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Analysis with the TANNOMETER

Example: Analysis of beer

The following descriptions concerning the automatic modes relate to the analysis of beer. They are written with the help of Prof. em. Lucien Chapon. There are, however, analogue relations to other solutions.

  1. Equilibrium Protein-Tannin- (PT)
  2. Tannoid content
  3. Sensitive Proteins (Special function 1)
  4. Reducing power 1+2
  5. Chill Haze
  6. Ammonium sulphate titration limit (Special function 2)

 The equilibrium PT - Key to quality

The concept according to which an equilibrium occurs between proteins (P) and tannoids (T) P+T=PT allows us to understand that a wort and the corresponding beer cannot simultaneously be rich in proteins and tannoids.

The control of these two classes of components gives the brewer precise information about the quality of the raw materials malt and hops.

The maltster uses the Tannometer for the purchase of his barley and the control of his production.

At the different stages of beer production, rapid analytical methods give the possibility, to follow the dissolving of tannoids, the precipitation of the proteins and the efficiency of stabilisation treatment aimed either at the tannoids or at the proteins.

This is a very simple way for optimising the amount of stabilising agent needed.

Literatur

Conclusion

The analysis encompasses both tannoids and proteins. Both are particularly important for the chemical-physical stability. Additionally, reducing substances which buffer the damaging dissolved oxygen can be determined. Likewise the Alcohol chill haze test, which allows fast determination of the total turbidity building substances, is of significant value.

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1. Tannoids

The tannoids are defined as the fraction of polyphenolic compounds which can be precipitated by polyvinylpyrrolidon (PVP). They include the low and medium molecular polyphenols, the polymers of catechin and anthocyanogens. Tannoids come from the malt and hops. Although present at relatively low concentration, they play an important part in the colloidal and taste stability of beers. On the one hand they can precipitate the sensitive proteins of the wort and beer, on the other hand they act as protective agents. The tannoid content of beer, wort, barley, malt and hop extracts can be determined by precipitation with PVP.

This polymer which can be considered as a structural analog of proteins binds with tannoids by hydrogen bonding to give an insoluble complex which leads to the formation of a haze.

On continous injection of a solution of PVP into the sample a haze develops until all the tannoids are bound. Beyond this point an excess of PVP brings about a progressive dissolution of the haze.

The amount of PVP necessary to reach the maximum is proportional to the tannoid content of the sample. The Tannometer measures the amount of haze formed versus the amount of PVP injected and expresses the result in mg PVP/litre. The curve and the result are printed by the inbuilt plotter.

(literature: Der Begriff Tannoide, Monatsschrift für Brauwissenschaft, No. 7/8 93, page 263-279)

Literature

 

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2. Sensitive Proteins

During the lagering of beers their tannoids condense into true tannins. They are then capable of binding themselves with certain proteins to give associations of low solubility. Such a process corresponds to the first step towards the formation of permanent hazes. It proceeds at a very low speed, even at 40°C or 60°C, for strongly stabilised beers. To simulate the spontaneous increase of the true tannin concentration a solution of gallic tannin is injec-ted into the beer. The substances which are protein like in nature and with the strongest affinity with the tannin are in-solubilised first. They are known as “sensitive proteins”.

(literature: Der Begriff Eiweißempfindlichkeit, Monats-schrift für Brauwissenschaft, part 1 to 3, No. 9/10 95,
1/2 96, 3/4 96) further
Literature

 

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3. Reducing Power

 

Reducing Substances
according to MEBAK by DPI,
(similar to ITT-Test)

 

Reducing Substances
according to Chapon by DPFe3-complex

Beer contains important oxidisable components. The oxidation of some of them impairs the colloidal stability of the beverages as well as its organoleptic quality. The initial freshness gives way to an oxidised taste. Such a beer, impaired by the oxygen in the air, loses its appeal to the consumer.

Malt and hops give the beer protective substances endowed with reducing capacity. They are mainly phenolic in nature, and of low molecular weight, but also include melanoidins formed during the kilning process of the malt and the boiling of the wort. They are able to slow down, if not prevent, oxidation harmful to the quality.

Since beers are exposed to adverse conditions during transportation and storage which can affect their original quality, knowledge of their reducing capacity is of great interest.

Direct determination of the reducing power is not possible on account of the sluggish reactivity of the molecular oxygen. Nevertheless it is possible to take advantage of the reactivity of the ferric dipyridyle complex (DPFe3, according to Chapon) or that of the 2.6. Di-chlorphenolindophenol (DPI, according to Hartong) toward the above reducing substances to determine the buffer-capacity of malt or hop extracts and that of beers.

Practical experience has proved that the taste stability of beers with a large reducing capacity was generally good. However there is no reference value which could be taken into account when predicting the actual behaviour towards oxygen.

Literature

 

Reducing Substances acc. to Mebak:

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Reducing Substances acc. to Chapon:

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4. Chill Haze - Alcohol-Chilling-Test (ACT)

A beer sample cooled down below freezing point (downto -8°C) develops a chill haze dependent on its condition. This haze is caused by insolubility of polyphenol-protein complexes. The test carried out immediately after filtration or bottling gives accurate information regarding the potential haze of the beer and the efficency of the stabilisation treatment which can be adapted if required.

During distribution and storage the ACT gives information regarding haze forming condensation phenomena leading to an increase in tannin power against haze sensitive proteins. This phenomenon, during which the molecular weight of the tannoids increases, is caused mainly by oxidation to which beers poor in reducing components are especially sensitive.

The addition of ethanol decreases the solubility of the PT-complex and enhances the chill haze. In the ACT one can add upto 6% vol. ethanol. The addition of 1% vol. alcohol has the same effect as lowering the temperature 1°C. The Tannometer measures the chill haze as a function of temperature and time. The result expresses the haze formed in EBC units after a preset time (40 minutes).

Literature

 

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5. Ammonium Sulphate titration limit (Hartong)

This rapid analytical method gives information about the hydrophilie character of the colloidal constituents of beer. The addition of ammonium sulphate to beer induces a haze formation.

The greater the amount necessary to achieve a given haze value the higher the chances of stability. The limit of precipitation is expressed as the volume of saturated ammonium sulphate solution which induces the beginning of the haze formation.

There is however no linear relationship between the precipitation limit and the colloidal stability, since it depends not only on the proteins but also on other factors such as tannin and oxygen content.

Literature

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