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Course: CHEM 122, Fall 2010
School: Simon Fraser
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1&quot;t Example: Order Rate Law 2N2O5 Question l: -+ + 02 4NO2 . Is this a First-Order Reaction? Question 2: What is the rate constant? Answer: We can't tell without an experiment! + Half-life of lst Order Reactions . Measure how concentration varies with time: 0.10 Rat&quot; = 0.00 - dlNzo'l dt = t[N,o,l hard to tell from [NzOr] vs Time How to determine fr? 0.04 aA -+ products...

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1"t Example: Order Rate Law 2N2O5 Question l: -+ + 02 4NO2 . Is this a First-Order Reaction? Question 2: What is the rate constant? Answer: We can't tell without an experiment! + Half-life of lst Order Reactions . Measure how concentration varies with time: 0.10 Rat" = 0.00 - dlNzo'l dt = t[N,o,l hard to tell from [NzOr] vs Time How to determine fr? 0.04 aA -+ products Rate= ...if it's fust order 0lr Definition: Half-life Half-life : time taken for concentration to fall to half its original value. #=urot \ Therefore^ hrfl l hr[a]= -frt+kr[A]o and r wi)=o' 0.o2 ofr l0 20 T:@(s) when Plot: ln[NrOr] vs Time First order: -3.() ln[NrOr] d i a {.m Straight line? -5.0 So,kr[2]:ktyz-ffi : -h + order = ln[NrOr]o .g ,r[#)=0,,, rAr=ry l't sloPe: -k l(. 5 m 3m ,(! Tnc(s) Half Lives: Radioactivity Half Life or a.Qj,brder --Reaction . Example: Decay of Polonium 210Po 2N2O5+4NO2+02 -+ 206Pb + aHe (alpha radiation) . Radioactive Decay: First Order process t r,r(ztoP o) : I3 . Minimum lethal dose lN,o,L-o o,\$o . Excreted in -30 o.(xD ogrfl) - 8.376 days - I pg for 80 kg person 50 days Former KGB agent Alexander Litvinenko o_lm ] lxgL-o.oco i:. t Dose: l0 pg (@ \$l million per pg) 'oo- Before 0.o3n hiro'L4 o,o:(n After E;ot--*r, 50 ,t: 0 L50 :tI) a50 f!: lv= 3\$ ,150 100 Tm(sl 4L.--100s . Compare with . Half life : 238U' 238U 4.5 billion years = -) 234Th + 4He much lower toxicity
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Simon Fraser - CHEM - 122
2ndOrder lntegrated Rate LawSecond-Order Rate Processes1laA + productsDifferential rate law:Rste:-(Ddt4ldt=tAI-[A]oIf [A]o andkareknown, [A] canbe= klAf'calculated at any later timeRearranging,Second-order Integrated Rate Law: equation
Simon Fraser - CHEM - 122
.!rIZero-Order Rate ProcessesTODAY'S LECTURE,REACTION KINETIGS&quot;I.Differential rate law+aAproductsIIiRate.Zero Order Reactions.Rate Law for &gt;1 Reactant.The Isolation Method.- M:klAfo-kdtReaction MechanismslAl:-frr+[A]o_&quot;v2 [A]
Simon Fraser - CHEM - 122
What lf We Have &gt; 1 Reactant?Summary: Kinetics for Reactionsof the TYPe: aA + ProductsFor more complex reactions such as:5\^RaE:lawfRate =klAlRate =vtlAI2l,t!=-rt+lt\ r[z],=-tr+t'['a] k=&quot;.frIntegratedRate LawPlot need togive astraight li
Simon Fraser - CHEM - 122
Reaction MechanismsReaction Mechanism:series of steps that make upthe overall chemical reactionGOAL: To determine the reaction mechanism fromexperimental kinetic data that we have measuredOverall mechanism: composed ofa sequenceof&quot;elementary rea
Simon Fraser - CHEM - 122
Rates and Molar RatiosL5ToDAY,S LECTURE:Reaction rate oC-.REACTION KINETICS'..Number of molecules consumedor produced by each reaction stepExample: For the first order reaction2A-+28+CRates and Molar RatiosdTCl.Rates and equilibrium.dtPr
Simon Fraser - CHEM - 122
Pre-equilibriumIn reactions with a fast initial equilibrium step:FastSlowk'k,A+B -i- lntermediate-a&gt;k_rExample: Pre-Equilibrium.Decomposition of Ozone2ot@) -+ProductsExperimentally determined Rate Law:FastRate:DeterminingltcO *, and *-,
Simon Fraser - CHEM - 122
Steady-State Approxi mati ontL\$ T.DAY,S LECTURE:Inmultiple step reaction:k,k,A+B _-i* Intermediar&quot;t.REACTION KINETICS'IaproductsCan't choose a rate determining step?Steady-state approxim ation+Temperature Dependence ofReaction Ratesuse&quot;S
Simon Fraser - CHEM - 122
Testing the Rate LawExperimentallySteady-State Approxi mationStep-by-StepVary reactant concentrations -+GOAL: To write the rate law without including anyintermediatesDoes rate law predict experiment result?O High tHzlk2lH2l=&gt;O Write reaction m
Simon Fraser - CHEM - 122
Ghemical ExampleBiological ExampleThermal decomposition of acetaldehydeCH3CHO -+ CFL + CORare = _dtcH_3_cHolDatak) vs 1000I'\700t6mol-t stl0.01l -y7300.0357ffi0_1057m0338100-7E9840t4s 419x llTo&gt;FgU,Yio]Goolrj201000L2-t7
Simon Fraser - CHEM - 122
Gollision Model for KineticsActivation Energyi/7 TODAY'S LECTIJRE:IIINO + NrO -+ NO, +ry.REACTION KINETIGS&quot;IIiI-s,ffi. Collision Model for Kinetics4h\Reaction ProfilesIn this reaction N-O bond must be brokenTransition StatesN-O bond d
Simon Fraser - CHEM - 122
Reaction Profiles andTransition StatesMulti-Step Reaction Profiles. Rate of reaction determined by activationRate of reaction determined by activation energy, Euenergy, E o (and frequency factor, A)(and frequency factor, A).Fgr single step reactio
Simon Fraser - CHEM - 122
EnzymesEnzyme example: GatalaseEnzymes = biological catalystsVery efficient catalysis under bioloeical conditionsDecomposition of hydrogen peroxide (toxic)2HrO, -+ 2H2O + 02Example: Conversion of N, to NH,:Humans: Haber processNatureN2+3H2#flb2N
Simon Fraser - CHEM - 122
Question 3: An &quot;exothermic reaction follows the two step mechanism:A+B -+ CC+D-+E(1)(2)The activation energy for the first step is L25 kJ /mol an for the secondstep is 200 kJ/mol.a) Draw a rough sketch of the reaction profile on the provided graph.
Simon Fraser - CHEM - 122
Relationship between K and KpEquilibrium ExpressionsFor Gases.To describe equilibria involving gases can use:To describe equilibria involving gases usually usepartial pressures instead of concentrationsPartial pressure:independent pressure exerte
Simon Fraser - CHEM - 122
Heterogeneous EquilibriaReactants and/or products in difrerent phasesFrom experiment:Position of heterogeneous equilibria do notdepend on the amounts of pure liquids or solidsWhy? Activities of pure solids &amp; liquids =Example:CaCO3(s)=-CaO(s) + CO
Simon Fraser - CHEM - 122
Equilibrium GalculationsExample 1, Continued.Equilibrium CalculationsExample I6Define change to get to equilibrium and writeexpressions for equilibrium conc.st.O Write balanced equation for reaction:Hr(s)+ rz@) :2HI (g)Lt.c.B.O Write equilibr
Simon Fraser - CHEM - 122
Approximation Method forSmall Equilibrium Constants2NzG)+OzG).= Simpliff:2N2O(g)terrrs in denominator:(0.0482-2x) = 0.0482 (0.0933-x) = 0'0933Q'+t)-' &quot;':l:)&amp;&gt;)-. o.cl3)'.ffisubsurute@checkvalue2X/o-rriro-)ru'is correctdLlsA=g-gygv-ZX
Simon Fraser - CHEM - 122
h,\$qluhility Equilibria6',a1ie\th3TODAY'S LECTUREIonic salts dissolved in water are inequilibrium between the solid and the ions&quot;Ghemical Equilibria&quot;.Zn(OH), (s).Solubility EquilibriaEquilibriumconstant: t\:- lzn2.lloH-1'?lz(orD,l.Solubility
Simon Fraser - CHEM - 122
Effect of Change in Concentration(at Constant Tem perature)Add reactant or product+system shifts away from added componentChange in Equilibrium ConcentrationsExample: Effect of change in concentration2SOr(g)Remove reactant or product+ Oz(g) =:Equ
Simon Fraser - CHEM - 122
Effect of Change inTemperatureChenge in Temperature -+ Change inThe Effect of a Gatalyston Equilibriaff.Hgiveoutheatenergy*)Catalyst reduces.Treat heat energy as product or reactantSpeeds+%(absorbheatenergy)-fheat energt-+Products\k)Equ
Simon Fraser - CHEM - 122
TODAY'S LECTURE&quot;Acids and Bases&quot;The Nature of Acids and Bases.Arrhenius concept:(H') ItBases produce hydroxide ions (oHJfAcids produce hydrogen ions*tto.The Nature of Acids and Bases.Acid Strength.BasesAcids in Aqueous SolutionsWater acts
Simon Fraser - CHEM - 122
Acid StrengthHA(aq)Acid:&lt;lT1 &lt;IE.lct-l arrrConjugate baseRelativeIo)ilconjugatebase strength()4a0JnqEE.H*(aq1+ A-(aq)Relativeacid strengtho!T1Bv!)+)jt\v/CSP'-rO(D=av.&lt; +EH6 ri 5,=v)&gt;-8!-*,Ashong acidhasaweakScD
Simon Fraser - CHEM - 122
roThe pH ScaleI pg:- tog\Ffl and poH: -log[oHlpKo: -logKo and pKr:-logKupKw: -logK*Kw:tH+ltOH1:l0-r4+ pK*:pH Scale : -log Scale14.mt.iffi.ffipH(Vinegar):3[fI*]:tOH-l:10-7,pH:7, pOH:pH(Stomach7acidl:2[H+]sto*&quot;r,&quot;ia: 10 x [F]vio&quot;*_
Simon Fraser - CHEM - 122
roThe pH ScaleI pg:- tog\Ffl and poH: -log[oHlpKo: -logKo and pKr:-logKupKw: -logK*Kw:tH+ltOH1:l0-r4+ pK*:pH Scale : -log Scale14.mt.iffi.ffipH(Vinegar):3[fI*]:tOH-l:10-7,pH:7, pOH:pH(Stomach7acidl:2[H+]sto*&quot;r,&quot;ia: 10 x [F]vio&quot;*_
Simon Fraser - CHEM - 122
LtlropAYSoLECTuRE:.'ACIDS AND BASES'..Water as an Acid and a BaseAutoionaation;ffirttora -+' Kw: [Icfw_3O*][OH-]: 1g-r+ @25 C. True in Neutral and Acid andBasicsolutionspH of Mixtures of AcidsFor:Any%tct=kb=CWdlDHA(aq)+ Icfw_2o(DLHAA-(
Simon Fraser - CHEM - 122
pH of Weak Acid Solution. Problem: Calculate the pH of a 0.100 MpH of Strong BasesExample: NaOH o'oz4Strong Base: Dissociatessolution of acetic acid.Stratery:+NaOH(aq)O Identifr Major Species in SolutionIdentify the major species in solutionO
Simon Fraser - CHEM - 122
?,&gt;Yt -w f,rt^)LtAH+=zxrd'T)te [Hl - tcfw_Tl 1&gt;1= o,otlt + bz:Acids =o.:1/b o'-tirrt z+ flWv-PolyproticPolyprotic Acids (e.g. Icfw_2CO:, Icfw_rPOo)dissociate in a stepwise manner'AGIDS AND BASES'..o@r-r+-4_v@ FIPO+2-\$.7*.10'6rup
Simon Fraser - CHEM - 122
Salts That Produce AcidicSolutionsSalts That Produce BasicSolutions1) Anion = conjugate base of weak acid?2) Cation has no effect?r) Cation = conjugate acid of weak base?2) Anion has no effect?Acidic solution=*) e4ut'cfw_'rvttnkP;ample: NHoBr
Simon Fraser - CHEM - 122
o.Summary: Acid-BaseProperties of SaltsAcid-Base Properties of AqueousSolutions of Various Types of SaltsI*cfw_ !.1C-r-lsircfw_-q.4Ci.rri-rql*ahtXHO-i(-.-i-rIocfw_rc*i*-ri:qrl)\$(I NrNO6\rCrH.O!(]L iirF\lL(lxll\$s!\ldcfi,O5:cfw_cfw_dcfw_-
Simon Fraser - CHEM - 122
Goncept of EquilibriumLgState in which [Reactantsl and [Products]remain constant with time.T'DAY,S LECTURE:*CHEMICAL EQUILIBRIUM'.Equilibrium is dynamic.Law of mass action.BUT Equilibrium is \namic not StaticExpressions involving pressure.Fo
South Australia - POL - 13
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How does the legislative branch provide checks and balances against the abuse of power?1.Since a government needs a majority of votes in both houses of Parliament to pass its bills and sincegovernment rarely control both houses, a review of bills is li
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House of RepresentativesContains 150 members elected for 3 yearsLower house (the peoples house)Each member represents an electorateNo. of members is decided on the populationof each state (except Tas.) because each originalstate must have at least 5
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Area of Study One: Parliament and the CitizenAustralia is a Constitutional Monarchy:1.We have a constitution (the central document that determines the structure of government, power &amp; lawmaking)2.Commonwealth of Australia Constitution Act 19003.Bas
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