1

The effect of brewing water and grist composition on the pH of the mash
2009
Dipl. Ing. Kai Troester, braukaiser.com Mash pH is an important brewing parameter that lays the foundation for the pH of subsequent brewing processes and the final product. During the mash, a proper mash pH is important for optimal enzymatic activity. While home brewers have a general understanding of how brewing water mineral content and acidity of the grist affect each other to settle on a mash pH, little has been published about the quantitative effects. This paper tries to shed some light on how malt and water react with each other. t also proposes a means of estimating mash pH from water and grist composition. The distilled water mash pH of various base malts has been determined as well as the titratable acidity of specialty malts. n both cases it was found that dar!er malts are in general more acidic but a number of e"ceptions to this rule e"ists. #f the specialty malts tested, $ara and base malts have more acidity per color than roasted malts which showed little difference in their acidity despite their fairly large color range. The effect of water al!alinity and calcium and magnesium hardness was evaluated. t was found that %olbach&s pH change based on residual al!alinity is generally used incorrectly in 'home( brewing and that it depends on more factors than )ust the residual al!alinity of the brewing water when mash pH is of interest. Different sources of al!alinity were evaluate. $hal! that is added to brewing water without being dissolved by $#* does a very poor )ob in raising mash pH and looses most of its effectiveness at addition rates higher than +,,-.,, ppm. n order to be effective chal! needs to be dissolved with $#*. /inally mash thic!ness and girst preparation 'milling( were evaluated. Mash thic!ness had a profound impact on how much pH changes when the residual al!alinity changes while milling has the same effect but to a much lesser e"tend.

1 Introduction
When grist and brewing water are mi ed at dough!in the mash will settle at a p" that is determined b# the bu$$er strength and other p" characteristics o$ both the water and the grist. Depending on the mashing procedure used and the grist, that p" ma# change during mashing. % mash p" in the range o$ &.' ( &.) is generall# accepted as ade*uate $or brewing . +arl# on in brewing, brewers noticed that some beers do better with their water while others don,t come out right. This was a ma-or $actor in the de.elopment o$ regional st#les and was the result o$ $inding the a suitable grist composition $or the brewing water that was a.ailable at that location. During the mid 20th centur# Kolbach in.estigated the relation between brewing water composition and 12 /lato cast out wort p". The result o$ that work was the disco.er# that mash p" is a$$ected b# the water,s alkalinit# and its calcium and magnesium hardness. "e de$ined 0esidual %lkalinit# as1

KH: carbonate hardness CH: calcium hardness MH: magnesium hardness %ll hardness .alues are gi.en in degree ;erman "ardness <d"= which is an e*ui.alent measure o$ the molar concentration o$ the ions and their charges. 0esidual %lkalinit# is the %lkalinit# that is le$t a$ter the alkalini# neutrali3ing reactions betrween malt phosphates and calcium and magnesium ions in the water ha.e been considered. Kolbach,s work also $ound that changing the residual alkalinit# b# 10 d" changes the cast out wort p" b# 0.' units. I.e. the use o$ a water with a residual alkalinit# o$ 10 d" <'.&& m+*8l= results in a cast out wort p" that is 0.' units higher than the p" o$ a cast out wort that has been prepared with the same grist and brewing procedure but with distilled water. De7ange modeled the reaction between phosphate and calcium which releases protons and thus counteracts the p" raising e$$ect o$ alkalinit#2. This reaction is the basis o$ Kolbach,s residual alkalinit#. "e $ound that the e$$ecti.eness o$ calcium, i.e. how much calcium e*ui.alents are needed to neutrali3e 1 e*ui.alent o$ alkalinit#, depends on the amount o$ phosphate a.ailable, the mash p" and the alkalinit# itsel$.
2 %.6. De7ange, %lkalinit#, "ardness, 0esidual %lkalinit# and 2alt /hosphate1 >actors in the +stablishment o$ 2ash p". ?op# a.ailable at1 http188a-del.wetnew$.org19185rewing:articles8?ere.esia8>inal:galle# @ome rights reser.ed, 2009 Kai Troester, braukaiser.com, Act '1, 2009 see http188creati.ecommons.org8licenses8b#!nc8'.08 $or license details

1 $H MH 2 0esidual 1l!alinity = %H '.&

where1
1 /aul Kolbach, Der 2influss des 3rauwassers auf das pH von W4rze und 3ier, 2onats3eitschri$t $4r 5rauerei, 5erlin 19&', Translation b# %.6.de7ange a.ailable at1 http188a-del.wetnew$.org19185rewing:articles8Kolbach/aper.pd$

/igure *5 Mashing the mash samples in a water bath.

brewing parameters on the mash p" e ists and was the moti.ation $or the work presented in this paper. /igure 65 relationship between beer color and optimal water residual al!alinity '7almer(

2 Methods and Materials

Cnless otherwise noted in 0esults and Discussions, the $ollowing methods and materials were used The e periments $or this paper were small scale mashes done in bab# $ood -ars set in a water bath. <see >igure 2= That water bath was used to preheat the strike water and maintain a mash temperature that was between E0 and E& ?. While there were temperature di$$erences between di$$erent series, all mashes within a gi.en series were done at the same temperature. The mash time was 10 min. +ach series consisted o$ up to 12 e periments. Ance the mash time e pired, samples were cooled to 2B ( 2E ? within '!& min in an ice bath and their p" was tested with a 2ilwaukee @2101 p" meter. The meter was calibrated be$ore each series o$ e periment using B.00 and ).00 bu$$er solutions at 2& ?. To minimi3e measurement errors associated with weighing .er# small amounts o$ salts, stronger solutions o$ .arious brewing salts and distilled water were made and the desired water pro$ile was created b# mi ing these stronger solution and, i$ necessar#, distilled water. The distilled water was obtained $rom a drugstore and tested 0 with a TD@ meter. Weights were either measured with a precision 0!100 g scale <the precision o$ that scale is 0.01g= or a 0!2000g scale <the precision o$ that scale is 1g=. The latter was used $or weighing the water used to create batches o$ stronger brewing salt solutions mentioned earlier. The standard strike water amount used was &0g. The standard mash thickness was B l8kg which resulted in a standard grist weight o$ 12.& g. @ome e periments,
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De7ange also proposed the use o$ the titrateable acidit# o$ base and specialt# malts to estimate the amount o$ alkalinit# that can be neutrali3ed b# the use o$ these malts'. 1 m+* o$ titrateable malt acidit# would neutrali3e 1 m+* o$ water alkalinit# i$ the titration end p" matches the mash p" that is achie.ed with that grist and the water used. To guide brewers in estimating the needed residual o$ their brewing li*uor when brewing a beer with a gi.en color /almer proposed the relationship shown in >igure 1B. The top residual alkalinit# cur.e represents .alues that should be used $or beers that get most o$ their color $rom roasted malts while the low residual alkalinit# cur.e is $or beers that get all or most o$ their color $rom base and8or caramel8cr#stal malts. The relati.e a$$ordabilit# o$ re.erse osmosis water s#stems allow man# home brewers to build their brewing water $rom .er# so$t water and based it on their brewing needs. This gi.es brewers an unprecedented le.el o$ control o.er their brewing water and allows the brewer to match the water to the grist. %s a result a need $or a better understanding o$ the e$$ects o$ grist and brewing water composition as well as .arious
' %.6. De7annge, Cnderstanding %lkalinit# and "ardness /art II, ?op# a.alable at1 http188a-del.wetnew$.org19185rewing:articles85T:%lkalinit#:II8%lkali nit#/tII.pd$ 6ohn /almer, 2ash 0esidual %lkalinit# %d-ustment Worksheet Dersion 2.&, a.aila.ble at1 http188howtobrew.com8section'8/almers:2etric:0%:.er2e. ls

'
howe.er, changed that. 2ost e periments were done with a pul.eri3ed grist. The grist was ground to a $ine power using a small electrical co$$ee grinder <"amilton 5each 1&!cup ?o$$ee ;rinder, model Fo 90'BB = on its $inest setting. % $ull# ad-ustable 6@/ 2altmill set to the desired mill gap spacing with a $eeler gauge was used to crush malt $or e periments that used a crushed grist. In this paper the +uropean 5rewing ?on.ention,s <+5?= measure $or malt and beer color is used. When the malt color was onl# a.ailable in degree 7o.ibond, the $ollowing $ormula was used $or con.ersion&

3.1 Distilled water mash pH of base malts

When base malts are mi ed with water, the resulting mash p" depends on the acidit# o$ the malt. 2ost malt has a natural bu$$er that creates a distilled water mash p" o$ about &.) ( &.9. That mash p" can be lowered b# acidic melanoidins present in more highl# kilned malts. This series o$ e periments e.aluated the distilled water mash p" o$ a number o$ commonl# used base malts. The results are shown in >igure & and Table 2. While a loose correlation <02H0.&B= between malt color and distilled water mash p" e ist, there are a number o$ notable e ceptions. The sample o$ We#ermann 2unich I malt, which has hal$ the color o$ the darker We#ermann 2unich II malt, had a lower distilled water mash p" than a sample o$ the darker darker malt. % number o$ lightl# kilned malts, around a malt color o$ B +5?, showed distilled water mash p" .alues ranging $rom &.&E to E.0B. 5ased on these results it cannot be said that a darker base malt color alwa#s results in a lower distilled water mash p". The distilled water mash p" o$ a gi.en base malt needs to be known i$ a reasonabl# accurate mash p" prediction is e pected.

8 23$ = 8 92.E& : 1.2

Titration e periments were either done with a 0.1 2 FaA" <sodium h#dro ide= solution or muriatic acid <"?l= diluted to about 0.& G <w8w=. The sodium h#dro ide solution was obtained $rom a home brew suppl# store while the muriatic acid was purchased at a hardware store The correct strength o$ each batch o$ diluted muriatic %cid was determined $rom the initial muriatic %cid strength, its weight and the weight o$ distilled water that was added. It was then recorded and used calculate the amount o$ acid e*ui.alents added during titration. %lkalinit# was determined b# titration to a p" o$ B.' measured with a p" meter. Anl# @I units are used in this paper. Wile it is .er# common to e press alkalinit# as either ppm as ?a?A' or d" <;erman "ardness=, m+*8l is used as the measure o$ alkalinit# in this paper. The $ollowing con.ersion can be used to calculate ppm as ?a?A' or d"1 1 m+*8l H &0 ppm as ?a?A' H 2.91 d"

3.2 Mixing base malts

I$ malts act like acids and the distilled water mash p" is an indication o$ the amount o$ acid contained in a malt and not the strength o$ the acid, the distilled water mash p" o$ a mi o$ base malts is e pected to be the weighted a.erage o$ the distilled water mash p" .alues o$ the indi.idual base malts. This assumption was supported b# this e periment where We#ermann /ilsner, We#ermann 2unich T#pe I and We#ermann 2unich T#pe II were mi ed with each other. >igure E and Table 2 show the results. The mash p" $or these base malt mi es was slightl# lower than e pected $rom the weighted a.erage o$ the contributing base malts. 5ut since the numbers $or 100G /ilsner, 2unich I and 2unich II were taken $rom the pre.ious series, it is possible that another, not controlled, $actor caused that p" shi$t. >or the purpose o$ predicting the distilled water mash p" o$ a base malt mi it is assumed that it is su$$icient to use the weighted a.erage o$ the distilled water mash p" .alues o$ the used base malts.

3 Results and Discussion

The order in which the results are listed here is not necessaril# the order in which the e periments ha.e been per$ormed. The $irst sections $ocus on the distilled water mash p" o$ base malts and specialt# malts as well as the titrateable acidit# o$ specialt# malts. Fe t are e periments and discussions about the e$$ect that water composition has on mash p". The $inal set o$ e periments e.aluates the e$$ects o$ mash thickness and grist preparation.

pH = pH b ig b i
where pHb i5 distilled water mash pH of the base malt gb i5 grist portion of the base malt i 'between , and 6(
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& http188www.unc.edu8Irowlett8units8dictD.html, 0uss 0owlett, Cni.ersit# o$ Forth ?arolina at ?hapel "ill

/igure .5 Distilled water mash pH for various base malts. 'pulverized grist, + l;!g mash thic!ness, 6, min at <. $(

/igure =5 The acidity of various specialty malts. The orange points represent some of the the dar!er base malts that have been evaluated in the previous section. The grouping of crystal type and roasted malts is remar!able. 'pulverized grist, mash thic!ness > l;!g, 6, min at <. $, cooled to *. $ for titration(

/igure <5 The distilled water mash pH for mashes made with = different malts and each mash used up to two different malts in the grist. The triangle represents the arithmetic mean of the grist color and distilled water mash pH. 'pulverized grist, + l;!g mash thic!ness, 6, min at <. $(

/igure +5 correlation between the distilled water mash pH of base and specialty malts and their specific acidity.'pulverized grist, mash thic!ness > l;!g, 6, min at <. $, cooled to *. $ for titration(

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&
3.3 The acidit of specialt malts
%nother source o$ color and acidit# in grists is specialt# malts. @ince the# tend to be used in onl# small amounts compared to base malts but pro.ide a lot o$ acidit# to the grist, a di$$erent approach in e.aluating them was taken. In addition to e.aluating the p" o$ distilled water mashes prepared with these malts, these mashes were titrated to a p" o$ &.) with sodium h#dro ide. >igure ' shows the results. Ane obser.ation is that roasted and cr#stal t#pe malts $orm distinct clusters. While the speci$ic acidit# <titratable acidit# per kg o$ malt= o$ cr#stal malts increases at a slope o$ about 0.1' m+*Jkg!1J+5?!1 <r2 H 0.))=, roasted malts ha.e a speci$ic acidit# o$ about B0 m+*Jkg!1 regardless o$ their color. %s with the distilled water mash p" $or base malts there are also outliers among the cr#stal malts. The tested sample o$ We#ermann ?ara2unich II, $or e ample, had with B9 m+*Jkg!1 a higher speci$ic acidit# than the darker ?ara2unich III <'1.2 m+*Jkg!1 =. The same was true $or 5riess, ?r#stal E07 when compared to ?r#stal 907 and ?r#stal 1207. The $ollowing $ormula can be used to estimate the acidit# o$ cr#stal t#pe specialt# malts <r2 H 0.))=1 where1 ai5 specific acidity of the specialty malt i in m2q?!g-6 Ci5 color of the specialty malt in 23$ % stronger correlation e ists between speci$ic acidit# and the distilled water mash p" o$ specialt# malts. This is shown in >igure B. While not linear, the correlation is strong enough that it could be used as a reliable means o$ determining the malts speci$ic acidit# $rom its distilled water mash p". %cidulated malt <We#ermann @auermal3= was also included in the titration tests. Ane titration test determined a speci$ic acidit# o$ '1& m+*Jkg!1 while another test determined '&9 m+*Jkg!1. This corresponds to a lactic acid content o$ 2.9& G and '.22 G b# weight and matches We#ermann,s speci$ication o$ I 'G <w8w=

3.! Distilled water mash pH of grists with specialt malts

When specialt# malts become part the grist, the# lower the distilled water p" o$ that grist though the addition o$ acids. 5ut since the relationship between the distilled water p" o$ specialt# malts and their speci$ic acidit# is not linear, the p" shi$t caused b# specialt# malts was e.aluated as a $unction

a i=1B 0.1'$ i

/igure @5 the distilled mash pH of a grist with pilsner malt and = different specialty malt. 7ilsner malt was mi"ed with = different specialty malts at different grist percentages. This data confirms that the $arafa malt has a lower acidity per color than the $araMunich and the $ara1roma malt 'pulverized grist, mash thic!ness + l;!g, 6, min at <=$(

/igure >5 The distilled water pH of mashes with varying amounts of different specialty malts plotted over the specialty malt acidity per unit of stri!e water. 'pulverized grist, mash thic!ness + l;!g, 6, min at <=$(

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E
o$ the resulting a.erage grist color and the speci$ic acidit# added b# that specialt# malt. "ow increasing amounts o$ a specialt# malt in a grist a$$ect the distilled water mash p" is shown in >igure ) and Table &. %gain it is apparent that cr#stal malts pro.ide a stronger acidit# per color than roasted malts like We#ermann,s ?ara$a I special. Together with the speci$ic malt acidit# data that was determined in '.' KThe acidit# o$ specialt# maltsK it is possible to plot the distilled water mash p" o.er the specialt# malt acidit# di.ided b# the amount o$ strike water. The resulting unit is m+*8lL the same unit as alkalinit# which will be discussed later. The $orm o$ the plot shown in >igure 9 suggests that the decrease in mash p" caused b# the specialt# malt is a linear $unction o$ the acidit# that the specialt# malt added to the grist. In other words, i$ the acidit# o$ the specialt# malt is known the mash p" decrease can be calculated based on mash thickness and the grist percentage o$ the specialt# malt. The slope o$ the linear $unction was determined as $ollows1
malt t pe Carafa I special CaraMunich III CaraArom a all

pHb i5 distilled water mash pH of the base malt i gb i5 grist portion of the base malt i 'between , and 6( gs j5 grist portion of the specialty malt ) 'between , and 6( as i5 specific acidity of specialty malt ) 'm2q?!g-6( R5 mash thic!ness 'l?!g-6( In +nglish, the a.erage o$ the distilled water mash p" .alues $or the base malts and p" &.) <the titration end point= $or the specialt# malts is ad-usted b# the p" shi$t caused b# the acidit# o$ the specialt# malts.

3.# The effect of water al$alinit

@o $ar onl# the grist,s e$$ect on the distilled water mash p" has been e.aluated. 5ut brewing water is not distilled water. It,s mineral content, in particular bicarbonates, calcium and magnesium also a$$ect mash p". %lkalinit# is a measure o$ the bu$$er capacit# o$ the water,s carbonate bu$$er s#stem. It is well known that it has a pro$ound impact on mash p". The initial e periment e.aluated how ' di$$erent grists <single base malt, base malt mi and base malt with specialt# malt= reacted with water o.er a wide alkalinit# range. Water samples were prepared with distilled water and h#drochloric acid <negati.e alkalinit#= or distilled water and sodium bicarbonate <positi.e alkalinit#=. The results are shown in >igure 9 and Table '. The mash p" .alues can reasonabl# well appro imated with a linear $unction with a slope o$ 0.0E1 p"JlJm+*!1 <r2 H 0.9)=. The p" .alue at an alkalinit# o$ 0 m+*Jl!1 corresponds to the distilled water p" o$ the grists which has been discussed earlier. 5ased on these $indings the e pected mash p" can be written as a $unction o$ the grist,s distilled water mash p" and the water,s alkalinit#1

pH%l%m&'(1
0.12 0.15 0.12 0.14

r2 0.99 0.99 0.99 0.97

%nd with that the p" delta caused b# specialt# malts can be written as1

ApH =
where1

0.1B a ig i 0

pH = pH grist distilled water s pH1l! water

where pHgrist distilled water5 is the distilled water pH of the grist as calculated in the previous section spH5 the pH over al!alinity slope which has been found to be B,.,< pH?l?m2q-6 for + l;!g mashes Alkwater5 is the al!alinity of the water in m2q?l-6. 7ater e periments show that the p"!alkalinit# slope sp" depends on mash thickness and to some e tend also on grist preparation <milling=. It can be argued that an e ponential $unction the the data $or

gs j5 grist portion of the specialty malt i 'between , and 6( as i5 specific acidity of specialty malt i 'm2q?!g-6( R5 mash thic!ness 'l?!g-6(

3." Distilled water mash pH of a grist containing base and specialt malts
5ased on the pre.ious $indings the $ollowing $ormula is proposed $or estimating the distilled water mash p" o$ a grist containing base and specialt# malts1

pH =
where

0.1B a s )g s ) the pilsner malt grist better than a linear $unction. While this pH big b i &.) g s ) is true a linear $it is not $ar o$$, especiall# in the alkalinit# 0
range that e.entuall# matters in brewing, and makes $urther discussion o$ the e$$ects o$ alkalinit# on mash p" easier.

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/igure C5 various grists and their mash pH over an e"tended al!alinity range. 'pulverized grist, mash thic!ness + l;!g, 6, min at <=$, water general hardness , m2q;l(

/igure 6,5 mash pH as a function of the calcium content of the brewing water 'pulverized grist, mash thic!ness + l;!g, 6, min at <= $(.

+speciall# since it allows the de$inition o$ a p"8alkalinit# slope sp". I$ the slope sp" is e pressed as p"8d" where d" is the alkalinit# e pressed as ;erman "ardness, it is 0.022 p"8d" which is di$$erent $rom the 0.0' p"8d" that Kolbach $ound in his work. 5ut Kolbach,sE work measured the p" o$ the cast out wort and not the p" o$ the mash. The cast out wort is more dilute and e*ui.alent to a much thinner mash. '.10 K2ash thicknessK Will show that this slope increases as the mash thickness decreases.

3.) The effect of calcium and magnesium in the brewing water

?alcium and magnesium are known to a$$ect mash p" though acidic reactions with malt phosphates. These reactions are the basis o$ Kolbach,s concept o$ residual alkalinit#. To e.aluate the e$$ects o$ calcium and magnesium, two series o$ 12 mashes each were done with /ilsner malt. The $irst series e.aluated the e$$ect o$ calcium and the second series e.aluated the e$$ect o$ magnesium. >or the calcium series waters with di$$erent alkalinit# and calcium concentrations were prepared. The results are shown in >igure 10 and Table E.
E /aul Kolbach, Der 2influss des 3rauwassers auf das pH von W4rze und 3ier, 2onats3eitschri$t $4r 5rauerei, 5erlin 19&', Translation b# %.6.de7ange a.ailable at1 http188a-del.wetnew$.org19185rewing:articles8Kolbach/aper.pd$

/igure 665 pH over the magnesium hardness of the brewing water for waters with = different al!alinities '7ilsner malt, pulverized grist, mash thic!ness + l;!g, 6, min at <= $(.

5# e pressing the calcium content o$ the brewing water as as m+*8l, which is the unit o$ alkalinit#, the slope o$ the p" decrease with increasing calcium content was $ound as1
m&' *a to neutrali+e ,l$alinit -m&'.l/

pH %l%m&' (1
-0.031 -0.028 -0.026 -0.028

r2

1 m&' al$alinit

0 2.3 4.6 a era!e

0.984 0.965 0.971

2.6 2.8 3.1

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9
In in these e periments a.erage p" o.er alkalinit# slope $or constant concentrations o$ calcium was 0.090 p"JlJm+*!1 which is di$$erent to the 0.0E1 p"JlJm+*!1 that was $ound in '.E KThe e$$ect o$ water alkalinit#K. It is possible that ?alcium has an e$$ect on that relationship as well it addition to its own p" lowering properties. This has not been in.estigated $urther. 5ased on that a.erage p"JlJm+*!1 slope, that was $ound during these e periments $or waters with the same calcium content, 2.E ( '.1 e*ui.alents o$ calcium are needed to neutrali3e one e*ui.alent o$ alkalinit#. This is similar to Kolbach,s results, who $ound that '.& m+*Jl!1 calcium neutrali3e 1 m+*Jl!1 alkalinit#. De7ange showed that the amount o$ calcium needed to neutrali3e 1 e*ui.alent depends on the phosphate concentration) which is dependent on mash thickness. The results were similar $or magnesium with the di$$erence that the p" lowering e$$ect o$ magnesium is onl# hal$ that o$ calcium. >igure 11 and Table ) show the results. The sp" slope $or waters with the same calcium content in these e periments was 0.0E) p"JlJm+*!1. This is $airl# close to the 0.0E1 p"JlJm+*!1 that was $ound in '.E KThe e$$ect o$ water alkalinit#K. The $ollowing slopes were determined $or the relationship between the magnesium hardness and the mash p"1
m&' Mg to neutrali+e ,l$alinit -m&'.l/

di$$erences in the resulting mash p"9 between the two. This topic was e plored in more detail with the $ollowing set o$ e periments. ?alk was suspended in distilled water at a concentration o$ I1200 mg8l. This chalk suspension was di.ided into two .essels while maintaining an e.en distribution. Ane .essel was pressuri3ed with ?A2 and shaken to dissol.e that ?A2 in the water. >ollowing a rest the chalk dissol.ed and the water cleared. %n# chalk that didn,t dissol.e settled at the bottom. During the test the clear li*uid was decanted and used to prepare waters o$ di$$erent chalk concentrations through the addition o$ .ar#ing amounts o$ distilled water. To .eri$# the alkalinit# o$ the produced waters <with suspended chalk and with dissol.ed chalk= samples o$ both waters were titrated to a p" o$ B.' with "?l o$ known concentration. The $ollowing alkalinit# .alues were $ound1
calcula"e# al$alini"% m&'(l suspen#e# chal$ 24.1 #issol e# chal$ 24.1 "i"ra"e# al$alini"% m&'(l 22.6 23.4

5oth samples titrated to the same alkalinit# within e pected error o$ measurement. The sample with suspended chalk showed a slower p" response to addition o$ "?l since the chalk had to be dissol.ed b# acid.

the the the the

pH%l%m&'
-0.014 -0.010 -0.012 -0.012

(1

1 m&' al$alinit

0 2.29 4.57 a era!e

0.980 0.985 0.985

4.8 6.5 5.7

The e periments were done with We#ermann /ilsner malt and a 90820 mi o$ >ranco 5elges light 2unich malt and We#ermann ?ara2unich II malt. The results are shown in >igure 12 and Table 9. When chalk is dissol.ed in water the p" rise is proportional to the chalk concentration in the brewing water. I$ chalk is not dissol.ed it is less e$$ecti.e in raising the mash p" and the slope $lattens out at concentrations higher than &00 mg8l. %s a result chalk dissol.ed with ?A2 has more p" raising potential than chalk suspended in the brewing water or chalk added to the mash. To compare the residual alkalinit# o$ brewing water prepared with dissol.ed chalk it was compared to brewing water prepared with sodium bicarbonate. '.E KThe e$$ect o$ water alkalinit#K alread# showed that a nearl# linear relationship e ists between the alkalinit# o$ brewing water prepared with sodium bicarbonate and the mash p". >igure 1' compares that relationship between sodium bicarbonate water and dissol.ed chalk water. The raw data is a.ailable in Table 9 and Table 10.
9 Kai Troester, "ow much %lkalinit# does 1 ppm o$ chalk reall# addM <http188braukaiser.com8li$et#pe28inde .phpM opHDiew%rticleNarticleIdH129NblogIdH1= @ome rights reser.ed, 2009 Kai Troester, braukaiser.com, Act '1, 2009 see http188creati.ecommons.org8licenses8b#!nc8'.08 $or license details

Depending on the water,s alkalinit# it took B.9 to E.) e*ui.alents o$ 2agnesium to neutrali3e one e*ui.alent o$ alkalinit#. Which is again close to the ) that were reported b# Kolbach. Within the errors o$ measurement, Kolbach,s $indings that that magnesium is about hal$ as e$$ecti.e as calcium in neutrali3ing alkalinit# and lowering p", ha.e been con$irmed.

3.0 1ource of ,l$alinit

@o $ar, the source o$ brewing water alkalinit# was sodium bicarbonate <Fa"?A'=. 5ut earlier e periments with suspended .s. dissol.ed chalk in the brewing water showed
) %.6. De7ange, %lkalinit#, "ardness, 0esidual %lkalinit# and 2alt /hosphate1 >actors in the +stablishment o$ 2ash p". ?op# a.ailable at1 http188a-del.wetnew$.org19185rewing:articles8?ere.esia8>inal:galle#

/igure 6*5 The pH as a function of the $hal! '$a$#=( concentration in the mash water. Duspended and dissolved chal! data is shown here for the two different grists '6,,E Weyermann 7ilsner and >,;*,E /ranco 3elges 9ight Munich;Weyermann $araMunich (. 'pulverized grist, mash temp <>$, mash time *. min, mash thic!ness + l;!g(

/igure 6=5 pH vs. residual al!alinity of sodium bicarbonate and dissolved chal! waters. Dee te"t for e"planation. '6,,E Weyermann 7ilsner malt and >,E;*,E /ranco 3elges light Munich ; Weyermann $araMunich malt, pulverized grist, mash temp <>$, mash time *. min, mash thic!ness + l;!g(

/igure 6+5 pH for waters prepared with sodium bicarbonate and waters prepared with suspended chal!. '6,,E Weyermann 7ilsner malt and >,E;*,E /ranco 3elges light Munich ; Weyermann $araMunich malt, pulverized grist, mash temp <>$, mash time *. min, mash thic!ness + l;!g(

/igure 6.5 pH for mashes prepared with sodium bicarbonate '01F1( or sodium bicarbonate and calcium chloride waters '01F1-$a;=..( '6,,E Weyermann 7ilsner malt and >,E;*,E /ranco 3elges light Munich ; Weyermann $araMunich malt, pulverized grist, mash temp <>$, mash time *. min, mash thic!ness + l;!g(

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10
0% H % labels the data $or the sodium bicarbonate water. @ince it doesn,t contain an# calcium or magnesium, its residual alkalinit# e*uals the alkalinit# contributed b# the bicarbonate. ?halk, howe.er, also adds calcium in addition to alkalinit# and its residual alkalinit#, as de$ined b# Kolbach, is 0% H % ( ?a8'.&. In addition to that, another .ariation o$ the chalk water p" data is plotted. '.) KThe e$$ect o$ calcium and magnesium in the brewing waterK showed that the alkalinit# neutrali3ing power o$ calcium is about 182.9 its molar concentration. "ence a graph assuming 0% H % ! ?a82.9 is plotted as well. >or the /ilsner malt grist this assumption < 0% H % ! ?a82.9= was a better $it to the sodium bicarbonate cur.e while $or the 7ight 2unich 8 ?ara2unich grist the assumption 0% H % ( ?a8'.& was a better $it. The $ollowing slopes <unit p"JlJm+*!1= were determined $rom the data RA = A/2 - Ca/3.5 1 In this case 100 ppm o$ suspended chalk contribute onl# &0 ppm alkalinit# as ?a?A' or 1 m+*8l. %ll o$ its calcium takes part in the alkalinit# reducing reaction. This is what is assumed b# most <home= brewing water calculation spreadsheets. RA - A/2 - Ca/7 1 In this case 100 ppm o$ suspended chalk contribute onl# &0 ppm alkalinit# as ?a?A' or 1 m+*8l. 5ut since onl# hal$ the alkalinit# is contributed it is assumed that onl# hal$ the calcium takes part in the alkalinit# reducing reaction. Instead o$ '.& e*ui.alents it takes ) e*ui.alents o$ calcium to neutrali3e 1 e*ui.alent o$ alkalinit#.

While the data is not precise enough to con$irm this, it appears as i$ up to a residual alkalinit# contribution o$ I'!B m+*8l onl# hal$ the chalk,s alkalinit# and hal$ its calcium should be considered in residual alkalinit# calculations <i.e. + a , C3C aC . C3 2 ) A * A ) A * A -C a (3 .5 ) A * A -C a (2 .8 0% H %82 ! ?a8)=. 1 0 0 / 0 ils n e r 0 .0 4 2 0 .0 3 5 0 .0 3 9 The surprising data $or suspended chalk needed some 0 .0 0 .0 4 8 0 .0 5 4 8 0 (2 0 / 1 " M u n ic h (C a ra M II5 0 $urther in.estigation. >or that a strong sodium bicarbonate solution <'9)0 ppm Fa"?A'= and a strong calcium chloride solution <'&)0 ppm ?a?l2O2"2A= were prepared. These The same comparison with sodium bicarbonate water was solutions were mi ed to produce a water pro$ile that done $or suspended chalk waters. @ince no ?A2 was used to matched the alkalinit# and calcium content o$ the dissol.ed dissol.e the chalk the ma-orit# o$ the chalk remained chalk water that was prepared $or the earlier e periments. undissol.ed in the brewing water. Anl# the amount that Cpon standing it was apparent that this resulting water was could be dissol.ed b# the atmospheric ?A2 had a chance to o.er saturated with ?a?A since a precipitate was $orming ' dissol.e. This amount was considered small and neglected and settling. in these e periments. The results are shown in >igure 1&, Table 12 and Table 1'. The results are shown in >igure 19, Table 11 and Table 12. % cur.e similar to what was obser.ed $or suspended chalk %s seen be$ore, suspended chalk is not able to raise the p" can be seen $or water prepared with sodium bicarbonate and abo.e a certain threshold. That threshold, howe.er, calcium chloride. There are some irregularities that were not correlates with the distilled water mash p" and thus the in.estigated $urther. The cur.e $or the /ilsner malt grist and grist composition and not the actual p" o$ the mash. This the Fa"?A'P?a?l2 water is $latter than the one $or the indicates that it is a $unction o$ the chalk concentration and 2unich8?ara2unich malt grist. Ane e planation is, that the Fa"?A'P?a?l2 water mi $or the /ilsner malt e periments not the mash p". was prepared more than 2B hrs be$ore the e periment and There is some ambiguit# around the alkalinit# and residual had more time to precipitate chalk while the water $or the alkalinit# that is contributed b# undissol.ed chalk. 2ost 2unich8?ara2unich malt e periments was mi ed within 20 spreadsheets used b# home brewers, assume that chalk min o$ the e periment and had less time to precipitate chalk. contributes onl# hal$ its alkalinit# potential to the mash <i.e. The waters $or these e periment were created b# preparing the addition o$ 100 ppm ?a?A' results in an alkalinit# o$ a batch o$ mi ed Fa"?A and ?a?l water and then ' 2 onl# &0 ppm as ?a?A'=. To e.aluate that, the cur.es $or diluting that batch with distilled water to create water suspended chalk ha.e been plotted $or ' di$$erent residual samples o$ desired strength. alkalinit# $ormulas1 %nother irregularit# is apparent i$ the data $rom these RA = A - Ca/3.5 1 In this case 100 ppm o$ suspended chalk e periments is compared with the data $rom '.) QThe e$$ect actuall# contribute 100 ppm o$ alkalinit# as ?a?A' or 2 o$ calcium and magnesium in the brewing waterQ. Those m+*8l and all o$ its calcium takes part in the alkalinit# e periments also used sodium bicarbonate and calcium neutrali3ing reaction where it takes '.& e*ui.alents o$ chloride to create speci$ic brewing water samples but the calcium to neutrali3e 1 e*ui.alent o$ alkalinit# <Kolbach,s p" o.er 0% slope was steeper and matched that o$ -ust data= sodium bicarbonate water. %t this point it is assumed that

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11
the lower concentrations o$ ions, that were mi ed during these e periments, ma# not ha.e caused chalk to precipitate. Two mash samples o$ the last e periments were titrated with sodium h#dro ide to determine their bu$$er strength. @ample ? was part o$ the sodium bicarbonate series $or the light 2unich 8 ?ara2unich grist and had a mash p" o$ &.)& at an alkalinit# o$ ).1& m+*8l. @ample 7 was part o$ the Fa"?A'P?a?l2 series $or the same grist. It,s mash p" was &.) and the calculated residual alkalinit# was I1) m+*8l. @ample ? re*uired 2.'B m+*8l sodium h#dro ide to reach a p" o$ E.0 and sample 7 re*uired 2.B2 m+*8l sodium h#dro ide to reach the same p". This means that both samples had about the same bu$$er capacit# and the $latter p" o.er 0% cur.e was not the result o$ a stronger bu$$er capacit# o$ the mash prepared with Fa"?A'P?a?l2 water. %t this point no e planation can be gi.en $or the di$$erent p" beha.ior between waters with dissol.ed and undissol.ed chalk. In particular since both waters showed the same alkalinit# in titration e periments.

/igure 6@5 The pH;al!alinity slope 'spH( over mash thic!ness

'pulverized grist, 6, min mash at <= $( 20G We#ermann ?ara2unich II malt. The mash thickness was B l8kg. 0.1 2 sodium h#dro ide was used to titrate the cooled mash sample <2& ?= to a p" o$ E.2E. The results are shown in >igure 1E and Table 1B. I$ this titration cure is e pressed as m+*8l where l is the .olume o$ the strike water used in the mash9 and plotted together with a p" o.er alkalinit# cur.e $or the same mash, the titration cure has a slope that is about twice as steep as the slope $or the alkalinit# cur.e. The slope $or the mash titration was $ound as 0.10B p"JlJm+*!1 while the slope $or the p"!alkalinit# cur.e was onl# 0.0&0 p"JlJm+*!1. % similar relationship was $ound $or the p" lowering e$$ect specialt# malt malt acidit# has.

3.2 mash titration

>or this e periment a mash sample was prepared with distilled water and 90G >ranco 5elges 7ight 2unich and

3.13 Mash thic$ness

%s e pected, mash thickness has an e$$ect on mash p" as well. It was e.aluated with a 100G /ilsner <We#ermann= and a 100G 7ight 2unich <>ranco 5elges= grist. The data is shown in >igure 19, Table 1E and Table 1&. 6ust like most o$ the other results the relationship seems to be linear $or both mash thickness and alkalinit# within the e amined range o$ parameters. In these e periments the water did not contain an# calcium or magnesium. The higher the residual alkalinit# o$ the water, the more does mash thickness a$$ect mash p". @ince the# contain more water per malt and there$ore more alkalinit# per unit o$ malt, thinner mashes show a higher mash p" than thick mashes $or waters with the same alkalinit#. The slope o$ that p" increase o.er the increase o$ the mash thickness is similar between /ilsner and 2unich malt mashes. 2ashes
9 The amount o$ water added b# the sodium h#dro ide solution was neglected $or simplicit#. @ome rights reser.ed, 2009 Kai Troester, braukaiser.com, Act '1, 2009 see http188creati.ecommons.org8licenses8b#!nc8'.08 $or license details

/igure 6<5 mash titration curve compared to a pH over al!alinity curve. '>,E;*,E /ranco 3elges light Munich ;
Weyermann $araMunich malt, distilled water, pulverized grist, mash temp <>$, mash time *. min, mash thic!ness + l;!g, titration temperature *. $(

12

/igure 6>5 mash thic!ness and pH. Graphs showing the reaction between 7ilsner malt 'left hand side(, light Munich malt 'right hand side( and waters with varying residual al!alinity. The top graphs show the dependency between mash thic!ness and mash pH for different 01 waters while the bottom charts show the dependency between residual al!alinity for different mash thic!nesses. 'pulverized grist, 6, min mash at <= $(

with specialt# malts were not e.aluated but are e pected to beha.e similar based on the obser.ation made in >igure 9. ?on.ersel#, the thicker the mash the less e$$ect does a change in alkalinit# ha.e on mash p". I.e. mash thickness a$$ects sp", the p"JlJm+*!1 slope that is used to predict mash p" changes $rom <residual= alkalinit# changes. >or the $our mash thicknesses e.aluated, the $ollowing p" o.er m+*8l slopes were determined1
mash "hic$ness l($! 2 3 4 5 Munich li!h" p,(#, p,2l(m&' 0.035 0.012 0.049 0.018 0.066 0.023 0.077 0.027 0ilsner p,2l(m&' p,(#, 0.042 0.015 0.058 0.021 0.066 0.023 0.080 0.029

which can be appro imated with the $ollowing e*uation <>igure 1)=1

s pH = 0.01'00.01'
where spH5 the pH over al!alinity slope in pH?l?m2q-6 R5 mash thic!ness in l;!g Kolbach,s work showed showed a slope o$ 0.0' p"8d" or 0.09B p"JlJm+*!1. In these e periments this matched the data $or mashes with a mash thickness o$ about & l8kg. In contrast to this anal#sis, Kolbach,s work $ocused on a 12 /lato cast out wort p". This is a wort that is more dilute than a mash and would be e*ui.alent to much thinner
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1'
mashes.

3.11 4rist preparation

@o $ar the e periments ha.e been done with pul.eri3ed grists which are not a common $orm o$ grist preparation $or most breweries. The last series o$ e periments $or this paper e.aluated the e$$ect that the mill gap setting o$ a 2!roller mill has on the mash p" o$ a /ilsner malt <We#ermann= and a 7ight 2unich malt <>ranco 5elges= girst. >igures 19, 20 and 21 as well as tables 1) and 19 show the results. The mill gap setting has a slight impact on s p" to the e$$ect that it is $latter $or more $inel# ground grists and steeper $or more coarsel# ground grists. In particular these .alues were determined $rom the data1 0ilsner Mal" p"JlJm+*!1 0.063 0.075 0.082 0.094 1i!h" Munich p"JlJm+* !1 0.056 0.068 0.068 0.084

/igure 6C5 pH over brewing water al!alinity for malt milled at different mill gap settings. Weyermann 7ilsner malt '7ils( and /ranco 3elges 9ight Munich '9M( were evaluated. 1 mill cap setting of , mm refers to pulverized grist 'water prepared with HaH$#=, mash temperature <= $, mash time 6, min, mash thic!ness + l;!g(

mill !ap 3mm4 0 0.5 0.8 1.2

These di$$erences are likel# the result o$ a greater release o$ bu$$ering compounds $rom the more $inel# ground malt which make it more di$$icult $or the water alkalinit# to raise the mash p". The distilled water mash p" o$ more $inel# ground malt tends to be slightl# higher than that o$ coarsel# ground malt. This might not alwa#s be true and the result o$ measurement errors. It could, howe.er, be e plained through the assumption that acidic compound are more readil# released $rom the malt compared to strongl# bu$$ering compounds that reside in the endosperm and whose release into the mash depends on the accessibilit# o$ that endosperm to the mash li*uid.

/igure *,5 pH over mill gap setting for waters with = different al!ainity values. 1 mill gap of , mm refers to a pulverized grist. '/ranco 3elges 9ight Munich, water prepared with HaH$#=, mash temperature <= $, mash time 6, min, mash thic!ness + l;!g(

! *onclusion
In.estigation o$ a number o$ parameters that a$$ect mash p" in brewing showed that the relationships commonl# used $or predicting mash p" are based on a misinterpretation o$ Kolbach,s work who e.aluated the e$$ect o$ brewing water composition on a cast out wort o$ 12 /lato. 5ut it has been shown that Kolbach,s $indings still appl# *ualitati.el# and that his de$inition o$ residual alkalinit# is close to the obser.ations made in the e periments conducted $or this paper. In particular it was demonstrated to what e tend calcium and magnesium reduce the mash p"
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/igure *65 pH over mill gap setting for waters with = different al!alinity values1 mill gap of , mm refers to a pulverized grist. 'Weyermann 7ilsner, water prepared with HaH$#=, mash temperature <= $, mash time 6, min, mash thic!ness + l;!g(

1B
through acidic reactions with the malt. In these reactions calcium is twice as e$$ecti.e than magnesium. In addition to that the relationship between mash p" and alkalinit# is linear o.er the range that was e.aluated and is o$ interest in brewing practice. This allows $or a prediction o$ the p" change based on the water,s alkalinit# as well as calcium and magnesium content. The slope o$ that linear $unction depends on mash thickness and to a lesser e tend on grist preparation. When chalk is added to the brewing water or the mash, it needs to be dissol.ed with ?A2 in order to contribute its $ull alkalinit# potential. I$ that is not done or chalk is allowed to precipitate $rom the water it looses its e$$ecti.eness at higher concentrations. Without being dissol.ed ?halk additions past &00 ppm ha.e little or no e$$ect on mash p" The grist composition e$$ects mash p" as well. In general, the higher the weighted a.erage color o$ the malts used in the grist, the lower the mash p". % number o$ e ceptions howe.er e ist to this rule. @ome base malts which are lighter in color ma# ha.e a lower mash p" than darker base malts. @pecialt# malts reduce the mash p" b# contributing acidit# to the mash. When tested and put in relation to the malts color, cr#stal malts ha.e more acidit# per unit o$ color than roasted malts. %ll the roasted malts that were tested, showed nearl# the same acidit# while ha.ing a $airl# wide range o$ colors. While additional work is needed to con$irm the results $rom these small scale mashing e periments in large scale mashes, su$$icient data has been presented in order to gi.e the interested brewer guidance in estimating a mash p" based on a gi.en grist composition and brewing water composition or the e pected change o$ mash p" based on grist and8or brewing water changes.

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1&

" ,ppendix
".1 Tables
short name 0ilsner 3514 Munich II Maris -""er 0ale 39:;4 Munich I 6-ro= 0ilsner 3>M4 5hea" 2-ro= Munich 1i!h" 39>4 0ilsner 3524 ?ienna maltster 5e%ermann 5e%ermann <omas 9ace"" : ;on 5e%ermann >riess >es" Mal@ 5e%ermann )ahr 9ranco >el!es 5e%ermann 5e%ermann lot number 647& 35&74 633A 35&74 <9:; 293 I34A 35&74 >riess >es" Mal@ AB20080364 6088 35&74 )ahr 9ranco >el!es 6109 35&74 633A 35&74 color -&5*/ 3.581 2583 4.6380.5 1583 3.5781 3.880.2 481 3.5781 17.3582 3.581 7.581.5

Table 65 3ase malts used for the e"periments

malt name 0ilsner 3514 Munich II Maris -""er 0ale Munich I 6-ro= 0ilsner 3>M4 5hea" 2-ro= Munich 1i!h" 39>4 0ilsner 3524 ?ienna malt color -&5*/ 3.581 2583 4.6380.5 1583 3.5781 3.880.2 481 3.5781 17.3582 3.581 7.581.5 distilled water pH 5.76 5.43 5.77 5.3 5.79 5.73 6.04 5.56 5.46 5.75 5.56

Table *5 0esults of the base malt and distilled water mash pH e"periments 'pulverized grist, mash temp <= $, mash time 6, min, mash thic!ness + l;!g(
R, -dH/ -15.75 -9.85 -4.92 0 5.02 10.05 15.07 20.09 25.12 30.14 35.16 40.18 R, -m&'.l/ -5.61 -3.5 -1.75 0 1.79 3.58 5.36 7.15 8.94 10.73 12.51 14.3 1336 7ilsner pH 5.2 5.43 5.59 5.74 5.88 5.99 6.11 6.19 6.26 6.33 6.4 6.46 "36 7ilsner8 "36 Munich I 0"6 7ilsner8 pH 5.13 5.26 5.4 5.54 5.67 5.81 5.91 6.01 6.1 6.17 6.26 6.32 1"6 *araMunich II pH 5.13 5.27 5.4 5.55 5.69 5.81 5.91 6.02 6.09 6.18 6.25 6.29

Table =5 various grists mashed with waters over an e"tended range of al!alinities 'pulverized grist, mash thic!ness + l;!g, 6, min at <=$, water general hardness , m2q;l(

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1E
malt name Munich II Munich I Munich 1i!h" ?ienna Cara Munich III Cara Munich II Cara Munich I Cara Aroma Cr%s"al 101 Cr%s"al 201 Cr%s"al 401 Cr%s"al 601 Cr%s"al 901 Cr%s"al 1201 Cr%s"al 1501 roas" Carle% Clac$ pa"en" carafa iii carafa i carafa I 3sp4 >uiscui" ;auermal@ sauermal@ maltster 5e%ermann 5e%ermann 9ranco >el!es 5e%ermann 5e%ermann 5e%ermann 5e%ermann 5e%ermann >riess >riess >riess >riess >riess >riess >riess >riess >riess 5e%ermann 5e%ermann 5e%ermann un$no=n 5e%ermann 5e%ermann malt color -&5*/ acidit -m&'.$g/ 22 83 5.6 15 82 8.4 17.35 3 7.5 81.5 1.6 150 810 120 810 90 810 400 850 25.3 8D 51.8 8D 104.8 8D 157.8 8D 237.3 8D 316.8 8D 396.3 8D 793.8 8D 1323.8 8D 1400 8100 31.2 49 22.4 74.4 9.6 14.2 25.6 50.4 45 46 59.8 39.6 44.8 35.4 42 46.4 20.2 315.2 358.2 DI pH t pe

5.54 Case 5.44 Case 5.62 Case 5.65 Case 4.92 cr%s"al 4.71 cr%s"al 5.1 cr%s"al 4.48 cr%s"al 5.38 cr%s"al 5.22 cr%s"al 5.02 cr%s"al 4.66 cr%s"al 4.77 cr%s"al 4.75 cr%s"al 4.48 cr%s"al 4.68 cr%s"al 4.62 roas"e# 4.81 roas"e# 4.71 roas"e# 4.73 roas"e# 5.08 o"her 3.43 o"her 3.44 o"her

900 8100 900 8100

un$no=n 5 82 5 82

Table +5 base and specialty malt titration 'pulverized grist, mash thic!ness > l;!g, 6, min at <. $, cooled to *. $ for titration(
!ris" / 1 2 4 8 !ris" / 6 12 23 45 !ris" / 0 4 8 17 Carafa I special !ris" color 3&>C4 11.97 20.43 37.36 71.22 CaraMunich III !ris" color 3&>C4 12.29 21.08 37.2 69.43 CaraAroma !ris" color 3&>C4 3.5 19.36 35.22 70.91 p, 5.71 5.69 5.66 5.61 p, 5.66 5.58 5.43 5.21 p, 5.75 5.64 5.54 5.36

Table .5 Distilled water mash pH of a pilsner malt grist with = different specialty malts. 'pulverized grist, mash thic!ness + l;!g, 6, min at <=$(

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1)
,l$ -m&'.l/ 0 0 0 0 2.29 2.29 2.29 2.29 4.57 4.57 4.57 4.57 *a -m&'.l/ 0 3.16 7.91 15.82 0 3.16 7.91 15.82 0 3.16 7.91 15.82 pH 5.71 5.58 5.41 5.22 5.92 5.77 5.62 5.46 6.05 5.92 5.78 5.63 Al$ * 0 m&'(l slope )2 -0.0306 0.9842

Al$ * 2.3 m&'(l

slope )2

-0.0282 0.9653

Al$ * 4.6 m&'(l

slope )2

-0.0259 0.9710

Table <5 effect of calcium on the mash pH of a pilsner mash 'pulverized grist, mash thic!ness + l;!g, 6, min at <= $( 4H -m&'.l/ ,l$ -m&'.l/ pH 0 0 5.8 Al$ * 0 m&'(l slope -0.014 3.23 0 5.73 r2 0.980 8.07 0 5.66 16.14 0 5.57 0 2.29 5.93 Al$ * 2.3 m&'(l slope -0.010 3.23 2.29 5.88 r2 0.985 8.07 2.29 5.83 16.14 2.29 5.76 0 4.57 6.07 Al$ * 4.6 m&'(l slope -0.012 3.23 4.57 6.05 r2 0.985 8.07 4.57 5.97 16.14 4.57 5.89 Table @5 pH as a function of magnesium hardness and water al!alinity '7ilsner malt, pulverized grist, mash thic!ness + l;!g, 6, min at <= $(
026 <ight Munich malt -=ranco 5elges/ > 236 *araMunich II -9e ermann/ ppm *a*:3 suspended dissol;ed 0 5.3 5.3 241 5.4 5.42 483 5.46 5.57 724 5.49 5.78 965 5.49 5.94 1207 5.51 6.11

1336 7ilsner Malt -9e ermann/ ppm *a*:3 suspended dissol;ed 0 5.76 5.72 241 5.83 5.84 483 5.88 5.97 724 5.87 6.15 965 5.88 6.18 1207 5.81 6.33

Table >5 3rewing water chal! concentration and pH 'pulverized grist, mash temperature <> $, mash time *. min, mash thic!ness + l;!g(

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19
AaH*:3 water R, ? , 0.0 3.6 7.2 10.7 14.3 17.9
slope 3p,2l(m&'4 r2

*a*:3 > *:2 water R, ? , @ *a.3." 0.0 3.5 6.9 10.4 13.8 17.3
slope 3p,2l(m&'4 r2

pH 5.75 5.96 6.14 6.31 6.42 6.5 0.042 0.974

pH 5.7 5.8 6.0 6.2 6.2 6.3

R, ? , @ *a.2.2 0.0 2.6 5.3 7.9 10.6 13.2

pH 5.7 5.8 6.0 6.2 6.2 6.3 0.046 0.982

0.035 slope 3p,2l(m&'4 0.982 r2

Table C5 pH for brewing water prepared with different concentrations of sodium bicarbonate and chal! dissolved with $#*. '6,,E Weyermann 7ilsner malt, pulverized grist, mash temperature <> $, mash time *. min, mash thic!ness + l;!g(
AaH*:3 water R, ? , pH 0.0 5.29 3.6 5.52 7.2 5.71 10.7 5.92 14.3 6.05 17.9 6.17
slope 3p,2l(m&'4 r2

R, ? , @ *a.3." 0.0 3.5 6.9 10.4 13.8 17.3

slope 3p,2l(m&'4 r2

*a*:3 > *:2 water pH R, ? , @ *a.2.2 5.30 0.0 5.42 2.6 5.57 5.3 5.78 7.9 5.94 10.6 6.11 13.2 0.048 slope 3p,2l(m&'4 0.995 r2

pH 5.30 5.42 5.57 5.78 5.94 6.11 0.063 0.995

0.050 0.986

Table 6,5 pH for brewing water prepared with different concentrations of sodium bicarbonate and chal! dissolved with $#*. '>,E /ranco 3elges 9ight Munich ; *,E Weyermann $araMunich , pulverized grist, mash temperature <> $, mash time *. min, mash thic!ness + l;!g(
AaH*:3 water R, ? R, -7ils/ m&'.l pH 0.0 5.75 3.6 5.96 7.2 6.14 10.7 6.31 14.3 6.42 17.9 6.50 R, ? , @ *a.3." -7ils/ m&'.l pH 0.0 5.76 3.5 5.83 6.9 5.88 10.4 5.87 13.8 5.88 17.3 5.81 *a*:3 water R, ? ,.2 @ *a.) -7ils/ m&'.l pH 0.0 5.76 1.7 5.83 3.5 5.88 5.2 5.87 6.9 5.88 8.6 5.81 R, ? ,.2 @ *a.3." -7ils/ m&'.l pH 0.0 5.76 1.0 5.83 2.1 5.88 3.1 5.87 4.2 5.88 5.2 5.81

Table 665 pH for 6,,E pilsner grist and brewing waters prepared with sodium bicarbonate or suspended chal! 'pulverized grist, mash temperature <> $, mash time *. min, mash thic!ness + l;!g(
AaH*: 3 water R, ? R, -<M.*M/ m&'.l pH 0.0 5.3 3.6 5.5 7.2 5.7 10.7 5.9 14.3 6.1 17.9 6.2 R, ? , @ *a.3." -<M.*M/ m&'.l pH 0.0 5.30 3.5 5.40 6.9 5.46 10.4 5.49 13.8 5.49 17.3 5.51 *a*: 3 water R, ? ,.2 @ *a.) -<M.*M/ m&'.l pH 0.0 5.30 1.7 5.40 3.5 5.46 5.2 5.49 6.9 5.49 8.6 5.51 R, ? ,.2 @ *a.3." -<M.*M/ m&'.l pH 0.0 5.30 1.0 5.40 2.1 5.46 3.1 5.49 4.2 5.49 5.2 5.51

Table 6*5 pH for >,E light Munich and *,E $araMunich grist and brewing waters prepared with sodium bicarbonate or suspended chal! 'pulverized grist, mash temperature <> $, mash time *. min, mash thic!ness + l;!g(

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19
7ilsner AaH*:3>*a*l2 water
R, ? , @ *a.3." -m &'.l/ pH

AaH*:3 water
R, ? , -m &'.l/ pH

036 light Munich8 236 *araMunich II AaH*:3 water AaH*:3>*a*l2 water

R, ? , -m &'.l/ pH R, ? , @ *a.3." -m&'.l/ pH

0 3.58 7.15 10.73 14.3 17.88

5.75 5.96 6.14 6.31 6.42 6.5

0.0 3.3 6.7 10.0 13.4 16.7

5.79 5.85 5.9 5.94 5.98 5.97

0 3.58 7.15 10.73 14.3 17.88

5.29 5.52 5.71 5.92 6.05 6.17

0.0 3.5 6.9 10.4 13.8 17.3

5.3 5.42 5.53 5.61 5.65 5.7

Table 6=5 pH for mashes prepared sodium bicarbonate or sodium bicarbonate and calcium chloride waters. 'pulverized grist, mash temperature <> $, mash time *. min, mash thic!ness + l;!g(

m&'.l pH 0 5.32 slope 0.104 p,2l(m&' 0.74 5.41 r2 0.995 1.78 5.54 2.34 5.61 2.98 5.67 3.84 5.78 4.52 5.85 5.16 5.91 6.02 6 7.08 6.11 8 6.18 8.74 6.24 9.04 6.26 Table 6+5 Mash titration. '>,E;*,E /ranco 3elges light Munich ; Weyermann $araMunich malt, distilled water, pulverized grist, mash temp <>$, mash time *. min, mash thic!ness + l;!g, titration temperature *. $(

7ilsner -9e ermann/

B, * 0 m&'(l mash "hic$ness 3l($!4 2 3 4 5 p,(#3l($!4 r2 p, a" 0 l($! )A* 0 m&'(l 5.63 5.68 5.72 5.74 0.0370 0.9675 5.56 mash p, )A*2.7 m&'(l 5.75 5.83 5.9 5.98 0.0760 0.9993 5.6 )A*5.3 m&'(l 5.86 6 6.08 6.18 0.1040 0.9869 5.67 p,2l(m&' 0.042 0.058 0.066 0.080 r2 0.999 0.999 1.000 0.997

Table 6.5 data for the effect of mash thic!ness and water al!alinity on the mash pH of a 7ilsner malt. 'pulverized grist, 6, min at <= $(

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20
Munich <ight -=ranco 5elges/
B, * 0 m&'(l mash "hic$ness 3l($!4 2 3 4 5 p,2$!(l r2 p, a" 0 l($! )A* 0 m&'(l 5.33 5.4 5.42 5.48 0.0470 0.9625 5.24 =a"er )A*2.7 m&'(l 5.43 5.53 5.61 5.68 0.0830 0.9934 5.27 )A*5.3 m&'(l 5.52 5.67 5.78 5.9 0.1250 0.9955 5.28 p,2l(m&' 0.035 0.049 0.066 0.077 r2 0.999 1.000 0.999 0.999

Table 6<5 data for the effect of mash thic!ness and water al!alinity on the mash pH of a 9ight Munich malt. 'pulverized grist, 6, min at <= $(

,l$alinit mash pH for =ranco 5elges <ight Munich m&'.l pul;eri+ed -<M/ 3." mm -<M/ 3.0 mm -<M/ 1.2 mm -<M/ 0 5.41 5.37 5.38 5.35 2.86 5.59 5.59 5.58 5.6 5.71 5.73 5.76 5.77 5.83 pHBl.m&' 0.056 0.068 0.068 0.084 R2 0.995 0.995 1.000 0.999

Table 6@5 mash pH for different mill gap settings and water al!alinities for a /ranco 3elges 9ight Munich grist 'water prepared with HaH$#=, mash temperature <= $, mash time 6, min, mash thic!ness + l;!g(.

,l$alinit mash pH for 9e ermann 7ilsner m&'.l pul;eri+ed -7ils/ 3." mm -7ils/ 3.0 mm -7ils/ 0 5.78 5.74 5.73 2.86 5.98 5.98 6.01 5.71 6.14 6.17 6.2 0.063 0.075 0.082 pHBl.m&' R2 0.996 0.996 0.988

1.2 mm -7ils/ 5.73 6.02 6.27 0.095 0.998

Table 6>5 mash pH for different mill gap settings and water al!alinities for a Weyermann 7ilsner malt grist 'water prepared with HaH$#=, mash temperature <= $, mash time 6, min, mash thic!ness + l;!g(.

use# for <he effec" of calcium mash "hic$ness "he effec" of calcium an# ma!nesium al$alini"% sources al$alini"% sources eF"en#e# al$alini"% ran!e al$alini"% sources al$alini"% sources al$alini"% sources al$alini"% sources "he effec" of ma!nesium

EI =a"er =ei!h" ! 1005 1022 1384 1461 2429 1500 403.2 403.2 1500 1500 502

+a,C-3 ! 1.57 1.33

CaCl222,2! 2.34

M!;-427,20 !

CaC-3 !

"o"al har#ness m&'(l 31.64

Al$alini"% m&'(l 18.27 11.43 21.2 12.72 17.88 47.22 24.12 24.12

"i"ra"e# al$alini"% m&'(l 18.94 11.97 19.99 12.22 18.05 37.6 22.62 23.37

1.55 1.55 2.21 1.6 1.44 1.81 1.81 2

21.15 12.75

48.44 24.06 24.06 32.28

Table 6C5 The different batches of brines used to create the waters used in the e"periments

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