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Chapter 5 Signals & Noise

Problems: 1, 2, 4, 5, 7, lab Avery measurement contains 2 components, the wanted signal and the unwanted noise. Sometimes this noise is very apparent, other times is it so small that you can ignore it. This chapter discusses some of the common sources of noise and how the effects fo the noise can be minimized 5A The Signal-to-Noise Ratio Figure 5-1a a signal from a strip chart recorder. A what you really see, and B what the signal probably actually was. Most experiments strength noise (N) is constant and independent of signal (S) The % error in the signal become larger as signal get smaller For this reason use the figure of merit Signal-to-noise (S/N) instead of just the noise to describe the performance of an instrument For a DC signal like first figure use mean value for signal and standard deviation of the noise:

Note the signal-to-noise is inverse of RSD (relative standard deviation) has back in chapter 1 so: S/N = 1/RSD For signal like that shown in figure 5 easy way to estimate S is to take the peak-to-peak noise by 5. This is because, in a random signal, 99% of the signal is within +/- 2.5 standard deviation. As a general rule if S/N is <2 or 3, cant detect a signal 5B Sources of noise in Instrumental Analysis 5B-1 Chemical Noise From a source of uncontrollable variables in the chemistry Changes in pressure or T of Reaction, Changes in humidity, vibrations that cause solid samples to settle unevenly, light affecting photo reactions, chemical fumes interacting with your reaction etc

2 5B-2 Instrumental Noise Electrical and/or mechanical noise associated with each component of instrument Noise is a complex composite of lots of things Helpful to break down into some recognizable components to see if can be fixed or not 1. Thermal or Johnson Noise 2. Shot noise 3. Flicker or 1/f noise 4. Environmental noise Thermal Noise or Johnson Noise Caused by thermal agitation of electrons and other charge carriers in any part of the electronics (resistors, capacitors, Integrated chips, transistors, wires, connections etc) Random inhomogeneities of charge and therefore voltage at readout Magnitude in a resistive circuit can be derived from thermodynamics

vrms is root-mean-square of noise voltage lying in a frequency Frequency bandwith of )f k is Boltzmann constant R is resistance in Ohms T is temp in K Didnt do section 3B-2 so lets look a bit more at frequency bandwidth, )f Has to do with how fast a circuit can respond to a change in voltage Can see from equation that k and R are fixed, so there are only 2 things you can do to lower this kind of noise Reduce T (keep instrument cool, perhaps put some elements in liquid N2) Reduce )f How do you do this? )f is the response time of the circuits in the instrument. The more slowly they respond to a signal, the lower the thermal noise.

3 Also note that this noise is independent of frequency, also called white noise because present at all frequencies in a constant amount Shot Noise Arises when electrons cross a junction Can be junctions between n and p material in a transistor, Electrons jumping across a vacuum in a vacuum tube, solder joints in the circuit board, etc Arises because electrons are quanta of charge, and flow of charge across a junction is therefor a multiple quanta event, and has to be dealt with using statistics

So the rms noise in the current is due to I average direct current E charge on the electron )f bandwidth of frequencies again I and e fixed So again the only way to minimize is to slow response of circuit Again is a white noise, uniform across all frequencies Flicker Noise Inversely proportional to frequency If 1/f That is why also called 1/f noise Cause not well understood Recognized by frequency dependence Becomes significant in signals <100 HZ Worst for 0 Hz, or DC drift! Better in wire-wound or metallic film resistors Worse in standard carbon resistors So can be improved by using different electronic components in your circuit Environmental Noise Composite of noise from surroundings Figure 5-3 Every wire in your instrument can act like an antenna to pick up

4 electromagnetic energy and convert it into an electrical signal inside your instrument As you can see from the figure, there are lots of things in the environment that are putting out Electromagnetic signals Note there are two region that are relatively noise free 3Hz ro 60Hz and 1 kHz to 500 kHz Will often design instruments around these frequencies to take advantage to this low environmental noise 5C Signal-to-Noise Enhancements For many things we do in the lab, we have plenty of signal so we dont have to worry about S/N. Its only when we are pushing the limits of sensitivity or accuracy of an instrumental method where we really have to try to get the optimal S/N out of a machine Both Hardware and software methods to improve S/N Hardware methods -properly design instrument include choppers, shields modulators and other things in instrument design Software methods - computer algorithms to extract signal from under noise usually done with digital data so need to convert data from analog to digital, going to be done on a computer 5C-1 Hardware methods for Noise reduction Grounding and Shielding Noise from environment can often be dramatically reduced by shielding, grounding, and minimizing wire lengths Shielding - surrounding a circuit or the wires in the circuit with a conducting material then attaching that to ground. Environmental EM radiation cant penetrate the conductor where it gets absorbed Arranging optimum shielding is something of an art., something of hit and miss Very important in high resistance transducers (like glass electrodes or pH electrodes Here even tiny noise get dramatically amplified Difference and Instrumentation Amplifiers Any noise in transducer is bad because this is the signal that gets amplified and interpreted by the rest of the instrument To amplify signal but not noise, instruments typically use a

5 difference amplifier for first stage of amplification If this isnt enough a circuit called an instrumentation amplifier is used With these kinds of electronics can amplify signal 1000x and reject 106 of noise So if you ever start do actually design an instrument, learn these circuits Analog Filtering Most common way of improving A/N is with a low-pass filter Figure 5-5 Low pass means that it passes slow moving signals (low frequency) but it stops signals with high frequencies, the jiggling noise Can be done with just a resistor and a capacitor as shown This method is most common used in alder analog instruments. You have a switch on the consol where you change either the capacitor or the resistor, that changes the time response of the instrument. Does reduce high frequency noise, but can also damage signal, so you have to be careful how this is used (See CD lab) At other times can use a high pass filter to pass a high frequency signal but block a low frequency drift Also can use narrow band or band pass filters to let just certain frequencies through (will use a lot in NMR) Modulation Have seen that drift or flicker noise is a problem One way to relieve this problem is to change this low frequency signal to a higher frequency by modulation This is what a chopper does in a double beam instrument But can also do electronically with the signal alone Can do as shown in figure 5-6 Once signal is high frequency is in a region that has less background noise, and can amplify. Without amplifying noise. Then demodulate and read it off

6 Signal Chopping: Chopping amplifiers Lock in amplifiers Both have to do with circuits used for chopping. Since we arent dealing with electronics that much in this course we will skip. One important point out of discussion is that you want to chop or modulate the signal as close to the source as possible, since the modulation only eliminates noise that occurs in the circuit AFTER the modulation event. 5C-2 Software Methods Now that lots of instrument are computer controlled, there are lots of computer methods and programs that can be used to reduce noise, lets look at them Ensemble Averaging Also called coaddition Adding signals from identical runs together Can be entirely in computer digital memory Can be hard wired into the circuitry with capacitors Example in figure 5-9 Without going through the equations, the important point of math is this section is: S/N % sqrt(n) Bottom line you want to double your S/N you need to take 4x as many point (sqrt(4)=2) This also applies to other averaging techniques like boxcar averaging and digital filtering (will see in next sections) Will see this used much in NMR and FTIR, since can obtain a spectrum in a few seconds, so can send time to accumulate lots of signal and average together To have ensemble averaging accurately reflect extract all the information in a signal need to measure points at a frequency that is at least 2x the highest frequency in the signal. This is called the Nyquist sampling theorem Lets explain better than book Say we have a cosine wave that has a frequency of 1 Hz. Wave repeats itself every second

7 This theory saws we need to sample at 2 Hz or 2x/second Draw a 1 second cosine function on the board Now shows what happens when you sample at 1 Hz (every second) Get a flat line, would assume a DC signal of 0Hz so get it wrong Now show what happens when sample at 2 hz (every second) Get peak and valley so accurately get this wavefunction Important in NMR and FTIR where need to recognize and sometimes use this parameter in setting up your experiment for optimum resolution Sampling at a higher frequency probably doesnt hurt, although this extra sampling only introduced extra noise. Most instruments set up to sample at 10x the nyquist frequency to have a goo margin for error above the minimum. Also note that for proper addition of signal you must add only signals that are in sync start and end at exactly the sem place and have data points that are at exactly the same time Effects of ensemble averaging shown in figure 5-10 Will talk more about Nyquist in FT NMR chapter Boxcar Averaging Digital procedure for smoothing out noise Assumes that signal varies slowly Assumes that the average of several points is a better representative than any single point Essentially take anywhere between 2 and 50 points and average together to replace a point See figure 5-11 Some detail is lost in this process Not good for rapidly changing signals Can be done via computer Or via a hardware device called a boxcar integrator Time over the average is called the aperture time Same sqrt(N) S/N improvement as in ensemble averaging

8 Digital Filtering Lots more techniques, but here will look at two Fourier Transform Least squares polynomial Fourier Transform See figure 5-12 Acquire data in time domain (as a function of time) Do FT to change to frequency domain Since signal changes slowly - it has a low frequency Noise changes quickly - has a high frequency Keep only the low frequency components Zero out high frequency Inverse FT to get back original data But no high frequency noise remains Do variations of this on NMR all the time for noise reduction or resolution enhancement Built in to many programs (including excel?) Linear Least Squares best fit