Question 22.11: Consider a mixture of Cd(OH)2(s) and Cu(OH)2(s), for which t......

Consider a mixture of Cd(OH)_{2}(s) and Cu(OH)_{2}(s), for which the values of K_{sp} at 25°C are 7.2 × 10^{−15}\ M^{3} and 2.2× 10^{−20}\ M^{3}, respectively. Can this mixture be separated by adjusting the pH of the solution?

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Let’s begin by considering the Cd(OH)_{2}(s). The dissolution equation and corresponding K_{sp} expression for Cd(OH)_{2}(s) are

Cd(OH)_{2}(s) ⇋ Cd^{2+}(aq) + 2\ OH^−(aq)

and

K_{sp} = [Cd^{2+}][OH^−]^2 = 7.2 × 10^{−15}   M^3

The solubility of Cd(OH)_{2}(s) in water can be calculated from the K_{sp} expression:

s = [Cd^{2+}] =\frac{7.2 × 10^{–15}\ M^3}{[OH^–]^2}                (22.26)

The concentration of OH^−(aq) can be related to [H_{3}O^+] by using the ion product constant expression for water:

[OH^–] =\frac{K_{w}}{[H_{3}O^+]} =\frac{1.0 × 10^{–14}\ M^2}{[H_{3}O^+]}

Substitution of this equation into Equation 22.26 yields

s = [Cd^{2+}] =\frac{7.2 × 10^{–15}\ M^3\ [H_{3}O^+]^2}{(1.0 × 10^{–14} M^2)^2}                          (22.27)

Now let’s consider the Cu(OH)_{2}(s), for which we have

Cu(OH)_{2}(s) ⇋ Cu^{2+}(aq) + 2\ OH^−(aq)

and

K_{sp} = [Cu^{2+}][OH^−]^2 = 2.2× 10^{−20}   M^3

We can find the solubility of Cu(OH)_{2}(s) in a manner analogous to that for Cd(OH)_{2}(s) by using the K_{sp} expression for Cu(OH)_{2}(s) and ion product concentration expression of water to obtain

s = [Cu^{2+}] =\frac{2.2 × 10^{–20}\ M^3}{[OH^–]^2} =\frac{2.2 × 10^{–20}\ M^3\ [H_{3}O^+]^2}{(1.0 × 10^{-14}\ M^{2})^{2}}              (22.28)

From Equations 22.27 and 22.28, we can calculate the solubility of Cd(OH)_{2}(s) and Cu(OH)_{2}(s) at various pH values, as shown in Table 22.4 and Table 22.5. These results are plotted in Figure 22.13. From Figure 22.13 we see that Cd(OH)_{2}(s) can be separated from Cu(OH)_{2}(s) by adjusting the pH of the solution to about 6.5 using a buffer solution. At pH 6.5, the Cd^{2+}(aq) dissolves, but the Cu(OH)_{2}(s) remains in solution.

TABLE 22.4 Solubility of Cd(OH)_{2}(s) in water at 25°C at various pH values
pH [H_{3}O^+]/M [H_{3}O^+]^2/M^2 [Cd^{2+}]/M
7.00 1.0 × 10^{-7} 1.0 × 10^{-14} 0.72
7.20 6.3 × 10^{-8} 4.0 × 10^{-15} 0.29
7.40 4.0 × 10^{-8} 1.6 × 10^{-15} 0.11
7.60 2.5 × 10^{-8} 6.3 × 10^{-16} 0.045
7.80 1.6 × 10^{-8} 2.6 × 10^{-16} 0.018
8.00 1.0 × 10^{-8} 1.0 × 10^{-16} 0.0072

 

TABLE 22.5 Solubility of Cu(OH)_{2}(s) in water at 25°C at various pH values
pH [H_{3}O^+]/M [H_{3}O^+]^2/M^2 [Cu^{2+}]/M
4.20 6.3 × 10^{-5} 4.0 × 10^{-9} 0.88
4.40 4.0 × 10^{-5} 1.6 × 10^{-9} 0.35
4.60 2.5 × 10^{-5} 6.3 × 10^{-10} 0.14
5.00 1.0 × 10^{-5} 1.0 × 10^{-10} 0.022
5.20 6.3 × 10^{-6} 4.0 × 10^{-11} 0.0088
5.40 4.0 × 10^{-6} 1.6 × 10^{-11} 0.0035
figure 22.13

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