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    Entropy: Spontaneity and Free Energy

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    heretolearnscience
    1. Entropy is a measure of disorder or randomness in a system. It increases as a system moves from an ordered to a more disordered state, such as from ice to liquid water to steam. 2. The second law of thermodynamics states that the entropy of the universe is always increasing, meaning all processes lead to greater disorder. 3. Gibbs free energy (G) can predict if a reaction will occur spontaneously. A negative ∆G value means the reaction is spontaneous.

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    Entropy: Spontaneity and Free Energy

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    heretolearnscience
    48 views25 pages
    1. Entropy is a measure of disorder or randomness in a system. It increases as a system moves from an ordered to a more disordered state, such as from ice to liquid water to steam. 2. The second law of thermodynamics states that the entropy of the universe is always increasing, meaning all processes lead to greater disorder. 3. Gibbs free energy (G) can predict if a reaction will occur spontaneously. A negative ∆G value means the reaction is spontaneous.

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    Entropy 2011

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    1. Entropy is a measure of disorder or randomness in a system. It increases as a system moves from an ordered to a more disordered state, such as from ice to liquid water to steam. 2. The second law of thermodynamics states that the entropy of the universe is always increasing, meaning all processes lead to greater disorder. 3. Gibbs free energy (G) can predict if a reaction will occur spontaneously. A negative ∆G value means the reaction is spontaneous.

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    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    48 views25 pages

    Entropy: Spontaneity and Free Energy

    Uploaded by

    heretolearnscience
    1. Entropy is a measure of disorder or randomness in a system. It increases as a system moves from an ordered to a more disordered state, such as from ice to liquid water to steam. 2. The second law of thermodynamics states that the entropy of the universe is always increasing, meaning all processes lead to greater disorder. 3. Gibbs free energy (G) can predict if a reaction will occur spontaneously. A negative ∆G value means the reaction is spontaneous.

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    ENTROPY

    Spontaneity and Free Energy

    ENTROPY
    Entropy

    is a term invented to keep track of the natural tendency for the components of the universe to become disordered. Entropy is defined as a measure of disorder or randomness. It is designated by the letter S and its unit is Joules per Kelvin, J/K
    2

    ENTROPY
    As

    randomness increases, S increases.

    Example: Ice molecules have a crystal lattice work of elements that vibrate around a fixed position. Liquid water molecules slip past one another. Steam molecules are widely dispersed. As ice melts to liquid water and evaporates as steam, the value of S increases.

    ENTROPY
    The

    second law of thermodynamics states that the entropy of the universe is always increasing. That means that all processes that occur in the universe lead to a net increase in the disorder of the universe.

    ENTROPY
    Entropy

    is a thermodynamic property because it describes the number of arrangements (positions and/or energy levels) that are available to a system existing in a given state. Entropy is also closely associated with probability. The more ways a particular state can be achieved the greater is the probability of finding that state.
    5

    ENTROPY
    Nature

    spontaneously proceeds toward the states that have the highest probabilities of existing. The objective of thermodynamics is to predict if a reaction will occur at specific conditions.
    Those

    conditions include temperature, pressure for gases, and concentration

    ENTROPY
    On

    an atomic or molecular scale, the concept of entropy can be applied: a. PHYSICAL STATES:

    For a given substance, entropy of a gas is greater than of a liquid or a solid, liquid is greater than solid. Entropy increases in reactions in which solids give liquid or gas products.
    7

    ENTROPY
    b.

    NUMBER OF PARTICLES:

    Entropy increases when a substance is divided into parts, therefore entropy is greater when the total number of product molecules is greater than the total number of reactant molecules. This is especially true with gaseous reactions.

    ENTROPY
    C.

    TEMPERATURE

    Entropy increases with a temperature increase because the molecular motion is more chaotic.

    D.

    MOLECULAR VOLUME/ENERGY LEVELS


    The

    larger the molecule or the more energy levels it possesses means an increase in entropy.
    9

    SUMMARY- ENTROPY REACTIONS


    1.

    Physical state change solid<liquid<gas 2. Atoms with more electrons or greater mass have greater entropy. 3. Certain processes: melting, vaporization, dissolving, heating increase entropy

    10

    SUMMARY- ENTROPY REACTIONS


    4.

    Equations with more product particles have increase in entropy. 5. Temperature change usually exothermic reactions have greater entropy.

    11

    ENTROPY UNITS
    The

    S. A. The units are J/K.( Joules / Kelvin) B. When calculated as a per mole substance, the unit is J/K.mol. C. The standard entropy of a substance in its most stable state at 25 C and 1 atm is S . Entropies of elements and compounds are positive.

    symbol for entropy of a substance is

    12

    ENTROPY IN REACTIONS

    Entropies change according to the physical state. If a reaction involves a change in state the entropy for the change is S = Sf - Si (f= final, I= initial) If the change results in an increase in disorder, then Sf is greater than Si. Sf and Si are positive but S can be either.

    13

    CALCULATING ENTROPY
    Calculating:
    Srxn

    aA + bB cC + dD

    Srxn = [cS (C) + dS (D)] [aS (A) + bS (B)]

    14

    SPONTANEOUS

    I. If a reaction occurs without outside intervention it is call spontaneous.

    Spontaneous processes may be fast or slow. Ex. A diamond should change spontaneously to graphite. The fact that we do not observe this process does not mean the prediction is wrong: it simply means the process is very slow.

    15

    SPONTANEOUS
    I.

    A spontaneous reaction occurs in only one direction. A spontaneous reaction takes place because it decreases the energy of the system. So, most ,but not all, exothermic reactions are spontaneous. And, a few endothermic reactions are spontaneous.
    16

    SPONTANEOUS
    Exothermicity favors spontaneity but does not guarantee it. Enthalpy is not the only predictor of spontaneity, Entropy is important. The driving force for a spontaneous process is an increase in the entropy of the universe.

    17

    SPONTANEITY
    Suppose a reaction is exothermic but involves an increase in order. The H is negative and the S is small or negative. The entropy change tends to prevent the reaction from occurring and the enthalpy change tends to make it occur spontaneously, how can you decide if it will occur?
    18

    Gibbs Free Energy


    Gibbs Free Energy named for Josiah Gibbs, physics professor at Yale 1871-1903. Gibbs introduced a quantity called free energy that will indicate whether a reaction will occur or not. It is a physical state function. Symbol is G.

    19

    FREE ENERGY AND WORK

    Free energy is that energy free to do work. It is the maximum amount of work possible at a given temperature and pressure. It is never really achieved because some of the free energy is changed to heat during a reaction, so it cant be used to do work.

    20

    GIBBS FREE ENERGY


    G is the change in Gibbs free energy. G is defined in terms of enthalpy and entropy. Unit is kJ for Grxn and kJ/mol for Gf G = H TS (T = temp in K) G = H TS It can be shown, by experiments and in theory, that in a spontaneous change, G is always negative.

    21

    GIBBS FREE ENERGY

    If a reaction takes place at a low temp and involves little change in entropy (S), then TS is negligible and G is reliant on H (change in enthalpy). So most reactions occurring at room temp have a negative H. Highly endothermic reactions can occur only if TS is large. (T can be high or S can be high)
    22

    GIBBS FREE ENERGY


    H and S have same sign, there will be some temp at which H and TS will be numerically equal and G will be exactly zero. This is the thermodynamic definition of equilibrium.
    If

    23

    GIBBS FREE ENERGY


    1.

    Summary: G is neg = spontaneous reaction G is pos = nonspontaneous reaction G = 0 means equilibrium

    24

    G= H-T S
    S H

    Spontaneous?

    + + -

    At all Temperatures
    At high temperatures, entropy driven At low temperatures, enthalpy driven Not at any temperature, Reverse is spontaneous
    25

    + +

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