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    Chapter 23-Entropy & Gibbs Energy

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    WENDY MENDIOLA
    Entropy is a measure of disorder in a system. It increases when energy is dispersed from a system to its surroundings. Reactions that increase the total entropy are more likely to be spontaneous. Calculating entropy changes involves determining the entropy changes of the system and surroundings separately and adding them to find the total entropy change. If total entropy increases, the reaction is feasible and will proceed spontaneously. Temperature also affects entropy, with higher temperatures generally resulting in higher entropy states.

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    Chapter 23-Entropy & Gibbs Energy

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    WENDY MENDIOLA
    49 views26 pages
    Entropy is a measure of disorder in a system. It increases when energy is dispersed from a system to its surroundings. Reactions that increase the total entropy are more likely to be spontaneous. Calculating entropy changes involves determining the entropy changes of the system and surroundings separately and adding them to find the total entropy change. If total entropy increases, the reaction is feasible and will proceed spontaneously. Temperature also affects entropy, with higher temperatures generally resulting in higher entropy states.

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    CHAPTER 23-ENTROPY & GIBBS ENERGY

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    Entropy is a measure of disorder in a system. It increases when energy is dispersed from a system to its surroundings. Reactions that increase the total entropy are more likely to be spontaneous. Calculating entropy changes involves determining the entropy changes of the system and surroundings separately and adding them to find the total entropy change. If total entropy increases, the reaction is feasible and will proceed spontaneously. Temperature also affects entropy, with higher temperatures generally resulting in higher entropy states.

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    Download as pptx, pdf, or txt
    49 views26 pages

    Chapter 23-Entropy & Gibbs Energy

    Uploaded by

    WENDY MENDIOLA
    Entropy is a measure of disorder in a system. It increases when energy is dispersed from a system to its surroundings. Reactions that increase the total entropy are more likely to be spontaneous. Calculating entropy changes involves determining the entropy changes of the system and surroundings separately and adding them to find the total entropy change. If total entropy increases, the reaction is feasible and will proceed spontaneously. Temperature also affects entropy, with higher temperatures generally resulting in higher entropy states.

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    ENTROPY AND GIBBS

    FREE ENERGY
    CHAPTER 23:
    The Laws of Thermodynamics, Entropy, and Gibbs Free
    Energy

     https://
    www.youtube.com/watch?v=8N1BxHgsoOw
    What is entropy? - Jeff Phillips

     https://www.youtube.com/watch?v=YM-uykVfq_E
    Introducing entropy

     Entropy is a measure of the  The system of magnesium reacting


    dispersal of energy at a specific with sulfuric acid in a test tube to
    temperature. Entropy can also be form magnesium sulfate and
    thought of as a measure of the hydrogen releases energy to the
    randomness or disorder of a surroundings. The surroundings
    system. The higher the randomness include:
    or disorder, the greater the  ■■ the solvent (in this case water)
    entropy of the system.
     ■■ the air around the test tube
     A system is the part under
    investigation. In chemistry this is  ■■ the test tube itself
    the chemical reaction itself, i.e.  ■■ anything dipping into the test
    reactants being converted to tube (e.g. a thermometer).
    products.
    Introducing entropy

     Changes that tend to continue to  Entropy can also be thought of as a


    happen naturally are called dispersal of energy, either from
    spontaneous changes. the system to the surroundings or
     When a light is applied, methane gas from the surroundings to the
    reacts with oxygen in a spontaneous system. The system becomes
    reaction to form carbon dioxide and energetically more stable when it
    water. The reaction is spontaneous becomes more disordered.
    because the methane continues to burn
    in the oxygen until either the methane
    or oxygen is completely used up. For a
    reaction to be spontaneous, it does not
    need to happen rapidly. Many
    spontaneous reactions are slow or need
    an input of energy to start them.
    Chance and spontaneous change

     Diffusion If you spill a few drops of


    perfume in a closed room with no air
    draughts, the smell spreads gradually
    throughout the room. The molecules
    in the perfume vapour, which are
    responsible for the smell, move
    randomly in straight lines until they
    collide with air molecules, other
    perfume molecules or with the walls
    of the room. After collision, the
    perfume molecules change direction.
    This process of random movement and
    random collisions of molecules is
    called diffusion.
    Diffusion and number of ways
    Comparing entropy values

     To make any comparison of  ■■ a pressure of 105Pa


    entropy values fair, we must  ■■ a temperature of 298K (25
    use standard conditions. These °C)
    standard conditions are the
    same as those used for ΔH:  ■■ each substance involved in
    the reaction is in its normal
    physical state (solid, liquid or
    gas) at 105Pa and 298K.
    From the values in the table and other
    data we can make some generalisations:
     Gases generally have much higher entropy values than liquids, and liquids
    have higher entropy values than solids. There are exceptions to this. For
    example, calcium carbonate (solid) has a higher entropy value than
    mercury (liquid).

     Simpler substances with fewer atoms have lower entropy values than more
    complex substances with a greater number of atoms. For example, for
    calcium oxide, CaO, S —O(standard entropy) = 39.7 JK–1mol–1 but for
    calcium carbonate, CaCO3, S —O(standard entropy) = 92.9 JK–1mol–1.
    Carbon monoxide, CO, has a lower entropy value than carbon dioxide,
    CO2.
    From the values in the table and other
    data we can make some generalisations:
     For similar types of substances, harder substances have a lower entropy value. For example,
    diamond has a lower entropy value than graphite and calcium has a lower entropy value than lead.

     For a given substance the entropy increases as a solid melts and then changes to a vapour (see
    Figure 23.5). For example, the molar entropy of ice just below its melting point is 48.0 JK–1mol–1;
    the molar entropy for water is 69.9 JK–1mol–1, but just above its boiling point, the value increases
    to 188.7 JK–1mol–1.
     There is a gradual increase in entropy as the temperature of a substance is increased. Increasing
    the temperature of a solid makes the molecules, atoms or ions vibrate more. Increasing the
    temperature of a liquid or gas increases the entropy because it increases the disorder of the
    particles.
     When a substance melts or vaporises, there is a large increase in entropy because there is a very
    large increase in the disorder of the particles.
    When a solid changes to a liquid:

    ■ the regularly arranged lattice of particles close


    together in the solid changes to

     ■■an irregular arrangement of particles, which


    are close together but rotate and slide over each
    other in the liquid.
    When a liquid changes to a vapour:

     ■■ the irregular arrangement of


    particles in the liquid which are
    close together and rotating changes
    to

     ■■ an irregular arrangement of
    particles, which are free to move
    around rapidly because they are far
    apart from each other.
    Entropy changes in reactions
     In a chemical reaction, if we compare the entropies of the reactants and
    products, we can try to explain the magnitude of the entropy change and
    whether or not it increases or decreases.
     We will assume that gases have high entropy and solids have low entropy. If
    there is a change in the number of gaseous molecules in a reaction, there is
    likely to be a significant entropy change. This is because high values of
    entropy are associated with gases. The more gas molecules, there are, the
    greater is the number of ways of arranging them and the higher the entropy.
    For example in the reaction:
    Calculating entropy changes

    Entropy changes in exothermic and endothermic reactions

     ■ For an exothermic reaction, the energy released to the surroundings


    increases the number of ways of arranging the energy. This is because the
    energy goes into rotation and translation (movement from place to place) of
    molecules in the surroundings. So there is likely to be an increase in entropy
    and an increased probability of the chemical change occurring spontaneously.

     ■■ For an endothermic reaction, the energy absorbed from the surroundings


    decreases the number of ways of arranging the energy. So there is likely to be
    a decrease in entropy and a decreased probability of the chemical change
    occurring spontaneously.
    Total entropy change

     If the total entropy change


    increases, the entropy change is
    positive, e.g. ΔS —O total is +40
    JK–1mol–1 . The reaction will then
    occur spontaneously. We say that
    the reaction is feasible.
     If the total entropy change
    decreases, the entropy change is
    negative, e.g. ΔS —O total is –40
    JK–1mol–1. The reaction is then not
    likely to occur.
    Calculating the entropy change of the system
    Calculating the entropy change of the system
    Calculating the entropy change of the
    surroundings
    Calculating the entropy change of the
    surroundings
    Calculating total entropy change
    Entropy in equilibrium reactions

     As mixing proceeds, the rate of


    increasing disorder decreases as
    more and more NO2 molecules
    are formed from N2O4. At some
    stage in the reaction, the rate of
    the forward reaction equals the
    rate of the backward reaction.
    Equilibrium has been reached.
    Entropy and temperature

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