Plasma Chromatography

Transcription

1 Plasma Chromatography Edited by Timothy W. Carr IBM Corporation Hopewell Junction, New York Plenum Press New York and London

2 Contents 1. Instrument Design and Description G. E. Spangler and M. J. Cohen 1. Introduction 1 2. Equipment Description 3 3. Performance Description Generation of Negative Sample Ions Ion Extraction and Shutter Grid Operation Separation of Ions by Mobility Generation of the Ion Mobility Spectrum (Ion Arrival Time Spectrum) Spectral Interpretation Ion Mobility Reaction Chemistry Theoretical Description ReactorTheory Drift Theory Sample Handling Sample Wire Probe Syringe Injection Exponential Dilution Flask Calibrated Standard Generators Inlet Oven Ambient Air Sampling Plasma Chromatography as a GC Peak Identifier Background of PC Pure Sample into PC Background of GC Sample Injection FID Response PC Response Plasma Chromatography and Mass Spectrometry 37 References Ion Mobility: Its Role in Plasma Chromatography E. A. Mason 1. Introduction Kinetic Theory of Ion Transport 46 ix

3 x CONTENTS 2.1. Summary of Main Results Elementary Derivations Ion-Molecule Forces and Mobility Inelastic CoUisions and Nonspherical Ion-Molecule Interactions Applications to Plasma Chromatography Consistency with Drift-Tube Data Comparison with Polarization Limit Variation of Electric Field Strength and Drift-Gas Pressure Variation of Drift Gas Multiply-Charged Ions Mass-Mobility Correlation Correlation with Vapor Diffusion Coefficients Pulse Width and Shape Ion-Molecule Reactions in the Drift Region Concluding Remarks 89 References Atmospheric Pressure lonization M. W. Siegel 1. Introduction Rate Equations Describing API Reagent Ion Production Sample Ion Production Sample Molecule Depletion Summary of Processes Application of Rate Equations to a 63 Ni API Source Primary lonization Diffusion Recombination Reagent Ion Density Sample Ion Density Sample Ion Current Flow Rate Optimization Source Radius Optimization Meaning of "Small Sample Limit" Sample Quantity vs. Sample Concentration Summary, Conclusions, and Thoughts on Future Work 110 Notation 110 References and Notes Characterization of Isomers by Plasma Chromatography D. F. Hagen 1. Introduction Sampling Requirements and Data Acquisition 116

4 CONTENTS xi 2.1. Sampling Interfaces Sample Size Reactant Ion Level Derivative Stabilization Timing Factors Molecular Ion Characteristics Ion Behavior Rearrangements of Molecular Ions Ion Molecule, Size-Mass Relationships Aromatic Positional Isomers Substituted Toluenes and Chlorobenzoate Ester Homologs Phthalate Ester Homologs Trisubstituted Benzene Isomere Isomeric Perfluidones and Methoxyperfluidones Branched Chain Isomers Cis-Trans Isomers Polynuclear Aromatics Aromatic Nitrogen Compounds Dipyridyls, Phenyl Pyridines Naphthalene Related Nitrogen Isomers Picoline-Pyrazine Isomers Concluding Remarks 140 References Plasma Chromatography as a Gas Chromatographie Detection Method Herbert H. Hill and Michael A. Baim 1. Ambient Pressure lonization Detectors for Gas Chromatography Sample Introduction Qualitative Analysis Moving Second Gate Method Single-Scan Method Signal Averaging Method Qualitative GC Detection Continuous Mobility Monitoring Quantitative Analysis Calibration Graphs Precision Accuracy Interferences Overload Solvent Effects Column Bleed Matrix Interference Residence Time A Detector for Capillary Chromatography 171 References 175

5 xii CONTENTS 6. Analysis of Toxic Vapors by Plasma Chromatography R. J. Dam 1. The Role of Plasma Chromatography in Toxic Gas Monitoring Introduction Advantages of Plasma Chromatography Disadvantages of Plasma Chromatography Selecting Suitable PC Monitoring Applications PC Monitor Development Program at Du Pont Plasma Chromatograph Calibration Requirements of a Calibration Technique Basic Concepts and Theory Calibration Apparatus and Methods Calibration Example Sampling Systems Design Goals System Description Measuring System Performance System Enclosure Instrument Control and Data Processing General Considerations Plasma Chromatograph Data Acquisition Instrument Control and Hardware Status Monitoring Software Toxic Monitoring Applications Workplace Characterization Improved Instrument Proven Reliable Maintenance Procedura Future Work 213 References Analysis of Semiconductor Devices and Microelectronic Packages by Plasma Chromatography/Mass Spectroscopy T. W. Carr 1. Introduction Analysis of Organic Surface Contaminants Introduction Experimental Discussion Discussion of Surface Analysis Analysis of Water in Sealed Electronic Packages Introduction Negative Ion Measurements Positive Ion Measurements Analysis of Headspace Vapor of Sealed Packages Plasma Chromatography as a Process Monitor Extension of PC/MS to Small-Area Surface Analysis. 233

6 CONTENTS *'" 7. Conclusion 234 References Instrument Design and Automation Roger F. Wernlund 1. Introduction Hardware Central Processing Unit (CPU) Peripherals Interfacing Software Basic Data Acquisition Basic Data Storage and Retrieval Basic Data Reduction Higher Level Command Structure 247 Subject Index 257 Author Index 257