Chapter 2.

CHEMICAL BONDS
IONIC BONDS
2.1 2.2 2.3 2.4 The Ions That Elements Form Lewis Symbols The Energetics of Ionic Bond Formation Interactions Between Ions

COVALENT BONDS
2.5 2.6 2.7 2.8 Lewis Structures Lewis Structures of Polyatomic Species Resonance Formal Charge

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 Chemical bond is the link between atoms. - ionic bond - covalent bond - metallic bond i.e. Na+, Cli.e. NH3 i.e. Cu

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IONIC BONDS (Sections 2.1-2.4)

ionic model: the description of bonding in terms of ions ionic solid: an assembly of cations and anions stacked together in a regular pattern

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2.1 The Ions That Elements Form

Cations: Remove outermost electrons in the order np, ns, (n-1)d

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Anions: Add electrons until the next noble-gas configuration is reached

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2.2 Lewis Symbols

- valence electrons depicted as dots; a pair of dots for paired electrons

- cations and anions

2.3 The Energetics of Ionic Bond Formation

Na(g) Na+(g) + e- (g) Cl(g) + e- (g) Cl-(g) Na+(g) + Cl- (g) NaCl(s) Na(g) + Cl(g) NaCl(s) 494 kJmol-1 -349 kJmol-1 -787 kJmol-1 -642 kJmol-1

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2.4 Interactions Between Ions

- In an ionic solid, each cation is attracted to all the anions to a greater or lesser extent. a global characteristic of the entire crystal Lattice energy: the difference in energy between the ions packed together in a solid and the ions widely separated as a gas - strong electrostatic interactions in ionic solids high melting points and brittleness

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60 - Coulomb potential energy of the interactions of two individual ions

e is the fundamental charge; z1 and z2 are the charge numbers of the two ions; r12 is the distance between the centers of the ions; 0 is the vacuum permittivity. - molar potential energy of a three-dimensional crystal

The factor A is the Madelung constant, dependent on how the ions are arranged about one another

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61 - In a one-dimensional crystal in which cations and anions alternate along a line,

; A = 2 ln2 or 1.386 - real potential energy of an ionic solid attractive and repulsive interionic interactions Born-Mayer equation

with d* = 34.5 pm 2012 General Chemistry I

repulsive effect

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COVALENT BONDS (Sections 2.5-2.8)

2.5 Lewis Structures
covalent bond - a pair of electrons shared between two atoms - octet rule: In covalent bond formation, atoms go as far as possible toward completing their octets by sharing electron pairs. - Valence of an atom is the number of bonds it can form. - A line (-) represents a shared pair of electrons. - lone pairs of electrons electron pairs not involved in bonding - Lewis structure atoms by chemical symbols, covalent bonds by lines, and lone pairs by pairs of dots

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2.6 Lewis Structures of Polyatomic Species

- Lewis structure does not portray the 3D shape of a molecule or ion, but simply displays which atoms are bonded together.

- bond order: the number of bonds that link a specific pair of atoms.

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65 Writing a Lewis structure - terminal atom: bonded to only one other atom central atom: bonded to at least two other atoms

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2.7 Resonance
-

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- double-headed arrows (), indicating a blend of the contributing structures

- delocalization: a shared electron pair is distributed over several pairs of atoms and cannot be identified with just one pair of atoms. 2012 General Chemistry I

69 Benzene, C6H6

- No reactions typical of compounds with double bonds - All the carbon-carbon bonds with the same length - Only one 1,2-dichlorobenzen exists.

2010, 2008, 2005, 2002 by P. W. 2012 General Chemistry I Atkins and L. L. Jones

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2.8 Formal Charge

Formal charge the charge it would have if the bonding were perfectly covalent in the sense that the atom had exactly a halfshare in the bonding electrons

V = the number of valence electrons in the free atom L = the number of electrons present on the bonded atom as lone pairs B = the number of bonding electrons on the atom - A Lewis structure in which the formal charges of the individual atoms are closest to zero typically represents the lowest energy arrangement of the atoms and electrons.

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71 - Formal charge exaggerates the covalent character of bonds by assuming that the electrons are shared equally. - Oxidation number exaggerates the ionic character of bonds. It represents the atoms as ions, and all the electrons in a bond are assigned to the atom with the lower ionization energy. formal charge oxidation state

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Chapter 2. CHEMICAL BONDS

EXCEPTIONS TO THE OCTET RULE
2.9 Radicals and Biradicals 2.10 Expanded Valence Shells 2.11 The Unusual Structures of Some Group 13/III Compounds

IONIC VERSUS COVALENT BONDS

2.12 Correcting the Covalent Model: Electronegativity 2.13 Correcting the Ionic Model: Polarizability

THE STRENGTH AND LENGTHS OF COVALENT BONDS

2.14 Bond Strength 2.15 Variation in Bond Strength 2.16 Bond Lengths
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2.9 Radicals and Biradicals

Radicals: species with an unpaired electron, highly reactive Biradicals: molecules with two unpaired electrons

2.10 Expanded Valence Shells

- more than 8 electrons associated with an atom in a Lewis structure - hypervalent compound: a compound that contains an atom with more atoms attached to it than is permitted by the octet rule - variable covalence: the ability to form different numbers of covalent bonds

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2.11 The Unusual Structures of Some Group 13/III Compounds

- incomplete octet: fewer than eight valence electrons - boron and aluminum

- completing octets by a coordinate covalent bond, in which both electrons come from one of the atoms

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IONIC VERSUS COVALENT BONDS (Sections 2.12-2.13)

2.12 Correcting the Covalent Model: Electronegativity
- partial charges: the charges on the atoms - polar covalent bond: a bond in which ionic contributions to the resonance result in partial charges lower energy structure - electric dipole: a partial positive charge next to an equal but opposite partial negative charge - electric dipole moment (): size of an electric dipole Debye Cl-H bond: = ~1.1 D 2012 General Chemistry I

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77 Electronegativity () Electron-pulling power of an atom when it is part of a molecule (by Linus Pauling) - Mulliken scale: = (I + Eea) average of the ionization energy and electron affinity - Increases from left to right and from bottom to top - rough rules of thumb ionic polar covalent covalent i.e. NaCl or KF : ionic C-O : polar covalent Ca-O : ionic 2012 General Chemistry I

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2.13 Correcting the Ionic Model: Polarizability

- All ionic bonds have some covalent character. - highly polarizable atoms and ions: readily undergo a large distortion of their electron cloud i.e. large anions and atoms such as I-, Br-, and Cl- polarizing power: property of ions (and atoms) that cause large distortions of electron clouds - increases with decreasing size and increasing charge of a cation i.e. the small and/or highly charged cations Li+, Be2+, Mg2+, and Al3+

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THE STRENGTHS AND LENGTHS OF COVALENT BONDS (Sections 2.14-2.16)

2.14 Bond Strength
Dissociation energy (D): energy required to separate the bonded atoms - The bond breaking is homolytic, which means that each atom retains one of the electrons from the bond.

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- average dissociation energy for one type of bond found in different molecules i.e. C-H single bond: average strength of bonds in a selection of organic molecules, such as methane (CH4), ethane (C2H6), and ethene (C2H4) 2012 General Chemistry I

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2.15 Variation in Bond Strength

- Factors influencing bond strength

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2.16 Bond Length

Bond length: the distance between the centers of two atoms joined by a covalent bond - corresponding to the internuclear distance at the potential energy minimum for the two atoms - affecting the overall size and shape of a molecule evaluated by using spectroscopy or x-ray diffraction methods - Factors influencing bond length

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Covalent radius: contribution an atom to the length of a covalent bond - Approximately the sum of the covalent radii of the two atoms

- Decreases from left to right (increasing Zeff ) - Increases in going down a group (size of valence shells and better shielding by inner core electrons)

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INFRARED SPECTROSCOPY
Infrared radiation: electromagnetic radiation with longer wavelengths (lower frequencies) than red light ~ 1000 nm or ~ 31014 Hz - Molecules by infrared radiation become vibrationally excited. - stretching mode: the atoms moving closer and away again. bending mode: bond angles periodically increase and decrease. Vibrational frequencies - The stiffness of a bond measured by its force constant, k Force = -k displacement by Hookes law - Vibrational frequency, , of a bond between two atoms A and B of mass mA and mB = =
= effective mass (or reduced mass)

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91 Normal modes of vibration A nonlinear molecule consisting of N atoms 3N-6 normal modes A linear molecule 3N-5 normal modes i.e. H2O, n = 3 3 normal modes CO2, n = 3 4 normal modes Characteristic frequencies of functional groups detectable in a spectrum - fingerprint region: a complex series of absorptions

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