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Question 1

Answer the following questions related to manganese compounds.
(a) Manganese has several common oxidation states.
(i) Write the complete electron configuration for an \( \mathrm{Mn} \) atom in the ground state.
(ii) When manganese forms cations, electrons are lost from which subshell first? Identify both the number and letter associated with the subshell.
A student performs an experiment to produce a manganese salt of unknown composition, \( \mathrm{Mn}_{x}\mathrm{Cl}_{y}(aq) \), and determine its empirical formula. The student places a sample of \( \mathrm{Mn}(s) \) in a beaker containing excess \( \mathrm{HCl}(aq) \), as represented by the following equation.
\( x\,\mathrm{Mn}(s) + y\,\mathrm{HCl}(aq) \rightarrow \mathrm{Mn}_{x}\mathrm{Cl}_{y}(aq) + \dfrac{y}{2}\,\mathrm{H}_{2}(g) \)
The student heats the resulting mixture until only \( \mathrm{Mn}_{x}\mathrm{Cl}_{y}(s) \) remains in the beaker. The data are given in the following table.
Mass of empty beaker\( 60.169\ \mathrm{g} \)
Mass of beaker and \( \mathrm{Mn}(s) \)\( 61.262\ \mathrm{g} \)
Mass of beaker and \( \mathrm{Mn}_{x}\mathrm{Cl}_{y}(s) \) after heating to constant mass\( 62.673\ \mathrm{g} \)
(b) Calculate the mass of \( \mathrm{Cl} \) in the sample of \( \mathrm{Mn}_{x}\mathrm{Cl}_{y}(s) \) remaining in the beaker.
(c) Calculate the number of moles of \( \mathrm{Cl} \) in the sample of \( \mathrm{Mn}_{x}\mathrm{Cl}_{y}(s) \) remaining in the beaker.
(d) The student determines that \( 0.0199\ \mathrm{mol} \) of \( \mathrm{Mn} \) was used in the experiment. Use the data to determine the empirical formula of the \( \mathrm{Mn}_{x}\mathrm{Cl}_{y}(s) \).
(e) The student repeats the experiment using the same amounts of \( \mathrm{Mn} \) and \( \mathrm{HCl} \) and notices that some of the \( \mathrm{Mn}_{x}\mathrm{Cl}_{y} \) splatters out of the beaker as it is heated to dryness. Will the number of moles of \( \mathrm{Cl} \) calculated for this trial be greater than, less than, or equal to the number calculated in part \( \mathrm{(c)} \)? Justify your answer.
(f) Another compound of manganese, \( \mathrm{MnO}_{2} \), is used in alkaline batteries, represented by the following diagram. Some half-reactions are given in the table.
(i) Based on the half-reactions given in the table, write the balanced net ionic equation for the reaction that has the greatest thermodynamic favorability.
(ii) Calculate the value of \( E^\circ_{\mathrm{cell}} \) for the overall reaction.
(iii) Calculate the value of \( \Delta G^\circ \) in \( \mathrm{kJ/mol}_{\mathrm{rxn}} \).
(iv) A student claims that the total mass of an alkaline battery decreases as the battery operates because the anode loses mass. Do you agree with the student’s claim? Justify your answer.

Most-appropriate topic codes (AP Chemistry):

• Topic \( 1.5 \) — Atomic Structure and Electron Configuration (Parts \( \mathrm{(a)(i)} \), \( \mathrm{(a)(ii)} \))
• Topic \( 1.3 \) — Elemental Composition of Pure Substances (Parts \( \mathrm{(b)} \), \( \mathrm{(c)} \), \( \mathrm{(d)} \), \( \mathrm{(e)} \))
• Topic \( 9.8 \) — Galvanic (Voltaic) and Electrolytic Cells (Parts \( \mathrm{(f)(i)} \), \( \mathrm{(f)(iv)} \))
• Topic \( 9.9 \) — Cell Potential and Free Energy (Parts \( \mathrm{(f)(ii)} \), \( \mathrm{(f)(iii)} \))
▶️ Answer/Explanation

(a)(i)
Accept one of the following:
\( 1s^2\,2s^2\,2p^6\,3s^2\,3p^6\,4s^2\,3d^5 \)
or \( [\mathrm{Ar}]\,4s^2\,3d^5 \)

(a)(ii)
\( 4s \)

(b)
\( 62.673\ \mathrm{g} – 61.262\ \mathrm{g} = 1.411\ \mathrm{g\ Cl} \)

(c)
\( 1.411\ \mathrm{g\ Cl} \times \dfrac{1\ \mathrm{mol\ Cl}}{35.45\ \mathrm{g\ Cl}} = 0.03980\ \mathrm{mol\ Cl} \)

(d)
\( \dfrac{0.03980\ \mathrm{mol\ Cl}}{0.0199\ \mathrm{mol\ Mn}} = 2.00 \)
Therefore, the empirical formula is \( \mathrm{MnCl}_{2} \).

(e)
Less than. If some of the \( \mathrm{Mn}_{x}\mathrm{Cl}_{y} \) splatters out, the final measured mass is smaller, so the calculated mass and moles of chlorine are smaller.

(f)(i)
\( \mathrm{2\,MnO}_{2}(s) + \mathrm{H}_{2}\mathrm{O}(l) + 2\,e^- \rightarrow \mathrm{Mn}_{2}\mathrm{O}_{3}(s) + 2\,\mathrm{OH}^-(aq) \)
\( \mathrm{Zn}(s) + 2\,\mathrm{OH}^-(aq) \rightarrow \mathrm{ZnO}(s) + \mathrm{H}_{2}\mathrm{O}(l) + 2\,e^- \)
Overall:
\( \mathrm{2\,MnO}_{2}(s) + \mathrm{Zn}(s) \rightarrow \mathrm{Mn}_{2}\mathrm{O}_{3}(s) + \mathrm{ZnO}(s) \)

(f)(ii)
\( E^\circ_{\mathrm{cell}} = 0.15\ \mathrm{V} – (-1.28\ \mathrm{V}) = 1.43\ \mathrm{V} \)

(f)(iii)
\( \Delta G^\circ = -nFE^\circ \)
\( \Delta G^\circ = -(2)(96{,}485)(1.43)\left(\dfrac{1\ \mathrm{kJ}}{1000\ \mathrm{J}}\right) = -276\ \mathrm{kJ/mol}_{\mathrm{rxn}} \)

(f)(iv)
Disagree. The battery is sealed, so the total mass remains the same.

Question 2

In the gas phase, \( \mathrm{AlCl}_{3} \) is a molecular substance. A reaction of gaseous \( \mathrm{AlCl}_{3} \) at high temperature is represented by the following balanced equation.
Reaction \( 1 \): \( \mathrm{AlCl}_{3}(g) \rightarrow \mathrm{Al}(g) + 3\,\mathrm{Cl}(g) \qquad \Delta H^\circ_{1} = ? \)
(a) How many grams of \( \mathrm{Cl}(g) \) can be formed from \( 1.25\ \mathrm{mol} \) of \( \mathrm{AlCl}_{3}(g) \)?
Additional reactions that involve \( \mathrm{Al} \) or \( \mathrm{Cl} \) are shown in the following table.
Reaction NumberEquation\( \Delta H^\circ_{\mathrm{rxn}} \) \( \mathrm{(kJ/mol}_{\mathrm{rxn}}\mathrm{)} \)
\( 2 \)\( \mathrm{Al}(s) + \dfrac{3}{2}\,\mathrm{Cl}_{2}(g) \rightarrow \mathrm{AlCl}_{3}(g) \)\( -583 \)
\( 3 \)\( \mathrm{Al}(s) \rightarrow \mathrm{Al}(g) \)\( +326 \)
\( 4 \)\( \mathrm{Cl}_{2}(g) \rightarrow 2\,\mathrm{Cl}(g) \)\( +243 \)
(b) Calculate the value of \( \Delta H^\circ_{1} \), in \( \mathrm{kJ/mol}_{\mathrm{rxn}} \), for reaction \( 1 \) above using reactions \( 2 \), \( 3 \), and \( 4 \).
(c) A potential energy diagram for \( \mathrm{Cl}_{2} \) is shown in the following graph.
(i) Based on the graph, what is the bond length, in picometers, for \( \mathrm{Cl}_{2} \)? ____________
(ii) A student finds that the average \( \mathrm{Al-Cl} \) bond length is \( 220\ \mathrm{pm} \) and the average bond energy is \( 425\ \mathrm{kJ/mol} \). Draw the potential energy curve for the average \( \mathrm{Al-Cl} \) bond on the preceding graph.
(d) Three proposed Lewis diagrams for the \( \mathrm{AlCl}_{3}(g) \) molecule are shown.
(i) The \( \mathrm{AlCl}_{3}(g) \) molecule has a trigonal planar geometry. Which diagram \((1,\ 2,\ \text{or}\ 3)\) can be eliminated based on geometry? Justify your choice based on VSEPR theory.
(ii) Which of the three diagrams is the best representation for the bonding in \( \mathrm{AlCl}_{3} \)? Justify your choice based on formal charges.
\( \mathrm{AlCl}_{3} \) is known to dimerize reversibly in the gas phase. The dimerization equilibrium is represented by the following equation.
\( \mathrm{2\,AlCl}_{3}(g) \rightleftharpoons \mathrm{Al}_{2}\mathrm{Cl}_{6}(g) \)
(e) Write the expression for the equilibrium constant, \( K_p \), for this reaction.
A particle-level diagram of an equilibrium mixture of \( \mathrm{AlCl}_{3}(g) \) and \( \mathrm{Al}_{2}\mathrm{Cl}_{6}(g) \) at \( 400^\circ\mathrm{C} \) in a \( 25\ \mathrm{L} \) closed container is shown.
(f) Using the particle-level diagram, calculate the value of \( K_p \) for the reaction if the total pressure in the container is \( 22.1\ \mathrm{atm} \).

Most-appropriate topic codes (AP Chemistry):

• Topic \( 4.5 \) — Stoichiometry (Part \( \mathrm{(a)} \))
• Topic \( 6.9 \) — Hess’s Law (Part \( \mathrm{(b)} \))
• Topic \( 2.2 \) — Intramolecular Force and Potential Energy (Parts \( \mathrm{(c)(i)} \), \( \mathrm{(c)(ii)} \))
• Topic \( 2.7 \) — VSEPR and Hybridization (Part \( \mathrm{(d)(i)} \))
• Topic \( 2.6 \) — Resonance and Formal Charge (Part \( \mathrm{(d)(ii)} \))
• Topic \( 7.3 \) — Reaction Quotient and Equilibrium Constant (Part \( \mathrm{(e)} \))
• Topic \( 7.4 \) — Calculating the Equilibrium Constant (Part \( \mathrm{(f)} \))
• Topic \( 7.8 \) — Representations of Equilibrium (Part \( \mathrm{(f)} \))
▶️ Answer/Explanation

(a)
For the correct calculated value reported with the correct number of significant figures:
\( 1.25\ \mathrm{mol\ AlCl}_{3} \times \dfrac{3\ \mathrm{mol\ Cl}}{1\ \mathrm{mol\ AlCl}_{3}} \times \dfrac{35.45\ \mathrm{g\ Cl}}{1\ \mathrm{mol\ Cl}} = 133\ \mathrm{g\ Cl} \)

First use the mole ratio from reaction \( 1 \), then convert moles of \( \mathrm{Cl} \) to grams using its molar mass.

(b)
For the correct algebraic manipulation of either \( \Delta H^\circ_{2} \) or \( \Delta H^\circ_{4} \) (may be implicit):
Accept one of the following:

• Reversing reaction \( 2 \):
\( \mathrm{AlCl}_{3}(g) \rightarrow \mathrm{Al}(s) + \dfrac{3}{2}\,\mathrm{Cl}_{2}(g) \qquad \Delta H^\circ_{\mathrm{rxn}} = -(-583) = +583\ \mathrm{kJ/mol}_{\mathrm{rxn}} \)

• Multiplying reaction \( 4 \) by \( \dfrac{3}{2} \):
\( \dfrac{3}{2}\,\mathrm{Cl}_{2}(g) \rightarrow 3\,\mathrm{Cl}(g) \qquad \Delta H^\circ_{\mathrm{rxn}} = \dfrac{3}{2}(243) = +365\ \mathrm{kJ/mol}_{\mathrm{rxn}} \)

For the correct calculated value:
\( \Delta H^\circ_{1} = -\Delta H^\circ_{2} + \Delta H^\circ_{3} + 1.5(\Delta H^\circ_{4}) = -(-583) + 326 + 1.5(243) = 1274\ \mathrm{kJ/mol}_{\mathrm{rxn}} \)

This is a Hess’s law problem: reverse reaction \( 2 \), keep reaction \( 3 \), and multiply reaction \( 4 \) by \( \dfrac{3}{2} \), then add.

(c)(i)
For the correct answer:
\( 200\ \mathrm{pm} \) \((\pm 10\ \mathrm{pm})\)

The bond length is the internuclear distance at the minimum point of the potential energy curve.

(c)(ii)
For a curve with a minimum at an internuclear distance of \( 220 \pm 10\ \mathrm{pm} \):
See sample curve below.

For a curve with a minimum energy value of \( -425 \pm 20\ \mathrm{kJ/mol} \) that approaches zero as the internuclear distance approaches \( 500\ \mathrm{pm} \):

Because the \( \mathrm{Al-Cl} \) bond is longer than the \( \mathrm{Cl-Cl} \) bond, its minimum is shifted slightly to the right. Because its bond energy is greater, the well is deeper.

(d)(i)
For the correct answer and a valid justification:
Diagram \( 2 \). Aluminum has four electron domains in Diagram \( 2 \), which would be trigonal pyramidal, not trigonal planar.

A trigonal planar molecule has \( 3 \) electron domains around the central atom, not \( 4 \).

(d)(ii)
For the correct answer and a valid justification:
Diagram \( 1 \). All atoms in diagram \( 1 \) have a formal charge of zero, whereas atoms in diagrams \( 2 \) and \( 3 \) have nonzero formal charges.

The best Lewis structure is usually the one with the smallest magnitude of formal charges, especially when all formal charges can be zero.

(e)
For the correct answer:
\( K_p = \dfrac{P_{\mathrm{Al}_{2}\mathrm{Cl}_{6}}}{\left(P_{\mathrm{AlCl}_{3}}\right)^2} \)

The exponent \( 2 \) on \( P_{\mathrm{AlCl}_{3}} \) comes directly from the coefficient \( 2 \) in the balanced equilibrium equation.

(f)
For the correct calculated value, consistent with part \( \mathrm{(e)} \):
From the particulate diagram, there are \( 3 \) molecules of \( \mathrm{Al}_{2}\mathrm{Cl}_{6} \) and \( 7 \) molecules of \( \mathrm{AlCl}_{3} \).
Therefore, \( \chi_{\mathrm{Al}_{2}\mathrm{Cl}_{6}} = \dfrac{3}{10} \) and \( \chi_{\mathrm{AlCl}_{3}} = \dfrac{7}{10} \)

So, \( P_{\mathrm{Al}_{2}\mathrm{Cl}_{6}} = \dfrac{3}{10}(22.1) \) and \( P_{\mathrm{AlCl}_{3}} = \dfrac{7}{10}(22.1) \)

\( K_p = \dfrac{\chi_{\mathrm{Al}_{2}\mathrm{Cl}_{6}}(P_{\mathrm{total}})}{\left(\chi_{\mathrm{AlCl}_{3}}(P_{\mathrm{total}})\right)^2} = \dfrac{\dfrac{3}{10}(22.1)}{\left(\dfrac{7}{10}(22.1)\right)^2} = 0.0277 \)

Thus, \( \boxed{K_p = 0.0277} \).

Question 3

Answer the following questions about an experiment in which \( \mathrm{CaCO}_{3}(s) \) is combined with \( \mathrm{HCl}(aq) \), represented by the following balanced equation.
\( \mathrm{CaCO}_{3}(s) + 2\,\mathrm{HCl}(aq) \rightarrow \mathrm{CaCl}_{2}(aq) + \mathrm{CO}_{2}(g) + \mathrm{H}_{2}\mathrm{O}(l) \)
(a) Write the balanced net ionic equation for the reaction.
A student performs an investigation to study factors that affect the rate of the reaction. In each trial the student combines \( 50.0\ \mathrm{mL} \) of \( \mathrm{HCl}(aq) \) at \( 21.2^\circ \mathrm{C} \) with \( 1.00\ \mathrm{g} \) of \( \mathrm{CaCO}_{3}(s) \) and measures the time required for the reaction to go to completion. The data are given in the following table.
TrialConcentration of \( \mathrm{HCl}(aq) \) \( (\mathrm{M}) \)Particle Size of \( \mathrm{CaCO}_{3}(s) \)Time of Reaction \( (\mathrm{s}) \)
\( 1 \)\( 1.00 \)Fine powder\( 67 \)
\( 2 \)\( 1.00 \)Small chunks\( 112 \)
\( 3 \)\( 1.00 \)Large chunk\( 342 \)
\( 4 \)\( 3.00 \)Fine powder\( 22 \)
\( 5 \)\( 3.00 \)Small chunks\( 227 \)
\( 6 \)\( 3.00 \)Large chunk\( 114 \)
(b) The student correctly identifies that trial \( 5 \) is inconsistent with the other trials. Explain why the student’s claim is correct using the data in the table.
(c) Based on the reaction conditions and the collisions that occur between particles, explain the reason for the difference in the reaction times for trial \( 2 \) and trial \( 3 \).
(d) The student claims that the reaction is zero order with respect to \( \mathrm{HCl}(aq) \). Do you agree or disagree with the student’s claim? Justify your answer using the student’s data.
(e) The \( \mathrm{HCl}(aq) \) was present in excess in all trials of the experiment. Determine the molarity of the \( \mathrm{HCl}(aq) \) in the beaker after the reaction is complete in trial \( 2 \). Assume that the volume of the mixture remains constant at \( 50.0\ \mathrm{mL} \) throughout the trial. (The molar mass of \( \mathrm{CaCO}_{3} \) is \( 100.09\ \mathrm{g/mol} \).)
In order to measure the enthalpy of the reaction shown, the student repeats trial \( 1 \) by mixing \( 50.0\ \mathrm{mL} \) of \( \mathrm{HCl}(aq) \) with \( 1.00\ \mathrm{g} \) of \( \mathrm{CaCO}_{3}(s) \) using a coffee cup calorimeter. The student records the temperature of the system every \( 20\ \mathrm{s} \). The data are given in the following table.
Time \( (\mathrm{s}) \)Measured Temperature of Solution \( \left( ^\circ \mathrm{C} \right) \)
\( 0 \)\( 21.20 \)
\( 20 \)\( 21.51 \)
\( 40 \)\( 21.70 \)
\( 60 \)\( 21.85 \)
\( 80 \)\( 21.90 \)
\( 100 \)\( 21.90 \)
(f) Is the reaction endothermic or exothermic? Justify your answer using the information in the table.
(g) Based on the experimental data, the mass of the system is \( 51.0\ \mathrm{g} \), and the specific heat of the reaction mixture is \( 4.0\ \mathrm{J/(g \cdot ^\circ C)} \).
(i) Calculate the magnitude of heat transfer, \( q \), in joules.
(ii) Calculate the enthalpy of reaction in units of \( \mathrm{kJ/mol}_{\mathrm{rxn}} \). Include the algebraic sign on your answer.

Most-appropriate topic codes (AP Chemistry):

• Topic \( 4.2 \) — Net Ionic Equations (Part \( \mathrm{(a)} \))
• Topic \( 5.1 \) — Reaction Rates (Parts \( \mathrm{(b)} \), \( \mathrm{(d)} \))
• Topic \( 5.5 \) — Collision Model (Part \( \mathrm{(c)} \))
• Topic \( 5.2 \) — Introduction to Rate Law (Part \( \mathrm{(d)} \))
• Topic \( 4.5 \) — Stoichiometry (Part \( \mathrm{(e)} \))
• Topic \( 6.1 \) — Endothermic and Exothermic Processes (Part \( \mathrm{(f)} \))
• Topic \( 6.4 \) — Heat Capacity and Calorimetry (Part \( \mathrm{(g)(i)} \))
• Topic \( 6.6 \) — Introduction to Enthalpy of Reaction (Part \( \mathrm{(g)(ii)} \))
▶️ Answer/Explanation

(a)
For the correct balanced equation (state symbols not required):
Accept one of the following:

• \( \mathrm{CaCO}_{3}(s) + 2\,\mathrm{H}^{+}(aq) \rightarrow \mathrm{Ca}^{2+}(aq) + \mathrm{CO}_{2}(g) + \mathrm{H}_{2}\mathrm{O}(l) \)
• \( \mathrm{CaCO}_{3}(s) + 2\,\mathrm{H}_{3}\mathrm{O}^{+}(aq) \rightarrow \mathrm{Ca}^{2+}(aq) + \mathrm{CO}_{2}(g) + 3\,\mathrm{H}_{2}\mathrm{O}(l) \)

Chloride is a spectator ion, so it does not appear in the net ionic equation.

(b)
For a correct explanation:
Accept one of the following:

• Even though the concentration of \( \mathrm{HCl} \) is greater in trial \( 5 \) than in trial \( 2 \), the reaction time is significantly longer. Both trial \( 2 \) and \( 5 \) occur under otherwise identical conditions. The trend for trial \( 1 \) and \( 4 \) indicates that higher concentration of \( \mathrm{HCl} \) results in a shorter time of reaction.

• The time of reaction in trial \( 5 \), with small chunks of calcium carbonate, is longer than trial \( 6 \) with large chunks. Both trial \( 5 \) and \( 6 \) occur under otherwise identical conditions. The trend for trials \( 1 \), \( 2 \), and \( 3 \) shows that larger chunks of the solid result in longer time of reaction.

So trial \( 5 \) does not fit the pattern shown by the other trials and is therefore inconsistent.

(c)
For a correct explanation of the effect of surface area on reaction time:
The time of reaction in trial \( 2 \) is shorter than trial \( 3 \) because the calcium carbonate in trial \( 2 \) has a larger surface area \( (\text{meaning that more particles of calcium carbonate are exposed to the } \mathrm{H}^{+} \text{ particles in solution}) \).

For a correct explanation of the effect of particle collisions on reaction rate:
The larger interface between the two reacting substances means there will be more collisions between the particles in a given amount of time, and thus, a higher frequency of successful collisions in which the particles react to form the products.

In short, more exposed surface means more opportunities for acid particles to collide with the solid each second.

(d)
For the correct answer and a valid justification:
Accept one of the following:

• Disagree. If the reaction was zeroth order with respect to \( \mathrm{HCl} \), then changing the concentration of \( \mathrm{HCl} \) would not affect the rate of reaction, and the time of reaction would be the same for trials in which the only difference was \( [\mathrm{HCl}] \). The student’s data for trials \( 1 \) and \( 4 \) \( (\text{and likewise for } 3 \text{ and } 6) \) show that changing \( [\mathrm{HCl}] \) significantly alters the time of reaction.

• Disagree. The reaction appears to be first order, not zeroth order, with respect to \( [\mathrm{HCl}] \). Tripling \( [\mathrm{HCl}] \) results in a reaction time that is about \( \dfrac{1}{3} \) of that when \( [\mathrm{HCl}] = 1.00\ \mathrm{M} \), which means the reaction rate has also tripled, indicating a first-order process.

Since rate changes when concentration changes, the order with respect to \( \mathrm{HCl} \) cannot be zero.

(e)
For the correct calculated moles of \( \mathrm{HCl} \) reacted (may be implicit):
\( 1.00\ \mathrm{g\ CaCO}_{3} \times \dfrac{1\ \mathrm{mol}}{100.09\ \mathrm{g}} = 0.00999\ \mathrm{mol\ CaCO}_{3} \)

\( 0.00999\ \mathrm{mol\ CaCO}_{3} \times \dfrac{2\ \mathrm{mol\ HCl}}{1\ \mathrm{mol\ CaCO}_{3}} = 0.0200\ \mathrm{mol\ HCl\ reacted} \)

For the correct calculated \( [\mathrm{HCl}] \) remaining, consistent with the number of moles reacted:
\( 0.0500\ \mathrm{L} \times \dfrac{1.00\ \mathrm{mol\ HCl}}{1\ \mathrm{L}} = 0.0500\ \mathrm{mol\ HCl\ initially\ present} \)

\( 0.0500\ \mathrm{mol} – 0.0200\ \mathrm{mol} = 0.0300\ \mathrm{mol\ remaining} \)

\( \dfrac{0.0300\ \mathrm{mol}}{0.0500\ \mathrm{L}} = 0.600\ \mathrm{M\ HCl\ remaining} \)

Therefore, the molarity of \( \mathrm{HCl}(aq) \) after completion in trial \( 2 \) is \( \boxed{0.600\ \mathrm{M}} \).

(f)
For the correct answer and a valid justification:
Exothermic. The solution temperature increases as the reaction proceeds, rising from \( 21.20^\circ \mathrm{C} \) to \( 21.90^\circ \mathrm{C} \). This means thermal energy is released by the reaction to the surroundings.

Since the solution warms up, \( q_{\mathrm{sur}} \) is positive and the reaction itself must have \( q_{\mathrm{sys}} < 0 \).

(g)(i)
For the correct calculated value (sign not required):
\( q_{\mathrm{sur}} = mc\Delta T = (51.0\ \mathrm{g})(4.0\ \mathrm{J/(g \cdot ^\circ C)})(21.90^\circ \mathrm{C} – 21.20^\circ \mathrm{C}) = 140\ \mathrm{J} \)

Here, \( \Delta T = 0.70^\circ \mathrm{C} \), so the heat absorbed by the solution is \( \boxed{140\ \mathrm{J}} \).

(g)(ii)
For the correct calculated value, consistent with part \( \mathrm{(g)(i)} \), and the correct sign, consistent with part \( \mathrm{(f)} \):
\( q_{\mathrm{sys}} = -q_{\mathrm{sur}} = -140\ \mathrm{J} = -0.14\ \mathrm{kJ} \)

\( 1.00\ \mathrm{g\ CaCO}_{3} \times \dfrac{1\ \mathrm{mol\ CaCO}_{3}}{100.09\ \mathrm{g\ CaCO}_{3}} \times \dfrac{1\ \mathrm{mol}_{\mathrm{rxn}}}{1\ \mathrm{mol\ CaCO}_{3}} = 0.00999\ \mathrm{mol}_{\mathrm{rxn}} \)

\( \Delta H^\circ_{\mathrm{rxn}} = \dfrac{-0.14\ \mathrm{kJ}}{0.00999\ \mathrm{mol}_{\mathrm{rxn}}} = -14\ \mathrm{kJ/mol}_{\mathrm{rxn}} \)

Therefore, the enthalpy of reaction is \( \boxed{-14\ \mathrm{kJ/mol}_{\mathrm{rxn}}} \).

Question 4

A student is asked to prepare a buffer solution made with equimolar amounts of \( \mathrm{CH_3NH_2}(aq) \) and \( \mathrm{CH_3NH_3Cl}(s) \). The student uses \( 25.00\ \mathrm{mL} \) of \( 0.100\ \mathrm{M\ CH_3NH_2}(aq) \), which contains \( 0.00250\ \mathrm{mol} \) of \( \mathrm{CH_3NH_2} \), to make the buffer.
(a) Calculate the mass of \( \mathrm{CH_3NH_3Cl}(s) \) that contains \( 0.00250\ \mathrm{mol} \) of \( \mathrm{CH_3NH_3Cl} \).
The student has the following materials and equipment available.
• Distilled water      • Electronic balance      • \( 50\ \mathrm{mL} \) beaker      • Pipets
• \( 0.100\ \mathrm{M\ CH_3NH_2}(aq) \)      • Weighing paper      • \( 10.0\ \mathrm{mL} \) graduated cylinder      • pH meter
• Solid \( \mathrm{CH_3NH_3Cl} \)      • \( 50.00\ \mathrm{mL} \) buret      • Small spatula
(b) The following table contains a partial procedure for making the buffer solution. Fill in steps \( 1 \) and \( 4 \) to complete the procedure using only materials and equipment selected from the choices given. (Not all materials listed will be used. Assume that all appropriate safety measures are already in place.)
StepProcedure
\( 1 \) 
\( 2 \)Place the solid in the \( 50\ \mathrm{mL} \) beaker.
\( 3 \)Clean the buret and rinse with distilled water.
\( 4 \) 
\( 5 \)Use the buret to add \( 25.00\ \mathrm{mL} \) of \( 0.100\ \mathrm{M\ CH_3NH_2}(aq) \) to the beaker.
\( 6 \)Mix well.
\( 7 \)Check the pH with the pH meter.
The value of \( K_b \) for \( \mathrm{CH_3NH_2}(aq) \) is \( 4.4 \times 10^{-4} \), and the pH of the buffer the student prepared is \( 10.64 \).
(c) The student prepares a second buffer solution. The student uses \( 25.00\ \mathrm{mL} \) of \( 0.050\ \mathrm{M\ CH_3NH_2}(aq) \) instead of \( 25.00\ \mathrm{mL} \) of \( 0.100\ \mathrm{M\ CH_3NH_2}(aq) \), and half the mass of \( \mathrm{CH_3NH_3Cl}(s) \) that was used in the first buffer. Is the pH of the second buffer greater than, less than, or equal to the pH of the first buffer? Justify your answer.

Most-appropriate topic codes (AP Chemistry):

• Topic \( 4.5 \) — Stoichiometry (Part \( \mathrm{(a)} \))
• Topic \( 8.4 \) — Acid-Base Reactions and Buffers (Part \( \mathrm{(b)} \))
• Topic \( 8.9 \) — Henderson-Hasselbalch Equation (Part \( \mathrm{(c)} \))
▶️ Answer/Explanation

(a)
For the correct calculated value:
\( 0.00250\ \mathrm{mol\ CH_3NH_3Cl} \times \dfrac{67.52\ \mathrm{g}}{1\ \mathrm{mol}} = 0.169\ \mathrm{g} \)

A quick check: the problem says the buffer uses equimolar amounts, so the salt must also provide \( 0.00250\ \mathrm{mol} \), matching the moles of \( \mathrm{CH_3NH_2} \).

(b)
For a correct description of step \( 1 \):
Accept one of the following:

• Use the spatula, balance, and weighing paper to measure out exactly \( 0.169\ \mathrm{g} \) of \( \mathrm{CH_3NH_3Cl}(s) \).
• Use the balance to weigh out the mass of solid found in part \( \mathrm{(a)} \).

For a correct description of step \( 4 \):
Rinse the buret with a small amount of \( 0.100\ \mathrm{M\ CH_3NH_2}(aq) \), drain, and refill with \( 0.100\ \mathrm{M\ CH_3NH_2}(aq) \).

The buret should be rinsed with the solution it will contain so the concentration is not changed by leftover water.

(c)
For the correct answer and a valid justification:
Equal to. The ratio of weak acid to conjugate base is still \( 1:1 \).

In the second buffer, both the base \( \mathrm{CH_3NH_2} \) and its conjugate acid \( \mathrm{CH_3NH_3^+} \) are reduced by the same factor, so \( \dfrac{[\mathrm{CH_3NH_2}]}{[\mathrm{CH_3NH_3^+}]} \) stays the same.
Since buffer pH depends on this ratio, the pH remains unchanged.

Question 5

\( \mathrm{HCl} \) is a molecular gas as a pure substance but acts as an acid in aqueous solution.
(a) A sample of \( \mathrm{HCl}(g) \) is stored in a rigid \( 6.00\ \mathrm{L} \) container at \( 7.45\ \mathrm{atm} \) and \( 296\ \mathrm{K} \).
(i) Calculate the number of moles of \( \mathrm{HCl}(g) \) in the container.
(ii) The rigid \( 6.00\ \mathrm{L} \) container of \( \mathrm{HCl}(g) \) is cooled to a temperature of \( 271\ \mathrm{K} \). Calculate the new pressure, in atm, of the \( \mathrm{HCl}(g) \).
(b) When \( \mathrm{HCl} \) ionizes in aqueous solution, \( \mathrm{Cl^-}(aq) \) ions are formed. In the following box, draw three water molecules with proper orientation around the \( \mathrm{Cl^-} \) ion. Use to represent water molecules.
The \( K_a \) values for three acids are shown in the preceding table.
Acid \( (\mathrm{HA}) \)Anion \( (\mathrm{A^-}) \)\( K_a \) Value
\( \mathrm{HNO_2} \)\( \mathrm{NO_2^-} \)\( 5.6 \times 10^{-4} \)
\( \mathrm{HCl} \)\( \mathrm{Cl^-} \)\( 2.0 \times 10^{7} \)
\( \mathrm{HClO_4} \)\( \mathrm{ClO_4^-} \)\( 1.6 \times 10^{15} \)
(c) The following particulate diagram represents the ionization of one of the acids in the data table. Water molecules have been omitted for clarity. Which acid \( (\mathrm{HNO_2},\ \mathrm{HCl},\ \text{or}\ \mathrm{HClO_4}) \) is represented in the diagram? Justify your answer using the information in the table.
 

Most-appropriate topic codes (AP Chemistry):

• Topic \( 3.4 \) — Ideal Gas Law (Parts \( \mathrm{(a)(i)} \), \( \mathrm{(a)(ii)} \))
• Topic \( 3.7 \) — Solutions and Mixtures (Part \( \mathrm{(b)} \))
• Topic \( 8.6 \) — Molecular Structure of Acids and Bases (Part \( \mathrm{(b)} \))
• Topic \( 8.3 \) — Weak Acid and Base Equilibria (Part \( \mathrm{(c)} \))
▶️ Answer/Explanation

(a)(i)
For the correct calculated value:
\( n = \dfrac{PV}{RT} = \dfrac{(7.45\ \mathrm{atm})(6.00\ \mathrm{L})}{(0.08206\ \mathrm{L \cdot atm \cdot mol^{-1} \cdot K^{-1}})(296\ \mathrm{K})} = 1.84\ \mathrm{mol} \)

Since pressure, volume, and temperature are given, the ideal gas law directly gives the number of moles of \( \mathrm{HCl}(g) \).
So, the container holds \( \boxed{1.84\ \mathrm{mol}} \) of \( \mathrm{HCl}(g) \).

(a)(ii)
For the correct calculated value:
Accept one of the following:

• \( \dfrac{P_1}{T_1} = \dfrac{P_2}{T_2} \)
\( P_2 = \dfrac{(P_1)(T_2)}{T_1} = \dfrac{(7.45\ \mathrm{atm})(271\ \mathrm{K})}{296\ \mathrm{K}} = 6.82\ \mathrm{atm} \)

• \( P = \dfrac{nRT}{V} = \dfrac{(1.84\ \mathrm{mol})(0.08206\ \mathrm{L \cdot atm \cdot mol^{-1} \cdot K^{-1}})(271\ \mathrm{K})}{6.00\ \mathrm{L}} = 6.82\ \mathrm{atm} \)

Because the container is rigid, \( V \) and \( n \) stay constant, so pressure is directly proportional to temperature.
Therefore, the new pressure is \( \boxed{6.82\ \mathrm{atm}} \).

(b)
For a correct drawing:
The drawing should show three water molecules with a hydrogen atom \( (\text{dark circle}) \) oriented toward the \( \mathrm{Cl^-} \) ion.

Water is polar, so the partially positive hydrogen ends point toward the negative \( \mathrm{Cl^-} \) ion.
The oxygen ends point away from the anion.

(c)
For the correct answer and a valid justification:
\( \mathrm{HNO_2} \). The diagram shows most of the molecules in their unionized form, indicating a weak acid with a \( K_a \) value less than \( 1 \), which is consistent with \( \mathrm{HNO_2} \).

In the particulate diagram, there are many \( \mathrm{HA} \) particles and only a smaller number of \( \mathrm{H_3O^+} \) and \( \mathrm{A^-} \) ions, so the acid only partially ionizes.
Since \( \mathrm{HCl} \) and \( \mathrm{HClO_4} \) have very large \( K_a \) values, they would ionize much more completely. Thus, the acid shown must be \( \boxed{\mathrm{HNO_2}} \).

Question 6

Answer the following questions related to \( \mathrm{HBr}(l) \) and \( \mathrm{HF}(l) \).
(a) In the following table, list all of the types of intermolecular forces present in pure samples of \( \mathrm{HBr}(l) \) and \( \mathrm{HF}(l) \).
Liquid\( \mathrm{HBr}(l) \)\( \mathrm{HF}(l) \)
Intermolecular forces present  
(b) The enthalpy of vaporization, \( \Delta H^\circ_{\mathrm{vap}} \), for each liquid is provided in the following table.
Liquid\( \mathrm{HBr}(l) \)\( \mathrm{HF}(l) \)
\( \Delta H^\circ_{\mathrm{vap}} \)\( 17.3\ \mathrm{kJ/mol} \)\( 25.2\ \mathrm{kJ/mol} \)
(i) Based on the types and relative strengths of intermolecular forces, explain why \( \Delta H^\circ_{\mathrm{vap}} \) of \( \mathrm{HF}(l) \) is greater than that of \( \mathrm{HBr}(l) \).
(ii) Calculate the amount of thermal energy, in \( \mathrm{kJ} \), required to vaporize \( 6.85\ \mathrm{g} \) of \( \mathrm{HF}(l) \).
(c) Based on the arrangement of electrons in the \( \mathrm{Br} \) and \( \mathrm{F} \) atoms, explain why the bond length in an \( \mathrm{HBr} \) molecule is greater than that in an \( \mathrm{HF} \) molecule.

Most-appropriate topic codes (AP Chemistry):

• Topic \( 3.1 \) — Intermolecular and Interparticle Forces (Parts \( \mathrm{(a)} \), \( \mathrm{(b)(i)} \))
• Topic \( 6.5 \) — Energy of Phase Changes (Part \( \mathrm{(b)(ii)} \))
• Topic \( 1.7 \) — Periodic Trends (Part \( \mathrm{(c)} \))
▶️ Answer/Explanation

(a)
For the correct answer:
\( \mathrm{HBr}(l) \): London dispersion forces, dipole-dipole attractions
\( \mathrm{HF}(l) \): London dispersion forces, dipole-dipole attractions, hydrogen bonding

Both molecules are polar, so both have dipole-dipole forces and London dispersion forces. Only \( \mathrm{HF} \) has hydrogen bonding because hydrogen is directly bonded to fluorine.

(b)(i)
For a correct explanation:
\( \Delta H^\circ_{\mathrm{vap}} \) is greater for \( \mathrm{HF}(l) \) than \( \mathrm{HBr}(l) \) because the overall intermolecular forces in \( \mathrm{HF}(l) \) are stronger than those in \( \mathrm{HBr}(l) \) due to hydrogen bonding attractions present in \( \mathrm{HF}(l) \). Therefore, more energy is required to separate the molecules in \( \mathrm{HF}(l) \).

Since vaporization requires molecules to overcome intermolecular attractions, the liquid with stronger attractions has the larger \( \Delta H^\circ_{\mathrm{vap}} \).

(b)(ii)
For the correct calculated value:
\( 6.85\ \mathrm{g\ HF} \times \dfrac{1\ \mathrm{mol}}{20.01\ \mathrm{g}} \times \dfrac{25.2\ \mathrm{kJ}}{1\ \mathrm{mol}} = 8.63\ \mathrm{kJ} \)

First convert grams of \( \mathrm{HF} \) to moles, then multiply by \( \Delta H^\circ_{\mathrm{vap}} \).
Therefore, the thermal energy required is \( \boxed{8.63\ \mathrm{kJ}} \).

(c)
For a correct explanation:
\( \mathrm{Br} \) has two additional occupied electron shells \( (n = 3\ \text{and}\ n = 4) \) compared to \( \mathrm{F} \) \( (n = 2) \). The extra electron shells increase the distance between the \( \mathrm{H} \) and \( \mathrm{Br} \) nuclei, giving \( \mathrm{HBr} \) the greater bond length.

In simple terms, bromine is a larger atom than fluorine, so the bonded nuclei in \( \mathrm{HBr} \) are farther apart than in \( \mathrm{HF} \).

Question 7

Strontium hydroxide dissolves in water according to the following equation. The \( K_{sp} \) expression for strontium hydroxide is provided.
\( \mathrm{Sr(OH)}_{2}(s) \rightleftharpoons \mathrm{Sr}^{2+}(aq) + 2\,\mathrm{OH}^{-}(aq) \qquad K_{sp} = [\mathrm{Sr}^{2+}][\mathrm{OH}^{-}]^{2} \)
(a) A student draws the particulate diagram shown to represent the ions present in an aqueous solution of \( \mathrm{Sr(OH)}_{2} \). (Water molecules are intentionally omitted.) Identify the error in the student’s drawing.
(b) The student prepares a saturated solution by adding excess \( \mathrm{Sr(OH)}_{2}(s) \) to distilled water and stirring until no more solid dissolves. The student then determines that \( [\mathrm{Sr}^{2+}] = 0.043\ \mathrm{M} \) in the solution.
(i) Calculate the value of \( [\mathrm{OH}^{-}] \) in the solution.
(ii) Calculate the value of \( K_{sp} \) for \( \mathrm{Sr(OH)}_{2} \).
(c) The student prepares a second saturated solution of \( \mathrm{Sr(OH)}_{2} \) in aqueous \( 0.10\ \mathrm{M\ Sr(NO}_{3})_{2} \) instead of water. Will the value of \( [\mathrm{OH}^{-}] \) in the second solution be greater than, less than, or equal to the value in the first solution? Justify your answer. (Assume constant temperature.)

Most-appropriate topic codes (AP Chemistry):

• Topic \( 7.11 \) — Introduction to Solubility Equilibria (Parts \( \mathrm{(a)} \), \( \mathrm{(b)(i)} \), \( \mathrm{(b)(ii)} \))
• Topic \( 7.12 \) — Common-Ion Effect (Part \( \mathrm{(c)} \))
▶️ Answer/Explanation

(a)
For a correct answer:
Accept one of the following:

• The student’s drawing shows an incorrect ratio of \( \mathrm{Sr}^{2+} \) and \( \mathrm{OH}^{-} \) ions.
• The student’s drawing is not charge-balanced.

Since each \( \mathrm{Sr}^{2+} \) ion must be accompanied by two \( \mathrm{OH}^{-} \) ions, the diagram should show twice as many hydroxide ions as strontium ions.

(b)(i)
For the correct calculated value:
\( 0.043\ \mathrm{mol\ Sr}^{2+}\!/\mathrm{L} \times \dfrac{2\ \mathrm{mol\ OH}^{-}}{1\ \mathrm{mol\ Sr}^{2+}} = 0.086\ \mathrm{M\ OH}^{-} \)

The coefficient \( 2 \) in the dissolution equation means hydroxide concentration is twice the strontium ion concentration.
Therefore, \( \boxed{[\mathrm{OH}^{-}] = 0.086\ \mathrm{M}} \).

(b)(ii)
For the correct calculated value, consistent with part \( \mathrm{(b)(i)} \):
\( K_{sp} = [\mathrm{Sr}^{2+}][\mathrm{OH}^{-}]^{2} = (0.043)(0.086)^{2} = 3.2 \times 10^{-4} \)

Squaring \( [\mathrm{OH}^{-}] \) is important because there are \( 2 \) hydroxide ions in the balanced dissolution equation.
Thus, \( \boxed{K_{sp} = 3.2 \times 10^{-4}} \).

(c)
For the correct answer and a valid justification:
Less than. Because the \( \mathrm{Sr(NO}_{3})_{2}(aq) \) solution already contains a common ion, \( \mathrm{Sr}^{2+}(aq) \), the solubility of \( \mathrm{Sr(OH)}_{2} \) will be decreased, resulting in a lower value of \( [\mathrm{OH}^{-}] \).

Adding extra \( \mathrm{Sr}^{2+} \) shifts the dissolution equilibrium to the left, so less \( \mathrm{Sr(OH)}_{2} \) dissolves and fewer hydroxide ions are produced.

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