Quantum capacitance - Revision history

en>Magioladitis: /* Experiments */Replace unicode entity nbsp for character [NBSP] (or space) per WP:NBSP + other fixes, replaced: → (2) using AWB (10331)

2014-07-30T07:22:25Z

Experiments: Replace unicode entity nbsp for character [NBSP] (or space) per WP:NBSP + other fixes, replaced: → (2) using AWB (10331)

← Older revision		Revision as of 09:22, 30 July 2014
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	~~{{redirect\|Dissociative reaction\|the disorder formerly known as dissociative reaction\|dissociative identity disorder}}~~

	'''Dissociative substitution''' describes a pathway by which compounds interchange [[ligand]]s. The term is typically applied to [[Coordination chemistry\|coordination]] and [[Organometallic chemistry\|organometallic]] complexes, but resembles the [[SN1 reaction\|Sn1 mechanism]] in [[organic chemistry]]. This pathway can be well described by the [[cis effect]], or the labilization of CO ligands in the cis position. The opposite pathway is [[associative substitution]], being analogous to [[SN2 reaction\|Sn2 pathway]]. Intermediate pathways exist between the pure dissociative and pure associative pathways, these are called [[interchange mechanism]]s.<ref>[[Fred Basolo\|Basolo]], F.; Pearson, R. G. "Mechanisms of Inorganic Reactions." John Wiley: New York: 1967. ISBN 0-471-05545-X</ref><ref>R. G. Wilkins "Kinetics and Mechanism of Reactions of Transition Metal Complexes," 2nd Edition, VCH, Weinheim, 1991. ISBN 1-56081-125-0</ref>

	~~Complexes that undergo dissociative substitution are often [[coordinative unsaturation\|coordinatively saturated]]~~ and ~~often have [[octahedral molecular geometry]]. The [[entropy~~ of ~~activation]] is characteristically positive~~ for ~~these reactions~~, ~~which indicates that~~ the ~~disorder~~ of the ~~reacting system increases~~ in ~~the rate determining step.~~		It involves expertise and knowledge of various tools and technologies used for creating websites. This means you can setup your mailing list and auto-responder on your wordpress site and then you can add your subscription form to any other blog, splash page, capture page or any other site you like. Should you go with simple HTML or use a platform like Wordpress. Keep reading for some great Word - Press ideas you can start using today. You can easily customize the titles of the posts in Word - Press blog in a way that only title comes in the new post link and not the date or category of posts. <br><br>Most Word - Press web developers can provide quality CMS website solutions and they price their services at reasonable rates. But as expected the level of support you get with them can be hit or miss based on the developer's free time and desire. This may possibly also permit it currently being seriously straightforward to modify the hues within your Ad - Sense code so the ads blend nicely with the many term broad internet word wide web web page in case you can come to your conclusion to run the adverts. Apart from these, you are also required to give some backlinks on other sites as well. But in case you want some theme or plugin in sync with your business needs, it is advisable that you must seek some professional help. <br><br>This gives a clearer picture that online shoppers are familiar with the WP ecommerce system. Word - Press has different exciting features including a plug-in architecture with a templating system. For a much deeper understanding of simple wordpress themes", check out Upon browsing such, you'll be able to know valuable facts. Provide the best and updated information to the web searchers and make use of these wonderful free themes and create beautiful websites. " Thus working with a Word - Press powered web application, making any changes in the website design or website content is really easy and self explanatory. <br><br>The next thing I did after installing Wordpress was to find myself a free good-looking Wordpress-theme offering the functionality I was after. If you're ready to find more on [http://dinky.in/?WordpressBackupPlugin772230 wordpress backup] visit our web page. And, make no mistake,India's Fertility Clinics and IVF specialists are amongst the best in the world,and have been for some time. Normally, the Word - Press developers make a thorough research on your website goals and then ingrain the most suitable graphical design elements to your website. If you just want to share some picture and want to use it as a dairy, that you want to share with your friends and family members, then blogger would be an excellent choice. Word - Press offers constant updated services and products, that too, absolutely free of cost. <br><br>Millions of individuals and organizations are now successfully using this tool throughout the world. I don't want that for my visitors and I'm quite sure they don't either. Useful Plugins Uber - Menu Top Megamenu Now it is the time of sticky Top navbar. You should stay away from plugins that are full of flaws and bugs. 95, and they also supply studio press discount code for their clients, coming from 10% off to 25% off upon all theme deals.

	~~==Kinetics==~~
	~~Dissociative pathways are characterized by~~ a ~~[[rate determining step]]~~ that ~~involves release of a ligand from~~ the ~~coordination sphere of~~ the ~~metal undergoing substitution. The concentration of the substituting [[nucleophile]] has no influence on this rate, and an intermediate~~ of ~~reduced coordination number can be detected~~. ~~The reaction can be described with k<sub>1~~<~~/sub~~>~~, k~~<~~sub~~>-~~1</sub>~~ and ~~k<sub>2</sub>, which are~~ the ~~[[rate constant]]s~~ of ~~their corresponding intermediate reaction steps:~~

	~~[[File:General reaction~~ with ~~dissociative mechanism~~.~~png\|center\|400px\|]]~~

	~~Normally~~ the ~~rate determining step is~~ the ~~dissociation of L from~~ the ~~complex, and [L'] does not affect~~ the ~~rate of reaction~~, ~~leading~~ to ~~the simple rate equation:~~

	~~:<math> Rate = {k_1 [L_nM-L]}</math>~~

	~~However,~~ in some ~~cases~~, ~~the back reaction (k~~<~~sub~~>-1<~~/sub~~>~~) becomes important, and [L'] can exert an effect on~~ the ~~overall rate of reaction~~. ~~The backward reaction k<sub>~~-~~1</sub> therefore competes~~ with the ~~second forward reaction (k<sub>2</sub>), thus~~ the ~~fraction~~ of ~~intermediate (denoted as~~ "~~Int") that can react~~ with ~~L' to form~~ the ~~product~~ is ~~given by the expression~~ <~~math~~> ~~\frac{k_2[L'][Int]}{k_-1[L][Int]+k_2[L'][Int]}~~<~~/math~~>~~, which leads us~~ to ~~the overall rate equation:~~

	~~:<math> Rate_{overall} = (\frac{k_2[L'][Int]}{k_{~~-~~1}[L][Int]+k_2[L'][Int]})({k_1 [L_nM~~-~~L]}) = \frac{k_1k_2[L~~'][~~L_nM-L]}{k_{-1}[L]+k_2[L']}<~~/~~math>~~

	~~When [L] is small and negligible, the above complex equation reduces to the simple rate equation that depends on k<sub>1<~~/~~sub> and [L<sub>n<~~/~~sub>M-L~~] ~~only~~.

	~~==Dissociative interchange pathway==~~
	~~Interchange pathways apply to substitution reactions where intermediates~~ are ~~not observed, which is more common than pure dissociative pathways. If~~ the ~~reaction rate is insensitive to the nature of the attacking nucleophile,~~ the ~~process is called dissociative interchange~~, ~~abbreviated ''I''<sub>d</sub>. An illustrative process comes from the "anation" (reaction with an anion) of cobalt(III) complexes:<ref>G. L. Miessler~~ and D. ~~A. Tarr “Inorganic Chemistry” 3rd Ed~~, ~~Pearson/Prentice Hall. ISBN 0~~-~~13-035471-6~~.~~</ref>~~
	~~::[Co(NH<sub>3</sub>)<sub>5</sub>(H<sub>2</sub>O)]<sup>3+</sup> + [[Thiocyanate\|SCN<sup>-</sup>]] {{eqm}} {[Co(NH<sub>3</sub>)<sub>5</sub>(H<sub>2</sub>O)], NCS}<sup>2+</sup>~~
	~~::{[Co(NH<sub>3</sub>)<sub>5</sub>(H<sub>2</sub>O)], NCS}<sup>2+</sup> {{eqm}} [Co(NH<sub>3</sub>)<sub>5</sub>NCS]<sup>2+</sup> + H<sub>2</sub>O~~

	~~==Water exchange==~~
	~~The exchange between bulk~~ and ~~coordinated water is of fundamental interest~~ as a ~~measure of the intrinsic kinetic lability of metal ions. This rate is relevant~~ to ~~toxicity~~, ~~catalysis, [[magnetic resonance imaging]], and other effects~~. ~~For octahedral mono~~- and ~~dicationic [[aquo complex]]es~~, ~~these exchange processes occur via an interchange pathway~~ that ~~has more or less dissociative character~~.<~~ref~~>~~Lothar Helm, André E. Merbach "Inorganic and Bioinorganic Solvent Exchange Mechanisms" Chemical Reviews 2005, volume 105, 1923-1959. {{DOI\|10.1021/cr030726o}}~~<~~/ref~~> ~~Rates vary by a factor~~ of ~~10<sup>18</sup>, [Ir(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup> being the slowest~~ and ~~[Na(H<sub>2</sub>O)<sub>6</sub>]<sup>+</sup> being one of~~ the ~~fastest~~ for ~~octahedral complexes~~. ~~Charge has a significant influence on these rates but non~~-~~electrostatic effects are also important.~~

	~~==Sn1CB mechanism==~~
	~~The rate for the [[hydrolysis]] of cobalt(III) ammine (NH<sub>3</sub>-containing) halide complexes are deceptive, appearing to be associative but proceeding by a pathway that~~ is ~~dissociative in character. The hydrolysis of [Co(NH<sub>3</sub>)<sub>5</sub>Cl]<sup>2+</sup> follows second order kinetics:~~ the ~~rate increases linearly with concentration~~ of ~~hydroxide as well as the starting complex~~. ~~Studies show, however,~~ that ~~in the hydroxide deprotonates one NH<sub>3</sub> ligand to give the [[conjugate base]]~~ of ~~the starting complex, i.e~~., ~~[Co(NH<sub>3</sub>)<sub>4</sub>(NH<sub>2</sub>)Cl]<sup>+</sup>. In this mono[[cation]]~~, ~~the chloride spontaneously dissociates~~ from ~~this conjugate base of the starting complex. This pathway is called the [[Sn1CB mechanism]]~~.

	~~==References==~~
	~~<references/>~~

	~~[[Category:Organometallic chemistry]]~~
	~~[[Category:Coordination chemistry]]~~
	~~[[Category:Chemical reactions]]~~
	~~[[Category:Reaction mechanisms]]~~

en>Edgar.bonet: Formatting as per Wikipedia:Manual of Style/Dates and numbers

2013-10-07T09:25:18Z

Formatting as per Wikipedia:Manual of Style/Dates and numbers

← Older revision		Revision as of 11:25, 7 October 2013
Line 1:		Line 1:
	~~Next - GEN Gallery is~~ a ~~full incorporated Image Gallery plugin for Word - Press~~ which ~~has a Flash slideshow option~~. This ~~one is one~~ of the ~~most beneficial features of Word - Press as this feature allows users~~ to ~~define~~ the ~~user roles~~. ~~Step~~-~~4 Testing: It is the foremost important~~ of ~~your Plugin development process~~. ~~Dead links~~ are ~~listed out simply because it will negatively~~ have ~~an influence on the website's search engine rating~~. It is ~~found~~ that ~~most~~ of the ~~visitors only look for~~ the ~~results~~ that ~~are displayed on~~ the ~~first page~~ of the ~~search engines~~ and ~~so if you get the service from professional service providers then they strive for the first page ranking~~ of ~~your site and improve the online visibility~~. <br><br>~~As you know today Word~~ - ~~Press has turn out to be a tremendously popular open source publishing~~ and ~~blogging display place. The higher your blog ranks on search engines~~, the ~~more likely people will find your online marketing site~~. ~~We also help to integrate various plug-ins to expand~~ the ~~functionalities~~ of the ~~web application. This is identical to doing a research as in depth above~~, ~~nevertheless you can see various statistical details like~~ the ~~number~~ of ~~downloads and when~~ the ~~template was not long ago updated. W3C compliant HTML and a good open source powered by Word~~ - ~~Press CMS site is regarded as~~ the ~~prime minister.~~ <br><br>~~ve labored so hard to publish~~ and ~~put up~~ on ~~their website~~. The ~~following piece~~ of ~~content is meant~~ to ~~make your choice easier and reassure you that~~ the ~~decision to go ahead with this conversion~~ is ~~requited with rich benefits:. After age 35~~, ~~18% of pregnancies will end in miscarriage. You can allow visitors~~ to ~~post comments~~, ~~or you can even allow your visitors~~ to ~~register~~ and ~~create their own personal blogs~~. ~~Websites using this content based strategy~~ are ~~always given top scores by Google~~. <br><br>~~Word - Press installation is very easy and hassle free~~. ~~php file in~~ the ~~Word - Press root folder and look for this line~~ (~~line 73 in our example~~):. ~~To do this~~, ~~you should link your posts to other relevant posts that you've created~~. ~~A whole lot worse~~, ~~your site will likely be useless~~ as ~~well as your merchandise won't sell if no one has~~ the ~~endurance~~ to ~~wait for the web pages to load~~. ~~Word~~ - ~~Press offers constant updated services~~ and ~~products~~, that ~~too~~, ~~absolutely free~~ of ~~cost.~~ <br><br>~~More it extends numerous opportunities where your firm is at comfort and rest assured of no risks & errors. If you loved this post~~ and ~~you would like to receive extra details regarding~~ [~~http:~~//~~ad4~~.~~fr/wordpress_backup_6086201 wordpress dropbox backup] kindly take~~ a ~~look at~~ the ~~web~~-~~page. Automated deal feed integration option~~ to ~~populate your blog with relevant deals. It's not~~ a ~~secret~~ that ~~a lion share~~ of ~~activity on~~ the ~~internet is takes place on~~ the ~~Facebook~~. ~~Page speed is an important factor~~ in ~~ranking~~, ~~especially with Google~~. ~~I have never seen a plugin with such a massive array of features~~, this ~~does everything that platinum SEO and All In One SEO~~, ~~also throws in~~ the ~~functionality found within SEO Smart Links and a number~~ of ~~other plugins it~~ is ~~essentially~~ the ~~swiss army knife of Word - Press plugins~~.		{{redirect\|Dissociative reaction\|the disorder formerly known as dissociative reaction\|dissociative identity disorder}}

			'''Dissociative substitution''' describes a pathway by which compounds interchange [[ligand]]s. The term is typically applied to [[Coordination chemistry\|coordination]] and [[Organometallic chemistry\|organometallic]] complexes, but resembles the [[SN1 reaction\|Sn1 mechanism]] in [[organic chemistry]]. This pathway can be well described by the [[cis effect]], or the labilization of CO ligands in the cis position. The opposite pathway is [[associative substitution]], being analogous to [[SN2 reaction\|Sn2 pathway]]. Intermediate pathways exist between the pure dissociative and pure associative pathways, these are called [[interchange mechanism]]s.<ref>[[Fred Basolo\|Basolo]], F.; Pearson, R. G. "Mechanisms of Inorganic Reactions." John Wiley: New York: 1967. ISBN 0-471-05545-X</ref><ref>R. G. Wilkins "Kinetics and Mechanism of Reactions of Transition Metal Complexes," 2nd Edition, VCH, Weinheim, 1991. ISBN 1-56081-125-0</ref>

			Complexes that undergo dissociative substitution are often [[coordinative unsaturation\|coordinatively saturated]] and often have [[octahedral molecular geometry]]. The [[entropy of activation]] is characteristically positive for these reactions, which indicates that the disorder of the reacting system increases in the rate determining step.

			==Kinetics==
			Dissociative pathways are characterized by a [[rate determining step]] that involves release of a ligand from the coordination sphere of the metal undergoing substitution. The concentration of the substituting [[nucleophile]] has no influence on this rate, and an intermediate of reduced coordination number can be detected. The reaction can be described with k<sub>1</sub>, k<sub>-1</sub> and k<sub>2</sub>, which are the [[rate constant]]s of their corresponding intermediate reaction steps:

			[[File:General reaction with dissociative mechanism.png\|center\|400px\|]]

			Normally the rate determining step is the dissociation of L from the complex, and [L'] does not affect the rate of reaction, leading to the simple rate equation:

			:<math> Rate = {k_1 [L_nM-L]}</math>

			However, in some cases, the back reaction (k<sub>-1</sub>) becomes important, and [L'] can exert an effect on the overall rate of reaction. The backward reaction k<sub>-1</sub> therefore competes with the second forward reaction (k<sub>2</sub>), thus the fraction of intermediate (denoted as "Int") that can react with L' to form the product is given by the expression <math> \frac{k_2[L'][Int]}{k_-1[L][Int]+k_2[L'][Int]}</math>, which leads us to the overall rate equation:

			:<math> Rate_{overall} = (\frac{k_2[L'][Int]}{k_{-1}[L][Int]+k_2[L'][Int]})({k_1 [L_nM-L]}) = \frac{k_1k_2[L'][L_nM-L]}{k_{-1}[L]+k_2[L']}</math>

			When [L] is small and negligible, the above complex equation reduces to the simple rate equation that depends on k<sub>1</sub> and [L<sub>n</sub>M-L] only.

			==Dissociative interchange pathway==
			Interchange pathways apply to substitution reactions where intermediates are not observed, which is more common than pure dissociative pathways. If the reaction rate is insensitive to the nature of the attacking nucleophile, the process is called dissociative interchange, abbreviated ''I''<sub>d</sub>. An illustrative process comes from the "anation" (reaction with an anion) of cobalt(III) complexes:<ref>G. L. Miessler and D. A. Tarr “Inorganic Chemistry” 3rd Ed, Pearson/Prentice Hall. ISBN 0-13-035471-6.</ref>
			::[Co(NH<sub>3</sub>)<sub>5</sub>(H<sub>2</sub>O)]<sup>3+</sup> + [[Thiocyanate\|SCN<sup>-</sup>]] {{eqm}} {[Co(NH<sub>3</sub>)<sub>5</sub>(H<sub>2</sub>O)], NCS}<sup>2+</sup>
			::{[Co(NH<sub>3</sub>)<sub>5</sub>(H<sub>2</sub>O)], NCS}<sup>2+</sup> {{eqm}} [Co(NH<sub>3</sub>)<sub>5</sub>NCS]<sup>2+</sup> + H<sub>2</sub>O

			==Water exchange==
			The exchange between bulk and coordinated water is of fundamental interest as a measure of the intrinsic kinetic lability of metal ions. This rate is relevant to toxicity, catalysis, [[magnetic resonance imaging]], and other effects. For octahedral mono- and dicationic [[aquo complex]]es, these exchange processes occur via an interchange pathway that has more or less dissociative character.<ref>Lothar Helm, André E. Merbach "Inorganic and Bioinorganic Solvent Exchange Mechanisms" Chemical Reviews 2005, volume 105, 1923-1959. {{DOI\|10.1021/cr030726o}}</ref> Rates vary by a factor of 10<sup>18</sup>, [Ir(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup> being the slowest and [Na(H<sub>2</sub>O)<sub>6</sub>]<sup>+</sup> being one of the fastest for octahedral complexes. Charge has a significant influence on these rates but non-electrostatic effects are also important.

			==Sn1CB mechanism==
			The rate for the [[hydrolysis]] of cobalt(III) ammine (NH<sub>3</sub>-containing) halide complexes are deceptive, appearing to be associative but proceeding by a pathway that is dissociative in character. The hydrolysis of [Co(NH<sub>3</sub>)<sub>5</sub>Cl]<sup>2+</sup> follows second order kinetics: the rate increases linearly with concentration of hydroxide as well as the starting complex. Studies show, however, that in the hydroxide deprotonates one NH<sub>3</sub> ligand to give the [[conjugate base]] of the starting complex, i.e., [Co(NH<sub>3</sub>)<sub>4</sub>(NH<sub>2</sub>)Cl]<sup>+</sup>. In this mono[[cation]], the chloride spontaneously dissociates from this conjugate base of the starting complex. This pathway is called the [[Sn1CB mechanism]].

			==References==
			<references/>

			[[Category:Organometallic chemistry]]
			[[Category:Coordination chemistry]]
			[[Category:Chemical reactions]]
			[[Category:Reaction mechanisms]]

en>EleferenBot: r2.7.3) (Robot: Adding ru:Квантовая ёмкость

2012-07-07T20:29:24Z

r2.7.3) (Robot: Adding ru:Квантовая ёмкость

New page

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