💏Intro to Chemistry Unit 16 – Thermodynamics

Key Concepts and Definitions

• Thermodynamics studies the relationships between heat, work, temperature, and energy
• System refers to the specific part of the universe being studied or of interest
• Surroundings include everything outside the system
• Open system allows both energy and matter to be exchanged with the surroundings
  • Example: Boiling water in an open pot
• Closed system permits energy but not matter to be exchanged with the surroundings
  • Example: A sealed container with hot liquid inside
• Isolated system does not allow either energy or matter to be exchanged with the surroundings
• State functions depend only on the current state of the system, not on how it got there (pressure, temperature, volume, energy)
• Path functions depend on the route taken to reach a particular state (heat, work)

Laws of Thermodynamics

• First Law of Thermodynamics states that energy cannot be created or destroyed, only converted from one form to another
  • Also known as the Law of Conservation of Energy
  • Mathematically: ΔU = Q + W, where ΔU is the change in internal energy, Q is heat, and W is work
• Second Law of Thermodynamics states that the entropy of the universe always increases in a spontaneous process
  • Entropy is a measure of disorder or randomness in a system
  • Spontaneous processes occur without external intervention
• Third Law of Thermodynamics states that the entropy of a perfect crystal at absolute zero is zero
  • Absolute zero is the lowest possible temperature, at which point molecules stop moving
• Zeroth Law of Thermodynamics defines thermal equilibrium
  • If two systems are in thermal equilibrium with a third system, they are in thermal equilibrium with each other

Energy and Heat Transfer

• Energy is the capacity to do work or transfer heat
• Kinetic energy is the energy of motion, dependent on an object's mass and velocity
• Potential energy is stored energy due to an object's position or composition
  • Examples: Gravitational, chemical, and elastic potential energy
• Heat is the transfer of thermal energy between systems or surroundings due to a temperature difference
• Temperature is a measure of the average kinetic energy of the particles in a system
• Thermal equilibrium occurs when two systems in contact have the same temperature and no heat flows between them
• Conduction is heat transfer through direct contact between particles
• Convection is heat transfer through the movement of fluids or gases
• Radiation is heat transfer through electromagnetic waves without requiring a medium

Enthalpy and Entropy

• Enthalpy (H) is the total heat content of a system at constant pressure
  • Mathematically: H = U + PV, where U is internal energy, P is pressure, and V is volume
• Change in enthalpy (ΔH) is the heat absorbed or released by a system during a process at constant pressure
  • Exothermic processes release heat and have a negative ΔH
  • Endothermic processes absorb heat and have a positive ΔH
• Entropy (S) is a measure of the disorder or randomness in a system
• Change in entropy (ΔS) is the change in disorder or randomness of a system during a process
  • Positive ΔS indicates an increase in disorder (more spontaneous)
  • Negative ΔS indicates a decrease in disorder (less spontaneous)
• Gibbs free energy (G) predicts the spontaneity of a process at constant temperature and pressure
  • Mathematically: ΔG = ΔH - TΔS, where T is the absolute temperature
  • If ΔG is negative, the process is spontaneous; if ΔG is positive, the process is non-spontaneous

Chemical Reactions and Energy Changes

• Chemical reactions involve the rearrangement of atoms to form new substances
• Exothermic reactions release heat to the surroundings and have a negative ΔH
  • Example: Combustion of fuels
• Endothermic reactions absorb heat from the surroundings and have a positive ΔH
  • Example: Photosynthesis
• Activation energy is the minimum energy required for a reaction to occur
  • Catalysts lower the activation energy without being consumed in the reaction
• Hess's Law states that the total enthalpy change of a reaction is independent of the route taken
  • Allows for the calculation of enthalpy changes for reactions that are difficult to measure directly
• Calorimetry measures the heat transfer during a chemical or physical process
  • Example: Using a bomb calorimeter to determine the heat of combustion

Thermochemical Equations

• Thermochemical equations include the enthalpy change of a reaction as part of the equation
• Stoichiometric coefficients in a balanced thermochemical equation indicate the molar ratios of reactants and products
• Standard states are used as reference points for thermodynamic properties (1 atm, 298 K, 1 M concentrations)
• Standard enthalpy of formation (ΔH°f) is the enthalpy change when one mole of a compound is formed from its elements in their standard states
• Standard enthalpy of reaction (ΔH°rxn) can be calculated using the standard enthalpies of formation of the reactants and products
  • Mathematically: ΔH°rxn = ΣΔH°f (products) - ΣΔH°f (reactants)
• Enthalpy changes for phase transitions (melting, freezing, vaporization, condensation) can also be included in thermochemical equations

Real-World Applications

• Thermodynamics plays a crucial role in designing efficient engines and power plants
  • Example: Carnot cycle, which sets the upper limit for the efficiency of heat engines
• Understanding thermodynamics helps in optimizing industrial processes and chemical reactions
  • Example: Haber-Bosch process for ammonia synthesis
• Thermodynamic principles are used in the development of materials with desired properties
  • Example: Phase diagrams to determine the stability of different phases
• Biological systems rely on thermodynamic principles for energy transfer and regulation
  • Example: ATP (adenosine triphosphate) as the energy currency in cells
• Environmental studies use thermodynamics to model climate change and its effects
  • Example: Greenhouse effect and global warming
• Thermodynamics is essential in the design of heating, ventilation, and air conditioning (HVAC) systems
  • Example: Heat pumps and refrigeration cycles

Problem-Solving Strategies

• Identify the system and surroundings, and determine the type of system (open, closed, or isolated)
• Determine the state functions (U, H, S, G) and path functions (Q, W) relevant to the problem
• Apply the appropriate laws of thermodynamics and thermodynamic relationships
  • Example: ΔU = Q + W for the First Law of Thermodynamics
• Use Hess's Law to calculate enthalpy changes for reactions when direct measurements are not possible
• Apply the Gibbs free energy equation (ΔG = ΔH - TΔS) to determine the spontaneity of a process
• For calorimetry problems, use the equation q = mcΔT to calculate heat transfer
  • Where q is heat, m is mass, c is specific heat capacity, and ΔT is the change in temperature
• When working with thermochemical equations, balance the equation and use stoichiometric coefficients to determine molar ratios
• Double-check units and ensure they are consistent throughout the problem