Wine pH & Acidity

Concepts and chemistry of pH,

organic acids, buffer capacity and
wine quality implications of pH
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Effects of pH on wine
 biological stability – spoilage organisms are
generally inhibited at lower pH, whereas high pH
may favour them
 colour - particularly of reds, lower pH wines
exhibit more purple and ruby tones, higher pH
wines more brick and orange tones
 oxidation rate – increased at higher pH
 protein stability – lower pH tends to foster more
rapid precipitation of unstable proteins
Effects of pH on wine (cont)
 effectiveness of preservatives – the active
(molecular) forms of sulphites and sorbic
acid exist at higher levels at lower pH
 tartrate stability – dissociation of tartaric
acid is pH dependent
 Overall palatability is affected by wine pH
 Definition of pH
 pH is related to the concentration of the H+ ion in
solution
 pH = -log[H+]
 pH in fruit juices ranges from around 2 in lemon
juice to around 4 for warm climate grapes
 Hydrogen ions are produced by the dissociation of
acids in solution (under equilibrium)
 HA  H+ + A-
 pH versus Titratable Acidity
 pH is a measure of [H+] only
 pH in wine depends on both the concentration of
acids present and their relative degrees of
dissociation
 Titratable acidity measures free [H+] plus all
undissociated acids that can be neutralised by a
base
 pH and TA are not the same thing, nor do they
have a linear relationship!
 Organic acids in wine
 Diprotic acids:  Monoprotic acids:
 Tartaric acid  Acetic acid
 Malic acid  Lactic acid
 Succinic acid
 Acetic, Lactic and
 Triprotic acids: Succinic acids are
 Citric acid products of
fermentation
Weak Acid Dissociation in Wine
 The degree of dissociation is specific to each acid
 denoted by the dissociation constant (Ka)
Ka = [A-][H+]
[HA]
 Diprotic and triprotic acids have a K value for
each hydrogen ion (K1, K2 etc)
 In wine, K values are typically around 10-5
 This represents only about 1% dissociation
 Tartaric acid is the ‘strongest’ acid – 50%
dissociation of first H+ at pH 3.14
Dissociation Constants of Organic Acids
in Wine
Acid KA pK in Wine
(12% Alc, 20 deg)
Tartaric (1) 9.1 x 10-4 3.14
(2) 4.26 x 10-5 4.32
Malic (1) 3.5 x 10-4 3.55
(2) 7.9 x 10-6 5.05
Citric (1) 7.4 x 10-4 3.23
(2) 1.74 x 10-5 4.64
(3) 4.0 x 10-7 -
Acetic 1.76 x 10-5 4.79

Succinic (1) 6.16 x 10-5 4.29

(2) 2.29 x 10-6 5.56
Lactic 1.4 x 10-4 3.96
Example: Distribution of tartaric
acid species at various pH
Wine is a Chemical Buffer System!
 A buffer solution resists changes to pH
when addition of acid or base is made
 Buffer solutions consist of a weak acid and
its conjugate base (or vice versa) in
chemical equilibrium
 The buffer capacity of wine is a result of the
combined effects of different organic acids
in both their dissociated and salt forms
 Mechanics of Wine Buffer
Chemistry
 Simple buffer equilibrium (weak acid buffer)
HA  H+ + A-
 Upon addition of acid, free H+ consumed by A-:
A- + H+  HA
 Upon addition of base, OH- reacts with H+ to
produce water: OH- + H+  H2O
 Limited change in pH will occur, due to these
interactions
 In each case, the original equilibrium will be re-
established at the new pH based on Ka values
Wine Acidity Titration Curve
 Weak acid vs. Strong Base,
therefore endpoint is >pH 7
 Flat areas of curve show
areas of greatest buffer
capacity
 Although wine is a mixture
of weak acids, it is not
possible to separate them by
titration as the pKa values
are too similar
 Therefore we only see the
one inflection point
 Effect of Potassium Ions on
Wine Acidity
 Titratable acidity values will vary with potassium
ion content
 Potassium is a significant component of grape
juice
 Potassium ions modify the dissociation
equilibrium of organic acids
 This is due to binding of organic acid ions
(particularly bitartrate) as the potassium salt
 Some potassium acid salts react with NaOH
during titration, others do not.
 Effect of Alcohol on
Wine pH and acidity
 Equilibrium chemistry of
wine acids and salts is
modified by presence of
alcohol
 Solubility of some species
is lower in alcoholic
solution, particularly
tartrate salts
 Wine has a lesser buffer
capacity than juice
Consequences for Winemaking
 Difficult to significantly alter high pH levels in
juice or wine by acid additions
 Winemakers must judge effect on pH against
effect on flavour and wine balance
 Buffer capacity of individual wines will vary
depending on their organic acid profile
 Cannot easily predict the effect on pH of a given
acid addition
 Only slight changes in pH during fermentation
Case Study – Tartrate Stability
 Unstable wines can precipitate tartrate salts
over long storage time
 Includes potassium tartrate, potassium
bitartrate and calcium tartrate salts
 Particularly likely if wine is stored cold
 Unsightly in bottled white wines
Tartrate Stability – pH Issues
H2T
Distribution of tartaric acid species at typical HT-
wine pH range T=
80
70
% concentration of total

60
50
40
30
20
10
0
2.8 3 3.2 3.4 3.6 3.7185 3.8
pH

Equations
 HT- + K+  KHT H2T  H+ + HT-
 HT-  H+ + T= T= + H2O  HT- + OH-
 Tartaric Acid Dissociation in Wine
(Simplification, ignores effects of other weak acids)
pH H2 T HT- T= New pH pH change
2.8 67.41 31.61 0.98 2.53 -0.27
3 56.19 41.75 2.06 2.68 -0.32
3.2 44.06 51.89 4.05 2.84 -0.36
3.4 32.29 60.26 7.45 3.05 -0.35
3.6 22.04 65.19 12.77 3.36 -0.24
3.7185 16.99 66.02 16.99 3.7185 0
3.8 14 65.63 20.37 4.51 0.71

 At pH 3.718 the dominant form is HT-, with the other two forms H2T
and T= present at equal concentrations
 Precipitation of KHT occurs when [K+] and [HT-] exceed the solubility
product constant
 HT- concentration decreases dramatically with precipitation of KHT
 Equilibria of other tartaric acid species will shift to compensate
Consequences of KHT Precipitation

 At pH 3.718, the equilibria shifts result in equal quantities of H+

and OH- being produced
 hence no net change in pH despite loss of KHT
 At lower pHs, [H2T] is dominant species
 H2T equilibrium shift produces more H+ than OH- produced by
T= equilibrium shift
 therefore pH is decreased
 At higher pHs,[T=] is dominant species
 T= equilibrium shift produces more OH- than H+ produced by
H2T equilibrium shift
 therefore pH is increased
 In all cases of KHT precipitation, titratable acidity decreases
Potassium Bitartrate Stabilisation
 Wine is cooled to force precipitation of salts
 Temperature range -2°C to +2°C
 As KHT is less soluble at lower temperatures, wine
becomes ‘supersaturated’
 Formation of crystal nuclei requires energy
 Winemakers assist by ‘seeding’ the chilled wine with
powdered KHT
 ‘seed’ provides nuclei for crystals to precipitate from
solution
 Wine is held at low temperature and filtered cold once
precipitation is complete
References
 Zoecklin, Fugelsang, Gump & Nury, Production Wine
Analysis, Van Nostrand Reinhold, ©1990
 Ribéreau-Gayon, Glories, Maujean & Dubourdieu,
Handbook of Enology Vol 2, Wiley ©2000
 Harris, Quantitative Chemical Analysis, Freeman ©1991
 Delfini & Formica, Wine Microbiology: Science &
Technology, Marcel Dekker ©2001