Group 16: Oxygen and Sulphur

[He] 2s22p4 and [e] 3s23p4 17/10/2012

General remarks about Group 6A

They show non-metallic to metallic properties with increasing atomic number within the periodic group. Oxygen and sulphur are non-metals, selenium and tellurium are semiconductors and polonium is metallic.

 Elements can combine and forming octets- by gaining two electrons to form the 2-valent ion, e.g. O2-, S2-, except for polonium which is too metallic, Same stable state occurs when forming two covalent bonds, e.g. the hydrides H2O, H2S, H2Se, H2Te, H2Po. Sulphur, selenium, tellurium and polonium have vacant d orbitals that can be utilized without too great an energy change, they are able to form covalent compounds in which the octet of electrons is expanded: for instance, the valences of sulphur in H2S, SCl4, SF6 are two, four and six respectively.

Occurrence and preparation of oxygen

Oxygen occurs in the atmosphere to the extent of about 21 % by volume. Oxygen can be obtained in the laboratory in different ways: By the thermal decomposition of the oxides of metals low in the electrode potential series The oxides of most metals are thermally stable. However, the oxides of silver and mercury are thermally unstable: 2Ag2O(s) 4Ag(s) + O2(g) 2HgO(s) 2Hg(l) + O2(g) By the thermal decomposition of higher oxides So-called higher oxides such as Pb3O4 and PbO2 decompose thermally into the lower oxide and oxygen: 2Pb3O4(s) 6 PbO(s) + O2(g) 2PbO2(s) 2PbO(s) + O2(g)

preparation of oxygen
By the decomposition of peroxides Hydrogen peroxide is readily decomposed into water and oxygen by catalysts such as finely divided metals and manganese dioxide: 2H2O2(aq) 2H2O(l) + O2(g) Solid peroxides such as sodium peroxide evolve oxygen on the addition of water: 2Na2O2(s) + 2H2O(l) 4NaOH(aq) + O2(g)

By electrolysis Electrolysis of aqueous solution of alkalis and acids results in the discharge of hydrogen at the cathode and oxygen at the anode. Pure water also decomposes in the same way but, since pure water is a very poor conductor of electricity, hydrogen and oxygen are only discharged slowly. Industrially oxygen is obtained from the atmosphere by first removing carbon dioxide and water vapour. The remaining gases are then liquefied and fractionally distilled to give nitrogen and oxygen.

The properties of oxygen

Physical properties Oxygen is a colourless and odourless diatomic gas. It liquefies at 183 C and freezes at 218 C. Its electron configuration is [He]2s22p4.

Chemical properties
Chemically it is very reactive, forming compounds with all other elements except the noble gases and, apart from the halogens and some unreactive metals. The action of a silent electrical discharge upon oxygen gives ozone concentrations of up to 10%. Its importance in normal respiration and combustion processes: oxygen is used in oxyacetylene welding and cutting, in the manufacture of many metals particularly steel and in hospitals for breathing in patients. high altitude flying and in mountaineering. The combustion of fuels, e.g. kerosene in liquid oxygen, provides the tremendous thrust required to put satellites into space. It also used to bleach pulp and paper.

Ozone, O3 an allotrope of oxygen

Ozone is a layer protects the earths surface from an excessive concentration of ultraviolet radiation.

Characteristics: Ozone is a pale blue, poisonous gas with a sharp, irritating odour. Side effects: Exposure to 1 ppm produces a headaches, burning eyes and irritation of respiratory passage. Occurrence: Ozone comes from stratosphere (second major layer of the Earth atmosphere) and is too reactive to remain for long in the atmosphere at sea level, but at a height of about 20 kilometers it is formed from atmospheric oxygen by the energy of sunlight.

Ozone Preparation
Preparation When a slow dry stream of oxygen is passed through a silent electrical discharge up to 10% conversion to ozone occurs to give hydrides. 3O2 2O3 H(298 K) = +284 kJ mol-1
+ +

Ozone
Ozone is prepared by passing air or oxygen between two plates that are charged with several thousand volts of alternating current. The electrical discharge produces ozone. 3O2 2O3 H(298 K) = +284 kJ mol-1 At ordinary temperature, the yield is low, However at liquid air temperature the yield is near 90%. SIMPLE OZONIZING APPARATUS: The apparatus consists of two glass tubes. one enclosing the other, Tin or Aluminum foil is wrapped around each tube and connected to two wires to a source of high voltage current. When the current flows, the pieces of foil become highly charged so that there is a silent electric discharge from one to the other. Some of the oxygen passes between the two pieces of metal, during the discharge is converted into ozone. This silent discharge produces more ozone when compared to the spark discharge.

Properties of ozone
Ozone is a much more powerful oxidizing agent than molecular oxygen; it will oxidize lead sulphide to lead sulphate, iodide ions to iodine and iron(II) ions to the iron(III) state: PbS(s) + 4O3(g) PbSO4(s) + 4O2(g) 2I-(aq) + H2O(l) + O3(g) 2OH- (aq) + I2(s) + O2(g) 2Fe2+(aq) + 2H+(aq) + O3(g) 2Fe3+(aq) + H2O(l) + O2(g) The iodine liberated when ozone reacts with an excess of potassium iodide solution (acidified to remove the hydroxyl ions that are formed) can be titrated with a standard solution of sodium thiosulphate. This is a quantitative method for estimating the gas.

Ozone layer
nitrogen oxide combines with ozone, Which leads to the possibility that nitrogen oxide emission from the exhaust systems of supersonic aircraft, which normally operate in the stratosphere, might be slowly depleting the concentration of the ozone layer in the upper atmosphere. Another threat to the ozone layer is probably posed by the use of two fluorochloromethanes, i.e. CFCl3 and CF2Cl2, which are used in aerosol sprays and as refrigerants. Laboratory experiments have shown that short wavelength ultraviolet radiation of the type present in the stratosphere, and which the ozone layer effectively filters out, decomposes these compounds forming chlorine atoms, which then rapidly react with ozone. Ozone tails mercury, partially converting it into the oxide so that it sticks to the walls of the vessel containing it. This serves as a conclusive test for the presence of ozone in the presence of excess oxygen. Ozone is used in the treatment of domestic water supplies, and in the production of some important pharmaceuticals.

Oxides The preparation of oxides

methods used to obtain the oxides of metals include the thermal decomposition of hydroxides, carbonates and nitrates, e.g. Cu(OH)2(s) CuO(s) + H2O(l) CaCO3(s) CaO(s) + CO2(g) 2Mg(NO3)2(s) 2MgO(s) + 4NO2(g) + O2(g) The oxides of some non-metals and of weak metals can be obtained by oxidation of the element with nitric acid e.g. C(s) + 4HNO3(aq) CO2(g) + 4NO2(g) + 2H2O(l) Sn(s) + 4HNO3(aq) SnO2(s) + 4NO2(g) + 2H2O(l)

Water

Water has the chemical formula H O meaning that one molecule 2 of water is composed of two hydrogen atoms and one oxygen atom. It can also be described ionically as HOH, with a hydrogen ion (H+) that is bonded to a hydroxide ion (OH-). It is in dynamic equilibrium between the liquid and vapor states at standard temperature and pressure. At room temperature, it is a nearly colorless, tasteless, and odorless liquid. It is often referred to in the sciences as the universal solvent and the only pure substance found naturally in all three states of matter.

Cont
Liquid water's high boiling point is due to the high number of hydrogen bonds each molecule can have relative to its low molecular mass. Water is unique because its oxygen atom has two lone pairs and two hydrogen atoms, meaning that the total number of bonds of a water molecule is four. Consider hydrogen fluoride - which has three lone pairs on the F atom but only one H atom - can have a total of only two bonds H-F...H-F...H-F The exact number of hydrogen bonds which a molecule experiences in liquid water fluctuates with time and depends on the temperature.

SULPHUR
Occurrence and preparation of sulphur valuable source of sulphur dioxide is iron pyrites, FeS2. Many sulphur minerals occur, including anhydride, CaSO4, gypsum, CaSO4.2H2O, and Epsom salts, MgSO4.7H2O.

Occurrence and Frasch process

Elemental sulphur deposits are found in volcanic or sedimentary areas of Italy, USA, Russia and the Ukraine

Frasch process
Holes are drilled down through the overlying rock into the sulfur deposits. A special series of pipes are then inserted into the drill hole. The pipes are arranged in a circular pattern. The outer pipes will contain superheated steam (usually about 160170C) which is pumped down into the deposit. Since the melting point of sulfur is so low (115.21 C, just a little over the boiling point of water), it readily liquefies. As the sulfur becomes molten, it is removed by pumping air down the central pipe. When the molten sulfur reaches the surface, it is pumped onto wooden blocks where the sulfur again solidifies. The Frasch process is able to produce sulfur of very high purity, often above 99%.

The allotropy of sulphur

rhombic sulphur, monoclinic sulphur, amorphous sulphur and plastic sulphur. The first two main allotropes contain S8 molecules, in which single bonds unit sulphur atoms into a puckered octagonal ring.

Chemical properties of sulphur

Sulphur combines with most metals when heated, finely divided metals such as magnesium and aluminium (which are high up in the electrode potential series) reacting with considerable vigour, eg, Mg(s) + S(s) MgS(s)

 Non-metals that combine with sulphur directly include fluorine, chlorine, oxygen and carbon; hydrogen combines reversibly to a slight extent when passed through molten sulphur near its boiling point. S(s) + 3F2(g) SF6(g) 2S(s) + Cl2(g) S2Cl2(l) S(s) + O2(g) SO2(g) C(s) + 2S(s) CS2(l) H2(g) + S(l) H2S(g) Sulphur is oxidized by concentrated nitric and sulphuric acid; with hot concentrated solutions of alkalis a sulphide and a sulphite are formed, which react with more sulphur to form polysulphides and a thiosulphate respectively. S(s) + 6HNO3(aq) 2H2O(l) + H2SO4(aq) + 6NO2(aq) S(s) + 2H2SO4(aq) 2H2O(l) + 3SO2(g)

Applications
Sulfur is also used in batteries, detergents, the vulcanization of rubber, fungicides, and in the manufacture of phosphate fertilizers. Sulfites are used to bleach paper and as a preservative in wine and dried fruit. Because of its flammable nature, sulfur also finds use in matches, gunpowder, and fireworks. Sodium or ammonium thiosulfate is used as photographic fixing agents. Magnesium sulfate, better known as Epsom salts, can be used as a laxative, a bath additive, an exfoliant( a gently abrasive cosmetic product designed to remove dead cells from the skin's surface), or a magnesium supplement for plants. Sulfur is used as the light-generating medium in the rare lighting fixtures known as sulfur lamps.

Hydrogen sulphide, H2S

Occurrence and preparation of hydrogen sulphide

It is usually prepared in the laboratory by the action of dilute hydrochloric acid on iron(II) sulphide in a Kipps apparatus: FeS(s) + 2H+(aq) + 2Cl-(aq) Fe2+(aq) + 2Cl(aq) + H2S(g)

Physical properties of hydrogen sulphide

hydrogen sulphide is a gas, since the electronegativity of the sulphur atom is insufficient to allow it to participate in hydrogen bonding. It is an extremely poisonous substance (as little as 1 part per 1000 parts of air is fatal) but fortunately its smell becomes intolerable long before the fatal concentration is reached

Chemical properties of hydrogen sulphide Acid properties H2O(l) + 2H2S(g) H3O+(aq) + HS(aq) H2O(l) + HS- (aq) H3O+(aq) + S2-(aq) the reaction with sodium hydroxide solution produces the hydrosulphide and sulphide, ie., NaHS and Na2S. OH(aq) + H2S(g) H2O(l) + HS- (aq) OH(aq) + HS-(aq) H2O(l) + S2-(aq)

Uses of sulphur dioxide

Sulfur dioxide is sometimes used as a preservative in alcoholic drinks, or dried apricots and other dried fruits. The preservative is used to maintain the appearance of the fruit rather than prevent rotting. This can give fruit a distinctive chemical taste. Sulfur dioxide is also a good reductant. In the presence of water, sulfur dioxide is able to decolorize substances that can be reduced by it; thus making it a useful reducing bleach for papers and delicate materials such as clothes. This bleaching effect normally does not last very long. Oxygen in the atmosphere reoxidizes the reduced dyes, restoring the color. This might explain why older newspapers turn yellow, because paper used for newspaper is naturally yellow.

Cont
Sulfur dioxide is also used to make sulfuric acid, being converted to sulfur trioxide, and then to oleum, which is made into sulfuric acid. Sulfur dioxide for this purpose is made when sulfur combines with oxygen. This is called the contact process. Prior to the development of Freon's, sulfur dioxide was used as a refrigerant in home refrigerators. H2SO3 is also called "hydrogen sulfite" or sulphurous acid.

Manufacture of sulphuric acid Essentially the manufacture of this acid involves the conversion of sulphur dioxide into sulphur trioxide which is then dissolved in water to form sulphuric acid.

The Contact process

Reactions: SO3(g) + H2SO4(g) H2S2O7(l) H2S2O7(l) + H2O(l) 2H2SO4(l) Catalyst: vanadium oxide; temperature : 430oC

 A mixture of sulphur dioxide and air (approximately 8,5 % SO2 and 12,5 % O2 by volume) is passed over a vanadium(V) oxide catalyst at a temperature of about 430 C. The reaction is exothermic and the temperature to about 600 C; the mixture is cooled to about to heat the initial sulphur dioxide/air mixture, and at this stage the conversion of sulphur dioxide to sulphur trioxide is about 66 % complete. The mixture is then passed through three more converters, at each stage the emerging gas stream being cooled to 430 C as described above before passing from one converter to another. The final gas stream (overall conversion of sulphur dioxide to sulphur trioxide being about 98 % complete) is then cooled, and the sulphur trioxide absorbed in 98 % sulphuric acid to give 100 % sulphuric acid, if the absorption is carried further, fuming sulphuric acid or oleum, H2S2O7. Dilution of the fuming sulphuric acid with water gives sulphuric acid.

Uses of sulphuric acid

Paint manufacture - titanium(IV) oxide and lithopone Synthetic fibres - rayon and plastics Acid production - hydrochloric acid and hydrofluoric acid Metallurgy - picking steel and sulphates for electrolysis Detergents - mostly alkyl-aryl sulphonates Petroleum refining - dyestuffs and explosives and drug When used in the manufacture of dyestuffs and explosives its purpose is in enhancing the nitrating property of nitric acid.

Sulfates Uses
Sulfates, also known as sulfur oxides, are important in both the chemical industry and biological systems: The Lead-acid battery typically uses sulfuric acid. Some anaerobic microorganisms, such as those living near deep sea thermal vents utilize sulfates as electron acceptors. Copper sulfate is a common algaecide. Magnesium sulfate, commonly known as Epsom salts, is used in therapeutic baths. Gypsum, the natural mineral form of hydrated calcium sulfate, is used to produce plaster. The sulfate ion is used as counter ion for some cationic drugs.

Oxyacids of sulphur
Sodium thiosulfate

Thiosulfate anion characteristically reacts with dilute acids to produce sulfur, sulfur dioxide and water: S2O32(aq) + 2H+ (aq) S(s) + SO2(g) + H2O(l)