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12.

2 Solubility

and Factors Affecting Solubility

Dr. Fred Omega Garces


Chemistry 200
Miramar College

Solubility

January 13

Properties of Solution
Characteristics:
Distribution of particles is uniform
Components in solution do not separate upon standing
Components cannot be separated by filtration.
Solute / Solvent mixes in ratios - up to the solubility limit.
Solution is almost always transparent.
Compounds of solution may be separated by other
methods i.e., distillation or chromatography.

Solubility

January 13

Suspended in Solution: Solubility Process


Solubility - The process in which substances dissolve at the molecular level.
Solubility - The maximum mass of solute capable of dissolving in a given
amount of solvent at a given temperature.

Unsaturated

A solution that has


the capacity to
dissolve more solute.

Saturated

A solution that contains


the maximum solute it
can dissolve. (There are
no residue)

A solution that contains


more solute (in dissolved
form) than the solubility
limit

Immiscible - When
two liquids are not
soluble in each other

Miscible - When two


liquids are soluble in
all proportion.

supersaturated

Solubility

January 13

1) Nature of Solute and Solvent


Dissolving Process: Why is water soluble in alcohol
yet water is insoluble in oil ?
Solubility Factor:
Solute and Solvent characteristic:
In aqueous solution, water will form strong
intermolecular forces with only other polar molecules
(the dissolution process)
Oil is a nonpolar substance and therefore will only
form strong IMF with other nonpolar substances
such as organic compounds.

An oil layer floating on water. For


a substance to dissolve, the
water-water hydrogen bonds must
be broken to make a hole for
each solute particle. However,
the water-water interactions will
break only if they are replaced by
similar strong interactions with
the solute.

The result is the immisciblity of water and oil.


(Later the Energetics of this process will be discuss)

Organic Chemist saying


Like Dissolves Like

Solubility

January 13

Dissolution of Solid Solute


What is the driving force which causes solutes
to dissolve to form solutions?
Covalent versus Ionic solute
1. Covalent solutes dissolve by H-bonding to water or by
2. Ionic solutes dissolve by dissociation into their ions.

LDF

Ionic

Covalent

Picture of Ethanol and NaCl dissolving


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Solubility

January 13

Dissolving at the molecular Level: Ionic Compounds


Ionic substances NaCl, MgCl2, AgCl

The salt; NaCl or the ionic compound is a 3-D lattice.

The Na+ and Cl- are


arranged in 3-D
alternating ion lattice

The negative Cl- attracts the (+) of hydrogen


in H2O while the positive Na+ attracts the ( -)
of oxygen in H2O. Occurs due to coulombic
(opposite) attracts.

The solvent (H2O)


interaction to the ion is
the Hydration process

H2O literally pulls the lattice arrangement of the solid salt apart because of the attraction
between the + or - of water to the - or + ions.
Consider:
1) M+ & X- (i.e., Na+ and Cl - )
2) M+ to - oxygen of H2O & X- to + hydrogen of H2O

If (1) is favorable (lattice energy) then solute does not dissolve (insoluble) i.e., AgCl
if (2) is favorable then hydration, solute does dissolve (soluble). NaCl
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Solubility

January 13

Equilibrium:
Dissolution = Crystallization
Observe: After some
time, no change in
amount of solid
precipitate at the
bottom of the beaker.
Concentration of the
solution is maintained

[Solute]

D
Solid

[Solute]

Solution
Solubility

At the molecular level:


Amount of salt
dissolving into solution
equals to amount of
salt recrystalizing
January 13

Dynamic Equilibrium
Equilibrium
Situation in which changes occur at equal rates so there is no
apparent net change.

LeChatelier Principle
A change (stress) on a system at equilibrium will cause the
system to self adjust itself to reduce the stress until a new
equilibrium is re-established.

Example:
Traffic at a toll bridge
Vapor Pressure
Sugar dissolving
13_07

Solubility

January 13

Ionic Vs Covalent Compounds: Electrolyte


Vs. Nonelectrolyte
Substance when dissolve can break-up to ions or stay
intact. i.e., NaCl and sugar.
Type:

% ionization:

Solubility (in H2O)

Electrolyte: conducts electricity.


Strong electrolyte

100 % ionization

Weak electrolyte

less 100% ionization

very soluble
slightly to very soluble

Nonelectrolyte: Do not conduct electricity


no conduction

0 % ionization

Solubility

insoluble or soluble

January 13

Dissolution at the molecular level?


Spontaneity of dissolving process:

Consider the Spontaneity due to Gravity:


Object drops and impact floor spontaneously.
The driving force is gravity.
High Energy
Objects
spontaneously
fall because of
the tendency
for systems to
be at a lower
energy state.

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When systems proceed to


a lower energy state, the
process is exothermic:
Energy is released.
(Tends to be spontaneous)
Low Energy
Solubility

January 13

Driving Force for Dissolution


Reaction exothermic H (-)
Downhill g Spontaneous
Reaction exothermic H (+)
Uphill g Spontaneous ???

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Solubility

January 13

Dissolution at the molecular level?


Consider the dissolution of NaOH in H2O

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Solubility

January 13

Exothermic: Dissolution Process


Solution process as
indicated by the
enthalpy heat of
solution: Dissolution
via Hsoln can be
thought of as the
sum of three
enthalpy changes;
Hsolvent, Hsolute and
Hmix. The result is
Hsolution.
Note, If Hsoln < O,
Then it is a downhill,
Spontaneous

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Solubility

January 13

Hmix or Hhydration
Closer Look, Hmix:
Hhydr is

always negative

based on Columbs Law.


E = k |Q1Q2|
d
Trends in ionic heats of hydration.
Heats of hydration (Hhydr) are always
negative because ions and water attract
each other and release heat. Values for
the Group 1A(1), 2A(2), and 7A(17) ions
are shown as descending posts, with the
ionic radius on top. The Hhydr values
depend on charge density smaller down a
group as ionic size increases and larger
from Group 1A(1) to Group 2A(2) as ionic
charge increases.
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Solubility

January 13

Consider the Dissolution of NH4Cl


In the dissolution of ammonium chloride,NH4Cl, the
system feels cold, indicating an Endothermic process.

An uphill
process that is
spontaneous.
How is this
possible ?

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Solubility

January 13

Endothermic, Dissolution Process


Hmix small, Hsoln (+)

Down hill (Exothermic) vs. up hill (Endothermic)

Will an unfavorable process (uphill) proceed spontaneously ?


Will a substance dissolve if Hsoln g (+)
When a solute and
solvent mixes, the
magnitude of three
H processes will
determine if the
dissolution process
is exothermic, or
endothermic.
Factors
determining
spontaneity will be
determine by
thermodynamic
factors and not
only by enthalpies
value
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Solubility

January 13

Second Law of Thermodynamics


Why does ink spread or gas expand or your
room gets chaotic?
Greater probability of disorder than order.

One of the Basic Law of Nature


2nd Law of Thermodynamics:
Process in which disorder increases
occur spontaneously

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Solubility

January 13

Enthalpy Diagram for


Series of Dissolution Processes
NaCl in H2O

NaOH in H2O

NH4NO3 in H2O

Enthalpy diagrams for


dissolving three ionic
compounds in water. The enthalpy
diagram for dissolving an ionic
compound in water includes the negative
of the Hlattice (Hsolute; always positive)
and the heat of hydration (Hhydr; always
negative). A, For NaCl, the magnitude
of Hlattice is slightly greater than that of
Hhydr, so Hsoln is small and positive.
B, For NaOH, Hhydr dominates, so
Hsoln is large and negative. C, For
NH4NO3, Hlattice dominates, so Hsoln is
large and positive.

NaCl in Heptane

Hexane in Heptane

Enthalpy diagrams for dissolving


NaCl and octane in hexane. A,
Since attractions between ions and hexane
molecules are weak, Hmix is much
smaller than Hsolute. Thus Hsolute is so
positive that NaCl does not dissolve in
hexane. B, Intermolecular forces in octane
and in hexane are so similar that Hsolute is
very small. Octane dissolves in hexane
because the solution has greater entropy
(more disorder) than the pure components.

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Solubility

January 13

Factors Affecting Solubility


1. Nature of Solute / Solvent. - Like dissolves like (IMF)
2. Temperate Factor i) Solids/Liquids- Solubility increases with Temperature
Increase K.E. increases motion and collision between solute /
solvent.

ii) gas - Solubility decreases with Temperature


Increase K.E. result in gas escaping to atmosphere.

3. Pressure Factor i) Solids/Liquids - Very little effect


Solids and Liquids are already lose together, extra pressure will
not
increase solubility.

ii) gas - Solubility increases with Pressure.


Increase pressure squeezes gas solute into solvent.
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Solubility

January 13

2 i) Temperature on Solubility:
Solids & Liquids
Temperature -

(Solid and Liquid)

Consider the extent in which sugar or NaCl dissolves in


water. What are the conditions which will increase the
solubility of sugar or salt in water.

[Solute]

Solid

[Solute]
Solution

As the temperature
increase, both solute
and solvent will be
moving faster, this will
result in the mixing of
both substance to be
more effective.

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Solubility

January 13

Equilibrium Revisited
[Solute]

Solid

[Solute]

Solution

Observe: After some time, no change in amount of solid


precipitate at the bottom of the beaker.
Concentration of the solution is maintained
Equilibrium
Situation in which changes occur at equal rates so there is no
apparent net change.
LeChatelier Principle
A Change (i.e., stress) on a system at equilibrium will cause
the system to self adjust itself to reduce the stress until a
new equilibrium is re-establish.
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Solubility

January 13

LeChatelier Principle
TeeterTooter
At Equilibrium

Stress applied
Self Adjust

Re-establish Equilibrium
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Solubility

January 13

Equilibrium: Stress / Relief on Reactant


Stress on Reactant, Rxn shift right

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Relief on Reactant, Rxn shift left

Solubility

January 13

Equilibrium: Stress / Relief on


Stress on Product, Rxn shift left

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Product

Relief on Product, Rxn shift right

Solubility

January 13

Exothermic Heats of Solution


R

Energy +

Exothermic Process.
Energy is a product

Heating a solution
in which the Hsoln
is exothermic
(Energy is a
product) results in
a shift of the
reaction to the left
or more solute
precipitating out of
solution.

Temp increase

R
+ Energy

R
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Energy +

Solubility

January 13

Endothermic Heats of Solution


R+

Energy

Temp increase

P
R

R
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+ Energy

+ Energy

P
Solubility

Endothermic Process
Energy is a reactant
Heating a solution
in which the Hsoln
is endothermic
(Energy is a
reactant) results
in a Shift of the
reaction to the
right or more
solute dissolving
in solution.

January 13

Solubilities of Solids Vs Temperature


Solubilities of
several ionic solid as
a function of
temperature.
Some salts have
negative enthalpy of
solution, (exothermic
process) i.e.,
Ce2(SO4)3 and they
become less soluble
with increasing
temperature.
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Solubility

January 13

2ii) Temperature & Solubility: Gases


Temperature - (Gas)

Consider the extent in which O2 or CO2 dissolves in


water. What are the conditions which will increase
the solubility of gas in water.
[Solute]

gas

As the temperature
increase, both solute
and solvent will be
moving faster, the
gas solute however
will now have enough
energy to leave the
liquid interface.
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Solubility

[Solute]

Solution

January 13

Gas solute; Exothermic Hsoln


P

Energy +

Gas above soln


Gas in solution

Temp increase

As the temperature
increase, both solute and
solvent will be move faster.
The gas solute however will
now have enough energy to
leave the liquid interface
because IMF can be
overcome

+ Energy

R
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Energy +

Solubility

January 13

Disaster: (1700 dead)


from Gas Solubility

In the African nation of Cameroon in


1986 a huge bubble of CO2 gas escaped
from Lake Nyos and moved down a river
valley at 20 m/s (about 45 mph).
Because CO2 is denser than air, it
hugged the ground and displaced the air
in its path. More than 1700 people
suffocated. The CO2 came from springs
of carbonated groundwater at the
bottom of the lake. Because the lake is
so deep, the CO2 mixed little with the
upper layers of water, and the bottom
layer became supersaturated with CO2.

Lake Nyos in Cameroon, the site of


a natural disaster. In 1986 a huge
bubble of CO2 escaped from the
lake and asphyxiated more than
1700 people.
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Solubility

When this delicate situation was


changed, perhaps because of an earthquake or landslide, the CO2 came out of
the lake water just like it does when a
can of soda is opened.
January 13

3 i) Pressure on Solubility:
Solids / Liquid
Pressure - (Solid and Liquid)
The solubility of solids and liquids are
hardly affected by pressure.
Solids and liquids
are already very
close to each other.
An increase in
pressure will not
affect solubility

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Solubility

January 13

3 ii) Pressure on Solubility: Gas


Pressure - (Gas)
Solubility of gas is greatly affected by pressure
Gas solute is very sensitive to
pressure. Gas particles are
separated by large void space, an
increase in pressure will increase
these particles to come closer
together thereby increasing the
solubility of the gas.
Divers must be careful when diving
to great depth because the
potential of dissolved N2 gas in
blood. Clinical term is the Bends.
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Solubility

January 13

Pressure Affect:
Teeter Totter Analogy
R (gas)

[Solute] D [Solute]
Pressure
Sensitive

P (Soln)

Pressure Sensitive

Pres increase

P
R

Pressure
Sensitive

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Pressure
Sensitive

P
Solubility

gas

Solution

In utilizing LeChatelier
Principle to determine the
direction of solubility for a
gaseous solute with variation
in pressure, the first thing
that must be establish is
which side is more sensitive
to pressure. In our case the
gas is more sensitive than the
solution.
January 13

Henrys Law
At pressure of few atmosphere or less, solubility of gas solute
follows Henry Law which states that the amount of solute gas
dissolved in solution is directly proportional to the amount of
pressure above the solution.

c = k P

where, c = solubility of the gas (usually molality)


k = Henrys Law Constant, (solute-solvent pair)
P = partial pressure of gas over solution
Henrys Law Constant (25C)

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Gas

N2
O2
CO2

8.42 10-7
1.66 10-6
4.4810-5

M/mmHg

Solubility

January 13

Henrys Law: Example


The solubility of ethylene (C2H4) in water at 20C and a pressure
of 0.300 atm is 1.2710-4 m.
a) calculate the Henrys Law constant, k in (m/torr)
b) How many grams of ethylene are dissolved in one kilogram of
water at 20C at 500 torr. ?
Detm k from c = kP, k= c / P
k=
1.2710-4 m
0.300 atm (760torr/1atm)
a)
k = 5.5710-7 m / torr

= 1.2710-4 m
228 torr

c = kP k is constant which depends only on T


c = 5.5710-7 m / torr 500 torr
= 2.79 10-4 m = 2.79 10-4 m /kg H2O
b)

mass = 2.7910-4 mol 28.0 g / mol


mass = 7.8010-3 g

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Solubility

January 13

Summary of Pressure Temperature


Affect on Solubility
H (s, l or g)
(+) Endothermic
(+) i

Temp
h
f React

Direction
g Product
i decrease

Solubility
h increase

(-) Exothermic
(-) Exothermic

h
i

f React
g Product

i decrease
h increase

Pressure

Direction

Solubility

h
i

g Product
f React

h increase
i decrease

Gas solute
Gas solute

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Solubility

January 13