4.1 INTRODUCTION TO ALKANES AND CYCLOALKANES 1. Hydrocarbons: 1) Atkanes: C,H i) Cycloalkanes: (saturated) ‘vH2, (containing a single ring) ii) Alkanes and cycloalkanes are so similar that many of their properties can be considered side by side. (containing one double bond) (containing one triple bond) 4.1A SOURCES OF ALKANES: PETROLEUM 1, The primary source of alkanes is petroleum. 4.1B PETROLEUM REFIT! G 1, The first step in refining petroleum is distillation, 2. More than 500 different compounds are contained in the petroleum distillates boiling below 200 °C, and many have almost the same boiling points. Mixtures of alkanes are suitable for uses as fuels, solvents, and lubricants. 4, Petroleum also. contains small amounts of oxygen-, nitrogen-, and sulfur-containing compounds, Table 4.1 Typical Fractions Obtained by distillation of Petroleum Boiling Range of | Number of Carbon Fraction (°C) Atoms per Molecules wz) Below 20 CC, Natural ges, bottled gas, petrochemicals 20-60 Cla, Petroleum ether, solvents 60-100 CHCy Ligroin, solvents 40-200 Clio Gasoline (straight-run gasoline) 175-325 CC Kerosene and jet fuel 250-400 Cy: and higher Gas oil, fuel oil, and diesel oil Nonvolatile liquids Cinand higher Refined mineral oil, lubricating oil, grease Nonvolatile solids Cap and higher Paraffin wax, asphalt, and tar4.1C CRACKING 1, Catalytic cracking: When a mixture of alkanes from the gas oil fraction (Cis and higher) is heated at very high temperature (~300 °C) in the presence of a variety of catalysts, the molecules breck apart and rearrange to smaller, more highly branched alkanes containing 5-10 carbon atoms. 2. Thermal cracking: tend to produce unbranched chains which have very low “octane rating”. 3. Octane rating: 1) Isooctane: 2,24-trimethylpentane burns very smoothly in internal combustion engines and has an octane rating of 100. iss HyC—¢— Cit) CH-Clls CH; 2,2,4-trimethylpentane (“isooctane”) 2) Heptane [CHs(CH:) unbranched alkanes => contain only 1° and 2° carbon atoms, Branched-chain alkanes: re Butane and isobutene are constitutional-somers. @ @ « & © g & BOS: 869-6 ch ev ¢ ere & eSe «Se © © H,;C—CH—CH, We-CR Ge OHS nye—t—cHr, CH, cH; CH; Isobutane Isopentane Neopentane Figure 4.2 Ball-and-stick models for three branched-chain alkanes. In each of the compounds one carbon atom is attached to more than two other carbon atoms. 5. Constitutional-isomers have different physical properties. Table 4.2 Physical Constants of the Hexane Isomers Index of Molecular bp (°C) Density® . Structural Formula mp (°C) )) Refraction’ Formula (atm) (gmL") (itp 20°C) CiHiy— CHsCH:CH:CH,CH;—-95 68.7 0.6594 1.3748 CH3CHCH;CH,CH3 CH I 153.7 60.30.6532" 1.3714 CH, CH,CH,CHCH,CH, CHis I -118 63.3 0.6643" 1.3765 CHa CH,CH—CHCH, io “1288 580.0616" 1.3750 H.C CH; CH; I Cay HACC CH Cy 98 49.7 0.6492 1.3688 CH;