Ammonia with hydrogen chloride

Countess, R., and Heicklen, J. (1973) Kinetics of particle growth. II. Kinetics of the reaction of ammonia with hydrogen chloride and the growth of particulate ammonium chloride, J. Phys. Chem., 77, AAA- 1. 

In this reversible reaction, the amine is acting as a weak base. This reaction can be likened to the reaction of ammonia with hydrogen chloride. However, amines tend... 

When ammonia gas, which is injected into Ihe left arm of the lube, comes in contact with hydrogen chloride, which is injected into the right arm of the tube, they react to form solid ammonium chloride ... 

Though ammonia and hydrogen chloride both dissolve in water, these two gases are very-different in other properties. For example, they behave differently when placed in contact with the dye, litmus. This dye, when moistened, turns red if it is placed in hydrogen chloride. However, if it is placed in ammonia, it turns blue. 

The treatment of dialkyl N-(3-cyanophenyl)aminomethylenemalonates with hydrogen chloride in a mixture of dioxane and an alcohol at 2-4°C for 7 days afforded imino ethers (1588) in 50-68% yields, which were then converted with ammonia in an alcohol into amidines (1589) in 70-78% yields (76PHA145). 

The Arrhenius theory also has limitations for explaining certain reactions. For example, aqueous solutions of ammonia are basic. They react with acids in neutralization reactions, even though ammonia does not contain the hydroxide ion. Many aqueous solutions of salts with no hydroxide ions are basic, too. Some reactions take place without any liquid solvent. For example, ammonium chloride can be formed by the reaction between ammonia and hydrogen chloride, which are both gases ... 

The chemical behavior of the cyclic dimer is quite analogous to that of other uretidine diones (69). Some characteristic reactions are summarized in Table III. As can be seen in Table III the mechanism of the reactions with ammonia and hydrogen chloride is not quite clear. The isolated products can be obtained either via a uretidine-dione or via a linear intermediate. 

Trimethylamine replaces PH3 quantitatively in BH3 PH3 to give BH3 N(CH3)3. Liquid or gaseous ammonia also replaces phosphine in the compound BH3 PH3 to the extent of 52-58% or up to 75%, respectively. The hydrogen atoms bonded to boron are partially, or completely, replaced by chlorine on treatment with hydrogen chloride, depending on the reaction conditions. The first stage of the reaction with hydrogen chloride is the formation of the colourless, viscous liquid BHjCl PH3 (see below). 

Hexammino-ferrous Chloride, [Fe(XH3)8]Cl2.—Ferrous chloride absorbs six molecules of ammonia at ordinary temperature with production of a white powder, the hexammine. It readily oxidises in air, and if heated to 100° C. in an atmosphere of hydrogen loses ammonia, and is transformed into diammino-ferrous chloride, [Fe(NH3)2]Cl2-1 It is probable that the monammine, [Fe(NH3)]Cl2, also exists.2 From a study of the tension of dissociation, the reaction of ammonia with ferrous chloride appears to be reversible between the temperatures of —18° and 350° C., hexammino-ferrous chloride being stable only at low temperature.8... 

To a flask containing a solution of 0.5 mole of ethylmagnesium bromide in 300 ml of ether is added dropwise 16 gm (0.285 mole) of propionitrile. The mixture is refluxed for 4 hr and then decomposed with 2.0 moles of anhydrous methanol. The ketimine is isolated as the hydrochloride by treatment of the filtrate with hydrogen chloride, and then regenerated with anhydrous ammonia to yield on distillation 12.2 gm (50.5 %), b.p. 86.5°C (730 mm), nD 1.4626 (20°C) hydrochloride, m.p. 104°C. 

It is important to recognize acid-base as a behavior. We say, for example, that hydrogen chloride behaves as an acid when mixed with water, which behaves as a base. Similarly, ammonia behaves as a base when mixed with water, which under this circumstance behaves as an acid. Because acid-base is seen as a behavior, there is really no contradiction when a chemical like water behaves as a base in one instance but as an acid in another instance. By analogy, consider yourself. You are who you are, but your behavior changes depending on whom you are with. Likewise, it is a chemical property of water to behave as a base (accept H+) when mixed with hydrogen chloride and as an acid (donate H+) when mixed with ammonia. 

The anhydrous salt yields yellowish-white crystals of density2 7-3 at 15° C. and melting point 3 1042° C. The specific heat is 4 0-0728 and the molar heat 05-4. The index of refraction is 2 2-14. It is insoluble in water, aqueous ammonia and in solutions of ammonium salts,5 and only slightly soluble in aqueous alkali or brine.6 It is decomposed when heated with hydrogen chloride,7 forming lead and arsenic chlorides, and in hot nitric acid it dissolves to form arsenic acid and lead nitrate, the latter being precipitated if the acid is sufficiently concentrated.8... 

CARBON SUBOXIDE. Cy02, formula weight 68.03, colorless, toxic, gas at room temperature, very unpleasant odor, sp gr 2.10 (air = 1.00). 1.24 (liquid at -87°C). mp — I07 C. bp 7°C (760 lorr). bums with a blue smoky Haute, producing CO . When condensed to liquid, the oxide slowly changes at ordinary temperature to a dark red solid, soluble in water to a red solution. Reacts with water to form malonic acid, with hydrogen chloride to form malonyl chloride, with ammonia to form malonamide. Made by heating malonic acid or its ester at 300°C under diminished pressure, and separation from simultaneously formed carbon dioxide and ethylene by condensation and fractional distillation. 

The ammonia-radicle theory.—The oldest hypothesis concerning the nature of the ammonia-compounds, and that adopted by A. L. Lavoisier, supposed ammonia to be an independent base or radicle, saturating acids, and forming salts. This theory has been likened to the etherin theory of J. B. A. Dumas and P. F. G. Boullay. The radicle is NHS sal-ammoniac is NH3+HCI etc. The theory makes no attempt to explain the nature of the other classes of ammonia-compounds nor does it explain the relation of ammonia to ordinary bases, which are metallic oxides, nor the differences between the ammoniacal salts from metallic sails of the same acid. Later on, the theory became associated with the mol. compound theory, so that sal ammoniac was represented by F. A. Kekule as an associated complex of ammonia and hydrogen chloride, in which the ammonia remained tervalent. These compounds were considered to be analogous to double salts, and to substances with water of crystallization. This view was supported by the ready dissociation of sal ammoniac by heat—a subject discussed in connection with ammonium chloride (2. 20, 16). H. Rose also emphasized the analogy between compounds of ammonia and of water in various salts as exemplified by the use of the term ammonia of crystallization. 

The ammonium theory.—In the ammonium theory of H. Davy, A. M. Ampere, and J. J. Berzelius, it was assumed. that the ammonium compounds contain a metallic radicle, NH4 (4.31,38), which may replace potassium, sodium, etc., in different salts. When ammonia unites with hydrogen chloride, the NH4-radicle is formed which unites with chlorine to form ammonium chloride in the same way that potassium united with chlorine forms potassium chloride. The ammonium theory thus corresponds with the ethyl theory of J. J. Berzelius, and J. von Liebig. The nitrogen is assumed to be quinquevalent, and this is in harmony with the work of V. Meyer and M. T. Lecco, A. Ladenburg, and W. Lossen on the quaternary ammonium baseb, and with the isomorphism of the ammonium and the potassium salts. 

The practice of assuming an increased valency for nitrogen when ammonia unites with hydrogen chloride, says A. Werner, if consistently carried out, would make antimony tervalent in antimony trichloride, and quinquevalent in SbCl3.KCl, etc. Bivalent iron in ferrous cyanide, FeCy2, would become decivalent in potassium ferrocyanide, K4FeCy6. J. Piccard and J. H. Dardel, and P. Pfeiffer discussed this subject. 

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