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This is possible provided the total entropy change of the system plus the surroundings is positive as required by the second law: ΔS tot = ΔS + ΔS R > 0. For the three examples given above: 1) Heat can be transferred from a region of lower temperature to a higher temperature in a refrigerator or in a heat pump. These machines must provide ...
The concepts of Hess's law can be expanded to include changes in entropy and in Gibbs free energy, since these are also state functions. The Bordwell thermodynamic cycle is an example of such an extension that takes advantage of easily measured equilibria and redox potentials to determine experimentally inaccessible Gibbs free energy values.
For an isolated ideal gas (with fixed total energy and fixed total number of particles), the function H is at a minimum when the particles have a Maxwell–Boltzmann distribution; if the molecules of the ideal gas are distributed in some other way (say, all having the same kinetic energy), then the value of H will be higher.
Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like G (Gibbs free energy) or H . [1] 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 ...
However, in some cases the enthalpy and entropy do change dramatically with temperature. A first-order approximation is to assume that the two different reaction products have different heat capacities. Incorporating this assumption yields an additional term c / T 2 in the expression for the equilibrium constant as a function of ...
In a stretched out piece of rubber, for example, the arrangement of the molecules of its structure has an "ordered" distribution and has zero entropy, while the "disordered" kinky distribution of the atoms and molecules in the rubber in the non-stretched state has positive entropy. Similarly, in a gas, the order is perfect and the measure of ...
Since an entropy is a state function, the entropy change of the system for an irreversible path is the same as for a reversible path between the same two states. [22] However, the heat transferred to or from the surroundings is different as well as its entropy change. We can calculate the change of entropy only by integrating the above formula.
A = (ek B T/h) exp(ΔS ‡ /R), while for bimolecular gas reactions A = (e 2 k B T/h) (RT/p) exp(ΔS ‡ /R). In these equations e is the base of natural logarithms, h is the Planck constant, k B is the Boltzmann constant and T the absolute temperature. R′ is the ideal gas constant. The factor is needed because of the pressure dependence of ...