Swimming Pool Age & Spa Merchandiser, November 1985

however, manufacturers of ozone

PPM or ORP: generators and industry consultants have
called for the use of ORP to monitor the
effectiveness of disinfection in ozone/
Which Should Be Used? chlorine systems.

Water treatment experts are Oregon Study

This June, James C. Brown, a
becoming increasingly aware that consultant formerly with the Oregon
water disinfection is dependent upon ORP State Health Department, presented
and not the free residual chlorine ratio. to the National Environmental
Health Association Conference in
Las Vegas the results of a remarkable field
study on “Chemical and
BY JACQUES M. STEININGER Microbiology Water Quality Constituents
of 30 Public Spas” in metropolitan
Portland, Ore.
Over the past few years, there coli organisms in swimming pool water is
Brown (et al.) found that: “Total
has been an increasing recognition among dependent on ORP and not on the free
and fecal coliform parameters proved
water treatment specialists and health residual chlorine level. As shown in Figure
to be unreliable indicators of
officials that the oxidation-reduction 1, the kill time is just a fraction of a second
bacteriological water quality (but) the
potential (ORP or Redox) can provide an at a Redox level of 650 mV, but it increases
oxidation reduction potential (ORP) was
effective measure of sanitizer activity in rapidly to several hours at lower ORP
found to be a reliable indicator of
pool or spa water. values.
bacteriological water quality. Waters
ORP technology has been In Germany and other European
having an ORP equal to or higher
recognized and incorporated into European countries where public health standards are
than 650 mV were well within accepted
and world water standards for several years. very high, a minimum ORP level of 750
bacterial parameters.”
In 1972, the World Health Organization mV is required by DIN Standard 19643
The key data from this study has
recognized in its Standards for Drinking (adopted in 1982) for public pools and DIN
been computer-sorted and listed by
Water (WHO 1972) that at an ORP level Standard 19644 for spas (December
decreasing ORP values in Table 1.
of 650 millivolts (mV), water is 1984).
The ORP values range from a high of
disinfected and viral inactivation is almost In the U.S., many public pools and
867 mV to a low of 296 mV, with an
instantaneous. spas use ORP controllers for automatic
average of 643 mV. As noted by
In 1968, a laboratory study by chlorine control but this is disguised by
Brown, both the plate count and the
Carlson, Hasselbarth and Mecke of the fact that the controller readouts usually
pseudomonas count showed a high
the Water Hygiene Institute of the are labeled in parts per million (ppm) of
degree of correlation with the ORP
German Federal Health Office free chlorine instead of the more
level — the high counts being found
showed that the rate of killing of E. meaningful ORP mV. More recently,
systematically in the bottom half of
the list, below the 650 mV mark.
The free chlorine level in the 30
spas included in the study varied
from a low of 0.72 ppm to a high of
30 ppm, with an average of 3.8 ppm
in spas without cyanurates and 6.7
ppm in spas using cyanurates. The
pH varied from a low of 5.8 to a high
of 8.2.
The cyanuric acid level varied from
zero in the five spas using sodium or
calcium hypochlorite to a high of
1,300 ppm in spas using cyanurates,
with an average of 228 ppm in the
cyanurated spas. This, of course, is
well in excess of the maximum
recommended values - 100 ppm, for
instance, in California

Figure 1 — Kill time of E. Coli as a function of ORP.

San Diego
. Survey
These results unfortunately confirm
those of a recent survey of commercial
It is remarkable that the key indicator of
spas in San Diego, Calif., where more than bacteriological water quality was not ppm of free
50 percent of the spas were found out of
compliance with health department
chlorine, as generally expected, but the ORP level,
regulations. clearty confirming the earlier study in Germany.
In view of the wide variations in
the levels of free chlorine, pH and
cyanuric acid in the Oregon study, it water sanitation, this ratio with some simplification by reactions of
is remarkable that the key indicator should be as high as possible. Whenever it the type:
of bacteriological water quality was not is allowed to fall below 5:1 by weight
ppm of free chlorine, as generally (either through chlorine loss or by NH2CONH2 + 6 HOCl --->
Ammoniated Free
expected, but the ORP level, introduction of waste products),
Compounds Chlorine
clearly confirming the earlier study of essentially all the chlorine in
swimming pool waters in .Germany. the water is converted into compounds N2+ 6 C l+ CO2 + 5 H20 (4)
In addition, both studies found the called monochloramines, such as NHCl2:
same minimum ORP level of 650 mV This last equation corresponds to
for safe water quality, whether cyanuric NH2CONH2 + 2 HOCl ---> what is generally known as “breakpoint
acid is used or not. Ammoniated Free chlorination.” To prevent chloramine
These results are expected to have Compounds Chlorine formation, a constant state of breakpoint
a profound impact on water treatment chlorination is required. In other words,
2NH2Cl + CO2 + H2O (2) the free chlorine level must be at least 10
procedures in this country, particularly in
Monochloramine times the level of ammoniated compounds
commercial spas but also in all public
in the water at all times. This can be
pools and spas. There is a need, therefore,
At a pH of seven to eight, this accomplished only with frequent testing
for a new and comprehensive analysis of of the water or, more easily and reliably,
reaction takes place in a fraction of a
sanitizer chemistry in order to provide a with automated equipment.
second. Although chloramines have
better understanding of the reasons why
some bactericidal properties, their kill
ORP readings have been so successful in Two Forms of Free Chlorine
ratios for various micro-organisms
monitoring sanitizer performance. Up to this point, we have assumed
are as much as 80 to 100 times lower
that the pH of the water remains low,
than those of free chlorine, HOCl.
Free and Combined Chlorine (i.e. below 7.0). Now, the picture is
When the ratio of chlorine to further complicated by the fact that
When chlorine in any form is
nitrogen is progressively increased back there are two forms of free chlorine:
introduced into pool or spa water, it
above 5:1 by the addition of small
forms free chlorine (HOCl), which is
amounts of chlorine, the • the molecular form, hypochlorous
an excellent bactericide:
monochloramines are transformed into acid, HOCl, which is the fast-acting
other types of compounds called free chlorine, and
Cl2 + H2O ---> HOCl + HCl (1) • the ionic form, OCl-, which is a
Chlorine Water Free Hydrochloric
dichloramines, such as NHCl2:
slow-acting sanitizer.
Chlorine Acid
NH2CONH2 + 4 HOCl --->
Ammoniated Free HOCl is a weak acid. As the pH
Free chlorine, however, readily Compounds Chlorine increases, it dissociates to produce
combines with organic waste materials that the hypochlorite ion and a hydrogen
are present in the water (such as body 2 NHCL2 + CO2 + 3 H20 (3) ion:
perspiration, urine, cosmetics, hair sprays Dichloramine
or other ammoniated compounds) to form HOCl <---> OCl- + H+ (5)
combined chlorine compounds called Dichloramines are even worse than Hypochlorous Hypochlorite Hydrogen
chloramines, which are poor bactericides Acid Ion Ion
monochloramines. They are notorious for
and have obnoxious properties. their bad smell (the so-called “chlorine The equilibrium constant at 20°C
By now, everybody in the pool and odor”) and for eye irritation. They are the is 3.3 x 10-8. Figure 2 shows the familiar
spa industry is or should be familiar source of most customer complaints about ionization curve for HOCl, representing
with chloramines. However, the public pools and spas. the above reaction. Note that the
mechanisms of formation and destruction Finally, when more chlorine is concentration of HOCl, the fast-acting
of chloramines generally are poorly added to the water and the ratio of sanitizer, decreases very rapidly with
understood in the industry. chlorine to nitrogen is increased to increasing pH in the range of interest for
The chemistry of chlorine in water 10:1, the mono- and dichloramines pools and spas (7 to 8):
is controlled by a very important factor: are almost completely destroyed and • At a pH of 7.0, about 75 percent
the ratio of free chlorine divided are converted back into inoffensive of the free chlorine is HOCl
by the concentration of nitrogen or compounds, such as nitrogen compounds .
ammonia radicals in the water. For proper and chloride salts. This can be represented
 range, from a few hundred mV to 800 mV
or more.
The Handbook of Chlorination, by
Geo. Clifford White (Van Nostrand
Reinhold Co., 1972) gives the half-
cell oxidation-reduction potential Eo
at 25°C for HCOl:

HCOl + H+ + 2e ---> Cl + H20 (6)

E0 = 1.49V

If one assumes that Cl- is the

reduced state for chlorine, the variation of
ORP for HCOl is given by an expression
of the form:

ORP = E0 +
0.059/N*log[(HOCl)/(Cl-) - Eh (7)

where N is the number of electrons

e- and E„ is the potential of the reference
electrode. The actual relationship for ORP
is in fact more complex due to the need to
Figure 2 — lonization curve of HOCl as a function of pH.
consider the various oxidation and
• At a pH of 7.5, it is about 50/50 The increase in pH can take place reduction states of chlorine. In general,
HCOl and OCl-. very easily, especially if the water is though, one can see that ORP increases
• At a pH of 8.0, it is about 20 percent chlorinated with one of the alkaline logarithmically with increasing HCOl
HCOl and 80 percent OCl. forms of chlorine — sodium hypochlorite concentration.
HCOl is 80 to 300 times more (liquid bleach), NaOCl or, to a OCl has a much lower ORP value
effective than OCl-. For instance, it is much lesser extent, calcium hypochlorite, than HCOl, consistent with its much
more than 100 times more effective Ca(OCl)2 — or if the total alkalinity levels lower activity as a sanitizer:
than OCl- against cysts and 60 to 70 are too low to adequately buffer the water
times more effective against E. coli. against pH changes. OCl + H2O + 2e ---> Cl + OH (8)
The activity of OCl- as a sanitizer Remember, above a pH of 8, almost E0 = 0.90V
therefore can be compared to that of all the free chlorine is useless - The expression for the ORP of the
chloramines, (i.e. much below that of and the DPD test kit does not show hypochlorite ion OCl- is similar to
HCOl). it that of HCOl in Equation 7, but
For good bacteriological quality, it since Eo is lower, the ORP values are
is therefore essential to maintain a Free Chlorine and ORP much lower than those of HCOl. As
proper HCOl level in the water at all Fortunately, there is another way a result, when HCOl is present, it
times. Total free chlorine readings, of testing the water that is both simple and tends to “mask” the ORP of OCl-.
which combine both HCOl and reliable. It is called ORP. The same effect applies to chloramines,
OCl , cannot be depended upon for ORP or Redox refers to the oxidation- too. This is why the ORP sensor is said to
proper water maintenance. reduction potential - a measure of the read only the fast-acting free chlorine,
Unfortunately, the DPD test kit oxidizing properties of the sanitizer in HCOl.
and other free chlorine test kits do water - which is determined by a sensor
not differentiate between the two with a noble metal electrode, usually ORP and pH
forms of free chlorine. Therefore, platinum, and a standard Ag/AgCl The variations of the ORP of free
they cannot show the decrease in reference electrode. chlorine with pH are shown in Figure
HCOl concentration when the pH is When an ORP sensor is placed in 3. The experimental curves were
increased. This is no problem if the water containing a sanitizer - such determined at the Uniloc Co. in Irvine,
pH remains where it should be - at as chlorine, bromine or ozone - Calif, in the early 1970s. Close analysis
7.4 to 7.6. However, if the pH is allowed which is also an oxidizer, it acts like of the apparently complex set of
to rise - through the addition a small battery and creates a small curves shows that they simply reflect
of an alkaline sanitizer, of alkaline but measurable electric potential. the effect of HCOl ionization (Equation
make-up water or just body perspiration - The value of this potential varies with 5) on the expression for ORP
the concentration of HCOl can decrease the type of sanitizer and its concentration. (Equation 7).
to almost zero even though the DPD test As shown by the Oregon spa study data in This is illustrated in Figure 4, a
kit still shows the same level of free Table I, this potential can vary over a wide previously unpublished combination
chlorine. of data from Figures 2 and 3. The
 PPM Free Chlorine

ORP and Cyanuric Stabilizers

Introduced in 1956, cyanuric acid

and other stabilizers are now widely
used in pools and spas, but unfortunately
often without regard to their limitations.
The key advantage of stabilizers is that they
react with chlorine to form compounds
that - unlike free chlorine - are not
pH

destroyed by the UV rays in sunlight.

Field tests on outdoor pools in the St.
Louis, Mo. area showed that, without
stabilizers, chlorine residuals would be 90
percent destroyed in two to three hours on
sunny days. With 25 to 50 ppm of cyanuric
acid in the water, only 10 to 15 percent
were destroyed during the same period of
time.

650 750 850

ORP mV
Figure 3 — Variation of ORP for Free Chlorine as a function of pH.

solid lines show the variation of ORP

readings (from Figure 3) in the pH
range of 7 to 8 for total free chlorine
levels of 0.3, 0.5, 1.0 and 3.0 ppm,
respectively. As the pH increases between
7 and 8, the ORP sensor shows a marked
decrease in value for all chlorine levels.
For comparison, the dissociation
curve of HOCI (from Figure 2) is
superimposed on Figure 4 as a broken
line. It shows that the decrease of the
ORP reading with increasing pH
closely parallels the decrease in
concentration of HOCI. This comparison
of the curves for ORP and HOCI
is a key factor in understanding the
meaning of ORP measurements. It
explains why the ORP sensor can be
used very effectively to monitor
HOCI in the water. This is true not
only when the pH varies but also
when a cyanuric stabilizer is used, as
evidenced by the results of the Oregon
study.

Figure 4 — Comparison of ORP and HOCI variations as a function of pH.

 The chemistry of chlorocyanurates
is somewhat similar to the formation The data of the Oregon study shows that the
of chloramines. If cyanuric acid is presence of cyanuric acid reduces the ORP reading
represented by H(CYA), the following
reversible reaction takes place:
of the sensor. We understand now that this is because
it reduces the concentration of HOCI in the water.
H(CYA) + HOCI <---> Cl(CYA) + H20 (9)
Cyanuric Free Chlorocyanurate
Acid Chlorine cyanuric acid (up to 100 ppm). How- the sensor. We understand now that this is
ever, it is recommended to use higher because it reduces the concentration of
The difference with chloramine levels of chlorine residuals in stabilized HOCI in the water. It is therefore very
formation is that the equilibrium water, (i.e. two or three times the “normal” important not to exceed the maximum
constant for the reaction in Equation values). recommended concentration in the water
9 is much higher (about 10 -4 instead Cyanuric stabilization is used in (normally 100 ppm). If that concentration
of 10 -10 ). This means that the two ways: is exceeded, all or part of the water must
chlorocyanurates are much more unstable • By dissolving cyanuric acid into be dumped and replaced with fresh
than chloramines and can readily the water until a level of 25 to 30 water.
dissociate to recreate HOCI when it is ppm is reached. This is the method
needed. The reverse reaction of used with chlorine gas, sodium Analysis of Oregon Study Data
Equation 9 takes place automatically hypochlorite or calcium hypochlorite in In view of the above analysis of
as HOCI is used up in the water. The outdoor pools. ORP, it is useful at this stage to take
chlorocyanurate therefore constitutes • By using cyanurated chlorine a new look at Table I, the data of the
a reservoir - or a bank - of free compounds - either trichloroisocy- Oregon study.
active chlorine protected from the anurate tablets (trichlor) or sodium It is now evident that the ORP
destructive effects of UV rays. dichloroisocyanurate powder or value reflects the effects of at least
Field studies have shown that the granules (dichlor). three separate factors - free chlorine level,
bactericidal properties of chlorine in The data of the Oregon study in pH and cyanuric acid concentration. High
pool water are not affected by the Table I shows that the presence of ORP values result from a combination of
presence of normal concentrations of cyanuric acid reduces the ORP reading of high ppm levels, low pH values and low
cyanuric levels. The data shows that high
pH values and high cyanuric levels can
Commercial Spas Study, Portland, Oregon lead to low ORP levels, even though
the ppm of free chlorine is above the
Sample# ORP Total Free pH Cyanuric Plate Pseudo- minimum recommended value.
mV Cl Cl Acid Count monas The Oregon study confirms that
good water bacteriological quality
7 867 25.00 21.00 6.77 275 0 0
6 805 5.10 3.92 5.78 15 0 0 can be maintained in the presence of
13 795 34.00 30.00 7.13 200 0 0 cyanuric acid, if the proper ORP
3 787 10.00 8.54 6.83 0 0 0 level is maintained.
30 769 9.00 6.35 6.21 185 4 0
14 754 17.00 13.60 7.28 240 0 0 In other words, a low ORP value
27 741 3.95 2.41 7.19 0 6 0 (defined by Brown as below 650 mV)
23 736 2.90 2.50 7.49 250 0 0 should be used as an alarm signal to
16 732 6.62 4.38 7.42 150 0 0
12 696 7.50 5.62 7.61 390 1 0 alert the pool or spa operator or the
17 695 23.00 18.40 7.47 550 0 0 health department inspector that one
15 686 30.00 25.00 7.47 200 0 0 or more of these three factors -
26 681 4.40 3.75 7.30 95 2 0
2 668 6.62 4.92 7.90 0 0 0 ppm, pH or stabilizer - or their
22 653 3.50 2.30 7.81 175 0 0 combination - has resulted in unsanitary
28 634 3.80 2.35 6.97 130 13 0 water conditions.
8 633 8.94 7.34 7.49 720 0 0
9 623 3.84 2.28 7.83 150 12 2
5 618 3.08 1.20 7.06 225 170 12,400 ORP and Bromine
21 605 3.84 2.34 7.23 0 0 0 When dissolved in water in the
25 595 3.75 2.23 7.56 200 30 23
10 590 1.93 0.78 7.84 200 310 2,400 presence of a strong oxidizer, such as
18 564 1.87 0.83 7.87 0 150 94 chlorine or monopotassium persulfate,
29 554 3.54 1.88 7.39 185 15 0 bromine forms hypobromous acid (HOBr)
24 551 2.62 1.31 7.48 130 69 13
20 537 4.00 2.41 6.95 1,300 140 1,600 and the hypobromite ion (OBr). The
19 509 2.98 1.14 7.89 235 4,600 920 respective oxidation-reduction reactions
11 480 1.98 0.67 8.25 95 15,000 2,400 are similar to those of chlorine but with
4 412 1.43 0.72 8.25 57 2,200 540
1 296 1.59 1.20 7.79 150 640 1,600 lower E0 values:

Average 643 7.93 6.05 7.38 217

HOBr + H+ + 2e- ---> Br- + H20 (10) mostly ineffective in the prevention of plus the results of the Oregon
E0 = 1.33V algae growth. study and the new scientific understanding
OBr + H20 + 2e- ---> Br- + 2 OH- (11) Ozone is commonly used in Europe of ORP, it is recommended that pool and
E0 = 0.70V prior to chlorination or bromination. This spa professionals and health department
allows the operator to reduce the chlorine officials agree on a new standard for water
The same ORP sensor can be used or bromine levels in the water while quality in commercial or public pools and
for either chlorine or bromine, but maintaining high ORP values and good spas based on a clearly defined minimum
there are several key differences: water clarity. ORP level.
• Because of the lower E0 values, the It is further recommended that the
recommended bromine levels are ORP Controllers minimum ORP level be set at least
about twice the amount for chlorine, Chemical controllers used in the 650 mV or at 750 mV.
(i.e. between 3 and 6 ppm for spas). pool and spa industry normally use The ORP standard should apply to
• Bromamines are reputed to be an ORP sensor to monitor the sanitizer all sanitizers - including all forms of
effective sanitizers and to have no level as well as a pH sensor to chlorine, stabilized and nonstabilized, and
unpleasant odors. monitor the pH. The controller bromine - as well as to systems using
• Hypobromous acid (HOBr) automatically turns appropriate chemical ozone or other sterilization methods.
dissociates into hypobromite ions, OBr- feeders on and off, as required to
- just like chlorine - but this takes maintain the proper sanitizer and pH
place at a higher pH level, (i.e. above levels. Very close control can be Dr. Steininger is president of Santa
the normal pH range used in pools maintained, typically within 0.1 ppm Barbara Control Systems, Santa
and spas). At a pH of 8, there is of the chlorine setpoint and 0.1 pH Barbara, Calif., the manufacturer of the
about 83 percent of HOBr. Even at a units. This results in good water Chemtrol line of chemical automation
pH of 9, the ionization ratio is still quality and elimination of chloramines and equipment for pools and spas.
about 33 percent compared to 4 percent other unpleasant products, as well as in
for chlorine. The “pH shift” for savings in chemicals and labor.
bromine compared to chlorine is As mentioned earlier, most U.S.- REPRINTED WITH PERMISSION
about one full pH unit. In addition, built ORP controllers have readouts
bromine solutions are nearly neutral labeled in ppm free chlorine. The
in pH, so that they do not affect the more recent controllers show the
pH of the water nearly as much as variation of fast-acting free chlorine
most chlorine compounds. associated with variations in pH.
• There is no stabilizer for bromine, Older controllers use a correction
but it is reputed to be more stable based on the curves shown in Figure
than chlorine in the presence of sunlight 3 to mask this effect and display only
(65 percent loss in two hours). total free chlorine. This correction, A DIVISION OF
however, is not applicable if there is SANTA BARBARA CONTROL SYSTEMS
ORP and Ozone any cyanuric acid or chlorine-based Santa Barbara, CA 93111
Ozone is another strong oxidizer cyanurate in the water.
used in pool and spa water sanitation. Its For certain applications, such as CALL TOLL FREE
ORP value is very high: smaller pools and spas, it is also possible
to use an ORP-only controller, 800-621-2279
03 ---> 2H+ + 2e- + 02 + H20 (12) that is, without pH control. This is
E0 = 2.07V normally limited to the use of neutral-type
sanitizers such as a “dichloro” chlorine
www.sbcontrol.com
Ozone also can be monitored with (sodium dichloro-S-triazinetrione)
ORP sensors. Because of its short solution or bromine ”dihalo” (bromo-
lifetime and lack of residual value, chloro-dimethylhydantoin) sticks.
health departments require the Generally, ORP controllers without pH
maintenance of a chlorine or bromine control should not be used with alkaline
residual if ozone is used on public sanitizers such as sodium hypochlorite or
pools or spas. In addition, it also calcium hypochlorite. If the pH remains
may be required for safety reasons to fairly constant, these inexpensive
reduce the ozone level in the water controllers provide a very cost-
with activated charcoal before re- effective solution to the problem of
turning it to the pool. chemical control in small commercial
Ozone is very effective in destroy- installations.
ing bacteria and bad odors and gives
the water a “polished” look. It is also very ORP Standard Recommendation
good in oxidizing oil and grease, especially
in spas and hot tubs and in filters, but it is In view of the European experience,