Reference conversion and calibration
A change of reference is an additive shift for the same working-electrode state. It does not predict how the chemistry changes when pH, electrolyte or solvent is changed. Define each reference offset as the potential of that reference versus SHE.
Eout = ESHE − Eref,out vs SHE
ERHE = ESHE + [ln(10) RT/F] × pH
The RHE relation assumes unit hydrogen fugacity (1 bar standard state). At 25 °C, its slope is about 59.1593 mV per pH unit. Temperature changes that term, but they also change real reference electrodes: this calculator therefore refuses tabulated Ag/AgCl or SCE offsets away from 25 °C. Choose a calibrated Custom offset at the actual temperature.
Worked example
−0.250 V vs Ag/AgCl (3 M KCl), pH 7, 25 °C:
ESHE = −0.040 V; ERHE ≈ +0.374115 V.
Nonaqueous / ferrocene mode
Measure E½(Fc⁺/Fc) against your laboratory reference in the same solvent, supporting electrolyte and experimental conditions. The calibrated mode subtracts this measured value for A → Fc; it adds it for the inverse transformation. No universal Fc⁺/Fc-to-SHE offset is assumed.
Common questions
Why is saturated Ag/AgCl shown as +0.199 V, not +0.197 V?
The bundled table uses the +0.199 V saturated-KCl convention in the cited ACS Omega table. Published tabulations differ by a few millivolts. For your electrode, select Custom and use a documented or calibrated value; the label “Ag/AgCl” alone does not specify the reference potential.
Where are Hg/HgO and other reference electrodes?
Use Custom with the offset measured for the actual filling solution and temperature. In particular, do not replace a calibrated Hg/HgO potential by a universal number while changing hydroxide concentration. Nonaqueous reference-pair shifts should use the calibrated mode rather than an assumed bridge to SHE.
Sources and conventions
- IUPAC Gold Book · Nernst equation
- ACS Omega (2021) · Reference-potential conventions, Table 2
- Gamry Instruments · Reference electrodes and nonaqueous calibration
Method version 1.0.0 · 19 September 2026. Display precision is not measurement accuracy. Read the full scope and validation limits.
