Change in enthalpy

A change in enthalpy indicates the heat absorbed or released during a chemical reaction at constant pressure. 

The lattice model that served as the basis for calculating ASj in the last section continues to characterize the Flory-Huggins theory in the development of an expression for AHj . Specifically, we are concerned with the change in enthalpy which occurs when one species is replaced by another in adjacent lattice sites. The situation can be represented in the notation of a chemical reaction ... 

If the amount of evaporation is small, the change in enthalpy in the Hquid phase can be taken as a result of temperature change alone. Using an average (av) hquid flow rate, the following is derived ... 

Example 4 Evaporative Cooling Air at 95 F dry-bulb temperature and 70 F wet-bulb temperature contacts a water spray, where its relative humidity is increased to 90 percent. The spray water is recirculated makeup water enters at 70 F. Determine exit dry-bulb temperature, wet-bulb temperature, change in enthalpy of the air, and quantity of moisture added per pound of dry air. 

Solution. Figure 12-8 shows the path on a psychrometric chart. The leaving dry-bulb temperature is obtained directly from Fig. 12-2 as 72.2 F. Since the spray water enters at the wet-bulb temperature of 70 F and there is no heat added to or removed from it, this is by definition an adiabatic process and there will be no change in wet-bulb temperature. The only change in enthalpy is that from the heat content of the makeup water. This can be demonstrated as follows ... 

Put in another way, since in equation (5.3) we have in effect only added FAT to each side of equation (5.1) it follows that energy will only be available to do work when the heat absorbed (FAS) exceeds the change in enthalpy, i.e. when AF has a negative value. 

Any reaction has associated with it changes in enthalpy (A//), entropy (A5), and free energy (AG). The principles of thermodynamics assure us that Aff, AS, and AG are... 

The scale-up of exothermic processes is greatly enhanced through the use of the coefficient of thermal stability. Kafarov [2] defined this as the ratio of the slope (tan ttj) of the line representing the heat removal (due to the heat transfer medium and changes in enthalpy) to the slope (tan ttj) of the line representing heat generation (by the reaction) at the intersection of the two lines when plotted on the T versus Q coordinates. This is expressed as... 

If a phase change occurs in the process stream for which heat duties are being calculated, it is best to perform a flash calculation and determine the heat loss or gain by the change in enthalpy. For a quick hand approximation it is possible to calculate sensible heat for both the gas and liquid phases of each component. The sum of all the latent and sen -i-ble heats is the approximate total heat duty. 

To calculate the heat duty it must be remembered that the pressure drop through the choke is instantaneous. That is, no heat is absorbed or lost, but there is a temperature change. This is an adiabatic expansion of the gas w ith no change in enthalpy. Flow through the coils is a constant pressure process, except for the small amount of pressure drop due to friction. Thus, the change in enthalpy of the gas is equal to the heat absorbed. 

Chemistry can be divided (somewhat arbitrarily) into the study of structures, equilibria, and rates. Chemical structure is ultimately described by the methods of quantum mechanics equilibrium phenomena are studied by statistical mechanics and thermodynamics and the study of rates constitutes the subject of kinetics. Kinetics can be subdivided into physical kinetics, dealing with physical phenomena such as diffusion and viscosity, and chemical kinetics, which deals with the rates of chemical reactions (including both covalent and noncovalent bond changes). Students of thermodynamics learn that quantities such as changes in enthalpy and entropy depend only upon the initial and hnal states of a system consequently thermodynamics cannot yield any information about intervening states of the system. It is precisely these intermediate states that constitute the subject matter of chemical kinetics. A thorough study of any chemical reaction must therefore include structural, equilibrium, and kinetic investigations. 

The efficiency of the cycle, ignoring work done by the boiler feed pumps, is given by change in enthalpy as follows ... 

The enthalpy of a substance, like its volume, is a state property. A sample of one gram of liquid water at 25.00°C and 1 atm has a fixed enthalpy, H. In practice, no attempt is made to determine absolute values of enthalpy. Instead, scientists deal with changes in enthalpy, which are readily determined. For the process... 

As noted earlier, for a reaction at constant pressure, such as that taking place in an open coffee-cup calorimeter, the heat flow is equal to the change in enthalpy. If a reaction is carried out at constant volume (as is the case in a sealed bomb calorimeter) and there is no mechanical or electrical work involved, no work is done. Under these conditions, with w = 0, the heat flow is equal to the change in energy, AE. Hence we have... 

AH, the change in enthalpy (Chapter 8) a negative value of AH tends to make a reaction spontaneous. 

Students often ask, What is enthalpy The answer is simple. Enthalpy is a mathematical function defined in terms of fundamental thermodynamic properties as H = U+pV. This combination occurs frequently in thermodynamic equations and it is convenient to write it as a single symbol. We will show later that it does have the useful property that in a constant pressure process in which only pressure-volume work is involved, the change in enthalpy AH is equal to the heat q that flows in or out of a system during a thermodynamic process. This equality is convenient since it provides a way to calculate q. Heat flow is not a state function and is often not easy to calculate. In the next chapter, we will make calculations that demonstrate this path dependence. On the other hand, since H is a function of extensive state variables it must also be an extensive state variable, and dH = 0. As a result, AH is the same regardless of the path or series of steps followed in getting from the initial to final state and... 

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. 

The activation parameters from transition state theory are thermodynamic functions of state. To emphasize that, they are sometimes designated A H (or AH%) and A. 3 4 These values are the standard changes in enthalpy or entropy accompanying the transformation of one mole of the reactants, each at a concentration of 1 M, to one mole of the transition state, also at 1 M. A reference state of 1 mole per liter pertains because the rate constants are expressed with concentrations on the molar scale. Were some other unit of concentration used, say the millimolar scale, values of AS would be different for other than a first-order rate constant. 

Consider a process at constant pressure for which the change in internal energy is AU and the change in volume is A V. It then follows from the definition of enthalpy in Eq. 9 that the change in enthalpy is... 

The implication of this equation is that, because chemical reactions typically take place at constant pressure in vessels open to the atmosphere, the heat that they release or require can be equated to the change in enthalpy of the system. It follows that if we study a reaction in a calorimeter that is open to the atmosphere (such as that depicted in Fig. 6.11), then the measurement of its temperature rise gives us the enthalpy change that accompanies the reaction. For instance, if a reaction releases 1.25 kj of heat in this kind of calorimeter, then we can write AH = q — —1.25 kj. 

The change in enthalpy of a system is equal to the heat supplied to the system at constant pressure. For an endothermic process, AH > 0 for an exothermic process, AH < 0. 

Similarly, because heat transferred at constant pressure can be identified with the change in enthalpy, AH, we can define the heat capacity at constant pressure, Cr, as... 

When a phase transition takes place at constant pressure, as is most common, the heat transfer due to the phase change is the change in enthalpy of the substance. 

The standard enthalpy of combustion, AH°, is the change in enthalpy per mole of a substance that is burned in a combustion reaction under standard conditions. The products of the combustion of an organic compound are carbon dioxide... 

A bond dissociation energy (Section 2.14) is strictly the energy required to break the bond at T = 0 a bond enthalpy is the change in enthalpy at the temperature of dissociation (typically 298 K). The two quantities differ by a few kilojoules per mole. 

STRATEGY Decide which bonds are broken and which bonds are formed. Use the mean bond enthalpies in Table 6.8 to estimate the change in enthalpy when the reactant bonds break and the change in enthalpy when the new product bonds form. For diatomic molecules, use the information in Table 6.7 for the specific molecule. Finally, add the enthalpy change required to break the reactant bonds (a positive value) to the enthalpy change that occurs when the product bonds form (a negative value). 

The individual contributions of the changes in enthalpy of the reactants and products are depicted in Fig. 6.36. 

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