CHM12-3

Lecture Unit No.3

 SOLUTIONS
– Physical Properties

 Engr. E. L. Estopace
 School of Chemical Engineering and Chemistry
 Mapua Institute of Technology 1
 Scope
1. Types of Intermolecular Forces of
Attraction
2. Types of Concentration Units
3. Factors Affecting Solubility
4. Colligative Properties of Solutions
5. Determining Molar Mass Using
Colligative Properties of Solutions
6. Colligative Properties of
Electrolytes

2
INTRODUCTION:
Solutions in Everyday Life
• Morning coffee
• Solutions of solids (sugar, coffee) in liquid (water)
• Gasoline
• Solution of liquid hydrocarbons
• Soda
• Solution of sugar, water and carbon dioxide
• Air
• Solution of oxygen and nitrogen
INTERMOLECULAR FORCES of ATTRACTION
 STRENGTH OF IMF
 London<dipole-dipole<H-bonding<ion-dipole<ionic bonding

SUMMARY
IONIC  ionic bonding
NONPOLAR COMPOUNDS  London Dispersion forces

POLAR MOLECULES
 With ions  Ion-dipole
 With H bonded to O, F and N  H-bonding
 Without hydrogen  dipole-dipole

4
Solutions
 Solutions are homogeneous mixtures of two
or more substances.
– Dissolving medium is called the solvent.
– Dissolved species are called the solute.
 There are three states of matter (solid, liquid,
and gas) which when mixed two at a time
gives nine different kinds of mixtures.
–.

5
 Solutions
 Existin all 3 physical states
 Can be mixtures of solids, liquids and
gases

Type of Solution Examples

Gas in gas Air
Gas in liquid Carbonated drinks.
Gas in solid Hydrogen in Pd metal.
Liquid in liquid Motor oil, vinegar.
Solid in liquid Ocean water, sugar-water.
Solid in solid Bronze, 14K gold.
 Solutions
Like dissolves like
If solute and solvent intermolecular forces are:
• Similar… the pair will be soluble.
 polar dissolves polar;
 non-polar dissolves non-polar

• Dissimilar
= insoluble.
Solutions
Substances dissolve when:
solvent-solute attraction > solvent-solvent
attraction,
and > solute-solute
attraction
 Solutions
Miscible liquids dissolve in all proportions.
e.g. ethanol and water (both H-bonded polar liquids).

Immiscible liquids form distinct separate phases.

e.g. gasoline (non-polar) and water (polar).

Carefully layered liquids

(different d):

(a) colorless CCl4; green

NiCl2(aq); colorless C7H16(l).

(b) After mixing and settling.

 Solutions
Name Formula Solubility (g/100g H2O @20°C)
methanol CH3OH miscible
ethanol C2H5OH miscible
London
1-propanol C3H7OH miscible
forces
1-butanol C4H9OH 7.9
increasing
1-pentanol C5H11OH 2.7
1-hexanol C6H13OH 0.6

Solubility in water decreases as alcohols grow larger

because:
Solute-solute attraction grows
Solute-solvent attraction stays ≈ constant.
Solutions

 Nonpolar molecules essentially “slide”

in between each other.
– For example, carbon tetrachloride and
benzene are very miscible.
H
Cl H C H
C C
Cl C Cl
C C
Cl H C H

H 11
WAYS OF EXPRESSING
CONCENTRATION OF
SOLUTIONS

12
 Percent by mass
1. % by mass/weight of solute

mass of solute
% w/w = 100%
mass of solution

13
 Percent by mass
Mass Solute
Mass fraction =
Total Mass of Solution
Weight percent = Mass fraction x 100%

Example
Saline solutions (NaCl in water) are often used in
medicine. What is the weight percent of NaCl in a solution
of 4.6 g of NaCl in 500. g of water?
4.6 g
mass fraction = = 0.0091
500. g + 4.6 g
weight percent = 0.0091 x 100% = 0.91 %
 Molarity
2. Molarity
moles of solute
M =
Liters of solution
• V of solution not solvent.
• Shorthand: [NaOH] =1.00 M

The brackets [ ] represent

“molarity of ”

15
 Molarity
Calculate the molarity of sodium sulfate in a
solution that contains 36.0 g of Na2SO4 in
750.0 mL of solution.
36.0 g = 0.2534 mol
nNa2SO4 =
142.0 g/mol

0.2534 mol
[Na2SO4 ] = Unit change!
0.7500 L (mL to L)

[Na2SO4 ] = 0.338 mol/L = 0.338 M

 Molality and Mole Fraction
 Molality is a concentration unit based on
the number of moles of solute per
kilogram of solvent.
moles of solute
m
kg of solvent
in dilute aqueous solutions molarity and
molality are nearly equal
17
 Molality and Mole Fraction
 Mole fraction is the number of moles of one
component divided by the moles of all the
components of the solution
– Mole fraction is literally a fraction using moles of one
component as the numerator and moles of all the
components as the denominator.
 In a two component solution, the mole fraction of
one component, A, has the symbol XA.

number of moles of A
XA
number of moles of A + number of moles of B
18
 Molality and Mole Fraction
 The mole fraction of component B - XB

number of moles of B
XB
number of moles of A + number of moles of B
Note that X A X B 1
The sum of all the mole fractions must equal 1.00.

19
 Molality and Mole Fraction
Calculate the molality of a solution that contains
7.25 g of benzoic acid C6H5COOH, in 2.00 x 102
mL of benzene, C6H6. The density of benzene is
0.879 g/mL. 1 mol C6H5COOH = 122 g
You do it!

? mol C 6 H 5COOH 7.25g C 6 H 5COOH 1 mL C 6 H 6

kg C 6 H 6 200.0 mL C 6 H 6 0.879 g C 6 H 6
1000 g C 6 H 6 1 mol C 6 H 5COOH
0.338 m C 6 H 5COOH
1 kg C 6 H 6 122 g C 6 H 5COOH
20
 Molality and Mole Fraction
 Example : What are the mole fractions of
glucose and water in a 10.0% glucose
solution (Example 14-1)?
You do it!
2
In 1.00 10 g of this solution t here are
10.0 g of glucose and 90.0 g of water.
? mol C 6 H12O 6 10.0 g C 6 H12O 6
1 mol C 6 H12O 6
0.0556 mol C 6 H12O 6
180 g C 6 H12O 6
21
 Molality and Mole Fraction
 Example 14-3: What are the mole fractions of
glucose and water in a 10.0% glucose solution ?

1 mol H 2 O
? mol H 2O 90.0 g H 2O 5.00 mol H 2 O
18 g H 2 O

22
Molality and Mole Fraction
 Now we can calculate the mole fractions.
5.00 mol H 2 O
X H 2O
5.00 mol H 2 O + 0.0556 mol C 6 H 12 O 6
0.989
0.0556 mol C 6 H 12 O 6
X C6 H12 O 6
5.00 mol H 2 O + 0.0556 mol C 6 H 12 O 6
0.011
1.00 0.989 0.011

23
Parts per Million, Billion and Trillion
% = Parts per hundred = mass solute x 102
mass solution

Very dilute = low mass fraction.

Units for high dilution (trace solute):

Parts per million (ppm) = mass solute x 106

mass solution

Parts per billion (ppb) = mass solute x109

mass solution

Parts per trillion (ppt) = mass solute x1012

mass solution
Parts per Million, Billion and Trillion

1 ppm of solute in water = 1 mg / 1000 g of

solution

Since 1L of water has a mass ≈ 1000 g.

1 ppm ≈ 1 mg/L

Similarly 1 ppb ≈ 1 μg/L

1 ppt ≈ 1 ng/L
Conversions Between Concentration Units
• To convert between units, first decide on a fixed amount
of solution to start with:

When the original Choose

concentration is
Mass percent 100 g solution

Molarity (M) 1.00 L solution

Molality (m) 1.00 kg solvent

Mole fraction (X) 1.00 mol solution

Changing Molarity to Molality

If we know the
density of the
solution, we can
calculate the
molality from the
molarity, and vice
versa.
Solubility
• The process by which one substance
dissolves in another is ordinarily a physical
change
• The resulting mixture is a solution
• Solutions may be classified by the relative
amount of solute and solvent
• Saturated: maximum amount of solute
• Unsaturated: less than maximum amount of
solute
• Supersaturated: more than maximum amount of
solute
Figure 3.1 – Sugar Crystals
Factors Affecting
Solubility
Figure 3.2 – Solubility and Temperature
 Supersaturation
“seed” crystal
of sodium The solution warms…
acetate
…heat is released as crystals form

Excess sodium
Supersaturated acetate begins to More and more
sodium acetate crystallize around crystallizes until
solution the seed a saturated
solution remains.
 Dissolution of Gases in Liquids
 Polar gases are more soluble in water
than nonpolar gases.
– This is the “like dissolves like” rule in action.
 Polar gases can hydrogen bond with water
 Some polar gases enhance their solubility
by reacting with water. + -
HBr + H 2 O H 3O aq Br aq

strong acid
SO 2 + H 2 O H 2SO 3 aq
H 2O -
+
H 2SO 3(aq) H 3O aq HSO 3 aq
33
weak acid
 Effect of Temperature on Solubility
 According to LeChatelier’s Principle when stress is
applied to a system at equilibrium, the system
responds in a way that best relieves the stress.
– Since saturated solutions are at equilibrium, LeChatelier’s
principle applies to them.
 Possible stresses to chemical systems include:
1. Heating or cooling the system.
2. Changing the pressure of the system.
3. Changing the concentrations of reactants or products.

34
 Effect of Temperature on Solubility
 What will be the effect of heating or cooling the
water in which we wish to dissolve a solid?
– It depends on whether the dissolution is exo- or
endothermic.
 For an exothermic dissolution, heat can be
considered as a product.
H 2O + -
LiBr s Li aq Br aq 48.8kJ / mol
 Warming the water will decrease solubility and cooling the
water will increase the solubility.
 Predict the effect on an endothermic dissolution like this one.
H 2O + -
KMnO 4 s 43.6 kJ / mol K aq MnO 4 aq

35
Effect of Temperature on Solubility

36
Effect of Temperature on Solubility

• For a gas, the dissolution process is

exothermic, so the reverse process
(gas evolving from solution) is
endothermic
• Therefore, for gases, solubility
decreases with increasing
temperature
Effect of Pressure on Solubility
 Pressure changes have little or no effect
on solubility of liquids and solids in
liquids.
– Liquids and solids are not compressible.
 Pressure changes have large effects on
the solubility of gases in liquids.
– Sudden pressure change is why
carbonated drinks fizz when opened.
– It is also the cause of several scuba diving
related problems including the “bends”.
38
Effect of Pressure on Solubility
• Pressure has a major effect on the
solubility of a gas in a liquid, but little
effect on other systems
• At low to moderate pressure, the
concentration of a gas increases with
the pressure (Henry’s law):
• Cg = kPg, where
• Pg is the partial pressure of the gas over the
solution
• Cg is the concentration of the gas
• k is a constant (the Henry’s Law constant)
 Effect of Pressure on Solubility
 The effect of pressure on the solubility of gases in
liquids is described by Henry’s Law.
Pgas
gas
kkMM
gasgas

where M
where M gas
gas
molar
molarconcentrat ion of
concentrat iongasof gas
k = Henry' s Law constant, unique number for each
gas - liquid combinatio n
Pgas = partial pressure of gas

40
Colligative Properties of
Solutions
 Colligative properties are properties of
solutions that depend solely on the
number of particles dissolved in the
solution.
– Colligative properties do not depend on the
kinds of particles dissolved.
 Colligative properties are a physical
property of solutions.
41
Colligative Properties of
Solutions
 There are four common types of
colligative properties:
1. Vapor pressure lowering
2. Freezing point depression
3. Boiling point elevation
4. Osmotic pressure
 Vapor pressure lowering is the key to
all four of the colligative properties.
42
 Lowering of Vapor Pressure and
Raoult’s Law
 Addition of a nonvolatile solute to a
solution lowers the vapor pressure of the
solution.
– The effect is simply due to fewer solvent
molecules at the solution’s surface.
– The solute molecules occupy some of the
spaces that would normally be occupied by
solvent.
 Raoult’s Law models this effect in ideal
solutions. 43
 Lowering of Vapor Pressure and
Raoult’s Law
 Derivation of Raoult’s Law.
0
Psolvent X solvent Psolvent
where Psolvent vapor pressure of solvent in solution
0
Psolvent vapor pressure of pure solvent
X solvent mole fraction of solvent in solution

44
Lowering of Vapor Pressure and
Raoult’s Law
 Lowering of vapor pressure, Psolvent, is defined
as:
0
Psolvent Psolvent Psolvent
0 0
Psolvent - ( X solvent)( P solvent )
0
(1 X solvent)P solvent

45
 Lowering of Vapor Pressure and
Raoult’s Law
 Remember that the sum of the mole
fractions must equal 1.
 Thus Xsolvent + Xsolute = 1, which we can
substitute into our expression.
X solute 1 - X solvent
0
Psolvent X solute P
solvent

which is Raoult' s Law

46
Lowering of Vapor Pressure and
Raoult’s Law
 This graph shows how the solution’s vapor
pressure is changed by the mole fraction of the
solute, which is Raoult’s law.

47
 Boiling Point Elevation
 Addition of a nonvolatile solute to a
solution raises the boiling point of the
solution above that of the pure solvent.
– This effect is because the solution’s vapor
pressure is lowered as described by Raoult’s
law.
– The solution’s temperature must be raised to
make the solution’s vapor pressure equal to
the atmospheric pressure.
 The amount that the temperature is
elevated is determined by the number of
moles of solute dissolved in the solution.
48
Boiling Point Elevation

 Boiling point elevation relationship is:

Tb Kbm
where : Tb boiling point elevation
m molal concentrat ion of solution
K b molal boiling point elevation constant
for the solvent

49
 Boiling Point Elevation
 Example 14-4: What is the normal boiling
point of a 2.50 m glucose, C6H12O6,
solution?
Tb K bm
Tb (0.512 0 C/m)( 2.50m)
Tb 1.280 C
Boiling Point of the solution = 100.00 C + 1.280 C = 101.280 C

50
 Freezing Point Depression
 Addition of a nonvolatile solute to a
solution lowers the freezing point of the
solution relative to the pure solvent.
 See table 14-2 for a compilation of boiling
point and freezing point elevation
constants.

51
 Freezing Point Depression
 Relationship for freezing point depression
is: T K m
f f
where: Tf freezing point depression of solvent
m molal concentration of soltuion
Kf freezing point depression constant for solvent

52
Freezing Point Depression
 Notice the similarity of the two
relationships for freezing point depression
and boiling point elevation.
Tf K f m vs. Tb Kbm
 Fundamentally, freezing point depression and boiling
point elevation are the same phenomenon.
– The only differences are the size of the effect which is
reflected in the sizes of the constants, Kf & Kb.
 This is easily seen on a phase diagram for a solution.

53
 Freezing Point Depression

 Example 14-5: Calculate the freezing

point of a 2.50 m aqueous glucose
solution. Tf K f m
Tf (1.86 0 C/m)( 2.50m)
Tf 4.650 C
Freezing Point of solution = 0.000 C - 4.650 C = - 4.650 C

54
Freezing Point Depression

 Example 14-6: Calculate the freezing

point of a solution that contains 8.50 g
of benzoic acid (C6H5COOH, MW =
122) in 75.0 g of benzene, C6H6.
You do it!

55
 Freezing Point Depression
1. Calculate molality!
? mol C 6 H 5 COOH 8.50 g C 6 H 5 COOH
kg C 6 H 6 0.0750 kg C 6 H 6
1 mol C 6 H 5 COOH
0.929m
122 g C 6 H 5 COOH
2. Calculate the depression for this solution.
Tf Kf m
Tf (5.12 0 C/m)( 0.929m) 4.76 0 C
F.P. = 5.480 C - 4.76 0 C = 0.72 0 C
56
Determination of Molecular
Weight by Freezing Point
Depression
 The size of the freezing point depression
depends on two things:
1. The size of the Kf for a given solvent, which are
well known.
2. And the molal concentration of the solution which
depends on the number of moles of solute and
the kg of solvent.
 If Kf and kg of solvent are known, as is
often the case in an experiment, then we
can determine # of moles of solute and use
it to determine the molecular weight. 57
 Determination of Molecular
Weight by Freezing Point
Depression
 Example 14-7: A 37.0 g sample of a new
covalent compound, a nonelectrolyte, was
dissolved in 2.00 x 102 g of water. The
resulting solution froze at -5.58oC. What is
the molecular weight of the compound?

58
 Determination of Molecular
Weight by Freezing Point
Depression
T K m thus the
f f

Tf 5.580 C
m 3.00m
Kf 1.860 C
In this problem there are
200 mL 0.200 kg of water.
? mol compound in 0.200 kg H 2 O = 3.00 m 0.200 kg
0.600 mol compound
37 g
Thus the molar mass is 61.7 g/mol
0.600 mol
59
 Colligative Properties and
Dissociation of Electrolytes
 Electrolytes have larger effects on boiling point
elevation and freezing point depression than
nonelectrolytes.
– This is because the number of particles released in
solution is greater for electrolytes
 One mole of sugar dissolves in water to produce
one mole of aqueous sugar molecules.
 One mole of NaCl dissolves in water to produce
two moles of aqueous ions:
– 1 mole of Na+ and 1 mole of Cl- ions

60
 Colligative Properties and
Dissociation of Electrolytes
 Remember colligative properties depend on
the number of dissolved particles.
– Since NaCl has twice the number of particles we
can expect twice the effect for NaCl than for
sugar.
 The table of observed freezing point
depressions in the lecture outline shows this
effect.

61
Colligative Properties and
Dissociation of Electrolytes
 Ion pairing or association of ions
prevents the effect from being exactly
equal to the number of dissociated ions

62
 Colligative Properties and
Dissociation of Electrolytes
 The van’t Hoff factor, symbol i, is used to
introduce this effect into the calculations.
 i is a measure of the extent of ionization or
dissociation of the electrolyte in the
solution.
Tf actual
i
Tf if nonelectrolyte

63
 Colligative Properties and
Dissociation of Electrolytes
 i has an ideal value of 2 for 1:1 electrolytes like NaCl,
KI, LiBr, etc.

Na + Cl- H 2O
Na +aq Cl-aq 2 ions
formula unit
 i has an ideal value of 3 for 2:1 electrolytes like
K2SO4, CaCl2, SrI2, etc.

Ca 2+ Cl-2 H 2O
Ca 2aq+ 2 Cl-aq 3 ions
formula unit
64
 Colligative Properties and
Dissociation of Electrolytes
 Example 14-8: The freezing point of 0.0100 m
NaCl solution is -0.0360oC. Calculate the van’t
Hoff factor and apparent percent dissociation of
NaCl in this aqueous solution.
 meffective = total number of moles of solute
particles/kg solvent
 First let’s
T calculate the i factor.
f actual K f meffective meffective
i
Tf if nonelectrolyte K f mstated mstated
65
 Colligative Properties and
Dissociation of Electrolytes

Tf actual K f meffective meffective

i
Tf if nonelectrolyte K f mstated mstated
Tf actual 0.0360 0 C
Tf actual K f meffective meffective
Kf 1.86 0 C m
meffective 0.0194 m
meffective 0.0194 m i 194
.
mstated 0.0100 m

66
 Osmotic Pressure
 Osmosis is the net flow of a solvent between
two solutions separated by a semipermeable
membrane.
– The solvent passes from the lower concentration
solution into the higher concentration solution.
 Examples of semipermeable membranes
include:
1. cellophane and saran wrap
2. skin
3. cell membranes

67
 Osmotic Pressure
semipermeable membrane

H2O H2O

sugar dissolved H2O H2O net2solvent flow

H2O O
in water
H2O H2O

68
Osmotic Pressure

69
 Osmotic Pressure
 Osmosis is a rate controlled phenomenon.
– The solvent is passing from the dilute solution into the
concentrated solution at a faster rate than in opposite
direction, i.e. establishing an equilibrium.
 The osmotic pressure is the pressure exerted by
a column of the solvent in an osmosis
experiment.
MRT
where: = osmotic pressure in atm
M = molar concentration of solution
L atm
R = 0.0821
mol K
70
T = absolute temperature
 Osmotic Pressure

 For very dilute aqueous solutions,

molarity and molality are nearly equal.
M m
mRT
for dilute aqueous solutions only

71
 Osmotic Pressure
 Osmotic pressures can be very large.
– For example, a 1 M sugar solution has an
osmotic pressure of 22.4 atm or 330 p.s.i.
 Since this is a large effect, the osmotic
pressure measurements can be used to
determine the molar masses of very large
molecules such as:
1. Polymers
2. Biomolecules like
• proteins
• ribonucleotides 72
 Osmotic Pressure
 Example 14-18: A 1.00 g sample of a
biological material was dissolved in enough
water to give 1.00 x 102 mL of solution. The
osmotic pressure of the solution was 2.80
torr at 25oC. Calculate the molarity and
approximate molecular weight of the
material.
You do it!

73
 Osmotic Pressure
MRT M
RT
1 atm
? atm = 2.80 torr 0.00368 atm =
760 torr
0.00368 atm 4
M = L atm
150
. 10 M
0.0821 mol K 298 K

74
 Osmotic Pressure
MRT M
RT
1 atm
? atm = 2.80 torr 0.00368 atm =
760 torr
0.00368 atm 4
M = L atm
150
. 10 M
0.0821 mol K
298 K
?g 1.00 g 1L
4
6.67 10 4 g mol
mol 0.100 L 150. 10 M
typical of small proteins
75
End of Lecture 3
 Human Beings are solution chemistry in
action!

76
 Scope
1. Types of Intermolecular Forces of
Attraction
2. Types of Concentration Units
3. Factors Affecting Solubility
4. Colligative Properties of Solutions
5. Determining Molar Mass Using
Colligative Properties of Solutions
6. Colligative Properties of
Electrolytes

77
 CHM12-3
Lecture Unit No.3

 SOLUTIONS
– Physical Properties

 Engr. E. L. Estopace
 School of Chemical Engineering and Chemistry
 Mapua Institute of Technology 78