Private: Chapter Twenty One
Key Terms, Key Equations, and Exercises (Chapter 21)
Key Terms
addition reaction reaction in which a double carbon-carbon bond forms a single carbon-carbon bond by the addition of a reactant. Typical reaction for an alkene.
alcohol organic compound with a hydroxyl group (–OH) bonded to a carbon atom
aldehyde organic compound containing a carbonyl group bonded to two hydrogen atoms or a hydrogen atom and a carbon substituent
alkane molecule consisting of only carbon and hydrogen atoms connected by single (σ) bonds
alkene molecule consisting of carbon and hydrogen containing at least one carbon-carbon double bond
alkyl group substituent, consisting of an alkane missing one hydrogen atom, attached to a larger structure
alkyne molecule consisting of carbon and hydrogen containing at least one carbon-carbon triple bond
amide organic molecule that features a nitrogen atom connected to the carbon atom in a carbonyl group
amine organic molecule in which a nitrogen atom is bonded to one or more alkyl group
aromatic hydrocarbon cyclic molecule consisting of carbon and hydrogen with delocalized alternating carbon- carbon single and double bonds, resulting in enhanced stability
carbonyl group carbon atom double bonded to an oxygen atom
carboxylic acid organic compound containing a carbonyl group with an attached hydroxyl group
ester organic compound containing a carbonyl group with an attached oxygen atom that is bonded to a carbon substituent
ether organic compound with an oxygen atom that is bonded to two carbon atoms
functional group part of an organic molecule that imparts a specific chemical reactivity to the molecule
ketone organic compound containing a carbonyl group with two carbon substituents attached to it
organic compound natural or synthetic compound that contains carbon
saturated hydrocarbon molecule containing carbon and hydrogen that has only single bonds between carbon atoms
skeletal structure shorthand method of drawing organic molecules in which carbon atoms are represented by the ends of lines and bends in between lines, and hydrogen atoms attached to the carbon atoms are not shown (but are understood to be present by the context of the structure)
substituent branch or functional group that replaces hydrogen atoms in a larger hydrocarbon chain
substitution reaction reaction in which one atom replaces another in a molecule
Summary
Hydrocarbons
Strong, stable bonds between carbon atoms produce complex molecules containing chains, branches, and rings. The chemistry of these compounds is called organic chemistry. Hydrocarbons are organic compounds composed of only
carbon and hydrogen. The alkanes are saturated hydrocarbons—that is, hydrocarbons that contain only single bonds. Alkenes contain one or more carbon-carbon double bonds. Alkynes contain one or more carbon-carbon triple bonds. Aromatic hydrocarbons contain ring structures with delocalized π electron systems.
Alcohols and Ethers
Many organic compounds that are not hydrocarbons can be thought of as derivatives of hydrocarbons. A hydrocarbon derivative can be formed by replacing one or more hydrogen atoms of a hydrocarbon by a functional group, which contains at least one atom of an element other than carbon or hydrogen. The properties of hydrocarbon derivatives are determined largely by the functional group. The –OH group is the functional group of an alcohol. The –R–O–R– group is the functional group of an ether.
Aldehydes, Ketones, Carboxylic Acids, and Esters
Functional groups related to the carbonyl group include the –CHO group of an aldehyde, the –CO– group of a ketone, the –CO2H group of a carboxylic acid, and the –CO2R group of an ester. The carbonyl group, a carbon-oxygen double bond, is the key structure in these classes of organic molecules: Aldehydes contain at least one hydrogen atom attached to the carbonyl carbon atom, ketones contain two carbon groups attached to the carbonyl carbon atom, carboxylic acids contain a hydroxyl group attached to the carbonyl carbon atom, and esters contain an oxygen atom attached to another carbon group connected to the carbonyl carbon atom. All of these compounds contain oxidized carbon atoms relative to the carbon atom of an alcohol group.
Amines and Amides
The addition of nitrogen into an organic framework leads to two families of molecules. Compounds containing a nitrogen atom bonded in a hydrocarbon framework are classified as amines. Compounds that have a nitrogen atom bonded to one side of a carbonyl group are classified as amides. Amines are a basic functional group. Amines and carboxylic acids can combine in a condensation reaction to form amides.
Exercises
21.1 Hydrocarbons
Write the chemical formula and Lewis structure of the following, each of which contains five carbon atoms:
(a) an alkane
(b) an alkene
(c) an alkyne
What is the difference between the hybridization of carbon atoms’ valence orbitals in saturated and unsaturated hydrocarbons?
On a microscopic level, how does the reaction of bromine with a saturated hydrocarbon differ from its reaction with an unsaturated hydrocarbon? How are they similar?
On a microscopic level, how does the reaction of bromine with an alkene differ from its reaction with an alkyne? How are they similar?
Explain why unbranched alkenes can form geometric isomers while unbranched alkanes cannot. Does this explanation involve the macroscopic domain or the microscopic domain?
Explain why these two molecules are not isomers:
Explain why these two molecules are not isomers:
How does the carbon-atom hybridization change when polyethylene is prepared from ethylene?
Write the Lewis structure and molecular formula for each of the following hydrocarbons:
(a) hexane
(b) 3-methylpentane
(c) cis-3-hexene
(d) 4-methyl-1-pentene
(e) 3-hexyne
(f) 4-methyl-2-pentyne
Write the chemical formula, condensed formula, and Lewis structure for each of the following hydrocarbons:
(a) heptane
(b) 3-methylhexane
(c) trans-3-heptene
(d) 4-methyl-1-hexene
(e) 2-heptyne
(f) 3,4-dimethyl-1-pentyne
Give the complete IUPAC name for each of the following compounds:
(a) CH3CH2CBr2CH3
(b) (CH3)3CCl
(c)
(d) CH3CH2C≡CH CH3CH2C≡CH
(e)
(f)
(g) (CH3)2CHCH2CH=CH2
Give the complete IUPAC name for each of the following compounds:
(a) (CH3)2CHF
(b) CH3CHClCHClCH3
(c)
(d) CH3CH2CH=CHCH3
(e)
(f) (CH3)3CCH2C≡CH
Butane is used as a fuel in disposable lighters. Write the Lewis structure for each isomer of butane.
Write Lewis structures and name the five structural isomers of hexane.
Write Lewis structures for the cis–trans isomers of CH3CH=CHCl.
Write structures for the three isomers of the aromatic hydrocarbon xylene, C6H4(CH3)2.
Isooctane is the common name of the isomer of C8H18 used as the standard of 100 for the gasoline octane rating:
(a) What is the IUPAC name for the compound?
(b) Name the other isomers that contain a five-carbon chain with three methyl substituents.
Write Lewis structures and IUPAC names for the alkyne isomers of C4H6.
Write Lewis structures and IUPAC names for all isomers of C4H9Cl.
Name and write the structures of all isomers of the propyl and butyl alkyl groups.
Write the structures for all the isomers of the –C5H11 alkyl group.
Write Lewis structures and describe the molecular geometry at each carbon atom in the following compounds:
(a) cis-3-hexene
(b) cis-1-chloro-2-bromoethene
(c) 2-pentyne
(d) trans–6-ethyl-7-methyl-2-octene
Benzene is one of the compounds used as an octane enhancer in unleaded gasoline. It is manufactured by the catalytic conversion of acetylene to benzene:
3C2H2⟶C6H6
Draw Lewis structures for these compounds, with resonance structures as appropriate, and determine the hybridization of the carbon atoms in each.
Teflon is prepared by the polymerization of tetrafluoroethylene. Write the equation that describes the polymerization using Lewis symbols.
Write two complete, balanced equations for each of the following reactions, one using condensed formulas and one using Lewis structures.
(a) 1 mol of 1-butyne reacts with 2 mol of iodine.
(b) Pentane is burned in air.
Write two complete, balanced equations for each of the following reactions, one using condensed formulas and one using Lewis structures.
(a) 2-butene reacts with chlorine.
(b) benzene burns in air.
What mass of 2-bromopropane could be prepared from 25.5 g of propene? Assume a 100% yield of product.
Acetylene is a very weak acid; however, it will react with moist silver(I) oxide and form water and a compound composed of silver and carbon. Addition of a solution of HCl to a 0.2352-g sample of the compound of silver and carbon produced acetylene and 0.2822 g of AgCl.
(a) What is the empirical formula of the compound of silver and carbon?
(b) The production of acetylene on addition of HCl to the compound of silver and carbon suggests that the carbon is present as the acetylide ion, C22−. Write the formula of the compound showing the acetylide ion.
Ethylene can be produced by the pyrolysis of ethane:
C2H6⟶C2H4+H2
How many kilograms of ethylene is produced by the pyrolysis of 1.000 × 103 kg of ethane, assuming a 100.0% yield?
21.2 Alcohols and Ethers
Why do the compounds hexane, hexanol, and hexene have such similar names?
Write condensed formulas and provide IUPAC names for the following compounds:
(a) ethyl alcohol (in beverages)
(b) methyl alcohol (used as a solvent, for example, in shellac)
(c) ethylene glycol (antifreeze)
(d) isopropyl alcohol (used in rubbing alcohol)
(e) glycerine
Give the complete IUPAC name for each of the following compounds:
(a)
(b)
(c)
Give the complete IUPAC name and the common name for each of the following compounds:
(a)
(b)
(c)
Write the condensed structures of both isomers with the formula C2H6O. Label the functional group of each isomer.
Write the condensed structures of all isomers with the formula C2H6O2. Label the functional group (or groups) of each isomer.
Draw the condensed formulas for each of the following compounds:
(a) dipropyl ether
(b) 2,2-dimethyl-3-hexanol
(c) 2-ethoxybutane
MTBE, Methyl tert-butyl ether, CH3OC(CH3)3, is used as an oxygen source in oxygenated gasolines. MTBE is manufactured by reacting 2-methylpropene with methanol.
(a) Using Lewis structures, write the chemical equation representing the reaction.
(b) What volume of methanol, density 0.7915 g/mL, is required to produce exactly 1000 kg of MTBE, assuming a 100% yield?
Write two complete balanced equations for each of the following reactions, one using condensed formulas and one using Lewis structures.
(a) propanol is converted to dipropyl ether
(b) propene is treated with water in dilute acid.
Write two complete balanced equations for each of the following reactions, one using condensed formulas and one using Lewis structures.
(a) 2-butene is treated with water in dilute acid
(b) ethanol is dehydrated to yield ethene
21.3 Aldehydes, Ketones, Carboxylic Acids, and Esters
Order the following molecules from least to most oxidized, based on the marked carbon atom:
Predict the products of oxidizing the molecules shown in this problem. In each case, identify the product that will result from the minimal increase in oxidation state for the highlighted carbon atom:
(a)
(b)
(c)
Predict the products of reducing the following molecules. In each case, identify the product that will result from the minimal decrease in oxidation state for the highlighted carbon atom:
(a)
(b)
(c)
Explain why it is not possible to prepare a ketone that contains only two carbon atoms.
How does hybridization of the substituted carbon atom change when an alcohol is converted into an aldehyde? An aldehyde to a carboxylic acid?
Fatty acids are carboxylic acids that have long hydrocarbon chains attached to a carboxylate group. How does a saturated fatty acid differ from an unsaturated fatty acid? How are they similar?
Write a condensed structural formula, such as CH3CH3, and describe the molecular geometry at each carbon atom.
(a) propene
(b) 1-butanol
(c) ethyl propyl ether
(d) cis-4-bromo-2-heptene
(e) 2,2,3-trimethylhexane
(f) formaldehyde
Write a condensed structural formula, such as CH3CH3, and describe the molecular geometry at each carbon atom.
(a) 2-propanol
(b) acetone
(c) dimethyl ether
(d) acetic acid
(e) 3-methyl-1-hexene
The foul odor of rancid butter is caused by butyric acid, CH3CH2CH2CO2H.
(a) Draw the Lewis structure and determine the oxidation number and hybridization for each carbon atom in the molecule.
(b) The esters formed from butyric acid are pleasant-smelling compounds found in fruits and used in perfumes. Draw the Lewis structure for the ester formed from the reaction of butyric acid with 2-propanol.
Write two complete, balanced equations for each of the following reactions, one using condensed formulas and one using Lewis structures:
(a) ethanol reacts with propionic acid
(b) benzoic acid, C6H5CO2H, is added to a solution of sodium hydroxide
Write two complete balanced equations for each of the following reactions, one using condensed formulas and one using Lewis structures.
(a) 1-butanol reacts with acetic acid
(b) propionic acid is poured onto solid calcium carbonate
Yields in organic reactions are sometimes low. What is the percent yield of a process that produces 13.0 g of ethyl acetate from 10.0 g of CH3CO2H?
Alcohols A, B, and C all have the composition C4H10O. Molecules of alcohol A contain a branched carbon chain and can be oxidized to an aldehyde; molecules of alcohol B contain a linear carbon chain and can be oxidized to a ketone; and molecules of alcohol C can be oxidized to neither an aldehyde nor a ketone. Write the Lewis structures of these molecules.
21.4 Amines and Amides
Write the Lewis structures of both isomers with the formula C2H7N.
What is the molecular structure about the nitrogen atom in trimethyl amine and in the trimethyl ammonium ion, (CH3)3NH+? What is the hybridization of the nitrogen atom in trimethyl amine and in the trimethyl ammonium ion?
Write the two resonance structures for the pyridinium ion, C5H5NH+.
Draw Lewis structures for pyridine and its conjugate acid, the pyridinium ion, C5H5NH+. What are the geometries and hybridizations about the nitrogen atoms in pyridine and in the pyridinium ion?
Write the Lewis structures of all isomers with the formula C3H7ON that contain an amide linkage.
Write two complete balanced equations for the following reaction, one using condensed formulas and one using Lewis structures.
Methyl amine is added to a solution of HCl.
Write two complete, balanced equations for each of the following reactions, one using condensed formulas and one using Lewis structures.
Ethylammonium chloride is added to a solution of sodium hydroxide.
Identify any carbon atoms that change hybridization and the change in hybridization during the reactions in Exercise 21.26.
Identify any carbon atoms that change hybridization and the change in hybridization during the reactions in Exercise 21.39.
Identify any carbon atoms that change hybridization and the change in hybridization during the reactions in Exercise 21.51.