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I have been intrigued by one of the principles of chemistry lately- electrolysis. In my knowledge, electrolysis is a quite dangerous operation as the decomposition of water produces hydrogen and oxygen gas, both which are flammable. However, its potent to be volatile isn't what I am concerned with; rather, it is the production of these gases sufficiently and cheaply that I have been wondering about.

Thus, what is the cheapest way available right now to build an efficient electrolysis apparatus that could be used for a relatively long amounts of time? In addition to this, what are the side effects with electrolysis of water? In addition to this, could solar panels be used in the process of electrolysis? I want this electrolysis apparatus to be as independent from the grid as possible!

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    $\begingroup$ Note: oxygen is not flammable, it merely enhances the combustion of other flammable stuff. $\endgroup$ Apr 5, 2016 at 7:28
  • $\begingroup$ Flammable means "easily set on fire", I think oxygen qualifies. Sometimes words go beyond the concepts they represent. $\endgroup$
    – HighInBC
    Oct 6, 2016 at 4:17

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Electrolysis of water involves the splitting (lysis) of water molecules using electricity.

$\ce{2H_{2}O(l) \rightarrow 2H_{2}(g) + O_{2}(g)}$

From the above equation, we see that the production of hydrogen will occur twice as fast as oxygen (on a volume basis). The electrode materials must be inert (non-reactive with water or its constituents). Platinum is good but very expensive, so titanium and/or nickel alloy catalysts are sometimes used. The current flows into the anode where oxygen gas is produced, whereas hydrogen gas is produced at the cathode. Generally, the higher the current, the higher the rate of production of hydrogen gas.

Since this is not a spontaneous reaction, energy is required from an external source in order to drive it. This is provided by a direct current (DC) electrical power supply, such as a battery or solar cell. The amount of energy required can be determined from the Gibbs energy of formation of water, which is -237.2 kJ/mol (at 298.15 K or 25 °C).

The theoretical minimum voltage needed for the reaction to occur is the standard electrode potential of oxygen, which is +1.23V. In practice, a slightly higher voltage (about 1.48V) is needed because of an over-potential of about 0.25V which is used up as heat.

Pure (demineralised) water can be expensive and has very low electrical conductivity, so some impurities in the water are desirable. Salt (sodium chloride) dissolved in the water will increase its conductivity dramatically, thereby reducing the current necessary to produce a produce hydrogen at a given rate. However, the chlorine gas can be produced at the anode (instead of oxygen) which is highly corrosive and hazardous. Minerals such as magnesium or calcium (present in sea water) will form insoluble precipitants on the cathode which could build up a 'passive' layer, reducing the rate of hydrogen production. Some acids or bases such as sulfuric acid or sodium hydroxide are therefore sometimes preferred.

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    $\begingroup$ Just a note, the easier way of typing chemical equations is via mhchem. See meta.chemistry.stackexchange.com/a/88/22 $\endgroup$ Dec 22, 2012 at 21:31
  • $\begingroup$ Speaking of chlorine gas, I have heard that they were used during World War II in gas bombs; therefore it would be impractical for me to do electrolysis with a solution containing sodium chloride . What other ionic compounds could I add to tap water (or any ordinary, dirty water) that will produce conduct electricity but is non-toxic at the same time? Thanks in advance. $\endgroup$
    – PotatoIn
    Dec 27, 2012 at 4:32
  • $\begingroup$ Chlorine gas was used on the battlefields of WW-1 by Germany, being heavier than air, would settle in the trenches of their enemies, forming hydrochloric acid and mucous in the lungs and thereby suffocating/choking the soldiers. Use of sodium hydroxide can be used as an electrolyte instead of sodium chloride so as not to produce chlorine gas. Also, using a manganese oxide coated anode is preferred for oxygen production at the anode (instead of chlorine) with high efficiency. $\endgroup$
    – theo
    Dec 28, 2012 at 0:17
  • $\begingroup$ You could also use sodium bicarbonate (baking soda), which is cheaper, but probably quite a bit less efficient. $\endgroup$ Apr 5, 2016 at 7:29

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