Solid–solid and solid–liquid equilibria in the n-alkanols family: C18H37OH–C20H41OH system
Abstract
C18H37OH–C20H41OH is an example of a binary system showing isopolymorphism. The two alkanols display the same polymorphic behaviour. At low temperatures, they crystallize into the same ordered form γ
(C2/c, Z = 8). On heating, γ transforms into the rotationally disordered form R′IV
(C2/m, Z = 4), at a few degrees below the melting point of the latter. However, in most mixed samples of this system a β form (P21/c, Z = 8), metastable in the two pure components, has also been observed at low temperatures. At high temperatures, the β form transforms into the R′II form (Rm, Z = 3). This R′II form is also metastable in the two pure components. The β form presents conformational defects, and molecules with all-trans conformation co-exist with molecules with CO-gt-conformation, in contrast, all the molecules in the γ form present all-trans conformation. In the R′II form the rotational disorder is more accentuated than in the R′IV form. The disorder of composition (molecular alloys) stabilizes over wide ranges of compositions the β
(disorder of conformation) and R′II
(disorder of rotation) forms. Five solid–solid domains ([γ + β], [β + R′II], [γ + R′II], [γ + R′IV] and [R′II + R′IV]) related by two peritectoid and eutectoid invariants, and two solid–liquid domains ([R′IV + L] and [R′II + L]) related by a eutectic and a peritectic invariant, are present. The [β + R′II] domain has a minimum. All these domains are observed for compositions rich in the two pure components. The experimental phase diagram data are fully supported by the thermodynamically calculated phase diagram. The R′II + liquid domain has a width of less than 1 K; therefore, and due to the large heat effect, the system's alloys are good candidates for the storage of thermal energy.