Gibbs Free Energy and Spontaneity

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Questions and Answers

Which conditions define the standard state for thermodynamic measurements?

  • 1M concentration of reactants and products, 25°C, and pH = 7 (correct)
  • Standard Temperature and Pressure (STP)
  • Any temperature and pressure, with concentrations at equilibrium
  • 0.1M concentration of reactants, 0°C, and any pH

The Gibbs free energy change (∆G) is calculated using what equation?

  • ∆G = -∆H + T∆S
  • ∆G = ∆H + T∆S
  • ∆G = ∆H - T∆S (correct)
  • ∆G = -∆H - T∆S

What does it mean if a reaction has a negative ∆G?

  • The reaction is endergonic and requires energy input to proceed.
  • The reaction is exergonic and can occur spontaneously. (correct)
  • The reaction is exothermic and releases heat.
  • The reaction is at equilibrium.

Which statement correctly describes an endergonic reaction?

<p>It causes an increase in the free energy of the system, with ∆G &gt; 0. (C)</p> Signup and view all the answers

For the reaction A <=> B, what is the value of ∆G at equilibrium?

<p>∆G = 0 (B)</p> Signup and view all the answers

How does increasing the temperature affect a reaction's spontaneity, assuming ∆H and ∆S are constant?

<p>It depends on the signs and magnitudes of both ∆H and ∆S. (A)</p> Signup and view all the answers

What is the role of ATP hydrolysis in coupled reactions?

<p>To provide energy for non-spontaneous reactions. (C)</p> Signup and view all the answers

Consider a reaction where ∆H is positive and ∆S is negative. Under what conditions, if any, will this reaction be spontaneous?

<p>This reaction will never be spontaneous. (D)</p> Signup and view all the answers

Given the triosephosphate isomerase reaction converts dihydroxyacetone phosphate (DHAP) to glyceraldehyde 3-phosphate (GA3P) with a ∆G = +7.67 kJ/mol, and knowing that $∆G = -RT\ln{K_A}$, how can the reaction proceed spontaneously in the cell?

<p>Because the forward reaction is unfavorable, but is driven by the next step in the pathway. (A)</p> Signup and view all the answers

If a chemical reaction has a $K_A$ value of 1000 $M^{-1}$, what does this indicate about the relative concentrations of reactants and products at equilibrium, and what would be the sign of $∆G$?

<p>More products than reactants, $∆G$ would be negative (D)</p> Signup and view all the answers

Flashcards

What is ∆Gº´?

The free energy change of a reaction under standard conditions: 1M concentration of reactants, 25°C (298 K), pH = 7 (for biological systems).

What is Gibbs Free Energy (∆G)?

The portion of a reaction's enthalpy change that is available to do work, accounting for entropy.

What is an Exergonic Reaction?

A reaction that can only occur spontaneously if the change in Gibbs free energy (∆G) is negative.

What is an Endergonic Reaction?

A reaction that cannot occur spontaneously because the change in Gibbs free energy (∆G) is positive.

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What is Equilibrium?

The point at which the rate of the forward reaction equals the rate of the reverse reaction, resulting in no net change in the ratio of reactants to products.

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What is cellular respiration?

A process where glucose is burned in oxygen to form carbon dioxide and water.

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What is a Coupled Reaction?

A reaction that releases free energy may be coupled to another reaction.

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What is the Equilibrium Constant (K A)?

The value of the ratio of product concentrations to reactant concentrations at equilibrium.

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What makes a reaction spontaneous?

Where the change in Gibbs free energy is negative and the reaction proceeds towards equilibrium.

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What is the equation for Gibbs Free Energy?

The change in Gibbs free energy is equal to the change in enthalpy minus the product of temperature and the change in entropy.

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Study Notes

  • The value of ΔG depends on reactant and product concentrations
  • Textbook values are for standard free energy change, denoted as ΔG°' (delta G nought prime)
  • ΔG°' is the free energy change in standard conditions: 1M concentration of reactants/products, 25°C (298 K), pH = 7 (biological systems)

Gibbs Free Energy Change

  • Both enthalpy and entropy changes determine if a reaction occurs
  • The equation ΔG = ΔH - TΔS defines changes in Gibbs free energy, representing the available energy from a reaction
  • T is temperature in Kelvin, and ΔG is measured in J mol⁻¹ (or kJ mol⁻¹)

Exergonic and Endergonic Reactions

  • Reactions can only occur spontaneously if ΔG is negative, indicating an exergonic reaction
  • Reactions cannot occur spontaneously if ΔG is positive, indicating an endergonic reaction.
  • Exergonic processes decrease the system's free energy (ΔG < 0), while endergonic processes increase it (ΔG > 0)
  • Exothermic processes decrease the system's enthalpy (ΔH < 0), while endothermic processes increase it (ΔH > 0)
  • Reactions can be exergonic and endothermic, meaning they are energetically favorable but enthalpically unfavorable

Spontaneous Reactions

  • Reactions occur spontaneously if ΔG is negative, but this does not indicate reaction rate

Equilibrium and ΔG

  • As reactions proceed towards equilibrium, the value of ΔG changes
  • At equilibrium, ΔG = 0

Triosephosphate Isomerase Equilibrium

  • For the reaction catalyzed by triosephosphate isomerase
  • Dihydroxyacetone phosphate ↔ Glyceraldehyde 3-phosphate,
  • The standard free energy change (ΔG) is +7.67 kJ mol⁻¹
  • The forward reaction is unfavorable

Chemical Reaction Equilibrium Thermodynamics

  • The combustion of hydrogen to form water: 2H₂ + O₂ = 2H₂O
  • ΔG = -237 kJ mol⁻¹, ΔH = -286 kJ mol⁻¹, TΔS = -49 kJ mol⁻¹
  • The combustion of glucose in oxygen: C₆H₁₂O₆ + 6O₂ = 6CO₂ + 6H₂O
  • ΔG = -2883 kJ mol⁻¹, ΔH = -2813 kJ mol⁻¹, TΔS = +70 kJ mol⁻¹

ATP and Coupled Reactions

  • ATP hydrolysis releases free energy, producing ADP (adenosine diphosphate) and inorganic phosphate (Pi): ATP + H₂O → ADP + Pi + H⁺
  • ΔG = -30.5 kJ mol⁻¹, making it a very favorable (exergonic) reaction
  • In cells, the actual free energy change is closer to -50 kJ mol⁻¹ due to non-unity concentrations
  • Hydrolyzed ADP is rapidly re-phosphorylated to regenerate ATP, maintaining constant ATP levels

Spontaneity in Cells

  • Cellular conditions are not standard (concentrations are typically 10⁻³ to 10⁻⁶ M), ΔG°' indicates reaction spontaneity.

Non-Spontaneous Reactions

  • Glutamate + NH₄⁺ → glutamine + H₂O (ΔG = +15 kJ mol⁻¹) is not spontaneous alone
  • ATP + H₂O → ADP + Pi + H⁺ (ΔG = -30 kJ mol⁻¹) is spontaneous

Coupled Reactions

  • Favorable processes that generate energy can drive unfavorable systems to allow that system
  • Free energy change = ΔG₁ - ΔG₂ (coupled reaction)
  • Unfavorable reactions are frequently linked to ATP hydrolysis:
  • Glutamate + NH₄⁺ → glutamine + H₂O; ΔG = +15 kJ mol⁻¹; (No)
  • ATP + H₂O → ADP + Pi + H⁺; ΔG = -30 kJ mol⁻¹; (Yes)

Chemical Equilibrium

  • For A + B ↔ AB, the equilibrium constant is KA = [AB]/([A]x[B])
  • ΔG = -RT ln KA; where ΔG is Gibbs free energy change, R is the gas constant, and T is temperature
  • ΔG = ΔH - TΔS; where ΔH is enthalpy change and ΔS is entropy change

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