Be prepared to describe and identify the intermolecular/interparticle forces present in matter and relate these forces to the relative magnitude of physical properties such as vapor pressure, boiling point, melting point, viscosity, surface tension, and solubility.
Be prepared to develop an equilibrium constant expression for a chemical reaction. Know the significance of a large Keq versus a small Keq. Know how to apply Le Châtelier’s Principle (Law of Mass Action) to perturbations of an equilibrium system. Make sure you could calculate a reaction quotient (Q), and determine the direction of “shift” to reach equilibrium and determine the new equilibrium concentrations of all species in a chemical reaction.
Be prepared to work problems using the ideal gas law. Know how to rearrange this expression to solve for gas density or to find the molecular weight or mass of a gas. Know under what conditions one can utilize Boyle’s Law, Charles’ Law, Avogadro’s Law, or the Combined Gas Law and be able to solve problems related to these laws.
Know the key points of the Kinetic Molecular Theory for an Ideal Gas and know under what conditions gases tend to behave non-ideally. Know, in general terms, what corrections have to be made to the ideal gas law under non-ideal conditions.
Be able to write and balance a chemical equation. Be able to perform basic stoichiometry problems, including limiting reagent problems.
Know how to calculate enthalpy changes associated with chemical reactions by utilizing the reaction stoichiometry. Know how to apply Hess’ Law.
Describe how one could make a specific volume of a desired solution of known concentration or prepare a given volume of a dilute solution (concentration given) from a more concentrated solution.
Atomic Structure and Periodic Properties
You should be able to describe the quantum mechanical view of the atom and assign quantum numbers for electrons within an atom. You should be able to generate electron configurations for atoms or ions. You should be able to identify and describe the importance of “valence” electrons. You should know the origins of paramagnetic versus diamagnetic behavior. You should know the meaning of “effective nuclear charge” and be able to express how the “n” value and the ENC give rise to the periodic trends of atomic size and ionization energy.
You should be able to describe ways to “speed up” a chemical reaction. You should be able to draw and/or interpret a reaction energy diagram (i.e., be able to identify: reactants, intermediates, transition states, activation energies, rate-determining step, overall energy changes…). You should know the general form for a rate law and be able to generate a rate law from experimental data. You should know the concept of “order” with respect to an individual reactant and the overall reaction. You should be able to evaluate the plausibility of suggested reaction mechanisms by comparison to a known rate law.
What characteristics of an alkyl halide are important in determining whether nucleophilic displacement will proceed by an SN1 or an SN2 reaction, and why do these characteristics play a part? What characteristics of the attacking nucleophile leaving group and solvent play a part? How would one determine experimentally (two ways) whether a reaction of this sort would be SN1 or SN2?
Electrophilic Addition of Alkenes
Upon addition of unsymmetrical molecules across an unsymmetrical carbon-carbon double bond, what factors govern the regio-selectivity for the molecular fragments and the final structure of the product? How can one control the selectivity? Use mechanisms and intermediate stability in your explanations.
Be able to discuss electrophilic aromatic substitution with emphasis on how and why the inductive effects of ring substituents affect structures of products and the rate of the reactions. Know the 5 reactions that fall in this category and ways of modifying the groups already on the benzene ring.
Structural Determination from Spectroscopy and Spectrometry
Be able to suggest a structure for a substance based on NMR, FTIR, and mass spectrometry data. Alternatively, be able to draw the above spectra if molecular structures are given. Know the most important absorption values for proton NMR and IR.
Be able to discuss the Grignard reaction, identifying starting materials, different products and when each product would be expected, and the complexities of actually running Grignard reactions. Show the mechanisms by which the products are formed.
Types of Reactions
Be able to identify reactions as addition, condensation, hydrolysis, elimination, rearrangement, substitution, oxidation or reduction.
Be prepared to describe the components of a buffer and know which factors determine “buffering capacity”. You should know the basic biologic mechanisms for buffering the body’s fluids and the reasons behind the requirement for buffering of the body’s fluids. You should know how one would select and then prepare a buffer for use in the lab. (Implicit in this is that you must know the Henderson-Hasselbach equation and be able to work problems utilizing this equation.) You should be able to generate and/or interpret titration curves for both monoprotic and polyprotic acids.
Hemoglobin and Myoglobin
You should be able to discuss the structural and functional similarities and differences between hemoglobin and myoglobin. Be able to discuss in detail the various species that influence hemoglobin’s affinity for oxygen (i.e. cooperativity of O2 binding, H+, CO2, 2,3-DPG). You should also be able to compare and contrast important isoforms of hemoglobin including HbA, HbS, HbF, and HbA1c.
Enzyme Regulation and Signal Transduction
Be able to discuss different ways that enzymes’ activities are regulated, including both reversible and irreversible regulation. This means that you should be able to discuss competitive, noncompetitive, and uncompetitive inhibitors as well as allosteric effectors. You should know the roles of kinases and phosphatases. You should understand the concepts of zymogen activation and feedback inhibition. You should also be able to describe the signal transduction cascade responsible for generating the second messenger cAMP and the activation of Protein Kinase A.
Physical Chemistry I
Be prepared to discuss various thermodynamic variables (ex., heat, work, temperature, internal energy, enthalpy, entropy, Gibbs free energy, etc.) and how they relate to one another. Know the steps in the Carnot Cycle and how to calculate efficiency. Be able to determine the sign (i.e. positive, negative, or zero) for q, w, DT, DU, DH, DS and DG for an isothermal or reversible adiabatic expansion or compression of a gas.
Quantum Mechanics and Electronic Spectroscopy
Be prepared to discuss what information is contained in a wavefunction and how this information is obtained (energies, probability densities). You should know the general form of the Schrödinger equation and how it is used with particular reference to a “particle in a box” and the Hydrogen atom. Be able to discuss how “particles in a box” may be used to model electronic spectra of conjugated organic molecules.
Physical Chemistry II
Be able to write the equilibrium expression for an ideal gas mixture (the KPº equation). Be prepared to discuss the relationship between Gibbs free energy and the equilibrium constant. Be able to write the equilibrium expression for a nonideal system (examples: saturated aqueous solution of a salt, weak acid aqueous solution, autoprotolysis of water).
Kinetic Molecular Theory
Be prepared to discuss the Boltzmann distribution and the various physical properties of an ideal gas. You should be able to calculate the root-mean-square speed of a gas at room temperature. You should know the dependence of collision frequency and mean-free-path upon the various physical properties.
Crystal Field Stabilization Energy
Be prepared to explain what is meant by the term “crystal field stabilization energy,” CFSE. Be able to calculate the CFSE for octahedral and tetrahedral complexes. Be able to predict whether particular coordination complexes are high or low spin. Be able to relate the CFSE to the color of coordination complexes.
Be able to determine the symmetry point group for a given compound. Be prepared to predict the vibrational spectra (infrared and Raman) of compounds from character tables. Be able to write a representation (the characters) of parts of a molecule (orbitals, bonds, angles, SALCs), given the point group, and to use the character tables to identify the irrep that corresponds to this representation.
Be prepared to describe trends in ionization energy, electronegativity, size, polarizability, metallicity, and electron affinity. Be able to account for exceptions to broad trends. Be prepared to predict Hard/Soft acid base behavior and solubility based on these trends.
Be prepared to identify the oxidation states of all elements in compounds and ions. Be able to balance Redox half reactions and complete reactions and to calculate reduction potentials given tables of standard reduction potentials and initial cell concentrations.
Be able to describe the instrumental set-up for both Gas and Liquid Chromatography. That should include the types of injectors, columns, and detectors. As part of the discussion you should be able to delineate characteristic advantages and disadvantages of each component. For LC, be able to distinguish between normal phase and reversed phase separation. You should be able to tell what type of instrument is best for different types of samples. An ability to discuss the instrumentation and capabilities of the hyphenated techniques of GC-MS and LC-MS is also important.
Atomic and Molecular Spectroscopy
Be able to describe the instrumental set-up for the following types of spectrometers: AA, ICP-AE, MS, UV-Vis, and IR (both dispersive and FT). You should have an intuitive feel for what’s happening to the atoms or molecules during the analysis process.
NMR, IR, and Mass Spec
Know numerical values for NMR and IR spectra. Be able to go from spectra to molecular structure and visa versa for proton NMR, carbon-13 NMR and IR. Understand the role of decoupling and shift reagent experiments in elucidating complex NMR spectra.
Laser Spectroscopy and Fluorescence
Be able to discuss the parts of a laser and how a laser works. Be able to discuss the various processes a molecule may undergo following electronic excitation (including fluorescence, phosphorescence, intersystem crossing, etc.) and how these processes and their time scales relate to fluorescence spectra.