Statistics & Error propagation

N →∞
xi N
xi
µ= ∑
i =0 N
x=∑
i =1 N

N N

∑ (x i − µ)2 ∑ (x i − x) 2
σ= lim
i =0
s= i =1

N →∞
N N −1

µ = x ± zσ N µ = x ± ts N

Na Nb

∑(x
i =1
ai − xa ) 2 + ∑ ( xbj − xb ) 2
j =1
2
( N a − 1) sa + ( N b − 1) sb
2
Spool = or Spool =
Na + Nb − 2 Na + Nb − 2

N
Sxx = ∑ (x
i =1
i − x)2 Intercept = b = y -m x

S r 1 1 ( yc − y ) 2
For the method of External Calibration Sc = + +
m M N m 2 S xx
The method of Standard Additions requires extrapolating a linear equation to a single
point. Therefore the 1/N term is removed and y = 0 in the above. Since it is an
extrapolation to a single point “N” = 1 in the confidence interval calculation.

Propagation of error into a result (x) from variables (p,q,r,y) with standard deviations (Svariable)

Addition & subtraction x=p+q–r Sx2 = Sp2 + Sq2 +Sr2

Multiplication & division x = pq/r 2 2 2 2
 S x   S p   Sq   Sr 
  =   +   +  
 x   p  q   r 
Exponentiation x = py Sx Sp
=y
x p
Logarithm x = log10p Sp
S x = 0.434 ×
p
Antilogarithm x = antilog10p Sx
= 2.303 × S p
x
Basic constants of this universe, may differ in other universes or singularities
Constant Symbol Value

Speed of light (vacuum) c 2.99 x 108 m/s

Plank’s constant h 6.626 x 10-34 Js
Avogadro’s number N 6.022 x 1023 particles/mole
Faraday’s constant F 96485 C/mole
Gas constant R 8.3145 J/(K mole)
R 0.0820 L atm / (K mole)
Boltzmann’s constant k 1.3806 x 10-23 J/K
Mass of electron (rest) me 9.109 x 10-31 kg

Odds & Ends

P P
Transmittance T= Percent transmittance %T = × 100%
Po Po
Absorbance A = abc
−E j
Nj Pj
Boltzmann’s equation = e kT
No Po
Chromatography
L L
M.P. velocity u= Analyte velocity v=
tm tr
KVs tr − tm Cs Kb k b′
k'= k'= K= α= =
Vm tm Cm Ka k a′
CmVm 1 1 1
v=u =u =u =u
CmVm + CsVs 1 + CsVs 1 + KVs 1+ k'
CmVm Vm
2 2 2 2
 tr  tr α   1 + kb′ 
N = 5.54  = 16  = 16 Rs2    k ′ 
 W1 / 2  W   α − 1  b 

k b′ − k a′ N
Rs = ×
1 + k b′ 4
2
NH (1 + kb′ ) 16 Rs2 H  α  (1 + kb′ )
3
trb = =  
 α − 1  (kb′ )
2
u u

B 2γDm fs (k ' )d 2f fm(k ' )d p2 π r2

A = 2λd p = Cs u = u Cmu = u H ex = u
u u Ds Dm 24 Dm
Polarity indices of common liquid chromatography solvents
Fluoroalkanes -2 Dioxane 4.8
n-hexane 0.1 Methanol 5.1
Toluene 2.4 Acetonitrile 5.8
Ethanol 4.3 Water 10.2
 Grubbs table ** Number of Q table
90% 95% 99% Measurements 90% 95% 99%
1.1531 1.1543 1.1547 3 0.941 0.970 0.994
1.4625 1.4813 1.4963 4 0.765 0.829 0.926
1.6714 1.7150 1.7637 5 0.642 0.710 0.821
1.8221 1.8871 1.9728 6 0.560 0.625 0.740
1.9381 2.0200 2.1391 7 0.507 0.568 0.680
2.0317 2.1266 2.2744 8 0.468 0.526 0.634
2.1096 2.2150 2.3868 9 0.437 0.493 0.598
2.1761 2.2900 2.4821 10 0.412 0.466 0.568
2.4090 2.5483 2.8061 15 0.338 0.384 0.475
2.5566 2.7082 3.0008 20 0.300 0.342 0.425
2.7451 2.9085 3.2361 30 0.260 0.298 0.372
** NB: the Grubbs critical values MUST be used out to their full number of decimal places

Ttable
Confidence level % 80 90 95 99 99.9
Degrees of freedom
1 3.078 6.314 12.706 63.656 636.578
2 1.886 2.920 4.303 9.925 31.600
3 1.638 2.353 3.182 5.841 12.924
4 1.533 2.132 2.776 4.604 8.610
5 1.476 2.015 2.571 4.032 6.869
6 1.440 1.943 2.447 3.707 5.959
7 1.415 1.895 2.365 3.499 5.408
8 1.397 1.860 2.306 3.355 5.041
9 1.383 1.833 2.262 3.250 4.781
10 1.372 1.812 2.228 3.169 4.587
11 1.363 1.796 2.201 3.106 4.437
12 1.356 1.782 2.179 3.055 4.318
20 1.325 1.725 2.086 2.845 3.850
∞ 1.282 1.646 1.962 2.581 3.300

Ftable at confidence level = 95%

Degrees of freedom of numerator
2 3 4 5 6 7 8 9 10 11 12 20
2 19.000 19.164 19.247 19.296 19.329 19.353 19.371 19.385 19.396 19.405 19.412 19.446
Degrees of freedom of denominator

3 9.552 9.277 9.117 9.013 8.941 8.887 8.845 8.812 8.785 8.763 8.745 8.660
4 6.944 6.591 6.388 6.256 6.163 6.094 6.041 5.999 5.964 5.936 5.912 5.803
5 5.786 5.409 5.192 5.050 4.950 4.876 4.818 4.772 4.735 4.704 4.678 4.558
6 5.143 4.757 4.534 4.387 4.284 4.207 4.147 4.099 4.060 4.027 4.000 3.874
7 4.737 4.347 4.120 3.972 3.866 3.787 3.726 3.677 3.637 3.603 3.575 3.445
8 4.459 4.066 3.838 3.688 3.581 3.500 3.438 3.388 3.347 3.313 3.284 3.150
9 4.256 3.863 3.633 3.482 3.374 3.293 3.230 3.179 3.137 3.102 3.073 2.936
10 4.103 3.708 3.478 3.326 3.217 3.135 3.072 3.020 2.978 2.943 2.913 2.774
11 3.982 3.587 3.357 3.204 3.095 3.012 2.948 2.896 2.854 2.818 2.788 2.646
12 3.885 3.490 3.259 3.106 2.996 2.913 2.849 2.796 2.753 2.717 2.687 2.544
20 3.493 3.098 2.866 2.711 2.599 2.514 2.447 2.393 2.348 2.310 2.278 2.124