Skip to main content
4 of 12
added 271 characters in body
Poutnik
  • 44.7k
  • 3
  • 54
  • 111

(in progress...)
One thing should catch you eyes immediately. The first way creates $\ce{4 H+}$ for $\ce{1 [Cd(NH3)4]^2+}$, your way creates $\ce{1 H+}$ for $\ce{1 [Cd(NH3)4]^2+}$. And there can be formulated three other versions with $\ce{0 H+}$, $\ce{2 H+}$ and $\ce{3 H+}$ $\ce{H+}$ for $\ce{1 [Cd(NH3)4]^2+}$.

It is obvious maximally one of five versions can be true. And, in fact, not even one.

All five possible equilibrium constants $K_\text{eq} = K_\text{f} \cdot K_\text{a}^N$, $N=0..4$ for

$$\ce{Cd^2+(aq) + $(4-N)$ NH3(aq) + $N$ NH4+(aq) <=> [Cd(NH3)4]^2+(aq) + $N$ H+(aq)}$$

are formally correct and equilibrium concentrations will honor them in contexts of concentration = activity simplification.

BUT: The equilibrium equations do not say there is formed $\ce{$N$ H+}$ ions for each $\ce{[Cd(NH3)4]^2+}$ ion. It would have been true if concentration of $\ce{NH3}$ had been constant during the complex formation.


Let perform this formal substitution for easier expression manipulation:
$\ce{h = [\ce{H+}]}$, $\ce{n1 = [\ce{NH4+}]}$, $\ce{n2 = [\ce{NH3}]}$, $\ce{c1 = [\ce{Cd^2+}]}$, $\ce{c2 = [\ce{[Cd(NH3)4]^2+}]}$

and we can now formulate visually compact equations for equilibrii,

$$K_\text{a} = \frac{h \cdot n_2}{n_1}$$

$$K_\text{f} = \frac{c_2}{c_1 \cdot n_2^4}$$

for mass balances:

$$n_1 +n_2 + 4 c_2 = c_\text{N,tot}$$

$$c_1 + c_2 = c_\text{Cd,tot}$$

and for charge balance:

$$h + n_1 + 2 c_1 + 2 c_2 = c_\text{chrg}$$

$\ce{OH-}$ is neglected and furthermore due unknown temperature we do not know $K_\text{w}$.


$$K_\text{a} = \frac{h \cdot n_2}{n_1}$$

$$K_\text{f} = \frac{c_2}{c_1 \cdot n_2^4}$$

for mass balances:

$$n_1 +n_2 + 4 c_2 = c_\text{N,tot}$$

$$c_1 + c_2 = c_\text{Cd,tot}$$

and for charge balance:

$$h + n_1 + 2 c_1 + 2 c_2 = c_\text{chrg}$$

Poutnik
  • 44.7k
  • 3
  • 54
  • 111