An original Thinka practice paper modelled on the structure and difficulty of the May 2024 SL (TZ2) IB Diploma Programme Chemistry paper. Not affiliated with or reproduced from IB.
Paper 1
Answer all questions. Choose the best response for each question on the answer sheet.
30 Question · 30 marks
Question 1 · multiple-choice
1 marks
Which of the following species has a central atom with a formal charge of +1?
A.\(\text{H}_3\text{O}^+\)
B.\(\text{NH}_3\)
C.\(\text{BF}_4^-\)
D.\(\text{CO}_2\)
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Worked solution
Formal charge is calculated as: Valence electrons - Non-bonding electrons - 0.5 * Bonding electrons. For \(\text{H}_3\text{O}^+\), the central oxygen atom has 6 valence electrons, 2 non-bonding electrons (one lone pair), and 6 bonding electrons (three single bonds). This gives a formal charge of: \(6 - 2 - \frac{1}{2}(6) = +1\).
Marking scheme
Award [1] for the correct option A. No marks for any other response.
Question 2 · multiple-choice
1 marks
An element \(\text{M}\) in Period 3 of the periodic table has the following successive ionization energies (in \(\text{kJ}\,\text{mol}^{-1}\)): \(\text{IE}_1 = 578\), \(\text{IE}_2 = 1817\), \(\text{IE}_3 = 2745\), \(\text{IE}_4 = 11577\), \(\text{IE}_5 = 14842\). Which formula represents the oxide of this element?
A.\(\text{MO}\)
B.\(\text{M}_2\text{O}_3\)
C.\(\text{MO}_2\)
D.\(\text{M}_2\text{O}\)
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Worked solution
There is a very large relative jump between the third (2745) and fourth (11577) ionization energies. This indicates that the fourth electron is being removed from an inner core shell, meaning the element has three valence electrons (Group 13). Thus, the element forms a \(\text{M}^{3+}\) ion. Since the oxide ion is \(\text{O}^{2-}\), the empirical formula of the oxide is \(\text{M}_2\text{O}_3\).
Marking scheme
Award [1] for the correct option B. No marks for any other response.
Question 3 · multiple-choice
1 marks
A hydrocarbon is analyzed and found to contain 85.6% carbon and 14.4% hydrogen by mass. What is its empirical formula? (Relative atomic masses: \(\text{C} = 12.01\), \(\text{H} = 1.01\))
A.\(\text{CH}\)
B.\(\text{CH}_2\)
C.\(\text{CH}_3\)
D.\(\text{C}_2\text{H}_5\)
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Worked solution
Convert the mass percentages to moles per 100 g: \(n(\text{C}) = \frac{85.6}{12.01} = 7.13\,\text{mol}\), \(n(\text{H}) = \frac{14.4}{1.01} = 14.26\,\text{mol}\). Dividing each by the smallest value (7.13) yields a ratio of \(1\,\text{C} : 2\,\text{H}\). The empirical formula is therefore \(\text{CH}_2\).
Marking scheme
Award [1] for the correct option B. No marks for any other response.
Question 4 · multiple-choice
1 marks
When \(50.0\,\text{cm}^3\) of \(1.00\,\text{mol}\,\text{dm}^{-3}\ \text{HCl(aq)}\) is mixed with \(50.0\,\text{cm}^3\) of \(1.00\,\text{mol}\,\text{dm}^{-3}\ \text{NaOH(aq)}\) in a coffee-cup calorimeter, the temperature rises by \(6.0\,^\circ\text{C}\). Assuming the total mass of the mixture is \(100.0\,\text{g}\) and the specific heat capacity is \(4.18\,\text{J}\,\text{g}^{-1}\,\text{K}^{-1}\), which expression calculates the enthalpy change of neutralization, \(\Delta H^\ominus\), in \(\text{kJ}\,\text{mol}^{-1}\)?
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Worked solution
The heat released in the reaction is calculated by \(q = m \cdot c \cdot \Delta T = 100.0 \times 4.18 \times 6.0\) (in J). To convert this heat to kilojoules, it is divided by 1000. The number of moles of water formed is calculated from the limiting reactant: \(n = 0.0500\,\text{dm}^3 \times 1.00\,\text{mol}\,\text{dm}^{-3} = 0.0500\,\text{mol}\). The enthalpy change of neutralization is defined as \(\Delta H^\ominus = -\frac{q}{n}\), which gives \(-\frac{100.0 \times 4.18 \times 6.0}{0.0500 \times 1000}\).
Marking scheme
Award [1] for the correct option A. No marks for any other response.
Question 5 · multiple-choice
1 marks
In which reaction does the dihydrogen phosphate ion, \(\text{H}_2\text{PO}_4^-\), act as a Brønsted–Lowry base?
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Worked solution
A Brønsted–Lowry base is defined as a proton (\(\text{H}^+\)) acceptor. In reaction C, the \(\text{H}_2\text{PO}_4^-\) ion accepts a proton from the hydronium ion (\(\text{H}_3\text{O}^+\)) to form phosphoric acid (\(\text{H}_3\text{PO}_4\)), acting as a base.
Marking scheme
Award [1] for the correct option C. No marks for any other response.
Question 6 · multiple-choice
1 marks
A proposed reaction mechanism for the reaction between nitrogen dioxide and fluorine is shown below. Step 1 (slow): \(\text{NO}_2\text{(g)} + \text{F}_2\text{(g)} \rightarrow \text{NO}_2\text{F(g)} + \text{F(g)}\). Step 2 (fast): \(\text{NO}_2\text{(g)} + \text{F(g)} \rightarrow \text{NO}_2\text{F(g)}\). What is the expected rate expression for this reaction?
A.\(\text{Rate} = k[\text{NO}_2]^2[\text{F}_2]\)
B.\(\text{Rate} = k[\text{NO}_2][\text{F}_2]\)
C.\(\text{Rate} = k[\text{NO}_2][\text{F}]\)
D.\(\text{Rate} = k[\text{NO}_2]^2\)
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Worked solution
The slow step in a reaction mechanism is the rate-determining step. The rate expression depends on the concentrations of the reactants in the rate-determining step, each raised to the power of its stoichiometric coefficient in that step. For Step 1, the reactants are \(\text{NO}_2\) and \(\text{F}_2\), giving \(\text{Rate} = k[\text{NO}_2][\text{F}_2]\).
Marking scheme
Award [1] for the correct option B. No marks for any other response.
Question 7 · multiple-choice
1 marks
What is the average oxidation state of sulfur in the thiosulfate ion, \(\text{S}_2\text{O}_3^{2-}\)?
A.\(-2\)
B.\(+2\)
C.\(+4\)
D.\(+6\)
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Worked solution
Let the oxidation state of sulfur be represented by \(x\). Oxygen typically has an oxidation state of \(-2\). The sum of the oxidation states in the polyatomic ion must equal the overall charge: \(2(x) + 3(-2) = -2 \Rightarrow 2x - 6 = -2 \Rightarrow 2x = +4 \Rightarrow x = +2\).
Marking scheme
Award [1] for the correct option B. No marks for any other response.
Question 8 · multiple-choice
1 marks
Which of the following condensed structural formulas represents a compound containing both an ester and a ketone functional group?
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Worked solution
Option A, \(\text{CH}_3\text{COCH}_2\text{COOCH}_3\), contains a ketone carbonyl group (\(\text{-CO-}\) bonded to two carbon atoms) and an ester group (\(\text{-COO-}\) linked to a methyl group). Option B contains an alcohol and an ester. Option C contains a ketone and a carboxylic acid. Option D is an ester only.
Marking scheme
Award [1] for the correct option A. No marks for any other response.
Question 9 · multiple-choice
1 marks
Which of the following species has a bond angle closest to \( 120^\circ \)?
A.\( \text{O}_3 \)
B.\( \text{H}_2\text{O} \)
C.\( \text{NH}_4^+ \)
D.\( \text{CO}_2 \)
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Worked solution
\( \text{O}_3 \) has 3 electron domains around the central oxygen atom (one lone pair, one single bond, one double bond). The electron domain geometry is trigonal planar, and repulsion from the lone pair reduces the bond angle from \( 120^\circ \) to approximately \( 117^\circ \), which is closest to \( 120^\circ \). \( \text{H}_2\text{O} \) is bent with \( 104.5^\circ \), \( \text{NH}_4^+ \) is tetrahedral with \( 109.5^\circ \), and \( \text{CO}_2 \) is linear with \( 180^\circ \).
Marking scheme
[1 mark] Correct choice is A. Award 1 mark for identifying that ozone has trigonal planar electron domain geometry leading to a bond angle of approximately 117 degrees.
Question 10 · multiple-choice
1 marks
Consider the reaction \( \text{A(g)} + 2\text{B(g)} \rightarrow \text{C(g)} \). The experimental initial rates under different concentrations of reactants are given: Trial 1: \( [\text{A}] = 0.10\text{ mol dm}^{-3} \), \( [\text{B}] = 0.10\text{ mol dm}^{-3} \), Rate = \( 2.0 \times 10^{-4}\text{ mol dm}^{-3}\text{ s}^{-1} \). Trial 2: \( [\text{A}] = 0.20\text{ mol dm}^{-3} \), \( [\text{B}] = 0.10\text{ mol dm}^{-3} \), Rate = \( 4.0 \times 10^{-4}\text{ mol dm}^{-3}\text{ s}^{-1} \). Trial 3: \( [\text{A}] = 0.10\text{ mol dm}^{-3} \), \( [\text{B}] = 0.20\text{ mol dm}^{-3} \), Rate = \( 8.0 \times 10^{-4}\text{ mol dm}^{-3}\text{ s}^{-1} \). What is the overall order of this reaction?
A.1
B.2
C.3
D.4
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Worked solution
Comparing Trial 1 and Trial 2: \( [\text{B}] \) is constant, \( [\text{A}] \) doubles, and the rate doubles, so the reaction is first-order with respect to A. Comparing Trial 1 and Trial 3: \( [\text{A}] \) is constant, \( [\text{B}] \) doubles, and the rate quadruples, so the reaction is second-order with respect to B. The rate expression is \( \text{Rate} = k[\text{A}][\text{B}]^2 \). The overall order is \( 1 + 2 = 3 \).
Marking scheme
[1 mark] Correct choice is C. Award 1 mark for deducing that the order with respect to A is 1 and with respect to B is 2, and summing them to get 3.
Question 11 · multiple-choice
1 marks
An oxide of phosphorus contains 43.6% phosphorus by mass. What is its empirical formula? (Relative atomic masses: \( \text{P} = 30.97 \), \( \text{O} = 16.00 \))
A.\( \text{PO}_2 \)
B.\( \text{P}_2\text{O}_3 \)
C.\( \text{P}_2\text{O}_5 \)
D.\( \text{P}_4\text{O}_{10} \)
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Worked solution
Assume 100 g of the compound. Moles of P = \( 43.6 / 30.97 \approx 1.41\text{ mol} \). Moles of O = \( (100 - 43.6) / 16.00 = 56.4 / 16.00 \approx 3.53\text{ mol} \). Divide by the smaller number of moles: \( \text{P} = 1.41 / 1.41 = 1 \), \( \text{O} = 3.53 / 1.41 \approx 2.5 \). Multiplying by 2 to get whole numbers gives a ratio of \( \text{P}_2\text{O}_5 \).
Marking scheme
[1 mark] Correct choice is C. Award 1 mark for calculating the mole ratio of P to O as 1 : 2.5 and simplifying to the empirical formula of P2O5.
Question 12 · multiple-choice
1 marks
When \( 5.0\text{ g} \) of a metal hydroxide, \( \text{MOH} \) (molar mass = \( 40.0\text{ g mol}^{-1} \)), is dissolved in \( 100.0\text{ g} \) of water, the temperature of the water increases by \( 10.0\text{ K} \). Assume the specific heat capacity of the solution is \( 4.18\text{ J g}^{-1}\text{ K}^{-1} \) and the mass of the solution is equal to the mass of the water. Which expression represents the enthalpy of solution, \( \Delta H_{\text{sol}} \), in \( \text{kJ mol}^{-1} \)?
[1 mark] Correct choice is A. Award 1 mark for correctly formulating heat q, moles n, and combining them with a negative sign indicating an exothermic reaction.
Question 13 · multiple-choice
1 marks
At \( 50\ ^\circ\text{C} \), the ionic product of water, \( K_{\text{w}} \), is \( 5.5 \times 10^{-14}\text{ mol}^2\text{ dm}^{-6} \). Which statement is correct for pure water at this temperature?
A.The water is acidic because its \( \text{pH} \) is less than 7.
B.The water is neutral and its \( \text{pH} \) is less than 7.
C.The water is basic because its \( \text{pH} \) is greater than 7.
D.The water is neutral and its \( \text{pH} \) is equal to 7.
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Worked solution
For pure water, \( [\text{H}^+] = [\text{OH}^-] \), so the water is neutral regardless of the temperature. Since \( K_{\text{w}} = 5.5 \times 10^{-14} \), \( [\text{H}^+] = \sqrt{K_{\text{w}}} = \sqrt{5.5 \times 10^{-14}} \approx 2.3 \times 10^{-7}\text{ mol dm}^{-3} \). The \( \text{pH} = -\log[\text{H}^+] \approx 6.6 \), which is less than 7.
Marking scheme
[1 mark] Correct choice is B. Award 1 mark for realizing that pure water is always neutral and that a larger Kw value results in pH < 7.
Question 14 · multiple-choice
1 marks
In the reaction \( 3\text{Cl}_2\text{(g)} + 6\text{OH}^-\text{(aq)} \rightarrow \text{ClO}_3^-\text{(aq)} + 5\text{Cl}^-\text{(aq)} + 3\text{H}_2\text{O(l)} \), which statement is correct?
A.Chlorine is oxidized only.
B.Chlorine is reduced only.
C.Chlorine is both oxidized and reduced.
D.Hydrogen is oxidized and chlorine is reduced.
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Worked solution
The oxidation state of chlorine in \( \text{Cl}_2 \) is 0. In \( \text{ClO}_3^- \), the oxidation state of chlorine is +5 (oxidized). In \( \text{Cl}^- \), the oxidation state of chlorine is -1 (reduced). Therefore, chlorine undergoes both oxidation and reduction (disproportionation).
Marking scheme
[1 mark] Correct choice is C. Award 1 mark for calculating the oxidation states of Cl in reactants and products to identify disproportionation.
Question 15 · multiple-choice
1 marks
Which class of organic compound is represented by the formula \( \text{CH}_3\text{CH}_2\text{CONHCH}_3 \)?
A.Amine
B.Amide
C.Ester
D.Ketone
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Worked solution
The structure contains the \( \text{-CONH-} \) group, which consists of a carbonyl group (\( \text{C=O} \)) bonded directly to a nitrogen atom. This is the characteristic functional group of an amide (specifically, a secondary amide).
Marking scheme
[1 mark] Correct choice is B. Award 1 mark for identifying the amide functional group from the molecular formula.
Question 16 · multiple-choice
1 marks
What is the ground-state electron configuration of the \( \text{Co}^{2+} \) ion?
A.[\text{Ar}] \( 4\text{s}^2 3\text{d}^5 \)
B.[\text{Ar}] \( 4\text{s}^1 3\text{d}^6 \)
C.[\text{Ar}] \( 3\text{d}^7 \)
D.[\text{Ar}] \( 4\text{s}^2 3\text{d}^7 \)
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Worked solution
Cobalt (atomic number 27) has the ground-state electron configuration \( [\text{Ar}] 4\text{s}^2 3\text{d}^7 \). When transition metals form cations, they lose the outer s-orbital electrons first. Therefore, the \( \text{Co}^{2+} \) ion loses the two \( 4\text{s} \) electrons, leaving the configuration \( [\text{Ar}] 3\text{d}^7 \).
Marking scheme
[1 mark] Correct choice is C. Award 1 mark for correctly identifying that 4s electrons are lost before 3d electrons, resulting in the [Ar] 3d7 configuration.
Question 17 · Multiple Choice
1 marks
A sample of an ideal gas has volume \(V\) at pressure \(P\) and temperature \(T\) (in Kelvin). If the absolute temperature is doubled and the pressure is increased by a factor of 4, what is the new volume?
A.0.5\(V\)
B.2\(V\)
C.4\(V\)
D.8\(V\)
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Worked solution
Using the combined gas law, \(\frac{P_1 V_1}{T_1} = \frac{P_2 V_2}{T_2}\). Rearranging to solve for the final volume \(V_2\): \(V_2 = V_1 \cdot \frac{P_1}{P_2} \cdot \frac{T_2}{T_1}\). Substituting the given values: \(V_2 = V \cdot \frac{P}{4P} \cdot \frac{2T}{T} = V \cdot \frac{1}{4} \cdot 2 = 0.5V\).
Marking scheme
Award [1] for the correct answer A.
Question 18 · Multiple Choice
1 marks
Which statement is correct regarding the first ionization energy of Period 3 elements?
A.It decreases steadily across the period from Na to Ar.
B.It is lower for sulfur than for phosphorus because sulfur has a fully filled d-subshell.
C.It is lower for sulfur than for phosphorus because of the repulsion between the paired electrons in the 3p subshell.
D.It is higher for aluminum than for magnesium because aluminum has more protons.
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Worked solution
Sulfur has a first ionization energy slightly lower than phosphorus. This discontinuity occurs because sulfur's outer electron configuration is \(3s^2 3p^4\), which contains one pair of electrons in a 3p orbital. The repulsion between these paired electrons makes it easier to remove one electron compared to the half-filled \(3s^2 3p^3\) configuration of phosphorus.
Marking scheme
Award [1] for the correct explanation of spin-pair repulsion (C).
Question 19 · Multiple Choice
1 marks
Which change corresponds to the standard enthalpy of atomization of bromine, \(\Delta H^\theta_{\text{at}}\text{(Br)}\)?
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Worked solution
The standard enthalpy of atomization is defined as the enthalpy change when 1 mole of gaseous atoms is formed from the element in its standard state. The standard state of bromine is a liquid, \(\text{Br}_2(l)\). Therefore, the equation for the production of 1 mole of gaseous bromine atoms is \(\frac{1}{2}\text{Br}_2(l) \rightarrow \text{Br}(g)\).
Marking scheme
Award [1] for identifying the correct equation representing standard state and 1 mole of gaseous atoms (B).
Question 20 · Multiple Choice
1 marks
A student combusts \(1.60\text{ g}\) of methanol (\(M_r = 32.0\text{ g mol}^{-1}\)) to heat \(200.0\text{ g}\) of water. The temperature of the water increases by \(30.0\text{ }^\circ\text{C}\). Assuming no heat loss, what is the enthalpy of combustion of methanol in \(\text{kJ mol}^{-1}\)? (Specific heat capacity of water = \(4.18\text{ J g}^{-1}\text{ K}^{-1}\))
A.-502
B.-251
C.-25.1
D.-1000
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Worked solution
1. Calculate moles of methanol: \(n = \frac{1.60\text{ g}}{32.0\text{ g mol}^{-1}} = 0.0500\text{ mol}\). 2. Calculate heat absorbed by water: \(q = m c \Delta T = 200.0\text{ g} \times 4.18\text{ J g}^{-1}\text{ K}^{-1} \times 30.0\text{ K} = 25080\text{ J} = 25.08\text{ kJ}\). 3. Calculate enthalpy of combustion: \(\Delta H_c = -\frac{q}{n} = -\frac{25.08\text{ kJ}}{0.0500\text{ mol}} = -501.6\text{ kJ mol}^{-1}\), which rounds to -502.
Marking scheme
Award [1] for calculating the correct enthalpy change (A).
Question 21 · Multiple Choice
1 marks
The reaction \(2\text{A} + \text{B} \rightarrow \text{C}\) has the experimental rate expression: \(\text{Rate} = k[\text{A}][\text{B}]\). Which mechanism is consistent with this rate expression?
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Worked solution
For a multi-step reaction mechanism, the rate-determining step (slow step) determines the rate law. In mechanism A, the slow step is Step 1: \(\text{A} + \text{B} \rightarrow \text{I}\). Because this is an elementary step, its rate law is \(\text{Rate} = k[\text{A}][\text{B}]\), which matches the experimental rate law. Mechanism C would have a rate law of \(\text{Rate} = k[\text{A}]^2[\text{B}]\).
Marking scheme
Award [1] for identifying the mechanism where the reactants in the slow step match the rate expression (A).
Question 22 · Multiple Choice
1 marks
In an acidic solution, bromate ions (\(\text{BrO}_3^-\)) react with bromide ions (\(\text{Br}^-\)) to form bromine liquid (\(\text{Br}_2\)) and water. What is the ratio of \(\text{BrO}_3^-\) to \(\text{Br}^-\), respectively, in the fully balanced ionic equation?
A.1 : 1
B.1 : 3
C.1 : 5
D.2 : 5
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Worked solution
The two half-reactions are: Oxidation: \(2\text{Br}^- \rightarrow \text{Br}_2 + 2e^-\). Reduction: \(2\text{BrO}_3^- + 12\text{H}^+ + 10e^- \rightarrow \text{Br}_2 + 6\text{H}_2\text{O}\). To balance electrons, multiply the oxidation half-reaction by 5: \(10\text{Br}^- \rightarrow 5\text{Br}_2 + 10e^-\). Add the two half-reactions: \(2\text{BrO}_3^- + 10\text{Br}^- + 12\text{H}^+ \rightarrow 6\text{Br}_2 + 6\text{H}_2\text{O}\). Dividing all coefficients by 2 gives the simplest whole-number ratio: \(\text{BrO}_3^- + 5\text{Br}^- + 6\text{H}^+ \rightarrow 3\text{Br}_2 + 3\text{H}_2\text{O}\). The ratio of \(\text{BrO}_3^-\) to \(\text{Br}^-\) is therefore 1 : 5.
Marking scheme
Award [1] for the correct ratio 1:5 (C).
Question 23 · Multiple Choice
1 marks
How many sigma (\(\sigma\)) and pi (\(\pi\)) bonds are present in a molecule of methyl propenoate, \(\text{CH}_2=\text{CHCOOCH}_3\)?
A.10 sigma, 2 pi
B.11 sigma, 1 pi
C.11 sigma, 2 pi
D.12 sigma, 2 pi
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Worked solution
Examine the structure of methyl propenoate: \(\text{H}_2\text{C}=\text{CH}-\text{C}(=\text{O})-\text{O}-\text{CH}_3\). Sigma (\(\sigma\)) bonds: 6 \(\text{C}-\text{H}\) single bonds, 1 \(\text{C}-\text{C}\) single bond, 1 \(\text{C}-\text{O}\) single bond, 1 \(\text{O}-\text{C}\) single bond, 1 from the \(\text{C}=\text{C}\) double bond, and 1 from the \(\text{C}=\text{O}\) double bond. Total = 11 \(\sigma\) bonds. Pi (\(\pi\)) bonds: 1 from the \(\text{C}=\text{C}\) double bond and 1 from the \(\text{C}=\text{O}\) double bond. Total = 2 \(\pi\) bonds.
Marking scheme
Award [1] for the correct counts of 11 sigma and 2 pi bonds (C).
Question 24 · Multiple Choice
1 marks
A weak acid \(\text{HA}\) has \(K_a = 1.0 \times 10^{-5}\text{ mol dm}^{-3}\) at \(298\text{ K}\). What is the pH of a \(0.10\text{ mol dm}^{-3}\) aqueous solution of this acid?
A.1.0
B.3.0
C.5.0
D.6.0
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In one of the resonance structures of dinitrogen monoxide, \(\text{N}_2\text{O}\), the bonding sequence is \(\text{N}\equiv\text{N}-\text{O}\). What are the formal charges on the terminal nitrogen, central nitrogen, and oxygen atoms in this Lewis structure?
A.Terminal N: 0; Central N: +1; Oxygen: -1
B.Terminal N: -1; Central N: +1; Oxygen: 0
C.Terminal N: 0; Central N: 0; Oxygen: 0
D.Terminal N: +1; Central N: 0; Oxygen: -1
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Worked solution
The formal charge (FC) can be calculated using the formula: \(FC = V - N - \frac{1}{2}B\), where \(V\) is the number of valence electrons, \(N\) is the number of non-bonding valence electrons, and \(B\) is the number of bonding electrons. For the terminal nitrogen atom (which has one lone pair and forms a triple bond): \(FC = 5 - 2 - \frac{1}{2}(6) = 0\). For the central nitrogen atom (which forms a triple bond and a single bond): \(FC = 5 - 0 - \frac{1}{2}(8) = +1\). For the oxygen atom (which has three lone pairs and forms a single bond): \(FC = 6 - 6 - \frac{1}{2}(2) = -1\). Therefore, the formal charges are: Terminal N: 0; Central N: +1; Oxygen: -1.
Marking scheme
Award [1] for the correct answer (A).
Question 26 · multiple-choice
1 marks
The following equilibrium reaction takes place in a closed \(2.0\text{ dm}^3\) container at a constant temperature: \(2\text{A(g)} \rightleftharpoons \text{B(g)} + \text{C(g)}\). At equilibrium, the mixture contains \(0.40\text{ mol}\) of \(\text{A}\), \(0.80\text{ mol}\) of \(\text{B}\), and \(0.80\text{ mol}\) of \(\text{C}\). What is the value of the equilibrium constant, \(K_c\)?
A.1.0
B.2.0
C.4.0
D.8.0
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Worked solution
First, determine the equilibrium concentrations of each species: \([\text{A}] = 0.40\text{ mol} / 2.0\text{ dm}^3 = 0.20\text{ mol dm}^{-3}\), \([\text{B}] = 0.80\text{ mol} / 2.0\text{ dm}^3 = 0.40\text{ mol dm}^{-3}\), \([\text{C}] = 0.80\text{ mol} / 2.0\text{ dm}^3 = 0.40\text{ mol dm}^{-3}\). Next, write the expression for the equilibrium constant: \(K_c = \frac{[\text{B}][\text{C}]}{[\text{A}]^2}\). Substitute the equilibrium concentrations: \(K_c = \frac{0.40 \times 0.40}{(0.20)^2} = \frac{0.16}{0.04} = 4.0\). Alternatively, because the total number of moles on both sides is equal, volume cancels out, and using moles directly gives: \(K_c = \frac{0.80 \times 0.80}{0.40^2} = 4.0\).
Marking scheme
Award [1] for the correct answer (C).
Question 27 · multiple-choice
1 marks
Which of the following mixtures will produce a buffer solution with a pH greater than 7 at \(298\text{ K}\)?
A.\(50\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{NH}_3\text{(aq)}\) and \(25\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{HCl(aq)}\)
B.\(50\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{CH}_3\text{COOH(aq)}\) and \(25\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{NaOH(aq)}\)
C.\(25\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{NH}_3\text{(aq)}\) and \(50\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{HCl(aq)}\)
D.\(50\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{CH}_3\text{COOH(aq)}\) and \(50\text{ cm}^3\) of \(0.10\text{ mol dm}^{-3}\) \(\text{NaOH(aq)}\)
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Worked solution
A buffer solution is formed when a weak acid/base is in excess compared to a strong base/acid. In option A: we have \(5.0\text{ mmol}\) of \(\text{NH}_3\) (weak base) reacting with \(2.5\text{ mmol}\) of \(\text{HCl}\) (strong acid). This leaves \(2.5\text{ mmol}\) of unreacted \(\text{NH}_3\) and produces \(2.5\text{ mmol}\) of \(\text{NH}_4^+\) (its conjugate acid), forming a basic buffer with pH greater than 7. In option B: we have \(5.0\text{ mmol}\) of \(\text{CH}_3\text{COOH}\) reacting with \(2.5\text{ mmol}\) of \(\text{NaOH}\), which forms an acidic buffer with pH less than 7. In option C: \(\text{HCl}\) is in excess, so the solution is strongly acidic. In option D: equal stoichiometric amounts react, leaving only the salt \(\text{CH}_3\text{COONa}\) (not a buffer).
Marking scheme
Award [1] for the correct answer (A).
Question 28 · multiple-choice
1 marks
Which equation represents the change corresponding to the second ionization energy of calcium?
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Worked solution
The second ionization energy is defined as the energy required to remove one mole of electrons from one mole of gaseous 1+ ions to form one mole of gaseous 2+ ions. Thus, the corresponding equation is: \(\text{Ca}^+\text{(g)} \rightarrow \text{Ca}^{2+}\text{(g)} + \text{e}^-\).
Marking scheme
Award [1] for the correct answer (B).
Question 29 · multiple-choice
1 marks
A student dissolved \(2.00\text{ g}\) of an unknown salt (molar mass \(= 80.0\text{ g mol}^{-1}\)) in \(50.0\text{ g}\) of water in a simple calorimeter. The temperature of the mixture decreased from \(20.0^\circ\text{C}\) to \(14.0^\circ\text{C}\). Assuming the specific heat capacity of the solution is \(4.18\text{ J g}^{-1}\text{ K}^{-1}\) and the mass of the resulting solution is \(52.0\text{ g}\), what is the enthalpy of solution (\(\Delta H_{\text{sol}}\)) of the salt in \(\text{kJ mol}^{-1}\)?
A.\(-52.2\text{ kJ mol}^{-1}\)
B.\(+52.2\text{ kJ mol}^{-1}\)
C.\(-50.2\text{ kJ mol}^{-1}\)
D.\(+50.2\text{ kJ mol}^{-1}\)
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Worked solution
1. Calculate heat absorbed, \(q\): \(q = m \cdot c \cdot \Delta T\) where \(m = 52.0\text{ g}\) (mass of solution), \(c = 4.18\text{ J g}^{-1}\text{ K}^{-1}\), and \(\Delta T = 20.0 - 14.0 = 6.0\text{ K}\). \(q = 52.0 \times 4.18 \times 6.0 = 1304.16\text{ J} = 1.30416\text{ kJ}\). 2. Calculate moles of salt, \(n\): \(n = 2.00\text{ g} / 80.0\text{ g mol}^{-1} = 0.0250\text{ mol}\). 3. Calculate \(\Delta H_{\text{sol}}\): Since the temperature decreased, the process is endothermic, so \(\Delta H_{\text{sol}}\) is positive. \(\Delta H_{\text{sol}} = +\frac{1.30416\text{ kJ}}{0.0250\text{ mol}} = +52.2\text{ kJ mol}^{-1}\).
Marking scheme
Award [1] for the correct answer (B).
Question 30 · multiple-choice
1 marks
A proposed mechanism for the reaction \(2\text{NO}_2\text{(g)} + \text{F}_2\text{(g)} \rightarrow 2\text{NO}_2\text{F(g)}\) is: Step 1: \(\text{NO}_2\text{(g)} + \text{F}_2\text{(g)} \rightarrow \text{NO}_2\text{F(g)} + \text{F(g)}\) (slow), Step 2: \(\text{NO}_2\text{(g)} + \text{F(g)} \rightarrow \text{NO}_2\text{F(g)}\) (fast). Which of the following statements is correct?
A.The rate equation for the reaction is \(\text{rate} = k[\text{NO}_2]^2[\text{F}_2]\).
B.Fluorine atoms (\(\text{F}\)) act as a catalyst in this reaction.
C.The overall order of the reaction is 2.
D.Increasing the concentration of \(\text{NO}_2\) has no effect on the rate of the reaction.
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Worked solution
The rate-determining step is the slow step (Step 1). The rate equation is derived directly from the reactants of this step: \(\text{rate} = k[\text{NO}_2][\text{F}_2]\). Since the rate equation is first-order with respect to \(\text{NO}_2\) and first-order with respect to \(\text{F}_2\), the overall order of the reaction is \(1 + 1 = 2\), which makes statement C correct. Statement A is incorrect because the coefficient of \(\text{NO}_2\) in the overall reaction does not dictate the rate equation. Statement B is incorrect because \(\text{F}\) is an intermediate, not a catalyst. Statement D is incorrect because changing the concentration of \(\text{NO}_2\) will affect the rate of the reaction.
Marking scheme
Award [1] for the correct answer (C).
Paper 2
Answer all questions in the spaces provided. A calculator and the Chemistry Data Booklet are required.
6 Question · 49.98 marks
Question 1 · Structured Written
8.33 marks
Sulfur forms various fluorides, including sulfur tetrafluoride, \(\text{SF}_4\), and sulfur hexafluoride, \(\text{SF}_6\).
(a) Draw the Lewis (electron dot) structure of \(\text{SF}_4\), showing all valence electrons. [2]
(b) Deduce the molecular geometry of \(\text{SF}_4\) and state its approximate bond angles. [2]
(c) Explain why \(\text{SF}_6\) is non-polar, whereas \(\text{SF}_4\) is polar, even though both contain polar S–F bonds. [2]
(d) Deduce the number of sigma (\(\sigma\)) and pi (\(\pi\)) bonds in a molecule of sulfur dioxide, \(\text{SO}_2\), and state the hybridization of the sulfur atom in \(\text{SO}_2\). [2]
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Worked solution
(a) The Lewis structure of \(\text{SF}_4\) has sulfur in the center single-bonded to four fluorine atoms, with one lone pair on the sulfur atom. Each fluorine atom has three lone pairs. S has 10 valence electrons surrounding it (an expanded octet).
(b) The sulfur atom in \(\text{SF}_4\) has 5 electron domains (4 bonding pairs, 1 lone pair). According to VSEPR theory, this corresponds to a see-saw (or sawhorse) molecular geometry. The approximate bond angles are less than 90\(^\circ\) (axial-equatorial) and less than 120\(^\circ\) (equatorial-equatorial) due to the greater repulsion from the lone pair.
(c) \(\text{SF}_6\) is symmetrical (octahedral geometry), so the individual S–F bond dipoles cancel each other out, resulting in a net dipole moment of zero (non-polar). \(\text{SF}_4\) is asymmetrical (see-saw geometry), so the individual S–F bond dipoles do not cancel each other out, resulting in a net dipole moment (polar).
(d) In \(\text{SO}_2\) (which has resonance structures with a double and single bond, or two double bonds), there are 2 sigma (\(\sigma\)) bonds and either 1 or 2 pi (\(\pi\)) bonds. The sulfur atom has 3 electron domains (2 bonding domains, 1 lone pair), so its hybridization is \(\text{sp}^2\).
Marking scheme
(a) - Award [1] for showing four S–F single bonds and one lone pair on the central sulfur atom. - Award [1] for showing three lone pairs on each of the four fluorine atoms. [2 marks]
(b) - Award [1] for see-saw / sawhorse geometry. - Award [1] for stating bond angles are < 90\(^\circ\) and < 120\(^\circ\) (accept approx. 90\(^\circ\) and 120\(^\circ\)). [2 marks]
(c) - Award [1] for stating that \(\text{SF}_6\) is octahedral/symmetrical, so S–F bond dipoles cancel out. - Award [1] for stating that \(\text{SF}_4\) is see-saw/asymmetrical, so S–F bond dipoles do not cancel out. [2 marks]
(d) - Award [1] for stating 2 sigma (\(\sigma\)) and 1 pi (\(\pi\)) bond (or 2 pi (\(\pi\)) bonds). - Award [1] for stating \(\text{sp}^2\) hybridization of the sulfur atom. [2 marks]
Question 2 · Structured Written
8.33 marks
The reaction between nitric oxide and hydrogen gas is represented by the following equation: \(2\text{NO}(g) + 2\text{H}_2(g) \rightarrow \text{N}_2(g) + 2\text{H}_2\text{O}(g)\)
The following initial rates data were collected at a constant temperature of 800 K:
(a) Determine the order of reaction with respect to \(\text{NO}\) and \(\text{H}_2\), explaining your reasoning. [3]
(b) Write the rate expression (rate law) for the reaction. [1]
(c) Calculate the rate constant, \(k\), for this reaction, including its units. [2]
(d) A proposed mechanism for this reaction is: Step 1: \(2\text{NO}(g) \rightleftharpoons \text{N}_2\text{O}_2(g)\) (fast equilibrium) Step 2: \(\text{N}_2\text{O}_2(g) + \text{H}_2(g) \rightarrow \text{N}_2\text{O}(g) + \text{H}_2\text{O}(g)\) (slow step) Step 3: \(\text{N}_2\text{O}(g) + \text{H}_2(g) \rightarrow \text{N}_2(g) + \text{H}_2\text{O}(g)\) (fast step)
Show that this mechanism is consistent with the experimentally determined rate expression. [2]
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Worked solution
(a) To find the order with respect to \(\text{NO}\), compare Experiments 1 and 2 where \([\text{H}_2]\) is kept constant at \(0.010\text{ mol dm}^{-3}\). As \([\text{NO}]\) doubles from \(0.010\) to \(0.020\text{ mol dm}^{-3}\), the rate increases by a factor of \(\frac{4.8 \times 10^{-4}}{1.2 \times 10^{-4}} = 4\) (or \(2^2\)). Therefore, the reaction is second order with respect to \(\text{NO}\). To find the order with respect to \(\text{H}_2\), compare Experiments 2 and 3 where \([\text{NO}]\) is kept constant at \(0.020\text{ mol dm}^{-3}\). As \([\text{H}_2]\) doubles from \(0.010\) to \(0.020\text{ mol dm}^{-3}\), the rate increases by a factor of \(\frac{9.6 \times 10^{-4}}{4.8 \times 10^{-4}} = 2\) (or \(2^1\)). Therefore, the reaction is first order with respect to \(\text{H}_2\).
(b) The rate expression is: \(\text{Rate} = k[\text{NO}]^2[\text{H}_2]\).
(c) Substituting data from Experiment 1 into the rate expression: \(1.2 \times 10^{-4}\text{ mol dm}^{-3}\text{ s}^{-1} = k (0.010\text{ mol dm}^{-3})^2 (0.010\text{ mol dm}^{-3})\) \(1.2 \times 10^{-4} = k (1.0 \times 10^{-6})\) \(k = 120\) Units of \(k\): \(\frac{\text{mol dm}^{-3}\text{ s}^{-1}}{(\text{mol dm}^{-3})^3} = \text{mol}^{-2}\text{ dm}^6\text{ s}^{-1}\).
(d) The rate-determining step (slow step) is Step 2: \(\text{Rate} = k_2[\text{N}_2\text{O}_2][\text{H}_2]\) Since \(\text{N}_2\text{O}_2\) is an intermediate, we express its concentration using the fast equilibrium of Step 1: \(K_c = \frac{[\text{N}_2\text{O}_2]}{[\text{NO}]^2} \Rightarrow [\text{N}_2\text{O}_2] = K_c[\text{NO}]^2\) Substituting this back into the rate equation for Step 2: \(\text{Rate} = k_2(K_c[\text{NO}]^2)[\text{H}_2] = k[\text{NO}]^2[\text{H}_2]\), where \(k = k_2 K_c\). This is consistent with the experimental rate expression.
Marking scheme
(a) - Award [1] for second order with respect to \(\text{NO}\) and showing comparison of Exp 1 and 2. - Award [1] for first order with respect to \(\text{H}_2\) and showing comparison of Exp 2 and 3. - Award [1] for clear explanation logic. [3 marks]
(b) - Award [1] for \(\text{Rate} = k[\text{NO}]^2[\text{H}_2]\). [1 mark]
(c) - Award [1] for the value \(120\). - Award [1] for correct units: \(\text{mol}^{-2}\text{ dm}^6\text{ s}^{-1}\) (or \(\text{dm}^6\text{ mol}^{-2}\text{ s}^{-1}\)). [2 marks]
(d) - Award [1] for identifying that \(\text{Rate} = k_2[\text{N}_2\text{O}_2][\text{H}_2]\) from the rate-determining step. - Award [1] for substituting \([\text{N}_2\text{O}_2] = K_c[\text{NO}]^2\) from the fast equilibrium to obtain the overall rate expression. [2 marks]
Question 3 · Structured Written
8.33 marks
Propanoic acid, \(\text{C}_2\text{H}_5\text{COOH}\), is a weak monoprotic acid with a dissociation constant, \(K_a\), of \(1.35 \times 10^{-5}\text{ mol dm}^{-3}\) at 298 K.
(a) Write an equation for the dissociation of propanoic acid in water, identifying the conjugate acid-base pairs. [2]
(b) Calculate the pH of a \(0.100\text{ mol dm}^{-3}\) aqueous solution of propanoic acid at 298 K, showing your working and any assumptions made. [3]
(c) A buffer solution is prepared by mixing \(50.0\text{ cm}^3\) of \(0.100\text{ mol dm}^{-3}\) propanoic acid with \(50.0\text{ cm}^3\) of \(0.0500\text{ mol dm}^{-3}\) sodium hydroxide solution. Calculate the pH of the resulting buffer solution. [3]
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(a) - Award [1] for a balanced dissociation equation with equilibrium arrows. - Award [1] for identifying conjugate acid-base pairs correctly. [2 marks]
(b) - Award [1] for stating the assumption \([\text{H}^+] \approx [\text{C}_2\text{H}_5\text{COO}^-]\) OR \([\text{C}_2\text{H}_5\text{COOH}] \approx 0.100\text{ mol dm}^{-3}\). - Award [1] for calculating \([\text{H}^+] = 1.16 \times 10^{-3}\text{ mol dm}^{-3}\). - Award [1] for \(\text{pH} = 2.93\) (accept 2.9 or 2.94). [3 marks]
(c) - Award [1] for calculating initial moles of both reactants (\(5.00 \times 10^{-3}\text{ mol}\) and \(2.50 \times 10^{-3}\text{ mol}\)). - Award [1] for establishing that after reaction, \([\text{acid}] = [\text{conjugate base}]\). - Award [1] for calculating \(\text{pH} = \text{p}K_a = 4.87\). [3 marks]
Question 4 · Structured Written
8.33 marks
A voltaic cell is constructed using a copper electrode in a \(1.0\text{ mol dm}^{-3}\text{ Cu}^{2+}(aq)\) solution and a nickel electrode in a \(1.0\text{ mol dm}^{-3}\text{ Ni}^{2+}(aq)\) solution under standard conditions.
(a) Identify the anode and write the half-equation for the reaction occurring at this electrode. [2]
(b) Calculate the standard cell potential, \(E^\theta_{\text{cell}}\), for the cell and write the overall spontaneous cell reaction. [2]
(c) Draw a cell diagram (using IUPAC standard cell notation) for this voltaic cell. [2]
(d) State the direction of electron flow in the external circuit and describe the movement of cations in the salt bridge. [2]
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Worked solution
(a) The anode is where oxidation occurs. Since nickel has the more negative reduction potential (\(-0.25\text{ V}\) vs \(+0.34\text{ V}\) for copper), it is oxidized and serves as the anode. Half-equation: \(\text{Ni}(s) \rightarrow \text{Ni}^{2+}(aq) + 2e^-\)
(c) Standard IUPAC cell notation (anode on left, cathode on right): \(\text{Ni}(s) \mid \text{Ni}^{2+}(aq) \parallel \text{Cu}^{2+}(aq) \mid \text{Cu}(s)\)
(d) Electrons flow from the nickel anode to the copper cathode through the external wire. Cations in the salt bridge move towards the copper half-cell / cathode (to balance the decrease in positive charge as \(\text{Cu}^{2+}\) ions are reduced to \(\text{Cu}(s)\)).
Marking scheme
(a) - Award [1] for identifying Nickel (Ni) as the anode. - Award [1] for the correct oxidation half-equation: \(\text{Ni}(s) \rightarrow \text{Ni}^{2+}(aq) + 2e^-\). [2 marks]
(b) - Award [1] for calculating \(E^\theta_{\text{cell}} = +0.59\text{ V}\). - Award [1] for correct overall equation: \(\text{Ni}(s) + \text{Cu}^{2+}(aq) \rightarrow \text{Ni}^{2+}(aq) + \text{Cu}(s)\). [2 marks]
(c) - Award [2] for correct standard cell notation: \(\text{Ni}(s) \mid \text{Ni}^{2+}(aq) \parallel \text{Cu}^{2+}(aq) \mid \text{Cu}(s)\). - Award [1] if the positions of anode/cathode are reversed but the phases are correct. [2 marks]
(d) - Award [1] for stating electrons flow from Ni to Cu through the external circuit. - Award [1] for stating cations in the salt bridge move towards the copper half-cell / cathode. [2 marks]
Question 5 · Structured Written
8.33 marks
A sample of an unknown volatile liquid with a mass of 0.324 g was vaporized completely in a gas syringe at 98.0\(^\circ\)C and a pressure of 101.3 kPa. The volume of the vapor produced was measured as 118.0 cm\(^3\).
(a) Calculate the molar mass of the volatile liquid using the ideal gas equation. [4]
(b) Explain why real gases deviate from ideal behavior at high pressures and low temperatures. [2]
(c) Calculate the density of the vapor in g dm\(^{-3}\) under these experimental conditions. [2]
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Using the ideal gas equation: \(PV = nRT\) \(n = \frac{PV}{RT} = \frac{1.013 \times 10^5 \times 1.180 \times 10^{-4}}{8.31 \times 371.15}\) \(n = \frac{11.953}{3084.26} = 3.876 \times 10^{-3}\text{ mol}\)
Molar mass (\(M\)): \(M = \frac{m}{n} = \frac{0.324\text{ g}}{3.876 \times 10^{-3}\text{ mol}} = 83.6\text{ g mol}^{-1}\) (Accept 83.5 to 84.0 depending on rounding).
(b) Real gases deviate from ideal behavior because: 1. At high pressure, the volume of gas molecules themselves is no longer negligible compared to the total volume of the container. 2. At low temperatures, gas molecules move slower and intermolecular attractive forces become significant.
(c) Volume in \(\text{dm}^3\): \(V = 0.1180\text{ dm}^3\). Density (\(d\)): \(d = \frac{m}{V} = \frac{0.324\text{ g}}{0.1180\text{ dm}^3} = 2.75\text{ g dm}^{-3}\).
Marking scheme
(a) - Award [1] for correct unit conversions: \(T = 371.15\text{ K}\) (or 371 K) AND \(V = 1.180 \times 10^{-4}\text{ m}^3\). - Award [1] for correct rearrangement of ideal gas equation: \(n = \frac{PV}{RT}\). - Award [1] for calculating \(n = 3.88 \times 10^{-3}\text{ mol}\). - Award [1] for calculating molar mass \(83.6\text{ g mol}^{-1}\) (accept value in the range \(83.5 - 84.0\)). [4 marks]
(b) - Award [1] for explaining high pressure deviation: volume of molecules is significant. - Award [1] for explaining low temperature deviation: intermolecular forces become significant. [2 marks]
(c) - Award [1] for volume conversion to \(0.1180\text{ dm}^3\). - Award [1] for density = \(2.75\text{ g dm}^{-3}\). [2 marks]
Question 6 · Structured Written
8.33 marks
The Born-Haber cycle is a series of thermodynamic steps used to determine the lattice enthalpy of an ionic compound.
Consider the following thermodynamic data for magnesium chloride, \(\text{MgCl}_2\): - Enthalpy of formation of \(\text{MgCl}_2(s)\): \(\Delta H_f^\theta = -641\text{ kJ mol}^{-1}\) - Enthalpy of atomization of \(\text{Mg}(s)\): \(\Delta H_{\text{at}}^\theta = +148\text{ kJ mol}^{-1}\) - First ionization energy of \(\text{Mg}(g)\): \(\text{IE}_1 = +738\text{ kJ mol}^{-1}\) - Second ionization energy of \(\text{Mg}(g)\): \(\text{IE}_2 = +1451\text{ kJ mol}^{-1}\) - Bond enthalpy of \(\text{Cl}_2(g)\): \(\text{E}(\text{Cl}-\text{Cl}) = +242\text{ kJ mol}^{-1}\) - Electron affinity of \(\text{Cl}(g)\): \(\text{EA} = -349\text{ kJ mol}^{-1}\)
(a) Define the term *lattice enthalpy* of dissociation of an ionic compound. [1]
(b) Write chemical equations, including state symbols, that correspond to: (i) the standard enthalpy of formation of \(\text{MgCl}_2(s)\). [1] (ii) the electron affinity of chlorine. [1]
(c) State how the bond enthalpy of chlorine, \(\text{E}(\text{Cl}-\text{Cl})\), relates to the standard enthalpy of atomization of chlorine. [1]
(d) Calculate the standard lattice enthalpy of dissociation of \(\text{MgCl}_2(s)\) using the provided data. [4]
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Worked solution
(a) Lattice enthalpy of dissociation is the enthalpy change required to separate one mole of an ionic solid into its gaseous ions under standard conditions.
(c) The bond enthalpy of chlorine (\(\text{Cl}-\text{Cl}\)) corresponds to breaking 1 mole of \(\text{Cl}_2(g)\) bonds to form 2 moles of \(\text{Cl}(g)\). The standard enthalpy of atomization of chlorine is half of the bond enthalpy: \(\Delta H_{\text{at}}^\theta(\text{Cl}) = \frac{1}{2} \text{E}(\text{Cl}-\text{Cl}) = +121\text{ kJ mol}^{-1}\).
Therefore, the standard lattice enthalpy of dissociation is \(+2522\text{ kJ mol}^{-1}\).
Marking scheme
(a) - Award [1] for stating: enthalpy change to form gaseous ions from 1 mole of solid ionic compound. [1 mark]
(b) - (i) Award [1] for: \(\text{Mg}(s) + \text{Cl}_2(g) \rightarrow \text{MgCl}_2(s)\) (must include state symbols). - (ii) Award [1] for: \(\text{Cl}(g) + e^- \rightarrow \text{Cl}^-(g)\) (must include state symbols). [2 marks]
(c) - Award [1] for stating that the bond enthalpy is twice the enthalpy of atomization (or \(\Delta H_{\text{at}}^\theta = \frac{1}{2} \text{E}\)). [1 mark]
(d) - Award [1] for correctly multiplying the electron affinity of chlorine by 2 (\(-698\text{ kJ mol}^{-1}\)). - Award [1] for recognizing that 2 moles of gaseous Cl atoms require 1 mole of Cl2 bonds to be broken (no division of bond enthalpy by 2 needed). - Award [1] for setting up the Born-Haber cycle equation correctly: \(\Delta H_{\text{lat}} = 148 + 738 + 1451 + 242 - 698 - (-641)\). - Award [1] for correct final answer: \(+2522\text{ kJ mol}^{-1}\). [4 marks]
Paper 3
Answer all questions in Section A, and all questions from one chosen Option in Section B.
6 Question · 35 marks
Question 1 · Data Analysis and Experimental
7.5 marks
A student investigated the kinetics of the decomposition of hydrogen peroxide, \(2\text{H}_2\text{O}_2(aq) \rightarrow 2\text{H}_2\text{O}(l) + \text{O}_2(g)\), catalyzed by manganese(IV) oxide, \(\text{MnO}_2(s)\).
The volume of oxygen gas evolved was measured at regular intervals using a gas syringe. The data collected at \(298\ \text{K}\) is shown below:
(a) Identify the independent and dependent variables in this experiment. [1]
(b) (i) Calculate the average rate of reaction between \(0\) and \(20\ \text{s}\), and between \(40\) and \(60\ \text{s}\), including units. [2]
(ii) Explain the change in the rate of reaction over time with reference to collision theory. [1.5]
(c) A systematic error occurs because there is a delay between adding the catalyst and sealing the reaction vessel with the stopper.
(i) Deduce the effect of this error on the calculated initial rate of reaction. [1]
(ii) Suggest an experimental modification to minimize this error. [2]
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Worked solution
(a) Independent variable: Time Dependent variable: Volume of oxygen gas (or gas evolved)
(b) (i) Average rate between \(0\) and \(20\ \text{s}\): \(\text{Rate} = \frac{26.0\ \text{cm}^3 - 0.0\ \text{cm}^3}{20.0\ \text{s} - 0\ \text{s}} = 1.30\ \text{cm}^3\ \text{s}^{-1}\)
Average rate between \(40\) and \(60\ \text{s}\): \(\text{Rate} = \frac{46.0\ \text{cm}^3 - 40.0\ \text{cm}^3}{60.0\ \text{s} - 40.0\ \text{s}} = \frac{6.0\ \text{cm}^3}{20.0\ \text{s}} = 0.30\ \text{cm}^3\ \text{s}^{-1}\)
(ii) Over time, the concentration of the reactant (\(\text{H}_2\text{O}_2\)) decreases. This results in a lower frequency of collisions between reactant particles per unit volume, reducing the rate of successful collisions and thus decreasing the rate of reaction.
(c) (i) The calculated initial rate of reaction will be lower than the actual initial rate, because some oxygen gas escapes before the stopper is sealed, leading to an underestimate of the early volume of gas produced.
(ii) Use a reaction vessel where the catalyst is suspended above the solution (e.g., in a small vial or on a thread) and can be dropped into the reactant by tilting or releasing without opening the system, OR use a syringe to inject the liquid reactant through a rubber septum into a flask containing the catalyst.
Marking scheme
(a) Award [1] for both identified correctly, or [0.5] for only one. - Independent variable: Time - Dependent variable: Volume of oxygen gas (or gas evolved)
(b) (i) Award [1] for: \(1.30\ \text{cm}^3\ \text{s}^{-1}\) (or \(\text{cm}^3/\text{s}\)) Award [1] for: \(0.30\ \text{cm}^3\ \text{s}^{-1}\) (or \(\text{cm}^3/\text{s}\)) *Note: Units must be present in at least one of the answers to gain full marks.*
(ii) Award [1.5] maximum: - Concentration of hydrogen peroxide / reactant decreases [0.5] - Fewer reactant particles per unit volume, leading to lower frequency of collisions [0.5] - Fewer successful collisions per unit time [0.5]
(c) (i) Award [1] maximum: - Initial rate is lower/underestimated [0.5] - Gas escapes before the system is sealed, so initial volumes are recorded as lower than actual [0.5]
(ii) Award [2] maximum: - Suspend the catalyst in a small container/vial inside the flask and shake/tilt to start the reaction without opening [1] OR inject hydrogen peroxide via a syringe through a rubber septum into the flask containing the catalyst [1] - Award [1] for any other logical setup that allows mixing without opening the system to the atmosphere.
Question 2 · Data Analysis and Experimental
7.5 marks
An experiment was conducted to determine the molar mass of an unknown volatile organic liquid using the vapor density method. A sample of the liquid was placed in a pre-weighed flask covered with aluminum foil containing a tiny pinhole. The flask was heated in a boiling water bath until all the liquid vaporized, filling the flask with vapor at the surrounding atmospheric pressure and temperature. The flask was then cooled, and the mass of the condensed liquid was measured.
The following data were recorded: - Mass of empty flask and foil cap: \(85.250 \pm 0.001\ \text{g}\) - Mass of flask, foil cap, and condensed liquid: \(85.834 \pm 0.001\ \text{g}\) - Temperature of boiling water bath: \(99.5 \pm 0.5\ ^\circ\text{C}\) - Atmospheric pressure: \(100.8 \pm 0.1\ \text{kPa}\) - Volume of the flask: \(250.0 \pm 0.5\ \text{cm}^3\) - Gas constant, \(R\): \(8.31\ \text{J}\ \text{K}^{-1}\ \text{mol}^{-1}\)
(a) (i) Calculate the mass of the condensed vapor, in \(\text{g}\), and its absolute uncertainty. [1.5]
(ii) Calculate the percentage uncertainty of the volume of the flask. [1]
(b) Determine the molar mass of the volatile liquid, in \(\text{g}\ \text{mol}^{-1}\), using the ideal gas equation, \(PV = nRT\). State your answer to three significant figures. [3]
(c) Suggest how each of the following systematic errors would affect the calculated molar mass of the liquid (whether it would be higher, lower, or unaffected compared to the literature value):
(i) The liquid was not completely vaporized when the temperature was measured. [1]
(ii) The outside of the flask was wet when it was weighed after condensation. [1]
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Worked solution
(a) (i) Mass of condensed vapor = \(85.834\ \text{g} - 85.250\ \text{g} = 0.584\ \text{g}\) Absolute uncertainty of mass = \(\pm(0.001 + 0.001) = \pm 0.002\ \text{g}\)
(ii) Percentage uncertainty of volume = \(\frac{0.5}{250.0} \times 100 = 0.20\%\) (or \(0.2\%\))
Using \(PV = \frac{m}{M}RT\), rearrange for \(M\): \(M = \frac{mRT}{PV}\) \(M = \frac{0.584\ \text{g} \times 8.31\ \text{J}\ \text{K}^{-1}\ \text{mol}^{-1} \times 372.65\ \text{K}}{100.8 \times 10^3\ \text{Pa} \times 2.500 \times 10^{-4}\ \text{m}^3}\) \(M = \frac{1808.49}{25.2} = 71.765\ \text{g}\ \text{mol}^{-1}\) Rounding to 3 significant figures: \(71.8\ \text{g}\ \text{mol}^{-1}\) (accept \(71.7\ \text{g}\ \text{mol}^{-1}\) if \(373\ \text{K}\) or \(273\ \text{K}\) conversion is used).
(c) (i) Higher. If the liquid does not completely vaporize, excess liquid remains in the flask, artificially increasing the measured mass of condensed vapor (\(m\)), which leads to a higher calculated molar mass.
(ii) Higher. Water on the outside of the flask adds to the measured mass of the flask + condensed liquid, resulting in an overestimate of the vapor mass (\(m\)) and a higher calculated molar mass.
(b) Award [3] maximum: - Temperature conversion to \(372.65\ \text{K}\) / \(373\ \text{K}\) AND Volume conversion to \(2.500 \times 10^{-4}\ \text{m}^3\) (or compatible units for \(P\) and \(V\)) [1] - Correct rearrangement: \(M = \frac{mRT}{PV}\) [1] - Final answer to 3 significant figures: \(71.8\ \text{g}\ \text{mol}^{-1}\) (accept \(71.7\ \text{g}\ \text{mol}^{-1}\)) [1] *Note: Award [2] max if units are missing/incorrect, or if the number of significant figures is incorrect.*
(c) (i) Award [1]: - Higher / Overestimated AND because excess liquid remains which increases the mass (\(m\)).
(ii) Award [1]: - Higher / Overestimated AND because the external water increases the final mass reading of the flask, overestimating the vapor mass (\(m\)).
Question 3 · Option-based Written
5 marks
Aspirin (acetylsalicylic acid) is a widely used mild analgesic.
(a) Salicylic acid is reacted with ethanoic anhydride in the presence of an acid catalyst to produce aspirin. State the name of a suitable acid catalyst for this reaction and write the formula of the organic side-product formed. [2]
(b) Aspirin has low solubility in aqueous solutions, limiting its rate of absorption. Describe how aspirin can be chemically modified to increase its water solubility, and write a balanced equation for this reaction using the molecular formula of aspirin (\(\text{C}_9\text{H}_8\text{O}_4\)). [3]
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Worked solution
Part (a): In the preparation of aspirin, salicylic acid is acetylated using ethanoic anhydride. This reaction is catalyzed by a strong acid, typically concentrated sulfuric acid (\(\text{H}_2\text{SO}_4\)) or concentrated phosphoric acid (\(\text{H}_3\text{PO}_4\)). The reaction produces aspirin along with ethanoic acid (\(\text{CH}_3\text{COOH}\)) as a side-product.
Part (b): Aspirin is relatively insoluble in water due to the presence of the hydrophobic benzene ring and carboxylic acid group. Its solubility (and thus bioavailability) is improved by converting it into an ionic salt, sodium acetylsalicylate, by reacting it with a strong base such as sodium hydroxide (\(\text{NaOH}\)) or sodium hydrogencarbonate (\(\text{NaHCO}_3\)). The ionic nature of the salt allows it to form strong ion-dipole interactions with polar water molecules. Equation: \(\text{C}_9\text{H}_8\text{O}_4\text{(s)} + \text{NaOH(aq)} \rightarrow \text{NaC}_9\text{H}_7\text{O}_4\text{(aq)} + \text{H}_2\text{O(l)}\) (Alternative with sodium hydrogencarbonate is also accepted: \(\text{C}_9\text{H}_8\text{O}_4\text{(s)} + \text{NaHCO}_3\text{(aq)} \rightarrow \text{NaC}_9\text{H}_7\text{O}_4\text{(aq)} + \text{H}_2\text{O(l)} + \text{CO}_2\text{(g)}\))
Marking scheme
Part (a): - Award [1] for concentrated sulfuric acid / \(\text{H}_2\text{SO}_4\) OR concentrated phosphoric acid / \(\text{H}_3\text{PO}_4\). Reject \(\text{HCl}\) or dilute acids. - Award [1] for \(\text{CH}_3\text{COOH}\) / ethanoic acid.
Part (b): - Award [1] for stating that aspirin is reacted with a strong base / \(\text{NaOH}\) / \(\text{NaHCO}_3\) to convert it to an ionic/sodium salt. - Award [1] for explaining that this increases solubility because the ionic salt forms stronger intermolecular forces (ion-dipole) with water. - Award [1] for a correct balanced equation: \(\text{C}_9\text{H}_8\text{O}_4 + \text{NaOH} \rightarrow \text{NaC}_9\text{H}_7\text{O}_4 + \text{H}_2\text{O}\) (or alternative with \(\text{NaHCO}_3\)). State symbols are not required.
Question 4 · Option-based Written
5 marks
Morphine, codeine, and diamorphine (heroin) are strong analgesics that interact with opioid receptors in the brain.
(a) State the name of the functional group present in morphine that is converted to an ester group in diamorphine. [1]
(b) Explain why diamorphine is significantly more potent and faster-acting than morphine. Refer to the polarities of both compounds and the blood-brain barrier in your answer. [3]
(c) Identify the reaction type and the reagent used to synthesize diamorphine from morphine. [1]
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Worked solution
Part (a): Morphine contains two hydroxyl (\(-\text{OH}\)) groups (one phenolic and one aliphatic) that undergo conversion to ester groups during the synthesis of diamorphine.
Part (b): Morphine contains polar hydroxyl groups that participate in hydrogen bonding, making it relatively polar and less soluble in lipids. Diamorphine contains two ester groups, which are much less polar. Consequently, diamorphine is more lipid-soluble. The blood-brain barrier consists of a lipid-rich, non-polar membrane. Because of its lipophilic character, diamorphine crosses this barrier much more rapidly and efficiently than morphine, leading to higher concentration at opioid receptors and a stronger, faster effect.
Part (c): Diamorphine is synthesized from morphine via an esterification (or condensation/acetylation) reaction using ethanoic anhydride (or acetyl chloride) as the reagent.
Marking scheme
Part (a): - Award [1] for "hydroxyl" or "phenol" or "alcohol". Do NOT accept hydroxide.
Part (b): - Award [1] for stating that morphine is polar/hydrophilic due to hydroxyl groups AND diamorphine is less polar/hydrophobic/lipophilic due to ester groups. - Award [1] for stating that the blood-brain barrier is lipid-based / non-polar / lipid-soluble. - Award [1] for concluding that diamorphine penetrates / crosses the blood-brain barrier more readily/faster.
Part (c): - Award [1] for esterification / condensation / acetylation AND ethanoic anhydride / acetyl chloride.
Question 5 · Option-based Written
5 marks
Stomach acid consists mainly of hydrochloric acid (\(\text{HCl}\)), which is produced by parietal cells.
(a) Formulate a chemical equation for the neutralization of excess stomach acid by magnesium hydroxide, \(\text{Mg(OH)}_2\). [1]
(b) Calculate the mass, in grams, of \(\text{Mg(OH)}_2\) needed to neutralize \(150.0\text{ cm}^3\) of \(0.120\text{ mol dm}^{-3}\) hydrochloric acid. (\(M_{\text{r}}(\text{Mg(OH)}_2) = 58.33\text{ g mol}^{-1}\)). [2]
(c) Contrast the mechanisms of action of ranitidine (Zantac) and omeprazole (Prilosec) in controlling stomach acidity. [2]
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Worked solution
Part (a): The neutralization of hydrochloric acid by magnesium hydroxide produces magnesium chloride and water: \(\text{Mg(OH)}_2\text{(s)} + 2\text{HCl(aq)} \rightarrow \text{MgCl}_2\text{(aq)} + 2\text{H}_2\text{O(l)}\)
Part (b): 1. Calculate the amount in moles of \(\text{HCl}\): \(n(\text{HCl}) = 0.120\text{ mol dm}^{-3} \times 0.1500\text{ dm}^3 = 0.0180\text{ mol}\) 2. Determine the moles of \(\text{Mg(OH)}_2\) required from the stoichiometric ratio (1:2): \(n(\text{Mg(OH)}_2) = \frac{0.0180\text{ mol}}{2} = 0.00900\text{ mol}\) 3. Calculate the mass of \(\text{Mg(OH)}_2\): \(m = 0.00900\text{ mol} \times 58.33\text{ g mol}^{-1} = 0.525\text{ g}\)
Part (c): - Ranitidine is an \(\text{H}_2\)-receptor antagonist. It acts by blocking histamine receptors on parietal cells, preventing the signal that triggers gastric acid production. - Omeprazole is a proton pump inhibitor (PPI). It works downstream by directly binding to and inhibiting the \(\text{H}^+/\text{K}^+\)-ATPase enzyme (the proton pump) that releases hydrogen ions into the gastric juice.
Marking scheme
Part (a): - Award [1] for a correct balanced equation: \(\text{Mg(OH)}_2 + 2\text{HCl} \rightarrow \text{MgCl}_2 + 2\text{H}_2\text{O}\). State symbols are not required.
Part (b): - Award [1] for calculating \(n(\text{HCl}) = 0.0180\text{ mol}\) AND \(n(\text{Mg(OH)}_2) = 0.00900\text{ mol}\). - Award [1] for \(0.525\text{ g}\) (accept answers in range \(0.52\) to \(0.53\)). Award [2] for correct final answer.
Part (c): - Award [1] for stating ranitidine blocks \(\text{H}_2\) / histamine receptors (in parietal cells). - Award [1] for stating omeprazole inhibits proton pumps / \(\text{H}^+/\text{K}^+\)-ATPase enzyme.
Question 6 · Option-based Written
5 marks
Oseltamivir (Tamiflu) and zanamivir (Relenza) are antiviral drugs used to combat the influenza virus.
(a) Identify the specific viral enzyme that both oseltamivir and zanamivir inhibit, and explain how this inhibition prevents the spread of the virus. [2]
(b) The structural formula of zanamivir contains several polar groups. Identify two functional groups present in zanamivir that are absent in oseltamivir. [2]
(c) State one environmental concern associated with the widespread use and disposal of antiviral drugs like oseltamivir. [1]
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Worked solution
Part (a): Both oseltamivir and zanamivir are neuraminidase inhibitors. The enzyme neuraminidase is responsible for cleaving sialic acid on the glycoprotein receptors of host cell membranes, allowing newly formed viral particles (virions) to escape the host cell. By inhibiting this enzyme, the virions remain trapped on the host cell surface, halting further viral replication and spreading to healthy cells.
Part (b): Comparing their structures, zanamivir has a guanidino group (\(-\text{NH}-\text{C}(=\text{NH})-\text{NH}_2\)) and multiple hydroxyl (\(-\text{OH}\)) groups (polyhydroxyl tail) which are absent in oseltamivir (oseltamivir contains an ester and an ether group instead).
Part (c): Large quantities of oseltamivir and its active metabolite are excreted into waterways through sewage systems. This continuous low-dose exposure in aquatic environments, particularly to wild fowl (natural reservoirs of influenza), can lead to the natural selection and emergence of antiviral-resistant strains of the influenza virus, rendering the medication ineffective.
Marking scheme
Part (a): - Award [1] for naming the enzyme neuraminidase. - Award [1] for explaining that inhibition prevents newly formed virus particles / virions from escaping/being released from infected cells.
Part (b): - Award [1] each for identifying any two of: guanidino group (accept guanidine) / hydroxyl group (accept alcohol / polyhydroxyl). Do NOT accept amine, carboxamide, or carboxylic acid (as these are not absent/distinguishing in the same way, or are not in zanamivir).
Part (c): - Award [1] for any of: leads to development of drug-resistant strains of influenza (in wild bird populations/aquatic environments) OR bioaccumulation in food chains OR toxicity to aquatic ecosystems.
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