Chemistry 9701 · AS & A Level · Carboxylic acids and derivatives

Carboxylic acids and derivatives — practice question

(a)[3]

Compare and explain the relative acidities of 2-chloropropanoic acid, 3-chloropropanoic acid, and propanoic acid. Give your explanation.

(b(i))[1]

The $K_a$ values for methanoic acid, $\text{HCO}_2\text{H}$, and pyruvic acid, $\text{CH}_3\text{COCO}_2\text{H}$, are supplied. An equilibrium mixture containing the two acid-base pairs is set up: $\text{HCO}_2^- + \text{CH}_3\text{COCO}_2\text{H} \rightleftharpoons \text{HCO}_2\text{H} + \text{CH}_3\text{COCO}_2^-$ Use the $K_a$ values to calculate the equilibrium constant, $K_{eq}$, for this equilibrium.

(b(ii))[1]

Use your value of $K_{eq}$ to predict where this equilibrium lies. Show this by placing a tick ($\checkmark$) in the correct box in the table. Explain your answer.

(b(iii))[2]

Ethanedioic acid, $\text{HO}_2\text{CCO}_2\text{H}$, has two dissociation constants, $K_{a1}$ and $K_{a2}$, and their $pK_a$ values are 1.23 and 4.19. Write equations to represent the two dissociation steps that correspond to these $pK_a$ values.

(b(iv))[1]

State the mathematical relationship connecting $pK_a$ and the acid dissociation constant $K_a$.

(c)[5]

Three tests were performed on separate samples of the organic acids shown in the table, and the results below were recorded. $\checkmark$ = change observed, $\times$ = no reaction seen. Fill in the table with the reagent(s) and conditions, plus the observed change for each test. Assume that all of these organic acids have similar acid strength.

(a(iii))[2]

Ethanedioic acid, HO$_2$CCO$_2$H, has two dissociation constants, $K_{a1}$ and $K_{a2}$, and their $pK_a$ values are 1.23 and 4.19. Suggest equations to show the two dissociations that correspond to these $pK_a$ values. $pK_{a1}$ 1.23 $pK_{a2}$ 4.19

(a(iv))[1]

State how $pK_a$ is related to the acid dissociation constant $K_a$.

(d)[2]

A sample of pyruvic acid, CH$_3$COCO$_2$H, is analysed by carbon-13 NMR spectroscopy. Three peaks are observed. Complete the table by: • circling the carbon atom responsible for the chemical shift • stating the hybridisation of the circled carbon atom.

(e)[3]

An ester of pyruvic acid, F, is dissolved in CDCl$_3$ and analysed by proton NMR spectroscopy. The proton NMR spectrum of F is shown. Use the proton NMR spectrum of F to complete the table.

(f)[2]

Deuterium oxide, D$_2$O, where D is $^{2}_{1}$H, can be used as a solvent in proton NMR spectroscopy. The proton NMR spectrum of alanine in CDCl$_3$ has 4 peaks. The proton NMR spectrum of alanine in D$_2$O$ has 2 peaks. On the diagram of alanine, circle the protons that show peaks in both NMR spectra. Explain your answer.

(g(i))[1]

The ionic product, $K_w$, for D$_2$O has a value of $1.35 \times 10^{-15}\ \text{mol}^2\text{dm}^{-6}$ at 298 K. Write the expression for the $K_w$ of D$_2$O.

(g(ii))[2]

Calculate the pH of pure, neutral D$_2$O at 298 K. Treat $[\text{D}^+]$ as equivalent to $[\text{H}^+]$ when doing the pH calculation.

Worked solution & mark scheme

This 26-mark question has a full step-by-step worked solution and mark scheme. One marking point: Order of acidity: 2-chloropropanoic acid > 3-chloropropanoic acid > propanoic acid.

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