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Of your surname here

FAMILY NAME: ...........................................................................................

OTHER NAMES: ............................................................................................

STUDENT I.D. : ............................................................................................

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THE UNIVERSITY OF NEW SOUTH WALES

SCHOOL OF CHEMISTRY

SEMESTER 1 2014

CHEM1031 / CHEM1051 Chemistry A

1. TIME ALLOWED 2 hours.
2. READING TIME 10 minutes.
3. THIS EXAMINATION PAPER HAS 20 PAGES.
4. TOTAL NUMBER OF QUESTIONS 10 WRITTEN AND 10 MULTI-CHOICE.
5. ATTEMPT ALL QUESTIONS.
6. TOTAL MARKS AVAILABLE 120 MARKS = 60% OF THE COURSE MARK.
7. THE 10 WRITTEN QUESTIONS IN PART A ARE WORTH 10 MARKS EACH, AND THE 10 MULTI-
CHOICE QUESTIONS IN PART B ARE WORTH 2 MARKS EACH.
8. ALL ANSWERS TO PART A MUST BE WRITTEN IN INK. EXCEPT WHERE THEY ARE EXPRESSLY
REQUIRED, PENCILS MAY BE USED ONLY FOR FILLING IN THE GENERALISED ANSWER SHEET,
DRAWING, SKETCHING OR GRAPHICAL WORK.
9. THIS PAPER MAY NOT BE RETAINED BY THE CANDIDATE.
10. PRINT YOUR NAMES AND I.D. NUMBER AT THE TOP OF THIS PAGE, AND WRITE YOUR
SIGNATURE.
SPECIAL INSTRUCTIONS
11. PART A: WRITE ANSWERS TO PART A INTO THIS EXAM PAPER, USING BLUE OR BLACK INK. ALL
WORKING MUST BE SHOWN. APPROPRIATE UNITS MUST BE GIVEN FOR ALL NUMERICAL
ANSWERS. IF MORE SPACE IS NEEDED, USE THE ADDITIONAL WORKING PAGES PROVIDED,
AND INDICATE THE NUMBER OF THE ADDITIONAL PAGE USED ON THE QUESTION PAGE.
12. PART B: FOR EACH QUESTION CIRCLE THE LETTER NEXT TO YOUR SELECTED ANSWER, AND
FILL IN THE LETTER CORRESPONDING TO THE ANSWER ON THE GENERALISED ANSWER
SHEET. MARKS WILL BE AWARDED WHEN THE CORRECT ANSWER, ALONE, IS FILLED IN.
13. ENSURE YOUR PERSONAL DETAILS AND ANSWERS ARE ENTERED ON THE GENERALISED
ANSWER SHEET BEFORE THE END OF THE EXAM PERIOD. THE ANSWERS ON THE
GENERALISED ANSWER SHEET WILL BE USED TO DETERMINE THE MARKS FOR PART B.
14. CANDIDATES MAY BRING TO THE EXAMINATION: UNSW-APPROVED CALCULATOR.
15. THE FOLLOWING MATERIALS WILL BE PROVIDED: GENERALISED ANSWER SHEET, PERIODIC
TABLE AND DATA SHEET.
 WORKING PAGE

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 2

 PART A
WRITTEN QUESTIONS
QUESTION 1

(a) At 290.0K and 1.000 105 Pa, a 25.0 L sample of gas contains 0.3500 moles of argon, 0.6100 moles of neon.

(i) What is the total number of moles in this sample? [1 mark]

(ii) Are argon and neon the only components of the sample? Why? [2 marks]

(iii) What are the partial pressures of each gas? [2 marks]

(iv) If the volume was increased to 50.0 L and the temperature maintained at 290 K, what would the pressure be?
[1 mark]

(b) Which element am I?

(i) I have a high electron affinity. The element on my left in the Periodic Table has a lower electron affinity.
The element on my right in the Periodic Table has a higher ionization energy and basically no electron affinity. I
am toxic in my elemental state, but I am more commonly found in my non-toxic ionic state. Within my group, I
have the highest ionization energy.

(ii) I am a metal. My atomic radius is smaller than the atomic radius of the element with one fewer protons, but
my +1 ionic radius is larger than the +1 ionic radius of the element with one fewer protons. Of the two elements
in my group that have biological importance, I am the one with lower electronegativity.

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 3

QUESTION 2

(a) (i) Calculate the wavelength of light emitted when a hydrogen atom undergoes a transition from the n = 4
electronic state to the ground electronic state. [2 marks]

(ii) An emission spectrum from hydrogen atoms excited into the n = 4 electronic state displays six lines. Write
down the six pairs of values for n1 and n2 for these lines. [2 marks]

(iii) Write down the values for n1 and n2 for the transition from (ii) above which gives the shortest wavelength of
light. [1 mark]

2
(b) Using '1s ' notation, write the complete ground state electronic configurations of the following gaseous atoms
and ions. [2 marks]

(i) Zn

2+
(ii) Cu

(c) Write down all the species from part (b) which are paramagnetic. [1 mark]

2+ 2 3 +
(d) The ions F , Mg ,O ,N and Na are isoelectronic.

(i) What does isoelectronic mean? [1 mark]

(ii) Do these ions have identical radii? Why / why not? [1 mark]

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 4

QUESTION 3

(a) For each of the following, draw a Lewis diagram, describe the shape of the molecule, and describe the
hybridisation at the central atom.

(i) ClF3 (ii) SF6

Shape: Shape:

Hybridisation: Hybridisation:

3
(b) Draw four resonance structures for PO4 . Choose one of the structures at random, and indicate the formal
charges of all the atoms in that structure.

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 5

QUESTION 4
(a) Indicate the types of intermolecular forces possible between the two molecules listed as pairs in the table below,
by writing the word 'yes' or 'no' in the space provided to indicate if each force is possible or not.

The two molecules dipoledipole forces dispersion forces hydrogen bonds

(i) H2 and CH3OH

(ii) O2 and HCN

(iii) CH3OCH3 and H2O

(iv) CH3F and CH3F

(b) For each of the solutes in Column 1 of the table below, choose the solvent from Column 2 in which it will have
the greatest solubility, and write the name of the chosen solvent into Column 3.

Column 1: solute Column 2: solvent choices Column 3: chosen solvent

sodium bromide water, hexane, methanol

bromine water, carbon tetrachloride, ethanol

(c) Can the molecule He2+ exist? What is the bond order?

(d) Can the molecule O2+ exist? What is the bond order?

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 6

QUESTION 5
1
(a) At 25.0 C the vapour pressure of pure benzene (C6H6, molar mass = 78.1 g mol ) is 12300 Pa and that of pure
1
toluene (C7H8, molar mass = 92.1 g mol ) is 3540 Pa.

(i) Calculate the total vapour pressure of a mixture of 60.0 g of benzene and 120.0 g of toluene at 25.0 C,
assuming ideal behaviour of the mixture and assuming the liquid/gas phases are both present in equilibrium.

(ii) Calculate the mole fraction of toluene in the gas phase above the mixture described in (i) above.

n
(b) Use the van der Waals equation: (P + a( )2) (V nb) = nRT to calculate the pressure of 1.00 mol of argon in a
V
2 2
1.00 L container at 380 C. The van der Waals constants for argon are: a = 1.35 atm L mol
1
and b = 0.0322 L mol .

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 7

QUESTION 6
(a) In the Chemical Equilibrium laboratory experiment that you performed this Semester, you investigated the
reactions of calcium hydroxide and its products:

Reaction 1. Carbon dioxide gas was bubbled through a saturated solution of calcium hydroxide. A white precipitate
immediately formed.
Reaction 2. The mixture obtained in Reaction 1 was treated by passing more carbon dioxide through it. The white
precipitate disappeared.
Reaction 3. The solution obtained in Reaction 2 was heated to boiling. The white precipitate reappeared.

Write net ionic chemical equations for each of the chemical reactions described above.
Reaction 1:

Reaction 2:

Reaction 3:

(b) In the Chemical Equilibrium laboratory experiment that you performed this Semester, you investigated the
reaction of chromate ions with nitric acid to give dichromate ions. Write a net ionic equation for this reaction.

(c) Barium nitrate solution was added to the solution obtained in part (b). No change was observed. However when
sodium hydroxide solution was subsequently added, a precipitate formed. Write a net ionic equation for the
precipitation reaction.

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 8

QUESTION 7
(a) For the reaction: 2HI(g) H2(g) + I2(g) a mixture of the three gases in equilibrium at 425 C was found to
3 4 4
contain these concentrations: [HI] = 3.53 10 M, [H2] = 4.79 10 M, [I2] = 4.81 10 M.
(i) Write an expression for Kc in terms of the equilibrium concentrations.

(ii) Calculate Kc for the reaction.

(iii) What would be the effect on the equilibrium concentation of HI if the volume of the vessel containing the
gases was reduced, keeping the temperature constant?

(iv) It was found that on increasing the temperature of the mixture at equilibrium the concentation of HI
increased. Is the above reaction endo- or exothermic? Briefly justify your answer.

(b) For the reaction: N2(g) + O2(g) 2NO(g) Kc = 6.2 104 at 2000C (standard state = 1 mol L1)
(i) Calculate whether a net reaction will occur and, if so, in which direction (to the left, or to the right), for the
following initial conditions:
a 1.0 L flask containing 0.010 mol of N2, 0.010 mol of O2 and 0.010 mol of NO at 2000C.

(ii) Calculate Kc at 2000C for the reaction: NO(g) N2(g) + O2(g)

(iii) If additional N2 (g) was added to a mixture of N2(g), O2(g), and 2NO(g) at equilibrium, what effect would
this have on the amount of O2 present as equilibrium was restored (temperature and volume being kept
constant)?

(iv) Would the value of Kp be the same or different to Kc for this reaction? Briefly justify your answer.

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 9

QUESTION 8

(a) Fill in the missing entries in the table below for an aqueous solution at 25C.

+
[H ] /mol L1 pH [OH ] /mol L1 pOH

4
9.0 10

(b) Write down the formula and name for the conjugate acid of each of these species:

Formula of conjugate acid Name of conjugate acid

(i) ClO3

(c) In no more than two sentences, explain the meaning of the term 'zwitterion'.

(d) Calculate the pH of a 0.020 M solution of Ba(OH)2. You may assume that the barium hydroxide dissolves
completely.

(e) (i) The pKa of HF is 3.17. Calculate the pH of a 0.10 M solution of sodium fluoride.

(ii) Calculate the pH of a solution containing 0.100 M sodium fluoride and 0.120 M HF.

(iii) Calculate the pH of the solution from (ii) after adding 0.20 g (equivalent to 0.0050 mol) of NaOH to 1.00 L
of the solution, assuming there is no change in the volume of the solution.

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 10

QUESTION 9
(a) Solid copper has a heat capacity of 0.39 J K1 g1. Calculate the heat required to increase the temperature of
1.00 kg of solid copper by 60 C.

(b) Diborane (B2H6) is a highly reactive compound, a gas at room temperature and pressure, which was once
considered as a possible rocket fuel for the US space program.
(i) Write a chemical equation that represents the formation of diborane from its constituent elements in their
reference states.

(ii) Calculate the enthalpy of formation of diborane from the enthalpy changes for following reactions:
1
rH / kJ mol
2B(s) + 3/2 O2(g) B2O3(s) 1273
B2H6(g) + 3O2(g) B2O3(s) + 3H2O(g) 2035
H2(g) + O2(g) H2O(l) 286
H2O(l) H2O(g) +44

(c) Copper metal can be extracted from copper ores by Data (at 25 C, standard state = 1 bar)
heating in oxygen: fH / kJ mol1 S/ J K1 mol1
Cu2S(s) + O2(g) 2Cu(s) + SO2(g) Cu(s) 0 33
SO2(g) 297 248
(i) Calculate H for the above reaction at 25 C.
Cu2S(s) 80 121
O2(g) 0 205

(ii) Calculate S for the above reaction at 25 C.

(iii) Calculate G for the above reaction at 25 C.

(iv) Calculate the equilibrium constant for the above reaction at 25 C.

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 11

QUESTION 10

(a) What is the oxidation number of the element indicated in each of the following species?
2
Species P4 PH3 Cr2O7 H2 O2

Element P P Cr O

Oxidation Number

(b) Calculate the mass of copper produced in 25 minutes by the electrolysis of CuSO 4 solution with a current of
12 A.

3+ 2+
(c) The standard cell potential for the cell Al(s) | Al (aq) || Fe (aq) | Fe(s) is +1.24 V. Use the Nernst Equation to
3+ 2+
calculate the cell potential at 298K for the cell: Al(s) | Al (aq, 0.18 M) || Fe (aq, 0.85 M) | Fe(s).

(b) For the following electrochemical cell:

2+ 1 + 1
Mg(s) | Mg (aq, 1.00 mol L ) || Ag (aq, 1.00 mol L ) | Ag(s)
(i) Write a balanced halfequation for the reaction occurring at the anode.

(ii) Write a balanced halfequation for the reaction occurring at the cathode.

(iii) Write a balanced equation for the overall reaction occurring in the cell.

(iv) Using data from the adjacent table calculate the standard potential Standard reduction potentials, E / V
(emf) for this cell. 1
(at 25 C, standard state = 1 mol L )
2+
Mg | Mg 2.36
+
Ag | Ag +0.80

(v) Use the standard cell potential (emf) to calculate G for the cell reaction.

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 12

THIS SECTION OF THE
PAPER IS NOT
AVAILABLE
 CHEM1031

DATA SHEET

0 C = 273 K
1 atm = 760 mmHg = 101.3 kPa = 760 Torr
1 1 1 1
Ideal Gas Constant R = 8.314 J mol K = 0.08206 L atm mol K
23 1
Avogadro Number NA = 6.022 10 mol

1 atm = 760 mmHg = 101.3 kPa = 760 Torr = 1.013 bar

1
Faraday Constant F = 96,485 C mol

RT
Nernst Equation Ecell = Ecell nF ln Q

Faraday Equation Q=i t = amount electrons (mole) F

34
Planck Constant h = 6.626 x 10 Js

8 1
Speed of Light c = 2.998 x 10 m s

Planck Equation E = h = hc

Ideal Gas Law PV = nRT

1
Rydberg equation = RH (n12
1
n22
)
1

7 1
RH = 1.097 10 m

PLEASE SEE OVER

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 19

UNSW CHEM1031 & CHEM1051 FINAL EXAMINATION June 2014 20