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CHEM 1AA3 - Chemical Kinetics Chapter 14.docx

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Department
Chemistry
Course
CHEM 1AA3
Professor
Jeff Landry
Semester
Fall

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CHEM 1AA3: Intro. Chemistry II Chapter 14: Chemical Kinetics Chem 1AA3Chem 1AA3 2 Preface The 3 big questions in any chemical reaction: (1) What are the products? (2) What is the equilibrium position? A G H J ? ? ? Chem 1AA3Chem 1AA3 3 Preface (3) How fast is the reaction? Chem 1AA3Chem 1AA3 3 Preface (3) How fast is the reaction? Chem 1AA3Chem 1AA3 4 Preface Why we measure rates: (1) predict/control reactions: -industrial syntheses-environmental reactions (e.g., smog formation, ozonelayer breakdown) (2) monitor biological or chemical systems: -clinical diagnostics (e.g., liver damage) -polymerization (e.g. strength of plastics) Chem 1AA3Chem 1AA3 5 Preface (3) understand reaction mechanisms: -reaction order (e.g., SN1 vs SN2) -structure/function relationships (e.g. rate vs. leaving group ability in SN2) (4) tell the temperature: -count rate of crickets chirping: T (°C) = 4 3 s25inchirps# + Chem 1AA3Chem 1AA3 6 14-1. The rate of a chemical reaction • rate = change in concentration of reactants and products over time •e.g. A . (1) • 1 min after starting reaction, [G] = 1 M • What is the rate of the reaction over 1 min? Chem 1AA3Chem 1AA3 5 Preface (3) understand reaction mechanisms: -reaction order (e.g., SN1 vs SN2) -structure/function relationships (e.g. rate vs. leaving group ability in SN2) (4) tell the temperature: -count rate of crickets chirping: T (°C) = 4 3 s25inchirps# + Chem 1AA3Chem 1AA3 6 14-1. The rate of a chemical reaction • rate = change in concentration of reactants and products over time •e.g. A . (1) • 1 min after starting reaction, [G] = 1 M • What is the rate of the reaction over 1 min? Chem 1AA3Chem 1AA3 7 14-1. The rate of a chemical reaction • average rate = 1 M / 1 min. time (min) 0.0 0.5 1.0 1.5 2.0 [G] (M) 0.0 0.5 1.0 1.5 2.0 .t = 1 min .[G] = 1 M A . G Chem 1AA3Chem 1AA3 7 14-1. The rate of a chemical reaction • average rate = 1 M / 1 min. time (min) 0.0 0.5 1.0 1.5 2.0 [G] (M) 0.0 0.5 1.0 1.5 2.0 .t = 1 min .[G] = 1 M A . G Chem 1AA3Chem 1AA3 8 14-1. The rate of a chemical reaction (2) • rates are always positive .put a negative sign in front of [A]: (3) • stoichiometry is important: A . 2G (4) (5) .t .[G]rateaverage = .t .[A]-rateaverage = .t .[G] 2 1 .t .[A]-rateaverage == Chem 1AA3Chem 1AA3 9 14-1. The rate of a chemical reaction • In general: aA + bB .gG + hH (6, 14.5) (7, 14.2) • Key concepts: -rate is change in concentration over time -rates are always positive -stoichiometry matters t [H]1 t [G]1 t [B]1 - t [A]1 -rateaverage ..= ..= ..= ..= hgba Chem 1AA3Chem 1AA3 9 14-1. The rate of a chemical reaction • In general: aA + bB .gG + hH (6, 14.5) (7, 14.2) • Key concepts: -rate is change in concentration over time -rates are always positive -stoichiometry matters t [H]1 t [G]1 t [B]1 - t [A]1 -rateaverage ..= ..= ..= ..= hgba Chem 1AA3Chem 1AA3 10 14-2. Measuring reaction rates • The food colouring expt showed that rate can change during a reaction. • Many reactions could give an average rate of 1 M/min for 1 min. time (min) 0.0 0.5 1.0 1.5 2.0 [G] ( M) 0.0 0.5 1.0 1.5 2.0 .t = 1 min .[G] = 1 M 14-2. Measuring reaction rates 0.0 0.5 1.0 1.5 2.0 [G] (M) 0.0 0.5 1.0 1.5 2.0 14-2. Measuring reaction rates 0.0 0.5 1.0 1.5 2.0 [G] (M) 0.0 0.5 1.0 1.5 2.0 time (min) • average rate = 1 M/min over 1 min for all 3 curves • average rate provides limited information Chem 1AA3Chem 1AA3 11 Chem 1AA3Chem 1AA3 12 • instantaneous rate (v): – the exact reaction rate at a defined time • v = tangent to the line when plotting [G] vs. time. 14-2. Measuring reaction rates time (min) 0.0 0.5 1.0 1.5 2.0 [G] (M) 0.0 0.5 1.0 1.5 2.0 v = 0.69 M/min @ t = 1 min Chem 1AA3Chem 1AA3 13 14-2. Measuring reaction rates • measuring .[A] or .[G] over a finite time interval, .t, gives the average rate • we want the instantaneous rate, v, the rate over an infinitely short time interval • taking an infinitely short time interval is the same as differentiating an equation in calculus (N.B. -"v" is an italicized letter vee (not the Greek letter nu). "v" comes from velocity, the other common term for rate. The textbook just writes out "rate of reaction" every time.) Chem 1AA3Chem 1AA3 13 14-2. Measuring reaction rates • measuring .[A] or .[G] over a finite time interval, .t, gives the average rate • we want the instantaneous rate, v, the rate over an infinitely short time interval • taking an infinitely short time interval is the same as differentiating an equation in calculus (N.B. -"v" is an italicized letter vee (not the Greek letter nu). "v" comes from velocity, the other common term for rate. The textbook just writes out "rate of reaction" every time.) Chem 1AA3Chem 1AA3 14 14-2. Measuring reaction rates (7, 14.2) (8) t [G]1rateaverage ..= g dt d[G]1 .t .[G]1 0 ggt lim = ..=v Chem 1AA3Chem 1AA3 15 Average vs. instantaneous rate • Experimental rates: -always average rates -we want instantaneous rates • What can we do to ensure that experimentally observed rates are as close as possible to instantaneous rates? – measure .[A] over the shortest possible .t – measure average rate as close as possible to t = 0 Chem 1AA3Chem 1AA3 15 Average vs. instantaneous rate • Experimental rates: -always average rates -we want instantaneous rates • What can we do to ensure that experimentally observed rates are as close as possible to instantaneous rates? – measure .[A] over the shortest possible .t – measure average rate as close as possible to t = 0 Chem 1AA3Chem 1AA3 16 Average vs. instantaneous rate • e.g., food colouring expt: (Data from Berti section.) time (s) 0 50 100 150 200 [red] (mM) 0.0 0.2 0.4 0.6 0.8 1.0 time (s) 0 5 10 15 20 25 [red] (mM) 0.0 0.2 0.4 0.6 0.8 1.0 Chem 1AA3Chem 1AA3 17 Average vs. instantaneous rate 0.0280.4420 0.0320.6810 0.0400.922 0.0400.961 1.000 (mM/s)(mM)(s) calculated average rate calc'd [red]time v0 = 0.041 mM/s (Data from Berti section.) Chem 1AA3Chem 1AA3 17 Average vs. instantaneous rate 0.0280.4420 0.0320.6810 0.0400.922 0.0400.961 1.000 (mM/s)(mM)(s) calculated average rate calc'd [red]time v0 = 0.041 mM/s (Data from Berti section.) Chem 1AA3Chem 1AA3 18 14-2. Measuring reaction rates • initial rate is v0 – rate at t = 0 – when discussing enzymatic reactions, we use v0 almost exclusively: • avoids complications from reactant depletion, product inhibition, equilibrium effects, enzyme inactivation over time. Chem 1AA3Chem 1AA3 19 14-2. Measuring reaction rates Key concepts: – want to know instantaneous rates – experimental rates are average rates – to approach instantaneous rates experimentally, use short measurement times & measure rates near t = 0 – use initial rates for enzymatic reactions Chem 1AA3Chem 1AA3 19 14-2. Measuring reaction rates Key concepts: – want to know instantaneous rates – experimental rates are average rates – to approach instantaneous rates experimentally, use short measurement times & measure rates near t = 0 – use initial rates for enzymatic reactions Chem 1AA3Chem 1AA3 20 PH Formative iClicker Question #18 For the following reaction, which statement is correct? (a) avg. rate = .O2/.t (b) avg. rate = .H2O/.t (c) avg. rate = -½ × .O2/.t (d) avg. rate = -2 × .O2/.t CH4 + 2 O2 CO2 + 2 H2O Chem 1AA3Chem 1AA3 21 PB Formative iClicker Question #18 For the following reaction, which statement is not correct? (a) v = ½ × dO2/dt (b) v = ½ × dH2O/dt (c) v = -dCH4/dt (d) v = dCO2/dt CH4 + 2 O2 CO2 + 2 H2O Chem 1AA3Chem 1AA3 21 PB Formative iClicker Question #18 For the following reaction, which statement is not correct? (a) v = ½ × dO2/dt (b) v = ½ × dH2O/dt (c) v = -dCH4/dt (d) v = dCO2/dt CH4 + 2 O2 CO2 + 2 H2O Chem 1AA3Chem 1AA3 22 JV Formative iClicker Question #18 For the following reaction, which statement is correct? (a) v = dNH3/dt (b) v = ½ × dNH3/dt (c) v = 2 × dNH3/dt (d) v = dN2/dt N2 + 3 H2 2 NH3 Chem 1AA3Chem 1AA3 23 HS Formative iClicker Question #18 For the following reaction, which statement is not correct? (a) avg. rate = .N2/.t (b) avg. rate = -1/3 × .H2/.t (c) avg. rate = ½ × .NH3/.t (d) v = ½ × dNH3/dt N2 + 3 H2 2 NH3 Chem 1AA3Chem 1AA3 23 HS Formative iClicker Question #18 For the following reaction, which statement is not correct? (a) avg. rate = .N2/.t (b) avg. rate = -1/3 × .H2/.t (c) avg. rate = ½ × .NH3/.t (d) v = ½ × dNH3/dt N2 + 3 H2 2 NH3 14-3. Effect of concentration on reaction rates: The rate law • in the food colouring experiment, v0 .[A]: 0.0 0.5 1.0 1.5 2.0 v0 (M/min) 0.0 1.0 2.0 3.0 4.0 [A] (M) Chem 1AA3Chem 1AA3 24 14-3. Effect of concentration on reaction rates: The rate law • v0 = constant is also possible 4.0 v0 (M/min) 3.0 2.0 1.0 0.0 0.0 0.5 1.0 1.5 2.0 [A] (M) Chem 1AA3Chem 1AA3 25 Chem 1AA3Chem 1AA3 26 14-3. Effect of concentration on reaction rates: The rate law • v0 .[A]2 [A] (M) 0.0 0.5 1.0 1.5 2.0 v0 (M/min) 0.0 1.0 2.0 3.0 4.0 Chem 1AA3Chem 1AA3 27 14-3. Effect of concentration on reaction rates: The rate law • dependence of v0 on [A] gives information about mechanism • relationship between concentration and rate is the rate law or rate equation: aA + bB .gG + hH (6, 14.5) v0 = k[A]m[B]n (9, 14.6) • m does not (necessarily) equal a • n does not (necessarily) equal b • a & b are determined by stoichiometry Chem 1AA3Chem 1AA3 27 14-3. Effect of concentration on reaction rates: The rate law • dependence of v0 on [A] gives information about mechanism • relationship between concentration and rate is the rate law or rate equation: aA + bB .gG + hH (6, 14.5) v0 = k[A]m[B]n (9, 14.6) • m does not (necessarily) equal a • n does not (necessarily) equal b • a & b are determined by stoichiometry Chem 1AA3Chem 1AA3 28 14-3. Effect of concentration on reaction rates: The rate law v0 = k[A]m[B]n (9, 14.6) • m & n – determined experimentally – usually small, positive integers (0, 1 or 2) •overall order of a reaction is (m + n) – order w.r.t.* A is m – order w.r.t. B is n (* w.r.t. = with respect to) Chem 1AA3Chem 1AA3 29 14-3. Effect of concentration on reaction rates: The rate law • Method of initial rates • find m and n by measuring v0 at varying [A], [B] Zero-order m = 0, no effect of [A] First-order m = 1, v0 .[A] Second-order (m + n) = 2, v0 .[A]2 or [A][B] • once m & n are known, use v0 to derive the rate constant, k• k is a fundamental property of the reaction, whereas v0 reflects [A], [B] Chem 1AA3Chem 1AA3 29 14-3. Effect of concentration on reaction rates: The rate law • Method of initial rates • find m and n by measuring v0 at varying [A], [B] Zero-order m = 0, no effect of [A] First-order m = 1, v0 .[A] Second-order (m + n) = 2, v0 .[A]2 or [A][B] • once m & n are known, use v0 to derive the rate constant, k• k is a fundamental property of the reaction, whereas v0 reflects [A], [B] Chem 1AA3Chem 1AA3 30 14-3. Effect of concentration on reaction rates: The rate law • order of the reaction tells us how many species are present in the rate-limiting step of the reaction • Key concepts: – order . stoichiometry – order is determined experimentally – order = number of species involved at transition state of the rate-limiting step PH Formative iClicker Question #19 Chem 1AA3Chem 1AA3 31 Which of the following rate equations is not third order overall? (a) v0 = k[A]3 (b) v0 = k[B]3[C][D]-1 (c) v0 = k[A]3[B] (d) v0 = k[A][B]2 Chem 1AA3Chem 1AA3 32 PB Formative iClicker Question #19 Which of the following rate equations is fourth order overall? (a) v0 = k[A]3[B]0 (b) v0 = k[B]3[C][D]-1 (c) v0 = k[A]3[B] (d) v0 = k[A][B]2 JV Formative iClicker Question #19 Chem 1AA3Chem 1AA3 33 Which of the following rate equations is not fourth order overall? (a) v0 = k[A]3[B][D]-1 (b) v0 = k[B]3[C]2[D]-1 (c) v0 = k[B]3[C] (d) v0 = k[A]4 Chem 1AA3Chem 1AA3 34 HS Formative iClicker Question #19 Which of the following rate equations is third order overall? (a) v0 = k[A]2 (b) v0 = k[B]2[C][D]-1 (c) v0 = k[A]3[B] (d) v0 = k[A][B]2 Chem 1AA3Chem 1AA3 35 14-4. Zero-order reactions • v0 is independent of [A] v0 = k = constant (13) • units for v are concentration/time (e.g., M/s) (always) Concept check: What are the units of k for a zero-order reaction? • units for k are concentration/time, e.g., M•s-1 Chem 1AA3Chem 1AA3 35 14-4. Zero-order reactions • v0 is independent of [A] v0 = k = constant (13) • units for v are concentration/time (e.g., M/s) (always) Concept check: What are the units of k for a zero-order reaction? • units for k are concentration/time, e.g., M•s-1 Chem 1AA3Chem 1AA3 36 14-4. Zero-order reactions • integrated rate law: [A]t = [A]0 -kt (14, 14.10) time (min) 0.0 0.5 1.0 1.5 2.0 [A] ( M) 0.00 0.25 0.50 0.75 1.00 Chem 1AA3Chem 1AA3 37 14-4. Zero-order reactions • Zero-order processes: – evaporation / sublimation with constant surface area • Pseudo zero-order reactions: – reactions where catalyst is saturated with reactants (e.g., drug/alcohol metabolism) Key concepts: – rate = rate constant (k) – true zero-order reactions are rare Chem 1AA3Chem 1AA3 37 14-4. Zero-order reactions • Zero-order processes: – evaporation / sublimation with constant surface area • Pseudo zero-order reactions: – reactions where catalyst is saturated with reactants (e.g., drug/alcohol metabolism) Key concepts: – rate = rate constant (k) – true zero-order reactions are rare Chem 1AA3Chem 1AA3 38 14-5. First-order reactions • reaction of MeOH with tBu-Cl is SN1: Cl O + HClOH MeOH tBu-Cl MTBE Chem 1AA3Chem 1AA3 39 14-5. First-order reactions • reaction order w.r.t. tBu-Cl? 1st-order MeOH? 0th-order • overall reaction order? 1st-order • rate equation? v= k[tBu-Cl] = k[tBu-Cl]1[MeOH]0 [MeOH] (M) v0 (M/min) variable MeOH, constant tBu-Cl [tBu-Cl] (M) v0 ( M/min) variable tBu-Cl, constant MeOH Chem 1AA3Chem 1AA3 39 14-5. First-order reactions • reaction order w.r.t. tBu-Cl? 1st-order MeOH? 0th-order • overall reaction order? 1st-order • rate equation? v= k[tBu-Cl] = k[tBu-Cl]1[MeOH]0 [MeOH] (M) v0 (M/min) variable MeOH, constant tBu-Cl [tBu-Cl] (M) v0 ( M/min) variable tBu-Cl, constant MeOH Chem 1AA3Chem 1AA3 40 14-5. First-order reactions Why first order? • rate-limiting C-Cl bond cleavage • MeOH attack is fast .rate controlled by C-Cl bond cleavage Cl tBu-Cl Cl-SLOW O + H2O-CH3 + Cl- MTBE Cl-OH fast MeOH O H fast HO ++ Chem 1AA3Chem 1AA3 41 14-5. First-order reactions • MeOH does not enter until after the rate-limiting step, .no effect from [MeOH] • one molecule in the rate-limiting step, .1st-order v0 = k[A] (10, 14.12) Concept check: What are the units of k for a first-order reaction? – units for k are 1/time (e.g., s-1) Chem 1AA3Chem 1AA3 41 14-5. First-order reactions • MeOH does not enter until after the rate-limiting step, .no effect from [MeOH] • one molecule in the rate-limiting step, .1st-order v0 = k[A] (10, 14.12) Concept check: What are the units of k for a first-order reaction? – units for k are 1/time (e.g., s-1) Chem 1AA3Chem 1AA3 42 14-5. First-order reactions • Characteristics of k: (1) constant regardless of concentration (2) depends on the identity of the reactants, temperature, catalyst, solvent Che CheChe m mm 1AA3 1AA31AA3 43 14-5. First-order reactions • Integrated rate law for first-order reactions – rate equation gives v at every instant – integrating v vs. time gives [A] consumed (or [G] produced) – integrate d[A]/dt with respect to time: (11, 14.13) • ln[A] is unitless, so kt is unitless (integration is shown on p. 583 of the text) 0t 0 t ln[A]tln[A]ort [A] [A] - +=-= kkln 14-5. First-order reactions • rearrange eq. 11: [A]t = [A]0•e-kt • Half-life -t1/2 –1st-order reactions have constant t1/2 [A]t = ½•[A]0 at t1/2: () 1/2 1/2 t t [A] [A] 21 0 021 • • -= -= . . . . . . . . k k ln ln (11a) Che CheChe m mm 1AA3 1AA31AA3 44 Chem 1AA3Chem 1AA3 45 14-5. First-order reactions (12, 14.14)kk 6902 21 .lnt / == )ln 2lnthat( recall 21 = .. . . .. . . -= k 21 1/2tln Chem 1AA3Chem 1AA3 46 14-5. First-order reactions • Reactions involving gases – same as solution reactions, but use partial pressures (PA) in place of molarity, e.g.: (11b, 14.15)t )( )( 0 t k-= A A P Pln Chem 1AA3Chem 1AA3 47 14-5. First-order reactions • Examples of first-order reactions: (1) radioactive decay (2) SN1 nucleophilic substitutions • Key Concepts: – v0 .[A] –t1/2 = constant – rate and integrated equations Chem 1AA3Chem 1AA3 47 14-5. First-order reactions • Examples of first-order reactions: (1) radioactive decay (2) SN1 nucleophilic substitutions • Key Concepts: – v0 .[A] –t1/2 = constant – rate and integrated equations Chem 1AA3Chem 1AA3 48 14-6. Second-order reactions A second-order reaction: •SN2 nucleophilic substitution ClH3C O CH3 H3C + HClH3C OH MeOH Me-Cl Me2O Chem 1AA3Chem 1AA3 49 14-6. Second-order reactions • reaction order w.r.t. Me-Cl? 1st-order MeOH? 1st-order • overall reaction order? 2nd-order • rate equation? v= k[Me-Cl][MeOH] = k[Me-Cl]1[MeOH]1 [MeOH] (M) v0 (M/min) variable MeOH, constant Me-Cl [Me-Cl] (M) v0 (M/min) variable Me-Cl, constant MeOH Chem 1AA3Chem 1AA3 49 14-6. Second-order reactions • reaction order w.r.t. Me-Cl? 1st-order MeOH? 1st-order • overall reaction order? 2nd-order • rate equation? v= k[Me-Cl][MeOH] = k[Me-Cl]1[MeOH]1 [MeOH] (M) v0 (M/min) variable MeOH, constant Me-Cl [Me-Cl] (M) v0 (M/min) variable Me-Cl, constant MeOH Chem 1AA3Chem 1AA3 50 14-6. Second-order reactions • Why second order? – single concerted step with both reactants present at rate- limiting step • rate depends on the presence of both reactants ClH3C O CH3 H3C + HClH3C OH MeOH Me-Cl Me2O H HH O Cl H3C H d+ dtransition state Chem 1AA3Chem 1AA3 51 14-6. Second-order reactions v0 = k[MeOH][Me-Cl] (15) • units for v are concentration/time (e.g., M/s) • units of [MeOH] and [Me-Cl] are concentration (e.g., M) Concept check: What are the units of k for a second-order reaction? • units for k are 1/{concentration•time} (e.g., M-1•s-1) Chem 1AA3Chem 1AA3 51 14-6. Second-order reactions v0 = k[MeOH][Me-Cl] (15) • units for v are concentration/time (e.g., M/s) • units of [MeOH] and [Me-Cl] are concentration (e.g., M) Concept check: What are the units of k for a second-order reaction? • units for k are 1/{concentration•time} (e.g., M-1•s-1) Chem 1AA3Chem 1AA3 52 14-6. Second-order reactions • example from the textbook: 2A . products (16) •where: v0 = k[A]2 (17, 14.17) •SN2 example: A + B . products, •where: v0 = k[A][B] (17a) Chem 1AA3Chem 1AA3 53 14-6. Second-order reactions Pseudo first-order reactions –2nd-order reaction rates become very slow as reactants are depleted • e.g.: H3C O O R + H2O H3C OH O + HO-R H+ Chem 1AA3Chem 1AA3 53 14-6. Second-order reactions Pseudo first-order reactions –2nd-order reaction rates become very slow as reactants are depleted • e.g.: H3C O O R + H2O H3C OH O + HO-R H+ Chem 1AA3Chem 1AA3 54 time (min) [ester] (M) 0.00 0.05 0.10 time (min) [water] (M) 0.00 0.05 0.10 14-6. Second-order reactions • e.g., reaction of 0.1 M ester and 0.1 M H2O in acetone*: H3C O O R + H2O H3C OH O + HO-R H+ * calculations neglect reversibility of reaction, which will slow it even more Chem 1AA3Chem 1AA3 55 14-6. Second-order reactions • Pseudo first-order reactions – Run ester hydrolysis reaction in dilute aqueous acid. – Change in [H2O] is negligible. – Reaction appears to be first order. – behaves like a 1st-order irreversible reaction: v = k[ester] 0.1 M0.1 M55.4 M0 Mfinal 0 M0 M55.5 M0.1 Minitial [HO-R][AcOH][H2O][ester] Chem 1AA3Chem 1AA3 55 14-6. Second-order reactions • Pseudo first-order reactions – Run ester hydrolysis reaction in dilute aqueous acid. – Change in [H2O] is negligible. – Reaction appears to be first order. – behaves like a 1st-order irreversible reaction: v = k[ester] 0.1 M0.1 M55.4 M0 Mfinal 0 M0 M55.5 M0.1 Minitial [HO-R][AcOH][H2O][ester] Chem 1AA3Chem 1AA3 56 14-6. Second-order reactions • Pseudo first-order reactions time (min) [ester] or [water] (M) 0 0.05 0.1 20 40 60 H3C O O R + H2O H3C OH O + HO-R H+ Chem 1AA3Chem 1AA3 57 14-6. Second-order reactions • Key concepts: – rate depends on both reactants (or [A]2) – make pseudo-1st order with one excess reagent Chem 1AA3Chem 1AA3 57 14-6. Second-order reactions • Key concepts: – rate depends on both reactants (or [A]2) – make pseudo-1st order with one excess reagent Chem 1AA3Chem 1AA3 58 PH Formative iClicker Question #20 What is the rate constant, k, for a reaction with the following relationship between reactant concentration, [A], and initial velocity, v0? (a) k = 1.0 s-1 (b) k = 10 M•s-1 (c) k = 1.0 M•s-1 (d) k = 10 M-1•s-1 0.4 M•s-10.2 M 0.1 M•s-10.1 M v0[A] Chem 1AA3Chem 1AA3 59 PB Formative iClicker Question #20 What is the rate constant, k, for a reaction with the following relationship between reactant concentration, [A], and initial velocity, v0? (a) k = 100 s-1 (b) k = 1000 M-1•s-1 (c) k = 100 M•s-1 (d) k = 1000 M•s-1 90 M•s-10.3 M 10 M•s-10.1 M v0[A] Chem 1AA3Chem 1AA3 59 PB Formative iClicker Question #20 What is the rate constant, k, for a reaction with the following relationship between reactant concentration, [A], and initial velocity, v0? (a) k = 100 s-1 (b) k = 1000 M-1•s-1 (c) k = 100 M•s-1 (d) k = 1000 M•s-1 90 M•s-10.3 M 10 M•s-10.1 M v0[A] Chem 1AA3Chem 1AA3 60 JV Formative iClicker Question #20 What is the rate constant, k, for a reaction with the following relationship between reactant concentration, [A], and initial velocity, v0? (a) k = 10-3 M-1•s-1 (b) k = 10 M-1•s-1 (c) k = 0.01 s-1 (d) k = 10 s-1 20 mM•s-12 M 10 mM•s-11 M v0[A] HS Formative iClicker Question #20 velocity, v0? (a) k = 0.01 M-1•s-1 2 M 1 M [A] 4 mM•s-1 1 mM•s-1 v0 (b) k = 1.0 M-1•s-1 (c) k = 10-3 M-1•s-1 (d) k = 10 M-1•s-1 Chem 1AA3Chem 1AA3 61 What is the rate constant, k, for a reaction with the following relationship between reactant concentration, [A], and initial Chem 1AA3Chem 1AA3 62 14-7. Reaction kinetics: A summary Things you can calculate: (1) v0 when the rate law is known: v0 = k[A]m[B]n... (2) Instantaneous rate (v) from: (i) tangent to line in graph of [A] vs. t, (ii) -.[A]/.t (average rate) for short .t (iii) rate law (3) Order of reaction from: (i) v0 vs. concentration (ii) graph that gives a straight line (iii) constant t1/2 (1st-order) (iv) integrated rate law which gives a constant k Chem 1AA3Chem 1AA3 63 14-7. Reaction kinetics: A summary Things you can calculate: (4) k from: (i) slope of line in an appropriate graph (ii) substitute data into the appropriate integrated rate law (iii) from t1/2 (1st-order) (5) use integrated rate law to give [A]t and [G]t from k and [A]0. Chem 1AA3Chem 1AA3 63 14-7. Reaction kinetics: A summary Things you can calculate: (4) k from: (i) slope of line in an appropriate graph (ii) substitute data into the appropriate integrated rate law (iii) from t1/2 (1st-order) (5) use i
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