Course notes on the interpretation of infrared and Raman spectra

582 Pages·2003·13.787 MB·English

by  Dana W Mayo, Foil A Miller, R W Hannah

COURSE NOTES ON THE
INTERPRETATION OF
INFRARED AND
RAMAN SPECTRA
Dana W. Mayo
Foil A. Miller
Robert W. Hannah
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LibraryofCongressCataloging-in-PublicationData:
Miller,FoilA.
CoursenotesontheinterpretationofinfraredandRamanspectra/FoilA.Miller,
DanaW.Mayo,RobertW.Hannah.
p. cm.
Includesbibliographicalreferencesandindex.
ISBN0-471-24823-1(cloth)
1.Ramanspectroscopy. 2.Infraredspectra. I.Mayo,DanaW. II.Hannah,R.W.
(RobertWesley),1931- III. Title.
QD96.R34M55 2004
5430.57–dc22 2004000637
PrintedintheUnitedStatesofAmerica
10 9 8 7 6 5 4 3 2 1
Itis with great pleasureandaffectionthatwe dedicatethisbooktothe memory of
fourpersonswhoplayedenormouslyimportantrolesindevelopingandteachingthe
courseonwhichitisbased(theMIT/BowdoinCollegecourseonTheInterpretation
of Infrared and Raman Spectra), but who are no longer with us.
ProfessorRichardC.LordofMassachusettsInstituteofTechnologyfoundedthe
coursein1950,taughtinitfor32years,andmaintainedanactiveinterestuntilhis
death in 1989.
Professor Ellis R. Lippincott of the University of Maryland participated from
1952 to 1974. His colorful personality and unique lecturing style will long be
remembered.
Dr. Lionel J. Bellamy of the Explosives Research and Development Establish-
ment, Waltham Abby, England was a stalwart of the staff for 22 years. He is well
known as the author of several pioneering, widely-used, and influential books on
infrared group frequencies. Hewas as colorful lecturer with a tremendous amount
of information on the subject.
Dr.HarryWillisofImperialChemicalIndustries,Englandbroughtanextensive
knowledge of polymer spectroscopy to his lectures, which extended from 1978 to
1990 (13 years).
All of these individuals contributed to the notes contained herein, and are all
greatly missed.
THE AUTHORS
CONTENTS
Foreword ix
Preface xv
1 Introduction 1
FoilA.Miller
2 Characteristic Frequencies of Alkanes 33
DanaW.Mayo
3 Characteristic Frequencies of Alkenes (Olefins) 73
FoilA.Miller
4 Characteristic Frequencies of Molecules with Triple Bonds
and Cumulated Double Bonds 85
RobertW.HannahandFoilA.Miller
5 Characteristic Frequencies of Aromatic Compounds
(Group Frequencies of Arenes) 101
DanaW.Mayo
Introduction to Exercises 141
Exercise Section I 145
6 Spectra of X–H Systems (With Emphasis on O(cid:1)(cid:1)H and
N(cid:1)(cid:1)H Groups) 163
FoilA.Miller
7 Spectra of Carbonyl Compounds of All Kinds (Factors Affecting
Carbonyl Group Frequencies) 179
DanaW.Mayo
8 Amides, Carboxylate Ion, and C(cid:1)(cid:1)O Single Bonds 205
FoilA.Miller
9 Groups Containing N(cid:1)(cid:1)(cid:1)(cid:1)O Bonds, or Si, P, S, or Halogen Atoms 217
RobertW.Hannah
Exercise Section II 247
vii
viii CONTENTS
10 Infrared Spectra of Polymers: Introduction 261
RobertW.HannahandDanaW.Mayo
11 Infrared Spectra of Inorganic Materials 297
FoilA.Miller
12 Survey of Infrared and Raman Group Frequencies 355
DanaW.Mayo
Exercise Section III 399
13 Sample-Handling Techniques 425
RobertW.Hannah
14 Infrared Spectra of Mixtures 461
RobertW.Hannah
Answers to Chapter 5 Figure 5.30 505
Answers to Exercises 509
Bibliography 549
Index 559
FOREWORD
HISTORY OF THE MIT–BOWDOIN COLLEGE SUMMER INFRARED
COURSE: FIRST 51 YEARS—1950–2000
FOIL A. MILLER
TheMIT–BowdoinCollegesummercourseoninfraredspectroscopyistheworld’s
longest running short course on this subject. During its first 51 years of operation,
over 6900 student-weeks of training have been offered. Consequently it has had a
large impact on the use of this technique.
Apparatus for infrared spectroscopy became commercially available at the end
of World War II. After a few years, instrument manufacturers became concerned
thattheirsaleswouldbelimitedbyascarcityofuserswhowereknowledgeablein
the measurement and interpretation of infrared spectra. In 1949 Walter Baird and
Bruce Billings of Baird Associates and Van Zandt Williams of the Perkin-Elmer
Corporation came separately to Professor Richard C. Lord of Massachusetts
Institute of Technology (MIT), a leading academic researcher in the field. They
explained their concern and asked him to present a short course to provide rapid
traininginthesubject.Lordwasinterestedbutdidnotwanttoundertaketheproject
by himself, so he invited the author to join him in the venture.
For the first two years the course consisted of two identical five-day sessions
held in successiveweeks. The enrollment was restricted to 28 students each week
becauseofequipmentandmanpowerneedsforthelaboratory.Therewere15hours
of lectures in the morning, all given by Professor Lord and the author. They were
divided about equally between the basic optics of infrared spectrometers and the
theory and applications of infrared spectroscopy. Four afternoons were devoted to
hands-on laboratory experiments. Three of the experiments were devoted to the
propertiesanduseofdouble-beaminstrumentsandthefourthtosingle-beamoptics
andsamplehandling.Studentsweredividedintogroupsofsevenandrotatedamong
the four experiments. In addition to obtaining various spectra, they did such
fundamental operations as cleaving and polishing rocksalt, assembling sealed
liquid cells, and focusing a parabola with the Foucault knife-edge test.
The first year tuition was $90, a dormitory room was $2 per night, and meals
were paid for by students at the MIT cafeterias. Lectures were held in a room
whichwasnotairconditionedandwasuncomfortablyhot.Therewasconstruction
work outside, and the lecturers had to compete with the din of jack hammers.
ix
x FOREWORD
However,itwasaverystimulatingexperience.Anumberofknowledgeablepeople
from the instrument companies were present, including Van Zandt Williams of
Perkin-Elmer, Bruce Billings and David Z. Robinson from Baird Associates, and
William S. Gallaway of Beckman Instruments. They commented freely, and the
ensuing class discussion was lively and instructive.
It soon became apparent that there were two types of students with different
needs. One group had almost no experience in infrared spectroscopy and wanted
fundamental information on apparatus, experimental techniques, and applications.
The second group had substantial laboratory experience in infrared spectroscopy
and wanted much more emphasis on the interpretation of spectra. Therefore,
starting with the third year (1952), two separate courses were given in successive
weeks. The first was devoted to experimental aspects. In addition to morning
lectures,eachstudenthad10hoursoflaboratoryintheafternoons(2hoursperday
for five days). The second course concentrated on the theory and applications of
infrared spectra with heavy emphasis on characteristic group frequencies. An
important feature was 10 hours devoted to solving problems in the interpretation
of unknown spectra.
A laboratory course is labor intensive, requiring instructors and equipment for
small groups of students. Attendance in the laboratory course (the first week) was
thereforelimitedto60.Thestudentswere dividedinto10groups ofsixeach.Five
of these groups were in the laboratory from 1:00 until 3:00 pm, and the other five
from3:00until5:00pm.Thegroupsrotatedamongfiveexperiments,oneforeach
afternoon. Instrument manufacturers provided their most recent instruments and
also sent skilled personnel to supervise the experiments in which the instruments
wereused.InadditionProfessorLord’sgraduatestudentswereeachassignedtoan
experiment.
Also in 1952 guest lecturers were added. Some of them were invited to return
and ultimately became full-fledged members of the lecture staff. In this way Drs.
Ellis Lippincott, Dana Mayo, and Lionel Bellamy became regular lecturers while
the course was still at MIT.
The course was well received. By 1955 the demand for the first week had
exceededthe limit of60. (A fewexcess students took only the lectures butnotthe
laboratory.)Attendanceforthesecondweekwasover100.Thecoursewasheldat
MITeachsummerfor22years(1950–1971inclusive),withannualtotalattendance
during the first 20 years varying between 53 and 207 per year.
In 1970 two new experiments were added, one on Fourier transform infrared
spectroscopy andthe otheronRamanspectroscopy with laser excitation.This was
the last year of the laboratory offering. In 1971 there was a precipitous drop in
attendance, perhaps related to the sharp economic downturn, and the first week
(containingthelaboratory)hadtobecanceled.Only29personsattendedthesecond
week.MITinformedProfessorLordthatitnolongerwantedtosponsorthecourse,
soheasked Lippincott,Miller,andMayowhetheranyofthem wanted toofferthe
course at their institution. Lippincott and Miller could not do so, but Mayo, who
by then was at Bowdoin College in Brunswick, Maine, was enthusiastic. Hence
after 22 years at MIT, the coursewas moved to Bowdoin College, where the 1972
FOREWORD xi
and all subsequent courses have been offered under the direction of Professor
Dana W. Mayo. The course has now been at Bowdoin considerably longer than it
wasatMITandhashadmanymorestudents.ProfessorMayocontinuedasDirector
through 2000, the period covered by this history. He was succeeded in 2001 by
Professor Peter Griffiths of the University of Idaho.
Several changes were madewhen the course was moved to Bowdoin. First, the
laboratory portion was abandoned because neither the physical facilities nor the
necessary manpower was available. The course therefore consisted of lectures and
problem sessions. From 1972 through 1976 only one week was presented.
Second, the daily schedule was changed. Monday morning and afternoon were
devotedtolectures,followedbyalobsterbakeintheevening.Tuesday,Wednesday,
and Thursday mornings contained lectures, the afternoons were free, and the
evenings were devoted to problem sessions. The course ended Friday at noon.
This gave the participants an opportunity to explore the area during three after-
noons,averypopularfeature.Manyattendeesbroughttheirfamiliesandmadethe
stay part of their vacations.
In 1977 a second week of lectures on advanced topics was added at Bowdoin.
Thecontentofthetwoweeksvariedsomewhatovertheyears,butgraduallythefirst
week became devoted mainly to infrared and Raman characteristic group frequen-
ciesplusafewlecturesoninstrumentationandsamplehandling.Animportantpart
of the course was the evening exercise sessions, when each student interpreted
about 50 unknown spectra. The second week had lectures on more advanced
topics. It always had a heavy component on polymers, sampling techniques,
instrumentation, and Raman spectroscopy. Other subjects at various times
included forensic applications of infrared, quantitative analysis, small samples
and microspectroscopy, biological applications, and near-infrared spectroscopy.
There were two evenings of problems on polymer spectra, and another evening
was devoted to Jeanette Grasselli’s famous lecture on the use of combined
techniques.
In 1989 a third week was added. Peter Griffiths and James de Haseth had
presentedaworkshoponFouriertransforminfrared spectroscopy attheUniversity
ofGeorgia for threeyears (1986–1988). Theyproposed movingittoBowdoin and
appending it to the two one-week courses that were already operating there. This
wasdone.Thethirdweekdiffersfromthefirsttwoincontainingalargeamountof
hands-on work with instruments. Up toeightmanufacturers send their instruments
and provide personnel to supervise experiments using them. The attendance has
beenlimitedto40(eightgroupsof5studentseach)togiveeverystudentadequate
time on the instruments.
Registrants could take the three weeks in any combination they wished. Most
tookaweekineachofseveralsummers,butafewhavetakentwoweeksandeven
all three weeks the same year.
DuringtheperiodthatthecoursehasbeenofferedatBowdoin,thestaffhasbeen
saddened by the deaths of Ellis Lippincott, Lionel Bellamy, Professor Lord, and
Harry Willis. Fortunately Drs. Robert Hannah, Jeanette Grasselli, Peter Griffiths,
James de Haseth, and Bruce Chase have been excellent replacements.
xii FOREWORD
SOME DETAILS
A. Attendance. AtMIT,about2965peopletookthecourse.(Apersonattending
fortwoweekswascountedtwice.The1958attendancefiguresaremissing.)
At Bowdoin the number through 2000 was 3938. Thus over 6900 student-
weeks of training have been provided.
B. Regular lecturers have been (in the order in which they joined the course):
1.Richard C. Lord, 1950
2.Foil A. Miller, 1950
3.Ellis R. Lippincott, 1956
4.Dana W. Mayo, 1960
5.Lionel J. Bellamy, 1962
6.Jeanette G. Grasselli, 1977
7.Robert W. Hannah, 1977
8.Harry Willis, 1978
9.Peter R. Griffiths, 1983
10.James A. de Haseth, 1989
11.Bruce Chase, 2000
C. There were also many guest lecturers over the years. In 1959 they were
Norman Colthup, Norman Jones, Norman Sheppard, and Norman Wright.
Professor Lord referred to this as ‘‘the Norman invasion of infrared.’’
D. The 40th year of the course in 1989 was marked with a symposium and a
gala celebration held during the weekend between weeks 1 and 2.
E. Some traditions
1. Thelecturersgreatlyenjoyworkingtogethertopresentthecourse.There
isalongtraditionofhumor,joviality,kidding,andremarksfromtheback
row.Unexpectedslidesoccasionallyappearonthescreenwithcomments
such as ‘‘Baloney,’’ ‘‘Hogwash,’’ ‘‘Don’t believe a word of what
follows,’’ or ‘‘You have exceeded your time limit.’’ There is a famous
slide of Bob Hannah impudently sticking out his tongue. Jeanette
Grasselli is notorious for introducing her featured lecture (always an
outstanding hit) with a series of slides embarrassing the other lecturers
(which, ruefully, is also a hit).
2. A much-appreciated tradition is the weekly Monday night lobster bake.
3. Theendofthemidmorningcoffeebreakissignaledbytheringingofone
oftwobells.OneisacowbellfromIndia—loudbutunmusical.Theother
is a small melodious ship’s bell presented by the students one year
because they couldn’t stand the tone of the Indian bell.
4. Another tradition is Foil Miller’s presentation concerning the course
neckties that the staff has acquired over the years and their analogies to
infrared bands.
F. Courses given abroad. The course has been presented abroad 13 times as a
one-weekoffering.Thematerialwastakenmainlyfromthefirstweekofthe
U.S.course,withsomeomissionstomakeroomforalittlematerialfromthe
second week.
FOREWORD xiii
Year Date Place
1982 May 10–14 Kristiansand, Norway
1983 May 16–27 Shanghai, Peoples’ Republic of China
(One week of material presented over two weeks because of the
need to use interpreters.)
1984 Mar. 26–30 RoyalHolloway CollegenearWindsor,
England
1985 May 20–24 Stro¨mstad, Sweden
1985 May 28–31 Utrecht, Netherlands
1987 Jan. 26–30 Mexico City, Mexico
1988 May 16–20 Near Malmo, Sweden
1988 May 24–27 Breda, Netherlands
1990 Mar. 19–23 Queretaro, Mexico
1992 Apr. 26–30 Budapest, Hungary
1992 May 4–8 Stro¨mstad, Sweden
1995 May 28–June 2 Lerum, near Gothenburg, Sweden
1999 May 3–7 Halmstad, Sweden
G. Amoredetailedhistoryofthecoursehasbeenpreparedandcanbeobtained
from any of the regular lecturers.