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Breaking and making chemical bonds involves energy release or uptake, often as heat that may be either absorbed by or evolved from the chemical system. Energy released (or absorbed) because of a reaction between chemical substances ("reactants") is equal to the difference between the energy content of the products and the reactants.
The internal energy of a thermodynamic system is the energy of the system as a state function, measured as the quantity of energy necessary to bring the system from its standard internal state to its present internal state of interest, accounting for the gains and losses of energy due to changes in its internal state, including such quantities as magnetization.
The Van 't Hoff equation relates the change in the equilibrium constant, K eq, of a chemical reaction to the change in temperature, T, given the standard enthalpy change, Δ r H ⊖, for the process. The subscript r {\displaystyle r} means "reaction" and the superscript ⊖ {\displaystyle \ominus } means "standard".
In the case of chemical reactions this is usually the number of particles or mole fractions, subject to the conservation of elements. At equilibrium, these will take on their equilibrium values, and the internal energy will be a function only of the chosen value of entropy . By the definition of the Legendre transform, the Helmholtz free energy ...
The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy, and volume for a closed system in thermal equilibrium in the following way. d U = T d S − P d V {\displaystyle \mathrm {d} U=T\,\mathrm {d} S-P\,\mathrm {d} V\,}
The path or series of states through which a system passes from an initial equilibrium state to a final equilibrium state [1] and can be viewed graphically on a pressure-volume (P-V), pressure-temperature (P-T), and temperature-entropy (T-s) diagrams. [2] There are an infinite number of possible paths from an initial point to an end point in a ...
For example, in many cases of such evolution, internal mechanical equilibrium is established much more rapidly than the other aspects of the eventual thermodynamic equilibrium. [57] Another example is that, in many cases of such evolution, thermal equilibrium is reached much more rapidly than chemical equilibrium. [60]
The laws of thermodynamics are only directly applicable to systems in thermal equilibrium. If we wish to describe phenomena like chemical reactions, then the best we can do is to consider suitably chosen initial and final states in which the system is in (metastable) thermal equilibrium.