热力学定律 Laws of thermodynamics

热力学定律 The laws of thermodynamics定义了许多物理量，如 温度 temperature、 能量 energy和熵 entropy，这些物理量表征处于热力学平衡的热力学系统。这些定律描述了这些物理量之间的关系，并构成了排除某些现象的可能性的基础，例如永动机。除了在热力学中的应用之外，它们也是基础物理学中的重要基本定律，也适用于其他自然科学。

传统上， 热力学 Thermodynamics描述了三个基本定律：（简单的按顺序命名为）第一定律、第二定律和第三定律。此外，在前三个定律确立之后，人们认识到可以提出另一个相对于这三个定律更为基本的定律，即第零定律。

热力学第零定律 zeroth law of thermodynamics定义了 热平衡 thermal equilibrium，并为温度定义奠定了基础：如果两个系统各与第三个系统处于热平衡，则它们彼此也处于热平衡。

热力学第一定律 first law of thermodynamics：当能量以 功 work、 热 heat或物质的形式进入或离开一个系统时，根据能量守恒定律, 系统的内能 internal energy发生变化。同样地，第一类永动机机器(不需要能量输入就可以做功的机器)是不可能造成的。

热力学第二定律 second law of thermodynamics：在自然热力学过程中，相互作用的热力学系统的熵的总和增加。同样地，第二类永动机(自发地把热能转化为机械功的机器)是不可能制造出的。

热力学第三定律 third law of thermodynamics：当温度趋于 绝对零度 absolute zero时，系统的熵趋于一个定值。除非晶固体(玻璃)外，系统在绝对零度时的熵通常接近于零。

有人提出了其他的定律，但没有一个达到公认的四个定律的普遍性，也没有在标准教科书中被讨论。^[1]^[2]^[3]^[4]^[5]

热力学零定律 Zeroth law

热力学第零定律可以用以下形式表示：

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如果两个系统都各与第三个系统处于热平衡状态，则它们彼此处于热平衡状态.

该定律旨在允许一个经验参数存在，即温度，作为热力学系统的一种性质，即相互处于热平衡的系统具有相同的温度。这里所述的定律适用于特定的物质(例如一定量的气体物质）来匹配其他物质的温度，但不能证明温度是一个可以用实数来衡量的量。

虽然这个版本的定律是最常见的陈述版本之一，但它只是被称为“第零定律”的众多陈述之一。有些陈述更进一步，提供了一个重要的物理事实，即温度是一维的，并且从概念上把物体按实数顺序由冷到热排列。^[6]^[7]^[8]也许对于“第零定律”并没有唯一的“最佳的表述”，因为在文献中有一系列的热力学原理的表述，每一种都要求对热力学定律作出各自适当的说明。

虽然这些关于温度和热平衡的概念是热力学的基础，并在19世纪得到了清楚的阐述，但是直到20世纪30年代福勒和古根海姆这样做的时候，人们才普遍感觉到需要对上述定律进行明确编号，而这时第一定律、第二定律和第三定律已经得到广泛的理解和认可。因此，它被称为第零定律。该定律作为早期定律基础的重要性在于，它允许以非循环的方式定义温度，而无需参考熵及其共轭变量。这样的温度定义被称为“经验主义的”。^[9]^[10]^[11]^[12]^[13]^[14]

第一定律 First law

热力学第一定律是 能量守恒 conservation of energy定律的一个版本，适用于热力学系统。

能量守恒定律指出，一个孤立系统的总能量是恒定的;能量可以从一种形式转化为另一种形式，但能量既不会凭空产生也不会凭空消失。

对于一个没有物质转移的热力学过程，第一定律通常用公式表示为：

[math]\displaystyle{ \Delta U_{\rm system} = Q - W }[/math],

其中 $Δ U system$ 表示一个封闭系统内部能量的变化， $Q$ 表示外界以热的形式提供给系统的能量， $W$ 表示该系统对周围环境所做的热力学功(在这里用负号表示)。

(定义对系统所做的功在本文中没有使用的另一个符号约定。)

在封闭系统的两级 热力循环thermodynamic cycle中，该循环回到其原始状态，在循环的一个阶段向系统提供的热量 $Q in$ ，减去另一个阶段从系统中去除的热量 $Q out$ ，加上对系统做的的热力学功 $W in$ ，

等于离开系统的做的热力学功 $W out$ 。

[math]\displaystyle{ \Delta U_{\rm system\,(full\,cycle)}=0 }[/math]

因此，对于一个完整的循环,

Or [math]\displaystyle{ Q - W = Q_{\rm in} - Q_{\rm out} - (W_{\rm out} - W_{\rm in}) =0 }[/math].

对于绝热系统（绝热隔离）的特殊情况，绝热隔离系统内能的变化只能是系统做功的结果，因为绝热假设是: $Q = 0$ 。

[math]\displaystyle{ \Delta U_{\rm system} = U_{\rm final} - U_{\rm initial} = W_{\rm in} - W_{\rm out} }[/math]

对于包括物质转移的过程，还需要进一步的说明: ‘在充分考虑了各个系统的基准参考状态后，当两个系统----

它们可能由不同的化学成分组成，最初只是被防渗墙隔开，或者是被隔离---- 通过移除墙体的热力学操作结合成一个新系统，那么

[math]\displaystyle{ U_{\rm system} = U_1 + U_2 }[/math],

其中 $U system$ 表示组合系统的内能， $U 1$ and $U 2$ 表示各自分离系统的内能

第一定律包括以下几个原则:

能量守恒定律

能量既不能被创造也不能被消灭。但是，能量可以改变形式，能量可以从一个地方流动到另一个地方。能量守恒定律的一个特殊结果是，孤立系统的总能量不变。

内能的概念及其与温度关系。

如果系统具有确定的温度，则其总能量具有三个可区分的成分，分别称为动能（由与系统整体运动产生的能量），势能（由外部施加的立场产生的能量，比如重力）和内能（热热力学的基本量）。内能概念的确立将热力学第一定律与一般的能量守恒定律区分开来。

 ——Solitude(讨论)

[math]\displaystyle{ E_{\rm total} = \mathrm{KE}_{\rm system} + \mathrm{PE}_{\rm system} + U_{\rm system} }[/math]

物质的内能可以解释为其组成原子的不规则微观运动的不同动能和它们之间相互作用的势能的总和。这些微观能量统称为物质的内能，并由宏观热力学性质来解释。组成原子的微观运动的总和随着系统温度的升高而增加; 这假设在系统的微观层次上没有其他的相互作用，例如化学反应、组成原子相互间的势能。

做功是一种以某种方式向系统传递能量或从系统传递能量的过程，其方式可以用作用在系统外部及其周围环境之间的宏观机械力来描述。例如，外部驱动的轴在系统内搅动，或外部施加的电场使系统材料极化，或活塞压缩系统。除非另有说明，习惯上把做功看作是在不影响周围环境的情况下发生的。实际上，在一切自然过程中，有些功是因内摩擦或粘黏而消失的。系统所做的功，可以来自于它的总动能，总势能或者它的内能。

例如，当一台机器(不是系统的一部分)将系统向上提升时，一些能量就会从机器转移到系统。系统的能量随着系统所做功的增加而增加，在这种特殊的情况下，系统的能量增加表现为系统的重力势能的增加。机器将系统向上提升时对系统做的功增加了系统的势能:

[math]\displaystyle{ W = \Delta \mathrm{PE}_{\rm system} }[/math]

或者一般来说，以功的形式加入系统的能量可以分为动能、势能或内能:

[math]\displaystyle{ W = \Delta \mathrm{KE}_{\rm system}+\Delta \mathrm{PE}_{\rm system}+\Delta U_{\rm system} }[/math]

当物质转移到一个系统中时，物质相关的内能和势能也随之转移。

[math]\displaystyle{ \left( u \,\Delta M \right)_{\rm in} = \Delta U_{\rm system} }[/math]

其中

u

表示在周围环境中测量的转移物质的单位质量的内能;

Δ M

表示被转移物质的数量。

热的流动是能量传递的一种形式。

加热是一个将能量转移到系统中或从系统中转移出的自然过程，而不是通过做功或物质的转移。热量只能从较热的系统直接传递到较冷的系统。

如果系统具有不渗透物质的刚性壁，那么能量不能通过做功传入或传出系统，而且没有外部的远程力场影响系统以改变其内能，那么内能只能通过以热的形式进行传递来改变:

[math]\displaystyle{ \Delta U_{\rm system}=Q }[/math]

其中

Q

表示以热量形式传递到系统中的能量。

结合这些原理，就可以得出传统的热力学第一定律的表述: 不可能制造一台在没有等量能量输入的情况下不断做功的机器。或者更简单地说，第一类永动机是不可能造成的。

第二定律 Second law

热力学第二定律表明了自然过程的不可逆性，并且在许多情况下，自然过程的趋向于物质和能量的空间均匀性，特别是温度。它可以用各种有趣而重要的方式来表达。

这意味着热力学系统中存在一个叫做熵的量。就这个数量而言，它意味着当两个最初隔离的系统分别位于彼此独立但不一定彼此处于热力学平衡的空间区域中，然后彼此相互作用时，它们最终将达到相互的热力学平衡。最初隔离的系统的熵之和小于或等于最终组合的总熵。当两个初始系统各自的强变量(温度、压力)相等时，才发生平等。那么最终的系统也有相同的值。

第二定律适用于可逆和不可逆的多种过程。所有的自然过程都是不可逆的。可逆过程是一个有用的和方便的理论假设，但不发生在自然界。

这种不可逆性的一个主要例子是通过传导或辐射进行的热传递。早在熵的概念被发现之前，人们就已经知道，当两个最初温度不同的物体直接进行热连接时，热量总是从较热的物体流向较冷的物体。

第二定律也告诉我们除了热传递之外的不可逆性，例如摩擦力和粘度，以及化学反应。该定律应给熵的概念提供更广泛的范围。

根据热力学第二定律，在理论上和假设的可逆传热中，传热元素δQ是系统和热源或热目的地的温度(t)与系统共轭变量熵（S）的增量(dS)的乘积

[math]\displaystyle{ \delta Q = T\,dS\, . }[/math]^[1]

当只知道宏观状态时，熵也可以被看作是对系统运动和构型的微观细节有关的物理度量。这种细节通常在微观或分子尺度上被称为无序。该定律声称，对于一个系统的两个给定的宏观指定状态，它们之间存在一个被称为熵差的量。这种熵的差异定义了需要多少额外的微观物理信息来指定一个宏观指定状态，给定另一个宏观指定状态-通常是一个方便选择的参考状态，这可能是假定存在的，而不是明确陈述的。自然过程的最终条件始终包含着微观上特定的影响，而这些影响，从过程初始条件的宏观规定来看是无法被完全准确预测的。这就是为什么熵在自然过程中会增加——熵的增加告诉我们需要多少额外的微观信息来区分最终的宏观指定状态和最初的宏观指定状态。^[15]

This information entropy difference defines how much additional microscopic physical information is needed to specify one of the macroscopically specified states, given the macroscopic specification of the other – often a conveniently chosen reference state which may be presupposed to exist rather than explicitly stated. A final condition of a natural process always contains microscopically specifiable effects which are not fully and exactly predictable from the macroscopic specification of the initial condition of the process. This is why entropy increases in natural processes – the increase tells how much extra microscopic information is needed to distinguish the final macroscopically specified state from the initial macroscopically specified state.

第三定律 Third law

热力学第三定律可以表示为：

当温度接近绝对零度时，任何纯物质的完整晶体的熵接近零。

在零温时，系统必须处于热能最小的状态。如果完美晶体只有一种能量最小的状态，则该说法成立。熵与可能的微状态数有关:

[math]\displaystyle{ S = k_{\mathrm B}\, \mathrm{ln}\, \Omega }[/math]

其中 s 是系统的熵，k_B是玻尔兹曼常数，以及Ω是微状态数(例如:可能的原子结构)。在绝对零度下只有一种微状态(Ω=1，因为纯物质的所有原子都是相同的，所以所有阶数都是相同的，因为只有一个组合)和 ln (1)=0。

第三定律的一个更普遍的形式，适用于像玻璃这样的系统，可能有一个以上的微观上截然不同的能量状态，或可能有一个微观上截然不同的“冻结状态”，虽然不是一个严格意义上的的最低能量状态，也不是严格意义上的热力学平衡，在绝对零度的温度下:

系统的熵随着温度接近绝对零度而接近一个恒定值。

这个常数(不一定是零)被称为系统的余熵。

历史 History

热学和统计物理学的哲学

大约在1797年，拉姆福德(出生于本杰明·汤普森)表明，无休止的机械作用可以从固定数量的工作物质中产生无限量的热量，从而挑战了热量理论。该理论认为在固定数量的工作物质中会有有限的热量 / 能量。1824年，萨迪·卡诺 Sadi Carnot建立了第一个热力学原理，也就是后来的热力学第二定律。到1860年，正如鲁道夫·克劳修斯 Rudolf Clausius和威廉·汤姆森 William Thomson等人的著作所正式规定的那样，已经确立的两个热力学原理得到了发展，第一个原理和第二个原理，后来被重新定义为热力学定律。例如，1873年，热力学学家乔赛亚·威拉德·吉布斯 Josiah Willard Gibbs在他的回忆录《流体热力学的图解法》中明确阐述了热力学的前两个绝对定律。整个20世纪的一些教科书对这些定律进行了不同的编号。在一些与化学无关的领域，第二定律被认为仅仅处理热机的效率问题，而所谓的第三定律则处理熵增问题。直接定义熵计算的零点不被认为是一条定律。这种分离逐渐形成了第二定律，现代第三定律被广泛采用。

==See also==
另请参阅

化学热力学 Chemical thermodynamics

守恒定律 Conservation law

熵增 Entropy production

金斯伯格定理 Ginsberg's theorem

宇宙热寂 Heat death of the universe

H定理 H-theorem

科学规律 Laws of science

昂萨格倒易关系（有时被描述为热力学第四定律） Onsager reciprocal relations (sometimes described as a fourth law of thermodynamics)

统计力学 Statistical mechanics

热力学方程表 Table of thermodynamic equations

==References==
参考文献

↑ ^1.0 ^1.1 Guggenheim, E.A. (1985). Thermodynamics. An Advanced Treatment for Chemists and Physicists, seventh edition, North Holland, Amsterdam,

.

↑ Kittel, C. Kroemer, H. (1980). Thermal Physics, second edition, W.H. Freeman, San Francisco,

.

↑ Adkins, C.J. (1968). Equilibrium Thermodynamics, McGraw-Hill, London,

.

↑ Lebon, G., Jou, D., Casas-Vázquez, J. (2008). Understanding Non-equilibrium Thermodynamics. Foundations, Applications, Frontiers, Springer, Berlin,

.

↑ Chris Vuille; Serway, Raymond A.; Faughn, Jerry S. (2009). College physics. Belmont, CA: Brooks/Cole, Cengage Learning. p. 355. ISBN 978-0-495-38693-3. https://books.google.com/books?id=CX0u0mIOZ44C&pg=PT355.
↑ Sommerfeld, A. (1951/1955). Thermodynamics and Statistical Mechanics, vol. 5 of Lectures on Theoretical Physics, edited by F. Bopp, J. Meixner, translated by J. Kestin, Academic Press, New York, p. 1.

↑ Serrin, J. (1978). The concepts of thermodynamics, in Contemporary Developments in Continuum Mechanics and Partial Differential Equations. Proceedings of the International Symposium on Continuum Mechanics and Partial Differential Equations, Rio de Janeiro, August 1977, edited by G.M. de La Penha, L.A.J. Medeiros, North-Holland, Amsterdam,

, pp. 411–51.

↑ Serrin, J. (1986). Chapter 1, 'An Outline of Thermodynamical Structure', pp. 3–32, in New Perspectives in Thermodynamics, edited by J. Serrin, Springer, Berlin,

.

↑ Adkins, C.J. (1968/1983). Equilibrium Thermodynamics, (first edition 1968), third edition 1983, Cambridge University Press,

, pp. 18–20.

↑ Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York,

, p. 26.

↑ Buchdahl, H.A. (1966), The Concepts of Classical Thermodynamics, Cambridge University Press, London, pp. 30, 34ff, 46f, 83.

↑ *Münster, A. (1970), Classical Thermodynamics, translated by E.S. Halberstadt, Wiley–Interscience, London,

, p. 22.

↑ Pippard, A.B. (1957/1966). Elements of Classical Thermodynamics for Advanced Students of Physics, original publication 1957, reprint 1966, Cambridge University Press, Cambridge, p. 10.
↑ Wilson, H.A. (1966). Thermodynamics and Statistical Mechanics, Cambridge University Press, London, pp. 4, 8, 68, 86, 97, 311.

↑ Ben-Naim, A. (2008). A Farewell to Entropy: Statistical Thermodynamics Based on Information, World Scientific, New Jersey,

.

External links

In Our Time: Perpetual Motion, BBC discussion about the Laws, with Ruth Gregory, Frank Close and Steven Bramwell, hosted by Melvyn Bragg, first broadcast 24 September 2015.

Category:Scientific laws

类别: 科学定律

This page was moved from wikipedia:en:Laws of thermodynamics. Its edit history can be viewed at 热力学定律/edithistory

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[Guggenheim_1985-1] 1.0 ^1.1 Guggenheim, E.A. (1985). Thermodynamics. An Advanced Treatment for Chemists and Physicists, seventh edition, North Holland, Amsterdam,
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[Kittel_and_Kroemer_1980-2] Kittel, C. Kroemer, H. (1980). Thermal Physics, second edition, W.H. Freeman, San Francisco,
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[Adkins_1968-3] Adkins, C.J. (1968). Equilibrium Thermodynamics, McGraw-Hill, London,
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[LJCV_2008-4] Lebon, G., Jou, D., Casas-Vázquez, J. (2008). Understanding Non-equilibrium Thermodynamics. Foundations, Applications, Frontiers, Springer, Berlin,
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[5] Chris Vuille; Serway, Raymond A.; Faughn, Jerry S. (2009). College physics. Belmont, CA: Brooks/Cole, Cengage Learning. p. 355. ISBN 978-0-495-38693-3. https://books.google.com/books?id=CX0u0mIOZ44C&pg=PT355.

[6] Sommerfeld, A. (1951/1955). Thermodynamics and Statistical Mechanics, vol. 5 of Lectures on Theoretical Physics, edited by F. Bopp, J. Meixner, translated by J. Kestin, Academic Press, New York, p. 1.

[7] Serrin, J. (1978). The concepts of thermodynamics, in Contemporary Developments in Continuum Mechanics and Partial Differential Equations. Proceedings of the International Symposium on Continuum Mechanics and Partial Differential Equations, Rio de Janeiro, August 1977, edited by G.M. de La Penha, L.A.J. Medeiros, North-Holland, Amsterdam,
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, pp. 411–51.

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[8] Serrin, J. (1986). Chapter 1, 'An Outline of Thermodynamical Structure', pp. 3–32, in New Perspectives in Thermodynamics, edited by J. Serrin, Springer, Berlin,
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[9] Adkins, C.J. (1968/1983). Equilibrium Thermodynamics, (first edition 1968), third edition 1983, Cambridge University Press,
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[10] Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York,
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[11] Buchdahl, H.A. (1966), The Concepts of Classical Thermodynamics, Cambridge University Press, London, pp. 30, 34ff, 46f, 83.

[12] *Münster, A. (1970), Classical Thermodynamics, translated by E.S. Halberstadt, Wiley–Interscience, London,
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