Page 179 - Thermodynamics of Biochemical Reactions
P. 179

Thernwdyanamics of Biochemical Reactions. Robert A. Alberty
                                                                               Copyright 0 2003 John Wiley & Sons, Inc.
                                                                                              ISBN 0-471-22851-6






































                         ,i+ 11.1  Introduction to Semigrand  Partition Functions
                         5 11.2  Transformed  Gibbs Energy for a System
                                   Containing a Weak Acid and Its Basic form at a
                                   Specified pH
                         W  11.3  Semigrand Partition Function for a System
                                   Containing Two Pseudoimsomer  Groups at a
                                   Specified pH
                          2;  11.4  Semigrand Partition Function for a Biochemical
                                   Reaction  System at Specified Concentrations
                                   of Coenzymes
                         +  11.5  Discussion





                        The introduction of  transformed  thermodynamic  properties to biochemical ther-
                        modynamics owes a lot to statistical mechanics because these calculations follow
                        the pattern of  calculations on reaction equilibria in systems of  gaseous hydrocar-
                        bons at specified partial  pressures  of  molecular  hydrogen, ethylene, or acetylene.
                        Alberty  and  Oppenheim  (1989) used  a semigrand  partition  function  to describe
                        the  equilibrium  distribution  of  alkyl  benzenes  at  elevated  temperatures  as  a
                        function of  the partial  pressure  of  ethylene. The transformed  Gibbs energy  G‘ of
                        a system at a specified pH can be calculated  using a semigrand partition  function
                        (Alberty,  2001~). The  further  transformed  Gibbs  energy  G”  of  a  system  of
                        biochemical reactions can be calculated using a semigrand partition  function with
                         the  steady  state  concentrations  of  coenzymes  as  intensive  variables  (Alberty,
                         2001g, 2002a).
                            Statistical mechanics provides  a bridge between  the properties  of  atoms and
                         molecules (microscopic view) and the thermodynmamic  properties of bulk matter
                         (macroscopic  view).  For  example,  the  thermodynamic  properties  of  ideal  gases
                         can  be  calculated  from  the  atomic  masses  and  vibrational  frequencies,  bond
                         distances,  and  the  like,  of  molecules.  This  is,  in  general,  not  possible  for
                         biochemical  species in  aqueous solution  because  these  systems  are very  compli-
                         cated  from a  molecular  point  of  view. Nevertheless,  statistical  mechanmics  does
                         consider  thermodynamic  systems from  a very  broad point  of  view, that  is, from
                         the  point  of  view  of  partition  functions.  A  partition  function  contains  all  the
                         thermodynamic  information  on a  system. There is  a  different partition function
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