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30        Basics



             Acids and bases
                                                              B. pH values in the organism
                                                              pH values in the cell and in the extracellular
             A. Acids and bases
                                                              fluid are kept constant within narrow limits.
             In general, acids are defined as substances      In the blood, the pH value normally ranges
             that can donate hydrogen ions (protons),         only between 7.35 and 7.45 (see p. 288). This
             while bases are compounds that accept pro-       corresponds to a maximum change in the H    +
             tons.                                            concentration of ca. 30%. The pH value of
                Water enhances the acidic or basic proper-    cytoplasm is slightly lower than that of blood,
             ties of dissolved substances, as water itself    at 7.0–7.3. In lysosomes (see p. 234; pH
                                                                            +
             can act as either an acid or a base. For exam-   4.5–5.5), the H concentration is several hun-
             ple, when hydrogen chloride (HCl) is in aque-    dred times higher than in the cytoplasm. In
             ous solution, it donates protons to the solvent  the lumen of the gastrointestinal tract, which
             (1). This results in the formation of chloride   forms part of the outside world relative to the
                     –
             ions (Cl ) and protonated water molecules        organism, and in the body’s excretion prod-
             (hydronium ions, H 3 O+, usually simply re-      ucts, the pH values are more variable. Ex-
                             +
             ferred to as H ). The proton exchange be-        treme values are found in the stomach (ca.
             tween HCl and water is virtually quantitative:   2) and in the small bowel (> 8). Since the
             in water, HCl behaves as a very strong acid      kidney can excrete either acids or bases, de-
             with a negative pK a value(seep.18).             pending on the state of the metabolism, the
                Bases such as ammonia (NH 3 )takeover         pH of urine has a particularly wide range of
             protons from water molecules. As a result of     variation (4.8–7.5).
                                        –
             this, hydroxyl ions (OH )and positively
                                            +
             charged ammonium ions (NH 4 , 3)form. Hy-
             dronium and hydroxyl ions, like other ions,      C. Buffers
             exist in water in hydrated rather than free      Short–term pH changes in the organism are
             form (see p. 26).                                cushioned by buffer systems.These are mix-
                Acid–base reactionsalwaysinvolve pairs of     tures of a weak acid, HB, with its conjugate
                                                                     –
             acids and the associated conjugated bases        base, B , or of a weak base with its conjugate
             (see p.18). The stronger the acid or base, the   acid. This type of system can neutralize both
             weaker the conjugate base or acid, respec-       hydronium ions and hydroxyl ions.
                                                                                                 –
             tively. For example, the very strongly acidic       In the first case (left), the base (B )binds a
                                                                                                         +
             hydrogen chloride belongs to the very weakly     large proportion of the added protons (H )
             basic chloride ion (1). The weakly acidic am-    and HB and water are formed. If hydroxyl
                                                                       –
             monium ion is conjugated with the moder-         ions (OH ) are added, they react with HB to
                                                                    –
             ately strong base ammonia (3).                   give B and water (right). In both cases, it is
                                                                                   –
                The equilibrium constant K for the acid—      primarily the [HB]/[B ] ratio that shifts, while
             base reaction between H 2 Omolecules (2)is       the pH value only changes slightly. The titra-
             very small. At 25 °C,                            tion curve (top) shows that buffer systems are
                                                              most effective at the pH values that corre-
                             –
                      +
                K= [H ] [OH ]/ [H 2 O] = 2  10 –16  mol  L –1  spond to the pK a value of the acid. This is
                                                              where the curve is at its steepest, so that the
             In pure water, the concentration [H 2 O] is      pH change, ∆pH, is at its smallest with a given
                                              –1
                                                                                        –
                                                                               +
             practically constant at 55 mol  L .Substitut-    increase ∆cin [H ]or[OH ]. In other words,
             ing this value into the equation, it gives:      the buffer capacity ∆c/ ∆pH is highest at the
                                                              pK a value.
                        +
                               –
                K w =[H ] [OH ]= 1  10   –14  mol  L –1
                                    –
                             +
             The product [H ] [OH ]—the ion product of
             water—is constant even when additional
             acid–base pairs are dissolved in the water.
                                              +
                                                       –
             At 25 °C, pure water contains H and OH at
             concentrations of 1  10 –7  mol  L –1  each; it is
             neutral and has a pH value of exactly 7.


           Koolman, Color Atlas of Biochemistry, 2nd edition © 2005 Thieme
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