Spring 2017 CHEMISTRY 105

Instrumental Methods in Analytical Chemistry

Lecture: MW 9 AM 10 AM 219 Dwinelle
Labs: MTuWTh 1 5 PM 305 Latimer

Lecture 2. Error Analysis & Noise

Prof. Ke Xu

1
Q&A

What is population standard deviation vs. sample standard deviation?

Population standard deviation Sample standard deviation

(x x ) (N 1)
N N

(x )
2
= lim i
2
N s= i
N i =1 i =1

Distribution: 1-200 time points

Distribution: 201-400 time points

Definition of detection limit? 20

Detection limit: Count

10
defined as S/N = 3
0
-2 -1 0 1 2 3 4 5 6
Bin Center

2
Normal (Gaussian)
distribution:

1 1 x 2
f ( x) = exp
2 2

Highest probability for close to

Wider spreading for larger

3
Confidence intervals (CI) for a single measurement, known

For a confidence level of 68%,

should be in the interval:
CI for = x z
x

Confidence
z
level
0.8 1.2816
For a confidence level of 95%,
should be in the interval: 0.9 1.6449
0.95 1.9600
1.96 x 1.96 0.98 2.3263
Most often used! 0.99 2.5758
0.995 2.8070
0.998 3.0902
0.999 3.2905
For a confidence level of 99.7%,
should be in the interval:
0.9999 3.8906
0.99999 4.4172
x 3 0.999999 4.8916

4
Propagation of uncertainty
N
= lim (x )
2
i N
For addition or subtraction of data N i =1

For x = x1 x2 x3 ... = 12 + 2 2 + 3 2 ...

Example: total weight

For multiplication or division of data

dxy ydx xdy dxy dx dy

dxy = ydx + xdy = + = +
xy xy xy xy x y

2 2
xy y
= x +
xy x y

Use relative uncertainly for the calculation!

2 2 2
x p q r
For x = p q / r... = + + ...
x p q r
Example: R = U/I
Everything is unit-less 5
 6
Repeated measurements averaging of results
Repeated measurements of the same signal: each measurement has the same

Sum: Sum = x1 + x2 + x3 + ... + x N

2 2 2
Uncertainty of sum: sum = 1 + 2 + 3 ... = N 2 = N

1.0

Uncertainty of mean
Mean: x = Sum / N 0.8

0.6

Uncertainty of mean: m = sum / N = / N 0.4

0.2

Uncertainty of Uncertainty of 0.0

the averaged each single 1 2 3 4 5 6 7 8 9 1011121314151617181920
# of measurements
5
value measurement

Improvement in S/N
4

Signal Signal
S/N: = N 2

m 1

0
Improved S/N for repeated measurement! 1 2 3 4 5 6 7 8 9 1011121314151617181920
# of measurements
Improving S/N through averaging

5
Improvement in S/N
4

0
1 2 3 4 5 6 7 8 9 1011121314151617181920
# of measurements

7
Confidence intervals (CI) for mean, known

Confidence
z
level
0.8 1.2816
0.9 1.6449
0.95 1.9600
0.98 2.3263
0.99 2.5758
0.995 2.8070
0.998 3.0902
0.999 3.2905
m = / N 0.9999 3.8906
0.99999 4.4172
For a confidence level of 95%, should be in the interval: 0.999999 4.8916

x 1.96 m
CI for = xz
N

x 1.96
N
8
 9
CI when is unknown: using s to estimate
With known With unknown

Normal distribution: Student's t-distribution

X-axis is in unit of X-axis is in unit of s

Degree of freedom: = N 1
Approaches normal distribution for
Distribution broadens for smaller : extra
uncertainty when using s to estimate
CI when is unknown
Values of t for different confidence levels

80% 90% 95% 98% 99% 99.9%

1 3.078 6.314 12.710 31.820 63.660 636.600
2 1.886 2.920 4.303 6.965 9.925 31.600
3 1.638 2.353 3.182 4.541 5.841 12.920
4 1.533 2.132 2.776 3.747 4.604 8.610
5 1.476 2.015 2.571 3.365 4.032 6.869
6 1.440 1.943 2.447 3.143 3.707 5.959
7 1.415 1.895 2.365 2.998 3.499 5.408
s
CI for = xt 8 1.397 1.860 2.306 2.896 3.355 5.041
N
9 1.383 1.833 2.262 2.821 3.250 4.781
10 1.372 1.812 2.228 2.764 3.169 4.587
Compared to known :
15 1.341 1.753 2.131 2.602 2.947 4.073

= xz 20 1.325 1.725 2.086 2.528 2.845 3.850
N
50 1.299 1.676 2.009 2.403 2.678 3.496
t>z
100 1.290 1.660 1.984 2.364 2.626 3.390
t z for
1.282 1.645 1.960 2.326 2.576 3.291
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Example (a1-6)
95% CI for three measurements: 0.084, 0.089, and 0.079
N

x i
0.084 + 0.089 + 0.079
x= i =1
= = 0.084
N 3

(x x )
N
0 + (0.005) 2 + (0.005) 2
(N 1) =
2
s= i = 0.005
i =1 2

s
95% CI: = x t = 2, for 95% CI: t = 4.303
N
0.005
= 0.084 4.303 = 0.084 0.012
3

However, if is known to be 0.005 from previous tests:

0.005
95% CI: = x z = 0.084 1.96 = 0.084 0.006
N 3 11
Experimental sources of noise/uncertainty

Improve S/N by reducing noise!

Chemical Noise
Undesired chemical reactions / interactions
Interfering chemical compounds: needle in a haystack
Fluctuation in humidity

Reduction:
Improve selectivity
Separation
Multidimensional analysis

Instrumental Noise
Associated with each component of the instrument

Thermal (Johnson) Noise

Shot Noise
Flicker (1/f) Noise
Environmental Noise
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Instrumental noise white noises (f-independent)
Thermal (Johnson) Noise
Thermal (kT) agitation of electrons and other charge carriers

V rms = 4kTRf
Bandwidth
Temperature Resistance
Reduction:
Lower R of the circuits
Lower T: e.g., Liquid-nitrogen cooled detectors
Lower bandwidth of instrument
1
However, f = f t r
3t r Response time (rise time)

Shot Noise
When charged particle crosses a junction. Quantized events statistical fluctuation

= N irms = 2 Ief
Reduction:
Lower bandwidth of instrument 13
Instrumental noise 14

Flicker Noise (1/f noise; pink noise)

Higher noise at lower frequency!

Environmental noise
Hardware devices for noise reduction
Grounding and shielding

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Thanks!

http://xkcd.com/1347/