Signals and Noise

Signal to Noise Ratio

signal - the information about the analyte that
is of interest to the chemist

noise - extraneous information that is

unwanted because it degrades the accuracy
and precision of an analysis and also places
a lower limit on the amount of analyte that
can be detected
 Signal to Noise Ratio
Effect of Noise
"Effect of noise on a current measurement
(a) Experimental strip chart recording of a 0.9 X 10-15A direct current
(b) Mean of the fluctuations."
 Signal to Noise Ratio
Definition
S/N = mean/standard deviation = x/s

S/N = 1/ RSD
where RSD => relative standard deviation, s/x
 Signal to Noise Ratio

"Effect of signal-to-
noise ratio on the
NMR spectrum of
progesterone:
(a) S/N = 4.3
(b) S/N = 43."
 Sources of Noise in
Instrumental Analyses
Chemical Noise

Instrumental Noise
 Sources of Noise in
Instrumental Analyses
Chemical Noise
results from uncontrollable variables that
affect the chemistry being investigated
 Sources of Noise in
Instrumental Analyses
Instrumental Noise
Types of Instrumental Noises
Thermal Noise
Shot Noise
Flicker Noise
Environmental Noise
 Sources of Noise in
Instrumental Analyses
Instrumental Noise
Thermal Noise, or Johnson Noise
– results from thermal agitation of electrons in
electrical components
– random
– periodically creates charge inhomogeneities
which in turn create voltage fluctuations
 Sources of Noise in
Instrumental Analyses
Instrumental Noise
Thermal Noise, or Johnson Noise
rms = (4kTRf)1/2
where rms => root-mean-square voltage
k => Boltzmann constant, 1.38 X 10-23 J/K
T => absolute temperature
R => resistance of resistive element
f => frequency band width = 1/tr
where tr = response time to abrupt change in input
 Sources of Noise in
Instrumental Analyses
Instrumental Noise
Shot Noise
– results from current moving across a junction
such as in solid state electronic devices
 Sources of Noise in
Instrumental Analyses
Instrumental Noise
Shot Noise
irms = (2Ief)1/2
where irms => root-mean-square current
I => average direct current
e => charge on the electron
 Sources of Noise in
Instrumental Analyses
Instrumental Noise
Flicker Noise
– frequency dependent, worse at low frequencies,
can be reduced by changing type of resistor
Sources of Noise in Instrumental Analyses
Instrumental Noise
Environmental Noise
"Some sources of environmental noises in a
university laboratory."
 Signal-to-Noise Enhancement
Some Hardware Devices
for Noise Reduction
Grounding and Shielding
Difference Amplifiers
Analog Filtering
Modulation
Signal Chopping; Chopper Amplifiers
Lock-in Amplifiers
 Signal-to-Noise Enhancement
Some Hardware Devices
for Noise Reduction
Grounding and Shielding
– surrounding a circuit, or some of the wires of
the circuit, with conducting material that is
attached to earth ground
 Signal-to-Noise Enhancement
Some Hardware Devices
for Noise Reduction
Difference Amplifiers Rk
V1 -

Vo
V2  +
Rk Vo = (Rk/Ri)(V2-V1)
 Signal-to-Noise Enhancement

Some Hardware Devices

for Noise Reduction
Analog Filtering
"Use of a low-pass
filter with a large time
constant to remove
noise from a slowly
changing dc voltage."
 Signal-to-Noise Enhancement
Some Hardware Devices
for Noise Reduction
Modulation
– low frequency or dc signals from transducers
are converted to a higher frequency
– after amplification, the modulated signal is
filtered with a high-pass filter; demodulated;
filtered with low-pass filter
 Signal-to-Noise Enhancement
Some Hardware Devices
for Noise Reduction
Signal Chopping; Chopper Amplifiers
– input signal converted to square wave chopped
by electronic or mechanical means
– filtered with high-pass filter
 Signal-to-Noise Enhancement
Some Hardware Devices
for Noise Reduction
Lock-in Amplifiers
– the reference signal must be of the same
frequency as the analytical signal
– must bear a fixed phase relationship to the later
 Signal-to-Noise Enhancement
Software Methods
S/N enhanced by n0.5, where n is the
number of measurements averaged
 Signal-to-Noise Enhancement
Software Methods
Ensemble Averaging
Boxcar Averaging
Digital Filtering
Correlation Methods
 Signal-to-Noise Enhancement

Software Methods
Ensemble Averaging
"Ensemble averaging of
a spectrum."
 Signal-to-Noise Enhancement
Software Methods
Ensemble Averaging
"Effect of signal
averaging.” Note that the
vertical scale is smaller as the
number of scans increases.
That is, the noise grows in
absolute value with increased
number of scans; its value
relative to the analytical
signal decreases; however.
 Signal-to-Noise Enhancement
Software Methods
Boxcar Averaging
"Effect of boxcar averaging.
(a) Original data.
(b) Data after boxcar
averaging."
 Signal-to-Noise Enhancement
Software Methods
Digital Filtering
– time-domain signal is converted to frequency-
domain with Fourier transformation
– frequency signal is then multiplied by the
frequency response of a digital filter
– time-domain signal regenerated by reverse
Fourier transformation
 Signal-to-Noise Enhancement
Software Methods
Correlation Methods
– complex mathematical data manipulations by a
digital computer