WELCOME TO CHEM 1A

UNIT 2: MATTER-CHANGES IN
INORGANIC SUBSTANCES

Topic 2.7

Equilibrium, Ions & Solutions, Solubility

& Precipitation
 ORGANIZER

1.EQUILIBRIUM
2. IONS & SOLUTIONS-
3.SOLUTIONS & PROPERTIES
4.TYPES OF SOLUTION
5.ENERGY CONSIDERATION
6. SOLUBILITY & PRECIPITATION-
1.Equilibrium

a)Reversible Reactions-forward and reverse

aA + bB ⇌ cC + dD

 ReactionQuotient (Q) is an algebraic expression relating

the mole ratio concentrations[ ] of reactants[R] and
products [P] at any time during a chemical reaction.

Q=[C]c[D]d/[A]a[B]b

 Note Q varies with concentrations

b) Dynamic equilibrium is achieved when rate of forward
equals rate of reverse reaction.

 ReactionQuotient (Q) at dynamic equilibrium has a

special name called equilibrium constant Kc defined as:

Kc=[C]c[D]d/[A]a[B]b

 Note Kc is constant

A reaction graph shows the position of equilibrium.

(draw a graph showing how concentrations of reactants and

products vary over time)
Example: The Haber process is run at 450ºc. At this temperature
concentrations measurements were [H2]=2.17 molL-1 ,[N2]=0.725 molL-
1
, [NH3] = 0.256 molL-1..Calculate Kc.

Reaction : N2(g) + 3H2(g) ⇌ 2NH3(g)

Kc=[NH3]2/[N2][H2]3
=(0.256)2/(0.725)(2.17)3
=8.85 * 10-3
c)Solids & Liquids in Equilibria Expressions

 Solidsand solvents are not included in the

equilibrium expressions.

Example 1: For Lead(II) chloride dissolving in water:

PbCl2(s) ⇌Pb2+aq) + 2Cl-(aq)

Because PbCl2(s) is constant kc is defined as

solubility constant,(or solubility product) ks.

Thus ks=[Pb2+][Cl-]2
Example 2: For ethyl ethanoate dissolving in water:

CH3COOC2H5 (aq) + H2O(l) ⇌ C2H5OH (aq) + CH3COOH (aq)

Because [H2O](l) is constant (55.6 molL-1) it is

excluded from calculations of k

Thus k=[C2H5OH][CH3COOH]/[CH3COOC2H5]
Metal solid/aqueous ion equilibria.
 If placed in a solution of their own ions, metals will

establish an equilibrium. For zinc metal placed in a

solution of zinc ions Zn2+(aq)

 Zn(s) ⇌Zn2+(aq) + 2e

 Thus k=[Zn2+]

 Theequilibrium position depends upon the

reactivity of the metals
d)Phase Change Equilibria
 Water in a sealed container will soon reach an equilibrium

with the water vapour saturating the spaces above the

liquid surface

H2O(l) ⇌ H2O(g)

 Solidsand liquids have a compact structure and set

volume and cannot readily be compressed under standard
conditions. Their concentrations are considered constant.

 Becausethe concentration of H2O(l) is constant and is

thus ignored, the equilibrium expression is

k=[H2O(g)]
The effect of solids, liquids and gases on the
equilibrium constant k can be summarised in the
following Table:
Reaction Equilibrium expression

N2(g) + 3H2(g)⇌2NH3(g) Kc=[NH3]2/[N2][H2]3

H2(g) + I2(g)⇌2HI(g) Kc=[HI]2/[H2][I2]

2SO2(g)+O2(g)⇌2SO3 (g) Kc=[SO3]2/[SO2]2[O2]

2CO(g) + 2NO(g)⇌2CO2(g) +N2(g) Kc=[CO2]2[N2]/[CO]2 [NO]2

CaCO3(s) ⇌CaO(s) + CO2(g) Kc=[CO2]

CH3COOH(aq)+H2O(l) ⇌ CH3COO- (aq)+H3O+ (aq) k=[CH3COO-][H3O+]/[CH3COOH]

e)Catalyst & equilibrium
Catalysts are substances which alter the rate of a
chemical reaction without themselves being used up
in the overall reactions.

Because catalysts alter the rate of forward and

reverse reactions equally, there is NO overall effect
on the position of equilibrium.

The equilibrium constant k is not altered by a

catalyst.
f)Factors affecting equilibrium

The equilibrium position is affected by:

 Concentration of reactants or products

 Pressure if any gases are involved

 Temperature
(i)Concentration
 Concentration is the ratio of the quantity of solute

to either the quantity of solvent or to the quantity

of solution

Example . concentration of salt in sea water is

3g/100 g sea-water.

This is a solute-to- solution ratio. This is called the

solutions percentage concentration.

Some concentration units are affected by changes in

temperature.
Temperature- independent units
 Weight Fraction
Wcomponent=mass comp /mass solution

 Weight Percentage (w/w) or parts per hundred

W%=WFraction x 100

Example : 0.9% NaCl means 0.9g NaCl to 100gNaCl

solution
 parts per thousand (ppt)=1g /103g of mixture

 parts per million (ppm)=1g /106g of mixture

 parts per billion(ppb)= 1g/109g of mixture

 Molality-number of moles of solute per kilogram
of solvent(not solution).

Molality (m)=mol of solute/kg of solvent

When water is solvent a solutions molality

approaches its molarity ( density of water is 1g/ml)

In other solvents molality is not equal to molarity

Example: 1mol Br2 fills up 680 mL CCl4

Problem 1: what is the molality of 10.0% aqueous
NaCl?

Solution: 10.0g NaCl/100.0 g NaCl sol

to
?moles of NaCl/1kgwater

First calculate moles of NaCl in100g sol

10.0gNaCl x 1mol NaCl/58.44gNaCl =0.171 mol

Next calculate kg water in 100g solution but first
subtract mass of solute

(100-10=90 g=0.090kg water)

Thus

molality(m)=0.171mol/0.0900 kg=1.90molal

So 10.0% NaCl =1.90m

Problem 2: A student is asked to prepare 0.150m
solution of sodium chloride in water. What mass of
NaCl is required to dissolve in 500g of water?

Solution:

500g water x 0.150 mol NaCl/1000g water =0.0750

mol NaCl
Now
0.0750 mol NaCl x 58.44g NaCl/1 mol NaCl=4.38g

So 4.38g NaCl dissolves in 500g of water to yeild

0.150molal
Temperature- dependent units

 Molarity(M)- moles of solute per litre of solvent

Molarity (M)=mol of solute/L of solvent

Concentration (c)=moles (n)/volume (v)

OR

c=n/v

 Molarity changes with temperature!

 Calculating molarity from weight % requires density.

Problem 3: A certain supply of concentrated hydrochloric

acid has a concentration of 36.0% HCl. The density of the
solution is 1.19g/ml. Calculate the molar concentration
of HCl(molar mass=36.46)

Solution: 36.0g HCl/100.0 g HCl

to
?moles HCl / 1litre of HCl sol

First calculate moles of HCl in100g sol of 36% HCl

36.0gHCl x 1mol HCl/36.46gHCl =0.987 mol

Next calculate the volume(mLs) of HCl solution in
100g HCl

100.0gHCl x 1mL HClsol/1.19gHClsol =84.0 mL

Thus volume occupied by 100g of 36.0%HCl is

0.0840L

Therefore

Molarity (M)=0.987mol HCl/0.0840 L HCl

=11.8M HCl
Normality
 Useful for acid/base and redox reactions

A concentration unit that expresses the number of

equivalents of solute per litre of solution.

Example:

1 mol HCl = 1 eq HCl

1 mol H2SO4 = 2eq H2SO4 Or 98.07g H2SO4 =2eq

H2SO4
 Normality =equivalents of solute/1L of solution

Example: 2N H2SO4 contains 2eq H2SO4 per litre

 Normality = molarity x no of eq per mol

(ii)Pressure

 Some gases are soluble at high pressure

Example: Oxygen & nitrogen

 Increasing pressure, results in reduction of

volume so some gas particles must go into
solution.(eqm shifts right)

Gas + solvent ⇆ solution

 Lowering pressure on solution results in
equilibrium shift to the left and some dissolve gas
leaves the solution.

Gas + solvent ⇆ solution + pressure

Example??

Opening a can of fizzy drink

(iii)Temperature

 Some solutes dissolve more at high temperatures

( endothermic reactions)

Eg. Solute (undissolved) + heat ⇆ solute (dissolved)

 Other solutes are soluble at low temperature

(exothermic reactions)
Eg. Solute (undissolved) ⇆ solute (dissolved) + heat

NH3 89.9 at 0°C, 51.8 at 20°C,

28.4 at 50°C, 7.4 at 100°C
g) Le Chartelier’s Principle

Le Chartelier’s Principle governs the specific manner

in which these factors (concentration, pressure,
temperature) affect the equilibrium position.

Le Chartelier’s Principle States that ‘if a change is

made to a reaction at equilibrium, the position of
equilibrium alters to oppose the effect of the
change”
2. Ions & Solution.
Ions. Ionic solids are made up of cations and anions.
Important cations are shown in following Table:
Name Symbol Appearace (s) Appearance(aq)
sodium Na+ white colourless
potassium K+ white colourless
ammonium NH4+ white colourless
calcium Ca+2 white colourless
aluminium Al+3 white colourless
Iron(ii) Fe+2 Dark grey- Pale blue-green
green
Iron(iii) Fe+3 Red-brown Yellow-orange
Chromium(iii) Cr+3 Dark blue- Blue-violet
violet
Zinc Zn+2 white colourless
 Important cations continue:
Name Sym Appearace (s) Appearance(aq)
Copper(ii) Cu+2 CuO black insoluble
CuSO4.xH2O blue blue
CuSO4 white blue
Cu(NO3)2.xH2O blue blue
CuCl2.xH2O green Green-blue
CuCO3. Cu(OH)2 Green insoluble

silver Ag+ Ag2O brown insoluble

AgCl white insoluble

AgNO3 white colourless
 The colours of ionic compounds depend on
cation(s) present.
 When copper sulphate dissolves in water it

produces Cu2+(aq)-blue and SO42-(aq)-colourless.

 Cations become hydrated through ion-dipole
attraction
 # of H2O involved depends on size of cation

 Shape of hydrated ions depends on # of H2O

involved

 Example1 [Fe(H2O)6.]3+ is octahedral

 Example 2 [Cu(OH)4.]2+ is tetrahedral

 Important anions are shown in following Table:
Name Symbol Appearace (s) Appearance(aq)
chloride Cl- white colourless
bromide Br- white colourless
sulfide S-2 white colourless
hydroxide OH- white colourless
carbonate CO3-2 white colourless

nitrate NO3- white colourless

sulfate SO4-2 white colourless

chromate CrO4-2 yellow/red yellow

dichromate Cr2O7-2 orange orange

permanganate MnO4- Purple/black purple

thiosulfate S2O3-2 white colourless

bicarbonate HCO3- white colourless

3.Solutions & Properties

a) Definition-Solution: a mixture of a solvent and a

solute

A solution is a homogeneous mixture.

 All
the particles in solutions are very small(0.05-
0.25 nm)

 Solute
particles are larger and regarded as colloid
and suspension.
b) Driving forces

Driving force #1-Randomness

 The spontaneous mixing of liquids as in gases

illustrate one of natures strongest driving forces:

The tendency of a system, left to itself, to become

increasingly disordered

Because of natural motions of molecules the order

state becomes improbable.
Polar Solvents: usually dissolve polar and ionic
substances

Example 1: NaCl(s)-(ordered state) dissolve in H2O to

yield Na+(aq) Cl-(aq)-(disordered state)

Example 2: Sugar(s)-(ordered state) dissolve in H2O

to yield sugar +(aq) sugar-(aq)-(disordered state)
Driving force #2-Solute/solvent Attraction

 Inliquid, attraction forces between particles are a

major factor in solution formation.
Example 1: NaCl(s) dissolve in H2O to yield[Na+∂-
(OH2)] and [Cl- ∂+ H2O] because both NaCl/NaCl ionic
(solute/solute) attraction and hydrogen bonding
between H2O/ H2O (solvent/solvent) are weaker than
ion-dipole attraction(solute/solvent) between [Na+∂-
(OH2)] and [Cl- ∂+ H2O]
Example 2: Iodine(s) readily dissolve in cyclohexane
because both are non-polar covalent and
(solute/solute) attraction is weaker than
(solute/solvent) attraction between I2 and
cyclohexane

This force sometimes work against formation of

solutions when solute particles are strongly held
together
Example 1: Iodine(s) does not readily dissolve in H2O
because both I2/I2 covalent (solute/solute) attraction
is stronger than (solute/solvent) attraction between
I2 and H2O.

Example 2: Sodium Chloride(s) does not readily

dissolve in cyclohexane because it is polar and
(solute/solute) attraction is stronger than
(solute/solvent) attraction between NaCl and
cyclohexane
c) Colligative properties

 These are solution properties which depend only

on total concentration of solute particles.

Example: lowering of freezing points

& raising of boiling points

 When the same amounts of NaCl(s),CaCl2(s) and

glucose,C6H12O6 (s) are dissolved in water, they
produce different amounts of dissolved particles
(i) Lowering Freezing Point

1 mole Glucose 1 mole solute particles

And lowers freezing point of water by 1.86ºC per L of

water ie 0ºC -1.86ºC= -1.86ºC

But 1 mole NaCl(s)  2 mole solute particles thus

lowers freezing point of water by 2 x 1.86ºC= 3.72ºC
per L of water ie = -3.72ºC

And 1 mole CaCl2(s)  3 mole solute particles thus

lowers freezing point of water by 3 x 1.86ºC= 5.58ºC
per L of water ie = -5.58ºC
(ii) Raising Boiling Point

Solutes raise the boiling point by 0.5ºC per mole of

solute particles per kg of solvent.

Thus 1 mole Glucose would raise the boiling point of

1kg water by 100ºC + 0.5ºC =100.5ºC

similarly 1 mole CaCl2(s) would raise the boiling

point of 1kg water by 100ºC + 3 x 0.5ºC =101.5ºC
(iii). Effects of Solute on Pressure of Solutions

Solutes lower the vapour pressure of solutions

Raoult’s Law: The vapour pressure of solution equals

the product of mole fraction of solvent( xsolvent)
and vapour pressure of pure solvent(P°solvent)

Psolution = xsolvent P°solvent

And
ΔPsolution = xsolute P°solvent

Plot Psolution vs xsolvent gives a linear graph

Problem 1: What is the vapour pressure at 23°C of a
solution prepared by dissolving 10.0g of wax(C22H46-
molar mass=311) in 40.0g of CCl4(molar mass=154,
p=100 torr at 23°C)?

Solution: need vp of solution. Need mole fraction of

solute. So calculate:
mole fractions of CCl4 =0.260
mole fraction of C22H46=0.0322
Total= 0.292
XC22H46 =0.0322/0.292=0.110

ΔP=0.110 x 100= 11.0 torr

So presence of wax lowers pressure from 100 torr to 89.0 torr

Dalton’s Law: For two(A,B) or more volatile
components the total vapour pressure is the sum
of the partial pressures of the components.

PTotal = xsolvent A P°solvent A + xsolvent B P°solvent B

The equation contains Raoult’s law as a special case.

Thus if one component is nonvolatile ,it has no
vapour pressure and drops out from Dalton’s
equation
Problem: Acetone dissolves both water and benzene.
Vapour pressure for acetone at 20°C=162 torr

Vapour pressure for water at 20°C=17.5 torr

Assuming mixture obeys Raoult’s law,

what is the vapour pressure of a solution of acetone

and water with 50.0 mol % of each?
Solution: a concentration of 50.0mol% corresponds
to a mole fraction of 0.500.

Thus partial pressures are:

PAcetone= xAce P°Ace =0.500 x 162 = 81.0 torr

Pwater= xwater P°water =0.500 x 17.5 = 8.75 torr

And

PTotal = xacetone P°acetone + xwater P°water

= 89.8 torr
(iv)Effects of Solute on Phase of Solutions

a). Lowering of the freezing point of solution-

freezing point depression (ΔTf).

The solute lowers vapour pressure and the triple point value.

ΔTf = molal point depression constant x molality

= Kfm

Note Kf for water is 1.86°C/m. This means that 1.00m solution

of water now freezes at 1.86°C below 0°C.
(v) Elevates the boiling point of solution- boiling point
elevation(ΔTb)

The solute increases the boiling point value.

ΔTb= molal boiling point elevation constant x molality

= Kbm

Note Kb for water is 0.51°C/m. This means that 1.00m solution

of water now boils at 0.51°C above 100°C.
Problem 1.Estimate the freezing point of an
antifreeze solution made up of 100.0g of ethylene
glycol, C2H6O2 (molecular mass 62.07), and 100.0g
water (molar mass 18).

Solution: First calculate molality (moles/kg solvent)

of solution.
100.0g C2H6O2 x 1 mol C2H6O2/62.07gC2H6O2=1.611mol

So molality=1.611mol/0.1000kg=16.11m

Now ΔTf = Kfm=(1.86°C/m)(16.11m) = 30.0°C.

Thus solution is expected to freeze at - 30.0°C

Problem 2: A solution made by dissolving 5.65g of a
unknown molecular compound in 110.0g of
benzene(mp 5.45°C, Kf=5.07°C/m) froze at 4.39°C.

What is the molecular mass of the solute?

Solution: First calculate ΔTf

Now ΔTf =(5.45°C)- (4.39°C)=1.06 °C

And molality = ΔTf /Kf=1.06 °C/5.07°C/m=0.209m

so solution contains 0.209 mol solute /kg
benzene
and
mol of sample solute (same as 5.65g of solute)
=0.110kg benzene x 0.209 mol solute/1 kg benzene
=0.0230 mol solute

So molecular mass= 5.65g/0.0230 mol=246g/mol

Thus the molecular mass of the solute is 246g/mol

d) Conductivity of solutions

 High conductivity indicates the presence of a

strong electrolyte.
 Strong electrolytes undergo total dissociation to

give high concentrations of ions which conduct

electricity.

 Examples
of strong electrolytes: soluble ionic
compounds, molten ionic salt, polar substances

 Examples
of weak electrolytes: soluble ionic
compounds, molten ionic salt,polar substances
e) Solutions & pH,

 H+ionsdo not exist on their own in solutions they

react with H2O to form H3O+

 pH is a measure of concentration of H+ or H3O+

pH=-log[H3O+]

Thus when [H3O+] >[OH-] acidic solution pH<7

[H3O+]=[OH-]neutral solution pH=7
[H3O+] <[OH-acidic solution pH>7
f) Species in Solutions

 When substance dissolve in water they release

species which either:
Associate but do not react with H2O-unreactive
ions
OR
React chemically with H2O-hydrolysis
(i) Consider Unreactive ions

Example1: Unreactive ions are group 1&2 cations,

halides, sulfates, nitrates
NaCl(s)Na+(aq) + Cl-(aq)

Example 2: Other unreactive ions are those released

by strong acids and strong bases

HCl(l)H+(aq) + Cl-(aq)

NaOH(s) Na+(aq) + OH-(aq)

Dissolving of unreactive ions is purely a physical

process
(ii) Consider Unreactive molecules

Example1: Unreactive carbohydrate molecules such

as sucrose, do not hydrolyse water
C12 H22O11(s) C12 H22O11(aq)

Example 2: Glucose

C6 H12O6(s) C6 H12O6(aq)

Dissolving of unreactive molecules is purely a

physical process
(iii) Consider acid Salts- from a strong acid & weak
base

Example 1: Ions from some Salts undergo hydrolysis-

form hydronium ions in a chemical process. Consider
ammonium chloride(formed from HCl & NH3)

Salt first dissolves(physical)

NH4Cl(s)NH4+(aq) + Cl-(aq)

than reacts with H2O ((hydrolysis- chemical process)

NH4+(aq) ⇆ NH3 (aq) + H+(aq)-solution is acidic

(iv) Consider alkaline Salts- from a weak acid &
strong base

Example 1: Ions from these salts undergo hydrolysis-

form hydroxyl ions in a chemical process. Consider
sodium sulphide (formed from H2S & NaOH)

Salt first dissolves(physical)

Na2S(s)2Na+(aq) + S2-(aq)

than reacts with H2O ((hydrolysis- chemical process)

S2-(aq) + H2O (l) ⇆ HS-(aq) + OH-(aq)

Example 2: Consider sodium ethanoate (formed
from CH3COOH & NaOH)

Salt first dissolves(physical)

CH3COONa(s)Na+(aq) + CH3COO-(aq)

than reacts with H2O ((hydrolysis- chemical process)

CH3COO-(aq)+ H2O (l) ⇆ CH3COOH (aq) + OH-(aq)

solution is basic
(v) Consider hydrolysis of molecules

Example 1: hydrolysis of molecules-form hydronium

or hydroxyl ions in a chemical process. Consider
HCl(g), SO3(g),CH3COOH(aq), NH3(aq),

Salt first dissolves(physical)

HCl(g)H+(aq) + Cl-(aq)

than reacts with H2O ((hydrolysis- chemical process)

H+(aq) ⇆ H3 O+ (aq) + H+(aq)

solution is very acidic
g)Summary of Effects of dissolving in water
h) Properties & Composition

 Comparing concentrations using colligative,

conductivity,pH,properties using same
amount( 0.1mol, 1L,) construct a graph

(i) consider neutral molecular solution- no other

species are produced.

Note mol H2O =1000g/18g mol-1=55.55 mol

[H2O] =55.55 mol/1L =55.55mol/L

Example 1: Consider 0.1MC2H5OH(aq),neutral
molecular solution
No reaction of product with water. solution is
neutral. .(note: 0.1 mol of products formed)
Example 1: Consider 0.1MHCl(g), strong acid
No reaction of product with water. solution is acidic
because 0.1 M has been added to water.(note: 0.2
mol of products formed)
Problem : Account for species in solution when the
following substances dissolve in water:

❑a) NaCl(s)
❑b) CaCl2
❑c) NaOH(s)
❑d)NH4Cl(s)
❑e)CH3COOH(s)
❑f) NH3(g)
❑g) CH3COONa(s)
4.Types of Solutions

a).Liquid/Liquid- Solutions are formed when

strengths of intermolecular attractions in solutes
and solvents are similar. ”Like –dissolves- like”
rule.
Miscible liquids form solutions. Immiscible liquids
do not form solutions.

Example: ethanol is miscible in water because

both liquids are polar. Benzene is non-polar and
thus immiscible in water.
b) .Solids/Liquids- Two factors :solutions are formed
when:

(i). polar solutes dissolve in polar solvents.ie- Like

dissolves like rule still applies.

Solvation-surrounding of solute particles by

solvent molecules.

Example: hydration of sodium ions, Na+

(ii). A change in potential energy, enthalpy (ΔH)
between separation of ions during bond severing
phase and ions attraction solution phase.

(ΔH)sol= (H)sol- (H)components

c).Gases/Liquids

 Formationof gas/liquid solution is usually

exothermic when water is solvent.

 Onlythe solvent molecules need a little expansion

requiring a small amount of energy

 The net heat of solution depends on the strength

of attraction between gas and solvent molecules

Example: For strong attraction potential energy is

lowered thus solution formation potential is
exothermic
5. Energy Consideration
 Lattice energy = energy supplied(endothermic) to separate
ions in a solid to gas phase.

Eg. KI(s)→K+(g) + l-(g) (ΔH)L=+632 kJ/mol (step1)

 Solvation energy-potential energy(exothermic) due to attraction of
ions in the formation of solution.

Eg. K+(g) + l-(g) → K+(aq) + l-(aq) (ΔH)S=-619 kJ/mol (step2)

 Solution energy-Net: KI(s)→ K+(aq) + l-(aq)

(ΔH)sol= (ΔH)L + (ΔH)S =13 kJ/mol (step3)

Two cases for Liquid/liquid solutions:

1.Ideal Solution : (ΔH)sol= 0

In ideal solution all attractive forces are equal.

Expanded solute and solvent steps are endothermic while
mixing solute/solvent step is exothermic.

The sum of energy output of steps 1 & 2 is equal to step 3

Δ H1 + ΔH2= -ΔH3
2.Real Solutions: (ΔH)sol≠ 0
For some solutions, the sum of energy output of
steps 1 & 2 is less than for step 3 thus (ΔH)sol<0

Example: in a mixture of acetone and water-acetone

molecule attracts water molecules more.

For other solutions, the sum of energy output of steps 1 &

2 is greater than step 3 thus (ΔH)sol>0

Example: In a mixture of Ethanol and hexane-ethanol

molecules attract each other more than they attract the
hexane molecules.
6. Solubility
a)Solubility for strongly hydrated gas:

 The more soluble gases react with water as follows:

CO2(aq) + H2O ⇆ H2CO3(aq) ⇆ H+(aq) + HCO3-(aq

SO2(aq) + H2O ⇆ H+(aq) + HSO3-(aq

NH3(aq) + H2O ⇆ NH4+(aq) + OH- (aq)

SO3(g) + H2O ⇆ H2SO4 (aq

b) Dissolution Reactions & Solubility Product.
❑Dissolution reactions involve dissolving substances
in solvents
❑Consider a sparingly soluble salt AxBy dissolved in
water.
❑At equilibrium: AxBy(s) ⇌ xAy+ (aq) + yBy-(aq)

❑The Quotient Q=[Ay+]X [BX-]y at any time

❑The solubility product Ks(AB)=[Ay+]X [BX-]y at

equilibrium

Study as in Next Test

c) Ks expressions-

 For AB,
ratio- cation : anion=1:1

Eq expression AB(s) : AB(s) ⇌ A+ (aq) + B-(aq)

Ks expression Ks(AB)=[A+] [B-]

Example: CaSO4(s) ⇌ Ca2+(aq) + SO42-(aq)

Ks(CaSO4)=[Ca2+] [SO42-]
d) Ks expressions-

 For A2B,
ratio- cation : anion=2:1

Eq expression AB(s) : A2B(s) ⇌ 2A+ (aq) + B2-(aq)

Ks expression Ks(A2B)=[A+]2+ [B2-]

Example: Ag2SO4(s) ⇌ 2Ag2+(aq) + SO42-(aq)

Ks(Ag2SO4)=[Ag+]2 [SO42-]
e) Ks expressions-

 For AB2,
ratio- cation : anion=1:2

Eq expression AB2(s) : AB2(s) ⇌ A2+ (aq) + 2B-(aq)

Ks expression Ks(AB2)=[A2+] [B-]2

Example: Ca(OH)2(s) ⇌ Ca2+(aq) + 2OH-(aq)

Ks(Ca(OH)2=[Ca2+] [OH-]2
f) Solubility-expressed in g/L or mol/L or
g/100gH2O

Mass and mole calculations: n=mass/molar mass

Problem: What is the concentration of silver chloride

when 1.435g of the compound dissolves in 1litre of
water?
solution
mole =1.435g/143.5g/mol =0.01
Solubility=0.01mol/L
g) Solubility-of AB compounds

Calculated from Ks value

[A]=[B]=x so ks=x2
Hence x=( ks(AB))1/2 mol/L

h) Solubility-of A2B & AB2 compounds

Calculated from Ks value by first dividing by 4 then
taking the cube root of the solubility product of the
compound.

Hence x=( ks/4)1/3 mol/L

7. Precipitation.

a) Ionic Product.
 If ionic Product (IP)> Ks-precipitation occurs
 If ionic Product (IP)= Ks-saturated solution
 If ionic Product (IP)< Ks-no precipitation
b)Saturated solution & Solubility Products(Ks) of
salts:

A saturated solution at a given temperature is

formed when a salt is added to water until no more
can dissolve.

Example: A saturated solution of barium sulfate can

be represented by :

BaSO4(s) ⇆ Ba2+ (aq) + SO42-(aq)

So Ks=[Ba2+][SO42-] is true only for saturated
solutions.

If Ks<[Ba2+][SO42-] indicates solution

oversaturated(ppt can form)

if Ks>[Ba2+][SO42-] indicates solution is unsaturated

Problem: The solubility product of Cu(OH)2 is
4.8 x10-20.Calculate the solubility of Cu(OH)2 .

Solution:

Cu(OH)2(s) ⇆ Cu2+ (aq) + 2OH-(aq)

So Ks=[Cu2+][OH-]2 Let [Cu2+] =x, [OH-]=2x

4.8 x10-20=(x)(2x)2

Therefore x= (4.8 x10-20/4)1/3

=2.29 x 10-7 molL-1
c)Common Ion effect reduces solubility of a salt

The solubility of a salt AB is reduced if it is added to

a solution that already contains A+ or B- ions

Example: AgCl(s) ⇆ Ag+ (aq) + Cl-(aq)

Ks=[Ag+][Cl-]
When aqueous NaCl is added [Cl-] increases and
eqm shifts to reactant side and more ppt forms.

Adding more AgCl(s) will not dissolve since [Ag+]

and[Cl-] are already at maximum.
d) effect of pH change on solubility

For any solution [H+][OH-] = 1 * 10-14

When a solute reacts with either H+ or OH- ions its

solubility is greatly affected by pH.

Example: For Ca(OH)2 ks =4 * 10-6 at 25ºC. Thus its

solubility x=( ks/4)1/3 mol/L= 1.0 * 10-2 mol/L at
pH= 12.3
At pH=13, [H+]= 1.0 * 10-13 and [OH-] =1.0 * 10-1
Since IP=Ks and Ks=[Ca2+][OH-]2

Thus [Ca2+]=Ks/[OH-]2
= 4 * 10-6 / 1.0 * 10-2
= 4 * 10-4 mol/L

For an increase of pH of (12.3/13), Solubility has

decreased by 1.0 * 10-2 /4 * 10-4 mol/L/ =25 times
 THANK YOU FOR LISTENING

Do tutorial 2.7 questions in study guide

Experiment 9- Chemical Equilibrium