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Questions and Answers

What condition must be met for a system to be considered at equilibrium?

  • ΔS > 0
  • ΔG = 0 (correct)
  • ΔH < TΔS
  • ΔG < 0
  • What does the equation ΔG° = -RTlnKeq indicate?

  • The temperature dependence of ΔG at constant pressure.
  • The change in entropy at equilibrium.
  • The relationship between the change in free energy and equilibrium constant. (correct)
  • The relationship between ΔG° and the standard reaction quotient.
  • Which statement accurately describes the implications of ΔG° being greater than zero?

  • The reverse reaction is not favored.
  • The reaction will not occur spontaneously. (correct)
  • The reaction is at equilibrium.
  • The reaction is spontaneous in the forward direction.
  • Which of the following equations reflects the relationship necessary for a spontaneous process?

    <p>ΔG = ΔH - TΔS</p> Signup and view all the answers

    What is the condition for a process to be spontaneous according to Gibbs free energy?

    <p>ΔG &lt; 0</p> Signup and view all the answers

    What must the relationship between ΔG and Keq be at equilibrium?

    <p>ΔG° = 0</p> Signup and view all the answers

    In a process controlled by enthalpy, what would be the characteristics of ΔH and ΔG?

    <p>ΔH large and negative; ΔG small and negative</p> Signup and view all the answers

    For a reaction where the change in Gibbs free energy is zero, which of the following statements is true?

    <p>The concentrations of reactants and products are constant.</p> Signup and view all the answers

    What happens to the Gibbs free energy (ΔG) at chemical equilibrium?

    <p>ΔG = 0</p> Signup and view all the answers

    Given that ΔS represents entropy, which condition must be satisfied for a process to favor an increase in disorder?

    <p>ΔG &lt; 0</p> Signup and view all the answers

    What is the significance of a large positive ΔS in a process?

    <p>It can drive a spontaneous process despite unfavorable ΔH</p> Signup and view all the answers

    If isomerization of glucose-6-phosphate results in ΔG° of 2.1 kJ mol−1, what does this suggest about the reaction favorability under standard conditions?

    <p>The reaction does not favor product formation.</p> Signup and view all the answers

    For the reaction ATP → ADP + Pi with ΔG° = -30.5 kJ mol-1, what does this indicate about the reaction?

    <p>The reaction is spontaneous under standard conditions</p> Signup and view all the answers

    What is the significant condition for a spontaneous process at constant temperature and pressure?

    <p>ΔH - TΔS &lt; 0</p> Signup and view all the answers

    What does the term 'irreversible change' in a spontaneous process imply?

    <p>The reaction continues in one direction without reversing.</p> Signup and view all the answers

    In the unfolding of a protein with ΔH° = 250.8 kJ mol−1 and ΔS° = 752 J K−1 mol−1, above what temperature will the process be spontaneous?

    <p>Approximately 332.1 °C</p> Signup and view all the answers

    What is the standard state of free energies denoted by G°?

    <p>Value of G for a pure substance under specific conditions</p> Signup and view all the answers

    If ΔH is small and positive, and ΔS is significant and positive, what inference can be made about the overall process?

    <p>The process can still be spontaneous due to high entropy change</p> Signup and view all the answers

    How does temperature (T) influence the balance between ΔH and ΔS in determining ΔG?

    <p>Amplifies the effect of ΔS with increasing T</p> Signup and view all the answers

    Study Notes

    Equilibrium

    • Equilibrium is defined by equilibrium constants (Keq)
    • Equilibrium constants predict the structure of systems
    • Systems are stable at equilibrium
    • Systems are unstable when not at equilibrium

    Energy

    • Energy is defined by the first law ( enthalpy, H ) and second law (entropy, S) of thermodynamics
    • The change in Gibbs Free Energy (G) = H – TS
    • A system is at equilibrium when G = 0
    • A system undergoes spontaneous change when G < 0

    Relationship between ΔG and Keq

    • At equilibrium, G° = −RTlnKeq
    • This relationship holds true at equilibrium
    • When not at equilibrium, use G − G° = RTlnKeq
    • G is the free energy of the system
    • G° is the free energy of the process at equilibrium

    Tutorial: ΔG, Keq problem

    • The concentration of a solution of G3P was initially 0.05 M.
    • Isomerase was added.
    • After the mixture reached equilibrium at 25 °C, the concentration of G3P was 0.002 M.
    • ΔG° for the reaction can be calculated using the given data

    Energy and Equilibrium of Systems

    • The first law of thermodynamics states that enthalpy (H) is equal to the heat (qp) transferred at constant pressure, or:
      • H = qp= U + PV
    • Enthalpy concerns energy changes to the system during processes
    • Processes that lower enthalpy are favored
    • The second law of thermodynamics states that entropy (S) is equal to the heat (q) transferred divided by the temperature (T), or:
      • S = q
    • Entropy concerns changes in the disorder of the system during processes
    • Processes that increase entropy are favored
    • We need a thermodynamic concept that captures both of these concepts

    Criterion for the Direction of Spontaneous Change

    • For any spontaneous process at constant T and P:
      • S > 𝑞𝑖𝑟𝑟𝑒𝑣  𝑇 or qirrev < TS
    • A spontaneous process implies irreversible change
    • q = H (const.T, P)
    • Therefore, H < TS or H − TS < 0
    • The process will continue as long as H − TS < 0

    Gibbs Free Energy

    • We need a relationship such that H − TS < 0
    • Define Gibbs Free Energy as G = H − TS
    • The process will proceed as long as G < 0
    • G is known as the Gibbs free energy
    • G is a thermodynamic state function

    ΔG = ΔH − TΔS

    • If G < 0, the process is favored in that direction
    • Equilibrium is reached when G = 0
    • If the H term dominates, have an enthalpy controlled process ( H large and –ve)
    • If the TS term dominates, have an entropy controlled process

    Enthalpy vs. Entropy

    • The analysis of Mg2+ using complexation by EDTA is a good example
    • EDTA tetra sodium salt is widely used for the analysis of Mg ions in aqueous solution
    • Mg2+ ion is highly solvated by water
    • The method is used pharmaceutically, in pharmacology, biochemistry, etc.
    • Note, that the process goes essentially to completion i.e., fully to the right-hand side as drawn above

    Enthalpy vs. Entropy

    • Can determine the relative contributions of enthalpy and entropy to the process.
    • We can determine the thermodynamic driving forces for the process and…
    • …infer the molecule-level processes
    • We find that H is small and +ve
    • But that S is significant and +ve
    • The release of five H2O molecules and two NaCl increases disorder, leading to more components generated
    • Overall G is –ve, making the process spontaneous from left to right as drawn

    Standard States of Free Energies

    • G°: is the value of G for a pure substance under 1 atmosphere of pressure, at a specified temperature
    • G°: is the change in free energy when 1 mole of products in their standard states are converted to 1 mole of products in their standard states

    Using ΔG Values, Example

    • ATP, ADP, and AMP are key molecules in biochemical energy transfer
    • We can use standard free energy values to calculate the change in free energy for a reaction

    Tutorial: ΔG = ΔH − TΔS

      1. ATP → ADP + Pi G° = −30.5 kJ mol−1
      • (from thermal analysis, H° = −20.1 kJ mol−1)
      • Calculate S° at 37 °C
      • Comment on the significance of G, H and S values.
      1. H° and S° for the unfolding of a protein are 250.8 kJ mol−1 and 752 J K−1 mol −1 respectively.
      • Above what temperature (in °C) will unfolding of the protein be spontaneous?
      • Comment on the values.

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