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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
• Gas–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
• 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–]
−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
• 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
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
O O H O
C6 H5 C C C6H5
2 C6 H5 C O H O H O
benzoic acid benzoic acid dimer