Analytical Methods in Mass Spectrometry

Introduction	1
Experimental Procedure	3
Analytical Methods	4
Correlation Studies	4
Mass Spectra of Alcohols	4
Mass Spectra of Trimethylsilyl Derivatives	9
Mass Spectra of Acetyl-Type Compounds	12
Mass Spectra of Ketenes	17
Mm Spectra of Esters: Formation of Rearrangement Ions	19
Type-Analysis of Paraffin-Naphthene Mixtures	25
Analysis of oils derived from Coal	29
Methods of Analysis	29
Application of Methods	35
Special Analytical Techniques	40
Mass Spectrometric Determination of the Ratio of Branched to Normal Hydrocarbons up to C₁₅in Fischer-Tropsch product	40
Analysis of Hutches and Pentene's by Hydrochlorination	47
Mass Spectrometric Analysis of Mixtures Containing Nitrogen Dioxide	48
Mass Spectrum of Nitric Acid	56
Determination of H₂S and Vapor-Phase H₂0	57
Mass Spectrum of Hydrogen Denteride (HD)	57
Instrumentation and Studies of Anomalous Peaks	60
Conditioning of Mass Spectrometer Filaments: Tungsten Carbide Formation	60
Rhenium Filaments for Mass Spectrometry	65
Automatic Manometer for Constant-Pressure Gas Sampling	66
Self-Filling Micropipet for Liquid Introduction	67
Anomalous Negative Peaks in Mass Spectra	69
Conclusions	71
References	72

ILLUSTRATIONS

1	Parent-Minus-15 Peak Intensities of Trimethylsilyl Ethers, Derivatives of Normal Alcohols	13
2	Rate of Decomposition of Mass 61 Fragment from Hemiformal of Methanol	14
3	Variation with Time of Several Mass Peaks in a blend of Formaldehyde-Methanol-Water	15
4	Rate of Decomposition of Mass 61 Fragment from the Hemiacetal of Methanol	16
5	Partial Identification of an Ester from Rearrangement Peaks	24
6	Fischer-Tropsch of Product, Ester Distribution form Rearrangement Peaks	24
7	Preliminary Separation and Mass Spectrometric Analytical Scheme for High-Boiling Oils from Coal	30
8	Typical Ionization Efficiency Curve for Molecular Ions from Hydrocarbons	31
9	Partial Mass Spectrum of Naphthalene, Normal and Reduced Ionizing Voltages	32
10	Low-Ionizing-Voltage Sensitivity Data for Phenolic Types	33
11	Low-Ionizing-Voltage Sensitivity Data for Alkyl-Substituted Phenols	34
12	Variation of Sensitivity Factor with Number of Alkyl Substituents on the Phenol Ring	34
13	Carbon Number Distribution of Phenols and Indanols in a Tar-Acid Fraction	35
14	Sensitivities of Phenols and Their Trimethylsilyl either derivatives at Low-Ionizing Voltage	36
15	Catalytic Cracking of Phenols from Coal-Tar Distillate as Evidenced Low-Ionizing-Voltage Mass Spectra	37
16	Carbon Number Distribution of Phenols, Indans, and Benzenes in Blended Fractions of a Coal-Hydrogenation Oil	38
17	Separation and Analysis of >170° C Fraction of Fischer-Tropsch Synthesis Product	42
18	Sensitivity Data for Paraffin's in Fischer-Tropsch Product	43
19	Carbon Number Distribution for Paraffins in Hydrogenated Fischer-Tropsch Products	45

ANALYTICAL METHODS IN MASS SPECTROMETRY
20	Predicted Values for Carbon Number Distribution of Paraffins in Hydrogenated Fischer-Tropsch Product	46
21	Variation in Proportion of n-isomer with Carbon Number for Paraffins	46
22	Preliminary Test for Proper Conditioning with NO₃	50
23	Test for proper conditioning with NO₃ by Consecutive Runs	50
24	NO₃ Mass Spectral Patterns at Various Pressures	51
25	NO₃ Mass Spectral Sensitivities at Various Pressures	52
26	Working Curve, NO₃ Pressure versus Mass 46 Peak Heights	56
27	Schematic Diagram of Flow System in Mass Spectrometer Inlet System	58
28	Rate of Diffusion Curve for Determination of H₂ Impurity and Relative Abundance of D+ from HD	59
29	Change of Conductance with Carbon Content for Tungsten at Room Temperature	61
30	Schematic Diagram of a Longitudinal Section of a Well-Conditioned Filament Showing Locations of Crystalline Phases	62
31	Schematic Diagram of a Longitudinal Section of an over Conditioned Filament Showing Locations of Crystalline Phases	63
32	Conductane Change with Carbon Content for a Tungsten Filament at 2,475ºC	63
33	Current Changes Observed with the Introduction of Oxygen or Hydrocarbon	64
34	Manometer for Obtaining Uniform Gas Pressure during Sampling	66
35	Self-Filing 0.001-ml micropipet	66
36	Possible Source of Negative Perks	69
37	Portion of CO Spectrum	69

TABLES
1	Comparison of Spectrum of Primary Straight-Chain Alcohol with Corresponding Olefin	5
2	Ionization Distribution for Alcohols Among Various Types of Fragmentation Peaks	6
3	Comparison of Spectrum of Primary, S-Branched Alcohol with Corresponding Olefin	6
4	Total Ionization of Aliphatic Alcohols	7
5	Groups Identifiable in Unknown Alcohol by Mass Spectra	8
6	Mass Spectral Analysis of Alcohol Synthetic Blends	8
7	Mass Spectral Type-Analysis of C3 to C5 Alcohols	9
8	Matrix for Type-Analysis of C to C, Alcohols	9
9	Fragmentation Peaks in Mass Spectra-A of Normal Aliphatic Trimethylsilyl Ethers	10
10	Rearrangement Structures in Trimethylsilyl Ethers	11
11	Type Identification of Alcohols by Trimethylsilyl Ether Derivatives	11
12	Evidence of Hemiformal in Vapor Phase of Formaldehyde-Methanol-Water Blend	14
13	Evidence of Hemiformal in vapor phase of acetaldehyde-methanol blend	16
14	Acetals formed in alcohol-aldehyde blends	17
15	Correlation of Ketone Structure with Rearrangement Peaks	19
16	Identification of Ketones from Mass Spectral Characteristics	20
17	Origin of Base Peaks in Mass Spectra of Esters	20
18	Correlation of Rearrangement Peaks in Mass Spectra of Esters	21
19	Examples of Mass Spectral Rearrangement Ions	22
20	Formation of Rearrangement Ions	23
21	Mass Spectral Type-Analysis of Naphthenes, General Calibration Peaks	25
22	Outline of Type - Analysis of Naphthane - Paraffin Blends, C, Matrix	26
23	Outline of Type - Analysis of Naphthane - Paraffin Blends, 5 - Component C₅ Matrix	27
24	Outline of Type - Analysis of Naphthane - Paraffin Blends, 7 - Component C, Matrix	27
25	Mass Spectral Type - Analysis of C, and Cyclohexane Paraffin - Naphthene Synthetic Blends	28
26	Mass Spectral Type - Analysis of C₅ Paraffin - Naphthene Synthetic Blends	28
27	Type - Analysis of C, Paraffin - Naphthene Mixtures from Coal-Hydrogenation Product	29
28	Type - Analysis of C₇ Paraffin - Naphthene Mixture from Coal-Hydrogenation Product	29
29	Approximate Ionization Potentials	31
30	Low-Ionizing-Voltage Sensitivities of Methylindanols	35
31	Low-Ionizing-Voltage Analysis of a Synthetic Blend of Phenols	35
32	Identification of Samples Analyzed	36
33	Analysis of High-Boiling Tar Acids from Coal Tar Research Association (CTEA), Leeds, England	37
34	Mass Spectral Analysis of Methanol - Extract of Low Temperature tar from Texas Lignite	38
35	Mass Spectral Analysis of a Coal-Hydrogenation Oil	38
36	Mass Spectral Analysis of Distillable neutral oil from hydrogenation of a high temperature tar	39
37	Mass Spectral Analysis of Saturated Neutral Oils Produced by Hydrogenation of Low-Temperature Tar	39
38	Analysis of 120º to 290º C Fraction of Neutral Oil from Carbonization of Subbitominous Western Coal at 500º C	39
39	Mass Spectral Analysis of 120º to 290º C Fraction of Neutral Oil from Carbonization of Subbitominous Western Coal at 500º C	39
40	Mass Spectral Carbon Number Distribution Data from Neutral Oil From 500º C of a Subbitominous Western Coal	40
41	Carbon Number Distribution for Paraffins in Hydrogenated Fractions of Fischer-Tropsch Product	41
42	Determination of n-Paraffins in Hydrogenated Fischer-Tropsch Synthesis Product, bp > 170º C	42
43	Distribution of Normal Paraffins in 170º to 323º C Fraction of Fischer-Tropsch Synthesis Product	45
44	Mass Spectral Analysis of a Synthetic Blends of C₄ and C₅ Hydrocarbons	46
45	Mass Spectral Analysis of a Synthetic Blend of C₅ and C₆ Hydrocarbons	47
46	Mass Spectral Patterns of NO₃ at various pressures	52
47	Apparent Impurities Produced in Spectrometer by Nitrogen Dioxide	53
48	NO₃ Patterns at 100 Microns Obtained with two Different Mass-Spectrometer Filaments	53
49	NO₃ Mass Spectral Patterns at Ionizing Currents of 10 and 50 _ua	53
50	Mass Spectral Synthetic Blends analysis at 50 _ua	53
51	Mass Spectral Patterns of Nitric Oxide, Nitrous Oxide, and Nitrogen Dioxide	54
52	Mass Spectral Analysis of Synthetic Blends Containing NOs and NO	54
53	Nonreactivity of NO and O₂ in Micron Pressure Range	55
54	Successive Mass Spectral Patterns of Red-Fuming Nitric Acid	57
55	Mass Spectrometer of Analysis of Synthetic Blends of Nitric Acid and Nitrogen Dioxide	59
56	Mass Spectra of H2, HD, And D	59
57	Calculation of Equilibrium constants at 500º C for H₂ + D₂ = 2HD from Mass Spectral Analysis	60
58	Reproducibility of Constant-Pressure Gas Samples, with Various Introduction	67
59	Mass Spectral Test for Fractionation through Sintered Disk	67
60	Reproducibility of Liquid Introduction into Mass Spectrometer by 0.001 - ml Self-Filing Micropipet	68
61	Mass Spectral Analysis of Synthetic Blend Introduced with 0.001-ml Self-Filing Micropipet	69
62	Ratio of Negative to Positive Ion Peaks	70