For those who are interested in knowing the time tested methods from "Inorganic Laboratory Preparations": Of the six methods given here, the first three may be used for the production of gaseous hydrogen bromide as well as for aqueous solutions of the gas; IV, V, and VI can be employed only for making the constant-boiling acid.
H2 + Br2 --> 2HBr
The following apparatus is assembled in order:
A steady flow of hydrogen is started through the apparatus to displace the air. This operation requires about thirty minutes, during which time the bromine is kept in the cooling bath.
The furnace is now slowly warmed to 350-375' C and the flow of hydrogen is increased to a point where the bubbles are just too rapid to count. A bath of water at 40-45' C is now placed under the vessel containing the bromine; under these conditions, conversion to hydrogen bromide is complete in about 20 minutes. No vapors of bromine should be visible at the outlet of the reaction tube; otherwise the bromine must be cooled somewhat in water.
At the end of the experiment the two wash bottles are removed and the hydrobromic acid absorbed is determined from the gain in weight; if the smaller volume of water was used, the concentration of acid should be 60-65% by weight. If constant-boiling acid is desjred, the solution should be distilled and the fraction boiling at 122-127' C collected as 47-48% hydrobromic acid. A rapid method for determining the concentration of the solution produced is by a rough determination of specific gravity. 65%, 1.78; 60%, 1.68; 55%, 1.60; 50%, 1.52; 45%, 1.44.
2P + 3Br2 --> 3HBr + H3PO4
In a distilling flask fitted with a dropping funnel are placed 25 g of clean sand and, over this, a mixture of 25g of red phosphorus and 100 g of sand. The mass is moistened with 40-45ml of water, and 50 ml of bromine are introduced into the funnel. A U-tube and absorption bottles as described under (I) are connected to the flask. The reaction flask is cooled in ice while the bromine is added dropwise at a very slow rate; the phosphorus may glow with each addition of halogen. In order to avoid a suck-back of the water in the absorption flasks, it is advisable to place an empty safety trap between the U-tube and the water traps. As the reaction proceeds, the evolution of gas is more readily controlled and the cooling bath may be removed. When all the bromine has been added, the distilling flask is gently warmed to drive off the remaining acid vapors. The working-up of the hydrobromic acid solutions is the same as previously described.
Yield in I and II is over 90% of theory
C10H12 + 4Br3 ---> 4HBr + C10H8Br4
If anhydrous hydrogen bromide is desired, the procedure is carried out in the absence of water, using dry reagents. The apparatus of method II is used.
Thirty-five grams of tetrahydronaphthalene (Tetralin) are placed in the flask with either 150 or 200ml of water, depending on the desired concentration of the acid. At first the flask is cooled in ice while 50ml of bromine are slowly added dropwise; about one gram of iron filings catalyzes the bromination. As the reaction proceeds, the flask may be allowed to warm up to room temperature. After all the bromine has been added the flask should be shaken for some time; the aqueous layer should be colorless. The acid layer is then separated from the organic material and worked up as in I. Yield about 90%.
H2SO4 + KBr ---> HBr + KHSO4
A mixture of 120g of potassium bromide and 200ml of water is cooled in ice while 90ml of concentrated sulfuric acid is slowly added. The temperature must not rise over 75' C during this addition; otherwise free bromine may be formed, causing a loss in yield. The reaction mixture is cooled to room temperature and the potassium bisulfate is filtered off by suction through a fritted funnel or a hardened filter paper. The filtrate is then fractionated and the material boiling from 122-127' C is collected as constant-boiling acid. Yield = 85%
In all cases where a mixture of sulfuric and hydrobromic acids is obtained, a redistillation is necessary to remove about 0.01% of sulfate in the first fractionation; only the acid with a steady boiling point is retained. This operation entails a loss of about 15% in yield.
Br2 + SO2 + 2H2O --> 2HBr + H2SO4
Fifty milliliters of bromine are covered with 200ml of water and sulfur dioxide is passed into the mixture, under the hood, until a straw-colored liquid results. Fractionation yields about 300g of 47-48 % acid, which is an almost theoretical yield. As this reaction proceeds, the bromine dissolves in the hydrobromic acid that is formed, yielding a homogeneous liquid into which the sulfur dioxide may be more rapidly introduced - HBr+Br2 <=> HBr2
Hydrobromic acid may be prepared conveniently by the interaction of bromine and sulfur dioxide in the presence of water [1] (Note 7).
In a 3-l. round-bottomed flask are placed 1200 g. (377 cc., 7.5 moles) of bromine, 500 cc. of water, and 1500 g. of crushed ice. A fairly rapid stream of sulfur dioxide is allowed to pass from a pressure tank into the flask, the outlet of the gas-tube being placed below the surface of the bromine layer. The flow of sulfur dioxide is adjusted at such a rate that the gas is completely absorbed. It is advisable to agitate the mixture occasionally during the first stage of the reduction (Note 8). About two hours will serve for the completion of the reduction, at which time the mixture will assume a yellow color (Note 9) which is not removed by further addition of sulfur dioxide, an excess of which is to be avoided (Note 10). To prevent loss by gaseous hydrogen bromide, it is advisable to cool the mixture during the progress of the reduction.
When the reduction is completed, the flask is connected with a condenser and the mixture subjected to distillation. The boiling point of constant boiling hydrobromic acid is 125–126° /760 mm., but it must be remembered that, in distilling the product from the sulfuric acid mixture, the thermometer reading should not be relied upon as an index to the composition of the distillate. Towards the end of the distillation the thermometer may rise to 130° and above, when water with only traces of acid distils from the sulfuric acid residue. Upon redistillation of the product the thermometer reading may be relied upon. For many uses a product free from traces of sulfuric acid is not required and one distillation is sufficient. In such cases the progress of the distillation is followed by determinations of the specific gravity of the distillate.
According to the above procedure, 20 kg. of 48% hydrobromic acid (92% of the theoretical amount) may be prepared from 10.3 kg. of bromine. The actual time required by one person for the preparation of this quantity is twenty-three hours.
7. In the sulfur dioxide reduction of bromine, it should be noted that the proportion of water used depends upon whether the reduction mixture is to be distilled for the preparation of 48 per cent hydrobromic acid, or whether it is to be used directly for the manufacture of alkyl bromides.
8. During the first stage of the reduction, the flask should be shaken from time to time in order to avoid the accumulation of sulfur dioxide, or possibly of sulfuryl bromide, which would result in a violent reaction owing to a large quantity of the material reacting at one time. In more than a hundred reduction experiments conducted with quantities of bromine varying from 0.5 to 2 kg., this sudden reaction was noted in only one or two instances, in spite of the fact that there was usually no agitation other than that furnished by the entering gas stream.
Mechanical stirring is frequently important in obtaining successful yields. In Fig. 2, A and B represent two convenient types of stirring devices [2] where refluxing and stirring are desired at the same time. When the stopper of the flask is so small that it will hold only the mechanical stirrer, a Y-tube such as is shown in Fig. 3 B fitted with either form of stirrer is suitable. It often happens that a separatory funnel or thermometer must also be inserted in the flask in addition to the reflux condenser. A three-necked flask such as is shown in Fig. 3 A is especially convenient, the middle opening being used for the stirrer, the two smaller ones for thermometer and reflux condenser.
9. The intensity of the color in the reduced bromine solution depends somewhat on the quality of bromine used, and with the technical product special care is needed in noting the end point of the reduction, i.e., the transition from the bromine color to a yellowish-brown color.
10. An excess of sulfur dioxide is to be avoided for the reason that evolution of gas during the distillation of the product will result in a considerable loss of alkyl bromide through volatilization. This loss is especially marked in the preparations of ethyl and allyl bromides if this precaution is not observed.
[1] Scott, J. Chem. Soc. 77, 648 (1900); Pickles, Chem. News, 119, 89 (1919).
[2] Brühl, Ber. 37, 923 (1904).
2S + Br2 --> S2Br3
S2Br3 + 5Br2 +8H2O -->12HBr + 2H2SO4
One hundred and fifty grams of bromine are weighed into a glass-stoppered bottle in the hood and l0g of powdered sulfur are quickly introduced. The bottle is then agitated and the sulfur rapidly dissolves to yield a red oily liquid.
Two hundred grams of ice are placed in a 500ml glass-stoppered bottle and the vessel is immersed in ice. About one-third of the sulfur-bromine mixture is added; over the course of about one hour the red oil disappears. Cooling is maintained throughout the hydrolysis. The second third of the sulfur-bromine compound is now added, followed by the last portion about 30 minutes later. When all the material has dissolved and reacted, a pale yellow liquid remains which is fractionally distilled as usual; b.p. 122-127' C; Yield about 300g of acid. Hydrobromic acid may be kept colorless for long periods of time by storage in a dark bottle in the refrigerator.
References: (I) 1. I, vol. 1:152. (II) 2. FILETI AND CROSA, Gazz. chim. ital., 21:64 (1891); B:71 (III)3. I, vol. 1:151; footnote, p. 152. (IV) 4. I, vol. 1:155. (V) 5. Organic Syntheses, Collective Vol. 1, p. 23, Wiley, 1936. (VI) 6. FARKAS et oL, J. Soc. Chem. Ind., 66:116 (1947). 7. P:464. Title . G.G. Schlessinger, Inorganic Laboratory Preparations,,Chemical Pub. Co., N.Y. (1962)