Chapter 58: Problem 15
For a certain chemical reaction \(\Delta G^{\circ}=-200 \mathrm{~kJ} / \mathrm{mol}\). When the reactants are mixed, no chemical reaction is apparent. Is this reaction under thermodynamic or kinetic control?
Short Answer
Expert verified
The chemical reaction is under kinetic control.
Step by step solution
01
Understand the concept of \(\Delta G^{\circ}\)
Gibbs Free Energy, represented by \(\Delta G^{\circ} \), determines if a reaction is spontaneous or not. If \(\Delta G^{\circ} \) is negative, the reaction is spontaneous, and if it's positive, the reaction is non-spontaneous.
02
Understand the implications of the given thermodynamic value
Here we are given that \(\Delta G^{\circ} = -200 \mathrm{~kJ} / \mathrm{mol}\), which means the reaction is spontaneous thermodynamically. But remember, spontaneous reactions don't necessarily happen quickly.
03
Consider the observation – no apparent chemical reaction
Even with a spontaneous \(\Delta G^{\circ} \), it's clear that no chemical reaction is apparent when the reactants are mixed. This implies that the reaction might have a significant energy barrier (activation energy) that needs to be overcome for the reaction to proceed, even if it is feasible from a thermodynamics point of view.
04
Decide whether the reaction is under kinetic or thermodynamic control
Remember, if the reaction rate determines the product ratio, it's under kinetic control. Here the reaction seems to be slow, indicating that the kinetic factor (i.e., the activation energy) is dominant in this case, despite a thermodynamically spontaneous \(\Delta G^{\circ}\). Hence, we can conclude that the reaction is under kinetic control.
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Key Concepts
These are the key concepts you need to understand to accurately answer the question.
Gibbs Free Energy
Gibbs Free Energy, symbolized as \( \Delta G \), is an incredibly valuable function in predicting the direction of a chemical reaction. It combines enthalpy, entropy, and temperature to provide information about the spontaneity of a reaction under constant pressure and temperature conditions. A negative value for \( \Delta G \) indicates a spontaneous reaction, which means that it can occur without external influence. For example, a reaction with \( \Delta G = -200 \mathrm{~kJ} / \mathrm{mol} \) signifies that it is energetically favorable and should proceed spontaneously.
However, free energy only tells us about the thermodynamics of a process — whether the products are at a lower energy level than the reactants — it doesn't account for the speed at which that process will occur. This is why, despite the negative \( \Delta G \) in the given exercise, the reaction might not be noticeable immediately upon mixing the reactants, leading to the common confusion between thermodynamic favorability and reaction kinetics. Understanding Gibbs Free Energy is crucial in predicting the potential of a reaction without considering time as a factor.
However, free energy only tells us about the thermodynamics of a process — whether the products are at a lower energy level than the reactants — it doesn't account for the speed at which that process will occur. This is why, despite the negative \( \Delta G \) in the given exercise, the reaction might not be noticeable immediately upon mixing the reactants, leading to the common confusion between thermodynamic favorability and reaction kinetics. Understanding Gibbs Free Energy is crucial in predicting the potential of a reaction without considering time as a factor.
Spontaneous Reaction
The term \'spontaneous reaction\' refers to a process that can occur without needing to be driven by external energy. It's a concept rooted deeply in the thermodynamics of a system. The key metric for spontaneity is the sign of \( \Delta G \): a negative \( \Delta G \) means the reaction should be spontaneous, while a positive one suggests the opposite.
However, \'spontaneous\' does not necessarily mean \'immediate\'. Reactions that are spontaneous can still be slow. This discrepancy occurs because spontaneity doesn't account for the reaction mechanism or the energy required to initiate the process, known as activation energy. As a result, a reaction with a highly negative \( \Delta G \) might not be apparent, as noted in our exercise, because although it's driven to occur eventually, it has not overcome the activation energy barrier yet. This key distinction highlights the importance of differentiating between a reaction's thermodynamic properties and its kinetics.
However, \'spontaneous\' does not necessarily mean \'immediate\'. Reactions that are spontaneous can still be slow. This discrepancy occurs because spontaneity doesn't account for the reaction mechanism or the energy required to initiate the process, known as activation energy. As a result, a reaction with a highly negative \( \Delta G \) might not be apparent, as noted in our exercise, because although it's driven to occur eventually, it has not overcome the activation energy barrier yet. This key distinction highlights the importance of differentiating between a reaction's thermodynamic properties and its kinetics.
Activation Energy
Activation energy, often symbolized as \( E_a \), is a kinetic concept that describes the minimum amount of energy required for reactants to transform into products. It's essentially an energy barrier that must be overcome for a chemical reaction to proceed. Even when a reaction is spontaneously favorable (\( \Delta G < 0 \)), if the activation energy is not met, the reactants are unable to convert into products at a perceivable rate.
In the context of our example, the absence of apparent change upon mixing reactants suggests a high \( E_a \). It implies that the energy needed to initiate the reaction is not available under normal conditions, thereby hindering the process that is otherwise thermodynamically spontaneous. This is why assessing activation energy is just as important as \( \Delta G \) in determining the overall feasibility and timeframe of a chemical reaction.
In the context of our example, the absence of apparent change upon mixing reactants suggests a high \( E_a \). It implies that the energy needed to initiate the reaction is not available under normal conditions, thereby hindering the process that is otherwise thermodynamically spontaneous. This is why assessing activation energy is just as important as \( \Delta G \) in determining the overall feasibility and timeframe of a chemical reaction.