Solution and properties

Solution
Any homogeneous mixture

Solute Solvent Resulting Examples

Solution
gas gas
gas liquid
gas solid
liquid liquid
solid liquid
solid solid
Solvent – The substance in a solution that causes the solution to
be made. Usually it is the most abundant substance in the
mixture.

Solute – The substance that is dissolved. There can be more

than one solute in a solution. In the most common solution, the
solute is a solid or a liquid and the solvent is a liquid.
some concentration terms:

1. Wt. % =
Sometimes this is written as g solute/ 100 g solution
Moles of A
2. Mole Fraction of A = XA =
total moles of all components

3. Molality (m) = The # of moles of solute dissolved in 1 kg

of solvent
Saturated Solution – A solution in which the maximum
amount of solute that will dissolve is present. Each
solute-solvent system is unique

Unsaturated Solution – A solution in which less than the

maximum amount of solute is dissolved.
Supersaturated Solution – Occasionally, during the
dissolving process, more than the theoretical maximum
amount of solute has dissolved. This is an unstable
situation. In time, some of the solute crystallizes out of the
solution. Frequent stirring during the solution process can
help prevent this.
Solubility - Usually expressed as g solute/
100 g solvent (sometimes for aqueous
solutions [any solution in which H2O is the
solvent] g solute/ 100 mL solvent)
In order for a solute to dissolve in a solvent, the solute particles have to fit in
between the solvent particles. This usually can help us predict which solutes will
dissolve in which solvents. This is usually accomplished with solute-solvent
attractions. There is a general Rule of Thumb for solubility: Like Dissolves Like.

Some solutions have complete miscibility (gas in gas, many liquids in liquids).
Miscibility means complete solubility in any proportion.
Effect of pressure on gas
solubility

 The solubilities of solids

and liquids are not
affected appreciably by
pressure

 When the pressure of a

gas is increased, as in
(b), the rate at which gas
molecules enter the
solution increases

 The concentration of
solute molecules at
equilibrium increases in
proportion to the
pressure

 So the solubility of a gas

increases with pressure
Pressure and Solubility of Gases
Solubility decreases as pressure decreases

 Soft drink bottled under

CO2 pressure greater than
1 atm

 When the bottle is opened,

partial pressure of CO2
above the solution
decreases

 Solubility of CO2
decreases -> bubbles

13.5
 Pressure and Solubility of Gases
Solubility decreases as pressure decreases

n many consumer beverages such as soft drinks, carbonation is used to give "bite
ontrary to popular belief, the fizzy taste is caused by the dilute carbonic acid
nducing a slight burning sensation, and is not caused by the presence of bubbles
his can be shown by drinking a fizzy drink in a hyperbaric chamber at the same
ressure as the beverage. This gives much the same taste, but the bubbles are
ompletely absent.

13.5
Henry’s Law
The solubility of a gas in a liquid is proportional to the pressure
of the gas over the solution (Henry’s law).

 The mass of a gas (m2)

dissolved by a given
volume of solvent at
constant T is proportional to
the pressure of the gas (P2)
above and in equilibrium
with the solution.
m2 = k 2 P 2
where k2 is the Henry’s law
constant.

10
Henry’s Law

 For a mixture of gases

dissolved in a solution.
Henry’s law can be
applied for each gas
independently.
 The more commonly
used forms of Henry’s
law are:
P2 = k’ x2
P2 = k” c2

11
Henry’s Law
 The vapor pressure of a
solute, P2 , in a solution in
which the solute has a mole
fraction of x2 is given by:
P2 = x2 P2*
where P2* is the vapor pressure
of the solute in a pure liquefied
state.
 It is also found that at the
limits of infinite dilution, the
vapor pressure of the solute
obeys Henry’s law.
12
SAMPLE EXERCISE A Henry’s Law Calculation

Calculate the concentration of CO 2 in a soft drink that is bottled with a partial pressure of CO 2 of 4.0 atm over
the liquid at 25°C. The Henry’s law constant for CO 2 in water at this temperature is 3.1  10–2 mol/L-atm.

Solution
Analyze: We are given the partial pressure of CO2, and the Henry’s law constant, k, and asked to calculate the
concentration of CO2 in the solution.
Plan: With the information given, we can use Henry’s law to calculate the solubility.

Solve:
2
Check: The units are correct for solubility, and the answer has two significant figures consistent with both the
partial pressure of CO2 and the value of Henry’s constant.

PRACTICE EXERCISE
Calculate the concentration of CO 2 in a soft drink after the bottle is opened and equilibrates at 25°C under a
CO2 partial pressure of 3.0  10–4 atm.
Blood gases and deep sea diving
 Solubility increases as pressure increases
 Divers who use compressed gases must be concerned about the solubility of the gases in their blood
 At depth, the blood contains higher concentrations of dissolved gases
 Ascension, if too rapid, will cause the blood to fizz similar to 7-UP when opened!
 This is called decompression sickness, or “the bends”, which is painful and can be fatal because the
bubbles affect things like nerve impulses
 Temperature and Solubility
Solubility of most solid solutes in water In contrast, solubility of gases in water
increases with increasing temperature decreases with increasing temperature

13.4
 Temperature and Solubility
 Carbonated beverages go “flat”
as they warm due to a decreased In contrast, solubility of gases in water
decreases with increasing temperature
solubility of dissolved CO2

 Bubbles form on the inside wall

of a cooking pot when water is
heated even though the
temperature is well below boiling

 Thermal pollution of lakes and

streams causes low oxygen levels
in deeper layers

Most gases obey Henry’s Law with some notable exceptions, especially if the gas
reacts with water. In those cases much higher solubilities can be obtained. A good
example is ammonia in water. 13.4
 Effect of solutes on the
properties of the solvent
 Properties of pure solvents are affected when solutes are
dissolved in the solvent.

 The presence of the solute affects the interactions between

solvent molecules.

 COLLIGATIVE properties: properties of solvents which are

affected by the concentration of the solute
 Example: boiling point, freezing point, vapor pressure
The Vapor Pressure of a Liquid
Vapor pressure is the pressure of a
vapor in equilibrium with its non-
vapor phases. All liquids and solids
have a tendency to evaporate
(escape) to a gaseous form, and all Vapor
gases have a tendency to condense pressure
back into their original form (either
liquid or solid). At any given
temperature, for a particular
substance, there is a pressure at
which the gas of that substance is in
dynamic equilibrium with its liquid
or solid forms. This is the vapor Liquid or
pressure of that substance at that solid
temperature.

18
The Vapor Pressure of a Liquid

Vapor
pressure
Increasing T

Liquid or
solid

19
Effect of Nonvolatile Solutes
on Vapor Pressure

20
Effect of solute on vapor pressure

 Consider an ideal solution of a volatile solvent with a non-volatile

solute.

 Since the solvent is volatile, but not the solute, the vapor pressure
above the solution is due to the solvent only.

 The vapor pressure of the solution is LOWER than the vapor

pressure of the pure solvent.

 Experiments indicate that, for ideal solutions, the vapor pressure of

the solution is directly proportional to the mole fraction of the
solvent in the solution.
Colligative Properties –

Depend only on the number of solute particles in a solution but not

on the nature of the solute particles.

1. Raoult’s Law – When a non-volatile solute (basically any

solid), the partial pressure of a solvent, PS, over a solution is
directly proportional to the mole fraction of the solvent, XS, and
the VP of the pure solvent, P.

PS = XS P
The net effect is that
the vapor pressure of
the solution is always
lower than the vapor 0
S
pressure of the pure
solvent. Raout’s Law
can be rewritten as:

P = Xsolute P
If both components are volatile, Raoult’s Law still works. It has to
be applied for each component, solute and solvent:

PA = XAP and

PB = XBP

Using Dalton’s Law of Partial Pressures

PT = PA + PB or

PT = XAP + XBP
Deviations from Raoult’s Law
Deviations from Raoult’s law
occur for nonideal solutions.
Consider a binary system made of
A and B molecules.
 Positive deviation occurs when
the attraction forces between A-
A and B-B pairs are stronger
than between A-B. As a result,
both A and B will have more
tendency to escape to the vapor
phase.
 Examples:
 CCl – C H OH system.
4 2 5
25
 n-C H – C H OH system
Deviations from Raoult’s Law
For a binary system made of A
and B molecules.
 Negative deviation occurs when
the attraction force between A-
B pairs is stronger than between
A-A and B-B pairs. As a result,
both A and B will have less
tendency to escape to the vapor
phase.
 Examples:
 CCl – CH CHO system.
4 3
 H2O – CH3CHO system
26
Normal boiling temperature:
The temperature at which the vapor pressure of the liquid
equals 1 atm
How does vapor pressure vary with temperature?

How do we measure vaporization enthalpy?

What’s ln(P)? Whats’ log(P)? *05

How do we measure vaporization enthalpy?
It has been found that by measuring the vapor pressure of a liquid as a
function of temperature, an exponential increase in vapor pressure is observed.
Furthermore, it has bee also found that by plotting the logarithm of vapor
pressure as a function of 1/T where T is in K, a linear plot is obtained.
We can express this line using the general equation for a straight line:
y = mx +b
in this case y = lnP, and x = 1/T; the slope of the line is found to be -
Hvap/R
Clausius Clapeyron Equation

ln(P) = 2.303 log(P)

Hvap = vaporization enthalpy
R=gas constant 1.987 cal/(K mol); 8.314 J/(mol K); 0.0821Latm/(K mol)
Antoine Equation

• Another form of this eq is the Antoine Equation

. A .
ln p* =( T+C ) +B

• The vapor pressure can be found from tables, charts

or empirical equations (the Antoine equation)

V – nb +
Change in Vapour pressure with change
in Temperature
Triple Point: A unique
temperature and pressure at
which three phases (usually The H2O Phase Diagram
solid, liquid, and gas) can
exist together.

Critical Point: The

temperature and pressure at
which gas and liquid merge
together to form a
supercritical fluid. Beyond  = 1.00 g/ml
this temperature, no amount
of pressure will condense the
gas to a liquid.
 = .92
Normal Melting Point – g/ml
At 1 atm pressure, the
temperature at which the
solid melts to liquid.
= .0006 g/ml
Normal Boiling Point –
At 1 atm pressure, the
temperature at which the
liquid vaporizes to become a
gas.