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Explanation of Ionic Sequences in Various Phenomena. VIII. The Structure of Aqueous Urea and DMSO and Their Mechanism as Dispersing Agents

 

作者: StigR. Erlander,   R. Tobin,  

 

期刊: Journal of Macromolecular Science: Part A - Chemistry  (Taylor Available online 1968)
卷期: Volume 2, issue 8  

页码: 1521-1542

 

ISSN:0022-233X

 

年代: 1968

 

DOI:10.1080/10601326808051913

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Many recent experiments have shown that urea behaves as a zwitterion. By measuring the solubility of urea in various aqueous salt solutions and by obtaining the effect of salts on the dispersing power of urea, the structure of urea and its mechanism for destroying hydrogen and hydrophobic bonds were elucidated. The zwitterion structure of urea was confirmed by means of these ionic sequence studies. The K+ion increases the dispersion power of urea and decreases its solubility more than any of the other monovalent cations because the K+ion forms a more insoluble salt bond with the negatively charged oxygen atom of the urea zwitterion. This salt bond is more insoluble than the urea-urea bond. Hence, more positively charged -NH2groups on urea are liberated by the addition of KCl. The dispersion power of the urea molecule is the result of the interaction of the negatively hydrated domain (B regions) surrounding these -NH2groups with the oxygen atoms involved in the hydrogen bonds between starch molecules. These B regions on urea -NH2 groups are more effective in destroying hydrogen bonds than normal water molecules. That is, the anionic sequences and the solubility of benzene in aqueous urea solutions show that the hydrated -NH2 groups of urea have an effective dielectric constant that is greater than that of water and is approximately equal to that of the hydrated guanidinium ion. However, the urea-urea salt complexes or polymers lower the effectiveness of urea at high urea concentrations. The charge density of the urea anion is between that of the C1- and F- anions and consequently does not contribute to the dispersing power of urea. By destroying water clusters, the -NH, groups of urea increase the domain which hydrocarbons can occupy and hence destroy hydrophobic bonds. The destruction of hydrogen and hydrophobic bonds by urea therefore involves the electrostatic interactions between the urea B regions and the surrounding hydrogen bonds. It is also shown that DMSO behaves as a stronger zwitterion than urea and that it has the properties of a small anionic detergent. Anhydrous DMSO dissolves polar polymers and molecules by complexing its strongly ionized oxygen atom with the polar group. Urea and formamide form aggregates with themselves and therefore are incapable of dispersing polymers in this manner.

 

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