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In chemical thermodynamics, an endergonic reaction (from Greek ἔνδον (endon) 'within' and ἔργον (ergon) 'work'; also called a heat absorbing nonspontaneous reaction or an unfavorable reaction) is a chemical reaction in which the standard change in free energy is positive, and an additional driving force is needed to perform this ...
and they have positive (endergonic) or negative (exergonic) Gibbs free energies of reaction . As Marcus calculations refer exclusively to the electrostatic properties in the solvent (outer sphere) Δ G ∘ {\displaystyle \Delta G^{\circ }} and λ 0 {\displaystyle \lambda _{0}} are independent of one another and therefore can just be added up.
The reaction will only be allowed if the total entropy change of the universe is zero or positive. This is reflected in a negative ΔG, and the reaction is called an exergonic process. If two chemical reactions are coupled, then an otherwise endergonic reaction (one with positive ΔG) can be made to happen.
Using the Eyring equation, there is a straightforward relationship between ΔG ‡, first-order rate constants, and reaction half-life at a given temperature. At 298 K, a reaction with ΔG ‡ = 23 kcal/mol has a rate constant of k ≈ 8.4 × 10 −5 s −1 and a half life of t 1/2 ≈ 2.3 hours, figures that are often rounded to k ~ 10 −4 s ...
Thus, G or A is the amount of energy "free" for work under the given conditions. Up until this point, the general view had been such that: “all chemical reactions drive the system to a state of equilibrium in which the affinities of the reactions vanish”. Over the next 60 years, the term affinity came to be replaced with the term free energy.
The ∆G° can be written as a function of change in enthalpy (∆H°) and change in entropy (∆S°) as ∆G°= ∆H° – T∆S°. Practically, enthalpies, not free energy, are used to determine whether a reaction is favorable or unfavorable, because ∆ H ° is easier to measure and T ∆ S ° is usually too small to be of any significance ...
The definition of the Gibbs function is = + where H is the enthalpy defined by: = +. Taking differentials of each definition to find dH and dG, then using the fundamental thermodynamic relation (always true for reversible or irreversible processes): = where S is the entropy, V is volume, (minus sign due to reversibility, in which dU = 0: work other than pressure-volume may be done and is equal ...
An endothermic process is a chemical or physical process that absorbs heat from its surroundings. [1] In terms of thermodynamics, it is a thermodynamic process with an increase in the enthalpy H (or internal energy U) of the system. [2] In an endothermic process, the heat that a system absorbs is thermal energy transfer into the system.