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Solutions of liquids in liquids

We know that some liquids mix with each other in all proportions; in other words, they have infinite mutual solubility and are said to be miscible    . Ethanol, sulfuric acid, and ethylene glycol (popular for use as antifreeze, pictured in [link] ) are examples of liquids that are completely miscible with water. Two-cycle motor oil is miscible with gasoline.

This is a photo of a 1 gallon yellow plastic jug of Preston 50/50 Prediluted Antifreeze/Coolant.
Water and antifreeze are miscible; mixtures of the two are homogeneous in all proportions. (credit: “dno1967”/Wikimedia commons)

Liquids that mix with water in all proportions are usually polar substances or substances that form hydrogen bonds. For such liquids, the dipole-dipole attractions (or hydrogen bonding) of the solute molecules with the solvent molecules are at least as strong as those between molecules in the pure solute or in the pure solvent. Hence, the two kinds of molecules mix easily. Likewise, nonpolar liquids are miscible with each other because there is no appreciable difference in the strengths of solute-solute, solvent-solvent, and solute-solvent intermolecular attractions. The solubility of polar molecules in polar solvents and of nonpolar molecules in nonpolar solvents is, again, an illustration of the chemical axiom “like dissolves like.”

Two liquids that do not mix to an appreciable extent are called immiscible    . Layers are formed when we pour immiscible liquids into the same container. Gasoline, oil ( [link] ), benzene, carbon tetrachloride, some paints, and many other nonpolar liquids are immiscible with water. The attraction between the molecules of such nonpolar liquids and polar water molecules is ineffectively weak. The only strong attractions in such a mixture are between the water molecules, so they effectively squeeze out the molecules of the nonpolar liquid. The distinction between immiscibility and miscibility is really one of degrees, so that miscible liquids are of infinite mutual solubility, while liquids said to be immiscible are of very low (though not zero) mutual solubility.

This is a photo of a clear, colorless martini glass containing a golden colored liquid layer resting on top of a clear, colorless liquid.
Water and oil are immiscible. Mixtures of these two substances will form two separate layers with the less dense oil floating on top of the water. (credit: “Yortw”/Flickr)

Two liquids, such as bromine and water, that are of moderate mutual solubility are said to be partially miscible    . Two partially miscible liquids usually form two layers when mixed. In the case of the bromine and water mixture, the upper layer is water, saturated with bromine, and the lower layer is bromine saturated with water. Since bromine is nonpolar, and, thus, not very soluble in water, the water layer is only slightly discolored by the bright orange bromine dissolved in it. Since the solubility of water in bromine is very low, there is no noticeable effect on the dark color of the bromine layer ( [link] ).

This figure shows three test tubes. The first test tube holds a dark orange-brown substance. The second test tube holds a clear substance. The amount of substance in both test tubes is the same. The third test tube holds a dark orange-brown substance on the bottom with a lighter orange substance on top. The amount of substance in the third test tube is almost double of the first two.
Bromine (the deep orange liquid on the left) and water (the clear liquid in the middle) are partially miscible. The top layer in the mixture on the right is a saturated solution of bromine in water; the bottom layer is a saturated solution of water in bromine. (credit: Paul Flowers)

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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