Electronegativity and Bond Polarity

Sharing of electrons to form covalent bonds and transfer of electrons to form ionic bonds represent two ends of a bonding continuum.
Bonding between the two ends of the bonding continuum is described using electronegativity and bond polarity.

Electronegativity
Electronegativity is the attraction of an atom for the shared electrons in a covalent bond.
Electronegativities are not measured quantities. Electronegativities are assigned based on factors such as atomic size, electron affinity, and ionization energy.

Electronegativity
The higher the electronegativity value, the more likely an element will attract extra electron density during compound formation.
Electronegativities increase from left to right across a period and from bottom to top for a group. Fluorine is the most electronegative element with an electronegativity of 4.0.

Electronegativity
Electronegativity values for elements.
Electronegativities increase from left to right for periods. Electronegativities increase from bottom to top for groups.

Bond Polarity
Electron density is not shared equally when elements with different electronegativities bond.
More than half of the electron density is associated with the more electronegative element.

Bond Polarity
The more electronegative element experiences an increase in electron density and a partial negative charge. The less electronegative element experiences a decrease in electron density and a partial positive charge. The two points of positive and negative charge constitute a dipole.

Bond Polarity
A bond along which a dipole exists is a polar bond.
Also referred to as a polar covalent bond since electrons are still being shared.

The greater the electronegativity difference, the more polar the bond. When the electronegativity difference is zero, the bond is classified as nonpolar covalent. When the electronegativity difference exceeds 2.0, the bond is classified as ionic.

Bond Polarity

The formation of the polar covalent HF bond.

The more electronegative F has a partial negative charge. The less electronegative H has a partial positive charge.

Bond Polarity
Before bonding, the electron density around H and F is spherical.
The negatively charged electrons and the positively charged nucleus offset each other.

Bond Polarity
When bonded, the more electronegative fluorine attracts shared electron density, creating a partial negative charge on F, and a partial positive charge on H.

Bond Polarity
The partial negative charge on F in PTFE forces the carbon backbone into a highly ordered shape.
PTFE packs into a crystal array more efficiently. Efficient crystal packing results in a higher melting temperature for Teflon.

Bond Polarity
The large bond polarity along the C-F bond in PTFE forces the carbon backbone into a highly ordered shape. Polymers with less polar bonds are not as highly ordered and are more branched.

Bond Polarity

The large bond polarity along the C-F bond in PTFE forces the carbon backbone into a highly ordered shape.

Bond Polarity
Polymers with less polar bonds are not as highly ordered and are more branched.

Intermolecular Forces
Intermolecular forces - the attractive and repulsive forces between molecules.

Forces Between Molecules

The attractive and repulsive intermolecular forces are weak in comparison to bonding forces.
Intermolecular forces are largely responsible for determining the structure and properties of condensed phases.

Dispersion Forces
Dispersion forces are common to all molecules.
Also called London forces. Also referred to as instantaneous dipoleinduced dipole forces. Dipoles exist for two oppositely charged points separated by some distance.

Dispersion Forces
An instantaneous dipole occurs when a fluctuation in electron density for an atom or molecule produces a dipole.
Instantaneous dipoles are short lived and constantly created.

Dispersion Forces
An induced dipole is created when an external electric field forces a dipole to exist.
A permanent dipole or an instantaneous dipole are the sources of the external electric field.

Dispersion Forces

An external electric field distorts the electron density around an atom, inducing a dipole.

Dispersion Forces

Molecules and atoms have symmetric charge distribution in the absence of an external electric field.

Dispersion Forces

The negative side of an external electric field repels negatively charged electrons, creating an induced dipole.

Dispersion Forces
Dispersion forces are incredibly weak.
The sum of dispersion forces over an Avogadros number of atoms results in a significant amount of energy. Dispersion energy holds many liquids and solids together.

Dispersion Forces
The strength of a dispersion force can be estimated from the polarizability of a molecule.
Polarizability is a measure of how susceptible a molecules electron density is to external electric fields. Large molecules are more polarizable than smaller molecules and experience stronger dispersion forces.

Dipole-Dipole Forces
Dipole-dipole forces are the attractive and repulsive forces for molecules with a permanent dipole.
The charge at the poles of a dipole is seldom more than a fraction of the charge on an electron. Molecules with stronger dipoles have stronger dipole-dipole forces. Dipole-dipole forces are typically stronger than dispersion forces.

Dipole-Dipole Forces
Dipole-dipole forces for 50 polar molecules.
At any given time, the number of attractive interactions is greater than the number of repulsive interactions.

Hydrogen Bonding
Hydrogen bonds are a special case of dipole-dipole forces.
Hydrogen bonds are especially strong compared to dipole-dipole forces. Hydrogen bonds occur only in compounds containing hydrogen bonded to the highly electronegative elements N, O, and F.

Intermolecular Forces
Intermolecular forces are weak compared to the average covalent bond. The large number of intermolecular forces make intermolecular forces a key factor in determining the bulk properties for materials.

Intermolecular Forces

Carbon atoms within a graphite sheet held together by covalent bonds. Intermolecular forces hold graphite sheets together.

Intermolecular Forces
Carbon atoms within a graphite sheet held together by covalent bonds.

Intermolecular Forces
Intermolecular forces holds graphite sheets together.

Condensed Phases - Liquids

Liquids are also a condensed phase.
Particles in condensed phases are in constant contact. Every particle in a solid vibrates around a fixed position. Every particle in a liquid is free to constantly move with respect to one another.

Vapor Pressure
Vapor pressure - the gas phase pressure of a substance in equilibrium with the pure liquid in a pure substance.
Vapor pressure is a characteristic property of a particular substance at a particular temperature.

Vapor Pressure
There is a distribution of kinetic energies for liquids at a given temperature.
Liquid molecules at the surface of the liquid with sufficient kinetic energy will pass into the gas phase. Vapor pressure increases with temperature. Liquids with strong intermolecular forces have lower vapor pressures. Liquids with high vapor pressures are described as volatile.

Vapor Pressure
To measure the vapor pressure of a solid or a liquid, the system must reach equilibrium.
The equilibrium is a dynamic equilibrium. The rate of evaporation equals the rate of condensation. The amount of gas and liquid does not appear to change.

Vapor Pressure

Liquids in closed containers will establish equilibrium with its vapor phase.

Vapor Pressure
Nonvolatile liquids evaporate more slowly due to their stronger intermolecular attractive forces and have low vapor pressures.

Vapor Pressure
Volatile liquids evaporate more quickly due to their weaker intermolecular attractive forces and have higher vapor pressures.

Boiling Point
Liquids boil when the vapor pressure for a liquid equals external pressure.
Normal boiling point - temperature where the vapor pressure of a liquid equals atmospheric pressure. The stronger the intermolecular forces in a liquid, the lower the vapor pressure, and the higher the boiling temperature.

Boiling Point

The vapor pressure of water varies dramatically as a function of temperature.

Boiling Point
Vapor pressures at 295 K for various substances. Substances with weaker attractive forces have higher vapor pressures and lower normal boiling points.

Surface Tension
Liquid molecules at the surface of a liquid experience fewer attractive forces than the molecules in the bulk material.
Surface tension is a liquids response to the imbalance in attractive forces. Liquids form spherical shapes. Spherical shapes have the greatest volumes with the least amount of surface area. Stronger attractive forces result in strong surface tension.

Surface Tension
Surface tension is the result of molecules at the surface of a liquid experiencing fewer intermolecular forces than liquid molecules inside the bulk liquid.

Surface Tension
The interaction between a liquid and the surface of a solid depends on two types of attractive forces.
Cohesion forces are liquid-liquid interactions. Adhesion forces are liquid-solid interactions. The relative strengths of the two forces dictate the shape of a liquids meniscus.

Surface Tension
The meniscus is the curved shape a liquid makes in contact with a solid.
Strong adhesion forces and weaker cohesion forces result in a concave meniscus. Weak adhesion forces and stronger cohesion forces result in a convex meniscus.

Surface Tension
The concave meniscus for water results from stronger adhesive forces. The convex meniscus for mercury results from stronger cohesive forces.