CARNEGIE MELLON UNIVERSITY
DEPARTMENT OF CHEMISTRY
09-248 Fall 2000
Lectures: Monday,Wednesday,Friday from 11.30-12.20
Place: Doherty Hall B103
Recitation: Tuesday from 11.30 -12.20
Place: Doherty Hall 1212
INSTRUCTOR: PROFESSOR GARRY WARNOCK
Rooms: MI 734-740
Phone: 8-4229 on campus and 268-4229 from off campus
Responsibilities: The construction and delivery of three lectures per
week for approximately fifteen weeks..Homework construction.. Construction
of exams and solution sets. Grading of the Final Exam.
TEACHING ASSISTANT: TBA
To photograph all class members during the first week of classes. Attending
lectures,keeping a brief summary of each lecture and leading the Tuesday
recitation tutorial.Monitoring the amount of homework set to ensure a
reasonable workload.Generating solution sets for homeworks.Grading Homeworks
and Friday Exams including photo-copying . Recording scores on Homeworks
and quizzes.Keeping the record of class performance. Offering a reasonable
number of office hours to help students.
This course is designed to take the student to a point of confidence
with inorganic chemistry such that an intelligent dialogue on general
topics would be possible..This is not a History of Chemistry Course yet
we will include historical anecdotes whenever this enhances understanding
of the material Although this is not an Advanced Inorganic Course the
student should finish up sufficiently well-prepared that they could embark
on the study of any topic in the Inorganic domain.I would like to emphasize
that this is also not a course in Inorganic Spectroscopy but some rudimentary
knowledge of this area including an understanding of Spectroscopic terms
for polyelectronic atoms will be important so that you can understand
how energy transitiuons in the molecules and structures are measured by
UV-Vis,UV-PES,IR,Raman, and multi-nuclear NMR.Brief discussions of these
techniques are to found in the text and should be re-viewed as soon as
possible.A short discussion of term symbols is found on pages 438-443
in Shriver.Further examples and information may be found in the textbooks
placed on reserve in the Engineering and Science library. The current
periodicals such as JACS,Inorganic,Chem Comm and JCS Dalton to be found
in the Mellon Library may also serve as a reservoir of examples of various
CONTENT OF THE COURSE
At the end of the course the student should have read the chapters [i.e.3,4,7,8,9,11
and 12] plus other parts of the text specifically referred to as supplementary
reading and paid particular attention to those topics in the lists below.These
lists are detailed accounts of the content material of every lecture and
will be followed as closely as possible. It is impossible in terms of
time to include all the topics from a particular chapter so you must use
the detailed listings that I have compiled to know what you are responsible
for on the four Friday exams.Of course the Friday exam is only 45 minutes
long and cannot possibly cover all the material from the lists for the
two chapters.A last chance check-list is also provided for each exam that
serves as a guide to the bare minimum of topics for you to revise.
See Chapter 3,Homework 1 and other sources.
 Be able to assign both average and individual Oxidation states to
atoms in molecules/ions.e.g NNO,C3O2,NO3-,N2O3.See rules on page 69 in
 Draw Lewis Structures including formal charge [If need be see the
formula for formal charge calculation on page 68 in Shriver] assignments
on each atom for simple molecules/ions
.e.g CNO-, SO42-,H2CO, C2H4, C2H2, [NMe3]2BH2+.
 Predict the correct shapes of molecules from numbers of domains.A
domain is defined as any of the following; sbp,dbp.tbp,lp,se.
[where sbp=single bond pair,dbp=double bond pair,lp=lone pair and se=single
electron.]For example predict the shapes of the following molecules/ions:
 Review bond enthalpy[see page 72 Shriver] and Pauling's definition
of electronegativity[see page 74, Shriver]
 Understand the importance of Isolobality [see page 80,Shriver] in
the prediction of the shapes of molecules e.g. cf P4 versus Ir4[CO]12
or Cl2 versus Mn2[CO]10.
 Use Molecular Orbital [MO] theory for homo-diatomics,hetero-diatomics
[e.g. CO] and some selected poly-atomics [e.g. BF3 ,SF6]
 See how the experimental results of photoelectron spectroscopy correlate
with MO diagrams.eg see N2 example on page 85 of Shriver
 Extend MO theory to include solids such as metals. Know the difference
between conductors,semi-conductors and insulators.Know about how bands
and band-gaps are created.Define the Fermi level.
See Chapter 4,Homework 2 and other sources
 Identify and distinguish symmetry operations and symmetry elements.See
table on page 118, Shriver.
 Be able to assign point groups to the special groups [ i.e.icosahedral,linear
and cubic] without using a flowchart.
 Know about the Platonic solids including why there are only five.
 Throughout the course we will re-inforce the skill of using a flow-chart
[see page 122 in Shriver] to assign point groups of molecules/ions.e.g.Assign
a point group to e.g. the following molecules :water,ammonia,benzene,hydrogen
peroxide[several cnformations need to be considered],napthalene,acetylene,sulfur
tetrafluoride,hydrogen chloride ,eclipsed ferrocene,staggered ferrocend
and buckminster fullerene.
 Possess a qualitative appreciation of the interpretation [see page
128-130,Shriver] and some uses of character tables.For those more interested
in this topic see the Further Info section on pages 687-690 of Shriver
or the text by Harris and Bertolucci [ pages 47-54]
 Obtain a reducible representation for the motional degrees of freedom
[translation,vibration and rotation] in a molecule such as water[for instance
see page 63 in Huheey,4th edition].Also see any of the following examples
in Huheey if you wish to practice how to generate a particular reducible
representation: pages 73,178,179, 416,421,431, and 633.
 Know that the number of vibrational modes in a molecule containing
"N" atoms is 3N-6 [or 3N-5 if linear]
 Decompose reducible representations within point groups into their
 Be able to assign the irreducible representations to translations,
rotations and vibrations.
 Given a real spectrum assign the IR and Raman bands e.g. How many
IR carbonyl stretching frequencies do you expect for each of the following
metal carbonyls: Ni[CO]4,Fe[CO]5 and Cr[CO]6.
Last Chance Checklist for Exam 1
1.Assignment of oxidation states.
2.Draw principal resonance contributors for molecules and ions.
3.Assign formal oxidation states to atoms within molecules/ions
4.Be able to draw MO diagrams for B2,F2, and CO.
5. Assign point groups with the help of a Flow-chart to molecules/ions.
6.Obtain Reducible Representations using an appropriate Character Table
for a vector set on a molecule/ion.
7.Decompose the latter into irreducible components.
See Chapter 7 ,Homework 3 and other sources.
 Be able to fill in the d block from memory into a blank periodic
table.This will appear on homework and exam.
 Know the names and abbreviations of a set of common ligands.eg What
are the names of the following when they act as ligands: H2O,NH3,Cl-,CN-,cod,en,tmeda,18C6,222Cryp,bipy,py,phen,CO,PR3.Be
able to draw Lewis Structures and assign point groups to these molecules.
 Know the relative positions of ligands in the Spectrochemical Series
I-, Br-, S2-, SCN-, Cl-, NO3-, N3-, F-, OH-, C2O42-, H2O, NCS-, CH3CN
,py, NH3, en, bipy, phen, NO2- PPh3 , CN-, CO
 Predict Chirality for complexes.Be able to draw isomers
 Given the name of a simple complex you should be able to draw the
correct structure.See nomenclature 677-681 in Shriver.
 Be able to assign configurations,calculate numbers of un-paired electrons
and.compute ligand field stabilisation energies for complexes.
 Understand the basics of crystal field and ligand field theory.
 Be able to spot which complexes exhibit Jahn Tellor distortion
 Be able to sketch from memory the molecular orbital diagram for a
typical octahedral complex.
Understand the difference between pi acceptor and pi donar ligands.Know
of examples of these types of ligands.
Be able to sketch an MO diagram for a octahedral complex with sigma
only,sigma and pi-donar or sigma and pi-acceptor ligands.
See Chapter 8 , Homework 4 and other sources
 Be able to assign Oxidation Numbers to the various atoms in hydrogen-containing
compounds or ions.. eg NH3,H2O,NaH,H2O2,ReH92-.
 Classify Hydrogen compounds as either Molecular,Ionic or Metallic.
 Have feeling for the various synthetic paths to hydrogen and some
selected hydrogen compounds.
 Be able to classify compounds as electron precise,electron rich or
 Be able to assign point groups to a selection of hydrogen compounds.
 Discuss the trends in Melting and Boiling points for hydrogen compounds
in terms of bonding types.e.g. explain the changes in the boiling points
as we progress through the series:LiH,BeH2,B2H6,CH4,NH3,H2O,and HF.
Last Chance Checklist for Exam 2
1. Be able to fill in the correct symbols of the elements of the d block
2. Be able to write down the formulas of named complexes e.g.potassium
3. Be able to drawer structures for some common ligands such as oxalate,
bipy,18c6,en and tmeda.
4. Arrange ligands in order of ability to split ligand field i.e. strength
5. Be able to compute ligand field stabilization energies.
6. Recognize common reactions of hydrogen compounds.
7. Be able to discuss the relative values of the boiling points for a
series of compounds such as CH4,NH3,H2O.
See Chapter 9 ,Homework 5 and other sources
Be able to identify the types of metals including the "f' block
in the Periodic Table.You do not need to memorize the sequence of f elements
in the periodic table.
 Know the names of the minerals that are common sources of Li,Na,K,Be,Mg,Ca,Al,Sn,Pb,Ti
,Fe, Mn, Cu, Zn,and U.
 Be able to write down the correct symbols for the metallic elements
in the s,p,and d blocks onto a blank periodic table.You should be able
to do this from memory.
Know what properties are considered typical of a metal.
Have a general feeling for how the metals are extracted from their
Know about complexes of s block elements
Know about electrides and alkalides
Know about the chemistry of the d block elements
Know about Al Ga,Sn and Pb
 Know a little about the f block elements.
See Chapter10 ,Homework 6 and other sources.
 Be able to fill in Group 13 and 14 into a blank Periodic Table
 Know how Group 13 and Group 14 elements are extracted from ores.
 Know about the preparation and reactions of Boron Halides,Oxides and
 Apply Lipscomb's STYX and Wade's Rules [see discussion of these rules
in Cotton and Wilkinson sixth edition on page 145] to the Boranes.Understand
the significance of 3c-2e and Nc-2e [N>3] bonding in the formation
of boranes and clusters in general.It will be assumed in exams that you
know what "s","t" "y" and"x" stand
i.e. s=#BHB 3c-2e , t=#BBB 3c-2e,y=#BB 2c-2e, x=#BH 2c-2e>p
Given a styx set you should be able to suggest and then draw a structure.
 Be able to describe and discuss the Allotropes of Carbon.[Films:The
age of Polymers and Nova's "Bucky Balls" may be shown if time
 Know about Silicon Oxygen Compounds and their importance in Minerals
and Rocks.Be able to draw diagrams of the simple silicates.
Last Chance Checklist for Exam 3
1.Be able to insert the s,p and d metals from memory into a blank periodic
2.Know the names of the common minerals of the metals mentioned above.See
3.Be familiar with the common reactions of the Groups 1 and 2 metals.
4.Be able to write down the possible styx numbers for a typical boron
hydride e.g. B5H9 or B12H122-.Re-call that you will be given the styx
equations on the quiz.
5.Know how metals such as sodium,potassium,tin,and iron are obtained in
industry from their ores.
6.Know about the structures of the simple silicates.
See Chapter11,Homework 7 and other sources,
Be able to fill in Group 15 and 16 into a blank periodic table
Be aware of the various oxidation states of Groups 15 and 16
Know about the sources of Nitrogen,Phosphorus,Oxygen and Sulfur
Know about Explosives and detonators [Film :Kaboom]
Know about the compounds of the elements
 Know about Ozone layer controversy.[Film: The two faces of Ozone]
See Chapter12 ,Homework 8 and other sources.
Be able to fill in Group 17 and 18 into a blank Periodic Table
Know about the common Oxidation Sates of Groups 17 &18 elements.
Know about the sources of these elements [e.g. How Henri Moissan figured
out how to isolate Fluorine] including the discovery of the noble gases.
Know about the discovery of Helium and Ramsey's discovery of the noble
Know about Pseudohalogens, Interhalogens,Cationic polyhalogens and
anionic poly iodides.
Know about the oxides of the Halogens.
Know about the chemistry of the noble gases and the work of Neil Bartlett.
Last Chance Checklist for Exam 4
1.Know about the chemistry and structures of Groups 15 and 16 compounds.
2.Be able to assign point groups to these structures.
3.Know about the synthesis of nitric acid from basic starting materials.
4.Be able to speculate on whether a particular molecule is real or not.For
instance consider the following group of possible molecules:IBr7, FI7,
NeI4 , I9-.
5.Know about how William Ramsey discovered the noble gases.
ABOUT THE CHOICE OF TEXTBOOK
The textbook "Inorganic Chemistry" by Duward Shriver and Peter
Atkins is considered by most Inorganic Chemists to be one of the best
currently available.It is well organised and highly readible. It will
be followed closely for most but not all of the course.Of course you must
realize that these textbooks serve also as reference books.No-one is expected
to memorize the entire book.However the more facts you have at your fingertips
the more extensive is the "Scafold' you can build to hang more facts
on .In this way you set up your own "building" that determines
your understanding of the connections in Natural Philosopy.If we knew
no facts we could not make any connections.It must be emphasized that
any real serious student must read many authors on the same subject.In
fact Wittgenstein defines true understanding in the following way [slightly
paraphrased] : "Understanding is seeing that the same thing said
in different ways is the same thing ".So the different angles revealed
by lecturer ,teaching assistants and book authors are not put in to confuse
people but if anything should act as a help towards the achievement of
true understanding.Remember that everyones viewpoint is in the end quite
unique. Some books are on reserve in the Engineering and Science Library
on the 4th floor of Wean Hall.These six or so are excellent reference
books that contain a wealth of information for anyone wishing to pursue
an advanced topic.They also serve as good sources of ideas for a topic
for your 10 minute presentation.
At the first recitation on Tuesday the TA will photograph everyone in
the class for our records.This is particularly useful if any of you need
a reference in the next few years so I can attach a face to a name as
well as just looking up your grade etc.
Recitations are an excellent opportunity for you to ask questions about
Homework problems but the TA will also periodically lead discussions and
hand out "Blackboard" exercises to randomly selected students
to test that lecture material is being absorbed and that people are handing
in well thought out answers to the Homework problems .
The T.A. has also been asked to keep a record of attendence at Recitation
meetings.The T.A is also to keep a record of the topics dealt with in
Recitations and particularly of questions raised by students.Those students
who cannot attend Recitations must arrange to get notes from other students
in the class or make an alternate appointment at the convenience of the
At the recitation immediately prior to a Friday exam the T.A is very likely
to hand out blackboard problems that relate strongly to the exam questions.
BOOKS ON RESERVE, AND AUTHORS
"Advanced Inorganic Chemistry", F.Albert Cotton , Geoffrey
Wilkinson et al.
"Chemistry of the Elements", N. N. Greenwood, A. Earnshaw
"Symmetry and Spectroscopy", D. C. Harris, M. D.Bertolucci
"The Elements", John Emsley
"Structural Inorganic Chemistry", A. F. Wells
"Inorganic Chemistry", J. E. Huheey et al.
GRADED COURSE MATERIAL
Eight Homework Problem Sets, each covering a chapter will be given out
at the start of the course.The completed problem sets must be submitted
to the Teaching Assistant at the beginning of the designated thursday
recitation help session.Consult the course calendar for the eight hand-in
dates. Any problem set handed in late receives a maximum of half the possible
points unless accompanied by a Doctor's note.Please do not hand in Problem
sets to Dr Warnock or at irregular times or during lectures.Please do
not hand in Problem Sets at the chemistry offices in either Doherty or
Four Friday 45 minute quizzes or exam's if you like will be administered,photocopied,
graded by the TA and handed back at the end of the Monday class.Any queries
about the Grading should be addressed to the TA at the end of the following
Thursday recitation. .Each Friday quiz [Four in all, see calendar for
dates]will cover material from 2 chapters.Each quiz will be closed text
and closed notebooks.It should go without saying that these quizzes are
not comprehensive.The limit of 45-50 minutes means we cannot ask questions
on all aspects of the Chapter.The final exam will be no more comprehensive
since. all eight chapters included.It will be closed text and closed notes.This
exam will be photo-copied ,graded and handed back by the TA. as soon as
possible.The T.A. will select the best time and place. The questions on
the Final Exam will be heavily influenced by parallel questions that have
appeared in Friday quizzes ,Bi-monthly Homeworks and Weekly Recitation
Finally a Ten minute presentation will be given by each member of the
class on a chemical element [of your own choice] or a previously agreed
upon topic.These presentations will be scheduled throughout the course,
particularly on the week before the Final and including the use of recitation
time if need be.The presentation should be made on transparencies ,obtained
from Ellen Reichenbach in Doherty Hall.2114.
It is hoped that we will be able to do some chemistry demonstrations in
this course and consequently I will need some volunteers willing and able
to help with the setting-up and taking down of any equipment used.If you
would like to do this and you have time before and/or after any of the
classes please contact me as soon as possible.
Attendance will be taken at Recitation and occasionally at lectures to
yield an overall picture of who shows up.This can not effect your grade
in any way .
The grade will be apportioned over student work as follows:
Problem Sets 40%
Four Friday Examination 40%
Final Examination 15%
Ten -minute presentation 5%
COURSE POLICY ON CHEATING AND PLAGIARISM
In all its courses, the faculty of the University has generally agreed
with the student body that a statement should be made at the beginning
of the course on what constitutes proper practice in submitting material
for evaluation by the Teaching Assistant and Principal Lecturer/Professor.
(1) Read the University Policy about Cheating and Plagiarism.
(2) In this course you are encouraged to discuss problems with your peers
and to seek help from others ,such as the Teaching Assistant, in understanding
the topic. Material submitted for grading should be your own synthesis
of your own ideas and the input you have received. Instances discovered
of UNFAIR ADVANTAGE being taken of any other individual or group will
result in a loss of grade substance.
(3) If you have specific questions about whether or not a given practice
constitutes the taking of UNFAIR ADVANTAGE, please discuss it first with
the professor.I think it is perfectly reasonable for a student to raise
such issues and can guarantee it will not be held against the student
in any way whatsoever.In fact I am grateful to any one who point's out
a potential weakness in how the course is structured and how grades are