Page 228 - Thermodynamics of Biochemical Reactions
P. 228

228      Mathematica Solutions to Problems


        it involves an important issue that often arises in enzyme-catalyzed reactions, and that is the problem of water as a reactant  in
        dilute aqueous solutions.  The problem  is that the activity of  water is taken as unity by convention, and so its concentration
        does not appear in the expression for the apparent equilibrium constant.  The conservation matrix at constant pH is
                    G6P    H2 0  Glu   Pi
        A=  C       6      0     6     0
              0     9      1     6     4
              P      1     0     0     1
        Since the activity of  water is taken as unity  in dilute aqueous solutions independent of the extent of reaction, the Hz 0 column
        and the oxygen row must be deleted from the conservation matrix:
                     G6P   GIU   Pi
        A'=  C      6      6     0
              P      1     0     1

        Therefore the conservation matrix is given by


                as= ({6t 6, O},  (1, 0, I}};
        The standard transformed Gibbs energies of the reactants at 298.15 K, pH 7, and 0.25 M ionic strength are

                glucose6ghos /. gH + 7 /. is + 0.25

                -1318.92

                glucose /. gH -+  7 /. is + 0.25
                -426.708

                pi /. pH -+  7  /. is + 0.25

                -1059.49

                h20 /. gH+ 7 /. is + 0.25
                -155.658

        The standard further transformed Gibbs energies of formation in kJ  rno1-l  are

                glucose6phoSft= -1318.92 -9 (-155.66)

                82.02

                glucoseft = -426.71 - 6 (-155.66)
                507.25

                pift =  -1059.49 - 4 (-155.66)

                -436.85
        The equilibrium composition  is calculated using


                equcalcc  [as, -   {82.02,  507.25, -436.85)  I  (0.1, 0, 011
                                    8.314510.29815
                {0.0000919341, 0.0999081, 0.0999081)
   223   224   225   226   227   228   229   230   231   232   233