Reaction Kinetics
Reaction Kinetics
Reaction kinetics is the branch of chemistry that deals with the study of the rates at
which chemical reactions occur and the factors that affect these rates. It involves
understanding the speed of a reaction, the mechanism through which reactants are
transformed into products, and how different conditions such as temperature,
concentration, and catalysts affect the reaction rate.
2. Rate of Reaction
The rate of reaction refers to the change in the concentration of reactants or products
per unit time. It is typically expressed as:
The rate can be defined mathematically in terms of the concentration of reactants and
products:
Average Rate:
The average rate gives a general idea of the speed of a reaction over a given period of
time.
Instantaneous Rate:
The instantaneous rate refers to the rate of reaction at a specific moment in time. It is
determined by finding the slope of the concentration vs. time curve at that particular
point. Mathematically, the instantaneous rate can be expressed as the derivative of the
concentration with respect to time:
Where:
The instantaneous rate gives a more precise measurement of how fast a reaction is
occurring at any given time and is usually used when the reaction rate changes over
time.
Example:
For a reaction where the concentration of reactant decreases over time, the
instantaneous rate at any point will give how fast the reactant is being consumed at that
exact moment, whereas the average rate gives an overall speed across a time interval.
The velocity constant (also known as the rate constant or reaction constant,
denoted as kkk) is a proportionality constant that relates the rate of reaction to the
concentrations of the reactants. It is specific to a given reaction and is dependent on
temperature.
Where:
The unit of kkk depends on the order of the reaction. For example:
Order of Reaction
The order of reaction refers to the power to which the concentration of a reactant is
raised in the rate law equation. It gives an indication of how the rate of the reaction
depends on the concentration of reactants.
2. Half-Life Period
The half-life (t1/2t_{1/2}t1/2) is the time required for the concentration of a reactant to
decrease to half of its initial value. The half-life is an important concept in reaction
kinetics as it is often used to characterize the speed of a reaction.
The rate-determining step (RDS) is the slowest step in a reaction mechanism that
determines the overall rate of the reaction. In a complex reaction with multiple steps, the
rate of the reaction is governed by the step that has the highest activation energy and
the slowest reaction rate.
● The RDS limits how fast the overall reaction can proceed. Even if other steps are
faster, the overall reaction rate will depend on the rate of the rate-determining
step.
● Example: In a reaction involving multiple steps:
○ If Step 1 is slower than Step 2, then the overall reaction rate is determined
by Step 1.
○ If Step 2 is the slowest, it becomes the rate-determining step.
The rate-determining step is typically studied to understand and control reaction rates in
industrial processes, such as the manufacture of chemicals and pharmaceuticals.
The rate of a chemical reaction can be determined using both physical and chemical
methods. These methods help us understand the speed of the reaction and the factors
that influence it.
a) Physical Methods
Physical methods involve measuring changes in physical properties of the system that
occur as the reaction progresses. Some common physical methods are:
b) Chemical Methods
1. Titration:
○ Regular sampling of the reaction mixture at different times can be titrated
to determine the concentration of a reactant or product. For example, if the
concentration of a reactant decreases over time, titration can be used to
measure how the concentration changes.
2. Colorimetry:
○ For reactions involving colored species, the concentration of reactants or
products can be determined by measuring the color intensity at different
times using colorimetric analysis.
3. Gravimetric Method:
○ This method is used when a solid product is formed in the reaction. The
change in mass of the system is measured at various time intervals to
determine the reaction rate.
4. Gas Volume Measurement:
○ If the reaction produces a gas, the volume of gas evolved over time can
be measured to determine the reaction rate.
5. Manometry:
○ This involves measuring the pressure changes during a reaction, which
can be used to determine the rate of gas-phase reactions.
Activation energy is the minimum energy required for a chemical reaction to occur. It
represents the energy barrier that must be overcome for reactants to transform into
products. The greater the activation energy, the slower the reaction, as fewer molecules
will have enough energy to react at a given temperature.
● Mathematically, the rate constant kkk is related to the activation energy
EaE_aEathrough the Arrhenius equation:
Where:
The order of reaction refers to the relationship between the rate of reaction and the
concentration of the reactants. There are various methods to determine the order of a
reaction, including the half-life method and the method of large excess.
a) Half-Life Method
The half-life method is based on observing how the half-life of a reactant changes as
the concentration changes during the reaction. The half-life is the time taken for the
concentration of a reactant to reduce to half of its initial value.
● Zero-Order Reactions:
○ For a zero-order reaction, the rate is independent of the concentration of
the reactant.
○ The half-life is directly proportional to the initial concentration.
○ Formula: t1/2=[A]02kt_{1/2} = \frac{[A]_0}{2k}t1/2=2k[A]0Where:
■ [A]0[A]_0[A]0is the initial concentration,
■ kkk is the rate constant.
● First-Order Reactions:
○ For a first-order reaction, the rate is directly proportional to the
concentration of one reactant.
○ The half-life is independent of the initial concentration and is constant.
○ Formula: t1/2=0.693kt_{1/2} = \frac{0.693}{k}t1/2=k0.693Where kkk is the
rate constant.
● Second-Order Reactions:
○ For a second-order reaction, the rate depends on the square of the
concentration of one reactant.
○ The half-life is inversely proportional to the initial concentration.
○ Formula: t1/2=1k[A]0t_{1/2} = \frac{1}{k[A]_0}t1/2=k[A]01Where:
■ [A]0[A]_0[A]0is the initial concentration,
■ kkk is the rate constant.
To find the order of the reaction, you can measure the half-life at different initial
concentrations and analyze how the half-life changes:
The method of large excess involves carrying out the reaction with one reactant
present in a large excess compared to the other. This method helps simplify the rate law
by treating the excess reactant as if its concentration remains constant during the
course of the reaction.
● Steps:
○ Excess Reactant: Take one reactant in large excess, so its concentration
effectively does not change during the reaction.
○ Rate Law Simplification: For a reaction aA+bB→productsaA + bB
\rightarrow \text{products}aA+bB→products, if AAA is in excess, the rate
law simplifies to: Rate=k′[B]n\text{Rate} = k' [B]^nRate=k′[B]n Where k′k'k′
is the effective rate constant considering the excess concentration of AAA,
and nnn is the order of reaction with respect to BBB.
○ Experimental Measurements: Measure the rate of reaction for different
concentrations of the limiting reactant BBB. Plot the rate against the
concentration of BBB and determine the order of reaction from the graph.
● Applications:
○ This method is useful for reactions where one reactant is much more
concentrated than the others, allowing the reaction to behave as if it
depends only on the concentration of the limiting reactant.
○ It is often used in reactions involving gases or large quantities of one
reactant.
● Example: In a reaction 2A+B→products2A + B \rightarrow
\text{products}2A+B→products, if reactant AAA is present in large excess, the
reaction rate can be written as:
Rate=k′[B]n\text{Rate} = k' [B]^nRate=k′[B]n
By varying [B][B][B] and measuring the rate, you can determine the order nnn
with respect to BBB.
● Applications:
1. Pharmaceutical Industry: Activation energy and reaction order can help in
determining how fast drugs are metabolized in the body.
2. Chemical Engineering: This method is used to optimize reaction rates in
industrial reactors.
3. Environmental Chemistry: Understanding reaction kinetics aids in studying
pollutant degradation and its effect on ecosystems.
1. Concentration of Reactants
2. Temperature
3. Presence of a Catalyst
● Effect on Rate: The larger the surface area of reactants, the faster the reaction.
A larger surface area allows more particles to be exposed to other reactants,
leading to more collisions and a faster reaction.
● Why It Happens: A greater surface area means more area for collisions between
reactant molecules, which increases the frequency of successful collisions and,
consequently, the reaction rate.
● Example: A powdered solid reactant will react faster than a large chunk of the
same material because it has more exposed surface area.
5. Nature of Reactants
● Effect on Rate: The chemical nature of the reactants affects the rate of reaction.
Some substances react more readily than others. For example, ionic compounds
tend to react more quickly than covalent compounds.
● Why It Happens: The strength of bonds between atoms in molecules plays a
role in determining how easily reactants can form products. For example,
reactions involving ionic compounds are generally faster than those involving
covalent compounds because the bonds in ionic compounds are more easily
broken.
● Example: The reaction between sodium metal and water is much faster than the
reaction between magnesium metal and water due to the difference in reactivity
between the two metals.
6. Pressure (for Gas-phase Reactions)
● Effect on Rate: For reactions involving gases, increasing the pressure can
increase the rate of reaction. This is because increasing the pressure decreases
the volume, increasing the concentration of the gas molecules, which leads to
more frequent collisions.
● Why It Happens: At higher pressures, gas molecules are compressed into a
smaller volume, leading to more molecules in the same space and, therefore,
more collisions per unit time.
● Example: In the reaction between nitrogen and hydrogen to form ammonia (the
Haber process), increasing the pressure increases the rate of reaction.
● Effect on Rate: Light, particularly ultraviolet (UV) light, can affect the rate of
certain reactions by providing energy to molecules, making them more reactive.
● Why It Happens: In photochemical reactions, light provides energy that can
break bonds or excite molecules to higher energy states, facilitating the reaction.
● Example: The decomposition of hydrogen halides (e.g., HCl) in the presence of
UV light is an example of a photochemical reaction.
● Effect on Rate: The ionic strength of the solution (i.e., the concentration of ions)
can influence the rate of reactions involving ions. Higher ionic strength can
increase the rate of reactions by increasing the frequency of collisions between
reactants.
● Why It Happens: Higher ionic strength can reduce the repulsion between
charged species in the solution, facilitating collisions between oppositely charged
ions and increasing the reaction rate.
● Example: In reactions involving ionic compounds in solution, such as
precipitation reactions, increasing the ionic strength of the solution can speed up
the reaction.
Applications:
1. Chemical Industry: Control of reaction rates is vital in industrial processes, such
as in the production of chemicals, fertilizers (Haber process), and polymers.
2. Environmental Chemistry: Understanding how temperature, pressure, and
catalysts affect the rate of pollution breakdown is crucial for environmental
protection.
3. Pharmaceuticals: In drug manufacturing, controlling the rate of reaction ensures
product consistency and efficiency.
Arrhenius Equation
The Arrhenius equation is a mathematical formula that describes how the rate
constant (kkk) of a chemical reaction depends on temperature. It provides insight into
the effect of temperature on the rate of reaction and the activation energy required for
the reaction to occur.
Where:
Key Concepts
1. Activation Energy (Ea): The minimum energy that must be overcome for a
reaction to occur. Higher EaE_aEameans slower reaction rates at a given
temperature.
2. Pre-exponential Factor (A): Also known as the frequency factor, this represents
the number of times reactants approach each other in the proper orientation to
react. It reflects the frequency of collisions and the probability that collisions will
result in a reaction.
3. Effect of Temperature: The rate constant kkk increases with an increase in
temperature because the exponential term e−EaRTe^{-\frac{E_a}{RT}}e−RTEa
becomes larger at higher temperatures.
4. Exponential Dependence: The exponential term
e−EaRTe^{-\frac{E_a}{RT}}e−RTEasuggests that as the temperature increases,
the rate constant increases exponentially because more molecules have
sufficient energy to overcome the activation energy barrier.
Graphical Representation
● Plot: If you plot lnk\ln klnk versus 1T\frac{1}{T}T1(where TTT is in Kelvin), the
slope of the line will be −EaR-\frac{E_a}{R}−REa.
● Intercept: The y-intercept of the graph will be lnA\ln AlnA.
Suppose you have the rate constant of a reaction at two different temperatures:
You can use the Arrhenius equation to find the activation energy:
Catalysis
Types of Catalysis
Catalysis can be classified into two main types based on how the catalyst interacts with
the reactants:
1. Homogeneous Catalysis
2. Heterogeneous Catalysis
● Autocatalysis occurs when one of the products of the reaction itself acts as a
catalyst to accelerate the reaction.
● Example: The reaction between potassium permanganate and oxalic acid is
autocatalytic, where one of the products, manganese (II), acts as a catalyst for
the reaction.
Characteristics of Catalysts
Activation of a Catalyst
The activation of a catalyst involves a process where the catalyst interacts with the
reactants to form an intermediate complex that has a lower activation energy than the
uncatalyzed reaction. This complex then decomposes or reacts to give the final
products, regenerating the catalyst in the process.
● For Heterogeneous Catalysts: The reactants are adsorbed onto the surface of
the solid catalyst. The reaction takes place on the surface, where the activation
energy is lowered.
● For Homogeneous Catalysts: The catalyst is in the same phase as the
reactants, so it can easily collide and interact with them, facilitating the reaction.
Types of Catalysts
3. Autocatalyst
Enzyme Catalysis
Enzyme catalysis is a type of biological catalysis where enzymes (proteins that act as
catalysts) speed up biochemical reactions in living organisms. Enzymes are highly
specific and efficient catalysts.
1. Specificity:
○ Enzymes are highly specific for their substrates (the molecules they act
upon). This specificity arises from the enzyme's three-dimensional shape,
which matches the substrate precisely.
○ Example: Amylase is an enzyme that specifically catalyzes the
breakdown of starch into sugars.
2. Lower Activation Energy:
○ Enzymes lower the activation energy required for biochemical reactions,
allowing reactions to proceed at the temperatures commonly found in
living organisms (body temperature, 37°C).
3. Efficiency:
○ Enzymes are extremely efficient, with some enzymes being able to
catalyze thousands or even millions of reactions per second.
4. Regulation:
○ Enzyme activity is often regulated, allowing cells to control metabolic
pathways. For example, the activity of enzymes can be regulated by the
presence of specific molecules called inhibitors or activators.
5. Reusability:
○ Enzymes are not consumed in the reaction and can be reused repeatedly
to catalyze the same reaction.
6. Temperature and pH Sensitivity:
○ Enzymes are sensitive to changes in temperature and pH. Most enzymes
function best within a specific temperature and pH range. For example,
human enzymes typically work best at 37°C and near neutral pH (around
pH 7).
7. Co-factors and Coenzymes:
○ Some enzymes require non-protein molecules called co-factors or
coenzymes for their activity. Co-factors can be metal ions like zinc or iron,
and coenzymes are organic molecules, often vitamins or their derivatives.
○ Example: Vitamin B12 acts as a coenzyme in enzyme catalysis.
Applications of Catalysis: