Group 1: Alkali metals

Li, Na, K, Rb and Cs 3Li: [He] 2s1 ;37Rb: [Kr] 5s1 ;11Na: [Ne] 3s1 ; 55Cs: [Xe] 6s1 ;19K: [Ar] 4s1 ;Fr: [Rn] 7s1

General remarks
They are body centered cubic structure and atoms are surrounded by 8 nearest neighbours with six more atoms at a distance metals are extremely reactive and electropositive (prone to lose electrons) and exist in combination with other elements or radicals as positive ions, e.g. NaCl, K2SO4. All alkali metal atoms have one electron in the outer shell preceded by a closed shell containing eight electrons except for lithium which has a closed shell of two.

Cont
The alkali metals have lower ionisation energies than any other group of elements The atoms and ions of the alkali metals increase in size with increasing atomic number, since each succeeding member has an extra closed shell of electrons. Question: Why Li ion have high NEP:b/c Li being smaller than those of other alkali metals it is strongly hydrated in aqueous solution and it becomes a better reducing agent than group 1 metals in aqueous solution. The value = {Li++(aq) + e Li(s) E = -3.04 V Oxdn = +3.04V}

Properties of the alkali metals

Physical properties The metals are soft and silvery colored; they are extremely good conductors of heat and electricity. Lithium, sodium and potassium are less dense and rubidium and cesium more dense than water. Because they rapidly tarnish and lose their silvery appearance in air, and they are generally stored under oil.

Chemical properties
The metals are very reactive, increasingly so with increasing atomic number; thus lithium reacts quietly with water, 2Li(s) + 2H2O (l) 2LiOH (aq) + H2 (g) sodium and potassium react with increasing vigour (strength), and rubidium and cesium with exceptional violence. In all cases an alkali and hydrogen are produced, e.g.
2K(s) + 2H2O(l) 2KOH(aq) + H2(g) They react with a variety of non-metals when heated to give oxides, sulphides, halides, hydrides, etc., e.g. 4Li(s) + O2(g) 2(Li)2O(s) 2Na(s) + S(s) (Na)2S(s) 2K(s) + Cl2(g) 2KCl(s) 2Rb(s) + H2(g) 2RbH(s)

Reactions of Metals that burn in a stream of HCl

The metals(Na) burn in a stream of hydrogen chloride and react with ammonia when heated, e.g. 2Na(s) + 2HCl(g) 2NaCl(s) + H2(g) 2Na(s) + 2NH3(g) 2NaNH2(s) + H2(g) sodium amide Use: production of indigo, hydrazine and sodium cyanide

Oxides of the alkali metals

All three oxide ions are unstable in the presence of water, e.g. Lithium (Li)2O(s) + H2O(l) 2LiOH(aq) or O2- + H2O(l) 2OH-(aq) Sodium (Na)2O2(s) + 2H2O(l) 2NaOH(aq) + H2O2(l) or O22- + 2H2O(l) 2OH-(aq) + H2O2(l) Potassium 2KO2(s) + 2H2O(l) 2KOH(aq) + H2O2(l) + O2(g) or 2O2 - + 2H2O(l) 2OH-(aq) + H2O2(l) + O2(g)

The hydroxide of sodium and potassium

by Castner-Kellner process and the Gibbs diaphragm cell process. Saturated solution of sodium chloride flows through the cell in the same direction as a shallow stream of mercury which constitutes the cathode; the anode consists of a number of titanium blocks. On electrolysis chlorine is discharged at the anode and sodium at the cathode, where it dissolves in the mercury and is removed from the cell. The sodium amalgam is passed through water the sodium reacts to form 50% sodium hydroxide solution of high purity, the reaction being catalysed by the presence of iron grids. The mercury is then returned to the cell. The products are thus sodium hydroxide (NaOH), chlorine (Cl2) and hydrogen (H2).

Castner Kellner process

 Cathode Anode Na+ discharge NaCl Cl- discharge .............................................................................................................. .................... 2Na+ + 2e 2Na H2O H+ + OH2Cl- Cl + 2e Na + Hg Na/Hg 2Na/Hg + 2H2O 2NaOH + H2 + 2Hg Sodium is discharged in preference to hydrogen in the cell, since hydrogen has a high overvoltage at a mercury electrode. This amounts to saying that mercury is a poor catalyst for either or both the discharge of hydrogen ions and the combination of hydrogen to H2. Since the sodium dissolves in the mercury which is circulated through the cell, the formation of sodium hydroxide and hydrogen in the electrolytic cell itself is prevented.

Castner Kellner process

Reactions of sodium and potassium hydroxides

Sodium and potassium hydroxides are white deliquescent solids which are caustic, and slimy to touch; they dissolve readily in water with the vigorous evolution of heat. NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) or OH-(aq) + H+(aq) H2O(l) NaOH(aq) + NH4Cl(aq) NaCl(aq) + H2O(l) + NH3(g) or OH-(aq) + NH4+(aq) H2O(l) + NH3(g) In aqueous solution they react with many salts and precipitate the corresponding basic hydroxide, e.g. CuSO4(aq) + 2NaOH(aq) Cu(OH)2(s) + (Na)2SO4(aq) or Cu2+(aq) + 2OH-(aq) Cu(OH)2(s)

Uses of sodium and potassium hydroxides

Sodium hydroxide is used in the laboratory for absorbing carbon dioxide and other acidic gases, in a number of organic reactions involving hydrolysis, and in volumetric analysis. Industrially :it is used in the manufacture of soap (essentially sodium stearate) and sodium formate (obtained by heating sodium hydroxide with carbon monoxide under pressure). A solution of potassium hydroxide in alcohol is used in organic chemistry; industrially the main use of potassium hydroxide is in the manufacture of soft soap.

The manufacture of sodium carbonate - the Solvay process

CaCO3(s) + 2NaCl(s) (Na)2CO3(s) + CaCl2(s) The raw materials are sodium chloride, calcium carbonate and ammonia (practically all recovered in the process), plus energy (fuel). The calcium carbonate is strongly heated to give quicklime (CaO) and carbon dioxide: CaCO3(s) CaO(s) + CO2(g) NH3(g) + H2O(l) NH3H2O(aq) NH4+(aq) + OH-(aq) Na+(aq) + Cl-(aq) + NH4+(aq) + OH-(aq) + CO2(g) Na+(aq) + HCO3-(aq) + NH4+(aq) + Cl-(aq) Na+(aq) + HCO3-(aq) NaHCO3(s) Sodium hydrogen carbonate which is not very soluble in sodium chloride solution - the common ion effect - is filtered and heated to produce sodium carbonate: 2NaHCO3(s) (Na)2CO3(s) + H2O(l) + CO2(g) :rain water H2O(l) + CO2(g) H2CO3 (aq)

Cont
The sodium carbonate at this stage is contaminated with ammonium salts. If required to be pure, it is dissolved in water and carbon dioxide is blown through the solution. The precipitate of sodium hydrogen carbonate is filtered and heated to produce pure sodium carbonate; recrystallisation from water produces washing soda, (Na)2CO310H2O. (Na)2CO3(aq) + H2O(l) + CO2(g) 2NaHCO3(s) 2NaHCO3(s) (Na)2CO3(s) + H2O(l) + CO2(g)

The manufacture of potassium carbonate

Potassium carbonate cannot be made by the Solvay process since potassium hydrogen carbonate is rather too soluble in water to be precipitated. It can, however, be made by passing carbon dioxide into a solution of potassium hydroxide; evaporation and subsequent ignition give the carbonate: KOH(aq) + CO2(g) KHCO3(aq) 2KHCO3(aq) (K)2CO3(s) + H2O(l) + CO2(g) Reaction for bleach Bleaching powder reaction: Ca(OH)2 + Cl2CaOCl2 + H2

Uses of sodium and potassium carbonates

Reaction:CaCl2(aq) + (Na)2CO3(aq) CaCO3(s) + 2NaCl(aq) Sodium carbonate is often used in the laboratory as a volumetric reagent. Industrially: it is used in a wide variety of ways, including the manufacture of glass, in the preparation of sodium salts, in the treatment of hard water, for the manufacture of soap, and in papermaking. Potassium carbonate, which is more expensive, is used as a drying agent in organic chemistry since it is deliquescent (melts);and mixed with sodium carbonate it is used as fusion mixture for getting insoluble salts into solution during analytical procedures.

Reaction of hydrogen carbonates of sodium and potassium

It is obtained by passing carbon dioxide through a cold concentrated solution of the corresponding carbonate, e.g. (Na)2CO3(aq) + H2O(l) + CO2(g) 2NaHCO3(s) 2KHCO3(aq) (K)2CO3(s) + H2O(l) + CO2(g) Sodium hydrogen carbonate is much less soluble in water than potassium hydrogen carbonate and both solutions are alkaline by hydrolysis, but not to the same extent as the corresponding carbonates: HCO3-(aq) + H2O(l) H2CO3(s) + OH-(l) Because sodium hydrogen carbonate solution is less alkaline than sodium carbonate solution, the former is often used to precipitate normal carbonates which would otherwise be formed as basic carbonates. Cu2+(aq) + 2HCO3-(aq) CuCO3(s) + H2O(l) + CO2(g)

The nitrates
Sodium nitrate occurs as Chile saltpetre in the desert
regions in Chile, along with sodium iodate (NaIO3) (from which iodine is extracted). NaNO3 can be separated from NaIO3 by recrystallisation from an aqueous solution, as it is less soluble than the iodate. Both sodium and potassium nitrates are used as nitrogenous fertilizers. The latter is a constituent in gunpowder. Sodium nitrate is also used as a meat preservative. When heated, the nitrates decompose to give the nitrite and oxygen, e.g. 2KNO3(s) 2KNO2(s) + O2(g)

The nitrites
The nitrites can be made by the thermal decomposition 2NaOH(aq) + NO2(g) + NO(g) 2KNO2(aq) + H2O(l)

The nitrites can be purified by crystallisation from water. Sodium nitrite is used extensively in the production of dyes. Sulphates 2NaOH(aq) + H2SO4(aq) Na2SO4(aq) + H2O(l) Sodium sulphate crystallises as the decahydrate Na2SO410H2O which is efflourescence to give the anhydrous salt; when heated above 32.5C.

Cont
Potassium sulphate crystallises as the anhydrous salt and it is found as such in the Strassfurt deposits in Germany. It is used for making up potassium deficiency in soil, as a drying agent and for making potash alum KAl(SO4)212H2O, which is used as a mordant in dyeing Hydrolysis of alkali metal salts alkali metal halides, nitrates and sulphates are neutral in aqueous solution; but other salts, for example hydrogen carbonates, carbonates, cyanides and sulphides, show an alkaline reaction in solution: CO32-(aq) + H2O(l) HCO3-(aq) + OH-(aq) HCO3-(aq) + H2O(l) H2CO3(aq) + OH-(aq) CN-(aq) + H2O(l) HCN(aq) + OH-(aq) S2-(aq) + H2O(l) HS-(aq) + OH-(aq) HS-(aq) + H2O(l) H2S(aq) + OH-(aq)

Potash alum

Questions
Why is lithium a poor reducing agent extraction and occurrence Chemical and physical properties and reactions Explain of Castner Kellner process Explain Solvay process and uses of carbonates Bromides and iodides: reactions Hydrogen sulphates and hydrolysis of alkali metals