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Estimation of Measurement Uncertainty in Determination of Chloride Ion in

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Estimation of Measurement Uncertainty in Determination
of Chloride Ion in Water by Mohr’s method

A. G. Piyal Aravinna*
Chemical and Environmental Research Laboratory
CECB Laboratory Services
Central Engineering Consultancy Bureau (CECB)
Sri Lanka.

August 2022

* A.G. Piyal Aravinna, Quality Manager

 piyalaravinna@yahoo.com, envlabcecb@gmail.com
 CECB Laboratory Services, 11, Jawatta Road, Colombo 50500, Sri Lanka

Technical Report –2022/QC1-Rev1

 Copyright and Disclaimer

© Central Engineering Consultancy Bureau (CECB), 2022. To the extent permitted

by law, all rights are reserved and no part of this publication covered by copyright
may be reproduced or copied in any form or by any means except with the written
permission of CECB.

Acknowledgments

Mr. K. Suranjith, Research Student, University of Sabarabamuwa, and the Technical

staff of Chemical and Environmental Research Laboratory, CECB are highly
appreciated for their involvement in taking measurements.

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 CONTENT

1 Methodology used in the estimation 4

2 Description of the test 4
2.1 Scope 4
2.2 Principle of the test method 4
2.3 Apparatus 4
2.4 Reagents 4
2.5 Procedure 5
2.6 Calculations 5
3 Measurements, calculations and results 7
4 Estimation of measurement uncertainty 8
4.1 Uncertainty of weighing NaCl 8
4.1.1 Sources of uncertainty 8
4.1.2 Standard uncertainty (u) in weighing, and method of estimation 8
4.1.3 Combined standard uncertainty in weighing NaCl 9
4.2 Uncertainty of purity of NaCl 9
4.3 Uncertainty of equivalent mass of NaCl 10
4.3.1 Combined standard uncertainty of equivalent mass of NaCl 10
4.4 Standard uncertainty in volume preparation of standard NaCl solution 11
4.4.1 Sources of uncertainty 11
4.4.2 Standard uncertainty (u) and method of estimation 11
4.4.3 Combined standard uncertainty of volume preparation of NaCl 13
4.5 Uncertainty in preparation of AgNO3 solution 13
4.6 Uncertainties associated with standardization of AgNO3 solution 13
4.6.1 Uncertainty in measuring NaCl solution for the standardization 13
4.6.2 Uncertainty in measuring AgNO3 solution (for standardization) 15
4.7 Uncertainty in measuring sample volumes 17
4.7.1 Sources of uncertainty and method of estimation 17
4.7.2 Standard uncertainty (u) and method of estimation 17
4.7.3 Combined standard uncertainty in measuring 50 mL of sample by bulb pipette 19

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 4.7.4 Combined standard uncertainty in measuring 25 mL of sample by bulb pipette 19

4.7.5 Combined standard uncertainty in the calculation of (𝑆 − ), uc(𝑆 − ) 19

4.8 Uncertainty in measuring AgNO3 volumes (𝑉 𝑎𝑛𝑑 𝑉 ) in titrating sample volumes 19

4.8.1 Sources of uncertainty 20
4.8.2 Standard uncertainty (u) and the method in estimation 20
4.8.3 Combined standard uncertainty in measuring 𝑉 from the burette, uc(𝑉 ) 20
4.8.4 Combined standard uncertainty in measuring 𝑉 from the burette, uc(𝑉 ) 20
4.8.5 Combined standard uncertainty in the calculation of (𝑉 − 𝑉 ) 20
4.9 Uncertainty in the determination of the endpoint 21
4.10 Summary of values of uncertainties 21
4.11 Calculating the combined standard uncertainty in the determination of chloride content 21
4.12 Coverage factor (k) 22
4.13 Expanded uncertainty of chloride content 22
5 Reporting results 22
6 References 23

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 Estimation of Measurement Uncertainty in Determination of Chloride Ion in Water

1 Methodology Used in the Estimation

Estimation of measurement uncertainty in determination of chloride ion in water was carried out
in accordance with Evaluation of Measurement Data (Guide to the expression of uncertainty in
measurement) [1].

2 Description of the Test

2.1 Scope

This test method covers the determination of chloride ions in water, wastewater, and brines. The
method has been validated for the concentration range from 8 to 250 mg L -1 of Cl− [2].

2.2 Principle of the test method

In this method, the chloride ion in the sample is titrated with standard silver nitrate solution (Reaction
1) with the presence of CrO42- ion as an indicator. Red-brown precipitate [Ag2CrO4] is formed at the
endpoint of titration (Reaction 2). The level of chloride ion in the samples is determined using a
standard silver nitrate solution.

Ag+(aq) + Cl-(aq) ⇌ AgCl(s) Reaction 1

2Ag+(aq) + CrO42-(aq) ⇌ Ag2CrO4(s) Reaction 2

If sulfite ions are present in the sample it is eliminated using hydrogen peroxide, and pH of the sample
is adjusted to 8.3 for the removal of interfering hydroxides.

2.3 Apparatus

 Analytical Balance capable of measuring 0.1 mg

 Burette (Grade A or Grade B, Capacity: 25 mL, with 0.01 mL graduation intervals)
 Bulb pipette (Grade A or Grade B, Capacities: 25 mL and 50 mL)
 Volumetric flasks (Grade A or Grade B, Capacity: 1 L, )

2.4 Reagents

 Hydrogen Peroxide (30 %)

 Sulfuric Acid Solution (1 + 19)
 Sodium Hydroxide Solution (10 g L-1)
 Phenolphthalein Indicator Solution (10 g L -1) [3]
 Potassium Chromate Indicator Solution[3]
 Sodium Chloride (Primary Standard Solution): 1.4613 g of Analytical Reagent (AR) grade
sodium chloride (NaCl) dried for 2 h at 110 °C is dissolved in water, and diluted to 1 L at 25 °C
in a volumetric flask.
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  Silver Nitrate (Standard solution): 4.2473 g of silver nitrate (AgNO3), died at 40 °C is dissolved
in water, and is diluted to 1 L. This solution is standardized against the standard NaCl solution
using the procedure described in Step 2 of Section 2.5.

2.5 Procedure

Step 1

A known volume of sample (S) is transferred into a conical flask. If sulfite ions are present, 0.5 mL of
hydrogen peroxide (30%) is added to the sample, mixed, and kept for 1 minute. The volume of the
sample is adjusted to 50 mL by using reagent water. the pH of the sample is adjusted to the
phenolphthalein endpoint (pH = 8.3) using phenolphthalein indicator (10 g L-1) and H2SO4, or NaOH
solution.

Step 2

Approximately 1.0 mL of K2CrO4 indicator solution is added to the sample prepared in Step 1. Then
the sample is titrated with standard AgNO3 solution until the brick-red (or pink) color persists, and
the volume of titrant is recorded (𝑉 ).

Step 3

The procedure described in Steps 1 and 2 is repeated for exactly one-half of the sample (Therefore,
the volume is ), and the volume of titrant required for the titration is recorded (𝑉 ).

2.6 Calculations

The concentration of chloride [Cl-] in the sample in mg L-1 is calculated as follows [2]:

( )× ×
[Cl ] = Equation 1

where,

𝑁 = The normality of the stranded AgNO3 solution,

𝑆 = The volume of sample used in Step 2,
𝑉 = The volume of standard AgNO3 solution added in titrating sample (S) in Step 2, and
𝑉 = The volume of standard AgNO3 solution added in titrating half of the sample ( ) in Step 3.

Since it is required to illustrate all sources of uncertainty, all measurements taken in the
determination of [Cl ] are incorporated into Equation 1, and It can be illustrated as follows:

( )× × ×
[Cl ] = Equation 2
( )

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 where,

= The volume of sample used in Step 3

𝐴𝑊 = Atomic mass of chloride

The normality ratio between Cl- and Ag+ is based on 1:1. Therefore, the normality of 𝑁 can be
expressed as follows:

𝑁 ×𝑉 ( .)
𝑁 = Equation 3
𝑉

where,

𝑁 = The normality of the standard NaCl solution,

𝑉 ( .) =The volume of standard NaCl solution, used for the standardization of AgNO 3, and
𝑉 = The volume of AgNO3 solution added in titrating standard NaCl solution.

Therefore, Equation 2 and Equation 3 can be combined as follows:

(𝑉 − 𝑉 ) × 𝐴𝑊 × 1000 𝑁 ×𝑉 ( .)
[Cl ] = × Equation 4
𝑆 𝑉
(𝑆 − )
2

𝑁 can be expressed as follows [4]:

𝑚
𝑀
𝑁 = Equation 5
𝑉

where,

𝑚 = Mass of 𝑁𝑎𝐶𝑙, used in preparation of normality solution,

𝑀 = Equivalent mass of NaCl, and
𝑉 =The volume of standard NaCl solution prepared (in liter)

The NaCl, used in preparation of standard NaCl solution is not 100% pure so that purity correction
has to be incorporated into the mass of NaCl. Therefore, the actual mass of NaCl (𝑚 ) in a
measured mass of NaCl (m) can be expressed as follows:

𝑚 .
= 𝑚×𝑃 Equation 6

where,

𝑃 = Percentage purity of NaCl, and

𝑚 = measured mass of NaCl (with the purity of 𝑃 )

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 Equation 5 and Equation 6 can be combined as follows:

𝑚×𝑃 1
𝑁 = × Equation 7
𝑀 𝑉

Therefore, from Equation 5, the chloride ion concentration in the water the sample[Cl ] can be
expressed as follows:

( )× × × ( .)
[Cl ] = × × × Equation 8
( )

3 Measurements, Calculations and Results

Measurements and data, used in the determination of [Cl ] in unknown water sample are given
in Table 1 and Table 2.

Concentrations of solutions, and level of Cl in the sample, calculated from direct data and
measurements are given in Table 3.

Table 1: Measurement taken in the analysis

Symbol/
Measurement Value
Abbreviation
Mass of 𝑁𝑎𝐶𝑙, used in preparation of normality solution 𝑚 1.4613 g
The volume of standard NaCl solution prepared 𝑉 1L
The volume of standard NaCl solution used for the standardization 𝑉 ( .) 25 mL
of AgNO3
The volume of AgNO3 solution added in titrating standard NaCl 𝑉 26.8 mL
solution
The volume of sample used in titration in Step 1 S 50 mL
The volume of sample used in titration in Step 2 𝑆 25 mL
2
The volume of standard AgNO3 solution added in titrating sample 𝑉 50 mL
in Step 2 (for sample volume S)
The volume of standard AgNO3 solution added in titrating sample 𝑉 25 mL
volume in Step 3 (for sample volume )

Table 2: Data used in the calculations

Symbol/
Parameter Value
Abbreviation
Purity of 𝑁𝑎𝐶𝑙, used in preparation of normality solution 𝑃 99.9 %
(from certificate of manufacturer)
Equivalent mass of NaCl [4] 𝑀 58.44 g/eq

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 Table 3: Calculations and results
Symbol/
Sample Titration Equation used Value
Abbreviation
Normality of the NaCl 𝑁 𝑚×𝑃 1 0.025 N
= ×
standard solution 𝑀 𝑉
Normality of the AgNO3 𝑁 𝑁 ×𝑉 ( .) 0.023 N
=
solution 𝑉
Level of chloride [Cl-] in the [Cl-] (𝑉 − 𝑉 ) × 𝑁 × 70906 234.8
=
sample 𝑆 mg L-1

4 Estimation of Measurement Uncertainty

Sources of uncertainty, standard uncertainty (u) and combined standard uncertainty (uc) of
measurement is described separately in the subsection below [5-7].

4.1 Uncertainty of weighing NaCl

4.1.1 Sources of uncertainty

Linearity and sensitivity and repeatability are sources of uncertainty in weight measurement
(Figure 1).

The uncertainty associated with linearity is estimated from the data of the calibration report of the
analytical balance used for the measurement. The sensitivity of the balance can be neglected
because the weight by difference is done on the same balance over a narrow range.

Figure 1: Cause and effect diagram showing uncertainty contributions in weighing

4.1.2 Standard uncertainty (u) in weighing, and method of estimation

Standard uncertainties of linearity and repeatability with method of estimation are given in Table 4.

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 Table 4: Standard uncertainties of weighing NaCl
Symbol of Value of
Sources of uncertainties standard Method of estimation standard
uncertainty uncertainty
a. Linearity (this has u(BL) u(BL)=B/z [8] ±0.000051 g
been considered in the where, B, the uncertainty of weighing of
calibration report). balance is extracted from the calibration
report of the balance (B =± 0.1 mg).
z, the z-score at 95% confidence coefficient
of normal probability distribution (1.96).
b. Repeatability u(BR) Repeated measurements of tare and gross of ±0.000175 g
(repeated weight a selected weight were taken for selected
measurements) mass within the range of 1.0 g to 2.0 g (Table
I, Appendix 1).

u(BR) = 𝑠 = ∑ (𝑚 − 𝑚)

Where

s is the standard deviation of weight

measurements, m is the value of individual
weight measurements taken, n is the number
of measurements taken. 𝑚 is the mean of
measurements.

4.1.3 Combined standard uncertainty in weighing NaCl

As per Rule 1, Appendix 2, the combined standard uncertainty in weighing NaCl, 𝑢 (𝑚) can be
expressed as follows:

𝑢 (𝑚) = u(BL(tare)) + u(BL(gross)) +u(R)

= (0.00051 + 0.00051 + 0.000175

= ± 0.000189401 g

4.2 Uncertainty of purity of NaCl, u(PNaCl)

The supplier has provided the purity of NaCl in its certificate of analysis, and it is used to estimate
the standard uncertainty purity of NaCl, u(PNaCl) and details are given in Table 5

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 Table 5: Standard uncertainty of purity of NaCl
Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Purity of sodium u(PNaCl) The supplier quotes the purity of the sodium chloride ±0.00058%
chloride in its certificate of analysis as 99.9 ±0. 1% (P=0.999
±0.001) without mentioning its degree of confidence.

As there is no idea of the confidence limited of this

purity, the standard uncertainty of purity is taken
from the rectangular distribution as given below.

u(PNaCl)=
√
where

𝑠 = uncertainty of the purity (±0.001%)

4.3 Uncertainty of equivalent mass of NaCl

There is an uncertainty in the determination of individual atomic weight. Uncertainty of atomic

weights of elements, published by the IUPAC [9-10] is used to estimate the standard uncertainties of
atomic masses Na and Cl. Standard uncertainties with the method of estimation are given in
Table 6.

Table 6: Standard uncertainties of atomic weight

Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
The atomic 𝑢(𝐴𝑊 ) As given in Table II, Appendix 1.
weight of Na
The standard uncertainty of Atomic weight is ±0.000001 g
taken from the rectangular distribution as given
below.
u(AW) = √
The atomic 𝑢(𝐴𝑊 )
weight of Cl where
s, Standard Deviation of atomic weights: ±0.000520 g

4.3.1 Combined standard uncertainty of equivalent mass of NaCl

As per Rule 1, Appendix 2, the combined standard uncertainty of equivalent mass of

NaCl, 𝑢 (𝑀 ) can be expressed as follows:

𝒖𝒄 (𝑀 )= u(𝐴𝑊 ) + u(𝐴𝑊 )

= 0.000001 + 0.000520

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 = ±0.000519617 g

4.4 Standard uncertainty in volume preparation of standard NaCl solution

4.4.1 Sources of uncertainty

Standard NaCl solution is prepared in 1 L volumetric flask. Therefore, major sources of uncertainties
associated with volume preparation are (Figure2); Volume of the volumetric flask used (at the time
of manufacturer’s volume calibration), Repeatability of volume measurements (uncertainty in filling
up to the volume designated), and Volume expansion due to temperature variation (from the
temperature of the manufacturer’s calibration).

Figure 2: Cause-and-Effect Diagram of the uncertainty of volume measurements

4.4.2 Standard uncertainty (u) and method of estimation

Standard uncertainties of; the volume of the volumetric flask, repeatability of volume, and volume
expansion with their methods of estimation are reported in Table 7.

Table 7: Standard uncertainties of volume preparation in volumetric flask

Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Uncertainty of u(VF,V,1L) The manufacturer’s catalog states that the 1 L
the volume of flask comes with an uncertainty of ± 0.400 mL
the volumetric without mentioning the degree of confidence. So
flask used the standard uncertainty of the volume of flask is
taken from the rectangular distribution as given
below.
±0.00023094 L
u(VF,V,1L)=
√
where

s, the uncertainty of the volume of the flask (±

0.400 mL)

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 Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Uncertainty in u(VF,R,1L) The standard deviation volume of filling of the
filling up to the volumetric flask is calculated from a series of
volume replicated filling and weighing of water to mark.
designated The volume of each measurement is calculated
from the mass and density relationship (Volume =
Mass/Density). Data is given in Table III, Appendix
1.

±0.0000426 L
u(VF,R,1L) = 𝑠 = ∑ (𝑣 − 𝑣)

Where
s is the standard deviation of volume
measurement, 𝑣 is the value of individual volume
estimated (using the relationship “Volume =
Mass/Density”), n is the number of
measurements taken, and 𝑣 is the mean of
measurements.
Volume u(∆VF,T,1L) According to the manufacturer, the flask has been
expansion due calibrated at 20 °C. But laboratory temperature is
to temperature 25 °C. Therefore, the volume expansion of the
variation from solution (∆V) is calculated from the formula given
the below
manufacturer
calibration. ∆V = V0×β×∆T = 0.00105 L
mL

where,
V0 = Initial volume of the solution (1 L)
β = Coefficient of volume expansion for water (2.1
× 10-4 °C -1)
±0.000535714 L
∆T = temperature change (5 °C)

(Assumption: Coefficient of volume expansion for

water is considerably greater than that of the
volume expansion of flask made of glass)

Confidence level of
Volume measurement due to temperature factor
is 95%.

u(∆VF,T,1L)= ∆V /z
Where,
z is teh z-score at 95% confidence coefficient of
normal probability distribution (z=1.96).

Technical Report –2022 /QC1

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 4.4.3 Combined standard uncertainty in volume preparation of NaCl

As per Rule 1, Appendix 2, the combined standard uncertainty in volume preparation of NaCl,
uc(𝑉 ) can be expressed as follows:

uc (𝑉 )= u(VF,R,1L) + u(VF,R,1L) +u(∆VF,T,1L)

= 0.00023094 + 0.0000426 + 0.000535714 = ±0.000584926 mL

4.5 Uncertainty in preparation of AgNO3 solution

AgNO3, a secondary standard is used to determine the level of chloride in the sample. As AgNO 3 is
standardized against the primary standard (standard NaCl solution), the uncertainty of the
measurements taken in preparation of AgNO3 solution does not affect the results. Therefore, the
uncertainties of those measurements are neglected.

4.6 Uncertainties associated with standardization of AgNO3 solution

A known volume of standard NaCl solution (25 mL), measured by bulb pipette is titrated with
AgNO3 solution (from the Burette), those measurements are taken accurately. Therefore, relevant
uncertainties affect the results.

4.6.1 Uncertainty in measuring NaCl solution for the standardization

a) Sources of uncertainty

Standard NaCl solution is taken from 25 mL-bulb pipette. Therefore major sources of uncertainties
associated with volume preparation are; a) the volume of the bulb pipette used (at the time of
manufacturer’s volume calibration), b) repeatability of volume measurements (uncertainty in filling
up to the volume designated, and c) volume expansion due to temperature variation (from the
manufacture calibration). Cause-and-Effect Diagram shown in Figure 2 can be used to illustrate the
sources of uncertainty in volume preparation.

b) Standard uncertainty (u) and method of estimation

Standard uncertainties of; the volume of the pipet, repeatability of volume, and volume expansion
with their methods of estimation are reported in Table 8.

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 Table 8: Standard uncertainties in measuring volume from bulb pipette
Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Uncertainty of 𝑢(VP,V,25mL) The pipette manufacturer states that the pipette used ±0.01732051
the volume of has an uncertainty of ± 0.03 mL. Therefore, the mL
the pipette (25 standard uncertainty of the volume of the pipette is
ml) used taken from the rectangular distribution as given below.

u(VP, F25 mL)=

√

where
s, uncertainty of the volume of the pipette (± 0.03)
Uncertainty in u(VP,R, 25mL) The standard deviation for the variation of the total ±0.03186353
the filling of volume of the pipette is calculated from a series of mL
the pipette to replicated filling and weighing of water to mark. The
25 mL volume of each measurement is calculated from the
mass and density relationship (Volume =
Mass/Density). Data is given in Table IV, Appendix 1.
u(VP,R, 25mL) 𝑠 = ∑ (𝑣 − 𝑣)
s is the standard deviation of volume measurement, v
is the value of individual volume estimated (using the
relationship “Volume = Mass/Density”), n is the
number of measurements taken, and 𝑣 is the mean of
measurements.
Volume u(∆VP,T, 25 mL) According to the manufacturer, pipette has been ±0.01339286
expansion due calibrated at 20 °C. mL
to But laboratory temperature is 25 °C. Therefore, the
temperature volume expansion of the solution (∆V) is calculated
variation from from the formula given below
the
manufacture ∆V = V0×β×∆T = 0.02625 mL
calibration.
Where
V0 =Initial volume of the solution (25 mL)
β = Coefficient of volume expansion for water (2.1 ×
10-4 °C -1)
∆T = temperature change (5 °C)
(Assumption: Coefficient of volume expansion for
water is considerably greater than that of the volume
expansion of pipette made of glass)

The confidence level of volume measurement due to

the temperature factor is 95%.

u(∆VP,T, 25 mL)= ∆V/z

Where,
z is the z-score at 95% confidence coefficient of
normal probability distribution (1.96).
Technical Report –2022 /QC1
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14
 c) Combined standard uncertainty in measuring NaCl standard solution for standardization

As per Rule 1, Appendix 2, the combined standard uncertainty in measuring NaCl standard solution for
standardization, uc(𝑉 ( .) ) can be expressed as follows:

uc(𝑉 ( .) ) = u(VP, V, 25mL) + u(VP, R, 25mL ) + u(∆VP,T,25mL)

= 0.017320508 + 0.031863527 + 0.013392857) = ±0.038660742 mL

4.6.2 Uncertainty in measuring AgNO3 solution (for standardization)

a) Sources of uncertainty

AgNO3 solution is added to standard NaCl solution by 25 mL-burette. Therefore, major sources of
uncertainties associated with measuring volume from burette are; a) volume measurement of
burette used (at the time of manufacturer’s volume calibration), b) repeatability of volume
measurements (uncertainty in filling-up/running rundown), and c) volume expansion due to
temperature variation (from the temperature of the manufacturer's calibration). Cause-and-Effect
Diagram shown in Figure 2 can be used to illustrate the sources of uncertainty in volumetric
measurement.

b) Standard uncertainty (u) and method of estimation

Standard uncertainties of; the volume of the burette, repeatability of volume, and volume expansion
with their methods of estimation are reported in Table 9.

Table 9: Standard uncertainties in measuring burette reading of AgNO3 solution

Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Uncertainty u(VB,V,25 mL) The manufacturer states that the burette used
of the has an uncertainty of ± 0.030 mL. In the
Burette glassware certification process, the nominal
reading (25 value is more likely than the extremes.
mL) Therefore, triangular distribution is better
than the rectangular one in the estimation of ±0.012247449
uncertainty of the burette reading as follows: mL

u(VB,V,25 mL) =
√
where
s, the uncertainty of the volume of the
burette (± 0.030 mL)

Technical Report –2022 /QC1

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 Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Uncertainty in u(VB,R,25 mL) The standard deviation of volume of the 25
filling and mL-burette is calculated from a series of filling
draining a of water to mark, draining and weighing. The
known volume volume of each measurement is calculated
from the
from the mass and density relationship
burette
(Volume = Mass/Density). Table V, Appendix
1.

±0.050539799
u(VB,R,25 mL) = 𝑠 = ∑ (𝑣 − 𝑣)
mL
where

s is the standard deviation of volume

measurement, 𝑣 is the value of individual
volume estimated (using the relationship
“Volume = Mass/Density”), n is the number of
measurements taken, and 𝑣 is the mean of
measurements.
Volume u(∆VB,T,25mL) According to the manufacturer, the burette
expansion has been calibrated at 20 °C. But laboratory
due to temperature is 25 °C. Therefore, the volume
temperature expansion of the solution (∆V) is calculated
variation from the formula given below;
from the
manufacturer ∆V = V0×β×∆T = 0.026 mL
calibration.
where
V0 =Initial volume of the solution (25 mL)
β = Coefficient of volume expansion for water
(2.1 × 10-4 °C -1) ±0.013392857
∆T = temperature change (5 °C) mL
(Assumption: Coefficient of volume expansion
for water is considerably greater than that of
the volume expansion of Burette made of
glass).
The confidence level of volume measurement
due to the temperature factor is 95%.

u(∆VP,T, 25 mL)= ∆V/z

where,
z is the z-score at 95% confidence coefficient
of normal probability distribution (1.96).

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 c) Combined standard uncertainty in measuring AgNO3 volume for standardization

Burette reading = Initial volume – final volume.

When the volume is measured from the burette, the burette reading is taken on two occasions so
that the uncertainty of the burette reading [u(VB,V,25mL)] has to be considered on two occasions in the
estimation.

Therefore, as per Rule 1, Appendix 2, the combined standard uncertainty in measuring titrated
AgNO3 volume from the burette for standardization, uc(𝑉 ) can be expressed as follows:

uc(𝑉 ) = 2×u(VB,V,25mL) + u(VB,R,25mL) + u(∆VB,T,25mL)

= 2×(0.012247449 ) + 0.050539799 + 0.013392857 = ±0.055078488 mL

4.7 Uncertainty in measuring sample volumes

4.7.1 Sources of uncertainty

As described in Step 1 and Step 2 of the method, sample volumes of 50 mL ( therefore, S =50 mL)
and 25 mL (S =25 mL) are measured using 50 mL and 25 mL bulb pipettes, respectively.

As bulb pipettes are used for the measurements, sources of uncertainty are similar to the sources
that are already described in Section 4.6.1.

4.7.2 Standard uncertainty (u) and method of estimation

As bulb pipettes are used for the measurements, the method of estimation of uncertainty in
measuring the volumes of sample is similar to the method which was described in Section 4.6.1.

Standard uncertainty in measuring sample volumes with the method of estimation, in brief, is
reported in Table 10.

Table 10: Standard uncertainties in measuring sample volumes from bulb pipettes
Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Measuring 50 mL sample
Uncertainty of u(VP,V, 50 mL) The method of estimation has already been
the volume of described in Table 8.
the pipette (50
ml) used ±0.028867513
u(VP, F 50 ml)=
√ mL
where
s, the uncertainty of the volume of the pipette (±
0.03)
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 Symbol of Value of
Sources of
standard Method of estimation standard
uncertainties
uncertainty uncertainty
Uncertainty in u(VP,R,50 mL) The method of estimation has already been
the filling described in Table 8, and relevant data is given
pipette to 50 in Table VI, Appendix 1.
mL
±0.028473054
u(VP,R,50 mL)= s
mL
where, s is the standard deviation of the
measurements. n is the number of
measurements
Volume u(∆VP T, 50 mL) The method of estimation has already been
expansion due described in Table 8.
to
temperature ∆V = V0×β×∆T = 0.0525 mL
variation from
the where
manufacturer V0 =Initial volume of the solution (50 mL)
calibration. β = Coefficient of volume expansion for water
(2.1 × 10-4 °C -1) ±0.026785714
∆T = temperature change (5 °C) mL

The confidence level of volume measurement

due to the temperature factor is 95%.

u(∆VP T, 50 mL)= ∆V/z

Where,
z is the z-score at 95% confidence coefficient of
normal probability distribution (1.96).
Measuring 25 mL sample
Uncertainty of 𝑢(VP,V,25mL) The method of estimation has already been ±0.017320508
the volume of described in Table 8. mL
the pipette (25
mL) used
Uncertainty in u(VP,R, 25mL) ±0.031863527
the filling of mL
the pipette to
25 mL
Volume u(∆VP,T, 25 mL) ±0.013392857
expansion due mL
to
temperature
variation from
the
manufacturer
calibration.

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 4.7.3 Combined standard uncertainty in measuring 50 mL of sample by bulb pipette

As per Rule 1, Appendix 2, the combined standard uncertainty in measuring 50 mL of sample by bulb
pipette, uc(𝑆) can be expressed as follows:

uc(𝑆)= u(VP,V,50mL) + u(VP,R,50mL ) + u(∆VP,T,50mL)

0.028867513) + 0.028473054) + 0.026785714) = 0.0485955

4.7.4 Combined standard uncertainty in measuring 25 mL of sample by bulb pipette

As described in Section 4.7.3, the combined standard uncertainty in measuring 25 mL of sample by

bulb pipette, uc ( ) can be expressed as follows:

uc( ) = u(VP, 25 ml) + u(VP, R 25 ml) + u(∆VT, 25 mL)

= 0.017320508 + 0.031863527 + 0.013392857) = ± 0.038660742 mL

As the analyst uses another 25 mL-bulb pipette for the measurement of sample volume, the
combined standard uncertainty in measuring 25 mL of the sample by bulb pipette, u(VP, R 25 ml) is
aging applied for the estimation in uc( ) in this section without considering the estimation previously
taken into consideration in Part C of the Section 4.6.1.

𝑺
4.7.5 Combined standard uncertainty in the calculation of (𝑺 − )
𝟐

Combined standard uncertainty in the calculation of 𝑆 − , uc(𝑆 − ) can be expressed as follows:

uc(𝑆 − ) = 𝑢 (𝑆) + 𝑢 ( )

= 0.0485955 + 0.03866074 = 0.062098113 mL

4.8 Uncertainty in measuring AgNO3 volumes (𝑽𝟏 𝒂𝒏𝒅 𝑽𝟐 ) in titrating sample volumes

The volume of standard AgNO3 solution added in titrating sample volumes of 50 mL (S) and 25 mL
( ) are 𝑉 and 𝑉 , respectively. All burette measurements are taken from the same burette used in
Section 4.6.2.

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 4.8.1 Sources of uncertainty

The same burette is used in titrating both the standard solution and the sample. Therefore, sources
of uncertainty are similar to which was described in section 4.6.2.

4.8.2 Standard uncertainty (u) and the method in estimation

The same burette is used in titrating both the standard solution and the sample. Therefore, standard
uncertainties, methods of estimation, and values of uncertainties are similar to the methods and
their values that were described in Section 4.6.2. However, the volumes measured in titrating
samples may be varied as per the levels of chloride in the samples. Therefore, the maximum burette
volume is considered for the V0 ( in Table 9) to estimate the uncertainty of thermal expansion.

4.8.3 Combined standard Uncertainty in measuring 𝑽𝟏 from the burette

As per Rule 1, Appendix 2, the combined standard uncertainty in measuring 𝑉 from the burette,
uc(𝑉 ) can be expressed as follows:

uc(𝑉 ) = 2×u(VB,V,25mL) + u(VB,R,25mL) + u(∆VB,T,25mL)

The same burette (which is used in the standardization of NaCl) is used in titrating samples.
Therefore, u(VB,R,25mL) is already adopted in the estimation, therefore this component is removed
from the formula above.

Therefore,

uc(𝑉 ) = 2×u(VB,V,25mL) + u(∆VB,T,25mL)

2×(0.012247449 ) + 0.013392857 = ±0.021894488 mL

4.8.4 Combined standard uncertainty in measuring 𝑽𝟐 from the burette

This calculation is similar to the method of combining standard uncertainties in Section 4.8.3.
Therefore, combined standard uncertainty in measuring 𝑉 from the burette, uc(𝑉 )

uc(𝑉 ) = uc(𝑉 )= 0.021894488

4.8.5 Combined standard uncertainty in the calculation of (𝑽𝟏 − 𝑽𝟐 )

Combined standard uncertainty in the calculation of (𝑉 − 𝑉 ), uc(𝑉 − 𝑉 ) can be expressed as

follows:

uc(𝑉 − 𝑉 ) = 2 × 𝑢 (𝑉 )

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 2 × 0.021894488 = 0.021894488 mL

4.9 Uncertainty in the determination of the endpoint

When Cl- ion is reacted with Ag+ ion in the titration , clear white precipitate is formed in the conical
flask, and red-brown precipitate [Ag2CrO4] is formed at the endpoint of the titration. Therefore, the
colour change at the endpoint is from white to Red-brown, and it is easily identified by the analyst
by adding one drop (0.05 mL) of AgNO3 from the burette (Reaction 2). Therefore, considering
rectangular distribution, the standard uncertainty in determination of the endpoint, uc(𝑉 ) can be
expressed as below.

.
𝑢(𝑉 ) = = = ±0.028867513 mL
√ √

where,

s is the volume of a drop of AgNO3 from the pipette (±0.05 mL)

However, the uncertainty in the determination of the endpoint is already included in the combined
standard uncertainty in measuring volume from the burette. Therefore, it is not reconsidered.

4.10 Summary of values of uncertainties

Summary of the measurements, their standard uncertainties, and combined standard uncertainties
are summarized in Table 11

Table 11: Summary of values of uncertainties

Parameter (x) The uncertainty u(X) 𝒖(𝑿) 𝐮(𝑿)
𝟐

Symbol Value* Symbol Value 𝐮 (𝑿) 𝑿 𝑿

𝑚 1.4613 u (𝑚) 0.000189 0.000130 0.00000002
𝑃NaCl 99.9 𝑢 (𝑃NaCl) 0.000577 0.000006 0.00000033
𝑀 58.44 u (𝑀 ) 0.000520 0.000009 0.0000000001
𝐴𝑊 35.453 u (𝐴𝑊 ) 0.00052 0.000015 0.0000000002
𝑉 1 u (𝑉 ) 0.000585 0.000585 0.00000034
𝑉 ( .) 25 u 𝑉 ( .) 0.038661 0.001546 0.00000239
𝑉 26.8 u 𝑉 0.055078 0.002055 0.00000422
𝑆 25 𝑆
𝑆− 𝑢 𝑆− 0.00000617
2 2 0.062098 0.002484
𝑉 − 𝑉 25 𝑢 (𝑉 − 𝑉 ) 0.030963 0.001239 0.00000153
* Values without units

4.11 Calculating the combined standard uncertainty in the determination of chloride content

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 The chloride content of the sample can be expressed by the simple multiplicative expression in
Equation 8. Since the model involves only a product or quotient, Rule 2 (Appendix 2), can be applied
in the estimation of combined standard uncertainty.

Therefore, the combined uncertainty in the determination of chloride content in the sample,
uc([𝐶𝑙 ]) can be expressed as follows:

⃓
⃓ 𝑢 (𝑚 ) 𝑢 (𝑃NaCl) 𝑢 (𝑀 ) 𝑢 (𝐴𝑊 ) 𝑢 (𝑉 )
⃓ + + + +
⃓
⃓ 𝑚 𝑃NaCl 𝑀 𝐴𝑊 𝑉
⃓
⃓
([ ])
= ⃓ 𝑆
⃓ 𝑢 𝑉 ( .) 𝑢 𝑉 𝑢 𝑆− 𝑢 (𝑉 − 𝑉 )
[ ] ⃓ + + 2 +
⃓
⃓ 𝑆
⃓ 𝑉 ( .) 𝑉 𝑆− (𝑉 − 𝑉 )
⃓
⃓ 2
⎷

([ ])
[ ]
= 0.00387456

𝑢 ([𝐶𝑙 ]) = [Cl ] ×0.00387456

The chloride level of the sample is 234.81 mg L-1.

Therefore,

𝑢 ([𝐶𝑙 ]) = 234.81 ×0.00387456 = ± 0.9098 mg L-1

4.12 Coverage factor (k)

It is considered most of the measurements are reported at level of confidence of approximately

95%. Therefore, coverage factor of 2 (k=2) is used to calculate expanded uncertainty.

4.13 Expanded uncertainty of chloride content

As per the relationship given in the Appendix 2, the expanded uncertainty in determination of
chloride content, U[𝐶𝑙 ] can be expressed as follows:

U[𝐶𝑙 ] = 𝑢 ([𝐶𝑙 ]) × 𝑘

= 0.9098 × 2 = ± 1.82 mg L-1

5 Reporting Results

Chloride content of water (tested in accordance with ASTM D512-10) is 234.8 mg L -1 ± 1.8 mg L-1
with a coverage factor of 2 (k=2)

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 6 References

1. Evaluation of measurement data - Guide to the expression of uncertainty in measurement

(JCGM 100:2008), Joint Committee for Guides in Metrology (JCGM), 1 St ed, 2008.

2. Standard Test Methods for Chloride Ion In Water (ASTM D512 – 12), American Society for
Testing and Materials (ASTM), 2012

3. Standard Practice for Preparation, Standardization, and Storage of Standard and Reagent
Solutions for Chemical Analysis (ASTM E200 – 08), American Society for Testing and Materials
(ASTM), 2012

4. Jeffery, G. H., Bassett, J., Mendham, J. Denney, R. C., Eds., (1989). Vogel’s textbook of
quantitative chemical analysis, 5th ed. New York: John Wiley & Sons.

5. Multi-Agency Radiological Laboratory Analytical Protocols Manual, USEPA, USDOD, USDOE,

USDHS, USNRC, USFDA, USGS and USNIST, Volume I: Chapters 10 - 17 and Appendix F, July
2004.

6. Aravinna, A.G.P., Basic Concepts of Measurement Uncertainty, Technical report, CECB

Laboratory Technical Awareness Program, CECB, March 2018.

7. De Silva G.H.S., Aravinna, A.G.P and , Estimation of Measurement Uncertainty in

Determination of Water (Moisture) Content of Soil and Rock by Mass (Test Method: ASTM
D22I6 -10), Technical report, CECB laboratory Services, CECB, November 2019.

8. A Guide on Measurement Uncertainty in Chemical & Microbiological Analysis, Technical Guide

2, SAC-SINGLAS Technical Guide, SPRING Singapore, 2 Bukit Merah Central,
159835,Singapore, 2nd Edition, March 2008.

9. Coplen, Tyler B., Holden, Norman E., Ding, Tiping, Meijer, Harro A. J., Vogl, Jochen, and Zhu,
Xiangkun. The Table of Standard Atomic Weights—an exercise in consensus. Nuclear Science
and Technology Department, Brookhaven National Laboratory, U.S. Department of Energy,
United States: May 2020.

10. Uncertainty of atomic weights of elements, IUPAC Journal of Pure and Applied Chemistry, vol.
69, pp. 2471-2473 (1997).

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 APPENDIX 1

Table I: Repeatability measurements of analytical balance

Balance repeatability
Measurement no Value(𝒎) /g
1 1.4618
2 1.4617
3 1.4616
4 1.4615
5 1.4615
6 1.4616
7 1.4613
8 1.4613
9 1.4613
10 1.4616
Number of measurements (n) 10
Sum(∑ 𝑚) 14.6152
Mean(𝑚) 1.46152
Standard deviation (s) ± 0.000175

Table II: Individual atomic weight of Cl and Na and associated uncertainty

Element Atomic weight/(g mol-1) Uncertainty quoted/(g mol-1)
Sodium (Na) 22.98977 ± 0.000002
Chlorine (Cl) 35.4527 ± 0.0009
Calcium (Ca) 40.078 ± 0.004
Carbon (C) 12.0107 ± 0.0008
Oxygen (O) 15.9994 ±0.0003
Source: Uncertainty of atomic weights of elements published by the IUPAC Journal of Pure and
Applied Chemistry, vol. 69, pp. 2471-2473 (1997).

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 Table III: Repeatability measurements volume (filling) of 1 L volumetric flask
Weight of the flask Weight of the empty Mass of 1 L of
Measurement Volume(𝒗)*
with water flask water
No. /L
/g /g /g
1 1222.50 228.47 994.03 0.996891
2 1222.54 228.47 994.07 0.996931
3 1222.55 228.47 994.08 0.996941
4 1222.57 228.47 994.10 0.996961
5 1222.53 228.47 994.06 0.996921
6 1222.50 228.47 994.03 0.996891
7 1222.62 228.47 994.15 0.997011
8 1222.59 228.47 994.12 0.996981
9 1222.49 228.47 994.02 0.996881
10 1222.57 228.47 994.10 0.996961
Number of measurements (n) 10
Sum(∑ 𝑣) 19.96937
Mean(𝑣) 0.996937
Standard deviation (s) ±0.0000426
* 𝑣 = 𝑚/𝑑, where 𝑑 = density of water, 𝑑 at 25 °C is 997.13 g L-1

Table IV: Repeatability measurements volume (filling and draining) of 25 mL-volumetric pipette
Mass of 25 mL of water drained
Volume(𝒗)*
Measurement No. from the pipette
/mL
/g
1 24.9278 24.9995
2 24.9052 24.9769
3 24.8665 24.9381
4 24.9795 25.0514
5 24.8820 24.9536
6 24.9163 24.9880
7 24.8888 24.9604
8 24.9056 24.9773
9 24.8839 24.9555
10 24.8920 24.9636
Number of measurements (n) 10
Sum(∑ 𝑣) 259.7644
Mean(𝑣) 24.9764
Standard deviation (s) ±0.031864
* 𝑣 = 𝑚/𝑑, where 𝑑 = density of water, 𝑑 at 25 °C is 997.13 g L-1

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 Table V: Repeatability measurements volume (filling & draining) of 25 mL-burette
Mass of 25 mL of water
Volume(v)*
Measurement No. measured from the burette
/mL
/g
1 24.8301 24.7588
2 24.9119 24.8404
3 24.9015 24.8300
4 24.8830 24.8116
5 24.8737 24.8023
6 24.8024 24.7312
7 24.9583 24.8867
8 24.8254 24.7542
9 24.9181 24.8466
10 24.8251 24.7539
Number of measurements (n) 10
Sum(∑ 𝑣) 258.0156
Mean(𝑣) 24.8016
Standard deviation (s) ±0.05054
* 𝑣 = 𝑚/𝑑, where 𝑑 = density of water, 𝑑 at 25 °C is 997.13 g L-1

Table VI: Repeatability measurements volume (filling & draining) of 50 mL-volumetric pipette
Mass of 50 mL of water drained
Volume(v)*
Measurement No. from the pipette
/mL
/g
1 49.8029 49.6600
2 49.7984 49.6555
3 49.7182 49.5755
4 49.7650 49.6222
5 49.8049 49.6620
6 49.7866 49.6437
7 49.7550 49.6122
8 49.7440 49.6012
9 49.7748 49.6319
10 49.7924 49.6495
Number of measurements (n) 10
Sum(∑ 𝑣) 506.3137
Mean(𝑣) 49.6314
Standard deviation (s) ±0.028473
* 𝑣 = 𝑚/𝑑, where 𝑑 = density of water, 𝑑 at 25 °C is 997.13 g L-1

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View publication stats

APPENDIX 2

Expression of Combined Standard Uncertainty

The general relationship between the combined standard uncertainty uc(y) of a value y and the
uncertainty of the independent parameters x1, x2,...xn on which it depends is

Where, y(x1,x2,..) is a function of several parameters x1,x2..., ci is a sensitivity coefficient evaluated as

ci=∂y/∂xi, the partial differential of y with respect to xi , and u(y,xi) denotes the uncertainty in y arising
from the uncertainty in xi. Each variable's contribution u(y,xi) is just the square of the associated
uncertainty expressed as a standard deviation multiplied by the square of the relevant sensitivity
coefficient. These sensitivity coefficients describe how the value of y varies with changes in the
parameters x1, x2 etc.

In some occasions, the expressions of combining uncertainties reduce to simpler Forms. Two simple
rules for combining standard uncertainties are given below.

Rule 1

For models involving only a sum or difference of quantities of input quantities p,q, … [therefore, y =
k(p+q+...), the combined standard uncertainty, uc (𝑦(𝑝, 𝑞 … )) is given by:

uc (𝑦(𝑝, 𝑞 … )) = k u(p) + u(q) + ⋯

Where k is constant, u(p) and u(q) are uncertainties of the input estimates of p and q, respectively

Rule 2

For models involving only a product or quotient, p,q, … [therefore , y = k (pq...) or y= k (p/q...)], the
combined standard uncertainty uc(y) is given by:

( ) ( )
uc(𝑦 )/y = k + +⋯

where k is constant, u(p) and u(q) are uncertainties of the input estimates of p and q, respectively.

Expanded uncertainty (U)

U=𝑢 ×𝑘

Where, u and k are combined standard uncertainty and coverage factor, respectively.
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