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Rotating Cylinder Electrochemistry (RCE)

Last Updated: 4/30/19 by Neil Spinner

Article Contents/Section Navigation
  1. General Theory
  2. References

1General Theory

The rotating disk and ring-disk electrodes were developed primarily as a result of academic electroanalytical chemistry research.  In contrast, the theory for the rotating cylinder electrode (RCE) was developed by industrial researchers  Gabe, D. R.; Walsh, F. C.  Enhanced mass transfer at the rotating cylinder electrode. I. Characterization of a smooth cylinder and roughness development in solutions of constant concentration.  J. Appl. Electrochem., 1984, 14(5), 555–564.
Gabe, D. R.; Walsh, F. C.  Enhanced mass transfer at the rotating cylinder electrode. II. Development of roughness for solutions of decreasing concentration.  J. Appl. Electrochem., 1984, 14(5), 565–572.
Gabe, D. R.; Walsh, F. C.  Enhanced mass transfer at the rotating cylinder electrode: III. Pilot and production plant experience.  J. Appl. Electrochem., 1985, 15(6), 807–824.
 in the corrosion and electroplating communities.  While the flow of solution at a rotating disk (or ring-disk) is laminar over a wide range of rotation rates, the flow at the surface of a rotating cylinder is turbulent  Gabe, D. R.; Walsh, F. C.  The rotating cylinder electrode: a review of development.  J. Appl. Electrochem., 1983, 13(1), 3–21.  at all but the slowest rotation rates.  Thus, the RCE is an excellent tool for creating and controlling turbulent flow conditions in the laboratory, and it is most commonly used to mimic turbulent corrosion conditions found in large scale industrial settings such as oilfield pipeline corrosion.  Silverman, D. C.  Rotating Cylinder Electrode for Velocity Sensitivity Testing.  Corrosion, 1984, 40(5), 220–226.
Silverman, D. C.  Rotating Cylinder Electrode-Geometry Relationships for Prediction of Velocity-Sensitive Corrosion.  Corrosion, 1988, 44(1), 42–49.
Silverman, D. C.  Corrosion prediction in complex environments using electrochemical impedance spectroscopy.  Electrochim. Acta, 1993, 38(14), 2075–2078.
Silverman, D. C.  Technical Note: On Estimating Conditions for Simulating Velocity-Sensitive Corrosion in the Rotating Cylinder Electrode.  Corrosion, 1999, 55(12), 1115–1118.
Silverman, D. C.  Technical Note: Simplified Equation for Simulating Velocity-Sensitive Corrosion in the Rotating Cylinder Electrode at Higher Reynolds Numbers.  Corrosion, 2003, 59(3), 207–211.
Silverman, D. C.  The Rotating Cylinder Electrode for Examining Velocity-Sensitive Corrosion—A Review.  Corrosion, 2004, 60(11), 1003–1023.
Silverman, D. C.  Technical Note: Conditions for Similarity of Mass-Transfer Coefficients and Fluid Shear Stresses between the Rotating Cylinder Electrode and Pipe.  Corrosion, 2005, 61(6), 515–518.
Wranglen, G.; Berendson, J.; Karlberg, G.  Apparatus for Electrochemical Studies of Corrosion Processes in Flowing Systems.  In Physicochemical Hydrodynamics, 1st ed.; Spalding, B.; Prentice-Hall: Englewood Cliffs, NJ, 1977.
Holser, R. A.; Prentice, G.; Pond, R. B.; Guanti, R.  Use of Rotating Cylinder Electrodes to Simulate Turbulent Flow Conditions in Corroding Systems.  Corrosion, 1990, 46(9), 764–769.
Chen, T. Y.; Moccari, A. A.; Macdonald, D. D.  Development of Controlled Hydrodynamic Techniques for Corrosion Testing.  Corrosion, 1992, 48(3), 239–255.
Nesic, S.; Solvi, G. T.; Skejerve, S.  Comparison of rotating cylinder and loop methods for testing CO2 corrosion inhibitors.  Br. Corros. J., 1997, 32(4), 269–276.
  ASTM G170-01a Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory.  In ASTM International ATSM International: West Conshohocken, PA, 2012.
ASTM Editors  ASTM G185-06 Standard Practice for Evaluating and Qualifying Oil Field and Refinery Corrosion Inhibitors Using the Rotating Cylinder Electrode ATSM International: West Conshohocken, PA, 2012.
 
The turbulent flow at a rotating cylinder electrode conveys material from the bulk solution towards the electrode surface.  While the bulk solution remains well stirred by the main vortex induced by the rotating electrode, the layer of solution adjacent to the cylinder surface tends to rotate with the electrode.  Thus, a high shear condition is set up at the surface of the rotating cylinder, spinning off smaller Taylor vortices adjacent to the rotating electrode.
 
Net movement of material to the surface of a rotating cylinder was first characterized by Morris Eisenberg  Eisenberg, M.; Tobias, C. W.; Wilke, C. R.  Ionic Mass Transfer and Concentration Polarization at Rotating Electrodes.  Journal of The Electrochemical Society, 1954, 101(6), 306.
Eisenberg, M.; Tobias, C. W.; Wilke, C. R.  No title.  Chemilca Engineering Progress Symposium Series, 1955, 51, 1.
 in 1954 (about the same time that Levich was describing the rotating disk electrode).  Eisenberg’s work eventually led to the Eisenberg equation which gives the limiting current at a rotating cylinder electrode
 
\displaystyle{i_L = 0.0487nFA d_{cyl}^{+0.4} D^{+0.644}\nu^{-0.344}\omega^{+0.7}C}
 
in terms of the concentration (C) and diffusion coefficient (D) of the molecule or ion being studied, the Faraday constant (F = 96485 coulombs per mole), the electrode area (A), the diameter of the cylinder (dcyl), the kinematic viscosity of the solution (ν), and the angular rotation rate (ω = 2πf/60 , where f is the rotation rate in revolutions per minute).  In the years since Eisenberg’s initial work with the rotating cylinder, additional work by Gabe, Kear, Walsh, and Silverman has described industrial applications of the RCE.   Gabe, D. R.  The rotating cylinder electrode.  J. Appl. Electrochem., 1974, 4(2), 91–108.
Gabe, D. R.; Walsh, F. C.  The rotating cylinder electrode: a review of development.  J. Appl. Electrochem., 1983, 13(1), 3–21.
Gabe, D. R.; Walsh, F. C.  Enhanced mass transfer at the rotating cylinder electrode: III. Pilot and production plant experience.  J. Appl. Electrochem., 1985, 15(6), 807–824.
Kear, G.; Barker, B. D.; Stokes, K.; Walsh, F. C.  Flow influenced electrochemical corrosion of nickel aluminium bronze – Part I. Cathodic polarisation.  J. Appl. Electrochem., 2004, 34(12), 1235–1240.
Silverman, D. C.  The Rotating Cylinder Electrode for Examining Velocity-Sensitive Corrosion—A Review.  Corrosion, 2004, 60(11), 1003–1023.
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