The Nernst heat theorem was formulated by Walther Nernst early in the twentieth century and was used in the development of the third law of thermodynamics.
The Nernst heat theorem was formulated by Walther Nernst early in the twentieth century and was used in the development of the third law of thermodynamics.
The Nernst heat theorem says that as absolute zero is approached, the entropy change ΔS for a chemical or physical transformation approaches 0. This can be expressed mathematically as follows:
The above equation is a modern statement of the theorem. Nernst often used a form that avoided the concept of entropy. [1]
Another way of looking at the theorem is to start with the definition of the Gibbs free energy (G), G = H - TS, where H stands for enthalpy. For a change from reactants to products at constant temperature and pressure the equation becomes .
In the limit of T = 0 the equation reduces to just ΔG = ΔH, as illustrated in the figure shown here, which is supported by experimental data. [2] However, it is known from thermodynamics that the slope of the ΔG curve is -ΔS. Since the slope shown here reaches the horizontal limit of 0 as T → 0 then the implication is that ΔS → 0, which is the Nernst heat theorem.
The significance of the Nernst heat theorem is that it was later used by Max Planck to give the third law of thermodynamics, which is that the entropy of all pure, perfectly crystalline homogeneous materials in complete internal equilibrium is 0 at absolute zero.
Walther Nernst.- The labels on the figure have been modified. The original labels were A and Q, instead of ΔG and ΔH, respectively.
Absolute zero is the lowest limit of the thermodynamic temperature scale; a state at which the enthalpy and entropy of a cooled ideal gas reach their minimum value, taken as zero kelvin. The fundamental particles of nature have minimum vibrational motion, retaining only quantum mechanical, zero-point energy-induced particle motion. The theoretical temperature is determined by extrapolating the ideal gas law; by international agreement, absolute zero is taken as −273.15 degrees on the Celsius scale, which equals −459.67 degrees on the Fahrenheit scale. The corresponding Kelvin and Rankine temperature scales set their zero points at absolute zero by definition.
Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes of state within the confines of the laws of thermodynamics. Chemical thermodynamics involves not only laboratory measurements of various thermodynamic properties, but also the application of mathematical methods to the study of chemical questions and the spontaneity of processes.
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In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction from the standard electrode potential, absolute temperature, the number of electrons involved in the redox reaction, and activities of the chemical species undergoing reduction and oxidation respectively. It was named after Walther Nernst, a German physical chemist who formulated the equation.
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In thermodynamics, the Gibbs free energy is a thermodynamic potential that can be used to calculate the maximum amount of work, other than pressure-volume work, that may be performed by a thermodynamically closed system at constant temperature and pressure. It also provides a necessary condition for processes such as chemical reactions that may occur under these conditions. The Gibbs free energy is expressed as
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A thermodynamic potential is a scalar quantity used to represent the thermodynamic state of a system. Just as in mechanics, where potential energy is defined as capacity to do work, similarly different potentials have different meanings. The concept of thermodynamic potentials was introduced by Pierre Duhem in 1886. Josiah Willard Gibbs in his papers used the term fundamental functions.
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In thermodynamics, an isothermal process is a type of thermodynamic process in which the temperature T of a system remains constant: ΔT = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and a change in the system occurs slowly enough to allow the system to be continuously adjusted to the temperature of the reservoir through heat exchange (see quasi-equilibrium). In contrast, an adiabatic process is where a system exchanges no heat with its surroundings (Q = 0).
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