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
– Osmotic Pressure 4
 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
– Dissolved substance in liquid solution 5
 1.1 Introduction to solutions
and solubility
Solvent
The dissolving
medium - most
abundant
component of a Solution
given 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
 1.2 Factors Affecting
Solute-Solvent 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
 1.2 Factors Affecting Solubility
Solute-Solvent 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
 1.2 Factors Affecting
Solute-Solvent 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 Effect
Factors Affecting Solubility
of Temperature
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

Sgas  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
gas 21
 Henry’s law
Gas-Liquid Solutions

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
S2 and P2 refer to final conditions
23
 Liquid-liquid
1.3 Solutions
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
H H C C
H C H
H
Ethanol
Benzene

hydrogen bond H H
H O H O
C2H5 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)
Ksp = [Mc+]a[Xd–]b 29
 Solid-liquid Solutions

• 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 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–]

m 1. 3  10  4 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, PbI2,
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
s = 1.3 × 10–3
33
The molar solubility of PbI2(s) = 1.3 × 10–3 molL–1
 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
PbCl2 is precipitated 34
 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

Ksp = s(0.10)2 = 7.9 × 10–9
Molar solubility of PbI2 in 0.10 M NaI solution is 7.9×10–735M
1.4 Quantification of solubility:
Solid-liquid Solutions
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 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

xA = nA
nA + n B +nC

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 % of Component

= Mole of component in solution X 100

total mole of 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 of component
= mass of component in solution X 106
total mass of 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 of component
= mass of component in solution X 109
total mass of solution

if with respect to concentration of solute in water

 1 ppb = 1 g/L
 1.3 Expressing Concentration
Example
Example:
What is the mass percentage of iodine (I2) in a
solution containing 0.045 mol I2 in 115 g of CCl4 ?

Solution:
massof component
mass%   100
total masssolution
253.8 g
massof solute  0.045 mol I2   11.42 g I2
mol
11.421g
mass%   100  9.0 %I2
11.421g  115 g
 1.3 Expressing Concentration
Example

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
 2
10 6

1000 g H 2 O  0.0079 g Sr
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 (M) = moles of solute

liters 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 (m) = moles of solute
kilograms of 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 of
Colligative Properties
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
 osmotic pressure of a solution
 1.6 Colligative
1.4 Colligativeproperties ofof
Properties
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
propertiesofof
solutions
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
 1.41.6 Colligative
Colligative properties
Properties of of
solutions
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
51
 1.41.6 Colligative
Colligative properties
Properties of 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
 1.41.6 Colligative
Colligative properties
Properties of 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
bm- molality of the solution (mol kg–1) 53
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
= 13.8 g
 1.4 Colligative Properties of
Osmotic Pressure
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
1.4 Colligative properties
Properties of
solutions
Solutions
Osmosis and osmotic pressure

58
1.6 Colligative
1.4 Colligativeproperties ofof
Properties
solutions
Solutions

Osmotic pressure, 

In dilute aqueous solution:

n
 = 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
1.4 Colligativeproperties ofof
Properties
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, ΔTb = iKbm
• Freezing-Point Depression, ΔTf = iKfm
• 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 PHo2 O . Justify your
answers.
(i) XNaCl = 0.015
(ii) XMg(OH)2 = 0.008
(iii)Xsucrose = 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

70