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<title>Castner–Kellner process</title>

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<span id="openzim-page-title" class="mw-page-title-main"><span class="mw-page-title-main">Castner–Kellner process</span></span>

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</style><div role="note" class="hatnote navigation-not-searchable">Not to be confused with <a href="Castner_process" title="Castner process">Castner process</a>.</div>

<p>The <b>Castner–Kellner process</b> is a method of <a href="Electrolysis" title="Electrolysis">electrolysis</a> on an <a href="Aqueous" class="mw-redirect" title="Aqueous">aqueous</a> <a href="Alkali" title="Alkali">alkali</a> <a href="Chloride" title="Chloride">chloride</a> solution (usually <a href="Sodium_chloride" title="Sodium chloride">sodium chloride</a> solution) to produce the corresponding alkali <a href="Hydroxide" title="Hydroxide">hydroxide</a>,<sup id="cite_ref-1" class="reference"><a href="#cite_note-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup> invented by American <a href="Hamilton_Castner" title="Hamilton Castner">Hamilton Castner</a> and Austrian <a href="Carl_Kellner_(mystic)" title="Carl Kellner (mystic)">Carl Kellner</a> in the 1890s.<sup id="cite_ref-2" class="reference"><a href="#cite_note-2"><span class="cite-bracket">[</span>2<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-3" class="reference"><a href="#cite_note-3"><span class="cite-bracket">[</span>3<span class="cite-bracket">]</span></a></sup>

It is a type of <a href="Chloralkali_process" title="Chloralkali process">chloralkali process</a>, but in this role it is gradually being replaced by <a href="Membrane" title="Membrane">membrane</a> electrolysis which has lower energy cost and fewer environmental concerns.<sup id="cite_ref-4" class="reference"><a href="#cite_note-4"><span class="cite-bracket">[</span>4<span class="cite-bracket">]</span></a></sup>

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<div class="mw-heading mw-heading2"><h2 id="History">History</h2></div>

<p>The first patent for electrolyzing <a href="Brine" title="Brine">brine</a> was granted in England in 1851 to Charles Watt. His process was not an economically feasible method for producing sodium hydroxide though because it could not prevent the chlorine that formed in the brine solution from reacting with its other constituents. American chemist and engineer, <a href="Hamilton_Castner" title="Hamilton Castner">Hamilton Castner</a>, solved the mixing problem with the invention of the mercury cell and was granted a U.S. patent in 1894.<sup id="cite_ref-5" class="reference"><a href="#cite_note-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> Austrian chemist, <a href="Carl_Kellner_(mystic)" title="Carl Kellner (mystic)">Carl Kellner</a> arrived at a similar solution at about the same time. In order to avoid a legal battle they became partners in 1895, founding the Castner-Kellner Alkali Company, which built plants employing the process throughout Europe. The mercury cell process continues in use to this day.<sup id="cite_ref-6" class="reference"><a href="#cite_note-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> Current-day mercury cell plant operations are criticized for environmental release of mercury<sup id="cite_ref-7" class="reference"><a href="#cite_note-7"><span class="cite-bracket">[</span>7<span class="cite-bracket">]</span></a></sup> leading in some cases to severe <a href="Mercury_poisoning" title="Mercury poisoning">mercury poisoning</a> (<a href="Minamata_disease" title="Minamata disease">as occurred in Japan</a>). Due to these concerns, mercury cell plants are being phased out, and a sustained effort is being made to reduce mercury emissions from existing plants.<sup id="cite_ref-8" class="reference"><a href="#cite_note-8"><span class="cite-bracket">[</span>8<span class="cite-bracket">]</span></a></sup>

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<div class="mw-heading mw-heading2"><h2 id="Process_details">Process details</h2></div>

<p>The apparatus shown is divided into two types of cells separated by <a href="Slate" title="Slate">slate</a> walls. The first type, shown on the right and left of the diagram, uses an electrolyte of sodium chloride solution, a <a href="Graphite" title="Graphite">graphite</a> <a href="Anode" title="Anode">anode</a> (A), and a <a href="Mercury_(element)" title="Mercury (element)">mercury</a> <a href="Cathode" title="Cathode">cathode</a> (M). The other type of cell, shown in the center of the diagram, uses an electrolyte of <a href="Sodium_hydroxide" title="Sodium hydroxide">sodium hydroxide</a> solution, a mercury anode (M), and an iron cathode (D). The mercury electrode is common between the two cells. This is achieved by having the walls separating the cells dip below the level of the electrolytes but still allow the mercury to flow beneath them.<sup id="cite_ref-9" class="reference"><a href="#cite_note-9"><span class="cite-bracket">[</span>9<span class="cite-bracket">]</span></a></sup>

</p><p>The reaction at anode (A) is:

</p>

<p>The <a href="Chlorine" title="Chlorine">chlorine</a> gas that results vents at the top of the outside cells where it is collected as a byproduct of the process. The reaction at the mercury cathode in the outer cells is

</p>

<dl><dd>Na<sup>+</sup> + e<sup>−</sup> → Na (amalgam)</dd></dl>

<p>The <a href="Sodium" title="Sodium">sodium</a> metal formed by this reaction dissolves in the mercury to form an <a href="Amalgam_(chemistry)" title="Amalgam (chemistry)">amalgam</a>. The mercury conducts the current from the outside cells to the center cell. In addition, a rocking mechanism (B shown by fulcrum on the left and rotating eccentric on the right) agitates the mercury to transport the dissolved sodium metal from the outside cells to the center cell.

</p><p>The anode reaction in the center cell takes place at the interface between the mercury and the sodium hydroxide solution.

</p>

<dl><dd>2Na (amalgam) → 2Na<sup>+</sup> + 2e<sup>−</sup></dd></dl>

<p>Finally at the iron cathode (D) of the center cell the reaction is

</p>

<p>The net effect is that the concentration of sodium chloride in the outside cells decreases and the concentration of sodium hydroxide in the center cell increases. As the process continues, some sodium hydroxide solution is withdrawn from center cell as output product and is replaced with water. Sodium chloride is added to the outside cells to replace what has been electrolyzed.

</p>

<ul><li><a href="Electrochemical_engineering" title="Electrochemical engineering">Electrochemical engineering</a></li>

<li><a href="Castner_Medal" title="Castner Medal">Castner Medal</a></li>

<li><a href="Chloralkali_process" title="Chloralkali process">Chloralkali process</a></li></ul>

<div class="mw-heading mw-heading2"><h2 id="References">References</h2></div>

<li id="cite_note-1"><span class="mw-cite-backlink"><b><a href="#cite_ref-1">^</a></b></span> <span class="reference-text">Pauling, Linus; <i>General Chemistry</i> 1970 ed. pp. 539–541 Dover publishing</span>

</li>

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</style><cite id="CITEREFTrinder,_Barrie_StuartStratton,_Michael2000" class="citation book cs1">Trinder, Barrie Stuart; Stratton, Michael (2000). <i>Twentieth century industrial archaeology</i>. London: E&FN Spon. pp. <span class="nowrap">80–</span>81. <a href="ISBN_(identifier)" class="mw-redirect" title="ISBN (identifier)">ISBN</a> <bdi>978-0-419-24680-0</bdi>.</cite></span>

</li>

<li id="cite_note-3"><span class="mw-cite-backlink"><b><a href="#cite_ref-3">^</a></b></span> <span class="reference-text"><cite class="citation web cs1"><a rel="nofollow" class="external text" href="https://web.archive.org/web/20070514034157/http://www.saltsense.co.uk/hist-chem12.htm">"The Electrolysis of Brine"</a>. Salt and the Chemical Revolution. Salt Manufacturers' Association. Archived from <a rel="nofollow" class="external text" href="http://www.saltsense.co.uk/hist-chem12.htm">the original</a> on May 14, 2007.</cite></span>

</li>

<li id="cite_note-4"><span class="mw-cite-backlink"><b><a href="#cite_ref-4">^</a></b></span> <span class="reference-text"><cite class="citation web cs1"><a rel="nofollow" class="external text" href="https://www.eurochlor.org/topics/mercury/">"Mercury"</a>.</cite></span>

</li>

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</style><span class="citation patent" id="CITEREFCastner1984"><a rel="nofollow" class="external text" href="https://worldwide.espacenet.com/textdoc?DB=EPODOC&IDX=US528322">US 528322</a>, Castner, H.Y., "Process of and apparatus for electrolytic decomposition of alkaline salts", issued 30 Oct 1984</span><span class="Z3988" title="ctx_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Apatent&rft.number=528322&rft.cc=US&rft.title=Process+of+and+apparatus+for+electrolytic+decomposition+of+alkaline+salts&rft.inventor=Castner&rft.date=30 Oct 1984"><span style="display: none;"> </span></span></span>

</li>

<li id="cite_note-6"><span class="mw-cite-backlink"><b><a href="#cite_ref-6">^</a></b></span> <span class="reference-text"><cite id="CITEREFKiefer2002" class="citation journal cs1">Kiefer, David M. (April 2002). <a rel="nofollow" class="external text" href="http://pubs.acs.org/subscribe/journals/tcaw/11/i04/html/04chemistry.html">"When the Industry Charged Ahead"</a>. <i>Today's Chemist at Work</i>. Chemistry Chronicles. <b>11</b> (3). American Chemical Society: 9.</cite></span>

</li>

<li id="cite_note-7"><span class="mw-cite-backlink"><b><a href="#cite_ref-7">^</a></b></span> <span class="reference-text"><cite class="citation web cs1"><a rel="nofollow" class="external text" href="https://web.archive.org/web/20110720142805/http://www.oceana.org/index.php?id=1707">"Chlorine Plants: Major, Overlooked Source of Mercury Pollution"</a>. Oceana. Archived from <a rel="nofollow" class="external text" href="http://www.oceana.org/index.php?id=1707">the original</a> on 20 Jul 2011.</cite></span>

</li>

<li id="cite_note-8"><span class="mw-cite-backlink"><b><a href="#cite_ref-8">^</a></b></span> <span class="reference-text"><cite class="citation web cs1"><a rel="nofollow" class="external text" href="https://web.archive.org/web/20110525111624/http://www.chem.unep.ch/Mercury/partnerships/progress-reports/WCC%20Submission.pdf">"World Chlorine Council Submission on Global Mercury Partnership for the Reduction of Mercury in the Chlor-alkali Sector"</a> <span class="cs1-format">(PDF)</span>. Archived from <a rel="nofollow" class="external text" href="http://www.chem.unep.ch/Mercury/partnerships/progress-reports/WCC%20Submission.pdf">the original</a> <span class="cs1-format">(PDF)</span> on 2011-05-25.</cite></span>

</li>

<li id="cite_note-9"><span class="mw-cite-backlink"><b><a href="#cite_ref-9">^</a></b></span> <span class="reference-text">Newell, Lyman C.; <i>Descriptive Chemistry</i> p. 291; D. C. Heath and company, 1903</span>

</li>

</ol></div>

<div class="mw-heading mw-heading2"><h2 id="External_links">External links</h2></div>

<ul><li><a rel="nofollow" class="external text" href="https://www.eurochlor.org/about-chlor-alkali/how-are-chlorine-and-caustic-soda-made/mercury-cell-process/">Animation showing the mercury cell process</a></li>

<li><a rel="nofollow" class="external text" href="https://old.iupac.org/didac/Didac%20Eng/Didac03/Content/R18%20-%20R19.htm">Producing chlorine in the chlorine-alkali industry</a> - <a href="International_Union_of_Pure_and_Applied_Chemistry" title="International Union of Pure and Applied Chemistry">IUPAC</a></li>

<li><a rel="nofollow" class="external text" href="https://www.washingtonpost.com/wp-dyn/content/article/2009/01/26/AR2009012601831.html">now a health issue </a></li></ul>

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</style><div id="Articles_related_to_electrolysis_/_Standard_electrode_potential135" style="font-size:114%;margin:0 4em">Articles related to <a href="Electrolysis" title="Electrolysis">electrolysis</a> / <a href="Standard_electrode_potential" title="Standard electrode potential">Standard electrode potential</a></div></th></tr><tr><th scope="row" class="navbox-group" style="width:1%">Electrolytic processes</th><td class="navbox-list-with-group navbox-list navbox-odd hlist" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Betts_electrolytic_process" title="Betts electrolytic process">Betts electrolytic process</a></li>

<li><a href="Castner_process" title="Castner process">Castner process</a></li>

<li><a href="Chloralkali_process" title="Chloralkali process">Chloralkali process</a></li>

<li><a href="Downs_cell" title="Downs cell">Downs cell</a></li>

<li><a href="Electrochemical_reduction_of_carbon_dioxide" title="Electrochemical reduction of carbon dioxide">Electrolysis of carbon dioxide</a></li>

<li><a href="Electrolysis_of_water" title="Electrolysis of water">Electrolysis of water</a></li>

<li><a href="Electrowinning" title="Electrowinning">Electrowinning</a></li>

<li><a href="Hall%E2%80%93H%C3%A9roult_process" title="Hall–Héroult process">Hall–Héroult process</a></li>

<li><a href="Hofmann_voltameter" title="Hofmann voltameter">Hofmann voltameter</a></li>

<li><a href="Kolbe_electrolysis" title="Kolbe electrolysis">Kolbe electrolysis</a></li>

<li><a href="Hoopes_process" title="Hoopes process">Hoopes process</a></li>

<li>Dow process

<ul><li><a href="Dow_process_(bromine)" title="Dow process (bromine)">Bromine</a></li>

<li><a href="Dow_process_(magnesium)" class="mw-redirect" title="Dow process (magnesium)">Magnesium</a></li></ul></li>

<li><a href="Electrochemical_fluorination" title="Electrochemical fluorination">Electrochemical fluorination</a></li>

<li><a href="Wohlwill_process" title="Wohlwill process">Wohlwill process</a></li></ul>

</div></td></tr><tr><th scope="row" class="navbox-group" style="width:1%">Materials produced by electrolysis</th><td class="navbox-list-with-group navbox-list navbox-even hlist" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Hall%E2%80%93H%C3%A9roult_process" title="Hall–Héroult process">Aluminium</a> <a href="Bayer_process" title="Bayer process">(extraction)</a></li>

<li><a href="Calcium" title="Calcium">Calcium metal</a></li>

<li><a href="Chlorine" title="Chlorine">Chlorine</a></li>

<li><a href="Copper_extraction#Electrorefining" title="Copper extraction">Copper</a></li>

<li><a href="Electrolysed_water" title="Electrolysed water">Electrolysed water</a></li>

<li><a href="Fluorine" title="Fluorine">Fluorine</a></li>

<li><a href="Hydrogen_evolution_reaction" title="Hydrogen evolution reaction">Hydrogen evolution reaction</a></li>

<li><a href="Lithium" title="Lithium">Lithium metal</a></li>

<li><a href="Magnesium" title="Magnesium">Magnesium metal</a></li>

<li><a href="Potassium" title="Potassium">Potassium metal</a></li>

<li><a href="Sodium" title="Sodium">Sodium metal</a></li>

<li><a href="Sodium_hydroxide" title="Sodium hydroxide">Sodium hydroxide</a></li>

</div></td></tr><tr><th scope="row" class="navbox-group" style="width:1%">See also</th><td class="navbox-list-with-group navbox-list navbox-odd hlist" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Electrochemistry" title="Electrochemistry">Electrochemistry</a></li>

<li><a href="Gas_cracker" title="Gas cracker">Gas cracker</a></li>

<li><a href="Standard_electrode_potential_(data_page)" title="Standard electrode potential (data page)">Standard electrode potential (data page)</a></li>

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