Difference between revisions of "Reference Electrode Potentials"

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(The Calomel Electrode)
(The Calomel Electrode)
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'''Notes'''
 
'''Notes'''
:SCE, saturated calomel electrode: Hg/Hg<sub>2</sub >Cl<sub>2</sub>, KCl (sat'd)
+
: LJ, liquid junction
:SSCE, saturated salt calomel electrode: Hg/Hg<sub>2</sub >Cl<sub>2</sub>, NaCl (sat'd)
+
 
:NCE, normal calomel electrode: Hg/Hg<sub>2</sub >Cl<sub>2</sub>, KCl (1 M)  
 
:NCE, normal calomel electrode: Hg/Hg<sub>2</sub >Cl<sub>2</sub>, KCl (1 M)  
 
:NHE, normal hydrogen electrode
 
:NHE, normal hydrogen electrode
 +
:SCE, saturated calomel electrode: Hg/Hg<sub>2</sub >Cl<sub>2</sub>, KCl (sat'd)
 +
:SSCE, saturated salt calomel electrode: Hg/Hg<sub>2</sub >Cl<sub>2</sub>, NaCl (sat'd)
 +
  
 
'''References'''
 
'''References'''

Revision as of 13:22, 4 August 2014

The Calomel Electrode

The calomel electrode is usually constructed from a platinum wire inserted into a mixture of calomel (mercurous chloride, Hg2Cl2) and liquid mercury, with an electrolyte solution of KCl or NaCl. The relevant half equation is: Hg2Cl2 + 2e → 2Hgliq + 2Cl

As this equation implies the electrode potential is dependent on chloride concentration, but independent of hydrogen ion (acid) concentration.


Table 1. Potential (V) of the Calomel Electrode at 25°C
Conditions vs NHE vs SCE LJ Reference
Hg/Hg2Cl2, KCl (0.1 M) 0.3337 0.0925 - 1,3
Hg/Hg2Cl2, KCl (0.1 M) 0.336 0.092 Yes 2
NCE 0.2801 0.0389 - 1,3
NCE 0.283 0.039 Yes 2
Hg/Hg2Cl2, KCl (3. 5M) 0.250 0.006 Yes 2
SCE 0.2412 0 - 1,3
SCE 0.244 0 Yes 2
SSCE 0.2360 -0.0052 - 1

Notes

LJ, liquid junction
NCE, normal calomel electrode: Hg/Hg2Cl2, KCl (1 M)
NHE, normal hydrogen electrode
SCE, saturated calomel electrode: Hg/Hg2Cl2, KCl (sat'd)
SSCE, saturated salt calomel electrode: Hg/Hg2Cl2, NaCl (sat'd)


References

(1) "Electrochemical Methods: Fundamentals and Applications", AJ Bard and LR Faulkner, John Wiley & Sons, NY (2000). See the table on inside back cover.

(2) "Electrochemistry for Chemists, Second Edition", DT Sawyer, AJ Sobkowiak, J Roberts, Jr., John Wiley & Sons, NY (1995). See Section 5.2.

(3) "Handbook of Analytical Chemistry", L Meites (ed.), McGraw Hill, NY (1963). See Section 5.