Nitric thermodynamics

Table 2. Thermodynamic Properties of Nitric Acid and Its Hydrates...

Nitric oxide is a colourless, monomeric, paramagnetic gas with a low mp and bp (Table 11.9). It is thermodynamically unstable and decomposes into its elements at elevated temperatures (1100-1200°C), a fact which militates against its direct synthesis from N2 and O2. At high pressures and moderate temperatures... 

Nitric acid is one of the three major acids of the modem chemical industiy and has been known as a corrosive solvent for metals since alchemical times in the thirteenth centuiy. " " It is now invariably made by the catalytic oxidation of ammonia under conditions which promote the formation of NO rather than the thermodynamically more favoured products N2 or N2O (p. 423). The NO is then further oxidized to NO2 and the gases absorbed in water to yield a concentrated aqueous solution of the acid. The vast scale of production requires the optimization of all the reaction conditions and present-day operations are based on the intricate interaction of fundamental thermodynamics, modem catalyst technology, advanced reactor design, and chemical engineering aspects of process control (see Panel). Production in the USA alone now exceeds 7 million tonnes annually, of which the greater part is used to produce nitrates for fertilizers, explosives and other purposes (see Panel). 

The modem process for manufacturing nitric acid depends on the catalytic oxidation of NH3 over heated Pt to give NO in preference to other thermodynamically more favour products (p. 423). The reaction was first systematically studied in 1901 by W. Ostwald (Nobel Prize 1909) and by 1908 a commercial plant near Bochum. Germany, was producing 3 tonnes/day. However, significant expansion in production depended on the economical availability of synthetic ammonia by the Haber-Bosch process (p. 421). The reactions occurring, and the enthalpy changes per mole of N atoms at 25 C are ... 

The Af-HjO diagrams present the equilibria at various pHs and potentials between the metal, metal ions and solid oxides and hydroxides for systems in which the only reactants are metal, water, and hydrogen and hydroxyl ions a situation that is extremely unlikely to prevail in real solutions that usually contain a variety of electrolytes and non-electrolytes. Thus a solution of pH 1 may be prepared from either hydrochloric, sulphuric, nitric or perchloric acids, and in each case a different anion will be introduced into the solution with the consequent possibility of the formation of species other than those predicted in the Af-HjO system. In general, anions that form soluble complexes will tend to extend the zones of corrosion, whereas anions that form insoluble compounds will tend to extend the zone of passivity. However, provided the relevant thermodynamic data are aveiil-able, the effect of these anions can be incorporated into the diagram, and diagrams of the type Af-HjO-A" are available in Cebelcor reports and in the published literature. 

The thermodynamic properties of nitric acid and its hydrates are given in Table 2 (Refs 32 34)... 

The formation of nitric acid in various states results in the following thermodynamic quantities (Ref 32)... 

Arrhenius parameters for nitration of 4-aikylphenyltrimethyiammonium ions in nitric acid-sulphuric acid mixtures (Table 12). It was argued that the observed Baker-Nathan order of alkyl substituent effect was, in fact, the result of a steric effect superimposed upon an inductive order. However, a number of assumptions were involved in this deduction, and these render the conclusion less reliable than one would like it would be useful to have the thermodynamic parameters for nitration of the methyl substituted compound in particular, in order to compare with the data for the /-butyl compound, though experimental difficulties may preclude this. It would not be surprising if a true Baker-Nathan order were observed because it is observed for all other electrophilic substitutions in this medium1. 

Thus far we have studied thermodynamics and kinetics imder the assumption that the systems of interest are in equilibrium. However, some natural systems have reaction rates so slow that they exist for long periods under non-equilibrium conditions. The formation of nitric oxide serves as an interesting example. 

The book focuses on three main themes catalyst preparation and activation, reaction mechanism, and process-related topics. A panel of expert contributors discusses synthesis of catalysts, carbon nanomaterials, nitric oxide calcinations, the influence of carbon, catalytic performance issues, chelating agents, and Cu and alkali promoters. They also explore Co/silica catalysts, thermodynamic control, the Two Alpha model, co-feeding experiments, internal diffusion limitations. Fe-LTFT selectivity, and the effect of co-fed water. Lastly, the book examines cross-flow filtration, kinetic studies, reduction of CO emissions, syncrude, and low-temperature water-gas shift. 

Some wet dissolution/decomposition reagents such as hydrofluoric or hydrochloric acid may have strong completing action. Very often, the complex formed may prevent the determination proper from being performed, because it is kinetically or thermodynamically very stable. In many cases the dissolution/decomposition reagents are used to destroy an organic substrate. For example, the use of nitric-perchloric or nitric-sulphuric-perchloric acid mixtures is well known. 

Nitric oxide has a very low ionization potential and could ionize at flame temperatures. For a normal composite solid propellant containing C—H—O—N—Cl—Al, many more products would have to be considered. In fact if one lists all the possible number of products for this system, the solution to the problem becomes more difficult, requiring the use of advanced computers and codes for exact results. However, knowledge of thermodynamic equilibrium constants and kinetics allows one to eliminate many possible product species. Although the computer codes listed in Appendix I essentially make it unnecessary to eliminate any product species, the following discussion gives one the opportunity to estimate which products can be important without running any computer code. 

From the thermodynamic data of Appendix C, show that the product of the reaction of ammonia gas with oxygen would be nitrogen, rather than nitric oxide, under standard conditions and in the absence of kinetic control by, for example, specific catalysis of NO formation by platinum. (Assume the other product to be water vapor.)... 

Classical methods of group analysis and separation take advantage of the stability of the [Ag(NH3)2]+ ion to separate silver from mercury. Treatment of a precipitate containing AgCl with dilute ammonia leads to the reaction in equation (3) bringing the silver into solution. To confirm the presence of Ag+, nitric acid must then be added to cause reprecipitation of AgQ. In aqueous ammonia, the diammine was the highest species formed, and thermodynamic data for its formation are collected in Table 3.20-23... 

Matrix isolation methods of synthesis have also been used to prepare and study coordination compounds. These involve the vaporization of a metal and a potential ligand, which are then rapidly carried in a stream of inert gas to a very cold surface, where the compound which has been formed is quickly trapped in the solid matrix. It is possible to determine the type of bonding, the structure and the thermodynamic properties of the compounds formed. Only small ligand molecules have been used thus far carbon monoxide, nitric oxide, nitrogen and oxygen, for example, but molecules of great interest have been formed. Some such are [Pd(C2H4)], [Pd(N2)3], [Ni(N2)202], [Ni(N2)4] and [Ni(CO)(N2)3].41... 

Type Ia-PSCs are solid particles composed of nitric acid/ice (approximately 50-50 wt %), especially in the form of the most thermodynamically stable nitric acid trihydrate, (NAT, HNO,.3I O) with size ranging between 0.3 and 3 pm [21-23]. The condensation temperatures for NAT under stratospheric conditions are typically 5-7 K higher than for... 

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