Structure and Nomenclature of Hydrocarbons

What Is an Organic Compound? Rotation Around C C Bonds The Saturated Hydrocarbons, or Alkanes The Nomenclature of Alkanes The Cycloalkanes The Unsaturated Hydrocarbons: Alkenes and Alkynes

What is an Organic Compound? When you drive up to the pump at some gas stations you are faced with a variety of choices. You can buy "leaded" gas or different forms of "unleaded" gas that have different octane numbers. As you filled the tank, you might wonder, "What is 'leaded' gas, and why do they add lead to gas?" Or, "What would I get for my money if I bought premium gas, with a higher octane number?" You then stop to buy drugs for a sore back that has been bothering you since you helped a friend move into a new apartment. Once again, you are faced with choices (see the figure below). You could buy aspirin, which has been used for almost a hundred years. Or Tylenol, which contains acetaminophen. Or a more modern pain-killer, such as ibuprofen. While you are deciding which drug to buy, you might wonder, "What is the difference between these drugs?," and even, "How do they work?"

"What is cholesterol?" and "Why do so many people worry about it?" Answers to each of these questions fall within the realm of a field known as organic chemistry. What he expected is described by the following equation. H2NCONH2." without worrying about why one of these plastics is flexibile while the other is rigid. which brings up the questions. when Friederich Wohler synthesized urea from inorganic starting materials. For more than 200 years. It was a white. While you're eating. where you sit in a "plastic" chair to eat a sandwich that has been wrapped in "plastic. The first step in the decline of the vital force theory occurred in 1828. Those isolated from plants and animals were classified as organic. At one time. while those that trace back to minerals were inorganic. chemists have divided materials into two categories. AgOCN(aq) + NH4Cl(aq) AgCl(s) + NH4OCN(aq) The product he isolated from this reaction had none of the properties of cyanate compounds. crystalline material that was identical to urea. which could be isolated from urine. Wohler was trying to make ammonium cyanate (NH4OCN) from silver cyanate (AgOCN) and ammonium chloride (NH4Cl). .You then drive to campus. a friend stops by and starts to tease you about the effect of your diet on the level of cholesterol in your blood. chemists believed that organic compounds were fundamentally different from those that were inorganic because organic compounds contained a vital force that was only found in living systems.

It is therefore tempting to identify organic chemistry as the chemistry of carbon.Neither Wohler nor his contemporaries claimed that his results disproved the vital force theory. including the hydrogen. We will therefore define organic chemistry as the chemistry of compounds that contain both carbon and hydrogen. Carbon therefore forms covalent bonds with a large number of other elements. as well as the elemental forms of carbon diamond and graphite that are clearly inorganic. But this definition would include compounds such as calcium carbonate (CaCO3). although it did not lead to the death of the theory. . and the atomic radius of carbon atoms (see the table below). including the number of valence electrons on a neutral carbon atom. But his results set in motion a series of experiments that led to the synthesis of a variety of organic compounds from inorganic starting materials. and too large for carbon to lose electrons to form C4+ ions. nitrogen. If the difference between organic and inorganic compounds isn't the presence of some mysterious vital force required for their synthesis.077 nm Carbon has four valence electrons 2s2 2p2 and it must either gain four electrons or lose four electrons to reach a rare-gas configuration. The special role of carbon in the chemistry of the elements is the result of a combination of factors.ions. more than 95% of the compounds that have isolated from natural sources or synthesized in the laboratory are organic. and sulfur found in living systems.55 Covalent radius 0. The electronegativity of carbon is too small for carbon to gain electrons from most elements to form C4. which still had proponents more than 90 years later. what is the basis for distinguishing between these classes of compounds? Most compounds extracted from living organisms contain carbon. phosphorus. the electronegativity of carbon. oxygen. Even though organic chemistry focuses on compounds that contain carbon and hydrogen. This inevitably led to the disappearance of "vital force" from the list of theories that had any relevance to chemistry. The Physical Properties of Carbon Electronic configuration 1s2 2s2 2p2 Electronegativity 2.

The ability of carbon to form multiple bonds to other nonmetals. • • • The ease with which carbon atoms form bonds to other carbon atoms. O. It can even form double bonds to elements such as phosphorus or sulfur that do not form double bonds to themselves. The simplest alkane is methane: CH4. carbon atoms can come close enough together to form strong C=C double bonds or even C C triple bonds. The Lewis structure of methane can be generated by combining the four electrons in the valence shell of a neutral carbon atom with four . The strength of C C single bonds and the covalent bonds carbon forms to other nonmetals. the unmanned Viking spacecraft carried out experiments designed to search for evidence of life on Mars. These factors provide an almost infinite variety of potential structures for organic compounds. These experiments were based on the assumption that living systems contain carbon. O. Carbon also forms strong double and triple bonds to nitrogen and oxygen. and the absence of any evidence for carbon-based life on that planet was presumed to mean that no life existed. P. P. and S. The saturated hydrocarbons are also known as alkanes. and S atoms. such as N. The Saturated Hydrocarbons. or Alkanes Compounds that contain only carbon and hydrogen are known as hydrocarbons. N. Those that contain as many hydrogen atoms as possible are said to be saturated. including C. such as vitamin C shown in the figure below. Several factors make carbon essential to life. Several years ago. No other element can provide the variety of combinations and permutations necessary for life to exist.Because they are relatively small.

To minimize the repulsion between pairs of electrons in the four C H bonds. . The four-carbon alkane is butane.hydrogen atoms to form a compound in which the carbon atom shares a total of eight valence electrons with the four hydrogen atoms. it forms a total of four bonds in almost all of its compounds. with the formula C4H10. Practice Problem 1: Use the fact that carbon is usually tetravalent to predict the formula of ethane. the geometry around the carbon atom is tetrahedral. the alkane that contains two carbon atoms. which has the formula C3H8 and the following skeleton structure. Click here to check your answer to Practice Problem 1 The alkane that contains three carbon atoms is known as propane. as shown in the figure below. Methane is an example of a general rule that carbon is tetravalent.

in which the carbon atoms form a chain that runs from one end of the molecule to the other.7 -95 -90.8 Boiling Point (oC) -164 -88. alkanes molecules that contain three or four carbon atoms can no longer be thought of as "linear. or Alkanes Molecular Name Formula methane CH4 ethane C2H6 propane C3H8 butane C4H10 pentane C5H12 hexane C6H14 heptane C7H16 octane C8H18 nonane C9H20 decane C10H22 undecane C11H24 dodecane C12H26 eicosane C20H42 triacontane C30H62 Melting Point (oC) -182.The names." as shown in the figure below.8 65.1 -0. formulas. the carbon skeleton of the ethane molecule is linear. Because the bond angle in a tetrahedron is 109.8 174.4 -129.9 216. as shown in the figure below. and physical properties for a variety of alkanes with the generic formula CnH2n+2 are given in the table below. The boiling points of the alkanes gradually increase with the molecular weight of these compounds.7 -138.1 195. .5. the midweight alkanes are liquids.6 36.4 124.5 -183.3 -189. for every n carbon atoms there must be 2n + 2 hydrogen atoms: CnH2n+2.6 -9.6 -42. Because two points define a line.3 343 449.7 150.8 -51 -29. The Saturated Hydrocarbons.7 State at 25oC gas gas gas gas liquid liquid liquid liquid liquid liquid liquid liquid solid solid The alkanes in the table above are all straight-chain hydrocarbons.5 36.6 -56. Thus. and the heavier alkanes are solids.1 68. the lighter alkanes are gases. At room temperature. The generic formula for these compounds can be understood by assuming that they contain chains of CH2 groups with an additional hydrogen atom capping either end of the chain. or tars.7 -24.9 98.

alkanes also form branched structures. "equal. One contains two CH3 groups and two CH2 groups.Propane Butane In addition to the straight-chain examples considered so far. A branched isomer is also possible. When it was first discovered. or n-pentane. but a different structure. the branched isomer with the formula C4H10 was therefore given the name isobutane. the other contains three CH3 groups and one CH group. Butane Isobutane Butane and isobutane are called constitutional isomers because they literally differ in their constitution. it was named neopentane (the new isomer of pentane)." and meros. This compound has the same formula as butane (C4H10). C5H12. The smallest hydrocarbon in which a branch can occur has four carbon atoms. . When a more highly branched isomer was discovered. Compounds with the same formula and different structures are known as isomers (from the Greek isos. The first is "normal" pentane. "parts"). Isobutane The best way to understand the difference between the structures of butane and isobutane is to compare the ball-and-stick models of these compounds shown in the figure below. There are three constitutional isomers of pentane. which was originally named isopentane.

Which of these structures represent the same molecule? . n-Pentane Isopentane Neopentane Practice Problem 2: The following structures all have the same molecular formula: C6H14.Ball-and-stick models of the three isomers of pentane are shown in the figure below.

which is very much smaller than the 109. The angle between adjacent C C bonds is only 60.Click here to check your answer to Practice Problem 2 Practice Problem 3: Determine the number of constitutional isomers of hexane. three isomers of C5H12. C6H14. Cycloalkanes therefore have two less hydrogen atoms than the parent alkane and a generic formula of CnH2n. Click here to check your answer to Practice Problem 3 There are two constitutional isomers with the formula C4H10. for example. C3H6.5 angle in a tetrahedron. . we can envision the two ends coming together to form a cycloalkane. as shown in the figure below. The smallest alkane that can form a ring is cyclopropane. and five isomers of C6H14. The Cycloalkanes If the carbon chain that forms the backbone of a straight-chain hydrocarbon is long enough. in which the three carbon atoms lie in the same plane. There are over 4 billion isomers for C30H62. The number of isomers of a compound increases rapidly with additional carbon atoms. One hydrogen atom has to be removed from each end of the hydrocarbon chain to form the C C bond that closes the ring.

Cyclopropane is therefore susceptible to chemical reactions that can open up the threemembered ring. out of the ring. a puckered structure can be formed by displacing a pair of carbon atoms at either end of the ring from the plane of the other four members of the ring. Any attempt to force the four carbons that form a cyclobutane ring into a plane of atoms would produce the structure shown in the figure below. One of these carbon atoms is tilted up. which is close to the ideal angle around a tetrahedral carbon atom. in which the angle between adjacent C C bonds would be 90. whereas the other is tilted down to form the "chair" structure shown in the figure below. The angle between adjacent C C bonds in a planar cyclopentane molecule would be 108. By the time we get to the six-membered ring in cyclohexane. Cyclopentane is not a planar molecule. because displacing two of the carbon atoms from the plane of the other three produces a puckered structure that relieves some of the repulsion between the hydrogen atoms on adjacent carbon atoms in the ring. as shown in the figure below. One of the four carbon atoms in the cyclobutane ring is therefore displaced from the plane of the other three to form a "puckered" structure that is vaguely reminiscent of the wings of a butterfly. .

At room temperature.Rotation Around C C Bonds As one looks at the structure of the ethane molecule." as shown in the figure below. There is another way in which the ethane molecule can move. the molecule passes through an infinite number of conformations that have slightly different energies. When this happens. the molecule is tumbling around its center of gravity like an airplane out of control. it is easy to fall into the trap of thinking about this molecule as if it was static. The highest energy conformation corresponds to a structure in which the hydrogen atoms are "eclipsed. . Nothing could be further from the truth." If we view the molecule along the C C bond. The CH3 groups at either end of the molecule can rotate with respect to each around the C C bond. At the same time. The lowest energy conformation is a structure in which the hydrogen atoms are "staggered. the C H and C C bonds are vibrating like a spring at rates as fast as 9 x 1013 s-1. the hydrogen atoms on one CH3 group would obscure those on the other. the average velocity of an ethane molecule is about 500 m/s more than twice the speed of a Boeing 747. While it moves through space. as shown in the figure below.

Eclipsed Staggered The difference between the energies of these conformations is relatively small. there are several conformations of some of the cycloalkanes described in the previous section. Because of the ease of rotation around C C bonds. the ethane molecule spends a slightly larger percentage of the time in the staggered conformation. forms both the "chair" and "boat" conformations shown in the figure below. The different conformations of a molecule are often described in terms of Newman projections. for example. Cyclohexane.The difference between the eclipsed and staggered conformations of ethane are best illustrated by viewing these molecules along the C C bond. as shown in the figure below. But it is large enough that rotation around the C C bond is not smooth. Although the frequency of this rotation is on the order of 1010 revolutions per second. These line drawings show the six substituents on the C C bond as if the structure of the molecule was projected onto a piece of paper by shining a bright light along the C C bond in a ball-and-stick model of the molecule. only about 12 kJ/mol. . Newman projections for the different staggered conformations of butane are shown in the figure below.

• Find the longest continuous chain of carbon atoms in the skeleton structure. however. is about 30 kJ/mol. as the size of the hydrocarbon chain increases. They become less useful. in which the hydrogen atoms are staggered.Chair Boat The difference between the energies of the chair conformation. we can assume that most cyclohexane molecules at any moment in time are in the chair conformation. . The International Union of Pure and Applied Chemistry (IUPAC) has developed a systematic approach to naming alkanes and cycloalkanes based on the following steps. The Nomenclature of Alkanes Common names such as pentane. is a derivative of pentane because the longest chain contains five carbon atoms. The following compound. and the boat conformation. As a result. for example. Name the compound as a derivative of the alkane with this number of carbon atoms. and neopentane are sufficient to differentiate between the three isomers with the formula C5H12. in which they are eclipsed. even though the rate at which these two conformations interchange is about 1 x 105 s-1. isopentane.

tri-.• Name the substituents on the chain. for example. or four times on the same chain of carbon atoms. • • Use the prefixes di-. • Number the chain starting at the end nearest the first substituent and specify the carbon atoms on which the substituents are located. Use the lowest possible numbers. Practice Problem 5: Name the following compound. three. This compound contains a methyl (CH3-) substituent.to describe substituents that are found two. Practice Problem 4: Name the following compound. Arrange the names of the substituents in alphabetical order. This compound. and tetra. is 2-methylpentane. Substituents derived from alkanes are named by replacing the -ane ending with -yl. . not 4-methylpentane.

We do the same thing to one of the bonds between the carbon atoms in an alkene. we can transform an alkene into the parent alkane by adding an H2 molecule across a C=C double bond.The Unsaturated Hydrocarbons: Alkenes and Alkynes Carbon not only forms the strong C C single bonds found in alkanes. (They tend to remain oily liquids when cooled.) These compounds are now called alkenes. "to make an oil") because they were hard to crystallize. such as piece of nickel metal. In practice. this reaction only occurs at high pressures in the presence of a suitable catalyst. . in theory. We start by breaking the bond in an H2 molecule so that one of the electrons ends up on each of hydrogen atoms. The simplest alkene has the formula C2H4 and the following Lewis structure. Thus. The relationship between alkanes and alkenes can be understood by thinking about the following hypothetical reaction. Compounds that contain C=C double bonds were once known as olefins (literally. We then allow the unpaired electron on each hydrogen atom to interact with the unpaired electron on a carbon atom to form a new C H bond. it also forms strong C=C double bonds.

Compounds that contain C C triple bonds are called alkynes. The simplest alkyne has the formula C2H2 and is known by the common name acetylene. These compounds have four less hydrogen atoms than the parent alkanes. The IUPAC nomenclature for alkenes names these compounds as derivatives of the parent alkanes. They were once named by adding the suffix -ene to the name of the substituent that carried the same number of carbon atoms. The presence of the C=C double bond is indicated by changing the -ane ending on the name of the parent alkane to -ene. The names of substituents are then added as prefixes to the name of the alkene. so the generic formula for an alkyne with a single C C triple bond is CnH2n-2. the generic formula for an alkene with one C=C double bond is CnH2n. Alkenes are examples of unsaturated hydrocarbons because they have fewer hydrogen atoms than the corresponding alkanes. The IUPAC nomenclature for alkynes names these compounds as derivatives of the parent alkane. The location of the C=C double bond in the skeleton structure of the compound is indicated by specifying the number of the carbon atom at which the C=C bond starts. . with the ending -yne replacing -ane.Because an alkene can be thought of as a derivative of an alkane from which an H2 molecule has been removed.

In addition to compounds that contain one double bond (alkenes) or one triple bond (alkynes). Alkenes. | . and Alkynes | Hydrocarbons Petroleum and Coal | Chirality and Optical Activity The | Periodic Table | Periodic Table | Glossary | Cool Applets Gen Chem Topic Review | General Chemistry Help Homepage Search: The general chemistry web site. we can also envision compounds with two double bonds (dienes). three double bonds (trienes). or a combination of double and triple bonds. Organic Chemistry: Structure and Nomenclature of Hydrocarbons Structure and Nomenclature of Hydrocarbons | Isomers | Reactions of Alkanes.