WADEMC02 0131478710.QXD 11/8/04 8:06 AM Page...

39

upward displacement

downward displacement

rest position

+

−

rest positiond

d

Á Figure 2-1A standing wave. The fundamentalfrequency of a guitar string isa standing wave with the stringalternately displaced upwardand downward.

Structure and Propertiesof Organic Molecules

2C C HH

In Chapter 1, we considered how atoms bond together to gain noble-gas configura-tions, forming molecules in the process. Using the octet rule, we drew Lewis struc-tures for organic molecules and used these diagrams to determine which bonds are

single bonds, double bonds, and triple bonds. We discussed various ways of drawingorganic structures, and we saw how resonance structures represent molecules whoseactual bonding cannot be described by a single Lewis structure.

Chapter 1 does not explain the actual shapes and properties of organic mole-cules. To understand these aspects of molecular structure we need to consider how theatomic orbitals on an atom mix to form hybrid atomic orbitals and how orbitals on dif-ferent atoms combine to form molecular orbitals. In this chapter, we look more close-ly at how combinations of orbitals account for the shapes and properties we observe inorganic molecules.

2-1Wave Properties of Electrons in Orbitals

We like to picture the atom as a miniature solar system, with the electrons orbitingaround the nucleus. This solar system picture satisfies our intuition, but it does notaccurately reflect today’s understanding of the atom. About 1923, Louis de Brogliesuggested that the properties of electrons in atoms are better explained by treating theelectrons as waves rather than as particles.

There are two general kinds of waves, traveling waves and standing waves.Examples of traveling waves are the sound waves that carry a thunderclap and the waterwaves that form the wake of a boat. Standing waves vibrate in a fixed location. Stand-ing waves are found inside an organ pipe, where the rush of air creates a vibrating aircolumn, and in the wave pattern of a guitar string when it is plucked. An electron in anatomic orbital is like a stationary, bound vibration: a standing wave.

To understand the features of an orbital (a three-dimensional standing wave)more easily, let’s consider the vibration of a guitar string as a one-dimensionalanalogy (see Figure 2-1). If you pluck a guitar string at its middle, a standing waveresults. In this mode of vibration, all of the string is displaced upward for a fractionof a second, then downward for an equal time. An instantaneous picture of thewaveform shows the string displaced in a smooth curve either upward or down-ward, depending on the exact instant of the picture.

The waveform of a 1s orbital is like this guitar string, except that it is three-dimensional. The orbital can be described by its wave function, which is themathematical description of the shape of the wave as it vibrates. All of the wave ispositive in sign for a brief instant; then it is negative in sign. The electron density

c,

39

WADEMC02_0131478710.QXD 11/8/04 8:06 AM Page 39

40 Chapter 2: Structure and Properties of Organic Molecules

+−

or

+−

node

Á Figure 2-3First harmonic of a guitar string.The two halves of the string areseparated by a node, a point withzero displacement. The two halvesvibrate out of phase with each other.

Electron densityis highest atthe nucleus

nucleus

nucleus

represented by

represented by

+

nucleus

−

wave function (�)with positive sign

wave function (�)with negative sign

probability function �2

(electron density)

distance

distance

distance

electrondensity

» Figure 2-2The 1s orbital. The 1s orbital issimilar to the fundamental vibrationof a guitar string. The wave functionis instantaneously all positive or allnegative. The square of the wavefunction gives the electron density.A circle with a nucleus is usedto represent the sphericallysymmetrical s orbital.

at any point is given by the square of the wave function at that point. Noticethat the plus sign and the minus sign of these wave functions are not charges. Theplus or minus sign is the instantaneous sign of the constantly changing wave func-tion. The 1s orbital is spherically symmetrical, and it is often represented by a cir-cle (representing a sphere) with a nucleus in the center and with a plus or minussign to indicate the instantaneous sign of the wave function (Figure 2-2).

If you gently place a finger at the center of a guitar string while plucking thestring, your finger keeps the midpoint of the string from moving. The displacement

at the midpoint is always zero; this point is a node. The stringnow vibrates in two parts, with the two halves vibrating in opposite directions. Wesay that the two halves of the string are out of phase: When one is displacedupward, the other is displaced downward. Figure 2-3 shows this first harmonic ofthe guitar string.

The first harmonic of the guitar string resembles the 2p orbital (Figure 2-4). Wehave drawn the 2p orbital as two “lobes,” separated by a node (a nodal plane). The twolobes of the p orbital are out of phase with each other. Whenever the wave function hasa plus sign in one lobe, it has a minus sign in the other lobe.

1movement + or -2

c2,

�

�

��

��nucleus

nucleus

wave function(instantaneous picture)

�

�

nucleus

equivalent wave function(instantaneous picture)

represented by

represented by

nucleus

nodal plane

nodal plane

nodal plane

nodal plane

» Figure 2-4The 2p orbital. The 2p orbital has twolobes, separated by a nodal plane.The two lobes are out of phase witheach other. When one has a plus sign,the other has a minus sign.


2-2 Molecular Orbitals 41

« Figure 2-5Electron density in a molecularorbital. A bonding molecular orbitalplaces a large amount of electrondensity in the bonding region, thespace between the two nuclei.

+

−

+

nucleus 2nucleus 1

−

bonding region

electrons in this regionattract both nuclei

and mask the positivecharges from repelling each other

2-1A Linear Combination of Atomic OrbitalsAtomic orbitals can combine and overlap to give more complex standing waves. Wecan add and subtract their wave functions to give the wave functions of new orbitals.This process is called the linear combination of atomic orbitals (LCAO). The num-ber of new orbitals generated always equals the number of orbitals we started with.

1. When orbitals on different atoms interact, they produce molecular orbitals(MOs) that lead to bonding (or antibonding).

2. When orbitals on the same atom interact, they give hybrid atomic orbitals thatdefine the geometry of the bonds.

We begin by looking at how atomic orbitals on different atoms interact to givemolecular orbitals. Then we consider how atomic orbitals on the same atom can inter-act to give hybrid atomic orbitals.

2-2Molecular Orbitals

The stability of a covalent bond results from a large amount of electron density in thebonding region, the space between the two nuclei (Figure 2-5). In the bonding region,the electrons are close to both nuclei, resulting in a lowering of the overall energy. Thebonding electrons also mask the positive charges of the nuclei, so the nuclei do notrepel each other as much as they would otherwise.

There is always an optimum distance for the two bonded nuclei. If they are toofar apart, their attraction for the bonding electrons is diminished. If they are too closetogether, their electrostatic repulsion pushes them apart. The internuclear distancewhere attraction and repulsion are balanced, which also gives the minimum energy(the strongest bond), is called the bond length.

2-2A The Hydrogen Molecule; Sigma BondingThe hydrogen molecule is the simplest example of covalent bonding. As two hydrogenatoms approach each other, their 1s wave functions can add constructively so that theyreinforce each other, or destructively so that they cancel out where they overlap.Figure 2-6 shows how the wave functions interact constructively when they are inphase and have the same sign in the region between the nuclei. The wave functionsreinforce each other and increase the electron density in this bonding region. Theresult is a bonding molecular orbital (bonding MO).

The bonding MO depicted in Figure 2-6 has most of its electron density centeredalong the line connecting the nuclei. This type of bond is called a cylindrically sym-metrical bond or a sigma bond ( bond). Sigma bonds are the most common bonds inorganic compounds. All single bonds in organic compounds are sigma bonds, andevery double or triple bond contains one sigma bond. The electrostatic potentialmap of shows its cylindrically symmetrical sigma bond, with the highest electrondensity (red) in the bonding region between the two protons.

H2

s



Constructive Interaction: The two 1sorbitals are in phase and have the same sign.

1s 1s

� �

1s 1s

�

add

represented by:

bonding molecular orbital

�-bonding MO

� ��

» Figure 2-6Formation of a MO.When the 1s orbitals of two hydrogenatoms overlap in phase, they interactconstructively to form a bondingMO. The electron density in thebonding region (between the nuclei)is increased. The result is acylindrically symmetrical bond,or sigma bond, designated s.

s-bonding

�

�

� � �

�

�

add

represented by:

antibonding molecular orbital

�* antibonding MO

node

node

Destructive interaction: The two 1s orbitals are out of phase.

» Figure 2-7Formation of a antibonding MO.When two 1s orbitals overlap outof phase, they interact destructivelyto form an antibonding MO. Thepositive and negative values of thewave functions tend to cancel outin the region between the nuclei,and a node separates the nuclei.We use an asterisk to designateantibonding orbitals such as thissigma antibonding orbital, s*.

1*2

s*

When two hydrogen 1s orbitals overlap out of phase with each other, anantibonding molecular orbital results (Figure 2-7). The two 1s wave functionshave opposite signs, so they tend to cancel out where they overlap. The result is anode (actually a nodal plane) separating the two atoms. The presence of a nodeseparating the two nuclei usually indicates that the orbital is antibonding.

WADEMC02_0131478710.QXD 11/8/04 8:06 AM 2

2-2 Molecular Orbitals 43

antibonding

�*

�

1s1s

energy

atomic orbitalatomic orbital

molecular orbital

bonding

node

« Figure 2-8Relative energies of atomic andmolecular orbitals. When the twohydrogen 1s orbitals overlap, a sigmabonding MO and a sigma antibondingMO result. The bonding MO is lowerin energy than the atomic 1s orbital,and the antibonding orbital is higherin energy. Two electrons (representedby arrows) go into the bonding MOwith opposite spins, forming a stable

molecule. The antibondingorbital is vacant.H2

Figure 2-8 shows the relative energies of the atomic orbitals and the molecu-lar orbitals of the system. When the 1s orbitals are in phase, the resultingmolecular orbital is a sigma bonding MO, with lower energy than that of a 1satomic orbital. When two 1s orbitals overlap out of phase, they form an antibond-ing orbital with higher energy than that of a 1s atomic orbital. The two elec-trons in the system are found with paired spins in the sigma bonding MO,giving a stable molecule. In stable molecules, the antibonding orbitals (such as

) are usually vacant.

2-2B Sigma Overlap Involving p OrbitalsWhen two p orbitals overlap along the line between the nuclei, a bonding orbital andan antibonding orbital result. Once again, most of the electron density is centeredalong the line between the nuclei. This linear overlap is another type of sigma bondingMO. The constructive overlap of two p orbitals along the line joining the nuclei formsa bond represented as follows:

+

σ bonding MOpxpx

+ +− − −− +

s

s*H2

H2

1s*2

H2

SOLVED PROBLEM 2-1

Draw the antibonding orbital that results from the destructive overlap of the two orbitals just shown.

SOLUTIONThis orbital results from the destructive overlap of lobes of the two p orbitals with opposite phases. If the signs are reversed on one ofthe orbitals, adding the two orbitals gives an antibonding orbital with a node separating the two nuclei:

��

�* antibonding MOpxpx

� ��

node

pxs*



Overlap of an s orbital with a p orbital also gives a bonding MO and an anti-bonding MO, as shown in the following illustration. Constructive overlap of the sorbital with the orbital gives a sigma bonding MO with its electron density centeredalong the line between the nuclei. Destructive overlap gives a antibonding orbitalwith a node separating the nuclei.

�

σ bonding MOspx

��

(−) s

�

�

��

�* antibonding MOpx

��

node

s*px

2-3Pi Bonding

A pi bond ( bond) results from overlap between two p orbitals oriented perpendicularto the line connecting the nuclei (Figure 2-9). These parallel orbitals overlap sideways,with most of the electron density centered above and below the line connecting thenuclei. This overlap is parallel, not linear (as in a sigma bond), so a pi molecular orbitalis not cylindrically symmetrical. Figure 2-9 shows a pi bonding MO and the correspon-ding antibonding MO.

2-3A Single and Double BondsA double bond requires the presence of four electrons in the bonding region betweenthe nuclei. The first pair of electrons goes into the sigma bonding MO, forming astrong sigma bond. The second pair of electrons cannot go into the same orbital or thesame space. It goes into a pi bonding MO, with its electron density centered above andbelow the sigma bond.

p*

p

�

� bonding MO

energy

� �

� �

� �

� �

�

�* antibonding MO

constructive (bonding) interaction

destructive (antibonding) interaction

�

�

� �

� �

node

» Figure 2-9Pi bonding and antibondingmolecular orbitals. The sidewaysoverlap of two p orbitals leads to a pibonding MO and a antibondingMO. A pi bond is not as strongas most sigma bonds.

pi*


2-4 Hybridization and Molecular Shapes 45

half of � bond

half of � bond

� bond CCH H

H HC C

H H

H HLewis structure of ethylene

« Figure 2-10Structure of a double bond. The firstpair of electrons forms a sigma bond.The second pair forms a pi bond.The pi bond has its electron densitycentered in two lobes, above andbelow the sigma bond. Together, thetwo lobes of the pi bonding molecularorbital constitute one bond.

109.5° 109.5° 121.7°

116.6°

180°

109.5°

methane, 109.5° ethylene, close to 120° acetylene, 180°

H H H

H H

HH H

H

HC C C C C

Á Figure 2-11Common bond angles. Bond angles in organic compounds are usually close to 109°, 120°, or 180°.

The combination of a sigma bond and a pi bond is the normal structure of adouble bond. Figure 2-10 shows the structure of ethylene, an organic moleculecontaining a carbon–carbon double bond.

Thus far, we have discussed only bonds involving overlap of simple s and patomic orbitals. Although these simple bonds are occasionally seen in organic com-pounds, they are not as common as bonds formed using hybrid atomic orbitals. Hy-brid atomic orbitals result from the mixing of orbitals on the same atom. The geometryof these hybrid orbitals helps us to account for the actual structures and bond anglesobserved in organic compounds.

2-4Hybridization and Molecular Shapes

If we predict the bond angles of organic molecules using just the simple s and porbitals, we expect bond angles of about 90°. The s orbitals are nondirectional, and thep orbitals are oriented at 90° to one another (see Figure 1-3). Experimental evidenceshows, however, that bond angles in organic compounds are usually close to 109°,120°, or 180° (Figure 2-11). A common way of accounting for these bond angles is thevalence-shell electron-pair repulsion theory (VSEPR theory): Electron pairs repeleach other, and the bonds and lone pairs around a central atom generally are separatedby the largest possible angles. An angle of 109.5° is the largest possible separation forfour pairs of electrons; 120° is the largest separation for three pairs; and 180° is thelargest separation for two pairs. All the structures in Figure 2-11 have bond angles thatseparate their bonds about as far apart as possible.

The shapes of these molecules cannot result from bonding between simple s andp atomic orbitals. Although these orbitals have the lowest energies for isolated atomsin space, they are not the best for forming bonds. To explain the shapes of commonorganic molecules, we assume that the s and p orbitals combine to form hybrid atomicorbitals that separate the electron pairs more widely in space and place more electrondensity in the bonding region between the nuclei.



» Figure 2-12Formation of a pair of sp hybridatomic orbitals. Addition of an s orbitalto a p orbital gives an sp hybrid atomicorbital, with most of its electrondensity on one side of the nucleus.Adding the p orbital with oppositephase gives the other sp hybrid atomicorbital, with most of its electrondensity on the opposite side of thenucleus from the first hybrid.

s p

s (−)p

++− + −

+ −

constructiveoverlap

destructiveoverlap

destructiveoverlap

constructiveoverlap

++ −

sp hybrid

second sp hybrid

2-4A sp Hybrid OrbitalsOrbitals can interact to form new orbitals. We have used this principle to form molec-ular orbitals by adding and subtracting atomic orbitals on different atoms, but we canalso add and subtract orbitals on the same atom. Consider the result when we combinea p orbital and an s orbital on the same atom (Figure 2-12).

The resulting orbital is called an sp hybrid orbital. Its electron density is con-centrated toward one side of the atom. We started with two orbitals (s and p), so wemust finish with two sp hybrid orbitals. The second sp hybrid orbital results if we addthe p orbital with the opposite phase (Fig. 2-12).

The result of this hybridization is a pair of directional sp hybrid orbitals pointedin opposite directions. These hybridized orbitals provide enhanced electron density inthe bonding region for a sigma bond toward the left of the atom and for another sigmabond toward the right. In addition, these hybrid orbitals give a bond angle of 180°, sep-arating the bonding electrons as much as possible. In general, sp hybridization resultsin this linear bonding arrangement.

SOLVED PROBLEM 2-2

Draw the Lewis structure for beryllium hydride, Draw the orbitals that overlap inthe bonding of and label the hybridization of each orbital. Predict the bond angle.

SOLUTIONFirst, we draw a Lewis structure for

H:Be:H

There are only four valence electrons in (two from Be and one from each H), so the Beatom cannot have an octet of electrons. The bonding must involve orbitals on Be that give thestrongest bonds (the most electron density in the bonding region) and also allow the two pairsof electrons to be separated as far as possible.

Hybrid orbitals concentrate the electron density in the bonding region, and sp hybridsgive 180° separation for two pairs of electrons. Hydrogen cannot use hybridized orbitals, sincethe closest available p orbitals are the 2p’s, and they are much higher in energy than the 1s.The bonding in results from overlap of sp hybrid orbitals on Be with the 1s orbitals onhydrogen. Figure 2-13 shows how this occurs.

BeH2

BeH2

BeH2.

H ¬ Be ¬ HBeH2,BeH2.


2-4 Hybridization and Molecular Shapes 47

� � � ��

� �

� ��

�

�

� �

s px py sp2 hybrid orbitals

three sp2 hybrid orbitals superimposed sp2 hybrid carbon atom(viewed from the side)

sp2sp2

sp2

unhybridizedpz

orbital120� 120�

120�

« Figure 2-14Trigonal geometry with

hybrid orbitals.Hybridization of an s orbitalwith two p orbitals gives aset of three hybridorbitals. The bondangles associated with thistrigonal structure are about120°. The remaining porbital is perpendicular tothe plane of the three hybridorbitals.

sp2

sp2

+ +

+

−

+−

H HBe

180° (linear) bond angle for sp hybrid

Be(sp)

H(1s)

Be(sp)

H(1s)

180°

Superimposed picture

First bond

Second bond « Figure 2-13Linear geometry in the bonding of

To form two sigma bonds,the two sp hybrid atomic orbitalson Be overlap with the 1s orbitalsof hydrogen. The bond angle is180° (linear).

BeH2.

2-4B Hybrid OrbitalsTo orient three bonds as far apart as possible, bond angles of 120° are required. Whenan s orbital combines with two p orbitals, the resulting three hybrid orbitals are orient-ed at 120° angles to each other (Figure 2-14). These orbitals are called hybridorbitals because they are composed of one s and two p orbitals. The 120° arrangementis called trigonal geometry, in contrast to the linear geometry associated with sphybrid orbitals. There remains an unhybridized p orbital perpendicular to theplane of the three hybrid orbitals.sp2

1pz2

sp2

sp2



Methanotrophs are bacteria thatgrow using methane as their onlyfood source. It may be possible toharness this capability and producevarious chemicals (like methanol)from methane or to reduce themethane levels in the atmosphere.High levels of methane are believedto contribute to global warming.

PROBLEM-SOLVING HintThe number of hybrid orbitals formedis always the same as the totalnumber of s and p orbitals hybridized.

Number of Orbitals Hybrid Angle

2 sp 180°3 120°4 109.5°sp3

sp2

SOLVED PROBLEM 2-3

Borane is not stable under normal conditions, but it has been detected at lowpressure.(a) Draw the Lewis structure for borane.(b) Draw a diagram of the bonding in this molecule, and label the hybridization of each

orbital.(c) Predict the bond angle.

SOLUTIONThere are only six valence electrons in borane. Boron has a single bond to each of the threehydrogen atoms.

The best bonding orbitals are those that provide the greatest electron density in thebonding region while keeping the three pairs of bonding electrons as far apart as possi-ble. Hybridization of an s orbital with two p orbitals gives three hybrid orbitalsdirected 120° apart. Overlap of these orbitals with the hydrogen 1s orbitals gives aplanar, trigonal molecule. (Note that the small back lobes of the hybrid orbitals havebeen omitted.)

2-4C Hybrid OrbitalsMany organic compounds contain carbon atoms that are bonded to four other atoms.When four bonds are oriented as far apart as possible, they form a regular tetrahedron(109.5° bond angles), as pictured in Figure 2-15. This tetrahedral arrangement canbe explained by combining the s orbital with all three p orbitals. The resulting fourorbitals are called hybrid orbitals because they are composed of one s and threep orbitals.

Methane is the simplest example of hybridization (Figure 2-16). TheLewis structure for methane has eight valence electrons (four from carbon and onefrom each hydrogen), corresponding to four single bonds. Tetrahedral geome-try separates these bonds by the largest possible angle, 109.5°.

C ¬ H

sp31CH42

sp3

sp3

H

H H

B

sp2

sp2 sp2

120� 120�

120�

sp2

BHH

H

H ¬ B ¬ H

1BH32

� � �

s px py pz four sp3 hybrids

109.5�» Figure 2-15Tetrahedral geometry with hybridorbitals. Hybridization of an s orbitalwith all three p orbitals gives four

hybrid orbitals with tetrahedralgeometry and 109.5° bond angles.sp3

sp3


2-5 Drawing Three-Dimensional Molecules 49

PROBLEM-SOLVING HintWhen showing perspective, do notdraw another bond between the twobonds in the plane of the paper. Sucha drawing shows an incorrect shape.

2-5Drawing Three-Dimensional Molecules

. .

H H

H

H

H

HH

H

sp3

sp3sp3

sp3

HH HH

C

C

CHH

Hmethane

H

C109.5°

« Figure 2-16Several views of methane. Methanehas tetrahedral geometry, using four

hybrid orbitals to form sigmabonds to the four hydrogen atoms.sp3

CCH3H3C

H

Hincorrect

CCH3H3C

HH

correct

CH

HH

H

N�

HH

H

H

PROBLEM 2-1

(a) Use your molecular models to make ethane, and compare the model with the precedingstructures.

(b) Make a model of propane and draw this model using dashed lines and wedgesto represent bonds going back and coming forward.

1C3 H82,

C

H

HH

H

ethane ethane ethane

H

H

C

away fromthe reader

towardthe reader

in the planeof the page

Figures 2-15 and 2-16 were more difficult to draw than the earlier figures because theydepict three-dimensional objects on a two-dimensional piece of paper. The orbitalshould look like it points in and out of the page, and the tetrahedron should look three-dimensional. These drawings use perspective and the viewer’s imagination to add thethird dimension.

The use of perspective is difficult when a molecule is large and complicated.Organic chemists have developed a shorthand notation to simplify three-dimensionaldrawings. Dashed lines indicate bonds that go backward, away from the reader.Wedge-shaped bonds depict bonds that come forward, toward the reader. Straight linesare bonds in the plane of the page. Dashed lines and wedges show perspective in thesecond drawing of methane in Figure 2-16.

The three-dimensional structure of ethane, has the shape of two tetrahedrajoined together. Each carbon atom is hybridized, with four sigma bonds formedby the four hybrid orbitals. Dashed lines represent bonds that go away from theviewer, wedges represent bonds that come out toward the viewer, and other bond linesare in the plane of the page. All the bond angles are close to 109.5°.

sp3sp3

C2 H6,

pz



2-6General Rules of Hybridization and Geometry

At this point, we can consider some general rules for determining the hybridization oforbitals and the bond angles of atoms in organic molecules. After stating these rules,we solve some problems to show how the rules are used.

Rule 1: Both sigma bonding electrons and lone pairs can occupy hybridorbitals. The number of hybrid orbitals on an atom is computed by adding thenumber of sigma bonds and the number of lone pairs of electrons on that atom.

Because the first bond to another atom is always a sigma bond, the number of hybridorbitals may be computed by adding the number of lone pairs to the number of atomsbonded to the central atom.

Rule 2: Use the hybridization and geometry that give the widest possible sepa-ration of the calculated number of bonds and lone pairs.

Summary of Hybridization and Geometry

Hybrid Orbitals Hybridization Geometry Approximate Bond Angles

2 linear 180°3 trigonal 120°4 tetrahedral 109.5°

The number of hybrid orbitals obtained equals the number of atomic orbitals com-bined. Lone pairs of electrons take up more space than bonding pairs of electrons, thusthey compress the bond angles.

Rule 3: If two or three pairs of electrons form a multiple bond between twoatoms, the first bond is a sigma bond formed by a hybrid orbital. The secondbond is a pi bond, consisting of two lobes above and below the sigma bond,formed by two p orbitals (see Figure 2-17). The third bond of a triple bond isanother pi bond, perpendicular to the first pi bond (Fig. 2-18).

s + p + p + p = sp3s + p + p = sp2

s + p = sp

Á Figure 2-17Planar geometry of ethylene. The carbon atoms in ethylene are hybridized, with trigonal bond angles of about 120°. All the carbonand hydrogen atoms lie in the same plane.

sp2

C CH H

Csp2 sp2

sp2

sp2sp2

sp2H H

H H

half of � bond

half of � bond

ethylene� bond framework (viewed from above the plane)

� bond(viewed from alongside the plane)

H

H

H

HC CC

H H

Solved Problems 2-4 through 2-8 show how to use these rules to predict the hy-bridization and bond angles in organic compounds.

SOLVED PROBLEM 2-4

Predict the hybridization of the nitrogen atom in ammonia, Draw a picture of thethree-dimensional structure of ammonia, and predict the bond angles.

SOLUTIONThe hybridization depends on the number of sigma bonds plus lone pairs. A Lewis structureprovides this information.

H

NH

H

orH NH

H lone pair

NH3.


In this structure, there are three sigma bonds and one pair of nonbonding electrons. Four hybridorbitals are required, implying hybridization and tetrahedral geometry around the nitrogenatom, with bond angles of about 109.5°. The resulting structure is much like that of methane,except that one of the hybrid orbitals is occupied by a lone pair of electrons.

Notice that the bond angles in ammonia (107.3°) are slightly smaller than the idealtetrahedral angle, 109.5°. The nonbonding electrons are more diffuse than a bonding pair ofelectrons, and they take up more space. The lone pair repels the electrons in the bonds,compressing the bond angle.

PROBLEM 2-2

(a) Predict the hybridization of the oxygen atom in water, Draw a picture of its three-dimensional structure, and explain why its bond angle is 104.5°.

(b) The electrostatic potential maps for ammonia and water are shown here. The structureof ammonia is shown within its EPM. Note how the lone pair creates a region of highelectron potential (red), and the hydrogens are in regions of low electron potential(blue). Show how your three-dimensional structure of water corresponds with its EPM.

SOLVED PROBLEM 2-5

Predict the hybridization, geometry, and bond angles for ethylene

SOLUTIONThe Lewis structure of ethylene is

Each carbon atom has an octet, and there is a double bond between the carbon atoms. Each car-bon is bonded to three other atoms (three sigma bonds), and there are no lone pairs. The carbonatoms are hybridized, and the bond angles are trigonal: about 120°. The double bond is com-posed of a sigma bond formed by overlap of two hybridized orbitals, plus a pi bond formedby overlap of the unhybridized p orbitals remaining on the carbon atoms. Because the pi bond re-quires parallel alignment of its two p orbitals, the ethylene molecule must be planar (Fig. 2-17).

PROBLEM 2-3

Predict the hybridization, geometry, and bond angles for the central atoms in(a) 2-butene,(b)

SOLVED PROBLEM 2-6

Predict the hybridization, geometry, and bond angles for the carbon atoms in acetylene,

SOLUTIONThe Lewis structure of acetylene is

Both carbon atoms have octets, but each carbon is bonded to just two other atoms, requiring twosigma bonds. There are no lone pairs. Each carbon atom is sp hybridized and linear (180° bond

H:C:::C:H or H ¬ C ‚ C ¬ H

C2 H2.

CH2 “ NCH3

CH3 CH “ CHCH3

sp2sp2

C CHH

HHor CC

H

H

H

H

1C2 H42.

NH3 H2O

H2 O.

N ¬ H

H HH

N

107.3°

sp3

sp3

2-6 General Rules of Hybridization and Geometry 51



PROBLEM-SOLVING HintBegin with a good Lewis structure,and use hybrid orbitals for the sigmabonds and lone pairs. Use pi bondsbetween unhybridized p orbitals forthe second and third bonds of doubleand triple bonds.

» Figure 2-18Linear geometry of acetylene. Thecarbon atoms in acetylene are sphybridized, with linear (180°) bondangles. The triple bond contains onesigma bond and two perpendicularpi bonds.

C CCH Hsp spspsp

pz pz

pypy

C HH

acetylene acetylene

OC

C

H

H

H sp2

sp2sp2

pp

sp2

sp2

sp3

sp2 HOC

CH

HH

H

109.5�

120�

Á Figure 2-19Structure of acetaldehyde. The carbon in acetaldehyde is hybridized, with tetrahedral bond anglesof about 109.5°. The carbonyl carbon is hybridized, with bond angles of about 120°. Theoxygen atom is probably hybridized, but we cannot measure any bond angles to verify this prediction.sp2

sp21C “ O2sp3CH3

PROBLEM 2-4

Predict the hybridization, geometry, and bond angles for the carbon and nitrogen atoms inacetonitrile 1CH3 ¬ C ‚ N:2.

SOLVED PROBLEM 2-7

Predict the hybridization, geometry, and bond angles for the carbon and oxygen atoms in acetaldehyde

SOLUTIONThe Lewis structure for acetaldehyde is

The oxygen atom and both carbon atoms have octets of electrons. The carbon atom is sigma bonded to four atoms, so it ishybridized (and tetrahedral). The carbon is bonded to three atoms (no lone pairs), so it is hybridized and its bond

angles are about 120°.The oxygen atom is probably hybridized because it is bonded to one atom (carbon) and has two lone pairs, requiring a total of

three hybrid orbitals. We cannot experimentally measure the angles of the lone pairs on oxygen, however, so it is impossible to confirmwhether the oxygen atom is really hybridized.

The double bond between carbon and oxygen looks just like the double bond in ethylene. There is a sigma bond formed by overlapof hybrid orbitals and a pi bond formed by overlap of the unhybridized p orbitals on carbon and oxygen (Figure 2-19).sp2

sp2

sp2

sp2C “ Osp3CH3

CH

HH

HC

Oor H C

H

C

H H

O

1CH3 CHO2.

angles). The sp hybrid orbitals are generated from the s orbital and the orbital (the p orbital di-rected along the line joining the nuclei). The orbitals and the orbitals are unhybridized.

The triple bond is composed of one sigma bond, formed by overlap of sp hybridorbitals, plus two pi bonds. One pi bond results from overlap of the two orbitals and anotherfrom overlap of the two orbitals (Figure 2-18).pz

py

pzpy

px


2-6 General Rules of Hybridization and Geometry 53

PROBLEM-SOLVING HintTo predict the hybridization andgeometry of an atom in a resonancehybrid, consider the resonance formwith the most pi bonds to that atom.An atom involved in resonancegenerally will not be hybridizedbecause it needs at least oneunhybridized p orbital forpi-bonding overlap.

sp3

PROBLEM 2-5

1. Draw a Lewis structure for each of the following compounds.2. Label the hybridization, geometry, and bond angles around each atom other than

hydrogen.3. Draw a three-dimensional representation (using wedges and dashed lines) of the

structure.(a) (b) (c)(d) HCOOH (e) HCN (f)(g) ozone bonded OOO

PROBLEM 2-6

Allene, has the structure shown below. Explain how the bonding in allenerequires the groups at its ends to be at right angles to each other.

SOLVED PROBLEM 2-8

In Chapter 1, we considered the electronic structure of Predict its hybridiza-tion, geometry, and bond angles.

SOLUTIONThis is a tricky question. This ion has two important resonance forms:

When resonance is involved, different resonance forms may suggest different hybridizationand bond angles. Only electrons can be delocalized, however. The molecule can have onlyone set of bond angles, which must be compatible with all the important resonance forms.Looking at either resonance form for we would predict hybridization(120° bond angles) for the carbon atom; however, the first resonance form suggests hy-bridization for nitrogen (109° bond angles), and the second suggests hybridization(120° bond angles). Which is correct?

Experiments show that the bond angles on both carbon and nitrogen are about120°, implying hybridization. Nitrogen cannot be hybridized because there mustbe an unhybridized p orbital available to form the pi bond in the second resonance form.In the first resonance form we picture the lone pair residing in this unhybridizedp orbital.

In general, resonance-stabilized structures have bond angles appropriate for the largestnumber of pi bonds needed at each atom; that is, with unhybridized p orbitals available for allthe pi bonds shown in any important resonance form.

C��

N CH

HH

H H

HH

HN

sp3sp2

sp2sp3

sp2[CH2 NH2]+,

C�

N

H

H

H

H

�

N

H

H

H

H

C �

resonance forms

N

Hd

H

H

H

C� d�

combinedrepresentation

[CH2 NH2]+.

CC

H

H

CH

H

allene

two “ CH2

CH2 “ C “ CH2,

1O32,CH3 CH “ CH2

1CH323 NCH3 ¬ O ¬ CH3CO2



PROBLEM 2-7

1. Draw the important resonance forms for each compound.2. Label the hybridization and bond angles around each atom other than hydrogen.3. Use a three-dimensional drawing to show where the electrons are pictured to be in each

resonance form.

(a) (b) (c) (d) B1OH23[H2 CCN]-

O

CCH2H

�

[H2 COH]+

PROBLEM-SOLVING HintDrawings that differ only by rotationsof single bonds usually represent thesame compound. For example, thefollowing drawings all representn-butane:

2-7Bond Rotation

Some bonds rotate easily, but others do not. When we look at a structure, we must rec-ognize which bonds rotate and which do not. If a bond rotates easily, each moleculecan rotate through the different angular arrangements of atoms. If a bond cannot ro-tate, however, different angular arrangements may be distinct compounds (isomers)with different properties.

2-7A Rotation of Single BondsIn ethane both carbon atoms are hybridized and tetrahedral.Ethane looks like two methane molecules that have each had a hydrogen pluckedoff (to form a methyl group) and are joined by overlap of their orbitals (Fig. 2-20).

We can draw many structures for ethane, differing only in how one methyl groupis twisted in relation to the other one. Such structures, differing only in rotations abouta single bond, are called conformations. Two of the infinite number of conformationsof ethane are shown in Figure 2-20. Construct a molecular model of ethane, and twistthe model into these two conformations.

sp3

sp31CH3 ¬ CH32,

σ bondsp3sp3

methyl group methyl group

eclipsed

ethane

C

H H

H HH

C

H

HH

C

H

HH

C

H

HH

H

C

H

HH

C

H

HH

C

H

staggered

H

H

C

rotaterotate» Figure 2-20Rotation of single bonds. Ethane iscomposed of two methyl groupsbonded by overlap of their hybridorbitals. These methyl groups mayrotate with respect to each other.

sp3

H3CCH3CH2CH2CH3 C

H

Hn-butanen-butane

H

C

CH3

H

H

H C

Hn-butane

C

CH3

H

H

CH3

H C

n-butane

C

CH3

CH3 H

H

Which of these structures for ethane is the “right” one? Are the two methylgroups lined up so that their bonds are parallel (eclipsed), or are theystaggered, as in the drawing on the right? The answer is that both structures, and allthe possible structures in between, are correct structures for ethane, and a real ethanemolecule rotates through all these conformations. The two carbon atoms are bondedby overlap of their orbitals to form a sigma bond along the line between the car-bons. The magnitude of this overlap remains nearly the same during rotationbecause the sigma bond is cylindrically symmetrical about the line joining the carbonnuclei. No matter how you turn one of the methyl groups, its orbital still overlapswith the orbital of the other carbon atom.sp3

sp3

sp3–sp3sp3

C ¬ H


2-7 Bond Rotation 55

2-7B Rigidity of Double BondsNot all bonds allow free rotation; ethylene, for example is quite rigid. In ethylene, thedouble bond between the two groups consists of a sigma bond and a pi bond.When we twist one of the two groups, the sigma bond is unaffected but the pibond loses its overlap. The two p orbitals cannot overlap when the two ends of themolecule are at right angles, and the pi bond is effectively broken.

We can make the following generalization:

Rotation about single bonds is allowed, but double bonds are rigid and cannotbe twisted.

Because double bonds are rigid, we can separate and isolate compounds that differonly in how their substituents are arranged on a double bond. For example, the doublebond in 2-butene prevents the two ends of the moleculefrom rotating. Two different compounds are possible, and they have different physicalproperties:

The molecule with the methyl groups on the same side of the double bond is called cis-2-butene, and the one with the methyl groups on opposite sides is called trans-2-butene. These kinds of molecules are discussed further in Section 2-8B.

PROBLEM 2-8

For each pair of structures, determine whether they represent different compounds or a sin-gle compound.

(a)

(b)

(c)

(d)Br

HH

HF

Cl

andC C

FCl

H

Br

HH C C

Br

H

F

Cl

andC C

Cl

F H

Br

C C

H3C CH2CH3

CH3

H3C

CH2CH3

CH3

HH H

HH

Hand

Hand

H3C CH2CH3

CH3 H

H3C

CH2CH3

CH3

H3C

H

C

cis-2-butenebp � 3.7�C

trans-2-butenebp � 0.9�C

C

CH3

H

H3C

H

C C

H

CH3

1CH3 ¬ CH “ CH ¬ CH32

try to twisthold in position

C

overlap destroyed

H

H

CCH H

CH HHH

CH2

CH2



PROBLEM 2-9

Two compounds with the formula are known.(a) Draw a Lewis structure for this molecule, and label the hybridization of each carbon and

nitrogen atom.(b) What two compounds have this formula?(c) Explain why there is only one compound known with the formula 1CH322 CNCH3.

CH3 ¬ CH “ N ¬ CH3

2-8Isomerism

Isomers are different compounds with the same molecular formula. There are severaltypes of isomerism in organic compounds, and we will cover them in detail in Chapter5 (Stereochemistry). For now, we need to recognize the two large classes of isomers:constitutional isomers and stereoisomers.

2-8A Constitutional IsomerismConstitutional isomers (or structural isomers) are isomers that differ in their bond-ing sequence; that is, their atoms are connected differently. Let’s use butane as anexample. If you were asked to draw a structural formula for either of the fol-lowing structures would be correct:

These two compounds are isomers because they have the same molecular formula.They are constitutional isomers because their atoms are connected differently. Thefirst compound (n-butane for “normal” butane) has its carbon atoms in a straightchain four carbons long. The second compound (“isobutane” for “an isomer ofbutane”) has a branched structure with a longest chain of three carbon atoms and amethyl side chain.

There are three constitutional isomers of pentane whose commonnames are n-pentane, isopentane, and neopentane. The number of isomers increasesrapidly as the number of carbon atoms increases.

Constitutional isomers may differ in ways other than the branching of theircarbon chain. They may differ in the position of a double bond or other group or byhaving a ring or some other feature. Notice how the following constitutional iso-mers all differ by the ways in which atoms are bonded to other atoms. (Check thenumber of hydrogens bonded to each carbon.) These compounds are not isomersof the pentanes just shown, however, because these have a different molecularformula 1C5 H102.

n-pentane

CH39CH29CH29CH29CH3

isopentane neopentane

CH3

CH39CH9CH29CH3

CH3

CH39C9CH3

CH3

1C5 H122,

n-butaneCH39CH29CH29CH3

isobutane

CH3

CH39CH9CH3

C4 H10,

H2C CH2CH2CH3CH1-pentene

CH3 CH CH2CH3CH2-pentene cyclopentane methylcyclobutane

CH3

PROBLEM-SOLVING HintConstitutional isomers (structuralisomers) differ in the order in whichtheir atoms are bonded.


2-8 Isomerism 57

PROBLEM-SOLVING HintSimilar groups on the same side of thedouble bond: cis.Similar groups on opposite sides ofthe double bond: trans.

2-8B StereoisomersStereoisomers are isomers that differ only in how their atoms are oriented in space.Their atoms are bonded in the same order, however. For example, cis- and trans-2-butene have the same connections of bonds, so they are not constitutional isomers.They are stereoisomers because they differ only in the spatial orientation of the groupsattached to the double bond. The cis isomer has the two methyl groups on the sameside of the double bond, and the trans isomer has them on opposite sides. In contrast,1-butene is a constitutional isomer of cis- and trans-2-butene.

Cis and trans isomers are only one type of stereoisomerism. The study of thestructure and chemistry of stereoisomers is called stereochemistry. We will encounterstereochemistry throughout our study of organic chemistry, and Chapter 5 is devotedentirely to this field.

Cis-trans isomers are also called geometric isomers because they differ in thegeometry of the groups on a double bond. The cis isomer is always the one with simi-lar groups on the same side of the double bond, and the trans isomer has similar groupson opposite sides of the double bond.

To have cis-trans isomerism, there must be two different groups on each end ofthe double bond. For example, 1-butene has two identical hydrogens on one end of thedouble bond. Reversing their positions does not give a different compound. Similarly,2-methyl-2-butene has two identical methyl groups on one end of the double bond.Reversing the methyl groups does not give a different compound.

PROBLEM 2-10

Which of the following compounds show cis-trans isomerism? Draw the cis and trans iso-mers of those that do.(a) (b) (c)

(d) (e) (f)

PROBLEM 2-11

Give the relationship between the following pairs of structures. The possible relation-ships are

same compound constitutional isomers (structural isomers)

cis-trans isomers not isomers (different molecular formula)

CHCH3CHCHCH3CHCH3

CH2 “ CH ¬ CH2 ¬ CH3F2 C “ CH2CHF “ CHF

CH3

C

2-methyl-2-buteneno cis or trans

C

CH3

H

CH3

identicalC C

H

identical

1-buteneno cis or trans

CH2CH3

H

H

H3C

H

C

cis-2-butene

C

CH3

H

H3C

H

C C

H

CH3

trans-2-butene

H2C

H

C C

CH3

H2

1-butene

constitutional isomers

stereoisomers

PROBLEM-SOLVING HintIdentical groups on one of thedouble-bonded carbons implies no cis-trans isomerism.

Stereoisomers can have very diff-erent therapeutic effects. Quinine,a natural product isolated fromthe bark of the cinchona tree,was the first known compoundused to treat malaria. Quinidine, astereoisomer of quinine, is used totreat irregular heartbeat.



(a)

(b) (c)

(d) (e)

(f)

(g) and (h) and (i) and

(j) (k)

CH3

and

CH3

CH3

CH3

and

CH3

CH3

CH3 CH2 CH2 CH “ CH2CH2 “ CHCH2 CH2 CH3

CH3 ¬ CH “ CH ¬ CH2 CH3CH2 “ CH ¬ CH2 CH2 CH3

CH3 ¬ CH “ CH ¬ CH3CH3 ¬ CH2 ¬ CH2 ¬ CH3

CH3

CH3

H9C99C9H and H9C99C9CH3

H CH3

H H H

H

Cl

H9C9C9H and H9C9C9H

H Cl Cl Cl

H H H

C C

H

Br

Br

H

and C C

H

Br

Br

H

C C

H

Br

Br

H

and C C

H

Br H

Br

C C

H

Br

Br

H

and C C

H

BrBr

H

CH2CH3

CH3CH2CHCH2CH3

CH3

CH3CH2CHCH2CH2CH3and

2-9Polarity of Bonds and Molecules

In Section 1-6, we reviewed the concept of polar covalent bonds between atoms withdifferent electronegativities. Now we are ready to combine this concept with molecu-lar geometry to study the polarity of entire molecules.

2-9A Bond Dipole MomentsBond polarities can range from nonpolar covalent, through polar covalent, to totallyionic. In the following examples, ethane has a nonpolar covalent bond. Methyl-amine, methanol, and chloromethane have increasingly polar ( and

) covalent bonds. Methylammonium chloride ( ) has an ionicbond between the methylammonium ion and the chloride ion.

The polarity of an individual bond is measured as its bond dipole moment, defined as

where is the amount of charge at either end of the dipole and d is the distancebetween the charges.

Dipole moments are expressed in units of the debye (D), wherecoulomb meters. If a proton and an electron (charge

coulomb) were 1 Å apart (distance ), the dipole momentwould be

m = 11.60 * 10-19 coulomb2 * 110-10 meter2 = 1.60 * 10-29 coulomb meter

10-10 meter1.60 * 10-191 debye = 3.34 * 10-30

d

m = d * d

m,

H3C9CH3

ethane

H3C9NH2

methylamine

H3C9OHmethanol

H3C9Clchloromethane

H3CNH3 Cl�

methylammoniumchloride

increasing polarity ionicnonpolar

�

CH3 NH3+ Cl-C ¬ ClC ¬ N, C ¬ O,

C ¬ C


2-9 Polarity of Bonds and Molecules 59

TABLE 2-1 Bond Dipole Moments (Debye) for Some Common Covalent Bonds

Bond Dipole Moment, Bond Dipole Moment,

0.22 D 0.3 D

0.86 D 1.31 D

1.51 D 1.53 D

1.56 D 2.4 D

1.48 D 3.6 D

1.29 DC9 I

C#NC9Br

C"OC9Cl

H9OC9F

H9NC9O

H9CC9N

MM

Expressed in debyes,

A simple rule of thumb, using common units, is that

Dipole moments are measured experimentally, and they can be used to calculate otherinformation such as bond lengths and charge separations.

Bond dipole moments in organic compounds range from zero in symmetricalbonds to about 3.6 D for the strongly polar triple bond. Table 2-1 shows typi-cal dipole moments for some of the bonds common in organic molecules. Recall thatthe positive end of the crossed arrow corresponds to the less electronegative (partialpositive charge) end of the dipole.

C ‚ N:

m 1in debyes2 = 4.8 * d 1electron charge2 * d 1in angstroms2

m =

1.60 * 10-29 C # m

3.34 * 10-30 C # m>D= 4.8 D

SOLVED PROBLEM 2-9

Calculate the charge separation for a typical single bond, with a bond length of 1.43 Åand a dipole moment of 0.86 D.

SOLUTION

Using the formula for the dipole moment, we have

The amount of charge separation is about 0.125 electronic charge, so the carbon atomhas about an eighth of a positive charge, and the oxygen atom has about an eighth of a neg-ative charge.

PROBLEM 2-12

The double bond has a dipole moment of about 2.4 D and a bond length of about 1.21 Å.(a) Calculate the amount of charge separation in this bond.(b) Use this information to evaluate the relative importance of the following two resonance

contributors:

O

C

R R

C�

R R

O �

C “ O

d

d = 0.125 e

0.86 D = 4.8 * d * 1.43 Å

m� 0.86 D

OC� dd

1.43 Å

�

C ¬ O



2-9B Molecular Dipole MomentsA molecular dipole moment is the dipole moment of the molecule taken as a whole.It is a good indicator of a molecule’s overall polarity. Molecular dipole moments canbe measured directly, in contrast to bond dipole moments, which must be estimated bycomparing various compounds. The value of the molecular dipole moment is equal tothe vector sum of the individual bond dipole moments. This vector sum reflects boththe magnitude and the direction of each individual bond dipole moment.

For example, formaldehyde has one strongly polar bond, and carbondioxide has two. We might expect to have the larger dipole moment, but its dipolemoment is actually zero. The symmetry of the carbon dioxide molecule explains thissurprising result. The structures of formaldehyde and carbon dioxide are shown here,together with their electrostatic potential maps. These electrostatic potential mapsshow the bond dipole moments, with red at the negative ends and blue at the positiveends of the dipoles. In carbon dioxide, the bond dipole moments are oriented in oppo-site directions, and they cancel each other.

Figure 2-21 shows some examples of molecular dipole moments. Notice that thedipole moment of bonds is small, so we often treat bonds as nearly non-polar. Also note that the tetrahedral symmetry of positions the four dipolemoments in directions so that they cancel. A partial canceling of the bond dipole mo-ments explains why with three bonds, has a smaller molecular dipolemoment than with only one.

Lone pairs of electrons contribute to the dipole moments of bonds and mole-cules. Each lone pair corresponds to a charge separation, with the nucleus having apartial positive charge balanced by the negative charge of the lone pair. Figure 2-22shows four molecules with lone pairs and large dipole moments. Notice how the lonepairs contribute to the large dipole moments, especially in the and bonds. Also notice the red areas in the electrostatic potential maps, indicating highnegative potential in the electron-rich regions of the lone pairs.

PROBLEM 2-13

The bond is more polar than the bond, but has a smaller dipole momentthan Explain this curious result.

m = 1.5 D m = 0.2 D

NH3 NF3

NH3.NF3N ¬ HN ¬ F

C ‚ NC “ O

CH3 Cl,C ¬ ClCHCl3,

C ¬ ClCCl4

C ¬ HC ¬ H

formaldehyde EPM carbon dioxide EPMm m

H

H

C O C OO

� 2.3 D � 0formaldehyde carbon dioxide

CO2

C “ O

» Figure 2-21Molecular dipole moments. Amolecular dipole moment is thevector sum of the individual bonddipole moments.

Cl H C

µ = 1.9 Dchloromethane

µ = 1.0 Dchloroform

Cl

µ = 0carbon tetrachloride

C

H

HH

Cl

ClCl

C

Cl

ClCl

� 1.9 Dcis-1,2-dibromoethene

C

H

H

Br

Br

C


2-10 Intermolecular Forces 61

« Figure 2-22Effects of lone pairs. Lone pairs mayhave large effects on moleculardipole moments.

NHH

µ = 1.5 Dammonia

NO

µ = 1.9 Dwater

C

CH3

CH3

CH3

µ = 2.9 Dacetone

µ = 3.9 Dacetonitrile

CO

H

HH

PROBLEM 2-14

For each of the following compounds1. Draw the structure.2. Show how the bond dipole moments (and those of any nonbonding pairs of electrons)

contribute to the molecular dipole moment.3. Predict whether the compound has a large small, or zero dipole moment.

(a) (b) (c) (d)(e) (f) HCN (g) (h)(i) (j) (k) (l)(m)

PROBLEM 2-15

Two isomers of 1,2-dichloroethene are known. One has a dipole moment of 2.4 D; the other haszero dipole moment. Draw the two isomers and explain why one has zero dipole moment.

1,2-dichloroetheneCHCl “ CHCl

NH4+

BeCl2BF3CH2 “ CHCl1CH323 NH2 C “ NHCH3 CHOO3

CH3 OHCF4CH3 FCH2 Cl2

171 D2,

2-10Intermolecular Forces

When two molecules approach, they attract or repel each other. This interaction can bedescribed fairly simply in the case of atoms (like the noble gases) or simple moleculessuch as or In general, the forces are attractive until the molecules come so closethat they infringe on each other’s atomic radius. When this happens, the small attractiveforce quickly becomes a large repulsive force, and the molecules “bounce” off eachother. With complicated organic molecules, these attractive and repulsive forces aremore difficult to predict. We can still describe the nature of the forces, however, and wecan show how they affect the physical properties of organic compounds.

Attractions between molecules are particularly important in solids and liquids.In these “condensed” phases, the molecules are continuously in contact with eachother. The melting points, boiling points, and solubilities of organic compounds showthe effects of these forces. Three major kinds of attractive forces cause moleculesto associate into solids and liquids: the dipole–dipole forces of polar molecules, theLondon forces that affect all molecules, and the “hydrogen bonds” that link moleculeshaving or groups.¬ NH¬ OH

Cl2.H2



2-10A Dipole–Dipole ForcesMost molecules have permanent dipole moments as a result of their polar bonds. Eachmolecular dipole moment has a positive end and a negative end. The most stablearrangement has the positive end of one dipole close to the negative end of another.When two negative ends or two positive ends approach each other, they repel, but theymay turn and orient themselves in the more stable positive-to-negative arrangement.Dipole–dipole forces, therefore, are generally attractive intermolecular forces result-ing from the attraction of the positive and negative ends of the dipole moments ofpolar molecules. Figure 2-23 shows the attractive and repulsive orientations of polarmolecules, using chloromethane as the example.

Polar molecules are mostly oriented in the lower-energy positive-to-negativearrangement, and the net force is attractive. This attraction must be overcome when theliquid vaporizes, resulting in larger heats of vaporization and higher boiling points forstrongly polar compounds.

» Figure 2-23Dipole–dipole interactions.Dipole–dipole interactions resultfrom the approach of two polarmolecules. If their positive andnegative ends approach, theinteraction is an attractive one. If twonegative ends or two positive endsapproach, the interaction is repulsive.In a liquid or a solid, the moleculesare mostly oriented with the positiveand negative ends together, and thenet force is attractive.

attraction (common)

symbolized by

repulsion (uncommon)

C�

�Cl

HH

H

� � � � � �

� � � ��

C�

�Cl

HH

H

C

��

Cl

HH

H

or

2-10B The London Dispersion ForceCarbon tetrachloride has zero dipole moment, yet its boiling point is higherthan that of chloroform Clearly, there must be some kind of force otherthan dipole–dipole forces holding the molecules of carbon tetrachloride together.

In nonpolar molecules such as carbon tetrachloride, the principal attractive force isthe London dispersion force, one of the van der Waals forces (Fig. 2-24). The Londonforce arises from temporary dipole moments that are induced in a molecule by othernearby molecules. Even though carbon tetrachloride has no permanent dipole moment,the electrons are not always evenly distributed. A small temporary dipole moment isinduced when one molecule approaches another molecule in which the electrons areslightly displaced from a symmetrical arrangement. The electrons in the approachingmolecule are displaced slightly so that an attractive dipole–dipole interaction results.

C

Cl

ClCl

Cl

�m m 0carbon tetrachloride, bp � 77°C

C

Cl

ClCl

H

� 1.0 Dchloroform, bp � 62°C

1m = 1.0 D2.1CCl42


2-10 Intermolecular Forces 63

++

−−

+++

−−

−

−

−

+

+

�

�

�

�

� �

�

�

� �

random temporary dipoles when separated

correlated temporary dipoles when in contact

« Figure 2-24London dispersion forces. Londondispersion forces result from theattraction of correlated temporarydipoles.

« Figure 2-25Hydrogen bonding. Hydrogenbonding is a strong intermolecularattraction between an electrophilic

or hydrogen atom anda pair of nonbonding electrons.

N ¬ HO ¬ H

These temporary dipoles last only a fraction of a second, and they change con-tinuously; yet they are correlated so their net force is attractive. This attractive forcedepends on close surface contact of two molecules, so it is roughly proportional to themolecular surface area. Carbon tetrachloride has a larger surface area than chloroform(a chlorine atom is much larger than a hydrogen atom), so the intermolecular van derWaals attractions between carbon tetrachloride molecules are stronger than they arebetween chloroform molecules.

We can see the effects of London forces in the boiling points of simple hydro-carbons. If we compare the boiling points of several different isomers, the isomerswith larger surface areas (and greater potential for London force attraction) have high-er boiling points. The boiling points of three isomers of molecular formula aregiven here. The long-chain isomer (n-pentane) has the greatest surface area and thehighest boiling point. As the amount of chain branching increases, the molecule be-comes more spherical and its surface area decreases. The most highly branched isomer(neopentane) has the smallest surface area and the lowest boiling point.

C5 H12

CH3

CH3

CH3

H

Hmethanol, methylamine,δ+ δ−

Oδ+ δ−

H H

O

H H

O

O

CH3

CH3

CH3

H

H N

H

N

CH3

H

N H

N

CH3

H

hydrogenbonds

hydrogenbonds

n-pentane, bp � 36°C

CH39CH29CH29CH29CH3

isopentane, bp � 28°C

CH3

CH39CH9CH29CH3

CH3

CH39C 9CH3

neopentane, bp � 10°CCH3

2-10C Hydrogen BondingA hydrogen bond is not a true bond but a particularly strong dipole–dipole attraction.A hydrogen atom can participate in hydrogen bonding if it is bonded to oxygen, nitro-gen, or fluorine. Organic compounds do not contain bonds, so we consider only

and hydrogens to be hydrogen bonded (Figure 2-25).O ¬ HN ¬ HH ¬ F



Hydrogen bonding is also essentialfor the structural integrity of manybiological molecules. For example,the double helix structure of DNAis maintained, in part, by hydrogenbonds between the bases: adeninepairs with thymine and guaninepairs with cytosine. Figure 23-25shows this base-pairing.

The and bonds are strongly polarized, leaving the hydrogen atomwith a partial positive charge. This electrophilic hydrogen has a strong affinity for non-bonding electrons, and it forms intermolecular attachments with the nonbonding elec-trons on oxygen or nitrogen atoms.

Although hydrogen bonding is a strong form of intermolecular attraction, it ismuch weaker than a normal or covalent bond. Breaking a hy-drogen bond requires about 5 kcal/mol (20 kJ/mol), compared with about 100kcal/mol (about 400 kJ/mol) required to break a or bond.

Hydrogen bonding has a large effect on the physical properties of organic com-pounds, as shown by the boiling points of ethanol (ethyl alcohol) and dimethyl ether,two isomers of molecular formula

ethanol, bp 78°C dimethyl ether, bp

These two isomers have the same size and the same molecular weight. Alcohols likeethanol have hydrogens, however, so they are extensively hydrogen bonded.Dimethyl ether has no hydrogen, so it cannot form hydrogen bonds. As a resultof its hydrogen bonding, ethanol has a boiling point more than 100° C higher than thatof dimethyl ether.

The effect of hydrogen bonding on boiling points can be seen in the iso-mers of formula shown below. Trimethylamine has no hydrogens, so it isnot hydrogen bonded. Ethylmethylamine has one hydrogen atom, and the result-ing hydrogen bonding raises its boiling point about 34° C above that of trimethylamine.Propylamine, with two hydrogens, is more extensively hydrogen bonded and hasthe highest boiling point of these three isomers.

Alcohols form stronger hydrogen bonds than amines, probably because oxygenis more electronegative than nitrogen. Thus, the bond is more strongly polar-ized than the bond. This effect is seen in the boiling points of the preceding iso-mers, with more than 100° difference in the boiling points of ethanol and dimethylether, compared with a 34° difference for ethylmethylamine and trimethylamine.

PROBLEM 2-16

Draw the hydrogen bonding that takes place between(a) two molecules of ethanol.(b) two molecules of propylamine.

SOLVED PROBLEM 2-10

Rank the following compounds in order of increasing boiling points. Explain the reasonsfor your chosen order.

C

CH3

CH3

CH3CH3

neopentane n-hexane 2,3-dimethylbutane

OH

pentan-1-ol

OH

2-methylbutan-2-ol

N ¬ HO ¬ H

CH39N9CH3

trimethylamine, bp 3.5°CCH3

CH3CH29N9CH3

ethylmethylamine, bp 37°CH

CH3CH2CH29N9H

propylamine, bp 49°CH

N ¬ H

N ¬ HN ¬ HC3 H9 N

N ¬ H

O ¬ HO ¬ H

-25°C

CH3 ¬ CH2 ¬ OH CH3 ¬ O ¬ CH3

C2 H6 O:

O ¬ HC ¬ H, N ¬ H,

O ¬ HC ¬ H, N ¬ H,

N ¬ HO ¬ H


2-11 Polarity Effects on Solubilities 65

SOLUTIONTo predict relative boiling points, we should look for differences in (1) hydrogen bonding,(2) molecular weight and surface area, and (3) dipole moments. Except for neopentane,these compounds have similar molecular weights. Neopentane is the lightest, and it is acompact spherical structure that minimizes van der Waals attractions. Neopentane is thelowest-boiling compound.

Neither n-hexane nor 2,3-dimethylbutane is hydrogen bonded, so they will be next high-er in boiling points. Because 2,3-dimethylbutane is more highly branched (and has a smallersurface area) than n-hexane, 2,3-dimethylbutane will have a lower boiling point than n-hexane.So far, we have

The two remaining compounds are both hydrogen-bonded, and pentan-1-ol has morearea for van der Waals forces. Therefore, pentan-1-ol should be the highest-boiling compound.We predict the following order:

10°C 58°C 69°C 102°C 138°C

The actual boiling points are given here to show that our prediction is correct.

PROBLEM 2-17

For each pair of compounds, circle the compound you expect to have the higher boiling point.Explain your reasoning.(a) and (b) and (c) and (d) and

(e) NH and NH2

1CH3 CH223 N1CH3 CH2 CH222 NH1CH323 CCH1OH2CH3HOCH2 ¬ 1CH224 ¬ CH2 OH

CH31CH225 CH2 OHCH31CH226 CH3

1CH322 CH ¬ CH2 CH2 ¬ CH1CH3221CH323 C ¬ C1CH323

neopentane 6 2, 3-dimethylbutane 6 n-hexane 6 2-methylbutan-2-ol 6 pentan-1-ol

neopentane 6 2, 3-dimethylbutane 6 n-hexane 6 the others

2-11Polarity Effects on Solubilities

In addition to affecting boiling points and melting points, intermolecular forces determinethe solubility properties of organic compounds. The general rule is that “like dissolveslike.” Polar substances dissolve in polar solvents, and nonpolar substances dissolve innonpolar solvents. We discuss the reasons for this rule now, then apply the rule in laterchapters as we discuss the solubility properties of organic compounds.

We should consider four different cases: (1) a polar solute with a polar solvent,(2) a polar solute with a nonpolar solvent, (3) a nonpolar solute with a nonpolar sol-vent, and (4) a nonpolar solute with a polar solvent. We will use sodium chloride andwater as examples of polar solutes and solvents, and paraffin “wax” and gasoline asexamples of nonpolar solutes and solvents.

Polar Solute in a Polar Solvent (Dissolves) When you think about sodiumchloride dissolving in water, it seems remarkable that the oppositely charged ionscan be separated from each other. A great deal of energy is required to separate theseions. A polar solvent (such as water) can separate the ions because it solvates them(Figure 2-26). If water is the solvent, the solvation process is called hydration. Asthe salt dissolves, water molecules surround each ion, with the appropriate end ofthe water dipole moment next to the ion. In the case of the positive (sodium) ion, theoxygen atom of the water molecule approaches. The negative ions (chloride) areapproached by the hydrogen atoms of the water molecules.

Because water molecules are strongly polar, a large amount of energy is releasedwhen the sodium and chloride ions are hydrated. This energy is nearly sufficient toovercome the lattice energy of the crystal. The salt dissolves, partly because of strong

PROBLEM-SOLVING HintTo predict relative boiling points, lookfor differences in1. hydrogen bonding,2. molecular weight and surface

area, and3. dipole moments.



» Figure 2-26Polar solute in water (a polarsolvent). The hydration of sodiumand chloride ions by water moleculesovercomes the lattice energy ofsodium chloride. The salt dissolves.

HHO

+

+ + +

+ ++−

− − −

−−−

+ + +

+ ++

− − −

−−−

ionic crystal lattice hydrated ions(dissolves)

H2O

strong ionic forces does not dissolve

nonpolarsolvent

+ −+ −+ −

++ −+ −−

+ −+ −+ −

++ −+ −−

+ −+ −+ −

++ −+ −−

+ −+ −+ −

++ −+ −−

» Figure 2-27Polar solute in a nonpolar solvent.The intermolecular attractions ofpolar substances are stronger thantheir attractions for nonpolar solventmolecules. Thus, a polar substancedoes not dissolve in a nonpolarsolvent.

solvation by water molecules and partly because of the increase in entropy (random-ness or freedom of movement) when it dissolves.

Polar Solute in a Nonpolar Solvent (Does Not Dissolve) If you stir sodiumchloride with a nonpolar solvent such as turpentine or gasoline, you will find that thesalt does not dissolve (Figure 2-27). The nonpolar molecules of these solvents do notsolvate ions very strongly, and they cannot overcome the large lattice energy of the saltcrystal. This is a case where the attractions of the ions in the solid for each other aremuch greater than their attractions for the solvent.

Nonpolar Solute in a Nonpolar Solvent (Dissolves) Paraffin “wax” dissolvesin gasoline. Both paraffin and gasoline are mixtures of nonpolar hydrocarbons (Figure2-28). The molecules of a nonpolar substance (paraffin) are weakly attracted to eachother, and these van der Waals attractions are easily overcome by van der Waalsattractions with the solvent. Although there is little change in energy when the nonpo-lar substance dissolves in a nonpolar solvent, there is a large increase in entropy.

nonpolarsolvent

CH 3CH

3

CH2 CH2 (CH 2) n

nonpolar solid(weak intermolecular forces)

dissolves

» Figure 2-28Nonpolar solute in a nonpolarsolvent. The weak intermolecularattractions of a nonpolar substanceare overcome by the weak attractionsfor a nonpolar solvent. The nonpolarsubstance dissolves.


2-11 Polarity Effects on Solubilities 67

...

...

... ...

......

...

...

...

...

. . .

. . .

...

...

. . .

. . .

nonpolar solid does not dissolve

H2O

HHO

H

HO

H

H

O H

H

O

H

H

O

H

HO

H

H

O

H

HO

H

HO

HH

O

H

HOH

HO

« Figure 2-29Nonpolar solute in a polar solvent(water). Nonpolar substances do notdissolve in water because of theunfavorable entropy effectsassociated with forming a hydrogen-bonded shell of water moleculesaround a nonpolar molecule.

Figures 2-26 through 2-29 show why the saying “like dissolves like” is generallytrue. Polar substances dissolve in polar solvents, and nonpolar substances dissolve in non-polar solvents. This general rule also applies to the mixing of liquids. Everyone knowsthat water and gasoline (or oil) do not mix. Gasoline and oil are both nonpolar hydrocar-bons, however, and they mix freely with each other. They do not dissolve in water becausethey would have to break up the hydrogen bonds of the water molecules.

Ethanol is a polar molecule, and it is miscible with water; that is, it mixes freelywith water in all proportions. Ethanol has an group that forms hydrogen bondswith water molecules. When ethanol dissolves in water, it forms new ethanol–waterhydrogen bonds to replace the water–water and ethanol–ethanol hydrogen bonds thatare broken:

O ¬ H

Nonpolar Solute in a Polar Solvent (Does Not Dissolve) Anyone who doeshome canning knows that a nonpolar solid such as paraffin does not dissolve in a polarsolvent such as water. Why not? The nonpolar molecules are only weakly attracted toeach other, and little energy is required to separate them. The problem is that the watermolecules are strongly attracted to each other by their hydrogen bonding. If a nonpo-lar paraffin molecule were to dissolve, the water molecules around it would have toform a cavity. Water molecules at the edge of the cavity have fewer available neighborsfor hydrogen bonding, resulting in a tighter, more rigid, ice-like structure around thecavity. This tighter structure results in an unfavorable decrease in the entropy of thesystem: and is small in most cases. Therefore, the negativevalue of makes positive (unfavorable), and the nonpolar substance does notdissolve (Figure 2-29).

¢G¢S¢H¢G = ¢H - T¢S,

Motor oil and water do not mixbecause the nonpolar oil moleculescannot displace the strongintermolecular attractions betweenwater molecules.

+

H

CH3 CH2 OH

CH3 CH2 OOHH

OHH

OHH

OHH

In Section 2-12, we will see many kinds of organic compounds with a wide vari-ety of “functional groups.” As you encounter these new compounds, you should lookto see whether the molecules are polar or nonpolar and whether they can engage inhydrogen bonding.



Most vitamins consist of chargedgroups, making them water-solu-ble. As a result, they are rapidlyeliminated and generally nontoxic.Vitamins A and D, however, arenonpolar and are stored in the fattissue of the body, which is alsononpolar. Hence, these two vita-mins are potentially toxic in largedoses.

PROBLEM 2-18

Circle the member of each pair that is more soluble in water.(a) or (b) or (c) or

(d)

O

C

H3C CH3

O

or

CH3 CH2 CH2 CH2 OHCH3 CH2 OHCH3 CH2 CH2 CH3CH3 CH2 NHCH3

CH3 CH2 CH2 CH2 CH3CH3 CH2 OCH2 CH3

2-12Hydrocarbons

In future chapters, we will study many different types of organic compounds. The var-ious kinds of compounds are briefly described here so that you can recognize them asyou encounter them. For the purpose of this brief survey, we divide organic com-pounds into three classes: (1) hydrocarbons, (2) compounds containing oxygen, and(3) compounds containing nitrogen.

The hydrocarbons are compounds composed entirely of carbon and hydro-gen. The major classes of hydrocarbons are alkanes, alkenes, alkynes, and aromatichydrocarbons.

2-12A AlkanesAlkanes are hydrocarbons that contain only single bonds. Alkane names generallyhave the -ane suffix, and the first part of the name gives the number of carbonatoms. Table 2-2 shows how the prefixes in the names correspond with the numberof carbon atoms.

The cycloalkanes are a special class of alkanes that are in the form of a ring.Figure 2-30 shows some cycloalkanes.

TABLE 2-2 Correspondence of Prefixes and Numbers of Carbon Atoms

Alkane Name Number of Carbons Alkane Name Number of Carbons

methane 1 hexane 6ethane 2 heptane 7

propane 3 octane 8butane 4 nonane 9pentane 5 decane 10

methane ethane propane butane isobutaneCH39CH9

9

CH3

CH3

CH39CH29CH29CH3CH39CH29CH3CH39CH3CH4

C CCH H

H H

H H

H HCC

H H

cyclopentane

cyclopentane

or or

cyclohexane

cyclohexane

C C

C C

C

C

H H

H H

H HH H

H H

H H» Figure 2-30Cycloalkanes. Cycloalkanes arealkanes in the form of a ring.


2-12 Hydrocarbons 69

Alkanes are the major components of heating gases (natural gas and liquefiedpetroleum gas), gasoline, motor oil, fuel oil, and paraffin “wax.” Other than combus-tion, alkanes undergo few reactions. In fact, when a molecule contains an alkane por-tion and a nonalkane portion, we often ignore the presence of the alkane portionbecause it is relatively unreactive. Alkanes undergo few reactions because they haveno functional group, where reactions usually occur. Functional groups are reactiveparts such as double bonds, hydroxyl groups, or halogen atoms. Most organic com-pounds are characterized and classified by the functional groups they contain.

A molecule with a functional group may be represented as the functional groupwith alkyl groups attached. An alkyl group is an alkane portion of a molecule, withone hydrogen atom removed to allow bonding to the functional group. Figure 2-31shows how an alkyl group is named, using a substituted cycloalkane as the example.

We are often concerned with the structure of only the most important part of amolecule. In these cases, we often use the symbol R as a substituent. The R group issimply an alkyl group. We presume that the exact nature of the R group is not important.

H H

HH

Hethane ethyl groupH

C C H

HH

HH

C C H

HH

HH

C C CH

CH2

CH2

CH2

CH2

CH2ethylcyclohexane ethylcyclohexane

or

Á Figure 2-31Naming of alkyl groups. Alkyl groups are named like the alkanes they are derived from, with a -yl suffix.

2-12B AlkenesAlkenes are hydrocarbons that contain carbon–carbon double bonds. A carbon–car-bon double bond is the most reactive part of an alkene, so we say that the double bondis the functional group of the alkene. Alkene names end in the -ene suffix, as shown bythe following examples:

ethene (ethylene) propene (propylene)

1-butene 2-butene

Carbon–carbon double bonds cannot rotate, and many alkenes show geometric(cis-trans) isomerism (Sections 2-7B, 2-8B). The following are the cis-trans isomers ofsome simple alkenes:

CH2 “ CH ¬ CH2 ¬ CH3 CH3 ¬ CH “ CH ¬ CH3

CH2 “ CH ¬ CH3CH2 “ CH2

R

an alkylcyclopentane

might be CH3

methylcyclopentane

CHor

isopropylcyclopentane

CH3

CH3

or other compounds

H

CH3

H

CH3

C C

cis-2-buteneH

CH3

CH3

H

C C

trans-2-butene cis-2-hexene trans-2-hexene

Cycloalkenes are also common. Unless the rings are very large, cycloalkenes arealways the cis isomers, and the term cis is omitted from the names. In a large ring, atrans double bond may occur, giving a trans-cycloalkene.



2-12C AlkynesAlkynes are hydrocarbons with carbon–carbon triple bonds as their functional group.Alkyne names generally have the -yne suffix, although some of their common names(acetylene, for example) do not conform to this rule. The triple bond is linear, so thereis no possibility of geometric (cis-trans) isomerism in alkynes.

ethyne (acetylene) propyne (methylacetylene)

1-butyne 2-butyne

In an alkyne, four atoms must be in a straight line. These four collinear atoms are noteasily bent into a ring, so cycloalkynes are rare. Cycloalkynes are stable only if thering is large.

2-12D Aromatic HydrocarbonsThe following compounds may look like cycloalkenes, but their properties are differ-ent from those of simple alkenes. These aromatic hydrocarbons (also called arenes)are all derivatives of benzene, represented by a six-membered ring with three doublebonds. This bonding arrangement is particularly stable, for reasons that are explainedin Chapter 16.

Just as a generic alkyl group substituent is represented by R, a generic aryl groupis represented by Ar. When a benzene ring serves as a substituent, it is called a phenylgroup, abbreviated Ph.

CHC

H

CH

CH

CH C

H

CRC

H

CH

CH

CH C

H

CC

H

CH

CH

CH C

H

CH2CH3

CH2CH3 R

or or or

an alkylbenzeneethylbenzenebenzene

H ¬ C ‚ C ¬ CH2 ¬ CH3 CH3 ¬ C ‚ C ¬ CH3

H ¬ C ‚ C ¬ CH3H ¬ C ‚ C ¬ H

trans-cyclodecenecyclohexenecyclopentene

The presence of a methyl or ethylgroup can sometimes make a bigdifference. For example, benzene isquite toxic and causes leukemia,while methyl benzene (and ethylbenzene) are much less toxicbecause enzymes can oxidize themethyl or ethyl group.

an arylcyclopentane

Armight be or other compounds

phenylcyclopentane

Ph�


2-13 Organic Compounds Containing Oxygen 71

PROBLEM 2-19

Classify the following hydrocarbons, and draw a Lewis structure for each one. A compoundmay fit into more than one of the following classifications:

alkane cycloalkane aromatic hydrocarbon

alkene cycloalkene

alkyne cycloalkyne

(a) (b) (c)

(d) (e) (f)

(g) (h) (i)

CCCH3

CH2CH(CH3)2

CHCH2CH2 C C CH2

CH2 CH2 CH2 CH2

CH3 CCCH2 CH2 CH3CH3 CHCHCH2 CH3CH31CH223 CH3

2-13Organic Compounds Containing Oxygen

Many organic compounds contain oxygen atoms bonded to alkyl groups. The majorclasses of oxygen-containing compounds are alcohols, ethers, ketones, aldehydes, car-boxylic acids, and acid derivatives.

2-13A AlcoholsAlcohols are organic compounds that contain the hydroxyl group as theirfunctional group. The general formula for an alcohol is Alcohols areamong the most polar organic compounds because the hydroxyl group is stronglypolar and can participate in hydrogen bonding. Some of the simple alcohols likeethanol and methanol are miscible (soluble in all proportions) with water. Names ofalcohols end in the -ol suffix from the word “alcohol,” as shown for the followingcommon alcohols:

R ¬ OH.1¬ OH2

R9OH2-propanol

(isopropyl alcohol)

OH

CH39CH9CH3

1-propanol(n-propyl alcohol)

CH39CH29CH29OHethanol

(ethyl alcohol)

CH3CH29OHmethanol

(methyl alcohol)

CH39OHan alcohol

Alcohols are some of the most common organic compounds. Methyl alcohol(methanol), also known as “wood alcohol,” is used as an industrial solvent and as anautomobile racing fuel. Ethyl alcohol (ethanol) is sometimes called “grain alcohol”because it is produced by the fermentation of grain or almost any other organic materi-al. “Isopropyl alcohol” is the common name for 2-propanol, used as “rubbing alcohol.”

2-13B EthersEthers are composed of two alkyl groups bonded to an oxygen atom. The general for-mula for an ether is (The symbol represents another alkyl group,either the same as or different from the first.) Like alcohols, ethers are much morepolar than hydrocarbons. Ethers have no hydrogens, however, so they cannothydrogen bond with themselves. Ether names are often formed from the names of thealkyl groups and the word “ether.” Diethyl ether is the common “ether” used for start-ing engines in cold weather and once used for surgical anesthesia.

O ¬ H

R¿R ¬ O ¬ R¿.



CH3 Odimethyl ether

CH3 CH3CH2 O CH2CH3

diethyl etherO CH3

cyclohexyl methyl etherROR�, an etherR O R�

2-13C Aldehydes and KetonesThe carbonyl group, is the functional group for both aldehydes and ketones.A ketone has two alkyl groups bonded to the carbonyl group; an aldehyde has onealkyl group and a hydrogen atom bonded to the carbonyl group. Ketone names gener-ally have the -one suffix; aldehyde names use either the -al suffix or the -aldehydesuffix.

The carbonyl group is strongly polar, and most ketones and aldehyder aresomewhat soluble in water. Both acetone and acetaldehyde are miscible with water.Acetone, often used as nail polish remover, is a common solvent with low toxicity.

C “ O,

CH3

O

C CH3 CH3

O

C CH2CH3

RCOR′, a ketone 2-propanone (acetone) 2-butanone (methyl ethyl ketone)

O

cyclohexanone

an aldehyde

CH3

O

C H

ethanal (acetaldehyde)

CH3CH2

O

C H

propanal (propionaldehyde)

CH3CH2CH2

O

C H

butanal (butyraldehyde)or or CH3CHO or CH3CH2CHO or CH3CH2CH2CHO

O

C

R R′

O

CR H

RCHO

2-13D Carboxylic AcidsCarboxylic acids contain the carboxyl group, as their functional group.The general formula for a carboxylic acid is The carboxylgroup is a combination of a carbonyl group and a hydroxyl group, but this combinationhas different properties from those of ketones and alcohols. Carboxylic acids owe theiracidity ( of about 5) to the resonance-stabilized carboxylate anions formed bydeprotonation. The following reaction shows the dissociation of a carboxylic acid:

pKa

R ¬ COOH 1or RCO2 H2.¬ COOH,

R C HO

O

� H2O R C

O

O � R C

O �

O � H3O�

carboxylate anioncarboxylic acid

Systematic names for carboxylic acids use the -oic acid suffix, but historicalnames are commonly used. Formic acid was first isolated from ants, genus Formica.Acetic acid, found in vinegar, gets its name from the Latin word for “sour” (acetum).Propionic acid gives the tangy flavor to sharp cheeses, and butyric acid provides thepungent aroma of rancid butter.

methanoic acid(formic acid)

H9C9OHbutanoic acid(butyric acid)

CH39CH29CH29C9OH

O O

propanoic acid(propionic acid)

CH39CH29C9OH

O

ethanoic acid(acetic acid)

CH39C9OH

O

Carboxylic acids are strongly polar, like ketones, aldehydes, and alcohols. Theyare relatively soluble in water; in fact, all four of the carboxylic acids shown here aremiscible (soluble in all proportions) with water.


2-14 Organic Compounds Containing Nitrogen 73

PROBLEM 2-20

Draw a Lewis structure, and classify each of the following compounds. The possible classifi-cations are as follows:

alcohol ketone carboxylic acid

ether aldehyde

(a) (b) (c)

(d) (e) (f)

(g) (h) (i)

2-13E Carboxylic Acid DerivativesSeveral related functional groups can be formed from carboxylic acids. Each containsthe carbonyl group bonded to an oxygen or other electron-withdrawing element.Among these functional groups are acid chlorides, esters, and amides. All of thesegroups can be converted back to carboxylic acids by acidic or basic hydrolysis.

CH2OHCHOO

OCOOH

CH3 CH2 OCH2 CH3

CH3 COCH2 CH3CH3 CH2 CH1OH2CH3CH3 CH2 CHO

2-14Organic Compounds Containing Nitrogen

Nitrogen is another element often found in the functional groups of organic compounds.The most common “nitrogenous” organic compounds are amines, amides, and nitriles.

2-14A AminesAmines are alkylated derivatives of ammonia. Like ammonia, amines are basic.

Because of their basicity (“alkalinity”), naturally occurring amines are often called alk-aloids. Simple amines are named by naming the alkyl groups bonded to nitrogenand adding the word “amine.” The structures of some simple amines are shown below,together with the structure of nicotine, a toxic alkaloid found in tobacco leaves.

R9NH2 R9NH3 Kb � 10−3−OHH2O++

carboxylic acidor R9COOH

CH39C9OH

acetic acidor CH3COOH

O

acid chlorideor R9COCl

CH39C9Cl

acetyl chlorideor CH3COCl

O

esteror R9COOR�

CH39C9O9CH2CH3

ethyl acetateor CH3COOCH2CH3

O

amideor R9CONH2

CH39C9NH2

acetamideor CH3CONH2

O

R9C9OH

O

R9C9Cl

O

R9C9O9R�

O

R9C9NH2

O

aminesor or

NH2CH3

NH

N

CH3(CH3CH2)3NN

piperidinemethylamineNHCH3 CH2CH3

ethylmethylamine triethylamine nicotine

NH2R NHR R′ NR R′′

R′



2-14B AmidesAmides are acid derivatives that result from a combination of an acid with ammonia oran amine. Proteins have the structure of long-chain, complex amides.

Amides are among the most stable acid derivatives. The nitrogen atom of anamide is not as basic as the nitrogen of an amine because of the electron-withdrawingeffect of the carbonyl group. The following resonance forms help to show why amidesare very weak bases:

2-14C NitrilesA nitrile is a compound containing the cyano group, The cyano group wasintroduced in Section 2-6 as an example of sp hybridized bonding.

All of these classes of compounds are summarized in the table of CommonOrganic Compounds and Functional Groups, given on the front inside cover forconvenient reference.

PROBLEM 2-21

Draw a Lewis structure, and classify each of the following compounds:(a) (b) (c)(d) (e) (f)

(g) (h) (i)

(j) (k) (l)

(m) (n) (o) (p)COCH3

CN

O

O

O

N

CH3

N C

O

CH3

O

N CH3N CH3

O

O

O

O1CH323 CCH2 CH2 COOH

CH3 CH2 CH2 CN1CH3 CH222 O1CH3 CH223 CCH2 COCl1CH322 CHCOOCH31CH3 CH222 NHCH3 CH2 CONHCH3

CH3 C N CH3CH2 C N C N

benzonitrilepropionitrileacetonitrilea nitrile

NR C

¬ C ‚ N.

C NH2R

O

C NH2R

very weak baseO�

�

or oramides

O

CCH3 NH2

O

C NH

N-methylacetamide

CH3 CH3 C

O

N

CH3

CH3

N,N-dimethylbenzamideacetamide

O

CR NH2

O

CR NHR�

O

CR NR�2


Chapter 2 Glossary 75

PROBLEM 2-22

Circle the functional groups in the following structures. State to which class (or classes) ofcompounds the structure belongs.(a) (b) (c)(d) (e) (f)

(g) (h) (i)

(j) (k)

CH3

CH3

CH3

HO

OCH3

(CH2CH2CH2C

CH3

H)3 CH3

vitamin EO

OH

CH2OH

OHO

hydrocortisone

O

CNCH2OH

R ¬ COOHCH3 NHCH3HCONH2

CH3 CHOCH3 ¬ O ¬ CH3CH2 “ CHCH2 CH3

Chapter 2 Glossary

acid chloride An acid derivative with a chlorine atom in place of the hydroxyl group.(p. 73)

alcohol A compound that contains a hydroxyl group; (p. 71)aldehyde A carbonyl group with one alkyl group and one hydrogen; (p. 72)

alkanes Hydrocarbons containing only single bonds. (p. 68)alkenes Hydrocarbons containing double bonds. (p. 69)alkynes Hydrocarbons containing triple bonds. (p. 70)alkyl group A hydrocarbon group with only single bonds; an alkane with one hydrogenremoved, to allow bonding to another group; symbolized by R. (p. 69)amide An acid derivative that contains an amine instead of the hydroxyl group of the acid. (p. 74)

amine An alkylated analogue of ammonia; or (p. 73)aromatic hydrocarbons (arenes) Hydrocarbons containing a benzene ring, a six-memberedring with three double bonds. (p. 70)bond dipole moment A measure of the polarity of an individual bond in a molecule, defined as

where is the dipole moment in debyes ( esu - Å), d is the bondlength in angstroms, and is the effective amount of charge separated, in units of the electroniccharge. (p. 58)carbonyl group The functional group, as in a ketone or aldehyde. (p. 72)

carboxyl group The functional group, as in a carboxylic acid. (p. 72)carboxylic acid A compound that contains the carboxyl group; (p. 72)

R9C9OH

O

¬ COOH

OC

d10-10mm = 14.8 * d * d2,

R3 N.R ¬ NH2, R2 NH,

R9C9NH2

O

R9C9NHR�

O

R9C9NR�2

O

C ‚ CC “ C

R9C9H.

O

R ¬ OH.

R9C9Cl

O



cis-trans isomers (geometric isomers) Stereoisomers that differ in their cis-trans arrangementon a ring or a double bond. The cis isomer has similar groups on the same side, and the transisomer has similar groups on opposite sides. (p. 57)constitutional isomers (structural isomers) Isomers whose atoms are connected differently;they differ in their bonding sequence. (p. 56)cyano group The functional group, as in a nitrile. (p. 74)dipole–dipole forces Attractive intermolecular forces resulting from the attraction of thepositive and negative ends of the molecular dipole moments of polar molecules. (p. 62)dipole moment See bond dipole moment and molecular dipole moment. (p. 58)double bond A bond containing four electrons between two nuclei. One pair of electronsforms a sigma bond, and the other pair forms a pi bond. (p. 44)ester An acid derivative with an alkyl group replacing the acid proton. (p. 73)

ether A compound with an oxygen bonded between two alkyl groups; (p. 71)functional group The reactive, nonalkane part of an organic molecule. (p. 69)geometric isomers See cis-trans isomers. (p. 57)hybrid atomic orbital A directional orbital formed from a combination of s and p orbitals onthe same atom. Two orbitals are formed by sp hybridization, three orbitals by hybridization,and four orbitals by hybridization. (p. 45)

sp hybrid orbitals give a bond angle of 180° (linear geometry).hybrid orbitals give bond angles of 120° (trigonal geometry).hybrid orbitals give bond angles of 109.5° (tetrahedral geometry).

hydrocarbons Compounds composed exclusively of carbon and hydrogen.alkanes: Hydrocarbons containing only single bonds. (p. 68)alkenes: Hydrocarbons containing double bonds. (p. 69)alkynes: Hydrocarbons containing triple bonds. (p. 70)cycloalkanes, cycloalkenes, cycloalkynes: Alkanes, alkenes, and alkynes in the form of aring. (p. 68)aromatic hydrocarbons: Hydrocarbons containing a benzene ring, a six-membered ringwith three double bonds. (p. 70)

hydrogen bond A particularly strong attraction between a nonbonding pair of electrons and anelectrophilic or hydrogen. Hydrogen bonds have bond energies of about5 kcal/mol (21 kJ/mol), compared with about 100 kcal/mol (about 400 kJ/mol) for typical

bonds. (p. 63)hydroxyl group The functional group, as in an alcohol. (p. 71)isomers Different compounds with the same molecular formula. (p. 56)

constitutional isomers (structural isomers) are connected differently; they differ in theirbonding sequence.stereoisomers differ only in how their atoms are oriented in space.cis-trans isomers (geometric isomers) are stereoisomers that differ in their cis-transarrangement on a ring or a double bond.stereochemistry is the study of the structure and chemistry of stereoisomers.

ketone A carbonyl group with two alkyl groups attached. (p. 72)

linear combination of atomic orbitals (LCAO) Wave functions can add to each other to pro-duce the wave functions of new orbitals. The number of new orbitals generated equals the orig-inal number of orbitals. (p. 41)London dispersion forces Intermolecular forces resulting from the attraction of correlatedtemporary dipole moments induced in adjacent molecules. (p. 62)molecular dipole moment The vector sum of the bond dipole moments (and any nonbondingpairs of electrons) in a molecule; a measure of the polarity of a molecule. (p. 60)

R9C9R�

O

¬ OHC ¬ H

N ¬ HO ¬ H

benzene

C ‚ CC “ C

sp3sp2

sp3sp2

R ¬ O ¬ R¿.

R9C9OR�

O

¬ C ‚ N


Study Problems 77

molecular orbital (MO) An orbital formed by the overlap of atomic orbitals on differentatoms. MOs can be either bonding or antibonding, but only the bonding MOs are filled in moststable molecules. (p. 41)

A bonding molecular orbital places a large amount of electron density in the bonding re-gion between the nuclei. The energy of an electron in a bonding MO is lower than it is in anatomic orbital.An antibonding molecular orbital places most of the electron density outside the bond-ing region. The energy of an electron in an antibonding MO is higher than it is in an atomicorbital.

nitrile A compound containing a cyano group, (p. 74)node In an orbital, a region of space with zero electron density. (p. 40)pi bond ( bond) A bond formed by sideways overlap of two p orbitals. A pi bond has its elec-tron density in two lobes, one above and one below the line joining the nuclei. (p. 44)sigma bond ( bond) A bond with most of its electron density centered along the line joiningthe nuclei; a cylindrically symmetrical bond. Single bonds are normally sigma bonds. (p. 41)stereochemistry The study of the structure and chemistry of stereoisomers. (p. 57)stereoisomers Isomers that differ only in how their atoms are oriented in space. (p. 57)structural isomers (IUPAC term: constitutional isomers) Isomers whose atoms are connect-ed differently; they differ in their bonding sequence. (p. 56)triple bond A bond containing six electrons between two nuclei. One pair of electrons forms asigma bond and the other two pairs form two pi bonds at right angles to each other. (p. 52)valence-shell electron-pair repulsion theory (VSEPR theory) Bonds and lone pairs arounda central atom tend to be separated by the largest possible angles: about 180° for two, 120° forthree, and 109.5° for four. (p. 45)van der Waals forces The attractive forces between neutral molecules, including dipole–di-pole forces and London forces. (p. 62)

dipole–dipole forces: The forces between polar molecules resulting from attraction of theirpermanent dipole moments.London forces: Intermolecular forces resulting from the attraction of correlated temporarydipole moments induced in adjacent molecules.

wave function The mathematical description of an orbital. The square of the wave functionis proportional to the electron density. (p. 39)

Essential Problem-Solving Skills in Chapter 2

1. Draw the structure of a single bond, a double bond, and a triple bond.

2. Predict the hybridization and geometry of the atoms in a molecule.

3. Draw a three-dimensional representation of a given molecule.

4. Identify constitutional isomers and stereoisomers.

5. Identify polar and nonpolar molecules, and predict which ones can engage in hydro-gen bonding.

6. Predict general trends in the boiling points and solubilities of compounds, based ontheir size, polarity, and hydrogen-bonding ability.

7. Identify the general classes of hydrocarbons, and draw structural formulas for examples.

8. Identify the classes of compounds containing oxygen or nitrogen, and draw structuralformulas for examples.

1c22(C)

s

p

¬ C ‚ N.

Study Problems2-23 Define and give examples of the following terms:

(a) bonding MO (b) antibonding MO (c) hybrid atomic orbital(d) sigma bond (e) pi bond (f) double bond(g) triple bond (h) constitutional isomers (i) cis-trans isomers(j) stereoisomers (k) bond dipole moment (l) molecular dipole moment



(m) dipole–dipole forces (n) London forces (o) hydrogen bonding(p) miscible liquids (q) hydrocarbons (r) alkyl group(s) functional group

2-24 Give a definition and an example for each class of organic compounds.(a) alkane (b) alkene (c) alkyne(d) alcohol (e) ether (f) ketone(g) aldehyde (h) aromatic hydrocarbon (i) carboxylic acid(j) ester (k) amine (l) amide(m) nitrile

2-25 If the carbon atom in were flat, there would be two stereoisomers. The carbon atom in is actually tetra-hedral. Make a model of this compound, and determine whether there are any stereoisomers of

2-26 Cyclopropane ( a three-membered ring) is more reactive than most other cycloalkanes.(a) Draw a Lewis structure for cyclopropane.(b) Compare the bond angles of the carbon atoms in cyclopropane with those in an acyclic (noncyclic) alkane.(c) Suggest why cyclopropane is so reactive.

2-27 For each of the following compounds,1. Give the hybridization and approximate bond angles around each atom except hydrogen.2. Draw a three-dimensional diagram, including any lone pairs of electrons.

(a) (b) (c)(d) (e) (f)(g) (h) (i)

2-28 For each of the following compounds,1. Draw a Lewis structure.2. Show the kinds of orbitals that overlap to form each bond.3. Give approximate bond angles around each atom except hydrogen.

(a) (b) (c)(d) (e) (f)

(g) (h) (i)

2-29 In most amines, the nitrogen atom is hybridized, with a pyramidal structure and bond angles close to 109°. Informamide, the nitrogen atom is found to be planar, with bond angles close to 120°. Explain this surprising finding.(Hint: Consider resonance forms and the overlap needed in them.)

2-30 Predict the hybridization and geometry of the carbon and nitrogen atoms in the following ions. (Hint: Resonance.)

(a) (b)2-31 Draw orbital pictures of the pi bonding in the following compounds:

(a) (b) HCN (c)(d)

2-32 (a) Draw the structure of cis- showing the pi bond with its proper geometry.(b) Circle the six coplanar atoms in this compound.(c) Draw the trans isomer, and circle the coplanar atoms. Are there still six?(d) Circle the coplanar atoms in the following structure.

CH3

CH3 ¬ CH “ CH ¬ CH2 CH3

CH3 ¬ C ‚ C ¬ CHOCH2 “ CH ¬ CH “ CH ¬ CNCH3 COCH3

H2 N ¬ CH “ CH ¬ C+

H2CH39C9CH2

O�

H9C9NH2

O

formamide

sp3

OOO

CH39C9CH3

O

H2 N ¬ CH2 ¬ CNCH3 ¬ C ‚ C ¬ CHOCH3 ¬ CH “ C1CH322

CH3 ¬ CH “ N ¬ CH3CH3 CH2 OH1CH322 NH

CH2 OCH3 OHCH3 CH “ NHCH3 COOH1CH324 N+1CH323 NNH2 NH2

-OHH3 O+

C3 H6,

H9C9Cl

H

Cl

Cl9C9Cl

H

H

CH2 Cl2.CH2 Cl2CH2 Cl2


Study Problems 79

2-33 In 2-pentyne there are four atoms in a straight line. Use dashed lines and wedges to draw a three-dimensional representation of this molecule, and circle the four atoms that are in a straight line.

2-34 Which of the following compounds show cis-trans isomerism? Draw the cis and trans isomers of the ones that do.

(a) (b) (c)

(d) (e)

2-35 Give the relationships between the following pairs of structures. The possible relationships are: same compound, cis-transisomers, constitutional (structural) isomers, not isomers (different molecular formula).(a) (b)

(c) (d)

(e) (f)

(g) (h)

2-36 Sulfur dioxide has a dipole moment of 1.60 D. Carbon dioxide has a dipole moment of zero, even though bondsare more polar than bonds. Explain this apparent contradiction.

2-37 For each of the following compounds,1. Draw the Lewis structure.2. Show how the bond dipole moments (and those of any nonbonding pairs of electrons) contribute to the molecular

dipole moment.3. Predict whether the compound will have a large small, or zero dipole moment.

(a) (b) (c) (d)

(e) (f) (g)

2-38 Diethyl ether and 1-butanol are isomers, and they have similar solubilities in water. Their boiling points are very different,however. Explain why these two compounds have similar solubility properties but dramatically different boiling points.

diethyl ether, bp 35°C 1-butanol, bp 118°C8.4 mL dissolves in 100 mL 9.1 mL dissolves in 100 mL

2-39 N-methylpyrrolidine has a boiling point of 81°C, and piperidine has a boiling point of 106°C.(a) Explain this large difference (25°C) in boiling point for these two isomers.(b) Tetrahydropyran has a boiling point of 88°C, and cyclopentanol has a boiling point of 141°C. These two isomers

have a boiling point difference of 53°C. Explain why the two oxygen-containing isomers have a much larger boilingpoint difference than the two amine isomers.

N CH3

N-methylpyrrolidine, bp 81°C piperidine, bp 106°C

N H

tetrahydropyran, bp 88°C

O OH

cyclopentanol, bp 141°C

H2 OH2 O

CH3 CH2 CH2 CH2 ¬ OHCH3 CH2 ¬ O ¬ CH2 CH3

Cl

N

H

C C

CN

CN

CN

CN

H3C C CH3

O

CBr4CH3 ¬ CNCH3 ¬ CH “ N ¬ CH3

171 D2,

S ¬ OC ¬ O

and

O O

and

CH2 CH2

CH2CH3

CH3

and CH2 CH2

CH3 CH2CH3

and

CH3

H3C

CH3 CH3

and

CH3

H3

C

C

CH2

CH3 CH3 CH3

CH3

and

CH2 “ CH ¬ CH2 Cl and CHCl “ CH ¬ CH3CH3 CH2 CH2 CH3 and 1CH323 CH

CH39CH"C9CH29CH3

CH2CH2CH3

cyclopentene,

CH2 “ C1CH322CH3 ¬ C ‚ C ¬ CH3CH3 CH “ CHCH3

1CH3 CCCH2 CH32



2-40 Which of the following pure compounds can form hydrogen bonds? Which can form hydrogen bonds with water?(a) (b) (c)(d) (e) (f)(g) (h) (i)

( j) (k) (l)

2-41 Predict which compound in each pair has the higher boiling point. Explain your prediction.(a) (b)(c) (d)

2-42 Circle the functional groups in the following structures. State to which class (or classes) of compounds the structure belongs.

(a) (b) (c)

(d) (e) (f)

(g) (h)

2-43 Dimethyl sulfoxide (DMSO) has been used as an anti-inflammatory rub for racehorses. DMSO and acetone seem to havesimilar structures, but the carbon atom in acetone is planar, while the sulfur atom in DMSO is pyramidal.Draw correct Lewis structures for DMSO and acetone, predict the hybridizations, and explain these observations.

2-44 Many naturally occurring compounds contain more than one functional group. Identify the functional groups in the fol-lowing compounds:(a) Penicillin G is a naturally occurring antibiotic.(b) Dopamine is the neurotransmitter that is deficient in Parkinson’s disease.(c) Thyroxine is the principal thyroid hormone.(d) Testosterone is a male sex hormone.

CH2CHO

HO

OHO

I

I

CH2

I

I

H2

NH2

CH COOH

NH2

C

O

NH

N

S

COOHpenicillin G

O

dopamine

thyroxineO

OH

testosterone

CH2

CH39S9CH3

O

CH39C9CH3

O

DMSO acetone

S “ OC “ O

CCH3 COOCH3

NH2

H

CH2OCH3

CN

O

N H

O

O

O

CHOCOOHO

O

CH3 CH2 CH2 CH2 CH3 or CH3 CH2 CH2 CH2 CH2 ClCH3 CH2 CH2 CH2 CH3 or 1CH322 CHCH2 CH3

CH3 CH2 CH2 CH3 or CH3 CH2 CH2 CH2 CH3CH3 CH2 OCH3 or CH3 CH1OH2CH3

H3C C NH2

OO OO

CH3 CH2 CHOCH3 CH2 COOHCH3 COCH3

CH2 “ CH ¬ CH2 CH3CH31CH223 CH31CH3 CH2 CH222 OCH3 CH2 CH2 OH1CH3 CH223 N1CH3 CH222 NH


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