Chapter 5: Signals and Noise

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.

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Example: Figure 5-1

(a) signal 0.9 x 10-15 A with noise present.

(b) theoretical depiction if noise wasnt

Problem: Make a rough estimate of the S/N for the signal shown in Figure 5.1(a). Answer:
S x 9 10 16 A S = = = 4.1 4 = 16 N s 2.2 10 A N

B: Source of Noise in Instrumental Analysis Two main types of noise effect chemical analyses: chemical and instrumental noise. (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
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is hard to predict or calculate, such as thermal noise, shot noise, flicker noise, and environmental noise. (a) Thermal Noise (or Johnson Noise, white noise, Nyquist) Results from random motions of electrons or other charge carriers. Even when no current in a system, thermal noise can be observed.

rms = 4kTRf
where rms is the root mean square voltage associated with this noise k = (Boltzmanns constant)= 1.38 x 10-23 J/K; ( 1 J = 1 V2s-1) T = temperature in K R = resistance in ohms () f = frequency bandwidth =
1 3t r

where tr is the rise-time, where

rise-time is an instruments response to an abrupt increase in signal or output in seconds If tr = 0.05 s then f = 6.6 Hz. White noise independent of absolute frequency (b) Shot Noise (Schottky Noise, quantum noise) Generated when electrons or other charged particles cross a junction.

irms = 2Ief
Where: irms = root mean square of the current fluctuation I = average dc current e= charge on an electron = 1.60 x 10-19 C f = frequency bandwidth Independent of absolute frequency sort of a white noise also.
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(c)

Flicker Noise (or 1/f noise or pink noise) Physical origins of this noise are not well understood. Related to # electrons or photons arriving at a surface, and is proportional to the magnitude of the signal. Depends on frequency; so as frequency decreases, noise increases. Significant as frequency is 100 Hz or lower.

(d)

Environmental Noise Due to surroundings:

Instrument components can act as antennas pick up environmental signals. At small frequencies high levels of noise Good regions in frequency spectrum: 3-60 Hz and 1 kHz to 500 kHz.

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C: Signal to Noise Enhancement When higher sensitivities and accuracy is required, S/N can start to limit our precision. (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 - Why use modulation? Useful when we have a low frequency sample, and there is low frequency noise as well (such as flicker noise) we can use a process called modulation to reduce noise - What does modulation do? modulation involves taking a low frequency signal and converting it into a high frequency signal - Why would we want to do that? the use of a high pass filter can remove lower frequency noise- or reduce the amplification of the low frequency noise and therefore amplifying the signal (now at higher frequency) and overall increasing S/N ratio. - 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).

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Example: The signal of interest may be a signal of low frequency (Fig 5-6)

Left picture (A): On left is original signal. 1. The signal has a maximum power of ~ 6 (or 6 x 100). 2. The signal has a maximum at 0-0.001 Hz (so its low in frequency). 3. 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. 4. So the signal is modulated (a frequency is added to it by chopping the signal). The modulation frequency is 400 Hz (400 cycles per second) can be accomplished with a mechanic chopper- rotating disk.) Middle picture (B): the modulated and amplified signal. 5. Now the signal can be detected or worked with at a frequency of 400 Hz. 6. At this place, while at its new frequency, the signal is amplified by a factor of 105. The signal amplitude increases from 6 to 6 x 105 . The flicker noise in the region of 10 Hz and lower, is amplified also, but weve moved the signal to a different frequency. Most of noise hasnt moved in frequency. Right picture (C): Demodulation occurs taking the signal back to its original frequency. The original signal has been amplified, and the noise is not nearly so amplified.

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(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- 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

where n is the

o the signal is positively reinforced, while the noise varies, constructive and destructively interfering- ends up not increasing as much.

S/N increases

to

where n = # of scans

Used widely in NMR and FTIR

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(b)

Boxcar averaging

- This increases the signal-to-noise ratio (also) by a factor of the number of repetitions

where n is

- Assumes the analytical signal of interest varies slowly with respect to the noise on the signal which varies more erratically at a higher frequency. - 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. - In the figure shown below every three points are averaged and that average is used to replace them. - Detail can be lost this way, but S/N can be improved.

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(c)

Digital Filtering:

- Fourier Transform: one method of digital filtering. Fourier transform is accomplished as follows: - Signal is initially collected in the time domain {signal vs. time} see figure a below. - 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. frequency. - 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. - An inverse FT (Fourier transfer) is use to re-generate the signal back into the user-friendly time domain.

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

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