CHARACTERISTICS OF INORGANIC COMPOUNDS
Course Perspective (html)
Chemistry 531 Syllabus - pdf format
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Coverage for the First Examination (pdf format)
Second Exam Coverage (html) Coverage for the Second Examination (pdf format)
Third Exam Coverage (html)
Coverage for the Third Examination (pdf format)
Chemistry 531 Abbreviated Lectures
Announcements & Assignments
CH 531
Fall Semester
Text: "Chemistry of the Elements," by N. N. Greenwood and A Earnshaw, Pergamon Press, second edition, 1997.
The text is fact oriented. It is intended to provide general and specific factual material relevant to the lectures which will be oriented toward a practical, theoretical understanding of the chemical and physical behavior.
Lecturer: Professor Jamie L. Adcock, BU 501, ph (865) 974-3391, Department of Chemistry, The University of Tennessee, Knoxville, TN 37996-1600, JAdcock@utk.edu.
Course Organization: Three Examinations (25% each), Term Paper (15%), Class Participation and Chapter Outlines (10%). Written chapter outlines are turned in no later than one class period after due date for credit. Chapter outlines are used for reference on examinations. No class notes may be transcribed into chapter outlines!
Course Perspective
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The chapter outlines are designed to help you digest the material in the text. You should expect on average about one page of outline per 10 pages of text. These will be turned in and checked by the instructor. The first one or two will be returned with comment. The chapter outlines are to be turned in within one class period of the due date for course credit. Once outlining meets expectations of the instructor they will be kept and returned just prior to the examination on which they will be used. MAKE PHOTOCOPIES FOR STUDY PURPOSES! ONLY ORIGINAL HANDWRITTEN OUTLINES MAY BE TURNED IN OR USED ON EXAMINATIONS. The outlines may be used during the three examinations. You should structure the outlines accordingly. The questions on the examinations will test your understanding of the material in the text, the outlines should provide you with the specifics you need to fully answer questions provided in the exam coverages, specifics you understand but do not wish to memorize. You will be expected to have read the chapter before coming to lecture and in most cases have prepared the outline. Lectures may be downloaded from the website as pdf handouts. You may bring these to class and annotate them during the lecture. The lectures will not be comprehensive but will spend time on specific aspects of the chemistry of that group of elements. The examinations will not therefore cover just the lecture notes. It is your responsibility to bring to the attention of the instructor in class, or privately, those concepts you find difficult to comprehend, or wish to discuss.
The last two weeks of the course will be a necessarily rushed coverage of the transition metals, we cannot cover the lanthanides and actinides. In the last nine chapters (20-29) you should read the material but outline only those aspects pertaining to organometallic chemistry and catalysis. During the "fall break" you should try to get ahead on your reading and possibly read these chapters. The familiarity with metals will make the lectures on carbon/organometallics more understandable.
The examinations will each cover the third of the course which they conclude. There may be some instances in which concepts will be carried forward or where there is overlap but generally the exams will be limited to the material in their respective third. The examinations will be held out of class period at a time agreeable to the class as a group. They will be two to three hours in length. Ample time (3 hours) will be provided for their completion.
The term paper will be a specific, incisive research-oriented, investigative piece with references. It is not to exceed 15 double-spaced typed/printed pages with 12 pitch font or larger. Large figures of moderate information content can be excluded from the page limit on approval of the instructor.
The term paper is to be a specific investigation and discussion of essential chemistry in some area of art, science or technology not generally perceived to be chemical, for example: a) metallurgical alloys, b) logic circuits, c) molecular switching, d) preservation or analysis of archeological remains, e) biological mutations and adaptations, f) ceramics, etc. This topic may be related to your research but it may not be a reiteration of that research, or your proposal defense.
THE EXAMINATIONS:
THE EXAMINATIONS WILL CONSIST OF DISCUSSION QUESTIONS. YOU WILL HAVE
A CHOICE OF QUESTIONS TOTALING 180 POINTS, 120+ POINTS WILL CONSTITUTE AN
"A" GRADE. CHAPTER OUTLINES MUST BE TURNED IN TO INSTRUCTOR BY
THEIR DUE DATES TO BE USED. THEY WILL BE RETURNED TO THE STUDENT IMMEDIATELY
PRIOR TO THE EXAM (MAKE COPIES TO STUDY BY!).
STUDY GUIDE TO THE FIRST EXAMINATION
THE FIRST EXAM WILL COVER CHAPTER 1 THROUGH CHAPTER 7.
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1) Consider the data necessary to determine the size, temperature, distance and velocity of stars relative to the earth. How can the rate of expansion of the universe be determined? What is that rate? Describe the evolution of a G class star, what nuclear processes occur at the various stages.
2) Using the theories describing the formation of the universe and the elements it contains, address questions: of abundance of elements with special attention to element groups which have unusually high or low abundances; of stellar processes in which nucleogenesis occurs giving balanced nuclear reactions in serial processes.
3) Consider property trends in the periodic chart, the characteristics of a group (family, column) and how those characteristics can be related to electronic structure, how those characteristics change proceeding down a group. Consider trends in a period as one proceeds across a "block" (d-block, p-block, f-block). Be able to rationalize exceptions to general trends especially those which can be related to electronic structure.
4) Consider: the nature of saline and transition metal hydrides; band structure and bonding in metals; theories of bonding in transition metal hydrides. Consider how these theories explain the properties of metals semiconductors, insulators and transition metal hydrides.
5) Consider the nature of the hydrogen bond, the bonding in [F-H-F]-, the electron deficient hydrogen bridge bond, bonding in H3+ cation, hydrogen as a ligand, mechanistically distinct pathways leading to formation of metal-hydrogen bonds.
6) Consider factors which affect the acidity of hydrogen atoms in molecules; the nature of metal ammonia solutions; the choice of bridging elements in Be and Mg organometallics; the selectivity of crown ethers and crypts; the volatility of ionic compounds.
7) Consider: the bonding elements found in boron hydrides; the electronic requirements of closo, nido, arachno and hypho hydridoboranes and hydridoborates (Wades rules); the structural relationships between the above classes; the topological (valence bond) approach to non-closo hydridoboranes; the styx numbers; the molecular orbital approach to bonding in closo-hydridoborates; properties and characteristics of closo-hydrido-borates rationalized by the molecular orbital bonding model.
8) Regiospecific reactions in hydridoboranes: halogenations, cage expansion, isomerizations, additions. Structure and bonding in boron halides, boron subhalides and clusters. Boric Acid, borate bonding units, boron nitride, borazines, amino-boranes; their structures and bonding.
9) Consider anomalies in Group 13 vs Group 3; the low melting point of Ga and how it relates to Hg; the acidities of group 13 hydrates and oxides; the tendencies 3c-2e bridging; the stabilities of III/I oxidation states and oxidation potentials; Aluminum alkyls, the "growth reaction" and Ziegler Natta catalysis.
STUDY GUIDE TO THE SECOND EXAMINATION
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THE SECOND EXAMINATION WILL COVER CHAPTER 8 THROUGH CHAPTER 18.
1) .Consider graphite intercalation compounds, the idealized stoichiometries of Stage 1-4 potassium intercalates. Suggest reasons for the uniform staging of intercalates from an energy standpoint, the long-range order of the cations (and by analogy anions). The intercalates of the halogens other than fluorine are analogous but differ, how so. Why does fluorine behave differently.
2) .Consider the geometry of fullerenes, what generalizations can be made about those individuals which are most readily prepared and hence more stable. Consider the electron density distributions in C60, in La@C60. Consider the composition and electronic properties of the alkali fullerides. Using a simple concentric shell model and the covalent radii of C, F, Cl, Br calculate the idealized stoichiometries of C60Xn. Into what reaction category do the unsaturated rings of C60 fall? What are some example reactions. What is the structural relationship of one structural model of the Ti8C12 metallocarbohedranes to the fullerenes. What other structural models can be used to describe them.
3) Give a basic description of the early transition metal interstitial carbides. Why is this description not applicable to the carbides of TM's beyond group 6. Use the delocalized bonding model of metallic bonding to explain the remarkable changes in metallic properties which occur on incorporation of carbon into the early TMs.
4) Consider the environment of a carbido-carbon atom at the center of a closo-octahedral cluster of metal atoms. What molecular orbital bonding scheme might you derive for the CM6 unit in the vicinity of the carbon atom. What similarities/differences do you notice between molecular orbitals derived for a closo-octahedral cluster of metal atoms with and without the carbon atom (a Oh character table might be helpful).
5) Consider the effect on the chemical properties of organic functional groups when they are bonded to alkyl/aryl (R) groups versus the corresponding perfluoroalkyl (Rf) groups. Consider the ligating ability of CO2 and CS2.
6) What are the basic structural units of silicates? How may they be structurally related to the various types of silicones? Describe the Rochow synthesis and how the products are used in silicone synthesis. What property gives the silicates and silicones great stability. What property causes the higher silanes to decompose?
7) Be able to compare/contrast the properties and behavior of carbonic vs silicic acid and CO2 vs SiO2; C-X vs Si-X vs Ge-X vs Sn-X vs Pb-X bond strengths where X = themselves, C, Si, H, F, Cl, Br, I, O, N; basicity between amines and silyl amines, relative stabilities or ethers, silicones, "germaneones". Compare/contrast structures, properties and reactivities of Fluorides and chlorides of C, Si, Ge, Sn, Pb; the trends in metallic behavior, electronegativities of Group 14 elements.
8) Compare the ligating ability of NF3, PF3 and AsF3 with transition metals. The bonding/structure, aggregation and F- acceptor ability of PF5 , AsF5, SbF5 and BiF5. The gaseous and solid phase bonding of PF5, PCl5 and PBr5. Compare and/or contrast a) the structure and bonding in nitrogen and phosphorous oxides, oxoacids and oxoanions; b) the stability of covalent and ionic azides; c) The ligating ability and bonding of amines, phosphines and arsines to transition metals; d) The ligating ability, modes of bonding of NO2(-) and NO to transition metals.
9) Be able to describe and compare the structures and bonding in cyclophosphazenes having six and eight membered rings. Describe a phosphorous alkylidene phosphorane (Ylid). Account for the unusual strength and stability of the P=O group.
10) The following clusters have been characterized: Bi(3+) (D3h), Ge4(2-) (Td), P4 (Td), Sn5(2-), (tbp), Bi5(3+) (tbp), Bi8(2+) (sq. antiprism), Sn9(4-) (capped sq. antiprism). Be able to use Wades rules to determine the number of electron pairs needed to satisfy each structural type, determine the electrons available for bonding in each cluster, determine electron deficiency, sufficiency or excess and possible reflections in chemical behavior. Determine for each cluster the orbitals and electron utilization in cluster and non cluster binding. Be able to draw the structures and indicate pictorially the kinds of orbital overlaps that can occur.
Ch 14 - Oxygen:
Be able to describe/explain a) the electronic states and the molecular orbital diagram of O2; b) the orbital overlaps, bonding and energy level diagram for O2 bonded to a transition metal in Dewar Duncanson mode; c) other modes of O2 to transition metal bonding. d) Bonding in O2F2 and O2H2; ozone. e) Reactions of "singlet oxygen" and explanation of similarities of TM and dye sensitized oxidations.
Ch 15/16 - Sulfur; Selenium, Tellurium and Polonium:
Bonding in and similarities between S42+ and S2N2; S82+ and S4N4; Modes of bonding of S and S2 to transition metals. Reactions which make S-S bonds; structures of sulfanes. Sulfur fluorides, chlorides: synthesis, structures and reactions. Structures/names of oxoacids/oxoanions of sulfur. Acid strengths/structures of oxoacids and hydrides -group trends. S, Se & Te cations. Structure/bonding in [Te6]4+ cluster application of Wade's rules.
Ch 17/18 - Halogens/Noble Gases:
Molecular Orbital diagrams for halogens, explanation of color changes of iodine in donor and non-polar solvent solutions. Miscibility behavior of water-hydrogen halides. Structures of interhalogen compounds, noble gas fluorides and oxides and their anions and cations. Effect of fluorine on the stability of pi bonds.
STUDY GUIDE TO THE THIRD EXAMINATION
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Ch 19 - Coordination Compounds:
1) Stereochemistry of coordination numbers 2-10. Types of isomerism. Crystal field theory. Molecular orbital diagram of Oh complex. Complementary Colors of absorption and observation. Free ion terms, splitting of free ion term in cubic fields. The "hole" formalism and state inversions on Oh to Td. Crystal field stabilization energies (CFSE) of "d" electron configurations. Relative value of o vs t. The effect on color of complexes of an octahedral to tetrahedral transformation, effect on absorption intensity. Magnetism of complexes, spin only moment, spin orbit coupling (SOC), effect of SOC on magnetic moment, occurrence of SOC. The spectrochemical series, pi donor ligands, pi acceptor ligands, their effect on , molecular orbital diagrams explaining this effect. The effect of tetragonal distortions on octahedral ligand fields and orbital energies, Jahn-Teller distortions and where they occur. A familiarity with Tanabe Sugano Diagrams, there use in interpreting UV-VIS spectra.
2) Be able to describe/illustrate the sigma and pi bonding of a transition metal atom(s) to a) an alkyl ligand, b) an alkylidene (carbene) ligand, c) an alkylidyne (carbyne, cf nitrido). Consider the (de)stabilizing effect of alpha-substituent groups or heteroatoms on the strength of the metal-carbon bonding. Consider the influence of beta-hydrogen atoms on the stability of each of the above. Consider whether the ligand is acting as an electron donor or acceptor in each sigma and pi bonding interaction.
3) Be able to describe/illustrate the sigma and pi bonding of a transition metal atom(s) to a) an 2 olefin (alkene) ligand, b) a two-electron donor acetylene ligand, c) a four-electron acetylene donor ligand, d) an µ2 2 acetylene ligand, e) an allyl ligand and f) 5cyclopentadienyl ligand. In parts a) and b) consider the effect on the Dewar-Duncanson bonding model of extensive ligand -acceptor/metal donor character. Describe an alternative bonding model which reflects this extreme state of affairs. Be sure to consider orbital overlaps, types of bonds, bond orders, bond angles, hybridization, relative bond lengths and how substituents will affect sigma and pi bonding. Be able to describe and use the "hapto" system and illustrate how a given ligand may have variable hapticities and how this is independent of the electron contribution.
4) Consider the various ways carbon monoxide may bond to transition metals. Be able to describe the bonding, molecular orbital diagram, illustrate the molecular orbital shapes in a terminal CO, illustrate orbital overlaps for a bridging CO. Be able to describe the bonding of NO its similarities and differences to CO. Ditto N2.
Use the following subjects to construct outlines for the final chapters.
Ch 20/21/22 - Sc, Y, La, Ac; Ti, Zr, Hf; V, Nb, Ta:
d vs p orbitals on metal bonding. Prevalence of beta elimination
of H from M-alkyls, Ziegler-Natta Catalysis mechanism of olefin polymerization.
Fluxional behavior in tetrakiscyclopentadienyl titanium. Binary carbonyls
of vanadium and the EAN. Structure and magnetism in M6X12n+ (n = 2,
3, 4) Clusters. Properties and magnetism in bis cyclopentadienyl metal
derivatives.
Ch 23/24/25 - Cr, Mo, W; Mn, Tc, Re; Fe, Ru, Os:
Jahn-Teller distortions in CrF6(4-). Metal-metal bonding in
[M2Cl9](3-) clusters of Cr, Mo, W. Bonding in [M6Cl8]4+ clusters of
Cr, Mo, W. Metal-metal bonding (bond order and bond length) in [Mo2Cl8](4-),
[Mo2OAc4], [Re2Cl8](2-), [Tc2Cl8](2-), [Tc2Cl8](3-). Be able to draw
orbital overlaps showing how a quadruple bond is made. Be able to describe
the metallocyclobutane mechanism of the "olefin metathesis" reaction in which
propylene is catalytically converted into ethylene and butylene. Show
the active catalyst and describe the active site. Describe the structure
of the simplest binary carbonyls of each metal and the following anions: Fe(CO)4(2-),
Mn(CO)5(-), Fe2(CO)8(2-). Describe the manipulations required to construct
the molecular orbital diagram of the "osmyl" group (p 1261), the [Cl5Ru-O-RuCl5](4-)
and obtain the proper bond orders. Structures and bonding in Re3Cl9
clusters. Structures and EAN in clusters: [Fe4(CO)13](2-), [Os6(CO)18].
Properties and magnetism in bis cyclopentadienyl metal derivatives.
Ch 26/27/28 - Co, Rh, Ir; Ni, Pd, Pt, Cu, Ag, Au:
The effect of ligand field on the Co(II)/Co(III) couple. The
effect of changing the Cl- concentration in an aqueous solution of Co(2+)
(color changes blue to pink). Mechanism of the hydrogenation of olefins
by Wilkinson's catalyst, RhCl(PPh3)3. The mechanism of hydroformylation
of propylene with Wilkinson's Rh(CO)H(PPh3)3. Describe the structure
of the simplest binary carbonyls of Co and Ni; the differences in structure
of [M4(CO)12], M = Co, Rh and Ir. The Reppe synthesis. Structure
and EAN in Clusters: Ir4(CO)12, Rh6(CO)12, [Ni5(CO)12(2-), [Ni6(CO)12(2-),
[Pt3(CO)6]n(2-) (n = 2,3), [CuXL]4 (L = PR3, AsR3, X = hal.), [Cu4(SPh)6](2-),
CuOCl6(OPPh3)4. Properties and magnetism in bis cyclopentadienyl metal
derivatives.
Review B6H6 closo-hydridoborane anion BONDING from Ch 7 (Boron). Review Wade's rules as they apply to closo-clusters of M3-12.
Materials Chemistry:
The Solid State taken from “Inorganic
Chemistry”, by Catherine E. Housecroft & Alan G. Sharpe.
Consider the following: close packing of spheres;
alloys/intermetallic cmpds; crystal defects & F-centers; band
structure of insulators, metals, semiconductors (intrinsic/extrinsic);
conduction in ionic solids (electron & ion); basics of CVD
methods.
First Examination Coverage Second Exam Coverage Third Exam Coverage