Total acidity vs pH

I think we might be veering a bit off topic, but I figure I might as well ask while it may be at least slightly germane. In “Beyond Flavour: The Indispensable Handbook to Blind Wine Tasting”, Nick Jackson (MW) describes different “acid structures” for grape varietals and how to assess these qualities during blind tasting to make more accurate predictions (instead of relying mostly on fairly unreliable flavor/aroma markers). In particular, he talks about the “shape” of the acidity as perceived on the palate during tasting and how this differs from one grape varietal to another (this is mostly in the context of white wines).

I suppose what I am wondering is in what manner any of what we have discussed above (pH, TA, proportions of different acids) affect how a wine is perceived on the palate and if there is some substance to the notion that we can use these perceptions to differentiate between something like a Grüner Veltliner and an Albariño.

Yes, it’s well established that different varieties have different “shapes” to the acidity. Simple wines have simple shapes (think square, triangle, the ever boring circle). More complex wines get into more interesting shapes, like oval, trapezoid, isosceles triangle. Once you get to First Growths and Grand Cru Burgundies, you’re talking exotic multi-dimensional shapes, almost impossible to define with conventional mathematics. Natural wines veer into the imaginary plane. You don’t even want to try wines in the fractal shapes, those can be mind altering.

As the original poster, I have found these responses to be informative, entertaining (nerd alert!), and a wonderful example of what this board can be. Can you imagine how much legwork would go in to getting this information and clearly worded technical explanations anywhere else?

Answering a question that was asked or at least alluded to unthread: I am using this information (along with information on type of oak and %new) when I am on the fence for an online purchase where I can not taste the wine beforehand. When I am entirely reliant on website descriptions that use lots of !!! It’s helpful to have some objective information. From what I’ve read here, I think I can put total acidity in the same bucket as clone varieties. The bucket is labeled “things I am sure are helpful to somebody who is not me”

As a math nerd, I really liked this tidbit:

Taking the log of a value is notated with a lower case “p” (which seems unique to chemistry, it’s not a general math expression)

I can confirm this is not the norm in mathematics, but interesting nonetheless.

While I do prefer my wines to be topologically homeomorphic to a Klein bottle, it is a somewhat serious question about how the acidity of different grape varietals are perceived, particularly in the context of a differentiating feature to be used during blind tasting.

lol, glad you didn’t take it the wrong way, these folks just make me laugh with their descriptors.

I mean, different varieties have so many differences, obvious and subtle, that trying to break it down to unique properties of acidity seems like a fool’s errand. I guess that implies there are other aspects that can be broken down as well, and you can use the weighted ensemble to uniquely describe any wine. I’m not will to go down that road, it seems more like something a television preacher would come up with than a serious wine professional.

Sure, to be fair, Nick Jackson is not a chemist; I believe he is a theologian by training. However, there is something to be said for the amount of practice and experience that goes into achieving the credential of MW. Whether or not the observation (“shapes” of acidity) can be explained by some simple attribute of a wine’s composition is not so important as whether or not it can be a reliable indicator of the varietal. From somebody who simply finds the endeavor of blind tasting to be fairly fascinating in and of itself, I am always seeking to learn more about how we can connect the physical properties of a wine to the subjective perceptions of tasting a wine.

Here’s the thing, though - yes, pH and titratable acidity or TA run in opposite directions . . . generally, the lower the pH, the higher the TA. BUT - there are many factors, including buffering capacity and changes in soil chemistry - that can alter this relationship.

Therefore, looking only at the pH instead of looking at that AND the TA can give a false sense of ‘acidity’. For instance, if the juice from white grapes has a pH of 3.1 or 3.2, winemakers would in general feel that there is ‘enough acidity’ in the case they are trying to make an austere wine. And most of the time, they would be correct . . .

But the last few years, this has not been the case in many instances. pHs and TAs did not track in a predictable manner, and more often that one might think, a low pH was not indicative of a high TA. In fact, in many cases, TA’s were more in line with much higher pHs . . . and therefore, by only looking at this one factor, one might be led to believe that there was sufficient acidity when there really was not.

Cheers

Alan’s post is excellent. Thank you Alan for a clear and entertaining overview of such a complex topic.

I’ll add some more wine-specific analytical chemistry details here, including a couple things that conflict with parts of Alan’s (generally great!) post.

TA = Titratable Acidity
It’s with good reason that the two professionally trained chemists who’ve commented on this post so far both mentioned how irritating/confusing the term “total acidity” is. Let me be very clear here: the term “total acidity” is not used by anyone in the wine industry except as an error/misunderstanding (with a few niche exceptions). Annoyingly, “total” and “titratable” both begin with a “t”, so when we talk about “TA” people understandably get confused. In general, 99% of the time you hear someone say “total acidity” in a wine, they actually mean “titratable acidity”. Yes, this includes on wine labels, in marketing material, and on some supposedly educational websites. “Total acidity” is actually an important concept in the abyssal depths of nerdy wine chemistry but I think it should be separated from this discussion for the sake of clarity.

But what is Titratable Acidity?
Titratable acidity (“TA”) can be thought of as a measure of the “effective acidity” of a wine. First, I will explain what TA is and how we measure it, then we can go on to how this relates to sensory experience and pH.
Remembering from Alan’s post that acids are compounds that can release, or “donate” a proton (a.k.a. hydrogen ion), each acid in wine exists in multiple forms: some of the molecules will have their donatable hydrogen(s) attached, others will not (this is a simplification but the general point is true). The ratio of these forms depends on the pH of the wine, which is determined by the overall chemistry of the mixture.

To measure TA, we perform a titration! We add a strong base (sodium hydroxide), which essentially gobbles up all of the available protons it can. As you add the base, first the most easily donated protons are released from the acids and consumed by the base*. As you add more and more base, less easily donated protons start to be donated. As you add the base and it takes away these protons, the pH of the mixture increases (because there are fewer free protons around!), but the extent to which the pH rises as you add the base is dependent on how much of each acid you have, and how strong each of those acids is. We keep adding the base until we get to a specific pH (usually 8.2). Then, to calculate TA, we take the amount of base we added and use a conversion factor that basically says, “if all of the acid was tartaric acid, how much would react with this amount of base to take the wine from its original pH to 8.2?” This is why TA is reported as “tartaric acid equivalents”. It’s a handy convention to account for the fact that acidity in wine comes from roughly 6-10 important acids, depending on the wine. I think in France they traditionally refer to TA in sulfuric acid equivalents…so be aware of that if you’re comparing numbers to those originating in Europe - they’ll look quite strange.

How are pH and TA related?
To a first approximation, high TA should = low pH, and in general it is true that wines with lower pH tend to have higher TA, and vice versa. However, we’ve got to bear in mind that wines are, chemically speaking…SO COMPLICATED. I’m actually not going to go into the details of how the other components in wine - and some winemaking processes - can obscure the relationship between pH and TA, partly because I’m mid-harvest so my brain is a bit mushy, and partly because I really don’t fully understand it myself and I would rather be brief (hah) than give people incorrect information.

What I will say is that a huge variety of factors are at play here. It is hard to overstate the complexity of wine as a matrix. Potassium plays a really important role in modulating pH and TA in wine, but it’s only one (important) component, and there are a lot of others. Among the inorganic cations, calcium, sodium, and magnesium may all be important in certain circumstances, and that is just barely scratching the surface. Anyone who tells you they know the answer probably doesn’t, though they may have interesting things to contribute to the conversation.

What are the relevance of pH and TA to wine’s sensory characteristics?
pH is not well correlated with people’s perception of acidity in wine. However, TA is very well correlated: higher TA = higher perceived acidity. You can, in both theory and practice, have a Cabernet Sauvignon at pH 3.9 that tastes more acidic than a Pinot Noir at pH 3.4. Having said that, one area of wine chemistry that is, in my mind, woefully understudied - at least from what I’ve read - is in characterizing types of perceived acidity. If you have three wines with similar TA, residual sugar, alcohol, and acid profiles, why does one taste “juicy” while another tastes “sour” and the third tastes “zingy”? I think this is the kind of thing Nick Jackson was trying to get at. Sometimes spatial analogy is more helpful than chemistry. We can’t measure EVERYTHING.

pH does have an impact on the color of red wines because anthocyanin speciation is pH-dependent. Lower-pH wines will generally be brighter red, while higher-pH wines may be more purple or blueish (don’t read too deeply into this though, because color is also dependent on the populations of different anthocyanins, which varies across grape varieties). TA is not relevant to this.

pH, TA, and the relationship between the two, have quite a number of important implications for both viticultural and winemaking processes, but that’s getting a bit out of my wheelhouse so I will let the actual viticulturists and winemakers on this board talk about that while I scurry back into my lab :slight_smile:



*In the case of titrating with sodium hydroxide, the reaction can be thought of as sodium hydroxide + tartaric acid → sodium tartrate(aqueous) + water). A similar titration happens during red winemaking, as potassium released from the skins reacts with tartaric acid in the liquid, leading to an increase in pH/decrease in TA and, ultimately, saturating the wine with potassium hydrogen tartrate, which then gives us our beloved(?) tartrate crystals. The effect of this crystallization on the pH depends on the starting pH of the wine, but it will always decrease TA…this is one of the things that can give you variation in TA vs. pH.

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I scanned, so forgive me if this was covered.

The two primary acids are Tartaric and Malic. Later, if a wine is through ML, Tartaric and Lactic.

In functional terms, if the TA is high for a given pH it means that more of the acid is Malic and less is Tartaric. If a wine has a relatively low TA and low pH it means that more of the acid is tartaric, since tartaric is the stronger acid. Stronger meaning that it gives up h+ more freely at lower pHs and thus has more impact on pH per gram of acid that the others.

I’m pretty sure you meant pH 3.0 - I’ve had some nice wines at around pH 2.9 to 2.8 but they’ve always been ridiculously high in acidity. I’ve never seen a wine nowhere near pH 2.0, let alone below.

One way to learn about your own perceptions is to find some Sherries and Madeiras with similar levels of residual sugar, for which you can also find good tech sheets with both TA and pH. Sherry is one of the few wines that often has both relatively low pH and low-ish (not high, anyway) TA. I think it’s because Palomino is not a high acid grape, and the grapes are so underripe at harvest and then are (typically) acidified, but I’m not really sure. In any case, those comparisons can teach you a lot about how you perceive these differences.

I’ve never seen anywhere that Palomino grapes would be picked underripe. To my understanding, they are always harvested at full (not over-) ripeness. Agree on Palomino’s low acidity, but haven’t heard of acidification and I doubt that at least traditionalists like Bodegas Tradicion or almacenistas do really anything with the grapes except for crushing them and at some point fortifying the must.

It’s true that Sherry tends to have a low TA (normally around 4,2-4,8 g/l, high TA a bit over 5 g/l - only some Sherries aged for a very long time, like VORS and Dos Cortados, seem to have very high acidities - probably due to evaporation that concentrates acids and other non-volatiles). Don’t know where Sherry pH normally is, but I wonder if the biological aging (the flor yeast consuming different compounds from the wine and producing acetaldehyde in the process) might have something to do with it as well?

Thanks, pH 3.0.

Ben’s post is excellent, and much better laid out than mine for what it covers, thanks!

So if I got this,

titratable acidity = what chemists measure,

pH = how chemists quantify and talk about free ions,

total acidity = a wine geek term like “minerality” that mostly means how sour something tastes

More seriously, that study by Boulton was fantastic. Thanks for the link Chris!

And thanks to Alan et. al. for the lesson!

This is kind of what I’ve always assumed is at play when winemakers talk about the relationship between pH and TA, and how that translates to the perception of acidity in any particular wine.

To take it one step further, we’ve talked about the strength of an acid. That strength is reflected in a constant unique to each compound called pKa (again, meaning the negative log of the acid dissociation constant). The lower the pKa, the stronger the acid. Diprotic acids (with two dissociable protons) have two pKa values. The second pKa is always higher, as it becomes much more difficult to strip away the second proton after the first is gone. The values for the three most common acids in wine are

Tartaric (diprotic)
pKa1= 2.89
pKa2= 4.40

Malic (diprotic)
pKa1 = 3.40
pKa2 = 5.20

Lactic (monoprotic)
pKa = 3.86

In practical terms, if the pH of a solution is less than the pKa of an acid, the protonated form of the acid will be the dominant species. For most wines, tartaric acid will be the most prevalent form, with very little tartrate anion. OTOH, a wine with pH of 3.3 would have more lactate ion than the protonated lactic acid. I can’t say I know exactly how the balance between the two forms impacts taste and perception of acidity, but it surely does.

An interesting math tidbit is that when the pH of the wine is equal to the pKa of an acid, that acid will have equal amounts of its protonated form, and its deprotonated anion form. As the pH changes, near the pKa value, that equilibrium between protonated and deprotonated changes as well. So, by coincidence, the equilibrium behaviors of prominent acids in wine (where pH values are typically in the range of between 3 - 4) are highly susceptible to pH. It’s not much of a stretch from there to recognize that these various equilibria are the underlying source of our perceptions of acidity in any given wine. Then throw in the monkey wrench of the interaction with your own mouth’s acid environment, where the balances can quickly change, even while tasting the wine.

While it may be a little complicated, I’m convinced that this simple science goes a long way in explaining our perceptions of wine acidity, it’s not all that difficult.

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Well, they talk about fully ripe grapes in Champagne too, so I guess it’s all about context. I think the high yields are a significant factor here. I guess there’s no point in discussing this further as it’s quite subjective.

As far as acidification, I’m surprised you haven’t heard of it. I suspect you have at least read about it. It’s almost universal, from what I’ve been told. I don’t know what sources you’ll find trustworthy, but here are a few. You’ll note the language used is often not that it sometimes happens, but that it happens, implying it’s done as a matter of course. I remember an MW (wish I could remember who) telling me years ago that it’s pretty much always done, including by the traditionalists. I know most producers don’t like to talk about it, and some outright deny it, as is the case with so many “interventions”. I think the idea that it’s necessary for microbial stability is not always true, but it’s thought of as part of the process, so producers simply do it regardless.

Oxford Companion, Sherry entry:

Today acid levels are adjusted with the addition of tartaric acid prior to fermentation

https://www.sherrynotes.com/2018/background/8-things-wine-folly-got-wrong-about-sherry/:

The pH in Palomino grape juice is troubling and often has to be corrected to avoid bacterial contamination.

https://www.sherry.wine/sherry-wine/production/vinification:

After filtration the clear the must is subjected to a process of pH correction by adding tartaric acid.

Before fermentation commences, the must is usually acidified and sulfured

There are several academic studies on the topic because it’s so common.

https://www.researchgate.net/publication/285704374_Study_of_the_acidification_of_sherry_musts_with_gypsum_and_tartaric_acid

https://www.bio-conferences.org/articles/bioconf/abs/2016/02/bioconf-oiv2016_02023/bioconf-oiv2016_02023.html:
(from the abstract)

Calcium sulphate addition has traditionally been used in Sherry winemaking to reduce the necessary dose of tartaric acid.

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Except for Champagne being on the northern limits of where it’s still possible to grow grapes, whereas Jerez is one of the hottest spots in whole Europe. Apples and oranges.

And actually the first link you gave (and quoted) says, fully quoted:

The nature of Palomino grapes and the fact that they are picked late results in low acidity wines: an average total acidity of 3.7 g/l and virtually no malic acid. The pH in Palomino grape juice is troubling and often has to be corrected to avoid bacterial contamination.

As Palomino grapes in Canary Islands that are also picked ripe, but harvested a bit earlier and grown in a cooler climate tend to make wines with TA around 5.5-6.0 g/l, I’d say the grapes in Jerez are picked quite late, not early, as you imply.

As far as acidification, I’m surprised you haven’t heard of it. I suspect you have at least read about it. It’s almost universal, from what I’ve been told. I don’t know what sources you’ll find trustworthy, but here are a few. You’ll note the language used is often not that it > sometimes > happens, but > that > it happens, implying it’s done as a matter of course. I remember an MW (wish I could remember who) telling me years ago that it’s pretty much always done, including by the traditionalists. I know most producers don’t like to talk about it, and some outright deny it, as is the case with so many “interventions”. I think the idea that it’s necessary for microbial stability is not always true, but it’s thought of as part of the process, so producers simply do it regardless.

Oxford Companion, Sherry entry:

Today acid levels are adjusted with the addition of tartaric acid prior to fermentation

8 things Wine Folly got wrong about sherry | SherryNotes> :

The pH in Palomino grape juice is troubling and often has to be corrected to avoid bacterial contamination.

Vinification | Production - Sherry Wines> :

After filtration the clear the must is subjected to a process of pH correction by adding tartaric acid.

https://www.guildsomm.com/webupload/webdocs/sherry.pdf?Redirected=true

Before fermentation commences, the must is usually acidified and sulfured

There are several academic studies on the topic because it’s so common.

https://www.researchgate.net/publication/285704374_Study_of_the_acidification_of_sherry_musts_with_gypsum_and_tartaric_acid

Development of a chemical model to predict the doses of calcium sulfate and tartaric acid to acidify musts in Sherry area - ProQuest

https://www.bio-conferences.org/articles/bioconf/abs/2016/02/bioconf-oiv2016_02023/bioconf-oiv2016_02023.html> :
(from the abstract)

Calcium sulphate addition has traditionally been used in Sherry winemaking to reduce the necessary dose of tartaric acid.

Great list of sources, thanks! Looking into them right now.

Almost, but not quite. Total acidity and titratable acid are more or less interchangeable. Since titration is typically the way it’s measured, TA on a wine tech sheet should probably be thought of as “titratable”. They’re not exactly equivalent, only because titration is an imperfect way of determining exactly how many acidic protons are available in a wine. But they should be pretty close. It’s like measuring the dimensions of a room by walking steps along the sides, or using a laser measuring device.

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Nice discussion!

There are four primary acids (referring and merging the before/after ML discussion above): the three mentioned above (Tartaric, Malic, and Lactic)…the other is Potassium Bitartrate, which is an acid salt, is monoprotic and has a pKA of 2.72 (I believe this is correct). It functions as a spoiler in wine, as far as I can tell. I mention this only because Potassium Bitartrate is the main (or one of the main) cause of 'High pH/High TA syndrome. In addition, if you want to achieve a low pH low TA wine (Chardonnay for example, cuz why not), then preventing most or all Potassium BiTartrate would be a requirement.

Correct me if I’m wrong, but isn’t potassium bitartrate an acid salt - exactly as you said - and not an acid?

Secondly, isn’t potassium bitartrate the same thing as wine crystal? Which is basically one of the most common things a wine drinker might encounter in their wines? So how it is a spoiler in the wine?

I’m also interested to hear how one prevents potassium bitartrate in winemaking!

I’ve never seen anywhere that Palomino grapes would be picked underripe. To my understanding, they are always harvested at full (not over-) ripeness. Agree on Palomino’s low acidity, but haven’t heard of acidification and I doubt that at least traditionalists like Bodegas Tradicion or almacenistas do really anything with the grapes except for crushing them and at some point fortifying the must.

Adding gypsum to the must or fruit is the traditional way to acidify sherries.

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