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20, 136) has shown that the colloids of beer and wort migrate towards'
the cathode when subjected to an electric field. The particles arc
therefore positively charged, and it is probable that the charge is due
to hydrogen ions which they have adsorbed.
Recently, van Lacr (Ann. Brass, el Disl., 1920, 19, 19, 23; this
Journ, 1920, 26, 568) has put forward the view that the action of
hydrolytic enzymes is merely a modification of the normal catalytic
action of the hydrogen ions. It is well known that acids will catalyse
many non-biochemical organic reactions, such as the decomposition
of diazo acetic ester, the inversion of cane sugar, and many others,
and van Laer believes that one stage in the mechanism of those
enzyme reactions which can also be catalysed by hydrogen ions alone, ■
is the adsorption of hydrogen ions by the colloidal enzymo particles
from the suspending acid medium. Thus a high concentration of hydro
gen ions will be produced on the surface of the particles, and this will
have the effect of rapidly hydrolysing any substrate which may have been
adsorbed from the solution. The velocity of the reaction will depend on
the product of the concentrations of the substrate and hydrogen ions
in the surface zone of the enzyme particles, and not on the concentrations
in the solution. A definite relation, however, will exist between the
hydrion concentration in the solution and that on the colloidal surface.
The velocity of the reaction will attain a maximum value when the
surface is completely saturated. Beyond the optimum hydrion con
centration the particles coagulate, and hydrolysis is arrested.
According to Compton (Proc. Roy. Soc., 1914, 87b, 245 ; 88b, 258,408),
the optimum temperature for enzyme action is independent of the con
centrations of substrate and enzyme; it is, however, affected by the
hydrion concentration in the medium. Moreover, the entire activity
of enzymes appears to be intimately connected with hydrogen ions,
and the study of enzymes is gradually reducing itself to a study of
pB values. It is therefore evident that this free acidity is one of the
important factors to be considered in brewing processes.
Each brewery is dependent on the water to be found in its vicinity,
and it follows that waters of different alkalinities are used in the
mashing process in various parts of the country. Chabot (Ann. de la
Brass., 1923, 310) has shown that this alkalinity has a significant effect
on the yield of extract obtained from the malt. By acidifying a natural
water to methyl-orange neutrality he found that there was an increase
of about 2 per cent, in the extract. The acidity of the mash was also,
thereby increased, the pu value falling from 6-35 to 5*8.
u 2
300 HAOUES : THE EFFECT OF HYDROGEN IONS, ETC.
x
«CTIVIIY
•H
tt- so
Fig. 1. Fio. 2.
is due to the preformed acid in the grain, the greater part being pro
duced by the action of a group of enzymes known as phosphatases. They
attack the complex insoluble organic phosphates and break them down
into organic and inorganic phosphates. Northrop and Nelson (Brewing
Trade Review, 1921, Feb.) have been successful in isolating from starch
one of these complex phosphates containing 4-9 per cent, of phosphorus
in the organic state. The temperature most favourable to the phos
phatases, according to Adler {Biochem. Zeilschr., 1915, 70, 1), is 58° C,
and their action is comparatively vigorous between 42° and 60° C.
Graphs I and II (Fig. 3) illustrate the effect of' temperature on the
percentage " Total dissolved phosphoric acid," and " dissolved inorganic
phosphoric acid " respectively.
Adler attributes the action to at least two phosphatases, one of which
acts on the insoluble complex phosphates splitting them up into simpler
Fig. 3.
t
IOC
\ i 3 is « ' „ •
Fig. 4.
enzymes, but not to diastase. His results indicate that the optimum
pa value for these enzymes is 4-4—4-5, thus confirming the observations
of Fernbach and Hubert {Compt. rend., 1900, 130, 1783; 131, 293)
that the optimum acidity is the same for the amylolytic and proteolytic
actions of malt extract.
According to Schjerning, the various reactions which take place in
the autolysis of the original protein matter, may be represented by the
following scheme.
Insoluble Albumin II Albumin I v „ ,
ProWn (EdKilln) (Uuooeln) ~^~ Peptones->-nnlmo add* ■§». ammonia.
■
Sjluble albuminoids.
Fig. 5.
So
TOTAL NITRCOSN
t
7o
60-
SO
40
30
20
10
3-7—4-3 in the case of kilned malt, and 3-2 in the case of green malt.
Tiypsin has its region of maximum action between pu 6*2—6-4, and
the optimum pu value for autolysis is 4 -4, which is intermediate between
those for the two enzymes.
The presence of cmulsin and lipase in malt is suggested by Van Laer
(Gomples rend. Soc. Bid., 1921, 84, 471, 473 ; this Journ., 1921,
27, 321). His evidence is based on the comparison of the amounts
of reducing sugar formed in a malt extract, treated with 1 per cent.
306 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC.
Time of
Method employed. Extract. [oh. Saccharifi-
cation.
mms.
KOH TmATion
Fig. 7.
• * * * *
8o
60.
40
a©.
W'«-O YtAST
5-5
Pm
Fig. 8.
79 ; this Journ., 1914, 20, 221) has shown, by fermenting sugar solu
tions of different hydrion concentrations, with and without nutrient salts,
that the same pu value was finally attained. With brewery worts this
was not always the case, and he suggests that the phenomenon is
possibly due to the great buffer action of the wort, and to adsorption of
hydrogen ions by the colloids, thus preventing the pa value from ever
reaching the optimum. This property of producing its own favourable
hydrion concentration does not depend on the living state of the yeast,
since free zymasc behaves similarly. Emslander finds that all enzymes
and yeasts have an analogous action, but, contrary to the above sugges
tion of Luere, he also states that the pa value for the optimum reaction
of yeast varies considerably with the different nutrient solutions. For
worts which are brewed from carbonate waters the pu optimum is
4-5, and for those from gypseous waters 4-2. Emslandcr's results
arc supported by the observations of Van Laer (Petit Journ. du Brass.,
1922, 30, 887; this Journ., 1922, 28, 907) who has shown that the
optimum hydrion concentration for yeast development depends not
only on the chemical constitution and nutritive values of the medium,
but also on the presence or absence of antiseptics, such as hops. His
method was to seed different culture media with equal quantities of a
pure brewery yeast, and to count the number of cells per cc. of solution
after several days' fermentation. In this way he found that the
optimum pu values for Pasteur mineral (a liquid), unhopped wort (50 per
cent, malt -f- 50 per cent, raw grain) and hopped wort were 6*8,4-6 and
6-0 respectively, and that the yeast could support more acidity the
more nutritive the medium. According to Fodor (Fermentforsch., 1920,
3, 193 ; this Journ., 1920, 26, 599) the optimum pu value depends on
the' individual properties of the ferment colloids and the amphoteric
substrate, on their mutual relationships, and in particular on the
difference in acidic nature between colloid and substrate. This influence
of the composition of the medium undoubtedly accounts for the various
values for the optimum hydrion concentration reported by different
investigators. Thus by measuring the rate of evolution of carbon
dioxide, Euler and Heintze {Arkiv fur Kemi Mineralogi och geologi,
1917, 7, 5, 21) studied the fermentation of cane sugar and glucose by
yeast at 28° C. in the presence of sodium phosphate and hydrochloric
acid. They carried out experiments with and without the use of nutrient
nitrogenous substances, and they give the pa value as 5. Similar
investigations were made by Euler and Emberg (Zeilschr.fur Bid., 1919,
69, 349 ; this Journ., 1919, 25, 314) using phosphoric acid instead of
312 HAGOES : THE EFFECT OF HYDROGEN IONS, ETC.
hydrochloric acid to produce the required free acidity, and their value
is the same (pH5), but the limits of pa for rapid action are more
narrow, as is shown by the graphs. Svanberg (Zeitschr. tech. Bid., 1920,
8, 1) gives the pu values for the optimum growth of yeasts, whether
grown in beer wort or solutions of ammonium salts with phosphates,
as : top yeast, pu 3-6 ; bottom yeast, pa 4-6. The optimum tempera
ture for reproduction, according to Zikes (Zenlralb. Bait. II, 1919,49,
353 ; this Journ., 1920, 26, 530) is 25° C.
It is well known that the presence of phosphates in wort contributes
to the efficiency of the alcoholic fermenting power of yeast. Harden
and Young {Proc. Roy. Soc. B., 1908, 80, 299 ; this Journ., 1908, 14,
547) found that the addition of a phosphate to a fermenting mixture
of glucose and yeast juice not only produced a temporary acceleration
00. COj Relative
per boar. reaction
velocity.
Fraction
Unxlm.
Action.
Fiu. 12.
IIAGUES I THE EFFECT OF HYDROGEN IONS, KTO. 315
Fig. 13.
7. -7-O7
6.
S-
4 6 I* 16 cc. alkali.
Fig. 14.
advantageous than the one in general use, except when large proportions
of diluents deficient in protein matter, such as flaked maize, arc added
to the malt (this Journ., 1923, 29, 576).
Another factor which is influenced by the hydrion concentration is
the production of oxalic acid. According to Geys (Zeilschr. ges. Brau.,
1922,2, 9 ; this Journ., 1922,28, 417), the more frequent appearance
of calcium oxalate in beer recovered from yeast than in beer from
the vats, is due to the lower acidity of the former. In a particular
case vat beer was found to have a pa of 4-64 as compared with
pn 6-54 for beer from the yeast. Thus for almost all the maladies of
beer there seems to be one diagnosis; namely, lack of free acidity
during the process.
Finally, we must consider the head retention and the taste of the beer.
Berry (this Journ., 1909, 15, 391) tried the effect of varying acidities
on the time of duration of the " head " of samples of the same beer.
He found that as a beer increases in acidity the carbon dioxide bubbles
become larger, giving a coarser head. With -05—1 per cent, of acid
there was no decrease in the head retention, but as soon as this value
was exceeded the retentivity fell until the limit of -3 per cent, was
attained. According to Rohland {Wochensch. Brau., 1923, 40, 23, 27)
only those liquids which contain colloids, together with free acidity
or alkalinity, will give a strong permanent head. These conditions
are present in wort and beer, but not in aerated waters.
Many and futile have been the experiments carried out on the subject
of taste. The opinions of different people on the taste of buffer solutions
are by no means alike. Harvey (S.A.S.G., 1920, 42 (1), 712) has pub
lished an interesting paper in which a serious attempt is made to illustrate
graphically how taste varies with the free and total acidities to the
solution. There is no doubt that beers of high protein content have
the greatest palatefulness, but although the hydrion concentration
contributes to the sensation produced on the palate, taste is not tts yet
a quantitative science, and its dimensions as a mathematical quantity
are still unknown.
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