G.C.E.
(A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Introduction
This section describes the physical and chemical properties of elements in s, p and d
blocks. This section will help to identify trends and patterns among elements in the
periodic table.
s Block Elements
4.1 Group 1 elements
All Group 1 elements are metals except hydrogen which is a nonmetal. Unlike most other
metals, they have low densities. All Group 1 elements have the valence shell electron
configuration of ns1 therefore, they are highly reactive.
Sodium can be found naturally as various salts such as NaCl (rock salt) and
Na2B4O7·10H2O (borax). Some examples of naturally occurring potassium salts are KCl
(sylvite) and KCl·MgCl2·6H2O (carnallite).
4.1.1 Group trends
All alkali metals are lustrous. They are high electrical and thermal conductors. These
metals are soft and become even softer when progress down the group. The melting point
of Group 1 metals decreases down the group. The values given in Table 4.1 below can be
used to understand the trends among these elements. Group 1 metals always show
oxidation number of +1 when they form compounds. Most compounds are stable ionic
solids.
Table 4.1 Properties of Group 1 elements
Li Na K Rb Cs
Ground state electronic
[He]2s1 [Ne]3s1 [Ar]4s1 [Kr]5s1 [Xe]6s1
configuration
Metallic radius/ pm 152 186 231 244 262
Melting point/ °C 180 98 64 39 29
Radius of M+/ pm 60 95 133 148 169
1st ionization energy/ kJ mol-1 520 495 418 403 375
2nd ionization energy/ kJ mol-1 7298 4562 3052 2633 2234
Increase in the atomic radius from Li to Cs makes the ionization energy of these elements
to decrease down the group, and this can be used to explain the chemical properties of
Group 1 elements. Reactivity of the Group 1 elements increases down the group.
** When writing equations in inorganic chemistry, it is not always essential to indicate
the physical state of reactants or products. However, always balance equations must be
written to consider as a complete answer.
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4.1.2 Reactions of Group 1 elements
With oxygen (O2) 4M + O2 2M2O
With excess oxygen (O2) Na form peroxides 2Na + O2 Na2O2
With excess oxygen (O2) K, Rb and Cs form M + O2 MO2
superoxides
With nitrogen (N2) only Li forms stable 6Li + N2 2Li3N
nitride
With hydrogen (H2) 2M + H2 2MH
With water (H2O) 2M + 2H2O 2MOH + H2
With acids (H+) 2M + 2H+ 2M+ + H2
Reaction with water
Group 1 metals show an increase in reactivity with water down the group. The reactivity
trend with water is as follows.
Li Na K Rb Cs
Vigourously
Gently Vigorously Explosively Explosively
with ignition
Lithium reacts non-vigorously with water or with water vapour available in the air to
produce lithium hydroxide and hydrogen gas. However, both sodium and potassium react
vigorously with water to produce metal hydroxide and hydrogen gas. These reactions are
highly exothermic except with Li.
Reactions with oxygen/ air
Lithium can react both with oxygen and nitrogen. When heated, lithium burns to produce
lithium oxide (Li2O), a white powder. With nitrogen gas, lithium gives lithium nitride
(Li3N). However, both sodium and potassium do not react with nitrogen gas. When
sodium is burnt in air, sodium peroxide is mainly produced with some sodium oxide. In
contrast, when potassium is burnt in air, potassium superoxide is formed as the main
product with some potassium oxide and peroxide. Oxidation numbers of oxygen in
sodium or potassium peroxide are -1 and in potassium superoxide, oxidation numbers are
-1 and 0.
Group 1 metal oxides react with water to produce metal hydroxides as shown below.
Na2O(s) + H2O(l) 2NaOH(aq)
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
When heated, lithium forms lithium nitride with nitrogen. Only lithium forms a stable
alkali-metal nitride. With water, lithium nitride produces ammonia and lithium hydroxide.
Li3N(s) + 3H2O(l) 3LiOH(aq) + NH3(g)
Group 1 hydroxides react with carbon dioxide to produce relevant carbonates. These
carbonates can further react with carbon dioxide to produce metal hydrogen carbonates.
2NaOH(aq) + CO2(g) Na2CO3(aq) + H2O(l)
Na2CO3(aq) + CO2(g) + H2O(l) 2NaHCO3(s)
Sodium hydrogen carbonate is less soluble than sodium carbonates in water.
Reactions with hydrogen gas
Group 1 elements react with hydrogen to produce solid, ionic metal hydrides. In these
hydrides, hydrogen has the oxidation number of –1. These metal hydrides react
vigorously with water to produce hydrogen gas.
2Na(s) + H2(g) 2NaH(s)
NaH(s) + H2O(l) NaOH(aq) + H2(g)
Reactions with acids
Lithium, sodium and potassium react vigorously with dilute acids to produce hydrogen
gas and relevant metal salts. These reactions are highly exothermic and explosive. A few
selected reactions are shown below.
2Li(s) + dil. 2HNO3(aq) 2LiNO3(aq) + H2(g)
2Na(s) + dil. H2SO4(aq) Na2SO4(aq) + H2(g)
4.1.3 Thermal stability of salts
Decomposition of nitrates
Group 1 nitrates are used as fertilizers and explosives. These nitrates decompose upon
heating. LiNO3 decomposes to produce lithium oxide, nitrogen dioxide and oxygen.
However, the other Group 1 nitrates on heating produce relevant metal nitrite and oxygen.
4LiNO3(s) 2Li2O(s) + 4NO2(g) + O2(g)
2KNO3(s) 2KNO2(s) + O2(g)
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Decomposition of carbonates
Carbonates are stable and they will melt before they decompose into oxides. However,
Li2CO3 is less stable and decomposes readily.
Li2CO3(s) Li2O(s) + CO2(g)
Decomposition of bicarbonates
Decomposition of bicarbonates of Group 1 is shown below.
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
Thermal stability increases down the group.
4.1.4 Solubility of Group 1 salts
All Group 1 salts are soluble in water except some lithium salts such as LiF, Li2CO3 and
Li3PO4. All these salts are white solids unless the salt anion is a coloured ion.
Solubility of Group 1 halides increase down the group is shown in Table 4.2.
Table 4.2 The solubility of halides of sodium
Salt Solubility/ mol L-1
NaF 0.99
NaCl 6.2
NaBr 9.2
NaI 12.3
Variation in the solubility can be understood using the energy cycle for the solvation of
ionic solids. The solubility can be explained using Gibbs free energy. For almost all ionic
solids of Group 1, are soluble in water due to the negative Gibbs free energy in the
solvation process.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Enthalpy and entropy cycles for the solvation process are shown below.
Figure 4.1 Enthalpy and entropy cycles for the solvation process
Using these two energy cycles, enthalpy and entropy change of solvation can be
calculated and these calculated values are given in Table 4.3. Free energy is calculated
using the equation,
ΔGϴ = ΔHϴ - T ΔSϴ
Table 4.3 Free energy change of salts during solvation
Salt Enthalpy change/ Entropy change × T Free energy change/
kJ mol-1 (K × kJ mol-1 K-1) kJ mol-1
NaF +1 -2 +3
NaCl +4 +13 -9
NaBr -1 +18 -19
NaI -9 +23 -32
Calculated Gibbs free energies match with the solubility trend for the sodium halides. The
free energy change gets more negative from sodium fluoride to sodium iodide.
4.1.5 Flame test
The flame test can be used to identify alkali metals and their compounds. Flame colours
of Group 1 metals and compounds are given below.
Lithium – Crimson red Sodium – Yellow
Rubidium – Red-violet Caesium – Blue - violet
Potassium – Lilac
4.2 Group 2 elements
Group 2 elements are known as alkaline earth metals. They are less reactive than Group
1 metals due to its valence shell ns2 electron configuration.
Both calcium and magnesium can be found naturally in dolomite (CaCO3∙MgCO3).
Magnesite (MgCO3), kieserite (MgSO4∙H2O) and carnallite (KMgCl3∙6H2O) are
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examples of minerals with magnesium. Fluoroapatite [3(Ca3(PO4)2)∙CaF2] and gypsum
(CaSO4∙2H2O) are commercially important calcium contacting minerals.
4.2.1 Group trends
Beryllium and magnesium are greyish metals and other Group 2 metals are soft and
silvery in colour. Group 2 metal oxides produce basic oxides except for BeO which shows
amphoteric properties. Beryllium behaves similar to Al and this can be understood using
the diagonal relationship between Al and Be in the periodic table.
Elements of Group 2 have higher densities and stronger metallic bonds compared to the
Group 1 metals. This is due to the availability of a greater number of electrons to form a
stronger metallic bond and their smaller size in atomic radii.
The first ionization energies of Group 2 elements are higher than that of Group 1 elements
due to their electron configuration of ns2. Elements become more reactive and produce
+2 oxidation state easily down the group. The properties of Group 2 elements are given
in Table 4.4.
Table 4.4 Properties of Group 2 elements
Be Mg Ca Sr Ba
Ground state electronic
[He]2s2 [Ne]3s2 [Ar]4s2 [Kr]5s2 [Xe]6s2
configuration
Metallic radius/ pm 112 160 197 215 224
Melting point/ °C 1560 923 1115 1040 973
Radius of M2+/ pm 30 65 99 113 135
1st ionization energy/ 899 736 589 594 502
kJ mol-1
2nd ionization energy/ 1757 1451 1145 1064 965
kJ mol-1
3rd ionization energy/ 14850 7733 4912 4138 3619
kJ mol-1
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
4.2.2 Reactions of alkaline earth Group 2 elements
With oxygen (O2) 2M + O2 2MO
With excess oxygen (O2) Ba forms its Ba + O2 BaO2
peroxide
With nitrogen (N2), at high 3M + N2 M3N2
temperatures
With water (H2O(l)), at room M + 2H2O M(OH)2 + H2
temperature (e.g.: Ca, Sr and Ba)
With hot water (H2O(l)) Mg + 2H2O Mg(OH)2 + H2
(e.g.: Mg reacts slow)
With steam (H2O(g)) Mg + H2O MgO + H2
With acids (H+) M + 2H+ M2+ + H2
With hydrogen (H2), at high M + H2 MH2
temperatures with Ca, Sr, Ba at high
pressure with Mg
With concentrated acids Mg + 2H2SO4 MgSO4 + SO2 + 2H2O
Mg + 4HNO3 Mg(NO3)2+2NO2+2H2O
Reaction with water
Beryllium does not react with water, but it reacts with steam. The reaction of magnesium
with water at room temperature is negligible. However, magnesium reacts slowly with
hot water. Calcium, strontium and barium react readily with cold water. Reaction with
water produces metal hydroxide and hydrogen gas.
Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g)
Reactions with hydrogen
All Group 2 elements, except Be, react with hydrogen to produce metal hydrides which
are ionic solids. In these hydrides, hydrogen has an oxidation number of – 1. These metal
hydrides (not violent as Group 1) react vigorously with water to produce hydrogen gas.
Ca(s) + H2(g) CaH2(s)
CaH2(s) + 2H2O(l) Ca(OH)2(aq) + 2H2(g)
Reaction with nitrogen
All Group 2 elements burns in nitrogen to form M3N2, nitrides. These nitrides react with
water to produce ammonia in the same way as lithium does.
3Mg (s) + N2(g) Mg3N2(s)
Mg3N2(s) + 6H2O(l) 3Mg(OH)2(aq) + 2NH3(g)
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
4.2.3 Thermal stability of salts
Decomposition of nitrates
Upon heating, Group 2 nitrates behave much similar to lithium nitrate. Group 2 nitrates
decompose to produce metal oxide, nitrogen dioxide and oxygen. All Group 2 nitrates are
soluble in water.
2Mg(NO3)2(s) 2MgO(s) + 4NO2(g) + O2(g)
Decomposition of carbonates
Thermal stability of these carbonates increases down the group. Thermal stability of these
carbonates increases with the size of the cation. The polarizing power of the cation
decreases down the group due to the decrease of charge density of the cation. Carbonate
anion attached to Mg2+ cation is highly polarized than that of carbonate attached to Ba2+.
Highly polarized carbonate anion can undergo decomposition easily and this explains the
lower decomposition temperature of MgCO3 than that of [Link] general
decomposition of metal carbonates is shown below.
MCO3 MO + CO2
Decomposition temperature increases from 540 °C for MgCO3 to 1360 °C for BaCO3.
Decomposition of bicarbonates
Group 2 hydrogen carbonates are only stable in aqueous solutions and solid Group 2
hydrogen carbonates are not stable at room temperature.
Ca(HCO3)2(aq) CaCO3(s) + CO2(g) + H2O(l)
4.2.4 Solubility of Group 2 salts
Solubility of Group 2 changes depending on the compound. Some compounds such as
nitrate, nitrite, halides, hydroxides, sulphides, bicarbonates all are soluble in water.
The solubility varies down the group for certain compounds such as hydroxides, sulphate,
sulphite, carbonate, phosphate and oxalate showing the patterns given in Table 4.5.
Salts of Group 2 metals with uninegative anions, such as chloride and nitrates are
generally soluble. However, salts formed with anions containing more than one negative
charge, such as carbonates and phosphates, are insoluble. All carbonates are insoluble
except BeCO3. Hydrogen carbonates are more soluble than carbonates. The solubility of
Group 2 sulphates changes from soluble to insoluble when comparing solubility from
MgSO4 to BaSO4. On the other hand, hydroxides change solubility from insoluble to
soluble when moving down the group. For example, Mg(OH)2 is sparingly soluble
whereas Ba(OH)2 is soluble and produces a strongly basic solution.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Table 4.5 Solubility of Group 1 and 2 compounds
Na+ K+ Mg2+ Ca2+ Sr2+ Ba2+
Cl- aq aq aq aq aq aq
Br- aq aq aq aq aq aq
-
I aq aq aq aq aq aq
-
OH aq aq IS SS SS aq
CO32- aq aq IS IS IS IS
HCO3- aq aq aq aq aq aq
NO2- aq aq aq aq aq aq
-
NO3 aq aq aq aq aq aq
S2- aq aq aq aq aq aq
SO32- aq aq SS IS IS IS
2-
SO4 aq aq aq SS IS IS
PO43- aq aq IS IS IS IS
CrO42- aq aq aq aq IS IS
C2O42- aq aq SS IS IS SS
aq – soluble, IS – insoluble, SS – sparingly soluble
4.2.5 Flame test
Alkaline earth metals and compounds produce characteristic colours with the flame, and
the flame test can be used to identify these elements using the flame colors shown below.
Calcium – Orange-red Strontium – Crimson red Barium – Yellowish-green
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