8/2/2019 LU 4 Slides Reaction Kinetics http://slidepdf.com/reader/full/lu-4-slides-reaction-kinetics 1/88 4.1 rate of reaction 4.2 collision theory of chemical reaction LU4 Reaction kinetics Theimagecannot bedisplayed.Your computer may nothaveenough memory to open theimage,or theimagemay havebeen corrupted.Restartyour computer, and then open thefileagain.Ifthe red x stillappears,you may haveto deletethe imageand then insertitagain. . rans n sae e ry 4.4 rate law 4.5 Factors affecting rate & rate constant 4.6 Homogeneous & heterogeneous catalyst PRK 1026 CHEMISTRI II UNIMAS (C) NOT FOR SALE
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4.1 rate of reaction4.2 collision theory of chemical reaction
LU4 Reaction kinetics
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Rates of Chemical ReactionsConcentration ofreactant
Concentration ofproduct
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Time
As the reactionproceeds, the
[reactant] decreases.
Time
As the reactionproceeds, the
[product] increases.PRK 1026 CHEMISTRI II UNIMAS (C) NOT
where a, b, c & d are the stoichiometric coefficients
a A + b B c C + d D
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the reactionBr2(aq)+ HCOOH(aq) →2Br−(aq) +2H+(aq) + CO2(g)
Time / s [Br2]/ mol L−1
0.0 0.0120
50.0 0.0101
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100.0 0.00846150.0 0.00710
200.0 0.00596
300.0 0.00420400.0 0.00296
What do you notice [Br2] ?PRK 1026 CHEMISTRI II UNIMAS (C) NOT
the reactionBr2(aq)+ HCOOH(aq) →2Br−(aq) +2H+(aq) + CO2(g)
Average rate = ∆[Br2]
∆t
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the reactionBr2(aq)+ HCOOH(aq) →2Br−(aq) +2H+(aq) + CO2(g)
InstantaneousRateThe rate of
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the reactionBr2(aq)+ HCOOH(aq) →2Br−(aq) +2H+(aq) + CO2(g)
When t=0,a special instant
Such rate known
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2H2O2(aq) →O2(g) + H2O(l)
As gas has pressure, can also measurepressure changes over time
If involve colour changes, usecolourimetric method
How to determine rate experimentally?
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To result in chemical productsreactant molecules must collide
A chemical reaction
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( The Collision Theory )
Minimum energy needed to
bring about product formation
( Activation energy )PRK 1026 CHEMISTRI II UNIMAS (C) NOT
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A constant at a fixed TemperatureIf T , then k will
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The hydrolysis of CH3Br by OH- isgiven by the rate law
Rate = k[CH3Br][OH-]
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Consider another reactionCH3COOCH3 + OH−→CH3COO− + CH3OH
Write the rate law for the reaction.
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. . .
Doubling [F2] while holding [ClO2] constant
will double the rate of reaction.
∴The rate is directly proportional to [F 2 ] The reaction is first order in F 2
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Quadrupling [ClO2] while holding [F2]constant
will quadruple the rate of reaction.
∴The rate is directly proportional to [ClO 2 ]
The reaction is first order in ClO 2
y = 1 PRK 1026 CHEMISTRI II UNIMAS (C) NOTFOR SALE
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• Since the reaction is first order for both [F2]and [ClO2], the rate law is written as
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In the reaction A → B , the initial rate is 1.7x10− 4 mol
L− 1
s− 1
when the concentration of A is 0.25 mol L− 1
a) What will be the initial rate of reaction if [A] is 0.75
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mol L− with zero order of reaction?
b) What will be the initial rate of reaction if [A] is 0.75
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How long (in seconds) will it take to decrease from 0.88
mol L−1
to 0.14 mol L−1 ?
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The reaction 2N 2O5 → 4NO2 + O2 is a first order reaction with a rate constant of
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. x − s− a .
If the initial concentration of N 2O5 is 0.25 mol L− 1 ,
Time required for the initialamount of reactant to decrease
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examplethe decomposition of cyclopropane to propene
is a first order reaction with a rate constant
of 6.7x10−
4 s−
1 at 500 °C.
Calculate the half-life of the reaction.
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The half-life of first order reactionis 84.1 minute.
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order reaction isindependent of amount of active substance
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what fraction of active materialis left after 4 half-lives?
Half-life
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a) Most reaction goes to productthrough a number of steps
Reaction mechanism
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Step 2 M + A → Y fast
Step 1 + 2A + B → X + Y
Step 2
So, rate = k[A][B]PRK 1026 CHEMISTRI II UNIMAS (C) NOT
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Step 2 NO 3 + NO → 2NO 2
Given that, rate = k[NO] 2 [O 2 ] Which step is rate determining? Why?
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Ea reduced in presence of a catalyst∆H not changed
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•Catalyst provides alternative routewith a lower Ea
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•ata yst ta es part n react on
•Catalyst not used up
Note: catalyst does not changethe products nor its quantity
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– Catalyst provides an alternative reaction withE a = E a catalysed .
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2 8
I2 (aq) +SO42-(aq)
Reaction takes place in 2 stepsPRK 1026 CHEMISTRI II UNIMAS (C) NOT
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More reasonable for reaction tooccur with opposite charges
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.........
Y + XC → XYC ........(2) XYC → CZ .........(3)
CZ →
C + Z .........(4)
State the intermediates.PRK 1026 CHEMISTRI II UNIMAS (C) NOT
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Use surface adsorption theory to explain therole of Fe in increasing the rate of reaction
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H2 and N2 molecules adsorbed on surfaceDissociation happens to give H and N atoms
2 4• The hydrogenation of ethene to ethane iscatalysed by nickel:
)(CHCH)(H)(CHCH 33222 ggg −→+=
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• The radical uses the unpaired electron to
bond to the surface.PRK 1026 CHEMISTRI II UNIMAS (C) NOT
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• Desorption of ethane from the surface of
nickel occurs.PRK 1026 CHEMISTRI II UNIMAS (C) NOT
•Collision theory to explain reaction•A reaction needs activation ener
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•Reaction has a mechanism•Catalyst changes route of reaction
but not ∆H nor quantity of products•Catalyst is specific in action