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PROC-TC-012
Procedure for calibration
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PROC - C

WORK PROCEDURE

FOR

CALIBRATION OF Flasks and Cylindres

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Table of contents

CONTENTS PAGE NO.

1. Purpose 3
2. Scope 3
3. Normative References 3
4. Terms And Definition 3
5. General Requirements 5
6. Weighing Equipment Used 6
7. Gravimetric Procedure for Calibration 7
8. Calculations 8
9. Calculations for Measurement Uncertainty 9
10. Associated Documents 14
11. APPENDIX A 18

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1.0 Purpose
Purpose of this Lab Calibration Procedure is to provide guideline for the calibration of Flask
and Cylinder to Contain.

2.0 Scope

 Calibration of Flask. From 5ml to 2000 ml

 Calibration of Cylinder. 10ml to 1000 ml

3.0 Normative references

 ISO 4787 Laboratory glassware - Volumetric instruments - Methods for testing of

capacity and for use Operating Manual of Mettler balance.
 ISO/TR 20461:2000: Determination of uncertainty for volume measurements made using
the gravimetric method
 Quality Manual of Calibration Services ISO/IEC 17025.

4.0 Terms and definitions

For the purpose of this Lab Calibration Procedure following definitions shall apply:
4.1 Calibration
The set of operations which establishes under specific conditions the relationship between
value indicated by a measuring instrument or measuring system or values represented by a
material measure and the corresponding known value of the measurand.
4.2 Traceability
The property of a measurement result whereby it can be related to appropriate standards
generally national or international standards through an unbroken chain of comparisons.
4.3 Measurement Standards
A Material measure, measuring instrument or system intended to define, realize, conserve or
reproduce a unit by one or more known value of a quantity, in order to transmit them to other
measuring instruments by comparison.
Note
In this method a measurement standard is the “Unit under Calibration”.
4.4 UUC (Unit under Cal)
Unit under Cal is the instrument, which is being calibrated by this method statement.
4.5 Reference Standard
A standard generally of a highest metrological quality available from which measurements
made at a given location are derived.

4.6 Uncertainty of Measurement

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It is an estimate of the uncertainty of the result of a calibration. The estimate is obtained by

multiplying the combined uncertainty by a coverage factor.
4.7 Internal Uncertainty or Type “A”
The component of uncertainty, which is caused by type “A” errors and is evaluated from the
measurement results using statistical methods.
4.8 External Uncertainty or Type “B”
It is the component of uncertainty, which is caused by Type “B” errors and is evaluated by
non-statistical methods from the external factors having influence on the measurement
4.9 Repeatability
The degree of agreement between results of successive measurements of the same measurand
carried out under identical conditions, with identical methods and over a short period of time.
4.10 Resolution
Smallest difference that can be meaningfully distinguished (e.g. a change of one (1) in the last
place of a digital display)
4.11 Maximum permissible error
Extreme values of error permitted by specification / class
4.12 Adjustment
Altering the pipette or burette so that the dispensed volume is within the specifications.
4.13 Dispense
To deliver the sample.
4.14 Ambient pressure
The pressure surrounding a device, often equal to the prevailing atmospheric pressure.

5.0 General Requirements

5.1 Laboratory Environment
The Calibration is carried out in controlled environment i.e. Temperature 20 °C ± 0.1°C and
temperature stability of ± 1 °C during calibration, Relative Humidity 35~65 % rh ± 5% rh
and ambient pressure 1014 ± 10 hPa. If the environmental conditions are exceeding specified
limits, calibration will be stopped and measures will be initiated to control the environment
within specified limits. The apparatus and samples should be allowed to stabilize in the
laboratory before any work is carried out. Two hours is normally adequate for this.

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 Identification:
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5.2 Temperature of calibration liquid

The temperature of the water used for the calibration shall be measured to ±0.1 °C.
Corrections for differences in temperature from the reference temperature shall be applied in
accordance with Annex B.

5.3 Cleanliness of glass surface

The volume contained in, or delivered by, a volumetric instrument depends on the cleanliness
of the internal glass surface. Lack of cleanliness results in errors through a poorly shaped
meniscus involving two defects:
 incomplete wetting of the glass surface, i.e. the liquid surface meets the glass at an arbitrary
angle instead of forming a curve such that it meets the glass tangentially;
 a generally increased radius of curvature, due to contamination of the liquid surface reducing
the surface tension.
The ascending or descending liquid meniscus shall not change shape (i.e. it shall not crinkle at its
edges). To ascertain whether a piece of glass apparatus is satisfactorily clean, it shall be
observed during filling and dispensing. Additionally, an experienced operator can recognize
the shape of an uncontaminated meniscus, in relation to its diameter.
Lack of cleanliness causes additional errors with volumetric instruments used for delivery due
to the film of liquid on the walls being irregularly distributed or incomplete, e.g. forming
drops on the glass surface. Furthermore, chemical residues can introduce an error in the
analytical result by contamination. Therefore, where volumetric instruments are fitted with
ground stoppers, special attention shall be paid to cleaning the ground zone.
5.4 Quality of used volumetric instruments
The glass surface shall be free from obvious damage, the graduations and inscriptions shall be
clearly readable and especially with instruments adjusted to deliver the jet shall be free from
damage and allow an unrestricted outflow of liquid.
5.5 Setting the meniscus
Most volumetric instruments employ the principle of setting or reading a meniscus (the
interface between air and the liquid) against a graduation line or ring mark. Wherever
practicable, the meniscus should descend to the position of setting. The tubing of the
volumetric instrument shall be in a vertical position. The eye of the testing person shall be in
the same horizontal plane as the meniscus or the graduation line (ring mark).

6 Weighing Equipment

1. Performance of gravimetric calibration procedure of a pipette requires use of a weighing

instrument with metrological parameters as described in norm ISO 8655-6.

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In case, where standard deviation of liquid measurement is specified, than it is possible to use
it as acceptance criterion instead of repeatability and linearity parameters of a weighing
instrument. However, it needs to be assumed, that standard uncertainty is not bigger than
twofold or threefold of reading unit d.

In order to maintain measurement re-traceability, a weighing instrument that is utilized for

pipette calibration, should have valid calibration certificate.

7 Gravimetric Procedure for calibration

7.1 For Flask to Contain

1- After cleaning and drying, weigh the empty flask including the stopper.

2- Place an appropriate sized funnel in the flask to discharge the water below the stopper.

3- Fill from beaker or supply line, maneuvering the funnel So as to wet the entire neck
below the stopper. Let stand for about 2 min to allow the walls to drain.

4- Place the flask under a burette and complete filling and setting the meniscus, taking care
not to splash water on the walls, after which place stopper in neck to lessen evaporation
and weigh.

NOTE: A pipette or dropper with a finely drawn tip may be used to adjust the meniscus instead of
the burette.

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5- Determine the temperature by placing a thermometer in the filling beaker or in one

which has been filled from the water supply. The temperature may be taken after final
weighing by placing a thermometer directly in the flask, provided the flask is of
sufficient size to accommodate it.

7.1 For Cylinder to Contain

Using the same Procedure as Flask

9.0 Calculations

a) Calculate the mass of water Contain for each cycle by subtracting the balance reading
recorded at the end of the previous cycle from the reading recorded at the end of the cycle. If
appropriate, add the mass of water lost by evaporation as determined in the previous
paragraph.
b) To convert each mass value to a volume at 20 °C (the standard reference temperature for the
calibration of Flask) it must be divided by the density of water corrected to 20 °C. A
correction for air buoyancy, which varies with the air density, must also be applied. Both
these factors are taken into account by multiplying the each mass value by a correction factor
Z. A table specifying the value of Z for a temperatures range of 15 °C and 30 °C and air
pressure range of 80 kPa to 105 kPa. The correction factor is also given as an equation in
ISO/TR 20461:2000.

The volume V is calculated according to the following

V=W .Z.Y (2)

Where net weighed value,

W =W2-W1 (3)

(4)

(5)

(6)
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Where,
V = volume in ml
W2 = weighed value of the vessel with calibration liquid in g
W1 = weighed value of the empty vessel in g
ρL = density of the air in g/cm³
ρG = density of the weights in g/cm³ (standardized value for steel weights: 8000 kg/m³
= 8 g/cm³)
ρw = density of the calibration liquid in g/cm³
αc = cubic expansion coefficient in 1/K
td = temperature of the volumetric apparatus in °C (for simplification equated with the
temperature of the calibration liquid)
tb = reference temperature in °C
The water density ρw and the air density ρL can be calculated with the formulas stated in
appendix A

c) Add together each of the 10 volumes calculated in the previous paragraph and divide by 10 to
give the mean volume at 20 °C. This can be expressed in microliters or milliliters.

(7)

1. Random error is expressed in volumetric units: microliters [ul] and percent’s [%]. Random
error is marked with CV symbol. The measure of random error is standard deviation
calculated by a formula

(10)

(11)

10.0 Calculation of a Measurement Uncertainty

Determination of uncertainty is calculated according to the Technical Report ISO/TR

20461:2000 – edition 1 together with a correction note ISO/TR 20461:2000/Cor.1:2008

1. A conventional volume of a calibrated pipette in temperature 20 ºC is determined by the

following formula:

V20  mw  mevap  Z  Y (12)

where: mW – mass of distilled water ejected from a pipette

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mevap – mass of distilled water evaporated from a pipette

Z – coefficient determined in norm PN-EN ISO 8655-6 expressed by
formula (4)
Y – temperature coefficient related to a pipette determined in ISO/TR
20461 norm expressed by formula (5)

2. General formula of uncertainty of measurement:

2
 F 
u (V20 )   c  u ( x i )  
2 2
i
2
  u 2 ( x i ) (13)
i i  x i 
2
 F 
  
2
ci  (14)
 x i 

where: u2(xi) – particular uncertainties included in the measuring process

ci 2 – particular coefficients of sensitivity

Uncertainty of measurement formula:

u 2 (V20 )  u 2 (Uw )  u 2 (Lw )  u 2 (Rw 1 )  u 2 (Rw 2 )  u 2 (d w 1 )  u 2 (d w 2 )  u 2 ( m )  u 2 ( mevap )

(15)
 u 2 (V20 )  u 2 (t w )  u 2 (t a )  u 2 ( )  u 2 ( pa )  u 2 ( c )

where Uw – uncertainty of a balance calibration

Lw – a balance linearity
Rw1 – a balance repeatability (for the first indication)
Rw2 – a balance repeatability (for the second indication)
dw1 – a balance resolution (for the first indication)
dw2 – a balance resolution (for the second indication)
m – distilled water mass
mevap – mass of water evaporated during the measuring
V20 – calculated volume value in 20 ºC
tw – water temperature
ta – air temperature
φ – relative air humidity
pa – air pressure
αc – coefficient of material volume expansion of a piston-cylinder kit of the
calibrated piston vessel in 1/°C

2.1 Uncertainty of a balance calibration, Uw -

U
u(Uw )  (16)
3
U – Standard uncertainty of a balance
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2.2 A balance linearity Lw :

L
u(Lw )  (17)
3

2.3 A balance repeatability Rw :

R
u(Rw )  (18)
3
R – Balance repeatability

2.4 A balance resolution dw :

d
u (d w )  (19)
2 3
Where: d – a balance interval

2.5 Distilled water mass m:

d
u ( m)  m (20)
2 3

Note: According to the above formula you need to determine uncertainty of particular
measurements in a series, and then determine standard uncertainty for a series of 10
measurements:

 d  2 
u (m)  10   m   c w 
2
(21)
 2  3  

cw – coefficient of sensitivity related to mass measurement described further in this

procedure in issue 3.1

2.6 Evaporated water mass during calibration process mevap:

mevap
u(mevap )  (22)
3
δmevap – correction for water evaporation – constant 0,02 mg

2.7 Determined volume value in 20 ºC V20:

s
u(V20 )  d (23)
n
sd – standard deviation of n calculation results V = m · Z · Y
n - Number of measurements = 10

2.8 Water temperature tw:

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d tw
u (t w )  (24)
3
dtw –Thermometer resolution of water temperature measuring
2.9 Air temperature ta:
d
u(t a )  ta (25)
3
dta –Thermometer resolution of air temperature measuring

2.10 Air relative humidity φ:

d
u( )   (26)
3
dφ – hygrometer resolution

2.11 Air pressure pa:

d
u( pa )  pa (27)
3
dpa – barometer resolution

2.12 Coefficient of material volume expansion of a-cylinder kit αc:


u( c )  c (28)
3

3. Determine a sensitivity coefficient for every quantity according to chapter 4 of ISO/TR

20461:2000 document.

3.1 Coefficients related to mass measurement (balance):

Uw – balance calibration uncertainty

Lw – balance linearity
Rw1 – balance repeatability (for the first indication)
Rw2 – balance repeatability (for the second indication)
dw1 – balance resolution (for the first indication)
dw2 – balance resolution (for the second indication)
m – distilled water mass
mevap – mass of water evaporated during the measuring

The above coefficients are calculated according to the formula:

F V20
cw  
m m (29)

3.2 A coefficient related to volume determination V20 is calculated in the following formula:
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V20
cV 20  1 (30)
V20

3.3 A coefficient related to water temperature determination is calculated in the following formula:

c tw  2,1 10 7  m (31)

3.4 A coefficient related to air temperature determination is calculated in the following formula:

m  ( k 2  t a 0  k 3 )  k1 p a
c ta   (32)
w2 (t a  t a 0 )2

3.5 A coefficient related to relative air humidity determination is calculated in the following
formula:

m k2  ta  k3
c   (33)
w2 t a  t a0

3.6 A coefficient related to air pressure determination is calculated in the following formula:

m k1
c pa   (34)
w t a  t a0
2

3.7 A coefficient related to αc parameter determination is calculated in the following formula:

cc  10 3  m  (t d  20C ) (35)

td – pipette temperature expressed in [ºC] = ta

4. Determine standard uncertainty according to the below formula:

2 2 2 2 2
u 2 (V20 )  u 2 (Uw )  cw  u 2 (Lw )  cw  u 2 (Rw 1 )  cw  u 2 (Rw 2 )  cw  u 2 (d w 1 )  cw
2 2 2 2 2 2
 u 2 (d w 2 )  cw  u 2 ( m )  cw  u 2 (mevap )  cw  u 2 (V20 )  cv 20  u 2 (t w )  c tw  u 2 (t a )  c ta (36)
2 2 2
 u 2 ( )  c  u 2 ( pa )  c pa  u 2 ( c )  cc

5. Determine expanded uncertainty according to the below formula:

U  k  u(V20 )
(37)
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Using an extension coefficient k = 2 which corresponds to the confidence level 95%

The final Uncertainty Budget

11.0 Associated Documents

11.1 Calibration Data Sheet (……/……/……..)

11.2 Calibration Certificate (……/……/……..)
11.3 Calibration Sticker (……/……/……..)

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APPENDIX A

The density of pure water is normally provided from formulations given in the literature.
Batista and Paton provide an overview of common formulations used in practice. However it
is generally accepted that the formulation given by Tanaka provides a good basis for
standardization.

g/ml A.1

Where:
t = water temperature, in °C
a1 = -3,983035 ºC
a2 = 301,797 ºC
a3 = 522528,9 (ºC)2
a4 = 69,34881 ºC
a5 = 0,999974950 g/mL

Note: a5 is the density of SMOW water under one atmosphere at this temperature. Many
users of water rely on tap water instead of SMOW. Thus a5 must be changed accordingly to
reflect the density of the water used. The full equation of state for water provided by the
International Association for Properties of the Water Substance (IAPWS) can also be used to
determine the density of the used water and a formulation based on this equation is given in
ref. This provides an alternative to Tanaka and should be used if temperatures above 30 °C
are used.
Where pure water is not available, the relative density of the water may be determined and the
chosen formulation used to determine the temperature expansion factors with insignificant
loss of accuracy.
The air density can be determined according to the formula for the density of moist air -
CIPM-2007

A.2

p =ambient pressure, in Pa
T =thermodynamic temperature = 273,15 + t / ºC, in K
Xv= mole fraction of water vapour
xCO2= mole fraction of carbon dioxide in laboratory air
Z =compressibility factor

If the laboratory ambient conditions are within the limits given then Spieweck’s equation can
be used. The limits are: pressure between 940 hPa and 1080 hPa; temperature between 18 ºC
and 30 ºC; humidity less than 80 %,
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A.3
Where :
tA= ambient temperature, in °C
pA= ambient pressure, in hPa
hr= relative air humidity, in %
k1 = 3,4844 x 10-4 ºC/hPa
k2 = -2,52 x 10-6 g/mL
k3 = 2,0582 x 10-5 ºC

APPENDIX B
PHV-1

PHV-2

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APPENDIX C
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Calibration Certificate

Calibration Certificate
Central Organization for Standardization and Quality Control (COSQC)
Metrology Department - PHYSICS SECTION
P.O. Box13032 Algadria street, Baghdad ,Tel:7785180 - E-Mail : [email protected]
Certificate No.: PHV
Date of issue :

Customer
Name:  
Address:  

Item under calibration

Description:  
Manufacturer:  
Model:  
Serial number (CODE)  
Other identification:  
Date of reception:   Order No.      
Condition of reception:  

Standard(s) used in the calibration

Description:  
Manufacturer:  
Model:  
Serial number:  
Other identification:  

Calibration information
Date of calibration:   Due to:  
Place of calibration: Physics measurement lab
Method(s) of
 
calibration:
Calibrated quantity:  
Results of calibration: Attached a complete result in Annex 1 of this certificate
Measurement There reported expanded uncertainty is based on GUM Standard and the standard
uncertainty: Uncertainty multiplied by coverage factor k=2 to give confidence level of 95%
Metrological The traceability of measurement results to the SI units is assured by the Nationals tandard maintained at
traceability: Central Organization for standardization and Quality Control through calibration at :
Environmental
conditions of Temp. ( C): ±1ºC R. H.( %) ±5% Pressure ( mbar) ±1mbar
calibration:
Observations, opinions
The results and corrections in Annex 1 should be taken into consideration
or recommendations:

Approved by:

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Calibration Certificate
Central Organization for Standardization and Quality Control (COSQC)
Metrology Department - PHYSICS SECTION
P.O. Box13032 Algadria street, Baghdad ,Tel:7785180 - E-Mail : [email protected]
Certificate No.: PHV
Date of issue :
Annex 1 ( Results )

SIZE Volume Errors

ml ml Uncertainty ± ml
ml
1 1.020 0.020
0.8 0.807 0.007
0.6 0.593 -0.007 0.012
0.4 0.430 0.030
0.2 0.218 0.018

Performed by: Reviese by: Approved by:

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