USP37 791 pH值测定法 (双语版)
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<791> pH
<791> pH值测定法
For compendial purposes, pH is defined as the value given by a suitable,
properly standardized, potentiometric instrument (pH meter) capable of
reproducing pH values to 0.02 pH unit using an indicator electrode sensitive to
hydrogen-ion activity, the glass electrode, and a suitable reference electrode.
The instrument should be capable of sensing the potential across the electrode
pair and, for pH standardization purposes, applying an adjustable potential to
the circuit by manipulation of “standardization,” “zero,” “asymmetry,” or
“calibration” control, and should be able to control the change in millivolts per
unit change in pH reading through a “temperature” and/or “slope” control.
Measurements are made at 25 ± 2º, unless otherwise specified in the
individual monograph or herein.
按照药典要求，pH值系至采用合适的完全标准化的电位测量仪器（pH计）测得的结果。pH计由对氢离子活度灵敏的指示电极，玻璃电极以及合适的参比电极组成，从而产生以0.02pH单位的pH值。作为pH值标准校验目的时，pH计应能够感应通过电极对的电动势，通过控制“标准校验”“归零” “不对称”或“校准”使可调的电势应用于电路，并能够通过“温度”和/或“斜率”来控制每个单位毫伏数的变化。除正文项下或此项中另有规定外，在（25±2）℃条件下测量。
The pH scale is defined by the equation:
pH = pHs + (E – ES)/k
in which E and ES are the measured potentials where the galvanic cell contains
the solution under test, represented by pH, and the appropriate Buffer Solution
for Standardization, represented by pHs, respectively. The value of k is the
change in potential per unit change in pH and is theoretically [0.05916 +
0.000198(t – 25º)] volts at any temperature t.
按下式确定pH值。
pH = pHs ＋ (E－Es)/k
式中，E和Es分别为待测溶液（pH）和标准缓冲液（pHs）的电动势；k值是每pH单位变化的电势差，在任何温度t条件下理论值均为［0.05916＋0.000198（t－25℃）］V。
It should be emphasized that the definitions of pH, the pH scale, and the values
assigned to the Buffer Solutions for Standardization are for the purpose of
establishing a practical, operational system so that results may be compared
between laboratories. The pH values thus measured do not correspond exactly
to those obtained by the definition, pH = – log aH+. So long as the solution
being measured is sufficiently similar in composition to the buffer used for
standardization, the operational pH corresponds fairly closely to the theoretical
pH. Although no claim is made with respect to the suitability of the system for
measuring hydrogen-ion activity or concentration, the values obtained are
closely related to the activity of the hydrogen-ion in aqueous solutions.
必须强调，pH值的定义、pH计的刻度以及标准缓冲液的赋值，旨在建立一个实用的、可操作的体系，以便于各实验室的数据具有可比性。尽管测得的pH值不能精确的与其定义的数值（pH=－lgaH+,及理论值）完全一致，只要待测溶液与标准缓冲液的组成足够相似，实测pH值将非常接近于理论值。虽然没有说明测定氢离子活度或浓度的系统适用性，但测得的值非常接近于水溶液中实际的氢离子活度。
Where a pH meter is standardized by use of an aqueous buffer and then used
to measure the “pH” of a nonaqueous solution or suspension, the ionization
constant of the acid or base, the dielectric constant of the medium, the
liquid-junction potential (which may give rise to errors of approximately 1 pH
unit), and the hydrogen-ion response of the glass electrode are all changed.
For these reasons, the values so obtained with solutions that are only partially
aqueous in character can be regarded only as apparent pH values.
当pH计采用以水配制的缓冲溶液进行校准，用于测定非水溶液或混悬液的“pH”
时，酸或碱的离子化常数、溶剂的介电常数、液接电势（可能会产生1个pH单位的误差）和玻璃电极的氢离子响应均会发生变化。因此，对具有部分水溶液特性的待测溶液测得的是表现pH值。
BUFFER SOLUTIONS FOR STANDARDIZATION OF THE PH METER
pH计较正用标准缓冲液
Buffer Solutions for Standardization are to be prepared as directed in the
accompanying table.* Buffer salts of requisite purity can be obtained from the
National Institute of Science and Technology. Solutions may be stored in hard
glass or polyethylene bottles fitted with a tight closure or carbon
dioxide-absorbing tube (soda lime). Fresh solutions should be prepared at
intervals not to exceed 3 months using carbon dioxide-free water. The table
indicates the pH of the buffer solutions as a function of temperature. The
instructions presented here are for the preparation of solutions having the
designated molal (m) concentrations. For convenience, and to facilitate their
preparation, however, instructions are given in terms of dilution to a 1000-mL
volume rather than specifying the use of 1000 g of solvent, which is the basis
of the molality system of solution concentration. The indicated quantities
cannot be computed simply without additional information.
校正用标准缓冲液的制备见附表*，缓冲盐所要求的纯度可从国家科学技术研究所（National Institute of Science and Technology）中获得。溶液需贮存在紧
* Commercially available buffer solutions for pH meter standardization, standardized by
methods traceable to the National Institute of Standards and Technology (NIST), labeled with a
pH value accurate to 0.01 pH unit may be used. For standardization solutions having a pH
