三乘积法则

三乘积法则triple product rule)是关于偏导数的一个恒等关系式,其表达式为:
:\left(\frac{\partial x}{\partial y}\right)_z\left(\frac{\partial y}{\partial z}\right)_x\left(\frac{\partial z}{\partial x}\right)_y = -1.
::注释:每一个变量可视作另外两个变量的函数。偏导数的下标表示在此变量为常数的条件下求导。

三乘积法则用于热力学关系式的推导。例如温度、压力和体积之间的关系满足:
:\left(\frac{\partial p}{\partial T}\right)_V\left(\frac{\partial V}{\partial p}\right)_T\left(\frac{\partial T}{\partial V}\right)_p = -1.

利用三乘积法则,可以将不易测量的关系用容易测得的物理量代替,如:
:\left(\frac{\partial x}{\partial y}\right)_z = - \frac{\left(\frac{\partial z}{\partial y}\right)_x}{\left(\frac{\partial z}{\partial x}\right)_y}。

推导
下面给出一个非正式的推导。设有函数f(x, y, z) = 0。若将z表示为xy的函数,则全微分dz等于

:dz = \left(\frac{\partial z}{\partial x}\right)_y dx + \left(\frac{\partial z}{\partial y}\right)_x dy

dz = 0的轨迹上,xy之间满足

:dy = \left(\frac{\partial y}{\partial x}\right)_z dx

于是将dz = 0带入上式,

:0 = \left(\frac{\partial z}{\partial x}\right)_y \, dx + \left(\frac{\partial z}{\partial y}\right)_x \left(\frac{\partial y}{\partial x}\right)_z \, dx

重排得

:\left(\frac{\partial z}{\partial x}\right)_y = -\left(\frac{\partial z}{\partial y}\right)_x \left(\frac{\partial y}{\partial x}\right)_z

将所有偏导数移到等式左边,

:\left(\frac{\partial x}{\partial y}\right)_z\left(\frac{\partial y}{\partial z}\right)_x\left(\frac{\partial z}{\partial x}\right)_y = -1

此证明假定了偏导数存在,以及全微分dz存在,偏导数不为零从而能取倒数。数学分析的正式证明能避免这些隐含假定。

参见

  • 全微分
  • 变量和标量的三重积

参考资料

  • Elliott, JR, and Lira, CT. Introductory Chemical Engineering Thermodynamics, 1st Ed., Prentice Hall PTR, 1999. p. 184.
  • Carter, Ashley H. Classical and Statistical Thermodynamics, Prentice Hall, 2001, p. 392.

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