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CHAPTER 1

Properties of
Solutions

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.
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SCOPE
1.1 Introduction to Solutions and Solubility
1.2 Factors Affecting Solubility:
Solute-solvent interactions
Temperature
Pressure

SCOPE
1.3 Quantitative Ways of Expressing
Concentration
Molarity, Molality
Parts by mass and by volume, Mole Fraction
1.4 Colligative Properties of Solutions
Vapor Pressure Lowering
Boiling Point Elevation
Freezing Point Depression

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
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1.1 Introduction to solutions


and solubility
Solvent
The dissolving
medium - most
abundant
component of a
given solution
Solute
A substance that
dissolves in the
dissolving medium
(solvent)

Solution
A
homogeneous
mixture of two
or more
substance

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
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Water
molecules

Undissolved NaCl

Dissolution process
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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
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solution.

1.2 Factors Affecting


Solubility

Solute - solvent interaction


Temperature
Pressure - for gases

1.2 Factors Affecting


Solute-Solvent Interactions
Solubility
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
Ionic bond

Hydrogen bond
Dipole-dipole
London dispersion force

Strength
increases

1.2
Factors
Affecting
Example
Solubility

Example (solute-solvent interaction):


Dissolving NaCl in H2O compared to dissolving
NaCl in benzene
NaCl experience ionic bond, H2O hydrogen
bond these bond is 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


Solute-Solvent 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

1.2 Factors Affecting


Solute-Solvent Interactions
Solubility

London Dispersion forces increases with


increasing molecular mass, leads to higher
solubilities
Eg: Solubility of gas in water
Gas

MW
(g/mol)

N2

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Solubility in H2O
at 20oC (M)
0.69 X 10-3

O2
Ar

32
40

1.38 X 10-3
1.50 X 10-3

Kr

83.8

2.79 X 10-3

1.2 Factors Affecting


Effect of Temperature
Solubility

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

1.2 Factors Affecting


Solubility

1.2 Factors Affecting


Effect of Pressure
Solubility
Pressure

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,

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.

1.2
Factors Affecting
Effect
of Pressure
Solubility

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, Henrys 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 Henrys law constant and is unique to each
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gas

Henrys Gas-Liquid
law
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 Henrys 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
Solutions
1.3 Liquid
solutions

Equation (Henrys Law) is only true at low


concentrations and pressures

An alternative expression of Henrys law is:


S1 S 2

P1 P2
S1 and P1 refer to initial conditions
S2 and P2 refer to final conditions

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Liquid-liquid
1.3 Liquid
solutionsSolutions

Formation of a liquidliquid 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
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Liquid-liquid Solutions
H
H


O H

C
C

C
C

H
H

Ethanol

Benzene
hydrogen bond H
H
C2 H5

H
H

H
C2H5

Likedissolveslike (ethanol is dissolved in H 2O)


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RECALL
CHEMISTRY I

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Liquid-solid
Solutions
1.3
Liquid solutions

Liquidsolid 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
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Liquid-solid
Solutions
1.3
Liquid solutions

Liquidsolid 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
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1.4 Quantification of
Liquid-solid
Solutions
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


(RECALL CHEMISTRY I)
MaXb(s)

aMc+(aq) + bXd(aq)

Ksp = [Mc+]a[Xd]b

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Liquid-solid 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

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Liquid-solid Solutions
Example:
The solubility of AgBr in water is 1.3 104 g L1 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

6
.
9

10
mol

1
M 187.77gmol
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Liquid-solid Solutions
Solution (cont):
[Ag+] = [Br] = 6.9 107 mol L1
Ksp = [Ag+][Br] = (6.9 107 mol L1)(6.9 107 mol L1)
Ksp = 4.8 1013 at 25 C

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1.4 Quantification of
Liquid-solid
Solutions
solubility:
the solubility
product

Example:

Calculate the molar solubility of lead iodide, PbI2,


given that Ksp(PbI2) = 7.9 109
Solution:
PbI2(s) Pb2+(aq) + 2I(aq), Ksp = [Pb2+][I]2
Define the molar solubility of PbI2(s) as s (mol L1)
[Pb2+] = s, [I] = 2s
Ksp = (s)(2s)2 = (s)(4s2) = 4s3 = 7.9 109
s = 1.3 10

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Liquid-solid 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

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1.4 Quantification of
Liquid-solid
Solutions
solubility:
the solubility
product
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 = 7.9 109
PbI2(s)

Pb2+(aq) +

2I(aq)

Initial concentration (M)

0.10

Change in concentration (M)

+s

+2s

Equilibrium concentration (M)

0.10 + 2s

Ksp = s(0.10 + 2s)2 = 7.9 109


2

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1.4 Quantification of
Liquid-solid
Solutions
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 1010
[Ag+] = 5.0 107 mol L1
[Cl] = 5.0 105 mol L1
Qsp = 2.5 1011
Qsp < Ksp no precipitate will form

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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 +
n +n
A + n BB +nCC

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 in
in solution
solution XX
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
mass of
of component
component in
in solution
solution XX
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10
10
total
total
mass
of solution
solution
mg/Kg
= mass
ppm
wtof
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
mass of
of component
component in
in solution
solution XX
9
10
109
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 Concentration


Example
Example:
What is the mass percentage of iodine (I 2) in a
solution containing 0.045 mol I2 in 115 g of CCl4 ?
Solution:
massof component
mass%
100
totalmasssolution
253.8g
massof solute 0.045molI2
11.42gI2
mol
11.421g
mass%
100 9.0%I2
11.421g 115g

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
6

10
1000 g H 2 O 0.0079 g Sr 2
7.9 ppm Sr

Quantitative Ways of Expressing Concentration


1.3
Expressing Concentration

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

Quantitative Ways of Expressing Concentration


1.3
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
moles of
of solute
solute
kilograms
kilograms of
of solvent
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

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,

1.6
properties
of of
1.4Colligative
Colligative
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
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1.6
Colligative
properties
of
1.4 Colligative Properties of
solutions Solutions

The vapor pressure of solvent above the


solution is expressed by Raoults Law:

Psolution = xsolvent P*solvent


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

For a simple two component system


Provided the solution is sufficiently49 dilute

1.6 Colligative Properties


properties of
1.4
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
P = xsoluteP*solvent
P = P*solvent Psolution
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Colligative
properties
1.41.6
Colligative
Properties
of
of solutions
Solutions
Raoults law
A solution that obeys Raoults law is called an ideal
solution
These solutions are
generally dilute and have
only small interactions
between their constituent
molecules

51

Colligative
properties
1.41.6
Colligative
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

Colligative
properties
1.41.6
Colligative
Properties
of
of solutions
Solutions
ii. Boiling point elevation and
Freezing point depression
boiling point elevation, Tb = Kbb
freezing point depression, Tf = Kfb
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
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1
b - molality of the solution (mol kg )

1.4 Colligative Properties of


Solutions

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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
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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 Colligative
Colligative Properties
properties of
1.4
of solutions
Solutions
Osmosis and osmotic pressure

58

1.6
properties
of of
1.4Colligative
Colligative
Properties
solutions Solutions
Osmotic pressure,
In dilute aqueous solution:

n
= cRT, c
V

V = nRT
This is the vant Hoff equation for osmotic
pressure
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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/mol

1.6
properties
of of
1.4Colligative
Colligative
Properties
solutions Solutions
Measurement of solute dissociation
E.g.
Molal freezing point depression constant for water
is 1.86 K mol1
1.00 mol kg1 NaCl freezes at about 3.72C
Based on NaCl(s) Na+(aq) + Cl(aq)
Solution has a total molality of dissolved solute
particles of 2 mol kg1
Thus, theoretically, a 1.00 mol kg1 NaCl solution
should freeze at 3.72 C NOT at 1.86 C !!!!!!

1.4 Colligative Properties of


Solutions

Boiling-Point Elevation, T = iK m
Freezing-Point Depression, T = iK m
Osmotic Pressure, = iMRT
b

E.g.

Solute

nonelectrolytes

NaCl

CaCl2

3
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The End
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