The Rate of a Chemical Reaction

The rate of a chemical reaction can be defined as the amount of the reaction which occurs in unit time. The rate of a
reaction is measured by choosing certain properties of the reaction which will indicate how far the reaction has gone, and
whose magnitude can be observed with time without disturbing the reaction.

For example, a reaction which shows color change: the rate of such reaction can be measured by observing how the
intensity of color formed changes with time. In a similar way, a reaction which involves gases can have it’s rate measured
by collecting the gas and observing the way its volume or mass increases with time. Note: increase in rate of reaction
corresponds to decrease in time taken for the reaction, and vice versa.

I.e., rate of reaction is inversely proportional to time,

R α1/T

Factors which affect The Rate of Chemical Reactions

Factors which can affect the rate of a chemical reaction include:

1. Temperature

By the kinetic theory, chemical reactions occur due to collisions of molecules, atoms or ions involved in the reaction. When
the temperature of a reacting system is increased by way of heating, the reacting particles gain energy and are able to
move faster, resulting in increased collisions, which increases the rate of the reaction.

An illustration of this can be found in the reaction between sodium trioxosulphur sulphate(VI) solution and hydrochloric
acid. The reaction leads to the precipitation of sulphur.

By observing the precipitation of sulphur at various temperatures with time, the result obtainable would indicate that: as
the temperature of the reaction is increased, the time taken to precipitate sulphur is decreased (i.e. rate of reaction
iincreases).

Note: the way by which the intensity of the precipitate can be measured is to carry out the entire reaction in a beaker, and
by placing the beaker and its contents on a white piece of paper with a cross marked on it. The time for the disappearance
of the cross when the contents of the beaker are viewed from above will give a measure of the time taken for a certain
fraction of the reaction to occur (i.e. the rate of the reaction) - a stop clock or a watch is used to note this time.

By plotting the graph of temperature over time of reaction, we obtain the curve:

Note: the curve slopes from left to right indicating that increase in temperature leads to decrease in time (i.e., increase in
rate of reaction) and vice versa. Thus, temperature is inversely proportional to time (Temp α 1/Time).

In general, increase in temperature of a reaction by 100 results in doubly the rate of reaction (i.e. decrease in time taken
by half).

2. Concentration of Reactants
The concentration or density of reacting substances affect their closeness to one another, and consequently the
frequency of their collision - this ultimately affects the rate of reaction. The higher the concentration of reactants, the
greater the rate of reaction and vice-versa.

To investigate the effect of concentration on the rate of reaction, the reaction between dilute HCl and sodium
trioxosulphursulphate(VI) solution to precipitate sulphur may be studied.

By observing the reactions of different concentrations of sodium trioxosulphursulphate(VI) with fixed concentration of HCl,
it would be observed, from the result of the reaction that the higher the concentration, the shorter will be the time taken for
sulphur to precipitate, i.e., the higher the concentration, the greater the rate of reaction.

To observe the intensity of sulphur produced at any given moment (this represents the extent of the reaction, i.e. the rate
of the reaction), the reaction is carried out in a beaker, placed on a piece of paper with a cross marked on it. The time
taken for the cross to be invisible when the content of the beaker is viewed from above is noted using a stop clock or a
watch - this is the time taken for a certain fraction of the reaction to occur.

By plotting the graph of concentration against time of reaction, the following curve is obtained:

The curve indicates concentration varying inversely with time, i.e., conc. α 1/T. Hence, increasing the concentration of
reacting masses leads to decrease in time of reaction (i.e. increase in rate of reaction). Decreasing the concentration of
reacting masses leads to increase in the time of reaction (i.e. decrease in rate of reaction).

Another study to show the effect of concentration of reactants on the rate of reaction is “the iodine-clock reaction” - this is
the reaction between hydrogen peroxide solution and acidified potassium iodide solution. Iodine is produced and is
indicated by the observation of a dark-blue coloration with starch.

2I-(aq),+ 2H+(aq) + H2O2(aq) → 2H2O (l) + I2(aq)

The procedure is to use a fixed concentration of one reactant together with a variable concentration of the other, and to
observe the rate of reaction in each combination.

The result of the study would show that the rate of reaction increases with increase in concentration of the reactants. For
gaseous reactions, increase of pressure implies increase of concentration - the rate of the reaction tends to increase as a
result of increase in collisions.

Note: generally, increase in the concentration (in moles per dm3 or mmHg for gases) of reactants will result in increase in
rate of reaction - i.e. decrease in reaction time - and vice versa. The graph above applies to all similar cases.

3. Surface Area of Reactants

In heterogeneous reactions - reactions in which all the reactants are not in the same phase (i.e. different states) - the
surface area of the reactants have been found to affect the rate of the reactions. For example, comparing the rate of
reactions of:

(i) dilute HCl and marble chips.

(ii) Dilute HCl and powdered marble of the same mass as

(i). CaCO3(s) + 2HCl(aq → CaCl2(aq) + CO2(s) + H2O

(l) Both reactions produce CO2 gas. This causes a reduction in the mass of the reacting vessel with time, and this may be
taken as a measure of the rate of the reaction.

The result of both reactions would show that the rate of reaction of the powdered marble is greater than that of the chip
(as shown in the graph below - the mass of the reacting vessel of the powdered marble reduces at shorter time than the
mass of the reacting vessel of the lump of marble).

The reason for this is that the surface area of the powdered marble, being very large compared with that of the chip is
responsible for the difference in their reaction rates.

The graph of the mass of reacting vessel against time of reaction is similar to the diagram below:

Note: The two curves level off at the same point. The reason for this is that the chip (or large piece) completely dissolves
after some time, then the rate of it’s reaction becomes equal to that of the powdered one.

In general, for heterogeneous reactions, reactants of large surface areas have greater rates of reaction (i.e., reactions
occur at shorter time) than reactants of small surface areas. The surface area of powder is greater than that of lumps or
large piece.

Another way the rates of the above reactions can be measured is to measure their increasing volume of CO 2 produced
with time. The graph of volume of CO2 produced against time will give:

4. The Use of Catalyst

The presence of catalysts in chemical reactions would increase their rate. Read more about it here: Catalysts and Chemical
Reactions.

Rate Equation

The rate of a chemical reaction

Considering the hypothetical reaction: A + B → C+ D

The rate of a reaction may be defined as the decrease in concentration of reactants A or B with time;

i.e. rate = -d[A]/dt or -d[B]/dt

Or, as increase in concentration of products C or D with time i.e.

+d[C]/dt or +d[D]/dt

Example, 2HI(g) → I2(g) + H2(g).

Find the rate of the reaction if it is found that during an interval of 100s, the concentration of HI decreased by 0.5M

Solution

Rate = decrease in conc. of reactants/change in time

= 0.5/100 = 0.005m/s

he Rate Law

Last updatedOct 17, 2015

The Relationship Between Order and Mechanisms

Order of Reaction Experiments

In studying a chemical reaction, it is important to consider not only the chemical properties of the reactants, but also the
conditions under which the reaction occurs, the mechanism by which it takes place, the rate at which it occurs, and the
equilibrium toward which it proceeds. According to the law of mass action, the rate of a chemical reaction at a constant
temperature depends only on the concentrations of the substances that influence the rate. The substances that
influence the rate of reaction are usually one or more of the reactants, but can occasionally include products. Catalysts,
which do not appear in the balanced overall chemical equation, can also influence reaction rate. The rate law is
experimentally determined and can be used to predict the relationship between the rate of a reaction and the
concentrations of reactants.

Order of Reactions

Chemical reactions are often classified as zero-order, first-order, second-order, mixed-order, or higher-order. The
general reaction aA + bB → cC + dD will be used in the following discussion. First, the meanings of these orders are
defined in terms of initial rate of reaction effect:

Zero-order in the reactant: there is no effect on the initial rate of reaction

First-order in the reactant: the initial rate of reaction doubles when the reactant is doubled

Second order in the reactant: the initial rate of the reaction quadruples when the reactant is doubled

Third order in the reactant: the initial rate of reaction increases eightfold when the reactant is doubled

Zero-Order Reactions
A zero-order reaction has a constant rate that is independent of the reactant's concentrations. The rate law is as follows:

rate=k(14)

where k has units of Ms−1 . In other words, a zero-order reaction has a rate law in which the sum of the exponents is
equal to zero. A reaction is zero order if concentration data are plotted versus time and the result is a straight line. The
slope of this resulting line is the negative of the zero order rate constant, −k .

At times, chemists and researchers are also concerned with the relationship between the concentration of a reactant
and time. An expression that shows this relationship is called an integrated rate law, in which the equation expresses the
concentration of a reactant as a function of time (remember, each order of reaction has its own unique integrated rate
law). The integrated rate law of a zero-order reaction is given below:

[A]t=−kt+[A]0(15)

See the article on zero-order reactions for the derivation of this law. Notice, however, that this model is not entirely
accurate because this equation predicts negative concentrations at sufficiently large times. In other words, if one were
to graph the concentration of A as a function of time, at some point, the line would cross the x-axis. This is physically
impossible because concentrations cannot be negative. Nevertheless, this model is a sufficient model for ranges of time
where concentration is predicted to be greater than zero.

The half life ( t1/2 ) of a reaction is the time required for the concentration of the radioactive substance to decrease to
one-half of its original value. The half-life of a zero-order reaction can be derived as follows:

For a reaction involving reactant A and from the definition of a half-life, t1/2 is the time it takes for half of the initial
concentration of reactant A to react. These new conditions can be substituted into the integrated rate law form to
obtain the following:

12[A]0=−kt1/2+[A]0(16)

Solving for t1/2 gives the following:

t1/2=[A]02k(17)

First-Order Reactions

A first-order reaction has a rate proportional to the concentration of one reactant.

rate=k[A] or rate=k[B](18)

First-order rate constants have units of sec-1. In other words, a first-order reaction has a rate law in which the sum of
the exponents is equal to 1.

The integrated rate law of a first-order reaction is the following:

ln[A]t=−kt+ln[A]0(9)

or

ln[A]t[A]0=−kt(20)

or

[A]=[A]0e−kt(20)

Moreover, a first-order reaction can be determined by plotting a graph of ln[A] vs. time t: a straight line is produced with
slope -k.

The classic example of a first-order reaction is the process of radioactive decay. The concentration of radioactive
substance A at any time t an be expressed mathematically below:

[A]t=[A]0e−kt(21)

where [A]0 is initial concentration of A, [A]t is the concentration of A at time t, k is the rate constant, and t is the
elapsed time.

The half-life of a first-order reaction can be calculated in a similar fashion as with the half-life of the zero order reaction,
giving the following:

\[t_{1/2} = \dfrac{\ln{2}}{k} \tag{22}]

where k is the first-order rate constant. Notice that the half-life associated with the first-order reaction is the only case
in which half-life is independent of concentration of a reactant or product. In other words, [A] does not appear in the
half-life formula above.
Second-Order Reactions

A second-order reaction has a rate proportional to the product of the concentrations of two reactants, or to the square
of the concentration of a single reactant. For example, each of the equations below describe a second-order reaction:

rateraterate===k[A]2k[B]2k[A][B](14)(15)(16)

In other words, a second-order reaction has a rate law in which the sum of the exponents is equal to 2.

The integrated rate law of a second-order reaction is as follow (see second-order reactions for the derivation):

1[A]=1[A]0+kt(23)

The half-life of a second-order reaction is given below:

t1/2=1k[A]0(24)

Zero order reactions are reactions whose rate does not depend upon the concentration of reactants, eg. photo-chemical
reactions, catalytic reactions,etc.

First order reactions are those where the rate is proportional to the concentration of reactants in such a way that the
sum of the powers is one. Rate= k[A]^a[B]^b; such that a+b=1, or it may depend on the concentration of only one
reactant raised to the power one.

Similarly, second order reactions can be understood.

Order of a reaction is determined experimentally and can't be deduced theoretically.