Further aspects of the physical chemistry of some non‐ionic detergents *
Further aspects of the physical chemistry of some non‐ionic detergents *
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一些非离子洗涤剂物理化学的其他方面 *
DOI：
10.1111/j.2042-7158.1965.tb07632.x
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发表时间：
1965
期刊：
影响因子：
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通讯作者：
C. B. Macfarlane
中科院分区：
文献类型：
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作者：
P. Elworthy;C. B. Macfarlane
洗涤剂在溶液中最有趣的性质是它们的表面和胶束行为以及影响它们的因素。非离子洗涤剂的水溶液是胶体的，因此他们研究中应用的技术与胶体科学中通常使用的技术相似。现在已经被接受的是，具有足够大的聚氧乙烯链以产生疏水部分的水溶性的非离子洗涤剂分子在胶束中定位，其中疏水部分在内部，乙二醇链在外部。乙二醇链通过以某种方式捕获水分子来赋予水的溶解性(Goto，Sugano&Koizumi，1954；Ferguson，1955)。由于直到最近，还没有独立的方法来测量胶束的水溶液体积，因此被捕获的水的确切数量和实现这一结果的方法是推测的。氢离子、氢键和乙醚氧基周围或乙二醇结构内水分子的各种排列已被提出(Chwala&Martin，1937,1947；Wurzchmitt，1950；Trin Chieri，1952；Hsaio，Dunning&Lorenz，1956；Kehren&Rosch，1956；Rosch，1956；Bailey&Callard，1959；Schick，1963b)。根据粘度和胶束研究，Kushner&Hubbard(1954)估计，在Triton X 100(N10)的胶束中，每个聚氧乙烯链上有43个水分子。在这一数字中，他们认为有20个分子是通过氢键与乙醚氧合而保持的，其余的分子是物理上被链捕获的。Nakagawa&Inoue(1958)发现聚氧乙烯链的每个氧原子上的水合水分子数随着链长的增加而增加。其他工人(Karabinos，Hazdra&Ballun，1955；Karabinos&Metziger，1955；Kehren&Rosch，1956；Reich，1956；Rosch，1956；Boehmke&Heusch，1960)，使用粘度、旋光度和水合热的数据，给出了每醚1，2，3或4个水分子的氧气，具体取决于链长和相关工人。我们最近描述了一种基于蒸气压力测量来估计胶束水合的方法(Elworth&Macfarlane，1964)。洗涤剂凝胶和浓缩液上的蒸气压力作为洗涤剂浓度的函数进行测量，并通过适当的外推程序，确定溶液的浓度(在实验误差范围内)具有相同的表观
The most interesting properties of detergents in solution are their surface and micellar behaviour and the factors affecting this. Aqueous solutions of non-ionic detergents are colloidal, thus the techniques applied in their study have been similar to those generally used in colloid science. It has now been accepted that molecules of non-ionic detergents having a polyoxyethylene chain sufficiently large to produce water solubility of the hydrophobic moiety, orientate themselves in micelles with the hydrophobic moiety inside and the glycol chains outside. The glycol chain confers water solubility by trapping water molecules in some way (Goto, Sugano & Koizumi, 1954; Ferguson, 1955). The exact amount of water trapped and the means by which this is effected is conjectural as, until recently, no independent method of measuring the aqueous covolume of the micelle had been reported. Hydroxonium ions, hydrogen bonding and various arrangements of the water molecules around the ether oxygens or within the glycol structure have been suggested (Chwala & Martin, 1937, 1947; Wurzchmitt, 1950; Trinchieri, 1952; Hsaio, Dunning & Lorenz, 1956; Kehren & Rosch, 1956; Rosch, 1956; Bailey & Callard, 1959 ; Schick, 1963b). From viscosity and micellar studies, Kushner & Hubbard (1954) estimated that there were 43 molecules of water per polyoxyethylene chain in a micelle of Triton X 100 (nl0). Of this number, they suggested 20 molecules were held by hydrogen bonding to the ether oxygens, the rest being physically trapped by the chain. Nakagawa & Inoue (1958) showed the number of hydrating water molecules per oxygen atom of the polyoxyethylene chain increased with chain length. Other workers (Karabinos, Hazdra & Ballun, 1955; Karabinos & Metziger, 1955; Kehren & Rosch, 1956; Reich, 1956; Rosch, 1956; Boehmke & Heusch, 1960), using data from viscosity, polarimetry, and heat of hydration, have given 1, 2, 3 or 4 water molecules per ether oxygen, depending on the chain length and the workers concerned. We have recently described a method, based on vapour pressure measurements, of estimating the micellar hydration (Elworthy & Macfarlane, 1964). The vapour pressures over gels and concentrated solutions of detergents were measured as a function of detergent concentration and, by a suitable extrapolation procedure, the concentration determined at which the solution had (within experimental error), the same apparent