{"id":13645,"date":"2015-03-17T21:40:10","date_gmt":"2015-03-17T21:40:10","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=13645"},"modified":"2015-03-18T11:14:08","modified_gmt":"2015-03-18T11:14:08","slug":"a-5-high-straight-flush-of-water-ionised-acids","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645","title":{"rendered":"A 5-high straight flush of water-ionised acids?"},"content":{"rendered":"
\n

I do not play poker,\u2021<\/sup> and so I had to look up a 5-4-3-2<\/strong><\/span>-1(A), which Wikipedia informs me is a 5-high straight flush<\/em>, also apparently known as a steel wheel<\/em>. In previous posts<\/a> \u00a0I have suggested acids which can be ionised by (probably)\u00a05, 4, 3 or \u00a01 discrete water molecules in the gas phase; now to try to track down\u00a0\u00a0a candidate for ionisation by the required\u00a0two<\/strong> water molecules to form\u00a0that straight flush.<\/p>\n

As the counter-anion to quaternary ammonium cations, bis<\/em>(trifluoromethylsulfonyl)imide is a component of some ionic liquids. Its conjugate acid is thought[1]<\/a><\/span>,[2]<\/a><\/span> to protonate on the nitrogen.<\/p>\n

\"Click

Click for 3D<\/p><\/div>\n

My first obvious attempt was to place two waters near that N-H to see if it would ionise from that position.[3]<\/a><\/span> The proton remains attached to the nitrogen(-:
\n\"ZURWEO-N\"<\/p>\n

Next, how about re-locating the waters so that they are closer to the sulfonyl oxygens? This time we do have the characteristic hydronium cation forming.[4]<\/a><\/span> However, the free energy of this isomer is +6.7 kcal\/mol\u00a0higher relative to the NH form. So not a\u00a05-high straight flush<\/em> in a strict sense, but it perhaps does give a hint of how one might design the missing card.<\/p>\n

\"Click

Click for 3D<\/p><\/div>\n

\n

\u2021<\/sup>Confession time. I did spend many a Wednesday afternoon as an undergraduate playing the card game bridge.<\/p>\n

\n

References<\/h2>\n
  1. \"Structures of bis(fluorosulfonyl)imide HN(SO<sub>2<\/sub>F)<sub>2<\/sub>, bis(trifluoromethylsulfonyl)imide HN(SO<sub>2<\/sub>CF<sub>3<\/sub>)<sub>2<\/sub>, and their potassium salts at 150 K\", Zeitschrift f\u00fcr Kristallographie - Crystalline Materials<\/i>, vol. 213, pp. 217-222, 1998. https:\/\/doi.org\/10.1524\/zkri.1998.213.4.217<\/a>\n\n<\/li>\n
  2. Zak, Z.., and Ruzicka, A.., \"CCDC 119129: Experimental Crystal Structure Determination\", 1999. https:\/\/doi.org\/10.5517\/cc3zyww<\/a>\n\n<\/li>\n
  3. H.S. Rzepa, \"C 2 H 5 F 6 N 1 O 6 S 2\", 2015. https:\/\/doi.org\/10.14469\/ch\/191136<\/a>\n\n<\/li>\n
  4. H.S. Rzepa, \"C 2 H 5 F 6 N 1 O 6 S 2\", 2015. https:\/\/doi.org\/10.14469\/ch\/191137<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    I do not play poker,\u2021 and so I had to look up a 5-4-3-2-1(A), which Wikipedia informs me is a 5-high straight flush, also apparently known as a steel wheel. In previous posts \u00a0I have suggested acids which can be ionised by (probably)\u00a05, 4, 3 or \u00a01 discrete water molecules in the gas phase; now […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2},"jetpack_post_was_ever_published":false},"categories":[4],"tags":[40,145,1324],"ppma_author":[2661],"class_list":["post-13645","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-free-energy","tag-gas-phase","tag-steel-wheel"],"yoast_head":"\nA 5-high straight flush of water-ionised acids? - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"A 5-high straight flush of water-ionised acids? - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"I do not play poker,\u2021 and so I had to look up a 5-4-3-2-1(A), which Wikipedia informs me is a 5-high straight flush, also apparently known as a steel wheel. In previous posts \u00a0I have suggested acids which can be ionised by (probably)\u00a05, 4, 3 or \u00a01 discrete water molecules in the gas phase; now […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2015-03-17T21:40:10+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2015-03-18T11:14:08+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2015\/03\/ZURWEO.jpg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"1 minute\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"A 5-high straight flush of water-ionised acids? - Henry Rzepa's Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645","og_locale":"en_GB","og_type":"article","og_title":"A 5-high straight flush of water-ionised acids? - Henry Rzepa's Blog","og_description":"I do not play poker,\u2021 and so I had to look up a 5-4-3-2-1(A), which Wikipedia informs me is a 5-high straight flush, also apparently known as a steel wheel. In previous posts \u00a0I have suggested acids which can be ionised by (probably)\u00a05, 4, 3 or \u00a01 discrete water molecules in the gas phase; now […]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645","og_site_name":"Henry Rzepa's Blog","article_published_time":"2015-03-17T21:40:10+00:00","article_modified_time":"2015-03-18T11:14:08+00:00","og_image":[{"url":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2015\/03\/ZURWEO.jpg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"1 minute"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"A 5-high straight flush of water-ionised acids?","datePublished":"2015-03-17T21:40:10+00:00","dateModified":"2015-03-18T11:14:08+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645"},"wordCount":255,"commentCount":0,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2015\/03\/ZURWEO.jpg","keywords":["free energy","gas phase","steel wheel"],"articleSection":["Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13645","name":"A 5-high straight flush of water-ionised acids? 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I justify it (probably only to myself) as an exercise in how a scientist might approach a problem, and how it linearly develops with time, not necessarily\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":13618,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13618","url_meta":{"origin":13645,"position":1},"title":"Ionizing ultra-strong acids with water molecules.","author":"Henry Rzepa","date":"March 15, 2015","format":false,"excerpt":"My previous posts have covered the ionization by a small number of discrete water molecules of the series of halogen acids, ranging from HI (the strongest,\u00a0pKa -10) via HF (weaker, pKa 3.1) to the pseudo-halogen HCN (the weakest, pKa 9.2). Here I try out some even stronger acids to see\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":15395,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=15395","url_meta":{"origin":13645,"position":2},"title":"I\u2019ve started so I\u2019ll finish. Kinetic isotope effect models for a general acid as a catalyst in the protiodecarboxylation of indoles.","author":"Henry Rzepa","date":"January 10, 2016","format":false,"excerpt":"Earlier I explored models for the heteroaromatic electrophilic protiodecarboxylation of an 3-substituted indole, focusing on the role of water as the proton transfer and delivery agent. Next, came\u00a0models for both water and the general base catalysed\u00a0ionization of indolinones. Here I\u00a0explore\u00a0general acid\u00a0catalysis by evaluating the properties of two possible models for\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":13506,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13506","url_meta":{"origin":13645,"position":3},"title":"How many water molecules does it take to ionise HCN\/HNC? An NCI exploration.","author":"Henry Rzepa","date":"March 2, 2015","format":false,"excerpt":"HCN is a weak acid (pKa +9.2, weaker than e.g. HF), although it does have an isomer, isocyanic\u00a0acid or HNC (pka < +9.2 ?) which is simultaneously stronger and less stable. I conclude my halide acid series\u00a0by investigating how many water molecules (in gas phase clusters) are required for ionisation\u2026","rel":"","context":"In "General"","block_context":{"text":"General","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":15924,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=15924","url_meta":{"origin":13645,"position":4},"title":"How many water molecules does it take to form ammonium hydroxide from ammonia and water?","author":"Henry Rzepa","date":"March 20, 2016","format":false,"excerpt":"This is a corollary to the previous post\u2021 exploring how many molecules are needed to ionise HCl. Here I am asking how many water molecules are required to form the ionic ammonium hydroxide from ammonia and water. As Wikipedia will inform you, \"it is actually impossible to isolate samples of\u2026","rel":"","context":"In "General"","block_context":{"text":"General","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":13488,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13488","url_meta":{"origin":13645,"position":5},"title":"How many water molecules does it take to ionise HI?","author":"Henry Rzepa","date":"February 28, 2015","format":false,"excerpt":"Why is this post orphaned from the previous? In order to have the opportunity of noting that treating iodine computationally can be a little different from the procedures used for F, Cl and Br. As the nuclear charge increases proceeding down the periodic table, the inner electron shells start becoming\u2026","rel":"","context":"In "General"","block_context":{"text":"General","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/13645","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=13645"}],"version-history":[{"count":22,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/13645\/revisions"}],"predecessor-version":[{"id":13675,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/13645\/revisions\/13675"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=13645"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=13645"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=13645"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=13645"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}