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Thermodynamics
Thermodynamics
Theory that is concerned with energetic and macroscopic, bulk properties of matter Deals especially well with large amount of matter and properties of matter under changes in temperature and pressure Link between thermodynamics and molecular process = statistical mechanics
Basic concepts
System part of universe with which experimentalist is concerned Open system both matter and heat exchange with surroundings Closed system only heat exchanges with surroundings Isolated or adiabatic system neither matter nor heat exchange with surroundings State functions properties relating to changes in a system which are dependent only on its initial and final states e.g. internal energy, enthalpy, entropy and Gibbs free energy
Enthalpy
Heat content of a system H = U + pV = U + nRT As most biochemical reactions occur in solution, volume change is negligible H = U
Standard states
For a substance = form of substance at a specified temperature that is stable at 1 atm of pressure For a solute = solution of concentration 1M G! = H ! TS !
Thermodynamical activity of solute in solution at a concentration of 1M at 25oC and 1 atm of pressure is assigned 1.0 Standard state of H+ in solution is originally defined as 1M solution but as the pH = 0 incompatible with most forms of life define biological standard state for solutes in which all components except H+ are at a concentration of 1M, while H+ is present at 10-7M (pH = 7) G!" = H !" TS !"
= !" + ! (vanHoff isochore at constant volume) 0 Assume H and S0 independent of temperature, plot ln K against 1/T
!" !!
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