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Calibration methods,
Digital and analog signals
Lecture 2
Systematic errors
Present in all measurements made in the same way
and introduce bias.
Instrumental errors
Wacky instrument behavior, bad calibrations, poor
conditions for use
Electronic drift, temperature effects, 60Hz line noise,
batteries dying, problems with calibration equipment.
Personal errors
Originate from judgment calls
Reading a scale or graduated pipette, titration end points
Method errors
Non-ideal chemical or physical behavior
Evaporation, adsorption to surfaces, reagent degradation,
chemical interferences
Noise
A signal is only of analytical value if it can be
definitively attributed to the species/system of interest
in the presence of noise.
2.5 2.5
2 2
signal
signal
1.5 1.5
1 1
0.5 0.5
0 20 40 60 80 100 0 20 40 60 80 100
data point data point
What is signal and noise?
Signal-to-noise ratio
Signal-to-noise ratio is a measure of the quality of a
method or of instrument performance
Ratio of the mean and the standard deviation of the signal
Higher value of S/N means that its easier to resolve
signal.
x
S
N s
1
S
N RSD
rms 4kTRf
Supposedly 1/f
mostly at low
frequencies
Occurs at discrete
frequencies
Enhancing signal-to-noise
Hardware methods Software methods
Grounding and shielding Ensemble averaging
Difference and Boxcar averaging
Instrumentation Digital filtering
Amplifiers Correlation methods
Analog Filtering
Lock-In Amplifiers
Modulation and
Synchronous
Demodulation
Ensemble averaging
Averaging multiple
data sets taken in
succession
Divide sum of data
sets by number of
data sets
n
S
i 1
i
Sx
n
J. Chem. Educ., 1979, 56, 148-153.
Ensemble averaging
continued
Signal-to-noise improves with increasing
number of data sets
S N n
N
n S
i
Instrument calibration
Determine the relationship between response
and concentration
Dose response curve
Calibration methods typically involve standards
Comparison techniques
External standard*
Standard addition*
Internal standard*
* calibration curve is required
Comparison techniques
Titrations
Does not require standards
Direct comparisons
Null measurements
sb sr
x 2
i
N x x
2
2
i i
Appendix a1D
Now what about the unknown concentration
determined from this calibration curve?
If the mean value is <y> from M replicate analyses,
and the calibration curve contains N data points,
then the error in the determined concentration is
1 1 y y mean
2
sr
sc
m M N m 2 Sxx
kVs cs kVx cx
Vt Vt
Vs cs Vx cx
Vs cs
cx
Vx cs
sc sv
Vx
Internal standard
A substance added in a constant amount to all
samples, blanks, and standards or a major
component of a sample at sufficiently high
concentration so that it can be assumed to be
constant.
Plotting the ratio of analyte to internal-standard as a
function of analyte concentration give the calibration
curve.
Accounts for random and systematic errors.
Difficult to apply because of challenges associated
with identifying and introducing an appropriate
internal standard substance.
Similar but not too similar; cant be present in sample