CHEM F313: Instrumental Methods of Analysis

Lecture 02
Energy & Electromagnetic Spectrum
8/18/2023
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Outline

 Last Class

 Analytical Chemistry
 Sensitivity and Detection Limit
 Signal and Noise

 Today’s Class

 Signal to Noise Ratio

 Error
 Precision and Accuracy
 Electromagnetic waves

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Signal & Noise

• Signal: Instrumental output responding to the chemical system of

interest (analytes)

• Noise: Instrumental output caused by other components (matrix)

and instrument during operation
Noise reduction is one primary consideration in obtaining meaningful
information during analysis

TWO principle methods for signal enhancement

1. Use of electronic hardware devices (filters etc.) or software
algorithms to process signals
2. Post-measurement mathematical methods (statistical)
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Signal-to-Noise Ratio (S/N)
Ability of an instrument system to discriminate between Signals and Noise,
usually expressed as,

Once the acquisition is over and an electrical current is recorded, S/N cannot
be changed by mere amplification
Fundamental Noise
Originating from fundamental, intrinsic properties
of the measuring system due to the discontinuous
nature of matter & energy
Noise Types
Limits accuracy, precision, Detection limit
Environmental Noise
Originating from environment external to the
measuring system Easy Identification and reprisal
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Noise Types for Solid State
Devices
THERMAL NOISE: Originates from thermally induced
motion in charge carriers. Also known as WHITE noise.
Expressed as 𝑎𝑣
Vav = Avg. voltage due to thermal noise, k = Boltzman’s const., T =
Abs. Temp., R = Resistance, ∆f = bandwidth of measurement freq.

SHOT NOISE: Originates from movement of charge carriers

Fundamental across n-p junctions, electrodes. It is Signal dependent.
Noise Expressed as 𝑎𝑣
iav = Shot noise, e = electron charge, I = Intensity of signal, Df = bandwidth
of measurement freq.

FLICKER NOISE: Origin not known. Observed for low

frequency signals (< 300Hz). Expressed as 𝑎𝑣 2
Vav = Avg. voltage due to flicker noise, K = Const. depending on geometry
and material, I = Current, f = frequency

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Noise Types for Solid State
Devices
Environmental Noise

 It involves transfer of energy to the measurement system from

surrounding.
 It typically occurs at specific frequencies or a narrow frequency of
bandwidths.
 TWO common sources of environmental noise are the electric and
magnetic fields produced by 60-Hz electrical transmission lines

Other sources of Environmental Noise

• Reflected Radiant energy

• Mechanical Vibration
• Electrical interaction between different
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Minimization of Noise
Thermal Noise
• Reducing temperature e.g. sensitive radiation detectors are often cooled
• Narrowing the frequency bandwidth
Shot Noise
• Reducing the bandwidth
• Can be problematic at large signal values
Flicker Noise
• Neglecting the effect of 1/f term, at higher f values (> 300 Hz)
• Field effect transistors are more effective than the bipolar devices
Environmental Noise
• Shielding of circuits from external sources of energy
• Proper grounding of equipments
• Proper choice of transmission frequencies
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Software Techniques for S/N
Enhancement
Commonly used digital techniques are
• Boxcar Averaging
A group of closely-spaced digital data points depicting a slowly changing
analog signal is replaced by a single point (avg.)
– can be implemented in real time
– Enhancement of S/N ratio is calculated as
where, n : number points averaged in each boxcar
– Mostly used for slow-changing analog signals

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Software Techniques for S/N
Enhancement
Effect of Boxcar averaging on a
simulated noisy spectrum; the no of
points included in the boxcar in the
right side

Boxcar Averaging

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Software Techniques for S/N
Enhancement
Ensemble Averaging
• Applicable for fast-changing signals
• The results of ‘n’ repeated sets of measurements of the same
phenomenon are added and the sum is divided by ‘n’ to obtain an
average scan.

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Software Techniques for S/N
Enhancement
Commonly used digital techniques are
• Smoothing (Weighted Digital Filtering)
Salient features are
– Each data point contributes equally for calculation of average
– Different weights are assigned to points as a function of their
position w.r.t. central point
– Adjustable filtering parameter, moving average points used

• Fourier Transformations
– Mathematical FT operation performed
– Most widely used method

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Error in Analysis: Types
Random Error is indeterminate. Intrinsically uncertain nature of the
measurement technique is the source of random error.

• Occurs in every analysis.

• The magnitude is generally small and filtering methods can be
used to minimize them
• Thermal, Shot, Flicker noise are sources of Random error.
Systematic Error is determinate. It is purely procedural and causes
results to deviate from expected values in a constant manner.

• Sources : improper instrument calibration, analyte purity, improper

instrument handling etc.
• Cannot be reduced by statistical methods, it need to beIdentified and
minimized by modifying analytical procedures
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Expression of Errors
• Error (d) may be expressed in absolute terms as the difference
between an analytical result (x), and the known true value (μ)
d = μ-x
• Absolute error: When the error is expressed as an unsigned
number. It is insignificant when separated from the true value
• Relative error: Used to measure the accuracy of a measurement &
is the percentage of the true value

Analysis of Pb and Zn in a sample yield the following results: Pb = 653

μg/mL, dPb = 4.3 μg/mL; and Zn = 4.5 μg/mL, dZn = 0.15 μg/mL

Erel for both???

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 Precision and Accuracy
Accuracy is defined as the agreement of a measurement with the true
value for the quantity being measured
Precision is defined as the ability to reproduce the same values for a
set of parallel observation

Accurate and precise NOT Accurate BUT precise

Significant figures is the number of decimals defined by any entity/
authority as a measure of the precision while reporting the original
(initial) data.
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 Energy and Electromagnetic waves

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Electromagnetic waves
1. Wavelength, l
2. Frequency, ν
3. Wave number, ῡ
4. Radiant Power, P
5. Intensity, I
6. Monochromatic/Polychromatic
7. Interference
8. Polarised/non-polarized

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Electromagnetic spectrum
Energy Change

Nuclear Inner shell Ionization Molecular Spin Orientation

electrons of Atoms & Vibration
Molecules (stretch, bend)

8/18/2023 Valance Electrons 17

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Interaction of EMR and molecule
Electric/magnetic component of EMR may interact with the molecule.
How?
• Electric component may interact with the electric dipole moment of
the molecule: Rotational-, vibrational-, and electronic-
spectroscopy.
• Magnetic component may interact with the magnetic dipole
moment of the molecule: NMR-, EPR- spectroscopy.

Bohr frequency
condition h = 

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Conclusions
 Signal to Noise Ratio
 Error
 Precision and Accuracy
 Electromagnetic waves

 Next Class

 Fundamental Law
 Types of absorption band
 MO involved in electronic structure
 Solvent Effect

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