Alberty R A, Goldberg R N
Chemistry Department, Massachusetts Institute of Technology, Cambridge 02139.
Biochemistry. 1992 Nov 3;31(43):10610-5. doi: 10.1021/bi00158a025.
The criterion for chemical equilibrium at specified temperature, pressure, pH, concentration of free magnesium ion, and ionic strength is the transformed Gibbs energy, which can be calculated from the Gibbs energy. The apparent equilibrium constant (written in terms of the total concentrations of reactants like adenosine 5'-triphosphate, rather than in terms of species) yields the standard transformed Gibbs energy of reaction, and the effect of temperature on the apparent equilibrium constant at specified pressure, pH, concentration of free magnesium ion, and ionic strength yields the standard transformed enthalpy of reaction. From the apparent equilibrium constants and standard transformed enthalpies of reaction that have been measured in the adenosine 5'-triphosphate series and the dissociation constants of the weak acids and magnesium complexes involved, it is possible to calculate standard Gibbs energies of formation and standard enthalpies of formation of the species involved at zero ionic strength. This requires the convention that the standard Gibbs energy of formation and standard enthalpy of formation for adenosine in dilute aqueous solutions be set equal to zero. On the basis of this convention, standard transformed Gibbs energies of formation and standard transformed enthalpies of formation of adenosine 5'-trisphosphate, adenosine 5'-diphosphate, adenosine 5'-monophosphate, and adenosine at 298.15 K, 1 bar, pH = 7, a concentration of free magnesium ions of 10(-3) M, and an ionic strength of 0.25 M have been calculated.
在特定温度、压力、pH值、游离镁离子浓度和离子强度下,化学平衡的判据是转化吉布斯自由能,它可由吉布斯自由能计算得出。表观平衡常数(用反应物如腺苷5'-三磷酸的总浓度表示,而非用各物种表示)可得出反应的标准转化吉布斯自由能,温度对特定压力、pH值、游离镁离子浓度和离子强度下的表观平衡常数的影响可得出反应的标准转化焓。根据在腺苷5'-三磷酸系列中测得的表观平衡常数和反应的标准转化焓以及所涉及的弱酸和镁配合物的解离常数,可计算出零离子强度下所涉及物种的标准生成吉布斯自由能和标准生成焓。这需要约定在稀水溶液中腺苷的标准生成吉布斯自由能和标准生成焓等于零。基于此约定,已计算出在298.15K、1巴、pH = 7、游离镁离子浓度为10(-3)M且离子强度为0.25M时,腺苷5'-三磷酸、腺苷5'-二磷酸、腺苷5'-单磷酸和腺苷的标准转化生成吉布斯自由能和标准转化生成焓。