5 For Examiner's Use 3 One reaction which occurs in air polluted with nitrogen oxides is shown below. 2NO(g) + O2(g) 2NO2(g) Two experiments were carried out to find the relationship between the initial concentration of NO and of O2 and the volume of NO2 produced. The results were plotted below.
(a) The results of experiment 1 allowed the order of reaction with respect to one of the reagents to be found.
(i) State which reagent and explain your reasoning.
n O2. In Expt 1, a huge excess of NO is used. Hence [NO] remain relatively constant as reaction proceeds. The apparent overall order of reaction depends only on the order with respect to O2, which will determine the shape of the graph.
(ii) Deduce the order of reaction with respect to the reagent, showing your working on the graph for Experiment 1. n 1st order [3]
(b) In the boxes above, suggest possible concentrations for NO and O2 in experiment 2. [1]
H2 Chemistry 9647/02/NYJC J2/10 PX [Turn Over
6 For Examiner's Use (c) Catalytic converters are used to remove nitrogen oxides from vehicle exhaust gases. They consist of a chamber of porous material coated with platinum through which the exhaust gases must pass. The platinum will catalyse the reduction of the nitrogen oxides to nitrogen.
Explain how platinum is able to catalyse the reduction of nitrogen oxides.
The reactants molecules are chemically adsorbed on neighbouring active sites on
the catalyst, increasing the surface concentration of the reactant molecules. n The activation energy decreases due to the weakening of the covalent bonds within the reactant molecules n and aid in the formation of the product molecules. [2]
[Total: 6]
4 The table below shows the dissociation equations of hydrofluoric acid, methanoic acid and disodium hydrogen phosphate and the values of their respective dissociation constants. You are to use the following information to answer (a) and (b).
HF + H2O F + H3O+ Ka = 6.8 x 104 HCOOH + H2O HCOO + H3O+ Ka = 1.8 x 104 HPO42 + H2O H2PO4 + OH Kb = 1.6 x 107
(a) For the following reaction:
H2PO4 + F HPO42 + HF
(i) identify the one conjugate acid-base pair,
H2PO4/ HPO42 or HF/ F [1]
(ii) predict, with reasons whether the equilibrium constant will be greater than or less than 1. [3]
The equilibrium constant will be less than 1.
HF has a larger Ka than H2PO4 and will donate proton more readily. HPO42 has a larger Kb than F and will accept proton more readily. Thus the reaction between HF and HPO42 takes place more readily, favouring the backward equation.
1 mark for the correct prediction; award only if explanation shows
understanding 1 mark for the correct explanation
H2 Chemistry 9647/02/NYJC J2/10 PX [Turn Over
2 Hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe’s elemental mass. Hydrogen gas was first produced in the early 16th century, via the mixing of metals with strong acids. While hydrogen is not very reactive under standard conditions, it does form compounds with most elements.
(a) At 700 °C, hydrogen and nitrogen monoxide react as follows:
2H2(g) + 2NO(g) o N2(g) + 2H2O(g)
An experiment is performed to determine the order of reaction with respect to hydrogen. The initial concentration of hydrogen is 0.010 mol dm–3 and nitrogen monoxide is used in large excess so that the order of reaction with respect to hydrogen can be deduced. The concentration of hydrogen at various times in the reaction mixture is found as follows:
(i) Explain why nitrogen monoxide is used in large excess.
Nitrogen monoxide was used in large excess to ensure that the concentration remains constant.
(ii) Use the graph to deduce the order of reaction with respect to hydrogen.
Since half–life is constant at 200s, it is first order with respect to hydrogen.
(iii) On the axis above, draw the graph for an experiment using 0.006 mol dm3 of hydrogen and excess nitrogen monoxide.
Graph with initial concentration 0.006 mol dm–3, half life 200s, plot at least 2 points. [3]
(b) The order of reaction with respect to nitrogen monoxide can be investigated experimentally by varying the partial pressure of the two gases involved and determining the initial rate of the reaction.
(ii) Hence, write a rate equation for the reaction between nitrogen monoxide and hydrogen.
rate = k[NO]2[H2]
(iii) Suggest a reason why the reaction is slow.
The rate determining step involve three molecules, thus it will be difficult for the molecules to collide in the correct orientation and with minimum energy greater than the activation energy.
(iv) Calculate the partial pressure of H2, y, in experiment 3.
1.0 2 u 0.25 0.48
2.0 2 y 1.44
y = 0.188 atm [5]
(c) Hydrogen can also react with chlorine and iodine respectively to form hydrogen halides. (i) Write equations for the reactions that occur.
H2 + I2 2HI H2 + Cl2 → 2HCl
(ii) Hydrogen halides generally dissolve in water to form strong acids. Using relevant data from the Data Booklet, explain whether hydrogen chloride or hydrogen iodide has a lower pH when dissolved in water.
When both [NaOH] and [(chloromethyl)benzene] are increased to 1.5 times,
initial rate increased to 1.5 times. Since the order with respect to (chloromethyl)benzene is 1, the rate of reaction is independent of [NaOH]. Hence, the reaction is zeroth order with respect to NaOH.
(iii) rate = k[(chloromethyl)benzene]
k = (4.8249 × 10–5 mol dm–3 min–1) / 0.0100 mol dm–3 = 4.82 × 10–3 min–1 OR
k = (7.6477 × 10–5 mol dm–3 min–1) / 0.0150 mol dm–3 = 5.10 × 10–3 min–1 OR
(v) 4-chloromethylbenzene will not undergo hydrolysis with NaOH(aq) as there is
partial double bond character in the C–Cl bond due to the overlap of the p orbital of the Cl atom with the S electron cloud system of the benzene ring.
River Valley High School 9647/03/PRELIM/10
Preliminary Examination 2010 5 (a) (ii) Add aqueous NaOH to a separating funnel containing the mixture of phenol and propanone. Shake thoroughly and drain off the aqueous layer. Acidify the aqueous layer with dilute HCl to recover the phenol.
5 (b) (i) & (ii)
Step Reagents & Conditions Product 1 NaCN + dil HCl(to generate HCN) OH trace amt of base CH3 C CH3 CN
2 dil H2SO4 reflux OH CH3 C CH3 COOH
4 CH3OH, conc H2SO4
Reflux
5 (c) (i) Iodine – oxidizing agent
H2SO4 – catalyst
5 (c) (ii) NaHCO3 – quench reaction by reacting with the catalyst, H2SO4: conc of iodine present at diff time intervals can then be found.
NaOH – cannot be used as it can react with iodine producing sodium iodide and sodium iodate.
5 (c) (iii) Zero order wrt iodine
First order wrt sulphuric acid (support answers with relevant explanation or working)
5 (c) (iv) Extrapolate curve to y-axis to find volume of thiosulfate required to react with the iodine present initially or at t = 0 min in a 10.0 cm3 reaction mixture. Vol of thiosulfate reqd = 20.0 cm3 Use the equation I2 + 2S2O32 o 2I + S4O62 to find amount of thiosulfate required to react with iodine present in 10.0 cm3 reaction mixture and hence conc of thiosulfate used. Conc. of thiosulfate used = 1.00 x 104 mol dm3
5 (c) (v) Overall order of reaction is 2.
Since reaction is 1st order wrt sulphuric acid, zero order wrt iodine, hence it is 1st order wrt propanone
7 4 (a) increased risk of respiratory symptoms [1]
(b) O3 o O + O2 (fast) NO + O o NO2 (slow) [1 for correct steps; 1 for indicating r.d.s.]
(c) (i) [O3] = [NO] during the course of the reaction (because from overall chemical equation, NO reacts with O3 in a 1:1 ratio) [1]
[1 for identifying [NO]2 and rate correctly; 1 for correctly calculating
[NO]2; 1 for correctly calculating rate]
Note:
Notice that [NO] = [NO]0 – [NO2], where [NO] represents concentration
of NO at a particular time, [NO]0 represents initial concentration of NO and [NO2] represents concentration of NO2 at a particular time. Hence, [NO]2 = (1.0 × 10–6 – [NO2])2.
