Pertemuan 2

Kinetika Kimia
Introduction
Termodinamik – meninjau keberlangsungan reaksi?
Kinetika – kecepatan berlangsungnya reaksi?

Reaksi Kimia

Kendali Termodnamika Kendali Kinetika

∆G < O → Spontan Laju Reaksi

∆G = O → Kesetimbangan Ea
∆G > O → Tidak Spontan Pemakaian katalis menurunkan
∆G = ∆H - T∆S
Ea.
∆F = ∆U - T∆S
∆H < O → Eksoterm mempercepat
∆H > O → Endoterm Katalis
memperlambat
Kinetics: Laju and Mekanisme Reaksi

Kinetika kimia menjelaskan tentang:

… bagaimana reaksi berlangsung
…bagaimana molekul berreaksi (MECHANISM)

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 Factors Affecting the rate:

1. concentration:
2. temperature:
generally a 10oC increase will double the rate

3. nature of the reactant: i.e. surface area

4. catalyst: (two types: homogenous and heterogeneous)

5. mechanism: (orientation, shape, & order)

COLLISION THEORY = CAPPING A MARKER
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 Rate of RXN =

The increase in concentration of a product per unit time.

or
The decrease in concentration of a reactant per unit time.
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 Conc. is usually measured in M (Molarity= mol/L)
for solutions.
Rate = M = mol
time L•s or mol•L-1•s-1 or M•s -1

Square brackets [ ] are often

used to express molarity
(i.e. [HCl] means Molarity of
HCl)
Since many reactions involve gases, P is often used for
concentration.
n n
from PV  nRT, P  RT and has units of ...
V V
moles/L 6
 Consider the reaction (net ionic eq.):

3ClO- (aq)  2Cl-(aq) + ClO3-(aq)

Rate could be defined in at least 3 ways: (3 coefficients and ions)

[ClO 3 ]
1. appearance of ClO3- rate 
time
[Cl - ]
2. appearance of Cl- rate 
time Disappearance

 [ClO- ]
3. disappearance of ClO- rate 
time

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 Consider the reaction (net ionic):

3ClO- (aq)  2Cl-(aq) + ClO3-(aq)


-
1. appearance of ClO3 rate  [ClO 3 ]
time
[Cl - ]
2. appearance of Cl- rate 
time
Disappearance
3. disappearance of ClO-  [ClO- ]
rate 
time

Question: Are these three rates equal?

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Consider the reaction (net ionic):

3ClO- (aq)  2Cl-(aq) + ClO3-(aq)

Let’s make these three rates equal.

[ClO-3 ] [Cl - ]  [ClO- ]

rate   
time 2time 3time

Note the use of

coefficients and the -
sign
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 General Form:
aA + bB  cC + dD

rate =  [C] = [D] = - [A] = - [B]

ctime dtime atime btime

“PRODUCTS” “REACTANTS”

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  conc
rate 
 time Average rate = slope (over time period)

PRODUCT

0.30 - 0.74
slope  -
 0.0146 6 2. 0 - 0 7. 0
40 - 10 7 4 1 0. 0   epo l s
01 - 04

negative sign

REACTANT

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  conc (changing)
rate 
 time instantaneous rate = tangent slope
WHY?

Collision Theory!

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 y
Slope   tangent at point of interest
x 13
 Molecularity
The molecularity of chemical reaction is defined as
the number of molecules of reactant participating in
a simple reaction consisting of a single elementary
step. Most elementary reactions have a molecularity
of one or two, although some reactions involving
three molecules colliding simultaneously have a
molecularity of three, and in very rare cases in
solution, the molecularity is four.
1. Unimolecular reactions
A unimolecular reaction involves a single reactant
molecule , and is either an isomerisation
A B or a decomposition A B + C
Some examples of unimolecular reaction are:
CH2
CH2 CH2 CH3CH=CH2

CH3NC CH3CN
2. Bimolecular reactions
A bimolecular reaction is one in which two like or unlike
reactant molecules combine to give a single product or a
number of product molecules. They are either association
reactions (the reverse of a decomposition reaction)
A + B AB 2A A2
Or exchange reactions
A + B C + D 2A C+D
Some examples of bimolecular reactions are
C2H4 + HI C2H5I
O3 + NO O2 + NO2
CH3COOH + C2H5OH CH3COOC2H5 + H2O
3. Termolecular Reactions
Termolecular reactions are relatively rare since they
involve the collision of three molecules
simultanously to give a product or products.
A + B + C Products
Some examples of termolecular reactions are
2NO + O2 2 NO2
2NO + Cl2 2NOCl
 Elementary Rate Laws
1. Rate equation
Consider a chemical reaction in which a reactant A
decomposes to give two products, B and C
A B + C
During the course of the reaction, the concentration
of A decreases while the concentration of B and C
increases. A typical concentration-time graph for A is
shown in figure 1.
Figure 1. Typical concentration-time curve
Concentration of A

Rate of reaction is a slope this curve

Time
Any rate is given by the change in a measureable
quantity with time, and the rate of chemical reaction
is expressed in term of change in concentration of
reactant in a given time.
The rate could equally be given by the increase in the
concentration of B or C with time.
𝑑𝐴 𝑑𝐵 𝑑𝐶
𝑅𝑎𝑡𝑒 = − = =
𝑑𝑡 𝑑𝑡 𝑑𝑡
The rate of a chemical reaction is therefore expressed
as a rate of formation of a product.
The rate of a reaction depends on the concentration of
the reactants, so that as the concentration of A in the
above reaction decreases, the rate of reaction also
decreases. Therefore,
Rate α [A]n
Where n is a constant know as the order of the reaction.
The relationship between the rate and concentration is
called the rate equation and takes the form
𝑑[𝐴]
− = 𝑘𝑟 [𝐴]𝑛
𝑑𝑡
Where kr is a constant for any reaction at one
temperature and is called the rate constant.