EURAMET Cg-19 V 2.0 Guidelines in Uncertainty Volume 01

Guidelines on the determination
of uncertainty in gravimetric
volume calibration
EURAMET cg-19
Version 2.0 (03/2011)

European Association of National Metrology Institutes

Cal i br at i on Gui de
EURAMET cg-19
Ver si on 2.0 ( 03/ 2011)

Gui del i nes on t he det ermi nat i on of
uncert ai nt y i n gravi met ri c vol ume
cal i brat i on

Pur pose
This document has been produced t o enhance t he equivalence and mut ual recognit ion of calibrat ion
result s obt ained by laborat ories performing calibrat ions of gravimet ric volume.

Aut hor shi p and I mpr i nt
This document was developed by t he EURAMET e.V., Technical Commit t ee for Flow.

2nd version March 2011
1st version Sept ember 2009

EURAMET e.V.
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I SBN 978-3-942992-16-9
Gui dance Publ i cat i ons
This document gives guidance on measurement pract ices in t he specified fields of measurement s. By
applying t he recommendat ions present ed in t his document laborat ories can produce calibrat ion result s
t hat can be recognized and accept ed t hroughout Europe. The approaches t aken are not mandat ory and
are for t he guidance of calibrat ion laborat ories. The document has been produced as a means of
promot ing a consist ent approach t o good measurement pract ice leading t o and support ing laborat ory
accredit at ion.
The guide may be used by t hird part ies e.g. Nat ional Accredit at ion Bodies, peer reviewers wit nesses t o
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EURAMET cg- 19
Ver si on 2.0 ( 03/ 2011)

GUI DELI NES ON THE DETERMI NATI ON
OF UNCERTAI NTY I N GRAVI METRI C
VOLUME CALI BRATI ON

Cont ent s

1. I nt roduct ion ................................................................................................................................... 1
2. Gravimet ric met hod ........................................................................................................................ 1
3. Paramet ers t hat affect t he uncert aint y in gravimet ric det erminat ion of volume ................................... 3
3.1 Weighing ........................................................................................................................... 3
3.2 Wat er densit y..................................................................................................................... 3
3.3 Wat er t emperat ure ............................................................................................................. 3
3.4 Ambient condit ions ............................................................................................................. 3
3.5 I nst rument charact erist ics ................................................................................................... 3
3.6 Operat or ............................................................................................................................ 4
4. General procedure for t he uncert aint y calculat ion ............................................................................. 4
5. Procedure f or calculat ing uncert aint y in gravimet ric det erminat ion of volume ..................................... 4
5.1 Mat hemat ical expression of t he volume V
0
........................................................................... 4
5.2 Sources of uncert aint y in volume det erminat ion ................................................................... 5
5.3 St andard uncert aint y of each input quant it y ......................................................................... 5
5.4 Sensit ivit y coef ficient of each input quant it y ......................................................................... 9
5.5 Combined st andard uncert aint y of measurand .................................................................... 10
5.6 Evaluat ion of any exist ing covariances ............................................................................... 11
5.7 Choice of an appropriat e k-fact or ...................................................................................... 11
5.8 Expanded uncert aint y ....................................................................................................... 11
6. Pract ical applicat ion ...................................................................................................................... 11
7. References ................................................................................................................................... 16

EURAMET cg-19, Version 2.0 ( 03/ 2011) Page 1

EURAMET cg- 19
Ver si on 2.0 ( 03/ 2011)

Gui del i nes on t he det er mi nat i on of
uncer t ai nt y i n gr avi met r i c vol ume
cal i br at i on

1. I nt r oduct i on
Volume measurement is an import ant st ep in most indust rial and analyt ical measurement operat ions.
Volume inst rument s are used in many fields like chemist ry, healt h, biology and pharmacy. Laborat ories
must ensure t hat result s obt ained using t hese inst rument s are reliable. I n order t o reduce and ident ify
possible errors in liquid handling, it is necessary t o calibrat e t he volume inst rument s using t he correct
met hods. I t is also necessary t o evaluat e t he measurement uncert aint ies as t his must be displayed wit h
t he final result of t he measurement t o give t he end use confidence in t he measurement .
Volume inst rument s can be calibrat ed by filling, or empt ying, t he volumet ric inst rument using a reference
volume measurement , i.e. by comparing t wo volumes. This is a secondary met hod. At t he highest level of
t he t raceabilit y chain, t he volume can be det ermined by t he primary met hod of weighing t he cont ent s of
a suit able liquid of known t emperat ure and densit y (gravimet ric met hod). I n t his guide, t he evaluat ion of
measurement uncert aint y is out lined for t he lat t er met hod, following t he int ernat ional recommendat ions
[ 1] .
I t should be not ed t hat only Type A uncert aint y component s can be comput ed on t he basis of st at ist ical
calculat ions, such as t he det erminat ion of an experiment al st andard deviat ion, or t he det erminat ion of
t he expect ed drift of a measurement inst rument based on several previous calibrat ions. All ot her
component s (t he many Type B component s) must be evaluat ed on t he basis of all available sources of
informat ion, and t hrough t he operat ors knowledge and expert ise. The crit eria and formulae suggest ed in
t his Guide are not int ended t o, nor can t hey replace t he personal j udgment and responsible evaluat ion
individually made by t he met rologist in any part icular applicat ion and laborat ory.
2. Gr avi met r i c met hod
The gravimet ric met hod is t he st andard met hod used bot h by Nat ional Met rology I nst it ut es (NMI s) and
by accredit ed laborat ories t o calibrat e volume inst rument s. The met hod consist s on weighing t he
inst rument under calibrat ion when empt y and again when full. The procedures adopt ed t he use of t he
reference lines or marks t o have t he purpose t o provide an exact measure of liquid volume and t he
draining or drying procedures should be followed caref ully because t hey all affect t he measurement . The
difference obt ained in t he weighing measurement s gives t he mass of cont ained or delivered liquid. The
liquid used is generally pure wat er (dist illed, bi-dist illed, or deionized) wit h a conduct ivit y lower t han
5 S/ cm [2] and chosen t o suit the level of accuracy required relative to t he amount of water used. A
conversion is t hen performed from mass t o volume at a reference t emperat ure of t
0
( normally 20 C).
The recommended equat ion is described in I SO 4787 st andard [ 3] and given below (1)
| | ) t t (

) I I ( V
0
B
A
A W
E I 0
1 1
1
|
.
|
\
|

= (1)


Where:
V
0
volume, at t he reference t emperat ure t
0
, in mL

weighing result (or result of t he subst it ut ion, double subst it ut ion or ot her met hod of weighing) of
t he recipient full of liquid, in g
E
weighing result (or result of t he subst it ut ion, double subst it ut ion or ot her met hod of weighing) of
t he empt y recipient , in g
W
liquid densit y, in g/ mL, at t he calibrat ion t emperat ure t , in C, according t o equat ion (2)
A
air densit y, in g/ mL, according t o equat ion (3)
B
densit y of masses used during measurement (subst it ut ion) or during calibrat ion of t he balance,
assumed t o be 8,0 g/ mL
cubic t hermal expansion coefficient of t he mat erial of t he inst rument under calibrat ion, in C
-1
(Not e t he cubical expansion coefficient is normally assumed t o be 3 t imes t he linear expansion
coef ficient for t he given mat erial.)
t liquid t emperat ure used in t he calibrat ion, in C
t
0
reference t emperat ure, in C

Not e: it can be shown t hat t he air densit y t o be considered is (in principle) t he densit y of t he air inside
t he volumet ric inst rument (see 5.3.4) and displaced when t he inst rument is filled wit h liquid. I t is
generally assumed t hat t he ambient air densit y (t he densit y of air surrounding t he inst rument ) does not
change signif icant ly bet ween and during bot h weighings. This ensures t he buoyancy ef fect exert ed on
t he volumet ric inst rument is const ant . I f t he ambient air densit y changes, t he (t rue) mass of t he
inst rument must be det ermined for each weighing as a condit ion f or an accurat e measurement of t he
mass of t he cont ained liquid.

The densit y of pure wat er is normally provided from formulat ions given in t he lit erat ure. Bat ist a and
Pat on [ 4] provide an overview of common formulat ions used in pract ice. I s however generally accept ed
t hat t he formulat ion given by Tanaka [ 5] provides a good basis f or st andardizat ion:
g/mL 1
4 3
2
2
1
5 (
+
+ +
=
) a t ( a
) a t ( ) a t (
a
Tanaka
(2)
Where:
t = wat er t emperat ure, in C
a
1
= -0,003983035 C
a
2
= 0,301797 C
a
3
= 522,5289 ( C)
2

a
4
= 0,06934881 C
a
5
= 0,999974950 g/ mL

Not e: a
5
is t he densit y of SMOW wat er under one at mosphere at t his t emperat ure. Many users of wat er
rely on t ap wat er inst ead of SMOW. Thus a
5
must be changed accordingly t o reflect t he densit y of t he
wat er used.

The full equat ion of st at e f or wat er provided by t he I nt ernat ional Associat ion for Propert ies of t he Wat er
Subst ance (I APWS) can also be used t o det ermine t he densit y of t he used wat er and a formulat ion based
on t his equat ion is given in ref. [ 4] . This provides an alt ernat ive t o Tanaka and should be used if
t emperat ures above 30 C are used.

Where pure wat er is not available, t he relat ive densit y of t he wat er may be det ermined and t he chosen
formulat ion used t o det ermine t he t emperat ure expansion fact ors wit h insignificant loss of accuracy.
The air densit y can be det ermined according t o t he formula for t he densit y of moist air - CI PM-2007 [ 6] :


( ) | | ( )
V co a
x
ZT
p
x m kg + =

3780 , 0 1 0004 , 0 4446 , 1 483740 , 3 ) 10 /(
2
3 3
(3)
p ambient pressure, in Pa
T t hermodynamic t emperat ure = 273,15 + t / C, in K
x
v
mole fract ion of wat er vapour
x
CO2
mole fract ion of carbon dioxide in laborat ory air
Z compressibilit y fact or

I f t he laborat ory ambient condit ions are wit hin t he limit s given t hen Spiewecks [ 7] equat ion ( 4) can be
used. The limit s are: pressure bet ween 940 hPa and 1080 hPa; t emperat ure bet ween 18 C and 30 C;
humidit y less t han 80 %,
( )
g/mL
15 273
a
3 a 2 r a 1
, t
k t k h p k
a
+
+ +
= (4)
Where :
t
a
ambient t emperat ure, in C
p
a
ambient pressure, in hPa
h
r
relat ive air humidit y, in %
k
1
= 3,4844 x 10
- 4
C/ hPa
k
2
= -2,52 x 10
-6
g/ mL
k
3
= 2,0582 x 10
-5
C
3. Par amet er s t hat af f ect t he uncer t ai nt y i n gr av i met r i c
det er mi nat i on of v ol ume
During t he gravimet ric calibrat ion of volume inst rument s, t he main paramet ers t hat can influence t he
qualit y of t he result are described.
3.1. Wei ghi ng
Weighing is t he most import ant st ep in gravimet ric calibrat ion. The weighing result s are influenced by
several fact ors such as t he resolut ion and sensit ivit y of t he balance, t he calibrat ion of t he balance
(eccent ricit y, linearit y, and repeat abilit y), t he class and densit y of t he weight s used t o calibrat e a
elect ronic scale or wit h a balance.
3.2. Wat er densi t y
Mass is convert ed int o volume by det ermining t he value of t he calibrat ion liquid densit y. This value can
be obt ained from t he lit erat ure [ 4] or from direct measurement s if pure wat er is not available.
3.3. Wat er t emper at ur e
The wat er t emperat ure influences t he det erminat ion of t he wat er densit y; t hus it should be caref ully
measured in each measurement . Met hods f or est imat ing t he t emperat ure of t he wat er wit hout changing
t he volume have t o be est ablished.
3.4. Ambi ent condi t i ons
The ambient condit ions mainly influence gravimet ric measurement during t he air densit y det erminat ion.
3.5. I nst r ument char act er i st i cs
The charact erist ics of t he inst rument (t ank, volume measure, pipet t e, et c) under calibrat ion, e.g. t he
scale or t he expansion coef ficient of t he mat erial, must also be considered.


3.6. Oper at or
The operat or can direct ly influence t he measurement in t he meniscus reading, in t he filling and empt ying
procedure or in t he handling of t he equipment .
4. Gener al pr ocedur e f or t he uncer t ai nt y cal cul at i on
I n t his document , t he evaluat ion of measurement uncert aint y f ollows t he met hods described in t he Guide
t o t he Expression of Uncert aint y in Measurement (GUM) [ 1] . The met hod consist s of t he following st eps.
1. Expressing, in mat hemat ical t erms, t he relat ionship bet ween t he measurand and it s input quant it ies.
2. Det ermining t he expect at ion value of each input quant it y.
3. Det ermining t he st andard uncert aint y of each input quant it y.
4. Det ermining t he degree of freedom for each input quant it y.
5. Det ermining all covariance bet ween t he input quant it ies.
6. Calculat ing t he expect at ion value for t he measurand.
7. Calculat ing t he sensit ivit y coefficient of each input quant it y.
8. Calculat ing t he combined st andard uncert aint y of t he measurand.
9. Calculat ing t he ef fect ive degrees of freedom of t he combined st andard uncert aint y.
10. Choosing an appropriat e coverage fact or, k, t o achieve t he required confidence level.
11. Calculat ing t he expanded uncert aint y.
I t should be not ed t hat for st eps 6 t o 11 well suit ed comput er programs exist which can avoid t he error-
prone manual calculat ion. St ep 1 is t he most import ant part in t he whole GUM procedure.
5. Pr ocedur e f or cal cul at i ng uncer t ai nt y i n gr av i met r i c
det er mi nat i on of v ol ume
5.1 Mat hemat i cal expr essi on of t he vol ume V
0

( ) ( )
( )
| |
rep evap
V V V ) t t (
h , p , t
h , p , t t
m
V + + + |
.
|
\
|

=
men 0
B
r A A A
r A A A W W
0
1 1 (5)
wit h
m I I m + = ) (
E I

W W0 W
t t t + =
A A0 A
t t t + =
t t t + =
W

( ) ( )
form W, W form W, W W
+ = t t
( ) ( )
form A, r A A form A, r A A A
, , , , + = h p t h p t


where
m mass of filling at act ual condit ions
m component arising because of influences not covered by u(I
I
) and u(I
E
)
t
W0
measured wat er t emperat ure
t
W
deviat ion arising from wat er t emperat ure inhomogeneit y
t
A0
measured air t emperat ure
t
A
deviat ion arising from air t emperat ure inhomogeneit y
t difference bet ween wat er and vessel t emperat ure
W, form
used wat er densit y formula (e.g. Tanakas equat ion)
A,form
used air densit y formula (e.g. Spieweks equat ion)
W,form
est imat ed deviat ion from formula condit ions ( for wat er densit y)
A,form
est imat ed deviat ion from formula condit ions ( for air densit y)
V
men
auxiliary quant it y t o t reat t he meniscus reading
V
evap
auxiliary quant it y t o t reat t he evaporat ion
V
rep
auxiliary quant it y t o t reat t he repeat abilit y
Not e: all x have usually expect at ion value 0! They are auxiliary quant it ies t o t reat uncert aint ies and
degrees of freedom.
5.2. Sour ces of uncer t ai nt y i n vol ume det er mi nat i on
Once ident ified t he input quant it ies of t he measurand, i.e. t he volume V, in equat ion ( 1), it is possible t o
ident ify t he sources of uncert aint y coming from t he diff erent input quant it ies, which are:
Mass
Wat er t emperat ure
Wat er densit y
Air densit y
Mass pieces densit y
Cubic t hermal expansion coefficient of t he mat erial of t he inst rument under calibrat ion
Meniscus reading
Evaporat ion
Measurement repeat abilit y
Not e: t he gravimet ric primary calibrat ion of volume st andards is normally performed by means of
repeat ed, independent measurement s: in t his connect ion, it should be not ed t hat t he measurand (volume
of t he cont ained liquid) is not generally t he same f or repeat ed measurement s, mainly owing t o t he
variabilit y of t he quant it y of wat er wet t ing t he empt y vessel (if it is not t o be weighed in t he dry st at e)
and t he variabilit y of meniscus shape and posit ioning. I n ot her words, t he measurand is not perfect ly
reproducible f or all measurement s and it s own variabilit y frequent ly exceeds t he uncert aint y of each
single volume det erminat ion.
5.3. St andar d uncer t ai nt y of each i nput quant i t y
I n t he f ollowing, t he different expressions of t hese uncert aint ies are displayed.
5.3.1. Mass
Equat ion (6) is a possible expression for t his uncert aint y component :
( ) ( ) ( ) ( ) ( ) ( ) ( ) | |
2
1
2
E I E I E
2
I
2
, 2 m u I u I u I I r I u I u m u + + = (6)


Not e 1: Measurement uncert aint y of I
I
and I
L
should include: mass st andards used, balance resolut ion
eccent ricit y, repeat abilit y and linearit y.

Not e 2: Some correlat ions are present bet ween t he t wo readings of t he balance (alt hough t hey are
obt ained at different loads) as balance performance and ambient condit ions do not change in a short
t ime int erval; moreover, a single set of mass st andards is normally used as a reference. However, t he
weak covariance, expressed by a low value of t he correlat ion coefficient r, may be negligible when
compared wit h t he ot her uncert aint y component s.
5.3.2. Wat er t emper at ur e
Equat ion (7) is a possible expression for t his uncert aint y component :
( ) ( )
2
1
2 2
2
) (
) (
(
(
+ + |
.
|
\
|
= t u t u
k
ther u
t u
(7)
Where:
u(ther) - measurement s uncert aint y of t he t hermomet er, in C or K;

I n general, if t he calibrat ion cert ificat e of t he t hermomet er is based upon a normal dist ribut ion of
measurement s wit h a high number of degrees of freedom t he covering fact or will be k= 2.

t - est imat e of t he uncert aint y caused by possible drif t and ageing of t he t emperat ure measuring syst em
aft er it s calibrat ion.

t - est imat e of t he uncert aint y of t he average wat er t emperat ure caused by t emperat ure differences
(and t emperat ure gradient s) t hat can be measured or est imat ed bet ween bot t om and t op of t he
inst rument under calibrat ion.

Not e: t he maximum t emperat ure difference bet ween various part s of t he vessel can be reduced t o
negligible values (10 t o 20 mK) if t he wat er is effect ively st irred wit h a rod soon aft er weighing ( care has
t o be t aken t o ensure t he rod is at t he same t emperat ure as t he wat er before use t o avoid heat t ransfer).
I f t his is not possible, t emperat ure can be measured in different , represent at ive locat ions; having defined
t
max
and t
min
as t he highest and lowest t emperat ures found, t he st andard deviat ion of a rect angular
dist ribut ion, namely ( ) 12 /
min max
t t , is an upper limit for t he uncert aint y of t he mean t emperat ure.
5.3.3. Wat er densi t y
The uncert aint y of t he wat er densit y should be evaluat ed according t o t he used formula and t ype of
wat er (impurit ies, air cont ent , et c).
For t he formulat ion provided by Tanaka [ 5] has an est imat ed expanded uncert aint y of 9 10
- 7
g/ mL. This
however is t he uncert aint y of t he formulat ion and t he uncert aint y of t he purit y and t emperat ure of t he
wat er used must be added.

I f t he informat ion about t he wat er preparat ion is insuf ficient or assuming t here is a possible wat er
cont aminat ion, possibly occurring bot h at t he beginning (residual cont aminat ion of t he volumet ric
inst rument ) and at t he end of calibrat ion (newly int roduced impurit ies), a correct ion wit h an associat ed
uncert aint y can be made, if t he densit y of t he working wat er is measured, or compared t o t hat of a
freshly prepared sample of pure wat er, t ypically by means of a high resolut ion ( 1 ppm) densit y met er. I f
no such measurement is carried out , an appropriat e uncert aint y cont ribut ion should be evaluat ed. This
might range from a few ppm for highly pure wat er of known and cont rolled isot opic composit ion used for
glassware calibrat ion, t o 20 ppm for lower qualit y dist illed or de-ionised wat er from a reput able source
used in proving t hanks.


5.3.4. Ai r densi t y
The uncert aint y of t he air densit y should be evaluat ed according t o t he chosen formula [ 6,7] and t he
input uncert aint ies.

For t he CI PM air densit y formula (3), t he relat ive st andard uncert aint y is 22 10
-6
.
I f Spiewecks formula (4) is used, t he air densit y uncert aint y may be expressed according t o equat ion
(8):
( )
3
10 5
7
=
A
u g/ mL

(8)
Not e: t he air t hat is act ually displaced by wat er is t hat inside t he volumet ric inst rument . I n case of dry
volume det erminat ions it s densit y is equal t o t hat of ambient air, t herefore it is correct t o measure
pressure, t emperat ure and relat ive humidit y j ust nearby. Also in case of int ernally wet volumet ric
inst rument s, t he present pract ice is t o measure t he t hree paramet ers in ambient air. At 20 C t he
maximum dif ference in densit y bet ween dry and fully sat urat ed air is + 0,9 %. However, t he effect of
humidit y above 90 % inside t he volumet ric inst rument is part ially compensat ed by a generally lower
t emperat ure, caused by evaporat ion. The ef fect s on air densit y of such int ernal t emperat ure and
humidit y may deserve more at t ent ion, now t hat volume st andards wit h reproducibilit y in t he order of
0,001 % are available. I n any case, it appears point less t o use accurat e hygromet ers and t hermomet ers
if humidit y and t emperat ure are not measured in t he appropriat e spot .
5.3.5. Densi t y of mass pi eces
The value present ed in t he calibrat ion cert ificat e of t he set of masses, or of t he analyt ical balance can be
used. Alt ernat ively t he uncert aint ies corresponding t o t he used weight class according t o OI ML R 111-1
[ 8] can be used.
5.3.6. Cubi c t her mal expansi on coef f i ci ent of t he mat er i al of t he cal i br at ed i nst r ument
The t hermal expansion coefficient s are dependent on knowledge of t he act ual mat erial of t he vessel and
on t he source of dat a which provides t he user wit h an appropriat e value. Dat a from t he lit erat ure or
manufact urer should be used and t his would be expect ed t o have an (st andard) uncert aint y of bet ween
5 % and up t o 10 %.
5.3.7. Meni scus r eadi ng
The variabilit y of meniscus set t ings and scale readings made by a single operat or depends upon his/ her
individual expert ise. This reading influences direct ly t he experiment al st andard deviat ion; t heref ore only
Type B component s of meniscus and scale reading uncert aint y should be est imat ed and composed.
These component s are int ended t o t ake int o account t he unavoidable bias (or average deviat ions of t he
posit ioning of meniscus t hat is charact erist ic of a given operat or in a given art ifact ) wit h reference t o t he
ideal posit ion defined by ref. [ 3] ( t he meniscus shall be set so t hat t he plane of t he upper edge of t he
graduat ion line is horizont ally t angent ial t o t he lowest point of t he meniscus, t he line of sight being in t he
same plane ). I t is recommended t hat t he est imat e of t his cont ribut ion t o uncert aint y be separat ely
declared in calibrat ion cert ificat es, in order t o allow users (who are responsible for evaluat ing act ual
uncert aint ies occurring during t he use of t here own inst rument ) t o est imat e and compose a
supplement ary cont ribut ion if t hey t hink not t o be able t o approximat e, t he proper meniscus posit ioning
wit hin t he same uncert aint y limit s.

Several approaches can be used t o det ermine t he uncert aint y of t he meniscus.


5.3.7.1. Uncer t ai nt y i n r eadi ng t he posi t i on of a concave meni scus wi t h r espect t o a
gr aduat ed scal e of a vol umet r i c appar at us
I n t his case t he uncert aint y due t o t he meniscus could be est imat ed as t he uncert aint y in t he volume
det erminat ion due t o t he resolut ion (2) of t he scale of t he volumet ric apparat us. The usual pract ice is t o
assume a rect angular dist ribut ion and est imat e t he st andard uncert aint y as 3 / . However, t his
approach could underest imat e t he act ual t echnical skills of t he operat or. Usually, t he meniscus posit ion is
det ermined using opt ical aids and f or t his reason it is highly probable t o t ake t he reading closer t o t he
right posit ion of t he meniscus t angent ially t o t he corresponding scale mark t han away from it . Therefore,
it is recommended and more realist ic t o consider as an upper uncert aint y limit t he one which is est imat ed
assuming a t riangular dist ribut ion inst ead, as shown in Fig. 1.

+ = 6,8 mL

- = 6,6 mL

= ( + - -) = 0,1 mL

Depending on t he assumed
dist ribut ion of t he meniscus reading
bet ween posit ions + and -, t he
uncert aint y will be:

u(
er
) = u(V
men
) =
3
= 0,058 mL
(rect angular)

u(
er
) = u(V
men
) =
6
= 0,041 mL
(t riangular)

Fi g 1. Concave meniscus in a graduat ed volumet ric
device
5.3.7.2. Uncer t ai nt y i n r eadi ng t he posi t i on of a concave meni scus i n a one- mar k vol umet r i c
appar at us
I n t his case t he uncert aint y in t he volume due t o t he reading of t he posit ion of t he meniscus could be
evaluat ed as t he product of t wo geomet ric fact ors:
The uncert aint y in t he posit ioning and det erminat ion of t he meniscus lowest point , u
P.

The area E of t he cross sect ion of t he volumet ric inst rument where t he air-wat er meniscus is locat ed,
which can be a cylindrical neck or a sect ion of a different shape. Theref ore, t he uncert aint y due t o
meniscus reading is approximat ed as:
( )
3
E u
V u
p
men
= (9)
As t he qualit y of t he engraving is one of t he most import ant fact ors, a possible crit erion f or det ermining
t he uncert aint y in set t ing and reading correct ly t he posit ion of t he lowest point of t he meniscus surface is
t o assume t hat uncert aint y not larger t han one half of t he widt h of t he scale mark ( u
p
= 0,5 d). However,
a skilled operat or can reduce his own uncert aint y t o a fract ion of t he widt h of t he mark; t he use of a
simple magnif ying glass in a good art ifact may allow a st andard uncert aint y as low as 0,05 mm t o be
achieved.


5.3.7.3. Uncer t ai nt y due t o t he f or mat i on of a convex meni scus
This t ype of meniscus is present in t he case of overflow pipet t es. The uncert aint y due t o meniscus
format ion is ent irely at t ribut ed t o t he repeat abilit y in t he lengt h of t he short radius of t he meniscus, since
t he area of it s base is const ant and equal t o t he cross sect ion of t he overf low pipe of t he pipet t e.
5.3.8. Evapor at i on
Weighing of t he filled inst rument should be carried out as soon as possible aft er having set t he meniscus
in order t o reduce errors due t o any evaporat ion. When a procedure is adopt ed which requires t he wat er
cont ained in t he inst rument under calibrat ion t o be t ransferred int o an auxiliary vessel inst alled on t he
balance, a correct ion caused by increased evaporat ion (or even minut e loss t hrough spray or droplet
format ion) from t he wat er j et and bubbles produced in t he receiving t ank should be evaluat ed, together
with its own contribution to uncertainty.
5.3.9. Measur ement r epeat abi l i t y
Equat ion (10) is a possible expression for t his Type A uncert aint y component :
( )
( )
n
V s
V u
o
rep
= (10)

Where:
s(V
0
) st andard deviat ion of a series of independent volume measurement s, in mL.
n number of measurement s

Not e: t he value of volume t hat will be given as a result of n repeat ed measurement s is t he arit hmet ic
mean of t he n result s, t herefore it s only Type A uncert aint y component is t he st andard deviat ion of t he
mean, ( )
rep
V u as defined above. However, it is recommended t hat t he number of measurement s n
and t heir st andard deviat ion s(V
0
) be quot ed in calibrat ion report s or cert ificat es, because if t he user is
going t o make single, not averaged measurement s, his Type A uncert aint y cont ribut ion will not be
( )
rep
V u , but t he st andard deviat ion of t he whole populat ion of possible measurement s, whose best
est imat e can be det ermined knowing n and s(V
0
).
5.4. Sensi t i vi t y coef f i ci ent of each i nput quant i t y
Defining t he t erms A, B and C by:
A w

A
=
1
; |
.
|
\
|
=
B
A
B 1 ; ( )
0
1 t t C = and wit h m = I
L
- I
E
, equat ion (1) can be rewrit t en as:
rep evap men
V V V C B A m V + + + =
0
(11)
The procedure saves some comput at ional eff ort in developing t he sensit ivit y coefficient s, necessary for
t he comput at ion of t he combined st andard uncert aint y of V
0
.
For each input quant it y, we now display t he result s of t he calculat ion of t he sensit ivit y coefficient based
on t he new formulat ion of equat ion (1) as equat ion (11).
5.4.1. Mass
C B A
m
V
=
|
.
|
\
|
0
(12)


( ) B A m
t
V
=
|
.
|
\
|
0
(13)
( )
2
0
1
A W
W

C B m
= |
.
|
\
|
= - m A
2
B C (14)
(
|
.
|
\
|

= |
.
|
\
|
B B
A
A w A

A C m
V 1
1
1
0
= m A C (B A 1/
B
) (15)
5.4.5. Mass pi eces densi t y
2
0
B
A
B

C A m
V
= |
.
|
\
|
(16)
)) t t ( ( B A m
V
0
0
= |
.
|
\
|
(17)
1
0
=
men
V
V
(18)
1
0
=
evap
V
V
(19)
1
0
=
rep
V
V
(20)
5.5. Combi ned st andar d uncer t ai nt y of measur and
Wit hin t he hypot hesis of t he applicabilit y of t he propagat ion law of uncert aint ies, t he combined st andard
uncert aint y of t he measurand is expressed as:
( ) ( )
2
0
0
2
|
.
|
\
|

=
i
i
i
x u
x
V
V u (21)


Using t he expressions of t he part s 5.3. and 5.4., t he result ant combined st andard uncert aint y of t he
measurand is:
( ) ( ) ( ) ( ) ( ) ( )|
2
1
2 2 2 2
2
0 2
2
0 2
2
0 2
2
0 2 0 2
2
0
0
) ( ) ( ) ( ) (
rep evap men B
B
A
A
w
w
V u V u V u u
V
u
V
u
V
u
V
t u
t
V
m u
m
V
V u
+ + +
|
|
.
|
\
|
+
|
|
.
|
\
|
+
|
|
.
|
\
|
|
|
.
|
\
|
+ |
.
|
\
|
+ |
.
|
\
|
=
(22)
5.6. Eval uat i on of any exi st i ng covar i ances
Equat ion (21) and Equat ion (22) do not include any covariances t erms. I f some ot her correlat ions are
ident ified t hey must be evaluat ed and int roduced if influent ial.
5.7. Choi ce of an appr opr i at e cover age f act or ( k)
Having comput ed t he st andard uncert aint y of t he measurand t hrough t he composit ion of all
cont ribut ions, assuming t hat t he dist ribut ion of t he st andard uncert aint y is normal, it s number of degrees
of freedom
eff
, can be est imat ed by means of t he Welch-Sat t ert hwait e formula:

=
=
N
i i
i
V
eff
u
u
1
4
4
(23)

u
V
combined uncert aint y of t he det ermined volume
u
i
st andard uncert aint y of each component
i
degrees of freedom

which allows to calculate an appropriate coverage factor (k) for a 95% confidence level (see GUM Annex
G).
5.8 Expanded uncer t ai nt y
Wit h t he value of t he coverage fact or k and of t he combined st andard uncert aint y of t he measurand, t he
expanded uncert aint y is deduced by:
U = k u(V
0
) (24)
6. Numer i cal ex ampl e
6.1 Measur ement pr obl em
I n order t o apply numerical values t o t he uncert aint y calculat ion procedure described above, a 1000 mL
flask was calibrat ed. The dat a is summarized in t able 1.


Table 1 Summary of dat a for gravimet ric calibrat ion of a 1000 mL flask
(average values)
I nput Quant it y
x
i

Value of t he input
quant it y
Mass 996,9499 g
Wat er t emperat ure 20,5 C
Wat er densit y 0,9981 g/mL
Air densit y 0,0012 g/mL
Densit y of t he mass pieces 7,96 g/mL
Coefficient of expansion from t he
flask mat erial
110
-5
/C
Meniscus reading 0,036 mL
Measurement repeat abilit y 0,011 mL

Aft er analyzing t he measurement problem (6.1) and det ermining t he volume of t he flask according t o t he
correct mat hemat ical model (equat ion 1), V
20
= 999,880 mL, is necessary t o det ermine t he st andard
uncert aint y of each input quant it y, t he sensit ivit y coef ficient s, t he combined uncert aint y, t he degrees of
freedom and corresponding k fact or and finally t he expanded uncert aint y. The pert inent aspect s of t his
example as discussed in t his and t he f ollowings subclauses are summarized in t able 2.
6.2. Det er mi nat i on of t he st andar d uncer t ai nt y of each i nput quant i t y
6.2.1. Mass
The st andard uncert aint y of t he mass (for bot h I
L
and I
E
) was obt ained from t he value of t he calibrat ion
of t he weighing scale U(bal)= 0,007 g, using a coverage fact or of 2 and from t he resolut ion of t he
weighing scale u(res) = 0,0005 g, using a rect angular dist ribut ion, t hen:
( ) ( ) | | 00351 , 0
3
2
001 , 0
2
007 , 0
) ( ) (
2
1
2
2
2
1
2 2
=
(
(
(
|
|
|
.
|
\
|
+ |
.
|
\
|
= + = = res u bal u I u I u
E I
g

I f we consider t hat t he correlat ions can be neglect ed and t hat m = 0, equat ion 6 can be rewrit t en as:
( ) ( ) ( ) | | | | 0048 , 0 00351 , 0 00351 , 0
2
1
2 2
2
1
E
2
I
2
= + = + = I u I u m u g
The st andard uncert aint y of t he wat er t emperat ure was obt ained from t he value of t he t hermomet er
calibrat ion U(ther)= 0,01 C, using a coverage fact or of 2. I f we consider t = 0 and t = 0, equat ion 7
can be rewrit t en as:
005 , 0
2
01 , 0 ) (
) (
2
1
2
= =
(
(
|
.
|
\
|
=
k
ther u
t u
C


The st andard uncert aint y of t he wat er t emperat ure was obt ained from t he value provided by Tanaka =
9 10
-7
g/ mL, at which a coverage fact or of 2 must be used and also from t he uncert aint y of t he
t hermomet er, wit h a value of 1,22 10
-6
g/ mL, t hen:
( )
6
2
1
2
6
2
7
10 52 , 1 10 22 , 1
2
10 9
) (

=
(
(
+
|
|
.
|
\
|
=
W
u
g/mL
The st andard uncert aint y of t he wat er t emperat ure was obt ained from t he value provided by Spiewecks:
( )
7
7
10 89 , 2
3
10 5

=
A
u
g/mL

6.2.5. Densi t y of mass pi eces
The value present ed in t he calibrat ion cert ificat e of t he set of masses was used, 0,06 g/ mL, at which a
coverage fact or of 2 is associat ed:
( ) 03 , 0
2
06 , 0
= =
B
u
g/ mL
The t hermal expansion coefficient of t he flask is given by t he manufact urer as = 1 10
-5
/ C, wit h an
expanded uncert aint y of 5 %; in t he lack of a more informat ive st at ement , a rect angular probabilit y
dist ribut ion is assumed. The relevant st andard uncert aint y is t herefore:
( )
7
7
10 89 , 2
3
10 5

= u
/C
The meniscus posit ion was det ermined using opt ical aids and for t his reason t he st andard uncert aint y is
0,036 mL, wit h a rect angular dist ribut ion:
( ) 021 , 0
3
036 , 0
= = men u
mL
Weighing of t he flask was carried out as soon as possible aft er having set t he meniscus, t heref ore t he
errors and uncert aint y due t o any evaporat ion are negligible.
Following equat ion ( 10), t he t ype A uncert aint y component can be det ermined by:
( )
( )
011 , 0
10
034 , 0
= = =
n
V s
V u
o
rep
mL


6.3. Sensi t i vi t y coef f i ci ent of each i nput quant i t y
For each input quant it y, t he result s of t he calculat ion of t he sensit ivit y coef ficient are display below, t aken
in t o account equat ion 11.
6.3.1. Mass
1
0
= = |
.
|
\
|
C B A
m
V
mL/g
( )
2 0
10 1

= = |
.
|
\
|
B A m
t
V
mL/C
( )
2
0
1
A W
W

C B m
= |
.
|
\
|
= - m A
2
B C = -100 mL
2
/g
(
|
.
|
\
|

= |
.
|
\
|
B B
A
A w A

A C m
V 1
1
1
0
= m A C (B A 1/
B
) = 877 mL
2
/g
6.3.5. Mass pi eces densi t y
2
0
B
A
B

C A m
V
= |
.
|
\
|
= 1,8710
-2
mL
2
/g
6.3.6. Cubi c t her mal expansi on coef f i ci ent of t he mat er i al of t he f l ask
9 , 499 )) ( (
0
0
= =
|
|
.
|
\
|
t t B A m
V
C mL
1
0
=
men
V
V

1
0
=
rep
V
V


6.4. Combi ned st andar d uncer t ai nt y of measur and
The combined uncert aint y u(V
20
) is calculat ed from equat ion 22. The individual t erms are collect ed and
subst it ut ed int o t his expression t o obt ain:
( )
( ) ( ) ( ) ( ) ( )| 024 , 0
) ( ) ( ) ( ) (
2
1
2 2 2 2
2
0 2
2
0
2
2
0 2
2
0 2 0 2
2
0
0
= + + +
|
|
.
|
\
|
+
|
|
.
|
\
|
+
|
|
.
|
\
|
|
|
.
|
\
|
+ |
.
|
\
|
+ |
.
|
\
|
=
rep evap men B
B
A
A
w
w
V u V u V u u
V
u
V
u
V
u
V
t u
t
V
m u
m
V
V u

mL

6.5. Eval uat i on of any exi st i ng covar i ances
There are no significant covariances.
6.6. Choi ce of an appr opr i at e cover age f act or ( k)
To calculat e t he coverage fact or ( k), it s necessary t o est imat e t he degrees of freedom,
eff
,

using t he
Welch-Sat t ert hwait e formula:
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
4
4 4 4 4 4 4 4
4
1
4
4
20
20
rep
rep
men
men
B
B
A
A
W
W
V
N
i i
i
V
eff
V
V u
V
V u u u u u
t
t u
m
m u
u
u
u
V

+ + + + + + +
= =
=

9
10 46 , 1
50000
10 94 , 1
50000
10 30 , 4
500000
10 98 , 9
500000
10 10 , 4
3492
10 34 , 5
50
10 25 , 6
203
10 40 , 5
10 61 , 3
) (
8 7 16 14 15 12 18 10
7
20

= V
eff

221 ) (
20
= V
eff
, Which corresponds t o a coverage fact or k = 2 and probabilit y of approximat ely 95 %.

6.7 Expanded uncer t ai nt y
The expanded uncert aint y is deduced by:
U = k u(V
20
) = 2 0,024 = 0,048 mL


Table 2 Summary f or t he st andard uncert aint y component s
St andard
uncert aint y
component
u(x
i
)
Source of
uncert ait y
Value of st andard
uncert aint y
u(x
i
)
i
i
x
f
c

( )
i i i
x u c V u ) (
0

(mL)
Degrees of
freedom
u(m) Mass 0,0048 g 1,00 4,82 10
-3
203
u(t) Wat er
t emperat ure
0,005 C -110
-2
5,00 10
-5
50
u(
W
) Wat er densit y 1,52 10
-6
g / mL -100 1,52 10
-3
3492
u(
A
) Air densit y 2,89 10
-7
g / mL 877 2,53 10
-4

u(
B
) Densit y of t he
mass pieces
0,03 g / mL 1,87 10
-2
5,62 10
-4

u() Coefficient of
expansion from t he
flask mat erial
2,89 10
-7
/ C -499,9 1,44 10
-4

u(V
men
) Meniscus reading 0,021 mL 1 0,021
u(V
rep
) Measurement
Repeat abilit y
0,011 mL 1 0,011 9
( ) ( )
4
20
2
20
2
10 01 , 6

= =

V u V u
i c
mL
( ) 024 , 0
20
= V u
c
mL
( ) 221
20
= V
eff

7. Ref er ences
1. BI PM et al, Guide t o t he Expression of Uncert aint y in Measurement (GUM), 2nd ed., I nt ernat ional
Organizat ion f or St andardizat ion, Genve, 1995
2. I SO 3696 (1987) Wat er f or analyt ical laborat ory use: specificat ion and t est met hods
3. I SO 4787 - Laborat ory glassware - Volumet ric glassware - Met hods for use and t est ing of capacit y;
Genve 1984
4. Bat ist a, E., Pat on R. The select ion of wat er propert y f ormulae for volume and flow calibrat ion,
Met rologia, 2007, 44, 453-463
5. Tanaka, M., et . al; Recommended t able for t he densit y of wat er bet ween 0 C and 40 C based on
recent experiment al report s, Met rologia, 2001, 38, 301-309
6. A. Picard, R.S. Davis, M. Glaser and K Fuj ii, Revised formula for t he densit y of moist air
Met rologia, 2008, Vol. 45, p 149-145
7. F Spieweck; H. Bet t in, Review: Solid and liquid densit y det erminat ion , Tm-Technisches Messen
59(1992) 7/ 8
8. OI ML R 111 (2004) - Weight s of classes E1, E2, F1, F2, M1, M2, M3
9. ASTM E542: St andard Pract ice for Calibrat ion of laborat ory Volumet ric Apparat us, 1
st
ed., American
St andard, 1
st
ed., 2000

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, Which corresponds t o a coverage fact or k = 2 and probabilit y of approximat ely 95 %.

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