BackIntermolecular Forces and Solution Formation: Chapter 13 Study Notes
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Intermolecular Forces
Introduction to Intermolecular Forces
Intermolecular forces are the attractive or repulsive forces that exist between molecules, influencing physical properties such as boiling point, melting point, solubility, and viscosity. These forces explain why some solids dissolve in water, why noble gases can liquefy, and why substances exist as gases, liquids, or solids at room temperature.
Intermolecular forces may be attractive or repulsive.
Johannes D. van der Waals first postulated intermolecular forces to explain the properties of real gases.
Types of Intermolecular Forces
van der Waals forces include:
London (dispersion) forces
Dipole-dipole forces
Dipole-induced dipole forces
Other intermolecular forces:
Ion-dipole interactions
Ion-induced dipole interactions
Hydrogen bonding
London (Dispersion) Forces
Origin and Properties
London forces arise from temporary variations in electron density in atoms and molecules. At any instant, the electron distribution may be unsymmetrical, producing an instantaneous dipole that can induce a dipole in neighboring molecules.
Present between all molecules, whether polar or nonpolar.
Stronger in molecules that are easily polarizable.
Larger and heavier molecules exhibit stronger dispersion forces than smaller and lighter ones.
Example: Neon atoms do not have a permanent dipole, but can exhibit dispersion forces.
Magnitude of Dispersion Forces
Cylindrical-shaped molecules (e.g., n-pentane) have greater surface area and stronger dispersion forces than spherical-shaped molecules (e.g., neopentane).
Dipole-Dipole and Dipole-Induced Dipole Forces
Dipole-Dipole Forces
These forces occur between molecules with permanent dipoles. The positive end of one molecule is attracted to the negative end of another.
Dipole-Induced Dipole Forces
These operate between polar molecules (with permanent dipoles) and nonpolar molecules. The polar molecule induces a dipole in the neighboring nonpolar molecule.
Interaction energy depends on the dipole moment of the polar molecule.
Examples:
Oxygen gas dissolves in water because water's permanent dipole induces a dipole in oxygen.
Nonpolar iodine dissolves in polar ethanol due to dipole-induced dipole forces.
Ion-Dipole and Ion-Induced Dipole Interactions
Ion-Dipole Interactions
These occur between ions and polar molecules. The strength depends on the charge and size of the ion and the magnitude of the dipole moment of the polar molecule.
Hydration of ions: Sodium ions (Na+) and chloride ions (Cl-) are surrounded by water molecules in solution, stabilizing them through ion-dipole interactions.
Hydrogen Bonding
Definition and Conditions
Hydrogen bonding is an electrostatic force of attraction between a covalently bonded hydrogen atom (attached to a highly electronegative atom such as fluorine, oxygen, or nitrogen) and the electronegative atom of another molecule.
A hydrogen atom attached to a relatively electronegative atom is a hydrogen bond donor.
The electronegative atom (F, O, N) is a hydrogen bond acceptor.
Effects of Hydrogen Bonding
Higher boiling point in ethanol compared to diethyl ether.
Higher viscosity of sulfuric acid and glycerol.
Water is a liquid at room temperature, whereas H2S is a gas.
Formation of dimers in carboxylic acid molecules.
Cage-like structure of water molecules in ice causes lower density of ice.
Comparison of Intermolecular Forces
Relative Strengths and Examples
Type | Model | Interaction | Energy (kJ/mol) | Example |
|---|---|---|---|---|
Ion-dipole | Ion + dipole | Charge-dipole | 40–600 | Na+ in H2O |
H bond | Dipole + dipole | Polar H bond | 10–40 | H2O, HF |
Dipole-dipole | Dipole + dipole | Dipole-dipole | 3–20 | HCl, CH3Cl |
Ion-induced dipole | Ion + induced dipole | Charge-induced dipole | 3–15 | Fe2+ in O2 |
Dispersion (London) | Induced dipole + induced dipole | Polarizable | 1–10 | H2, I2 |
Solutions: Effect of Intermolecular Forces
Mixing Solute and Solvent
For a solution to form, solute-solute and solvent-solvent attractive forces must be overcome (endothermic), and new solute-solvent attractions must be formed (exothermic).
Both processes are endothermic, but the formation of new attractions is exothermic.
Oil and water do not mix because oil is nonpolar and water is polar. "Like dissolves like" principle applies.
Common Types of Solutions
Solute Phase | Solvent Phase | Example |
|---|---|---|
Gas | Gas | Air (O2 and N2) |
Gas | Liquid | Carbonated water (CO2 in H2O) |
Liquid | Liquid | Vodka (ethanol and water) |
Solid | Liquid | Seawater (NaCl in water) |
Solid | Solid | Brass (Cu and Zn) |
Solution Process and Enthalpy of Solution
Steps in Solution Formation
Separating the solute into its constituent particles (, endothermic)
Separating the solvent particles from each other (, endothermic)
Mixing the solute particles with the solvent particles (, exothermic)
The overall enthalpy change () is:
If the sum of endothermic terms is approximately equal to the exothermic term, is about zero.
If the sum of endothermic terms is less than the exothermic term, is negative (exothermic).
If the sum of endothermic terms is greater than the exothermic term, is positive (endothermic).
Solubility Limit and Saturation
Saturated solution: Contains the maximum amount of solute that can dissolve at a given temperature.
Unsaturated solution: Contains less solute than saturation.
Supersaturated solution: Contains more solute than saturation; unstable.
Temperature and Pressure Dependence of Solubility
Solids in Water
Solubility of most solids increases with temperature.
Solubility curves can predict saturation, unsaturation, or supersaturation.
Gases in Water
Solubility of gases decreases with increasing temperature.
Solubility of gases increases with increasing pressure.
Henry's Law: The solubility of a gas () is directly proportional to its partial pressure () at a given temperature.
Where is Henry's law constant.
Solution Concentration Terms
Unit | Definition |
|---|---|
Molarity (M) | Amount solute (in mol) / volume solution (in L) |
Molality (m) | Amount solute (in mol) / mass solvent (in kg) |
Mole fraction (x) | Amount solute (in mol) / total amount of solute and solvent (in mol) |
Mass percent (%) | Mass solute / mass solution × 100% |
Parts per million (ppm) | Mass solute / mass solution × 106 |
Parts per billion (ppb) | Mass solute / mass solution × 109 |
Summary Table: Common Laboratory Solvents
Common Polar Solvents | Common Nonpolar Solvents |
|---|---|
Water (H2O) | Hexane (C6H14) |
Acetone (CH3COCH3) | Diethyl ether (CH3CH2OCH2CH3) |
Methanol (CH3OH) | Toluene (C6H5CH3) |
Ethanol (CH3CH2OH) | Carbon tetrachloride (CCl4) |
Key Equations
Enthalpy of Solution:
Henry's Law:
Examples and Applications
Oil and water: Do not mix due to polarity differences.
Solubility curves: Used to determine saturation status at different temperatures.
Hydrogen bonding: Explains water's high boiling point and ice's low density.
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