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Descripción: É o ramo da Física que estuda os efeitos da mudança em temperatura, pressão e volume em sistemas físicos na escala macroscópica. A grosso modo, calor significa "energia" em trânsito, e dinâmica se ...
TEMA 10
EL TERCER PRINCIPIO DE LA TERMODINÁMICA
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Fenómenos de bajas temperaturas. Postulados de Nernst y Planck. Propiedades de los sistemas en el cero absoluto.
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FENÓMENOS DE BAJAS TEMPERATURAS. •
El diseño de dispositivos para conseguir bajas temperaturas ha sido, uno de los problemas más interesantes de la Termodinámica experimental.
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Desde los primeros trabajos realizados por Kirk en 1860, en que consiguió temperaturas de 234,0 K (-39ºC), se han ido encontrando y desarrollando diversos sistemas de enfriamiento hasta alcanzar, mediante procesos de desimanación nuclear la
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A la temperatura cero absoluto se presentan dos problemas muy problemas muy peculiares: 1. La temperatura T = 0 K K no se puede considerar igual que las demás temperaturas, pues representa una singularidad singularidad en el integrando integrando de la ecuación: d 'Q . De este modo, no nos podría extrañar que el comportamien comportamiento to T
de los sistemas reales fuese de tal modo que impida que esta singularidad se presente. 2. Lo mi mism smoo se se po podr dría ía de deci cirr de un unaa máquina de Carnot trabajando entre una temperatura cualquiera y el cero absoluto. Su rendimiento rendimiento sería sería del 100 %. %.
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Se pueden observar los siguientes hechos en el laboratorio: laboratorio : 1.
Una temp tempera eratur turaa apare aparente ntemen mente te peque pequeña ña como como 5 K, resu resulta lta ser ser gra grande nde si se se tiene en cuenta que a una temperatura inferior (2.2 K) el He He sufre sufre transiciones que modifican sustancialmente sus propiedades físicas.
2. Cu Cuan ando do se al alca canz nzan an te temp mper erat atur uras as del del or orde denn de de 10-3 K, los calores específicos de ciertas sales paramagnéticas tienen máximos muy pronunciados.
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No existe, por tanto, ningún motivo para afirmar que determinada temperatura es grande o pequeña, al menos menos a priori.
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OBJETIVO: El problema que se plantea es saber si los resultados experimentales permiten poner de manifiesto ciertos rasgos comunes de los sistemas cuando la temperatura absoluta tiende a cero.
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Si podemos hacer esto, reagruparemos esos comportamientos comunes en un enunciado de validez general que se conoce como el Tercer Principio Princip io de la Termodi Termodinámica námica..
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Postulados de Nernst y Planck . El tercer principio de la Termodinámica se puede introducir de varias formas: 1. A partir de la Mecánica Estadística Cuántica (enunciado de Planck).
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POSTULADO DE NERNST
Nernst introduce el postulado que lleva su nombre como consecuencia del estudio de la afinidad de las reacciones químicas. El primer concepto que es necesario introducir es el de afinidad química. •
Resulta familiar el hecho de la existencia de especies químicas químicas que
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Resulta difícil traducir la afinidad en una magnitud física, susceptible de ser medida. Cronológicamente la primera solución fue facilitada por Berthelot quien
propuso: la energía en forma de calor que se pone en
juego en la verificación de una reacción química es una medida de la afinidad .
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Una vez definida la afinidad, nuestro próximo objetivo consiste en la evaluación,
a fin de conocer previamente si una reacción se puede o no
producir. Si se tiene en cuenta la relación de Gibbs-Helmholtz Gibbs-Helmholtz::
H
G T
G T
A
H T
A T
H 2
( A / T ) T
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Nernst,
como
consecuencia
del
estudio
experimental
del
comportamiento de varias sustancias, observó observó que la velocidad de cambio era siempre un número finito finito y que el término A / T
p
disminuía cuando disminuía cuando nos acercamos a la temperatura de 0 K,
tendiendo a cero. cero. En consecuencia se puede escribir que:
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Si se hubiese considerado un proceso isocórico y definido la afinidad afinidad como como
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De cualquiera de las dos ecuaciones se puede obtener que:
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Puesto que las transformaciones a p y V constantes en el 0 K, son
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Propiedades de los sistemas en el cero absoluto.
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2.- COEFICIENTES TÉRMICOS EN EL CERO ABSOLUTO.
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