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Final Exam Study Guide

1) Ionization energy, Electron Affinity
a. What is the definition of ionization energy?
It is the energy required to remove the least tightly bound electron from a neutral atom in
the gas phase.
b. What is the periodic trend in ionization energy?
Ionization energy is lowest at the bottom left corner of the table, and increases going up and
to the right, with the highest ionization energy being for Helium. This is the same trend as
for effective nuclear charge, as well as atomic radii (a smaller radius means higher Ei).
c. What is the real reason that a half filled subshell is so stable?
A half-filled subshell serves to maximize the stabilizing interactions, while minimizing the
destabilizing interactions among electrons.
d. What is the exchange interaction? Is it stabilizing or destabilizing?
The exchange interaction, πe, is the stabilizing interaction, and it is a result of electrons
pairing in degenerate orbitals with parallel spin.
e. What is the pairing energy? Is it stabilizing or destabilizing?
The pairing energy is a destabilizing interaction, the Coulomb interaction, πC, and it is the
energy of electron-electron repulsion in a filled orbital.
f. What is harder to ionize, a high energy electron or a low energy
electron?
A high energy electron is easier to ionize. It already contains more energy, so the input to
remove it from the atom is less.
g. If a 3d series metal is ionized, what orbital loses the electron? What
happens to the valence configuration?
If a d series metal has the configuration 4s23dn, the first electron to be ionized will come
from the 4s orbital. The remaining s orbital will then enter a d orbital, giving the
configuration of the +1 cation 4s03dn+1.
h. What is the Lanthanide Contraction?
It is the reduction in atomic radius following the lanthanide series, contrary to the overall
trend observed for the periodic table. The lanthanides are elements 57 through 71, and are
the first appearance of filled f orbitals. F orbitals are poor at shielding, so any electrons
added into the subshell following the f orbital experience a higher Zeff, shrinking their radius
over what is to be expected from overall trends.
i. Describe Slater’s Rules.
Slater’s Rules tell us what the effective nuclear charge will be.
Formally, it is written as Zeff= Z – σ.
Z is the atomic number, and σ=Σsi
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Si is the number of electrons in a given subshell multiplied by a weighting coefficient.

The weighting coefficients are:
1) A. For s and p valence electrons, (n-2) groups or lower contribute 1.00 to si (weighting
coefficient of 100%). 1.00xne
B. (n-1) groups contribute 0.85 to si. 0.85xne
C. N(s,p) groups (the valence groups) contribute 0.35 to si. 0.35xne
2) For d and f valence electrons:
A. electrons in the valence shell contribute 0.35 to si. 0.35xne
B. electrons in any lower group contribute 1.00 to si. 1.00xne
j. What is shielding?
Shielding is the reduction in charge attraction between the nucleus and electrons, due to
electrons between the nucleus and the electron in question. An electron is ‘between’ the
nucleus and the electron being considered if it has a lower energy.
k. What is penetration?
Penetration is when an electron of a higher atomic orbital is found within the shell of
electrons of lower atomic number. That is to say that an electron of higher energy is found
within an orbital of lower energy.
l. What is electron affinity?
Electron affinity is the difference in energy for a neutral gaseous atom, and the gaseous
anion. It is often used interchangeable with electron gain enthalpy, which is the change in
standard molar enthalpy when an atom or molecule gains an electron. A more positive
electron affinity means that the atom is more stable with the additional electron, while a
more negative electron gain enthalpy is indicative of greater stability.
m. What is the combination of electron affinity and ionization energy
called?
The total effect of electron affinity and ionization energy is known as electronegativity. It is
the overall measure of an atom’s ability to attract electrons to itself when part of a
compound. Fluorine has the highest electronegativity.
To explain electronegativity, theories have been proposed by Mulliken, Allred-Rochow, and
Pauling. Pauling’s theory is used most commonly.
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n. What is polarizability?
It is an atom’s ability to be distorted by an electric field. Basically, it means that regions of a
molecule can take on partial positive, or partial negative charge.
2) Hydrogenic Systems
a. Why do we have to use the hydrogenic system approximation?
Systems involving multiple electrons are much more complex, and they require the use of
quantum mechanics.
b. What is the formula for the energy of a hydrogenic orbital?
En= -13.6(eV)*(Z2/n2)
13.6(eV) is the result of h*c*R, and converting to eV. The negative is a result of the sign
convention of energy levels. R is the Rydberg constant, which = 1.09737x105 cm-1, c is the
speed of light in cm, 2.998x1010 ms-1-, and h is Plank’s constant, 6.626x10-34 Js.
c. What is another way of expressing the energy? Joules, and…
Wavenumbers, which are the inverse of wavelength, expressed as inverse centimeters.
3) Quantum Numbers
a. Define and describe the quantum numbers n, l, ml, ms.
N: The principle quantum number. It defines the energy and size of the orbital.
L: Orbital angular momentum quantum number: it defines the magnitude of the orbital
angular momentum, as well as the angular shape of the orbital. L can have values of 0 to n-1.
Ml: Magnetic Quantum number: Describes the orientation of the angular momentum. Ml can
have values of 0 to +/- l.
Ms: Spin magnetic quantum number: Defines the intrinsic angular momentum of an
electron. Ms can have values of either +1/2 or -1/2.
It can be seen from these definitions that every electron in an atom or molecule will have a
different set of quantum numbers.
b. What is the radial wavefunction?
The radial wavefunction (R(r)), along with the angular wavefunction (spherical harmonic),
gives us the orbitals. With a wavefunction, it is possible to completely characterize a particle.
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The wavefunction does not go to zero at the nucleus, they go to zero at infinity. When
graphed, these produce the characteristic shapes of the orbitals we are used to seeing.
c. What is the radial distribution function?
It is a plot of R2(r)r2 vs the radius. It tells us the probability of finding an electron at a certain
distance from the nucleus. Every orbital has a different radial distribution function, and a
node on the graph is a region of zero probability.
d. What is the Bohr radius?
The Bohr radius is the most probably distance to find the electron in a one proton, one
electron system.
It is: a0= (ε0ђ2)/(πmee2)= 52.9 pico-meters.
e. What orbitals correspond to l=0 through l=4?
L=0=s, l=1=p, l=2=d, l=3=f, l=4=g.
f. What is the building up principle/Hund’s Rules?
When degenerate orbitals are available for occupation, electrons occupy separate orbitals
with parallel spin.
g. What is the Pauli exclusion principle?
No more than two electrons can occupy a single orbital, and to do so, their spins must be
paired.
4) Molecular Geometry
a. Describe Valence Shell Electron Pair Repulsion Theory.
The purpose of VSEPR theory is to predict molecular geometries. The basic assumption to
the theory is that regions of enhanced electron density take positions as far apart as
possible, in order to minimize repulsive forces. The relative repulsive strengths of electron
dense regions are: lone pairs > multiple bonds > single bonds.
b. Be able to predict molecular shapes based on VSEPR theory.

c. Describe valence bond theory.

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Valence bond theory explains chemical bonding by considering the overlap of atomic
orbitals. The wave patterns of atomic orbitals interfere constructively to form a bond. A σ
bond is formed when orbital overlap of atomic orbitals with cylindrical symmetry. A π bond
forms when atomic orbitals overlap side by side, after the formation of a σ bond.
Hybridization is used to explain bonding where the number of equivalent bonds exceeds the
number of valence orbitals.

d. What is the effect of a lone pair on geometry?

A lone pair pushes strongly against all other substituents. It is the strongest steric force
governing the shape of a molecule.
e. Describe Molecular Orbital Theory.
It is an improvement over valence bond theory in that the bonding description extends to all
atoms in a molecule, and handles polyatomic molecules easily. Atomic orbitals combine to
form molecular orbitals, which are delocalized descriptions of electron distribution. MO
theory makes several key assumptions:
1. The orbital approximation: The wavefunction describing all of the electrons of a
molecule can be written as a product of the one electron wavefunctions.
2. Linear Combinations of Atomic Orbitals: the superposition of multiple atomic orbitals of
same type along with weighting coefficients.

Orbitals of the same symmetry can and will mix.

Construction Molecular Orbital Diagrams

Homonuclear Diatomics

1) H2 and H2-like molecules

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The 1s orbitals are of equal energy, so they lie at the same level of the diagram. The
atomic orbitals combine to form one σ orbital which is lower in energy, and one σ*
orbital which is higher in energy.

2) Period 2: Li2 through N2

Since we’re still dealing with diatomics, the energy of the contributing atomic orbitals of
each atom is the same. The 2s orbitals combine to form a bonding 1σg and an
antibonding 1σu, as well as a bonding 2σg, although that MO is mainly 2p in character.
The 2p orbitals combine as follows: the lowest energy orbitals are two degenerate π
orbitals, denoted 1πu. The next lowest is a single 2σg orbital (which has some 2s
character). Next in energy are the antibonding orbitals, 1πg (doubly degenerate), and
2σu.

Remember: to order the molecular orbitals, (Lowest energy) σ, σ, π, σ, π, σ (highest

energy)
3) Period 2: O2, F2, and shit, why not let Ne2 join the party
The only difference between this MO diagram and the preceding one is the relative
energies of the bonding orbitals 1πu and 2σg. They are reversed.
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Remember: to order the molecular orbitals, (lowest energy) σ, σ, σ, π, π, σ (highest

energy)
Heteronuclear Diatomics
1) H-X
For simplicity’s sake, this discussion is restricted to H-(something that bonds through
2p and 2s orbitals). Because we are now working with two different atoms, we need
to take into account the relative energies of the atomic orbitals. In a molecule that is
hydrogen bonded to some other atom, the H1s orbital will always be higher in
energy than the highest energy orbital of the other atom (this is not a universal
truth, but for molecules that actually form, it is a good rule of thumb). The 4 atomic
orbitals of the X atom mix with the 1s of H to give 5 molecular orbitals. From lowest
E to the highest, the order of the orbitals is 1σ, 2σ, 1π (doubly degenerate), and 3σ.
The antibonding 3σ is mostly H in character, while the other 4 are mainly X in
character.
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What is the bonding orbital here? It is the only occupied orbital with contributions
from both hydrogen and fluorine.
2) X-Y
To properly construct this diagram, we need to consider the relative energies of the
bonding orbitals of both atoms. The more electronegative the atom, the lower in
energy its orbitals will be. So for both the p, and s orbitals, Li > Be > B > C > N > O > F.
The relative energies of the MO’s are: 4σ > 2π > 3σ > 1π > 2σ > 1σ.

Polyatomics
In order to construct a MO diagram for a polyatomic, we have to use one of the
approximations of MO theory. Linear Combinations of Atomic Orbitals (LCAO’s)
create a cumulative approximation of the atomic orbitals of its constituent atoms.
The notation for LCAO’s is as follows: a, b= non-degenerate, e = doubly degenerate, t
= triply degenerate. To determine what orbitals will mix with what, compare the
energies. To determine how to set up the LCAO, just remember that a is lowest in
energy, then e, then finally t. For example, 3 H1s orbitals in NH3 combine to form
LCAO’s of 1a, and 2e’s. They don’t form 1 set of t LCAO’s because that is not the
order in which the orbitals are filled.
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f. What is bond order, and how is it calculated?

Bond order is a method to assessing overall bond strength between two atoms in a
molecule. It directly assesses the net number of bonds between them. The higher the bond
order, the stronger the bond.
B=1/2(n-n*) n= # electrons in bonding orbital, n*= # electrons in antibonding orbital
g. Know how to assign bonding character (bonding, nonbonding, and
antibonding).
A bonding orbital will lie lower in energy than its substituent atomic orbitals. An antibonding
orbital will lie higher in energy than its substituent atomic orbitals. A nonbonding orbital will
equal in energy to its corresponding atomic orbitals.
h. Know the significance of HOMO/LUMO interactions.
HOMO: highest occupied molecular orbital. It is where the highest energy electrons reside.
LUMO: lowest unoccupied molecular orbital. It is the energy level directly above the HOMO.
HOMO/LUMO interactions are critical to electronic structure. When an excited state is
formed, an electron is promoted from the HOMO to the LUMO. The bonding and
antibonding characteristics of the frontier orbitals are of great importance to the stability of
the molecule. Basically, whereas in neutral atoms we treat valence shell electrons as the
point of interaction, the frontier orbitals are the point of interaction and basis of
understanding for molecular interactions.
i. How is paramagnetism identified through a MO diagram?
If there are two unpaired electrons, the species is paramagnetic.
5) Solids
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a. Define the following:

1. Metallic bonding: the bonding and ordering of metals into pure solids, or solid
solutions, viewed as enormous molecules with continually overlapping atomic orbitals.
2. Ionic bonding: ions of different elements held together in rigid, symmetrical arrays
as a result of attraction between their opposite charges.
3. Lattice: A 3D infinite array of (lattice) points which define the repeating structure of a
crystal.
4. Unit Cell: an imaginary, parallel sided region from which the entire crystal can be
built, such that it fits perfectly together, giving rise to a crystal system. There are 7 types
of crystal systems: cubic, tetragonal, orthorhombic (3 different length dimensions,
identical angles), monoclinic (3 different dimensions, defining angle between two sides),
triclinic (3 different dimensions, 3 different angles), rhombohedral (all 3 sides the same
length, all angles are equal and non-90), and hexagonal.
5. Primitive unit cell: Contains only one lattice point.
6. Body Centered: two lattice points per unit cell.
7. Face Centered: Four lattice points per unit cell.
8. Body Centered Cubic: 3D version of (6)
9. Close Packed: Structure type with the least unfilled space.
10. Coordination number: The number of nearest neighbors. It is the number of
other spheres that a single sphere is touching in its unit cell.
11. Cubic close-packed: ABCABC repeating layers of spheres. (ABAB results in
hexagonally close packed).
12. Face-centered cubic: The same thing as cubic close packed.
13. Hole: Unoccupied space between spheres. Holes can be octahedral, where they lie
between two triangles, and form a hexagon. They can also be tetrahedral, where it is
formed by a planar triangle of touching spheres.
14. Polymorphism: The ability of a metal to adopt different crystal structures based on
the temperature and pressure.
15. Alloy: A blend of different metals. More formally called a solid solution.
16. Substitutional solid solution: When solute metal atoms take up the positions of
solvent metal atoms in the crystal structure.
17. Interstitial solid solution: When the solute metal atoms take up positions in the
holes (interstices) of the solvent crystal structure.
18. Lattice Enthalpy: The standard enthalpy change of accompanying the formation of
a gas of ions from a solid. It is a measure of the strength of the solid.
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19. Born-Haber Cycle: A type of flow chart used to determine lattice enthalpies and
other parameters governing how a solid behaves.
20. Van der Waals interaction: Non-electrostatic contributions to the lattice
enthalpy. The London Dispersion interaction is the most dominant van der Waals
interaction. It is the transient fluctuations in electron density that result in temporary,
induced dipoles.
21. Non-stoichiometric compound: A substance that exhibits variable
composition, but retains the same structure type.
22. Conductor: A substance with an electric conductivity that decreases as temperature
is increased.
23. Semi-Conductor: A substance with an electric conductivity that increases as
temperature is increased.
24. Insulator: Negligible conduction, but if it is possible to measure, it increases with
temperature.
25. Super-Conductor: have zero electrical resistance below a critical temperature.
26. Band: A near continuous array of energy levels, due to the large number of
symmetrically oriented atomic orbitals in a solid with very similar energy levels.
27. Band Gap: A separation of bands, due to there being no energy value for the
molecular orbital.
28. s/p band: The bands built from s and p orbitals.
29. Fermi level: The highest occupied energy level in a solid at T=0.
b. What are the parameters for a substitutional solid solution?
1) The atomic radii of the elements are with about 15% of each other.
2) The crystal structures of the two pure metals are the same. This indicates that the
directional forces between the two atom types are compatible with each other.
3) The electropositive characteristics of both compounds are similar. Otherwise, electron
transfer would be likely.
c. What are the parameters for an interstitial solid solution?
Interstitial solid solutions usually form between metals and small atoms (group 2). In order
for the compound to form, the small atom must not transfer electrons, or an ionic species
would result. For the small atom to fit in the hole, its radius must be close to 0.414x(radius
metal). Interstitial compounds can have a recognizable molecular formula, or they can form
non-stoichiometric compounds.
d. Describe how to write a Born-Haber cycle, and give an example.
Starting from the solid of interest, of form MX(s):
1. Standard molar enthalpy of decomposition, ΔdH0 (the negative of the standard molar
enthalpy of formation, ΔfH0).
MX(s) -> M(s) + X(s, l, g) (elements are now in their reference states)
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2. Standard molar enthalpy of atomization for a solid, ΔatomH0 is the same thing as
sublimation
M(s) -> M(g), ΔatomH0
3. Standard molar enthalpy of atomization for an element is the same thing as the standard
enthalpy of dissociation, ΔdisH0
X2(g) -> 2X(g), ΔdisH0
4. The standard molar enthalpy of formation of ions from neutral atoms is the enthalpy of
ionization (cations) and election gain enthalpy (anions).
M(g) -> M+(g) + e-, ΔionH0
X(g) + e- -> X-(g), ΔegH0
For a complete cycle, the total change in enthalpy will be zero. ΔdH0, ΔatomH0, ΔdisH0, and
ΔionH0 are all positive, and ΔegH0 is negative. The value required to make this equal zero is
the value for the lattice enthalpy, ΔHL0, and it will be negative.

e. What is the most stabilizing influence on a solid? Set up a proportion to

show how it changes along with the values, and relate this to different
types of systems.
Lattice enthalpy is the most stabilizing influence on a solid.
ΔHL0 ≈ q1q2/d, if the charge is high and distance small, lattice enthalpy is very strongly
stabilizing. If the charge is small and the distance is great, the solid is not especially stable.
ΔHL0 values are at their highest when the solid is tightly packed, and the ions are charge
dense.
f. Discuss the importance of the Born-Mayer equation.
The Born-Mayer equation allows us to estimate the lattice enthalpy from charge and
separation, at T=0.

( ) ( ( ))×𝐴
23 2 2 *
ΔHL0= (
6.022×10 )× (𝑞1𝑞2) ×𝑒 𝑑
4πϵ𝑑
× 1− 𝑑

Where d is the distance between neighboring cations and anions, d* is a constant, A is the
Madelung constant, and ε is the permittivity.
g. Why does solubility depend on lattice enthalpy?
Solubility can be described as a product of lattice enthalpy and hydration enthalpy. Since
lattice enthalpy is the energy required to break apart an ionic solid, it is logical to conclude
that solubility will depend on that value. It can be put concisely that if there is a large
difference between ionic sizes, the compound is likely to be soluble in water. This is because
of the ways in which lattice enthalpy and hydration enthalpy depend on the radius.
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1
ΔHL0 ∝ 𝑟+𝑟

ΔhydH ∝ (1/r+) + (1/r-)

This means that as the difference in ionic size increases, the lattice enthalpy decreases, while
the hydration enthalpy increases.
Separation of the ions in solution is also entropically favored, given that the hydration
enthalpy for one is greater than the other.
h. What is solvent levelling?
Solvent levelling is the ordering of water molecules around a dissolved ion. The more charge
dense an ion is, the more it orders the water. This is entropically unfavorable, so it acts
against processes that seek to break apart ions in solution.
Considering the discussion in the previous section, this demonstrates that when considering
enthalpy, entropy can’t be ignored. While solubility is proportional to the lattice and
hydration enthalpies, it is also proportional to the overall enthalpy AND entropy. The
entropic effects of solvent levelling push back against the favorable hydration enthalpy.
i. Discuss band theory, including the consequences for conductors and
insulators.
The best way to describe band theory is to immediately draw analogies to molecular orbital
theory. In MO theory, the molecular orbitals formed by the constituent atomic orbitals
reside at different energy levels; have specific orientations, and a degree of overlap. The
combination of all of these factors leads to the characterization of MO’s as bonding,
nonbonding, or antibonding, separated by the previously mentioned energy levels. In band
theory, instead of the orbitals of just a few atoms overlapping, there is a near continuum of
overlapping orbitals. The lowest energy orbitals have no nodes between neighboring atoms,
whereas the highest energy orbitals have a node between every pair of neighbors. Because
of the near continuum of MO’s, the energy separation between neighboring orbitals
approaches zero, creating a near continuous energy spectrum.
The s-band forms between s orbitals, the p-band between p orbitals, etc…
There may be a gap (band gap) between orbital bands, or they may overlap.
Conductors have partially filled bands at low energy levels, so electrons are promoted easily.
Vigorous vibrations, such as those due to thermal energy, disrupt the band structure, and
decrease conductivity.
Insulators have filled bands with a large energy differential separating them. The filled band
is called the valence band, and the next higher band is called the conduction band.
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j. What are the different types of semiconductors? Thoroughly describe.

1) Intrinsic Semiconductors: like insulators, they have a filled s-band and empty p-band,
but the energy gap is very small. This makes it so that electrons can be promoted by
thermal energy. The promotion of electrons results in positive holes in the valence band,
amounting to a charge separation, which allows current to flow. The population of the
conduction band shows an Arrhenius-like dependence on temperature.
2) Extrinsic Semiconductors: A material gains the ability to be a semiconductor because of
intentionally added impurities (dopants), which increase the number of electron
carriers.
a. N-type: the N meaning negative, the dopant supplies additional electrons to the
solid structure. These electrons lie above the valence band in energy, and close to
the conduction band, so the gap is much easier to jump, thanks to the donor band.
b. P-type: The P means positive, the dopant material has less valence electrons than
the parent material. The holes it creates lie just above the valence band in energy, so
electrons can jump to the acceptor band to allow current to flow.

k. What conditions are needed for electrons to flow through a solid?

A small energy difference and unfilled orbitals
6) Acids and Bases
a. Define a Lewis acid/base.
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A Lewis acid is an electron pair acceptor, and a Lewis base is an electron pair donor.
b. Define a Bronsted-Lowry acid/base.
A Bronsted acid is a proton donor, and a Bronsted base is a proton acceptor. Obviously, this
theory focuses on proton transfer as the source of acidity.
c. Define hard/soft acid/base theory (HSAB).
Hard acids bond in order of: I- < Br- < Cl- < F-
Soft acids bond in order of: F- < Cl- < Br- < I-
Soft acids/bases are larger and more polarizable. Hard acids/bases are small and charge
dense.
Hard will tend to bond to hard, soft tends to bond to soft.
d. How does covalence apply to HSAB?
Use these as a rule of thumb, not a law.
1. For a given cation, covalence increases as the size of the anion increases.
2. For a given anion, covalence increases as the size of the cation decreases.
3. Covalence increases as charge increases.
4. Covalence is larger for non-noble configurations.
e. What contributes to the Gibb’s energy of complex formation, other
than the type of bond formed?
1. Competition with solvent
2. The rearrangement of the substituents of the acid and base that may be necessary to
permit formation of the complex.
3. Steric repulsion between substituents on the acid and base.
f. What are the criteria for categorization of HSAB?
Other than what was stated in part (c), there are no definite criteria. It is based on
experimentally determined evidence, usually to do with complex formation.
g. What is an amphiprotic substance?
It is a molecule that can act as both a Bronsted acid and base.
h. What is the relationship between a strong acid and its conjugate base?
A strong acid will have a weak conjugate base. A strong base will have a weak conjugate acid.
A strong acid seeks to remain deprotonated, while a strong base seeks to remain
protonated.
i. Write the expression for the acidity constant (Ka) for a Bronsted acid.
Discuss the range of experimentally observed Ka values and what they
mean.
Ka=([A-][H3O+])/[HA]
The strongest (aqueous) acid out there is hydroiodic acid, with a Ka on the order of 1011. This
means that once introduced to solution, HI immediately and completely converts to I- and
H3O+ (well, except for 1 molecule in every 1011). Some very weak acids have Ka on the order
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of 10-15. Just about no molecules lose a proton with a Ka that small. Most acids fall
somewhere between 10-5 and 101, such that they establish an actual equilibrium.
j. What is autoprotolysis? Why does this make some calculations much,
much easier?
It is the proton transfer from one water molecule to another. This establishes a constant
equilibrium, even in neutral water, between hydronium and hydroxyl ions.
This comes in handy in calculations, because we can set up the expression Kw=[H3O+][OH-].
Kw= 1.0x10-14 (at 25o C), and we can define Ka and Kb in terms of Kw, allowing us to easily
convert between the two. KaKb=Kw
k. Discuss proton affinity and proton gain enthalpy.
Proton affinity (AP) and proton gain enthalpy (ΔpgH0) relate acidity to enthalpy changes
during a proton transfer. Proton gain enthalpy is reported as a positive number, and the
proton affinity is the negative of it. A high AP indicates strong basicity, if only slightly
negative, it is only weakly basic or possibly acidic.
Proton gain can be described by these 3 steps:
1. Electron loss from A-: A-(g) → A(g) + e- - ΔegH0(A) = Ae(A)
The reverse of electron gain by A
2. Electron gain by H+: H+(g) + e- → H(g) - ΔiH0(H) = -I(H)
The reverse of ionization of H
3. Combination of H and A: H(g) + A(g) → HA(g) -B(H-A)
The reverse of H-A bond dissociation

The proton gain enthalpy is the sum of the preceding enthalpy changes:

ΔpgH0(A-) = Ae(A) – I(H) – B(H-A), AP(A-) = B(H-A) + I(H) – Ae(A)

l. What is the dominant factor in determining acid character?

Electron affinity is the dominant factor. Electron affinity and proton affinity are inversely
related, so observing the trend of Ae increasing from left to right, the proton affinity
increases right to left. As proton affinity decreases, acidity increases, so Ae and stronger acid
character have a positive, direct correlation. A higher Ae corresponds to a more stable
conjugate base.
m. Construct a Born plot for the thermodynamic cycle for a general proton
gain reaction.
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n. Discuss solvent levelling.

Solvent levelling in water is the fact that any strong acid or strong base in aqueous solution is
only as strong of an acid as H3O+ or as strong of a base as OH-. The relative strengths of
strong acids can be measured by using an anhydrous weak acid as the solvent. The same
idea can be applied to bases.
o. What are the equations for Ka and Kb when considering the solvent
levelling effect of water?
Ka=[H2Sol][A-]/[HA]
Kb= [HB+][Sol-]/[B]
p. How is the Bronsted definition of acids and bases extended by the
solvent system definition?
The Bronsted definition is only concerned with proton transfer. The solvent system definition
defines an acid as any solute that increases the concentration of the cation generated by
auto ionization of the solvent. It defines a base as anything that increases the concentration
of the anion generated by the auto ionization of the solvent.
q. Define and discuss aqua acids.
The acidic proton is on a water molecule coordinated to the central metal ion.
Acid strength increases as the covalent character of the M-O(H2) bond increases. Across the
periodic table, covalence increases left to right, and top to bottom. Generally, the heavier
the metal, the stronger the acid will be.

r. Define and discuss hydroxoacids.

The acidic proton is from a hydroxyl group coordinated to a central metal ion, but without a
neighboring oxo- group.
s. Define and discuss oxo-acids.
The acidic proton is from a hydroxyl group coordinated to a central metal ion, with an oxo-
group adjacent to it. The stability of the conjugate base is the primary factor in determining
acid strength. The conjugate base’s stability is determined by resonance, polarizability, and
charge density. A rough formula to estimate the pKa is 8 – 5(# of oxo groups).
Page 18 of 43

A few more generalized points about oxo-acids

Non-metals form acidic oxides, due to electronegativity
Metals form basic oxides
Going down a group, atoms are bigger, polarizes water better, and higher hydration enthalpy
and entropy
Amphoteric compounds form weak acids and weak bases. One member of group 2 and
several toward the bottom of groups 13, 14, and 15 are amphoteric (Beryllium, aluminum,
gallium, indium, germanium, tin, lead, arsenic, antimony, and bismuth).
Bases donate electron density
Hard/soft, soft/hard makes the conjugate less stable by making it more soluble
t. What are some types of non-aqueous solvents?
Liquid ammonia, hydrogen fluoride, anhydrous sulfuric acid, dinitrogen tetroxide
u. Discuss the Lewis acidity of the different columns of the periodic table.
Alkali metals act as Lewis acids with water, forming hydrated ions.
Group 13: Boron tri-halides act as Lewis acids. Acid strength increases with atomic mass of
the halogen. Aluminum halides form dimers in the gas phase, and are used as Lewis acid
catalysts.
Group 14: Except carbon, group 14 elements exhibit hypervalence and act as Lewis acids,
tin(II) chloride acts as both a Lewis acid and base.
Group 15: Oxides and halides of the heavier elements act as Lewis acids.
Group 16: Sulfur dioxide can act as a Lewis base when it forms a complex with a
trialkylamine that acts as a Lewis base. Sulfur trioxide is a strong Lewis acid.
Halogens: Bromine and Iodine act as mild Lewis acids.
v. What’s the difference between hard-hard and soft-soft interactions?
Hard preferentially bonds to hard, soft preferentially bonds to soft. H-H and S-S are more
thermodynamically stable than H-S or S-H.
Soft-soft is more covalent in character, whereas hard-hard is more ionic in character.
Factors influencing the Gibb’s energy of complex formation:
1. Competition with solvent
2. Rearrangement of the substituents of the acid and base that may be necessary to permit
formation of the complex
3. Steric repulsion between substituents on the acid and the base

Soft acid/soft base interactions tend to be exothermic.

7) Redox
a. Define reduction, oxidation, reducing agent, and oxidizing agent.
Reduction: The gain of electrons
Oxidation: The loss of electrons
Reducing agent: the species which supplies the electrons (it is oxidized)
Oxidizing agent: the species which receives the electrons (it is reduced)
Page 19 of 43

Together, they make the redox couple.

b. What is the significance of oxidation numbers?
Oxidation are not tangible, or observable, they are merely a bookkeeping method. They are
used to describe the ionic state of an atom.
c. Why do we write half reactions to express reduction potentials?
Because of the fact that in a redox reaction we are following the movement of electrons,
breaking a reaction up into half reactions to separate reduction and oxidation gives us a
clear view on the electron transfer, and simplifies balancing a reaction. When written as a
complete reaction, the electrons cancel out, and are not written. Remember that all half
reactions are written as reductions (in data tables, etc…), so the sign on the reduction
potential may need to be reversed.
d. Know how to charge balance a redox reaction.
Example Problem: Balance redox reaction in acid solution: MnO4- + H2SO3 → Mn2+ + HSO4-?
MnO4-(aq) + H2SO3(aq) -> Mn2+(aq) + HSO4-(aq)
First, separate it into half reactions
MnO4-(aq) + 5e- + 8H+ -> Mn2+(aq) + 4H2O(l) Eo= +1.51V
*This half reaction was obtained from a Latimer diagram. The Latimer diagram only shows
the species which are present, the oxidation state, and the standard cell potential. You have
to be able to figure out the number of electrons to add, and because the problem specified
that it is in acid, how many H+ to add.
HSO4-(aq) + 2e- + 3H+(aq) -> H2SO3(aq) + H2O(l) Eo= +0.158V
*Same as for the other half reaction, make sure everything adds up
We have to get the number of electrons to equate. They will be on opposite sides of the
reaction when it is written out completely.
Multiply the top by 2, and the bottom by 5
Because HSO4- is the product, we need to reverse the half reaction containing that species.
2MnO4-(aq) + 10e- + 16H+ + 4H2SO4 + 5H2O -> 2Mn2+ + 8H2O + 5HSO4 + 10e- + 15H+
1H+ 3H2O
Final balanced equation: 2MnO4-(aq) + H+(aq) + H2SO3(aq) -> 2Mn2+(aq)+3H2O(l)+5HSO4-(aq)

e. Why is the electrochemical series so hard to predict?

It is difficult to predict because it involves a number of thermochemical cycles, including
heat of sublimation, ionization energy, standard enthalpy of hydration (for the metal and H),
bond dissociation energy, and the overall reaction enthalpy.
f. What is the effect of multiplying a half reaction?
Multiplying the reaction does not change the potential, but it does change the free energy.
g. What values of K and Eᶲ indicate a spontaneous reaction?
If Eo > 0, then K>1, and it is thermodynamically favorable (spontaneous).
Page 20 of 43

h. Define anode, cathode, and galvanic cell.

Anode: the site of oxidation
Cathode: the site of reduction
Galvanic cell: An electrochemical cell in which a reaction drives an electric current, which
travels through an external circuit for measurements.
i. Write the equation for Gibb’s free energy change involving the
standard cell potential.
ΔGo=-nFEo
F is the Faraday constant, F=9.648x104C/mol
N is the number of electrons
j. What makes something a strong oxidizing agent? A strong reducing
agent?
When considering a redox couple, the oxidized member is a strong oxidizing agent if Eo is
large and positive. The reduced member is a strong reducing agent if Eo is large and negative.
If the standard potential is negative (Eo<0), the reduced species of the redox couple is a
reducing agent for H+ under standard conditions.
k. Write and discuss the Nernst equation.
The Nernst equation gives the cell potential at any composition.
It gives the ΔrG value, not just the ΔGo value.
ΔrG= ΔrGo + RT(lnQ) Q=[redox products]/[redox reactants]
o
-nFE=-nFE + RT(lnQ)
E=Eo – (RT/nF)(lnQ) at equilibrium, E=0 and Q=K
The pH dependent version: E=Eo-((0.0059xnH)/ne-)xpH, as the pH increases E decreases, and
vice versa.
l. Under what conditions might a reaction be thermodynamically
favorable, but kinetically slow?
If Eo>0, it is spontaneous, but if it requires the movement of multiple electrons
simultaneously, it will be slow.
m. Discuss the pH dependence of redox reactions.
As the pH increases, E decreases. As the pH decreases, E increases. This is due to the fact
that many redox reactions require H+ ions, and a greater abundance of them increases the
amount of current that can be transferred.
n. What is a passivating layer? Why is it used?
A passivating layer is a kind of ‘skin’ of a metal oxide that forms over a metal’s surface, which
protects the metal from reacting further. This layer forms when the metal begins to react
with water or acid, and sticks to it, in effect encapsulating it. It is not necessarily used but
utilized so that the metal (particularly magnesium and aluminum), will not corrode in open
air.
o. What conditions will make water an oxidizing agent?
Page 21 of 43

This will happen spontaneously if the metal is from the s-block, group 3 to group 9, or a
lanthanoid. If the standard reduction potential for a metal is negative, it will be oxidized by
1M acid. H2 forms as the reaction progresses.
p. What conditions will make water a reducing agent?
If the standard reduction potential for a redox couple is +1.23V or greater, they can oxidize
water. Because H+ is produced in the reaction, a higher pH encourages formation of the
products (the couple of interest here is O2, H+/H2O).
These types of reactions, though spontaneous, are kinetically very slow because of the
number of electrons which need to be moved.
q. Be able to interpret a graph of the stability field of water.
The stability field of water is the range of values of potential for which water is
thermodynamically stable toward both oxidation and reduction.

As seen from the chart, natural waters are stable between pH4 and pH9, between the redox
potentials of H+/H2 and O2/H2O.
r. Under what conditions will water be unstable?
It will be unstable outside of the boundaries previously stated.
s. Define disproportionation and comproportionation.
Disproportionation: the oxidation number of an element is simultaneously raised and
lowered, such that a species at a certain oxidation state is converted to a species that is
more oxidized, and a species that is reduced. In a Latimer diagram, if the potential on the
right is higher than the potential on the left, it will tend to disproportionate.
Comproportionation: the reverse of disproportionation, two species of the same element in
different oxidation states will form a common product of the same oxidation state. In a
Latimer diagram, if the potential on the left is higher than that on the right, it will tend to
comproportionate.
t. How would I use the standard cell potential to determine the solubility
product?
If an aqueous metal ion and its precipitate are in equilibrium, the solubility product (Ksp) can
be determined by the reduction potentials for the half reaction that returns the metal to its
neutral state, both as an individual ion and as the precipitate.
Mn+ + ne- -> M
Page 22 of 43

Ln(Ksp)= (nF(Eo(MX/M,X-) – Eo(Mn+/M)))/RT

u. Provide an example of, and then discuss how to use, a Latimer
diagram.
Latimer diagrams are a type of flow chart that are used to follow the oxidation and reduction
of a particular element or compound.

As seen here (and in 7d), a Latimer diagram can be used to quickly determine the number of
electrons transferred in redox reaction, and it gives the standard potentials associated with
them.
8) Molecular Symmetry
a. Define the symmetry operators, E, Cn, σ, I, Sn
E: The identity operator. It’s always there.
Cn: Rotation by 360o/n. If n=2, there is only one rotation operation involved. If n=3, there are
two operations associated with it, C3 and C3’. There will always be n-1 rotational operations
involved, only considering that axis. The principal axis is the highest order rotational axis,
and it defines the z-axis of the molecule.
σ: Mirror plane. A mirror plane is a vertical mirror plane, σv, if it contains the z-axis, as
defined by rotational symmetry. The horizontal mirror plane, σh, is in the plane of the
molecule, or alternatively, perpendicular to σv. There can also be a dihedral mirror plane, σd,
which bisects two C2 axes.
I: Center of Inversion. The inversion operation has each atom of the molecule projected
through a single point, and out the same distance on the other side, succeeding to
interchange diametrically opposite pairs. Only Oh, D ∞h, , D4h, D2h, and Ci point groups have
the inversion operator.
Sn: Improper rotation/Screw axis. This operation consists of a rotation through a certain
angle followed by a reflection in a mirror plane perpendicular to the rotation.
Page 23 of 43

b. Know how to assign a point group. Give written out procedures for the
flow chart.
The procedure to assign a point group is to first identify all of the symmetry elements. The
standard procedure is to then consult the flow chart, or table.
However, since that is not allowed for the exam:
1. Is it linear? If yes, there are only two options. If it has a center of inversion it is D∞v, if it
does not, it is C∞v.
2. If it is not linear, then we first consult the rotational symmetry elements.
If it has two or more unique Cn axes with n>2, given the axes are not collinear, it is Td, Oh,
or Ih. If it does not have a center of inversion, it is Td. If it does have a center of inversion
and a C5 axis it is Ih. If it does not have a C5 axis it is Oh.
3. If it does not have two unique C axes that are not colinear, does it have rotational
symmetry? If yes, then…
a. Is the principal axis perpendicular to the C2 axes? If it is, it is Dnh, Dnd, or Dn. If it has
σh symmetry, it is Dnh. If no, consult, σd. If it has σd symmetry, it is Dnd, if not, it is Dn.
b. If the C axes are not perpendicular, it is either Cn, S2n, Cnv, or Cnh. To determine the
point group, consult the σh symmetry element. If it does have a horizontal mirror
plane, it is Cnh. If there is no horizontal mirror plane, if it has a vertical mirror plane it
is Cnv. If it has a screw axis it is S2n. If it is does not, it is Cn.
4. If there is no rotational symmetry, it is Cs, Ci, or C1. Does it have a mirror plane? If yes, it
is Cs if no, does it have a center of inversion? If yes, it is Ci, if no, it is C1.
c. Which groups are high symmetry? Low symmetry?
The high symmetry groups are D∞v, C∞v, Ih, Oh, Td. The low symmetry groups are Cs, Ci, C1.
d. Explain how to use a character table.
There is a character table corresponding to every point group. The table contains all of the
symmetry species (Γ) and all of the symmetry operators. In the table are values
corresponding to how they transform under the operations.

This is the character table for the C4v point group. The numerical elements in the body of the
table are the characters, χ, and these are what tell us how the symmetry species transform
under the operation. A value of 1 means it is unchanged, a value of -1 means it changes sign,
Page 24 of 43

0 means it undergoes a more complicated change (higher math, and such). The letters in the
column directly to the right of the main body are translations, rotations, and components of
dipole moments (s and p orbitals) which are relevant to IR activity. In the column to the right
of those are the quadratic functions (d orbitals) which are of relevance to Raman activity.
The letter A in the symmetry species column means that it is symmetric with respect to
rotation about the principal axis. B means that it is inverted with respect to rotation about
the principal axis. If it is labeled A1, then it is symmetric with respect to all symmetry
operators. The subscript one means that it is symmetric with respect to reflection in the
principal vertical plane, the subscript two means it is inverted with respect to reflection in
the principal vertical plane. If the letter E is used for a symmetry species, it is a degenerate
species, and the number of degenerate orbitals is given under the identity operator.
e. What is an irreducible representation?
An irreducible representation is the row of characters for the given symmetry species.
f. How is symmetry used to identify a polar molecule?
A polar molecule is one which has a permanent electric dipole moment. In terms of
symmetry, there are 3 rules to follow to assign polarity:
1. A molecule cannot be polar if it has a center of inversion (Oh, D ∞h, , D4h, D2h, and Ci)
2. A molecule cannot have an electric dipole moment perpendicular to any mirror plane.
3. A molecule cannot have an electric dipole moment perpendicular to any axis of rotation
g. How is symmetry used to identify a chiral molecule?
A molecule cannot be chiral if it has an improper rotation axis, or a mirror plane.
h. What is the relationship between degrees of freedom and the
character tables?
For a molecule of N atoms, there are 3N degrees of freedom. 3 are translational, 3 are
rotational, so 3N-6 vibrational modes (if non-linear). If it is linear, there is no rotation about
the axis of the molecule, so there are 3N-5 vibrational modes in a linear molecule.
The symmetry species of the vibration must be the same as that of x, y, or z in the character
table for the vibration to be IR active, and the same as that of a quadratic function, such as
xy or x2, for it to be Raman active.
i. What is a SALC?
A SALC is a symmetry adapted linear combination of atomic orbitals. These are analogous to
LCAO’s encountered earlier. These are atomic orbitals which can be combined to a single
symmetry type in order to construct a MO diagram.
j. How is a SALC used to construct a MO diagram?
A SALC is matched with an atomic orbital of the same symmetry. Here is the procedure:
1. Assign a point group to the molecule
2. Look up the shape of the SALCs in a data table
3. Arrange the SALCs of each molecular fragment in increasing order of energy, while
noting whether they stem from s, p, or d orbitals.
Page 25 of 43

4. Combine SALCs of the same symmetry type from the two fragments, and from N SALCs
from N molecular orbitals.
5. Estimate the relative energies of the molecular orbitals from considerations of overlap
and relative energies of the parent orbitals, and draw the levels on a molecular orbital
energy level diagram
6. Confirm, correct, and revise this qualitative order by carrying out a molecular orbital
calculation (if applicable)
k. How is an irreducible representation used to identify Raman and IR
stretches?
If a molecule has a center of inversion, none of its modes can be both IR and Raman active. A
vibrational mode is IR active if it has the same symmetry as a component of the electric
dipole moment (x,y,z and rotations). A vibrational mode is Roman active if it has the same
symmetry as a component of the molecular polarizability (the quadratic functions).
l. How do you reduce a representation?
A reducible representation is one which is obtained by considering the displacements of the
atoms under all of the symmetry operations of a point group. The numbers we are left with
often don’t correspond to any one symmetry species, but are combinations of multiple. To
determine which symmetry species are present the analysis can be done visually, by adding
different irreducible representations together, through trial and error. Or, multiply the
reducible representation by the class number and then by each symmetry species’
irreducible representation, add them all together for each Γ, and divide by the order. This
gives the number of times that symmetry species appears in the irreducible representation
under the transformation being considered.

9) Coordination Compounds
a. What is the system for nomenclature of coordination compounds?
To write a formula, the cation is listed first, followed by the anion. Ligands are then listed in
alphabetical order.
To name the compounds, first the ligands are listed in alphabetical order (preceded by
mono, bi, tri, etc…), then followed by the metal and its charge. If a ligand acts as a bridge
between two metal centers, it is preceded by the Greek letter μ.
b. What are mono-, bi-, tri-dentate, etc… ligands? How do you identify
them?
1. Mono: One point of attachment
2. Bi: Two points of attachment
3. Tri: Three points of attachment
The atoms which bind to the central metal typically have lone pairs, or carry a negative
charge. It is important to note that carbon is rarely the site of attachment.
Page 26 of 43

c. What is an ambidentate ligand? How do you identify an ambidentate

ligand?
An ambidentate ligand is one which has multiple donor atoms, but only binds through one.
Ambidentate ligands typically carry a negative charge, and are resonance stabilized.
d. What is a chelate?
A chelate is the term for a complex which forms when a polydentate ligand binds to a metal
with more than one of its donor atoms. They tend to bind at adjacent sites in a cis
configuration.
e. In the terms of coordination chemistry, what is an acid and what is a
base?
The metal ion is Lewis acid (electron pair acceptor), and the ligand is a Lewis base (electron
pair donor).
f. What are the factors governing the coordination number of a complex?
1. The size of the central atom or ion. Larger atomic radii correlate to higher coordination
numbers. Remember that radii increase down a group and to the left.
2. The steric interactions between the ligands.
3. Electronic interactions between the central atom/ion and ligands
g. What group on the periodic table is known to form 2 coordinate
complexes?
Members of group 11 are by far the most common to form 2 coordinate complexes.
h. What is the favored symmetry and point group for four coordinate
complexes? Five coordinate? Six coordinate?
1. Four: Tetrahedral is the most common configuration, occurring with a small cation and
large ligands. If the ligands are all the same, the point group is Td. If the central metal ion
has a d8 configuration, it will tend to adopt a square planar configuration, and have D4h
symmetry if the ligands are all the same.
2. Five: Five coordination is uncommon, but if it happens it will be square pyramidal (C4v
with identical ligands) or trigonal bipyramidal (D3h with identical ligands). Steric
distortions are common, and deviations from the ideal geometries happen frequently.
3. Six: Six coordinate are almost always octahedral, with the point group Oh.
i. For what atoms/ions will we observe high coordination numbers?
High coordination occurs most frequently for members of the f block.
j. What are the four types of isomers?
1. Linkage isomers: these form only with ambidentate ligands, and are the result of the
different donor atom binding.
2. Ionization isomers: these occur when a ligand and a counter-ion (dissolved in solution)
exchange places.
Page 27 of 43

3. Hydrate isomers: occur when water trades places with a ligand.

4. Coordination isomers: occur when two different complex ions can have the same
molecular formula, through different bonding orders.
k. What are meridional and facial isomers?
They occur only for 6 coordinate complexes with octahedral geometry, and only for those
with the general formula MA3B3. Meridional isomers have one set of ligands around the
metal ion’s meridian, and the other set along the meridian perpendicular to the other.
Facial isomers are best visualized by putting all 3 of one ligand into a triangle, and the other
3 into a diametrically opposite triangle.

l. What isomers are observed for four, five, and six coordinate
complexes?
For four coordinate square planar complexes, only cis/trans isomers occur. For four
coordinate tetrahedral, enantiomers are the only isomers. For five coordinate complexes,
just don’t even worry about it. For six coordinate complexes, cis/trans is one possibility, as
well as facial and meridional, which were discussed in the previous section.
m. What is a formation constant, and how is it determined?
It is an equilibrium constant, denoted Kf, and is a measure of the strength of ligand binding
relative to water. If it is large, it binds the incoming ligand well.
The formula is: Kf=[MLn]/[M][L]
Stepwise formation constants are those that represent successive ligand binding.
n. What is the trend of stepwise formation constants? What causes them
to deviate?
They tend to decrease with the addition of each successive ligand. If a Kf(n+1) is greater than
Kfn, it is indicative of a change in coordination, showing that the complex is more stable at a
lower coordination number than for the previous set of ligands.
o. What is the chelate effect?
A complex with chelating ligands is more stable than one with non-chelating ligands, as
observed by formation constants.
10) Tanabe-Sugano diagrams
Page 28 of 43

a. What does the diagram depict?

The Tanabe-Sugano diagrams depict the energies of electronic states of complexes as a
function of the ligand field strength. More specifically, it shows terms splitting into different
microstates.
b. How are the term energies expressed on the axes?
The term energies, E, are expressed as E/B and are plotted against Δo/B, where in both cases
B is the Racah parameter.
c. What does a curved line mean?
A curved line is the result of mixing of orbitals due to same symmetry.
d. What is the non-crossing rule?
If the increasing ligand field causes two weak field terms to approach, they bend apart rather
than cross.
e. What is the name of the term of lowest energy? Where is it on the
graph?
The term of lowest energy is the ground term, and it is the X axis of the graph.
f. By analyzing the graph, what can we determine? How do we do this?
They allow us to determine the ligand field splitting parameter, Δ. The Tanabe-Sugano
diagrams are constructed from electronic absorbance spectra of complexes with more than
one d electron, while taking into account electron-electron repulsions. To do this, we fit the
observed transitions to the correlation lines, and identify the values of Δo and B where the
observed transition energies match the pattern.

g. What spectrum does the graph represent?

It is the electronic absorbance spectrum.
h. What transitions are forbidden?
Transitions which change the spin state are forbidden.
Page 29 of 43

i. What are the Racah parameters?

The energy due to repulsions, and is expressed as a collection of 3 terms, A, B, and C. A is the
average of total inter-electron repulsion. B and C are repulsion energies between individual d
electrons.
11) Term symbols
a. What is a microstate?
Microstates are the different ways in which electrons can occupy orbitals.
b. What is a term?
Terms are spectroscopically distinguishable energy levels of microstates with the same
energy when electron-electron repulsions are considered.
c. How do electron-electron repulsions affect a spectrum?
Electron-electron repulsions result in multiple absorptions. If they are treated as negligible,
then the microstates have the same energy.
d. What energies are spin forbidden?
The lowest energies are spin forbidden.
e. What are, in order, the two most important properties of 3-d series
and light elements?
The most important property is the relative orientation of electron spin, followed by the
relative orientation of orbital angular momenta.
f. Describe S (big S) and L (big L).
S is the total spin quantum number, which comes from the relative orientations of individual
spins.
L is the total orbital angular momentum quantum number, which comes from the relative
orientation of individual orbital angular momenta of each electron.
g. How do we assign values to L?
L can take on values of l1+l2, l1+l2-1… [l1-l2].
h. What is spin-orbit coupling?
It is the relative orientation of spin and angular momenta of each electron.
i. How do we assign values to S?
S can take on values of s1+s2, s1+s2-1, … [s1-s2].
j. What are the ranges of ML and MS?
ML ranges from positive L to negative L, so it encompasses 2L+1.
MS ranges from positive S to negative S, so it encompasses 2S+1.
k. What is Russel-Saunders coupling?
It is used for 3d metals, and is the process of combining electron angular momenta by first
summing spins, then orbital momenta, and then combining the. This procedure is the
combination of Questions 2g through 2j.
Page 30 of 43

l. What is the word for total spin? What is its one letter abbreviation and
how is it determined?
Total spin is called multiplicity, and is abbreviated with P. It is 2S+1.
m. Describe the two steps to using Hund’s Rule to assign energies.
First, identify the microstate with the highest value of MS. This tells us the highest
multiplicity of the configuration.
Next, identify the highest permitted value of ML for the multiplicity. This tells us the highest L
value for the multiplicity.
It is important to note that we are only concerned with the term of lowest energy, which is
what Hund’s rule tells us how to find.
n. How do you identify the ground term in a set of terms?
By using Hund’s rules, which were explained in the previous question.
o. What are the letters corresponding to different values of L? What
orbitals do they represent?
L=0 -> S -> A1g
L=1 -> P -> T1g
L=2 -> D -> T2g, Eg
L=3 -> F -> A2g, T1g, T2g
L=4 -> G -> A1g, Eg, T1g, T2g
They continue in this fashion, but we rarely need to consider anything higher than G.
p. What metals is L considered a very important factor? For what metals
is it not considered important?
L is used primarily for 3d metals, it is not as important of a consideration in 4d and 5d. For
those series, spin orbit coupling is the most important factor in determining the energy.
12) Charge Transfer
a. What are the two types of charge transfers?
Ligand to metal charge transfer (LMCT), and metal to ligand charge transfer (MLCT).
b. What is a charge transfer?
A charge transfer occurs when an electron that is primarily ligand (or metal) in character
migrates to an orbital that is primarily metal (or ligand) in character.
c. What is solvatochromism?
It is variation in the transition frequency with change in the solvent permittivity. This is a
better indicator of a metal/ligand interaction than a ligand-ligand or metal-metal interaction.
d. When do LMCT reactions occur in the visible region?
There are two causes for this. It may be a result of the ligand having high energy lone pairs,
or because the metal has low lying empty orbital.
e. What reduces what?
The ligand reduces the metal ion.
Page 31 of 43

f. Are these transitions localized or delocalized?

These are localized transitions (hence the term charge transfer).
g. What characteristic of the metal atom will give a strong CT band?
A metal ion in a high oxidation state.
h. What characteristic of the complex makes a MLCT likely to occur?
If a complex has ligands with low lying π* orbitals, especially with aromatics, a MLCT is likely
to occur.
i. Describe the relative proximity of ligand and metal orbitals in a MLCT.
The metal d orbitals are low in energy, lying very close to the empty ligand orbitals.
j. What are the most common ligands to result in MLCT?
Diimines are the most common ligands to result in a MLCT.
13) Selection Rules
a. What is Εmax?
It is a measure of the absorption strength for ligand field transitions.
b. What is the approximate Emax for octahedral complexes? Tetrahedral?
Square planar?
For both octahedral (and almost octahedral) and square planar complexes, it is about 100
dm3/mol*cm. Tetrahedral complexes have Emax of about 250 dm3/mol*cm.
c. What is a transition dipole moment?
The transition dipole moment is the impulse of a transition on an electromagnetic field,
which is a measure of the strength of transition.
d. What is the transition dipole moment for an allowed transition?
Forbidden?
The transition dipole moment for an allowed transition is nonzero, whereas forbidden
transitions have a dipole moment of zero.
e. Describe spin allowed transitions in terms of singlet to triplet
transition, and the value of ΔS.
A singlet (s=0) cannot undergo a transition to a triplet (s=1), it is a forbidden transition.
f. What can relax the rules regarding spin transitions?
Spin orbit coupling can relax the spin transition rules, but these transitions are weak,
although they do increase with atomic mass.
g. What are the Laporte selection rules?
Laporte selection rules state that in a centrosymmetric molecule or ion, the only allowed
transitions are those accompanied by a change in parity.
Transitions from g to u terms are allowed, but those from g to g, and u to u are forbidden.
For s and d orbitals, forbidden transitions are s-s, p-p, d-d, f-f, s-d, p-f, while the allowed
transitions are s-p, p-d, d-f.
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h. What can relax the Laporte rules?

The selection rules are relaxed if the complex departs (slightly) from perfect centrosymmetry
in its ground state, or if asymmetric vibrations destroy the centre of inversion.
i. Based on the energies of the transition, classify them as spin and
Laporte allowed or forbidden.
E<1: spin forbidden, Laporte forbidden
E<10: Spin allowed, Laporte forbidden (vibrational motion)
E<100: Spin allowed, Laporte forbidden (static distortion)
E<50000: Spin allowed, Laporte allowed (charge transfer)
14) Crystal and Ligand Field theory
a. What is the ligand field splitting parameter?
It is the energy difference between sets of orbitals of different energy in the same sub shell.
b. What is a barycenter?
It is the energy level corresponding to a spherical distribution of electric charge. For an
octahedral molecule, the two eg orbitals (dx^2-y^2, dz^2), lie at 3/5 Δo above the barycenter,
while the three t2g orbitals (dxy, dyz, dzx) lie 2/5 Δo below the barycenter.
c. What will cause Δo to increase?
It will increase with an increasing oxidation state, and down a group. This corresponds to the
smaller size of more highly charged ions (hard acids and bases), which results in shorter
metal-ligand bond distances.
d. What is the ligand field stabilization energy?
It is the stabilizing energy imparted to a d orbital splitting into eg and t2g orbitals relative to
the barycenter.
e. What is the pairing energy?
It is the coulombic repulsion that results from electrons pairing. Pairing energy is taken into
account only when the pairing of electrons is in addition to that of a spherical field.
f. Define the weak field and strong field cases.
Weak field is when Δo is less than P, and strong field is when Δo is more than P. In the weak
field case, the electron will be promoted to the eg orbital, and in the strong field case the
electron will stay in t2g.
g. Define high spin and low spin.
High spin is when there are more electrons unpaired than in a free ion (spherical electron
distribution), and low spin is when there are more electrons paired than otherwise.
h. What configurations are unambiguous?
3d1, 3d2, 3d3, 3d8-3d10
i. For 3d ion complexes, considering the ligands, how do high spin and
low spin correlate to the spectrochemical series?
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Low spin complexes generally have ligands that are high in the spectrochemical series, while
high spin complexes generally have ligands that are low in the spectrochemical series.
j. Define diamagnetic and paramagnetic.
Diamagnetic compounds are repelled by a magnetic field, while paramagnetic compounds
are attracted to a magnetic field. They are measured by their magnetic dipole moment.
k. Describe the orbital configurations for octahedral, tetrahedral, and
square planar complexes.
Tetrahedral: t2 orbitals are higher in energy than e orbitals, they are separated by Δt, with
the t2 orbitals lying at 2/5 Δt above the barycenter, and e orbitals at 3/5 below it. Tetrahedral
complexes are always high spin.
Square Planar: Highest in energy is the x2-y2, followed by xy, then yz and zx at an equal level,
and then z2 lying lowest in energy. Square planar complexes are higher in energy than
tetrahedral, they are favored for d8 complexes, and are common in 4d8 and 5d8 complexes.
For 3d ions, Ni2+- halogen complexes will almost always be square planar. Low spin is favored.
Octahedral:
l. What is the Jahn-Teller effect?
If the ground electronic configuration of a nonlinear complex is orbitally degenerate and
asymmetrically filled, the complex distorts to remove degeneracy and to lower the energy.
The d orbitals take on the configuration of x2-y2 highest in energy, followed by the z2, then
the zy and zx at a degenerate level, and the xy lying lowest in energy. The xy orbital falls in
energy relative to before the distortion.
m. What will cause a molecule to experience the JT effect?
It is caused by unstable geometry, but more specifically, electrons with degenerate spin
states in eg orbitals.
n. For what numbers of d electrons can we expect to see the JT effect?
It is common in d9 complexes, but also seen in high spin d4 and low spin d7. Also, there will
be no JT effect in low spin d3, d5, d8, d10 because of their electron configurations.
o. How do the energies of the orbitals change with distortion?
Compression:
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As seen in the above diagram, the energies of orbitals with a z component are raised, while
those without a z component are lowered. This is due to the ligand z orbitals having greater
overlap.
Elongation:

Elongation stabilizes the orbitals with a z component, and destabilizes those without one.
There is greater metal-ligand orbital overlap in the dxy and dx^2-y^2 orbitals.
Remember, it is always the z-ligand bonds being altered. In both cases, the molecule distorts
from Oh to D4h symmetry. “Compression pushes the z’s up, and elongation pulls the z’s
down.”
p. What symmetries can we expect to see for the JT effect?
Oh, C4V, D4h
q. What effect does JT distortion have on spectra?
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Absorbance peaks will be asymmetric. Both the ground state and the excited state (which
can be the result of multiple transitions) are detected, so the peak may have a ‘shoulder’, or
overlapped peaks.

r. What are the symmetry labels and degeneracy for a metal s orbital, px
py pz orbitals, and all five d orbitals?
S orbital: a1g, degeneracy of 1
Px, py, pz orbitals: t1u, degeneracy of 3
Dx^2-y^2, dz^2 orbitals: eg, degeneracy of 2
Dxy, dyz, dxz orbitals: t2g, degeneracy of 3
s. What ligand SALCs share symmetry with what metal orbitals, how
many molecular orbitals are formed, and what are the bonding and
anti-bonding characteristics?
SALC a1g= σ1 + σ2 + σ3 + σ4 + σ5 + σ6 -> 2 MO’s 1 bonding, 1 anti-bonding
SALC t1u= σ1 – σ3, σ2 - σ4, σ5 - σ6 -> 4 MO’s 2 degenerate bonding, 2 degenerate anti-bonding
SALC eg= σ1 – σ2 + σ3 - σ4, 2σ5 + 2σ6 - σ1 - σ2 - σ3 - σ4 -> 6 MO’s 3 degenerate bonding, 3
degenerate anti-bonding
t. What are the frontier orbitals?
The molecular eg and t2g orbitals are the frontier orbitals. When considering only σ bonding,
the t2g molecular orbitals are entirely metal in character, and non-bonding.
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u. Ligand π orbitals include SALCs of what symmetry?

Ligand π orbitals include SALCs of t2g symmetry. In the previously discussed σ bonding, the
t2g orbitals were localized on the metal. It now has characteristics of both, so it is delocalized.
v. Π donor ligands are also known as what? Π acceptor ligands are also
known as what?
Pi donor ligands are called pi bases. They have filled pi orbitals about the M-L axis, and are
lower in energy than the σ orbitals.
Pi acceptor ligands are called pi acids. They have empty pi orbitals available for occupation
about the M-L acis.
w. What will increase Δo, and what will decrease Δo?
Pi donor ligands decrease Δo. They do this by raising the energy of the LUMO. Pi acceptor
ligands increase Δo. They do this by lowering the energy of the HOMO.
x. Draw an MO diagram for a π donor and π acceptor.

15) X-ray absorbance spectroscopy

a. What electrons are ejected in XAS?
Electrons are ejected from the core.
b. What is the range of energy for the photons?
The energy of the photo-electron ranges from 0.1 keV to 100 keV.
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c. What does the photon energy correspond to?

They are related to the binding energy of core electrons.
d. What is the edge region?
The edge region is where the photo-electron energy is in the range of Ei to Ei + 10eV.
e. What is the K edge (pre edge)?
It is where the core electrons are not ejected, but promoted to higher energy empty orbitals.
It provides information on energies of excited electronic states and local symmetry of the
atom.
f. What is the continuum?
When referring to a continuous absorption spectrum, a continuum is where absorbance is
shown continuously throughout the given range (think from initial to infinity).
g. What is the energy range for the K edge, Li edge, L2,3 edge, and M edge?
What orbitals do these edges correspond to?
K edge: 4500-9700 eV -> 1s (to continuum)
Li edge: 570-1200 eV -> 2s (to continuum)
L2,3 edge: 400-1020 eV -> 2p (to continuum)
M edge: 28-1.4 eV -> 3 (to continuum)
h. How do dipole transitions appear in the spectra?
Dipole transitions are forbidden.
i. Describe the XANES.
XANES stands for X-ray absorption near edge fine structure. The energy lies between Ei and Ei
+ 10eV. It gives information on oxidation state, coordination environment, and subtle
geometric distortions. It can be used as a fingerprint, as it is characteristic of the
environment and valence state, and also can be used to determine the presence and
quantity of a compound in a mixture.
j. Describe the NEXAFS.
NEXAFS stands for near edge X-ray absorption fine structure. The energy lies between Ei and
Ei + 50eV. It gives information on the orientation of adsorbed molecules.
k. Describe the EXAFS.
EXAFS stands for extended x-ray absorption fine structure. The energy range is anything
greater than the NEXAFS region. The back scattering of photons by adjacent atoms can be
detected by observing periodic trends in intensity at energies just above the absorption
edge. It provides information on electron density, the number of nearby atoms, as well as
the separation of atoms. It will also tell us the bond lengths of species in amorphous
samples.
l. What are the relative strengths of dipole and quadripole transitions?
Dipole transitions are about 100 times stronger than quadripole.
j. X-ray absorption spectrum
Page 38 of 43

Use this picture to better characterize the previously discussed absorption regions.
16) Photoelectron Spectroscopy
a. Define PES.
Photo-electron spectroscopy is the measurement of kinetic energies of electrons emitted by
the ionization of a sample that is irradiated with high energy monochromatic radiation.
More simply put, a sample is irradiated with a single wavelength light source, and this causes
emissions of photoelectrons.
b. What is the formula for the energy of PES?
Ek= hν-Ei
c. What is Koopman’s theorem?
It states that the ionization energy is equal to the negative of the orbital energy.
d. What are the two types of PES?
X-ray photo-electron spectroscopy and ultraviolet photo-electron spectroscopy.
e. Describe XPS.
It is used mostly to study the band structure of solids. The photons which cause ionizations
in samples are photo-electrons emitted from an anode made of either magnesium (Ek
photo-electron = 1.254keV) or aluminum (Ek photo-electron = 1.486keV). The
photo-electrons causing the ionization are the result of an ejection of a 1s electron, followed
by a 2p electron moving down to fill the vacancy. XPS gives broad signals, the half widths are
about 1eV.
f. Describe UPS.
It is used to characterize valence shell energy levels and vibrational fine structure. The
radiation source is a helium discharge lamp. He(I) emits light at 21.22eV, and He(II) emits
light at 40.8eV. There is much greater resolution than in XPS, due to smaller line widths.
g. What does the spectra look like for an electron ejected from a
non-bonding orbital?
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A single, sharp line is produced, and the product is formed in its vibrational ground state.
h. What does the spectra look like for an electron ejected from a bonding
or anti-bonding orbital?
Extended fine structure is observed, with many peaks. The product is formed in multiple
vibrational states.
i. How can we tell if the electron was ejected from a bonding or
anti-bonding orbital?
If it were ejected from a bonding orbital, it will have a lower frequency than the original
molecule. If it were ejected from an anti-bonding orbital, it will have a higher frequency than
the original molecule.
j. What causes peaks to appear in the spectra?
Peaks appear if the ejected electron has significant influence on geometry.

Remember that binding energy and ionization energy are used interchangeably as the label
for the x-axis.
Vibrations within an excited state will produce multiplets.
17) Mass Spectrometry
a. What is mass spec?
It is a destructive analytical technique, in which a sample is bombarded with particles, which
induces both vaporization and ionization. The ions are then accelerated through an electric
field, and deflected with a magnetic field. Considering the order and time in which the ions
hit the detector, we can determine the particle’s mass and charge.
b. What is it used to determine?
It is used to determine the charge to mass ratio of gaseous ions (molecular weight).
Page 40 of 43

c. What resolution is needed to determine the crude molecular mass, and

what resolution is needed to determine the mass defect?
Crude mass: 1 part in 10000
Mass defect: 1 part in one billion
d. What is EI?
EI is electron impact mass spec. The sample is bombarded by high energy electrons (tends to
cause decomposition in large molecules).
e. What is FAB?
FAB is fast atom bombardment mass spec. The bombardment is with small, fast, neutral
atoms. Less fragmentation is observed.
f. What is MALDI?
MALDI is matrix assisted laser desorption/ionization mass spec. It is similar to EI, but uses
laser pulses.
g. What is TOF?
TOF is time of flight analysis. The ions are rapidly accelerated, then allowed to fly freely. It
causes the lighter ions to accelerate faster, and strike the detector sooner. MALDI-TOF is a
common analytical technique.
18) Electron Paramagnetic Resonance spectrometry
a. What is EPR?
EPR is electron paramagnetic resonance spectrometry. The application of a magnetic field
produces different energies in the magnetic angular orientation of electrons (ms=+1/2 and
ms=-1/2). We observe the resonant absorption of unpaired electrons.
b. What type of atoms is it used to study?
It is used to study paramagnetic species.
c. What effect does the magnetic field have on the electrons?
Depending on the spin state of the electron, it will either raise or lower the energy, and the
energy difference is observed.
d. What is the equation for the change in energy?
ΔE=gμbBo
ΔE=hv
μb is the Bohr magneton. Its value is 9.274*10-24 J/T (T= tesla= 1kg/C*s)
e. Describe a continuous wave spectrometer.
The sample is irradiated with a constant microwave frequency and a varying magnetic field.
f. What are the resonant frequencies for most spectrometers, an S band,
a Q band, and a W band? What is the typical magnetic field strength?
The resonance frequencies for most spectrometers are about 9GHz.
S band: 3GHz
Q band: 35 GHz
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W band: 95 GHz
Magnetic field strength is about 0.3T (tesla)
g. How do you improve resolution? What causes the improved
resolution?
Resolution is improved by using high magnetic fields. This reduces the interactions between
paramagnetic centers, which sharpens and simplifies the spectra.
Also, using a pulsed EPR spectrometer provides time resolution, making it possible to
measure dynamic properties. This is analogous to using Fourier transform to improve NMR.
h. What is the g value, and what is it for a free electron?
The g value, also known as the Londe factor, is the measure of the molecule or atom being
studied. It is a product of L, S, and J (the total angular momentum).
The g value for a free electron= 2.0023.
i. What perturbs the g value in compounds?
Spin orbit coupling alters the g value in complexes.
j. Define isotropic, axial, and rhombic.
Isotropic: All 3 g values are the same (along 3 perpendicular axes)
Axial: 2 are the same
Rhombic: All are different
G values are often graphed as derivative plots. For each g value in a plot, there will be a
change in the sign of the slope. 1 change in sign is observed for isotropic, 2 for axial, and 3
for rhombic.

The plot shown has 3 changes in sign, so the sample has a rhombic spin system.
k. Why is resolution improved in frozen samples versus liquid?
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In a liquid sample, the molecules are not stationary. The g values are anisotropic
(directionally dependent), so molecular motion makes them very difficult to measure. The
peaks are often too broad to characterize. A frozen (crystallized) sample locks the atoms in
place, so the g values can be measured.
l. Describe hyperfine structure.
It is a multiplet structure due to coupling of electron spin to magnetic nuclei. A nucleus with
spin I will split the EPR line into 2I+1 lines of the same intensity.
19) Cyclic Voltammetry
a. What is CV, and what does it tell us?
CV stands for cyclic voltammetry, and it tells us the redox potential of a complex, and from
that, we can determine its stability. It also gives us information on thermodynamic and
kinetic properties.
In CV, the current between two electrodes is measured as the potential difference, and it is
changed cyclically, to produce a triangular waveform.
b. What metals are typical of the working electrode?
The working electrode is usually made out of Pt, Ag, Au, or graphite.
c. What metals are typical of the reference electrode?
The reference electrode is usually made of Ag/Agcl.
d. What two critical species are contained in the solution? How
concentrated are they?
CV is performed with a redox couple. The solution is very dilute, on the micro-molar scale or
lower.
e. Detail the process (3 steps)
Step 1: The current is turned on, and as it approaches the reduction potential of the redox
couple, the reduced species is oxidized at the working electrode, and the current starts to
flow.
Step 2: The current rises to a peak, then decreases as the reduced species is depleted.
Step 3: Once the upper limit is reached, the sweep reverses.
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f. How do we approximate the redox potential?

The average of the 2 peaks is the approximate redox potential. To do this from the graph,
with the y axis being the voltage, divide the distance between them by two.
g. What is the separation between the oxidation and reduction potential?
Ideally, the oxidation and reduction peaks are separated by 59mV/#e-.