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1 (a) (i) [Ar]3d9 (ii) Period 4, Group 10 (iii) - The size (or radius) increases - The nuclear charge remains the same but repulsion resulting from the additional electron(s) enlarges the domain of the electron cloud (b) Before the reaction : B = sp2, N = sp3; After the reaction: B = sp3, N = sp3 2 (a) (i) Line I II III IV R.M.M 2 4 81 83 2 2 81 2 Formula H+ H+2 Br+ H8135Br+ 1 1 35 1 (ii) The hydrogen & bromine reacted together before ionization (b) Order of reaction with respect to BrO3- = x
4 2
r1 B rO3 = r3 B rO3
1.2x10 2.4x10
3 3
[ [
] ]
1 3
1 1
0.10 = , 0.20
x=1
r1 Br 1 = r2 Br 2
[ ] [ ]
, y=1 1
r3 H = r4 H +
[ ] [ ]
+
rate of reaction = k[BrO3-]1[Br-]1[H+]2 moldm-3s-1 1+1+2= 4 from rate = k[BrO3-]1[Br-]1[H+]2 moldm-3s-1 1.2 x 10-3 = k(0.10)(0.10)(0.10)2 k = 1.2 x 10-3/ 1.0 x 10-4 = 12 mol-3dm9s-1
1 1 2
3 (a) (i)
UV Cl2 2Cl (ii) Propagation steps CH4 + Cl CH3 + HCl CH3 + Cl2 CH3Cl + Cl (iii) The methyl radical, CH3Cl is the intermediate organic substance (b) (i) H CH4 + Cl2 CH3Cl + HCl H = Hf (products) - Hf (reactants) = [Hf (CH3Cl) + Hf (HCl)] [Hf (CH4) + Hf (Cl2)] = [-82 + (-92)] [-75 + 0] = -99 kJ mol-1 (ii) Energy Cl Ea = 16 kJmol-1 CH3
1 1 1 1
2 CH4 + Cl2 H = -99kJmol-1 CH3Cl + HCl R.P. The function of the energy from the UV light is to overcome the Ea. After the reaction has commenced, the energy released by the exothermic process (-99 kJmol-1) is enough for the reaction to proceed to completion without any further assistance from the UV light. Boiling point of oxides
(c)
4 (a) (i)
(b) (i)
Ionic bonds are found in the oxides of Na, Mg and Al, the electrostatic force between the positive metallic ions and the negative oxide ion is very strong. Therefore the boiling point of the metallic oxides are high. - SiO2 has a giant molecular structure where the Si and O atoms are held by strong covalent bonds. Hence SiO2 has a very high boiling point - P4O10, SO3 and Cl2O7 are simple covalent molecules. The force of attraction between the molecules are Van der Waals forces. Therefore, these molecules have low boiling point. As the strength of the V.D.W force depends on the size of the molecule (P4O10 > Cl2O7 > SO3) the boiling point of P4O10 > Cl2O7 > SO3. From Al3+ + 3e Al E = - 1.66 V 2+ SO 4 + 2e + 4H SO2 + H2O E = + 0.17 V Ecell = + 0.17 - (-1.66) = + 1.83 V As the Ecell is positive the reaction will occur spontaneously. 3SO2-4(aq) + 2Al(s) + 12H+(aq) 3SO2(g) + 6H2O(l) + 2Al3+ (aq) Section B To halt the reaction abruptly. - Le Chateliers principle states that if the conditions of a reversible reaction is altered and the equilibrium of the system is disturbed, the position of equilibrium will change to minimize the effects of altering the conditions. - Addition of C2H5OH will increase [C2H5OH], thus according to L. C. P., in order to reduce [C2H5OH], the equation position will shift to the right causing the [CH3CO2C2H5] to increase.
[CH 3COOC 2 H 5][ H 2O] [C 2 H 5OH ][ CH 3COOH ]
1 3
1 2 2 2
(c) Kc = 1
C2H5OH + CH3COOH CH3CO2C2H5 + H2O 0.05 0.05 0.0333 0.0333 0.0333 0.0333 0.0167 0.0167 0.0333 0.0333
n (ethanol)o = 2.3/46 = 0.05 mol n (ethanoic acid)o = 3/60 = 0.05 mol n (NaOH)o = MV/1000 = 1.0 (50)/1000 = 0.05 mol n (NaOH) at equilibrium = n (HCl) required = MV/1000 = 1.0 (33.3)/1000 = 0.0333 mol n (NaOH) reacted = n (NaOH) o n (NaOH) at equilibrium = 0.05 0.0333 = 0.0167 mol n (NaOH) reacted = n (ethanoic acid) at equilibrium n (CH3COOH) eq = 0.0167 mol
Assume the total volume is V Kc = (0.0333/V) (0.0333/V) = 3.98 (0.0167/V) (0.0167/V) (d) (e) (i) Ethylethanoate O C H H 6 (a) (i) (b) (i) C H O H C C H O C H C H O H C H H C H 1 1 1 H 1 1
1 1
H (ii)
H H H Lowry Bronsted base = proton acceptor [H+] = KaC = 6.3x10-5 (0.020) = 1.1 x 10-3 mol dm-3
(ii)
25 V of NaOH/cm3 (iii) Thymolphthalein because the pKa value of it (9.7) falls within the pH range of 6.5 10.5 thus it will change colour at this pH range to indicate the end-point. (c) HA + NaOH NaA + H2O Weak acid From pH = pKa + lg [NaA]/[HA] 4.30 = pKa + lg 1 pKa = - lg Ka = 4.30 Ka = 5.01 x 10-5 mol dm-3 pH = 2.50 = -lg [H+] [H+] = 10-2.50 = 3.16x10-3 moldm-3 From [H+] = KaC (3.16x10-3)2 = 5.01 x 10-5 x C C = 0.199 mol dm-3 7a(i) Enthalpy of solution = the enthalpy change that takes place when one mole of a substance dissolves in a solvent to give an infinitely dilute solution under standard conditions Hsolution = +ve AgNO3 (s) Ag2+(aq) + NO3-(aq) , Hsolution = +ve As temperature increases, according to Le Chateliers Principle, the system will absorb the extra heat energy, equilibrium position shifts to right, indicating the solubility of AgNO3 increases
1+1
1 1 1 1 1 1 2
(ii)
1 1 1
7b(i)
1 1 1
98 (ii) -
100
132
Temp/oC 5 max
water & C6H5Cl are immiscible the total v.p of the mixture is the sum of the partial pressure of the two individual liquids at the same temperature [Ptotal mixture = PH2O + PC6H5Cl] when the total v.p equals the atmospheric pressure, the mixture will boil the boiling point of the mixture is lower than either of the individual liquid the boiling mixture will yield a distillate of a constant composition as below:
mass of C6H5Cl = v.p of C6H5Cl x Mr (C6H5Cl) mass of H2O v.p of H2O x Mr (H2O) The distillate will contain a large portion of C6H5Cl due to its high molar mass (the steam distillation is useful for the extraction of organic compound that decomposes at a temperature near its B.P since in steam distillation, this organic compound can be distilled at a temperature below its normal B.P) (iii) mass of C6H5Cl mass of H2O = v.p of C6H5Cl x Mr (C6H5Cl) v.p of H2O x Mr (H2O) 1 1 4 max
structural isomerism exists in compounds that have the same molecular formula but different structural formula
H -C H-C-C-C-H H H Br
1-bromo-2 -methylpropane
8a
H -C H-C-C-C-H H Br H 2-bromo-2-methylpropane D = 2-bromobutane H HH H H-C-C-C-C-H H H Br H if a haloalkane compound is hydrolysed with aqueous NaOH, alcohol is formed - when alcohol is oxidised, a carbonyl compound C=O is formed - as this carbonyl compound give positive iodoform test, it is a ketone that contains group - C CH3 O -CCCChydrolysis -CCCC + NaOH + NaBr Br OH oxidation -CCCC+ [O] - C C C C - + H2O OH O -
CH3 CH2CCH3 + 3I2 + NaOH CHI3 + CH3CH2COONa yellow precipitate (iodoform) O 8b Hydrolysis of a haloalkane compound produces a tertiary alcohol that cannot be oxidised by acifified KMnO4 Thus E = 2- bromo-2-methylpropane C -CCC Br C -CCC Br C -CCC OH 3 alcohol 8c F = 1-bromobutane -CCCC Br The elimination of HBr from F, -CCCC Br oxidation reaction: - C-C-C == C + 2[O] - C C C-H O propanal + C O methanal
NaOH ethanol
1 1
NaOH
1 1
-CCC=C 1-butene
HBr
or
- C-C-C == C
+ 5[O]
9a(i)
H2N- C COOH HO- C COOH + HNO2 nitric(III) acid or amino ethanoic acid nitrous acid H2N- C COOH
2 + N2(g) + H2O
(ii)
2 + H2O
(iv)
H2N- C COOH
9b
CH3- C Cl 3- C N CCOOH +HCl(g) CH + O O The PE polymer formed by the addition polymerisation process using the Ziegler-Natta catalyst is - a linear polymer - high density & high melting point CH2=CH2 ClCH2-CH2Cl step 1, reagent : Cl2 in CCl4 condition: room temperature step 2, reagent: NaOH in ethanol condition: reflux
step 1 step 2
9c
CH2=CHCl 1 1 1
10a(i) 2Al(s) + 2OH (aq) + 6H2O(l) 2[Al(OH)4] (aq) + 3H2(g) (ii) PV = nRT (1.01x105) x 10-3 = n(8.31)(298) n = 0.0408 mol H2(g) From equation, 3 mol H2(g) 2 mol Al(s) 0.0408 mol H2 ? 0.0408 x = 0.0272 mol Al(s) mass of Al(s) = 0.0272 x 27 = 0.734g % of Al in alloy = 0.734 x 100% 1.00 = 73.4% N2(g) + 3H2(g) 2NH3(g) H = -ve A high temperature will lower the production of NH3 a lower temperature is chosen to increase the yield of NH3 but this will slow down the rate of reaction a catalyst is used to increase the rate the equation N2(g) + O2(g) 2NO(g) H = +ve A high temperature will increases the rate of reaction & at the same time increases the yield of NO, therefore there is no need for a catalyst - there is hydrogen bonding between NH3 molecules - the N atom in NH3 is very electronegative & makes use of its lone pair of electrons to attract a H atom of another molecule - therefore the BP of NH3 is high - PH3 & AsH3 molecules cannot form H bonds. Only weak Van der Waals forces are formed. Therefore, they have low BP
1 2 1 1 1
1 1 1 2
10b
10c
1 1 1 1