JlDkDi-Thermodynamics - part 2 - enthalpy

Page 1: Enthalpy

Overview

  • Introduction to Enthalpy concepts relevant for thermodynamics.


Page 2: Key Concepts

Contents Covered

  • Standard Conditions and Standard State.

  • Bond Energies to Calculate Enthalpy Changes.

  • Standard Enthalpies of Formation.

  • Enthalpies from ΔfH⦵ directly.

  • Calorimetry techniques.

  • Hess’s Law in thermodynamics.


Page 3: Reaction State Dependency

The Role of States in Reactions

  • Example Reaction: C(s) + O2(g) → CO2(g)

  • Importance of the State of Carbon: diamond, graphite, C60.

  • For a reaction to occur, reactants must be in their standard state and at a specified temperature.

  • All products should also be in their standard states during calculations.


Page 4: Definition of Standard State

Standard Enthalpy

  • Denoted as ΔHo or ΔH⦵.

  • Defined for 1 mole at given temperature:

    • Pure substances in their most stable form at 1 bar.

    • Gases at a pressure of 1 bar (105 Pa).

    • Solutions at 1 M concentration.

  • Typically measured at room temperature (298 K).

  • Definition of a mole, approximately 6 * 10^23 atoms (Avogadro's number).


Page 5: Calculating ∆H

Bond Enthalpies Explanation

  • Calculate ΔHo using average bond enthalpies.

  • Energy needed to break 1 mole of bonds.

  • Bond Breaking:

    • Requires energy (ΔH⦵ > 0) - Endothermic reaction.

  • Bond Making:

    • Releases energy (ΔH⦵ < 0) - Exothermic reaction.

  • Units are expressed in kJ/mol.


Page 6: Example Calculation of Bond Energies

Breakdown of Energy in Reactions

  • Example: Breaking a mole of C-H bonds in methane (CH4):

    1. Enthalpy of dissociation for C(s) → C(atoms) = +610 kJ/mol

    2. Break 2 moles of H-H: 2 * 436 kJ/mol = +872 kJ/mol

    3. Making 4 moles of C-H bonds: –4 * X kJ/mol

    4. Calculation:

    ΔH⦵ = -76 = +610 + 872 - 4X

    Solving collectively leads to X = 389.5 kJ/mol.


Page 7: Properties of Graphite

Energy Characteristics

  • In graphite, approximately 1 C=C bond per carbon.

  • Sublimation ΔH⦵ = +704 kJ/mol;

  • C=C bond ΔH⦵ = +610 kJ/mol.

  • Comparison with ΔH⦵sublimation pointing to larger values.


Page 8: Further Breakdown of Bond Energies

Calculation Framework

  • Detailed energy changes for the reaction of C(graphite) + 2H2(g) → CH4(g).

  • Use of enthalpy values:

    C(graphite) + 2 H2 (g):

    • Reactions and products considering ∆H and summing energies for both reactants and products.

    Σ H(making products) - Σ H(breaking reactants).


Page 9: Energy Landscapes

Visual Representation of Reactions

  • Description of the 'energy mountains' with a focus on the reaction coordinate and energy landscape throughout the reaction path.


Page 10: Reaction Using Bond Energies

Calculation of ΔH⦵ for CH3Cl

  • Reaction: C(graphite) + 1.5 H2(g) + 0.5 Cl2(g) → CH3Cl(g).

  • Applying known bond enthalpies for calculations:

    ΔH⦵ = Σ Hmaking-products - Σ Hmaking-reactants = -99 kJ/mol.


Page 11: Summary of Bond Energies

Single and Multiple Bonds Data

  • Display of bond energies for various elements (e.g., H, C, N) in single and multiple bonds.

  • Important to reference standard bond energies in thermodynamics.


Page 12: Measuring Enthalpy of Combustion

Bomb Calorimetry

  • Measurement defined as the enthalpy change when a compound is burned fully in oxygen.

  • Calculation based on heat transfer (ΔT, mass, specific heat capacity) and the moles participating in the reaction.


Page 13: Understanding Reaction Enthalpy

Comprehensive Approach

  • Overall equation: REACTANTS → PRODUCTS, ∆H⦵ calculation as:

    • ∆H⦵ = Hproducts - Hreactants.

  • Conceptual analogy to age calculation as it deals with differences in value.


Page 14: Exothermic vs Endothermic Reactions

Example of Water Formation

  • Reaction: H2(g) + 0.5 O2(g) → H2O(l) demonstrating exothermic nature (∆H⦵ = -286 kJ/mol).

  • Clarification on manipulating coefficients for clarity in thermodynamic equations.


Page 15: Standard Enthalpy of Formation

Core Definition

  • ΔH⦵ denotes standard enthalpy when 1 mole of a substance is formed from its elements under standard conditions.


Page 16: Example of Standard Enthalpy of Formation

Ethanol Formation

  • Reaction: 2 C(s) + ½ O2(g) + 3 H2(g) → C2H5OH(l) with ∆fH⦵ = -277 kJ/mol.

  • Emphasizes accuracy over bond energies by taking into account the physical state of substances.


Page 17: Calculate ΔH⦵ from Standard Enthalpies of Formation

Methodology for Calculation

  • Using standard enthalpies to determine ΔHo through the equation:

    ΔH⦵ = Σ (∆fH⦵)products - Σ (∆fH⦵)reactants.


Page 18: Table of Standard Enthalpies of Formation

Detailed Reference Table

  • Listing of various substances and their formation enthalpies in kJ/mol.

  • Useful for quick reference during calculations.


Page 19: Allotropes

Brief Discussion

  • Overview of the concept of allotropes and their relevance in chemistry.


Page 20: Combustion of Benzene

Benzene Reaction Setup

  • Reaction: C6H6(l) + x O2(g) → y CO2(g) + z H2O(l) with focus on determining ∆H⦵.


Page 21: Calculating Enthalpy Change for Benzene

Detailed Calculation

  • Balanced combustion reaction for benzene:

    • C6H6(l) + 7.5 O2(g) → 6 CO2(g) + 3 H2O(l).

    • ΔH⦵ for total enthalpy change calculation.


Page 22: Understanding Hess’s Law

Fundamental Principle

  • Discussion on how reactions may proceed non-linearly.

  • Introduction to Hess's Law, emphasizing energy change independence from the path taken.


Page 23: Application of Hess's Law in Reactions

Example Calculation

  • Reactants and products application illustrating Hess’s law via described reactions.


Page 24: Standard Enthalpy for Acetylene

Detailed Enthalpy Calculation

  • Consideration of reactions and combustion heat requirements in acetylene formation.


Page 25: Summation of Reactions (Hess’s Law)

Example with Acetylene

  • Detailed working to find standard enthalpy using Hess’s Law based on various reactions.


Page 26: Hard Example of Hydrogenation Reaction

Reactions and Enthalpy Changes

  • Calculation involving hydrogenation of benzene, including combustion reactions with their enthalpy values.


Page 27: Continued Example Analysis

Simplifying and Summing Reactions

  • Further breakdown and use of Hess's Law for clear enthalpy calculations.


Page 28: Final Steps in Calculation

Closing the Example

  • Final summation and simplification of reaction enthalpy calculations for clarity.