MEASUREMENT UNCERTAINTY EVALUATION IN OIL INDUSTRY

LABORATORIES : THE ONLY REASONABLE WAY TO DO IT

P. Pestiaux1,*, F. Chebana2 , Ph. Dutot 1,** and F. Espinoux3,**

1
TOTAL FRANCE Research Center of Gonfreville PO Box 27 76700 Harfleur France
*Chairman of the Statistical Advisory Group of the GFC and the BNP, Expert member of the statistical groups ISO TC 69
and Afnor X06. Youden Award 2004 of the American Statistical Association.
2
Laboratoire de Statistique Thorique et Applique, University Paris VI- 175 rue du Chevaleret 75013 Paris France
3
TOTAL FRANCE Research Center of Solaize PO Box 22 69360 Solaize France
** Member of the CFM (French College of Metrology)

Abstract des essais inter-laboratoires (ISO 5725) ou dites dans les

Oil major companies have more than twenty research and
production laboratories practicing since more than ten years
a hundred of normalized measurement methods.
On the other side, large round robin tests are performed in
order to evaluate the repeatability and reproducibility of the
methods used to control the quality of their products. These
round robin tests include all the laboratories involved in the
measurement process, internal or contractors. They are
performed in most of the cases twice a year. All the results
are recorded in historical databases since the years 90s.
Two standard measurements largely used in the oil industry
have been selected: the density at 15C (ISO 12185) and the
viscosity (ISO 3104) at 20C.
The global uncertainty of the measurement system is clearly
defined in terms of dispersion statistics like the standard
deviations.
The uncertainty of global measurement system is then
estimated by using the GUM and is compared to
uncertainties derived from the reproducibility of round robin
tests (ISO 5725) or published in the corresponding
measurement standards.
A robust and practical methodology is then proposed as an
introduction to a discussion on industrial implementations of
uncertainty estimation and its consequences.
Rsum
Les compagnies ptrolires importantes disposent de plus
de vingt laboratoires de recherche et de production
pratiquant depuis plus de dix ans une centaine de mthodes
de mesure normalises.
D'autre part, les essais inter-laboratoires sont excuts afin
d'valuer la rptabilit et la reproductibilit des mthodes
employes pour contrler la qualit des produits. Ces essais
incluent tous les laboratoires impliqus dans le processus de
mesure, tans les laboratoires internes que les sous-traitants.
Ces essais interlaboratoires sont raliss au moins deux fois
par an. Tous les rsultats sont enregistrs dans des bases de
donnes historiques depuis les annes 90.
Deux mesures trs largement utilises dans l'industrie
ptrolire ont t choisies: la densit (ISO 12185) et la uncertainty is defined in the VIM [10] as a parameter
viscosit (ISO 3104).
L'incertitude globale du systme de mesure est clairement
dfinie en termes de statistiques de dispersion comme les
carts-type. Elle est alors estime en employant le GUM et
est compare aux incertitudes drives de la reproductibilit result of the measurement that may be expected to
normes dcrivant les mthodes de correspondantes. On
propose alors une mthodologie robuste et pratique comme
introduction une discussion sur des implmentations
industrielles destimation de l'incertitude et ses
consquences.
Introduction
In the oil industry two standard measurements largely used
have been selected: the density at 15C (ISO 12185) [3] and
the viscosity (ISO 3104) [5] at 20C.
The uncertainty evaluation is critical for the estimation of
the variability of measures used for the determination of
production specifications and production targets. In the oil
industries, too large variances leading to a bad
reproducibility can have large environmental and economic
impacts.
The object of this paper is to apply the two accepted
approaches for the evaluation of the measurement
uncertainty of the viscosity and the density: GUM (Guide to
the expression of Uncertainty in Measurement) [7] and RRT
(Round Robin Tests, ISO 5725) [1]. The first one consists to
follow the GUM [7] guide by identifying the influent
factors, finding the measurement model and deriving the
factors uncertainties to assess the global uncertainty. The
second recognized approach is the statistics exploitation of
Round Robin Tests following the ISO 5725 standard [1].
Since all the used methods are normalized, published
reproductibilities and repeatabilities are available, and if the
laboratory is accredited for a particular method it has to
regularly perform Round Robin Tests as described in the
ISO 17025 standard [16].
Uncertainty
When making a set of measurements for the same
measurand, the results are never identical; hence there is
variability in the measurement results. The uncertainty
quantifies the dispersion of the measurement data. The
associated with the result of a measurement that
characterizes the dispersion of the values that could
reasonably be attributed to the measurand.
The expanded uncertainty defines an interval about the
encompass a fraction p, 0<p<1, of the distribution of values
that could reasonably be attributed to the measurand.
Following the FD X 07-021 [17], the statistical evaluation of
Round Robin Tests in laboratories (RRT) following the ISO
5725 and the GUM are two accepted methods to evaluate
the uncertainty of measurement.
For the GUM approach, a very important step to evaluate
uncertainty is to identify sources that affect the result and its
uncertainty. These sources are set out in a cause and effect
diagram. This helps to avoid multiple counting of sources
and also assists in the grouping of components whose
combined effect can be evaluated more easily (Appendix D
in EURACHEM guide [11] about analysing uncertainty
sources).
Density
The measurement of the density is, among others, used for:
Determination of the concentration of a component in a
product resulting from a mixture, monitoring product quality
and safety, determination of the correction coefficients for
volumes evaluation
Density measurement is one of the most important
characteristics of liquids. It is defined as the mass m of the
substance (expressed in g) divided by its volume V
(expressed in cm3), following the ISO 12185 [3]. Explicitly,
the density is given by the equation
m
= [g/cm3] (1)
V dimensions of the viscometer as described by the Poiseuille
It is convenient that the reference temperature for which the
density is measured should be either 15 C or 20 C.
The relationships to the state equation can only be made
empirically like the Tait equations (see e.g. [14])
P + b
+ a ln
1 1
= g : gravitational constant [m. sec. 2],
ref Pref + b
where a, b and ref are correlated with temperature by
means of polynomial functions with degrees 2, 2 and 3
respectively.
Viscosity
Viscosity is one of the main physical properties used to
study the behaviour of a liquid.
The absolute viscosity (or dynamic viscosity) of a liquid is
the force per unit area necessary to maintain a unit velocity
gradient between two parallel plans separated by a unit
distance.
Figure 1 Viscosity Newtons assumption.
It is formulated as
= [Pa. sec] (2)
dv
dx
where
: force per unit area acting parallel to the plans [Pa],
dv/dx: velocity gradient perpendicular to these plans [sec-1].
When this ratio is constant the liquid is, by definition
Newtonian.
It is commonly used to measure the kinematic viscosity ,
which is defined as the ratio of the dynamic viscosity on the
density of the liquid (= ). This paper concerns
essentially with the kinematic viscosity.
The determination of the viscosity depends on the field of
application and on the material. In the case of petroleum
fluids, the instrument is the capillary viscometer that
measures the flow rate of liquid through a capillary under
constant pressure.
The kinematic viscosity measurement is related to the
equation (ISO 3105 [6]):
10 6 HgD 4 t
= (3)
128lV
where : kinematic viscosity [mm. s-1],
H : liquid head [m],
D : Diameter of capillary [m],
t : time of flow [sec.],
V : volume of flow [m3],
l : length of capillary [m].
The kinematic viscosity is the most used and since it is
independent on the density and hence on the pressure, it
helps to construct the cause and effect diagram.
Uncertainty of the density derived from GUM
In this section, firstly we state the nature and the mathematic
model of the measurand and the procedure used for the
measurement, secondly, we construct a cause and effect
diagram based on the model and the measurement
procedure, which helps to describe the effect of the
significant factors and to assess the corresponding
uncertainties.
Then, these uncertainties are combined to give the global
uncertainty of the measurand. Finally, the result and its
uncertainty are expressed.
1. Specifications represented by a principal branch because it affects the
whole measurand. Note that there is no correlation between
The density of the oil fluids is generally a specification these factors.
whose measurement contributes, at all the stages of the All the results about density are summarized in Table 1.
industrial processes, to better led process or the precise
determination of the quantities and produced qualities.
Repeatability T (period) Temperature
The measurand is the density of the gasoil, which is given
by
calibration
m
= 3
[g/cm ]
V

The ISO 12185 [3] standard is used to determine the density
with an Oscillating U-tube densimeter (Mettler Toledo DA-
300 M Density Meter). A small fraction of the sample (1.2
ml) of the test is introduced into a cell at controlled
temperature (15 C). The frequency of oscillation is noted A W TA Tw
and the density of the sample of test is derived by the cell
Figure 2 Cause-effect diagram for density
constants prior determined by measuring of the oscillation
frequencies of calibration fluids with known densities.
We evaluate the uncertainties of the input factors in the
From the instructions of the measurement instrument, the diagram (all branches) by appropriate A or B type GUM
density and the period of oscillation are related as follows methods; and the mean values of the main factors (principle
branches).
K mc
= T2 (4)
4 Vc
2 Vc Repeatability:
From the control charts, the repeatability uncertainty is
estimated by the value
where : density of sample in measurement tube [g/cm3] u(rep)=0.01
Vc : volume of sample (capacity of the tube) [cm3]
mc : mass of measurement tube [g] Temperature:
K: measurement tube constant From the manufacture instructions and the standard ISO
T : period of oscillation [sec.]. 12185, the measurement temperature is 15C 0.1C. The
contribution of the temperature in the global uncertainty is
Since K is constant and both mc and Vc are fixed (for the evaluated by
tube), this relation takes the simple form = AT 2 + B .
2
2
u ( ) =
2 .u (Temp )
Temp
The constants A and B are calculated by measuring the
period of oscillation T of two standard substances of known
density, e.g. air and water. The equation (4) is then
where the term is the variation of the density with
Temp
= 2A W 2 T 2 + A 2A W 2 T A 2 f temp (5)
T T T T respect to temperature, it has been evaluated by exploiting
A W A W
the data derived from the Tait equation published in [14], its
where
A : density of air, value (absolute value) is approximated by
W : density of water, 0.000683783. The uncertainty type of the temperature is
0.1
TA : Period of oscillation of the air measurement, u (Temp ) = = 0.0575C
TW : Period of oscillation of the water measurement, 3
and the additional factor ftemp represents the influence of assuming a rectangular distribution. Finally, we have
the temperature on the measurand with value one.
u ( ) = 0.0000393175.
2. Inputs uncertainties:

We should take into account the automatic measurement

method. Since the viscosity of the gasoil is less than 100
mPa, there is no viscosity effect on its density measurement Oscillation period:
(ISO 12185 [3] and the instrument instructions).
A mean value of the gasoil oscillation at 15C is
The cause and effect diagram (Figure 2) is based on the T= 103759 sec
definition and the measurement method. The temperature is
and the corresponding uncertainty is evaluated by W Density of 0.9991 0.0001 0.000100
u(T)= 2.7684617 sec water g/cm3
TA Period Osci. 85394 sec 2.76846175 3.24 10-5
Densities and oscillation periods of water and air: of air
Tw Osci. Period 109592 sec 2.76846175 2.53 10-5
of water
The calibration instrument gives (at 15C) the following
values both of density and oscillation period of water and air T Osci Period 103759 sec 2.76846175 2.67 10-5
respectively Rep Repeatability 1 0.0001 0.0001
A =0.0012 g/cm3, TA= 85394 sec.
W =0.9991 g/cm3, Tw=109592 sec. ftemp Temperature 1 3.9317 10-5 3.931 10-5
factor
Density 0.73589 0.00021858 0.000297
From the instrument characteristics we have u( W )= g/cm3
u( A )=0.0001. This helps to find the oscillation uncertainty
of water and air as Table 1 Values and uncertainties for density
u(TW)= u(TA)= 0,27684617
4. The expression of the result and its uncertainty
3. Global uncertainty

Collecting the results of the previous step and by applying The result of measurement is expressed as
the propagation of the uncertainty law, we get
ku c ( ) or U [g/cm3]
= 2A W 2 T 2 + A 2A W 2 T A 2
T T T T
A W A W
U is the expanded uncertainty, and the coverage factor k is
= 0.73589 g/cm3 generally taken 2 providing a level of confidence of 95 %

and
2 2 2 = 0.73589 0.43716 *10 3 g/cm3 at 15C
2 2 2
u 2 ( ) = .u (TA ) + .u (TW ) +
T .u ( A )
A
T W A
2 Uncertainty of the viscosity derived from GUM
2
2
2
+ .u ( W ) + .u (T ) + u ( ) + u (rep)
2 2 2

W T In this section, firstly we state the nature and the mathematic
model of the measurand and the procedure used for the
(4.63 *10 ) .(2.768) + ( 3.41*10 ) .(2.768)
5 2 2 5 2 2
+
measurement, secondly, we construct a cause and effect
diagram based on the model and the measurement
= (0.2637 ) .(10 ) + (3.8272 ) .(10 ) +
2 4 2 2 4 2
procedure, which helps to describe the effect of the
(4.3889 *10 ) .(2.768)
5 2 2
+ 3.9317 *10-5 + (0.73589) 2 (0.001) 2
significant factors and to assess the corresponding
uncertainties. Then, these uncertainties are combined to give
the global uncertainty of the measurand. Finally, the result
and its uncertainty are expressed.
=(0.00021858) .
1. Specifications
All the derivatives were obtained using the symbolic The measurand is the kinematic viscosity of the gasoil at
computation software Maple [21]. 20C under atmospheric pressure according to ISO 3104 [5]
using Ubbelohde glass capillary viscometer ISO 3105 [6].
The examples are given for standardized gasoil, which have
a viscosity from 2 to 5 mm/s at 20C.
The viscosity is given by the model:

10 6 HgD 4 t
= ftemp (6)
128lV
where the additional factor ftemp represents the influence of
the temperature on the measurand with value one.

Description Value Uncertainty Relative

x u(x) uncertainty The procedure used to determine the viscosity is the ISO
u(x)/x
3104 [5]. It consists of measuring the flow time of a volume
A Density of 0.0012 0.0001 0.083333
under its own weight through a glass capillary kinematic
air g/cm3
viscometer. The kinematic viscosity is the product of the
 flow time by the viscometer constant. The temperature is mm 2 % (0.0116 mm). As before, the rectangular
controlled with precision. distribution is assumed and the corresponding uncertainty is
The Ubbelohde viscometer is used. That type of viscometer
is widely used for the determination of kinematic viscosity 0.0116
of oil products is described in the ISO 3105 [6]. u ( D) = = 0.0067mm =0.0067*10-3 m
3
Length of capillary
2. Inputs uncertainties
The length of the capillary is l = 90 mm =90*10-3 m
The previous (6) gives the following cause-effect diagram (ISO 3105 [6] pages 30-31). By the same way as for H, the
uncertainty type is
t (time) repeatability V temperature
readability calibration
(end point) (bulb) 0.2
calibration u (l ) = = 0.115mm =0.115*10-3 m
pressure 3
Volume of bulb

calibration calibration calibration calibration Since the measurements are done at atmospheric pressure,
the effects of pressure on hydrocarbons are only sensitive
for pressure variations up to 50 bars (viscosity is multiply by
2 if the pressure increase of 300 bars). So we neglect the
g H D l pressure effect.
Figure 3 Cause-effect diagrams for viscosity
The volume of bulb is V = 3 0.15 ml. Generally and
Note that the temperature has an important effect on the according to the measurement art, the measurement of a
viscosity measurement: it affects the time of flow the and volume of 3 ml is carried out with an uncertainty better than
liquid volume at the same time. In order to avoid a multiple 30 l (with an appropriate mass sensor), so the
counting uncertainty of the temperature, we make it as a uncertainty type is
principle branch in the cause-effect diagram Figure 3. Note 0.03
that there is no correlation between these input factors. u (V ) = = 0.0173ml =0.0173*10-6 m3
3
In order to evaluate the global uncertainty of viscosity (see Temperature
step 3 bellow) and according to the above diagram, we
evaluate the uncertainty corresponding to each branch. The In theory, the temperature of liquid must be
results are summarized in Table 2. 20C 0.02C ( 6.3 ISO 3104 [5])
In reality, it is difficult to obtain an homogeneity lower than
Liquid head 0.5 C. The contribution of the temperature in the global
The length of the liquid head is H = 40 mm=40*10-3 m (ISO uncertainty is evaluated by
3105). Generally and according to the measurement art, the
2
measurement of a length of 40 mm is carried out with an 2
uncertainty of +/- 0.2 mm. u 2 ( ) = .u (T ) .
T
The rectangular distribution is assumed, because there is no
additional information about the uncertainty value. To
The term is the variation of viscosity with respect to
obtain the standard uncertainty the value of 0.2 has to be T
temperature. Since viscosity range of the gasoil is greater
divided by 3 , so the uncertainty type is
than 2 mm/sec, from the NF T60-148 [13], viscosity is
0.2
u(H)= = 0.115mm =0.115*10-3 m related to the temperature via the equation
3 A
(T + 273.15 ) B
Gravitation
= 1010 0.7 ,
where for a standard gasoil we have
We measure the acceleration due to gravity on the site of the A=17.79682748 and B=7.25586948
research center (CReS-TOTAL), we have g = 9.80630 0.00004
m/s2. Since there is no additional information about the Then the derivative is
uncertainty, the rectangular distribution is assumed. The
uncertainty is then B
(T + 273.15)
B ln(10)10 ( + 0.7)10
A
=
u( g ) =
0.00004
= 2.31 *10 5 m / s T (T + 273.15) B +1
3
= -0.216845877 (for T = 20C)
Diameter of tube
The variation of the temperature in the bath can be taken
From Table B.4 in ISO 3105 [6] and kinematic viscosity in 0.5C which contains the homogeneity and stability of the
the range 2 to 10 mm/s, inside diameter of tube is D=0.58
 bath, the determination of temperature and regulation. The 2 2 2 2
corresponding uncertainty is u(H ) u( g ) u (t ) u (rep)
+ + +
H g t rep
0.5 u c ( ) =
u (T ) = = 0.2887 C 4u ( D)
2
u (l )
2
u (V )
2
u ( )
2
3 + + +
In conclusion D l V

u 2 ( ) = (0.21684587).(0.2887) =(0.062598013) =
Time of flow 0.115* 103
2
2.309* 105
2 2
0.1
For gasoil a mean value of flow time is 260 sec, and a global + + +
40 * 103 9.80630 260
evaluation of the uncertainty on the time is

2 2
u(t)=0.1 sec
0,0067
2 4 * 0.0067* 103 0.115* 103
1,0486 + +
1 0.58 * 103 90 * 103
Repeatability

This is a type A uncertainty. It is commonly used to 2
0.0173* 10-6 0.062598
2
+
estimate them by control charts. Hence it is approximated
+
by 3 * 106 1.0486
u(rep)=0.0067.

Descriptio Value Uncertainty Relative =0.0797589622 mm/sec

n x u(x) uncertainty
u(x)/x 4. The expression of the result and its uncertainty:
H Liquid head 40 mm 0.115473441 0.002887
V Volume 3 ml 0.017321016 0.005774 The result of measurement is expressed as
g Gravitation 9.8063 ku c ( ) or U [mm. s-1]
m/sec 2.30947 10-5 0.000002
U is the expanded uncertainty, and coverage factor k may be
t Time 260 sec 0.1 0.000385 taken 2 providing a level of confidence of 95 % (classical
D Diameter 0.58 mm 0.00669746 0.011547 value in petroleum activities). With the expanded
l lengh 90 mm 0.115473441 0.001283 uncertainty the result is expressed as
Rep Repeatabili
ty 1 0.0067 0.006700
Temperature
= 1.0486 0.1595 mm/s
ftemp 1 0.062598013 0.062598013
Viscosity 1.0486 0.0797589622 0.076063
mm/sec Monte Carlo Simulations
The propagation of the distributions of the influencing
Table 2 Values and uncertainties for viscosity factors using Monte Carlo simulations has been evaluated
The most important contribution is due to temperature by using the Crystal Ball software [19].
variations. It is why the requirement on temperature
homogeneity is high. In a second range, we find the That approach has been recently approved by normalisation
diameter effect. The other geometric characteristics of the bodies. Using the mean and standard deviations given in
tube have a small contribution. The contribution of tables 1 and 2 together with the models (5) and (6), the
gravitation could be neglected. simulation is performed by the random extraction of 10 000
samples belonging to the corresponding input distributions
3. Global uncertainty: and directly propagating these numbers through the model
equations before computing the corresponding means and
In the basis of equation (3) and the uncertainty propagation standard deviations.
low, we get The Monte Carlo simulation approach is particularly
interesting in the case of complicated models and to evaluate
10 6 HgD 4 t
= the most influent factors. It is often more accurate and
128lV efficient than the first derivative approximation. Everybody
10 (40 * 10 3 )9.80630 (0.58 * 10 -3 ) 4 3.14 * 260
6
knows that is a substantial risk of mistake in computing
= analytical derivatives of complicated functions.
128(90 * 10 -3 )(3 * 10 -6 )
Furthermore, the first order Taylor expansion is only a local
= 1,0486 mm/sec approximation.
 Density uncertainty evaluation by Monte Carlo simulation
It is therefore strongly recommended to use a Monte Carlo
The three most influent factors in the variance approach in the case of complicated or non linear
decomposition are the measured oscillation period T (47%), measurement models.
the oscillation period of water Tw (31%) and the density of
water w (15%). Round robin tests approach
.024
Statistical Analysis of Industrial Round Robin
Tests in ISO 5725
.018
ISO 5725, Accuracy (trueness and precision) of
.012 measurement methods and results , allows to guarantee the
accuracy of a measurement method and therefore, is
.006 determinant in many areas: product exchanges, performance
estimation, quality
.000
In most of the cases, the official standards describing the
0.7354 0.7356 0.7358 0.7361 0.7363 measurement method include the repeatability and the
Figure 3. Probability distribution of the density resulting
reproducibility derived from an official Round Robin Test
from the Monte Carlo simulation using the input
(RRT).
distributions of table 1

The standard deviation issued of the propagation of the input
distributions trough the density model (5) is 0.00017758,
which is to be considered as the uncertainty u and compared
to 0.00021858 value given by the first derivative approach.
Viscosity uncertainty evaluation by Monte Carlo
simulation
The two most influent factors are the diameter of the
capillary D (98%) and the volume of the flow V (1%).
.01
6
.01
2
Schematically, a round robin test includes:
p laboratories which are representative of a normal
population of laboratories that are able to apply the
measurement method. This will ensure a good
practice of the measurement method from one
laboratory to another
q batches of material, representing q different
levels of the test, the study is then lead level by
level
n replicate test results obtained by each laboratory
at each level to ensure a good practice of the
measurement method within each laboratory
Within a laboratory, the tests are performed independently
of others and are not influenced by the results from other
laboratories. The laboratory measurement should be made in
the natural classical work environment without any
particular preparation or selected operator.
All tests are performed on samples coming from a same
population and by using the same procedure. This ensures
that all the results follow the same distribution, i.e. in this
case, a normal distribution.

.00
Figure 4. Probability distribution of the viscosity resulting The following notation will be used:
8from the Monte Carlo simulation using the input
distributions of table 2 nij is the number of test results for laboratory i at
level j. In most of the cases, we have nij = n = 2
yijk is any one of these test results (k=1, 2,, nij)
pj is the number of the laboratories reporting at
The standard deviation issued from the propagation of the least one test result for level j
.004
input distributions trough the viscosity model (6) is 0.0493, nij
1
which is to be considered as the uncertainty u and compared
to 0.0797 value given by the first derivative approach.
mij =
nij
y
k =1
ijk is the mean of the

These results tend to confirm that, for these two measures, measurement results of laboratory i at level j
the first derivative approximation tends to overestimate by
more than 20% the Monte Carlo estimation of the
.000
uncertainty.

0.928 0.985 1.050 1.114 1.171

 n is the round robin variance where
1 ij

sij =
nij 1 k =1
( yijk mij ) 2 is the standard
nij (mij m j )
1 p
s dj2 =
2
deviation of the measurement result of laboratory i p 1 i =1
at level j.
1 p p

A fundamental aspect of the measure is the result agreement
=
p 1 i =1
nij mij m j nij
2 2

with:
i =1

p


the true value or an accepted reference value
another result measured in the same laboratory nij2
1 p 1 p
another result measured in a different laboratory, m j = mij and n j = nij i =p1
p i =1 p 1 i =1
assuming that all the measures are done by applying the


i =1
nij

same measurement method, generally described in the norm.

ISO 5725 [1] uses two terms: trueness and precision s Rj2 = s rj2 + s Lj2 (9)
to describe the accuracy of a measurement method.
Trueness refers to the closeness of agreement between the
arithmetic mean of a large number of test results and the true is the reproducibility variance
or accepted reference value. Precision refers to the
closeness of agreement between the different test results.
r = ts rj 2 (10)

The fidelity and its two conditions, termed repeatability and

reproducibility conditions, are the subject of part 2 of this is the repeatability where t = T p 1;0.05 is the Student
standard.
associated statistics.

The repeatability, r, is the precision under

conditions where independent test results are
obtained with the same method on identical test
items in the same laboratory by the same operator
using the same equipment within short intervals of
time. These conditions define the repeatability
conditions.
The reproducibility, R, is the precision under
conditions where test results are obtained with the
same method on identical test items in different
laboratories with different operators using different
equipment. These conditions define the
reproducibility conditions.
Three variances are then calculated for each level: a
repeatability variance, a round robin variance and a
reproducibility variance in order to obtain r and R values.
R = ts Rj 2 (11)
is the reproducibility where t = T p 1;0.05 .
Uncertainty of the density using the RRT
The evolution of the repeatability and reproducibility of the
density derived from the last Round Robin Tests shows a
stabilization of the Reproducibility at 0.0005525.
Knowing that 50 laboratories were involved in these Round
Robin Tests and using the relationship (11), the
Reproducibility Standard Deviation can be evaluated as
0.0001942 and considered as the RRT estimation of
Uncertainty.

The evolution of the repeatability and reproducibility of the

(n 1)sij2
p
viscosity derived from the last Round Robin Tests shows a
ij
stabilization of the Reproducibility at 0.056.
s rj2 = i =1
(7)
(n 1)
p

ij
i =1

is the repeatability variance

s dj2 s rj2
s =
2
Lj (8)
nj
 Repeatibility (r) and Reproducibility (R) of density
As it can be seen, that reproducibility standard deviation can
0.0006
be considered as a reasonably good estimation of the
uncertainty.
0.0005

For the methods under accreditation, it is strongly

0.0004
recommended to perform regular Round Robin Tests and, if
it is the case, it is strongly recommended to exploit the
0.0003
reproducibility evaluations in order to derive an uncertainty.
0.0002

Conclusions
0.0001

0 1 2 3 4 5 6 7 8
r
R
Two of the most commonly used measures in the oil
RRT in increasing chronomogical number
industry have been selected: the density and the viscosity.

Figure 5. Evolution of the repeatability and

Reproducibility of the last density Round Robin Tests Measure uG uG_Monte Carlo uR uR_standard
Density 0.0002186 0.0001776 0.0001942 0.0001757
Uncertainty of the viscosity using the RRT
Viscosity 0.07975 0.049 0.019 0.014
Knowing that 30 laboratories were involved in these Round
Robin Tests and using the relationship (11), the
Reproducibility Standard Deviation can be evaluated as Table 3. Comparison of the uncertainties derived from the
0.019 and considered as the RRT estimation of uncertainty. GUM first derivative approximation, uG , the Gum Monte
Carlo, uG_Monte Carlo, the Round Robin Tests of the concerned
laboratories uR , and the official Round Robin Test used in
Repeatibility (r) and Reproducibility (R) of viscosity the Standard uR_standard
0.09

0.08
The uncertainties derived from the GUM first derivative
0.07 approximation have a tendency to overestimate by more
0.06 than 20 % the ones derived by Monte Carlo simulations.
0.05
The uncertainties derived from the exploitation of the field
0.04
Round Robin Tests give reasonable estimations when
0.03
compared to those directly derived from the standard Round
0.02 Robin Tests. They are slightly higher due to the fact that the
0.01 r
used products where true production samples coming
0 1 2 3 4 5
RRT in increasing chronological order
R
directly from the refineries.

Figure 6. Evolution of the repeatability and Reproducibility
of the last viscosity Round Robin Tests
Methodology of uncertainty evaluation
Before tackling the problem of uncertainty evaluation of the
measurement system, the first question to consider is the
existence of an officially published reference method by a
normalization body (ISO, CEN, ASTM, API, ).
Since most of the measurements related to the final quality
of our products are subject to the accreditation, they refer to
such an official standard in most of the cases.
These standards are the result of an international consensus
and they contain precise information on the influent factors
and the practical settings of the experiment. It is useless to
reconsider the work of the working groups responsible for
the development of these methods.
In most of the cases, these norms are finalized by an official
Round Robin Test giving the official reproducibility that can
be used to derive a reproducibility standard deviation.
In the case of the viscosity, it is quite difficult to
demonstrate that the GUM direct modeling approach was
able to evaluate realistic uncertainties while for the density
there are equivalent.
A considerable effort has been given for the evaluation of
the uncertainties by the classical GUM approach, starting by
the measurement model, evaluating the variance
contributions of the different factors and propagating the
errors.
The human resources needed to reach that very humble
status of uncertainty evaluation have been precisely
evaluated to more than two month - man per method. This
means roughly 10 000 per method. Knowing that more
than hundred methods are currently practiced in oil industry
laboratories, the cost of evaluating such a number of
methods is about 1 000 000 .
When available, the exploitation of the Round Robin Tests
is, for the oil industry laboratories, the most credible way to
derive and follow the uncertainties of the measurements.
They allow also the dynamical control of the performance of
all the laboratories involved in the quality control of the
products.

Acknowledgments
The authors are grateful to Professor Nieto de Castro
(Department of Chemistry and Biochemistry, University of
Lisbon), M. Dsenfant (Quality management, National
testing laboratory, LNE, Paris) for their helpful comments
and suggestions. We thank M. Reminiac and P. Bonnet
(Analysis Department of TOTAL-FRANCE Research
Center of Gonfreville) for providing information about the
measurements and instruments.
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