The Group Ia Elements (Li, Na, K, Rb, Cs) and

Their Principle Ions (Me+)

Lithium is the lightest of all metals, with a density only about half that of water (0.534
g/ml at 0 C). It has a low melting point of 180.5 C. Lithium is silvery in appearance,
much like Na and K.

Sodium is a soft, bright, silvery metal which floats on water (melting point: 97.8 C). It
oxidises rapidly in moist air and is therefore kept under solvent naphtha or xylene.

Potassium is one of the most reactive and electropositive of metals. It is the second
lightest known metal, is soft, easily cut with a knife, and is silvery in appearance
immediately after a fresh surface is exposed (melting point: 63.3 C). Potassium is
rapidly oxidised in moist air, becoming covered with a blue film.

Rubidium is a soft, silvery-white metal (melting point: 38.9 C), and is the second most
electropositive and alkaline element.

Caesium is silvery with a golden-yellow appearance, soft, and ductile metal (melting
point: 28.4 C). It is the most electropositive and most alkaline element.

Solubility in aqueous solutions

Alkali metals decompose water with the evolution of hydrogen and the formation
of the hydroxide.

2 Me + 2 H2O 2 MeOH + H2

Caesium reacts explosively with cold water. Rubidium ignites spontaneously in air and
reacts violently in water, setting fire to the liberated hydrogen. Potassium catches fire
spontaneously on water. Sodium may or may not ignite spontaneously on water,
depending on the amount of oxide and metal exposed to water. Lithium reacts with water,
but not as vigorously as sodium.

7
Flame test

Compounds of alkali metals (and also some of the others, see later) are volatilized
in the non-luminous Bunsen flame and impart characteristic colours to the flame, which
can be used to identify the metal.

The physic-chemical process which

produce the characteristic colour can be
summarised as follows: 6p 4f
6s 5d
1. salt is evaporated 5p
4d
2. molecule decompose to its 5s
4p
constituents; e.g. NaCl Na + Cl 4s 3d
3. thermal excitation of valence shell 3p
electron of the metal atom; 3s
Na Na* 2p
2s
4. instant relaxation of the excited states
with ejecting photons: 1s
Na* Na + h

If the photons ejected are in the visible Na (3p 3s)= 589 nm (yellow light
region, coloration of the flame is
observed.

Chlorides are among the most volatile compounds and readily decompose in the flame of
the Bunsen burner, thus the best way to carry out the flame test is to prepare chlorides in
situ by mixing the compound with a little concentrated hydrochloric acid before carrying
out the tests.
The procedure is as follows. Put a few
crystals or a few drops of the solution
into a porcelain crucible, add
hydrochloric acid, and zinc chips. The
hydrogen gas liberated in the reaction
between zinc and hydrochloric acid
carries fine drops of the solution into the
flame, where the latter are volatilised.

The colours imparted to the flame:

Lithium carmine-red
Sodium golden-yellow
Potassium violet (lilac)
Rubidium dark-red
Caesium blue

8
Characteristic reactions of lithium ions

The solubilities of lithium carbonate, Li2CO3, the phosphate, Li3PO4, and the
fluoride, LiF, in water are little, definitely much less than the corresponding sodium and
potassium salts, and in this respect lithium resembles the alkaline earth metals. All other
important inorganic lithium salts are soluble in water.

For example: compound solubility ( g / 100 ml

water)
at 18 C: LiF 0,27
Li3PO4 0,039
0 C: LiCl 63,7

To study these reactions use a 1 M solution of lithium chloride.

1. Sodium phosphate solution: partial precipitation of lithium phosphate, Li3PO4, in

neutral solutions.
+ 3
3 Li + PO4 Li3PO4

Precipitation is almost complete in the presence of sodium hydroxide solution.

2. Sodium carbonate solution: white precipitate of lithium carbonate from

concentrated solutions:
+ 2
2 Li + CO3 Li2CO3

3. Ammonium carbonate solution: white precipitate of lithium carbonate from

concentrated solutions.
+ 2
2 Li + CO3 Li2CO3

No precipitation occurs in the presence of high concentration of ammonium chloride

since the carbonate ion concentration is reduced to such an extent that the solubility
product of lithium carbonate is not exceeded:

+ 2
NH4 + CO3 NH3 + HCO3

4. Ammonium fluoride solution: a white, gelatinous precipitate of lithium fluoride is

slowly formed in ammoniacal solution.

+
Li + F LiF

5. Flame test: carmine-red colour.

9
 +
Sodium, Na

Almost all sodium salts are soluble in water. There are, however, some special
reagents which a crystalline precipitate is formed with if it is added to a fairly
concentrated solution of sodium salts.
To study these reactions use a 1 M solution of sodium chloride.

1. Uranyl magnesium acetate solution: yellow, crystalline precipitate of sodium

magnesium uranyl acetate NaMg(UO2)3(CH3COO)9.9H2O from concentrated
solutions:
+ 2+ 2+
Na + Mg + 3 UO2 + 9 CH3COO NaMg(UO2)3(CH3COO)9

2. Uranyl zinc acetate solution: yellow, crystalline precipitate of sodium zinc uranyl
acetate NaZn(UO2)3(CH3COO)9.9H2O :

+ 2+ 2+
Na + Zn + 3 UO2 + 9 CH3COO NaZn(UO2)3(CH3COO)9

3. Flame test: intense yellow colour.

+
Potassium, K

Most of the potassium salts salts are soluble in water.

To study the reactions which produce water insoluble or little soluble salts, use a
1 M solution of potassium chloride. Remember, the sizes of K+ and NH4+ ions are almost
identical, thus their reactions in general are very similar.

1. Perchloric acid solution (HClO4): white crystalline precipitate of potassium

perchlorate KClO4 from not too dilute solutions. You may use concentrated HClO4
solution. (This reaction is unaffected by the presence of ammonium salts.)

+
K + ClO4 KClO4

2. Tartaric acid solution (or sodium hydrogen tartrate solution): white crystalline
precipitate of potassium hydrogen tartrate:
+ +
K + H2C4H4O6 KHC4H4O6 + H

The solution should be buffered with sodium acetate. The precipitate is slightly soluble in
water (3.26 g/l). (Ammonium salts yield a similar precipitate.)

10
3. Sodium hexanitritocobaltate(III) solution, Na3[Co(NO2)6]: yellow precipitate of
potassium hexanitritocobaltate(III):

+ 3
3 K + [Co(NO2)6] K3[Co(NO2)6]

The precipitate is insoluble in dilute acetic acid. In alkaline solutions a brown precipitate
of cobalt(III) hydroxide is obtained. (Ammonium salts give a similar precipitate.)
If larger amounts of sodium salts are present (e.g. reagent is added in excess) a mixed salt
is formed:
+ + 3
2 K + Na + [Co(NO2)6] K2Na[Co(NO2)6]

The test is more sensitive if sodium hexanitritocobaltate(III) and silver nitrate solutions
are added together to halogen free solutions; the compound K2Ag[Co(NO2)6] forms,
which is less soluble in water than the corresponding salt, K2Na[Co(NO2)6].

5. Flame test: violet colour.

Summarise the solubility of common inorganic salts of Li+, Na+, and K+:

2 3 2
CO3 PO4 F Cl NO3 SO4

+
Li

+
Na

+
K

11
 The Group IIa Elements (Be, Mg, Ca, Sr, Ba) and
Their Principle Ions (Me2+)

Beryllium is a steel grey, light but very hard, brittle metal, one of the lightest of all
metals, and has one of the highest melting points of the light metals (1278 C). Beryllium
objects are oxidised on the surface, but the oxide layer protects the objects from further
oxidisation, which is similar to that of aluminium. Beryllium resembles closely
aluminium in chemical properties; it also exhibits resemblances to the alkaline earth
metals.

Magnesium is a light, silvery-white, malleable and ductile metal with a melting point of
649 C. Magnesium objects have a protective oxide layer on the surface, similarly to that
of beryllium and aluminium. It burns upon heating in air or oxygen with a brilliant white
light, forming the oxide and some nitride.

Calcium has a silvery colour, is rather soft, but definitely much harder than the alkali
metals (melting point: 839 C). It is attacked by atmospheric oxygen and humidity, when
calcium oxide and/or calcium hydroxide is formed.

Strontium is a silvery-white, malleable and ductile metal (melting point: 769 C).
Strontium is softer than calcium and decomposes water more vigorously. It should be
kept under kerosene to prevent oxidation. Freshly cut strontium has a silvery appearance,
but rapidly turns a yellowish colour with the formation of the oxide

Barium is a silvery-white, soft, malleable and ductile metal (melting point: 725 C). It
oxidises very easily and should be kept under petroleum to exclude air.

Solubility in water and acids

Beryllium does not reacts with water at ordinary conditions.
Magnesium is slowly decomposed by water at ordinary temperature, but at the
boiling point of water the reaction proceeds rapidly:

Mg + 2 H2O Mg(OH)2 + H2

Calcium, strontium, and barium decompose water at room temperature with the
evolution of hydrogen and the formation of the hydroxide.

2+
Me + 2 H2O Me + 2 OH + H2

Be, Mg, Ca, Sr, and Ba dissolve readily in dilute acids (unless water insoluble salt
forms):
+ 2+
Me + 2 H Me + H2

Concentrated nitric acid renders beryllium passive (like aluminium).

12
 2+
Characteristic reactions of magnesium ions, Mg

The magnesium oxide, hydroxide, carbonate, and phosphate are insoluble in

water; the other common inorganic salts are soluble.
To study these reactions use a 0.1 M solution of magnesium chloride or sulphate.

1. Ammonium carbonate solution: in the absence of other ammonium salts a white

precipitate of basic magnesium carbonate:

2+ 2
5 Mg + 6 CO3 + 7 H2O 4 MgCO3.Mg(OH)2.5 H2O + 2 HCO3

In the presence of ammonium salts no precipitation occurs, because the following

equilibrium is shifted towards the formation of hydrogen carbonate ions (remember,
magnesium hydrogen carbonate is soluble in water):

+ 2
NH4 + CO3 NH3 + HCO3

2. Sodium carbonate solution: white, voluminous precipitate of basic magnesium

carbonate:

2+ 2
5 Mg + 6 CO3 + 7 H2O 4 MgCO3.Mg(OH)2.5 H2O + 2 HCO3

3. Ammonium hydroxide solution: partial precipitation of white, gelatinous

magnesium hydroxide, solubility product constant: Ksp(25C)= 5.61x1012:
2+ +
Mg + 2 NH3 + 2 H2O Mg(OH)2 + 2 NH4

The precipitate is readily soluble in solutions of ammonium salts.

4. Sodium hydroxide solution: white precipitate of magnesium hydroxide:

2+
Mg + 2 OH Mg(OH)2

5. Disodium hydrogen phosphate solution: a white flocculant precipitate of

magnesium hydrogen phosphate is produced in neutral solutions:

2+ 2
Mg + HPO4 MgHPO4

White crystalline precipitate of magnesium ammonium phosphate MgNH4PO4.6H2O in

the presence of ammonium chloride (to prevent precipitation of magnesium hydroxide)
and ammonia solutions:
2+ 2
Mg + NH3 + HPO4 MgNH4PO4

The precipitate is soluble in acetic acid and in mineral acids.

13
6. Titan yellow reagent and magneson reagent:

Titan yellow and magneson (I and II)

O2N N N OH
are water soluble dyestuffs. They are
absorbed by magnesium hydroxide HO
producing a deep-red colour with titan
yellow and a blue colour with magneson.
Magneson I

Pour a little amount of the test solution

into two test tubes, add 1-2 drops of the
O2N N N OH
titan yellow reagent to one test tube and
1-2 drops of the magneson reagent to the
other test tube. Render the solutions in
both test tubes alkaline with sodium
hydroxide solutions. Magneson II

Calcium, Ca2+

Calcium chloride and nitrate are readily soluble in water.

Calcium oxide (similarly to strontium and barium oxides) readily reacts with
water producing heat and forming the hydroxide.
Calcium sulphide (and also other alkaline earth sulphides) can be prepared only in
the dry; it hydrolyses in water forming hydrogen sulphide and hydroxide:
2 CaS + 2 H2O 2 Ca2+ + 2 SH- + 2 OH-
Calcium carbonate, sulphate, phosphate, and oxalate are insoluble in water.

To study the reactions of Ca2+ ions, use a 0.1 M solution of calcium chloride.

1. Ammonium carbonate solution: white amorphous precipitate of calcium carbonate,

solubility product constant: Ksp(25C)= 4.96x109, (the precipitate is soluble in acids
even in acetic acid):

2+ 2
Ca + CO3 CaCO3

2. Dilute sulphuric acid: white precipitate of calcium sulphate, solubility product

constant: Ksp(25C)= 7.10x105:

2+ 2
Ca + SO4 CaSO4

3. Ammonium oxalate solution: white precipitate of calcium oxalate, solubility

product constant: Ksp(CaC2O4.H2O, 25C)= 2.34x109 (insoluble in acetic acid, but
soluble in mineral acids):
2+ 2
Ca + (COO)2 Ca(COO)2

14
4. Disodium hydrogen phosphate solution: white precipitate of calcium hydrogen
phosphate is produced from neutral solutions:

2+ 2
Ca + HPO4 CaHPO4

5. Potassium hexacyanoferrate(II) solution: white precipitate of a mixed salt:

2+ + 4
Ca + 2 K + [Fe(CN)6] K2Ca[Fe(CN)6]

In the presence of ammonium chloride the test is more sensitive. In this case potassium is
replaced by ammonium ions in the precipitate. The test can be used to distinguish
calcium from strontium; barium and magnesium ions however interfere.

6. Flame test: yellowish-red colour to the Bunsen flame.

2+
Strontium, Sr

Strontium chloride and nitrate are readily soluble in water.

Strontium carbonate, sulphate, phosphate, and oxalate are insoluble in water.

To study the reactions of Sr2+ ions, use a 0.1 M solution of strontium chloride or
strontium nitrate.

1. Ammonium carbonate solution: white precipitate of strontium carbonate,

Ksp(SrCO3, 25C)= 5.60x1010 (the precipitate is soluble in acids even in acetic acid):
2+ 2
Sr + CO3 SrCO3

2. Dilute sulphuric acid: white precipitate of strontium sulphate, Ksp(SrSO4, 25C)=

3.44x107:
2+ 2
Sr + SO4 SrSO4

3. Saturated calcium sulphate solution: white precipitate of strontium sulphate,

formed slowly in the cold, but more rapidly on boiling.

2+ 2
Sr + SO4 SrSO4

4. Ammonium oxalate solution: white precipitate of strontium oxalate:

2+ 2
Sr + (COO)2 Sr(COO)2

15
5. Disodium hydrogen phosphate solution: white precipitate of strontium hydrogen
phosphate is produced from neutral solutions:

2+ 2
Sr + HPO4 SrHPO4

6. Potassium chromate solution: yellow precipitate of strontium chromate:

2+ 2
Sr + CrO4 SrCrO4

The precipitate is appreciably soluble in water, thus no precipitate occurs in dilute

solutions of strontium ions.
The precipitate is soluble in acetic acid and in mineral acids.

The addition of acid to potassium chromate solution causes the yellow colour of
the solution to change to reddish-orange, owing to the formation of dichromate. The
addition of acetic acid or mineral acid to the potassium chromate solution lowers the
CrO42 ion concentration sufficiently to prevent the precipitation of SrCrO4.

The equilibria are the following: c= 0.1 M (K2CrO 4)

[CrO 42-] (m ol/l)

0.10
+
H2CrO4 HCrO4 + H 0.08
2 +
HCrO4 CrO4 + H 0.06

0.04
2
2 HCrO4 H2O + Cr2O7
0.02
2 +
HCr2O7 Cr2O7 + H 0.00

0 2 4 6 8 10
pH

7. Flame test: crimson-red colour to the Bunsen flame.

2+
Barium, Ba
Barium chloride and nitrate are readily soluble in water.
Barium carbonate, sulphate, phosphate, and oxalate are insoluble in water.

To study the reactions of Ba2+ ions, use a 0.1 M solution of barium chloride or
barium nitrate.

1. Ammonium carbonate solution: white precipitate of barium carbonate, Ksp(BaCO3,

25C)= 2.58x109 (the precipitate is soluble in acids even in acetic acid):
2+ 2
Ba + CO3 BaCO3

16
2. Dilute sulphuric acid: white, finely divided precipitate of barium sulphate,
Ksp(BaSO4, 25C)= 1.07x1010:

2+ 2
Ba + SO4 BaSO4

3. Saturated calcium sulphate solution: immediate white precipitate of barium

sulphate.

4. Saturated strontium sulphate solution: white precipitate of barium sulphate.

5. Ammonium oxalate solution: white precipitate of barium oxalate (readily dissolved

by hot dilute acetic acid and by mineral acids):

2+ 2
Ba + (COO)2 Ba(COO)2

6. Disodium hydrogen phosphate solution: white precipitate of barium hydrogen

phosphate is produced from neutral solutions:

2+ 2
Ba + HPO4 BaHPO4

6. Potassium chromate solution: yellow precipitate of barium chromate, practically

insoluble in water, Ksp(BaCrO4, 25C)= 1.17x1010:

2+ 2
Ba + CrO4 BaCrO4

The precipitate is insoluble in dilute acetic acid (distinction from strontium), but soluble
in mineral acids.

7. Flame test: yellowish-green colour to the Bunsen flame.

Compare the solubility product constants of CaSO4, SrSO4, and BaSO4, and
calculate the sulphate ion concentration in saturated solutions.

CaSO4 SrSO4 SrSO4

solubility product 5 7 10
7.10x10 3.44x10 1.07x10
constant: Ksp

2
SO4
concentration

17
 2+ 2+ 2+ 2+
Summarise the reactions of Mg , Ca , Sr , and Ba ions:

2+ 2+ 2+ 2+
Mg Ca Sr Ba

NH3 soln.

NaOH

Na2CO3

(NH4)2CO3
+ NH4Cl

(NH4)2CO3

Na2HPO4

(NH4)2(COO)2
add hot acetic acid
to the precipitate

K2CrO4 1. add acetic acid

add acetic acid to to the precipitate
neutral soln.
the precipitate 2. add mineral acid
to the prec.

dilute H2SO4

satd. CaSO4 soln.

satd. SrSO4 soln.

Flame test

18
 The Group IIIa Elements: Boron and Aluminium, and
Their Principle Ions (B(OH)4 and Al3+)

Boron has properties that place it on the borderline between metals and nonmetals, but
chemically it must be classed as a nonmetal. Boron is a hard, steel-grey solid with a high
melting point of 2079 C. Crystalline boron is extremely inert chemically.

Aluminium. Pure aluminium is a silvery-white metal (melting point (m.p.): 660.4 C). It
is light, malleable and ductile, can easily be formed, machined, or cast, has a high
thermal conductivity, and has an excellent corrosion resistance. The aluminium powder is
grey. Exposed to air, aluminium objects are oxidised on the surface, but the oxide layer
protects the objects from further oxidisation.

Solubility in aqueous acids and alkali

Boron is unaffected by nonoxidising acids (e.g. boiling HCl or HF).
It is only slowly oxidised by hot, concentrated nitric acid, and also only slowly attacked
by other hot concentrated oxidising agents (e.g. aqua regia, or a mixture of concentrated
nitric acid and hydrogen fluoride).
Boron is soluble in alkali with the evolution of hydrogen gas.

B + HNO3 + H2O H3BO3 + NO

2 B + 2 HNO3 + 4 H2F2 2 H[BF4] + 2 NO + 4 H2O
+
2 B + 2 NaOH + 6 H2O 2 Na + 2 B(OH)4 + 3 H2

Aluminium is soluble in dilute or concentrated hydrochloric acid with the

liberation of hydrogen:
2 Al + 6 HCl 2 Al3+ + 6 Cl- + 3 H2

Dilute sulphuric acid dissolves the metal with the liberation of hydrogen and
concentrated sulphuric acid with the liberation of sulphur dioxide:

2 Al + 3 H2SO4 2 Al3+ + 3 SO42 + 3 H2

2 Al + 6 H2SO4 2 Al3+ + 3 SO42 + 3 SO2 + 6 H2O

Concentrated nitric acid renders aluminium passive, but dilute nitric acid dissolves the
metal:
Al + 4 HNO3 Al3+ + 3 NO3 + NO + 2 H2O

Aluminium is soluble in alkali hydroxides when a solution of tetrahydroxoaluminate is

formed:
2 Al + 2 OH- + 6 H2O 2 [Al(OH)4] + 3 H2

19
Reducing power of aluminium
Aluminium is a very reactive metal, in particular towards electronegative
partners, but this extreme reactivity can only be observed when the stable oxide layer at
the metal surface is destroyed or the metal is in a finely divided form.

1. Termite reaction: no reaction occurs between iron(III) oxide and aluminium powder
at room temperature, but an exothermic, violent reaction takes place when it is initiated
by a thermal ignition mixture.

Fe2O3 + 2 Al Al2O3 + 2 Fe

The reaction is extremely violent and is accompanied by the formation of a large amount
of sparks.

2. Reaction with iodine: add only one drop of water to a mixture of fine aluminium
powder and powdered iodine.

2 Al + 3 I2 Al2I6

The reaction is induced by water, the heat which is set free at the beginning of the
reaction sufficing to convert the whole mixture to dialuminium hexaiodide and to
sublime the excess iodine.

Aluminium(III) ions, Al3+

Solubility: aluminium chloride, bromide, iodide, nitrate, and sulphate are soluble
in water.
Aluminium fluoride is hardly soluble in water. Aluminium oxide, hydroxide,
phosphate, and carbonate are practically insoluble in water.

For example: compound solubility ( g / 100 ml

water)
at 15 C AlCl3 69,9
25 C AlF3 0,559
-Al2O3 0,000098
-----
AlPO4

Aluminium sulphide can be prepared in the dry state only, in aqueous solutions it
hydrolyses and aluminium hydroxide is formed.

Use a 0.1 M solution of aluminium chloride or sulphate to study the reactions of

aluminium(III) ions.

20
1. Ammonium sulphide solution: a white precipitate of aluminium hydroxide.

2 Al3+ + 3 S2 + 6 H2O 2 Al(OH)3 + 3 H2S

2. Sodium hydroxide solution: white precipitate of aluminium hydroxide. The

precipitate dissolves in excess reagent, when tetrahydroxoaluminate ions are formed.

Al3+ + 3 OH Al(OH)3
Al(OH)3 + OH [Al(OH)4]

The reaction is a reversible one, and any reagent which will reduce the OH- ion
concentration sufficiently should cause the reaction to proceed from right to left.

3. Ammonia solution: white gelatinous precipitate of aluminium hydroxide. The

precipitate is only slightly soluble in excess of the reagent, the solubility is decreased in
the presence of ammonium salts.

Al3+ + 3 NH3 + 3 H2O Al(OH)3 + 3 NH4+

4. Sodium phosphate solution: white gelatinous precipitate of aluminium phosphate,

solubility product constant: Ksp(AlPO4, 25C)= 9.83x1021:

Al3+ + HPO42 AlPO4 + H+

Strong acids and also sodium hydroxide dissolve the precipitate.

5. Sodium acetate solution: no precipitate is obtained in cold, neutral solutions, but on

boiling with excess reagent, a voluminous precipitate of basic aluminium acetate is
formed:
Al3+ + 3 CH3COO- + 2 H2O Al(OH)2CH3COO + 2 CH3COOH

6. Sodium alizarin sulphonate (Alizarin-S) reagent: O OH

C OH
red precipitate in ammoniacal solution, which is
fairly stable to dilute acetic acid. C
Add to the solution of Al3+ ions, dilute ammonia
SO 3 Na
O
solution and 2-3 drops of the solution of the reagent, and Alizarin-S
then acidify it with acetic acid.
HO OH
7. Morin reagent: add little solid sodium acetate and 1-
2 drops of the reagent to the solution of Al3+ ions. HO O

Investigate the characteristic green fluorescence of the

OH
solution in UV light. OH O
Morin

21
Oxides of Boron and Aluminium

B2O3 Al2O3

B2O3 is a white , hygroscopic solid. Al2O3 is very hard and resistant to

It is acidic, reacting with water to give hydration and attack by acids.
boric acid, B(OH)3. Al2O3 readily takes up water and
dissolves in acids.

Boric acid and borate ions in aqueous solution

Boric acid, H3BO3 or B(OH)3, is a very weak and exclusively monobasic acid that

acts not as a proton donor, but as a Lewis acid, accepting OH :

+
B(OH)3 + H2O B(OH)4 + H KS= 6x1010

In aqueous, concentrated borate solutions polymeric ions are also present, due to the

polymerisation between B(OH)3 and B(OH)4 , the most important ions for example:

4 B(OH)3 + B(OH)4 B5O6(OH)4 + 6 H2O

2 B(OH)3 + B(OH)4 B3O3(OH)4 + 3 H2O
2
2 B(OH)3 + 2 B(OH)4 B4O5(OH)4 + 5 H2O

In acidic solution (pH<4) orthoboric acid B(OH)3, in basic solution (pH>12) B(OH)4

ions exist exclusively, and at medium pH (4<pH<12) besides B(OH)4 , polyanions
2
B5O6(OH)4 , B3O3(OH)4 , and B4O5(OH)4 are also present.
2
The species B5O6(OH)4 , B3O3(OH)4 , and B4O5(OH)4 are formed successively with
increasing pH.

In dilute solutions depolimerization rapidly occurs; at concentrations <0.025 M,

essentially only mononuclear species B(OH)3 and B(OH)4 are present.

Borates, BO33, B4O72, BO2

The borates are formally derived from the three boric acids:
orthoboric acid, H3BO3 (a well known white, crystalline solid),
metaboric acid, HBO2 (not known in solution and can not be isolated) and
pyroboric acid, H2B4O7 (not known in solution and can not be isolated).
Most of the salts are derived from the meta- and pyroboric acids, and only very few salts
of orthoboric acid are known.
Solubility: the borates of the alkali metals are readily soluble in water.
The borates of the other metals are, in general, sparingly soluble in water, but fairly
soluble in acids and in ammonium chloride solution.

22
The soluble salts are hydrolysed in solution, owing to the weakness of boric acid, and
therefore react alkaline:
BO33 + 3 H2O H3BO3 + 3 OH
B4O72 + 7 H2O 4 H3BO3 + 2 OH
BO2 + 2 H2O H3BO3 + OH

To study the reactions of borates use a 0.1 M solution of sodium tetraborate

(sodium pyroborate, borax) Na2B4O7.10H2O.

1. Barium chloride solution: white precipitate of barium metaborate from fairly

concentrated solutions:
B4O72 + 2 Ba2+ + H2O 2 Ba(BO2)2 + 2 H+

The precipitate is soluble in excess reagent, in dilute acids, and in solutions of

ammonium salts.

2. Silver nitrate solution: white precipitate of silver metaborate from fairly concentrated
solution:
B4O72 + 4 Ag+ + H2O 4 AgBO2 + 2 H+

The precipitate is soluble in both dilute ammonia solution and in acetic acid. On boiling
the precipitate with water, it is completely hydrolysed and a brown precipitate of silver
oxide is obtained.
AgBO2 + 2 NH3 + 2 H2O [Ag(NH3)2]+ + B(OH)4
AgBO2 + H+ + H2O Ag+ + H3BO3
2 AgBO2 + 3 H2O Ag2O + 2 H3BO3

3. Hydrochloric acid: there is no visible change with dilute hydrochloric acid, but if
concentrated hydrochloric acid is added to a concentrated solution of borax, boric acid is
precipitated:
B4O72 + 2 HCl + 5 H2O 4 H3BO3 + 2 Cl

4. Concentrated sulphuric acid and alcohol (flame test)

If a little borax is mixed with 1

ml concentrated sulphuric acid and 5
ml methanol in a small porcelain
basin, and the alcohol ignited, the
latter will burn with a green-edged
flame due to the formation of methyl
borate B(OCH3)3:

B4O72- + H2SO4 + 5 H2O 4 H3BO3 + SO42-

H3BO3 + 3 CH3OH B(OCH3)3 + 3 H2O

23
 The Group IVa Elements (C, Si, Ge, Sn, Pb) and
Their Principle Ions

Carbon has three allotropic forms: diamond, graphite, and fullerenes.

Diamond is the hardest solid known. It has a high density and the highest melting point (
4000 C) of any element. The chemical reactivity of diamond is much lower than that of
carbon in the form of macrocrystalline graphite or the various amorphous forms.
Diamond can be made to burn in air by heating it to 600 to 800 C.
Graphite has a layer structure and the forces between layers are relatively slight. Thus the
observed softness and particularly the lubricity of graphite can be attributed to the easy
slippage of these layers over one another.
Fullerenes belongs to the family of carbon-cage molecules, discovered during the last
two decades of the XXth century, of which C60 and C70 are the most known members.
Both C60 and C70 are highly coloured crystalline solids that are sparingly soluble in
common organic solvents.

Silicon has a solid structure which is isostructural with diamond. Crystalline silicon has
a metallic lustre and greyish colour. Melting point (m.p.): 1410 C.

Germanium is isostructural with diamond. It is a grey-white metalloid, and in its pure

state is crystalline and brittle, retaining its lustre in air at room temperature. (m.p.: 937.4
C)

Tin has two crystalline modifications: -tin or grey tin, and or white tin (metallic
form). -tin has the diamond structure.
Tin (-form) is a silver-white metal which is malleable and ductile at ordinary
temperatures, but at low temperatures (below 13.2 C) it becomes brittle due to
transformation into the allotropic modification. Tin melts at 232 C.

Lead exists only in a metallic form. It is a bluish-grey metal with a high density, is very
soft, highly malleable, and ductile. Melting point: 327.5 C. Lead is very resistant to
corrosion.

Solubility of group IVa elements in aqueous acids and alkali

Carbon is very unreactive at normal conditions, but the reactivity of IVa group
elements is increasing down the group, from the carbon toward the lead.
Carbon is not soluble in aqueous acids or alkalis.
Silicon is rather unreactive. It is not attacked by acids except the mixture of HF
and HNO3; presumably the stability of SiF62- provides the driving force here. Silicon is
soluble in alkalis giving solutions of silicates.

3 Si + 18 HF + 4 HNO3 3 H2SiF6 + 4 NO + 8 H2O

Si + 2 KOH + H2O K2SiO3 + 2 H2

24
 Germanium is somewhat more reactive than silicon, and dissolves in concentrated
H2SO4 and HNO3, when GeO2.xH2O is formed. It is not attacked by alkalis and non
oxidising acids, soluble, however, in alkalis containing hydrogen peroxide.

3 Ge + 4 HNO3 + (x-2) H2O 3 GeO2.xH2O + 4 NO

Tin and lead dissolve in several acids. Tin is attacked slowly by cold alkali,
rapidly by hot, lead only by hot, to form stannates and plumbites.

Sn + 2 NaOH + 2 H2O Na2[Sn(OH)4] + H2

Tin dissolves slowly in dilute hydrochloric acid and sulphuric acid with the
formation of tin(II) salts:
Sn + 2 H+ Sn2+ + H2

Dilute nitric acid dissolves tin slowly without the evolution of any gas, tin(II) and
ammonium ions being formed:

4 Sn + 10 H+ + NO3 4 Sn2+ + NH4+ + 3 H2O

In hot, concentrated sulphuric acid and in aqua regia tin(IV) ions are formed at
dissolution:
Sn + 4 H2SO4 Sn4+ + 2 SO42 + 2 SO2 + 4 H2O
3 Sn + 4 HNO3 + 12 HCl 3 Sn4+ + 12 Cl + 4 NO + 8 H2O

Tin reacts vigorously with concentrated nitric acid, and a white solid, usually formulated
as hydrated tin(IV) oxide SnO2.xH2O and also known as metastannic acid, is produced:
3 Sn + 4 HNO3 + (x-2) H2O 3 SnO2.xH2O + 4 NO

Lead readily dissolves in medium concentrated (8M) nitric acid with the
formation of nitrogen oxide. The colourless nitrogen oxide gas, when mixed with air, is
oxidised to red nitrogen dioxide:

3 Pb + 8 HNO3 3 Pb2+ + 6 NO3- + 2 NO + 4 H2O

2 NO (colourless) + O2 NO2 (reddish-brown)

With concentrated nitric acid a protective film of lead nitrate is formed on the surface of
the metal and prevents further dissolution.
Dilute hydrochloric or sulphuric acid have little effect owing to the formation of a
protective film of insoluble lead chloride or sulphate on the surface.

25
Principle oxides of IVa group elements
C Si Ge Sn Pb
*
CO, CO2 SiO2 GeO2 SnO red() PbO yellow (red)*
colourless gases white solid white solid SnO2 white PbO2 black
*
white SnO.xH2O and white PbO.xH2O precipitates from aqueous solutions

Only CO2 is soluble in water; the solubility strongly depends on the pressure and
temperature. (1 litre water dissolves 0.9 litre of CO2 of 1 atm pressure at 20 C.)
SiO2 and GeO2 are hardly soluble in water; e.g. the solubility of GeO2 is 0.4 g in 100 g
water at 20 C.
SnO2 and PbO2 are insoluble in water.

CO2 is acidic, and the acidic character of oxides of the IVa group elements decreases
form the carbon dioxide toward the lead oxide. Carbon, silicon, and germanium oxides
are acidic, tin oxides are amphoteric, and lead oxide has also some basic character.

CO2, SiO2, and GeO2 are not soluble in acids, but soluble in alkalis giving carbonates,
silicates, and germanates, respectively. Silicate and germanate anions are polymeric.
SnO2 is not soluble in acids and alkalis, and PbO2 is only little soluble in acids.

SnO is soluble in acids and alkalis, forming tin(II) salts or stannates.

PbO is soluble in acids, forming lead(II) salts.

Lead(IV) oxide, PbO2, is a strong oxidising agent (Pb2+/ PbO2= +1.455 V), thus it
liberates chlorine by boiling with concentrated hydrochloric acid:

PbO2 + 4 HCl PbCl2 + 2 H2O + Cl2

Principal ions of IVa group elements and their characteristic reactions

C Si Ge Sn Pb
CO32 SiO32 * GeO32 * Sn2+ Pb2+
HCO3 Sn4+
* Does not exist in this form in aqueous solution.

26
Carbonates, CO32

All normal carbonates, with the exception of those of the alkali metals and of
ammonium, are insoluble in water.
The hydrogen carbonates (or bicarbonates) of the alkali metals are soluble in
water, but are less soluble than the corresponding normal carbonates.
The hydrogen carbonates of calcium, strontium , barium, magnesium, and possibly of
iron exist in aqueous solution; they are formed bye the action of excess carbonic acid
upon the normal carbonates either in aqueous solution or suspension:

CaCO3 + H2O + CO2 Ca2+ + 2 HCO3

Hydrogen carbonates are decomposed to carbonates on boiling the solution.

The following equilibria exists in aqueous solution:

CO2 + 3 H2O H2CO3 + 2 H2O H3O+ + HCO3- + H2O 2 H3O+ + CO32-

In acid solutions the equilibria shifted towards the left, while in alkaline medium they are
shifted towards the right.

To study the reactions of carbonates, use a 0.5 M solution of sodium carbonate,

Na2CO3.10H2O.

1. Dilute hydrochloric acid: decomposition with the evolution of carbon dioxide:

CO32- + 2 H+ CO2 + H2O

the gas can be identified by its property of

rendering lime water or baryta water turbid:

CO2 + Ca2+ + 2 OH- CaCO3 + H2O

CO2 + Ba2+ + 2 OH- BaCO3 + H2O

Any acid which is stronger than carbonic acid

will displace it, especially on warming. Thus
even acetic acid will decompose carbonates; the
weak boric acid and hydrocyanic acid will not.

2. Barium chloride (or calcium chloride) solution: white precipitate of barium (or
calcium) carbonate:
CO32- + Ca2+ CaCO3
CO32- + Ba2+ BaCO3
Only normal carbonates react; hydrogen carbonates do not. The precipitate is soluble in
mineral acids and carbonic acid.

27
3. Silver nitrate solution: white precipitate of silver carbonate, solubility product
constant Ksp(Ag2CO3, 25 C)= 8.45x1012:

CO32- + 2 Ag+ Ag2CO3

The precipitate is soluble in nitric acid and in ammonia. The precipitate becomes yellow
or brown upon addition of excess reagent owing to the formation of silver oxide; the
same happens if the mixture is boiled:

Ag2CO3 Ag2O + CO2

Hydrogen carbonates, HCO3

Most of the reactions of hydrogen carbonates are similar to those of carbonates.

The tests described here are suitable to distinguish hydrogen carbonates from carbonates.

To study the reactions of hydrogen carbonates, use a freshly prepared 0.5 M solution of
sodium hydrogen carbonate, NaHCO3.

1. Boiling. When boiling, hydrogen carbonates decompose:

2 HCO3- CO32- + H2O + CO2

carbon dioxide, formed in this way, can be identified with lime water or baryta water.

2. Magnesium sulphate. Adding magnesium sulphate to a cold solution of hydrogen

carbonate no precipitation occurs, while a white precipitate of magnesium carbonate is
formed with normal carbonates.
Heating the mixture, a white precipitate of magnesium carbonate is formed:

Mg2+ + 2 HCO3- MgCO3 + H2O + CO2

carbon dioxide, formed in this way, can be identified with lime water or baryta water.

3. Mercury(II) chloride. No precipitate is formed with hydrogen carbonate ions, while

in a solution of normal carbonates a reddish-brown precipitate of basic mercury(II)
carbonate (3HgO.HgCO3 = Hg4O3CO3) is formed:

CO32- + 4 Hg2+ 3 H2O Hg4O3CO3 + 6 H+

the excess of carbonate acts as a buffer, reacting with the hydrogen ions formed in the
reaction.

28
4. Solid test On heating some solid alkali hydrogen carbonate in a dry test tube carbon
dioxide is evolved:
2 NaHCO3 Na2CO3 + H2O + CO2

The gas can be identified with lime water or baryta water.

Silicates, SiO32

The silicic acids may be represented by the general formula xSiO2.yH2O. Salts
corresponding to orthosilicic acid, H4SiO4 (SiO2.2H2O) metasilicic acid, H2SiO3
(SiO2.H2O), and disilicic acid H2Si2O5 (2SiO2.H2O) are definitely known. The
metasilicates are sometimes designated simply as silicates.

Solubility. Only the silicates of the alkali metals are soluble in water; they are
hydrolysed in aqueous solution and therefore react alkaline.

SiO32 + 2 H2O H2SiO3 + 2 OH

To study these reactions use a 1 M solution of sodium silicate, Na2SiO3.

1. Dilute hydrochloric acid. Add dilute hydrochloric acid to the solution of the silicate;
a gelatinous precipitate of metasilicic acid is obtained, particularly on boiling:

SiO32 + 2 H+ H2SiO3

2. Ammonium chloride or ammonium carbonate solution: gelatinous precipitate of

silicic acid:

SiO32 + 2 NH4+ H2SiO3 + 2 NH3

3. Silver nitrate solution: yellow precipitate of silver silicate:

SiO32 + 2 Ag+ Ag2SiO3

Precipitate is soluble in dilute acids and in ammonia solution.

4. Barium chloride solution: white precipitate of barium silicate, soluble in dilute nitric
acid:
SiO32- + Ba2+ BaSiO3

29
5. Ammonium molybdate solution. Add acidified (NH4)2MoO4 solution to the solution
of the silicate; a yellow coloration of the solution is obtained due to the formation of the
ammonium salt of silicomolybdic acid, H4[SiMo12O40]:

SiO32- + 12 MoO42- + 4 NH4+ + 22 H+ (NH4)4[Si(Mo3O10)4] + 11 H2O

Add tin(II) chloride to the solution; the ammonium salt of silicomolybdic acid is reduced
to 'molybdenum blue'.

Tin(II) ions, Sn2+

In acid solution the tin(II) ions Sn2+ are present, while in alkaline solutions
tetrahydroxo-stannate(II) ions [Sn(OH)4]2 are to be found. They form an equilibrium
system:
Sn2+ + 4 OH [Sn(OH)4]2

Use a 0.1 M solution of tin(II) chloride, SnCl2.2H2O, for studying the reactions
of tin(II) ions. The solution should contain a few per cent hydrochloric acid to prevent
hydrolysis.

1. Hydrogen sulphide: brown precipitate of tin(II) sulphide, solubility product constant

Ksp(SnS, 25 C)= 3.25x1028, from not too acidic solutions:

Sn2+ + H2S SnS + 2 H+

The precipitate is soluble in concentrated hydrochloric acid (distinction from arsenic(III)

sulphide and mercury(II) sulphide); it is also soluble in ammonium polysulphide, but not
in ammonium sulphide solution, to form a thiostannate. Treatment of the solution of
thiostannate with an acid yields a yellow precipitate of tin(IV) sulphide:
SnS + S22 SnS32
SnS32 + 2 H+ SnS2 + H2S

2. Sodium hydroxide solution: white precipitate of tin(II) hydroxide, Ksp(Sn(OH)2, 25

C)= 5.45x1027, which is soluble in excess alkali:

Sn2+ + 2 OH Sn(OH)2
Sn(OH)2 + 2 OH [Sn(OH)4]2

With ammonia solution, white tin(II) hydroxide is precipitated, which can not be
dissolved in excess ammonia.

3. Mercury(II) chloride solution: a white precipitate of mercury(I) chloride (calomel) is

formed if a large amount of the reagent is added quickly:

Sn2+ + 2 HgCl2 Hg2Cl2 + Sn4+ + 2 Cl

30
If however tin(II) ions are in excess, the precipitate turns grey, especially on warming,
owing to further reduction to mercury metal:

Sn2+ + Hg2Cl2 2 Hg + Sn4+ + 2 Cl

4. Bismuth nitrate and sodium hydroxide solutions: black precipitate of bismuth metal:

3 Sn2+ + 18 OH + 2 Bi3+ 2 Bi + 3 [Sn(OH)6]2

5. Metallic zinc spongy tin is deposited which adheres to the zinc.

6. Iron(III) nitrate and ammonium rhodanide solutions: the red solution of Fe(SCN)3
is decolorised due to the reduction of iron(III) to iron(II) by tin(II) ions.
Tin(II) ions must be in excess.

7. Luminescence test (chemiluminescence of SnH4).

This test is based upon the fact that
soluble compounds of tin are reduced by
'nascent' hydrogen in acid solution to
SnH4:

Sn2+ + 3 Zn + 4 H+ SnH4 + 3 Zn2+

SnH4 is decomposes to Sn and H2 when

brought into the hot flame of a Bunsen
burner, with yielding a characteristic
blue light.

Tin(IV) ions, Sn4+

In acid solution the tin(IV) ions Sn4+ are present, while in alkaline solutions
hexahydroxostannate(IV) ions [Sn(OH)6]2 are to be found. They form an equilibrium
system:
Sn4+ + 6 OH [Sn(OH)6]2

1. Hydrogen sulphide: yellow precipitate of tin(IV) sulphide SnS2 from dilute acid
solutions:
Sn4+ + 2 H2S SnS2 + 4 H+

The precipitate is soluble in concentrated hydrochloric acid (distinction from arsenic(III)

sulphide and mercury(II) sulphide), in solutions of alkali hydroxides, and also in
ammonium sulphide and polysulphide. Yellow tin(IV) sulphide is precipitated upon
acidification:

31
 SnS2 + S2 SnS32
SnS2 + 2 S22 SnS32 + S32
SnS32 + 2 H+ SnS2 + H2S

2. Sodium hydroxide solution: gelatinous white precipitate of tin(IV) hydroxide, which

is soluble in excess alkali:

Sn2+ + 4 OH Sn(OH)4
Sn(OH)4 + 2 OH [Sn(OH)6]2

With ammonia and with sodium carbonate solutions, a similar white tin(IV)
hydroxide is precipitated, which, however, is insoluble in excess reagent.

3. Mercury(II) chloride solution: no precipitate (difference from tin(II)).

4. Metallic iron: reduces tin(IV) ions to tin(II):

Sn4+ + Fe Sn2+ + Fe2+

If pieces of iron are added to a solution, and the mixture is filtered, tin(II) ions can be
detected e.g. with mercury(II) chloride reagent.

5. Luminescence test (chemiluminescence of SnH4). (see in previous page)

2+ 4+
Summarise the redox reaction of Sn and Sn :

2+ 3+
Hg Zn Fe Fe

2+
Sn

4+
Sn

Standard electrode potentials at 25 C:

2+ 4+ 2+ 2+
Sn / Sn : +0.151 V Hg2 :/ Hg : +0.920 V
2+
Hg/ Hg2 : +0.7973 V
2+ 2+ 3+
Sn/ Sn : 0.1375 V Fe / Fe : +0.771 V
2+
Fe/ Fe : 0.447 V
2+
Zn/ Zn : 0.7618 V

32
Lead(II) ions, Pb2+

A 0.2 M solution of lead nitrate or lead acetate can be used to study these
reactions.

1. Dilute hydrochloric acid (or soluble chlorides): a white precipitate in cold and not
too dilute solution, solubility product constant Ksp(PbCl2, 25 C)= 1.17x105:

Pb2+ + 2 Cl PbCl2

The precipitate is soluble in hot water, but separates again in long, needle-like crystals
when cooling. (The solubility of PbCl2 in water at 100 C and 20 C is 33.4 g/l and 9.9
g/l, respectively.)
The precipitate is soluble in concentrated hydrochloric acid or concentrated potassium
chloride when the tetrachloroplumbate(II) ion is formed:

PbCl2 + 2 Cl [PbCl4]2

If the PbCl2 precipitate is washed by decantation and dilute ammonia is added, no visible
change occurs, though a precipitate-exchange reaction takes place and lead hydroxide is
formed, Ksp(Pb(OH)2, 25 C)= 1.42x1020:

PbCl2 + 2 NH3 + 2 H2O Pb(OH)2 + 2 NH4+ + 2 Cl-

2. Hydrogen sulphide: black precipitate of lead sulphide in neutral or dilute acid

medium, Ksp(PbS, 25 C)= 9.04x1029:

Pb2+ + H2S PbS + 2 H+

Precipitation is incomplete if strong mineral acids are present. It is advisable to buffer the
mixture with sodium acetate.
The precipitate decomposes when concentrated nitric acid is added, and white, finely
divided elementary sulphur is precipitated:

3 PbS + 8 HNO3 3 Pb2+ + 6 NO3 + 3 S + 2 NO + 4 H2O

If the mixture is boiled, sulphur is oxidised by nitric acid to sulphate which immediately
forms white lead sulphate precipitate with the lead ions.

3. Ammonia solution: white precipitate of lead hydroxide, solubility product constant

Ksp(Pb(OH)2, 25 C)= 1.42x1020:

Pb2+ + 2 NH3 + 2 H2O Pb(OH)2 + 2 NH4+

The precipitate is insoluble in excess reagent.

33
4. Sodium hydroxide: white precipitate of lead hydroxide:

Pb2+ + 2 OH Pb(OH)2

The precipitate dissolves in excess reagent, when tetrahydroxoplumbate(II) ions are

formed:
Pb(OH)2 + 2 OH [Pb(OH)4]2

Hydrogen peroxide when added to a solution of tetrahydroxoplumbate(II), forms a black

precipitate of lead dioxide by oxidising bivalent lead to the tetravalent state:
[Pb(OH)4]2 + H2O2 PbO2 + 2 H2O + 2 OH

5. Dilute sulphuric acid (or soluble sulphates): white precipitate of lead sulphate,
solubility product constant Ksp(PbSO4, 25 C)= 1.82x108:

Pb2+ + SO42- PbSO4

The precipitate is insoluble in excess reagent. It is soluble in sodium hydroxide and in

more concentrated solution of ammonium tartarate in the presence of ammonia, when
tetrahydroxoplumbate(II) and ditartaratoplumbate(II) ions are formed, respectively:

PbSO4 + 4 OH [Pb(OH)4]2 + SO42

PbSO4 + 2 C4H4O62 [Pb(C4H4O6)2]2 + SO42

6. Potassium chromate: yellow precipitate of lead chromate in neutral, ecetic acid, or

ammonia solution:
Pb2+ + CrO42- PbCrO4

Nitric acid or sodium hydroxide dissolve the precipitate (reactions are reversible):
2 PbCrO4 + 2 H+ 2 Pb2+ + Cr2O72 + H2O
PbCrO4 + 4 OH [Pb(OH)4]2 + CrO42

7. Potassium iodide: yellow precipitate of lead iodide, solubility product constant

Ksp(PbI2, 25 C)= 8.49x109:
Pb2+ + 2 I PbI2

The precipitate is moderately soluble in boiling water to yield a colourless solution, from
which it separates on cooling in golden yellow plates.

8. Sodium sulphite: white precipitate of lead sulphite in neutral solution:

Pb2+ + SO32 PbSO3

The precipitate is less soluble than lead sulphate, though it can be dissolved by both
dilute nitric acid and sodium hydroxide.

34
9. Sodium carbonate: white precipitate of a mixture of lead carbonate and lead
hydroxide:
2 Pb2+ + 2 CO32 + H2O Pb(OH)2 + PbCO3 + CO2

On boiling no visible change takes place. The precipitate dissolves in dilute nitric acid
and in acetic acid and CO2 gas is liberated.

10. Disodium hydrogen phosphate: white precipitate of lead phosphate:

3 Pb2+ + 2 HPO42- Pb3(PO4)2 + 2 H+

Strong acids and also sodium hydroxide dissolve the precipitate.

11. Dithizone (diphenylthiocarbazone, C6H5-NH-NH-C(S)-NN-C6H5) reagent:

brick-red complex salt in neutral, ammoniakal, alkaline, or alkalicyanide solution.

NH NH NH N N N
2+
2 S C + Pb S C Pb C S + 2 H+
N N N N N HN

The reaction is extremely sensitive, but it is not very selective. Heavy metals (silver,
mercury, copper, cadmium, antimony, nickel, and zinc, etc.) interfere, but this effect may
be eliminated by conducting the reaction in the presence of much alkali cyanide.

Summarise the solubility of Sn, Pb, and Al metals in acids and alkali:

Al Sn Pb

HCl

H2SO4

HNO3

aqua regia

NaOH

35