C618 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017)

Development of an Electrochemical Balance to Measure

Quantitatively Hydrogen Generation during Electrochemical
Processes
Luca Bottini,a,b Monica Santamaria,b,∗ and Michele Curionia,∗,z
a Schoolof Materials, Corrosion and Protection Centre, University of Manchester, M139PP Manchester,
United Kingdom
b ElectrochemicalMaterials Science Laboratory, DICAM, Università di Palermo, 90128 Palermo, Italy

A new method to measure the amount of hydrogen generated from the surface of an immersed electrode is presented in this work. The
method consists of a mechanical balance with a horizontal arm attached to two hydrogen-collecting containers that are submerged in
two independent electrochemical cells. One of the two cells (the test cell) contains the electrode of interest, generating an unknown
amount of hydrogen, whereas the other cell (the measurement cell) contains an inert electrode that is used to evolve an amount of
hydrogen equal to that generated in the test cell, such as the mechanical equilibrium between the sides of the balance is constantly
maintained. Adequate electrical connections and circuitry ensures that, as hydrogen is evolved from the electrode of interest in the
test cell, the displacement of the balance arms activates an electrical contact, which triggers the hydrogen evolution in the measuring
cell. Once a sufficient amount of hydrogen is evolved from the measuring cell, the horizontal arm is displaced in the opposite direction
and the electrical contact to the measuring cell is interrupted. The measurement of the current flowing through the measuring cell
enables precise estimation of the amount of hydrogen generated in the test cell.
© The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.0441712jes] All rights reserved.

Manuscript submitted June 26, 2017; revised manuscript received July 28, 2017. Published August 5, 2017.

Proton reduction, resulting in generation of hydrogen gas, is ob-
served in many applications involving electrochemical reactions and
often during corrosion of light alloys. It can be a side reaction during
metal electrodeposition,1–3 a parasitic reaction for batteries4–6 and sac-
rificial anodes,7–10 or the cathodic reaction for corrosion of metals with
low electrochemical potential, such as for example magnesium11–23 or
aluminum.24–34 The accurate measurement of the amount of hydrogen
gas generated during an electrochemical process is important both
to aid fundamental understanding and to optimize technological pro-
cesses. The present work has originated from the authors’ activity
focusing on the measurement of the hydrogen evolved from magne-
sium during corrosion in aqueous environments; however the method
presented here could be applied to virtually any study where quan-
titative measurement of gas evolving from an immersed electrode is
required.
The most simple and most widely applied method to measure
the hydrogen generated from an immersed surface is the (volumet-
ric) hydrogen collection method, widely used in corrosion studies on
magnesium and magnesium alloys.11–18,35–37 The volumetric method
involves the use of a graduated cylinder that is closed at the top and
open at the bottom, and initially filled with test electrolyte. The bot-
tom of the electrolyte-filled graduated cylinder is immersed in a cell
containing the same electrolyte, and a specimen evolving an unknown
amount of hydrogen is then placed below the cylinder (sometimes
with a funnel to aid complete bubbles collection). The hydrogen bub-
bles generated from the specimen float toward the top of the graduated
cylinder, where they are collected, and the gas volume can be mea-
sured. The advantage of such method is the simplicity and the use
of inexpensive materials, enabling many long-term tests to be run in
parallel with minimal expense and setup time. On the other hand,
the main disadvantage is the relatively low sensitivity and precision,
which is the consequence of the fact that a relatively large amount
of hydrogen (at least fractions of a milliliter) must be accumulated
at the top of the cylinder, before a reliable estimation of the volume
can be made. Reducing the diameter of the cylinder can, to some ex-
tent, increase the precision of the volumetric measurement, but as the
diameter of the cylinder becomes small, the relative error, associated
with the hydrogen bubbles sticking to the cylinder walls instead of
immediately floating at the top, increases.
∗ Electrochemical Society Member.
z
E-mail: michele.curioni@manchester.ac.uk; curionimichele@gmail.com
A far more advanced, faster and precise method was proposed
by Lebouil et al.,11 who used a micro electrochemical flow cell ar-
ranged in such way that the hydrogen evolved from the electrode
was immediately pumped, together with the flowing electrolyte, in
a small capillary. Once inside the capillary, images of the small hy-
drogen bubbles could be automatically acquired and their volume
could be estimated by automated image analysis, almost in real-
time. This method is precise and fast, but the small scale of the
electrochemical cell poses a serious limitation for macroscopic cor-
rosion studies, and the required hardware is relatively complex and
expensive.
Recently, a gravimetric method based on the measurement of the
weight of a submerged hydrogen collecting container was introduced
by Curioni et al.,20,22,23,38 and subsequently improved by Fajardo
et al.38 The method is based on the continuous measurement of the
weight of a submerged hydrogen-collecting container. Specifically, a
hydrogen evolving specimen is mounted rigidly below a hydrogen
collecting container, open at the bottom and closed at the top, and
initially filled by the test electrolyte. Both specimen and container
are completely immersed in a test cell, and connected rigidly to a
laboratory scale. When hydrogen evolves from the corroding sur-
face, it is collected in the submerged container, producing a buoyancy
force since the hydrogen gas replaces and displaces some of the test
electrolyte within the collecting container. Such buoyancy force is
directly proportional to the amount of hydrogen evolved and can be
easily recorded by the laboratory scale. The method has very high
sensitivity and resolution (less than a mA of hydrogen current can be
easily measured by using a scale with 0.1 mg resolution) and it enables
the investigation of the real-time the behavior of freely corroding or
electrochemically polarized macroscopic electrodes. Further, as long
as the specimen is rigidly connected to the submerged collecting cylin-
der, no error is introduced when bubbles stick either to the specimen
or to the container wall, since the buoyancy force is transmitted to the
scale and accounted for immediately. However, a possible disadvan-
tage is that the laboratory scale is relatively expensive and bulky, and
therefore the setup it is not practical for running in parallel a large
number of long-term tests.
This work presents a new method that uses the same principle, i.e
based on the buoyancy force produced by the evolved hydrogen on a
submerged collecting container, but instead of using a laboratory dig-
ital scale, exploits the principle of the mechanical balance to estimate
the amount of hydrogen evolved.

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 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017)
Figure 1. Schematic operational principle of the hydrogen balance: a) hydro-
gen is generated in the test cell inducing (b) a displacement of the balance
arm. The displacement closes the electrical circuit in the measurement cell,
triggering hydrogen evolution. The hydrogen evolved in the measurement cell
balances the hydrogen evolved in the test cell (c) and the electrical contact is
interrupted.
Operating Principle
The method presented here exploits the principle of the mechanical
balance, schematically illustrated in Figure 1. A horizontal arm with a
central support is rigidly connected by insulated metallic rods to two
hydrogen collecting containers. The electrodes are rigidly connected
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C619
to the collecting cylinders and electrically connected to the metal rods
(in the interest of clarity, detailed electrical connections are discussed
later). The two containers-electrodes assembly are immersed in two
independent electrochemical cells, referred to hereon as the “test cell”
(containing the electrode producing an unknown amount of hydrogen)
and as the “measuring cell”, containing an inert electrode used to
evolve hydrogen (Figure 1a). Above the horizontal arm, in the side of
the arm above the measuring cell, a metallic needle is placed, such as
when (an unknown amount of) hydrogen evolves from the specimen in
the test cell, the horizontal arm moves upwards in the measuring cell
side (and downwards in the other), until it contacts a metallic needle
(Figure 1b). When the arm contacts the needle, adequate circuitry
induces hydrogen evolution on the electrode in the measuring cell.
Once sufficient hydrogen is evolved in the measuring cell, the balance
arm moves upwards in the measuring cell side and downwards in the
test cell side, opening the electrical contact and interrupting hydrogen
evolution in the measuring cell (Figure 1c). The mechanical system is
self-equilibrating, i.e. it maintains equal amounts of hydrogen in both
cells. The simple measurement of the current flowing in the measuring
cell, by acquiring the potential difference across the measuring resistor
Rm , enables estimation of the amount of hydrogen produced in the test
cell.
Electrical Circuitry
From the electrical viewpoint, the hydrogen balance requires 3
key components: i) the base (schematically represented in Figure 2a),
ii) the balance arm (schematically represented in Figures 2b, 2c) and
iii) the supported contact pin (schematically represented in Figures
2c, 2d). The base (Fig. 2a) consists of two coplanar conductive flat
surfaces that are electrically insulated from each other. An electrical
cable is soldered to each of the two surfaces, such that the 2 electrical
cables are attached to the base, but there is no electrical connection
between the two cables. On the base, the arm is suspended trough two
metallic needles (Figures 1a, 1b), such that each of the two needles is in
electrical contact with one of the two conductive surfaces of the base,
but not with the other. This provides electrical continuity between
the cables connected to the base (labelled as 1B and 2B in Figure
2a) and the cables placed on the balance arm (labelled as 1A and 2A
respectively in Figure 2a), without introducing significant friction or
spring back forces that might affect the response of the balance. In the
configuration used for this work, only cables 2B and 2A are used to
connect a potentiostat to the electrode placed in the test cell, and cables
1B and 1A are not connected. More advanced electrical configurations
require connection of cables 1B and 1A, but they are not discussed
here. Overall, the electrical connections can be seen in Figures 2b,
2c. Specifically, the electrode in the test cell is electrically connected
to cable 2B, through the support and electrical contact needles, while
the electrode in the measurement cell is electrically connected to the
contact needle (when the balance’s arm move upwards) through the
contact pad placed on the balance arm (Figure 2c).
From the electrical viewpoint, the overall principle of operation
is simple; when the balance arm move upwards in the test cell side,
the contact pad touched the contact needle and this contact closes the
circuit in the measuring cell side, developing hydrogen. The contact
is maintained until sufficient hydrogen is developed in the measuring
cell to balance that developed in the test cell. The overall test circuit
used in this work is schematically presented in Figure 3. An Ivium
Vertex potentiostat is used to apply a measured current to a titanium
electrode attached to the balance arm in the test cell side. A 9 V
battery, connected in series with a measuring resistor, provides the
voltage to generate hydrogen on a titanium electrode connected to the
balance’s arm in the measurement cell side. The potential difference
across the measuring resistor is recorded by using a NI-USB6009
analogue to digital converter, acquiring the voltage difference across
the measuring resistor at a rate of 5 kHz. The high-frequency data are
subsequently averaged to produce a time record at 1 Hz.
 C620 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017)
Figure 2. Schematic representation of the key elements and of the electrical
connections of the hydrogen balance. a) Support plate and connection to the
balance arm through support needles, b) top view of the balance arm c) side
view of the balance arm with external contact needle and d) top and side view
of the flexible aluminum support.
Mechanical Considerations
From the mechanical viewpoint, the behavior of the balance can
be schematically represented as in Figure 4. Ignoring all the balanced
components of the forces, when hydrogen is generated in the test cell,
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a buoyancy force F1 is generated at a distance b from the support
point. Such force generates a moment M1
M1 = F1 · b [1]
The rotation angle of the arm (α), and the displacement d, are a
function of the applied moment M1 , of the distance (h) between the
center of gravity and the support point, and of the weight of the arm
(Fp ). With reference to Figure 4, if the arm is in equilibrium before
the application of the force F1 , the center of gravity is located in
position 1 and aligned vertically with the support point. When F1 is
applied, the arm rotates counter-clockwise and the center of gravity is
displaced from position 1 to position 2. The force Fp associated with
the weight of the displaced center of gravity, has now a component,
FP ⊥ , perpendicular to the line passing through the center of gravity
and the support point. FP ⊥ generates a moment M2, opposing to the
moment M1 , that can be calculated as:
M2 = Fp⊥ · h [2]
Where
Fp⊥ = Fp · sin (α) [3]
At the equilibrium, the two moments are equal (M1 = M2 ) and, con-
sidering that the displacement d can be written as
d = b · sin (α) [4]
it is possible to write calculate the displacement d as a function of
the buoyancy force F1 , the length of the arm b, the weight of the arm
Fp and the vertical distance between the support point and the arm’s
center of gravity, h:
b2 · F1
d= [5]
h · Fp
For example, considering a 200 mm arm that weights 200 g (1.961
N), and a change in weight of 7.6 mg (74.6 × 10−6 N), which is
equivalent to the quantity of hydrogen produced in a minute by 1 mA
of cathodic current in water, the displacement (d) equals 0.152 mm if
the center of gravity of the arm is located 10 mm below the support
point and 1.52 mm if the center of gravity is located 1 mm below
the support point. If the center of gravity of the balance is above the
support point, the considerations above are not applicable, since the
balance would be unstable. In this case, any horizontal displacement of
the center of gravity from the support point would create a momentum
in the same direction of the applied force F1 causing the arm to fall.
Based on the mechanical analysis, two key conclusions can be
made; 1) the center of gravity of the balance must be below the
support point at all times, such that the balance is stable and the arm
has a horizontal equilibrium position and 2) that for a given force
applied to one side, the displacement of the arm increases (and hence
the sensitivity of the balance) when the distance between the center
of gravity of the arm and the fulcrum decreases. It follows that to
improve the sensitivity of the hydrogen balance it is essential to be
able to adjust the position of the center of gravity with respect of the
position of the support point.
Practical Implementation
The hydrogen balance used to obtain the results presented in this
work consists of a glass support, the conductive base, the balance arm
with the attached hydrogen collecting containers and electrodes, and
a holder for the contact pin. The two key components of the balance
that deserve detailed discussion are the balance arm and the contact
pin. The balance arm is graphically illustrated in Figure 2. The mate-
rial used for constructing the arm was 2 layer copper clad glass fiber
reinforced polymer with total thickness of 1.6 mm and 200 mm long.
This is a material that is commonly used for prototyping printed circuit
board and it is readily available on the market. Mechanical connections
between the various parts of the balance arm were made by solder-
ing, using solder wire (Ag 4%, Sn 85.5%, Cu 0.5%.) The aluminum
 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017)
rods, connecting the arm to the hydrogen collecting cylinders were
connected to the arm by epoxy resin, and electrical connection was
made directly using insulated copper wires as needed. The aluminum
rods were insulated from the test electrolyte by heat-shrinking plastic
sleeves. The hydrogen collecting cylinders were made of glass, 2 cm
diameter by 3 cm height. The electrodes were connected to the rod
by using insulated electric wire, and the connections were insulated
from the electrolyte by epoxy resin.
In order to increase the precision and sensitivity of the balance,
the key element is the center of gravity adjustment system. This is
realized by attaching with epoxy resin two 8 mm internal diameter
nuts sustaining a bolt in the horizontal direction and two similar bolts
sustaining a screw in the vertical direction, as schematically illustrated
in Figure 2b. Moving the horizontal bolt enables the adjustment of
the position of the center of gravity in the horizontal direction, while
the vertical bolt enables the adjustment of the position of the center
of gravity in the vertical direction. Before starting a measurement, the
Figure 4. Schematic view of the movement of the balance arm as a result of
the application of a force F1 .
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C621
Figure 3. Schematic representation of the experimental
setup and electrical connections used to evaluate the per-
formance of the hydrogen balance.
position of the center of gravity must be carefully adjusted by turning
the horizontal and vertical bolt such that, when the arm is horizontal,
the center of gravity of the arm is as close as possible, but below, the
support point.
The contact for the closure of the circuit was made with a pin, held
either with a rigid support or a flexible aluminum support. The flexible
aluminum support was obtained by cutting from a 0.9 mm 99.95 wt%
Al sheet an isosceles triangle of 2 cm base and 5 cm height, with the
contact pin mounted on the tip, as schematically described in Figure
2d. In both cases, the pin was connected to the negative pole of the 9 V
battery by a copper cable. In order to measure the current the positive
pole of the battery was connected to the counter electrode, placed in
the measuring cell, through a measuring resistance.
The test electrolyte in the two electrochemical cells was a 3.5
wt.%NaCl aqueous solution, which is commonly employed for corro-
sion tests. Therefore, in both cells the only available cathodic half-cell
reactions are hydrogen evolution and oxygen reduction. Due to the
high potential difference across the working and the counter elec-
trodes, it is possible to assume that oxygen reduction occurred under
mass transport control, with a limiting current density at room tem-
perature of ∼10 μA cm−2 ,39 thus being almost negligible with respect
to the current measured during the experiments. Similarly to oxygen,
the effects associated with the solubility of hydrogen in the solution
are expected to be equivalent on both sides, and therefore to cancel
out. This is due to the fact that the volume of the solution in the test
cell is closely similar to that in the measurement cell, and the amount
of hydrogen evolved in both cells is virtually identical.
High purity titaniumfoils were used both as anode and cathode
materials in the two cells. The area of the hydrogen evolving cathodes
was ∼1 cm2 , while the area of the anodes was ∼100 cm2 .
Experimental Validation
In order to verify the accuracy and the limitations of the hydrogen
balance, the balance arm was prepared as described in Figure 3, such
that a known current was applied by the potentiostat to (and hence a
known amount of hydrogen could be generated from) the electrode
placed in the measuring cell. Preliminary testing indicated that a value
of measuring resistance of 100 ohm provided the most accurate results,
and hence only results obtained with this value of measuring resistance
are presented hereon. Two types of current-time profiles were applied
to the electrode in the measuring cell. The first current-time cycle
 C622 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017)

4 4 Balance
Balance - 50 pts average
Balance Potentiostat
3 Balance - 50 pts. average 3
Potentiostat

Current / mA
Current / mA

2 2

1 1

0 0

0 5000 10000 15000 20000 0 5000 10000 15000 20000

Time / s time /s

14000
14000 Potentiostat
Potentiostat
12000 Balance
12000 Balance
10000
10000
Charge / mC
Charge / mC

8000
8000
6000
6000
4000
4000
2000
2000
0
0
0 5000 10000 15000 20000
0 5000 10000 15000 20000
time / s
Time / s
Figure 6. Current (a) and charge (b) applied by the potentiostat to the hydro-
Figure 5. Current (a) and charge (b) applied by the potentiostat to the hydro- gen evolving electrode in the test cell (red lines) and resulting current (a) and
gen evolving electrode in the test cell (red lines) and resulting current (a) and charge (b) recorded in the measurement cell. The test was performed by using
charge (b) recorded in the measurement cell. The test was performed by using a 100 ohm resistor (Rm ) and a contact pin mounted on a flexible aluminum
a 100 ohm resistor (Rm ) and the contact pin mounted on a rigid support. support.

(Figures 5, 6 red lines) involved: i) no current applied for the first 600
seconds, ii) 0.5 mA applied for 3600 s, iii) no current applied for 3600
s, iv) 1 mA for 3600 s, v) no current applied for 3600 s, vi) 2 mA
for 3600 seconds and vii) no current applied for 3600 s. The second
current-time cycle (Figure 7) was similar, i.e. it comprised periods of
3600 s when the current was applied, separated by periods of 3600 s
when the current was not applied. For the second current-time cycle,
the values of applied current were varied from 0.5 mA to 0.1 mA at
0.1 mA intervals. The purpose of the first current-time cycle was to
evaluate the accuracy of the response for relatively large values of
current and the time required to the balance to respond to a change in
current, while the purpose of the second cycle is to identify the lower
limit of current detection.
Figure 5 presents the results obtained by using a contact pin
mounted on a rigid support. In Figure 5, the current applied in the
test cell by the potentiostat (red curve) is overlapped on the current
measured from the measuring cell (black). If the balance behaved
ideally, the two curves should overlap. However, it is evident that
the current measured by the hydrogen balance is relatively noisy, and
does not follow immediately the current applied by the potentiostat,
but a transient of about 400 seconds is observed when the current is
increased or decreased stepwise. However, smoothing of the current
curves reveals that the average values are closely similar, albeit with
some noise. Scrutiny of the time evolution of the charge, obtained by
integrating the current over time, reveals that at the end of the experi-
ment an error of 7% of the total charge passed is observed. Such error
could be considered not excessive for most corrosion measurements.
Figure 6 presents the results obtained in a similar experiment,
conducted under nominally identical conditions, except for the fact
that the contacting pin was not mounted on a rigid support but on the
triangular aluminum sheet, such as the contact pin could move slightly
upward after touching the contact pad on the balance arm. It is evident
that the noise levels were significantly reduced at high current, and
virtually no current was detected by the balance when no current
was applied by the potentiostat. For the higher values of current, the
transient time was also reduced. Comparison of the values of charge
(Figure 6b) indicates that the charge measured by the balance was
closely similar to that measured by the potentiostat (approximately
2% error).
Figure 7 presents the result obtained by applying the second
current-time cycle, with the contact pin mounted on the aluminum
support, a setup identical to that of the data presented in Figure 6.
It is evident that for currents below 0.3 mA, the noise in the signal
recorded from the balance becomes substantial and it is difficult to

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 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017) C623

2.2 Balance through the measurement cell during the time when the contact pin
2.0 Balance - 50 pts average touches the contact pad on the arm. Thus, for a constant contact time
Potentiostat between pin and pad, the current (and hence the charge) delivered to
1.8 the measurement cell increases with decreasing values of resistance.
1.6 Similarly, for a constant value of measuring resistance, the charge de-
1.4
livered to the measurement cell per time unit increases with increasing
Current / mA

contact time between pin and pad. However, the same contact time can
1.2
be achieved equivalently by a low number of relatively long contacts
1.0 or by a high number of short contacts. Overall, for a fixed position of
0.8 the center of gravity, the contact time depends on the imbalance be-
tween the hydrogen present in the measurement cell and the hydrogen
0.6
present in the test cell; the more the hydrogen in the test cell exceeds
0.4 that in the measurement cell, the longer the contact time per time unit.
0.2 The position of the center of gravity with respect to the support point
also contributes to the overall behavior, since, for a given imbalance in
0.0
hydrogen amounts between measurement and test cell, the displace-
0 10000 20000 30000 ment of the arm increases for decreasing distance between center of
time / s gravity and support point.
Another important consideration is that, when the contact pad
connected to the balance arm moves upwards touching the contact
pin, it has a tendency to bounce back (downwards) as a result of the
6000
(relatively elastic) collision between pad and pin and of the inertial
Potentiostat forces. In addition, during the contact time, hydrogen is evolved in the
5000 Balance measurement cell, producing a buoyancy force that tends to displace
the contact pad downwards. Thus, the two effects (bouncing of the pad
on the pin and generation of hydrogen in the measurement cell) act in
4000
the same direction and the balance shows some degree of oscillation.
Charge / mC

3000
2000
1000
0
0 5000 10000 15000 20000 25000 30000 35000 40000
time/sec
Figure 7. Current (a) and charge (b) applied by the potentiostat to the hydro-
gen evolving electrode in the test cell (red lines) and resulting current (a) and
charge (b) recorded in the measurement cell. The test was performed by using
a 100 ohm resistor (Rm ) and a contact pin mounted on a flexible aluminum
support.
clearly resolve the values of current. However, integration of the cur-
rent measured by the balance shows that, overall, the values of charge
measured from the balance were closely similar to those measured
from the potentiostat, even for the lower values of current. As the
applied current decreased, the transients in the curve measured by the
balance become longer, and hence it was difficult to separate the steps.
Discussion
The operation of the hydrogen balance relies on the buoyancy force
generated by the evolved hydrogen on the two collecting cylinders. For
relatively long experimental times the balance is able to equilibrate
and the current flowing across the measurement cell reflects accurately
the amount of hydrogen evolved in the test cell, regardless of the fine
details of the experimental setup. However, the transient behavior of
the balance is affected by several practical details, such as the value
of the measurement resistor, the mechanical behavior of contact pin,
and the position of the center of gravity relative to the support point.
The value of the measurement resistor, for a fixed voltage sup-
plied to the measurement cell and provided that the electrodes in the
measurement cell are not excessively small (as in the experiments
presented here), is the main factor that limits amount current flowing
Such oscillation is barely visible by the naked eye, but it can be clearly
resolved with an optical microscope, as illustrated in Figures 8a–8d.
From the figure, the relative position of pin and pad can be evaluated
by looking at the reflected image of the pin on the pad. When the tip
of the pin touches the tip of the reflected image, pin and pad are in
contact, whereas when the tip of the pin is visually separated from
the tip of the pin in the reflected image, there is no electrical contact
between pin and pad. In Figure 8, the red lines are added as a guide
to the eye to identify the tip of the pin and the tip of the pin in the
reflected image.
As a result of the combination of all the effects described above, the
way in which the contact pin reacts to the impact with the moving bal-
ance arm, has a significant impact on the quality of the measurement,
because the current is delivered differently to the measurement cell.
Figures 8e–8f clearly illustrates this issue. In Figure 8e, the potential
across the measuring resistor (and hence the current flowing to the
test cell) has been recorded at high frequency (5 kHz) approximately
in the middle of the 2 mA step in Figures 5 and 6. Figure 8e displays
the behavior recorded for a contact pin mounted on a rigid support,
while Figure 8f shows the behavior for the pin mounted on the flexible
aluminum support, schematically described in Figure 2d. It is evident
that (for approximately the same value of current measured) the rigid
support produces a lower number of longer contacts, while the flexible
support produces a higher number of shorter contacts, since the arm
oscillates less. Unreported microscope videos of the pin contacting
the pad also show that the amplitude of the oscillation of the bal-
ance arm is significantly larger when the pin is mounted on the rigid
support.
Based on the considerations above, it can be concluded that an
ideal hydrogen balance should be perfectly damped, such as the con-
tact pin only touches the contact pad on the arm for the time re-
quired to produce enough hydrogen in the measurement cell, and
once the hydrogen produced is sufficient to balance that in the test
cell, the contact between arm and pad is interrupted by an infinites-
imally small displacement of the arm. In this case, since the dis-
placement of the arm would be infinitesimally small, the vertical
distance between center of gravity and support point would have no
effect.
In practice, the balance behaves non-ideally, since the mechanical
and electrical behaviors are inherently interlinked by complex inter-
actions as described above. For example, sometimes the hydrogen in
the test cell might slightly exceed the hydrogen on measurement cell

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 C624 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017)
but the duration of a single contact between pad and pin might not be
sufficient to exactly re-balance the amount of hydrogen in both sides
because the pin might bounce on the pad before sufficient current is
passed. Similarly, when the amount of hydrogen is equal in the two
sides, the arm’s oscillation might produce unwanted contact between
pin and pad, unbalancing the amount of hydrogen in the two cells.
As a result, the current measured by the balance is relatively noisy
and transients are long. Similarly, when the current in the test cell is
stepwise reduced to zero, residual oscillations of the arm will induce
occasional contact between pin and pad. Each contact will produce an
excess of hydrogen in the measurement cell side, and some oscilla-
tion of the arm, which might induce another (unwanted) contact, with
associated hydrogen excess. If this process proceeds for some time,
eventually the excess hydrogen in the measurement cell will prevent
any further contact between pin and pad, but some current has been
already measured even when the electrical current applied to the test
cell was zero.
Based on the discussion above, it is clear that, for long measure-
ment times (minutes to hours) and relatively constant rate of hydrogen
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Figure 8. a-d) Optical images of the contact pin and contact
pad. Red lines are a guide to the eye and highlight the relative
position of the pin tip and of the reflected image of the pin
tip. e-f) Potential difference across the measuring resistor as
a function of time measured at 5 kHz during the 2 mA step
of Figures 5 and 6. e) pin mounted on rigid support, f) pin
mounted on flexible aluminum support.
evolved in the test cell (as in many free corrosion-related scenarios),
the charge measurements obtained from the hydrogen balance are
very reliable, since sufficient time is available to achieve a dynamic
equilibrium between the oscillations and the current delivered in the
measurement cell. However, if the current varies substantially within a
short period of times (seconds to minutes), the hydrogen balance is not
suitable to perform reliable measurements. Overall, the hydrogen bal-
ance appears to have substantially higher time and current resolution
compared to the traditional volumetric hydrogen collection method
and comparable current resolution compared the gravimetric method
using a commercial precision scale. However, the hydrogen balance
behaves significantly worse in terms of time resolution compared to
the gravimetric hydrogen collection method using a digital laboratory
scale, since transients of the order of hundreds of seconds are ob-
served before a steady reading is attained. The main advantage of the
hydrogen balance is the relatively low cost of the equipment. Further,
the principle of measuring a weight change by measuring the current
associated to an electrochemical reaction, introduced here for the first
time and exemplified by the hydrogen balance, might be useful in a
 Journal of The Electrochemical Society, 164 (12) C618-C625 (2017)
variety of other applications where detecting the variation of weight
of an immersed specimen is of interest.
Conclusions
In this work, a new method to measure hydrogen evolving from a
submerged electrode was presented. The method consists of a mechan-
ical balance with a horizontal arm attached to two hydrogen-collecting
containers that are submerged in two independent electrochemical
cells. When hydrogen is developed in the test cell, the balance arm is
displaced, closing an electrical contact that triggers hydrogen develop-
ment in the other cell. Measuring the current flowing in the measuring
cell enables accurate estimation of the hydrogen evolved in the test
cell. The hydrogen balance is significantly more accurate and provides
accurate estimation of hydrogen evolved that the usual volumetric hy-
drogen collection method. However, a time delay of the order of tenths
or hundreds of seconds (depending on the detailed configuration) is
present before the current can be accurately measured. This prevents
the use of the hydrogen balance for real-time coupled, relatively short,
electrochemical and hydrogen measurement. On the other hand, the
hydrogen balance is simpler and less expensive than the gravimetric
methods based on the use of a precise digital laboratory scale and
could be used for all those applications where several long term tests
must run in parallel.
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