Salt Water Pool Electrolysis

The most common disinfectant used for swimming pools is chlorine. This is a combination of
free available chlorine (FAC) and combined available chlorine (CAC). While FAC is
composed of the free chlorine that is available for sanitizing the water, the CAC includes
chloramines which are formed by the reaction of the free chlorine with amines (produced by
a number of biological mechanisms such as perspiration, saliva, mucus, insects and other
pests). Chloramines are responsible for the "chlorine smell" of pools, as well as skin and eye
irritation. These problems are the result of insufficient levels of free available chlorine, and
indicate a pool that must be "shocked" by the addition of 5-10 times the normal amount of
chlorine.
In saltwater pools, the generator uses electrolysis to continuously produce free chlorine. As
such, a saltwater pool is not actually chlorine-free; it simply utilizes added salt and a chlorine
generator instead of direct addition of chlorine. It also burns off chloramines in the same
manner as traditional shock (oxidizer). As with traditionally chlorinated pools, saltwater pools
must be monitored in order to maintain proper water chemistry. Low chlorine levels can be
caused by insufficient salt, incorrect (low) chlorine-generation setting on the Salt Water
Generator (SWG) unit, higher-than-normal chlorine demand, low stabilizer, sun exposure,
insufficient pump speed, or mechanical issues with the chlorine generator. Salt count can be
lowered due to splash-out, backwashing, and dilution via rainwater.

Operation of a Salt Water Pool

The chlorinator cell consists of parallel titanium coated with ruthenium or iridium. Electrolysis
naturally attracts calcium and other minerals to the plates. Thus, depending on water
chemistry and magnitude of use, the cell will require periodic cleaning in a mild acid
solution (1-part Hydrochloric Acid to 15-parts water) which will remove the build-up of
calcium compound crystals (such as calcium carbonate or calcium nitrate). Excessive build-
up can reduce the effectiveness of the cell. Running the chlorinator for long periods with
insufficient salt in the pool can strip the coating off the cell which then requires an expensive
replacement, as can using too strong an acid wash.
Saltwater pools can also require stabilizer (Cyanuric Acid) to help stop the sun's UV rays
from breaking down free chlorine in the pool. Usual levels are 20 – 50 ppm. They also
require the pH to be kept between 7.2 and 7.6 with the chlorine being more effective if the
pH is kept closer to 7.2. The average salt levels are usually in the 3000-5000 ppm range,
which is only 10% of that commonly found in sea water. In swimming pools, salt is typically
poured across the bottom and swept with the pool brush until it dissolves; if concentrated
brine is allowed into the return-water system it can cause the chlorinator cell to malfunction
due to super-conductivity.

The Chemistry of Salt Water Electrolysis

Salt water chlorination produces an excess of hydroxyl ions, and this requires the frequent
addition of hydrochloric acid (HCl, also known as muriatic acid) to neutralise the alkalinity.
The initial chlorine chemistry is as follows:

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 1. Salt is dissolved in the pool water to produce sodium ions (Na+) and chloride ions
(Cl-)

4NaCl → 4Na+ + 4Cl-

2. The sodium and chloride ions flow dissolved in the pool water flow over the
energised electrode plates to produce metallic sodium (Na) and chlorine gas (Cl2)
4Na+ + 4Cl- → 4Na + 2Cl2

3. The highly reactive metallic sodium immediately reacts with water (H2O) to produce
yet more sodium ions plus hydroxide ions (OH-) and gaseous hydrogen (H2)
4Na + 4H2O → 4Na+ + 4OH- + 2H2

4. The gaseous chlorine produced in step 2 is hydrolysed by the pool water to produce
hypochlorous acid (HClO) plus hydrogen ions (H+) and chloride ions
2Cl2 + 2H2O → 2HClO + 2H+ + 2Cl-

5. The hypochlorous acid is unstable at normal temperatures (around 25°C) and

moderately elevated pH levels (between 7.2 and 7.6) and so dissociates into
hypochlorite ions (ClO-) and hydrogen ions
2HClO → HClO + ClO- + H+

By adding all the above steps together, you get the following chemical equation:

4NaCl + 3 H2O → 4Na+ + HClO + ClO- + OH- + 2Cl- + 2H2

Thus, the overall reaction produces an excess of hydroxide ions. These raise the pH of the
pool water. This increase in pH level can cause irritation to shin and eyes. In order to return
the pH to ‘normal’ levels, hydrochloric acid (HCl) is added:

HCl + 4Na + HClO + ClO- + OH- + 2Cl- +2H2 → HClO + OCl- + H2O + 4Na+ + 3Cl- + 2H2.

Adding these last two equations together one gets the final resulting equation

NaCl + HCl + 2H2O → HClO + OCl- + Na+ + 2H2

It is this hypochlorous acid and hypochlorite ions that do the job of sanitising the pool.

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The Pros and Cons of a Salt Water Pool

Pros

The benefits of salt systems in pools are the convenience and the constant delivery of pure
chlorine-based sanitiser. The reduction of irritating chloramines versus traditional
chlorinating methods and the "softening" effect of electrolysis reducing dissolved
alkali minerals (such a sodium) in the water are also perceived as benefits. For some people
that have sensitivities to chlorine, these systems may be less offensive. Salt water pools are
cheaper to maintain throughout the year, since salt is significantly cheaper than the
commercial chlorines.

Cons

Disadvantages are the initial cost of the system, maintenance, and the cost of replacement
cells. Salt is corrosive and will damage some metals and some improperly-sealed stone.
However, as the ideal saline concentration of a salt-chlorinated pool is very low (<3,500ppm,
the threshold for human perception of salt by taste. Seawater is about ten times greater than
this concentration), damage usually occurs due to improperly-maintained pool chemistry or
improper maintenance of the electrolytic cell.
Pool equipment manufacturers typically will not warrant against stainless steel products
being damaged by saline pools. Calcium and other alkali precipitate will build up naturally on
the cathode plates, and sometimes in the pool itself as “scaling”. This is the same effect as is
seen when one has “hard” water running through domestic pipes. Regular maintenance of
the cell is necessary. Failure to do so will reduce the effectiveness of the cell. Certain
designs of saline chlorinators use a "reverse-polarity" method that will regularly switch the
roles of the two electrodes between anode and cathode, causing this calcium build up to
dissolve off the accumulating electrode. Such systems reduce but do not eliminate the need
to clean the electrolytic cell and the occurrence of calcium scale in the water.
As chlorine is generated, pH will rise causing the chlorine to be less effective. Many systems
with chemistry automation can sense the rising pH and automatically introduce Hydrochloric
Acid in order to bring the pH back to the target level.
Automation systems will also manage levels of sanitizer by monitoring the redox levels of the
water. This ensures that only the needed amount of chlorine to be generated based on the
demand.