The Chemistry of Solutes

and Solutions
William Francois
Henry Raoult
.1774-1836 .1830-1901
.Henry’s Law .Raoult’s Law

2
The Solution Process
.Solutes and solvent are components of the solution •
In the process of making solutions with condensed •
.phases, intermolecular forces become rearranged
:Consider NaCl (solute) dissolving in water (solvent) •
,the water H-bonds have to be interrupted –
,-NaCl dissociates into Na+ and Cl –
.ion-dipole forces form: Na+ … -OH2 and Cl- … +H2O –

+δ
-δ H
+
Na
-
Cl H O
O
H H

3
The Solution Process

4
The Solution Process
Rule”: LIKE DISSOLVES LIKE“ •
.polar solvents dissolve polar solutes •
.Non-polar solvents dissolve non-polar solutes •
.Water is polar (because it’s bent)
.It will therefore tend to dissolve other polar molecules or ions
.For example, most salts, alcohols and sugars dissolve in water
:Alcohols and sugars all contain the O-H part of a molecule which makes them polar

..
X . .O

H
5
The Solution Process
.Most organic substances (compounds of carbon) are non-polar
.That is why they in general do not dissolve in water (which is polar)

H H H H

C C
C C
H H
H
H

.Generally, carbon chains are non-polar (no dipole moment)

Since the electronegativities of hydrogen and carbon are virtually
,the same, hydrocarbons are non-polar. Gasoline is non-polar
.because it is a hydrocarbon

6
Solute-Solvent Interactions
.Miscible liquids: mix in any proportions •
.Immiscible liquids: do not mix •
.Soluble liquids: mix in certain proportions •
Intermolecular forces are important: water and ethanol •
are miscible because the broken hydrogen bonds in
.both pure liquids are re-established in the mixture
The number of carbon atoms in a chain affect solubility: •
.the more C atoms the less soluble in water

7
Degree of saturation
Saturated solution •
Solvent holds as much 
solute as is possible at
.that temperature
Undissolved solid 
.remains in flask
Dissolved solute is in 
dynamic equilibrium
with solid solute
.particles
 Degree of saturation

Unsaturated Solution •
Less than the
maximum amount of
solute for that
temperature is
dissolved in the
.solvent
No solid remains in
.flask
 Degree of saturation

Supersaturated •
Solvent holds more solute than is normally
.possible at that temperature
These solutions are unstable; crystallization can
often be stimulated by adding a “seed crystal”
.or scratching the side of the flask
 Degree of saturation

?Unsaturated, Saturated or Supersaturated

? How much solute can be dissolved in a solution

 Factors Affecting Solubility

Chemists use the rule •

:”“like dissolves like
Polar substances tend to
dissolve in polar
.solvents
Nonpolar substances
tend to dissolve in
.nonpolar solvents
 Factors Affecting Solubility

The stronger the

intermolecular
attractions
between solute and
Example: ethanol in water solvent, the more
Ethanol = CH3CH2OH
likely the solute will
.dissolve
Intermolecular forces = H-bonds; dipole-dipole; dispersion

.Ions in water also have ion-dipole forces

 Factors Affecting Solubility

Glucose (which has

hydrogen bonding)
is very soluble in
.water
Cyclohexane (which
only has dispersion
forces) is not water-
.soluble
 Factors Affecting Solubility
Vitamin A is soluble in nonpolar compounds •
.(like fats)
.Vitamin C is soluble in water •
Which vitamin
is water-
soluble and
which is fat-
?soluble
 Gases in Solution

In general, the •
solubility of gases in
water increases with
.increasing mass
?Why
Larger molecules •
have stronger
.dispersion forces
 Gases in Solution

The solubility of •
Increasing
pressure above liquids and solids
solution forces does not change
more gas to
.dissolve appreciably with
.pressure
But, the solubility of a •
gas in a liquid is
directly proportional
.to its pressure
 Henry’s Law
Sg = kPg
where
Sg is the solubility of the •
;gas
k is the Henry’s law •
constant for that gas in
;that solvent
Pg is the partial pressure •
of the gas above the
.liquid
Temperature

Generally, the
solubility of solid
solutes in liquid
solvents increases
with increasing
.temperature
 Temperature
The opposite is true of •
gases. Higher
temperature drives
.gases out of solution

Carbonated soft drinks 

are more “bubbly” if
stored in the
.refrigerator
Warm lakes have less O2 
dissolved in them than
.cool lakes
Ways of Expressing
Concentrations of
Solutions
 Mass Percentage

mass of A in solution
= Mass % of A  100
total mass of solution
 Parts per Million and
Parts per Billion
Parts per Million (ppm)
mass of A in solution
= ppm  106
total mass of solution

Parts per Billion (ppb)

mass of A in solution
= ppb  109
total mass of solution
 Mole Fraction (X)
moles of A
= XA
total moles in solution

In some applications, one needs the mole •

fraction of solvent, not solute—make sure
!you find the quantity you need
 Molarity (M)

mol of solute
=M
L of solution

Because volume is temperature dependent, •

.molarity can change with temperature
 Molality (m)

mol of solute
=m
kg of solvent

Because neither moles nor mass change with

temperature, molality (unlike molarity) is
.not temperature dependent
 Ma
ss
/M
ass
s
ole
/M
les
Mo

s /L M
ole ole
M
s /M
as
s
 SAMPLE EXERCISE 13.4 Calculation of Mass-Related Concentrations

A solution is made by dissolving 13.5 g of glucose (C 6H12O6) in 0.100 kg of water. What is the )a(
mass percentage of solute in this solution? (b) A 2.5-g sample of groundwater was found to contain
?5.4g of Zn2+ What is the concentration of Zn 2+ in parts per million

PRACTICE EXERCISE
Calculate the mass percentage of NaCl in a solution containing 1.50 g of NaCl in 50.0 g of water. )a(
(b) A commercial bleaching solution contains 3.62 mass % sodium hypochlorite, NaOCl. What is the
?mass of NaOCl in a bottle containing 2500 g of bleaching solution

PRACTICE EXERCISE
A commercial bleach solution contains 3.62 mass % NaOCl in water. Calculate (a) the molality and (b) the mole
.fraction of NaOCl in the solution
Properties of Liquids: Surface
Tension
 Surface Tension and Capillary Action

Surface Tension-a force that tends to pull adjacent parts of a

liquid’s surface together, thereby decreasing surface area to
.the smallest possible size
The higher the attraction forces (intermolecular forces), the~
higher the surface tension. Surface tension causes liquid
.droplets to take a spherical shape
Capillary action- the attraction of the surface of a liquid to the
.surface of a solid
Capillary action is the reason of raise of water from the roots~
of a tree goes to the leaves. It is also responsible for the
.liquid surface called the meniscus
 Surface Tension
The surface of any liquid behaves as if it was a •
stretched membrane. This phenomenon is
known as surface tension
Surface tension is caused by intermolecular •
forces at the liquid’s interface with a gas or a
.solid
Surface tension depends on the nature of the •
.liquid, the surrounding media and temperature
Liquids that have strong intermolecular forces •
will have higher values of surface tension than
.liquids that have weak intermolecular forces
 Intermolecular forces acting on a
molecule

gas

liquid

а, б) – inside the volume of liquid

в) – in the surface layer
 Surface and interfacial tensions
It is well known that short-range forces of attraction exist
between molecules, and are responsible for the existence of the
liquid state. The phenomena of surface and interfacial tension are
readily explained in terms of these forces. The molecules which
are located within the bulk of a liquid are, on average, subjected
to equal forces of attraction in all directions, whereas those
located at, for example, a liquid-air interface experience
.unbalanced attractive forces resulting in a net inward pull
As many molecules as possible will leave the liquid surface for
the interior of the liquid; the surface will therefore tend to
contract spontaneously. For this reason, droplets of liquid and
.bubbles of gas tend to attain a spherical shape
Drops of liquid takes the form of
sphere
Intermolecular forces at interfaces:
The short-range intermolecular forces which are
responsible for surface/interfacial tensions include van
der Waals forces (in particular, London dispersion
forces, which are universal) and may include hydrogen
bonding (as, for example, in water) and metal bonding
(as, for example, in mercury). The relatively high values
of the surface tensions of water and mercury (see Table
4.1) reflect the contributions of hydrogen bonding and
.metal bonding, respectively
It is easy to demonstrate that the surface energy of
a liquid actually gives rise to a ‘surface tension’
or force acting to oppose any increase in surface
.area

Surface tension: is the force or tension required to

break the film and is defined as the force in dynes
acting upon a line cm long on the surface of the
.liquid

Unit of the Surface tension are N/m, J/ m2 , D/cm •

Dependence of surface tension on
temperature

The surface tension of most liquids decreases with

increasing temperature
Measurement of surface tension by
Stalagmometer
drop-weight methods
n0 
  0
n 0
n0, ρ0, σ0 – number of droplets,
density and surface tension
,of water
n, ρ, σ – …… of investigated
liquid
Capillary rise method
,For zero contact angle

1
  rhg
2
Where g is gravity = 9,8
m/s2
For the rise of a liquid up a narrow capillary

N.B. In practice, the capillary rise method is only used when

the contact angle is zero, owing to the uncertainty in
measuring contact angles correctly
Cohesion is the interaction between molecules
.inside one phase (homogeneous system)
Adhesion is the interaction between molecules
inside of the different phases
Heterogeneous formation of a new phase

Spreading of the liqid on the surface of other

liquid
Formation of spherical drops
 Sorption Processes
Adsorption – the phenomenon of higher concentration of
molecular species on the surface of a solid than in the bulk

Absorption is the process of arbitrary absorption of the

substance by volume

Chemisorption - chemical interaction adsorbent with

adsorbate
Adsorbent – an adsorptive material, such as activated
charcoal
Adsorbate – an adsorbedsubstance
The solid substance on the surface of which
.adsorption occurs is known as adsorbent
The substances that get adsorbed on the solid surface
due to intermolecular attraction are called
.adsorbate
The adsorbent may be a solid or a liquid and the
adsorbate may be a gas or a solute in some
.solution
Difference between Adsorption and Absorption
 Viscosity
.Defined as “resistance to flow” of a fluid •
.Viscous liquids move slower •
The greater the intermolecular forces the •
.more is the viscosity
)Viscosity and molecular size interactive simulation(
)video on different density liquids(
 Physical Properties of Water
Highest density at 4 degrees celsius. Ice is one of •
the few solids to have a lower density in solid
phase as compared to liquid phase. This property
is very useful in ice skating, and fishes in lakes
.etc
Because of H Bonding water has a much higher •
b.p. and m.p.as compared to other liquids. This
property is making water one of the best
.coolants
)Ex: Perspiration, In car radiators etc ( •
)Water and Ice at molecular level(
 Liquid- Vapor Equilibrium
Vapor Pressure: The pressure exerted on •
the surface of a liquid by the vapor that is
in equilibrium with the liquid is called as
”“vapor pressure
Once equilibrium between a liquid and •
vapor is reached, the number of molecules
per unit volume in a vapor does not change
with time. Hence, the vapor pressure over
the liquid remains constant at a given
.temperature
 Vapor Pressure Vs. Temperature
.Vapor pressure increases with the increase in temperature
 Evaporation
Vaporization-the process by which a liquid or solid
.changes to gas
Evaporation- is the process where particles escape
from the surface of a non boiling liquid and
.enters the gas state
Evaporation takes place because the particles of ~
liquids have different kinetic energies,
therefore some of the particles with higher
kinetic energy overcome the intermolecular
.forces and evaporate to go in the gas phase
 Boiling
Boiling- is the change of a liquid to bubbles or vapor. Boiling occurs when
.the vapor pressure becomes equals atmospheric pressure
A liquid boils at the temp. at which its vapor pressure •
is equal to the pressure above its surface. (usually
atmospheric pressure)
If the pressure above the liquid’s surface is 1 atm, •
then this temperature is called as its “Normal Boiling
”Point
B.P. of a liquid is reduced by lowering the pressure •
.above it
?Why does it take longer to cook at high altitudes •
 Boiling: A liquid boils at a temp. when the vapor
pressure P1 becomes equal to the external pressure P2
above the liquid
 Phase Transitions
.Melting: change of a solid to a liquid •
H2O(s)  H2O(l)
.Freezing: change a liquid to a solid • H2O(l)  H2O(s)

Vaporization: change of a solid or liquid • H2O(l)  H2O(g) or

to a gas. Change of solid to vapor often H2O(s)  H2O(g)

.called sublimation H2O(g)  H2O(l) or
H2O(g)  H2O(s)
Condensation: change of a gas to a •
liquid or solid. Change of a gas to a solid
.often called deposition
 Vapor Pressure
In a sealed container, •
some of a liquid
evaporates to establish a
pressure in the vapor
.phase
Vapor pressure: partial •
pressure of the vapor over
the liquid measured at
equilibrium and at some
.temperature
Dynamic equilibrium •
 Temperature Dependence of
Vapor Pressures
The vapor pressure above the •
liquid varies exponentially
with changes in the
.temperature
The Clausius-Clapeyron •
equation shows how the
vapor pressure and
temperature are related. It
:can be written as

Hvap 1
ln P    C
RT T
 Clausius – Clapeyron Equation
A straight line plot results when ln P vs. •
1/T is plotted and has a slope of
.Hvap/R
Clausius – Clapeyron equation is true •
.for any two pairs of points

Write the
Hequation for each and •
vap 1
ln P   :combine
  Cto get
RT T

P2 Hvap  1 1 
ln    
P1 RT  T1 T2 
 Using the Clausius – Clapeyron
Equation
Boiling point the temperature at which •
the vapor pressure of a liquid is equal
to the pressure of the external
.atmosphere
Normal boiling point the temperature •
at which the vapor pressure of a liquid
is equal to atmospheric pressure (1
.atm)
 Colligative Properties
Colligative properties depend only on the •
number of solute particles present, not on
.the identity of the solute particles
Among Colligative properties are •
Vapor pressure lowering
Boiling point elevation
Melting point depression
Osmotic pressure
 Vapor Pressure
As solute molecules are
added to a solution, the
solvent become less
volatile (=decreased
.vapor pressure)
Solute-solvent interactions
.contribute to this effect
 Vapor Pressure

Therefore, the vapor

pressure of a solution
is lower than that of
.the pure solvent
 Raoult’s Law

PA = XAPA
where
XA is the mole fraction of compound A •
PA is the normal vapor pressure of A at that •
temperature

NOTE: This is one of those times when you want

to make sure you have the vapor pressure of
.the solvent
 SAMPLE EXERCISE 13.8 Calculation of Vapor-Pressure Lowering

Glycerin (C3H8O3) is a nonvolatile nonelectrolyte with a density of 1.26 g/mL at 25°C. Calculate the vapor
pressure at 25°C of a solution made by adding 50.0 mL of glycerin to 500.0 mL of water. The vapor pressure of
.pure water at 25°C is 23.8 torr (Appendix B)

PRACTICE EXERCISE
The vapor pressure of pure water at 110°C is 1070 torr. A solution of ethylene glycol and water has a vapor
pressure of 1.00 atm at 110°C. Assuming that Raoult’s law is obeyed, what is the mole fraction of ethylene
?glycol in the solution
 Boiling Point Elevation and
Freezing Point Depression
Solute-solvent
interactions also
cause solutions to
have higher boiling
points and lower
freezing points than
.the pure solvent
 Boiling Point Elevation
The change in boiling point
is proportional to the
:molality of the solution
Tb = Kb  m

where Kb is the molal

boiling point elevation
constant, a property of
Tb is added to the normal boiling point of .the solvent
.the solvent
 Freezing Point Depression
The change in freezing •
point can be found
:similarly
Tf = Kf  m

Here Kf is the molal •

freezing point
T is subtracted from the normal freezing point of
depression constant of
.the solvent
f
.the solvent
 Boiling Point Elevation and
Freezing Point Depression
In both equations, T
does not depend on
T b = K b  m
what the solute is, but
only on how many
.particles are dissolved
Tf = Kf  m