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Chemical Kinetics IPE

Chemical Kinetics IPE

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Published by AdiChemAdi
Easy study material for 10+2 AP chemistry students. Specially prepared for Intermediate Public Examination, Andhra Pradesh.
Easy study material for 10+2 AP chemistry students. Specially prepared for Intermediate Public Examination, Andhra Pradesh.

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Published by: AdiChemAdi on Aug 23, 2009
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07/20/2013

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1Chemical kineticsPrepared by V. Aditya vardhanadichemadi @ gmail.com
   P   r  e   p  a   r  e  d    b   y
   V .    A   D   I    T   Y   A    V   A   R   D   H   A   N
   V   A   A   G   D   E   V   I   J   U   N   I   O   R    C   O   L   L   E   G   E    W   A   R   A   N   G   A   L
CHEMICAL KINETICS
Chemical kinetics deals with1) Study of rates of reactions2) Factors affecting rate of reaction3) Study of mechanisms of reactions
Rate of reaction :
The rate of reaction is defined as the change in molar concentration of eitherreactants or products in unit time.
change in concentrationrater=time intervalLet ‘dc’ is the decrease in concentration of reactants in a small interval of time ‘dt’ then
dcr=-dt
( negative sign indicates decrease in concentration )If ‘dx’ is the increase in concentration of products in a small interval of time ‘dt’ then
dxr=dt
( positive sign indicates increase in concentration )E.g., For a reaction,AB
 
dAdBrate rdtdt
In general for a reaction,pP + qQ
rR + sSthe relations between rates of reaction with respect to P,Q,R and S can be written as
dPdQdRdS1111-=-=+=+pdtqdtrdtsdt
Eg., for the reaction,
2g2g3g
N+3H2NH
 
, the relations can be expressed as
223
dNdHdNH11--dt3dt2dt
 
Factors affecting the rate of reaction1) Nature of reactants:
Rate of a reaction depends on the nature of bonding in the reactants. Ioniccompounds react faster than covalent compounds.The reactions between ionic compounds in water occur very fast as they involve only exchange of ions.Eg., AgCl is precipitated out immediately when AgNO
3
solution is added to NaCl solution.
33
AgNO+NaClAgClNaNO
This reaction involves only exchange of ions as shown below and hence occurs very fast.
+-+-+-33
Ag+NO+Na+ClAgClNaNO
Reactions between covalent compounds take place slowly because they require energy for thecleavage of existing bonds.Eg., Following esterification of acetic acid occurs slowly as the breaking of bonds require energy.
CH
3
COHOO C
2
H
5
HCH
3
COC
2
H
5
O
+
OH
2
+
H
2
SO
4
 
2Chemical kineticsPrepared by V. Aditya vardhanadichemadi @ gmail.com
   P   r  e   p  a   r  e  d    b   y
   V .    A   D   I    T   Y   A    V   A   R   D   H   A   N
   V   A   A   G   D   E   V   I   J   U   N   I   O   R    C   O   L   L   E   G   E    W   A   R   A   N   G   A   L
2) Concentration:
Rate of a reaction is directly proportional to the concentration of reactants.rate (r)
 
c
n
wherec = concentrationn = order of the reactionorr = kc
n
wherek = specific rateThe number of collisions increases with increase in concentration and hence the rate of the reactionalso increases.The rate of a reaction decreases with time as the concentration of reactants is decreasing. This canbe shown graphically as follows.
  c  o  n  c  e  n   t  r  a   t   i  o  n  o   f  r  e  a  c   t  a  n   t  s
Time
3) Temperature :
The average kinetic energy and hence the number of collisions increase with abso-lute temperature. Hence rate of reaction increases with increase in temperature.Usually the rate of a reaction is doubled when the temperature is increased by 10
o
C.
Temperature Coefficient :
The ratio of rate constants of a reaction at two different temperatureswhich differ by 10
o
C is called temperature coefficient.
oo
t+10CtC
Temperaturecoefficient=2to3
The relation between rate constant and temperature can be shown by Arrhenius equation.k = A.e
-Ea/RT
Where k = specific rate constantA = Frequency factorE
a
= Activation energyR = Universal Gas constantT = Absolute TemperatureMultiplying by 'ln' (natural logarithm) on both sides,ln k = ln
a
EA-RT
or2.303 log k = 2.303 log
a
EA-RT
orlog k =
a
Elog A-2.303 RT
When a graph is plotted by taking log k on y - axis and 1/T on x-axis, a straight line with negative slopeis obtained.slope =
a
E-2.303 R
=
a
E-4.576
where R = 1.987 cal / K / mole
 
3Chemical kineticsPrepared by V. Aditya vardhanadichemadi @ gmail.com
   P   r  e   p  a   r  e  d    b   y
   V .    A   D   I    T   Y   A    V   A   R   D   H   A   N
   V   A   A   G   D   E   V   I   J   U   N   I   O   R    C   O   L   L   E   G   E    W   A   R   A   N   G   A   L
log A1TE
a
slope = -2.303 Rlog k
Relation between two rate constants at two different temperatures can be given as
a2112
Ek11log=-k2.303RTT
or
21a2112
T-TElog=k2.303RTT
4) Catalyst:
Catalyst is a substance which alters the rate of reaction without being consumed or withoutundergoing any chemical change during the reaction.A catalyst increases the rate of reaction by providing a new path with lower activation energy for thereaction. In case of reversible reactions, catalyst lowers the activation energies of both forward andbackward reaction to the same extent and helps in attaining the equilibrium quickly. 
Reaction coordinate
   P  o   t  e  n   t   i  a   l  e  n  e  r  g  y
without catalystin presence of catalyst
Problems :
1) Write the relations between the rates with respect to reactants & products in the following reaction.2N
2
O 2N
2
+ O
2
Rate Equation or Rate Expression or Rate Law:
Equation that describes mathematical dependanceof rate of reaction on the concentration terms of the reactants is called Rate Equation.For a general reaction,xA+yB+zC
products.
r=kABC
 x y z
wherek= rate constant or specific ratex,y and z are orders with respects to A,B and C respectively.
Order of reaction :
Sum of the powers of the concentration terms in the rate equation is called orderof reaction.For a general reaction,xA + yB + zC
products.

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