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‫תהליכים כימיים ביישון יין בחבית ובבקבוק‬

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OXIDATION–REDUCTION
PHENOMENA
 Varying quantities of oxygen are dissolved in wine during aging, depending on
winery practices and the temperature at which the various operations are carried
out.
 Saturation is on the order of 10 mg/l at 5C and 7 mg/l at 25C.
 This molecular oxygen fixes directly on certain substances described as auto-
oxidizable (Fe2+ and Cu+), forming unstable peroxides that, in turn, oxidize other
oxygen accepting substances.
 These molecules are not directly oxidized by molecular oxygen, as it is a very weak
oxidant.
 Peroxides have a greater oxidizing capacity than molecular oxygen.
 The operations to which wine is subjected are therefore responsible for causing
oxidative phenomena. These vary in intensity, according to the composition of the
medium.
 In airtight vats and bottles, wine is deprived of oxygen from the air and is affected
Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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General Reminder of Oxidation–Reduction Concepts

 Substances are oxidized when they fix oxygen or lose either hydrogen or one or
more electrons.
 Reduction is the reverse of these reactions. In organic molecules, oxidation
produces compounds with a higher oxygen or lower hydrogen content.
 When an oxidation reaction occurs, there is always a parallel reduction reaction:

Examples of oxidation

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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General Reminder of Oxidation–Reduction Concepts

Oxidizing–reducing systems are divided into three categories:

1. Directly electroactive substances that react with Pt. These are often pairs of
metals: Fe2+/Fe3+ and Cu+/Cu2+.

2. Weakly electroactive substances that do not react with Pt, but are nevertheless
active in the presence of these substances. These molecules have a conjugated
dienol:

3. Electroactive substances in the presence of dehydrogenases:

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Measuring Dissolved Oxygen

 When a wine is in contact with air, the longer and the more vigorously it is agitated, the
more oxygen is dissolved. When the wine is no longer in contact with air, this oxygen reacts
with the compounds in wine and disappears.

 This reaction is faster at higher temperatures and in wines with a high

concentration of oxidizable molecules.

 Although the quantity of dissolved oxygen depends on many factors, a wine’s oxygen
content is still a useful parameter in analyzing its condition.

 The currently preferred method is polarographic analysis, developed by Clark (1960). The
apparatus consists of two electrodes, a silver anode and a gold cathode, linked by
potassium chloride gel. They are separated from the medium by a membrane selectively
permeable to oxygen. The difference in potential established between the two electrodes (on
the order of 0.6 to 0.8 volts) is modified by circulating oxygen through the membrane.

 The following reactions take place:

1. At the cathode: O2 + 2H2 + 4e− → 4OH−, the oxygen consumes electrons.

2. At the anode: Ag + Cl− → AgCl + e−, electrons are released.

 The intensity of the electrical current, caused by the movement of electrons, is directly
proportional to the quantity of dissolved oxygen, expressed in mg/l.

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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OXIDATION–REDUCTION POTENTIAL
Measuring the Oxidation–Reduction Potential in a Simple Medium

 … the oxidation–reduction potential EH, measured in volts (V), is expressed by

the Nernst equation:

Where,
E0 = normal potential of the system
R = perfect gas constant = 8.31 J/mole/ K
T = measured temperature (inK)
n = number of electrons involved
F = Faraday number = 96 500 coulombs
At 25◦C, with decimal logarithm:

 The Nernst equation, as described above, is only strictly valid for mineral
oxidation–reduction systems; for example:

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Measuring the Oxidation–Reduction Potential in a Simple Medium

 In organic systems involving proton exchanges, the pH must be taken into account:

 A combined electrode is used for measurements of oxidation–reduction potential in

wine. It consists of a platinum measuring electrode and an Ag/AgCl, KCl reference
electrode, with a constant potential in relation to the standard hydrogen electrode, on the
order of 200 mV at 25C. When this combined electrode is immersed in distilled water at
25C, the positive potential measured is due to the following reactions:

 The potential is then expressed as follows:

 For distilled water at 25C : [H2O] = 55.55 mole/l and E0 = 1.229 V.

Therefore EH(V) = 1.178 − 0.059 pH + 0.014 log[O2]
 In an aqueous solution, EH depends on pH and oxygen content. At a constant oxygen
content, any increase in pH leads to a decrease in EH. At a set pH, any additional dissolved
oxygen leads to the opposite phenomenon.
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Measuring the Oxidation–Reduction Potential in Wine

 It is very difficult to obtain reliable measurements in a complex medium such as

wine.

 It has been observed that the readings do not stabilize and that electrode
calibration is disturbed due to pollution.

 In view of these difficulties in making measurements, the electrodes has been

changed to take into account the composition of wine.

Correlation Between Dissolved Oxygen and the Oxidation–

Reduction Potential
 Of course, the oxygen concentration has a major effect on the value of EH. Differences of
150–250 mV have been observed at oxygen levels ranging from 1 to 6 mg/l. The wine’s
degree of aeration is, therefore, one of the main factors involved in oxidative phenomena.

 According to Zamora (1989), the equation that integrates all of these phenomena
is as follows:
EH = E0 + A pH + B log[O2]

where A and B are the characteristic coefficients of pH and log [O2], respectively.

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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INFLUENCE OF VARIOUS FACTORS ON THE

OXIDATION–REDUCTION POTENTIAL

Influence of Oxidation–Reduction Agents

Influence of iron (8 mg/l of FeII) and copper (2
mg/l of Cu) on the oxygen consumption and
oxidation–reduction potential of a red and white
wine

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Influence of Compounds in Wine and Certain External Factors

 Varying the composition of a model medium produces the following results:

1. Ethanol increases the instantaneous oxidation rate and slightly reduces the potential.
2. Tartaric, malic and lactic acids produce only a few minor modifications. Although EH
decreases when pH increases, variations are small, remaining between 3 and 4.
3. Glycerol has no effect on oxidation mechanisms.
4. Phenols inhibit variations in potential. Anthocyanins, in particular, consume oxygen rapidly,
leading to a rapid drop in potential. Catechins and oligomeric procyanidins are more active
than polymers. A wine with a high concentration of flavonols and not very highly condensed
tannins consumes more oxygen than one that only contains condensed tannins.
5. Furthermore, temperature causes wide variations in the oxidation–reduction potential of
wine (100 mV between 0 and 30◦C), in proportion to the quantity of dissolved oxygen.
Between +5 and +35◦C, the amount of oxygen required to saturate wine drops from 10.5
to 5.6 mg/l.
6. Finally, the types of containers used for aging and storing wine have an influence on the
oxidative process, depending on their permeability to air. It is possible to maintain a constant
concentration of oxygen and a higher oxidation–reduction potential when wine is aged
in oak barrels rather than vats. This feature is attenuated with age, as the pores of the barrels
gradually become clogged.
Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Influence of Compounds in Wine and Certain External Factors

Influence of the main components of wine on the oxygen consumption and
oxidation–reduction potential in a model medium

Influence of the container on the oxidation–reduction

condition of a red wine stored for 8 months

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Influence of Various Winemaking Operations

1. Racking oxidizes wine. The quantity of oxygen dissolved ranges from 2 to 5 mg/l, according
to the technique (air pump, mechanical pump, etc.). This oxygen is consumed in 8–10 days.
At the same time, the oxidation–reduction potential initially increases from 50 to 100 mV,
then decreases sharply until it reaches a minimum value, before returning to its initial level
in 15–20 days.

Influence of racking (at time 0) on the development

of the mean EH of two red barrel-aged wines

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Influence of Various Winemaking Operations

2. Air penetration via the bunghole does not depend on the age of the barrel, but rather on the
type of bung (silicon, wood, cork, glass, etc.). Every year, 0.5 mg of O 2/l may be absorbed
into the wine through this orifice. The increase in EH is mostly noticeable in the 20 cm of
wine nearest the bung, where it may reach 20–30 mV.

3. Topping up also causes an increase in EH in the upper 20–30 cm of wine. This may be on
the order of 20 mV, depending on the type of wine. Approximately 1 mg/l of oxygen is added,
which is capable of initiating surface oxidation reactions.

Influence of topping-up operations on the EH profile of red wines

in the barrel according to the level of the wine

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Influence of Various Winemaking Operations

4. Filtration, centrifugation and pumping may be major oxidation factors if proper precautions
are not taken to minimize aeration. These operations may lead to oxygen saturation of the
wine and a 50–150 mV increase in the oxidation–reduction potential. Furthermore, the addition
of ellagic tannins (major components in oak) in the absence of oxygen leads to a significant
increase in the oxidation–reduction potential. This value may reach 30–50 mV in both
red and white wines, following the addition of 300–500 mg/l of ellagitannins.

5. It is possible to monitor changes in the oxidation–reduction potential of a wine during

fermentation and in the early stages of aging. It has been Observed that pre-fermentation
treatment of the grapes involves rapid oxidation, reinforced by the presence of
olyphenoloxidases. Highly reducing media are produced during alcoholic and malolactic
fermentation. The oxidation–reduction potential then stabilizes at an average level
between 200 and 300 mV. Measuring the oxidation–reduction potential makes it possible to
predict the reduction problems that are likely to occur at potentials ≤150 mV.

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Influence of Various Winemaking Operations

Example showing changes in the oxidation–reduction potential of a red wine during

the winemaking process: AF, alcoholic fermentation; MLF, malolactic fermentation

Example showing changes in the oxidation–reduction potential of a white wine

during winemaking with stirring of the lees: AF, alcoholic fermentation

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Impact of Aerating Wine

Estimated quantities of oxygen absorbed

during vatting (results are expressed in mg O 2. l−1 wine)

Overall estimate of the quantities of oxygen

dissolved via aeration during the aging of red wines
(results are expressed in mg O 2. l−1 wine)

*Depending on the type and position of the bung

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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DEVELOPMENT OF THE PHENOLIC CHARACTERISTICS

OF RED WINES (COLOR AND FLAVOR) DURING AGING
Wine Development
 The aging of red wine should be characterized by harmonious development of the various
components of color, aroma and flavor. The color gradually changes from cherry red to deep red
and then brick red. The oldest wines even take on an orange tinge. The flavor also evolves,
becoming softer, with less astringency. There is, however, a risk that the wine may become thinner
and dry out on the palate as it ages. Furthermore, the rate at which these changes occur is
different for each wine, depending on both outside conditions and the wine’s specific composition:

1. External conditions include oxidative phenomena (O 2 and SO2), temperature and time. A
great deal of research has focused on the aging of wines prior to bottling . There are, however, very
few publications on bottle aging.

2. The way a wine ages depends on its phenol composition, characterized by the total quantity
of phenols (OD 280), the ratio of the various pigments (tannins/anthocyanins) and the type of
tannins (seed tannins consisting of procyanidins polymerized to varying degrees and skin tannins
with more complex structures). The presence of polysaccharides of both plant
and yeast origin also affect aging potential. Anthocyanins and tannins extracted from grapes
are involved in various reactions that depend to a great extent on external conditions and produce a
variety of compounds. These reactions include degradation, modification, and stabilization of the
color, polymerization of tannins and condensation with other components.

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Wine Development

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Changes in Color Intensity

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Changes in Color Intensity

More influences…

 Development of a Yellow–Orange Color

 Changes in Tannins Produce an Impression of Softness

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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BOTTLE AGING RED WINES

Aging Phenomena

Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”
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Aging Phenomena

To be continued…
Adapted from: Ribéreau-Gayon, et al. (2007): “Handbook of Enology: The Chemistry of Wine”