The Solubility Product Constant Ksp

Salts differ in their solubilities. In general, compounds of alkali metals are soluble in water.
Many ionic compounds however, are insoluble. (See solubility chart)
Most insoluble salts will dissolve to some e!tent in water. "hese salts are said to be
slightly soluble in water. #or e!ample, when the insoluble salt $g%l is mi!ed with water, a
very small amount of it dissolves.
$g%l(s) $g
&
(a') & %l
(
(a')
)ecause $g%l is a solid it is left out of the e'uilibrium e!pression*
+sp , -$g
&
.-%l
(
.
+sp is e'ual to the product of the concentration terms each raised to the power of the coefficients
of the substance in the dissociation e'uation.
+sp for $g%l at /0
1
% is 2.3 ! 21
(21
(from solubility table)
4!ample 52*
6hat is the concentration of silver chloride ions in a saturated silver chloride solution at /0
1
%7
+sp , 2.3 ! 21
(21
$g%l(s) $g
&
(a') & %l
(
(a')
+sp , -$g
&
.-%l
(
. , 2.3 ! 21
(21
Since -$g
&
. , -%l
(
.
-$g
&
.
/
, 2.3 ! 21
(21
-$g
&
. , 2.8 ! 21
(0
"he e'uilibrium constant Ksp called the solubility constant indicates how soluble
a substance is.
2) If the +sp is low, the solid is not very soluble.
/) If the +sp is high, the solid is soluble.
The Common Ion Effect
6hat would happen if silver nitrate was added to the above solution7
Immediately after the addition, the product of the -$g
&
.-%l
(
. would be greater than the +sp value
(this is because the $g9:8 will dissociate and add more $g
&
). ;e%hatelier<s principle applies
here, the stress of the additional $g
&
could be relieved by shifting the reaction to the left. "his
would create additional $g%l solid (precipitate). "his process would continue until the product
of the -$g
&
. ! -%l
(
. once again was e'ual to 2.3 ! 21
(21
.
In this e!ample, the silver ion is called a common ion, because it is found in both salts. $dding
silver nitrate to a saturated solution of silver chloride causes the solubility of $g%l to decrease.
"he lowering of the solubility of a substance by the addition of a common ion is called the
common ion effect.
Predicting Precipitate Formation
6hen the product of the concentration of the ions e!ceeds the value of +sp, they cannot e!ist
in e'uilibrium anymore. "hey will form a precipitate in order to reduce the concentrations of the
ions in solution back to the e'uilibrium value.
+sp can be used to predict whether a precipitate will form when two solutions are mi!ed
together.
2) If the ion product concentration, =, is greater than the +sp value, a precipitate will form.
(= > +sp supersaturated solution)
/) If it e'uals the +sp, no precipitate forms. ( = , +sp saturated solution)
8) If it is less, no precipitate forms. (= ? +sp unsaturated solution)
4!ample 5/*
@oes a ppt. of $g%l form when 2 m; of 1.2 molA; $g9:8 is added to a beaker containing 2; of
tap water with a %l
(
ion concentration of 2.1 ! 21
(0
molA;7
-%l
(
. , 2.1 ! 21
(0
molA;
-$g
&
. calculation* Start with the given info, 2 m; of 1.2 molA;
Set up a ratio that states, if there are 1.2 moles of $g
&
in 2111 m;, how many moles will be
in 2 m;7
1.2 mol , !B
2111m; 2 m;
! , 1.1112 moles of $g
&
are present. ("his is how many moles there are, this is not the
concentration)
"he -$g
&
. will be this many moles of $g
&
dissolved in the volume of solution in this
'uestion. "herefore*
-$g
&
. , 1.1112 mole , 1.1112 mole , 2.1 ! 21
(C
molA;
2111 m; & 2 m; 2.112 ;
= , -$g
&
.-%l
(
.
, (2.1 ! 21
(C
)(2.1 ! 21
(0
)
, 2.1 ! 21
(D
"he +sp for $g%l is 2.3 ! 21
(21
therefore = > +sp so a ppt. will form.
4!ample 58*
01 m; of 1.1121 M 9a%l is mi!ed with 01 m; of 1.111/1 M $g9:8. 6ill a
precipitate form7 "he +sp of $g%l is 2.3 ! 21
(21
.
If a precipitate forms, it will either be $g%l or 9a9:8.
"he +sp of $g%l(s) is lower. ($ll nitrates are soluble).
#ind the concentrations of $g
&
and %l
(
after the / solutions are mi!ed.
original 5 moles of $g
&
, % ! E , 1.111/1M ! 1.101 ; , 2.1 ! 21
(0
moles
-$g
&
. , molesAtotal volume
-$g
&
. ,2.1 ! 21
(0
molesA1.211 ; , 2.1 ! 21
(C
M
original 5 moles of %l
(
, % ! E , 1.1121M ! 1.101 ; , 1.11110 mol , 0.1 ! 21
(0
moles
-%l
(
. , molesA total volume , 0.1 ! 21
(0
molesA1.211 ; , 0.1 ! 21
(C
M
= , -$g
&
. -%l
(
. , (2.1 ! 21
(C
) (0.1 ! 21
(C
) , 0.1 ! 21
(F
"his product is greater than the +sp value (0.1 ! 21
(F
> 2.3 ! 21
(21
). $ precipitate will form.
S"4GS ": #:;;:6*
2. @etermine which ions will form what compound
/. %alculate the number of moles of each ion (n , % ! E)
8. @etermine the total volume of the solutions after mi!ing
C. %alculate the concentration of each ion (% , n A E)
0. Substitute the concentrations of the ions into the +sp e!pression to solve for =
3. %ompare = and +
Hiven the initial concentration, we can predict which way a reaction will go
%omparing = and + does this*
= > +sp $ precipitate forms and a supersaturated solution e!ists, reaction goes to left
"he ions will precipitate until their individual concentrations multiplied together
e'ual the value of +sp.
= , +sp $ saturated solution e!ists, e'uilibrium is established
"he solution cannot hold more dissolved ions without a precipitate forming.
= ? +sp 9o precipitate forms and an unsaturated solution e!ists, reaction goes to right
"here are not enough ions dissolved to form a precipitate.
Answers to Practice Problems:
p. I8F
+sp , -Gb
/&
.-%r:C
/(
. , (2.8D ! 21
(I
)(2.8D ! 21
(I
) , 2.D ! 21
(2C
p. IC/
If there is a precipitate, it would be %a(:J)/.
-%a
/&
. , 1.2M ! 2; , 1.2 molA2.11/ ; , 1.1DDFM
-:J
(
. , 1./M ! 1.11/; , C ! 21
(C
molA2.11/ ; , 8.DD ! 21
(C
M
%a(:J)/ (s) %a
/&
(a') & /:J
(
(a') +sp , F.1 ! 21
(3
= , -%a
/&
.-:J
(
.
/
= , (1.1DDF)(/ ! 8.DD ! 21
(C
)
/
, 3.C ! 21
(F
3.C ! 21
(F
? F.1 ! 21
(3
(= ? +sp, therefore a precipitate will not form)