Pseudo-reference electrodes

Research output: Chapter in Book/Report/Conference proceedingChapter

29 Citations (Scopus)

Abstract

Both the terms of pseudo-reference (literally “false” reference) electrode and quasireference (“almost” or “essentially”) electrode are used in the literature, often synonymously or interchangeably. The essential difference between a true reference electrode (as defined in Chap. 1) and a pseudo-reference electrode is the lack of thermodynamic equilibrium in the latter case [1-4]. In many cases simply platinum or silver or Ag/AgCl wires serve as pseudo- or quasi-reference electrodes. Obviously, thermodynamic equilibrium cannot exist, since there is no common component (anion or cation) in the two adjacent phases. However, usually they are calibrated by a reference redox system by adding the internal reference during the experiments into the electrolyte (preferred) or measuring their potential after the experiments by using a reference redox system or a conventional reference electrode. Sometimes when a reference redox system(e.g., ferrocene or cobaltocane) [5] is also used in situ, this reference electrode is called a quasi-reference electrode. These types of reference electrodes are used almost exclusively in nonaqueous systems (See Chaps. 2 and 6), in molten salts or at elevated temperatures, in ionic liquids (see Chap. 7), and mostly in three-electrode potentiostatic or potentiodynamic experiments. The advantages of the use of pseudo-reference electrodes are their simplicity, and because those are immersed directly into the electrolyte used in the cell, the ohmic resistance (impedance) effect is small, no liquid junction potential appears, and usually there is no contamination of the test solution by solvent molecules or ions that a conventional reference electrode might transfer. There are several disadvantages of the use of these reference electrodes. First is the lack of the thermodynamic equlibrium; therefore, one cannot calculate their potential. Second, because these are not ideally nonpolarizable electrodes, there is a shift of their potential during the measurements, which depends on the current density applied. Third, most pseudo-reference electrodes work over a limited range of conditions such as pH or temperature; outside of this range the electrodes’ behavior becomes unpredictable. However, it should be mentioned that, although under suitably selected conditions the potential of the pseudoreference electrode, although unknown, might be surprisingly constant during the experiments.

Original languageEnglish
Title of host publicationHandbook of Reference Electrodes
PublisherSpringer Berlin Heidelberg
Pages331-332
Number of pages2
ISBN (Electronic)9783642361883
ISBN (Print)9783642361876
DOIs
Publication statusPublished - Jan 1 2013

Fingerprint

Electrodes
Thermodynamics
Electrolytes
Experiments
Ionic Liquids
Acoustic impedance
Platinum
Silver
Anions
Cations
Molten materials
Contamination
Current density
Salts
Wire
Ions
Temperature
Molecules
Liquids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Inzelt, G. (2013). Pseudo-reference electrodes. In Handbook of Reference Electrodes (pp. 331-332). Springer Berlin Heidelberg. https://doi.org/10.1007/978-3-642-36188-3_14

Pseudo-reference electrodes. / Inzelt, G.

Handbook of Reference Electrodes. Springer Berlin Heidelberg, 2013. p. 331-332.

Research output: Chapter in Book/Report/Conference proceedingChapter

Inzelt, G 2013, Pseudo-reference electrodes. in Handbook of Reference Electrodes. Springer Berlin Heidelberg, pp. 331-332. https://doi.org/10.1007/978-3-642-36188-3_14
Inzelt G. Pseudo-reference electrodes. In Handbook of Reference Electrodes. Springer Berlin Heidelberg. 2013. p. 331-332 https://doi.org/10.1007/978-3-642-36188-3_14
Inzelt, G. / Pseudo-reference electrodes. Handbook of Reference Electrodes. Springer Berlin Heidelberg, 2013. pp. 331-332
@inbook{b6f1570fdd904181bcfe94ac859bd5f0,
title = "Pseudo-reference electrodes",
abstract = "Both the terms of pseudo-reference (literally “false” reference) electrode and quasireference (“almost” or “essentially”) electrode are used in the literature, often synonymously or interchangeably. The essential difference between a true reference electrode (as defined in Chap. 1) and a pseudo-reference electrode is the lack of thermodynamic equilibrium in the latter case [1-4]. In many cases simply platinum or silver or Ag/AgCl wires serve as pseudo- or quasi-reference electrodes. Obviously, thermodynamic equilibrium cannot exist, since there is no common component (anion or cation) in the two adjacent phases. However, usually they are calibrated by a reference redox system by adding the internal reference during the experiments into the electrolyte (preferred) or measuring their potential after the experiments by using a reference redox system or a conventional reference electrode. Sometimes when a reference redox system(e.g., ferrocene or cobaltocane) [5] is also used in situ, this reference electrode is called a quasi-reference electrode. These types of reference electrodes are used almost exclusively in nonaqueous systems (See Chaps. 2 and 6), in molten salts or at elevated temperatures, in ionic liquids (see Chap. 7), and mostly in three-electrode potentiostatic or potentiodynamic experiments. The advantages of the use of pseudo-reference electrodes are their simplicity, and because those are immersed directly into the electrolyte used in the cell, the ohmic resistance (impedance) effect is small, no liquid junction potential appears, and usually there is no contamination of the test solution by solvent molecules or ions that a conventional reference electrode might transfer. There are several disadvantages of the use of these reference electrodes. First is the lack of the thermodynamic equlibrium; therefore, one cannot calculate their potential. Second, because these are not ideally nonpolarizable electrodes, there is a shift of their potential during the measurements, which depends on the current density applied. Third, most pseudo-reference electrodes work over a limited range of conditions such as pH or temperature; outside of this range the electrodes’ behavior becomes unpredictable. However, it should be mentioned that, although under suitably selected conditions the potential of the pseudoreference electrode, although unknown, might be surprisingly constant during the experiments.",
author = "G. Inzelt",
year = "2013",
month = "1",
day = "1",
doi = "10.1007/978-3-642-36188-3_14",
language = "English",
isbn = "9783642361876",
pages = "331--332",
booktitle = "Handbook of Reference Electrodes",
publisher = "Springer Berlin Heidelberg",

}

TY - CHAP

T1 - Pseudo-reference electrodes

AU - Inzelt, G.

PY - 2013/1/1

Y1 - 2013/1/1

N2 - Both the terms of pseudo-reference (literally “false” reference) electrode and quasireference (“almost” or “essentially”) electrode are used in the literature, often synonymously or interchangeably. The essential difference between a true reference electrode (as defined in Chap. 1) and a pseudo-reference electrode is the lack of thermodynamic equilibrium in the latter case [1-4]. In many cases simply platinum or silver or Ag/AgCl wires serve as pseudo- or quasi-reference electrodes. Obviously, thermodynamic equilibrium cannot exist, since there is no common component (anion or cation) in the two adjacent phases. However, usually they are calibrated by a reference redox system by adding the internal reference during the experiments into the electrolyte (preferred) or measuring their potential after the experiments by using a reference redox system or a conventional reference electrode. Sometimes when a reference redox system(e.g., ferrocene or cobaltocane) [5] is also used in situ, this reference electrode is called a quasi-reference electrode. These types of reference electrodes are used almost exclusively in nonaqueous systems (See Chaps. 2 and 6), in molten salts or at elevated temperatures, in ionic liquids (see Chap. 7), and mostly in three-electrode potentiostatic or potentiodynamic experiments. The advantages of the use of pseudo-reference electrodes are their simplicity, and because those are immersed directly into the electrolyte used in the cell, the ohmic resistance (impedance) effect is small, no liquid junction potential appears, and usually there is no contamination of the test solution by solvent molecules or ions that a conventional reference electrode might transfer. There are several disadvantages of the use of these reference electrodes. First is the lack of the thermodynamic equlibrium; therefore, one cannot calculate their potential. Second, because these are not ideally nonpolarizable electrodes, there is a shift of their potential during the measurements, which depends on the current density applied. Third, most pseudo-reference electrodes work over a limited range of conditions such as pH or temperature; outside of this range the electrodes’ behavior becomes unpredictable. However, it should be mentioned that, although under suitably selected conditions the potential of the pseudoreference electrode, although unknown, might be surprisingly constant during the experiments.

AB - Both the terms of pseudo-reference (literally “false” reference) electrode and quasireference (“almost” or “essentially”) electrode are used in the literature, often synonymously or interchangeably. The essential difference between a true reference electrode (as defined in Chap. 1) and a pseudo-reference electrode is the lack of thermodynamic equilibrium in the latter case [1-4]. In many cases simply platinum or silver or Ag/AgCl wires serve as pseudo- or quasi-reference electrodes. Obviously, thermodynamic equilibrium cannot exist, since there is no common component (anion or cation) in the two adjacent phases. However, usually they are calibrated by a reference redox system by adding the internal reference during the experiments into the electrolyte (preferred) or measuring their potential after the experiments by using a reference redox system or a conventional reference electrode. Sometimes when a reference redox system(e.g., ferrocene or cobaltocane) [5] is also used in situ, this reference electrode is called a quasi-reference electrode. These types of reference electrodes are used almost exclusively in nonaqueous systems (See Chaps. 2 and 6), in molten salts or at elevated temperatures, in ionic liquids (see Chap. 7), and mostly in three-electrode potentiostatic or potentiodynamic experiments. The advantages of the use of pseudo-reference electrodes are their simplicity, and because those are immersed directly into the electrolyte used in the cell, the ohmic resistance (impedance) effect is small, no liquid junction potential appears, and usually there is no contamination of the test solution by solvent molecules or ions that a conventional reference electrode might transfer. There are several disadvantages of the use of these reference electrodes. First is the lack of the thermodynamic equlibrium; therefore, one cannot calculate their potential. Second, because these are not ideally nonpolarizable electrodes, there is a shift of their potential during the measurements, which depends on the current density applied. Third, most pseudo-reference electrodes work over a limited range of conditions such as pH or temperature; outside of this range the electrodes’ behavior becomes unpredictable. However, it should be mentioned that, although under suitably selected conditions the potential of the pseudoreference electrode, although unknown, might be surprisingly constant during the experiments.

UR - http://www.scopus.com/inward/record.url?scp=84986594828&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84986594828&partnerID=8YFLogxK

U2 - 10.1007/978-3-642-36188-3_14

DO - 10.1007/978-3-642-36188-3_14

M3 - Chapter

AN - SCOPUS:84986594828

SN - 9783642361876

SP - 331

EP - 332

BT - Handbook of Reference Electrodes

PB - Springer Berlin Heidelberg

ER -