(1) Laju reaksi (reaction rate):

Laju reaksi adalah perubahan konsentrasi reaktan atau produk terhadap waktu (M/s) (Change in

concentration of a reactant or product per unit time)

Chemical Kinetics (Kinetika Kimia) A → B

reaktan → produk

Chemical Kinetics (Kinetika Kimia) (1) Reaction rates (laju reaksi)

(2) The factors affecting reaction rates (faktor-faktor yang
Selama reaksi berlangsung, molekul reaktan bereaksi, sedangkan molekul produk terbentuk. Hasil yang
dapat diamati adalah menurunnya konsentrasi reaktan dan meningkatnya konsentrasi produk.
mempengaruhi laju reaksi)
Change in conc, A At - A0 A
= =
(3) Reaction mechanisms (mekanime reaksi) Change in time, t t t - t0 t
[A] [B]
laju = − OR laju =
t t

Dengan [A] dan [B] adalah perubahan konsentrasi (dalam molaritas) selama waktu t.

Untuk reaksi berikut: Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
rate  [Br2]
aA + bB → cC + dD rate = k [Br2]
rate
1 [A] 1 [B] = 1 [C] = 1 [D] k= = rate constant
Laju = −
a t
=−
c t c t [Br2]
b t
Contoh: = 3.50 x 10-3 s-1
Tuliskan rumus laju untuk reaksi-reaksi berikut ini ditinjau dari hilangnya reaktan dan slope of
terbentuknya produk: tangent
(1) 3 O2(g) → 2 O3(g) slope of
(2) 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2(g) tangent
slope of
tangent Rate constant (konstanta laju) yaitu proporsionalitas
Penyelesaian: (kesebandingan) antara laju reaksi dan konsentrasi reaktan.
(1) Koefisien stoikiometrinya adalah 3 dan 2, sehingga
2A B Dua mol A menghilang untuk 1 [O2] 1 [O3]
setiap mol B, artinya laju hilangnya laju = − =
[Br2] [Br2]final – [Br2]initial Hukum laju (rate law) adalah persamaan yang
3 t 2 t
A adalah 2 x lebih cepat dibanding (2) Dalam reaksi ini, average rate = - =- menghubungkan Laju reaksi dengan konstanta laju dan
1 [A]
OR laju =
[B]
kan laju terbentuknya B.
t tfinal - tinitial konsentrasi reaktan.
laju = − 1 [NH3] 1 [O2] = 1 [NO]= 1 [H2O]
2 t t laju = − =−
4 t 5 t 4 t 6 t instantaneous rate = rate for specific instance in time

Contoh:
The Rate Law F2 (g) + 2ClO2 (g) 2FClO2 (g)
(2) Factors that Affect Reaction Rate The rate law expresses the relationship of the rate of a reaction to the rate constant and
F2(g) + 2ClO2(g) → 2FClO2(g) the concentrations of the reactants raised to some powers.
1. Temperature (Hukum laju (rate law) adalah persamaan yang menghubungkan laju reaksi dengan
• Collision Theory: When two chemicals react, their molecules have konstanta laju dan konsentrasi reaktan).
rate = k [F2]x[ClO2]y
Data laju untuk reaksi antara F2 dan ClO2 to collide with each other with sufficient energy for the reaction
[F2] (M) [ClO2] (M) Laju awal (M/s) to take place.
• Kinetic Theory: Increasing temperature means the molecules aA + bB cC + dD
1. 0,10 0,010 1,2 x 10-3
move faster.
2. 0,10 0,040 4,8 x 10-3 Double [F2] with [ClO2] constant
2. Concentrations of reactants Rate = k [A]x[B]y
3. 0,20 0,010 2,4 x 10-3 • More reactants mean more collisions if enough energy is present
Rate doubles
3. Catalysts
• Speed up reactions by lowering activation energy x=1
Jika nilai k, x dan y serta konsentrasi A dan B diketahui
k= laju = 1,2 x 10-3 M/s
4. Surface area of a solid reactant maka hukum laju dapat digunakan untuk menghitung
reaction is xth order in A
rate = k [F2][ClO2]
= 1,2 /M  s Quadruple [ClO2] with [F2] constant
(0,10 M) (0,010 M) • Bread and Butter theory: more area for reactants to be in contact laju reaksi.
[F2] [ClO2] reaction is yth order in B
5. Pressure of gaseous reactants or products k, x dan y harus ditentukan melalui percobaan.
Rate quadruples
• Increased number of collisions jumlah dari pangkat-pangkat setiap konsentrasi reaktan
yang ada dalam hukum laju disebut orde reaksi (reaction reaction is (x +y)th order overall
order).
y=1

Rate Laws Determine the rate law and calculate the rate constant
Run # Initial [A] Initial [B] Initial Rate (v0) for the following reaction from the following data:
([A]0) ([B]0) Initial Rate
[NO(g)] (mol dm-3) [Cl2(g)] (mol dm-3) • Rate laws are always determined experimentally. S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)
(mol dm-3 s-1)
1 1.00 M 1.00 M 1.25 x 10-2 M/s
0.250 0.250 1.43 x 10-6 • Reaction order is always defined in terms of reactant Initial Rate
2 1.00 M 2.00 M 2.5 x 10-2 M/s Experiment [S2O82-] [I-]
0.250 0.500 2.86 x 10-6 (not product) concentrations. (M/s) rate = k [S2O82-]x[I-]y
3 2.00 M 2.00 M 2.5 x 10-2 M/s 0.500 0.500 1.14 x 10-5 1 0.08 0.034 2.2 x 10-4 y=1
• The order of a reactant is not related to the x=1
2 0.08 0.017 1.1 x 10-4
stoichiometric coefficient of the reactant in the
balanced chemical equation. 3 0.16 0.017 2.2 x 10-4 rate = k [S2O82-][I-]
What is the order with respect to A? 0 What is the order with respect to Cl2? 1

What is the order with respect to B? 1 What is the order with respect to NO? 2 Double [I-], rate doubles (experiment 1 and 2)
F2 (g) + 2ClO2 (g) 2FClO2 (g)
Double [S2O82-], rate doubles (experiment 2 and 3)
What is the overall order of the 1 What is the overall order of the
reaction? reaction? 3 rate = k [F2][ClO2] 1 2.2 x 10-4 M/s
rate
k= = = 0.08/M•s
[S2O82-][I-] (0.08 M)(0.034 M)
 First-Order Reactions
Decomposition of N2O5 The reaction 2A B is first order in A with a rate
[A] constant of 2.8 x 10-2 s-1 at 80C. How long will it take for
A → produk rate = - rate = k [A] 2N2O5 → 4NO2 + O2
t A to decrease from 0.88 M to 0.14 M ?
[A] 1 𝑀
k=- k= = det-1
[A] t 𝑀 𝑑𝑒𝑡 t (det) [N2O5] ln[N2O5]
0 0.91 -0.094 [A] = [A]0e-kt
dA dA [A]0 = 0.88 M
- = k [A] - = k dt 300 0.75 -0.29
𝑑𝑡 [A] 600 0.64 -0.45 ln[A] - ln[A]0 = - kt
[A] = 0.14 M
1200 0.44 -0.82
[A] is the concentration of A at any time t
ln[A]0 - ln[A] = kt
ln[A] - ln[A]0 = - kt 3000 0.16 -1.83
[A]0 0.88 M
[A]0 is the concentration of A at time t=0 ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
[A]
k = 5,7 x 10-4 detik-1 k k 2.8 x 10-2 s-1
ln = - kt [A] = [A]0 e-kt
A0

13.3 13.3

First-Order Reactions Second-Order Reactions

First-order reaction
The half-life, t½, is the time required for the concentration of a reactant to decrease to half of
A product [A] [A] is the concentration of A at any time t
its initial concentration (waktu yang diperlukan agar konsentrasi reaktan turun menjadi setengah rate = - rate = k [A]2
t [A]0 is the concentration of A at time t=0
dari konsentrasi awalnya)
t½ = t when [A] = [A]0/2 k = rate/[A]2 Half life for second order
half-life [A] = [A]0/n 1 1
- = kt t½ = t when [A] = [A]0/2
[A]0 1 2 M/dt 1 [A] [A]0
= = .dt 1
ln M2 M t½ =
[A]0/2 ln 2 0.693 2 4 k[A]0
t½ = = =
k k k
3 8
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?
4 16
t½ = ln 2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10-4 s-1
How do you know decomposition is first order?
units of k (s-1)

Zero-Order Reactions A+B C+D

Temperature Dependence of the Rate Constant
[A] Summary of the Kinetics of Zero-Order, First-Order Exothermic Reaction Endothermic Reaction
rate = - rate = k [A]0 = k and Second-Order Reactions
t
Jika produk lebih stabil
[A] is the concentration of A at any time t dibandingkan reaktan, maka
k = A • exp -Ea/RT
[A] - [A]0 = kt [A]0 is the concentration of A at time t=0 Concentration-Time reaksi akan diiringi dengan
pelepasan kalor (eksotermik).
(Arrhenius equation)
Half life for zero order Order Rate Law Equation Half-Life
Sebaliknya, jika produk kurang
Ea is the activation energy (J/mol)
t½ = t when [A] = [A]0/2 [A]0 stabil dibandingkan reaktan, R is the gas constant (8.314 J/K•mol)
0 rate = k [A] - [A]0 = - kt t½ = maka kalor akan diserap dari
2k
[A]0 lingkungan oleh campuran yang T is the absolute temperature
t½ = Ln 2 bereaksi dan reaksinya bersifat
2k t½ =
1 rate = k [A] ln[A] - ln[A]0 = - kt endotermik. A is the frequency factor
k
1 1 1 -Ea 1
2 rate = k [A]2 - = kt t½ = The activation energy (Ea) is the minimum amount of energy required to initiate a chemical ln k = - + lnA
[A] [A]0 k[A]0 R T
reaction.
𝐸𝑎
Spesi yang terbentuk sementara oleh molekul reaktan sebagai akibat tumbukkan sebelum ln k = ln A -
𝑅𝑇
membentuk produk dinamakan kompleks teraktifasi (activated complex).

(3) Reaction Mechanisms Rate Laws and Elementary Steps

Reaction Intermediates Rate Laws and Rate Determining Steps
The overall progress of a chemical reaction can be represented at the
Unimolecular reaction A products rate = k [A]
molecular level by a series of simple elementary steps or elementary Writing plausible reaction mechanisms:
reactions. Intermediates are species that appear in a reaction mechanism
but not in the overall balanced equation. • The sum of the elementary steps must give the overall Bimolecular reaction A+B products rate = k [A][B]
The sequence of elementary steps that leads to product formation is the balanced equation for the reaction.
reaction mechanism (tahap elementer yang mengarah pada pembentukkan An intermediate is always formed in an early elementary step and Bimolecular reaction A+A products rate = k [A]2
produk disebut mekanisme reaksi. consumed in a later elementary step. • The rate-determining step should predict the same rate
law that is determined experimentally.
2NO (g) + O2 (g) 2NO2 (g)
Banyaknya molekul yang bereaksi dalam tahap elementer menentukan molekularitas reaksi
N2O2 is detected during the reaction! Elementary step: NO + NO N2O2 (molecularity of reaction). Setiap tahap elementer yang baru dibahas disebut reaksi bimolecular
The rate-determining step is the slowest step
+ Elementary step: N2O2 + O2 2NO2 in the sequence of steps leading to product (bimolecular reaction), yaitu tahap elementer yang melibatkan dua molekul. Reaksi
Elementary step: NO + NO N2O2
Overall reaction: 2NO + O2 2NO2 formation. unimolekular (unimolecular reaction) ialah reaksi yang tahap elementernya hanya melibatkan
+ Elementary step: N2O2 + O2 2NO2 satu molekul yang bereaksi.
Overall reaction: 2NO + O2 2NO2
 A catalyst is a substance that increases the rate of a ENERGY DIAGRAMS
chemical reaction without itself being consumed. The experimental rate law for the reaction between NO2
and CO to produce NO and CO2 is rate = k[NO2]2. The
Ea k reaction is believed to occur via two steps:
Step 1: NO2 + NO2 NO + NO3
Step 2: NO3 + CO NO2 + CO2
What is the equation for the overall reaction?
NO2+ CO NO + CO2
What is the intermediate? Catalyst? Write the rate law for this reaction. Rate = k [HBr] [O2]
Exothermic Endothermic
NO3 NO2
List all intermediates in this reaction. HOOBr, HOBr
uncatalyzed catalyzed (a) Activation energy (Ea) for the forward 50 kJ/mol 300 kJ/mol
reaction What can you say about the relative rates of steps 1 and 2?
150 kJ/mol 100 kJ/mol List all catalysts in this reaction. None
(b) Activation energy (Ea) for the reverse
ratecatalyzed > rateuncatalyzed reaction
-100 kJ/mol +200 kJ/mol rate = k[NO2]2 is the rate law for step 1, so
step 1 must be slower than step 2
(c) Delta H
13.6

Ostwald Process Catalytic Converters Enzyme Catalysis Type of reactions

Pt catalyst Vigorous reactions
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)
2K(s) + 2H2O(l) → 2KOH(aq) + H2(g)
2NO (g) + O2 (g) 2NO2 (g)
Very rapid reactions
2NO2 (g) + H2O (l) HNO2 (aq) + HNO3 (aq)
Formation of insoluble salts

3HNO2 (aq) → HNO3 (aq) + H2O(l) + 2NO(g) Ag+(aq) + Cl−(aq)→ AgCl(s)

NO dapat didaur
ulang untuk meng- Digunakan untuk Very rapid reactions
hasilkan NO2 . catalytic Potassium reacts with Formation of insoluble bases
produksi pupuk, CO + Unburned Hydrocarbons + O2 CO2 + H2O water vigorously
Obat-obatan, zat converter
Warna dan bahan Fe3+(aq) + 3OH−(aq)→ Fe(OH)3(s)
peledak catalytic
2NO + 2NO2 converter 2N2 + 3O2

Hot Pt wire
Pt-Rh catalysts used
in Ostwald process
over NH3 solution
13.6 13.6

Slow reactions
Extremely slow reactions
Fermentation of glucose
Very rapid reactions CaCO3(s) + 2H+(aq) → Ca2+(aq) + CO2(g) + H2O(l)
C6H12O6(aq) → 2C2H5OH(aq) + 2CO2(g)
Acid-alkali neutralization reactions Before corrosion After corrosion
−
H+(aq) + OH (aq)→ H2O(l)

Rapid or moderate reactions

Displacement reactions of metals:
Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s) Very slow reactions
Rusting of iron
Amount is usually expressed in
4Fe(s) + 3O2(g) + 2nH2O(l) → 2Fe2O3 · nH2O(s)
Concentration mol dm−3
Average rate of reaction
Total change in amount of a product or a reactant Mass g
=
Total time taken for the change to occur Volume cm3 or dm3
Displacement reactions of halogens:
Pressure atm
Cl2(aq) + 2Br−(aq) → 2Cl−(aq) + Br2(aq)