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Reaction mechanism is a series of steps which are proposed to explain how the reactants change to the products. In most mechanisms there is one slow or rate determining step and one or more fast steps which do not affect the rate. The partial order of any species appearing in the mechanism after the slow rate-determining step will be zero order. The mechanism can be deduced by finding the order of reaction with respect to each reactant.
Reaction mechanism is a series of steps which are proposed to explain how the reactants change to the products. In most mechanisms there is one slow or rate determining step and one or more fast steps which do not affect the rate. The partial order of any species appearing in the mechanism after the slow rate-determining step will be zero order. The mechanism can be deduced by finding the order of reaction with respect to each reactant.
Reaction mechanism is a series of steps which are proposed to explain how the reactants change to the products. In most mechanisms there is one slow or rate determining step and one or more fast steps which do not affect the rate. The partial order of any species appearing in the mechanism after the slow rate-determining step will be zero order. The mechanism can be deduced by finding the order of reaction with respect to each reactant.
1. Reaction mechanism: A series of steps which are proposed to explain how the reactants change to the products.
2. A proposed mechanism must agree with: (i) The balanced equation i.e. when the steps are added together they should give the overall equation/reaction in terms of reactants and products. (ii) The mechanism must agree with the reaction kinetics or the rate expression. 3. In most mechanisms there is one slow or rate determining step and one or more fast steps which do not affect the rate. The slow rate-determining step can be derived form the rate expression. The partial order of any species appearing in the mechanism after the rate determining step will be zero order confirming it has no effect on the rate.
Mechanism for the hydrolysis of halogenoalkanes There are two possible mechanisms for the hydrolysis of halogenoalkanes. The chemical equation does not give any information about the mechanism of the reaction. The mechanism can be deduced by finding the order of reaction with respect to each reactant. Only substances involved in (or before) the rate-determining step appear in the rate equation. 2
The order with respect to a reactant indicates the number of that particles of that reactant involved in the rate-determining step.
Examples: S N 1 and S N 2 mechanisms of the hydrolysis of halogenoalkanes
(a) S N 1 mechanism (Nucleophilic substitution Unimolecular) The term unimolecular indicates that there is only one species involved in the slow rate determining step. Consider the reaction between 2-bromo-2-methylpropane, (CH 3 ) 3 CBr, a tertiary halogenoalkane and OH - from aqueous sodium hydroxide solution:
(CH 3 ) 3 CBr + OH - (CH 3 ) 3 COH + Br -
Rate = k [ halogenoalkane]
The reaction is FIRST order with respect to (CH 3 ) 3 CBr and zero order with respect to the OH - . Only (CH 3 ) 3 CBr is taking part in the slow rate determining step of the reaction. The OH - are involved in a relatively fast step following the rate determining step and do not affect the rate. Energy profile diagram for a two-step reaction
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The activation energy fort he production of the intermediate is greater than the activation energy fort he intermediate going to the products. This means that the first step is rate-determining step.
The second activation energy is greater, so the second step is the rate determining step. (Unstable) Intermediate product: formed in the slow rate determining step which then reacts further to form the products. Reactions which involve a single intermediate are ususally referred to as two-step reactions. Note that each step has its own transition state and activation energy. (b) S N 2 mechanism: (Nucleophilic substitution Bimolecular)
The term bimolecular refers to the molecularity of the reaction i.e. the number of species involved in the slow rate-determining step.
Consider the reaction between bromoethane, CH 3 CH 2 Br, a primary halogenoalkane and hydroxide ions, OH - from aqueous sodium hydroxide solution:
CH 3 CH 2 Br + OH - CH 3 CH 2 OH + Br -
Rate = k [CH 3 CH 2 Br] [OH - ]
The reaction is FIRST order with respect to both CH 3 CH 2 Br and + OH - . Both of these species must be taking part in the slow rate-determining step of the reaction. The reaction must happen by a straightforward collision between them.
Energy profile diagram for a one step reaction 4
Transition step: This often represents a condition where old bonds are half broken and new ones are half formed. This transition state breaks down directly to the final products without forming a more stable intermediate, which could then be involved in a futher step.
There is one transition state for each step. The transition state is formed when reacting particles have required activation energy E A . The activation energy is the difference in energy between the reactants and the transition state.
(c) While the mechanisms proposed for the alkaline hydrolysis of primary and tertiary halogenoalkanes are consistent with the experimentally determined orders of reaction and the overall equation for the reaction, the reaction between propanone and iodine is not clear.
Propanone will react with iodine in the presence of acid as follows:
CH 3 COCH 3 (aq) + I 2 (aq) CH 3 COCH 2 I (aq) + HI(aq)
Experiments are performed to deduce the order with respect to each reactant. The relative concentrations are shown below.
Deduce the order of reaction with respect to each of the substances given in the table and give the rate equation for the reaction.
A suggested mechanism is as follows:
Propanone will react with iodine in the presence of alkali as follows: 6
CH 3 COCH 3 (aq) + I 2 (aq) CH 3 COCH 2 I (aq) + HI(aq)
Experiments performed to deduce the orders with respect to each reactant reveal that the reaction first order with respect to propanone, zero order with respect to iodine and first order with respect to hydroxide ions, which do not even appear in the equation.
The rate equation for this reaction therefore is:
Rate = k [CH 3 COCH 3 ] [OH - ]
A likely explanation for the mechanism of this reaction is that iodine enters after the rate-determining step.
A suggested mechanism is as follows:
Step 1: the base removes a proton from a CH 3 group, which is the rate determining step.
CH 3 COCH 3 + OH - CH 3 COCH 2 - + H 2 O
Step 2: the lone pair of electrons on the C - of the carbanion forms a bond with an iodine atom in I 2 and I 2 bond breaks.
CH 3 COCH 2 - + I 2 CH 3 COCH 2 I + I -
Since the reaction is first order with respect to both propanone and hydroxide ions and zero order with respect to iodine, the first step must be the rate determining step. This fact can be confirmed by carrying out the same reaction but using bromine or chlorine instead of iodine, where it is found that the overall rate of reaction is the same.
Second or subsequent step is rate determining OH -
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If the second or a subsequent step is rate determining, the derivation of the overall rate equation is more complex.
Consider the reaction: A + 2b + C D + E Step 1 is a rapid step that is reversible: A + B Int where Int is an intermediate Step 2 is the slowest step and hence is rate determining: Int +B X Step 3 is faster than step 2: C + X D + E The overall rate is determined by the rate of the slowest step 2: Overall rate = rate of step 2 = k[B] [Int]
Examples: Finding the slowest step in the reaction mechanism
The rate expression for the reaction: 2A (g) + 3B (g) C (g) + 2D (g)
is found to be Rate = k [A] 2 [B] 8
(a) Does this reaction have a mechanism? Yes, because if there were no reaction mechanism, the rate expression of the given reaction would be: Rate = k [A] 2 [B] 3
But, the given rate expression is different from the rate expression we find. In that case the reaction has a mechanism.
b) If it has a mechanism, write the slowest step. Rate = k [A] 2 [B] So, 2A + B products.
Finding the rate expression of a reaction The mechanism proposed for the reaction:
2 ICl + H 2 2 HCl + I 2 is as follows: (I) H 2 + ICl HI + HCl (slow) (II) HI + ICl HCl + I 2 (fast)
a) Which step is the rate-determining step? Step I b) What is the rate expression for this reaction?
Rate = k [H 2 ] [ICl] The rate expression can be written form the rate-determining step directly. The rate of the reaction is directly proportional to the concentration of the reactants of the rate- determining step.
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c) If the concentrations of H 2 and ICl are doubled, how many times will the rate of the reaction change? Increase by factor 4 (Because the rate of reaction is directly proportional to the both of the concentrations of H 2 and ICl.
d) If the concentrations of HI and HCl are tripled, how many times will the rate change? HI and HCl do not appear on the rate equation, so they do not cause any change.
Finding the rate-determining step The rate equation for the reaction: 2NO (g) + Cl 2 (g) 2 NOCl (g) is found to be Rate = k [NO] 2 [Cl 2 ] which of the following mechanisms will likely belong to this reaction? A. 2NO (g) N 2 O 2 (slow) N 2 O 2 (g) + Cl 2 (g) 2 NOCl (g) (fast)
B. Cl 2 (g) 2Cl (slow) NO (g) + Cl (g) NOCl (g) (fast)
C. NO (g) + NO (g) + Cl 2 (g) 2 NOCl (g)
Answer: C
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Finding the rate expression
The reaction, 2A + B + K L + F + 120 kJ
has a mechanism with three steps. The first two steps of the mechanism are as follows: 2A + B C + D (fast) C + E K + L (fast)
a) Deduce the rate expression for the reaction. The sum of the reactions in the mechanism gives the net (overall) reaction. Therefore, the slowest step which is not given can be found by subtracting the given steps from the net equation. 2A + B + K L + F (overall reaction) -2A + B -C + D (fast) -C + E -K + L (fast) ____________________________________________ K - E - K - D + F or 2K + D F + E which is the slowest step. Therefore, Rate = k [K] 2 [D] b) How many times does the rate increase when the concentration of K and D are tripled? The rate of reaction is directly proportional to [K] 2 [D] If only [K] is tripled, the rate increases 3 2 = 9 times If only [D] is tripled, the rate increases 3 times If both are tripled, the rate = (3) 2 x (3) = 27 times. 11
THE ARRHENIUS EQUATION The Arrhenius equation gives the relationship between the rate constant, k; the temperature, T (in Kelvin) and the activation energy E A which is the minimum energy that the reacting particles should have to collide to start the reaction.
The Arrhenius equation: k = A e E A /RT
where: k = The rate constant (determined at various temperatures) T = Temperature of reaction in kelvin. E A = Activation energy R = Gas constant 12
A = The Arrhenius constant which depends on Using the Arrhenius equation Taking natural logs (ln) on both sides, we obtain a more important form of the expression:
(a) The effect of a change of temperature The fraction of the molecules able to collide successfully almost doubles by increasing the temperature by 10 0 C. This causes the rate of reaction to almost double. This is the value in the rule-of-thumb often used in simple rate of reaction work. (b) The effect of a catalyst A catalyst will provide a route for the reaction with a lower activation energy. As a result, there is a massive increase in the fraction of the molecules which are able to collide successfully, so the rate of reaction increases.
The rate constant is determined at a number of temperatures
The rate constant (ln k) is plotted against 1/T and from the graph a value for the activation energy E A can be found.
ln k
ln A
1/T/K -1
lnk = lnA E A /RT 13
Note: Since gradient is negative, E A is always positive. Units of E A are kJ mol -1
Study question The second-order rate constant for the reaction of 1-bromopropane with aqueous hydroxide ions was measured as a function of temperature.
Tempertaure /K 1/T/K -1 k/mol dm -3 s -1 lnk 298 1.4 X 10 -4
308 3.0 X 10 -4
318 6.8 X 10 -4
328 1.4 X 10 -3
Plot a graph of lnk against 1/T. Measure the gradient of the line and hence calculate the activation energy of the reaction.
2. The activation energy of the oxidation in acid solution of iodide ions by iodate(V) ions can be found by experiment: Place 25 cm 3 of a solution of potassium iodate(V) in a beaker and add 5 drops of starch solution.
Place 25 cm 3 of a solution of potassium iodide and 5 cm 3 of a solution of sodium thiosulfate in another beaker.
Mix the two solutions, start a stop clock immediately and stir with a thermometer. Read and record the temperature of the mixture.
Record the time when the solution turns intense blue.
Repeat the experiment with the same volumes of the solutions but at a higher temperature.
Repeat the experiment at two more different temperatures. 14
(a) Write the ionic equation for the formation of the iodine.
(b) Write the ionic equation for the reaction of iodine with thiosulfate ions.
When all the sodium thiosulfate has been used up, the next iodine that is produced forms an intense blue colour with starch. The results are shown in the table below. Time/s 1/Time/s -1 ln(1/Time) Temperature/K 1/Temp./K -1 135 298 46 313 14 333
Complete the table and then plot a graph of ln(1/Time) on the y-axis against 1/T on the x-axis. Measure the gradient of the line and evaluate the activation energy. You may measure that the gradient of this line is the same as that of lnk against 1/T. Activation energy and types of catalysts Catalysts can be divided into two types: - Homogeneous catalysts - Heterogeneous catalysts Homogeneous catalysts A homogeneous catalyst is in the same phase as the reactants, usually the gas phase or in solution. The rate of reaction depends on the concentrations of the catalyst and one of the reactants. An example is the oxidation of iodide ions by persulfate ions.
2I - (aq) + S 2 O 8 2- (aq) I 2 (aq) + 2SO 4 2- (aq) This is a slow reaction because it requires two negative ions to collide. The reaction is catalysed by iron () ions. The catalysed, route is oxidation of iodide ions by iron() 15
ions, followed by reduction of persulfate ions by iron () ions and the regeneration of the catalyst of iron() ions: 2Fe 3+ (aq) + 2I - (aq) I 2 (aq) + 2Fe 2+ (aq) 2Fe 2+ (aq) + S 2 O 8 2- (aq) 2Fe 3+ (aq) + 2SO 4 2- (aq)
Heterogeneous catalysts A heterogeneous catalyst is in a different phase from the reactants. Many industrial processes use this type of catalyst; they have the advantage that the catalyst can be separated from the equilibrium mixture by simple physical means. For example, in the Haber process the solid iron catalyst catalyses the reaction between two gases, hydrogen and nitrogen. Heterogeneous catalysts are frequently transition metals- for example iron, platinum and nickel. The catalyst has active sites on its surface that rapidly become saturated by reactants, which are then slowly converted into products. These leave the metal surface, thus allowing more of the reactant to be adsorbed. This means that the rate of a reaction is not altered by an increase in pressure of the gaseous reactants.
Exercise: The second-order rate constant for the reaction of 1-bromopropane with aqueous hydroxide ions was measured as a function of temperature.