Return to Bulletins

Analytical Methods in Mass Spectrometry - 1967.

Sharkey Jr., A. G.
Shultz, J. L.
Friedel, R. A.

United States Department of the Interior

In this pdf format, this document has 83 pages and is 6.09MB

Table of Contents

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 C15 in 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 2,475C 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 120 to 290 C Fraction of Neutral Oil from Carbonization of Subbitominous Western Coal at 500 C 39

39

Mass Spectral Analysis of 120 to 290 C Fraction of Neutral Oil from Carbonization of Subbitominous Western Coal at 500 C 39

40

Mass Spectral Carbon Number Distribution Data from Neutral Oil From 500 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 > 170 C 42

43

Distribution of Normal Paraffins in 170 to 323 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 500 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