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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".
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.
Thermodynamic relations are then employed to derive the well-known Gibbs entropy formula. However, the equivalence between the Gibbs entropy formula and the thermodynamic definition of entropy is not a fundamental thermodynamic relation but rather a consequence of the form of the generalized Boltzmann distribution. [38]
Boltzmann's equation—carved on his gravestone. [1]In statistical mechanics, Boltzmann's equation (also known as the Boltzmann–Planck equation) is a probability equation relating the entropy, also written as , of an ideal gas to the multiplicity (commonly denoted as or ), the number of real microstates corresponding to the gas's macrostate:
(Note - the relation between pressure, volume, temperature, and particle number which is commonly called "the equation of state" is just one of many possible equations of state.) If we know all k+2 of the above equations of state, we may reconstitute the fundamental equation and recover all thermodynamic properties of the system.
As the entropy is a function of state the result is independent of the path. The above relation shows that the determination of the entropy requires knowledge of the heat capacity and the equation of state (which is the relation between P,V, and T of the substance involved). Normally these are complicated functions and numerical integration is ...
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 Mollier enthalpy–entropy diagram for water and steam. The "dryness fraction", x , gives the fraction by mass of gaseous water in the wet region, the remainder being droplets of liquid. An enthalpy–entropy chart , also known as the H – S chart or Mollier diagram , plots the total heat against entropy, [ 1 ] describing the enthalpy of a ...