3.

1: Bonding
 Atoms of elements can combine to form molecules 
 Except for some noble gases 
 Atoms in molecules are held together by chemical bonds (strong attractive forces) 
 Chemical bonds are formed by the interaction of valence e- 
 Chemical and physical properties of molecule is usually different than elements that
make it up 
 Atoms usually bond according to the octet rule 
 Octet rule: atoms tend to bond with other atoms so that it has eight electrons in its
valence shell → noble gas configuration (stable) 
 Many elements form bonds that are exception to the octet rule
 Hydrogen can only have 2 valence e- 
 Helium can only have 2 valence e- 
 Lithium can only have 2 valence e- 
 Beryllium can only have 4 valence e- 
 Boron can only have 6 valence e- 
 All elements in period 3 and greater can expand valence shell to hold more than 8
e- by using d-orbitals 
 Molecule with an odd number of valence e- cannot distribute the e- to give eight to each
atom (i.e. NO has 7 valence e-) 
 Nonmetals gain electrons (anions) while metals lose electrons (cation) to achieve their
octet 
 Types of bonds 
 Ionic bonding 
 One or more e- from an atom with low IE (usually a metal) is transferred
to an atom with high EA (nonmetal) 
 Results in cation and anion → electrostatic attraction between the
oppositely charged ions hold them together 
 Forms lattice structures with repeating rows of cation and anions 

 Covalent bonding 
 Each atom donates an e- to the shared pair
 Electron pair is shared between two atoms that have relatively similar EN
values (usually nonmetals) 
  Shared equally (close EN values) → nonpolar covalent bond 
 Shared unequally (far EN values) → polar covalent bond 
 Coordinate covalent bond: bond in each the shared e- are contributed by
only one of the two atoms 
 Covalent compounds consist of individually bonded molecules

3.2: Ionic Bonds 

 Ionic bonds form between two atoms that have significantly different EN values 
 One that loses e- → cation and the one that gains e- → anion 
 Electrostatic force of attraction between the oppositely charged ions → ionic
bond 
 Electrons are not shared but transferred from one atom to another 
 In order for transfer to occur, the difference in EN values must be greater than 1.7 on
pauling scale 
 Generally form between metal (cation) and nonmetal (anion) 
 Physical properties of ionic bonds 
 Electrostatic force is strong → high BP and MP 
 Dissolve readily in water and other polar solvent 
 Good conductors of electricity in molten or aqueous state 
 Form crystalline lattice in solid state 
 Repeating positive and negative ions 
 Attraction is maximized and repulsion is minimized 
3.3: Covalent Bonds
 When two atoms with similar EN values interact it is energetically unfavorable to create
ions 
 Energy required to transfer e- > energy released when ion is formed 
 Atoms share e- rather than transfer them 
 Attraction that each electron in the shared pair has for the positive nuclei of the
bonded atom 
 The electrons that are shared are attracted to both nuclei 
 Discrete molecular units with relatively weak intermolecular interaction → lower
MP and BP
 Do not break into ions → poor conductors of electricity 
 Properties of covalent compounds 
 One covalent bond may not be enough to fill the valence shell for a given atom,
so many atoms can form multiple covalent bonds 
  One covalent bond - single bond
 Two covalent bonds - double bond 
 Three covalent bonds - triple bond 
 Bond order = the number of shared electron pairs between two atoms 
 One covalent bond - one
 Two covalent bonds - two  
 Three covalent bonds - three
 Bond length 
 Average distance between the two nuclei of atoms in a bond 
 Number of shared e- increases (greater bond order) → atoms are pulled
closer → decreased bond length 
 Single bond > double bond > triple bond 
 Bond energy
 Energy required to break a covalent bond by separating the atoms into
their gaseous atomic states 
 Greater bond order → more energy to break the bonds 
 Triple bond > double bond > single bond 
 Greater bond energy = stronger bond 
 Polar covalent bond 
 Polarity (Occurs when two atoms have relative difference in EN) 
 Atom with higher EN will get larger share of electron density
 Difference in EN → dipole moment
 Partial positive on less EN atom and partial negative end on
EN atom 
 Dipole moment is a vector quantity given by p=qd (measured in
Debye units or coulomb-meters)
 p= dipole moment 
 q= magnitude of charge 
 d= displacement vector separating the two partial charges 
 EN difference between 0.5 and 1.7 
 Nonpolar covalent bond means atoms have nearly identical EN, so they
share electron density equally 
 No separation of charge across the bond so no dipole 
 Only bonds between the same atom will have the same EN →
purely equal electron density distribution 
 i.e. the seven diatomic atoms (H2, N2, F2,O2,I2,Cl2,Br2)
 Considered nonpolar if EN difference is less than 0.5 
 Coordinate covalent bond 
 Both of the shared e- are from the same atom 
 Usually means an atom with lone pair attacks an atom with un unhybridized p
orbital 
 Once the bond is formed, it cannot be distinguished from other covalent bonds 
 Typically found in lewis acid-base (electrophile-nucleophile)reactions 
 Lewis acid (electrophile): accepts e- 
 Lewis base(nucleophile): donates e- 
 Coordinate bond notation 
 e- involved in covalent bond are in the valence shell (valence e-) and referred to
as bonding e- 
 e- that are in valence shell (valence e-) but NOT involved in covalent bond are
nonbonding e- 
 Unshared e- pairs are called lone pairs 
 Associated only with one atomic nucleus 
 Atoms can bind with other atoms in many different combos → lewis structure
system (bookkeeping method for e-) 
 Keeps track of the bonded and nonbonded e- pairs 
 Number of valence e- an atom has in a lewis structure may not be the same
number of valence e- the atom has in the neutral atom 
 Difference is accounted for in the formal charge of an atom in a lewis
structure (FC = valence electrons - sticks(bonding) - dots(nonbonding) 
 More than one lewis structure can usually be drawn for a molecule 
 If lewis structures differ in connectivity or arrangement → different
compounds 
 If lewis structures have the same connectivity and different only in
arrangement of e- → same compounds, different resonance forms
 Lewis structure do NOT represent the actual or theoretical geometry 
 They only show different possible ways that atoms can be combined to
form different compounds or resonance forms of a single compound 
 When more than one lewis structure is possible, assess the formal charge to
determine likelihood of arrangement 
 Arrangement that minimizes the number and magnitude of formal charges
is most stable arrangement of compound 
 Lewis structures (lewis dot diagrams)
 Chemical symbol of an element surrounded by dots 
 Each dot represents one of the s or p valence e- of an atom 
 Lewis structures can represent
 Valence e- of an atom 
 Valence e- in an ion 
 Valence e- in a molecule 
 Rules for drawing lewis structures 
 Place the least EN atom (not hydrogen) at the center 
 Hydrogen (always) and halogens (usually) are in the terminal
position
 Count the total valence e- 
 Add all the valence e- of the atoms that make up the molecule 
 Draw single bond between central atom and the atoms surrounding it 
 Place the remaining valence e- around the surrounding atoms until their
octet rule is fulfilled
 Remember exceptions (i.e. hydrogen only gets 2 e-)
 If there are valence e- left after satisfying the octet rule of surrounding
atoms, place the remaining e- on the central atom 
 To complete the octet of the central atom, draw double and triple bonds
between the central atom and the surrounding atoms using the lone pairs
on the surrounding atom (if needed) 

 Formal Charge 
 Use formal charge to determine if the lewis structure is representative of the
actual arrangement of atoms in a compound 
 Assume perfect sharing of all bonded e- pairs even if there is a different in EN 
 Basically assume each electron pair is split evenly (both atoms use the e-
in the pair to the same degree) 
 FC is the difference between number of e- assigned to an atom in a lewis structure
and the number of e- normally in the atom’s valence shell 
 FC = Valence electrons - sticks (bonding electrons) - dots (nonbonding
electrons) 
 The charge of an ion or compound = sum of FC of the individual atoms that make
up the ion or compound 
 Difference between formal charge and oxidation state 
  FC underestimates EN
 Assumes e- density is shared evenly even with difference in EN
 oxidation state overestimates EN 
 Assumes that e- density is not shared at all 
 More EN atom will receive all the e- density 
 Resonance  
 structures with same connectivity but different arrangements of e- 
 Resonance structures are represented by double headed arrows between the
structures 
 Actual e- distribution and nature of bonds is a hybrid/mix of all the structures
(resonance hybrid) 
 More stable resonance structure → contribute more to the hybrid resonance
structure 
 Major contributor 
 Small or no FC (minimize FC) 
 Less separation between opposite charges 
 Negative FC on more EN atoms 
 Geometry and Polarity 
 Valence shell electron pair repulsion (VSEPR) theory 
 Uses lewis dot structures to predict the molecular geometry of covalently
bonded molecules 
 3D arrangement of atoms surrounding a central atom is determined by the
repulsion between bonding and nonbonding e- pairs in the valence shell of
the central atom 
 e- pairs arrange themselves as far apart as possible → minimizing
repulsive forces 
 Steps used to predict VSEPR 
 Draw Lewis dot structure of molecule
 Count the regions of electron density 
 Note how many lone pairs are present
 Match the bonding and nonbonding count to the table 
 Electronic geometry: arrangement of all electron pairs around the central
atom including bonding and lone pairs (nonbonding) 
 Molecular geometry: arrangement of only the bonding pairs of electrons 
 Use of coordination number (number of atoms that surround and
are bonded to the central atom) to determine molecular geometry 
 Match areas of electron density and number of lone pairs to chart
above to find molecular geometry 
 Ideal bond angles are found from electronic geometry 
 Electronic geometry ignores effect of lone pairs and expresses the
ideal bond angles 
 IRL, lone pairs exert more repulsion and decrease bond angle bc
they are closer to the nucleus
 Polarity of molecules 
 Two atoms of different EN (0.5 to 1.7) bond covalently → polar covalent bond 
 More EN atom receives partial negative and less EN atom receives
parietal positive 
 Presence of bond dipole does NOT mean the molecule will have a dipole 
 Must consider molecular geometry and vector addition of bond dipoles to
determine if molecule will have dipole 
 Compound with nonpolar bonds → always nonpolar 
 Compound with polar bonds may be polar or nonpolar 
 Molecular geometry cancels the dipoles → nonpolar 
 Molecular geometry does not cancel dipole → polar 

  ←  NONPOLAR MOLECULAR SHAPES

 Atomic and molecular orbitals 

  Two atoms bond to form a compound → atomic orbitals interact to form a
molecular orbital 
 Describes the probability of finding the bonding e- in a given space 
 MO are obtained by combining the wave function of the atomic orbitals 
 Same sign → bonding mo
 Different sign → nonbonding mo 
 Patterns of overlap between AOs can occur when forming MOs 
 Head to head or tail to tail → sigma bond 
 Free rotation possible 
 Side to side 
 No free rotation because there is e- density above and below

3.4: Intermolecular Forces 

 Atoms and compounds participate in weak electrostatic interactions 
 Strength of intermolecular forces can impact physical properties (i.e. MP or BP) 
 Strength 
 Dispersion (london) forces < dipole-dipole interactions < H-bonds 
 NOTE: H-bonding does not involve actual sharing or transfer of e- 
 All of these forces are weaker than covalent, so they require smaller amount of energy to
break them 
 London dispersion forces (type of van der waals force) 
 e- in a nonpolar bond are shared equally, but at any moment in time the e- can be
located randomly throughout orbital 
 If the e- density if unequally distributed → rapid polarization and
counterpolarization → short-lived dipole moment 
 Dipole will interact with neighboring e- clouds which will induce formation of
more dipoles 
 Negative end of dipole near one side of cloud → side of cloud to become
positive while the other side becomes negative
  The negative side of cloud will interact with another cloud and cycle
continues 
 Weakest bc they are based on induced dipoles that change from moment to
moment 
 Do not extend over long distances so work best when molecules are close 
 Strength depends on polarizability of molecule (how easily the e- cloud can be
shifted) 
 Larger molecules are easier to shift so they have higher dispersion forces 
 Even though they are weak, millions of dispersion forces can have a great impact 
 Dipole-dipole interactions 
 Polar molecules usually orient to where the oppositely charged ends are closer to
each other 
 Energetically favorable bc attractive electrostatic force is formed 
 Attractive force is indicated by dashed lines (shows temporary bonding
interaction) 
 Present in solid and liquid but not gas due to distance between molecules 
 Higher MP and BP 
 Different from london forces because they last longer than dispersion forces 
 Hydrogen bonding 
 Specific, unusually strong dipole-dipole interaction 
 Can be intra- or intermolecular 
 Not actually a bond 
 No transferring or sharing of e- 
 When H is bonded to F, O, or N, the hydrogen will have a partial positive while
the more EN atom will have a partial negative 
 Positive charged H will interact with negative of F,O, or N on nearby
molecules 
 Substance with H-bonding have very high BP and MP bc it takes a lot of energy
to break H-bond