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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".
It is therefore the change in these functions that is of most interest. The isobaric change in enthalpy H above the common reference temperature of 298.15 K (25 °C) is called the high temperature heat content, the sensible heat, or the relative high-temperature enthalpy, and called henceforth the heat content.
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 ...
The above derivation uses the first and second laws of thermodynamics. The first law of thermodynamics is essentially a definition of heat, i.e. heat is the change in the internal energy of a system that is not caused by a change of the external parameters of the system.
Enthalpy is the transfer of energy in a reaction (for chemical reactions, it is in the form of heat) and is the change in enthalpy. Δ H {\displaystyle \Delta H} is a state function, meaning that Δ H {\displaystyle \Delta H} is independent of processes occurring between initial and final states.
The law states that the total enthalpy change during the complete course of a chemical reaction is independent of the sequence of steps taken. [2] [3] Hess's law is now understood as an expression of the fact that the enthalpy of a chemical process is independent of the path taken from the initial to the final state (i.e. enthalpy is a state ...
Transfers of energy as work, or as heat, or of matter, between the system and the surroundings, take place through the walls, according to their respective permeabilities. Matter or energy that pass across the boundary so as to effect a change in the internal energy of the system need to be accounted for in the energy balance equation.
In contrast, the Gibbs free energy or free enthalpy is most commonly used as a measure of thermodynamic potential (especially in chemistry) when it is convenient for applications that occur at constant pressure. For example, in explosives research Helmholtz free energy is often used, since explosive reactions by their nature induce pressure ...