10 Solutions

and solubility
10.1 Introduction to solutions
and solubility
Solution
•
Homogeneous mixture of two or more pure substance
–
May be gaseous, liquid or solid
–
Solvent
•
Liquid of a liquid solution
–
Solute
•
Dissolved substance in liquid solution
–
10.1 Introduction to solutions
and solubility
Solubility
•
Maximum amount of solute that dissolves completely in a given amount of solvent at a particular temperature,
–T

Saturated solution
•
Solution in which no more solute will dissolve
–
Dissolution
•
Process of dissolving a solute in a solvent to give a homogeneous solution
–
 10.2 Gaseous solutions

• All gases mix

completely with all
other gases in all
proportions
• Gases mix
spontaneously
hence ΔG for mixing
process negative
10.2 Gaseous solutions
Enthalpy change when two gases are mixed is usually small
•
Large positive Δmix S term ensures Δmix G negative
•
Intermolecular forces between individual gas molecules are tiny, and gas molecules are far
• apart

No impediment to the mixing of gases

•
10.2 Gaseous solutions

• The magnitude of interatomic and

intermolecular attractions in the
condensed phase can determine
whether or not two substances
can mix
 10.3 Liquid solutions

• Gas–liquid solutions

– For a gas to dissolve in a liquid, the gas molecules must be

able to disperse themselves evenly throughout the solvent
 10.3 Liquid solutions

• Gas–liquid solutions
– Intramolecular forces between the
solvent molecules are not negligible
– Neither therefore is the value of ΔsolH, the
enthalpy of solution
 10.3 Liquid solutions

• Gas–liquid solutions
 10.3 Liquid solutions

• Gas–liquid solutions
– Solubility of gases vary significantly with
temperature
– Solubility of gases vary significantly with
pressure
 10.3 Liquid solutions

• Gas–liquid solutions
– For gases that do not react with the solvent,
Henry’s law gives the relationship between gas
pressure and gas solubility
c gas = kHpgas( constant
T)
– cgas is the concentration of the gas
– pgas is the partial pressure of the gas above the
solution
– kH is called the Henry’s law constant and is
unique to each gas
 10.3 Liquid solutions

• Gas–liquid solutions
– Equation is only true at low concentrations
and pressures
– An alternative expression of Henry’s law
is:
c1 c 2
=
p1 p2

– c1 and p1 refer to initial conditions

– c2 and p2 refer to final conditions
 10.3 Liquid solutions

• Liquid–liquid solutions
– Formation of a liquid–liquid solution requires that
the attractive forces present between the
molecules of the two pure liquids is overcome
– Two substances are MISCIBLE when they mix
completely in all proportions
– Two substances are IMMISCIBLE when they
form two layers upon the addition of one to the
other
 10.3 Liquid solutions

• Liquid–liquid solutions H
H C H
C C
H H
δ− δ+ C C
H C C O H H C H
H H H
Ethanol Benzene
hydrogen bond H H
H O H O
C2H5 O H O H
H O C2H5
H
Like–dissolves–like
 10.3 Liquid solutions

• Liquid–solid solutions
– Basic principles remain
the same
– Solvation is when a solute
molecule is surrounded by
solvent molecules
– Hydration occurs when
solutes become surrounded
by water molecules
 10.3 Liquid solutions

• Liquid–solid solutions
– Like-dissolves-like
– When intermolecular attractive forces within
solute and solvent are sufficiently different,
the two do not
form a solution
 10.3 Liquid solutions

• Liquid–solid
solutions
 10.3 Liquid solutions

• Liquid–solid solutions
 10.3 Liquid solutions

• Liquid–solid
solutions
– Temperature can
have a significant
effect on the
solubility of a
solid solute in
a liquid
 10.4 Quantification of
solubility: the solubility
product
• Ionic salts are generally classified as being
either soluble or insoluble in water
AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq)
AgCl(s) Ag+(aq) + Cl–(aq)
Ksp = [Ag+][Cl–]

• Ksp is called the solubility product

MaXb(s) aMc+ (aq) + bXd– (aq)
Ksp = [Mc+ ]a[Xd– ]b
 10.4 Quantification of
solubility: the solubility
product
• The relationship between Ksp and
solubility
– Molar solubility (s)
molar concentration of a salt in its
saturated solution
– Molar solubility can be used to calculate
Ksp , assuming that all of the salt that
dissolves is 100% dissociated into its ions
 10.4 Quantification of
solubility: the solubility
product
The solubility of AgBr in water is 1.3 × 10–4 g L–1 at
25 °C. Calculate Ksp for AgBr at this temperature
AgBr(s) Ag+(aq) + Br–(aq)
Ksp = [Ag+][Br–]
m 1.3 × 1 0− 4 g −7
n= = − 1
= 6 .9 × 10 mol
M 1 8 7.77 gmol

[Ag+] = [Br–] = 6.9 × 10–7 mol L–1

Ksp = [Ag+][Br–] = (6.9 × 10–7 mol L–1 )(6.9 × 10–7 mol L–1 )
Ksp = 4.8 × 10–13 at 25 °C
 10.4 Quantification of
solubility: the solubility
product
Calculate the molar solubility of lead iodide, PbI2, given that Ksp (PbI2) =
7.9 × 10–9
PbI2(s) Pb2+ (aq) + 2I–(aq)
Ksp = [Pb2+ ][I–]2
Define the molar solubility of PbI2(s) as s mol L–1
[Pb2+ ] = s mol L–1
[I–] = 2s mol L–1
Ksp = (s)(2s)2 = (s)(4s2) = 4s3 = 7.9 × 10–9

−9
3s = 7 .9 × 10
s = 1.3 × 10
–3

4 in water at 25 °C is
The molar solubility of PbI2(s)
1.3 × 10–3 mol L–1
 10.4 Quantification of
solubility: the solubility
product
• The common ion effect
– Any ionic salt is less soluble in the presence
of a common ion, an ion that is in the salt
PbCl2(s) Pb2+ (aq) + 2Cl–(aq)
Ksp = [Pb2+ ][Cl–]2
Add Pb(NO3)2(aq) to saturated solution of PbCl2
instantaneously increases [Pb2+ ] and therefore Qsp
(ionic product).
Qsp > Ksp
PbCl2 is precipitated
 10.4 Quantification of
solubility: the solubility
product
What is the molar solubility of PbI2 in a 0.10 M NaI solution?
PbCl2(s) Pb2+ (aq) + 2Cl–(aq)
Ksp = [Pb2+ ][Cl–]2 = 7.9 × 10–9

PbI2(s) Pb2+ (aq) + 2I–(aq)

Initial concentration (M) 0 0.10
Change in concentration (M) +s +2s
Equilibrium concentration (M) + 2s)2 = 7.9 ×s10–9
K = s(0.10 0.10 + 2s
sp

Ksp = s(0.10)2 = 7.9 × 10–9

Molar solubility of PbI2 in 0.10 M NaI solution is 7.9 × 10–7 M (s)
 10.4 Quantification of
solubility: the solubility
product
• Prediction of precipitation
– Qsp > Ksp precipitate will form
– Qsp < Ksp no precipitate will form
AgCl(s) Ag+(aq) + Cl–(aq)
Ksp = [Ag+][Cl–] = 1.8 × 10–10
[Ag+] = 5.0 × 10–7 mol L–1
[Cl–] = 5.0 × 10–5 mol L–1
Qsp = 2.5 × 10–11
Qsp < Ksp no precipitate will form
10.5 Colligative properties of
solutions
• Nonvolatile solutes
– Solutes that can’t evaporate from solution
– Vapour pressure of a solution of nonvolatile
solutes is lower than the pure solvent

• Colligative properties
– Depend on number of solute particles in
solution rather than chemical identities
10.5 Colligative properties of
solutions
• Molarity
– Amount of substance in a particular
volume of solution
amount of solute (mol)
molarity (c ) =
volume of solution (L)
– Solutions (usually) increase in volume
with increasing temperature
– The molarity of a solution changes as the
temperature changes
10.5 Colligative properties of
solutions
• Molality
– Preferred method of expressing solution
composition when colligative properties
involved
– Amount of solute per kilogram of solvent
amount of solute (mol)
molality (b ) =
mass of solvent (kg)
– Temperature independent
10.5 Colligative properties of
solutions
• Mole fraction
– The number of moles of a particular
component divided by the total number
of moles of material in the solution
– The mole fraction of A, XA, in a solution
containing substances A, B and C
nA
XA =
nA + nB + nC
– Temperature independent
10.5 Colligative properties of
solutions
• Raoult’s law
– Boiling point of a solution containing a
nonvolatile solute is higher than that of the
pure solvent
– Boiling point of a solvent is the
temperature at which the vapour pressure
of the solvent is equal to the atmospheric
pressure
10.5 Colligative properties of
solutions
• Raoult’s law
psolution = Xsolvent p*solvent
– psolution – vapour pressure of the solution
– Xsolvent – mole fraction or solvent in the
solution
– p*solvent – vapour pressure of pure solvent
– For a simple two component system
– Provided the solution is sufficiently dilute
 10.5 Colligative properties
of solutions
• Raoult’s law
psolution = Xsolvent p*solvent
Xsolvent = 1 – Xsolute
psolution = (1 – Xsolute)p*solvent
psolution = p*solvent – Xsolutep*solvent
Δp = Xsolutep*solvent
Δp = p*solvent – psolution
 10.5 Colligative properties
of solutions
• Raoult’s law
– A solution that obeys Raoult’s law is called an ideal
solution
– These solutions
are generally
dilute and have
only small
interactions
between their
constituent
molecules
 10.5 Colligative properties
of solutions
• Solutions containing more than one
volatile component
– For component A
pA = XAp*A

– For component B
pB = XBp*B

– Total pressure
ptotal = XAp*A + XBp*B
 10.5 Colligative properties
of solutions
• Boiling point elevation and freezing point
depression
– boiling point elevation
ΔTb
ΔTb = Kbb

– freezing point
depression
ΔTf
ΔTf = Kfb
10.5 Colligative properties of
solutions
• Boiling point elevation and freezing
point depression
– Molal boiling point elevation constant
• Kb
• Units – K mol–1 kg

– Molal freezing point depression constant

• Kf
• Units – K mol–1 kg
10.5 Colligative properties of
solutions
• Boiling point elevation and freezing
point depression
– Molality of the solution
•b
• Units – mol kg–1

– Kbb and Kf b are properties of the solvent

only and independent of the identity of
the solute
10.5 Colligative properties of
solutions
• Osmosis and osmotic pressure
– A membrane keeps mixtures and solutions
organised and separated.
– Semipermeable membranes allow selective
substances to pass through
– Dialysis occurs when a dialysing membrane
allows both water and small solute particles
through
– Osmosis is a net shift of only solvent through
an osmotic membrane
10.5 Colligative properties
of solutions
• Osmosis and osmotic pressure
10.5 Colligative properties of
solutions
• Osmosis and osmotic pressure
– Osmotic pressure
• Π
– In dilute aqueous solution
Π = cRT n
c =
ΠV = nRT V

– This is the van’t Hoff equation for osmotic

pressure
 10.5 Colligative properties
of solutions
• Osmosis and osmotic pressure

Isotonic Hypertonic Hypotonic

Osmometer
10.5 Colligative properties of
solutions
• Measurement of solute dissociation
– Molal freezing point depression constant for
water is 1.86 K mol–1
– 1.00 mol kg–1 NaCl freezes at about –
3.37 °C
– NaCl(s)  Na+(aq) + Cl–(aq)
– Solution has a a total molality of dissolved
solute particles of 2 mol kg–1
– Theoretically, a 1.00 mol kg–1 NaCl solution
should freeze at –3.72 °C
10.5 Colligative properties of
solutions

( ∆Tf ) measured
i =
( ∆Tf ) calculatedas nonelectrolyte
10.5 Colligative properties
of solutions
• Measurement of solute dissociation
10.5 Colligative properties of
solutions

∆Tf 1.9 0K mol of ionised

b= = −1
%ionisation= × 100 %
Kf 1.8 6K mol kg mol of acid available
−1 0.02
b = 1.0 2 mol kg %ionisation= × 10 0%
1.00
%ionisation= 2%
10.5 Colligative properties of
solutions

O O H O
C6 H5 C C C6H5
2 C6 H5 C O H O H O
benzoic acid benzoic acid dimer