TYPES OF REACTIONS

1) Homogeneous Reaction - All the reactants are in the same phase/state. e.g. a reaction between two gases is a homogeneous reaction, a reaction between two solutions (liquids) is a homogeneous reaction. 2) Heterogeneous Reaction - The reactants are in different phases/states. e.g a reaction between a solid piece of zinc and a hydrochloric acid solution (liquid) is a heterogeneous reaction, a reaction between steel wool (solid) and oxygen in the air (gas) is a heterogeneous reaction.

RATE OF REACTION
Reaction rate is defined as the rate of appearance of a product or rate of disappearance of a reactant. It is therefore a study of: - how quickly reactants are used, or - how quickly products are made

Note: Units for rate are always "amount of material/time" e.g. moles/s or g/s Note: Reactants disappear and products appear at a rate which is proportional to the coefficients in a balanced equation. Example: Rate of the reaction can be expressed by the following expressions:

Note that a negative () sign indicates a rate of consumption of reactant and positive (+) sign indicates a rate of production of product. The numerical value x can therefore be an absolute value. We should specify the substance whose concentration is changing when we describe rates of reaction, because the concentration of the reactant may not change in a 1:1 ratio with the concentration of the product. The following Sample Problem illustrates this.

Graphical methods of finding the rate of reaction:

Average Rate of Reaction

c1

c2 c1 t2 t1

c2

t1

t2

Instantaneous rate of reaction at A

cA tA

Instantaneous rate of reaction at B

cB tB

Methods used to measure reaction rates depends on the kinds of substances and type of reaction. Examples: a) measurement of gas production during a reaction CaCO3 (s) + 2HCl(aq) --> CaCl2(aq) + CO2(g) + H2O(l) b) conductivity measurement c) measuring the colour change using a spectrophotometer

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An example of experimental determination of reaction rate of: CaCO3 (s) + 2HCl(aq) --> CaCl2(aq) + CO2(g) + H2O(l)

Factors affecting rate of reaction: - Concentration (solutions)

- Temperature - Pressure (gases) - Surface area (solids)

- Catalyst
Note: It is important to know if the reaction is homogeneous or heterogeneous, because surface area is only important in heterogeneous reactions.

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Example: 2H2(g) + O2(g) --> 2H2O(g)

H = 285.8 kJ mol
o

a) The H2(g) disappears at the same rate as the H2O(g) appears. b) The O2(g) disappears at 1/2 the rate as the H2O(g) appears. Heres five ways to increase the reaction rate of the reaction: 1) Increase T 2) Increase [O2] 3) Increase [H2] 4) Add a catalyst, such as Pt. 5) Increase pressure by decreasing volume. (Note that this increases the concentration of both gases) Practice sample questions: 1)

2)

3)

4)

Answers: 1)

2) 4)

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Order of Reaction:
When a series of kinetics experiments is performed on a given system, the rates of reaction (1/time) are measured for different initial concentrations of a reactant. When the evidence is graphed, you may see one or more of these results.

In this plot, r [A]0. The reaction is zeroth order with respect to [A]

In this plot, r [A]1. The reaction is first order with respect to [A]

In this plot, r [A]n, where n isgreater than 1

In this plot, r [A]2. The reaction is second order with respect to [A]

Half-Life: the time for half of the nuclei in a radioactive sample to decay, or for half the amount of a reactant to be used up (in a first order reaction) For a first-order reaction of some reactant A,

This equation can be applied only to a reaction based on first-order kinetics.

Answer:

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Rate Law Equation (rate expressions):
Consider the general reaction, aA + bB + c C

products
x y z

Then the rate law equation or rate expresson can be written as, rate law equation, r = k [A] [B] [C] where: k = x= y= z= (x + y + z) =

and,

a rate constant order of reaction with respect to reactant A order of reaction with respect to reactant B order of reaction with respect to reactant C total order of the reaction

Note that x, y, and z can only be determined empirically, and they can have any real number value, including fractions or zero, and do not have to equal the coefficients (a, b and c) in the balanced equation. They describe the relationship between rate and initial concentration. The rate law is most accurate only for the initial concentrations at a specified temperature. In most reactions, the concentrations and temperature change as soon as the reaction begins. Rate law equations must be determined empirically, by measuring initial rates of reaction for systems in which many trials are performed with different initial concentrations of reactants. Example:
Mixing an acidic solution containing iodate, IO3 (aq), ions with another solution containing I (aq) ions begins a reaction that proceeds, in several reaction steps, to finally produce molecular iodine as one of the products.

The data in the Table are obtained for rate of production of iodine (I2):

(a) What is the rate equation for this reaction? ] = 0.20 mmol/L, [ I ] = 0.40 mmol/L, and [H+] = 0.10 (b) What will the rate of reaction be when [ IO3 mmol/L? Solution (a) We assume that the rate equation follows the pattern
x - y + z r = k IO- 3 I H

Comparing Trials 1 and 2, we find that only [ IO3 ] changes:

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As the [ IO ] doubles, the rate doubles, so rate . The rate is first order with respect to IO
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the initial concentration of iodate ions. Comparing Trials 1 and 3, we find that only [ I ] changes:

As the [ I ] triples, the rate triples, so rate [ I ]1. The rate is first order with respect to the initial concentration of iodide ions. Comparing Trials 3 and 4, we find that only [H_] changes:

As the [H+] doubles, the rate quadruples, so rate [H+]2. The rate is second order with respect to the initial concentration of hydrogen ions. The rate equation for this reaction is

Using the data from Trial 1 to find k, we see that

The rate constant for the equation is 5.0 L3/(mmol3s). (b) Substituting the given concentrations, we see that

The rate at the new set of conditions is 4.0 X 103 mmol/(Ls). Practice problems: 1)

2) The experimental observations in the following Table are obtained for the reaction 2A + B + 2C 3X

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(a) What is the order of reaction with respect to each of the reactants? (b) Write an expression for the rate equation. (c) Calculate a value for the rate constant. (d) Calculate the rate of production of X when [A] = [B] = [C] = 0.40 mol/L. Answer: 1)

2)

Figure 1 Temperature is a measure of the average kinetic energy of the particles. This graph shows how the distribution of kinetic energies changes when a substance is heated or cooled. At any temperature there are some particles with low kinetic energy and some with high kinetic energy. The higher the temperature, the more particles there are with higher kinetic energies.

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Activation Energy:

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Reaction Mechanisms:

rate-determining step (RDS) the slowest step in a reaction mechanism reaction intermediates molecules formed as short-lived products in reaction mechanisms

Sample problem: (a) What is the (overall) activation energy for the following reaction in the potential energy diagram in the following Figure? reactants products (b) What is the reaction enthalpy (H) for the reaction? (c) What is the rate-determining step for the reaction? (d) Is the reaction exothermic or endothermic? (e) Which letters represent activated complexes? (f) Which letters represent reaction intermediates?