Thermodynamics

Rucete ✏ Chemistry In a Nutshell


1. Energy

  • Energy is the capacity to do work.

  • Two major forms:

    • Thermal energy: energy due to particle motion (heat).

    • Chemical energy: stored in chemical bonds.

  • Unit: kilojoules (kJ)

2. Temperature vs. Heat

  • Temperature: average kinetic energy of particles in a substance.

  • Heat: thermal energy transferred due to temperature difference.

3. System vs. Surroundings

  • System: the part of the universe being studied.

    • Open system: exchanges mass and energy.

    • Closed system: exchanges energy only.

    • Isolated system: no exchange of mass or energy.

  • Surroundings: everything outside the system.

4. State Functions

  • Properties that depend only on the current state, not the path (e.g., ΔH, ΔS, ΔG).

  • Examples: pressure, volume, temperature, enthalpy.

5. Standard State

  • Conditions: 1 atm, 1 M concentration, 298 K (25°C).

  • Standard enthalpy (ΔH°), entropy (ΔS°), and free energy (ΔG°) values are measured under these.

6. Laws of Thermodynamics

First Law:

  • Energy cannot be created or destroyed, only transformed.

  • ΔE = q + w (change in internal energy = heat + work)

Second Law:

  • In any spontaneous process, entropy (ΔS) increases.

  • Systems tend toward disorder.

Third Law:

  • Entropy of a perfect crystal at 0 K = 0.

7. Enthalpy (ΔH)

  • Measure of heat at constant pressure.

  • Exothermic (ΔH < 0): releases heat.

  • Endothermic (ΔH > 0): absorbs heat.

8. Spontaneity

  • A reaction is spontaneous if it occurs without external input.

  • Driven by enthalpy (ΔH) and entropy (ΔS).

9. Hess’s Law

  • The total enthalpy change is the same, regardless of how the reaction occurs.

  • ΔH (overall) = sum of ΔH for each step.

10. Heat of Formation

  • Heat change when one mole of a compound forms from its elements.

11. Specific Heat and Heat Capacity

  • Specific heat (c): energy needed to raise 1 g of a substance by 1°C.

  • Heat capacity (C): energy needed to raise a given mass by 1°C.

  • Formulas:

    • q=mcΔT

    • q=CΔT

12. Calorimetry

  • Measurement of heat flow in a system.

  • Used to determine:

    • Heat of neutralization

    • Heat of dilution

  • qrxn=qsolutionqcalorimeter

13. Entropy (ΔS)

  • Measure of randomness/disorder.

  • More gas molecules = higher entropy.

  • ΔS increases with temperature, volume, and number of particles.

14. Gibbs Free Energy (ΔG)

  • Combines enthalpy and entropy to predict spontaneity.

  • ΔG=ΔHTΔS

  • Spontaneity:

    • ΔG < 0 → spontaneous

    • ΔG > 0 → non-spontaneous

    • ΔG = 0 → equilibrium

15. Energy Diagrams

  • Activation energy (Ea): barrier that must be overcome for a reaction.

  • ΔH is the difference between products and reactants.

    • Exothermic: products lower than reactants.

    • Endothermic: products higher than reactants.

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