MK Kinetika Kimia

2 sks 2 js
Ruang Lingkup

1. Konsep-konsep Dasar Kinetika Kimia:

Konsep Laju, Persamaan Laju, Tetapan Laju, orde, kemolekulan, Faktor-faktor yang mempengaruhi laju

2. Analisis data kinetik: Cara diferensial, cara integral

3. Cara-cara pengukuran laju: Cara kimia, cara fisik

4. Konsep dan Prediksi Mekanisme Reaksi:

Konsep MR, Pendekatan Steady State, Pendekatan Kesetimbangan, Mekanisme Katalisis, Mekanisme Reaksi
Rantai

5. Teori Reaksi Kimia:

Teori Tumbukan, Teori Keadaan Transisi
Referensi

 Wilkinson, Chemical Kinetics and Reaction Mechanisms

 Griffiths and Thomas, Calculation in Advanced Physical Chemistry

 Dari B Fauzia
Evaluasi
1. Tes Bagian I (Analisis data kinetik dan Cara-cara
pengukuran laju)  30%

2. Tes Bagian II (Mekanisme Reaksi)  30%

3. Tes Bagian III (Teori Reaksi)  10%

4. Tugas dan Keaktifan  30%

1-Fundamental Concepts of Chemical Kinetics
1.1Reaction Rates
Chemical kinetics is the branch of chemistry
which deals with the study of rate of reaction that addresses
the question:
"how fast do reactions go?" and mechanism by which the
reaction proceed.

If Chemistry is making new substances out of old substances

(i.e., chemical reactions), then there are two basic questions
that must be answered:
1. Does the reaction want to go? This is the subject of chemical
thermodynamics.
2. If the reaction wants to go, how fast will it go? This is the
subject of chemical kinetics.
 2 H2(g) + O2(g) → 2 H2O(l).

We can calculate ΔrGo for this reaction from tables of free energies of
formation (actually this one is just twice the free energy of formation of
liquid water). We find that ΔrGo for this reaction is very large and
negative, which means that the reaction wants to go very strongly. A
more scientific way to say this would be to say that the equilibrium
constant for this reaction is very very large.
However, we can mix hydrogen gas and oxygen gas together in a
bulb or other container, even in their correct stoichiometric proportions,
and they will stay there for centuries, perhaps even forever, without
reacting. (If we drop in a catalyst - say a tiny piece of platinum - or
introduce a spark, or even illuminate the mixture with sufficiently high
frequency U.V. light, or compress and heat the mixture, the mixture will
explode.) The problem is not that the reactants do not want to form the
products, they do, but they cannot find a "pathway" to get from reactants
to products.
 C(diamond) → C(graphite).

If you calculate ΔrGo for this reaction from data in the

tables of thermodynamic properties you will find once
again that it is negative (not very large, but still
negative). This result tells us that diamonds are
thermodynamically unstable. Yet diamonds are highly
regarded as gem stones ("diamonds are forever") and are
considered by some financial advisors as a good long-
term investment hedge against inflation. On the other
hand, if you were to vaporize a diamond in a furnace,
under an inert atmosphere, and then condense the
vapor, the carbon would come back as graphite and not
as diamond.
How can all these things be?
The answer is that thermodynamics is not the
whole story in chemistry. Not only do we have
to know whether a reaction is
thermodynamically favored, we also have to
know whether the reaction can or will proceed
at a finite rate. The study of the rate of
reactions is called chemical kinetics
1.2 Classification of Reaction Rates
C2H4(g) + O3(g)  C2H4O(g) + O2(g)

Konsentrasi O3
Waktu (s)
(mol/L)
0,0 3,20 x 10-5
10,0 2,42 x 10-5
20,0 1,95 x 10-5
30,0 1,63 x 10-5
40,0 1,40 x 10-5
50,0 1,23 x 10-5
60,0 1,10 x 10-5
Reaction Rates
Consider the reaction,
2 NO(g) + O2(g) → 2 NO2(g).

We might try to write the rate variously as,

or
as
aA + bB → cC + dD,               
Laju Sesaat
1.4 Rate Laws (Rate Expression )

where x, y, z, are small whole numbers or simple fractions and k is called the "rate
constant." The sum of x + y + z + . . . is called the "order" of the reaction.
Conclusions can be deduced from above table :
The rate law just be determined from experiment site, not from
stoikchiometry eq.
3- Dependence of Rates on Concentration
Order and Molecularity
3.1 Order of Reaction.
Is defined as the sum of all exponenents to which the
concentration in the rate equation are raised.
n1A + n2B + n3C = x dx
  kC An1 C Bn2 CCn3
dt
Order (n) = n1 + n2 + n3 , k = is specific rate constant
3.2 Molecularity

Is defined the number of molecules of reactants that are used to

form the activated complex A → A* → Product
Both order and molecularity can not always predicted from the
stoichiometric equation, but must be investigated kinetically by
experiments
Examples.

1- Decomposition of phosgene COCl 2 ═ CO + Cl2

dx first order and unimolecular

 kC COCl 2
dt
2- CH3COOC2H5 + NaOH CH
═ COONa + C H OH
3 2 5

dx
 kC ester .C NaOH second order and bimolecular
dt
 
3. 3KClO 
 KClO3 + 2 KCl

dx
 kC KClO
2
second order and trimolecular
dt
Analisis Data Kinetik

 Cara Differensial
 Cara Integral
Cara Differensial
Differential form of rate law of

A = product is

d [ A]
r  k[ A] n

dt ………..*)

n and k can be determined by plotting r vs [A]

 n=1

[A]
Exact just for n = 1
Change *) to be Linear
For n ≠ 1 ??? equation
1.2
12

1 10

0.8 8
n>1 n=1
0.6 6

0.4 4

0.2 2

0
0
0 2 4 6 8 10 12
0 1 2 3 4 5 6 7 8 9

12
12
10
10
8
8
6 0<n<1
6 n<0
4
4
2
2
0
0 2 4 6 8 10 12 0
0 2 4 6 8 10 12

Orde yang pasti hanya jika n=1

1.2
12
1
10
0.8 8
n>1 n=1
0.6 6

0.4 4

0.2 2

0 0
0 2 4 6 8 10 12
0 1 2 3 4 5 6 7 8 9

12
12
10
10
8
8
6 0<n<1
6 n<0
4
4
2
2
0
0 2 4 6 8 10 12 0
0 2 4 6 8 10 12

Orde yang pasti hanya jika n=1

r  k[ A] n
ln r  ln k  n ln[ A]
The orde (n) and k can be
determined from:
1. Plot of ln r vs ln [A]
2. LR from data of ln r and ln [A]
3. Elimination-substitution
Example:
The decomposition of nitrogen pentoxide dissolved in carbon
tetrachloride at 45°C takes place according to the
equation:
2 N2O5 = 4 NO2 + O2

Time / [N2O5] / mol dm-3

s
0 2.33
319 1.91
867 1.36
1198 1.11
1877 0.72
2315 0.55

Show the reaction is first order and determine

the first order rate constant

ln r  ln k  n ln[ A]
 ln r  ln k  n ln[ A]

ln [A]
t [A] r [A] rata2 ln r rata2
0 2.33 0.00132 2.12 -6.632692 0.751416
319 1.91 0.001 1.635 -6.904112 0.491643
867 1.36 0.00076 1.235 -7.188413 0.211071
1198 1.11 0.00057 0.915 -7.46223 -0.08883
1877 0.72 0.00039 0.635 -7.854176 -0.45413
2315 0.55
0.0014

0.0012

0.0010

0.0008
r

0.0006

0.0004

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

[A]
Linearitas kurva [A] vs r
membuktikan r = k [A]
 -6.6

-6.8

-7.0

-7.2
ln r -7.4

-7.6

-7.8

-8.0
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8
ln [A]

Intercept = -7.39121
Slope = 1.00355
k = 4.06 x 10-8 s-1
n=1
 HOW ABOUT?

r  k[ A] [ B]n m

ISOLATION METHOD
INITIAL RATE METHOD
3.4 Integrated Forms of Rate Laws
Soal-soal Latihan

1. A first order reaction 40% complete after 8 min. How long will it be before it is
90% complete?What is the value of the first order rate constant?

 A = A0 exp (-kt)        
 0.6 = exp (-8k)
 k = 0.063853 min-1
 0.1 = exp (-tk)
 t = 36.0606
 2. Equal concentration of triethylamine and methyl iodide were reacted
in nitrobenzena solution to form the quartenary ammonium salt. If the
concentration of of methyl iodide varies with time as follows, show that
the reaction is first order with respect to both reactants and calculate
the half life under this condition

[CH3I]/mol dm-3 0.01 0.0069 0.0044 0.0035 0.0031 0.0026

Time/s 0 650 2100 2600 3100 4000

Solution 1: Observation the k value

t [A} 1/[A] k

k = 1/t ( 1/[A] - 1/[A]0 ) 0 0.01 100

650 0.0069 144.9275 0.069119

K rata2 = 0.0688 2100 0.0044 227.2727 0.060606

2600 0.0035 285.7143 0.071429

3100 0.0031 322.5806 0.0718

4000 0.0026 384.6154 0.071154

 400

350

300

250
1/[A]

Slope = k = 0.07
200

150

100

0 1000 2000 3000 4000

t
 3. The reaction between isobutyl bromide and sodium ethoxide in ethanol at
95ºC is first order in both reactants. If the initial concentration of C4H9Br is
0.050 mol dm-3 and that of NaOEt varies with time as follows, determine the
second order rate constant for this reaction given that 1 mol of C4H9Br react
with 1 mol of NaOEt
t/min 0 10 20 30 40 50 60
[NaOEt]/mol dm-3 0.076 0.066 0.058 0.053 0.049 0.045 0.043

Solution 1: Observation the k value

ln[(A0 - x)/(B0-x)]=k(A0 - B0)t +ln(A0/B0)

k=ln[B0(A0 - x)/A0(B0-x)]/(A0-B0)t

A0 (A0-x) B0 (B0-x) t k
0.05 0.04 0.076 0.066 10 0.3156
0.032 0.058 20 0.3385
0.027 0.053 30 0.3279
0.023 0.049 40 0.3246
0.019 0.045 50 0.3411
0.017 0.043 60 0.3265

The values of k are relatively

constant with mean value = 0.3290
Solution 2: Observation of linierity of ln[B0(A0 - x)/A0(B0-x)] vs t Curve

t ln[B0(A0 - x)/A0(B0-x)]
0 0
10 -0.082064953 0.0
y = a + b*x

20 -0.175996773
Equation
Weight No Weighting
Residual Sum of 3.03985E-4
Squares
-0.1 Adj. R-Square 0.99825

30 -0.255744713
Value Standard Error
Intercept 7.20964E-4 0.00531
B
Slope -0.00862 1.47354E-4

-0.2
40 -0.337615747

B
-0.3
50 -0.443513176
60 -0.509276437
-0.4

-0.5

-0.6
0 10 20 30 40 50 60
A

slope= -0.00862
k=-0.00862/-0.026

=0.332
2-Experimental Methods of Measuring Reaction Rate:

 These determine directly changes in concentrations of reactants and products

with time, but they may have the disadvantages of sampling and speed of
analysis. When reaction is sufficiently fast to result in significant reaction
occurring during the time of sampling and analysis, the rate of reaction is
slowed down by reducing the temperature of the sample drastically, called
‘quenching’; reaction rate generally decreases dramatically with decreasing
temperature. Alternatively, reaction can be stopped by adding a reagent
which will react with the remaining reactant. The amount of this added
reagent can be found analytically, and this gives a measure of the amount of
reactant remaining at the time of addition.
  
2.1- Chemical Methods
These are mainly titration methods (volumetric or
gravimetric) and they can be highly accurate. They are
generally reserved for simple reactions in solution where
either only the reactant or the product concentrations are
being monitored. Here sampling errors and speed of
analysis are crucial. Chemical methods have been
largely superseded by modern black box techniques,
though, in certain types of solution reaction, they can still
be very useful.
2.2 Physical Methods
These use a physical property dependent on
concentration and must be calibrated, but are still
much more convenient than chemical methods.
Measurement can often be made in situ, and
analysis is often very rapid. Automatic recording
gives a continuous trace. It is vital to make
measurements faster than reaction is occurring.
The following problems illustrate typical physical
methods used in the past.
 Soal-soal Latihan

1
2. The hydrolysis of bromomethane is a first order reaction whose
progress may be followed chemically by titrating samples of
reaction mixture with silver nitrat. The volume required for 10 cm 3
samples at 330 K in typical experiment are:

t/s 0 528 18000 24720 ~

AgNO3 /cm3 0 5.9 17.3 22.1 49.5

Calculate the velocity constant for this reaction

 3. Inversion of sucrose
C12H22O11 + H2O = C6H12O6 + C6H12O6

Follow a first order law. The following

results were obtained in a study of the
reaction at 25°C

Time / s 0 1800 3600 5400 7800 10800

Sucrose 0 0.1350 0.2626 0.3737 0.5028 0.6312
inverted/M

The initial concentration of sucrose 1.352 M.

Calculate the first order rate constant!
 4. Observation from the alkaline hydrolysis of
ethyl 2-methylpropenoate in 84.7% ethanol at
40ºC: initial concentration both ester and
alkali was 0.0508 M. 10 cm3 of the reaction
mixture were remove from the reaction vessel
at the time stated, pipetted into 10 cm3 of
0.0668 M hydrochloric acid and the excess acid
titrated with 0.0511 M sodium hydroxide:

Time/s 600 1500 2400 3600 4800 6600

NaOH titre/cm3 4.03 5.11 5.98 6.86 7.57 8.36

Calculate the mean value of the second order

rate constant
 5. In a spectrophotometric study of the first order solvolysis reaction
of cinnamal chloride in ethanolic sodium hydroxide at 22.6°C, the
reaction was followed by noting the rate of disappearance of
the absorption maximum at 260 nm. The following
observations were made:

Time/hours 0 0.167 0.516 1.23 2.21

Absorbance(at 0.406 0.382 0.338 0.255 0.184
260 nm)

Calculate the rate constant of the reaction