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Chemical Reaction: - The process involving the breaking and making and reshuffling a of chemical bonds
is known as chemical reaction. A chemical reaction should fulfill the following conditions:
Rate of reaction: - The rate of chemical reaction means the speed with which the reactants change into
products. It is generally expressed as the decrease in concentration of reactants or increase in
concentration of products per unit time. Thus the rate of a chemical reaction may be defined as the
change in the concentration of nay one of the reactants or products per unit time.
Since the rate of reaction depends upon the molar concentrations of the reactants which generally keep
one decreasing with the passage of time (while concentrations of the products keep on increasing)
therefore the rate of reaction is expressed either as the average rate of reaction or instantaneous rate
of reaction.
Average or Reaction:- This is the approximate way of expressing the rate of reaction and is defined as
the rate of change of concentration per unit time. I t is calculated by dividing the total change in
concentration of any one of reactant or product by the total time taken to do so. Thus
Average rate of reaction =
The rate calculated in this way cannot be exact (but approximate) because it is assumed that the
rate would be constant for the whole spam of time for which it is calculated. But on the contrary the
rate of reaction is not constant but varies with time, since rate of reaction changes at every moment
(due to change in concentration of reactants), Therefore, it is more appropriate to express the rate
of reaction as instantaneous rate which is defined as under
Instantaneous rate of reaction: - It is defined as the decrease in concentration of any one of the
reactants or increase in concentration of any one of the products at a particular instant of time.
If c is the concentration of nay reactant and x is the concentration of any product formed at any
time t, then rate of reaction is given by
[] []
= =
[] []
= =
Where square brackets represents the molar concentrations (moles/litre) of the reactants and
products. The ve sign indicate the decrease in concentration of reactants and +ve sign indicate the
increase in the concentration f products. When time interval is made infinitesimally small (dt)
then change in concentration is represented by dx (very small) change in concentration) and the
expression becomes dx/dt i.e. average rate approaches instantaneous rate.
+ +
The rate of reaction is expresses as
1 [] 1 [] 1 [] 1 []
= = = =
Expressions for rates of some reactions are as follows:
I) 2 + 32 23
[2 ] 1 [2 ] 1 [3 ]
=
= 3
= +2
II) 22 5 22 4 + 2
1 [2 5 ] 1 [2 4 ] [2 ]
= = = +
2 2
III) + 3 2 + 2
[] [3 ] [2 ] [2 ]
= = = =
IV) 2 + 2 2
[2 ] [2 ] 1 []
=
=
=2
V) 5 3 + 2
[5 ] [2 ] [2 ]
= = + =
Since concentration is expressed in moles/litre and time expressed in second or minutes, therefore
the unit of the rate of reaction are moles litre -1 sec-1 or moles litre-1min-1.
In case of gaseous reaction pressure is used in place is expressed in atmospheres therefore the units
of the rate of reaction will be Atmp. Sec-1 or Atmp. Min-1.
Factors affecting the rate of reaction:- the rate of any particular reaction depends upon the
following factors:
1. Concentration of the reactants:- Since the concentration of the reactants is maximum at the
start of the reaction and , therefore the rate of change of concentration is also maximum. As
the concentration of the reactants decrease, t brings about e corresponding decrease in the rate
of reaction. This means that the rate of a reaction is directly proportional to the concentration
of the reactants. For example the rate of burning of wood depends upon the concentration of
oxygen. A piece of wood burns slowly in air but burns rapidly in pure oxygen. Also, the rusting of
iron accelerates during rainy seasons because of high concentration of water.
2. Presence of Catalyst:- A Catalyst is substance which influence the rate of reaction without
undergoing any permanent chemical change in itself. Many reactions proceed at an increased
rate by the presence of certain catalyst. For example, a mixture of H2 and O2 does not react at
room temperature. However, in the presence of a catalyst such as finely divide platinum, the
reactions become quite vigorous. In case of reversible reactions, a catalyst helps to attain to
equilibrium quickly without disturbing the state of equilibrium.
3. Temperature:- The rate of reaction increases with increase of temperature. In most of the cases,
the rate of reaction becomes nearly double for every 10 rise of temperature. In some cases,
reactions do not takes place at room temperature but take place at high temperature. In general
, an increase in the temperature increases the rate of almost all chemical reactions, on the other
hand, a decrease in temperature decrease the rate.
4. Nature of reactants and products. Rates of reactions are influenced by the nature of reactants
and products. A chemical reaction involves the breaking of bonds in reaction and formation of
new bonds in products. The reactivity of a substance can, therefore, be related to the ease with
which he specific bonds are broken or formed and the number of such bonds involved. For
example the oxidation of nitric oxide to Nitrogen dioxide takes place fast while oxidization of
carbon monoxide to carbon dioxide takes place slowly.
5.
2() + 2 () 22 () Fast
2() + 2 () 22 () Slow
In these two reactions the reaction species appear to be very similar to each other. Still
they differ in reaction rates because energy of activation is low in case of NO and high in case of
CO.
6. Surface Area:- The larger the surface area of the reactant, the faster is rate of reaction. I have
been observed that if one of the reactants in a solid, then the rate of reaction depends upon the
state of sub-division of the solid. This face is supported by the general observation that finely
divided solid reacts faster than massive substance. For example a log of wood burns slowly but if
it is cut into smaller wooden chips , the burning takes
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And may or may not be equal p ad q ( the values of p and q are determined experimentally and cannot
be deduced from balanced equation, p+q represents the order of the reaction). However, in on
elementary reaction p and q may be equal to a and b.
On the other hand, the law of mass action gives the rate expression on the basis of overall balanced
equation for the reaction e.g. in the following reaction. XXXXXXXXXXXXX the rate expression on the
basis of law of amass action is
While as the rate of this reaction as found experimentally is proportional to the product of single
concentration term NO2 and F2 and therefore according to rate law
Where K is a constant called velocity constant or rate constant or specific reaction rate.
Rate = k
Hence, rate constant may be defined as the rate of reaction when concentration of each reactant is
taken as unity. It is for this reason that rate constant is also called as specific reaction rate.
Molecularity:- The number of reacting atoms, ions or molecules that colloid simultaneously with another
to bring about a chemical reaction in a single actual step is called Molecularity of the reaction. However
Molecularity cannot be zero, negative or factional and also Molecularity beyond three has no
significance.
If a reaction involves the decomposition of only one species, the reaction is called as unimolecular
reaction e.g.
XXXXXX
If the reaction involves the collision of two species, the reaction is called as bimolecular reaction
XXXXX
If three species take part in collision leading to the formation of products, the reaction is called as
termolecular or tri molecular reaction e.g.
XXXXXX
All above reactions are simple or one step reactions and are known as elementary reactions. The
Molecularity of such reactions is equal to the number o molecules of the reactants taking part in a
chemical reaction i. e. the sum of the molecules of the reactants is balanced chemical equation.
However, the simultaneous collisions between more than three atoms, ions or molecules are usually
uncommon and therefore, for most of the reactions the Molecularity does not exceed there.
Order of reaction:- It is not always possible that the concentration of all the reactants which participate
in chemical reaction (step) can determine the rate of reaction. But only those reacting species whose
concentrations get altered during a chemical change can determine the rate of that reaction. The
dependence of reaction rates on concentration is expressed in terms of order of reaction which is
determined experimentally and is defined as , the total number of atoms, molecules or ions whose
concentration actually alters during a chemical reaction.
For a general reaction, it is defined as the sum of the powers to which the concentration of pressure
terms are raised in the rate low expression to express the observed ate of reaction.
XXXXXX
XXXXXX
Then the order of above equation if equal to (p+q). The values of p and q are determined
experimentally and have no relation to the stoichiometric coefficients a and b of the balanced
chemical equation. Order of reaction with respect o A is P and that with reapect to B is q and overall
order of the reaction is (p+q). if (p+q) =1 , the reaction is said to be first order reaction. If (p+q) =2 or 2,
the reaction is called second order or third order reaction respectively. So, the order of reaction can be
negative, zero, fractional first, second, third or higher some common examples of reactions of different
orders are as under
i.e. the rate of the reaction depends on only one concentration terms, therefore the reaction is said to
be of first order.
1. XXXXXX
2. XXXXXX
3. XXXXXX
4. XXXXXX
5. XXXXXX
6. XXXXXX
1. XXXXXX
The Molecularity of the reaction is two because it involves two reacting species viz ethyl-acetate and
water. However the concentration of ethyl-acetate changes. During the reaction while water is present
in such as large excess that its concentration remains practically unchanged. Therefore the rate of the
reaction as determined experimentally depends only on the concentration of ethyl-acetate and hence
the order of reaction is one
Similarly acidic hydrolysis of sucrose (inversion of cane sugar) is a pseudo first order reaction whose
Molecularity is two but order is one. As XXXXXX
Units of rate constant:- the rate constant K has different units for reactions having different orders. IN
general, then its of rate constant for the reaction of nth order are
1. XXXXXX
K= []
or K= ()
1 1
K= ( 1 )
or K = ( 1 )1
A ----------> Products
If it is a reaction of zero order.
Rate = -d[A] = K[A]o = K
dt
or d[A] = -kdt
Integrating both sides, we get
[A] = -kt + I -------------------------> (i)
Where I is a constant of integration at, t=0, [A] = [A]o
, [A]o = I
Substituting this value of I in equation (i), we get
[A] = -kt + [A]o -------------------------------> (ii)
Or kt = [A]o -[A]
Any reaction of zero order must obey equation (ii). As it is an equation of a straight line (y = mn+c), the
plot of [A] versus t will be a straight line with slope = -k and intercept on the concentrations axis =[A]o as
shown in fig.
Half-life period: Half-life Period (t ) is the time in which half of the substance has reacted. This implies
that when [A] = [A]o /2 , t = t .
Substituting these values in equation (iii), we get
1 []
t = { [A]o - 2
}
= [Ao] / 2k.
i.e. t = [A]o / 2k
The half-life period of a zero reaction is directly proportional to initial concentration i.e. t x [A]o.
Hence a plot of t versus [A]o will be a straight line passing through the origin and slope = k.
(Plot of Half life (t ) versus initial concentration for a zero order reaction )
A reaction is said to be of the first order if the rate of the reaction depends upon one concentration
term only.
Let us consider the simple reaction viz
A ---------------------------------> Products
Suppose we start with A moles per liter of the reactant A. After time t, suppose x moles per litre of it
have decomposed. Therefore, the concentration of A after time t = (a-x) moles per litre. Then according
to law of mass action.
Rate of reaction x (a-x)
i.e.
x (a-x)
or
= k (a-x) ------------------> (i)
Where k is called the rate of constant or the specific reaction rate for the reaction of the first order.
The expression for the rate constant k may be derived as follows:
Equation (i) may be rewritten in the form
= -------------------> (ii)
-ln(a-x)= kt+(lna)
Or kt =ln*a/a-x (v).
Or k = 2.303/T*log*a/a-x (vi)
Equation (vi) is sometimes written in another form which is obtained as follows;
If the initial concentration is [A]o and the concentration after time t is [A], then
Putting a [A]o and (a-x)=[A] ,equation (iv) becomes
K = 2.303/t*log*[A}o/[A].(vii)
Further putting a =[A]o and (a-x)=[A] in equation (v), we get
Kt = ln[A]o/[A]
Which can be written in the exponent form as
[A]o/[A]=ekt or [A]/[A]o
Graphical Method:-
Equation (vii) may be written as
[]
= = log[] = log[]
2.303 []
Or log[A] = -2.303 + log[] ----------------------------------------> (ix)
This is the equation of a straight line (y=mx+c). This if log[A] or log(a-x) values are plotted against time t
the graph obtained should be a straight line if the reaction is of the first order. The intercept made on
the y-axis would be log[Ao] and the scope of the line would be equal to (-k/2-303)
i.e. Slope =
from this, the value of K can be calculated
The time taken for any fraction of the reaction to be completed is independent of the intitial
concentration
Since, k= 2.303 /k log a/a-x ----------->(x)
When half of the reaction is completed x = a/2. Representing the time taken for half of the reaction ot
be completed by t1/2, equation (x) becomes
Temperature has a great effect on the rate of a reaction. For most of the reactions, the rate of the
reaction becomes double or more for every 10o rise of temperature. This effect is usually expressed in
terms of temperature coefficient which is expressed by the following expressions:
+10 308
Temperature coefficient =
= 298
For most of the reactions temperature coefficient lies between 2 and 3. The ratio of rate constants
differing by 10o rise of temperature (preferably for 298 k and 308k) is known as temperature coefficient
of the reactions
The most satisfactory method for expressing the influence of temperature on reaction velocity was
studied by svante Arrhenius in 1889 and proposed the following postulates: -
1) During a chemical reaction molecules collide with each other but every collision is not effective.
2) The active molecules undergo effective collisions, hence lead to product formation. (the
remaining molecules are called passive molecules). There is equilibrium between active and
passive molecules. When temperature is increased the equilibrium is shifted to right).
Passive molecules active molecules
3) In order to get effective collisions, the energy of colliding molecules should be greater than
activation energy. To deduce a quantitative relationship between the rate constant and
temperature, he proposed an equation called Arrhenius equation which is as follows
K = A. e-Ea/RT
Where K = rate constant
R= gas constant
A= frequency factor or Arrhenius factor or pre exponential factor and is related to binary collisions per
second per litre.
Ea = Energy of activation
e-Ea/RT = Botzman factor which gives the fraction of molecules having energy equal to or greater than the
activation energy Ea.
From the Arrhenius equation is clear that the rate of reaction increases exponentially with the increase
in temperature.
K = A. e-Ea/RT
Taking Logarithm,
Lnk = lnA -
Dividing both sides by 2.303, we get
Log K = log A - 2.303
Calculation of energy of activation of two different temperatures
If K1 and K2 are the rate constants at two different temperatures T1 and T2 respectively, then the above
equation becomes
Log K1 = log A - 2.3031 --------------------------> (i)
Log K2 = log A - --------------------------> (ii)
2.3032
Log k2 log k1 =
2.3031 2.3032
2 1 1
Log 1 = 2.303 [1 2
]
2 21
Log = [ ]
1 2.303 12
Thus knowing the value of rate constant k1 and k2 at two different temperatures t1 and t2, the value of
Ea can be calculated. Alternatively, knowing the rate constant at any one temperature. its value at
another temperature can be calculated provided the value of Ea is known for that reaction. When log k
is plotted against 1/t , we get a straight line whose intercept is equal to logA and slope is equal to 2.303
Therefore slope =
2.3031
The minimum amount of energy which the colliding molecules of reactant should possess to break the
bonds Is known as threshold energy. It is denoted by Eth.
The activation energy depends upon the nature of the chemical bonds which are joins to break. It is
independent of the initial and final energy constant of the reacting species (i.e. regardless of the fact
that a reaction is exothermic or endothermic) but depends upon mechanism or path followed by
reaction.
Each reaction has a definite value of Ea and this decides the fraction of total collisions which are
effective. If the activation energy for reaction is low, large number of molecules can have this energy
and the fraction of effective collisions will be large. The reactions will proceed at high rate. On the other
hand, if the activation energy is high, the fraction of effective collisions will be small and the reaction
may be quite slow.
, (. ) + = (. )
I.e. Rate = =
Orders Molecularity
1) It is the sum of the exponents of 1) It is the number of molecules of
molar concentration of reactant reactants taking part in a single step
given by equation of chemical reaction
2) It may or may not have relation with 2) It is calculated for reaction
stoichiometric equation for reaction. mechanism.
3) It depends on experimentally 3) It depends upon the rate
determined rate for the overall determining step of the reaction (in
reaction. the reaction)
4) It may be a whole number or 4) It is always whole number
fraction 5) It is a theoretical concept and can be
5) It is determined experimentally and calculated by adding the molecules
cannot be obtained from the of the slowest (rate determining)
balanced chemical equation step of reaction.
6) It can have all types of values i.e. 6) Its vale can never be zero and values
negative, zero and positive. more than three are least possible.