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Reading: Sections 5A-5C (only cover major ideas) Suggested Text Problems (Skoog 6th ed): Ch. 5: 7, 8, 10, 11 Overview of our coverage of this chapter (A) (B) (C) What is meant by Signal, Noise and their ratio? Where does noise come from? What can we do to reduce noise or enhance S/N ?

A: Signal, Noise and the S/N ratio S = signal N = noise “Signal” carries the analyte information “Noise” Unwanted signal that hurts the accuracy and precision and detection limits of the signal we care about So we use a signal-to-noise ratio expression to convey this ratio or as a ‘figure of merit’: For a dc signal:

**S mean x 1 = = = N std dev of mean s RSD
**

Std dev can be estimated at a 99% confidence level by measuring the difference between the max and min of the signal and dividing by 5. In general: when

S N

becomes less than 2-3, it becomes difficult to get useful

information from the signal.

Page 1 of 10

Example: Figure 5-1 (a) signal 0.1(a). (1) Chemical Noise Generally uncontrollable and specific to the chemistry of the system of interest (2) Instrumental Noise Each part of an instrument can have noise ramifications – so usually the noise observed in a signal is made up of many different kinds of noise and Page 2 of 10 .9 x 10-15 A – with noise present.2 × 10 A N B: Source of Noise in Instrumental Analysis Two main types of noise effect chemical analyses: chemical and instrumental noise. Answer: S x 9 × 10 −16 A S = = = 4. (b) theoretical depiction if noise wasn’t Problem: Make a rough estimate of the S/N for the signal shown in Figure 5.1 ≈ 4 = −16 N s 2.

60 x 10-19 C Δf = frequency bandwidth Independent of absolute frequency – sort of a white noise also.6 Hz.05 s then Δf = 6.is hard to predict or calculate. flicker noise. quantum noise) Generated when electrons or other charged particles cross a junction. Even when no current in a system. white noise. Nyquist) Results from random motions of electrons or other charge carriers. thermal noise can be observed. shot noise. such as thermal noise. where rise-time is an instruments response to an abrupt increase in signal or output in seconds If tr = 0. “White noise” – independent of absolute frequency (b) Shot Noise (Schottky Noise. νrms = 4kTRΔf where νrms is the root mean square voltage associated with this noise k = (Boltzmann’s constant)= 1. ( 1 J = 1 V2sΩ-1) T = temperature in K R = resistance in ohms (Ω) Δf = frequency bandwidth = 1 3t r where tr is the rise-time. Page 3 of 10 . and environmental noise. (a) Thermal Noise (or Johnson Noise.38 x 10-23 J/K. irms = 2IeΔf Where: irms = root mean square of the current fluctuation I = average dc current e= charge on an electron = 1.

and is proportional to the magnitude of the signal. At small frequencies – high levels of noise Good regions in frequency spectrum: 3-60 Hz and 1 kHz to 500 kHz. Related to # electrons or photons arriving at a surface. (d) Environmental Noise Due to surroundings: Instrument components can act as antennas – pick up environmental signals.(c) Flicker Noise (or 1/f noise – or ‘pink noise’) Physical origins of this noise are not well understood. noise increases. so as frequency decreases. Page 4 of 10 . Depends on frequency. Significant as frequency is 100 Hz or lower.

Why would we want to do that? the use of a high pass filter can remove lower frequency noise. .How is modulation accomplished? Modulation is accomplished by using a chopper to physically disrupt the signal – results in a signal with a new frequency dependent on speed of chopper (fluctuates between full signal ‘on’ and then full signal blocked ‘off’).C: Signal to Noise Enhancement When higher sensitivities and accuracy is required.or reduce the amplification of the low frequency noise and therefore amplifying the signal (now at higher frequency) and overall increasing S/N ratio.Why use modulation? Useful when we have a low frequency sample. (1) Some Hardware devices for Noise Reduction Adjusting the instrument design: (a) (b) (c) (d) Grounding and Shielding Difference and Instrumentation Amplifiers Analog Filtering Modulation .What does modulation do? modulation involves taking a low frequency signal and converting it into a high frequency signal . S/N can start to limit our precision. Page 5 of 10 . and there is low frequency noise as well (such as flicker noise) we can use a process called modulation to reduce noise .

1. If we just amplified the signal as it is – since it lies in a region where flicker noise is high for amplified signals – the signal and the noise will be amplified – no gain in S/N will be realized. the signal is amplified by a factor of 105.Example: The signal of interest may be a signal of low frequency (Fig 5-6) Left picture (A): On left is original signal.) Middle picture (B): the modulated and amplified signal. 6. 4. The signal has a maximum at 0-0. Most of noise hasn’t moved in frequency. The signal has a maximum power of ~ “6” (or 6 x 100). Page 6 of 10 . 5. Now the signal can be detected or worked with at a frequency of 400 Hz.001 Hz (so it’s low in frequency). The flicker noise in the region of 10 Hz and lower. Right picture (C): Demodulation occurs – taking the signal back to its original frequency. is amplified also. At this “place”. The modulation frequency is 400 Hz (400 cycles per second) – can be accomplished with a mechanic chopper. and the noise is not nearly so amplified. The signal amplitude increases from ‘6’ to ‘ 6 x 105 ’.rotating disk. The original signal has been amplified. but we’ve ‘moved’ the signal to a different frequency. So the signal is modulated (a frequency is ‘added’ to it by chopping the signal). while at its new frequency. 3. 2.

while the noise varies. S/N increases ∝ to n where n = # of scans Used widely in NMR and FTIR Page 7 of 10 .and then summed point by point “co-addition” and then averaged (divided by number of repeats) o This increases the signal-to-noise ratio by a factor of number of repetitions n where n is the o the signal is positively reinforced.ends up not increasing as much. constructive and destructively interfering.(2) Software methods for Noise Reduction Computer algorithms pull signals from noisy data: (a) Ensemble Averaging o several repetitions of a the signal are taken and stored as arrays.

Page 8 of 10 .In the figure shown below – every three points are averaged and that average is used to replace them.(b) Boxcar averaging .By averaging a group of adjacent points (that are close in time). it is assumed that the differences in the magnitude of these data points will be due mainly to noise deviations.This increases the signal-to-noise ratio (also) by a factor of the number of repetitions n where n is . but S/N can be improved.Assumes the analytical signal of interest varies slowly with respect to the noise on the signal which varies more erratically at a higher frequency.Detail can be lost this way. . . .

This is then multiplied by the frequency response of a digital low-pass filter – this essentially removes signals of frequencies higher than some cut-off. . . time} see figure ‘a’ below.An inverse FT (Fourier transfer) is use to re-generate the signal back into the ‘user-friendly’ time domain. Page 9 of 10 .Fourier Transform: one method of digital filtering. frequency. . Fourier transform is accomplished as follows: .Signal is initially collected in the “time domain” {signal vs.The Fourier transform (a mathematical algorithm process) converts the ‘time domain’ signal into a frequency domain signal – see figure ‘b’ which is a new function of frequency plotted vs.(c) Digital Filtering: .

A different yet complimentary figure: Figure 7-41: Time domain vs. frequency domain. Page 10 of 10 .

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