Full Paper

Evaluation of a Compact Differential Cell for Secondary pH

Measurements by a Bilateral Interlaboratory Comparison
Fabiano Barbieri Gonzaga,*a Jlio Cesar Dias,a Diana Jehnert,b Barbara Werner,b Karin Schrpler,b Leos Vyskocilc
a Chemical Metrology Division, National Institute of Metrology, Quality and Technology (INMETRO), Av. Nossa Senhora das
Graas, 50, Xerm, 25250-020 Duque de Caxias, RJ, Brazil
b Zentrum fr Messen und Kalibrieren -ANALYTIK- GmbH (ZMK), Areal A, Filmstrae Nr. 7, Chemiepark Bitterfeld-Wolfen,

06766 Wolfen, Germany

c Slovensky metrologicky stav (SMU), Karlovesk 63, SK 842 55 Bratislava 4, Slovakia
*e-mail: fbgonzaga@inmetro.gov.br

Received: March 20, 2013

Accepted: May 16, 2013
Published online: June 21, 2013

Abstract
This work presents a new differential potentiometric cell for the standardization of pH buffer solutions and its eval-
uation, by means of a bilateral interlaboratory comparison, in relation to a traditional Baucke cell. The results ob-
tained with the two cells were exactly the same for three of the pH buffer solutions analyzed (1.68, 4.01, and 6.86)
and similar to each other for the remaining buffer solution (9.18). The new cell showed an average measurement
time of only 21 minutes, in comparison with one to three hours for other cells described in the literature (including
the Baucke cell).

Keywords: Differential cell, Potentiometry, pH, Standardization, Buffer solution

DOI: 10.1002/elan.201300135

1 Introduction quires the establishment of a metrological calibration hi-

The most widely used measurement for the acidity of sol-
utions is pH, which is defined as the negative logarithm
of the activity of hydrogen ions [14]. It is one of the
most common and frequent quantitative measurements in
chemical analyzes [57]. This status of pH was achieved
not only because its measure is usually fast, inexpensive,
and easy to perform, but also because it has many areas
of application, such as health care and safety, biochem-
istry, geochemistry, industrial processes, and environmen-
tal monitoring. The rate of important chemical reactions
within industrial processes can be altered by changing the
pH level. For geochemistry and environmental science,
measuring the pH values of fresh waters accurately is of
great importance. Moreover, research in environmental
science and in biochemistry has given evidence that the
measurement uncertainty in pH forms a central contribu-
tion to the uncertainty budget of thermodynamic data as
well as to geochemical transport models. In addition,
since the solubility and bioavailability of substances are
functions of the pH value, it is also a critical input quanti-
ty for climate modeling [712].
Practical pH measurements of real samples are mostly
performed by potentiometry using a glass indicating elec-
trode connected to a digital pH meter, which must be
calibrated using reference buffer solutions [13, 14]. Confi-
dence in the reliability of the measurement results re-
erarchy linking the quantity in the sample to a unit in the
International System of Units (SI) or, where this is not
possible, to another valid international reference. For pH,
a traceability chain can be established by calibration
using primary reference buffer solutions, for which the
pH values are obtained by utilizing the internationally
recognized measurement procedure [3]. This procedure,
called primary pH measurement, is based on potentio-
metric measurements for electrochemical cells without
liquid junctions (frequently called Harned cells), with
each cell containing the pH buffer solution, a hydrogen-
bubbled platinum/platinized (or palladinized) electrode
(also called a hydrogen electrode), a silver/silver chloride
electrode, and a known amount of chloride [2, 3, 911].
However, in some cases, these primary standards are
too expensive for common laboratories dealing with rou-
tine pH measurements. In these cases, laboratories can
achieve traceability by means of secondary reference
buffer solutions. These solutions can be standardized in
comparison with primary buffer solutions using a proce-
dure that is typically simpler and faster and employs
cheaper instrumentation [9]. This secondary pH measure-
ment is also internationally recognized and was first de-
scribed in 1994 by F. G. K. Baucke [15], who designed
a cell that was later named the Baucke cell. This stand-
ardization procedure usually makes use of a differential
potentiometric cell with a single junction (without a salt

Electroanalysis 2013, 25, No. 8, 1955 1959  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1955
Full Paper
bridge) separating two half-cells: one contains the pri-
mary buffer solution and a hydrogen electrode (reference
potential), and the other contains the secondary buffer
solution and another hydrogen electrode. The two buffer
solutions must have the same nominal composition, and
the two electrodes must be as similar as possible to each
other. Since the hydrogen pressures in the half-cells are
about the same, and because the quasi-identical solutions
can hardly cause any interdiffusion, the liquid junction
potential (LJP, developed in the junction between the
two half-cells) is only on the order of microvolts, and its
effect on the pH result measured for the secondary buffer
solution can be neglected. Thus, the pH of the secondary
buffer solution (pHS) is obtained using Equation 1:
DECell F
pHS pHP 
RT ln 10
where pHP is the pH of the primary buffer solution,
DECell is the potential difference between the hydrogen
electrodes after stabilization (in V), F is the Faraday con-
stant, R is the universal gas constant, and T is the temper-
ature (in K) [3, 4, 15]. Using his cell, F. G. K. Baucke re-
ported measurement times between one and three hours
(the time required for stabilization of the potential differ-
ence) [15]. More recently, two papers [7, 16] have report-
ed on modified cells for secondary pH measurement. The
last one [7], from 2011, reported measurement times of
about one hour.
Although the Baucke cell is still used, it presents some
drawbacks, such as the relatively large amount of solution
required to fill the cell and the long measurement time.
Thus, this paper presents a new differential potentiomet-
ric cell for the standardization of pH buffer solutions. The
new cell was evaluated by means of a bilateral interlabor-
atory comparison, where one of the laboratories used
a traditional Baucke cell.
2 Experimental
2.1 Bilateral Interlaboratory Comparison
A bilateral interlaboratory comparison on secondary pH
measurement was performed, with participation of
a German calibration laboratory (Zentrum fr Messen
und Kalibrieren ZMK, DAkkS accreditation number
D-K-15186-01-00) and the Brazilian metrology institute
(National Institute of Metrology, Quality and Technology
INMETRO), in order to evaluate the new differential
potentiometric cell, used by INMETRO, in comparison
with a Baucke cell, used by ZMK. The results from both
laboratories were compared to each other using the nor-
malized error statistical test (En) [17], as shown in Equa-
tion 2:
1956 www.electroanalysis.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
F. B. Gonzaga et al.
 
xpart  xref 
q
En   2
Upart 2 Uref 2
where xpart is the result of the participating laboratory, xref
is the result of the reference laboratory, Upart is the ex-
panded uncertainty (coverage factor of 2) of the partici-
pating laboratory, and Uref is the expanded uncertainty of
the reference laboratory. As the Baucke cell is the cell
traditionally employed for secondary pH measurements,
ZMK was defined as the reference laboratory.
2.2 Equipment
Two similar measurement systems were employed by
ZMK and INMETRO. In addition to the cell, each mea-
1 surement system was composed of a digital multimeter
(for measuring voltage and temperature), a thermostatic
bath, a temperature sensor (immersed into the bath), and
a gas flow controller (for controlling the hydrogen flows
entering the cells). For the system containing the Baucke
cell (ZMK), a Fluke 8508A digital multimeter, a Schott
CT44 thermostatic bath, two Pt 100 resistance thermome-
ters, and an Agilent ADM1000 gas flow controller were
used. For the system containing the new cell (INME-
TRO), an Agilent 34970A digital multimeter, a Hart Sci-
entific 7011 thermostatic bath, a type J thermocouple,
and two MKS 1479A gas flow controllers were employed.
Both potentiometric cells used in this work are made
of glass and have a D4 porosity sintered-glass disk (10 to
16 mm pore width) separating the two half-cells (contain-
ing the hydrogen electrodes and the buffer solutions).
The Baucke cell has two glass tubes for inserting hydro-
gen into the two half-cells, each tube with a D3 porosity
sintered-glass disk (16 to 40 mm pore width) at one end.
For saturating the hydrogen with water vapor, the distan-
ces between the porous disks and the electrodes are kept
at a minimum of 20 mm. The depths of the disks in the
solutions are about the same in order to have the same
hydrogen pressure in the two half-cells. The hydrogen
flows leaving the half-cells are combined within a T-
shaped tube and bubbled through a flask containing
water. The volume of solution required to fill both half-
cells of the Baucke cell is about 200 mL. A more detailed
description of the Baucke cell and an in-depth description
for preparing the platinum/platinized (or palladinized)
electrodes can be found in the literature [15]. The new
cell presented in this work also has two glass tubes for in-
serting hydrogen into the two half-cells. However, before
entering each half-cell by a D1 porosity sintered-glass
disk (100 to 160 mm pore width), the hydrogen flow from
each tube passes through two additional compartments
(containing buffer solutions for the prehumidification of
hydrogen), also connected to each other by a D1 glass
disk. The depths of the porous disks at the bottom of
each half-cell are about the same in order to have the
same hydrogen pressure in the two half-cells. The hydro-
gen flows leave the cell by two holes (about 1 mm diame-
Electroanalysis 2013, 25, No. 8, 1955 1959
Compact Differential Cell for Secondary pH Measurements
Fig. 1. Schematic representation of a system for secondary pH
measurement (left side) and, in details, a drawing of the new po-
tentiometric cell presented in this work (right side): (a) digital
multimeter, (b) thermostatic bath, (c) hydrogen flow controllers,
(d) hydrogen gas, (e) potentiometric cell, (f) temperature sensor,
(g) tubes for connecting the hydrogen flows, (h) hydrogen elec-
trodes, (i) D4 porosity sintered-glass disk, and (j) D1 porosity
sintered-glass disks.
ter, not shown in Figure 1), one in the upper side of each
half-cell. Due to its small size, the volume of solution re-
quired to fill both half-cells of the new potentiometric
cell is only about 20 mL. Figure 1 shows a schematic rep-
resentation of a system for secondary pH measurements
and, in details, a drawing of the new cell.
The new electrochemical cell is an improved version of
an old cell already described in the literature [16]. The
main difference between the old cell and the new cell is
that a capillary U-shaped tube formed the connection be-
tween the two half-cells (a free-diffusion junction) in the
old cell. In addition, each half-cell in the old cell had only
one compartment for the prehumidification of hydrogen.
It is also important to point out that there is no descrip-
tion in the literature of a measurement comparison be-
tween this old cell and the Baucke cell.
2.3 Samples
Four pH buffer solutions, having the following composi-
tions (as recommended by IUPAC [3]), were analyzed for
secondary standardization (secondary buffer solutions) in
the interlaboratory comparison: 0.05 mol kg1 potassium
tetroxalate (called the TO sample), 0.05 mol kg1 potassi-
um hydrogen phthalate (called the PT sample),
0.025 mol kg1 disodium hydrogen phosphate
/0.025 mol kg1 potassium dihydrogen phosphate (called
the PP sample), and 0.01 mol kg1 disodium tetraborate
Electroanalysis 2013, 25, No. 8, 1955 1959  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(called the TB sample). Therefore, and as explained
before, four primary buffer solutions (the pH values were
obtained by primary pH measurements [24]) with the
same compositions as described above were also used in
the measurements.
2.4 Experimental Procedure
Similar measurement procedures were employed by
ZMK and INMETRO. Aliquots of a primary and a secon-
dary buffer solution (with the same nominal composi-
tions) were added to the potentiometric cell, with each
solution in one of the half-cells containing the hydrogen
electrodes. Then, the cell was immersed into a thermostat-
ic bath (set to 25.0 8C), the hydrogen flows were turned
on (8 to 10 cm3 min1), and the potential difference and
the temperature were taken after the potential difference
stabilized. This procedure was carried out three or four
times (measurement replicates) for each secondary buffer
solution. Finally, the average potential difference and the
average temperature (between the three or four repli-
cates) were used (Equation 1) for calculating the pH
result.
The two laboratories employed different criteria for
measuring the potential difference. For each replicate
using the Baucke cell (ZMK), and according to the mea-
surement times reported in the literature [15], 30 meas-
urements were taken (one per minute) after a stabilization
time of 90 minutes, giving a total measurement time of
120 minutes. Then the average result was used. As the
new potentiometric cell was significantly smaller than the
Baucke cell, a different approach was employed in order
to verify the possibility of using shorter measurement
times. Therefore, for each replicate using the new cell
(INMETRO), measurements were taken periodically
(every one minute) without any initial stabilization time,
while employing a continuous evaluation of the measure-
ments stability. Thus, the measurements were considered
stable when the last five measured values presented,
three times in a row, a variation along time (slope from
linear regression) lower than 5 mV min1 and an ampli-
tude (difference between the highest and lowest values)
lower than 10 mV. The average result from the last seven
measurements was then used.
Before the analysis of each buffer solution, INMETRO
and ZMK checked the proper functioning of the poten-
tiometric cells by measuring the potential difference
when both half-cells contained the same solution (pri-
mary or secondary). The measured value, DEBias, was ne-
glected if j DEBias j was lower than 3 mV. Otherwise, if
j DEBias j was higher than 3 mV, it was used to correct the
potential difference measured for the subsequent ana-
lyzes.
2.5 Estimation of Measurement Uncertainty
A measurement uncertainty was estimated for the pH
result of each secondary buffer solution analyzed, accord-
www.electroanalysis.wiley-vch.de 1957
Full Paper F. B. Gonzaga et al.

Fig. 2. Ishikawa diagram related to the measurement uncertain-

ty estimation of the secondary pH measurements.

Fig. 3. Variation of the potential difference (squares) over time,

ing to international guidelines [17, 18]. An Ishikawa dia- and its first derivative (circles), for one measurement replicate
gram [19] (also called a cause-and-effect diagram) related using the new potentiometric cell.
to these uncertainty estimations, showing the uncertainty
sources taken into account in the calculation, is given in
Figure 2. 21 minutes, in comparison with one to three hours for
other cells (including the Baucke cell) [7, 15]. This shorter
measurement time can be explained by the small size of
3 Results and Discussion the new cell, allowing faster saturation (with hydrogen)
of the solutions into the half-cells. In addition, and as
The pH results (with expanded uncertainties) obtained in cited previously, the new cell has two compartments for
the secondary pH measurements from ZMK and INME- the prehumidification of hydrogen before entering each
TRO are given in Table 1, together with the En results for half-cell, which may also have contributed to this shorter
comparing them. This table also shows the pH values of measurement time. For illustrative purposes, Figure 3
the primary buffer solutions used in the calculation of the presents the variation of the potential difference over
secondary pH results. time, and its first derivative, for one measurement repli-
As can be seen, all En results were lower than 1, mean- cate taken with the new cell, showing the prompt stabili-
ing that the results obtained with the new potentiometric zation of the potential difference within a relatively short
cell and the Baucke cell were statistically similar to each measurement time.
other considering the corresponding measuring uncertain- Table 2 shows the uncertainty budget related to the un-
ties. Moreover, the results from both cells were exactly certainty estimation for one of the secondary pH results,
the same for three of the four samples, showing that the as an example. It is important to point out that, although
results of the new potentiometric cell are quite reliable.
The small difference found between the results of the two
cells for the TB buffer solution may have been caused by Table 2. Uncertainty budget for one of the secondary pH results
some carbon dioxide (from air) interference in the new of INMETRO.
cell, since the hydrogen outputs in the new cell are in Uncertainty Standard un- Sensitivity co- Uncertainty con-
direct contact with air (unlike the Baucke cell). source certainty (ui) efficient (ci) tribution (ui  ci)
The use of the new potentiometric cell allowed signifi- pHP uncer- 0.001 1 0.001
cantly shorter measurement times compared to other tainty
cells described in the literature. The average measure- DECell re- 1.2  105 V 16.9 V1 2.1  104
ment time for one replicate using the new cell was about peatability
LJP 7.2  106 V 16.9 V1 1.2  104
Multimeter 1.5  107 V 16.9 V1 2.5  106
Table 1. The pH results with expanded uncertainty (coverage (Voltage)
factor of 2) and statistical comparison using the normalized error T repeatabili- 0.1 K 4.1  106 K1 4.1  107
test (En). ty
Multimeter 0.1 K 4.1  106 K1 4.1  107
Buffer solution pHP pHS Baucke cell pHS new cell En
(Temp.)
TO 1.680  0.002 1.679  0.003 1.679  0.002 0.00 Combined 0.001
PT 4.006  0.002 4.010  0.003 4.010  0.002 0.00 uncertainty
PP 6.863  0.006 6.863  0.006 6.863  0.006 0.00 Expanded (coverage 0.002
TB 9.170  0.003 9.180  0.003 9.178  0.003 0.47 uncertainty factor of 2)

1958 www.electroanalysis.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2013, 25, No. 8, 1955 1959
Compact Differential Cell for Secondary pH Measurements
the liquid junction potential is usually neglected in the
calculation of the pH results, it is considered an uncer-
tainty source. Its uncertainty contribution to the potential
difference measured is estimated as 10 % when the two
half-cells contain buffer solutions with the same nominal
composition [9, 20, 21].
In addition, as can be seen in Table 2 and as already
known [3, 4], the most important uncertainty source in
secondary pH measurements is the uncertainty of the pH
value of the primary buffer solution used in the measure-
ments. In this example, it accounted for more than 97 %
of the total uncertainty of the secondary pH measure-
ment. That is why the final uncertainty value of a secon-
dary pH measurement, after rounding to three decimal
places, is usually the same as that from a primary pH
measurement.
4 Conclusions
A new differential potentiometric cell was described and
successfully evaluated in comparison with a Baucke cell
for the standardization of pH buffer solutions. The results
obtained using the two cells were exactly the same for
three of the four buffer solutions analyzed and statistical-
ly similar to each other for the remaining buffer solution,
demonstrating the good performance of the new poten-
tiometric cell. The new cell is compact, requires a smaller
volume than the Baucke cell and has specific compart-
ments for the prehumidification of hydrogen. These char-
acteristics allowed significantly faster measurements in
comparison with other cells described in the literature
(including the Baucke cell). On the other hand, the small
difference found between the results of the two cells for
the one alkaline buffer solution analyzed may indicate
that the results of the new cell can be affected by some
carbon dioxide interference when measuring alkaline sol-
utions. The new cell will contribute to the certification of
pH reference materials with a shorter analysis time, lower
cost, and lower waste generation. This will enable new
commercial laboratories to certify and sell pH reference
materials, extending traceability to a higher number of
common analytical laboratories dealing with pH measure-
ments.
Electroanalysis 2013, 25, No. 8, 1955 1959  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Acknowledgements
J. C. Dias wishes to thank FAPERJ for a fellowship (Pro-
cess E-26/101.936/2008).
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