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Question #44364

Difficulty: 8/10 | 🟢 Free

The Question

An aqueous solution of D-glucose at 298 K298\text{ K} is at mutarotation equilibrium, consisting of 36%36\% α\alpha-D-glucopyranose and 64%64\% β\beta-D-glucopyranose (open-chain form ≈0.02%\approx 0.02\%). At t=0t=0, a large excess of a trapping reagent is added. This reagent reacts instantaneously and irreversibly \textit{exclusively} with the open-chain aldehyde form of D-glucose. Let kαk_\alpha and kβk_\beta be the first-order rate constants for the ring-opening of the α\alpha and β\beta anomers, respectively, where kα≠kβk_\alpha \neq k_\beta. Which of the following statements correctly describes the kinetic decay of the total unreacted cyclic glucose concentration, [G]total[G]_{total}, and the evolution of the α/β\alpha/\beta ratio during the reaction?

Options

  • A.

    [G]total[G]_{total} decays as a biphasic function [α]0e−kαt+[β]0e−kβt[\alpha]_0 e^{-k_\alpha t} + [\beta]_0 e^{-k_\beta t}, and the α/β\alpha/\beta ratio changes continuously over time.

  • B.

    [G]total[G]_{total} decays as a single exponential function ([α]0+[β]0)e−kobst([\alpha]_0 + [\beta]_0) e^{-k_{obs} t} where kobs=0.36kα+0.64kβk_{obs} = 0.36 k_\alpha + 0.64 k_\beta, maintaining a constant α/β\alpha/\beta ratio.

  • C.

    [G]total[G]_{total} decays following pseudo-zero-order kinetics because the concentration of the reactive open-chain intermediate is thermodynamically buffered at 0.02%0.02\%.

  • D.

    [G]total[G]_{total} decays as a single exponential function ([α]0+[β]0)e−(kα+kβ)t([\alpha]_0 + [\beta]_0) e^{-(k_\alpha + k_\beta) t}, and the α/β\alpha/\beta ratio rapidly shifts to 1:11:1.

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Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Mechanism_Trap

Don't get tricked by the process! Learn the mechanical traps used in competitive exam questions.

Concepts Behind This Question

Optical Activity and Enantiomers|D-Glucose Anomeric Equilibrium|Reducing Sugar Criteria

Why This Question Is Tricky

Common Mistakes

This question tests the 'Hidden Variable' of kinetic decoupling in a classic thermodynamic equilibrium.

Students memorize that mutarotation maintains an equilibrium ratio via Le Chatelier's principle and exhibits first-order kinetics.

The trap is assuming that the α\alpha and β\beta anomers remain in rapid pre-equilibrium when a reagent consumes the intermediate.

By irreversibly scavenging the open-chain form, the interconversion pathway is severed.

The anomers are forced into independent, parallel kinetic pathways, changing the macroscopic decay from a single exponential to a biphasic function and continuously altering the anomeric ratio.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterHaloalkanes and Haloarenes - Class 12
ConceptOptical Activity and Enantiomers
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree