202-NYB - KINETICS

Figure 16.2

The wide range of reaction rates.

Figure 16.1

Reaction rate: the central focus of chemical kinetics

Factors That Influence Reaction Rate

Under a specific set of conditions, every reaction has its own characteristic rate, which depends upon the chemical nature of the reactants.

Four factors can be controlled during the reaction: 2. 3. 4. 5. Concentration - molecules must collide to react; Physical state - molecules must mix to collide; Temperature - molecules must collide with enough energy to react; The use of a catalyst.

Figure 16.3

The effect of surface area on reaction rate.

Figure 16.4

Collision energy and reaction rate.

Expressing the Reaction Rate
reaction rate - changes in the concentrations of reactants or products per unit time reactant concentrations decrease while product concentrations increase for

A

B =conc A2-conc A1 t2-t1

rate of reaction = -

change in concentration of A change in time

-

∆ (conc A) ∆t

Table 16.1 Concentration of O3 at Various Time in its Reaction with C2H4 at 303K
C2H4(g) + O 3(g) Time (s) 0.0 10.0 20.0 30.0 40.0 50.0 60.0 C 2H4 O(g) + O2(g) Concentration of O3 (mol/L) 3.20x10-5 2.42x10-5 1.95x10-5 1.63x10-5 1.40x10-5 1.23x10-5 1.10x10-5

-

∆ (conc A) ∆t

Figure 16.5

The concentrations of O3 vs. time during its reaction with C2H4
C2H4(g) + O 3(g) C 2H4 O(g) + O2(g)

rate = ∆ [C2H4] ∆t ∆ [O3] ∆t =

Figure 16.6

Plots of [C2H4] and [O2] vs. time.

Tools of the  Laboratory

In general, for the reaction aA + bB cC + dD

rate =

-

1 a

∆[A] ∆t

= -

1 b

∆[B] ∆t

= +

1 c

∆[C] ∆t

= +

1 d

∆[D] ∆t

The numerical value of the rate depends upon the substance that serves as the reference. The rest is relative to the balanced chemical equation.

Sample Problem 16.1 PROBLEM:

Expressing Rate in Terms of Changes in Concentration with Time

Because it has a nonpolluting product (water vapor), hydrogen gas is used for fuel aboard the space shuttle and may be used by Earth-bound engines in the near future. 2H2(g) + O2(g) 2H2O(g)

(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with time. (b) When [O2] is decreasing at 0.23 mol/L*s, at what rate is [H2O] increasing? PLAN: Choose [O2] as a point of reference since its coefficient is 1. For every molecule of O2 which disappears, 2 molecules of H2 disappear and 2 molecules of H2O appear, so [O2] is disappearing at half the rate of change of H2 and H2O. SOLUTION: ∆[H2] ∆[O2] ∆[H2O] 1 1 ==+ (a) rate = - 2 2 ∆t ∆t ∆t ∆[O2] ∆[H2O] ∆[H2O] (b) = - 0.23mol/L*s = + 1 ; = 0.46mol/L*s ∆t 2 ∆t ∆t

Sample Problem 16.2 Determining Reaction Order from Rate Laws PROBLEM: For each of the following reactions, determine the reaction order with respect to each reactant and the overall order from the given rate law. 2NO2(g); rate = k[NO]2[O2] CH4(g) + CO(g); rate = k[CH3CHO]3/2 I3-(aq) + 2H2O(l); rate = k[H2O2][I-]

(a) 2NO(g) + O2(g) (b) CH3CHO(g)

(c) H2O2(aq) + 3I-(aq) + 2H+(aq)

PLAN: Look at the rate law and not the coefficients of the chemical reaction. SOLUTION: (a) The reaction is 2nd order in NO, 1st order in O2, and 3rd order overall. (b) The reaction is 3/2 order in CH3CHO and 3/2 order overall. (c) The reaction is 1st order in H2O2, 1st order in I- and zero order in H+, while being 2nd order overall.

Table 16.2 Initial Rates for a Series of Experiments in the Reaction Between O2 and NO
2NO(g) + O2(g) 2NO2(g) Initial Rate (mol/L*s) 3.21x10-3 6.40x10-3 12.8x10-3 9.60x10-3 28.8x10-3

Experiment 1 2 3 4 5

Initial Reactant Concentrations (mol/L)

O2 1.10x10-2 2.20x10-2 1.10x10-2 3.30x10-2 1.10x10-2

NO 1.30x10-2 1.30x10-2 2.60x10-2 1.30x10-2 3.90x10-2

Determining Reaction Orders
Using initial rates Run a series of experiments, each of which starts with a different set of reactant concentrations, and from each obtain an initial rate. See Table 16.2 for data on the reaction O2(g) + 2NO(g) 2NO2(g) rate = k [O2]m[NO]n

Compare 2 experiments in which the concentration of one reactant varies and the concentration of the other reactant(s) remains constant. rate2 rate1 = k [O2]2m[NO]2n k [O2]1 [NO]
m n 1

=

[O2]2m [O2]1m m ;

=

[O2]2 [O2]1 2 = 2m

m

6.40x10-3mol/L*s 3.21x10-3mol/L*s

=

2.20x10-2mol/L 1.10x10-2mol/L

m=1

Do a similar calculation for the other reactant(s).

Sample Problem 16.3 Determining Reaction Order from Initial Rate Data PROBLEM: Many gaseous reactions occur in a car engine and exhaust system. One of these is NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO2]m[CO]n

Use the following data to determine the individual and overall reaction orders. Experiment 1 2 3 PLAN: Initial Rate(mol/L*s) Initial [NO2] (mol/L) Initial [CO] (mol/L) 0.10 0.0050 0.10 0.080 0.0050 0.40 0.10 0.10 0.20

Solve for each reactant using the general rate law using the method described previously. rate = k [NO2]m[CO]n First, choose two experiments in which [CO] remains constant and the [NO2] varies.

SOLUTION:

Sample Problem 16.3 Determining Reaction Order from Initial Rate Data continued rate 2 rate 1 0.080 0.0050 rate 3 rate 1 0.0050 0.0050 k [NO2]m2[CO]n2 k [NO2] 1 [CO]
m n 1

=

=

[NO2] 2 [NO2] 1

m The reaction is 2nd order in NO2.

=

0.40 0.10

m

;

16 = 4m and m = 2 [CO] 3 [CO] 1 1 = 2n and n = 0 n

=

k [NO2]m3[CO]n3 k [NO2]m1 [CO]n1 0.20 0.10 n ;

=

The reaction is zero order in CO.

=

rate = k [NO2]2[CO]0 = k [NO2]2

Integrated Rate Laws
rate = ∆[A] ∆t = k [A]

first order rate equation [A]0 [A]t = - kt ln [A]0 = -kt + ln [A]t

ln
rate = ∆[A] ∆t = k [A]2

second order rate equation 1 [A]0 = kt 1 [A]t = kt + 1 [A]0

1 [A]t
rate = ∆[A] ∆t = k [A]0

zero order rate equation

[A]t - [A]0 = - kt

Table 16.3 Units of the Rate Constant k for Several Overall Reaction Orders

Overall Reaction Order 0

Units of k (t in seconds) mol/L*s (or mol L-1 s-1)

1

1/s (or s-1)

2

L/mol*s (or L mol -1 s-1)

3

L2 / mol2 *s (or L2 mol-2 s-1)

Sample Problem 16.4 Determining Reaction Concentration at a Given Time PROBLEM: At 10000C, cyclobutane (C4H8) decomposes in a first-order reaction, with the very high rate constant of 87s-1, to two molecules of ethylene (C2H4). (a) If the initial C4H8 concentration is 2.00M, what is the concentration after 0.010 s? (b) What fraction of C4H8 has decomposed in this time? PLAN: Find the [C4H8] at time, t, using the integrated rate law for a 1st order reaction. Once that value is found, divide the amount decomposed by the initial concentration. SOLUTION: [C4H8]0 2.00 ln ; ln = (87s-1)(0.010s) = kt [C4H8]t (a) [C4H8] [C4H8] = 0.83mol/L (b) [C4H8]0 - [C4H8]t [C4H8]0 = 2.00M - 0.87M 2.00M = 0.58

Figure 16.7

Integrated rate laws and reaction order

1/[A]t = kt + 1/[A]0

ln[A]t = -kt + ln[A]0

[A]t = -kt + [A]0

Figure 16.8

Graphical determination of the reaction order for the decomposition of N2O5.

Figure 16.9

A plot of [N2O5] vs. time for three half-lives. for a first-order process t1/2 = ln 2 k = 0.693 k

Sample Problem 16.5 Determining the Half-Life of a First-Order Reaction PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its 600 bond angles allow poor orbital overlap, its bonds are weak. As a result, it is thermally unstable and rearranges to propene at 10000C via the following first-order reaction: CH2 ∆ H3C CH CH2 (g) H C CH (g)
2 2

The rate constant is 9.2s-1, (a) What is the half-life of the reaction? (b) How long does it take for the concentration of cyclopropane to reach one-quarter of the initial value? 0.693 PLAN: Use the half-life equation, t1/2 = , to find the half-life. k One-quarter of the initial value means two half-lives have passed. SOLUTION: (a) t1/2 = 0.693/9.2s-1 = 0.075s (b) 2 t1/2 = 2(0.075s) = 0.150s

Table 16.4 An Overview of Zero-Order, First-Order, and Simple Second-Order Reactions
Zero Order Rate law Units for k Integrated rate law in straight-line form Plot for straight line Slope, y-intercept Half-life rate = k mol/L*s [A]t = k t + [A]0 [A]t vs. t k, [A]0 [A]0/2k First Order rate = k [A] 1/s ln[A]t = -k t + ln[A]0 ln[A]t vs. t -k, ln[A]0 ln 2/k Second Order rate = k [A]2 L/mol*s 1/[A]t = k t + 1/[A]0 1/[A]t = t k, 1/[A]0 1/k [A]0

Figure 16.10

Dependence of the rate constant on temperature

The Effect of Temperature on Reaction Rate
The Arrhenius Equation

Ea − RT k = Ae
ln k = ln A - Ea/RT k2 k1

where k is the kinetic rate constant at T Ea is the activation energy R is the energy gas constant T is the Kelvin temperature A is the collision frequency factor

ln

Ea = RT

1 T2

1 T1

Figure 16.11 Graphical determination of the activation energy

ln k = -Ea/R (1/T) + ln A

Sample Problem 16.6 Determining the Energy of Activation PROBLEM: The decomposition of hydrogen iodide, 2HI(g) H2(g) + I2(g)

has rate constants of 9.51x10-9L/mol*s at 500. K and 1.10x10-5 L/mol*s at 600. K. Find Ea. PLAN: Use the modification of the Arrhenius equation to find Ea. -1

SOLUTION: ln

k2 k1

= -

Ea R

1 T2

-

1 T1

Ea = - R ln 1 600K -

k2 k1 1 500K

1 T2

-

1 T1

Ea = - (8.314J/mol*K) ln

1.10x10-5L/mol*s 9..51x10-9L/mol*s

Ea = 1.76x105 J/mol = 176 kJ/mol

Figure 16.12

Information sequence to determine the kinetic parameters of a reaction.
Series of plots of concentration vs. time Determine slope  of tangent at t0 for  each plot

Initial rates

Reaction Rate constant orders (k) and actual Compare initial  rate law rates when [A]  Substitute initial rates,  changes and [B] is  orders, and concentrations  Find k  at  held constant and  into general rate law:      varied T m n vice versa rate = k [A] [B] Rate constant and reaction order Rearrange to  linear form and  graph Activation energy, Ea Find k  at  varied T

Plots of concentration vs. time

Integrated rate law (half-life, t1/2) Use direct, ln or  inverse plot to  find order

Figure 16.13

The dependence of possible collisions on the product of reactant concentrations.
A A B 4 collisions B A Add another molecule of A A B A Add another molecule of B A A A B B B

B 6 collisions

Table 16.5 The Effect of Ea and T on the Fraction (f) of Collisions with Sufficient Energy to Allow Reaction
Ea (kJ/mol) 50 75 100 T 250C(298K) 350C(308K) 450C(318K) f (at T = 298 K) 1.70x10-9 7.03x10-14 2.90x10-18 f (at Ea = 50 kJ/mol) 1.70x10-9 3.29x10-9 6.12x10-9

Figure 16.14

The effect of temperature on the distribution of collision energies

Figure 16.15

Energy-level diagram for a reaction
ACTIVATED STATE

Collision Energy

Ea (reverse)

REACTANTS

PRODUCTS The forward reaction is exothermic because the reactants have more energy than the products.

Collision Energy

Ea (forward)

Figure 16.16

An energy-level diagram of the fraction of collisions exceeding Ea.

Figure 16.17

The importance of molecular orientation to an effective collision.

NO + NO3

2 NO2

A is the frequency factor A = pZ where Z is the collision frequency p is the orientation probability factor

REACTION MECHANISMS Table 16.6 Rate Laws for General Elementary Steps
Elementary Step A product Molecularity Unimolecular Rate Law Rate = k [A]

2A

product

Bimolecular

Rate = k [A]2

A+B

product

Bimolecular

Rate = k [A][B]

2A + B

product

Termolecular

Rate = k [A]2[B]

Figure 16.22

Reaction energy diagram of a catalyzed and an uncatalyzed process.

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