Question Bank PG 1 58

1
Objective Questions
4
Matter
1. Alpha particles, 2 He2+, are emitted when a radioactive nucleus disintegrates. Which of the following species has the same number of electrons as one alpha particle? A H+ C Li+ B H D H2 2. In a mass spectrum, the peak at m/e 22 is caused by A CO2+ C CO+ 2+ B CO2 D CO2+ 3. A sample of oxygen gas which contains atoms of two isotopes 16O and 18O is analysed in a mass spectrometer. Which of the ions below will be deflected most in the magnetic field? A 16O2+ C 16O 18O+ B 18O2+ D 16O22+ 4. The mass spectrum of a metal Q is shown below.
What is the relative atomic mass of Q? (85 23) + (87 7.5) A 100 (85 21.5) + (87 8.5) B 100
(85 23) + (87 7.5) C 23 + 7.5 (85 21.5) + (87 8.5) D 21.5 + 8.5
5. When potassium chlorate(V) is heated strongly at its melting point, a mixture of potassium chlorate(VII), KClO4 and potassium chloride is produced. The equation for the reaction is 4KClO3(s) 3KClO4(s) + KCl(s) What amount of potassium chlorate(V) must be used to produce 0.075 mol of potassium chlorate(VII)? A 0.05 mol B 0.10 mol C 0.15 mol D 0.20 mol
Oxford Fajar Sdn. Bhd. (008974-T) 2008
Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 1
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6. The reaction between sulphur dichloride dioxide, SCl2O2 and water is represented by the chemical equation: SCl2O2 + 2H2O H2SO4 + 2HCl What is the volume (in dm3) of 2.0 mol dm3 NaOH required to neutralise completely the reaction products when 2.0 mol of sulphur dichloride dioxide reacts with excess water? A 4 C 8 B 6 D 12 A 1 only is correct B 1 and 2 only are correct C 2 and 3 only are correct D 1, 2 and 3 are correct
7. Which of the formulae given below can be used to calculate the value of the Avogadro constant, L? Mass of one mole of hydrogen gas 1 L= Mass of two atoms of hydrogen 2 3 Volume of one mole of hydrogen gas (cm3) L= Volume of one molecule of hydrogen (cm3) Mass of one mole of carbon12 L= Mass of one atom of carbon12
8. Which of the following compounds contain(s) the same number of atoms as 1.0 mol of oxygen gas? 1 1.0 mol of nitrogen gas 2 0.5 mol of ammonia gas 3 0.5 mol of carbon monoxide
Structured Questions
1. The mass spectrum for an element is shown below.
50
relative abundance %
40
30
20
10
90
91
92
93
94
m/e
(a) Calculate the relative atomic mass of this element. (b) With the help of the Periodic Table, identify the element. 2. A sample of hydrogen chloride molecules consists of the isotopes 1H, 35Cl and 37Cl. The relative abundance of 35Cl and 37Cl isotopes are 75% and 25% respectively. (a) Write down the formulae of all the different ions produced in the ionisation chamber of the mass spectrum.
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(b) Sketch the mass spectrum of this sample of hydrogen chloride molecules, ignoring the peak at m/e 1. (c) Comment on your answer in (b). (d) Calculate the relative molecular mass of the hydrogen chloride in this sample.
Essay Question
1. The mass spectrum of rhombic sulphur is shown below.
(a)
(i) Explain why the mass spectrum of rhombic sulphur consists of a number of peaks. (ii) Identify the species which is most abundant in the sample of sulphur vapour. (iii) From the mass spectrum, deduce the formula of rhombic sulphur. (b) Cisplatin, Pt(NH3)2Cl2, is used to treat certain types of cancer. It is prepared by the following reaction K2PtCl4(aq) + 2NH3(aq) 2KCl(aq) + Pt(NH3)2Cl2(aq) The percentage yield for the reaction is 93.2% where actual yield from experiment percentage yield = 100 theoretical yield If a student wants to prepare 5.72 g of Pt(NH3)2Cl2, what is the mass of K2PtCl4 he should use?
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ANSWER
CHAPTER 1 Matter
Objective Questions 1. A Alpha-particles are helium nuclei, 4 He2+ 2
relative abundance
2. (a) 1H+, 35Cl+, 37Cl+ 1 H 35Cl+, 1H 37Cl+ (b)

100 80 60
Species Helium nuclei H

+
Number of protons 2 1 1 3 2
Number of electrons 0 0 2 2 2
H Li+ H2
40 20
2. B
Ion m/e CO
+ 2
30
35
40
m/e
CO2
2+
CO
CO
2+
44/1 = 44
44/2 = 22
28/1 = 28
28/2 = 14
3. D 16O22+ has the smallest mass and highest charge. 4. D 5. B From the equation, 3 mol of KClO4 is obtained from 4 mol of KClO3 0.075 mol KClO4 is obtained from 4 0.075 = 0.10 mol KClO3 3 6. A SCl2O2 + 2H2O H2SO4 + 2HCl 2 mol of SCl2O2 produces 2 mol of H2SO4 and 4 mol of HCl, that is, 8 mol of H+ ions. H+(aq) + OH(aq) H2O(l) Number of moles of NaOH required = 8.0 8.0 = MV = 2.0 V V = 4 dm3 7. D 1 mol of H2 gas = L 2 hydrogen atoms (1 correct) 1 mol of H2 gas = L molecules of H2 Volume of 1 mol of H2 = L volume of 1 molecule of H2 (2 correct) 1 mol of carbon = L atoms of carbon (3 correct) 8. B 1.0 mol of O2 contains 2 (6.02 1023) oxygen atoms. 1.0 mol of N2 contains 2 (6.02 1023) nitrogen atoms. (1 correct) 0.5 mol of NH3 contains 0.5 x (6.02 1023) nitrogen atoms and (3 0.5) (6.02 1023) hydrogen atoms. (2 correct) 0.5 mol of CO contains 0.5 (6.02 1023) carbon atoms and 0.5 (6.02 1023) oxygen atoms. (3 incorrect) Structured Questions 1. (a) Relative (90 52) + (91 9) + (92 12) atomic + (93 14) + (94 13) = mass 52 + 9 + 12 + 14 + 13 = 91.3 (b) Zirconium (Zr)
4
(c) m/e 35 : 35Cl+; m/e 37 : 37Cl+ Relative heights of these two lines: 3 : 1 m/e 36 : 1H 35Cl+; m/e 38 : 1H 37Cl+. Relative heights of these two lines: 3 : 1 (36 3) + (38 1) (d) Mr of HCl = = 36.5 3+1 Essay Question 1. (a) (i) The mass spectrum of sulphur molecules is caused by the formation of molecular ions and fragmented molecular ions. (Note: The mass spectrum of sulphur as shown in the question is not caused by the isotopes of sulphur). (ii) The most abundant species is the fragmented ion, 32S2+ (or 32S 32S+) which produces the peak at m/e 64. (iii) From the mass spectrum, Mr of sulphur = 256 The relative atomic mass of sulphur = 32 Number of atoms in 1 molecule of rhombic sulphur 256 = =8 32 Thus, the structure of rhombic sulphur is made up of simple molecules. Each molecule contains 8 atoms, that is, the molecular formula of sulphur is S8. 5.72 (b) 92.3 = 100 theoretical yield Theoretical yield = 6.20 g Mr of Pt(NH3)2Cl2 = 195 + 2 (17) + 2 (35.5) = 300 Mr of K2PtCl4 = 2 (39) + 195 + 4 (35.5) = 415 6.20 Number of moles of Pt(NH3)2Cl2 = 300 = 0.0207 1 mol of K2PtCl4 1 mol of Pt(NH3)2Cl2 Number of moles of K2PtCl4 needed = 0.0207 Mass of K2PtCl4 needed = 0.0207 415 = 8.59 g
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2
Objective Questions
The Gaseous State
1. A gaseous hydride of nitrogen, X, contains 87.5 % by mass of nitrogen. The relative molecular mass of X is 32. When X is heated, it gives off a mixture of nitrogen gas and hydrogen gas. What is the total volume of the mixture of gases produced when 100 cm3 of X is heated? A 200 cm3 C 400 cm3 3 B 300 cm D 600 cm3 2. A closed container at s.t.p. contains 11 g of P (carbon dioxide) and 8 g of Q (oxygen). Which of the following statements is true? A The average kinetic energy of P is higher than the average kinetic energy of Q. B The partial pressure of P is higher than the partial pressure of Q. C The partial pressure for each gas becomes 0.5 atm when 1 dm3 of P is mixed with 1 dm3 of Q. D P and Q do not contain the same number of molecules.
3. The graph of against p for a gas, X, at 273 K is shown below. p
( = density of gas in g dm3; p = gas pressure in atm; R = gas constant) What is the relative molecular mass of X at a pressure of p = 0 and a temperature T = 273 K? 273Y A 273 RY C R 273Y RY B D R 273 4. A gaseous mixture contains 64 g of methane, 64 g of oxygen and 64 g of sulphur dioxide. The gaseous mixture exerts a pressure of 210 kPa. What is the partial pressure of methane? [Relative atomic mass: C, 12, O, 16, S, 32] A 30 kPa B 60 kPa C 70 kPa D 120 kPa 5. A 1.0 dm3 flask contains oxygen at 114 kPa and a 2.0 dm3 flask contains nitrogen at 67.5 kPa. The two flasks are connected and the two gases allowed to mix. What is the total pressure of the gaseous mixture? [The temperature is assumed to remain constant.] A 7 kPa B 38 kPa C 45 kPa D 83 kPa
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A 1 only is correct
B 1 and 2 only are correct
C 2 and 3 only are correct
D 1, 2 and 3 are correct
6. Which of the following formulae represent(s) the properties of an ideal gas? ( = density; m = mass of gas; M = relative molecular mass) 1 p = RT 3 pV = MrRT Mr 2 RT pV =
7. A 10.0 dm3 glass bulb contains 2.0 g of hydrogen, 9.98 g of argon and 3.42 g of oxygen. We can deduce that 1 the amount of moles of oxygen in the mixture is 0.214 mol. 2 the total amount of gases in the mixture is 1.357 mol. 3 the total pressure of the gaseous mixture is 3.34 atm. (Relative atomic mass: H, 1.0; Ar, 39.9; O, 16; temperature = 27 C) 8. A gaseous mixture contains 0.8 mol of Cl2, 0.8 mol of PCl3 and 0.2 mol of PCl5. At 423 K, the pressure of the mixture is 96 000 Pa. Which of the following statements is/are true? 1 The partial pressure of chlorine is 10 667 kPa. 2 The partial pressure of PCl3 is 42 667 kPa. 3 The partial pressure of PCl5 is 10 667 kPa. 9. Which of the following graphs represent(s) the behaviour of an ideal gas? 1 p 2 p 3 p
1 v
t (C)
1. (a) Explain why a decrease in the volume of a gas causes an increase in its pressure. (b) State the law that shows the relationship between the pressure and volume of a gas. (c) A sample of chlorine gas occupies a volume of 45.2 dm3 at a pressure of 340 kPa and a temperature of 57 C. Calculate the mass of chlorine gas in the sample. 2. Nitric oxide reacts rapidly with oxygen as represented by the following equation 2NO(g) + O2(g) 2NO2(g) The apparatus shown below can be used to carry out this reaction.
NO
O2 2 dm3 1.0 atm
4 0.5 atm
dm3
When the tap T is opened, a fast reaction occurs. Calculate (a) the amount (in moles) of NO and O2 present before the reaction. (b) the amount (in moles) of NO2 produced in the reaction. (c) the number of moles of gases remaining after the experiment. (d) the partial pressure for every gas in the resultant mixture.
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Essay Question
1. (a) Describe qualitatively in terms of kinetic theory the essential difference between the gaseous, liquid and solid states. (b) Explain why the behaviour of a real gas differs from that predicted by the ideal gas behaviour. (c) When a gas is collected over water, it is saturated with water vapour. A sample of hydrogen (45.5 cm3) was collected over water at 25 C and 0.992 atm. The vapour pressure of water at 25 C is 0.0313 atm. What is the amount (in mol) of hydrogen collected in this experiment?
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ANSWER
CHAPTER 2 The Gaseous State
Objective Questions 1. B
Element Mass No. of moles Mole ratio 87.5 87.5 = 6.25 14 6.25 = 1 6.25 N H 100 87.5 = 12.5 12.5 = 12.5 1 12.5 = 2 6.25
2.0 7. C nhydrogen = = 1.0 2.0 9.98 nargon = = 0.25 39.9 3.42 = 0.107 (1 incorrect) noxygen = 32 Total number of moles = 1.0 + 0.25 + 0.107 = 1.357 (2 correct) nRT 1.357 0.0821 300 PT = = V 10.0 = 3.34 atm (3 correct) 8. C Total number of moles = 0.8 + 0.8 + 0.2 = 1.8 0.8 Partial pressure of Cl2 = 96 000 1.8 = 42 667 kPa (1 incorrect) 0.8 96 000 Partial pressure of PCl3 = 1.8 = 42 667 kPa (2 correct) 0.2 Partial pressure of PCl5 = 96 000 1.8 = 10 667 kPa (3 correct) 9. D Graphs 1 and 2 are different representations of Boyles law. Graph 3 represents the effect of temperature on pressure. As the temperature increases, the kinetic energy of the gaseous particles increases and the frequency of collisions on the walls of the container increases. Thus, the pressure increases. (1, 2, 3 correct) Structured Questions 1. (a) According to the kinetic theory of gases, the pressure of a gas is caused by the collisions of gaseous particles on the walls of the container. When the volume of the gas decreases, the number of molecules per unit volume increases. This increase causes the molecules to collide more frequently with the walls and therefore increases the pressure. (b) Boyles law: The volume of a given mass of gas is inversely proportional to its pressure if the temperature of the gas is kept constant. (c) pV = nRT pV (340 103) (45.2 103) n= = RT 8.31 (273 + 57) = 5.60 mol Mass of chlorine = 5.60 71 = 397.6 g 2. (a) Before reaction Number of moles of nitrogen oxide (NO) pV 0.5 4 2 = = = RT RT RT
Empirical formula of X is NH2. nNH2 = 32 n(14 + 2) = 32 n=2 Molecular formula of X is N2H4. N2H4 N2 + 2H2 1 mol 1 mol + 2 mol = 3 mol 1 vol 3 vol 100 cm3 300 cm3 11 11 g of P (CO2) = = 0.25 mol 44 8 8 g of Q (O2) = = 0.25 mol 32 mRT RT 3. A Mr = = pV p where p = 0; T = 273, = Y p Mr = YRT = 273RY 4. D Relative molecular mass: CH4 = 16, O2 = 32, SO2 = 64 64 Number of moles of CH4 = =4 16 64 =2 Number of moles of O2 = 32 64 Number of moles of SO2 = =1 64 7 mol of gases exert a pressure of 210 kPa. 4 4 mol of CH4 exert a pressure of 210 7 = 120 kPa. 5. D p1V1 = p2V2 114 1.0 Partial pressure of O2 = = 38 kPa 3 67.5 2.0 Partial pressure of N2 = = 45 kPa 3 Total pressure = 38 + 45 = 83 kPa 6. A mRT RT Mr = = pV p p = ( )RT (1 correct) Mr
8
2. C
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Number of moles of oxygen (O2) 1.0 2 2 = = RT RT (b) Amount of NO2 produced 2NO(g) + O2(g) 2NO2(g) 2 mol of nitrogen oxide (NO) reacts with RT 1 mol of oxygen (O2) to produce RT 2 mol of nitrogen dioxide (NO2). RT (c) After the experiment Number of moles of O2 remained 2 1 1 = = (1) RT RT RT Number of moles of NO2 produced 2 = (2) RT (d) pV = nRT For oxygen Volume of oxygen after mixing = 2 + 4 = 6 dm3 1 Partial pressure of oxygen 6 = RT RT From equation (1) 1 Partial pressure of oxygen = = 0.167 atm 6 For nitrogen dioxide Volume of NO2 after mixing = 6 dm3 Partial pressure of nitrogen dioxide 6 From equation (2) 2 = RT RT 2 Partial pressure of nitrogen dioxide = 6 = 0.33 atm Essay Question 1. (a) Kinetic theory: all matter is composed of tiny particles in constant motion. The essential distinction between the gaseous, liquid and solid states is the energy content of the molecules. An increase in temperature
causes an increase in the average kinetic energy of the particles. Gaseous state Molecules are in constant motion (vibrational, rotational and translational motion). Molecules are more widely separated. Molecules have very high energy content. Liquid state Molecules have vibrational, rotational and translational motion. Molecules in the liquid state are much closer together than in gases. Greater intermolecular forces restrict molecular movement. Solid state Molecules have vibrational and rotational motion but no translational motion. The particles are close together and are arranged in a denite pattern, held together by strong intermolecular forces. Molecules have lowest energy content. (b) The behaviour of a real gas differs from the behaviour of an ideal gas because of the existence of attractive forces between the gaseous molecules and the volume occupied by the gas molecules. At high pressures, the volume is decreased. The volume occupied by the molecules and the attractive forces cannot be ignored. Hence real gases do not obey the ideal gas equation, pV = nRT. (c) Total pressure = 0.992 atm 0.992 = Phydrogen + Pwater vapour Phydrogen = 0.992 0.0313 = 0.961 Volume = 45.5 cm3 = 0.0455 dm3 pV = nRT 0.961 0.0455 n= 0.0821 298 = 1.79 103 mol
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3
Objective Questions
The Liquid and Solid States
1. The phase diagram for iodine is shown below.

16 15 pressure (kPa) 14 B 13 12 11 O C
A 100 110 120 130 140
temperature (C)
Which of the following statements is true? A The line OC represents the effect of pressure on the melting point of iodine. B Point C is the critical temperature. C At point B, solid iodine and liquid iodine exist in equilibrium. D Iodine sublimes when heated from room temperature to 120 C at a constant pressure of 14 kPa. 2. A permanent gas is a gas that cannot be liquefied at 25 C. A non-permanent gas is a gas that can be liquefied at 25 C. Which of the following gas is a permanent gas?
Substance Critical temperature (K) 191 324 431 647 Critical pressure (atm) 46 82 78 218
A B C D
Methane Hydrogen chloride Sulphur dioxide Water
3. Which of the following does not exhibit allotropy? A Chlorine C Phosphorus B Ozone D Carbon 4. Diamond and graphite A have the same bond length. B have delocalised electrons in their lattice structure. C produce carbon dioxide and water on combustion. D contain covalent bonds between carbon atoms. A 1 only is correct B 1 and 2 only are correct C 2 and 3 only are correct D 1, 2 and 3 are correct
5. When a few crystals of ice are added to supercooled water at 5 C, 1 more ice is precipitated. 3 the temperature of water increases. 2 the vapour pressure increases. 6. Dry ice is used as refrigerant in the food industry because 1 its melting point is well below 0 C. 2 it is non-toxic and non-carcinogenic. 3 it does not melt to form a liquid at room conditions.
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7. Which of the following statements is/are true? 1 The combustion of fullerene in excess oxygen produces carbon dioxide only. 2 Fullerene and graphite have similar bonding and structure. 3 Fullerene is a macromolecule with thousands of carbon atoms. 8. The crystal structure of an iodine crystal is shown below.
What conclusion(s) can be made about the iodine crystal? 1 The iodine crystal has a face-centred cubic lattice. 1 2 Each unit cell has I2 molecule at each corner. 8 1 3 Each unit cell has I2 molecule at each face. 2
Structured Question
1. The phase diagram for water is shown below.
C P (N m2)
A X
612 D B
0.0076
(a) Name the points O and A. (b) Name the phases in equilibrium (i) at the point O, (ii) along OA, (iii) within AOC. (c) What is the signicance of (i) the point A, (ii) the point D. (d) Explain why the line OC slopes to the left. (e) Explain what happens if ice at point X is gently heated, keeping the pressure constant.
Essay Question
1. (a) (i) Dene freezing point. (ii) Explain freezing using simple kinetic molecular theory. (b) Describe the structure of fullerene.
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ANSWER
CHAPTER 3 The Liquid and Solid States
Objective Questions 1. A When solid iodine at room temperature is heated to 120 C at a constant pressure of 14 kPa, it changes from solid to liquid. 2. A A gas can be liqueed only at temperatures below its critical temperature. For methane, its critical temperature is 191 K (82 C). 3. A 4. D Diamond and graphite contain carbon atoms only. Therefore, the combustion of diamond and graphite gives carbon dioxide only. 5. D A supercooled liquid is metastable. The presence of ice-crystals or even dust particles will cause ice-crystals to be precipitated. This process is called seeding. (1 correct) The vapour pressure and temperature increase as more ice-crystals are formed. (2 and 3 correct). 6. D (1, 2, 3 correct) 7. A Fullerene is an allotrope of carbon. (1 correct) 8. D Each of the six faces has I2 molecules at the centre. (1correct) Each I2 molecule at the corner of the unit cell is shared between eight unit cells. (2 correct) Each I2 molecule on the face of the unit cell is shared between two unit cells. (3 correct) Structured Question 1. (a) O : triple point A : critical point (b) (i) Solid, liquid and vapour (ii) Liquid and vapour (iii) Liquid (c) (i) Point A corresponds to the critical temperature and pressure of the substance. At higher temperatures and pressures beyond this point, the liquid phase and vapour phase are indistinguishable. H2O(l) system at point (ii) The H2O(s) D is metastable. (d) OC shows the effect of increasing pressure on the melting point of ice. The line OC slopes towards the left because there is a decrease in volume when ice (solid) changes into water (liquid). (e)
pressure
Hence, increase in pressure favours the formation of water.
(I) X
(II)
temperature
At condition X water exists in the solid state (in the form of ice). At condition (I) ice melts. Equilibrium exists between ice and water. Between (I) and (II) only water is present. At (II) water evaporates. Equilibrium exists between water and water vapour. At temperatures above (II), only water vapour is present. Essay Question 1. (a) (i) The freezing point is the temperature at which a solid and a liquid exist in equilibrium. (ii) When the temperature of a liquid is lowered, the kinetic energy of the particles decreases, the motion of particles in the liquid is slowed down. At the freezing point, the attractive forces can hold the particles together in a xed position and the liquid freezes (change from liquid state to solid state). (b) Fullerenes: carbon allotropes, cage-like hollow carbon molecules whose atoms are bonded into structures having hexagonal and pentagonal faces. Carbon atom uses sp2 hybridised orbitals to form C C bonds. Hence, fullerenes contain electrons.
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4
Objective Questions
The Electronic Structure of Atoms
1. The figure below shows the lines in the Lyman series of the hydrogen spectrum.
The line M is caused by the transition of electrons A from n = 3 to n = 1 B from n = 6 to n = 1 C from n = 4 to n = 1 D from n = 3 to n = 2 2. The electron configuration of a species which is isoelectronic with H2O is A Li+ C N3 2 B S D Cl 3. Which of the following elements have all the electrons in the p valence shell orbitals unpaired? A Nitrogen B Oxygen C Sulphur D Fluorine 4. An element forms a stable ion of charge +2. Which of the following electronic configuration represents this element? A 1s22s22p4 B 1s22s22p63s23p63d14s2 C 1s22s22p63s23p2 D 1s22s22p63s23p63d104s2 5. In the emission spectrum of hydrogen, how many lines are formed due to electron transitions involving energy levels n = 1 and n = 6? A 5 C 10 B 6 D 15
Structured Question
1. (a) Draw the non-directional orbital which are found in an atom with the proton number 6. (b) Write the electronic configuration for the following: (i) Fe in FeSO4 (ii) Mn in MnO2 (c) Write the valence electronic configuration of S in SF6 by using the box diagram and arrows to repesent the electrons.
Essay Question
1. (a) The frequencies of the first six lines in the Lyman series (1014 Hz) are: 24.7, 29.3, 30.9, 31.6, 32.0 and 32.2. Sketch a labelled energy level diagram to show the electron transitions responsible for forming the lines. By using the above frequencies, draw a suitable line graph that will enable you to calculate the ionisation energy of hydrogen. (b) By using an energy level diagram of orbitals, show the electronic configuration of Fe in Fe2O3. Explain why it is difficult to find Fe(IV) compounds in nature.
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ANSWER
CHAPTER 4 The Electronic Structure of Atoms
1. C The Lyman line series are formed when electrons return to the lowest energy level n = 1. M is the third line. Therefore it involves electron transition from n = 4 to n = 1. 2. C The total number of electrons in H2O = 2(1) + 8 = 10 Nitrogen has 7 electrons and it receives 3 more electrons to form N3. Therefore there are 10 electrons in N3. 3. A The valence shell of nitrogen has the electronic conguration 2s22p3. Therefore each of the three 2p orbitals have a single unpaired electron. Essay Question 1. (a)
n=7 n=6 n=5 energy (kJ mol1) n=4 n=3 n=2
n=1 24.7 29.3 30.9 31.6 32 32.2 frequency (X 1014 Hz)
f (x1014 Hz) f
2s 2p
24.7 4.6
29.3 1.6
30.9 0.7
31.6 0.4
32.0 0.2
32.2
4. D The element must be from Period 4, Group 12 as shown by the electronic conguration. It is zinc. Zinc only has a +2 charge. 5. D Total number of lines = 5 + 4 + 3 + 2 + 1 = 15 Structured Question 1. (a) Carbon has proton number 6. Electronic configuration of carbon is 1s22s22p2. The nondirectional orbitals are 1s and 2s.
z y z y
4 3 2 1 33.1 f (x1014 Hz)
1s
2s
(i) Fe in FeSO4 has +2 charge. The electronic configuration of Fe2+ is 1s22s22p63s23p63d 6. (ii) Mn in MnO2 has + 4 charge. The electronic configuration of Mn4+ is 1s22s22p63s23p63d 3. (c) S has electronic conguration 1s22s22p63s23p 4. In SF6, the 3s and 3p electrons are excited to the empty 3d orbitals. Hence there are six unpaired electrons which will share electrons with an electron of each of the six uorine atoms. The valence electronic conguration of S in SF6 is: (b)
From the graph above, the frequency of the convergence limit is 33.1 1014 Hz. E = hfNA = 6.63 1034 33.1 1014 6.02 1023 = 1321.1 103 J/mol1 = 1321.1 103 /1000 kJ mol1 = 1.32 103 kJ mol1 (b) Fe in Fe2O3 has a charge of +3. The electronic configuration of Fe in Fe2O3 is
3d 5 3p 6 3s 2 energy
2s 2
2p 6
1s 2
3s
3p
3d
To form iron(IV), the electron has to be removed from the Fe3+ ion. Fe3+ Fe4+ + e Fe3+ has the electronic configuration 1s22s22p6 3s23p63d 5. It is stable because it has halffilled 3d orbitals. So it is difficult to remove an electron from the stable Fe3+ ion.
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5
Objective Questions
The Periodic Table
1. A metal X has only one oxidation state in all its compounds. Atom X is most likely to have the electronic configuration of A 1s2 2s2 2p3 C 1s2 2s2 2p6 3s2 2 2 5 B 1s 2s 2p D 1s2 2s2 2p6 3s2 3p6 3d5 4s1 2. Beryllium (Be), carbon (C), fluorine (F) and lithium (Li) are Period 2 elements. Which element has the lowest melting point and which element has the highest melting point?
Lowest melting point Highest melting point C Li C Li
A B C D
Be Be F F
3. In which of the following pairs is the atomic size of the first atom larger than the second atom? A Na, Mg C Li, Na B Al, Mg D F, Cl 4. Which of the following pairs of elements will form a compound with the highest ionic character? A Cs and F C Ba and F B Li and I D Ba and I 5. The successive energies (in kJ mol1) of an element, X, are shown below. 1020 (1st), 2150, 3400, 4650, 7080, 27 300, 32 100 This element is expected to form an ion with the formula A X 2+ C X 2 3+ B X D X 3 6. Which of the following pairs of elements has giant structures? A Carbon and phosphorus B Boron and silicon C Silicon and sulphur D Boron and phosphorus A 1 only is correct B 1 and 2 only are correct C 2 and 3 only are correct D 1, 2 and 3 are correct
7. Which of the following properties increases on going across Period 3 (sodium to chlorine)? 1 Atomic size 3 First ionisation energy 2 Electronegativity 8. On descending from beryllium to barium in Group 2 of the Periodic Table, 1 the first ionisation energy decreases. 2 the metallic character increases. 3 the metallic radius increases.
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electronegativity
electronegativity
C B Be Li 3 4 5 6 proton number
electronegativity
9. Which of the following graphs correctly represent(s) the variation of electronegativity against proton number? 1 2 3 C
N O F 4 5 6 7 proton number Li Na K 5 10 15 20 proton number
1. The physical properties of four elements, P, Q, X and Y are shown below.
Element Melting point (C) First ionisation energy (kJ mol1) Electrical conductivity (25 C) P 937 762 Poor Q 650 736 Good X 1535 762 Good Y 7.2 1140 Non-conductor
(a) Which element is a (i) Group 2 element? (ii) Group 15 element? (iii) Group 17 element? (iv) d-block element? Give a reason for your choice. (b) Identify the s and p elements from the list. 2. (a) The electronic configuration of an ion, X2+, is shown below. 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 (i) What is the proton number of element X? (ii) Write the electronic configuration of element X. (iii) Classify element X as s-, p-, d- or f-block element. (b) (i) Using aluminium as an example, explain what is meant by first ionisation energy. (ii) State the factors that influence ionisation energy. (c) Explain the trend in the first ionisation energy on going down Group 1 elements.
Essay Question
1. (a) Explain the term first ionisation energy using chlorine as an example. (b) Explain the factors that influence the ionisation energy of an atom. (c) Explain the variation of first ionisation energy for the first row d-block elements.
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ANSWER
CHAPTER 5 The Periodic Table
Objective Questions 1. C Group 1 and Group 2 metals have only one oxidation state. 2. C Fluorine: Simple covalent molecule (lowest melting point) Carbon: Giant covalent molecule (highest melting point) 3. A Atomic size decreases across Periods 2 and 3. Atomic size increases down a group. 4. A Cs is the most electropositive, compared to Li and Ba. F is the most electronegative, compared to I. Hence, the ionic compound, CsF has the highest ionic character. 5. D 1st 2nd 3rd 4th 5th 6th 7th 1020 2150 3400 4650 7080 27 300 32 100 1130 1250 1250 2430 20 220 4800 It is Group 15 element. Since the 1st I.E. is very high, it is expected to be a non-metal. A Group 15 non-metal will tend to form the X3 ion. 6. B The elements, phosphorus and sulphur have simple covalent structures. 7. C 8. D 9. B Electronegativity increases across periods but decreases down a group. Structured Questions 1. (a) (i) Q Reason: Q is a Group 2 element because Group 2 elements are metals, with low rst ionisation energy, good conductor in the solid state and relatively low melting point. (ii) P Reason: P is a metalloid (poor conductivity and fairly high melting point). P is Group 15 element. On going down Group 15, the metallic character changes from non-metals, to metalloid to metals. (iii) Y Reason: Y is a non-metal (high rst ionisation energy and non-conductor). Y is a Group 17 element such as chlorine, which has a very low melting point. (iv) X X is a metal (low rst ionisation energy, good conductor in the solid state). (b) 2. (a) X is a d-block element because it has a very high melting point. s-block element: Element Q p-block elements: Elements P and Y (i) 38 There are 36 electrons in X2+ ion. Thus there are 38 electrons in element X. (ii) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 5s2 (iii) X is a s-block element. (i) The rst ionisation energy is the energy required to remove one mole of electrons from one mole of atoms in the gaseous state. Al(g) Al+(g) + e; H = First ionisation energy of aluminium (ii) The nuclear charge, that is, the number of protons in the nucleus. The screening effect, that is, the effect of shielding of the outermost electrons from the attraction of the nucleus by the repelling effect of the electrons in the inner shells. On going down Group 1 elements, the rst ionisation energy decreases. This is because of the increase in atomic radius. The further the electron is from the nucleus, the weaker is the force of attraction of the nucleus on the electron and the more easily the electron can be removed. the increase in the shielding effect. This causes the electron to be held less strongly by the nucleus.
(b)
(c)
Essay Question 1. (a) The first ionisation energy is the minimum energy required to remove one mole of electrons from one mole of atoms in the gaseous state. Cl(g) Cl+(g) + e (b) Ionisation energy is influenced by the atomic size, the nuclear charge and the screening effect. The larger the atomic size, the lower the ionisation energy. The higher the nuclear charge, the higher the ionisation energy. The higher the screening effect, the lower the ionisation energy. (c) The first ionisation energy remains fairly constant. The slight increase in ionisation energy is due to the fact that the effect of increased nuclear charge is roughly cancelled by the increasing shielding effect of the inner 3d electrons.
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6
Objective Questions
Chemical Bonding
1. The diagram shows the effect of a charged rod on a liquid flowing out a burette.
polar liquid
charged rod (positive or negative)
jet of deflected liquid
Which of the following liquids will be deflected by the charged rod? A Br2 C SiCl4 B BCl3 D PCl3 2. The formula of sodium peroxide is Na2O2. Which of the dot-and-cross diagrams represents the structure of the peroxide ion? [Key: o = electron from first oxygen atom, x = electron from second oxygen atom, = electron from sodium atom] A C
3. Which of the following pairs contains both molecules that have linear shape? A CS2 and XeF2 B SCl2 and SO2 C CS2 and SCl2 D XeF2 and SO2 4. Which of the following molecules has six bonding electrons? A NF3 C C2H4 B CO2 D H2O 5. Chloromethane forms a carbonium ion R+ when it reacts with aluminium chloride as shown in the chemical equation below. CH3Cl + AlCl3 CH3+ + AlCl4 This reaction occurs because A AlCl3 is a simple covalent molecule. B the aluminium atom in AlCl3 does not have eight electrons in the valence shell. C the chlorine atom in AlCl3 does not have eight electrons in the valence shell. D the chlorine atom in CH3Cl has an empty p orbital.
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A 1 only is correct
6. Which of the following compounds contain(s) ionic bonds? 1 Sodium chloride, NaCl 2 Aluminium chloride, AlCl3 3 Silicon(IV) chloride, SiCl4 7. Iron forms a complex with the formula, [Fe(CN)6]Cl3. This complex contains 1 electrovalent bond 2 covalent bond 3 coordinate bond 8. Which of the following molecules contain(s) both sigma () and pi () bonds? 1 NH3 2 CO2 3 C2H4 9. Tetraethyllead has the formula (C2H5)4Pb. Which of the following statements is/are correct? 1 It is soluble in water. 2 It is a covalent compound. 3 It has a tetrahedral shape.
1. (a) Show the dot-and-cross structures for the following species: (i) CO (ii) IF3 (iii) H3O+ (b) Describe and explain the molecular shape of (i) IF3 and (ii) H3O+? (c) The carbonyl group, C = O, contains a -bond and a -bond. With the help of a diagram, explain the terms (i) -bond and (ii) -bond. 2. Consider the elements and compounds given below: potassium, silicon, helium, trichloromethane, sodium bromide Select from this list, an element or a compound that shows the following properties: (a) A monatomic gas (b) A giant molecule that consists of atoms covalently bonded (c) A polyatomic molecule with low boiling point (d) A solid that conducts electricity in molten state but not in solid state (e) A substance that contains delocalised electrons
Essay Question
1. (a) The structure of propanoic acid is shown below. OH a CH3 bCH2 cC = O Describe the hybridised orbitals used by the carbon atoms marked a, b and c to form covalent bonds. (b) Explain the effect of temperature on the electrical conductivity of (i) iron, (ii) silicon.
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ANSWER
CHAPTER 6 Chemical Bonding
Objective Questions 1. D Br2 (linear), BCl3 (trigonal planar) and SiCl4 (tetrahedral) have symmetrical shapes. PCl3 (pyramidal shape) has resultant dipole. 2. D In the peroxide ion, each oxygen atom carries a negative charge, O O. Hence each oxygen atom receives one electron from each sodium atom. x x 3. A x x x x x x x S C S x
x x
(ii)
x x x x x x x x x x x x x x x F x x x
x x
(iii) H xO H
x
H (b) (i)
F F
Linear shape The XeF2 molecule Xe : 8e (Group 18) 2F : 2e Total : 10e The geometry of the electron-pairs and the shape of the molecule is shown below:
F
T shaped Explanation: IF3 is T shape because the iodine atom is surrounded by three bond pairs of electrons and two lone pairs of electrons. (ii)
+ O H H H
pyramidal structure 4. A
x x x x x x
F xN x F x x x x x F
x x
5. B The central Al atom in AlCl3 is surrounded by six electrons. So, it can accept 2 electrons from Cl ion to complete the octet.
+ + +
(c)
Explanation: H3O+ has a pyramidal structure because the oxygen atom is surrounded by three bond pairs of electrons and one lone pair of electrons. (i) A -bond is a covalent bond formed due to the head-on overlapping of two atomic orbitals.
++
++
++
+ +
+ +
++
+ +
or
(ii) A -bond is a covalent bond formed by the sideways overlapping of atomic orbitals. 6. A AlCl3 and SiCl4 are covalent compounds. 7. D Electrovalent bond between [Fe(CN)6l3+ and Cl ions. Covalent bond between C and N in CN ion. Coordinate bond between Fe3+ and CN ion. 8. C - and -bonds are found in a double bond. O = C = O and CH2 = CH2 contain double bonds. 9. C (C2H5)4Pb is a covalent compound. The C H and C Pb bonds are covalent bonds. Covalent compounds are insoluble in water. Structured Questions 1. (a)
20
(i)
x x
x x
2. (a) (b) (c) (d) (e)
Helium Silicon Trichloromethane Sodium bromide Potassium
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Essay Question 1. (a)

a b
CH3 sp3 hybrid orbitals CH2 sp3 hybrid orbitals. Carbon atom in the excited state: 1 1 1 2s2 2s1 2px 2py 2pz The sp3 hybrid orbitals are formed when the one 2s orbital combines with three 2p orbitals. H c C = O sp2 hybrid orbitals Carbon atom in the excited state: 1 1 1 2s2 2s1 2px 2py 2pz .
The sp2 hybrid orbitals are formed when the one 2s orbital combines with two 2p orbitals. (b) (i) Iron is a metal. Electrical conductivity decreases with increase in temperature. Reason: Vibration of ions in the metal lattice impede the free movement of electrons in the conduction band. (ii) Silicon is a metalloid. Electrical conductivity increases with increase in temperature. Reason: More electrons in the valence band gain thermal energy and are able to move into the conduction band.
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7
Objective Questions
Intermolecular Forces of Attraction
1. The compound that has the highest boiling point is A CH3CH2CH2OH C CH3 O CH3 B (CH3)2CHOH D CH3CH2CH2Cl 2. Which of the following organic liquids dissolves most readily in water? C CH3(CH2)4COOH A CCl4 B CH3CH2CH2OH D C6H5OH 3. What is the intermolecular bonding that is present in dry ice (solid carbon dioxide)? A Ionic bond B Covalent bond C Van der Waals forces D Hydrogen bond 4. The structure of an amino acid, H2NCH2COOH is shown below. Which of the hydrogen atoms, labelled as I, II or III can form intermolecular hydrogen bonds. H H O H NCCOH (I) (III) H (II) A I only B II only A 1 only is correct B 1 and 2 only are correct C I and II only D I and III only C 2 and 3 only are correct D 1, 2 and 3 are correct
5. Which of the following pairs of liquids are miscible? 1 Water with methanol 2 Benzene (C6H6) with methylbenzene (C6H5CH3) 3 Benzene with water 6 Hydrogen bonding exists in 1 liquid ammonia 2 liquid hydrogen chloride
liquid methane
7. Which of the following can be explained in terms of hydrogen bonding? 1 The density of ice is less than water. 2 NH3 has a higher boiling point than PH3. 3 HI has a higher boiling point than HCl. 8. Which of the following organic compounds are polar molecules? 1 Chloromethane, CH3Cl 2 Trichloromethane, CHCl3 3 Tetrachloromethane, CCl4
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1. The boiling points of some organic compounds are shown below.
Compound Structural formula I CH3(CH2)3CH3 II CH3(CH2)4CH3 III CH3 CH3 C CH3 CH3 9.5 IV CH3 CH3 C CH3 OH 82.5
Boiling point (oC)
36.3
68.7
Explain why the boiling point of (a) compound II is higher than compound I. (b) compound I is higher than compound III. (c) compound IV is higher than compound II. 2. Water, ethanol, CH3CH2OH and 1-propanol, CH3CH2CH2OH are compounds containing the OH group and can form intermolecular hydrogen bonding. (a) Which of these compounds forms the strongest hydrogen bonds. (b) Explain your choice in (a).
Essay Question
1. (a) Which of the molecules, Br2 or ICl, is expected to have a higher boiling point? Explain your answer. (b) The standard enthalpy of vaporisation, Hvap for four compounds are shown below.
Compound Hvap (kJ mol )
1
H2Se 19.9
H2S 18.7
H2O 41.1
RbCl 154
Explain the trend of the standard enthalpy of vaporisation of these four compounds in terms of chemical bonding and intermolecular forces.
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ANSWER
CHAPTER 7 Intermolecular Forces of Attraction
Objective Questions 1. A CH3CH2CH2OH is a straight chain alcohol with hydrogen bonding. 2. B The OH group is hydrophilic and causes organic compounds to be soluble in water through hydrogen bonding. The hydrocarbon chain is hydrophobic which decreases the solubility of organic compounds in water. The organic compound becomes less soluble as the length of the carbon chain increases. 3. C The bond within CO2 is covalent bond. The bond between CO2 molecules is van der Waals forces. 4. D A hydrogen atom attached to a carbon atom cannot form hydrogen bond. 5. B Water and methanol molecules have the same type of intermolecular forces, hydrogen bonding. Hence they are miscible. Benzene and methylbenzene molecules have the same type of intermolecular forces, van der Waals forces. Hence they are miscible. Benzene and water molecules have different types of intermolecular forces. Hence they are immiscible. 6. A 7. B Hydrogen bonds do not exist in HI and HCl. 8. B CCl4 has symmetrical shape. It has polar bonds but the molecule is non-polar. Structured Questions 1. (a) Compounds I and II are simple covalent molecules. The van der Waals forces in compound II is stronger because it has a larger molecular size. (b) Compounds I and III are isomers. Compound III is a branched isomer. Hence it has a smaller molecular size and therefore weaker van der Waals forces. (c) Compound IV contains the OH group. Hence, intermolecular hydrogen bonding is present in compound IV. 2. (a) Water molecules (b) Water has the highest boiling point compared to ethanol and 1-propanol. Hence it has the strongest hydrogen bond. Water molecules do not contain the alkyl groups, whereas ethanol and 1-propanol contains the alkyl groups. The van der Waals forces of attraction between ethanol molecules or between 1-propanol molecules weakens the hydrogen bonds in these molecules. Essay Question 1. (a) Mr of Br2 = 160 Mr of ICl = 162.5 They have similar relative molecular mass. But Br2 is non-polar and ICl is polar and has a dipole moment. Hence, ICl should have a higher boiling point. (b) RbCl has the highest Hvap because it is an ionic compound. Ionic bond is a very strong bond. H2Se, H2S and H2O are simple covalent molecules. The intermolecular forces are much weaker than ionic bond. Hence, the values of Hvap are much smaller. The molecular size of H2Se > H2S. Hence the van der Waals forces in H2Se are stronger. Hence, H2Se has a higher value of Hvap. Hydrogen bonds exist between water molecules. Hydrogen bonds are stronger than van der Waals forces. Hence, H2O has a much higher value of Hvap than H2Se or H2S.
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8
Objective Questions
Kinetics
1. The rate equation for a reaction is given as follows Rate = k [A]2 [B] Which of the following is the unit of the rate constant, k? A s1 C mol1 dm3 s1 B mol dm3 s1 D mol2 dm6 s1 2. The table below shows the result of an experiment for the reaction at 25 C. X(aq) + Y(aq) Z(aq)
No. of experiment 1 2 3 [X] x 2x 2x [Y] y y 3y Initial rate of reaction r 8r 24r
What is the rate equation for the reaction? A Rate = k [X] [Y] C Rate = k [X]3 [Y] 2 B Rate = k [X] [Y] D Rate = k [X]3 [Y]2 3. The mechanism of the reaction between diazonium ions with iodide ions is given below. slow C6H5N2+ C6H5+ + N2 fast C6H5+ + I C6H5 I Which of the following is true of the reaction between diazonium ions with iodide ions? A The unit of the rate constant is time1. B The reaction is first order with respect to diazonium ions and iodide ions. C The rate is doubled when the concentration of iodide ions is doubled. D The half-life of the reaction is inversely proportional to the initial concentration of diazonium ions. 4. Iodine reacts with propanone in the presence of dilute acids as represented by the following equation: I2 + CH3COCH3 HI + ICH2COCH3 The graph of the concentration of iodine in the reaction mixture measured at regular time intervals is given as follows
[I2]
time
Based on the graph, which of the following statements is true of the reaction above? A The half-life of the reaction is a constant. B The rate of reaction is inversely proportional to [I2]. C The rate-determining step in the reaction mechanism is independent of I2. D The reaction is first order with respect to I2.
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A 1 only is correct
5. Which of the following statements is true about the rate constant, k in the equation of a reaction? 1 k will increase when the temperature is increased. 2 k will increase when the activation energy is increased. 3 k will increase when the concentration of the reactants is increased. 6. Which of the following statement is true about a catalysed reaction? 1 A catalyst provides a different mechanism for the reaction. 2 A catalyst changes the order of the reaction in the rate equation. 3 A catalyst reaction speeds up the forward reaction more than the backward reaction.
1. The table below shows the results of an investigation of the rate of reaction between hydroxide ion, OH and phosphinate ion, PH2O2 at 80 C. The overall reaction is PH2O2(aq) + OH(aq) PHO32(aq) + H2(g)
No of experiment 1 2 3 4 Initial concentration [PH2O ] (mol dm3) 0.1 0.3 0.6 0.6
2
[OH] (mol dm3) 6.0 6.0 1.0 2.0
Initial rate for the production of hydrogen gas (dm3 min1) 14.4 43.2 2.4 9.6
(a) (b) (c) (d) (e) (f)
What is the order of reaction with respect to phosphinate ion? What is the order of reaction with respect to hydroxide ion? What is the overall order of reaction? Write down the rate equation for the reaction above. Calculate the value of the rate constant at 80 C. Predict the rate of production of hydrogen gas when the initial rate of phosphinate ions and hydroxide ions are 0.6 mol dm3 and 3.0 mol dm3 respectively.
2. Trichloromethane, CHCl3 reacts with sodium hydroxide solution as represented by the following equation: 2CHCl3 + 7OH CO + HCOO + 6Cl + 4H2O The reaction is first order with respect to each reactant. (a) Write the rate equation for the reaction between trichloromethane and sodium hydroxide. (b) Determine the rate of production of chloride ions at 28 C when the rate of loss of trichloromethane is 2.0 105 mol s1. (c) If the rate of reaction is r when the concentrations of both trichloromethane and sodium hydroxide are both 2.0 mol dm3, what is the rate of reaction in terms of r when half of the hydroxide ion is reacted? (d) Sketch a graph of the rate of reaction against the concentration of trichloromethane if sodium hydroxide is in excess such that the hydroxide ion concentration remains practically constant in the reaction mixture.
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Essay Question
1. (a) Explain what is meant by the rate-determining step of a reaction mechanism. (b) Nitrogen monoxide reacts with fluorine to produce the compound nitrosyl fluoride, NOF as represented the equation 2NO(g) + F2(g) 2NOF(g) It is found the reaction is first order with respect to both nitrogen monoxide and fluorine. Suggest a two-step mechanism for the reaction if the free radical fluorine, F is identified as an intermediate for the reaction. Justify your answer in terms of reaction kinetics. (c) Describe and explain how the initial rate of reaction in (b) is affected by (i) an increase in temperature, (ii) an increase of 100 % of partial pressure of each reactant.
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ANSWER
CHAPTER 8 Kinetics
Objective Questions unit of rate 1. D Unit of k = [unit of reactant]3 mol dm3 s1 = (mol dm3)3 = mol2 dm6 s1 Experiment 2 8r k (2x)n(y)m 2. C = = Experiment 1 r k (x)n (y)m 8 = 2n n = 3 Experiment 3 24r k (2x)n(3y)m = = Experiment 2 8r k (2x)n(y)m 3 = 3m m = 1 Rate = k [X]3 [Y]1 Since the rst step is the slowest step, it is the rate-determining step. Hence the rate is rst order with respect to diazonium ions only (B and C incorrect). The unit of the rate constant of a rst order reaction is time1 (A correct). The half-life of a rst order reaction is a constant (D incorrect). The graph of [I2] against time is a straight line indicating that the gradient (which is the rate of reaction) is constant. Hence the rate is independent of [I2]. The rate is zero order with respect to I2. (C correct; A, B and D incorrect). k will increase when the temperature is increased (1 correct) and when the activation energy is decreased (2 incorrect) according to the Arrhenius equation: k = A eEa/ RT k is the proportional constant in the rate equation and is independent of the concentration of the reactants (3 incorrect). A catalyst will provide an alternate mechanism which involves a lower activation energy (1 correct). The rate-determining step in the reaction mechanism is different, hence the order of reaction will be different (2 correct). A catalyst speeds up the forward reaction and the backward reaction by the same amount (3 incorrect). 3 = 3n n=1 The reaction is rst order with respect to phosphinate ion. (b) Rate = k[PH2O2]n[OH]m By substituting the values of rate, [PH2O2] and [OH] from the results of experiments 3 and 4: 9.6 k[0.6]n[2.0]m = 2.4 k[0.6]n[1.0]m 4 = 2m m= 2 The reaction is second order with respect to hydroxide ion. (c) The overall order of reaction is third order. (d) The rate equation is rate = k[PH2O2] [OH]2 (e) By substituting the values of rate, [PH2O2] and [OH] from the results of experiment 1 in the rate equation 14.4 = k[0.1]1 [6.0]2 14.4 dm3 min1 k = (0.1 36) mol3 dm9 = 4 mol3 dm12 min1 (f) By substituting the values of k, [PH2O2] and [OH] into the rate equation: Rate = 4 0.6 (3.0)2 = 21.6 dm3 min1 2. (a) The rate equation is: Rate = k[CHCl3] [OH] 1 d[CHCl3] 1 d[Cl] (b) Rate = = 2 dt 6 dt d[Cl] = 3 2.0 105 mol s1 dt = 6.0 105 mol s1 (c) When half of the hydroxide ion is reacted, [OH]remaining = 2.0 = 1.0 mol dm3 According to the equation, 7 mol of OH ions react with 2 mol of CHCl3. When 1.0 mol of OH ions has reacted, 2 number of moles of CHCl3 reacted = 1.0 7 2 12 [CHCl3]remaining = 2.0 1.0 = 7 7 By substituting the values of r, [CHCl3] and [OH] into the rate equation: Rate = k [CHCl3] [OH] and assuming the rate of reaction when half of the hydroxide ion is reacted is r r k (12/7) (1.0) = r k (2.0) (2.0) 3r r = 7 (d) Graph of the rate of reaction against the concentration of trichloromethane.
3. A
4. C
5. A
6. B
Structured Questions 1. (a) Rate = k[PH2O2]n[OH]m By substituting the values of rate, [PH2O2] and [OH] from the results of experiments 1 and 2: 43.2 k[0.3]n[6.0]m = 14.4 k[0.1]n[6.0]m
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rate of reaction (mol dm-3 time-1)
The rate of reaction increases when the rate constant, k is increased. According to the Boltzman distribution curve, the fraction of molecules having a kinetic energy equal or greater than the activation energy, Ea is very much larger at the higher temperature.
[CHCI3] (mol dm-3)
Shaded area = fraction of molecules with E > Ea At higher temperature, T2, fraction of molecules with E > Ea increases signicantly
Essay Question 1. (a) The rate-determining step is the slowest step of a reaction mechanism. The order of reaction with respect to the reactant in the rate equation is determined by the number of moles of reactants in the slowest step. (b) The two-step mechanism: NO + F2 NOF + F F + NO NOF The slowest step of the mechanism involves one mole of NO and one mole of F2. This is consistent with the rate equation in which the order of reaction is rst order with respect to NO and also rst order with respect to F2: Rate = k [NO] [F2]. (c) (i) When temperature increases, the rate constant, k increases as represented by Arrhenius equation: k = A eEa/RT
fast
Graph of fraction of molecules with a particular energy at two different temperatures
slow
(ii) Partial pressure is directly proportional to the number of moles of the reactant. An increase in 100% of partial pressure of each reactant will result in a doubling of the concentration of each reactant. According to the rate equation: Rate = k [NO] [F2]; when [NO] increases by 2 times and [F2] also increases 2 times, the rate will increase by 4 times.
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9
Objective Questions
Chemical Equilibrium
1. The graph below shows the yield of gas X at different temperatures and pressures.
Based on the graph only, what conclusion can be drawn? A There is a decrease in volume when the forward reaction proceeds. B The forward reaction is endothermic. C The reaction rate increases in the presence of a catalyst. D Pressure has no effect on the position of equilibrium. 2. A mixture of iron and steam is allowed to reach equilibrium at 800 K: 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)
The equilibrium pressures for hydrogen and steam are 3.5 kPa and 2.4 kPa respectively. The equilibrium constant, Kp, for the reaction is A 1.46 B 4.5 C 6.0 D 9.0 3. Hydrogen and carbon dioxide react as represented by the equation: H2(g) + CO2(g) CO(g) + H2O(g)
When 4 mol of hydrogen and 0.9 mol of carbon dioxide were used for this reaction, 0.1 mol of CO2 was found in the equilibrium mixture. Calculate Kc for the experiment. A 0.4 B 0.8 C 2.0 D 2.4 4. Consider the following equilibrium: 2NO2(g) N2O4(g)
At 350 K and 7000 kPa pressure, an equilibrium mixture contains 48 % by volume of N2O4. What is the value of Kp for the equilibrium? A 2.54 103 (kPa)1 B 2.54 104 (kPa)1 C 3.92 102 kPa D 3.92 103 kPa
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5. 2.0 mol of sulphur dioxide was allowed to react with 1.0 mol of oxygen at 10 atm pressure and at a fixed temperature. When equilibrium was achieved, 1.0 mol of sulphur dioxide was converted to sulphur trioxide. 2SO2(g) + O2(g) 2SO3(g) Calculate Kp for the reaction. A 0.5 atm1 B 1.0 atm1 C 3.0 atm1 D 4.0 atm1 A 1 only is correct 6. For the reaction: N2(g) + O2(g) 2NO(g) the equilibrium constant, Kp, is 1.3 1015 at 298 K and 5.5 102 at 2000 K. These data show that 1 the forward reaction is endothermic. 2 the value of Kp depends on the amount (in mol) of nitrogen used. 3 the value of Kp increases as the pressure exerted on the system increases. 7. For the reversible reaction, 2SO2(g) + O2(g) 2SO3(g) ; H = 198 kJ mol1 B 1 and 2 only are correct C 2 and 3 only are correct D 1, 2 and 3 are correct
the proportion of sulphur trioxide in the equilibrium mixture can be increased by 1 increasing the total pressure on the system. 2 increasing the temperature of the system. 3 using a catalyst.
1. In the Contact process for the production of sulphuric acid(VI), sulphur dioxide and oxygen are converted into sulphur trioxide. 2SO2(g) + O2(g) 2SO3(g) ; H = 198 kJ
(a) How would you expect the equilibrium position to vary with (i) increasing temperature? (ii) increasing pressure? (iii) the presence of a catalyst? (b) (i) What are the industrial conditions for this process? (ii) Explain why these conditions are used. 2. The reaction as shown by the equation below represents the first step in the manufacture of nitric(V) acid from ammonia. 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) ; H = 909 kJ mol1
(a) How would the yield of NO(g) be affected if (i) the pressure is increased at constant temperature? (ii) the temperature is increased at constant pressure? (b) In the industrial process, a temperature of 900 C is used. Based on your answer in (a)(ii), suggest a reason for using this temperature. (c) In the industrial process, the mixture of NH3(g) and O2(g) is allowed to pass through platinum gauze. (i) Suggest a reason why platinum is used in this reaction. (ii) Give one advantage of using platinum in the form of platinum gauze.
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Essay Question
1. (a) What is the effect of (i) temperature, (ii) pressure and (iii) catalyst on the equilibrium constant for the reaction: N2O4(g) 2NO2(g) ; H = +58 kJ mol1 CH3COOC2H5(aq) + H2O(l)
(b) At 25 C, the equilibrium constant for the reaction, CH3COOH(aq) + C2H5OH(aq)
is 4.0. Calculate the molar composition of the mixture at equilibrium at 25 C starting from (i) 1 mol of CH3COOH and 2 mol of C2H5OH, (ii) 1 mol of CH3COOH, 1 mol of H2O and 2 mol of C2H5OH. Comment on the results in terms of position of equilibrium.
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ANSWER
CHAPTER 9 Chemical Equilibrium
Objective Questions 1. A The graph shows that the yield is increased by low temperatures and high pressures. Hence, the forward reaction is exothermic and accompanied by a decrease in the number of molecules (that is, a decrease in volume). pH 4 3.5 2 2. B Kp = = ( )4 = 4.5 pH O 2.4 (i) Temperature: 450 C Pressure: 1 or 2 atm Catalyst: V2O5 (ii) Increase in pressure will increase the yield of SO3 but the effect is small for this reaction. Hence, a pressure of 1 or 2 atm is used to cut down the cost of maintaining high pressures. 2. (a) (i) The number of moles of products is more than the number of moles of the reactants. Thus an increase in pressure will cause the equilibrium position to shift to the left. That is, the yield of NO(g) will decrease. (ii) The reaction is an exothermic reaction. Thus, an increase in temperature will cause the equilibrium position to shift to the left, that is, the yield of NO(g) will decrease. (b) If the temperature is lowered, the yield of NO(g) will increase. However, at low temperatures, the rate of reaction is very low. A temperature of 900 C is used so that a reasonable yield of NO(g) is obtained at a relatively high rate of reaction. (c) (i) Platinum is used as a catalyst in this reaction to speed up the reaction. (ii) Platinum gauze is used because it has a larger surface area and this increases the rate of catalytic reaction. Essay Question 1. (a) (i) In a reversible reaction, a change of temperature will affect the rates of both forward and reverse reactions, but not necessarily to the same extent. Thus, equilibrium constant varies with temperature. The given reaction is an endothermic reaction. For endothermic reaction, the equilibrium constant increases as temperature increases. (ii) A change in the total pressure on the system does not change the equilibrium constant, even though the composition of the equilibrium mixture is changed. (iii) A catalyst increases the rates of both forward and reverse reactions to the same extent. Hence, the catalyst has no effect on the equilibrium constant. (b) (i) CH3COOH(aq) + C2H5OH(aq) Initial 1 2 (mol) Eqm(mol) 1 x 2x CH3COOC2H5(aq) + H2O(l) Initial(mol) 0 0 Eqm(mol) x x
(b)
3. C Amount of CO2 reacted = 0.9 0.1 = 0.8 mol Amount of CO/H2O formed = 0.8 mol Amount of H2 at equilibrium = 4 0.8 = 3.2 mol Initial (mol) Eqm (mol) H2(g) + CO2(g) 4 0.9 3.2 0.1 CO(g) + H2O(g) 0 0 0.8 0.8
0.8 0.8 Kc = = 2.0 3.2 0.1 4. B 2NO2(g) N2O4(g) 48 pN O = 7000 = 3360 kPa 2 4 100 100 48 pNO = 7000 = 3640 kPa 2 100 pN O 3360 2 4 Kp = = (pNO )2 36402 2 = 2.54 104 (kPa)1 5. A 2SO2(g) + O2(g) 2SO3(g) Initally(mol) 2.0 1.0 0 Equilibrium 2.0 1.0 1.0 0.5 1.0 (mol) Total number of moles at equilibrium = (2.0 1.0) + (1.0 0.5) + 1.0 = 2.5 1.0 pSO = 10 = 4.0 atm 3 2.5 1.0 pSO = 10 = 4.0 atm 2 2.5 0.5 pO = 10 = 2.0 atm 2 2.5 (pSO )2 2 4.0 3 Kp = = = 0.5 atm1 2 2 (pSO ) pO 4.0 2.0 2 2 6. A Kp increases as the temperature increases. So, the forward reaction is endothermic. 7. A Structured Questions 1. (a) (i) Equilibrium position shifts to the left (ii) Equilibrium position shifts to the right (iii) No effect
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x2 4= (1 x)(2 x) x = 0.845 Amount of CH3COOC2H5 = 0.845 mol Amount of water = 0.845 mol Amount of CH3COOH = 1 0.845 = 0.155 mol Amount of alcohol = 2 0.845 = 1.16 mol (ii) CH3COOH(aq) + C2H5OH(aq) Initial 1 2 (mol) Eqm(mol) 1 x 2x Initial(mol) Eqm(mol) CH3COOC2H5(aq) + H2O(l) 0 1 x 1+x
[CH3COOC2H5] [H2O] Kc = [CH3COOH] [C2H5OH] x(1 + x) 4 = (1 x)(2 x) x = 0.7427 Amount of CH3COOC2H5 = 0.743 mol Amount of water = 1 + 0.743 = 1.743 mol Amount of CH3COOH = 1 0.743 = 0.257 mol Amount of C2H5OH = 2 0.743 = 1.26 mol Comment: In the presence of H2O, equilibrium shifts to the left. Hence amount of CH3COOC2H5 decreases while the amounts of CH3COOH and C2H5OH increase.
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10
Objective Questions
1. In the following reaction, H2O(l) + NH3(g)
Acid-base Equilibria and Buffer Solutions
NH4+(aq) + OH(aq)
water acts as a A Bronsted-Lowry acid B Bronsted-Lowry base C conjugate acid D conjugate base 2. The acid dissociation constant of propanoic acid, CH3CH2COOH is 1.3 105 mol dm3. What is the concentration of H3O+ ions in 0.010 mol dm3 propanoic acid? 1.3 105 2 A ( ) mol dm3 102 1.3 105 B ( ) mol dm3 102 1.3 105 C ( ) mol dm3 102 3 105 2 D ( ) mol dm3 102 3. When a monoprotic acid (in the conical flask) is titrated with a base, the pH changes abruptly from 3 to 7 at the equivalence point. This shows that it is a A strong acid-strong base titration B strong acid-weak base titration C weak acid-strong base titration D weak acid-weak base titration 4. 25.0 cm3 of 1.0 mol dm3 of ammonia solution is added to 25.0 cm3 of 1.0 mol dm3 of ammonium chloride solution. What is the pH of the mixture? (Kb of ammonia is 1.75 105 mol dm3) A 3.5 B 6.4 C 9.2 D 12.0 A 1 only is correct 5. B 1 and 2 only are correct C 2 and 3 only are correct D 1, 2 and 3 are correct
Name of indicator Congo red Methyl yellow Diphenol purple
pH range of indicator 3.0 5.0 2.9 4.0 7.0 9.0
Based on the information given above, we can infer that 1 Congo red is suitable for the titration of aqueous ammonia with ethanoic acid. 2 methyl yellow is suitable for the titration of aqueous ammonia with hydrochloric acid. 3 diphenol purple is suitable for the titration of aqueous sodium hydroxide with ethanoic acid.
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6. In the following reaction, 8NH3 + 3Cl2 N2 + 6NH4Cl ammonia acts as a 1 Lewis acid 2 Lewis base 3 reducing agent 7. The graph below shows the changes in pH for the titration between a monoprotic acid and aqueous sodium hydroxide.
Which of the following statements is/are correct? 1 Addition of 10.0 cm3 of sodium hydroxide produces an acidic buffer solution in the conical flask 2 Addition of 20.0 cm3 of sodium hydroxide produces a basic buffer solution in the conical flask 3 Addition of 40.0 cm3 of sodium hydroxide produces an acidic buffer solution in the conical flask 8. Which of the following pairs of substance can act as a buffer solution? 1 CH3COOH and CH3COO 2 NH4+ and NH3 3 HCO3 and CO32 9. When a little acid is added separately to the following mixtures, which mixture will show a marked change in pH? 1 A mixture of NaHSO4 and Na2SO4 2 A mixture of NaH2PO4 and Na2HPO4 3 A mixture of CH3CH2COOH and CH3CH2COONa
1. (a) The values of Kw for water at 10 C, 30 C and 40 C are shown below.
Temperature (C) Kw 10 (mol dm )
14 2 6
10 0.29
30 1.5
40 2.9
(i) From the data given, what inference can you make regarding the dissociation of water? (ii) Calculate the pH of water at 40 C. (iii) Calculate Kc at 30 C for the following equilibrium. H2O H+ + OH (Assume the density of water at 30 C = 1 g cm3)
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(b) The formula of an acid-base indicator can be represented by HIn. HIn(aq) [In] (i) Show that pH = pKIn + lg [HIn] (ii) An acid-base indicator has pKIn = 4.0. The colour of HIn(aq) is yellow and the colour of In(aq) is blue. Calculate the pH of a solution if the colour of the indicator in the solution is green. 2. The graph below shows the changes in pH when 20.0 cm3 of saturated sulphur dioxide solution are added to 1.0 mol dm3 sodium hydroxide solution in a titration. H+(aq) + In(aq)
(a) Write the chemical equation for the reaction that occurs at (i) the first equivalence point and (ii) the second equivalence point of the titration. (b) Suggest a suitable indicator that can be used to show the first equivalence point. (c) Write the chemical equation for the complete reaction between sulphur dioxide and sodium hydroxide. (d) Calculate the concentration in mol dm3 for sulphur dioxide in the original solution.
Essay Question
1. (a) Define an acid based on (i) Arrhenius theory (ii) Bronsted-Lowry theory (iii) Lewis theory. (b) Calculate the pH of a solution formed by mixing 49 cm3 of 0.1 mol dm3 aqueous sodium hydroxide with 51 cm3 of 0.1 mol dm3 hydrochloric acid. (c) Ammonia soluion is 4.2% dissociated at 25 C in 0.01 mol dm3 solution. Calculate pKb for ammonia at this temperature.
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ANSWER
CHAPTER 10 Acid-base Equilibria and Buffer Solutions
Objective Questions 1. A H2O donates H+ to NH3(g) 2. B For a weak acid, [H+] = Ka c 3. B At the equivalence point, an acidic solution is obtained. Hence it is a strong acid-weak base titration. [salt] 4. C pOH = lg Kb + lg [base] 1.0 25.0 = lg 1.75 105 + lg 1.0 25.0 = 4.76 pH = 14 4.76 = 9.2 5. C The pH range for Congo red and methyl yellow shows that they are indicators suitable for strong acid-weak base titration. For diphenol purple, the pH range shows that it is suitable for weak acidstrong base titration. 6. C The formation of NH4+ in NH4Cl shows that NH3 acts as a Lewis base (an electron-pair donor). NH3 reduces Cl2 to Cl. Thus it is a reducing agent. 7. A The pH change shows that it is a strong baseweak acid titration. Before the end point, the solution in the conical ask contains excess acid and salt of the weak acid. Thus it is an acidic buffer solution. After the end point, the solution contains excess alkali and salt of the weak acid. Hence, it is not a buffer solution. 8. D 9. A A mixture of NaHSO4 and Na2SO4 is not a buffer solution. Structured Question 1. (a) H+ + OH (i) H2O + Kw = [H ][OH] When the temperature is increased, the value of Kw increases. This shows that more H+ and OH ions are produced. That is, equilibrium position shifts to the right. Thus, the dissociation of water is an endothermic process. (ii) At 40 C, Kw = 2.9 1014 mol2 dm6 [H+] = (2.9 1014) = 1.7 107 mol dm3 pH = lg [H+] = lg (1.7 107) = 6.8 [H+][OH] Kw (iii) Kc = = [H2O] [H2O]
38
(b)
1000 = 55.6 mol dm3 [H2O] = 18 1.5 1014 Kc = 55.6 = 2.7 1016 mol dm3 (i) HIn(aq) H+(aq) + In(aq) [H+(aq)][In(aq)] KHIn = [HIn] By taking negative logarithm (lg) and rearranging, we have [In] lg [H+] lg = lg KHIn [HIn] [In] pH = pKHIn + lg [HIn] (ii) A mixture of yellow and blue gives green. Thus, green shows that [HIn] = [In] and pH = 4.0 + lg 1 = 4.0. (i) SO2(aq) + NaOH(aq) NaHSO3(aq) (ii) NaHSO3(aq) + NaOH(aq) Na2SO3(aq) + H2O(l) Methyl orange SO2(aq) + 2NaOH(aq) Na2SO3(aq) + H2O(l) (M1V1)SO 1 2 = (M2V2)NaOH 2 Concentration of aqueous SO2 1.0 25.2 = = 0.63 mol dm3 20
2. (a)
(b) (c)
(d)
Essay Question 1. (a) (i) An acid is a substance that dissociates in water to produce H+ ions. (ii) An acid is a substance that can donate a proton to a base. (iii) An acid is a substance that accepts a pair of electrons from a base. (b) 49 cm3 of 0.1 mol dm3 would neutralise 49 cm3 of 0.1 mol dm3 HCl. 2 cm3 of 0.1 mol dm3 HCl remained in (49 + 51) = 100 cm3 solution. Number of moles of H+ in 100 cm3 solution 0.1 2 = = 2 104 1000 100 cm3 0.1 dm3 (2 104) [H+] = = 2 103 mol dm3 0.1 pH = lg (2 103) = 2.7 2c (c) Kb = 1 0.0422 0.01 = 1 0.042 = 1.84 105 mol dm3 pKb = lg (1.84 105) = 4.74
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11
Objective Questions
Heterogeneous Ionic Equilibrium
1. A metal forms a salt with formula M2X. If the solubility of the salt is s mol dm3, its solubility product is A 2s2 mol2 dm6 C 4s3 mol3 dm9 2 2 6 B 4s mol dm D 2s4 mol4 dm12 2 At 15 C, the solubility of lead(II) iodide, PbI2 is 0.6 g dm3. What is the solubility product of lead(II) iodide at this temperature? (Mr of PbI2 = 461) 0.6 3 A ( ) mol3 dm9 461 0.6 3 B 2 ( ) mol3 dm9 461 0.6 3 C 4 ( ) mol3 dm9 461 461 3 D 4 ( ) mol3 dm9 0.6 3. A solution containing 7 107 mol dm3 Ag+ ions is required for a reaction. Which of the following saturated solution can be used for this purpose?
Saturated solution of the silver salt Ksp of the silver salt 2.0 1010 mol2 dm6 5.0 1013 mol2 dm6 2.0 105 mol3 dm9 1.3 1012 mol3 dm9
A B C D
AgCl AgBr Ag2SO4 Ag2CrO4
4. 150 cm3 of aqueous silver nitrate is added to 150 cm3 of 0.8 mol dm3 aqueous sodium chloride. What is the minimum concentration of aqueous silver nitrate needed to cause the precipitation of silver chloride? [Ksp of AgCl = 2.0 1010 mol2 dm6] A 1.0 108 mol dm3 B 2.0 108 mol dm3 C 1.0 109 mol dm3 D 2.0 109 mol dm3 5. 50 cm3 of a saturated solution of Ca(OH)2 required 10 cm3 of 0.1 mol dm3 HCl for complete neutralisation. The solubility product of Ca(OH)2 is 1 1 1 2 A ( ) mol3 dm9 2 50 50 1 1 1 2 B ( ) mol3 dm9 2 100 100 1 2 2 C ( ) mol3 dm9 50 50 1 2 2 D ( ) mol3 dm9 50 100
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A 1 only is correct
6. Which of the following observations can be explained in terms of common ion effect? 1 BaSO4(s) is less soluble in dilute sulphuric acid than in water. 2 When solid NaCl is added to a saturated solution of silver chloride, AgCl will precipitate out. 3 The concentration of OH ions is increased when solid NH4Cl is added to ammonia solution. 7. Silver chloride is sparingly soluble in water. When aqueous ammonia is added to silver chloride in water, it dissolves to form a clear solution because 1 soluble silver hydroxide is formed. 2 the complex ion, [Ag(NH3)2]+ is formed. 3 the ionic product of silver chloride is less than its solubility product.
1. (a) Write an equation to show the equilibrium that exists in a saturated solution of barium fluoride, BaF2. (b) Write the solubility product expression for barium fluoride and state its units. (c) A solution is 0.10 mol dm3 with respect to both Ba2+ and Ca2+ ions. Sodium fluoride is slowly added to precipitate BaF2. (i) Calculate the concentration of F ions at which BaF2 begins to precipitate. (ii) Hence, calculate the concentration of Ca2+ ion that remains unprecipitated at this point. [Ksp for BaF2 = 1.7 106 mol3 dm9; Ksp for CaF2 = 1.7 1010 mol3 dm9] 2. (a) The solubility products at 298 K for AgCl, Fe(OH)2 and Mn(OH)2 are shown below. Ksp for AgCl = 1.0 1010 mol2 dm6 Ksp for Fe(OH)2 = 8.0 1016 mol3 dm9 Ksp for Mn(OH)2 = 1.9 1013 mol3 dm9 Which of the following pairs of solution would produce a precipitate when the solutions are mixed? [Kb for ammonia = 1.8 105 mol dm3] (i) 25.0 cm3 of 1.0 103 mol dm3 AgNO3(aq) and 50.0 cm3 of 1.0 105 mol dm3 KCl(aq) (ii) 25.0 cm3 of 3.0 103 mol dm3 FeSO4(aq) and 75.0 cm3 of 1.0 104 mol dm3 NaOH(aq) (iii) 50.0 cm3 of 0.05 mol dm3 NH3(aq) and 50.0 cm3 of 0.025 mol dm3 MnSO4(aq) (b) A saturated solution Z contains calcium hydroxide and calcium sulphate. (i) If the pH of solution Z is 12.5, calculate the concentration of Ca2+ in solution Z. [Ksp for Ca(OH)2 is 5.5 106 mol3 dm9] (ii) Calculate the concentration of SO42 ions in solution Z. [Ksp for CaSO4 is 2.4 105 mol2 dm-6]
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Essay Question
1. (a) The values of Ksp for iron(II) hydroxide and iron(III) hydroxide are shown below.
Compound Fe(OH)2 Fe(OH)3 Ksp at 298 K 7.9 1016 mol3 dm9 2.0 1039 mol4 dm12
Iron(III) compounds react with potassium iodide as represented by the equation 2Fe3+(aq) + 2I(aq) 2Fe2+(aq) + I2(s)
When aqueous iodine is added to iron(II) hydroxide solid that contains a few drops of alkali solution, the iodine solution is decolourised and iron(II) hydroxide is converted to iron(III) hydroxide. Explain this observation. (b) The concentration of Cl(aq) ion in aqueous solution can be determined by titration with silver nitrate. The indicator used is potassium chromate(VI). At the end point, a red precipitate of silver chromate(VI), Ag2CrO4 is produced. Ksp of AgCl = 1.0 1010 mol2 dm6 ; Ksp of Ag2CrO4 = 2.4 1012 mol3 dm9 (i) Calculate the minimum concentration of Ag+ required to cause precipitation of AgCl. (ii) Calculate the minimum concentration of Ag+ required to cause precipitation of Ag2CrO4. (iii) Based on your answers in (b)(i) and (ii), describe what happens when silver nitrate solution is run into a solution of chloride ions, using potassium chromate(VI) as indicator.
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ANSWER
CHAPTER 11 Heterogeneous Ionic Equilibrium
Objective Questions 2M + X 1. C M2X [M] = 2s, [X] = s Ksp = [M]2[X] = (2s)2(s) mol3 dm9 2. C Ksp for PbI2 = [Pb2+][I]2 0.6 0.6 2 = (2 ) mol3 dm9 461 461 3. B [Ag+][Br-] = 5 1013 mol2 dm6 [Ag+] = 5 1013 = 7.1 107 mol dm3 Ag2CrO4 2Ag+ + CrO42 + Let [Ag ] = 2x Ksp = [Ag+]2[CrO42] 1.3 1012 = (2x)2(x) x = 6.9 105 2x = 1.38 104 [Ag+] = 1.38 104 mol dm3 4. C [Cl] after mixing = 0.8 = 0.4 mol dm3 (as volume is doubled) For precipitation to occur, ionic product of AgCl must exceed the Ksp of AgCl. [Ag+] 0.4 = 2.0 1010 [Ag+] = 5 1010 mol dm3 M1V1 before mixing = M2V2 after mixing M1 150 = 5 1010 (150 + 150) M1 = 5 1010 2 = 1.0 109 mol dm3 5. A OH + HCl H2O + Cl M1V1 = M2V2 0.1 10 Concentration of OH = 50 1 = mol dm3 50 Ca(OH)2 Ca2+ + 2OH 1 1 Concentration of Ca2+ = mol dm3 2 50 Ksp = [Ca2+][OH]2 1 1 1 )2 mol3 dm9 = ( 2 50 50 6. B BaSO4(s) Ba2+(aq) + SO42(aq) H2SO4(aq) 2H+(aq) + SO42(aq) Common ion, SO42 causes BaSO4 to be less soluble. (1 correct) AgCl(s) Ag+(aq) + Cl(aq) NH4Cl(aq) NH4+(aq) + Cl(aq) Common ion, Cl shifts the AgCl equilibrium to the left, hence AgCl precipitates out. (2 correct) NH3(g) + H2O(l) NH4+(aq) + OH(aq) NH4Cl(s) + water NH4+(aq) + Cl(aq) The concentration of OH decreased due to common ion effect. (3 incorrect) 7. C Silver hydroxide is insoluble. (1 incorrect) AgCl(s) Ag+(aq) + Cl(aq) When aqueous NH3 is added, it reacts with silver to form [Ag(NH3)2]+(aq). (2 correct)
42
Aqueous NH3 solution added causes [Ag+] and [Cl] to decrease hence ionic product [Ag+] [Cl] < Ksp. (3 correct) Structured Questions 1. (a) BaF2(s) Ba2+(aq) + 2F(aq) 2+ (b) Ksp = [Ba ][F]2 mol3 dm9 (c) (i) BaF2 begins to precipitate when ionic product = Ksp (saturated solution). [Ba2+][F]2 = 1.7 106 0.1 [F]2 = 1.7 106 1.7 106 [F] = 0.1 = 4.1 103 mol dm3 2+ (ii) [Ca ][4.1 103]2 = 1.7 1010 10 1.7 10 [Ca2+] = 3 2 (4.1 10 ) = 1.0 105 mol dm3 25 2. (a) (i) [Ag+] = (1 103) 75 = 3.33 104 mol dm3 50 [Cl] = (1 105) 75 = 6.67 106 mol dm3 Ionic product = (3.33 104) (6.67 106) = 2.22 109 mol2 dm6 Ionic product > Ksp Precipitation of AgCl occurs. 25 (ii) [Fe2+] = (3.0 103) 100 = 7.5 104 mol dm3 75 [OH] = (1 104) 100 = 7.5 105 mol dm3 Ionic product = (7.5 104) (7.5 105)2 = 4.2 1012 mol3 dm9 Ionic product > Ksp Precipitation of Fe(OH)2 occurs. 50 (iii) [Mn2+] = 0.025 100 = 0.0125 mol dm3 50 [NH3] = 0.050 100 = 0.025 mol dm3 [OH ] = Kb c = (1.8 105) 0.025 = 6.7 104 mol dm3 Ionic product = 0.0125 (6.7 104)2 = 5.6 109 mol3 dm9 Ionic product > Ksp Precipitation of Mn(OH)2 occurs. (b) (i) pH = 14 + lg[OH] lg[OH] = 12.5 14 = 1.5
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[OH] = 0.032 mol dm-3 Ksp for Ca(OH)2 = [Ca2+][OH]2 5.5 106 = [Ca2+] (0.032)2 [Ca2+] = 0.0054 mol dm3 (ii) Ksp = [Ca2+][SO42] 2.4 105 [SO42] = = 0.0044 mol dm3 0.0054 Essay Question 1. (a) In the presence of iodine, equilibrium shifts to the left (le Chateliers principle) and Fe3+ ions are produced. Fe3+ ions react with OH ions from the alkali to form Fe(OH)3. The Ksp for Fe(OH)3 is very much lower than the Ksp for Fe(OH)2. Thus, Fe(OH)3 can be precipitated more readily than Fe(OH)2. (b) (i) Ksp for AgCl = 1.0 1010 mol2 dm6 [Ag+] = 1.0 1010 = 1.0 105 mol dm3 If [Ag+] is higher than 1.0 105 mol dm3, precipitation of AgCl will occur.
(ii) Ksp for Ag2CrO4 = 2.4 1012 mol3 dm9 [Ag+]2[CrO42] = 2.4 1012 mol3 dm9 Let concentration of Ag+ needed to precipitate Ag2CrO4 = x mol dm3 Ag2CrO4(aq) 2Ag+(aq) + CrO42(aq) [CrO42] = x mol dm3 x2 (x) = 2.4 1012 x3 = 4.8 1012; x = 1.69 104 mol dm3 If [Ag+] is higher than 1.69 104 mol dm3, precipitation of Ag2CrO4 will occur. (iii) The answers in (b)(i) and (ii) show that a higher concentration of Ag+ ions is need to cause the precipitation of Ag2CrO4. When silver nitrate solution is run into a solution of Cl ions, Ag2CrO4 does not precipitate until all the Cl ions have precipitated as AgCl. When the precipitation of AgCl has completed, the addition of one drop of silver nitrate will cause the precipitation of Ag2CrO4, which corresponds to the end point of the titration.
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12
Objective Questions
Phase Equilibrium
1. Which of the following liquid mixture shows positive deviation from Raoults law? A Hexane and heptane B Ethanol and water C Hydrogen bromide and water D Nitric acid and water 2. Two miscible liquids X and Y form an ideal solution, containing 3 mol of X and 1 mol of Y. The total vapour pressure at 20 C is 48 kPa. The vapour pressure of pure X is 52 kPa at 20 C. What is the vapour pressure of pure Y at 20 C? A 36 kPa C 92 kPa B 48 kPa D 192 kPa 3. The partition coefficient of butanoic acid (CH3CH2CH2COOH) between ether and water is 3.0. If 1.0 g of butanoic acid is shaken with a mixture of water and ether until equilibrium is established, what is the volume of 1 mol dm3 sodium hydroxide solution required to neutralise all the acid in the ether layer? [Mr of butanoic acid = 88; the mixture contains equal volumes of water and ether] A 2.84 cm3 B 8.52 cm3 C 17.1 cm3 D 28.4 cm3 4. When a mixture of compound X and water is steam distilled at a pressure of 97.1 kPa and a temperature of 98 C, a distillate containing compound X and water in the ratio of 0.188 : 1 (by mass) is obtained. If the vapour pressure of water at 98 C is 94.5 kPa, what is the relative molecular mass of X? A 98 C 196 B 123 D 246 5. Which of the following solutions has the lowest vapour pressure at 30 C? A Distilled water B 0.1 mol dm3 MgSO4 solution C 0.1 mol dm3 MgCl2 solution D A mixture of water and phenylamine A 1 only is correct B 1 and 2 only are correct C 2 and 3 only are correct D 1, 2 and 3 are correct
6. When propanone (CH3COCH3) is mixed with chloromethane, heat energy is liberated and the increase in temperature is T1. If the experiment is repeated using CHCl3 and CCl4, the results as shown in the table below are obtained. In each experiment, the volumes of both the organic compounds are kept constant.
Mixture CH3COCH3 + CH3Cl CH3COCH3 + CHCl3 CH3COCH3 + CCl4
44
Increase in temperature T1 T2 T3
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Which of the following relationships concerning the increase in temperature is/are correct? 1 T1 = T2 = T3 2 T1 < T2 3 T3 < T2 7. A mixture of two liquids, X and Y shows positive deviation from Raoults law. This implies that 1 the two liquids are immiscible. 2 the vapour pressure-composition curve shows a maximum point. 3 the azeotropic mixture has a lower boiling point than pure X or pure Y. 8. The boiling point-composition diagram for a mixture of two miscible liquids, A and B, is shown below.
temperature
va p
ou
ui liq d
r
X composition
0% A 100% B
Y 100% A 0% B
Based on the diagram above, we can conclude that 1 pure A and pure B cannot be obtained from fractional distillation of mixture X. 2 fractional distillation of mixture Y produces pure B. 3 the mixture of A and B shows positive deviation from Raoults law.
1. (a) A mixture of water and methanol obeys Raoults law but a mixture of water and 1-propanol forms an azeotropic mixture. Explain the behaviour of these two mixtures. (b) Explain why water is immiscible with hexanol, CH3(CH2)5OH. 2. Butanedioic acid (HOOCCH2CH2COOH) is added to a separating funnel which contains equal volumes of water and ether. When equilibrium is established, the concentrations of the acid in aqueous and ether layers are determined by titration. The results of four experiments are shown below.
Volume of alkali required to neutralise 10 cm3 of the ether layer (cm3) 1.4 1.8 2.0 2.5 Volume of alkali required to neutralise 10 cm3 of aqueous layer (cm3) 9.0 12.0 13.5 17.5
(a) Name an alkali and a suitable indicator which can be used for the titration above. (b) Is butanedioic acid more soluble in ether or in water? Justify your answer. (c) Plot a graph and determine the partition coefficient of butanedioic acid between ether and water from the graph. (d) 1.0 g of butanedioic acid is dissolved in 20 cm3 water. The acid in the solution is extracted by using 40.0 cm3 of ether. Calculate the percentage of butanedioic acid that still remains in the aqueous layer after extraction. (e) If the acid is extracted twice using two separate portions of 20 cm3 of ether, what is the mass of ethanoic acid still remaining in water after the second extraction?
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Essay Question
1. (a) The boiling point-composition diagram for hydrogen fluoride and water is shown in the figure below.
120
vap o ur
100 80
ou r
liqu
id
vap
60 40
20 X 20 80
0 100
liqu
40 60
id
60 40
80 20
100 0
H2O HF
(i) A solution with composition X is heated until boiling. What is the boiling point of this solution? What is the composition of the vapour at the boiling point? (ii) Explain why a mixture of hydrogen uoride and water shows negative deviation from Raoults law. (b) The liquids P and Q form an ideal mixture. At 30 C, the vapour pressures of pure P and pure Q are 120 kPa and 40 kPa respectively and the mole fraction of P in the solution is 0.60. (i) Calculate the total vapour pressure for the liquid mixture at 30 C. (ii) Calculate the composition of vapour at equilibrium with the liquid mixture at 30 C.
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ANSWER
CHAPTER 12 Phase Equilibrium
Objective Questions 1. B Hexane and heptane ideal solution HBr/H2O negative deviation HNO3/H2O negative deviation 3 2. A Mole fraction of X = = 0.75 4 Mole fraction of Y = 1 0.75 = 0.25 Vapour pressure of X = 52 0.75 = 39 kPa Vapour pressure of Y = 48 39 = 9 kPa 9 = PYo 0.25; PYo = 36 kPa 3. B Let mass of butanoic acid in ether layer = x g Mass of butanoic acid in water = (1.0 x) g x = 3.0 1.0 x x = 0.75 g Number of moles of butanoic acid 0.75 = = 0.00852 88 CH3CH2CH2COOH + NaOH CH3CH2CH2COONa + H2O Number of moles of alkali required = number of moles of acid present = 0.00852 MV 1V 0.00852 = = 1000 1000 V = 8.52 cm3 mA pA MA 4. B = mH O pH O 18 2 2 0.188 (97.1 94.5) MA = 1 94.5 18 MA = 123 5. C MgCl2(aq) Mg2+(aq) + 2Cl(aq) MgCl2 solution contains the most number of ions per dm3 solution. 6. C The stronger the intermolecular forces of attraction, the greater the energy liberated in forming a non-ideal solution. CHCl3 is the most polar because it has three chlorine atoms per molecule. Both CHCl3 and CH3Cl can form hydrogen bonding with CH3COCH3. CCl4 molecule does not contain hydrogen atom. Hence, it cannot form hydrogen bonds with CH3COCH3. 7. C 8. B X is an azeotropic mixture. Its composition and boiling point remains unchanged during distillation. (1 correct) Fractional distillation of Y produces pure B. (2 correct) The mixture shows negative deviation. (3 incorrect) Structured Questions 1. (a) Both water and methanol molecules form intermolecular hydrogen bonds. The intermolecular forces of attraction between water molecules, between methanol molecules and between water-methanol molecules are almost the same. Hence, the mixture of methanol and water obeys Raoults law. The intermolecular forces of attraction between 1-propanol and water in the mixture is weaker than the intermolecular forces of attraction between 1-propanol-1-propanol molecules and between water-water molecules. Hence, a mixture of 1-propanol and water shows positive deviation from Raoults law and forms an azeotropic mixture with minimum boiling point. (b) Two liquids are immiscible if the intermolecular forces in the liquids are vastly different. In water, the molecules are held strongly by hydrogen bonds. Hexanol is a much bigger molecule than water. The van der Waals forces in hexanol is very strong. Hence, it is immiscible with water. 2. (a) Sodium hydroxide solution; phenolphthalein (weak acid strong base titration). (b) More soluble in water because more alkali is required for neutralisation as shown in the table. (c)
AB Gradient = BC (2.42 1.60) = = 0.13 (17.0 10.5) (d) Let mass of butanedioic acid remaining in water = m g Mass of butanedioic acid in ether = (1.0 m) g (1.0 m) 40 0.13 = m 20 m = 0.79 0.79 %= 100 = 79% 1
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(e) First extraction Let mass of acid in water = x g Mass of acid in ether = (1.0 x) g (1.0 x) 20 0.13 = x 20 x = 0.88 g Second extraction Let mass of acid in water = y g Mass of acid in ether = (0.88 y) g (0.88 y) 20 0.13 = y 20 y = 0.78 g Essay Question 1. (a) (i) 60 C; 8% H2O and 92% HF.
(ii) The intermolecular forces of attraction between HF --- HF in pure HF and between H2O --- H2O in pure H2O are hydrogen bonds. In aqueous solution, HF dissociates to form H+ and F- ions. The ion-solvent attraction between H+ and F ions with water is stronger than hydrogen bonds. Hence aqueous HF shows negative deviation from Raoults law. (b) (i) Partial pressure of P = 120 0.6 = 72 kPa Partial pressure of Q = 40 0.4 = 16 kPa Total vapour pressure = 72 + 16 = 88 kPa 72 (ii) Mole fraction of P in the vapour = 88 = 0.82 16 Mole fraction of Q in the vapour = 88 = 0.18
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13
Objective Questions
Electrochemistry
1. The standard electrode potential of some half-cells are given as follows:

Half-reaction Cl2 + e Cl Br2 + e Br I2 + e I H2O2 + H + e H2O O2 + 2H + 2e H2O2
+ +
E (V) +1.36 +1.07 + 0.54 +1.77 + 0.68
Which of the following pair of reagents does not result in a chemical reaction under standard conditions? A H2O2 with Cl2 B H2O2 with Br2 C H2O2 with I2 D H2O2 with KI 2. The cell diagram of an electrochemical cell is given as Pt(s) Fe2+(aq), Fe3+(aq) Cr2O72(aq), Cr3+(aq) Pt(s) Which of the following will increase the e.m.f. of the electrochemical cell? A Increase the concentration of Fe3+ ions B Increase the concentration of Cr3+ ions C Increase the concentration of Fe2+ ions D Decrease the concentration of Cr2O72 ions 3. The electrode potential of two half-cells are given below: Fe3+(aq) + e Fe2+(aq) Fe(CN)63 + e Fe(CN)64 ; ; E = + 0.76 V E = + 0.36 V
Which of the following statements is correct with regards to the cells above? A Fe(CN)64 is more stable than Fe2+(aq). B Fe(CN)63 is more stable than Fe3+(aq). C Fe(CN)63 is a stronger oxidising agent than Fe3+(aq). D Fe(CN)64 is a stronger reducing agent than Fe2+(aq). 4. What is the total volume of gas produced at 25.0 C when 0.20 A of current is passed through dilute sulphuric acid for 4825 seconds? (Faraday constant is 9.65 104 C mol1, molar volume of gas at 25.0 C is 24.4 dm3 mol1) A 0.061 dm3 B 0.122 dm3 C 0.183 dm3 D 0.244 dm3 5. Electrolysis is used to remove ions in industrial waste. Which of the following ions is removed in the treatment of effluent using electrolysis? A Al3+ ions B Cr3+ ions C PO43 ions D Cr2O72 ions
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A 1 only is correct
6. Chlorine gas is produced by electrolysis of brine in a diaphragm cell. Which of the following is also produced besides chlorine in the electrolysis process? 1 Hydrogen gas 2 Sodium hydroxide 3 Sodium chlorate(I) 7. The electrode potential of two half-cells are given below: Sn4+(aq) + 2e Sn2+(aq) Fe3+(aq) + e Fe2+(aq) ; ; E = + 0.15 V E = + 0.77 V
Which of the following statement(s) is true of the electrochemical cell formed from these two half-cells? 1 The cell diagram is represented by Pt(s) Fe2+(aq), Fe3+(aq) Sn4+(aq), Sn2+(aq) Pt(s) 2 3 The e.m.f. of the cell produced is 0.62 V. The cell e.m.f. will increase if the concentration of Sn4+ is decreased.
1. The half-equations and standard electrode potential at 25 C for two half-cells are Hg2Cl2(l) + 2e 2Hg(l) + 2Cl(aq) Fe3+(aq) + e Fe2+(aq) ; ; E = + 0.24 V E = + 0.77 V
(a) Write a cell diagram for the electrochemical cell constructed using the two half-cells above. (b) Calculate the e.m.f. of the electrochemical cell at standard conditions. (c) Name a substance that can be used as salt bridge for the cell above and explain how it works. (d) An oxidising substance Y is added to the Fe3+/Fe2+ half-cell and the e.m.f. of the cell is observed. The e.m.f. of the cell can be calculated using the Nernst equation. (i) Explain how the addition of the oxidising agent Y causes the change of the e.m.f. of the cell. (ii) Sketch a graph showing the change of e.m.f. versus the volume of oxidising agent Y added into the Fe3+/Fe2+ half-cell. [Fe2+] (iii) Calculate the cell e.m.f. if the ratio of is 1.00 103 while the concentration of [Fe3+] Cl remains unchanged. 2. In an electrolysis experiment, two electrolytic cells cell A and cell B are connected in series as show below. Cell A consists of two copper electrodes immersed in aqueous copper(II) sulphate solution. Cell B consists of silver electrodes immersed in silver nitrate solution.
copper electrodes silver electrodes
copper(II) sulphate solution cell A cell B
silver nitrate solution
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When a current of 0.50 A is allowed to pass through the two cells for 20.0 min, the mass of copper and silver deposited in cell A and cell B are 0.197 g and 0.672 g respectively. [Relative atomic mass: Cu, 63.5, Ag, 108] (a) Calculate the number of coulomb that passed through the two cells. (b) Calculate the number of coulomb that is required to deposit 1.0 mol of (i) copper atoms, (ii) silver atoms. (c) Comment on the results obtained in (b) in relation to the charge of the ions. (d) If the charge of an electron is 1.60 1019 C, calculate Avogadros constant using the result obtained in (b)(i). (e) Predict the number of coulomb that is required to deposit 1.0 mol of gold when AuCl3 is electrolysed with gold electrodes using the result obtained in (b)(i).
Essay Question
1. (a) The overall chemical change taking place during the industrial electrolytic manufacture of aluminium metal is represented by 2Al2O3 + 3C 4Al + 3CO2 (i) Explain all the chemical changes that take place in the process that result in the overall equation in the electrolyic process. (ii) Using the electrode potential values, explain why aluminium metal cannot be produced from the electrolysis of aluminium salt solutions using graphite electrodes. (b) Explain what is anodisation. An aluminium object with a surface area of 100 cm3 is to be anodised. Calculate the quantity of electricity (in coulomb) required to increase its oxide layer by 1.00 104 cm in thickness. [Density of Al2O3 is 4.00 g cm3]
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ANSWER
CHAPTER 13 Electrochemistry
Objective Questions 1. C Cl2 + H2O2 2Cl + O2 + 2H+; E = (+1.36 0.68) V = + 0.68 V Br2 + H2O2 2Br + O2 + 2H+ ; E = (+1.07 0.68) V = + 0.39 V The difference of the standard redox potential, E of the overall reactions are positive. Hence H2O2 will react with Cl2 and Br2. I2 + H2O2 2I + O2 + 2H+; E = (+ 0.54 0.68) V = 0.14 V E of overall reaction is negative. Hence H2O2 does not react with I2. 2I + H2O2 + 2H+ I2 + 2H2O; E = ( 0.54 + 1.77) V = + 1.23 V E of overall reaction is positive. Hence H2O2 will react with KI. 2. C The reaction that takes place in the electrochemical cell is 6Fe2+(aq) + Cr2O72(aq) + 14H+(aq) 6Fe3+(aq) + 2Cr3+(aq) + 7H2O(l) According to the Nernst equation: 0.059 [Fe2+]6 [Cr2O72] E = E + log 6 [Fe3+]6[Cr3+]2 0.059 [reactants]x Or: E = E + log 6 [products]y Hence the increase in the concentration of the reactants or the decrease in the concentration of the products will increase the E value. 3. B A more positive E value indicates that Fe3+(aq) has a higher tendency to be reduced to Fe2+ (aq) than Fe(CN)63 to Fe(CN)64 (C and D incorrect). Hence Fe(CN)63 is more stable than Fe3+ (aq) and Fe2+ (aq) is more stable than Fe(CN)64 (A incorrect, B correct). 4. C Q = 0.20 A 4825 s = 965 C = 0.01 F At the cathode: 2H+ + 2e H2 0.01 F electricity will produce 0.01 24.4 = 0.122 dm3 of H2 gas. At the anode: 4OH O2+ 2H2O + 4e 0.01 F electricity will produce 0.01 24.4 = 0.061 dm3 of O2 gas. Total volume of gas produced = 0.122 + 0.061 = 0.183 dm3 5. B Heavy metal ions are removed from the efuent using electrolysis under certain conditions. Al3+ ions are not discharged because of its very
52
positive E value. Anions are not removed in electrolysis. 6. B The ions present in brine solution are H+, Na+, OH and Cl. H+ ions are discharged at the cathode forming H2 gas. (1 correct) Cl ions are discharged forming Cl2 gas, leaving Na+ and OH ions in the electrolyte forming NaOH. (2 correct) Cl2 and NaOH are prevented from reacting by the diaphragm, hence NaClO is not formed. (3 incorrect) 7. C Sn4+/ Sn2+ will be the negative terminal of the cell since it has a less positive E value. The cell diagram is Pt(s) | Sn2+(aq), Sn4+(aq) || Fe3+(aq), Fe2+(aq) | Pt(s). (1 incorrect) E.m.f. of cell = (0.77 0.15) V = 0.62 V (2 correct) According to the Nernst equation: 0.059 [Sn2+] [Fe3+ ]2 E = E + log 2 [Sn4+][Fe2+]2 The cell e.m.f. will increase when [Sn4+] is decreased. (3 correct) Structured Questions 1. (a) Pt(s) | Hg(l),Hg2Cl2(l) || Fe3+(aq),Fe2+(aq) | Pt(s) (b) Ecell = E Fe3+ / Fe2+ E Hg+ / Hg = + 0.77 0.24 = + 0.53 V (c) Ammonium chloride / potassium chloride / any suitable electrolyte. The salt allows the movement of ions so as to maintain electrical neutrality of the two halfcells and also prevent the electrolytes of the two half-cells from mixing. (d) (i) The reaction of the cell is: 2Hg(l) + 2Cl(aq) + 2Fe3+(aq) Hg2Cl2(l) + 2Fe2+(aq) According to the Nernst equation: 0.059 [Cl]2 [Fe3+]2 E = E + log 2 [Fe2+]2 The addition of the oxidising agent Y will increase the concentration of Fe3+ ions and hence the e.m.f. of the cell is increased. (ii) e.m.f of cell (V)
0.53
volume of Y (cm3)
0.059 [Cl]2 [Fe3+]2 (iii) Ecell = Ecell + log 2 [ Fe2+ ]2
2/20/08 11:31:08 AM
2. (a)
(b)
(c)
(d)
(e)
0.059 1 = 0.53 + log 2 (1.00 103)2 = + 0.707 V Number of coulomb = I t = 0.50 20.0 60 = 600 (i) 0.197 g of Cu is deposited by 600 C. l.0 mol of Cu is deposited by 63.5 600 C = 193 000 C 0.197 (ii) 0.672 g of Ag is deposited by 600 C. l.0 mol of Ag is deposited by 108.0 600 C = 96 400 C 0.672 193 000 C is approximately equals to 2 96 400 C. The number of coulomb required to deposit 1.0 mol of Cu is twice that required to deposit 1.0 mol of Ag. This is because the charge of Cu2+ ions is twice of that of Ag+ ions. 193 000 = NA e 2 96 500 = NA 1.60 1019 NA = 6.03 1023 mol1 Since Au3+ has a charge of 3/2 times of Cu2+, the number of coulomb to deposit 1.0 mol of Au is 3/2 193 000 C = 289 500 C
Essay Question 1. (a) (i) Aluminium is manufactured by the electrolysis of molten aluminium oxide using graphite electrodes. Molten Al2O3 dissociates into Al3+ ions and O2 ions. The reactions that take place at the electrodes are anode: 2O2 O2 + 4e (1) cathode: Al3+ + 3e Al (2) The O2 gas evolved at the anode reacts
with the carbon electrode to produce carbon dioxide gas: C + O2 CO2 (3) The overall equation = (1) 3 + (2) 4 + (3) 3 4Al3+ + 6O2 + 3C 4Al + 3CO2 Or: 2Al2O3 + 3C 4Al + 3CO2 (ii) Al3+ + 3e Al ; E = 1.66 V 2H+ + 2e 2 ; E = 0 V The electrode potential of Al3+/Al is much more negative than that of H+/H2, resulting in a much higher discharge potential for Al3+ ions to be discharged. Electrolysis of aluminium salt solutions using graphite electrodes will result in H+ ions being discharged to produce hydrogen gas instead of aluminium metal. (b) Anodisation is a process in which the thickness of aluminium oxide of an aluminium object is thickened by electrolysis. In this process, the aluminium object is made the anode, using dilute sulphuric acid or chromic acid as the electrolyte. Volume of Al2O3 to be deposited on the aluminium object = 100 cm2 1.0 104 cm = 0.01 cm3 Mass of Al2O3 to be deposited = density volume = 4.0 0.01 = 0.04 g During anodising at the anode: 4OH O2 + 2H2O + 4e 1 mol of O2 to be formed requires 4 Faradays. O2 reacts with the aluminium anode object: 3O2 + 4Al 2Al2O3 1 mol (102 g) of Al2O3 requires 4 3/2 Faradays to be formed. 0.04 g Al2O3 requires 4 3/2 96 500 0.04 = 227 C 102
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14
Objective Questions
Thermochemistry
1. Which of the following chemical changes releases heat energy? A O2(g) 2O(g) B O(g) + e O(g) C O(g) + e O2(g) D Mg+(g) Mg2+(g) + e 2. The standard enthalpy change of neutralisation for dilute sulphuric acid and sodium hydroxide is the heat liberated when A 1.0 g of aqueous H2SO4 reacts with 1.0 g of aqueous NaOH. B mol of aqueous H2SO4 reacts with 1.0 mol of aqueous NaOH. C 1.0 mol of aqueous H2SO4 reacts with mol of aqueous NaOH. D 1.0 mol of aqueous H2SO4 reacts with 2.0 g of aqueous NaOH. 3. The standard enthalpy change of formation of carbon monoxide is the standard enthalpy change for the reaction A C(s) + O(g) CO(g) B C(s) + O2(g) CO(g) C C(g) + O(g) CO(g) D C(g) + O2(g) CO(g) 4. Which of the following represents the correct ascending order of the lattice energies of ionic compounds? A NaBr < NaCl < NaI B KI < LiF < NaCl C KI < NaBr < LiCl D KCl < KBr < KI 5. The second ionisation energy of magnesium is +1450 kJ mol1. Which of the following thermochemical equations represents the second ionisation energy of magnesium? A Mg+(g) Mg2+(g) + e ; H = +1450 kJ mol1 B Mg+(s) Mg2+(g) + e ; H = +1450 kJ mol1 C Mg(s) Mg2+(s) + 2e ; H = +1450 kJ mol1 D Mg(g) Mg2+(s) + 2e ; H = +1450 kJ mol1 6 Which of the following ions has the highest (most exothermic) enthalpy of hydration? Ion Charge Ionic radius (nm) A +1 0.095 B 2 0.14 C +2 0.065 D +2 0.11
7. By using the following information, calculate the standard enthalpy of formation of ethanol. Standard enthalpy of combustion of graphite = 393 kJ mol1 Standard enthalpy of combustion of hydrogen = 286 kJ mol1 Standard enthalpy of combustion of ethanol = 1367 kJ mol1 A 191 kJ mol1 B +191 kJ mol1 C 277 kJ mol1 D +277 kJ mol1
54
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A 1 only is correct
8. Which of the following processes is/are always exothermic? 1 Na+(g) + water Na+(aq) 2 Cl(g) + e Cl(g) 3 Na+(g) + Cl(g) NaCl(s) 9. Na(s) + Cl2(g) Na(g) + Cl2(g) Na(g) + Cl2(g) Na+(g) + Cl(g) Na+(g) + Cl(g) NaCl(s) ; ; ; H1 = +108 kJ mol1 H2 = +257 kJ mol1 H3 = -766 kJ mol1
Based on the information given above, which of the following statements is/are true? 1 H1 is the enthalpy of atomisation of sodium. 2 The enthalpy of formation of sodium chloride is -401 kJ mol1. 3 H2 is the sum of electron affinity for chlorine and the first ionisation energy for sodium.
1. (a) Each cyclohexene molecule, C6H10, has one C = C bond. 1 mol of cyclohexene reacts with 1 mol of hydrogen to form cyclohexane, C6H12. C6H10 + H2 C6H12 ; H1 Calculate the value of H1 from the following data: Enthalpy of formation of cyclohexene = 36 kJ mol1 Enthalpy of formation of cyclohexane = 156 kJ mol1 (b) Benzene, C6H6 undergoes similar reaction with hydrogen to form cyclohexane. C6H6 + 3H2 C6H12 ; H2 Predict the value of H2 assuming that each benzene molecule contains three C = C bonds. (c) The value of H2 as determined by experiment is 207 kJ mol1. What inference can you make with regard to the stability of the benzene ring. 2. The enthalpies of hydration of some ions are shown below.
Ion H (kJ mol1) Na+ 390 Mg2+ 1891 Al3+ 4613 Cl 381 Br 350 I 307
(a) Why are the hydration energies of both anions and cations negative? (b) What is the hydration energy of MgI2? (c) Why does the hydration energy get progressively less exothermic for the series (i) Cl, Br , I (ii) Al3+, Mg2+, Na+ (d) Given that, NaCl(s) Na+(g) + Cl(g) ; H = +776 kJ mol1 Calculate the heat of solution of sodium chloride.
55
2/20/08 11:31:13 AM
Essay Question
1. (a) When 0.20 g of magnesium powder is dissolved in dilute hydrochloric acid in a polystyrene cup, the temperature of the solution increases by 8.6 C. In another experiment, the plastic cup and its contents are found to require 500 J of heat to raise the temperature by 1 C. (i) Write a chemical equation for the reaction between magnesium and hydrochloric acid. (ii) Calculate the heat liberated in the experiment. (iii) Hence, calculate the enthalpy change of reaction for 1 mol of magnesium. (b) In a similar experiment, it was found that when magnesium carbonate is dissolved in excess hydrochloric acid, the enthalpy change is 90 kJ per mole of magnesium carbonate. Use your results in (a)(iii) to calculate the enthalpy change of formation of magnesium carbonate. (Standard enthalpy changes of formation of water and carbon dioxide are 285 kJ mol1 and 393 kJ mol1 respectively.) (c) Calcium carbonate and magnesium carbonate decompose on heating. Which would decompose at a higher temperature, calcium carbonate or magnesium carbonate? Explain your answer.
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ANSWER
CHAPTER 14 Thermochemistry
Objective Questions 1. 2. 3. 4. B B mol of H2SO4 contains 1 mol of H+ ions. B C The ions in all these ionic compounds carry the same charge. Lattice energy is inversely proportional to interionic distance. Interionic distance decreases in the order: KI > NaBr > LiCl Lattice energy increases in the order: KI < NaBr < LiCl A C The higher the charge, the higher the enthalpy of hydration. The smaller the ionic radius, the higher the enthalpy of hydration. C C2H5OH + 3O2 2CO2 + 3H2O; x 0 2 (393) 3 (286) H = 1367 kJ mol1 1367 = [2 (393) + 3 (286)] x x = 277 D Na+(g) + water Na+(aq) ; Hydration energy Cl(g) + e Cl(g) ; First electron afnity Na+(g) + Cl(g) NaCl(s) ; Lattice energy B In equation (1), Na(s) Na(g). Hence, H1 is enthalpy of atomisation for sodium. (1 correct) On adding equations (1), (2) and (3), we have Na(s) + Cl2(g) NaCl(s) ; H f Thus, H f = (+108) + (+257) + (766) = 401 kJ mol1 (2 correct) Cl2(g) Cl(g) is not electron afnity for chlorine. (3 incorrect) ions while the O atoms (negative polarity) of H2O are attracted to the positive ions. The formation of ion-solvent bonds results in a release of energy, known as hydration energy. (b) 1891 + 2 (307) = 2505 kJ (c) The smaller the ionic size, the stronger the ion-solvent bond and the greater the energy released. (i) The ionic size decreases from I to CI. Hence, hydration energy decreases from Cl to I. (ii) The ionic size decreases from Na+ to Al3+. Hence hydration energy decreases from Al3+ to Na+. (d) NaCl(s) Na+(g) + Cl(g) ; H = +776 kJ mol1 Na+(g) + water Na+(aq) ; H = 390 kJ mol1 Cl(g) + water Cl(aq) ; H = 381 kJ mol1
NaCl(s) + water Na+(aq) + Cl(aq) ; H
5. 6.
7.
8.
390 kJ +776 kJ
381 kJ
Na+(g) + CI(g)
9.
H = (+776) + (390) + (381) = +5 kJ mol1 Essay Question 1. (a) (i) Mg + 2HCl MgCl2 + H2 (ii) Heat liberated = 500 8.6 = 4300 J = 4.3 kJ (iii) Number of moles of Mg 0.2 = 24.3 = 8.23 103 Enthalpy change of reaction per mole of Mg 4.3 = 8.23 103 = 522.5 kJ mol1 That is, Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g) H1 = 522.5 kJ mol1 (1) (b) Let the enthalpy change of formation of MgCl2, HCl and MgCO3 be x, y and z kJ mol1 respectively. MgCO3 + 2HCl MgCl2 + H2O + CO2 (2) x 2y z 285 393
Structured Questions 1. (a) C6H10 + H2 C6H12 ; H1 36 0 156 H1 = (156) [(36) + 0] = 120 kJ mol1 (b) H2 = 3 (120) = 360 kJ mol1 (c) The actual heat energy released is less than the theoretical value. This implies that benzene has a more stable structure than the predicted structure with three C = C bonds. The structure of a benzene molecule is a resonance hybrid of two Kekule structures. The delocalised electrons confer stability on the benzene ring. 2. (a) In the hydration process, the H atoms (positive polarity) of H2O are attracted to the negative
57
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H2 = 90 kJ mol1 H of reaction = Hf (products) Hf (reactants) 90 = [z + (285) + (393)] [x + 2y] That is x + 2y z = 588 (3) From equation (1), we have Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g) (1) 0 2y z 0 H of reaction = Hf (products) Hf (reactants) 522.5 = z 2y (4) Substituting equation (4) into equation (3), x + 522.5 = 588
x = 1110.5 kJ mol1 That is, the enthalpy change of formation of magnesium carbonate is 1110.5 kJ mol1 (c) MgCO3 MgO + CO2 CaCO3 CaO + CO2 Ca2+ ion has a bigger ionic radius than Mg2+ ion. Therefore Ca2+ ion has a weaker polarising power. As a result, the polarisation of CO32 ion by Ca2+ ion is weaker. Hence, it is difcult to decompose the CO32 ion to give CO2 and O2 ions. This means that CaCO3 is stable towards thermal decomposition and decomposes at a higher temperature.
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Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 1

Oxford Fajar Sdn. Bhd. (008974-T) 2008

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 2

Oxford Fajar Sdn. Bhd. (008974-T) 2008

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 3

2. (a) 1H+, 35Cl+, 37Cl+ 1 H 35Cl+, 1H 37Cl+ (b)

Species Helium nuclei H

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 4

The Gaseous State

3. The graph of against p for a gas, X, at 273 K is shown below. p

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 5

B 1 and 2 only are correct

C 2 and 3 only are correct

D 1, 2 and 3 are correct

O2 2 dm3 1.0 atm

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 6

Oxford Fajar Sdn. Bhd. (008974-T) 2008

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 7

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 8

Oxford Fajar Sdn. Bhd. (008974-T) 2008

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 9

The Liquid and Solid States

1. The phase diagram for iodine is shown below.

A 100 110 120 130 140

Methane Hydrogen chloride Sulphur dioxide Water

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 10

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 11

Hence, increase in pressure favours the formation of water.

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Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 12

The Electronic Structure of Atoms

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 13

n=1 24.7 29.3 30.9 31.6 32 32.2 frequency (X 1014 Hz)

4 3 2 1 33.1 f (x1014 Hz)

Oxford Fajar Sdn. Bhd. (008974-T) 2008

Ace Ahead Chemistry (Question Bank) 5th (19/2/08).indd 14

The Periodic Table

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charged rod (positive or negative)

jet of deflected liquid

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B 1 and 2 only are correct

C 2 and 3 only are correct

D 1, 2 and 3 are correct

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2. (a) (b) (c) (d) (e)

Helium Silicon Trichloromethane Sodium bromide Potassium

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Essay Question 1. (a)

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Intermolecular Forces of Attraction

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Boiling point (oC)

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