Scribd Logo
Upload

Welcome to Scribd!

  • Kuliah 4 - Thermodynamics 2017 PDF

    Uploaded by

    Goblin Ikan
    4 views35 pages

    Original Title

    88241_Kuliah 4 - thermodynamics 2017.pdf

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Report this Document

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Flag for inappropriate content
    4 views35 pages

    Kuliah 4 - Thermodynamics 2017 PDF

    Uploaded by

    Goblin Ikan

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Flag for inappropriate content
    of 35

    THERMODYNAMICS &

    CHEMICAL EQUILIBRIUM
    Basic Geochemistry Teaching Team
    FTG
    2017
    GEOCHEMICAL SYSTEM
    geochemical system is an open system that may be studied within 2 basic
    frameworks:
    ➤ thermodynamic system
    a state of equilibrium where environmental parameters, such as
    pressure and temperature, are imposed on the bulk composition of the
    system. This approach is used to predict the system stability and the impact
    of changing environmental condition
    ➤ kinetic system
    wherein the pathway along the system are moving toward some state of
    local equilibrium, which in turn determines the rate of change along the
    pathway. in the context of kinetic approach, which is relevant to geochemical
    process, dissolution-precipitation, exchange-adsorption, oxidation-reduction,
    vaporisation and formation of new phases.
    “
    THERMODYNAMICS
    Thermodynamics
    a system:
    Some portion of the universe that you wish to study

    the surroundings:
    The adjacent part of the universe outside the system

    Changes in a system are associated with the transfer of energy


    Energy States

    Unstable:
    falling or rolling

    Stable:
    at rest in lowest energy state

    Metastable:
    in low-energy perch

    Figure 5-1. Stability states. Winter (2001) An


    Introduction to Igneous and Metamorphic Petrology.
    Prentice Hall.
    A review of basic thermodynamics: A refresher

    The ball represents


    mass exchange

    The arrow represents


    energy exchange
    THERMODYNAMICS
    study about the “heat” (thermo) and “work” (dynamics)
    First law of thermodynamics:
    ➤ Energy is neither created nor destroyed.
    ➤ In other words, the total energy of the universe is a constant;
    if the system loses energy, it must be gained by the
    surroundings, and vice versa.
    The First Law of Thermodynamics
    • Heat and work are equivalent

    • Energy is conserved in any transformation

    • The change of energy of a system is independent of the path taken

    Energy can be neither created nor destroyed


    ΔE = q - w or dE = dq - dw dE = dq - P dV

    E = internal energy P = pressure


    q = heat V = volume
    w = work
    Enthalpy
    dE = dq - P dV
    H = E + PV
    dH = dq

    H = enthalpy

    The change in the enthalpy of a system (ΔH) during a reversible


    change in state at constant pressure is equal to the heat absorbed
    by the system during that change in state.

    The enthalpy of formation of compounds and their ions and


    molecules in aqueous solution is the heat absorbed or given off by
    chemical reactions in which the compounds, ions, and molecules
    form from the elements in the standard state (25°C, 1 atm)
    Heats of Reaction

    ΔH = Σ nH (products) - Σ nH (reactants)

    n = molar coefficient of each reactant/product

    When ΔH is positive, the reaction is endothermic (heat flows


    from the surroundings to the system);

    When ΔH is negative, the reaction is exothermic (heat flows


    from the system to the surroundings
    Heats of Reaction

    ΔH = Σ nH (products) - Σ nH (reactants)

    For example, evaporation: H2O(l) H2O(g)

    ΔH = H(H2O(g)) - H(H2O(l))
    ΔH = (-57.80) - (-68.32) = 10.52 kcal
    The reaction is endothermic (i.e., sweating is a mechanism
    for cooling the body)
    Heat Capacity
    When heat is added to a solid, liquid, or gas, the temperature
    of the substance increases:

    dq = C dT
    dq = dH
    dH = C dT, at constant pressure (important in geochemistry)

    C = heat capacity
    T = temperature

    Heat capacities vary with temperature…


    The Second Law of Thermodynamics:
    Entropy
    The entropy of the universe always increases
    ΔS = Σ nS (products) - Σ nS (reactants)

    For example: H2O(l) H2O(g)

    ΔS = S(H2O(l)) - S(H2O(g))
    ΔS = 45.10 - 16.71 = 28.39 cal/deg
    When ΔS is positive, entropy of the system increases with
    the change of state;

    When ΔS is negative, entropy decreases


    THE THIRD LAW OF THERMODYNAMICS
    the entropy of a perfectly crystalline
    material at the absolute zero (0 K) is zero
    ➤ entropy allows prediction of the feasibility of reactions
    “
    CHEMICAL EQUILIBRIUM
    “
    FREE ENERGY
    Gibbs Free Energy
    Gibbs free energy is a measure of chemical energy

    All chemical systems tend naturally toward states of


    minimum Gibbs free energy

    G = H - TS
    Where:
    G = Gibbs Free Energy
    H = Enthalpy (heat content)
    T = Temperature in Kelvins
    S = Entropy (can think of as randomness)
    Gibbs Free Energy
    • Products and reactants are in equilibrium when their Gibbs
    free energies are equal

    • A chemical reaction will proceed in the direction of lower


    Gibbs free energy (i.e., ΔGr < 0)

    …so the reaction won’t proceed if the reaction produces


    an increase in Gibbs free energy
    Gibbs Free Energy

    ΔG°r = ΣnG°f (products) - ΣnG°f (reactants)

    ΔG°r > 0, backwards reaction with deficient energy


    ΔG°r < 0, forwards reaction with excess energy
    ΔG°r = 0, reaction is in equilibrium
    ΔG°r is a measure of the driving force
    Thermodynamics
    Summary thus far:
    – G is a measure of relative chemical stability for a phase
    – We can determine G for any phase by measuring H and S for
    the reaction creating the phase from the elements

    If we know G for various phases, we can determine which is most


    stable
    • Why is melt more stable than solids at high T?
    • Is diamond or graphite stable at 150 km depth?
    • What will be the effect of increased P on melting?

    You might also like