Physics, Chemistry and Biology of WATER The Tenth Annual Water Conference Bulgaria, October 1-4. 2015 Carlos U. Häubi Segura, PhD [email protected] Homeopathy Memory of water Messages from water Bulk water vs. structured water vs. EZ Energy from light? Chronic dehydration And what about …pH? “Discovery is seeing what everybody else has seen, and thinking what nobody else has thought.” Albert Szent-Györgi Canadian physiologist http://www.acidbase.org/ University of Manitoba (1943) . MSc in physics and mathematics (1949) PhD in biophysics (1951) Emory University , Physiology (1954) Brown University , Medical science (1965-1983) Stewart, P.A. (1981). How to Understand Acid-Base. A Quantitative Acid-Base Primer for Biology and Medicine, Elsevier Nordholland, New York http://issuu.com/acidbase/docs/htuab Stewart, P.A. (1983). Modern quantitative acid-base chemistry. Can J Physiol Pharmacol. 61: 1444-1461 Kellum, John A; Elbers, Paul WG, eds. (2009). Stewart's Textbook of Acid-Base. ISBN 978-1-4092-5470-6 If the data does not fit the theory, it is time to change the theory What is an acid diet? What is an alkaline diet? What makes it acid? What makes it alkaline? What are biological limits? Blood? What is biologicaly apt pH? Cells? Acids taste sour Bases taste bitter acids change blue litmus to red feel slippery or soapy their aqueous (water) solutions bases turn red (acidified) litmus conduct electricity back to blue react with bases to form salts their aqueous (water) solutions and water as the only products conduct electricity evolve hydrogen gas (H2) upon react with acids to form salts reaction with an active metal, and water as the only products such as alkali metals, alkaline An alkali is a substance which earth metals, zinc, iron, forms OH- ions as the only aluminum, forming a salt as the negative ion in aqueous only other product solution. An acid is a substance which A base is an insoluble forms H+ ions as the only hydroxide. positive ion in aqueous solution Author A theory of Hydrogen A theory of Oxygen PARACELSUS Discovers Hydrogen upon (S.XV) acting on a metal ROBERT BOYLE (Pointy corpuscules?) (1671) ANTOINE LAVOISIER Oxy = acid (1777) All acids contain “O” HUMPHREY DAVY Not all acids contain “O” (1800) Hydracids (HCl, HF, HI) “H” = Principle of acidification J.P. DULONG Union of an electronegative (1820) compound (Oxygen, halogen) with an electropositivo compound (H) and this can be substituted by a metal J.J. BERZELIUS Oxides of metaloides (1830) produce acids in water Oxygen = Sauerstoff (German for “acid substance”) JUSTUS VON LIEBIG An acid contains a H-atom (1838) which can be subtituted by a metal GRAHAM Monobasic and polibasic (1880) acids: H is subsituted by a base Arrhenius (1887) ◦ An acid is a substance which forms H+ ions as the only positive ion in aqueous solution. HCl ---> H+ + Cl- ◦ An alkali is a substance which forms OH- ions as the only negative ion in aqueous solution. A base is an insoluble hydroxide Brønsted-Lowry (1923) HCl(g) + NH3(g) ---> NH4Cl(s) ◦ An acid is a proton donor. 2HCl + MgO ---> MgCl2 + H2O A base is a proton acceptor. Lewis (1923) ◦ An acid is an electron acceptor, and a base is an electron donor. ◦ This totally removes the concept of hydrogen ions being a pre-requisite for an acid. But like the Brønsted-Lowry definiton above, it still includes every acid and base under the Arrhenius definition, and all those under the Brønsted-Lowry definition. + 2- Zn(OH)2 + 2NaOH(aq) ---> 2Na (aq) + [Zn(OH)4] (aq) Water is an acid or a base? Bicarbonate is a base or an acid? - Where does HCO3 come from? From NaHCO3 Where does the OH- come from? From NaOH H2CO3 is an acid or a conjugated acid? Classical theories of acids Old theories are ◦ Theory of dissociation, Arrhenius-Ostwaldt (1887) ◦ pH scale (pH = -log [H+]), Sørenson (1909) still actual? ◦ Henderson-Hasselbalch equation (1916) ◦ Proton donors, Brønsted-Lowry (1923) ◦ Electron donars, Lewis acids (1923) General definitions of solvents Any new theories? ◦ Effects of solutes on the solvent (Germann, 1925) ◦ Quantitative theory of acids (Stewart,1981) Concepts of acids in Medicine Iatrogenic? ◦ Dissociation of strong acids and bases ◦ Partial pressure of CO2 (PCO2) ◦ Buffers Qualitative or ◦ Henderson-Hasselbalch – only one variable Quantitative? -- -- O H + Water is really weird... 104.5° H + It forms a permanent dipole d+ - ◦ H d d+ - + O H d d d- O H H + - d+ - ◦ It hydrates other molecules, even other O d H d H H d H + - O O d H d + - + - molecules of water H d H d H d H d d+ - O + H d H d d- O + - O H H d H d H ◦ It forms liquid crystals with moving electric O O H d+ - + - O H d H d H d H charges O O H H It dissociates with difficulty (Kd) but re- H H + associates rapidly (K ) : H3O O a Protonic H ◦ It is the main donador and receptor of hydrogen H jumps O ions (= protons: H+) and hydroxile ions (OH-) H + H ◦ Protons (H ) cannot live freely; they associate O + and hydrate : H3O (H2O)n H H + O H O ◦ Water has a high concentration of H2O: 55.5 M 3 H One molecule in each 10 million dissociates spontaneously: ◦ 0.1 ppm , 1/107 , 10-7 (pH=7) How is this possible? The reaction is the following: + - + + H2O H + OH H + H2O H3O The proton binds to another molecule of water H + - O + O - H + H + + + H3O H H - + H + + O H O -H H + + O - O -H OH- H + H + Theory of dissociation, Arrhenius-Ostwaldt (1887) General definitions of solvents The neutral charge El protón no tiene vida libre, se forma el ion H + + O - in water is always hidrogenion H3O + H C C maintained H + - + O + O - H H Matriz de agua: H + Donador y receptor ÁcidoÁcido no disociado:-disociado: H2O de protones NoCarga tiene (carga-) = anión H O+ 3 y iones OH- H + H + - - O - Saltos protónicos O H + O + + + H H + Dónde quedó la bolita? H - H + O H + O - O - H Ac H H+ + H + H + H + H + - - O O H + Cristal de agua tiene carga H + Acido orgánico se protoliza: neutra se forma un anión solvatado Por cada carga negativa se genera un protón H+ According to Germann (1925) + ◦ Cation of water (H3O ): “Lyonium” ◦ Anion of water (OH-): “Lyate” For a given solvent: ◦ Acid: a substance that increments the concentration of the “Lyonium” ion and reduces the concentration of the “Lyate” ion ◦ Base: a substance that increases the concentration of the “Lyate” ion and decreases the concentration of “Lyonium” ion. In the case of water, acids and bases can be defined as : ◦ Acid: A negative charge that produces a mayor dissociation of water and an increase in the concentration of protons, [H+] ◦ Base: A positive charge that produces a mayor dissociation of water molecules and an increase in the concentration of hydroxile ions, [OH-] Three factors that affect pH but could not be reconciled... now braught together by a quantitative method Cationes P CO2 Na+ fuertes SID= Variables dependientes Strong ? pH [A-] ? PCO2= Ion - + HCO + 2+ [HA] 3 - HA Ca Difference [H ] OH H3O Presiуn [OH-] Parcial de - ? + Henderson-Hasselbalch A = [HCO ] K CO TOT 3 pH = pKa + Log [A-]/[HA] ? 2 2- - Total de A [CO3 ] ? 2- 2- Mg2+ aniones CO SO4 3 dйbiles Aniones Aniones dйbiles Seis ecuaciones fuertes Cl- ? simultбneas Dissociation of strong acids and bases SID – Strong Ion Difference Partial pressure of CO2 – PCO2 Partial pressure of CO2 – PCO2 Dissociation of weak acids ATOT – Total of weak anions Strong Ion Difference: Protein concentration Atot] Na + K + Ca +Mg pCO : 2 Phosphates, ammonia, etc. -Cl – strong ions = SID Weak acids: VFA Lactate Chemistry laws: - Mass action: - Electro-neutrality: - Dissociation of: water, carbonic acid, weak acids, weak bases, ammonia, etc. + - - 2- - [H ] [OH ] [HCO3 ] [CO3 ] [A ] [Pi] [VFAs] [Lactates] Stewarts theory is based on the effect of three basic principles of chemistry, on the balance of electrical charges in aqueous solutions: 1) Principle of electro-neutrality, 2) Law of Mass Action, 3) Law of Mass Conservation 1) Principle of electro-neutrality the sum of all positive charged ions must equal the sum of all the negatively charged ions: [Na+] + [K+] + [Ca2+] + [Mg2+] + [H+] - [Cl-] – - - - 2- [Anion ]-[OH ] - [HCO3 ] - [CO3 ] = 0 160 OH- 140 Pi 120 Atot 100 HCO3- 80 Otros Aniones mmol/L 60 Cl- 40 H+ Ca2+ 20 K+ 0 Na+ Cationes Aniones 2) Law of Mass Action States that all incompletely dissociated substances reach a dissociation equilibrium: [A] * [B] = K * [C] where K is the rate constant for the reaction. Water has a very small dissociation constant: -14 KW (KW = 1*10 ) but a very large association constant: 14 (1/KW = 1*10 ) 3) Law of Mass Conservation States that the amount of a substance remains constant unless it is added, removed, generated or destroyed: - [HA] + [A ] = [ATOT] The total of a weak acid (ATOT) is an independent variable and can be present as a dissociated acid (A-) or non-dissociated (HA), both being dependent variables. The dissociation of water into H+ ions (pH) and OH- and the behavior of other weak acids (organic acids, carbonates, phosphates and proteins) and bases (ammonia), depends on three independent variables: 1) The Strong Ion Difference (SID) + + 2+ 2+ - 2- Na + K + Ca + Mg - Cl - SO4 2) The partial pressure of carbon dioxide (PCO2) + - + 2- CO2 + H2O H2CO3 H + HCO3 2 H + CO3 3) The total amount of weak anions (ATOT) - HAlb + Alb = AlbTOT Water is the primary and inexhaustible source and sink for hydrogen ions.