Introduction to Spectroscopy

by Pavia, Donald L.; Lampman, Gary M.; Kriz, George S.

• ISBN13: 9780030319617
• ISBN10: 0030319617
• Edition: 3rd
• Format: Paperback
• Copyright: 2000-07-13
• Publisher: Brooks Cole

Summary

A true introductory text for learning the spectroscopic techniques of Nuclear Magnetic Resonance, Infrared, Ultraviolet and Mass Spectrometry. It can be used in a stand alone spectroscopy course or as a supplement to the sophomore-level organic chemistry course.

Table of Contents

Molecular Formulas and What Can be Learned from Them	1	(12)
Elemental Analysis and Calculations	1	(2)
Determination of Molecular Mass	3	(1)
Molecular Formulas	4	(1)
Index of Hydrogen Deficiency	4	(3)
The Rule of Thirteen	7	(3)
A Quick Look Ahead to Simple Uses of Mass Spectra	10	(3)
Problems	11	(1)
References	12	(1)
Infrared Spectroscopy	13	(89)
The Infrared Absorption Process	14	(1)
Uses of the Infrared Spectrum	15	(1)
The Modes of Stretching and Bending	16	(2)
Bond Properties and Absorption Trends	18	(2)
The Infrared Spectrometer	20	(3)
Dispersive Infrared Spectrometers	20	(3)
Fourier Transform Spectrometers	23	(1)
Preparation of Samples for Infrared Spectroscopy	23	(1)
What To Look for When Examining Infrared Spectra	24	(3)
Correlation Charts and Tables	27	(1)
How to Approach the Analysis of a Spectrum (Or What You Can Tell at a Glance)	28	(1)
Hydrocarbons: Alkanes, Alkenes, and Alkynes	29	(12)
Alkanes	29	(2)
Alkenes	31	(2)
Alkynes	33	(8)
Aromatic Rings	41	(4)
Alcohols and Phenols	45	(3)
Ethers	48	(2)
Carbonyl Compounds	50	(22)
Factors That Influence the C = O Stretching Vibration	52	(2)
Aldehydes	54	(2)
Ketones	56	(4)
Carboxylic Acids	60	(2)
Esters	62	(6)
Amides	68	(2)
Acid Chlorides	70	(1)
Anhydrides	71	(1)
Amines	72	(3)
Nitriles, Isocyanates, Isothiocyanates, and Imines	75	(2)
Nitro Compounds	77	(1)
Carboxylate Salts, Amine Salts, and Amino Acids	78	(1)
Sulfur Compounds	79	(3)
Phosphorus Compounds	82	(1)
Alkyl and Aryl Halides	82	(20)
Problems	84	(17)
References	101	(1)
Nuclear Magnetic Resonance Spectroscopy
PART ONE: BASIC CONCEPTS	102	(65)
Nuclear Spin States	102	(1)
Nuclear Magnetic Moments	103	(1)
Absorption of Energy	104	(2)
The Mechanism of Absorption (Resonance)	106	(2)
Population Densities of Nuclear Spin States	108	(1)
The Chemical Shift and Shielding	109	(2)
The Nuclear Magnetic Resonance Spectrometer	111	(6)
The Continuous-Wave (CW) Instrument	111	(2)
The Pulsed Fourier Transform (FT) Instrument	113	(4)
Chemical Equivalence---A Brief Overview	117	(1)
Integrals and Integration	118	(2)
Chemical Environment and Chemical Shift	120	(1)
Local Diamagnetic Shielding	121	(4)
Electronegativity Effects	121	(2)
Hybridization Effects	123	(1)
Acidic and Exchangeable Protons: Hydrogen Bonding	124	(1)
Magnetic Anisotropy	125	(3)
Spin-Spin Splitting (n + 1) Rule	128	(3)
The Origin of Spin-Spin Splitting	131	(2)
The Ethyl Group (CH3CH2--)	133	(1)
Pascal's Triangle	134	(1)
The Coupling Constant	134	(3)
A Comparison of NMR Spectra at Low and High Field Strengths	137	(1)
Survey of Typical 1H NMR Absorptions by Type of Compound	138	(29)
Alkanes	139	(1)
Alkenes	140	(1)
Aromatic Compounds	140	(2)
Alkynes	142	(1)
Alkyl Halides	143	(1)
Alcohols	144	(1)
Ethers	145	(1)
Amines	146	(1)
Nitriles	147	(1)
Aldehydes	148	(1)
Ketones	149	(1)
Esters	150	(1)
Carboxylic Acids	150	(2)
Amides	152	(1)
Nitroalkanes	153	(1)
Problems	154	(12)
References	166	(1)
Nuclear Magnetic Resonance Spectroscopy
PART TWO: CARBON-13 SPECTRA, INCLUDING HETERONUCLEAR COUPLING WITH OTHER NUCLEI	167	(50)
The Carbon-13 Nucleus	167	(1)
Carbon-13 Chemical Shifts	168	(3)
Correlation Charts	168	(2)
Calculation of 13C Chemical Shifts	170	(1)
Proton-Coupled 13C Spectra---Spin-Spin Splitting of Carbon-13 Signals	171	(2)
Proton-Decoupled 13C Spectra	173	(1)
Nuclear Overhauser Enhancement (NOE)	174	(2)
Cross-Polarization: Origin of the Nuclear Overhauser Effect	176	(3)
Problems with Integration in 13C Spectra	179	(1)
Molecular Relaxation Processes	180	(2)
Off-Resonance Decoupling	182	(1)
A Quick Dip into DEPT	182	(3)
Some Sample Spectra---Equivalent Carbons	185	(2)
Compounds with Aromatic Rings	187	(2)
Carbon-13 NMR Solvents---Heteronuclear Coupling of Carbon to Deuterium	189	(4)
Heteronuclear Coupling of Carbon to Fluorine-19	193	(1)
Heteronuclear Coupling of Carbon to Phosphorus-31	194	(23)
Problems	195	(21)
References	216	(1)
Nuclear Magnetic Resonance Spectroscopy
PART THREE: SPIN-SPIN COUPLING	217	(89)
Coupling Constants: Symbols	217	(1)
Coupling Constants: The Mechanism of Coupling	218	(10)
One-Bond Couplings (1J)	219	(1)
Two-Bond Couplings (2J)	220	(3)
Three-Bond Couplings (3J)	223	(4)
Long-Range Couplings (4J--nJ)	227	(1)
Magnetic Equivalence	228	(3)
Nonequivalence Within a Group---The Use of Tree Diagrams when the n + 1 Rule Fails	231	(3)
Measuring Coupling Constants from First Order Spectra	234	(3)
Simple Multiplets---One Value of J (One Coupling)	234	(1)
More Complex Multiplets---More Than One Value of J	235	(2)
Alkenes	237	(1)
Mechanisms of Coupling in Alkenes; Allylic Coupling	238	(3)
Measuring Coupling Constants---Analysis of an Allylic System	241	(5)
Is the n + 1 Rule Ever Really Obeyed?	246	(1)
Second-Order Spectra---Strong Coupling	247	(8)
First-Order and Second-Order Spectra	247	(1)
Spin System Notation	248	(1)
The A2, AB, and AX Spin Systems	248	(3)
The AB2 ... AX2 and A2B2 ... A2X2 Spin Systems	251	(3)
Simulation of Spectra	254	(1)
The Absence of Second-Order Effects at Higher Field	254	(1)
Deceptively Simple Spectra	255	(1)
Some Other Patterns	255	(1)
Aromatic Compounds---Substituted Benzene Rings	255	(9)
Monosubstituted Rings	256	(3)
para-Disubstituted Rings	259	(2)
Other Substitution	261	(3)
Coupling in Heteroaromatic Systems	264	(1)
Long-Range Coupling	265	(3)
Homotopic, Enantiotopic, and Diastereotopic Systems	268	(2)
Spectra of Diastereotopic Systems	270	(36)
Diastereotopic Methyl Groups: (S)-(+)-3-Methyl-2-butanol	270	(3)
Diastereotopic Hydrogens: 1,2-Dichloropropane	273	(1)
Diastereotopic Fluorines: 1-Bromo-2-chloro-1,1,2-trifluoroethane	273	(2)
Problems	275	(29)
References	304	(2)
Nuclear Magnetic Resonance Spectroscopy
PART FOUR: OTHER TOPICS IN ONE-DIMENSIONAL NMR	306	(220)
Protons on Oxygen: Alcohols	306	(3)
Exchange in Water and D2O	309	(3)
Acid/Water and Alcohol/Water Mixtures	309	(1)
Deuterium Exchange	310	(1)
Peak Broadening Due to Exchange	311	(1)
Other Types of Exchange: Tautomerism	312	(2)
Protons on Nitrogen: Amines	314	(4)
Protons on Nitrogen: Quadrupole Broadening and Decoupling	318	(1)
Amides	319	(3)
The Effect of Solvent on Chemical Shift	322	(1)
Chemical Shift Reagents; High-Field Spectra	323	(3)
Chiral Resolving Agents	326	(1)
Spin Decoupling Methods; Double Resonance	326	(3)
NOE Difference Spectra	329	(24)
Problems	332	(20)
References	352	(1)
Ultraviolet Spectroscopy	353	(37)
The Nature of Electronic Excitations	353	(2)
The Origin of UV Band Structure	355	(1)
Principles of Absorption Spectroscopy	355	(1)
Instrumentation	356	(1)
Presentation of Spectra	357	(1)
Solvents	358	(1)
What is a Chromophore?	359	(3)
The Effect of Conjugation	362	(1)
The Effect of Conjugation on Alkenes	363	(3)
The Woodward-Fieser Rules for Dienes	366	(3)
Carbonyl Compounds: Enones	369	(3)
Woodward's Rules for Enones	372	(2)
α ,β-Unsaturated Aldehydes, Acids, and Esters	374	(1)
Aromatic Compounds	374	(9)
Substituents with Unshared Electrons	376	(2)
Substituents Capable of π-Conjugation	378	(1)
Electron-Releasing and Electron-Withdrawing Effects	378	(1)
Disubstituted Benzene Derivatives	378	(3)
Polynuclear Aromatic Hydrocarbons and Heterocyclic Compounds	381	(2)
Model Compound Studies	383	(1)
Visible Spectra: Color in Compounds	384	(1)
What To Look for in an Ultraviolet Spectrum: A Practical Guide	385	(5)
Problems	387	(2)
References	389	(1)
Mass Spectrometry	390	(76)
The Mass Spectrometer	390	(3)
Gas Chromatography-Mass Spectrometry	393	(1)
The Mass Spectrum	394	(3)
Determination of Molecular Weight	397	(2)
Determination of Molecular Formulas	399	(5)
Precise Mass Determination	399	(1)
Isotope Ratio Data	400	(4)
Some Fragmentation Patterns	404	(41)
Alkanes	405	(3)
Cycloalkanes	408	(2)
Alkenes	410	(2)
Alkynes	412	(1)
Aromatic Hydrocarbons	413	(4)
Alcohols and Phenols	417	(5)
Ethers	422	(1)
Aldehydes	423	(2)
Ketones	425	(3)
Esters	428	(3)
Carboxylic Acids	431	(2)
Amines	433	(4)
Selected Nitrogen and Sulfur Compounds	437	(4)
Alkyl Chlorides and Alkyl Bromides	441	(4)
Additional Topics	445	(1)
Computerized Matching of Spectra with Spectral Libraries	446	(20)
Problems	448	(17)
References	465	(1)
Combined Structure Problems	466	(60)
Example 1	468	(2)
Example 2	470	(2)
Example 3	472	(4)
Example 4	476	(2)
Problems	478	(47)
Sources of Additional Problems	525	(1)
Nuclear Magnetic Resonance Spectroscopy
PART FIVE: ADVANCED NMR TECHNIQUES	526
Pulse Sequences	526	(2)
Pulse Widths, Spins, and Magnetization Vectors	528	(4)
The DEPT Experiment	532	(4)
Determining the Number of Attached Hydrogens	536	(4)
Methine Carbons (CH)	536	(1)
Methylene Carbons (CH2)	537	(2)
Methyl Carbons (CH3)	539	(1)
Quaternary Carbons (C)	539	(1)
The Final Result	540	(1)
Introduction to Two-Dimensional Spectroscopic Methods	540	(1)
The COSY Technique	540	(5)
An Overview of the COSY Experiment	541	(1)
How To Read COSY Spectra	542	(3)
The HETCOR Technique	545	(5)
An Overview of the HETCOR Experiment	546	(1)
How To Read HETCOR Spectra	546	(4)
Magnetic Resonance Imaging	550
Problems	552	(27)
References	579
ANSWERS TO SELECTED PROBLEMS	1	(1)
APPENDICES
Appendix 1 Infrared Absorption Frequencies of Functional Groups	2	(6)
Appendix 2 Approximate 1H Chemical Shift Ranges (ppm) for Selected Types of Protons	8	(1)
Appendix 3 Some Representative 1H Chemical Shift Values for Various Types of Protons	9	(3)
Appendix 4 1H Chemical Shifts of Selected Heterocyclic and Polycyclic Aromatic Compounds	12	(1)
Appendix 5 Typical Proton Coupling Constants	13	(4)
Appendix 6 Calculation of Proton (1H) Chemical Shifts	17	(4)
Appendix 7 Approximate 13C Chemical Shift Ranges (ppm) for Selected Types of Carbon	21	(1)
Appendix 8 Calculation of 13C Chemical Shifts	22	(9)
Appendix 9 13C Coupling Constants	31	(1)
Appendix 10 1H and 13C Chemical Shifts for Common NMR Solvents	32	(1)
Appendix 11 Tables of Precise Masses and Isotopic Abundance Ratios for Molecular Ions Under Mass 100 Containing Carbon, Hydrogen, Nitrogen, and Oxygen	33	(6)
Appendix 12 Common Fragment Ions Under Mass 105	39	(3)
Appendix 13 Handy-Dandy Guide to Mass Spectral Fragmentation Patterns	42	(3)
Appendix 14 Index of Spectra	45
Index	1