2009_Book_FoodChemistry

984 22 Spices, Salt and Vinegar
provide or enhance the sour, acidic taste of food
(cf. 8.12.5).
22.3.1 Production
Vinegar is produced microbiologically from
ethanol or by dilution of acetic acid.
CH 3 CH 2 OH + O 2
−→ CH 3 COOH + H 2 O + 494 kJ (22.11)
Fermentation of ethanol is conducted as a top fermentation
and increasingly as a submerged oxidative
process. In top fermentation the bacteria
are cultivated on spongy, porous laminated carriers
(usually beechwood shavings) with the alcoholic
solution trickling down over carrier surfaces
while a plentiful supply of air is provided from
below. The fermentation is stopped at a 0.3% by
volume residual ethanol level to avoid overoxidation,
i. e., oxidation of acetic acid to CO 2 and
water.
22.3.1.2 Chemical Synthesis
22.3.1.1 Microbiological Production
Acetobacter species are cultivated in aqueous
ethanol solution or, to a lesser extent, in wine,
fermented apple juice, malt mash or fermented
whey. Ethanol, as shown in Fig. 22.2, is dehydrogenated
stepwise to acetic acid; the resulting
reduced form of the cosubstrate methoxatin
(PQQH 2 ) is oxidized via the respiratory chain.
Part of the energy formed by oxidation is
released as heat which has to be removed by
cooling during the processing of vinegar. If
there is an insufficient supply of oxygen, the
microorganisms disproportionate a proportion
of the acetaldehyde, the intermediate compound
(cf. Fig. 22.2) in this aerobic reaction pathway:
2CH 3 CHO −→ CH 3 COOH + CH 3 CH 2 OH
(22.12)
Fig. 22.2. Oxidation of ethanol to acetic acid by Acetobacter
species (according to Rehm, 1980)
Acetic acid is usually synthesized by catalytic
oxidation of acetaldehyde:
CH 3 CHO + 1 2 O 2
cat. −−→ CH 3 COOH (22.13)
Acetaldehyde is obtained by the catalytic hydration
of acetylene or by the catalytic dehydrogenation
of ethanol. Formic acid and formaldehyde
are by-products of acetic acid synthesis. They are
removed by distillation. Chemically pure acetic
acid is diluted with water to 60–80% by volume
to obtain the vinegar essence. The essence
is a strongly corrosive liquid and is sold with special
precautions. It is diluted further with water
for production of food grade vinegar.
22.3.2 Composition
There are 5–15.5 g acetic acid in 100 g of vinegar.
The blending (or adulteration) of fermented
vinegar with synthetic acid can be detected
by mass spectrometric determination of the
13 C/ 12 C-isotope ratio (cf. 18.4.3); fermented
vinegar has 5‰ more 13 C isotope than acetic
acid synthesized petrochemically. In addition
fermented vinegar can be distinguished from
synthetic vinegar by analyzing the accompanying
compounds. With this method fermented vinegars
of different origin can also be distinguished from
each other; e. g. spirit vinegar (fermented from
aqueous ethanol) from wine, apple, malt and/or
whey vinegar. The fermented vinegars contain
metabolic by-products of Acetobacter strains,
such as amino acids, 2,3-butylene glycol and