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Chemical Kinetics - Unit 4

Chemistry 101

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Christopher John Kwong
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15 views17 pages

Chemical Kinetics - Unit 4

Chemistry 101

Uploaded by

Christopher John Kwong
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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CHEMICAL KINETICS

Factors Affecting Reaction Rates


1. Physical state of reactants
Homogeneous (involving either all gases or reactants)
Heterogeneous (reactants are in different phases)
o reactions that involve solids tend to proceed more rapidly if the surface area of
the solid is increased.

2. Reactant concentrations
Most chemical reactions proceed faster if the concentration of one or more reactants
is increased.
o as the concentration of reactants increases, the frequency of reactant
molecular collisions increases, leading to increased rates.

3. Reaction Temperature.
Reaction rates generally increase as temperature is
increased.
o Increasing temperature increases the kinetic energies
of molecules which results in greater frequency
of molecular collisions leading to increased reaction
rates.

4. The presence of a catalyst.


Catalysts are agents that increase reaction rates without being consumed in a
chemical reaction
The Rate of a Reaction
the change in the concentration of a reactant or a product with time (M/s)

∆[𝐴] ∆[𝐵]
rate = − 𝑜𝑟 𝑟𝑎𝑡𝑒 =
∆𝑡 ∆𝑡

∆[𝐵𝑟2 ] [𝐵𝑟2 ]𝑓𝑖𝑛𝑎𝑙 − [𝐵𝑟2 ]𝑖𝑛𝑖𝑡𝑖𝑎𝑙


average rate = − =−
∆𝑡 𝑡𝑓𝑖𝑛𝑎𝑙 − 𝑡𝑖𝑛𝑖𝑡𝑖𝑎𝑙

What is the average rate from t = 0.0 to t = 100.0?

∆[𝐵𝑟2 ] (0.00846 − 0.0120)M


average rate = − =− = 3.54 𝑥 10−5 𝑀/𝑠
∆𝑡 (100.0 − 0.0)s
Reaction Rates and Stoichiometry

1 ∆[𝐴] 1 ∆[𝐵] 1 ∆[𝐶] 1 ∆[𝐷]


rate = − =− = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

*solids (s) and liquids (l) are not included in the rate expression

∆[𝐶𝐻4 ] 1 ∆[𝑂2 ] ∆[𝐶𝑂2 ] 1 ∆[𝐻2 𝑂]


rate = − =− = =
∆𝑡 2 ∆𝑡 ∆𝑡 2 ∆𝑡
𝑨𝒏𝒔𝒘𝒆𝒓 ∶ 𝑨)0.013 𝑀/𝑠 𝐁) − 0.052 M/s
The Rate Law

𝑟𝑎𝑡𝑒 = 𝑘[𝐴]𝑥 [𝐵]𝑦

1. Rate laws are always determined experimentally. From the concentrations of


reactants and the initial reaction rates we can determine the reaction order and then the
rate constant of the reaction.

2. Reaction order is always defined in terms of reactant (not product) concentrations.

3. The order of a reactant is not related to the stoichiometric coefficient of the reactant in
the overall balanced equation.
𝑨𝒏𝒔𝒘𝒆𝒓 ∶ 𝑟𝑎𝑡𝑒 = 𝑘[𝑆2 𝑂82−][𝐼− ] 𝑘 = 0.081 𝑀 −1𝑠 −1

1st Order Kinetics

[A]t ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0


ln = −kt
[A]0
𝑨𝒏𝒔𝒘𝒆𝒓 ∶ 𝑡 = 66 𝑠𝑒𝑐
Reaction Half-life (1st Order Kinetics)
1 0.693
𝑡1/2 = ln 2 =
𝑘 𝑘
2nd Order Kinetics

1 1
= kt +
[A]t [A]0

1
𝑡1/2 =
𝑘[𝐴]0
Zero Order Reactions

The rate law is given by : 𝑟𝑎𝑡𝑒 = 𝑘[𝐴]0 = 𝑘

Thus the rate of a zero-order constant, independent of reaction concentration

[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0

[𝐴]0
𝑡1/2 =
2𝑘
Reaction Rate and Temperature

The temperature dependence of the reaction rate is contained in the rate


constant, k (which is actually a constant only when the temperature remains
constant).
An increase in temperature generally results in an increase in k, which results in
a faster rate.

Activation energy (Ea), which is the minimum amount of energy required to initiate a
chemical reaction. When molecules collide they form an activated complex (also called
the transition state), a temporary species formed by the reactant molecules as a result
of the collision before they form the product.

The frequency factor (A) as the number of times that the reactants approach the
activation barrier per unit time.

Arrhenius equation shows the relationship between the rate constant (k) and the
temperature in kelvin (T)

𝐸𝑎 𝐸𝑎 1
ln 𝑘 = ln 𝐴 − ln 𝑘 = − ( ) + ln 𝐴
𝑅𝑇 𝑅 𝑇

𝑦= 𝑚 𝑥 + 𝑏
By linear regression method (Excel/Calculator)

0
0.0012 0.00125 0.0013 0.00135 0.0014 0.00145
-0.5
-1
-1.5
-2
Series1
-2.5
Linear (Series1)
-3
-3.5
y = -21620x + 26.34
-4
R² = 0.998
-4.5
-5

𝐸𝑎
− = −2.16 × 104 𝐾
𝑅
𝐽
𝐸𝑎 = (2.16 × 104 𝐾 ) (8.314 ) = 1.80 × 105 𝐽/𝑚𝑜𝑙 = 180 𝑘𝐽/𝑚𝑜𝑙
𝐾 • 𝑚𝑜𝑙
𝑘1 𝐸𝑎 𝑇1 − 𝑇2
ln = ( )
𝑘2 𝑅 𝑇1 𝑇2

Catalysis

Catalyst is a substance that increases the rate of a reaction by lowering the


activation energy
In heterogeneous catalysis, the reactants and the catalysts are in different phases.
Haber synthesis of ammonia

Ostwald process for the production of nitric acid

Catalytic converters

In homogeneous catalysis, the reactants and the catalysts are dispersed in a single
phase, usually liquid.
Acid catalysis
Base catalysis
Enzymes: Biological Catalysts

catalysts that increase the rates of biochemical reactions

Sucrase catalyzes the conversion of sucrose into glucose and fructose by weakening
the bond that joins the two rings.

Chymotrypsin in Protein Digestion

The pancreas secretes an enzyme called chymotrypsin, into the small intestine to break
down the peptide bonds.
Nitrogenase converts N2 into NH3, a process that, in the absence of a catalyst, has
a very large activation energy. This process is a reduction reaction in which the
oxidation state of N is reduced from 0 in N2 to -3 in NH3.

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