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Exothermic and endothermic reactions

Paper 1Paper 2Paper 3Paper 4Paper 5Paper 6

This topic is examined in Paper 1, Paper 2, Paper 3, and Paper 4. Practical skills related to measuring temperature changes are tested in Paper 5 and Paper 6.

Types of Energy Transfer
Chemical reactions always involve energy changes. We classify them based on the direction of thermal energy transfer between the reaction mixture (the chemicals reacting) and the surroundings (the air, the container, the thermometer).
Enthalpy Change ($\Delta H$)
Negative (-) value.
Positive (+) value.
Why does the temperature change?

In an exothermic reaction, energy is released from the chemical bonds into the surroundings. This extra thermal energy causes the particles in the surroundings to move faster, resulting in a higher temperature.

In an endothermic reaction, energy is absorbed from the surroundings to break bonds. This removal of thermal energy causes the particles in the surroundings to slow down, resulting in a lower temperature.

Enthalpy Change (\Delta H)

Enthalpy change is the term used to describe the transfer of thermal energy during a reaction at constant pressure.

  • For exothermic reactions, \Delta H is negative (e.g., -286 \text{ kJ mol}^{-1}). This indicates that the system has lost energy to the surroundings.
  • For endothermic reactions, \Delta H is positive (e.g., +50 \text{ kJ mol}^{-1}). This indicates that the system has gained energy from the surroundings.
Reaction Pathway Diagrams

A reaction pathway diagram (or energy profile) shows how the energy of the system changes as reactants turn into products.

Axes:

  • Y-axis: Energy level (usually in kJ or kJ mol⁻¹).
  • X-axis: Reaction progress (time/extent of reaction).

Interpreting the Diagrams:

  1. Reactants and Products: The horizontal lines represent the energy levels of the starting materials (reactants) and the final materials (products).
  2. The Curve: The curve shows the energy change during the reaction. It must start at the reactant level, go up to a peak, and come down to the product level.
  3. Activation Energy (E_a): This is the minimum energy colliding particles must have to react. On the diagram, it is the vertical distance from the reactant line to the highest point (peak) of the curve.
  4. Enthalpy Change (\Delta H): This is the difference in energy between the products and the reactants. It is the vertical distance between the product line and the reactant line.

Drawing Reaction Pathway Diagrams:

When asked to draw a diagram from provided information, follow these steps:

  1. Draw Axes: Label Y-axis 'Energy' and X-axis 'Reaction Progress'.
  2. Draw Reactant Line: Draw a horizontal line at the starting energy level. Label it 'Reactants'.
  3. Determine Product Level:
    • If exothermic: Draw the product line lower than the reactant line.
    • If endothermic: Draw the product line higher than the reactant line.
    • Label this line 'Products'.
  4. Draw the Curve: Start at the reactant line, curve upwards to a peak, and curve downwards to meet the product line. Ensure the curve is smooth and does not cross the axes.
  5. Label E_a: Draw a vertical arrow starting from the reactant line pointing up to the peak. Label it 'E_a'.
  6. Label \Delta H: Draw a vertical arrow starting from the product line pointing up to the reactant line (or vice versa, but clearly indicating the gap). Label it '\Delta H'. Note: For exothermic, the arrow points down; for endothermic, it points up.
Endothermic Diagram
Products are higher than reactants.
Starts low, ends high.
Positive (+)
Activation Energy (E_a)
Activation energy is defined as the minimum energy that colliding particles must possess in order to react successfully.

Even in exothermic reactions (which release net energy), energy is required initially to break the bonds in the reactant molecules. This initial 'energy barrier' is the activation energy.

Bond Breaking and Bond Making
To understand why reactions are exothermic or endothermic, we look at the bonds:

  1. Breaking bonds always requires energy input. Therefore, bond breaking is an endothermic process.
  2. Making bonds always releases energy. Therefore, bond making is an exothermic process.

The overall enthalpy change (\Delta H) depends on the balance between these two processes:

\Delta H = \text{Energy required to break bonds} - \text{Energy released when bonds form}

Calculating Enthalpy Change from Bond Energies:

  • If Energy in (breaking) > Energy out (making), the reaction is endothermic (\Delta H is positive).
  • If Energy out (making) > Energy in (breaking), the reaction is exothermic (\Delta H is negative).
Calculating Enthalpy Change using Bond Energies

Question: Calculate the enthalpy change for the reaction: H_2 + Cl_2 \rightarrow 2HCl

Given Bond Energies:

  • H-H: 436 \text{ kJ mol}^{-1}
  • Cl-Cl: 242 \text{ kJ mol}^{-1}
  • H-Cl: 431 \text{ kJ mol}^{-1}
Step 1: Calculate energy required to break bonds (Reactants)
We need to break 1 mole of H-H and 1 mole of Cl-Cl.
\text{Energy in} = 436 + 242 = +678 \text{ kJ mol}^{-1}
Step 2: Calculate energy released when bonds form (Products)
We form 2 moles of H-Cl bonds.
\text{Energy out} = 2 \times 431 = +862 \text{ kJ mol}^{-1}
(Note: We use positive values for the calculation and apply the sign in the final formula)
Step 3: Calculate \Delta H
\Delta H = \text{Energy in} - \text{Energy out}
\Delta H = 678 - 862
\Delta H = -184 \text{ kJ mol}^{-1}

Since \Delta H is negative, the reaction is exothermic.

⚠︎ Confusing Temperature Change Direction
Mistake: Assuming that an endothermic reaction makes the mixture hotter because 'energy is involved'.

Correction: In an endothermic reaction, energy is taken from the surroundings. Therefore, the temperature of the surroundings (and the reaction mixture) decreases. Only exothermic reactions cause a temperature increase.

⚠︎ Incorrectly Interpreting Reaction Pathway Diagrams

Mistake: Stating 'the reactants have more energy than the products' without specifying that this means the reaction is exothermic, or confusing the height of the peak with the overall energy change.

Correction: Always compare the final energy level (products) to the initial energy level (reactants).

  • If Products < Reactants: Exothermic.
  • If Products > Reactants: Endothermic.
    The height of the peak only tells you about the activation energy (E_a), not whether the reaction is exo- or endothermic.
Describing Exothermic/Endothermic Reactions

When to use: When asked to explain why a reaction is exothermic or endothermic based on a diagram or temperature data.

Why examiners accept this: Examiners look for the specific link between energy transfer and temperature change. Simply saying 'energy is released' is often insufficient without mentioning the effect on the surroundings.

Correct Phrasing Example:

  • For Exothermic: "The reaction is exothermic because thermal energy is transferred to the surroundings, causing the temperature of the surroundings to increase."
  • For Endothermic: "The reaction is endothermic because thermal energy is taken from the surroundings, causing the temperature of the surroundings to decrease."
Labeling Reaction Pathway Diagrams

When to use: When drawing or labeling a reaction pathway diagram.

Why examiners accept this: Precision in labeling is critical. The arrow for \Delta H must clearly span the gap between reactant and product levels, and E_a must start from the reactant level.

Correct Phrasing/Labeling Example:

  • Ensure the arrow for \Delta H connects the reactant line to the product line.
  • Ensure the arrow for E_a starts at the reactant line and ends at the peak of the curve.
  • Do not label the peak as 'activation energy'; label the arrow or the distance as E_a.
Past Paper Style Questions
Q:
State what is meant by the term 'exothermic reaction'.
A:
A reaction that transfers thermal energy to the surroundings.
Q:
Explain how the reaction pathway diagram shows that this reaction is endothermic.
A:
The energy level of the products is higher than the energy level of the reactants.
Q:
State the definition of activation energy, E_a.
A:
The minimum energy that colliding particles must have to react.
Q:
Calculate the enthalpy change for a reaction where 500 kJ is required to break bonds and 620 kJ is released when new bonds form. State whether the reaction is exothermic or endothermic.
A:
\Delta H = 500 - 620 = -120 \text{ kJ mol}^{-1}. The reaction is exothermic.
Q:
Which row describes what happens during an endothermic reaction?
A:
Thermal energy taken in from surroundings; Temperature of surroundings decreases.
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