EQUILIBRIUM: ASSIGNMENT
Q 1: List four general characteristics common to systems (both physical and chemical)
once they attain equilibrium.
A: Four general characteristics of a system at equilibrium are:
(i) Equilibrium is possible only in a closed system at a given temperature.
(ii) Both the opposing processes (forward and reverse reactions/processes)
occur simultaneously at the same rate, resulting in a dynamic but stable
condition.
(iii) All measurable properties of the system remain constant.
(iv) When equilibrium is reached for a physical process, it is characterized by a
constant value of one of its parameters at a given temperature (e.g., vapour
pressure for liquid-vapour equilibrium).
Q2: State the Equilibrium Law (Law of Chemical Equilibrium) for a general reversible
reaction, aA+bB⇌cC+dD.
A: The Equilibrium Law states that at a given temperature, the product of
concentrations of the reaction products raised to their respective stoichiometric
coefficients in the balanced chemical equation, divided by the product of
concentrations of the reactants raised to their individual stoichiometric coefficients,
has a constant value. For the general reaction aA+bB⇌cC+dD, the equilibrium constant
(Kc) is expressed as: Kc=[A]a[B]b / [C]c[D]d.
Q3: In the liquid-vapour equilibrium of water in a closed container, why is the
equilibrium state described as dynamic rather than static, even though the vapour
pressure remains constant?
A: Although the vapour pressure remains constant because the system has reached an
equilibrium state, this equilibrium is not static. Instead, it is dynamic because there is
continuous activity at the boundary between the liquid and the vapour phases. At
equilibrium, the rate of evaporation (molecules leaving the liquid surface into the
vapour phase) is equal to the rate of condensation (molecules returning from the
vapour phase to the liquid surface). Since both opposing processes are occurring
simultaneously at equal rates, the system appears macroscopically unchanging, but
microscopically, activity is continuous.
Q4: For the reaction PCl5⇌PCl3+Cl2 at 500K, the equilibrium concentrations are:
[PCl3] =1.59M, [Cl2]=1.59M, and [PCl5]=1.41M. Calculate Kc for the reaction.
(Solve yourself)
Q5: The industrial production of Calcium Oxide (CaO) involves the thermal
decomposition of CaCO3 in a closed kiln: CaCO3(s)⇌CaO(s)+CO2(g). How is the
continuous removal of the product CO2 utilized commercially to maximize the yield
of CaO?
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A: This utilization is explained by Le Chatelier’s principle. Continuous removal of the
product, CO2 (a volatile substance), maintains the reaction quotient (Qc) at a value less
than the equilibrium constant (Kc). To minimize the effect of removing the product
(stress relieved by replenishing the removed substance), the reaction continues to
move in the forward direction (right to left), driving the decomposition of CaCO3
closer to completion and maximizing the yield of CaO.
Q6. The equilibrium constant (Kc) for the hydrolysis of sucrose at 300K is 2×1013.
Calculate the standard Gibbs energy change (ΔG∘) for the reaction at 300K.
(Use R=8.314 J mol−1K−1).
A: The relationship between ΔG∘ and Kc is ΔG∘=−2.303 RT log Kc.
Substituting the given values: ΔG∘=−2.303 (8.314 J mol−1K−1)×(300K)× log (2×1013). The
calculation yields: ΔG∘=−7.64×104 J mol−1.
Q7: Write the equilibrium constant expression (Kc) for the following heterogeneous
equilibrium: Ni(s)+4CO(g)⇌Ni(CO)4(g)
A: Do it yourself
Q8: If the equilibrium constant for the reaction H2(g)+I2(g)⇌2HI(g) is Kc = x, what is
the equilibrium constant (Kc′′) if the reaction is rewritten as 1/2H2(g)+1/2 I2(g)⇌HI(g)?
A: When a balanced chemical equation is multiplied throughout by a factor (in this
case, n= 1/2), the equilibrium constant for the new reaction (Kc′′) is equal to the
original equilibrium constant (Kc) raised to that power (Kc′′=Kcn). Thus, Kc′′=Kc1/2 or
x1/2.
Q9: A reaction has an equilibrium constant Kc=4.0×1031. What does the magnitude of
this constant suggest about the concentration of products relative to reactants at
equilibrium?
A: Since Kc is very large (Kc>103), this magnitude suggests that the products
predominate over the reactants. This means the reaction proceeds nearly to
completion.
Q10: Consider the gaseous reaction CO(g)+3H2(g)⇌CH4(g)+H2O(g). If the system is
compressed to half its original volume at a constant temperature, predict the direction
in which the equilibrium will shift.
A: In this reaction, there are 4 moles of gaseous reactants (1CO+3H2) and 2 moles of
gaseous products (1CH4+1H2O). Compressing the system halves the volume, which
doubles the total pressure. According to Le Chatelier’s principle, the equilibrium shifts
in the direction that reduces the pressure, which corresponds to the side with the
fewer number of moles of gas. Since the product side has fewer moles (2 moles vs. 4
moles), the equilibrium will shift in the forward direction.
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Q11: Determine the relationship between Kp and Kc for the general gaseous reaction
aA+bB⇌cC+dD. Also define the variable Δn.
A: Do it yourself
Q12: How is the equilibrium involving the dissolution of a gas in a liquid, such as:
CO2(gas) ⇌ CO2(in solution), governed, and how does temperature affect this
equilibrium?
A: This equilibrium is governed by Henry’s law. Henry's law states that the mass of a
gas dissolved in a given mass of a solvent at any temperature is proportional to the
pressure of the gas above the solvent. The amount of gas dissolved decreases with an
increase of temperature.
Q13: When creating a saturated sugar solution, if you drop some radioactive sugar
crystals into the solution containing non-radioactive sugar, how does this demonstrate
the dynamic nature of solid-solution equilibrium?
A: In a saturated solution, a dynamic equilibrium exists where the rate of dissolution
of solid sugar equals the rate of crystallisation of sugar. Initially, the solution contains
no radioactive sugar molecules. However, since the equilibrium is dynamic, there is a
continuous exchange between the radioactive and non-radioactive sugar molecules
between the solid phase and the solution phase. After some time, radioactivity is
observed in both the solid sugar and the solution, confirming that dissolution and
crystallisation processes are still occurring simultaneously.
Q14: Explain why a catalyst, despite increasing reaction rates significantly, does not
alter the equilibrium composition of a reaction mixture.
A: A catalyst increases the rate of the chemical reaction by making available a new,
low-energy pathway (lowering the activation energy) for the conversion of reactants
to products. Crucially, the catalyst increases the rate of the forward and reverse
reactions by exactly the same amount because both pass through the same transition
state. Since the rates increase equally, the ratio of product concentration to reactant
concentration at equilibrium (Kc) remains unchanged, meaning the equilibrium
composition is unaffected.
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