1.
Introduction and Review Statistics and Error Analysis
·
A
basic tutorial on charting and basic functions from Microsoft
·
Search
for least squares tutorial from Yahoo
·
Tutorial from Widener
University
·
Student t-test
from Rice University , link 2,
o
A
t-test calculator (for comparison of two sets of data)
·
Problem Set for Electrochemistry
3. Potentiometric Membrane Electrodes
·
Problem Set for Potentiometry
·
Latest
Review Literature on ISE's from Google Scholar
4. Voltammetry
·
Voltammetry Problem Set, Answer to Problem 6.
·
CV
Modeling Programs
o
DigiElch CV and titration
simulation
o
The
EC Mechanism
in Cyclic Voltammetry
o
A
Study of an EC’
Mechanism from my research group
·
Modern
Hg drop Electrode System Links - 1, 2
·
ASV
from Wikipedia,
Cypress Systems,
o
Forensic Analysis
of Ba and Pb in Gunshot residue
o
EPA
Method 7063 analysis of As by Anodic Stripping Voltammetry
Problem Set for
5-9 Spectroscopy
·
A Simple
Single Beam Spectrophotometer
·
Jablonski
Diagram (link 2)
and a Bio
·
Noise
& Hear the Noise
o
1/f
Flicker Noise or pink noise and its appearance
in nature
o
Light
Chopper and 1/f
noise
o
Shot
Noise from IEEE - Publication indicating that Thermal and Shot (both are
white) noise emanate from the same mechanism.
o
1/f
and Shot Noise Power Spectrum (see Fig 1.)
o
60 Hz
o
Noise Filters A text that focuses on
digital filters but covers fundamental aspects
o
Faraday
Cage - Wikipedia, A demonstration from Youtube
·
Luminescence
o
Fluorescence
and Structure
o
Excitation
vs. Emission Spectra
o
Chemiluminescence
– Luminol detection of iron in
blood at crime scenes (Link 2)
6. Components of Optical Instruments
·
Sources
o
D2 Lamp
o
W Lamp
·
Wavelength
Isolation
o
Echelle & Echellette
(Link 2)
Gratings
·
Transducers
·
Diode
Array Spectrophotometer a description
·
CCD
Array Spectrophotometer (Ocean Optics CCD
Spectrometer)
·
Sources
- Nernst Glower, Globar
·
Sample
holders - Salt
Plates - Internal
Reflection (see Figure 2)
·
IR
Regions, NIR,
Database of Common Organics from NIST, Applied
Spectroscopy,
·
Example
of Analyses Using IR
o
Wood
o
Wheat
from UI Ag Extension
o
Plastics
o
MTBE in
Gasoline. ASTM, MIDAC
·
Detectors
– Ewing’s
Analytical Instrumentation Handbook
o
Heat
Detectors-DTGS, TGS
o
Photon Detectors-PbS,
InSb, HgCdTe
·
FT-IR
- Wikipedia,
Keck, Newport, Nicolet
o
Apodization
– Math from
Wikipedia, “Ringing”
also Wolfram
Research, A Training Course from Varian
(see slides 39-40), From Columbia
U (see figure 10)
o
Signal
Averaging – Chemometrics
In Analytical Chemistry.
·
Brief
Tutorials - Kaiser
Optical Systems - Wikipedia
- Washington
University - Venkata
Raman Bio
·
Lasers
(link 2, 3, 4, 5)
types
·
Why
FT-Raman has not overtaken dispersive Raman. Link 1,
2,
3
·
Example
of MTBE analysis
with Raman.
·
Forensic
analysis of inks using a Raman microscope (Link 2).
Of cocaine
on fingernails.
·
Atomic
Absorption - University
of Michigan Tutorial, RSC
start on page 2
o
Slot
Burner
·
Flame
Temperature and Fuel Mixtures
·
Flame
Structure
o
Nebulizers
·
Pneumatic
·
Ultrasonic
·
Electrothermal
(See Graphite Furnace below)
o
Pressure
Broadening
o
Doppler effect and broadening in AAS
o
Ionization
Suppression
·
Interferences
from Molecular Species
·
Continuum
Source Correction (Link 2, 3, 4)
·
Smith-Heiftje
·
Graphite
Furnace AAS (Link 2,
3
see Figures 6.10-12)
·
Atomic Emission
– University
of Vermont
·
Relative
LOD for Flame AAS, AES, GFAAS, and ICP
·
Applications
o
Horiba
o
Cholesterol via colloidal
Au
Problem Set for
10-13 Separations
10. Introduction to Separations
·
Introduction
- Chapter 26 - Wikipedia
- Library
for Science
o
Stationary
Phase
o
Mobile
Phase
·
Martin
and Synge work on LC and the 1952
Nobel Prize
o
Partition
Coefficient, K
o
Retention
Time, tr
o
Dead
Time, tm
o
Capacity
Factor, k’
o
Relative
Retention Factor (selectivity), α
·
Band
Broadening
o
Plate Height, H
o
Longitudinal
Diffusion, B/u
o
Mass
Transfer Effects, Cu
1.
Within the Stationary Phase, Cs
2.
Within the Mobile Phase, Cm
o
Multiple
Paths for Solute Flow, A
o
The
van Deemter
Equation, H = A + B/u + Cu
·
Efficiency
of Separation
o
Plates,
N = L/H
o
N and Rs
o
Rs
α L1/2
·
GC
Block Diagram
o
Injection
Port
§
Split Injections
o
Carrier
Gas
o
Column
o
Makeup
Gas
o
Detectors
·
Packed
vs. Capillary Columns
o
Van
Deemter Equation Considerations
§
Effect of A – Single Path for
Capillary Columns
§
B/u effects – Largest in the gas
phase, fast u desirable
§
Cu effects – Thin s.p.
·
Types
of GC stationary phases (Link 1)
o
Example
of a effects on a chromatogram, another link
o
Almost
Always He
o
N2
and H2 are possible
·
Sample Injection
(see page 3) Also Link 2.
o
Splitess
o
Solid
Phase Microextraction (SPME)
§
An
example of explosives detection from the FBI
§
GC/MS
screening for amphetamines from the DOJ
§
Los Alamos National Lab
Forensics Science Center
·
Detectors
for Gas Chromatography
o
Make-up
Gas
o
Thermal
Conductivity Detector (TCD) Link 2
o
Flame
Ionization Detector (FID) Link 2
§
NPD
§
FPD
o
Electron
Capture Detector (ECD) Link 2, Link 3
o
Photoionization
Detector (PID) Link 2
o
FT-IR
o
Mass
Spectrometers
·
Quantitative
Analysis
o
Calibration
Curve
o
Standard
Addition
o
Method
of Internal Standard (from
Cal State – Fresno)
·
GC
troubleshooting guide for HP-GC's (now Agilent)
o
Capillary
columns from Sigma-Aldrich
·
AJP Martin and RLM
Synge’s Original Paper on Liquid Chromatography, Synge’s
Biography
o
Liquid
Mobile Phase
o
Pump
o
Injection
Valve
o
Separation
Column
o
Detector
·
Band
Broadening in LC
o
Van
Deemter Considerations, H = A + B/u + Cu
o
B/U
effects – diffusion is 100x less in liquids when compared to gases
o
Cu
effects largest in LC
o
Minimizing
Cu effects requires smaller packing particles – Surface area/ Volume – High
pressures
o
Effect
of particle size on separation efficiency, see
Figure 2, Link
2
·
HPLC
Pumps
o
Pressures
to 6000 psi +
o
Pulse
free – prevents solute remixing
o
Control Flow Rates 0.1 to 10 mL/min
o
Reciprocating
Pumps
o
Coils
o
Diaphragms
·
Pre-Column
Filters
·
Analytical
HPLC Columns (images)
o
Silica
o
Modified
Silica, C-18, C-8, others
o
Reversed
(polar m.p.-nonpolar s.p.) vs. Normal Phase (nonpolar m.p. – polar s.p.) Separations
o
Partition
(modified silica) vs. Adsorption
(unmodified silica) Chromatography
o
Column Care, Link 2
·
Mobile
Phases
o
Polar
vs. non polar
o
Most
Separations handled by C-18 s.p. and H2O/MeOH or H2O/CH3CN
m.p.
o
Isocratic
(constant composition) vs. Gradient (variable composition) elutions
o
Column
Heaters, improvement of Cu characteristics
·
Detectors
o
Refractive
Index (RI), page
2
o
UV-vis
Absorbance
§
Diode
Array (2 pages)
o
Conductivity
(read all three pages)
o
FT-IR
o
Evaporative
Light Scattering Detector (2 pages)
o
Electrochemical
Detectors
o
Mass
Spectrometry
·
UPLC
Link
1
·
User’s
Guide From University
of Kentucky
·
HPLC
troubleshooting guides Link 1, 2,
3, 4, 5, 6, A
Google Search
13. Capillary Electrophoresis (CE)
·
Electrophoresis vs. CE
·
Basic
Block Diagram
·
Van
Deemter Equation Considerations (H = A + B/u + Cu)
o
A
= 0, as only one path is possible
o
Cu
= 0, as there is no s.p. in CE
·
Theoretical
Plates
o
HPLC
– 2,000 to 10,000
o
CE
– 50,000 to 500,000
·
Theory
of Electrophoresis
·
Electrophoretic
mobility
·
Electro-osmosis
·
tr
trends cations < neutrals < anions
·
flow
velocity profiles, CE vs. HPLC
·
Theoretical
Plates
·
Sample
Injections
·
Pressure
Injection
·
Electro-kinetic
·
Microfluidic
Chips, See this animation
from Stanford
·
Detectors see Table
1 page 298A
·
Challenges
o
Narrow
capillary/channels (20-75 μm)
·
UV-vis
Absorbance
·
Fluorescence
o
Tagging
agents (an
example from Beckman)
o
CE-LIF
o
CE-arrays
·
Mass
Spec
o
Electrospray
– 2002
Nobel Prize for John B. Fenn of Virginia Commonwealth University
·
Modified
CE separations
·
Surfactant
Modified, Anions < Neutrals < Cations
·
Micellar
Electrokinetic Chromatography (1)
o
A
Comparison of LC vs. MEC-CE
·
Analytical
Chemistry Articles
·
1989 Analytical
Chemistry A-page article by AG Ewing
·
"How
capillary electrophoresis sequenced the human genome.", N. J. Dovichi
and J. Z. Zhang, Angew. Chem. Int. Ed., 39 4463 (2000).
·
Analytical
Chemistry “How
Analytical Chemists Saved the Human Genome Project…or at least gave it a
helping hand”
·
A
CE-LIF array from
DOE’s Joint Genome Institute.
·
“Ultra-high-speed
DNA fragment separations using microfabricated capillary array electrophoresis
chips” AT Wooley, RA Mathies, Proc. Natl Acad Sci. 91, 1994 11348-11352
·
Coupled with PCR
Amplification
Problem Set for Mass Spectroscopy
·
Basic
Block Diagram
·
Sample
Inlet
à Ion Source*
à Mass Analyzer*
à Ion Transducer*
à Signal Processing
à Mass Spectrum
·
*
indicates under vacuum conditions
·
Ion
Sources
·
Electron
Impact (Hard)
·
Fragmentation
·
Chemical
Ionization (Soft)
·
MW
information
·
Ionization
of solid and nonvolatiles
·
Matrix-Assisted Laser
Desorption/Ionization (MALDI)
·
Direct
Probe
·
Electrospray
– 2002
Nobel Prize for John B. Fenn of Virginia Commonwealth University
·
Atmospheric
Pressure Chemical Ionization
·
Recent
Developments in Ionization Techniques
o
Direct Analysis in Real
Time (DART)
o
Desorption
Electrospray Ionization (DESI)
o
Atmospheric
Pressure Photoionization Source (APPI)
o
Desorption
atmospheric pressure photoionization (DAPPI)
·
Summary
from Aglient
·
Mass
Analyzers
·
Resolution
·
Quadrapole, a tutorial from
LCGC magazine
·
Ion
Trap
·
Orbitrap (A
review publication)
·
MS-MS
systems
·
Quad-Quad
·
QTOF
·
Electron
Multiplier
·
ICP-MS
·
Guides
to MS
·
ASMS
15. Ion Exchange, Ion, and Molecular Exclusion Chromatographies (IEC, IC,
MEC)
·
IEC
and IC Background
from Wikipedia
·
IEC
from
Amersham Biosciences
o
Anion
Exchangers
§
Quaternary and tertiary ammonium
groups
o
Cation
Exchangers
§
Sulfonate and carboxyl groups
o
Resins
·
Ion
Exchange Selectivity
o
X-
A+ + B+ = X- B+ + A+
o
·
Analytical
Ion Chromatography
o
IC
vs. IEC what’s the difference?
·
Molecular
Exclusion Chromatography
o
Gel
Filtration
o
Gel
Permeation
16. Interpretation of MS Spectra
·
Isotope Distribution and Mass
Spectrum Calculator
o
Calculation of
Isotope Abundances
o
·
Fragmentation
·
General
Rules Regarding Interpretation
17. Advanced Topics in Statistics
·
R2
·
Uncertainty
of Least Squares Fitted Lines (form MathWorld)
·
The t-test for
assessment of two different groups of data. Wikipedia
·
F-Test
·
A
t-test calculator (for comparison of two sets of data)
·
Horwitz Trumpet
(link 2,
3)
18. Grading
-
Exam 1 (100 points) February xx
-
Exam 2 (100 points) March xx
-
Exam 3 (100 points) April xx
-
Final Exam May xx, 12:30 pm (150 points)
-
Laboratory (150 points)
19. Old Exam
Files – Please note that the
exams from previous years will not correspond to this year's course materials
or exam subject matter. They can provide you with an idea as to the exam format
and additional homework assignments.
·
MIT
Courseware Advance Chemical Experimentation and Instrumentation