Standard hydrogen

electrode

The standard hydrogen electrode

(abbreviated SHE), is a redox electrode
which forms the basis of the
thermodynamic scale of oxidation-
reduction potentials. Its absolute electrode
potential is estimated to be 4.44 ± 0.02 V at
25 °C, but to form a basis for comparison
with all other electrode reactions,
hydrogen's standard electrode potential
(E0) is declared to be zero volts at any
temperature.[1] Potentials of any other
electrodes are compared with that of the
standard hydrogen electrode at the same
temperature.

Hydrogen electrode is based on the redox

half cell:

2 H+(aq) + 2 e− → H2(g)

This redox reaction occurs at a platinized

platinum electrode. The electrode is dipped
in an acidic solution and pure hydrogen gas
is bubbled through it. The concentration of
both the reduced form and oxidised form is
maintained at unity. That implies that the
pressure of hydrogen gas is 1 bar (100 kPa)
and the activity coefficient of hydrogen ions
in the solution is unity. The activity of
hydrogen ions is their effective
concentration, which is equal to the formal
concentration times the activity coefficient.
These unit-less activity coefficients are
close to 1.00 for very dilute water solutions,
but usually lower for more concentrated
solutions. The Nernst equation should be
written as:
where:

aH+ is the activity of the hydrogen ions,

aH+ = fH+CH+ / C0
pH2 is the partial pressure of the
hydrogen gas, in pascals, Pa
R is the universal gas constant
T is the temperature, in kelvins
F is the Faraday constant (the charge per
mole of electrons), equal to
9.6485309 × 104 C mol−1
p0 is the standard pressure, 105 Pa

Relationship between the

normal hydrogen electrode
(NHE) and the standard
hydrogen electrode (SHE)
During the early development of
electrochemistry, researchers used the
normal hydrogen electrode as their
standard for zero potential. This was
convenient because it could actually be
constructed by "[immersing] a platinum
electrode into a solution of 1 N strong acid
and [bubbling] hydrogen gas through the
solution at about 1 atm pressure". However,
this electrode/solution interface was later
changed. What replaced it was a
theoretical electrode/solution interface,
where the concentration of H+ was 1 M, but
the H+ ions were assumed to have no
interaction with other ions (a condition not
physically attainable at those
concentrations). To differentiate this new
standard from the previous one it was
given the name 'Standard Hydrogen
Electrode'. [2]

In summary,

NHE: potential of a platinum electrode in

1 M acid solution
SHE: potential of a platinum electrode in
a theoretical ideal solution (the current
 2 D+(aq) + 2 e− → D2(g)

Also difference occurs when hydrogen

deuteride is used instead of hydrogen in
the electrode.[7]

Construction

Scheme of the standard hydrogen electrode

The scheme of the standard hydrogen
electrode:

1. platinized platinum electrode

2. hydrogen blow
3. solution of the acid with activity of H+
= 1 mol dm−3
4. hydroseal for preventing oxygen
interference
5. reservoir through which the second
half-element of the galvanic cell
should be attached. The connection
can be direct, through a narrow tube
to reduce mixing, or through a salt
bridge, depending on the other
 electrode and solution. This creates
an ionically conductive path to the
working electrode of interest.

See also

Wikimedia Commons has media

related to Standard hydrogen
electrode.

Table of standard electrode potentials

Reversible hydrogen electrode
Palladium-hydrogen electrode
Reference electrode
Dynamic hydrogen electrode
Quinhydrone electrode