John-Chapter 3 Chemistry 111

Chapter 3: Bonding - General Concepts

Learning Outcomes

  • Describe the differences between ionic and covalent bonding and the properties of each type of compound.

  • Predict relative ion sizes based on ionic radii trends.

  • Calculate lattice energy using Coulomb’s Law and Hess’s Law.

  • Name and write formulas for ionic compounds.

  • Name and write formulas for covalent compounds.

  • Understand how electronegativity of elements impacts covalent bond polarity.

  • Draw Lewis structures for covalent compounds.

  • Draw resonance structures for compounds that have more than one possible Lewis structure.

  • Calculate the formal charge of elements in a molecule and use it to optimize structure.

  • Use bond energies to calculate enthalpy changes for chemical reactions.

3-1: Types of Chemical Bonds

  • Atoms bond to achieve greater stability.

  • The most stable electron configurations belong to noble gases because they have filled outer (valence) shells:

    • He: 1s²

    • Ar: 1s² 2s² 2p⁶ 3s² 3p⁶

  • Other atoms achieve a stable filled valence shell by:

    • Sharing or transferring electrons with nearby atoms, forming chemical bonds.

Lewis Dot Symbols

  • Lewis Dot symbols represent an element's symbol along with its valence shell electrons.

  • For hydrogen and helium, a full and stable outer shell contains 2 electrons.

  • For larger elements, a full valence shell typically contains 8 electrons.

  • Example Lewis dot symbols:

    • Na: •

    • H: •

    • Cl: ••

Achieving Noble Gas Configuration

Ionic Bonds
  • Lewis Dot diagrams showcase how sodium (Na) and chlorine (Cl) can transfer electrons to achieve noble gas configurations.

  • The resulting electrostatic attraction between these ions is known as an ionic bond.

Covalent Bonds
  • Lewis Dot diagrams show how hydrogen (H) and chlorine (Cl) can share electrons to obtain noble gas configurations.

  • The pair of shared electrons between these two atoms is known as a covalent bond.

Ionic and Covalent Compounds

Ionic Compounds
  • Examples: NaCl, NaHCO₃

  • Comprise metals (or NH₄⁺) and nonmetal ions.

  • Electrons are transferred between atoms.

  • Features:

    • Solid, brittle, crystalline.

    • High melting points.

    • Dissolve in water to form ions that conduct electricity.

    • Conduct electricity in molten states.

Covalent Compounds (Molecular)
  • Examples: H₂O, C₆H₁₂O₆

  • Comprise 2 or more nonmetals.

  • Electrons are shared between atoms.

  • Features:

    • Can exist as solids, liquids, or gases.

    • Typically have lower melting and boiling points compared to ionic compounds.

    • Some dissolve in water, but do not form ions and do not conduct electricity.

3-3: Ions - Electron Configurations and Size Trends

  • When atoms become ions, they acquire noble gas electron configurations, stabilizing them.

  • Example for Calcium:

    • Calcium atom configuration: 1s² 2s² 2p⁶ 3s² 3p⁶ 4s²

    • Calcium ion configuration (lost 2 electrons): 1s² 2s² 2p⁶ 3s² 3p⁶

    • Formula for calcium ion: Ca²⁺

  • Example for Oxygen:

    • Oxygen atom configuration: 1s² 2s² 2p⁴

    • Oxide ion configuration (gained 2 electrons): 1s² 2s² 2p⁶

    • Formula for oxide ion: O²⁻

Relative Sizes of Ions
  • Ion size trends:

    • Increases down a group, decreases left to right across a period.

    • Exception occurs when cations switch to anions; anions have one more electron shell than cations.

  • Ranking of ions from smallest to largest:

    • Al³⁺ < Mg²⁺ < Na⁺ < Cl⁻

Isoelectronic Ions
  • Isoelectronic ions share the same electron configuration.

  • Size decreases as atomic number increases due to increased nuclear charge pulling electrons closer to the nucleus.

  • Example: Na⁺ (smaller than F⁻) despite having the same electron configuration (1s² 2s² 2p⁶).

Ionic Radii Trends

  • Summary of ionic radii in picometers (pm):

    • Li⁺: 60 pm, Na⁺: 116 pm, Mg²⁺: 72 pm, Al³⁺: 50 pm, Ca²⁺: 99 pm.

Energy Effects in Binary Ionic Compounds

  • Ionic bonds form through the attraction of a cation and an anion, resulting in lower energy than separated ions.

  • Lattice energy (LE) is defined as the energy of attraction between ions, calculable by Coulomb’s Law:

    • LE=kracQ<em>1Q</em>2rLE = k rac{Q<em>1 Q</em>2}{r} where Q represents the charges of the ions and r is the distance between the ions.

  • Factors increasing lattice energy:

    • Higher opposing ion charges (Q1 and Q2).

    • Decreased ionic size/distance (r).

Determining Lattice Energy with Hess’s Law

  • Hess’s Law states that the energy change for a reaction is independent of the pathway taken.

  • Lattice Energy can be inferred using Hess’s Law through a series of measurable reactions.

Example Calculation for Lattice Energy
  • For lithium fluoride (LiF): From the Hess’s Law equation,

    • LE=extEnthalpychangefromallprocessescontributingtoformationLE = ext{Enthalpy change from all processes contributing to formation}

    • 612kJ/mol=+158kJ/mol++520kJ/mol++72kJ/mol+328kJ/mol+LELiF-612kJ/mol = +158kJ/mol + +520kJ/mol + +72kJ/mol + -328kJ/mol + LE_{LiF}

    • Result: LELiF=1,034kJ/molLE_{LiF} = -1,034 kJ/mol

Naming Simple Compounds

Binary Ionic Compounds
  • Contain a simple type I cation (same name as element) and an anion (named with “ide”).

  • No prefixes for subscripts existing; overall compound charge is neutral.

  • Examples:

    • LiF: Lithium Fluoride.

    • CaCl₂: Calcium Chloride.

    • Al₂O₃: Aluminum Oxide.

Common Monoatomic Ions

Cation Name

Anion Name

H⁺ Hydrogen

H⁻ Hydride

Li⁺ Lithium

F⁻ Fluoride

Na⁺ Sodium

Cl⁻ Chloride

K⁺ Potassium

Br⁻ Bromide

Cs⁺ Cesium

I⁻ Iodide

Be²⁺ Beryllium

O²⁻ Oxide

Mg²⁺ Magnesium

S²⁻ Sulfide

Ca²⁺ Calcium

N³⁻ Nitride

Ba²⁺ Barium

P³⁻ Phosphide

Al³⁺ Aluminum

Type II Binary Ionic Compounds
  • Type II Metals: metals that can have different charge states indicated with Roman numerals following the cation.

  • Examples:

    • CuCl₂: Copper (II) Chloride.

    • Only transition metals except Ag⁺, Zn²⁺, and Cd²⁺ fall under this definition.

Polyatomic Ions in Naming Compounds

  • Oxyanions: ions with an atom of a given element and varying amounts of oxygen.

  • Two Oxyanions:

    • Lesser oxygen: ends in “-ite”.

    • Greater oxygen: ends in “-ate”.

  • Example: Chlorate = ClO₃⁻ and Chlorite = ClO₂⁻.

Naming Polyatomic Ions
  • Prefixes used in multi-oxyanion series:

    • Hypo- for the fewest oxygens.

    • Per- for the most oxygens.

  • Examples:

    • Perchlorate = ClO₄⁻ and Hypochlorite = ClO⁻.

Common Polyatomic Ions to Memorize

Name

Formula

Nitrate

NO₃⁻

Nitrite

NO₂⁻

Carbonate

CO₃²⁻

Bicarbonate

HCO₃⁻

Chlorate

ClO₃⁻

Chlorite

ClO₂⁻

Perchlorate

ClO₄⁻

Hypochlorite

ClO⁻

Sulfate

SO₄²⁻

Sulfite

SO₃²⁻

Phosphate

PO₄³⁻

Phosphite

PO₃³⁻

Naming Acids

Binary acids
  • Contain hydrogen and one other element:

    • Use the “hydro” prefix, the ion name, and “-ic acid”.

    • Example: HF = hydrofluoric acid.

Oxoacids
  • Contain hydrogen, oxygen, and another element.

  • Use ion name:

    • “-ate” becomes “-ic acid”; “-ite” becomes “-ous acid”.

    • Examples: HNO₃ = nitric acid, HNO₂ = nitrous acid.

Strong and Weak Acids
  • Strong acids dissociate fully in water producing a high concentration of H₃O⁺ ions. Examples include:

    • HCl, HBr, HI, HNO₃, HClO₄, H₂SO₄

  • All other acids are classified as weak acids.

Strategy for Naming Compounds

  • Classify the compound before naming:

    • Ionic: metal and nonmetals.

    • Covalent: all nonmetals.

    • Acids: those with hydrogen or acid in the name.

    • Hydrates: those with . H₂O present.

Lewis Structures

  • To predict molecular structure, use the Localized Electron Model, which assumes atoms are bound by shared pairs of electrons.

Procedure for Lewis Structures
  1. Sum the valence electrons.

  2. Draw skeletal structure based on electronegativity (lowest in center).

  3. Use pairs of electrons to form bonds.

  4. Satisfy outer atoms’ octets first, followed by inner.

  5. Use double/triple bonds if necessary to satisfy octets.

  6. Check and minimize formal charges across all atoms.

Formal Charge Calculation
  • Formal Charge = (Group #) - (Non-bonding electrons) - 1/2 (Bonding electrons)

Exceptions to the Octet Rule

  • Some elements like Beryllium and Boron do not follow the octet rule, typically holding 4 or 6 electrons.

  • Elements in period 3 and beyond can expand their octets, utilizing available d orbitals.

Resonance Structures

  • Certain structures allow for multiple valid Lewis structures; the actual molecule is a resonance hybrid averaging these structures.

Bond Energies

  • Bond Energy: The energy required to break a chemical bond.

    • Tabulated values rank bonds: single < double < triple.

  • Example Bond Energies:

    • ΔH=(EnergyRequiredtoBreakBonds)(EnergyReleasedwhenBondsForm)ΔH = (Energy Required to Break Bonds) - (Energy Released when Bonds Form)