C6320 Chemická kinetika:

                                     Historie chemické kinetiky

                                     Historie chemické kinetiky
        Ref: "The World of Physical Chemistry," by K. J. Laidler, Oxford Univ. Press, 1993)

l      •1850: Wilhelmy (Germany) studied the rate of inversion of sucrose (hydrolysis into
D-(+)-glucose and D-(-)-fructose in the presence of an acid) and found it to be proportional to the
concentrations of both the sugar and the acid. (viz experimentální úloha v praktiku fyzikální
chemie)



l      •1864: Guldberg and Waage (Norway) formulated their "law of mass action," according to which
the reaction "forces" are proportional to the product of the concentrations of the reactants: K=[R]r
[S]s/([A]a [B]b) where a, b, r and s are the stoichiometric coefficients in the chemica equation
A+B=R+S. So the rate of the forward reaction is proportional to [A]a [B]b and that of the reverse
reaction is proportional to {R]r [S]s.







l      •1865: Harcourt and Esson (UK) analyzed the reactions between H2O2 and HI and between KMnO4
and (COOH)2. They wrote the corresponding differential equations, integrated them and determined the
concentration vs. time relationships. They also proposed an equation for the temperature dependence
of the reaction rate, k = A TC.



l      •1884: van't Hoff (The Netherlands) published his "Studies of Chemical Dynamics" (Études de
dynamique chimique), in which he generalized and further developed the work of Wilhelmy,







l      Harcourt and Esson. In particular, he introduced the differential method of analysis. He also
analyzed the temperature dependence of the equilibrium constant (now called the "van't Hoff
equation") and of forward and reverse reaction rates.



l      •1887: Ostwald (Germany; Latvia) introduces the terms "reaction order" and "half-life" in his
"Lehrbuch der allgemeinen Chemie.„



l      •1889: Arrhenius (Sweden) further analyzed the temperature dependence of reaction rate, k = A
exp(-B/T), and gave it an "energy barrier" interpretation; this is now called the "Arrhenius
equation."







l     Mentenová (Maude Lenora Menten)

  Michaelis-Menten equation (1912), enzymová kinetika (profesorkou v 60-ti letech)













                                           Termodynamika

                                    Shrnutí poznatků z historie

l    Řada pojmů a představ se kterými se setkáváme v chemické kinetice je již dlouho známých.

l    Získání některých kinetických informací je velmi náročné (mechanismy reakcí, reakční
koordináta,…)

l    Moderní kinetika je interdisciplinární (biochemická kinetika, molekulová dynamika , kvantová
chemie)

                                             Literatura