Carnegie Mellon University, Department of Chemistry

 

Dr. Warnock's Inorganic Chemistry (Chem 09-348)

Syllabus, Fall Term 2000


CARNEGIE MELLON UNIVERSITY
DEPARTMENT OF CHEMISTRY

INORGANIC CHEMISTRY

09-248 Fall 2000

CLASS SCHEDULE:
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
Email: warnock@andrew.cmu.edu
Rooms: MI 734-740
Phone: 8-4229 on campus and 268-4229 from off campus
Fax:
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
Email:
Phone:
Responsibilities:
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.

 

COURSE OBJECTIVES

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 spectroscopic measurements.

 

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.

[1] 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 Shriver.
[2] 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+.
[3] 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: H2O,BF3,NCl3,SF4,PCl5,H5IO6,NO3-,NO43-]
[4] Review bond enthalpy[see page 72 Shriver] and Pauling's definition of electronegativity[see page 74, Shriver]
[5] 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.
[6] Use Molecular Orbital [MO] theory for homo-diatomics,hetero-diatomics [e.g. CO] and some selected poly-atomics [e.g. BF3 ,SF6]
[7] See how the experimental results of photoelectron spectroscopy correlate with MO diagrams.eg see N2 example on page 85 of Shriver
[8] 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

[1] Identify and distinguish symmetry operations and symmetry elements.See table on page 118, Shriver.
[2] Be able to assign point groups to the special groups [ i.e.icosahedral,linear and cubic] without using a flowchart.
[3] Know about the Platonic solids including why there are only five.
[4] 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.
[5] 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]
[6] 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.
[7] Know that the number of vibrational modes in a molecule containing "N" atoms is 3N-6 [or 3N-5 if linear]
[8] Decompose reducible representations within point groups into their
irreducible components.
[9] Be able to assign the irreducible representations to translations, rotations and vibrations.
[10] 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.

[1] Be able to fill in the d block from memory into a blank periodic table.This will appear on homework and exam.
[2] 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.
[3] Know the relative positions of ligands in the Spectrochemical Series eg
I-, Br-, S2-, SCN-, Cl-, NO3-, N3-, F-, OH-, C2O42-, H2O, NCS-, CH3CN ,py, NH3, en, bipy, phen, NO2- PPh3 , CN-, CO
[4] Predict Chirality for complexes.Be able to draw isomers
[5] Given the name of a simple complex you should be able to draw the correct structure.See nomenclature 677-681 in Shriver.
[6] Be able to assign configurations,calculate numbers of un-paired electrons and.compute ligand field stabilisation energies for complexes.
[7] Understand the basics of crystal field and ligand field theory.
[8] Be able to spot which complexes exhibit Jahn Tellor distortion
[9] Be able to sketch from memory the molecular orbital diagram for a typical octahedral complex.
[10]Understand the difference between pi acceptor and pi donar ligands.Know of examples of these types of ligands.
[11]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

[1] Be able to assign Oxidation Numbers to the various atoms in hydrogen-containing compounds or ions.. eg NH3,H2O,NaH,H2O2,ReH92-.
[2] Classify Hydrogen compounds as either Molecular,Ionic or Metallic.
[3] Have feeling for the various synthetic paths to hydrogen and some selected hydrogen compounds.
[4] Be able to classify compounds as electron precise,electron rich or electron deficient.
[5] Be able to assign point groups to a selection of hydrogen compounds.
[6] 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 from memory.
2. Be able to write down the formulas of named complexes e.g.potassium pentachloronitridoosmate[II]
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

[1]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.
[2] 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.
[3] 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.
[4]Know what properties are considered typical of a metal.
[5]Have a general feeling for how the metals are extracted from their ores.
[6]Know about complexes of s block elements
[7]Know about electrides and alkalides
[8]Know about the chemistry of the d block elements
[9]Know about Al Ga,Sn and Pb
[10] Know a little about the f block elements.

See Chapter10 ,Homework 6 and other sources.

[1] Be able to fill in Group 13 and 14 into a blank Periodic Table
[2] Know how Group 13 and Group 14 elements are extracted from ores.
[3] Know about the preparation and reactions of Boron Halides,Oxides and Nitrides.
[4] 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 for.
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.
[5] 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 permits]
[6] 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 table.
2.Know the names of the common minerals of the metals mentioned above.See [2].
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,

[1]Be able to fill in Group 15 and 16 into a blank periodic table
[2]Be aware of the various oxidation states of Groups 15 and 16
[3]Know about the sources of Nitrogen,Phosphorus,Oxygen and Sulfur
[4]Know about Explosives and detonators [Film :Kaboom]
[4]Know about the compounds of the elements
[5] Know about Ozone layer controversy.[Film: The two faces of Ozone]

See Chapter12 ,Homework 8 and other sources.

[1]Be able to fill in Group 17 and 18 into a blank Periodic Table
[2]Know about the common Oxidation Sates of Groups 17 &18 elements.
[3]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 gases.
[4]Know about Pseudohalogens, Interhalogens,Cationic polyhalogens and anionic poly iodides.
[5]Know about the oxides of the Halogens.
[6]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.

 

RECITATIONS

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 T.A.
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 Mellon.
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 Sessions.


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 assessed.

Dr. Warnock's Inorganic Chemistry--Course Directory

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