High Ester Rum

[distiller_dresden]

Thanks for tips Otis; I think between you and der wo I will order some and get into this. I just have certain episodes of Breaking Bad running over and over in my mind, and it's a different acid, and that's fiction on TV, and I know logically that sulfuric acid at 99% isn't going to immediately bubble through the table and my foot like xenomorph blood even were I to spill the bottle. It's not quite a 'phobia', but it's an unrealistic and irrational aversion nonetheless. I'm certain it will go away once it comes, replaced by excitement and curiosity, which in my case of course I will need to be extra careful to maintain caution.

It's like when I began mashing/distilling; I wore latex gloves and even dipped my long stainless spoon in rubbing alcohol and let dry before I aerated my mash to pitch. The lengths I went to for 'sterilization' or near it were monumental. Now I wash stuff with soap and water before a mash in, and will wipe down everything with a paper towel wet with vodka (cheap), but I don't really take precautions. I haven't had a single infection or issue of any kind in 5 months. I'll just have to remember that working with sulfuric isn't mashing in; I'm not risking a little bacteria, it's freaking dangerous. It's also not xenomorph blood, so moderation in my butt-clenching.

[OtisT]

Otis,
without infection no extra acids and no catalysed esters.

Yes, but now I have a baseline for what happens to uninflected dunder under these conditions. I do believe there are some fatty acids in there already and the infection simply makes new ones of a different type. Once my infected batch has had enough time to grow, I will retest and see how infected dunder behaves and if/how it is different that the uninflected.

FYI, my current dunder pit has a new infection in it. Not that bread smelling lacto I have been running, but something between sweaty socks and poop. I have not IDed the type of infection yet, but I am hoping it is one of the putrification infections you have been telling folks they want for a rum. It does not smell like dead flesh, like the smell some bad infections produce. The source was a dormant lacto infection on a jug of backset. I am guessing that my lacto was dormant, but this other infection was not and it is what came through when I propagated it. I have pics and am sending to an expert for input.

And airing is a bad idea: The volatile esters you produce will directly evaporate away.

I am learning this. . So does it matter then, if we air or don’t? Sounds like it don’t matter. I need to air after the spirit run regardless, so won’t these light eaters just go away then? This issue is one reason I let these samples sit a week out in the air. I wanted to know what stayed around and what floated away.

If you want to have an easy successful experiment with sulfuric acid and esters, mix in a small jar vinegar and any strong alcohol you have at hand (low wines, feints, neutral) 50:50, add a few drops sulfuric acid, close the jar, shake it and wait an hour. Then open it and you will smell it.

I will do the test you recommended in addition to expanding my test with infected dunder. Do you have any advice on how long an infection should be active in order to create sufficient acids to be noticed? I’m sure that longer is better. My past use has been with infections ranging from 2 to 5 months old. I do adjust PH up into the 5s, so they stay fairly active.

Thanks, Otis

[Birrofilo]

@disdiller_dresden

For not knowing anything, I thing you should buy diluted Sulphuric acid, i.e. liquid for lead batteries.
Good quality products are used in both batteries and food and farmaceutical industry.

http://www.marchi-industriale.it/it/pro ... ri-diluito" onclick="window.open(this.href);return false;" rel="nofollow

I suppose the one for batteries is very close to the one for farmaceutical industry, if it comes from the same process.

You only need a tiny quantity of acid as a catalyzer. Using the diluted form is probably much more practical and much safer than the pure form. I perfectly understand the "phobia" ragarding chemicals.

[der wo]

Acid burns with sulfuric acid are not like in a horror movie. It will not damage your skin immediately. You will be able to wash your hands after a contact (washing means 15min, not only a few seconds!). I think the most dangerous scenarion is that you don't recognize a contact of your fingers or gloves with the acid (a drop on the side of the bottle when you screw the cap on) and then you touch your eyes or other sensible parts with it.
And besides gloves and glasses wear long pants and good shoes. No sandals. Because another scenario is that the bottle drops down. Such shit happens.
And probably the highest danger is to have children growing older, more and more exploring the house and one day they find the bottle you have forgotten long time ago.

[distiller_dresden]

Well, if I'm going to work with sulfuric, I may as well use the purest. If you're going to Red Lobster, order the fecking lobster, I always say. And sandals, kids; not a problem, I'm not a sandals guy any longer, back in college that was so, but those days are past. Kind of like, "When I was a child I spake as a child..." I've outgrown sandals, lol, they are shite for support. For that matter I see people wearing flip-flops and can't for the life of me understand why you'd do that to your poor feet and arches (unless you're next to a pool, or at the beach). I live with my father and don't have kids, so we're good there! 40, though, it's possible, I do still reserve some small, maybe deluded hope that it's something someday...

As to airing and esters... This is back to Otis and I, zapata experienced it too recently, we all lost banana esters recently following distillation that were there right away then airing and nada any longer. Though mine did come back once I aged for 3 weeks on oak, that was also rum I had several over ripe pounds of mashed bananas in the mash.

My practice of airing has been 48 hours with a paper towel just placed loosely over my jars, maybe a spoon or something on top to hold it there. What if we did 'more', like doubled up the paper towel, and made 'squares' and then screwed the jar tops on without the cap part, just the screw part, and the doubled paper towel in between. Would this allow enough air to evaporate the undesirable compounds from the fresh distillate while still perhaps retaining the desirable esters like banana that we've been losing to the air?

This is important to me especially because this weekend I distill my apple brandy and I've ready conflicting things; Cranky says he airs his, while another experienced member says to immediately cap the jars following distillation lest you 'lose' the good fruit essences, which I'm going to assume he is referring to esters whether he knew or not.

[der wo]

My advice not to air is only for such an experiment. The goal of such an experiment is to get the clearest possible result.
And later after distilling: Unfortunately it simply depends on the volatility what evaporates mostly. So we have to get much good flavors, then we can sacrifice some while airing out also the bad ones. Volatility depends also on the abv, most esters are less volatile the higher the abv is. This is a benefit of cask strength editions btw: When you add water, also long open bottles will give you a fresh fruitiness.

Cranky vs "another experienced member": I prefer airing over cutting. I don't cut much fores and heads, but air long. My observation is, that airing cuts even better than a long packed reflux column.

[distiller_dresden]

Thanks for advice der wo; also I wasn't being abstract, I don't remember whose apple brandy thread I read the other in, but it was a longer one, or from context he's been making it for decades.

[zapata]

I do believe there are some fatty acids in there already and the infection simply makes new ones of a different type. Once my infected batch has had enough time to grow, I will retest and see how infected dunder behaves and if/how it is different that the uninflected.

Uninfected dunder should in fact have some acids, and even native esters. Perhaps varying a good bit with how you handle your yeast as I imagine a lot of both will be trapped in live yeast from quick fermentations but gets released when the cells die. For this reason (and tradition) I have been including lees in my dunder. Both the live lees from fermentation and the sediment of boiled yeast that settles from the dunder as it cools. But certainly it is far less and different in composition from infected dunder.

I think when you rerun these tests with infected dunder, the difference will be pronounced. Especially for the differences in fractions. Thats not to knock what youve done at all. This meticulous work is fabulous, even if the results are not earth shattering it is still good and useful info and sets a helluva baseline for comparing exactly what carboxylic acids from infected dunder add.

The sediment piques my curiosity though. I'm not aware of anything alcohol + sulphuric that should precipitate. Perhaps it is simple sulphate salts, and the precipitation is caused by the alcohol? Sodium sulphate for example is virtually insoluble in ethanol, but highly soluble in water. The same is true for calcium sulphate, though it has much less solubility in water to begin with. I dont think you mentioned the % of the fractions, but presumably they decrease in alcohol content, explaining the progressive decrease in sediment. Have you investigated the precipitate? Separated it, felt it, dare even taste it?

[distiller_dresden]

Zapata is a chemist; you're a chemist, or have a chemistry background, don't you zap? I'd like to get zapata, der wo, Otis, and myself together in cabin in the woods for 2-3 weeks with a couple of 55 gallon drums of high quality molasses, blackstrap molasses, several barrels of rainwater, 4 or 5 different yeasts, a microwave, a small lab, a wall stacked with cases of unopened mason jars, and several more barrels for fillin'.

Basically I'm saying I'd love to have nothing but time to devote entirely and completely to making rum and then experimenting with you 3, no distractions. I think the rum coming from that experiment would be world fricking class and quite possibly unrivaled for personal distillers.

[OtisT]

The sediment piques my curiosity though. I'm not aware of anything alcohol + sulphuric that should precipitate. Perhaps it is simple sulphate salts, and the precipitation is caused by the alcohol? Sodium sulphate for example is virtually insoluble in ethanol, but highly soluble in water. The same is true for calcium sulphate, though it has much less solubility in water to begin with. I dont think you mentioned the % of the fractions, but presumably they decrease in alcohol content, explaining the progressive decrease in sediment. Have you investigated the precipitate? Separated it, felt it, dare even taste it?

ABV of the feints I used:
Heads = 90%.
H/H = 86%
Tails = 80%
Oil = ??? Did not measure.
Dunder = very low. I boiled this down pretty far.

I speculated at the time that the sediment was coming from a heads alcohol (Ethyl Acetate), due to the progressive nature of the sediment depth and knowledge that the H/H and Tails were close in ABV. After sitting a week, there is little difference in depth between the H/H and Tails jar sediment level and I don't think there is that much Ethyl Acetate in my tails, so my revised assumption is it is likely Ethanol or a combination of alcohols including ethanol, and not just heads alcohols causing the sediment.

I did spend a little time looking at the sediment a few days back. I pulled some sediment out with a dropper and also pulled clear mix to compare to. Both smelled the same as far as I could tell. I know there was some dunder liquid mixed in with the sediment, so the smell is likely the liquid (dunder/alc mix) and the sediment is either the same smell or inert.

OK, I just tried a taste test. Yuk! The things we do for science.

For tasting I sampled from the H/H with Acid, one sample from the clear top liquid and the other from the sediment. I pulled a third sample from the HH mix that did not get Acid, to compare things to. First, the two with Acid were indistinguishable, both equally the worst taste I have experienced in some time. Nasty, bitter, sharp, and I wanted/needed to spit it out right away. I then tried the same mix with no acid. While it was not pleasant, it did not have the same sharp/bitter/make you want to spit it out right now kind of taste to it like the acid versions did. Not sure what I learned, other than I don't want to taste that shit again.

Otis

[distiller_dresden]

OK, I just tried a taste test.

Well, for me at least, this is what Otis is working with:

[der wo]

Uninfected dunder should in fact have some acids, and even native esters.

But those acids are the ones which didn't get esterified the last batch. Why should they get esterified this time? I think, those acids are not the ones we will smell as fruity esters next round. And from fermenting backset sugarheads (with uninfected backset) I know, such spirits come out relative neutral. That's why I don't see uninfected dunder being something much increasing the flavor.

The sediment piques my curiosity though.

I also recognized this sediment after adding sulfuric acid. I think that perhaps it's proteins? Proteins fall out when you lower the pH.

[zapata]

I'm not sure that it tells me anything either, but good on you for trying!

Protein coagulation makes sense.

And for the record I am no chemist. I have taken a number of chemistry classes, and have always been interested in the chemistry of various hobbies and pursuits so I have a halfway decent amount of lab gear. But at best I am a hack. A conversation between me and a real chemist is like a shadetree mechanic talking to an engineer. I could build a hotrod, but it'd be by slapping together parts that someone else designed. Some of which I'd understand, a lot of which I'd just accept and put to use.

[distiller_dresden]

Well to me I'm the shadetree mechanic, so in all things there are degrees, zapata! I'm a really smart guy, but my smarts lean toward words and writing and wordplay, I'm one hell of a cook/chef, and in all things creative I always excel. I love algebra and trigonometry, but when I got to calculus there was just this wall that I never identified and got over. That same wall seemed to be in place for chemistry, which I've always been enamored by, but when it came to the mathematics of chemistry and those chemical equations I was as helpful as a three-legged dog on a sled team.

Physics is real intuitive to me, but when we get to the molecular scale it's like voodoo, so I'm glad to have guidance from people like you, der wo, and Otis to lead me into and through this dunder thing because I LOVE this what we do. Making a better rum is important to me because I like to try and do the best version of anything I get into and put my mind at, and with all these experiments and the banana esters thread, this stuff has just expanded my imagination and my desire to make better, great rum.

[SaltyStaves]

Do you have any advice on how long an infection should be active in order to create sufficient acids to be noticed? I’m sure that longer is better. My past use has been with infections ranging from 2 to 5 months old. I do adjust PH up into the 5s, so they stay fairly active.

If you have summer temperatures, then not long at all.
My pit experiments have taught me a lesson in leaving things too long. Bacteria don't stop eating like yeast do and wait patiently for their next sugar hit... They'll turn your dunder to water if you leave them to it. I drew muck off at various stages, but I didn't recognize when it was done until it was too late. pH quickly climbed towards neutral and the acids were lost. I now have to reconstruct something usable from the samples I drew, but summer is gone and I have missed out this year.

The pit can go through stages where things seem to be going backwards. Horrible aromas can suddenly fall off and the sweet smell of the dunder comes forward. Then its suddenly back to smelling like something crawled in it and died. Knowing when to act and when to leave it alone, is tricky.

Make no mistake though, this isn't an overly long process. I think this notion of year-long muck pits culturing some finely aged soup, is one of pure myth. You can do it all in a summer. If you can create an artificial summer, then you can do it more often.

[zapata]

Actually Otis, if you don't mind I'd like to throw in a little rant, and some praise.
Our world is becoming both more scientific, and frightengly less so by the day. While the effect of science on our daily lives is undeniable, the number of people actually DOING any science seems to be dropping. 400 years ago a gentleman would have an alchemy lab in his basement, while even peasants were doing the proto-scientific work of breeding livestock or building ships. 200 years ago, much was the same, though the science was better, people were actually doing it. Granted it is better documented amongst the privileged classes, but I like to think that's more a matter of whose work was immortalized via documentation. With the rise of the middle class, chemistry, electronics, and physics was carried out in basements, garages and workshops around the world.

But in the modern era of secular consumerism, everybody "believes" in science, but nobody is doing it. You buy stuff, it works, and you thank science, as if science is the new God. It's leading to a strange kind of psuedoscientific fundamentalism where the average person espouses science but hasn't actually ever done any in their daily life. Unsurprisingly, these people actually know very little about science, and have an understanding of the world more akin to some puritanical pop culture. They retweet Neil deGrasse Tyson and pat themselves on the back. But their daily lives consist of either consumption, or the completely unscientific age old processes of trial and error, emulation, and old wives tails.
They make a recipe from "cooking for engineers" and claim to take a scientific approach to cooking. But they haven't once taken a scientific approach to cooking themselves, only repeated someone else's conclusion. They build something from a maker zine, and make a snarky social media post extolling the virtues of science. Yet all they did was the modern equivalent of a Sunday school craft project.
All this to say, Otis is doing good work here. He is exploring, hypothesizing, and testing. In an age where science is the new religion, this is God's work.

[kiwi Bruce]

Make no mistake though, this isn't an overly long process. I think this notion of year-long muck pits culturing some finely aged soup, is one of pure myth. You can do it all in a summer. If you can create an artificial summer, then you can do it more often.

Remember too, the pits in the islands are being constantly feed with new dunder, and the pros control the pH in order to control the constitution of the pit...keep it alkaline and everything is put on hold, the bacteria go dormant. Bump the pH down again...H2SO4...and it all comes back to life.
Don't be overly afraid of sulfuric acid, use caution :- glasses, gloves, apron, etc...I worked with the strong acids all my working life and believe me alkaline spills and burns are far worse than the acids and something to be very very careful with.

[SaltyStaves]

Remember too, the pits in the islands are being constantly feed with new dunder, and the pros control the pH in order to control the constitution of the pit...keep it alkaline and everything is put on hold, the bacteria go dormant. Bump the pH down again...H2SO4...and it all comes back to life.

I believe you may have that backwards. For dormancy, the muck is acidified. Lime is added to restart putrefactive development.

[zapata]

My current dunder infection was started this past week. The propionic bacteria I'm using makes 1 unit of CO2 for every 2 units of propionic acid and 1 unit of acetic acid. This gives me a visual indicator of how fast it is working. And its about as fast as a moderate speed wash fermenting. So it's working pretty quickly. I never even got it in the incubator before I noticed the bubbles and decided to let it go at shed temp of 70's.

So it may be different in different pits, different microbes, different temps, but I plan on using this in a few days.

[kiwi Bruce]

Thanks KIWI ...Now I'll have to look at the lost papers from Rafael Arryo again...
for anyone who doesn't have these...
https://www.bostonapothecary.com/rafael ... rs-on-rum/" onclick="window.open(this.href);return false;" rel="nofollow

[der wo]

My pit experiments have taught me a lesson in leaving things too long. Bacteria don't stop eating like yeast do and wait patiently for their next sugar hit... They'll turn your dunder to water if you leave them to it. I drew muck off at various stages, but I didn't recognize when it was done until it was too late. pH quickly climbed towards neutral and the acids were lost. I now have to reconstruct something usable from the samples I drew, but summer is gone and I have missed out this year.

The pit can go through stages where things seem to be going backwards. Horrible aromas can suddenly fall off and the sweet smell of the dunder comes forward. Then its suddenly back to smelling like something crawled in it and died. Knowing when to act and when to leave it alone, is tricky.

Make no mistake though, this isn't an overly long process. I think this notion of year-long muck pits culturing some finely aged soup, is one of pure myth. You can do it all in a summer. If you can create an artificial summer, then you can do it more often.

Reading this I think you are right with what you observed, but I think the causes are different than you think and you draw the wrong consequences:

Yes, if the pH rises, the pit can smell horrible like a dead animal and also will your Rum if you use this dunder. It's from bacterias which like such a high pH I think. And perhaps it's the high pH plus ammonia problem. But are the acids really destroyed? Acids in solution are two ions, the "body" of the acid and the acidity of the acid. This means for example for acetic acid (C2H4O2), the body C2H3O2- and the acidity H+. The H+ is part of every type of acid, no matter which one. If you now add a base the H+ gets destroyed (H+ and OH- connect to water). So you have destroyed the acidity, but not the body of the acid. If you now add any acid, no matter which, the pH drops, the acetic acid will be complete again. Or at least noone would know which of the acid is complete and which not. Exactly it doesn't matter which one is complete, it's the wrong question.
But why did your pH rise? Did you add a base? Probably not. But did you use for example oyster shells anywhere in the process? This would rise the pH very slowly. Or the minerals from the molasses go slowly into solution and rise the pH faster than the bacterias lower it, because there is not much food left for them.

For esterification the acidity is necessary. You can stop and reverse esterification by rising the pH. But you don't destroy the acids this way. At least in theory you can activate them again by adding any acid you have at hand. In reality everything is much more complicated probably. At least I don't think the long years mucks are a myth.

Or for example when we add sodium to heads, we do deesterification, we get acetic acid and ethanol from ethyl acetate. And acetic acid is way less smelling and way less volatile than ethyl acetate. That's why it works.

If your dunder smelled like a dead animal, you simply reacted too slow. You should have checked the pH regularily and lower it with for example citric acid when it rises over 5.5. Not to protect the acids, but to hinder the wrong bacterias.

[SaltyStaves]

I've drawn samples along the way and tested with sulfuric acid for aroma. It had very positive fruity esters at its peak, but now is almost identical to samples without H2SO4.
Whether fischer esterification could unlock those acids, I'm not sure.

[zapata]

Yes it certainly could. Derwo makes some good points about maintaining the culture, particular old pits with no food which certainly could happen at the hobby scale.

But you could be seeing other things as well. Esters and acids could be evaporating. Desireable esters can transesterify into less desireable ones. Acids can form insoluble salts and precipitate out. Lots of stuff can happen, we only know a slice of all the chemistry going on in a pit.

I for one will heed your warning. While I may play with a long lived pit, I will also save some peak dunder long term so I can take rum breaks and get started again readily whenever I want.

[der wo]

Yes, evaporation is also my suspicion. In the "pure acids and esters production"-thread I mixed for example wheat flour with neutral alcohol and added one drop sulfuric acid. Only 20ml all in all. I got interesting fruity flavors. But after a few sniffs they were gone. I think it's simply evaporation. But perhaps there are other causes we don't know too. At least this experiment is the reason why adding sulfuric acid is always the last step before distilling for me. I wouldn't lower the pH with it and then let the muck develop for months, I would use citric acid for pH and then directly before distilling sulphuric acid.

[CatCrap]

We have gotten really technichal on this thread, and gotten into dunder pits... which is a thread in of itself. Or 12 threads. 12 pages each. Fascinating subject.. but..

Otis, i too applaud your work This is getting into some serious distillation science and chemistry. But, we can quote arroyo etc etc all day and debate which acids do what and when and esterification... what i love, is that Otis is doing real life real time experiments. The MOST difficult part about all this, is that taste and aroma is highly subjective. it's so so difficult to pin down what TASTES GOOD. Because, for example, what tastes like cilantro to me, tastes like soap to you. What tastes like delicious year old UJSM to you, tastes like pig swill to me(not citing anything specific or any offense to anyone intended). And what tastes like funky ass dunder pit to many, tastes like pure delicious liquid gold to us!!!

Good on ya,Otis, keep up the good fight. You're a god damned inspiration.

[OtisT]

HER 1 Update - 14 weeks in the barrel

After three months I sampled my first batch of double pot stilled molasses rum (HER 1) that was in a toasted new american oak Badmo barrel.
It smells wonderful. I still smell the base of my molasses rum with all sorts of sweet fruitiness. The first few new smells that hit me were Vanilla and Butter. The Vanilla hits me first thing, while the butter seems to come and go. I can lightly smell the toasted oak underneath the heavier scents. There is also something new that may be caramel, or similar. Just can't quite name it. Any hint of tails or dunder that was in the barrel cut is no longer detectable.

It tastes a lot stronger of oak/toast than it smells. I would loved to have put this in a once used barrel, but I only had new. I don't what to over oak this so for me it's enough. I decided to pull the rum now, before too much more oak flavor gets in there. 6.5 liters at 65%. ( I was both lightly sampling and topping off this barrel over the three months.)

HER 1 pulled from the barrel

I really do want to give some of this more time on oak, so I decided to blend half of what I just pulled 50/50 with some of my triple pot distilled white molasses rum (HER2). So, half of my 14 week rum went back in with an equal amount of white triple distilled rum. I saved a small bottle of this blend to compare to later.

Half aged and half new rum going back in

I bottled some up to share and will figure out what to do with the rest at a later date. I think the remaining HER 2 white will be saved for adding to that barrel at a later date if/when I need to stretch out that oak some more.

All that's left

Otis

[zapata]

Sweet, all around success then. Love the labels!

[distiller_dresden]

Beautiful Otis! What was the toast finish on the wood for that barrel you had the rum in? I need to figure out what I am going to do for 2 BadMo barrels...

[Saltbush Bill]

There is also something new that may be caramel,

Otis I doubt you would have been disappointed had you let it oak longer, I believe the caramel would have developed further given time,that seems to be the case with mine anyway.

[OtisT]

Sweet, all around success then. Love the labels!

Thanks. I totally stole the idea from a scotch clearing house someone here on HD posted about. “Elements of Islay” is one of their blends you can look up to see different labels. It is intended to mimicking some form of elemental table chart or the like. The format works well for making similar labels for various styles of drink. Otis