QUALI (2011-2012)

QUALITATIVE CHEMICAL ANALYSIS

Qualitative analysis deals with the identification of elements and compounds respectively,
with the detection of individual components in their mixtures. Often from the physical
properties some conclusion may be drawn about the quality. Thus, density, melting point,
boiling point, color, odor, etc. may carry partial information. Since reliable conclusion, as
regards the composition, can be drawn only from chemical behavior, the chemical reactions of
a sample should be studied. Various reagents should be added and the physical-chemical
changes observed. The reactions should be rapid, sensitive and selective.

Most of the reactions are carried out in aqueous solutions and the observable changes
are as follows:

a) The reagent reacts with one or more components of the sample forming an insoluble
precipitate. Further information can be drawn from the color of the precipitate and its
behavior against other reagents.

b) In other cases the reaction is accompanied with gas evolution. Then, the physical-
chemical properties of the gas may be informative.

c) The reagent brings about a color-change in the solution.

d) Certain substances placed into gas flame change its color (flame test).

Depending on the amounts of the samples and the expenses, test-tube, spot and
microchemical reactions can be carried out. Test-tube reactions are performed with 1-2 cm3
of the sample in test tubes. The reagent is added dropwise with shaking, occasionally with
gentle heating. Spot reactions mean using 1-2 drops of the reactants on a watch-glass, a
porcelain dish or a filter paper. Microchemical reactions are carried out under a microscope
with very little amounts.

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 QUALI (2011-2012)

Precipitation reactions

A precipitate is an insoluble solid compound formed during a chemical reaction in solution.

To predict whether a precipitate will form when you mix together two solutions of ionic
compounds, you need to know whether any of the potential products that might form are
insoluble or not.
For the practice, one of the most important properties of compounds is their solubility. The
water-solubility of the most common inorganic salts is tabulated below.

Solubility rules for ionic compounds

Soluble in water

Anions Statement Exceptions

NO3¯ every nitrate is soluble
Cl¯ most of chlorides are soluble AgCl, Hg2Cl2, PbCl2
Br¯ most of bromides are soluble AgBr, Hg2Br2, HgBr2 és PbBr2
I¯ most of iodides are soluble AgI, Hg2I2, HgI2 és PbI2
2
SO4 ¯ most of sulfates are soluble CaSO4, SrSO4, BaSO4, PbSO4,
Hg2SO4, Ag2SO4
ClO3¯ every chlorate is soluble
C2H3O2- every acetate is soluble

Insoluble in water

Anions Statement Exceptions

S2¯ most of sulfides are insoluble alkali-, alkaline-earth metal and
ammonium sulfides
OH¯ most of hydroxides are insoluble alkali hydroxides
CO32¯ most of carbonates are insoluble alkali metal and ammonium
carbonates
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SO3 ¯ most of sulfites are insoluble alkali metal and ammonium sulphites
PO43¯ most of phosphates are insoluble alkali metal and ammonium
phosphates.

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 QUALI (2011-2012)

Detection of cations

During the systematic qualitative analysis the test for cations always precedes that of
anions since the previous knowledge of the present cations simplifies the analysis of anions.

The most common cations are classified into five analytical groups taking advantage
of the different solubility of their derivatives formed with the reagents added subsequently in
the order: hydrochloric acid, hydrogen sulphide, ammonium sulphide and ammonium
carbonate. The formulas of physiologically important (essential or poisonous) ions are
underlined. They will be studied in the laboratory course.

To Group 1 belong cations which form a precipitate with hydrogen sulphide in nitric
acid solution, and the sulphide is insoluble in ammonium sulphide. The group is subdivided
into two subgroups according to the solubility of their chlorides.
Members of Group 1a give a precipitate with hydrochloric acid: Ag+, Pb2+, Hg22+.

Chlorides of cations of Group 1b are soluble in water. To this group Hg2+, Cu2+, Bi3+,
Cd2+ belongs.

Group 2 consists of cations forming insoluble sulphides with hydrogen sulphide in

nitric acid solution. However, these sulphides are soluble in ammonium sulphide in form of
thio salts: As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+.

Group-3 cations form insoluble sulphides only in neutral or slightly basic medium
with ammonium sulphide. These sulphides are soluble in dilute hydrochloric acid: Co2+,
Ni2+, Fe2+, Fe3+, Cr3+, Al3+, Zn2+, Mn2+.
Group-4 cations do not react with the above reagents. They form insoluble carbonate
precipitate with ammonium carbonate in a neutral medium: Ca2+, Sr2+, Ba2+.

Group-5 cations have no group reactions. They have to be detected with specific
reactions: Mg2+, Na+, K+, NH4+, Li+, H+.

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 QUALI (2011-2012)

Classification of cations

Group-1 Group-2 Group-3 Group-4 Group-5

Alkaline-earth- Mg and alkali
H2S-csoport (NH4)2S group
metal’s group metal’s group
a. HCl-group As-group
+
Ag As3+ Co2+ Ca2+ Mg2+
Pb2+ As5+ Ni2+ Sr2+ Na+
Hg22+ Sb3+ Fe2+ Ba2+ K+
b. Cu-group Sb5+ Fe3+ NH4+
Hg2+ Sn2+ Cr3+ Li+
Cu2+ Sn4+ Al3+ H+
Bi2+ Zn2+
Cd2+ Mn2+

To perform a systematic investigation of all cations is not possible in two practices

and some reactions require reagent (H2S, (NH4)2S) with disgusting (rotten egg) odor. For
these reasons the number of cations to be analyzed is decreased and they are arranged in
groups according their location in the periodic system. The schedule of the identification of
unknown cation is simplified, too.

Selective qualitative analysis of monatomic and polyatomic ions

1. Reactions of alkali metals

1.1. Flame tests of alkali metals

1 M solutions of alkali metal chlorides (LiCl, NaCl, KCl) are used for the test. Heat
the wire-loop, dip it into the test solution, and then put it into the flame of a Bunsen
burner.

Flame coloration: Li+

Na+
K+ ....................., when the light from a flame passes through a blue
prism, the yellow flame of Na+ is absorbed and the violet flame of
potassium becomes visible.

Alkali metal ions do not react with reagents used on practice.

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2. Reactions of alkaline-earth metals

2.1. Reactions of Ca2+ ion

2.1.1. CaCl2 + H2SO4 = CaSO4↓ + 2 HCl

2.1.2. CaCl2 + 2NaOH = Ca(OH)2↓ + 2 NaCl
2.1.3. Flame coloration:

2.2. Reactions of Ba2+ ion

2.2.1. BaCl2 + H2SO4 = BaSO4↓ + 2 HCl

2.2.2. BaCl2 + 2NaOH = Ba(OH)2↓ + 2 HCl
2.2.3. Flame coloration:

2.3. Reactions of Sr2+ ions

2.3.1. SrCl2 + H2SO4 = SrSO4↓ + 2 HCl

2.3.2. SrCl2 + 2 NaOH = Sr(OH)2↓+ 2 NaCl
2.3.3. Flame coloration:

3. Reactions of transition elements

3.1. Reaction of Hg22+ and Hg2+ ions

3.1.1. Hg2(NO3)2 + H2SO4 = Hg2SO4↓ + 2 HNO3

3.1.2. Hg2(NO3)2 + 2 NaOH = Hg↓ + HgO↓ + H2O + 2 NaNO3
3.1.3. Hg2(NO3)2 + 2 KI = Hg2I2↓ + 2 KNO3
3.1.4. Hg2I2 + 2 KI = Hg↓ + K2[HgI4]
3.1.4. Hg2(NO3)2 + 2 HCl = Hg2Cl2↓ + 2 HNO3
3.1.5. HgCl2 + 2 NaOH = HgO↓ + 2 NaCl + H2O
3.1.6. HgCl2 + 2 KI = HgI2↓ + 2 KCl
HgI2 + 2 KI = K2[HgI4]

3.2. Reaction of Ag+ ion

3.2.1. AgNO3 + KCl = AgCl↓ + KNO3

3.2.2. AgNO3 + KBr = AgBr↓ + KNO3
3.2.3. AgNO3 + KI = AgI↓ + KNO3
3.2.4. 2 AgNO3 + 2 NaOH = 2 NaNO3 + 2 AgOH → Ag2O↓ + H2O
3.2.5. K2CrO4 + 2 AgNO3 = Ag2CrO4↓ + 2 KNO3

3.3. Reactions of Fe2+and Fe3+ ions

3.3.1. FeSO4 + 2 NaOH = Fe(OH)2↓ + Na2SO4

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3.3.2. 3 FeSO4 + 2 K3[Fe(CN)6] = Fe3[Fe(CN)6]2↓ + 3 K2SO4

3.3.3. 10 FeSO4 + 2 KMnO4 + 8 H2SO4 = 5 Fe2(SO4)3 + 2 MnSO4 + K2SO4 + 8 H2O
3.3.4. FeCl3 + 3 NaOH = Fe(OH)3↓ + 3 NaCl
3.3.5. 4 FeCl3 + 3 K4[Fe(CN)6] = Fe4[Fe(CN)6]3↓ + 12 KCl
3.3.6. FeCl3 + 3 KSCN = Fe(SCN)3 + 3 KCl

3.4. Reactions of Cd2+ ion

3.4.1. CdSO4 + 2 NaOH = Cd(OH)2↓ + 2 NaCl

3.4.2. CdSO4 + Na2S = CdS↓ + Na2SO4

4. Reactions of earth metals

4.1. Reactions of Al3+ ion

4.1.1. AlCl3 + 3 NaOH = Al(OH)3↓ + 3 NaCl in the excess of NaOH as follows:

4.1.2. Al(OH) 3↓ + NaOH = Na[Al(OH)4]
4.1.3. Al(OH) 3↓ + 3 HCl = AlCl3 + 3 H2O

4.2. Reactions of Pb2+ ion

4.2.1. Pb(NO3)2 + H2SO4 = PbSO4↓ + 2 HNO3

4.2.2. Pb(NO3)2 + 2 KI = PbI2↓ + KNO3
4.2.3. Pb(NO3)2 + 2 NaOH = Pb(OH) 2↓ + 2 NaNO3
4.2.4. Pb(OH) 2↓ + 2 HNO3 = Pb(NO3)2 + 2 H2O
4.2.5. Pb(OH) 2↓ + 2 NaOH = Na2[Pb(OH)4]
4.2.6. Pb(NO3)2 + K2CrO4 = PbCrO4 + 2 KNO3

4.3. Reactions of NH4+ (ammonium) ion

4.3.1. NH4Cl(sz) + NaOH = NaCl + NH3↑ + H2O (..................... odor)

NH2
4.3.2. NH4Cl + 2 K2[HgI4] + 4 KOH = HgO Hg + 7 KI + KCl + 3 H2O
I
(with Nessler reagent (K2[HgI4])

Detection of anions

Similarly to cations, anions are classified by testing with HCl, BaCl2 and AgNO3
solutions. It should be noted that while the cations are separable by means of the group
reagents, anions cannot be so.

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Group-1 anions react with strong acids to form gases or a precipitate: CO32-, HCO3-,
SO32-,S2O32-, S2-, SiO32-, ClO-.

Group-2 anions do not react with strong acids but react with BaCl2 to form a
precipitate: SO42-, PO43-, BO33-, F-, IO3-, BrO3-.

Group-3 anions give a precipitate with AgNO3: Cl-, I-, Br-, CN-, SCN-, [Fe(CN)6]4-,
[Fe(CN) ]4-.
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Group 4 consists of anions having no common reaction. These ions should be

detected individually: NO -, NO -, ClO -, OH-, CH COO-, (COO) 2-.
3 2 3 3 2

5.1. Reactions of Cl  (chloride) ion

5.1.1. NaCl + AgNO3 = AgCl↓ + NaNO3

5.1.2. Pb(NO3)2 + 2 NaCl = PbCl2↓ + 2 NaNO3

Check basicity of chloride ion solution by using universal indicator paper

5.2. Reactions of Br (bromide) ion

5.2.1. AgNO3 + KBr = AgBr↓ + KNO3

5.2.2. 2 KBr + Cl2 = Br2 + 2 KCl (..................... color after extraction (shaking)
with chloroform)
Check basicity of bromide ion solution by using universal indicator paper

5.3. Reaction of I  (iodide) ion

5.3.1. AgNO3 + KI = AgI↓ + KNO3

5.3.2. 2 KI + Cl2 = I2 + 2 KCl (.....................color, shows ..................... color
after extraction (shaking) with chloroform)
5.3.3. I2 + 5 Cl2 + 6 H2O = 2 HIO3 + 10 HCl
Check basicity of iodide ion solution by using universal indicator paper

6. Reactions of the oxygen group

6.1. Reaction of OH- (hydroxide) ion

6.1.1. 2 AgNO3 + 2 NaOH = 2 NaNO3 + 2 AgOH → Ag2O↓ + H2O (see at 3.2.4.!)

Check basicity of hydroxide ion solution by using universal indicator paper

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 QUALI (2011-2012)

6.2. Reaction of O22- (peroxide) ion

6.2.1. H2O2 + 2 KI + H2SO4 = 2 H2O + K2SO4 + I2↓

6.2.2. 5 H2O2 + 2 KMnO4 + 3 H2SO4 = 2 MnSO4 + K2SO4 + 8 H2O + 5 O2↑

Check basicity of peroxide ion solution by using universal indicator paper

6.3. Reaction of SO42 (sulphate) ion

6.3.1. BaCl2 + Na2SO4 = BaSO4↓ + 2 NaCl (white precipitate)

Check basicity of peroxide ion solution by using universal indicator paper

7. Reactions of the carbon group

7.1. Reaction of CO32 (carbonate) ion

7.1.1. Na2CO3 + 2 HCl = 2 NaCl + H2O + CO2↑

7.1.2. Na2CO3 + 2 AgNO3 = Ag2CO3 + 2 NaNO3

Check basicity of carbonate ion solution by using universal indicator paper

7.2 Reaction of SiO32 (silicate) ion

7.2.1 Na2SiO3 + 2 HCl = 2 NaCl + H2SiO3

7.2.2 Na2SiO3 + 2 AgNO3 = Ag2SiO3 + 2 NaNO3

Check basicity of silicate ion solution by using universal indicator paper

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 QUALI (2011-2012)

Simple analysis of cations and anions

The simple analysis of cations and anions of medical importance – in cases when only
one cation and one anion are present – is performed as shown in Tables below.

Procedure:

Every student get two test tubes: one of them contains 1M solution of the unknown
cation, the other one 0.1M solution of unknown anion. Dilute a small portion of 1M solution
ten times with distilled water and use the diluted solution for chemical reaction. Make the
flame test from the 1M solution if necessary.

After the identification of the ion according to Tables 1 and 2, the characteristic
reactions of the suspected ion should be positive to accept the analysis correct. The analysis
process should be described in details in the notebook, including visual observations and
chemical equations.

Identification of unknown cation

Pour about 1-1-1 cm3 solution with unknown cation into 3 clean test tubes. Add 1 cm3 30%
H2SO4 to the first, 1 cm3 KI solution to the second and 1 cm3 NaOH solution to the third test
tube. The reagent is added dropwise with shaking, occasionally with gentle heating. From the
chemical reactions identify the unknown cation.

Identification of unknown anion

Pour about 1-1-1 cm3 solution with unknown anion into 3 clean test tubes. Add 1 cm3 AgNO3
solution to the first, 1 cm3 HCl solution to the second test tube and test the basicity in the
third tube with universal indicator paper. The reagent is added dropwise with shaking,
occasionally with gentle heating. From the chemical reactions identify the unknown anion.

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 QUALI (2011-2012)

Determination of unknown cation

30%-os H2SO4
KI NaOH Special reaction

Ca2+

Ba2+

Sr2+

Hg22+

Hg2+

Ag+

Fe2+

Fe3+

Cd2+

Al3+

Pb2+

NH4+

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 QUALI (2011-2012)

Determination of unknown anion

AgNO3 HCl basicity Special reaction

Cl

Br

I

OH

H 2O 2

SO42

CO32

SiO32

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 QUALI (2011-2012)

Laboratory report: Name: .........................................................

Group: ..................................................
Data: ....................................................

Qualitative analysis of iorganic ions

1. Determination of unknown cation:

30% H2SO4 KI NaOH Special reaction

unknown
cation

………….. + H2SO4 =
………….. + KI =
………….. + NaOH =

Special reaction:

According to the chemical reaction, the unknown cation is the following:

2. Determination of unknown anion

basicity AgNO3 HCl Special reaction

unknown
anion

………….. + AgNO3 =
………….. + HCl =
Basicity:
Special reaction:

According to the chemical reaction, the unknown cation is the following:

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