Kinetika Kimia

Lecture Presentation
Chapter 14
Kinetika Kimia
John D. Bookstaver
St. Charles Community College
Cottleville, MO
© 2012 Pearson Education, Inc.
Kinetika
• DaIam kinetika yang dipelajari adl
rate/laju dimana proses kimia terjadi.
• Disamping informasi tentang speed
dimana reaksi terjadi, kinetika juga
menjelaskan mekanisme reaksi
(secara tepat bagaimana reaksi terjadi).
Chemica
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© 2012 Pearson Education, Inc. Kinetics
Faktor-faktor yang Mempengaruhi
Laju Reaksi
• Keadaan Fisik dari reaktan.

– Agar bereaksi, molekul harus terjadi
kontak antara molekul tersebut.
– Semakin homogen campuran reaktan
ini, semakin lebih cepat molekul-
molekul dapat bereaksi.
Chemica
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Faktor-faktor yang
Mempengaruhi Laju Reaksi
• Konsentrasi reaktan.
– Jika konsentrasi
dari reaktan
bertambah besar,
kemungkinan besar
molekul-molekul
reaktan akan
bertumbukan.
Chemica
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Laju Reaksi
• Temperatur
– Pada suhu lebih tinggi, molekul
reaktan mempunyai energi kinetik
lebih besar, bergerak lebih cepat,
dan tumbukan lebih sering dan
dengan energi lebih besar.
Chemica
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Laju Reaksi
• Adanya katalis.
– Katalis mempercepat reaksi dengan
perubahan mekanisme reaksi.
– Katalis tidak dikonsumsi selama
jalannya reaksi ini.
Chemica
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Laju Reaksi
Laju reaksi dapat ditentukan dengan

monitoring perubahan konsentrasi dari baik
reaktan atau produk sebagai fungsi waktu.
Chemica
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Laju Reaksi
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
Dalam reaksi ini,

konsentrasi dari
butil klorida,
C4H9Cl, diukur
pada berbagai
waktu.
Chemica
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Laju Reaksi
Laju rata-rata dari

reaksi ini atas tiap-tiap
interval adl perubahan
konsentrasi dibagi
dengan perubahan
waktu :
Δ[C4H9Cl]
Average rate =
Δt
Chemica
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Laju Reaksi
• Catatan bhw laju
rata-rata mengecil
seiring berjalan
nya reaksi.
• Ini dikarenakan
sebagai reaksi
berlangsung,
adanya tumbukan
antar molekul
reaktan yang Chemica
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© 2012 Pearson Education, Inc. mengecil. Kinetics
Laju Reaksi
• Alur dari [C4H9Cl] vs

waktu untuk reaksi ini
menghasilkan kurva
seperti ini.
• Slop dari garis tangent
ke kurva ini pada titik
dimana saja adalah
instantaneous rate
pada waktu itu.
Chemica
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Laju Reaksi
• Semua reaksi berjalan

melambat dalam waktu.
• Karenanya, indikator
terbaik dari laju reaksi
adl the instantaneous
rate dekat dengan
beginning dari reaksi.
Chemica
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Laju Reaksi
• Dalam reaksi ini,
rasio dari C4H9Cl thd
C4H9OH adl. 1:1.
• Maka, laju dari
disappearance of
C4H9Cl sama dengan
laju of appearance of
C4H9OH.
−Δ[C4H9Cl] Δ[C4H9OH]
Rate = = Chemica
Δt Δt l
Kinetics
© 2012 Pearson Education, Inc.
Laju Reaksi dan Stoikiometri
• Berapa jika rasio bukan 1:1?

2 HI(g) ⎯⎯→ H2(g) + I2(g)
•Dalam
kasus, 1 Δ[HI Δ[I2]
Rate = =
2 ] Δt
−
Δt
Chemica
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Laju Reaksi dan Stoikiometri
• Selanjutnya untuk mengeneralisasi,

untuk reaksi ini
aA + bB cC + dD
1 Δ[A 1 Δ[B 1 Δ[C 1 Δ[D

Laju = a ] = b ] = c ] = d
]
− −
Δt Δt Δt Δt
Chemica
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Konsentrasi dan Laju
Seseorang dapat memperoleh tentang

laju suatu reaksi dengan melihat
bagaimana perubahan laju dengan
perubahan konsentrasi.
Chemica
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NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)
Jika membandingkan Eksperimen 1 dan 2,

terlihat bhw bila [NH4+] diduakalikan, laju awal
dua kali. Chemica
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NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)
Serupa, bila membandingkan Eksperimen 5

dan 6, terlihat bhw bila [NO2−] diduakalikan,
lau awal dua kali. Chemica
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• Berarti
Rate ∝ [NH4+]
−
Rate ∝ [NO2 ]
karenanya,
−
Rate ∝ [NH ] [NO2 ]
4
+
Jika ditulis dalam persamaan, menjadi

−
Rate = k [NH ] [NO2 ]
4
+
• Persamaan ini disebut the rate law, dan k adl. Chemica

l
the rate constant.
Hukum Laju
• Hukum laju menunjukkan hubungan antara laju
reaksi dan konsentrasi dari reaktan.
• Eksponen menceritakan order reaksi terhadap
masing-masing reaktan.
• Since the rate law is
Rate = k[NH4+] [NO2−]
the reaction is
First-order in [NH4+]
and
Chemica
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First-order in© 2012
[NO 2 ]Education, Inc.
Pearson Kinetics
Rate Laws
Rate = k[NH4+] [NO2−]
• The overall reaction order can be found

by adding the exponents on the
reactants in the rate law.
• This reaction is second-order overall.
Chemica
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Integrated Rate Laws
Using calculus to integrate the rate law
for a first-order process gives us
[A]t
ln =
[A]0 −kt
where
[A]0 is the initial concentration of A, and
[A]t is the concentration of A at some time, t,

Chemica
during the course of the reaction. l
Integrated Rate Laws
Manipulating this equation produces

[A]t
ln =
[A]0
−kt
ln [A]t − ln [A]0 = −kt
ln [A]t = −kt + ln [A]0
which is in the form
y = mx + b Chemica
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First-Order Processes
ln [A]t = −kt + ln [A]0
Therefore, if a reaction is first-order, a

plot of ln [A] vs. t will yield a straight
line, and the slope of the line will be −k.
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Consider the process in

which methyl isonitrile is
converted to acetonitrile.
CH3NC CH3CN
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CH3NC CH3CN
This data were

collected for this
reaction at 198.9 °C.
Chemica
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• When ln P is plotted as a function of time, a

straight line results.
• Therefore,
– The process is first-order.
Chemica
– k is the negative of the slope: 5.1 × 10−5 s−1. l
Second-Order Processes
Similarly, integrating the rate law for a

process that is second-order in reactant
A, we get
1 1
= kt +
[A]t [A]0
also in the form

y = mx + b Chemica
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1 1
= kt +
[A]t [A]0
So if a process is second-order in A, a
1
plot of [A] vs. t yields a straight line, and
the slope of that line is k.
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The decomposition of NO2 at 300 °C is described by
the equation 1
NO2(g) NO(g) + 2 O2(g)
and yields data comparable to this table:
Time (s) [NO2], M

0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
Chemica
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• Plotting ln [NO2] vs. t yields
the graph at the right.
• The plot is not a straight
line, so the process is not
first-order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 −4.610
50.0 0.00787 −4.845
100.0 0.00649 −5.038
200.0 0.00481 −5.337
300.0 0.00380 −5.573 Chemica

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1
• Graphing ln [NO2]
vs. t, however,
gives this plot
Fig. 14.9(b).
• Because this is a
Time (s) [NO2], M 1/[NO2]
straight line, the
0.0 0.01000 100
process is second-
50.0 0.00787 127
order in [A].
100.0 0.00649 154
200.0 0.00481 208
300.0 0.00380 263 Chemica

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Half-Life
• Half-life is defined
as the time required
for one-half of a
reactant to react.
• Because [A] at t1/2 is
one-half of the
original [A],
[A]t = 0.5 [A]0.
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Half-Life
For a first-order process, this becomes
0.5 [A]0
ln = −kt1/2
[A]0
ln 0.5 = −kt1/2
−0.693 = −kt1/2
0.693
= t1/2
k
Note: For a first-order process, then, the half-life does not
Chemica
depend on [A]0. l
Half-Life
For a second-order process,
1 1
= kt1/2 +
0.5 [A]0 [A]0
2 1
= kt1/2 +
[A]0 [A]0
2− 1
= = kt1/2
1 [A]0
[A]0 1
= t1/2
k[A]0 Chemica
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Temperature and Rate
• Generally, as temperature
increases, so does the
reaction rate.
• This is because k is
temperature-dependent.
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The Collision Model
• In a chemical reaction, bonds are

broken and new bonds are formed.
• Molecules can only react if they collide
with each other.
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The Collision Model
Furthermore, molecules must collide with the
correct orientation and with enough energy
to cause bond breakage and formation.
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Activation Energy
• In other words, there is a minimum amount of energy
required for reaction: the activation energy, Ea.
• Just as a ball cannot get over a hill if it does not roll
up the hill with enough energy, a reaction cannot
occur unless the molecules possess sufficient energy
to get over the activation-energy barrier.
Chemica
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Reaction Coordinate Diagrams
It is helpful to
visualize energy
changes
throughout a
process on a
reaction
coordinate
diagram like this
one for the
rearrangement of
methyl isonitrile. Chemica
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Reaction Coordinate Diagrams
• The diagram shows the
energy of the reactants
and products (and,
therefore, ΔE).
• The high point on the
diagram is the
transition state.
• The species present at the transition state is
called the activated complex.
• The energy gap between the reactants and the
activated complex is the activation-energy
Chemica
barrier. l
Maxwell–Boltzmann Distributions
• Temperature is
defined as a
measure of the
average kinetic
energy of the
molecules in a
sample.
• At any temperature there is a wide
distribution of kinetic energies.
Chemica
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• As the temperature
increases, the
curve flattens and
broadens.
• Thus, at higher
temperatures, a
larger population of
molecules has
higher energy.
Chemica
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• If the dotted line represents the activation

energy, then as the temperature increases,
so does the fraction of molecules that can
overcome the activation-energy barrier.
• As a result, the
reaction rate
increases.
Chemica
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This fraction of molecules can be found through the expression
−Ea/RT
f=e
where R is the gas constant and T is the Kelvin temperature.
Chemica
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Arrhenius Equation
Svante Arrhenius developed a mathematical
relationship between k and Ea:
k = Ae −Ea/RT
where A is the frequency factor, a number

that represents the likelihood that collisions
would occur with the proper orientation for
reaction.
Chemica
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Arrhenius Equation
Taking the natural
logarithm of both
sides, the equation
becomes
Ea 1
ln k = − ( T ) + ln A
R
y = mx + b
Therefore, if k is determined experimentally at
several temperatures, Ea can be calculated
1
from the slope of a plot of ln k vs. T . Chemica
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Reaction Mechanisms
The sequence of events that describes

the actual process by which reactants
become products is called the reaction
mechanism.
Chemica
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Reaction Mechanisms
• Reactions may occur all at once or

through several discrete steps.
• Each of these processes is known as
an elementary reaction or elementary
process.
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Reaction Mechanisms
The molecularity of a process tells how

many molecules are involved in the process.
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Multistep Mechanisms
• In a multistep process, one of the steps will
be slower than all others.
• The overall reaction cannot occur faster than
this slowest, rate-determining step.
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Slow Initial Step
NO2(g) + CO(g) ⎯⎯→ NO(g) + CO2(g)
• The rate law for this reaction is found

experimentally to be
Rate = k[NO2]2
• CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its
concentration.
• This suggests that the reaction occurs in two
steps.
Chemica
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Slow Initial Step
• A proposed mechanism for this reaction is
Step 1: NO2 + NO2 ⎯⎯→ NO3 + NO (slow)
Step 2: NO3 + CO ⎯⎯→ NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second step.
• As CO is not involved in the slow, rate-determining
step, it does not appear in the rate law.
Chemica
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Fast Initial Step
2 NO(g) + Br2(g) ⎯⎯→ 2 NOBr(g)
• The rate law for this reaction is found

to be
Rate = k[NO]2 [Br2]
• Because termolecular processes are
rare, this rate law suggests a two-step
mechanism.
Chemica
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Fast Initial Step
• A proposed mechanism is
Step 1: NO + Br2 NOBr2 (fast)
Step 2: NOBr2 + NO ⎯⎯→ 2 NOBr (slow)
Step 1 includes the forward and reverse

reactions.
Chemica
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Fast Initial Step
• The rate of the overall reaction depends

upon the rate of the slow step.
• The rate law for that step would be
Rate = k2[NOBr2] [NO]
• But how can we find [NOBr2]?

Chemica
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Fast Initial Step
• NOBr2 can react two ways:

– With NO to form NOBr.
– By decomposition to reform NO and Br2.
• The reactants and products of the first
step are in equilibrium with each other.
• Therefore,
Ratef = Rater
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Fast Initial Step
• Because Ratef = Rater,
k1[NO] [Br2] = k−1[NOBr2]
• Solving for [NOBr2], gives us

k1
[NO] [Br2] = [NOBr2]
k−1
Chemica
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Fast Initial Step
Substituting this expression for [NOBr2]

in the rate law for the rate-determining
step, gives
k2k1
Rate = [NO] [Br2] [NO]
k−1
= k[NO]2 [Br2]
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Catalysts
• Catalysts increase the rate of a reaction by
decreasing the activation energy of the
reaction.
• Catalysts change the mechanism by which
the process occurs.
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Catalysts
One way a
catalyst can
speed up a
reaction is by
holding the
reactants together
and helping bonds
to break.
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Enzymes
• Enzymes are
catalysts in
biological systems.
• The substrate fits
into the active site of
the enzyme much
like a key fits into a
lock.
Chemica
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Lecture Presentation

• Keadaan Fisik dari reaktan.

Laju reaksi dapat ditentukan dengan

Dalam reaksi ini,

Laju rata-rata dari

• Alur dari [C4H9Cl] vs

• Semua reaksi berjalan

• Berapa jika rasio bukan 1:1?

• Selanjutnya untuk mengeneralisasi,

1 Δ[A 1 Δ[B 1 Δ[C 1 Δ[D

Seseorang dapat memperoleh tentang

NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Jika membandingkan Eksperimen 1 dan 2,

NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Serupa, bila membandingkan Eksperimen 5

Jika ditulis dalam persamaan, menjadi

• Persamaan ini disebut the rate law, dan k adl. Chemica

Rate = k[NH4+] [NO2−]

• The overall reaction order can be found

[A]t is the concentration of A at some time, t,

Manipulating this equation produces

ln [A]t = −kt + ln [A]0

Therefore, if a reaction is first-order, a

Consider the process in

This data were

• When ln P is plotted as a function of time, a

Similarly, integrating the rate law for a

also in the form

Time (s) [NO2], M

50.0 0.00787 −4.845

100.0 0.00649 −5.038

200.0 0.00481 −5.337

300.0 0.00380 −5.573 Chemica

200.0 0.00481 208

300.0 0.00380 263 Chemica

• In a chemical reaction, bonds are

• If the dotted line represents the activation

where A is the frequency factor, a number

The sequence of events that describes

• Reactions may occur all at once or

The molecularity of a process tells how

• The rate law for this reaction is found

• The rate law for this reaction is found

Step 1 includes the forward and reverse

• The rate of the overall reaction depends

Rate = k2[NOBr2] [NO]

• But how can we find [NOBr2]?

• NOBr2 can react two ways:

• Because Ratef = Rater,

k1[NO] [Br2] = k−1[NOBr2]

• Solving for [NOBr2], gives us

Substituting this expression for [NOBr2]

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