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Monash University


Semester One Examination Period
2011
Faculty of Science

EXAM CODES: CHM1011

TITLE OF PAPER: CHEMISTRY

EXAM DURATION: 3 hours writing time

READING TIME: 10 minutes

THI S PAPER I S FOR STUDENTS STUDYI NG AT:( tick where applicable)
Berwick Clayton Malaysia Off Campus Learning
Open Learning Caulfield Gippsland Peninsula
Enhancement Studies Sth Africa Pharmacy
Other (specify)

During an exam, you must not have in your possession, a book, notes, paper, electronic
device/s, calculator, pencil case, mobile phone or other material/item which has not been
authorised for the exam or specifically permitted as noted below. Any material or item on
your desk, chair or person will be deemed to be in your possession. You are reminded that
possession of unauthorised materials in an exam is a discipline offence under Monash Statute 4.1.

No examination papers are to be removed from the room.

AUTHORISED MATERIALS

CALCULATORS YES NO
* Calculators with School of Chemistry/Faculty of Science authorization label only

OPEN BOOK YES NO

SPECIFICALLY PERMITTED ITEMS YES NO

There are 3 sections in this paper for a total of 180 marks.
The questions are not of equal weight.
You should spend approximately 1 minute for each mark available.
Answer all questions in this booklet.


Candidates must complete this section if required to write answers within this paper


STUDENT ID __ __ __ __ __ __ __ __ DESK NUMBER __ __ __ __

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DATA SHEET

Useful equations


v = c


E = hv





Bond order =

1
2
(# bonding electrons - # anti-bonding electrons)


Physical constants

c = 2.998 x 10
8
ms
-1

h = 6.626 x 10
-34
J.s

R = 1.097 x 10
7
m
-1

N
A
= 6.022 10
23



1

= R
1
n
f
2

1
n
i
2
|
\


|
.
|
|
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Part A Physical Chemistry
(75 marks, 75 minutes)

QUESTION A1 (4 + 2 + 2 + 1 = 9 marks)

(a) The Rydberg equation may be used to calculate the energy difference between any
pair of orbitals in a single electron atom or ion. Calculate the wavelength (in
nanometers) of the transition from the n=1 to n=4 levels in atomic hydrogen. Express
your answer to four significant figures.















(b) Convert the wavelength you determined in part (a) into frequency.








(c) Convert the frequency you determined in part (b) into energy.








(d) Does this transition correspond to an emission or an absorption event?




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QUESTION A2 (3 + 2 + 1 + 1 = 7 marks)

(a) Using the set of three dimensional axes below, sketch an s, p
z
and a

d
x
2
y
2
atomic
orbital.

s p
z


d
x
2
y
2


(b) Using the labeled axes below, sketch the radial distribution function for a 3s
atomic orbital.


(c) What value for the angular momentum quantum number l corresponds to the seven
f atomic orbitals.





(d) What values for the magnetic quantum number m
l
are permitted for the subshell
with l = 2.




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QUESTION A3 (3 + 6 = 9 marks)

(a) Write both the full and condensed electronic configurations for each of the
species listed below :

Cl


Ti



Se
2-



(b) Use electronic configurations below to answer parts (i) - (vi):
A: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6

B: 1s
2
2s
2
2p
6
3s
1
3p
5

C: 1s
2
2s
2
2p
6
3s
3
3p
5
4s
2
3d
10
4p
3

D: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1

E: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
5


(i) Which of the electronic configurations above represents at atom in the ground
state?



(ii) Which of the electronic configurations above disobey the Pauli Exclusion
Principle?



(iii) Which of the electronic configurations above represents at atom in an excited
state?



(iv) Which of the electronic configurations above represent a neutral noble gas?



(v) Which of the electronic configurations above represent a transition metal?



(vi) Which of the electronic configurations above represent an alkali metal?


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Question A4 (1 + 2 + 3 = 6 marks)

(a) Which Group of the Periodic Table has the second most exothermic values for
electron affinity (EA
1
):
atom(g) + e
-
ion
-
(g) U = EA
1






(b) X is an atom from the third row of the Period Table. The data below
corresponds to the first five ionization energies of X.

IE
1
IE
2
IE
3
IE
4
IE
5

789
kJ/mol
1580
kJ/mol
3230
kJ/mol
4360
kJ/mol
16100
kJ/mol


Identify element X. Briefly explain your reasoning.







(c) In each of the three groupings listed below, rank the species in order from
largest to smallest size.

Cl , S , F





Be , Na , Mg




Br , Br
-
, Br
+



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Question A5 (6 + 3 + 4 + 4 = 17 marks)
This question refers to the molecule, SO
3
and the anion, SO
3
2-
.

(a) (i) Draw a Lewis structure for each species, being sure to show lone pairs and
any formal charges.












(ii) What are the bond angles in each of these species?



SO
3
_____________________



SO
3
2-
. ___________________

(b) In the table below, enter the number of electron domains about the central
atom, and use VESPR theory to predict the parent geometry and the molecular
geometry for each species.


Species # of Electron
Domains
Parent
Geometry
Molecular
Geometry
SO
3








SO
3
2-







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Question A5 continued
(c) The SO
3
2-
anion displays resonance.
(i) Draw Lewis structures to show the possible resonance structures.










(ii) Based on these resonant structures, what is the bond order of the sulfur-
oxygen bonds in the SO
3
2-
anion? Explain your answer.








(d) (i) Does the molecule SO
3
have a permanent dipole moment? Be sure to
justify your answer.









(ii) Does the SO
3
2-
anion have a permanent dipole moment? Be sure to justify
your answer.

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Question A6 (8 marks)

Develop a hybridisation scheme for the molecule acetonitrile, H
3
C-CN. Draw
separate diagrams for the o and t bonding arrangements. Include all hybrid orbitals
and appropriate labels.
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Question A7 (2 + 1 + 1 + 1 + 6 + 1 + 1 = 13 marks)
A spectroscopist at the University of Hong Kong recently made an unexpected
discovery during an experiment. He was mixing gaseous C
2
H
4
and B
2
H
6
over hot Mg
in attempt to make Mg C and MgB, which have been proposed as molecules in space.
To his surprise, this experiment actually produced the diatomic molecule, BC.

a) Identify how many valence electrons there are for both atomic boron and
carbon, and indicate which atomic orbitals these electrons occupy.







b) Comparing boron and carbon, which is the more electronegative element?



c) In molecular orbital theory, namethe two molecular orbitals (MOs) created
when two 2s atomic orbitals overlap.






d) In molecular orbital theory, 2p atomic orbitals may also overlap to create the
same kind of MOs from part c) above. Yet 2p atomic orbitals may also overlap
in a different way, creating two different kinds of MOs. Name these two
orbitals.







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Question A7 cont
e) Using your answers from parts a), b), c) and d) above and the MO framework
below, draw the MO diagram for BC. Include all necessary labels.

e)
f) How does the MO diagram indicate whether this molecule is diamagnetic or
paramagnetic?




g) What is the bond order for the BC molecule?




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Question A8 (2 + 4 = 6 marks)
Strong hydrogen bonding is observed for both hydrogen fluoride, HF, and water,
H
2
O. This is ultimately due to the large difference between the electronegativity of
hydrogen (2.1) and fluorine (4.0) and oxygen (3.5).

a) When comparing the hydrogen bonds for the two dimers in the figure below,
which would you expect to exhibit the strongest hydrogen bond. Explain.








b) The boiling point for H
2
O is actually higher than the boiling point of HF,
indicating that the overall hydrogen bonding is stronger in water. Draw a
diagram, and give an explanation to explain this observation.





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Part B Organic Chemistry
(60 Marks)

Question B1 (5 marks)

a) Draw a structural formula for each of the following compounds:

i) 4,4-Dichloro-2-methylhexane









ii) Triethylamine










b) Give the systematic name for each of the following compounds:

i)



Answer:


ii)



Answer:

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Question B1 cont

c) Draw a cyclic constitutional isomer of the molecule drawn in Question 1b, part ii).






















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Question B2 (9 marks)


Consider the following transformation:







a) Draw the structures of the two alkenes which could be used to generate alkyl
bromide A.












Alkene #1 Alkene #2


b) One of these viable alkenes leads to a better synthetic yield of A. Identify the
preferred alkene and explain your choice. (Hint: Consider reaction
intermediates).


Preferred Alkene #:


Reason:










A
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Question B2 cont


c) Write a reaction mechanism for the transformation of your preferred alkene into alkyl
bromide A.





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Question B3 (12 marks)

Complete the following reaction scheme by providing reagents and products in the
boxes provided.

Also clearly label the following terms on the scheme:

- A Grignard reagent
- A substitution reaction




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Question B4 (4 marks)

Molecular nano-figures can be prepared via the reaction drawn below:







a) What is the name of the new functional group created in molecule B.






b) Draw the structure of the diol used to create molecule B.






c) Define the term protecting group and briefly account for its use in organic
synthesis.








B
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Question B5 (10 Marks)

Benzene is a remarkable example of an aromatic compound, discovered in 1825 and
whose structure was proposed in 1872. Consider the following compounds:



(i) Define Hckels rule and indicate which of the structures shown above is
aromatic.
Show your calculations.







(ii) Based on your answer to part (i), which compounds would react directly
with bromine?






(iii) For each compound A to D, write how many signals you would expect to
observe in the
13
C-NMR spectrum

A = C =


B = D =


(iv) For each compound A to D, write how many signals you would expect to
observe in the
1
H-NMR spectrum. Also provide integration values for each
signal.

A = C =



B = D =
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Question B6 (8 Marks)

1
H-NMR spectroscopy is a powerful tool for determining the structure of organic
compounds.
(i) What are the three types of information you can obtain from a
1
H-NMR
spectrum and what do they tell you about the structure of an unknown
compound?













(ii) Consider the following compound drawn below. Indicate the splitting of
each of the three types of hydrogens shown in bold and numbered a-c.










(i) Define the rule that determines the splitting of a signal and using a simple
diagram describe why this rule allows you to predict the number of
signals.





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Question B7 (6 Marks)

Various types of bonding interactions define the properties of molecules. Consider the
following table:























(i) What type of secondary bonding causes the different boiling points
observed in this table?




(ii) Explain your answer to part (i) by discussing an appropriate pair of
molecules in the table. Use a diagram in which the secondary bonding is
shown.









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Question B8 (6 Marks)

Draw a full mechanism for the following reactions

(i)
















(ii)



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PART C Inorganic p-block Chemistry
(45 marks, 45 minutes)

Question C1 (7 + 2 + 9 = 18 marks)

(a) (i) Non-metal elements such as N (nitrogen) or S (sulfur) form basic oxides

True False [Tick the correct answer]


(ii) Write down the formula for one oxide of sulfur and give its name.




(iii) Write a balanced equation, with reaction conditions given above the arrow,
for the preparation of the oxide you gave as answer in (a)(ii).




(iv) Briefly describe a good/beneficial use of the oxide of S you gave in
(a)(ii).[this might involve converting it in to another compound]:





and an environmentally bad effect of this oxide:





(b) Write down the oxidation state for the N or P elements in each of the following
group 15 oxide or oxoacid compounds:

- NO
2




- H
3
PO
4




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Question C1 cont
(c) (i) Draw a Lewis structure showing all bonds and all electron dots on O atoms.
Indicate the central element. Then, by use of VSEPR theory, predict and name the
molecular geomery around the central element for the following oxoacid:

- H
3
PO
4
(orthophosphoric acid)









(ii) How many lone pairs of electrons are on P in your Lewis structure for H
3
PO
4
?




(iii) The four P-O bond distances in H
3
PO
4
are not all equal. Explain what relevance
this has with respect to the Lewis structure you have drawn in c(i), and comment on
how this changes for the fully deprotonated species PO
4
3-
.













(iv) The three protons in H
3
PO
4
dissociate in water with different pK
a
values.
Complete the following statement:

The proton that is lost first, to yield H
2
PO
4
-
(dihydrogen phosphate), has the
____________________highest / lowest) pK
a
value and thus is the
____________________most / least) acidic. A possible reason for this is
_____________________________________________________________________
___________________________________________________________________
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Question C2 (2 + 6 + 2 = 10 marks)
(a) What bonding property of nitrogen, N
2
, makes it useful as an inert blanket of gas
for preparing reactive chemicals under (e.g. in a N
2
-filled glove-box)? Why is it
unreactive under normal laboratory conditions?





(b) Fritz Haber, an early industrial chemist in Germany, made the important discovery
that N
2
could, in fact, be used to make ammonia, NH
3
, a compound widely used in
industry as well as to make other useful, and sometimes dangerous, chemicals.

In view of the equilibrium shown;

N
2
+ 3H
2
= 2NH
3
(H = -92 kJ mol
-1
)

Complete the following statement by inserting the correct choice of word (see
parentheses) or sentence:

The reaction shown by the above equilibrium is
____________________ (endothermic / exothermic) but occurs at a very
____________________ (slow / fast) rate. By Le Chateliers principle, that states that
_____________________________________________________________________
_____________________________________________________________________
an increase in pressure will ____________________ (favour / disfavour) NH
3

formation. Therefore a ____________________ (deactivator / catalyst) is used , such
as____________________ (sodium chloride / iron oxide ) which increases
the rate of reaction by reducing the activation energy, but at sufficiently low T so that
N
2
and H
2
are minimised.
(c) In the 1
st
year chemistry laboratory, students would expect the Safety/OHS
instructions for a bottle of concentrated aqueous ammonia (so-called 0.88 NH
3
) to
state the following:




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Question C3 (1 + 2 + 2 + 3 = 8 marks)

In regard to the chemistry and environmental aspects of ozone:

(a) Complete the following statement using one of the options in parentheses:
Ozone, O
3
, is an important constituent of the upper atmosphere as it shields
organisms from ____________________ (invaders from Mars / UV radiation /
IR radiation).

(b) Photochemical processes are involved in ozone production and these usually
involve radical production. What is a radical?





(c) Identify the missing species A and B

O
2(g)
+ h A
(g)
+ A
(g)


A
(g)
+ O
2(g)
B
(g)



A =

B =

(d) To reverse the detrimental environmental effects that sprays containing CFCs
(chlorofluorocarbons/freons) have on the ozone layer, these CFCs are being
phased out of common usage.

(i) Identify the missing species X in the following reaction

CFCl
3
+ h X + Cl
(freon-11)

X =

(ii) Which of X or Cl reacts with and destroys ozone?




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Question C4 (3 + 2 + 1 + 3 = 9 marks)

The following questions relate to electrically conducting p-block materials used
widely in the electronics and computer industries.

(a) Draw a labeled band energy diagram for the intrinsic semiconductor
germanium, Ge, (Group 14) indicating the band gap, the valence band (VB)
and the conduction band (CB), and shade filled molecular orbital levels.











(b) Does the band gap increase or decrease as one goes down Group 14 from C
(diamond), Si, Ge to Sn. Give a brief reason.





(c) In view of your answer to (b), state which of these elements gives the largest
electrical conductivity in the solid state.



(d) The computer chip industry dopes pure germanium crystals with, for
example, traces of gallium, Ga, (Group 13) to accurately increase the
conductivity of the resulting extrinsic semiconductor.

(i) Indicate, with a reason, if the charge carriers are positive holes (h
+
) or
electrons (e
-
).




(ii) Why is the conductivity increased after doping with Ga?





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END OF PAPER