Acid decomposition of paper

Schematic diagram of the strategy for solving the problem of the acid decomposition of paper.

The type of problem solving illustrated by investigation of the acid decomposition of paper is quite typical of that which a practicing chemist confronts daily. The first step in successful problem solving is to identify the... 

Decomposition of Metal Chlorides by Acids. Two commercial processes employing the acidic decomposition of metal chlorides are the salt—sulfuric acid process and the Hargreaves process. Although these processes are declining in importance, they are used mainly because of the industrial demand for salt cake [7757-82-6] by the paper (qv) and glass (qv) industries. In the United States, however, Httle HCl is produced this way. 

The kinetics of the solvolysis of linalyl p-nitrobenzoate were published in note form 18 years ago, but a full discussion of the reaction, including the mechanism for retention of optical activity in the cyclized products, has now been published as one of the Winstein memorial papers. Another paper on the reaction of linalool with phosphorus pentachloride reports 88 % yield of a ca. 3 1 mixture of geranyl and linalyl chlorides (after 4 h at —10 °C). Acetylation of linalool is notoriously fickle on account of ready rearrangements now a method using t-butyl acetate and sodium methoxide is said to give a 90% yield of the unrearranged acetate. The rearrangements involved in the acid decomposition of the... 

Dissolve 20 g, (19 -6 ml.) of anihne in a mixture of 55 ml. of concentrated hydrochloric acid (1) and 55 ml. of water contained in a 350 ml, conical flask. Place a thermometer in the solution and immerse the flask in a bath of crushed ice (2) cool until the temperature of the stirred solution falls below 5°, Dissolve 16 g. of sodium nitrite in 75 ml. of water and chUl the solution by immersion in the ice bath add the sodium nitrite solution (3) in small volumes (2-3 ml. at a time) to the cold anihne hydrochloride solution, and keep the latter weh stirred with the thermometer. Heat is evolved by the reaction. The temperature should not be allowed to rise above 10° (add a few grams of ice to the reaction mixture if necessary) otherwise appreciable decomposition of the diazonium compound and of nitrous acid wih occur. Add the last 5 per cent, of the sodium nitrite solution more slowly (say, about 1 ml. at a time) and, after stirring for 3-4 minutes, test a drop of the solution diluted with 3-4 drops of water with potassium iodide - starch paper (4) if no immediate blue colour... 

A review of earlier results is included in a paper by Kiyoura and Urano [946] on the decompositions of (NH4)2S04 (413—513 K) and NH4HS04 (433-473 K). The intermediate formation at 433 K of the double salt (NH4)3H(S04)2 was detected by X-ray diffraction and this salt decomposed to NH4HS04 at 453 K. Decomposition of the ammonium hydrogen sulphate at 473 K proceeded through the formation of molten sulphamic acid... 

Gold forms a continuous series of solid solutions with palladium, and there is no evidence for the existence of a miscibility gap. Also, the catalytic properties of the component metals are very different, and for these reasons the Pd-Au alloys have been popular in studies of the electronic factor in catalysis. The well-known paper by Couper and Eley (127) remains the most clearly defined example of a correlation between catalytic activity and the filling of d-band vacancies. The apparent activation energy for the ortho-parahydrogen conversion over Pd-Au wires wras constant on Pd and the Pd-rich alloys, but increased abruptly at 60% Au, at which composition d-band vacancies were considered to be just filled. Subsequently, Eley, with various collaborators, has studied a number of other reactions over the same alloy wires, e.g., formic acid decomposition 128), CO oxidation 129), and N20 decomposition ISO). These results, and the extent to which they support the d-band theory, have been reviewed by Eley (1). We shall confine our attention here to the chemisorption of oxygen and the decomposition of formic acid, winch have been studied on Pd-Au alloy films. 

The halic acids may not be industrially important, but their salts certainly are. Sodium chlorate is produced in enormous quantities and used in processes in which its oxidizing strength makes it a versatile bleach. One such use is in making paper, and potassium chlorate is used as the oxidizing agent in matches. The decomposition of potassium chlorate was discussed in Chapter 13 in connection with the laboratory preparation of oxygen. 

Some of the investigations carried out in the first half of the twentieth century were related to CL associated with thermal decomposition of aromatic cyclic peroxides [75, 76] and the extremely low-level ultraviolet emission produced in different reaction systems such as neutralization and redox reactions involving oxidants (permanganate, halogens, and chromic acid in combination with oxalates, glucose, or bisulfite) [77], In this period some papers appeared in which the bright luminescence emitted when alkali metals were exposed to oxygen was reported. The phenomenon was described for derivatives of zinc [78], boron [79], and sodium, potassium, and aluminum [80]. 

In our laboratories, a cycle time of 90 sec can be achieved with a dilution factor of 1 25 for a given sample concentration, allowing the purity and identity control of two and a half 384-well microtiter plates per day. The online dilution eliminated an external step in the workflow and reduced the risks of decomposition of samples in the solvent mixture (weakly acidic aqueous solvent) required for analysis. Mao et al.23 described an example in which parallel sample preparation reduced steps in the workflow. They described a 2-min cycle time for the analysis of nefazodone and its metabolites for pharmacokinetic studies. The cycle time included complete solid phase extraction of neat samples, chromatographic separation, and LC/MS/MS analysis. The method was fully validated and proved rugged for high-throughput analysis of more than 5000 human plasma samples. Many papers published about this topic describe different methods of sample preparation. Hyotylainen24 has written a recent review. 

In a note on the decomposition of cellulose by a mixed culture of Vibrio perimastrix, Perlin and Michaelis84 reported about 5.6% of filter paper was fermented in 8 days. The agreement between this percentage and the percentages of accessible cellulose in native cellulose as found by hydrolysis may be fortuitous. However, there is enough similarity in acid and enzymatic hydrolysis to warrant further work along this line. 

Several octahedral dihydrazine metal (II) salts of this class were prepared and thermally decomposed. The succinates and malonates of nickel and cadmium decomposed explosively [1]. A later paper on mixed metal bis-hydrazine malonates of cobalt with magnesium, manganese, nickel, zinc or cadmium recommends that decomposition, in a pre-heated crucible at 500°C, be of small quantities only. The same workers have reported exothermic decomposition of similar hydrazine complexed salts of other small organic acids. 

The results given in this paper show that aliphatic amines do not catalyze the decomposition of peroxides, and compared with their effect at the start of reaction, they have much less effect on the later stages of oxidation, although they appear to retard the decomposition of peracetic acid. The reactions of radicals with aliphatic amines indicate that an important mode of inhibition is most probably by stabilization of free radicals by amine molecules early in the chain mechanism, possibly radicals formed from the initiation reaction between the fuel and oxygen. For inhibition to be effective, the amine radical must not take any further part in the chain reaction set up in the fuel-oxygen system. The fate of the inhibitor molecules is being elucidated at present. 

In 1790 Dr. Adair Crawford (1748—1795) published a paper on The medicinal properties of the muriated barytes (barium chloride) (18). The muriated barytes exhibited in St. Thomas s Hospital since the month of May, 1789, said he, was obtained by the decomposition of the heavy spar. Having procured some specimens of a mineral which is sold at Strontean [sic], in Scotland under the denomination of aerated barytes, I was in hopes that the salt might be formed with less difficulty by immediately dissolving that substance in the muriatic acid. It appears, however, from the following facts, which have been verified by the experiments of my assistant, Mr. Cruikshank, as well as by my own, that this mineral really possesses different properties from the terra ponderosa [baryta] of Scheele and Bergman (49). 

Measurement of pH is a potentiometric technique frequently used for measuring the degree of the deterioration of materials that are subjected to natural aging. The determination of pH levels is commonly carried out on ethnographic objects manufactured with parchment or leather, and it is especially relevant in altered paper due to the formation of acidic compounds from the decomposition of the woodpulps and other raw materials, which can induce the hydrolysis of the cellulose and then decrease the resistance and mechanical properties of the document [29]. 

---