Ions in Solutions (5A)

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MCAT Chemical and Physical Foundations of Biological Systems › Ions in Solutions (5A)

Questions 1 - 10
1

A desalting step uses an anion-exchange resin in the OH$^-$ form. When a solution containing HCl passes through, exchange occurs: R–N$^+$(CH$_3$)$_3$ OH$^-$(s) + Cl$^-$(aq) $\rightleftharpoons$ R–N$^+$(CH$_3$)$_3$ Cl$^-$(s) + OH$^-$(aq). In the effluent, H$^+$(aq) + OH$^-$(aq) $\rightarrow$ H$_2$O(l). Which outcome would be expected from the described ion interaction?

Chloride concentration increases because the resin releases Cl$^-$ into solution

No change occurs because ion exchange cannot alter pH

Effluent becomes less acidic because OH$^-$ is released and neutralizes H$^+$

Effluent becomes more acidic because OH$^-$ is consumed by the resin

Explanation

This question tests understanding of anion exchange coupled with acid-base neutralization. The OH--form resin exchanges OH- for Cl- from the HCl solution, releasing OH- into the effluent. This OH- immediately neutralizes H+ from HCl to form water, effectively removing both H+ and Cl- from solution and decreasing acidity. The correct answer B states that effluent becomes less acidic because OH- is released and neutralizes H+. Answer A incorrectly suggests acidification, while D incorrectly claims ion exchange cannot alter pH. When using OH--form anion exchangers with acids, expect neutralization as OH- is released to react with H+.

2

A protein purification step uses a cation-exchange resin bearing fixed negative sulfonate groups (Resine). A sample in low-salt buffer contains Naba, Cababa, and a positively charged peptide Pba. The resin is initially in the Naba form. Ion exchange can be represented as: Resineb7Naba + Pba cc Resineb7Pba + Naba. Which outcome would be expected when the NaCl concentration in the buffer is increased substantially during elution?

Pba is more likely to elute because Naba competes with Pba for binding sites on the resin.

Pba is more likely to elute because added Cle binds to the negative resin and neutralizes it.

Pba is more likely to remain bound because higher ionic strength increases electrostatic attraction to the resin.

Pba is more likely to remain bound because added NaCl decreases the number of ions in solution.

Explanation

This question tests understanding of ion exchange chromatography, where ions compete for binding sites based on concentration and charge. The principle is that cation exchange resins have fixed negative charges that attract and bind positively charged ions, with binding equilibria that can be shifted by changing ion concentrations. In this system, the peptide P+ is initially bound to the negatively charged resin, but increasing NaCl concentration floods the system with Na+ ions. The correct answer B follows because the mass action principle dictates that high Na+ concentration drives the equilibrium toward Na+ binding to the resin, displacing P+ into solution. Choice D incorrectly suggests that higher ionic strength increases binding, when actually it shields electrostatic interactions and promotes elution. A useful strategy is to apply Le Chatelier's principle: adding excess of one ion (Na+) shifts the equilibrium to consume that excess, displacing the originally bound ion.

3

A patch-clamp experiment uses an extracellular solution containing 150 mM NaCl and 2 mM CaCl. A chelator is added that selectively binds free Cababa, decreasing its free concentration without changing total chloride. Which outcome is most consistent with ion behavior in solution and charge balance?

The solution becomes net positive because binding Cababa releases additional Cle into solution.

The solution can remain overall electroneutral because Cababa is replaced by an equivalent amount of bound (nonfree) Cababa within the chelator complex.

Free Cle concentration must decrease to maintain electroneutrality, even though no chloride-binding agent is added.

The solution becomes net negative because removing free Cababa removes positive charge from the solution entirely.

Explanation

This question tests understanding of electroneutrality and the distinction between free ions and complexed ions in solution. The principle of electroneutrality states that the sum of positive charges must equal the sum of negative charges in any solution. When the chelator binds Ca2+, it forms a complex where Ca2+ is still present but no longer free - the calcium is now part of a larger complex that maintains the same overall charge. The correct answer B follows because the Ca2+ isn't removed from solution entirely, just converted from free Ca2+ to chelator-bound Ca2+, maintaining the same total positive charge to balance the negative charges from Cl- and other anions. Choice A incorrectly suggests Cl- concentration must change even though no chloride-binding occurs, violating mass conservation. A key concept is that electroneutrality considers all charges present, whether in free ions or complexes, and chelation changes the form but not the total charge balance.

4

A chromatography resin with fixed negative charges (Re) is equilibrated with Cababa (Reb7Cababa). A sample containing Naba is applied. A simplified exchange is: Reb7Cababa + 2Naba cc 2(Reb7Naba) + Cababa. Which outcome is expected when a high concentration of NaCl is flowed through the column?

No change occurs because ion exchange requires a change in pH, not salt concentration.

Cababa is displaced into solution because increased [Naba] drives the exchange equilibrium to the right.

Cle binds to Re and displaces Cababa because opposite charges repel on the resin surface.

More Cababa remains bound because high [Naba] drives the equilibrium left by the common-ion effect.

Explanation

This question tests understanding of ion exchange equilibria in chromatography systems. The principle is that ion exchange follows mass action laws, where high concentrations of competing ions can displace bound ions from the resin. In this system, Ca2+ is initially bound to the negatively charged resin sites, but flowing high concentration NaCl through provides excess Na+ ions. The correct answer B follows because the equilibrium R-·Ca2+ + 2Na+ ⇌ 2(R-·Na+) + Ca2+ is driven to the right by the high Na+ concentration, displacing Ca2+ into solution for elution. Choice A incorrectly invokes the common-ion effect, which applies to solubility equilibria not ion exchange, and gets the direction wrong - high [Na+] drives the equilibrium right, not left. A key strategy is to apply Le Chatelier's principle to ion exchange: excess of the competing ion (Na+) shifts equilibrium to consume that excess, displacing the originally bound ion.

5

A conductivity probe is placed in two solutions at 25C, each prepared to the same formal concentration (0.10 M): Solution 1 contains NaSO; Solution 2 contains NaCl. Both salts fully dissociate: NaSO d2 2Naba + SOb2e; NaCl d2 Naba + Cle. Ignoring differences in ionic mobility, which outcome is expected for conductivity?

Solution 1 has lower conductivity because sulfate ions are larger and therefore eliminate current flow.

Solution 1 has higher conductivity because it produces a greater total concentration of ions per formula unit dissolved.

Solution 2 has higher conductivity because monovalent ions always carry charge more efficiently than divalent ions.

Both solutions have identical conductivity because formal concentration fixes the number of charge carriers.

Explanation

This question tests understanding of how dissociation stoichiometry affects ion concentration and conductivity. The principle is that conductivity depends on the total concentration of ions, which varies with how many ions each formula unit produces upon dissociation. In this system, 0.10 M Na2SO4 dissociates to give 2(0.10) = 0.20 M Na+ and 0.10 M SO42- for 0.30 M total ions, while 0.10 M NaCl gives 0.10 M Na+ and 0.10 M Cl- for 0.20 M total ions. The correct answer B follows because Na2SO4 produces 3 ions per formula unit (2 Na+ + 1 SO42-) while NaCl produces only 2 ions per formula unit, giving Na2SO4 solution 50% more total ion concentration and thus higher conductivity. Choice A incorrectly generalizes about monovalent versus divalent ions without considering the actual ion count. A reliable strategy is to calculate total ion concentration by multiplying molarity by the number of ions produced per formula unit.

6

A solubility study examines CaF in the presence of added NaF. The equilibrium is: CaF(s) cc Cababa(aq) + 2Fe(aq). A researcher adds NaF to a saturated CaF solution while keeping temperature constant. Which outcome would be expected from the described ion interaction?

CaF solubility increases because adding Fe shifts the equilibrium right to produce more Cababa.

CaF solubility decreases because added Naba forms insoluble NaF(s), removing Fe from solution.

CaF solubility is unchanged because NaF is a strong electrolyte and does not affect equilibria.

CaF solubility decreases because added Fe drives the equilibrium left, favoring precipitation of CaF(s).

Explanation

This question tests understanding of the common-ion effect on solubility equilibria. The principle is that adding a common ion (one already present in the equilibrium) shifts the equilibrium according to Le Chatelier's principle, typically decreasing solubility of sparingly soluble salts. In this system, CaF2 is in equilibrium with Ca2+ and F- ions, and adding NaF increases the F- concentration. The correct answer B follows because the added F- from NaF shifts the equilibrium CaF2(s) ⇌ Ca2+ + 2F- to the left, favoring the solid form and decreasing CaF2 solubility - this is the classic common-ion effect. Choice A incorrectly predicts the equilibrium shift direction, suggesting added F- would somehow produce more Ca2+, which violates Le Chatelier's principle. A key strategy is recognizing that adding a product of an equilibrium (F-) always shifts the equilibrium toward reactants (CaF2(s)), reducing solubility.

7

To compare electrolyte strength, equal volumes of 0.050 M solutions are prepared at 25C: HCl, NH, and MgCl. Relevant equilibria: HCl(aq) d2 Hba + Cle; NH(aq) + Hbae cc NHba + OHe; MgCl(s) d2 Mgbaba + 2Cle. Which statement best reflects ion behavior affecting conductivity at equal molarity?

HCl will conduct poorly because Hba is covalently bound to water and not a charge carrier.

HCl and MgCl will both conduct strongly because they produce substantial ion concentrations in solution.

NH will conduct best because it produces both NHba and OHe, doubling charge carriers.

MgCl will conduct poorly because multivalent ions reduce mobility enough to dominate conductivity.

Explanation

This question tests understanding of how ion concentration from different electrolytes affects solution conductivity. The principle is that conductivity depends on the total concentration of all ions in solution, with strong electrolytes producing more ions than weak electrolytes. In this system, HCl is a strong acid producing 0.050 M H+ and 0.050 M Cl-, NH3 is a weak base producing very few ions, and MgCl2 dissociates completely to give 0.050 M Mg2+ and 0.100 M Cl-. The correct answer B follows because both HCl and MgCl2 are strong electrolytes that fully dissociate, producing substantial ion concentrations (0.100 M total for HCl, 0.150 M total for MgCl2). Choice C incorrectly assumes multivalent ions have such reduced mobility that it dominates over their contribution to conductivity, when in reality the higher total ion concentration from MgCl2 more than compensates. A useful approach is to calculate total ion concentration for each solution, recognizing that conductivity generally increases with total ion concentration.

8

A dialysis experiment uses a membrane permeable to $\mathrm{Na^+}$ and $\mathrm{Cl^-}$ but impermeable to a large anion $\mathrm{P^{3-}}$ (a polyanion). Side 1 contains 50 mM NaCl plus 10 mM $\mathrm{Na_3P}$; Side 2 contains 50 mM NaCl only. Which outcome would be expected at equilibrium based on ion behavior (Donnan effect) and electroneutrality constraints?

Side 1 becomes net negative because impermeant $\mathrm{P^{3-}}$ cannot be balanced by mobile ions across a membrane.

Side 1 retains extra $\mathrm{Na^+}$ relative to Side 2 to balance impermeant $\mathrm{P^{3-}}$, with corresponding redistribution of $\mathrm{Cl^-}$.

Side 2 accumulates $\mathrm{Na^+}$ because cations always diffuse toward the side with fewer total solutes.

All ions equalize to identical concentrations on both sides because diffusion eliminates any gradient regardless of impermeant ions.

Explanation

This question tests understanding of the Donnan equilibrium effect with impermeant ions. When a membrane separates solutions containing both permeant ions (Na⁺, Cl⁻) and an impermeant ion (P³⁻), the impermeant ion creates an unequal distribution of permeant ions at equilibrium. Side 1 contains impermeant P³⁻ which carries negative charge that must be balanced by mobile cations. This causes Side 1 to retain extra Na⁺ relative to Side 2, and Cl⁻ redistributes accordingly to maintain electroneutrality on both sides and satisfy the Donnan equilibrium condition. Choice B incorrectly ignores the constraint imposed by the impermeant ion, while choice C violates electroneutrality. The key principle is that impermeant ions create asymmetric distributions of permeant ions while maintaining electroneutrality. To solve Donnan problems, remember that the product [cation]×[anion] must be equal on both sides for permeant ions.

9

A weak base anesthetic (B) is formulated as its hydrochloride salt (BH+Cl−) to improve aqueous solubility. In water: $\mathrm{BH^+ \rightleftharpoons B + H^+}$ and $\mathrm{BH^+Cl^- \rightarrow BH^+ + Cl^-}$. Which statement best reflects the behavior of ions in the solution when a small amount of NaOH is added?

$\mathrm{OH^-}$ consumes $\mathrm{H^+}$, shifting $\mathrm{BH^+ \rightleftharpoons B + H^+}$ toward neutral B and decreasing the fraction of charged species.

NaOH decreases solubility by precipitating $\mathrm{NaCl}$, removing counterions required for dissolution.

$\mathrm{OH^-}$ increases the fraction of $\mathrm{BH^+}$ because bases protonate amines, increasing ionization.

NaOH has no effect because $\mathrm{Cl^-}$ is a spectator ion and spectators fix the $\mathrm{BH^+}$/$\mathrm{B}$ ratio.

Explanation

This question tests understanding of acid-base equilibria and ion speciation in drug formulations. The hydrochloride salt BH⁺Cl⁻ dissociates completely to give BH⁺ (protonated base) and Cl⁻. When NaOH is added, the OH⁻ ions react with H⁺ from the equilibrium BH⁺ ⇌ B + H⁺, removing H⁺ and shifting the equilibrium toward the neutral base B. This decreases the fraction of charged BH⁺ species in solution. Choice B incorrectly suggests OH⁻ would protonate the amine, but bases deprotonate acids, not protonate bases. The principle is that adding base shifts weak acid equilibria toward their conjugate bases. For similar problems involving drug ionization, track how pH changes affect the protonation state using Henderson-Hasselbalch concepts.

10

A physiologist adds EDTA (a chelating agent) to plasma to reduce free $\mathrm{Ca^{2+}}$ activity and prevent clotting. EDTA binds calcium: $\mathrm{Ca^{2+} + EDTA^{4-} \rightleftharpoonsCaEDTA^{2-}}$. Which outcome would be expected from this ion interaction in solution?

Free $\mathrm{Ca^{2+}}$ decreases because complex formation sequesters calcium into a soluble anionic complex.

EDTA decreases conductivity to zero by removing all ions, including $\mathrm{Na^+}$ and $\mathrm{Cl^-}$, from plasma.

EDTA causes calcium to precipitate as $\mathrm{Ca(OH)_2(s)}$ because chelation always reduces solubility of metal ions.

Free $\mathrm{Ca^{2+}}$ increases because binding to EDTA releases additional $\mathrm{Ca^{2+}}$ from the complex by mass action.

Explanation

This question tests understanding of chelation and complex ion formation in biological systems. EDTA is a hexadentate ligand that forms stable complexes with metal ions like Ca²⁺. When EDTA binds Ca²⁺, it forms the soluble complex [CaEDTA]²⁻, effectively sequestering the calcium and reducing the concentration of free Ca²⁺ ions in solution. This prevents calcium from participating in clotting reactions that require free Ca²⁺. Choice B incorrectly suggests complex formation would increase free Ca²⁺, which contradicts the equilibrium direction. Choice D wrongly claims chelation causes precipitation, but EDTA complexes are highly soluble. The key concept is that chelation removes free metal ions by incorporating them into soluble complexes. To approach chelation problems, recognize that complex formation reduces free ion concentration without precipitation.

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