UNIVERSITY OF SCIENCE VIETNAM NATIONAL UNIVERSITY, HCM CITY, VIETNAM E-mail: ctthien@hcmus.edu.vn
(15 h theory & problem solver)
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1. Chemical kinetics and reaction dynamics, Paul L.
Houston, Mc Graw Hill Ed. Cornell University, 2001. 2. Chemical kinetics, K.J. Laidler, Harper Row Publ. 3rd ed., NY, 1987. 3. Chemical kinetics and reaction dynamics, Santosh K. Upadhyay, Springer Ed. 2006. 4. Physical chemistry 3: Chemical Kinetics, F. Temps, D- 24098 Kiel, Germany, 2014. 5. Giáo trình Hóa lý tập III, Trần Văn Nhân, NXB GD, 2011. 6. Động hóa học, Lê Cộng Hòa, NXB BKHN 2008. 7. Hóa lý, Trần Khắc Chương, ĐHBK TP.HCM, 1999. 3
Objectives of this course
§ Know how to define and determine the rates of
disappearance of a reagent and the formation of a product. § Know how to define the reaction rate and relate it to the disappearance and formation rates of different species § Know the influence of various kinetic factors: ü Know how to define and determine the order of a chemical reaction, the degeneration of order. ü Arrhenius Empirical Law, Activation Energy § Know how to express and integrate the corresponding speed law for simple orders. Half reaction time 4
1) First-order reactions The order of a reaction is defined as the sum of the exponents in the rate law. A → P t=0 a 0 t a–x x
d [ A] dC The rate equation: v=- ó v=- = k.C dt dt Where: Co = a ; Ct = a –x 𝑑C! − = k(a − x) dt ! #$% 𝑑(a − x) = kdt ; - ó - ó -ln(a-x) = kt ó a−x " # 6
3 18/10/2021 gure 2.5: Kinetics of first-order reactions.
• The half lifetime t1/2 is the
time after which [A] has dropped to 1/2 of its initial value.
1 0,693 k= ln 2 ® t 1/ 2 = t1/ 2 k
• The half lifetime for a
first-order reactions is independent of the initial concentration! Kinetics of first-order reactions. 7
me constant:Experimental The rate coefficient determinationhas of kthe dimension of an inverse time. Thus,
1 line with slope m = −k (see slide 5):
• Plot of ln[A] vs. t gives a straight = (2.39) ln ([A]/[Ao]) = −kt
Advantage: We do not need to know the absolute concentration
1 of [A]. s dimension of time and is the time after which [A] has dropped to (= 36 8 %) of initial value: • Numerical fit of k to the exponential decay curve using the Marquardt-Levenberg non- linear least-squares fitting−algorithm. [A]0This method [A]0 is useful in particular for analyzing [A] = decay experimental = [A]curves 0 = with a ≈ constant background term. Again, we(2.40) do not need to 2 718 know the absolute concentration of [A].
• Anybody who wants to do least-squares fitting is urged to consult appropriate literature
1 before alf lifetime: The halfdoing the fitting! lifetime 1 2 isAs thethetime saying goes: after With [A] which threehas parameters, droppedyou to canofdraw an elephant. With a fourth parameter, you can make him walk. 2 initial value (Fig. 2.5): £ ¡ ¢¤ − [A]0 8 A = 1 2 = [A]0 1 2 = (2.41) 8 2
− 1 1 2 = (2.42) 2 (2.43) 4 1 2 = ln 2
ln 2 18/10/2021
Example 1. Typical problem of 1st order reaction
The decomposition of A is first order, and [A] is monitored. The following data are recorded: t / min 0 2 4 8 [A]/[M] 0.100 0.0905 0.0819 0.0670 Calculate k (What is the rate constant? k = 0.0499) Calculate the half life (What is the half life? Half life = 13.89) Calculate [A] when t = 5 min. (What is the concentration when t = 5 min?) Calculate t when [A] = 0.0100. (Estimate the time required for 90% of A to decompose.)
Example 2. After 14 days, a radioisotope has decayed 6.85 wt%. Determine rate constant k, haft-lifetime t1/2 and calculate the time it was decayed 90 wt% and 75 wt%.
Solution.
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Examples for the first order reaction:
1. N2 O → N2 + O
2. •C3H7 → •CH3 + C2H4
3. C12H22O11 + H2 O → C6H12O6 + C6H12O6
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A. KINETICS OF IRREVERSIBLE REACTIONS
2) Second-order reactions: different initial concentration
A + B → P t=0 a b 0 t=t a−x b−x x
Substitution: dx dC dC W =+ = - A - B = k (a - x)(b - x) dt dt dt dx = kdt (a - x)(b - x) 12
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Integration using partial fractions:
1 A B bA - xA + aB - xB bA + aB - x( A + B) = + = = (a - x)(b - x) a - x b - x (a - x)(b - x) (a - x)(b - x)
Left equation = 1 => (A + B) = 0 ó bA + aB = 1.
Therefore: A = − B => bA + a(− A) = 1 → (b − a)A = 1 => A = 1/(b − a) B = − 1/(b − a) Therefore: 1 1 é 1 1 ù = - (a - x)(b - x) b - a êë a - x b - x úû 13
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è 1 é 1 1 ù - dx = kdt b - a êë a - x b - x úû After integration: 1 b-x ln = kt + I b-x b-a a-x ln a-x 1 b Substitution t = 0, x = 0: I = ln b-a a 1 a(b - x) k= ln t (b - a) b(a - x) ó
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7 18/10/2021 2.4 Kinetics of second-order reactions
I Figure 2.9: Kinetics of second-order reactions.
A. KINETICS OF IRREVERSIBLE REACTIONS 3) Second-order reactions: The same initial concentration A + A → P t=0 a a 0 t=t a−x a−x x The reaction rate: d (a - x) W =- = k (a - x)(a - x) = k (a - x) 2 dt Intergration: a- x t d ( a - x) - netics of second-order reactions ò a (a - x) 2 ò0 = kdt 25
Initial value condition at t = 0 1 1 1æ 1 1 ö
Þ - = kt Û k = çç - ÷÷ a-x a t è C C0 ø 15
igure 2.9:15Kinetics of second-order reactions.
I Half lifetime: £ ¡ ¢¤ [A]0 A 1 2 = 2 y 2 1 = +2 1 2 [A]0 [A]0 y 1 1 2 = 2 [A]0 y The half lifetime for a second-order reactions The half lifetime for a depends second-order on the initial reactions depends on the ini Kinetics of second-order reactions. concentration! 16
A + B ® C Initial concentration [A] and B are 0.100M, rate constant k = 10-2 l/mol.s. After 100 s, concentration of [A] is: a) 0.91 M b) 0.091 M c) 9.1 M d) 0.0091 M 17
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A. KINETICS OF IRREVERSIBLE REACTIONS
8) n-order reactions: The same initial concentration The rate equation: dC dC - = kC n Û - n = kdt dt C Integration: C t C t dC - ò n = ò kdt ® - ò C - n dC = ò kdt C0 C 0 C0 0
1 ®- C - n +1 C C0 = kt Û 1 é 1 1 ù - n +1 ®k = ê n -1 - n -1 ú (n - 1)t ë C C0 û 2 n -1 - 1 ® t 1/ 2 = k (n - 1)C0n -1 ® [k ] = C 1- nt -1 18
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A. KINETICS OF IRREVERSIBLE REACTIONS
9) Zero-order reactions: In a zero order reaction the rate does not depend on the concentration of reactant. The decomposite reaction with solid catalysts, reaction rate is independent with the reactant concentration. Example:
[A], M The reaction rate: dC - = kC 0 = k dt ó – dC = kdt After intergration: C = – kt + C0
1 t, min k= (C0 - C ) t C - 0,5C0 0,5C0 t 1/ 2 = 0 = 19 k k 19
5.7. Caractéristiques comparées des réactions
d’ordre 0, 1 et 2 Pour la réaction : A B C D
représentation ordre p [A](t) t1/2 unité de k linéarisée
[A]0 0 A0 k t A (t) A0 k t t 1/ 2 mol.L-1.s-1 2 k
αkt ln 2 1 A0e ln A ln A 0 k t t 1/ 2 = s-1 k
A0 1 1 1 2 k t t 1/ 2 L.mol-1.s-1 1 k t A0 A A0 k A0 20
