Slovak Institute of Metrology

Karloveská 63, SK-842 55 Bratislava 4, Slovakia

Key comparison CCQM-K34.2

Assay of potassium hydrogen phthalate
Final report

Michal Máriássy,
Alena Skutina (UNIIM), Paulo Paschoal Borges (INMETRO)

Bratislava, June 2009

Slovak Institute of Metrology Final report of CCQM-K34.2 Page 2/12

Abstract
The CCQM-K34.2 key comparison was organised as a subsequent key comparison to CCQM-
K34 Assay of Potassium Hydrogen Phthalate to demonstrate the new and improved capability of
INMETRO and UNIIM, resp., to measure the amount content of acid in potassium hydrogen
phthalate. The key comparisons and the previous pilot study CCQM-P36 were organised jointly
by the working groups of inorganic analysis and electrochemistry analysis. All participants used
high-accuracy constant current coulometry for measurement. The agreement of the results was
very good. Slovak Institute of Metrology acted as the coordinating laboratory and served as
a link to the reference value of CCQM-K34.
Slovak Institute of Metrology Final report of CCQM-K34.2 Page 3/12

1 INTRODUCTION
The CCQM-K34.2 subsequent key comparison “Assay of Potassium Hydrogen Phthalate” was
proposed and approved at the April 2008 CCQM Inorganic and Electrochemical Analysis
Working Group meetings in Paris as a follow-up for the CCQM-K34 [1] and CCQM-K34.1 [2].
UNIIM has improved its procedure used in CCQM-K34 and wanted to have its better
performance confirmed by a key comparison. Additionally INMETRO after having recently
acquired this capability wanted to benchmark it.

Scope of the comparison:

The scope is the same as in CCQM-K34 and CCQM-K34.1. The comparison tested the
capabilities and methods used for assay of high purity materials. For coulometric methods, good
results indicate good performance in assaying both strong and weak solid acids.

2 LIST OF PARTICIPANTS

The participating NMIs and contact persons are given in Table 1.

Table 1 List of participants

Institution Country Contact person
INMETRO Brasil Paulo P. Borges
Instituto Nacional de Metrologia, Normalização e Qualidade
Industrial
UNIIM Russia Alena Skutina
The Ural Research Institute for Metrology
SMU Slovakia Michal Máriássy
Slovak Institute of Metrology

3 SAMPLES

An UNIIM material was used for comparison. The material was sieved through plastic sieves
and the major fraction was homogenised in a large bottle and filled into 5 glass bottles. The
bottles were tested for homogeneity by analysing three bottles in triplicate by coulometry. Data
were treated using ANOVA one-way analysis [3]. The results indicate that the between bottle
variation is negligible compared to the repeatability of the measurement.
The samples were sent from UNIIM to INMETRO and SMU on September 5, 2008 by DHL.
The samples arrived to their destination without damage on Sept 11 (SMU) and Sept 17
(INMETRO).

4 INSTRUCTIONS TO PARTICIPANTS

The instructions sent to the participants by e-mail consisted of technical protocol and results
report form.
Slovak Institute of Metrology Final report of CCQM-K34.2 Page 4/12

The technical protocol contained background information, timing of the comparison, and
information on the participating institutes (Appendix 1). Information on sample homogeneity
and sample preparation for measurements was given. The participants were free to choose the
measurement procedure. Some possible problems with measurement were highlighted.
Participants were requested the results as amount content of acid and to provide uncertainty
evaluation according to GUM [4].
The results report form contained entries relating to the measurement results, detailed uncertainty
evaluation and description of the measurement procedures.
The deadline for reporting results was set to 31 December 2008 so that draft A report can be
prepared for discussion at the CCQM WG meeting in April 2009. All participants reported their
results in time.

5 METHODS OF MEASUREMENT

The methods of measurement were left free to be selected by the participating institutes. The
potential pitfalls for different methods were mentioned in the protocol. They included significant
interference of carbon dioxide (the pH of the solution is alkaline during the final titration) for
volumetric and coulometric titrations. For coulometric titration, there is in addition the
possibility of electrochemical reduction yielding low results. Indirect methods had to take into
account the dependence of the assay on the H/K (or other metals) ratio and the water content.
All participants used coulometric titration for assay determination. Some information on the
measurements are given in Appendix 2.

6 RESULTS AND DISCUSSION

The reported values and uncertainties are summarised in Table 2 and also displayed graphically
in Figure 1.

Table 2 Results (amount content of weak acid, combined standard uncertainty, relative
combined standard uncertainty, relative standard deviation and number of
measurements)

Result uC,
Institute Measurement date uC,r RSD n
/mol.kg-1 /mol.kg-1

INMETRO Sept 30 – Oct 3, 2008 4,89643 0,00018 0,0036% 0,0043% 4

UNIIM Nov 12 – Dec 22, 2008 4,89656 0,00034 0,0070% 0,0082% 7

SMU Sept 30 – Oct 30, 2008 4,89683 0,00015 0,0031% 0,0009% 6

There is good agreement among the results.

Slovak Institute of Metrology Final report of CCQM-K34.2 Page 5/12

Results of CCQM-K34.2
(standard uncertainty shown)
Amount content /mol.kg -1

4,8972 100,011%
4,8970 100,007%
4,8968 100,003%
4,8966 99,999%
4,8964 99,995%
4,8962 99,991%
4,8960 99,987%
4,8958 99,983%
UNIIM

SMU
INMETRO

Figure 1 Results of CCQM-K34.2 (standard uncertainties, k=1 are given)

7 REFERENCE VALUE
SMU result is used as a link to KCRV from CCQM-K34. The results in both comparisons differ
by less than 0,1%, so the degrees of equivalence are directly comparable. The degree of
equivalence for UNIIM and INMETRO is calculated from the formula:
Di = DSMU(K34) + νi(s) – νSMU(s)
where DSMU(K34) – degree of equivalence of SMU in CCQM-K34
νi(s) – UNIIM or INMETRO result in CCQM-K34.2
νSMU(s) – SMU result in CCQM-K34.2

The uncertainty of degree of equivalence of UNIIM and INMETRO, UDi will contain three
contributions: the uncertainty of reference value in CCQM-K34, the uncertainty of UNIIM or
INMETRO result and the uncertainty arising from the link provided by SMU. The latter
uncertainty is assumed to be equal to uncertainty of the SMU result in the current comparison.
Therefore
UDi  2  u SMU
2
, s  ui , s  u KCRV , K 34
2 2

where uKCRV,K34 – standard uncertainty of KCRV in CCQM-K34

ui,s – standard uncertainty of UNIIM or INMETRO result in CCQM-K34.2
uSMU,s – standard uncertainty of SMU result in CCQM-K34.2

The degree of equivalence between a laboratory and other laboratory j is calculated from the
respective degrees of equivalence:
Slovak Institute of Metrology Final report of CCQM-K34.2 Page 6/12

Di , j  Di  Dj
The uncertainty of degree of equivalence between a laboratory and other laboratories is
calculated according to the formula:

UDi , j  2  u SMU
2
, s  ui , s  u j
2 2

The degrees of equivalence relative to CCQM.K34 reference value are given in Table 3.

Table 3 Degrees of equivalence in CCQM-K34.2 in absolute values and in terms of mass

fraction

Di UDi
Institute Di UDi
/mol.kg-1 /mol.kg-1
INMETRO -0,00042 0,00057 -0,0086% 0,012%

UNIIM -0,00028 0,00082 -0,0058% 0,017%

The results for CCQM-K34.1, and CCQM-K34.2 linked to the original CCQM-K34 key
comparison are presented in Figure 2.

Degrees of equivalence for CCQM-K34,

CCQM-K34.1 and CCQM-K34.2
0,04%

0,00%

-0,04%
UNIIM(s2)
UNIIM

BAM(s1)
AIST

KRISS

NIM

INMETRO(s2)
NIST
SMU

CCQM-K34
CCQM-K34.2
CCQM-K34.1

Figure 2 Degrees of equivalence in CCQM-K34.2 (expanded (k=2) uncertainties are given)

Slovak Institute of Metrology Final report of CCQM-K34.2 Page 7/12

8 CONCLUSIONS

The results of the comparison confirmed good performance of the participating institutes. The
SMU provided the necessary link for calculation of UNIIM and INMETRO degree of
equivalence for CCQM-K34.

References
[1] Máriássy M., Breitenbach M., Oberroeder C., Hwang E., Lim Y., Pratt K.W., Hioki A.,
Suzuki T., Liandi M., Bing W., Yu S., Skutina A.V., Terentiev G.I., CCQM-K34 Final
Report: Assay of potassium hydrogen phthalate, Metrologia, 2006, 43, Tech. Suppl.,
08008
[2] Máriássy M., Final report on key comparison CCQM-K34.1: Assay of potassium hydrogen
phthalate, Metrologia, 2007, 44, Tech. Suppl., 08009
[3] Van der Veen A.M.H., Linsinger T., Pauwels J., Accred. Qual. Assur. 6, 26-30 (2001)
[4] BIPM, ISO, IEC, OIML, Guide to the expression of Uncertainty in Measurement (1995) 1st
ed., ISO, Geneva.
Appendix 1
Slovak Institute of Metrology, Bratislava

CCQM-K34.2 Assay of potassium hydrogen phthalate

Technical protocol
Introduction

This key comparison is done to underpin measurement capabilities to assay solid strong and
weak acids. It is done as a subsequent to the comparison CCQM-K34.

Time schedule
Dispatch of the samples: 5 September 2008
Deadline for receipt of the report: 31 December 2008
Distribution of Draft A for comments: January 2008
Draft A discussion: IAWG meeting in April 2009.

Samples

The samples will be provided by UNIIM. Each participant will receive one numbered bottle
containing about 20 g of material. Shipment to all participants will be performed at the same
time. The bottles are shipped in a cardboard box by courier and the consignment number is
reported by email to the contact person of the receiving laboratory for tracking purposes. The
contents will be marked “potassium hydrogen phthalate” for research purposes and value 1 USD;
please be attentive of possible customs delays, etc. The measurement protocol is sent by e-mail.
The homogeneity of the sample material was measured by UNIIM based on assay using sample
size of about 500 mg and found to be adequate for the key comparison.
The assay is expected to be in the range of 99.9 – 100.1 % of the theoretical value.

Actions at receipt of samples

Please inspect the received bottles for damage. Please inform the contact person of receipt and
report any mishaps to the coordinating laboratory. The sample should be stored at laboratory
temperature in the original container until used.

Sample preparation for measurement

The material should be dried at 110°C for 2 h without crushing or grinding the material.

Measurement method

Any method or method combination can be used for this comparison. The results will be
reported as amount content [mol/kg] of monoprotic weak acid, to be accompanied by a full
Slovak Institute of Metrology CCQM-K34.2 Appendix 1 – Protocol Page 9/12

uncertainty budget. Information on the assay dependence on sample mass is also welcome. At
least four determinations should be performed (where applicable).
Indirect methods must take into account the dependence of the assay on the H/K(or other metals)
ratio and the water content.

Reporting
The report should be sent to the coordinating laboratory before December 31, 2008, preferentially
by e-mail. The coordinator will confirm the receipt of each report. If the confirmation does not
arrive within one week, contact the coordinator to identify the problem.
A template for the report will be enclosed (Excel sheet). If possible the requested data should be
entered into the corresponding boxes, if not the format can be modified or the data can be reported
in another form.
Information requested:
1. Report the results as amount content [mol/kg] of weak monoprotic acid, accompanied by a
full uncertainty budget. Information on impurities is welcome also from participants not
using (100% - impurities) approach.
2. If the assay is determined from impurity analysis, results for all the elements/compounds
sought must be included.
3. A detailed description of the measurement procedure is to be given (for coulometry this
should include also: cell description, volume of electrolyte in working chamber, endpoint
evaluation procedure, example titration curve for initial and final titration), and of the
equipment used.
4. The complete measurement equation has to be given, as well as the values of the constants
used and variables (raw data) for at least one measurement. The data should enable the
recalculation of the result of this measurement.
5. State all the individual results, not only the final mean value.
6. The uncertainty budget has to include instrumental sources of uncertainty (mass, time,
voltage, volume, ...) as well as chemical ones (endpoint estimation, equilibria, CO2
interference, impurities, purity of calibration standards, ...). The uncertainty calculations
should conform to the ISO document: Guide to the expression of Uncertainty in
Measurement (1995) 1st ed., ISO, Geneva. Both Type A and Type B uncertainty components
and a summary of how they are calculated have to be included.
7. In order to facilitate comparisons of your measured masses (for assay measurements), please
also provide either (1) the air density used for each buoyancy correction, or (2) the air
temperature, humidity and pressure in your laboratory at the time of each mass measurement.
8. Report the details of the procedure used (a separate text file can be used).

Reference value
SMU will act as the connecting laboratory to the reference value of CCQM-K34.

Participation
The comparison is organised as a subsequent to CCQM-K34 based on the request of UNIIM;
INMETRO joined this comparison.
Slovak Institute of Metrology CCQM-K34.2 Appendix 1 – Protocol Page 10/12

The Draft A Report, based on the reported results will be prepared and sent to the participants
for comments and will be discussed at the April 2009 meeting of CCQM Working Groups on
Electrochemical Analysis and on Inorganic Analysis. The individual reports will be distributed
among the participants.

Coordinating laboratory and contact person

Michal Máriássy
Slovenský metrologický ústav (Slovak Institute of Metrology, SMU)
Karloveská 63
SK-84255 Bratislava 4
SLOVAK REPUBLIC
Tel.: +421 2 602 94 522 Fax: +421 2 654 29 592
E-mail: mariassy@smu.gov.sk

Participants

Alena V. Skutina
The Urals Research Institute for Metrology (UNIIM)
Krasnoarmeyskaya st. 4
RU-620000 Ekaterinburg
Russia

Michal Máriássy,
Slovenský metrologický ústav,
Karloveská 63,
SK-842 55 Bratislava,
SLOVAKIA

Paulo Paschoal Borges

Diretoria de Metrologia Científica
Divisão de Metrologia Química
Laboratório de Eletroquímica
INMETRO
Av. N. Sra das Graças, 50, Xerém, Prédio 04
Duque de Caxias, RJ, CEP 25250-020
Brasil
Slovak Institute of Metrology CCQM-K34.2 Appendix 2 - Procedures Page 11/12

Appendix 2

Description of measurements at UNIIM

Coulometric acidimetric titration method.
Equipment:
1. Microbalance ME 5 (“Sartorius”);
2. Current Source Model 8011A (“Applied Precision”);
3. Digital nanovoltmeter 2182A (“Keithley”);
4. 10 Ohm standard resistor MC3050 (“Krasnodarskyi ZIP“);
5. pH-meter Э-001-1 (“Econics-Expert”) with combined glass electrode (InLab Expert Pro, “Mettler Toledo”).
Measuring cell:
a vertical type cell consists of three compartments: working (cathodic), intermediate and auxiliary (anodic).
Intermediate and auxiliary chambers have a glass frites, in the anodic chamber there is agar-agar gel plug. Volume
of catholyte is 200 cm3, volume of anolyte is 100 cm3.Generating cathode is Pt net (S ~ 28 cm2), generating anode
is Ag rod (S ~ 31 cm2).
Measurement procedure:
The supporting electrolyte (1 M KCl) is acidified by 0.1 M HCl (50 μl) to pH ~ 5.2 and then deaerated by argon
during 45 min (intermediate chamber for 5 min, then cathodic and anodic chambers for 40 min and then during the
whole measurement). The initial titration is carried out using charge increments of 1.2 mA*20 s, after each
increment the electrolyte from the intermediate chamber is pushed out and into by argon pressure and a PTFE spray
shield above the solution is rinsed.
The end point of the initial titration is determined by potentiometric method using a set of 10-11 points pH vs. time
symmetrically located near the point of the largest pH change. After sample introduction the main titration is carried
out using generating current 100 mA. During main titration the electrolyte from the intermediate chamber is pushed
up slowly into the working chamber to decrease a migration of the sample to the anodic chamber.
After main titration the intermediate chamber is rinsed as well as spray shield to obtain stable pH value (± 0.002).
Then final titration is carried out using charge increments of 4 mA*20 s with intermediate chamber and spray shield
rinsing after each increment. The end point of final titration is determined by a similar way as for initial titration.

Description of measurements at INMETRO

The analytical method used was coulometric titration with constant current and potentiometric end-point detection
by using combined pH glass electrode. The sample of KHP was dried at the temperature of 110 oC during 2 hours.
The coulometric cell is made of glass and has vertical design with two separate compartments: the cathodic and the
anodic. The anodic compartment stays inside the intermediate compartment (IC) which is separated from the
cathodic one through an agar-agar plug. The supporting electrolyte (250 mL) was a solution of 1 mol/L of potassium
chloride (Merck, 99.5%). A platinum wire (99.99%) in "www" shape with 0.25 mm diameter and 200 mm length
was the cathode; a spiral silver electrode (purity 99.99%) with dimensions of 50 x 55 x 5 mm was the anode.The
necessary current to the coulometric titration of KHP sample (weighing on the range of 500 mg by using a
microbalance Mettler Toledo, UMX 5, resolution 0.1 mg) was passed on 3 different phases: it was passed a current
of 2 mA for the initial titration; to the main titration, it was passed 200 mA and for the final titration, it was passed
10 mA. All the weighing was corrected for buoyancy and the coulometric cell was maintained at temperature of 25
oC by using a water bath (Lauda RE 204) during the experiment. Argon gas of high purity (99.999%) was passed
through the both cathodic and anodic compartiments for deaeration or maintained above the cathodic compartiment
during the main titration. In all titrations the catholyte was stirred with magnetic stirrer.

Description of measurements at SMU

Equipment used:
CURRENT SOURCE 7961 (Applied Precision)
INDICATION UNIT 8971 (Applied Precision)
valve unit (Applied Precision)
digital voltmeter Solartron 7071 (Schlumberger)
microbalance S4 (Sartorius)
standard 1 ohm resistor (Metra)
piston burette 665 Dosimat (Metrohm)
thermostats E203, and E206T (Lauda)
stirrer RH3
muffle furnace LM 212.11
Slovak Institute of Metrology CCQM-K34.2 Appendix 2 – Procedures Page 12/12

Titration parameters
catholyte 0.55 mol/L KCl, 250 mL
anolyte 1 mol/L KCl
generation electrode Pt wire, ca 7 cm2
counter electrode Ag wire, ca 85 cm2
high current 200 mA
low current 1.6 and 10 mA, resp.
indication potentiometric, glass combined electrode
endpoint determination inflexion point from non-linear regression
fraction titrated in main titration ~0.999

After deaeration of the acidified supporting electrolyte (5 min intermediate compartment +cell, 30 min cell only;
final pH~5.8) the sample is suspended in a glass cup into the cell (above the solution) and the initial titration
started; after reaching pH~6.3 the intermediate compartment and the PTFE spray shield above the solution are
rinsed until the pH change is less than a predefined limit (0.01) and the intermediate compartment is filled with
about 27 mL of the electrolyte being titrated. The initial titration is then continued with constant charge
increments until 5 points after the largest pH change are recorded.
After sample introduction, the main titration is started and the solution in the intermediate compartment is slowly
pushed into the working compartment to minimise sample diffusion out of the cell (during the whole main
titration). After main titration, the intermediate compartment and the spray shield are rinsed (pH change limit
0.002). Afterwards, final titration is started with constant increments and rinse after each increment. When 5
points after the largest pH change are recorded, the titration ends and the result is calculated and output.