Vaporization enthalpy change

Although we have focused so far primarily on the thermal energy effects resulting from chemical reactions, many physical processes also involve the absorption or release of heat. Examples include phase transformations, such as the melting of ice or the condensation of water vapor. Enthalpy changes occur as well when a solute dissolves in a solvent or when a solntion is diluted. 

The stoichiometric flame temperature ( Tg ) is used to characterize the burning gas surrounding the droplets because combustion naturally predominates at a distance where the fastest burning mixture is produced. This mixture approximates to the stoichiometric composition. The selection of the droplet surface temperature BP is discussed below. The enthalpy change for vaporization AH is given by... 

For a gas, — Hm is the change in enthalpy as the gas at pressure, p, is expanded into a vacuum, For a liquid (or solid), - Hm is the enthalpy change as the liquid (or solid) is vaporized (or sublimed) into a vacuum. It has been called the ideal enthalpy of vaporization (or sublimation) since it represents the enthalpy change as the liquid (or solid) becomes an ideal gas. 

Sublimation is the direct conversion of a solid into its vapor. Frost disappears on a cold, dry morning as the ice sublimes directly into water vapor. Solid carbon dioxide also sublimes, which is why it is called dry ice. Each winter on Mars, solid carbon dioxide is deposited as polar frost, which sublimes when the feeble summer arrives (Fig. 6.24). The enthalpy of sublimation, AHsub, is the molar enthalpy change when a solid sublimes ... 

FIGURE 6.28 The enthalpy changes for the reactions in which 1 mol CH4(g) burns to give carbon dioxide and water in either the gaseous (left) or the liquid (right) state. The difference in enthalpy is equal to 88 k), the enthalpy of vaporization of 2 mol H20(l). 

Estimate the enthalpy change of the reaction between gaseous iodoethane and water vapor ... 

In addition to chemical reactions, the isokinetic relationship can be applied to various physical processes accompanied by enthalpy change. Correlations of this kind were found between enthalpies and entropies of solution (20, 83-92), vaporization (86, 91), sublimation (93, 94), desorption (95), and diffusion (96, 97) and between the two parameters characterizing the temperature dependence of thermochromic transitions (98). A kind of isokinetic relationship was claimed even for enthalpy and entropy of pure substances when relative values referred to those at 298° K are used (99). Enthalpies and entropies of intermolecular interaction were correlated for solutions, pure liquids, and crystals (6). Quite generally, for any temperature-dependent physical quantity, the activation parameters can be computed in a formal way, and correlations between them have been observed for dielectric absorption (100) and resistance of semiconductors (101-105) or fluidity (40, 106). On the other hand, the isokinetic relationship seems to hold in reactions of widely different kinds, starting from elementary processes in the gas phase (107) and including recombination reactions in the solid phase (108), polymerization reactions (109), and inorganic complex formation (110-112), up to such biochemical reactions as denaturation of proteins (113) and even such biological processes as hemolysis of erythrocytes (114). 

The terms enthalpy of fusion, enthalpy of vaporization, enthalpy of combustion, and many more cause some students to believe that there are many different kinds of enthalpies. There are not. These names merely identify the processes with which the enthalpy term is associated. Thus, there are processes called fusion (melting), vaporization, sublimation, combustion, and so forth. The corresponding enthalpy changes are called by names that include these descriptions. 

Ans. (a) The change of a liquid into a gas. (b) The change of a solid into a liquid, U) The enthalpy change accompanying a vaporization process, (d) The enthalpy change accompanying a melting (fusion) process. 

All partitioning properties change with temperature. The partition coefficients, vapor pressure, KAW and KqA, are more sensitive to temperature variation because of the large enthalpy change associated with transfer to the vapor phase. The simplest general expression theoretically based temperature dependence correlation is derived from the integrated Clausius-Clapeyron equation, or van t Hoff form expressing the effect of temperature on an equilibrium constant Kp,... 

For each of the phase transitions, there is an associated enthalpy change or heat of transition. For example, there are heats of vaporization, fusion, sublimation, and so on. 

Vaporization and condensation are opposite processes. Thus, the enthalpy changes for these processes have the same value but opposite signs. For example, 6.02 kJ is needed to vaporize one mole of water. Therefore, 6.02 kJ of energy is released when one mole of water freezes. 

Molar entropy of an adsorbed layer perturbed by the solid surface Total enthalpy change for the immersion of an evacuated solid in a solution at a concentration at which monolayer adsorption occurs Heat of dilution of a solute from a solution Enthalpy change for the formation of an interface between an adsorbed mono-layer and solution Integral heat of adsorption of a monolayer of adsorbate vapor onto the solid surface... 

Any chemical reaction that is accompanied by enthalpy changes can be followed by calorimetric methods [3,24,29], DSC is widely used to study polymerizing systems, especially epoxides [55-57]. Both the rate and the extent of reaction can be monitored using either isothermal or scanning modes of operation [3,24,29]. If volatile products are formed, the reaction must be carried out in sealed pans or under pressure [58] to conserve mass and avoid an uncertain correction for vaporization or to pressure-shift simultaneous vaporization events. 

If a substance undergoes a transformation from one physical stale to another, such as a polymorphic transition, the fusion or sublimation of a solid, or the vaporization of a liquid, the heat adsorbed hy the substance during the transformation is defined as the latent heat of transformation (transition, fusion, sublimation or vaporization). It is equal in the enthalpy change of the process, which is the difference between the enthalpy of the substance in the two states at (he temperature of the transformation. For the purpose of thcrmochemical calculations, i( is usually reported as a molar quantity with die units of calories (or kilocalories) per mule (or gram formula weight). The symbol L or AH. with a subscript i.f (or in), s. and n is commonly used and the value is usually given at the equilibrium temperature of the transformation under atmospheric pressure, or at 25 C. 

Those heal effects can be easily calculated when the enthalpies of formation and the enthalpy-temperature relations are available for the substances considered. Usually, the heat of reaction is defined as the heat evolved by the process, and it is equal to the enthalpy change but opposite in sign, while heats of fusion or vaporization always refer to ihe heat adsorbed, and for heals of solution the usage varies. In order to avoid any confusion, it is recommended to express heat effects of chemical process by reporting the enthalpy change. AH. 

This relation, which we can trace back to the first law of thermodynamics, is illustrated in Fig. 6.21. If we find, for example, that the enthalpy of vaporization of mercury is 59 kj-mol-1 at its boiling point, then we immediately know that the enthalpy change occurring when mercury vapor condenses at that temperature is —59 kj-mol. This value tells us that 59 kj of heat is released when 1 mol Hg(g) condenses to a liquid. 

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