UNIVERSITY OF PRETORIA UNIVERSITEIT VAN PRETORIA ` DEPARTEMENT OF CHEMISTRY DEPARTMENT CHEMIE DATE / DATUM: TIME / TYD: MARKS / PUNTE:

2008.05.30 120 min 80

Outeursreg voorbehou

Fakulteit Natuur- en Landbouwetenskappe CHM 171 EXAMINATION / EKSAMEN

Internal Examiners / Interne Eksaminatore: External Examiner / Eksterne Eksaminator: Surname and Initials Van en Voorletters Signature Handtekening

Dr FR Vogel Dr RJ Bowen Dr EMM Venter Prof WJ Schoeman

Student number Studentenommer

Marks / Punte Question 1 / Vraag 1 Section A Afdeling A Question 2 / Vraag 2 Question 3 / Vraag 3 Question 4 / Vraag 4 Question 5 / Vraag 5 Questtion 6 / Vraag 6 Section B Afdeling B Total / Totaal Section A / Afdeling A: Instructions / Instruksies 5 5 7 6 13 9 38 80(+3 bonus)

Examiner / Eksaminator

1. Answer all questions in ink. Answers in pencil will not be marked. Beantwoord alle vrae in ink. Antwoorde in potlood sal nie nagesien word nie. 2. Silent calculators may be used. Geluidlose sakrekenaars mag gebruik word. 3. Do not use Tipp-Ex or any similar liquid paper product on your paper. Answers that should not be marked must be clearly indicated. Geen Tipp-Ex of soortgelyke vloeibare papiermiddels mag op die antwoordstel gebruik word nie. Antwoorde wat nie nagesien moet word nie, moet duidelik doodgetrek word. 4. All cellphones must be switched off. Alle selfone moet afgeskakel wees.

Section A / Afdeling A: Show all calculations / Toon alle berekeninge Question 1/ Vraag 1 [5]

Fluorocarbonyl hypofluorite has the composition 14.6% C, 39.0% O, and 46.3% F. If the molar mass of the compound is 82 g/mol, determine the molecular formula of the compound. Fluoorkarbonielhipofluoriet bestaan uit 14.6% C, 39.0% O, en 46.3% F. Indien die molekulre massa van die verbinding 82 g/mol is, bepaal die molekulre formule van die verbinding.

Question 2/ Vraag 2

[5]

Silver nitrate is added to a 25 cm3 sample of hydrochloric acid. A white precipitate of silver chloride is then filtered off. If the dry precipitate weighs 0.3537 g, determine the pH of the hydrochloric acid solution. Silwernitraat word by 25 cm3 soutsuur oplossing gevoeg. n Wit presipitaat van silwerchloried vorm wat dan afgefiltreer word. Indien die gedroogde presipitaat 0.3537 g weeg, bepaal die pH van die soutsuur oplossing.

Vraag 3/ Question 3

[7]

Apply Hesss Law, use the data of the given reaction and data from the data table to calculate the enthalpy change for the formation of nitrogen monoxide from its elements. (Hint: Which reaction is described with the data: H f H2O(g) = 241.8 kJ / mol ) Pas die Wet van Hess toe, gebruik die data van die gegewe reaksie en data uit die datatabel en bereken die entalpie verandering vir die vorming van stikstofmonoksied vanuit sy elemente. (Wenk: Watter reaksie word beskryf met die data: H f H2O(g) = 241.8 kJ / mol ) 4 NH3 (g) + 5 O2(g) 4 NO(g) + 6 H2O(g) H rxn = 906.2 kJ

Vraag 4 / Question 4

[6]

How much heat is released when a mixture containing 10.0 g CS2 and 10.0 g C2 reacts by the equation Hoeveel warmte word afgegee wanneer 10.0 g CS2 met 10.0 g C2 reageer volgens die vergelyking CS2(g) + 3 C2(g) S2C2(g) + CC4(aq) H = -232 kJ

Vraag 5 / Question 5 Consider the following reaction: Beskou die volgende reaksie: Ni(s) Hf(kJ/mol) S(J/Kmol) a) 0 29.87 + 4CO(g) -110.525 197.674 Ni(CO)4(g) -602.9 410.6

[13]

Is the reaction product-favoured at 25C? Is die reaksie produkbevoordeeld by 25C? [6]

b)

Is the reaction enthalpy or entropy driven? Explain. Is die reaksie entalpie of entropie gedrewe? Verduidelik. [2]

c)

What is the value of K at 25C? Wat is die waarde van K by 25C? [2]

d)

At what temperature, in C, will this reaction become spontaneous? By watter temperatuur, in C, sal hierdie reaksie spontaan wees? [3]

Question 6 / Vraag 6 Consider the following reaction: Beskou die volgende reaksie: 2MnO4(aq) + 5Zn(s) + 16H+(aq) 2Mn2+(aq) + 5Zn2+(aq) + 8H2O() a)

[9]

Determine the cell potential, Ecell, at 25C when the cell is operated at pH 2.00 with [MnO4] = 0.12 mol/dm3, [Mn2+] = 0.0010 mol/dm3, and [Zn2+] = 0.015 mol/dm3. Bepaal die selpotensiaal, Esel, by 25C van die sel by n pH van 2.00 met [MnO4] = 0.12 mol/dm3, [Mn2+] = 0.0010 mol/dm3 en [Zn2+] = 0.015 mol/dm3. [5]

b)

Calculate the standard free energy of the cell. Bepaal die standaard vrye energie van die sel. [2]

c)

Calculate the equilibrium constant for the reaction at 25C. Bereken die ewewigskonstante vir die reaksie by 25C. [2]

Section B / Afdeling B/: Multiple choice / Veelvuldige keusevrae Instructions: Answer all the questions on side 2 on the answer sheet provided. Complete the biographical section on side 2. Mark only one oval per question. Mark only one oval per question. Use a pencil only. Instruksies: Beantwoord die vrae op die gegewe antwoordblad op kant 2. Voltooi die biografiese inligting op kant 2. Merk net een ovaal per vraag. Gebruik alleenlik n potlood. Question 1 / Vraag 1 For quality control of the optical reader, please colour the oval 1(i). Kleur asseblief die sirkel 1(i), vir die kwaliteitskontrole van die optiese merkleser, in. [0] Question 2 / Vraag 2 When the Fe3+ cation forms from a neutral Fe atom, the following electrons are lost: Wanneer die Fe3+-katioon uit n neutrale Fe-atoom vorm, word die volgende elektrone afgegee:

a) b) c) d) e)

one 4s and two 3d electrons / een 4s en twee 3d elektrone one 4s, one 3d and one 3p electrons / een 4s, een 3p en een 3s elektrone two 4s and one 3d electrons / twee 4s en een 3d elektrone one 4s, one 3p and one 3s electrons / een 4s, een 3d en een 3p elektrone None of the above / Nie een van bogenoemde nie. [2]

Question 3 / Vraag 3 Which of the following orbitals can not exist according to the quantum theory? Watter van die volgende orbitale kan nie volgens die kwantumteorie, bestaan nie?

a) 3s g) 4d

b) 3p h) 4f

c) 3d d) 3f i) none / geeneen.

e) 4s

f) 4p [2]

Question 4 / Vraag 4 Consider the first three elements of the fourth period. Which element will have the largest second ionization energy, IE2? Beskou die eerste drie elemente van die vierde periode. Watter element sal die grootste tweede ionisasie energie, IE2, besit?

a) Li g) K

b) Be h) Ca

c) B i) Sc

d) Na e) Mg j) none / geeneen.

f) Al [3]

Question 5 / Vraag 5 Consider the first three elements of the fourth period. Which element will have the largest electron affinity? Beskou die eerste drie elemente van die vierde periode. Watter element sal die grootste elektronaffiniteit besit?

a) Li g) K

b) Be h) Ca

c) B i) Sc

d) Na e) Mg j) none / geeneen.

f) Al [2]

Question 6 / Vraag 6 Consider the densities of the five unknown elements, A E, found in the same period. Which element will be the smallest? Beskou die digthede van die vyf onbekende elemente, A E wat in dieselfde periode voorkom. Watter element sal die kleinste wees?

a) A ( 0.9 g/cm3) e) E ( 6.2 g/cm3) Question 7 / Vraag 7

b) B ( 1.8 g/cm3) f) none / geeneen.

c) C ( 3.1 g/cm3)

d) D ( 4.5 g/cm3) [2]

Consider ClO2F2 + . The electron pair geometry and molecular geometry for this ion will be ___ and ___. Beskou ClO2F2 +. Die elektronpaargeometrie en die molekulre geometrie sal __ en ___ wees.

a) b) c) d) e) f) g)

Trigonal Bipyramidal and Trigonal Bipyramidal / Trigonaal Bipiramidaal en Trigonaal Bipiramidaal. Trigonal Bipyramidal and and See-saw / Trigonaal Bipiramidaal en Wipplank. Octahedral and Square Pyramidal / Oktahedraal en Vierkantig Piramidaal. Octahedral and Square Planar / Oktahedraal en Vierkantig Planr Tetrahedral and Tetrahedral / Tetrahedraal en Tetrahedraal Tetrahedral and Trigonal Pyramidal / Tetrahedraal en Trigonaal-piramidaal None of the above / Nie een van bogenoemde nie. [3]

Question 8 / Vraag 8 The approximate sizes of the bonding angles in the following molecule is the following: Die benaderde groottes van die bindingshoeke in die volgende molekule is die volgende:

H
b) 109 & 180 e) only / slegs 109 c) 90 & 180 f) None / Geeneen [2]

a) 109 & 120 d) only / slegs 120 Question 9 / Vraag 9 Which molecule(s) will be polar? Watter molekule(s) is polr?

a) BF3

b) BF4

c) CF3+

d) CF4

e) BrF3

f) BrF4 3+

g) both CF3+ and BrF3 / beide CF3+ en BrF3 i) none/ geeneen

h) both CF4 and BrF4 3+ / beide CF4 en BrF4 3+ [5]

Question 10 / Vraag 10 A hypothetical element consists of two naturally occurring isotopes with the following relative masses: 76.76 amu and 80.94 amu. The percent abundance of the former isotope is 76.31%. The average relative atomic mass of this element is: n Hipotetiese element bestaan uit twee natuurlike isotope met die volgende relatiewe massas: 76.76 ame en 80.94 ame. Die natuurlike voorkoms van die eersgenoemde isotoop is 76.31%. Die gemiddelde relatiewe atoommassa van hierdie element is:

a) 120.3 amu e) none / geeneen

b)

78.85 amu

c)

77.75 amu

d)

60.17 amu

10

[3] Question 11 / Vraag 11 Which species below is the nitride ion? Watter van die volgende spesies is die nitriedioon? a) e) Na+ N3 b) f) NO3 c) none / geeneen NO2 d) NH2 [1]

Question 12 / Vraag 12 When 175 g water at 24.1C is mixed with an unknown mass of water at a temperature of 55.1C, the final temperature of the mixture is 36.6C. What is the mass of the second sample of water? The specific heat of water is 4.184 J/gK. Indien 175 g water by 24.1C met n onbekende hoeveelheid water by 55.1C gemeng word, is die finale temperatuur van die mengsel 36.6C. Wat is die massa van die tweede monster water? Die spesifieke warmte van water is 4.184 J/gK. a) e) 32.8 g 259 g b) f) 75.0 g c) none / geeneen 102 g d) 118 g [4]

11

Questions 13 to 17 refer to the following unbalanced reaction equation: Vrae 13 tot 17 verwys na die volgende ongebalanseerde reaksie-vergelyking: C2(g) CO3(aq) + C(aq) (in basic solution/ in basiese oplossing) Balance the given reaction equation, using the half-reaction method. Balanseer die gegewe reaksievergelyking, deur gebruik te maak van die halfreaksie-metode.

Question 13 / Vraag 13 What is the oxidation number of chlorine in the chlorate ion? Wat is die oksidasiegetal van chloor in die chloraat ioon? a) g) -6 +4 b) h) -5 +5 c) i) -4 +6 d) j) -2 e) 0 none / geeneen f) +2 [1] Question 14 / Vraag 14 How many electrons are transferred in total in this redox reaction ? Hoeveel elektrone word in totaal in hierdie redoks-reaksie oorgedra ? a) g) 1 12 b) h) 2 c) 3 none / geeneen d) 6 e) 8 f) 10 [2]

12

Question 15 / Vraag 15 What is the stoichiometric coefficient of C2 in the final reaction? Wat is die stogiometriese koffisint van C2 in die finale reaksie? a) g) 1 8 b) h) 2 10 c) i) 3 12 d) 4 e) j) none / geeneen 5 f) 6 [2] Question 16 / Vraag 16 What is the stoichiometric coefficient of CO3 in the final reaction? Wat is die stogiometriese koffisint van CO3 in die finale reaksie ? a) g) 1 8 b) h) 2 10 c) i) 3 12 d) 4 e) j) none / geeneen 5 f) 6 [2] Question 17 / Vraag 17 What is the stoichiometric coefficient of OH in the final reaction? Wat is die stogiometriese koffisint van OH in die finale reaksie? a) g) 1 8 b) h) 2 10 c) i) 3 12 d) 4 e) j) none / geeneen 5 f) 6 [2]

Table / Tabel

Species Spesie
C2H6(g) H2(g)

Hf [kJ.mol1] (298.15 K) -83.85

S [JK-1mol-1] (298.15 K) 229.2 130.7 127.19 239.7 213.74 256.77 248.21

G [kJmol1] (298.15 K) -31.89 -166.14 -162.5 -393.36 -371.04 -300.13

Species Spesie
Cl2(g) H2O (l) H2O (g) Ag (aq) NH3 (g) HCl (g) C (s, graphite / grafiet)
+

Hf [kJ.mol1] (298.15 K)

S [JK-1mol-1] (298.15 K) 223.08 69.95 188.83 192.77 64.46 42.55 5.6

G [kJmol1] (298.15 K) -237.15 -228.59 77.1 -16.37 -95.3 -203.9

-285.83
-241.8 45.9 92.3

CH3OH (l) -238.4 CH3OH (g) -201.0 CO2 (g) SO3 (g) SO2 (g) O2 (g) NaHCO3(s) -947.7 -393.5 -395.77 -296.84

NH4Cl (s) -315.4

205.07 102 -851.9

Na2CO3(s) -1130.77

134.79

-1048.08

Avogadros number / Avogadro se getal = 6.0221357 1023; (Faraday)=96485 Coulomb.mol!1 General Gas Constant / Algemene Gaskonstante: R = 8.314510 Jmol!1K!1 or/of R = 0.082057 L.atm.mol!1 1 cal = 4.184 J 13

0 C = 273.15 K (1) E = q + w; Wmax=n E, q = .m.T

(2) Hrxn = 3Hrxn(prod) - 3Hrxn(react/reakt) (3) Suniv = Ssys + Ssurr (4) Ssurr = qT!1 = ! HsysT!1 (5) Ssys = 3Ssys(prod) - 3Ssys(react/reakt) (6) Gsys = Hsys -T Ssys (7) G = 3Gf(prod) - 3Gf(react/reakt) (8) G = G + RTlnQ (9) E = E - R.T(n. )!1lnQ (10) E = E - 0.0257(.n!1).lnQ. (11) G = !n. . E (12) G = RTlnK (13) 1Amp.1sec = 1Coulomb (14) 1Watt.1sec = 1Joule (15) 1Joule = 1Volt.1Coulomb (16) At equilibrium, E = 0 and Q = K.

14

Standaard Reduksie Potensiale in Waterige Oplossing by 25.00C*

Standard Reduction Potentials In Aqueous at 25.00C*

E (V) F2 (g) + 2 e H2O2 (aq) + 2 H3O (aq) + 2 e PbO2 (s) + Au

3+ +

2F (aq) 4 H2O () PbSO4 (s) + 6 H2O () Mn

2+

+2.87 +1.77 +1.685 +1.52 +1.50 +1.229 +1.08 +0.96 +0.89 +0.80 +0.789 +0.77 +0.535 +0.40 +0.337 +0.15 0.00 -0.125 -0.14 -0.25 -0.255 SO2 4 (aq) -0.356 -0.40 -0.44 -0.763 -0.8277 -1.26 -1.66 -2.37 -2.714 -2.925 -3.045
-

SO2 4

(aq) + 4 H3O (aq) + 2 e

+

MnO (aq) + 8 H3O (aq) + 5 e 4 (aq) + 3 e

+

(aq) + 12 H2O ()

Au (s) 6 H2O () 2 Br (aq) NO (g) + 6 H2O () Cl (aq) + 2 OH (aq) Ag (s) 2 Hg () Fe

2+

O2 (g) + 4 H3O (aq) + 4 e Br2 () + 2 e NO (aq) + 4 H3O+ (aq) + 3 e 3 OCl (aq) + H2O () + 2 e Ag (aq) + e Hg2+ 2 Fe
3+ +

(aq) + 2 e (aq) + e

(aq)

I2 (s) + 2 e O2 (g) + 2 H2O () + 4 e Cu Sn Pb Ni

2+

2 I (aq) 4 OH (aq) Cu (s) Sn

2+

(aq) + 2 e (aq) + 2 e
+

4+

(aq)

2 H3O (aq) + 2 e
2+ 2+

H2 (g) + 2 H2O () Pb (s) Sn (s) Ni (s) V2+ (aq) Pb (s) + Cd (s) Fe (s) Zn (s) H2 (g) + 2 OH (aq) Zn (s) + 4 CN (aq) Al (s) Mg (s) Na (s) K (s) Li (s)

(aq) + 2 e (aq) + 2 e (aq) + 2 e

Sn

2+

V3+ (aq) + e PbSO4 (s) + 2 e Cd Fe Zn

2+

(aq) + 2 e (aq) + 2 e (aq) + 2 e

2-

2+ 2+

2 H2O () + 2 e [Zn(CN)4] Al
3+

(aq) + 2 e

(aq) + 3 e

Mg2+ (aq) + 2 e Na (aq) + e K (aq) + e Li (aq) + e

+ + +

15

16

Periodic table of the elements / Periodieke tabel van die elemente

1A 1 H 1,0079 3 Li 6,941 11 Na 22,9898 19 K 39,0983 37 Rb 85,4678 55 Cs 132,9054 87 Fr (223)

8A 2 He 4,0026 10 Ne 20,1797 18 Ar 39,948 36 Kr 83,80 54 Xe 131,29 86 Rn (222)

2A 4 Be 9,0122 12 Mg 24,3050 20 Ca 40,078 38 Sr 87,62 56 Ba 137,327 88 Ra 226,0254

3A 5 B 10,811 13 Al 26,9815 30 Zn 65,39 48 Cd 112,411 80 Hg 200,59 31 Ga 69,723 49 In 114,82 81 Tl 204,3833

4A 6 C 12,011 14 Si 28,0855 32 Ge 72,61 50 Sn 118,710 82 Pb 207,2

5A 7 N 14,0067 15 P 30,9738 33 As 74,9216 51 Sb 121,757 83 Bi 208,9804

6A 8 O 15,9994 16 S 32,066 34 Se 78,96 52 Te 127,60 84 Po (209)

7A 9 F 18,9984 17 Cl 35,4527 35 Br 79,904 53 I 126,9045 85 At (210)

3B 21 Sc 44,9559 39 Y 88,9059 57 La* 138,9055 89 Ac** 227.0278

4B 22 Ti 47,88 40 Zr 91,224 72 Hf 178,49 104 Rf (261)

5B 23 V 50,9415 41 Nb 92,9064 73 Ta 180,9479 105 Ha (262)

6B 24 Cr 51,9961 42 Mo 95,94 74 W 183,85 106 Sg (263)

7B 25 Mn 54,9380 43 Tc (98) 75 Re 186,207 107 Ns (262)

8B 26 Fe 55,847 44 Ru 101,07 76 Os 190,2 108 Hs (265) 27 Co 58,9332 45 Rh 102,9055 77 Ir 192,22 109 Mt (266) 28 Ni 58,693 46 Pd 106,42 78 Pt 195,08
Discovered

1B 29 Cu 63,546 47 Ag 107,8682 79 Au 196,9665

Discovered

2B

110

111

Nov 94

Dec 94

LANTHANIDES*

58 Ce 140,115 90 Th 232,0381

59 Pr 140,9076 91 Pa 231,0359

60 Nd 144,24 92 U 238,0289

61 Pm (145) 93 Np 237,0482

62 Sm 150,36 94 Pu (244)

63 Eu 151,965 95 Am (243)

64 Gd 157,25 96 Cm (247)

65 Tb 158,9253 97 Bk (247)

66 Dy 162,50 98 Cf (251)

67 Ho 164,9303 99 Es (252)

68 Er 167,26 100 Fm (257)

69 Tm 168,9342 101 Md (258)

70 Yb 173,04 102 No (259)

71 Lu 174,967 103 Lr (260)

ACTINIDES**

R = 8.314 JK1 mol1

F = 9.65 x 104 C

17