Formation, enthalpy change

Table 5.1 gives a sample calculation of the NHVj for toluene, starting from the molar enthalpies of formation of the reactants and products and the enthalpies of changes in state as the case requires. 

The enthalpy (strictly, the enthalpy change) for a reaction can readily be calculated from enthalpies of formation AHf which can often be obtained from tables of data. 

The above Born-Haber cycle represents the enthalpy changes in the formation of an alkali metal halide MX from an alkali metal (Li. Na, K, Rb. Cs) and a halogen (Fj. CI2. Br2 or I2). 

A more useful quantity for comparison with experiment is the heat of formation, which is defined as the enthalpy change when one mole of a compound is formed from its constituent elements in their standard states. The heat of formation can thus be calculated by subtracting the heats of atomisation of the elements and the atomic ionisation energies from the total energy. Unfortunately, ab initio calculations that do not include electron correlation (which we will discuss in Chapter 3) provide uniformly poor estimates of heats of formation w ith errors in bond dissociation energies of 25-40 kcal/mol, even at the Hartree-Fock limit for diatomic molecules. 

If you are running an updated version (V 8.0) of PC Model, click on force fields mm3. Omit this step for older versions. Click on Analyze (or compute depending on the version of PCMODEL) to obtain a menu of options. Select minimize. The geometry changes can be seen on the screen and a sequence of numbers appears in the right panel of the CRT screen, ending in Hf, the enthalpy of formation. This is the PCMODEL-MM3 calculated value of for cis-2-... 

Heat of formation (AH ) the enthalpy change for formation of a compound directly from the ele ments is one type of heat of reaction In cases such as the formation of CO2 or H2O from the combustion of carbon or hydrogen respectively the heat of forma tion of a substance can be measured directly In most... 

Equations (1) and (2) are the heats of formation of carbon dioxide and water respectively Equation (3) is the reverse of the combustion of methane and so the heat of reaction is equal to the heat of combustion but opposite in sign The molar heat of formation of a substance is the enthalpy change for formation of one mole of the substance from the elements For methane AH = —75 kJ/mol... 

An estimate of the enthalpy change which conesponds to the activation energy of the collision theory analysis of 167kJmoP may be made by assuming that the formation of tire dimer from two molecules of the monomer is energetically equivalent to tire dipole-dipole and dispersion interactions of two HI molecules. These exothermic sources of interaction are counterbalanced... 

Table 8-11. Enthalpy Change for Boron Trifluoride Complex Formation with Donors al 25°C...

Thermochemistry is concerned with the study of thermal effects associated with phase changes, formation of chemical compouncls or solutions, and chemical reactions in general. The amount of heat (Q) liberated (or absorbed) is usually measured either in a batch-type bomb calorimeter at fixed volume or in a steady-flow calorimeter at constant pressure. Under these operating conditions, Q= Q, = AU (net change in the internal energy of the system) for the bomb calorimeter, while Q Qp = AH (net change in the enthalpy of the system) for the flow calorimeter. For a pure substance. 

The standard molar enthalpy of formation of a compound, AH , is equal to the enthalpy change when one mole of the compound is formed at a constant pressure of 1 atm and a fixed temperature, ordinarily 25°C, from the elements in their stable states at that pressure and temperature. From the equations... 

The standard enthalpy change, Aff°, for a given thermochemical equation is equal to the sum of the standard enthalpies of formation of the product compounds minus the sum of the standard enthalpies of formation of the reactant compounds. 

Strictly speaking, AH° calculated from enthalpies of formation listed in Table 8.3 represents the enthalpy change at 25°C and 1 atm. Actually, AH is independent of pressure and varies relatively little with temperature, changing by perhaps 1 to 10 kj per 100°C. 

Enthalpy changes for reactions in solution can be determined using standard enthalpies of formation of aqueous ions, applying the general relation... 

The Gibbs-Helmholtz equation can be used to calculate the standard free energy of formation of a compound. This quantity, AGf, is analogous to the enthalpy of formation, AH . It is defined as the free energy change per mole when a compound is formed from the elements in their stable states at 1 atm. 

That w changes with phase has been shown49 for the tetragonal CuAu superlattice and the face-centered cubic solid solution from measurements of the enthalpies of formation of these two phases. Such measurements for the f.c.c. phase lead to w = 373 cal/g atom, in good agreement with the 350 cal/g atom derived by... 

As already mentioned, the enthalpy change A//° involved in an elementary propagation step corresponds to the equilibrium constant S. The parameter a, however, is purely entropically influenced mainly due to the steric restrictions during the formation of a helical nucleus. The determination of a, since it is related to the same power (3n - 2) of s, requires the consideration of the dependence of the thermodynamic parameters on the chain length (Eq. (9 a)). 

The first ACH° is AfH for C02 at 298.15 K, since elements in their naturally occurring state are combining to give C02(g). This combustion reaction is the standard state enthalpy of formation if we carry it out at p = 1 bar and make small corrections to change the C02(g) to the ideal gas condition. 

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