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THE UNIVERSITY OF NEW SOUTH WALES SAMPLE FINAL EXAMINATION PAPER 2011 CHEM1031 Higher Chemistry 1A and CHEM1051 Higher Chemistry (Medicinal) 1A

For details of the instructions on the front page of your exam paper, see the the document published on Blackboard.

Sample Exam Paper

2 QUESTION 1 Write balanced ionic equations for the following chemical reactions. Include states of matter, but do not include spectator ions. (i) Solid barium hydroxide reacts with an excess of 0.1 M sulfuric acid to produce a precipitate of barium sulfate and water.

(ii)

A solution of copper(II) nitrate is added to a solution of sodium hydroxide to produce a precipitate of copper(II) hydroxide.

(iii)

Solid sodium oxide reacts with water to produce a basic solution.

(iv)

Solid calcium hydride reacts with water to produce a basic solution.

(v)

Sulfur dioxide gas reacts with water to produce an acidic solution.

(vi)

Solid zinc oxide reacts with sodium hydroxide solution to give a colourless solution.

3 QUESTION 2 (a) Calculate the frequency of electromagnetic radiation which has a wavelength of 532 nm.

(b)

Calculate the energy of one photon of electromagnetic radiation which has a frequency of 90.0!MHz.

(c)

Use the Rydberg equation:

1 1 1 ! = RH (n 2 n 2 ) 1 2

where RH = 1.097 " 107 m1 to calculate the wavelength of light required to cause a hydrogen atom to undergo a transition from the n = 1 electronic state to the n = 3 electronic state.

(d)

(i) Write down the values of the n and l quantum numbers for these orbitals: 3s 4d n= n= l= l=

(ii) Write down all the allowed values of the quantum number ml for the orbitals in a 3p sublevel. ml = (e) In the upper atmosphere chloromethane can be decomposed by light according to the reaction: CH3Cl # CH3(g) + Cl(g) The energy required for this reaction is 428 kJ mol1. If each molecule of chloromethane is decomposed by one photon, what is the maximum wavelength that photon can have?

4 QUESTION 3 (a) Using 'arrowsinlabeledboxes' notation, write the complete ground state electronic configurations of the following atoms and ions. (i) N

(ii) Mg

(iii) Cr

(iv) F

(v) V+

(b) Write down all the species from part (a) which are paramagnetic.

(c) Write down all the species from part (a) which are isoelectronic with a noble gas.

(d)

For each of the following molecules draw a Lewis diagram, describe the shape of the molecule, and describe whether the molecule has a permanent dipole moment.

(i)

BeCl2

(ii) PF3

Shape: Polar? yes / no

Shape: Polar? yes / no

5 QUESTION 4 For each of the following species draw a Lewis diagram, describe the shape of the species, and describe the hybridisation at the central atom. (i) BF3 (ii) SiCl4

Shape: Hybridisation: (iii) CO2

Shape: Hybridisation: (iv) H3O+

Shape: Hybridisation: (v) XeF2

Shape: Hybridisation:

Shape: Hybridisation:

6 QUESTION 5 (a) Would you expect the HOH angle in water to be larger or smaller than the HNH angle in ammonia (NH3)? Justify your answer in no more than two sentences.

(b)

(i) Draw all resonance structures for CO32.

(ii) Write down the hybridization of the carbon atom in CO32.

(iii) What type of orbitals on the carbon atom and oxygen atoms in CO32 overlap to produce the " bonds in this ion?

(iv) Would you expect the CO bond in CO32 to be longer or shorter than the CO bond in methanol, H3COH?

(c)

The table below shows the normal boiling points of the group 17 hydrides. Compound Normal boiling point / C (i) HF 20 HCl 85 HBr 67 HI 35

What is the dominant type of intermolecular force which determines the normal boiling points of the compounds HCl, HBr, and HI?

(ii) What is the dominant type of intermolecular force which determines the normal boiling point of HF?

(d)

Calculate the pressure exerted by 100.0 mol of xenon in a 15.0 L vessel at 300 K using the van n der Waals equation: (P + a(V)2) (V nb) = nRT where, for xenon, a = 4.19 atm L2 mol2 and b = 0.0511 L mol1

7 QUESTION 6 In the week 3 laboratory experiment the concentration of a sodium hydroxide solution was determined by titration with a standard potassium hydrogenphthalate (KHP) solution. (a) Calculate the concentration of KHP standard solution obtained by dissolving 5.10 g of KHP (molar mass 204.22 g mol1) into 250.0 mL of water, in a volumetric flask.

(b)

Four 25.00 mL samples of the KHP standard solution were each titrated with the unknown sodium hydroxide solution. The results are given in the table below. Titration Initial Reading (0.05 mL) 0.05 0.40 0.45 1.60 Final Reading (0.05 mL) 35.55 35.50 35.55 36.70 Titre (0.1 mL) Used in calculation? (Yes/No)

1 2 3 4

(i)

Complete the Titre data in the table.

(ii) Make use of data in the table to calculate the concentration of the sodium hydroxide solution, assuming that KHP is a monoprotic acid.

(iii) Complete the Used in calculation? data in the table, to indicate which titres were used in the calculation of the sodium hydroxide solution. Comment briefly on how you decided which titres to use in the calculation.

8 QUESTION 7 (a) A 340 mL cylinder contained xenon gas at 123 kPa and 20.0 mL of liquid 2-butanone at 25 C. (Data: the vapour pressure of 2-butanone is 13.3 kPa at 25 C.) (i) The volume of the container is increased to 1.00 L keeping the temperature constant. What is the total pressure in the container?

(ii) 100 mL of argon gas (measured at 101 kPa and 25 C) is then added to the 1.00 L container. What is the total pressure in the container, assuming the volume of liquid is still 20.0 mL?

(b) (i)

On the template below, sketch a labelled phase diagram for SO ,

2

using the data supplied below it.

pressure p/atm 78

0.00165 0.0013 temperature T/C 95

2

75.5

72.7

10

157

Data for SO : normal boiling point 10C; normal melting point 72.7C; triple point 75.5C at 0.00165 atm; critical point 157C at 78 atm. Solid SO has a vapour pressure of
2

0.0013 atm at 95C. (ii) Label the appropriate regions of the phase diagram as solid, liquid, and gas. (iii) Write down the highest temperature at which liquid sulfur dioxide can exist. (iv) In what state does sulfur dioxide exist as at 25 C and 40 atm? (v) Is solid sulfur dioxide more dense than liquid sulfur dioxide? Justify your answer.

9 QUESTION 8 (a) At 25 C the vapour pressure of pure benzene (C6H6, molar mass = 78.1 g mol1) is 95.1 Torr and that of pure toluene (C6H5CH3, molar mass = 93.1 g mol1) is 28.4 Torr. (i) Calculate the total vapour pressure of a solution containing 40.0 g of benzene and 20.0 g of toluene at 25 C, assuming ideal behaviour of the solution.

(ii) Calculate the partial pressure of benzene in the gas phase above the mixture.

(iii) A sample of the vapour in equilibrium with the mixture was isolated and cooled until the vapour completely condensed into liquid. Calculate the mole fraction of benzene in this liquid.

(b)

A solution of glucose in water freezes at 1.86 C. Calculate the concentration of glucose, expressed as mol kg1 (molality). (Molal freezing point depression constant for water = 1.853!K!kg!mol1)

(c)

Calculate the osmotic pressure (in atm) at 25 C of an aqueous solution containing 1.00 g of calcium chloride (CaCl2; molar mass = 111.0 g mol1) in 100.0 mL of solution.

10 QUESTION 9 (a) Complete the following table, writing none where appropriate:

Conjugate Acid

Species NH3 CH3CH2COOH HCO3

Conjugate Base

(b)

Supply the missing information in the table below:

+ [H ] 1 (mol L ) (i) 4 3.4 x 10

pH

[OH ] 1 (mol L )

pOH

(ii) 8.2

(c)

The pKa for hydrazoic acid (HN3) is 4.65. What is the pH of a 0.20 M HN3 solution?

11 QUESTION 10 (a) Complete the following table, by writing "increase", "decrease" or "no change" to indicate the effect each of the listed changes will have when applied to the mixture of gases in the following equilibrium reaction: 2 NO(g) + O2(g) 2 NO2(g) + heat Effect on amount of NO2 at equilibrium

Change Removing some NO from container Adding a catalyst Adding O2 to container Increasing temperature Compressing the container to a smaller volume (at constant temperature) (b)

Effect on Kp

Consider the electrochemical cell represented by the following cell diagram: Zn(s) | Zn2+(aq) || Ag+(aq) | 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 this cell.

(iv) Using data from the adjacent table calculate the standard emf for this cell. Standard reduction potentials, E / V (at 25 C, standard state = 1 mol L1) 0.76 Zn2+ | Zn Ag+ | Ag (v) Use the cell emf to calculate #G for the cell reaction. 0.80

(b)

Calculate the current required (in amps) to deposit 0.500 g of chromium metal from a solution containing Cr3+(aq) in a period of 1.00 hour.

12

PART B MULTIPLE CHOICE

There are 20 multiple choice questions in this section, each worth 2 marks. Each multiple choice consists of a statement or question followed by 5 possible choices. Select the choice that best answers the statement or question by CIRCLING the appropriate letter.

There is only one correct answer to each question. TRANSFER YOUR ANSWERS TO THE GENERALISED ANSWER SHEET WITH THE PENCIL PROVIDED.

(THIS SECTION OF THE EXAM PAPER IS NOT INCLUDED IN THIS DOCUMENT)

13 PART C OPTIONAL MULTIPLE CHOICE There are 8 multiple choice questions in this section. Each multiple choice consists of a statement or question followed by 5 possible choices. Select the choice that best answers the statement or question by CIRCLING the appropriate letter. There is only one correct answer for each question. TRANSFER YOUR ANSWERS TO THE GENERALISED ANSWER SHEET WITH THE PENCIL PROVIDED. YOUR MARK FOR THIS PART WILL BE DETERMINED FROM YOUR ENTRIES ON THE GENERALISED ANSWER SHEET.

(THIS SECTION OF THE EXAM PAPER IS NOT INCLUDED IN THIS DOCUMENT)

14

DATA SHEET 0 C = 273 K 1 atm = 1.031 bar = 760 mmHg = 101.3 kPa = 760 Torr Gas Constant R = 8.314 J mol1 K1 = 0.08206 L atm mol1 K1 Avogadro Number Speed of Light Planck Constant Planck equation : Faraday Constant Nernst Equation Faraday Equation NA = 6.022 " 1023 mol1 c = 2.99 " 108 m s1 h = 6.626 " 1034 J s E = h$ = hc/! F = 96,500 C mol1 Ecell = Ecell
RT nF

ln Q

Q = i " t = amount electrons (mole) " F

Periodic Group Numbers 6 7 8 9

2

10

11

12

13

14

15

16

17

18

The!Periodic!Table

H
5 6 7 8 9

He
4.003 10

1.008

Li
10.81 13 14 15 12.01 14.01 16

Be

O
16.00

F
19.00 17

Ne
20.18 18

6.941

9.012

11

12

Na
26.98 24 25 26 27 28 29 30 31 32 28.09

Mg

Al

Si

P
30.97 33

S
32.07 34

Cl
35.45 35

Ar
39.95 36

22.99

24.31

19

20

21

22

23

K
52.00 42 44 45 46 47 48 49 54.94 43 99Tc 55.85 58.93 58.69 63.55 65.39 69.72

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge
72.59 50

As
74.92 51

Se
78.96 52

Br
79.90 53

Kr
83.80 54

39.10

40.08

44.96

47.88

50.94

37

38

39

40

41

Rb
95.94 74 75 76 77 78 79 80 (98.91) 101.1 102.9 106.4 107.9 112.4

Sr

Zr

Nb

Mo

Ru

Rh

Pd

Ag

Cd

In
114.8 81

Sn
118.7 82

Sb
121.8 83

Te
127.6

I
126.9

Xe
131.3

85.47

87.62

88.91

91.22

92.91

55

56

57

72

73

Cs
183.9 186.2 190.2 192.2 195.1 197.0

Ba

La

Hf

Ta

Re

Os

Ir

Pt

Au

Hg
200.6

Tl
204.4

Pb
207.2

Bi
209.0

84 210Po (210.0)

85 210At (210.0)

86 222Rn (222.0)

132.9

137.3

138.9

178.5

180.9

87 223Fr 59 60 62

88 226Ra

89 227Ac 63 64 65 66 67 68 69 70 71

(223.0)

(226.0)

(227.0)

58

Ce
140.9 92 144.2 (144.9)

Pr

Nd

61 145Pm

Sm
150.4

Eu
152.0

Gd
157.3

Tb
158.9

Dy
162.5

Ho
164.9

Er
167.3

Tm
168.9

Yb
173.0

Lu
175.0

KEY
91 231Pa

140.1

Atomic N !

90

Symbol ! C Atomic Weight ! 12.01 U

(231.0)

Th

93 237Np (237.0)

94 95 96 97 239Pu 243Am 247Cm 247Bk (239.1) (243.1) (247.1) (247.1)

98 252Cf (252.1)

99 252Es (252.1)

100 101 102 257Fm 256Md 259No (257.1) (256.1) (259.1)

103 260Lr (260.1)

232.0

238.0

) is the relative atomic mass of the most common radioactive isotope, the mass number of which is given as a superscript.