CHEMISTRY 3080 4.

0
Instrumental Methods of Chemical Analysis
Course Director: Dr. Robert McLaren
Petrie Science 301
ext. 30675
e-mail: [email protected]

Office Hours: - by appointment or

- M,W,F @ 2:30-3:30pm
Course Grading
Laboratories 30%
Research Essay 10%
Quizzes (3) 24 %
Assignments 6%
Final Exam 30%

Important Dates:
Classes: Sept. 08 - Dec. 02* (36 classes)
Exams: Dec. 04 - Dec. 19
Labs start: Sept. 22-26 (start)
Tests: Wed. Oct 08, Wed. Nov 05, Fri. Nov 28
Research Essay: Oct 15 (Approval deadline), Nov 16 (due)

Holidays:
Mon Oct 06 Yom Kippur (no classes, University open )
Mon Oct 13 Thanksgiving (no classes, University closed)

* Note 1: December 2 is the last day of classes for terms F and Y (Fall term). This day will be used to replace
missed Monday classes. The lecture schedule will be that of a Monday.

Course Details
Textbook: “Principles of Instrumental Analysis”, 5th edition,
1998 by Skoog, Holler & Nieman, Harcourt Brace Publishers

Reference Books (on reserve in Steacie Science Library):

“Electronics and instrumentation for scientists”, Malmstadt, Enke, Crouch.
“Electrochemical methods : fundamentals and applications”, Bard, Faulkner
“Instrumental methods of analysis”, Willard, Merritt, Dean.
“Gas chromatography : a practical course” Schomburg.
“Fundamentals of Analytical Chemistry”, 7th ed., Skoog,West,Holler
“Quantitative Chemical Analysis”, 2th ed., D.C. Harris
“Quantitative Analysis”, 6th ed., R.A. Day and A.L. Underwood
“Analytical Chemistry - Principles and Techniques”, L.G. Hargis

Laboratories: manuals are available from the lab coordinator, C.Hempstead, 360CCB
all laboratory conflicts go through Carolyn .

Note: the laboratory portion if the course represents a significant fraction of your final grade. To complete the
experiments and reports satisfactorily, you must read and understand the experiment in the manual and the
background information in the textbook before coming to the lab. The demonstrators may quiz you on your
knowledge of the experiment at the beginning of the laboratory. Marks may be deducted for those who are not
prepared.

1
 Chemistry 3080 4.0 Course Outline
Topic Chapter
1) Introduction 1
• instrumental analysis
• figures of merit
C calibration methods
2) Electronics, signals and noise 2, 3, 4, 5
• basic electronics and devices
• digital electronics
• computers & interfaces
• signals and noise
3) Analytical Separations 26, 27, 28
• principles of chromatography
• gas chromatography
• high performance liquid chromatography
• other methods
4) Analytical Spectroscopy 6(Review)
• components for optical spectroscopy 7, 8, 9, 10, 13, 14
• UV/VIS absorbance spectrophotometry
• luminescence (fluor-, phosphor- and chemilumin-escence)
• atomic emission and atomic absorption
5) Electroanalytical Methods 22, 23, 25
• potentiometry
• voltammetry
6) Mass Spectrometry 11, 20
• the mass spectrometer
• ion sources
• hyphenated methods

Introduction
Classification of Analytical Chemistry

Classical methods

• separations performed by precipitation, solvent extraction or distillation.

• quantitative analysis performed by gravimetric and volumetric (titrimetric) methods
• detection limits in the ppb - % range.
• precision can often be excellent
• these methods are often labour intensive

Instrumental Analysis

• often these are semi to fully automated techniques that involve the manipulation of
molecules, photons and electrons to provide simultaneous (often) qualitative and
quantitative analysis.
• detection limits in the pp 10-15 - % range
• precision is dependent less on the operator and more on the instrument and sources
of noise.

2
 The Analytical Method

Decision

Sampling

Separation

Measurement

Evaluation

DSS ME !

Subfields of Instrumental Analysis

Analytical Separations (chemical equilibrium + detectors)
● gas chromatography
● liquid chromatography, ion chromatography
● supercritical fluid chromatography
● electrophoresis & capillary electrochromatography

Electroanalytical methods (chemical potential + electrons)

● coulometry
● voltammetry
● potentiometry

Analytical Spectroscopy (chemical energy + photons)

● absorbance
● fluorescence, phosphorescence
● Raman
● infrared
● photothermal
● atomic absorption/atomic emission
● inductively coupled plasma

3
 Cont’d
Other Methods
● mass spectrometry (m/e ratio + ion mobility)
● radiochemical
● thermal methods
● surface analysis
● nuclear magnetic resonance (NMR)
● X-Ray spectroscopy

Hyphenated Methods

separation method / detection method

- liquid chromatography + mass spectrometry (LC/MS)

-Electrophoresis + inductively coupled plasma + mass spectrometry (CE/ICP-MS)

sampling/separation/ion generation/detection method

solid phase microextraction/gas chromatography/electrospray ionization-mass

spectrometry (SPME/GC/EI-MS)

Instrumental methods of Chemical Analysis

(vs classical techniques)

Advantages

● less labour intensive

● easy to automate
● simultaneous multi component analysis
● fast analysis
● lower detection limits

Disadvantages

● higher expense
● harder to trouble shoot problems, more technical expertise
● black box syndrome

4
 Components of an analytical instrument
sampler

chemical sample
separation

chemical components

signal generator

analytical signal
detector

input signal

signal processor

output signal

readout

Sampler
A sampler included in an instrument can have many functions:
• to transport a prepared sample to the separation or measurement region.
May involve the beginning of quantitation where a highly reproducible
fixed volume is delivered.
eg. - autosampler and injector used in HPLC or GC.

• to transform the prepared sample in a form suitable for the measurement

process.
eg.- an atomizer in atomic absorption will nebulize (desolvation) and
atomize (break chemical bonds to produce free atoms and ions) the
sample, preparing it for the absorbance measurement in the flame.

• to process the raw sample making it ready for chemical analysis

eg. derivitization reactions in flow injection type apparaus will selectively
react with one component of the matrix making it more distinguishable
from the other components (ie- addition of an absorbing or fluorescent
chromophore to the molecule)

5
 Accelerated Solvent Extraction (ASE)
Instrumented sample preparation

Separation

Separates components of the sample into

different chemical entities, ready for the
measurement process.

- chromatographic column achieves

separation based upon differences in
equilibrium adsorption processes.

- capillary zone electrophoresis separates

components of a sample based upon their
ionic mobility in the solvent medium.

- in mass spectrometry, molecular ions are

separated based upon their m/z (m=mass,
z = charge) ratio in a mass analyzer.

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 Signal generator
the instrumental components and chemical system that produce some signal
that is related (hopefully linearly) to the presence and quantity of analyte.

eg.-absorption of UV/VIS radiation, the signal generator includes light

source, optics, absorbance cell and the absorbing molecules.

analytical signal: A = -log T = εbC

eg. polarography - signal generator is the voltage source, mercury drop

generator, cell and analyte.
analytical signal: id = KD½ m⅔ t1/6C
id = diffusion current
D = diffusion coefficient
K = constant
m = Hg mass rate
t = time of Hg drops C = analyte concentration

Detector

a component (input transducer) that converts one form of energy to another

OR converts an analytical signal to an electrical signal (usually voltage or
current).

examples-photomultiplier tube (PMT), photodiode, electron multipliers

(ions), voltammeter.

Photodiode Array or Charge Coupled device

7
 Signal Processor:
Modifies the detector signal to make it more convenient for interpretation.

The signal processor is usually an electronic module or circuit that can

perform one or more of the following functions:

- amplification - multiplying the signal by a constant >1

- attenuation - multiplying the signal by a constant <1,
- filtering - reducing noise in a given frequency range
- rectification - change from an AC to a DC signal
- voltage to frequency conversion- change from AC to DC
- mathematical - integration, exponentiation, ratioing.

Gaseous Carbonyls by Automated DNPH Cartridge/µ-

HPLC/CCD Absorption detection

8
 Automated DNPH/ µ-HPLC/CCD Carbonyl
Measurement Instrument Schematic
60 psi UHP He
KI O3 Trap Sampling Manifold
Sample
H2O ACN DNPH
Inlet
3 45
216 Syringe Pump
A
DNPH Cartridge
Pump
MFC
B C
HPLC Waste
System
UV Detector

HPLC Column
1 mm x 25 cm
3 um C18

Gaseous Organic Carbonyls by Automated

DNPH/µ−HPLC/CCD System
1.00
0.60
acetaldehyde
0.80 0.50
rain
Mixing Ratio (ppb)

rain
Mixing Ratio (ppb)

0.60 0.40

formaldehyde 0.30
0.40
0.20
0.20
0.10

0.00
0.00
17-Aug 18-Aug 19-Aug 20-Aug 21-Aug 22-Aug 23-Aug
Date 17-Aug 18-Aug 19-Aug 20-Aug 21-Aug 22-Aug 23-Aug
Date

1.80
acetone 0.60
1.60
Glyoxal
0.50
Mixing Ratio (ppb)

1.40
Mixing Ratio (ppb)

1.20
0.40
1.00
0.30
0.80

0.60 0.20
0.40 rain rain
0.10
0.20

0.00 0.00
17-Aug 18-Aug 19-Aug 20-Aug 21-Aug 22-Aug 23-Aug 17-Aug 18-Aug 19-Aug 20-Aug 21-Aug 22-Aug 23-Aug
Date
Date

9
 Sumas: Gas Phase Carbonyls, 2001
2.5
formaldehyde
2.3
Acetaldehyde
2.0
Acetone
1.8

1.5
ppb

1.3

1.0

0.8

0.5

0.3

0.0
8/17 8/19 8/21 8/23 8/25 8/27 8/29 8/31 9/2

High Volume Filter Sampling for Organic Analysis of Aerosols

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 Organic carbonyls in Particulates

Filter
Injection &
pre-
pre-concentration
Sampling
Extraction &
derivatization
HPLC Separation
& Detection

DNPH Preparation

• Large injections require very pure DNPH since

+ small impurities are pre-
pre-concentrated
DNPH / H
ACN / H O
ACN • Extraction solution passed through C-
C-18 to trap
2

contaminants

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 DNPH Extractions

General Reaction:

DNPH Hydrazone

• 25 ml of 10-3 M DNPH solution

• 65% H2O , 35% Acetonitrile, pH = 3
• Temp. = 85 0C

Particulate methylglyoxal in the LFV

1.6

1.4 Slocan Langley Sumas

1.2

1.0
( ng/m 3)

0.8

0.6

0.4

0.2

0.0
8/15 8/17 8/19 8/21 8/23 8/25 8/27 8/29 8/31 9/2

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 Instrumental set-up for DOAS

Sumas Site
305m asl

DOAS Receiver
th
pa 200 m asl
km
3.3

T33 Station

DOAS Transmitter
65m asl

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 DOAS Receiver
diffuser &
fiber optic coupler
8” x 1 m
Newtonian
reflector
Laptop/AD interface telescope

cooled fiber optic

CCD spectrometer

Absorption Spectrum*, λ2

∫ A (λ )dλ
'

Aug 31, 4:00 am. λ1

e

Intensity (counts)
NO3
-0.076
Absorbance

-0.077

-0.078

-0.079

H2O
600 610 620 630 640 650 660 670 680
Wavelength (nm)

*reference spectrum is an early morning spectrum just after

sunrise when NO3 is at negligible levels but other atmospheric
species (ie- H2O) are still present.

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 NO3 Levels by DOAS: Sumas
20 60
Aug 15/16, 2001 Aug 20/21, 2001
50
15
40
NO3 (ppt)

NO3 (ppt)
10 30

5 20
10
0
0
-5 -10
08:00 PM 12:00 PM 04:00 AM 08:00 AM 08:00 PM 12:00 PM 04:00 AM 08:00 AM
Time (hour) Time (hour)
60 40
Aug 29/30, 2001 Aug 30/31,2001
50
30
40
NO3 (ppt)

NO3 (ppt)
30 20

20 10
10
0
0
-10 -10
08:00 PM 12:00 PM 04:00 AM 08:00 AM 08:00 PM 12:00 PM 04:00 AM 08:00 AM
Time (hour) Time (hour)

Aerosol Mass Spectrometer

signal generator detector

sampling separation (electron impact ionization) ion/electron multiplier

signal processor and readout

(not shown)

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