905

THE INSTITUTE OF BREWING RESEARCH SCHEME.

THE EFFECT OF HYDROGEN IONS IN BREWING
PROCESSES.—PART II.

The Influence of varying Hydrogen Ion Concentration in

the Mashing Process.—Part I.
Treatment of Brewing Waters.
By G. Hagues, M.Sc, A.I.C.
Of the many and varied chemical changes which take place in brewing,
those which occur in the mash ton are of the utmost interest to the brewer,
and a knowledge of them is of vital importance in preparing the way
for a good fermentation and a sound palatable beer. In this initial stage,
malt is mashed with water, and, as every brewer knows, the success
of the operation depends in no small measure upon the saline content
of the mashing liquor. Apart from the simple solution effects, the
conversion of substances in the malt into aqueous solute is due almost
entirely to the catalytic activity of the enzymes present. These
substances have been shown to exercise their maximum effect in media
containing specific ionic concentrations. In the light of modern theory,
we regard enzymic action .as the indirect catalytic effect of the ions
present in the medium, and it is possible that every type of ion has the
power of stimulating the velocities of biochemical reactions. Some
ions are undoubtedly more effective in this capacity than others, but
what order and mechanism this catalysis follows at present we can only
conjecture. The mobility of the ion appears to be an important factor,
for the position is dominated by the ion which has by far the greatest
mobility, and the influences of all metallic and acidic ions shrink into
comparative insignificance in the presence of the hydrogen ion.
There arc three principal reactions which occur in the mash tun,
namely :—
(1) The conversion of starch into sugars by the diastase.
The well known paper by Sherman, Thomas and Baldwin
(Journ. Amer. Chem. Soc., 1519, 41, 231) gives pH 4-4 as the
diastatic optimum, whereas other authors favour the more
alkaline values of pa 4-9 (Adler, Biochem. Zeitschr., 1916, 77,
150) and pa 5-0(EulerandSvanberg, Wochenschr. Brau., 1921,
38, 111).
906 HAGUES I THE EFFECT OF HYDROGEN IONS, ETC.

(2) The decomposition of complex nitrogenous compounds into

simpler soluble substances by the proteolytic enzymes.
Lundin (Biochem. Zeitschr., 1922,131,193) gives the optimum
hydrion concentration of this reaction as pa 4-4.
(3) The liberation of phosphates by the phosphatases.
Adler (Biochem. Zeitschr., 1915, 70, 1) finds that the optimum
hydrion concentration is pa 5-4.
When alkaline waters are used in the mash, the optimum hydrion
concentration required by any one of these three groups of enzymes
is never attained. For this reason many Continental chemists have
been considering what advantages may be derived by increasing the
hydrion concentration of the mash, and they chum a considerable
increase of extract by the addition of acid. The method which they
use is first to determine the alkalinity of the mash to methyl orange
pa 4*4), and then to add sufficient acid to neutralise one-half to three-
quarters of that alkalinity. Addition of acid beyond this amount is"
said to inhibit saccharification. Mr. D. McCandlish has suggested
that in the " infusion " method, as practised in English breweries, an
increased extract may be obtained by neutralising the alkalinity of the
brewing water with sulphuric acid. The costly decarbonating methods,
such as boiling, are thus replaced by a cheap and more simple operation.
At the same time the sulphuric acid produces in solution an equivalent
amount of gypsum. It will be shown in this paper that such treatment
also lowers the pa value of the wort, and in the later stages in the
brewery this increased acidity may greatly assist in the suppression of
bacteria, which, as a rule, thrive more readily in the more alkaline
media.
It was our object, therefore, in the following experiments to ascertain
the influence of the gradual neutralisation of the mashing liquor on the
amount of extract. Extracts of a standard malt were made with samples
of an alkaline water to which different amounts of acid had been added,
all other factors being identical. The method we employed was the
standard laboratory method adopted by the Institute of Brewing
(this Journ., 1922, 28, 775), but with slight modifications. Since the
success of the results depended upon small differences of extract,
it was arranged that corresponding steps throughout the series of
experiments should occupy the same period of time and should be as
identical as possible in every way. Again, the malt was usually ground
at Seek 10 (roller gauge = j$jq in.) instead of Seek 25, in order to
produce a more homogeneous reaction in the mash, and the period of
 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC. 907

extraction, in several cases, was extended to two hours in order that

the reaction might be more complete. We found that the method thus
modified, was fairly accurate, and yielded interesting results.
The actual extracts obtained are given in the following tables and
graphs, also the corrected values obtained by deducting the sp. gr.
due to the mashing liquors, the assumption being made that the extract
value added to the water gravity would remain unchanged experi
mentally. We have investigated the effect on the extract by mashing
with an alkaline water gradually neutralised with increasing amounts
N N
°f J^ sulphuric and — hydrochloric acids under various conditions of
mashing, and with different malts. The influence of gypsum, calcium
chloride and calcium carbonate solutions has also been determined.
The alkaline water used in these experiments was a mixture of a well
water and Leeds city water. On an average, the pa value of the water
N
was 8-0, and required about 48 c.c. of — acid per litre to bring it to

methyl orange neutrality. %\\&&°*

Hydrogen ion concentrations were measured by the colorimotrio
method of Clark and Lubs, which is described by R. H. Hopkins (this
Journ., 1921,27, 401). The indicators used for the worts were methyl
red (pu 4-4-6-0), and brom-cresol purple (pa 5-2-6-8).

EXPERIMENTAL.
Table I.
Mashings of a Palo English Malt.
Duration of mash=ono hour.
Malt ground at Seek 10.
N
Mashing liquor: x c.c. — H.S0, + alkaline water = 500 c.c.

Extract
X. ptt ot water. pu wort.
(uncorrected).

c.c. Lb.
A 0 8-0+ 95-8 6-3
1 7-8 95-9 016
2 7-6 98-1 0-1
3 7-3 98-8 01
4 7-0+ 9S-8 005
C 6-86 97-0 0-05
0 6-8 97-7 0-05
7 6-7 97-7 00
8 6-7 97-9 60

3Q
908 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC.

Table I—continued.

Extract
X. j>h of water. Pa wort.
(uncoriected).

3 9 6-8 97-9 5-9+

10 6-8 98-3 5-9
11 6-7 98-4 5-85
12 6-0 98-7 5-85
13 6-65 98-7 5-85
14 6-5 98-4 5-8+
16 . 0-15 98-4 5-8
10 6-4 98-8 5-8

C 17 61 98-6 5-6
18 6-9 99-0 5-6
19 5-75 99-2 5-6
20 5-5 99-4 5-55
21 4-75 99-3 5-5
22 4-1 99-3 5-4
23 3-6 99-4 5-35
24 3-45 99-S 5-35
25 3-3 99-7 5-3

The three scries of mashes, A B and C, were carried out on three

separate days.
EXTRACT (uncorrected)
in lb./brl./qr.
100

97

12 10 20

c.c. ^ H.SO, }>er 500 c.o.

mashing water.
Fio. 1.

Table II.

Mashings of a Pale Californian Malt.

Malt ground at Seek 10.
Duration of mash = one hour.
N
Mashing liquor: x c.c. — H,SO« + alkaline water = 500 c.c.
 HAOUES I THE EFFECT OF HYDROGEN IONS, ETC. 911

Table V.

Mashings of a Pale Australian Malt. Duration of mash = two hours.

Malt ground at Seek 10.
N
Mashing liquor: x c.c. — H,S04 + alkaline water = 500 o.c.
Waters not heated above mashing temperature.

Mashing waters. Worts.

X. Sp. gr. Extract. Corrected

Sp.gr. Extract. Pa-
Extract.

c.c. lb./brl./qr. lb./brl./qr. Ib./brl./qr.

0 7-05 1000-491 1-65 1028-259 04-05 03-3 6-45
4 0-8 •523 1-75 •307 95-11 93-4 0-2+
8 6-0 •495 1-06 •343 95-23 93-0 6-0
12 0-45 •519 1-74 •407 95-45 93-7 5-85
16 505 •497 1-67 •543 0500 94-2 5-75
20 53 •517 1-72 •769 96-06 94-0 5-6+
24 3-2 •555 1-86 •869 07-00 05-1 5-5

EXTRACT in
lb./brl./qr.

— -

— —

93
12 10 20

c.c. jt: HjSO4 per 500 (

of mashing water.
Fio. 5.

Table VI.

Mashings of a Pale Australian Malt. Duration of mash = two hours.

Malt ground at Seek 10.

Mashing liquor: x c.c. — HjSO, -\- alkaline water = 500 c.c.

Waters boiled, cooled, and then remade to volume with boiled distilled
water.
912 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC.

Mashing waters Worts.

Corrected
X. Pa- Sp. gr. Extract. Sp. gr. Extract. Pn-
Extract.

c.c. lb./brl./qr. lb./brl./qr. lb./brL /qr.

0 8-85 1000-397 1-33 1028-503 95-77 94-4 01
4 0-4 •381 1-28 •557 90-02 94-7 0-0
8 9-2 •427 1-43 •085 90-38 950 5-9
12 90 •433 1-46 •739 90-60 95-1 5-8
10 91 •478 100 •93S 97-22 95-0 5-7
20 80- •451 1-51 •915 97-15 95-6 5-55
24 3-3 •489 1-04 •941 97-24 95-0 5-4

EXTRACT in
lb./brl./qr.
IX)

OS

01
0 4 8 12 16 20 21

c.c. ^ HSSO« per 500 c.c.

of mashing water.
Fio. 6.

Table VII.

Mashings of a Palo Australian Malt. Duration of mash = one hour.

Malt ground at Seek 0.
N
Mashing liquor: x c.c. — HjSO, + alkaline water = 500 c.c.

Waters not heated above mashing temperature.

Mashing waters. Worts

Corrected
X. Sp.gr. Extract. Sp.gr. Extract.
Extract.

0.0. lb./brl./qr. lb./brl./qr. lb./brl./qr.

0 8-25 1000-707 2-37 1028-054 94-26 91-9 0-5
4 7-05 ■701 2-30 •346 95-24 92-9 0-4
8 00 •725 2-43 •502 95-76 93-3 0-2
12 0-8 •737 2-48 •532 95-87 93-4 0-05
10 0-4 •747 2-51 •010 96-13 93-0 5-95
20 5-8 •767 2-54 •704 90-45 93-9. 5-8
24 3-4 •707 2-58 •900 97-10 94-5 5-55
 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC. 909

Extract,
X. 2>K of water. pa of wort.
(anoorreoted).

o.c. lb.
0 8-0 92-1 6-5
5 0-9 92-6 6-35
10 6-7 93-5 6-15
15 6-2 94-0 5-95
20 ■5-3 94-3 5-7
25 3-5 94-7 6-55

EXTRACT (uncorrected)
in lb./brl./qr.

93

0 5 10 13 20 23
N ■-
o.c. rrr H,SO« per 500 c.o.

mashing water.
Fig. 2.

Table III.
Mashings of a Pale Australian Malt. Duration of mash = one hour.
Malt ground at Seek 10.
N
Mashing liquor: x c.c. — H8SOi + alkaline water = 500 c.c.

Waters not heated above mashing temperature.

Mashing waters Worts •

Sp. gr. Extract. Corrected

X. Ph. Sp. gr. Extract.
Extract.

o.c. lb./brl/qr. lb./brL/qr. lb./brl./qr.

0 8-0+ 1000-067 1028-238 94-88 92-6 0-0
4 7-0 •671 2-25 •298 95-08 92-8 6-4
8 6-7 •075 2-28 -316 95-14 92-9 6-2
12 6-5 •687 2-32 ■448 95-58 93-3 6-0
16 6-2 •681 2-29 •588 96-06 93-8 5-7
20 5-55 -663 2-23 •726 96-52 94-3 5-5
24 3-4 •649 2-18 •788 96-73 94-6 5-4-

3 Q2
910 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC.

EXTRACT in
]b./brl./qr.

84

on
■—
—•

0 4 8 12 10 20 24

c.c. j^ HSSO4 per 500 o.c.

of mashing water.
Fig. 3.

Table IV.
Mashings of a Pale Australian Malt. Duration of mash = one hour.
Malt ground at Seek 10.

Mashing liquor : x c.c. — H,S0i + alkaline water = 500 c.c.

Waters, boiled, cooled and then remade to volume with boiled distilled
water.

Mashing waters. Worts

Corrected
X. Pa- Sp. gr. Extract. Sp. gr. Extract. Pn-
Extract.

C.C. lb./brl./qr. lb. /brl./qr. lb./brl. /qr.

0 9-3 1000-467 1-57 1028-514 95-81 94-2 0-2
4 8-6 •511 1-72 •590 06- 00 94-3 6-0
8 9-4 •479 1-61 •682 96-37 94-8 5-8-
• 12 9-3 •547 1-95 •694 96-41 94-5 5-7—
16 9-4 •617 2-07 •900 97-10 95-0 5-65
20 8-1 •679 2-28 ■956 97-29 950 5-6
24 3-4 •710 2-38 1029 032 97-54 95-2 5-4

EXTRACT in
lb./brl./qr.
OS

05

8 12 10 20 24
N
cc. jr. HSSO4 per 600 c.c.

mashing water.
Fro. 4.
 HAGXJES : THE EFFECT OF HYDROGEN IONS, ETC. 913
EXTRACT in
lb./brl./qr.
D5

02

12 16 20 24
N
c.c. -p^ HjSOj per 500 c.o.
10
of mashing water.
Fw. 7.

Table VIII.
Mashings of a Fale Australian Malt. Duration of mash = two hours.
Malt ground at Seek 0.
N
Mashing liquor: x c.c. — HSSO« + alkaline water = 500 c.c.

Waters boiled, cooled, and then remade to volume with boiled distilled
water.

Mashing waters. Worts.

Corrected
X. Pa- Sp. gr. Extract. Sp. gr. Extract. - P..
Extract.

c.c. lb./brl./qr. lb./brl./qr. lb./brl./qr.

0 8-85 1000-424 1-42 1,029-122 97-85 96-4 6-35
4 9-3 •412 1-38 •214 98-15 96-8 6-05
8 9-2 •428 1-44 •402 98-79 97-3 5-9
12 9-4 •480 1-61 •358 98-64 97-0 5-8
16 9-3 •484 1-63 •598 99-45 97-8 5-65
20 5-8. •510 1-71 ■048 09-61 97-9 5-45
24 3-2-- •530 1-78 ■090 99-76 98-0 5-3

EXTRACT in
lb./brl./qr.

07

12 10 20 24

c.c. rrj HjSO^ per 500 c.o.

mashing water.
Fw. 8.
 914 HAGUES I THE EFFECT OF HYDROGEN IONS, ETC.

Table IX.

Slashings of a Pale Australian Malt. Duration of mash = one hour.

Malt ground at Seek 10.

Mashing liquor: x c.c. — HtSOt -f distilled water = 500 c.c.

Waters not heated above mashing temperature.

Mashing waters. Worts.

Corrected
X. Ph. Sp.gr. Extract. Sp. gr. Extract.
Extract.

c.c. lb./brl./qr. lb./brl./qr. lb./brl./qr.

0 5-65 1000-000 •00 1028-322 95-16 95-2 5-75
4 3-25 •047 •10 •378 95-35 95-2 5-6
8 30- •103 •35 •530 95-88 95-5 5-4-
12 2-75 •137 •40 •538 95-89 95.4 5-25
16 2-65 •179 •00 •506 95-78 95-2 5-2-
20 2-5 •205 •09 •450 95-59 94-9 51-
24 2-35 •227 •70 •380 95-37 94-0 4-85

EXTRACT in
lb./brl./qr.

95

91
8 12 16 SO 24

c.c. ^ ILSO4 per 500 c.c.

mashing water.
FlO. 9.

Table X.

Location of the oplimum final pu of tcort giving the maximum extract.

Mashings of a Pale Australian Malt. Duration of mash = two hours.
Malt ground at Seek 10.
N
Mashing liquor: a; c.c. rr H,S0« + alkaline water = 500 c.c.

Waters not heated above mashing temperature.

 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC. 919

EX1 fRACl1 in
)b./l)ri./qr.
08

— —
97

BO ** —
/
05
0 4 8 12 16 20 2»

c.c. ^HClperoOOc.c.
mashing water.
Fig. 14.

Table XVI.
Mashings of a Pale Australian Malt. Duration of mash = two hours.
Malt ground at Seek 0.
N
Mashing liquor : x c.c. — HC1 + alkaline water = 500 c.c.

Waters not heated above meshing temperature.

Mashing waters. Worte.

Corrected
X. Pa- Sp. gr. Extract. Sp. gr. Extract. J»n-
Extract.

O.C. lb./brl./qr. lb./brl./qr. lb./brl./qr.

0 8-0 1000-725 2-44 1028-440 05-58 03-1 6-3
4 71 ■701 2-50 •518 05-82 03-3 6-2
8 6-8 •743 2-50 •610 00-13 03-0 60
12 60 •070 2- 20 •602 00-30 04-0 5-05
10 6-4 ^ -087 2-32 •800 00-70 04-5 5-85
20 5-3 •085 2-30 •854 00-OS 04-7 6-75
24 3-2 ■083 2-20 •030 07-22 94-9 5-0

EXTRACT in
lb./brl./qr.
OS

94

03

12 16 20 24

c.c jtj HC1 per 500 c.c.

mashing water.
Fia. 15.
 Table XVII.
N N
Comparison of the relative effects of — HCl and — HZSO4 on the extract value.
10 10

Malt ground at Seek 10.

N
Mashing liquor : 10 c.c. — acid -f- alkaline water = 500 c,c.

Waters not heated aoove mashing temperature.

Each Mash was done in duplicate.

Mashing waters. Worts.

Duration Corrected Mean

Acid added per 000 c.c. Sp. gr. Extract. Sp. gr. Extract. Extraot, ^11-
of Mash. Extract.

.b./brL/q, Ib./brl./qr. lb./brl./qr. lb./brl./qr.

lhour 8-0 1000-490 1028-843 96-91 95-26 95-26 6-4+

f1028-980 97-39 95-62\ 5-9

10 c.c. HBSO« 1 hour 6-8+ •528 1*77 95*64
\ -994 97-42 95-65/

f1028-809 96-79 95-22\ 5-9 +

10 c.c. HCl Ibour 6-9- -460 1-57 95*20
\ -793 96-74 95-17J

f1029-106 08-00 96-43\

10 c.c. HCl 2 hours 6-9- •460 1-57 96-45 5-9 +
\ -180 98-04 96-47/
 hagues : the effect of hydrogen ions, etc. 917

Table XIIIb.

Mashings of a Pale Australian Malt. Duration of mash = one hour.

Malt ground at Seek 10.
N
Mashing liquor: x c.c. — HC1 ■+■ alkaline water = 500 c.c.

Waters not heated above mashing temperature.

Mashing waters. Work3.

X. Pa Sp.gr. Extract. Sp. gr. Extract. Correoted

Extract.

c.c. lb./brl./qr. lb./brl./qr. lb./brl./qr.

0 81 1000-093 2-33 1028-280 95-04 92-7 0-45
4 7-3 •683 2-29 •290 95-05 92-8 6-4
8 7-0 •659 2-21 •382 95-30 03-2 0-2
12 6-8 •667 2-24 •500 95-98 93-7 0-0+
10 0-65 •669 2-25 •058 90-29 94-0 6-0
20 5-8 •655 2-20 •000 90-32 94-1 5-8
24 3-0 •659 2-21 •080 90-38 94-2 5-6

.EXTRACT in
lb./brL/qr.

ei

OS

n?,
S 12 16 20 2*
N
c.c. r^ HC1 por 500 c.o.

mashing water.
Fig. 12.

Table XIV.

Mashings of a Pale Australian Malt. Duration of mash = two hours.

Malt ground at Seek 10.
N
Mashing liquor: x c.c — HCl -f- alkaline water = 500 c.c.

Waters not heated above mashing temperature.

918 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC.

Mashing waters. Worts ■

Corrected
X. P*- Sp.gr. Extract. Sp.gr. Extract. Pil
Extract.

C.C. lb./brl./qr. lb./brl./qr. lb./brl./qr.

0 8-1 1000-719 2-42 1028-476 95 68 03-3 6-44
4 7-3 •723 2-43 . -589 96 06 93-6 6-3
8 6-95 •731 2-46 •598 90 09 93-6 0-15
12 0-8 •711 2-41 •738 96 •56 94-2 00
16 0-5 •679 2-29 •874 97 •02 94-7 5-85
20 5-8 •671 2-25 •974 97 ■35 95-1 6-7
24 3-5 •651 2-19 •922 97 •17 95-0 5-5

EXTRACT in
Ib./l>rL/qr.
00

~
OS

A3

0 4 8 12 10 20 24

c.c. y0 HC1 per 500 c.c.

mashing water.
FlO. 13.

Table XV.

Masbings of a Palo Australian Malt. Duration of mash = one hour.

Malt ground at Seek 0.

Mashing liquor : x c.c. — HC1 + alkaline water = 500 c.c.

Waters not heated above mashing temperature.

Mashing waters. Wort i.

Corrected
X.
Pa- Sp.gr. Extract. Sp.gr. Extract. Pa-
Extract.

0.0. lb.'brl./qr. lb./brl./qr. lb./brl./qr.

0 8-1 1000-394 1-32 1028-928 97-20 95-9 0-1
4 7-0 •428 1-44 •930 97-21 95-8 00
8 6-8 •404 1-36 •940 97-20 95-9 5-9
12 6-4 •420 1-41 •968 97-33 95-9 0-8
16 6-9 •357 1-20 1029-210 98-13 96-0 6-6
20 3-2 •396 1-33 •288 98-41 97-1 5-45
24 2-8 •367 1-23 •286 98-40 97-2 5-35
 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC. 915

Mashing waters. Worts.

Corrected
X. Pa- Sp. gr. Extract. Sp. gr. Extract. Pa-
Extract.

c.c. lb./brl./qr. lb./brl./qr. lb./brl./qr.

20 6-0 1000-755 2-54 1029-323 98-53 96-0 5-7
25 5-3 •779 2-62 •523 99-20 96-0 5-5
30 3-3 •779 2-62 ■495 99-10 96-5 5-35
35 2-9 •799 2-68 •639 99-56 96-9 5-2
40 2-8 •837 2-81 •691 99-76 97-0 5-0.
45 2-7 •871 2-93 •773 100-03 97-1 4-8
50 2-7 •on 3-08 •527 99-21 96-2 4-0-

EXTRACT in
lb./brl./qr.
08

06
25 30 35 40 45 60

c.c. jj. HjSO, per 500 c.c.

mashing water.
Fia. 10.

Table XI.
Comparison of mashes of one and two hours' extraction with the malt
ground at Seek 0 and Seek 10. Each mash was done in duplicate.
N
Mashing liquor : 10 c.c. — HjSO, + alkaline water = 500 c.c.

Sp. gr. = 1000-562. Extract value = 1-89 lb./brl./qr. ya = 6-6.

WorU.

Duration Fineness
of of Corrected Mean
Sp.gr. Extract.
mash. grinding. Extract. Extract.

Hour. Seek. lb. lb. ;

1029-016 97-49 95-60
1
1029-010 07-47 95-58
\ 05-59 5-65

1 10 { 1028-986
1029-002
97-39
97-45
95-50
\ 95-53 5-65
05-66

2 0 1029-142 97-93 96-04 96-04 5-65

10 {
1029-122 97-85 95-96
2
1029-122 97-85 95-96
\ 95-96 5-65
916 HAGXJES : THE EFFECT OF HYDROGEN IONS, ETC.

Table XII.
Table for use in converting the proportions of acid used in these
experiments into the equivalent amounts in English units.

c.c.5hsSO4, Amount of 98 per cent.

HjSO4 per barrel of
Usual p,, of our alkaline
water.
per 500 o.c. water.

c.c. fluid oz.

8-0
4 016 7-0
8 0-31 • 6-7
12 0-47 6-45
16 0-62 6-3
20 0-78 5-7
24 0-94 3-4

Table XIIIa.
Mashings of a Pale Australian Malt. Duration of mash = one hour.
Malt ground at Seek 10.
N
Mashing liquor : x c.c. — HC1 + alkaline vrater"= 500 c.c.

Waters not heated above mashing temperature.

Mashing waters. Worts

Corrected
Sp.gr. Extract. Sp.gr. Extract. Tb-
X. Pi Extract.

c.c. ,b./brW<l, lb./brL/qr.

8-0 1000-609 1028-074 92-3 6-2+
0
4 7-0 •623 2-09 •128 94-51 92-4 6-1
8 6-7 •629 2-11 •298 95-07 93-0 6-0
6-4 •593 1-99 •478 95-65 93-7 5-9
12
16 6-6 •621 2-08 •512 95-77 93-7 5-8
4-9 •653 2-19 •558 95-93 93-7 5-6
20
2-6 •691 2-32 •726 96-53 94-2 5-35
24
EXTRACT in
lb./brl./qr.

91

03

09.
/
8 12 10 20 24

c.c. ^j HC1 per 500 c.c.

of mashing water.
Fio. 11.
 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC. 921

Table XVIII.
Mashings of an undergrown badly modified Scotch malt. Time allowed
for extraction = two hours.
Malt ground at Seek 10.
N
Mashing Liquor: x c.c. — H.S0, + alkaline water = 500 c.c.

Waters not heated above mashing temperature.

JXoshing w&tors. i
Work

Corrected
X. Pa- Sp. gr- Extract. Sp. gr. Extract. Pa-
Extraot.

c.c. lb./brl./qr. lb./br l.for. lb./brl./qr.

0 8 0!> 1000 •783 2-63 1028-824 96 85 94 2 6- 5
4 7 0 761 256 •804 96 80 94 2 6- 3
8 6 75 799 2-68 1029-188 98 07 95 4 6- 1
12 0 55 803 2-70 •216 98 16 95 5 «• 0
10 0 3 815 2-74 •427 98 87 96 1 5- 8
20 4 8 789 2-64 •503 99 13 96 5 6- 6
24 3 2 803 2-70 •331 98 15 95 9 5- 35

EXTRACT in
lb./brl./qr.

ro

05

M
/
12 16 20
N
c.c. j^ HjSO4 per 500 o.o.

mashing water.
Fio. 16.

Table XIX.

N
Correctionfor the displacement of alkaline water by — add in our method of

varying the pa of the mashing liquor.

Mashings of a Pale Australian Malt. Time allowed for extraction = one
hour.
Malt ground at Seek 10.
922 HAGUES : THE EFFECT OF HYDROGEN IONS, ETC.

Mashing Liquor: x c.c. distilled water + alkaline water = 500 c.c.

Waters not heated above mashing temperature.

Mashing Waters. Worts

Corrected
X. Pn- Sp. gr. Extract. Sp. Extract. Pn-
Extract.

c.c. Ib./brl./qr. lb./brl./qr. lb./brl./qr.

0 805 1000-525 1-76 1028< 103 04 •63 92-9 6 •5
4 8-05 •529 1-78 •
203 94 •76 93-0 6 •6
8 8-05 •499 1-68 127 94 ■60 92-8 6 ■5
12 8-05 •527 1-77 131 94 •52 92-8 6 •5
16 8-05 •495 1-66 159 94 •62 930 6 •5

EXTRACT in
lb./brl./qr.
94

03

0 4 8 12 16
c.c. distilled water per
500 c.c. mashing water
Fio. 17.

Table XX.
The effect of Calcium Carbonate on the extract value.
Mashings of a Pale Australian Malt. Duration of mash = one hour.
Malt ground at Seek 10.
Mashing liquor: x c.c. alkaline water + distilled water = 500 c.c.
Waters not heated above mashing temperature.

Mashing waters. WorU

Corrected
X. Pn- Sp. gr. Extract. Sp. gr- Extraet. Pn-
Extract.

c.e. lb./brl./qr. lb./brl./qr. lb./brl./qr.

0 5-6 1000000 — 102J •178 04 •68 94-7 5 •7
100 70 • 165 0-62 •280 95 •02 94-6 6 •85
200 7-8 •247 0-83 •382 95 •46 940 6 •0
300 8-0 •421 1-43 •434 95 •53 94-1 6 •2+
400 8-0 •483 1-62 •450 95 •59 940 6 •46
 HAOUKS : THE EFFECT OF HYDROGEN IONS, ETC. 923

EXTRACT in
lb./brl./qr.

04

03
100 200 300 400
c.c. alkaline water per
GOO c.c. mashing liquor.
Fio. 18.

Table XXI.

Variation of extract with variation of Gypsum in the mashing liquor.

Slashings of a Pale English Malt. Duration of mash = one hour.
Malt ground at Seek 10.
Mashing liquor : x grains gypsum per gallon of distilled water.
Waters not heated above mashing temperature.

Mashing waters Worts.

X. Pn. Sp. g, Extract. Sp. gr- Corrected

Extract. i
Extract.

grains
gull. lb./brl./qr. Ib./brl./qr. lb./brl./qr.
0 5 •8 1000 ■000 1028 836 96-89 96-9 a
,r) ti •1 084 0 28 876 97 02 96-7 5 8
10 ti 144 0 48 926 97 19 96-7 5 7
15 ti 188 0 03 882 97 04 96-4 5 OH
20 ti ■2 2U4 0 88 1029 042 97 58 96-7 fi ft
25 ti 309 1- 04 154 97 95 90-9 5- 6-

Table XXII.

Variation of extract with variation of Calcium Chloride in the mashing water.

A solution of calcium chloride in distilled water was made, and the
strength estimated by means of standard silver nitrate solution.
Mashing waters were then prepared from the calcium chloride solution
by diluting with distilled water.
Mashings of a Pale English Malt. Duration of mash = one hour.
Malt ground at Seek 10.
3b
924 1IAGUES : THE EFFECT OF HYDROGEN IONS, ETC.

Mashing liquor: x grains of calcium chloride per gallon of distilled

water.

Mashing waters Wortsi.

Corrected
X. Ph. Sp. gr. Extract. Sp. gr- Extract. Pa-
Extract.

grains
gall. lb./brl./qr. lb./brl./qr. lb. ,'brl. 'qr.
0 5 -8 1000-000 1,028 •734 96 •55 96-6 0 •y

5 5 •9 •020 0 07 -748 96 -59 96-5 o •8

10 5 •9 ■110 0 37 ■782 96 •72 96-4 5 •6
15 5 •9 ■158 0 53 ■850 96 •94 96-4 5 -4+
20 6 •0 •204 0 68 ■926 97 •19 96-5 5 •4—
25 6 •1 ■264 0 89 ■948 97 •26 96-4 5 ■35

Conclusions.

It will be observed from the foregoing results that the extract of a

malt mashed with a partially neutralised alkaline water increases with
decreasing alkalinity. With acid waters the extract value increases
still further to a maximum and then begins to decrease, the optimum
occurring when the final wort indicates a pa of 5-0—5 • 4. If the greater
part of this increase is due to sugars and the final pa is assumed to be
the controlling value, the results are more closely allied with the diastatic
optima of Adler and of Eulcr and Svanberg than that of Sherman,
Thomas and Baldwin.
In our method of preparation of the mashing liquor the amount of
alkaline water in the mixture decreases with increasing amounts of
added acid. We have shown that carbonates diminish the extract
value, but the correction necessary for the small amount of alkaline
water displaced is negligible. Calcium sulphate and calcium chloride
have but little effect on the extract.
Although wort is a buffered liquid the addition of these small amounts
of acid in the neutralisation of the water produce a remarkable alteration
in the pa of the final wort. Neutralisation by sulphuric acid appears
to produce a slightly more acid wort than the equivalent of hydro
chloric acid, this being due, possibly, to the formation of gypsum in the-
mashing water.
Mashes of one hour show a larger increase of extract than those of
two hours' duration, but comparisons of the net extracts indicate that
the reaction is by no means complete at the end of one hour. Sulphuric
acid produces a larger extract than hydrochloric acid.
 HAQUES : THE EFFECT OF HYDROGEN IONS, ETC. 925

The series of mashes with Pale Australian Malt arc not comparable
with each other as the composition of the alkaline water varied slightly
from day to day, and several samples of Australian malt were used.
The individual mashes in each table were, however, carried out under
strictly identical conditions. Grinding at Seek 0 gave but little increase
of extract over the value obtained at Seek 10 with the malts in question.
The results in this part of the paper refer only to the quantitative
increase observed. Investigations are now in progress as to the
composition of these extracts.

I should like to thank the members of the pa research committee for

their helpful suggestions and for correction of the manuscript.

Tetley's Brewery,
. Leeds.
18/7* July, 1924.

Errata.
April, 1924, issue.
P. 305, Fig. C—Ordinate: per cent, total nitrogen.
P. 310, Fig. 8.—Ordinate : per cent, maximum action.
P. 314, Fig. 12.—Ordinate: per cent, total nitrogen.
Abscissa: autolysis time in hours.
P. 315, Fig. 13.—Abscissa : pn values.
P. 317, 1. 26.-(S.A.S.C., 1920, 42 (1), 712) should read (Journ. Amer.
Chem. Soc., 1920, 42, 712).

3 R 2