inorganic 2 final

Atomic Orbitals

Solution to SWE

n

• principal quantum number

• radial part of the wave function

l

• orbital quantum number (angular momentum quantum number)

• 0, 1, 2... (n-1) => s, p, d, f…

• determines the shape of the atomic orbitals.

ml

• magnetic quantum number

• +l -> -l

• determines directionality of atomic orbitals => px, py, pz

Degenerate Orbitals

possess the same energy

ms

• magnetic spin quantum number

• +½ or -½

• therefore, there are only 2 electrons per orbital

Effective Nuclear Charge (Zeff)

arises from incomplete shielding of the nuclear charge by the atomic electrons

Slater’s Rule

method of estimating Zeff experienced by electrons in different atomic orbitals

Zeff = Z – S

Z = nuclear charge

S = screening (or shielding) constant

Ionization Energy

• energy required to remove a valence electron from an atom in

the gas phase

Electron Infinity

• minus the internal energy for the gain of an electron by an atom in

the gas phase

Electronegativity

the electron withdrawing power of an atom in a molecule (x)

Covalent Radius

half of the internuclear separation in a homonuclear X-X single bond

Van der Waals Radius

half of the distance of closest approach of two non-bonded atoms of X

Soft Acids

prefer to bond to soft bases

Hard Acids

prefer to bond to hard bases

Lewis Structures

• show patterns of bonding in molecules.

• dots represent electrons.

• lines represent shared electron pairs

Lone Pairs

unshared pairs of valence electrons on atoms (influence shape and chemical

reactivity)

Resonance Structures

occurs when there are two or more structures with the same

possibility

VSEPR (Valence Shell Electron Pair Repulsion)

model for predicting molecular shape in molecules with central p-block atoms

Linear

Bent

Trigonal Planar

T-Shaped

Trigonal Pyramidal

Tetrahedral

See-Saw

Square Planar

Trigonal Bypyramidal

Square-Based Pyramidal

Pentagonal Planar

Octahedral

Pentagonal Bipyramidal

Square Antiprismatic

Cis Isomer

Trans Isomer

fac-isomer

mer-isomer

Valence Bond (VB) Theory

describes bonds in terms of the spin pairing of electrons

Pi

unhybridized p- and d-orbitals may participate in the formation of ___ bonds

Molecular Orbital Theory

• the valence shell atomic orbitals are combined to give molecular orbitals (spread over the entire molecule); the method is termed the Linear Combination of Atomic Orbitals (LCAO)

• valence electrons are then added to the resulting molecular orbitals; we assume the core electrons are not involved in bonding

Inert Pair Effect

As you go down a group and atoms get larger, the stability of the +1 oxidation state increases, indicating that the atom does not want to give away their s electrons. Their s electrons become more inert.

e.g. Tl: [Xe]6s²4f¹⁴5d¹⁰5p¹

Tl⁺: [Xe]6s²4f¹⁴5d¹⁰

Metallic Radius

half of the distance between the nearest neighbour atoms in a solid state metal lattice, and is dependent on coordination number

Metallic Structures

• strong, non-directional cohesive forces

• many metals are polymorphic (exist in more than one crystalline form)

Increases

the electrical conductivity of a semiconductor _________ with temperature

Extrinsic Semiconductors

contain dopants, impurities introduced into a semiconductor in minute amounts (1 in 106 atoms) to enhance electrical conductivity.

P-Type

Ga-doped Si yields a _____ semiconductor

N-Type

As-doped Si yields an ______ semiconductor

Intrinsic semiconductors

the extent of occupation of the upper band increases with increasing temperature

Band Gap

Label A

Conduction Band

Label B

Valence Band

Label C

Band Gap

occurs when there is a significant energy difference between two bands

Metals

exhibit high electrical conductivity

Electrical conductor

offers a low resistance to the flow of electrical current

Increases

the electrical conductivity of a wire _______ with temperature

A Band

(in Band Theory) a group of MOs, the energy difference between which are so small that the system behaves as a continuum, non-quantized variation of energy within the band is possible

Ionic Bonding

non-directional electrostatic interactions between charged species (ions)

Lattice Energy

change in internal energy that accompanies the formation of one mole of solid from its constituent gas-phase ions.

Coordination Complex

central atom or ion is coordinated by one or more molecules or ions (ligands) which act as Lewis bases (electron donors), forming coordinate bonds with the central atom or ion

Donor Atoms

In a coordination complex, atoms that are directly bound to the central atom or ion are ________

Lewis Acid

In a coordination complex, the central atom acts as a ________ (electron acceptor)

coordinate (dative) bond

donation of an electron pair from a Lewis base to a Lewis acid; results in the formation of an adduct

Chelate Effect

• when dealing with comparable uncharged ligands, polydentate ligands form more stable complexes than monodentate ones

• largely driven by a favorable increase in entropy (disorder, S > 0)

Denticity

the number of donor atoms through which a ligand coordinates to a metal ion

Chelate Ring

Coordination of a polydentate ligand to an ion leads to the formation of a _______

6-Membered

small metal cations (e.g. 1st row transition metals) favour the formation of __________ rings

5-Membered

large metal cation favour the formation of ___________ rings

Cryptand

Crown Ethers

Macrocycles

form more stable complexes than with open-chain complexes (favoured by Go )

Macrocyclic Ligands

Crown ethers, cryptands

Reduction

• gain of one or more electrons.

• loss of oxygen (or any other more electronegative element).

• gain of hydrogen (or any less electronegative element).

Oxidation

• loss of one or more electrons.

• gain of oxygen (or any other more electronegative element).

• loss of hydrogen (or any less electronegative element)

0

the oxidation state of an element is _____, whether it exists as atoms (e.g. Ne), molecules (e.g. O2 , P4 , S8 ), or an infinite lattice (e.g. Si).

the charge on the ion

in monatomic ions, the oxidation number is equal to _____

-2

the oxidation number of oxygen is usually ____

-1

In H₂O₂ and O₂^2- the oxidation number of oxygen is _____

-1

the oxidation number of hydrogen is +1 except when it is bonded to metals in binary compounds. In these cases, its oxidation number is ____

0

The oxidation number of oxygen in ozone (O₃) is _____

-1

the oxidation number of fluorine is always ____

Bronsted Acid

can act as a proton donor

Bronsted Base

can act as a proton acceptor

HF

hydrofluoric acid

HCl

Hydrochloric Acid

HBr

Hydrobromic Acid

HI

Hydroiodic Acids

HX

Hydrogen Halides

Oxoacids

a compound that contains oxygen, at least one other element, at least one hydrogen bound to oxygen, and produces a conjugate base by proton loss.

perchloric acid

HClO₄

chloric acid

HClO₃

chlorous acid

HClO₂

hypochlorous acid

HClO

Monobasic Acids

donate only one hydrogen ion () or proton per molecule to a base during an acid-base reaction

Dibasic Acids

compounds containing two replaceable hydrogen atoms (protons) per molecule, which dissociate in two steps to produce two hydronium ions (H⁺) in aqueous solution

Sulfurous Acid

• H₂SO₃

• prepared by dissolving SO₂ (g) in H₂O

• is not isolable in its pure form

Bell’s Rule

• empirical method for estimating Ka

• n = number of “hydrogen free” oxygen atoms

Hydroxides

NaOH, KOH, RbOH, CsOH, LiOH

Lewis Acid

electron pair acceptor

Lewis Base

electron pair donor

Hydration

solvation by water