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Chemist ry 121 Review Package
Table of Contents:
p1 Extra Questions
p7 - Answer Key to Extra Questions
p17 Review Session Key


2


1. Consider the structure to the right:
State the shape and hybridization of all non-H atoms.




2. Draw the Lewis structures, state the shape, and draw the perspective diagram for XeO
3
.

3. Sketch R
3s
(r), R
2
3s
(r), and 4r
2
R
2
3s
(r) vs. r.
4. Rank in order of increasing ionization energy: Rb
+
, Ca
+
, K
+
.
5. Rank the following in order from smallest to largest: Mg
+
, Na
+
, Ne, O
2-
.
6. Rank the Lattice energies from lowest to highest between NaCl, NaF and NaI

7. Rank in order of increasing ionization energy: O, N
-
, Ne
+
, F
+
, P

8. Rank in order of increasing electron affinity: Ne, Fr, B, Li.

9. Rank in order of increasing size: F, Ne
+
, O
-
, B
2-
, C
3-
.

10. Classify each of the bonds in the following molecules as Polar, Non-Polar, or Ionic, and draw a
Lewis Structure for all of the non-ionic structures.
a) CSCl
2


b) MgO

c) NOF
3


d) [NO]
+




3

11. Which of the following bonds is most polar?
a) C-N
b) Li-N
c) B-N
d) Rb-N
e) Na-N

12. Which of the following contain double bonds?
a) N
2

b) NOBr
3

c) MgO
c) CO
2


13. Which oI the Iollowing molecules can`t exist?
a) MgO
2

b) N
2
H
4

c) N
3

14. Draw all chemically reasonable resonance structures of [BN
2
]
3-
(connectivity N-B-N).

15. Arrange the following in order of increasing melting point:
a) NaCl, H
2
O, CH
3
CH
2
OH, PCl
5


b) AsBr
3
, Kr, SiS
2
, PBr
5
, PCl
5

16. A factory was recently built in an area which subsequently experienced rising levels of acid rain.
Which chemical is the factory most likely emitting into the atmosphere?
a) PCl
5

b) H
2
S
c) SO
3

d) ClO
2

4

17. Sketch
3pz
vs. y.

18. Sketch vs. for the 3d
xy
orbital Irom 0 to .

19. On April Fool`s morning, you get to the lab extra early to obtain an emissions spectrum Ior a
freshly prepared sample of B
4+
ions you`ve been experimenting with all week. You have
discovered how to excite the lone electron in each ion to the 5f orbital, and you want to record
the emissions spectrum of this unique species. Unfortunately, although the lab seemed deserted,
the printout oI your spectrum has more lines on it than you think it should..someone must be
playing an awful, secretive prank.

a) Given this list of photon wavelengths (nm) emissions, determine which should not exist:
162, 75.0, 51.3, 26.3, 19.5, 17.4, 4.9, 4.1, 3.9, 3.8


b) At the end of the experiment, assuming the sample is exposed to no other light sources, will
all the electrons end up in the ground state (ie. the 1s orbital)?

20. Write out an equation for the following reactions (this question just asks you for the reactions
you`re supposed to know, which were summarized in the package tables; consider it more
optional than the other questions):

a) Potassium with excess oxygen?


b) Lithium with limited oxygen?


c) Sodium Oxide with water?


d) Calcium with Chlorine gas?


e) Be with carbon dioxide?


f) Gallium (Ga) with oxygen?


g) Boron undergoing a thermite reaction?


h) Aluminum with water?



5

i) The Hall-Heroult process?


j) Silicon with water?


k) Formation of Silica (at 1000C)?


l) Germanium (Ge) with Bromine gas?


m) Germanium (Ge) with limited Oxygen at room temperature?


n) The formation of Phosphorous acid?


o) Arsenic (As) with limited bromide gas?


p) Production of sulfur trioxide?


q) The formation of sulfurous acid?


r) The formation of sulfuric acid?





21. Balance these reactions
a) _ NaBr
(aq)
+ _ H
2
O
(l)
_ Br
2(g)
+ _ H
2(g)
+ _ NaOH
(aq)



b) I
2(g)
+ H
2
O
(l)
HOI
(aq)
+ HI
(aq)








6

22. Rationalize why elements in the first 2 rows of the periodic table cannot expand their octet

23. What is the hybridization of the carbon atom(s) in each of the following species?
CCl
2
O
SiCl
2
(CH
3
)
2

CO
2


24. Draw a diagram depicting the orbital cross sections in BF
3



25. Draw an orbital overlap diagram for ammonia


26. Which will have a stronger pi bond, CO
2
or CS
2
?


27. Will the molecule H
2
Si=Si=SiH
2
be planar or twisted?


28. Draw out energy level diagrams for B
2
and F
2
and explain any differences between them. Also,
calculate the bond order of each compound.




29. II I tell you that
1
,
2
,
3
, and
4
MOs in a molecule have 0, 1, 2, and 3 nodal planes
respectively, then rank these orbitals in terms of increasing antibonding nature.



30. Why are the noble gases found as single atoms? (Hint: Draw out the MO for Ne!)




31. Look back at the N
2
MO diagram we drew during the session. How would the diagram look if
the molecule was N
2
+
?




7


1. Consider the structure to the right:
State the shape and hybridization of all non-H atoms.
1,2,3,15 - tetrahedral (O`s are bent) so sp
3

4,5,6,7,8,9,10,11 - trigonal planar so sp
2





2. Draw the Lewis structures, state the shape, and draw the perspective diagrams for XeO
3
.


tetrahedral - trigonal pyramidal


3. Sketch R
3s
(r), R
2
3s
(r), and 4r
2
R
2
3s
(r) vs. r.
Please not that the begi nning of the graph should contact the y-axis at some point; the
function I graphed were j ust not conducive to showing it on a reasonable scale.


















Xe
O
O O

8

4. Rank in order of increasing ionization energy: Rb
+
, Ca
+
, K
+
.
Ca
+
, Rb
+
, K
+
5. Rank the following in order from smallest to largest: Mg
+
, Na
+
, Ne, O
2-
.
Na
+
, Ne, O
2-
, Mg
+

6. Rank the Lattice energies from lowest to highest between NaCl, NaF and NaI
Ans: NaF>NaCl>NaI
7. Rank in order of increasing ionization energy: O, N
-
, Ne
+
, F
+
, P
N
-
<P<O<F
+
<Ne
+

Reasons:
- Ne^+ al ready lost one electron. The usually noble gas does not want to lose another
elect ron, therefore, its ionization energy is high
- F^+ is highly electronegative, and therefore would rather get electrons than lost another
one. However, because Ne is a noble gas, it still has a higher ionization energy
- N^- has gained an electron - it wouldn`t mind returning to its neutral state and therefore
has a low ionization energy
- P has valence elect rons in the n = 3 shell. The valence electrons are therefore not held very
tightly, and are easy to remove.
8. Rank in order of increasing electron affinity: Ne, Fr, B, Li.
Ne<Fr<Li<B
Reasons:
- Ne is al ready a very stable noble gas and therefore does not want an extra electron
- Fr is the least elect ronegative atom and therefore has the a very low att raction for an extra
elect ron
- B has a greater # of protons than Li, therefore adding an extra electron into the same shell
in both elements is more favourable for B
9. Rank in order of increasing size: F, Ne
+
, O
-
, B
2-
, C
3-
.
Ne<F<O<C<B
Reasons:
- Ne^+ and F are isoelect ronic, but Ne has more protons, therefore has more pull for the
elect rons, and is therefore smaller than F

9

- O^- and F are isoelect ronic, but O^- has 1 less proton than F, therefore the electrons are
not held as close and O^- is larger than F
- C^3- and F are isoelect ronic, but for the same reason as O^2-, F is smaller. C^3- has more
elect rons for the number of protons that it has, which is why it is bigger than O^2-
- B^2- is the largest because it has the least number of protons, and there is therefore less
pull for the electrons that it has.
10. Classify each of the bonds in the following molecules as Polar, Non-Polar, or Ionic, and draw a
Lewis Structure for all of the non-ionic structures.
a) CSCl
2

covalent, polar
b) MgO
ionic
c) NOF
3

polar covalent
d) [NO]
+

polar covalent

11. Which of the following bonds is most polar?
a) C-N
b) Li-N
c) B-N
d) Rb-N
e) Na-N

12. Which of the following contain double bonds?
a) N
2

b) NOBr
3

c) MgO
c) CO
2



10

13. Which oI the Iollowing molecules can`t exist?
a) MgO
2

b) N
2
H
4

c) N
3


14. Draw all chemically reasonable resonance structures of [BN
2
]
3-
(connectivity N-B-N).







15. Arrange the following in order of increasing melting point:
a) NaCl, H
2
O, CH
3
CH
2
OH, PCl
5
PCl
5
< CH
3
CH
2
OH < H
2
O < NaCl

b) AsBr
3
, Kr, SiS
2
, PBr
5
, PCl
5
PCl
5
< CH
3
CH
2
OH < H
2
O < NaCl

16. A factory was recently built in an area which subsequently experienced rising levels of
acid rain. Which chemical is the factory most likely emitting into the atmosphere?
a) PCl
5

b) H
2
S
c) SO
3

d) ClO
2

17. Sketch
3pz
vs. y.
no graph here; 3p
z
exists along z-axis.







11


18. Sketch vs. for the 3d
xy
orbital Irom 0 to .



















19. On April Fool`s morning, you get to the lab extra early to obtain an emissions spectrum for a
freshly prepared sample of B
4+
ions you`ve been experimenting with all week. You have
discovered how to excite the lone electron in each ion to the 5f orbital, and you want to record
the emissions spectrum of this unique species. Unfortunately, although the lab seemed deserted,
the printout oI your spectrum has more lines on it than you think it should..someone must be
playing an awful, secretive prank.

a) Given this list of photon wavelengths (nm) emissions, determine which should not exist:
162, 75.0, 51.3, 26.3, 19.5, 17.4, 4.9, 4.1, 3.9, 3.8

Fi rst, draw out the possible transitions. Starting f rom the 5f, the 3d and 4d orbitals are
accessible, but no 5 to 2 or 1 transitions are possible. These cor respond to wavelengths of
17.4 and 3.8nm. Next, f rom the 4d we can access the 3p or 2p, but not the 1s orbital, so 4 to
1 transition is forbidden - the wavelength for this is 3.9nm. From the 3d we can access the
2p, and f rom the 2p we can access the 1p, so all other transitions are allow between
principal electrons shells.

b) At the end of the experiment, assuming the sample is exposed to no other light sources, will
all the electrons end up in the ground state (ie. the 1s orbital)?
No, since if they transition f rom the 3p to the 2s they cannot decay further, nor can they be
excited because there is no light energy being provided to give them energy to get out of

12

that orbital. They are ~trapped. (You get to the 3p orbital as explained in (a).)

20. Write out an equation for the following reactions:

a) Potassium with excess oxygen?

Ans: 2K
(s)
+ O
2(g)
K
2
O
2(s)



b) Lithium with limited oxygen?

Ans: 2Li
(s)
+ (1/2)O
2(g)
Li
2
O
(s)



c) Sodium Oxide with water?

Ans: Na
2
O
(s)
+ H
2
O
(l)
2NaOH
(aq)


d) Calcium with Chlorine gas?

Ans: Ca
(s)
+ Cl
2 (g)
CaCl
2(s)



e) Be with carbon dioxide?

Ans: 2Be
(s)
+ CO
2(g)
2BeO
(s)
+ C
(s)


f) Gallium (Ga) with oxygen?
Ans: 4Ga
(s)
+ 3O
2(g)
2Ga
2
O
3(s)


g) Boron undergoing a thermite reaction?

Ans: 2B
(s)
+ Fe
2
O
3(g)
B
2
O
3(s)
+2Fe
(l)
+ Energy

h) Aluminum with water?
Ans: Al
(s)
+ H
2
O
(l)
No Reaction!

i) The Hall-Heroult process?
Ans: 2Al
2
O
3(l)
+3C
(s)
4Al
(l)
+ 3CO
2(g)


j) Silicon with water?
Ans: Si
(s)
+ H
2
O
(l,g)
No Reaction

k) Formation of Silica (at 1000C)?
Ans: Si
(s)
+ O
2(g)
SiO
2(g)


13


l) Germanium (Ge) with Bromine gas?
Ans: Ge
(s)
+ 2Br
2(g)
GeBr
4(l)


m) Germanium (Ge) with limited Oxygen at room temperature?
Ans: Ge
(s)
+ 2O
2(g)
No Reaction

n) The formation of Phosphorous acid?
Ans: P
4
O
6(s)
+ 6H
2
O
(l)
4H
3
PO
3(aq)


o) Arsenic (As) with limited bromide gas?
Ans: As
4(s)
+ 6Cl
2(g)
4AsCl
3(l)

p) Production of sulfur trioxide?
Ans: 2SO
2(g)
+ O
2(g)
2SO
3(g)


q) The formation of sulfurous acid?
Ans: SO
2(g)
+ H
2
O H
2
SO
3(aq)


r) The formation of sulfuric acid?
Ans: SO
3(g)
+ H
2
O H
2
SO
4(aq)


21. Balance these reactions
a) _ NaBr
(aq)
+ _ H
2
O
(l)
_ Br
2(g)
+ _ H
2(g)
+ _ NaOH
(aq)

Ans: 2 NaBr
(aq)
+ 2 H
2
O
(l)
1 Br
2(g)
+ 1 H
2(g)
+ 2 NaOH
(aq)

b) I
2(g)
+ H
2
O
(l)
HOI
(aq)
+ HI
(aq)
Ans: 1 I
2(g)
+ 1 H
2
O
(l)
1 HOI
(aq)
+1 HI
(aq)


22. Rationalize why elements in the first 2 rows of the periodic table cannot expand their octet

No d-orbitals to hybridize

23. What is the hybridization of the carbon atom(s) in each of the following species?
CCl
2
O sp
2

SiCl
2
(CH
3
)
2
sp
3

CO
2
- sp
24. Draw a diagram depicting the orbital cross sections in BF
3







14

25. Draw an orbital overlap diagram for ammonia









26. Which will have a stronger pi bond, CO
2
or CS
2
?
CO
2
, because it is formed f rom the 2p orbitals. Similar orbitals have better
overlap than dissimilar orbitals.

27. Will the molecule H
2
Si=Si=SiH
2
be planar or twisted? Twisted


28. Draw out energy level diagrams for B
2
and F
2
and explain any differences between them. Also,
calculate the bond order of each compound.


15














29. II I tell you that
1
,
2
,
3
, and
4
MOs in a molecule have 0, 1, 2, and 3 nodal planes
respectively, then rank these orbitals in terms of increasing antibonding nature.
1
S ,
2
S ,
3
S ,
4
S

30. Why are the noble gases found as single atoms? (Hint: Draw out the MO for Ne!)



BO = 0, therefore Ne
2
does not exist




BO = 1 for both molecules

Differences:
- F
2
has more electrons than B
2
since atomic fluorine has more electrons than boron
- The energies of the sigma-2p and pi-2p orbitals are reversed for F
2
, due to mixing
between 2s and 2p orbitals of boron (F
2
has same relative energies of orbitals as O
2
)

16

31. Look back at the N
2
MO diagram we drew during the session. How would the diagram look if
the molecule was N
2
+
?


1.













1s 1s
1s
1s
E
2p 2p
2s 2s
1s
1s
N
2

N N
+

17

Periodic Trends:
Know your periodic table
1) The 4 blocks: s, p, d, and f
2) The special names for elemental categories.
al kali metals, al kaline earth, pnictogens, chalgogens, halogens, noble gases, (bottom)
lanthanides, actinides.
3) Z
eff
increases in which direction? left to right
4) Ionization energy increases from: bottom to top, left to right. SO if i were to ask you a
question like which has higher ionization energy, Al or Mg, you`d say? Al? You`d be
wrong, because of the exception in the trend due to the p orbitals being higher in
energy - examine the graph at the end of Ch9 if you need to.
5) Electron Affinity increases from: bottom to top, left to right (again) except for noble
gases. Why??? because they have full valence octets.
6) Atomic radius increases from: right to left, top to bottom (opposite I E).

1. Rank the following in terms of increasing ionization energy, then size, and then identify any
special groups they belong to in their elemental states.
S
2-
, Cl
-
, Ar, Ca
2+
, Ge
4+
, U

size: Ge
4+
, Ca
2+
, Ar, Cl
-
, S
2-
, U
ionization energy: U, S
2-
, Cl
-
, Ar, Ca
2+
, Ge
4+
.
naming: do it quickly
2. Which of the following statements is INCORRECT?
a) The radius of F
-
is smaller than that of Cl
-
.
b) The radius of Cl
+
is greater than that of Al.
c) The radius of Cl is smaller than that of P.
d) The radius of I is larger than B.

Lattice energy describes the energy required to break one mole of crystal into the ions in gas
phase (at infinite separation). Not describable by coulomb`s law oI attraction Ior two points,
because ions are packed in crystal lattices. However, certain properties still matter; size, and
charge. Smaller atoms will take more energy to separate because they will influence each other
more. Larger charges also have a large influence because they will more strongly attract each
other. The online package will have more practice with all of these trends if you want it.
I ntermolecular Forces:
Different types of interactions exist between molecules. The relative strength of these bonds is:
London Dispersion Forces < Dipole-Dipole Interactions <Hydrogen Bonds < Ionic < Network
Covalent
London Forces, also known as dispersion forces, are caused by the movement of electrons to

18

induce a dipole within individual molecules. This results in an attraction between molecules.
Polarizability is how easily electrons are moved in a molecule. Larger molecules are more
polarizable and have higher melting points.
Dipole-Dipole I nteractions arise from the attraction between species that have a permanent
dipole moment. Electronegativity difference increases dipole moment, which increases melting
point.
Hydrogen Bonds are special cases of dipole-dipole interactions
3. Which of the following pure substances will exhibit the strongest hydrogen bonding?
a) CH
3
CH
2
NH
2

b) PCl
3

c) CH
3
OCH
3

d) CH
3
CHO
e) BH
3


4. Arrange the following in order of increasing boiling point: CH
3
OH, NaF, Ar, MgO, and H
2
O
Ar (noble gas), methanol, water (better H-bonding than methanol), NaF, then MgO
(stronger attractive forces due to larger charge on the ions). bp NaF = 1695; bp MgO 3600.
Lewis/Resonance Structures and VSEPR Theory:
First: Hybridization
- Why do we need it?
Consider ethylene. The shape at each carbon is ______________. How can we achieve this
shape using s and p orbitals? We MUST hybridize, and in doing so, we can
rationalize almost any bonding geometry.
I n this case, we combine the outer s-orbital of each carbon with 2 of its p-
orbitals to get 3 planar hybrid orbitals, as show below. These 3 sp2 orbitals
are use in bonds. This leaves 1 p-type orbital for use in the -bond between the carbons.





19


The wavefunctions of atomic orbitals can be added or subtracted to give new wavefunctions
called hybrid orbitals. Only orbitals in the same shell can be mixed together.


- How do we recognize it?
We can determine the hybridization by determining the SHAPE of the atom.

*Note that links are not the same as bonds. Double and triple bonds count as one link.


5. Label the structures with the hybridizations of the non-hydrogen atoms in the structures below.









6. Your experiments indicate that PCl
3
has a dipole moment, but AlCl
3
does not. Propose a
molecular geometry for each molecule.
Al Cl
3
is trigonal planar (dipoles cancel), PCl
3
is
tetragonal (overall dipole ~down as drawn)



NOW HOW CAN WE MA K E T HESE?
P
4(s)
+ 6Cl
2(g)
4PCl
3(l)

2Al
(s)
+ 3Cl
2(g)
2Al Cl
3(s)
- but is this how this molecule prefers to exist? No!


7. Draw Lewis structures for the following two molecules:
Number of Links*
+ Lone Pai rs
Hybridization VSEPR Parent Shape Bond Angles
2 sp Linear 180
o

3 sp
2
Trigonal Planar 120
o

4 sp
3
Tetrahedral 109.5
o
5 sp
3
d Trigonal Bipyramidal 120 and 90
o
6 sp
3
d
2
Octahedral 90
o


20

a) C-N-O (all atoms have full octets you determine the charge)
b) H
3
PO
4
does it have a dipole moment?

(b) does have a dipole moment, since the
~top O can withdraw electrons through
resonance; also, sp
2
orbitals are more
elect ronegative than sp
3
orbitals
Notice that we can draw a resonance
structure of this, with a negative formal
charge on the O and a positive on the P - perfectly reasonable. F rom this, we can see that
that O withdraws through resonance AND EN. The others only withdraw through EN.
ALSO: what is the hybridization of each oxygen? The sp
2
orbitals have more s-character
and are more elect ron withdrawing as they are closer to the nucleus.

How can we make (b)? P
4
O
10(s)
+ 6H
2
O
(l)
4H
3
PO
4(aq)


8. Deprotonated tetrazole is used in solid phase DNA synthesis. Draw all reasonable resonance
structures of this anion.









9. Consider the structure to the right:
How many atoms can lie in the same plane?
i] 5 ii] 10 iii] 15 iv] 16 v] 18











21

Quantum Mechanics:
There are several equations you should have memorized by now for the quantum
mechanics section (Ch7), which I will reproduce on this power point deal.
c
E
k
= E
light
- E
binding
h(-
0
) (binding energy) > E hc/ h (energy of light)

xp h/4 (Heisenberg`s Uncertainty. Cannot find exact position and exact momentum
of subatomic particles at the same time.)
E
k
= mu
2

3-D One Electron Systems:
There exist 3 quantum numbers for electrons in 3D boxes: n, l, and m
l
. Each combination that
satisIies Schrodinger`s equation gives an atomic orbital. The way we describe the electron in
3D space, we use spherical polar coordinates (you`ll be introduced to polar coordinates in
Math 200) instead oI Cartesian coordinates, where a point is described by 3 variables: r, , .
These help express a wavefunction which can be separated into a product of two functions: the
radial wave function R
n,l
(r) and the angular wave function Y
l, ml
(,). R describes the size of the
orbital and Y describes the shape of the orbital.

Only certain values for the quantum numbers describe an orbital and give solutions to
Shrodinger`s equation.

n can be any integer >0. l can be anything up to n-1. m
l
can be anything f rom - l to + l.


10. Sketch (a) the

orbital, then (b)

vs. from = 0 to 2.




22


Spectroscopy of One-Electron Species
The energy associated with an orbital is given by

where Z is the
atomic number and n is the principle quantum number. Notice that for a one-electron system, the
orbital energy depends only on the principal shell number, not on the subshell - this is due to the
degenerate energies of all but the s-orbitals.

When light shines through a sample, atoms absorb certain wavelengths of light which correspond
to the specific energy differences between orbitals. These energy differences can be calculated
using

. The wavelength of light required to provide

precisely this energy is Iound using Planck`s equation:

- notice that a higher

wavelength corresponds to a lower energy.

The absorption of energy causes an electron to jump to a higher energy orbital. The energy that
doesn`t get absorbed passes through the sample and is then detected by our eyes or by a detector.
In an absorption spectrum, energies will be recorded for transitions between all states, for
example, 12, 13, 14. On an energy level diagram, in contrast, only the specific energy of
each orbital is shown.
Selection rules
The above spectra were determined using only changes in the principal quantum number n. If we
want to assign transitions to specific pairs of orbitals (1s, 2s, etc.), we must take into account the
other quantum numbers. When we do, certain transitions are not allowed, and these are
determined by the following rules:
- Only non-zero changes in n are allowed
- l can only change by +1 or -1

11. A sample of hydrogen ions in the ground state is irradiated with ultraviolet light of wavelength
95nm. Which emission below is not possible?

23

Now draw all possible transitions; the elect rons must be in a 5p orbital if it was excited
f rom g.s. hydrogen atoms. Notice the transition f rom 4 to 1 is i mpossible and use that to
calculate a wavelength emission.

Crystal Structures
Simple Cubic

Atoms per cell: 1
Cubic holes per cell: 1
Tetrahedral holes per cell: 0
Octahedral holes per cell: 0

Body-Centred Cubic

Atoms per cell: 2
Cubic holes per cell: 0
Tetrahedral holes per cell: 0
Octahedral holes per cell: 3


Face-Centred Cubic

Atoms per cell: 4
Cubic holes per cell: 0
Tetrahedral holes per cell: 8
Octahedral holes per cell: 4
*In FCC if half of the tetrahedral holes are filled, there is a 1:1
ratio of ions



24


Coordination number is the number of other ions that each ion touches
Stoichiometric ratio is inversely proportional to the coordination number, but proportional to
the ratio of ions in the unit cell to the number ions in holes

Ions in each position of a cell contribute a different fraction to the cell:
Vertex ions contribute 1/8 of an ion
Edge ions contribute
Face ions contribute
Body ions contribute 1 ion

To determine the number of ions in a cell, count the number of ions in each position and multiply
by the fraction that they contribute. The sum of the contributions from each position is the
number of ions in the cell.


8. The oxygen atoms in MgAl
2
O
4
form a face centred cubic cell with Mg atoms in tetrahedral holes
and Al atoms in octahedral holes. What fraction of each type of hole is filled?
14 Oxygen atoms in the diagram of the F CC in cell, but these are all shared: the corners
are shared with 8 cells, so each is 1/8 belonging to a given unit cell. Each facial atom is split
between to cells, so each is 1/2 belonging to this cell. thus, we have 4 atoms in our cell,
which makes this question simple; we must have 2 Al atoms and 1 Mg. This means the
tetrahedral holes are 1/8 filled with Mg and the octahedral holes are filled with Al.

9. A graduate student found a bottle of unknown crystals of a metal on a dusty shelf in the lab, but
the bottle label had faded over time and was totally unreadable. He analyzed the crystals and
found them arranged in a simple cubic packing structure. The density of the compound was
determined to be 9.142 g/cm
3
and the atomic radius was measured to be 168pm. Identify the
metal.

Wor k backwards starting f rom the atomic radi us; r = 1.68x10
-8
cm. The side length is 2r =
3.36x10
-8
cm, and (2r)
3
= Vol. of cell = 3.80x10
-23
cm
3
/cell. Vol. x N mol
-1
= 22.84cm
3
/mol.

Units of molar mass are g/mol, so we need to use the density in g/cm
3
to get us there,
dimensionally speaking.
22.84cm
3
/mol x 9.142 g/cm
3
= 209 g/mol This is Po.




25

Chapter 3

1. Oxidation States:

Oxidation States show what molecules are losing electrons and gaining electrons.
x If losing electrons, atoms become positive
x If gaining electrons, atoms become negative

Rules:

1) The sum of the oxidation states of all the atoms or ions in a neutral compound is zero. If the
entire compound is charged it will most likely be indicated.
2) Oxidation problems have at least one a cation and one anion.
3) Approach each question like a simple math questions as will be explained below:

1. What is the oxidation state of Mg 2+?

Ans: 2+

2. What is the oxidation state of X, in X
2
O
6
-
?

Ans: 2X + 6O = -1
2X + 6(-2) = -1
2X = -1 - 6(-2)
2X = -1 (-12)
2X = -1 + 12
2X = 11
X = 11/2




S-block Metals

Ionic Compounds are formed through the reaction of 2 species:

x One species loses electrons
x One species gains electrons

x Please Note: Elements in the same column react the same way.
x The trick to mastering these reactions lies in writing them out on flash cards and review
alittle every day.





26

1. Al kali Metals:

x Alkali Metals are elements in group 1
x They have 1 valence electron and therefore, are really reactive as they want to get rid of
their lone valence electron to have a full octet.
x Cannot use Oxidation states in these reactions

Reactions that you have to know for Alkali Metals!

Reaction Conditions
2Na
(s)
+ (1/2)O
2(g)
Na
2
O
(s)


Oxygen is limited, Sodium Oxide
is produced
2Na
(s)
+ O
2(g)
Na
2
O
2(s)


Oxygen is in excess, Sodium
Peroxide is produced
2Na
(s)
+ 2H
2
O
(l)
2NaOH
(aq)
+ H
2 (g)
+ Energy

Na
2
O
(s)
+ H
2
O
(l)
2NaOH
(aq)


Na
2
O
2(s)
+ 2H
2
O
(l)
2NaOH
(aq)
+ H
2
O
2(aq)


2. Al kaline Earth Metals:
x Alkaline Earth Metals are elements in group 2
x They have 2 valence electrons and are therefore, highly reactive.
x Use Magnesium`s oxidation state of +2 in reactions:

Reaction Conditions
Mg
(s)
+ (1/2)O
2(g)
MgO
(s)


Magnesium Oxide Produced
Mg
(s)
+ 2H
2
O
(l)
Mg(OH)
2 (aq)
+ H
2 (g)


Magnesium oxide coating must be removed
by boiling water or using dilute HCl
Mg
(s)
+ Cl
2 (g)
MgCl
2(s)


2Mg
(s)
+ CO
2(g)
2MgO
(s)
+ C
(s)





27

Chapter 6
1. Group 13 Elements- Aluminum
x Alumina or Aluminum Oxide (Al2O3) is found as a mineral on earth.
x The Hall-Heroult process takes alumina and makes Aluminum:
x 2Al2O3(l) +3C(s) ---------------------- 4Al(l)+ 3CO2(g)
Na3AlF6
x Please note that for the reactions below, Aluminum has a +3 oxidation state.
Generally oxidation states are thought of as the number of electron a species can
donate or receive.
x Remember that oxygen has an oxidation state of -2
x Reactions that you have to know:
Reactions Conditions
4Al(s) + 3O2(g) 2Al2O3(s) Pure Aluminum is very reactive with oxygen
and therefore forms Alumina
2Al(s) + Fe2O3(g) Al2O3(s) +2Fe(l) + Energy This is a Thermite Reaction! It releases a lot
of energy!
Al(s) + H2O(l) No Reaction! This is because Aluminum has a thin coat
that protects aluminum from getting in
contact with water
2Al(s) + 3H2O(l) Al2O3(s) +3H2(g) Once HCl or NaOH is used, the protective
coat can be dissolved
2Al(s) + 3Cl2(g) 2AlCl3(s) (dimer) Al2Cl6 is a dimer as AlCl3 does not have a full
octet
Al2Cl6 + 2N(CH3)3 2(AlCl3-N(CH3)3)

Questions:
1. Draw out 2AlCl3(s)







2. Group 14 Elements- Silicon
x Like Aluminum, elemental silicon does not exist naturally on earth

28

x In order to produce elemental Silicon:
x SiO2(s) +2C(s) --- Si(s)+ 2CO(g) occurs at 3000C
x Please note that Silicon has an oxidation state of +4 and reacts accordingly in the
reactions below
x Reactions that you have to know:
Reactions Conditions
Si(s) + H2O(l,g) No Reaction At room temperature, no rxn due to
protective coating
Si(s) + O2(g) No Reaction At room temperature, no rxn due to
protective coating
Si(s) + O2(g) SiO2(g) At 1000C, Silica is formed
Si(s) + 2Cl2(g) SiCl4(l) At 300C, Silicon can react with Halogens

3. Group 15 Elements- Phosphorous
x Nany of the woilus militaiy weapons contain phosphoious theiefoie think of
phosphorous as very reactive and unstable.
x Phosphorous has an oxidation state of +3 and +5
x Covalently bonded phosphorous atoms like to form rings of P4 molecules
x White Phosphorous> Red Phosphorous> Black Phosphorous
Most Reactive --------------------------------- Least Reactive
x Draw White Phosphorous
x







x Draw Red Phosphorous






29

x Reactions that you have to know:
Reactions Conditions
2Ca3(PO4)2(s) + 10C(s) + 6SiO2(s) P4(l) +10CO(g)
+6CaSiO3(s)
Produces White Phosphorous
P4(s) + 3O2(g) P4O6(s) Reacts under limited Oxygen
P4(s) + 5O2(g) P4O10(s) Reacts under excess Oxygen
P4O6(s) + 6H2O(l) 4H3PO3(aq) Phosphorous Acid Forms
P4O10(s) + 6H2O(l) 4H3PO4(aq) Phosphoric Acid Forms
P4(s) + 6Cl2(g) 4PCl3(l) Reacts under limited chlorine gas
P4(s) + 10Cl2(g) 4PCl5(s) Reacts under excess chlorine gas

4. Group 16 Elements- Sulfur
x The Frasch process obtains Pure Sulfur:
1. 2H2S(g) + 3O2(g) 2SO2(s) + 2H2O(g)
2. 2H2S(g) + SO2(g) 3S(l) + 2H2O(g) (300C)
3. Cannot use Oxidation states in the reactions belo


x Reactions that you have to know:

Reactions Conditions
S(s) + O2(g) SO2(g) Formation of Sulfur dioxide
2SO2(g) + O2(g) 2SO3(g) Sulfur dioxide reacts with oxygen to
produce sulfur trioxide
SO2(g) + H2O H2SO3(aq) Sulfurous Acid produced
SO3(g) + H2O H2SO4(aq)
Sulfuric Acid produced






30

5. Group 17 Elements- Chlorine
x This row of elements have a very high affinity for electrons and therefore, they are
never found in the elemental form e.g. Cl but found in the diatomic form e.g. Cl2(g)
x Reactions that you have to know:
Reactions Conditions
2NaCl(aq) + 2H2O(l) Cl2(g) + H2(g) +
2NaOH(aq)

Cl2(g) + H2O(l) HOCl(aq) + HCl(aq)
A strong acid (Hydrochloric acid) and a weak acid
(Hypochlorous acid) is produced. This reaction
has equilibrium arrows and through Le
Chatelieis piinciple the ieaction can be pusheu
backwards
HOCl(aq) + HCl(aq) Cl2(g) + H2O (l)
2NaClO3(aq) + SO2(aq) 2ClO2(g) +
Na2SO4(aq)
Formation of ClO2(g) (Chlorine dioxide)is a very
dangerous chemical

6. Group 18 Elements- No Reactions!




Electronic Configurations:

1. Ground State: The ground state is the lowest energy arrangement of an electron or
electrons within the orbitals of an atom or ion.

e.g: Li= 1s2 2s1



The Pauli Exclusion principle:
x No two electrons in a single atom can have the same four quantum numbers; if n, l,
and ml are the same, ms must be different such that the electrons have opposite
spins, and so on.
x ms can be both +1/2 and -1/2

31

Bunus iule
x Bunus iule states that when uegeneiate oibitals aie available such as the thiee p
orbitals, electrons occupy them singly with the same spin before being paired within
the same p orbital
x To rationalize this; remember that electrons are negative and therefore repel one
another
Aufbau principle:
x The builiuing up piinciple
x Electrons fill the orbitals from lowest energy to highest energy
x Think of the ground state as you rarely have only one electron in the 3s orbital and
electrons in the 3p orbitals
Exceptions to regular orbital filling:
1. Chromium and Copper- The 4s orbital is lower in energy than the 3d orbital.
Generally, the 4s orbital is filled up before the 3d orbital. However, in the case of
chromium and copper, it is more favorable place an electron from the 4s orbital to
the 3d orbital.

Questions:
a) Draw the orbital diagrams for a) Chromium and b) Copper
See your CHiRP for this
2. When transition metals are ionized (lose electrons), they first lose electrons from
their p orbitals, then s orbitals then d orbitals
a) What is the energy configuration of Copper (I) ion?
b) What is the energy configuration of Chromium (I) ion?


32

Excited States:
x The Excited states are anything but the ground state
x There can only be one ground state but infinite excited states
a) Write an excited state for phosphorous (I) ion
b) Write an excited state for Chromium

Magnetic Properties:
x Species that have one or more unpaired electrons are paramagnetic
x Species with NO un paired electrons are called diamagnetic (think of dice at a craps
table you always neeu uice hence ui
Questions:
a) Write out the electronic configuration for Kr+, draw out its oibital uiagiam anu
state whether it is paramagnetic or diamagne

33


b) While we are generally taught that Ionization energy increases from left to right on
the periodic table, explain why 1) The ionization energy of Be is less than B. (Group
13 vs Group 2) 2) Rationalize why Oxygen has a lower ionization energy than
Nitrogen (Group 16 vs Group 15)?

Synthesis Question: In a chemical factory, solid lithium (100.00 mol) reacts with limited
oxygen gas (25.00 mol) to produce Compund X (50.00 mol). Compound X reacts with
water (50.00 mol) to produce Compound Y (100.00 mol). Finally, Compound Y reacts
with H2SO4 (aq) to produce Mixture Z which consists of water and 2 charged species.
Write the reactions that form Compound X, Compound Y and Mixture Z.










34




Valence Bond Theory

Bonds between atoms are represented as the overlap of two orbitals containing one unpaired
electron each, and with opposite spins using either orbital diagrams or orbital cross sections.

Sigma bonds are formed by orbitals that lie on the same axis (orbitals have to point towards
each other)

35

Pi bonds are formed by orbitals that lie above and below the axis.

* There is always exactly one sigma bond (no more and no less) between two covalently bonded
atoms.
*Hybrid orbitals are never involved in pi bonds.

Diffuse (large) orbitals have poor overlap, and thus form very weak bonds. 2p orbitals form the
best pi bonds.
Orbitals of si milar size have better overlap than dissimilar orbitals, and thus form stronger
bonds.

Questions:

1. Draw the valence bond diagram for carbon dioxide.





















2. Which of the d-orbitals can form a pi bond and which can form a sigma bond with a 2p
z

orbital?

Sigma: d
z
2 pi : d
xz
d
yz



36

Molecular Orbital Theory:

This model of atomic bonding wor ks thus: two atoms with thei r elect rons in the atomic
orbitals come close together, and the electrons wavefunctions interfere either
constructively or destructively.


























Some key points for MO theory:
1) Number of MOs formed = number of AOs they were formed from.
2) Wave functions of similar phase reinforce each other and cause bonding interactions;
wavefunctions of opposite phase weaken each other and cause antibonding interactions.
Each of these interactions gives a possible MO for the new system. Bonding orbitals
contribute to bond strength, while antibonding orbitals lessen bond strength. Therefore,
if you have equal bonding and antibonding interactions, you have no bond!
3) Bonding interactions are greater Ior species with similar 'size oI atomic orbitals
(similar principal quantum number n) due to better orbital overlap.
4) Pauli exclusion, Hund`s rule, and the AuIbau principle must be observed.
5) Delocalized MOs are symmetrical




1s 1s
s 1
V
1s
s 1
*
V
1s
2s 2s
s 2
*
V
s 2
V
1s
Li Li
2

Li
E
+
- +
- Same phase wave functions
interfere constructively
- Bonding molecular orbital
(MO) formed
- Bonding MO < Atomic Orbital
(AO) (favourable)
- Opposite phase wave functions
interfere destructively
- Antibonding molecular orbital
(MO) formed
- Antibonding MO > AO
(unfavourable)
ENERGY is
CONSERVED!!!
Node: less electron density
than there was before, so
positive nuclei repel each
other
More nodes = higher energy
HOMO
(highest occupied
molecular orbital)
LUMO
(lowest unoccupied
molecular orbital)

37

1. Draw the energy level diagram for N
2
.






REMEMBER: the
2p
orbital is higher in energy than the
2p
orbitals for B
2
, C
2
, and N
s
,
but they switch for O
2
and F
2
. Why? Because the 2s and 2p orbitals are very close in
energy and mix to disrupt the energy of the system, so the relative ordering of orbitals is
perturbed. Memorize this, keeping the rationale in mind.

Bond Order:
This equation makes sense since the bonding electrons provide stability for the system,
while antibonding electrons provide instability to the molecule.







38

2. Benzene (C
6
H
6
) has a planar ring structure with delocalized S bonds. A S molecular orbital (
1
S
) of C
6
H
6
is shown below (top view). The phase of the orbital is either shaded (+) or not shaded
(-).










a) Draw line(s) to indicate the nodal plane(s) in
1
S

b) What is the total number of S molecular orbitals in C
6
H
6
? 6

c) Below are 5 drawings of molecular orbitals for 6-membered ring structures. Four of them
show molecular orbitals of benzene. Circle the diagram that does not show the molecular
orbital of benzene.


















d) State whether
2
S and
5
S are higher, lower, or equal in energy to
1
S .
Pi-2: lower in energy
Pi-5: equal in energy





1
S

6
S
5
S

4
S

3
S
2
S


39

e) Calculate the average S -bond order and then the average BO.


























2
# # gelectrons antibondin ctrons bondingele
BO

3
2
0 6

electrons g antibondin electrons bonding S S

2
1
6
3

bonds
BO averageS
2
1
1
2
3
. totalBO avg