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where k is the rate constant. A was referred to as the frequency factor (now called the pre-exponential coefficient), and E a is regarded as the activation energy. By the early 20th century many had accepted the Arrhenius equation, but the physical interpretation of A and E a remained vague.
A primary kinetic isotope effect (PKIE) may be found when a bond to the isotopically labeled atom is being formed or broken. [3] [4]: 427 Depending on the way a KIE is probed (parallel measurement of rates vs. intermolecular competition vs. intramolecular competition), the observation of a PKIE is indicative of breaking/forming a bond to the isotope at the rate-limiting step, or subsequent ...
where log(k s /k CH 3) B is the ratio of the rate of the base catalyzed reaction compared to the reference reaction, log(k s /k CH 3) A is ratio of a rate of the acid catalyzed reaction compared to the reference reaction, and ρ* is a reaction constant that describes the sensitivity of the reaction series. For the definition reaction series, ρ ...
The general form of the Eyring–Polanyi equation somewhat resembles the Arrhenius equation: = ‡ where is the rate constant, ‡ is the Gibbs energy of activation, is the transmission coefficient, is the Boltzmann constant, is the temperature, and is the Planck constant.
These phenomena are due to exothermic or endothermic reactions occurring faster than heat transfer, causing the reacting molecules to have non-thermal energy distributions (non-Boltzmann distribution). Increasing the pressure increases the heat transfer rate between the reacting molecules and the rest of the system, reducing this effect.
Hess's law states that the sum of the energy changes of all thermochemical equations included in an overall reaction is equal to the overall energy change. Since Δ H {\displaystyle \Delta H} is a state function and is not dependent on how reactants become products as a result, steps (in the form of several thermochemical equations) can be used ...
Free energy relationships establish the extent at which bond formation and breakage happen in the transition state of a reaction, and in combination with kinetic isotope experiments a reaction mechanism can be determined. Free energy relationships are often used to calculate equilibrium constants since they are experimentally difficult to ...
Entropy of activation determines the preexponential factor A of the Arrhenius equation for temperature dependence of reaction rates. The relationship depends on the molecularity of the reaction: for reactions in solution and unimolecular gas reactions A = (ek B T/h) exp(ΔS ‡ /R), while for bimolecular gas reactions A = (e 2 k B T/h) (RT/p ...