Although this is a very basic reaction between a haloacid and an alcohol, SWID thought he would post his notes here for the future reference of anyone interested. Also, its good practice for when he has something useful to relay.
SWID started with the methodology of Alfred E. Holt as outlined here
https://www.thevespiary.org/rhodium/Rhodium/chemistry/tcboe/chapter4.html
. Not having the 5L flask, SWID made do with a one liter flask, and scaled the reaction down to a 'half batch'.
1st Run:
400mL 74% H2SO4 (4.69mol), followed by 263mL 95% EtOH (4.29mol) were added to the flask placed in an ice bath on a stirring hotplate, with the stir bar added before any of the reagents. After the solution in the flask had cooled to 5-10C, the stirrer was started and 164.6g of NaBr (1.59mol) were poured slowly into solution, allowing for not letting the stir bar stop. The distillation setup was attatched with ice cold water in the condenser and a 500mL recieving flask also in an ice bath. At this point it is worth noting that there was quite a bit of salts in the reaction flask, and SWID was unsure if this was undissolved sodium bromide or precipitated sodium sulfate. (More on that on second run.) The water bath was brought to 50C, and the contents of the reaction flask allowed to come to thermal equilibrium. Although some small amount of effervescence was observed in the flask, no distillate was coming over. The water bath was brought up to 75C, at which point the distillate began to come over. The temp was allowed to drop to 65C in an effort to find the "lowest temperature that the ethyl bromide will distill", but this was too slow. It was found that a 73C water bath (deep enough to cover the flask up to the 450mL point, with ~700mL of fluid in flask) produced a distillate at a rate of one drop every two seconds. The temperature of the distillate was, interestingly enough, 50-52C. This process was allowed to continue for about eight hours (2-3 hours my ass!), at which point the reaction was stopped, and SWID measured 62mL of crude EtBr in the recieving flask. He sighed, cleaned up the mess, threw stoppers on both the reaction and recieving flasks, threw them in turn into the fridge, and went to get some sleep.
The next day, the reaction flask had a thick crsytal cake in it, and pouring off the supernatent liquid revealed a rather beautiful crystal formation, like a porcupine with 2-3cm long crystal spikes. The cake, after admiration and hesitancy, was dissolved in a large amount of water and disposed of. SWID set down and did the math regarding the molar equivivalents, and realizing the ridiculous limitation of only ~1.6mol of NaBr, decided that was the reason for the low yield. Thus, he began run 2.
2nd Run:
Same setup, 400mL of H2SO4 + 263ml EtOH, chilled to 5-10C. This time however, SWID unthinkly dumped the entire portion of 329.3g NaBr (3.2mol), freezing the stirbar in the cake formed at the bottom. The water bath was brought to 75C for six hours, during which another measly ~50mL distilled over, at 50-52C. SWID let the setup cool, then added another 50mL of ethanol which resulted in spontaneous crystallization in the upper layer of the liquid portion of the flask. On swirling, it redissolved. The water bath was then raised to 90C, at which point the distillate came over at a much more respectable rate (roughly 1.5 drops a second), and still maintained the 50C. SWID noted that the bubbles in the reaction flask were not just being formed on the salt cake, but actually were forming as the cake was dissolving, which has led SWID to believe that to some extent the NaBr is coated by a passifying layer (at lower temps) of precipitated sodium sulfate. Another six hours and the crystallized salt on the bottom had disappeared. (Note that once the stirbar was finally freed, the distillation went MUCH faster.) Soon after the distillate temp began to climb while the volume decreased, and so the water bath was allowed to cool to room temp. The reciever flask had 300mL of crude EtBr in it at this point. (Note that the same reciever was used for both runs, with the run from 1 still in it.)
Purification:
Took the ~300mL distillate, washed 2x50mL dH20, 1x50mL of brine, and once more 50mL of dH20. Placed in a clean 1L flask with a "handful" of calcium chloride and a stirbar, and vigorous stirring was started. After roughly thirty minutes, the water bath (same one from before) was heated to 40C, and the EtBr began to distill at a very rapid rate (almost pouring out of condenser, but a ballon on the sidearm of the recieving flask indicated that it was all being condensed). The temp of the distillate was exactly 38C. After distillation was finished, SWID had 290mL of clean EtBr in reciever. SWID thinks it probably isn't 100% dry though, as after distillation it was distinctly cloudy.
Notes of changes from referenced methodology:
1. Unless, like Alfred E. Holt, Sodium Bromide is a difficult or expensive reagent to obtain, do not use such an excess of sulfuric and ethanol. It is just a waste. In fact, SWID would recommend scaling down some the molar ratios even if NaBr is harder to get.
2. SWID got the impression from the paper that a lower temp. water bath was needed. Not so. Just heat that sucker up to 90C, and do your purification in subsequent steps if your concerned. (SWID doesn't think diethyl ether is a serious byproduct of this reaction, even at 90C, considering that anything below 130C in the optimized synth of ether results in very low yields.)
3. Two hours is a joke, even with a 90C water bath. With vigorous stirring, maybe four or five.
4. The reaction isn't done until the cake in the lower portion of the flask is solvated.
5. Definetly pour in the NaBr slowly or in aliquats, with good stirring. Don't let the stir bar freeze up.
And there you have it.