From Free Fatty Acids to Aromatic Esters: Esterification in the Still Made Simple(r)

For sale: birectifier ($900USD)

More important than esters is the mysterious congener class often referred to as rum or Cognac oil and I have unraveled its mysteries in other more recent posts. Decisions made to maximize rum oil will also maximize noble esters. Esters can be faked in contrived ways while rum oil is still divine.

This is an excerpt from the book on distillation I’ve been working on forever now. I’m trying to re-frame the text in a way that explores and emphasizes three main concepts:

1. Distillation is simple or fractional. Simple distillation is the separation of the volatile from the non-volatile while fractional distillation involves the further subdividing of the volatile.

2. Distillation is non-equilbrium like a pot still or can approach equilibrium such as in a column still. Volatility is effected by more than boiling point, and the relative miscibility of a substance in water or ethanol can make something with a boiling point higher than water extremely volatile.

3. Aromas are either created in the still or not depending on the presence of aroma precursors. Many fractions are recycled not only to salvage alcohol but also to allow more time under heat to turn aroma precursors into aroma compounds.

One of my goals was to give an introduction to the topic and some general advice for distillers of low levels of involvement. Many of the ideas are speculative. I was hoping to shed light on the science just below the surface of many distilling rules of thumb.

It is a complicated topic full of tangents but I kept it down to 2105 words!

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Many of the most revered aroma compounds are born in the still. Under certain conditions with the right precursors to feed the various processes, significant amounts of new aroma compounds are formed. The main process of aroma creation is esterification where free fatty acids react with alcohols under heat to form esters. Esters are very volatile and their fatty acids precursors are also volatile, even though they have boiling points higher than water. Many fractions of the distillation process are recycled into subsequent runs to give more opportunity for esterification. The recycling phenomenon means that you cannot just produce one batch of product because the final distillate is actually the product of many integrated batches. Aroma creation is not always maximized and restraint is often practiced to produce an elegant spirit. Pot stills are highly regarded for their ability to create new aroma compounds, but if column stills are operated with certain methods of recycling fractions, they can also produce very full flavored high ester spirits given the right inputs. Garbage in, garbage out is always the rule of the game.

Many processes are responsible for aroma creation, but likely the only process that can be controlled to any significant degree during still operation is esterification. Other processes like maillard reactions, hydrolysis and oxidation are definitely important, but when it comes to handling the still, they are likely just byproducts of decisions made regarding esterification [there are minor problems with this claim]. Full flavored spirits in pot stills differ from column stills by how the byproduct processes happen [I’m slowly learning the chemical ins and outs of articulating this]. If a pot still and column still were operated in such a way as to end up with the same ester content they would differ greatly in compounds created by other minor processes and the pot distilled product would likely be regarded as more complex.

To get esters to form in the still, the distilling material needs free fatty acids as precursors. Some source material is higher in fatty acids than others and some fatty acids are more noble than others. For example, apple varieties differ by fatty acid content with the higher being better suited for distilling material. The same is true of grapes. Not all esters are formed in the still or during fermentation. Esters are often already present in the source material and typically the higher the better. In fruit, esters form by enzymatic processes during ripening, more form by fermentation, even more form in the still, and believe it or not, even more form in the barrel. High total acidity in the source material often correlates to both high ester contents and high fatty acid contents which is why the wines of Cognac can yield a product with a higher ester content than the acid deficient wines used for California brandies. [What I’m missing here is that at the same time esters are forming they are also breaking up due to hydrolysis but at a different rate. Often they even reform. The first distillation, due to its significant total acidity, may be characterized by a positive net ester formation while the second distillation which has no significant non-volatile total acidity (to catalyze esterification) is characterized by a net loss of esters. [What I need is better research papers to support this. Most research projects only look at the first distillation and none (known to me) compare and contrast the processes at work in each distillation of double distillation.]

Yeasts are big sources of fatty acids and a percentage of the lees are retained in distilling material to produce esters from those fatty acids. Most full flavored spirits do not incorporate all of the lees due to off aromas produced as a result of having too many solids in the still. If there are too many solids there is a tendency for scorching. The relatively ordinary aromas produced from the lees may also overshadow the singularity and terroir of the source material. Some traditions exist of making brandies from accumulated amounts of left over lees, but these distillers likely have stills designed to handle high concentrations of solids such as the steam jacketed stills used for grappa production or “rousers” which continuously stir the distilling material. [A big thing this misses is how distillation on the lees traps certain non-desirable congeners possibly through a fixative effect of reducing their volatility.]

High total acidity in distilling material may be important to catalyze esterification during the first distillation phase of double distillation in a pot still. There are many approaches to having a high total acidity as seen in high ester spirits like Cognac, Bourbon, and Jamaican rum. The wines used for Cognac are naturally high in total acidity which might be why Cognac distillers have always favored slow double distillation in a pot still as opposed to a column still. California brandies may have opted for a column still because they never had enough total acidity to justify the extra time and fuel expense of a pot still.

Distillers of Bourbon increase the total acidity of their distilling material with the sour mash process where a portion of the non-volatile fraction of the first distillation phase, often called backset, is recycled into the next fermentation. The sour mash process has the three fold effect of increasing micro-biological stability, recycling fatty acids, and inducing acid-catalyzed esterification in the still.

The use of dunder to make high ester Jamaican rums is very similar to the sour mash process. Dunder is the non-volatile fraction of a sugar cane fermentation after distillation and characterized by high acidity. Molasses is so concentrated a sugar source that significant amounts of dunder can be used to bring the sugar content down to a reasonable level. Dunder can represent as much as 50% of a molasses based wash for a high ester style of rum. High total acidity creates slow, inefficient fermentations where secondary bacteria produce numerous extra aroma compounds [I have recently learned many of the finer points of this and attached the evolution of dunder’s use to some first names and specific dates]. In the 19^th century, high ester styles of Jamaican rum were produced as concentrates for exportation which would be diluted with relatively neutral spirits before bottling. The distilling material used for high ester Jamaican rums may have had 2.5 times the total acidity of the wines used for Cognac. Such high acidity would likely shorten the lifespan of a copper boiler but it is unknown (to me) whether Jamaican distillers used copper or wooden boilers [both and I’ve found more specifics on that!].

Another idea for increasing the total acidity of distilling material to catalyze esterification is with freeze concentration also known as jacking. Freeze concentration, which is sometimes called freeze distillation or fractional freezing, separates compounds by melting points. Distilling material that is freeze concentrated ends up higher in alcohols, aroma compounds, and total acidity.

Ciders are known to have been freeze concentrated and the process may have given early American cider brandies the name Applejack. There is no clear historical references to ciders being freeze concentrated before distillation, but it seems likely that it was practiced if inadvertently. Ciders were probably distilled later in the winter when there were less farm chores to be done and by that time casks of cider stored in the barn would start to freeze. Ice crystals would form on the top which could be separated and a zingingly tart, higher alcohol beverage would result. Supposedly, concentrations as high as 30% alcohol can be achieved. The elevated alcohol content may have even negated the need for a second distillation. Freeze concentration before distillation was rumored by the mid 20^th century flavor chemist Joseph Merory to create the highest quality fruit eau-de-vies, but no explanation of the underlying science accompanied his claim and it is not known if any commercial producers use the technique. The increased total acidity that results from freeze concentration likely increases aroma creation in the still through acid-catalyzed esterification.

Each phase of double distillation in a pot still is carried out slowly to maximize esterification [this may not be true if the second phase can be characterized by a net loss due to hydrolysis]. Applying too much energy can result in super heated hot spots in the boiler. Hot spots may break down yeast cells and reducing sugars generating favorable aroma compounds, but too many may also create off aromas by scorching. A pot still is thought to operate at non-equilibrium because there is no reflux beyond what naturally condenses on the walls of the still, but running the still too fast by increasing the energy applied to the boiler has been observed to change the distribution of the fractions. The observation may be the result of super heated hotspots volatilizing components in unpredictable ways [This is incorrect and the real reason is that reflux, due to the shape of a pot still, is more significant than you’d think. Run the still too fast and you challenge that natural reflux thus altering the fractions.]. Avoiding hot spots with a slow distillation may increase the predictability of fractions and therefore also increase product consistency. [Not challenging the natural reflux of the pot still in the second distillation will lead to a higher proof product and thus less spread out congeners and therefore opportunity for a larger hearts section.]

Not all fatty acids form esters in the first run. Often more time under heat is required so many of the fractions that are separated are recycled in the next batch. When you consider the linkage of batches, double distillation in a pot still ends up employing more fractions than people think and distillers often use various names confusingly. To understand double distillation it is useful to consider where every fraction ends up and why.

The first phase of double distillation in a pot still, often called a stripping run yields a foreshots (this term has different meanings historically) fraction that is discarded, a heads and tails fraction that are both recycled, a hearts fraction that is passed on to the second distillation phase and a non-volatile fraction that is often employed to recycle fatty acids that do not volatilize and to increase the total acidity of the next fermentation.

Under non-equilibrium distillation, what appears in the very beginning of the run can change significantly depending on the alcohol content. Besides above recognition threshold amounts of ethyl-acetate and acetaldehyde (that smell like nail polish remover) as well as methanol, the discarded foreshots of the first phase of double distillation may contain a lot of fusel oils that eventually moves to the tails of the second distillation where the starting alcohol content is significantly higher [k’ phenomenon] [The foreshots may even contain very high boiling point fatty acids that physically clung to the condenser, but are dissolved by the high ethanol content of the beginning of the next run. This residue becomes significant when a still is shared across different product categories.]. Fusel oils do not benefit from being recycled and are often only desired in low concentrations. Fractioning is used to separate fusel oils but they are also limited by manipulating fermentation variables to minimize their production. Fusel oils are the byproduct of stressing yeasts so distilling material is typically fermented to much lower alcohol levels than yeasts are known to produce in theory.

Not all distillers make a heads and tails cut during the stripping run. Some opt to pass everything along to the second distillation. The first phase of double distillation sees much more time under heat than the second phase as well as contains significant acidity to catalyze esterification so separating fractions high in aroma precursors and recycling them to the next batch’s first phase may result in the best opportunities for aroma creation. Some distillers only opt to return a portion of these heads and tails fractions to the next batch. These distillers are not trying to create the fullest flavored spirit possible but rather something elegant and refined.

During the second phase of double distillation, the alcohol content of the distilling material is much higher and all the non-volatile acids have been separated leaving nothing to catalyze esterification. Esterification continues to happen to fatty acids that have made it over into the second phase [Esterification continues, but so does hydrolysis which breaks up the esters and there may actually be a net loss of esters but no literature states a rule of thumb for what happens to ordinary esters versus more desirable extraordinary esters]. The increased alcohol content increases the rate of esterification in a way that may partially make up for the lack of significant total acidity. The second phase is separated into five fractions. A foreshots fraction is discarded while a heads and tails fraction is taken and a percentage recycled during the next batch’s second phase. The hearts fraction becomes the final distillate while the non-volatilized fraction is discarded. The non-volatilized fraction of the second phase which is mostly water also likely has a lot of congeners in common with the foreshots of the first phase.

When cuts are made and it is decided how much of the heads and tails fractions will be recycled or discarded, it is important to note that not all fatty acids and their esters are created equal. They are definitely not all desirable. The esters of longer chain fatty acids are typically more desirable than the esters of shorter chain fatty acids like acetic and butyric. Cutting a spirit will often involve separating undesirable shorter chain fatty acids and their esters, but like the higher alcohols, many of these components are better controlled and minimized by manipulating fermentation variables.

A column still also has many options to generate aromas in the still by the continuous recycling of small fractions that are high in aroma precursors. Once the still comes close to equilibrium a fraction that is high in volatile fatty acids is isolated and recycled through the column to increase its time under heat. A column still can increase the time under heat of small fractions while not investing in heating the rest of the volatile fractions which saves significant amounts of energy. The juggling of small fractions can produce large amounts of esters but the process becomes detached from other secondary aroma creation processes that typically happen alongside esterification during a slow double distillation in a pot still. [I don’t know how to explain this relative to the simultaneous esterification/hydrolysis phenomenon. I suspect the the fractions are relocated to a part of the column where alcohol is particularly high favoring ester formation over ester break up. Where alcohol is particularly high there is little water to break up the esters.]

Believe it or not, fatty acids have the potential of escaping esterification and making it all the way to the barrel. Barrel aging presents yet another opportunity for esterification (or even the breakdown of esters and other aroma compounds), but some distillers choose to remove many fatty acids by filtering through activated charcoal or using the chill filtration process. Untreated spirits have the potential to become cloudy upon dilution which many consumers are thought to object to. Particularly high fatty acid contents can also cause the distillate to appear cloudy after either phase of double distillation in a pot still.

Following the path of aroma precursors and their reactions can help distillers make more sense of the various fractions and where they end up. The extent to which fractions are recycled illustrates how integrated production runs are. Understanding the various options for operating a still when new aromas can be formed provides a basis for the experimentation required to sculpt distillates. This look at aroma creation is probably oversimplified by focusing on fatty acids and esterification as there are so many other reactions. Esterificaiton is just a starting point and eventually as involvement deepens, distillers will eventually build an understanding of the other aroma creation processes.

Creating beautiful spirits is more than just operating a still. Aromas born in the still, whether a fault or a feature, have precursors that can be traced back to fermentation variables or the source material. Reasonable guidelines for operating a still will free the distiller to take a deeper look back at fermentation and then eventually a further investigation of the source material, be it grains or grapes. Extraordinary aroma born in the still comes from extraordinary precursors. So many variables may be daunting, but that is why spirits are so revered and so special. Exploring the potential for aroma creation from selection of the source material all the way to bottling may help small distilleries create new classes of full flavored spirits which allow them to differentiate themselves from larger distilleries making more restrained styles of spirit. Awareness of all the considerations that go into producing a full flavored spirit will certainly increase appreciation for the work of any deeply involved producer.

[edited to add: One things this post doesn’t do is differentiate the common esters. In another post I spend a little bit of time musing about the most generic of esters, ethyl-acetate which is not widely understood. I connect this congener to the threshold idea where for some reason we want as much of it in a spirit as we can without recognizing it. This can be said as we want it above the absolute threshold but below the threshold of recognition. Understanding these thresholds might teach us about the distillation of highly aromatic spirit concentrates that eventually get blended down. Certain terroirs of sugar cane or grapes or even certain apple varieties from a diverse orchard might be treated differently during production to maximize aroma. These concentrates cannot stand on their own but have to be blended down to keep certain key generic congeners in check. I haven’t found any great literature that specifically explains the concentrate idea so I’m just musing about it in theory.

Another ester issue of note that can differentiate the pot still from the column still is that because higher alcohols tend to stratify and bunch up in a column, more esters of higher alcohols have the opportunity to form such as amyl esters which are undesirable and considered flaws.]