CHEM F313: Instrumental Methods of Analysis

Lecture 02
Signal, Data and Analysis (contd)
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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,

in case of DC signals

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

Noise Types Limits accuracy, precision, Detection limit

Environmental Noise
Originating from environment external to the
measuring system
Easy Identification and reduce

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 Noise Types for Solid State
Reduction of thermal
Devices
noise THERMAL NOISE (Nyquist noise): Originates from thermally
• Cooling of Sensitive induced motion in charge carriers. Also known as WHITE noise.
radiative detector Expressed as
𝑉𝑎𝑣 = 4𝑘𝑇𝑅∆𝑓
• Narrowing the Vav = Avg. voltage due to thermal noise, k = Boltzman’s const., T = Abs. Temp.,
frequency band- R = Resistance of the electronic device, Df = bandwidth of measurement freq.
of detector
width
SHOT NOISE: Originates from movement of charge carriers
across n-p junctions, electrodes. It is Signal dependent.
Fundamental
Noise Expressed as 𝑖𝑎𝑣 = 2𝐼𝑒∆𝑓
iav = Shot noise, e = electron charge, I = Intensity of signal, Df = bandwidth
of measurement freq.

White noise:
independent of FLICKER NOISE: Origin not known. Observed for low
absolute value of frequency signals (< 300Hz). Expressed as 𝑉 = 𝐾𝐼 2 𝑓
𝑎𝑣
frequency
Vav = Avg. voltage due to flicker noise, K = Const. depending on geometry and
material, I = Current, f = frequency
TWO common sources of environmental noise are electric and magnetic fields
produced by 60 Hz electrical transmission lines and their harmonics (120,
180Hz) (others are reflected radiation energy, mechanical vibration and
electrical interaction etc) BITSPilani, Pilani Campus
 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 (software based)
• 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 (along with acquisition of data)

– Enhancement of S/N ratio is calculated as

where, n : number points averaged in each boxcar;
(S/N)0 = signal/noise ratio for untreated data
– Mostly used for slow-changing analog signals

• Ensemble Averaging (complement to Boxcar averaging, for signals

changing rapidly)
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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 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 (contd)

• Ensemble Averaging (continued)

 If each set of measurements is recorded in the same way,
the data contained in the measurements will sum coherently,
whereas the random noise should average to a value smaller
than the enhanced signal.
 Computer-managed ensemble averaging has been used to
extract small signals from background noise for the case of
C-13 NMR
 Liability is the time

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Software Techniques for S/N
Enhancement (contd)

Effect of ensemble averaging on a

simulated noisy spectrum

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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 and flicker noise are the sources

Systematic Error 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
• Identified 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: 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

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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

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Energy and Electromagnetic waves

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Electromagnetic waves

TWO principle methods for signal enhancement

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

Nuclear Inner shell Ionization Molecular Spin Orientation

electrons of Atoms & Vibration
Molecules (stretch, bend)

Valance Electrons
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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.
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 EMR-Molecule Interaction - Processes

E2

Energy
Absorption

Emission
h

E1
• Bohr frequency condition h = 

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Factors on which absorption depends
Lambert – Beer Law
Absorbance, A = log (I0/I)
Also, A = ε[c]L
Where, I0 and I are the
intensity of the incident and
transmitted radiations,
[c] = concentration
L = path length of the
radiation through the sample
e= molar absorption coefficient,
unit of e = 1/[conc.][length]
Transmittance, T = I/I0 hence, A = - log T
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 Representation of spectrum

Y-axis :
Intensity of
Absorption/
Transmission
/
Emission
X- axis : λ (wavelength) or related
entity such as wavenumber,
frequency etc.
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Spectral characteristics & transition moments
 For a molecule to be able to interact with the
electromagnetic field and absorb or create a photon of
frequency ν, it must posses, at least transiently, a dipole
oscillating at that frequency.
 This transient dipole is expressed quantum mechanically
in terms of the transition dipole moment, μfi, between
states Ψi and Ψf; where, μ = electric dipole moment
operator. μfi = ∫(Ψf* μ Ψi dτ)
2
Transition probability ∞ ∫(Ψf* μ Ψi dτ)
If μfi is nonzero, then the transition contribute to the
spectrum. Therefore, to identify the selection rules,
the condition for which μfi ≠ 0 should be established.
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