Solubility Equilibria Regarding AgCl(s) and Complex-Ion Formation Ag(NH_3)_2^+ Question?

Silver chloride, (K_(sp) = 1.8*10^-10), can be dissolved in solutions containing ammonia due to the formation of the soluble complex ion Ag(NH_3)_2^+ (K_f = 1.0*10^8). What is the minimum amount of NH_3 that would need to be added to dissolve 0.010mol of AgCl in 1.00L of solution?

I've added the equilibria together into a solubility equation, but can't reason how the answer is 0.095mol.

3 Answers
Dec 1, 2017

If in the end you manage to dissolve "0.010 M" of "Cl"^(-) in solution for your first equilibrium, and the two sequential reactions occurring are

"AgCl"(s) rightleftharpoons "Ag"^(+)(aq) + "Cl"^(-)(aq) " "bb((1))

K_(sp) = ["Ag"^(+)]["Cl"^(-)]

"Ag"^(+)(aq) + 2"NH"_3(aq) -> "Ag"("NH"_3)_2^(+)(aq) " "bb((2))

K_f = (["Ag"("NH"_3)_2^(+)])/(["Ag"^(+)]["NH"_3]^2),

then these add to be:

"AgCl"(s) + 2"NH"_3(aq) -> "Cl"^(-)(aq) + "Ag"("NH"_3)_2^(+)(aq)

and the net equilibrium constant beta would be the product.

beta = K_(sp)K_f = 1.8 xx 10^(-10) cdot 1.0 xx 10^8 = 1.8 xx 10^(-2)

= cancel(["Ag"^(+)])["Cl"^(-)] cdot (["Ag"("NH"_3)_2^(+)])/(cancel(["Ag"^(+)])["NH"_3]^2)

= (["Ag"("NH"_3)_2^(+)]["Cl"^(-)])/(["NH"_3]^2)

The ICE table for the net reaction could then look like:

"AgCl"(s) + 2"NH"_3(aq) -> "Cl"^(-)(aq) + "Ag"("NH"_3)_2^(+)(aq)

"I"" "-" "" "" "["NH"_3]_i" "" ""0 M"" "" "" ""0 M"
"C"" "-" "" "-2s" "" "" "+s" "" "" "+s
"E"" "-" "["NH"_3]_i - 2s" ""0.010 M"" "" "" "s

where ["NH"_3]_i is the initial concentration of ammonia added to cause "0.010 M" of "Cl"^(-) to dissolve in solution from the initially added "AgCl"(s).

Note that the "0.010 M" is after adding "NH"_3(aq), *so it is assigned to the FINAL concentration, and not the initial.*

The initial, whatever it would have been without ammonia, would have been much less than the "Cl"^(-) that does dissociate from "AgCl"(s) from addition of "NH"_3(aq).

At this point, you know s, the solubility, is "0.010 M" of "Cl"^(-), so 2s = "0.020 M" and you can then set up the mass action expression:

1.8 xx 10^(-2) = ("0.010 M")^2/(["NH"_3]_i - "0.020 M")^2

This is a perfect square, so:

0.1342 = ("0.010 M")/(["NH"_3]_i - "0.020 M")

Flipping the fraction gives:

7.454 = (["NH"_3]_i - "0.020 M")/("0.010 M")

And solving for the "NH"_3 you added gives:

color(blue)(["NH"_3]_i = "0.0946 M")

And since this was in "1.00 L" solution, you added "0.095 mols" of "NH"_3(aq) to two sig figs.

Dec 1, 2017

AgCl(s) rightleftharpoons Ag^(+) + Cl^(-) with K_(sp) = 1.8*10^-10
Ag^(+)(aq) + 2NH_3(aq) rightleftharpoons Ag(NH_3)_2^(+)(aq) with K_f = 1.0*10^8

AgCl(s) + 2NH_3(aq) rightleftharpoons Ag(NH_3)^+ + Cl^(-) where,

K_(sp) * K_f = ([Ag(NH_3)^+][Cl^-])/([NH_3]^2) approx 1.8*10^-2

1.8*10^-2 = (0.01x)/(2x)^2
0.072x^2-0.01x= 0
therefore x = 0.13

Dec 1, 2017

I get 0.095 mol/L.

Explanation:

You want to dissolve 0.01 mol of "AgCl", so you will have 0.010 mol of "Ag"("NH"_3)_2^"+" and 0.010 mol of "Cl"^"-" at equilibrium. The initial amount of "NH"_3 is unknown.

The equilibrium reactions and the ICE table will look like this:

color(white)(mmmmmm)"AgCl(s)"color(white)(mmmmmmll) ⇌ "Ag"^"+""(aq)" +color(white)(m) "Cl"^"-""(aq)"; K_text(sp)
ul(color(white)(mmmmmm)"Ag"^"+""(aq)" + "2NH"_3"(aq)" ⇌ "Ag"("NH"_3)_2^"+" + "Cl"^"-""(aq)"; K_text(f))
color(blue)(color(white)(mmmmmm)"AgCl(s)" color(white)(l)+ "2NH"_3"(aq)" ⇌ "Ag"("NH"_3)_2^"+" + "Cl"^"-""(aq)"; K_text(oa) = K_text(sp)K_text(f))

"I/mol·L"^"-1":color(white)(mmmmmmmml)xcolor(white)(mmmmmml)0color(white)(mmmmm)0
"C/mol·L"^"-1":color(white)(mmmmmmll)"-0.020"color(white)(mmmll)"+0.010"color(white)(mm)"+0.010"
"E/mol·L"^"-1":color(white)(mmmmmm)x"-0.020"color(white)(mmmml)0.010color(white)(mmm)0.010

K_text(oa) = K_text(sp)K_text(f) = 1.8 × 10^"-10" × 1.0 × 10^8 = 0.018

K_text(oa) = ([ "Ag"("NH"_3)_2^"+"]["Cl"^"-"])/ (["NH"_3]^2) = 0.010^2/(x"-0.020")^2= 0.018

0.010/(x"-0.020") = 0.134

0.010 = 0.134(x"-0.020") = 0.134x - 0.00268

x = (0.010 + 0.00268)/0.134 = 0.01268/0.134= 0.095

Check:

0.010^2/("0.095 - 0.020")^2 = 0.00010/0.075^2 = 0.00010/0.00562 = 0.018

It checks!