Spring 2017 CHEMISTRY 105

Instrumental Methods in Analytical Chemistry

Lecture: MW 9 AM 10 AM 219 Dwinelle
Labs: MTuWTh 1 5 PM 305 Latimer

Lecture 1. Introduction

Prof. Ke Xu

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Course information

Instructor: Prof. Ke Xu E-mail: [email protected]

478 Stanley Hall (666-2784)
Office Hours: Wed 4:306:00 pm

Prof. Marcin Majda (Electrochemical methods on 3/8-3/22)

Office Hours: on the day of lecture at 1 pm, or by appointment
(E-mail: [email protected]).

Teaching Seonah Moon E-mail: [email protected]

Assistants: Eugene Kapustin E-mail: [email protected]
Teng Lei E-mail: [email protected]
Rui Yan E-mail: [email protected]

Web Site: https://bcourses.berkeley.edu/courses/1457451

Note: pre-class and final slides will be uploaded to bCourse

Text: A. Skoog, F. J. Holler and S. R. Crouch, Principles of Instrumental

Analysis, 6th Edition (Cengage Learning)
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What is a (chemical) measurement?

Sample number / conclusion

Qualitative:
Test: Exist or non-exist; positive or negative
Identity: Which elements? Which form (oxidation states, isomer, chirality, isoform)?

Quantitative:
Result: A number, e.g., concentration or amount
Error bar uncertainty of the result

Chemical/classical: Chemical reactions. Titration, gravimetric,

Easy to see what is being done

Instrumental: Relies on instruments.

Underlying mechanism is hidden

Sample number / conclusion

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Instrumental Methods: Aims of the Course
For each method:
pivot
Key things to learn Calibrated arm
What info does the method provide?
What chemical/physical principles are used?
Key components of the instrument. Counterweight
Working range? Detection limit? Example:
steelyard balance
How to calibrate? How to measure?

More advanced levels:

Optimization for best results

Identify the most suitable method for a given problem
Combination of different methods
Invention of new methods new chemical/physical principle? Translation from a
different field?

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How to weigh an elephant with a steelyard balance?

Steelyard
balance
+
Archimedes'
principle
+
AD 201, Cao Chong, Extensive
Age 6 property of
mass (additive)

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Contents Part A. Lectures
I. INTRODUCTION (Chapter 1 (review), Chapter 5, Appendix 1)
A. Measurement, signal and noise
B. Statistics and error analysis

II. ATOMIC SPECTROSCOPY (Chapter 6 (review), 8, 9,10)

A. Atomic absorption spectroscopy
B. Atomic emission spectroscopy
C. Ionization and instrumentation

III. MASS SPECTROMETRY (Chapter 20)

A. Ionization methods
B. Mass selection and analyzers
C. Introduction to tandem mass spectrometry

IV. ELECTROCHEMICAL METHODS Prof. Majda (Chapters 22 (review), 23, 25)

A. Review of basic electrochemical concepts
B. Kinetic vs. mass transfer limitations
C. Voltammetric and pulse-polarographic techniques
D. Microelectrodes

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Contents Part A. Lectures

V. SEPARATIONS (Chapters 26-30)

A. Basic principles and theories
B. Gas chromatography
C. Liquid chromatography
D. Electrophoresis

VI. SURFACE & MICROSCOPY TECHNIQUES (Chapter 21)

A. Electron spectroscopy
B. Electron microscopy and microanalysis
C. Scanning-probe microscopy
D. Optical & super-resolution microscopy

Problem Sets (25 points)

Midterm (75 points): Monday, March 6th in class

Final Exam (150 points): TBA

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Contents Part B. Experiments

Work in groups on experiments, but each student submit individual laboratory

reports

Pick five from

Atomic Absorption/Emission Spectrometry

Whiskey Analysis with Gas Chromatography
Caffeine Analysis with GC/MS
Inductively Coupled Plasma - Atomic Emission Spectroscopy
Peptides Analysis using HPLC
Capillary Electrophoretic Separations of Proteins Using a Microfabricated Lab-on-a-Chip
Voltammetric Methods of Analysis

Lab Due Dates and Late Policy noted in syllabus

Laboratory Reports (50 points each x 5) = 250 points

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 9
Instruments for chemical analysis: Typical elements
Signal
separation

Signal
detection
and
(Signal generation)
processing
Performance characteristics of instruments 10

Precision: variance;
uncertainty between
repeated measurements

Accuracy:
bias; systematic error

Three key components

of a measurement result:
Number
Unit
Uncertainty
Statistics, uncertainty, and noise
For repeated measurements of N times:
N True value, or

Sample mean:
x i
x= i =1 Absolute error: E = x xt
Limited by N N
x xt
Population mean: = lim x Relative error: Er = 100%
true value N xt

Standard deviation: the amount of variation from the average -uncertainty

Population standard deviation Sample standard deviation

(x x )
N N

(xi ) (N 1)
2
= lim 2
N s= i
N i =1 i =1

Use of square: every term (+/- deviation) gets positive!

Use of square root: final result has the same unit as measurement
s is an estimation of : larger by sqrt[N / (N-1)] to account for uncertainty
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 Signal and noise
Signal x = 1 Signal x = 2
Noise = 1 Noise = 2
6 Measured data 6
Actual value

4 4

2 2

Signal
Signal

0 0

-2 Amplified -2
by 2-fold
-4 -4

0 200 400 0 200 400

Time Time

When a signal (change in measured value) is below the detection limit:

Signal too weak?
Noise too high!
Simple amplification doesnt help!

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Signal-to-noise ratio Signal
S/N = standard deviation
Signal x = 1 Signal x = 3
6 Noise = 1 Measured data 6 Noise = 1
Actual value

4 4

2 2
Signal

Signal
0 0

-2 -2

-4 -4

0 200 400 0 200 400

Time Time

Distribution: 1-200 time points

Distribution: 201-400 time points
Detection limit: Distribution: 1-200 time points
Distribution: 201-400 time points

defined as
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S/N =3! 20

Count
Count

10 10

0
-2 -1 0 1 2 3 4 5 6
Histograms 0
-2 -1 0 1 2 3 4 5 6
Bin Center Bin Center
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Distribution of data
Spreadsheet
# Value # Value
Data plot 10
1 8.96083 27 6.71161
2 9.73824 28 7.62878 8
3 7.56979 29 7.24221

Value
4 6.37268 30 7.43603 6
5 8.16635 31 8.55514
4
6 8.37627 32 7.44322
7 7.77305 33 7.10489
2
8 6.85109 34 7.59067
9 10.02433 35 7.83911 0
10 5.64048 36 8.40933 10 20 30 40 50
11 7.49003 37 7.04736 Measurement #
12 6.67837 38 8.31732
13 7.36387 39 8.07802
14 8.31785 40 9.32439
Histogram: 10
15 8.13805 41 7.78683
16 7.28926 42 7.86552 groups 8
17 8.77700 43 6.82864
numbers into
18 8.62239 44 6.61474

Count
19 8.64738 45 8.31051
ranges 6
20 7.57437 46 7.75051
4
21 9.04858 47 8.50374
22 8.66071 48 7.10734
2
23 10.50877 49 9.90851
24 9.06346 50 8.12223
0
25 9.15692 51 9.04703 5 6 7 8 9 10 11
26 8.05298 52 7.77308 Value
Noise/uncertainty is often treated as normal distribution

Normal (Gaussian) distribution:

Related to quantities that grow
linearly (e.g. errors, offsets)

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Bell curve
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Count

0
5 6 7 8 9 10 11
Value
http://www.mathsisfun.com/data/quincunx.html

A result of: multiple random factors that are not controllable in experiment

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