Review For Exam Three (as of April 7th, 2004 - to be updated after lecture Monday)
Chapter One (all sections) nuclear particles (proton, electron, neutron), atomic number Z, Mass number A, isotopes, relative atomic mass (12C = 12.0000 amu), simple quantum theory (ΔE = hν, c = λν, Balmer and other Hydrogen spectral series and the Rydberg equation), Simple Bohr theory, wave-particle duality (de Broglie relation, λ = h/mv and uncertainty principle), Schrödinger equation and the wavefunction (Ψ, probability of finding the particle and Ψ2), Radial and Angular wavefunctions and their behaviors for different types of orbitals, atomic orbitals and quantum numbers (n, ℓ, mℓ, ms), orbitals and letters (ℓ), degeneracy, normalization of Ψ, hydrogen-like orbitals (shapes, energies, radial and angular nodes, signs of lobes, g and u notation for inversion symmetry), ground and excited states, Many-electron atoms (electronic configurations, Aufbau principle, penetration, shielding and Zeff, Hund’s Rule, Pauli exclusion principle, exceptions to Aufbau configurations), Periodic Table and its relation to Quantum Mechanics, valence and core electrons, diagrams of electron configurations, Ionization Energies (IE) and Electron Affinities (EA) (definitions, periodic trends), Bonding models - covalent and ionic, Valence Bond (VB) and Molecular Orbital (MO) theories, VB and Lewis Dot structures (octet rule and exceptions, resonance), paramagnetic and diamagnetic, MO diagrams for homonuclear and heteronuclear diatomic molecules (orbital energies, symmetries, overlap, bonding, antibonding, non-bonding), Electronegativity (three definitions – Pauling, Mulliken, Allred and Rochow - periodic trends), polar bonds and dipole moments in molecules (see symmetry), isoelectronic molecules and ions, molecular shape and VSEPR theory (bonds and lone pairs (LP), coordination number (CN), LP-LP, LP-bond and bon-bond repulsions and angles, know all possibilities for CN 6 and less (see handout), shape for CN 7 and CN 8), geometric isomerism (square planar - cis and trans; octahedral - cis and trans, fac and mer; trigonal bipyramidal - axial and equatorial sites).
HW Chapter 1: 1, 2, 6, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 25, 27, 28, 29, 31, 32.
Chapter Two (sections 1, 2, 3, 4, 5, 6, 8, 9, 11) Nuclear particles (n, p, e, etc.), Mass defect, nuclear binding energy (ΔE = Δmc2), binding energy per nucleon vs. mass number (56Fe most stable nucleus, before this fusion exothermic, after this fission exothermic); types of particles and radiation (α, β, γ, neutrons, etc.) their relative energies and shielding requirements; Radioactivity – units and nuclear reactions; radioactive kinetics - 1st order, half-life, rate constant; artificial isotopes, types and balancing of nuclear reactions, fusion and fission reactions; brief applications of isotopes in kinetic isotope effect, IR and NMR spectroscopies.
HW Chapter 2: 1, 2, 4, 5, 6, 7, 9, 10.
Chapter Three (Sections 1-4, 8) Symmetry operations and elements (Cn, σ, i, Sn, E) definitions and identification in molecules or ions, Point Groups and the use of the flowchart to identify a molecule or ion’s point group, Symmetry and chirality (absence of σ, i, Sn) and polarity (only molecules or ions belonging to one of these point groups may have a permanent dipole moment: Cn (including C1); Cnv and Cs. In the case of Cn and Cnv, the dipole moment, if present, must lie along the Cn axis).
HW Chapter 3: 1, 4, 5, 7, 8, 9, 10, 12, 15, 16, 17, 19, 20 (find point group of each molecule or ion, even if not asked to in problem)
Chapter Four (all sections) Bonding in polyatomics; Hybridization of atomic orbitals in VB theory to form localized sigma bonds; sp – linear, sp2 – trigonal planar, sp3 – tetrahedral, other schemes for higher geometries (sp3d, sp3d2, etc.); pi bonds from non-hybridized orbitals (p and d); examples of all these and comparisons to Lewis structures; Ligand Group Orbital (LGO) approach in MO theory and what are LGOs; examples – linear XH2, bent H2O, trigonal planar BH3, trigonal pyramidal NH3, tetrahedral CH4; MO diagrams - orbital overlap, bonding, non-bonding and anti-bonding orbitals, degeneracy, delocalized bonding; molecular orbitals formed and their symmetry, nodes, etc.; comparison of VB and MO theories; Qualitative partial MO diagrams (CO pi bonds); electron deficient bonding (3-center 2-electron or banana bonds) – example of B2H6.
HW Chapter 4: 1ab, 5, 6, 7, 8, 9, 10, 11, 13ab, 19.
Chapter Five (all sections but 16) Solid state structures of metals and ionic compounds; closest packing of spheres – hexagonal (ABABAB…, hcp) and cubic (ABCABCABC… , ccp or face centered cubic, fcc), 12-coordinate spheres, octahedral (1 per sphere) and tetrahedral (2 per sphere) interstitial holes; unit cell and seven types of crystal lattices (cubic a=b=c, α=β=γ=90o, 1 degree of freedom (DOF); trigonal or rhombohedral a=b=c, α=β=γ (not 90o), 2 DOF; hexagonal a=b, c, α=β=90o γ=120o, 2 DOF; tetragonal a=b, c, α=β=γ=90o, 2 DOF; orthorhombic a, b, c, α=β=γ=90o, 3 DOF; monoclinic a, b, c, β, α=γ=90o, 4 DOF; triclinic a, b, c, α, β, γ, 6 DOF); other arrays – simple cubic, body centered cubic (bcc), actual examples from elements, metals; polymorphism; metallic radii and coordination number; melting points and standard enthalpies of atomization; alloys– substitutional, interstitial, and intermetallic compounds; bonding in solids – the band theory – metals (conductors of electricity), insulators, semiconductors; resistivity and conductivity and their temperature dependence in metals and semiconductors; semiconductors – intrinsic and extrinsic (p and n types); ionic radii and their trends; ionic lattices – structure types; examples follow, but look at stoichiometry, coordination number, number of ions and formula units per unit cell for each – NaCl, CsCl, CaF2, antifluorite, Zinc blende (cubic ZnS) and the diamond lattice, wurtzite (hexagonal ZnS), β-cristobalite (SiO2), rutile (TiO2), layer structures CdX2 (X = Cl, I), Perovskite; Counting atoms per unit cell and four possible types (corner or vertex, edge, face and body); Lattice energy – Coulombic and Born forces, Madelung constants, Born-Lande’ equation (semi-theoretical), Born-Haber equation (thermochemical cycle); Crystal defects – Frenkel, Schottky, and F center, and their effects on overall stoichiometry, density and entropy of the crystal.
HW Chapter 5: 1, 2, 3, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 17.
Chapter Six (all sections) Properties of water as a solvent, structure, hydrogen bonding, dipole moment, density, other physical and thermodynamic properties; Kw and self-ionization, Acid / base chemistry theories – Arrhenius, Brønsted, Lewis; Water as a Brønsted acid or base; Ka, Kb, and Kw for weak acids and bases, conjugate acid/base pairs; molarity, molality, standard state, activity; mono- di- and poly – basic (or protic) acids; inorganic acids (oxoacids, acid halides) and bases (hydroxides, nitrogen bases); brief energetics of acid dissociation; trens within a series of oxoacids; water as a Lewis base and ligand – aquated (metal) cations, their formation and acidity, hydration shell; amphoteric oxides and hydroxides; solubility of (ionic) salts, saturated solutions, Ksp – solubility product / constant and its uses; metal coordination complexes, types of ligands (monodentate, chelates, crowns, cryptands, etc.), common ligands (table) and coordination number; stability constants, chelate effect and factors affecting stability of complexes; hard and soft metals and ligands; handout on isomerism in complexes.
HW Chapter 6: 1, 2, 4, 7, 8, 9, 11, 12, 13, 16, 18, 23, 25, 27.
Chapter Seven (sections 1, 2, 3, 4, 5) Electrochemistry, oxidation and reduction reactions, balancing redox reactions, electrolytic and galvanic cells; Oxidation states; Standard reduction potentials for half cells and overall cells, Eo, and their relations to ΔGo and K; dependence of potential on cell conditions – the Nernst equation; Complex formation and precipitation and their effects on metal reduction potentials; sacrificial anodes and cathodeic protection; Disproportionation reactions; Potential (Latimer) diagrams, finding Eo for a reaction not given explicitly.
HW Chapter 7: 1, 2, 3, 4, 5, 6, 7, 14, 18, 20.
Chapter Nineteen (sections 1, 2, 3, 5, 7, 8)
Physical properties and electron configurations of d block metals; lanthanoid contraction; colors of ionic compounds and d electron configurations, color wheel; paramagnetism and diamagnetism; variable oxidation states; review of coordination numbers, CN = 2, 3, 4, 5, 6 covered previously (see Ch. 6 notes); Higher CN have less fixed geometries (size and energy constraints make various geometries ~equal); isomerism (again, see handout and Ch. 6 notes) structural vs. stereo isomers; structural – ionization, hydration, coordination, linkage, and ‘polymerization’ isomers (plus ligand isomers); stereo - geometrical (cis/trans, fac/mer) and optical isomers.
HW Chapter 19: 6, 7, 9, 13, 14, 17, 18
Chapter Twenty (sections 1, 2, 3, 4, 5, 6, 8)
High spin (HS) and low spin (LS) states; brief VB theory in d-metal complexes; crystal field and ligand field theories, especially for octahedral, tetrahedral and square planar complexes; octahedral - splitting (10 Dq or Δoct) and the barycenter, eg and t2g orbitals; the spectrochemical series, weak and strong field ligands and their effects on splitting and HS vs. LS; electron pairing energy (P); caluclating LFSE (ligand field stabilization energy); oxidation state of the metal, its position in triad and these effects on splitting; brief Jahn-Teller distortions; brief MO theory of d-metal complexes; pi-donor and pi-acceptor ligands and their effect on splitting; brief 18 electron rule (see Ch. 23); NO a one or three electron donor; Electronic spectra of d-metal complexes; d-d and charge transfer transitions (LMCT and MLCT); number and type of transitions for various dn configurations; selection rules (spin and Laporte), forbidden and allowed transitions and examples; Orgel diagrams; Term symbols for ground states (handout); brief magnetic properties (mu effective, Gouy balance, paramagnetism and diamagnetism, ferro-, antiferro- and ferri-magnetism, superexchange).
HW Chapter 20: 1, 3, 4, 5, 6, 8.
Chapter Twenty-Three (sections 1, 2, 3, )
Hapticity and eta notation; common ligand types and their bonding modes – sigma bonded alkyl and aryl, carbonyl (terminal, various bridging), hydride (terminal, various bridging, interstitial), phosphines and phosphites (cone angle, electronic properties), pi bonded organics (alkenes, allyl, butadiene, N2 and H2; 18 electron rule and ligand electron donors.
Best Guess for exam three: Section 23.7 Types of organometallic reactions (CO ligand substitutions, oxidative addition, reductive elimination, alkyl and H migrations, beta H elimination, alpha H abstraction).
HW Chapter 23: 5, 7, 10a, 14, 16.
For the final exam we will hopefully cover some of Chapter Twenty-Five (sections 1, 2, 3, 4, 5)