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AP Chemistry 1.7 Periodic Trends- Exam Style questions - FRQs- New Syllabus

Question

Sterling silver is an alloy that is commonly used to make jewelry and consists of \( 92.5\% \) silver and \( 7.5\% \) other metals, such as copper, by mass. Over time, the alloy can form a tarnish of \( \mathrm{Ag_2S(s)} \) when it reacts with hydrogen sulfide, as represented by the following equation.
\( \mathrm{2\,Ag(s) + H_2S(g) \rightarrow Ag_2S(s) + H_2(g)} \)
(a) What are the oxidation numbers of silver in \( \mathrm{Ag(s)} \) and \( \mathrm{Ag_2S(s)} \)?
\( \mathrm{Ag(s)} \) __________      \( \mathrm{Ag_2S(s)} \) __________
(b) The following table contains the atomic radii for silver and copper.
ElementSilver \( \mathrm{(Ag)} \)Copper \( \mathrm{(Cu)} \)
Atomic radius \( \mathrm{(pm)} \)\( 165 \)\( 145 \)
(i) Explain why sterling silver is better classified as a substitutional alloy than as an interstitial alloy.
(ii) Using principles of atomic structure and Coulomb’s law, explain why silver has a larger atomic radius than copper does.
The \( \mathrm{Ag_2S} \) tarnish on sterling silver can be removed until only sterling silver remains. A student weighs a tarnished sterling silver sample both before and after removing the \( \mathrm{Ag_2S(s)} \) \((\mathrm{molar\ mass}\ 247.80\ \mathrm{g/mol})\) and records the data in the following table.
 Before Tarnish RemovalAfter Tarnish Removal
Mass\( 409.21\ \mathrm{g} \)\( 398.94\ \mathrm{g} \)
(c) Assuming that only \( \mathrm{Ag_2S(s)} \) is removed, calculate the number of moles of silver atoms removed.
Rhodium plating is a process used to protect sterling silver from tarnishing. This involves electroplating (depositing) solid rhodium, \( \mathrm{Rh(s)} \), onto the surface of the metal from an acidified solution of \( \mathrm{Rh_2(SO_4)_3(aq)} \). Oxygen gas is produced during this process.
(d) A table of half-reactions related to the overall reaction is provided.
Half-Reaction\( E^\circ \) \( \mathrm{(V)} \)
\( \mathrm{Rh^{3+}(aq) + 3\,e^- \rightarrow Rh(s)} \)\( +0.80 \)
\( \mathrm{O_2(g) + 4\,H^+(aq) + 4\,e^- \rightarrow 2\,H_2O(l)} \)\( +1.23 \)
(i) Write the balanced net ionic equation for plating \( \mathrm{Rh(s)} \) from the acidified \( \mathrm{Rh_2(SO_4)_3(aq)} \) solution.
(ii) Calculate the value of \( E^\circ_{\mathrm{cell}} \) for the reaction in part \( \mathrm{(d)(i)} \).
(iii) Based on your answer to part \( \mathrm{(d)(ii)} \), explain why this process requires the use of an external power source.
(e) Calculate the length of time, in seconds, required to plate \( 2.8\ \mathrm{g} \) of \( \mathrm{Rh(s)} \) onto a piece of sterling silver if \( 2.0\ \mathrm{C/s} \) of current is applied.

Most-appropriate topic codes (AP Chemistry):

• Topic \( 4.9 \) — Oxidation-Reduction (Redox) Reactions (Part (a))
• Topic \( 3.2 \) — Properties of Solids (Part (b)(i))
• Topic \( 1.7 \) — Periodic Trends (Part (b)(ii))
• Topic \( 4.5 \) — Stoichiometry (Part (c))
• Topic \( 9.8 \) — Galvanic (Voltaic) and Electrolytic Cells (Part (d)(i))
• Topic \( 9.9 \) — Cell Potential and Free Energy (Parts (d)(ii), (d)(iii))
• Topic \( 9.11 \) — Electrolysis and Faraday’s Law (Part (e))
▶️ Answer/Explanation

(a)
For the correct answer:
\( \mathrm{Ag(s)} \): \( 0 \)      \( \mathrm{Ag_2S(s)} \): \( +1 \)
An element in its standard form has oxidation number \( 0 \). In \( \mathrm{Ag_2S} \), sulfur is typically \( -2 \), so the two silver atoms together must total \( +2 \), giving each silver atom \( +1 \).

(b)(i)
For a valid explanation:
Sterling silver is better classified as a substitutional alloy because silver and copper have similar atomic radii, \( 165\ \mathrm{pm} \) and \( 145\ \mathrm{pm} \), so copper atoms can replace silver atoms in the metal lattice rather than fitting into small holes between them.

(b)(ii)
For a valid explanation:
Silver has more occupied electron shells \((n=5)\) than copper \((n=4)\), so its valence electrons are farther from the nucleus and experience weaker Coulombic attraction. Therefore, silver has the larger atomic radius.

(c)
For the correct calculated mass of \( \mathrm{Ag_2S} \):
\( 409.21\ \mathrm{g} – 398.94\ \mathrm{g} = 10.27\ \mathrm{g} \)

For the correct calculated moles of silver atoms:
\( 10.27\ \mathrm{g\ Ag_2S} \times \dfrac{1\ \mathrm{mol\ Ag_2S}}{247.80\ \mathrm{g\ Ag_2S}} \times \dfrac{2\ \mathrm{mol\ Ag}}{1\ \mathrm{mol\ Ag_2S}} = 0.08289\ \mathrm{mol\ Ag} \)

So, the number of moles of silver atoms removed is \( \boxed{0.0829\ \mathrm{mol}} \).

(d)(i)
For the correct balanced equation (state symbols not required):
\( \mathrm{4\,Rh^{3+}(aq) + 6\,H_2O(l) \rightarrow 4\,Rh(s) + 3\,O_2(g) + 12\,H^+(aq)} \)
The reduction half-reaction is multiplied by \( 4 \), and the oxidation of water is the reverse of the given oxygen reduction half-reaction, multiplied by \( 3 \), so that \( 12 \) electrons cancel.

(d)(ii)
For the correct calculated value, consistent with part \( \mathrm{(d)(i)} \):
\( E^\circ_{\mathrm{cell}} = 0.80\ \mathrm{V} – 1.23\ \mathrm{V} = -0.43\ \mathrm{V} \)

The plating reaction uses the \( \mathrm{Rh^{3+}/Rh} \) reduction and the oxidation of water.
Because the oxidation potential of water is \( -1.23\ \mathrm{V} \) when written from the reduction table, the total cell potential is negative.

(d)(iii)
For a correct explanation, consistent with part \( \mathrm{(d)(ii)} \):
Since \( E^\circ_{\mathrm{cell}} \) is negative, the reaction is not thermodynamically favorable as written. Therefore, an external power source is required to drive the electroplating process.

(e)
For the correct calculated value of moles of electrons:
\( 2.8\ \mathrm{g\ Rh} \times \dfrac{1\ \mathrm{mol\ Rh}}{102.9\ \mathrm{g\ Rh}} \times \dfrac{3\ \mathrm{mol\ e^-}}{1\ \mathrm{mol\ Rh}} = 0.0816\ \mathrm{mol\ e^-} \)

For the correct calculated value of time:
\( 0.0816\ \mathrm{mol\ e^-} \times \dfrac{96{,}485\ \mathrm{C}}{1\ \mathrm{mol\ e^-}} \times \dfrac{1\ \mathrm{s}}{2.0\ \mathrm{C}} = 3.94\times10^3\ \mathrm{s} \)

Therefore, the time required is approximately \( \boxed{3900\ \mathrm{s}} \).
The small difference between \( 3940\ \mathrm{s} \) and \( 3900\ \mathrm{s} \) is due to rounding.

 
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