Chapter 7 Reese Recto ao Crema Eat 202 (The NO is recycled back into the reaction, Uses of HNO, include explosives, polymers, and fertilizers. 26. shifts lefts shifts right; shifts left; no change; no change 27. (a) Conditions of low pressure and high temperature will maximize the production of polystyrene. (b) Conditions of low pressure and high temperature are diffcule to achieve in industrial applications. To maxi- mize the yield, the polystyrene must be extracted as the reaction continues, keeping the equilibrium shifted to the right. {€) The products of the reaction between steam and carbon are carbon monoxide and hydrogen gas. (d) The super-heated steam supplies energy to a reaction that is endothermic, This will shift the equilibrium to the right, favouring the production of polystyrene. MHR © Unit 4 Chemical Systems and Equiioium (6) Super-heated steam 2t 600°C will increase the reaction ‘temperature, without having to heat the rection vessel itself If che steam were only at 100°C, additional heat ‘would be needed to maximize polystyrene production. (8 The iron oxide catalyst is used to increase the (6) If the temperature is raised, possible degradation of the catalyst can occur; as wel, the pressure of the system Would likely increase, thereby shifting the equilibrium back to the left. (h) The ethyl benzene is evaporated from the reaction mixture, condensed, and re-used in further polystyrene production. Q“ we 17. (8) SOx) + HF y * Sg + 3Hj0p (6) [S05] = 2.9 mol + 47 L = 0.62 mol/L (HF) = 9.1 mol + 4.7 L = 1.94 mol/L. Concerzaton] S0uq | +] Shy ]=] SFom] */ Oy (mov) ee 194 ° 0 Change _[-x or x | [ae Equitovvm Jose—x] | 194-6 | [x ax (6) When the equilibrium conditions are put into the equi- librium expression for the reaction, the equation con- tains terms to the 6th power. This proves to be very dificue to solve using simple mathematics. 18. For Experiment 1 _ 1805? a K= Basoge * Tanase ~ 436 For Experiment 2 2 2 rr 10,]150,}? ~ (0.0450)(0.590y ‘Within experimental error, these values may be considered equal. 19, ANHyy) + 50ny & AND + GH; INO}S(2.016 K* GosINH, {NO} = [NH] K=026 Answers to Communication Questions 20, A student answer mighe read: Energy is conserved in a chemi- cal reaction. Energy gained by the system is equal tothe energy lost by the surroundings, or vie versa. Therefore, the ‘combination ofa reaction system and its surroundings cannot sain any additional energy; the best you can do, in other ‘words, is break even. However, since che entropy of the uni- verse is always increasing, you cannot even break even. 21, (a) This graph should show the concentration of H decreasing with time, and the concenteation of FIL increasing with time. (b) The graph of I} and [HI] with time should look simi lar to the graph sketched in (a). The concentrations of I, and H, should decrease at the same rate, and that of Hi should increase. (@ The value of Q will increase until ic reaches the same value of K. 22. Adding a small crystal roa saturated solution of copper(I) sulfate disrupts the equilibrium of the system. CuSO, can no longer dissolve and the reaction shifts co adjust co the addition of the solid. Thus, the ions come out of solution (0 form a solid Answers to Making Connections Questions 23, A student answer might read: The second law of thermody- namics says chat the entropy ofthe universe is always increasing. Western societies lead lives of high entropy. By using numerous products, we also produce large quantiries of waste (high entropy). Consumer products originate through industrial processes chat make use of the Earth’ energy resources (low entropy matter). The impact ofthis is scen through the buildup of garbage on our streets as our Jandfils cannot keep up with the demand. 2A, In 1 L of at, chere is 0.80 L of N, and 0.20 L of O, Concentration of N, = (0.80 L + 22.4 L/mol) + 1 L = 0.0357 mol/L Concentration of O, = (0.20 L + 22.4 Umol) + 1 L = 0.0089 mol. Ne + | Px =] N | Tal [00357 oon 0 change | = = v_| Equilibrium | 0.0357 —x 0.0089 —x a {NO} KIN 471073! = (2x)? (0357 = (0.0089 — Using the aproximation method x= G11 x 10718 (NO) = 1.2.x 10717 Although this concentration of NO appears to be very small, additional amounts of NO are received from auo- mobile and industrial pollution. 25. (a) A decrease in pressure, or the removal of heat fom the system, (b) A catalyst lowers che activation energy and increases the rate ofthe reaction, but i does not change the equlib- rium position. (0 This reaction must be carried out at selatively high temperatures to improve the rate at which NO is pre- duced. Although the reaction appears to be favoured by low temperature, high temperatures are required for NO to be produced at an optimum rate. (@) Since there are more gaseous product molecules, che product side exerts a greater pressure than the reactant Side. By lowering the pressure, the equilibrium will shift tothe right. (6) The gascous products are cooled to shift the reaction equilibrium to the right, favouring the production of NO,, The extracted heat is used to increase che temper ature of the surroundings. a Chapter 7. Reversible Reactions and Chemical Equilibrium * MERChapter 7 Revensisue REACTIONS ANO CHEMICAL EQULBRIUM .50mol/1OL = 0.05mol/L. 8. An increase in pressure will result in a decrease in volume. 13,(CO] = (H,0) = ‘Since the reactant side of the equation has fewer molecules than the product side, the equilibrium will shife co the ef. [ Concentration [CO [+]H20) |= | Hay 9. (a) The increase in pressure will increase che concentration | (OVL) of reactants, while the concentration of products will intial 005 005 0 dec me equim wil aio Be ighs whee PY = algae (b) Once equilibrium is re-established, CH, and HO will | Equilibrium [0.05 ~ x] [005 - x x x show an increase in concentration. c= Halley Answers to Inquiry Questions — 10. ] = 5.6 x 10-4 mol 3=aR oF ‘The volume is constant. The concentration of Hl and H is calculated using mole ratios. [j}H,] are in 1:1 ratio. 2.88 7 ‘Therefore, (H] = 5.6 X 10~4mol/L. [I:(HI] are in a oe ie = y~ 4m ae 1:2 ratio. Therefore, [HI] = 5.6 x 10~4molL. x 2 eee = 1.12 x 1073 me a eer [CO] = [H,0} = 0.05 ~ 0.037 = 0.013 mol/L. 11, [Concentration | 250, [+ = [28059 |] 14. Change in concentration of Sg) = 9.2 X 1073 mol/L tov = 23 X 1073 mol/L = 0.0069 mol/L. Concentration of ntl W W 0 Sajg 2€ equilibrium = 0.0069 moVL. X 4 = 0.028 mol/L. Ee ve] gat 5 Gal ili fe 2 facia (0.0284 _ (soy? 23 x 1073 = Boo] K.=25x 10-4 use che approximation method 15. According to the second law of thermodynamics, the total oo eas entropy of the universe is increasing, Heat released by the (L707) machine will radiate into the surroundings, causing an = 0.066 increase in the random motion of particles, thereby inceas- [503] = 20.066) = 0.13 mol. ing te eopy of the soundings: Say cen, In esate tects oe ‘nature, a state of increased entropy is favoured, so energy Meare med eh deel edd will spontaneously move from the machine to the sur- Ipropancic acid] = 40.0 g + 74 g/mol = 0.54 mol roundings, increasing the sate of disorder. The energy will not be recycled back into the machine, causing its motion Concenration | GH,OH | +] CHC [= [OKC | +] 4,0 to eventually sop. trol) ooH | | oot, 16. (0) AHCly + Oxy w 2H,0y + Clyy Initial 085 054 0 mK [H,OF ICL? _ (7.8 x 1073.6 x 10-3 Change | -x “* +e A THCIMIO,) = @.7 x 10-)48.6 x 107) Equiiovium [oss-x | [ose—x] [x “17 x 10 0.65 — 9054-9 752 — 9.94x + 2.64 =0 <= 0.38 0F 0.96 <= 0.38 mol Mass of ethyl propanoate = 0.38 mol X 102 g/mol = 374g 735 200 | MHR + Unit 4 Chemical Systems and Equilibrium3. (@) no change () right (0 left {) no change (liquid volumes are largely unaffected by pressure changes) 4. (2) Nag + 3Hayy) = 2NHy) + 92K) (8) Changes thar can increase the yield of ammonia include: adding N2 or H2, removing NH3, increasing the pressure, lowering the temperature 5.(a) 2509) + Ory) = 20g) + energy AH is negative (energy is released) » (©) Changes hac can increase the yield of sulfur trioxide include: adding SO, or O,, removing SOs, increas ng the pressure, lowering the temperature (0 This reaction isearied out at high temperatures becouse at lower temperatures the yield of SO, is relatively low High temperatures increase pressure ofthe reaction mi ture, thereby shifing che equilibrium tothe right. (a) A vanadium pentoxide catalyst i required to increase che yield of SO, at lower, more manageable temperature: Careers in Chemistry Student Textbook page 371 Answers to Making Career Connections 1. Anesthesiologists can also be found in the recovery room watching patients emerging from the effects of the anesthesia, in a doctor's office or dencal office assisting with pain management, asisting with critical care and trauma medicine, oceasionaly assisting in stax ing patients during transfer, as well as in situations involving non-surgical treatments, diagnostic proce- dures, and research laboratories. 2, Beyond ensuring patient comfort, an anesthesiologist ‘must act also make crucial medical judgments to pro- tect and regulate a patient’ life functions. Anesthes- iologists, must know, understand, and evaluate a patient's medical condition, monitor body functions, and be aware of any interactions that could possibly ‘occur between the anesthetics and a patients current medication and diet 3. Local anesthetics: ae used to control pain in a specific area ofthe body and are commonly used in minor med- ical procedures (e-,, receiving stitches or hernia repa) Regional anesthetics: also known as a regional block are used to block pain in a specific part of the body (eg, a hand or a ke) General anestheti are used to stop pain from being, fele during a medical procedure such as surgery, by ren- dering a person unconscious. ME AU Ud Student Textbook pages 372-375 Answers to Knowledge/Understanding Questions 1. The rate ofa reaction isthe time required fora particular amount of product co form. The extent of a reaction is the relative concentration of products to reactants at equilibrium 2. The state of equilibrium involves dynamic change atthe ‘microscopic level, even though there is no change at the ‘macroscopic level. Reactant and product molecules are constantly moving in the forward and reverse reactions 3. Ina reaction that goes co completion, the products are favoured. The numerator in the equilibrium equ ‘which represents the concentration of products, must be large compared ro the denominator. Therefore, Ki very large 4.0) ~AHand +S contribute ca favourable reaction (b) +AHand —AS contribute wan unfavourable reaction. 5. Factors that ean affect the equilibrium ofa reaction are emperature, enthalpy, and entropy. 6. The solubility ofa solid in aliquid increases asthe temper ature rises beeause of the larger entropy associated with the molecules in a liquid. The motion of molecules in aliquid is much more random and chaotic chan in a solid. On the other hand, the solubility of a gas decreases as the tempera ture inereases because of che decrease in entropy asthe gaseous molecules reac ro form a liquid, 7. A decrease in temperature wil shift the equilibrium to the right. The lower temperature relieves the heat produced in the exothermic eacton. A decrease in volume will have 10 effect on the equilibrium because there ae che same nun’ bets of molecules on either side of the reaction equation. (Chapter 7. Reversible Reactions and Chemical Equibrium + MR[TIED chapter 7 reverse Reactions ano Chemacat Eouusmuts Assessment and Evaluation Thoughtlab/ Assossment ExpressLab/ | Curriculum Tools/ Achievement — Investigation | Expectations Techniques | Chart Categories | Learning Skills Investigation 7-B:| Specific Expectations = Rubricfor —|[m Knowledge/ —|m Work Habits Perturbing Investigation 7- | Understanding |m Organization Developing Skills of Inquiry and Equilibrium, Communication B:Perturbing | = Communication ages 358-361 | "{cSe702 apply Le Chieti’ principle | Eaiboum topredietnaw varous actrsafacta | SP2Assss- chomical system ateqiium, and. | Rt confirm their predictions through Teacher's experimentation Teachars CD-ROM) 7 Suen Textbook page 364 BSS ea UTS ST ‘Adecreaseinvolume prompis an Student Textbook page 362 increase the concentration ofa tvge species. The concenvatons Aewers to Making Connes of $0, and Oar intially ns Questions increased duoto the reductonot t+ Two other examples that illustrate che Le Chatelier’ Principle are: (a) che equilibrium ‘volume, butthen decrease asthe between two bodies of water, one fresh and the other salt, that are connected to each ‘qultriumis sited tthe let, other (there will be a constant movement of fresh water into the salt water body and increasing the concentration of vice versa, with both of these movements occusring,at the same rate); (b) equilibrium ‘0 This occurs because there for the binding becween hemoglobin and oxygen in the bloodstream (high concentra- yg) are fewer gas molecules onthe tions of O, will shift the equilibrium to che right, causing the blood to become oxy- left side of the reaction than on genated, while inside the cells, O, is consumed as the equilibrium shifis to the lef, the right making more O, available to the cells). 2. Scudents should be encouraged to sketch graphs or flow charts initially indicating a bal- ance between two components of an ecological, physiological, or economical system. Next, some change should be introduced to the system and the resulting shifts in popu- lation, pH, $, etc. should be shown as well as he new equilibrium thae is reached. Solutions for Practice Problems Student Textbook pages 366 and 367 See Solutions Manual for solutions to Practice Problems. Bs el ed Student Textbook page 370 4. (@)righe temperature (bight {b)low temperature {no change {€ high temperature (aright {@) high cemperacure (edlete he 198 | tiie © Unita Chemical systems and Equilibrium2, & 3.The following chart summarizes expected observations. = | Part | Step | Increase concentration | concentration at of product’ | of reactant) StuienTexhook pone 99 decrease in | decrease in cat + ¢0,2-— ceca, concentration | concentration ‘During a hot spell, the ofreactant | of product é concentration of CO,2- wit lower ina chicken’ blood 2 yes no H* added, shift to right: orange siroam, theraby reducing the 3 no yes OH” edidad, shit to lett: yellow concentration of carbonate ' i ions avaiable frm calcium # yes no QH™ removed, shift to right: orange | | carbonate in the egg shel. 5 no yes Cr0,2~ removed, shift to left: yellow| | Looking atthe above reacticn, = the reduction of CO; wil 3 no ves NH,* added, shift to left solution | | shit the ecuitrimta the ei, ‘becomes more acigic (clear) reducing the concentration 2 [a ves no OH” removed, shift to right: a ot CaCO, | reduction in OH~ should cause the mixture to clear up 4 no yes H,0 added, shift to let: pink | 5 ves 0 I> added, shift to right: blue a [6 no yes CI removed, shift to let pink i yes 0 energy added, shit to right: blue | 8 no yes energy removed, shift to left: pink | & iho) | yes no energy added, shift to right: brown teold) | no yes ‘energy removed, shift to let: 4 | colourless | 4 10 ves pressure increased, shifto left. | colourless | 4, (2) Both syscems are endothermic. (b) Upon heating these systems should shift fom left o right, coward the exothermic side of the reaction, because the equilibrium will shift in the direction that rids the system of | the added energy. (€) The value of K. should change because a change in temperature shifts the equilibrium, the equilibrium concentration, and the values used forthe equilibrium expres 5. (a) When the plunger was depressed, the total pressure of the mixture increased. (b) When the pressure increase inside the syringe, there isan increase in collision frequency beeween the gas molecules and the walls ofthe syringe. Ifthe total number of gas mole- cles decreases, s0 will the number of collisions and, hence, the pressure will drop. Conversely if the number of gas molecules is inereased, the number of collisions on the walls ofthe syringe will increase and so 100 will the pressure. (€) When the plunger was pushed down, the pressure increased and the equilibrium shifted co the left (increasing the coneentration of N,O,) so that there are fewer gas molecules Jn the equilibrium mixcure. This shift reduces the total amount of gas in the and will reduce the pressure inside the syringe. (a) Since the same numbers of gas molecules exist on both sides ofthe chemical equation, ~~ change in pressure will not alec the equilibrium of the system. ringe, ‘Chapter 7 Reversible Reactions and Chemical Equilibrium * WHR | 497PINT chapter 7. reveoaue Reacnons ano Chevncat Equusmurs Paris 1-3 of Investigation 7-8 ‘may be done in a 24-well plate. Store the solutions in ge pipettes. ry ees | Please ensure that students have read “Safty in Your Chemistry Leboratory and Classroom” on pages vil-x of the student textbook. Also ‘ensure that they follow all safety precautions outined for ths Investigation inthe student textbook. = Try using analogies to explain the concepts of equilibrium and Le Chitelier’s princi- ple. For example: Imagine an island connected to the mainland by a bridge (two lanes ic only). At any given time, there should be an equal number of vehicles enter- ing and leaving the island—assuming the population of the island remains constant. of tra However, along comes che long weekend, when mainland residents flock to the island, There will be an increase in the population of people on the island initially (the tate of those going to the island will be greater chan those leaving) but as time passes, the rate of vehicles coming and going will stabilize and a new equilibrium will be established. A similar analogy, using a shopping mall, escalators, and a sale on the second floor, could also be used = Investigation 7-B: Perturbing Equilibrium is an excellent activity for visual learners having difficulty in grasping how Le Chatelier’s principle pertains to chemical systems in equilibrium, st The February 2002 issu of Te Jounal af Chemical Edwaton contains a csscom activity (p. 200 A) entitled "Rubber Bands, Free Energy, and Le Chitelier’ Principle”. This activity uses rubber bands to help illustrate che concepts of Gibbs free energy, entropy, and enthalpy. = BLM 7-4: Chapter 7 Test/Ascessment can be used to evaluate students understanding of equilibrium concepts before moving on to Chapter 8 Solutions for Practice Problems Student Textbook page 356 See Solutions Manual for solutions to Practice Problems. Investigation 7- Student Textbook pages 358-361 Approximate Time Required: 120 min if scudents carry out Parts 1, 2, and 3; 60 minutes if ll four parts are done as a teacher demonstration. Note: Pare 4 may only be done as a teacher demonstration Tips If time isa concern, all four parts of this investigation could be done as a demonstra tion, with students recording their observations. Caution: For Part 4, NO, and NO, are both toxic by inhalation and poisonous: therefore, any reaction involving these chemicals should be carried out in a fume hood, with suitable attention to protective clothing. The photographs provided in the student textbook (pages 360-361) provide an alternative means for students to “do” Part 4 ifa fume hood is unavailable. = Caution: Potassium chromate and barium chloride are toxic. = Caution: Hydrochloric acid and sodium hydroxide are corrosive. = If glass cubes are not available, NO, can be produced by reacting Cu turnings with concentrated nitric acid in a gas-generating apparatus, and then stored in 250 mL Exlenmeyer flasks Answers to Analysis Questions 4, Students could discuss and resolve any differences herween their results and predictions in groups. Encourage students to think beyond experimental etror in considering any differences. 196 | MAR + Unit & Chemical Systems and Equiiorumlsd 5. (a) 48 1036-x(036-a Concentvaion | HO] = [aay ]* [Ory x 32 or 0.247, ere amount of SOs. = (0.247 mol)(5.0L) = 1.2 mol Initia 0.055 o ot | ‘ range | owss—2x| | ax x 1) Concentration | PCy + [Ch [= | Poljg] [Eaitbrom | oss asx] [rex] nav _ [HFO3] Initial 0.094 0.094 o {H,0P change [ooo x | [aos — x x je eignt = Tt Equilibrium — | 002s 085 089 Oat = 178x107 PCL) eel (8) Ac thes high temperatures, the concentrations of rae U.09Y~ 0-054 Idan ae cage ae 0 ow oak pr fee fe cal method of deromposing wae. © = Toosk [0094-9 a } 058 = = 075 010.059 | 7.4 | Predicting the Direction of a Reaction Not all chemical systems exist initially a equilibrium, nor do they stay at equilibrium when changes are made to the system. The focus of this section is on systems not at equi= librium, either due to the reaction quotient not being equal ro the equilibrium constant, ‘or an external stress that is placed on the system. Le Chatelir’s principle is introduced and its use in predicting the direction of equilibrium shift is examined and investigated. Teaching Strategies The reaction quotient, Q. and its associated expression, are identical in format to that of the equilibrium expression. The only dference is that the concentration data used to determine Q_ might not necessarily be the concentrations at equilibrium. Students should not get hung up thinking they need to learn yet another new formula: they simply need to realize that the conditions for determining Q and K_ are different. = The relationship between values of Q. and K_ provides a good starting point to discuss the changes that can occur to a system not at equilibrium and Le Chatelier’s principle. ‘Students can become confused when statements regarding Le Chateier’s principle make claims that solids do not affect equilibrium mixeures. Many students tend to believe that “you cannot alter the amount of solid in an equilibrium mixture’ this is obviously untrue, as solids and pure liquids do nor have a concentration value. Challenge students to prove this using specific examples (€-., the heterogencous equilibrium for the heat- ing of CaCOy in a sealed vessel: CaCO = C0 jg + CO29) by examining the relationship between the amount of solid present initially and at equilibrium. Inform students that the concentration of a solid is much like its densiry; both are intensive properties that do nor depend on the physical amount of sold present. Thus, the con- centration terms for solids in a chemical reaction are themselves constants and are not included in the equilibrium expression. Students must also understand that solids can be added to an equilibrium mixture, without affecting the equilibrium position, = Students should be made aware that Le Chateier’s principle is only valid for systems initially ac equilibrium and is not applicable co any irreversible process. Chapter 7. Reversible Reactions and Chemical Equlibrium + MR | 195hope 7 Revasms Racrens 0 CroncA EQuuonM CONCEPT CHECK | student Textbook page 349 194 Valuos of K, donot indie rato in ihich a reaction ‘occurs. They anly predict the ‘outcome ofthe reaction ‘amount of product ‘generated —which will vary for diferent reaction condi _[Fe(SCN?*] (Fe }+1SCN J ate the | 3. Another expression that can be evaluated is: | An theory, only the true expression for K. will yield consistent results for the four data the oe the actual reaction, (b) The value of K, would be different. The concentration of thiocyanate ions ac equi sets collected in this investigation 4, (a) Because this investigation relics on the students’ ability to compare the colour of ‘wo vials of liquids to determine equilibrium concentrations, itis very likely thac the concentrations used in the calculations will differ from chose of the product in librium will be reduced and che equilibrium expression will be altered. Assessment and Evaluation Measuring an Equilibrium Constant, pages 340-343 Developing Skills of Inquiry and Communication = [CSE 203] carry out experiments to determine equilibrium constants (e.9., , for iron thiocyanate) Investigation 7-4: Measuring an Equilibrium Constant (see Assessment Rubrics on the Teacher's Resource cb-ROM) Understanding = Inquiry = Communication| Thoughtlaby ‘Assessment ExpressLab/ | Curriculum Tools/ Achievement Investigation _| Expectations Techniques Chart Category | Learning Ski Investigation 7-A:| Specific Expectations Rubric for = Knowledge? | m Teamwork = Organization Solutions for Prac! :¢ Problems Student Textbook pages 347-350, and 352 See Solutions Manual for solutions to Practice Problems. Student Textbook page 353 1a) K IN3ILH, [sbcl) SCA} cl 201 THFINO? [concentration | 2NI (mov) Hag | | Nao | +] Hag Initial 20 o 0 Change = 040 020 060 Equilibrium | 16 020 060 MHR + Unit 4 Cheri ical Systems and Equilibrium (NAIC? __ {0.20)10.60)9 © = Nae qe 7 007 3. Concentration }$0ygy | +|NOygy | = |NOjg)| + | $0yQ) imal) Initia 036 o_o 0 change __|o36—x|_|o6 ~x| x x Enuitrium [0.1 on [025 025 {NO|ISO,] [SO,}[NO,] -ww You can use 1 mL microti Pipettes in this ab to reduce the volume of solutions ‘needed. Use walls AT-Ad to : ute te ron solution, Place 5 | Tips tops ofthis solution and 5 Grogs ofthe thiocyanate solution into well 1 to act as ‘the contro reference calou') ‘Student Textbook pages 340-343 Approximate Time Required: 75 min 18 Before starting this lab, prepare students for the steps necasary to complete this investigation in a reasonable time period. Have al students predict the equilibrium expression for the equilibrium being studied in this reactin: a Place 5 drops ofthe [Fe(SCN)?*] thoseote soon ito wets <= TES FISCN=] AI, BI2,CiT,and B10. Now Potassium thiocyanate, sodium phosphate dibasic, and iron nitrate are all eye irritants | a6 drops ofweterto wels and are harmful if they are ingested, inhaled, or come in contact with skin. AV-AA. Ad 4 drops 0.20 mol/L iron solution to Al. Drew up this solution into another claan ‘mL pipato, then disgense ¢ Arops into A2, and § drops into ‘AI Mix A2 solution as before and place 4 drops into A3, ard = Ifa spectrophoromerer or a colorimeter is available, students can perform the Chemistry 12 Probeware Investigation 7-A. A spectrophotometer or colourimecet micasures the absorbance of each equilibrium system, By comparing the absorbance of each solution to that of a standard, the equilibrium concentrations of [FeSCN]?* can be more accurately determined. © The solutions of Fe(NO3); should be prepared in 1.0 M HNO, rather than water. S dropsinto B12. Continue fo- ‘The presence of the H* ion will prevent the formation of Fe(OH)?* (a brown- the remaining two diuions to coloured complex), which can interfere with making absorbance/colout intensity provide a roference colour fer determinations comparing the four duns. = Flat-bottom vials eliminate error due to the curvature of atest tube. However if these | Use aclean mL microti are not available, small rest tubes (e.g, 16 mm X 125 mm) may be substituted. pipet to deve up the = Emphs reference solution in wet 8. ions present. Place the tray over a bright = Preparation of Stock Solutions: M(KSCN) = 97.2 g/mol. bet mee eae re = To make 1.0 L of 0,002 mol/L solution, dissolve 0.19 g in distilled water and make | “ePaper Then addins up to 1.0 L in a volumetric flask, NaSCN can be substicuted. Hepat | = M(Fe(NO3)3) = 241.9 g/mol: To make 1.0 L of 0.002 mol/L solution, dissolve 0.48 ize the use of toral volume of solution when calculating the concentration of numbor of ops when the gin about 500 mL. of distilled water. The solution should be in 1.0 mol/L nitric acid, | golur matches B10, then Ch, 0 carefully add 63 mi. of concentrated nittic acid to the Fe(NO5),qy then bring | B12 and inal Alt, Theratc the toral volume to 1.0 L in a volumetric flask. ‘ofthe drop countto the = IFFe(NOs);*9H,0 (M = 404 g/mol) is used to make this solution, then dissolve reference 10 drops) gives he | 0.81 g in about 500 mL. of disiled water and make the selution up as above. concentration ofthe colouree = To make 1.0 L of 0.200 mol/L. Fe(NO3)yi,9 follow the above directions using 48 g | ant euibrism. Tiss the of Fe(NO,), oF 81 g of Fe(NO,),*9H,0. srlro-aquvlent of meaning Stock solutions should be prepared well in advance, but equilibrium mixtures should i ae nee not be mixed in advance as the solutions are light-sensitive and the colour will Fade ‘quickly in a 24-hour period. Answers to Analysis Questions 4. As the volume of SCN~ in che vials increases, the colour intensity of the Fe(SCN)?* complex should increase as the equilibrium is being shifted to the right. 2. Values of K- will vary greatly from one lab group to the next, depending on the accu- racy of the students in comparing the colour intensity of the vial vs. that of the stan= dard. K_ values should be much closer in value if a spectroshotometer or colourimeter is used. Chapter 7 Reversible Reactions and Chemical Equilibrium * MHR. | 193[TITTY chapter 7 eversnue Reacrons so Coenacat Equuenuns ICEPT CHECK Suden Textbook page 35 | The ExpressLab cariod out in | saction 7.1 modo reaction approaching equitsiom by showin the navement at vata between wo graduated | ovina When aquirium | was oachod tho rate of water | moving in both he orvaré and revere dractons was equa The equifbrium expression can be expanded to use both mole fraction andor pressure data. BLM 73.Chemical Eculriam cof Geses/Enrchment, Invoduces motivated students tothe equirium constant bbased on pressures. CONCEPT CHECK | Sudent Textbook page 39 ‘At oguitbrium, the concentration of the products and reactants are notin the same ratio as the coefficients | of the chemical equation. Only the change in concentration ‘om to intial conconraton of the products and reactants to the equltrium concentration willbe in the same rato as that ofthe cosficients ofthe | comical equation. The Equilibrium Constant Student Textbook pages 334-353 Systems in equilibeium have a constant ratio berween the concentrations of products and reactants, In section 7.3, this ratio is examined and is quantified through the definitions of the equilibrium expression and equilibrium constant, This expression is then used in solving number of diferent equilibrium problems involving the concentrations of productions and reactants, Investigation 7-A will enable students to collect data for 2 system in equilibrium, and determine the equilibrium constant for a mixture of Fe** and SNC- ions in solution. Teaching Strategies = This section hegins with a discussion about equilibrium concepts covered in section 7.1, Before working through calculations involving the equilibrium constant, it is best 10 ensure that students are well versed in the “requirements” for systems at equilibrium and the associated changes taking place at the microscopic level. = Conceptually, che idea of chemical equilibrium does not differ very much from that of physical systems in equilibrium, Nevertheless, the concept can still prove to be a stumbling block for many students. Use the example and images (Figure 7.7) on page 334 of the student texcbook to help students better visualize the meaning of the law of chemical equilibrium. Ensure that students are aware that placing molecular formulas in square brackets (€-g.5 [NOp]) signifies the concentration of the molecule. © For students with weak math skills, the development of the equilibrium constant, Ks may prove challenging. The key skill for students to develop is chac of applying the general format of the equilitrium expression co a chemical system in equilibrium. = Reinforce that in order to determine the value of the equilibrium constant, concen tration values for the chemical species must be used. 1 Before moving on to the subsection abou “The Equilibrium Constant and “Temperature” (page 337), verify students understanding of reaction rates and kinetics, as ‘well as relating equilibrium conditions and concentrations to a stoichiometric formula Discuss why values of K. have no units. In general, che units of concentration (or pressure) should cancel our during X, calculations Stress the use of ICE rables, as shown on page 339 of the student text = Students are expected co be able co solve three types of equilibrium calculations: sim- ple, perfect square, and approximation. Be sure to work through practice problems of each type before moving past section 7.3. This section includes a number of concepts that a student must understand to be sue- cessful in working through the remainder ofthis unit. Once section 7.3 is completed, it might be a good idea to develop a set of “rules” that can be used for solving prob- lems invotving the equilibrium constant, and how to deal with small values of K, Solutions for Practice Problems Student Textbook pages 336 and 338 See Solutions Manual for solutions to Practice Problems 192 | MR + Unie 4 Chemical Systems and Equlbium~ concept office energy. This section concludes by examining the relationship between free energy and its impact on chemical systems in equilibrium. Teaching Strategies To support the discussion of favourable (spontaneous) change presented in the text, you could lead students through questions such as (in relation to a ball at the top of a hill): How do you know energy is released? There isa change from gravitational poten- tial energy to kinetic energy (energy of motion), and the motion is spontancous. Is the movement of a ball from the bottom of a kill back to the top a favourable change? No—energy must be applied 10 move the ball up the bil a non-spontaneous change). Entropy isa very diffcule concept to fully understand in high school chemi According to the Second Law of Thermodynamics, the universe is forever undergoing, an increase in entropy. When determining sign convention for entropy changes, stu- dents must only consider the change in entropy of the system and not the surround- ings or they can be forever dealing with a positive change in entropy. Emphasize to students thar a non-spontaneous chemical reaction can be forced to react by adding energy ftom outside the system—for example, the dissociation of water into hydrogen and oxygen using a Hoffman apparatus. = BLM 7-2: More on Entropy and Free Energy/Skill Builder can be photocopied and dis- tributed to students to work with the free energy equation and help them better under- sand the relationships bewween entropy, Gibb’ free energy, and reactions at equilibrium, A quick demo: To help illustrate an endothermic reaction, demonstrate the ra between barium hydroxide and ammonium thiocyanate as pictured on page 328 of the student textbook. Combine 20-30 g each of barium hydroxide and ammonium thio- cyanate in a 250 mL Erlenmeyer flask. Swirl the contents ofthe fask and then place the flask on a small puddle of water. To enhance the demo, put the puddle of water on «block of wood or an inverted beaker and then life the ask to show the flask can be frozen to another object. This demo will help students understand how chemical reac- tions are not favoured in terms of enthalpy change, but are entropically favoured. is ‘Student Textbook page 329 ‘The situation described inthis figure is based on the assumption thatthe gas inthe flasks is ideal, An ideal gas is ‘one that undergoes perfectly elastic collsions with itself end with the walls ofthe vessel hence, no energy is lost in the movement of gas molecules hetwaen the two flasks the ges were notideal, then a change in energy wauld be detected as the gas maved ‘rom one flask tothe other. Student Textbook page 2 Exargni:a spontaneous chemical reaction which there a et lease ore energy. An example ical | respiration Cyt, + 6.0, 6.60, + | 6H,0.AG = ~2270 nol | fndergonic: non- spontaneous chemical reaction in whieh ra is absorbed from the surroundings. An example is photosynthesis: 80, + 8H,0 + CH,0, > 60,AG~ Zi70ku/mol orgy Section Review Answ: Student Textbook page 333 aT 1. A favourable chemical change i a change that has'a natural tendency to occur under certain conditions—for example, cellular respiration and exposed stel on an old automobile that begins to rust. An unfavourable chemical change is one thar does noc have a natural tendency to occur unde cer- tain conditions—for example the decomposition of HgO at toom temperature and the formation of water from oxy- igen and hydrogen gas at room temperature. 2. The signs of AH and AS help determine whether a chemi- cal reaction is fvourable. As shown on Table 7.1 on page 333 of che student textbook, there are a number of ther- modynamic possibilities that will lead to a favourable reac- tion. The values of AM and AS, along with the reaction temperature, can be used to help determine the Gibb’s free energy for the reaction in question. When Gis ncgative, thermodynamic laws dictate that che reaction is favourable. ‘When AGis positive, the reverse reaction is Favourable. 3. (a) entropy increases (b) entropy decreases (9) catropy increases (@ entropy decreases (6) entropy increases 4. (@) positive () negative (2m (2) negative (e) nope (°F + 5. When water feces, there is a decrease in entropy (ASis n ative). Based on enthalpy alone, the reaction is favourable, bur the reetion is not entopically fvourable. This reaction isonly favourable at low temperatures (below 0°C) where calculation of the value for AG will become negative Chapter 7. Reversible Reactions and Chemical Equilibrium + MiKR | 491MBER chapter 7 acsisms Reacrons ano Chemica Eovucm 190 4, A system is in equilibrium when the rate of forward and reverse reactions is equal (Ge., volume of warer in reactant and product eylinder are no longer changing), or when a graph of volume vs. time becomes constant. 5. The volumes of water in che two tubes were not equal at equilibrium. This indicates that concentrations of product and reactant do not have to be equal at equilibrium; they must, however, remain unchanged. 6. The addition of more water is analogous to increasing the concentration of a reactant in a chemical reaction; this should, in turn, increase the amount of product present at equilibrium 7. The two ratios should be the same (within experimental error). 8. The relative volumes of water were determined by the diameter ofthe tubes, which model the relative concentrations of reactants and produets. At chis early point in the chapter, students likely will suggest tersperature as a factor that affects the relacive concentrations of products and reactants at equilibrium. Some students may also suggest pressure. In fact, any of the factors related to Le Chitelier’s principle are factors; you might want to have students look again at this atvey, and this question in particular, atthe end of the chapter. 8. The system is closed because it does not allow for the input or escape of any compo- rnent of the equilibrium system, Assessment and Evaluation Thought) ‘Assessment Expresstab/ | Curriculum Tools) ‘Achievement Investigation __| Expectations Techniques Chart Categories | Learning Skills Express Lab: | Overall Expectations m Student Inquiry = Teamwork Modeling [CSE V.02] investigate the behaviour of Answers to | m Communication| m Work Habits Equilibrium, different equilibrium systems, and sole | Questions. page 325 problems involving the law of chemical equilibrium Section Review Answe: Student Textbook page 7 4. Two physical processes that are examples of reversible changes noe at equilibrium area pot of boiling water with the ld off and disolving satin waver co make an unsatu- rated solution, Two chemical processes that are examples of reversible changes not at equilibrium are the dissociation of ‘water using a Hoffman apparatus and the heating of cobalt chloride hexahydrate to decompose it into anhydrous cobalt chloride and water vapour: the addition of water to the anhydrous product causes the formation of the original cobalt chloride hexahydeate. 2. When a reversible reaction approaches equilibrium, the concentrations of both the produets and reactants will st bilize and the rate of the forward reaction will equal che rate of the reverse reaction. i ‘Student Textbook page 228 lFthe stopper were removed, the odour of ammonia would 3. (a) Ac the molecular level, there is a constant movement of Cp) molecules from the space above the liquid dis- solving into the liquid, ane! molecules leaving the liquid into the space above it (b) Pressure, cemperacure, composition, and amount of particles present will say constant. 4. Ina sale jar, the numbers of molecules in dhe liquid and gaseous state are nor equal. Oly the rate of change of water molecules undergoing condensation and evaporation are el. 5. lee and slush will form an equilibrium mixeure at O"C, At temperatures above °C, both ice and slush will end to mel, and at temperatures below 0°C, the slush will begin to freeze. AACO°C, the rate ofthe water molecules moving between a slush (Liquid) state and ehe sold sate will be equa EX im Student Textbook pages 328-333 be detected. “This section makes the connection between the thermodynamics of physicalichemical reactions and equilibrium. Concepts of enthalpy (previously learned in Unit 3 of this course) and entropy are examined and their effects on a chemical reaction are deter- mined. Changes in entropy, enthalpy, and temperature are chen combined through the MHR « Unit a Chemica Systems and Equilibrium J wv= Over the course of the chapter, encourage students to review “The Four Conditions That Apply to All Equilibrium Systems” box on pages 326-27. This is especially important once students begin examining che equilibria of chemical rections in deal in section 7.3. You could use the following analogy to help students understand the concept of dynamic ‘equilibrium: Ifa person is rowing a boat upstream ac the same speed as the current is mov- ing downstream, the boat will appear motionless to an observer on the bank of the stream, and yet both the rower and the water are doing work in opposte directions. Students could bbe challenged to come up with their own analogies—a useful way to check for comprehen- sion and/or misconceptions = If possible, dedicate a full cass period in completing the Express Lab: Modelling Equilibrium, as itis extremely important for students in developing quantiative insights into systems at equilibrium. = Use BLM 7-1, Illustrating a Chemical System in Equilibrium/Overhead Master, to visually illustrate the macroscopic concepts ofa system in equilibrium to students and reinforce the conditions necessary for a system in equilibrium. Students can easily confuse the terms (and concepts) “steady state” and “equilibrium.” Steady states refer to systems whose components are moved from one location to another in a single direction (e.g., water flowing downstream from a pond to a lakes the water level in the pond never decreases and that ofthe lake never increases, but the warer is moving in only one direction). Equilibrium sitations involve compo- nents moving in both directions (at the same rate) berween two locations. Coe Modelling Equilibrium Student Textbook page 325, Approximate Time Required: 30-45 min Tips = Prepare water and food dye 1-3 days beforehand. 8 The glass tubing should be cut co equal lengths, approximately 20 em long, if25 ml. grad- uated cylinders are used, CAUTION: Fire-polish the ends. Surws are nor recommended as a substitute because students are more likely to use their mouths to draw up liquid. = Encourage students to predict the outcome (and sketch a graph of volume vs. num- ber of transfers) before they begin this activity = The activity can be expanded into a classtoom demonstration by putting unequal amounts of water into two large aquariums or translucent storage containers. Give one student a small beaker (250 mL) t0 scoop water from container 1 into container 2, and givea larger beaker (600 mL.) to another student to scoop water from container 2 into container 1 simultaneously. Allow this process to continue until equilibrium is reached. A similar chought experiment using coins (or students) is described in The Journal of Chemical Education, Vol. 77, No. 8, August 2000, page 1013. Answers to Analysis Questions 4. See the answer to question 2 below 2. The slopes of the graph will provide insight into che rate at which the reactions occurred. The graph should show that the rate of the forward reaction slowed over time, while the rate of the reverse reaction slowly increased as the reaction proceeded. 3. The reaction rates are equal to the slopes of che graph, not the point where the two lines meet, which indicates when the Volumes of product znd reactant were equal rman ‘Stent Textbook page 223 ‘systom Bis in equitrium bocausa ‘the system i closed; the water molecules that escape tho liquid phase are trapped by the ar io and eventually tur tothe lieu phase. Thus, the volume of wetar in tho jr at equibrium is constant ‘System Ais open, so the water ‘molecules inthe gaseous stat2 can escape slay reducing tie volume of the puddle, ‘Student Textbook page 224 ‘System B isin equlirium, which can be changed by increasing the temperature ofthe solution, thereby allowing more copper) sulfate to dissolve, and increasing ‘the concentration of CuS0, in he aqueous phase. Neither system sin equi; the second system wil be in equilrium once the crystal stops its growth and the solution goes ‘com supersaturated to saturatod, NCEPT CHECK Student Toxook page 25 | Conca of redet an rnacaneso there tobe aul teqibrim Te rae otto and ove rus ea | a Pare TCLS Ploaso ensure that studonts have read "Safety in Your (Chemistry Laboratory and Classroom’ on pages vi-xio the student textbook. Chapter 7. Reversible Reactions and Chernical Equilibrium # MER