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CHAPTER 4

SOLUTIONS
&
THEIR PROPERTIES
SOLUTIONS

Learning objectives:
 Discuss different kinds of solutions
Types of Homogeneous Mixtures
Solutions
• most important class of homogeneous mixtures
• contain particles with diameters in range 0.1-2 nm
• transparent, do not separate on standing (salt water, sugar water)

Colloids
• contain particles with diameters in the range 2-500nm
• murky, do not separate on standing (milk, fog,)

Suspensions
• having larger particles than colloids
• Not truly homogeneous
• Particles separate on standing (blood, paint)
Solutes and Solvents
• A solution consists of a solute and a solvent:
 solute  the substance which is being dissolved.
 solvent  the substance (usually a liquid) that
dissolves the solute (usually, the solvent is the most
abundant component in the mixture).
• Aqueous solution are solutions in which the solvent is
water.

Solute Solvent Solution


Kinds of Solutions
Solution Solute Solvent Examples
Phase
Gaseous Gas Gas Air (O2, N2, Ar, CO2, H2O, and other
solution gases)
Gas Liquid Carbonated water (CO2 in water)
Liquid Liquid Liquid Gasoline (Mixture of hydrocarbons),
solutions
vodka (ethanol and water)
Solid Liquid Seawater (NaCl and other salts in
water)
Solid Gas Solid H2 in palladium metal
solutions Liquid Solid Dental amalgam (mercury in silver)
Solid Solid Metal alloys such as sterling silver
(Ag and Cu), brass (Cu and Zn) and
bronze (Cu and Sn); waxes
ENERGY CHANGES & THE
SOLUTION PROCESS
Learning objectives:
 Identify intermolecular forces in solution
 Explain types of solution interactions
 Identify intermolecular forces in solutions
 Describe dissolution of NaCl in water
 Explain the rule of thumb "like dissolves like.“
 Define the entropy and enthalpy of solution
Intermolecular Forces in Solutions
Relative strengths of intermolecular forces must be
considered between solute and solvent particles that
promote or prevent the formation of a solution.

Intermolecular Forces (in order of decreasing strength):

 ion-dipole forces — solvent molecules cluster around


ions in hydration shells, disrupting the bonding in the
crystal lattice.

 Hydrogen bonds— substances with O—H and N—H


bonds are often soluble in water because of H-bonding
(unless the molecules are large).
Intermolecular Forces in Solutions
 dipole-dipole forces —polar solutes interact well
with polar solvents through attraction of partial
charges.

 ion - induced dipole forces — responsible for the


attraction between Fe2+ and O2 molecules in the
bloodstream.

 dipole - induced dipole forces —responsible for the


solvation of gases (nonpolar) in water (polar).

 London (dispersion) forces —the principal attractive


force in solutions of nonpolar substances (e.g.,
petroleum).
Solution Interactions

Solutions form when solvent-solvent, solute-solute, and


solute-solvent forces are similar.
Solution Interactions
Relative Interaction and Solution Formation
Solvent-solute interaction > Solution forms
Solvent-solvent and solute-solute
interaction
Solvent-solute interaction = Solution forms
Solvent-solvent and solute-solute
interaction
Solvent-solute interaction < Solution may or
Solvent-solvent and solute-solute may not form
interaction depending on
relative disparity
Dissolution of NaCl in water
The General Solubility Rule
The general rule in solubility is that “like dissolves like”
Water, a polar molecule, dissolves ethanol, which is also
polar, but does not dissolve hexane and dichloromethane
which are both nonpolar.

 Ethanol and water are miscible—completely soluble


in each other in all proportions.

 Hexane and water are immiscible—they do not mix


with each other at all.

 Hexane and dichloromethane are miscible with each


other.
Entropies of solutions
Entropy is a measure of the
disorder or energy
randomization in a system.

Entropies of solution are


usually positive because
molecular randomness
usually increases when
(a) a solid dissolves in a
liquid or
(b) one liquid dissolves in
another.
Enthalpy of solution
• Enthalpy of solution measures how much energy is either absorbed
or released when a solution is prepared.

• The value of ΔHsoln is the sum of three terms:

Solvent-solvent interactions:
Energy is required (+ ΔH) to overcome intermolecular forces
between solvent molecules because the molecules must be
separated and pushed apart to make room for solute particles

Solute-solute interactions:
Energy is required (+ ΔH) to overcome intermolecular forces holding
solute particles together in a crystal.

Solvent-solute:
Energy is released (- ΔH) when solvent molecules cluster around
solute particles and solvate them
Energy Changes and the Solution
Process

The solute-solvent interactions


are greater than the sum of
the solute-solute and solvent-
solvent interactions.
Energy Changes and the Solution
Process

The solute-solvent
interactions are less than
the sum of the solute-solute
and solvent-solvent
interactions.
Enthalpy of solution
UNITS OF CONCENTRATION

Learning objectives:
 Interconvert units of concentration
 Perform calculations using solution density,
molarity,mole fraction, weight percent, parts per
million, parts per billion, and molality.
Units of Concentration
• Concentration: The amount of solute present in a given
amount of solution.

• Molarity (M):
Moles of solute
Molarity 
Liters of SOLUTION

• Mole Fraction (X):

Moles of A
XA 
Total number of moles
Units of Concentration
• Mass percent: The ratio of the mass of a solute to the
mass of a solution, multiplied by 100%.

mass of solute
% by massof solute =  100%
mass of solution
mass of solution =mass of solute +mass of solvent
Units of Concentration
• Parts per Million (ppm): Mass of solute
x 10 6
Total mass of solution
• One ppm gives 1 gram of solute per 1,000,000 g or one
mg per kg of solution.

For solid samples: ppm = µg/g = mg/kg

• For dilute aqueous solutions this is about 1 mg per liter


of solution.

For liquid samples: ppm = µg/mL = mg/L


Units of Concentration
• Parts per Billion (ppb): Mass of solute
x 109
Total mass of solution

For solid samples: ppm = µg/g = mg/kg

For liquid samples: ppm = µg/mL = mg/L

• Molality (m):
Moles of solute
Molality =
Kilograms of SOLVENT
Units of Concentration
FACTORS AFFECTING
SOLUBILITY
Learning objectives:
 Define saturated, unsaturated and supersaturated
solutions
 Describe crystallization process
 Discuss the effect of temperature and pressure on
solubility
 State Henry’s Law and its examples
Saturated and Unsaturated Solutions
• Saturated: Contains the maximum amount of solute that
will dissolve in a given solvent.

• Unsaturated: Contains less solute than a solvent has


the capacity to dissolve.

• Supersaturated: Contains more solute than would be


present in a saturated solution; these solutions are
unstable, and a slight disturbance causes the “extra”
solute to precipitate out.

• Crystallization: The process in which dissolved solute


comes out of the solution and forms crystals.
Precipitation from a supersaturated
solution

a) A supersaturated solution of sodium


acetate in water

b) When a tiny seed crystal is added,


larger crystals begin to grow and
precipitate from the solution until
equilibrium is reached
Effect of Temperature on Solubility
Solubilities are temperature-dependent.
The solubility of most molecular and ionic solids
increases with temperature, although some are almost
unchanged, and some decrease
For a solute with ΔHsoln > 0:
solute + solvent + heat saturated solution
 solubility increases with temperature.
For a solute with ΔHsoln < 0:
solute + solvent saturated solution + heat
 solubility decreases with temperature.
Effect of Temperature on Solubility
Solids:

Solubilities of some common solids in water as a function of temperature.


Most substances become more soluble as temperature rises, although
the exact relationship is often complex and nonlinear.
Effect of Temperature on Solubility
Gases:

• Solubilities of some gases in water as a function of temperature.


• Most gases become less soluble in water as the temperature rises.
 Soft drinks become “flat” as they warm up and lose carbon dioxide.
 Aquatic life is affected by decreasing amounts of dissolved oxygen
as a result of thermal pollution.
Effect of Pressure on the Solubility
Pressure has little effect on the solubility of solids and
liquids, but has a large effect on gases.
At a given pressure, there is an equilibrium between the
gas which is dissolved in the solution and the gas in the
vapor phase.
If the pressure increases, more gas dissolves to reduce
the “extra” pressure; the new equilibrium is established
with more gas dissolved.
Effect of Pressure on the Solubility
• Henry’s Law:
The solubility(Sgas, in mol/L) of a gas is
proportional to the pressure of the gas (Pgas, in
atm) over the solution

Sgas = k . Pgas

(The Henry’s law constant, k is a proportionality


constant, unique to each gas, at a given
temperature, with units of mol L-1 atm-1.)
Effect of Pressure on the Solubility
Examples of Henry’s – law behavior:
• When a can of soda is opened, bubbles of gas fizzing out
of solution because the pressure of CO2 in the can drops
and CO2 suddenly becomes less soluble.

• If a deep sea diver comes up to the surface too quickly, N2


which has dissolved in his bloodstream at higher
pressures comes back out of solution.
 The N2 forms bubbles which block capillaries and inhibit
blood flow, resulting in a painful, and potentially lethal,
condition called the “bends.”
 Less soluble gases, such as He, are often used in the
breathing mixtures to reduce this problem.