Chem.

Educator 2011, 16, 1–3 1

Construction of a Novel Reversible Hydrogen Electrode (RHE)

Teresa Buendía-Delgadillo†, Fernando Delgadillo-Núñez†, Norberto Casillas‡, Jorge G.

Ibanez*,§, Maximiliano Barcena-Soto‡

†Departamento de Ingeniería Química, ‡Departamento de Química. Centro Universitario de Ciencias Exactas e

Ingenierías, Universidad de Guadalajara. Blvd. Marcelino García Barragán #1451, Guadalajara, Jal., 44430,
México, §Depto. de Ing. y C. Químicas, Universidad Iberoamericana, Prol. Reforma #880, Lomas de Santa Fe,
México, D.F. 01219, México, jorge.ibanez@uia.mx
Received June 17, 2010. Accepted September 2, 2010.

Abstract: A novel reversible hydrogen electrode (RHE) is built and applied to the measurement of equilibrium
potentials of several redox couples. Its operating principle is similar to that of a Normal Hydrogen Electrode
(NHE) in that the potential for both is set by the H+/H2 couple. The proposed construction of this novel RHE is
simpler and safer. Here, a Pt wire is placed inside a glass tube sealed at one end and filled with an H+ solution of
unit activity. H2 gas is generated by electrolysis and becomes trapped at the top of the tube so that one section of
the Pt wire is in contact with this gas and another section with an H+ solution of unit activity. This experimental
setup avoids the requirement for bubbling H2 gas on platinized Pt foil at P = 1 atm as in a typical NHE.

Introduction gauges to control the pressure and gas outflow. A stream of

In each half-reaction of an electrochemical cell an interfacial
potential difference is established between an electrode and the
ions in the solution, i.e., Mn+/M. Although the absolute value
of the potential of an electrode in contact with its ions in
solution is a key parameter in electrochemistry, it cannot be
measured experimentally because the procedure itself would
introduce a new interface [1]. One then has to select,
standardize, and use a half cell as a reference electrode.
Commercial reference electrodes are readily available,
although their cost can be relatively high. Home-made
reference electrodes include the calomel electrode (Hg+/Hg)
[2, 3], the Ag/AgCl electrode [4–6], and the Cu2+/Cu electrode
[7, 8].
The Standard Hydrogen Electrode, SHE (or Normal
Hydrogen Electrode, NHE) is internationally accepted as a
primary reference for measuring the potential of other redox
couples in solution. Here, the potential is fixed by the H+/H2
pair in the cell: Pt|H2(P = 1 atm)|H+(a = 1)||Mn+|M.
The reaction involved is:
2H   aq   2e H2  g 
This reaction is reversible and has a small temperature
coefficient. By international convention it is assigned a
potential of 0.00 V at any temperature under standard
conditions [1, 9]. The physical construction of an NHE varies,
but the fundamental design involves bubbling H2 at a pressure
of 1 atm on a Pt surface (typically platinized with
hexachloroplatinic acid) placed in a solution of H+ unit activity
[1]. The H2 supply remains constant (P = 1 atm) using a
pressurized high purity H2 tank, equipped with valves and
*
Address correspondence to this author.
†
Departamento de Ingeniería Química, Universidad de Guadalajara
‡
Departamento de Química, Universidad de Guadalajara
§
Depto. de Ing. y C. Químicas, Universidad Iberoamericana
fine H2 bubbles is directed towards the electrogenerated thin
layer of Pt immersed in an H+ solution of unit activity [1,9].
This has the inherent risk of managing a high-pressure gas
which is also a fuel. A clever simplified design uses a Pt wire
enclosed in a plastic pipette and immersed in an acidic
solution; hydrogen gas is electrolytically produced and some
bubbles remain adhered to the Pt surface during the potential
measurement [10].
An alternative to this involves the use of a reversible
hydrogen electrode (RHE), which operates similarly to a NHE
in the sense that the potential is fixed with the same ion pair
H+/H2. Unlike a typical NHE, a RHE does not require a
continuous flow of hydrogen or the preservation of hydrogen
bubbles on the Pt surface [1, 10]. Instead, a small amount of H2
is produced in situ by electrolysis and accumulates inside a
glass tube (e.g., a Pasteur pipet barrel or a clear normal plastic
pen sealed at one end) equipped with a Pt wire in contact with
the electrolytically produced H2 gas and with an H+ solution of
unit activity. This electrode assembly requires only a small Pt
wire and makes the electrode more stable, rugged and easier to
manipulate than earlier proposals [10].
(1)
Experimental
Construction of the RHE. A small Pt wire (e.g., 1.5 cm long, 1
mm in diameter) is Au-soldered to a 5-cm long Cu wire (φ = 1 mm).
This wire system is placed inside a glass tube (e.g., 5 cm long, 6 mm
ID); one end is sealed with epoxy covering the Pt-Cu joint and leaving
out about 10 mm of the Pt wire protruding out of the epoxy plug at the
end of the tube seal (see Figure 1). A piece of commercial Teflon tape
(ca. 1.5 cm wide, 8 cm long) is then wrapped around the epoxy-sealed
end of the tube, and either a transparent automatic delivery pipet
plastic tip or a transparent ventilated cap from a writing ball point pen
(e.g., Bic crystal grip that has a hole at the tip) is tightly fitted at the
bottom of the enclosure. This Teflon tape seal prevents both the
escape of H2 and the admission of atmospheric O2. With a hypodermic
syringe, the tip of the new electrode is filled with 1.2 M HCl (i.e., a
solution of unit activity) as shown in Figure 2.

© 2011 The Chemical Educator, S1430-4171(11)0xxxx-x, Published xx/xx/2011, 10.1333/s00897112403a, xxxxxxaa.pdf

2 Chem. Educator, Vol. 16, 2011
Figure 1. Preparation of the RHE body.
Figure 2. Filling the automatic delivery pipet tip with a unit activity
HCl solution (1.2 M).
Figure 3. HCl electrolysis to produce H2 in the RHE.
This electrode is then placed in 1.2 M HCl and the cell completed
with a Pt auxiliary electrode or a graphite rod. A potential difference
is applied between the RHE and the auxiliary electrode by means of
an external 10–20 V DC power source or a commercial 9-V battery
(the positive terminal to the auxiliary electrode and the negative
terminal to the RHE, see Figure 3).
Some electrolytically produced H2 is allowed to accumulate at the
top of the RHE so as to cover about one half of the Pt wire. This will
maintain the Pt wire in contact with H2 gas while the rest remains in
contact with the H+ solution of unit activity. The auxiliary electrode
can now be removed from the cell and replaced with the desired
unknown redox couple in a separate container. The circuit is closed
© 2011 The Chemical Educator, S1430-4171(11)0xxxx-x, Published xx/xx/2011, 10.1333/s00897112403a, xxxxxxaa.pdf
Ibanez et al.
with a conventional ionic bridge or filter paper impregnated with a
saline or an HCl solution (see Figure 4). This experimental setup
allows the measurement of the reversible potentials of selected redox
couples using a commercial high impedance digital multimeter.
Preparation and measurement of the potentials of different
redox couples. Solutions of different redox couples can replace the
Cu2+/Cu test half cell of Figure 4. Examples include a 0.1 M solution
of Fe3+ and 0.1 M Fe2+ in contact with a Pt wire; a 0.1 M solution of
Cu2+ in contact with a Cu wire; and 0.1 M Zn2+ in contact with a Zn
wire. The potential of commercial or home-made reference electrodes
(for example, SCE and Ag/AgCl) [2–6] may be tested as well.
Results and Discussion
This novel electrode assembly provides a minute amount of
confined H2 in contact with a Pt wire and allows for stable
potential measurements during reasonable periods of time
(e.g., one week). The internal pressure is slightly greater than 1
atm due to the liquid column displaced; this is why this
electrode is a RHE and not a NHE. Contrary to a NHE, no
further electrocatalytic activation of the Pt surface is required
to obtain fast, reliable and reproducible potential
measurements [1]. The operation of a RHE can be rationalized
in terms of a conventional reference electrode.
When connecting the RHE redox couple to a redox pair with
a more positive potential, the RHE acts as an anode and part of
the H2 gas becomes oxidized, producing H+ ions that enter the
solution. On the contrary, when the RHE is connected to a test
redox couple with a less positive potential, the RHE will act as
a cathode reducing H+ ions in the solution and producing H2
gas that becomes trapped in it. The sign of each measured
potential matches the value listed in the standard potential
tables when connecting the RHE directly to the earth (ground)
terminal of the digital multimeter (i.e., the black or common
terminal).
As shown in Table 1, the potential values for some redox
couples measured using this RHE and corrected for the
Nernstian effect of concentrations agree well with those
reported using a NHE [1]. The differences are usually due to
the potential drop caused by the salt bridge or filter paper used
as ion conductors, the entry of atmospheric O2 in the RHE due
to defects in the Teflon tape insulation, or the inherent
inaccuracy of the measurement (e.g., the use of a low internal
impedance multimeter).
An ammeter may be connected in series to monitor the
current flow during electrolysis; this information, together with
the electrolysis time, can be used to estimate the amount of
hydrogen produced. A typical run involves the passage of 50-
150 mA for 2 min (this may vary with the potential drop in a
particular cell). A higher hydrogen column reflects a slightly
higher pressure. These systems can remain in operation for a
week or longer without significant potential changes.
Conclusions
A primary, reversible reference electrode (the reversible
hydrogen electrode, RHE) that operates with the H+/H2 redox
couple can be easily constructed that avoids the risk and
complications associated with the operation of a high pressure
H2 cylinder. The potentials measured for several redox couples
are very close to those reported in the literature. These RHEs
are stable for up to a week or longer.
Construction of a Novel Reversible Hydrogen Electrode (RHE) Chem. Educator, Vol. 16, 2011 3

Table 1. Redox potentials measured with a RHE and corrected with the Nernst equation
Redox couple Eº vs. NHENHE NHE NHE(V) E, calculated vs. NHE(V) E, measured vs. RHE(V) %error 100  1  Emeasured 
 
 Ecalculated 

Cu2+(0.1 M)/Cu 0.340 0.234 0.254 8.54
Zn2+(0.1 M)/Zn -0.763 -0.871 -0.785 9.82
Ag/AgCl 0.222 0.222 0.215 3.15
Fe3+(0.1 M)/Fe2+(0.1 M) 0.771 0.765 0.765 0
Hg2Cl2/Hg 0.241 0.240 0.235 2.08
* Data from reference [1]. See the Supplementary materials section for a sample calculation.

activity by using tabulated mean molar activity coefficients for

HCl as a function of the molar concentration [11], b) the
calculation of the estimated quantity (i.e., moles) and volume
of H2 trapped inside the RHE using the current and the
electrolysis time for the generation of H2, c) the experimental
determination of equilibrium potentials of different redox
couples already known, d) the calculation of emf of cell
reactions taking into account the concentration of the solutions
and using the Nernst equation, and e) calculation of the free
energy involved (http://dx.doi.org/10.1333/s00897112403a).

References and Notes

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Fundamentals and Applications, 2nd ed., Wiley, New York, 2001.
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86, 355.
6. Kauffman, C. A.; Muza, A. L.; Porambo, M. W.; and Marsh, A. L.
Chem. Educ., 2010, 15, 178.
7. Gronneberg, T.; Eggen, P. -O.; and Kvittingen, L. J. Chem. Educ.,
Figure 4. Measurement of the reversible potential of a redox couple
2007, 84, 671.
(e.g., Cu2+/Cu) vs. RHE, using a salt bridge to avoid contamination.
8. Riyazuddin, P. J. Chem. Educ., 1994, 71,167

Acknowledgements. TBD thanks the Electrochemistry and 9. Daniels, F.; and Alberty, R. A. Physical Chemistry, 6th printing,
CECSA, Mexico 1975.
Corrosion Laboratory (LEC) of the University of Guadalajara
for support, and JGI acknowledges partial support from 10. Eggen, P.-O. J. Chem. Educ., 2009, 86, 352.
CONACYT (Mexico). 11. Barrow, G. M. Physical Chemistry, 6th ed., McGraw-Hill, New York
1996.
Supplementary Materials. a) the calculation of the
concentration needed to prepare a solution of HCl of unit

© 2011 The Chemical Educator, S1430-4171(11)0xxxx-x, Published xx/xx/2011, 10.1333/s00897112403a, xxxxxxaa.pdf