CHAPTER 1

Properties of Solutions

1
 Learning Outcomes
 Able to distinguish the factors affecting
solubility.
 Able to express different types of solution
concentrations and conduct calculations
involved.
 Able to understand colligative properties
effect and conduct calculations involved.
2
 SCOPE
1.1 Introduction to Solutions and Solubility

1.2 Factors Affecting Solubility:

– Solute-solvent interactions
– Temperature
– Pressure
– Solutions

3
 SCOPE
1.3 Quantitative Ways of Expressing Concentration
– Molarity, Molality
– Mass %, ppm, ppb, Mole Fraction

1.4 Colligative Properties of Solutions

– Vapor Pressure Lowering
– Boiling Point Elevation
– Freezing Point Depression
4
– Osmotic Pressure
 1.1 Introduction to solutions and
solubility
• Solution
– Homogeneous mixture of two or more pure
substance

• Solvent
– May be gaseous, liquid or solid
– Liquid of a liquid solution

• Solute
5
– Dissolved substance in liquid solution
 1.1 Introduction to solutions and
solubility
Solvent
The dissolving
medium - most
abundant component
of a given solution Solution
A homogeneous
mixture of two or
Solute more substance
A substance that
dissolves in the
dissolving medium
(solvent)

Miscible: Substances (liquid) that are soluble in each other in

any proportion
 1.1 Introduction to solutions and
solubility
• Solubility, S
– Maximum amount of solute that dissolves
completely in a given amount of solvent at a
particular temperature, T
For NaCl, S = 39.12 g/100 mL H2O @ 100oC
For AgCl, S = 0.0021 g/100 mL H2O @ 100oC

• Dissolution
– Process of dissolving a solute in a solvent to give
a homogeneous solution 7
 Water molecules

Undissolved NaCl

Dissolution process
8
 1.1 Introduction to solutions and
solubility
Types of solution
• Saturated solution
– contains the maximum amount of dissolved
solute at a given temperature in the presence of
undissolved solute.
– Solute (undissolved)  solute (dissolved)

• Unsaturated solution
– contains less than the maximum amount of
dissolved solute, it has the capacity to dissolve
more solute
 1.1 Introduction to solutions and
solubility

•Supersaturated solution:
– contains more than the equilibrium amount of
dissolved solute.
– unstable relative to the saturated solution.
– If a seed crystal is added, the excess solute will
crystallize immediately, leaving a saturated
10
solution.
 1.2 Factors Affecting Solubility

• Solute - solvent interaction

• Temperature
• Pressure - for gases
 1.2Solute-Solvent
Factors Affecting Solubility
Interactions

Solute - solvent interaction

• The stronger the attractions between solute and solvent
molecules, the greater the solubility
• Solute will dissolve in the solvent if the intermolecular forces of
the molecules in the solutes is comparable compared to the
intermolecular forces of the molecules of the solvent

Comparable
Ionic bond
Hydrogen bond
Strength increases
Dipole-dipole
London dispersion force
 Example
1.2 Factors Affecting Solubility

• Example (solute-solvent interaction):

– Dissolving NaCl in H2O compared to dissolving
NaCl in benzene

– NaCl - ionic bond, H2O – hydrogen bond

 these bonds are comparable in the strength order
  can dissolve

– Benzene experience LDF  too much weak

compared to ionic bond  cannot compensate to
the forces of solute  NaCl cannot dissolve
 1.2Solute-Solvent
Factors Affecting Solubility
Interactions

• The number of carbon atoms effects its solubility in

water.
• As the length of carbon chain increases the polar OH
group become a smaller part of the molecule, the
molecule become more likely hydrocarbon, thus the
solubility decreases
• If the number of OH group along the carbon chain,
increases more solute-water hydrogen bonding,
therefore increase solubility
e.g. Glucose C6H12O6
 1.2Solute-Solvent
Factors Affecting Solubility
Interactions

• London Dispersion forces increases with increasing

molecular mass, leads to higher solubilities
Eg: Solubility of gas in water
Gas MW Solubility in H2O
(g/mol) at 20oC (M)
N2 28 0.69 X 10-3
O2 32 1.38 X 10-3
Ar 40 1.50 X 10-3
Kr 83.8 2.79 X 10-3
 1.2 Factors
Effect of Affecting
TemperatureSolubility
Temperature
• In general, the solubility of solid solutes in water increases
with increasing temperature.
(e.g: next slide - exceptions in the curve for Ce2(SO4)3 )

• In contrast to solid solutes, the solubility of gases in water

decreases with increasing temperature.
(e.g: next slide)
• The decrease in gas solubility as temperature increases is
primarily a function of kinetic energy
– As temperature increases, the kinetic energy of dissolved gas
will increase, making it easier for the gas molecules to escape
the solution
1.2 Factors Affecting Solubility
 1.2 Factors Affecting
Effect of Pressure Solubility
Pressure (gas-liquid system)
• If the pressure of a gas increase (at constant T)  more gas
molecules are striking the surface of the container in a given
amount of time (Kinetic Molecular Theory)

• A gas in contact with a solution is "dissolved" when gas

molecules strike the surface of the solution (and are
surrounded and dispersed by the solvent).

• Thus, increasing the pressure (at constant T) results in more

collisions of the gas molecules, per unit time, with the surface
of the solvent  This results in greater solubility.
 1.2 Factors Affecting Solubility

• The solubility of gas in any solvent increased as

the pressure of the gas over the solvent
increases (at constant T).

• The solubilities of solids and liquids are not

appreciably (clearly noticed) affected by pressure.
 EffectAffecting
1.2 Factors of PressureSolubility

Dynamic equilibrium:
• Rate gas molecules enter the solution(liq.phase) = the rate
solute molecules enter the gas phase.
• If piston is pushed down, gas volume decreases and pressure
increases. More gas dissolves until equilibrium is established
 Gas-Liquid Solutions

• Solubility of gases vary significantly with pressure

• For gases that do not react with the solvent, Henry’s law
gives the relationship between gas pressure and gas
solubility
S gas  k H Pgas  constant T 
Sgas is the concentration/solubility of the gas (molarity)
Pgas is the partial pressure of the gas above the solution
kH is called the Henry’s law constant and is unique to each
21
gas
 Gas-Liquid Solutions
Henry’s law

Example:
Calculate the concentration of CO2 in a soft drink:

Bottle with pressure of CO2 of 4.0 atm over the liquid at

25oC. The Henry’s law constant : 3.1 X 10-2 mol/L.atm.
Sgas = kHPgas
= (3.1 X 10-2 mol/L.atm)(4.0atm)
= 0.12 mol/L
= 0.12 M
 Gas-Liquid
1.3 Solutions
Liquid solutions

• Equation (Henry’s Law) is only true at low

concentrations and pressures
• An alternative expression of Henry’s law is:
S1 S 2

P1 P2

S1 and P1 refer to initial conditions

23
S2 and P2 refer to final conditions
 Liquid-liquid Solutions
1.3 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
24
 Liquid-liquid Solutions
H
H H H C H
  C C
H C C O H
C C
H H H C H
H
Ethanol
Benzene

hydrogen bond H H
H O H O
C2 H5 O H O H
H O C2H5
H
Like–dissolves–like (ethanol is dissolved in H2O)
25
RECALL
CHEMISTRY I

26
 Solid-liquid
1.3 LiquidSolutions
solutions

• Solid–liquid 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
27
 Solid-liquid
1.3 LiquidSolutions
solutions
• Solid–liquid solutions
– Like-dissolves-like
– When intermolecular attractive forces within
solute and solvent are sufficiently different,
the two do not
form a solution
– Temperature can have a
significant effect on the
solubility of a solid solute
in a liquid
28
 Solid-liquid Solutions
• 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

(RECALL CHEMISTRY I)
MaXb(s) aMc+(aq) + bXd–(aq)
29
Ksp = [Mc+]a[Xd–]b
 Solid-liquid Solutions

• The relationship between K sp 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 30
 Solid-liquid Solutions
Example:

The solubility of AgBr in water is 1.3 × 10–4 g L–1 at

25 °C. Calculate Ksp for AgBr at this temperature.
Solution:
AgBr(s) Ag+(aq) + Br–(aq)
Ksp = [Ag+][Br–]
4
m 1 . 3  10 g 7
n   1
 6 . 9  10 mol
M 187 .77 gmol 31
 Solid-liquid Solutions

Solution (cont):

[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

32
 Solid-liquid Solutions
Example:
Calculate the molar solubility of lead iodide, PbI 2,
given that Ksp(PbI2) = 7.9 × 10–9

Solution:
PbI2(s)  Pb2+(aq) + 2I–(aq), Ksp = [Pb2+][I–]2

Define the molar solubility of PbI2(s) as s (mol L–1)

[Pb2+] = s, [I–] = 2s
Ksp = (s)(2s)2 = (s)(4s2) = 4s3 = 7.9 × 10–9
33
s = 1.3 × 10 –3
 Solid-liquid Solutions

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 34
PbCl is precipitated
 Solid-liquid Solutions
Example:
What is the molar solubility of PbI2 in a 0.10 M NaI solution?
Pbl2(s) Pb2+(aq) + 2l–(aq)
Ksp = [Pb2+][I–]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) s 0.10 + 2s

Ksp = s(0.10 + 2s)2 = 7.9 × 10–9 35

2 –9
1.4 Quantification of solubility: the
Solid-liquid Solutions
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 36

 1.3 Expressing Concentration

• Mass / mole fraction

• Mass / mole percent
• Part per million (ppm)
• Part per billion (ppb)
• Molarity , M
• Molality , m
 Quantitative Ways of Expressing
1.3 Expressing Concentration
Concentration

Mole fraction, X
– 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

xxA == nnA
A A
nnA ++ nnB +n+nC
A B C

The sum of the mole fractions must equal 1.

– Temperature independent
 Quantitative Ways of Expressing
1.3 Expressing Concentration
Concentration

Mole percentage of a component

Mole
Mole %
% of
of Component
Component

== Mole
Mole of
of component
component inin solution
solution X
X 100
100
total
total mole
mole of
of solution
solution

e.g. A solution of hydrochloric acid that is 36% HCl

by mass contains 36 g HCl for each 100 g of solution.
36% Vol or 36% wt
 Quantitative Ways of Expressing
1.3 Expressing Concentration
Concentration
Parts per million (ppm)
ppm
ppm of
of component
component
==mass of component in solution X
mass of component in solution X 10 10 66

total
total mass
mass of
of solution
solution
mg/Kg = ppm wt
l/L = ppm vol
1 mg of solute per kilogram of solution = 1 ppm
if with respect to concentration of solute in water
 1 ppm = 1 mg/L
 Quantitative Ways of Expressing
1.3 Expressing Concentration
Concentration
Parts per billion (ppb)
1 ppb = 1g of solute per billion (109) grams of solution,
or 1 microgram (g) of solute per Liter of solution

ppb
ppb of
of component
component
== mass of component in solution
mass of component in solution X 10 X 10 99

total
total mass
mass of
of solution
solution
if with respect to concentration of solute in water
 1 ppb = 1 g/L
 1.3 Expressing
ExampleConcentration
Example:
What is the mass percentage of iodine (I2) in a
solution containing 0.045 mol I2 in 115 g of CCl4 ?

Solution:
mass of component
mass %   100
total mass solution
253.8 g
mass of solute  0.045 mol I2   11.42 g I2
mol
11.421 g
mass %   100  9.0 % I2
11.421 g  115 g
 1.3 Expressing
ExampleConcentration

Example:
Seawater contains 0.0079 g Sr2+ per kilograms of
water. What is the concentration of Sr2+ measured
in ppm?

Solution:
mass of component
ppm   106
total mass solution
2
0.0079 g Sr
  10 6

1000 g H 2 O  0.0079 g Sr 2
2
 7.9 ppm Sr
 1.3 Expressing Concentration
Quantitative Ways of Expressing Concentration

Molarity, M
Amount of substance in a particular volume of
solution
Molarity
Molarity (M)
(M) == moles
moles ofof solute
solute
liters
liters solution
solution
Solutions (usually) increase in volume with
increasing temperature
The molarity of a solution changes as the
temperature changes
 1.3 Expressing Concentration
Quantitative Ways of Expressing Concentration

Molality, m
– Preferred method of expressing solution composition
when colligative properties involved
– Defined as the number of moles of solute per kilogram
of solvent:
Molality
Molality(m)
(m) == moles
molesof
ofsolute
solute
kilograms
kilogramsof
ofsolvent
solvent
– Temperature independent

Note:
i. Molarity is defined in terms of the volume of solution
ii. Molality is in terms of the mass of solvent
 1.3 Expressing Concentration

Example :
Ascorbic acid (Vitamin C, C6H8O6) is a water soluble
vitamin. A solution containing 80.5 g of ascorbic acid
dissolved in 210 g of water has a density of 1.22 g/ml
at 55oC. Calculate:
a. mass percentage,
b. mole fraction,
c. molality,
d. molarity of ascorbic acid in this solution.
 1.4 Colligative Properties
Colligative Properties of Solutions

• Colligative properties :
– Depend only on the number of dissolved particles in solution
and not on their identity.

• Example: Ethylene glycol added to water in car radiator

– Lowers the freezing point of solution
– Raises the boiling point of solution, so that car can operate at
high temperature

• Colligative properties affect:

 vapor pressure,
 boiling point,
 freezing point, and

 1.6 Colligative properties of
1.4 Colligative Properties of Solutions
solutions

i. Vapor pressure lowering

– 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 vapor pressure of the solvent is
equal to the atmospheric pressure

48
 1.6 Colligative properties of
1.4 Colligative Properties of Solutions
solutions

• The vapor pressure of solvent above the

solution is expressed by Raoult’s Law:

Psolution = Xsolvent P*solvent

Psolution - vapor pressure of the solution
Xsolvent - mole fraction or solvent in the solution
P*solvent - vapor pressure of pure solvent

- For a simple two component system

- Provided the solution is sufficiently dilute 49
 1.6Colligative
1.4 ColligativeProperties
propertiesofofSolutions
solutions
How does amount of of solute affect
the magnitude of the vapor pressure
lowering?

Psolution = xsolvent P*solvent

xsolvent = 1 – xsolute
Psolution = (1 – xsolute)P*solvent
Psolution = P*solvent – xsoluteP*solvent
ΔP = xsoluteP*solvent
ΔP = P*solvent – Psolution
50
 1.6 Colligative properties of
1.4 Colligative Properties
solutions 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
51
molecules
 1.6 Colligative properties of
1.4 Colligative Properties of Solutions
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
52
 1.6 Colligative properties of
1.4 Colligative Properties of Solutions
solutions
ii. Boiling point elevation and
Freezing point depression

– boiling point elevation, ΔTb = Kbm

– freezing point depression, ΔTf = Kfm
Kb , Kf - molal boiling point elevation and freezing
point depression constant, respectively (K mol–1 kg)
Kb , Kf are properties of the solvent only and
independent of the identity of the solute
53
bm- molality of the solution (mol kg )–1
1.4 Colligative Properties of Solutions

54
1.4 Colligative Properties of Solutions

Example:

Given that Kb = 2.53oC/m for benzene,

what mass of acetone (CH3COCH3) must be

dissolved in 200 g of benzene to raise the
boiling point of benzene by 3.00oC.
55
 1.4 Colligative Properties of Solutions
Solution:

T = Kbm = Kb (moles acetone)

(kg benzene)

Moles acetone = (T/Kb) (kg benzene)

= (3.000C/ (2.530C/m))(0.2 kg benzene)
= 0.238 mol
Mass of acetone = (0.238 mol)(58.09 g/mol) =
56
 1.4 Colligative Properties
Osmotic Pressure of Solutions

iii. Osmotic Pressure

• Osmosis: the movement of a solvent from low solute
concentration to high solute concentration through
semipermeable membrane
(or from high solvent concn to low solvent concn)

• As solvent moves across the membrane the fluid

levels becomes uneven.

• The pressure difference between the arms stops

osmosis. Osmotic pressure () is the pressure
required to stop osmosis.
 1.6 Colligative properties of
1.4 Colligative Properties of Solutions
solutions
Osmosis and osmotic pressure

58
 1.6 Colligative properties of
1.4 Colligative Properties of Solutions
solutions

Osmotic pressure, 
In dilute aqueous solution:
n
p = MRT, M=
V

V = nRT
– This is the van’t Hoff equation for osmotic
pressure
59
1.4 Colligative Properties of Solutions

Example:

When 0.200 g of a high molecular weight compound is

dissolved in water to form 12.5 mL of solution at
250C, the osmotic pressure of the solution is found to
be 1.10 x 10-3 atm. What is the molar mass of the
compound?
60
 1.4 Colligative Properties of Solutions
Solution:
M = / RT = 1.10 X 10-3 atm
(0.0821 L.atm/K.mol)(298K)
= 4.50 X 10-5 mol/L

The number of moles in 0.200 g of the compound in 12.5

mL is:
Moles = (4.50 X 10-5 mol/L) (1L/1000mL)(12.5mL)
= 5.60 X 10-7 mol
 1.4 Colligative Properties of Solutions

Solution (cont.):

Molar mass of the compound:

0.200 g = 5.60 X 10-7 mol
molar mass

Molar mass = 0.200 g ( 1/5.60 X 10-7mol)

= 3.56 X 105 g
 1.6 Colligative properties of
1.4 Colligative Properties of Solutions
solutions
Measurement of solute dissociation
• E.g.
– 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
Based on NaCl(s)  Na+(aq) + Cl–(aq)
Solution has a total molality of dissolved solute
particles of 2 mol kg–1
– Thus, theoretically, a 1.00 mol kg–1 NaCl solution
should freeze at –3.72 °C NOT at –1.86 °C !!!!!!
1.4 Colligative Properties of Solutions
• Boiling-Point Elevation, ΔT = iK m
b b

• Freezing-Point Depression, ΔT = iK m
f f

• Osmotic Pressure,  = iMRT

Solute i

nonelectrolytes 1
E.g.
NaCl 2

CaCl2 3
64
 Question 1

•Arrange
  the following aqueous solutions having the
indicated mol fraction (X) of solute in increasing value
of vapour pressure of solution (Psolution). The pure
vapour pressure of water is . Justify your answers.
(i) = 0.015
(ii) = 0.008
(iii) = 0.010

65
 Question 2

A mixture was prepared by mixing 32.0 g of

nickel(II) nitrate in 250 mL of water. The final density
of the mixture was 1.10 g•mL-1. Given that Kf for
water is 1.86 oC•m-1, atomic mass of Ni, O and N is
58.69 g•mol-1, 16.00 g•mol-1 and 14.00 g•mol-1
respectively, calculate the: 
(i) concentration of the solution in molarity
(ii) osmotic pressure of the solution at 25°C
(iii) freezing point of the solution
66
 Question 3
Wastewater treatment is important to keep the
ecosystem healthy because it removes biological
and chemical wastes from the wastewater before it
enters the receiving water. Iron (III) chloride is
commonly used to remove phosphorous from the
wastewater. A 1.28 m iron (III) chloride (aq) solution
was prepared for this purpose. The solution has a
density of 1.163 g/mL. Determine the following:
(i) Molarity of the solution
(ii) Osmotic pressure of the solution
(iii) Boiling point of the solution 67
 Question 4
Wastewater treatment is important to keep the
ecosystem healthy because it removes biological
and chemical wastes from the wastewater before it
enters the receiving water. Iron(III) chloride is
commonly used to remove phosphorous from the
wastewater. A 1.28 m iron(III) chloride (aq) solution
was prepared for this purpose. The solution has a
density of 1.163 g/mL. Determine the following:
(i) Molarity of the solution
(ii) Osmotic pressure of the solution
(iii) Boiling point of the solution 68
 Question 5

A biochemical engineer isolates a bacterial gene

fragment and dissolves a 0.10 g sample of the
material in enough water to make 30 mL solution.
The osmotic pressure and density of the solution at
25oC are 840.0 atm and 0.807 g mL-1, respectively.
 (i) What is the molar mass of the gene fragment?
(ii) Calculate the freezing point depression, Tf of
this solution.

69
The End

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