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Chapter
15 - Understanding the Mash pH

15.3
Residual Alkalinity and Mash pH

Before you
conduct your first mash, you probably want to be assured that it will
probably work. Many people want to brew a dark stout or a light
pilsener for their first all-grain beer, but these very dark and very
light styles need the proper brewing water to achieve the desired mash
pH. While there is not any surefire way to predict the exact pH,
there are empirical methods and calculations that can put you in the
ballpark, just like for hop IBU calculations. To estimate your
base-malt-only mash pH, you will need the calcium, magnesium and
alkalinity ion concentrations from your local water utility report.
Unfortunately, you rarely want to brew a base-malt-only beer.

To estimate
your recipe mash pH, you will need the calcium, magnesium and
alkalinity ion concentrations from the water report, plus the
approximate color of the beer you are trying to brew.

Background:
In 1953, P. Kohlbach determined that 3.5 equivalents (Eq) of calcium
reacts with malt phytin to release 1 equivalent of hydrogen ions
which can "neutralize" 1 equivalent of water alkalinity.
Magnesium, the other water hardness ion, also works but to a lesser
extent, needing 7 equivalents to neutralize 1 equivalent of
alkalinity. Alkalinity which is not neutralized is termed
"residual alkalinity" (abbreviated RA). On a per volume
basis, this can be expressed as:
mEq/L RA = mEq/L Alkalinity - [(mEq/L Ca)/3.5 + (mEq/L Mg)/7]
where mEq/L is defined as milliequivalents per liter.

This residual
alkalinity will cause an all-base-malt mash to have a higher pH than
is desirable (ie. >6.0), resulting in tannin extraction, etc. To
counteract the RA, brewers in alkaline water areas like Dublin added
dark roasted malts which have a natural acidity that brings the mash
pH back into the right range (5.2-5.6). To help you determine what
your RA is, and what your mash pH will probably be for a 100% base
malt mash, I have put together the following nomograph that allows
you to read the base-malt-mash-pH after marking-off your water's
calcium, magnesium and alkalinity levels. To use the chart, you mark
off the calcium and magnesium levels to determine an
"effective" hardness (EH), then draw a line from that value
through your alkalinity value to point to the RA and the approximate
pH. The effective hardness is not the same as the "Total
Hardness as CaCO3" you may see on your water report, it is a
calculation of the effect that calcium and magnesium have on
alkalinity.

After
determining your RA and probable pH, the chart offers you two
options:
a) You can plan to brew a style of beer that approximately matches
the color guide above your RA, or
b) You can estimate an amount of calcium or bicarbonate to add to the
brewing water to hit a targeted residual alkalinity, one that is more
appropriate to the color of the style you want to brew.
I will show you how this works in the following example.

Determining
the Beer Styles That Best Suit Your Water
1. A water report for Los Angeles, CA, states that the three ion
concentrations are:
Ca (ppm) = 70
Mg (ppm) = 30
Alkalinity = 120 ppm as CaCO3
2. Mark these values on the appropriate scales. (Denoted by red and
green circles here.)

3. Draw a line
between the Ca and Mg values to determine the Effective Hardness.
(Denoted by a red square.)
4. From the value for EH, draw a line through the Alkalinity value
(green circle) to intersect the RA/pH scale. This is your estimated
base-malt-mash pH of 5.8 (blue square).
5. Looking directly above the pH scale, the color guide shows a range
of color which corresponds to most amber, red and brown ales and
lagers. Most Pale Ale, Brown Ale and Porter recipes can be brewed
with confidence. The amount of acidity in the specialty grains used
in these styles should balance the residual alkalinity to achieve the
proper mash pH (from 5.8 down to 5.2-5.6, depending on the darkness
of the recipe).

Determining
Calcium Additions to Lower the Mash pH
But what if you want to brew a much paler beer, like a Pilsener or a
Helles? Then you will need to add more calcium to balance the
alkalinity that your malt selection cannot.

1. Go back to
the nomograph and pick a point on the RA scale that is within the
desired color range. In this example, I picked an RA value of -50.

2. Draw a line
from this RA value back through your Alkalinity value (from the water
report), and determine your new EH value.
3. From the original Mg value from the report, draw a line through
the new EH value and determine the new Ca value needed to produce
this effective hardness.
4. Subtract the original Ca value from the new Ca value to determine
how much calcium (per gallon) needs to be added. In this example, 145
ppm/gal. of additional calcium is needed.
5. The source for the calcium can be either calcium chloride or
calcium sulfate (gypsum). See the following section for guidelines on
just how much of these salts to add.

Determining
Bicarbonate Addition to Raise the Mash pH
Likewise, you can determine how much additional alkalinity (HCO_{3})
would be needed to brew a dark stout if you have water with low alkalinity.

1. You
determine your initial RA and base-malt-mash pH from your water
report, and then determine your desired RA for the style you want to
brew. In this example, I have selected an RA of 180 (base-malt-mash
pH 6), which corresponds to a dark beer on the color guideline.
2. The difference is that this time you draw a line from the desired
RA to the original EH, passing through a new Alkalinity.
3. Subtract the original alkalinity from the new alkalinity to
determine the additional bicarbonate needed. The additional
bicarbonate can be added by either using sodium bicarbonate (baking
soda) or calcium carbonate. Using calcium carbonate additions would
also affect the EH, causing you to re-evaluate the whole system,
while using baking soda would also contribute high levels of sodium,
which can contribute harsh flavors at high levels. You will probably
want to add some of each to achieve the right bicarbonate level
without adding too much sodium or calcium.

Note: The full size nomograph now
contains an approximate numeric correlation to beer color (SRM
scale). This is intended to better help you target a residual
alkalinity level based on the color of the beer style, but it is an approximation. There is a lot of variation in the
malt-acidity to malt-color relationship. [Oct.'06]

Figure 81: Full size nomograph for approximating your mash pH from
your local water report. Click to bring up the full size pdf file.

New and Improved Residual Alkalinity Spreadsheets! (Feb. 2011)

Click
Here to download an Excel spreadsheet that makes the same calculations (US units, Version 3.0).

Click
Here to download an Excel spreadsheet that makes the calculations in metric. (SI units, Version 3.0).

Note: This version corrects the amount of potential contributed alkalinity as CaCO3, assuming that all salts dissolve in the wort. Unfortunately, in the real world this does not always happen. But this version gives you a benchmark for best case scenario. Chalk is not very soluble, even in the mash at a pH of 5-6.