Applied Solution Chemistry

The Solution Process

Applied Solution Chemistry
Intermolecular Forces
1. Solubility (§13.3, §13.4)
2. Colligative Properties (§13.6)
3. Surfactants, Soaps and Colloids (§13.1, §13.2, §13.7)
 Solutions
• A solution is a homogenous mixture of two or more
substances in a single phase
• The solute (least abundant) is dissolved in the solvent (in
excess)
• Solutions can be concentrated or dilute
• The solubility is the maximum amount (in units of g/L) of a
substance that can dissolve in a given solvent
• A solute will dissolve if the attractive forces between
solute-solvent is comparable to those between solute-
solute and solvent-solvent
• “Like dissolves like”
 Expressing Concentration
• Mole fraction:
• The amount of a specific component, divided by the total amount of
all components n
xB  B
n A  nB
• Molarity and Molality:
• Number of moles of solute in 1 L of solution (molarity) or number of
moles of solute in 1 kg of solvent (molality)
nB nB
MB  (mol/L) mB  (mol/kg)
V massA
• Parts by mass or volume:
• Can be either mass (w/w) or volume (v/v). Note, ppm (parts per
million) in mass
massB
100  mass percent
massA  massB
 Molality
Calculate the mass of I2 that must be
dissolved in 115 grams of carbon disulfide
to create a 0.097 m solution.
 Molality
Calculate the molality of a solution
containing 17 grams of glucose, C6H12O6,
dissolved in 225 grams of water.
 Parts by mass or volume
massB
100  mass percent
massA  massB %v/v

What is the Molarity of 30% H2O2? Or

Density = 1.11 g cm-3
%w/w
Salon Lab @Home
Or
% w/v
 Parts per million (ppm)
mass B %v/v
 10 6  ppm %w/w
mass A  mass B % w/v

Water quality mg/L or ppm or ppb?

Molecular Forces

d+

d-
+
 Intermolecular Forces
• Solubility is influenced by the forces (or energies) between
solute and solvent molecules
• Factors such as the charge on ions, the polarity of
solvent/solute molecules and their polarisibility, as well as the
shape of molecules, are important
• In solution, a range of intermolecular forces can occur:
• Ion-dipole, e.g. in electrolytes, ions in solution
• Dipole-dipole, e.g. polar molecules
• Hydrogen bonding, e.g. in aqueous solutions
• Induced-dipole/dipole or ion, e.g. ions in non-polar solvents
• Dispersion, e.g. in non-polar solutions such as fuels
 Polar Interactions
d+
ethanal (CH3CHO) chloroform (CHCl3)
d-
d- water (H2O) d+
+ d+ d-

sodium (Na+)
dipole-dipole ~ 5 – 25 kJ/mol

Ion-dipole ~ 40 – 600 kJ/mol xenon (Xe) water

d- d+ d+
d- d-
- d+
-
chloride (Cl ) Dipole-induced dipole~ 2 – 10 kJ/mol

Ion-induced dipole ~ 3 – 15 kJ/mol

hexane (C6H14)
 The Effect of Dipole-Dipole Interaction
• Boiling points correlate with the energy required to separate
molecules as they change from high density liquids to lower
density gases. An increase in boiling point accompanies an
increase in dipole moment
acetaldehyde
dimethyl ether

400 acetonitrile

propane methyl chloride

300

200

100

0
dipole moment (100D)

boiling point (K)

 Hydrogen Bonding
• This is a special type of dipole-dipole interaction between
molecules with an H-atom bonded to a small, highly
electronegative atom, and a second electronegative atom
• The small electronegative atom makes the hydrogen atom
highly positive
• This allows for additional strong interaction with the
electrons of the second electronegative atom
• Most important electronegative atoms are N, O
electronegative
electronegative
atom —A· · ·H —D— atom
d- d- d-
d+ d+ d+
—F · · ·H —O— —O · · ·H —N— —N · · ·H —F
H-Bonding in DNA
 The Effect of Hydrogen Bonding
• Ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3)
have the same empirical formula, but the boiling point
of ethanol is 78.3°C whereas the ether is -24.8°C!
dimethyl ether

ethanol

no hydrogen bonds are

Can form hydrogen bond, so possible
molecules in liquid have
strong attractive forces
between them
 Dispersion (London Forces)
• Dispersion is responsible for attractive interaction between
non-polar molecules
• The motion of electrons can distort their shape and create
instantaneous dipole moments. These dipole moments can
couple, and dispersion interaction, or London interaction
(named after Fritz London), arises
• The strength is depended on the number of electrons, i.e. the
size (or molar mass) of the compound
d+
d-

d+
d-
Time-averaged electron density
Instantaneous fluctuations, however, create
is spherically symmetrical
coupled instantaneous dipole moments
Summarising Intermolecular
Forces
 Effects on Solubility
• A solute will dissolve if the attractive forces between solute-solvent is
comparable to those between solute-solute and solvent-solvent

(water) (hexane)

(methanol) completely soluble 1.2 mol/kg

(propanol) completely soluble completely soluble

(butanol) 1.1 mol/kg completely soluble

(hexanol) 0.058 mol/kg completely soluble

 Degree of Saturation
• In a saturated solution:
• the solvent holds as much solute as is possible at that
temperature
• undissolved solid remains in the flask
• dissolved solid is in dynamic equilibrium with solid solute
• In an unsaturated solution:
• less than the maximum amount of solute is dissolved
• no solid remains in the flask
• In a supersaturated solution:
• solvent holds more solute than is normally possible at that
temperature
• These solutions are unstable, and can be brought to
crystallisation by adding a “seed crystal”
 The Dissolution Process
• The dissolution process can be broken down into three steps:
1) Solute particles separate, H solute  0
A thermochemical solution cycle

2) Solvent particles separate, H solvent  0

Heat of solution
3) Solute and solvent mix, H mix  0
H soln  H solute
 H solvent
 H mix
 The Heat of Hydration
• For ionic solutes, the heat of hydration is defined as the
enthalpy change for separating the solvent and mixing the
solute (ions) and solvent
enthalpy change
• For ions, this contribution is always negative to hydrate
M  ( g )  X  ( g ) H

2O
 M  (aq)  X  (aq) (surround with
water molecules)
H soln  H solute  Hhydr gas phase ions

• The enthalpy to form gaseous ions, from a solid, is the negative

(reverse) of the lattice enthalpy (which is always negative)
• This contribution is always positive
enthalpy change to
M  X  ( s) 
 M  ( g )  X  ( g ) separate solute atoms
H soln  Hlattice  Hhydr into gaseous ions

• Whether the solution process is exothermic or endothermic

depends on the relative sizes of these terms (hydration and
lattice enthalpy)
Use the following data to calculate the heat of hydration, ΔHhydr, for the ions (K+
and BrO3−) in potassium bromate (KBrO3). Also write a chemical equation
describing this hydration process.
ΔHlattice = -745 kJ mol−1 ΔHsoln = 41.1 kJ mol−1
 Exothermic and Endothermic Dissolution

+ -
Na+ (g) + OH- (g) NH4 (g) + NO3 (g)

NaOH (s)
NH4+ (aq) + NO3- (aq)
the water in
the flask will
feel hot the water in
the flask will
Na+ (aq) + OH- (aq) NH4NO3 (s) cool down

Dissolving sodium Dissolving ammonium

hydroxide is exothermic nitrate is endothermic
 Entropy of Solution
• Ssoln is always positive for dissolution
• For a solution process where Hsoln < 0, Gsoln < 0 and dissolution
is favoured
• When Hsoln > 0, Ssoln must outweigh this contribution for the
solution process to occur
H soln  TSsoln  0
Entropy change not large
enough to counter endothermic
solute separation and weak
solute-solvent interaction

 Hlattice  0 H mix  0 Ssoln  0

H soln  TSsoln  0
H mix  0 Entropy outweighs the solute-solvent
interactions that are weak, and
Ssoln  0 similar in order to solute-solute and
solvent-solvent interactions
 Temperature Affects on Solubility
• The solubility of most solids (in water) increases
with an increase in temperature
• The solubility of gases decrease with increasing
temperature

CH4

Solubility O2
Solubility

CO2

Ce2(SO4)3

Temperature Temperature
 Pressure Affects on Solubility
• Pressure has little effect on the solubility of solids in
liquids
• However, an increase in pressure will increase the
solubility of gases
• Henry’s Law expresses
the relationship
between the partial
pressure of a gas above
a solution, and its
solubility partial
pressure
• Sgas  k H  Pgas (atm)

Solubility Henry’s Law constant

(mol/L) (mol/L·atm)
 Pressure Affects on Solubility
How many grams of O2 will dissolve in 2.50 L of water that is in contact
with O2 at a partial pressure of 0.209 atm and 20°C? The Henry’s Law
constant for O2 (kH) in water at 20°C is 1.28 × 10−3 mol L−1 atm−1.
Henry’s Law & Soft Drinks
• Soft drinks contain “carbonated
water” – water with dissolved
carbon dioxide gas.
• The drinks are bottled with a CO2
pressure greater than 1 atm.
• When the bottle is opened, the
pressure of CO2 decreases and the
solubility of CO2 also decreases,
according to Henry’s Law.
• Therefore, bubbles of CO2 escape
from solution.
Sample Problem 13.2 Using Henry’s Law to Calculate Gas Solubility

PROBLEM: The partial pressure of carbon dioxide gas inside a bottle of

cola is 4 atm at 25oC. What is the solubility of CO2? The
Henry’s law constant for CO2 dissolved in water is 3.3 x10-2 mol
L-1 atm-1 at 25oC.