Home Page and Syllabus for Chem 454
Instrumental Analysis – Spring 2012
Frank Cheng, Renfrew 26A, 885-6387, ifcheng@uidaho.edu
Office Hours 2:30-4:30 MW, You are welcome to stop by and ask questions anytime.
Class Averages on American Chemical Society Instrumental Analysis Exams
Recommended Texts - Recent Editions of:
·
Principles of Instrumental Analysis, Douglas Skoog et. al
·
Contemporary Instrumental Analysis Rubinson and Rubinson
·
Quantitative Chemical Analysis, DC Harris
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1.
Introduction and Review of
Statistics and Error Analysis
Basic Nomenclature
Technique vs. Method
Qualitative v. Quantitative
Accuracy v. Precision
Chem 253 v. Chem 454
‘Wet’ Techniques & Methods
Analyte Concentrations, typical 1-10%
Accuracy +/- 0.1% or 1 ppt
Precision 1%
Instrumental Techniques & Methods
Analyte Concentrations, typical 1ppt to 1ppm or less
Accuracy +/- 10%
Precision 10%
About
Horwitz’s Trumpet
A basic tutorial on charting and basic functions from Microsoft
-Detection limit
-Sensitivity
-Background and Noise
-Linear Range
-Dynamic Range
-Correlation Coefficient
What’s the
difference between calibration curve and standard addition?
-When should you a calibration curve vs.
standard addition?
Problem Set for Electrochemistry
Standard
Electrode Potentials
Single
Electrode Potentials
Precipitation
Reactions on Electrodes
3. Potentiometric Membrane
Electrodes
·
Problem Set for
Potentiometry
·
Ion Selective Electrodes From Warsaw
University of Technology
·
Beginner’s Guide From Nico2000
·
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, A Theoretical Treatment
AC 1987,
59, 386-389,
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
Atomic Spectra NIST Database
Spectrum of Benzene Vapor vs. Benzene in Hexane – Why the difference?
Shot Noise from IEEE - Publication indicating that Thermal and Shot (both are white) noise emanate from the same mechanism.
1/f and Shot Noise Power Spectrum (see Fig 1.)
Noise Filters A text that focuses on digital filters but covers fundamental aspects
Faraday Cage -
Wikipedia,
A
demonstration from Youtube
Luminescence
Fluorescence and Structure
Excitation vs. Emission Spectra
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
-
Multiple Paths for Solute Flow, Eddy Diffusion 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
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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
·
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+
·
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
·
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 8
· Exam 2 (100 points) March 7
· Exam 3 (100 points) April 25
·
Final Exam (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
·
Link to the Chem 454 Laboratory Syllabus
·
Analytical Sciences Digital Library