Hydrophobic Interactions by Arieh Y. Ben-Naim

By Arieh Y. Ben-Naim

My own involvement with the matter of hydrophobic interactions (HI) all started approximately ten years in the past. at the moment i used to be requested to put in writing a assessment article at the houses of aqueous ideas of nonpolar solutes. whereas surveying the literature in this topic i discovered quite a few discussions of the idea that of hello. My curiosity in those interactions elevated in particular after interpreting the now classical evaluate of W. Kauzmann (1959), during which the significance of the hello to biochemical methods is under pressure. but, even with having learn particularly commonly at the a number of elements of the topic, I received just a very imprecise inspiration of what humans really had in brain while relating hello. in reality, it grew to become really transparent that the time period hello used to be utilized through assorted authors to explain and interpret really various phenomena taking place in aqueous suggestions. therefore, even the main basic query of the very definition of the concept that of hello remained unanswered. yet different questions undefined, e. g. : Are hello relatively a good­ confirmed experimental truth? Is there any relation among hello and the atypical houses of water? Is the phenomenon really unusual to aqueous options? ultimately, possibly the main the most important query I sought to reply to was once even if there exists tough facts that hello are relatively very important -as usually claimed-in organic processes.

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6 Very Dilute SalutioRs anEi Hy"rf),filtlelitic mteractieFl 41 have given a secoRd interpretation in terms of the difference in the couplisg work of S in the two phases, this cannot be done for iJt-t~;. 33) that iJt-t~; contains, in addition to W(S I E) - W(S I W), a term that depends on the densities of the pure solvents. Clearly the expression for iJt-t~rQ is simpler than that for iJt-t~;. But simplicity, although an important feature of iJt-t~rQ, cannot be used as the sol~ argument for favoring this particular standard quantity.

6 Chapter 2 of the biopolymer interacts with very few other groups that happen to be around it. 4(b) must also be chosen to have a similar low density of molecules. In the limit of very low density, the free energy of interaction of the darkened group with its surroundings must tend to zero. E -+ O. 35) which is certainly inconsistent with our expectation. This is a very fundamental difference between the two standard quantities. t Thus L1,u~rQ is the simplest quantity that conveys information on the solvation free energy of the solute in the two solvents.

The standard free energy of solution of a hard-sphere particle in any solvent is equal to the negative of the HI between two such hard spheres at zero separation. 3. 2. STANDARD FREE ENERGIES OF TRANSFER Consider the following experimental situation: pure water Wand pure ethanol E, at the same temperature and pressure, are separated by a partition that is permeable to a solute S only. 2) so that flSOlV and flsoE are independent of the solute densities (lsTr and esE, respectively. 5) Llfl~r(E ---+ W) = W(S I W) - W(S I E) Clearly if one phase is a rare gas (or vacuum) then W(S I G) = 0 (no coupling work) and the standard free energy of transfer turns into a standard free energy of solution, which in our notation will be written as Llfl~r(G ---+ E) or Llfl~r(G ---+ W).

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