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Transition State Theory

The document discusses Transition State Theory (TST), which explains chemical reaction rates through the concept of an activated complex that forms at a transition state. It compares TST with Collision Theory, highlighting that TST accounts for structural and energetic requirements, making it more accurate for complex reactions. The document also outlines key concepts such as activation energy, molecular motion, and the implications of TST in catalysis and biochemical reactions.

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7 views

Transition State Theory

The document discusses Transition State Theory (TST), which explains chemical reaction rates through the concept of an activated complex that forms at a transition state. It compares TST with Collision Theory, highlighting that TST accounts for structural and energetic requirements, making it more accurate for complex reactions. The document also outlines key concepts such as activation energy, molecular motion, and the implications of TST in catalysis and biochemical reactions.

Uploaded by

sangee34sit
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
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The **qualitative treatment of the theory of absolute reaction rates** (also known as

**Transition State Theory (TST)**) provides an intuitive understanding of how chemical


reactions occur at a molecular level. This theory, developed in the 1930s by Henry Eyring,
Meredith G. Evans, and Michael Polanyi, explains reaction rates based on the concept of an
**activated complex** or **transition state**.

### **Key Concepts in the Qualitative Treatment**


1. **Reaction Pathway and Energy Barrier:**
- Reactants must pass through a high-energy intermediate state (the **transition state**)
before forming products.
- The energy required to reach this state is called the **activation energy (Eₐ)**.
- The transition state is unstable and exists only momentarily.

2. **Formation of the Activated Complex:**


- Reactants form a temporary, unstable structure known as the **activated complex**.
- This complex is at the peak of the energy barrier.
- It can either decompose into products or revert to reactants.

3. **Molecular Motion and Energy Distribution:**


- Molecules move and collide with different kinetic energies.
- Only a fraction of molecules have enough energy to reach the transition state at a given
temperature.
- Temperature influences the number of molecules that can overcome the activation
barrier.

4. **Rate of Reaction:**
- The rate depends on how frequently reactants form the activated complex.
- The transition state theory introduces the **rate constant (k)**, which is given by the
**Eyring equation**:

k=(kBT/h)exp(−ΔG‡/RT)

where:
- kB is the Boltzmann constant,
- h is Planck’s constant,
- T is temperature,
- ΔG‡ is the Gibbs free energy of activation,
- R is the universal gas constant.

5. **Comparison to Collision Theory:**


- Unlike **collision theory**, which considers only molecular collisions and energy,
**TST** also includes the **structural and energetic requirements** for a successful
reaction.
- The transition state theory provides a more detailed and accurate description of reaction
rates, especially for complex reactions.

### **Implications and Applications**


- Helps in **understanding catalysis**, where a catalyst lowers the activation energy, making
the transition state more accessible.
- Used in **biochemical reactions**, particularly enzyme kinetics.
- Provides insights into **temperature dependence** of reaction rates.

Would you like a more detailed mathematical derivation or a real-world example?

### **Comparison Between Transition State Theory (TST) and Collision Theory**
Both **Transition State Theory (TST)** and **Collision Theory** explain how chemical
reactions occur, but they differ in their approach.

| Feature | **Transition State Theory (TST)** | **Collision Theory** |


|------------------------|---------------------------------|---------------------|
| **Key Idea** | Reactants form an **activated complex** at the transition state
before converting into products. | Reactants must collide with sufficient **energy** and
proper **orientation** to react. |
| **Reaction Pathway** | Proposes a continuous transformation from reactants to products
via a **transition state**. | Considers discrete molecular collisions leading to reaction. |
| **Energy Requirement** | Requires reaching the **activation energy (Eₐ)** to form the
activated complex. | Requires a **minimum collision energy (Eₐ)** to break bonds and
initiate the reaction. |
| **Orientation Effect** | Accounts for structural and energetic constraints in forming the
activated complex. | Introduces a **steric factor (P)** to account for correct orientation in
collisions. |
| **Rate Equation** | Derived from statistical mechanics and thermodynamics: \[ k = \
frac{k_B T}{h} e^{-\Delta G^\ddagger / RT} \] | Based on kinetic theory of gases: \[ k = Z P
e^{-Eₐ / RT} \] where **Z** is collision frequency. |
| **Temperature Dependence** | Derived from Gibbs free energy considerations. | Uses
the Arrhenius equation. |
| **Scope** | More accurate for complex reactions, including enzymatic and catalytic
reactions. | Simpler and mainly applicable to gas-phase reactions. |

---

### **Deriving Relation Between Activation Energy and Minimum Energy in Collision
Theory**
In **Collision Theory**, for a reaction to occur:
- **Molecules must collide with a minimum energy** to overcome the activation barrier.
- This energy is related to the **activation energy (Eₐ)**.

The rate constant in collision theory is given by:


\[
k = Z P e^{-Eₐ / RT}
\]
where:
- \( k \) = rate constant,
- \( Z \) = collision frequency,
- \( P \) = steric factor (accounts for correct orientation),
- \( Eₐ \) = activation energy,
- \( R \) = gas constant,
- \( T \) = temperature.

#### **Minimum Energy in a Collision**


The kinetic energy of two colliding molecules in a gas follows the **Maxwell-Boltzmann
distribution**. The fraction of molecules having kinetic energy greater than or equal to
**Eₐ** is:
\[
f(E) = e^{-Eₐ / RT}
\]
Thus, the **minimum energy required for a successful reaction** is **equal to the
activation energy** in ideal cases.

However, due to orientation effects and molecular dynamics, not all collisions with \( E \geq
Eₐ \) lead to a reaction. Hence, the **effective energy** for reaction is sometimes slightly
higher than \( Eₐ \) due to steric constraints.

---

### **Conclusion**
- **In Collision Theory**, molecules need a minimum energy (\( E_{\text{min}} \)) equal to
or greater than the activation energy (\( Eₐ \)) to react.
- **In TST**, the reaction is seen as a continuous transformation through a transition state,
which provides a more detailed molecular description.
- **Both theories agree** that \( E_{\text{min}} \geq Eₐ \), but TST accounts for structural
changes in the activated complex, making it more widely applicable.

Would you like an example or further elaboration on the mathematical derivation?

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