The Solution Process

Con't
Objectives :
• explain how the "like dissolves like" rule
depends on inter-particle forces of
interactions
The Solution Process
• gases mix freely.
• the formation of liquid and solid solutions requires
overcoming the solute-solute and solvent-solvent
inter-particle forces of attraction before the mixing
step.
• In liquids and solids, molecules are held together by
intermolecular attractions
 When one substance (the solute) dissolves in
another (the solvent), particles of the solute
disperse throughout the solvent
 solute particles occupy positions that are
normally taken by solvent molecules.
 CON’T
• A good rule of thumb for predicting solubility is that
“like dissolves like”.
• Substances with similar intermolecular forces form
solutions and substances with different
intermolecular forces do not.
• The solution process thus involves three basic steps;
i. breaking up the solute-solute inter-particle forces
ii. breaking up the solvent-solvent inter-particles forces
iii. formation of solute-solvent interaction.
 CON’T
• Thus, the extent of dissolution of a solute in a solvent is
governed by intermolecular forces.
• The energy change associated with the dissolution process
and entropy (the increase in disorder) that result when
molecules of the solute and solvent mix to form a solution
are the forces driving the solution process.
• Note that: the formation of a solution from a solute and a
solvent is a physical process, not a chemical change.
CON’T
Liquid Solutions and Inter-particle Forces of
Attractions
• The ease with which a solute particle replaces a solvent
molecule depends on the relative strengths of inter-particle
forces in the three types of interactions.
• " solute-solute interaction"
• " solvent-solvent interaction"
• " solute- solvent interaction"
 CON’T
• When one substance (the solute) dissolves in
another (the solvent), particles of the solute
disperse throughout the solvent.
Formation of a Liquid Solution
1. Separating the solute into its individual
components (expanding the solute).
2. Overcoming intermolecular forces in the
solvent to make room for the solute
(expanding the solvent).
3. Allowing the solute and solvent to interact to
form the solution
 The solution process involves three basic steps

1. Breaking up the 2. Breaking up the solute-

solvent-solvent inter- solute inter-particles forces
particle forces
• separation of solute • separation of solvent
molecules (H1): molecules (H2):
ENDOTHERMIC ENDOTHERMIC

• Formation of solute-solvent interactions

(H3): exothermic for solution to form
Hsoln = H1 + H2 + H3.
 CON’T
Like dissolve like
• water is polar
• oil is non polar oil and water do not mix
What is a like in like dissolve like
• polar solvents dissolve polar solute ( sometimes
ionic)
• Non –polar solvents dissolve non- polar
 CON,T
How can we Predict whether a molecule is polar or non-polar?
• In larger molecules, molecular polarity is determined by the net dipole
moment (imbalance of charge over the molecule); which in turn depends on
both shape and bond polarity.
• Dipole moment (μ) is a measure of molecular polarity, given in the unit debye (D)
derived from SI units of charge (coulomb, C) and length(m): 1 D = 3.34 x 10-30
C.m.
 CON’T
• Substances with zero or low electronegativity
difference in between the bonding atoms and having
zero net dipole moment are nonpolar
For example, H2 , O2 , N2 , CH4 , CCl4 are nonpolar
• Substances having high electronegativity difference
in between the bonding atoms and having net dipole
moment are polar compounds
For example, H2O, NH3 , CH3OH, NO, CO, HCl, H2 S,
PH3 , etc
 CON’T
• The useful rule-of-thumb “like dissolves like” says
that substances with similar types of intermolecular
forces dissolve in each other.
 when the inter-particle forces within the solute are
similar to those within the solvent, the forces
replace each other and a solution forms
 Inter-particle/Intermolecular Forces
• The covalent bonds are called intramolecular
forces. It is a force within a molecule
• Intermolecular forces are also called noncovalent
interactions. They are attractive or repulsive forces
between neighboring molecules.
 CON’T
These are:
• dipole-dipole interaction
• dipole-induced dipole interaction
• dispersion forces or London forces
• ion-dipole interaction
• ion-induced dipole
• hydrogen bonding
• Note: Dipole-dipole, dipole-induced dipole, and dispersion
forces make up as van der Waals forces, after the Dutch
physicist Johannes van der Waals.
 CON’T
• The relative strengths of these forces in order of weakest to
strongest is:
 Dispersion forces < dipole-induced dipole < dipole-dipole < H -
bonding < ion dipole bond
Dipole-Dipole Forces
• Electrostatic attraction force between polar molecules
• polar molecules, dissolve in polar liquids Eg, Solubility of HBr in
H2 O.
 CON’T
Dipole-induced dipole interaction
• Arise when a polar molecule distorts the electron cloud
of a nonpolar molecule.
• For example , the solubility in water of atmospheric
O2 , N2 and noble gases,
 CON’T
Dispersion Forces (London forces)
• weak, attractive intermolecular forces between two
atoms or two nonpolar molecules due to temporary
dipoles created by electrons’ motion.
• Dispersion forces occur between all neighboring
molecules and arise because the electron
distribution within molecules is constantly changing.
• This type of force is also called instantaneous dipole-
induced dipole force.
 CON’T
• This type of force is also called
instantaneous dipole-induced dipole force.
 CON’T
Ion-Dipole Forces
• Ion–dipole interactions are found in solutions of
ions.
• The strength of these forces is what makes it
possible for ionic substances to dissolve in polar
solvents.

e.g. NaCl dissolves in H2O via ion-dipole

interaction.
 CON’T

Two types of ion-dipole interaction

 Ion –induced dipole forces
• when the ion and the nonpolar molecule get closer,
the nonpolar molecule gets polarized
• when an ion’s charge distorts the electron cloud of a
nearby nonpolar molecule
• Polarizability - a measure of the extent to which the
electron cloud of an atom or molecule can be distorted
by an external electric charge
• Ion- induced dipole force initiates the binding of the
Fe2+ ion in hemoglobin to an O2 molecule entering a
red blood
 CON’T
The Hydrogen Bond
• Requires H atom covalently bonded to strongly
electronegative atom. Example: F, O, N.
CON’T
 Solutions of Ionic Solids in Water

• Many ionic compounds are soluble (at least 1 g

dissolves in 100 mL water) in water; however, not all
ionic compounds are soluble
• A substances can be soluble, slightly soluble, or
insoluble in a qualitative sense.
• For example , KCl is readily soluble in water where as
AgCl is insoluble. Ca(OH)2 is slightly soluble.
• Ionic compounds that are soluble in water exist in their
ionic state as hydrated cations and anions within the
solution
CON’T
 CON’T

• Consider what happens when a piece of sodium chloride, a

typical ionic solid, is placed in water
•
 The Solubility Rules for Ionic Solids
• Solubility is defined as the maximum amount of a
substance that can be dissolved in a given volume
(usually 100 mL) of solvent at a given temperature.
• The solubility rules for common ionic compounds
are listed below.
i. All common salts of the Group 1A elements (such as
Na+, K
+, Li +) and ammonium,NH4+, are soluble
ii. All common salts containing acetate (CH 3COO- ),
or nitrate (NO3-), and most perchlorates (ClO4-) are
soluble
 CON’T
iii. All common chlorides (Cl - ), bromides (Br- ), and
iodides (I - ) are soluble, except those of Ag +, Pb 2+, Cu
2+, and Hg2+. All common fluorides (F- ) are soluble,
except thoseof Pb2+ and Group 2A.
Iv. Most hydroxide salts are only slightly soluble.
Hydroxides of GI elements are soluble. Hydroxides of GII
elements (Ca, Sr, and Ba) are slightly soluble. Hydroxide
salts of transition metals and Al3+ are insoluble. Thus,
Fe(OH)3, Al(OH) 3, are not soluble.
 CON’T
v. All compounds containing sulfate (SO42-) are
soluble, except those of barium (Ba), strontium
(Sr), lead (Pb), calcium (Ca), silver (Ag), and
mercury (Hg)
vi. Except for those compounds following rule 1,
compounds containing carbonate (CO32-),
sulfides (S2-), oxides (O2-), and phosphates
(PO43-) are insoluble.
The dissolution of molecular solids also follows
the same rule.
 CON’T
• The dissolution of molecular solids also follows the
same rule.
• Molecular solids are made up of atoms or molecules
held together by London or dispersion forces, dipole-
dipole forces, or hydrogen bonds.
• Polar molecular solids such as ice, glucose, and
sucrose dissolve in polar solvents like water.
• Nonpolar molecular solids such as sulfur, solid
hydrocarbons, etc dissolve in nonpolar solvents like
benzene, hexane, etc.
 Solution of Liquids in Liquids
• Miscibility is used to describe the ability of one liquid
to dissolve in another.
• Polar liquids tend to interact strongly with and dissolve readily
in other polar liquids.
For example, grain alcohol (CH3 CH2 OH) is a polar
covalent molecule that can mix with water.
• When two similar liquids (in terms of polarity) are
placed together and are able to mix into a solution,
they are said to be miscible.
 CON’T
• Liquids that do not share similar characteristics
and cannot mix together are termed
immiscible.
For example, oil and water.
• The nonpolar molecules in oil do not attract
polar water molecules, so oil and water are
immiscible.
• there are only dispersion forces between
nonpolar molecules (whether alike or different),
which are weak and easily overcome.