Electrolysis of water

Electrolysis of water is the decomposition of water (H2O) into oxygen (O2) and hydrogen gas (H2) due to an
electric current being passed through the water. This electrolytic process is used in some industrial applications
when hydrogen is needed.

An electrical power source is connected to two electrodes, or two plates, (typically made from some inert metal
such as platinum or stainless steel) which are placed in the water. Hydrogen will appear at the cathode (the
negatively charged electrode, where electrons are pumped into the water), and oxygen will appear at the anode (the
positively charged electrode). The generated amount of hydrogen is twice the amount of oxygen, and both are
proportional to the total electrical charge that was sent through the water.

Electrolysis of pure water is very slow, and can only occur due to the self-ionization of water. Pure water has an
electrical conductivity about one millionth that of seawater. It is sped up dramatically by adding an electrolyte (such
as a salt, an acid or a base).

Historically, the first known electrolysis of water was done by William Nicholson and Anthony Carlisle in about
1800.

Equations

In the water at the negatively charged cathode, a reduction reaction takes place, with electrons (e−) from the cathode
being given to hydrogen cations to form hydrogen gas (the half reaction balanced with acid):

Cathode (reduction): 2H+(aq) + 2e− → H2(g) ;

At the positively charged anode, an oxidation reaction occurs, generating oxygen gas and giving electrons to the
anode to complete the circuit:

Anode (oxidation): 2H2O(l) → O2(g) + 4H+(aq) + 4e−;

The same half reactions can also be balanced with base as listed below. Not all half reactions must be balanced with
acid or base. Many do like the oxidation or reduction of water listed here. To add half reactions they must both be
balanced with either acid or base.

Cathode (reduction): 2H2O(l) + 2e− → H2(g) + 2OH−(aq);

Anode (oxidation): 4OH−(aq) → O2(g) + 2H2O(l) + 4e−;

Combining either half reaction pair yields the same overall decomposition of water into oxygen and hydrogen:

Overall reaction: 2H2O(l) → 2H2(g) + O2(g)

The number of hydrogen molecules produced is thus twice the number of oxygen molecules. Assuming equal
temperature and pressure for both gases, the produced hydrogen gas has therefore twice the volume of the produced
oxygen gas. The number of electrons pushed through the water is twice the number of generated hydrogen
molecules and four times the number of generated oxygen molecules.
Thermodynamics of the process

Decomposition of pure water into hydrogen and oxygen at standard temperature and pressure is not favorable in
thermodynamical terms. This is because, E(cell)=E(Oxidation) + E(Reduction). If E(cell) < 0, reaction is not
favorable.

Thus, the standard potential of the water electrolysis cell is 1.23 V at 25 °C.

The positive voltage indicates the Gibbs Free Energy for electrolysis of water is greater than zero for these
reactions. This can be found using the Nernst Equation at equilibrium. The reaction cannot occur without adding
necessary energy, usually supplied by an external electrical power source but also possible with thermal energy.

Hoffman voltammeter connected to a direct current power source converter.

Electrolyte selection

If the above described processes occur in pure water, H+ cations will accumulate at the anode and OH− anions will
accumulate at the cathode. This can be verified by adding a pH indicator to the water: the water near the anode is
acidic while the water near the cathode is basic. These charged ions will repel the further flow of electricity until
they have diffused away, a slow process. This is why pure water conducts electricity poorly and why electrolysis of
pure water proceeds slowly.

If a water-soluble electrolyte is added, the conductivity of the water rises considerably. The electrolyte disassociates
into cations and anions; the anions rush towards the anode and neutralize the buildup of positively charged H+ there;
similarly, the cations rush towards the cathode and neutralize the buildup of negatively charged OH− there. This
allows the continued flow of electricity.[1]

Care must be taken in choosing an electrolyte, since an anion from the electrolyte is in competition with the
hydroxide ions to give up an electron. An electrolyte anion with less standard electrode potential than hydroxide
will be oxidized instead of the hydroxide, and no oxygen gas will be produced. A cation with a greater standard
electrode potential than a hydrogen ion will be reduced in its stead, and no hydrogen gas will be produced.

The following cations have lower electrode potential than H+ and are therefore suitable for use as electrolyte
cations: Li+, Rb+, K+, Cs+, Ba2+, Sr2+, Ca2+, Na+, and Mg2+. Sodium and lithium are frequently used, as they form
inexpensive, soluble salts.

If an acid is used as the electrolyte, the cation is H+, and there is no competitor for the H+ created by disassociating
water. The most commonly used anion is sulfate (SO42-), as it is very difficult to oxidize, with the standard potential
for oxidation of this ion to the peroxydisulfate ion being −0.22 volts.

Strong acids such as sulfuric acid (H2SO4), and strong bases such as potassium hydroxide (KOH), and sodium
hydroxide (NaOH) are frequently used as electrolytes.
Techniques
Proton Exchange Membrane Water Electrolysis

A proton conducting membrane can also be used as to separate the anode from the cathode chamber. The typical
membrane used is NAFION and can be catalyst coated to form a HYDRion® membrane.

Fundamental Demonstration

Two leads, running from the terminals of a battery, are placed in a cup of water with a quantity of electrolyte added
to establish conductivity. Hydrogen and Oxygen gases will stream from the oppositely charged electrode. Oxygen
will collect at the anode and hydrogen will collect at the cathode.

Match test used to detect the presence of hydrogen gas.

Hofmann voltammeter
Main article: Hofmann voltammeter

The Hofmann voltammeter is often used as a small-scale electrolytic cell. It consists of three joined upright
cylinders. The inner cylinder is open at the top to allow the addition of water and the electrolyte. A platinum
electrode is placed at the bottom of each of the two side cylinders, connected to the positive and negative terminals
of a source of electricity. When current is run through the Hofmann voltammeter, gaseous oxygen forms at the
anode and gaseous hydrogen at the cathode. Each gas displaces water and collects at the top of the two outer tubes,
where it can be drawn off with a stopcock.

Industrial electrolysis

Many industrial electrolysis cells are very similar to Hofmann voltammeters, with complex platinum plates or
honeycombs as electrodes. Generally the only time hydrogen is intentionally produced from electrolysis is for
specific point of use application such as is the case with oxyhydrogen torches or when extremely high purity
hydrogen or oxygen is desired. The vast majority of hydrogen is produced from hydrocarbons and as a result
contains trace amounts of carbon monoxide among other impurities. The carbon monoxide impurity can be
detrimental to various systems including many fuel cells.

High-temperature electrolysis
Main article: High-temperature electrolysis

High-temperature electrolysis (also HTE or steam electrolysis) is a method currently being investigated for water
electrolysis with a heat engine. High temperature electrolysis is more efficient than traditional room-temperature
electrolysis because some of the energy is supplied as heat, which is cheaper than electricity, and because the
electrolysis reaction is more efficient at higher temperatures.

Applications

About four percent of hydrogen gas produced worldwide is created by electrolysis. The majority of this hydrogen
produced through electrolysis is a side product in the production of chlorine.
2 NaCl + 2 H2O → Cl2 + H2 + 2 NaOH

The electrolysis of brine, a water sodium chloride mixture, is only half the electrolysis of water since the chloride
ions are oxidized to chlorine rather than water being oxidized to oxygen. The hydrogen produced from this process
is either burned, used for the production of specialty chemicals, or various other small scale applications.

The majority of hydrogen used industrially is derived from fossil fuels. One example is fossil fuel derived hydrogen
used for the creation of ammonia for fertilizer via the Haber process and for converting heavy petroleum sources to
lighter fractions via hydrocracking. The production of this hydrogen usually involves the formation of synthesis gas
a mixture of H2 and CO. Synthesis gas can be hydrogen enriched through the water gas shift reaction. In this
reaction the carbon monoxide is reacted with water to produce more H2 with CO2 byproduct.

There is some speculation about future development of hydrogen as an energy carrier in a hydrogen economy,
although the rapid evolution of electric battery technology makes overall efficiency a major consideration.

Efficiency

Water electrolysis does not convert 100% of the electrical energy into the chemical energy of hydrogen. The
process requires more extreme potentials than what would be expected based on the cell's total reversible reduction
potentials. This excess potential accounts for various forms of overpotential by which the extra energy is eventually
lost as heat. For a well designed cell the largest overpotential is the reaction overpotential for the four electron
oxidation of water to oxygen at the anode. An effective electrocatalyst to facilitate this reaction has not been
developed. Platinum alloys are the default state of the art for this oxidation. The reverse reaction, the reduction of
oxygen to water, is responsible for the greatest loss of efficiency in fuel cells. Developing a cheap effective
electrocatalyst for this reaction would be a great advance.

The simpler two electron reaction to produce hydrogen at the cathode can be electrocatalyzed with almost no
reaction overpotential by platinum or in theory a hydrogenase enzyme. If other, less effective, materials are used for
the cathode then another large overpotential must be paid.

The energy efficiency of water electrolysis varies widely with the numbers cited below on the optimistic side. Some
report 50–70%[2], while the theoretical maximum efficiency of the electrolysis of water is between 80–94%.[3] These
values refer only to the efficiency of converting electrical energy into hydrogen's chemical energy. The energy lost
in generating the electricity is not included. For instance, when considering a power plant that converts the heat of
nuclear reactions into hydrogen via electrolysis, the total efficiency may be closer to 30–45%.[4]

See also

• Electrochemistry
• Electrolysis
• Hydrogen production
• Noryl
• Gas cracker

References

1. ^ Linus Pauling, General Chemistry, Section 15-2. San Francisco, 1970

2. ^ Werner Zittel; Reinhold Wurster (1996-07-08). Chapter 3: Production of Hydrogen. Part 4: Production
from electricity by means of electrolysis. HyWeb: Knowledge - Hydrogen in the Energy Sector. Ludwig-
Bölkow-Systemtechnik GmbH.
 3. ^ Bjørnar Kruse; Sondre Grinna, Cato Buch (2002-02-13). Hydrogen--Status and Possibilities (pdf). The
Bellona Foundation. Archived from the original on 2002-02-13. “Efficiency factors for PEM electrolysers
up to 94% are predicted, but this is only theoretical at this time.”
4. ^ Briefing Paper #73: Transport and the Hydrogen Economy. Uranium Information Centre's Briefing
Papers. Australian Uranium Association (January 2008). “[Fuel cells] catalyse the oxidation of hydrogen
directly to electricity at relatively low temperatures and the claimed theoretical efficiency of converting
chemical to electrical energy to drive the wheels is about 60% (or more). However, in practice about half
that has been achieved, except for the higher-temperature solid oxide fuel cells - 46%.”

• Electrolysis of Water. Experiments on Electrochemistry. Retrieved on November 20, 2005.

• Electrolysis of Water. Do Chem 044. Retrieved on November 20, 2005.

Questions - simple science experiments

I've done same research on this topic so far, but haven't seen anything concise that can help so I thought I'd pose
some questions here. I'm trying to help my son complete a science experiment for 5th grade. That experiment is to
demonstrate electrolysis of water using a 6v lantern battery and a salt solution (I am using filtered water and sea
salt, 1 tbsp salt in 1L of water). I have to admit I thought the experiment would be easy for him, but it failed. The
6V battery generated plenty of hydrogen gas but no oxygen that we could discern. We next tried to use a 9VDC
transformer powered by 110VAC and the results were similar. Finally I tried 110VAC directly and had success. My
questions are:

1. The thermodynamics section seems to indicate the potential for the reaction might take place at <2V. Under
what conditions and using AC or DC? Why did 6VDC and 9VDC fail to produce oxygen gas?
2. A substance is left in the salt water solution after the 110VAC (braided copper) wires are applied to the
solution. What is this?
3. It seems that a significant power source must be used to generate oxygen and hydrogen? Does that make
sense?

My apologies for what may be simple questions. (JT Pickering (talk) 16:23, 4 May 2008 (UTC))

This is really not the place, but you do note that if DC only produces hydrogen at one electrode, 110 V AC
will simply produce hydrogen at *both* electrodes because of the nature of the alternating current?
--Rifleman 82 (talk) 16:45, 4 May 2008 (UTC)
Retrieved from "http://en.wikipedia.org/wiki/Talk:Electrolysis_of_water"

Endothermic or Exothermic?

Is electrolysis of water endo or exo? —The preceding unsigned comment was added by 121.223.213.155 (talk) 11:24, August 22,
2007 (UTC)

Electrolysis of water is endothermic; energy is flowing through the water delivering energy. The result is the
exothermic release of heat, as excess energy is shed in an attempt to re-establish homeostasis with the
surrounding environmental temperature; the water can get rather hot, and actually in some poorly designed
electrolyzers the water can begin to boil. Noah Seidman 16:13, 14 September 2007 (UTC)
Endo and exothermic process are targeted towards reactions that are best described through enthalpies.
Electrochemical reactions are better described as galvanic (spontaneous or giving off energy) or electrolytic
(nonspontaneous or energy consuming). Electrolysis of water is an electrolytic reaction and requires energy.
Since that energy can not be delivered with perfect efficiency (the has an overpotential) extra energy is
poured into the system and is manifested as heat.--OMCV (talk) 05:57, 7 April 2008 (UTC)
Anodes/Electrodes

We seem to have had several edits and reverts pertaining to the beginning of the section, which says "Hydrogen
will appear at the cathode (the negatively charged electrode, where electrons are pumped into the water), and
oxygen will appear at the anode (the positively charged electrode)." -- especially, the words "positive" and
"negative" being switched around. There's also an accompanying graphic which would seem to imply that hydrogen
will appear at the negatively charged electrode, and oxygen will appear at the positively charged anode. Anyone
care to clarify? Mikaey (talk) 07:53, 19 November 2007 (UTC)

Methods for improving the efficiency of electrolysis

As is mentioned in the article, adding potentially free heat to the water will result in higher conversion rates. What
other methods are used to increase electrolysis efficiency? What research has been done on the effect of electrode
materials, electrode topologies, and brine/electrode chemistries? Does modulating the voltage across the electrodes
have any influence? —Preceding unsigned comment added by Voxelman (talk • contribs) 18:13, 12 January 2008 (UTC)

[edit] Scientific fraud

To begin, I'm glad you will be willing to work on this page, Nseidm1. To begin with on this electrolysis of water
page the concern is not directly the financial scam but the fraudulent information concerning electrolysis. I would
direct you to Internal combustion engine#Engine Efficiency however I suspect the second to last paragraph in that
section to have been installed by a sock puppet or one of your collaborators. The efficiency of an ICE is primarily
dictated by the difference between the lower and upper temperatures of the engine as described by the Carnot cycle.
For a terrestrial engine this means an ICE is limited by the upper thermal stability of the material used to make the
engine. As a result most engines don't do better than around 35% at their max efficiency. In a well designed engine
99.9% of the fuel is combusted to H2O and CO2. The small fraction that isn't fully combusted ends up as trace
quantities of CO and hydrocarbons. At the same time during combustion some of the nitrogen include in the fuel/air
mixture is converted to NOX. As stated before all of these trace exhaust materials are a fraction of a percent of the
fuel combusted. A more complete combustion would not add a measurable effect to the systems efficiency for a
well designed engine. Meaning no change in MPG. It is true that altering the fuel mixture (gasoline + another fuel)
as well as the air to fuel ratio effects the concentration and relative ratio amounts of these trace exhausts. I am not
surprised that a gasoline/H2 mixture burns more efficiently (say 99.9% vs 99.99%). I trust there has been extensive
studies into the gasoline/hydrogen fuel mixture since nearly every conceivable fuel mixture has been studied, thank
you for identifying this literature. I would however, like to point out that most manufactures find it more efficient to
add a catalytic converter rather than an exotic fuel mixture. The emission is a tangential point, the core interest is a
drastic increase in fuel efficiency and that is the basis of the fraud. Just to address all the issues you mentioned the
role of sludge popularized in TV commercial for various brand of gasoline is not an issue for a well designed
engine using a well formulated fuel. I have include this information here as a supplement since it is in appropriate
to include information on a page about water electrolysis. Please address any further concerns to this talk page.--
OMCV (talk) 02:52, 23 April 2008 (UTC)

First to clarify, I am only Noah Seidman and have no sockpuppets. I only represent myself (I have no
collaborators). I have edited these pages for a long time, and my knowledge and comprehension of the
subject matter is continuously improving. I revert all the hype, and bad info inserted regarding fuel
enhancement scams. I also wish to uphold the scientific integrity of wikipedia.
Some questions. Would an engine operating mostly 30:1 air/fuel ratios have better economy than an engine
operating at 14.7:1? Since there is a limit on air flow through the intake system to achieve 30:1 ratios
approximately 1/2 the fuel would have to be injected; 1/2 the fuel would entail an effect on economy. Am I
totally of base here? Would fuel vaporization, prior to direct injection increase the potential economy of the
engine being that only gasoline vapors are combustible? As the temperature of combustion decreases NOx
production will decrease, therefore wouldn't operating an engine under ultra lean conditions reduce
emissions the same way as running an engine rich? In an ultra lean burning engine what would the role be
 for a catalytic converter? My understanding of a catalyst is that it reduces the activation energy required for
a reaction to take place; therefore encouraging the formation of dioxides from monoxides.
To elaborate on my role and intentions. I believe that the combination of fuel vaporization, hydrogen
injection, and ultra lean burn conditions will allow an EC engine to operate slightly more efficiently, much
more economically, emit less monoxides, and eliminate NOx production entirely. Fuel enhancement is more
than just "hydrogen injection", its a combination of a variety of concepts with the intent to maximize the
potential for a IC engine. I see no reason that an IC engine should be running under rich conditions; to me
this is a waste of fuel in a cheap attempts to reduce combustion temperature. A large excess of atmosphere
(lean conditions) will achieve the same temperature reducing effect, while also improving economy.
Also, automotive applications are not my favorite application, and I find it quite frustrating that I find
myself involved in in depth debates on the subject. I want to apply the fuel enhancement concept to
residential and power production applications, which I feel is much more viable although less applicable to
the general public. I probably end up in automotive debates because it is the only engine that the general
public is familiar with. Noah Seidman (talk) 03:37, 23 April 2008 (UTC)
As for being concerned about info in oxyhydrogen, hydrogen fuel enhancement and other articles. The vast
majority of info regarding "fuel enhancement" is quotation from academic publication. There is little info in
those sections from patents, and all bold statements are from third party academia. As you precisely pointed
out efficiency cannot be effected much, which I always agreed with, but emissions and economy can be
effected. The position I have always held is that "hype", and these scam marketing tackings (ie. run your car
on water) are quite disturbing.
There is much academia that says the economy of an IC engine can be improved using the hydrogen fuel
enhancement concept in combination with lean burn conditions. These publications should be the
foundation of the information contained in Wikipedia regarding the subject. Noah Seidman (talk) 03:57, 23
April 2008 (UTC)

If I can presume your main point is that burning half the fuel doubles the economy. This is true if you get the same
result however burning half the fuel releases half the chemical energy. The capture of that chemical energy is still
governed by the Carnot cycle no matter how you dress it up. Your suggestions of using leaner fuel is comparable to
replacing a six cylinder engine with a four cylinder. Economy improves but performance decreases. In addition if
you concern is truly economy and not efficiency than many of your edits need significant revision.

Nothing you added here counters the fundamental points I made above. --OMCV (talk) 04:25, 23 April 2008 (UTC)

My intent is not to counter, it is to learn. Noah Seidman (talk) 04:42, 23 April 2008 (UTC)

The relevant description of the physical phenomenon was removed from the fraud section and substituted with a
redirect to a product review Hydrogen fuel enhancement which is a prime example of the relevant fraud. The
coverage of John Kanzius work may need rewording but the remainder of the information will be reverted to a form
that is relevant and meaningful for a page titled electrolysis of water. --OMCV (talk) 01:14, 25 April 2008 (UTC)

Nicely reworded. My main intent on wikipedia is to establish a clear distinction between what can work and
the gross perpetuation of fraud on the internet. I feel that we are effectively working toward this. Noah
Seidman (talk) 02:32, 25 April 2008 (UTC)

Nseidm1 please use fewer edits when working on pages. Figure out what you are going to write and submit a single
edit. This applies to all the pages you work on. In addition above you stated that you are learning this material and
as a result you should be very careful with your editing. If you do feel compelled to make them it would be best for
you to supply a rational for your edits on the talk page. As for the hydrogen fuel enhancement it is clearly a
financially motivated advertisement with serious POV issues. Those POV issues should not migrate beyond that
page.--OMCV (talk) 07:04, 26 April 2008 (UTC)

Section removed as unsourced WP:OR. A couple of links to youtube and news hype do not serve as sources. No
doubt there are fraudulent commercial/consumer claims out there, but the content presented requires adequate
sourcing and seems rather out of place in a general article on hydrolysis of water. I've added a see also link to
Hydrogen fuel enhancement where the subject can be discussed at length. Quite simply, a long unsourced section
here won't work. Vsmith (talk) 12:50, 26 April 2008 (UTC)