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P
D
2
1i
Rank
Group 1
1, 10 5.5 -4.5, 4.5 20.25, 20.25 40.5 4.5
10, 0 5.0 5.0, -5.0 25.00, 25.00 50.0 6
9, 0 4.5 4.5, -4.5 20.25, 20.25 40.5 4.5
Subsample
X X
X X
X
2
P
X
X
2
P
D
2
2i
Rank
Group 2
4, 4 4.0 0.0, 0.0 0.0, 0.0 0.0 1
5, 6 5.5 -0.5, 0.5 0.25, 0.25 0.5 2.5
5, 6 5.5 -0.5, 0.5 0.25, 0.25 0.5 2.5
Accred Qual Assur
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subjects are employed in the analysis. In this instance, it is
used a table of random numbers to select the scores for
each of the subsamples.
X
R
1
4:5 6 4:5 15 and
X
R
2
1 2:5 2:5 6:
U
1
, U
2
, and U are calculated as:
U
1
m
1
m
2
m
1
m
1
1
2
X
R
1
3 3
3 3 1
2
15 0 3
U
2
m
1
m
2
m
2
n
2
1
2
X
R
2
3 3
3 3 1
2
6 9 4
U
calculated
is the minimum value between U
1
and U
2
:
U
calculated
min U
1
; U
2
0
As U
calculated
0 U
critical
0, there is not a statisti-
cally signicant difference between the variances of
Groups 1 and 2.
Test of Bonett-Price [15]
This test is applied to data sets with nonparametric distri-
butions. In this situation, the condence interval is based
on a linear function of medians of the population.
The median (M
d
) of the data set and estimation the
variance, varM
d
, are calculated by
varM
d
Y
na1
Y
a
2z
2
Y
(i)
represents the quantitative score of the response vari-
able in the position i (ordered).
a and z are tabulated, in function of the data number and
level of signicance [15].
The condence interval, CI, can be calculated by:
CI M
d
z
a=2
varM
d
51:4 1:96150:91
27:33; 75:47.
Experimental
Four case studies, one for each procedure, are discussed in
this work.
Data were collected from Alberto Pasqualini Renery,
Canoas, Brazil.
In the rst study, ammoniacal nitrogen concentration in
efuent samples is determined by RT and PA. Validation is
performed using Procedure A. The process analyzer is GLI
International (IL, USA), model 750-500 ion selective
electrode whose work range is 020 mg L
-1
. The mea-
surement procedure is based on Standard Methods 4500.
In the second study, ethane amount of substance fraction
in the same sample hydrogen recycle is determined by RT
and PA. Validation follows Procedure B. The process
analyzer is a Yokogawa (Tokyo, Japan) chromatograph,
model GC 1000 Mark II, work range 01 mmol/mol. The
measurement procedure is correlated to UOP 539.
The next study involves ash point in diesel oil. The
process analyzer is an integrated ash point, Precision
Scientic Petroleum Instruments (IL, USA), model 45624,
work range 10121 C. The measurement procedure is
correlated with ASTM D93.
For the last study, propane amount of substance fraction
in a reference sample of hydrogen recycle is determined by
PA, validated by Procedure D and compared with the
certied result. The process analyzer is a Yokogawa
chromatograph model GC 1000 Mark II, work range
01 mmol/mol. The measurement procedure is correlated
with UOP 539.
Results and discussion
Nonparametric data from case studies are calculated by
both parametric and nonparametric tests, Table 5. Before
choosing one of these tests, it is necessary to assess whe-
ther or not the data follow a normal distribution. In this
work, the ShapiroWilk test, named as SW, is used to check
deviation from normality/normal distribution [16].
All calculations are conducted by Microsoft Excel, and
critical values are based on a condence level of 95 %. No
value is considered as an outlier by Grubbs and MAD tests.
Case study: Procedure A
Comparison of mean and median is evaluated by ten dif-
ferent samples that are analyzed by PA and RT. The mass
Table 8 Precision and comparing mean and median evaluations of results from the same sample for ethane determination by parametric and
nonparametric tests
Process analyzer (PA) [mmol/mol] Reference test (RT) [mmol/mol]
0.102 0.102 0.103 0.102
0.102 0.102 0.102 0.102
0.103 0.102 0.102 0.102
0.103 0.102 0.102 0.102
0.103 0.102 0.102 0.102
0.103 0.102 0.102
0.103 0.102 0.102
0.102 0.102 0.102
SW
calculated
= 0.591 \SW
critical
= 0.887 SW
calculated
= 0.311 \SW
critical
= 0.866
Non-normal distribution Non-normal distribution
Parametric statistics Nonparametric statistics
F-FischerSnedecor Moses
F
calculated
= 2.98 [F
critical
= 2.62 U
calculated
= 4.00 [U
critical
= 1.00
There is a statistically signicant difference between the
variances
There is not a statistically signicant difference between the
variances
Unpaired t test Wilcoxon rank-sum test
t
calculated
= 1.656 \t
critical
= 2.056 W
calculated
= 3.05 [W
critical
= 1.96
There is not a statistically signicant difference between the
means
There is a statistically signicant difference between the
medians
Accred Qual Assur
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concentrations are shown in Table 6. ShapiroWilk test
for the differences of each pair, between PA and RT:
SW
calculated
= 0.7253 \SW
critical
= 0.8420. The distribu-
tion is non-normal.
Precision is evaluated by comparing ten results of the
same sample that is analyzed either by PA or RT. The mass
concentrations and the results treated by parametric and
nonparametric tests are shown in Table 7.
Case study: Procedure B
Precision and mean/median are evaluated by the same
sample. PA and RT use sixteen and thirteen replicates,
respectively. The amount of substance, comparing preci-
sion (variance) and mean/median evaluations by
parametric and nonparametric tests, is shown in Table 8.
Case study: Procedure C
Only, comparison of mean and median is evaluated in this
procedure. Ten different samples analyzed by PAand RTare
compared. The ash points and comparison of mean and
median by parametric and nonparametric tests are shown in
Table 9. ShapiroWilk test for the differences of each pair,
between PA and RT: SW
calculated
= 0.8294 \SW
critical
=
0.8420. The distribution is non-normal.
Case study: Procedure D
Only, comparison of mean and median by parametric and
nonparametric tests is evaluated in this procedure. A con-
dence interval derived from twenty-three replicates of a
reference sample analyzed by PA is compared with the
certied value. The amount-of-substance fraction is shown
in Table 10.
Conclusions
New procedures for performance validation of process
stream analyzer systems have been developed to deal with
nonparametric data. The procedures can be applied to all
common situations faced in that activity, such as non-
availability of a reference test, impossibility of introduction
of the validation sample in the analyzer, and non-avail-
ability of a typical process sample. From the studied
Table 9 Comparison of mean and median of ash point results from ten different
samples by parametric and nonparametric tests
Process analyzer (PA) [C] Reference test (RT) [C]
40.0 39.0
40.0 41.0
41.0 41.0
41.0 41.0
40.5 40.0
39.5 39.5
43.0 43.0
43.0 43.0
41.5 41.5
42.0 41.0
Parametric statistics Nonparametric statistics
Paired t test Wilcoxon signed-rank test
t
calculated
= 0.818 \t
critical
= 2.262 W
calculated
= 4.00 \W
critical
= 8.00
There is not a statistically
signicant difference between the means
There is a statistically signicant
difference between the medians
Table 10 Comparison of mean and median of replicates of a reference sample for propane determination by parametric and nonparametric tests
Process analyzer (PA) [mmol/mol]
0.3011 0.3030 0.3041
0.3020 0.3030 0.3040
0.3020 0.3030 0.3052
0.3030 0.3030 0.3050
0.3029 0.3030 0.3050
0.3030 0.3030 0.3060
0.3030 0.3030 0.3061
0.3030 0.3030
SW
calculated
= 0.8531 \SW
critical
= 0.9140
Non-normal distribution
Parametric statistics Nonparametric statistics
t test Bonett-Price
Process Analyzer (PA) 0.30290.3040 0.30250.3035
Reference Sample (RS) 0.30370.3043 0.30370.3043
There is not a statistically signicant
difference between the means
There is a statistically signicant
difference between the medians
Accred Qual Assur
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examples, it is possible to observe that when parametric
statistics are applied to nonparametric data, different
results can be obtained, leading to wrong conclusions,
which highlight the importance of the use of the right
statistics in each case. This manuscript can be very useful
for readers to understand better this subject given that
international standards do not foresee and deal with it. In
2014, this study will be part of a new Brazilian standard in
order to cover this deciency.
Acknowledgments This work was supported by Petrobras, and the
original idea and the meetings to elaborate it were sponsored by
Marcia Beatriz Ruiz Del Frari, manager from Products Engineering
and Oil Stockpiling of the Downstream-Renery.
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