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#1

05-25-2007, 06:56 PM

chem geek
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Mar 2007
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Pool Water Chemistry


This thread presents my findings so far on pool water chemistry
including the following:
1. More Accurate Calcite Saturation Index (CSI) to
replace Langelier Saturation Index (LSI)
2. Calculation of ppm HOCl (disinfecting chlorine) at
various levels of Total Free Chlorine (FC) and
Cyanuric Acid (CYA)
3. Determination of pH and Alkalinity changes when
adding chemicals to the pool
4. Various reaction rates including chlorine breakdown
by UV
Disinfecting Chlorine (HOCl) vs. Total Free Chlorine (FC)
and Cyanuric Acid (CYA)
The most important finding was how little disinfecting chlorine
(HOCl) is left after chlorine combines with Cyanuric Acid (CYA)
to get "stored" as chlorinated cyanurates (aka cloramides). The
chart at the following link shows this relationship. (I recently
discovered that all forms of chlorine are measured as ppm
equivalents of chlorine gas, so all charts, graphs and the
spreadsheet have now been updated to reflect this.)
HOCl Chart
Note that the red in the linked chart above represents a cutoff

of 0.011 ppm HOCl which roughly corresponds to the 650 mV


ORP level that the U.S. and WHO set as the minimum required for
disinfection. The green color is a guess at 0.05 ppm HOCl of the
minimum level of chlorine needed to prevent algae. The actual
number may be quite different, from 0.02 or less to 0.1 or more,
but based on Ben's "Best Guess CYA Chart" which is based on
real-world experience, I suspect the actual number will be
somewhere in this range. So, red means bacterial growth while
green means possible algae growth. Blue is the safe area.
The following shows this same data in graphical form with lines
showing the same two (probably correct) "bacteria" and (totally
a guess) "algae" levels.

The following is an approximate formula you can use so long as


your CYA ppm is at least 5 times your FC (the formula really falls
apart terribly below a ratio of CYA/FC of 3).
(HOCl as ppm Cl2) = (FC as ppm Cl2) / ( 2.7*(ppm CYA) 4.9*(FC as ppm Cl2) + 5 )
and if you are interested in the FC for a given HOCl (to
construct the equivalent of Ben's table, for example), you can
use the following which just solves for ppm FC from the above.
(FC as ppm Cl2) = ( 2.7*(ppm CYA) + 5 ) / ( 4.9 + 1/(ppm
HOCl) )
The constants in the above formulas are for a pH of 7.5 (which
is the only parameter that significantly affects these constants).
With the spreadsheet I can easily calculate the constants for
other pH, but remember that the above formulas are
approximate. For example, with FC of 3 and CYA of 15 the
formula gives HOCl as 0.098 when the correct answer is 0.095.
That's not terrible (about an 3% error). However, with FC of 5
and CYA of 15 the formula gives HOCl as 0.239 while the correct
answer is 0.199 (about an 20% error) which isn't as good.
A rough rule of thumb that applies at a pH of 7.5 is that the
effective chlorine level is reduced by a factor about equal to the
ppm of the CYA. So, a CYA of 30 ppm reduces the disinfecting
chlorine (HOCl) level to about 1/30th of what it would be with no
CYA.

The inverse of the above chart may be seen at this link:


FC Chart
The chart columns from 0.02 to 0.1 ppm HOCl roughly
correspond to "Ben's Best Guess CYA Chart". Ben's chart
converted to show HOCl may be found here where you can see
that the rough Min FC corresponds to 0.03 ppm, the rough Max
FC corresponds to 0.07 ppm (implying an ideal target of 0.05
ppm) and the shock table is not consistent, but probably implies
a minimum of 0.3 ppm, at least for green algae. User experience
indicates that hard-to-kill yellow or mustard algae (and maybe
black algae) may need 1.0 ppm HOCl for shock. User experience
with black algae indicates that keeping active black algae from
growing requires around 0.07 ppm HOCl.
A comparison of the "traditional" HOCl/OCl- graph with the same
graph in the presence of CYA may be found at this post. This
also shows how CYA is a "chlorine (specifically HOCl) buffer" that
makes HOCl concentration about half as sensitive to changes in
pH.
The original source for the equilibrium constants was done in
1973 (and published in 1974) where the recommended maximum
CYA level was 25 ppm:
J. O'Brien, J. Morris and J. Butler, Equilibria in Aqueous
Solutions of Chlorinated Isocyanurate
, Chapter 14 in A. Rubin,
ed., Chemistry of Water Supply, Treatment and Distribution,
1973 Symposium, (published 1974), Ann Arbor Science, Ann
Arbor, MI, pp. 333-358.
[EDIT] A searchable PDF of this paper may be found on a link on
this web page. [END-EDIT]
A Little CYA Goes A Long Way
NOTE: The mechanism of protection of chlorine from sunlight
by CYA is currently under review in this post. Higher CYA levels
may protect even proportionately higher levels of chlorine
more, especially in deeper pools.
The following is a graph showing that a large amount of the
benefit of CYA protection of chlorine from UV (sunlight) is
already there at around 20 ppm. This data is approximate, not
only because it is dependent on the amount of sun exposure,
but because the rate constants themselves change with FC level
(because there is a mix of two different rates of destruction -one from HOCl and the other from the chlorinated cyanurates
which are more stable, but still breakdown from sunlight). The
limiting half-life for HOCl/OCl- is 35 minutes which is consistent
with pool studies, but some experimental studies give 11.6
minutes. The limiting half-life of the chlorinated cyanurates is 8.4
hours though some other data shows it could be 6 hours.

The following graph combines the two concepts of needing more


chlorine at higher CYA vs. the greater protection of chlorine by
CYA. The graph shows the total chlorine (FC) loss rate in
ppm/hour vs. CYA at different HOCl levels. Remember that this
rate of loss will slow down as chlorine gets used up.
Nevertheless, the absolute loss of chlorine is greater at higher
CYA levels (keeping HOCl constant) and is the downside to a
"high CYA & high Chlorine" approach. However, the primary
reason to have higher CYA and Chlorine is to have a sufficient
buffer of chlorine to prevent it from dropping to dangerous
levels. There is obviously a tradeoff here. Though using no CYA
results in the least amount of chlorine loss, the fact is that you
simply can't maintain a pool with only 0.05 ppm chlorine
everywhere in it -- hence a minimum level is needed as a buffer.

Salt Water chlorine Generation (SWG) pools seem to require a


higher level of CYA, about 70-80 ppm, to operate efficiently. The
theory is that the CYA is slow to "store" the chlorine as it is
being generated so without enough CYA there is a build-up of
chlorine that degrades the performance of the salt cell. I would
prefer that the SWG manufacturers offer a larger lower-power
(per length) cell that would work efficiently at lower CYA
concentrations.
pH Rising
If you find that your pH wants to keep rising, this may be due to

your pool outgassing CO2 to the air. The rate of outgassing


increases with lower pH, higher alkalinity, and aeration of water
(splashing, water fountains or slides, high wind, jets pointed up,
etc.). The aeration of pool water is a physical process that will
vary greatly from pool to pool, but the following chart shows the
relative outgassing rate as a function of pH and Total Alkalinity.
It is possible that the hydrogen gas bubble production from SWG
systems contributes to significant aeration and is a source of
rising pH in such SWG pools. The rate is actually a function of
Carbonate Alkalinity so this chart is for a CYA of 30, but the
variation with different amounts of CYA is not large. Note that
there is a large variation with pH (the Y-axis is logarithmic). I
have drawn a somewhat arbitrary "Limit" line at a relative rate of
15 that I have found is roughly the tolerance limit where many
people start complaining about rising pH, but again aeration is a
factor I cannot predict.
CO2 Chart

Spreadsheet For Detailed Calculations


The link to the spreadsheet (in a ZIP file) that calculates all of
the above data is PoolEquations.zip and was last updated 14Mar-2009. It also does some of the things that BleachCalc does,
but is not for novice users.
Also see Equations for Chlorine Chemistry.
Also see Oxidation-Reduction Potential (ORP) vs. HOCl
(I will continue to edit this post to add more detail and
discussion.)

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#2

05-25-2007, 06:58 PM

chem geek
Senior Member

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Mar 2007
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8,657

Chlorine/pH/CYA Relationships
OK everyone. Here are some graphs I put together so now you
can give me feedback as to whether this is what you are looking
for. First, I show the traditional HOCl/OCl- relationship on the
left including a total line (for HOCl + OCl-) that is always at
100%. It should be noted that the chart on the left is valid for
any Total Free Chlorine (FC) level.
The chart on the right shows the same situation when there is
30 ppm CYA and in this case the Total Free Chlorine (FC) level
matters and is 3 ppm for this chart though when CYA >> FC it is
roughly the ratio of CYA to FC that determines HOCl and OCllevels. Also note that the percentage of disinfecting chlorine
(HOCl) at a pH of 7.5 fell from about 50% on the chart on the
left to around 1.5% on the chart on the right. Note that the
total HOCl+OCl- level is not 100% when CYA is present. The
difference from 100% (the Cl-CYA curve) is the amount of
chlorine "bound" to CYA and though it is better protected from
degradation from sunlight, it is also not immediately available for
disinfection or oxidation (but is available "in reserve" as HOCl
gets used up). Finally, notice how much "flatter" the HOCl curve
is in the graph on the right indicating that the presence of CYA
has made the amount of HOCl less sensitive to changes in pH
(though we really need to look at a log scale for relative
changes -- more on that next).

If we want to see changes in disinfecting chlorine (HOCl) in


percentage terms, then a logarithmic scale is more appropriate
so that equal distances on the chart represent the same relative
amount of change. That is, it answers the question of how much
improvement there is in the relative amount of chlorine when you
lower pH. It is not quite as obvious in this graph, but the HOCl
curve is a bit flatter on the right with CYA present, though at
lower pH at around 7.0 the pH sensitivity of HOCl is about the
same at 30 ppm CYA as it is with no CYA (and below 7.0 the pH
sensitivity of HOCl is actually greater with 30 ppm CYA than with
no CYA, but this is mostly due to the fact that with no CYA and
at low pH most of the chlorine is already HOCl so there's no room
for relative "growth"). Also note that at higher pH above 7.5 that
the presence of CYA allows one to operate at higher pH without
losing that much chlorine effectiveness (without CYA the
effectiveness of chlorine drops rapidly above pH 7.5). The graph
on the left cannot show the 0% flat line for Cl-CYA since it is off
the chart (the 0% is at negative infinity since this is a
logarithmic scale).

How's that?
P.S.
It is interesting to note that the traditional HOCl/OCl- graph with
no CYA showed the large variation in HOCl percentage vs. pH,
but that this was rather pointless (for pools; not for drinking
water disinfection) because the absolute concentration of HOCl
was typically so large that it didn't really matter if only 10% of
the total was HOCl. The minimum HOCl concentration for
preventing algae is on the order of 0.05 ppm (disinfection
minimum is around 0.01 ppm) whereas even a pool with no CYA
and a pH of 8.4 (which is only 10% HOCl) with even a low total
FC of 1 ppm still gives 0.10 ppm HOCl which is double where we
normally run our pools today when we use CYA!
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#3

05-25-2007, 07:00 PM

chem geek
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Mar 2007
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Equations for Chlorine Chemistry


I'll do this in words and in symbols. Adding bleach is a basic
process; it is the using up of bleach (chlorine) that is an acidic
process so the net result is almost neutral. When I said "chlorine
usage" I didn't mean your using chlorine (i.e. adding it) -- I
meant when chlorine gets used up by "doing its thing" or
"breaking down". Sorry for the confusion I caused.
Adding Chlorine
NaOCl + H2O --> Na+ + HOCl + OH- (+ extra base Na+ + OH-)

HOCl --> H+ + OClSodium Hypochlorite (liquid chlorine or bleach) combines with


water to produce sodium ions (part of regular table salt) plus
disinfecting chlorine plus hydroxyl ion. The hydroxyl ion makes
this a basic reaction that raises pH, but because the disinfecting
chlorine is a weak acid this overall reaction raises the pH by less
than a strong base would. Note that there is a small amount of
extra base in the form of Sodium Hydroxide (lye or caustic soda)
that comes with Sodium Hypochlorite and is there to help
preserve it, but this amount is rather small.
Using Up Of Chlorine
Breakdown of Chlorine by Sunlight (UV)
2HOCl --> O2(g) + 2H+ + 2Cl-

2OCl- --> O2(g) + 2ClChlorine breaks down in the presence of ultraviolet radiation,

such as found in sunlight, and forms oxygen gas and chloride ion
(and hydrogen ion, if starting with HOCl hypochlorite). Because a
hydrogen ion is produced, this is an acidic process, but since
disinfecting chlorine is a weak acid, only some of it breaks down
in a way that lowers pH as shown above (i.e. only HOCl
produces H+; OCl- does not). During the process of chlorine
breakdown by sunlight, there are hydroxyl (OH), oxygen anion
(O-) and chlorine (Cl) radicals that are also produced as shortlived intermediates (technical details in this post). This can help
oxidize organics in the pool.
Net Chlorine To Breakpoint (Ammonia "Oxidation")
2NH3 + 3HOCl --> N2(g) + 3H+ + 3Cl- + 3H2O

OCl- + H+ --> HOCl


The disinfecting form of chlorine (HOCl) combines with ammonia
through a series of reactions (that I have not shown) with the
net result being the production of nitrogen gas (which is why it
is important to keep your cover off and have good circulation
when shocking) plus hydrogen ion and chloride ion. Though by
itself this would be a strong acid reaction, there is also OClpresent that will combine with hydrogen ion to form more HOCl
since the ratio of HOCl to OCl- will remain constant (and is about
50/50 at pH 7.5). So the net reaction is acidic, but not strongly
so.
Overall combination of adding chlorine and having it used
up
The net reactions are as follows if you combine the ones I
showed above.
2NaOCl --> 2Na+ + 2Cl- + O2(g)

3NaOCl + 2NH3 --> 3Na+ + 3Cl- + N2(g) + 3H2O


So the overall net reaction of adding sodium hypochlorite to your
pool and having it used up in its most typical ways is simply to
produce salt (yes, sodium chloride or table salt, dissolved in
water, of course) and either oxygen or nitrogen gas (and water).
Other things that could happen
If you do not have enough chlorine in your pool relative to your
bather load (ammonia demand), then the chlorine may not
completely oxidize ammonia and instead you will get chloramines
(first, monochloramine). This reaction is basic. However, sunlight
may break down monochloramine which will result in the rest of
the breakpoint process which overall is acidic (so it's the same
as I showed above overall).
It is also possible for chlorine to combine with organic
compounds to form chlorinated organics that are hard to
breakdown. When people talk about the health problems with
chlorine, it is usually about some of these chlorinated organics
(Disinfection By-Products, DBPs) known as Tri-HaloMethanes(THMs) such as chloroform. Also, some chloramines
such as nitrogen trichloride (NCl3) not only smell bad, but can
cause health problems (especially in indoor pools with poor air
circulation). In an outdoor pool exposed to sunlight and with a
good residual of chlorine you typically don't get these "bad"
compounds. If you are really concerned and have money to
burn, you can use a constant maintenance level of non-chlorine
shock (monopersulfate, MPS) to oxidize organics before chlorine
gets a chance, but this is probably overkill for an outdoor pool
(though may be a good idea for an indoor pool).

Salt (SWG) Pool


In a salt water pool you produce chlorine through the following
reactions:
At the anode (positive plate):
2Cl- --> Cl2(g) + 2eAt the cathode (negative plate):
2H2O + 2e- --> H2(g) + 2OHwhich nets out to the following where the chlorine gas dissolves
in water:
2H2O + 2Cl- --> Cl2(g) + H2(g) + 2OHCl2(g) + H2O--> HOCl + H+ + Cl-

H+ + OH- --> H2O


---------------------------------------------2H2O + Cl- --> HOCl + OH- + H2(g)
or equivalently
H2O + Cl- --> OCl- + H2(g)
Note that the products of HOCl and OH- are exactly the same as
you get when you add liquid chlorine or bleach (ignoring sodium
ion). This process is partly basic, but not strongly so due to the
HOCl weak acid. So the overall net result in a salt pool is simply
the production of oxygen or nitrogen gasses. The disinfecting
chlorine that was created from chloride ion gets converted back
to chloride ion as it is "used up".
[EDIT]
The net reactions in an SWG pool for chlorine addition from
the SWG and then breakdown from sunlight and oxidation of
ammonia are as follows:
2H2O --> O2(g) + 2H2(g)
2NH3 --> N2(g) + 3H2(g)
The chlorine is not "seen" in the above net reactions because
the chloride that became chlorine goes back to being chloride
again. The oxygen gas comes from water when chlorine gas
dissolved in it (i.e. from hypochlorite ion or hypochlorous acid)
while the nitrogen gas comes from the ammonia (the oxygen or
hydroxyl in the chlorine reverts back into water in this case,
using the hydrogen from the ammonia to do so).
[END-EDIT]
If you have a salt pool and don't use CYA (this isn't normal) then
you could also outgas chlorine in the same way that CO2 is
outgassed. This is more likely if you are aerating the water (e.g.
have water features, slides, fountains, jets pointed up, lots of
splashing, ...). This process is strongly basic and greatly
increases the pH (HOCl + Cl- --> Cl2(g) + OH-). The reason this
would tend to only happen in a salt pool without CYA is that a
high concentration of both chloride ion (Cl-) and disinfecting
chlorine (HOCl) are needed and it occurs more readily at lower

pH. [EDIT] If chlorine gas produced by the SWG did not fully
dissolve and instead was outgassed, then this would result in a
net pH rise and could be one factor for the pH rise seen in SWG
pools (the other factor being carbon dioxide outgassing from
slightly increased aeration from the SWG, but that is not enough
to fully explain most pH rise in SWG pools by itself). [END-EDIT]
I know, I know...more than you wanted to know. I hope it helps
and that you made it this far...
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#4

05-25-2007, 07:25 PM

chem geek
Senior Member

Oxidation-Reduction Potential (ORP) and HOCl


Oxidation-Reduction Potential (ORP) and HOCl
On page 5 of the following link is a summary of results from the
"Commercial Spas Study, Portland, Oregon".

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http://www.sbcontrol.com/ppmorp.pdf
The following linked table shows this same data, but with an
extra column I added where I calculated the ppm of HOCl (using
a temperature of 104F for spas). I also resorted the table in
order of decreasing HOCl (the table in the link is sorted by ORP).
ORP.htm
It appears that HOCl is about as good if not a little better than
ORP except for one case where the FC was low (0.83), the CC
was high (1.04) and there was no CYA (0). Perhaps the chlorine
demand was used up at some point or the high CC had some
adverse effect, but the low ORP (564) with chlorine present
without CYA is certainly strange. Having a rule of a minimum of
0.011 ppm HOCl and a minimum FC or 1.0 (or perhaps 2.0) would
work slightly better than the ORP rule of having a minimum of
650 mV. Of course, this is just one study, but I can't seem to
find any other data as comprehensive as this.
[EDIT] HOWEVER, note the following sort of the same table by
FC:
ORP-FCsort.htm
So perhaps using the HOCl concentration for predicting
disinfection rates isn't as good as using FC and FC may even
beat ORP. [END-EDIT]

When I first started looking at ORP, I was shocked to find how


inconsistent it was even from the same source. The rather
definitive work by Clifford White called "The Handbook of
Chlorination" had inconsistencies as did several different
manufacturers. Before looking at the absolute ORP to ppm
Chlorine readings, I first looked at something that shouldn't vary
that much between ORP sensors and that was the amount of mV
change for each doubling of ppm of Chlorine (everything else
constant, including pH, TDS, etc.). The following table shows
the results. I have put the sources for each as a link where
appropriate.
Code:
Product or Source
ORP mV per 2x Chlorine (nea
r pH 7.5)
---------------------- ---------------------Sensorex
83.0
Aquarius Technologies
45.7
Chemtrol (SBControl)
22.7 (at pH 7.5)
Uniloc/Stranco
not logarithmic
Siemens Strantrol
20.0 (same as Pe
talumawater from Fig. 4-19 Pools below)
CYA Paper
28.4
Theoretical 1 electron
17.8
Theoretical 2 electron
8.9
Clifford Whites Handbook of Chlorination:
Fig. 4-19 Distilled Water
10.0
Fig. 4-19 Pools
12.0 20.0
Fig. 9-93a (0-1 ppm)
35.0
Fig. 9-102 (0-0.035 ppm)
30-40
Fig. 9-103 (0-110 ppm)
15-20

Sensorex
Aquarius Technology
Chemtrol (SBControl)
Unilock/Stranco (link is dead; may need subscriber access)
Siemens Strancol (link is dead)
I also developed formulas for each of the manufacturers ORP vs.
ppm Chlorine relationships and they also vary in absolute ORP
readings by large amounts. It appears that the most accurate
and consistent and carefully controlled and measured readings
were from the Chemtrol (SBControl) paper so that is what I have
used in my spreadsheet though I no longer prominently use ORP
and have relegated it to a minor section of the spreadsheet.
This also does not mean that I believe they make better sensors
than the others (I simply do not know). The following shows the
variation in absolute ORP for these same sources.
Code:
<ORP>
Product or Source
0.2 ppm 1.0 ppm
2.0 ppm
--------------------------------- ------------Aquarius Technologies
635
730
775
Chemtrol (SBControl)
720
770
792
Uniloc/Stranco
635
794
822 (at 7.4: 650, 800, 826)
Siemens Strantrol
655
697
715
CYA Paper
702
767
796 (at 7.4: 716, 780, 810)
Clifford Whites Handbook of Chlorination:
Fig. 4-19 Distilled Water
755

Unfortunately, Clifford Whites Handbook of Chlorination is


inconsistent even when measuring the same waters under the
same conditions. The chart in Figure 4-18 that shows the
relationship between ORP and pH shows at a pH of 7.5 (the
same as Figure 4-19) ORP readings that are 35 mV lower for all
cities (i.e. Petaluma at 2.1 ppm is 680 mV) and 165 mV lower for
distilled water (i.e. at 1.8 ppm is 610 mV).
So what's the bottom line? I agree with Ben that though ORP is
measuring something, namely the oxidation potential of the
water, that this is not necessarily the important thing to
measure or that it is not always measured accurately or
consistently, etc. It should be noted that this is a rather
controversial assertion to make as an entire ORP industry was
created on the basis of ORP being the superior measurement to
use, but when people looked at studies, such as the Commercial
Spas Study mentioned earlier in this post, they only compared
ORP to variables such as Free Chlorine (FC), CYA and pH as
individual variables (possibly through correlation analysis) and it
does not appear that anyone looked at theoretically calculated
HOCl levels from those same variables (as I did, again results are
earlier in this post). It is possible that some combination of HOCl
concentration with H+ (pH) concentration determines the rate of
disinfection and oxidation, but that is something I will have to
look at later, probably using the Commercial Spas Study data
since that's all I've got right now.
[EDIT] I should also add that there is a difference between a
dynamic (i.e. real-time) measurement of a parameter such as
ORP or HOCl concentration vs. a static (i.e. test kit)
measurement since the former can result in a lower value due to
the continual introduction of organic load. This is especially true
when CYA is present since the half-life of converting a
chlorinated cyanurate into CYA and HOCl is relatively slow at
0.25 seconds for one pathway and 4 seconds for another (but
remember, this is the time it takes to convert half of the total
chlorine and that's generally quite a lot). Another place this
effect shows up is if you take a UV lamp and wave it over water
being measured for ORP where you can see the ORP drop and
then remove the lamp and the ORP rises again. So there is
clearly some dynamics going on and only a real-time
measurement is going to pick that up. Of course, if one could
measure HOCl directly, then that might be even better than ORP,
but as "bad" as ORP sensors have been, HOCl sensors appear to
be worse (in Ben's experience from seeing such products come
and go in the market). It does seem that once an ORP sensor is
calibrated then it does roughly track the HOCl concentration so
is at least something to use in automated chlorine control
systems, especially in a commercial pool environment where the
organic load from bathers (and the breakdown of chlorine from
sunlight) varies greatly throughout the day. [END-EDIT]
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot

cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#5

05-26-2007, 08:18 PM

chem geek
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Mar 2007
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CYA and Lifetime of Chlorine


After accumulating multiple pieces of conflicting evidence, I think
it's about time to discuss and investigate the mechanism of how
CYA protects chlorine from sunlight. The starting point for the
theory, that I'm starting to think is only partially correct and
needs to be enhanced, is that the chlorine that is in the form of
hypochlorous acid or hypochlorite ion breaks down in direct
noontime sunlight with a half-life of around 35 minutes while
chlorine that is attached to Cyanuric Acid (CYA), also known as
chlorinated isocyanurates, breaks down from the sun with a halflife of around 8.4 hours.
This graph shows the net result. The conclusion from this graph
is that a little CYA provides a lot of protection of chlorine and
that there are diminishing returns for using high CYA levels.
There are two pieces of evidence that are in conflict with this
theory:
1) Some users, most notably Janet (user name Aylad), report
that in their non-SWG pools using high levels of CYA shows
dramatic improvement in chlorine's staying power. In Janet's
case, with a CYA below 60 she found that the FC would go from
7-8 to 2-3 in one day (5 ppm FC per day) while with a CYA of
80-90 the FC would go from 8-9 and take 3 days to go below 5
(about 1.2 ppm FC per day). That is a huge improvement that is
wholly inconsistent with the graph.
2) Several users of SWG pools have found that raising the CYA
to higher levels, especially approaching 70-80 that some
manufacturers recommend, has a dramatic increase in FC levels
at the same SWG output. Though one theory is that the CYA
makes the SWG cell more efficient by combining with the
generated chlorine in the cell "hiding" it from the plates in terms
of equilibrium (thus making the generation proceed more quickly),
an alternative explanation proposed by some is that the higher
CYA levels simply protect the chlorine from destruction from
sunlight at a rate faster than the baseline theory outlined at the
start of this post.
I've been thinking of mechanisms that might explain the above
data and that could be added to the theory to make it predict
more accurately. One possibility is that CYA itself is able to
absorb UV radiation and possibly re-radiate it as non-UV
radiation at lower energy, with the rest of the energy becoming
kinetic (i.e. heat or temperature increase). This link shows that
indeed CYA does absorb UV at the pH found in pools, though it
absorbs even more in more basic/alkaline solutions.
If one adds direct CYA absorption and essentially shielding of UV
from lower depths of the pool, then the "CYA shielding chlorine"
description would in fact be accurate for this mechanism (while

it is not accurate to describe the chlorinated isocyanurates


which do not "shield" chlorine but are distinctly different
molecules with different absorption rates and affect disinfecting
chlorine levels). The net effect of this new mechanism would be
to have higher CYA levels reduce chlorine loss at a greater rate
than shown in the graph I linked to at the top of the post.
So how can we prove that this new mechanism exists (or is
likely) and explains what is being reported in (1) and (2) above?
Let's start with the easier of the two, namely the second item of
whether CYA improves SWG cell efficiency. This can readily be
determined by comparing SWG FC output at different CYA levels,
BUT with no sunlight shining on the pool (i.e. either at night or
with an opaque cover or with an indoor pool). To the degree
that CYA increases the SWG cell output to generate higher FC
levels, then this leads credence to the efficiency theory; if not,
then the protection from degradation from sunlight is more likely.
As for whether CYA "shields" chlorine through absorption of UV
(clearly it does absorb some UV, but the question is more one of
whether this is a significant mechanism in quantity), this should
be a function of the depth of the pool. The presence of higher
concentrations of CYA essentially lower the density of UV
radiation reaching lower depths in a pool. So this protective
effect of CYA should show up more in deeper pools where a
significant fraction of the water is at greater depths and should
be less effective in shallower pools. The chlorinated
isocyanurates, on the other hand, do not have this same effect
since they do in fact degrade (the chlorine attached to them
degrades to chloride ion) and are in fact less likely to interact
with sunlight in this way so light is more likely to continue to
lower depths (i.e. it doesn't act as a shield and even if it does,
it's a much smaller concentration than unbound CYA itself).
The experiment would be harder and would require measuring the
difference in the destruction of chlorine in waters of different
depths at varying CYA levels. The half-life of the chlorinated
isocyanurate would be the dominant factor in the shallowest
basin of water while CYA's "shielding" effect would be a greater
factor in the deepest basin of water.
The formula for determining the light intensity passing through a
solution is as follows:
I/Io = e-l
where (mu) is the absorption coefficient and is a function of
wavelength (so the above formula is for a specific wavelength).
"l" is the path length which for the units in the links I referred to
is in centimeters.
There is also a formula for absorbance defined as follows:
A = -log10(I/Io)
and there is a molar extinction coefficient defined by the
following equation:
A = *c*l
where (epsilon) is the molar extinction coefficient, c is the

molar concentration in moles/liter, and l is the path length in


centimeters.
so = / (log10(e) * c) = / (2.303 * c)
3 feet is about 91 centimeters and the molar concentration of 50
ppm CYA is 0.00039 moles/liter. So,
= 2.303 * c * = 0.00090 *
So to get any reasonable absorption from CYA (so that is near
1/91 so at 91 cm we have *l = 1) we need to be over 10.
This source gives an extinction coefficient (for gaseous HOCl) of
123 M-1cm-1 with an absorption peak at 220 nm. This source
gives an extinction coefficient for hypochlorite (OCl-) of 350 M1cm-1 at 290 nm. This link has graphs that show the molar
absorption coefficient for both HOCl and OCl-. It looks like CYA
absorption will protect HOCl from breakdown more than OClthough both are protected (so in theory that implies that lower
pH has less chlorine loss which is also true due to the greater
photolysis of OCl- and correspondingly shorter half-life).
This link gives an extinction coefficient for Cyanuric Acid (CYA)
of 6.283 OD220 units ml mol-1 which implies 6283 M-1cm-1 at
220 nm. The link given earlier that showed graphs of CYA
absorption are consistent with this measurement, but the
absorption drops rapidly at higher wavelengths and it is not clear
at which wavelengths HOCl dissociates (breaks down from UV).
The rate constant (k) for a first-order reaction is related to the
half-life (t 1/2) as follows:
C/Co = 0.5 = e-kt
t 1/2 = -ln(0.5)/k = 0.693/k
k = -ln(0.5)/t 1/2 = 0.693/t 1/2
and the rate constant (k) is presumed to be proportional to the
intensity of light.
This link provides interesting detailed information about chlorine
(and bromine and chlorine dioxide) in terms of half-life at various
depths (no CYA present). Interestingly, there is quite a
difference in half-life by depth at higher concentrations of
Dissolved Organic Carbon (DOC). Chlorine itself can shield lower
depths, but it is unclear what the overall net molar extinction
coefficient is independent of wavelength. The numbers in the
chart with the lowest DOC show an absorption coefficient of
0.010 at 1 meter, 0.0081 at 2 meters, 0.0067 at 3 meters and
0.0057 at 4 meters. These numbers are not far of from the
absorption of water itself as seen in this link though the DOC
may certainly be a contributor. Thus, the chlorine is most
depleted from water near the surface so having good
circulation is essential in order to keep chlorine levels more
uniform throughout the pool. It also appears, from the pH
dependence, that perhaps hypochlorous acid (HOCl) is less
susceptible to breakdown from sunlight than hypochlorite ion
(OCl-). This implies that having a pool at lower pH results not
only in more disinfecting chlorine, but has the chlorine last longer
(though the effect may not be very strong from, say, 7.8 to

7.2).
Also, note that there is a non-linear effect from the
concentration of whatever protective agent is present at the
shallower depths (be it hypochlorous acid itself or CYA). So if I
use a molar extinction coefficient of 10 and 50, then I would get
the following for I/Io at 3 foot depth:
CYA (ppm) ... I/Io (10) .. I/Io (20) .. I/Io (50)
0 ................. 1.00 ........ 1.00 ........ 1.00
10 ................ 0.85 ........ 0.72 ........ 0.44
20 ................ 0.72 ........ 0.52 ........ 0.20
30 ................ 0.61 ........ 0.38 ........ 0.09
40 ................ 0.52 ........ 0.27 ........ 0.039
50 ................ 0.44 ........ 0.20 ........ 0.017
60 ................ 0.38 ........ 0.14 ........ 0.0077
70 ................ 0.32 ........ 0.10 ........ 0.0034
80 ................ 0.27 ........ 0.074 ........ 0.0015
90 ................ 0.23 ........ 0.054 ........ 0.00067
100 .............. 0.20 ........ 0.039 ........ 0.00030
So to see the dramatic change seen from higher CYA levels, the
CYA shielding effect has to be strong enough to be the
predominant effect. The shielding effect would "shield" not only
unbound chlorine, but also chlorine bound to CYA. Note that
using an extinction coefficient of 20 in the above table one finds
the difference between 50 and 90 ppm CYA being a factor of 3.7
which is not far off from the factor of 4.2 that Janet was seeing.
So perhaps adding an additional protection factor similar to the
"20" column in the above table might be the thing to do. This link
indicates that the chlorinated isocyanurates are unstable in
sunlight, but it is unclear how much of that is due to breakdown
from the equilibrium hypochlorous acid vs. direct breakdown
itself. The study just shows that CYA is itself stable in sunlight.
If the CYA absorption effect is really this strong, then deeper
pools should be more protected at the same CYA level since
more of their water volume will be at deeper depths "shielded"
from the UV.
An experiment using shallow depth water with different levels of
CYA will help isolate the two effects. If the CYA "shielding" or
absorption is the main effect, then there should be little
protection of chlorine in shallow water. If instead the chlorine
combined with CYA has a longer half-life and that is the main
effect, then higher CYA levels even in shallow depths should
show significant protection and should roughly follow the curve
in this graph. I suspect that there will be a some of both
processes going on.
The original CYA patent by Fuchs may be seen at this link. There
were interesting laboratory tests that appear to have been made
at shallow depths and only show a small amount of the "depth"
variation one sees with higher chlorine levels. The UV lamp they
used appeared to have 1 ppm FC drop to 0.5 ppm FC in 1.7
hours so was not as strong as sunlight. The rate of chlorine loss
seemed to track the amount of unbound chlorine, but with
diminishing returns starting at a rate of 0.29 per hour at no CYA,
0.16 per hour with 1 ppm CYA, 0.13 per hour with 2 ppm CYA,
0.092 per hour with 5 ppm CYA, 0.071 per hour with 50 ppm CYA
and an actual increased loss of 0.088 per hour at 100 ppm CYA.
This is somewhat consistent with the original theory of a 35

minute half-life in direct sunlight with no CYA and an 8.4 hour


half-hour limit when bound with CYA. This is probably where the
industry got its original data for its tables. Note that CYA also
has a protective effect on chlorine loss from oxidation of iron
and copper. Though the patent speculates CYA may coat
metals, it appears that the effect is explained by the reduction
in disinfecting chlorine and therefore the rate of corrosion based
on its concentration. It should be noted that in the patent "real
pools" showed the greater protection effect of higher CYA levels
by about a factor of 2 at 10 ppm CYA and over a factor of 3 at
50 ppm CYA. Thus there does appear to be a "shielding" depth
factor for CYA protection separate from that explained solely by
Cl and Cl-CYA breakdown. The fact that the chlorine levels were
the same and only the CYA level increased, yet had a greater
effect in a real pool with "depth" is very strong evidence.
The good news with this new information is that at sufficiently
high CYA levels using a higher FC (to compensate for disinfection
and prevention of algae) should not result in larger losses. Going
from 30 ppm to 90 ppm requires about triple the FC level, but
the loss rate may be cut down by a factor of 7 for a net overall
savings of over a factor of 2. If we can validate this, then it
should be possible to run a high CYA pool with high FC levels
economically, especially in deeper pools.
To calculate the average intensity of light in the pool overall,
one needs to integrate it over depth as follows:
I = (Integral over 0 to D of Ioe-l dl) / D = (Io/(D))*(1 - e-D )
which with small expands to
I = Io*(1 - D/2 + (D)2/6 - ...)
so that as approaches 0, "I" approaches "Io" as expected.
In many real pools, there is less volume below around 3 feet as
the pool bottom drops only in the deep end such that the pool
can be seen as the sum of 3 pools, one with a depth equal to
the shallow end, one with a depth equal to the deep end, and
one with a depth that varies from the shallow depth to the deep
depth. If Ds is the depth of the shallow end and Dd is the depth
of the deep end, then the overall average intensity (that can be
used to calculate an average breakdown rate or whose inverse
can calculate an average half-life) is the following assuming
each section is one-third of the pool area:
I = ( (Io/Ds)*(1 - e-Ds) + (Io/(*(Dd-Ds)))*(Dd + e-Dd/ - Ds
- e-Ds/) + (Io/Dd)*(1 - e-Dd) ) / 3

[EDIT] See this post for an experiment Mark did that pretty
much conclusively proves that the improved salt cell efficiency
at higher CYA does not come from any internal chemistry in the
salt cell (since there was no such change seen at night) but
rather is from reduced chlorine loss from sunlight that more than
makes up for the higher FC needed at higher CYA to maintain
disinfection and prevention of algae. [END-EDIT]
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#6

03-17-2008, 09:59 PM

A couple of comments on the above.

cliff_s
Member
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Mar 2007
92

There is 2 ways to control pool chemistry, reactive or predictive.


When we measure the water parameters then and add agents to
correct these parameter
we are being reactive.
When we try to predict what the pool parameters are then then
add our agents we are being
predictive.
If we try to automate the pool correction parameters with the
various meters(or probes) we continously
try to correct to these parameters. How succesful we are is
determined by the accuracy of the continuous
measurements. As we have found ORP measurements are
difficult to maintain with godd accuracy, pH measurements
have proven somewhat more accurate.
Lets take another look from a different angle on pool parameter
corrections. We know that the biggest user of
FC is the Sun and its UV rays. So Chlorine use is mostly dictated
by the intensity and the length of time the
sun is exposed to the pool water. We have a good measure of
this by the sunrise and sunset times. We cannot
predict the bather load, but there is another way around this I
will mention later. Another parameter of Chlorine use is
the water temperature. The water temperature in a non-heated
pool will be a direct relation to the amount of sun
that strikes the pool, in a heated pool this of course won't apply.
With a SWG we know the amount of time the SWG is running
gives a set amount of Chlorine generation. I am only considering
running the SWG at 100% ouput. This is the most efficient for
the SWG and the shortest pump run time, because the pump
must be running for the SWG to work.
Now, we know the pool water temperature and the Chlorine
demands are directly related to the amount of sunshine
and water temperature, so if we time the operation of the SWG
to coordinate with the sunrise and sunset we can closely
match the Chlorine needs. I have found that actually as the
water temperature decreases the SWG will have to be run a
shorter
time because the Chlorine demands as less than just the
function of the Sunrise and Sunset. I have confirmed this over
the
last 2 years. The next step is to add the water temperature into
the pump time run calculations. As a practical problem I have to

find
a way to run a wire to get my pool water temperature.
Since a pool is a large volume of water the parameters change
rather slowly and it not necessary to try to correct them
minute by minute. The system I am testing is, to use a
predictive set of parameters to control Chlorine
addition(generation).
I have installed a CO2 system for pH control using the same type
parameters, because the pH control is needed as a function
of SWG run time. In the summer I have to make a correction for
pool water addition.
I find that these predictions are quite accurate over time. I
might add it does take some kind of computer controlled system
to do all these calculations. I do it with my home automation a
Elk M1G.
In summation, if by varying the SWG(pump) run time and the
time the CO2 is added I can control the pool water parameters
that correct for the various seasons and water temperature,
then I have almost a hands off system. Even with one of the
ORP-pH sytems you still have to periodically measure the water
parameters. The difficulty is that the probes are really
ment for laboratory usage and are not dependable enough for
unattended use. Their calibration is hard to maintain and
require periodic replacement.
As I mentioned earlier if you run the pool pump and SWG while
the pool is in use you will add enough extra Chlorine to
offset the bather load(in a residential pool only).
The bottom line is that are is more than one way to maintain
pool water chemistry.
Cliff s
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#7

03-18-2008, 11:08 AM

The Mermaid Queen


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Ack!! I just accidentally wandered into the 'deep end'!!


just ignore me as I make my way to the more easily navigable
waters...

Mar 2007
Northern KY
2,532

18x32 grecian IG vinyl; ~23000 gallons; 250# sand filter, Hayward


superpump with AO Smith motor 1HP SF1.0; booster pump for

polaris. Handy Links: Jason's Calculator, TF-100 Test Kit, Pool


School, CYA-Chlorine Chart
"Shock" is a process, not a product!
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#8

03-18-2008, 11:49 AM

duraleigh

Ack!! I just accidentally wandered into the 'deep end'!!

Senior Member
In the Industry

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just ignore me as I make my way to the more easily


navigable waters...

Apr 2007
Raleigh, NC
21,392

Dave S.
Site Owner 42k vinyl and concrete pool, 1.5hp pump, 140gpm filter, No
SWG
TFTestkits owner
TFTestkits , PoolMath , Pool School
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#9

03-18-2008, 01:45 PM

Cliff,

chem geek
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I understand your points, but I don't think we're really in that


much disagreement. Basically, though we start off by telling
people to measure and adjust water parameters, that's mostly
so people can get a "sense" of their pools and what they need.
Then, over time, people don't have to measure as often (at least
for some parameters) if they "know" their pools better. That is,
one starts off with measurements and adjustments to keep
things in line and then transitions more towards what you are
describing as practical ways of essentially maintaining the water
chemistry the same as would be done with measurements. In my
own pool, I don't measure chlorine every day, but rather twice a
week before I normally add chlorine since I know its usage rate
and never get too low (I have an opaque electric safety cover,
so loss from sunlight is minimized).
The problem we have found is that one can't really skip to the
second stage as you have without first doing the first stage of
measurements. The reason is that the factors in every pool are
complex and not easily calculated. Yes, one knows that if sun
hits the pool then there will be loss due to sunlight, but the
exact loss depends on many factors including sun angle (time of
year), pool depth, trees and other obstructions, CYA level, etc.
Bather load is also a difficult variable since people sweat
different amounts and this depends a lot on water temperature
and level of activity. Chlorine demand from other organics
depends on how much junk (leaves, pollen, etc.) gets into the
pool and that can change over time depending on what gets
caught in the filter, how often it is cleaned, etc.
So I don't disagree with what you are saying and I'm glad you've

found a timing approach that works well for you. I'm not so sure
that the 100% SWG ontime only when the pump runs is
necessarily more efficient. My understanding of SWG percentage
is that when it's on, it's fully on, so the percentage is just one of
the amount of on time during the pump run time. I don't think
the SWG cell necessarily lasts longer trying to have it run 100%
of the time that the pump is running. The pump run time should
be based on circulation needs while the SWG percentage time
(and when this occurs) should be based on chlorine demand and
those are separate factors that may not coincide. I do agree
with your "when to run the SWG" analysis such that it runs more
frequently during expected higher demand.
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#10

03-18-2008, 10:44 PM

still digesting all this. quite a bit here and some interesting
implications but no big surprises. We've always been pretty much
on the same page, Richard!

Guest

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#11

03-19-2008, 10:25 AM

JCJR
Senior Member

I accidently wandered in here myself and I think I got a Brian


aneurysm.
Hey Sean, you need to put a warning on this advance chemistry
section.

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#12

03-19-2008, 11:04 AM

chem geek

Originally Posted by waterbear

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still digesting all this. quite a bit here and some interesting
implications but no big surprises. We've always been pretty
much on the same page, Richard!

Evan,
Just FYI -- this is not a new thread. Only the post from cliff_s
was new and triggered this thread to show up in "View Posts
Since Last Visit". The information on pool water chemistry is
pretty old, much of it copied from the Pool Forum China Shop
where I originally posted it here.
JCJR and Grace, aren't the graphs pretty? I thought my choice
of color scheme was particularly well planned. Next time you see
the word "Advanced" in a forum name, run, do not walk, to your
nearest exit. I hope the aneurysm clears up soon so the dyslexic
typing gets cured (unless your name is Brian).
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#13

03-19-2008, 12:05 PM
Guest

Originally Posted by chem geek

Just FYI -- this is not a new thread.


Richard

They say when you get old the mind is the second thing to go!
(I was 54 on Feb. 24) Can't remember what the first thing is!
Been too long!
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#14

03-19-2008, 12:21 PM

The Mermaid Queen

Originally Posted by chem geek

Senior Member

JCJR and Grace, aren't the graphs pretty? I thought my


choice of color scheme was particularly well planned.

oooohhhh.... colors! I especially like the green!! 8)


(sorry to have hijacked this thread... just couldn't help myself!!!)

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18x32 grecian IG vinyl; ~23000 gallons; 250# sand filter, Hayward


superpump with AO Smith motor 1HP SF1.0; booster pump for
polaris. Handy Links: Jason's Calculator, TF-100 Test Kit, Pool
School, CYA-Chlorine Chart
"Shock" is a process, not a product!
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#15

03-19-2008, 12:43 PM

JCJR
Senior Member

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I am sure glad that others are able to understand this stuff and
debate/add to the findings because it benefits us all.

May 2007
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266

20x40 24,000 gal IG plaster/CircuPool RJ45 SWG/2 skimmer/2sp 2.5hp


Jandy Stealth/340sq ft cart filter/600sqftHeliocol Solar Panels/6ft semi circlr
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Navigator/3step 2ft raised bond beam
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#16

06-01-2008, 05:12 PM

chem geek
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I am adding a post that explains the chlorine/CYA relationship in


chemical terms at varying levels of detail as some people ask for
a more detailed explanation or derivation and the original 1974
O'Brien paper is hard to find [EDIT] (you can see a copy of the
paper here). [END-EDIT]
QUALITATIVE DESCRIPTION
Though Cyanuric Acid (CYA) absorbs ultraviolet (UV) radiation
directly thus shielding the lower depths of water and protecting
chlorine in those depths from breakdown, the primary result of
having CYA in the water with chlorine (hypochlorous acid) is that
it combines with chlorine to form a set of chemical species
collectively called chlorinated isocyanurates (and these
compounds also absorb UV without breaking down significantly).
The full chemistry is complicated (well, tedious) because there
are 6 different species of chlorinated isocyanurates (that is,
chlorine attached to CYA) and 4 different species of Cyanuric
Acid and its dissociated ions. There are 13 simultaneous
chemical equilibrium equations of the CYA, chorinated
isocyanurates, hypochlorous acid and their combinations though
only 10 of these are independent from each other.

Look at the chemical structure for CYA here and that of Trichlor
here and of Dichlor here and notice that essentially the Nitrogen
can have either hydrogen or chlorine attached to it and that
there are three such sites. Qualitatively, chlorine combines with
CYA to form new chemicals that are essentially not disinfectants
nor oxidizers (at least not even close to hypochlorous acid; more
like hypochlorite ion at best). CYA has a moderately strong
affinity for chlorine such that when CYA >> FC (when both are
measured in their respective ppm), then most of the chlorine is
attached to CYA. For example, when the pH is 7.5 and the FC is
3.5 ppm and the CYA is 30 ppm, then 97% of the chlorine is
attached to CYA. Nevertheless, the chlorine attached to CYA
gets measured in the FC test because the chlorine gets released
from the CYA quickly enough to replenish the chlorine that is
consumed by the test (by reacting with dye). [EDIT] Free
Chlorine (FC) does not measure active chlorine, but rather
the chlorine reserve or reservoir that is mostly inactive.
[END-EDIT]
In a very real sense, CYA acts as a hypochlorous acid buffer
holding chlorine in reserve, but significantly lowers its
concentration which determines the rate of any reaction in
which chlorine participates. You can see from the structure of
Hypochlorous Acid here that it looks similar to water with a
chlorine atom substituting for a hydrogen atom. When chlorine
combines with CYA, this is a chlorine substitution for a hydrogen
atom or essentially an exchange of the chlorine atom to the CYA
and the hydrogen atom from the CYA to make water. When
chlorine is released from CYA, then the opposite exchange
occurs.
SIMPLIFIED CHEMICAL EQUATIONS
To simplify the description, I will only talk about the most
dominant chemical species found at the pH of pool water. For
Cyanuric Acid (which I designate as H3CY), the species at
highest concentration is the one that has dissociated one
hydrogen ion which I will designate as H2CY -. For the chlorinated
isocyanurate species, it is CYA with one hydrogen, one chlorine,
and one open slot so is negatively charged which I will designate
as HClCY -. The following is the primary relevant chemical
equation to focus on:
HClCY - + H2O <--> H2CY - + HOCl
"Chlorine bound to CYA" + Water <--> "CYA ion" + Hypochlorous
Acid
Hypochlorous Acid is the strongly disinfecting and oxidizing form
of chlorine so is all I will talk about (as opposed to hypochlorite
ion). The chlorinated isocyanurates show little if any disinfecting
capability and minimal oxidation power. The above equation is
described by a chemical equilibrium constant as shown by the
following:
[H2CY -] * [HOCl] / [HClCY -] = 10-5.62 = 2.4x10-6
At 3.5 ppm Free Chlorine (FC), this is equivalent to 4.9x10-5
moles/liter concentration while 30 ppm CYA is 2.3x10-4
concentration. Since the CYA concentration is much higher than
the FC concentration, even if all the chlorine could attach to

CYA via the above equation, the net effect is that the total
amount of "chlorine bound to CYA" can't be more than the
amount of FC and the H2CY - does not drop very much.
Rearranging, we have:
[HOCl] = 2.4x10-6 * [HClCY -] / [H2CY -]
Hypochlorous acid (HOCl) is also in equilibrium with hypochlorite
ion (OCl-) where at a pH of 7.5 this is roughly split 50/50
between these two species. So we can rewrite the above in
terms of measured concentrations as follows where CYA and FC
are total concentrations:
FC = [HOCl] + [OCl-] + [HClCY -]
CYA = [H2CY -] + [HClCY -]
[HOCl] = 2.4x10-6 * ([FC] - [HOCl] - [OCl-]) / ([CYA] - [HClCY -])
and at a pH near 7.5,
[HOCl] = 2.4x10-6 * ([FC] - 2*[HOCl]) / ([CYA] - [FC] + 2*
[HOCl])
For practical purposes, because CYA is much larger than FC, the
HClCY - can be initially ignored in the above. The above equation
implies that the HOCl concentration must be very small and that
most of the chlorine is bound to CYA. The following is an
approximation we can test:
[HOCl] is approximately 2.4x10-6 * [FC] / [CYA]
The chlorine values of HOCl and FC can be measured in the same
units (as they are on both sides of the equation so any factors
cancel), but we can convert the [CYA] concentration into ppm
by multiplying the right hand side (numerator) by the molecular
weight of CYA, 129.075 g/mole, and 1000 mg/g (multiplying the
denominator by this number converts CYA into ppm) resulting in:
HOCl is approximately 0.3 * FC / CYA
The above approximation isn't terribly far off from the accurate
calculation. At an FC of 3.5 ppm and a CYA of 30 ppm, the
actual HOCl is 0.051 ppm while the above approximation gives
0.035 ppm. You can see where the FC/CYA ratio comes from
-- it is a direct result of the chemical equilibrium between
chlorine attached to CYA vs. separate chlorine and CYA. A
more accurate approximation is given by modification of the
formula not removing the [FC] term in the denominator (which
results in a factor that is the ratio of CYA and Cl2 molecular
weights):
HOCl is approximately 0.31 * FC / (CYA - (1.8 * FC))
which with the FC of 3.5 ppm and CYA of 30 ppm results in
0.046 which is within 10% of the correct result. However, the
above approximation falls apart rather quickly when the CYA/FC
ratio is less than 5 and it is still pH dependent (the assumptions
were at a pH of 7.5 for the dominant species which determines
the equilibrium constant).
COMPLEX CHEMICAL EQUATIONS

So how can one conclude what the dominant species are since
that is the assumption I started with above? Let's look at the
detailed equations and go through a process of elimination based
on the pH. We'll start with the easier case to analyze, namely
CYA and its dissociated species. Some of the following equations
use an adjusted equilibrium constant for the ionic strength in
typical pool water at 300 ppm CH, 100 ppm TA, 30 ppm CYA and
525 ppm TDS. All of the equilibrium constants come from the
original 1974 O'Brien paper I refer to in the first post in this
thread, but you can also see these constants (with some minor
errors due to using slightly different sources) in this link on
document page 12 ( PDF page 18 ).
H3CY <--> H2CY - + H+ ..... pK = -log10(K) = 6.83
H2CY - <--> HCY 2- + H+ ..... pK = 11.26
HCY 2- <--> CY 3- + H+ ..... pK = 13.32

Let's take a look at the first reaction's equilibrium expression:


[H+] * [H2CY -] / [H3CY] = 10-6.83
Taking the negative log10 of both sides gives:
pH - log10([H2CY -] / [H3CY]) = pK
log10([H2CY -] / [H3CY]) = pH - pK
So from the above, and generalizing, one can see that when pH
< pK then the ratio in the log10 is less than 1 while when pH >
pK the ratio in the log10 is greater than 1. So this means that at
a pH of 7.5, the following are true:
[CY 3-] << [HCY 2-]
[HCY 2-] << [H2CY -]
[H2CY - ] > [H3CY]

So this is where we get our initial assumption of H2CY - being the


dominant cyanurate species where we can see that the next
most dominant cyanurate species is H3CY.
For the chlorinated isocyanurates, we have the following (the pK
are adjusted for ionic strength):
H2ClCY <--> H+ + HClCY - ..... pK = 5.28
HClCY - <--> H+ + ClCY 2- ..... pK = 9.98
HCl2CY <--> H+ + Cl2CY - ..... pK = 3.70

where we can conclude the following at a pH near 7.5:


HClCY - >> H2ClCY
ClCY 2- << HClCY Cl2CY - >> HCl2CY
So of the above species, HClCY - and Cl2CY - are dominant, but
we cannot yet tell which is more dominant between these two.
There are additional chemical equations relating to the

interaction of chlorine with the chlorinated isocyanurates as


follows:
Cl2CY - + H2O <--> HClCY - + HOCl ..... pK = 4.51
HCl2CY + H2O <--> H2ClCY + HOCl ..... pK = 2.93
Cl3CY + H2O <--> HCl2CY + HOCl ..... pK = 1.80
Because the HOCl concentration is relatively small (pHOCl > 4.6),
this implies the following:
HClCY - > Cl2CY H2ClCY >> HCl2CY
HCl2CY >> Cl3CY
So the assumption that HClCY - is the dominant chlorinated
isocyanruate species is reasonable and the next most dominant
chlorinated isocyanurate species is Cl2CY -.
In spite of the above equilibrium, the rate of release of chlorine
from CYA is rather fast so all of the chlorine attached to CYA
measures as FC in the FC test because the HOCl gets used up
reacting with the dye in the test and more HOCl is released from
that attached to CYA (or from hypochlorite ion) in the time of
the test.
All of the chemical equations are solved for explicitly through
iteration (due to changes in ionic strength) in this spreadsheet.
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#17

06-06-2008, 03:26 AM

chem geek,

Titanium
Senior Member

the original 1974 O'Brien paper is hard to find.


Join Date:
Location:
Posts:

Jun 2007
SF Bay Area
442

It sounds like you have the 1974 O'Brien paper. Are you able to
post it to the forum or provide a link to the paper?
Thanks!
Titanium

24,000 gallon inground freeform pool/spa circa 1983 (113 ft perimeter, 625
sq ft) with 350 gallon attached spill-over spa
2007 2 HP, three-phase Hayward TriStar pump which is powered by an
Ikeric VS-200 variable speed drive system
1983 Laars XE Pool/Spa Heater Type ES 400,000 BTU, 1998 Hayward
Super Star-Clear C-4000 cartridge filter (400 sq ft, 4 separate cartridges)
1998 Polaris 380 pressure-side cleaner w/ 3/4 HP booster pump
One skimmer :( and one PoolSkim :), One Supervision Galaxy LED pool
lamp, Second story solar panels
Hayward/GoldLine AquaLogic PS4 (replaced 1983 vintage dual circuit
Intermatic timer)
Reply With Quote

#18

06-06-2008, 12:33 PM

Titanium,

chem geek
Senior Member

Join Date:
Location:
Posts:

Mar 2007
San Rafael, CA USA
8,657

It's copyrighted material so I can't post it (at least not in its


entirety). I have a copy of the out-of-print book that it is in:
Chemistry of Water Supply, Treatment and Distribution that I
refer to in my first post in this thread. I pretty much bought up
the world's supply of that book sending it to the most important
people in the world who should have that book -- the people on
the committee defining the APSP-11 standards as well as the
CDC and others who should be aware of the chlorine/CYA
relationship and that this isn't new. The only copy I can still see
available for purchase is here and it's much more expensive
because, well, it's now more rare.
Nevertheless, many university library systems have this book
which is where I originally found it (in an off-site archive facility,
since it's not a frequently accessed book) after I saw it
referenced in this EPA document. The most relevant information
from the paper are the equilibrium constants for the chlorinated
cyanurates (and cyanuric acid) in Table 14.IV of that paper. I
will quote a few paragraphs or partial paragraphs (as an excerpt)
from that paper below:
______________________________________________________
______
______________________________________________________
______ _______________
Moreover, chlorinated cyanurates, in addition to acting as
stabilizers, exhibit a limited degree of hydrolysis to yield a
relatively constant level of germicidally potent, free chlorine. In
other words, chlorinated cyanurates may be considered as
analagous to a protected reservoir which liberates a small but
relatively constant level of free chlorine in accordance with
clearly defined principles of chemical equilibrium.
:
Ordinarily, most of the reservoir chlorine consists of chlorinated
cyanurates. Although these provide a readily available source of
active chlorine, Andersen1 has submitted evidence that
chlorinated cyanurates, as such, are not particularly germicidal.
As a result, the germicidal activity must be borne by the
relatively small fraction of free chlorine present at any given
time. Since, in general, increase in cyanurate concentration
results in decreased free chlorine, the use of large cyanurate
concentrations to achieve maximum stability will tend to give
inadequate germicidal activity. For the same reason the
continual addition of chlorinated cyanurates as a source of

chlorine is not recommended since this will lead to build up of


cyanurate concentration and consequent repression of the
concentration of free chlorine below that necessary for effective
germicidal activity.
:
Although chlorinated cyanurates serve as a reservoir of free
chorine, bactericidal efficacy is more closely related to the
relatively small fraction of free chlorine present at equilibrium.
Therefore, the use of excessive cyanurate in an overly zealous
attempt to reduce photolysis may repress free chlorine to the
point of suppressing germicidal activity. For the same reason the
continual addition of chlorinated cyanurates as a source of
chlorine is not recommended because this will lead to build up of
cyanurate concentration.
:
REFERENCES
1. Anderson, J.B. "The Influence of Cyanuric Acid on the
Bactericidal Effectiveness of Chlorine," Ph.D. Thesis, University
of Wisconsin, Madison, Wisconsin, 1963.
______________________________________________________
______
______________________________________________________
______ _______________
The paper defines "free chlorine" as being the sum of
hypochlorous acid and hypochlorite ion while "reservoir chlorine"
is free chlorine plus all chlorinated cyanurate species. In our
modern terminology based on what is measured in the Free
Chlorine (FC) test, FC is actually reservoir chlorine. So when the
paper says that higher CYA levels lower Free Chlorine, they are
referring to hypochlorous acid and hypochlorite ion, not to what
we now call FC.
Over the subsequent years, especially in the 1980's, a series of
papers demonstrated chlorine's dramatic reduction in
effectiveness in the presence of Cyanuric Acid. The most careful
of such studies (this PDF file) shows that the germicidal effect
of chlorine (against a species of protozoan cyst) is based on the
hypochlorous acid concentration. Other studies show the effects
against bacteria, viruses, algae and oxidative power (against
amino acids).
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
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#19

06-06-2008, 04:07 PM

Titanium
Senior Member

Richard,
Thanks for your excellent reply.

Join Date:
Location:
Posts:

Jun 2007
SF Bay Area
442

sending it to the most important people in the world who


should have that book -- the people on the committee
defining the APSP-11 standards as well as the CDC and
others who should be aware of the chlorine/CYA relationship
and that this isn't new.
Are you making any headway with changing hearts and minds
yet? What kind of reception are you receiving? I would think that
the CDC - being scientists with no profit ax to grind - would be
more receptive as compared to the APSP committee?
In a couple of years, perhaps TFP will have a large enough
following (and corresponding political power) in order to either
influence the APSP committee. Or perhaps we will put our own
people on the APSP committee.
[Side note to Sean B: Is TFP able to become an APSP member? I
assume that TFP would have to be an APSP member in order to
be eligible for APSP committee positions.]

It's copyrighted material so I can't post it (at least not in its


entirety).
Have you considered contacting the publisher (Ann Arbor
Science ? ) directly and asking them for permission to reproduce
the paper for specific purposes? It is hard to imagine that Ann
Arbor Science, if they even exist any more, really cares that
much about an obscure 35 year old paper. If you wanted, I
would volunteer to do some legwork on contacting the publisher
for permission to reproduce this paper.
Titanium

24,000 gallon inground freeform pool/spa circa 1983 (113 ft perimeter, 625
sq ft) with 350 gallon attached spill-over spa
2007 2 HP, three-phase Hayward TriStar pump which is powered by an
Ikeric VS-200 variable speed drive system
1983 Laars XE Pool/Spa Heater Type ES 400,000 BTU, 1998 Hayward
Super Star-Clear C-4000 cartridge filter (400 sq ft, 4 separate cartridges)
1998 Polaris 380 pressure-side cleaner w/ 3/4 HP booster pump
One skimmer :( and one PoolSkim :), One Supervision Galaxy LED pool
lamp, Second story solar panels
Hayward/GoldLine AquaLogic PS4 (replaced 1983 vintage dual circuit
Intermatic timer)
Reply With Quote

#20

06-06-2008, 04:34 PM

chem geek
Senior Member

Titanium,
Yes, if you could find out if the publisher still exists or got
bought out and can get permission for me, that would be great.
I don't have a lot of time to add something like that to my plate

so you could certainly help me out.

Join Date:
Location:
Posts:

As for the APSP-11 developing standard, I gave rather extensive


comments on it. I was very encouraged that it contained some
information on the chlorine/CYA relationship though not to the
level of detail I would have preferred so I sent some graphs and
"rules of thumb" info in the comments. I have no idea what will
come of it since there is no feedback process back to those who
make comments. I proposed using an "FC as % of CYA" with a
minimum FC as a standard and said that this wasn't that
different than the LSI that is already a multi-parameter index
and is referred to in the standard. I also made the radical
proposal of allowing (at least not recommending against) a small
amount of CYA for indoor pools.

Mar 2007
San Rafael, CA USA
8,657

As for the CDC, they are very busy and generally underfunded
and besides, they don't set pool standards. They are mostly just
focussed on disease prevention. Nevertheless, I have written to
them about possible ways of handling Crypto, but I'm probably
just a PITA to them -- I don't have any relevant credentials and
don't work in the industry. They've always been cordial, but I
just don't think they have much time to devote to these issues.
Thanks,
Richard

16,000 gallon outdoor in-ground 16'x32' plaster pool; Pentair Intelliflo VF


pump; Pentair IntelliTouch i9+3s control system; Jandy CL-340 square foot
cartridge filter
12 Fafco solar panels; Purex Triton PowerMax 250 natural gas heater
(200,000 BTU/hr output); automatic electric pool safety cover; 4-wheel
pressure-side "The Pool Cleaner"
Reply With Quote

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