Chemistry: The Central Science - Chapter 13: Properties of Solutions

Properties of Solutions

Definition of Solutions

  • Solutions are homogeneous mixtures containing two or more pure substances.

  • In a solution, the solute is uniformly dispersed throughout the solvent.

  • The ability of different substances to form solutions relies on:

    • Natural tendency toward mixing.

    • Intermolecular forces.

Natural Tendency Toward Mixing

  • The mixing of gases occurs spontaneously.

  • Each gas behaves independently as it fills the container.

  • The randomness of molecules increases during mixing; this phenomenon is linked to a thermodynamic quantity known as entropy.

  • The formation of solutions is favored by the increase in entropy that accompanies mixing.

Intermolecular Forces of Attraction

  • Intermolecular forces can be the attraction between solute and solvent molecules.

Attractions Involved When Forming a Solution

  • Solute-Solute Interactions: Must be overcome to disperse solute particles when creating a solution.

  • Solvent-Solvent Interactions: Must also be overcome to create space for the solute.

  • Solvent-Solute Interactions: Occur as the particles mix, facilitating solution formation.

Solvation (Hydration)

  • Involves solvent-solute interactions allowing a solid to dissolve, illustrated with

    • Crystals of NaCl in water:

    • Hydrated Cl⁻ ion

    • Hydrated Na⁺ ion

Energetics of Solution Formation

  • For an endothermic reaction to occur, the process must be close to the sum of the individual disorders of the system (entropy will matter).

  • Exothermic solutions tend to be spontaneous, emphasizing energy release.

Aqueous Solution vs. Chemical Reaction

  • The disappearance of a substance in a solvent does not always indicate dissolution; the substance may react (e.g., nickel with hydrochloric acid).

Opposing Processes

  • The processes of solution formation and crystallization are oppositional.

  • A saturated solution exists when the rates of these opposing processes are equal; additional solute will not dissolve unless some crystallizes from the solution.

  • An unsaturated solution exists when the quantity of solute dissolved is less than the max solubility, preventing crystallization.

Solubility

  • Definition: Solubility is the maximum amount of solute that can dissolve in a certain quantity of solvent at a specified temperature.

  • Saturated solutions contain the maximum solute dissolved.

  • Unsaturated solutions contain less solute than the saturation point.

  • Supersaturated Solutions:

    • A rare type where the solvent holds more solute than normally possible at a specific temperature.

    • They are unstable and can crystallize by adding a “seed crystal” or through mechanical agitation.

Factors That Affect Solubility

  • Factors impacting solubility include:

    • Solute-solvent interactions.

    • Pressure (particularly for gaseous solutes).

    • Temperature variations.

Solute–Solvent Interactions


  • Fundamental principle: “Like dissolves like.”


  • Although this adage informs solubility behavior, it does not encompass all interactions.


  • Stronger solute-solvent interactions correlate with greater solubility of a solute in that solvent.


  • In Table 13.1, solubility for gases in water at 20°C at 1 atm shows the relationship between molecular mass of the gas and solubility:

    Gas

    Molar Mass (g/mol)

    Solubility (M)


    N₂

    28.0

    0.69 x 10⁻³


    O₂

    32.0

    1.38 x 10⁻³


    Ar

    39.9

    1.50 x 10⁻³


    Kr

    83.8

    2.79 x 10⁻³

    Organic Molecules in Water

    • Polar organic molecules tend to dissolve in water more effectively than their nonpolar counterparts.

    • Hydrogen bonding significantly boosts solubility because C–C and C–H bonds are poorly polar.

    Liquid/Liquid Solubility

    • Miscible Liquids: Liquids that mix in all proportions.

    • Immiscible Liquids: Liquids that do not mix with each other.

    • Example: Hexane is nonpolar while water is polar, making them immiscible.

    Solubility and Biological Importance

    • Fat-soluble vitamins (e.g., vitamin A) can be stored in body fats due to nonpolar characteristics.

    • Water-soluble vitamins (e.g., vitamin C) must be consumed regularly to meet dietary needs.

    Pressure Effects

    • Solubility of solids and liquids is largely unaffected by changes in pressure.

    • Conversely, the solubility of gases is significantly influenced by pressure conditions.

    Henry’s Law

    • States that the solubility of a gas is proportional to the partial pressure of the gas above the solution.

    Temperature Effects

    • General trends include:

      • For many solids, increased temperature corresponds to increased solubility. However, this may vary; some solids exhibit little change or reduced solubility with temperature changes.

      • For gases, increased temperatures typically decrease solubility; thus, colder rivers have a higher dissolved oxygen content than warmer ones.

    Solution Concentration

    • Discussion focuses on quantitative measures of solutions, moving beyond qualitative terms like saturated, unsaturated, and supersaturated.

    Units of Concentration

    • The specific measures of concentration include:

      1. Mass percentage.

      2. Parts per million (ppm).

      3. Parts per billion (ppb).

      4. Mole fraction (χ).

      5. Molarity (M).

      6. Molality (m).

    Mass Percentage

    • Defined as the ratio of the mass of solute to the total mass of the solution, multiplied by 100 to express as a percent.

    Parts per Million (ppm)

    • Relates to mass of solute to the total solution mass, conventionally defined as:

      • PPM: total mass/1,000,000

    Parts per Billion (ppb)

    • Similar to ppm, but on a much smaller scale, defined as:

      • PPB: total mass/1,000,000,000

    Mole Fraction (χ)

    • Ratios of the moles of a substance to the total moles within a solution.

    • Applications can include both solutes and solvents.

    Molarity (M) and Molality (m)

    • Molarity: Moles of solute per liter of solution (discussed within Chapter 4).

    • Molality: Moles of solute per kilogram of solvent.

    Molarity vs. Molality

    • In solutions where water is the solvent, molarity and molality yield similar values for dilute solutions.

    • Molality remains consistent regardless of temperature, while molarity fluctuates with temperature changes due to volume alterations.

    Converting Units

    • Conversion between molarity and molality requires application of dimensional analysis techniques, incorporating solution density as a crucial factor.

    Colligative Properties

    • Colligative properties rely solely on the quantity of solute particles rather than their identity. Key properties include:

      • Vapor-pressure lowering.

      • Boiling-point elevation.

      • Freezing-point depression.

      • Osmotic pressure.

    Vapor Pressure

    • Increased concentrations of nonvolatile solutes impede solvent escape into vapor, resulting in lower vapor pressures for solutions compared to pure solvents.

    Raoult’s Law

    • Asserts that the vapor pressure of a volatile solvent over a solution equals the product of the mole fraction of the solvent and the vapor pressure of the pure solvent.

    • Ideal solutions assume adherence to Raoult’s Law for component mixtures.

    Boiling-Point Elevation

    • Lower vapor pressures necessitate a temperature increase to achieve atmospheric pressure, subsequently raising the boiling point of the solution.

    Freezing-Point Depression

    • Phase diagrams illustrate that the freezing point is depressed while the boiling point is elevated for solutions.

    Boiling-Point Elevation and Freezing-Point Depression

    • The change in temperature correlates directly with molality, influenced by the van’t Hoff factor (number of particles a substance produces when it dissolves).

    Table 13.3: Molal Boiling-Point-Elevation and Freezing-Point Depression Constants

    Solvent

    Normal Boiling Point (°C)

    Kb (°C/m)

    Normal Freezing Point (°C)

    Kf (°C/m)

    Water, H₂O

    100.0

    0.51

    0.0

    1.86

    Benzene, C₆H₆

    80.1

    2.53

    5.5

    5.12

    Ethanol, C₂H₅OH

    78.4

    1.22

    -114.6

    1.99

    Carbon tetrachloride

    76.8

    5.02

    -22.3

    29.8

    Chloroform, CHCl₃

    61.2

    3.63

    -63.5

    4.68

    Osmosis

    • Refers to the net movement of solvent molecules from a solution with a lower solute concentration to one with a higher concentration across a semipermeable membrane, with the opposing pressure termed osmotic pressure.

    Osmotic Pressure

    • A colligative property, osmotic pressure indicates that if two solutions separated by a semipermeable membrane share equal osmotic pressure, no osmosis occurs.

    Types of Solutions and Osmosis

    • Isotonic solutions: Same osmotic pressure; solvent moves through the membrane at equal rates.

    • Hypotonic solution: Lower osmotic pressure; solvent exits at a higher rate than it enters.

    • Hypertonic solution: Higher osmotic pressure; solvent enters at a higher rate than it exits.

    Osmosis and Blood Cells

    • Red blood cells possess semipermeable membranes:

      • In hypertonic solutions, water exits the cell, causing crenation (shriveling).

      • In hypotonic solutions, water enters the cell, leading to hemolysis (bursting).

    • Intravenous (IV) solutions must maintain an isotonic balance with blood to prevent cellular distress.

    Colloids

    • Defined as suspensions of particles larger than separate ions or molecules, yet too small to settle by gravity.

    • Colloids serve as the boundary between solutions and suspensions.

    Table 13.5: Types of Colloids

    Phase of Colloid

    Dispersing Substance

    Dispersed Substance

    Colloid Type

    Example

    Gas

    Gas

    Gas

    None (all are solutions)

    Gas

    Liquid

    Aerosol

    Fog

    Smoke

    Liquid

    Gas

    Foam

    Whipped cream

    Liquid-Liquid

    Liquid

    Liquid

    Emulsion

    Milk

    Liquid-Liquid

    Solid

    Liquid

    Sol

    Paint

    Liquid-Liquid

    Solid

    Solid

    Solid foam

    Marshmallow

    Solid-Solid

    Solid

    Solid

    Solid emulsion

    Butter

    Solid-Solid

    Solid

    Solid

    Solid sol

    Ruby glass

    Solid-Solid

    Tyndall Effect

    • A phenomenon where colloidal suspensions can scatter light; solutions lack this ability. Examples illustrate the difference between solutions and colloids via visible scattering.

    Colloids and Biomolecules

    • Many biomolecules possess both hydrophilic and hydrophobic characteristics; the hydrophilic part faces outward in water, promoting solubility.

    Stabilizing Colloids by Adsorption

    • Ions can adhere to the surfaces of hydrophobic colloids, facilitating interaction with aqueous solutions, aiding in stabilization.

    Colloids in Biological Systems

    • Colloids play a role in emulsifying fats and oils in aqueous solutions. Emulsifiers enable substances that typically resist dissolution in a solvent to disperse.

    Brownian Motion

    • The agitation of colloids caused by multiple collisions with smaller solvent molecules contributes to their motion within the solution.

    Table 13.6: Calculated Mean Free Path for Uncharged Colloidal Spheres in Water at 20°C

    Radius of sphere (nm)

    Mean Free Path (mm)

    1

    1.23

    10

    0.390

    100

    0.123

    1000

    0.039

    Chapter 13 Homework

    • Homework problems to focus on:

      • #5, #7, #9, #15, #22, #25, #27, #29, #35, #39, #41, #45, #47, #51, #53 (a&c), #55, #73, #85, #90

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