D.

c M. Riffe (2013)
A Homebrewing Perspective on Mash pH II: Water

D. Mark Riffe∗
(Dated: October 2, 2013)
An overview of the effect that water composition has on mash pH is presented. In particular,
we discuss (i) how bicarbonate (HCO− 3 ), calcium (Ca
2+
), and magnesium (Mg2+ ) ions contribute
to determining the pH through the concept of residual alkalinity (RA) and (ii) the use of lactic
or phosphoric acids to adjust RA and thus also mash pH. After reviewing the experimental work
of Paul Kolbach and Kai Troester on RA, we describe the models used by three spreadsheets (EZ
Water, Brun Water, and Kaiser Water) to calculate the effects of these ions and acids on the pH
of the mash. Based on our analysis of KT’s data, we also develop a model that may be used to
calculate RA and estimate its effect on mash pH. We then apply the four models to a simple pilsner-
malt based recipe to see how Ca2+ and acid additions are predicted to affect mash pH. Finally,
we suggest a simple approach to mash-water construction for homebrewers who wish build suitable
brewing liquor from distilled (or reverse osmosis) water.

1. INTRODUCTION the end of the paper we describe a simple approach to

A key element of the brewing process is the mash,
where grain and water are mixed together to promote
enzymatic processes essential to creating the final prod-
uct – beer! A mash can involve a number of reactions
at various rests (each associated with a specific temper-
ature range). More typically, however, a homebrewer’s
mash consists of the single essential rest somewhere in
the range of 145 to 160◦ F. At these temperatures amy-
lase enzymes present in the grain degrade starches con-
tained within into simple (yeast consumable) sugars and
not-so-simple dextrins.
An important parameter associated with this degrada-
tion of starches is the pH of the mash. Properties of both
the grain and strike water that form the mash determine
the exact pH value. In a companion paper we discuss the
contribution that the grain makes to the mash pH [1].1
Here we discuss the influence of the ions dissolved in the
strike water. As in our companion paper, we lean heavily
on the experimental work of Kai Troester (KT) [2].
We start by briefly describing the chemistry associated
with pH and and the related topics of alkalinity and resid-
ual alkalinity (RA). We then review and analyze KT’s
data involving the strike-water ions. This is followed by
a discussion of three models currently available for calcu-
lating mash pH (contained in the spreadsheets EZ Water
[3], Brun Water [4], and Kaiser Water [5]), all of which
are all based on KT’s data. We compare these models
and point out several significant differences in their im-
plementation of KT’s results. Based on our own analysis
of KT’s data, we also develop a model to predict mash
pH. As our overall goal is to be able to reliably hit a tar-
get pH when performing a single-step infusion mash, at
∗ URL: http://homebrewingphysics.blogspot.com/
1 We recommend reading the companion paper before reading this
paper.
building mash liquor when starting from distilled water.
2. pH AND ENZYMES
Water in its purest form contains only two elements,
hydrogen (H) and oxygen (O). Most of the H and O ap-
pear in the molecular form H2 O. But in any sample of
water there will be a small percentage of H and O atoms
that appear in two other forms, the ions H+ and OH− .2
The one essential fact about water chemistry is that the
product of the concentrations of these two ions is a con-
stant, independent of any other ionic species that may
be lurking around. If, for example, the addition of some
other ionic species causes [OH− ] to decrease, then [H+ ]
will necessarily increase.3 For absolutely pure water the
conservation of charge implies that [H+ ] = [OH− ]. A pH
of 7 characterizes this condition. If it so happens that
[H+ ] > [OH− ], then the pH value is < 7. As the ratio
of [H+ ] to [OH− ] increases the pH value decreases, and
the water becomes more acidic (or equivalently, less al-
kaline). If, on the other hand, [H+ ] < [OH− ], then the
pH is > 7, with smaller [H+ ] to [OH− ] ratios equivalent
to larger pH values.
Now all of this might only be a curiosity were it not
for the fact that enzyme driven reactions proceed most
efficiently within narrow pH ranges. For example, the
conversion of starches to sugars by alpha and beta amy-
lase occurs most efficiently if the pH is in the range of
about 5.2 to 5.6 (a mildly acidic condition).4 Other mash
2 To be precise, H+ is really shorthand for the hydronium ion
H3 O+ .
3 Here we use standard nomenclature to represent concentration:
[ISn± ] is shorthand for the molar concentration of ionic species
ISn± ; the standard unit for molar concentration is mol/L.
4 All pH values mentioned here refer to values obtained at room
temperature.
D. M. Riffe A Homebrewing Perspective on Mash pH II: Water

based enzymatic processes that the brewer might want is the sum of the carbonate and intrinsic alkalinities of
to utilize (such as protein degradation) also have favored the strike water [8], and {ISn± } represents the normality
ranges of pH values [6]. If the pH is too far from the ideal of ionic species ISn± .9 Equation (1) tells us that when
range for a particular reaction, then the process will be the strike water is mixed with the grist to form the mash,
very slow or perhaps not proceed at all. the presence of Ca2+ and Mg2+ ions lowers the effective
alkalinity of the strike water. As discussed in detail be-
low, this lowered alkalinity results in a mash that has a
3. RESIDUAL ALKALINITY AND MASH pH lower pH than it would otherwise have.
An important thing to notice is that very different
brewing liquors can have identical RAs. As an example,
Although there are a number of ions found in the wa- let’s compare the RAs of distilled and Burton-on-Trent
ter from any source, there are three that affect mash pH waters. Distilled water (which is free of all ions aside
most directly: HCO− 3 , Ca
2+
, and Mg2+ .5 The concentra- from H+ and OH− ) necessarily has an RA of 0.10 In rep-
tion of the bicarbonate ion HCO− 3 is (usually) the main resentative Burton water HCO− 2+
, and Mg2+ have
3 , Ca
component of what is known as water alkalinity,6 while normalities of 4.43, 13.75, and 3.29 mEq/L, respectively,
the concentrations of the Ca2+ and Mg2+ ions define wa- which results in A− res = 0.03 mEq/L [4]. As we shall
ter hardness. Residual alkalinity, which is essentially the shortly see, this RA value is negligibly different from 0,
effective alkalinity of the strike water when mixed with which means that identical-grain mashes carried out with
the grist to form the mash, is a simple function of the these two waters will have pH values that are very close
alkalinity and hardness of the strike water. Mash pH is to each other.
is often assumed to be a linear function of the residual
So how is residual alkalinity related to mash pH? In his
alkalinity.
paper PK mentions experimental results for the change
in pH of 1.048 OG (knockout) wort produced by a modest
change in RA [7]. The results can be stated a follows: An
3.1. Paul Kolbach Experimental Work increase (decrease) in RA of 3.57 mEq/L raises (lowers)
the mash pH by about 0.3. This result suggests that we
In 1953 brewing chemist Paul Kolbach (PK) published write the expected mash pH as
a paper on how, within the restrictions of the German
Reinheitsgebot, brewers could manipulate the mash pH
[7].7 For our purposes here the key concept described pHM = pHG + SRA A−
res , (3)
in PK’s paper is residual alkalinity A− 8
res , which can be
mathematically expressed as where SRA = 0.084 L/mEq and pHG (the grist pH) is the
pH that would result if distilled water were used for the
mash [1, 2]. It is worth keeping in mind that this value
{Ca2+ } {Mg2+ } of SRA = 0.084 L/mEq is derived from the change in pH
A− −
res = A − − , (1) of runoff from the sparged mash; As KT points out [2],
3.5 7
this may not be identical to the pH change within the
where mash itself.

A− = {HCO− 2− − +
3 } + {CO3 } + {OH } − {H } (2) 3.2. Kai Troester Experimental Work

In his extensive experimental investigation KT made

5 The ions Na+ , SO− −
4 , and Cl also affect beer flavor, but not via
adjustments to mash pH.
6 The terms alkalinity and alkaline, while related, are not the same
thing. Alkaline refers to water that has a pH >7 and so is thus
only related to the ratio of OH− to H+ . One can also use alkaline
to compare waters with two different pHs: the water with a larger
pH is more alkaline (or less acidic) than the one with the lower
pH. Alkalinity is related to the ion content of several species of
ions, as discussed in detail in what follows. It is also true that
water that is high in alkalinity does tend to be more alkaline
than it otherwise would be.
7 An English translation of this paper by A. J. deLange is available
at http://wetnewf.org/pdfs/Brewing articles/KolbachPaper.pdf
8 Unfortunately alkalinity and acidity both begin with the same
letter. In [1] we use A to represent mash acidity, and so to
distinguish alkalinity from acidity we use the superscript “−” to
denote alkalinity.
a number of measurements directly related to RA and
its effect on mash pH [2]. Here we review these experi-
ments. Unless otherwise noted, in all of the experiments
the mash thickness and temperature were 4 L/kg and
63◦ C, respectively, the grist was pulverized (using a cof-
fee grinder), and (25◦ C) pH readings were taken at 10
minutes.
9 The standard unit for normality is Eq/L. Apologies to the chem-
ical equilibrium literature, where {ISn± } often represents the
activity of species ISn± .
10 Insofar as an RA of 0 is 0 when using any units, we need not
specify the units when the value of the RA (or any other quantity,
for that matter) is 0.

2
D. M. Riffe A Homebrewing Perspective on Mash pH II: Water

6.4 Initial Alkalinity (mEq/L)

6.0 0
2.29
6.2 4.57

5.8
6.0

5.8
MASH pH

5.6

5.6

5.4
5.4

(a)
5.2
5.2
100% Pils

MASH pH
0 5 10 15
5.0 50% Pils, 50% Munich I 2+
Ca NORMALITY (mEq/L)
85% Pils, 15% CaraMunich II
4.8 6.4
2+
-5 0 5 10 15 Ca Normality (mEq/L)
0
RESIDUAL ALKALINITY (mEq/L) 6.2 3.16
7.91
15.82
FIG. 1: KT experimental results for mash pH as a function 6.0
of RA. As indicated, three different grist compositions were
used. Solid lines are linear fits to data for RA values from
5.8
−5.6 to +5.4. For clarity the 85% Pils, 15% CaraMunich II
data are vertically offset by −0.2.
5.6

In Fig. 1 we plot the results of KT’s experiments on 5.4

mash pH as a function of RA for three different grists
(100% pilsner malt, 50% pilsner and 50% Munich I malt,
and 85% pilsner with 15% CaraMunich II). In these ex-
periments the RA was manipulated with either the ad-
dition of hydrochloric acid (for negative RA values) or
sodium bicarbonate (positive RA values), and so changes
in either Ca2+ or Mg2+ levels were not involved. As we
show in the graph, the data between RA values of −5.6
and +5.4 are well represented by a straight lines. The
averaged slope of the fitted lines in this figure is SRA
= 0.074 L/mEq, not far from the PK’s value of 0.084
L/mEq. We remark that KT fit these data with a linear
function over the whole range of measured RA values,
obtaining an averaged slope of 0.061 L/mEq. However,
from Fig. 1 it is clear that the data do not continue to
be linear above an RA value of ∼6 mEq/L.
In another set of experiments KT investigated the ef-
fects of Ca2+ and Mg2+ on mash pH. For each of these
ions a set of 12 mashes was measured, with the inde-
pendent variables being (i) the initial alkalinity of the
water (before Ca2+ or Mg2+ addition) and (ii) the Ca2+
or Mg2+ normality. In Fig. 2 we present the data for
Ca2+ . In (a) and (b) the mash pH is plotted as a function
of the normality {Ca2+ } and initial alkalinity, respec-
tively. Each set of data is reasonably well represented
by a straight line. As a function of the water alkalin-
ity (for fixed {Ca2+ }) the averaged slope is SRA = 0.080
L/mEq, while as a function of {Ca2+ }, the averaged slope
(b)
5.2
0 1 2 3 4 5
INITIAL ALKALINITY (mEq/L)
FIG. 2: KT experimental results for mash pH with addition
of Ca2+ for different initial water alkalinities. Straight lines
are least-squares fits to each data set.
is −0.028 L/mEq. The ratio of these two slopes (−0.36
= −1/2.8) indicates the relative effect that Ca2+ has on
mash pH. Notice that −1/2.8 is close to the factor of
−1/3.5 in Eq. (1). We again note that the slope SRA =
0.080 L/mEq is again quite close to that of PK.
KT’s results for the effect of Mg2+ on mash pH are
shown in Fig. 3. As for the Ca2+ experiments, the data
in Fig. 3 can be well approximated with linear functions.
In this case the averaged slope versus alkalinity is SRA
= 0.067 L/mEq, while the slope vs versus {Mg2+ } is
−0.012 L/mEq. Their ratio, −0.18 = −1/5.6, is not far
from PK’s ratio of −1/7 in Eq. (1).
There are two other experiments of KT worth review-
ing. In the first of these experiments the effect of mash
thickness R on alkalinity induced changes in mash pH was
investigated. The grist for this experiment consisted of

3
D. M. Riffe A Homebrewing Perspective on Mash pH II: Water

6.2 6.2
Initial Alkalinity (mEq/L)
0 (a)
6.1
2.29 6.0
4.57
6.0
5.8
5.9

MASH pH
5.8 5.6

5.7
5.4
5.6
(a) R (L/kg) Pils Munich
5.2 2
5.5
3
MASH pH

0 5 10 15 4
2+
Mg NORMALITY (mEq/L) 5.0 5

Mg
2+
Normality (mEq/L) 0 1 2 3 4 5
6.2 0 RESIDUAL ALKALINITY (mEq/L)
3.23
8.07 -2
16.14 8x10
(b)
6.0

SRA (L/mEq) 7

5.8
6

5.6 (b) 5
Pilsner
Munich
Average Fit
0 1 2 3 4 5 4
INITIAL ALKALINITY (mEq/L)
2 3 4 5
MASH THICKNESS (L/kg)
FIG. 3: KT experimental results for mash pH with addition
of Mg2+ for different initial water alkalinities. Straight lines
are least-squares fits to each data set. FIG. 4: KT experimental results for mash pH as a function of
mash thickness R. (a) Mash pH versus RA for four thicknesses
and 2 different grists. Straight lines are least-squares fits to
either pilsner or Munich malt. The results are displayed
each data set. (b) Fitted values of slopes SRA [of straight
in Fig. 4. Figure 4(a) plots mash pH vs RA for both lines in (a)] versus R. Dashed lines are individual fits; solid
grists at four different values of R. Least-square fits are line is average of two dashed lines.
represented by the straight lines. The values of the slopes
SRA obtained from these fits are shown in Fig. 4(b). The
dashed lines are individual fits to each set of slope val-
ues. The solid line in (b), which is the average of the two
individual fits, can be written as
We note that for R = 4 L/kg, Eq. (4) yields SRA = 0.068
L kg L/mEq.
SRA = 0.0132 + 0.0137 R (4)
mEq mEq
This equation is very close to that deduced by KT from The last of KT’s experiments that we discuss investi-
the same data (using a slightly different analysis), gated how the crush of the grain affects SRA . Recall that
in all of the experiments discuss so far the grist was pul-
L kg verized. For this experiment KT also performed mashes
SRA = 0.013 + 0.013 R. (5) with the grist crushed by a roller mill at gap settings of
mEq mEq

4
D. M. Riffe A Homebrewing Perspective on Mash pH II: Water

6 L kg
SRA = 0.037 + 0.014 R. (6)
mEq mEq
5
This equation has (essentially) the same dependence on
FREQUENCY

4 R as Eq. (4), but for R = 4 L/kg yields SRA = 0.093

3 pulverized grain plus a correction of 0.022 L/mEq due to
2 As for the effects of Ca2+ and Mg2+ on residual al-
1 1/3.5 and 1/7 in Eq. (1) be replaced by 1/2.8 and 1/5.6,
0
6 7 8 9x10
-2
SRA (L/mEq)
FIG. 5: Histogram of SRA values from KT’s experiments for
63 C, 4 L/kg mashes with pulverized grist and mash pH mea-
sured at 10 minutes. Solid line is a Gaussian fit to the data.
Gaussian is centered at 0.071 L/mEq and has a width of 0.005
L/mEq.
20, 31, and 47 mil.11 These measurements were again
made on grist comprising either pilsner or Munich malt.
Insofar as a typical mill setting for a homebrewer is some-
where in the range of 31 to 47 mils we concentrate on the
results for those settings. KT’s data show that the aver-
age value of SRA at the two largest gap settings is 0.022
L/mEq larger than that for the pulverized grist.12
So what is the take-away from KT’s experimental re-
sults? First, in doing the experiments just described, KT
collected 15 individual data sets on 4 L/kg, 63◦ C mashes
with pulverized grist from which we have obtained a value
for SRA . In Fig. 5 we display a histogram of these SRA
values along with a Gaussian fit of the histogram. The
Gaussian is centered at SRA = 0.071 L/mEq and has a
width of ∼0.01 L/mEq.13 Given the number of measure-
ments, this average SRA is probably the most reliable
number to be extracted from KT’s data.
What we would really like, though, is an expression
for SRA that is applicable to the homebrewer who (i)
uses a typical crush and (ii) may use a mash thickness
R different from 4 L/kg. To this end we propose the
following equation for SRA ,
11 For those of you keeping score strictly in SI units, these settings
correspond to 0.5, 0.8, and 1.2 mm).
12 In these experiments the pulverized grist yielded an average SRA
= 0.060 L/mEq while the average SRA for the two largest gap
settings was 0.082 L/mEq. As the pulverized-grist SRA values
in this experiment are two of the lowest values obtained from
KT’s work, in this experiment the most reliable number is likely
the difference in SRA arising from a coarser crush, which is 0.022
L/mEq.
13 We remark that a simple average of the SRA values also yields
0.071 L/mEq.
L/mEq, which equals the average of 0.071 L/mEq for
a typical homebrewer crush.
kalinity, KT’s results suggest that Kolbach’s factors of
respectively. We note that these factors are both 25%
larger than those in Eq. (1). This consistency gives some
indication that these values may be more accurate than
those of PK when one is interested in the pH of the mash
itself. It thus may be reasonable for the homebrewer to
use
{Ca2+ } {Mg2+ }
A− −
res = A − − (7)
2.8 5.6
rather than Eq. (1). However, it can certainly be ar-
gued that more data on this topic is warranted before
the canonical equation of PK is superseded.
4. CONCENTRATION AND NORMALITY
In order to make practical use of either Eq. (1) or (7),
one must calculate the ionic normality that results from
the addition of a certain amount of a brewing salt to
the sparge water. Here we discuss {Ca2+ }, as the most
useful mash additions for the homebrewer are CaSO4 and
CaCl2 .
In the water-calculation spreadsheets discussed below,
a common form for the concentration CIS of a particular
ionic species IS is the weight wIS of the species divided by
the volume Vw of water in which the ions are dissolved.
The conventional unit for CIS is mg/L.14 To convert from
the concentration CIS to normality {ISn± } one must di-
vide by the molecular weight uIS of the ion and multiply
by the magnitude n of the ionic charge (expressed in units
of electron charge). That is,
CIS
{ISn± } = n . (8)
uIS
We note in passing that the molar concentration [ISn± ]
is simply related to CIS via
CIS
[ISn± ] = , (9)
uIS
14 As water has a density of 1 kg/L, the combination mg/L is (es-
sentially) equivalent to parts per million (ppm).

5
D. M. Riffe
and so we also have the simple relationship between nor-
mality and molar concentration,
{ISn± } = n [ISn± ]. (10)
So let’s say a brewer adds x mg of CaCl2 to y L of strike
water. What will be the number of equivalents of Ca2+ in
solution? Well, the first thing one must know is that each
CaCl2 molecule is typically hydrated by 2 H2 O molecules.
That is, the salt CaCl2 is really CaCl2 ·2(H2 O). Therefore,
if x mg of CaCl2 ·2(H2 O) is added then 0.272 x mg of
that addition is due to Ca, as 27.2% of CaCl2 ·2(H2 O)
is Ca. Similarly, Ca makes up 0.232 of the brewing salt
CaSO4 ·(H2 O). Generically denoting ionic fractions (such
as 0.272 and 0.232) as fIS , we can thus express the ionic
concentration as
x mg
CIS = fIS . (11)
y L
Substituting this into Eq. (8) gives us
x n mg
{ISn± } = fIS . (12)
y uIS L
Also relevant to this discussion of concentration and
normality is a method commonly used to specify alka-
linity (including RA). In all of the relevant equations so
far [Eqs. (1) and (2), e.g.], alkalinity has the same unit
as normality, which is Eq/L. A less direct (but nonethe-
less popular) method used to describe alkalinity is “as
CaCO3 ,” which is shorthand for “the concentration of
(dissolved) CaCO3 that would result in a given amount
of alkalinity if all of the alkalinity happened to come from
CaCO3 .” Because each molecule of CaCO3 dissociates
into Ca2+ and some combination of negative ions (with
a total charge of −2), we can use Eq. (8) to find that
an alkalinity of 1 mEq/L corresponds to 50 mg/L (= 50
ppm) of alkalinity as CaCO3 .
5. USING ACID TO MODIFY MASH pH
The addition of acid to the mash has long been used
to modify the pH. Indeed, acidulated malt was devel-
oped so that practitioners of the German Reinheitsgebot
could use lactic acid to lower mash (and thus also wort
and beer) pH. For the homebrewer there are two readily
available acids – lactic and phosphoric – that can be used
to this end.
Each of these acids lowers RA (and consequently mash
pH) by increasing {H + } and/or decreasing {HCO− 3 } in
the strike water [see Eq. (2)].15 Lactic acid has the chem-
ical formula C3 H6 O3 . For pH values relevant to brewing,
15 If the strike water is initially carbonate free, then alkalinity is
6
A Homebrewing Perspective on Mash pH II: Water
lactic acid readily dissociates into C3 H5 O− +
3 and H . It
+
thus provides one equivalent of H for every mole added.
The behavior of phosphoric acid H3 PO4 can be somewhat
more complicated. This is because it can (in principle)
lose up to 3 H+ ions when dissolved in water. However,
at relevant values of pH the ion H3 PO− 4 is usually the
predominant species. We can thus again assume that
one equivalent of H+ is produced for every mole of acid
added. Therefore, for either lactic or phosphoric addi-
tion, a mole of acid molecules added to the strike water
reduces the RA by one equivalent per volume of strike
water.
For this last statement to be of any use we need to
know how much the RA changes when a volume Vac of
X% (by weight) of acid solution is added to a volume Vw
of strike water. The change in alkalinity from such an
acid addition is given by
X ρac Vac
A−
ac = − , (13)
100 uac Vw
where ρac is the acid-solution density and uac is the
molecular weight of the acid. As discussed in the Ap-
pendix, the density ρac is a function of the strength X of
the acid solution. We note that the molecular weight of
lactic (phosphoric) acid is 90.09 (98.00) g/mol.
If one adds lactic acid to the mash via acidulated
malt consisting of X% of lactic acid, then the alkaliinity
change is instead given by
X wac 1
A−
ac = − . (14)
100 uac Vw
Here wac is the weight of the acidulated malt that is
substituted for standard base malt in the beer recipe.16
6. MODELS OF MASH pH
In the next several sections we discuss the models used
by the spreadsheets EZ Water [3], Brun Water [4], and
Kaiser Water [5] for calculating (i) RA (arising from both
brewing-salt and acid additions) and (ii) how RA affects
mash pH. We then suggest an alternative model, based
on KT’s experimental results, that the homebrewer may
wish to use to estimate mash pH. In the last subsection
primarily reduced by an increase in {H + }. If carbonates are
present, then the acid addition primarily lowers RA by increasing
(neutral) carbonic acid (H2 CO3 ) concentration at the expense of
the bicarbonate ion (HCO− 3 ) concentration.
16 Acidulated malt is, of course, part of the grist, and so one might
decide to account for its effect upon mash pH through grist acid-
ity rather than strike-water alkalinity. While this is conceptually
more straightforward, insofar as acidulated malt adds lactic acid
to the mash, we prefer to think of its contribution as a change in
RA of the strike water. Either view of acidulated malt is valid.
D. M. Riffe A Homebrewing Perspective on Mash pH II: Water

TABLE I: Calculated alkalinity change A− ac produced by acid additions. Results from EZ Water (EZW), Brun Water (BW), and
Kaiser Water (KW) are shown, along with results from present model (PM), which uses either Eq. (13) or (14) (as appropriate).
Acid densities used in Eq. (13) are calculated from equations in the Appendix. Additions are assumed to be made to 4.8 gal
of water, which for 10 lb of grist produces a mash thickness of 4 L/kg.
Addition X(%) Amount A−
ac (mEq/L)
EZW BW KW PM

Phosphoric acid 85 10 mL −8.9 −8.0 −8.0

Phosphoric acid 10 100 mL −10.5 −6.1 −5.9
Lactic acid 88 10 mL −12.9 −6.6 −6.5 −6.5
Lactic acid 10 100 mL −14.7 −7.5 −6.2 −6.2
Acidulated malt 3a 1 lb −20.8 −5.2 −8.2 −8.3
a The percentage of lactic acid is not adjustable in Brun Water: it

is effectively fixed at 1.9%.

we compare these four models using a simple mash that
consists entirely of pilsner malt.
Before discussing the features of the individual spread-
sheets, we note that each spreadsheet allows the home-
brewer to input (i) all of the brewing-relevant ions that
might already be present in his/her source water and (ii)
a variety of potentially desirable salt additions (CaCl2 ,
NaHCO3 , etc.). While these capabilities can be quite
useful, our interest here is focused solely on the minimal
additions necessary to create a suitable mash liquor from
distilled (or reverse-osmosis) water. To do this using any
of the spreadsheets one can (i) set the initial water pro-
file to have no dissolved ions and (ii) (as discussed in
detail below) only consider additions of CaSO4 , CaCl2 ,
and phosphoric or lactic acid. We thus discuss only these
aspects of each spreadsheet.
For this simplified approach of modifying distilled wa-
ter with Ca salts and/or acid additions to create the mash
liquor, we can simplify the basic equation for residual al-
kalinity. As we are neglecting Mg2+ in the brewing water
and any acid addition serves to directly increase {H+ },
we can write both Eq. (1) and Eq. (7) as
{Ca2+ }
A− −
res = Aac − , (15)
ECa
where ECa = 3.5 (PK) or 2.8 (KT result) describes the
effectiveness of Ca2+ in reducing the residual alkalinity.
6.1. RA Calculations
All three spreadsheets (essentially) use the same equa-
tions to calculate Ca2+ ion concentration and the result-
ing contribution to RA. Specifically, for a given amount
of either CaCl2 or CaSO4 added to the strike water,
Eq. (11) is used to calculate the concentration CCa2+ .
Equation (12) is then used to find {Ca2+ }, and using
this normality Eq. (15) (with ECa = 3.5) is used to de-
termine the contribution of Ca2+ to the RA. There are
slight differences among the CCa2+ and RA values pro-
duced by the spreadsheets (likely due to round-off error);
however, the differences in resulting RA values are less
than 2%, and so for practical purposes all spreadsheet
calculated Ca2+ contributions to RA are the same.
In contrast to the salt additions, there are significant
differences among the spreadsheets when it comes to the
addition of acid. First, EZ Water does not provide for a
phosphoric-acid addition. Second, Brun Water and EZ
Water do not account for the dependence of acid density
ρac on acid concentration X%. Third, EZ Water appears
to have systematic errors in its handling of both lactic
acid and acidulated malt.
Brun Water has inputs for either lactic or phosphoric
acid and acidulated malt. For acid solutions Brun Water
uses Eq. (13) to determine the acid contribution to al-
kalinity. However, as Brun Water’s calculated values of
A−ac simply scale with the strength X, it is apparent that
the dependence of density ρac upon X is not included.
As for acidulated malt, Brun Water includes it as a grist
addition rather than a strike-water addition. Brun Wa-
ter assumes that acidulated malt adds 95 mEq/lb (209
mEq/kg) of acidity to the mash, which is equivalent (in
Brun Water’s calculations) to an alkalinity contribution
of (−95 mEq/lb)wac /Vw . We note that this acidity of
95 mEq/lb is equivalent to acidulated malt comprising
1.9% lactic acid. This value is somewhat less that the
∼3% acidity measured by KT for (Weyermann) acidu-
lated malt [2].
Kaiser Water is the most versatile of the spreadsheets
in that it has inputs for both lactic and phosphoric acids
as well as acidulated malt. In its handling of acid solu-
tions this spreadsheet does account for the dependence
of the density ρac on strength X by assuming a linear
relationship, ρac =(1 + b X) kg/L. For lactic (phosphoric)
acid Kaiser water sets the slope b using ρac = 1.2 kg/L
(1.685 kg/L) for X = 88% (85%). As discussed in the
Appendix, this linear approximation is excellent for lac-
tic acid, but not so good for phosphoric. Kaiser Water
calculates A− ac using Eqs. (13) and Eq. (14).
EZ Water has inputs for both lactic acid and acidulated

7
D. M. Riffe
TABLE II: Model pH values for 100% pilsner-malt mash (1.9 ◦ L) with R = 3.2 L/kg (1.5 qt/lb) and wg = 4.54 kg (10 lb).
Results from EZ Water (EZW), Brun Water (BW), Kaiser Water (KW), present model (PM), and Mash Chemistry and Brewing
Water Calculator (MCBWC) are shown. pH values are for distilled water, distilled water plus Ca, and Ca plus acid additions,
as indicated.
Mash Liquor
EZW
Distilled water (dw)
dw + 50 ppm Ca2+
dw + 50 ppm Ca2+ + 30 mL 10% phosphoric acid
dw + 50 ppm Ca2+ + 3 mL 88% lactic acid
dw + 50 ppm Ca2+ + 4 oz acidulated malt
malt, but it does not include phosphoric acid. Similar to
Brun Water it assumes a constant density for all lactic-
acid solutions, calculating the acid contribution to the
alkalinity using
X Vac gal
A−
ac = −(2) (176.1) (16)
100 mL Vw
Here A− ac is expressed in ppm as CaCO3 . Unfortunately,
the factor of 2 on the right-hand side of Eq. (16) appears
to have been inserted in error. If we use ρac = 1.2 kg/L
for 88% lactic acid, insert these values into Eq. (13), and
transform Eq. (13) into the form of Eq. (16), we then
obtain Eq. (16) sans this factor of 2. The upshot is that
in EZ Water the lactic acid contribution to alkalinity is
much larger than that calculated by the other two spread-
sheets.
In the case of acidulated malt EZ water uses
X wac gal
A−
ac = −(2.5) (4160.4) . (17)
100 oz Vw
to calculate the lactic-acid contribution to the alkalin-
ity, where (again) the units are ppm as CaCO3 . Similar
to the comparison between Eqs. (16) and (13) for lac-
tic acid, a comparison of Eq. (17) with Eq. (14) reveals
an extra factor of 2.5 in the equation used by EZ water,
which again results in an an alkalinity contribution that
is much larger than that calculated by either Brun Water
or Kaiser Water.
For comparison among the three spreadsheets, in Ta-
ble I we present values of A− ac calculated by all of the
spreadsheets for two different additions of lactic and/or
phosphoric acid as well as an acidulated malt addition.
We assume the acidulated malt to to be 3% lactic acid,
as measured by KT [2]. Table I also include values that
we have calculated using Eq. (13) for the acid solutions
and Eq. (14) for the acidulated malt. The acid densities
we have used in Eq. (13) are discussed in the Appendix.
The results in Table I highlight the differences among
the spreadsheets in calculated values of A− ac . First, the
much larger values calculated by EZ Water are (primar-
ily) due to the extra factors that appear in EZ Water’s
A Homebrewing Perspective on Mash pH II: Water
pH
BW KW PM MCBWC
5.70 5.69 5.54 5.72 5.75
5.66 5.57 5.49 5.65 5.67
4.89 5.34 5.47 5.44
5.40 5.14 5.33 5.45 5.43
5.30 5.28 5.32 5.44 5.42
equations, as described above. Second, the larger val-
ues from Brun Water (when compared to Kaiser Water,
e.g.) for the more dilute acid solutions are due to Brun
Water’s use of a constant acid density, independent of
X. Third, the smaller A− ac value from Brun Water for
acidulated malt is due to a smaller assumed value of X
for acidulated malt compared to the value of 3% used in
the Kaiser Water and the present calculations.
6.2. pH Calculations
As Eq. (3) indicates, one needs to not only know the
residual alkalinity A−
res , but also the slope SRA in order
to calculate the strike-water influence on mash pH. We
now discuss this aspect of each spreadsheet’s calculations.
We also discus our recommendation for SRA .
The calculations in Brun Water use SRA = 0.17
L/mEq. We remark that this same factor is used in Brun
Water’s calculation of the influence of malt acidity on
grist pH, which we now briefly review (see [1] for further
details). When malt acidity Am (in units of mEq/kg) is
divided by the mash thickness R (in units of L/kg), then
one ends up with malt acidity per (strike-water) volume,
which has the same units (mEq/L) as residual alkalin-
ity A−res . Brun Water treats water alkalinity and mash
acidity per volume on equal footing by multiplying both
acidity and alkalinity by 0.17 L/mEq to predict changes
in pH.
Kaiser Water uses the formula SRA = (0.02 L/mEq) R.
This proportional dependence on R is in stark contrast
to Brun Water’s constant slope. The upshot is that in
Kaiser Water the change in mash pH due to given salt
and/or acid additions is independent of the mash thick-
ness R (owing to the fact that A− res itself scales inversely
with R). For a mash thickness of 4 L/kg (the thickness
of most of KT’s experimental mashes), the Kaiser Water
slope is SRA = 0.08 L/mEq. This value is slightly larger
than the averaged value of 0.071 L/mEq obtained from
our analysis of KT’s pulverized-grist data. The value of
0.08 L/mEq is also about half of that used by Brun Water
(0.17 L/mEq).
EZ Water calculates the slope SRA using Eq. (5), which
8
D. M. Riffe
comes directly from KT’s analysis of his experimental
pulverized-grist mashes. Because Eq. (5) has both a
constant term and one proportional to R, there is some
mash-thickness dependence to the resulting pH, but it is
not as dramatic as that calculated by Brun Water. For
a mash thickness of 4 L/kg, we note that Eq. (5) gives
us SRA = 0.065 L/mEq, which is somewhat less than
the value of 0.08 L/mEq obtained from Kaiser Water’s
formula.
We remind the reader of our recommended expression
for SRA , Eq. (6). It has essentially the same dependence
on R as the expression used by EZ Water, but accounts
for the dependence on grain crush measured by KT. At R
= 4 L/kg, Eq. (6) produces SRA = 0.093 L/mEq, slightly
larger than the Kaiser Water value (0.08 L/mEq) at the
same mash thickness, but significantly larger than that
of EZ Water (0.065 L/mEq). Based on KT’s results for
mash pH, we further recommend that ECa = 2.8 be used
in Eq. (15).
In Table II we compared results from these four models
for the effects of Ca and Ca plus acid additions on mash
pH. The mash for this comparison consists of 4.54 kg (10
lb) of 100% pilsner malt mashed at a thickness of 3.2
L/kg (1.5 qt/lb), a typical homebrewer mash thickness.
Mash pH for distilled water for these four models has
been discussed previously [1]. From the table we see that,
in most cases, the pH results for our present model (PM)
are higher than the other three models. The other three
models predict lower pH values, each because of unique
reasons. (i) The EZ water values are lower primarily due
to the extra factors introduced in the equations for A− ac ,
although this is ameliorated somewhat by a relatively
smaller value of SRA . (ii) The Brun Water values are
lower due to its large value of SRA and, in the case of the
phosphoric acid addition, the fact that Brun Water uses a
constant density ρac for each acid. (iii) The lower values
for Kaiser Water are primarily due to its significantly
lower pH value for a distilled-water mash. In spite of our
model’s systematically larger pH values, we feel that it
is a better representation of KT’s experimental results.
As evidence that this may indeed be the case, we have
also included in Table II results for mash pH from an
online calculator (Mash Chemistry and Brewing Water
Calculator) available at the Brewer’s Friend website [9].
This calculator represents the most recent modeling effort
of KT with regards to mash pH. As shown in Table II,
the results from the Brewer’s Friend calculator are much
closer to the results from our model than the results from
the three spreadsheets.
7. SIMPLE APPROACH TO MASH LIQUOR
So what is a homebrewer to do with regards to mash
water chemistry? With the goal of keeping things as
simple as possible, we suggest the following approach.
We acknowledge that our recommendations lean heav-
ily on suggestions contained in Brewing Better Beer by
9
A Homebrewing Perspective on Mash pH II: Water
(renowned homebrewer and BJCP judge) Gordon Strong
[10].
(i) Water. First, we recommend that the homebrewer
start with water that has negligible ion content. If one is
lucky enough to have tap water that consistently resem-
bles the ultrasoft water of Plzen, then one need look no
further than the kitchen tap. Unfortunately, in many lo-
cations throughout the US there are two problems with
the water supply. First, in many areas the local water
supply is high in bicarbonate, which makes the alkalinity
undesirably high [see Eq. (2)]. There are methods to neu-
tralize the bicarbonate ion, but they are either time and
energy consuming (boiling, cooling, and decanting), or
they may raise certain ions concentrations to undesirable
levels through the requisite salt and/or acid additions.
Second, because many municipalities use water sources
that vary with the seasons, the ion content of the tap
water in these locals may not be constant. Thus, for
many homebrewers consistent mash water is most read-
ily achieved by starting with distilled or reverse-osmosis
water.
(ii) Calcium addition. In order to insure a healthy
mash, the Ca2+ concentration of the strike water should
be raised to ∼50 mg/L (ppm).17 Using Eq. (11) along
with the observation that fIS ≈ 0.25 for either CaSO4 or
CaCa2 , one can show that ∼50 mg/L Ca2+ is achieved
by the addition of 200 mg/L of either salt. For a typical
R = 1.5 qt/lb mash of wg = 10 lb of grain (for 5 gal of
beer), this translates into a salt addition of ∼3 gm, which
is ∼0.8 tsp of either salt [9]. Whether one uses CaSO4
or CaCa2 (or some combination) should be influenced by
the desire to emphasis hops (CaSO4 ) or malt (CaCa2 )
in the final beer. We point out that flavor considerations
may dictate further addition of these salts to the cast-out
wort (or even the finished beer).
(iii) Acid addition. Whether an acid addition is also
warranted depends upon the grain bill. The brewer, of
course, selects the grist according to the target charac-
teristics of the final product. As discussed in detail in
[1], darker grains tend to produce mashes with lower pH
values. Referring to Fig. 3 of [1] and noting that the ad-
dition of 50 mg/L of Ca2+ drops the mash pH by slightly
less than 0.1, we see for practically all beers styles that
the mash pH will likely be ≥5.4 without further mod-
ification of the strike water. For beers with color <20
SRM, however, the addition of some acid to further drop
the pH is likely desirable. As Table II shows, a 50 mg/L
Ca2+ addition to mashes of the lightest beers will typi-
cally result in a pH of ∼5.6. For a mash thickness of 3.2
L/kg (1.5 qt/lb), Table II indicates the amounts of vari-
ous acids that should put the pH of such mashes in the
vicinity of 5.4. Darker beers, of course, would typically
17 50 mg/L of Ca2+ is the recommended minimum level for the
mash. Levels above this are fine as far as the mash chemistry
goes, although the flavor consequences of larger additions should
be considered.
D. M. Riffe
1.7
phosphoric
1.6 lactic
1.5
DENSITY (kg/L)
1.4
1.3
1.2
1.1
1.0
0.0 0.2 0.4 0.6 0.8
ACID CONCENTRATION (X%/100)
FIG. 6: Phosphoric and lactic acid densities as a function
of concentration X. Circles and solid lines are experimental
data and fits to those data, respectively
need less additional acid.
We point out one further procedure that can simplify
strike-water treatment: one can leave out from the mash
both crystal and dark-roasted grains and, instead, sepa-
rately steep them (as when making a malt-extract based
beer). For many beer styles such removal leaves only a
light base malt to be mashed. Hence, for a wide variety
of beers the necessary acid addition will be the similar.
A benefit of steeping dark roasted grains, espoused by
Strong [10], is that a less acrid, smoother tasting beer
results if the dark-grain tea is added very late in the boil
or sometime thereafter.
So how should the homebrewer implement our sug-
gested approach? Partly this depends upon whether or
not the homebrewer is willing (and/or able) to measure
pH during the brewing process. If so, then the model
presented here should give the brewer some idea of the
amount of acid needed to achieve a target pH. If one in-
deed has a pH meter (or suitable pH strips), then acid can
be added incrementally until the proper pH is achieved.
Even without pH verification, (any of) the models we
have discussed will likely put the pH in the ballpark. For
those not inclined to implement model equations on their
own, we suggest the Mash Chemistry and Brewing Water
Calculator [9], which has a straightforward interface for
implementing both salt and acid additions.
Ultimately, any adjustments in water treatment should
be driven by the flavor of the final beer. Many homebrew-
ers, in an effort to produce the highest quality product,
will multiply rebrew a given beer with tweaks to the grain
bill, hops, and (possibly) yeast. John Palmer suggests
that mash pH is a critical component in determining beer
flavor [11]. This implies that tweaks to water treatment
10
A Homebrewing Perspective on Mash pH II: Water
should also be considered as part of the process of im-
proving any given recipe. This also indicates that any
(published) recipe is incomplete unless water composi-
tion is also included. Indeed, it is nice to see that some
of the winning NHC recipes recently reported in Zymurgy
now include information about water treatment [12].
8. SUMMARY AND CONCLUSIONS
We have presented an overview of how strike-water
ions and acid additions affect the pH of the mash. In
particular, we have (i) discussed the concept of residual
alkalinity (RA) and its impact on pH [2, 7], (ii) summa-
rized and analyzed the experimental work of Kai Troester
(KT) on this topic [2], (iii) described models (based on
KT’s experimental results) used by three spreadsheets
(EZ Water [3], Brun Water [4], and Kaiser Water [5]) for
calculating how salt and acid additions affect mash pH,
(iv) developed an alternative model for calculating RA
and mash pH, and (v) suggested a simple approach to
treating distilled (or reverse osmosis) water in order to
produce a suitable mash liquor.
In conjunction with our companion paper [1], we hope
that this paper gives the all-grain homebrewer some in-
sight into mash chemistry and its effect upon pH. Indeed,
the world of weak acids, ionic concentrations, alkalinity,
and pH can indeed be daunting. Because of this, many
homebrewers avoid the topic as long as possible. Person-
ally, I finally wrestled with this topic due to my desire to
nail down the classic style of German Pilsner. Although
rather technical, we hope that these two papers make un-
derstanding this topic a bit simpler for other homebrew-
ers who desire to understand how the fourth ingredient
– water – impacts their beer.
APPENDIX: DENSITIES OF LACTIC AND
PHOSPHORIC ACIDS
As the percentage X of acid in solution increases, the
density ρac of the solution increases. In Fig. 6 we plot the
density of both lactic [13] and phosphoric acid [14, 15] as
a function of acid concentration. As the figure shows the
density versus concentration relationship is quite linear
for lactic acid but slightly more complicated for phospho-
ric.
We have least-squares fit the lactic-acid density data
with a linear function and the phosphoric-acid data with
a quadratic function; the fits are the solid lines in Fig. 6.
These two fits can be expressed as ρlac = (1 + 0.237
X/100) kg/L and ρphos = [1 + 0.490 X/100 + 0.375
(X/100)2 ] kg/L. For 10% (88%) lactic acid the first equa-
tion yields ρlac = 1.023 kg/L (1.208 kg/L), while for 10%
(85%) phosphoric acid we likewise obtain ρphos = 1.052
kg/L (1.687 kg/L).
D. M. Riffe
[1] D. M. Riffe, A Homebrewing Perspective on Mash pH
I: The Grist (2013), URL http://homebrewingphysics.
blogspot.com/.
[2] K. Troester, The Effect of Brewing Water and
Grist Composition on the pH of the Wort (2009),
URL http://braukaiser.com/documents/effect_of_
water_and_grist_on_mash_pH.pdf.
[3] EZ Water Calculator 3.0.2 (2012), URL http://www.
ezwatercalculator.com/.
[4] M. Brungard, Brun Water Calculator 1.14us (2013),
URL https://sites.google.com/site/brunwater/.
[5] K. Troester, Kaiser Water Calculator US units 1.58
(2012), URL http://braukaiser.com/documents/.
[6] K. Troester, How pH Affects Brewing (2009), URL
http://braukaiser.com/wiki/index.php?title=How_
pH_affects_brewing.
[7] P. Kolbach, Der Einfluss des Brauwasser auf das pH von
Würze und Bier, Monatszeitschrift für Brauerei 6 (1953).
[8] G. L. Bowie, W. B. Mills, D. B. Porcella, C. L. Camp-
bell, J. R. Pagenkopf, G. L. Rupp, K. M. Johnson,
P. W. H. Chan, S. A. Gherini, and C. E. Chamberlin,
Rates, Constants, and Kinetic Formulations in Surface
11
A Homebrewing Perspective on Mash pH II: Water
Water Qaulity Modeling (1985), URL http://www.ecy.
wa.gov/programs/eap/models/rates_and_constants/.
[9] K. Troester, Mash Chemistry and Brewing Water Cal-
culator (2013), URL http://www.brewersfriend.com/
mash-chemistry-and-brewing-water-calculator/.
[10] G. Strong, Brewing Better Beer (Brewers Publications,
2011).
[11] B. Smith, BeerSmith Home Brewing Podcast (#60) (May
28, 2013).
[12] A. T. Scheppach, Zymurgy, p. 44 (September/October
2013).
[13] R. A. Troupe, W. L. Aspy, and P. R. Schrodt, Industrial
and Engineering Chemistry 43, 1143 (1951), URL http:
//pubs.acs.org/doi/abs/10.1021/ie50497a042.
[14] J. H. Christensen and R. B. Reed, Industrial and Engi-
neering Chemistry 47, 1277 (1955), URL http://pubs.
acs.org/doi/abs/10.1021/ie50546a061.
[15] E. P. Egan and B. B. Luff, Industrial and Engineering
Chemistry 47, 1280 (1955), URL http://pubs.acs.org/
doi/abs/10.1021/ie50546a062.