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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 1/11

JCSS
Uncertainty Estimate Guide
Classification related to registration:

Classification of concentration calibration method (name): Standard solution

(various types) (1st edition)

Revision: May 29, 2013

National Institute of Technology and Evaluation

Certification Center

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 2/11

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including electronic and mechanical (transcription) methods, cannot be used without the permission of the National Institute of Technology and
Evaluation Certification Center.

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 3/11

Guide to uncertainty estimation (concentration: standard solution)

1. 1. Foreword

Uncertainties in pricing the concentration (or pH value) of the practical standard solution include the following. (1) Standard uncertainty of the

concentration of the specified secondary standard solution (immediately after pricing) * The uncertainty of the concentration of the specified secondary

standard solution supplied by the designated calibration institution is the "jcss calibration certificate" issued by the designated calibration institution.

Given by. (2) Standard uncertainty of homogeneity of specified secondary standard solution (3) Standard uncertainty of stability of specified secondary

standard solution (4) Standard uncertainty of repeated measurement in pricing measurement of practical standard solution) (5) Uniformity of practical

standard solution Standard uncertainty of stability (if necessary) ÿ Uncertainty that impurities in the practical standard solution give to pricing (if necessary)

* If necessary, consider the standard uncertainty of the atomic weight of the target element.

In the pricing of standard materials (practical standard solutions), it is necessary to establish an appropriate evaluation method in order to ensure the reliability

of measurements performed by users. Therefore, it is important to select a significant factor among various uncertainty factors and estimate the uncertainty

appropriately.

Below are three examples of uncertainty estimation in the pricing of standard solutions. All cases are examples in which a sufficiently large degree of freedom
k evaluation
is secured and = 2 can be adopted as the inclusion coefficient corresponding to the confidence level of about 95%. The threecases
casesofshown
inorganic
in this
standard
guide are

solution, organic standard solution, and pH standard solution other than pH standard solution, respectively, but there are multiple uncertainty evaluation methods

related to homogeneity, stability, and repeatability. An example of is described across cases (the numerical values shown are for the purpose of explaining the

calculation and are not typical). Please also refer to cases that are not subject to registration application and select an appropriate evaluation method. The

method of estimating uncertainty associated with pricing in the JCSS system is not limited to these cases. In the future, when applying for a new standard

solution or when uncertainty is required to be reassessed, we would like to be able to utilize past measurement data (pool data). Other rational procedures are

acceptable.

It is not necessary to strictly observe and evaluate all preparation lots according to the procedure described in this guide. For example, at the time of new

application or when the pricing procedure is changed drastically, check the pricing ability of a typical standard solution by evaluation according to this procedure,

and other related standard solutions ( There is also a method of performing a simple check (for example, confirming that the standard deviation is the same with

a small number of sample measurements) for preparation and pricing using the same procedure. Would be acceptable.

As a general rule, 1% or less (relative) with standard solutions other than pH standard solution, and 0.015 or less with pH standard solution (type 2).

Mark expansion is uncertain. The

following are points to keep in mind for making a rational uncertainty assessment.

• High enough accuracy to properly assess uncertainty, homogeneity and stability uncertainty

Keep in mind the measurement. Check the measurement accuracy on a regular basis (such as the 3-sigma method using the range R).

• In stability tests (other than pH standard solution), it is desirable to measure the mass change of the standard solution during storage.

(To confirm the change in concentration due to evaporation of the solution).

2. Citation Specifications

• ISO Guide 34: 2009 (JIS Q 0034: 2012 General requirements regarding the capacity of standard material producers)

-ISO Guide 35: 2006 (JIS Q 0035: 2008 Standard Material-General and Statistical Principles for Certification)

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 4/11

• ISO / TS 21749: 2005 (JIS Z 8404-2: 2008 Measurement uncertainty-Part 2: Evaluation of measurement uncertainty
Guidelines for the use of repeated measurements and branching experiments in
• TS Z 0033: 2012 Guide to Expression of Uncertainty in Measurement (GUM)

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 5/11

3. 3. Uncertainty in pricing Estimation example 1 (Inorganic standard solution (other than pH standard solution), titration

method) Here, for pricing the practical standard solution, a specific secondary standard solution (prepared and prepared by the applicant company) Multiple bottles

(1 bottle of which is used for pricing the specified secondary standard solution) and the practical standard solution alternately 3 times

Titrate (direct titration), obtain three measured values by one-to-one comparison using the following formula, and use the average value as the calibration value.

I will describe the case.

ÿ C t: Practical standard solution concentration,Cr: Specified secondary standard solution IN t: Titration of practical standard solution,

IN concentration, r: Titration of specified secondary standard solution)

As the standard deviation of the repeated measurement, from the 20 times repeated measurement data (pool data) acquired in the past.

The obtained experimental standard deviation is used.

3-1 Standard uncertainty of the concentration of the specified secondary standard solution (immediately after pricing): in 1

The uncertainty of the concentration of the specified secondary standard solution is stated in the calibration certificate provided by the designated calibration body. phase

Relative standard uncertainty = = 0.25 (%) if the vs. extended uncertainty is 0.5% and the inclusion factor is 2. in1 is

in 1

Given in. (Degree of freedom ÿ)

3-2. Standard uncertainty of homogeneity of specific secondary standard: in2

Collect 10 sample bottles of the specified secondary standard solution that have been subdivided and filled at equal intervals, and repeat the measurement twice per sample.

The following measurement results were obtained.

Measurement result 1 Measurement result 2

Bottle No.
ÿmg/Lÿ ÿmg/Lÿ

1 1003.81 1002.77

2 1005.26 1001.72

3 1003.83 1002.01

4 1005.45 1005.29

5 1001.44 1003.29

6 1002.43 1005.28

7 1001.69 1003.17

8 1000.04 1005.63

9 1001.35 1003.13

10 1003.02 (full average: 1003.14 1002.27

mg/L)

Based on the obtained results, perform a one-way ANOVA. Unbiased dispersion between bottles B, repeatedIN
measurement times
A. The inside of the bottle is not unevenly dispersed.
IN
2
n
As a number, s bbbottles is given by JIS Q 0035 7.8 (4) as follows.
the estimated value of the inhomogeneous variance between
2
s bb =

The results of analysis of variance are shown below. ANOVA can be done with Excel's analysis tools.

(scattered analysis table)

Fluctuation factors Fluctuation degree of freedom Variance

Between bottles 1.76 15.86 9

Inside the bottle 3.28 32.83 10

total 48.69 19

2
s bb =
From this result Is a negative value. This is due to the homogeneity, where the parallel precision variance is greater than the inter-bottle variance.

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 6/11

This is because sufficient measurement parallel accuracy has not been obtained to evaluate the uncertainty. Therefore, JIS Q 0035 7.9

Therefore, it was decided to calculate the uncertainty due to the inhomogeneity between bottles. First, measurement using JIS Q 0035 7.9 (6)
in
The effect of the parallel accuracy standard deviation on the inter-bottle inhomogeneity standard deviation was determined as follows.
bb

in = =
bb
= 0.856 (mg/L)

(Here, INB: Unbiased dispersion in the bottle (mg2 /L2 ), n : Number of repeated measurements ,: INB degrees of freedom (= (2-1) x 10))

Sr= =
Next, the relative uncertainty of the former = 1.81 (mg / L) was obtained. 2a

and the latter of the measurement parallel standard deviation is calculated as inand in
2b

in =
2a
= 0.0853 (%) (degree of freedom: ÿ), respectively.

in =
2b
= 0.180 (%) (DOF: 10)

* It is desirable to sample at least 10 sample bottles for measurement for homogeneity evaluation. Number of sample bottles

If the number is small, reasonable results may not be obtained (see JIS Q 0035 5.8).

* It is also possible to use a simple method (for example, the method used in 4-4).

3-3 Standard uncertainty of storage stability of specified secondary standard solution: in

3

Immediately after preparation and 6 months after preparation (specified second) for 3 lots of specified secondary standard solution (preparation concentration 1000.2 mg / L) manufactured.

The concentration of the next standard solution) was measured, and the following measurement results were obtained.

Preparation lot Measurement result (mg / L) Rate of change (%)

Immediately after 6 1009.6

1 0.030
months after 1009.9

preparation 6 months 995.8

2 0.080
after preparation 6 996.6

months after 1004.8

3 0.19
preparation 6 months after preparation 1006.7

It was evaluated as having a rectangular distribution with a one-sided width with the largest rate of change of 0.19%. As a result, the relative of the specified secondary standard solution

Standard uncertainty 3inis

in = = 0.110 (%) (DOF: ÿ)

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3-4 Standard uncertainty of homogeneity of practical standard solution: in4

In the same procedure as in 3-2, measurements and data were collected for the prepared practical standard liquid lots, and analysis of variance was performed.

The obtained analysis of variance table is shown below. (Overall average: 1005.2 mg / L)

(scattered analysis table)

Fluctuation factors degrees of freedom dispersion

Fluctuations Between bottles 9 11.949

107.54 In bottles 84.27 10 8.427

Total 191.81 19

From the analysis of variance table, the estimated value of the inhomogeneity standard deviation between bottles was calculated using JIS Q s Is calculated as follows
bb

0035 7.8 (4).

s bb = =
= 1.33 (mg/L)

(Here, INA: Unbiased dispersion between bottles (mg2 /L2 ), INB : Unbiased dispersion in the bottle (mg2 /L2 ), n : Number of repeated measurements)

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 7/11

Second, the effect of the measurement parallel accuracy standard deviation on the inter-bottle inhomogeneity standard deviation. inbb Was calculated as follows.

inbb = =
= 1.37 (mg/L)

Comparing the two, here the larger and the inbb (Refer to JIS Q 0035 Annex B.4).

Sr=
measured parallel standard deviations are, = 2.90 (mg / L). Relative uncertainty between the former and the latter in4a and

in4b

in4a = = 0.136 (%) (DOF: ÿ)

in4b = = 0.288 (%) (DOF: 10)

* Insmany inbb In the case of s bb Is an uncertainty of homogeneity between bottles, but it is difficult to evaluate the degree of freedom and it is not rational.

cases, the value of bb> degree can be obtained (see GUM Annex H.5.2.6). If it affects the evaluation of the degree of freedom, it can also be in4

evaluated using the method of 4-4.

3-5 Standard uncertainty of storage stability of practical standard solution: in5

Measured and evaluated for 3 lots of practical standard solution manufactured by the same procedure as 3-3, and the following relative uncertainty of stability is obtained.

difference in5 Got

in5 = = 0.0808 (%) (DOF: ÿ)

3-6 Uncertainty of repeated measurement of practical standard in6

n The relative
solution: Pool data (Relative standard uncertainty
standard 6 of
deviation of =return
20) was 0.35%. Since the average of the three measured values is used as the calibration value, it is repeated.

measurement is in

in6 =
= 0.202 (%) (DOF: 19)

3-7 Uncertainty that impurities in the practical standard solution give to pricing: in7

Consider if necessary, but not here.

3-8 Synthesis of uncertainty of each factor: inc

inc =
=
= 0.513 (%)

3-9 Calculation of effective degrees of freedom: ÿ eff

F
The effective degree of freedom is calculated by the Welch-Satterthwaite formula. ( I: Freedom of each standard uncertainty)

ÿ = =
eff

ÿ ÿ ÿ

= 87

3-10 Calculation of extended uncertainty: IN

If the effective degree of freedom obtained in 3-9 is 10 or more, the inclusion coefficient k = 2 can be adopted. However, effective degrees of freedom 10
for the effective degree of freedom is used if it is less than the inclusion coefficient. That is,
IN = k × inc

k
Since the effective degree of freedom is 87 here, the inclusion coefficient = 2 can be adopted. Therefore, the relative expansion IN teeth,

IN uncertainty is calculated as 0.513 × 2 = 1.1 (%) (confidence level of about 95%).

4. Uncertainty of pricing estimation Case 2 (organic standard solution, GC method)

Here, in order to price the practical standard solution, the specified secondary standard solution (supplied by the designated calibration organization) and the practical standard solution are mixed.

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 8/11

A case is described in which measurements are made three times each, three measured values are obtained by one-to-one comparison, and the average value is used as the calibration value.

To.

4-1 Standard uncertainty of the concentration of the specified secondary standard solution (immediately after pricing): in 1

The uncertainty of the concentration of the specified secondary standard solution is stated in the calibration certificate provided by the designated calibration body. phase

Relative standard uncertainty when the vs. extended uncertainty is 0.5% and the inclusion factor is 2. in1 is

in =
1

Given in. (Degree of freedom ÿ)

4-2 Standard uncertainty of homogeneity of specified secondary standard: in2

When the specified secondary standard solution is prepared and supplied by a designated calibration institution, the uncertainty of its homogeneity is the designated school.

Included in the concentration uncertainty provided by the institution.

in here .
Therefore, 2 is not considered

4-3 Standard uncertainty of storage stability of specified secondary standard solution: in3

If data on storage stability is provided by a designated calibration laboratory, it may be used.

Relative standard uncertainty of storage stability from the storage stability data of the specified secondary standard solution obtained from the designated calibration laboratory.

in3 is

= 0.05(%)

Given in u3 . (Degree of freedom ÿ)

4-4 Standard uncertainty of homogeneity of practical standard solution: in4

Collect 10 sample bottles filled in small portions at equal intervals, measure twice for each sample bottle, and obtain the following measurement results.

Obtained.

Bottle No. Measurement result 1 Measurement result 2 Mean Unbiased

ÿmg/Lÿ ÿmg/Lÿ (mg / L) dispersion (mg2 /L2 )

1 1041.83 1044.82 1043.33 4.47

2 1042.84 1039.62 1041.23 5.18

3 1042.94 1038.28 1040.61 10.86

4 1044.42 1041.92 1043.17 3.13

5 1049.75 1043.70 1046.73 18.30

6 1051.01 1045.82 1048.42 13.47

7 1048.18 1042.22 1045.20 17.76

8 1037.62 1042.85 1040.24 13.68

9 1049.96 1052.38 1051.17 2.93

10 1049.29 1043.75 1046.52 All 15.35

average 1044.66

Standard deviation of mean 3.59

Sum of unbiased variances 105.12

The uncertainty of homogeneity is assessed using the standard deviation (3.59 mg / L) of the mean of the measured values (2 data) for each bottle. Average

Relative uncertainty 4 of quality isin

in4 = = 0.344 (%) (DOF: 9)

* It is also possible to use analysis of variance. This method is simpler than the analysis of variance method, but it has an error term for parallel accuracy.

Includes. When the data is evaluated by analysis of variance in4 = s bb (relative value) = 0.26%.

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 9/11

4-5 Standard uncertainty of storage stability of practical standard solution: in5

Stability was evaluated using 3 lots of the prepared practical standard solution in the same procedure as 3-3. From the measurement data

Relative standard uncertainty of obtained stability = in5 is

in5 0.232 (%) (degrees of freedom: ÿ)

4-6 Standard uncertainty of repeated measurement of practical standard in6

solution: The data obtained in 4-4 is used. From the sum of the unbiased variances (105.12) obtained from the two measurement data for each bottle

The standard deviation of the relative uncertainty of repeated in6 Got (Here, considering the inhomogeneity between bottles, all measurement days

measurements is not used according to the following formula. )

in6 = =
= 0.179 (%) (DOF: 10)

(Here, INsum : Sum of unbiased variance, n : Number of bottles to be measured, : Total average, n’ : Number of repeated measurements in pricing measurement)

4-7 Uncertainty that impurities in the practical standard solution give to pricing: Consider in7

if necessary, but not here.

4-8 Synthesis of uncertainty of each factor: inc

inc =

=
= 0.519 (%)

4-9 Calculation of effective degrees of freedom: ÿ eff

The effective degree of freedom is calculated by the Welch-Satterthwaite formula.

ÿ = = = 47
eff

ÿÿ

4-10 Calculation of extended uncertainty: IN

Since the effective degree of freedom is 47, the k = 2 can be adopted. Therefore, relative expansion uncertainty IN teeth,

IN inclusion coefficient = 0.519 × 2 = 1.1 (%) (confidence level of about 95%) is calculated.

5. Uncertainty of pricing Estimate case 3 (pH standard solution, neutral phosphate)

Here, in order to price the practical standard solution, the specified secondary standard solution (prepared by the applicant company, multiple bottles of preparation lots)

(1 bottle of which is used for pricing the specified secondary standard solution) and the practical standard solution are measured alternately 3 times each.

An example in which three measured values are obtained by one-to-one comparison and the average value is used as a calibration value will be described. Repeated measurement

As a constant standard deviation, an experimental standard obtained from 20 repeated measurement data (pool data) acquired in the past.

Deviation is used.

5-1 Standard uncertainty of pH of specified secondary standard solution (immediately after pricing): in 1

The uncertainty of the concentration of the specified secondary standard solution is stated in the calibration certificate provided by the designated calibration body. Expansion

Standard uncertainty when the tension uncertainty is 0.004 and the inclusion factor is 2. in1 is

in =1
=0.002

Given in. (Degree of freedom: ÿ)

5-2 Uncertainty of homogeneity of specified secondary standard solution: in2

As a result of evaluating the homogeneity of the specified secondary standard liquid lot prepared by the same procedure as in 3-2, the value s bb 2 is

in
was negative, so bb jump 2b (degree S 0.0004210)
of freedom: and 0.00086
was used. were obtained as r, respectively. this in2a (degree of freedom: ÿ) and

in

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JCG221S11 JCSS Guide to Uncertainty Estimate (Standard Solution) 10/11

5-3 Uncertainty of storage stability of specified secondary standard solution: in3

Stability was evaluated using 3 lots of the specified secondary standard solution prepared in the same procedure as 3-3. Measurement day
Uncertainty of stability obtained from data = in3 is

in 0.0012 (degree of freedom: ÿ)

3

5-4 Standard uncertainty of homogeneity of practical standard solution: in4

As a result of evaluating the homogeneity of the prepared practical standard liquid lots in the same procedure as in 3-2, the values s bb 2 is negative

in andS0.00071 were obtained as r. This is 4a (degree of freedom: ÿ) and 4b in

were obtained, and 0.00036 (degree of freedom: ÿ). in
bb and

10).

5-5 Standard uncertainty of storage stability of practical standard solution: in5

Stability was evaluated using 3 lots of the prepared practical standard solution in the same procedure as 3-3. From the measurement data
Uncertainty of obtained stability = in5 is

in 0.0012 (degrees of freedom: ÿ)

5

5-6 Uncertainty of repeated measurement of practical standard in

6

n The experimental
solution: Pool data (Uncertainty of return measurement
standard deviation of6= is
20) was 0.0009. Since the average of the three measured values is used as the calibration value, it is repeated.

in

in = = 0.00052 (DOF: 19)

6

5-7 Uncertainty of temperature fluctuation: Consider in7

if necessary, but not here.

Uncertainty regarding tolerance determination of 5-8 measured values and use of default values for calibration values: in
8

If the difference between the measured value and the judgment value (6.865) is within ± 0.005, the pH calibration value of the practical standard solution is set to the default value (6.86).

It is supposed to be. In this case, first, the distribution of the measured values is a rectangular distribution with a width of 0.005 on each side, and the standard uncertainty of the tolerance judgment is uncertain.

difference in To evaluate.
8a

in =
8a
= 0.0029 (DOF: ÿ)

Next, the uncertainty 8b due to the difference between the judgment value and theindefault value is evaluated as a rectangular distribution with | judgment value-default value | as one side width.

Worth.

in =
8b
= 0.0029 (DOF: ÿ)

* Obtain the measured value by one-to-one comparison with the specified secondary standard solution (specific secondary ÿ practical use ÿ specific secondary ÿ practical use ÿ specific secondary

(Measure in the order of ÿ…) In addition to the method, measure multiple practical standard solutions after calibrating the pH meter with a specific secondary standard solution.

Finally, there is also a method of forming a batch for measuring a specific secondary standard solution for the purpose of confirmation. In that case, practical standard

In addition to the liquid, it is necessary to confirm that the measured value of the last specified secondary standard liquid also falls within a certain tolerance.

In that case, inThe standard uncertainty of tolerance judgment is evaluated as a rectangular distribution in which the one-sided width of 8a is doubled.

5-9 Composition of standard uncertainty: inc

in =
c

= 0.00505

5-10 Calculation of effective degrees of freedom: ÿ eff

The effective degree of freedom is calculated by the Welch-Satterthwaite formula.

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ÿ =
eff

ÿ ÿ

= 7746

5-11 Calculation of extended uncertainty: IN

k coefficient = 2 can be adopted. Therefore, the expansion IN teeth,

Since the effective degree of freedom is 7746, the inclusion
IN uncertainty is calculated as 0.004900.00505 × 2 = 0.011 (confidence level of about 95%).

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