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James R. Dimond
Dimondale Co., Inc., PO Box 838, Middlefield, OH 44062
Reprinted from MATERIALS PERFORMANCE, Vol. 33, No. 11, pp 14-17 (1994) November
Copyright 1994 by NACE International, PO Box 218340, Houston, TX 77218-8340
CATHODIC & ANODIC PROTECTION
Light Effects electrolyte in which the composition simultaneously. The actual potential of
changes, such as Ag/AgCl/Seawater the electrode then becomes a composite of
Copper salts and silver salts are both references in a tidal estuary. The all the potentials established by the
photo-sensitive so it should not be electrolyte of wet and gelled references various reactions. Very often, the effect
surprising that light has an effect on the is permanent if the
reference potential. To measure this compound formed between
150
effect, special electrodes were made up the element metal and the
in which two elements shared the same Ag/AgCl -43 mV/decade
100 contaminant is more stable
electrolyte. One element was kept
P otential shift, m V
than the compound formed
permanently in the dark by a double 50 as part of the reference
baffle while the other was exposed electrode's intended reaction.
directly to ambient light. The 0
Chlorides are the
magnitude of the light effect on contaminant most likely to
-50
Ag/AgCl electrodes was usually less Cu/CuSO4 20 mV/decade cause a problem with a
than a millivolt and so it could be safely -100 Cu/CuSO4 reference. The
ignored. Cu/CuSO4 electrodes, however, 0.01 0.1 1 10 100 1000 effect, (Figure 5), is to shift
showed a high degree of light sensitivity. Salt concentration, g/l
the reference potential in the
At high noon on the summer solstice, a negative direction. Other
copper element in direct sunlight Figure 4
Effect of electrolyte concentration on the reference potential
halides (iodides, bromides)
measured -52 mV vs a second element of Cu/CuSO4 and Ag/AgCl reference electrodes. and sulfides will have a
kept in total darkness. In open shade, similarly deleterious effect
the value was closer to -10 mV while has a constant composition which on both Cu/CuSO4 and Ag/AgCl
interior fluorescent lights caused a -2 eliminates this source of uncertainty. electrodes. Sulfides in the atmosphere
mV shift. When the element was The concentration coefficient for will even affect dry Ag/AgCl references
removed to a dark location and then re- Cu/CuSO4 electrodes is about 20 in storage if proper precautions are not
exposed the following day, potential mV/decade in the negative direction taken to protect them.
shifts of a similar magnitude were again (Figure 4). This means that for each
observed. However, when the element order of magnitude drop in the Design Life of Permanent (Gel)
was left in the sun for several hours, it concentration of CuSO4 in the Cells
apparently became desensitized and electrolyte, the reference potential will
subsequent photo-errors seldom shift 20 mV in the negative direction. The useful life of a dry or wet
exceeded -10 mV. For Ag/AgCl references, the reference electrode can be indefinite if it
concentration coefficient is about 43 is properly maintained. A gel electrode,
Housings of commercial portable mV/decade in the positive direction. on the other hand, has a fixed life
electrodes are usually transparent red or expectancy. In both wet and gel
yellow with a clear stripe to check the Contamination Effects electrodes, a composition difference
liquid level. When the direct exists across the membrane separating
illumination was through the red Contamination of the electrolyte the element's electrolyte from the
portion, no photo-error was observed but will alter the reference potential of an environment. This difference acts as a
if the illumination was through the clear electrode because competing chemical driving force for diffusion, which is both
portion, then values similar to those reactions, each with their own outward for the active species and inward
above were measured. To get consistent characteristic potential are occurring for contaminants. As diffusion changes
readings with a portable reference, the the composition of the
photo-error must be eliminated. The electrolyte, the reference
0
simplest way would be to place a strip of potential changes. In a gel
tape over the clear window. Permanent electrode, this change is
Cu/CuSO4
P otential shift, m V
Three broad factors affect the distance from the element to the replaced on a regular basis in order
service life of a permanent reference membrane, increases the time for the for them to maintain their accuracy.
electrode: the environment in which it effects of diffusion to reach the
operates; the chemical make-up of the element/gel interface where the • Dry electrodes should only be used in
gel; and the physical design of the reference potential is established. This electrolytes known to have a
electrode itself. Environmental effects factor is particularly significant when consistent composition and which
include both temperature and using gels with low ionic mobility. contain nothing that can adversely
concentration difference across the When the electrolyte next to the element react with the element metal.
membrane. Increasing either one will becomes diluted, the reference potential • Permanently installed references are
reduce service life by increasing will shift thereby ending the useful life usually not affected by photo-errors
diffusion rate. Permanent electrodes use of the electrode. and their ambient temperature range
a saturated salt solution as the basis for is much narrower (not including
the electrolyte gel. The chemical make- Another very important design
concrete bridge deck applications).
up of the gel can be modified to provide criterion for a permanent reference
For this reason, they are more
a reserve of salt to make up for that electrode is that it be engineered
accurate than a portable reference.
which is lost by diffusion. Both the specifically for its intended service.
amount and distribution of this reserve There are a wide variety of applications References
affects electrode life. There are limits, for permanent reference electrodes. For
however, to the amount of excess that each application, it is necessary to 1. J. Morgan, Cathodic Protection, 2nd ed.,
consider such factors as size limitations, (Houston, TX: NACE, 1987).
can be added to the gel before its 2. D. G. Ives & G. J, Janz, Reference Electrodes,
properties are affected. ambient temperature range, operating Theory and Practice, (New York, NY: Academic
pressure and installation procedures. If Press, 1961).
Two design details of an electrode these requirements are ignored, service 3. M. H. Peterson & R. E. Groover, MP 11, 5
(1972): p.19.
have a significant effect on service life: life will be drastically shortened .4 4. F. J. Ansuini, J. R. Dimond, "Long-term
membrane type and electrolyte path Stability Testing of Reference Electrodes for
length. The nature of the membrane Conclusions Reinforced Concrete," CORROSION/94, paper no.
295, (Houston, TX: NACE, 1994).
controls the quantity of salt which • Accurate readings with portable ______________________________
diffuses through it. Reducing this references require that the ambient
quantity can extend the service life but it temperature be recorded and a
also will increase internal cell temperature correction be applied. More information is available in
resistance. Clearly, there are limits to CORROSION/94 paper no. 323,
the extent to which this technique can be • Light striking the element of a presented in Baltimore, Maryland.
used for life extension since a high portable Cu/CuSO4 reference
internal resistance will cause through the clear-view window can Note: This is an exact reprint of the
measurement errors. Electrolyte path induce significant photo-errors. 1994 MP article. It has been reset and
length is also important because This window should be covered color added when it was converted to
diffusion is a time dependent with tape. electronic format.
phenomenon. Increasing the internal • Portable reference electrodes should
electrolyte path length, that is the be cleaned and the electrolyte be
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