Problems and Solutions @ 14-31 Problems and Solutions 14-1. Ina Boyle's Law experiment (perfect gas law at constant temperature) the following data were taken Pressure (tort) _ Volume (ml) 904 270 827 295 760. 32 650 385 552 442 a) The volume value which was recorded incorrectly is most nearly (@) 27.0 (b) 295) 324) 385 b) The predicted volume for that pre © is most nearly (@ 260 () 31.1 (b) 28.5 (d) 37.5 Solution a) Boyle’s law and the perfect gas law state that PV should be constant at constant tempera ture. The PY products of the above data are 24408, 24396, 24396, 25025, and 24398, The fourth value, 25025, is inconsistent with the others. Therefore the volume value (d) 38.5 is incorrect, b) The average PV product for the four good readings is 24400. Then 24400/650 = 37.5, so the value of the volume at pressure 650 torr should have been (d) 37.5 ml 14-2. The volume of one mole of gaseous water at 100°C and | atmosphere pressure is (a) 18.0 mt (eo) 24L (b) 100 mil (d) 306L Solution The volume of one mole of any gas is 22.4 L at STP conditions (I atm pressure and 0°C), The conditions are one atm so there is no pressure correction. However the temperature correction is done by Charles’ Law (perfect gas law at constant pressure), after the temperature is con- verted to °K (Kelvin): WS AM. Bie q q14-32 ‘Ml Chemistry At constant pressure: (100 +273) °K T°K 22.4L x 30.61 ‘The answer is (d). 14-3. First ionization energy refers to: (a) removal of an electron from a gas atom. (b) energy to form the most probable ion (©) trapping an ion in a lattice structure. (d) formation of a1 anion lution (a) is the definition of ionization energy (b) is incorrect since the second and third ionization energy may be pertinent to forming the most probable ion (c) is incorrect since the ion formed does not have to be trapped in a lattice structure, and the energy is unrelated (d)is incorrect since a +1 cation forms ‘The answer is (a). 14-4, From the periodic table predict the molecular formula of silicon (Si) oxide (0). (@ SiO (b) SiO ©) SiO, @) SiO, Solution ‘Oxygen (Atomic No. 8) is in the second period and Group VIA of the periodic table. Silicon (Atomic No, 14) isin the third period and Group IVA of the periodic table. The most probable electronic structure for oxygen in a compound is to pick up two electrons to fill its outermost shell, giving it the electron configuration of neon (Atomic No. 10). icon, with four electrons in the outer shell, could either gain four electrons or lose four electrons to form a complete octet in the outer shell. However, since O wants to gain aU electrons, itis more likely that Si will lose them, making it also isoelectronic with neon. The ‘appropriate number of Si and O atoms must then combine so that the number of electron gained by the O atoms equals the number of electrons lost by the Si atoms. Therefore, there must be twice as many © atoms as Si atoms in the molecular formula, and the simplest mo- lecular formula is SiO,. The answer is (d),Problems and Solutions @ 14-33 14-5. Two metals, both of which commonly form +1 and +2 ions in solution are: (a) Cu and Hg. (©) Feand Cu (b) Awand Ag (d) Zn and Ca. Solution (a) is correct because Cu forms Cu* and Cu2* and Hg forms Hg* and Hg?*, although the ‘monovalent Hg ion is considered to be Hg,”*. Au forms Au’ and Au, Ag forms Ag*, Fe * and Fe", Zn forms Zn®*, and Cd forms Cd? forms Fe 14-6. The formula for potassium aluminum sulfate is (not including water of hydration) (a) KAISO, (©) K,AlSO, (b) KAUSO), (d) KASO,), Solution In this mixed salt (alum), the K has a valence of +1, the Al has a valence of +3, and (SO,) is The formula is KAI(SO,),, Alum also includes 12 H,O of ser is (b) a group with a valence of ~ hydration in the crystal. Th 14-7. To indicate a compound is pentahydrate, you would write as part of the formula: (a) +H") (©) + (OH) (b) +5) (d) + 5H,0 Solution Penta means 5, hydrate means water. This is one of the few times a coefficient shows up inside a formula, Some prefer to write: salt(H,O),. The answer is (4) 14-8. Hydroiodic acid contains how many elements? @l m2 ©3 wa Solution Any acid beginning with hydro contains hydrogen and only one other element. The answer is (b). 14-9. The common name of the oxide of nitrogen with the formula N,O, is, (a) nitrogen dioxide (©) nitric oxide. (b) nitrous oxide (4) dinitrogen oxide. Solution ‘There are six oxides of nitrogen with oxidation numbers of the nitrogen ranging from +1 t0 +5. The formulas are N,O, NO, N,0,, NO,, N,O,, and N,O,. Their common names are ni- tous oxide, nitric oxide, dinitrogen trioxide, nitrogen dioxide, and dinitrogen pentaoxide (or Pentoxide), respectively. N,O, is the dimer of NO, and N is +4 in both species. The system- atic name of NO is dinitrogen oxide and of NO is nitrogen monoxide. (b) is the correct I)Ua 14-34 Ml Chemistry common name for N,O. (d) is a correct name for N,O, but it is a systematic name, and the ‘on calls for the common name. ‘The answer is (b). ques 14-10. ‘The name of (NH,),Cr,0, is: (a) diammonium chromate (c) ammonium(Il) chromate. (b) ammonium chromate. (d) ammonium dichromate, Solution Chromium forms two oxyanions with Cr in the +6 oxidation state. These are the chromate ion, (CrO,)*, and the dichromate ion, (Cr,0,)>. (a), (b), and (c) are chromates, which is incorrect, (d) is systematically named but ignores the fact that the name of an ionic compound is built from the names of the ions present. The answer is (d). 14-11, 1.38 moles of manganese (IV) oxide contains: a) how many moles of manganese ions? (a) 100 (b) 2.76 (ce) 1.38 (@) 4.00 b) how many moles of oxygen ions? (a) 138 (b) 2.76 (c) 200d) 1.76 ¢) how many grams of material? (a.w. Mn = 54.9, 0 = 16.0) (a) 1.38 (b) 869 (ce) 2.76 (d) 120 Solution a) I mol MnO, = | mol Mn +2 mol 0; 1.38 mol MnO, x 1.0 mol Ma**/1.0 mol MnO, = 1.38 mol Mn**. The answer is (c). b) 1.38 mol MnO, x 2.0 mol O7/1.0 mol MnO, = 2.76 mol O-. The answer is (b). ©) maw. MnO, = 54.9 + (2 x 16.0) = 86.9; 1.38 mol MnO, x 86.9 g MnO,/1 mol MnO, = 120 g MnO,. The answer is (d). 14-12. A student in a chemistry laboratory wants to weigh out 2.00 moles of calcium car- bonate (CaCO, ) but picks up sodium chloride (NaCl) by mistake. How many moles of NaCl will the student weigh out? {m.w. CaCO, = 40.1 + 12.0 + (3x 16.0) = 100.1; NaCl = 23.0 + 35.5 = 58.5] (a) 342 (b) 187 (c) 1.16 (@) 2.00 Solu Thinking he or she has CaCO,, the student will weigh out: 2.00 mol x (100.1 g CaCO /mol) = 200.2 g. But since it was NaCl that was weighed, the number of moles of NaCl is: 200.2 g x (1 mol NaCV58.5 g) = 3.42 moles NaCl. The answer is (a)Problems and Solutions @ 14-35 14-13. A protein molecule is known to bind one molecule of oxygen (O,) per molecule of protein. If 12.2 g of protein bind 9.8 mg of O,, what is the molecular weight of the protein? (mw. 0, = 2x 16.0 = 32.0) (a) 25,700 (b) 79,600 (c) 38,900 (d) 39,800 Solution 9.8 mg O, x 10° g/l mg = 9.8 x 107 g 0, I molecule O,/1 molecule protein = | mol O,/1 mol protein I mol 0, = 32.00, 122g protein | 320g0, , tmolO, _ 98x107 gO, — TmolO, ~ I mol protein mw. protein = 39.8 x 10° = 39,800 or: 98x10" gO, 32:0 g/l mol O, 0.3062 x 10-4 molO, = 0.362 x 10° mol protein, g = mol x mw. g mw. = mol 12.2 g protein 0.3062. x 109 mol protein = 398 x 103 = 39,800 mw. protein The answer is (d) 14-14. An impure sample of FeSO, - 7H,O weighing 1.285 g is analyzed for Fe (Il) content by titration with 0.03820 M KMnO, in acid solution. The endpoint is 21.83 ml. What is the weight % of Fe (II) in the impure sample? (a.w. Fe= 55.85, K = 39.10, = 32.07, Mn = 54.94, (0 = 16.00, H = 1.008) (a) 18.12% (©) 9.060% (b) 36.76% (d) 20.09% Solution First calculate moles of KMnO, to reach the endpoint: LL 0.03820 mol 21.83 ml KMno, x 1 10° ml IL 8339 x 10 mol KMnO, We need the balanced equation to relate moles of KMnO, to moles of Fe (Il) Chemistry 5 Fe™ + MnO, +8 H* > 5 Fe + Mn? +4 1,0. Since moles of MnO,” = moles of KMnO,, S mol Fe 8.339 x 10-4 mol Mad,” x 2 MlFE 479 x 10-4 mol Fe mol MnO, 5,58 mol Fe 4.170 x 10‘ mol Fe” x = 0.2329 g Fe”’ in sampleUI 14-36 Ml Chemistry 0.2329 g Fe 12 x 100 = 18.12% Fe?* in sample g sample The answer is (a) 14-15. A student wishes to check the concentration of a bottle of hydrogen peroxide, H,0, To do so, the student carried out a redox titration of the H,O, with KMnO,, as shown in the reaction: 5 H,0,aq) + 2 KMnO, (aq) + 3 H,SO,(aq) > K,S0 (ag) + 2 MnSO,(aq) + 8 H,O(!) + 5 0,(g) Ut required 39.7 ml of 0.0103 M KMnO (aq) to react with 1.546 g of the hydrogen peroxide solution. What was the percent of HO, by mass in the solution? (a.w K = 39.10, H = 1.008, 0 = 16.00, Mn = 54.94, $ = 32.07) (a) 1.80% fe) 1.65% (b) 2.70% (a) 2.24% Solution Percent H,O, by mass is equal to: BH:02 5 109 g sample so we must find g H,O,. This information is supplied by the titration and the balanced equa. tion 0.0103 mol 0.0397 L moles KMnO, = —* x = 4.09 x 104 mol L titre From the balanced equation the reacting ratio is 5 mol 2 mol KMnO, SmolH,0, 4.09104 mol KMnO, 2 mol KMnO, sample = 1.02 x 107 mol H,0, 34.02 gH,0, = mol x mw. = 1.02 x 10 mol x = 347x102 0.0347 ¢ H,0, 1.546 g solution T mol percent HO, = x 100 = 2.24% H,0, The answer is (d). 14-16. What weight in g of SnCI, is needed to react with 40 ml of 0.10 normal I, solution as follows: Sn** +1, Sn +21 (aw. Sn = 118.70, 1 = 126.90, Cl = 35.45) (a) 038g (© 38% (b) 0.76 g (@) 019gProblems and Solutions w 14-37 Solution First calculate the number of equivalents of I, Equivalents = volume (L) x normality (N) = 0.040 L x 0.10 = 0,0040 equiv. 1, Since the values of normality and equivalents are taken with respect to the particular rea being considered: ion equivalents SnCl, = equivalents [, = 0.040 ‘The half-reaction for Sn? is: Sn? Sn¥* +26 AAs the oxidation number of Sn changes from +2 to +4, a change of two, the equivalent weight of SnCl, is formula weight _ 189.60 _ 94 59 2 2 94.80 ¢ weight SnCl = X 0.0040 equiv. = 0.38 g ‘equivalent ‘The answer is (a), 14-17. A solution is prepared by dissolving 5.88 g K,Cr,O, in dilute acid and diluting with water to 1.000 L, Calculate the normality of the solution assuming that the half-reaction for the Cr,0,” in solu- tion is I4 Ht + Cr,0,2 + 2Cr* +7 H,0 (a) 0.163N (©) 0.120N (b) 0.060 N (d) 0.050 N cell reaction for Cr,0,”, the oxidation state of Cr changes from +6 to +3. Since two Cr atoms are in the Cr,O,?> formula, the change for the species is six and the equivalent weight isthe molecular weight divided by six. This can also be seen by balancing the half-cell charges by the addition of six e° (0 the left side of the equation, 2 420 _ 49.03 6 equivalent weight K,Cr,0, (Note: Since we are relating this figure to the weight of dissolved K,Cr,O,, its the molecular weight—or formula weight—of the K salt that is used in the calculation.) 5.88 g equivalents K,Cr,0) = _ ae 49.03 equivalent _ 4 199 equivalem & NyUTS 14-38 Ml Chemistry m= 0.120N normality ‘The answer is (c). 14-18. Given the following standard electrode potentials: ADS 43 6 9 Al = 1.66 V CaP +20 > Cd; = -0.40 V Determine the standard cell potential for the reaction: Al+3Cd* 5 2 AP +3Cd (a) =2.06V (c) E°=1.23V (b) E9=-1.26V (d) B= 1.26V Solution The cell reaction shows Al as oxidized (loss of electrons). Therefore, the equation for the standard electrode potential must be rewritten as an oxidation reaction, and the sign of E® will be positive: AIS APY +365 B= 1.66 V ‘The cell reaction for Cd is written correctly, as Cd? is reduced (gain of electrons). However the equations must be multiplied by the appropriate factors so that cach has the same number of electrons. This will be 2 for the Al equation and 3 for the Cd equation, to give: 2Al> 2 AP +665 66 V 3Cd?* +66 9 3 Cd; B= -0.40V The equations are added to give: 2 Al +3 Cd* = 2 Al +3 Ca (the electrons cancel); E = 1.26 V Note that the values of £° are not multiplied by the coefficients used to balance the electron transfer in the equation. The answer is (d) 14-19. Calculate the standard cell potential, £°, for the reactions below, using the correct half-reactions and the corresponding standard electrode potentials, £°. State whether each ion is spontaneous or non-spontaneous at standard conditions. ‘Table of Standard Reduction Potentials Half-Reaction EY Fe"+2e=Fe(s) O41 Sw'+2e=Sn(s) -0.14V 2H +2e=Hi(e) 0.00V Sn" +2e=Sn" 01S V Curse O16 v Cur+2e=Cus) 034 Fel te onyProblems and Solutions wm 14-39 a) Fe(s) + 2 Ht Fe +H, (g) (a) -0.41 V (non-spontaneous) (©) O41 V (spontaneous) (b) 0.20 V (spontaneous) (d) 0.20 V (non-spontaneous) b) Cu(s) +2 HY > Cu + Hg) (a) 0.34 V (non-spontaneous) (©) -0.34 V (spontaneous) (b) 0.17 V (spontaneous) (d) -0.34 V (non-spontaneous) ¢) Sn** +2 Fe — Sn** 4.2 Fe (@) 0.62 V (spontaneous) (©) 0.62 V (non-spontaneous) (b) 0.92 V (spontaneous) (4) -0.62 V (spontaneous) Solution a) Fes) > Fe” +2" +0.41 V; (oxidation half-reaction, reversed from reduction half-reaction table, £° sign reversed) 2H +2et > Hg): 0.00 V; (reduction half-reaction from table, same sign of E°) Fe(s) +2 Ht = Fe + H,(g): 0.41 V; (add half-reactions, electrons cancel, £° additive) Reaction is spontaneous at standard conditions when E® positive The answer is (c) b) Culs) > Cu 4265 0.34 V; (oxidation half-reaction, reversed from reduction half-reaction table, E sign reversed) 2H +2e + Hye) 0.00 V; (reduction half-reaction from table, same sign of E°) Cu(s) +2 Ht > Cu?* + Hy (g) 0.34 V; (add half-reactions, electrons can: I, EY additive) Reaction is non-spontancous at standard conditions when £® negative. The answer is (d) ©) Sn? Sn +2 6 ~0.15 V; (oxidation half-reaction, reversed from reduction half-reaction table, E® sign PS reversed) Fel +e > Fe™ 0.77 V; (reduction half reaction from table, same sign of E°) 2Fe +26 42 Fe 0.77 V, (double equation so electrons will cancel; note E does not double) ‘Sn? 42 Fe 9 Sut +2 Fe® 0.62 V; (add half-reactions, electrons cancel, £° additive) Reaction is spontancous at standard conditions when E® positive. The answer is (a).nay 14-40 Chemistry 14-20. Given the cell Cu | Cu’* Ii Fe'*+Fe”* | Pt and the standard reduction potentials: Curt + 2e° > Cus); Y= 0.34 V Felt te Fe’; £1=0.77V calculate the cell potential (emf) of the cell at 25°C when [Fe?*] = 0.040 M, (Fe™* M, and [Cu*] = 0.050 M (a) 043V (by 035V— (&) LO7V (d) 039 Solution Cus) > Cu’? + 2€ £ =~ 0.34 V (anode half-reaction, reverse equation above and change sign of Eto give oxidation potential) 2Fel 4262 E°= 0.77 V (cathode half-reaction, double above equation so equal number electrons in each half-reaction, E*, reduction potential, remains the same) + +2 Fe £9 = 0.43 V (add half-reactions, electrons cancel Culs) +2 Fe > Ci ) IEMs B+ BP Cell potential at concentrations given is calculated using the Nernst equation: gE = po 2.0592 agi Ilr n [Fe3+] go — 00592, [0.050){0.04092 —_ ” {0.0020}; 2 = 043 ~ 99522 Joy 29 = 0143 ~ (0.0296)(1.301) = 043 ~ 0,038 = 039 The answer is (d), 14.21, A chromium salt-containing solution is electrolyzed using a current of 2.00 A (am Petes) for 2.00 hr (hours). The metallic chromium deposited weighs 2.59 g (grams). Deter mine a factor for moles of electrons needed per mole of chromium deposited and deduce the oxidation state of the chromium in the salt. For this problem | F (Faraday constant) = 96,485 C (coulomb) mol. (aw. Cr = 52.00) (a) 0.33, species in solution is Cr** (b) 3.0, species in solution is Cr+ (©) 2.0, species in solution is (Cr,0,)* (d) 2.0, species in solution is (CrO,) Solution 2.00 hr x 3600 sec/hr = 7200 see Time of electrolysi 4400 C Coulombs = amperes x seconds = 2.00 amp x 7200 se 14400¢ x —E 96185 = 0.1492 F = 0.1492 mol eProblems and Solutions m 14-41 mol 259gcrx J = 0.04981 mol Cr 52.00 ¢ Lmol Cr _ 0.04981 mol Cr rmole 0.1492 mol e~ = DME2 _ 2.995 = 30 0.04981 factor = LmelCe 3 mole ‘The oxidation state of the Cr in solution should be +3, so that: Cr'*(aq) ~ 3 e > Cr(s) (3 F, or 3 mol e° for I mol Cr deposited). The answer is (b). 14-22. Using a current of 3.75 A (amperes), how long (sec) would it take to electroplate 6.19 g metallic chromium from a solution in which the chromium was in the +3 oxidation state (Cr), a.w. Cr= 52.00, Faraday constant (F) = 96,485 C mol"! (a) 2.70 10° see (c) 1.29 x 10° see (b) 1.02 x 10° sec (d) 9.18 x 108 see Solution ‘The reaction for electroplating from Cr* in solution is CPM(aq) +3. 9 Crs) factor = LmolGr 3 mol ¢ 619 gCr x 1MICE _ 9.1190 mol Ce 52.00¢ Cr 3 mol & 0.1190 mol Cr x TimlCe > 0.3570 mol e~ used to electroplate 6.19 g Cr mmol Cr 96,4 0.357 mol e° x 22465€ _ 34. 445¢ | mole = 9185 see = 9.18 x 10° see amp 475 amp amp X sec sec = ‘The answer is (d). 14-23. A solution of nickel sulfate (NiSO,) was electrolyzed for 0.75 hr between inert elec trodes. If 17.5 g of nickel metal was deposited, what was the average current? (a.w, Ni = 58.69, Faraday constant, F = 96,485 C mol!) fa) Li x10! (©) 2.110! (b) 13x10" (d) 16x10!ay 14-42 Ml Chemistry Solution L mol 58.69 g Reaction is: Ni?* (aq) + 2 e° = Ni(s) Lmol Ni _ I mol Ni Moles of Ni 15g x Factor is: "2 _ 2mole 2F 2 96485 Coutombs = 2.98 x 10-1 mol Ni x —2F_ 96485 _ sos gs Tmol Ni” 1 C=amp x see sec = 0.75 hr x 3600 = 2.70 x 10° see 5.15 x 104C 2.70 x 10* sec amp = = 21 x 10! amp ‘The answer is (c) 14-24. A spoon, with a surface of 45 em’, is suspended in acell filled with 4 0.10 M solution of gold (ILI) chloride, AuCl,. A current of 0.52 amp has been passed through the cell, until a coating of gold, 0.10 mm thick, has plated on the spoon. How long did the current run? (den. sity Au = 19.3 g/cm’, aw. Au = 196.97, Faraday constant, F = 96,485) (a) 1.3% 10 see (3.6 hr) (©) 4.1 10 sec (11 hey (b) 2.5 x 10" see (6.9 hr) (d) 8.2 10" sec (2.3 hr) Solution The electrode reaction is: Au'*(aq) +3. = Au(s) L mol Au Factor is: L@0lAu 3 mole ‘The volume of Au deposited = 45cm? x 0.10mm x LSM _ 0.45 ema 10mm 1, 193g The weight of Au deposited is = 0.45 cm’ x : £ - $68 ¢Au am 3mole- 96485C x wee x Imol Au” mole The coulombs passed = 8.68 g Au x = 128 x 108 C = amp x sec see = © amp 1.28 x 10°C 0.52 amp Time of run = = 246 x 10° see X10* sec (6.9 hr) ‘The answer is (b). Assuming 100% dissociation, calculate the molarity of the H* (H,O*) ions in a solu- tion made by diluting 10.0 ml of 0.10 M HNO (aq) to 500.0 ml (a) 0.0010 M (©) 0.020M (>) 0.010M (d) 0.0020 MProblems and Solutions wm 14-43 Solution moles solute Molarity (M) = liters (L) solution ‘Therefore, moles solute = M x L solution moles solute = 0.10 x 0,010 L = 0.0010 mol HINO, A quantity of 0.0010 mol HINO, is diluted to 500 mi. The molarity (M) of the solution is given by 0.0010 m 0.500 L NOs — 0020 M= Since HNO,(aq) is 100% dissociated into ions, HNO, + H* + NO,~. the 0.0020 M solution will contain 0.0020 M H*(H,0*) and 0.0020 M (NO,”). The answer is (d), 14-26. How many ml of water need to be added to 30.0 ml of a 12.0 molar (M) solution of HCI o give a 3.00 M solution? (a) 120ml (b) 133ml) 90 mL (a) 60m Solution Since the number of moles of HCI remains the same, that is moles HCI = moles HCl, we can use the relationship: (volume,) x (molarity,) = (volume,) (molarity,). Substituting the values given: (30.0 ml) x (12.0 M) = (x ml) x (3.00 M) 20 ml for volume of solution, Since the original volume (solution,) is 30.0 ml, the volume of water to be added is 120 ~ 30 = 90 ml. The answer is (c) 14-27. _A stock solution is prepared by dissolving 30.0 g of NaOH in water and diluting to a final volume of 500 ml. How many ml of this stock solution are necessary to prepare 1.00 L of 0.100 M NaOH? (a.w. Na = 22.99, O = 16.00, H = 1.008) (a) 66.7 ml (b) 375ml (e) 150ml (d) 167 mi Solution First calculate the number of moles of NaOH dissolved, and the molarity (M) of the stock solution. 30.0 g NaOH 400 gimol = 0.750 mol NaOH en M = moles _ 0.750 mot iter 0.500 L 1.50 In 1.00 L of 0.100 M NaOH, there are: 0.100 mol 2100 MOH 1.00 L = 0.100 mol NaOHOS) 14-44 Ml Chemistry Now calculate the volume of 1.50 M NaOH solution which contains 0.100 mol NaOH. 9.100 010667 L = 66.7 mi 1.50 ‘The answer is (a). 14-28. In the laser cutting of polyvinyl chloride, hydrogen chloride gas is formed. In a certain laser-cutting process for polyvinyl chloride, the hydrogen chloride formed was dis- solved in water and titrated with 0.0100 M sodium hydroxide (NaOH) solution. The titration required 37.68 ml of NaOH to reach the endpoint as indicated by a color change of bromothymol bblue indicator. How many milligrams of hydrogen chloride were formed in this laser-cutting process? (a.w. H = 1,008, CI = 35.45) (a) 103mg (b) 137mg —(e) 103mg (@) 13.7 mg Solution First, calculate how many moles of NaOH were used in the titration 0 01 IL 20100 mOLNSOW 5 (37.68 mi NaOH) x = 3.77 x 10-4 mol NAOH IL 1000 mi The balanced equation for the reaction is: NaOH(aq) + HCl(aq) > NaCi(aq) + H,0 showing that | mol of NaOH neutralizes | mol HCI. Then, the weight of HC! can be calcu- lated from: Lmol HCl 36.46 g HCI (3.77 x 10 mol NaOH) x [mol NaOH” Tmol HCI , 1000 mg HCI = 13.7 mg HCI Tg HCl ne answer is (d). 14-29. Calculate the volume of 0.250 N Ca(OH), needed to completely neutralize 75.0 ml of 0.150 N HPO, (a) 450ml (b) 125ml (©) 225ml) 41.7 md Solution By definition one equivalent of acid is equal to one equivalent of base in a reaction. The number of equivalents of Ca(OH), at the neutralization point must be equal to the number of equivalents of H,PO, at the neutralization point. In a two step solution find the number of equivalents of HPO, first, from: equivalents = volume in Lx normality Equiv. = vol(L) x N = 0.0750 x 0.150 = 0.01125 Since the same number of equivalents of Ca(OH), was used in the reaction:Problems and Solutions m 14-45 0.01125 = x(L) x0.250 += 0,0450 L Ca(OH), solution A one step solution is: equivalents Ca(OH), = equivalents H,PO, equivalents, Since normality (N) = A volume solution (L) N, x vol(L), = N, x vol(L), (0.250) vol(L), = (0.150) (0.0750 L) vol(L), = 0.0450 L = 45.0 ml Ca(OH), Icis also convenient to multiply N, x vol(L), = =N, x vol(ml), and 1 X vol(L.), by 1000, so that N, x vol(ml), (0.150) (75.0) 0.250 vol(ml), = = 45.0 ml Ca(OH), The answer is (a). 14-30. Metallic elements are found where in the periodic table? (a) in the far left and far right hand groups (b) in the middle of the table and Group VINA (6) im the left hand and middle groups (@) only in Groups TA and 1A Solution ‘The metallic elements are found primarily in Groups IA and IIA at the left of the table and Groups IIIB-VIIIB and IB-IIB in the middle. They are also in the higher period elements of Groups IIIA-VIA. There are no metals in the far right Groups VIIA and VIILA, ruling out (a) and (b). There are metals in a number of groups besides [A and IIA, ruling out (4). The answer is (0). 14-31. Metals have: (a) both high electrical and high thermal conductivity (b) high electrical but low thermal conductivity () low cohesive strength and high luste : (©) lowe rength and high luster Chemistry (@) high luster and tow ductility Solution ‘The mobile electron cloud of outer electrons gives metals both high electrical and high ther- ‘mal conductivity. The mobile electrons and accompanying crystal structure also gives metals. high luster, high cohesive strength, and high ductility. The chemical reactivity of metals var ies from high (Li, Na) to low (Pt, Au). The answer is (a).Py 14-46 Ml Chemistry 1 32. Nonmetals are: (a) malleable but not ductile (b) very reactive with acids (c) good conductors of electricity (d) able to form halides which react with water to give an oxyacid Solution The nonmetals are generally neither malleable nor ductile. They do not react with acids and are poor conductors of electricity. Often they have low melting points and are volatile. How ever they do form covalent halides which re with water to give oxyacids. The answer is (d) 14-33. The following metals are in a single group in the periodic table: (a) lithium, sodium, potassium, strontium, and cesium (b) iron, cobalt, nickel, platinum, and gold (©) boron, aluminum, gallium, indium, and thallium (d) beryllium, magnesium, calcium, barium, and radium Solution Strontium is a member of Group IIA, not IA. Gold is in Group IB, while the other metals in choice (b) are in Group VIIIB, All the elements in choice (c) are in IIIA, but boron is not considered a metal. The elements in choice (d) are all metals in Group ITA. Germanium, tin, and lead are in Group IVA, and antimony and bismuth in VA. The answer is (d). 14-34, The halogens: (a) will not react with each other (b) are strong electron donors (©) form strong oxyacids of the formula HOX, (4) form strong covalent bonds with Group 1A metals tron acceptors. They do form strong oxyacids of the formula HOX,, as well as HOX,. Halogens form ionic bonds in compounds with Group IA metals. ‘The halogens bond with some nonmetals, such as sulfur and phosphorus, as well as other halogens. The answer is (©) 14-35. The dissolution of sulfur dioxide (SO,) in water produces: (a) @ weak solution of sulfuric acid, H,SO, (b) a weak solution of pyrosulfuric acid (disulfuric acid), H,S. (©) a solution used as an analytical reagent to precipitate metal cations (d) a weak solution of sulfurous acid, H,SO,Problems and Solutions wm 14-47 Solution Sulfuric acid forms from the reaction of SO, with water. Pyrosulfuric acid is formed from 80) and concentrated sulfuric acid, SO, solution is used ws a reducing agent, bu it is H,S that 'sused in analytical determination of metal cations. SO, can be converted to SO, by oxidation in the presence of a catalyst. A weak and unstable solution of sulfurous acid is formed upon dissolution in water. The answer is (4). 14-36. Nitrogen, N,, forms several oxides; two which exist in equilibrium at ambient tem- perature are: (a) NO, and N,O,, which exists in the equilibrium 2 NO, =N,O, (©) NO and NO,, which exist in the equilibrium 2 NO + 0, = 2NO, (©) NO and N,O, which exist inthe equilibrium 3 NO = N,O + NO, N,0, +0, (4) N,, and N,O,, which exist in the equilibrium 2.N,O, Solution Dark brown NO, and colorless NO, exist in equilibrium at ambient temperature, NO reacts rapidly with O, to form NO, at ambient temperature. NO is not normally in equilibrium with N,O and NO, but can decompose to yield these species when pressurized at moderate tem- Peratures, NO, decomposes at moderate temperatures to yield N,O, or NO, N,O, decon Poses when vaporized to NO + NO,, Although all the reactions above take place under appro- Priate conditions, (a) is the only one which could be considered in equilibrium at ambient temperature. The answer is (a), 14-37. A number of carbon compounds with metals hydrolyze to release: (a) carbon dioxide (CO,) (b) carbon monoxide (CO) (©) amixture of carbon dioxide and carbon monoxide (4) either acetylene (C,H.,) or methane (CH,) Solution Carbides of some metals (for example copper, silver, calcium) are believed to contain the acetylide ton, C,*, which hydrolyzes to acetylene. Carbides of other metals (for example Al) may contain a methanide ion, C*, and hydrolyze to methane. The answer is (d). 14-38. Silicon (Si) is important in the semiconductor industry because In (a) of its outer electron configuration of two electrons in s orbitals and two electrons in p orbitals (b) the energy band gap between valence electrons and conductance electrons in the crystal is relatively small (6) its melting point is low enough that it can be melted and cast into chips (4) itis the most dense of the Group [VA elements and this allows a high electron density in devicesuy 14-48 Ml Chemistry Solution The relatively small energy band gap makes silicon an intrinsic semiconductor and leads to its industrial use, The answer is (b) 14-39. The substitution of AI’ for Si in the compounds with St-O—Si is important to: (a) the use of Si in semiconductor chips (b) the production of silicone polymers (©) the formation of clays and zeolites (A) the production of specialty glasses Solution Semiconductor silicon is very pure Si until it is doped with a 3+ or 5+ element. Si-O—Si Si-O bonds. may occur in surface coatings. Silicone polymers have SiC bonds as well as Clays and zeolites often contain trivalent Alin the St—O—Si structure anda counterion such as Na® or K* to balance the charge. Glasses are supercooled liquids with oxides of boron, lead, sodium, and calcium mixed with silica. Quartz, with a high melting point, is essentially pute silica. The answer is (c) 14-40. The reaction below is carried out in a 5.00 L reaction vessel at 600 °K. CO(g) + H,O(g) = CO,(g) + H(z) At equilibrium it is found that 0.020 mol CO, 0.0215 mol H,O, 0.070 mol CO,, and 2.00 mol H, are present K for this reaction (a) 65.1 (b) 0.00307 (c) 236 (d) 326 Solution The chemical equation is balanced so: {CO,@)H,(2)) {CO,(g)][H,O(g)] [om roto, [200 mm) K nol HC Si: ie 020 mol 9] 2 021 SL Note that the units cancel, leaving K, dimensionless. The answer is (d). Consider the following reaction at equilibrium: N,O,(g) = 2 NO¥g) Ifa 5.00 L reaction vessel, held at constant temperature, is initially filled with 10.0 mol pure N,O,(g), and if 3.5 mol NO{g) are found in the vessel once equilibrium has been established, what is the value of the equilibrium constant, K,, for this reaction (at the temperature of the experiment)? (a) 0.297M —(b) 148M _— (©) 0.424M_—(d) 0.0594 MProblems and Solutions m 14-49 Solution A good general approach to equilibrium problems is 1) write the ba tion equation, 2) write the equilibrium constant expression in terms of the balanced equation and 3) identify in a simple tabular form what is known about the concentrations of species initially and at equilibrium, and what change(s) occur. For the above problem, these proc dures give: lanced equilibrium reac 1) (as given) N,O,(g) = 2NO,(g) 2k, = NOE (N,0,] 3 ‘Species: _NjO,mol_ NO, mol Initial amt. 10.0 0 Change (1.75) 43:50) Equilibrium (825) 3.50 amount ‘The values nor in parentheses are given with the problem and are filled in first. The blanks are filled in with the values in parentheses from the calculations below, In order to produce 3.50 mol NO,, the equation shows us that half this amount of NO, has decomposed, or: I mol N,0, 3.50 mol NO, x ** 2mol NO, = 1.75 mol NO, Therefore, at equilibrium, 10.0 ~ 1.75 = 8.25 mol N,O, remain, The equation for the equilib rium expression is then: 2 50 mol NO, = 4 S00], D70MP _ oom [ 25 ay (1.65 M} 500L Note that the presence of the square term dictates the equilibrium constant units (mol/L = M). Note also, that the vessel size (5.00 L) must be included in the calculations. The answer is (a). 14-42. Ata given temperature the equilibrium concentrations in a reactor were found to be PCI, = 0.25 M, Cl, = 0.25 M, and PCI, = 0.125 M. Calculate the equilibrium constant at the given temperature for the reaction: PCI, = PCI, + Cl, (a) 0.125M —(b) 20M_—(c) (SOM (d) 0.25M Chemistry Solution ‘The expression for the equilibrium reaction is: ch ICI 2 250 25 MJ? (PCH ICh] _ (0.25 MHIO.25 MJ _ 10.0625 MI" _ 4 55 ny K, 8 (PCI) (0.125 M] (0.125 Mj The answer is (c)ee 14-50 Ml Chemistry +43. What is the molarity of a solution prepared by dissolving 15.0 g of La(NO,), in 800 ml of water? (a.w. La = 138.91, N = 14.01, 0 = 16.00) (a) 0.093M —(b) 0.031M — (¢) 0.048M (A) 0.039M. Solution First, calculate the molecular weight of La(NO,), 1x (aw. La) +4 x (aw, N) + 12x (aw. O) 138.91 + (4x 14.01) + (12 x 16.00) = 386.9 150g 386.9 gimol Number of moles in 15.0 g La = 0.0388 mol 3 Motarity = m 20388 mol f 0.800 0.048 M ‘The answer is (c) 14-44. If 15.0 ¢ of 26% LiBr solution is diluted to a volume of 80.0 ml, what is the molarity of the resultant solution? (a.w. Li = 6.9, Br= 79.9) (a) 071M — (b) 036M = (©) 044M_—(d)._: 56M Solution The moles of solute before dilution equal the moles of solute after dilution moles = —— = volume (L) x molarity (M) 0.26 x 15.0 86.8 =0.080L x M M = 0.56 The answer is (d) 14-45. The vapor pressure of pure ethyl alcohol (C,H,OH) at 30°C is 71.2 torr and that of pure carbon tetrachloride (CCl,) is 121.6 torr. Calculate the pressure above a solution con- taining 20.0 g of C,H,OH and 60.0 g of CCL, assuming ideal behavior. (a.w. C= 12.01, H = 1.008, 0 = 16.00, Cl = 35.45) (a) 109 torr (b) 97Btorr —(c) 75.2t0 —(@)-95.0 torr Solution ‘The total pressure above an ideal solution is the sum of the partial pressures of nent multiplied by the mole fraction of each component: P=XP) + XP,Problems and Solutions m 14-51 20g Nesiga =! — = 0.434 mol ‘HON “46,07 g/mol 00g Nec, = eB = 0.390 mot «153.8 g/mol yyy = 0.434 + 0.390 = 0.824 mol 434 x, = 4 9527 e,H,on 0824 . 39 X, = 239 _ oanscer, > * 0.824 P= (0.527) (71.21t08r) + (0.473) (121.6 torr) = 37.5 + 57.5 = 95.0 torr The answer is (d). 14-46. A quantity of a covalent substance of molecular weight 73 is dissolved in 425 g water. If the resulting solution has a boiling point of 100.31 °C at 1.06 of this substance were added? (K,, = 0.512 °C mr for water) tm, how many grams (a) 104g (by 27g (CV SBE a) 19g Solution AT = K, m. Rearrange to: urec Ar = Oe = 01606 mol key, K, — 0512°Cm mw. = 73 g/mole 0.606 mol kg \ieu X73 g mol" = 44.2 ¢ ke 425 g water = 0.425 kg solvent 44.2 8 Ke incu X 0.425 kg solvent = 19 g The answer is (d). 14. ‘The following initial rate data were obtained for the reaction: 2 B > C. ym r= 2B ice Te ae (0245-29210 (290.490 4.13104 PUTS Find the exponential coefficient of the rate law, [BY for this ve 20 (@m=-05 (by n=05 ()n= 10 (WanChemistry 14-52 Chemistry Solution Divide equation for data (1) by equation for data (2) to find single value of nr=k [BI* TOME gn oh CBS Retcetatay k (Bh = (Bhs ‘Take log of both sides of the equation: tg EM gy I tee = I8 tae "PE Ca, Solve for nm: 2.92 x 104 Msec log 13x 104 Msect _ 0.151 hie X 104M sect _ = 0502 =05 r= k{Bps og lh Tog 024M 0.301 o 5 [Bh 0.490 M ‘The answer is (b) 14-48. Consider the following gas phase reaction: CH,CHO CH, +CO Can the order of this reaction be determined from the above balanced equation? If so, deter- mine the order and explain; if not, explain (a) Yes—the reaction is second order because each molecule of reactant must collide with a second molecule of reactant to decompose (b)_Yes—the reaction is third order because each molecule of reactant collides with other reactant species as well as with each of two species of product molecules (©) No—the reaction order can't be determined from balanced equation and reaction coefficients alone; must have experimental dat (d) Yes—itis a first order reaction because the only reactant is CH,CHO, which can only react with itself S lution ‘The rea n order can be obtained for a reaction represented by a balanced stoichiometric equation only by considering adequate experimental data. Such data would come from ex: periments wi the concentration of reactants is varied one at a t rate of disappearance of a reactant or appearance of a product. ‘There is possible confusion because the re e and compared with the ction written as a stoichiometric equation mentary reactions. The elementary re cular. When an elementary reaction step is es {ablished, the reaction order of that particular elementary step follows from its equation ‘The answer is (c) can derive from one or more steps called ef can be unimolecular, bimolecular, or termok jons14-49. Consider the following set of data Write the rate equation ( constant, k, in proper Problems and Solutions Rae (ad Set_mol/A. sec _ moll (0020 0.10 @ 0080 0.10 G) 008 9.20 @) 0060 030 (a) R =k [A] (BP, order = 3, k = 5.0 sec"! (b) R= k [AP [B], order = 3, k = 10 sec! (©) R=K IAP IBF, order (4) R=k [A] [B), order Solution From Set (1) and Set (2) of data: when the concentration of [8] doubles, the rate quadruples. Therefore, the reaction is second order in [B]. From Set (1) and Set (3) of data: when the concentration of [A] doubles, the rate doubles. Therefore, the reaction is first order in (Al. Overall order is 1 +2= 3, ‘The specific rate constant, k, can be calculated from any set of data Set a Q @) @ ‘The answer is (a), 14-50. An analysis of a 2,147 g sample of a hydrocarbon produced 7.260 g of carbon diox- 2.01, 0 = 16.00, H = 1.008) ide and 1.485 g of water. (a.w. r =I, k= 50 L mol sec"! 0.20 mol L* sec"! R=K (ABP Rae (Al ol ML soe mol 0020 0.10 0080 0.10 0040 0.20 0060 030 c (8) _molfl._k sec" 020 50 04050 0.20 5.0 020 50 (8) ol 020 00 020 020 = rate), the overall order of the reaction, and the specific rate Calculate the percentage composition of the hydrocarbon (a) 97.27% C, 2.73% H (b) 92.27% C, 7.73% H (c) 93.73% C, 6.27% H (d) 91.27% C, 8.73% H Ay14-54 Ml Chemistry Solution Al the carbon in the carbon dioxide and all the hydrogen in the water come from the hydro carbon 2.01 g Cimol %Cinco,: 20 ECO! 199 _ a7 296.6 * 44.01 g COy/mol £C=7.2602.CO, x 0.2729 = 1.981 gC 2.016 ¢ Wimol 18.016 g H,O/mot gH= 1485 gH,0x 0.1119 = 0.166 gH % Hin H,O. 100 = 11.19% H Calculate elemental percentages: we = — NEC ey < or 7K 2.147 g compound wu = —O16BH iy a agit 2.147 g compound Note: Since the compound is defined as a hydrocarbon, the percent of each element calculated independently should add to 100%. The answer is (b) 14.51. Cyclopropane is 85.7 % carbon. Cyc! (a) somewhat more than 85.7 % carbon (b) somewhat less than 85.7 % carbon (©) exactly 85.7 % carbon (d) exactly half the carbon percentage of cyclopropane Solution Both compounds contain only carbon and hydrogen. Cyclopropane is a ring structure of thr carbons singly bonded to each other and two hydrogen attached to each carbon, The forn is C,H, The ratio of carbon to hydrogen is 1:2. Cyclohexane is also a ring siructure of six carbons singly bonded to each other and two hydrogens attached to each carbon, The formula is CH, . The ratio of carbon to hydrogen in cyclohexane is 1:2. Therefore cyclohexane must have the san ize of carbon as cyclopropane. pere Check: 6 x 12.01 = 72.06 gC per mole cyclohexane; (84.16 m.w. cyclohexane) 12x 1.008 = 12.096 g H per mole cyclohexane BL 857100 = 482% Cia youn The answer is (c), 14-52. An organic compound has an empirical formula of C,H,O. This formula can represent (a) 3 alcohols (©) 2alcohols and I ether (b) L organic acid (d) 2ethers and | alcoholProblems and Solutions m 14-55 Solution Only alcohols (ROH) and ethers (R—-O—R fit the general formula C,H,O. Three struc tures are possible: the alcohols, CHC, and cere, OH oO H and the ether, CH; O—CH,CH,. The answer is (c), 14-53. Name the type of compout h of the following structural formulas a) CH,—CH,—OH (a) aldehyde (6) organic acid (b) aleohot (a) ketone b) H I cHy—C=0 (a) alcohol (©) alkyne (b) ester (4) aldehyde . oO CH,C—O—cH, (a) ester (6) organic acid (b) aldehyde (d) glycol 4d) CH—CH,—NH, (a) nitrile (c) amide (b) alkyne (d) amine CH,— ae aU (a) amine (c) amide (b) nitrile (d) azide p oO I CH;—C—cH, (a) aldehyde (c) ketone (b) alkane (@) etherPSE 14-56 Ml Chemistry Solution a) is an alcohol, characterized by the OH group bonded to a carbon. The answer is (b). b) is an aldehyde, characterized by the CHO group bonded to a carbon, ‘The answer is (d). ©) isan ester, characterized by the COO in which the characteristic carbon is double bonded to In the ester, the second O atom is an O atom and single bonded to another C and an O a also bonded to another C. The answer is (a) 4) isan amine, as the carbon chain ends in a carbon bond to the N of an NH, group. The answer is (d). €) is a nitrile, characterized by the triple bond between the end C atom and an N atom. The answer is (b). A isa ketone, characterized by the C=O group in which the C is bonded to each of two other C atoms. The answer is (c),