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AN EXPERIMENTAL SCIENCE




CHEMICAL EDUCATION MATERIAL STUDY



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<wi$, the one-millionth copy of 1

CHEMISTRY:

AN EXPERIMENTAL SCIENCE

isvrescntedto
die President and Regents oftlic University of-*
California to commemorate the University s
contribution to tlu eminently successfub :
development of a hujh school chemistry
cutriculum. rm 7his project was made-^
possible by arrant from thelsational
Science Foundation. CRoy aides were-^
returned to tlieU.S.Treasury as complete
repayment f the aran v. <~jlieyrojecZ y
directed by faculty of tlu University of
California and of Harvey Mudd College,
resulted iru> tins textbook, a laboratoiy
manual, a teadier'sguidej ancLo
twenty-seven associated funis.



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INTERNATIONAL ATOMIC WEIGHTS







ATOMIC


ATOMIC






ATOMIC


ATOMIC


NAME


SYMBOL


NUMBER


WEIGHT


NAME


SYMBOL


NUMBER


WEIGHT


Actinium


Ac


89


(227)


Mercury


Hg


80


200.6


Aluminum


Al


13


27.0


Molybdenum


Mo


42


95.9


Amencium


Am


95


(243)


Neodymium


Nd


60


144.2


Antimony


Sb


51


121.8


Neon


Ne


10


20.2


Argon


Ar


18


39.9


Neptunium


Np


93


(237)


Arsenic


As


33


74.9


Nickel


Ni


28


58.7


Astatine


At


85


(210)


Niobium


Nb


41


92.9


Barium


Ba


56


137.3


Nitrogen


N


7


14.01


Berkelium


Bk


97


245


Osmium


Os


76


190.2


Beryllium


Be


4


9.01


Oxygen


O


8


16.00


Bismuth


Bi


83


209.0


Palladium


Pd


46


106.4


Boron


B


5


10.8


Phosphorus


P


15


31.0


Bromine


Br


35


79.9


Platinum


Pt


78


195.1


Cadmium


Cd


48


112.4


Plutonium


Pu


94


(242)


Calcium


Ca


20


40.1


Polonium


Po


84


210


Californium


Cf


98


(251)


Potassium


K


19


39.1


Carbon


C


6


12.01


Praseodymium


Pr


59


140.9


Cerium


Ce


58


140.1


Promethium


Pm


61


(147)


Cesium


Cs


55


132.9


Protactinium


Pa


91


(231)


Chlorine


CI


17


35.5


Radium


Ra


88


(226)


Chromium


Cr


24


52.0


Radon


Rn


86


(222)


Cobalt


Co


27


58.9


Rhenium


Re


75


186.2


Copper


Cu


29


63.5


Rhodium


Rh


45


102.9


Curium


Cm


96


(247)


Rubidium


Rb


37


85.5


Dysprosium


Dy


66


162.5


Ruthenium


Ru


44


101.1


Einsteinium


Es


99


(254)


Samarium


Sm


62


150.4


Erbium


Er


68


167.3


Scandium


Sc


21


45.0


Europium


Eu


63


152.0


Selenium


Se


34


79.0


Fermium


Fm


100


(253)


Silicon


Si


14


28.1


Fluorine


F


9


19.0


Silver


Ag


47


107.9


Francium


Fr


87


(223)


Sodium


Na


11


23.0


Gadolinium


Gd


64


157.3


Strontium


Sr


38


87.6


Gallium


Ga


31


69.7


Sulfur


S


16


32.1


Germanium


Ge


32


72.6


Tantalum


Ta


73


180.9


Gold


Au


79


197.0


Technetium


Tc


43


(99)


Hafnium


Hf


72


178.5


Tellurium


Te


52


127.6


Helium


He


2


4.00


Terbium


Tb


65


158.9


Holmium


Ho


67


164.9


Thallium


Tl


81


204.4


Hydrogen


H


1


1.008


Thorium


Th


90


232.0


Indium


In


49


114.8


Thulium


Tm


69


168.9


Iodine


I


53


126.9


Tin


Sn


50


118.7


Iridium


Ir


77


192.2


Titanium


Ti


22


47.9


Iron


Fe


26


55.8


Tungsten


W


74


183.9


Krypton


Kr


36


83.8


Uranium


U


92


238.0


Lanthanum


La


57


138.9


Vanadium


V


23


50.9


Lead


Pb


82


207.2


Xenon


Xe


54


131.3


Lithium


Li


3


6.94


Ytterbium


Yb


70


173.0


Lutetium


Lu


71


175.0


Yttrium


Y


39


88.9


Magnesium


Mg


12


24.3


Zinc


Zn


30


65.4


Manganese


Mn


25


54.9


Zirconium


Zr


40


91.2


Mendelevium


Md


101


(256)











Parenthetical names refer to radioactive elements; the mass number (not the atomic weight) of the isotope with largest
half-life is usually given.

* Latest values recommended by the International Union of Pure and Applied Chemistry, 1961.



CHEMISTRY

AN EXPERIMENTAL SCIENCE



CHEMISTRY

Prepared by
CHEMICAL EDUCATION MATERIAL STUDY

Under a grant from
THE NATIONAL SCIENCE FOUNDATION




Editor: GEORGE C. PIMENTEL, University of California, Berkeley, California

Associate Editors

BRUCE H. MAHAN, University of California, Berkeley, California

A. L. McCLELLAN, California Research Corporation, Richmond, California

KEITH MacNAB, Sir Francis Drake High School, San Anselmo, California

MARGARET NICHOLSON, Acalanes High School, Lafayette, California

An Experimental Science



Contributors

ROBERT F. CAMPBELL

Miramonte High School, Orinda, California

JOSEPH E. DAVIS, JR.

Miramonte High School, Orinda, California

SAUL L. GEFFNER

Forest Hills High School, Forest Hills, New York

THEODORE A. GE1SSMAN

University of California, Los Angeles, California

MELVIN GREENSTADT

Fairfax High School, Los Angeles, California

CARL GRUHN

South Pasadena High School, South Pasadena, California

EDWARD L. HAENISCH

Wabash College, Crawfordsville, Indiana

ROLFE H. HERBER

Rutgers University, New Brunswick, New Jersey

C. ROBERT HURLEY

Sacramento State College, Sacramento, California

LAWRENCE D. LYNCH, JR.

Beverly Hills High School, Beverly Hills, California



LLOYD E. MALM

University of Utah, Salt Lake City, Utah

CLYDE E. PARRISH

Cubberley Senior High School, Palo Alto, California
ROBERT W. PARRY

University of Michigan, Ann Arbor, Michigan

EUGENE ROBERTS

Polytechnic High School, San Francisco, California

MICHELL J. SIENKO

Cornell University, Ithaca, New York

ROBERT SILBER

American Chemical Society, Washington, D.C.

HARLEY L. SORENSEN

San Ramon Valley Union High School, Danville, California

LUKE E. STEINER

Oberlin College, Oberlin, Ohio

MODDIE D. TAYLOR

Howard University, Washington, D.C.

ROBERT L. TELLEFSEN

Napa High School, Napa, California



Director: J. ARTHUR CAMPBELL, Harvey Mudd College, Claremont, California
Chairman: GLENN T. SEABORG, University of California, Berkeley, California



W. H. FREEMAN AND COMPANY, Cooperating Publishers

SAN FRANCISCO



© Copyright 1960, 1961, 1962, 1963 by The Regents of the University of California.

The University of California reserves all rights to reproduce this book,
in whole or in part, with the exception of the right to use
short quotations for review of the book.

Printed in the United States of America.

Library of Congress Catalog Card Number: 63-18323.

ISBN: 0-7 167-0001 -8

20



Preface



Chemistry deals with all of the substances that
make up our environment. It also deals with the
changes that take place in these substances —
changes that make the difference between a cold
and lifeless planet and one that teems with life
and growth. Chemistry helps us understand and
benefit from nature's wondrous ways.

Chemistry is an important part of what is
called science. Since every phase of our daily
life is affected by the fruits of scientific activity,
we all should know what scientific activity is,
what it can do, and how it works. The study of
chemistry will help you learn these things.

CHEMISTR Y — An Experimental Science pre-
sents chemistry as it is today. It does so with
emphasis upon the most enjoyable part of chem-
istry: experimentation. Unifying principles are
developed, as is appropriate in a modern chemis-
try course, with the laboratory work providing
the basis for this development. When we are
familiar with these widely applicable principles
we no longer have need for endless memorization
of innumerable chemical facts. To see these prin-
ciples grow out of observations you have made

January 1963



in the laboratory gives you a valid picture of
how all scientific advances begin. It permits you
to engage in scientific activity and thus, to some
extent, to become a scientist yourself.

At the end of this course you won't know all of
chemistry. We hope that you will know enough
chemistry and enough about science to feel that
the part you don't know is understandable, not
mysterious. Perhaps you will appreciate the great
power of scientific methods and appreciate their
limitations. We hope that you will have become
practiced in making unexpected observations, in
weighing facts, and in framing valid conclusions.
We hope that you will have formed the habit of
questioning and of seeking understanding rather
than being satisfied with blind acceptance of
dogmatic assertions. We expect that you will
share in the excitement of science and that you
will feel the rich pleasure that comes with dis-
covery. If most of these hopes are fulfilled, then
you have had an optimum introduction to sci-
ence through chemistry. Nothing could be a
more important part of your education at a time
when science is molding our age.

GEORGE C. PIMENTEL

Editor for the Chemical

Education Material Study



Foreword



This textbook was prepared over a three year
period by a group of university and high school
chemistry teachers under a grant from the Na-
tional Science Foundation. The project, called
CHEM Study, was organized and directed on
broad policy lines by a Steering Committee of
nationally known teachers and pre-eminent sci-
entists from a variety of chemical fields. The
Steering Committee, headed by Nobel Laureate
Glenn T. Seaborg, attempted to staff the study
with the country's most able university scientists
and high school teachers. The university profes-
sors were drawn from all over the United States
on the basis of demonstrated understanding of
science and recognized leadership in teaching it.
The names of the contributors to this text al-
ready appear on more than a dozen widely
accepted college level textbooks. An equal num-
ber of outstanding high school teachers were
named as contributors, each one individually
selected on the basis of enthusiastic recommen-
dations by his peers. These teachers participated
in every phase of the preparation of this course.
The effort of these highly qualified persons,
totaling over fifteen man-years, is summed in the
CHEM Study course. The National Science
Foundation deserves commendation for making
such activities possible; never before has such
an array of talent been assembled to construct
a high school chemistry course.



The textbook, CHEMISTR Y—An Experimen-
tal Science, is designed for a high school intro-
ductory chemistry course and it is meshed closely
with an accompanying Laboratory Manual and a
set of pertinent films. A comprehensive Teachers
Guide is available to aid teachers in gaining
familiarity with the course. The first editions of
the textbook and laboratory manual, written
during the summer of 1960, were used during
1960-1961 in 23 high schools and one junior
college by about 1300 students. During this first
year, there was weekly staff contact with the
pioneering teachers. On the basis of their experi-
ence, the materials were revised during the
summer of 1961 and the T eachers Guide was
written. This second edition was used in 123
high schools and 3 junior colleges scattered over
the country and involving 13,000 students. Again
the closely monitored field experience founded
the third and final revision. The course, essen-
tially in the form presented here, was used during
1962-1963 in 560 high schools in 46 states by
about 45,000 randomly selected students. Its
teachability is assured.

The title, CHEMISTRY— An Experimental
Science, states the theme of this one year course.
A clear and valid picture of the steps by which
scientists proceed is carefully presented and re-
peatedly used. Observations and measurements
lead to the development of unifying principles

vii



VI11



FOREWORD



and then these principles are used to interrelate
diverse phenomena. Heavy reliance is placed
upon laboratory work so that chemical prin-
ciples can be drawn directly from student ex-
perience. Not only does this give a correct and
nonauthoritarian view of the origin of chemical
principles, but it gives maximum opportunity
for discovery, the most exciting part of scientific
activity. This experimental theme is supported
by a number of films to provide experimental
evidence that is needed but not readily available
in the classroom because of inherent danger,
rarity, or expense.

The initial set of experiments and the first few
textbook chapters lay down a foundation for the
course. The elements of scientific activity are
immediately displayed, including the role of un-
certainty. The atomic theory, the nature of
matter in its various phases, and the mole con-
cept are developed. Then an extended section of
the course is devoted to the extraction of im-
portant chemical principles from relevant labo-
ratory experience. The principles considered
include energy, rate and equilibrium character-
istics of chemical reactions, chemical periodicity,
and chemical bonding in gases, liquids, and
solids. The course concludes with several chap-
ters of descriptive chemistry in which the ap-
plicability and worth of the chemical principles
developed earlier are seen again and again.

There are a number of differences from more
traditional courses. The most obvious are, of
course, the shift of emphasis from descriptive
chemistry toward chemical principles to repre-
sent properly the change of chemistry over the
last two decades. Naturally, this reconstruction
of the entire course gives a unique opportunity
to delete obsolete terminology and out-moded
material. Less obvious but perhaps more im-
portant is the systematic development of the
relationship between experiment and theory.
Chemistry is gradually and logically unfolded,
not presented as a collection of facts, dicta, and
dogma. We hope to convey an awareness of the
significance and capabilities of scientific activities
that will help the future citizen assess calmly and
wisely the growing impact of technological ad-
vances on his social environment. Finally, we



have striven for closer continuity of subject
matter and pedagogy between high school and
modern freshman chemistry courses for those
students who will continue their science training.

We do believe that the CHEM Study course
achieves the goals we have set. Experience has
shown that the course is interesting to and within
the grasp of the average high school chemistry
student and that it challenges and stimulates
the gifted student. The course content provides
a strong foundation for the college-bound stu-
dent. Inevitably the question arises, "Is this
course better than (or, as good as) the traditional
one?" An answer is not readily found in com-
parative tests. A CHEM Study student might be
handicapped in a test that has little emphasis
upon principles, that is heavily laden with de-
scriptive "recall questions," or that uses obsolete
terminology. Conversely, a test designed specif-
ically for the modern CHEM Study course
content would surely prejudice against a student
with a traditional preparation. The issue can-
not be completely resolved "objectively" be-
cause value judgments are ultimately involved.
Whether the CHEM Study goals are valid and
the approach is reasonable must be decided with
due consideration to the reported experience of
teachers and to the credentials of those who
developed the materials.

There are numberless ways in which CHEM
Study is indebted to the University of California
and to Harvey Mudd College for contributions
of facilities, personnel, and encouragement. We
acknowledge with thanks the stimulation and
support we have received from the National
Science Foundation. Finally, the Staff feels a
heavy debt of gratitude to all of those who
participated so energetically and enthusiastically
in the preparation of the CHEM Study mate-
rials. We thank the Steering Committee for their
valued and helpful guidance. We thank the con-
tributors listed on the title page for their dedica-
tion of time, interest, and their ample talents to
this effort. We acknowledge especially the key
roles of Mr. Joseph Davis, Mr. Saul Geffner,
Mr. Keith MacNab, Miss Margaret Nicholson,
and Mr. Harley Sorensen. These individuals not
only used the CHEM Study materials in the



FOREWORD



classroom but also served continuously as staff
members. Their contributions and critiques have
greatly increased the teachability of the CHEM
Study course. We thank the many teachers who
used the trial editions in their classrooms; their
careful scrutiny of the text and laboratory man-
ual and their many valuable suggestions pro-



vided a firm basis for revisions. Finally, we thank
the many students who labored through the trial
versions of CHEM Study; their every reaction —
pain or pleasure, enthusiasm or ennui, spark or
sputter— was noted and lent to the improvement
of the course.



J. ARTHUR CAMPBELL,

Director, Chemical Education Material Study
Harvey Mudd College

GEORGE C. PIMENTEL,

Editor, Textbook
University of California

Berkeley, California
January, 1963



LLOYD E. MALM

Editor, Laboratory Manual
University of Utah

A. L. MCCLELLAN

Editor, Teachers Guide

California Research Corporation

DAVID RIDGWAY

Producer, Films



Acknowledgments



Quotations appearing on the following pages are
used, with permission, from the indicated sources.

Page 1 History of Science, W. Dampier. New
York: Cambridge University Press, 1949.
17 Principia, Isaac Newton. Mott's transla-
tion revised by F. Cajori. Berkeley: Uni-
versity of California Press, 1934, p. 673.
38 New Systems of Chemical Philosophy,
John Dalton. Manchester, England, 1810.
49 Readings in the Literature of Science,
W. C. Dampier and M. Dampier. New
York: Harper and Row, 1959, p. 100.
65 Solutions, W. Ostwald. London: Long-
mans, Green and Co., 1891.
Letter by J. A. R. Newlands, Chemical
News, Vol. 10, 1864, p. 94.
Chemical Thermodynamics, A Course of
Study, Frederick T. Wall. San Francisco:
W. H. Freeman and Company, 1958, p. 2.

124 The Drift Toward Equilibrium, H. Ey-
ring, from Science in Progress, Fourth
Series, edited by G. A. Baitsell, New
Haven: Yale University Press, 1945, p.
169.

142 Thermodynamics, G. N. Lewis and
M. Randall. New York: McGraw-Hill
Book Co., Inc., 1923, p. 18.

163 Solubility of Non-electrolytes, J. H. Hilde-
brand. New York: Reinhold Publishing
Corp., 1936, p. 13.



85



108



179 Elements of Chemistry, A. Lavoisier. New
York, 1806, p. 14.

199 Predictions and Speculation in Chemis-
try, W. M. Latimer, Chemical and Engi-
neering News, Vol. 31, 1953, p. 3366.

224 Textbook of Quantitative Inorganic Anal-
ysis, I. M. Kolthoff and E. B. Sandell.
New York: Macmillan, 1936, p. 2.

233 The Rise of Scientific Philosophy, Hans
Reichenbach. Berkeley: University of
California Press, 1956, p. 168.

252 Valence, C. A. Coulson. New York: Ox-
ford University Press, 1961, p. 3.

274 Chemical Analysis by Infrared, Bryce
Crawford, Jr., New York: Scientific
American, Oct. 1953.

300 The Nature of the Chemical Bond,
L. Pauling. Ithaca: Cornell University
Press, 1939, p. 422.

321 Les Prix Nobel, 1947, Nobel lecture by
R. Robinson. Stockholm: Norstedt and
Soner, 1947, p. 110.

421 From Quantum Chemistry to Quantum
Biochemistry, Alberte Pullman and Ber-
nard Pullman, in Albert Szent-Gyoergyi
and Modern Biochemistry, edited by Rene
Wurmser. Paris: Institute of Biology,
Physics, Chemistry, 1962.

xi



Xll



ACKNOWLEDGMENTS



436 Genesis of Life, J. B. S. Haldane, in The
Earth and Its Atmosphere, edited by D. R.
Bates. New York: Basic Books, Inc.,
1960.

The following photographs are used with permission
from the indicated source.

Frontispiece The Candle— Illuminating Chemistry,
by Bernard Abramson.
Page 5 Ice melting, by Ross H. McGregor.
5 Aluminum melting, courtesy Alumi-
num Corporation of America.
5 Solder melting, by Charles L. Finance.
48 G. N. Lewis, courtesy the Hagemeyer
Collection, Bancroft Library, Univer-
sity of California.
94 Cutting potassium, by Charles L. Fi-
nance.
107 D. Mendeleev, courtesy the Univer-
sity of Leningrad.
141 H. Eyring, courtesy H. Eyring.
198 S. Arrhenius, courtesy The Bettmann
Archive.



299 L. Pauling, courtesy The California
Institute of Technology.

310 Network silicates, by Charles L. Fi-
nance.

312 Sodium chloride crystals, by Charles
L. Finance.

320 P. Debye, courtesy Cornell Univer-
sity.

351 R. Robinson, courtesy Canadian In-
dustries Limited.

386 A. Stock, courtesy The American
Chemical Society.

420 G. T. Seaborg, courtesy California
Research Corporation, Richmond
Laboratory, Richmond, California.

435 R. B. Woodward, courtesy The Am-
erican Chemical Society.

Color plate I Elements and compounds, by
Charles L. Finance.
II Indicator colors, by Charles L.

Finance.
Ill Spectrograph, by Charles L.
Finance.



Contents



Chapter 1. Chemistry: An Experimental Science 1

2. A Scientific Model: The Atomic Theory 17

3. Chemical Reactions 38

4. The Gas Phase: Kinetic Theory 49

5. Liquids and Solids: Condensed Phases of Matter 65

6. Structure of the Atom and the Periodic Table 85

7. Energy Effects in Chemical Reactions 108

8. The Rates of Chemical Reactions 124

9. Equilibrium in Chemical Reactions 142

10. Solubility Equilibria 163

11. Aqueous Acids and Bases 179

12. Oxidation-Reduction Reactions 199

13. Chemical Calculations 224

14. Why We Believe in Atoms 233

15. Electrons and the Periodic Table 252

16. Molecules in the Gas Phase 274

17. The Bonding in Solids and Liquids 300

18. The Chemistry of Carbon Compounds 321

19. The Halogens 352

20. The Third Row of the Periodic Table 364

21. The Second Column of the Periodic Table 377

22. The Fourth-Row Transition Elements 387

an



XIV CONTENTS

23. Some Sixth- and Seventh-Row Elements 41 1

24. Some Aspects of Biochemistry: An Application of Chemistry 421

25. The Chemistry of Earth, the Planets, and the Stars 436

Appendix 1. A Description of a Burning Candle 449

2. Relative Strengths of Acids in Aqueous Solution 451

3. Standard Oxidation Potentials for Half-Reactions 452

4. Names, Formulas, and Charges of Some Common Ions 454
Index 455




THE CANDLE — ILLUMINATING CHEMISTRY



CHAPTER



l



Chemistry:

An Experimental

Science



• • • those sciences are vain and full of errors which are not born from
experiment, the mother of all certainty. • • •

LEONARDO DA VINCI, 1452-1519



Many words have been spoken and written in
answer to the questions:

"What is the nature of scientific study?"
"What is the nature of chemistry?"

We shall try to find the answers in this course,
not through words alone, but through experi-
ence. No one can completely convey through
words the excitement and interest of scientific



discovery. Hence we shall see the nature of sci-
ence by engaging in scientific activity. We shall
see the nature of chemistry by considering prob-
lems which interest chemists.

Our starting point will be based on examples
of the activities of science, rather than on defini-
tions. We will perform these activities, beginning
on familiar ground. On such ground, where you
know the answer, you will best see the steps by
which science advances.



1-1 THE ACTIVITIES OF SCIENCE

Every form of life "feels" its surroundings in one
way or another. In response to the feel of the
surroundings, it behaves according to a pattern
which tends to prolong its existence.

A tree is illuminated by the morning sunshine.
In response, the leaves of the tree turn on their



stems to present full surface to the light. This
movement causes the leaves to intercept more
light, and light is the source of energy which runs
the amazing chemical factory operated by the
tree. The tree grows.
A bear feels that summer is over — perhaps by

l



chemistry: an experimental science I CHAP. 1



the length of the day or by the color of fall
leaves, perhaps by some ursine almanac humans



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