Melting point effects

Reagent A is particularly useful for the treatment of the lower aliphatic aldehydes and ketones which are soluble in water cf. acetaldehyde, p. 342 acetone, p. 346). The Recent is a very dilute solution of the dinitrophenylhydrazine, and therefore is used more to detect the presence of a carbonyl group in a compound than to isolate sufficient of the hydrazone for effective recrystallisation and melting-point determination. 

Effect of impurities upon the melting point. Let us take a specific example and examine the effect of the addition of a small quantity of naphthalene to an equilibrium mixture of pure solid and liquid a-naphthol at the temperature of the true melting point (95 5°) at atmospheric pressure. 

The bulkiness of the substituent groups increases moving down Table 4.2. Also moving down the table, the melting points decrease, pass through a minimum, and then increase again. As is often the case with reversals of trends such as this, there are two different effects working in opposition in these data ... 

The attitude we adopt in this discussion is that only those chain segments in the middle of the chain possess sufficient regularity to crystallize. Hence we picture crystallization occurring from a mixture in which the concentration of crystallizable units is Xj and the concentration of solute or diluent is Xg. The effect of solute on the freezing (melting) point of a solvent is a well-known result T j, is lowered. Standard thermodynamic analysis yields the relationship... 

To erase information by the transition amorphous — crystalline, the amorphous phase of the selected area must be crystallized by annealing. This is effected by illumination with a low power laser beam (6—15 mW, compared to 15—50 mW for writing/melting), thus crystallizing the area. This crystallization temperature is above the glass-transition point, but below the melting point of the material concerned (Eig. 15, Erase). 

Evaporation Retardants. Small molecule solvents that make up the most effective paint removers also have high vapor pressure and evaporate easily, sometimes before the remover has time to penetrate the finish. Low vapor pressure cosolvents are added to help reduce evaporation. The best approach has been to add a low melting point paraffin wax (mp = 46-57° C) to the paint remover formulation. When evaporation occurs the solvent is chilled and the wax is shocked-out forming a film on the surface of the remover that acts as a barrier to evaporation (5,6). The addition of certain esters enhances the effectiveness of the wax film. It is important not to break the wax film with excessive bmshing or scraping until the remover has penetrated and lifted the finish from the substrate. Likewise, it is important that the remover be used at warm temperatures, since at cool temperatures the wax film may not form, or if it does it will be brittle and fracture. Rapid evaporation occurs when the wax film is absent or broken. 

The decomposition kinetics of an organic peroxide, as judged by 10-h HLT, largely determines the suitabiUty of a particular peroxide initiator in an end use appHcation (22). Other important factors ate melting point, solubiUty, cost, safety, efficiency, necessity for refrigerated storage and shipment, compatibihty with production systems, effects on the finished product, and potential for activation. 

---