Chemistry Chapter on Thermodynamics and Equilibrium
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Questions and Answers

Which factor contributes to the negative enthalpy change in the formation of liquid water from gaseous hydrogen and oxygen?

  • Increase in temperature during the reaction
  • Increase in molecular complexity
  • Increase in the number of gas moles
  • Decrease in the number of moles from 3 to 2 (correct)
  • In the context of chemical reactions, what does the reaction quotient (Q) quantify?

  • The concentration of reactants only
  • The ratio of product concentrations to reactant concentrations (correct)
  • The equilibrium constant of a reaction
  • The total moles of all substances involved
  • What happens to the entropy of a substance as it transitions from solid to gas?

  • It remains constant
  • It decreases significantly
  • It increases dramatically (correct)
  • It first decreases and then increases
  • Which of these reactions would likely have a positive entropy change (ΔS > 0)?

    <p>Sublimation of dry ice into carbon dioxide gas</p> Signup and view all the answers

    What does the subscript 'P' in the equilibrium constant Kp refer to?

    <p>Pressure</p> Signup and view all the answers

    Which expression relates Kp and Kc in a chemical equilibrium?

    <p>Kp = Kc(RT) ∆n</p> Signup and view all the answers

    According to Le Châtelier's principle, what will happen if the concentration of a product is increased in a system at equilibrium?

    <p>The equilibrium will favor the formation of more reactants.</p> Signup and view all the answers

    What does the term 'Kw' conventionally refer to?

    <p>Equilibrium constant for water</p> Signup and view all the answers

    If 0.0150 M of butane is added to a system at equilibrium with an initial concentration of 0.0050 M, what is the adjusted expression for butane at equilibrium?

    <p>0.0050 + 0.0150 - x</p> Signup and view all the answers

    What effect does changing the volume of a gaseous system at equilibrium have according to Le Châtelier's principle?

    <p>It will favor the side with fewer moles of gas.</p> Signup and view all the answers

    What will be the final equilibrium concentrations if the original concentrations are [butane] = 0.0050 M and [isobutane] = 0.0125 M after adding 0.0150 M butane?

    <p>[butane] = 0.0200 - x M, [isobutane] = 0.0125 + x M</p> Signup and view all the answers

    When a system at equilibrium experiences a stress, what is the result according to Le Châtelier's principle?

    <p>The system shifts to minimize the effect of the stress.</p> Signup and view all the answers

    What is the definition of a state function?

    <p>A property that only depends on the current state of the system.</p> Signup and view all the answers

    Which of the following is a path function?

    <p>Work (w)</p> Signup and view all the answers

    What does $ rac{d}{f}H°$ represent?

    <p>Enthalpy of formation for 1 mole of a compound from elements</p> Signup and view all the answers

    According to the Second Law of Thermodynamics, what occurs in a spontaneous process?

    <p>Entropy of the universe increases.</p> Signup and view all the answers

    What is the standard state condition for the enthalpy of formation?

    <p>1 atm, 1 M, 25 °C, all phases</p> Signup and view all the answers

    What happens to the entropy of a perfect crystal as temperature approaches 0 K?

    <p>It approaches 0.</p> Signup and view all the answers

    What is the significance of the activation energy (Ea) in the Arrhenius equation?

    <p>It reflects the energy required for a reaction to occur.</p> Signup and view all the answers

    In the reaction $N_2(g) + 3 H_2(g) \rightarrow 2 NH_3(g)$ with $ riangle H° = -92.22 kJ$, which thermochemical equation represents the formation of 1 mol of NH3(g)?

    <p>$N_2(g) + 3 H_2(g) \rightarrow NH_3(g) + 46.11 kJ$</p> Signup and view all the answers

    How does temperature affect entropy?

    <p>Entropy increases with increasing temperature.</p> Signup and view all the answers

    Which factor does NOT affect the rate of a chemical reaction according to collision theory?

    <p>The presence of a catalyst</p> Signup and view all the answers

    In the Arrhenius equation, what does the constant A represent?

    <p>The frequency of collisions and orientation probability</p> Signup and view all the answers

    What must happen after the substrate binds to the enzyme for the reaction to proceed?

    <p>The chemical reaction must occur.</p> Signup and view all the answers

    Which of the following statements about the Arrhenius equation is accurate?

    <p>A and Ea vary depending on the specific reaction.</p> Signup and view all the answers

    Which model describes the interaction between substrates and enzymes where the enzyme undergoes a conformational change?

    <p>Induced fit model</p> Signup and view all the answers

    What is the likely outcome when a catalyst is added to a reaction?

    <p>It increases the fraction of effective collisions.</p> Signup and view all the answers

    What happens to the rate of a chemical reaction as temperature increases according to the Arrhenius equation?

    <p>The rate constant k increases.</p> Signup and view all the answers

    For a first-order reaction, how is the rate law expressed?

    <p>Rate = k[R]</p> Signup and view all the answers

    What is the mathematical expression for the integrated rate law of a first-order reaction?

    <p>ln[R] - ln[R]0 = kt</p> Signup and view all the answers

    What is the half-life expression for a first-order reaction?

    <p>t1/2 = 0.693/k</p> Signup and view all the answers

    Which of the following indicates the relationship between half-life and concentration for first-order reactions?

    <p>Half-life is independent of concentration.</p> Signup and view all the answers

    What does the activation energy represent in a chemical reaction?

    <p>The minimum energy needed for a reaction to occur.</p> Signup and view all the answers

    In the reaction of NO2 and CO, what is the activation energy barrier for the forward reaction?

    <p>132 kJ/mol-rxn</p> Signup and view all the answers

    What is the net energy change for the reaction of NO2 and CO?

    <p>-226 kJ/mol-rxn</p> Signup and view all the answers

    What is the best interpretation of the Gibbs free energy change (ΔG°) for a chemical reaction?

    <p>It determines the extent to which a reaction can occur spontaneously.</p> Signup and view all the answers

    Which of the following statements about standard molar free energies of formation (ΔfG°) is accurate?

    <p>ΔfG° equals zero for elements in their standard states.</p> Signup and view all the answers

    When calculating ΔG° for the reaction of propane ( ext{C3H8}) combustion, which factor significantly influences the outcome?

    <p>The standard free energy changes of the products and reactants.</p> Signup and view all the answers

    How does an increase in temperature generally affect the Gibbs free energy change (ΔG°) of an exothermic reaction?

    <p>It always increases ΔG° and therefore favors the reverse reaction.</p> Signup and view all the answers

    In nont-standard state conditions, how do pressure and concentration impact the Gibbs free energy change (ΔG)?

    <p>Higher pressure decreases ΔG, favoring product formation.</p> Signup and view all the answers

    Study Notes

    Course Information

    • Course name: Applied Introductory and Physical Chemistry
    • Course code: CHEM 10130
    • Year: Autumn 2024
    • Institution: UCD School of Chemistry, University College Dublin (UCD)

    Topics covered

    • Sources of energy and nature of energy transfer
    • Nature of work and heat
    • Nature of enthalpy and entropy
    • Nature of spontaneous processes and relationship to Gibbs free energy
    • Nature of equilibrium reactions and the equilibrium constant
    • Nature of binding reactions
    • Nature of the relationship between equilibria and Gibbs free energy
    • Nature of rates of reaction and relationship to collision theory
    • Nature of activation energy and catalysis
    • Nature of enzymes, enzyme kinetics, and enzyme inhibition

    What is Energy?

    • Energy is the capacity to supply heat or do work.
    • Energy can be converted from one form to another, but the total energy remains the same.
    • During a chemical or physical change energy cannot be created or destroyed, although it can change form.
    • The First Law of Thermodynamics states Energy can neither be created nor destroyed.
    • The total energy of the universe is constant.

    Heat and Specific Heat Capacity

    • Heat (q) is energy gained or lost as heat.
    • Specific heat capacity (C) is the heat required to raise the temperature of one gram of a substance by one degree Celsius (or Kelvin).

    Energy and Changes of State

    • Heat of fusion is the energy transferred as heat to convert a substance from a solid to a liquid at its melting point.
    • Heat of vaporization is the energy transferred as heat to convert a substance from a liquid to a gas at its boiling point.
    • Temperature is constant during a change of state.

    Enthalpy (H)

    • Enthalpy is the heat content of a chemical reaction carried out at constant pressure.
    • ∆H is the change in enthalpy.
    • ∆H = Hfinal - Hinitial = qp
    • ∆H is a state function.
    • ∆H= Hproduct - Hreactant

    What is a State Function?

    • A state function is a system property that depends only on the system's current state, not how it reached that state.
    • Examples include energy and enthalpy.
    • Work and heat are not state functions, as their values depend on the path taken.

    Hess's Law and Energy diagrams

    • Manipulate the equation by adding or subtracting reactions to find different enthalpy changes, which can then be added and subtracted to give the enthalpy change for the final reaction.
    • Add and subtract reactants and products.
    • What you do to reactants and products must be done to the enthalpy values.
    • Cancel what appears on both sides of an equation.
    • Look at what needs to be cancelled and placed on the correct side.
    • Focus on numbers last.

    ΔH° is the enthalpy of formation

    • ΔH° is the heat required to form one mole of a compound from its elements in their standard states.
    • Standard conditions: 1 atm, 1 M, s, l, g
    • ΔH° of an element is zero (by definition).

    Predicting Spontaneity under standard conditions

    • This table predicts whether a reaction is spontaneous under standard conditions by considering if enthalpy (ΔH°) and entropy (ΔS°) are positive or negative.

    Quantifying Entropy Changes

    • Entropy is the measure of disorder in a system.
    • Entropy increases with increasing temperature.

    Reaction Quotient

    • For a general chemical reaction, aA + bB ⇌ cC + dD, the reaction quotient can be expressed in terms of either the molar concentrations or partial pressures.

    Different equilibrium constants

    • Equilibrium constants can be expressed in terms of either molar concentrations or partial pressures.
    • The relationship between the constants is Kp = Kc(RT)∆n

    Disturbing a Chemical Equilibrium: Le Châtelier's principle

    • Equilibrium can be disturbed by changing temperature, concentration, or volume (for systems involving gases).
    • If a stress is applied to a system in equilibrium, the system will shift in a direction that reduces the stress.

    What is pH?

    • pH stands for "potentia hydrogenii" (power of Hydrogen).
    • p[H+] = -log10[H+]

    Equilibrium constant of water

    • 2H₂O ⇌ H₃O⁺ + OH⁻
    • Kw = [H₃O⁺] [OH⁻]/[H₂O]₂
    • The equilibrium constant at 25°C is Kw =1.0 x 10⁻¹⁴ mol²/L²

    Henderson-Hasselbalch equation

    • pH = pKa + log10([A⁻]/[HA]), where HA is the acid and A⁻ is its conjugate base.

    Gibbs Free Energy

    • Nature favors processes with negative enthalpy (-H) and positive entropy (+S).
    • The Gibbs free energy (G) predicts if a process is spontaneous.
    • ΔG = ΔH - TΔS where ΔH is enthalpy change, ΔS is entropy change, and T is temperature.

    How can we calculate the Gibbs Free Energy?

    • ΔG° is a state function.
    • ΔG° = Σn∆G°(products) – Σm∆G°(reactants)
    • ΔG° = ΔH° − TΔS°
    • Enthalpy (ΔH°) and entropy (ΔS°) changes at standard state conditions.

    Reaction Rate and Stoichiometry

    • Rate = change in concentration/change in time
    • aA + bB → cC + dD -1/aΔ[A]/Δt = -1/bΔ[B]/Δt = 1/cΔ[C]/Δt = 1/dΔ[D]/Δt
    • Rate of reaction is the change in concentration of a reactant or product over the change in time.

    Example: Peroxide decomposition

    • 2H2O2 → 2H2O + O2
    • Rate of peroxide decomposition can be calculated

    Integrated Rate Laws

    • Integrated rate laws relate reactant concentration to time for zero-order, first-order, and second-order reactions.
    • The rate of a zero-order reaction is constant.

    For 1st order reaction

    • For a first-order reaction, the half-life is independent of concentration.

    Activation energy (Ea)

    • The activation energy is the minimum energy required for a reaction to occur.

    Collision theory

    • Reaction rates are affected by collisions among molecules, the correct orientation of colliding molecules, and the energy of colliding molecules.

    Arrhenius equation

    • The Arrhenius equation relates the rate constant (k) to temperature (T), activation energy (Ea), and the frequency factor (A).
    • k = Ae-Ea/RT.

    Catalysis

    • Catalysts increase reaction rates by lowering the activation energy.
    • Enzymes are biological catalysts.

    Enzymes – Nature's catalysts

    • Enzymes are biological catalysts that accelerate reactions.
    • The reactant (substrate) binds to the enzyme, the chemical reaction takes place at the active site, and the products leave, repeating the cycle.

    Models for substrate binding to enzymes

    • Enzymes can exhibit either lock-and-key or induced-fit models for substrate binding.

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    Description

    This quiz covers important concepts in thermodynamics and chemical equilibrium, including entropy changes, enthalpy, and the reaction quotient. Understand how various factors affect the equilibrium state of reactions and the meaning of equilibrium constants. Test your knowledge on how entropy behaves during phase transitions and the implications of Le Châtelier's principle.

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