Standard reaction of formation

1 - THERMODYNAMIC PROPERTIES OF CHEMICAL SPECIES 1.1 - Standard reaction of formation 

Consider the reaction of formation of one mole of constituent Cj from the elements E, which it contains  

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In a number of cases the intermediate oxime has been isolated in the reaction of hydroxylamine and /3-keto esters. The reaction of ethyl acetoacetate with hydroxylamine generated an oxime which cyclized on base treatment (Scheme 144) (70MI41600). Likewise, treatment of an analogous amide with hydroxylamine generated a ring opened material which cyclized on treatment with HCl (Scheme 144) (67T831). The presence of a minor contaminant in the standard reaction of ethyl acetoacetate with hydroxylamine was discovered and identified as an isomeric isoxazolin-3-one. The mechanism of product formation has been discussed (70BSF2685). 

Entropy of Formation The ideal gas standard entropy of formation (AS°298) of a chemical compound is the increment of entropy associated with the reaction of forming that compound in the ideal gas state from the constituent elements in their standard state definea as the existing phase at a temperature of 298.15 K and one atmosphere (101.325 kPa). Thus ... 

The amonnt of energy that can be released from a given chemical reaction is determined from the energies (enthalpies of formation) of the individnal reactants and prodncts. Enthalpies are nsnally given for snbstances in their standard states, which are the stable states of pnre snbstances at atmospheric pressnre and at 25°C. The overall heat of reaction is the difference between the snms of the standard enthalpies of formation of the prodncts... 

Thus, the standard heat of a reaction is obtained by taking tlie difference between tlic standard heat of formation of tlie products and reactants. Once again, if the standard heat of reaction of formation is negative, as is the case of most combustion reactions, then energy is liberated due to tlie chemical reaction. Energy is absorbed if AH° is positive. 

Tables of standard entlialpies of formation, combustion and reaction are available in the literature for a wide variety of compounds. It is important to note that these are valueless imlcss tlie stoicliiomctric equation and tlie standard state of reactants and products are included.

The reverse reaction to give the gaseous species AlX(g) at high temperature accounts for the enhanced volatility of AIF3 when heated in the presence of A1 metal, and the ready volatilization of A1 metal in the presence of AICI3. Using calculations of the type outlined on p. 82 the standard heats of formation of the crystalline monohalides AIX and their heats of disproportionation have been estimated as ... 

The standard heat of formation ( AH ) of a chemical compound is the standard heat of reaction corresponding to the chemical combination of its constituent elements to form one mole of the compound, each existing in its standard state at 1 atm and 25°C. It has units of cal/g-mole. 

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

There are millions of possible reactions, and it is impractical to list every one with its standard reaction enthalpy. However, chemists have devised an ingenious alternative. First, they report the standard enthalpies of formation of substances. Then they combine these quantities to obtain the standard enthalpy of reaction needed. Let s look at these two stages in turn. 

The standard enthalpy of formation, AH°, of a substance is the standard reaction enthalpy per mole of formula units for the formation of a substance from its elements in their most stable form, as in the reaction... 

It follows from the definition just given that the standard enthalpy of formation of an element in its most stable form is zero. For instance, the standard enthalpy of formation of C(gr) is zero because C(gr) — C(gr) is a null reaction (that is, nothing changes). We write, for instance, AHf°(C, gr) = 0. However, the enthalpy of formation of an element in a form other than its most stable one is nonzero. For example, the conversion of carbon from graphite (its most stable form) into diamond is endothermic ... 

Now let s see how to combine standard enthalpies of formation to calculate a standard reaction enthalpy. To do so, we imagine carrying out the reaction in two steps we reverse the formation of the reactants from the elements, then combine the elements to form the products. The first step is usually to calculate the reaction enthalpy for the formation of all the products from their elements. For this step, we use the enthalpies of formation of the products. Then, we calculate the reaction enthalpy for the formation of all the reactants from their elements. The difference between these two totals is the standard enthalpy of the reaction (Fig. 6.31) ... 

EXAMPLE e.ll Using standard enthalpies of formation to calculate a standard enthalpy of reaction... 

STRATEGY We expect a strongly negative value because all combustions are exothermic and this oxidation is like an incomplete combustion. First, add up the individual standard enthalpies of formation of the products, multiplying each value by the appropriate number of moles from the balanced equation. Remember that the standard enthalpy of formation of an element in its most stable form is zero. Then, calculate the total standard enthalpy of formation of the reactants in the same way and use Eq. 20 to calculate the standard reaction enthalpy. 

Standard enthalpies of formation are commonly determined from combustion data by using Eq. 20. The procedure is the same, but the standard reaction enthalpy is known and the unknown value is one of the standard enthalpies of formation. 

Use standard enthalpies of formation to calculate the standard enthalpy of a reaction, and vice versa (Examples 6.11 and 6.12). 

Using standard enthalpies of formation from Appendix 2A, calculate the standard reaction enthalpy for each of the following reactions ... 

STRATEGY We write the chemical equation for the formation of HI(g) and calculate the standard Gibbs free energy of reaction from AG° = AH° — TAS°. It is best to write the equation with a stoichiometric coefficient of 1 for the compound of interest, because then AG° = AGf°. The standard enthalpy of formation is found in Appendix 2A. The standard reaction entropy is found as shown in Example 7.9, by using the data from Table 7.3 or Appendix 2A. 

Just as we can combine standard enthalpies of formation to obtain standard reaction enthalpies, we can also combine standard Gibbs free energies of formation to obtain standard Gibbs free energies of reaction ... 

STRATEGY The reaction is endothermic and, because a gas is produced from solid reactants, occurs with an increase in entropy. Because AHc > 0 and AS° > 0, the formation of products from pure reactants becomes spontaneous at temperatures for which AH° TAS°. The temperature at which the tendency for the reaction to occur begins solves to T = AH7AS°. We use data from Appendix 2A (and remember that the standard enthalpies of formation of elements are zero). 

What Do We Need to Know Already The concepts of chemical equilibrium are related to those of physical equilibrium (Sections 8.1-8.3). Because chemical equilibrium depends on the thermodynamics of chemical reactions, we need to know about the Gibbs free energy of reaction (Section 7.13) and standard enthalpies of formation (Section 6.18). Ghemical equilibrium calculations require a thorough knowledge of molar concentration (Section G), reaction stoichiometry (Section L), and the gas laws (Ghapter 4). 

STRATEGY Raising the temperature of an equilibrium mixture will tend to shift its composition in the endothermic direction of the reaction. A positive reaction enthalpy indicates that the reaction is endothermic in the forward direction. A negative reaction enthalpy indicates that the reaction is endothermic in the reverse direction. To find the standard reaction enthalpy, use the standard enthalpies of formation given in Appendix 2A. 

Standard reaction enthalpy (X = H) and Gibbs free energy (X = G) from standard enthalpies of formation ... 

When the partial pressure of each gaseous reagent is 1 bar and the concentration of each species in solution is 1 M, the conditions are defined to be standard. Under these conditions, the enthalpy change in a formation reaction is the standard enthalpy of formation (A... 

Our analysis of the reaction of nitrogen dioxide molecules is not unique. The same type of path can be visualized for any chemical reaction, as Figure 6-20 shows. The reaction enthalpy for any chemical reaction can be found from the standard enthalpies of formation for all the reactants and products. Multiply each standard enthalpy of formation by the appropriate stoichiometric coefficient, add the values for the products, add the values for the reactants, and subtract the sum for reactants from the sum for products. Equation summarizes this procedure ... 

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