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电解质溶液渗透系数理论在水分活度等物理化学特性量计量中的应用

王海峰 李佳

王海峰,李佳. 电解质溶液渗透系数理论在水分活度等物理化学特性量计量中的应用[J]. 计量科学与技术,待出版. doi: 10.12338/j.issn.2096-9015.2024.0191
引用本文: 王海峰,李佳. 电解质溶液渗透系数理论在水分活度等物理化学特性量计量中的应用[J]. 计量科学与技术,待出版. doi: 10.12338/j.issn.2096-9015.2024.0191
WANG Haifeng, LI Jia. Application of Osmotic Coefficient Theory of Electrolyte in Metrology of Physical Chemistry Quantities Including Water Activity[J]. Metrology Science and Technology. doi: 10.12338/j.issn.2096-9015.2024.0191
Citation: WANG Haifeng, LI Jia. Application of Osmotic Coefficient Theory of Electrolyte in Metrology of Physical Chemistry Quantities Including Water Activity[J]. Metrology Science and Technology. doi: 10.12338/j.issn.2096-9015.2024.0191

电解质溶液渗透系数理论在水分活度等物理化学特性量计量中的应用

doi: 10.12338/j.issn.2096-9015.2024.0191
基金项目: 中国计量科学研究院自筹基本业务经费(AKYZZ2331-23)。
详细信息
    作者简介:

    王海峰(1978-),中国计量科学研究院副研究员,研究方向:水分和有机元素计量技术,邮箱:wanghf@nim.ac.cn

Application of Osmotic Coefficient Theory of Electrolyte in Metrology of Physical Chemistry Quantities Including Water Activity

  • 摘要: 渗透系数(ϕ)反映了电解质溶液中溶剂偏离理想溶液的程度。渗透系数可采用蒸气压法和电动势法等多种方法测定。美国国家标准局统计了已发表的数据,以每种电解质溶液的多套科学数据的平均值,作为该电解质溶液的渗透系数的标准值,并给出了渗透系数的标准偏差。该渗透系数的标准数据以德拜-休克尔公式的形式表达,方便使用者代入电解质溶液的质量摩尔浓度计算对应的渗透系数。渗透系数可用于计算电解质溶液的水分活度、冰点和渗透压摩尔浓度,从而为相关特性量标准溶液定值,分别用于校准相关特性量的测量仪器。在众多的电解质中,最常用的是氯化钠。国际标准和国家标准规定的上述特性量的标准值,和根据渗透系数标准数据计算得到的结果一致性良好。根据渗透系数标准数据计算相关特性量的标准值,能够通过渗透系数标准数据间接地溯源至蒸气压和电动势等量值的SI单位。
  • 表  1  NaCl渗透系数原始数据的来源

    Table  1.   Source of the data of osmotic coefficient of NaCl

    编号测量方法作者年代
    1电势法Allmand, Polack[2]1919
    2电势法Harned[3]1929
    3电势法Harned, Nims[4]1932
    4电势法Brown, MacInnes[5]1935
    5电势法Sakong, Huang1962
    6电势法Lebed, Aleksandrov1964
    7电势法Wilke, Schrӓnkler1932
    8电势法Janz, Gordon[6]1943
    9电势法Caramazza1960
    10电势法Getman[7]1920
    11电势法Haas, Jellinek1932
    12双温法Stokes[8]1947
    13扩散法Harned[9]1959
    14蒸气压法Negus1922
    15蒸气压法Pearce, Nelson[10]1932
    16蒸气压法Olynyk, Gordon[11]1943
    17蒸气压法Petit[12]1965
    18露点法Hepburn[13]1928
    19等压法Robinson, Sinclair[14]1934
    20等压法Scatchard, Hamer[15]1938
    21等压法Robinson[16]1939
    22等压法Janis, Ferguson[17]1939
    23等压法Robinson[18]1945
    下载: 导出CSV

    表  2  NaCl溶液水分活度的计算值

    Table  2.   Calculated value of water activity of NaCl aqueous solution

    质量摩尔浓度
    (mol/kg)
    质量
    百分数
    ISO 21807推荐
    的水分活度[19]
    ϕ标准
    数据
    根据ϕ标准
    数据计算得到的
    水分活度
    0.1 0.58% 0.9966 0.933 0.9966
    0.2 1.15% 0.9934 0.924 0.9934
    0.3 1.72% 0.9900 0.921 0.9901
    0.4 2.28% 0.9868 0.921 0.9868
    0.5 2.84% 0.9835 0.922 0.9835
    0.6 3.39% 0.9802 0.923 0.9802
    0.7 3.93% 0.9769 0.926 0.9769
    0.8 4.47% 0.9736 0.929 0.9736
    0.9 5.00% 0.9702 0.932 0.9702
    1.0 5.52% 0.9669 0.936 0.9668
    1.2 6.55% 0.9601 0.944 0.9600
    1.4 7.56% 0.9532 0.953 0.9531
    1.6 8.55% 0.9461 0.963 0.9460
    1.8 9.52% 0.9389 0.973 0.9388
    2.0 10.46% 0.9316 0.984 0.9315
    2.2 11.39% 0.9242 0.995 0.9241
    2.4 12.30% 0.9166 1.007 0.9166
    2.6 13.19% 0.9089 1.020 0.9089
    2.8 14.06% 0.9011 1.032 0.9011
    3.0 14.92% 0.8932 1.046 0.8931
    3.2 15.75% 0.8851 1.059 0.8851
    3.4 16.58% 0.8769 1.073 0.8768
    3.6 17.38% 0.8686 1.087 0.8685
    3.8 18.17% 0.8600 1.101 0.8600
    4.0 18.95% 0.8515 1.116 0.8514
    5.0 22.61% 0.8068 1.192 0.8068
    6.0 25.97% 0.7598 1.270 0.7599
    下载: 导出CSV

    表  3  不饱和盐溶液的溶质、浓度、渗透系数和水分活度

    Table  3.   Solute, concentration, osmotic coefficient and water activity of unsaturated solution of salts

    溶质质量摩尔浓度(mol/kg)渗透系数水分活度
    LiCl13.4812.8510.250
    LiCl8.5332.2510.500
    NaCl5.9531.2660.762
    NaCl5.2091.2080.797
    NaCl4.0291.1180.850
    NaCl2.8251.0340.900
    NaCl1.4870.9570.950
    下载: 导出CSV

    表  4  NaCl溶液的质量分数、质量摩尔浓度和冰点下降值

    Table  4.   Mass fraction, molality and freezing point depression of NaCl solution

    质量摩尔浓度
    (mol/kg)
    质量
    百分数
    GB5413.38
    规定的冰点[22]
    (mK)
    ϕ标准
    数据
    根据ϕ标准数据
    计算得到的冰点
    (mK)
    0.1165 0.676% 400 0.9305 403
    0.1189 0.690% 408 0.9302 411
    0.1315 0.763% 450 0.9288 454
    0.1465 0.849% 500 0.9274 505
    0.1495 0.866% 510 0.9271 515
    0.1501 0.870% 512 0.9270 517
    0.1525 0.884% 520 0.9268 525
    0.1555 0.901% 530 0.9266 536
    0.1585 0.918% 540 0.9264 546
    0.1616 0.935% 550 0.9261 556
    0.1637 0.948% 557 0.9260 563
    0.1767 1.022% 600 0.9251 607
    下载: 导出CSV

    表  5  NaCl溶液的质量摩尔浓度、质量分数和渗透压摩尔浓度

    Table  5.   Molality, mass fraction and Osmolality of NaCl solution

    1kg溶剂所含的NaCl
    质量(g/kg)
    质量摩尔浓度
    (mol/kg)
    质量百分数 药典规定的渗透压摩尔
    浓度(mOsmol/kg)[22]
    ϕ标准数据 根据ϕ标准数据计算的渗透
    压摩尔浓度(mOsmol/kg)
    3.087 0.0528 0.3077% 100 0.9431 99.6
    6.260 0.1071 0.6221% 200 0.9318 199.6
    9.463 0.1619 0.9374% 300 0.9261 299.9
    12.684 0.2170 1.2525% 400 0.9229 400.6
    15.916 0.2723 1.5667% 500 0.9212 501.8
    19.147 0.3276 1.8787% 600 0.9204 603.1
    22.380 0.3829 2.1890% 700 0.9202 704.8
    下载: 导出CSV
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  • 收稿日期:  2024-06-15
  • 录用日期:  2024-07-08
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  • 网络出版日期:  2024-08-02

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