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NAME:_________________________ Fall 2009 INSTRUCTIONS: Section:_____ Student Number:________________ Chemistry 1000 Midterm #2A ____/ 55 marks 1) Please read over the test carefully before beginning. You should have 7 pages of questions, a blank page that can be used if you run out of space on any question, and 2 pages of data/formula/periodic table sheet. 2) If you use the “overflow” page, indicate this next to the question and clearly number your work on the “overflow” page. 3) If your work is not legible, it will be given a mark of zero. 4) Marks will be deducted for incorrect information added to an otherwise correct answer. 5) Marks will be deducted for improper use of significant figures and for missing or incorrect units. 6) Show your work for all calculations. Answers without supporting calculations will not be given full credit. 7) You may use a calculator. 8) You have 90 minutes to complete this test. Confidentiality Agreement: I agree not to discuss (or in any other way divulge) the contents of this exam until after 5pm Mountain Time on Tuesday, November 17th, 2009. I understand that, if I were to break this agreement, I would be choosing to commit academic misconduct and that is a serious offense which will be punished. The minimum punishment would be a mark of 0/55 on this exam and removal of the “overwrite midterm mark with final exam mark” option for my grade in this course; the maximum punishment would include expulsion from this university. Signature: ___________________________ Course: CHEM 1000 (General Chemistry I) Semester: Fall 2009 The University of Lethbridge Date: _____________________________ Question Breakdown Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8 Q9 Q10 / 16 /3 /5 /6 /3 /3 /6 /2 /7 /4 Total / 55 NAME:_________________________ Section:_____ Student Number:________________ 1. Answer the following questions by filling in the blanks. [16 marks] (a) In lab, you constructed face centered cubic unit cells from white foam spheres. If you were to construct a body centered cubic lattice from the same white foam spheres, would it have a higher or lower density than the face-centered cubic lattice? The density of the body-centered cubic lattice would be __lower__. (b) Lithium has very similar properties to one of the alkaline earth metals. That alkaline earth metal is _magnesium (Mg)__. (c) If there are no lone pairs on the phosphorus atom in PBr5 then the molecular geometry is _trigonal bipyramidal_. (d) Sodium metal is produced through the electrolysis of sodium chloride in what state of matter? _liquid_ (e) Aluminium metal reacts with some acids but not others. An example of an acid with which aluminium metal will not react is _nitric acid (HNO3)_. or any other oxidizing acid or any weak acid (f) The alkali metal that reacts most vigorously with water is _francium (Fr)_. (g) Give an example of a metal oxide that reacts with both acid and base. _beryllium oxide (BeO) or aluminium oxide (Al2O3)_ or any other oxide of a group 13 element (h) The correct name for CrCl3 is _chromium(III) chloride_. (i) The alkaline earth metal that produces salts giving green flame tests is _barium (Ba)_. (j) The gas produced when magnesium metal is added to hydrochloric acid is _hydrogen (H2)_. (k) Zinc(II) nitride has the molecular formula _Zn3N2_. (l) The two cations that contribute the most to the hardness of water are _Mg2+_ and _Ca2+_. (Credit will only be given if both symbol and charge are correct!) (m) An atom which has octahedral electron group geometry (two lone pairs + the appropriate number of bonded atoms) has _square planar_molecular geometry. (n) A face-centered cubic lattice has two types of holes. The _octahedral_ holes are larger than the _tetrahedral_ holes. NAME:_________________________ 2. Section:_____ Student Number:________________ Given that Ba2+(aq) is highly toxic, which of the compounds below would make a more effective rat poison? Briefly, justify your answer. Your justification should include at least one balanced chemical equation. [3 marks] BaCO3 or BaSO4? BaCO3 and BaSO4 are both insoluble in water; however, BaCO3 reacts with stomach acid, releasing toxic Ba2+(aq) cations. BaSO4 does not react with acid. 2+ + BaCO 3(s) + 2H (aq) → Ba (aq) + H 2 O (l) + CO 2(g) 3. In the gas phase, BeCl2 can exist as discrete molecules with polar covalent bonds. Under standard conditions, MgCl2 exists as an ionic lattice. [5 marks] (a) Draw the best Lewis structure for BeCl2. .. .. Cl .. Be [1 mark] .. . Cl .. . This is the Lewis structure that minimizes formal charge. It is preferable to a structure which has Be=Cl double bonds since those would give each Cl a formal charge of +1 and the much less electronegative Be a formal charge of -2. Group 2 and Group 13 elements can have less than a full octet (4 electrons for Group 2; 6 electrons for Group 13). (b) What is the molecular geometry for BeCl2? [1 mark] linear (c) What is the Cl-Be-Cl bond angle in BeCl2? [1 mark] 180° (d) Why would BeCl2 be a molecular compound when all of the other alkaline earth metals react with chlorine gas to give ionic compounds? [2 marks] The Be2+ cation is very small. Therefore, its charge density is much higher than any other M2+ cation formed from an alkaline earth metal. This makes Be2+ a much less stable cation than other M2+ cations. For this reason, beryllium atoms are more stable when part of molecular compounds (in which they usually have a neutral formal charge). NAME:_________________________ Section:_____ Student Number:________________ 4. (a) [6 marks] Draw all valid resonance structures for the sulfite ion ( SO 32- ). Include any non-zero formal [4 marks] charges on the appropriate atom(s). .. .. ..O -1 .. S .. ..O .. . -1 O .. . .. . -1 O .. . S .. ..O .. .. O .. (b) .. -1 What is the average S-O bond order in the sulfite ion? .. ..O .. -1 .. .. S .. O.. .. O .. -1 [1 mark] 1⅓ (b) Draw one valid Lewis structure for sulfurous acid ( H 2SO 3 ). Include any non-zero formal charges on the appropriate atom(s). [1 mark] H .. ..O .. S .. O .. H .. O.. Note that the hydrogen atoms MUST be bonded to oxygen – not sulfur. It is logical that the H+ would attach themselves to the O- of the SO32- anion. NAME:_________________________ Section:_____ Student Number:________________ 5. Write a balanced chemical equation for each of the following reactions. If no reaction [3 marks] occurs, instead write “NO REACTION”. Include all states of matter. (a) Bromine is poured over sodium. [1 mark] 2 Na (s) + Br2(l) → 2 NaBr(s) (b) Sodium is exposed to nitrogen. [1 mark] no reaction (c) Barium is dropped into water. [1 mark] 2+ Ba (s) + 2 H 2 O (l) → Ba (aq) + 2 OH -(aq) + H 2(g) It is acceptable to combine the barium and hydroxide ions, writing Ba(OH)2(aq) 6. Potassium metal exists as a body centered cubic lattice. Given that the radius of a potassium atom is 227.2 pm, what is the size of the unit cell? Express your answer as the length of one edge of the unit cell in pm. [3 marks] The relationships between the three sides of the triangle drawn at the right were derived in class using the Pythagorean theorem. x 3 As can be seen in the figure at the right, the distance between opposite corners of the BCC unit cell is equal to four atomic radii. x 2 x 3x = 4r 4r x= 3 4(227.2pm ) x= 3 x = 524.7pm NAME:_________________________ 7. (a) Section:_____ Student Number:________________ g at 25 °C. The metal exists as a cubic closest cm 3 [6 marks] packed lattice, and the edge of a unit cell is 392 pm long. An unknown metal has a density of 21.5 Calculate the atomic mass of this metal. Report your answer in g/mol. [5 marks] cubic closest packed = face-centered cubic therefore, one unit cell contains 4 atoms. 1m 100 cm x = 392 pm × 12 × = 3.92 × 10 −8 cm 10 pm 1m ( ) 3 V = x 3 = 3.92 × 10 −8 cm = 6.02 × 10 −23 cm 3 d= m V ( ) g ⎞ ⎛ mcell = d ⋅ V = ⎜ 21.5 3 ⎟ 6.02 × 10 − 23 cm 3 = 1.30 × 10 − 21 g cm ⎠ ⎝ mcell = 4matom matom = mcell 1.30 × 10 −21 g = = 3.24 × 10 −22 g 4 4 M = matom ⋅ N A = 3.24 × 10 − 22 g g 6.02214 × 10 23 atoms × = 195 atom mol 1mol (b) Identify the metal by referring to the periodic table given on the data sheet. You do not need to name the metal; the symbol is sufficient. platinum (Pt) 8. Which of the metal oxides below would you expect to have the highest melting point? Circle your choice and briefly justify your answer. [2 marks] Li2O MgO Al2O3 [1 mark] CO2 Eliminate CO2 as it is not a metal oxide. Of the remaining choices, compare the charge density of the ions. The lattice whose ions have the highest charge density would be expected to have the highest enthalpy of lattice formation and therefore the highest melting point. Li2O consists of Li+ and O2-. MgO consists of Mg2+ and O2-. Al2O3 consists of Al3+ and O2-. As such, Al2O3 would be expected to have the highest melting point since M3+ can be expected to have a higher charge density than M2+ or M+. NAME:_________________________ Section:_____ Student Number:________________ 9. We cannot measure the second enthalpy of electronic attraction (∆HEA2) of oxygen directly. It can, however, exist in the solid state where the high energy requirement for its formation [7 marks] is offset by the large lattice energies of ionic oxides. (a) Sketch a Born-Haber cycle diagram for MgO. Clearly label the enthalpy change involved [4 marks] with each step. (i.e. give the name or symbol for each enthalpy change) Steps to a Born-Haber cycle: - Write overall chemical equation for formation of ionic compound from its constituent elements (“enthalpy of formation”) - Convert each element into single gaseous atoms - Make the appropriate ions from those atoms (“ionization energy” to make cations; “enthalpy of electronic attraction” to make anions) - Bring ions together to form a lattice (“enthalpy of lattice formation”) Mg2+(g) + I2(Mg) ∆EA2H(O) Mg+(g) O-(g) ∆EA1H(O) I1(Mg) Mg(g) (b) ∆LFH (MgO) O(g) ∆sublH(Mg) Mg(s) O2-(g) ½ ∆BDH(O2) + ½ O2(g) ∆fH° (MgO) MgO(s) Use your Born-Haber cycle and the information from the data sheet to calculate ∆EA2H for [2 marks] oxygen. ∆ f H °( MgO ) = ∆ subl H ( Mg ) + I1 ( Mg ) + I 2 ( Mg ) + 12 ∆ BD H (O2 ) + ∆ EA1 H (O ) + ∆ EA 2 H (O ) + ∆ LF H ( MgO ) ∆ EA 2 H (O ) = ∆ f H °( MgO ) − [∆ subl H ( Mg ) + I1 ( Mg ) + I 2 ( Mg ) + 12 ∆ BD H (O2 ) + ∆ EA1 H (O ) + ∆ LF H ( MgO ) ] kJ kJ kJ kJ ) − [(146 mol ) + (737 .7 mol ) + (1451 mol )+ = (− 601 .7 mol 1 2 kJ kJ kJ (498 mol ) + (− 141.0 mol ) + (− 3925 mol )] kJ ∆ EA 2 H (O ) = +881 mol (c) Values for ∆EA1H are usually negative. Why do you think the value for ∆EA2H is positive? [1 mark] Adding an electron to an anion is not as favourable as adding an electron to a neutral atom due to increased charge repulsion (between the negative ion and the negative electron). NAME:_________________________ Section:_____ Student Number:________________ 10. Aluminium metal is prepared by electrolysis of aluminium oxide using a carbon (C(s)) anode. [4 marks] This process produces carbon dioxide as a byproduct. (a) Write a balanced chemical equation (including states of matter) for this reaction. [1 mark] 2Al 2 O 3(l) + 3C (s) → 4Al (l) + 3CO 2(g) Except for states of matter, all reactants and products were listed in the sentence at the top of the page. (b) Calculate the mass of carbon dioxide produced for every kilogram of aluminium prepared according to this method. (This does not, of course, include carbon dioxide generated by [3 marks] burning fuels in order to generate the necessary energy for this reaction.) Give your answer with three significant figures. 1 kg = 1000 g n Al = 1000 g Al × 1 mol = 37.1 mol Al 26.9815 g n CO 2 = 37.1 mol Al × 3 mol CO 2 = 27.8 mol CO 2 4 mol Al m CO 2 = 27.8 mol CO 2 × 44.0098 g = 1223 g CO 2 = 1.22 × 10 3 g CO 2 = 1.22 kg CO 2 1 mol Every stoichiometry problem should be approached with the same three-step process: 1. Find moles of known species (in this case, Al) 2. Use mole ratio to find moles of species of interest (in this case, CO2) 3. Answer question. (In this case, find mass of CO2.) You CANNOT use the mole ratio directly on masses! NAME:_________________________ Section:_____ Student Number:________________ Some Useful Constants and Formulae Fundamental Constants and Conversion Factors Atomic mass unit (u) 1.6605 × 10-27 kg Avogadro's number 6.02214 × 1023 mol–1 Bohr radius (a0) 5.29177 × 10-11 m 9 2 -2 Coulomb constant (1/(4πε0)) 8.988 × 10 N·m ·C Electron charge (e) 1.6022 × 10-19 C Electron mass 5.4688 × 10-4 u Ideal gas constant (R) 8.3145 J·mol-1·K-1 8.3145 m3·Pa·mol-1·K-1 Planck's constant Proton mass Neutron mass Rydberg Constant (RH) Speed of light in vacuum Standard atmospheric pressure 6.626 × 10-34 J·Hz-1 1.0072765 u 1.0086649 u 2.179 × 10-18 J 2.9979 × 108 m·s-1 1 bar = 100 kPa Formulae c = λυ rn = a0 E = hυ n2 Z E n = − RH λ= p = mv Z2 n2 Ek = 1 ( z + e)( z − e) F= 4πε d2 1 2 mv 2 h p ∆x ⋅ ∆p > h 4π PV = nRT 1 ( z + e)( z − e) E= 4πε d Some Thermodynamic Data ∆ sub H ( Mg ) I 1 ( Mg ) I 2 ( Mg ) ∆ EA1 H ( Mg ) kJ mol kJ + 737.7 mol kJ + 1451 mol kJ 0 mol + 146 ∆ BD H (O = O) I1 (O ) I 2 (O ) ∆ EA1 H (O ) kJ mol kJ + 1314 mol kJ + 3388 mol kJ - 141.0 mol + 498 ∆ LF H ( MgO) ∆ f H °(MgO) kJ mol kJ - 601.7 mol - 3925 NAME:_________________________ 1 Section:_____ Student Number:________________ CHEM 1000 Standard Periodic Table 18 1.0079 4.0026 H He 2 13 14 15 16 17 6.941 9.0122 10.811 12.011 14.0067 15.9994 18.9984 Li Be B C N O F Ne 3 22.9898 4 24.3050 5 26.9815 6 28.0855 7 30.9738 8 32.066 9 35.4527 10 39.948 1 2 20.1797 Na Mg 11 39.0983 12 40.078 3 4 5 6 7 8 9 10 11 12 44.9559 47.88 50.9415 51.9961 54.9380 55.847 58.9332 58.693 63.546 65.39 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 19 85.4678 20 87.62 21 88.9059 22 91.224 23 92.9064 24 95.94 26 101.07 27 102.906 28 106.42 29 107.868 30 112.411 31 114.82 32 118.710 33 121.757 34 127.60 35 126.905 36 131.29 Rb Sr 37 132.905 38 137.327 Cs Ba 55 (223) 56 226.025 Fr 87 Ra Y 39 La-Lu Ac-Lr 88 P S Cl Ar 15 74.9216 16 78.96 17 79.904 18 83.80 Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 41 180.948 42 183.85 43 186.207 44 190.2 45 192.22 46 195.08 47 196.967 48 200.59 49 204.383 50 207.19 51 208.980 52 (210) 53 (210) 54 (222) Hf Ta W Re Os Ir Pt Au 72 (261) 73 (262) 74 (263) 75 (262) 76 (265) 77 (266) 78 (281) 79 (283) Rf Db Sg 105 106 138.906 140.115 140.908 144.24 La Ce Pr Nd 57 227.028 58 232.038 59 231.036 60 238.029 Ac Si 14 72.61 40 178.49 104 89 25 (98) Al 13 69.723 Th 90 Pa 91 U 92 Bh 107 Hs Mt Dt Hg Tl Pb Bi Po At 80 81 82 83 84 85 174.967 Rg 108 109 110 111 (145) 150.36 151.965 157.25 158.925 162.50 164.930 167.26 168.934 173.04 Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 61 237.048 62 (240) 63 (243) 64 (247) 65 (247) 66 (251) 67 (252) 68 (257) 69 (258) 70 (259) 71 (260) Np 93 Pu 94 Am 95 Cm 96 Rn 86 Bk 97 Cf 98 Es 99 Fm 100 Md 101 No 102 Lr 103 Developed by Prof. R. T. Boeré