Heat of reaction, standard

The heat of formation (enthalpy of formation) of a compound is an important thermodynamic quantity, because a table of heats of formation of a limited number of compounds enables one to calculate the heats of reaction (reaction enthalpies) of a great many processes, that is, how exothermic or endothermic these reactions are. The heat of formation (enthalpy of formation) of a compound at a specified temperature T is defined [195] as the standard heat of reaction (standard reaction enthalpy) for formation of the compound at T from its elements in their standard states (their reference states). By the standard state of an element we mean the thermodynamically stablest state at 105 Pa (standard pressure, about normal atmospheric pressure), at the specified temperature (the exception is phosphorus, for... 

STANDARD HEAT OF REACTION, STANDARD FREE-ENERGY CHANGE, AND EQUILIBRIUM CONSTANT 1.67... 

The standard formation properties of species are set by convention at zero for the elements in their reference forms at each temperature. The standard formation properties of in aqueous solution at zero ionic strength are also set at zero at each temperature. For other species the properties are determined by measuring equilibrium constants and heats of reaction. Standard transformed Gibbs energies of formation can be calculated from measurements of K, and so it is really these Maxwell relations that make it possible to calculate five transformed thermodynamic properties of a reactant. 

Free energy is related to two other energy quantities, the enthalpy (the heat of reaction measured at constant pressure) and the entropy. S. an energy term most simply visualised as a measure of the disorder of the system, the relationship for a reaction taking place under standard conditions being... 

The standard Gibbs energy change of reaction, is used ia the calculation of equilibrium compositions the standard heat of reaction, is used iu... 

Two variables of primary importance, which are interdependent, are reaction temperature and ch1orine propy1ene ratio. Propylene is typically used ia excess to act as a diluent and heat sink, thus minimising by-products (eqs.2 and 3). Since higher temperatures favor the desired reaction, standard practice generally involves preheat of the reactor feeds to at least 200°C prior to combination. The heat of reaction is then responsible for further increases in the reaction temperature toward 510°C. The chlorine propylene ratio is adjusted so that, for given preheat temperatures, the desired ultimate reaction temperature is maintained. For example, at a chlorine propylene molar ratio of 0.315, feed temperatures of 200°C (propylene) and 50°C (chlorine) produce an ultimate reaction temperature of approximately 500°C (10). Increases in preheat temperature toward the ultimate reactor temperature, eg, in attempts to decrease yield of equation 1, must be compensated for in reduced chlorine propylene ratio, which reduces the fraction of propylene converted and, thus aHyl chloride quantity produced. A suitable economic optimum combination of preheat temperature and chlorine propylene ratio can be readily deterrnined for individual cases. 

Two standard estimation methods for heat of reaction and CART are Chetah 7.2 and NASA CET 89. Chetah Version 7.2 is a computer program capable of predicting both thermochemical properties and certain reactive chemical hazards of pure chemicals, mixtures or reactions. Available from ASTM, Chetah 7.2 uses Benson s method of group additivity to estimate ideal gas heat of formation and heat of decomposition. NASA CET 89 is a computer program that calculates the adiabatic decomposition temperature (maximum attainable temperature in a chemical system) and the equilibrium decomposition products formed at that temperature. It is capable of calculating CART values for any combination of materials, including reactants, products, solvents, etc. Melhem and Shanley (1997) describe the use of CART values in thermal hazard analysis. 

Figure 2-2. Heats of reaction at temperature other than standard condition.

Standard heats of reaction of each component, dHf, dHfg, dHf., and dHfp. 

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. 

The heal of reaction (see Section 4.4) is defined as tlie enthalpy change of a system undergoing chemical reaction. If the retictants and products are at tlie same temperature and in their standard states, tlie heat of reaction is temied tlie standard lieat of reaction. For engineering purposes, the standard state of a chemical may be taken as tlie pure chemical at I atm pressure. Heat of reaction data for many reactions is available in tlie literature. ... 

The material in this section is divided into three parts. The first subsection deals with the general characteristics of chemical substances. The second subsection is concerned with the chemistry of petroleum it contains a brief review of the nature, composition, and chemical constituents of crude oil and natural gases. The final subsection touches upon selected topics in physical chemistry, including ideal gas behavior, the phase rule and its applications, physical properties of pure substances, ideal solution behavior in binary and multicomponent systems, standard heats of reaction, and combustion of fuels. Examples are provided to illustrate fundamental ideas and principles. Nevertheless, the reader is urged to refer to the recommended bibliography [47-52] or other standard textbooks to obtain a clearer understanding of the subject material. Topics not covered here owing to limitations of space may be readily found in appropriate technical literature. 

Standard Heat of Reaction. This is the standard enthalpy change accompanying a chemical reaction under the assumptions that the reactants and products exist in their standard states of aggregation at the same T and P, and stoichiometric amounts of reactants take part in the reaction to completion at constant P. With P = 1 atm and T = 25°C as the standard state, AH (T,P) can be written 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. 

The standard heat of combustion (ziH") of a chemical substance (usually an organic compound) is the same as the standard heat of reaction for complete oxidation of 1 mole of the substance in pure oxygen to yield COj(g) and HjO(f) as products. A reference state of 25°C and 1 atm is assumed in quoting standard heats of combustion in cal/g-mole. The value of AH" is always negative because combustion is an exothermic reaction. Note that the standard heats of combustion for carbon and hydrogen are the same as the heats of formation for CO,(g) and HjO(f), respectively. 

Calculate the heat of reaction at the standard reference state (1 atm, 25°C) for... 

It does not matter that there is no known catalyst that can accomplish the reaction in Equation (7.21) directly. Heats of reaction, including heats of formation, depend on conditions before and after the reaction but not on the specific reaction path. Thus, one might imagine a very complicated chemistry that starts at standard conditions, goes through an arbitrary trajectory of temperature and pressure, returns to standard conditions, and has Equation (7.21) as its overall effect. A77. =-1-147,360 J/mol of styrene formed is the net heat effect associated with this overall reaction. 

C06-0135. The five stable oxides of nitrogen are NO, NOg, Ng O, Ng O4, and N2 O5. Balance each of the following oxidation reactions, and then use standard formation enthalpies to calculate the heats of reaction per mole of atomic nitrogen for each reaction ... 

In the feed pretreatment section oil and water are removed from the recovered or converted CCI2F2. The reactor type will be a multi-tubular fixed bed reactor because of the exothermic reaction (standard heat of reaction -150 kJ/mol). After the reactor the acids are selectively removed and collected as products of the reaction. In the light removal section the CFCs are condensed and the excess hydrogen is separated and recycled. The product CH2F2 is separated from the waste such as other CFCs produced and unconverted CCI2F2. The waste will be catalytically converted or incinerated. A preliminary process design has shown that such a CFC-destruction process would be both technically and economically feasible. 

Standard heat data are usually compiled at 298 K, and to calculate the heat of reaction at an arbitrary temperature, the temperature dependency of enthalpies of reaction species have to be considered. These are generally dependent on temperature as follows... 

The standard heat of reaction can be calculated from the heats of formation as... 

For this reaction the standard heat of reaction at 298 K, AH298, equals -393510 J. Now let the following two reactions, which also finally result in the formation of C02, be considered... 

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