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Filtering Data to Find Outliers and Calculating Uncertainty of Km Value

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Adian Fatchur Rochim

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 Filtering Data to Find Outliers and Calculating
Uncertainty of Km Value
Instructor : Prof.Dr. Ir. Harinaldi, M.Eng (HRN)
Adian Fatchur RochimAdian Fatchur Rochim
PhD Student - Department of Electrical Engineering, Faculty of Engineering
University of Indonesia, Depok, Indonesia
Email: adian@ieee.org
C.F Oduoza, A.A Wragg and M.A Patrick showed in Chem-
ical Engineering Journal, 68, (1997) that the local coefficient
of convective mass transfer in an electrochemical process be-
tween two electrodes can be determined by limiting di↵usion
current method. They pointed out that the local mass transfer
coefficients, Km (m/s) were then calculated using the equation:
where Ilim is the local limiting current (A) measured at local
cathode, z is the number of electrons exchanged, F is the
Faraday number (96 487 A.s/mol), A is the exposed mini-
cathode area (m2) and C is the bulk electrolyte concentration
(mol/m3). (Course homework - I use R language).
Ilim
Km = (1)
zF AC
Applying the above method, the attached time series data is
the result of Ilim measurement using a high precision Digital
Multi Meter (manufacturer calibration documents notes that
uncertainty is 0.5 %). If z = 2, A = 1.8 x 10-6 m2 (uncertainty
2 %) and C = 500 mol/m3 (uncertainty 2 %), find out:
(a) Filtered data suitable to be used for further analysis !
(b) what is the uncertainty in Km value?
I. Methodology and Data Analysis
Theorem 1. Peirce’s criterion is an in-depth derivation
formulated directly from the theory of probability. It was
based on the following principle: ” ...the proposed ob-
servations should be rejected when the probability of the
system of errors (my note: the actual deviations from the
mean) obtained by retaining them is less than that of the
system of errors obtained by their rejection multiplied by
the probability of making so many, and no more, abnormal
observations [2].
1) Methodology using Peirce’s Criterion Method to
throw “Outlier” data.
2) Programming language using R language
3) Timeseries data 303, I assume if N > 60, using N =
60 on Peirce’s Table.
4) Removing Outlier data
5) Calculating Standard deviation and mean
6) Finding uncertainty Km Value, using Combining
Uncertainty - Simple Method
The actual method of calculation used by Peirce was
mathematically cumbersome to use and a later paper by
Gould [1] took Peirce’s criterion and presented it in a more
easily usable format with tables he derived from Peirce’s
work. Peirce proposed three tables.
The first containing value of x for the double argument
m0 = m n
N and y = N , would include the values corre-
sponding to any given number of unknown quantities. The
second table, a table of single entry, would give log (Br).
Q for di↵erent calues of y, and the third contain log R, for
argument x , being deduced from the solution of equation
(D) [1]
II. Filter Data Using Peirce’s Criterion
Algorithm 1 Peirce’s Method [2]
1) Calculate the mean and the sample standar devia-
tion (SD) of the complete data set.
2) Obtain R corresponding to the number of measure-
ments taken from Peirce’s table.
3) Calculate the maximum allowable deviation: |xi –
xm| max .
4) For any suspicious data measurements, obtain |xi –
xm|.
5) Eliminate the suspicious measurements if:
|xi xn | > |xi xm |max (2)
6) If this results in the rejection of one measurement, .
Go to step 8.
7) If more than one measurement is rejected in the
above test.
8) Repeat the above calculations (steps 2 – 5),
9) Now obtain the new value of the mean and sample
standard deviation of the reduced data set.
Time series data is the result of measurement using a
high precision Digital Multi Meter, 303 samples, Figure 1.
shown the time series data.
Figure 1 shown of the identification an original data set.
The Identification of the appropriate data is not simple,
which of the data to deleted or thrown away from an
observation. Assume a data set with numeric variable x.
Suppose there are n observations in a dataset. We want to
throw away all observations which are ”not good enough”.
Several data sample is as suspicious “not good enough”
data.
 54.6
Result Measurements
54.4
54.2

0 50 150 250
times elapsed

Figure 1. Time Series Data Source

Several suspicous data is shown Figure 1 at time 150,

250 and 300. I try to throw outlier data with Peirce’s
Criterion. As follow algorithm my program code using
Peirce’s Criterion Algorithm.

Algorithm 2 Removing Outlier

Require: Read, data source (ds) and Peirce’s R table
1: Calc sd, mean, and max
2: Calc ds’s row number -> r ow1
3: rowx <- row1 + 1
4: rowy <- row1
5: while rowx 6= rowy do
Figure 2. Iteration step-by step
6: abs t = 0
7: for i : row y do
8: abs t[i] < abs(t[i] mean) No Iteration-n Data Outlier Removed
9: end for 1 1st 300 3
10: max dev < max(abs t) 2 2nd 298 2
11: Calc R = sd ⇤ R 3 3rd 295 3
12: Filtering dan store to row 2 4 4th 291 4
13: Remove xi 5 5th 289 2
14: calculate, row y, store to row 1 6 6th 289 0
15: row y = row1 Iteration-5th Total Outlier Removed 14
16: end while

Table I
Outlier removed on each iteration
Result of number outliers removed, standard deviation
and data mean:

1) Data have been iterated, at the 5th dan 6th iteration III. Combining Uncertainty - Simple Method
process data are same.
2) Outlier remove = 14
3) Standard Deviation = 0.071 Uncertainty calculation using Simple Method
4) Mean Data = 54.49

Ilim
the following is shown the result of each iteration process. Km = (3)
zF AC
 # Data file Input is got from a csv’s file -> d1.csv
# sd = standard deviation
54.65 # xm = mean
# R Peirce’s Table by Ross 2003 ( N>60 using N=60 )
# N > 60, using N = 60
Result Measurement

# (Ref: Mathworks Discussion Forum, 17 Nov 2015)

# Reference: http://www.mathworks.com/matlabcentral/
# /fileexchange/21562-peirce-s-method
54.50

# accessed 22 March, 2016

#
# D[row index,col index]
# row index = number of Sample
# col index = iteration n-
54.35

#===================================
usr.filename <- function()
{
readline(”Please enter filename (csv format: ”)
0 50 150 250 }
data.filename <- usr.filename()
times elapsed # ————
# R Table Ross
# ————
D <- read.csv(”/data/Ross.csv”, header = FALSE,
Figure 3. Data have been omitted their outlier (at iteration-5th) strip.white = TRUE)
# ———–
# Data Source
z=2 # ———–
Ilim = 54.49 (uncertainty 0.5 %) t <- read.csv(data.filename,
header = FALSE, strip.white = TRUE)
A = 1.8 x 10 6 m2 (uncertainty 2 %) t <- t[,1]
C = 500 mol/m3 (uncertainty 2 %) data awal <- t
xm <- mean (t)
F = 96 487 A.s/mol sd <- sd(t, na.rm = FALSE)
Ilim : max <- max(t)
row1 <- NROW(t)
Ilim (max) = 54.49 + 0,27245 = 54,76245 c <- 60
Ilim (min) = 54.49 - 0,27245 = 54,49 if (row1 < 60){
c <- row1
A: }
A(max) = (1.8 + 0.036) 10 6 m2 = 1.836 x10 6 m2 row x <- NROW(t)+1
row y <- NROW(t)
A(min) = (1.8 - 0.036) 10 6 m2 = 1.764x10 6 m2 iteration <- 1
C: while (row x != row y) {
abs t<-0
C(max) = 500 + 10 mol/m3 = 510 for(i in 1:row y)
C(min) = 500 + 10 mol/m3 = 590 {
# i-th element of t abs t -> absolute |xi-xm| max
Use Simple Method to Calculate Km Uncertainty abs t[i] <- abs(t[i]-xm)
Ilim (max) 54.76245 }
Km (max) = zF A(min)C(min) = 2⇤96487⇤1.764⇤10 6 ⇤510 = max deviation <- max(abs t)
0.315 allow1 <- sd*D[c,iteration]
Ilim (min) 54,49 f <- data.frame(t,abs t)
Km (min) = zF A(max)C(max) = 2⇤96487⇤1.836⇤10 6 ⇤590 = t2 <- abs t[abs t < allow1 ]
0.261 abs f<-0
fi1 <- data.frame(0,0)
UKm = Km (max) 2 Km (min) d =1
U Km = (0,315 2 0,261) for(i in 1:row y)
{
UKm = 0.027 if(f[i,2] < allow1 )
{
Result: fi1[i,2] <- f[i,2]
fi1[i,1] <- f[i,1]
UKm = 0.027 d < d+1
}
References }
t <- fi1[apply(!is.na(fi1), 1, any), ]
[1] Jr B. A Gould. On peirce’s criterion for the rejection of doubtful row2 <- NROW(t)
observations, with tables for facilitating its application. The t <- t[,1]
Astronomical Journal, IV(83), 1855. cat (”ITERATION -”, iteration , ”\n”)
print(t)
[2] Stephen M Ross. Peirce’s criterion for the elimination of suspect iteration <- iteration + 1
experimental data. Journal of Engineering Technology, 20(2):1– row x <- row y
12, 2003. row y <- row2
}
Appendix xm <- mean (t)
sd <- sd(t, na.rm = FALSE)
#===================================
max <- max(t)
# Created by Adian March 23, 2016 ( R language )
outlier removed <- abs(NROW(t)-NROW(data awal))
#———————————————————————————-
cat(”Standard Deviation =”,sd)
# Method Reference: Article (Ross2003) Ross, S. M.
cat(”Mean Data =”, xm)
# Peirce’s Method for the elimination of suspect data
cat(”Outlier Removed =”, outlier removed)
# Journal of Engineering Technology, 2003,20, 1-12
cat(”done...”)
# ———————————————————————————

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