1 Victoria Junior College 2007 H2 Chemistry Preliminary Examination (9476/3) 1 This question is about the compounds of nitrogen and

phosphorus. (a) One of the nitrogen compounds, hydrazine, N2H4, is used as a rocket fuel. Pure hydrazine is a colourless, oily liquid which can be prepared by the reaction of another nitrogen compound, ammonia, NH3, with hypochlorite ion (OCl-) in aqueous solution. (i) Draw a dot-and-cross diagram (involving only valence electrons) of hydrazine. [1]

H
x

Hx

N H
x

(ii) From the experiment, it is found that in tetrahydrofuran solution, 1 mole of hydrazine will react with 2 moles of BF3 to form a product with melting point of 260 Explain why these two molecules react in the given mole ratio. C. [1] 2 dative bonds are formed since there are two lone pairs of e- on two N atoms in N2H4. (iii) Predict the solubility of hydrazine in water. Explain your answer briefly. Hydrazine is soluble in water since its molecule can form hydrogen bonds with water. (iv) The following table shows the boiling points of PH3, NH3 and N2H4. Compound Boiling points / C
o

[1]

PH3 88

NH3 33

N2H4 114

Compare and contrast the differences in the boiling points in terms of the structure and bonding present in the three compounds. [3] Both NH3 and N2H4 molecules are held together to each other by hydrogen bond. However, there is only one hydrogen bond formed on average for each NH3 molecule while two H bonds formed on average for each N2H4 molecule. (OR more extensive hydrogen bond formed between N2H4 molecules due to greater number of lone pairs present.) Hence, N2H4 has a higher boiling point than NH3. On the other hand, PH3 molecules are held together by dipole- dipole attraction (OR dispersion forces), which is weaker than H bond, hence the lower boiling point of PH3.

2 (b) In the industry, ammonia, which is used to prepare hydrazine, is synthesised by the Haber process. N2 + 3H2 2NH3,

The figure below shows how percentage of ammonia in the equilibrium mixture varies with pressures at 500oC and 700oC respectively. % of NH3 at equilibrium 500 C 700 C

Pressure /atm (i) Use the above data to deduce whether the production of NH3 is an exothermic or endothermic process. Explain your answer. [1] The production of NH3 is an exothermic process since at higher temperature, there is a lower % of NH3 at equilibrium, implying that the backward reaction is favoured at higher temperature. OR forward reaction is favoured at lower temperature. (ii) The Kp of the reaction is 1.34 10-4 atm-2 at 472oC. A mixture contains 1 mol nitrogen and 3 mol hydrogen initially. When it was allowed to reach equilibrium at 472oC, the equilibrium mixture contains 1.5 mol NH3 were formed. Calculate the total pressure of the system at equlibrium. [3] N2 + 3H2 2NH3, Initial no. of 1 3 0 moles Change -1.50/2 -1.50(3/2) +1.50 Eqm no. of moles 0.25 0.75 1.50 For the correct calculation of no. of moles of N2 and H2 at eqm Total number of moles = 0.25 + 0.75 + 1.5 = 2.5 Kp = 1.34

PNH 3
3

PH 2 PN 2
10-4 = (1.50 / 2.50 x P) 2 / (0.75 / 2.50 x P)3 (0.25 / 2.50 x P)

P = 998 atm

3 (c) Porous ceramics containing calcium phosphate, Ca3(PO4)2 have recently increased their use as artificial teeth and bones since they have a high affinity to the living body. (i) Explain why nitrogen does not form an analogous anion, NO43-. NO43-, [2] N must be able to accommodate 10 electrons in its

To form valence shell. Since N is in period 2, it has no d-orbitals to expand its octet.

(ii) Calcium phosphate is a sparingly soluble solid with a solubility of 2.57 10-6 mol dm-3 in water at 25oC. Calculate the Ksp of calcium phosphate, including the correct units. [1] Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) (1) Ksp = (3 2.57 10-6)3 (2 2.57 10-6)2 = 1.21 10-26 mol5dm-15 (iii) A saturated solution A containing calcium hydroxide and calcium phosphate has a pH of 13. Given that the Ksp of calcium hydroxide is 4.0 10-5 mol3 -9 dm and by making use of your answer in c(ii), calculate the solubility of calcium phosphate in solution A. [3] [OH-] = 10-1 = 0.100 mol dm-3 [Ca2+][OH-]2 = 4.0 10-5 [Ca2+](0.100)2 = 4.0 10-5 [Ca2+] = 0.00400 mol dm-3 [ecf for wrong Ksp of calcium phosphate from (i)] [Ca2+]3[PO43-]2 = 1.21 10-26 0.0043 [PO43-]2 = 1.21 10-26 [PO43-] = 4.35 10-10 mol dm-3 Solubility = (4.35 10-10) = 2.18 10-10 mol dm-3 (iv) Comment on and explain the discrepancy in the solubilities of calcium phosphate in water and in solution A. [2] Solubility of calcium phosphate in solution A is lower. Presence of common ion, Ca2+, shifts position of equilibrium (1) above to the left by Le Chateliers Principle. (v) One of the steps in the manufacture of porous ceramics involves addition of a strong acid like hydrochloric acid to selectively dissolve the calcium phosphate present in the untreated ceramic. Explain, why addition of an acid increases the solubility of calcium phosphate. [2] + 3H reacts with PO4 to form the weakly dissociated acid, H3PO4. 3H+ + PO43H3PO4 3PO4 is removed from solution, position of equilibrium (1) shifts to the right, thus increasing solubility. [Total: 20]

4 2(a) The two plots, I and II in the graph below illustrates the trend in the firsonisation energy and the melting point of elements from proton numbers 21 to 30.
2500 First ionisation energy (kJmol-1) OR Melting point

2000

I
1500 (oC) 1000

II

500

0 20 21 22 23 24 25 26 27 28 29 30 31 Proton Number

(i)

Which physical property does plots I and II correspond to? I: II: Melting point First ionisation energy

[1]

(ii)

[2] The first ionisation energy is relatively constant across the transition series. Across the period, additional electron enters the penultimate 3d subshell, providing and effective shield between nucleus and the outer 4s electrons. As a result, the increase in nuclear charge is nullified by the increase in shielding effect and there is insignificant increase in effective nuclear charge across the period. State the full electronic configurations, and the number of unpaired electrons of (i) (ii) the Fe atom, the Cu+ ion. [3]

Account for the general trend in the first ionisation energy.

(b)

(i) (ii)

Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2 4 unpaired electrons Cu+: 1s2 2s2 2p6 3s2 3p6 3d10 No unpaired electron

5 (c) The use of the Data Booklet is relevant to this question. When aqueous iron(II) sulphate is boiled with an excess of potassium cyanide, a yellow solution A containing K4[Fe(CN)6] is obtained. When A was acidified, and chlorine gas was passed through it, a red solution, B was obtained. Aqueous iron(III) sulphate is found to catalyse the reaction between iodide and peroxodisulphate, S2O82-, whereas B does not affect the rate of this reaction. Explain these observations as fully as you can, with the aid of equations and reference to relevant Eo values. [7] Ligand exchange reaction takes place as six H2O molecules in [Fe(H2O)6]2+ is replaced by CN- to form the more stable [Fe(CN)6]4- (or CN- is a stronger ligand than H2O) which turns the solution yellow. B is [Fe(CN)6]3-. Cl2 oxidises [Fe(CN)6]4-: 2[Fe(CN)6]4- + Cl2 2[Fe(CN)6]3- + 2ClReaction is feasible under standard conditions as Eocell = +1.36 (+0.36) = +1.00 V > 0 Fe3+ can act as a catalyst for the reaction between I- and S2O82-: 2Fe3+(aq) + 2I(aq) 2Fe2+(aq) + I2(aq) Eocell = +0.77 (+0.54) = +0.23 V > 0 2Fe2+(aq) + S2O82(aq) 2Fe3+(aq) + 2SO42(aq) o E cell = +2.01 (+0.77) = +1.24 V > 0 The two reactions are feasible under standard conditions as the Eo of Fe3+/Fe2+ (+0.77 V) lies between that of I2/I- (+0.54 V) and S2O82-/SO42- (+2.01 V). The activation energy of the catalysed reaction is lowered and the reactions between oppositely charged ions are faster than the uncatalysed reaction involving negatively charged ions. Eo for [Fe(CN)6]4-/[Fe(CN)6]3- is +0.36 V, which is not within the required range. 2[Fe(CN)6]3 + 2I 2[Fe(CN)6]4 + I2 Eocell = +0.36 (+0.54) = 0.18 V < 0 Reaction is not feasible under standard conditions. Reaction with I- is also not favoured as both are negatively charged ions. [7]

6 (d) The special stability associated with the formation of chelates is called the chelate effect, and can be explained by looking at the entropy changes that occur when polydentate ligands bind to a metal ion. The molecule methylamine (CH3NH2) can act as a monodentate ligand. The following are equilibrium reactions and the thermochemical data at 298 K for reactions of methylamine and ethylenediamine (en) with Cd2+ (aq): Cd2+ (aq) + 4CH3NH2 (aq) [Cd(CH3NH2)4]2+ (aq) Ho = -57.3 kJmol-1; So = -67.3 Jmol-1K-1 Cd2+ (aq) + 2en (aq) Ho = -56.5 kJmol-1; (i) [Cd(en)2]2+ (aq) So = +14.1 Jmol-1K-1

Calculate the standard enthalpy change and the standard entropy change for the ligand exchange reaction and explain their values: [Cd(CH3NH2)4]2+ (aq) + 2en (aq) [Cd(en)2]2+ (aq) + 4CH3NH2 (aq) [2]

Adding the reverse of first reaction to the second reaction, [Cd(CH3NH2)4]2+ (aq) Cd2+ (aq) + 2en (aq) Cd2+ (aq) + 4CH3NH2 (aq) [Cd(en)2]2+ (aq)

Ho = +57.3 + (-56.5) = +0.8 kJmol-1 (reaction is endothermic) So = +67.3 + 14.1 = +81.4 Jmol-1K-1(reaction results in an increase in disorder) (ii) Calculate the standard Gibbs free energy and explain whether the formation of [Cd(en)2]2+ is thermodynamically preferred over the formation of [Cd(CH3NH2)4]2+. [2] o o o G = H -TS = +0.8 298(+81.4/1000) = -23.5 kJmol-1 The standard Gibbs free energy change is negative, indicating that the reaction takes place spontaneously, and the formation of [Cd(en)2]2+ is thermodynamically preferred over the formation of [Cd(CH3NH2)4]2+. (iii) Interpret your conclusion to (ii) with reference to the enthalpy and entropy changes of the reaction. [2] Although the reaction is endothermic, it still occurs spontaneously as it is favoured by a large increase in the disorder of the system. The large increase in disorder is attributable to the increase in the number of particles on the product side than on the reactant side (5 particles on the right versus 3 particles on the left) as there are more ways to arrange the greater number of particles.

7 (iv) State and explain briefly the sign of Ho for the following hypothetical reaction: [Cd(NH3)4]2+(aq) + 4CH3NH2 (aq) [1] 2+ o H is positive as CH3NH2 binds more tightly to Cd than NH3 due to availability of lone pair on N for dative bonding. [Total: 20] 3(a) Azomethane, CH3N=NCH3, is a common compound used in cancer research. It decomposes according to the following equation: CH3N=NCH3(g) CH3CH3(g) + N2(g) (i) Suggest a variable that can be monitored experimentally to study the rate of the reaction. Explain your answer. Pressure can be monitored as there is a change in the number of moles of gas as the reaction progresses. [1] The concentration of ethane, [CH3CH3], was determined at different times in a particular experiment and is shown below: t /s 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 (ii) [CH3CH3] /mol dm-3 0 0.0121 0.0176 0.0200 0.0211 0.0216 0.0218 0.0219 0.0220 0.0220 0.0220 [Cd(CH3NH2)4]2+ (aq) + 4NH3 (aq)

Using the given data, plot a suitable graph to determine the order of the reaction with respect to azomethane. Labelled axes Points plotted correctly Smooth curve Show two consistent half-lives graphically Since half-life is constant at 875 s, the reaction follows first order kinetics. [3]

8 (iii) Calculate the rate constant for this reaction and state its units. k = ln 2 / 875 = 7.92 10-4 s-1

[1]

(iv) Using relevant bond energy values from the Data Booklet, calculate the enthalpy change of this reaction. H H H H

H C N N C H H H

H C C H H H

N N

Bonds broken = 2(CN) + N=N = 2(305) + 410 = 1020 kJ mol-1 Bonds formed = (CC) + N N = 350 + 994 = 1344 kJ mol-1 Hrxn = 1020 1344 = 324 kJ mol-1 (v)

[2]

With the aid of the Boltzmann distribution, explain why the addition of a catalyst increases the rate of a reaction. Catalyst provides an alternative reaction pathway with lower activation energy. More molecules possess energy greater or equal to activation energy, as shown by shaded areas below. As frequency of effective collisions increases, rate increases. Number of molecules

Uncatalysed reaction Catalysed reaction

Ea Ea

Energy [2]

(b) (i)

When burnt in a limited supply of air, ethane forms carbon monoxide and water. The enthalpy change of the reaction is 1004 kJ per mol of ethane. Construct a balanced equation that represents this enthalpy change. C2H6(g) + 5/2O2(g) 2CO(g) + 3H2O(l) [1]

9 (ii) Ethane can be synthesized through the hydrogenation of ethene as shown in the following equation: CH2=CH2(g) + H2(g) CH3CH3(g) Calculate the enthalpy change of the hydrogenation reaction, using the following data in addition to the one given in (b)(i): Enthalpy change of combustion of CH2=CH2(g) Enthalpy change of formation of H2O(l) Enthalpy change of combustion of CO(g) Using the reaction in (b)(i), 1004 = Hc(C2H6) 2(283) Hc(C2H6) = 1570 kJ mol-1 H of hydrogenation reaction = 1411 286 (1570) = 127 kJ mol-1 = 1411 kJ mol-1 = 286 kJ mol-1 = 283 kJ mol-1

[3]

(c)

Ethane can be used to synthesize N-ethylpropanamide as shown in the following reaction scheme:
C2H6 I P V S CH3CH2CONHCH2CH3 (i) Identify the intermediate compounds P, Q, R and S. P = C2H5Cl R = C2H5CO2H (ii) Q = C2H5CN S = C2H5NH2 II Q III R IV CH3CH2COCl

[2]

State the reagents and conditions for steps I to V. I: Cl2, UV light, excess C2H6 II: alcoholic KCN, reflux III: H2O/H+(aq), reflux IV: PCl5, room temperature V: excess alcoholic NH3, heat in a sealed tube

[5] [Total: 20]

10 4(a) (i)
HO Br

Br

H H CH3 H C C C C C OH Br OH NH2

O OH

White ppt and decolourisation of reddish brown Br2.

(ii)

O CH3

H H CH3 H C O C C C OCOCH3 CH3 C C NH C O

O OH

Steamy fumes of HCl and / or sweet smell detected (iii)

-

C O O-

O CH3

H C C COONH2

Purple KMnO4 discharged / brown MnO2 formed (iv)

H H CH3 H K O
+ -

O O -K +

C C C OH

C C NH2

Emulsion disappears / compound dissolves (b) Melting point high as Q exists as zwitterions Strong ionic attractions require high energy to overcome. Solubility will be high as zwitterions can form Ion-dipole attractions with water.
H H CH3 H HO C C C OH C C
NH3+ O

11 4(c)
Step I LiAlH4 / ether, room temperature

H HO C CH=C(CH3)CH(NH2)Br OH

Step II alc. KCN, reflux

H HO C CH=C(CH3)CH(NH2)CN OH
Step III - H2O / H+ (e.g.dilute HC ), heat

H HO C CH=C(CH3)CH(NH2)COOH OH

(d)

(i) Add 2,4 dinitrophenylhydrazine to both compounds at room temperature. Only R will give orange ppt (or add aq. alkaline I2 at <70oC, see yellow ppt)
HO CH2CH2COCH3 C H(COOH)NH2

O2N

NHNH2 NO2

CH3 HO

O2N NO2

CH2CH2C N N C H(COOH)NH2 H

+ H2O

12 (ii)

Heat with aq. NaOH, pungent fumes of NH3 evolved for S which turned moist red litmus blue.

HO
S

CH2COCH2CH3 C H(OH)CONH2

+ 2NaOH

Heat

Na+O-

CH2COCH2CH3
+ NH3 + H2O

CH(OH)COO Na

5(a)(i) Denaturation refers to the disruption of shape of protein without affecting the primary structure but resulting in loss of biological activity and changes in chemical and physical properties.

E.g. The coagulation of egg white (albumin) during the application of heat when an egg is boiled due to disruption of weak forces and bonds between R groups; Addition of heavy metal ions or addition of acids / bases which disrupt ionic bonds; Addition of detergents / organic solvents that disrupts hydrophobic interactions; Addition of polar organic solvents (e.g. ethanol) that interfere with hydrogen bonds between R groups.
(a)(ii) Quaternary structure refers to the three dimensional structure of proteins with two or more polypeptide chains stabilised by R group interactions such as van der Waals forces, ionic bonds and hydrogen bonds.

E.g. The 22 structure of haemoglobin, which comprises of 4 polypeptide chains (two and two subunits)

13

(b)(i)

H2 N C CO2H and H

CH 2 CO 2H

CH 2 H 2N C CO 2H H

(b)(ii) CH2CO2H : hydrogen bonding with R groups containing OH / NH2 / C=O or CH2CO2H when ionised to CH2CO2 in aqueous medium can form ionic bonds / electrostatic attraction with cationic R groups e.g. those with NH3+

CH2C6H5 : dispersion forces with non-polar R groups

(b)(iii) Primary amine : Add aqueous CuSO4 blue complex formed

Carboxylic acid : Add NaHCO3/Na2CO3 effervescence of CO2 which gave a white precipitate with limewater. Note : There is no simple test for esters (hydrolysis and test for acid or alcohol)
(c)
CO2 H OH O 2N CO2 H OH H 2N OH OH F: O H2N O 2N CO2 H OH CO2 H OH

A:

B:

C:

D:

E:

[6 ]

C : H ratio of A 1 : 1 A is highly unsaturated A contains a benzene / aromatic ring

A, C8H8O3, reacts with dilute nitric acid to give B, C8H7NO5 Loss of 1H and gain of 1N and 2O 1 NO2 A is mononitrated (electrophilic substitution) to give B by the dilute HNO3 B, C8H7NO5 is oxidized to C, C7H5NO5 Loss of 1C and 2H CH2 side-chain oxidation (CH2CO2H CO2H)

14

25.0 0.15 250 = 0.015 mol 30.00 Number of moles of NaOH used = 1.0 1000 = 0.030 mol C is a dibasic acid Number of moles of & used =
C gives a violet colouration with neutral FeCl3 C contains phenolic group C effervesces with NaHCO3 C contains a carboxyl group, CO2H B, C8H7NO5, is reduced by Zn/conc HCl to D, C8H9NO3 Loss of 2O and gain of 2H NO2 group in B is reduced to NH2 in D D is crystalline and decompose before melting D is zwitterionic (NH3+ and CO2) held together by electrostatic attraction D, C8H9NO3, is reduced by LiAlH4 to E, C8H11NO2 Loss of 1O and gain of 2H CO2H group in D is reduced to CH2OH in E A, C8H8O3, is converted to F, C8H6O2 Loss of 1O and 2H 1 H2O (overall condensation) The carboxyl group, CO2H, in A is converted into an acyl chloride, COCl, by PCl5. The NaOH then deprotonates the phenol to give a phenoxide which then undergoes internal esterification (nucleophilic substitution), with loss of Cl, to yield the cyclic ester (lactone) F Hence, the carboxymethyl group, CH2CO2H, must be adjacent to phenolic OH group in A to enable ring formation [3]