Alkanes Bunsen burners burt natural gas, which is primarily methane, with sm: amounts of ethane, propane, and butane. 11-1 What Are Alkanes? In this chapter, we examine the physical and chemical properties of ‘lkanes, the simplest type of organic compounds. Actually, alkanes are cannon, of a larger class of organic compounds called hydrocarbons. A hydrocarbon is a compound composed of only carbon and hydrogen. Figure 11-1 shows the four classes of hydrocarbons, along with the char. aetoriatie type of bonding between carbon atoms in each class, Alknnes seeratureted hydrocarbons that is, they contain only carbon-carbon Single bonds, Saturated in this context means that each carbon i the hydrocarbon has the maximum number of hydrogens bonded to it, A hy- drocarbon that contains one or more carbon-carbon double bonds, triple ‘fied as an unsaturated hydrocarbon, bonds, or benzene rings is classi We study alkanes (saturated hydrocarbons) in this chapter, and alkenes, alkynes, and arenes (unsaturated hydrocarbons) in Chapters 12 and 13, Tye ethan refer 10 alkanes as aliphatic hydrocarbons because the Physical groperties of the higher members of this claas resemble those Of ihe tong exrbon-ehain molecules we find in animal fats and plant oils Greek: aleiphar, fat or oil). What Are Al 2 How Do We W 14-3 What Are 11-4 How Do We Name Alkanes? 11-5. Where Do We Obtain Alkanes? 11-6 What Are Cycloalkanes? 11-7 What Are the Shapes of Alkanes and Cycloalkanes? How To. . .Draw Alternative Chair Conformations of Cyclohexane 11-8. What Is Cis-Trans lsomerism in Cydoalkanes? 11-9. What Are the Physical Properties of Alkanes and Cycloalkanes? 411-10 What Are the Characteristic Reactions of Alkanes? 41-11 What Are Some Important Haloalkanes? Alkanes Saturated hydrocarbons ‘whose carbon atoms are arranged ina chain Hydrocarbon compound that contains only carton and hydrogen atoms Saturated hydrocarbons bons that contain ony carbon-carbon single bonds Aliphatic hydrocarbons alkanes Scanned with CamScanneror more One oF more One gre ote casted benzene i ad Scanned with CamScanner14-3 What Are Constitutional Isomers? Scanned with CamScannermolecular formula C,Hyp are draw, oer Notural formulas and as line-angle formulas, ‘are ball-and-stick models of each. A jerked 2.Methylpropane (hp 116°C) are different compounds and have different ‘Their boiling points, for example, differ by feral examples of constitutional iso. nat at the time. We saw, for example, formula C3H,O, two primary o aldehydes with the molec: Scanned with CamScanner11-3 What Are Constitutional Ibomers?, Scanned with CamScannerstrong, stable bonds with other carbon er of constitutional isomers, as the and hydrogen atoms, a very sible. In fact, the potential among organic molecules n, hydrogen, nitrogen, and m which its struc Scanned with CamScannerScanned with CamScannerScanned with CamScanner11-4 How Do We Nome Alkanes? Scanned with CamScanner282) Chapter 11-5 Where Do We Obtain Alkanes? as and petroleum. Natura) 5 to 10% et The two major sources of alkanes are he Bas consists of approximately 90 to 95% fly propa A mixture of other relatively low-boiling alkanes—chiefly prop and 2-methylpropane sands of compo Petroleum in a thick, viscous liquid mixture of thousands of compound ost of them hydrocarbons, formed from the decomposition. marine plants and animals, Petroleum and petroleum-derived produ mobi sages and lubricants requ ne greases a quired ialized society. Furtherm, arly 90% of the organic ra aireraft, and trains. They provide most of th for the machinery utilized by our highly industr provides ne petroleum, along with natural ga Thaterials forthe synthesis and manufacture if sithet fibers, tergents, drugs, dyes, and a multitude of other products. < The fundamental separation process in refining petroleum is fract distillation (Figure 11-2), Practically all erude petroleum that enters a r heated to tempe gach fraction contains ge finery goes to distillation units, where it is ‘45 870 to 425°C and separated into fractions. B ture of hydrocarbons that boils within a particular ra 11-6 What Are Cycloalkanes? A hydrocarbon that contains carbon atoms joined to form a ring is calle a eyelic hydrocarbon. When all carbons of the ring are saturated carbon-carbon single bonds are present), the hydrocarbon is Cycloalkcane A Saturated cycloalkane. Cycloalkanes with ring sizes ranging from 3 to more t hydrocarbon that contains carbon a ature, and in prince here is eee 30 carbon atoms are found in natu d in principle t ring size. Five-membered (cyclopentane) and six-mem rings are especially abundant in nature; for this reason, we con! ea them in this book, > Gases Boiling point range below (C\-C; hydrocarbons: used fuels and reactants to make — Gasoline (naphthas (Ce-Cyg hydrocarbons: motor fuels and industri —> Kerosene 175-275°C (C0 used for lamp oil, diese! material for catalytic crack 7 Rectal 250-400 9-61, used for catalytic cracking. ‘heatins diesel fuel) TACPE: Resting —* Lubricating oil above 850°C (Cie-Cag hydrocarbons; used as | ats (asphalt) FIGURE 11-2 Fractional distillation of petroleum, re removed from higher up th h ; removed from pase haetel ose ey ls The lighter, more volatile fractions vier, less volatile fractions are Scanned with CamScannerScanned with CamScannerWhat Are the i of Alkanes and Cycloalkanes ; ction, wo concentrate on ways to visualize molecules as thro. ohjoeta ad to visualize bond angles and relative distances be. atoms and functional groups within a molecule. At this point, id roview Section -10 and use of the valence-shell electron-pair bond angles and shapes of molecules u ‘models of these compounds and to study an fe those models, Organic molecules are three-dimensional objects, ial that you become comfortable in dealing with them as such, -VSEPR model gives us a way to predict the geometry about tom in an alkane, it provides us with no information about the ional shape of an entire molecule. There is, in fact, free rotation arbon bond in an alkane. As a result, even a molecule ¢ has an infinite number of possible three-dimensional ations. ‘three conformations for a butane molecule. Conforma- bl ‘the methyl groups at the ends of the four. formed by a rotation carbons 2 and 3. In this conformation, se the two methyl groups are closer sible conformations arious C—C bonds 's collisions t Even so, at stable, fully Scanned with CamScannerFIGURE 11-5 The most stable ‘conformation of cyclopentane. Scanned with CamScannerScanned with CamScanner11.7 What Are the Shapes of Alans and Cyclosianes? (2 Scanned with CamScannerBON! Chapter 11 Alkanos + CHy Cis-trans isomers Isomers that hhave the same connectivity of their atoms but a different arrangement of their atoms in space due to the presence of either a ring of carbon-carbon double bond (Chapter 12) (hy Axial metiyley vothyleyelohexnine » the three hydrogens of the methyl group are FIGURE 14-7 Mothylcyclohexane ra shown In green to make them stand out more ¢ rolecular models. Figure 11-7(a) shows a space With the methyl group in an equatorial position, In this position, the methyl group 18 En ven ate fron tther atome ofthe ring. Whon mothy! is axial (Figure 11-7(bi} ® auite Mer ally bangs into tivo axial hydrogen atoms on the same side of the ring. Thus, tho more stable conformation of a substituted mum number of its substituents groups in equatorial positions. volationship is to examine 1 filling model of methyleyclohexane J cyclohexane ring has a maxi. 11-8 What Is Cis-Trans Isomerism in Cycloalkanes? Cycloalkanes with substituents on two or more carbons of the ring show a type of isomerism called cés-¢rans isomerism. Cycloalkane cis-trans isomers have (1) the same molecular formula and (2) the same connectivity of their atom but (3), different arrangement of their atoms in space because of restricted rotation around the carbon-carbon single bonds of the ring. We study cis-tr isomerism in cycloalkanes in this chapter and that of alkenes in Chapter 12 We can illustrate cis-trans isomerism in eycloalkanes by using 1,2-dimethyleyclopentane as an example. Planar representations of # and six-membered rings are not spatially accurate because these rings r mally exist as envelope and chair conformations. Planar representatio are, however, adequate for showing cis-trans isomerism. In the follow: structural formulas, the cyclopentane ring is drawn as a planar penta viewed through the plane of the ring, Carbon-carbon bonds of the n: projecting toward you are shown as heavy lines. When viewed from ‘h'- perspective, substituents bonded to the cyclopentane ring project abo’ and below the plane of the ring. In one isomer of 1,2-dimethyleyclopentax* the methyl groups are on the same side of the ring (either both above « both below the plane of the ring); in the other isomer, they are on opposi't sides of the ring (one above and one below the plane of the ring). ‘The prefix eis (Latin: on the same side) indicates that the substituents are on the same side of the ring; the prefix trans (Latin: across) indicat’ that they are on opposite sides of the ring, a, I " Ww es nH Hon 4 H civ L.2Diovothyl —— frams-,2-Dimetbyt ‘eyclopantans eee: Scanned with CamScanner d11.8 Whats Ci Tans omesiem in Cyloatkanes? [20900 aregular pentagon « : Substituents on the Scanned with CamScanner296) chapter 14 Alkanos > Paraffin wax and mineral oil are mixtures of alkanes, Strategy Fora eyclonikane to show cis-trans isomerism, it must have at least two Substittionts, each on a different carbon of the ring Solution ism; it has ont (@) Methyleyctopontane doos not show cis-trans isomerism; it has only one substituent on the ring. Pieces. (b) 1s1-Dimethyleyciobutane does not show cis-trans i seats Oily one arguement i ponte forthe two methyl groups, Beene eioupe ame carbon, they must be oth methyl groups are bonded to the sa trans toweach other—one above the ring the other below it (©) 1,8-Dimethyleyclobutane shows cis-trans isomerism. The two methyl froups may be cis, or they may be trans. CH, a. CH, ay, H oe HC ee a. _ HC H.C u H i -Dimethyleyelobotane tran-1.9-Dimet Problem 11-7 Which of the following cycloalkanes show cis-trans isomerism? For each that does, draw both isomers. (a) 1,3-Dimethyleyclopentane (b) Ethyleyclopentane (©) 1,3-Dimethyleyclohexane 11-9 What Are the Physical Properties of Alkanes and Cycloalkanes? ‘The most important physical property of alkanes and cycloallcanes is the most complete lack of polarity. We saw in Section 3-4B that the electronezs ity difference between carbon and hydrogen is 2.52.1 = 0.4 on the Paul scale, Given this small difference, we classify a C—H bond as nonpolar cov ‘Therefore, alkanes are nonpolar compounds and the only interactions bet their molecules are the very weak London dispersion forces (Section A. Melting and Boiling Points ‘The boiling points of alkanes are lower than those of almost any other tye! compound with the same molecular weight. In general, both beiling andl ing points of alkanes increase with increasing molecular weight (Table 1+ Alkanes containing 1 to 4 carbons are gases at room temperature. Alkan containing 6 to 17 carbons are colorless liquids, High-molecular-weid?® alkanes (those containing 18 or more carbons) are white, waxy solids. © eral plant waxes are high-molecular-weight alkanes. The wax found i0 8? ple skins, for example, is an unbranched alkane with the molecular fo!" CoyHyy. 4 Paraffin wax, a mixture of high-molecular-weight alkanes, is us! for wax candles, in lubricants, and to seal home-canned jams, jellies. #2 other preserves, Petrolatum, so named because itis derived from petrol!” refining, is a liquid mixture of high-molecular-weight alleanes, It is 20! *= mineral oil and Vaseline and is'used ag an ointment base in gharmace!" cals and cosmetics and as a lubricant and rust prevents al Scanned with CamScannerScanned with CamScanner