Introductory Physical Chemistry Final Exam Points of Focus

Transcription

1 Introductory Physical Chemistry Final Exam Points of Focus Gas Laws: Understand the foundations of the basic SI units of Pressure and Temperature. Know and be able to use the ideal gas law. Know and be able to use Dalton's Law of Partial Pressures Know the deficicencies of the ideal gas law and what corrections are made in the Van der Waals and other equaitons of state. What corrections contribute to increased or decreased pressure corrections to the ideal gas law and why. Know the behavior of real gases as they are compressed under constant temperature conditions. Know the characteristics of such a compression curve and know what the critical point is and the behavior of gases below and above the critical point. Kinetic Theory and Gases: Know the basic principles or assumptions of Kinetic Theory. Be able to interpret a Boltzmann distribution and know how the distribution changes with mass and temperature. Understand how Kinetic theory leads to arithmetical descriptions of measureable values such as pressure, relative velocities, and rate constants. Be able to, given the relations, calculate such values. Know how collision theory leads to the calculation of reaction rates. Know how energy is distributed among the various motions of a molecular systemn. Be able to connect molecular properties including internal and translational motion to thermodynamic values including entropy, internal energy and heat capacity. First Law of Thermodynamics, Heat and Work Understand the basic concepts of what heat, work, internal energy and enthalpy are and how they relate to molecular motion and properties. What are each of these valeus and what do they represent? Know and understand the First Law of Thermodynamics. Know what a "state" function is and represents, which values are state functions and the advantages of being a state function. Know what a "reversible" process is and how it relates to the quantities above. Be able to carry out simple calculations necessary to evaluate the quantities listed above for: o Heating/cooling processes at constant pressure or volume. o Expansion and contraction to constant temperatures. o Adiabatic processes o Chemical reactions o Phase transfers at 298 K and at other temperatures.

2 Thermochemistry and Calorimetry Understand and know the thermodynamic reference value for enthalpy and how the reference values are obtained for substances. Be able to carry out basic constant volume (bomb) or constant pressure (open vessel) calorimetry calculations in order to determine reaction enthalpies. Be able to calculate heat of formation values for a substance from other reactions of known enthalpies and from calorimetry experiments. Be able to calculate reaction enthalpies at other temperatures under the assumptions of constant heat capacity. Second Law of Thermodynamics, Gibbs Free Energy and Spontaneity Understand the statistical basis for entropy. Know and understand the Second Law of Thermodynamics and why it works. Ba able to calculate theentropy change for elementary processes. Know and understand the Zeroth Law of Thermodynamics and how it establishes a reference point for entropy. Be able to use entropy and enthalpy in order to determine the spontaneity of a reaction system or process. Gibbs Free energy and Applications Know the development of Free Energy and its relationship to entropy, enthalpy and spontaneity. Know the reference point for Free Energy and be able to use such to calculate the Free energy change for chemical processes. Understand how the Gibbs Free enregy is used to develop equilibrium expressions for phase transitions. Be able to use the developed expressions in order to predict the phase change properties of a pure system at different temperatures and pressures involving melting point, boiling point and vapor pressure. Be able to apply the above concepts to the development of a phase diagram and be able to read a phase diagram in order to predict substance behavior under varying temperature and pressure conditions. Applications of Thermodynamics Chemical Equilibrium Know and understand the use of the Gibbs free Energy and also basic assumptions utilized in the development of an equilibrium constant and reaction quotient. Be able to calculate the Standard Free Energy, the reaction quotient and the equilibrium constant from standard values. Be able to calculate the equilibrium constant and equilibrium conditons of a system at different temperatures or be able to use such in order to calculate reaction free energies, enthalpies and entropies. Be able to use the connection between the equilibrium constant and thermodynamic values in order to predict properties of an equilibrium reaction system and a phase change system.

3 Activities and Solutions Be able to calculate concentrations and properties of ideal solutions using: o Raoult s Law o Henry s Law o Boiling Point Elevation/Freezing Point Depression o Osmotic Pressure Be able to use a boilimg point diagram in order to predict distillate concentrations. Understand the concept of a partial molar quantity and specifically, the partial molar Gibbs Free Energy, called the chemical potential.understand what the chemical potential represents. Understand the concept and use of the activity of a solution and how it connects thermodynamic values to real solutions. Be able to calcualte the activity and activity coefficient from experimentally measured values of: o Vapor pressures o Boiling/Freezing Points o Osmotic Pressure Be able to calculate the activity of an ionic solution from the Debye-Huckel formulation. Understand the different reference properties used to develop activites for solutions and the best application for each. Kinetics Understand and be able to use the defining quantities in kinetics including: o Rate of a reaction o Order o Rate constant Be albe to use phenomenological conditions in order to elucidate a rate law. Examples include but are not limited to: Method of initial Rates, Trial Plotting Methods, Half order methods, etc. Understand the concept of an Activation Energy and be able to calculate rate constants at other temperatures given an activation energy or use two rate constants at different temperatures in order to calculate an activation energy using the Arrhenius definition. Be able to derive a rate law from a proposed mechanism using prior equilibrium methods and steady state methods. Be able to connect experimental information in order to provide evidence to support or refute a mechanism. Be familiar with common reaction systems including equilibrium systems, successive reaction systems, polymer formation and multiple channel systems. Know and be able to define and discern the various mechanisms related to enzymesubstrate kinetics including inhibited and non-inhibited mechanisms.

4 Quantum Mechanics, Atoms, Molecules and Spectra Be able to readily transform between values of frequency, wavenumber, energy and wavelength. Know the experiments that produced problems in classical physics and gave insight into the development of quantum mechanics including black box radiation, the photoelectric effect, and line spectra in atoms leading to the Bohr model of the hydrogen atom Know and be able to use the debroglie relation and the Heisenburg Uncertainty Principle and understand how they effect what we observe and what we are unable to observe. Understand the concept of a wave function and know the requirements on the wave function as outlined be the First Postulate of Quantum Mechanics. Be familiar with the systems and energies of quantum models of: o Translational motion (1-D and 3-D particle in a box) o Vibrational motion (harmonic and anharmonic oscillator) o Rotational motion (rigid rotator and centrifugal correction) o Atomic theory (H-atom and multi-electronic atoms) o Molecular Orbital theory. Understand the concept of quantum mechanical tunneling and be able to give examples. Statistical Mechanics Understand the basic principles of statistical mechanics and the development and significance of the partition function. Be able to produce a partion function for a simple system and be able to calculate probabilities and average energies of such a system using the partion function. Be familiar with the complexities involved in properly accounting for quantum states including degeneracy, distinguishability and symmetry. Specifically, how are each of these elements incorporated into the calculation of quantum statistical quantities. Be able to calculate statistical thermodynamic quantities of molecules from knowledge of the partition functions including entropy, energy, and heat capacity. Be able to calculate an equilibrium constant for a simple reaction system. Atoms Be able to calculate the energies of a hydrogen-like atom using the quantum energy expression. Be able to calculate the energy differences between quantum levels and predict the wavelength of light emitted or absorbed by a transition between such levels. Understand and know the qualitative appearance of atomic orbitals including: o The radial distribution of s orbitals o The angular distribution of s, p, d, and f orbitals. Understand the origins of spin. Understand the nature of the magnetic fields generated by electrons from orbital and spin angular momentum and their effect on the energy of the atom. Be able to interpret an atomic Term Symbol to describe the orbital, spin and total angular momenta.

5 Molecules Understand the basic principles of Molecular Orbital Theory using the LCAO-MO approach. Be able to predict the bond order and molecular orbital structure using energy level diagrams for second period elements. Be able to describe the bonding in simple molecules using results from quantum calculations using MO theory describing bonding, anti-bonding, sigma, pi and hybrid orbitals. Spectroscopy Know the requirements for initiating a quantum transition using E-M radiation and the factors that determine relative radiation absorption intensity. Know and understand properties related to the absorption and emission of radiation and the spectral peaks including: o Selection Rules o The presence of a dipole moment in a system o Line Broadening from Doppler effects, transition lifetime effects and o instrument resolution Peak intensities as determined from the population of quantum states, concentration and the Franck-Condon principle. For a real or hypothetical quantum system, be able to predict the spectral quantities that would result. Understand the basic causes for appearance and be able to calculate molecular properties from simplespectra and compound spectra such as vibrational-rotational spectra and electronic-vibrational spectra. Be familiar with the concept and applications of Beers Law to single and multiple component systems. Be familiar with the Frank-Condon principle and it s application in the explanation of various radiative phenomena including fluorescence, phophorescence and lasing.