The Organic Chem Lab Survival Manual PDF
Preview The Organic Chem Lab Survival Manual
NINTH EDITION THE ORGANIC CHEM LAB SURVIVAL MANUAL A Student’s Guide to Techniques JAMES W. ZUBRICK Hudson Valley Community College VP & Executive Publisher Kaye Pace Associate Publisher Petra Recter Sponsoring Editor Joan Kalkut Editorial Assistant Ashley Gayle Marketing Manager Kristine Ruff Marketing Assistant Andrew Ginsberg Designer Seng Ping Ngieng Associate Production Manager Joyce Poh Production Editor Jolene Ling This book was set in 10/12 Times by Aptara®, Inc. and printed and bound by Courier Westford. The cover was printed by Courier Westford. This book is printed on acid free paper. Founded in 1807, John Wiley & Sons, Inc. has been a valued source of knowledge and understanding for more than 200 years, helping people around the world meet their needs and fulfi ll their aspirations. Our company is built on a foundation of principles that include responsibility to the communities we serve and where we live and work. 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Upon completion of the review period, please return the evaluation copy to Wiley. Return instructions and a free of charge return mailing label are available at www.wiley.com/go/returnlabel. If you have chosen to adopt this textbook for use in your course, please accept this book as your complimentary desk copy. Outside of the United States, please contact your local sales representative. Library of Congress Cataloging-in-Publication Data Zubrick, James W. The organic chem lab survival manual a student’s guide to techniques/James W. Zubrick, Hudson Valley Community College.—Ninth ed. p. cm. Includes index. ISBN 978-1-118-08339-0 (pbk. : alk. paper) 1. Chemistry, Organic—Laboratory manuals. I. Title. QD261.Z83 2012 547.0078—dc23 2012020179 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 For Zoë and Anne, who make it all worth the effort. PREFACE TO THE NINTH EDITION This Survival Manual again presents the basic techniques of the organic chemistry laboratory, with the usual emphasis on doing the work correctly the fi rst time. And once again, I have relied on the comments of users and reviewers in guiding the changes and additions that have been made. Safety in the laboratory, always a primary concern, now has to consider the addition of such technology as the iPad, the Nook, the Kindle, and even text mes- saging, where applicable. Microscale, also where applicable, has been reviewed and updated as well. And while currently resisting the deletion of double-beam spectro- photometers altogether, a discussion of the technique of Attenuated Total Refl ectance and associated practices has been added to the section on Infrared Spectroscopy (Chapter 32). The discussion and presentation of the section on Nuclear Magnetic Reso- nance (Chapter 33) has been re-worked such that the different methods of sample preparation, and instrument operation for continuous-wave and FT-NMR have been made to contrast more sharply. A number of NMR spectra, with suggestions on pre- sentation of the data, and basic interpretation have also been added. Presentation of a more modern outline of the instrumentation of HPLC (Chapter 31) includes discussion of automatic injectors, yet there is a bit of a loss as this instrument, now highly computer-controlled, no longer has visible pumps, valves, and miles of tubing and fi ttings, just a series of fairly quiet, putty-colored boxes that produce excellent data with ease and a bit of boredom. This kind of transition has put this edition of the Survival Manual into a bit of an “equilibrium mode,” as now, at the urging of reviewers, some older techniques have been removed as newer information has been included. The actual making of TLC plates on microscope slides, which apparently needs not be done anymore, has been removed, and comments about handling and cutting pre-prepared plates have been updated and expanded (Chapter 27). I’d like to thank my reviewers, Sean O’Connor, Clemson University; Lucy Moses, Virginia Commonwealth University; Christine Rich, University of Louisville; Sean O’Connor, University of New Orleans; Jeffrey Hugdahl, Mercer University; Kathleen Peterson, University of Notre Dame; Chavonda Mills, Georgia College & State University; Beatrix Aukszi, Nova Southeastern University; Robert Stockland, Bucknell University; Jennifer Krumper, UNC-Chapel Hill; Rui Zhang, Western Kentucky University; Holly Sebahar, University of Utah; Adam List, Vanderbilt University for their comments and suggestions, most of which have been iii incorporated in this work. Finally, I’d like to thank Petra Recter, Associate Publisher, Chemistry and Physics, for the chance to perform this update, and Joan Kalkut, Sponsoring Editor, for her tremendous patience and support during a personally diffi cult time. J. W. Zubrick Hudson Valley Community College iv PREFACE TO THE NINTH EDITION CONTENTS CHAPTER 1 SAFETY FIRST, LAST, AND ALWAYS 1 Accidents Will Not Happen 5 Disposing of Waste 5 Mixed Waste 7 Material Safety Data Sheet (MSDS) 8 Green Chemistry and Planning an Organic Synthesis 9 An iBag for Your iThing 10 Exercises 10 CHAPTER 2 KEEPING A NOTEBOOK 11 A Technique Experiment 12 Notebook Notes 13 A Synthesis Experiment 13 Notebook Notes 13 Calculation of Percent Yield (Not Yeild!) 23 Estimation Is Your Friend 25 The Acid Test 25 Notebook Mortal Sin 25 Exercises 26 CHAPTER 3 INTERPRETING A HANDBOOK 27 CRC Handbook 28 Entry: 1-Bromobutane 28 Entry: Benzoic Acid 29 Lange’s 31 Entry: 1-Bromobutane 31 Entry: Benzoic Acid 31 Merck Index 31 Entry: 1-Bromobutane 33 Entry: Benzoic Acid 34 There’s a CD 34 The Aldrich Catalog 35 Entry: 1-Bromobutane 35 Entry: Benzoic Acid 36 Not Clear–Clear? 36 Info on the Internet 37 Exercises 37 v vi CONTENTS CHAPTER 4 JOINTWARE 38 Stoppers with Only One Number 39 Another Episode of Love of Laboratory 40 Hall of Blunders and Things Not Quite Right 42 Round-Bottom Flasks 42 Columns and Condensers 43 The Adapter with Lots of Names 43 Forgetting the Glass 45 Inserting Adapter Upside Down 45 Inserting Adapter Upside Down sans Glass 46 The O-Ring and Cap Branch Out 46 Greasing the Joints 46 To Grease or Not to Grease 47 Preparation of the Joints 47 Into the Grease Pit 47 Storing Stuff and Sticking Stoppers 48 Corking a Vessel 48 CHAPTER 5 MICROSCALE JOINTWARE 50 Microscale: A Few Words 51 Uh-Oh Rings 51 The O-Ring Cap Seal 51 Skinny Apparatus 51 Not-So-Skinny Apparatus 52 Sizing Up the Situation 52 Why I Don’t Really Know How Vacuum-Tight These Seals Are 54 The Comical Vial (That’s Conical!) 54 The Conical Vial as Vial 55 Packaging Oops 55 Tare to the Analytical Balance 55 The Electronic Analytical Balance 56 Heating These Vials 56 The Microscale Drying Tube 57 Gas Collection Apparatus 58 Generating the Gas 59 Isolating the Product 61 CHAPTER 6 OTHER INTERESTING EQUIPMENT 62 Funnels, and Beakers, and Flasks—Oh My! 63 The Flexible Double-Ended Stainless Steel Spatula 63 CONTENTS vii CHAPTER 7 PIPET TIPS 66 Pre-Preparing Pasteur Pipets 67 Calibration 68 Operation 68 Amelioration 68 Pipet Cutting 70 Pipet Filtering—Liquids 70 Pipet Filtering—Solids 71 CHAPTER 8 SYRINGES, NEEDLES, AND SEPTA 73 The Rubber Septum 75 CHAPTER 9 CLEAN AND DRY 77 Drying Your Glassware When You Don’t Need To 78 Drying Your Glassware When You Do Need To 79 CHAPTER 10 DRYING AGENTS 80 Typical Drying Agents 81 Using a Drying Agent 82 Following Directions and Losing Product Anyway 82 Drying Agents: Microscale 83 Drying in Stages: The Capacity and Effi ciency of Drying Agents 83 Exercises 83 CHAPTER 11 ON PRODUCTS 84 Solid Product Problems 85 Liquid Product Problems 85 The Sample Vial 85 Hold It! Don’t Touch That Vial 86 CHAPTER 12 THE MELTING-POINT EXPERIMENT 87 Sample Preparation 88 Loading the Melting-Point Tube 89 Closing Off Melting-Point Tubes 90 Melting-Point Hints 90 The Mel-Temp Apparatus 91 Operation of the Mel-Temp Apparatus 92 The Fisher-Johns Apparatus 93 Operation of the Fisher-Johns Apparatus 94 The Thomas-Hoover Apparatus 95 Operation of the Thomas-Hoover Apparatus 97 viii CONTENTS Using the Thiele Tube 99 Cleaning the Tube 100 Getting the Sample Ready 101 Dunking the Melting-Point Tube 102 Heating the Sample 103 Exercises 103 CHAPTER 13 RECRYSTALLIZATION 104 Finding a Good Solvent 105 General Guidelines for a Recrystallization 106 My Product Disappeared 107 Gravity Filtration 107 The Buchner Funnel and Filter Flask 110 Just a Note 113 The Hirsch Funnel and Friends 113 Activated Charcoal 114 The Water Aspirator: A Vacuum Source 114 The Water Trap 115 Working with a Mixed-Solvent System—The Good Part 115 The Ethanol–Water System 116 A Mixed-Solvent System—The Bad Part 116 Salting Out 117 World-Famous Fan-Folded Fluted Paper 118 Exercises 119 CHAPTER 14 RECRYSTALLIZATION: MICROSCALE 120 Isolating the Crystals 121 Craig Tube Filtration 122 Centrifuging the Craig Tube 124 Getting the Crystals Out 125 CHAPTER 15 EXTRACTION AND WASHING 127 Never-Ever Land 128 Starting an Extraction 129 Dutch Uncle Advice 130 The Separatory Funnel 131 The Stopper 131 The Glass Stopcock 131 The Tefl on Stopcock 132 How to Extract and Wash What 134 The Road to Recovery—Back-Extraction 135 A Sample Extraction 136 Performing an Extraction or Washing 137 Extraction Hints 139 Exercises 140 CONTENTS ix CHAPTER 16 EXTRACTION AND WASHING: MICROSCALE 141 Mixing 142 Separation: Removing the Bottom Layer 142 Separation: Removing the Top Layer 143 Separation: Removing Both Layers 144 CHAPTER 17 SOURCES OF HEAT 145 Boiling Stones 146 The Steam Bath 146 The Bunsen Burner 147 Burner Hints 149 The Heating Mantle 150 Proportional Heaters and Stepless Controllers 152 Exercise 153 CHAPTER 18 CLAMPS AND CLAMPING 154 Clamping a Distillation Setup 157 Clipping a Distillation Setup 161 CHAPTER 19 DISTILLATION 164 Distillation Notes 165 Class 1: Simple Distillation 166 Sources of Heat 166 The Three-Way Adapter 167 The Distilling Flask 167 The Thermometer Adapter 168 The Ubiquitous Clamp 168 The Thermometer 168 The Condenser 168 The Vacuum Adapter 168 The Receiving Flask 169 The Ice Bath 169 The Distillation Example 169 The Distillation Mistake 170 Class 2: Vacuum Distillation 170 Pressure Measurement 171 Manometer Hints 173 Leaks 173 Pressure and Temperature Corrections 173 Vacuum Distillation Notes 177 Class 3: Fractional Distillation 178 How This Works 178 Fractional Distillation Notes 180 x CONTENTS Azeotropes 183 Class 4: Steam Distillation 183 External Steam Distillation 184 Internal Steam Distillation 185 Steam Distillation Notes 185 Simulated Bulb-to-Bulb Distillation: Fakelrohr 187 Exercises 189 CHAPTER 20 MICROSCALE DISTILLATION 190 Like the Big Guy 191 Class 1: Simple Distillation 191 Class 2: Vacuum Distillation 191 Class 3: Fractional Distillation 191 Class 4: Steam Distillation 191 Microscale Distillation II: The Hickman Still 192 The Hickman Still Setup 192 Hickman Still Heating 193 Recovering Your Product 193 A Port in a Storm 194 CHAPTER 21 THE ROTARY EVAPORATOR 195 Exercises 199 CHAPTER 22 REFLUX AND ADDITION 200 Standard Refl ux 201 A Dry Refl ux 202 Addition and Refl ux 204 Funnel Fun 204 How to Set Up 205 Exercise 207 CHAPTER 23 REFLUX: MICROSCALE 208 Addition and Refl ux: Microscale 209 CHAPTER 24 SUBLIMATION 211 CHAPTER 25 MICROSCALE BOILING POINT 214 Microscale Boiling Point 215 Ultramicroscale Boiling Point 216 CONTENTS xi CHAPTER 26 CHROMATOGRAPHY: SOME GENERALITIES 218 Adsorbents 219 Separation or Development 219 The Eluatropic Series 219 CHAPTER 27 THIN-LAYER CHROMATOGRAPHY: TLC 222 We Don’t Make Our Own TLC Plates Any More, But… 223 Pre-prepared TLC Plates 223 The Plate Spotter 223 Spotting the Plates 224 Developing a Plate 225 Visualization 227 Interpretation 228 Multiple Spotting 230 Cospotting 230 Other TLC Problems 231 Preparative TLC 232 Exercises 233 CHAPTER 28 WET-COLUMN CHROMATOGRAPHY 234 Preparing the Column 235 Compounds on the Column 237 Visualization and Collection 238 Wet-Column Chromatography: Microscale 239 Flash Chromatography 241 Microscale Flash Chromatography 241 Exercises 241 CHAPTER 29 REFRACTOMETRY 242 The Abbé Refractometer 243 Before Using the Abbé Refractometer: A Little Practice 245 Using the Abbé Refractometer 245 Refractometry Hints 247 CHAPTER 30 GAS CHROMATOGRAPHY 248 The Mobile Phase: Gas 249 GC Sample Preparation 250 GC Sample Introduction 250 Sample in the Column 252 xii CONTENTS Sample at the Detector 252 Electronic Interlude 254 Sample on the Computer 255 Parameters, Parameters 256 Gas Flow Rate 256 Temperature 256 Exercises 257 CHAPTER 31 HP LIQUID CHROMATOGRAPHY 258 The Mobile Phase: Liquid 259 A Bubble Trap 259 The Pump and Pulse Dampener Module 261 HPLC Sample Preparation 262 HPLC Sample Introduction 263 Sample in the Column 264 Sample at the Detector 265 Sample on the Computer 266 Parameters, Parameters 266 Eluent Flow Rate 266 Temperature 266 Eluent Composition 267 Exercises 267 CHAPTER 32 INFRARED SPECTROSCOPY (AND A BIT OF UV-VIS, TOO) 268 Molecules as Balls on Springs 269 Ah, Quantum Mechanics 270 The Dissonant Oscillator 271 But Wait! There’s More 271 More Complicated Molecules 272 Correlation Tables to the Rescue 272 Troughs and Reciprocal Centimeters 272 Some Functional Group Analysis 278 A Systematic Interpretation 278 Infrared Sample Preparation 281 Liquid Samples 281 Solid Samples 282 Running the Spectrum 287 The Perkin-Elmer 710B IR 289 Using the Perkin-Elmer 710B 290 The 100% Control: An Important Aside 291 Calibration of the Spectrum 293 IR Spectra: The Finishing Touches 294 Interpreting IR Spectra—Finishing Touches 295 CONTENTS xiii The Fourier Transform Infrared (FTIR) 296 The Optical System 296 A Refl ectance Attachment: Something to Think About 300 And UV-VIS Too! 300 Electrons Get to Jump 300 Instrument Confi guration 301 Source 301 Sample (and Reference) Cells 302 Solvents 303 Exercises 303 CHAPTER 33 NUCLEAR MAGNETIC RESONANCE 304 Nuclei Have Spin, Too 305 The Magnetic Catch 305 Everybody Line Up, Flip, and Relax 306 A More Sensitive Census 306 The Chemical Shift 307 T for One and Two 307 Be It Better Resolved . . . 308 Incredibly Basic FT-NMR 308 NMR Sample Preparation 309 Some NMR Terms and Interpretations 312 The Chemical Shift and TMS Zero 312 Integration and Labeling 314 Threaded Interpretations: Spectrum #1 (t-butyl alcohol) 315 Threaded Interpretations: Spectrum #2 (Toluene) and Spectrum #3 (p-Dichlorobenzene) 315 Threaded Interpretations: Spectrum #4 (Ethylbenzene) and Spectrum #5 (A Double Resonance Experiment) 319 Use a Correlation Chart 320 Exercises 323 CHAPTER 34 THEORY OF DISTILLATION 324 Class 1: Simple Distillation 325 Clausius and Clapeyron 327 Class 3: Fractional Distillation 328 A Hint from Dalton 328 Dalton and Raoult 329 A Little Algebra 329 Clausius and Clapeyron Meet Dalton and Raoult 330 Dalton Again 331 What Does It All Mean? 332 Reality Intrudes I: Changing Composition 335
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