Introductory Physical Chemistry
Final Exam Points of Focus
Gas Laws:
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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.
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
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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.
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.
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.
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
instrument resolution
o 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.