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Glucose
Fructose
(1)
First-Order Reactions:
When the rate of a reaction is proportional to the first power of the
concentration of a single reactant and may be expressed mathematically
in the form of Eq.1, the reaction is said to be first-order with respect to
the reactant
Eq.1 may be written
dc
= kdt
c
(2)
dc/c = K dt
ln c ln co = k (t 0)
ln c = ln co Kt
Converting to common logarithms yields
Log c = log co Kt/2.303
Or
2.303
K=
log
t
co
(4)
(5)
a
log
ax
(6)
Half-life :
The period of time required for a drug to decompose to one half the
original concentration is the half-life, t1/2 for a first order reaction.
Writing Eq 5 in the form
2.303
K=
log
t1/2
co
0.693
=
co1/2
(7)
t1/2
it is apparent that
0.693
t1/2 =
(8)
Second-Order Reactions:
A second-order reaction is one in which the experimentally
determined rate of reaction is found to be proportional to the
concentration of each of two reactants or to the second power of the
concentration of one reactant. If substances A and B undergo reaction at a
rate proportional to the concentration of each (CA and CB, respectively)
we may write
dcA
dt
dcB
dt
= K.cAcB
(9)
dx / dt = K (a x) ( b x)
(10)
(11)
dx / (a x)2
1
= K dt
ax
= Kt
a0
x
= Kt
(12)
a (a x)
Or
1
K =
(13)
at
a x
2.303
b (a x)
log
ab
= Kt
(14)
a (b x)
Or
2.303
K =
b (a x)
log
t (a b )
(15)
a (b x)
(16)
(17)
Ka
dcB
=
dt
dcC
=
dt
K. cA. cB. cC
(18)
dt
(19)
dt
When a = b = c
dx
= K ( a x)3
(20)
dt
K =
2t
( a x)2
(21)
a2
Ko
(22)
dt
The velocity of reaction is seen to be constant and independent of
the concentration reactant. The rate equation may be integrated between
the initial concentration Co at t = 0, and Ct, the concentration after t hours:
dC = Ko dt
Ct Co = Kot
Or
Ct = Co Kot
(23)
Co
2K
(24)
Determination of Order:
The order of a reaction may be determined by several methods.
1.
Substitution Method.
2.
Graphical Method.
3.
3. Half-life Method:
In general, the half-life of a reaction in which the concentrations of
all reactants are identical is
1
t1/2
(25)
an 1
in which n is the order of the reaction. Thus if two reactions are run
at different initial concentrations, a1 and a2 the half-lives t1/2(1) and t1/2(2)
are related as follows:
(a2)n 1
t1/2 (1)
=
a2
=
(a1)n 1
t1/2(2)
n1
(26)
a1
or in logarithmic form
a2
t1/2 (1)
log
= ( n 1 ) log
t1/2(2)
(27)
a1
and finally
+ 1
(28)
log (a2/a1)
(29)
E a/RT
(30)
2.303 RT
(31)
Ea
=
K1
T2 T1
=
2.303 R
(32)
T1T2
Activation energy:
When two molecules undergo chemical interaction, it is reasonable
to suppose that they must first come close enough to each other to effect a
collision and then, if conditions are right, undergo a rearrangement of
certain electrons to form the bonds characteristic of new molecules. The
colliding molecules must possess at least the amount of energy Ea before
reaction can occur. The greater this energy requirement is, the smaller the
proportion of colliding molecules that will have the necessary energy, and
the slower will be the reaction.
[AB] *
products
k observed = k1 (H + )
(33)
(34)
(35)
(36)
Kw
(37)
(H+)
(38)
dc / dt = k1 (H+) + k2 (OH) c
(39)
(40)
the hydrogen ion or hydroxide ion. The apparent first-order rate constant
for such a reaction is
k observed = ko + k1 (H +) + k2 (OH )
(41)
(Fig. 6). The alkaline branch of the rate-pH profile for this
dG
dt
(42)
= ko + kH [H+] + kA [Hac]
(43)
k = ko + k i c i
(44)
(45)
4- Ionic Strength:
In general the effects of increasing concentrations of electrolytes
on reaction rate can be predicted by consideration of the influence of
ionic strength on interionic attraction. Increased ionic strength would be
expected to decrease rate of reaction involving interaction between
oppositely charged ions, and increase rate of reaction between similarly
charged ions.
Reactions between ions and dipolar molecules, and reactions
between neutral molecules, are generally less sensitive to ionic stregth
effects than are reactions between ionic compounds. However, reactions
7- Catalysis:
The rate of a reaction is frequently influenced by the presence of a
catalyst. Although the hydrolysis of sucrose in the presence of water at
room temperature proceeds with a decrease in free energy, the reaction is
so slow as to be negligible. When the hydrogen ion concentration is
increased, by adding a small amount of acid, however inversion proceeds
at a measurable rate.
A catalyst is therefore defined as a substance that influences the
speed of a reaction without itself being altered chemically. When a
catalyst decreases the velocity of a reaction, it is called a negative
catalysts. Actually, negative catalyst often may be changed permanently
during a reaction, and these should be called inhibitors rather than
catalysts.
Catalysis is considered to operate in the following way. The
catalyst combines with the reactant known as the substrate and forms an
intermediate known as a complex, which then decomposes to regenerate
the catalyst and yield the products. Alternatively, a catalyst may act by
producing free radicals such as CH3 which brings about fast chain
reactions.
Catalytic action may be homogenous or heterogeneous and may
occur in either the gaseous or liquid state. Homogenous catalysis occurs
when the catalyst and the reactants are in the same phase, e.g.: acid-base
catalysis.. Heterogeneous catalysis occurs when the catalyst and the
reactants form separate phases in the mixture. The catalyst may be a
finely divided solid such as platinum, or it may be the walls of the
container. The catalysis occurs at the surface of the solid and is therefore
sometimes known as contact catalysis. The reactant molecules are