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    Measurement Canada

    Volumetric Engineering

    Technical Paper 003

    Gravimetric Calibration of

    Volumetric Standards

    Issued: June 2, 1999

    Revised Dec 1st, 2009

    By: Christian Lachance, P. Eng.

    Senior Engineer - Liquid Measurement

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    Table of Contents1.0 The Gravimetric Calibration of Volumetric Standards . . . . . . . . . . . . . . . 3

    2.0 Mathematical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

    2.2 Water Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

    2.3 Mass Determination of the Delivered Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

    2.3.1 Method A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

    2.3.2 Method B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

    2.3.3 The Use of Apparent Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

    3.0 Gravimetric Calibration Uncertainty Overview . . . . . . . . . . . . . . . . . . . . 12

    4.0 Uncertainty of the Base Volume Determination . . . . . . . . . . . . . . . . . . . . . 134.1 Volumetric Standard Temperature Uncertainty, u(Tshell) . . . . . . . . . . . . . . . . . . . . . . 14

    4.2 Cubical Coefficient of Expansion Standard Uncertainty, u(") . . . . . . . . . . . . . . . . . 154.3 Water Density u(D(Tw)) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

    4.3.1 Water Temperature Standard Uncertainty, u(Tw) . . . . . . . . . . . . . . . . . . . 16

    4.4 Mass Determination Standard Uncertainty, u(Mw) . . . . . . . . . . . . . . . . . . . . . . . . . . 17

    4.4.1 Air Density Standard Uncertainty, u(Da ) . . . . . . . . . . . . . . . . . . . . . . . . . . 204.4.1.1 Air Temperature Uncertainty, u(Ta) . . . . . . . . . . . . . . . . . . . . . . 20

    4.4.1.2 Relative humidity uncertainty u(RHa) . . . . . . . . . . . . . . . . . . . . . 20

    4.4.1.3 Atmospheric pressure uncertainty, u(Pa) . . . . . . . . . . . . . . . . . . . 21

    4.4.2 Reference Mass Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

    4.4.3 Reference Mass Density Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

    4.4.4 Comparator Uncertainty and Method Repeatability . . . . . . . . . . . . . . . . . . 21

    4.4.5 Water Density Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

    5.0 Volumetric Standard Reproducibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235.1 Leveling Error . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

    5.2 Scale Plate Reading Error . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

    5.3 Wetting Variance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

    6.0 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

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    V V T T Tref T ref shell 1

    V M T TTref w

    Tw

    ref shell 1

    1.0 The Gravimetric Calibration of Volumetric Standards

    Common large volumetric standards are calibrated to deliver a known volume. Gravimetric

    calibration of volumetric standards consist of weighing water delivered by the volumetric

    standard and then deriving the volume from the mass and density of the water. Since the volume

    of the standard is dependent on temperature, the reported value is corrected to a reference

    temperature.

    2.0 Mathematical Model

    2.1 General

    Volume is determined from mass and density by the following equation:

    (2.1)VM

    T

    T

    where T = temperature

    VT = volume @ T

    M = absolute mass

    DT = density @ T

    The volume of the standard is a function of the temperature such that:

    (2.2)

    where VTref = volume of standard @ Tref

    VT = volume of standard @ T

    Tref = reference temperature

    " = cubical coefficient of expansion of the standardTshell = temperature of the standard

    Combining (2.1) and (2.2) we obtain:

    (2.3)

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    SMOW Tw aTw a Tw a

    a Tw akg m

    5

    1

    2

    2

    3 4

    31

    where Mw = absolute mass of waterTw = temprature of water

    = density of water @ Tw Tw

    2.2 Water Density

    Water density values are obtained from published formulation by Tanaka 1 where the density is

    provided as a function of temperature and isotopic content. The formulation provides the density

    values and their uncertainties for Standard Mean Ocean Water (SMOW) at a pressure of 101 325

    Pa.

    (2.4)

    where a1 = -3.983 035

    a2 = 301.797

    a3 = 522 528.9

    a4 = 69.348 81

    a5 = 999.974 950

    DSMOW(Tw) = Standard Mean Ocean Water density

    SMOW is air free water characterized by isotopic content. Most sources of water will have

    isotopic content that differ from SMOW. When the highest accuracy is required, the isotopic

    abundance of the water source must be determined and the density correction applied.

    The expected difference between aerated and air free water density is calculated as per Bignell2

    with the following equation:

    Daerated = -0.004612 + 0.000106 Tw (2.5)

    Where Tw is in degrees C and Daeratedis in kg/m3.

    Water that has been distilled and not exposed to air is considered air-free water while water that

    has been exposed to air will become air saturated. The gravimetric calibration process and

    distilled water storage at MC laboratories are such that the water can be assumed to be fully

    saturated. The density of the water at Tw is then:

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    Tw Tw TwSMOW aerated

    Where

    )D(Tw) = is the deviation in the actual water density from SMOW with correction foraeration.

    2.3 Mass Determination of the Delivered Water

    Mass can be determined by the single substitution method using an electronic single pan balance.

    Two methods will be presented. Both methods require a container which can be the volumetric

    standard or a separate container into which the water is delivered.

    2.3.1 Method A

    Method A is a general purpose method where the weight of the water is obtained by subtracting

    the empty container weight from the weight of the filled container.

    This method is a 4 step process:

    1. Weighing of the empty container, record:

    IE

    2. Weighing of reference weights close in value to that of empty

    container, record:

    IREMREDR

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    3. Weighing of container and water, record:

    DaIFD(Tw)

    4. Weighing of reference weights close in value to that of container and the water, record:

    IRFMRFDR

    Where

    Mw = absolute mass of water delivered or contained

    ME = absolute mass of container empty

    MF = absolute mass of container filled

    MRE = absolute mass of reference weight for empty container

    MRF = absolute mass of reference weight for filled container

    D(Tw) = density of water @ Tw

    DR = density of reference weights

    Da = density of air during weighing

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    W gMa

    x

    1

    Kxx

    a

    1

    IE = scale indication of empty container

    IRE = scale indication of reference weights for container

    IF = scale indication of a filled container

    IRF = scale indication of reference weight for filled container

    Ww = weight of water

    WF = weight of filled container

    WE = weight of empty container

    The mass of water can then be calculated from the recorded data.

    The weight of an object is related to its mass by

    (2.7)

    where

    W = weight of objectg = acceleration due to gravity

    M = absolute mass of object

    Da = density of air surrounding objectDx = density of object

    let

    (2.8)

    For an electronic single pan balance the indication, I, is proportional to the weight applied, suchthat:

    I = $ M K (2.9)

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    M KI M K

    IE E

    E RE RE

    RE E

    1

    I M KE I E EE

    I M KRE I RE RERE

    M KI M K

    I M KE EE RE RE

    RE RE RE E

    where $ is a calibration factor which includes g.

    For the weighing method presented we have for the weighing of the empty container:

    (2.10)

    (2.11)

    The ideal balance will have a value of$ that is constant for all weighings. In practice, however,

    a number of factors will cause this parameter to vary. Of concern are the effects of the balancerepeatability, non- linearity, stability and off-center loading. These effects and their contribution

    to the weighing uncertainty can be mitigated by proper weighing method. Other factors such as

    ambient temperature, loading method and magnetism may be significant in certain applications

    or with certain equipment. These should be investigated to ensure that they are accounted for in

    the determination of the uncertainty if required.

    In order to account for the effects of linearity, eccentricity and stability in the estimate of the

    uncertainty, the difference between the sensitivity coefficients of the artefact and the subsequent

    reference mass weighing for the empty container is written as:

    (2.12) I I ERE E

    Combining (2.10), (2.11) and (2.12) we obtain:

    (2.13)

    Since the )$ terms is a small value and MREKRE is close in value to IRE, (2.13) can beapproximated by:

    (2.14)

    the same is true for MF, where:

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    M KI M K

    IF FF RF RF

    RF F ( )1

    M KI M K

    I

    I M K

    IW WF RF RF

    RF F

    E RE RE

    RE E

    ( ) ( )1 1

    MK

    K

    I M

    I

    I M

    IWR

    W

    F RF

    RF F

    E RE

    RE E

    ( ) ( )1 1

    M K M K M Kw w F F E E

    W W Ww F E

    K K KRF RE R

    (2.15)

    The weight of the water delivered is obtained by:

    (2.16)

    Combining (2.7) , (2.8) and (2.16) we obtain:

    (2.17)

    Combining (2.17), (2.14) & (2.15) we obtain:

    (2.18)

    If reference weights of the same density are used for the filled substitution and the empty

    subsitution, then:

    (2.19)

    By combining (2.18) and (2.19), we obtain:

    (2.20)

    The mass of the water is obtained by assuming a value of 0 for the )$ terms.

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    I I M KF E I I W W F E

    I I I IRF E F E

    I I M KRF E I I R RRF E

    MI I

    I I

    K

    KM

    W

    F E

    RF E

    R

    W

    R

    ( )

    ( ) 1

    2.3.2 Method B

    Method B tares the weight of the empty container thus only requiring one substitution weighing.

    It can be used when the substitution weight can be weighed with the empty container.

    This method is a 3 step process:

    1. Weigh the empty container, record Ie ( please note that this step is last when the standard test

    measure is used as the container).

    2. Weigh the filled container, record: IF , Da.

    3. Weigh the empty container and reference weight close in value to the water delivered, record:IRF , MR , DR.

    Because reference weights are added directly to the tare, the filled container indication less the

    tare indication will be proportional to the reference weights such that:

    (2.21)

    and

    (2.22)

    In order to account for the effects of linearity, eccentricity and stability in the estimate of the

    uncertainty, let:

    (2.23)

    combining (2.21), (2.22) and (2.23) and since the )$ term is a very small value and MRKR isclose in value to ( IRF - IE), we obtain the following:

    (2.24)

    The mass of the water is obtained by assuming a value of 0 for the )$ term.

    Since the weighing is done at filled load, the error introduced by the scale linearity, stability

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    and eccentricity MR/(1-)$) can be approximated with MF/(1-)$F). This is convenient if the

    estimate of)$F is available while )$ is not.

    2.3.3 The Use of Apparent Mass

    Apparent mass is related to absolute mass by the following:

    (2.25)M Mapparenta

    apparent

    a1 1

    Where: M = absolute mass

    Mapparnt = apparent mass

    Dapparnt = apparent densityDa = density of airD = density of mass

    The apparent mass of an object is thus a function of air density. The difference in the value of

    the apparent mass due to a difference in air density can be obtained by:

    (2.26)

    M M

    Mapparent

    a

    apparent

    a apparent

    1 1

    The difference of the apparent mass value, or resulting error, due to differing air density in

    calibration and in use is:

    (2.27) Errorapparent

    ai r du ri ng ca l ai dur in g use

    1 1

    _ _ _ _

    This error is small in relation to the uncertainty of the mass. For example for a situation wherethe apparent density is 8000 kg/m3 but the actual mass density is 8600 kg/m3 and where the

    difference between the air density during the calibration of the mass and it use differs by 0.1

    kg/m3 the error will be less than 1 ppm. Therefore the following approximation can be made:

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    (2.28)M Muse

    apparent

    use

    apparrentcal

    1 1

    ,

    Where Mapparnt, Dcal = apparent mass determined in calibration air density.

    3.0 Gravimetric Calibration Uncertainty Overview

    Gravimetric calibration gives rise to uncertainty due to two key factors: base volume

    determination and the volumetric standard reproducibility.

    The mathematical model for the base volume determination is provided by equation (2.3), it

    covers the following influence factors:

    1) uncertainty in the mass determination;

    2) uncertainty in the water density determination;

    3) uncertainty of the cubical coefficient of expansion; and

    4) uncertainty of the temperature of the volumetric standard.

    The uncertainty of the base volume determination is obtained by root sum square of the influence

    factors such that:

    (3.1)u u u u uT Mshell W W Volume determination2 2 2 2 2 ( )

    The amount of volume delivered by a volumetric standard can be expected to vary, this

    reproducibility characteristic is due to:

    1) leveling of the standard (u leveling);

    2) reading of the standard (u reading); and

    3) wetting and drip variances.

    The uncertainty due to the reproducibility of the standard will be the combined effect of theabove. Since these effects are independent they can be combined by a root sum square:

    (3.2)u u u ureproducibility leveling reading wetting2 2 2 2

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    u VfV

    uc Tref i

    nTref

    i

    i

    2

    1

    2

    2( )

    The combined standard uncertainty is the reproducibility of the standard combined with the

    uncertainty of the base volume determination. These can be combined by root sum square as perthe following equation:

    (3.3)

    u u u u u

    u u u

    V T M

    leveling reading wetting

    Tref shell W W

    2 2 2 2 2

    2 2 2

    ( )

    4.0 Uncertainty of the Base Volume Determination

    The mathematical model for the base volume determination was given in (2.3). Although Tw and

    Tshell are assumed to be the same value, we can also assume the error of the two values to beindependent since the error of Tshell is mostly due to the measurement process while the error of

    Tw is mostly due to the thermometer reading uncertainty. We will thus consider all influence

    factors independent. The combined standard uncertainty can then be calculated by the

    following:

    (4.1)

    where:

    uc = combined standard uncertainty

    xi = influence quantities

    u(xi) = standard uncertainties attributed to the influence quantities

    The following table lists the influence quantities, their sensitivity coefficients and the square of

    the uncertainty contribution of the influence factor. The uncertainty terms have been

    approximated, where appropriate.

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    M

    T T

    Twref shell

    w

    1

    2

    ( ) MTw

    u Tw

    w

    2

    2

    ( )( )

    VTref

    i

    u V ux Trefi

    ii

    2

    2

    2

    MT T

    Twwref shell

    ( )

    M

    T T

    Twref shell

    w

    1

    2

    ( )

    1 T T

    T

    ref shell

    w

    ( )

    Influence quantity Sensitivity coefficient Square of the uncertainty

    contribution of the

    influence factor (the

    sensitivity coefficient has

    been replaced by an

    equivalent approximation

    where appropriate)

    Pi

    Tshell M

    Tw

    w

    ( )

    (V " u(Tshell) )

    2

    " V T T uref shell ( )2

    SMOW wT M

    Twu T

    w

    SMOW w

    2

    2

    ( )( )

    MW

    u MTww

    ( )

    2

    )D(Tw)

    4.1 Volumetric Standard Temperature Uncertainty, u(Tshell)

    The volumetric standard temperature, Tshell, is assumed to be the same as that of the water Tw.

    The uncertainty of this value is influenced by the thermometer calibration uncertainty,

    thermometer drift and, for the most part, the uncertainty due to the temperature measurementmethod. The latter is a function of the following factors:

    - the assumption that the shell temperature is the same as that of the water, this is influenced

    by the temperature difference between ambient and the water;

    - possible temperature non-uniformity in the standard.

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    The volumetric standard temperature uncertainty is:

    (4.2)u T u calibration u drift u method shell2 2 2 2( )

    Where:

    u calibration can be obtained from calibration certificate;

    u drift can be obtained from manufacturer specifications, based on calibration history or based

    on ice point verification tolerance;

    u method is estimated based on expected ambient conditions and water temperature differential.

    4.2 Cubical Coefficient of Expansion Standard Uncertainty, u( )

    The uncertainty of the assumed cubical coefficient of expansion is estimated at +/- 10 %:

    (4.3) u

    01

    3

    .

    4.3 Water Density u( (Tw))

    The uncertainty of the water density determination is a function of the water temperature

    measurement uncertainty, the density model uncertainty and the level of purity of the water

    sample.

    The uncertainty of the water density due to the measured temperature is obtained as follows:

    (4.4) u u TSMOW w SMOW wT

    w

    w

    ( )

    ( )

    The uncertainty of the SMOW density formulation is reported at 0.9 ppm. However, certain

    isotopic ratio must be measured to obtain this level of uncertainty. Where the isotopic ratios

    have not been measured a value of 20 ppm is suggested4 as appropriate.

    The correction for aerated water density is approximately 2 to 3 ppm at room temperature. Sincethe correction is small relative to the 20 ppm uncertainty of air free water mentioned above, the

    uncertainty of this correction can be neglected.

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    u Tw kg m 0020 33

    . /

    In some instance, where large volumetric measure are calibrated and where the facilities do not

    provide a large supply of purified water such as the Measurement Canada gravimetric calibrationlaboratory, purified water can be re-circulated and re-used. In order to assess the quality level of

    the purified water used for gravimetric calibrations, the water density can be monitored by

    comparing the density of representative samples to that of ultrapure water such as that produced

    at the NRC facility. Comparisons should be conducted using a high precision densitometer. For

    very high accuracy applications the results can be used to estimate a correction for the water

    density when the reference water sample is traceable.

    Unless a density correction is used, the uncertainty due to deviations from SMOW ,with

    correction for aeration, is assumed to be +/- 20 ppm so that:

    (4.5)

    If a correction is used, the uncertainty of the correction must be estimated from the reference

    sample stated uncertainty and the densitometer measurement repeatability.

    4.3.1 Water Temperature Standard Uncertainty, u(Tw)

    The uncertainty of this value results from the thermometer calibration uncertainty and the

    uncertainty due to the temperature measurement method. The latter is a function of the

    following factors:

    - water temperature uniformity in the standard;- self-heating effect of the probe in static water.

    The volumetric standard temperature and water uncertainty is obtained by the root sum square of

    the above mentioned factors:

    (4.6)u T u calibration u drift u method W2 2 2 2( )

    Where:

    Ucalibration can be obtained from the thermometer calibration certificate;

    Udrift can be obtained from thermometer manufacturer specifications, calibration history or it

    can be estimated from ice point check tolerance;

    Umethod can be estimated from temperature gradients in the standard and self heating

    characteristics of the thermometer.

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    I M

    I

    K

    K

    F RF

    RF

    R

    wF

    1

    12

    I M

    I

    K

    K

    E RE

    RE

    R

    wF

    1

    12

    M uE E2 2

    cMw

    i

    i

    Mu

    w

    i

    i

    2

    2

    M

    I

    K

    K

    RF

    RF

    R

    w

    u IF2

    M IK

    K IRF F

    R

    W RF

    1 2

    u IRF2

    M

    I

    K

    K

    RE

    RE

    R

    w

    u IE2

    M I KK I

    RE E

    R

    w RE

    1

    2

    u IRE

    2

    4.4 Mass Determination Standard Uncertainty, u(Mw)

    The uncertainty of the mass determination is again determined as per equation (2.20) and (2.24)

    for methods A and B respectively.

    The following table lists the influence quantities and their associated sensitivity coefficients for

    method A:

    Influence quantity Sensitivity coefficient Square of the uncertainty

    contribution of the

    influence factor (the

    sensitivity coefficient has

    been replaced by an

    equivalent approximation

    where appropriate)

    i

    IF

    IRF

    )$F M uF F2 2

    IE

    IRE

    )$E

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    I

    I

    K

    K

    F

    RF

    R

    w

    I

    IM

    I

    IME

    RE

    REF

    RF

    RFw r w

    r w a

    2

    M uWw R

    a

    2

    2

    21 1

    I

    IM

    I

    IM

    K

    E

    RE

    RE

    F

    RF

    RF

    a

    R W

    2

    u MR W aR

    2

    2

    2

    I

    I M

    I

    I M

    E

    RERE

    F

    RFRF

    R a

    W a

    2

    M uWa

    ww

    2

    2

    2

    u MRF2

    I

    I

    K

    K

    E

    RE

    R

    w

    u MRE2

    Da

    Dr

    Dw

    MRF

    MRE

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    I uRF F2 2

    Mw

    i

    Mu

    w

    i

    i

    2

    2

    M

    I I

    K

    K

    R

    RF E

    R

    W( ) u IF2

    M I I

    I I

    K

    K

    R F E

    RF E

    R

    w

    ( )

    ( )

    2 u I

    RF

    2

    M I I

    I I

    K

    K

    R RF F

    RF E

    R

    w

    ( )( )

    2 ( )I IM u IRF F

    RFE

    2

    2

    2

    I I

    I IM k

    F E

    RF E

    R R

    w r w

    r w a

    2 M uR

    w R

    a

    2

    2

    21 1

    u MR RF aR

    2

    2

    2

    M K

    I I

    I IR R

    F E

    RF E

    a

    W a

    2

    M uR aW

    W

    2

    2

    2

    F E

    RF E

    R

    w

    a

    R

    M

    K

    2

    The following table lists the influence quantities and their associated sensitivity coefficients for

    method B:

    Influence quantity Sensitivity coefficient Square of the uncertainty

    contribution of the

    influence factor

    i

    IF

    IRF

    )$F see text section 2.3.2

    IE

    Da

    Dr

    Dw

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    I I

    I I

    K

    K

    F E

    RF E

    R

    w

    u MR

    2

    u RHaTolerance

    3

    MR

    4.4.1 Air Density Standard Uncertainty, u(Da )

    Air density is calculated using the equation provided by Davis3. The uncertainty of the air

    density is a function of air temperature, humidity and barometric pressure.

    The uncertainty of the air density can be estimated by the following equation:

    (4.7)u u T u P u RH a a a a2 2 2 5 2 2 4 2 2

    0 00415 118 10 122 10( ) ( . ) ( ) ( . ) ( ) ( . ) ( )

    The above influence factors are addressed individually below.

    4.4.1.1 Air Temperature Uncertainty, u(Ta)

    The uncertainty of the air temperature is a function of the following factors:

    - u thermometer calibration is obtained form calibration certificate;

    - u thermometer drift can be obtained from thermometer manufacturer specifications,

    calibration history or it can be estimated from ice point check tolerance;

    - u temperature measurement method is estimated from the expected temperature fluctuation

    during the calibration.

    (4.8)u T u calibration u drift u method a2 2 2 2( )

    4.4.1.2 Relative humidity uncertainty u(RHa)

    The magnitude of relative humidity uncertainty can be large without significantly affecting

    results. It can be estimated from manufacturers specifications as a type B and or from calibration

    process limits.

    (4.9)

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    u M ToleranceR

    3

    4.4.1.3 Atmospheric pressure uncertainty, u(Pa)

    The uncertainty of the air pressure is a function of the following factors:

    - u calibration;

    - u drift can be obtained from manufacturer specifications or calibration history;

    - u pressure measurement method is estimated from the expected barometric pressure

    fluctuation during the calibration.

    Combining the above by root sum square we obtain:

    (4.10)u P u calibration u drift u method a2 2 2 2( )

    4.4.2 Reference Mass Uncertainty

    Reference mass uncertainty can be obtained from the calibration certificate. Otherwise, the

    grading of the reference mass can be used to estimate the uncertainty.

    Most often the gravimetric calibration will be performed with class F1 weights which have a

    tolerance of +/- 0.0005 %. Assuming a square distribution this can be converted to uncertainty

    by:

    (4.11)

    4.4.3 Reference Mass Density Uncertainty

    The reference mass density uncertainty component may be included in the uncertainty statement

    of the reference mass. In this case, this uncertainty term need not be calculated. When stainless

    steel reference mass is used, a tolerance of +/-200 kg/m3 can be used as the density uncertainty.

    4.4.4 Comparator Uncertainty and Method Repeatability

    When an electronic balance is used as a comparator, the uncertainty of the balance indication is

    due to its repeatability, eccentricity, stability and linearity which are dependent on the weighingmethod. Linearity errors can usually be reduced to a negligible amount by using reference

    weights which are close in value to the object weighed otherwise it must be accounted for.

    Stability errors are usually reduced by the appropriate use of a substitution weighing method.

    The uncertainty due to the scale eccentricity, stability and linearity must be evaluated in

    conjunction with the weighing method.

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    The uncertainty due to the repeatability of the scale can be established as a type A uncertainty

    after an analysis of the scale characteristics and the repeatability conditions under which it willbe used. This will provide the value of u(I). This should be used when a limited number of

    calibration runs is carried out.

    Alternatively, if many calibrations runs are carried out then it is possible to lump all repeatability

    components under one factor which is estimated as a type A uncertainty from the standard

    deviation of the calibration runs. Since the average of the determinations is reported then the

    contribution of the repeatability is calculated as per:

    urepeatability = Standard deviation of volume determination/ sqrt(n)

    Where n = number of runs

    This last approach will account for the scale repeatability error and therefore u(I) factors are not

    counted.

    4.4.5 Water Density Uncertainty

    The density of the water during the weighing is very well known. As a result the uncertainty of

    the mass determination due to the water density uncertainty is very small in relation to the

    overall mass uncertainty. It can be neglected.

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    x

    2

    y tan( )

    V yd

    2

    2

    5.0 Volumetric Standard Reproducibility

    5.1 Leveling Error

    When open neck volumetric measures are used, it is necessary to obtain a reading of the water

    delivered in the measure. Two principal factors affect the accuracy of the reading, the operators

    ability to read the scale and the proper leveling of the measure.

    Improperly leveling of the volumetric measure will result in a reading error. This error is

    dependent on the distance between the center of the measure to the sight tube and is dependent

    on the neck diameter of the measure.

    The following equations apply:

    (5.1)

    (5.2)

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    Where:

    2 = leveling angle errorx = distance between center of neck and scale plate

    )V = volume errord = internal neck diameter of the volumetric standard

    as a result the leveling uncertainty is:

    (5.3)u levelingd

    ( )tan( )

    3 2

    2

    5.2 Scale Plate Reading Error

    When an open neck volumetric measure is used by filling to the nominal mark, the reading

    accuracy is assumed to be +/- 0.5 mm of scale such that:

    (5.4)u readingd cm

    ( ).

    2

    0 05

    3

    2

    5.3 Wetting Variance

    Volumetric standards that are calibrated to deliver a known volume will be subject to variances

    in the amount of liquid volume which is delivered. This will be influenced by the liquid

    properties, construction of the standard, drip time and method. Wetting variance is estimated

    based on the standards calibration history or know characteristics for typical standard design and

    construction.

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    6.0 References

    1.M. Tanaka, G. Girard, R.Davis, A. Peuto and N. Bignell,Recommended table for the density of

    water between 0C and 40 C based on recent experimental reports, Metrologia, 2001,38,301-

    309

    2.N. Bignell, Metrologia 19, 1983, 57

    3. R.S. Davis,Equation for the Determination of the Density of Moist Air, Metrologia, 29, 1992,

    67-70

    4. Elsa Batista, Richard Paton, The Selection of Water Property Formulae for Volume and Flow

    Calibration, Metrologia 44, 2007, 453-463