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第165行： − + − − − The most general kind of thermodynamic equilibrium of a system is through contact with the surroundings that allows simultaneous passages of all chemical substances and all kinds of energy. A system in thermodynamic equilibrium may move with uniform acceleration through space but must not change its shape or size while doing so; thus it is defined by a rigid volume in space. It may lie within external fields of force, determined by external factors of far greater extent than the system itself, so that events within the system cannot in an appreciable amount affect the external fields of force. The system can be in thermodynamic equilibrium only if the external force fields are uniform, and are determining its uniform acceleration, or if it lies in a non-uniform force field but is held stationary there by local forces, such as mechanical pressures, on its surface. − − The most general kind of thermodynamic equilibrium of a system is through contact with the surroundings that allows simultaneous passages of all chemical substances and all kinds of energy. A system in thermodynamic equilibrium may move with uniform acceleration through space but must not change its shape or size while doing so; thus it is defined by a rigid volume in space. It may lie within external fields of force, determined by external factors of far greater extent than the system itself, so that events within the system cannot in an appreciable amount affect the external fields of force. The system can be in thermodynamic equilibrium only if the external force fields are uniform, and are determining its uniform acceleration, or if it lies in a non-uniform force field but is held stationary there by local forces, such as mechanical pressures, on its surface. 第177行：
第172行： − Thermodynamic equilibrium is a [[primitive notion]] of the theory of thermodynamics. According to [[Philip M. Morse|P.M. Morse]]: "It should be emphasized that the fact that there are thermodynamic states, ..., and the fact that there are thermodynamic variables which are uniquely specified by the equilibrium state ... are ''not'' conclusions deduced logically from some philosophical first principles. They are conclusions ineluctably drawn from more than two centuries of experiments."<ref>[[Philip M. Morse|Morse, P.M.]] (1969), p. 7.</ref> This means that thermodynamic equilibrium is not to be defined solely in terms of other theoretical concepts of thermodynamics. M. Bailyn proposes a fundamental law of thermodynamics that defines and postulates the existence of states of thermodynamic equilibrium.<ref>Bailyn, M. (1994), p. 20.</ref>+ − − Thermodynamic equilibrium is a primitive notion of the theory of thermodynamics. According to P.M. Morse: "It should be emphasized that the fact that there are thermodynamic states, ..., and the fact that there are thermodynamic variables which are uniquely specified by the equilibrium state ... are not conclusions deduced logically from some philosophical first principles. They are conclusions ineluctably drawn from more than two centuries of experiments." This means that thermodynamic equilibrium is not to be defined solely in terms of other theoretical concepts of thermodynamics. M. Bailyn proposes a fundamental law of thermodynamics that defines and postulates the existence of states of thermodynamic equilibrium. − 热力学平衡是热力学理论的一个'''<font color="#ff8000">基本概念 Primitive Notion</font>'''。'''<font color="#ff8000">P.M.莫尔斯 P.M.Morse</font>'''说: “应该强调的是，存在热力学状态这一事实，以及存在由平衡态唯一指定的热力学变量这一事实，并不是从某些哲学第一原理得出的逻辑结论。这些结论不可避免地来自两个多世纪的实验。”这意味着热力学平衡不能仅仅用热力学的其他理论概念来定义。M.Bailyn提出了一个基本的热力学定律理论，它定义并假设了热力学平衡的存在。 − − − Textbook definitions of thermodynamic equilibrium are often stated carefully, with some reservation or other. − − Textbook definitions of thermodynamic equilibrium are often stated carefully, with some reservation or other. − + − For example, A. Münster writes: "An isolated system is in thermodynamic equilibrium when, in the system, no changes of state are occurring at a measurable rate." There are two reservations stated here; the system is isolated; any changes of state are immeasurably slow. He discusses the second proviso by giving an account of a mixture oxygen and hydrogen at room temperature in the absence of a catalyst. Münster points out that a thermodynamic equilibrium state is described by fewer macroscopic variables than is any other state of a given system. This is partly, but not entirely, because all flows within and through the system are zero.<ref>Münster, A. (1970), p. 52.</ref> − − For example, A. Münster writes: "An isolated system is in thermodynamic equilibrium when, in the system, no changes of state are occurring at a measurable rate." There are two reservations stated here; the system is isolated; any changes of state are immeasurably slow. He discusses the second proviso by giving an account of a mixture oxygen and hydrogen at room temperature in the absence of a catalyst. Münster points out that a thermodynamic equilibrium state is described by fewer macroscopic variables than is any other state of a given system. This is partly, but not entirely, because all flows within and through the system are zero. − − 例如，A. Münster写道：“当一个孤立系统中没有以可测量的速率发生状态变化时，系统处于热力学平衡状态。”这里有两项保留：系统是孤立的；任何状态的变化都是不可测量的缓慢。他通过对在室温且没有催化剂的情况下混合氧和氢的说明，讨论了第二个条件。Münster指出，描述热力学平衡状态所需要的宏观变量比给定系统任何其他状态都少。这是部分，但不完全是，因为系统内和流过系统的所有流都是零。 − − − − R. Haase's presentation of thermodynamics does not start with a restriction to thermodynamic equilibrium because he intends to allow for non-equilibrium thermodynamics. He considers an arbitrary system with time invariant properties. He tests it for thermodynamic equilibrium by cutting it off from all external influences, except external force fields. If after insulation, nothing changes, he says that the system was in ''equilibrium''.<ref>Haase, R. (1971), pp. 3–4.</ref> − − R. Haase's presentation of thermodynamics does not start with a restriction to thermodynamic equilibrium because he intends to allow for non-equilibrium thermodynamics. He considers an arbitrary system with time invariant properties. He tests it for thermodynamic equilibrium by cutting it off from all external influences, except external force fields. If after insulation, nothing changes, he says that the system was in equilibrium. − − R. Haase's的热力学演示并不从对热力学平衡的限制开始，因为他打算考虑非平衡态热力学。他考虑一个具有时间不变性质的任意系统。他通过切断除外力场以外的所有外部影响来测试它的热力学平衡。如果在绝缘之后，没有任何变化，他说，系统处于平衡状态。 − − − − In a section headed "Thermodynamic equilibrium", H.B. Callen defines equilibrium states in a paragraph. He points out that they "are determined by intrinsic factors" within the system. They are "terminal states", towards which the systems evolve, over time, which may occur with "glacial slowness".<ref>Callen, H.B. (1960/1985), p. 13.</ref> This statement does not explicitly say that for thermodynamic equilibrium, the system must be isolated; Callen does not spell out what he means by the words "intrinsic factors". − − In a section headed "Thermodynamic equilibrium", H.B. Callen defines equilibrium states in a paragraph. He points out that they "are determined by intrinsic factors" within the system. They are "terminal states", towards which the systems evolve, over time, which may occur with "glacial slowness". This statement does not explicitly say that for thermodynamic equilibrium, the system must be isolated; Callen does not spell out what he means by the words "intrinsic factors". − − 在一个标题为“热力学平衡”的章节中，H.B. Callen在一个段落中定义了平衡状态.他指出，它们“是由系统内部的内在因素决定的”。它们是“终端状态” ，随着时间的推移，系统会以“冰川般缓慢”的速度朝着这个终端状态演化。这个说法并没有明确，对于热力学平衡系统必须是孤立的;；Callen也没有说明他所说的“内在因素”是什么意思。 − − Another textbook writer, C.J. Adkins, explicitly allows thermodynamic equilibrium to occur in a system which is not isolated. His system is, however, closed with respect to transfer of matter. He writes: "In general, the approach to thermodynamic equilibrium will involve both thermal and work-like interactions with the surroundings." He distinguishes such thermodynamic equilibrium from thermal equilibrium, in which only thermal contact is mediating transfer of energy.<ref>Adkins, C.J. (1968/1983), p. ''7''.</ref>+ − Another textbook writer, C.J. Adkins, explicitly allows thermodynamic equilibrium to occur in a system which is not isolated. His system is, however, closed with respect to transfer of matter. He writes: "In general, the approach to thermodynamic equilibrium will involve both thermal and work-like interactions with the surroundings." He distinguishes such thermodynamic equilibrium from thermal equilibrium, in which only thermal contact is mediating transfer of energy. − 另一位教科书作者，C.J.Adkins，明确允许热力学平衡在非孤立的系统中发生。然而，他的系统在物质转移方面是封闭的。他写道: “一般来说，热力学平衡的方法包括热和类似功的形式与周围环境的相互作用。”他将这种热力学平衡与只有通过热接触才能进行能量传递的热平衡相区别。+ + − Another textbook author, [[J.R. Partington]], writes: "(i) ''An equilibrium state is one which is independent of time''." But, referring to systems "which are only apparently in equilibrium", he adds : "Such systems are in states of ″false equilibrium.″" Partington's statement does not explicitly state that the equilibrium refers to an isolated system. Like Münster, Partington also refers to the mixture of oxygen and hydrogen. He adds a proviso that "In a true equilibrium state, the smallest change of any external condition which influences the state will produce a small change of state ..."<ref>Partington, J.R. (1949), p. 161.</ref> This proviso means that thermodynamic equilibrium must be stable against small perturbations; this requirement is essential for the strict meaning of thermodynamic equilibrium. − Another textbook author, J.R. Partington, writes: "(i) An equilibrium state is one which is independent of time." But, referring to systems "which are only apparently in equilibrium", he adds : "Such systems are in states of ″false equilibrium.″" Partington's statement does not explicitly state that the equilibrium refers to an isolated system. Like Münster, Partington also refers to the mixture of oxygen and hydrogen. He adds a proviso that "In a true equilibrium state, the smallest change of any external condition which influences the state will produce a small change of state ..." This proviso means that thermodynamic equilibrium must be stable against small perturbations; this requirement is essential for the strict meaning of thermodynamic equilibrium. − +
→Definitions 定义
根据'''<font color="#ff8000">L.缇莎 L.Tisza</font>'''的说法: “ ... 在讨论接近绝对零度的现象时。经典理论的绝对预测变得特别模糊，因为在非平衡状态下发生冻结是非常普遍的。”<ref>Tisza, L. (1966), p. 119.</ref>
根据'''<font color="#ff8000">L.缇莎 L.Tisza</font>'''的说法: “ ... 在讨论接近绝对零度的现象时。经典理论的绝对预测变得特别模糊，因为在非平衡状态下发生冻结是非常普遍的。”<ref>Tisza, L. (1966), p. 119.</ref>
==Definitions 定义==
==定义==
一个系统最普遍的热力学平衡是通过与周围环境的接触，允许所有化学物质和各种能量同时通过。热力学平衡中的系统可能以均匀加速度在空间中运动，但此时不能改变其形状或大小; 因此它是由空间中的刚性体积来定义的。它可能存在于外力场中，由远远大于系统本身的外部因素决定，因此系统内的事件不会对外力场产生相当大的影响。只有当外力场是均匀的，并且确定了它的均匀加速度，或者它处于一个非均匀力场中，但是由于表面的局部力，例如机械压力，使它保持静止时，这个系统才能处于热力学平衡。
一个系统最普遍的热力学平衡是通过与周围环境的接触，允许所有化学物质和各种能量同时通过。热力学平衡中的系统可能以均匀加速度在空间中运动，但此时不能改变其形状或大小; 因此它是由空间中的刚性体积来定义的。它可能存在于外力场中，由远远大于系统本身的外部因素决定，因此系统内的事件不会对外力场产生相当大的影响。只有当外力场是均匀的，并且确定了它的均匀加速度，或者它处于一个非均匀力场中，但是由于表面的局部力，例如机械压力，使它保持静止时，这个系统才能处于热力学平衡。
热力学平衡是热力学理论的一个'''<font color="#ff8000">基本概念 Primitive Notion</font>'''。'''<font color="#ff8000">P.M.莫尔斯 P.M.Morse</font>'''说: “应该强调的是，存在热力学状态这一事实，以及存在由平衡态唯一指定的热力学变量这一事实，并不是从某些哲学第一原理得出的逻辑结论。这些结论不可避免地来自两个多世纪的实验。”<ref>[[Philip M. Morse|Morse, P.M.]] (1969), p. 7.</ref>这意味着热力学平衡不能仅仅用热力学的其他理论概念来定义。M.Bailyn提出了一个基本的热力学定律理论，它定义并假设了热力学平衡的存在。<ref>Bailyn, M. (1994), p. 20.</ref>
热力学平衡的教科书定义通常被仔细说明，并有些保留。
热力学平衡的教科书定义通常被仔细说明，并有些保留。
例如，A. Münster写道：“当一个孤立系统中没有以可测量的速率发生状态变化时，系统处于热力学平衡状态。”这里有两项保留：系统是孤立的；任何状态的变化都是不可测量的缓慢。他通过对在室温且没有催化剂的情况下混合氧和氢的说明，讨论了第二个条件。Münster指出，描述热力学平衡状态所需要的宏观变量比给定系统任何其他状态都少。这是部分，但不完全是，因为系统内和流过系统的所有流都是0。<ref>Münster, A. (1970), p. 52.</ref>
R. Haase's的热力学演示并不从对热力学平衡的限制开始，因为他打算考虑非平衡态热力学。他考虑一个具有时间不变性质的任意系统。他通过切断除外力场以外的所有外部影响来测试它的热力学平衡。如果在绝缘之后，没有任何变化，他说，系统处于平衡状态。<ref>Haase, R. (1971), pp. 3–4.</ref>
在一个标题为“热力学平衡”的章节中，H.B. Callen在一个段落中定义了平衡状态.他指出，它们“是由系统内部的内在因素决定的”。它们是“终端状态” ，随着时间的推移，系统会以“冰川般缓慢”的速度朝着这个终端状态演化。这个说法并没有明确，对于热力学平衡系统必须是孤立的;；Callen也没有说明他所说的“内在因素”是什么意思。<ref>Callen, H.B. (1960/1985), p. 13.</ref>
另一位教科书作者，C.J.Adkins，明确允许热力学平衡在非孤立的系统中发生。然而，他的系统在物质转移方面是封闭的。他写道: “一般来说，热力学平衡的方法包括热和类似功的形式与周围环境的相互作用。”他将这种热力学平衡与只有通过热接触才能进行能量传递的热平衡相区别。<ref>Adkins, C.J. (1968/1983), p. ''7''.</ref>
另一位教科书作者'''<font color="#ff8000">J.R.帕廷顿 J.R.Partington</font>'''写道: “(i)平衡状态是独立于时间的状态。”但是，在提到“只是明显处于平衡状态”的系统时，他补充说: “这样的系统处于‘虚假平衡’状态。帕廷顿的陈述没有明确指出平衡是指一个孤立的系统。和Münster一样，Partington也指的是氧和氢的混合物。他补充说：“在一个真正的平衡状态，任何影响状态的外部条件的微小变化都会产生一个微小的状态变化... ... ”这个条件意味着热力学平衡必须在小的扰动下保持稳定; 这个要求对于热力学平衡的严格意义是必不可少的。
另一位教科书作者'''<font color="#ff8000">J.R.帕廷顿 J.R.Partington</font>'''写道: “(i)平衡状态是独立于时间的状态。”但是，在提到“只是明显处于平衡状态”的系统时，他补充说: “这样的系统处于‘虚假平衡’状态。帕廷顿的陈述没有明确指出平衡是指一个孤立的系统。和Münster一样，Partington也指的是氧和氢的混合物。他补充说：“在一个真正的平衡状态，任何影响状态的外部条件的微小变化都会产生一个微小的状态变化... ... ”<ref>Partington, J.R. (1949), p. 161.</ref>这个条件意味着热力学平衡必须在小的扰动下保持稳定; 这个要求对于热力学平衡的严格意义是必不可少的。