My easy way of making K perchlorate

[WSM]

The Chlorates and Perchlorates one of the best page on the theme for amateurs. The site writes about all the important things for amateurs. Experiments tests like the graphite anode in pH controlled KClO3, NaClO3 cell using HCl where not crash so fast the graphite. From chlorate and perchlorate specific anodes detailed descriptions.

http://www.chlorates.exrockets.com/chlorate.html

 

 

Yes, there is a lot of information on this site. I have copies from many years ago and still find it to be a useful reference.

 

WSM

[kingkama]

This sounds good but the process is not trivial (or inexpensive). Platinum alone works as a perchlorate anode, why plate it with LD?

 

Swede made his own lead dioxide anode by plating LD on an MMO/titanium substrate. This eliminated the difficult task of carefully preparing the CP titanium substrate for lead dioxide plating.

 

None of these steps are simple or easy.

 

WSM

May be are not easy start but plating on platinum is easy than plating mmo which can be destroyed by perchlorate environment. The idea is that platinum is sensitive to lower level of one of the precursors (nacl or naclo3) so you have to prepare an electrolyte without anything else than naclo3 (which is hard) or works in continue saturation like industrial process (wixh is expensive) so from that i take the idea. Plating 4 or 5 mm of LD is question of an hour, switching from low and hi current.

[Arthur]

Commercially Perc is made NaCl via NaClO₃ because a saturated solution of the sodium salt contains about 900g/l whereas a saturated solution of KChlorate contains about 70g/l

[WSM]

May be are not easy start but plating on platinum is easy than plating mmo which can be destroyed by perchlorate environment. The idea is that platinum is sensitive to lower level of one of the precursors (nacl or naclo3) so you have to prepare an electrolyte without anything else than naclo3 (which is hard) or works in continue saturation like industrial process (wixh is expensive) so from that i take the idea. Plating 4 or 5 mm of LD is question of an hour, switching from low and hi current.

 

If I remember correctly, platinum is sensitive to high chlorides in a chlorate to perchlorate cell, so starting a perchlorate cell when using a platinum anode is best done with low to no chlorides in the electrolyte.

 

I plan to achieve this by making and drying purified (precursor-free) sodium chlorate crystals first. I do so using an MMO/titanium chlorate cell.

 

The next phase is to make up the perchlorate electrolyte from pure sodium chlorate crystals and run it in either a platinum/titanium OR a beta-form lead dioxide/titanium perchlorate cell; to make sodium perchlorate solution.

 

After the sodium perchlorate run is completed (by calculation, stopping it before degradation of the anode begins), the cooled raw NaClO₄ solution is treated with standardized sodium metabisulfite solution till the perchlorate solution tests chlorate-free. Only then is purified potassium chloride solution added to the sodium perchlorate solution.

 

I find that the potassium perchlorate drops out of solution instantly as a fine white powder, leaving all the other ions in solution. I remove the freshly prepared KClO₄ by vacuum filtration and rinse it with chilled water till a flame test indicates no sodium residue remains.

 

WSM

[WSM]

Commercially Perc is made NaCl via NaClO₃ because a saturated solution of the sodium salt contains about 900g/l whereas a saturated solution of KChlorate contains about 70g/l

 

 

Arthur is correct.

 

I will add that commercially, the less energy and effort used in the process, the more economical the product.

 

The next step (NaClO₃ to NaClO₄) approximately doubles the solubility; sodium chlorate - 1057g/liter H₂O 25^oC and sodium perchlorate - 2096g/liter H₂O 25^oC, if I'm reading the charts correctly.

 

WSM

[kingkama]

 

If I remember correctly, platinum is sensitive to high chlorides in a chlorate to perchlorate cell, so starting a perchlorate cell when using a platinum anode is best done with low to no chlorides in the electrolyte.

 

I plan to achieve this by making and drying purified (precursor-free) sodium chlorate crystals first. I do so using an MMO/titanium chlorate cell.

 

The next phase is to make up the perchlorate electrolyte from pure sodium chlorate crystals and run it in either a platinum/titanium OR a beta-form lead dioxide/titanium perchlorate cell; to make sodium perchlorate solution.

 

After the sodium perchlorate run is completed (by calculation, stopping it before degradation of the anode begins), the cooled raw NaClO₄ solution is treated with standardized sodium metabisulfite solution till the perchlorate solution tests chlorate-free. Only then is purified potassium chloride solution added to the sodium perchlorate solution.

 

I find that the potassium perchlorate drops out of solution instantly as a fine white powder, leaving all the other ions in solution. I remove the freshly prepared KClO₄ by vacuum filtration and rinse it with chilled water till a flame test indicates no sodium residue remains.

 

WSM

Q i guess we didn't understand each other, electrode degradation starts when nacl or naclo3 levels drop below 10%, this is the reason why industrial cells work in constant saturation, so that the product precipitates when the electrolyte is still saturated.

[Arthur]

I'm well aware of the violet ppt test for the presence of perc. Is anyone able to offer a spot test for chlorate please?

[mx5kevin]

Here the forum buy unnecessary tools many people, and many people are trying to find uncertain solutions that work poorly with by non-purpose devices. Professional tools are quickly destroyed if user make a mistake with them. On YT videos the KClO3 and KClO4 almost nowhere is it professionally cleansed. The K2S2O5 not used properly, and KClO3 and KClO4 not recrystallized just washed which is a serious mistake. It is very important to produce more with the possible less work, we do not work instead of tools. Who recommends methods like heating hypochlorite to make chlorate that are nonsense for people who really want to use chlorates/perchlorates.

 

Making anodes at home like PbO2 are not worth it. Under 1000ml NaClO4 solution not worth working for. Under 500g not worth to make KClO3 or KClO4/one time. The equipment costs a lot. For a 0,5l cell a 70mm long 3mm wide silver rod what is fully coated with 0,2mm thick pure platinum so that they are not attacked by chemicals a choice for life for chlorate and perchlorate production. Collecting in a 0,5l cell from 3 times the total chlorate/perchlorate what are cc 500g are the minimum what worth it to start to work with it. It must be made individually. For using 400-1000ml small cells are excellent. For making NaClO4 directly in one step from NaCl. And making KClO3 from KCl are perfect. For KClO3 and NaCl setup in every 500 ml solution added 5ml 30% HCl/Day In this case, precise pH control is not important with this 0,2mm thick pure platinum anode. 3 weeks total run time from NaCl to NaClO4 in one step 6V 4A are used the power source are a car batters charger. Cell temperature does not matter runs outdoor and impossible to winter and summer keep it the same temperature. It is covered with a seed bed plastic foil and a plastic paint bucket. It is prepared in the same time in summer and winter.In the NaClO4 setup when HCl added in a plastic bottle and no gases are formed no more hydrochloric acid should be added at this time. This point after a day running from pH6 possible a negative pH like pH -1. For a 0,2mm pure platinum, this is not a problem. If too much acid used in this raw pH controlling this is not problem in my setup. I use a graphite cathode it's not necessary using titan. Methyline blue, sensitive chlorate tests, pH meter in this setup unnecessary. A 2000ml beaker, stainless steel saucepan and a plastic bucket used to make the KClO4. The NaClO4 after sedimentation boiled with HCl and K2S2O5 to destroy chlorates in a beaker and not stainless steel. Proportionally to the K2S2O5 added the HCl and boiled the solution to generate SO2 gas this is very important for the reaction (5-max 10% K2S2O5 destroyed all the chlorate) i used 5%. After this the NaClO4 reacted with KCl saturated solutions at room temperature mixed at 80°C in a plastic bucket. Washed with NaHCO3 solution and ice cold water and recrystallized in pure water 2 times +washed the crystals every time. The KClO4 crystals dried in a hot plate using stainless steel saucepan. The fine powdered KClO4 crystals tested with 30% HCl. If stays white, no reaction means its pure. No matter how many times it is made always the same. The result are more purer than technical grade. With the KCl, NaClO4 I never dry out them. Stainless steel not tolerate KCl, NaClO4, NaCl to heat in this crystals. In the cell from every 100g NaCl i calculated to get 210g total NaClO4. And every 1g NaClO4 i calculated 0,6g KCl. 1g KCl dissolved 2,9g H2O. 1liter water calculated to 1Kg using a electric balance. And 1g NaClO4 dissolved 0,5g H2O. In the cell 1g NaCl dissolved in 2,8g H2O (using a 500ml cell the solution are 400ml and 142g NaCl i dissolved to start the process). By evaporating the excess water i get this solutions. The KCl i made from fertilizer i do not crystallize. Stainless still tolerate to heat it in KClO4 and KClO3. Or oven in a ceramic baking dish.

 

When PbO2 are used or few microns platinum in a titanium base first must made the chlorate with MMO anode. Then calculated using sugar+methyline blue test that point when the NaClO4 close to form and must change the anode to perchlorate specific anode. With these anodes must use precise pH controlling. pH papers are washed out by chlorine. pH meters must calibrate regularly using pH 7 and 4 pH buffers and it's not cheap. Towards the end of the process in a perchlorate cell must kept the pH 7-8 in a perchlorate cell. Under pH 7 a pH 6 cell after a day running the pH meter shows negative pH. When PbO2 used this must be paid close attention to. PbO2 anodes not tolerate too alkali pH more than pH 9 too. The few micron platinum coating in a titanium base very vulnerable, a lot of poor quality platinum anodes are sold on the internet what crash in a perchlorate cell. These should not be used for chlorate production.

 

If someone uses alternatives like homemade anodes, or you are not using the tools properly like heating wet NaCl, KCl crystals, acidic HCl solution in a stainless steel pan, heating up too fast the beaker. That multiplies the costs. These devices are quickly destroyed in this case. Example melting NaClO3 in a ceramic pan to get NaClO4 and later the pan are cracked. Or using crucible, household ceramic materials not for intended use, or not in the parameters which is required for the reaction. Too hot cells for perchlorate production, clorate and perchlorate cells unnecessary run indoor, i run it outdoor where chlorine gas are not problem. The pH meter not washed with NaHCO3 solution after used in the chlorate cell etc.

Edited April 10, 2022 by mx5kevin

[WSM]

I'm well aware of the violet ppt test for the presence of perc. Is anyone able to offer a spot test for chlorate please?

 

 

I have three:

1. aniline HCl - 0.4g aniline HCl + 1.0ml HCl concentrated (reagent grade). To a drop of test solution add one drop of aniline HCl solution. If chlorate is present the solution turns red then greenish blue.
2. indigo carmine - 0.001g indigo carmine + 1.0ml H₂O. To two drops of indigo carmine solution, add a few drops of HCL and then up to five drops of test solution. The indicator losing color (going clear) indicates chlorate.
3. N-phenylanthranilic acid (NPAA) - to three to five drops of test solution, add two to three drops of 3% NPAA solution (in ethanol or 99% isopropanol), followed by two or more drops of concentrated HCl, followed by gentle stirring with a glass rod. A purple coloration indicates chlorate.

These tests are very sensitive and can detect very small amounts of chlorate in a solution, especially numbers 2 and 3.

 

WSM

Edited April 12, 2022 by WSM

[kingkama]

Here the forum buy unnecessary tools many people, and many people are trying to find uncertain solutions that work poorly with by non-purpose devices. Professional tools are quickly destroyed if user make a mistake with them. On YT videos the KClO3 and KClO4 almost nowhere is it professionally cleansed. The K2S2O5 not used properly, and KClO3 and KClO4 not recrystallized just washed which is a serious mistake. It is very important to produce more with the possible less work, we do not work instead of tools. Who recommends methods like heating hypochlorite to make chlorate that are nonsense for people who really want to use chlorates/perchlorates.

 

Making anodes at home like PbO2 are not worth it. Under 1000ml NaClO4 solution not worth working for. Under 500g not worth to make KClO3 or KClO4/one time. The equipment costs a lot. For a 0,5l cell a 70mm long 3mm wide silver rod what is fully coated with 0,2mm thick pure platinum so that they are not attacked by chemicals a choice for life for chlorate and perchlorate production. Collecting in a 0,5l cell from 3 times the total chlorate/perchlorate what are cc 500g are the minimum what worth it to start to work with it. It must be made individually. For using 400-1000ml small cells are excellent. For making NaClO4 directly in one step from NaCl. And making KClO3 from KCl are perfect. For KClO3 and NaCl setup in every 500 ml solution added 5ml 30% HCl/Day In this case, precise pH control is not important with this 0,2mm thick pure platinum anode. 3 weeks total run time from NaCl to NaClO4 in one step 6V 4A are used the power source are a car batters charger. Cell temperature does not matter runs outdoor and impossible to winter and summer keep it the same temperature. It is covered with a seed bed plastic foil and a plastic paint bucket. It is prepared in the same time in summer and winter.In the NaClO4 setup when HCl added in a plastic bottle and no gases are formed no more hydrochloric acid should be added at this time. This point after a day running from pH6 possible a negative pH like pH -1. For a 0,2mm pure platinum, this is not a problem. If too much acid used in this raw pH controlling this is not problem in my setup. I use a graphite cathode it's not necessary using titan. Methyline blue, sensitive chlorate tests, pH meter in this setup unnecessary. A 2000ml beaker, stainless steel saucepan and a plastic bucket used to make the KClO4. The NaClO4 after sedimentation boiled with HCl and K2S2O5 to destroy chlorates in a beaker and not stainless steel. Proportionally to the K2S2O5 added the HCl and boiled the solution to generate SO2 gas this is very important for the reaction (5-max 10% K2S2O5 destroyed all the chlorate) i used 5%. After this the NaClO4 reacted with KCl saturated solutions at room temperature mixed at 80°C in a plastic bucket. Washed with NaHCO3 solution and ice cold water and recrystallized in pure water 2 times +washed the crystals every time. The KClO4 crystals dried in a hot plate using stainless steel saucepan. The fine powdered KClO4 crystals tested with 30% HCl. If stays white, no reaction means its pure. No matter how many times it is made always the same. The result are more purer than technical grade. With the KCl, NaClO4 I never dry out them. Stainless steel not tolerate KCl, NaClO4, NaCl to heat in this crystals. In the cell from every 100g NaCl i calculated to get 210g total NaClO4. And every 1g NaClO4 i calculated 0,6g KCl. 1g KCl dissolved 2,9g H2O. 1liter water calculated to 1Kg using a electric balance. And 1g NaClO4 dissolved 0,5g H2O. In the cell 1g NaCl dissolved in 2,8g H2O (using a 500ml cell the solution are 400ml and 142g NaCl i dissolved to start the process). By evaporating the excess water i get this solutions. The KCl i made from fertilizer i do not crystallize. Stainless still tolerate to heat it in KClO4 and KClO3. Or oven in a ceramic baking dish.

 

When PbO2 are used or few microns platinum in a titanium base first must made the chlorate with MMO anode. Then calculated using sugar+methyline blue test that point when the NaClO4 close to form and must change the anode to perchlorate specific anode. With these anodes must use precise pH controlling. pH papers are washed out by chlorine. pH meters must calibrate regularly using pH 7 and 4 pH buffers and it's not cheap. Towards the end of the process in a perchlorate cell must kept the pH 7-8 in a perchlorate cell. Under pH 7 a pH 6 cell after a day running the pH meter shows negative pH. When PbO2 used this must be paid close attention to. PbO2 anodes not tolerate too alkali pH more than pH 9 too. The few micron platinum coating in a titanium base very vulnerable, a lot of poor quality platinum anodes are sold on the internet what crash in a perchlorate cell. These should not be used for chlorate production.

 

If someone uses alternatives like homemade anodes, or you are not using the tools properly like heating wet NaCl, KCl crystals, acidic HCl solution in a stainless steel pan, heating up too fast the beaker. That multiplies the costs. These devices are quickly destroyed in this case. Example melting NaClO3 in a ceramic pan to get NaClO4 and later the pan are cracked. Or using crucible, household ceramic materials not for intended use, or not in the parameters which is required for the reaction. Too hot cells for perchlorate production, clorate and perchlorate cells unnecessary run indoor, i run it outdoor where chlorine gas are not problem. The pH meter not washed with NaHCO3 solution after used in the chlorate cell etc.

I'm with you a thick platinum anode could be the best choice, newer listen platinum on silver but to me souds perfect. I decide to plate pbo2 on platinum-titanium anode because the failure of a few microns coating and partially destruction of the anode itself, so, plating in pbo2 was the only solution viable. The plating itself is wery cheap, due the low price of the substances involved, 3 o 4 mm of pbo2 in acidic environment tolerate for the necessary time 400 mAh cm2. If the plating fail in an hour it can be remade. Thaks for the info shared.

[mx5kevin]

I'm well aware of the violet ppt test for the presence of perc. Is anyone able to offer a spot test for chlorate please?

 

The trouble is that the sensitive tests cost a lot and difficult to obtain. One such test is there for the price of an MMO anode. With KClO4 simple add fine powdered KClO4 to 30% HCl. Any yellowish color change show chlorate. It accurately detects even very small quantities chlorate in KClO4. When K2S2O5 the test show greyish color change if not clean. If this test does not show anything KClO4 completely suitable for pyrotechnic use. Reproduced the cell run time/parameters the same quality can be reproduced regularly. There will be little difference in how much chlorate it contains. Making pure absolute chlorate free NaClO4 from the cell not possible to made. Indigo carmine test can easy to use when destroying the clhorate with K2S2O5. High levels of chlorate can be detected by rough cheap tests. Heating NaClO4 on a gas flame in a spoon or a small amount in a foil using a hotplate. If the powder shows signs of melting, it indicates high levels of chlorate. If the NaClO3 and KCl solution are mixed with hot the KClO3 are disolwed and precipitates in large quantities as colored crystals upon cooling. When the NaClO4 solution K2S2O5 and HCl are added and it turns strongly yellow when boiled indicates the presence of high levels of chlorate. When NaClO4 mixed with sugar and few drops 98% sulfuric acid are added and if ignite that refers to large quantities of chlorate. I had pharmacopoeial pure KClO4 from a pharmacy. No difference could be detected with different home test. The homemade does not contain any impurities that would cause any chemical deviation for pyrotechnic purposes.

[mx5kevin]

I'm with you a thick platinum anode could be the best choice, newer listen platinum on silver but to me souds perfect. I decide to plate pbo2 on platinum-titanium anode because the failure of a few microns coating and partially destruction of the anode itself, so, plating in pbo2 was the only solution viable. The plating itself is wery cheap, due the low price of the substances involved, 3 o 4 mm of pbo2 in acidic environment tolerate for the necessary time 400 mAh cm2. If the plating fail in an hour it can be remade. Thaks for the info shared.

 

I made in the past a GSLD anode from a 8mm welding carbon rod. A smooth durable coating is very difficult to make. It required special equipment. It takes as much resources, time as the perchlorate itself. The electrode needed to spinned with a motor to make the coating smooth in my case. Platinum on titanium base if the electrode is of good quality it works for many years in a perchlorate setup (see: NurdRage on YT). If platinum has problems with destruction it is a poor quality electrode. These platinum electrodes are not need to coated with PbO2. There are more people have problem with fake poor quality platinum mesh anodes in titanium base. If purchased from trusted companies then there is no such problem. Many people use platinized titanium in perchlorate cells without problems see on Youtube. Some people are coating MMO anodes with PbO2 this, in turn, is very difficult. For most people, the best solution is to buy these electrodes ready. Many people make KClO3, and few KClO4. Even fewer can make a quality PbO2 anode. The 0,2mm platinum in a silver base an electrode that is made to order with costumer specific parameters. Silver is very important here as it is the best electrical conductor and it's a small electrode. I've had this for several years it cannot be ruined. Importantly, platinum completely wraps around the electrode. Silver not contact to any chemical effects. The idea comes from a professional who has been making such electrodes for several years. PbO2 in a chlorate cell are not worth it, it wears out too fast. If someone can make a new one quickly then this is not a problem. The easiest and fastest solution is to buy these electrodes. People can buy such electrodes everywhere from lot of sellers with worldwide shipping.

Edited April 11, 2022 by mx5kevin

[WSM]

I'm with you a thick platinum anode could be the best choice, newer listen platinum on silver but to me souds perfect. I decide to plate pbo2 on platinum-titanium anode because the failure of a few microns coating and partially destruction of the anode itself, so, plating in pbo2 was the only solution viable. The plating itself is wery cheap, due the low price of the substances involved, 3 o 4 mm of pbo2 in acidic environment tolerate for the necessary time 400 mAh cm2. If the plating fail in an hour it can be remade. Thaks for the info shared.

 

 

If your lead dioxide anode coating (as thick as you describe) wears out in one hour, I suspect you're making alpha form lead dioxide which is spongy and porous. The desired coating is beta form lead dioxide which is the hard crystalline form, and completely suitable for a perchlorate cell (also harder to do correctly).

 

This is important for a cell which will last long enough to survive several runs, at least, and hopefully many more.

 

WSM

Edited April 12, 2022 by WSM

[WSM]

 

The trouble is that 1)the sensitive tests cost a lot and difficult to obtain. One such test is there for the price of an MMO anode. With KClO4 simple add fine powdered KClO4 to 30% HCl. Any yellowish color change show chlorate. It accurately detects even very small quantities chlorate in KClO4. When K2S2O5 the test show greyish color change if not clean. If this test does not show anything KClO4 completely suitable for pyrotechnic use. Reproduced the cell run time/parameters the same quality can be reproduced regularly. There will be little difference in how much chlorate it contains. Making pure absolute chlorate free NaClO4 from the cell not possible to made. 2)Indigo carmine test can easy to use when destroying the clhorate with K2S2O5. High levels of chlorate can be detected by rough cheap tests. Heating NaClO4 on a gas flame in a spoon or a small amount in a foil using a hotplate. If the powder shows signs of melting, it indicates high levels of chlorate. If the NaClO3 and KCl solution are mixed with hot the KClO3 are disolwed and precipitates in large quantities as colored crystals upon cooling. When the NaClO4 solution K2S2O5 and HCl are added and it turns strongly yellow when boiled indicates the presence of high levels of chlorate. When NaClO4 mixed with sugar and few drops 98% sulfuric acid are added and if ignite that refers to large quantities of chlorate. I had pharmacopoeial pure KClO4 from a pharmacy. No difference could be detected with different home test. The homemade does not contain any impurities that would cause any chemical deviation for pyrotechnic purposes.

 

 

1)This is true, but worth the effort in my case.

 

2)I had a problem with the indigo carmine test when trying to use it during chlorate destruction of my raw NaClO₄ electrolyte. I was using Na₂S₂O₅ solution to destroy the residual chlorate but that method yielded H₂SO₄ in the NaClO₄ solution, which gave a false positive with the indigo carmine chlorate test.

 

My choice was to use the N-phenylanthranilic acid test, which gave no false positives for chlorate in the perchlorate solution. My treated sodium perchlorate solution then produced chlorate-free potassium perchlorate when KCl was added.

 

I use sodium metabisulfite rather than potassium metabisulfite, due to

1. the nature of my cell
2. the ready availability of the sodium metabisulfite
3. the lower cost of Na₂S₂O₅ vs. K₂S₂O₅

That said, I like your descriptions of low cost alternative tests and treatments for chlorate in perchlorate solutions. Can you give clear details so others can follow your descriptions easier?

 

I mean the particular details of the quality, concentration and quantity of materials to use for those tests and treatments? This information would be much more useful (and repeatable) than vague descriptions, and I'm sure would be appreciated by everyone here.

 

Thank you in advance for the extra effort.

 

WSM

[WSM]

 

I made in the past a GSLD anode from a 8mm welding carbon rod. A smooth durable coating is very difficult to make. It required special equipment. It takes as much resources, time as the perchlorate itself. The electrode needed to spinned with a motor to make the coating smooth in my case. Platinum on titanium base if the electrode is of good quality it works for many years in a perchlorate setup (see: NurdRage on YT). If platinum has problems with destruction it is a poor quality electrode. These platinum electrodes are not need to coated with PbO2. There are more people have problem with fake poor quality platinum mesh anodes in titanium base. If purchased from trusted companies then there is no such problem. Many people use platinized titanium in perchlorate cells without problems see on Youtube. Some people are coating MMO anodes with PbO2 this, in turn, is very difficult. For most people, the best solution is to buy these electrodes ready. Many people make KClO3, and few KClO4. Even fewer can make a quality PbO2 anode. The 0,2mm platinum in a silver base an electrode that is made to order with costumer specific parameters. Silver is very important here as it is the best electrical conductor and it's a small electrode. I've had this for several years it cannot be ruined. Importantly, platinum completely wraps around the electrode. Silver not contact to any chemical effects. The idea comes from a professional who has been making such electrodes for several years. PbO2 in a chlorate cell are not worth it, it wears out too fast. If someone can make a new one quickly then this is not a problem. The easiest and fastest solution is to buy these electrodes. People can buy such electrodes everywhere from lot of sellers with worldwide shipping.

 

 

I like the mention of making a GSLD anode. If I had one, I'd try the direct production of sodium perchlorate from sodium chloride (with NaF catalyst) described in old research papers. Can you describe how you made it? I'd love to try it myself one day.

 

I also like your description of the platinum on silver anode. 0.2mm is a thick coating (200 microns, correct?). The best I've found so far is 50 microns thick. Yours is obviously custom made. Very nice!

 

I agree that chlorates are best made using MMO on titanium. I reserve my Pt and PbO_2/beta plated anodes for perchlorate cells, exclusively. When I read of other amateur attempts to use LD anodes and experiencing failures or destruction of the anode in use, I supposed they ran them as though the electrodes were MMO. Fearing to destroy my expensive and hard-to-find anodes, I ran my experiments with lower voltage (~4.5 Vdc) and lower amperage (~1.0-1.5 Amps per cm²) , and they worked well with no detectable damage.

 

I ran my perchlorate experiments with all the commercially produced sodium chlorate I had (about 8 pounds or >3.6 Kg), and stopped due to the lack of available NaClO₃. Since that time, my efforts switched to learning to produce my own sodium chlorate as feed stock for further perchlorate research. That effort is continuing.

 

WSM

Edited April 12, 2022 by WSM

[WSM]

 

 

I have three:

1. aniline HCl - 0.4g aniline HCl + 1.0ml HCl concentrated (reagent grade). To a drop of test solution add one drop of aniline HCl solution. If chlorate is present the solution turns red then greenish blue.
2. indigo carmine - 0.001g indigo carmine + 1.0ml H₂O. To two drops of indigo carmine solution, add a few drops of HCL and then up to five drops of test solution. The indicator losing color (going clear) indicates chlorate.
3. N-phenylanthranilic acid (NPAA) - to three to five drops of test solution, add two to three drops of 3% NPAA solution, followed by concentrated HCl, two or more drops followed by gentle stirring with a glass rod. A purple coloration indicates chlorate.

WSM

 

 

I have used all three tests over the years, but the best choice for me was number three, since number two failed in use due to a false positive due to sulfuric acid residue in my treated sodium perchlorate solution.

 

I found that number three was not affected by other compounds dissolved in the treated sodium perchlorate electrolyte. This allowed me to be certain my sodium perchlorate solution was chlorate-free before converting it to potassium perchlorate by metathesis.

 

My greatest regret is that all three reagents are unstable in solution, and will last only a short time (weeks at best) when made up in bulk, so making up only enough reagent for immediate testing is advised. Number two is the easiest to acquire and low cost, but it has it's limitations. Number three is my first choice but expensive and very hard to find.

 

It's my opinion that using only the smallest about of these reagents, made immediately before use, in a spot plate (one or two drops only, sometimes) would make an excellent spot test for chlorates, while conserving these expensive and hard to source materials. I got this idea and notion from an esteemed colleague and friend many years ago, while we were discussing spot tests for pyrotechnic materials.

 

WSM

 

Edit: I forgot to mention that in chlorate test number 3, the NPAA reagent is a 3% solution in alcohol (both ethanol and 99% isopropanol have been used successfully). The alcohol with 3% reagent is followed by two or more drops of concentrated hydrochloric acid and then gentle stirring with a glass rod.

Edited April 12, 2022 by WSM

[mx5kevin]

The homemade chlorate and perchlorate project

 

This is my NaClO4, KClO4, NaClO3, KClO3, NH4ClO4 setup.

[kingkama]

 

 

If your lead dioxide anode coating (as thick as you describe) wears out in one hour, I suspect you're making alpha form lead dioxide which is spongy and porous. The desired coating is beta form lead dioxide which is the hard crystalline form, and completely suitable for a perchlorate cell (also harder to do correctly).

 

This is important for a cell which will last long enough to survive several runs, at least, and hopefully many more.

 

WSM

 

i Lost a comma, if fail,in an hour can be remade. If used at 300 mhA cm2 endure for weeks. If used at 500/700 you can end a kilo run without problem.

On Platinum substrate the difference between the two beta and alpha forms is less important than graphite anodes, the best solution is to plate the alpha form to make a thick layer and coat it with the beta form to increase The strength of the piece. As you know the current density differentiates the type of plated oxide.I have noticed in this group a tendency towards perfection greater than the need to obtain a result, we are all good at buying something perfect, but we would all be good at making it ourselves? It is obvious that the best solution is to buy quality perchlorate directly, which certainly costs less in terms of time spent and the cost of precursors and equipment. I think that here we do things as a hobby and not as a company so what's the point of wasting money on perfect and dedicated equipment. Then if the point of the question is to define who has it bigger or who is better or who is the best, I think that this forum was not born with this purpose and eventually it would take a competition Where to compare on the final product and not on the basic components. Having said that, however, thanks to everyone for the advice that is always always welcome

[kingkama]

 

 

I like the mention of making a GSLD anode. If I had one, I'd try the direct production of sodium perchlorate from sodium chloride (with NaF catalyst) described in old research papers. Can you describe how you made it? I'd love to try it myself one day.

 

I also like your description of the platinum on silver anode. 0.2mm is a thick coating (200 microns, correct?). The best I've found so far is 50 microns thick. Yours is obviously custom made. Very nice!

 

I agree that chlorates are best made using MMO on titanium. I reserve my Pt and PbO_2/beta plated anodes for perchlorate cells, exclusively. When I read of other amateur attempts to use LD anodes and experiencing failures or destruction of the anode in use, I supposed they ran them as though the electrodes were MMO. Fearing to destroy my expensive and hard-to-find anodes, I ran my experiments with lower voltage (~4.5 Vdc) and lower amperage (~1.0-1.5 Amps per cm²) , and they worked well with no detectable damage.

 

I ran my perchlorate experiments with all the commercially produced sodium chlorate I had (about 8 pounds or >3.6 Kg), and stopped due to the lack of available NaClO₃. Since that time, my efforts switched to learning to produce my own sodium chlorate as feed stock for further perchlorate research. That effort is continuing.

 

WSM

I'd like to give you some advice on how to make your own naclo3. Starting with a saturated solution of nacl, start the electrolysis and add a container full of nacl inside the reaction v Vessel, this will keep the solution saturated at all times. Given the solubility of naclo3 you will often have to add nacl in the prepared container, when the solution is saturated with naclo3 they will begin to form wonderful crystals you just have to fish them out and keep adding nacl. This is a similar process to that used in the industry, In this way, if you have two power supplies, you can build two identical cells but with different anodes and add the product of one into the other without ever stopping the process. Both sodium salts (naclo3 and naclo4) will sink to the bottom if you hold the solution, saturated with the precursor salt. This is a method that requires preparation but saves a lot of time. Edited April 13, 2022 by kingkama

[Arthur]

One important requirement is to ensure that the chlorate contains no lower oxidation ingredients (chlorite and hypochlorite ) and that the finished perc contains no chlorate (etc).

One reason why commercial production is done in two stages is to ensure that the chlorate is pure before being sent to the perc cells.

 

Remember the goal is not only to have perc it's to have have (commercially) pure, chlorate free perc.

 

I can get a posiive perc test easily BUT proving purity is very much less easy.

[WSM]

One important requirement is to ensure that the chlorate contains no lower oxidation ingredients (chlorite and hypochlorite ) and that the finished perc contains no chlorate (etc).

One reason why commercial production is done in two stages is to ensure that the chlorate is pure before being sent to the perc cells.

Remember the goal is not only to have perc it's to have have (commercially) pure, chlorate free perc.

I can get a posiive perc test easily BUT proving purity is very much less easy.

 

Yes, absolutely.

 

This is how my years of research/interest in this subject has ended up.

 

First I purify my newly formed chloride brine, then electrolyse it to make and next separate my crystals of sodium chlorate. The lesser salts break down as the sodium chlorate air dries, evidenced by the loss of chlorine smell (on the fully dry chlorate crystals). The second phase of the project is where the perchlorate electrolyte is made up from the fully dried sodium chlorate crystals and then electrolyzed using either a platinized titanium or beta-form lead dioxide on titanium anode paired with suitable CP titanium cathodes.

 

The second step proceeds in less time and with no chlorine smell. I suppose this is because we are only adding one oxygen atom to the chlorate ions and not making several ions simultaneously as in the chlorate process. The only odor I detect emanating from the perchlorate cell vent is ozone, which make sense since the perchlorate electrodes have a greater oxygen over-potential than MMO electrodes do (also why MMO doesn't produce perchlorate with any suitable efficiency).

 

So, to sum up, in my experience, the two step process (chloride to chlorate, then chlorate to perchlorate) appears to be the easiest path to make perchlorates for amateur electrochemists, without lots of extra effort or waste.

 

WSM

Edited April 22, 2022 by WSM

[eb666]

KingKama said:

 

"

 

I'd like to give you some advice on how to make your own naclo3. Starting with a saturated solution of nacl, start the electrolysis and add a container full of nacl inside the reaction v Vessel, this will keep the solution saturated at all times. Given the solubility of naclo3 you will often have to add nacl in the prepared container, when the solution is saturated with naclo3 they will begin to form wonderful crystals you just have to fish them out and keep adding nacl.

 

"

 

What temperature do you run the Sodium Chlorate cell at so that you can get solid Sodium Chlorate coming out of solution at the same time that you are getting Sodium Chloride

to go into the solution?

 

Cheers,

 

EB

[eb666]

The platinum-on-silver anodes are probably platinum CLAD anodes as opposed to platinum plated (electroplated onto the silver) anodes. This is the way all platinum anodes for industrial perk. making are made. I believe you cannot electroplate platinum past a thickness of 100 (rough guess) micron. Most large industrial Pt anodes are platinum clad copper.

 

I think copper would be good enough. There is not much difference between the conductivity of Cu and Ag.

 

EB

[mx5kevin]

The platinum-on-silver anodes are probably platinum CLAD anodes as opposed to platinum plated (electroplated onto the silver) anodes. This is the way all platinum anodes for industrial perk. making are made. I believe you cannot electroplate platinum past a thickness of 100 (rough guess) micron. Most large industrial Pt anodes are platinum clad copper.

 

I think copper would be good enough. There is not much difference between the conductivity of Cu and Ag.

 

EB

 

0,2mm pure platinum on a silver are not electroplated. Platinum is ironed on a silver base with a mashine. The minimum wall thickness are 0,2mm with this method. They can do it 0,4mm too double that much money. There are companies who deal specifically with this. They must be given the exact parameters and they make it for you that anode. It should be emphasized that the ends of the electrode are separately coated with platinum it cannot be a free piece uncoated where silver can contact the cell atmosphere or solution neither end of the anode. With such an costly electrode, it is not worth saving on silver. Copper would be the worst solution. I use this electrode for ten years. Using for 6V 4-6A cells are perfect. The downside is that it has a small surface area electrode 0,5-1 kg KClO3 or KClO4 it can be conveniently made with it using a 0,5-1,5l cell. This electrode guaranteed a lifetime investment.

 

 

Silver is not only the best electrical conductor but a hard metal, chemically very resistant does not rusted. A quality precious metal base Cu, Nb, Ti, it will not bring that quality. With such an expensive electrode, it is not worth the risk poor conductivity, poor quality base. The copper completely erodes in a chlorate perchlorate cell atmosphere. Titanium have poor conductivity. The electrode are tested and working in the long term with the specified parameters.

Edited April 22, 2022 by mx5kevin

[mx5kevin]

It is very important to use the right tools for the purpose. And that the tools are used professionally. Must avoid errors that could ruin these tools. The biggest costs are caused by these tools. It is necessary to consider whether the tool or method is suitable for this task in the long run. It is very costly if someone does not use the intended tools for their intended purpose. Bigger problems I've see:

 

Protecting the tools: The beaker: Use a Wire Gauze Heat Shield with Ceramic Center to protect the beaker from thermal shock or will be cracked or use a sand bath this is important. Do not heat directly intensive way in hot plate because this will crack the beaker. Hotplate: Protect it with aluminum foil from corrosion. Stainless steel saucepan: Do not heat it in wet NaCl, KCl, NaClO4, NaClO3 crystals in it this will rusted the saucepan immediately and contaminated the product. Do not boil HCl acidic solution in it. Use 18/10 stainless steel. Possible to heat in it wet KClO3 and KClO4 crystals without erosion. The electrodes: When used few micron platinum or PbO2 in perchlorate cells and make the chlorate with MMO anode. Keep the pH 6-7 or 7-8 to protect the MMO and PbO2 anode from too alkali or acidic solutions using a digital pH meter. Digital pH meter: Need to calibrate with pH buffers, and always wash it with NaHCO3 solution after used in the chlorate, perchlorate cell. Aluminum saucepan, ceramic pans, borosilicate glass baking tray in oven, or gas stove: In pure aluminum possible to heat wet KCl, NaCl, NaClO4, NaClO3 crystals and the pan not get rusted using a hotplate or gas stove. But pure aluminum not tolerate alkali or acidic solutions! Borosilicate glass or ceramic in baking tray in oven another choice to dry out these crystals.

 

Anyone who doesn’t have a routine buys a lot of unnecessary tools and chemicals. Which will not use later, or ruin it quickly. One of the biggest problem if someone make perchlorates.