2021 Kimia Dasar Pertemuan 5

KIMIA FISIKA
Pertemuan 5 : Kesetimbangan Ionik

Solubility and
Complex-ion
Equilibria
Precipitation
 Precipitation - The formation of a solid from solution. The reverse of
dissolution.
 Dissolution - The process by which a substance dissolves. The reverse
of precipitation.
 Importance - (a) Selective precipitation is an important industrial

purification process, especially when crystals are formed. (b) Scales
that form on boilers and teeth are to be prevented, as are kidney
stones. (c) Precipitation forms minerals - dissolution removes them.
Saturation
 Saturated Solution - One in which a dissolution - precipitation
equilibrium exist between a solid and its dissolved form. Here the
equilibrium is dynamic and the rate of dissolution is equal to the rate
of precipitation.
 Unsaturated Solution - One in which the concentration of dissolved
solid is not sufficient to cause precipitation.
 Obviously a quantitative description of this type of heterogeneous
equilibrium is subject to the law of mass action, and equilibrium
expressions can be written and deductions made concerning the
concentration of various species at equilibrium.
Solubility
Solubility - The greatest amount of a

substance that will dissolve in equilibrium in a
specified volume of solvent at a particular
temperature.
Example - The solubility of silver chloride in

water at 25 oC is .0018 g/L or 1.3 x 10-5 M.
Most solubilities increase with temperature.

Classification of Ionic Materials by Solubility
Soluble Ionic Materials - have solubilities in

excess of 10 gL-1.
Insoluble Ionic Materials - have solubilities
less than 0.1 gL-1.
Slightly Soluble Materials - have
solubilities between 0.1 and 10 gL-1.
The Nature of Ionic Equilibria
Most salts dissociate into ions when they

dissolve. Equilibrium then exists between the
solid salt and its aquated ions, and not between
the solid salt and dissolved molecules of the
salt. For example:
PbSO4(s) = Pb2+(aq) + SO42-(aq)
This equilibrium system may be described by
the mass-action expression:
Ksp = [Pb2+][SO42-]
Note that the pure solid does not enter into the
equilibrium.
Solubility and the Ksp
•One may provide solubility information as

the solubility, S or as the solubility product,
Ksp.
•These two quantities are obviously related

to each other.
Solubility Equilibria
 Many natural processes depend on the precipitation or dissolving of a slightly

soluble salt.
– Equilibrium constants of slightly soluble, or

nearly insoluble, ionic compounds can be
used to answer questions regarding
solubility and precipitation.
9
The Solubility Product Constant
 When an excess of a slightly soluble ionic compound is mixed with water, an

equilibrium is established between the solid and the ions in the saturated
solution.
– For the salt calcium oxalate, CaC2O4, you have the

following equilibrium.
10
 When an excess of a slightly soluble ionic compound is mixed with water, an

equilibrium is established between the solid and the ions in the saturated
solution.
– The equilibrium constant for this process is

called the solubility product constant.
11
 In general, the solubility product constant is the equilibrium constant for
the solubility equilibrium of a slightly soluble (or nearly insoluble) ionic
compound.
12
 In general, the solubility product constant is the equilibrium constant for the
solubility equilibrium of a slightly soluble (or nearly insoluble) ionic
compound.
13
compound.
14
Solubility and the Common-Ion Effect
 In this section we will look at calculating solubilities in the presence of
other ions.
15
 In this section we will look at calculating solubilities in the presence of
other ions.
– For example, suppose you wish to know the

solubility of calcium oxalate in a solution of
calcium chloride.
16
Precipitation Calculations
 Precipitation is merely another way of looking at solubility equilibrium.
– Rather than considering how much of a

substance will dissolve, we ask: Will
precipitation occur for a given starting
ion concentration?
17
Criteria for Precipitation
 To determine whether an equilibrium system will go in the forward or reverse

direction requires that we evaluate the reaction quotient, Qc.
18

– Consider the following equilibrium.

H2 O
19

– The Qc expression is
20
 To determine whether an equilibrium system will go in the forward or

reverse direction requires that we evaluate the reaction quotient, Qc.
21
Fractional Precipitation
 Fractionalprecipitation is the technique of

separating two or more ions from a solution by
adding a reactant that precipitates first one
ion, then another, and so forth.
22
Fractional Precipitation
 Fractional precipitation is the technique of

separating two or more ions from a solution
by adding a reactant that precipitates first
one ion, then another, and so forth.
23
Effect of pH on Solubility
 Sometimes it is necessary to account for other reactions aqueous ions might

undergo.
– For example, if the anion is the conjugate base of

a weak acid, it will react with H3O+.
24
– Consider the following equilibrium.
– Because the oxalate ion is conjugate to a weak

acid (HC2O4-), it will react with H3O+.
25
– According to Le Chatelier’s principle, as C2O42- ion

is removed by the reaction with H3O+, more
calcium oxalate dissolves.
26
Separation of Metal Ions by Sulfide
Precipitation
 Many metal sulfides are insoluble in water but dissolve in acidic solution.
27
Complex-Ion Equilibria
 Many metal ions, especially transition metals,

form coordinate covalent bonds with
molecules or anions having a lone pair of
electrons.
28
– For example, the silver ion, Ag+, can react

with ammonia to form the Ag(NH3)2+ ion.
29
 A complex ion is an ion formed from a metal ion with a Lewis base attached
to it by a coordinate covalent bond.
30
Complex-Ion Formation
 The aqueous silver ion forms a complex ion with ammonia in steps.
 
Ag (aq )  NH 3 (aq) Ag ( NH 3 ) (aq )
 
Ag ( NH 3 ) (aq )  NH 3 (aq) Ag ( NH 3 ) 2 (aq )
31
 The formation constant, Kf, is the equilibrium constant for the formation of a
complex ion from the aqueous metal ion and the ligands.
– The value of Kf for Ag(NH)2+ is 1.7 x 107.

32
– A large Kf value means that the complex ion is

quite stable.
33
 The dissociation constant, Kd, is the reciprocal, or inverse, value of Kf.
– The equation for the dissociation of Ag(NH3)2+ is
– The equilibrium constant equation is
34
Amphoteric Hydroxides
 An amphoteric hydroxide is a metal hydroxide that reacts with both acids

and bases.
35
 An amphoteric hydroxide is a metal hydroxide that reacts with both acids

and bases.
36
– When a strong base is slowly added to a solution

of ZnCl2, a white precipitate of Zn(OH)2 first forms.
Zn 2 (aq )  2OH  (aq )  Zn(OH ) 2 (s )
37
 Many natural processes depend on the precipitation or dissolving of a
slightly soluble salt. Insoluble does not mean 100% insoluble.
 In the next section, we look at the

equilibria of slightly soluble, or nearly
insoluble, ionic compounds.
 Their equilibrium constants can be used to
answer questions regarding solubility and
precipitation.
38
34.1 The Solubility Product Constant
 When an excess of a slightly soluble ionic compound is mixed
with water, an equilibrium is established between the solid
and the ions in the saturated solution.
 Insoluble salts will have extremely small quantities of salt

dissolve in water and a equilibrium will be established when
the salt reaches it saturation point; exchange solid to ions
in solution.
 For the salt calcium oxalate, CaC2O4, you have the
following equilibrium.
H2O 2 2
CaC 2O 4 ( s ) Ca (aq)  C 2O 4 (aq)
39
 When an excess of a slightly soluble ionic compound
is mixed with water, an equilibrium is established
between the solid and the ions in the saturated
solution and represented by a constant that is
temp dependent.
 The equilibrium constant for this process is called
the solubility product constant, Ksp.
H2O 2 2
CaC 2O 4 ( s ) Ca (aq)  C 2O 4 (aq)
2 2
K sp  [Ca ][C 2O 4 ]
Ksp basically relationship of amount of ions in solution at
saturation point; once product of concentration of ions = Ksp,
ppt occurs
40
 In general, the solubility product constant, Ksp, is
the equilibrium constant for the solubility
equilibrium of a slightly soluble (or nearly insoluble)
ionic compound. It is a constant that relates to
amount of substance that is dissolve in solution at
saturation point not amount in flask (only amount
dissolved)
 It equals the product of the equilibrium
concentrations of the ions in the compound.
Solids activity of 1.
 Each concentration is raised to a power equal to
the number of such ions in the formula of the
compound.
41
 For example, lead iodide, PbI2, is another
slightly soluble salt (insoluble salt). Its
equilibrium is:
H2 O
2 
PbI 2 ( s ) Pb (aq)  2I (aq)
 The expression for the solubility product constant is:
2  2
K sp  [Pb ][I ]
42
Calculating Ksp from the Solubility
 When 4.8 x 10-5 mol of solid dissolve it forms 4.8 x
10-5 mol of each ion.
H2 O 2
CaC 2O 4 ( s ) Ca 2  (aq)  C 2O 4 (aq)
Equilibrium 4.8 x 10-5 4.8 x 10-5
2  the equilibrium-constant expression.

2  substitute into
K sp  [Ca ][C 2O 4 ]
 You can now
K sp  ( 4.8  10  5 )(4.8  10  5 )
9
K sp  2.3  10
43
Calculating  Ksp from
By experiment, the
it is found thatSolubility
1.2 x 10 mol of lead(II) iodide, PbI ,
-3
2
dissolves in 1.0 L of water at 25°C to reach saturation pt. What is the
Ksp at this temperature?
 The following table summarizes.

H2 O 2+ -
PbI2(s) Pb (aq)+ 2I (aq)
Equilibrium 1.2 x 10-3 2 x (1.2 x 10-3)
Note: if 2:1 ratio you
double, etc.
44
 Substituting into the equilibrium-constant expression:
2  2
K sp  [Pb ][I ]
3 3 2
K sp  (1.2  10 )( 2  (1.2  10 ))
3 3 2
K sp  (1 . 2  10 )( 2 . 4  10 )
K sp  6.9  10  9
 note: conc of I is double due to 2:1 ratio. Also need to square due to
the order of this elementary rxn.
HW 40
code: glass
45
Sometimes you may want to determine the concentration of a species you
need to reach the saturation point. Let's look at example.
What is the [Ca2+] needed to form a saturated solution of Ca3(PO4)2
containing 1 x 10-5 M of phosphate ions? Ksp Ca3(PO4)2 =1 x 10-33
2 3
Ca 3 ( PO 4 ) 2 ( s ) 3Ca (aq)  2 PO 4 (aq)
? 1 x 10-5 M
note: didn't double phosphate; problem gave us total amount of phosphate; no
mol:mol etc. Must read problem.
33 3 2
K sp  1 10  [Ca ] [PO4 ]  [Ca 2 ]3[110 5 ]2
2 3
33
1  10
[Ca 2 ]3  5 2
 1 10 23
[1 10 ] yx y1/3 or ^ or x sq rt y
2 8
[Ca ]  2  10 M
46
 If the solubility product constant, Ksp, is known, the
solubility of the compound can be calculated.
 The water solubility of an ionic compound is amount

of compound that dissolves per unit volume of
saturated solution; typically g/L. If the units on the
solubility is mols/L called molar solubility.
47
Calculating the Solubility from Ksp
 The mineral fluorite is calcium fluoride, CaF2. Calculate the solubility (in
grams per liter) of calcium fluoride in water from the K sp (3.4 x 10-11)
 Let s be the molar solubility of CaF2.

H2O
2 
CaF2 ( s ) Ca (aq)  2F (aq)
Equilibrium s 2s
48
H2O 2 
CaF2 (s ) Ca (aq)  2F (aq)
Equilibrium s 2s
 You substitute into the equilibrium-constant equation
2  2
K sp  [Ca ][ F ]
 11
3 . 4  10  (s)(2s)  ( s )( 4 s )  4 s
2 2 3
 11
3 . 4  10  4s 3
49
 11
4s  3 . 4  10
3
3.4  10 -11
s 
3
4
3.4  10 -11
4
s 3  2.0  10 M = [Ca2+] = [CaF2]
4 note [F-] = 2s = 4.0 x 10-4 M
which equals the molar solubility of CaF2 but we

want solubility.
50
Calculating the Solubility from Ksp
 Convert to g/L (CaF2 78.1 g/mol).
2 .0  10 4 mol CaF2 78 .1g CaF2

solubility  
L 1 mol CaF2
2
 1 . 6  10 g CaF2 / L  0 . 016 g CaF2 / L
HW 41
code: solubility
51
34.1.1 Solubility and the Common-Ion
Effect
 In this section we will look at calculating solubilities in
the presence of other ions.
 Common ion problem similar to buffer except involves
insoluble and soluble salt.
 The importance of the Ksp becomes apparent
when you consider the solubility of one salt in the
solution of another having the same cation or
anion.
 By having a common ion, the equil will shift to the
left causing more to ppt out and decrease the
solubility of the substance. We take advantage of
this to get species to ppt out completely from a
solution.
52
Solubility and the Common-Ion Effect
For example, suppose you wish to know the
solubility of calcium fluoride in a solution of sodium
fluoride (soluble salt).
NaF (s) Na+ (aq) + F- (aq)
CaF2 (s) Ca2+ (aq) + 2 F- (aq) [CaF2 ]
 The salt contributes the fluoride to the system and

shifts the equil causing the solubility of calcium
fluoride to be less
 The effect is that calcium fluoride will be less
soluble than it would be in pure water.
53
 What is the molar solubility of calcium fluoride in 0.15 M
sodium fluoride? The Ksp for calcium fluoride is 3.4 x 10-11.
NaF (s)  Na+ (aq) + F- (aq)
0.15 M 0.15 M
CaF2 (s) Ca2+ (aq) + 2F- (aq)
[Ca2+] [F-]
Note: don’t double
Initial, [ ]o 0 0.15
Change, D[ ] +s +2s
Equilibrium, [ ]eq s 0.15 + 2s HW 42
[CaF2] in pure H2O was 2.0 x 10-4 M;

100,000 times more soluble in water
than in NaF
code: eight
54
34.2 Precipitation
 Rather than considering how much of a

ion concentration?
55
To determine whether an equilibrium system will go in the forward or

reverse direction requires that we evaluate the reaction quotient, Q
(or IP or P).
 To predict the direction of reaction, you compare Q

with Ksp.
 The reaction quotient has the same form as the
Ksp expression, but the concentrations of products
are starting values not necessarily saturated conc.
56
 Consider the following equilibrium.
H2 O
2 
PbCl 2 ( s ) Pb (aq)  2Cl (aq)
2  2
K sp  [Pb ] eq [ Cl ] eq
2  2
Q  [Pb ] i [ Cl ] i
where initial concentration is

denoted by i.
57
Criteria Iffor Precipitation
Q = K , the solution is just saturated with ions and any
sp
additional solid will not dissolve in solution but
instead will precipitate out.
solid ions Q = [ions]
 If Q < Ksp, the solution is unsaturated and more solid can be
dissolved in the solution; no precipitate forms. Shift
right increase Q
 If Q > Ksp, , the solution is supersaturated meaning the

solution contains a higher concentration of ions than
possible at equilibrium; a precipitate will form. Shift
to left decrease Q
 not really shifting but will give you where equil lies.
58
 The concentration of calcium ion in blood plasma is 0.0025 M. If the concentration of
oxalate ion is 1.0 x 10-5 M, do you expect calcium oxalate to precipitate? K sp for
calcium oxalate is 2.3 x 10 -9.
0.0025 M 1.0 x 10-52 M

CaC 2O 4 ( s ) Ca 2 (aq)  C 2O 4 (aq)
 The ion product quotient, Qc, is:
2 2
Q  [Ca ] [ C O 4 ] i
i 2
Q  (0.0025)  (1.0  10 ) -5
Q  2.5  10 -8
 This value is larger than the Ksp, so you expect

precipitation to occur past saturation point.
Q  2.5  10  K sp  2 . 3  10
-8 -9
59
• The concentration of lead ion is 0.25 M. If the concentration of chloride ion is
0.0060 M, do you expect lead chloride to precipitate? Ksp for lead chloride is 1.7
x 10-5.
PbCl2 (s) Pb2+ (aq) + 2Cl- (aq)

0.25 M 0.0060 M
Note: did not double chloride concentration
2  2
Q  [Pb ] i [ C l ] i
Q  ( 0 .25 )( 0 . 0060 ) 2
Q  9 .0 x 10 -6
Q < Ksp = 1.7 x 10-5, indicating that a no precipitate will form (below
the saturation point).
60
example: A student mixes 0.200 L of 0.0060 M Sr(NO3)2 solution with 0.100 L of
0.015 M K2CrO4 solution to give a final volume of 0.300L. Will a precipitate form under
these conditions? Ksp SrCrO4 = 3.6 x 10-5
Sr(NO3)2 (aq) + K2CrO4 (aq)  SrCrO4 (s) + 2 KNO3 (aq)
(aq)
HW 43
code: ppt
SrCrO4 (s) Sr2+ (aq) + CrO42- (aq)
0.0040 M 0.0050 M
we find that Q (2.0 x 10-5) < Ksp (3.6 x 10-5) indicating

that no precipitate will form (below saturation point)
61
34.2.1 Selective Precipitation
 Selective precipitation is the technique of separating two or more
ions from a solution by adding a reactant that precipitates first one
ion, then another, and so forth.
 For example, when you slowly add potassium

chromate, K2CrO4, to a solution containing Ba2+ and
Sr2+, barium chromate precipitates first due to its
lower solubility than SrCrO4.
62
Selective Precipitation
 After most of the Ba2+ ion has precipitated, strontium
chromate begins to precipitate.
 It is therefore possible to separate Ba2+ from Sr2+ by

selective precipitation using K2CrO4.
 Take advantage in qual/quan type analysis.
63
 Sometimes it is necessary to account for other reactions that
aqueous ions might undergo.
 For example, if the anion is the conjugate base of

a weak acid, it will react with H3O+.
 You should expect the solubility to be affected by
pH. By adding and complexing out ions you can
affect the pH of solution which could affect ppt
reactions.
64
 Consider the following equilibrium.
H2O 2 2
CaC 2O 4 ( s ) Ca (aq)  C 2O 4 (aq) s by
pH
 Because the oxalate ion is conjugate base, it will
react with H3O+ (added acid to lower pH).
2  H2 O 
C 2O 4 (aq )  H 3O (aq) HC 2O 4 (aq)  H 2O(l)
 According to Le Chatelier’s principle, as C2O42- ion is
removed by the reaction with H3O+, more calcium oxalate
dissolves (increase solubility).
 Therefore, you expect calcium oxalate to be more soluble in acidic
solution (lower pH) than in pure water. The acidity will react with
the oxalate and shift the equil toward the right and allow more
calcium oxalate to dissolve.
65
Separation of Metal Ions by Sulfide
Precipitation
Many metal sulfides are insoluble in water but dissolve in acidic

solution.
 Qualitative analysis uses this change in solubility

of the metal sulfides with pH to separate a mixture
of metal ions.
 By adjusting the pH in an aqueous solution of H2S,
you adjust the sulfide concentration to precipitate the
least soluble metal sulfide first.
 Typically do some qual experiment similar in lab.
66
Qualitative Analysis
Qualitative analysis involves the determination of the identity of

substances present in a mixture.
 In the qualitative analysis scheme for metal

ions, a cation is usually detected by the
presence of a characteristic precipitate.
 Next slide shows a figure that summarizes
how metal ions in an aqueous solution are
separated into five analytical groups.
67
Ebbing, D. D.; Gammon, S. D. General
Chemistry, 8th ed., Houghton Mifflin, New
York, NY, 2005.
68
34.3 Complex-Ion Equilibria
 Many metal ions, especially transition metals, form coordinate
covalent bonds with molecules or anions having a lone pair of
electrons.
 This type of bond formation is essentially a

Lewis acid (accepts share pair electrons)-
base (makes available share pair
electrons) reaction.
69
 For example, the silver ion, Ag+, can react with
ammonia to form the Ag(NH3)2+ ion.
 
Ag  2(: NH 3 )  ( H 3 N : Ag : NH 3 )
Ag+ (aq) + 2NH3 (aq) Ag(NH3)2+ (aq)
70
 A complex ion is an ion formed from a metal ion with a Lewis base
attached to it by a coordinate covalent bond.
Ag(NH3)2+
 A complex is defined as a compound

containing complex ions. Ag(NH3)2Cl
 A ligand is a Lewis base (makes electron

pair available) that bonds to a metal ion to
form a complex ion. Lewis Acid is the
cation. :NH3
71
 The aqueous silver ion forms a complex ion with ammonia in steps.
 
Ag (aq )  NH 3 (aq) Ag ( NH 3 ) (aq )
 
Ag ( NH 3 ) (aq )  NH 3 (aq) Ag ( NH 3 ) 2 (aq )
 When you add these equations, you get the overall
equation for the formation of Ag(NH3)2+.
 
Ag (aq )  2 NH 3 (aq) Ag ( NH 3 ) 2 (aq )
72
Complex-Ion

Formation 
Ag (aq )  2 NH 3 (aq) Ag ( NH 3 ) 2 (aq )
 The formation constant, Kf, is the equilibrium constant for the formation of a
complex ion from the aqueous metal ion and the ligands.
 The formation constant for Ag(NH3)2+ is:


[ Ag( NH 3 ) 2 ]
Kf   2
[ Ag ][ NH 3 ]
 The value of Kf for Ag(NH3)2+ is 1.7 x 107.
73
 The large value means that the complex ion is
quite stable.
 When a large amount of NH3 is added to a solution of

Ag+, you expect most of the Ag+ ion to react to form
the complex ion (large Kf - equil lies far to right).
 Handle calculations same way as any other K
74
The dissociation constant, Kd , is the reciprocal, or inverse, value of Kf.
The equation for the dissociation of Ag(NH3)2+ is


Ag ( NH 3 ) 2 (aq ) Ag  (aq )  2 NH 3 (aq)
The equilibrium constant equation is
 2
1 [ Ag ][ NH 3 ]
Kd   
K f [ Ag( NH 3 ) 2 ]
75
Equilibrium Calculations with Kf
What is the concentration of Ag+(aq) ion in 1.00 liters of
solution that is 0.010 M AgNO3 and 1.00 M NH3? The Kf for
Ag(NH3)2+ is 1.7 x 107.
1.) mols initially
AgNO3 (1.00L) (0.010 mol/L) = 0.010 mol
NH3 (1.00L) (1.00 mol/L) = 1.00 mol
2.) reaction
AgNO 3 ( aq )  2 NH 3 (aq) Ag ( NH 3 ) 2 N O 3 ( aq )
molo 0.010 1.00 0

Dmol -0.010 -0.020 (1:2) +0.010
molrxn 0.000 0.98 +0.010
76
3.) new conc
0.98 mols
[NH3] =  0 .98 M
1.00 L 0 .010 mols
[Ag(NH3)2NO3] = [Ag(NH3)2 ] = +  0 .010 M
1 .00 L
4.) complex ion diss

Ag ( NH 3 ) 2 (aq ) Ag  (aq )  2 NH 3 (aq)
Initial 0.010 0 0.98
Change -x +x +2x
Equilibrium 0.010-x x 0.98+2x
 2
1 1 8 [ Ag ][ NH ]
Kd    5 . 9 x10  3

K f 1.7 x10 7 [ Ag ( NH 3 ) 2 ]
77

8 [ Ag ][ NH 3 ] ( x )(0.98  2 x )
2 2
K d  5.9  10  

[ Ag ( NH 3 ) 2 ] (0.010  x )
2
( x )(0.98)
8
5.9  10 
( 0 .010 )
8  10
x  5 . 9  10  ( 0 . 010 )
( 0 . 98 ) 2  6 . 1  10 M = [Ag+]
78
 Solubility of a solid treated as with other equilibria. Solution is
saturated. No more solid will dissolve since dynamic equilibrium.
AgCl(s)  Ag+(aq) + Cl(aq) Ksp = [Ag+][Cl]
 Solid not included in the equilibrium expression.
 MyXz(s)  yM+p(aq)+zXq(aq) Ksp=[M+p]y[Xq]z
where Ksp = solubility product.
E.g. determine the equilibrium expression for each: PbCl 2,
Ag2SO4,Al(OH)3.
 Ksp can be determined if the solubility is known.
E.g. Determine Ksp for silver chromate (Ag2CrO4) if its solubility in
water is 0.0290 g/L at 25C.
 Determine molar solubility.
 Determine Ksp.
E.g. 2 Determine Ksp of CaF2 if its solubility is 2.20x10
John A.
4M.
Chapter
Schreifels
18-79
Chemistry 212
SOLUBILITY FROM Ksp
 Can be determined by using stoichiometry to express all quantities in terms of
one variable- solubility, x. i.e. for the reaction. Use equilibrium table to write
concentration of each in terms of the compound dissolving
E.g. determine the solubility of PbCl 2 if its Ksp = 1.2x105
PbCl2(s)  Pb2+(aq) + 2Cl(aq)
PbCl2(s)  Pb2+ + 2Cl
Initial conc. 0 0
C +x +2x
Equilibrium conc. +x +2x
E.g.1 Determine solubility of AgCl if its K sp = 1.8x1010M2.
AgCl (s)  Ag+ + Cl
Initial conc. 0 0
C +x +x
Equilibrium conc. +x +x
E.g.2 Determine solubility of Ag 2CO3 if its Ksp = 8.1x1012M3.

E.g.3 Determine solubility of Fe(OH)3 if its Ksp = 4x1038M4
John A. Schreifels
Chapter 18-80
Chemistry 212
Factors that Affect Solubility
 The common–Ion effect (Remember
LeChatelier’s Principle) a common–ion
E.g. Determine solubility of PbCl2 (Ksp = reduces the
1.2x105)in 0.100M NaCl. solubility of the
 Write equilibrium table in terms of x and [Cl ] compound.
PbCl2(s)  Pb2+ + 2Cl

Initial conc. 0 0.100 M
C +x +2x
Equilibrium conc. +x 0.100 M +2x
 Assume that [Cl]NaCl >>x

 Solve for x.
 E.g. determine the solubility of CaF2 in a solution of CaCl2. Ksp =
3.9x1011.
John A.
Chapter
Schreifels
18-81
Chemistry 212
Precipitation of Ionic Compounds
 Starting with two solutions, Qsp used to predict precipitation and even the extent of it.
 Precipitation = reverse of dissolution
 Precipitation occurs when Qsp > Ksp until Qsp = Ksp
 If Qsp < Ksp, precipitation won’t occur.
E.g. determine if precipitation occurs after mixing 50.00 mL 3.00x10 3 M BaCl2 and 50.00 mL
3.00x103 M Na2CO3.
Solution:
 CBaCl2 = 1.50x103 M; CNa2CO3 = 1.50x103 M
 Qsp = 1.50x103 M1.50x103 M = 2.25x106
 Qsp >1.1x1010.= Ksp precipitation.
E.g. 2 determine equilibrium concentration of each after precipitation occurs.
Solution:
 assume complete precipitation occurs;
 set up equilibrium table; and solve for equilibrium concentration of barium and carbonate ion
BaSO4 (s)  Ba + SO 24
2+
concentrations.
0 0
+x +x
x x
John A.
Chapter
Schreifels
18-82
Chemistry 212
Precipitation of Ionic Compounds
Eg. 3 determine the fraction of Ba2+ that has precipitated.
Solution:
 Use the amount remaining in solution (results of E.g. 2) divided by starting
concentration to determine the fraction of barium that is left in solution.
 Subtract from above.
E.g.4 determine the Br concentration when AgCl starts to precipitate
if the initial concentration of bromide and chloride are 0.100 M.
Ksp(AgBr) = 5.0x1013; Ksp(AgCl) = 1.8x1010.
John A.
Chapter
Schreifels
18-83
Chemistry 212
Factors that Affect Solubility-pH
 pH of the Solution: LeChatelier’s Principle again.
E.g. determine the solubility of CaF2 at a pH of 2.00. Ksp = 3.9x1011. Ka(HF) =
6.6x104.
Strategy:
 Determine the ratio of [F] and [HF] from the pH and Ka.
 Write an expression for solubility in terms of Ka and pH and
 Substitute into solubility equation to determine the solubility.
Solution:
 Ksp = 3.9x1011 = x[F]2 (pH changes the amount of free Fluoride.)
 Let x = solubility. Then 2x = [F] + [HF]
 From equilibrium equation: [F  ] Ka 6.6x10 4
 
[HF ] [H3 O  ] 1.00x10  2
 0.066
 2x = [F](1+1/0.066) = 16.15*[F] or
 [F] = 2*x/16.15 = 0.124*x
 3.9x1011 = x(0.0124*x)2
 x = 1.36x103 M vs. 2.13x104 M (normal solubility)
John A.
Chapter
Schreifels
18-84
Chemistry 212
Separation of Ions By Selective Precipitation
 Metal ions with very different Ksp can be separated.

 Divalent metal ions are often separated using solubility variations for the metal sulfides.
 Solution is saturated with H2S at 0.100 M; pH adjusted to keep one component soluble
and the other insoluble.
 H2S is diprotic acid; the overall reaction to get to sulfide is:
H2S (aq)+ H2O HS + H3O+ Ka1 = 8.9x108
HS + H2O S2 + H3O+ Ka2 = 1.2x1013
H2S + 2H2O S2 + 2H3O+ K = 1.1x1020
 Combine with solubility equilibrium reaction to get the overall equilibrium expression
and constant. 2+ 2
MS + M + S Ksp
S2 + 2H3O+ H2S + 2H2O K = 9.09x1019
2+
MS + 2H3O+ M + H2S Kspa = KKsp
[M2 ][H2S]
K spa 
[H3O  ]2
E.g. determine the solubility of 0.00500 M Zn 2+ in 0.100 M H2S at pH = 1. Ksp = 1.10x1021.
John A. Schreifels
Chapter 18-85
Chemistry 212
Complex Ions
 Formation of Complex Ions (Coordination Complexation ) = an
ion formed from a metal ion with a Lewis base attached to it by
a coordinate covalent bond.
Ag+(aq) + 2NH3(aq)  Ag(NH3)2(aq) Kf = 1.7x107
 Large equilibrium constant indicates that “free” metal is
completely converted to the complex.
Eg. What is the concentration of the silver amine complex
above in a solution that is originally 0.100 M Ag + and 1.00 M NH3?
E.g. determine the [Ag+] (free silver concentration) in 0.100 M
AgNO3 that is also 1.00 M NaCN.
Ag+ + 2CN  Ag(CN) 2 Kf = 5.6x1018
Initial 0 0.800 0.100M
Equil +x +2x x
Equil x 0.800+2x 0.100x
John A.
Chapter
Schreifels
18-86
Chemistry 212
Factors that Affect Solubility: Complexation
 Free metal ion concentration in solution is reduced when complexing
agent added to it;
 Free metal ion concentration needed in solubility expression.
E.g. determine if precipitation will occur in a solution containing

0.010 M AgNO3 and 0.0100 M Nal in 1.00 M NaCN. Recall Kf =
5.6x1018
Agl(s)Ag+ + l Ksp = 8.5.x1017
Strategy:
 Determine the free metal concentration in the solution.
 Use free metal concentration with iodide concentration to get Qsp
If Qsp < Ksp, no precipitation
If Qsp > Ksp, precipitation
John A.
Chapter
If Qsp = Ksp, precipitation is starting. Schreifels
Chemistry 212
18-87
Solubility with Complexing Agent
E.g. Determine the solubility of AgI in 1.00 M
NaCN. Recall Kf = 5.6x1018 the presence of a
Agl(s)Ag+ + l Ksp = 8.5.x1017 complexing agent
Strategy:
increases the
 Combine to equilibria equations to find a single
solubility
equation describing the equilibrium.
Agl(s)  Ag+ + l Ksp = 8.5.x1017
Ag+ + 2CN  Ag(CN) 2 Kf = 5.6x1018
Agl(s) + 2CN  Ag(CN) 2 + l K = 476
– Setup equilibrium table and solve.

AgI(s) + 2CN(aq)  Ag(CN) 2 I(aq)
Starting 1.00 M 0 0
 2x x x
Equil 1.00 – 2x x x
2
x
476 
(1.00  2 x )2
John A. Schreifels
Chapter 18-88
Chemistry 212
Chemical Equilibrium
Introduction
1.) Equilibria govern diverse phenomena

 Protein folding, acid rain action on minerals to aqueous reactions
2.) Chemical equilibrium applies to reactions that can occur in both directions:
 reactants are constantly forming products and vice-versa

 At the beginning of the reaction, the rate that the reactants are changing into the
products is higher than the rate that the products are changing into the reactants.
 When the net change of the products and reactants is zero the reaction has
reached equilibrium.
Then, system continually exchanges

products and reactants,
First, system reacheswhile maintaining
equilibrium
equilibrium distribution.
Reactants Product
At equilibrium the amount of reactants and products are constant,

but not necessarily equal
Equilibrium Constant
1.) The relative concentration of products and reactants at equilibrium is a

constant.
2.) Equilibrium constant (K):

 For a general chemical reaction
[C ]c [ D]d
Equilibrium constant: K
[ A]a [ B ]b
Where:
- small superscript letters are the stoichiometry coefficients
- [A] concentration chemical species A relative to standard state
2.) Equilibrium constant (K):

 A reaction is favored when K > 1
 K has no units, dimensionless
- Concentration of solutes should be expressed as moles per liter (M).
- Concentrations of gases should be expressed in bars.
► express gas as Pgas, emphasize pressure instead of concentration
► 1 bar = 105 Pa; 1 atm = 1.01325 bar
- Concentrations of pure solids, pure liquids and solvents are omitted
► are unity
► standard state is the pure liquid or solid
3.) Manipulating Equilibrium Constants

Consider the following reaction:
[ H  ][ A ]
K1 
[ HA]
Reversing the reaction results in a reciprocal equilibrium reaction:
[ HA]
K '1   1 / K1
 
[ H ][ A ]
If two reactions are added, the new K is the product of the two individual K values:
K1
K2
K3
[ H  ][ A  ] [CH  ] [ A  ][C H  ]
K1  K2  K3 
[ HA ] [ H  ][C ] [ HA ][C ]
[ H  ][ A  ] [C H  ] [ A  ][C H  ]
K 3  K1K 2   
[ HA ]  [ HA ][C ]
[ H ][C ]

 Example:
Given the reactions and equilibrium constants:
Kw= 1.0 x 10-14
KNH = 1.8 x 10-5

3
Find the equilibrium constant for the reaction:
Solution:
K1= Kw
K2=1/KNH3
K3=Kw*1/KNH3=5.6x10-10
Equilibrium and Thermodynamics
1.) Equilibrium constant derived from the thermodynamics of a chemical

reaction.
 deals with the relationships and conversions between heat and other forms of
energy
2.) Enthalpy
 DH – is the heat absorbed or released when the reaction takes place under
constant applied pressure
DH = Hproducts – Hreactants
 Standard enthalpy change (DHo) –

all reactants and products are
in their standard state.
 DHo – negative  heat released
- Exothermic
- Solution gets hot
 DHo – positive  heat absorbed
- Endothermic
- Solution gets cold
3.) Entropy
 Measure of a substances “disorder”
 Greater disorder  Greater Entropy
- Relative disorder: Gas > Liquid > solid
DS = Sproducts – Sreactants
 DSo – change in entropy when all species are in standard state.

- positive
product more disorder
- negative 
product less disorder
DSo = +76.4 J/(K.mol) at 25oC
More disorder for aqueous ions than solid

3.) Entropy
 Increase in temperature results in an increase in Entropy (S)
 Increase occurs for all products and reactants
 Primarily concerned with DS, which is only weakly temperature dependent

- generally treat DS and DH as temperature independent
4.) Free Energy

 Systems at constant temperature and pressure have a tendency toward
lower enthalpy and higher entropy
 Chemical reaction is favored if:

- DH is negative  heat given off
and
- DS is positive  more disorder
 Chemical reaction is not favored if:

- DH is positive and DS is negative
 Gibbs Free Energy (DG): determines if a reaction is favored or not when both
DH and DS are positive or negative
- A reaction is favored if DG is negative
Free energy:DG = DH -TDS

where T is temperature (Kelvin)
4.) Free Energy

 Example:
Is the following reaction favored at 25oC?

DHo = -74.85 x 103 J/mol
DSo = -130.4 J/K.mol
Free energy:DG = DH –TDS = (-74.85x103 J/mol) – (298.15K)(-130.4 J/K.mol)
DG = -35.97 kJ/mol  DG negative  reaction favored
Favorable influence of enthalpy is greater than unfavorable influence of entropy

5.) Free Energy and Equilibrium

 Relate Equilibrium constant to the energetics (DH & DS) of a reaction
 Equilibrium constant depends on DG:
  G o
K e RT
where
R (gas constant) = 8.314472 J/(K.mol)
T = temperature in kelvins
 The more negative DG  larger equilibrium constant

 Example:
DG = -35.97
 G
o
RT  e  (  35.97 x 10 J / mol )( 8 .314472J /( K mol )( 298.15 K )  2 . 00 x 10 6

3 .
K e
Because K is very large, HCl is very soluble in water and nearly completely ionized
5.) Free Energy and Equilibrium

 If DGo is negative or K >1 the reaction is spontaneous
 Reaction occurs by just combining the reactants
 If DGo is positive or K < 1, the reaction is not spontaneous

- Reaction requires external energy or process to proceed
Gas flows towards a vacuum. A vacuum does not naturally form.

spontaneous nonspontaneous
Le Châtelier’s Principal
1.) What Happens When a System at Equilibrium is Perturbed?

 Change concentration, temperature, pressure or add other chemicals
 Equilibrium is re-established
 Reaction accommodates the change in products, reactants, temperature,
pressure, etc.
 Rates of forward and reverse reactions re-equilibrate
1.) What Happens When a System at Equilibrium is Perturbed?

 Le Châtelier’s Principal:
- the direction in which the system proceeds back to equilibrium is such that
the change is partially offset.
Consider this reaction:
At equilibrium:
To return to equilibrium
(balance), some (not all)
CO and H2 are converted
Add excess CO(g): to CH3OH
If all added CO was converted to CH3OH, then reaction

would be unbalanced by the amount of product
2.) Example:
Consider this reaction:
[ Br - ][C r2 O 72 - ][ H  ]8
K  1  10 11 at 25 o C
[ B rO 3- ][C r 3  ]2
At one equilibrium state:
[H  ]  5.0 M [Cr2 O 72 - ]  0.10 M [Cr 3  ]  0.0030 M

[Br  ]  1.0 M [BrO 3- ]  0.043 M
2.) Example:
What happens when:
[Cr2 O 72 - ] increased from 0.10 M to 0.20 M

According to Le Châtelier’s Principal, reaction should go back to left to
off-set dichormate on right:
Use reaction quotient (Q), Same form of equilibrium equation, but not at
equilibrium:
Q
[ B r - ][ C r2 O 72 - ][ H  ]8

 1.0  0.20  5.0  8
 2  10 11  K
[ B rO 3- ][C r 3  ]2  0.043  0.0030  2
2.) Example:
Because Q > K, the reaction must go to the left to decrease numerator and
increase denominator.
Continues until Q = K:
1. If the reaction is at equilibrium and products are added (or reactants

removed), the reaction goes to the left
2. If the reaction is at equilibrium and reactants are added ( or products

removed), the reaction goes to the right
3.) Affect of Temperature on Equilibrium
Combine Gibbs free energy and Equilibrium Equations:
 G    H o  T S 
o

K e RT e RT
  H  S 
o
e RT R
 H o S o
e RT e R
Only Enthalpy term is temperature dependent:
 H o
K (T )  e RT
3.) Affect of Temperature on Equilibrium
1. Equilibrium constant of an endothermic reaction (DHo = +) increases if

the temperature is raised.
D
DH = +
2. Equilibrium constant of an exothermic reaction (DHo = -)decreases if the

temperature is raised.
D
DH = -
4.) Thermodynamics vs. Kinetics

 Thermodynamics predicts if a reaction will occur
- determines the state at equilibrium
 Thermodynamics does not determine the rate of a reaction
- Will the reaction occur instantly, in minutes, hours, days or years?
DG = -
spontaneous
Diamonds Graphite
- While reaction is spontaneous, takes millions of years to occur
Solubility Product
1.) Equilibrium constant for the reaction which a solid salt dissolves to give
its constituent ions in solution
 Solid omitted from equilibrium constant because it is in a standard state
 Example:
K sp  [ H g 22  ][ C l - ] 2  1 .2  10  18
Solubility Product
1.) Saturated Solution – contains excess, undissolved solid

 Solution contains all the solid capable of dissolving under
the current conditions
 Example:
Find [Cu2+] in a solution saturated with Cu4(OH)6(SO4) if [OH-] is fixed

at 1.0x10-6M. Note that Cu4(OH)6(SO4) gives 1 mol of SO42- for 4 mol
of Cu2+?
K sp  2 .3  10  69
Solubility Product
2.) If an aqueous solution is left in contact with excess solid, the solid will
dissolve until the condition of Ksp is satisfied
 Amount of undissolved solid remains constant
 Excess solid is required to guarantee ion concentration is consistent with K sp
3.) If ions are mixed together such that the concentrations exceed Ksp, the
solid will precipitate.
4.) Solubility product only describes part of the solubility of a salt

 Only includes dissociated ions
 Ignores solubility of solid salt
Common ion effect – a salt will be less soluble if one of

its constituent ions is already present in the solution.
Decrease in the solubility of MgF2 by PbCl2 precipitate because the

the addition of NaF
ion product is greater than Ksp.
Common Ion Effect
1.) Affect of Adding a Second Source of an Ion on Salt Solubility

 Equilibrium re-obtained following Le Châtelier’s Principal
 Reaction moves away from the added ion
Find [Cu2+] in a solution saturated with Cu4(OH)6(SO4) if [OH-] is

fixed at 1.0x10-6M and 0.10M Na2SO4 is added to the solution.
Complex Formation
1.) High concentration of an ion may redissolve a solid

 Ion first causes precipitation
 Forms complex ions, consists of two or more simple ions bonded to each other
ppt. formation
Complex forms and

redissolves solid
Complex Formation
2.) Lewis Acids and Bases

 M+ acts as a Lewis acid  accepts a pair of electrons
 X- acts as a Lewis base  donates a pair of electrons
 Bond is a coordinate covalent bond
ligand adduct
Lewis acid Lewis base

Complex Formation
3.) Affect on Solubility

 Formation of adducts increase solubility
Ksp
Implies low Pb2+ solubility: K sp  [ Pb 2  ][ I - ]2  7 .9  10  9
 Solubility equation becomes a complex mixture of reactions

- don’t need to use all equations to determine the concentration of any species
Only one concentration of Pb2+ in solution
Concentration of Pb2+ that

satisfies any one of the
equilibria must satisfy all
of the equilibria
All equilibrium conditions are satisfied simultaneously

Complex Formation

 Total concentration is dependent on each individual complex species
 Pb total   Pb2     PbI     PbI 2 ( aq )   PbI 3    PbI 42  
Total solubility of lead depends on [I-] and the

solubility of each individual complex formation.
Complex Formation

 Example:
Given the following equilibria, calculate the concentration of each zinc-containing

species in a solution saturated with Zn(OH)2(s) and containing [OH-] at a fixed
concentration of 3.2x10-7M.
Zn(OH)2 (s) Ksp = 3.0x10-16

Zn(OH)+ b1 = 2.5 x104
Zn(OH)3- b3 = 7.2x1015
Zn(OH)42- b4 = 2.8x1015
Acids and Bases
1.) Protic Acids and Bases – transfer of H+ (proton) from one molecule to
another
 Hydronium ion (H3O+) – combination of H+ with water (H2O)
 Acid – is a substance that increases the concentration of H3O+
 Base – is a substance that decreases the concentration of H3O+

- base also causes an increase in the concentration of OH - in aqueous solutions
acid
2.) Brønsted-Lowry – definition does not require the formation of H3O+

 Extended to non-aqueous solutions or gas phase
 Acid – proton donor
 Base – proton acceptor

acid base salt
Acids and Bases
3.) Salts – product of an acid-base reaction

 Any ionic solid
 Acid and base neutralize each other and form a salt
 Most salts with a single positive and negative charge dissociate completely
into ions in water
4.) Conjugate Acids and Bases
Products of acid-base reaction

are also acids and bases
A conjugate acid and its base or a

conjugate base and its acid in an
aqueous system are related to each
other by the gain or loss of H+
Acids and Bases
5.) Autoprotolysis – acts as both an acid and base

 Extent of these reactions are very small
water
K w  [ H  ][ O H - ]  1 .0  10  14
- H3O+ is the conjugate acid of water

- OH- is the conjugate base of water
 Kw is the equilibrium constant for the dissociation of water
Acetic acid K  3 .5  10  15
Acids and Bases
6.) pH – negative logarithm of H+ concentration

 Ignores distinction between concentration and activities (discussed later)
pH   log[ H  ]
pH  pO H   log[ K w ]  14 .00 at 25 o C
 A solution is acidic if [H+] > [OH-]
 A solution is basic if [H+] < [OH-]
 An aqueous solution has a neutral pH if [H +]=[OH-]

- This occurs when [H+] = [OH-] = 10-7M or pH = 7
Acids and Bases
6.) pH
 pH values for some common samples
Acids and Bases
6.) pH
 Example:
What is the pH of a solution containing 1x10-6 M H+?
What is [OH-] of a solution containing 1x10-6 M H+?

Acids and Bases
7.) Strengths of Acids and Bases

 Depends on whether the compound react nearly completely or partially to
produce H+ or OH-
 strong acid or base completely dissociate in aqueous solution

- equilibrium constants are large
- everything else termed weak
Strong  no undissociated HCl or KOH

Acids and Bases
7.) Strengths of Acids and Bases
 weak acids react with water by donating a proton

- only partially dissociated in water
- equilibrium constants are called Ka – acid dissociation constant
- Ka is small
Ka [ H  ][ A ]
Ka 
Equivalent Ka [ HA]
 weak bases react with water by removing a proton

- only partially dissociated in water
- equilibrium constants are called Kb – base dissociation constant
- Kb is small  
Kb [ BH ][OH ]
Kb 
Equivalent Kb
[ B]
Some Common Weak Acids (carboxylic acids)
ACID FORMULA Ka pKa ACID FORMULA Ka pKa

acetic acid H(C2H3O2) 1.74 E-5 4.76 hydrocyanic acid HCN 6.17 E-10 9.21
ascorbic acid (1) H2(C6H6O6) 7.94 E-5 4.10 hydrofluoric acid HF 6.31 E-4 3.20
ascorbic acid (2) (HC6H6O6)- 1.62 E-12 11.79 lactic acid H(C3H5O3) 8.32 E-4 3.08
boric acid (1) H3BO3 5.37 E-10 9.27 nitrous acid HNO2 5.62 E-4 3.25
boric acid (2) (H2BO3)- 1.8 E-13 12.7 octanoic acid H(C8H15O2) 1.29 E-4 4.89
boric acid (3) (HBO3)= 1.6 E-14 13.8 oxalic acid (1) H2(C204) 5.89 E-2 1.23
butanoic acid H(C4H7O2) 1.48 E-5 4.83 oxalic acid (2) (HC2O4)- 6.46 E-5 4.19
carbonic acid (1) H2CO3 4.47 E-7 6.35 pentanoic acid H(C5H9O2) 3.31 E-5 4.84
carbonic acid (2) (HCO3)- 4.68 E-11 10.33 phosphoric acid (1) H3PO4 6.92 E-3 2.16
chromic acid (1) H2CrO4 1.82 E-1 0.74 phosphoric acid (2) (H2PO4)- 6.17 E-8 7.21
chromic acid (2) (HCrO4)- 3.24 E-7 6.49 phosphoric acid (3) (HPO4)= 2.09 E-12 12.32
citric acid (1) H3(C6H5O7) 7.24 E-4 3.14 propanoic acid H(C3H5O2) 1.38 E-5 4.86
citric acid (2) (H2C6H5O7)- 1.70 E-5 4.77 sulfuric acid (2) (HSO4)- 1.05 E-2 1.98
citric acid (3) (HC6H5O7)= 4.07 E-7 6.39 sulfurous acid (1) H2SO3 1.41 E-2 1.85
formic acid H(CHO2) 1.78 E-4 3.75 sulfurous acid (2) (HSO3)- 6.31 E-8 7.20
heptanoic acid H(C7H13O2) 1.29 E-5 4.89 uric acid H(C5H3N4O3) 1.29 E-4 3.89
Some Common Weak Acids (Metals cations)
Some Common Weak Bases (amines)
BASE FORMULA Kb pKb

alanine C3H5O2NH2 7.41 E-5 4.13
Ammonia NH3 (NH4OH) 1.78 E-5 4.75
dimethylamine (CH3)2NH 4.79 E-4 3.32
ethylamine C2H5NH2 5.01 E-4 3.30
glycine C2H3O2NH2 6.03 E-5 4.22
hydrazine N2H4 1.26 E-6 5.90
methylamine CH3NH2 4.27 E-4 3.37
trimethylamine (CH3)3N 6.31 E-5 4.20
 The Ka or Kb of an acid or base may also be written in terms of “pK a” or “pKb”
pK a   log( K a ) pK b   log( K b )
 As Ka or Kb increase  pKa or pKb decrease
- a strong acid/base has a high K or K and a low pK or pk

Acids and Bases
8.) Polyprotic Acids and Bases – can donate or accept more than one proton
 Ka or Kb are sequentially numbered
- Ka1,Ka2,Ka3 Kb1,Kb2,Kb3
Acids and Bases
8.) Relationship Between Ka and Kb
[ H  ][ A ]
Ka 
[ HA]
[ HA][OH  ]
Kb 
[ A ]
K w  Ka  Kb
[ H  ][ A ] [ HA][OH  ]
   [ H  ][OH  ]
[ HA] [ A ]
K w  Ka  Kb
Acids and Bases
8.) Relationship Between Ka and Kb

 Example:
Write the Kb reaction of CN-. Given that the Ka value for

HCN is 6.2x10-10, calculate Kb for CN-.
Will it all dissolve, and if not, how much?
 Many natural processes depend on the precipitation or dissolving of a
slightly soluble ionic substance.
 Applies to the equilibria of slightly soluble, or nearly insoluble, ionic
compounds.
 Their equilibrium constants can be used to answer questions
regarding solubility and precipitation.
Formation of Precipitate
Limestone Cave (Luray Caverns, Virginia)
Source: ©E.R. Degginger

compound.
It equals the product of the equilibrium

concentrations of the ions in the compound.
Each concentration is raised to a power equal
to the number of such ions in the formula of
the compound.
 When an excess of a slightly soluble ionic compound is mixed with
water, an equilibrium is established between the solid and the ions
in the saturated solution.
 For the salt calcium oxalate, CaC2O4, you have the following
equilibrium.
CaC2O4(s)  Ca2+(aq) + C2O42-(aq)
 The equilibrium constant for the process is termed the solubility

product constant
Ksp = [Ca2+][C2O42-]
 Many ionic solids form saturated solutions with very small amounts of
solid added to water (a few micrograms)
 The extent of solubility in water is defined by a solubility product
constant (Ksp)
 For an ionic solid with the general formula MmXx(s) and ionic charges n
and y, respectively:
MmXx(s)  mMn+(aq) + xXy-(aq)
Ksp = [Mn+]m[Xy-]x
 For the ionic solid AgCl
AgCl(s)  Ag+(aq) + Cl-(aq)
Ksp = [Ag+][Cl-] = 1.8 x 10-10 (at 25 oC)
 Ksp expression is exactly the format used for all other
equilibria previously discussed; K is now applied to a
specific type of process: solubility of ionic substances
 The value of Ksp is measured by experiment from the
concentrations of ions in solution. For example, for
the solid PbBr2 at 25 oC, the equilibrium concentrations
of lead (2+) and bromide (-1) ions formed from a
saturated solution of lead bromide
PbBr2(s)  Pb2+(aq) + 2Br-(aq)
are found to be: [Pb2+] = 0.0120 M & [Br-] = 0.0240 M

Ksp = [Pb2+][Br-]2 = (0.0120)(0.0240)2 = 6.9 x 10-6
 The solubility of ionic substances can be determined from K sp values
 Q. Find the solubility of silver sulfate given a Ksp for silver sulfate of
1.2 x 10-5 at 25 oC.
 Write out equilibrium & set up equilibrium table
Ag2SO4(s)  2Ag+(aq) + SO42-(aq)
x 2x x
let x = solubility of silver sulfate
Ksp = [Ag+]2[SO42-] = (2x)2x = 4x3
5
1. 2 X 10
x3  0.014 M
4
Ksp Expressions
Write the solubility product expressions for the following ionic solids: (a)
BaCrO4; (b) NiS; (c) Pb3(AsO4)2
a. Ksp = [Ba2+][CrO42-]
b. Ksp = [Ni2+][S2-]
c. Ksp = [Pb2+]3[AsO43-]2
Solubility Relations
 General relations between solubility and Ksp are given
below (M = metal; X = anion or polyatomic ion):
 General formulas given as MmXx
General Formula Solubility, s

MX (e.g., AgCl) s = (Ksp)1/2
MX2, M2X (e.g., PbI2) s = [Ksp/4]1/3
MX3, M3X (e.g., Ag3PO4) s = [Ksp/27]1/4
M2X3, M3X2 (e.g., FeCl3)s = [Ksp/108]1/5
The exponent of each s expression equals 1/(m + x)

A 1.0-L sample of a saturated calcium oxalate solution, CaC2O4,
contains 0.0061-g of the salt at 25 oC. Calculate the Ksp for this
salt at 25 oC.
We must first convert the solubility of

calcium oxalate from 0.0061 g/liter to
moles per liter.
1 mol CaC 2O 4
M CaC 2O 4  ( 0.0061 g CaC2O 4 / L ) 
128g CaC 2O 4
 4.8  10  5 m ol CaC 2O 4 / L
A 1.0-L sample of a saturated calcium oxalate solution, CaC2O4, contains

0.0061-g of the salt at 25 oC. Calculate the Ksp for this salt at 25 oC.
When 4.8 x 10-5 mol of solid dissolve it

forms 4.8 x 10-5 mol of each ion.
2
CaC 2O 4 ( s ) H 2O
Ca 2 (aq)  C 2O 4 (aq)
Starting 0 0
Change +4.8 x 10-5 +4.8 x 10-5

Equilibrium 4.8 x 10-5 4.8 x 10-5
A 1.0-L sample of a saturated calcium oxalate solution, CaC2O4, contains

0.0061-g of the salt at 25 oC. Calculate the Ksp for this salt at 25 oC.
You can now substitute into the

equilibrium-constant expression.
2 2
K sp  [Ca ][C 2O 4 ]
K sp  ( 4.8  10  5 )( 4.8  10  5 )
K sp  2.3  10  9
Homework #78
 A. Pb3(PO4)2(s) ⇌ 3Pb2+(aq) + 2PO43(aq)
Initial 0 0
Change -x → +3x +2x
Equil. 3x 2x
 Ksp = [Pb2+]3 [PO43]2 = (3x)3(2x)2 = 108 x5,
 Ksp = 108(6.2 × 10-12)5 = 9.9 × 10-55
 B. Li2CO3(s) ⇌ 2 Li+(aq) + CO32-(aq)

Initial 0 0
Equil. 2s s
 Ksp = [Li+]2 [CO32] = (2s)2(s) = 4s3,
 Ksp = 4(7.4 × 10-2)3 = 1.6 × 10-3
Relative solubilities
 Ksp will only allow us to compare the solubility of solids that fall apart into
the same number of ions.
 The bigger the Ksp of those the more soluble.
 If they fall apart into different number of pieces you have to do the math.
Calculating Solubility from Ksp
Which of the following salts is the most soluble (mol/L)? Least soluble? Next to
most soluble?
Salt Ksp
a. BaCO3 8.1e-9
b. CaCO3 3.8e-9
c. CuCl 1.9e-7
d. BaSO3 8.0e-7
e. CaCrO4 7.1e-4
Common Ion Effect
Acid-base equilibria & common ions
 Consider solution containing HF (weak acid) and salt
NaF
 Species in solution: HF, H2O, Na+, F-
 What effect does presence of NaF have on dissociation
equilibrium of HF?
 HF(aq)  H+(aq) + F-(aq)
 Use Le Chatelier’s principle; extra F- (from NaF)
shifts equilibrium to the left
 Because of this, the [H+] will decrease
 What happens to the pH?
 This is the Common Ion Effect

Equilibrium calculations involving
common
 34.6 g ions
of NH Cl is added to 3.98 L of a 0.0145 M solution of NH .
4 3
Kb(NH3) = 1.8 x 10-5.
 What is the pH of the original solution before the addition of
NH4Cl? pH=10.7
 NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq)
 So – what’s the pH of the solution after the addition of the

NH4Cl (assume that the volume stays constant)?
 pH=8.2
Effect of adding common ions to
weak acids?
 What is the general statement that we can make about what happens to the
acidity of a weak acid upon addition of a common ion?
 Should go up!! Do to Lechatliers Principle.
 How does the presence of other ion effect the solubility calculations?
 The importance of the Ksp becomes apparent when you consider the solubility of
one salt in the solution of another having the same cations.

Each salt contributes the same cation (Ca 2+)
The effect is to make calcium oxalate less soluble than it would be in pure water.
For example, suppose you wish to know the solubility of calcium oxalate in a
solution of calcium chloride.
A Problem To Consider
What is the molar solubility of calcium oxalate in 0.15 M calcium chloride?

The Ksp for calcium oxalate is 2.3 x 10-9.
Note that before the calcium oxalate

dissolves, there is already 0.15 M Ca2+ in
the solution.
2
CaC 2O 4 ( s ) H O Ca 2 (aq)  C 2O 4 (aq)
2
Starting 0.15 0
Change +x +x
Equilibrium 0.15+x x

You substitute into the equilibrium-

constant equation
2 2
[Ca ][C 2O 4 ]  K sp
9
( 0.15  x )( x )  2.3  10

Now rearrange this equation to give

9 9
2.3  10 2.3  10
x 
0.15  x 0.15
We expect x to be negligible compared to
0.15.

Now rearrange this equation to give

9 9
2.3  10 2.3  10
x 
0.15  x 0.15
8
x  1.5  10

Therefore, the molar solubility of calcium

oxalate in 0.15 M CaCl2 is 1.5 x 10-8 M.
In pure water, the molarity was 4.8 x 10-5 M,
which is over 3000 times greater.
Precipitation Reactions
Factors Which Affect Solubility
 Important solution factors which may affect the solubility of ionic
substances in water
 Temperature - solubility is temperature dependent

 Common ions - the presence of common ions in solution lowers solubility
 pH - solution pH can affect solubility if the anion of the ionic solid (i.e., X)
is the conjugate base of a weak acid
 Complex ions - ammonia reacts with many metal ions in solution through
complexation reactions
Precipitation Calculations
Rather than considering how much of a

ion concentration?

To predict the direction of reaction, you

compare Qc with Kc (Chapter 13).
The reaction quotient has the same form as
the Ksp expression, but the concentrations of
products are starting values.

Consider the following equilibrium.

H2O 2 
PbCl 2 (s ) Pb (aq)  2Cl (aq)

The Qc expression is
2  2
Q c  [Pb ]i [Cl ]i
where initial concentration
is denoted by i.

If Qc exceeds the Ksp, precipitation occurs.

If Qc is less than Ksp, more solute can dissolve.
If Qc equals the Ksp, the solution is saturated.
Predicting Whether Precipitation
Will Occur
The concentration of calcium ion in blood plasma is 0.0025 M. If the

concentration of oxalate ion is 1.0 x 10-7 M, do you expect calcium oxalate to
precipitate? Ksp for calcium oxalate is 2.3 x 10-9.
The ion product quotient, Qc, is:

2 2
Q c  [Ca ]i [C 2O 4 ]i
-7
Q c  (0.0025)  (1.0  10 )
-10
Q c  2.5  10
Predicting Whether Precipitation
Will Occur
The concentration of calcium ion in blood plasma is 0.0025 M. If the

concentration of oxalate ion is 1.0 x 10-7 M, do you expect calcium oxalate to
precipitate? Ksp for calcium oxalate is 2.3 x 10-9.
This value is smaller than the Ksp, so you

do not expect precipitation to occur.
-10
Q c  2.5  10  K sp
When Does a Precipitate Form?
When solutions containing soluble ionic compounds are mixed, when

do we predict a precipitate will form?
Determine which compound may precipitate after addition (apply
solubility rules)
Calculate concentrations in solution assuming NO precipitation has
occurred
Determine Qsp, and compare with Ksp
Question: 50.00 mL of 0.00320 M Pb(NO3)2 is mixed with 50.00 mL of

0.111 M NaCl. Will a precipitate form?
1. potential ppt would be PbBr2 (NaNO3 is soluble)

When Does a Precipitate Form?
2. Look up Ksp of PbCl2 and write out solubility eq for PbCl2 in water
PbCl2(s)  Pb2+(aq) + 2 Cl-(aq) Ksp = 1.6e-5
Qsp = [Pb2+][Cl-]2 = (0.0016)(0.0555)2 = 4.93e-6
Qsp/Ksp <1 thus, no ppt formed

Homework #98
 The formation of Mg(OH)2(s) is the only possible precipitate. Mg(OH)2(s)
will form if Q > Ksp.
 Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH(aq)
Ksp = [Mg2+][OH]2 = 8.9 × 10-12 (Page A24)
 [Mg2+]o = 4
= 2.0 ×210-4 M
100.0 mL  4.0  10 mmol Mg / mL
100.0 mL  100.0 mL
 [OH]o = 4
= 1.0 × 10-4 M
100.0 mL  2.0  10 mmol OH / mL
200.0 mL
 Q = [Mg2+]o[OH]o = (2.0 × 10-4 M)(1.0 × 10-4 )2 = 2.0 × 10-12
 Since Q < Ksp, then Mg(OH)2(s) will not precipitate, so no precipitate

forms.
 Sometimes it is necessary to account for other reactions aqueous ions

might undergo.
For example, if the anion is the conjugate

base of a weak acid, it will react with H3O+.
You should expect the solubility to be

affected by pH.
 Consider the following equilibrium.

H 2O 2 2
CaC 2O 4 ( s ) Ca (aq)  C 2O 4 (aq)
 Because the oxalate ion is conjugate to a weak
acid (HC2O4-), it will react with H3O+.
2  H2O 
C 2O 4 (aq )  H 3O (aq) HC 2O 4 (aq)  H 2O(l)
According to Le Chatelier’s principle, as

C2O42- ion is removed by the reaction with
H3O+, more calcium oxalate dissolves.
Therefore, you expect calcium oxalate to
be more soluble in acidic solution (low
pH) than in pure water.
Complexation Effects on Solubility
 The formation of soluble metal complexes increases the
solubility of sparingly soluble ionic solids
 An example is the reaction of silver ion with ammonia:
AgCl(s)  Ag+(aq) + Cl-(aq) Ksp = 1.8 x 10-10
Ag+(aq) + 2 NH3(aq)  Ag(NH3)2+(aq) Kf = 2.0 x 107
Kc = KspX Kf = 3.6 x 10-3
Ag(NH3)2+ = complex ion
Ag+ = Lewis acid (electron pair acceptor)
NH3 = Lewis base (electron pair donor)
 The chemical processes are coupled, such that


[Ag(NH 3 )2 ][Cl  ] 3
K 
AgCl(s) c+ 2 NH3(aq)  Ag(NH
2
+ 3.6  10 -
3)2 (aq) + Cl (aq)
[NH 3 ]
Complex ion Equilibria
 A charged ion surrounded by ligands.

 Ligands are Lewis bases using their lone pair to stabilize the charged metal
ions.
 - -
Common ligands are NH , H O, Cl ,CN
3 2
 Coordination number is the number of attached ligands.
 2+
Cu(NH ) has a coordination # of 4
34
The addition of each ligand has its
own equilibrium
 Usually the ligand is in large excess.
 And the individual K’s will be large so we can treat them as if they go
to completion.
 The complex ion will be the biggest ion in solution.
Terima kasih

2021 Kimia Dasar Pertemuan 5

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

2021 Kimia Dasar Pertemuan 5

Uploaded by

Copyright:

Available Formats

KIMIA FISIKA

Pertemuan 5 : Kesetimbangan Ionik

 Importance - (a) Selective precipitation is an important industrial

Solubility - The greatest amount of a

Example - The solubility of silver chloride in

Most solubilities increase with temperature.

Soluble Ionic Materials - have solubilities in

Most salts dissociate into ions when they

•One may provide solubility information as

•These two quantities are obviously related

 Many natural processes depend on the precipitation or dissolving of a slightly

– Equilibrium constants of slightly soluble, or

 When an excess of a slightly soluble ionic compound is mixed with water, an

– For the salt calcium oxalate, CaC2O4, you have the

 When an excess of a slightly soluble ionic compound is mixed with water, an

– The equilibrium constant for this process is

– For example, suppose you wish to know the

 Precipitation is merely another way of looking at solubility equilibrium.

– Rather than considering how much of a

 To determine whether an equilibrium system will go in the forward or reverse

 To determine whether an equilibrium system will go in the forward or reverse

– Consider the following equilibrium.

 To determine whether an equilibrium system will go in the forward or reverse

 To determine whether an equilibrium system will go in the forward or

 Fractionalprecipitation is the technique of

 Fractional precipitation is the technique of

 Sometimes it is necessary to account for other reactions aqueous ions might

– For example, if the anion is the conjugate base of

– Consider the following equilibrium.

– Because the oxalate ion is conjugate to a weak

– According to Le Chatelier’s principle, as C2O42- ion

 Many metal ions, especially transition metals,

– For example, the silver ion, Ag+, can react

– The value of Kf for Ag(NH)2+ is 1.7 x 107.

– A large Kf value means that the complex ion is

 The dissociation constant, Kd, is the reciprocal, or inverse, value of Kf.

– The equation for the dissociation of Ag(NH3)2+ is

– The equilibrium constant equation is

 An amphoteric hydroxide is a metal hydroxide that reacts with both acids

 An amphoteric hydroxide is a metal hydroxide that reacts with both acids

– When a strong base is slowly added to a solution

Zn 2 (aq )  2OH  (aq )  Zn(OH ) 2 (s )

 In the next section, we look at the

 Insoluble salts will have extremely small quantities of salt

2  the equilibrium-constant expression.

 The following table summarizes.

 The water solubility of an ionic compound is amount

 Let s be the molar solubility of CaF2.

which equals the molar solubility of CaF2 but we

2 .0  10 4 mol CaF2 78 .1g CaF2

 The salt contributes the fluoride to the system and

[CaF2] in pure H2O was 2.0 x 10-4 M;

 Precipitation is merely another way of looking at solubility equilibrium.

 Rather than considering how much of a

 To predict the direction of reaction, you compare Q

where initial concentration is

 If Q > Ksp, , the solution is supersaturated meaning the

0.0025 M 1.0 x 10-52 M

 This value is larger than the Ksp, so you expect

PbCl2 (s) Pb2+ (aq) + 2Cl- (aq)

we find that Q (2.0 x 10-5) < Ksp (3.6 x 10-5) indicating

 For example, when you slowly add potassium

 It is therefore possible to separate Ba2+ from Sr2+ by

 For example, if the anion is the conjugate base of