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Rate-determining step
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==Reaction coordinate diagram== In a multistep reaction, the rate-determining step does not necessarily correspond to the highest [[Gibbs energy]] on the [[reaction coordinate]] diagram.<ref name=Laidler>[[Keith J. Laidler]]. ''Chemical Kinetics'' (3rd ed., Harper and Row 1987) p. 283β285. {{ISBN|0-06-043862-2}}.</ref><ref name=Atkins/> If there is a [[reaction intermediate]] whose energy is lower than the initial reactants, then the activation energy needed to pass through any subsequent [[transition state]] depends on the Gibbs energy of that state relative to the lower-energy intermediate. The rate-determining step is then the step with the largest Gibbs energy difference relative either to the starting material or to any previous intermediate on the diagram.<ref name=Laidler/><ref>{{Cite journal | doi = 10.1021/ed058p32 | last1 = Murdoch | first1 = Joseph R. | title = What is the rate-limiting step of a multistep reaction? |journal = Journal of Chemical Education | volume = 58 | issue = 1| pages = 32β36 | year = 1981 | bibcode = 1981JChEd..58...32M }}</ref> Also, for reaction steps that are not first-order, concentration terms must be considered in choosing the rate-determining step.<ref name=Laidler/><ref name=Atkins/>
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