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Solutions

Chapter 13

Properties of Solutions

Chemistry, The Central Science, 10th edition

Theodore L. Brown; H. Eugene LeMay, Jr.;

and Bruce E. Bursten

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• Solutions are homogeneous mixtures of two or more pure substances. • In a solution, the solute is dispersed uniformly throughout the solvent

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The intermolecular

forces between solute and solvent particles must be strong enough to compete with those between solute particles and those between solvent particles.

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How Does a Solution Form?As a solution forms, the solvent pulls solute particles apart and surrounds, or

solvates them.

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How Does a Solution Form

If an ionic salt is

soluble in water, it is because the ion- dipole interactions are strong enough to overcome the lattice energy of the salt crystal.

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Energy Changes in Solution

• Simply put, three processes affect the energetics of the process

Separation of solute particles

H

1(this is always

endothermic)

Separation of solvent particles H

2 (this too is

always endothermic)

New interactions between solute and solvent H

3 (this

is always exothermic)

The overall enthalpy change

associated with these three processes: H soln =H 1 +H 2+H 3

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• The process solution formation can be either endo or exothermic • Hot packs use MgSO

4and cold packs

use NH 4NO

3 and water.

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• The solvent solute interactions must be strong enough to make H

3 comparable

in magnitude to H 1 +H 2 • So NaCl will not dissolve in nonpolar liquids as the attraction between the ions and the nonpolar solvent will not compensate for the energies required to separate the ions.

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Energy Changes in Solution

The enthalpy

change of the overall process depends on DHfor each of these steps.

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Why Do Endothermic

Processes Occur?

Things do not tend to occur

spontaneously (i.e., without outside intervention) unless the energy of the system is lowered.

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Why Do Endothermic

Processes Occur?

Yet we know that in

some processes, like the dissolution of NH 4NO

3in water,

heat is absorbed, not released.

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Enthalpy Is Only Part of the Picture

The reason is that

increasing the disorder or randomness (known as entropy ) of a system tends to lower the energy of the system.

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Enthalpy Is Only Part of the Picture

So even though

enthalpy may increase, the overall energy of the system can still decrease if the system becomes more disordered.

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• The process occurring at a constant temperature in which the randomness in space or the entropy of the system increases tend to occur spontaneously

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Student, Beware!

Just because a substance disappears when it

comes in contact with a solvent, it doesn"t mean the substance dissolved.

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Student, Beware!

• Dissolution is a physical change-you can get back the original solute by evaporating the solvent. • If you can"t, the substance didn"t dissolve, it reacted. • The above example is the reaction of nickel with HCl resulting in the formation of NiCl 2

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Types of Solutions

• Saturated

Solvent holds as much solute as is possible at that temperature.Dissolved solute is in dynamic equilibrium with solid solute particles.

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Types of Solutions

• Unsaturated Less than the maximum amount of solute for that temperature is dissolved in the solvent.

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Types of Solutions

• Supersaturated

Solvent holds more solute than is normally possible at that temperature.These solutions are unstable; crystallization can usually be stimulated by adding a "seed crystal" or scratching the side of the flask.

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Solubility, saturation and supersaturation

Below saturation•Solvent is not yet holding the maximum amount of solute it can at that temperature

•More solute could still dissolve - if you add more, it will mix inAt saturation point •Solvent is holding the maximum amount of solute it can at that temperature •If you add any more solute, it will not dissolve (will fall to the bottom -precipitate) •Solubility= often measured in grams of solute per 100 mL of solventBeyond saturation •Solvent is holding more solute than it is able to at that temperature -situation is unstable •If you add anything to the solution, the excess (beyond saturation point) will crystallize out

As you add more solute to a solution

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Factors Affecting Solubility

Solute Solvent Interaction

• Chemists use the axiom "like dissolves like": Polar substances tend to dissolve in polar solvents. Nonpolar substances tend to dissolve in nonpolar solvents.

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The more similar the

intermolecular attractions, the more likely one substance is to be soluble in another.

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Glucose (which has

hydrogen bonding) is very soluble in water, while cyclohexane (which only has dispersion forces) is not.

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• Vitamin A is soluble in nonpolar compounds (like fats). • Vitamin C is soluble in water.

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Gases in Solution

• In general, the solubility of gases in water increases with increasing mass as the attraction between the gas and the solvent molecule is mainly dispersion forces. • Larger molecules have stronger dispersion forces.

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Effect of Pressure

• The solubility of solids and liquids is not affected by pressure. • However the solubility of gases is greatly affected by pressure.

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Gases in Solution

• The solubility of a gas in a liquid is directly proportional to its pressure.

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Henry"s Law

SgP g

Sg= kP

g where •S gis the solubility of the gas; •kis the Henry"s law constant for that gas in that solvent at that temperature •Pgis the partial pressure of the gas above the liquid.

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Calculate the concentration of CO

2in a soft drink that is bottled with a partial

pressure of CO

2of 4.0 atm over the liquid at 25C. The Henry"s law

constant for CO2in water at this temperature is 3.1 ´10-2 mol/L-atm.

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