K and The Solubility of Salts: Slide 2 To 9 Is A Revison: Study These On Your Own

Ksp AND THE SOLUBILITY
OF SALTS
SLIDE 2 TO 9 IS A REVISON: STUDY THESE
ON YOUR OWN.
CHEMICAL EQUILIBRIUM:A REVIEW
Kp
K
Kc Ksp
K K
} Q
THE RELATIONSHIP BETWEEN K, 1 AND Q
The relatonship between K and 1 and K and Q can tell
if the system is at equilibrium or not.
If K > 1 the reacton is product favored.

If K = 1 the equilibrium is symmetrical (is at equilibrium).
If K < 1 the reacton is reactant favored.
If K > Q the reacton is product favored.

If K = Q the equilibrium is symmetrical. (is at equilibrium)
If K < Q the reacton is reactant favored.
In this case K is given and Q have to be calculated.
REVISION OF NAMES AND FORMULAS
Study the table of names and

formulas.
Examples are:
C2O42- ---- Oxalate ion
(NH4)2C2O4-Ammonium oxalate
REVISION OF IONS IN SOLUTION AND
SOLUBILITY GIUDELINES
Revise the ions in soluton and
solubility.
Include the solubility table
given to you in CMY 117.
Some of such tables are shown
below.
PRECIPITATION REACTION CONT.
SOLUBILITY TABLE:
• Solubility Table
Generally soluble in water Exceptions
Na+, K+, NH4+ No common exception
Nitrates, NO3-, Nitrites, NO2- No common exception
Chlorates, ClO3- No common exception
Perchlorates, ClO4-,
Permanganates,MnO4-
Acetate ion, CH3COO- No common exception
SOLUBILITY TABLE:
Generally soluble in water Exceptions, Insoluble

Chlorides, Cl- AgCl, Hg2Cl2,PbCl2
Bromides, Br- AgBr, Hg2Br2,PbBr2
Iodides, I- AgI, Hg2I2, PbI2
Fluorides, F- SrF2, CaF2 BaF2, PbF2 MgF2
Sulphates, SO42- Ag2SO4, HgSO4, PbSO4,
SrSO4, CaSO4,, BaSO4
SOLUBILITY TABLE:
Generally insoluble in water Exceptions
Sulphides, S-2 Na+, K+, NH4+, Mg2+, Ca2+
Oxides, O-2, Hydroxide, OH- Na+, K+, NH4+, Li+, Ba2+,
Sr2+
Carbonate, CO32- Na+, K+, NH4+

Phosphate, PO42-, Arsnates,
AsO43-
Oxalates, C2O42- Na+, K+, NH4+
Chromates, CrO 2-
Na+, K+, NH +
EXAMPLES OF THE COMPOUNDS THAT
ARE NOT SOLUBLE IN WATER
AlPO4 Cu3(PO4)2
AgCN CuSCN
CdS Bi2S3
BaSO4 Zn3(ASO4)3
SrCO3 Mn(lO3)
PbCrO4 Ag2CrO4
Fe(OH)3
PbBr2 Hg2Br2
THE SOLUBILITY PRODUCT CONSTANT
Unlike in the previous sectons where we worked with
the homogeneous mixtures (acid-base soln), in this
secton we are going to work with the
heterogeneous mixture, viz precipitaton reactons.
Precipitaton reacton is an exchange reacton in
which one product is soluble in water while another
one is not soluble in water.
The compound having the water solubility of less than
0.01M, is said to be insoluble in water.
THE SOLUBILITY PRODUCT CONSTANT
• The solubility product constant , is the equilibrium
constant for the extent of the solubility of
insoluble solid substance in aqueous soluton. That
is, it represent the extent to which insoluble salt is
dissolved in aqueous soluton.
• It is indicated by ksp
• It difer from the solubility because the solubility is
a certain amount of solute in a solvent or in a
soluton.
• Example are molality, molarity, etc.
SOLUBITLITY OF SALTS
Example of such reactons is:
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
In this case AgCl(s) is a precipitate.
That is; its solubility is less than 0.01M (mol/L).
Although this is not soluble in water, it can dissolve to
a certain extent in water to form:
AgCl(s) ) → Ag+ (aq) + Cl-(aq)
THE SOLUBITLITY PRODUCT
CONSTANT
As in the case of AgCl, the solubility of AgBr is also
less than 0.01M.
If some AgBr is placed in pure water, a smallest
amount of this salt dissolves, and equilibrium is
established.
SOLUBITLITY OF SALTS
Calculate Ksp of the following reacton:
AgBr(s)↔ Ag+(aq, 7.35 x 10-7M) + Br-(aq, 7.35 x 10-7M)
The solubility equilibrium constant Ksp:

ksp = [Ag+][Br-]
=(7.35 x 10-7) (7.35 x 10-7)
=5.4 x 10-13
AgBr(s)↔ Ag+(aq) + Br-(aq,) Ksp = 5.4 x 10-13
When AgBr has dissolved and equilibrium is atained,
the soluton is said to be saturated.
CONSTANT, ksp
The solubility and the solubility product constant of a
compound should not be confused:
The solubility of a compound is the quantty of solute
present in a certain volume of solvent or soluton,
expressed in moles per litre, moles per kilograms,
grams per 100mL, etc.
The solubility product constant of a compound is the
solubility constant (it has no units).
CONSTANT, ksp
That is, it is the product of the concentratons of the
ions formed from the insoluble salts raised to the
power of their numerical coefcients.
Although the solubility and the solubility constant
difer from each other, the knowledge of one can
be used to calculate the other one.
THE SOLUBITLITY PRODUCT CONSTANT, ksp
The solubility product constants (ksp) are determined

by careful laboratory measurement of the
concentraton of the ions and are listed in Appendix L.
For an example:
Calcium fuoride (CaF2) dissolves to a slight extent in
water.
Calculate the ksp value for CaF2 if the calcium ion
concentraton has found to be 2.3 x 10-4 mol/L.
TEST ON RELATING SOLUBITLITY AND ksp
Calculate the ksp value for CaF2 if the calcium ion
concentraton has found to be 2.3 x 10-4 mol/L.
Soluton:
Write down an equilibrium chemical equaton
containing Ksp.
Calculate the fluoride ion concentraton from calcium
ion concentraton and get the ksp.
CaF2(s)↔Ca2+(aq)+2F-(aq) ksp = [Ca2+][F-]2
From the stoichiometric equaton; for every mol of
CaF2 that dissolves in water, one mole of Ca2+ and
two moles of F- are formed.
If [Ca2+] = 2.3 x 10-4.mol/L., then
The concentraton of F- is
[F-1] = 2(2.3 x 10-4 mol/L.)
=4.6 x 10-4.mol/L.
CaF2(s) ↔ Ca2+(aq) + 2F-(aq)
ksp = [Ca2+][F-]2
=[2.3 x 10-4 ][4.6 x 10-4]2
= 48.668 x 10-12
= 4.9 x 10-11
RELATING SOLUBITLITY AND ksp
• The Ksp of insoluble salts can be used to estmate
solubility of solid salt and determine weather a solid
will precipitate when the soluton of its anion and
caton are mixed.
Queston1
Which of BaSO4 and MgF2 is more soluble at 25oC?
Soluton
*The ksp of BaSO4 at 25oC is 1.1 x 10-10.
*Calculate the solubility of BaSO4 in pure water in
mole per liter and in gram per liter.
*The ksp of MgF2 at 25oC is 5.2 x 10-11
*Calculate the solubility of MgF2 in pure water in
mole per liter and in gram per liter.
*Write down the balance equaton and the ksp
expression for each salt.
*Set up an ICE table designatng the unknown

concentraton of Ba2+ and SO42- as x and x respectvely.
*Set up an ICE table designatng the unknown

concentraton of Mg2+ and F- as x and x respectvely.
BaSO4(s) ↔ Ba2+(aq) + SO42-(aq)

Inital (M))
Change (M)) +x +x
Equilibrium (M)) x x
Therefore: Ksp = [Ba2+][SO42-]
1.1 x 10-10 = (x)(x)
= x2
x2 = 1.1 x 10-10
 10
x  1.1x10
= 1.0 x10-5
[BaSO4] = 1.0 x10-5
= The solubility of BaSO4
To calculate this solubility in g/L, one may apply

dimension analysis:
5
1.0 x10 molBaSO4 233g
?g /L  x
1L 1molBaSO4
= 0.0024g/L
Therefore the concentraton of BaSO4 in mol/L is
= 1.0 x10-5M
and the concentraton of BaSO4 in g/L is
= 0.0024g/L
For MgF2:
Calculate the solubility of MgF2; if the ksp of MgF2 is 5.2
x 10-11 in mol per liter and in g per liter.
Soluton:
1. Write the balance equaton and the Ksp expression.
2. Set up an ICE table designatng the unknown
concentraton of Mg2+ and F- as x and 2x respectvely.
3 Apply conversion factors to get the concentraton in
g/L.
1. Write the balance equaton and the Ksp
expression.
MgF2 ↔ Mg2+ + 2F- ksp = [Mg2+][F-]2
= 5.2 x 10-11
concentraton of Mg2+ and F- as x and 2x and get the
value of x.
MgF2(s) ↔ Mg2+(aq) + 2F-(aq)

Inital (M))
Change (M)) +x +2x
Equilibrium (M)) x 2x
Therefore: Ksp = [Mg2+][F-]2
5.2 x 10-11 = (x)(2x)2
= 4x3
4x3 = 5.2 x 10-11
x3 = 1.3 x 10-11
3  11
x  1.3 x10
= 2.4 x 10-4
[MgF2] = 2.4 x 10-4
= The solubility of MgF2
To calculate this solubility in g/L, one may apply

dimension analysis:
4
2.4 x10 molMgF2 62.3 gMgF2
?g /L  x
1L 1molMgF2
= 0.015024g/L
Therefore the concentraton of MgF2 in mol/L is
= 2.4 x10-4M
And the concentraton MgF2 in g/L is
= 0.015 g/L
The ksp value cannot directly be used to compare the
solubility of two or more salts.
For an example, the ksp of BaSO4 = 1.1 x 10-10
and that of MgF2 = 5.2 x 10-11
One may think that BaSO4 is more soluble than MgF2 .

When comparing their solubility's in g/L
For BaSO4 = 0.0024 g/L
and that of MgF2 = 0.015 g/L
This shows that MgF2 is more soluble than BaSO4.
The reason for this is that the caton : anion rato of
BaSO4 is 1 : 1 while that of
MgF2 is 1 : 2.
Ksp values can be used to compare the solubilites of
salts only if they have the same caton : anion
ratos.
For example:
The caton : anion ratos of the following salts is 1:1

and their ksp values can therefore be used to predict
their solubilites.
AgI(Ksp=8.5x10-17)<AgBr(Ksp=5.4x10-13)<AgCl(Ksp=1.8 x 10-10)
Increasing Ksp and increasing solubility
The caton : anion ratos of the following salts is 1:2
and their ksp values can therefore be used to predict
their solubility's.
PbI2(Ksp=8.5x10-9)<PbBr2(Ksp=5.4x10-6)<PbCl2(Ksp=1.8 x 10-5)
Increasing Ksp and increasing solubility
Queston 3:
If the molar solubility of CaF2 at 35oC is 1.24 x10-3
mol/L. What is the ksp at this temperature?
Soluton
CaF2(aq) ↔ Ca2+(aq + 2F-(aq)
x 2x
x= 1.24 x10-3 M
2x= 2(1.24 x10-3 M)
= 2.48 x10-3 M
Queston 3:
If the molar solubility of CaF2 at 35oC is 1.24 x10-3
mol/L. What is the ksp at this temperature?
Soluton
CaF2(s) ↔ Ca2+(aq + 2F-(aq)
Inital (M))
Change (M)) +x +2x
Equilibrium (M)) x 2x
x= 1.24 x10-3 M
2x= 2(1.24 x10-3 M)
= 2.48 x10-3 M
Ksp = [Ca2+ ][F- ]2

Ksp = [1.24 x10-3 ][2.48 x10-3 ]2
= 7.63x10-9
•
Queston 4:
Calculate the solubility of Mn(OH)2 in grams per litre when
bufered at a pH of 7.00. Ksp of Mn(OH)2 is 1.6 x10-12.
Queston 5:
Calculate the solubility product constant for
lead(II)chloride, if 50mL of saturated soluton of
lead(II)chloride was found to contain 0.2207g of
lead(II)chloride dissolved in it.
Queston 4:
Calculate the solubility of Mn(OH)2 in grams per litre
when bufered at a pH of 7.00. Ksp of Mn(OH)2 is
1.6 x10-12.
Soluton.
pH + pOH = 14
pH + pOH = 14
p(OH) = 14.00-7.00
= 7.00
pOH = -log [OH-]
7.00 = -log [OH-]
log [OH] = -7
[OH- ] = 10-7
[OH- ] = 1.0 x 10-7M
Mn(OH)2(s) ↔ Mn2+(aq + 2OH-(aq)
Ksp = [Mn2+ ][OH- ]2
1.6 x10-12 = [Mn2+ ][1.0x10-7 ]2
 12
2 1.6 x10
[ Mn ]  7 2
(1.0 x10 )
[Mn2+ ] = 1.6 x 102M

[Mn(OH)2] = 1.6 x 102M
= solubility of Mn(OH)2 in mol/L
The solubility of Mn(OH)2 in g/L
160molMn(OH ) 2 288.9526 gMn(OH ) 2

?g /L  x
1L 1molMn(OH ) 2
= 14232.4g/L
=1.42x 104g/L
Queston 5:
Calculate the solubility product constant for
lead(II)chloride, if 50mL of saturated soluton of
lead(II)chloride was found to contain 0.2207g of
lead(II)chloride dissolved in it.
Soluton:
PbCl2(s) ↔ Pb2+(aq + 2Cl-(aq)
Ksp = [Pb2+ ][Cl- ]2

0.2207 gPbCl2 1molPbCl2
? molPbCl2  x
1 278.1gPbCl2
= 7.935994247 x 10-4 molPbCl2
50.0mL 1L
?L  x
1 1000mL
=0.05 L
n
C 
V
4
7.935994247 x10 molPbCl2
C
0.05L
=158.7198849 x 10-4 mol/LPbCl2

= 0.0159 mol/LPbCl2
OR
0.2207 gPbCl2 1molPbCl2 1000mLPbCl2

? mol / LPbCl2  x x
50mLPbCl 2 278.1gPbCl2 1LPbCl2
=158.7198849x10-4 mol/LPbCl2
=0.0159mol/LPbCl2
From the stoichiometric equaton; for each of every
mole of PbCl2 that dissolve; one mole of Pb2+ and
two moles Cl- will be formed.
If [Pb2+] = 0.0159 mol/L., then
The concentraton of Cl- is
[Cl-1] = 2(0.0159 mol/L.)
= 0.0318 mol/L.
ksp = [Pb2+][Cl-]2
Ksp = (0.0159) (0.0318 )2
= 1.60787 x 10-5
= 1.61 x 10-5
OR
For each of every mole of PbCl2 that dissolve; one
mole of Pb2+ and two moles Cl- will be formed.
Inital (M))
Change (M)) . 159 2( . 159)
Equilibrium (M)) . 159 . 318
Ksp = [Pb2+ ][Cl- ]2
Ksp = (0.0159 ) (0.0318 )2
= 1.60787x 10-5
= 1.61 x 10-5
FACTORS THAT AFFECT THE
SOLUBILITY OF INSOLUBLE SALTS
There are three factors that afect the solubility of
insoluble salt:
* Common Ion Efect
* Uncommon Ion Efect
Diverse Ion Efect
Salt Efect
* Ion Pair Efect
SOLUBILITY AND THE COMMON ION
EFFECT
This is the efect of the ion that is similar to at least
one of the ions formed from the insoluble salts.
For an example; when adding AgCl to the soluton of
NaCl that is in equilibrium; the equilibrium will shif
to the lef.
That is more AgCl will form because of the presence
of extra Cl- ions.
The common ion decrease the Ksp value of the
insoluble salt.
TEST ON SOLUBILITY AND THE
COMMON ION EFFECT
Queston1:
If a solid AgCl dissolved in water to form 1.00L of a
soluton. What mass of AgCl will dissolve.
Soluton:
1. Write a balanced equaton and the ksp for AgCl.
concentraton of Ag+ and Cl- as x respectvely.
3. Let [Cl-] and [Ag+] be +x at equilibrium.
EFFECT
In water:
AgCl(s) ↔ Ag+(aq) + Cl-(aq)

Inital (M) 0 0
Change (M) +x +x
Equilibrium (M) x x
Therefore: Ksp = [Ag+][Cl-]
1.8 x 10-10 = (x)(x)
= x2
x2 = 1.8 x 10-10
 10
x  1.8 x10
= 1.3 x 10-5
[AgCl] = 1.3 x 10-5 mol/L
In water:
1.3x10  5 molAgCl 143.32 gAgCl

? gAgCl  x
1 1molAgCl
= 186.316 X 10-5 g AgCl

= 1.9 x 10-3 g AgCl will dissolve
COMMON ION EFFECT
Queston1: In NaCl.
If a solid AgCl is placed in a 1.00L of a 0.55M soluton
of NaCl. What mass of AgCl will dissolve.
Soluton:
1. Write a balanced equaton and the ksp for AgCl.
concentraton of Ag+ and Cl- as x and (0.55+x)
respectvely.
3. Let [Cl-] be 0.55+x at equilibrium.
EFFECT
AgCl(s) ↔ Ag+(aq) + Cl-(aq)

Inital (M) 0 0.55
Change (M) +x +x
Equilibrium (M) x 0.55 + x
EFFECT
Ksp = [Ag+][Cl-]
1.8 x 10-10 = (x)(0.55 + x)
The value x is very small compared to 0.55M.

Therefore:
0.55 + x ≈ 0.55
EFFECT
Therefore: 1.8 x 10-10 = (x)(0.55)
= (0.55)(x)
= 0.55x
0.55x = 1.8 x 10-10
x = 1.8 x 10-10
0.55
= 3.33x 10-10M
In NaCl soluton
To calculate the mass in g, one may apply
dimension analysis:
 10
3.33x10 molAgCl 143.32 gAgCl
? gAgCl  x
1 1molAgCl
= 477.2556 X 10-10 g AgCl

In water:
In NaCl:

SOLUBILITY AND THE COMMON
ION EFFECT
The solubility of AgCl in pure water is 1.3 x 10-3M.
But the solubility of AgCl in the presence of Cl- is
3.3 x 10-10M.
This confrms Le chatelier’s principle and clearly
shows that the equilibrium is disturbed by adding
Cl- and the equilibrium shif to the lef (to the
reactant) to counteract the disturbance in order to
establish the new equilibrium.
This results into the formaton of more AgCl and
hence less solubility of AgCl.
SOLUBILITY AND pH (UNCOMMON SALT EFFECT)
This shows the way in which the basicity and/ or the
acidity of an insoluble salt or part of the insoluble salt
afect the solubility of that salt.
We are going to look at the EFFECT OF THE BASIC

ANION ON SALT SOLUBILITY.
EFFECT OF THE BASIC ANION ON SALT
SOLUBILITY
This is the efect of a strong base formed from an
insoluble salt on the solubility of that salt.
For an example: If you have:
AgI(s) ↔ Ag+(aq) + I-(aq)
In this case the efect of I-(aq) on the solubility of AgI(s)
is determined.
EFFECT OF THE BASIC ANION ON SALT SOLUBILITY
Remember:
An acid is a proton donor.
A base is a proton acceptor.
A strong basic anion is an anion that can accept a proton
more easily.
Examples of strong basic anions are: S2-
CO32-
PO43-
CN-
All these are conjugate bases of the weak acid
and they are therefore strong bases.
SOLUBILITY
These basic anions can undergo hydrolysis.
That is, they can accept a proton from the water
molecule.
For example:
S2-(aq) + H2O (ℓ) ↔ HS- (aq) + OH- (aq)

SOLUBILITY
M)ost of the salts of these are insoluble in water.
For example:
PbS
CaCO3
These salts have the solubility of less than 0.01M.
SOLUBILITY
Example:
When dissolving PbS in water you get:
PbS(s) ↔ Pb2+ (aq) + S2-(aq)--ksp= 3.0x 10-28.

This is followed by the hydrolysis of S2- which is a
strong base.
S2-(aq) + H2O (ℓ) ↔ HS- (aq) + OH- (aq) kb=1.0 x 105.
Which decreases the presence of S2- and force the
equilibrium to shif to the right.
SOLUBILITY
PbS becomes more soluble than it is expected.
The concentraton of Pb2+ increases.
This lead to the general conclusion that:
“Any salt containing an anion that is a

conjugate base of a weak acid will dissolve
in water to a greater extent than the given
ksp”
This shows that the salts of the following basic anions
are afected by this factor.
S2-
CO32-
PO43-
CN-
In general:
X-(aq) + H2O (ℓ) ↔ HX (aq) + OH- (aq)
SOLUBILITY
In additon:
“Insoluble salts in which the anion is the conjugate

base of a weak acid, is soluble in strong acids”
It is generally known that if an acid is added to an

insoluble salt, like the salts of the above-mentoned
anion, it dissolves.
SOLUBILITY
Remember:
The ka of the reverse reacton is equal to the reciprocal
of the former equaton: e.g
ka2= 1/ka1
When adding two or more equatons, the ka of the net
equaton is equal to the product of the added
equatons : e.g
knet= k1x k2x k3x etc
Ka, Ka1, Ka2 etc are obtained from Appendix H

For an example:
The dissoluton of CaCO3 in the absence of a strong acid,
gives:
CaCO3(s) ↔ Ca2+(aq) + CO32-(aq) ksp=3.4 x 10-9
When adding a strong acid like H3O+ to a soluton of
CaCO3, This salt will dissolve to a greater extend than
its Ksp.
CaCO3(aq) + 2H3O+(aq) →Ca2+(aq) + H2CO3(aq) + 2H2O(ℓ)
This is shown step by step on the next slide:

CaCO3(s) ↔ Ca2+(aq) + CO32-(aq) ksp=3.4 x 10-9
CaCO3(aq) + 2H3O+(aq) →Ca2+(aq) + CO2(aq) + 3H2O(ℓ)
knet = 1.7 x 108
CaCO3(aq) + H3O+(aq) ↔ Ca2+(aq) + HCO3-(aq) + H2O(ℓ)
1/ka2=1/4.8 x 10-11 = 2.1 x 1010
HCO3-(aq) + H3O+(aq) ↔ H2CO3(aq) + H2O(ℓ)
1/ka1=1/4.2 x 10-7 = 2.4 x 106
Overall reacton:
CaCO3(aq) + 2H3O+(aq) →Ca2+(aq) + CO2(aq) + 3H2O(ℓ)
knet= (ksp)(1/Ka2) (1/Ka1)
knet= (3.4 x 10-9)(2.1 x 1010)( 2.4 x 106) =1.7 x 108
SOLUBILITY
knet is greater than ksp .
Knet > ksp

This confesses that the additon of a strong acid (e.g.
H3O+) to an insoluble salt containing a basic anion
which is the conjugate base of a weak acid, makes
that salt to dissolve to the greater extent than ksp.
Remember that carbonic acid is not stable in air.
It will decompose into water and carbon dioxide.
From the above, we get:
CaCO3(s) ↔ Ca2+(aq) + CO32-(aq
CaCO3(aq) + H3O+(aq) ↔ Ca2+(aq) + HCO3-(aq) + H2O(ℓ)
HCO3-(aq) + H3O+(aq) ↔ H2CO3(aq) + H2O(ℓ)
CaCO3(aq)+ 2H3O+(aq)→ Ca2+(aq)+CO2(aq)+ H2O(ℓ) + 2H2O(ℓ)
CaCO3(aq)+ 2H3O+(aq)→ Ca2+(aq)+CO2(aq)+ 3H2O(ℓ)
In contrast:
The additon of a strong acid (e.g. H3O+) to an
insoluble salt containing an anion that is not a
strong basic anion, but a basic anion of a strong
acid, does not make that salt to dissolve to the
greater extent than ksp.
Example:
The solubility of AgCl is not afected by the additon of a
strong acid because Cl- is not a conjugate base of a weak
acid, but is a conjugate base of a strong acid.
It is therefore a weak basic anion and not a strong basic
anion.
SOLUBILITY
AgCl(s) ↔ Ag+(aq) + Cl-(aq) ksp = 1.8 x 10-10
Cl-(aq) + H3O+(aq) ↔HCl(aq) + H2O(ℓ) k<< 1
This shows that this salt is not afected by the

additon of H3O+(aq).
PRECIPITATION REACTION
Precipitaton reacton is the reacton in which
precipitate is formed.
How should one know that the precipitate is going to
form in a partcular reacton.
For an example: How do you know that the
precipitate will form in the following reacton?
In additon to the value of ksp one have to calculate
the value of Q and compare it with the value of Ksp.
Ksp AND REACTION QUOTIENT, Q
Q which is the reacton quotent have to be
calculated and compared with Ksp to decide
whether the precipitaton will occur or not:
Q, the reacton quotent and Ksp, equilibrium
constants are calculated in the same way, but the
diferent is that Ksp works on the equilibrium
reacton only, while Q is used for any reacton
including the reacton that is in equilibrium.
For the reacton:

ksp = [Ag+][Cl-] and
Q = [Ag+][Cl-]
ksp may be given but Q have to be calculated
If Ksp > Q , then the reacton is not yet at equilibrium.
The soluton is not yet saturated and no precipitate
will form.
If Ksp = Q , then the reacton is at equilibrium
The soluton is saturated and no precipitate will
form.
If Ksp < Q, then the reacton is not symmetrically at
equilibrium.
The soluton is supersaturated and the precipitate
will form.
Example1:
• Solid AgCl(s) has been placed in a beaker of water.
Afer some tme, the concentraton of Ag+(aq) and
Cl-(aq) are each 1.2 x 10-5mol/L..
Did the system reach equilibrium? If not, will more
AgCl(s) disolve?
Soluton: Write down a balanced equaton
Calculate the value of Q and compare it with the value
of ksp.
ksp = [Ag+][Cl-] =1.8 x 10-10
Q = [Ag+][Cl-]
= (1.2 x 1 -5 )(1.2 x 1 -5 )
=1.4 x 10-10
Ksp > Q , the reacton is therefore not yet at
equilibrium.
The soluton is not saturated and no precipitate will
form. M)ore of AgCl(s) will dissolve.
Ksp > Q,this is therefore a product favour reacton.
Ksp , THE REACTION QUOTIENT
AND PRECIPITATION REACTION
In this secton, if one knows the Ksp or Q and the
concentraton of one ion, the concentraton of
another ion can be calculated.
1. One can tell whether the precipitate will be formed
or not .
2. How much of one or another ion is needed for the
precipitate to form.
Test ON Ksp, THE REACTION QUOTIENT AND PRECIPITATION
Queston 1:
Suppose the concentraton of Mg2+ in an aqueous
soluton is 1.5 x 10-6M. If enough NaOH is added to
make the soluton to have a 1.0 x 10-4 M of OH-, will
the precipitaton of Mg(OH)2 occur. If not so will it
occur if the concentraton of OH- is increased to
1.0 x 10-2 ?
Soluton:
*Calculate Q and compare it with Ksp.
*Calculate Q again afer increasing the concentraton
of OH- and compare it with Ksp.
Test ON Ksp , THE REACTION QUOTIENT AND PRECIPITATIONREACTION
Mg(OH)2(s) ↔ Mg2+ (aq) + 2OH-(aq) ksp = 5.6 x 10-12
Q = [Mg2+][OH-] 2
= (1.5 x 1 -6)(1. x 1 -4 )2
= 1.5 x 10-14
ksp (5.6 x 10-12) >Q (1.5 x 10-14), then the reacton is
not yet at equilibrium.
The soluton is not saturated and no precipitate will
form.
Test ON Ksp , THE REACTION QUOTIENT
AND PRECIPITATIONREACTION
Q = [Mg2+][OH-] 2
= (1.5 x 1 -6M) )(1. x 1 -2 )2
= 1.5 x 1 -8
ksp (5.6 x 10-12) < Q (1.5 x 10-8), the reacton is not at
dynamic equilibrium. It is reactant favored.
The soluton is supersaturated and precipitate will
form.
Test ON Ksp , THE REACTION QUOTIENT AND
PRECIPITATIONREACTION
Queston 2:
25.0mL of a 2.0x10-3M soluton of potassium chromate
is mixed with 75.0 mL of 1.25 x10-4M lead (II) nitrate
soluton. Will a precipitate of lead(II) chromate form?
ksp of lead(II) chromate is 1.8 x 10-14.
Soluton
*Write down the overall and the net ionic equatons that
occurs when the two solutons are mixed.
*Write down the equilibrium expression.
* Use diluton equaton to determine the concentraton of
each species
K2CrO4(aq) + Pb(NO3)2(aq) ↔ PbCrO4(s) + 2KNO3(aq)
Pb2+ + CrO42-(aq) ↔ PbCrO4(s)
PbCrO4(s) ↔ Pb2+ + CrO42-(aq)
Ksp = [Pb2+][CrO42-]
The [Pb2+]= [Pb(NO3)2 ] in the fnal soluton.

The [CrO42- ]= [K2CrO4] in the fnal soluton.
The concentraton of K2CrO4 in the fnal soluton:
C1V1 = C2V2
(2.0x10-3M )(25.0mL) = (C2)( 100.0 mL)
C2 = 5.0 x 10-4M
The [CrO42- ]= 5.0 x 10-4M in the fnal soluton.
The concentraton of Pb(NO3)2 in the fnal soluton:
C1V1 = C2V2
(1.25 x10-4M )(75.0mL) = (C2)( 100.0 mL)
C2 = 9.38 x 10-5M
The [Pb2+]= 9.38 x 10-5M in the fnal soluton.
Q = [Pb2+][CrO42-]
Q = [9.38 x 10-5][5.0 x 10-4]

= 4.69 x 10-8
ksp (1.8 x 10-14 ) < Q (4.69 x 10-8 ), the reacton is not at symmetric
equilibrium. It is reactant favoured.
The soluton is supersaturated and the precipitate will form.
TEST ON SOLUBILITY AND THE COMMON ION EFFECT
Queston 3:
Calculate the final concentraton of K+(aq), C2O42-(aq),
Ba2+(aq) and Br-(aq) in a soluton prepared by adding
100.0mL of 0.200M K2C2O4 to 150.0mL of 0.250M
BaBr2 at 25oC.
Given: ksp of BaC2O4 =2.3 x10-8 at 25oC.
Hind: A solid will form at equilibrium.
Soluton:
*Write down a balanced equaton;
*Calculate the number of moles of each reactant.
*Determine the limitng reactant.
*Use the limitng reactant to calculate the number of
moles of each product.
* Use the moles above to calculate the concentraton
of each product in the fnal mixture.
K2C2O4(aq) + BaBr2 ↔ BaC2O4(s) + 2KBr(aq)
2K+(aq) + C2O42-(aq) + Ba2++ 2Br-↔ BaC2O4(s) + 2K+(aq) + Br-(aq)
C2O42-(aq) + Ba2+ ↔ BaC2O4(s)
BaC2O4(s) ↔ C2O42-(aq) + Ba2+
n = CV
n(K2C2O4) = (0.0200mol/L)(0.100L)
= 0.0200mol
n = CV
n(BaBr2) = ( .25 mol/L)( .15 L)
= 0.0375mol BaBr2
0.0200molK 2C2O4 1BaBr2
? molBaBr2  x
1 1molK 2C2O4
= 0.0200mol BaBr2
Therefore: K2C2O4 is a limitng react.
We have 0.0375 mol BaBr2 and we need only 0.02mol.
Excess mol = 0.0375 mol - 0.02mol BaBr2
= 0.0175 mol BaBr2
COMMON ION EFFECT
The total volume = 100.0mL + 150.00mL
= 250.0mL
n
C 
V
2(0.0200mol )
[K ] 

0.250 L
= 0.160M
COMMON ION EFFECT
n
C 
V
2(0.0375mol )
[ Br ] 

0.250 L
= 0.300M
COMMON ION EFFECT
[Ba2+]
n
C 
V
2 0.0175mol
[ Ba ] 
0.250 L
= 0. 070M +x
COMMON ION EFFECT
[C2O42-] = ?
At equilibrium:
BaC2O4(s) ↔ Ba2+(aq) + C2O42-(aq)

Inital (M) 0.070 0
Change (M) +x +x
Equilibrium (M) 0.070 +x +x
0.070 + x ≈ 0.070 Therefore [Ba2+]=0.070M
Ksp = [Ba2+][C2O4 2-]
2.3 x10-8 = (0.070-x)( x)
0.070 + x ≈ 0.070 because x is very small compared to
0.070M
2.3 x10-8 = (0.070)( x)
x = 2.3 x10-8 /0.070 = 3.286 x 10-7M
[C2O4 2-] = 3.29 x 10-7M
[Ba2+] = 0.0700M
Queston 4:
A soluton contains Ca2+ and Ba2+ ions, both at a
concentraton of 0.020 M. You wish to separate the
two ions from each other as completely as possible as
by precipitatng one but not the other using aqueous
soluton of NaSO4 as the precipitatng agent.
(a )Which salt will precipitate first as sodium
sulphate is added, CaSO4 or BaSO4?
(b) What will be the concentraton of the first ion
(Ca2+ or Ba2+) that precipitated, when the second,
more soluble salt precipitate?
(a) Soluton: For Ca2+ : CaSO4(s) ↔ Ca2+(aq) + SO42-(aq)

Ksp = [Ca2+][SO42-]
4.9 x 10-5 = (0.020)( x)
x = 4.9 x 10-5 /0.020
[SO42-] = 2.45 x 10-5M
For Ba2+ : BaSO4(s) ↔ Ba2+(aq) + SO42-(aq)
Ksp = [Ba2+][SO42-]
1.1 x 10-10 = (0.020)( x)
x = 1.1 x 10-10 /0.020
[SO42-] = 5.5 x 10-9M
BaSO4 will precipitate first, as it need less [SO42-] OR
Ksp of BaSO4 < Ksp of CaSO4

therefore BaSO4 will precipitate first
(b) What will be the concentraton of the first ion, (Ca2+
or Ba2+) that precipitated, when the second more soluble
salt precipitate?
(b) Soluton:
Ksp = [Ba2+][SO42-]
1.1 x 10-10 = (x)(2.45 x 10-5M)
x = 1.1 x 10-10 /2.45 x 10-5M
[Ba2+] = 4.49 x 10-6M
[Ba2+] = 4.5 x 10-6M
ST0P 16.8 POLYPROTIC ACIDS AND
BASES
Re member:
Polyprotc acids are acids that have more than one
proton:
There are two types of polyprotc acids
Inorganic polyprotic acids

e.g. H3PO4 Organic polyprotic acids
e.g. CH3CH3CO2H
H2SO4
H2CO3
HS
POLYPROTIC ACIDS AND BASES
The number of H3O+ ions generated during first
ionisaton step of a many inorganic polyprotc acid is
about million tmes more than the second step.
This shows that the pH of many inorganic polyprotc
acid depends primarily on the H3O+ ions generated
during first ionisaton step.
The number of H3O+ ions produced during second
ionisaton step is so small that it can be neglected.
POLYPROTIC ACIDS AND BASES
The same thing applies to the fully deprotonated
conjugate bases of polyprotc acid
The number of OH- ions generated during first
ionisaton step of a many inorganic polyprotc bases
is about million tmes more than the second step.
This shows that the pOH of many inorganic polyprotc
bases depends primarily on the OH- ions generated
during first ionisaton step.
The number of OH- ions produced during second
ionisaton step is so small that it can be neglected.
CALCULATING THE PH OF A
POLYPOLYPROTIC BASE
Example:
The carbonate ion, CO32- is a base in water, forming
the CO32- ion. Which in turn can form H2CO3.
What is the pH of a 0.10 M soluton of carbonate ion,
CO32-?
Soluton:
Write down a balanced equaton for the formaton of
both CO32- and H2CO3.
Include their Kb1 and Kb2.
Set up the ICE table for the reacton of carbonate ion.
CALCULATING THE pH OF THE SOLUTION
OF POLYPROTIC BASES
Calculate the pH of the 0.010M soluton of Na2CO3.
Soluton
Write down the frst and the second ionizaton steps
of the H2CO3.
Insert its Kb1 and the Kb2
Set up the ICE table for the reacton of carbonate ion.
OF POLYPROTIC BASES.
CO32-(aq) + H2O(ℓ)↔ HCO3-(aq) + OH-(aq)- Kb1 = 2.1 x10-4.
HCO3-(aq) +H2O(ℓ)↔ H2CO3(aq) + OH-(aq)- Kb2 = 2.4 x10-8.

CALCULATING THE pH AFTER THE REACTION
OF A WEAK BASE WITH A STRONG ACID
CO32-(aq) + H2O(ℓ)↔ HCO3-(aq) + OH-(aq)-
Inital (M) .1
Change (M) -x +x +x
EQUILIBRIUM (M) .1 -x x x
 _
[ HCO3 ][OH ]
K b1  
[ HCO3 ]
OF POLYPROTIC BASES .
 _
[ HCO3 ][OH ]
K b1  
[ HCO3 ]
4 ( x)( x)
2.1x10 
0.10  x
But .1 – x ≈ .1
OF POLYPROTIC BASES .
2
4 x
2.1x10 
0.10
4
x  2.1x10 x0.10
=4.6 x10-3
x = [HCO3-(aq) ] = [OH-] = 4.6 x10-3M
pOH = -log [OH- ]

= -log (4.6 x10-3)
= 2.34
pH + pOH = 14
pH = 14 –POH
= 14 -2.34
=11.66
CALCULATING THE pH AFTER THE REACTION
OF A WEAK BASE WITH A STRONG ACID
HCO3-(aq) + H2O(ℓ)↔ H2CO3(aq) + OH-(aq)-
Inital (M) 4.6x1 -3 4.6 x10-3
Change (M) -y +y +y
EQUILIBRIUM (M) 4.6x1 -3 -y y 4.6 x10-3 +y
_
[ H 2CO3 ][OH ]
Kb2  
[ HCO3 ]
3
8 ( y )(4.6 x10  y )
2.4 x10  3
4.6 x10  y
But 4.6 1 -3– x ≈ 4.6 1 -3
But 4.6 1 -3 + x ≈ 4.6 1 -3

3
8 [ y ]4.6 x10
2.4 x10  3
4.6 x10
y = 2.4 x 10-8M
= [H2CO3]
This shows that the amount of OH- produced in this is

negligibly small.
STOP Test ON Ksp , THE REACTION QUOTIENT
(b) Soluton:
Ksp = [Ba2+][SO42-]
1.1 x 10-10 = (x)(5.5 x 10-9M)
x = 1.1 x 10-10 / 5.5 x 10-9M
[Ba2+] = 2.0 x 10-2M
[Ba2+] = 2.0 x 10-2M
THE RELATIONSHIP BETWEEN K, 1 AND Q
The relatonship between K and Q can also tell if the reacton is at equilibrium or
not.
If K > Q the reacton is product favored.
If K = Q the equilibrium is symmetrical.
If K < Q the reacton is reactant favored.
OR
If Q < K the reacton is product favored.
If Q = K the equilibrium is symmetrical.
If Q < K the reacton is reactant favored.
In this case K is given and Q have to be calculated.
COMMON ION EFFECT
BaC2O4 is an insoluble salts, its solubility is therefore less
than 0.01M. The value of x is very small compared to
0.070M and 2.7 x10-8 why?
is very small compared to 0.070. Therefore:
0.070 + x ≈ 0.070 Therefore [Ba2+]=0.070M
Ksp = [Ba2+][C2O4 2-]
2.3 x10-8= (0.070)( x)
x = 2.3 x10-8 /0.070
[C2O4 2-] =3.286 x 10-7M
The ksp value cannot directly be used to compare the
solubility of two or more salts.
For an example, the ksp of BaSO4 = 1.1 x 10-10
and that of MgF2 = 5.2 x 10-11
One may think that BaSO4 is more soluble than MgF2 .

When comparing their solubility's in g/L
For BaSO4 = 0.0024 g/L
and that of MgF2 = 0.015 g/L
This shows that MgF2 is more soluble than BaSO4.
EXAMPLES OF RELATING
SOLUBITLITY AND ksp
EXAMPLES OF RELATING
SOLUBITLITY AND ksp

K and The Solubility of Salts: Slide 2 To 9 Is A Revison: Study These On Your Own

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K and The Solubility of Salts: Slide 2 To 9 Is A Revison: Study These On Your Own

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Ksp AND THE SOLUBILITY

If K > 1 the reacton is product favored.

If K > Q the reacton is product favored.

Study the table of names and

Generally soluble in water Exceptions, Insoluble

Carbonate, CO32- Na+, K+, NH4+

The solubility equilibrium constant Ksp:

The solubility product constants (ksp) are determined

CaF2(s) ↔ Ca2+(aq) + 2F-(aq)

*Set up an ICE table designatng the unknown

*Set up an ICE table designatng the unknown

BaSO4(s) ↔ Ba2+(aq) + SO42-(aq)

To calculate this solubility in g/L, one may apply

MgF2(s) ↔ Mg2+(aq) + 2F-(aq)

To calculate this solubility in g/L, one may apply

One may think that BaSO4 is more soluble than MgF2 .

BaSO4 is 1 : 1 while that of

The caton : anion ratos of the following salts is 1:1

Ksp = [Ca2+ ][F- ]2

[Mn2+ ] = 1.6 x 102M

160molMn(OH ) 2 288.9526 gMn(OH ) 2

Ksp = [Pb2+ ][Cl- ]2

=158.7198849 x 10-4 mol/LPbCl2

0.2207 gPbCl2 1molPbCl2 1000mLPbCl2

PbCl2(s) ↔ Pb2+(aq + 2Cl-(aq)

AgCl(s) ↔ Ag+(aq) + Cl-(aq)

1.3x10  5 molAgCl 143.32 gAgCl

= 186.316 X 10-5 g AgCl

AgCl(s) ↔ Ag+(aq) + Cl-(aq)

The value x is very small compared to 0.55M.

= 477.2556 X 10-10 g AgCl

= 1.9 x 10-3 g AgCl will dissolve

= 4.8 x 10-8 g AgCl will dissolve

We are going to look at the EFFECT OF THE BASIC

S2-(aq) + H2O (ℓ) ↔ HS- (aq) + OH- (aq)

PbS(s) ↔ Pb2+ (aq) + S2-(aq)--ksp= 3.0x 10-28.

“Any salt containing an anion that is a

“Insoluble salts in which the anion is the conjugate

It is generally known that if an acid is added to an

Ka, Ka1, Ka2 etc are obtained from Appendix H

This is shown step by step on the next slide:

Knet > ksp

AgCl(s) ↔ Ag+(aq) + Cl-(aq) ksp = 1.8 x 10-10

Cl-(aq) + H3O+(aq) ↔HCl(aq) + H2O(ℓ) k<< 1

This shows that this salt is not afected by the

For the reacton:

Mg(OH)2(s) ↔ Mg2+ (aq) + 2OH-(aq) ksp = 5.6 x 10-12

Pb2+ + CrO42-(aq) ↔ PbCrO4(s)

PbCrO4(s) ↔ Pb2+ + CrO42-(aq)

The [Pb2+]= [Pb(NO3)2 ] in the fnal soluton.

Q = [9.38 x 10-5][5.0 x 10-4]

BaC2O4(s) ↔ Ba2+(aq) + C2O42-(aq)

(a) Soluton: For Ca2+ : CaSO4(s) ↔ Ca2+(aq) + SO42-(aq)

Ksp of BaSO4 < Ksp of CaSO4

Inorganic polyprotic acids

CO32-(aq) + H2O(ℓ)↔ HCO3-(aq) + OH-(aq)- Kb1 = 2.1 x10-4.

HCO3-(aq) +H2O(ℓ)↔ H2CO3(aq) + OH-(aq)- Kb2 = 2.4 x10-8.

pOH = -log [OH- ]

But 4.6 1 -3– x ≈ 4.6 1 -3

But 4.6 1 -3 + x ≈ 4.6 1 -3

This shows that the amount of OH- produced in this is

One may think that BaSO4 is more soluble than MgF2 .

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