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Instrumental Analysis
• Contents
1. Basics
2. Spectroscopy
3. Instrumentation
• Chemical Analysis
separation, identification, and the determination of the relative
amount of the components in a sample (analyte) of matter
- stoichiometric relationship
aA + bB cC + dD
Classical vs. Instrumental Methods
• Classical
– Qualitative : identification by color, indicators,
boiling points, odors
– Quantitative : mass or volume
e.g. gravimetric, volumetric
• Instrumental
– Qualitative : identification by measuring physical property
e.g. spectroscopy, electrode potential,
chromatography, electrophoresis
– Quantitative : measuring property and determining
relationship to concentration
e.g. spectrophotometry, mass spectrometry
– Often, same instrumental method used for qualitative and
quantitative analysis
Types of Instrumental Methods
1) Emission
–Emission spectroscopy : fluorescence, phosphorescence,
luminescence
2) Absorption
–Absorption spectroscopy : spectrophotometry, photometry,
nuclear magnetic resonance, electron spin resonance
3) Scattering
–Turbidity, Raman
4) Refraction
– Refractometry, interferometry
6) Radiation rotation
– Polarimetry, circular dichroism
7) Electrical potential
– Potentiometry
8) Electrical charge
– Coulometry
9) Electrical current
– Voltammetry - amperometry, polarography
11) Mass
– Gravimetry
14) Thermal
– Thermal gravimetry, calorimetry
15) Radioactivity
– Activation, isotope dilution
– (Often combined with chromatographic or electrophoretic
methods)
Steps in a Chemical Analysis
• Steps in a chemical analysis
– Precision/Accuracy
– Amount of sample
– Range of analyte concentration
– Interferences
– Physical and chemical properties of sample matrices
– Number of sample
– Time required for analysis
– Professionalism
– Availability of instrument
– Cost
Characteristics of Instrument
• Precision/Bias
• Sensitivity
• Detection limit
• Concentration range
• Selectivity
Precision and Bias
• Precision : Deviation
– Measure of random, or indeterminate error
– Reproducibility
– Standard deviation, Coefficient of Variation
– Figure of merit
• Bias : Error
– Measure of systematic or determinate error
– Bias = (population mean) – (true value)
Sensitivity
• Sensitivity
- Time
– vary with time
– frequency, phase, pulse width
- Analog
– continuously variable magnitude
– current, voltage, charge
- Digital
– discrete values
– count, serial, parallel, number
Sensitivity
• Sensitivity
– Calibration sensitivity: S
– larger slope of calibration curve means
more sensitive measurement
• Analytical Sensitivity
– Mandel and Stiehler
– AS = slope of calibration curve/std.
deviation
– AS is unchanged with the increase in the
signal amplification of instrument, because
std. deviation also increases with the
increase in the slope of calibration curve
Detection Limit
• Minimum signal :
– Signal (min) = Average Signal of blank + ks (blank)
– From statistics k=3 or more
• (at 95% confidence level)
• Suggested by Long and Winefordner
Dynamic Range
• Selectivity coefficient
– kB,A = m(B)/m(A)
• Precision
- Variance: s2
• Standard Deviation
- rounding data
1) choose even or odd number
2) do not round until calculations are complete (guard digit)
Errors and Standard Deviations
• Accuracy
• Types of Errors
• Gaussian Distribution:
- Gaussian Curve: frequency vs. deviation from mean
Normal Error Curve: frequency vs. z {= (x- μ)/σ}
0.4
Relative Frequency
0.3
0.2
0.1
0.0
-3 -2 -1 0 1 2 3
Statistical Treatments for Indeterminate Errors
- standard deviation ~ σ
CL for μ = x ± z σ
for N replicate measurement, CL for μ = xm ± z σ/N1/2
- Standard deviation ~ s
CL for μ = x ± ts,
for N replicate measurement, CL for μ = xm ± ts/N1/2
Statistical Treatments for Indeterminate Errors
• Rejection of Outlyers
- T-test:
Tn = |xq – xm|/s,
for entire set including the questionable result
- Q-test:
Qexp = |xq – xn|/w, xn; the nearest neighbor of xq
Statistical Treatments for Indeterminate Errors