic test for the presence of ferric ions and for thiocyanate
ions.
❖ Cyanide ions are nowhere directly involved in the formation of ferric(III)
thiocyanate. If
we review the test procedure for the detection of cyanide ions, we find that we
add,
according to our choice, either thiosulphate ions or S22- ions.
❖ These ions disproportionate in the presence of cyanide ions, forming thiocyanate
ions.
❖ It is these thiocyanate ions that eventually react with the added ferric ions to give
the blood red complex formation
CN- + S2O32- -> SCN- + SO32-
CN- + S22- -> SCN- + S2-
Fe3+ + SCN- -> Fe(SCN)2+ (blood red complex formation).
4th Analytical Group of Anions
❖ The 4th groups of anions consist of Cl−, Br−, I− and SCN-. The group reagent for
Group 4 anion is concentrated sulphuric acid (H2SO4).
❖ After addition of the acid, chlorides, bromides and iodides will form precipitates
with silver nitrate. The precipitates are white, pale yellow, and yellow,
respectively.
❖ The silver halides formed are completely soluble, partially soluble, or not
soluble at all, respectively, in aqueous ammonia solution.
❖ Chlorides are confirmed by the chromyl chloride test. When the salt is heated
with K2Cr2O7 and concentrated H2SO4, red vapours of chromyl chloride
(CrO2Cl2) are produced.
❖ Passing this gas through a solution of NaOH produces a yellow solution
of Na2CrO4.
 ❖ The acidified solution of Na2CrO4 gives a yellow precipitate with the addition
of (CH3COO)2Pb.
❖ Bromides and iodides are confirmed by the layer test. A sodium carbonate extract
is made from the solution containing bromide or iodide, and CHCl3 or CS2 is
added to the solution, which separates into two layers:
✓ a brown colour in the CHCl3 or CS2 layer indicates the presence of Br−,
and
✓ a violet colour indicates the presence of I−.
❖ With ferric ions, thiocyanate ions give a blood red coloration of Fe(SCN)3.
❖ This test is not given by ferrous ions - and hence is confirmatory for the presence
of both ferric ions and for thiocyanate ions.
th
5 Analytical Group of Anions
❖ The 5th groups of anions consist of ClO3-, NO3-, NO2-.
❖ Nitrates give brown fumes with concentrated H2SO4 due to formation of NO2.
This is intensified upon adding copper turnings.
❖ Nitrate ion is confirmed by adding an aqueous solution of the salt to FeSO4 and
pouring concentrated H2SO4 slowly along the sides of the test tube, which
produces a brown ring around the walls of the tube, caused by the formation
of Fe(NO)2+.
❖ Nitrites give reddish brown fumes of NO2 when treated with dilute H2SO4.
❖ These fumes cause a solution of potassium iodide(KI) and starch to turn blue.
❖ It is added to some concentrated sulphuric acid. A red, orange or yellow colour
indicates the presence of Chlorate in a Perchlorate sample. The test is fairly
sensitive.