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There is an equilibrium constant, called the water dissociation constant, Kw, which has the form: K w = [H+ ][OH ] = 1 0 10 14 at 25o C Again, the concentration of water is a constant and is incorporated into Kw 14 + The numerical value of Kw of 10 10 is true for the product of the [H ] and [OH ] in pure water and for aqueous solutions of acids and bases + In the discussion of weak acids, we indicated that the [H ] = [A ] However, there are + + two sources of H in the system: the weak acid and water The amount of H that is due to the water dissociation is very small and can be easily ignored

The set of r equations resulting from this reduction procedure is a complete set of independent reactions for the N species considered present in the system However, more than one such set is possible, depending on how the reduction procedure is carried out, but all sets number r and are equivalent The reduction procedure also ensures the following relation:

W H AT I T TA K E S T O B E # 1

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The phase-equilibrium and chemical-reaction-equilibrium equations are the only ones considered in the foregoing treatment as interrelating the phase-rule variables However, in certain situations special constraints may be placed on the system that allow additional equations to be written over and above those considered in the development of Eq (1336) If the number of equations resulting from special constraints is s, then Eq (1336) must be modified to take account of these s additional equations The still more general form of the phase rule that results is:

(1337)

Duhem's theoremfornonreacting systems was developedin Sec 102 It states that for any closed system formed initially from given masses of particular chemical species, the equilibrium state is completely determined (extensive as well as intensive properties) by specification of any two independent variables This theorem gives the difference between the number of independent variables that completely determine the state of the system and the number of independent equations that can be written connecting these variables:

Because the concentration of the hydronium ion, H3O+, can vary tremendously in solutions of acids and bases, a scale to easily represent the acidity of a solution was developed + It is called the pH scale and is related to the [H3O ]:

KEEP THE PRESSURE ON Deep down, Lombardi understood that leaders don t truly motivate Lou Holtz, the successful Notre Dame coach who now coaches at the University of South Carolina, expressed his grasp of this simple truth when he said, Motivation is simple: You eliminate those who aren t motivated People motivate themselves Your task as a leader is to inspire your people with a motive to act, an incentive to adapt, if they haven t found one for themselves You inspire your people with the vision that they want to see brought to a successful conclusion Yet paradoxically, you also get people moving by painting a compelling picture of the consequences of not adapting to change You do this by showing what happened to companies that failed to adapt and by asking, Is this what we want to happen to us You do this by subjecting people to enough stress and pressure that they realize that they must either adapt or fail You create enough pressure to unfreeze the culture and the entrenched hierarchy enough stress to force people out of their comfort zone and the mind-set of This is the way we ve always done it here

When chemical reactions occur, a new variable ~j is introduced into the material-balance equations for each independent reaction Furthermore, a new equilibrium relation [Eq (138)] can be written for each independent reaction Therefore, when chemical-reaction equilibrium is superimposed on phase equilibrium, r new variables appear and r new equations can be written The difference between the number of variables and number of equations therefore is unchanged, and Duhem's theorem as originally stated holds for reacting systems as well as for nonreacting systems Most chemical-reaction equilibrium problems are so posed that it is Duhem's theorem that makes them determinate The usual problem is to find the composition of a system that reaches equilibrium from an initial state o f j x e d amounts of of reacting species when the two variables T and P are specified

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