Homework II

Dwiyana Yogasari
(20164642)

CHEMICAL REACTION
A chemical reaction is a process in which one set of substances, called reactants, is converted to a new set
of substances, called products. In other words, a chemical reaction is the process by which a chemical
change occurs. Chemical reactions happen at a characteristic reaction rate at a given temperature and
chemical concentration. For instance, milk is stored in a refrigerator to slow down the chemical reactions
that cause it to spoil. Current strategies to reduce the rate of deterioration of the ozone layer try to deprive
the ozone-consuming reaction cycle of key intermediates that come from chlorofluorocarbons (CFCs).
Catalysts are used to reduce the harmful emissions from internal combustion engines that contribute to
smog. These examples illustrate the importance of the rates of chemical reactions. Moreover, how fast a
reaction occurs depends on the reaction mechanism the step-by-step molecular pathway leading from
reactants to products.
The Rate of a Chemical Reaction
Rate, or speed, refers to something that happens in a unit of time. A car traveling at 60 mph, for example,
covers a distance of 60 miles in one hour. For chemical reactions, the rate of reaction describes how fast
the concentration of a reactant or product changes with time.
For the hypothetical reaction represented by the balanced equation,

aA+ bB +hH

is

rate of reaction=

1 [ A ] 1 [ B ] 1 [ G ] 1 [ H ]
=
=
=
a t
b t
g t
h t

In this expression, we take the negative value of

[ X ] / t , when

refers to a reactant to ensure

that the rate of reaction is a positive quantity. To determine a rate of reaction, we need to measure changes
in concentration over time.
The Rate Law
Most rate laws are obtained experimentally and are empirical. Consider the hypothetical reaction

aA+ bB +hH

where

a , b , .. . stand for coefficients in the balanced equation. We can often express the rate of such a

reaction as
m

rate of reaction=k [ A ] [ B ] .. .
The terms

[ A ] , [ B ] , . ..

represent reactant molarities. The required exponents, are generally small,

positive whole numbers, although in some cases they may be zero, fractional, or negative. They must be

Homework II

Dwiyana Yogasari
(20164642)

determined by experiment and are generally not related to stoichiometric coefficients

is, often

a , b , .. .

That

m a , n b and so on.

The exponents in the rate law are not necessarily equal to the stoichiometric coefficients in the chemical
equation. In addition, the value of

varies with temperature even though it is called a rate constant.

The term order is related to the exponents in the rate law and is used in two ways: (1) If
that the reaction is first order in A. If

m=1, we say

n=2, the reaction is second order in B, and so on. (2) The

overall order of reaction is the sum of all the exponents

m+ n+. . . The proportionality constant k

relates the rate of reaction to reactant concentrations and is called the rate constant of the reaction. Its
value depends on the specific reaction, the presence of a catalyst (if any), and the temperature. The larger
the value of k, the faster a reaction goes. The order of the reaction establishes the general form of the rate
law and the appropriate units of k (that is, depending on the values of the exponents). With the rate law
for a reaction, we can calculate rates of reaction for known concentrations of reactants and derive an
equation that expresses a reactant concentration as a function of time.
Zero Order Reaction
An overall zero-order reaction has a rate law in which the sum of the exponents,

m+ n .. . is equal to 0.

As an example, lets take a reaction in which a single reactant A decomposes to products.

products

If the reaction is zero order, the rate law is

0

rate of reaction=k [ A ] =k=constant

Another useful equation, called an integrated rate law, expresses the concentration of a reactant as a
function of time.

Homework II
The initial concentration of the reactant A is

Dwiyana Yogasari
(20164642)
[ A ] 0 that is [ A ] =[ A ] 0 , at t=0 . [ A ] decreases

in concentration until the reaction stops. This occurs at the time

t f , where [ A ] =0 The slope of the

line is

( 0 [ A ]0 ) [ A ] 0
=
tf
( t f 0 )

The rate constant is the negative of the slope:

k =slope=

[ A ]0
tf

With general straight line equation

y=mx +b

and substitute

y=[ A ]t (the concentration of A at some time t);

concentration of A at

t=0 time ); and m=k

x=t

(time);

b=[ A ] 0 (the initial

(m, the slope of the straight line), so that

[ A ] t=kt + [ A ] 0

First Order Reaction

An overall first-order reaction has a rate law in which the sum of the exponents,

m+ n .. . is equal to 1.

A particularly common type of first-order reaction is one in which a single reactant. For example:

products

The rate of reaction depends on the concentration of raised to the first power, that is,

rate of reaction=k [ A ]
An integrated rate law for first order reaction will result in

ln

[ A ]t
=kt
[ A ]0

Homework II

Dwiyana Yogasari
(20164642)

Or

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

Second Order Reaction

An overall second-order reaction has a rate law in which the sum of the exponents,

m+ n .. .

is equal

to 2. A particularly common type of second-order reaction is one in which a single reactant. For example:

products

The rate of reaction depends on the concentration of raised to the first power, that is,

rate of reaction=k [ A ]

An integrated rate law for first order reaction will result in

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

The Effect of Temperature on Reaction Rates

From practical experience, we expect chemical reactions to go faster at higher temperatures. To speed up
the biochemical reactions involved in cooking, we raise the temperature, and to slow down other
reactions, we lower the temperature as in refrigerating milk to prevent it from souring.
In 1889, Svante Arrhenius demonstrated that the rate constants of many chemical reactions vary with
temperature in accordance with the expression
Ea / RT

k =A e

By taking the natural logarithm of both sides of this equation, we obtain the following expression.

ln k =

Ea
+ln A
RT

A graph of

ln k

versus

1/T

is a straight line, thus giving us a graphical method for determining

the activation energy of a reaction. We can also derive a useful variation of the equation by writing it
twice each time for a different value of
constant

and the corresponding temperature and then eliminating the

ln A . The result, also called the Arrhenius equation, is

Homework II
ln

k2 Ea 1 1
=

k1 R T 1 T 2

Where

T 1 and

temperature,

8.3145 J mol K

T2

Ea

Dwiyana Yogasari
(20164642)

are two Kelvin temperatures,

k1

and

k 2 are the rate constants at these

is the activation energy in joules per mole. R is the gas constant expressed as
1

Ionic Strength
The ionic strength affects the activity of ions. For comparing experimental results, we work with solutions
that have comparable ionic strength, which is a quantity representing interactions of ions with water
molecules and other ions in a solution. This quantity is usually represented by

I , and an explicit form

will be given after we have defined the system.

The dissociation of an electrolyte

M x X m is,

x
m++ m X
M x X m=x M
Positive ions

m+

and negative ions

must be present together in one solution, and there is

no way to separate activities of positive and negative ions. Thus, we usually use a mean ionic activity

a ,

a=g C (m m x x )(m+ x)
for both positive and negative ions, C

being the stoichiometric concentration of the electrolyte. The

Debye-Huckel limiting law shows that the activity coefficient is related to the ionic strength,
following way:

I
+ z
ln g= A z

in the

Homework II

where

Dwiyana Yogasari
(20164642)

+ z the valence factor and

z

is a constant (= 1.172 at 298 K),

is the ionic strength

which is define by the equation:

2

I = S zi mi
where

mi is the concentration of the i th ion concentration. The summation, S , is taken over all

the possible ions in the solution.

For very concentrated solutions, using concentration based on weight of solvent may offer a better
approximation than using concentration based on volume.

Equilibrium Constants
The equilibrium constant expression is written as a ratio of the product concentrations divided by the
reactant concentrations. G. N. Lewis proposed a more appropriate way to represent the equilibrium
constant expression that uses the activities of the reactants and products.
For the hypothetical, generalized reaction

aA ( aq ) +bB ( aq ) . . . ( aq ) +hH ( aq ) . . .
The equilibrium constant expression has the form
g

( a G ) ( a H ) . .. 1
K=
o
a
b
( a A ) ( a B ) . .. c
where

( )

[G ] [ H ] . . . 1
=
[ A ] a [ B ]b . .. c o

n=g+h+. . .(a+b+ .. .)

of concentrations. The factor

1
co

( )

and

Kc

K c is an equilibrium constant expression written in terms

( )

ensures that

is a dimensionless quantity. The numerator of

an equilibrium constant expression is the product of the activities of the species on the right side of the
equation

aG , a H ,. . .

with each activity raised to a power given by the stoichiometric coefficient

g , h ,. . . The denominator is the product of the activities of the species on the left side of the equation
a A ,a B , .. .
a , b , .. .

and again, with each activity raised to a power given by the stoichiometric coefficient
As previously noted, where equilibrium systems are sufficiently close to ideal in their

behavior, equilibrium concentrations are acceptable approximations to true activities. The numerical value
of an equilibrium constant,

K , depends on the particular reaction and on the temperature.

Homework II

Dwiyana Yogasari
(20164642)

Solubility Product Constant

The solubility product constant,

K sp

, is the equilibrium constant for a solid substance dissolving in

an aqueous solution. It represents the level at which a solute dissolve in solution. The more soluble a
substance is, the higher the

K sp

value it has.

Consider the general dissolution reaction below (in aqueous solutions):

aA ( s ) cC ( aq )+ dD(aq)
To solve for the
and

K sp

it is necessary to take the molarities or concentrations of the products ( cC

dD ) and multiply them. If there are coefficients in front of any of the products, it is necessary to

raise the product to that coefficient power (and also multiply the concentration by that coefficient). This is
shown below:
c

K sp= [ C ] [ D ]

Note that the reactant,

aA , is not included in the

K sp

equation. Solids are not included when

calculating equilibrium constant expressions, because their concentrations do not change the expression;
any change in their concentrations are insignificant, and therefore omitted. Hence,

K sp

represents the

maximum extent that a solid that can dissolved in solution.

pH
Strong acids and bases are considered to be completely ionized in dilute solution, while weak acids and
bases are only partially ionized. Acids tend to increase the hydrogen-ion concentration in solution, while
bases increase the hydroxide concentration. The product of the activity (or approximately, the molar
concentration) of these two ions remains constant at a given temperature and equals

K w . Expression

of hydrogen-ion concentration in terms of molar concentration or activity is rather cumbersome, and so

the
The

pH
pH

method of expression was developed.

of water is a highly important characteristic as it affects equilibria between most chemical

species, effectiveness of coagulation, potential of water to be corrosive, suitability of water to support

living organisms, and most other quality characteristics of water.

Homework II

Dwiyana Yogasari
(20164642)

In 1909 Sorensen proposed to express the hydrogen-ion concentration in terms of its negative logarithm
and designated such value as

+
pH . His symbol has been superseded by the simple designation

pH . The terms may be represented by

+
H

pH=log
With water and in the absence of foreign materials, activity is expressed as molar concentration and

+
H

OH
equals
as required by electro-neutrality, and the product at 25 C

. These conditions mean that

+
H

OH

=, and the

pH

equals

equals

K w or 1014

7 , which is considered the "neutral"

pH for water. The pH scale is usually represented as ranging from 0 to 14. Values of pH lower than 7
indicate the hydrogen-ion concentration is greater than the hydroxide-ion concentration, and the water is
termed acidic. The opposite condition is implied when the pH exceeds 7, and the water is termed basic. It
should be noted that when pH is measured using a pH electrode, it is the hydrogen-ion activity that is
measured and not the molar concentration.

References:
Petrucci, R. H., Herring, F. G., Madura J. D., Bissonnette, C. 2010. General Chemistry: Principles and
Modern Applications. Pearson Prentice Hall, Toronto. 1303 pp.
Sawyer, C. N., McCarty, P. L., Palmer, S. H. Parkin, G. F. 2003 Chemistry for Environmental Engineering
and Science. McGraw-Hill, New York. 752 pp.