Solubility Parameters: Theory and ApplicationJohn Burke
A scheme to overcome the inconsistencies caused by hydrogen bonding was proposed by Harry Burrell in 1955. This simple solution divides the solvent spectrum into three separate lists: one for solvents with poor hydrogen bonding capability, one for solvents with moderate hydrogen bonding capability, and a third for solvents with strong hydrogen bonding capability, on the assumption that solubility is greatest between materials with similar polarities. This system of classification is quite successful in predicting solvent behavior, and is still widely used in practical applications. The classification according to Burrell may be briefly summarized as follows:
hydrocarbons, chlorinated hydrocarbons, and nitrohydrocarbons.
ketones, esters, ethers, and glycol monoethers
alcohols, amines, acids, amides, and aldehydes
Later systems assign specific values to hydrogen bonding capacity, and plot those values against Hildebrand values on a two dimensional graph. Although hydrogen bonding values are generally determined using IR spectroscopy (by measuring the frequency shift a particular solvent causes in deuterated methanol), another interesting method uses the speed of sound through paper that has been wet with the solvent being tested. Since paper fibers are held together largely by hydrogen bonds, the presence of a liquid capable of hydrogen bonding will disrupt the fiber-fiber bonds in preference to fiber-liquid bonds. This disruption of paper fiber bonding will decrease the velocity of sound travelling through the sheet. Water, capable of a high degree of hydrogen bonding, is used as a reference standard, and the hydrogen bonding value of a liquid is the ratio of its sonic disruption relative to water. In this test, alkanes have no effect on fiber hydrogen bonding, giving the same sonic velocities as air dried paper.
Hydrogen bonding is a type of electron donor-acceptor interaction and can be described in terms of Lewis acid-base reactions. For this reason other systems have attempted the classification of solvents according to their electron donating or accepting capability. Such extensions of the Hildebrand parameter to include acidity-basicity scales, and ultimately ionic systems, are relatively recent and outside the scope of this paper.
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