Senior Comprehensive Examinations

You must register for Senior Comprehensives (CHEM4999). The Chemistry Senior Comp consists of two components described below:

Completion of one of the following capstone courses with a grade of "C" or better. CAPSTONE COURSES: Molecular Structure and Organic Synthesis (CHEM 4320L), Synthesis (CHEM 4310L), Genomic and Proteomics (CHEM 4150L) and Introduction to Research with Undergraduate Research (CHEM 4080 and CHEM 4083).

**Take the Major Field Test in Chemistry and receive a passing score.** Review materials are below.

Review Materials

As with General Chemistry, review for the Organic Chemistry portion of the senior comps can be done through solving the Organic Chemistry 1 and Organic Chemistry 2 final exams found on the department's Organic Chemistry web site. You will find many additional materials on this web site.

For Organic Chemistry 1, here is the Practice Final Exam from the *Organic Chemistry Student Manual* with Key. Here is a Final Exam with Key from the fall of 1999. We also have a Final Exam with Key from the fall of 2000.

For Organic Chemistry 2, here is the Practice Final Exam from the *Organic Chemistry Student Manual* with Key. Here is a Final Exam with Key from the spring of 2000. We also have a Final Exam with Key from the spring of 2001.

**Review for the Quantitative Analysis Part of the Senior Comprehensive Exam **

- Thoroughly understand accuracy and precision and their relationship and ways of expressing accuracy and precision.
- Know the concept of significant figures and be able to determine the significant figures of results in calculations.
- Know what determinate (systematic) errors and indeterminate (random) errors are. Be able to determine the type of a given experimental error.
- Be able to calculate standard deviation, relative standard deviation, and propagation of error.
- Calculation of the confidence limit using statistically derived equations.
- Know how to do a Q test.
- Be familiar with the concepts of atomic, molecular, and formula weight, mole, molarity, equivalence, normality, and related calculations.
- Be familiar with the principles of volumetric analysis and the requirements of a successful titration.
- Be able to carry out stoichiometric calculations in the volumetric analysis.
- Know what the process of standardization is and the requirements of a primary standard. Be familiar with the calculations involved in the standardization process.
- Understand the concepts of chemical equilibrium, rate constant, and equilibrium constant.
- Be able to use the Le Chatelier's principle to predict the effects of temperature, pressure, and concentration on the position of equilibrium.
- Be able to do calculations involved in dissociation equilibria using equilibrium constant and systematic approach.
- Understand the concepts of activity, activity coefficient, ionic strength and their relationship to concentration. Be able to calculate the ionic strength and activity.
- Understand the Arrhenius and Bronsted-Lowry acid-base theories. Acids and their conjugate bases, bases and their conjugate acids.
- Know what strong electrolytes and weak electrolytes are. Be able to write ionization equations of acids and bases in aqueous solutions. Know the autoprotolysis of water. Be able to calculate the equilibrium concentrations of weak acids and weak bases.
- Be familiar with the pH scale of a solution. Calculation of the pH and pOH of a solution. Relationship between [H+] and [OH-], and pH and pOH.
- Understand the hydrolysis of the salts of weak acids and salts of weak bases. Be able to calculate the pH of salt solutions.
- Understand buffer and buffering mechanism. Henderson-Hasselbalch equation. Know how to prepare buffer solutions and how to calculate the pH of a buffer solution.
- Know what an acid-base titration is: equivalent point, end point, titrant, titration curve, etc.
- Characteristics of titrations involving strong acid vs. strong base.
- Know what an indicator is and how to choose an indicator for the titration of a given acid or base. Understand the ionization equilibrium of an indicator. Be able to determine the pH range of color change for an indicator of known pKa.
- Titration of weak acid versus strong base and weak base versus strong acid. Be able to sketch a titration curve and explain the buffer region. Understand the buffering capacity of a weak acid or base during titration. Understand the dependence of the titration curve on the strength of the weak acid or the weak base being titrated and this is reflected on the titration curve.
- Titration of sodium carbonate: titration curve and equivalent points.
- Know what complexometric reactions and titrations are. Be familiar with the following concepts: complexing agent, chelating agent, chelate, complexation equilibrium, formation constant, and dissociation constant.
- Know what EDTA is and why it is a chelating agent. Know the EDTA equilibria in stepwise dissociation of the four ionizable protons and the representation of EDTA as H4Y, H3Y-, H2Y2-, HY3-, and Y4-. Understand the effect of pH on EDTA equilibria.
- Be able to write the complexing reaction between EDTA and metal ions such as Ca2+ and Mg2+.
- Be able to draw EDTA titration curves for the titration of metal ion (pMetal versus mL EDTA). Know what indicator may be used in the Ca2+ and Mg2+ titration with EDTA. Be able to do calculations involved in the EDTA titration of metal ions. For example, the concentration of Ca2+ at equivalence point, the calcium content in the original sample solution.
- Understand the principles of precipitation titrations and be able to draw precipitation titration curves (pCl-, pBr-, etc vs. mL of titrant). Be able to calculate the concentration of the analyte ion at equivalence point.
- Understand the effect of the solubility of the precipitate on the titration end point.
- Know the two types of indicators used in precipitation titrations and how they function as indicators.
- Know what a galvanic cell and an electrolytic cell are. Be able to assign anode and cathode in an electrochemical cell. Be able to write half reactions occurring on the anode and the cathode.
- Know the reduction potentials of half-reactions and the convention by which all half reactions are expressed as reduction reactions. Understand the meanings of a positive reduction potential and a negative reduction potential. Know the standard hydrogen electrode (SHE) and its electrode potential.
- Know how to write a cell for a given redox system. Calculate cell potential.
- Be familiar with the Nernst equation. Calculations using the Nernst equation.
- Know what electromagnetic radiation is and its interaction with matter. Know the definition of wavelength and frequency and their relationship. Be able to interconvert l and n using correct units. Know the relation between the energy and frequency or wavelength. Be able to calculate the energy of electromagnetic radiation given the frequency or wavelength of the radiation. Know the wavelength region for ultraviolet, visible, and infrared radiation.
- Understand the principles of spectrometry based on absorption. Understand the types of electronic transitions involved in the absorption of UV-Vis radiation.
- Be familiar with the following: Beer's law and the relationship between absorbance, transmittance, molar absorptivity, cell pathlength, and concentration of the absorbing species. Calculations involving Beer's law.
- Know the basic components of a UV-Vis spectrometer and the types of spectrometers. Deviations from Beer's law.
- Principles of chromatography. Stationary phase, mobile phase, column efficiency, theoretical plate, number of theoretical plate, retention time, peak width. Understand van Deemter equation.
- Instrumental components of gas chromatography and high performance liquid chromatography.

Students should review the following topics and solve the appropriate example calculations in their Physical Chemistry textbook.

*Gas Properties *Perfect gas law, Dalton's law, partial pressure, kinetic theory, manipulation of gas law to determine gas density, formula weight.

Real gas, van der Waals equation, equipartition theorem, determine E and Cv, Cp of gas molecules.

*1st Law of Thermodynamics *Definition (open, closed, isolated) systems

Q, W, DU, DH for heating at constant volume or pressure

Q, W, DU, DH for isothermal or adiabatic process of perfect gas

Q, W, DU, DH for phase change and chemical reaction

Thermochemistry, Hess's law, Calorimetry, manipulation of DH = DU +DPV.

*2nd Law of Thermodynamics *Entropy and its application, state and path functions.

DS for phase change, gas expansion, and heating.

2nd law and spontaneity of a process

DU, DH, DS, and DG for varieties of processes

Gibbs energy and its significance to chemical reactions

Manipulation of DG = DH - T DS

*2nd /3rd Law of Thermodynamics *Definition of the 3rd law

Determination of S at any temperature

*Phase Equilibrium *Phase diagram

Effect of pressure or temperature

*Solution *Thermodynamics of mixing, ideal solution

Colligative properties

*Chemical Equilibrium *Relation of DG and K

Relation of K an Pi

Effect of temperature or pressure

Chemical equilibrium in solution, acid and bases

*Electrochemistry *Thermodynamics of a cell, Nernst equation

Reduction potentials, electrochemical series

*Kinetics *Rate, rate law, determination of rate law

Effect of temperature on rate and rate constant

Mechanism, write the rate from mechanism

Intermediate, catalyst

*EM radiation *Energy, frequency, wavelength, wavenumber, etc.

*MO theory *Atomic structure, electronic configuration, quantum numbers

Molecular orbital theory

*Laboratory *Typical lab set-ups: bomb calorimetry, V and P of a pure liquid,...

Measurement of temperature, pressure, adsorption,...

Error analysis, accuracy, precision, standard deviation,..