HOMEBREW Digest #5788 Sun 06 February 2011

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  Alkalinity ("A. J. deLange")
  Shoes, ships and Sankey Kegs /was: Sankey Kegs ("\\-s@roadrunner.com")

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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. Return to table of contents
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 Return to table of contents
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