problems in brewing What is the “free calcium ratio” and what is its relative importance to beer? How are in- adequacies treated? "The “tree calcium ratio,” ale so expressed as “free Ca as CaSO, oxalate as CaC0,," is a convenient way of expressing the position of the equilibrium bee tween calcium and oxalate existing in a given beet. The ratio is use ful in predicting beer stability and gushing tendencies. ‘The natural combination of eal- cium and oxalic acid and their con- mash vessel and carry on during boiling, wort cooling and fermenta- tion. A change in materials, brewing water, of method of water treatment can be responsible for an increase in calcium oxalate crystals. If insuffi- cient calcium is present in the wort to combine with all the available oxalic acid, the danger of subsequent turbidity is created. A “crystal hhaze” may be caused by the for- mation of deposited crystals and, in such an instance, the formation of calcium oxalate has assumed objec tionable proportions. Analytically, beer oxalate con tents are expressed in terms of calcium oxalate rather than as the oxalate ion, because some samples may contain oxalate precipitates at the time of examination. Also, the total calcium content of beer is ex- pressed as calcium sulfate rather than as the calcium ion, because this salt is the chief constituent of har- dening compounds. Furthermore, relatively litte of the calcium pre sent in a well stabilized beer can be attributed to the calcium bicarbo- nate present in the brewing water or in the calcium contained in normal malt. In predicting beer stability, the free calcium ratio is used. Extensive research has shown that free cal- ‘cium ratios of less than 0.25 and oxalate contents as CaCO, within a range of 50 ppm produce quite stable beers, provided that con- tamination by extraneous calcium ion is prevented. ‘Beers that have free calcium ra- tios of 0.25 to 5 and oxalate con- tents as CaCO, greater than 20 ppm are usually found to be colloi- dally unstable. Copious sediments of ‘oxalate and other matter, usually of proteinaceous nature, are gen- erally observed. Beers with free calcium ratios of 5 to 13 coupled with oxalate (as CaC;0,) of 15 to 20 ppm, and cal- cium ratios greater than 13, with oxalate (as CaCO) less than 15 ppm, are usually very stable. Such beers have highly favorable free calcium ratios and they are un- likely to develop an oxalate insta- Dility, even if small amounts of ex- traneous calcium ions accidentally ‘happen to contaminate them during cellar operations. To summarize, the relative levels shown in Table 1 will prove useful. In order to estimate a beer’s sta- Dility, it is necessary first to ascer- tain the oxalate content and the free calcium ratio of the beer in ques- Oxalate can be eliminated by hardening the water at different points in the brewing process. The common practice is to do so right at the start, either by mixing cor- rective salts with the brewing water beforehand or by adding them di- rectly to the main mash, the cooker mash, and to the mash during sparging. JE hardening treatment is applied in the kettle or at a latter stage, the beneficial action which the correc- tive compounds exert during the mashing process is lost. This loss ‘CaCs0s (opm) ee than 0:25 test thon 30 Feil table More than 023, |_—More than 20 Unnabie Ser leas thon 5 a ms 3 More than 5, toss than 20, Stable bot more than 15 4 Vary sable ‘August 1973—The BREWERS DIGEST 67 can be minimized by adjusting the pH of the brewing water with min- eral acid. ‘Addition of the hardening com- pound in the cellar is least desirable because of the difficulty in dissolving the material in the beer without thorough agitation. ‘The hardening salts used should be of a good soluble grade. Harden ing material of poor solubility is of little practical value. Can you inform me as to 1% Chea dabytnces exert acto ing and inhibitory effects on pro- teolytic enzyme (papain func- tion)? Papain is sensitive to a great ‘many reagents. In general, it is acti- vated by reducing agents and inhib- ited by oxidizing agents, the two ac- tions usually being reversible. Some common activators are hy- drogen sulfide, bisulfite, hydrosul- fite, cysteine, and urea. Examples of inhibitors are atmospheric oxygen, iodine, bromine, hydrogen peroxide, heavy metal ions (¢.¢., Fe, Cu, Ni), fresh _cuprous oxide, and methyl bromide. In addition to these reagents, many natural products are reported to contain gs yet unidentified acti- vators and/or inhibitors. Papai self is believed to contain materials that affect its protease components. Moreover, some agents alternate in their role as activator and inhibi- tor depending on their concentra- tion. Ascorbic acid is a reducing agent which is readily converted into dehydroascorbie acid which ‘acts as an oxidizing agent. This ac- counts for the fact that it is vari- ously reported as exerting both an activating and an inhibitory effect. To further complicate this matter, many agents affect papain in one way when it is reduced (thiol state) and in another when it is oxidized (disulfide state). How is malt vinegar pro- duced? What materials are used? Malt forms the basic material in the production of malt vinegar. The procedure involved is quite similar to beer production through the mill- ing and mashing processes. How- ever, the sweet wort is not boiled but is fermented with yeast and the resultant unhopped beer is acctified by acetic acid bacteria,