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William L Masterton

Cecile N. Hurley

Chapter 22
Organic Chemistry
Chapter Outline
• (22.1) Saturated hydrocarbons: alkanes
• (22.2) Unsaturated hydrocarbons: alkenes and
alkynes
• (22.3) Aromatic hydrocarbons and their
derivatives
• (22.4) Functional groups
• (22.5) Isomerism in organic compounds
• (22.6) Organic reactions

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Organic Chemistry
• Deals with compounds of carbon
• Over 90% of all known compounds contain carbon
• Carbon atoms bond to each other to a greater extent
than atoms of any other element
• Carbon atoms link together to form chains or rings

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Common Features of Organic Compounds
• Molecular rather than ionic
• Each carbon atom forms four covalent bonds
• Carbon atoms bond to atoms of other elements or to
other nonmetal atoms

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Hydrocarbon
• Simplest type of organic compound
• Contains hydrogen and carbon atoms
• Organic compounds contain nitrogen or oxygen
• Classification
• Alkanes
• Alkenes and Alkynes
• Aromatics

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Saturated Hydrocarbons: Alkanes
• Include substances in which all the carbon-carbon
bonds are single bonds
• Involve carbon atoms that are bonded to each other
in chains
• Long or short, straight or branched
• Contain maximum ratio of hydrogen to carbon atoms

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Saturated Hydrocarbons: Alkanes
• Formula when there are n carbon atoms is CnH2n+2
• Simple alkanes (n = 1, 2, 3)

• Carbons surrounded by four single bonds


• sp3 hybrid orbitals
• Bond angles approximately 109.5°
• Directed toward the corners of a regular tetrahedron

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Figure 22.1 - Three Simplest Alkanes

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Structural Isomers of Butane
• Two different alkanes with the formula C4H10

• Structural isomers: Compounds having the same


molecular formula but different molecular structures

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Figure 22.2 - Molecular Structures of Isomers of
Butane and 2-Methylpropane

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Example 22.1
• Draw structures for the isomers of C5H12
• Strategy
• Start by writing all five-carbon atoms in a straight
chain. Call this structure isomer (I)
• Write a four-carbon chain structure bonding the fifth
carbon atom to one of the C atoms in the straight
chain

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Example 22.1
• Note that bonding the fifth C atom to either end of the
straight chain gives you isomer (I). You have to attach
the C atom next to the terminal atom (on either end)
• Write a three-carbon chain. Do not attach the
remaining two carbon atoms as a chain to either end
of the three-carbon chain. You will get Isomer (I).
Attaching one carbon atom to each end of the three-
carbon chain also gives you isomer (I)

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Example 22.1
• Solution
• Isomer (I) five-C chain:

• Isomer (II) four-C chain:

• Isomer (III) three-C chain:

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Nomenclature
• IUPAC naming convention
• For straight chains, the name consists a single word
• For branched chains, the name is complex, consisting
of two parts
• Suffix identifies the parent straight-chain alkane
• Prefix identifies the branching alkyl group

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Table 22.1 - Nomenclature of Alkanes

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IUPAC Names for Isomers of Pentane

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Sources of Alkanes
• Natural gas
• 80-90% methane
• Small portions of C2H6, C3H3, and C4H10
• Bottled gas
• Used with campstoves, barbecue grills, and the like
• Contains liquid propane and butane
• Used in homes that do not have access to a gas line
• Petroleum
• Crude oil is the source of other hydrocarbons
• Distillation gives a series of fractions of different
boiling points
• Gasoline Copyright ©2016 Cengage Learning. All Rights Reserved.
Figure 22.3 - Bottled Gas

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Figure 22.4 - Petroleum distillation

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Gasoline
• Octane number is a measure of the gasoline’s
resistance to knock
• Isooctane has an octane number of 100 as it burns
smoothly
• Usage of additives of one type or another helps in
obtaining premium gasoline

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Gasoline
• Antiknock compounds
• Tetraethyllead (C2H5)4Pb
• Usage stopped as it poisoned catalytic converters and
caused contamination of the environment
• Ethanol (C2H5OH)
• Added to gasoline to promote smooth, complete
combustion

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Cycloalkanes
• Saturated hydrocarbons containing only single
bonds
• Contain two fewer hydrogens than chain alkanes

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Figure 22.5 - Molecular Structure of Cycloalkanes

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Unsaturated Hydrocarbons
• Contain at least one multiple bond
• Fewer hydrogen atoms in an unsaturated hydrocarbon
than in a saturated one
• Types
• Alkenes: Contain one carbon-carbon double bond in
the molecule
• Each double bond replaces a pair of hydrogen atoms
• General formula is CnH2n
• Alkynes: Contain one carbon-carbon triple bond in
the molecule
• Each triple bond replaces two pairs of hydrogens
• General formula is CnH2n-2
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Structures of Alkenes and Alkynes
• Alkene

• Alkyne

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Example 22.3
• What is the molecular formula of the alkane, alkene,
and alkyne containing six carbon atoms, and of the
alkane containing ten hydrogen atoms?
• Strategy
• Apply the formulas:
• CnH2n+2 for alkanes
• CnH2n for alkenes
• CnH2n-2 for alkynes

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Example 22.3
• Solution
• Six C atoms
• Alkane: n = 6; H atoms = 2n + 2 = 2(6) + 2 = 14 →C6H14
• Alkane: n = 6; H atoms = 2n = 2(6) = 12 → C6H12
• Alkane: n = 6; H atoms = 2n – 2 = 2(6) - 2 = 10 → C6H10
• Alkane with ten H atoms
• Alkane with 10 H atoms: 2n + 2 = 10; n = 4 → C4H10

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Alkenes
• Simplest alkene
• Ethene (common name, ethylene)

• Double bond consists of a sigma and a pi bond


• Ideal bond angles are 120
• Produced commercially in large quantities through
heating to about 700°C
C2 H 6 (g) 
 C2 H 4 (g) + H 2 (g)

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Alkenes
• Name is similar to alkanes, with an exception
• –ane is replaced by –ene

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Naming Alkenes
• Number is used to designate the double-bonded
carbon
• Number is made as small as possible

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Alkynes
• Name is derived from that of an alkene, with the
suffix changed from –ene to –yne

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Acetylene
• Important alkyne and the first member of the series
• Includes:
• One sigma and two pi bonds
• sp-hybridization
• Linear molecule with180 bond angles
• Thermodynamically unstable with respect to
decomposition into its elements

C2H2  g  
 2C  s  + H2  g  ΔG° = -209.2 kJ at 25°C

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Acetylene
• Stored in a cylinder packed with porous material as a
solution in acetone due to its unstable nature
• Burns at temperatures above 2000°C when mixed
with pure oxygen in a torch
• Heat comes from the following reaction
5
C2 H 2  g  + O 2  g  
 2CO 2 (g) + H 2O(l) ΔH = -1300 kJ
2

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Figure 22.7 - Two simplest Alkynes

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Aromatic Hydrocarbons and Their
Derivatives
• Otherwise known as arenes
• Considered as derivatives of benzene (C6H6)
• Exhibit high degree of unsaturation
• Regarded as a resonance hybrid of the two structures
by the atomic orbital model

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Electron Distribution in Benzene
• Based on molecular orbital theory
• Each carbon atom forms three sigma bonds
• One to a hydrogen and two to adjacent carbon atoms
• Three electron pairs remaining are spread
symmetrically over the entire molecule to form
delocalized pi bonds
• Represented by the structure:

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Derivatives of Benzene
• Various modern antiseptics are phenol derivatives
• Toluene has replaced benzene as a solvent as it is
less toxic
• Oxidation of toluene gives benzoic acid

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Groups Attached to the Benzene Ring
• Forms three isomers designated by the following
prefixes
• Ortho-
• Meta-
• Para-

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Groups Attached to the Benzene Ring
• Numbers are also used to refer to the compounds
• Become mandatory when three or more substituents
are present

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Example 22.5
• Name the following compounds as derivatives of
phenol

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Example 22.5
• Solution

• Parent compound OH is called phenol

• CH3 (methyl) is in the meta position


• Name: meta-methylphenol; common name: meta-
cresol
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Example 22.5

• Parent compound is phenol


• Number the carbon atom to which the OH group is
bonded C1
• NO2 groups are in the C2, C4, and C6 positions
whether counted in a clockwise or counterclockwise
manner
• Name: 2,4,6-trinitrophenol; common name: picric acid

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Condensed Ring Structures
• Fusion of three benzene rings gives two different
isomers
• Anthracene
• Phenanthrene

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Functional Groups
• Substituted to derive organic molecules from
hydrocarbons
• Nonmetal atom or a small group of atoms bonded to
carbon

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Table 22.2 - Common Functional Groups

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Alcohols
• Have the structural formula R—O—H
• R is an alkyl group
• Named by substituting the suffix -ol for the -ane suffix
of the corresponding alkane
• First four alcohols are represented with common
names in red

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Alcohols
• Properties
• Have higher boiling points than alkanes
• Molecules are strongly hydrogen-bonded to one
another
• Are water-soluble when the molar mass is low

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Ethers
• Have the structural formula R—O—R’
• Alkyl groups can be the same or different
• Are named by citing the two alkyl groups:
• CH3—O—CH3 dimethyl ether
• CH3—O—C2H5 ethyl methyl ether
• Properties
• Do not contain OH groups and have lower boiling
points
• Form hydrogen bonds with water by making use of the
OH groups in the water molecule

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Table 22.3 - Physical Properties

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Commercial Alcohols and Ethers
• Methanol
• Prepared from synthesis gas

CO (g ) + 2H2 (g ) 
Zn O,Cr2O3
250atm,350o C
 CH3OH(g )

• Otherwise known as wood alcohol as it is a byproduct


when charcoal is made by heating wood
• Used in jet fuels and as a solvent, gasoline additive,
and starting material for various industrial syntheses

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Commercial Alcohols and Ethers
• Ethanol
• Formed from fermentation of sugar or grain
• Common name - Grain alcohol
• Used as active ingredient of alcoholic beverages
• Is tasteless and colorless
• Formed by a reaction of ethylene with water and
sulfuric acid as the catalyst, for industrial use

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Commercial Alcohols and Ethers
• Alcohols containing two or more —OH groups per
molecule

• Ethylene glycol is used as an antifreeze


• Glycerol is formed as a byproduct in making soaps
• Used in making drugs, antibiotics, plastics, and
explosives

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Commercial Alcohols and Ethers
• Diethyl ether
• Otherwise known as ether
• Liquid ether, on contacts with air, tends to form
compounds called hydroperoxides

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Ketones and Aldehydes
• Ketones: Two hydrocarbon groups are bonded to
the central carbon atom

• Aldehydes: Includes minimum one hydrogen atom

• Carbonyl group

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Common Aldehydes and Ketones
• Acetone
• Water-soluble
• Common solvent
• Used in fingernail polish remover
• Formaldehyde
• Used in a water solution as formalin
• Preservative for biological specimens
• Carcinogenic

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Example 22.6
• Classify each of the following as an alcohol, ether,
aldehyde, or ketone

• Strategy
• Identify the functional group and use Table 22.2
• Note that more than one functional group may be
involved

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Example 22.6
• Solution

• Functional group: —O—


• The molecule is an ether

• Functional groups:
• The molecule is an aldehyde and an alcohol
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Example 22.6

• Functional groups:
• The molecule is a ketone and an alcohol

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Figure 22.10 - Aromatic Aldehydes

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Carboxylic Acids
• Have the following structure

• R is a hydrocarbon group or a hydrogen atom


• First two members of the series

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Properties of Carboxylic Acids
• Act as weak acids in water solutions
RCOOH(aq) H + (aq) + RCOO- (aq)
• Vary in strength
• Trichloroacetic acid has Ka = 0.20
• Strong acetic acid which is used in removing warts

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Properties of Carboxylic Acids
• Treatment with the strong base NaOH forms the
sodium salt of the acid
• Acid-base reaction with acetic acid

• Soaps are sodium salts of long-chain carboxylic


acids such as stearic acid

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Esters
• Formed by reactions between an alcohol and
carboxylic acid

• Reaction between acetic acid and methyl alcohol


gives methyl acetate

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Table 22.4 - Properties of Esters

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Amines
• Primary - Have two hydrogens which are bonded to
a nitrogen atom, giving a formula R—NH2
• Methylamine, CH3NH2 - First member of the series
• Flammable gas at 25°C and 1 atm
• Contains a fishy odor
• Weak base (Kb = 4 X 10-4)
• Reacts with strong acid
CH3 NH 2 (aq) + H + (aq) 
 CH3 NH3+ (aq)

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Isomerism in Organic Compounds

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Geometric (cis-trans) Isomers
• Geometric isomerism: Gives rise to an extra
compound
• Cis isomer: Formed when two CH3 groups are as
close to one another as possible
• Trans isomer: Consists of two identical groups which
are farther apart

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Optical Isomers
• Occur when at least one carbon is bonded to four
different atoms or groups
• Non-superimposable mirror images
• Resembles an individual’s right and left hands
• Mirror images
• Not superimposable on each other
• Carbon with four different bonded atoms or groups is
known as chiral
• Two different forms are called enantiomers
• Carbon atom serves as a chiral center

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Figure 22.11 - Optical Isomers

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Figure 22.12 - Mirror Images

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Interaction of Enantiomers with Light
• Plane is rotated from its original position when plane-
polarized light is passed through a sample of an
enantiomer
• Optical isomerism - Comes from the effect that
enantiomers have on plane-polarized light
• One isomer rotates to the right
• One isomer rotates to the left
• Racemic mixture: Formed if both isomers are
present in equal amounts
• Two rotations offset each other and there is no effect on
plane-polarized light

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Figure 22.13 - Polarimeter

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Enantiomers
• Physically identical, except for the direction of
rotation of plane-polarized light

• Interaction with biochemical molecules are different


due to the difference in the three-dimensional
structure

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Chiral Drugs

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Methods of Preparing Chiral Drugs
• Resolving a racemic mixture into its components
• Carried out by Louis Pasteur who used a magnifying
glass and a pair of tweezers to separate crystals of
enantiomers
• Asymmetric synthesis
• Optically inactive precursor is converted to the drug by
a reaction that uses a special catalyst
• Results in a single enantiomer with the desired
physiological effect

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Organic Reactions
• Species taking part in the reactions are molecules
rather than ions
• Take place between pure substances or in nonpolar
solvents
• Occur slowly

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Addition Reactions
• Small molecules add across a double or triple bond
• Hydrogenation
• Commercially used in the conversion of liquid to solid
fats

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Addition Reactions
• Hydration
• Adding water in the presence of an acid catalyst
C2 H4 (g) + H2O(l)  C2 H5OH(l) H+

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Figure 22.14 - Test for Alkene

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Elimination Reactions
• Reverse of an addition reaction
• Involve the elimination of two groups from adjacent
carbon atoms
• Convert a saturated molecule into one that is
unsaturated
• Dehydration of ethanol

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Condensation Reactions
• Occur when two molecules combine by splitting out
a small molecule such as water
• Example
• Methanol and acetic acid form methyl acetate

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Substitution Reactions
• Involve an atom or group of atoms that are replaced
by a different atom or group
• Chlorination of alkanes
CH 4 (g ) + Cl2 (g ) 
 CH3Cl(g ) + HCl(g )

• Reaction with benzene

C6 H 6 (l ) + Cl2 (g ) 
FeCl3
 C6 H5Cl(l ) + HCl(g )

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Example 22.12
• Classify each of the following as an addition,
elimination, condensation, or substitution reaction

(a) C2 H5OH(aq) + H + (aq) + Br  (aq) 


 C2 H5 Br(l ) + H 2O
(b) C6 H12 (l ) + Cl2 (g ) 
 C6 H12Cl2 (l )
(c) C7 H8 (l ) + 2Cl2 (g ) 
 C7 H6Cl2 (l ) + 2HCl(g )
(d) C5 H11Cl(l ) 
 C5H10 (l ) + HCl(g )

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Example 22.12

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Key Concepts
• Draw
• Structural isomers
• Geometric isomers
• Optical isomers (including chiral carbon atoms)
• Name
• Alkanes
• Unsaturated hydrocarbons
• Aromatic compounds
• Distinguish between alkanes, cycloalkanes, alkenes,
and alkynes

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Key Concepts
• Distinguish between alcohols, ethers, aldehydes,
ketones, carboxylic acids, esters, and amines
• Draw structural formulas for compounds containing
the functional groups listed in Table 22.2
• Determine equilibrium constants for the reaction of
amines with strong or weak acids
• Classify an organic reaction as an addition,
elimination, condensation, or substitution

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