Research Techniques for High Pressure and High Temperature

Research Techniques for High Pressure and High Temperature

Research Techniques for High Pressure and High Temperature Edited by Gene C. Ulmer Springer-Verlag New York Heidelberg Berlin 1971

All rights reserved No part of this book may be translated or reproduced in any form without written permission from Springer-Verlag. 1971 by Springer-Verlag N ew York Inc. Softcover reprint of the hardcover 1st edition 1971 Library of Congress Catalog Card Number 71-173285. ISBN 978-3-642-88099-5 DOl 10.1007/978-3-642-88097-1 ISBN 978-3-642-88097-1 (ebook)

PREFACE Within the last two decades, the experimental technology for the study of high temperature solid-vapor and liquid-vapor equilibria has mushroomed so fast that both academic and industrial researchers desirous of working in this field -- be they physical chemists, metallurgists, ceramists, petrologists, crystal chemists, or members of any of the several branches of materials science -- find themselves in the situation that in order to learn the art of the latest techniques, a period of apprenticeship or residency needs be spent at an institution or laboratory currently engaged in this type of solid-vapor or liquid-vapor research. The techniques for control of the vapor phase at total pressures of one atmosphere or greater have not been well defined in the literature. Therefore, the purpose of this volume will be to serve as a laboratory manual for the control, calibration, and measurement of high temperature-high pressure equilibria. The avowed aims of this treatment of experimental techniques are: (1) to give, in terms understandable at the graduate student level, the laboratory procedures necessary to the design and utilization of good experimental technique, (2) to list the limitations, dangers, and technical pitfalls inherent or intrinsic to the described techniques, (3) to give theory and specific data only where they are essential to the experimental design, (4) to give with each chapter references that are extensive enough to serve as a bibliography of the state-of-the-art of technique development within the last decade. The authors have attempted to delete jargon and make the most general description that is consistent with understanding the technique. With these aims fulfilled, the experimental details within this volume should be applicable to academic, institutional, and industrial research in all branches of chemical, physical, earth, and materials sciences. v

ACKNOWLEDGMENT This volume was initiated, planned, and the table of contents finalized in the hallways at three of the annual Washington meetings of the American Geophysical Union. Special thanks are due to Drs. H.P. Eugster, G. Kullerud, and E.F. Osborn whose encouragement was appreciated. The editor would also like to mention Drs. P.M. Bell, L.S. Walte~ and D.C. Presnall who served as "editorial sounding boards." Special thanks are due to Mrs. R. Krakow for copy editing, to Mr. R. Texter for drafting, and to Mrs. D. Wyszynski for typing. Only with the extreme cooperation and patience displayed by this editorial staff did the idea of this manuscript become a reality. Springer-Verlag, the authors, and editorial staff are to be recognized for their combined efforts to keep the costs of this book low enough that the average student might own a copy of this volume. vii

TABLE OF CONTENTS CHAPTER 1 An Introduction to High Pressure-High Temperature Technology Dr. G.C. Ulmer 1 CHAPTER 2 Gaseous Buffering for the Control of Oxygen Fugacity at One Atmosphere. Drs. R.H. Nafziger, G.C. Ulmer, E. Woermann 9 CHAPTER 3 Electrochemical Measurements and Control of Oxygen Fugacity and Other Gaseous Fugacities with Solid Electrolyte Systems Dr. M. Sato 43 CHAPTER 4 Direct Control of the Oxygen Vapor Phase Mainly at Pressures Greater than One Atm.osphere Dr. W.B. White 101 CHAPTER 5 Buffering Techniques for Hydrostatic Systems at Elevated Pressures. Dr. J.S. Huebner 123 CHAPTER 6 Temperature Calibration in Cold-Seal Pressure Vessels Drs. A.L. Boettcher, D.M. Kerrick 179 CHAPTER 7 Pressure Calibration in Piston-Cylinder Apparatus at High Temperature. Drs. P.M. Bell, D.W. Williams 195 ix

CHAPTER 8 Internally Heated Pressure Vessels Dr. J.R. Holloway 217 CHAPTER 9 Compressibility Measurements of Gases Using Externally Heated Pressure Vessels Dr. D.C. Presnall 259 CHAPTER 10 The Boiling-Point Technique for the Determination of Vapor Pressure of Silicate Mel ts................... Dr. L.S. Walter 279 CHAPTER 11 Experimental Techniques in Dry Sulfide Research.. Dr. G. Ku11erud 289 CHAPTER 12 Investigations in Hydrothermal Sulfide Systems. Dr. H.L. Barnes 317 INDEX. 357 x

LIST OF CONTRIBUTORS Dr. H. L. Barnes Department of Geochemistry and Mineralogy The Pennsylvania State University Dr. P.M. Bell Geophysical Laboratory Carnegie Institute Washington, D.C. Dr. A.L. Boettcher Department of Geochemistry and Mineralogy The Pennsylvania State University Dr. J.R. Holloway Department of Chemistry Arizona State University Dr. J.S. Huebner U.S. Geological Survey Washington, D.C. Dr. D.M. Kerrick Department of Geochemistry and Mineralogy The Pennsylvania State University Dr. G. Kullerud Geophysical Laboratory Carnegie Institute Washington, D.C. Dr. R. Nafziger U.S. Bureau of Mines Albany, Oregon Dr. D.C. Presnall Divisions of Geosciences University of Texas at Dallas Dr. M. Sato U.S. Geological Survey Washington, D.C. Dr. G.C. Ulmer Department of Geology Temple University xi

Dr. L.S. Walter Planetology Branch NASA-Goddard Space Flight Center Greenbelt, Maryland Dr. W.B. White Materials Research Laboratory Department of Geochemistry and Mineralogy The Pennsylvania State University Dr. D.W. Williams Electricity Council Research Center, Capenhurst Chester, England Dr. E. Woe rmann Institut fur Kristallographie Aachen, Germany xii