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#1
05-25-2007, 06:56 PM
chem geek
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#2
05-25-2007, 06:58 PM
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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).
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
#3
05-25-2007, 07:00 PM
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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
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
#4
05-25-2007, 07:25 PM
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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]
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
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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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
[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
#6
03-17-2008, 09:59 PM
cliff_s
Member
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92
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
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#8
03-18-2008, 11:49 AM
duraleigh
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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,
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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
#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
#11
03-19-2008, 10:25 AM
JCJR
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#12
03-19-2008, 11:04 AM
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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
#13
03-19-2008, 12:05 PM
Guest
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
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#15
03-19-2008, 12:43 PM
JCJR
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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
Miami
266
#16
06-01-2008, 05:12 PM
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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
#17
06-06-2008, 03:26 AM
chem geek,
Titanium
Senior Member
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)
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#18
06-06-2008, 12:33 PM
Titanium,
chem geek
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#19
06-06-2008, 04:07 PM
Titanium
Senior Member
Richard,
Thanks for your excellent reply.
Join Date:
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442
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)
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#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
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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
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