FORUM ON BEER, HOMEBREWING, AND RELATED ISSUES
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Contents:
Alkalinity ("A. J. deLange")
Shoes, ships and Sankey Kegs /was: Sankey Kegs ("\\-s@roadrunner.com")
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Spencer Thomas, and Bill Pierce
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Date: Sat, 05 Feb 2011 01:10:41 -0500
From: "A. J. deLange" <ajdel at cox.net>
Subject: Alkalinity
Bill Pierce please pass to John Palmer
Addition of calcium carbonate to water is simple in that adding 264.2
mg/L CaCO3 to 1 L of water yields an alkalinity of 264.2 mg/L only if:
1. Ideally dilute chemistry is assumed and 2. The end point pH of the
titration defining alkalinity is 4.35. 3. The acid used to dissolve the
chalk is carbonic. 4. Carbonic is added until pH 7 is reached.
Including the effects of ionic strength and using the more usual pH
(in brewing applications) of 4.3 to define alkalinity 264.2 mg/L
dissolved in water with CO2 gives an alkalinity of 268.3. The difference
is small enough that one can say that 100 mg/L chalk dissolved in
imitation of the way in which natural limestone is dissolved is 100 mg/L
as CaCO3 - hence the use of that unit of concentration.
Now if one dissolved 264 mg/L CaCO3 in 1L DI water with hydrochloric
acid and brought the pH to 7 the alkalinity of that water would be 109.8
and if using sulfuric acid 110.0. But if using phosphoric acid it would
be 155.9. OTOH if the water is brought to pH 6 the alkalinity of that
water using carbonic would be 276.3, using hydrochloric 42.8 and using
phosphoric 57.4.
The numbers I gave for phosphoric are bogus. They would apply for a
solution of sodium carbonate of equivalent strength but where calcium
and phosphate are involves another effect, the extremely low solubility
of hydroxyl appatite comes into play. When phosphoric acid is added to a
suspension of calcium carbonate the the lowered pH allows CaCO3 to
dissolve releasing CO3-- and Ca++ ions into the solution. Protons from
the phosphoric acid are consumed by CO3-- + H+ --> HCO3- and the pH
rises. When the pH rises the concentration of PO4--- increases and this
immediately forms Ca10(PO4)6(OH)2 which precipitates. This results in
removal of PO4--- which causes HPO4-- to give up a proton to replace it.
This causes depletion of HPO4-- so H2PO4- gives up a proton to replace
it and so also with H3PO4. All the protons are available to convert
HCO3- to CO2 gas which escapes and to lower the pH which shifts the
various phosphate species back towards acid and these effects continue
until equilibrium is reached. All this has a dramatic effect on the
alkalinity. Note: things don't happen in order the way I've described
them but thinking of them in this way helps me to get an idea of what to
expect at equilibrium.
Malt doesn't contain H3PO4 but it does contain the acid H2PO4- and
similar things happen with malt when calcium carbonate is added to it.
The chalk is basic and so the pH rises which causes a shift in the
distribution of phosphate species towards PO4---. This coalesces with
calcium to release protons by the mechanism of the last paragraph which
limits the extent to which the pH can rise. Thus much of the calcium
carbonate added to a mash for the purpose of increasing pH is
ineffective for that purpose - and a good thing it is too! Simple
laboratory experiments with phosphate solutions of strength similar to
that reported for malt seem to indicate that large chalk additions may
be unable to carry the pH above 7 but this is a tentative result.
All this can be modeled (or at least a phosphate model is possible - I'm
working on it) but the point I want to make is that calculating the
"alkalinity" of mash is certainly not a simple thing to do given
uncertainties in actual phosphate concentration and the fact that the
phosphate and carbonate systems aren't the only 2 buffers in grist,
especially where dark malts are involved.
There is more on this in discussions with Colin and Martin at the tail
end of the Version 2.0 of Palmer's Residual Alkalinity Spreadsheets
<http://www.thebrewingnetwork.com/forum/viewtopic.php?f=2&t=8762> thread
at BN.
A.J.
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Date: Sun, 06 Feb 2011 10:35:04 -0500
From: "\\-s at roadrunner.com" <"\\-s"@roadrunner.com>
Subject: Shoes, ships and Sankey Kegs /was: Sankey Kegs
A.J.deLange writes ....
> The rig I use is pictured and described at
> http://www.pbase.com/agamid/image/109220058
OMG - I've understood for years that AJ is an advocate of "go big or go
home", but the graphic proof is stunning, and doesn't even show the
obviously missing lab and fridges and ... So I'm assuming the blue and
black boxen with plumbing are the heat source and copper ? Based on
the amount of wiring I suspect he gray box on top is a control panel.
IIRC correctly AJ wrote about using a home furnace as a heat source - is
your home furnace doing dual duty here AJ ?
So - and I'm half serious here AJ - wouldn't it make more sense, to
form a nominal business, offer services for test/development brewing,
or brewery lab services ? Even if you never made a nickel of revenue
you could buy your toys with pre-tax dollars for a few years at a cost
of filing a schedule C.
-SteveA
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End of HOMEBREW Digest #5788, 02/06/11
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