Page 58 - Instant notes
P. 58

B3
                            THERMOCHEMISTRY



        Key Notes
                                The standard state for a material is defined as being the pure
                                substance at 1 atmosphere pressure, and at a specified
                                temperature. The temperature does not form part of the definition
                                of the standard state, but for historical reasons data are generally
                                quoted for 298 K (25°C). For solutions, the definition of the
                                standard state of a substance is an activity of 1. The standard
                                enthalpy change for a process is denoted as   with the
                                subscript denoting the temperature.
                                The definition of the biological standard state is identical to the
                                standard state, with the exception of the standard state of
                                                                       −7
                                hydrogen ion activity, which is defined as equal to 10  or pH=7.
                                Biological standard conditions are denoted by a superscript   ,
                                for example   . Thermodynamic values for a reaction under
                                standard biochemical conditions only differ from that of the
                                conventional standard state when a proton is lost or gained in that
                                reaction.
                                For the purposes of concise discussion, the enthalpy changes
                                associated with a number of common generic processes are given
                                specific names, although in thermodynamic terms, these
                                processes are treated identically.

                                Hess’s law of constant heat summation is primarily a restatement
                                of the first law of thermodynamics. It may be summarized as
                                ‘The overall enthalpy change for a reaction is equal to the sum of
                                the enthalpy changes for the individual steps in the reaction
                                measured at the same temperature’ Hess’s law is particularly
                                useful in calculating enthalpy changes which cannot be easily
                                measured.
                                Tabulated values of the enthalpy of formation of materials may
                                be used to calculate the enthalpy change associated with a
                                reaction using the following, derived from Hess’s law:
                                      ∆H reaction =Σ∆H f  (products)−Σ∆H f  (reactants)
                                The enthalpy of combustion of reactant and product materials
                                may be used to calculate the enthalpy change associated with a
                                reaction in a similar manner to that of the enthalpy of formation:
                                        ∆H reaction =Σ∆H c  (reactants)−Σ∆H c  (products)
                                The ease with which ∆H c  values may be obtained is offset by the
                                more limited scope of the expression.
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