152 IONIC EQUILIBRIA EN ANALYTICAL CHEMISTRY

above in a solution containing a total silver concentration of

0.01 M using the following stepwise formation constants:

log 1^ =3.32 and log k2 = 3.89.

As a result of log kx being less than log 1^, it can be

seen from Fig. IX-2 that there is no ligand concentration at

which the intermediate complex, Ag(NH3)+, predominates. Furth-

er, it can be seen that cross-points A and B correspond to pNH3

values equal to log k1 and log k2 respectively and that point C at

which [ Ag+] = [ Ag(NH3 )2 ] is at a pNH3 equal to the average of

Log lq and Log k2 .

The diagram also clearly shows that it is in a rather

narrow range of free ammonia concentration (from approximately

10"3M to 10"4.5 M) that it is necessary to consider more than one

species of stoichiometric significance. If the equilibrium ammonia

concentration is greater than 10"3M, this species is Ag(NH3)2h

whereas in solutions containing less than 10"4-5 M ammonia, it

is Ag+.

In the region where the Ag(NH3 )2 is the only one of

stoichiometric significance, it can be readily shown that the

slope of the variation of log [ Ag(NH3)+], and log [ Ag+] with

log [NH3] is -1 and -2 respectively. Similarly in the region

where [Ag+] predominates, the corresponding slopes for Ag(NH3)+

and Ag(NH3)2+ are +1 and +2 respectively.

Having considered two real cases in which stepwise

formation constants increase (a rare occurrence), or decrease,

let us now examine a hypothetical case in which the two stepwise

constants are identical. As shown in Fig. IX-3 the intermediate

complex never predominates but rises to a maximum 0 value

equal to 1/3 at point A, at the same time the other two species

do. Point A, it will be noticed, has a pL concentration (where L

is the ligand) equal to log 1^ .

From Figs. IX-1 and IX-2 we may conclude that the

curve for ML in Fig. EX-3 would reach a maximum at a point

above point A if log kx > log k2, and would have reached its maxi-

mum below point A if log kx < log k2. In either of these two situ-

ations, the intersections of the ML+ curve with those of M++ and

ML2 correspond to pL = log lq and log k2 respectively.

Up to this point we have considered cases of mono-

dentate ligands. However as far as the calculations are concerned,

precisely the same methods may be used for calculating /3 values

and obtaining graphs for metal chelate systems such as the

copper-ethylenediamine system shown in Fig. IX-4.

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