Chemistry: Atoms and Ions - Study Notes

Chapter 2: Atoms and Ions

Early Ideas in Atomic Theory

Dalton's Atomic Theory (Five Postulates)
  • Matter is composed of exceedingly small particles called atoms.

    • An atom is the smallest unit of an element that can participate in a chemical change.

  • An element consists of only one type of atom.

    • Each atom has a mass characteristic of the element.

    • The mass is the same for all atoms of that element.

  • Atoms of one element differ in properties from atoms of all other elements.

  • A compound consists of atoms of two or more elements combined in a small, whole-number ratio.

    • In a given compound, the number of atoms of each of its elements are always present in the same ratio.

  • Atoms are neither created nor destroyed during a chemical change.

    • Instead, they rearrange to yield different types of matter.

Law of Conservation of Matter
  • Dalton's atomic theory provides a microscopic explanation for macroscopic properties of matter.

  • Principle: If atoms are neither created nor destroyed during a chemical change, then the total mass of matter present when matter changes from one type to another will remain constant.

Law of Definite Proportions (Law of Constant Composition)
  • Principle: All samples of a pure compound contain the same elements in the same proportion by mass.

    • Example (Isooctane):

      • Sample A: Carbon = 14.82 \text{ g}, Hydrogen = 2.78 \text{ g} (Mass Ratio consistent)

      • Sample B: Carbon = 22.33 \text{ g}, Hydrogen = 4.19 \text{ g} (Mass Ratio consistent)

      • Sample C: Carbon = 19.40 \text{ g}, Hydrogen = 3.64 \text{ g} (Mass Ratio consistent)

Evolution of Atomic Theory

Important Discoveries of the 20th Century
  • Isotopes: Atoms of the same element that differ in mass.

  • Neutrons: Uncharged, subatomic particles found in the nucleus with a mass approximately the same as that of protons.

Atomic Structure and Symbolism

Atomic Composition
  • Nucleus: Contains the majority of an atom's mass.

    • Composed of protons and neutrons.

    • Diameter of a nucleus is approximately 10^{-15} \text{ m}.

  • Electrons: Occupy almost all of an atom's volume.

    • Much lighter than protons and neutrons.

    • Diameter of an atom is approximately 10^{-10} \text{ m} (100,000 times larger than the nucleus).

    • Analogy: If an atom were a football stadium, the nucleus would be the size of a single blueberry.

Units for Subatomic Particles
  • Atoms and subatomic particles are exceedingly small.

    • Carbon atom weighs less than 2 \times 10^{-23} \text{ g}.

    • Electrons have a charge of less than 2 \times 10^{-19} \text{ C}.

  • Atomic Mass Unit (amu):

    • 1 \text{ amu} = 1.6605 \times 10^{-24} \text{ g}.

    • Mass of a carbon-12 atom = 12 \text{ amu}.

  • Fundamental Unit of Charge (e):

    • e = 1.602 \times 10^{-19} \text{ C} (equivalent to the magnitude of charge on one electron or proton).

Properties of Subatomic Particles

Particle

Mass (amu)

Charge

Proton

1.0073

+1

Neutron

1.0087

0

Electron

0.00055

-1

Atomic Number (Z)
  • The number of protons in the nucleus of an atom.

  • Defining trait of an element: Its value determines the identity of the atom.

    • For example, any atom with six protons is carbon (Z = 6), regardless of neutron or electron count.

Neutral Atoms
  • Must contain the same number of positive and negative charges.

  • Number of protons equals the number of electrons.

  • Therefore, in a neutral atom, Z also indicates the number of electrons.

Mass Number (A)
  • The total number of protons and neutrons in an atom.

  • Calculation of Neutrons: Number of neutrons = A - Z.

    • Atomic number (Z) = number of protons.

    • Mass number (A) = number of protons + number of neutrons.

Ions
  • Atoms (or molecules) that are electrically charged because the number of protons and electrons are NOT equal.

  • Charge of an atom = number of protons - number of electrons.

  • Formed by gaining or losing electrons.

Types of Ions
  • Anion: An atom that gains one or more electrons, exhibiting a negative charge.

    • Example: A neutral oxygen atom (Z=8) has 8 electrons. If it gains two electrons, it becomes an anion with a 2- charge (8 - 10 = -2).

  • Cation: An atom that loses one or more electrons, exhibiting a positive charge.

    • Example: A neutral sodium atom (Z=11) has 11 electrons. If it loses one electron, it becomes a cation with a 1+ charge (11 - 10 = +1).

Chemical Symbols
  • An abbreviation used to indicate an element or an atom of an element.

    • Example: Hg for mercury.

  • Most symbols have one or two letters; three-letter symbols for elements past Z=112.

  • Only the first letter is capitalized.

    • (See Table 2.3 for common elements and their symbols, e.g., Fe from ferrum, Pb from plumbum, Au from aurum).

Isotope Notation
  • The symbol for a specific isotope places the mass number (A) as a superscript to the left of the element symbol.

  • The atomic number (Z) is sometimes written as a subscript to the left of the element symbol, but is often omitted because the element symbol already implies Z.

  • General form: ^{\text{A}}_{\text{Z}}\text{X} or simply ^{\text{A}}\text{X}.

    • Example: Magnesium isotopes are ^{\text{24}}\text{Mg}, ^{\text{25}}\text{Mg}, and ^{\text{26}}\text{Mg}.

      • All have 12 protons (Z=12), but differing numbers of neutrons.

  • Hydrogen Isotopes:

    • Protium (^{\text{1}}\text{H}): 1 proton, 0 neutrons.

    • Deuterium (^{\text{2}}\text{H} or ^{\text{2}}\text{D}): 1 proton, 1 neutron.

    • Tritium (^{\text{3}}\text{H} or ^{\text{3}}\text{T}): 1 proton, 2 neutrons.

Atomic Mass
  • The atomic mass of a single atom in amu is approximately equal to its mass number (since protons and neutrons each have mass \approx 1 \text{ amu}).

  • Most elements occur naturally as a mixture of two or more isotopes.

  • The periodic table lists the weighted, average mass of all isotopes present in a naturally occurring sample of that element.

    • Calculation Example (Boron):

      • 19.9\% ^{\text{10}}\text{B} with mass 10.0129 \text{ amu}.

      • 80.1\% ^{\text{11}}\text{B} with mass 11.0093 \text{ amu}.

      • Average Atomic Mass = (0.199 \times 10.0129 \text{ amu}) + (0.801 \times 11.0093 \text{ amu}).

Mass Spectrometry (MS)
  • An instrument used to experimentally determine the occurrence and natural abundances of isotopes.

  • Process: Sample is vaporized and exposed to a high-energy electron beam, causing atoms (or molecules) to lose electrons and become electrically charged cations.

  • These cations are then separated by their mass-to-charge ratio.

    • Produces a mass spectrum with peaks corresponding to different isotopes.

Chemical Formulas

Types of Chemical Formulas
  • Molecular Formula: A representation of a molecule or compound.

    • Consists of chemical symbols for types of atoms.

    • Subscripts after the symbol indicate the number of each type of atom (only if more than one).

    • Example: Methane (CH_4).

  • Structural Formula: Shows the same information as a molecular formula but also explicitly shows how the atoms are connected.

    • Can be represented as ball-and-stick models or space-filling models.

Elements That Exist as Molecules
  • Many elements exist as discrete, individual atoms (e.g., noble gases).

  • Some elements exist as molecules:

    • Diatomic Molecules: H2, N2, O2, F2, Cl2, Br2, I_2.

    • Polyatomic Molecules: Elemental sulfur typically exists as S_8.

  • Distinguishing Symbols:

    • H: One hydrogen atom.

    • 2H: Two separate hydrogen atoms.

    • H_2: One hydrogen molecule (two bonded hydrogen atoms).

    • 2H_2: Two hydrogen molecules.

Empirical Formula
  • Indicates the simplest whole-number ratio of the number of atoms (or ions) in a compound.

  • Contrast with Molecular Formula: A molecular formula indicates the actual numbers of atoms of each element in a molecule.

    • Example: Benzene

      • Molecular formula = C6H6.

      • Empirical formula = CH.

    • Example: Acetic Acid

      • Molecular formula = C2H4O_2.

      • Empirical formula = CH_2O.

    • Note: For some compounds, the molecular and empirical formulas are the same (e.g., H2O, TiO2).

Isomers
  • Compounds with the same chemical formula but different molecular structures and properties.

  • Structural Isomers: Differ in the bonding arrangement of atoms.

    • Example: Acetic acid (CH3COOH) and methyl formate (HCOOCH3) both have the molecular formula C2H4O_2.

  • Spatial Isomers (Stereoisomers): Differ only in the relative orientations of the atoms in space.

    • Example: Different forms of carvone (spearmint vs. caraway scent).

The Periodic Table

Historical Context
  • Dimitri Mendeleev (Russia, 1869) and Lothar Meyer (Germany, 1870): Independently recognized a periodic relationship among element properties.

  • Arranged elements according to increasing atomic mass.

  • Mendeleev's Contribution: Used his table to predict the existence and properties of unknown elements (e.g., gallium, germanium), which were later discovered, supporting his work.

The Modern Periodic Table
  • By the 20th century, it was realized that elemental properties are better correlated with atomic numbers.

  • Periodic Law: The properties of the elements are periodic functions of their atomic numbers.

  • Organization: Arranges elements in increasing order of their atomic numbers.

    • Groups (Vertical Columns): 1-18. Elements in the same group have similar chemical properties.

    • Periods (Horizontal Rows): 1-7. Properties gradually change across a period.

Classifications of Elements
  • By Physical & Chemical Properties:

    • Metals: Shiny, malleable, good conductors of heat and electricity (tend to lose electrons).

    • Nonmetals: Dull, poor conductors of heat and electricity (tend to gain or share electrons).

    • Metalloids (Semimetals): Possess properties intermediate between metals and nonmetals; conduct heat and electricity moderately well.

  • By Position on the Table:

    • Main Group Elements (Representative Elements): Groups 1, 2, 13-18.

    • Transition Metals: Groups 3-12.

    • Inner Transition Metals: Two rows at the bottom.

      • Lanthanides: Top row.

      • Actinides: Bottom row.

  • Specific Groups:

    • Group 1: Alkali Metals (except hydrogen).

    • Group 2: Alkaline Earth Metals.

    • Group 15: Pnictogens.

    • Group 16: Chalcogens.

    • Group 17: Halogens.

    • Group 18: Noble Gases (or inert gases).

Molecular and Ionic Compounds

Chemical Reactions and Electron Behavior
  • In ordinary chemical reactions, the nucleus (and thus element identity) remains unchanged.

  • Electrons participate by being gained, lost, or shared, leading to the formation of ions or molecules.

Predicting Ion Charge (for Main-Group Elements)
  • The periodic table guides the prediction of ionic charges for main-group elements.

  • Metals (Groups 1, 2, 13): Tend to lose electrons to achieve the electron count of the preceding noble gas (forming cations).

    • Group 1: Lose one electron, form 1+ charge (e.g., Na^+).

    • Group 2: Lose two electrons, form 2+ charge (e.g., Ca^{2+}).

    • Group 13 (Al): Lose three electrons, form 3+ charge (e.g., Al^{3+}).

  • Nonmetals (Groups 15, 16, 17): Tend to gain electrons to achieve the electron count of the next noble gas (forming anions).

    • Group 17 (Halogens): Gain one electron, form 1- charge (e.g., Br^-).

    • Group 16 (Chalcogens): Gain two electrons, form 2- charge (e.g., O^{2-}).

    • Group 15 (Pnictogens): Gain three electrons, form 3- charge (e.g., N^{3-}).

  • Transition Metals: Less reliable prediction; often form multiple cations with variable charges (e.g., Cu^+ and Cu^{2+}, Fe^{2+} and Fe^{3+}).

Polyatomic Ions
  • Monatomic Ions: Formed from only one atom (e.g., Na^+, Cl^-, O^{2-}).

  • Polyatomic Ions (Molecular Ions): Electrically charged molecules; groups of bonded atoms with an overall charge.

    • Oxyanions: Polyatomic ions that contain one or more oxygen atoms.

Naming Oxyanions (Systematic Approach)
  • Two Oxyanions from a Nonmetal:

    • -ate suffix: Used for the ion with the larger number of oxygen atoms (e.g., SO4^{2-} sulfate, NO3^{-} nitrate).

    • -ite suffix: Used for the ion with the smaller number of oxygen atoms (e.g., SO3^{2-} sulfite, NO2^{-} nitrite).

  • More than Two Oxyanions from a Nonmetal (using prefixes):

    • per- (largest number of oxygens): perchlorate (ClO_4^{-}).

    • -ate (one fewer oxygen): chlorate (ClO_3^{-}).

    • -ite (two fewer oxygens): chlorite (ClO_2^{-}).

    • hypo- (smallest number of oxygens): hypochlorite (ClO^{-}).

  • (See Table 2.5 for a partial list of common polyatomic ions).

Types of Chemical Bonds
  • Ionic Bond: Results when electrons are transferred between atoms, forming ions.

    • These are electrostatic forces of attraction between oppositely charged ions.

  • Covalent Bond: Results when electrons are shared between atoms, forming molecules.

  • Compounds are classified as ionic or molecular (covalent) based on the types of bonds present.

Ionic Compounds
  • Typically formed when a metal (readily loses electrons, forming cations) reacts with a nonmetal (readily gains electrons, forming anions).

  • Contain ions held together by ionic bonds.

  • Formation Examples:

    • Na (metal) + Cl (nonmetal) \rightarrow Na^+ + Cl^- \rightarrow NaCl

    • Ca (metal) + 2 Cl (nonmetal) \rightarrow Ca^{2+} + 2 Cl^- \rightarrow CaCl_2

  • Properties:

    • Typically solids at room temperature.

    • High melting and boiling points.

    • Nonconductive in solid form.

    • Conductive in molten (liquid) form or when dissolved in water (due to mobile ions).

Formulas of Ionic Compounds
  • Ionic compounds are electrically neutral overall.

  • The formula must show a ratio of ions such that the total positive and negative charges are equal.

  • These are not molecular formulas; they represent the simplest ratio of ions in the crystalline lattice.

    • Example 1: Al^{3+} and O^{2-} forms Al2O3.

      • 2 \times (+3) = +6 total positive charge.

      • 3 \times (-2) = -6 total negative charge.

  • Compounds with Polyatomic Ions: Treat polyatomic ions as discrete units.

    • Use parentheses to indicate a group of atoms behaving as a unit that appear more than once.

    • Example 2: Ca^{2+} and PO4^{3-} forms Ca3(PO4)2.

      • 3 \times (+2) = +6 total positive charge.

      • 2 \times (-3) = -6 total negative charge.

Molecular Compounds (Covalent Compounds)
  • Result when atoms share electrons.

  • Exist as discrete, neutral molecules.

  • Usually formed by a combination of two or more nonmetals.

  • Properties:

    • Often exist as gases, low-boiling liquids, and low-melting solids (compared to ionic).

Chemical Nomenclature

Overview
  • Nomenclature: A collection of rules for naming things.

  • Compounds are identified by both their formula and name.

  • Focus: Ionic and molecular binary compounds, ionic compounds with polyatomic ions, and acids.

Naming Ionic Compounds
  • General Rules:

    1. Name the cation first, followed by the name of the anion.

    2. Monoatomic Cation: Simply the name of the element (e.g., sodium).

    3. Monoatomic Anion: Name of the element with its ending replaced by the suffix -ide (e.g., chloride, oxide, sulfide, nitride, phosphide, carbide).

    4. Polyatomic Ion: Given the name of the ion directly (from Table 2.5).

  • Examples:

    • NaCl: sodium chloride

    • Na_2O: sodium oxide

    • KBr: potassium bromide

    • Mg3N2: magnesium nitride

    • KC2H3O_2: potassium acetate

    • (NH_4)Cl: ammonium chloride

    • CaSO_4: calcium sulfate

    • Al2(CO3)_3: aluminum carbonate

Naming Ionic Compounds with Metal Ions of Variable Charge
  • Primarily transition metals and some main group metals can form multiple cations with different charges.

  • The charge of the metal ion is specified by a Roman numeral in parentheses after the name of the metal element.

    • Example: FeCl2 is iron(II) chloride; FeCl3 is iron(III) chloride.

    • Example: Hg2O is mercury(I) oxide (note: Hg2^{2+} is a specific polyatomic ion); HgO is mercury(II) oxide.

Naming Ionic Hydrates
  • Hydrate: An ionic compound that contains one or more water molecules bound within its crystals.

  • Can be dehydrated by heating to yield the anhydrous compound (without water).

  • Naming Rules:

    1. Name the anhydrous compound according to usual rules.

    2. Add the word