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IB DP Chemistry Study Notes

5.2.2 Standard Enthalpy Changes

In the realm of thermochemistry, understanding how energy changes during reactions is pivotal. Standard enthalpy changes provide a snapshot of such energy transformations, allowing us to delve deeper into the very essence of chemical reactions.

Key Definitions

Standard Enthalpy Change of Formation (ΔHf°)

  • Definition: The standard enthalpy change of formation refers to the energy shift occurring when one mole of a substance is assembled from its elemental constituents under standard conditions, with everything in their standard states.
  • Implications:
    • A positive ΔHf° suggests that the formation process is endothermic (absorbs energy).
    • A negative ΔHf° implies that the formation process is exothermic (releases energy).
  • In-depth Illustration: Consider the synthesis of ammonia: N2(g) + 3H2(g) → 2NH3(g) The ΔHf° value for ammonia will encapsulate the energy changes intrinsic to the creation of ammonia from nitrogen and hydrogen gases.

Standard Enthalpy Change of Combustion (ΔHc°)

  • Definition: This metric measures the energy transformation when one mole of a substance is completely combusted in oxygen's presence under standard conditions, culminating in products also in their conventional states.
  • Implications:
    • It's always exothermic. Substances release energy as they burn.
    • ΔHc° values serve as crucial benchmarks, especially in energy and environmental sciences, where understanding fuel efficiencies is crucial.
  • In-depth Illustration: Ethanol’s combustion: C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l) Here, ethanol combusts to produce carbon dioxide and water, releasing energy in the process.

Standard Enthalpy Change of Neutralisation (ΔHn°)

  • Definition: Represents the energy shift when an acid and a base react to produce one mole of water under standard conditions.
  • Implications:
    • Neutralisation reactions between strong acids and bases are typically exothermic.
    • ΔHn° can help in identifying the strength of acids and bases.
  • In-depth Illustration: Sulphuric acid neutralising sodium hydroxide: H2SO4(aq) + 2NaOH(aq) → Na2SO4(aq) + 2H2O(l) Energy is released as the acid and base counteract each other's effects.

Calculations Using Standard Enthalpy Values

Harnessing Hess’s Law

Hess's Law dictates that the total enthalpy change is consistent, regardless of the pathway taken. It's grounded in the principle that enthalpy is a state function.

  • Enthalpy Cycle: Often, it's convenient to utilise an enthalpy cycle – a graphical representation linking different pathways between the same reactants and products. By summing up the enthalpy changes for known steps, one can deduce the enthalpy change for an unknown step.

Bond Energy Calculations

The energy profile of a reaction can be dissected further by looking at individual bond energies.

  • Breaking Bonds:
    • Energy input is necessitated to disrupt existing bonds.
    • This process, being endothermic, incurs a positive enthalpy change.
  • Forming Bonds:
    • As new bonds form, energy is liberated.
    • This process, being exothermic, results in a negative enthalpy change.

Examples of Calculations

Example 1: Using ΔHf° Values

Given: ΔHf° for CO2(g) = -394 kJ/mol, ΔHf° for H2O(l) = -286 kJ/mol, ΔHf° for C6H12O6(s) = -1273 kJ/mol

Find the ΔH for: C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l)

Calculation: ΔH = [6(-394) + 6(-286)] - (-1273) = -2820 kJ

Example 2: Bond Energy Method

To compute ΔH for: CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

Using known bond energies: ΔH = [4(413) + 2(498)] - [2(805) + 4(464)] = -802 kJ

FAQ

The magnitude of standard enthalpy changes isn't immune to external influences. Primarily, bond types hold significant sway. Breaking a triple bond, for instance, demands more energy than severing a single bond. Additionally, the reactants' and products' physical and chemical states can induce variations. Phase shifts, such as from solid to liquid or liquid to gas, can modify the energy landscape, thereby influencing the enthalpy change. The molecular structure and spatial arrangement of atoms in molecules can also come into play. Reactions with multiple intermediate stages or varying mechanisms can exhibit differing energy requirements or releases, even if they commence and conclude with analogous reactants and products. It's imperative to consider these nuances for an in-depth grasp of the subject matter.

While combustion and formation both engage in the formation of compounds, their operational mechanics and resulting products are divergent. The standard enthalpy change of combustion is anchored in the complete combustion of a mole of a substance in an oxygen-rich environment. Typical products for the combustion of hydrocarbons, for instance, are water and carbon dioxide. In stark contrast, the standard enthalpy change of formation focuses on the formation of a single mole of a compound derived directly from its individual elemental constituents in their quintessential standard states. The differing reactants and products in these processes significantly impact the respective energy changes, leading to their distinct enthalpy values. Understanding this distinction is imperative for accurate calculations and analyses in thermodynamics.

The standard enthalpy change, while instrumental, is not an exclusive or foolproof indicator of a reaction's feasibility. A reaction's exothermic nature (negative ΔH) might hint at spontaneity, but it's not a definitive sign. Gibbs free energy change (ΔG) is a more holistic measure, amalgamating both the enthalpy change (ΔH) and entropy change (ΔS) for a given temperature. When ΔG yields a negative value, it denotes the reaction's spontaneity. Hence, while ΔH is certainly a pivotal factor, for a comprehensive prognosis of a reaction's feasibility, entropy and other parameters must be simultaneously accounted for. This multi-pronged approach aids in cultivating a more nuanced understanding of chemical reactions and their propensities.

The standard enthalpy change of formation delineates the energy alteration occurring when a single mole of a substance emerges from its elementary components in their standard states. Given that elements in their standard states are regarded as the foundational reference, they are inherently in their purest, unformed configuration. As a result, they have not undergone any transformative process from simpler entities. Consequently, it's inherently understood that there's an absence of energy transformation related to their formation. By methodically assigning a zero value to these elements' enthalpy change of formation, it establishes a consistent benchmark. This, in turn, facilitates the comparative assessment of the enthalpy changes of compounds relative to a known and universally accepted baseline.

'Standard conditions' refers to a specific set of universally agreed-upon conditions utilised in thermodynamics. In the realm of chemistry, when discussing standard enthalpy changes, 'standard conditions' predominantly signify a temperature of 298 Kelvin (25°C) and a pressure of 100 kPa. At this juncture, substances should exhibit their standard states, the most stable physical state at the aforementioned conditions. For instance, for elements such as oxygen or nitrogen, the standard state is gaseous, whereas, for carbon, it's solid in the form of graphite. The rationale behind the implementation of 'standard conditions' is to ensure uniformity. By keeping the conditions consistent across various experiments or studies, the derived data remains coherent, and comparable, and eliminates discrepancies originating from varied experimental conditions.

Practice Questions

Define the standard enthalpy change of combustion. Using the given standard enthalpy change of formation values, calculate the standard enthalpy change of combustion for methane (CH4):

ΔHf° (CH4) = -74.8 kJ/mol ΔHf° (CO2) = -393.5 kJ/mol ΔHf° (H2O) = -285.8 kJ/mol

The standard enthalpy change of combustion refers to the energy transformation when one mole of a substance is completely combusted in the presence of oxygen under standard conditions, resulting in the formation of products also in their standard states. Using the given ΔHf° values and the combustion reaction CH4(g) + 2O2(g) → CO2(g) + 2H2O(l), we can calculate ΔHc° for methane: ΔHc° = [ΔHf°(CO2) + 2ΔHf°(H2O)] - ΔHf°(CH4) = (-393.5 + 2(-285.8) + 74.8) kJ/mol = -890.3 kJ/mol.

Describe the significance of the standard enthalpy change of neutralisation in the context of acid-base reactions and provide a reason why the values might differ between different acid-base combinations.

The standard enthalpy change of neutralisation is indicative of the energy change when an acid and a base react to produce one mole of water under standard conditions. It offers insight into the exothermic nature of acid-base reactions and is instrumental in discerning the strength and potency of acids and bases. Discrepancies in ΔHn° values among different acid-base pairings arise due to variations in the strength of the participating acids and bases. Stronger acid-base pairs typically exhibit larger (more exothermic) ΔHn° values than their weaker counterparts, as they donate and accept protons with greater zeal, leading to a more significant release of energy during neutralisation.

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