Review Review
● Formal Charge FC = nval – nnb – (½)nb or
- - -
FC=(# valence e )−(# non−bonding e )−(1/2)(# bonding e )
– Use to help decide on best resonance structures.
– Use to decide if need to expand the octet for period
3 (and below) central atoms.
– Can help pick best atom arrangement.
●
Quick Lewis Atom
H
Number of Bonds
1
Lewis Cartoon
H-
C 4
structure rules
(don't always N 3
O 2
work).
Exchange or sharing of e- to get nearest noble gas F (same for other 1
configuration halogens)
Review Systematic Lewis Structures
1) Count the total number of valence electrons using the periodic table as a guide.
●
Covalent Add or subtract from this to account for the overall charge on the species.
– Electrons shared to get noble gas configuration. 2) Draw single bonds from each of the outer atoms to the central atom in the
molecule. The central atom is usually the atom with the least negative electron
– Formed from atoms close together in the periodic affinity (or lowest electronegativity). Subtract two electrons from the total number
of electrons for each bond you have made.
table (primarily non-metals).
3) Put electrons on the outer atoms to give each atom a total of eight (an octet). H
– Using electronegativity to decide if bonds are non- (hydrogen) only needs two electrons, Be (beryllium) often only 4e-, B (boron)
often only 6e-. If you run out of electrons before filling the outer atoms' octets,
polar covalent, polar covalent or ionic. stop.
– Systematic rules for drawing Lewis structures. 4) Any electrons that were not used up in step 3 should be put on the central atom.
You should now have no unused valence electrons.
– Exceptions to the octet rule:
5) If any atoms do not have octets, make multiple bonds (double and triple) by
●
H gets duet, B gets sextet. sharing electron pairs from atoms that do have octets.
.
N=O↔ N=O.
: :
: : : :
●
Odd electron species (NO). 6) Look for resonance structures. If there are resonance structures, the molecule
:
: : :
is better modeled as an average of all the possible structures.
● Expanded octets (XeF2)
: 7) Use formal charge to identify the best resonance structures and check if an
: :
:F –Xe– F: expanded octet for period 3 and higher atoms gives better formal charges.
Review Review
●
For a single pair of atoms: ●
Electron group repulsions distort molecular
– Bond strength: triple > double > single geometry.
– Bond length: triple < double < single – The repulsions vary: nonbonding pair-nonbonding
●
VSEPR model predicts molecular geometry by pair > nonbonding pair-bond > bond-bond.
assuming the electron groups arrange – Lone (non-bonding) pairs push bonds closer
themselves around the central atom to be as far together.
apart as possible.
– :, ., –, = or ≡ each count as one group.
107.5˚
# of groups 2 3 4 5 6 109.5˚ 104.5˚
e- geom. Linear Trigonal Planar Tetrahedral Trigonal Bipyramidal Octahedral
FIGURE 4.19 Review
Review
●
Predicting molecular polarity from bond dipoles
and shapes.
– If outer atoms are the same and arranged
symmetrically about the central atom the molecule
is non-polar.
– Hydrocarbons (containing C & H only are non-
polar).
●
Multicenter molecules shape about each atom
can be predicted using VSEPR.
Review: Review
Valence Bond model of covalent bonding
●
Bonds are formed by electron orbitals on ●
Multiple bonds consist of end-on overlapping
different atoms overlapping and constructively orbitals (σ-bonds) and side-on overlapping
interfering. orbitals (π-bonds).
BOND CARTOONS/SKETCHES
++ = bond
S + S: • ↑↓ • or • ↑↓ •
A B
+- = no bond
• ↑↓ •
●
Double bond = 1 σ and 1 π
S + P:
●
Triple bond = 1 σ and 2 π.
Review:
Valence Bond model of Review
covalent bonding
●
Energy = capacity to do work
– Standard units = J =N•m = kg•m2s-2
●
Bonded atoms are
– Energy is conserved.
lower energy than
non-bonded – Forms: potential (ex. chemical), kinetic (ex. thermal),
electromagnetic.
atoms.
●
Thermochemistry = study of energy in chemical
●
Use hybridization reactions.
to get orbitals – System = what we are care about (at minimum all
pointing the reactants and products).
correct directions – If energy comes out (is produced) the process is
to form bonds. exothermic and q <0.
– If energy goes in (is used) the process is endothermic (q
> 0).
o
Substance ∆H f (kJ/mol)
Review Con't CH4
C2H6
C2H6O
-74.6
-84.7
-277.6
∆HoRXN = ∑n∆Hof(prod) - ∑n∆Hof(react)
• Calorimetry (measuring q) C8H18
C6H12O6
-249.9
-1274.4
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
– Heat capacity (C = q/∆T) – Specific heat (c = C/m)
– Molar heat capacity (cm = c(MM) )
– Relation of qs: qsys = -qsurr Appendix G
– Example 1 – System (e.g. metal) equilibrating with rest
of contents (surr):
Csys∆Tsys = -Csurr∆Tsurr
– Example 2 – RXN of two dilute solutions starting at
same temperature (assume surroundings is solvent):
qRXN = -Csoln∆T, where Csoln = msolncsoln
●
Note: in a research lab rather than this estimated Csoln,
Ctot = heat capacity of everything in the calorimeter would
be measured and used in the calculation.
Review Review
• U (internal energy) and H (enthalpy) are state functions. ●
Hess’s Law General
●
∆U = q + w (always) and ∆H = q (constant P). – Application of conservation of energy.
● ∆HRXN = the enthalpy change for a reaction as written. – You can calculate the overall ∆H by following any route
where you know the ∆H of each intermediate step.
● ∆Hfo = ∆HRXN of elements in their standard states to give
one mole of the compound in its standard state.
– ∆HRXN (A --> C) = ∆HRXN (A --> B)+ ∆HRXN (B --> C)
– ∆Hfo (elements in standard state) = 0.
– ∆HoRXN from ∆Hof is application of this:
reactants → elements → products
●
Hess’s law (conservation of energy) =>
- ∑n∆Hof(react) ∑n∆Hof(prod)
– ∆HRXN (A →C) = ∆HRXN (A→B)+ ∆HRXN (B → C)
– Maps to: ∆HoRXN (reac →prod) = Elements
– When combining reactions match reactants and products
0 to decide direction.
∆Hfo (reac → element in standard states) +
– Running reaction backwards changes sign of ∆H.
∆Hfo (element in standard states → prod) = ∆H o reac
– If you multiply a reaction by a coefficient the ∆H must be
Δ H oRXN =∑ n Δ H of (prod)−∑ n Δ H of (reac) ∆Horxn prod multiplied by the same coefficient.
