The Systematic Identification of Organic Compounds, Student Solutions Manual E-Book

Christine K. F. Hermann

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 204

Veröffentlichungsjahr: 2023

Beschreibung

The Student Solutions Manual to accompany The Systematic Identification of Organic Compounds, 9th Edition is an essential resource for any student using the parent text in class. Providing complete solutions to all practice problems provided in the textbook, this book allows you to assess your understanding of difficult material and clarify complex topics. Fully aligned with the text, this book details structures, formulas, mechanisms, and more to help you pinpoint areas of difficulty and focus your study time for more efficient learning.

Leseprobe

Table of Contents

Cover

Title Page

Copyright Page

Preface Page

Chapter 4: Preliminary Examination, Physical Properties, and Elemental Analysis

Chapter 5: Classification of Organic Compounds by Solubility

Chapter 6: Separation of Mixtures

Chapter 7: Nuclear Magnetic Resonance Spectrometry

Chapter 8: Infrared Spectrometry

Chapter 9: Mass Spectrometry

Chapter 10: Chemical Tests for Functional Groups

Chapter 11: The Preparation of Derivatives

Chapter 13: Structural Problems

PROBLEM SET 1

PROBLEM SET 2

PROBLEM SET 3

PROBLEM SET 4

PROBLEM SET 5

PROBLEM SET 6

PROBLEM SET 7

PROBLEM SET 8

PROBLEM SET 9

PROBLEM SET 10

PROBLEM SET 11

PROBLEM SET 12

PROBLEM SET 13

PROBLEM SET 14

PROBLEM SET 15

PROBLEM SET 16

PROBLEM SET 17

PROBLEM SET 18

PROBLEM SET 19

PROBLEM SET 20

End User License Agreement

Guide

Cover Page

Title Page

Copyright Page

Preface

Table of Contents

Begin Reading

Wiley End User License Agreement

Pages

iii

iv

vii

1

2

3

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

147

148

149

150

151

152

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

182

183

184

185

186

187

188

189

190

191

192

193

194

195

196

197

198

199

200

201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

227

228

229

230

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245

246

247

248

249

STUDENT SOLUTIONS MANUAL TO ACCOMPANY THE Systematic Identification OF ORGANIC COMPOUNDS

Ninth Edition

CHRISTINE K. F. HERMANN

TERENCE C. MORRILL

RALPH L. SHRINER

REYNOLD C. FUSON

Copyright © 2023 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per‐copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750‐8400, fax (978) 750‐4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748‐6011, fax (201) 748‐6008, or online at http://www.wiley.com/go/permission.

Trademarks: Wiley and the Wiley logo are trademarks or registered trademarks of John Wiley & Sons, Inc. and/or its affiliates in the United States and other countries and may not be used without written permission. All other trademarks are the property of their respective owners. John Wiley & Sons, Inc. is not associated with any product or vendor mentioned in this book.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762‐2974, outside the United States at (317) 572‐3993 or fax (317) 572‐4002.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com.

Library of Congress Cataloging‐in‐Publication Data applied for:

Paperback: 9781119799856

Cover design by Wiley

Preface

For the first six editions of this textbook, no solutions manual was available. As some of the problems presented throughout the textbook are quite difficult, I wrote the solutions manual as an aid to users of the textbook. The textbook contains no problems in Chapters 1, 2, 3, and 12.

I would like to thank Terence Morrill for the answers to Problem Sets 6–20 in Chapter 13, which is available on a companion website. These answers had been in handwritten form for many years. I would like to thank Danielle Davis for her assistance in writing the solutions manual for the seventh edition. I would like to thank Stephen Pond for his patience and support during the preparation of this edition.

Christine K. F. Hermann

Radford University

Chapter 5Classification of Organic Compounds by Solubility

N – alcohols, aldehydes, ketones, esters with one functional group and more than five but fewer than nine carbons, ethers, epoxides, alkenes, alkynes, some aromatic compounds (especially those with activating groups).

S

1

– monofunctional alcohols, aldehydes, ketones, esters, nitriles, and amides with five carbons or fewer.

A

2

– weak organic acids; phenols, enols, oximes, imides, sulfonamides, thiophenols, all with more than five carbons; β‐diketones; nitro compounds with α‐hydrogens.

Insoluble in water, soluble in 5% sodium hydroxide solution, soluble in 5% sodium bicarbonate solution.

Soluble in water and ether, litmus paper turned blue.

Insoluble in water, 5% sodium hydroxide solution, and 5% hydrochloric acid solution, but soluble in 96% sulfuric acid solution.

Soluble in water and ether; litmus paper is unchanged in color.

Soluble in water and ether; litmus paper is unchanged in color.

Insoluble in water and 5% sodium bicarbonate solution, but soluble in 5% sodium hydroxide solution.

A

1

S

B

N

S

1

S

1

A

2

Both acyl halides and anhydrides react with water, so any results would be of the carboxylic acid that is formed from the hydrolysis of these compounds.

1‐Propanol is more soluble in water than diethyl ether. 1‐Propanol can hydrogen bond with water, whereas diethyl ether does not hydrogen bond with water.

Pentanedioic acid is more soluble in water than butanedioic acid. Odd carbon number of dioic acids have less intracrystalline forces than even carbon number of dioic acids.

Methyl methacrylate is more soluble in water than poly(methyl methacrylate). Polymers are insoluble in water.

Butanoic acid is more soluble in water than 2‐Bromobutanoic acid. The addition of halogens increases the molecular weight and decreases the solubility.

2‐Methylpropanoic acid is more soluble in water than butanoic acid. Branching lowers the boiling point and lowers intermolecular forces. Thus, a branched compound is more soluble in water than a straight chain molecule.

1‐Chlorobutane is insoluble in water since it is an haloalkane. It is insoluble in 5% sodium hydroxide solution, 5% hydrochloric acid solution, and 96% sulfuric acid solution. Thus 1‐Chlorobutane is in solubility class I.

4‐Methylaniline is insoluble in water since it is an aniline. It is basic, due to the presence of the amino group, and therefore is insoluble in 5% sodium hydroxide solution, but soluble in 5% hydrochloric acid solution, and thus 4‐methylaniline is in solubility class B.

1‐Nitroethane is insoluble in water since it is a weak organic acid. It is soluble in 5% sodium hydroxide solution, but insoluble in 5% sodium bicarbonate solution, and thus 1‐nitroethane is in solubility class A

2

.

Alanine is an amino acid, thus is amphoteric, and soluble in water. Alanine is insoluble in ether and thus in solubility class S

2

.

Benzophenone is insoluble in water because it has more than five carbon atoms. Since it is a neutral compound, containing only carbon, hydrogen, and oxygen, it is insoluble in water, 5% sodium hydroxide solution, and 5% hydrochloric acid solution. It is soluble in 96% sulfuric acid solution. Therefore, benzophenone is in solubility class N.

As a strong organic acid, benzoic acid is insoluble in water, soluble in 5% sodium hydroxide solution, and soluble in 5% sodium bicarbonate solution. Therefore, benzoic acid is in solubility class A

1

.

As a saturated hydrocarbon, hexane is insoluble in water, 5% sodium hydroxide solution, 5% hydrochloric acid solution, and 95% sulfuric acid. Hexane is in solubility class I.

4‐Methylbenzyl alcohol is insoluble in water since it has more than five carbon atoms. It is a neutral compound with only carbon, hydrogen, and oxygen. It is insoluble in water, 5% sodium hydroxide solution and 5% hydrochloric acid solution. However, 4‐methylbenzyl alcohol is soluble in 96% sulfuric acid and thus in solubility class N.

As an amine with less than six carbons, ethylmethylamine is soluble in water. It is soluble in ether and its aqueous solutions turn litmus paper blue, therefore it is basic. Ethylmethylamine is in solubility class S

B

.

Propoxybenzene is insoluble in water because it has more than five carbon atoms. It is a neutral compound with only carbon, hydrogen, and oxygen and is insoluble in 5% sodium hydroxide solution, and 5% hydrochloric acid solution. However, propoxybenzene is soluble in 96% sulfuric acid solution and in solubility class N.

Propanal is soluble in water because it has less than five carbons. As a neutral compound, it is soluble in ether and its aqueous solutions do not change the color of litmus paper. Propanal is in solubility class S

1

.

As an aryl halide, 1,3‐Dibromobenzene is insoluble in water, 5% sodium hydroxide solution, 5% hydrochloric acid solution, and 96% sulfuric acid. 1,3‐Dibromobenzene is in solubility class I.

Propanoic acid is soluble in water because it contains less than five carbon atoms. It is soluble in ether, but its aqueous solutions turn litmus paper red. Propanoic acid is in solubility class S

A

.

As a weak organic acid, benzenesulfonamide is insoluble in water. It is soluble in 5% sodium hydroxide solution but insoluble in 5% sodium bicarbonate solution. Benzenesulfonamide is in solubility class A

2

.

1‐Butanol is soluble in water because it contains less than five carbon atoms. It is soluble in ether and its aqueous solutions do not change the color of litmus. 1‐Butanol is in solubility class S

1

.

Methyl propanoate is soluble in water since it contains less than five carbon atoms. It is soluble in ether and its aqueous solutions do not change the color of litmus. Methyl propanoate is in solubility class S

1

.

4‐Methylcyclohexanone is insoluble in water since it contains more than five carbon atoms. It is also insoluble in 5% sodium hydroxide solution and 5% hydrochloric acid solution, but soluble in 96% sulfuric acid. Therefore, 4‐methylcyclohexanone is in solubility class N.

Since 4‐Aminobiphenyl is an aniline, it is insoluble in water. It is insoluble in 5% sodium hydroxide solution, but soluble in 5% hydrochloric acid solution. 4‐Aminobiphenyl is in solubility class B.

Since 4‐Methylacetophenone contains more than five carbon atoms, it is insoluble in water. It is also insoluble in 5% sodium hydroxide solution and 5% hydrochloric acid solution, but soluble in 96% sulfuric acid. Therefore, 4‐methylacetophenone is in solubility class N.

Naphthalene is insoluble in water since it contains more than five carbon atoms. It is insoluble in 5% sodium hydroxide solution and 5% hydrochloric acid solution. However, naphthalene is soluble in 96% sulfuric acid, and therefore in solubility class N.

Phenylalanine is an amino acid, thus is amphoteric, and soluble in water. Phenylalanine is insoluble in ether and thus in solubility class S

2

.

Benzoin is insoluble in water since it has more than five carbon atoms. It is insoluble in water, 5% sodium hydroxide solution, and 5% hydrochloric acid solution. However, benzoin is soluble in 96% sulfuric acid, and therefore in solubility class N.

As a strong organic acid, 4‐hydroxybenzenesulfonic acid is insoluble in water. However, it is soluble in 5% sodium hydroxide solution and 5% sodium bicarbonate solution. 4‐Hydroxybenzenesulfonic acid is in solubility class A

1

.

Listed in order from least basic to most basic (see next question).

Benzanilide

Solubility class

N

Pentylamine

Solubility class

S

B

Diphenylamine

Solubility class

N

Benzylamine

Solubility class

S

B

4‐Methylaniline

Solubility class

B

Butanamide

Solubility class

S

1

Listed in order from least soluble to most soluble in water.

Smaller alcohols are more soluble.

More hydroxyl groups increase solubility.

Branching increases solubility.

N < S

1

–N < S

B

< S

2

Methanol

Solubility class

S

1

Isopropyl alcohol

Solubility class

S

1

Ethanol

Solubility class

S

1

1‐Butanol

Solubility class

S

1

Butane

Solubility class

I

1,4‐Butanediol

Solubility class

S

2

1‐Butanol

Solubility class

S

1

1‐Butanol

Solubility class

S

1

2‐Methyl‐2‐propanol

Solubility class

S

1

2‐Butanol

Solubility class

S

1

Ammonium butanoate

Solubility class

S

2

3‐Pentanone

Solubility class

S

1

–N

Benzaldehyde

Solubility class

N

Trimethylamine

Solubility class

S

B

The following compounds are listed in order of decreasing activity.

Chapter 6Separation of Mixtures

Pentane – volatile

D

‐glucose – low volatility, with certain exceptions these compounds cannot be distilled at atmospheric pressure

Diethylamine – readily distill, many compounds boil below 100 °C

2‐Butanone – readily distill, many compounds boil below 100 °C

Pentane – volatile with steam

D

‐Glucose – not volatile with steam

Diethylamine – volatile with steam

2‐Butanone – volatile with steam

Since glucose is also insoluble in ether, it would be filtered out as Residue 1.

To solve this problem, the number of moles of each substance must be determined.

Compound

grams

MW

moles

2‐Methyl‐2‐propanol

2.47

74.63

0.033

Benzyl alcohol

3.60

108.81

0.033

Benzaldehyde

3.53

106.79

0.033

Acetyl chloride

5.20

78.69

0.066

Acetophenone

4.00

120.92

0.033

N,N

‐Dimethylaniline

28.2

121.95

0.231

The acetyl chloride will react with the 2‐methyl‐2‐propanol and the benzyl alcohol to form the 1,1‐dimethylethyl acetate and the benzyl acetate, respectively.

The hydrogen chloride, produced from the above reactions, reacts with N,N‐dimethylaniline to form N,N‐dimethylanilinium chloride.

If complete reactions are assumed, then the following compounds would be present at the end of a week.

Compound

moles

1,1‐Dimethylethyl acetate

0.033

Benzyl acetate

0.033

Benzaldehyde

0.033

Acetophenone

0.033

N,N

‐Dimethylanilinium chloride

0.066

N,N

‐Dimethylaniline

0.165

Pentane – very nonpolar

Butanoic acid – polar

2‐Butanone – nonpolar

D

‐Fructose – very polar

Pentane < 2‐Butanone < butanonic acid <

D

‐fructose

Since these compounds are alcohols, gas chromatography could be utilized. These compounds would be separated by bp.

Extraction methods would be the preferred method of separating these compounds.

Gas chromatography could be utilized to separate these compounds. These compounds would be separated by bp.

The compounds must be soluble in a solvent and/or be able to be volatized in order to be separated by GC or LC. Esters are more volatile and are more easily dissolved than carboxylic acids.