Solubility Equilibria Chemistry Guide

Chapter 18:
Solubility and
Simultaneous Equilibria
Chemistry: The Molecular Nature
of Matter, 6E
Jespersen/Brady/Hyslop
Jespersen/Brady/HyslopChemistry:TheMolecularNature ofMatter,6E
Solubility of Salts
Precipitation reactions (C !"
Exchange reactions in which one product is water
insoluble compound
CaCl
2
(l ! "a
2
C#
$
(aq CaC#
$
(s ! 2 "aCl (aq
#nsoluble compoun$
Compound ha%ing water solubility o& less than '(')
mole o& dissol%ed material per liter o& solution
S * '(') +
2
Solubility of Salts
Ch ! Solubility %ules
,uidelines &or what is insoluble
-oesn.t mean compound won.t dissol%e at all
Just not %ery much
No& &ant to
/uantitate solubilities
Explore conditions under which some compounds
precipitate and others don.t
0pplications in separation o& ions
Especially toxic metal ions such as Hg
2!
1 2l
$!
1 3
$!
1 etc(
$
'hy Stu$y Solubility(
2ooth decay
0cids &rom &oods dissol%e enamel1 4Ca
5
(6#
7
$
#H8 9
hydroxyapatite
:educed by &luoride which replaces #H
;
to &orm
&luorapatite 9 4Ca
5
(6#
7
$
<8 and Ca<
=ower solubility means it doesn.t dissol%e as readily
in acid
3pper and =ower ,>
?@ray o& upper and lower gastrointestinal tract
Clari&ied by barium sul&ateA%ery insoluble
BaS#
7
toxic1 but sa&e1 as it doesn.t dissol%e
7
Solubility E)uilibria
Solids in equilibrium with ions in solution
Bhen ionic salt dissol%es in water
0ssume dissociates into separate hydrated ions
>nitially1 no ions in solution
Ca*
+
(s" Ca
+,
(a)" , + *
-
(a)"
0s dissolution occurs1 ions build up and collide
Ca
+,
(a)" , + *
-
(a)" Ca*
+
(s"
0t Equilibrium
Ca*
+
(s" Ca
+,
(a)" , + *
-
(a)"
"ow ha%e saturated solution
5
Solubility an$ Solubility Pro$uct
Solubility
0mount o& salt that dissol%es in gi%en amount o&
sol%ent to gi%e saturated solution
Concentration
>n&inite number o& %alues
Solubility pro$uct
6roduct o& molar concentrations o& ions in saturated
solution raised to appropriate powers
Equilibrium constant
#nly one %alue &or gi%en solid at gi%en temperature
Temperature $epen$ence
Solubilities and thus C
sp
change with 2
D
Solubility of Salts
Consider 0gCl in water
#nly a %ery small amount dissol%es
Equilibrium exists when solution is saturated
./Cl(s" ./
,
(a)" , Cl
-
(a)"
Equilibrium lawE
0
sp
1 2./
,
32Cl
-
3
0
sp
1 solubility pro$uct constant
Solubility equilibrium
:e&lects solubility o& compound
6roduct o& ion concentrations
F
Solubility an$ Solubility Pro$uct
Solubility
0mount o& salt that dissol%es in gi%en amount o&
sol%ent to gi%e saturated solution
Solubility pro$uct
6roduct o& molar concentrations o& ions in
saturated solution raised to appropriate powers
Temperature $epen$ence
Solubilites and thus C
sp
change with temperature
Table 1841
Solubility product constants at 25 GC
+ore in 2able C(D (0ppendix p( 075
H
#on Pro$uct 5s4 Solubility Pro$uct
<orE .
6
7
y
(s" 6 .
y,
(a)" , y 7
6-
(a)"
#on Pro$uct 8
sp
1 2.
y,
3
6
27
6-
3
y
=iIe solubility product1 except initial concentrations
are used
0ny dilution o& salt that results in an unsaturated
solution
Jaries with concentration
Solubility Pro$uct 0
sp
1 2.
y,
3
6
27
6-
3
y
>on product %alue &or saturated solution becomes
constant
3ses equilibrium concentration
K
'ritin/ 0
sp
E)uilibrium 9a&s
<orE .
6
7
y
(s" 6.
y,
(a)" , y 7
6-
(a)"
0
sp
1 2.
y,
3
6
27
6-
3
y
E64
BaS#
7
(s Ba
2!
(aq ! S#
7
2;
(aq C
sp
9 4Ba
2!
84S#
7
2;
8
Ca<
2
(s Ca
2!
(aq ! 2<
;
(aq C
sp
9 4Ca
2!
84<
;
8
2
0g
2
Cr#
7
(s 20g
!
(aq ! Cr#
7
2;
(aq C
sp
9 40g
!
8
2
4Cr#
7
2;
8
0uCl
$
(s 0u
$!
(aq ! $Cl
;
(aq C
sp
9 40u
$!
84Cl
;
8
$
)'
Calculation usin/ 0
sp
an$ Molar
Solubilities
Molar solubility
+oles o& salt dissol%ed in one liter o& saturated
solution
0ssume what little dissol%ed1 dissociates )''L
0ssumes there is some solid
/uantity is not important
Solid is not included in mass action expression
.4 :i5en Solubilites, Calculate 0
sp
74 :i5en 0
sp
, Calculate Solubility
))
.4 :i5en Solubilites , Calculate 0
sp
E6 14 0t 25 GC1 the solubility o& 0gCl is )($7 x
)'
;5
+( Calculate the solubility product &or 0gCl(
./Cl (s" ./
,
(a)" , Cl
-
(a)"
0
sp
1 2./
,
32Cl
-
3
C
sp
9 ()($7 x )'
;5
()($7 x )'
;5
C
sp
9148; 6 1;
-1;
./Cl (s" ./
,
(a)" , Cl
-
(a)"
> '('' '( ''
C
E
14<= 6 1;
-!
M 14<= 6 1;
-!
M
14<= 6 1;
-!
M 14<= 6 1;
-!
M
)2
>our Turn?
2he solubility o& a salt1 0
2
B
$
1 is &ound to be
$(')'
;5
+4 Bhat is the %alue o& C
sp
M
0( 2(D x )'
@2)
B( 5(7 x )'
@K
C( 2(7 x )'
@2$
-( )(F x )'
@2)
0
2
B
$
20
$!
! $B
2@
408 9 2($(' x )'
@5
4B8 9 $($(' x )'
@5
C 9 408
2
4B8
$
9 (D(' x )'
@5
2
(K(' x )'
@5
$
C 9 2(D x )'
@2)
)$
74 :i5en 0
sp
, Calculate Solubility
E64 + Bhat is the molar solubility o& Cu> in
waterM Bhat are the equilibrium
concentrations o& Cu
!
and >
;
M
Step 14 'rite balance$ e)uation for
$issociation of salt
Cu# (s" Cu
,
(a)" , #
-
(a)"
Step +4 'rite e)uilibrium la&
0
sp
1 2Cu
,
32#
-
3
Step <4 0
sp
for salt
0
sp
1 84; 1;
-8
)7
E64 + Molar Solubilities from 0
sp
Step =4 Concentration Table
Step !4 Plu/ into an$ sol5e 0
sp
e6pression
C
sp
9 H(' )'
;H
9 (x(x
x
2
9 H(' )'
;H
6 9 +48 1;
-=
M 9 calculated molar solubility
o& Cu> 1 2Cu
,
3 1 2#
-
3
Conc (+ Cu# (s" Cu
,
(a)" , #
-
(a)"
>nitial '('' '( ''
Change
Equil.m
+x +x
x x
x
)5
Molar Solubility an$ 0
sp
Problems
Strategy &or sol%ingE
)( Brite balanced equation &or dissociation o& salt
2( Brite equilibrium law
$( C
sp
&or salt (&rom table
7( Concentration table
5a( Sol%e &or x 9 solubility
#r
5b( ,i%en solubilities1 calculate C
sp
)D
sp
E64 < Calculate C
sp
&or Bi
2
S
$
gi%en solubility is
)(' x )'
;)5
+ at 25 GC(
Step 14 'rite balance$ e)uation for
$issociation of salt
7i
+
S
<
(s" + 7i
<,
(a)" , < S
+-
(a)"
Step +4 'rite e)uilibrium la&
0
sp
1 27i
<,
3
+
2S
+-
3
<
Step <4 @se Concentration Table to
$etermine concentrations of each ion
)F
sp
7i
+
S
<
(s" + 7i
+,
(a)" < S
+-
(a)"
> ("o entries '('' '(''
C in this
E column
+3(1.0 10
5
)
+2(1.0 10
15
)
3.0 10
15
2.0 10
15
K
sp
= (2.0 x 10
15
)
2
(3.0 x 10
15
)
3
K
sp
= (4.0 x 10
30
)(27 x 10
45
)
K
sp
= 1.1 x 10
73
Step =4 Sol5e for 0
sp
)H
74 :i5en 0
sp
, Calculate Solubilities
E64 = Calculate the solubility o& Ca<
2
in water
at 25 GC1 i& C
sp
9 7(' x )'
;))
(
Ca*
+
(s" Ca
+,
(a)" , +*
-
(a)"
Step 1: 'rite E)uilibrium 9a&
0
sp
1 2Ca
+,
32*
-
3
+
Step +: Concentration Table
Conc (+ Ca*
+
(s" Ca
+,
(a)" +*
-
(a)"
>nitial ("o entries '('' '(''
Change in this
Equil.m column
,+6 ,6
+6 6
)K
E64 = Molar Solubilities from 0
sp
Step <4 Plu/ into an$ sol5e 0
sp
e6pression
0
sp
1 2Ca
+,
32*
-
3
+
9 (x (2x
2
7(' )'
;))
9 7x
$
=
1; ; 4 =
6
11
<

= == =
<
11
1; ; 4 1

= == = 6
X = 2.15 10
4
M = molar solubility of Ca
2
!Ca
2+
" = X = 2.15 10
4
M
!
" = 2x = 2(2.15 10
4
M) = 4.3 10
4
M
2'
>our Turn?
,i%en C
sp
9 )(7 x )'
;F
&or Cu(>#
$
2
1 calculate
the solubility o& this salt(
0( 5(2 x )'
@$
B( $($ x )'
@$
C( 2(D x )'
@7
-( $(F x )'
@7
Cu(>#
$
2
(s Cu
2!
! 2>#
$
@
C
sp
9 )(7 x )'
@F
9 s (2s
2
s 9 $($ x )'
2)
>our Turn?
Bhat is the molar solubility o& 0g
$
6#
7
in waterM Bhat
is the molar concentration o& each ion in solutionM
C
sp
9 H(K )'
;)F
0( 5(7 x )'
@K
40g
!
8 9 5(7 x )'
@K
46#
7
$@
8 9 5(7 x )'
@K
B( 7($ x )'
@5
40g
!
8 9 )($ x )'
@7
46#
7
$@
8 9 7($ x )'
@5
C( 5(7 x )'
@K
40g
!
8 9 )(D x )'
@H
46#
7
$@
8 9 5(7 x )'
@K
-( K(F x )'
@F
40g
!
8 9 2(F x )'
@7
46#
7
$@
8 9 K(F x )'
@F
0g
$
6#
7
(s $0g
!
! 6#
7
$@
C
sp
9 H(K x )'
@)F
9 40g846#8 9 ($s
$
(s
s 9 7($ x )'
40g
!
8 9 $s 9 )($ x )'
@7
+
46#
7
$@
8 9 s 9 7($ x )'
@5
+
22
>our Turn?
Bhat is the solubility o& 6bCl
2
in grams per )''(' m=
at 25
o
M C
sp
9 )(F x )'
@5
(
0( '(5D g
B( '(F2 g
C( '(75 g
-( '($K g
6bCl
2
(s 6b
2!
! 2Cl
@
C
sp
9 )(F x )'
@5
9 46b
2!
84Cl
@
8
2
9 s (2s
2
s 9 )(D2 x )'
@5
+
()(D2 x )'
@5
mol/= x (2FH()) g/mol x '() = 9 '(75 g
in )'' m=
2$
%elati5e Solubilities
C
sp
gi%es in&ormation about solubility o& salts
+ust be care&ul when comparing relati%e
solubilities
2wo possible cases when comparingE
)( +ust compare salts that contain the same number
o& ions
0g>(s C
sp
9 )(5 x )'
;)D
Cu>(s C
sp
9 5(' x )'
;)2
CaS#
7
(s C
sp
9 D() x )'
;5
Each salt dissol%es to produce 2 ions
Salt cation ! anion
C
sp
9 4cation84anion8
27
)( +ust compare salts that contain the same number
o& ions
>& solubility 9 x
2hen 4cation8 9 4anion8 9 x
C
sp
9 x
2
So can compare solubilities by comparing C
sp
.s
CaS#
7
* Cu> * 0g>
most soluble least soluble
largest C
sp
smallest C
sp
solubility C x
sp
= =
25
2( Compare salts with di&&erent number o& ions
Each produces di&&erent number o& ions
Each uses di&&erent C
sp
expression
"o way to predict relati%e solubility based on C
sp
Bi
2
S
$
* 0g
2
S * CuS
+ost soluble least soluble
2D
Salt 0
sp
Aions CalcB$
Solubility (M"
CuS H(5 x )'
;75
2 K(2 x )'
;2$
0g
2
S )(D x )'
;7K
$ $(7 x )'
;)F
Bi
2
S
$
)() x )'
;F$
5 )(' x )'
;)5
Common #on Effect
3p until now all calculations in pure water
Bhat happens i& > add another salt to a solution
containing one o& the ions in our insoluble saltM
Consider Pb#
+
(s" Pb
+,
(a)" , +#
-
(a)"
Saturated solution o& 6b>
2
in water
<ilter
0dd C>
6b>
2
(yellow solid precipitates out
'hy(
=e Chatelier.s 6riniciple
0dd product >
;
Equilibrium mo%es to le&t and solid 6b>
2
&orms
2F
Common #on Effect
Common ion
>on in solution that is supplied by more than one
solute
Common #on Effect
=owering o& solubility o& ionic compound by
addition o& common ion
2H
E64 ! Common #on Effect
0( Bhat is the molar solubility o& 0g
2
Cr#
7
in
'()'+ 0g"#
$
solutionM C
sp
9 K(' )'
;)2
(
B( Bhat is the molar solubility o&
0g
2
Cr#
7
in pure waterM
C( Bhat is the molar solubility o&
0g
2
Cr#
7
in '()'' + "a
2
Cr#
7
M
0g
2
Cr#
7
(s 20g
!
(aq ! Cr#
7
2;
(aq
C
sp
9 40g
!
8
2
4Cr#
7
2;
8 9 K(' )'
;)2
2K
.4 +olar solubility o& 0g
2
Cr#
7
in '()'+ 0g"#
$
solutionM C
sp
9 K(' )'
;)2
C
sp
9 K(' )'
;)2
9 ('()'+
2
4x8
x 9 Solubility o& 0g
2
Cr#
7
9 K(' )'
;)'
+
40g
!
8 9 '()' +
4Cr#
7
2;
8 9 K(' )'
;)'
+
')' ( ' (
)' ' ( K
x
)2
=
./
+
CrC
=
(s" +./
,
(a)" , CrC
=
+-
(a)"
> ("o entries '()' + '(''
C in this
E column
+x +2x
x #0.10
$'
74 Solubility o& 0g
2
Cr#
7
in pure water
./
+
CrC
=
(s" +./
,
(a)" , CrC
=
+-
(a)"
> ("o entries '('' + '('' +
C in this
E column
+x +2x
x 2x
K
sp
= [Ag
+
]
2
[CrO
4
2
] = (2x)
2
(x) = 9.0 10
12
= 4x
3
$
)2
$
)2
)' 25 ( 2
7
)' ' ( K
x

=
? 9 Solubility o& 0g
2
Cr#
7
9 )($) )'
;7
+
4Cr#
7
2;
8 9 x 9 )($) )'
;7
+
40g
!
8 9 2x 9 2(D2 )'
;7
+
$)
C4 Solubility o& 0g
2
Cr#
7
in '()'' + "a
2
Cr#
7
M
./
+
CrC
=
(s" +./
,
(a)" , CrC
=
+-
(a)"
> ("o entries '('' + '()' +
C in this
E column
+x +2x
2x #0.10
K
sp
= (2x)
2
(0.10) = 9.0 10
12
= 4x
2
(0.10)
))
)2
)' 25 ( 2
7 ( '
)' ' ( K
x

=
2
Cr#
7
9 7(F )'
;D
+
4Cr#
7
2;
8 9 x 9 7(F )'
;D
+
40g
!
8 9 2x 9 K(5 )'
;D
+
$2
$$
C4 Solubility o& 0g
2
Cr#
7
in '()'' + "a
2
Cr#
7
M
./
+
CrC
=
(s" +./
,
(a)" , CrC
=
+-
(a)"
> ("o entries '('' + '()' +
C in this
E column +6 D;41;
C
sp
9 (2x
2
('()' 9 K(' )'
;)2
9 7x
2
('()'
))
)2
)' 25 ( 2
7 ( '
)' ' ( K
x

=
2
Cr#
7
9 7(F )'
;D
+
4Cr#
7
2;
8 9 x 9 7(F )'
;D
+
40g
!
8 9 2x 9 K(5 )'
;D
+
+x +2x
>our Turn?
Bhat e&&ect would adding copper(>> nitrate
ha%e on the solubility o& CuSM
0( 2he solubility would increase
B( 2he solubility would decrease
C( 2he solubility would not change
$7
>our Turn?
2he molar solubility o& 6b<
2
in '()' + 6b("#
$
solution
is $() )'
;D
+( Bhat is C
sp
&or 6b<
2
M
0( )(2 x )'
@D
B( $() x )'
@F
C( K(D x )'
@)$
-( $(H x )'
@)2
6b<
2
(s 6b
2!
! 2<
@
46b
2!
8 9 '()' + 4<
@
8 9 2($() x )'
@D
+
C 9 46b
2!
84<
@
8
2
9 ('()(D(2 x )'
@D
2
C 9 $(H x )'
@)2
$5
Pre$ictin/ if Precipitate &ill *orm
>n maIing a solution containing %arious ions1
will the salt precipitate at the gi%en
concentrationsM
<or precipitate o& salt to &orm1 solution must be
supersaturated(
Same as asIing i& gi%en mixture o& reactants
and products is an equilibrium mixture
Can Nudge by calculating ion product1 8
Comparing with solubility product1 0
sp
$D
>n maIing a solution containing %arious ions1
will the salt precipitate at the gi%en
concentrationsM
<or precipitate o& salt to &orm1 solution must be
supersaturated(
Same as asIing i& gi%en mixture o& reactants
and products is an equilibrium mixture
Can Nudge by calculating ion product1 8
Comparing with solubility product1 0
sp
$F
$H
<orE .
6
7
y
(s" 6 .
y,
(a)" , y 7
6-
(a)"
#on Pro$uct 8
sp
1 2.
y,
3
6
27
6-
3
y
Solubility Pro$uct 0
sp
1 2.
y,
3
6
27
6-
3
y
6recipitate
&ill &orm (until
satis&y C
sp
8
sp
* 0
sp
supersaturated
No precipitate
will &orm
8
sp
9 0
sp
8
sp
O 0
sp
saturated
unsaturated
Pre$ictin/ Precipitation
E64 6 -oes a precipitate o& 6b>
2
(C
sp
9)(7 x )'
H

&orm i& )''(' m= o& '('5'' + 6b("#
$
2
are mixed
with 2''('m= o& '( )'' + "a>M
Pb#
+
(s" Pb
+,
(a)" , +#
-
(a)"
C
sp
9 46b
2!
84>
;
8
2
9 )(7 )'
;H
Strate/y for sol5in/
)( Calculate concentrations in solution to be prepared
2( Calculate 8
sp
9 46b
2!
84>
;
8
2
$( Compare 8
sp
to 0
sp
$K
E64 6 Pre$ictin/ Precipitation
Step 14 Calculate concentrations
Here diluting )'' m= to $''m=
J
total
9 )''(' m= ! 2''(' m= 9 $''(' m=
46b
2!
8
o
9 )(DF )'
;2
+
4>
;
8 9 D(DF )'
;2
+
m=
m= mmol m=
' ( $''
/ )'' ( ' ( ' ( 2'' (
solution o& m=
> o& mmol
8 > 4 = =

m=
m= mmol m=
' ( $''
/ '5'' ( ' ( ' ( )'' (
solution o& m=
6b o& mmol
8 6b 4
2
2
= =
+
+
7'
Step +4 Calculate 8
sp
8
sp
9 46b
2!
84>
;
8
2
9 ()(DF)'
;2
+(D(DF)'
;2
+
2
8
sp
9F(7$ )'
;5
Step <4 Compare 8
sp
an$ 0
sp
8
sp
9 F(7$ )'
;5
0
sp
9 )(7 x )'
H
8
sp
E 0
sp
so precipitation &ill occur
How much precipitate will &orm and what will ion
concentrations be at the endM
C
sp
small
So most ions precipitate out as 6b>
2
:eaction essentially goes to completion
7)
>& reaction goes essentially to completion1 what
will &inal equilibrium concentrations beM
)( -o stoichiometric calculations &or precipitate
&ormation
2( 2hen do equilibrium calculations to determine ion
concentrations in solution(
Step 14 Stoichiometric Calculation
Pb
+,
(a)" , +#
-
(a)" Pb#
+
(s"
Be&ore
rxn
()''m=('('5''+
9 5('' mmol
(2''m=('()''+
9 2'('' mmol
"o e&&ect on C
sp
0&ter
:xn
!4;; - !4;; 1
;4;; mmol
+;4;; - +(!4;;"
1 1; mmol
72
Step +4 System at equilibrium
Some small amount o& 6b>
2
redissol%es to &orm
equilibrium 46b
2!
8
Basically a common ion problem
Pb#
+
(s" Pb
+,
(a)" , +#
-
(a)"
>nitial conc.ns '('' )'('mmol/$''m=
9 $($$ x )'
;2
+
Equilibrium
conc.ns
$($$ x )'
;2
+ ! 2x
P $($$ x )'
;2
+
!x
C
sp
9 )(7 )'
;H
9 46b
2!
84>
-
8
2
9 (x($($$ x )'
;2
2
8 6b 4 )' $ ( )
)' $$ ( $ (
)' 7 ( )
x
2 5
2 2
H
+
= =
= +
7$
$($$ x )'
;2
+ ** 2x1 so approximation %alid
<inal equilibrium concentrations o& 6b
2!
and
>
;
in )''(' m= o& '('5'' + 6b("#
$
2
mixed
with 2''('m= o& '( )'' + "a>
2#
-
3 1 <4<< 6 1;
-+
M
2Pb
+,
3 1 14< 6 1;
-!
M
77
E64 F Pre$ictin/ Precipitation
Suppose you mix )''(' m= o& '(2'' + BaCl
2
with 5'(' m= o& '('$'' + "a
2
S#
7
( Bill
BaS#
7
(C
sp
9 )() )'
;)'
precipitateM
7aSC
=
(s" 7a
+,
(a)" , SC
=
+-
(a)"
C
sp
9 4Ba
2!
84S#
7
2;
8
Step 14 Calculate concentrations
4Ba
2!
8 9 '()$$ +
m=
m=
mol
mol
+
' ( )5'
' ( )''
BaCl )
Ba )
BaCl 2'' ( ' 8 Ba 4
2
2
2
2
=
+
+
75
E64 F Pre$ictin/ Precipitation
4S#
7
2;
8 9 '(')'' +
Step +4 Calculate 8
sp
8
sp
9 4Ba
2!
84S#
7
2;
8 9 ('()$$('(')''
8
sp
9 )($$ )'
;$
Step <4 Compare 8
sp
an$ 0
sp
C
sp
9 )() )'
;)'
)($$ )'
;$
** )() )'
;)'
/
sp
** C
sp
So BaS#
7
will precipitate
m=
m=
mol
mol
+
' ( )5'
' ( 5'
(S# "a )
S# )
(S# "a '$'' ( ' 8 S# 4
7 2
2
7
7 2
2
7
=

7D
p an$ Solubility
M/(C"
+
(s" M/
+,
(a)" , +C
-
(a)"
#H
;
shi&t equilibrium to le&t
0dd H
!
shi&t equilibrium to right
=e Chatelier.s 6rinciple
./
<
PC
=
(s" <./
,
(a)" , PC
=
<-
(a)"
0dd H
!
solubility

,
(a)" , PC
=
<-
(a)" PC
=
+-
(a)"
./Cl(s" ./
,
(a)" , Cl
-
(a)"
0dd H
!
@ has no e&&ect on solubility BhyM
Cl
;
is %ery1 %ery weaI base1 so neutral anion
So adding H
!
doesn.t e&&ect Cl
;
concentration
7F
>our Turn?
Bhat is the molar solubility o& 6b>
2
in pure
waterM C
sp
9 K(H x )'
@K
0( 2() x )'
@$
B( )(F x )'
@$
C( 7(K x )'
@5
-( )(7 x )'
@$
6b>
2
(s 6b
2!
! 2>
@
C 9 K() x )' 9 46b
2!
84>
@
8 9 s (2s
2
s 9 )(7 x )'
@$
+
7H
>our Turn?
2
in '(2'+
"a> solutionM C
sp
9 F(K )'
;K
0( $(K x )'
@)'
B( 2(7 x )'
@F
C( D() x )'
@K
-( 2(7 x )'
@F
6b>
2
(s 6b
2!
! 2>
@
4>
@
8 9 '(2'+
C 9 F(K x )'
@K
9 46b
2!
84>
@
8
2
9 46b
2!
8('(2'
2
46b
2!
8 9 2(7 x )'
@F
+
+olar solubility 9 46b
2!
8 9 2(7 x )'
@F
+
7K
>our Turn?
2
in '(2'+
6b("#
$
solutionM C
sp
9 F(K )'
;K
0( 7(K x )'
@H
B( $(F x )'
@$
C( )() x )'
@7
-( 2(2 x )'
@7
6b>
2
(s 6b
2!
! 2>
@
4>
@
8 9 '(2'+
C 9 F(K x )'
@K
9 46b
2!
84>
@
8
2
9 ('(2' 4>
@
8
2
4>
@
8 9 2(2 x )'
@7
+
+olar solubility 9 )/2 4>
@
8 9 )() x )'
@7
+
5'
>our Turn?
<rom the pre%ious two Qour 2urn problems1
what can you conclude about the relati%e
e&&ect o& added 6b
2!
%s( added >
;
M
0( 0dding 6b
2!
increases the solubility o& 6b>
2
more than >
@
(
B( 0dding >
@
decreases the solubility o& 6b>
2
more than 6b
2!
(
C( 0dding 6b
2!
decreases the solubility o&
6b>
2
more than >
@
(
-( 2hey both ha%e the same e&&ect on the
solubility o& 6b>
2
(
5)
Solubility and Simultaneous
Equilibria
6art 2
Metal C6i$es @n$er/o %eaction
&ith 'ater
5$
3sually ignore reaction o& ionic solid with water
>& the anion o& a salt is %ery basic1 a subsequent
reaction o& the anion with water occurs
Such is the case o& many metal oxides
0
b
&or #
2;
9 ) R)'
22
So 0g
2
# actually dissociates to &orm 0g
!
and #H
;
0
sp
%alue listed taIes this subsequent reaction into account
0g
2
#(s 20g
!
(aq ! #
2;
(aq 0
sp
#
2;
(aq ! H
2
# 2#H
;
(aq 0
b
0g
2
#(s ! H
2
# 20g
!
(aq ! 2#H
;
(aq 0
net
Metal Sulfi$es .lso @n$er/o %eaction
'ith 'ater
57
Sul&ide ion (S
2;
is also %ery basic
-oesn.t exist in aqueous solution
+etal sul&ides also undergo a subsequent
reaction with water
0g
2
S(s 20g
!
(aq ! S
2;
(aq 0
sp
S
2;
(aq ! H
2
# #H
;
(aq ! HS
;
(aq 0
b
0g
2
S(s ! H
2
# 20g
!
(aq ! #H
;
(aq ! HS
;
(aq 0
net
.ctual 0
sp
940g
!
8
2
4#H
;
84HS
;
8
H
!
reacts with #
2;
to produce H
2
#
:eleases metal ion &rom solid
:ecall that oxide ion is too power&ul a base to exist in
aqueous solution
E64 <e
2
#
$
(s ! DH
!
(aq 2<e
$!
(aq ! $H
2
#
o& $o &aterGinsoluble metal o6i$es form(
3sually in basic solution
Elimination o& water is o&ten in%ol%ed
+etal ion must be capable o& reacting with #H
;
to extract
oxide ion and lea%e water or H
!
E6: 20g
!
(aq ! 2#H
;
(aq 0g
2
#(s ! H
2
#
2<e
$!
(aq ! $#H
;
(aq <e
2
#
$
(s ! $H
!
(aq
Most 'aterG#nsoluble Metal C6i$es
Hissol5e in .ci$
55
Sul&ur is below oxygen in ,roup J>0
0s a result1 metal sul&ides are similar to
metal oxides
S
2;
(liIe #
2;
is too strong o& a base to exist in
water
Sul&ides dissol%e by reacting with water
E64 "a
2
S(s ! H
2
# 2"a
!
(aq ! HS
;
(aq ! #H
;
(aq
*ormation of #nsoluble Metal Sulfi$es
5D
7asic Salts .re More Soluble #n
.ci$s
5F
Subsequent reactions assist the solubility o& solids
>& anion o& salt is basic1 it will react in acidic
solution to dissol%e more &ully
"et reaction o& such dissolutions is called C
spa
SnS(s Sn
2!
(aq ! S
2;
(aq 0
sp
S
2;
(aq ! H
!
(aq HS
;
(aq 1I0
a+
HS
;
(aq ! H
!
(aq H
2
S (g 1I0
a1
SnS(s ! 2H
!
(aq Sn
2!
(aq ! H
2
S(aq 0
spa
0
spa
(acidic an$ 0
sp
(basic are listed in 2able )H(2
9earnin/ ChecJ
5H
Bhat is the molar solubility o& BaC#
$
in $(' +
HClM
C
sp
BaC#
$
9 5(' x )'
TK
H
2
C#
$
E C
a)
9 7($ x )'
TF
C
a2
9 7(F x )'
T))
7aCC
<
(s" , +
,
(a)" 7a
+,
(a)" ,
+
CC
<
(a)"
K 114! M
%eaction of Metal ions &ith S
-
+etal sul&ides can &orm
Some metal ions are so reacti%e that they react
with H
2
S directly
2hese acti%e ions include Cu
2!
1 6b
2!
1 and "i
2!
0 typical reaction isE
Cu
2!
(aq ! H
2
S(aq CuS(s ! 2H
!
(aq
=arge %alue o& C indicates that
Equilibrium lies &ar to right
#nly &orward reaction important
Sul&ides require closer in%estigation
5K

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