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HWA CHONG INSTITUTION

C2 PRELIMINARY EXAMINATION 9746 H2 CHEMISTRY Paper 2 Structured 25 September 2009 1 hour 30 min

Do not open this booklet until you are told to do so.

READ THESE INSTRUCTIONS FIRST Write your name and class clearly in the spaces at the top of this page. Write in dark blue or black pen. You may use a soft pencil for any diagrams, graphs or rough working. Answer all questions in the spaces provided in this question booklet. A Data Booklet is provided. You may use a calculator. The number of marks is given in brackets [ ] at the end of each question or part question. You are reminded of the need for good English and clear presentation in your answers.

For Examiners Use 1 2 3 4 5 6 Total /6 / 13 / 10 /9 /9 / 13 / 60

This document consists of 14 printed pages.

2 Answer all questions. 1 (a) The alkaline earth metals (beryllium, magnesium, calcium, strontium and barium) all have an oxidation number of +2 in their compounds, and not +1 or +3. Explain the above statement as fully as you can. The alkaline earth metals exhibit +2 oxidation state in their compounds because .. they have 2 valence electrons which are lost to achieve stable octet configuration. [1] .. They do not exhibit +1 oxidation state due to the low lattice energy of the compounds formed. [1] .. The formation of +3 oxidation state is also not favourable due to the very high 3rd .. ionization energy required to remove the third electron from the inner quantum shell. [1] .. .[3] (b) The solubility products of some Group I I fluorides, at 25 oC, are given in the table below: Numerical values of Ksp 1.84 x 107 3.45 x 1011

BaF2 CaF2

A student accidentally mixed 25.0 cm3 of 0.100 mol dm3 CaCl2 solution with 25.0 cm3 of 0.100 mol dm3 BaCl2 solution in the laboratory. To separate the two metal ions, he added just enough solid KF to precipitate the maximum amount of CaF 2 from the mixture, without precipitating BaF2. (i) Determine the [F] required for this separation. Since equal volumes of CaCl2 solution and BaCl2 solution were mixed, [Ba2+] is halved after mixing. [Ba2+] = 0.05 mol dm3 [1/2] [Ba2+] [F-]2 = 1.84 x 107 [F-] = (1.84 x 107 / 0.05) = 1.92 x 103 mol dm3 [1]

(ii)

Determine the concentration of Ca2+ remaining in the final solution. [Ca2+]remaining = 3.45 x 1011 / (1.92 x 103)2 [1/2] = 9.38 x 106 mol dm3 [1]

[3]
9746/02/HCI/C2 Prelim/2009

3 [Total: 6] Glycolic acid CH2(OH)CO2H is an -hydroxy acid (AHA) used in various skin-care products. (a) 0.200 g of glycolic acid (Mr = 76.0) was dissolved in 20.0 cm3 water, and the solution was titrated with 0.100 mol dm3 aqueous NaOH. The following titration curve was obtained. (Ka of glycolic acid = 1.48 x 10 4 mol dm3) pH

0 (i)

Volume of NaOH / cm3

Calculate the volume of NaOH required to reach the equivalence point in the titration. No. of moles of glycolic acid = 0.20/76.0 = 2.63 x 103 mol [1/2] Volume of NaOH required = 2.63 x 103/0.10 x 1000 = 26.3 cm3 [1/2]

(ii)

Calculate the pH of the solution at the equivalence point. No. of moles of CH2OHCOO- salt formed at equivalence pt = 2.63 x 103 mol [CH2OHCOO-]= 2.63 x 103 /(26.3 + 20.0) = 0.0568 mol dm3 [1/2] CH2OHCOOInitial conc. / mol dm3 Eqm conc./ mol dm3 0.0568 0.0568 - x + H2O = CH2OHCOOH x + OH x

Kb of glycolate = Kw/Ka of glycolic acid = 1x 1014/ 1.48 x 104 = 6.76 x 1011 mol dm3 [1/2] Kb = x2/(0.0568 x) x2/0.0568 (assume x << 0.0568 mol dm3) x = 1.959 x 106 mol dm3 [1/2] Or apply formula [OH-] = cKb pOH = 5.708 pH = 14 5.708 = 8.29 [1/2]

9746/02/HCI/C2 Prelim/2009

(iii)

The table below lists the working ranges of some acid-base indicators. Indicator Bromophenol blue Methyl red Neutral red Metacresol purple Thymolphthalein Working range 3.0 4.6 4.4 6.2 6.8 8.0 7.6 9.2 9.310.5 Low pH color yellow red red yellow colorless High pH color purple yellow yellow purple blue

Suggest an indicator that can be used for this titration and give a reason for your choice. Metacresol purple [1] because its working range lies within the rapid pH change of the titration over the equivalence point (pH = 8.29) which lies in ... the alkaline pH region [1] .. [5] (b) Glycolic acid can undergo a series of reactions as shown below.
H O H C C OH OH Glycolic acid Multiple Steps O O Cl C C Cl C

Step 1

H H H C C H OH OH

Step 2

H H H C C H Cl Cl A Step 3

H H H C C Cl B

(i)

What reagents and conditions are required for the following steps? LiAlH4 in dry ether, rtp [1] Step 1 PCl5 (s), rtp [1] Step 2 Ethanolic KOH, heat [1] Step 3

9746/02/HCI/C2 Prelim/2009

(ii)

Arrange the three compounds A, B and C in order of increasing ease of hydrolysis, giving your explanations clearly. Increasing ease of hydrolysis: B< A <C [1] ... C is an acid chloride which undergoes hydrolysis more easily than A (halogenoalkane), because the carbon in the COCl group of C is .. bonded to two electronegative atoms, O and Cl, thus the carbon is more electron deficient and more readily attacked by nucleophile (H2O) ... to undergo nucleophilic substitution. [1] .. B undergoes hydrolysis less easily than A because in B, the CCl bond has partial double bond character due to the overlap of the p-orbital of ... Cl with the -electron cloud of the adjacent carbon atoms in the C=C bond. Thus the CCl bond in B is much stronger than in A, and is harder to break. [1] ... OR The carbon of CCl in B is less electron deficient than that in A due to the presence of the electron-rich electron cloud of the double bond.

[6] (c) Compounds D and E below are also common -hydroxy acids.
OH O H3C C C OH CH3
OH O H3C C C OH

H O H C C OH OH

H D

CH3

glycolic acid

State the reagents and conditions you would use and the observations you would expect to make, in a simple chemical test, to distinguish glycolic acid from (i) compound D K2Cr2O7, dilute H2SO4, heat [1/2] Reagents and conditions .. Orange dichromate turns green for glycolic acid. Observations .... Solution remains orange for D [1/2] (ii) compound E Iodine, aqueous NaOH, heat [1/2] Reagents and conditions .. Yellow precipitate for E. No yellow precipitate for glycolic acid [1/2] Observations .... [2] [Total: 13]

9746/02/HCI/C2 Prelim/2009

The decomposition of hydrogen peroxide solution to form water and oxygen gas can be catalysed by an enzyme, catalase. 2H2O2(aq) catalase 2H2O(l) + O2(g) A series of experiments were carried out to study the effect of pH on the efficiency of the enzyme catalase. The apparatus was set up as shown below and its mass monitored for 50 minutes at 25oC.

hydrogen peroxide potato disc containing catalase weighing balance

The rate of reaction can be followed by recording the mass loss over a period of time. The following graphs were obtained.

Mass of apparatus/ g

Time / min

9746/02/HCI/C2 Prelim/2009

(a)

Using the results shown on the graphs, sketch the graph of rate of decomposition of hydrogen peroxide against pH.

Rate of decomposition of H2O2 rate of reaction

1

pH

10

11

12

13

14

[1] (b) Explain the shape of your graph in (a) by considering the effect of pH on the structure of the enzyme catalase. At very low and very high pH, the enzyme is denatured. [1] .. This is due to the change in the shape of its tertiary structure / loss of the active site conformation / changes in the side-chain interactions of the peptide .. chain. [1] .[2] (c) Explain, with the aid of a suitable diagram, why the rate of decomposition of hydrogen peroxide at pH 7 is expected to proceed faster at 35 oC.
Fraction of molecules 25oC 35oC Proportion of molecules with KE Ea at 25oC Proportion of molecules with KE Ea at 35oC

[1] for Boltzmann distribution curve

Ea

Kinetic energy

When temperature is increased, number of reactant particles with Energy Activation Energy increases,[1/2]
9746/02/HCI/C2 Prelim/2009

8 frequency of effective collisions increases.[1/2] Since rate of reaction is proportional to the frequency of effective collisions, [1/2] rate of decomposition increases. [1/2]

.. 3]

(d)

Another series of experiments were carried out to study the effect of hydrogen peroxide concentration on the rate of reaction, by using different concentrations of hydrogen peroxide at constant pH 7. The following graph was obtained. rate of reaction

[H2O2]

Account for the shape of the graph. At low [H2O2], rate of reaction increases with increasing [H2O2] (or follow first order kinetics) as there are plenty of active sites available. [1] .. At high [H2O2], rate of reaction remains constant with increasing [H2O2] (or follow .. zero order kinetics) as the active sites are saturated. [1] . [2] (e) Oxygen, collected from the decomposition of hydrogen peroxide, can behave as an ideal gas under certain experimental conditions. (i) What do you understand by the term ideal gas? An ideal gas is a gas that obeys the ideal gas equation (pV=nRT), under all conditions of pressure and temperature. [1] (ii) Would you expect oxygen to behave as an ideal gas at a high pressure? Explain your answer. No. At high pressure, the gas molecules are close together such that the volume of the molecules is significant compared to the volume of the container (or such that intermolecular forces are stronger). [1] [2] [Total: 10]

9746/02/HCI/C2 Prelim/2009

(a)

2-oxopropanedioic acid is also known as mesoxalic acid. It has been used as an antidote to cyanide poisoning.
O HO O C C C OH mesoxalic acid O

(i)

When 15.0 cm3 of 0.250 mol dm3 mesoxalic acid was mixed with 20.0 cm3 of 0.400 mol dm3 sodium hydroxide, the rise in temperature was 2.8 oC. Calculate the enthalpy change of neutralization in this experiment. (The specific heat capacity of all solutions may be taken as 4.18 J cm3 K1.) Quantity of heat evolved = mc T = 35.0 x 4.18 x 2.8 = 409.6 J [1/2] H2A + 2NaOH 2NaA + 2H2O Number of moles of mesoxalic acid = (15.0/1000) x 0.250 = 0.00375 mol Number of moles of NaOH = (20.0/1000) x 0.400 = 0.008 mol Therefore mesoxalic acid is the limiting reagent. [1/2] Number of moles of water formed = 0.00375 x 2 = 0.0075 mol [1/2] Hneut = (409.6/1000) / 0.0075[1/2] = 54.6 kJ mol1 [1/2]

(ii)

What would be the temperature rise if 10.0 cm3 of 1.2 mol dm3 sodium hydroxide had been used instead? Number of moles of NaOH =(10.0/1000) x1.2 = 0.012 mol(still in excess)[1/2] Temperature rise = (35/25) x 2.8 = 3.92 C [1]

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[4] (b) State the reagents and conditions required for the conversion of compound P below into mesoxalic acid in 3 steps, and draw the structures of the intermediates Q and R in the spaces provided.

CH2 CH2 CHCH2CH2 OH Br P OH

CH2=CHCH(Br)CH=CH2 [1]

Q II

O HO

O C C C

O OH

III

CH2=CHCH(OH)CH=CH2 [1]

mesoxalic acid R Step I II III [5] [Total: 9] Reagents and conditions Excess concentrated H2SO4, 170 C [1] NaOH(aq), heat [1] KMnO4(aq), dilute H2SO4, heat [1]

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(a)

Sulfuric acid, under different conditions, can behave as a dehydrating agent, a catalyst, an acid or an oxidizing agent. (i) By means of equations, give one different reaction in each case where concentrated sulfuric acid behaves as a

dehydrating agent dehydration of alcohol to form alkene:

CH3CH2OH conc. H2SO4 H2C CH2 + conc. H2SO4 H2O RCO2R' + H2O

OR esterification:

RCO2H + R'OH

[1]

catalyst nitration of benzene:

+ conc. HNO3 conc. H2SO4

NO2 + H2O

OR esterification: RCO2H + R'OH OR hydration of alkene:

RCO2R' + H2O conc. H2SO4 CH3CH2OH CH2=CH2 + H2O

conc. H2SO4

[1] (ii) Using the reaction between concentrated sulfuric acid and solid sodium bromide, write an equation, including state symbols, to illustrate how concentrated sulfuric acid behaves as an

acid
H2SO4 (l) + NaBr (s) HBr (g) + NaHSO4 (aq) [1]

oxidizing agent
H2SO4 (l) + 2HBr (g) Br2 (g) + SO2 (g) + 2H2O (l) [1] [4]
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(b)

When chlorine gas is bubbled into a sodium halide solution, a brown coloration is observed. Upon addition of reagent X into the resulting mixture, a separate violet layer is observed. (i) Suggest a possible identity of reagent X. Tetrachloromethane / hexane (or any other non-polar organic solvent) [1/2] (ii) Deduce the identity of the halide present, and write an equation for its reaction with chlorine. The halide is iodide. [1/2] 2I (aq) + Cl2(g) 2Cl(aq) + I 2(aq) [1] [2]

(c)

Benzedrin is a stimulant and has the following structural formula:

H HO HO CH2 C CH3 NH2

Draw the structure of the organic products when benzedrin reacts with each of the following reagents. (i) dilute nitric acid O2N H HO HO [1] (ii) ethanoyl chloride O H3C C O H3C C O O CH2 H C CH3 NH C O CH3 [1] CH2 C CH3 NH3+

(iii)

NaOH (aq), followed by CH3I and heat

H H3CO H3CO CH2 C CH3 9746/02/HCI/C2 Prelim/2009 NHCH3

13

[1]

[3] [Total: 9]

The following reaction scheme shows the chemistry of some chromium-containing species in aqueous solution.

Cr2O72-

SO2

Zn

II

B [Cr(H2O)6]2+
blue solution

III Na2CO3 (aq)

VII dil H2SO4

C B

CO2

grey-green ppt
excess NaOH(aq)

excess concentrated NH3(aq) NH3 (aq)

IV
H2O2

D C
yellow solution

VI

[Cr(OH)6]3-

[Cr(NH3)6]3+ violet solution VIII excess H2NCH2CH2NH2

E D
(a) (i) Write the formulae of the following chromium-containing species. A [Cr(H2O)6]3+ [1] B [Cr(H2O)6]2+ [1] C Cr(OH)3 or Cr(H2O)3(OH)3 [1] D CrO42 or Na2CrO4 [1] Draw the structure of E in the space below.

(ii)

9746/02/HCI/C2 Prelim/2009

14
3+

H2 N N H2

H2N Cr H2N NH2 NH2

[1]

(iii)

Explain why CO2 is given off in reaction III. Cr3+ (aq) has a high charge density. Hence [Cr(H2O)6]3+ can undergo hydrolysis in water to produce H+ ions, forming CO2 with carbonate ions. [1] State the type of reaction that occurs in V. Ligand exchange [1] [7]

(iv)

(b)

Explain why [Cr(NH3)6]3+ is coloured. Chromium in [Cr(NH3)6]3+ has d3 electronic configuration and has partially filled 3d-orbitals [1] and a d electron undergoes d-d transition and is promoted to the higher d orbital [1] During the transition, the d electron absorbs a certain wavelength of light from the visible region of the electromagnetic spectrum and emits the remaining wavelength [1] which appears as the colour of the complex observed. [3]

(c)

In chromium electroplating, the electrolyte is a solution containing Cr3+(aq) ions. In a given electroplating experiment, a current of 3.0 A was passed through the circuit for 45 minutes to deposit a thin layer of chromium on a metal object. (i) Calculate the mass of chromium deposited on the metal object.

Mass of chromium =

1 3.0 45 60 52.0 [1] = 1.45 g [1/2] 3 96500

(ii)

Suggest why CrO42 (aq) is usually added to the electrolyte in chromium electroplating. As the Cr3+(aq) ions are discharged at the cathode, they are replenished by the reduction of CrO42-(aq) ions at the cathode. [1] CrO42-(aq) + 8H+(aq) + 3e Cr3+(aq) + 4H2O(l) [1/2]

9746/02/HCI/C2 Prelim/2009

15 [3] [Total: 13]

9746/02/HCI/C2 Prelim/2009