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5
 5
Comprehensive coverage of recent events and research as compiled by
the staff of the McGraw-Hill Encyclopedia of Science & Technology

McGraw-Hill
New York Chicago San Francisco Lisbon London Madrid Mexico City Milan
New Delhi San Juan Seoul Singapore Sydney Toronto
Library of Congress Cataloging in Publication data

McGraw-Hill yearbook of science and technology.

1962– . New York, McGraw-Hill.

v. illus. 26 cm.
Vols. for 1962– compiled by the staff of the
McGraw-Hill encyclopedia of science and technology.
1. Science—Yearbooks. 2. Technology—
Yearbooks. 1. McGraw-Hill encyclopedia of
science and technology.
Q1.M13 505.8 62-12028

ISBN 0-07-144504-8
ISSN 0076-2016

McGRAW-HILL YEARBOOK OF SCIENCE & TECHNOLOGY

Copyright
c 2005 by The McGraw-Hill Companies, Inc.
All rights reserved. Printed in the United States of America.
Except as permitted under the United States Copyright Act of 1976,
no part of this publication may be reproduced or distributed in any
form or by any means, or stored in a data-base or retrieval system,
without prior written permission of the publisher.
The following articles are excluded from McGraw-Hill Copyright:
Active Thermochemical Tables; Arctic mining technology; Distributed
generation (electric power systems); Hearing disorders; Solar storms;
Space flight; Submarine hydrodynamics; Ultrasonic aerosol concentration
and positioning.

1 2 3 4 5 6 7 8 9 0 DOW/DOW 0 10 9 8 7 6 5 4

This book was printed on acid-free paper.

It was set in Garamond Book and Neue Helvetica Black Condensed by

TechBooks, Fairfax, Virginia. The art was prepared by TechBooks.
The book was printed and bound by RR Donnelley, The Lakeside Press.
 Contents

Editorial Staff . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi

International Editorial Advisory Board. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi

Editing, Design, and Production Staff . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Consulting Editors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Article Titles and Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . x

Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii

Articles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1–393

Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
Editorial Staff
Mark D. Licker, Publisher

Elizabeth Geller, Managing Editor

Jonathan Weil, Senior Staff Editor
David Blumel, Editor
Alyssa Rappaport, Editor
Charles Wagner, Manager, Digital Content
Renee Taylor, Editorial Assistant

International Editorial Advisory Board

Dr. Neil Bartlett Dr. Koichi Shimoda
Emeritus Professor of Chemistry President
University of California, Berkeley Physics Education Society of Japan

Dr. A. E. Siegman
Prof. Richard H. Dalitz
Professor of Electrical Engineering
Department of Theoretical Physics
Edward L. Ginzton Laboratory
Oxford University, England
Stanford University

Dr. Freeman J. Dyson Dr. George W. Wetherill

Institute for Advanced Study Research Staff
Princeton, New Jersey Department of Terrestrial Magnetism
Carnegie Institution of Washington

Dr. Leon Knopoff

Dr. E. O. Wilson
Institute of Geophysics and Planetary Physics
Professor of Zoology
University of California, Los Angeles
Harvard University

Dr. H. C. Longuet-Higgins Dr. Arnold M. Zwicky

Emeritus Professor of Experimental Psychology Emeritus Professor of Linguistics
University of Sussex, Brighton, England Ohio State University

vi
 Editing, Design, and Production Staff
Roger Kasunic, Vice President—Editing, Design, and Production

Joe Faulk, Editing Manager

Frank Kotowski, Jr., Senior Editing Supervisor
Ron Lane, Art Director
Vincent Piazza, Assistant Art Director
Thomas G. Kowalczyk, Production Manager

Consulting Editors
Dr. Milton B. Adesnik. Department of Cell Biology, Prof. Laurie J. Butler. Department of Chemistry, Uni-
New York University School of Medicine, New versity of Chicago. PHYSICAL CHEMISTRY.
York. CELL BIOLOGY.
Dr. Mark Chase. Molecular Systematics Section,
Prof. William P. Banks. Chairman, Department of Jodrell Laboratory, Royal Botanic Gardens, Kew,
Psychology, Pomona College, Claremont, Cali- Richmond, Surrey, United Kingdom. PLANT TAX-
fornia. GENERAL AND EXPERIMENTAL PSYCHOLOGY. ONOMY.

Prof. Ted Barnes. Physics Division, Oak Ridge Na- Prof. Wai-Fah Chen. Dean, College of Engineering,
tional Laboratory, Oak Ridge, Tennessee. ELEMEN- University of Hawaii. CIVIL ENGINEERING.
TARY PARTICLE PHYSICS.
Dr. John F. Clark. Director, Graduate Studies, and
Dr. Paul Barrett. Department of Palaeontology, The Professor, Space Systems, Spaceport Graduate
Natural History Museum, London. VERTEBRATE PA- Center, Florida Institute of Technology, Satellite
LEONTOLOGY. Beach. SPACE TECHNOLOGY.
Prof. Ray Benekohal. Department of Civil and Envi- Dr. J. John Cohen. Department of Immunology, Uni-
ronmental Engineering, University of Illinois at versity of Colorado School of Medicine, Denver.
Urbana-Champaign. TRANSPORTATION ENGINEERING. IMMUNOLOGY.
Prof. Carrol Bingham. Department of Physics, Univer- Prof. Mark Davies. Department of Mechanical &
sity of Tennessee, Knoxville. NUCLEAR PHYSICS. Aeronautical Engineering, University of Limer-
Michael L. Bosworth. Vienna, Virginia. NAVAL ARCHITEC- ick, Ireland. AERONAUTICAL ENGINEERING.
TURE AND MARINE ENGINEERING.
Prof. Peter J. Davies. Department of Plant Biology,
Dr. Chaim Braun. Retired; formerly, Altos Manage- Cornell University, Ithaca, New York. PLANT PHYS-
ment Consultants, Inc., Los Altos, California. NU- IOLOGY.
CLEAR ENGINEERING.
Dr. M. E. EI-Hawary. Associate Dean of Engineer-
Robert D. Briskman. Technical Executive, Sirius Satel- ing, Dalhousie University, Halifax, Nova Scotia,
lite Radio, New York. TELECOMMUNICATIONS. Canada. ELECTRICAL POWER ENGINEERING.
Prof. Richard O. Buckius. Department of Mechani- Prof. Turgay Ertekin. Chairman, Department of Pet-
cal and Industrial Engineering, University of roleum and Natural Gas Engineering, Pennsyl-
Illinois at Urbana-Champaign. MECHANICAL ENGI- vania State University, University Park. PETRO-
NEERING. LEUM ENGINEERING.

vii
Barry A. J. Fisher. Director, Scientific Services Bu- Prof. Scott M. McLennan. Department of Geosciences,
reau, Los Angeles County Sheriff’s Department, State University of New York at Stony Brook.
Los Angeles, California. FORENSIC SCIENCE AND TECH- GEOLOGY ( PHYSICAL, HISTORICAL, AND SEDIMENTARY).
NOLOGY.
Prof. Joel S. Miller. Department of Chemistry, Univer-
Dr. Richard L. Greenspan. The Charles Stark Draper sity of Utah, Salt Lake City. INORGANIC CHEMISTRY.
Laboratory, Cambridge, Massachusetts. NAVIGA- Dr. Orlando J. Miller. Professor Emeritus, Center for
TION.
Molecular Medicine and Genetics, Wayne State
Dr. John P. Harley. Department of Biological Sciences, University School of Medicine, Detroit, Michi-
Eastern Kentucky University, Richmond. MICRO- gan. GENETICS.
BIOLOGY.
Prof. Jay M. Pasachoff. Director, Hopkins Observa-
Prof. Terry Harrison. Department of Anthropology, tory, Williams College, Williamstown, Massa-
Paleoanthropology Laboratory, New York Uni- chusetts. ASTRONOMY.
versity, New York. ANTHROPOLOGY AND ARCHEOLOGY. Prof. David J. Pegg. Department of Physics, Univer-
Dr. Ralph E. Hoffman. Associate Professor, Yale Psychi- sity of Tennessee, Knoxville. ATOMIC, MOLECULAR,
atric Institute, Yale University School of Medi- AND NUCLEAR PHYSICS.
cine, New Haven, Connecticut. PSYCHIATRY. Prof. J. Jeffrey Peirce. Department of Civil and En-
Dr. Gary C. Hogg. Chair, Department of Industrial vironmental Engineering, Edmund T. Pratt Jr.
Engineering, Arizona State University. INDUSTRIAL School of Engineering, Duke University,
AND PRODUCTION ENGINEERING. Durham, North Carolina. ENVIRONMENTAL ENGINEER-
ING.
Prof. Gordon Holloway. Department of Mechanical
Engineering, University of New Brunswick, Dr. William C. Peters. Professor Emeritus, Mining and
Canada. FLUID MECHANICS. Geological Engineering, University of Arizona,
Tucson. MINING ENGINEERING.
Dr. S. C. Jong. Senior Staff Scientist and Program
Director, Mycology and Protistology Program, Prof. Arthur N. Popper. Department of Biology, Uni-
American Type Culture Collection, Manassas, versity of Maryland, College Park. NEUROSCIENCE.
Virginia. MYCOLOGY. Dr. Kenneth P. H. Pritzker. Pathologist-in-Chief and Di-
Dr. Peter M. Kareiva. Director of Conservation and rector, Head, Connective Tissue Research Group,
Policy Projects, Environmental Studies Insti- and Professor, Laboratory Medicine and Patho-
tute, Santa Clara University, Santa Clara, biology, University of Toronto, Mount Sinai
California. ECOLOGY AND CONSERVATION. Hospital, Toronto, Ontario, Canada. MEDICINE AND
PATHOLOGY.
Dr. Bryan A. Kibble. National Physical Laboratory,
Teddington, Middlesex, United Kingdom. ELEC- Prof. Justin Revenaugh. Department of Geology and
TRICITY AND ELECTROMAGNETISM. Geophysics, University of Minnesota, Minnea-
polis. GEOPHYSICS.
Dr. Arnold G. Kluge. Division of Reptiles and Amphib-
ians, Museum of Zoology, Ann Arbor, Michigan. Dr. Roger M. Rowell. USDA–Forest Service, Forest
SYSTEMATICS. Products Laboratory, Madison, Wisconsin.
FORESTRY.
Prof. Robert E. Knowlton. Department of Biological
Sciences, George Washington University, Wash- Dr. Andrew P. Sage. Founding Dean Emeritus and
ington, DC. INVERTEBRATE ZOOLOGY. First American Bank Professor, University Pro-
fessor, School of Information Technology and
Dr. Cynthia Larive. Department of Chemistry, Univer- Engineering, George Mason University, Fairfax,
sity of Kansas, Lawrence. INORGANIC CHEMISTRY. Virginia. CONTROL AND INFORMATION SYSTEMS.
Prof. Chao-Jun Li. Canada Research Chair in Green Prof. Ivan K. Schuller. Department of Physics, Uni-
Chemistry, Department of Chemistry, McGill versity of California–San Diego, La Jolla, Cali-
University, Montreal, Quebec, Canada. ORGANIC fornia. CONDENSED-MATTER PHYSICS.
CHEMISTRY.
Dr. David M. Sherman. Department of Earth Sciences,
Dr. Donald W. Linzey. Wytheville Community College, University of Bristol, United Kingdom. MINERAL-
Wytheville, Virginia. VERTEBRATE ZOOLOGY. OGY.

Dr. Philip V. Lopresti. Retired; formerly, Engineering Prof. Arthur A. Spector. Department of Biochemistry,
Research Center, AT&T Bell Laboratories, Prince- University of Iowa, Iowa City. BIOCHEMISTRY.
ton, New Jersey. ELECTRONIC CIRCUITS.
Dr. Bruce A. Stanley. Director, Scientific Programs,
Dr. Philip L. Marston. Department of Physics, Wash- Section of Technology Development and Re-
ington State University, Pullman. ACOUSTICS. search Resources, Penn State College of Medi-
Dr. Ramon A. Mata-Toledo. Associate Professor of cine, Hershey, Pennsylvania. PHYSIOLOGY.
Computer Science, James Madison University, Prof. Anthony P. Stanton. Carnegie Mellon Univer-
Harrisonburg, Virginia. COMPUTERS. sity, Pittsburgh, Pennsylvania. GRAPHIC ARTS AND
PHOTOGRAPHY.
Prof. Krzysztof Matyjaszewski. J. C. Warner Professor
of Natural Sciences, Department of Chemistry, Dr. Trent Stephens. Department of Biological Sci-
Carnegie Mellon University, Pittsburgh, Pennsyl- ences, Idaho State University, Pocatello. DEVEL-
vania. POLYMER SCIENCE AND ENGINEERING. OPMENTAL BIOLOGY.

viii
Dr. Sally E. Walker. Associate Professor of Geology Canada. MATERIALS SCIENCE AND METALLURGIC ENGINEER-
and Marine Science, University of Georgia, ING.
Athens. INVERTEBRATE PALEONTOLOGY.
Prof. Thomas A. Wikle. Head, Department of Geogra-
Prof. Pao K. Wang. Department of Atmospheric and phy, Oklahoma State University, Stillwater. PHYS-
Oceanic Sciences, University of Wisconsin– ICAL GEOGRAPHY.
Madison. METEOROLOGY AND CLIMATOLOGY.
Prof. Jerry Woodall. School of Electrical and Com-
Dr. Nicole Y. Weekes. Pomona College, Claremont, puter Engineering, Purdue University, West
California. NEUROPSYCHOLOGY. Lafayette, Indiana. PHYSICAL ELECTRONICS.
Prof. Mary Anne White. Killam Research Professor Dr. James C. Wyant. University of Arizona Optical
in Materials Science, Department of Chemistry, Sciences Center, Tucson. ELECTROMAGNETIC RADIATION
Dalhousie University, Halifax, Nova Scotia, AND OPTICS.

ix
Article Titles and Authors
Acoustic viscometer Dinosaur growth
James B. Mehl Gregory M. Erickson
Active Thermochemical Tables Directed evolution
Branko Ruscic Kira J. Weissman
Adaptive wings Display manufacturing by inkjet printing
Mohamed Gad-el-Hak Linda T. Creagh
Adoptive tumor immunotherapy Distributed generation (electric power systems)
Jill E. Slansky Thomas S. Basso
Advanced wireless technology Document scanning
Michael D. Rauchwerk Elisa H. Barney Smith
Arctic mining technology Earth Simulator
John E. Udd Seiji Tsuboi
Atmospheric modeling, isentropic Electrospinning
Pao K. Wang Frank K. Ko
Atom economy Environmental management (mining)
Charlene C. K. Keh; Chao-Jun Li Sheila Ellen Daniel
Atomic-scale imaging of dynamic surfaces Environmental sensors
Thomas P. Pearl Joe Hartman
Autoimmunity to platelets
Evolutionary developmental biology (invertebrate)
Zoë Cohen; Alison Starkey
James W. Valentine
Aviation security
Evolutionary developmental biology (vertebrate)
Kathleen M. Sweet
Jonathan E. Jeffery
Biological pest control
Exchange bias
Gary C. Chang
Chris Leighton; Michael Lund
Bioterrorism
Experience and the developing brain
John P. Harley
Brain size (genetics) Robbin Gibb; Bryan Kolb; Ian Whishaw
Jianzhi Zhang Extensible Markup Language (XML) databases
Catalytic hydroamination Robert Tucker
Jan Antoinette C. Romero; Gary A. Molander Extreme programming and agile methods
Cell membrane sealing Christopher Fox
Ka Yee C. Lee Firefly communication
Change blindness (psychology) Marc A. Branham
Ronald A. Rensink Flapping-wing propulsion
Chimpanzee behavior Kirill V. Rozhdestvensky; Vladimir Ryzhov
John C. Mitani Forensic botany
Chinese space program Jane H. Bock; David O. Norris
James Oberg Fossil microbial reefs
Cirrus clouds and climate Constance M. Soja
K. N. Liou Genetically modified crops
Clinical yeast identification C. S. Prakash
George S. Kobayashi Glaciology
Cloning Terence J. Hughes
Don P. Wolf GPS modernization
Collective flux pinning Thomas A. Stansell, Jr.
José Luis Vicent Harmonics in electric power systems
Combinatorial materials science Bill Moncrief
David Ginley; Charles Teplin; Matthew Taylor; Hearing disorders
Maikel van Hest; John Perkins Andrew J. Griffith
Comparative bacterial genome sequencing Helper and regulatory T cells
Duncan J. Maskell Ciriaco A. Piccirillo
Computational intelligence High-altitude atmospheric observation
Lawrence O. Hall Stephan Borrmann
CT scanning (vertebrate paleontology) HIV vaccines
Richard A. Ketcham Derek T. O’Hagan
Denali earthquake Homo erectus
Charles M. Rubin Susan C. Antón

x
Human/machine differentiation Multiple ionization (strong fields)
Daniel Lopresti; Henry Baird Reinhard Dörner
Human-powered submarines Natural optical fibers
Wayne L. Neu Andrew D. Yablon; Joanna Aizenberg
Humans and automation Neoproterozoic predator-prey dynamics
Thomas B. Sheridan Brian R. Pratt
Hurricane-related pollution Network security and quality of service
J. Jeffrey Peirce Nong Ye
Integrated electric ship power systems Neurotrophic factors
Cyril Krolick Amelia J. Eisch
Intelligent transportation systems Neutral-atom storage ring
Ardeshir Faghri Jacob A. Sauer; Michael S. Chapman
Ionic liquids Nobel prizes
M. B. Turner; J. D. Holbrey; S. K. Spear; Olfactory system coding
R. D. Rogers Minghong Ma
Killer whales Optical coherence tomography
Terra Grandmason Amy L. Oldenburg; Stephen A. Boppart
Lake hydrodynamics
Origin of vertebrates
Daniel McGinnis; Alfred Wüest
David K. Elliott
Language and the brain
Orographic precipitation (meteorology)
Colin Phillips; Kuniyoshi L. Sakai
Yuh-Lang Lin
Lignin-degrading fungi
Pentaquarks
Carlos G. Dosoretz; Yitzhak Hadar
Kenneth H. Hicks
Lipidomics
Persistent, bioaccumulative, and toxic pollutants
Charles N. Serhan
Location-based security Daniel Vallero
Logan Scott Pharmaceutical crops
Low-speed aircraft Michelle Marvier
James D. DeLaurier Phosphoinositides
Macromolecular engineering Daniela Corda; Maria Antonietta De Matteis
Nikos Hadjichristidis; Hermis Iatrou; Photonic crystal devices
Marinos Pitsikalis K. J. Kasunic
Madagascan primates Photoprotection in plants
Laurie R. Godfrey William W. Adams III
Magnetorheological finishing (optics) Polymer recycling and degradation
Paul Dumas Mikael Gröning; Ann-Christine Albertsson
Mantle transition-zone water filter Polymer solar cells
David Bercovici; Shun-ichiro Karato Ingo Riedel; Jürgen Parisi; Vladimir Dyakonov
Mass extinctions Probiotics
Donald R. Prothero Gregor Reid
Mass spectrometry (carbohydrate analysis) Protein networks
Heather Desaire Jodi R. Parrish; Russell L. Finley, Jr.
Medicinal mushrooms Quorum sensing in bacteria
John E. Smith Juan E. González
Menopause
Radiation-curable inks and coatings
Jocelyn Scott Peccei
Don P. Duncan
Micro hydropower
Radio-echo sounding
Arthur A. Williams
Martin J. Siegert
Microcombustion
Alessandro Gomez Radio-frequency spectrum management
Mississippi River degradation S. B. Harris; D. Ladson
Stacey Solie Red yeast rice
Mobile satellite services with an ancillary Petra Patáková
terrestrial component Resveratrol
Peter D. Karabinis Shazib Pervaiz
Modern traditional sailing ships Ridge-flank hydrothermal circulation
Iver C. Franzen A. T. Fisher
Moisture-resistant housing Satellite climatology
John F. Straube Andrew M. Carleton
Molecular motors Segmentation and somitogenesis in vertebrates
Manfred Schliwa Olivier Pourquié

xi
Self-cleaning surfaces Surface plasmon resonance
David Quéré K. Scott Phillips; Thomas Wilkop; Quan Cheng
Serial data transmission Systematics in forensic science
Edmund H. Suckow Marc Allard; Bruce Budowie; Mark R. Wilson
Severe acute respiratory syndrome (SARS) Systems architecting
Susan M. Poutanen; Allison J. McGeer Andrew P. Sage
Shape memory alloys Tetraquarks
Ingo Müller Frank Close
Sloan Digital Sky Survey Thermoacoustic mixture separation
Gillian R. Knapp Gregory W. Swift
Small warship design Transits of Venus
Mark R. Bebar Jay M. Pasachoff
Smart card Transportation system security
Katherine M. Shelfer; Kevin Meadows Joyce Wenger; Nicholas Bahr
SMART 1
Two-photon emission
Bernard H. Foing
Hans Kleinpoppen
Solar storms
John Kohl Ultrasonic aerosol concentration and positioning
Space flight Gregory Kaduchak; Christopher Kwiatkowski;
Dipen Sinha
Jesco von Puttkamer
Space shuttle Visual illusions and perception
Jeffrey C. Mitchell Donald D. Hoffman
Spherical microphone arrays Vitamin D
Gary W. Elko; Jens Meyer Armin Zittermann
Spitzer Space Telescope Voice over IP
George Rieke Daniel Heer
Stereoscopic displays West Nile fever (encephalitis)
Hong Hua Marcia M. Pierce
Submarine hydrodynamics Wide-band-gap III-nitride semiconductors
George D. Watt Jung Han; Arto V. Nurmikko
Superconducting motors Wireless sensors
Philippe J. Masson; Steinar J. Dale Ray Lohr
Superheavy elements Xenoturbella (invertebrate systematics)
Mark A. Stoyer Sarah J. Bourlat

xii
 Preface

The 2005 McGraw-Hill Yearbook of Science & Tech- scale surface imaging, combinatorial materials sci-
nology provides a broad overview of important re- ence, macromolecular engineering, polymer recy-
cent developments in science, technology, and en- cling and degradation, pentaquarks, and tetraquarks.
gineering as selected by our distinguished board of Articles on change blindness, experience and the de-
consulting editors. At the same time, it satisfies the veloping brain, language and the brain, and visual
nonspecialist reader’s need to stay informed about illusions and perception survey recent advances in
important trends in research and development that psychology. And reviews in atmospheric modeling,
will advance our knowledge in the future in fields environmental sensors, glaciology, hurricane-related
ranging from agriculture to zoology and lead to im- pollution, and satellite climatology are among the ar-
portant new practical applications. Readers of the ticles in the earth and environmental sciences.
McGraw-Hill Encyclopedia of Science & Technol-
ogy, 9th edition (2002), also will find the Yearbook Each contribution to the Yearbook is a concise
to be a valuable companion publication, supplement- yet authoritative article prepared by one or more
ing and updating the basic information. experts in the field. We are pleased that noted re-
searchers have been supporting the Yearbook since
In the 2005 edition we continue to chronicle the its first edition in 1962 by taking time to share their
rapid advances in cell and molecular biology with knowledge with our readers. The topics are selected
articles on topics such as cloning, helper and regu- by our consulting editors in conjunction with our ed-
latory T cells, lipidomics, olfactory system coding, itorial staff based on present significance and poten-
and protein networks. Reviews in topical areas of tial applications. McGraw-Hill strives to make each
biomedicine, such as HIV vaccines, hearing disor- article as readily understandable as possible for the
ders, severe acute respiratory syndrome (SARS), and nonspecialist reader through careful editing and the
West Nile fever, are presented. Key scientific and extensive use of graphics, much of which is prepared
technical issues relating to security are covered in specially for the Yearbook.
articles on aviation security, bioterrorism, and trans-
portation system security. Advances in computing Librarians, students, teachers, the scientific com-
and communication are documented in articles on munity, journalists and writers, and the general
advanced wireless technology, computational intel- reader continue to find in the McGraw-Hill Yearbook
ligence, XML databases, extreme programming and of Science & Technology the information they need
agile methods, mobile satellite services, serial data in order to follow the rapid pace of advances in sci-
transmission, and Voice over IP, among others. Note- ence and technology and to understand the develop-
worthy developments in materials science, chem- ments in these fields that will shape the world of the
istry, and physics are reported in reviews of atomic- twenty-first century.

Mark D. Licker
PUBLISHER

xiii
 A–Z
The viscometer has been tested in the temperature
Acoustic viscometer range 273–373 K (32–212◦F) and the pressure range
The Greenspan acoustic viscometer, first inves- 0.2–3 MPa (2–30 atm).
tigated by M. Greenspan and F. N. Wimenitz in 1953, Design. The viscometer is an acoustic resonator
is a relatively compact and robust device for mea- designed to make the resonance response sensitive
suring the viscosity of gases using the principles of to the viscosity of the gas filling the resonator. A sim-
acoustic resonance. The viscometer was further de- plified resonator (Fig. 1) can be machined in three
veloped both experimentally and theoretically dur- pieces. The center piece forms a circular duct and
ing the past decade. a plate that separates two chambers. This system,
Viscosity is a physical parameter which charac-
terizes frictional processes in moving fluids. It has
units of pressure times time, and is used to calcu-
late the flow of gases in pipes and the frictional drag
of gases on moving objects. Viscosity can be deter-
mined by several methods, including measurements
of gas flow in capillaries and the damping of oscillat-
ing bodies in the gas. The acoustic viscometer is an
alternative to these classical methods.
Current versions of the viscometer are fabricated
entirely of metal. The only moving parts are the
gas sample and acoustic transducers mounted ex-
ternal to the resonator. The viscometer is normally
mounted in a sample chamber with provision for
temperature and pressure control, evacuation, and
change of gas composition. Because the gas sample
contacts only metal parts, the viscometer is partic-
ularly suitable for use on corrosive gases when a (a)
corrosion-resistant metal is used for fabrication. An
individual measurement of gas viscosity at a fixed
temperature and pressure takes several minutes. The fill capillary
experiment can be fully automated so that a series of end
measurements can be made under computer control plate
without a human attendant.
In principle, the Greenspan viscometer is an ab- acoustic
solute instrument from which the viscosity can be transducer
determined using apparatus dimensions and other
well-known thermophysical properties of the gas. In
practice, the accuracy can be improved through cal-
ibrating with a substance for which the viscosity is
well known, like helium or argon. An apparatus cali-
brated with helium was recently used to measure the
viscosity of four polyatomic gases (methane, nitro-
(b)
gen, propane, and sulfur hexafluoride). The results
agreed with well-accepted reference values for these Fig. 1. Simplified Greenspan viscometer. (a) Perspective
view. (End plates, acoustic transducers, and fill capillary
gases within ±0.5%. Measurements of similar accu- are omitted.) (b) Cross-sectional view. The size of the fill
racy should be possible for a wide range of gases. capillary is exaggerated for clarity.
2 Acoustic viscometer

known as a double-Helmholtz resonator, has a low- as the quality factor of the resonance, can be de-
frequency mode of oscillation in which the gas os- termined experimentally by fitting a theoretical res-
cillates transversely in the duct. As the gas moves to onance curve to the measured response. The qual-
the right, the gas in the right chamber is compressed ity factor of an oscillating system is approximately
and the gas pressure increases. The pressure in the equal to the average energy stored in the system
left chamber decreases as the gas moves to the right. divided by the energy dissipated in one oscillation
Both the higher-pressure gas in the right chamber cycle. The acoustic viscometer is designed so that the
and the lower-pressure gas in the left chamber major source of energy dissipation is viscous friction
exert a leftward force on the gas in the duct, which at the walls of the duct. If only viscous dissipation
decelerates the gas, eventually reversing its motion contributed to the resonance width, the viscosity
and completing a half cycle of oscillation. During η could be determined from the measured Q using
the second half cycle, the gas initially moves to the Eq. (2), where ρ is the gas density. In practice, this
left, is decelerated by the increasing pressure in the
left chamber and the decreasing pressure in the right η = ρ f0 A/Q2 (2)
chamber, and eventually reverses direction. Oscillat- formula overestimates the viscosity because of an-
ing systems of this type are referred to as Helmholtz other important dissipation process.
resonators, named after Hermann Helmholtz, who Effect of thermal dissipation. When a gas is com-
studied similar (but single-chambered) resonators in pressed rapidly, the gas temperature rises. The nor-
the nineteenth century. mal response to an elevated temperature is heat flow,
Resonance frequency. The resonance frequency f0 which tends to restore temperature uniformity. How-
of the Greenspan viscometer is given approximately ever, the compressions and rarefactions of gas in
by Eq. (1), where c is the speed of sound, A is the an acoustic wave are sufficiently rapid that there is
 insufficient time for significant heat flow to keep the
c 2A
f0 = (1) temperature uniform. Instead, the gas temperature
2π LV oscillates in phase with the pressure. Although the
cross-sectional area of the duct, L is the effective temperature oscillations cause negligible heat flow
length of the duct, and V is the chamber volume. As within the bulk of the gas, heat currents are gener-
an example, with a duct diameter of 5 mm, length ated near solid boundaries, because solids are much
35 mm, and chambers of radii and length 20 mm, in better conductors of heat than gases.
air at ambient conditions, the resonance frequency A full theoretical analysis shows that the oscillating
is 367 Hz. The wavelength of acoustic waves of this heat currents are confined to a thin region near the
frequency, 940 mm, greatly exceeds the dimensions resonator walls. This region, known as the thermal
of the viscometer. The wavelength determines the boundary layer, has an effective thickness δ t depen-
scale of spatial variations of the gas velocity and pres- dent upon the sound frequency f, the gas thermal
sure. Accordingly, the gas motion is very uniform conductivity K, the gas density ρ, and the specific
within the duct, and the acoustic pressure is very heat cp, as given by Eq. (3).
uniform within the chambers. 
Frequency response. The oscillations can be ex- δt = K/(πρ f cp ) (3)
cited and detected by acoustic transducers mounted
Within the duct, the gas velocity varies from zero
outside the resonator and coupling to the gas sam-
at the duct walls to a spatially uniform value well
ple through thin regions machined into the chamber
within the duct. This increase occurs within the vis-
walls. The frequency response of the resonator can
cous boundary layer, a region of effective thickness
be measured by sweeping the frequency of the ex-
given by Eq. (4). The lengths δ v and δ t have similar
citation transducer through f0 while measuring the

signal with the detector transducer. The resonance δv = η/(πρ f ) (4)
profile (Fig. 2) has a width f0/Q, where Q, known
magnitudes; they also depend on frequency and den-
sity in the same way.
An improved formula for the viscometer quality
factor is given by Eq. (5), where rd is the duct
1 δv Sδt
acoustic signal

= + (γ − 1) (5)
f0 /Q Q rd 2V

radius, S the internal surface area of one chamber,

and γ the ratio of the constant-pressure specific heat
to the constant-volume specific heat. This quantity
(γ ) is greater than unity for all gases, equal to 5/3 for
ideal monatomic gases, and trends toward unity as
f0
the complexity of the gas molecules increases. The
first term in Eq. (5) is the ratio of the viscous bound-
frequency
ary layer to the duct radius. This ratio is the approx-
Fig. 2. Resonance profile. imate fraction of the duct where viscous dissipation
 Active Thermochemical Tables 3

takes place. The second term is the ratio of the ef- consistent thermochemical values, and are rapidly
fective volume Sδ t where thermal dissipation takes becoming the archetypal approach to thermochem-
place to the total chamber volume V, multiplied by istry.
(γ − 1)/2. Knowledge of the thermochemical stability of vari-
Thermal dissipation can be reduced by making the ous chemical species (encompassing both stable sub-
chambers large compared with the duct so that V/S is stances and ephemeral moieties such as free radicals)
much larger than rd. Also, for many gases of practical is central to most aspects of chemistry and critical in
interest, γ is close to unity so the thermal dissipation many industries. This is because the outcome of all
is further reduced by the factor (γ − 1). Other cri- chemical reactions ultimately hinges on the under-
teria enter into a practical design. The compromises lying thermodynamics. In particular, the availability
chosen for a recent design led to a thermal contribu- of accurate, reliable, and internally consistent ther-
tion to 1/Q under typical measurement conditions mochemical values for a broad range of chemical
that was 36% of the viscous term for argon (γ ≈ 1.67) species is essential in various branches of physical
and 7% of the viscous term for propane (γ ≈ 1.14). chemistry, such as chemical kinetics, construction of
Although the ratio of the thermal conductivity to the reaction mechanisms, or formulation of descriptive
specific heat must be known in order to determine chemical models that have predictive abilities. Simi-
the viscosity, these quantities need not be known to larly, the availability of properly quantified uncertain-
high accuracy, owing to the low sensitivity of 1/Q to ties for thermochemical properties is essential for
thermal dissipation for gases with γ near unity. correctly assessing hypotheses, models, and simula-
Use of theoretical model. The preceding discussion tions.
of the contributions to 1/Q illustrates the physical Traditional thermochemical tables. Traditional ther-
principles of the viscometer operation. In actual mochemical tables are tabulations of thermochemi-
practice, a full theoretical model of the viscometer cal properties conveniently sorted by chemical
is used. This model accurately predicts a complex species. Their quality ranges from fully documented
resonance response function that is directly fitted to critical data evaluations, through compilations con-
the measured resonance response. The gas viscosity taining references but not explaining the reasons for
is determined as one of the fit parameters. favoring a particular value, to lists providing fully ref-
Experimental techniques. In laboratory environ- erenced multiple values without attempting an eval-
ments, gas viscometers are generally placed in a reg- uation, to tabulations that select values from other
ulated thermal environment so that the temperature compilations. The selection of listed properties
of the measurement can be well controlled. Gas- varies considerably. For example, the enthalpy of for-
handling plumbing is provided for filling the appa- mation is usually provided, and frequently the Gibbs
ratus with test gases, for controlling the pressure energy of formation, heat capacity, entropy, enthalpy
of the test gas, and for evacuation of the appara- increment (also known as the integrated heat capac-
tus prior to changing test gases. Materials and tech- ity), and so on. The temperatures for which these
niques suitable for maintaining gas purity are used. properties are listed typically include room tempera-
Actual viscosity measurements are made under com- ture (298.15 K or 77◦F) and sometimes a selection of
puter control. Appropriate electronic devices are other temperatures. Some compilations present the
used to generate sound within the viscometer and thermochemistry in the form of polynomials rather
to store the resonance profiles in computer memory. than tables. The most reliable thermochemical val-
Further computer analysis of the resonance profiles ues come from critical data evaluations, which in-
using the full experimental model is applied to yield clude an independent review of the original deter-
values of viscosity. minations (subject to random and systematic errors)
For background information see ACOUSTIC RES- of the physical quantities involved.
ONATOR; CONDUCTION (HEAT); KINETIC THEORY OF Customary sequential approach. The thermochem-
MATTER; Q (ELECTRICITY); RESONANCE (ACOUSTICS ical properties for any chemical species are derived
AND MECHANICS); SPECIFIC HEAT; VISCOSITY in the from basic determinations that fall into two cate-
McGraw-Hill Encyclopedia of Science & Technology. gories: species-specific and species-interrelating.
James B. Mehl Certain properties (such as heat capacity, entropy,
Bibliography. K. A. Gillis, J. B. Mehl, and M. R. and enthalpy increment) can be derived directly
Moldover, Theory of the Greenspan viscometer, J. from species-specific information such as spectro-
Acous. Soc. Amer., 114:166–173, 2003; J. J. Hury scopic measurements, electronic structure computa-
et al., The viscosity of seven gases measured tions of the electronic states for gas-phase species, or
with a Greenspan viscometer, Int. J. Thermophys., direct measurements of selected properties (for ex-
24:1441–1474, 2003. ample, heat capacity) for condensed-phase species.
However, the enthalpy and Gibbs energy of forma-
tion are obtained from determinations that express
these quantities relative to other chemical species.
Active Thermochemical Tables Examples of such species-interrelating determi-
Active Thermochemical Tables (ATcT; a software nations are bond dissociation energies, enthalpies
suite) are based on a distinctively different paradigm of chemical reactions, kinetic equilibria, electrode
of how to derive accurate, reliable, and internally potentials, and solubility data.
4 Active Thermochemical Tables

Species-interrelating determinations are tradition- related to the recent discovery that the generally
ally solved via a stepwise process usually following accepted value of the bond dissociation energy in
the “standard order of elements” (oxygen, hydro- water is in error. The primary vertices of the graph
gen, noble gases, halogens, and so on) pioneered by (boxes) represent the enthalpies of formation which
the National Bureau of Standards (NBS) compilation. need to be determined, while the secondary ver-
During each step, a new chemical species is adopted tices (ovals) represent the chemical reactions. Each
and available scientific information is scrutinized. of the numbers contained in the ovals reference one
The “best” species-interrelating measurements are thermochemically relevant species-interrelating de-
selected through a critical evaluation process and termination at a particular temperature. The directed
then are used to obtain, at one temperature, either edges (arrows) and their weights define participation
the enthalpy or Gibbs energy of formation for that in the chemical reactions.
species. One clear limitation is that only species- The graph conforms to a number of additional
interconnecting determinations that link the current rules. First-neighbor vertices are always of a differ-
species exclusively to species that have been com- ent kind, and second neighbors are always of the
piled during previous steps can be used. Once the same kind. The topology of the graph is driven by
enthalpy or Gibbs energy of formation is determined, the reactions it describes, which fixes the weights
the temperature dependence and the other thermo- for the edges and defines which vertices can be first
chemical properties can be computed from the and second neighbors.
available species-specific information. The thermo- In general, secondary vertices may have
chemical information for the chemical species under multiple degeneracies (reflecting competing species-
consideration is then adopted and used in subse- interrelating determinations of the same chemical
quent steps as a constant. reaction). The graph can be mapped onto one adja-
While the “standard order of elements” strategy cency matrix and two column vectors (Fig. 2). The
helps alleviate some of the problems of the sequen- columns and rows of the adjacency matrix corre-
tial process, the resulting tabulations have a num- spond to primary and secondary vertices (with each
ber of difficulties. The biggest problem is the hidden degenerate component forming a different row), and
progenitor/progeny dependencies across the tabula- the matrix elements reflect the weight and direction
tion. Consequently, traditional tabulations are nearly of the edges. The two column vectors have the same
impossible to update with new knowledge. At best, number of rows as the adjacency matrix, and their
one can use new species-interrelating data to update elements contain the values and adjunct uncertain-
the properties of one species, which is tantamount to ties of the species-interrelating determinations. Re-
revising one of the steps in the middle of the original moval of primary vertices that are considered fixed
sequence that produced the tabulation. While this (such as reference elements in their standard states),
improves things locally (for the species in question), coupled to modifications of the column vectors, as
it introduces new inconsistencies across the tabu- necessary, is a legitimate procedure in handling the
lation. Generally, there will be other species in the graph. The adjacency matrix and the two vectors
table that are linked directly or indirectly to the old correspond algebraically to a system of linear equa-
value of the revised species. These species also need tions. The matrix is sparse, and the system is usually
to be updated, but it is not explicit which species heavily overdetermined (the number of secondary
these may be. Other difficulties, such as cumulative vertices including all degeneracies normally exceeds
errors, are caused by lack of corrective feedback to the number of primary vertices).
the thermochemistry of species that have been de- Local thermochemical network. Another variant is a local
termined in previous steps and frozen. The sequen- thermochemical network, obtained by removing the
tial approach also produces uncertainties that are not primary vertices for which solutions are considered
necessarily properly quantified and do not reflect the to be firmly known from prior considerations. While
information content that is being used in other parts treatment of the global thermochemical network is
of the tabulation. Even under the best circumstances, the preferred approach, the use of local networks
the available information is exploited only partially can be helpful in some cases.
in this approach. A visual examination of the graph quickly reveals
Thermochemical network approach. The recogni- that there are many allowed paths between the two
tion that species-interconnecting information forms arbitrarily selected primary vertices. The traditional
a thermochemical network, together with general sequential approach uses only a small subset of pos-
pointers to proper statistical treatment, was formu- sible paths. Starting at a reference element in a stan-
lated a long time ago but never fully developed or dard state (which can be removed from the graph),
properly utilized. each of the sequential steps generally corresponds
Global thermochemical network. The thermochemical to selecting a trivial subgraph consisting of one sec-
network represented in Fig. 1 corresponds to a ondary vertex and one primary vertex, solving for the
global thermochemical network, where all primary primary vertex, fixing its value, and then removing
vertices except for reference elements in standard it from the network (together with any secondary
states (H2 and O2 at the bottom of the figure) are vertices that become disjointed during the proce-
treated as unknowns. Figure 1 provides a graphical dure). From the statistical viewpoint, the best solu-
representation of a small thermochemical network tion for the thermochemical network is obtained not
 Active Thermochemical Tables 5

1 20 21 1
OH+ 22 22a OH

OH → OH+ + e−
2
H2O → 1 1 H2O2 → 2 OH
OH+ + H + e− 1
16 17
14
18 19 15 H2O → OH + H

1
1
1
34
OH →
O+H
H2O 1 H2O2
1

1
1

1 1
H2O (
) → H2O 1 H2O2 (
) → H2O2

10 11
56
1/ H + 1/ O 12
H 2 2 2 2 O
→ OH

1 2 O2 → 2 O
H2 → 2 H 23 1

2 1
H2O (
) H2O2 (
)

1
1 1
1 1/
789 2 1/ 13
2
1
1
H2 + 1/2 O2 → H2O (
) 1/
1/
2 H2O2 (
) → H2O (
) + 1/2 O2
2

H2 O2

Fig. 1. Graphical representation of a small thermochemical network. The thermochemical network contains two types of
vertices and has directed and weighted edges. The primary vertices (denoted by boxes) represent the enthalpies of formation
of species which need to be determined (where the same chemical compound in a different aggregate state is properly
distinguished as a thermochemically different species). The two liquids bear the label (
), while the customary label indicating
gaseous state, (g), pertinent to all other species, has been omitted. The secondary vertices (ovals) represent the chemical
reactions. Each of the numbers contained in the ovals references one thermochemically relevant species- interrelating
determination at a particular temperature. The directed edges (arrows) define participation in the chemical reactions: arrows
pointing away from a species indicate reactants, and arrows pointing toward a species indicate products. The weights of the
edges (indicated next to the arrows) are determined by the stoichiometry of the reaction. The electrons balancing the
chemical reactions are not shown explicitly since the thermochemical network conforms to the “stationary electron
convention.”

by selecting a particular path but by considering all the presence of alternative paths in the graph. Dur-
paths. This is accomplished by finding the simultane- ing each iteration the uncertainty of one secondary
ous solution of the whole system via minimization of vertex (the current worst offender) is slightly ex-
a suitable statistical measure, such as the chi-square panded (usually by a few percent), and the proce-
distribution χ 2, if the adjunct uncertainties are an dure is repeated until the thermochemical network
honest representation of the underlying confidence is self-consistent, at which point the final solutions
in the species-interrelating determination present in for all primary vertices can be found. These are then
the thermochemical network. However, if the latter coupled to species-specific information to develop
is not fulfilled, “optimistic” uncertainties create out- the full complement of thermochemical information.
liers that will skew the results. Hence, simultaneous Advantages of thermochemical network approach.
solution needs to be preceded by a statistical anal- The solutions and their adjunct uncertainties are
ysis that will detect and correct possible optimistic guaranteed to be consistent both internally and with
uncertainties. Among various statistical approaches all the knowledge stored in the thermochemical net-
that are possible, the “worst offender” analysis has work, thus producing thermochemical values that
proven to be very successful. In this iterative ap- are superior to those obtained from a sequential ap-
proach, trial solutions are repeatedly used to uncover proach. In addition, the resulting thermochemistry
optimistic uncertainties in the thermochemical net- is easily updated with new knowledge. New infor-
work. The isolation of offenders is made possible by mation is simply added to the network and the
6 Active Thermochemical Tables

system is solved again, propagating properly the con- statistical analysis of the thermochemical network is
sequences throughout the resulting thermochemical capable of isolating the “weakest links” in the ex-
tables. isting knowledge, thus identifying new experiments
Another exciting feature is the possibility of run- or computations that will enhance the resulting ther-
ning “what if” scenarios (hypothesis testing). New mochemistry. This alone is a new paradigm for the
or tentative data are easily tested for consistency efficient use of limited laboratory and computational
against the existing body of knowledge. If the tested resources.
hypothesis is inconsistent with the existing knowl- The table lists the enthalpies of formation at
edge, the statistical analysis will identify the conflict- 298.15 K (77◦F) obtained by solving the small ther-
ing information, allowing its reanalysis. Similarly, a mochemical network shown in Fig. 1, and provides
an illustration of what can be expected from this
approach. The species involved in this network are
H2O (
) of fundamental importance and are generally consid-
H2 + 1/2 O2 → H2O (
) ered to be already well-established via conventional
1
789 approaches. Not surprisingly, the literature values for
1 1/
water (which is historically one of the most studied
2
substances) are not significantly affected. However,
H2 O2
the improvements for the other species are quite sig-
nificant.
Web and grid servers. Active Thermochemical
Tables are based on the thermochemical network
approach. While it is possible to run ATcT as a self-
standing application on a personal computer, ATcT is
currently available through a framework of Web and
grid services using servers at Argonne National Lab-
oratory near Chicago. These services are an integral
∆rH (7) +δ part of the Collaboratory for Multi-Scale Chemical
0 0 0 1 –1 –0.5 0 0 0 0 − r (7)
∆rH (8) +δ Science (CMCS) and are accessible to users via its
0 0 0 1 –1 –0.5 0 0 0 0 − r (8)
∆rH (8) +δ Web portal (Fig. 3).
0 0 0 1 –1 –0.5 0 0 0 0 − r (8)
CMCS is one of the Scientific Discovery through
Advanced Computing (SciDAC) National Collabora-
tory projects funded by the Office of Science of
the U.S. Department of Energy (DOE). CMCS
brings together leaders in scientific research and
technological development across multiple DOE

Enthalpies of formation at 298.15 K, f H ° (298 K),

obtained by solving the small thermochemical network
shown in Fig. 1, together with literature values
Eq. (7): ∆ f H(H2O <
>) − ∆ fH(H2) − 0.5 ∆ fH(O2) = ∆rH (7) ± δr (7)
Chemical fH (298 K) from f H (298 K) from

Eq. (8): ∆ f H(H2O <
>) − ∆ fH(H2) − 0.5 ∆ fH(O2) = ∆rH (8) ± δr (8) speciesa ATcT, kJ/mol literature, kJ/mol

O (g) 249.2291 0.0021 249.18 0.10b,c,d

Eq. (9): ∆ f H(H2O <
>) − ∆ fH(H2) − 0.5 ∆ fH(O2) = ∆rH (9) ± δr (9) H (g) 217.99781 0.00010 217.998 0.006b,c,d
H2 O ( ) 285.826 0.039 285.830 0.040b,c,d
Fig. 2. Mapping of a selected portion (a subgraph) of the small thermochemical network H2 O (g) 241.822 0.039 241.826 0.040b,c,d
depicted in Fig. 1 onto the adjacency matrix and column vectors. This selected subgraph OH (g) 37.325 0.047 38.99 1.2c
corresponds to the chemical reaction H2 + 1/2 O2 → H2O (
) and hence contains three 39.349 0.21d
primary vertices (gray boxes in the graph) denoting the chemical species and one 37.3 0.3e
secondary vertex denoting the reaction (the upper oval in the graph). The secondary OH (g) 1293.060 0.052f 1310.9 0.5f,c
vertex has a triple degeneracy, reflecting the fact that there are three competitive 1284.1 5.0f,d
experimental measurements for the enthalpy of this reaction, denoted by equations 1293.0 0.3f,e
(7), (8), and (9). The primary vertices denoting the enthalpies of formation of H2, O2, and H2 O2 ( ) 187.695 0.065 187.78 0.08d
H2O (
) correspond to the marked columns of the adjacency matrix. The triple degeneracy
H2 O2 (g) 135.805 0.086 136.106c
of the secondary vertex produces the three marked rows of the adjacency matrix and the
135.88 0.22d
two column vectors. The styles and directions of the edges (arrows) that connect the
primary and secondary vertices of the subgraph determine the algebraic signs and the a The suffix (g) denotes a species gaseous state, and ( ) denotes a
numeric values of the nonzero elements of the adjacency matrix. The appropriate
liquid.
elements of the two column vectors are populated by the three similar (but not quite b J. D. Cox, D. D. Wagman, and V. A. Medvedev, CODATA Key Values
identical) measured values and the adjunct uncertainties for the enthalpy of this reaction. for Thermodynamics, Hemisphere, New York, 1989.
The rows of the adjacency matrix and the column vectors map onto the linear equations c M. W. Chase, Jr. (ed.), NIST-JANAF Thermochemical Tables, 4th ed.,
at the bottom of the figure. It should be noted that the vertices that correspond to J. Phys. Chem. Ref. Data, Monog. No. 9, 1998.
d L. V. Gurvich, I. V. Veyts, and C. B. Alcock, Thermodynamic
enthalpies of formation of the species that are fixed (in the present case, H2 and O2, which
are elements in their reference states) can be removed from the graph, modifying, when Properties of Individual Substances, vol. 1, pts. 1 and 2, Hemisphere,
necessary, the values of the secondary vertex. The action is equivalent to moving the New York, 1989.
e B. Ruscic et al., J. Phys. Chem. A, 106:2727, 2002.
appropriate enthalpies of formation from the left side of the equations to the right side, f The value is given in the “stationary electron convention”; the
and modifying accordingly the elements of the column vectors (leading in this particular corresponding 298.15 K value in the “thermal electron convention” can
case to no numerical changes to the right side of the equations, since the enthalpies of be obtained by adding 6.197 kJ/mol.
formation of H2 and O2 are fixed to zero by thermochemical conventions).
 Active Thermochemical Tables 7

Fig. 3. Active Thermochemical Tables front-end portlet within the community portal of the Collaboratory for Multi-Scale
Chemical Science (http://www.cmcs.org). Users can access the full functionality of ATcT and associated services run at a
remote server. The configurable sidebar shows the various software tools available in the workspace, while the lower half of
the environment allows remote handling of data in the CMCS database.

laboratories, other government laboratories, and aca- ergy, Division of Chemical Sciences, Geosciences
demic institutions to develop an open “knowledge and Biosciences of the Office of Basic Energy Sci-
grid” for multiscale informatics–based chemistry ences, and by the Mathematical, Information, and
research. Computational Science Division of the Office of
ATcT is the central application on the thermo- Advanced Scientific Computing Research, under
chemical scale of CMCS. ATcT consists of several Contract No. W-31-109-ENG-38.
parts: the software kernel, the user interface with the For background information see CHEMICAL
framework of services, and the underlying databases. KINETICS; CHEMICAL THERMODYNAMICS; ENTHALPY;
Both the software and the databases are under con- ENTROPY; GIBBS FUNCTION; HEAT CAPACITY;
tinuous development at Argonne National Labora- PHYSICAL CHEMISTRY; PHYSICAL ORGANIC CHEM-
tory. The software suite allows queries of existing ISTRY; THERMOCHEMISTRY in the McGraw-Hill
data, as well as visualization and manipulation of ther- Encyclopedia of Science & Technology.
mochemical networks. Users can set a variety of op- Branko Ruscic
tions that direct the mode in which the databases Bibliography. B. Ruscic et al., Introduction to Active
are queried, in which the results presented, or in the Thermochemical Tables: Several “key” enthalpies of
handling of thermochemical networks. formation revisited, J. Phys. Chem. A, 108(45):9979–
The ATcT databases are organized as a series of li- 9997, 2004; B. Ruscic et al., Ionization energy of
braries. The main library contains a thermochemical methylene revisited: Improved values for the en-
network that currently has over 200 thermochemical thalpy of formation of CH2 and the bond dissocia-
species and is growing daily. The auxiliary libraries tion energy of CH3 via simultaneous solution of the
provide historical reference data from standard com- local thermochemical network, J. Phys. Chem. A,
pilations. Users have the opportunity to establish 103(43):8625–8633, 1999; B. Ruscic et al., On the
their own “mini libraries” in which they can store enthalpy of formation of hydroxy radical and gas-
data that supplements or modifies the information phase bond dissociation energies of water and hy-
contained in the central and auxiliary libraries. As droxyl, J. Phys. Chem. A, 106(11):2727–2747, 2002;
new scientific results are obtained from the thermo- B. Ruscic et al., Simultaneous adjustment of experi-
chemical network’s main library, they will be pub- mentally based enthalpies of formation of CF3X,
lished in the scientific literature. X = NIL, H, Cl, Br, I, CF3, CN, and a probe of G3
The development of Active Thermochemical theory, J. Phys. Chem. A, 102(52):10889–10899,
Tables is supported by the U.S. Department of En- 1998.
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