CHEM 502 - Instrumental Analysis
Section 001, Course# 11641, 3.0 Credit Hrs – Fall
2009
Time/Location: 12:30 - 1:45 TR / Sims 302
Professor: Dr. Cliff Calloway, callowayc@winthrop.edu
Office/Phone: 312-B Sims Hall / 323-4945
Office Hours: MWF 10:00 - 12:00 {And other times by
appointment….please don’t hesitate to contact me.}
Textbook: Skoog, D.A., Holler, F.J., Crouch, S.R. Principles
of Instrumental Analysis, 6thedition, 2007.
Pre-requisites: Grade of C or better in
Chem 313, 314 and Chem 301
Introduction:
Chemical analysis methods are frequently used in
biotechnology, pharmaceutical, environmental, geological, materials
development, forensic, medical, nutritional, and industrial labs. The scientists
and engineers conducting research and development for these industries often
seek answers to chemical identity, structure, or amounts. As such, chemical
analysis plays a critical role in scientific development. Qualitative and
quantitative methods of chemical analysis for organic, biochemical, and
inorganic compounds fall into two categories….classical (or wet) methods
and instrumental methods. In Chemistry 313/314, we surveyed some
classical methods of analysis, including titration, gravimetric and volumetric
analysis, as well as some instrumental methods of analysis (gas & liquid
chromatography, atomic & molecular spectrometry, and electrochemistry).
Although there is not always a clear barrier between the two, the primary
difference arises from the type of physical property used to provide
information. Classical methods often rely on reactivity or physical properties
such as solubility, color, melting and/or boiling points, odors, or refractive
indices for qualitative information, while gravimetric, volumetric, and
titrimetric measurements provide quantitative information. Classical methods
for the separation of mixtures are mainly solvent extractions, precipitation,
and distillation. Instrumental methods of analysis typically utilize other physical
properties such as absorption or emission of light, mass-to-charge ratio,
electrode potential, current, or charge measured with modern sophisticated
electronic devices. Separations are carried out by more efficient
chromatography and electrophoresis methods.
Instrumental
methods of analysis certainly extend well beyond the chemistry lab.
Unfortunately, some scientists view and utilize these instruments as
"black boxes". The term implies a device in which the scientist
places a sample and somehow a number is generated that influences the
scientist’s decision-making process. It should be apparent that this approach
could be dangerous, as the old saying "Garbage In/Garbage Out" is
often true. As such any scientist using sophisticated instrumental equipment
needs at least a basic understanding of how these devices are designed to work.
Course
Goals:
Instrumental
Analysis is a broad and continually expanding subject as new technologies
emerge, but these methods can generally be categorized as spectroscopic, electrochemical,
or chromatographic. In this course, we will essentially take the cover off
these "black boxes" to see how these instruments are constructed and
how measurements are made from the underlying chemical and physical properties
of the substance. In fact, you are likely to see instrumentation represented
from other courses you’ve taken, demonstrating the broad impact instrumentation
has in science. Quantitative problem solving will be utilized as a means to
demonstrate the chemical and physical principles applied to the design and
performance of instruments.
The goal of this
course is NOT to make you an "expert" on every type of
instrumentation to be encountered in a science lab, but rather to introduce and
educate you to the common principles as well as the variety of instrumentation
available for chemical analysis and the type(s) of information these
instruments provide. It is my hope that you will then expand your knowledge of
the instruments you come into contact with during your scientific career,
thereby avoiding the "black box" problem.
Specific Course Objectives:
By the end of this course, you should be able to
demonstrate:
- an
understanding of how chemical and physical properties of substances are
used in the design and construction of modern sophisticated
instrumentation used for chemical analysis
- a
broad knowledge of the types of instrumentation generally available and
the information provided by each
- a
knowledge of appropriate instrumental methods for addressing a chemical
analysis problem
- the
advantages, disadvantages, and limitations of different instruments used
for similar types of analyses
- rigorous
mathematical methods to evaluate instrument performance
Grading/Evaluation:
Student
Conduct Code: “Responsibility for good conduct rests with students as adult
individuals.” Since all graded work (including homework to be collected,
quizzes, papers, mid-term examinations, final examination, research proposals,
laboratory results and reports, etc.) are used in the determination of academic
progress, no collaboration on such work is permitted unless the instructor
explicitly indicates that some specific degree of collaboration is allowed.
This statement is not intended to discourage students from studying together,
seeking help from the instructor, or working together on assignments that are
not to be collected. Refer to the “Academic Misconduct Policy” in the online Student
Handbook: http://www2.winthrop.edu/studentaffairs/handbook/StudentHandbook.pdf
Grades in this course
will be determined from three sources, as follows:
- Homework
(20%): Periodically, homework problems will be assigned from the textbook
or as handouts, and collected. Due dates for each assignment are the final
date each assignment will be accepted. Your lowest homework assignment
will be dropped before averaging.
- Mid-term Exams (60%):
There will be 4 exams given during the term covering the topics listed
below. Make sure to bring pencil and scientific calculator to the exam.
Make-up exams will not be given except under extreme circumstances. If
you plan to miss an exam with valid excuse, let me know as soon as
possible. The exams are scheduled as follows:
- Exam
1: September 17
- Exam
2: October 15
- Exam
3: November 12
- Exam
4: December 1
- Final
Examination (20%): Friday, December 11, 11:30 a.m. – 2:00 p.m. This will be
a cumulative final examination given during exam week. If you score higher
on the final exam than your lowest mid-term exam, the final exam grade
will replace the lowest exam grade, before averaging.
Letter grades will be assigned as follows:
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94 - 100%:
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A
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90-93%:
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A-
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86-89%:
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B+
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82-85%:
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B
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78-81%:
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B-
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74-77%:
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C+
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70-73%:
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C
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66-69%:
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C-
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62-65%:
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D+
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58-61%:
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D
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55-57%:
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D-
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Attendance:
You
are expected to attend each class meeting for the full scheduled time.
Instrumental Analysis is a difficult upper-level course and this will help you to
concentrate on the appropriate material and reinforce the assigned readings and
problems. You are required to bring pencil, paper, textbook, and a scientific
calculator to each class. Cell phone calculators are not acceptable.
Students
with Disabilities:
Winthrop University is dedicated to providing access to
education. If you have a disability and require specific accommodations
to complete this course, contact Services for Students with Disabilities, at
323-3290. Once you have your official notice of accommodations from
Services for Students with Disabilities, please inform me as early as possible
in the semester.
Additional
Requirements for Graduate Level Credit:
Students
wishing to receive graduate level credit for this course are required to
complete a 5-7 page review paper on a cutting edge analytical technique.
Resources can be found by reviewing either the “Fundamentals Review” or
“Applications Review” issues of the journal, Analytical Chemistry (June
15th issue of even & odd years, respectively). The paper must
cite a minimum of 10 primary literature sources and must be submitted by
December 8, 2009. Graduate students should be aware that Winthrop’s +/-
grading system is not applicable to courses taken for graduate credit. Letter
grades will be assigned as follows: 92%-100% A; 83%-91% B; 74%-82% C, 55%-73%
D.
Syllabus
Changes:
While
unlikely, the Professor reserves the right to change the course syllabus if
circumstances dictate. You will be notified of any change through class
meetings and/or email.
Course
Calendar: *Revised – August 25, 2009
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Tentative
Schedule*:
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Date
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Lecture Sections
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T, 25-August
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Introduction,
Ch.1
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R, 27-August
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Ch. 2A
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T, 1-September
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Ch.
2B-C
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R, 3-September
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Ch. 3A-C
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T, 8-September
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Ch.
5A-B
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R, 10-September
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Ch. 5C
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T, 15-September
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Ch. 6A-B;
Review
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R, 17-September
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Exam 1 (Ch.
1-3C, 5)
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T, 22-September
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Ch. 6C-D
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R, 24-September
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Ch. 7A-B
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T, 29-September
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Ch. 7C-E
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R, 1-October
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Ch 7F-7I
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T, 6-October
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Ch.
13
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R, 8-October
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Ch. 15
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T, 13-October
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Ch.
16A; Review
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R, 15-October
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Exam 2 (Ch.
6-7, 13, 15)
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T, 20-October
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Fall Break
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R, 22-October
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Ch.
16B-C
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T, 27-October
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Ch. 18A
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R, 29-October
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Ch. 18B-C
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T, 3-November
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Ch.
19A-C
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R, 5-November
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Ch. 19D-H
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T, 10-November
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Ch. 26A-F;
Review
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R, 12-November
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Exam
3 (Ch. 16, 18, 19)
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T, 17-November
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Ch.
29A-C
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R, 19-November
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Ch.
30A-B
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T, 24-November
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Ch.
30C-E; Review
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R, 26-Novemberl
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Thanksgiving
Break
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T, 1-December
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Exam 4 (Ch.
26, 29, 30)
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R, 3-December
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Review &
Course Evaluation
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T, 8-December
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Study Day
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F, 11-December
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Final
Exam – 11:30 am
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*Subject to change, if weather or events make it
necessary.
Instrumental Analysis Student Competencies
Principles
of Instrumental Analysis, 6th. ed., Douglas A. Skoog, F. James Holler, Stanley R.
Crouch, 2007.
Chapter 1 Student
competencies
Upon
completion of this chapter, students should be able to:
- Differentiate
between Classical Methods of Analysis and Instrumental Methods of
Analysis.
- Describe
the different domains through which data is passed within a sophisticated
instrument.
- Understand
the terms detector, transducer, and sensor.
- Have
a general knowledge of how to select an analytical method for chemical
analysis.
- Calculate
and interpret analytical figures of merit, including accuracy, precision,
signal-to-noise ratio, sensitivity (calibration and analytical), limit of
detection (LOD), linearity via log-log plots, and linear dynamic range
(LDR)
- Utilize
calibration, standard addition, and internal standard methods of analysis,
as introduced in Quantitative Analysis.
Chapter 2 Student
competencies
Upon
completion of this chapter, students should be able to:
- Utilize
the basic laws of electricity, including Ohm’s Law, Kirchoff’s current and
voltage laws, and the power law to find voltage, current, resistance or
wattage.
- Determine
the total resistance in a series circuit or calculate voltage at various
points in a voltage divider.
- Determine
the total resistance in a parallel circuit or calculate the current at
various points in a current divider.
- Differentiate
between dc and ac circuits.
- Work
with expressions for sinusoidal currents, including terms related to
amplitude, period, frequency, angular velocity, and phase angle.
Chapter 3 Student competencies
Upon completion of this chapter, students should be able to:
·
Understand purpose of an operational amplifier in
instrument measurement including general structure of these integrated circuits
·
Understand difference between inverting and non-inverting
inputs
·
Understand the operational modes used including comparator,
voltage follower, and current follower
·
Know how operational amplifiers are used for current &
voltage amplification
Chapter 5 Student competencies
Upon
completion of this chapter, students should be able to:
- Determine
and interpret the meaning of the signal-to-noise ratio.
- Explain
sources of instrumental noise, including shot, flicker, and environmental
noise, and factors that influence the magnitude of each.
- Classify
an instrument as shot or flicker noise limited.
- Understand
the various hardware techniques used to reduce environmental and external
electronic noise sources.
- Describe
the purpose of differential and instrumental amplifiers in instrumental
design as well as contrast the advantages and disadvantages of each type
of amplifier
- Describe
the purpose of high pass; low pass; and narrow band pass analog filters in
instrument design.
- Discuss
the technique of modulation/demodulation in noise reduction of dc signals.
- Describe
how a lock-in amplifier works.
- Understand
the various software techniques used to reduce noise including ensemble averaging,
boxcar averaging, digital filtering, and Fourier transform.
Chapter 6 Student competencies
Upon
completion of this chapter, students should be able to:
- Describe
the wave and particle properties of electromagnetic radiation.
- Inter-convert
between wavelength, frequency, period, energy, and wavenumber.
- Describe
the relative ordering of the electromagnetic spectral regions and the
types of transitions that occur in each region.
- Describe
the superposition of wave theory, and how this relates to Fourier
transform
- Describe
diffraction of radiation.
- Define
coherent radiation, blackbody radiation, fluorescence, phosphorescence,
resonance fluorescence, Stokes and Anti-Stokes Shifts.
- Contrast
line, band, and continuum spectra.
- Inter-convert
between transmittance and absorbance data.
- Utilize
Beer’s Law to determine concentrations from absorbance data, and vice
versa.
Chapter 7 Student competencies
Upon
completion of this chapter, students should be able to:
- Describe
and diagram the basic components in absorption, emission, and luminescence
optical spectrometers
- List
and describe some common light sources used in the infrared, visible, and
UV regions of the electromagnetic spectrum
- Describe
the differences between line, continuum, and quasi-continuum light sources,
and the applications of each.
- Describe
the components of a laser.
- Describe
the four mechanisms involved in a laser and which processes contribute to
or attenuate laser power.
- Describe
various wavelength selectors including absorption filters, interference
filters, and monochromators (Bunsen, Czerny-Turner, and Echelle.
- Describe
how diffraction gratings disperse light.
- Utilize
the grating formula to calculate wavelengths at various incident and
reflected angles for various orders.
- Understand
the terms single channel and multi channel radiation transducer.
- List
and describe phototubes, photomultiplier tubes, and silicon photodiodes.
- List
and describe linear diode arrays, charge coupled devices, and charge
injection devices.
Chapter 13 Student competencies
Upon
completion of this chapter, students should be able to:
- Differentiate
between radiant power and intensity.
- Define
and calculate transmittance and absorbance.
- Differentiate
between absorptivity and molar absorptivity in Beer’s Law
- Derive
Beer’s Law.
- Give
limitations to Beer’s Law
- Utilize
Beer’s Law in solving for concentration of mixtures and equilibrium
concentrations.
- Describe
what is meant by photometric error.
- Describe
the components and arrangements of a single beam and double beam spectrophotometer
and the purpose of each design.
- Describe
common sources and detection systems used in molecular UV/Vis
spectrometry.
Chapter 15 Student competencies
Upon
completion of this chapter, students should be able to:
- Explain
the terms resonance fluorescence, Stokes shift, diamagnetic, paramagnetic,
singlet state, doublet state, and triplet state.
- Draw
energy level diagrams representing fluorescence and phosphorescence
indicating absorption, internal conversion, vibrational relaxation,
intersystem crossing, fluorescence, and phosphorescence.
- Distinguish
between fluorescence and phosphorescence.
- Define
quantum yield.
- Discuss
variables that affect fluorescent and phosphorescent quantum yield
including structure relationships, type of transition, dissolved oxygen,
heavy atoms, temperature and pH.
- Explain
relationship between fluorescent intensity and concentration leading to
quantitative methods of analysis
- Discuss
sources of deviation from linearity for fluorescence including
self-quenching and self-absorption
- Explain
the difference between Excitation and Emission Spectra.
- Describe
the typical components and arrangement of a typical spectrofluorometer.
- Describe
the components used for phosphorimetry.
- Discuss
standardization of fluorescence instruments
- Discuss
methods of analysis in molecular luminescence including the use of
fluorescent derivatives and measurement of luminescent lifetime.
- Use
calibration curve and standard addition methods of analysis for
concentration determination from luminescence measurements
Chapter 16 Student competencies
Upon
completion of this chapter, students should be able to:
- Describe
the various types of molecular vibrations and the factors that lead to
infrared radiation absorption.
- Describe
and utilize mathematical relationships from the classical and quantum
mechanical models for molecular vibration to calculate vibrational
frequencies.
- Calculate
the number of normal modes of vibration for linear and non-linear
molecules.
- Describe
vibrational coupling and its consequences.
- Discuss
various components of infrared spectrometers.
- Explain
time and frequency domain spectroscopy
- Describe
the frequency problem in time domain IR spectroscopy and a Michelson
interferometer.
- Use
mathematical relationships to relate interferogram to source frequencies.
- Use
mathematical relationships to calculate resolution in Fourier transform
instruments.
- Compare
dispersive and Fourier transform IR spectrometers.
Chapter 18 Student competencies
Upon
completion of this chapter, students should be able to:
- Describe
the mechanism leading to Raman and Rayleigh scattering, including
definition of virtual state, leading to Stokes and Anti-Stokes shifts.
- Compare
the factors that lead to Raman spectra with infrared spectra.
- Describe
the components of a typical Raman spectrometer.
- Convert
frequency shifts in Raman spectra to wavelength for a given source.
- Explain
how a depolarization ratio is determined in Raman and the information
gained.
Chapter 19 Student competencies
Upon
completion of this chapter, students should be able to:
- Describe
how a proton NMR spectrum arises quantum and classical descriptions,
including calculation of transition frequency and influence of magnetic
field strength.
- Use
Boltzman calculation for population of excited state.
- Describe
saturation and relaxation processes in NMR
- Describe
Fourier transform in NMR.
- Describe
environmental influences to NMR signals including chemical shift and
spin-spin splitting.
- Discuss
decoupling techniques in NMR
- Describe
the components of a typical FT-NMR.
- Describe
the purpose of locking and shimming an NMR spectrometer.
- Describe
and show how NMR can be used for qualitative analysis.
- Apply
NMR theory to carbon-13 nuclei.
- Discuss
application of 2-D NMR to structure elucidation.
Chapter 26 Student competencies
This chapter will be covered quickly for review of
separation concepts. You should be familiar with these and be able to:
·
Define chromatographic separation terms including partition
coefficient, retention time, retention volume, adjusted retention time and
volume, capacity factor, relative retention, number of plates, and plate height
·
Understand the major driving forces that lead to
chromatographic band broadening, including multiple path, longitudinal
diffusion, and mass transfer.
·
Understand the factors that influence resolution in
chromatographic systems.
·
Apply chromatographic systems to problems of qualitative
and quantitative analysis.
Chapter 29 Student competencies
Upon
completion of this chapter, students should be able to:
·
Describe
supercritical fluids including properties relative to gases and liquids, such
as density, diffusion, and viscosity.
·
Draw a
block diagram for SFC instrument.
·
Give
examples of types of detectors used in SFC
·
Compare
advantages & disadvantages of SFC relative to HPLC and GC.
·
Describe
the effect of pressure on chromatograms.
·
Describe
the advantageous properties of supercritical carbon dioxide
·
Compare
supercritical fluid and liquid-liquid extractions.
Chapter 30 Student competencies
Upon
completion of this chapter, students should be able to:
·
Describe
the separation mechanism in electrophoresis.
·
Describe
common current applications of electrophoresis.
·
Draw a
block diagram of a CE system.
·
Compare
CE and slab electrophoresis.
·
Relate
migration velocity to field strength and electrophoretic mobility.
·
Describe
how the structural features of substance influence electrophoretic mobility.
·
Calculate
plate height and number of plates in a capillary.
·
Describe
the mechanism of electroosmotic flow, and the effect on positive, negative, and
neutral analytes
·
Use
van Deemter’s equation to compare separation efficiency relative to HPLC &
GC
·
Discuss
electrokinetic and hydrodynamic (pressure) injection methods in CE
·
Give
examples of common detectors used in CE