Vaporisation

The flash curve of a petroleum cut is defined as the curve that represents the temperature as a function of the volume fraction of vaporised liquid, the residual liquid being in equilibrium with the total vapor, at constant pressure. 

Using this mixture as an example, consider starting at pressure A and isothermally reducing the pressure to point D on the diagram. At point A the mixture exists entirely in the liquid phase. When the pressure drops to point B, the first bubble of gas is evolved, and this will be a bubble of the lighter component, ethane. As the pressure continues to drop, the gas phase will acquire more of the heavier component and hence the liquid volume decreases. At point C, the last drop of liquid remaining will be composed of the heavier component, which itself will vaporise as the dew point is crossed, so that below... 

The diagram (Fig. 5.21) shows that as the pressure is reduced below the dew point, the volume of liquid in the two phase mixture initially increases. This contradicts the common observation of the fraction of liquids in a volatile mixture reducing as the pressure is dropped (vaporisation), and explains why the fluids are sometimes referred to as retrograde gas condensates. 

A volatile oil contains a relatively large fraction of lighter and intermediate oomponents which vaporise easily. With a small drop in pressure below the bubble point, the relative amount of liquid to gas in the two-phase mixture drops rapidly, as shown in the phase diagram by the wide spacing of the iso-vol lines. At reservoir pressures below the bubble point, gas is released In the reservoir, and Is known as solution gas, since above the bubble point this gas was contained in solution. Some of this liberated gas will flow towards the producing wells, while some will remain in the reservoir and migrate towards the crest of the structure to form a secondary gas cap. 

In such a plant the gas stream passes through a series of fractionating columns in which liquids are heated at the bottom and partly vaporised, and gases are cooled and condensed at the top of the column. Gas flows up the column and liquid flows down through the column, coming into close contact at trays in the column. Lighter components are stripped to the top and heavier products stripped to the bottom of the tower. 

There are many compounds in existence which have a considerable positive enthalpy of formation. They are not made by direct union of the constituent elements in their standard states, but by some process in which the necessary energy is provided indirectly. Many known covalent hydrides (Chapter 5) are made by indirect methods (for example from other hydrides) or by supplying energy (in the form of heat or an electric discharge) to the direct reaction to dissociate the hydrogen molecules and also possibly vaporise the other element. Other known endothermic compounds include nitrogen oxide and ethyne (acetylene) all these compounds have considerable kinetic stability. 

The fact that water is a liquid at room temperature with high enthalpies of fusion and vaporisation can be attributed to hydrogen bond formation. The water molecule is shown in Figure 10.3. 

Solid cadmium(II) iodide Cdlj has a layer lattice —a structure intermediate between one containing Cd " and P ions and one containing Cdl2 molecules—and this on vaporisation gives linear, covalent I—Cd—I molecules. In solution, iodo-complexes exist, for example... 

The basin A is then gently heated by a small Bunsen flame, which should be carefully protected from side draughts by screens, so that the material in A receives a steady uniform supply of heat. The material vaporises, and the vapour passes up through the holes into the cold funnel C. Here it cools and condenses as fine crystals on the upper surface of the paper B and on the walls of C. When almost the whole of the material in A has vaporised, the heating is stopped and the pure sublimed material collected. In using such an apparatus, it is clearly necessary to adjust the supply of heat so that the crude material in A is being steadily vaporised, while the funnel C does not become more than luke warm. 

Hydrolysis of Benzanilide. For this hydrolysis, it is necessary to use 70% sulphuric acid (see Hydrolysis of Acetanilide, p. 108). Add I g. of benzanilide to 10 ml. of 70% sulphuric acid, and boil the mixture gently in a small flask under a reflux water-condenser for 30 minutes. Hydrolysis will now be complete, but much of the benzoic acid will have vaporised in the steam and then solidified in the conden-... 

There is a tendency for the water produced by the combustion to condense in the narrow neck of the combustion tube, instead of passing right over into the absorption tube. To avoid this, two movable copper hooks Q are mounted on a copper rod, which can slide in and out of a hole cut in the mortar P these may be placed over the beak of the combustion tube and conduct sufficient heat from the mortar to vaporise the water once again so that it is driven over by the Oxygen stream into the absorption tube R. 

The vapour pressure of a liquid increases with rising temperature. A few typical vapour pressure curves are collected in Fig. 7,1, 1. When the vapour pressure becomes equal to the total pressure exerted on the surface of a liquid, the liquid boils, i.e., the liquid is vaporised by bubbles formed within the liquid. When the vapour pressure of the liquid is the same as the external pressure to which the liquid is subjected, the temperature does not, as a rale, rise further. If the supply of heat is increased, the rate at which bubbles are formed is increased and the heat of vaporisation is absorbed. The boiling point of a liquid may be defined as the temperature at which the vapour pressure of the liquid is equal to the external pressure dxerted at any point upon the liquid surface. This external pressure may be exerted by atmospheric air, by other gases, by vapour and air, etc. The boiling point at a pressure of 760 mm. of mercury, or one standard atmosphere, may be termed the normal boiling point. 

The processes of distillation and sublimation are closely related. There are three ways in which the vaporisation of a thermally stable substance may take place on heating —... 

The term distillation is applied to vaporisation and subsequent condensation according to (i) it should also be applied to (ii) since it is really the liquid which is converted into vapour and is first formed by condensation. Strictly speaking, the term sublimation should be applied to changes according to (iii). However, in practice, a substance when heated may first melt and then boil, but on cooling it may pass directly from the vapour to the solid the process is then also called sublimation. Indeed the mode of vaporisation, whether directly from solid to vapour or through the intermediate formation of a liquid, is of secondary importance it is the direct conversion of vapour to solid which is really the outstanding feature of sublimation in the laboratory. 

The large heat of vaporisation of water can reduce the economic feasibility of water in industrial processes. 

However, some semiaromatic nylons can give problems as a result of the high melt viscosity. A process for produciag polymers of hexamethylenediamine, adipic acid, terephthaUc acid, and isophthaUc acid has been developed, which iavolves vaporising the salt mixture ia a high temperature flash reactor followed by molecular weight iacrease ia a twia-screw extmder with efficient moisture removal (17). 

H. Lennartz and co-workers. Vaporisation Equilibrium of the Water—Sulfuric Acid System, Rep. Fur. 6783, Commission of European Communities, Hydrogen Energy Vector, Europe, 1980, pp. 60—70. 

Rapid heating of either borax decahydrate or pentahydrate causes the crystal to dissolve before significant dehydration, and at about 140°C, puffing occurs from rapid vaporisation of water to form particles having as high as 90% void volume and very low bulk density (78). 

Vapor decomposition (14,15) iavolves dryiag, decomposiag, and vaporising a spray of salt precursor solution ia a plasma, and subsequentiy nucleating and growing ceramic particles ia the vapor. Silicon carbide [12504-67-5] SiC, powder is produced by this method. 

At 70—140°C, peroxide is vaporised. Peroxide vapor has been reported to rapidly inactivate pathogenic bacteria, yeast, and bacterial spores in very low concentrations (133). Experiments using peroxide vapor for space decontamination of rooms and biologic safety cabinets hold promise (134). The use of peroxide vapor and a plasma generated by radio frequency energy releasing free radicals, ions, excited atoms, and excited molecules in a sterilising chamber has been patented (135). 

Types of columns and packings. A slow distillation rate is necessary to ensure that equilibrium conditions operate and also that the vapour does not become superheated so that the temperature rises above the boiling point. Efficiency is improved if the column is heat insulated (either by vacuum jacketing or by lagging) and, if necessary, heated to Just below the boiling point of the most volatile component. Efficiency of separation also improves with increase in the heat of vaporisation of the liquids concerned (because fractionation depends on heat equilibration at multiple liquid-gas boundaries). Water and alcohols are more easily purified by distillation for this reason. 

The behaviour at constant p is given by a horizontai cut through the diagram. The soiid melts at T, and vaporises at T . The phase diagram at constant pressure is a iine (shown on the right) aiong which the span of stabiiity of each phase is marked, as... 

The solubility parameter is thus an experimentally determinable property although special methods are necessary with polymers, which cannot normally be vaporised without decomposition. Such methods are discussed in Section 5.3.3. 

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