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 3. Measurement & Introduction to Spectroscopy

Prof. Ke Xu

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Homework due a week from today in class
Alice and Bob are re-enacting Cao Chongs weighing experiment. They found two
types of rocks, one type being ~50 kg in weight, and the other being ~20 kg in
weight. Now for an elephant that weighs ~1 ton, the measurement could be done
with 20 of 50 kg rocks, or 50 of 20 kg rocks.
Alice argues that the first approach gives a more precise result as more
rocks will introduce more error. Bob argues that the second approach is better as
the error from different rocks tends to cancel out each other.
Calculate the uncertainty of the final result for the two approaches for the
following two cases: (A) The absolute measurement uncertainty for each rock is
fixed to be 0.5 kg. (B) The relative measurement uncertainty for each rock is fixed at
2%. Which of the above two approaches win out for the two cases? (C) Is there a
mathematical form of error-weight relationship that would lead to equal uncertainty
of the final result for the two approaches?

+ Problem a1-12 (in Appendix 1)

& Problem 5-8 in text book Chapter 5

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Hardware devices for noise reduction
Analog filtering

A noise can be seen as a signal

and frequency, removing the
high frequency component.
the final result would be low
frequency. High frequency
can be more easily go through
the capacitor than low
frequency. than the output
voltage would be measured by
Vo. Vi is the input. Using one
resistor and one capacitor.

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Hardware devices for noise reduction

Modulation
Moves the measurement to higher f (reduces flicker noise)
Separation of real signal at the modulated frequency from random noise
Flicker noise is a form of noise that exhibits an inverse AC type of measurement. 1/f = flicker noise. removing
frequency power density curve. Flicker noise has a 1/f the 100hz frequency. doing spectroscopy. the sample is
characteristic, or a "pink noise" power density spectrum. emiting light. singanl chopping: a) plate with sluts
roates with fast speed, light can only pass through the
slut, using the rotation frequency chop the beam and
Signal chopping measure the frequency of the light.

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Lock-in amplifier

light pass through the flame cell. lock-in

amplifier can pick up signal with the
referency signal (the rotation frequency of
the rotator. can only pick up the true signal.
Removing the noise. (1 single frequency)

Picks up only signal at the exact same frequency as the reference signal
Reject signals/noises at other frequencies

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Improving S/N through averaging -repeated experiments

Software base.
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increasing the
measurement, the
Improvement in S/N
4 noise would be
reduced.
3

0
1 2 3 4 5 6 7 8 9 1011121314151617181920
# of measurements

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For moving targets, averaging and smoothing 8

Moving
average

single measurement, boxcar:

averaging every 3 points to
produce 1 single point. leave
with fewer points, but end up
with a smoother curve. Moving
average is better. Moving a point
per time to find the average.
Same number of points. but too
much would lose the resolution.

Works well for continuously evolving signal

Boxcar averaging Loose of signal details lower resolution in x
Piece-wise fitting and smoothing

Quadratic fitting

quartic fitting

Smoother results vs. preservation of signal details

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Digital filtering using Fourier transform

Fourier transform: define a cutofff point, and

remove all the higher frequency. Global removal
gives better result.

Cutoff frequency

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Performance characteristics of instruments

Sensitivity: Change in signal amplitude for given change in sample

property. Slope of response. e.g. Detector detects concentration.

Detection Limit: S/N = 3

Dynamic range: Useful working range with reasonable sensitivity (or, for
linearly calibrated systems: range of linear response)

Selectivity: Difference in sensitivity for different analytes

LOD: Limit of detection

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Generation of calibration / working curves 12

A. External-Standard Calibration Adding solution with unknown

concentration, using a series to
generate a curve. Extrapolation:
measurement is outside the
standard. Two ways: use another
standard, or dilute the sample.

Most
straightforward
Extrapolation
x Matrix effects
+ + Subject to
instrument
instability
Matrix Effects, impurites in the
sample. e.g. measure sea water using
+ Na+ standards. Instrument
instability.

http://www.chromedia.org

A series of known concentrations to generate calibration curve

Fit to calibration curves: linear fit, known models, curve fitting
Answer to unknown sample: determine with the curve. Avoid extrapolation!
Generation of calibration / working curves
B. Standard-Addition Method

Adding small amount of standards:

the matrix is nearly identical -removes
matrix effects

The response must be linear and

absolutely free from contributions of
other components

Still subject to instrument instability

Starting with the sample, then adding known amount of

standards. Using the linear ability, the x-intercept would be the
concentration. This method removes the matrix effect.

Spike the unknown sample with known amount of standards

Extrapolate to zero signal to obtain the unknown concentration
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Generation of calibration / working curves
C. Internal-Standard
Add into samples a component that
is not present in the test samples
produces a signal similar to, but distinguishable from
that of the analyte
is added in a constant amount to all samples and
standards

Gas chromatography: difficult to

control the loading amount. adding
another component as the reference
standards. producing a less scattering
graph.
Compensates for instrument instability! 14
The electromagnetic spectrum 15

Last absorbed by water

core valence
nuclear molecular nuclear
electron electron molecular
transition vibrations spin flip
transition transition rotations

micro-
wave
Visible light: 400-700 nm 16

Absorption of water
How to generate a spectrum: spectrometer/monochromator

Dispersion unit: Spread a

line-shaped light beam
into a band according to
wavelength

Recording the resultant

spectrum: directly, or slit +
scan

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Characteristics of monochromators

Dispersion

Angular dispersion: DA = d / d

Linear dispersion: Dl = dl / d = fDA

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Reciprocal linear dispersion: Dl = d / dl Unit: nm/mm

Resolving power
Unitless
R= Desired: >10,000 to separate Fe lines

Light-gathering capability

Output energy
L=
Input energy
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Spectra at different spectral resolution 19

Effect similar to
averaging/smoothing
Dispersive element: Prism

Difference in refraction index n for different wavelengths

Higher n for shorter wavelength higher energy and stronger interaction: bends
more

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Dispersive element: Diffraction gratings 21

n = d sin
n: order of diffraction
d: periodicity of grating
: angle

Denser pattern = wider angle

Longer wavelength = wider angle

Stronger dispersion and higher resolving power with denser grating

May be transmitting or reflecting
CDs as gratings 22

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