Sodium

and Potassium chlorate

synthesis, the complete guide

Made by Plante1999

It is know that chlorates can be easily made. Much of the chlorate made by individual are used
in pyrotechnic, but this thread will be mostly intended to use the chlorate as a general oxidizer in the
laboratory. It is also know that there is many way to make chlorates, this document will be
about electrolytic manufacture but other procedure are described as well.

Warning!
Chlorates are toxic to all life form and persistent in the environment use ''thermal'' disposition for
chlorate. Never mix chlorate with sulphur and/or sulphide, such mixture can set off without apparent
reason. Do not mix with ammonium compound, Ammonium chlorate could be formed and this
compound is an explosive. Reference for everything in the text is on demand in contact my tab of this
website.

General use of the chlorate in the laboratory

In the laboratory chlorate can be used as a general dry oxidizer, some of its property make
it reassemble to a mixture of hydroxide and nitrate which is very useful to dissolve some transition
metal element and bring them to high oxidation state. An example could be
dichromate production using chlorate and chromium trioxide.
2KClO3 + Cr2O3 -) K2Cr2O7 + Cl2 + O2
Such reaction cannot be used to make permanganate since manganese dioxide decompose it, the
second use of chlorate which is making oxygen in quantity without an oxygen gas cylinder, Manganese
dioxide catalyze the decomposition of chlorate to make chloride and oxygen, this decomposition start at
very low temperature and as such an alcohol burner give enough heat to make the reaction going.
2KClO3 -(MnO2)-) 2KCl + 3O2
The last general use is for pyrotechnics, I’m not familiar with this use but It could be used as
an oxidizer but usually perchlorate is preferred for safety reason.

OTC chemical based synthesis.

Sodium hypochlorite and calcium hypochlorite are very OTC and sold as disinfecting agent. There
disproportion affords chlorate and chloride. Boiling 10% sodium hypochlorite in a glass vessel to
decompose the hypochlorite and boil off water will make a concentred solution of sodium chlorate and
sodium chloride, adding saturated potassium chloride solution to it will add potassium ion which will
separate out with the chlorate ion producing solid potassium chlorate by metathesis reaction.. Passing
chlorine gas made from OTC calcium hypochlorite and hydrochloric acid in a boiling solution of
potassium carbonate will make potassium chlorate and potassium chloride by chlorine
disproportion, subsequent recrystallization will afford potassium chlorate.

3NaClO -) 2NaCl + NaClO3

3Cl2 + 3K2CO3 -) KClO3 + 5KCl + 3CO2

Electrochemical synthesis:
The last common synthesis of chlorates is by electrochemical synthesis starting from a chloride salt. The
mechanism of the reaction is not perfectly understood but the general idea is that chlorine form at the
anode and dissolves in the water of the solution to make hypochlorous acid and hydrochloric acid in
equilibrium. At the cathode hydrogen is formed which make OH- making alkali metal hydroxide. When
the dissolved chlorine react with the hydroxide it form back alkali metal chloride plus alkali metal
hypochlorite, as already know the hypochlorite disproportion in hot water to afford chloride and
chlorate, The chloride Is re-oxidized at the anode to make chlorine gas and the cycle continue making
more and more chlorate. This cycle is favored by a slightly acidic PH and hot temperature in the cell
electrolyte. When the cell run small amount of chlorine escape making slowly the solution basic and
stabilise at around PH 10 which is a lot less efficient since in acidic/neutral PH the hypochlorite
disproportion in chlorate and chloride but in basic condition this hardly happen and only anode
oxidation take place. This is hard to the anode and take 9 electron in place of the 6 in acidic PH.
Cl2 + H2O -) HClO + HCl
HClO + KOH -) KClO + H2O
3KClO -) 2KCl + KClO3

Do all synthesis outside!

Chemical synthesis1:
Reagents:
Sodium hydroxide, NaOH

Potassium hydroxide, KOH

Calcium hypochlorite 70%, Ca(OCl)2 (Chlorine chock for pool)

Hydrochloric acid 31%, HCl 31% (Muriatic acid , hardware store) can be substituted by Sodium chloride
and sodium hydrogen sulphate, NaHSO4 (Pool Ph -)
Distilled water

Material:
PVC tubing ¼ inch

Flask with a stopper with one hole (for the PVC tubing)

250ml beaker

Funnel

Filter paper

Method to keep the solution in the beaker at 70-80 degree Celsius

Equation:

KOH + 5NaOH + 3Cl2 -) 5NaCl + KClO3 + 3H2O

Experimental:
Dissolve 16g of potassium hydroxide and 44g of sodium hydroxide in 70 ml of distilled water. Fill the
flask with 85g of calcium hypochlorite, secure the PVC tube in the stopper hole. Bring the hydroxide
solution to 70 to 90 degree Celsius and depose the outlet of the tube in the solution, add 200g of
hydrochloric acid to the flask in small increment and close it each time with the stopper. Chlorine gas
will be produced in the flask and will react with the hot alkaline solution to make Chlorate and chloride
anion. After a few minutes all the calcium hypochlorite will have reacted to make chlorine gas and the
reaction will be considered as completed. Cool to 0 degree Celsius. On cooling Chlorate anion will
condense with the potassium cation to make crystals of potassium chlorate. Filter the solution to get the
crystals and Dry the potassium chlorate on a glass or polypropylene sheet. If the intended purpose is
pyrotechnics there is no need for recrystallization. Purification is done by recrystallization with three
times the weight of the crystals of distilled water.

Yield: 14-15g
Chemical synthesis2:
Reagents:
Sodium hypochlorite 10-12%, NaOCl (liquid chlorine for pool)

Potassium chloride, KCl (No salt substitute)

Distilled water

Material:
2x500ml beaker

Funnel

Filter paper

Method to boil the solution which will be in one of the beaker

Equation:
3NaOCl -) 2NaCl + NaClO3

NaClO3 + KCl -) KClO3 + NaCl

Experimental:
250g of 10-12% sodium hypochlorite solution is boiled to 1/9 of its starting volume and cooled. Dissolve
9g of potassium chloride in the minimum amount of cold distilled water. Filter the boiled sodium
hypochlorite solution in the potassium chloride solution. Cool to 0 degree Celsius and filter the
crystalline precipitate. Purify using the same method as the first chemical synthesis.

Small scale electrochemical synthesis:

Reagents:
Saturated sodium chloride, NaCl solution (can be found as salt)

Saturated potassium chloride solution, KCl (can be found as no salt substitute)

Optional: Sodium or potassium (di)chromate (cannot be found OTC)

Material:
Anode:
Carbon or graphite rod are the best since they are easy to find and cheap, you can get some at your local
hardware store in the lantern battery, tutorial can be found on internet. They can also be found as
‘’gouging’’ rod in a welder shop. These anodes will erode and it is recommended to use dichromate
additive. Carbon was the industrial choice before MMO (DSA) anode was invented.

Cathode:
Carbon will do the job very well and is cheap. If you can easily find titanium rod this is even better than
carbon but it will need to be cleaned after each run to remove titanium dioxide crust. In industry iron is
used but the solution need to have 7g/L of sodium dichromate which is carcinogenic, also iron which is
not in solution will need to be protected with rubber, epoxy will do the job for some time but it will
eventually flake of. Iron have a great advantage, it is very common and cheap. You might have heard of
stainless steel but from my own experimentation normal grade stainless steel will not do a better job
than iron but will cost much more. If iron ore stainless steel is used without dichromate a suspension of
iron hydroxide will form making necessary to filter your solution before precipitating your chlorate.

Cell body (container):

A glass beaker will do a great job but if PH control is not used the beaker will be corroded. If PH control
is not one of your priorities use a polypropylene container (recycling number 5). 100ml volume
minimum per amp for overheating protection.

Power supply:
You need a 3.3 to 6 volt power supply which can deliver at least 1ampere. This can be found in
electronic store.

Funnel

Filter paper

Running/processing:
First you need to know the maximum amperage your anode can take. For graphite/carbon this is 0.030
ampere per square centimeter. Don’t pass more amperage than you r anode can take or it will shred
into pieces. 3.3 volt is the best to protect erosion at your anode but up to 6volt is ‘’manageable’’. Put
the positive wire on the anode and the negative on the cathode. Fill you Cell body with the sodium
chloride solution and turn the power supply on. Keep your cell solution below 40 degree Celsius, if it go
to high place the cell in a water bath. Adding (di)chromates will increase your yield very much, in this
type of cell it is highly recommended, from 0.25 to 7g per L is a right proportion the yield goes up as the
(di)chromate concentration goes up. PH control is also highly recommendable to protect anode erosion.
To make PH control simply add 31% HCl in your cell solution time to time. It is much more easy to add
the right amount of HCl using dichromate additive, when the solution turn yellow add HCl30% until the
solution turn orange, repeat this every time the solution turn yellow. Dichromate also serve as a PH
buffer, When the PH is basic it will decompose to chromate increasing the acidity and when the PH is
acid the chromate will turn into dichromate removing excess acidity (Equation will be added in V 1.1).
To calculate how much time it will need to electrolyse do this equation, The %100 represent the
efficiency of your cell so for an amateur cell 35% is considered normal. The saltm is the number of mole
of salt in your cell electrolyte (For a rough idea use 0.5mole. per 100ml solution). Amp is the amperage
that goes in your cell.

Time(H)= ((171.6/amp)x saltm)x %100

This will give you the number of hour you need to lets The chloride convert in chlorate, Do not forget PH
control if you use it. After this run time filter the solution and add the same molar equivalent of
potassium chloride in the form of saturated solution. Cool the mixed solution to O degree Celsius and
filter the crystalline potassium chlorate precipitate. Purify it using the same procedure as the chemical
synthesis 1. Add few ml of methanol to your mixed solution if you were using (di)chromate additive and
add metabisulphite to reduce chlorate, then poor it down the drain.

Larger scale electrochemical synthesis:

Material:
Anode:
If you are planning to make chlorate on a larger scale buying an MMO anode sheet on ebay is a very
good idea. It won’t erode and will stop working after thousands of hour. They can run at 80 degree
Celsius nd at 0.200ampere per scare centimeter.

Cathode:
The same as small scale electrosynthesis

Cell body (container):

Same as small scale electrosynthesis.

Power supply:
Same as small scale electrosynthesis

Running/processing:
Very similar as the small scale synthesis but because of the MMO the cell solution is keep very hot (70-
80 degree Celsius) and you can directly run with saturated potassium chloride solution and purify the
precipitate (which will form in the cell) to get potassium chlorate. This type of production gives also the
chance to make sodium chlorate. When the cell is runned at 80 degree Celsius it will evaporation a lot.
For potassium chloride solution tap of is made with distilled water, but for sodium chloride the tap of is
done with saturated sodium chloride solution, after a few days of running a precipitate will form. This is
the sodium chlorate. Filter to get the sodium chlorate but do not purify. Do not use sodium chlorate for
pyrotechnics, use sodium chlorate for chemistry only.

This is the version 1.0 and is only a part of the complete guide.

Sources:

Dan2 website (link does not work)

Synthetic inorganic chemistry 5em, Blanchard 1937

Electrochemical process in chemical industry, Albert Regner