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Study Guide: Chemical Equilibrium: Principles and Thermodynamics

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Chemical Equilibrium: Principles and Thermodynamics Study Guide

Foundations of Chemical Equilibrium

Chemical equilibrium is characterized by the complete cessation of all molecular motion and reaction processes.

Answer: False

Explanation: Chemical equilibrium is a dynamic state characterized by equal forward and reverse reaction rates, not a cessation of molecular motion or reaction processes.

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Claude Louis Berthollet first proposed the concept of chemical equilibrium in 1803, based on his observations of reversible reactions.

Answer: True

Explanation: The concept of chemical equilibrium was first developed by Claude Louis Berthollet in 1803, stemming from his studies of reversible chemical reactions.

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The equilibrium position describes the specific rate constants governing the forward and reverse reactions.

Answer: False

Explanation: The equilibrium position refers to the relative amounts of reactants and products at equilibrium, not the specific rate constants.

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What defines the state of chemical equilibrium in a reaction?

Answer: The forward reaction rate equals the reverse reaction rate, resulting in constant concentrations.

Explanation: Chemical equilibrium is defined by the state where the rate of the forward reaction equals the rate of the reverse reaction, leading to constant macroscopic properties, including concentrations.

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Who is credited with developing the concept of chemical equilibrium based on the reversibility of reactions?

Answer: Claude Louis Berthollet

Explanation: Claude Louis Berthollet is credited with developing the concept of chemical equilibrium in 1803, based on his observations of reversible reactions.

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What does the 'equilibrium position' indicate about a reaction?

Answer: The relative amounts of reactants and products at equilibrium.

Explanation: The equilibrium position describes the relative concentrations or partial pressures of reactants and products present once equilibrium has been established.

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Kinetics and Equilibrium Expressions

The Law of Mass Action, proposed by Guldberg and Waage, accurately describes the rate of all chemical reactions, regardless of their complexity.

Answer: False

Explanation: The Law of Mass Action, while foundational, accurately describes the rate of elementary reactions; it does not universally describe the rate of all chemical reactions, particularly complex multi-step processes.

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The equilibrium constant (K) is defined as the ratio of the rate constant for the reverse reaction to the rate constant for the forward reaction.

Answer: False

Explanation: The equilibrium constant (K) is defined as the ratio of the rate constant for the forward reaction (k+) to the rate constant for the reverse reaction (k-), i.e., K = k+/k-.

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The reaction quotient (Qr) is used to determine the direction a reaction will proceed only when the system is already at equilibrium.

Answer: False

Explanation: The reaction quotient (Qr) is used to determine the direction a reaction will proceed at any point, not solely when the system is already at equilibrium.

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If Qr < Keq, the reaction will proceed in the reverse direction to reach equilibrium.

Answer: False

Explanation: If Qr < Keq, the reaction will proceed in the forward direction towards products to reach equilibrium.

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According to the Law of Mass Action, the rate of a chemical reaction is proportional to:

Answer: The product of the concentrations of reactants, each raised to its stoichiometric coefficient.

Explanation: The Law of Mass Action states that the rate of a chemical reaction is proportional to the product of the concentrations of the reactants, each raised to the power of its stoichiometric coefficient.

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If the reaction quotient Qr is greater than the equilibrium constant Keq, the reaction will proceed:

Answer: In the reverse direction towards reactants.

Explanation: If Qr > Keq, the ratio of products to reactants is too high, indicating that the reaction must proceed in the reverse direction to reach equilibrium.

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What is the relationship between the equilibrium constant (K) and the rate constants (k+ for forward, k- for reverse)?

Answer: K = k+ / k-

Explanation: The equilibrium constant (K) is fundamentally the ratio of the rate constant for the forward reaction (k+) to the rate constant for the reverse reaction (k-).

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Thermodynamics of Equilibrium

At equilibrium, the Gibbs free energy of a system reaches its maximum value.

Answer: False

Explanation: At equilibrium, the Gibbs free energy of a system reaches its minimum value under constant temperature and pressure.

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The van 't Hoff equation relates the change in equilibrium constant to changes in pressure and volume.

Answer: False

Explanation: The van 't Hoff equation relates the change in equilibrium constant to temperature and the standard molar enthalpy change (ΔH°) of the reaction.

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For an endothermic reaction, the equilibrium constant increases as temperature increases.

Answer: True

Explanation: For endothermic reactions (ΔH° > 0), the equilibrium constant (K) increases with increasing temperature, as predicted by the van 't Hoff equation.

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Minimizing the Gibbs free energy of a system requires solving equations based on the conservation of mass and the definition of chemical potential.

Answer: True

Explanation: The minimization of Gibbs free energy at equilibrium is achieved by solving a system of equations that incorporates mass conservation constraints and the relationships between chemical potentials.

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The relationship ΔrG° = -RTlnKeq shows that a positive standard Gibbs free energy change corresponds to a large equilibrium constant.

Answer: False

Explanation: The relationship ΔrG° = -RTlnKeq indicates that a negative standard Gibbs free energy change corresponds to a large equilibrium constant.

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The entropy of mixing is irrelevant to the determination of chemical equilibrium as it only affects the physical state, not the chemical composition.

Answer: False

Explanation: The entropy of mixing contributes to the overall Gibbs free energy and is therefore relevant to the determination of chemical equilibrium.

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The condition (dG/dξ)T,p = 0 signifies that the system has reached a state of minimum Gibbs free energy at constant temperature and pressure.

Answer: True

Explanation: The condition (dG/dξ)T,p = 0 signifies that the system has reached a state of minimum Gibbs free energy at constant temperature and pressure, which is the criterion for equilibrium.

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Which thermodynamic quantity reaches a minimum at equilibrium under constant temperature and pressure?

Answer: Gibbs Free Energy (G)

Explanation: Under conditions of constant temperature and pressure, a system reaches equilibrium when its Gibbs Free Energy (G) is minimized.

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The van 't Hoff equation relates the change in equilibrium constant (K) to temperature (T) and which other key reaction property?

Answer: Standard Enthalpy change (ΔH°)

Explanation: The van 't Hoff equation relates the temperature dependence of the equilibrium constant (K) to the standard molar enthalpy change (ΔH°) of the reaction.

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The equation ΔrG° = -RTlnKeq relates the standard Gibbs free energy change to:

Answer: The equilibrium constant.

Explanation: The equation ΔrG° = -RTlnKeq establishes a direct relationship between the standard Gibbs free energy change of a reaction and its equilibrium constant.

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How does temperature affect the equilibrium constant for an exothermic reaction?

Answer: K decreases as temperature increases.

Explanation: For an exothermic reaction (ΔH° < 0), an increase in temperature shifts the equilibrium to the left, decreasing the equilibrium constant (K).

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What does the condition αμA + βμB = σμS + τμT represent at equilibrium?

Answer: The equality of chemical potentials of reactants and products.

Explanation: At equilibrium, the sum of the chemical potentials of reactants, weighted by their stoichiometric coefficients, equals the sum of the chemical potentials of products, weighted by their stoichiometric coefficients.

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Factors Influencing Equilibrium

A catalyst shifts the equilibrium position towards the products by increasing the rate of the forward reaction more than the reverse reaction.

Answer: False

Explanation: A catalyst increases the rates of both forward and reverse reactions equally, thereby accelerating the attainment of equilibrium but not shifting its position.

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Le Chatelier's principle predicts that if a system at equilibrium is disturbed, it will shift in a direction that enhances the disturbance.

Answer: False

Explanation: Le Chatelier's principle states that a system at equilibrium, when disturbed, will shift in a direction that counteracts the applied change.

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What is the primary effect of a catalyst on a system at equilibrium?

Answer: It increases the rate at which equilibrium is reached.

Explanation: A catalyst accelerates both the forward and reverse reaction rates equally, thus reducing the time required to reach equilibrium without altering the equilibrium position or constant.

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According to Le Chatelier's principle, if the concentration of a product is increased in a system at equilibrium, the equilibrium will shift:

Answer: Towards the reactants to consume the excess product.

Explanation: According to Le Chatelier's principle, an increase in product concentration will cause the equilibrium to shift towards the reactants to counteract the change.

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Which principle helps predict how an equilibrium system will respond to changes in temperature, pressure, or concentration?

Answer: Le Chatelier's Principle

Explanation: Le Chatelier's Principle provides a framework for predicting the direction in which an equilibrium system will shift in response to external changes in conditions such as temperature, pressure, or concentration.

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Equilibrium in Real Systems

Pure solids and liquids are included in the equilibrium constant expression with their respective concentrations.

Answer: False

Explanation: Pure solids and liquids are excluded from equilibrium constant expressions because their activities are considered constant and equal to one.

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Homogeneous equilibrium occurs when reactants and products exist in different physical phases.

Answer: False

Explanation: Homogeneous equilibrium occurs when all reactants and products are in the same physical phase, whereas heterogeneous equilibrium involves multiple phases.

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Mass-balance equations ensure that the total concentration of each element remains constant throughout a reaction.

Answer: True

Explanation: Mass-balance equations are statements that ensure the total concentration of each element or species remains constant throughout the reaction, adhering to the law of conservation of mass.

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Activity coefficients are used to adjust concentrations in equilibrium expressions to account for non-ideal behavior in solutions.

Answer: True

Explanation: Activity coefficients are employed in equilibrium expressions to correct concentrations for non-ideal behavior in solutions, thereby ensuring accurate thermodynamic calculations.

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For gas-phase reactions, fugacity is used instead of partial pressure to account for non-ideal behavior.

Answer: True

Explanation: In gas-phase reactions, fugacity serves as the thermodynamic variable that accounts for non-ideal behavior, analogous to how activity coefficients adjust concentrations in solutions.

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In solutions, higher ionic strengths generally lead to activity coefficients that are closer to unity.

Answer: False

Explanation: In solutions, higher ionic strengths generally lead to activity coefficients that deviate further from unity, reflecting increased interionic interactions.

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What is the activity of a pure solid or liquid when included in an equilibrium constant expression?

Answer: It is equal to one.

Explanation: The activity of pure solids and liquids is conventionally taken as unity, meaning they do not explicitly appear in equilibrium constant expressions.

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Which type of equilibrium occurs when all reactants and products are in the same physical phase?

Answer: Homogeneous equilibrium

Explanation: Homogeneous equilibrium is defined as occurring when all reactants and products are present in the same physical phase (e.g., all gases or all dissolved in a single solution).

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Which of the following is NOT a valid approach for calculating the composition of a mixture at equilibrium?

Answer: Maximizing the system's enthalpy.

Explanation: Calculating equilibrium composition typically involves minimizing Gibbs free energy, manipulating equilibrium constants, or satisfying mass-balance equations; maximizing enthalpy is not a standard approach for determining equilibrium.

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What is the role of Lagrange multipliers in calculating equilibrium compositions?

Answer: To solve the constrained minimization of Gibbs free energy.

Explanation: Lagrange multipliers are mathematical tools used to solve the constrained optimization problem of minimizing the Gibbs free energy subject to conservation laws (mass balance).

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For gas-phase reactions, what term is used instead of activity to account for non-ideal behavior?

Answer: Fugacity

Explanation: For gas-phase reactions, fugacity is used as the thermodynamic variable to account for non-ideal behavior, analogous to how activity coefficients adjust concentrations in solutions.

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What is the relationship between Kc and the ionic strength in solutions?

Answer: Kc can vary with ionic strength due to changes in activity coefficients.

Explanation: The concentration-based equilibrium constant (Kc) can vary with ionic strength because ionic strength influences the activity coefficients of the reacting species.

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Applications and Specific Equilibria

The Boudouard reaction involves the equilibrium between carbon monoxide, carbon dioxide, and solid carbon.

Answer: True

Explanation: The Boudouard reaction describes the equilibrium between carbon monoxide, carbon dioxide, and solid carbon, represented as 2 CO(g) <=> CO2(g) + C(s).

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The Haber-Bosch process involves only a single equilibrium step: the direct reaction between nitrogen and hydrogen.

Answer: False

Explanation: The Haber-Bosch process is a complex industrial synthesis involving multiple equilibrium steps, including adsorption, dissociation, reaction, and desorption on a catalyst surface.

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The equilibrium constant expression for the Boudouard reaction includes a term for solid carbon.

Answer: False

Explanation: The equilibrium constant expression for the Boudouard reaction excludes solid carbon because its activity is considered unity.

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The self-ionization constant of water (Kw) is defined as the ratio of hydronium ion concentration to hydroxide ion concentration.

Answer: False

Explanation: The self-ionization constant of water (Kw) is defined as the product of the hydronium ion concentration and the hydroxide ion concentration.

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Multiple equilibria, like those in polybasic acids, can be calculated by multiplying the individual stepwise equilibrium constants.

Answer: True

Explanation: For processes involving multiple sequential equilibria, such as the dissociation of polybasic acids, the overall equilibrium constant is the product of the individual stepwise equilibrium constants.

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The hydrolysis of aluminum ions (Al3+) shows complex equilibrium behavior, including precipitation and the formation of soluble aluminate ions at different pH levels.

Answer: True

Explanation: The hydrolysis of aluminum ions illustrates complex equilibrium behavior, demonstrating how pH changes can lead to precipitation of aluminum hydroxide and the formation of soluble aluminate species.

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The self-ionization of water is represented by the equilibrium 2 H2O <=> H3O+ + OH-. What is Kw?

Answer: Kw = [H3O+] * [OH-]

Explanation: The ion product constant for water (Kw) is defined as the product of the molar concentrations of hydronium ([H3O+]) and hydroxide ([OH-]) ions.

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How are multiple equilibrium constants combined for a process that occurs in sequential steps?

Answer: They are multiplied together.

Explanation: For a process composed of sequential steps, the overall equilibrium constant is the product of the equilibrium constants for each individual step.

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The Boudouard reaction equilibrium constant expression is Kc = [CO2] / [CO]^2. Why is solid carbon excluded?

Answer: Because solid carbon's activity is considered one.

Explanation: Solid carbon is a pure substance and its activity is taken as unity, hence it is omitted from the equilibrium constant expression for the Boudouard reaction.

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The Haber-Bosch process for ammonia synthesis is given as an example of:

Answer: A process involving multiple equilibrium steps.

Explanation: The Haber-Bosch process, used for ammonia synthesis, is a complex industrial process that involves multiple sequential equilibrium steps, including adsorption and surface reactions.

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Advanced Equilibrium Concepts

The Curtin-Hammett principle states that equilibrium product ratios are determined solely by the relative thermodynamic stability of the products.

Answer: False

Explanation: The Curtin-Hammett principle addresses situations where product ratios are determined by the relative stability of transition states leading to products, particularly when secondary reactions occur.

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A metastable mixture is a system that has reached its true thermodynamic equilibrium state.

Answer: False

Explanation: A metastable mixture is kinetically stable but not thermodynamically stable; it has not reached its true equilibrium state due to a kinetic barrier.

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Which statement accurately describes the Curtin-Hammett principle?

Answer: It relates product ratios to transition state stability when secondary reactions occur.

Explanation: The Curtin-Hammett principle addresses situations where product ratios are determined by the relative stability of transition states leading to products, particularly when secondary reactions occur.

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What is a 'metastable mixture'?

Answer: A mixture that appears stable but has a kinetic barrier preventing true equilibrium.

Explanation: A metastable mixture is one that seems stable but is not at its lowest possible energy state; a kinetic barrier prevents it from reaching true thermodynamic equilibrium.

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