AP Chem: Chapter 7 - Thermochemistry

Important Vocab

  • Thermochemistry: the study of the relationships between chemistry and energy
  • Energy: the capacity to do work
  • Work: the result of a force acting through a distance
  • Thermodynamics: study of energy and its interconversions
  • Internal energy: the sum of the kinetic and potential energies of all of the particles that compose the system
  • Pressure–volume work: occurs when a force (caused by a change in volume) acts through a distance against an external pressure
  • Heat: the transfer of thermal energy
  • Thermal equilibrium: Surroundings & object are same temp, no additional net transfer of temp
  • Heat capacity: the quantity of heat required to change its temperature by 1 °C
  • Calorimetry: measure the thermal energy exchanged between the reaction (defined as the system) and the surroundings by observing the change in temperature of the surroundings
  • Enthalpy: the sum of a system’s internal energy and the product of its pressure and volume

Types of Energy

Kinetic

  • Associated with the motion of an object
  • Ex: Moving ball

Thermal

  • Associated with the temperature of an object
  • Type of kinetic energy
  • Arises from the motions of atoms or molecules within a substance
  • Ex: Hot cup of coffee

Potential

  • Associated with the position or composition of an object
  • Ex: compressed spring, ball held up above the ground

Chemical

  • Type of potential energy
  • Often stored in chemical bonds
  • Associated with the relative positions of electrons and nuclei in atoms and molecules

Thermodynamics

First Law of Thermodynamics

  • Also known as the law of energy conservation
  • Energy is neither created nor destroyed
  • Internal energy: the sum of the kinetic and potential energies of all of the particles that compose the system
    • Internal energy is a state system (value depends only on the state of the system)
  • Energy flow rules:
    • Reactants have a higher internal energy than the products, is negative and energy flows out of the system into the surroundings
    • If the reactants have a lower internal energy than the products, is positive and energy flows into the system from the surroundings

Heat

  • Heat: the transfer of thermal energy
  • Thermal equilibrium: Surroundings & object are same temp, no additional net transfer of temp
  • Heat capacity: the quantity of heat required to change its temperature by 1 °C
    • Depends on:
    • The amount of matter being heated
    • Specific heat capacity/molar capacity (q)
  • Pressure–volume work: occurs when a force (caused by a change in volume) acts through a distance against an external pressure
  • w = F * D
  • Calorimetry: measure the thermal energy exchanged between the reaction (defined as the system) and the surroundings by observing the change in temperature of the surroundings
    • Measurement tool: bomb calorimeter and coffee-cup calorimeter
    • Bomb calorimetry occurs at constant volume and measures ΔE for a reaction
    • Coffee-cup calorimetry occurs at constant pressure and measures ΔH for a reaction

Enthalpy

  • Enthalpy: the sum of a system’s internal energy and the product of its pressure and volume
  • H = E + PV
  • Negative delta H = endothermic reaction
  • Positive delta H = exothermic reaction
  • The value of ΔH for a chemical reaction is the amount of heat absorbed or evolved in the reaction under conditions of constant pressure
  • An endothermic reaction has a positive ΔH and absorbs heat from the surroundings. An endothermic reaction feels cold to the touch
  • An exothermic reaction has a negative ΔH and gives off heat to the surroundings. An exothermic reaction feels warm to the touch
  • Standard heat of formation
  • Standard State
    • For a Gas: The standard state for a gas is the pure gas at a pressure of exactly 1 atm.
    • For a Liquid or Solid: The standard state for a liquid or solid is the pure substance in its most stable form at a pressure of 1 atm and at the temperature of interest (often taken to be 25 °C).
    • For a Substance in Solution: The standard state for a substance in solution is a concentration of exactly 1 M.
  • Standard Enthalpy Change (ΔH°)
    • The change in enthalpy for a process when all reactants and products are in their standard states. The degree sign indicates standard states.
  • Standard Enthalpy of Formation ()
    • For a Pure Compound: The change in enthalpy when 1 mol of the compound forms from its constituent elements in their standard states.
    • For a Pure Element in Its Standard State: delta H = 0

Hess’ Law

  • If a chemical equation can be expressed as the sum of a series of steps, then for the overall equation is the sum of the heats of reaction for each step