Equations Nitric acid

In the net ionic equation, nitric acid is a strong acid and Bi(N03)3 is a soluble salt, so we need show only the reaction of the solid with the hydrogen ion forming the Bi ([Pg.277]

The sequence of steps for the nitration and sulfonation of benzene is similar to that for chlorination and bromination. For nitration, the electrophile is the nitronium ion, NOg, generated by the reaction of nitric acid with sulfuric acid. In the following equations nitric acid is written HONOg to show more clearly the origin of the nitronium ion. 

If this reaction takes place in air, the evolved nitrogen monoxide is oxidised to the dioxide and this dissolves again as in equation (9.1) hence virtually complete conversion of nitrogen dioxide to nitric acid can occur (see nitric acid, below). With alkalis, a mixture of nitrite and nitrate is formed ... 

Iodic acid may be made by oxidising iodine with excess fuming nitric acid according to the equation... 

Nitric acid being the solvent, terms involving its concentration cannot enter the rate equation. This form of the rate equation is consistent with reaction via molecular nitric acid, or any species whose concentration throughout the reaction bears a constant ratio to the stoichiometric concentration of nitric acid. In the latter case the nitrating agent may account for any fraction of the total concentration of acid, provided that it is formed quickly relative to the speed of nitration. More detailed information about the mechanism was obtained from the effects of certain added species on the rate of reaction. 

If it be assumed that the ionising characteristics of nitric acid are similar to those of the organic indicators used to define the scales of acidity, then a correspondence between the acidity-dependence of nitration and would suggest the involvement of the nitronium ion, whereas a correspondence with Hq would support the h)rpothesis that the nitric acidium ion were active. The analogies with and Hg are expressed in the first and last pairs of the followii equations respectively. The symbol AQ represents anthraquinone, the indicator originally used in this way for comparison with the acidity dependence of the rate of nitration of nitrobenzene ... 

Second-order rate coefficients for nitration in sulphuric acid at 25 °C fall by a factor of about 10 for every 10 % decrease in the concentration of the sulphuric acid ( 2.4.2). Since in sulphuric acid of about 90% concentration nitric acid is completely ionised to nitronium ions, in 68 % sulphuric acid [NO2+] io [HNO3]. The rate equation can be written in two ways, as follows ... 

If we consider the effect of nitrous acid upon zeroth-order nitration in organic solvents we must bear in mind that in these circumstances dinitrogen tetroxide is not much ionised, so the measured concentration of nitrous acid gives to a close approximation the concentration of dinitrogen tetroxide. Further, the negligible self-ionisation of nitric acid ensures that the total concentration of nitrate ions is effectively that formed from dinitrogen tetroxide. Consequently as we can see from the equation for the ionisation of dinitrogen tetroxide ( 4.3.1),... 

In partly aqueous nitric acid, the concentration of water is constant, and the corresponding equation is ... 

Since the first-order rate constant for nitration is proportional to y, the equilibrium concentration of nitronium ion, the above equations show the way in which the rate constant will vary with x, the stoichiometric concentration of dinitrogen tetroxide, in the two media. An adequate fit between theory and experiment was thus obtained. A significant feature of this analysis is that the weak anticatalysis in pure nitric acid, and the substantially stronger anticatalysis in partly aqueous nitric acid, do not require separate interpretations, as have been given for the similar observations concerning nitration in organic solvents. 

Nitrophosphates are made by acidulating phosphate rock with nitric acid followed by ammoniation, addition of potash as desired, and granulation or prilling of the slurry. The acidulate, prior to ammoniation, contains calcium nitrate and phosphoric acid or monocalcium phosphate according to the foUowiag equations ... 

Chemistry. Free-radical nitrations consist of rather compHcated nitration and oxidation reactions (31). When nitric acid is used in vapor-phase nitrations, the reaction of equation 5 is the main initiating step where NO2 is a free radical, either -N02 or -ON02. Temperatures of >ca 350° are required to obtain a significant amount of initiation, and equation 5 is the rate-controlling step for the overall reaction. Reactions 6 and 7 are chain-propagating steps. 

Absorption of Nitrogen Oxides. There have been numerous studies and reports on the reaction mechanisms and rate-controlling steps for the absorption of nitrogen oxides into water (43—46). The overall reaction to form nitric acid may be represented by equation 14, where Ai/298 K kJ/mol ofNO consumed. 

Potassium Nitrate. Potassium nitrate [7757-79-17, KNO, is produced commercially in the United States based on the reaction of potassium chloride and nitric acid (qv) (35). Ammonia (qv) oxidation is the source for the nitric acid and the reaction is manipulated chemically to yield chlorine as a co-product. The process is operated at an elevated temperature to drive the reaction to completion according to the following equation ... 

Nitration of > -hydroxyben2oic acid with filming nitric acid in the presence of sulfuric acid and acetic anhydride gives a mixture of the 2-nitro [602-00-6] and 4-nitro [619-14-7] substitution products. Bromination and iodination yield the 4-halogenated derivatives (4-bromo [14348-38-0] and 4-iodo [58123-77-6]). When > -hydroxyben2oic acid is treated with formalin in the presence of hydrochloric acid, 4-hydroxyphthahde [13161 -32-5] is obtained as shown in equation (10). 

In TBP extraction, the yeUowcake is dissolved ia nitric acid and extracted with tributyl phosphate ia a kerosene or hexane diluent. The uranyl ion forms the mixed complex U02(N02)2(TBP)2 which is extracted iato the diluent. The purified uranium is then back-extracted iato nitric acid or water, and concentrated. The uranyl nitrate solution is evaporated to uranyl nitrate hexahydrate [13520-83-7], U02(N02)2 6H20. The uranyl nitrate hexahydrate is dehydrated and denitrated duting a pyrolysis step to form uranium trioxide [1344-58-7], UO, as shown ia equation 10. The pyrolysis is most often carried out ia either a batch reactor (Fig. 2) or a fluidized-bed denitrator (Fig. 3). The UO is reduced with hydrogen to uranium dioxide [1344-57-6], UO2 (eq. 11), and converted to uranium tetrafluoride [10049-14-6], UF, with HF at elevated temperatures (eq. 12). The UF can be either reduced to uranium metal or fluotinated to uranium hexafluoride [7783-81-5], UF, for isotope enrichment. The chemistry and operating conditions of the TBP refining process, and conversion to UO, UO2, and ultimately UF have been discussed ia detail (40). 

Fluorine and nitrogen may be added to olefins with the nitrogen in different oxidation states Fluorine and a nilro group are added by reaction of an olefin with nitryl fluoride [131], nitronium tetrafluoroborate [195] (equation 32), or a combination of nitric acid and hydrogen fluoride [131, 196] (equation 33)... 

Oxidation of perfbtoroquinobne by fuming nitric acid yields pentafluoro-5,8-dioxo-5,8-dihydroquinoline or hexafluoro-2 oxo-l,2-dihydroquinoline in low yields ]98 (equation 90)... 

The conversion of cyclic sulfides to sulfones is accompbshed by more energetic oxidations. Perhalogenated thiolanes [106] and 1,3-dithietanes [107] are oxidized to sulfones and disulfones, respectively, by a mixture of chromium trioxide and nitric acid (equation 98) The same reagent converts 2,4-dichloro-2,4-bis(tnfluoromethyl)-l,3-dif/u cto cs to disulfone derivatives [107], whereas trifluoromethaneperoxysulfonic acid converts the starting compound to a sul-fone-sulfoxide derivative [2(equation 99). 

Nilrosated fluoro compounds are frequently prepared by electrophilic nitrosation on an electron-nch center of oxygen, nitrogen, or carbon The preparation of fluorochloronitronitrosomethane from the decarboxylation of fluorochloronitro-acetic acid in nitric acid is unique [f ] (equation 1)... 

Consider the reaction between silver and nitric acid for which the unbalanced equation is... 

A solution of potassium dichromate is made basic with sodium hydroxide the color changes from red to yellow. Addition of silver nitrate to the yellow solution gives a precipitate. This precipitate dissolves in concentrated ammonia but re-forms when nitric acid is added. Write balanced net ionic equations for all the reactions in this sequence. 

Write a balanced net ionic equation for the reaction of nitric acid with insoluble copper(II) sulfide the products include Cu2+, S(s), and N02(g). 

Strategy Follow the general procedure for writing and balancing redox equations in Chapter 4 and reviewed in Chapter 18. Note that because nitric acid is strong, it should be represented as H+ and N03 ions. 

Write a balanced net ionic equation for the reaction of nitric acid with... 

Cupric sulfide, copper(II) sulfide, reacts with hot nitric acid to produce nitric oxide gas, NO, and elemental sulfur. Only the oxidation numbers of S and N change. Write the balanced equation for the reaction. 

The ionisation may be attributed to the great tendency of the free hydrogen ions H+ to combine with water molecules to form hydroxonium ions. Hydrochloric and nitric acids are almost completely dissociated in aqueous solution in accordance with the above equations this is readily demonstrated by freezing-point measurements and by other methods. 

A process for production of K nitrate from K chloride and nitric acid, after several years of development, was placed in commercial production in the USA in 1963. The overall process is represented by the following equation ... 

Later, when nitric acid was manufd from synthetic ammonia at relatively low cost, synthetic sodium nitrate was made from it either thru the reaction between nitric acid and soda ash, or by direct absorption of nitrogen dioxide in an aq soln of Na carbonate (see above equation). The Na nitrate-nitrite soln was then heated with excess nitric acid to convert the nitrite to nitrate, and the NO thus produced was recycled to the nitric acid plant (Ref 6)... 

Although these compds are readily formed, they are also readily decompd, eg by the addition of a solvent that dissolves one of the two constituents. The nature of these non-covalent compds is discussed by Urbanski (Ref 35) Picric Acid is not resistant to strong oxidizing agents. It is oxidized by boiling nitric acid to yield oxalic add. Boiling with ammonium persulfate results in a complete oxidation, according to the equation ... 

A detailed study revealed that sulphides may react with nitric acid to give sulphoxides, sulphones and their nitro derivatives54. However, under suitable conditions the nitric acid oxidation of sulphides leads to a selective formation of sulphoxides. This is probably due to the formation of a sulphonium salt 30 which is resistant to further oxidation50 (equation 12). 

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