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Chemistry · Ch 10 — The s-Block Elements

Some Important Compounds of Sodium

10.4

Some Important Compounds of Sodium

Four sodium compounds dominate industrial chemistry: sodium carbonate, sodium chloride, sodium hydroxide and sodium hydrogencarbonate. Each is manufactured on a large scale by a distinct industrial process.

Sodium Carbonate (Washing Soda), Na2CO3⋅10H2ONa_2CO_3\cdot 10H_2O

Industrially, sodium carbonate is made by the Solvay process, which exploits the comparatively low solubility of sodium hydrogencarbonate. CO2CO_2 is passed into a concentrated brine solution that has been saturated with ammonia; the ammonia first forms ammonium carbonate, which is then further carbonated to ammonium hydrogencarbonate:

2NH3+H2O+CO2→(NH4)2CO32NH_3 + H_2O + CO_2 \rightarrow (NH_4)_2CO_3

(NH4)2CO3+H2O+CO2→2NH4HCO3(NH_4)_2CO_3 + H_2O + CO_2 \rightarrow 2NH_4HCO_3

This ammonium hydrogencarbonate then reacts with the sodium chloride present, precipitating sodium hydrogencarbonate — the least soluble species in the mixture:

NH4HCO3+NaCl→NH4Cl+NaHCO3↓NH_4HCO_3 + NaCl \rightarrow NH_4Cl + NaHCO_3\downarrow

The precipitated NaHCO3NaHCO_3 crystals are then heated (calcined) to give the carbonate:

2NaHCO3→Na2CO3+CO2+H2O2NaHCO_3 \rightarrow Na_2CO_3 + CO_2 + H_2O

Ammonia is regenerated (and recycled) by treating the leftover NH4ClNH_4Cl-containing liquor with slaked lime, which also yields calcium chloride as a by-product:

2NH4Cl+Ca(OH)2→2NH3+CaCl2+H2O2NH_4Cl + Ca(OH)_2 \rightarrow 2NH_3 + CaCl_2 + H_2O

This process cannot, however, be adapted to manufacture potassium carbonate, because potassium hydrogencarbonate is too soluble to precipitate out of a saturated potassium chloride solution the way its sodium analogue does.

Pure sodium carbonate is a white crystalline solid that normally exists as the decahydrate, Na2CO3⋅10H2ONa_2CO_3\cdot 10H_2O — this is washing soda — and dissolves freely in water. On heating it progressively loses its water of crystallisation, first to the monohydrate and then, above 373 K, to the fully anhydrous white powder known as soda ash:

Na2CO3⋅10H2O→375 KNa2CO3⋅H2O+9H2ONa_2CO_3\cdot 10H_2O \xrightarrow{375\,K} Na_2CO_3\cdot H_2O + 9H_2O

Na2CO3⋅H2O→>373 KNa2CO3+H2ONa_2CO_3\cdot H_2O \xrightarrow{>373\,K} Na_2CO_3 + H_2O

Its aqueous solution is alkaline because the carbonate ion is hydrolysed by water:

CO32−+H2O→HCO3−+OH−CO_3^{2-} + H_2O \rightarrow HCO_3^- + OH^-

Sodium carbonate is used for water softening, laundering and general cleaning; in the manufacture of glass, soap, borax and caustic soda; across the paper, paint and textile industries; and as a standard laboratory reagent for both qualitative and quantitative analysis.

Sodium Chloride, NaClNaCl

Sea water — roughly 2.7–2.9% salt by mass — is the most abundant natural source of sodium chloride, and in tropical countries such as India it is recovered simply by evaporating sea water in the sun (around 50 lakh tonnes are produced annually in India this way). The crude salt obtained by crystallising brine carries sodium sulphate, calcium sulphate, calcium chloride and magnesium chloride as impurities; the calcium and magnesium chlorides are particularly troublesome because they are deliquescent and pull moisture from the air. To purify the salt, the crude material is redissolved in the minimum amount of water, filtered to remove insoluble matter, and the filtrate is saturated with hydrogen chloride gas; pure sodium chloride crystallises out while the more soluble calcium and magnesium chlorides stay in solution.

Sodium chloride melts at 1081 K, and its solubility (36.0 g per 100 g of water at 273 K) barely changes with temperature. Beyond its everyday use as table salt, it is the starting material for the industrial production of Na2O2Na_2O_2, NaOHNaOH and Na2CO3Na_2CO_3.

Sodium Hydroxide (Caustic Soda), NaOHNaOH

Sodium hydroxide is manufactured commercially by electrolysing brine in a Castner–Kellner cell, using a mercury cathode and a carbon anode. Sodium metal deposited at the cathode immediately alloys with the mercury to form sodium amalgam, while chlorine gas is liberated at the anode:

Cathode:Na++e−→HgNa-amalgam\text{Cathode:}\quad Na^+ + e^- \xrightarrow{Hg} Na\text{-amalgam}

Anode:Cl−→12Cl2+e−\text{Anode:}\quad Cl^- \rightarrow \tfrac{1}{2}Cl_2 + e^-

Treating the amalgam with water then liberates the hydroxide together with hydrogen gas, regenerating the mercury:

2Na-amalgam+2H2O→2NaOH+2Hg+H22Na\text{-amalgam} + 2H_2O \rightarrow 2NaOH + 2Hg + H_2

Sodium hydroxide is a white, translucent solid, melting at 591 K, and dissolves readily in water to give a strongly alkaline solution. Its crystals are deliquescent, and a freshly exposed solution will slowly absorb atmospheric CO2CO_2 at the surface to form Na2CO3Na_2CO_3. …