NOTE

C H E M I S T R Y

HYDROGEN AND THE

S-BLOCK ELEMENTS
THE STORY OF CARBONATES AND BICARBONATES

What you already know

• Alkali metal solutions in liquid ammonia • Similarities between lithium and magnesium
• Alkali metal salts of oxo-acids • Compounds of sodium - Preparation,
• Anomalous properties of lithium properties and uses of sodium hydroxide

What you will learn

• Compounds of sodium continued -

Preparation, properties and uses of:

Sodium Carbonate (Na2CO3.10H2O)

Preparation of sodium carbonate

By Solvay (ammonia soda) process, this process takes place in several different steps.
Step 1: Saturation of brine with NH3 and CO2 (in ammonia absorber)
Brine is the saturated solution of NaCl.
2NH3 + CO2 + H2O (NH2)2CO3
Ammoniated brine is filtered to remove Ca and Mg impurities as their insoluble carbonates.

CaCl2 + (NH4) 2CO3 CaCO3 + 2NH4Cl

MgCl2 + (NH4) 2CO3 MgCO3 + 2NH4Cl

Step 2: Formation of insoluble NaHCO3 (in carbonation tower)

The (NH4)2CO3 formed in the first step is concentrated with CO2 and H2O to form NH4HCO3
(NH4)2CO3 + H2O + CO2 2NH4HCO3
30o C
NH4HCO3 + NaCl NaHCO3 + NH4Cl

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Sodium
bicarbonate

Dry ice Ammoniated Dry ice Sodium Filtrate

(Solid CO2) brine solution (Solid CO2) bicarbonate
solution
Fig. 1: Synthesis of sodium bicarbonate

The reaction is exothermic.

NaHCO3 is insoluble in cold brine solution because of the common ion effect. It is separated by
filtration and the filtrate is used for recovering NH3 & CO2.

Step 3: Calcination to get sodium carbonate.

150o C
2NaHCO3 Na2CO3 + CO4 + H2O

Sodium Sodium
bicarbonate carbonate

Fig. 2: Synthesis of sodium carbonate

Step 4: Recovery of NH3 and CO2 (in recovery tower).

△
NH4HCO3 NH3 + CO2 + H2O
Steam
△
2NH4Cl + Ca(OH)2 2NH3 + 2H2O + CaCl2
Steam

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Step 5: Preparation of CO2 (in lime kiln).

1375 K
CaCO3 CaO + CO2
CaO + H2O Ca(OH)2

Ca(OH)2 is called slaked lime.

Solvay process cannot be extended to the manufacture of K2CO3 because KHCO3 is too soluble
to be precipitated by the addition of NH4HCO3 to a saturated solution of potassium chloride.
Properties of sodium carbonate
1. It is a white crystalline solid. The common form is decahydrate, Na2CO3.10H2O. This
form is called washing soda. The decahydrate form on standing in air effloresces and
crumbles to powder. It is the monohydrate, Na2CO3.H2O. Above 373 K, the monohydrate
becomes completely anhydrous and changes to a white powder called soda ash.
375 K
Na2CO3.10H2O Na2CO3.H2O + 9H2O
Monohydrate
>373 K
Na2CO3.H2O Na2CO3 + H2O
Soda ash
2. It is readily soluble in water with the evolution of a considerable amount of heat. The solution
is alkaline in nature.
Na2CO3 + 2H2O ⇌ 2NaOH + H2CO3

Uses of sodium carbonate

1. It is used in water softening, laundering and cleaning.
2. It is used in the manufacturing of glass, soap, borax and caustic soda.
3. It is used in paper, paints and textile industries.
4. It is an important laboratory reagent.

Sodium Bicarbonate (NaHCO3)

Preparation of sodium bicarbonate

Obtained as an intermediate product in the Solvay's (ammonia-soda) process. Carbonate can be
changed to bicarbonate by passing CO2 through its saturated solution
Na2CO3 + CO2 + H2O 2NaHCO3
NaHCO3 is sparingly soluble.
Preparation of sodium bicarbonate
1. It is a white crystalline solid sparingly soluble in water. The solution is alkaline in nature.
NaHCO3 + H2O ⇌ 2NaOH + H2CO3

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2. The solution is weakly basic. It gives yellow colour with methyl orange but no colour with
phenolphthalein.
3. On heating, it loses CO2 and H2O forming Na2CO3
△
2NaHCO3 Na2CO3 + CO2 + H2O
NaHCO3 is known as baking soda because it decomposes on heating to generate bubbles
of CO2 which escapes to make the dough soft and fluffy.
Uses of sodium bicarbonate
1. It is largely used for making baking powder. Baking powder is a mixture of potassium
hydrogen tartrate and NaHCO3.
2. It is a mild antiseptic for skin infections.
3. It is used in fire extinguishers.

Sodium Chloride (NaCl)

Preparation of sodium chloride

1. Evaporation of seawater
The most abundant source of sodium chloride is seawater which contains 2.7 to 2.9% by
mass of the salt.
2. Crystallisation of brine solution
a. Crude NaCl contains sodium sulphate, calcium sulphate, calcium chloride and
magnesium chloride as impurities.
b. CaCl2 and MgCl2 are impurities because they are deliquescent.
Preparation of pure NaCl from crude salt
The crude salt is dissolved in a minimum amount of water and filtered to remove insoluble impurities.
The solution is then saturated with HCl gas to give crystals of pure NaCl. CaCl2 and MgCl2, being
more soluble than NaCl, remain in the solution.
Properties of sodium chloride
1. NaCl melts at 1081 K.
2. It has a solubility of 36.0 g in 100 g of water at 273 K.
3. The solubility does not increase appreciably with the increase in temperature.
Uses of sodium chloride
1. It is used as a common salt for domestic purposes.
2. It is used for the preparation of Na2O2, NaOH and Na2CO3.
Biological importance of sodium (Na) and potassium (K)
A typical 70 kg man contains about 90 g of Na and 170 g of K compared to only 5 g of iron
and 0.06 g of copper. Na+ ions are found primarily on the outside of a cell, participating in the
transmission of nerve signals, in regulating the flow of water across cell membranes and in the
transport of sugars and amino acids into cells. K+ ions are the most abundant cations within cell
fluids, where they activate many enzymes, participate in the oxidation of glucose to produce ATP
and, with Na, are responsible for the transmission of nerve signals. In blood plasma, Na is present
to the extent of 143 mmol L–1, whereas the K level is only 5 mmol L–1 within the red blood cells.

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These concentrations change to 10 mmol L–1 (Na+) and 105 mmol L–1 (K+). These ionic gradients
demonstrate a discriminatory mechanism, called the sodium-potassium pump.

Alkaline Earth Metals

Group 2

• Consists of Beryllium (Be), Magnesium (Mg), Calcium (Ca),

Strontium (Sr), Barium (Ba), Radium (Ra).
• General electronic configuration is [noble gas] ns2.
• These elements except beryllium are commonly known
as alkaline earth metals because their oxides and
hydroxides are alkaline in nature and these metal oxides
are found in the earth’s crust.

Fig.3: Group 2 metals

Some important properties/trends of alkaline earth metals

Electronic Configuration
Two valence
electrons
• Alkaline earth metals have two valence electrons ns2
outside the noble gas core.
• General valence shell electronic configuration is ns2
• They will readily lose electrons to give dipositive M2+ ions.
The compounds of these elements are predominantly
ionic

Fig. 4: Representation of
electronic configuration of Mg
Atomic and Ionic Radii

Corresponding alkali metals

Alkaline earth metals <
in the same period

• On moving from left to right across a period, as the effective nuclear charge (Zeff) increases,
there is a subsequent decrease in size. So, the atomic and ionic radii of alkaline earth metals
are smaller than their corresponding alkali metals in the same period. This is due to the
increased effective nuclear charge with no addition of new shells.
• Within the group, atomic and ionic radii increase with the increase in atomic number because
on moving down a group, as the atomic number increases (i.e, shells are added), the atom
becomes larger.

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Property Beryllium Magnesium Calcium Strontium Barium Radium

Atomic number 4 12 20 38 56 88

Atomic mass 9.01 24.31 40.08 87.62 137.33 226.03

Electronic
[He] 2s2 [Ne] 3s2 [Ar] 4s2 [Kr] 5s2 [Xe] 6s2 [Rn] 7s2
configuration

Ionisation
enthalpy (I) 899 737 590 549 503 509
(kJ mol–1)
Ionisation
enthalpy (II) 1757 1450 1145 1064 965 979
(kJ mol–1)
Hydration
enthalpy -2494 -1921 -1577 -1443 -1305 -
(kJ mol–1)

Metallic radius
111 160 197 215 222 -
(pm)

Ionic radius M2+

31 72 100 118 135 148
(pm)

Melting point
1560 924 1124 1062 1002 973
(K)

Boiling point (K) 2745 1363 1767 1655 2078 (1973)

Density
1.84 1.74 1.55 2.63 3.59 (5.5)
(g cm–3)

Standard
potential E–/ V -1.97 -2.36 -2.84 -2.89 -2.92 -2.92
for (M2+/M)

Occurrence in
2ppm 2.76* 4.6* 384ppm 390ppm 10-6ppm
lithosphere

* Percentage by weight.
Table 1: Atomic and physical properties of alkaline earth metals

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• Atomic number increases from Be to Ra.

• Atomic mass increases from Be to Ra in g mol–1.
• Ionisation enthalpy (in kJ mol–1) (the amount of energy that an isolated gaseous atom requires
to lose an electron in its ground state) decreases down the group. As the atomic radius
increases, there is less attraction of outermost electrons with the nucleus and hence less
energy is required to lose an electron. So here, the first ionisation energy of all the elements
in the group decreases from Be to Ba and at the end, there is a sudden increase towards
the radium and the same trend continues in the case of 2nd ionisation energy. This sudden
increase in the case of Ra is due to the poor shielding effect of f-electrons.
• Hydration enthalpy (in kJ mol–1) will decrease down the group.
• Metallic radius and ionic radius increases down the group. As the atomic number increases
(i.e., shells are added), the atom becomes larger.
Ionisation Enthalpy
• The amount of energy that an isolated gaseous atom requires to lose an electron in its ground
state.
Atomic Size: Be < Mg < Ca < Sr < Ba < Ra
Ionisation enthalpy: Be > Mg > Ca > Sr > Ra > Ba

Note

The ionization enthalpy of radium is more than barium due to the poor shielding of f electrons in
radium.

Trend in ionisation energy down the group

• The alkaline earth metals have low I.E. due to their fairly large size of atoms. However, the
first I.E. of the alkaline earth metals is greater than the corresponding group 1 metals due
to their small size as compared to the corresponding alkali metals as well as their stable
electronic configuration.
• The second I.E. of the alkaline earth metals is less than those of their corresponding alkali
metals because, in alkali metals, the second electron is to be removed from an inert gas
configuration.

IE1 IE2

Group 2 metal

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IE1 IE2

Group 1 metal
(IE1)group 1 < (IE1)group 2

(IE2)group 1 > (IE1)group 2

Fig. 5: Comparison of ionisation energies of alkali metals and alkaline earth metals
Hydration Enthalpy
• The energy released when one gram mole of an ion is dissolved in water to get it hydrated
is called hydration enthalpy.
• Hydration enthalpy is directly proportional to ionic charge and is inversely proportional to
ionic radius (ionic size).
• For divalent alkaline earth metal ions (M2+), the smaller the ionic size greater is the hydration
enthalpy. The smaller the ions, the higher is the charge density, which results in stronger
attraction with water i.e., hydration enthalpies of alkaline earth metal ions decrease with
increase in ionic size. Thus, the correct order of hydration enthalpies is
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+
• Compounds of alkaline earth metals are more extensively hydrated than those of alkali
metals due to their high charge densities compared to alkali metals.
Example: MgCl2 and CaCl2 exist as MgCl2.6H2O and CaCl2.6H2O but NaCl and KCl do not
form such hydrates.
Physical Properties
1. Alkaline earth metals are silvery-white, lustrous and relatively soft, but are harder than alkali
metals. Be and Mg appear to be somewhat greyish.
2. They are strongly electropositive in nature due to their low ionisation energies.
3. They have high electrical and thermal conductivities.
4. They have higher melting and boiling points due to their smaller sizes as compared to the
alkali metals.
Flame Test
• The alkaline earth metals and their salts impart characteristic colour to an oxidising flame.
• This is because the heat from the flame excites the outermost loosely held electrons (ns2) to
a higher energy level. When the excited electron comes back to the ground state, there is an
emission of radiation in the visible region.
• Group 2 elements mainly Ca, Sr and Ba impart characteristic brick red, crimson and apple
green colours respectively to flame.

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Calcium Strontium Barium

Brick red Crimson red Apple green

Fig. 6: Flame test of Ca, Sr and Ba

Note

The electrons in Be and Mg are too strongly bound to get excited by flame. To excite these electrons,
high energy is required because of which, during the de-excitation, the radiation emitted will not
lie in the visible region.

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