Enthalpy term

Many other mixed-feed arrangements are possible which combine the individual advantages of each type of arrangement. Figure 3.13 shows a three-stage evaporator in temperature-enthalpy terms, assuming that inlet and outlet solutions are at saturated conditions... 

Let us examine the enthalpy terms involved when an ionic crystal MX is dissolved in water. The energy diagram for a Group I halide is as shown in Figure 3.8. 

It IS a curious fact that substituents affect the entropy of ionization more than they do the enthalpy term m the expression... 

Based on the bench-scale data, two coal-to-acetylene processes were taken to the pilot-plant level. These were the AVCO and Hbls arc-coal processes. The Avco process development centered on identifying fundamental process relationships (29). Preliminary data analysis was simplified by first combining two of three independent variables, power and gas flow, into a single enthalpy term. The variation of the important criteria, specific energy requirements (SER), concentration, and yield with enthalpy are indicated in Figure 12. As the plots show, minimum SER is achieved at an enthalpy of about 5300 kW/(m /s) (2.5 kW/cfm), whereas maximum acetylene concentrations and yield are obtained at about 7400 kW/(m /s) (3.5 kW/cfm). An operating enthalpy between these two values should, therefore, be optimum. Based on the results of this work and the need to demonstrate the process at... 

Calculate AS° for ionization of each compound. Comment on the contribution of AH° and AS° to the free energy of ionization. Test the data for linear fiee-energy correlations. Are the linear free-energy correlations dominated by entropy or enthalpy terms ... 

It is seen that all the points lie on the same straight line, irrespective of the operating temperature and, thus, the enthalpy term is close to zero and the solutes are not retained by differential molecular forces. Thus, the curve shows the effect of... 

Finally, another important and interesting fact is established from the data treated in this manner. All the examples given confirm that the standard entropy term tends to increase with the standard enthalpy term. Consequently, the increase in retention is not as great as that which would be expected from the increase in standard enthalpy alone. 

The enthalpy term h includes both internal energy and flow work terms. Since dw=0 between compressor stations, the equation becomes ... 

The results were simple and clear-cut Only the two terms ofa° and Emin were involved for the a-cyclodextrin systems, and the two terms of k and Emin, for (S-cyclodextrin systems. This means that the stabilities of the inclusion complexes are mainly governed by the electronic and steric interactions in a-cyclodextrin systems and by the hydro-phobic and steric interactions in (i-cyclodextrin systems, regardless of the position of the substituents in the phenols. These observations agree well with those by Harata23), who showed that there is no appreciable difference in thermodynamic parameters between cyclodextrin complexes of m- and p-di substituted benzenes and that the contribution of the enthalpy term to the complexation is more significant in a-cyclodextrin systems than in P-cyclodextrin systems, where the inhibitory effect... 

The free-energy change AG is made up of two terms, an enthalpy term, AH, and a temperature-dependent entropy term, TAS. Of the two terms, the enthalpy term is often larger and more dominant. 

Enthalpy-pressure diagram for water-steam 813 Enthalpy term, energy balance equation 74 Entropy 3,28... 

In each case, both the entropy and enthalpy terms favour the formation of the chelated complex, regardless of the t/-electron configuration. Note, however, that outside the d block, i.e. with alkaline earths and other main group metals, it is often found that the entropy term is dominant. 

In some cases, the enthalpy term may actually oppose the formation of the chelated complex, although the entropy term outweighs it to give an overall favourable free energy term. In general, this situation is the exception rather than the rule. 

Although reactions in which molecules are cleaved into two or more pieces have favorable entropy effects, many potential cleavages do not take place because of large increases in enthalpy. An example is cleavage of ethane into two methyl radicals. In this case, a bond of 79 kcal mol (330 kJ mol ) is broken, and no new bond is formed to compensate for this enthalpy increase. However, ethane can be cleaved at very high temperatures, which illustrates the principle that entropy becomes more important as the temperature increases, as is obvious from the equation AG = AH — TAS. The enthalpy term is independent of temperature, while the entropy term is directly proportional to the absolute temperature. 

Again students are expected to realise that this does not represent a stand-alone chemical process, and electrons are not found free under usual conditions, and so this process would need to be coupled with one that provides a place for the electron to go. Students may meet this process as part of a simple redox process (say with the reduction of a less reactive metal), or as one component of the analysis of a more complex process using Hess s law to find an enthalpy change by aggregating the enthalpy terms of an indirect route. 

This is an integral balance written for the whole system. The various terms deserve discussion. The enthalpies are relative to some reference temperature, Tref. Standard tabulations of thermodynamic data (see Chapter 7) make it convenient to choose rre/ = 298K, but choices of 7 re/ = 0K or Tref = Q°C are also common. The enthalpy terms will normally be replaced by temperature using... 

The decomposition of N2 O4 requires a bond to break. This is the reason why the decomposition has a positive A 77 °. At the same time, the number of molecules doubles during decomposition, which is the reason AS° has a positive value. The positive enthalpy change means that energy Is removed from the surroundings and constrained, whereas the positive entropy change means that matter is dispersed. At temperatures below 315 K, the enthalpy term dominates and decomposition is not spontaneous, but at temperatures above 315 K, the entropy term dominates and decomposition is spontaneous. 

As in Section II,A,l,a, the thermal conductivities are assumed to be constant, and the liquid enthalpy is assumed to be only a function of temperature. The gas phase enthalpy term can be separated into two parts ... 

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. 

Table 6.1 summarizes the thermodynamic parameters relating to the macrocyclic effect for the high-spin Ni(n) complexes of four tetraaza-macrocyclic ligands and their open-chain analogues (the open-chain derivative which yields the most stable nickel complex was used in each case) (Micheloni, Paoletti Sabatini, 1983). Clearly, the enthalpy and entropy terms make substantially different contributions to complex stability along the series. Thus, the small macrocyclic effect which occurs for the first complex results from a favourable entropy term which overrides an unfavourable enthalpy term. Similar trends are apparent for the next two systems but, for these, entropy terms are larger and a more pronounced macrocyclic effect is evident. For the fourth (cyclam) system, the considerable macrocyclic effect is a reflection of both a favourable entropy term and a favourable enthalpy term. 

Enthalpies of interaction of Ca2+ with several aldopentoses and aldohexoses have been determined calorimetrically (652,653,656-658). Complex formation is generally characterized by the balance between a fairly large favorable enthalpy term and an almost equal but unfavorable entropy term - for ribose both AH and TAS° are — 24 kJ mol-1 a value of +5 cm3 mol 1 for AV° can be understood in terms of electrostriction (658). 

We now turn to the calculation of bond enthalpy terms. In a first approximation, the enthalpy required to break all the chemical bonds in, say, gaseous GeR4, the so-called... 

The calculation of other bond enthalpy terms, such as E (Ge—Ge), E (Ge—O), E (Ge—N) and E(Ge—S), can be made from data in Table 1. However, due to the above-mentioned controversy involving most of the data obtained with static-bomb combustion calorimeters, we refrain from tabulating those terms. 

Despite the previous remarks, organotin compounds are one of the few families of organometallic substances for which the thermochemical data justify the calculation of bond enthalpy terms. Some term values (consistent with the terms recommended by Pilcher and Skinner for hydrocarbons)27 are given in Table 4. A few words on this selection are, however, appropriate. 

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