a-level aes Col OVI AVG TARY) learn-by-example question-types from top colleges mee AUIS Wd) EA, thomas bond wai aaematehtn updated editionCHEMISTRY ADVANCED LEVEL challenging learn-by-example Updated Eaition Thomas Bond waccasat) Chris Hughes ws-(vonan) + according to syllabus for exam up to yeor 2016 * updated new questions from top schools & colleges since 2008 - end 2013 + first to provide teachers’ comments revecling common mistakes & wrong habits * arranged from easy-to-hard to facilitate easy absorption + most efficient method of learning, hence saves time * advanced trade book * complete edition & concise edition eBooks avoilable © also suitable for © Cambridge GCE AL (H1/H2) © Cambridge Internotional AL © Cambridge Pre-University"Formal edueation will make you. living; self-education vill make you a fortune." —sim Rohn YE\LOWREEF's mission ie tobring accurate knowledge tothe master. We firmly beliove that education isthe greatest enablerin envichin the lives of millions. This journey ‘began with the publication of ou frst book in 1994, Today, YELLOWREEF’s books in languages, arts, mathematics and sciences open upa whole world of pessblitios for the students by equipping them with a range of took to ‘master knowledge in an enjoyable and effortless manner. Well done, YELLOWREEF. PUBLISHED EY THEMIS PUBLISHING \vBox 888862 Singepere 919193, telephone: (+65) 8211-9218 (sales) (+65) 8273-7672 (delivery) (r65) 8211-6282 (sales admin) (+1306) 918-7079 {sales admin) (+65) 8155-5542 (fulfillment) office: (465) 8464-4668 (redemption, eBook fulfillment) email: eBooks@yellowreefcom (orders) soles@yellowreef.com (enquiries) website: wuvw yellourees com copyright since 1994 © YELLOWREEF LINITED, UK All rights reserved. No partof ths book shall be reproduced, stored ina database or retrieval system, lor transmitted in any form or by any means, electronic, mechanical, photocoaying, recording or otherwise, without the prior written permission ofthe Publisher. [No patent ibility is assumed with respect to the use ofthe information contained herein, The Publisher, the editors of and the contibutors to this publication have taken all reasonable care to ensure that the contents of this publication are error-free. Every efforthas been made to cantact the holders of copyright material, but if any have been inadvertently oxerlooked, the Publisher will be pleased to make the necessary arrangements a the frst opportunity. Use ofthis publication's at your own sk and its availability or updates are not guaranteed, By purchasing this publication, you agree to the terms and conditions above. No refund would be made. Pleasesendfeedbackto: eBoaks@yellowreefcom From time to time, we do provide addenda and errata, Inorder to ensure approprate updates to your books, please register at [www yellowreef.com] License: YELLOWREEF LIMITED, UK, the original copyright owner of ths publication, has licensed THEMIS. PUBLISHING, at its own co:ts, one-time only arinting and publishing ofthis booktitle at a sale quantity specified by private treaty between the two partes. No par of this beok shall be reproduced, stored in a database or retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the ptr written permission ofthe original copyright owner. YELLOWREEF LIMITED, UK hereby reserved al rights to the publicationaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.= (2012) Teachers’ Comments] Questions that relate to chemical thermodynamics need to be answered carefully and accurately; Answers must not be ambiguous. While there were many good responses to this question, there were also many candidates who lost credit through a lack of care with equations, definitions or calculations. (2) Many equations were incorrect because they were unbalanced, lacked or had incorrect state symbols, Defitions of enthalpy change of formation were often insufficiently rigorous and sometimes vague It was expected thatthe definition would begin with 2 phrase such as “the enthalpy change of formation isthe enthalpy change when... Statements which began “itis when 1 mol of.” were not accepted. Definitions that referred to ‘..the energy required to.” were nct accepted because enthalpy change ‘of formation can be ondothsrmicor exothermic. (0) () Many candidates obtained the correct answer. The main errors seen were having the eye the wrong way round and getting +49 ki mol, or using bond energies from the Data Booklet. Candidates were asked to include a sign in their answer; a significant number éid not do this and were penalised (il) Candidetes usually realsed that CO, was being used up inthe reaction so, as itis a greenhouse as, global warming would be reduces by the formation of methano) (e)__ Many candidates showed a good understanding of Le Chatelier's principlein their answers, Only the very bes: candidates appreciated that with a catalyst the yield does rot change because the ferward ‘and backward reactions are speeded up by the same amount. Some arswers talked about the rate of reaction for which no credit was awarded.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.94 92 93 94 95 10.1 102 Reaction kinetics 8.1 Simple rate equations; orders of reaction; rate constants 8.2 Concept of activation enerey 8.3 Effect of concentration, temperature, and catalysts on reaction rate 8.4 Homogeneous and heterogeneous catalysis 8.5 Enzymes as biological catalysts The Periodic Table: chemical periodicity 9.1.1 Periodicity of physical properties of the elements 9.1.2 Periodicity of chemical properties of the elements in the third Period Group I! 9.2.1 Similarities and trends in the properties of the Group Il metals magnesium to barium and their compounds Group Vil 9.3.1 Thesimilarities and trends in the physical and chemical properties of chlorine, bromine and iodine {An introduction to the chemistry of transition elements 9.4.1 General physical and characteristic chemical properties of the first set of transition elements, titanium to copper 9.4.2 Colour of complexes Group IV 9.5.1 Similarities and trends in the properties of the Group IV metals carbon to lead and their compounds Organic chemistry — introductory topics 10.1.1 Molecular, structural and empirical formulae 10.1.2 Functional groups and the naming of organic compounds 10.1.3 Characteristic organic reactions 10.1.4 Shapes of organic molecules; ¢ and n bonds 10.15 Isomerism: structural; geometrical; optical Hydrocarbons 10.21 Alkanes (exemplified by ethane) 10.22 Alkenes (exemplified by ethene) 10.23 Arenes (exemplified by benzene and methylbenzene) 10.2.4 Hydrocarbons as fuelsaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.MARK SCHEMES Every examination has a mark scheme. Mark schemes are prepared by the Chief Examiner and considered, together with the relevant questions, bya panel of subject teachers. The mark scheme includes any amendments made at the stendardisation meeting attended by all examiners and is the scheme which was used by them in the examination. The standardisation meeting ensures that the ‘mork scheme covers the candidates’ responses to questions and that every examiner understands and applies it in the same correct way. EXAM REPORTS Every examination has an examiner's report. The Examiners’ Report may refer in general terms to statistical outcomes. Statistical information on candidates’ performances in all examination components are provided when results are issued; as well as a review of the performance of candidates in the examinations and detailed analysis of the standards of answering, especially erroneous understanding and wrong application of relevant concepts. CONTROVERSY (One would have assumed that the aim of the examination is to gauge and qualify candidates according to his/her standard of achievement and competence in the subject matter. Hence, after every examination, the chief examiner (internel or external) through the exam board will issue both the mark scheme and exam report to every school as a guide for teachers and future candidates helping them handle examinations more accurately. Over the years, with the help of these relevant mark schemes and examiner's reports, candidates have steadily raised the quality and standard of answers. ‘The grades were concentrated at the top-end of the spectrum. This has caused problems to the exam boards trying to distinguish the better candidates from the poorer ones, Instead of implementing a better qualification process, some exam boards chose the easy way out. These exam boards completely removed access to these important mark schemes and examiner's reports and classified these documents as “confidential”, thus, running contrary to the original spirit of education. We donot believe in this opacity. We believe in educating students through total true knowledge. Hence, in all our publications, we have, as far as. practicable, included all relevant mark schemes and exam reports to as many question types as we could possibly get hold of. We have a duty to ensure “Knowledge is power. Total knowledge, acquired through accurate and completely true education, is absolute power.” One simply must know how an examiner marks and what constitutes a complete and correct answer assuring full credit.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.{d) The rolative formula mass of an ionic compounds the ratio of the average mass of one formula unit of the compound to 4 the mass of an atom of "C isotope, expressed on the “C scale. It has no units as it isa ratio. (ans) a Brample3 Calculate the relative molecular/formula mass of: (2) ethanol (b) calcium carbonate (0) carbonate ion (2) M, of ethanol = 2(12.0) +5(1.0) +16+1 = 46.0 (ans) (b) M, of calcium carbonate = 40.1 + 12.0 +3(16.0) = 100.1 (ans) (€)_ Relative formula mass of carbonate ion =12.0 + 3(16.0) =60.9 (ans) a Example Calculate the: (2) relative molecular mass of aluminium sulfate, A/s{SO.)s, (b) number of molecules of aluminium sulfate in 1.5 kg of aluminium sulfate, (c)_ number of ions in 1.5 kg of aluminium sulfate. (a) _M, of aluminium sulfate = 2(27.0) + 3{32.1 + 4(16.0)) = 342.3 (ans) (b) Number of moles of aluminium sulfate Number of molecules in 1.5 kg of aluminium sulfate = 4,38 x 6.02 x 10 = 2.64 x 10 (ans) (c) Number of ions in aluminium sulfate =5 x 2.64 x 10" =1.32 x 10° (ans) 1 ons mle and aon 1-3aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Example # i (a) (b) Calculate the concentration (in mol dm) of the solution obtained by dissolving 2.0 g of glucose, CéH.120¢, in water to make 250.cm’ of solution. Calculate the concentration (in mol dm *) of the solution obtained by ciluting 10.0 cm’ of a1.5 mol dm’? hydrochloric acid with water to give 250 om’, Solution: @) () 20 Number of moles of glucose = =—————______ 8 [6(12.0) +12(1.0)+6(460)] oe Concentration = 228 x 0.0111 .0444 mol dm (ans) Let the concentration of the diluted solution be c. 1.5.x (388) =cx (2B) ¢=0.06 moldm” (ans) @) (b) () (a) (e) (b) (e) Calculate the molarity ofa solution containing 3.6 g HC/ in 1 dm? of solution. Calculate the number of moles of copper sulfate in 500 cm’ of 0.5 M copper sulfate solution. Calculate the number of ions in 300.0 cm’ of 0.25 M aqueous aluminium chloride. Calculate the concentration (in gdm’) of a solution of 0.3 M sodium nitrate. Calculate the molarity of sodium hydroxide that contains 40.0 g sodium hydroxide in 250 cm’ of solution. 3.6 (5542.0) =0.0986 (ans) No. of moles of copper sulfate in500cm? = 0.5(500 x 10 *) =0.25 mol (ans) No. of moles of aluminium chloride = 0.25(300 « 107) .075 mol No. of moles of ions = 0.075 «4 No. of ions = 0.075 x 4 x 6.02 x 10 =1,81x 10" ions (ans) 1 ons mle and aon a7aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.ES 8. M,of gypsum = 40.1 +32.1 + 4(16.0) +2[2(2.0) + 16.0] = 172.2 No. of moles of gypsum used = 71%; = 0.58072 mol (5 sf) No. of moles of water los 48 =0,86667 mol (5 sf) Ratio of moles of water lost to moles of gypsum used. = 2.86662 aso =15 Since 1 mol of gypsum loses 1.5 mol of water to form plaster of Paris, the formula for plaster of Paris is CaSO,.0.5H;0. (ans) (0100.30.50) 1000 = 3.05 «107 9. No. of moles of Nao! Mole ratio of citric acid : NaOH. No. of moles of citric acid = 2. 3.05 «10° 1.02 «107 M, of citric acid = 6(12.0) + 8(1.0) + 7(16.0) = 192.0 Mass of citric acid = 1.02 x 10° x 192.0 0.196 8 Percentage by mass of citric acid = (2%) x 100 =0.799 % (ans) (hemsey~ Chaleging (BE =aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.kBE Ionic (electrovalent) bonding fundamental questions Example 1 Explain why noble gases de not form ionic bonds. Solution: Noble gases have completely filled s and p orbitals in their valence loutermost) shells, therefore the atoms of noble gases are inert and chemically stable. All other atoms are chemically unstable as they have an incomplete valence shell where they have less than 8 electrons. These atoms will give away or accept new electrons in order to achieve an outer configuration of 8 electrons and become chemically stable. When there is a transfer of electrons from one atom to another, an ionic bond is. formed. (ans) Example 2 (a) Define ionic bonding. (b) State the differences between a cation and an anion (c)_ State the conditions that favour ionic bonding (4) Draw the electron ‘dot and cross’ diagrams forthe following ionic compounds. () act (i), Mgo (iil) ALO Solution: {a) lonic bonding is defined as the strong electrostatic force of attraction between oppositely charged ions as a result of the transfer of electrons from one atom to another. (ans) {b)_ The atom giving away the electron(s) is known as the cation and it has a positive charge. The atom accepting the electron(s) is known as the anion andit has a negative charge. (ans) {@)_ Ionic bond formation is especially favourable between atoms with low ionization energy (elements in Group | and Il) as they lose electrons easily and those with high electron affinity (elements in Group VI and Vil) as they gain electrons easily, lonic compounds will only be formed if the energy released in the formation of the ionic crystal lattice is greater than the energy required to form bonds. ans] (d) (i) NaC Nae+ Ci > [Nal (:3:) (hemsey~ Chaleging (BEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Example 2 Draw the ‘dot and cross’ diagrams for the following molecules. (a) He (b) 0, (c) Ch (d) Nr e) Her () cor (8) Che (h) CMe Solution: fa) Hp Ho+:H > HoH Hydrogen has 1 valence electron. Therefore it shares the electron with another hydrogen atom to obtain a duet of electrons. (ans) (b) 0, 8084 %0% + 803 x0" Onygen has 6 valence elecirons. Therefore each oxygen atom shares 2 electrons to form a double bond (2 covalent bonds) and achieve an octet structure. (ans) () ch 8° +, + 8ereci® Chlorine has 7 valence electrons. Therefore each chlorine atom shares 1 electron to obtain octet structure, (ans) (d) No SNo+,Ni > NEN Nitrogen has 5 valence electrons. Thus each nitrogen atom shares 3 electrons with another nitrogen atom to obtain octet structure. (ans) (e) HCl Ho +g a HES Hydrogen has 1 valence electron while chlorine has 7 valence electrons. Therefore each chlorine atom shares 1 electron with a hydrogen atom to obtain octet structure. (ans) (f) CO, GOR + SCL +405 > 205565505 Carbon has 4 valence electrons while oxygen has 6 valence electrons. ‘Therefore one carbon atom shares 2 electrons each with two other oxygen atoms to obtain octet structure. (ans) CGhemsry~ Caleging (BE =aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.{a) CO,” has 3 electron pairs, therefore itis trigonal planar in o electron geometry. All of them are bonding pairs, therefore the Z molecular geometry is also trigonal planar, with a bond angle of 120" Ng 120°. (ans) (b) SO; has 3 electron pairs, therefore it is trigonal planar in electron geometry. 2 of them are bonding pairs, resulting ina bent molecular geometry, with a bond angle of 120°. (ans) {d) NH has 4 electron pairs, therefore it has a tetrahedral electron geometry. 3 are bonding pairs, resulting ina trigonal pyramidal molecular geometry, with a bond angle of about 107°. (ans) (e) H,0 has 4 electron pairs, therefore it has a tetrahedral electron geometry. 2 are bonding pairs, resulting in a V-shaped molecular geometry, with a bond angle of about 105". (ans) (f) PCI; has S electron pairs, therefore it has atrigonal bipyramidal cl electron geometry. AllS are bonding pairs, resulting ina trigonal |_|! bipyramidal molecular geometry, with a bond angle of 120° and “|. 90°. (ans) e (g) SF, has 6 electron pairs, therefore it has a octahedral electron r ‘geometry. 6 are bonding pairs, resulting in an octahedral Frce-bf molecular geometry, with a bond angle of 90°. (ans) (h) NHs" has 4 electron pairs, therefore it has a tetrahedral a yt electron geometry. 4 are bonding pairs, resulting in a asl tetrahedral molecular geometry, with a bond angle of ue Msi 109.5°, (ans) (i) Ni, has 4 electron pairs, therefore it has a tetrahedral - electron geometry. 2 are bonding pairs, resulting in a V- XP : N shaped molecular geometry, with a bond angle of 105°. Qe (ans) Example 9 Explain the difference in bond angle between methane, ammonia and water. Soluti Allthe electron pairs in methane are bonding pairs, therefore it has the usual tetrahedral angle of 109.5". ammonia has 3 bonding pairs and 1 lone pair. AS bonding pair-lone pair repulsion is grester than bonding pair-bonding pair repulsion, the bond angle in ammonia becomes smaller (107*). Water has 2 bonding pairs and 2 lone pairs. Lone pair-lone pair repulsion is even greater than bonding pair-lone pair repulsion, causing the bond angle in water to be even smaller (105°). (ans) (hemsey~ Chaleging (BEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.(b) Two examples are ammonia and water (shown below) 9 N a7 oh frtroseo bond N Paes tydrogen a \ bond Ammonia Water Explain the following phenomenon, (a) The density of ice is lower than water. (b) Boiling points of hydrides tend to increase down a group due te an increase in relative molecular masses. However, the hydrides of the first member of Group V, VI and Vil are higher than expected. (c)_ The viscosity of a diol (alcohol with two OH groups) is greater than that with a single OH group. itrophenol has a higher boiling point that 4-nitrophenol. (a) Inice the hydrogen bonds hold the molecules together in a rigid but open structure. As ice melts, only a small number of hydrogen bonds are broken. This allows the water molecules to be more compactly arranged, accounting for the decrease in density when ice melts, The property is what allows a layer of ice to form on top of water surfaces in winter, while the water below remains unfrozen so that aquatic animals can survive. (ans) {b) The hydrides of groups V, VI and Vil, ammonia, water and hydrogen fluoride respectively, have higher than expected boiling points due to the ability of these molecules to form hydrogen bonds. Hydrogen bonding occurs when a small, highly electronegative atom is attached to a hydrogen atom, More energy is required to overcome the hydrogen bonds as compared to molecules with only Van der Waals’ forces. (ans) {c) A diol with two OH groups can form more hydrogen bonds and thus have stronger intermolecular forces. As such, the diol is expected to flow slower than an alcohol with a single OH group. (ens) 3-14 (hemsey~ Chaleging (BEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.(c) Properties of metallic crystals 1. Good conductors of heat and electricity The delocalized electrons are mobile and can transfer electricity and heat easily. 2. Malleable and ductile 3. High melting and boiling points This is due to the strong forces of attraction between the delocalized electrons and the positive ions. 4. High density ‘The metallic crystals are closely packed, leading to high densities. (ans) Example 2 ‘Compare the melting point and electrical conductivity (in molten and aqueous, states) of beryllium fluoride and beryllium chloride. Solution Beryllium fluoride is an ionic solid whose lattice is held together by strong ionic bonds. Therefore it has a high melting point and conducts electricity in the molten and aqueous states as free ions are present. Beryllium chloride is a simple molecular solid with weak van der Waals’ forces of attraction between discrete molecules. Therefore it has a low melting point and does not conduct electricity in the molten state as free ions are absent. It conducts in the aqueous state as free ions are present after beryllium chloride is, hydrolysed in water (acidic solution). (ans) (hemsey~ Chaleging (BEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.3 Standard Problems 1. Name the forces present in the following molecules. fa) Bra (b) Os te) NHS Draw the ‘dot and cross’ diagrams for the following compounds. Predict the molecular structures, (a) PHs (b) SF: ( (d) BF: {e) PBrs {H:0] 3. For following pairs of elements, predict the empirical formulas and draw the ‘dot and cross’ diagrams. (a) Kand N (b) Bando Selenium dioxide, SeO, is a solid that melts at 315°C and does not conduct electricity in the molten state. Explain this observation in terms of structure and bonding. 5. Explain the following. (a) The nitronium ion NO,” is linear but the nitrite ion NO; is non-linear. (b) The bond energy of HC (413 ki/mol) is the average of the H-H (436 ki/mol) (c (d (e) (b) Gomey ) () and the C-C (391 ki/mol) bonds but the bond energy of H-F (568 ki/mol) is not the average of H-H and FF (158 ki/mol) bonds. ‘The thermal stability of the hydrogen halides decreases from HF to HI. At standard conditions, carbon dioxide exists as a gas while silican dioxide exists asa solid. NH; is more soluble in water than PH, The bond angle of CH, (109.5*) is different from that of NH; (107°) Although the nitrogen triple bond hase much higher bond energy than that of the phosphorus single bond, nitrogen exists as a gas at room temperature while phosphorus is a white solid. Explain why. Can nitrogen form an cxoanion NO,” ? Explain your answer. ‘haeging WBEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.the stronger repulsion between the three bond-pair electrons and one lone- pair electrons in the NHs molecule. There is no bond-pair/lone-pair repulsion inthe CH, molecule. (ans) a G. (a) The strength of the intermolecular forces determines the state of 2 substance and not the type of bonding between the atoms. Nitrogen and phosphorus both have Van der Waals’ forces, which is dependent on the number of electrons. As phosphorus has more electrons than nitrogen, it has stronger Van der Waals’ forces and thus it exists as a solid. (ans) (b) No. To form the oxoanion NO,””, the central nitrogen atom will have more than 8 electrons, which is not possible as nitrogen does not have d-orbitals for expansion of octet configuration. (ans) a 7. (a) Ithas a giant ionic lattice which consists of positive and negative ions. There are strong electrostatic forces of attraction between the positive and negative ions, and thus it has 2 high melting point. The ions are only mobile in the moken state, thus it can only conduct electricity in the molten state. (ans) (b) tis hard and brittle and only soluble in polar solvents. (ans) 8, Melting and High as a large amount of | High as a large amount of boiling points | energy is needed to break | energy is needed to break the strong covalent bonds | the strong covalent bonds Conductors of | Poor electrical Good conductor as the electricity conductivity due to its valence electrons can strong and rigid crystalline | move, but only along the structure layers Solubility Insoluble in all solvents as_| Insoluble in all solvents as the solvent molecules the solvent molecules cannot enter the diamond | cannot enter the graphite lattice due to the strong _| lattice due to the strong covalent bonds covalent bonds 9. WandX ate isomers consisting of discrete molecules held together by weak van der Waals’ forces of attraction. Therefore they have low boiling points. W has a higher boiling point as compared to X as it has a larger surface area and thus stronger van der Waals’ forces of attraction. (hemsey~ Chaleging (BE =aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.pV =nRT and its use in determining a value for M, fundamental questions Example (@) State the general gas equation. (b) Show how it can be used to find the M, of a gas. Solu (2) pv=naT where p= pressure in Pa V=volume in m? = no. of moles of gas R= universal gas constant (8.314 JK” mol) T=temperature in K (ans) m b) Sincen="” where m=massin (b) a 8 = molar mass aT RT => M=pr= pat Mm pv p Example? For an ideal gas, state, with illustrations, how the following quantities are related to each other. (2) Pressure and volume at constant temperature (b) Volume and temperature at constant pressure (©). Pressure, volume and temperature Solution: (2) Atconstant temperature, pv = constant or Vc 4 P ——"v w P {ans) 1 ais omar a5aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.4 Standard Problems Tk ‘The graph above shows how the volume of a fixed mass of ideal gas varies according to its temperature. Determine if each of the following are correct descriptions of the pressure of the gas. (a) The gas pressure did not change from x to Y (b) The gas pressure decreased from Z toX (c)_ The gas pressure increased from Y to Z Yo ° ‘An experiment was conducted to find out how the pressure of a fired mass of gas varies with its temperature when it is kept at constant volume. At the end of the experiment a graph was plotted as above. Which of the following statements are true? (a) The y-axis denotes pressure while the x-axis denotes temperature. (b)_ The gradient of the graph is equivalent to the volume of the gas. (0) yorefers to the temperature absolute zero, 0 K {a)_ State and explain whether the expansion of gas into a region of low pressure is exothermic or endothermic. (b) Explain why gases like carbon dioxide can be liquefied by increasing the pressure. (c)_ Explain why gases can only be liquefied by pressure alone if the temperature is lower than the critical temperature, a Cylinders of pressurized carbon dioxide were used to make carbonated drinks. One such cylinder, with an internal volume of 2.5 dm’, contains 2.2 kg of carbon dioxide. Calculate the pressure exerted by carbon dioxide Inside the cylinder at room temperature (298 K). Suggest why this value obtained is different from the actual pressure of 2.2 x 10’ Pa inside the cylinder. 1 eaiecofmater a9aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.7. (@) (b) () (4) fe) =76.4(3 sf) (ans) Gas particles have negligible intermolecular forces of attraction, and they have negligible volume and size. (ans) No. of neon atoms in 1 mol .02 = 107? (ans) Volume of one neon atom= ¥ m (0.065 x 10°)? = 115x107? m? 1.15 x 10°77 dm? Volume of 1 mol of neon atoms = 6.02 x 10x 1.15 x 1077 92 x 10 “dm? Volume occupied by 1 mol of neon at room temperature and pressure =24dm? Percentage of the volume occupied by neon atoms _(esem0") =2.88 x 107% ‘The small percentage occupied by the atoms shows that the neon atoms have negligible volume and size. 1 eaiecofmateraa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Example Define the following. (a) Enthalpy change, AH (b) Standard enthalpy change of neutralisation ()_ Standard enthalpy change of solution (4) Standard enthalpy change of formation (e) Standard enthalpy change of combustion (f) Thermochemical equation Solution: (2) Enthalpy change is the change in heat energy content measured at constant pressure, AM is givena negative sign for exothermic reactions and a positive sign for endothermic reactions, indicating whether the system loses or gains, energy as a result of the reaction. (ans) (b) The standard enthalpy change of neutralisation is the amount of heat, released when one mole of water is formed during the neutralization reaction of an acid and a base under standard conditions. It is always a negative value. (ans) (c)_ The standard enthalpy change of solution is the change in heat energy when one mole of a substance is completely dissolved in excess solvent under standard conditions. The amount of solvent must be large enough such that the addition of further solvent will produce no further heat change. If the standard enthalpy change of solution is a very positive value, the compound is insoluble in water. If the standard enthalpy change of solution is a very negative value, the compound is soluble in water. (ans) (4) The standard enthalpy change of formation is the enthalpy change when one mole of compound is formed under standard conditions from Cone mole of its constituent elements in their standard state. If the standard enthalpy change of formation is a negative value, it means that the compound is energetically more stable than its constituent elements and vice versa. (ans) (c) The standard enthalpy change of combustion (or the heat of, combustion) is the enthalpy change when one mole of compound reacts completely with excess oxygen under standard conditions. The standard enthalpy change of combustion is always a negative value as heat is always evolved. (ans) © Note that standard conditions re pressure of 1 atm, temperature of 298 K and the substences ore in ther mos stable physical form. (f) A thermochemical equation is an equation that provides the amount of, reactants and products (in moles) and the quantity of energy involved. (ans) 5 eemialenwete 5-3aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.(b) Relevant AH values for the reaction that syrthesises methanol are given in the table. Ole) -394 CHOHIe) =201 H,0(8) 242 (i) Use these values to calculate AM’ eacton for this synthesis of methanol. Include a sign in your answer. CO,(g) + 3HAg) = CH30H(g) + 42018) (i) Suggest one possible environmental advantage of this reaction. Explain youranswer, [5] (c)__The synthesis of methanol is carried out at about 500K with a pressure of between 40 and 100 atmospheres (between 4 x 106 Pa and 10 x 107 Pa) and Using a catalyst. The use of such conditions will affect both the rate of reaction and the equilibrium yield. In the spaces below, explain the effects of higher temperature, higher pressure, and the use of a catalyst on the equilibrium yield of methanol. higher temperature ~ effect ~ explanation higher pressure ~ effect ~ explanation use of catalyst ~ effect ~ explanation [6] (Total: 14] (a) C(s) +Onlg) > CO2(g) () the enthalpy change/energy change/neat change when ‘one mole of a compound/CO, (1) is formed from its elements in their standard states QB (b) (i) CO,(g) + 3g) = CH;OH(g) + H20(8) AHp/kimot? 394 0 201-202 MH pacson = 201 + (-242) — |-394) a 49 kJ mol (ay correct sign (i) (il) removal of CO, from the atmosphere ie CO; is a greenhouse gas/causes global warming (1) (5) (0) Inthis part, in each case, the ‘effect’ must be correctly stated in order to gain the explanation mark. higher temperature Yield is reduced/equilibrium goes to LHS () forward reaction is exothermic/reverse reaction is endothermic (1) 5 eemialenwete 5-7aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.640 Mecls) Mig + 148 4-738 +1650 + 243 — 2(349) =-640 MMi =-2521 kJ mol” (ans) Bamples When an ionic solid dissolves in water, two steps are involved, Firstly, the crystal lattice breaks down to form isolated gaseous ions (\H.), and secondly, the ‘gaseous ions are hydrated (Aya). Sketch the enthalpy cycle of the dissolution of ‘NaC! crystals in water. Solutio a5 ba? 5 5 Na‘) ——“ + na'fag)+cr"tea) Ss na‘(g)+ cre) MH May fans)aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Content 61 Redox processes: electron transfer and changes in oxition number (oxidation state} 62 Electrode potentials |i) Standard electrode (redox) potentials, the redox series lit) Standard cet potentials, £°.4, and their uses [it) Betteries and fuel eels 63 Flectrolysis |i) Factors affecting the amount of substance liberated during electrolysis lil) The Faraday constant; the Avegadro constant; thet relationship Iii) Industrial uses of eleetraiysis Learning Outcomes Candiates should be ableto: (a) describe and explain redox processes in terms of electron transfer and/or of changes in oxidation number (oxidation stato) (b) define the terms: (i) standard electrode (redox) potentia! (i) standard cell potential (©) describe the standard hydrogen electrode (4) describe methods used to measure the standard electrode potentials of (i) metas or non-metal in contact with their ions in aquecus selution (i) ons of the same elementin diferent oxidation states, (@) calculate a standard cell potential by combining two standard electrode potentials (0) use standard call potentials to (i) explain/deduce the direction of electron flow from a simple cell (i) predict the Feasibility ofa reaction (@ understand thelimitations in the use of standard cell potentials to precict the feasibilty of a roaction (h) construct redox equations using the relevant half-equations (see also Section 9.4) (predict quaitatwely how the value ofan electrode potential varies with the concentration of the aqueousion (state the possible advantages of developing other types of celle. the H./0; fue cell and Improved batteries (a in electric vehicles in terms of smaller size, lower mass and higher voltage (state the relationship, the chargeon the electron (0 predict the dertity of the substance liberated during electrolysis trom the state of électralyte (moten cr aqueous), postion inthe redox series (electrode potential) and concentration () aleulate: {the quantity of charge passed during electrolysis (i) the mass and/or volume of substance liberated during electrolysis, including those in the electrolysis of H:S0,(aq); Na;S0,(aq) (0) explain, interms ofthe electrode reactions, the incustral processes of: Je, between the Faraday constant, the Avogadro constant and (the anodlicing of aluminium (i) the eectrolyticpurification of copper [technical detals are not required] © leroehenry 6-1aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.‘Oxygen has a less positive E° value, thus itis produced at the anode. (ans) (c)_ The ions present are Cu", SO,”, H* and OH”. Cathode: Cu"(aq)+2e > Cu(s) =1034V 2H'(eq) +2e > Hale) BP=0v cu” has a more positive E° value, thus it is reduced at the cathode. Anode: $,05" +2e > 250," P=1201V 0,(g)+2H,0|l) +4e" > 40H (aq) = +0.40V Asthe copper electrode is not inert, it may dissolve to form copperttl) ions. Cus) —> Cu” (aq) +2e” =-034V Copper has the least positive E° value, thus it is oxidized at the anode. (ans) Examale 6 ‘Aqueous sulfuric acid is electrolysed using a graphite anode and an inert cathode. (a) Give the equations for the reactions at the electrodes. (b) If an inert anode is used, find the ratio of the products formed. Solution (a) Cathode: 2H"(aq) +2e” -> Hg) Anode: 40H (aq) — O2(g) +2H;0(I) + 4e- ‘The oxygen gas produced reacts with the graphite electrode to form carbon monoxide and carbon dioxide. 2Cig) + O.{g) > 2COjg) Clg) +02 > CO{g) ans} (b) fan inert anode is used, the overall reaction will be: 4H"(aq) + 40H (aq) > 0,{g) + 2H,0(I) + 2H,(e) Oxygen gas, water and hydrogen gas are formed ina ratio 1:2:2. (ans) Example 7 Calculate the time needed to deposit 100 g of silver when a current of 10 Ais passed through silver nitrate solution, Solution: Relative molecular mass of silver = 107.9 Amount of silver deposited = °°. =0.92678 mol (5 sf) Quantity of electricity needed = 0.92678 x 96500 = 89435 C (to S sf) Time needed 2985 = goad s = 2.48 hr (3 sf) (ans) 6-2 (hemsey~ Chaleging (BEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Calculate the E°.,) for the concentration cell containing silver ions at concentrations of 1.0 mol dm? and 0.001 mol dm” Give the equations of the reactions at the cathode and anode for the following, electrochemical cells. (2) Molten NaC/ using graphite electrodes (b) Na,S0.(aq) using graphite electrodes 7. Contacts of electronic circuit boards with a surface area of 1.2 cm’ are often coated with gold. The complex K[Au(CN):]is used as a source of Au’ ions in the electroplating process where a current of 0.60 A is passed through the electrolyte bath. Assuming 100 % current efficiency, calculate the time taken to deposit a layer of gold 3 x 10 * cm thick on the contacts of the circuit board. [Density of gold =19.3 g cm *] a 8. Calculate the Avogadro constant when a current of 0.25 A was passed through dilute aqueous sodium chloride for 32 min 10s. 56 cm” of gas was evolved at the cathode at stp. a 9. Chrome yellow (PbCr0,) is a yellow pigment used in oil paintings. Its colour changes when the painting is exposed to an atmosphere containing sulfur dioxide (a) Suggest a reason for the colour change using the data provided below. SO, +4H' +2e = $0,+2H,0 — £°=40.17V CrO, + 8H" +3e° = Cr +40 = 41.33V (b) State the colour change and explain why this colour change takes a long time to occur. a (hemsey~ Chaleging (BEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Example 2 Define degree of dissociation. ‘Solution: ‘The degree of dissociation is defined as the fraction of molecules that dissociate into ions. It determines the relative strengths of the acids. Strong acids and bases show @ high degree of dissociation while weak acids and bases show a low degree of dissociation. (ans) © The strength of an acids aiferent from the concentrotion of an acid The strength is determined by the degree of dissociation while the concentration is defined in terms ofthe ‘number of motes per unit volume. Therefore, a sirong acidcan be a diluted one white weak acid can be concentrated, Example 3 Calculate the pH and degree of dissociation, «, of a0.01 M week acid HA given that its Ky = 1.8 x 10. Solution: Kk, aio $ Kyexd = az J = a= x 0.01 x= 0.0424 (3 sf) (ans) we ‘ 5 Ky= = IH Yak, = (001)(1.810°) ¥ [1] =4.24 x 10“ mol dm? pH = ~log,» [H'] = 3.37 (ans) Eeample 4 The pH of a solution can be measured using indicators and pH meters. Calculate the pH of the following solutions at 25°C. {a) 2.010 *MOH (b) 0.5 MH" Solution PH = -logi0 [H'] ios (a) H)= 1.0x10 = 20x10 = +logi0 [H’] = “logo (5.0 x 10 ) = 11.3 (3sf) (ans) =5.0%10"%M 10810 [H'] = ~logio (0-5) = 0.301 (3 sf) (ans) 7-10 (hemsey~ Chaleging (BEaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.To check that the approximation is valid, we can compare the values of x and [HOCIo. 4 *—,.390% = £73210". s00%6 = 0.115% {HoOcI] 1s Since the expression is less than 5%, the value of x can be considered small enough that the approximation is valid. (b) The pH of the water should not be kept too low so it does not irritate the swimmers’ eyes. (ans) Example 6 ‘The pH fora weak acid, hydrofluoric acid, is 3.2. Calculate the dissociation constant of a 0.05 M solution of the acid. Solution: Initial concentrations: [HF lo. [H]o=0 [Flo =0 .05 M Let x be the change in concentration of HF that is needed to attain equilibrium. The equilibrium concentrations become: [HF] =0.05-x [H]=0+ [F]=0+x=x =x pH= 3.2 =-logio [H] [H'] = 6.3096 » 10° (to 5 sf) «- WUE] __x THE] (0.05=x 0.05 6.309610") é k= 7.96 «10813 54) fans) 0.05 Example 7 (a) Define buffered solution. (b) Explain how a buffered solution works. (c)_ Give an application of buffer solutions in daily life. Solution (a) A buffered solution is one that resists a change in its pH when either hydroxide ions or protons are added. There are two types of buffer solutions. The first type is the acidic buffer which has a pH less than 7 and is made by mixing a weak acid with the (hemsey~ Chaleging (BE(b) (2) sodium (or potassium) salt of that acid. The second type is the alkaline buffer which has a pH greater than 7 and is made by mixing a weak base and the salt of that base. (ans) A butfered solution contains a weak acid (or base) and its conjugate base (or acid) in approximately equal concentration, Suppose a buffer solution contains a large amount of a weak acid HA and its conjugate base A’. When hydroxide ions are added, the following reaction takes place. HA+OH > A +H,0 ‘The hydroxide ions react with HA to form A”, thus the concentration of hydroxide ions in the solution does not increase. Using the expression for the dissociation constant, ,-I) [ra] = IWI1=K7 THA) [a] [Ha] The pH ofthe solution i determinedby M4] wnen nydroxde ons are [*] [na] added, [A"] increases and the ratio ++ decreases, However, ifthe Ie] amounts of HA and A” are very large compared to the amount of hydroxide [HA ions sdees: om wnanse wean’ fl einmaan Thos prramanewenay Ie] constant and the pH is unchanged. Similarly, when protons are added to the buffered solution, it will react with A to form HA, thus the protons do not accumulate in the solution. There will be an increase in HA, but once again, if the amounts of HA and A are very large compared to the amount of protons added, the pH will have virtually no change. (ans) Our blood pH is maintained by a buffer system. The main buffer system in blood consists of hydrogen carbonate and carbonic acid. Blood can absorb the acids and bases produced in biological reactions without changing the pH. This is very important as cells can only work in a small pH range. When an acid enters the blood, the additional H;0" ions are removed by the HCO,~ions to form carbonic acid and water. Carbonic acid is unstable and decomposes to form water and carbon dioxide which is removed by the lungs. The pH of the blood remains virtually constant. When a base enters the blood, the hydroxide ions are neutralized by the carbonic acid molecules, thus the pH remains unchanged. (ans) 7 sia ra(a) A buffered solution contains 0.5 M NH; and 0.8 M NHACI. Calculate the pH of this solution if the K, of NH3 is 2.0 x 10°. {b) Calculate the pH of the solution if 0.2 mol hydrogen chioride gas is added to 2fof the buffered solution in (a). Solution (a) NH3(aq) + H20(1) = NHa'(aq) + OH (eq) [OH JINH,'] Ky=2.0 x10 INH] Initial concentrations: [NH3]o= 0.5 M INH. )=0.8M [OH Io Let x be the change in concentration of NHs that reacts with H.0. The equilibrium concentrations become: INH] = 0.5 —x INH, B+x [OH ]=0 +. Substituting these values into Ki: [OH JINH,”] _ (0.8 20x 10%= ae INH3] 0: x=125 10° [OH] =x=1.25 x 10° POH =—log(1.25 x 10°*) = 4.9030 (5 sf) pH = 14,00 ~ 4.9030 =9.10 (3 sf) (ans) (b) When HC/ig) Is added, NH, will react with It in the following reaction: Nii(aq) +H"(2q) > NH,'(aq) Initial amounts: [NH,]o= 2(0.5) = 1 mol tH), INH,"}, = 2(0.8) = 1.6 mol .2 mol From the amounts, it can be seen that H’ is the limiting reactant. Amount of NH3 and H’ used is 0.2mol each. Amount of NH,’ produced = 0.2 mol Amounts after reaction: INH3] = 1 - 0.2=0.8 mol [H']=0 mol CGhemsry~ Caleging (BE =INH] =1.6 +0: =18 mol Concentration after reaction: INH. 04M oom Using the Henderson-Hasselbaich equation, pH =p, + log) [ire [mw =8.95 (3sf) (ans) Note that the change in pH is minimal, asis expected of a buffer solution. Brampled) (2) Explain how to determine the equivalence point of an acid-base titration using an acid-base indicator. (0) A few drops of an acid-bese indicator HIn (K, = 2.9 10*) where Hn is yellow and In- is blue, is added to 50 cm? of 0.2 M NaOH. (i) State the initial colour of the solution. (ii) The solution is titrated with 0.2 M HCI. Determine the pH at which the solution will change colour. Solution: (2) An acid-base indicator works by marking the end point ofa titration by changing colour. It isimportant to choose the right indicator will ensure that, the equivalence point of a titration is virtually the same as the end point. (ans) (b) (i) The solution is blue intially. (ans) Ww [ft “ nolL) Ie] [Hin] [im] 4 ‘Assuming that the colour change is visible when [Hin] 10" ‘i K=1.0« 10" i] 40 [H']= 1.0 107 pH = log(1.0 x 10 ‘Therefore the colour change will occur at pH 7. (ans) 7 sia 7-15aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.pH = log 0.025 = 1.60 (3 sf) ‘When 100 cm’ of NaOH has been added, 50 Number of moles of HC/ before reaction = ——-(0.1) 1000) = 0.005 mol 100 Number of moles of NaOH before reaction = <> (0.05) 0,005 mol Number of moles of HC/ after reaction = 0.005 — 0.005, O mol Number of moles of NaOH after reaction = 0 mol t= x1000 =0m 150 pH = When 150 cm? of NaOH has been added, Number of moles of HC/ before reactio = 0.005 mol Number of moles of NaOH before reaction = sop (008) =0.0075 mol Number of moles of HC/ after reaction = 0.005 — 0.005 O mol Number of moles of NaQH after reaction = 0.0075 0.005 .0025 mol 0.0025 [oH] 1000 = 0.0125 M 200 a4 twy= 2280 — 50x10 0.0125 pH =—log(8.0 x 10°) = 12.1 (3 sf) When 200 cm’ of NaOH has been added, 50 Number of moles of HCI before reaction = (0.1) 1000 = 0.005 mol Number of moles of NaOH before reaction = ° (0.05) 1000 =0.01 mol Number of moles of HC/ after reaction = 0.005 — 0.005 =0 mol Number of moles of NaOH after reaction 0.01 ~ 0.005 = 0.005 mol 7 sia ar0.005 [oH] = “1000 = 0.02 M 7250 1.010 » Wy] =? — =50x10 0.02 —log(S.0« 107) =12.3 (3 sf) Pl The graph looks like this: pH aa 2 50 100 150 200 Volume of NaOH added (em") (b) The pi curves changes very gradually at first as there is a relatively large ‘amount of H’ at first, and addition of OH” results in a small change in pH. When the titration is close to the equivalent point, there is a large change in pH. This is because near the equivalence point, the amount of H" is relatively small, s0 addition of OH” will result in a large change in pH. (ans) ‘The indicator end point and the titration equivalence point should be as close as possible. In this case, bromothylmol blue is the most suitable indicator. The other two indicators are not suitable. (ans) Example 11 (a) Define solubility product (b) State the solubility product for the reaction CaCO,(s) = Ca*(aq) +C03* faq) (a) Solubility product, Ky is defined as the maximum number of undissociated ions, of an electrolyte in a saturated selution, capable at a given temperature of remaining in equilibrium with the undissolved phase of the solution. (ans) (b) Ky [Ca”1{C0,"] mol’ der-® fans) © tes onl affected by changes in temperature and gereraly the solubility product increases when the tenperatureis increase. © The sotpitty product will have afferent units depending on the power of the concentration terms. 7-18 (hemsey~ Chaleging (BEEE trample 2 The solubility product is commonly used to predict precipitation. state the relationship between solubility product, Kp and ionic product for the solution to be: (@) saturated (b) unsaturated (c)_ precipitated (2) Kp = ("1 1B°T” (ans) (b) Kp > lA" IBY)” (ans) (2) Keg STA“ IBY (ans) Example 13 (a) State the common ion effect. (b) Explain how the common ion effect affects the: (i) precipitation of metallic hydroxides (i) precipitation of metal sulfides (a) The common ion effect is defined as the reduction of the solubility of a sparingly soluble salt if the solution already contains one of the ions. (ans) (b) ()) When ammonium salts (NH, ) are present, only metal hydroxides with very low K., values will be precipitated. Thisis because the ammonium ions are common ions and thus reduce the Ionization of ammonia. Thus the ionic product cannot exceed the K, value and precipitation cannot occur. (ans) (i) When acids are present, only metal sulfides with very low Ky, values will be precipitated, e.g. Group Il metals. When bases are present, only metal sulfides with very high K.p values will be precipitated, e.g, Group IV metals. (ans) Example 14 (2) Silver iodide has a solubility of 1.2 x 10°* mol/L at 25°C. Calculate the Ky value. (b) Zinc carbonate has a solubility product of 2 x 10" at 25°C. Calculate its solubility at 25°C, (€) Calculate the solubility of BaF: (Kp = 2.4 x 10°) ina 0.01 M NaF solution. 7 sia 7-19aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.(b) (i) increasing temperature Yield of NO is decreased or reaction moves to LHS (1) forward reactions exothermic (1) (il) decreasing the pressure yield of NO is increased or reaction moves to RHS (1) more moles/molecules of gas on RHS or fewer moles/molecules of gas on LHS wf {c)_ let AH,” for NO be y KI mol * 4NH3(g) + SO,{g) = 4NO(g) + 6H,0(g) AH? 4x (-46.0) ay 6 x (-242) « AH ction = 4y + [6 x (-242)] - [4 x (-46.0)] (1) =4y- 1452 +184 actos 5 -906 kImol™* so 4y =-906 + 1452-184 = 362 () Hence y = AH° for NO = +90.5 ki mol” +sign is required (1) fa) [Teachers’ Comments] The ability to apply both Le Chatelier’s Principle and Hess’ Law correctly isimportant to success in A-level chemistry. There were many goad answers to (a) and (b) but (c) was less well answered with a significant number of candidates struggling with the calculation. (2) Many candidates confused K-and K, offering a K, expression involving square brackets which represent concentration in mol dm*. Those candidates who gave a correct expression fork, in terms of partial pressures Usually gave correct units for Kp, (b) Both parts of this question were generally well answered with good explanations in terms of Le Chatelier’s Principle. (6) While there were many fully correct answersin this part, there was a significant number of candidates who were awarded very little credit. The most common error was to not give a sign in the answer as the question required. Some candidates did not use the 4 and/or 6 from the stoichiometry of the equation in their algebraic equation. 7 esa| 7 Standard Problems 1. Explain how the following factors can affect the equilibrium of a system. Illustrate with reference to the endothermic reaction Nolg) +O.(e) = 2NO(g) (a) Concentration (b) Temperature (6). Pressure 2. Forthe reaction: (CH,CH,OH(!) + CH3CO,H(I) = CH5CO.CH.CHa(!) + H.0(!) Calculate the mass of ethanoic acid that must be mixed with 2.0 mol of ethenol to produce 1.5 mol of ethyl ethanoate at equilibrium, A(g) and B(g) react reversibly to form Clg), (a) From the graph below, deduce the equilibrium constant, K, for the reaction. ¢ 38h ae fos 5 ae) Eo 2 Cle) Boz 3 1 0 Time/min (b) Compare the rates of forward reaction and backward reaction at the 5” min and the 20" min. (c)_ If the same amount of A(g) and B(g) are allowed to react in a closed container half the size of the original one, will the amount of C(g) produced be the same? In the Contact Process, the reaction between SO,(g) and O2(g) is the key stage in the manufacture of sulfuric acid. 250,(8) + Ox(8) = 250;(8) AH: What factors are required for the high yield of sulfur trioxide? =197 J mol * {a) Explain why Mg(aq) ions gives a precipitate of Mg(OH)2 when dilute NHs(aq) is added, but no precipitate will be formed if ammonium chloride is first added. (b)_ Explain why Mg” (aq) ions will form a precipitate of MgS with H,S(aq) in alkaline conditions but not in acidic conditions. a 7-26 (hemsey~ Chaleging (BE6. Asolution contains two weak acids, HNO; and HOC/, both of concentration 2 M. Calculate the pH of the solution if the , of HNO; is 2.0 x 10"* and the K, of HOC/ is 2.0 x 10%. @ 7. Ammonia is a weak base. Calculate the pH of a2 M solution of ammonia if the Ky is 5 2.0 x10 B. HNO, a weak acid, is titrated with 0.1M of NaOH to determine its K, value. 0.01 mole of the solid acid was dissolved in 50 cm’ of water. After 10 cm’ of NaOH was added, the pH of the solution is 1.5. Calculate the K, value. a 9. Ata particular temperature, 75% of the sulfur trioxide dissociates, producing a pressure of 5 atm. Calculate K,. 10. Explain how buffers work using a solution of ethanoic acid and potassium ethanoate as an example of an acidic buffer, and a solution of aqueous ammonia and ammonium chloride as an example of an alkaline buffer. 11. Determine which of the following acids is most suitable for preparing a buffered solution of pH 5.5. (a) Acid A(K,=2.0 x10) (b) Acid B(K=2.0 x 10) (cq) Acid ¢ (K,=2.0 x 10°) 12. Calculate the pH of the buffered solution containing (2) 0.02 M sodium ethanoate ané 0.01 M ethanoic acid (K, = (b) 1M HNO; (K,=2.0 x 10 *) and 1M NaNO, 8x 10°) 13. Describe how to prepare an acidic buffer solution of pH 3.5. (Use methanoic acid, which has a pk, value of 3.75.) 14. (a) Sketch pH graphs to compare the change in pH when a strong acid is mixed with a strong base and a weak base respectively (b)_ Sketch pH graphs to compare the change in pH when a weak acid is mixed with a strong base and a weak base respectively. (q)_ State the effect on pH graphs of using dibasic and tribasic acids in titrations instead of monobasic ones. 7 sia ra15. HPO, is @ tribasic acid which ionizes in three stages to form, H;PO¢ (aq), HPO," (aq) and PO," (aq). (0) Give the three equations for the ionization of the acid (b) H2P0,"(eq)is amphoteric. State its conjugate acid and conjugate base. (c)_ Explain why the dissociation constants K, decreases with successive ionization stages, (d) Sketch the pH curve to show the neutralization of H3PO, with aqueous sodium hydroxide. 16. (a) Determine if a precipitate will form if equal volumes of 3.3 x 10° mol dm? nickel((l) sulfate and 4.1 x 10° mol dm * sodium hydroxide are mixed. [Kap of nickel!) hydroxide = 60 x 10° mol? dm (b) Calculate the volume of water required to dissolve 1 mol of nickel(I!) hydroxide if pH 5.2 is maintained a 17. Propane and butane form an ideal solution, Calculate the total pressure and mole fraction of propane in the vapour in an equimolar mixture of propane and butane at, 298 K. [vapour pressure of propane = 29.5 kPa; vapour pressure of butane = 10.2 kPa at 298K] 18. An organic liquid is distilled with steam at 90.5°C and 101 kPa. The distillate was found to contain 75% water by mass. Calculate the relative molecular mass of the organic liquid given that the vapour pressure of water at 90.5°Cis 97.8 kPa. 19. Given that the partition coefficient of a substance Z between methylbenzene and water is 12, Z being more soluble in methylbenzene than water. Calculate the mass of Z that will be extracted from 200 cm’ of an aqueous solution containing 8 g of Z by (a). shaking with 50 cm’ of methylbenzene, (b) shaking successively with two separate 25 cm’ portions of methylbenzene. (hemsey~ Chaleging (BE7 Standard Solutions 1. (2) When the concentration of a reactant or a product in an equilibrium system is changed, the equilibrium is affected as the rates of the forward and backward reactions are no longer equal. Thus the concentrations of the species in the system must change such that the rate of forward reaction is once again equal to the backward reaction. A change in concentration does not affect the value of the equilibrium constant, K. For example for the reaction Na(g) + 02g) == 2NO(e), IFN2 is added at constant volume, there will be an instantaneous increase in the concentration of N; and the rate of forward reaction also increases. The concentration of NO increases while the concentrations of Nz and Op decrease. This causes the rate of forward rate of reaction to decrease and the rate of backward reaction to increase until the two rates are equal gain. ‘The result is a shift in equilibrium to the right. Alternatively, if the concentration of Nj is decreased, the equilibrium shifts to the left. (ans) (b) When the temperature of a system is increased, the rates of both the forward reaction and the backward reactions will increase. However, the increase in rate will not be the same for both reactions as the activation energies are different, For a reaction with high activation energy, a temperature increase will result, ina significant increase in the proportion of molecules with energy greater than the activation energy. For a reaction with low activation energy, a temperature increase will result in a small increase in the proportion of molecules with energy greater than the activation energy, as most of the molecules already possess the required energy. An increas in temperature will cause a greater increase in reaction rate for 2 reaction with higher activation energy. ‘Thus the rate of forward reaction Is no longer equal to the rate of backward reaction and the equil rium must shift so as to make the rates equal again Acchange in temperature will change the value of the equilibrium constant, k. For the endothermic reaction Nig) +0,(g) <> 2NO(g), ifthe temperature of the system is increased, the ecuilibrium will counter the change by absorbing the added heat, therefore the equilibrium shifts to the right. Conversely, if the temperature is decreased, the equilibrium will counter the change by producing more heat, therefore the equilibrium shifts to the left. fans) 7 sia 7-29(ii) There are two ways in which pressure can be applied to a system — by physical compression and by addition of an inert gas. The equilibrium constant, k, is not affected. If the partial pressure of only one of the gases in the equilibrium mixture is changed, the effect is the same as the effects resulting from changes in the concentration of one species. For the reaction Ni(g) + Ox{g) = 2NO/e), = Pua)? (Py, NP) If the partial pressure of Ny is increased, itis equivalent to an increase in the concentration of N2 and the rate of forward reaction also increases. To counter the change, the equilibrium shifts to the right. Ifthe total pressure is changed, the equilibrium position of the system will also be changed. For the reaction Nu(g) +0.{g) = 2NOIe), (yo)? Pe Pay Mo, If the total pressure is doubled, the equilibrium will shift ina direction that will decrease the total number of moles of gases. Conversely, if total pressure Is decreased, the equilibrium will shiftin a direction that increases the total number of moles of gases. In this reaction, the number of moles of gaseous reactants is the same as that of the gaseous products, thus a change in pressure will have no effect on the equilibrium position. (ans) © The presence of acatayyst does rot offect the equilibrium constant; t only speeds up the rate of ection. a 2. Letx be the number of moles of ethanoic acid required. The equilibrium concentration can be represented as follows: [CH3CH,OH] =2.0 15 [CH3CH,OH], = 0.5 [CH,COsH]o=x -15 [CHsCOsH]_=x-1.5 ICHsCO.CHCHslo =0 15 [CH;CO,CHCHsJe=1.5 [H.0}o=0 1s (H20]e=15 Substituting the equilibrium concentrations into the equilibrium expression: [crcoycr,c¥ 40] [CHCH,OH][CH,CO,H] (hemsey~ Chaleging (BEwhere = volume of the vessel (dm°) Mass of ethanoic acid = 2.625 x [12.0 + 3(1.0) + 12.0 + 2(16.0) + 1.0] = 158 g (ans) 3. (2) From the graph, it can be seen that one mole of A(g) reacts with 2 moles of B{g) to form 1 mole of C(g) a Al alley (b) At the 5" minute, the rate of forward reaction is greater than the backward reaction as C(g) is being produced. (ans) (ans) At the 20" minute, the rate of forward reaction is equal to the rate of backward reaction as the concentration of C(g) remains constant. (ans) (c)_ The amount of Cig) produced will increase. A decrease in volume will increase the total pressure. By Le Chetelier’s principle, the equilibrium will shift to the right as there is a lesser number of moles of gas. (ans) 4, To obtain a high yield of sulfur trioxide, the air used to burn sulfurhas to be clean and free of impurities. Impurities in air will poison the catalyst, causing it to be ineffective. The catalyst has to be cooled, thereby shitting the position of equilibrium to the right. This increases the yield of sulfur trioxide. The reacting gas mixture must contain an excess of air which would serve also to shift the position of equilibrium to the right, increasing the concentration of sulfur trioxide. (ans) rr 5. (a) NH3+H,O = NH,’ + OH” Me” (aq) +20H (aq) —> Mg(OH)> When only dilute NH,(aq] is added, Mg(OH), is precipitated as the ionic product exceeds the Kip value, NHAC! > Ne +C/~ When ammonium chloride is first added, the ionitation of dilute NHs(aq) is reduced due to the common ion effect and the amount of OH is reduced. Thus the ionic product cannot exceed the Kp valve and precipitation cannot occur. (ans) 7 sia 7-31aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.7. The major species in solution are: NH3(aq) + H20(I) => NH,'(aq) + OH (aq) Ky =2.0x 10° H,0()) = H’(aq) + OH (aq) Ky =1.0% 10 ‘As ammonia is a stronger base than water, the contribution from water can be considered negligible. Initial concentrations: INH3} = 2M INHe'}o =0. [OH =0 Let xbe the change in concentration of NH; that is needed to attain equilibrium. ‘The equilibrium concentrations become: [we] =2—x [Wiig] <0+x=% fo] =0+K=% ke=2.0 «105 = OM IINHs] x ° INH) =x 2 3246 x 10-°(5 sf) le 10x10" w= = Ae 2OM10 Ly seni x 10 "(5 sf) OH 6.3246 10° pH =-log(1.5811 x 10") =11.8 (3 sf). (ans) To check that the approximation is valid, we can compare the values of x and INHs). 3 *_..90% = £:3246%10" 90% = 0.316% INH,} 2 Since the expression is less than 5%, the value of x can be considered small enough that the approximation is valid = ES 8, HNOaq) + OH (aq) > NO; (aq) +H,0(l) Amount before reaction: HNO,=0.01 mol on = (0.1) ~ 0.002 1000 Amount after reaction: 7 sia 7-33[vor] [HNO,] K Initial concentrations: [HNO,Jo= ——(1000) = 0.15M. 60 INO, J, = 0.0167 M {H Let x be the change in concentration of HNOs that is needed to attain equilibrium. Equilibrium concentrations: [HNO] (No, ]=0.0167 +x tH 10" = 0.031623 M (5 sf) osx [H’ [Now] _ (x(0.0167+x)_o.0267% THNO,, o15-x 015 = 0.00352 (3 sf) (ans) a 9. The reaction can be represented by: 2503(g) <= 250%(6) + Ox(8) ‘Assuming that there are 2 moles of SO; to begin with: 2803(g) == 280g) + ~——O24a) Moles at t= 2 0 0 Molesat equilibrium 0.5 as 0.75 05. 45 0.75 Mole fraction 054154075 054154075 054154075 =0.181 545 =0.272 Partial Pressure 0.181 «5=0.905 0.545 x5=2.73 0.272x5=136 (Po. } [%,] _ (2.73)°(.36) e 2 [Ao, | (0.905 = 12.4(3 sf (ans) a Gomi — Clana BE =10. For the acidic buffer, Ethanoic acid is partially dissociated. CHsCOOH = CH3COO +H Potassium ethanoate is fully dissociated. CHjCOOK —> CH;COO” +k" When H' ions are added, they are removed by CHsCOO” so that the pH remains virtually unchanged. H’ +CHsCOO” = HCOOH When OH ions are added, they are removed by CHCOOH so that the pH remains virtually unchanged. OH” + CHSCOOH <= CHsCOO™ +H. For the alkaline buffer, ‘Ammonia is partially dissociated. NH3+H20 <= NH,’ + OH” Ammonium chloride is fully dissociated. NHACI > Nia" +C/~ When H" ions are added, they are removed by NH so that the pH remains virtually unchanged, HY ANH = NHS When OH ions are added, they are removed by NH,’ so that the pH remains virtually unchanged. OH +NHg! = NH3+H,0 (ans) 11, From the Henderson-Hasselbalch equation, [x] = pK, + log] $= pA =pkt lol Tia) itcan be seen that the most effective buffering will occur when [HA] is equal to fa}. pH =-loglH'J=55 [H'] = 3.1623 x 10° soctunen tl oot LAL Use the expression [H'] i] tocalculate the ratio of H—> for each acid. A [*] 7 esaHi (a) 3.1623 « 10° = rome fl) a] | py = 158 fe] [Ha] fe (c) 3.1623 « 10 °= 2.9%10 ara al = 0.00158 fe] [Ha] Since the [] ratio for acid 6 Is closest to 1, it should be the acid used in the i buffered solution. (ans) a (salt) 12. (a) pH =pk,+ (loo tt “Hogyo (2.8 « 10-5) + loto( 222) pH =5.05 (3 sf) (ans) (b) HNO,faq) = H’(2a) +NO; (aa) =20x19¢= MUNOL [HNO,1] Since HNO, and NaNO: are present in relative large amounts, [HNOd = [HNOs}o=1M [INaNO;] =(NaNOz}o=1M (ans) tH) = (4, AN] - (2.0.10")4 =20 x10 10, 1 pH =-log(2.0 x 10*)=3.70(3sf) (ans) Alternatively, using the Henderson-Hasselbalch equation, [no] (2 H = pK, + log] ——~+ | = 3.70 +1og| ~]=3.70 (ans pH= pI hal (3) (ans) a (hemsey~ Chaleging (BE =" 13. p= Dk, + lon Fa) Substituting the values of pH and pK, A 35 =3.754 "08. Fra] f«] = 0.56234 (5 si) [Ha] From the ratio obtained, it can be seen that for every 1 mole of the acid used, 0.56234 mole of the corresponding conjugate base must be used. Therefore the mole ratio of methanoic acid : sodium methanoate =1: 0.562 (3sf) (ans) 14. (a) Strong acid with strong base Strong acid with weak base pH pH sat uy 2 2 10 10 8 8 /<— Equivalence point ‘ ° <— Equivalence point 4 4 2 2 Volume of acid Volume of acié (b) ‘Weak acid with strongbase ‘Weak acid with weak base cd pH af a 2 n 10 10 /<— Equivalence poi <— Equivalence point 8 8 6 6 4 4 2 2 ‘Volume of acid Volume of acid 7 sia 7-37(c). The titration curves for dibasic and tribasic acids have two and three inflection points respectively as there are more than one equivalence points. (ans) a SS 15. (a) H,POs/aq) +H,0(l) = H.0°laq) +H,PO, (aa) H,PO, (aq) + H20(I) => H,0°(aq) + HPO." (aq) HPO,” (aq) +H,0(I) = H,0"(aq) + PO,” (aq) (ans) {b) The conjugate acid is H3PO.(aq) and the conjugate base is HPO,” (aq). (ans) (c)_ The dissociation constant will decrease with successive ionizations. This is because after each hydrogen ion is removed, the remaining species will have an extra negative charge which increases the force of attraction of the hydrogen atoms. Therefore the degree of dissociation decreases. (ans) (d) Volume of N2OH(aq) added 16. (a) Ni(OH}.(s) = Ni*(aq) + 20H (aq) lonic product = [Ni*][OH (aa<10°) | (42x20) rs = 6.910" mol? dm > Nickellll) hydroxide is precipitated out since the ionic product exceeds the K,, value of nickel(II) hydroxide. (ans) (b) pOH=14-5.2=88 [OH] = 10°°* = 1.58 x 10° mol dm* lonic product ~ Ky (to dissolve nickel( I) hydroxide) [N*][0H"}? = 6.0 x 10° INi*1(1.58 x 10°) = 6.0 x10 [Ni] = 2.40 240 = 0.42. dm? [ans) 7-38 (hemsey~ Chaleging (BE =A, 47. Mole fractionof propane =0.5 Partial pressure of propane = 0.5» 29.5 = 14.75 kPa Partial pressure of butane =0.5 « 10.2 =5.1 kPa Total pressure = 14.75 +5.1 = 19.85 kPa 14.75 ‘Mole fraction of propane in the vapour = —— prope pour 79.85 =0.74 (ans) 18. vapour pressure of the organic liquid at 90.5°C = 101— 97.8 =3.2kPa ha MP ™ MP's Let A= organic liquid and B = water, 25 _Myx3.2 7518x978 Ma=1834 (ans) 19, (a) Let xbe the mass of Z extracted. Mass of Z rem ig in the aqueous solution = : Pla ae Ph. x=60g (ans) (b) On the 1° extraction, let x; be the mass of Z extracted. Mass of Z remaining in the aqueous solution = (8 ~ x) g fl. 7 esa 7-39fe x=48¢ On the 2” extraction, let x) be the mass of Z extracted. Mass of Z remaining in the aqueous solution =(8 ~ 4.8—x:) g =(3.2-m) 8 92.8 (ans) Total mass of Z extracted = 4.8+ 1.92 72g (ans) (hemsey~ Chaleging (BEContent 81 Simple rate equations; orders of resction; rate constants 82 Concept of activation eneray 83 Effect of concentration, temperature and catalysts reaction rate 84 Homogeneous and heterogeneous catalysis 85 Enzymes as biological catalysts Learning Outcomes ‘Candiates should be ableto: (0) explain and use the terms: rate of reaction; rate equation; order of reaction; rate ‘constant; hal-fe of a reaction, rate-determining step; activation energy; catalysis (6) construct and use rate equations of the form rate = KIAI"[" (limited to simple cases of single tep reactions and of multistep processes with a rate-determining step, For which ‘mand n are 0, 0F 2), Including (deducing the order of a reaction bythe intial rates method (i) Justitying, for zero- end fist-order reactions, the order of resction from concentration-time graphs (ii) verifying that a suggested reaction mechanism is consistent withthe observed kinetics (v)_ predicting the order that would result from agiven reaction mechanism (W) -caleuating an initia rate using concentration data [integrated forms of ate equations are not required.) (0 showunderstanding that the halfile ofa first-order reaction is independent of concentration (i) ase the native of a rst order reactions in calculations: (4) clevlate arate constant using the intial ratormothod (6) devise a suitable experimental technique for studying the rate ofa reaction, from given information (explain qualitatively, in terms of colisions, the effect of concentration changes on the rate of reaction (@) show understanding, including reference tothe Bottzmann distribution, of what is ment by the term activation energy (h) explain quaitatvely,n terms both of the Boltzmarn distribution and of collision frequency, the effect of temperature change on arate constant (and hence, onthe rate) of reaction (2 (explain that in the presence of a catalyst, a reaction has a diferent mechanism, i. one of lower activation energy, giving a larger rate constant (i) interpret this catalytic effect on arate constant in terms of the Beltemann Aistrivution (cutie the different modes of action of homogeneous and heterogeneous catalysis, snctuoing: () the Haber process (i) the catalytic removal of oxides of nitrogen in the exhaust gases from car engines (see also Section 10.2) (i) the catalytic role of atmospheric oxides of nitrogen inthe oxidation of atmospheric sulfur divide {v)_cataltic role of Fein the T/5;0,""reaction (8) describe enzymes as biological catalysts which may have specific activity (0 explain the relaionship between substrate concentration and therate of anenzyme- catalysed reaction in biochemical systems sc enw: aaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.1 Rate of reaction B «xe ——* [2(60)+25) RateofreactionA _ 145 Rateofreaction8 90 =1.61 (ans) Bramples Describe a method to follow the rate of reaction of the following reactions. (a) Decomposition of hydrogen peroxide 2H,0,(aq) > 2H,0(I) + 0,(8) (b) Alkaline hydrolysis of an ester CH,CO,C,H,(aq) +NaOH(aq) > CH,CO, Na"(aq) + C,HsOH(aq) Solution: (a) This reaction can be monitored by measuring changes in gas volume. A simple diagram is shown below. rubber bung. as sytinge T oxygen gas \— hydrogen peroxide manganese (WV) oxide catalyst ‘Some manganese(IV) oxide is added to hydrogen peroxide in a flask. As the reaction progresses, oxygen gas is collected in the syringe and the plunger of the syringe moves outwards. The volume of the oxygen is recorded at regular intervals after the start of the reaction. (ans) (b). This reaction can be monitored via the titrimetric method by determining. the amount of unreacted NaOH(aq) in the reaction mixture at different times. At various time intervals after the reaction has begun, a sample of the reaction mixture is withdrawn by pipette, and a large amount of cold water is added to ‘quench’ the reaction mixture. The dilution and cooling reduces the rate of reaction to almost zero. The reaction mixture is then titrated against an acid of known concentration with phenolpthalein as an indicator. The volume of unreacted NaOH(aq) can then be determined. (ans) a Examples Define the following terms. (2) Rate equation sc enw: a3aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Comparing experiments 2 and 3, [H,0;] and [H’] being constant, the initial rate is, doubled when [ I] is doubled. The reaction is first order with respect to I. Comparing experiments 3 and 4, [I ] and [H203] being constant, the initial rate is unchanged when [H"] is doubled. The reaction is zero order with respect to H Rate equation: rate =k[H,03]|I] (ans) Examples For the following reaction, experimental data was obtained as shown. 2N,0s(g) > 4NO2(g) + O2(8) 0.05 0.02 0.10 0.08 0.20 0.08 Find the rate constant for the reaction. From the information, it can be seen that as the concentration of N,O; varies directly with the rate of reaction, i.e, when the concentration of N,Osis doubled, the rate of reaction also doubles. AAs such, this i a first order reaction with respect to N,O., andits rate equation is: Rate = K(N,O.]* By substituting the values into the rate equation, 0.05 = k(0.02) 25h" (ans) Example7, Consider the reaction: A+ 28 —> products. The rate equation is: rate = MAILE] (2) State the overall order of reaction, and the unit for the rate constant. (b) The rate of reaction is x mol dm *s*, What will the new rate be if (i) The concentration of Ais halved, (li) The concentration of B is doubled, and (iil) The concentration of A is doubled and the concentration of Bis halved, assuming that all changes take place at the same temperature? Solutios (a) Overall order of reaction = 1+1 =2 sc enw: asaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.5 Concept of activation energy fundamental questions Baample (a) Explain the distribution of molecular speeds in a gas. (b) Define activation energy. (c)_ Sketch a Maxwell-Boltzmann distribution to show the variation of kinetic energy with temperature. Solution: (2) Ata given temperature, not all gas molecules are moving with the same speed, some faster and some slower. The kinetic energies of molecules are ‘not all equal. The fast moving ones have high kinetic energy, and they may have enough energy to overcome the reaction energy barrier E, ‘The Maxwell: Boltzmann distribution shows how the speeds (and hence the energies) of a mixture of moving particles varies at a particular temperature ‘An example is shown below. 4 Percentage of molecules Speed/ms* Some points to note: 1, There are no molecules at zero energy. 2, Few molecules at high energy. 3, For the reaction to occur, the particles involved need a minimum amount of energy ~ the Activation energy (E;). Ifa particle is not in the shaded area, then it will not have the required energy soit will not be able to participate in the reaction. 4, The area under the curve is @ nth measure of the total number of particles present. (ans) (b) Activation energy is defined as the minimum amount of energy required for areaction to occur. (ans) Percentage of molecules Speed/ms (c)_ From the graph it can be seen that at a higher temperature, the proportion of molecules with greater kinetic energy increases. There is also an increase in the proportion of molecules with energy equal or greater than the activation energy required for the reactions. (ans)Example 2 Given the following reactions: Reaction 1: CsH,C/laq) + NaOH{aq) —> C3H,OH(aq) + NaC/(aq) Reaction 2: HCi(aq) + NaOH(aq) — H,0(1) + NaCi(aq) {a) State and explain how the rate of reaction between C3H;Br and NaOH would compare to that of reaction 1. {b) Explain why reaction 1 must be heated before any reactions occurs while reaction 2 takes place almost instantaneously at room temperature. {e)_ Reaction 1is a second order reaction. Suggest how the rate of this reaction would be affected when the solution is diluted with an equal volume of solvent. Solution: (a) The reaction rate would increase as the C—Br bond is weaker than the C—C/ bond, and thus breaks more readily. (ans) (b) Inreaction 1, energy is required to break the C—C/ bond in C3H,C/ before a reaction takes place. In reaction 2, complete ionisation of HC/ and NaOH ‘occursin aqueous solution. Thus no bonds are broken. The OH and H’ ions ‘combine readily to produce water. As the activation energy of reaction 1 is higher than that of reaction 2, reaction 1 occurs only after heating whilst reaction 2 occurs almost instantaneously at room temperature. (ans) (c)_ The rate equation for reaction 1 is: rate = K[reactant]*. The concentration of reactant is halved when the solution is diluted with an equal volume of solvent. Therefore, the rate of the reaction would be a quarter of the original rate. (ans) a Example3 The energy profile of the reaction 2BrNO(g) —> 2NO(g) + Bra(g) is shown below. Activated complex Potentialenowy. Reaction progress {a) State if the reaction is exothermic or endothermic. (b) Use the transition stats theory to explain the formation of the activated complex. (c)_ Add in the following terms on the energy profile 1. Activation energy for forward reaction 2. Activation energy for backward reaction 3. Mofreaction (hemsey~ Chaleging (BESolution: (a) The reaction is exothermic as the products have less energy than the reactants. (ans) (b) The transition theory suggests that as molecules collide and reactions take place, they are momentarily less stable than either the reactants or the products, As energy is required to break the bonds between the atoms, the potential energy of the system increase and this results in an energy barrier that forms between the reactants and the products. An activated complex is then formed. (ans) () Potential energy Activated complex 2, Activation energy or backward 4. Activation energy for forward reactibn Reaction progressEffect of concentration, temperature sai and catalysts on reaction rate fundamental questions Example Using the collision theory, explain the effect of concentration changes on the rate of reaction. Solution For a reaction involving two species, they can only react if they come into contact with each other. They first have to collide, and then they may react. Secondly, it is not enough for the two species to collide — they have to collide in the right way, and they have to collide with enough energy for bonds to break. This is known as the activation energy. If the particles collide with less energy than the activation energy, no reaction takes place. They simply bounce apart. The activation energy is used to break the bonds inthe reactants and overcome the repulsive forces when the reactant molecules approach each other. When the concentration of the reactants increases, the frequency of collisions between the reactant particles will increase. The probability that the particles collide with the right orientation and with sufficient energy also increases. This, leads to an increase in the rate of reaction. (ans) Example 2 The endothermic reaction A(g) —> A’(g) isa single step reaction. In the presence of a catalyst, C, the reaction takes place by the following mechanism. Ag) +Cle) > ACle) AC(g) > A’(g) + Cle) Sketch the energy profiles for the reaction, with and without the catalyst. Solution For the uncatalyzed reaction: Potertial energy we) Ale) Reaction progross 8-10 homey ~ Chaleaing (BEExample? (2) Define heterogeneous catalyst. (b)_In the decomposition of hydrogen peroxide, manganese(|V) oxide is used as a catalyst. Explain how heterogeneous catalysts help to speed up the rate of reaction. Solution: (a) Aheterogeneous catalyst exists in a different phase from the reacting molecules, usually asa solid. (ans) (b) Heterogeneous catalysis usually involves gaseous reactants being adsorbed on the surface ofa solid catalyst. Adsorption is the build up of a molecule at a surface, Typically, heterogeneous catalysis involves four steps. 1. Adsorption and activation of the reactants. Reactant molecules are adsorbed at active sites onto the surface of the catalyst. This involves the formation of weak bonds between reactant molecules and the catalyst which causes other bonds in the reactant molecule to be stretched and weakened. This reduces the activation energy for the reaction. Adsorption is believed to increase the reaction rate in two ways. Firstly, as reactant molecules are adsorbed onto the surface of the catalyst, the bonds between the atoms in them are weakened, reducing the energy needed to break the reactant molecules apart. Secondly, the adsorbed molecules are held closely together on the metal surface, so the likelihood of a reaction occurring is much greater. 2. Migration of the adsorbed reactants on the surface. 3, Reaction of the adsorbed substances, Bonds between atoms begin to reform, producing product molecules. The catalyst effectively allows the activated complex to form gradually, as reactant molecules are adsorbed onto adjacent active sites, rather than requiring a collision in the correct orientation. 4, Escape, or desorption of the products. The product molecules leave the metal catalyst surface. (ans) (a) Define homogeneous catalyst. (b) Give an example of the use of a homogenous catalyst. Solution: (2) A homogeneous catalyst exists in the same phase as the reacting molecules. (ans) (b)_ Concentrated sulfuric acid is used as the catalyst for the formation of esters from carboxylic acids and alcohols. (ans) a sc enw: 15eee Enzymes as biological catalysts fundamental questions Example 1 (a) Define enzyme. (b) Give three characteristics of enzymes. (c)_ Explain how enzymes increase the rate of reaction. Soluti (a) An enzyme is a biological catalyst. (ans) (b) 1. Enzymes increase the rate of a reaction, but do not affect the reaction in any other way. 2. Enzymes are required in very small amounts, as they are not destroyed. 3. Unlike inorganic catalysts, enzymes are very specific to a particular type of reaction. (ans) (c)_ Enzymes catalyze reactions by lowering the activation energy required for the reaction to take place. Within the structure of the enzyme is an area known as the active site. It has a particular shape, and only one type of substrate will fit into the active site, The enzyme and substrate join together to form a complex. The substrate is able to react at a lower activation energy in this complex as the bonds in it have been deformed and weakened. Once the reaction is catalyzed, the products are no longer of the right shape to stay in the active site and the complex breaks up, releasing the products land the enzyme is once again free for more catalytic action. (ans) Example 2 (a) Define substrate. (b) State the relationship between substrate concentration and the rate of an enzyme-catalysed reaction. (c)_ Ina reaction whereby enzyme concentration is the limiting factor, why does increasing substrate concentration not increase the rate of reaction? (a) Substrates are substances upon which enaymes act. (ans) {b) As substrate concentration increases, the rate of reaction increases. (ans) (c) Atany given instant, every enzyme molecule in the system is occupied by its substrate, or saturated. Thus an increase in substrate concentration has no 8-18 (hemsey~ Chaleging (BE8 Standard Problems 1. For the reaction shown, the following set of data is obtained. AsB+C 30 1 005 0.05 0.05 1 2 010 0.05 0.08 2 3 0.10 0.10) 0.08 4 4 005 0.05 0.10 4 (a) Determine the order of reaction with respect to each reactant (b) Determine the overall rate law. (c)_ Determine the rate constant. 2. When lightis shone fora fixed period into a gaseous mixture of A and B, the following. reaction occurs: 2A(g) + Ble) —> A,8(e) The following table shows the experimental data obtained. (a) Determine the order of reaction with respect to each reactant. (b) Hence, write the rate equation, (c) Suggest a possible mechanism for the reaction between A and 3. 3. (a) Forthe reaction X > products, state the rate law if the reaction is: (i) zero order with respect to X, (ii) first order with respect to x. {iil) second order with respect to X. (b) Sketch the concentration-time graphs for each of the reactions above. (c) Acertain first order reaction has a halflife of 10 minutes. (i) Calculate the rate constant. (ii) Determine the amount of time needed for this reaction to be 25% complete. (hemsey~ Chaleging (BEF° 4, (a) The initial rate of reaction X +¥ > Zwas measured for different initial concentrations of X and Y, and the results are shown below. 1 on 01 10 2 0.2 01 2.0 3 03 01 3.0 4 0.3 02 60 5 03 03 9.0 (a) Find the rate law of the reaction. (b) Find the rate constant. (c)_ Determine the initial rate of reaction when [X] = 0.6 mol dm and [Y]=0.8 mol dv The reaction between HBr and O, is expected to occur in three steps. HBr+0, > HOOBr HOOBr +HBr —> 2HOBr HOBr+HBr > H,0+Bry (a) Write a balanced equation for the overall reaction (b) Identify the intermediates. (@)_ From the mechanism, the rate = K[HBr][O,]. Which is the rate determining step? Nitrosyl chloride, ONC/, can be produced from nitrogen monoxide and chlorine. 2NO(g) +Chalg) >» 2ONCI(g) The rate equation for this reaction is rate = K[NO]IC/:]. The mechanism has two steps, one of which produces ONC/ and the free radical Cle in equimolar amounts. (a) Suggest equations for the two steps of the mechanism, labeling the slow and fast step. (b) Justify your answer to (a) by considering the relative reactivities of the species involved, sc enw: a2aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.@ (o) 0 w ) 0 (m) describe the reactions of the oxides with water [treatment of peroxides and superoxides is not required] describe and explain the acid-base behaviour of oxides and hydroxides, including, vwévere relevant, amphoteric behaviour in reaction with sodium hydroxide (ony) end acids describe and expiain the reactions of chlorides with water interpret the varations ane trends in(f), (2), (h]and\()interms of tonding and ‘electronegativty suggest the types of chemical bonding present in chorides and oxides from ‘observations of their chemical and physical progerties In addition, candidates should be able to predict the characteristic properties of an element ina given Group by using knowledge of chemical perodicty deduce the nature, possible postion in the Periodic Table, and identity of unknown, ‘elements from given information of physical and chemical properties Chemsey~ Chaleging (BEPeriodicity of physical properties of the elements fundamental questions Example Give a brief description of the Periodic Table. Solution: Elements are arranged in order of increasing atomic number in the Periodic Table. The horizontal rows are called Periods and the vertical columns are called Groups. In each Period, the elements have a similar core of electrons with the number of electrons in the outermost shell increasing progressively by one. In each Group, the elements have the same number of valence electrons and thus the same outer electronic configuration. The elements can be grouped into s-block elements (Group |and Il), p-block elements (Group III, IV, ¥, IV and VI) and ¢-and f-block elements (transition metals) and noble gases. (ans) Beamplez Define the following terms. (2) Periodicity (b) Atomic radius Solution: (2) Periodicity is defined as the recurrence of similar properties at regular intervals when elements are arranged in increasing atomic number. The Periodic Table lists the elements in order of atomic number, thus the periodic properties are related to the atomic number. Such properties include first ionization enthalpies, atomic radii, electronegativities and melting points. {ans} (b) Atomic radius is defined as half the internuclear distance between two similar atoms bonded bya single bond. (ans) Example3 Explain the variation of atomic radius and ionic radius across the third Period. Solution: ‘Atomic size is affected by two factors — effective nuclear charge and screening effect. Across the period, the extra electron is added to the same electron shell, thus the screening effect remains approximately unchanged. The proton number '93,_The Prose able: hemi parity 9-3conductivity Atomic umber Bramples [Examined in 2013] This question refers to the elements in the section of the Periodic Table shown below. H He u Be B Cc N O F Ne Na Mg Asi Po oS Cl Ar K Ca roeunctransition elements. Ga Ge As Se Br kr (2) From this list of elements, identify in each case one element that has the property described. Give the symbol of the element. (i) An element that floats on cold water and reacts readily with it {ii)_ An element that forms an oxide that is a reducing agent. {ili) The element that has the smallest first ionisation energy. {iv) The element which has a giant molecular structure and forms an oxide which has a simple molecular structure (v)_ The element in Period 3 |Na to Ar) that has the smallest anion. (vi) The element in Period 3 [Na to Ar) which forms a chloride with a low. melting point and an oxide with a very high melting point. [6] (b) Use the elements in Period 3 (Na to Ar) in the section of the Periodic Table ‘opposite to Identify the oxides) referred to below. In each case, give the formula of the oxide(s) ())_An oxide which when placed in water for a long time has no reaction withit. (ii) An oxide which cissolves readily in water to give a strongly alkaline solution. (ili) Two acidic oxides formed by the same element. (iv) An oxide which is amphoteric. [5] (c)_ Fluorine reacts with other elements in Group VII to form a number of different compounds, Two such compounds and their boiling points are given in the table. iF Bers 12 127 (i) The two molecules have similar electronic configurations. Showing outer electrons only, draw a ‘dot-and-cross' diagram of the bonding in CIF. (ii) The two molecules have the same shape. Suggest why the boiling points are significantly different. [4] [Total: 15] ‘93 _The Prose eble: hemi parany 9-5CGhemsry~ Caleging (BE Solution: (a) penalise (-1) for names of elements ()) Na ork orti ) (ii) Sor Cor N orP « od a we @ wc a) (vi) Alorsi a 6) (b) (i) AkO30r SiO, @ (ii) Na30 a (iil) P,0, oF PO, and P05 oF POy, or SO, and SO; (141) {iv) AbOs QQ) [s) 0 seu s¥s neg 3 bonding pairs and 2 one pairs around Ciatom a 3 lone pairs on each of the F atoms a) (ii) either referring to van der Waal’ forces in BrF 3: van der Waals’ or intermolecular forces are greater/stronger Q) because there are more electrons in BrF; than in CIF @) OR referring to permanent dipoles: permanent dipole or intermolecular forces are stronger/greater in Br a) because BrFs has a larger permanent dipole than CIF: OR because difference in electronegativity is larger: between Br and F than between C! and F () part (i) has a maximum of 2 marks (max 2) [4] [Teachers’ Comments] The concept of periodicity lies at the heart of inorganic chemistry in the A-level chemistry syllabus. Those candidates who had studied periodicity carefully answered this question well. However, there were many answers that revealed a lack of knowledge and understanding of the relevant material. (a) Many candidates gave quite good answers to this part. A small number incorrectly gave names rather than symbols of the elements as required. {i)_ The majority of candidates gave a Group | element as their answer. The most common incorrect answer was Mg. (li) This was generally well answered although a metal was a popular incorrect response. (iil) This part was correctly answered by most candidates with Li as the most common incorrect response.Periodicity of chemical properties of the elements in the third Period fundamental questions Example Construct a table to show the reactions of sodium, magnesium, aluminum, silicon, phosphorus and sulfur with oxygen. State the equations of the reactions that occur. Solution: Sodium Sodium tarnishes in air and burns on heating with a yellow flame to form sodium monoxide, which is ionic. 4Ne +02 > 2Na:0 Magnesium | Magnesium undergoes superficial oxidation at room temperature and burns on heating with a brilliant white flame to form magnesium oxide, which is ionic. 2Mg +0, > 2Mg0 Aluminium | Aluminium undergoes superficial oxidation at room ‘temperature and burns to form aluminium oxide, which is ionic. AAl+ 302 -> 20/203 silicon Silicon does not react at room temperature but it burns, on heating to form silicon dioxide, which is covalent. Si+02 > SiOz Phosphorus | Phosphorus burns on heating to form phosphorus pentoxide, which is covalent. Pat50: > P.O Sulfur Sulfur burns on heating with a blue flame to form sulfur dioxide, which is covalent. $40, -> SO, Sulfur dioxide will be oxidized to sulfur trioxide in excess oxygen. 250, +02 -> 2503 © Note that phosphorus and silcan can show several andation states ue to expansion of ectet configuration. Example 2 Construct a table to show the reactions of sodium, magnesium, aluminium, silicon, phosphorus and sulfur with chlorine, State the equations of the reactions that occur. homey ~ Chaleaing (BESodium reacts with chlorine on heating to form sodium chloride, which is ionic. 2Na+Clz > 2NaCl Magnesium | Magnesium reacts with chiorine on heating to form magnesium chloride, which is ionic. MgCl > MgCl, Aluminium | Aluminium reacts with chlorine on heating to form aluminium chloride which is covalent. 2A1+3Cl > AlCl Silicon Silicon reacts with chlorine on heating to form silicon tetrachloride, which is covalent. Si+2Ch > SiCle Phosphorus | Phosphorus reacts with chiorine on heating to form phosphorus trichloride. P,+6Ch, > 4PCI; In excess chlorine, phosphorus pentachloride is formed. PCly+Ch > PCls ‘Sulfur Suifur reacts with chlorine on heating to form sulfur dichloride, S+Ch > SCh © Note that phosphorus can show two oxidation states in chlorides as it con use less than the ‘maximum number of valence electrons. Brample3 (a) Define amphoteric oxide. State one example of an amphoteric oxide and illustrate with equations. (b) Illustrate with equations, the acid/base behaviour of oxides. Solutio (2) An amphoteric oxide is an oxide which demonstrates both acidic and basic properties. Aluminium oxide is an amphoteric oxide which reacts with both acids and alkalis to form salts. Al,0,(s) + 6HCIaq) -> 2A/Cl,(aq) + 3H,0(I) ‘Alz0;(s) + 2NaOH(aq) + 3H20(I) > 2NaA/(OH)<(aa) (ans) (b) Basic oxides such as sodium monoxide and magnesium oxide react with acids to form salt and water. NazO(s) + 2HCI{I) > 2NaCi(aq) + H,0(1) MgO(s) + 2HCi(aq) >» MgCh(aq) + H20(") Acidic oxides such as silicon dioxide, phosphorus pentoxide and oxides of sulfur react with alkalis to form salt and water. ‘93 _The Prose eble: hemi parany PartyiE examples } (Oxides are compounds which usually contain oxygen combined with one other element. Oxides are classified as follows. acidic alkaline amphoteric_—_—basic (a) Using these terms only, complete the table to describe the oxides of the elements of the third period of the Periodic Table sodium to sulfur. [4] (b) Give the names of two elements from sodium to chlorine which form more than one oxide. [1] (6) Sodium reacts with water. (i) Describe, as fully as you can, what you would see when a piece of sodium is reacted with water. (ii). Write an equation for the reaction of sodium with water. [4] (4) Sulfur dioxide is present in small, but significant, amounts in the Earth’s atmosphere. (i) State one way by which sulfur dioxide enters the atmosphere. (il) Give the formula of another sulfur compound which is formed in the atmosphere from sulfur dioxide. (iii) What are the environmental consequences of the compound you have identified in (i)? [3] (€) Sulfur dioxide is used as a food preservative. What property of sulfur dioxide enables it to act in this way? [1] (f) Another sulfur compound which is present in the Earth's atmosphere is carbonyl sulfide, OCS. The sequence of atoms in the molecule is oxygen- carbon-sulfur and the molecule is not cyciic. (i) Draw a ‘dot-and-cross’ diagram of the OCS molecule. Show outer electrons only. (ii) Suggest a value for the O-C-S bond angle. [2] (Total: 15] Na,Ois alkaline — allow basic () MgQ is basic— allow alkaline () Alz0; is amphoteric ( SiOz, Peto, and SO, are all acidic (4 (b) any two from: sodium, phosphorus, sulfur and chlorine ‘two names required QQ) fa) ‘93 _The Prose eble: hemi parany(c) (i). any three from: floats vigorous/violent reaction occurs melts/forms a sphere moves disappears ~ allow dissolves effervescence/gas produced {any 3) (ii), Na+H,0 —» NaQH +%H; or 2Na +2H;0 > 2NaOH +H) a 4 (4) (i) combustion of fossil fuels ~ e.g. from car engines / exhausts or during the extraction of metals from sulfide ores or volcanic eruptions/burning sulfur from volcanoes or burning biomass a (ii) H:50, oF S03 allow H,503 formula required (a) (iil) acid rain, its consequences e.g. damage to buildings, damage to crops, plants, marine life, deforestation or 50, is toxic a) BI {e) itis a reducing agent/antioxidant or it kills bacteria qf) ) @ Soicis: a (ii) 180° @ 2 {Teachers’ Comments] It is important in the study of A-Level Chemistry that candidates are able to describe and explain the important reactions of the, elements of the third period of the Periodic Table. In this question there were some good answers to each part. However, many candidates’ answers were marred by the lack of a clear description when it was required. (a) Most candidates could recall this chemistry correctly; the most common error was describing SiO, as amphoteric. (b) Some candidates gave symbols here instead of names as required in the question {c) (i) Most candidates were able to give at least two correct observations. ‘Some, however, described things that were not relevant to the actual experiment such as ‘the solution will turn litmus blue’ (ii) Inthis part, the equation was often not balanced, or contained sodium oxide, Na,O, as a product. (d) () Many answers to this part were too vague, not specifying a chemical reaction. Examples included ‘car engines’ or ‘factory emissions. (ii) This was generally well answered. (iii) This too was well answered. {e) ‘Reducing agent’ or ‘anti-oxidant’ were well known reasons for the use of $0; asa food preservative, while ‘acidic’ was a common incorrect answer. CGhemsry~ Caleging (BE9.1 Standard Solutions 4, {a) The first ionization energies decrease down the group. The number of electron shells increases and the screening effect increases, thus leading to a decrease in effective nuclear charge. Thus less energy is required to remove the outermost electron, resulting in a decrease in first ionization energy from beryllium to barium. (ans) (b) The first ionization energies increase across the period The screening effect remains about the same as the electron is added to the same valence shell. Effective nuclear charge increases and thus more energy isneeded to remove the outermost electron, resulting In an increase in firstionization energy from sodium to argon. (ans) 2. {a) Melting point is defined as the temperature at which a pure solid is in ‘equilibrium wit pure liquid at atmospheric pressure. (ans) (b) The melting point of an element depends on the type of intermolecular forces between them. Metals such as sodium and magnesium possess ‘metallic bonding which is quite strong, thus they have relatively high melting points. The greater the charge density, the stronger is the metallic bonding, thus the melting point increases from Na to Al. Metalloids such as silicon have giant covalent structures which are held together by strong covalent bonds, thus leading to high melting points. Non-metals such as chlorine, sulfur, phosphorus and argon have van der Waals’ forces, which are weak forces of attraction, and therefore the melting points of non-metals are low. The strength of Van Der Waals’ forces depends on the number of electrons in the molecule, thus the melting point decreases in the order Sj>P,>Cl2> Ar. (ans) 3. {a) Sodium chloride is an ionic compound with strong ionic bonds between the ions. A lot of energy is required to break these bonds, thus it has a high melting point. Aluminium chloride is @ covalent compound with a layered structure. Some energy is required to separate these layers but the energy required is less than that for sodium chloride, thus it has a lower melting point than sodium chloride. icon tetrachloride is a covalent compound with weak Van der Waals forces of attraction between the molecules. Not much energy is required to overcome these forces of attraction, and thus it has the lowest melting point. (ans) (b) (i) P.Oiohas the lowest melting point as itis the only oxide with simple molecular structure with weak Van der Waals’ forces between the molecules. Na,O, MgO, A/,0, are ionic compounds while SiO, is a giant covalent structure with strong covalent bonds. Hence they have higher (hemsey~ Chaleging (BEmelting points than P,O,». (ans) (il) Only Na,0 and P,O,oare soluble in water. Na,0(s) + H:0(I) > 2NaOH(aq) P,O.0(5) + 6H20(l) > 4H5POs(aq) MgO and A/;0; are ionic compounds with higher charge density than 'Na,O and thus they are insoluble in water. SiO, is a giant covalent compound and the covalent bonds cannot be broken by water. Thus they are insoluble in water. (ans) a 4 (b) Lithium oxide reacts vigorously with water to give lithium hydroxide. Liz0(9) +H20(1) > 2LiOH(aq) Diboron trioxide reacts with water to give a weak acid. 8,045) +3H,0(l) > 2H,80aq) Carbon dioxide reacts with water to give a weak acid. O,(g) + H20(l) > H,COs(aq) Nitrogen dioxide reacts with water to give an acidic solution NOzlg) +H20(I) + HNO,{aq) + HNO,(aq) Fluorine monoxide reacts with water to give an acid. F,0(g) +H,0(I) > 2HF(2q) +02(g) (ans) Sodium monoxide reacts vigorously with water to give sodium hydroxide, Naz0(s) + H,0(I) > 2NaOH(aq) Sodium peroxide reacts vigorously with water to give hydrogen peroxide. Na0,(s) + 24,0(l) -» 2NaOH(aq) + 4,0,(aq] Phosphorus trioxide reacts slowly with cold water to form phosphorus acid. PxOe(s) + GH;0ll) > 4H;PO,faq) Phosphorus pentoxide reacts vigorously with cold water to give polyphosphoric(V) acid. P,Oso(s) + 6H2O(!) > 4H,PO.(aq) Sulfur dioxide reacts with water to form sulfurie(IV) acid, $0,(g) +H.01I) -> H,S0,(aq) Sulfur trioxide reacts violently with water to form sulfurie{VI) acid. $0,(!) + H,0(1) —» H;S0.{aq) Dichlorine oxide reacts with water to form hypachlorous acid. €1,0[g) +H,0(1) > 2HOCI(aq) (ans) ‘93 _The Prose eble: hemi parany 9-17‘ Content 92.1 Similarities and trends in the properties ofthe Group Il metals magnesium to barium and their compounds Learning Outcomes Candidates should be ableto: (0). descrbe the reactions ofthe elements with oxygen and water (b) describe the behaviour ofthe oxides with water (interpret and explain qualtatively the trend inthe therrial stability of the ‘of the charge density of the cation and the polarisabiity of the large anvon (@) interpret, and make predictions from, the trends in physical and chemical properties of the elements and their compounds erates in termsSimilarities and trends in the properties of Group II metals magnesium to barium and their compounds fundamental questions Erample (a) Which Group of elements in the Periodic Table is commonly known as ‘alkali earth metals’? (b) State the number of valence electrons for the elements in the above Group. (c)_ State two examples of ‘alkali earth metals’. Solution: {a) Group it. (ans) (b) 2 valence electrons. They usually have an oxidation state of +2. (ans) (c) Magnesium and calcium. (ans) Example? (a) Describe the reaction of Group II metals with oxygen. (b)_ State the general equation for the above reaction. Solution: (a) Allalkali earth metals burn brilliantly to form metal monoxide. Going down the group, the rate of reaction increases. (ans) {b) Assuming x is the metal atom, the general equation is: 2X(s) + Oa1g) > 2XO(s) (ans) Example3 (a) Describe the reactions of Group Il metals (magnesium to barium) with water. (b) Group metal must be stored under oil to prevent reaction with oxygen and water vapour in the air. Explain why this precaution is not necessary for magnesium. (c)_ Give the equation for the reaction between magnesium and water. 9-22 hemsry~ Chaleging (BE s(a) Beryllium does not react with water, but reacts with acids. Magnesium reacts slowly with water, readily with steam and rapidly with acids to form magnesium oxide. Calcium, strontium and barium react vigorously with cold water to form hydroxides. (ans) (b) Magnesium forms a protective oxide layer and prevents the metal from corrosion. (ans) (6). Mg(s) +2H20(1) + Mg(OH)laq)+Hsle) (ans) Example (a) Describe the reaction of Group II metals with acia. (b) State the general equation for the above reaction. Solution: (2) All alkali earth metals react with acids to form the corresponding salts and hydrogen gas. Reactivity with acids increases down the Group. (ans) (b) Assuming X is the metal atom, the general equation is: X(s) + 2H'(aq) > X" (aq) + Hale) (ans) Examples Describe the behaviour of Group il oxides with water. Solu ‘With the exception of beryllium oxide, which 's amphoteric, the other oxides are basic oxides. Group Il oxides tend to be less soluble than Group | oxides due to the higher lattice energies. Magnesium oxide is slightly soluble and forms an insoluble hydroxide. The other oxides all dissolve rapidly to produce alkaline solutions. XO(s) +H,0(l) > X"(g) + 20H (aq) where X is the metal atom (ans) Examples Calcium is in Group Il of the Periodic Table. (2) Write a balanced equation to show the action of heat on calcium nitrate. (b) Compare the thermal stability of calcium nitrate with barium nitrate. Solutio (a) 2Ca(NOs),(s) > 2CaO(s) + 4NO>(g) +0.(g) (ans) 3 Gopi 9-23(b) Assuming there is 100 g of magnesium nitride, s Mg. N 73 2 243 4 3,00 1.93 3 2 ‘Thus the empirical formula isMg;N2. (ans) (c)_ MgaNa(s) + 6H20(1) > 2Mg(OH)s) + 2NH3(g) (ans) a ied 3.83 g of BaO is produced when 4.23 g of a sample of BaO, is heated. Oxygen gas is also produced. (2) Write a balanced equation for the decomposition of 830, (b) Determine the value of x (c)_ Calculate the volume of oxygen (measured at s.t.p.) evolved in the experiment. (4) Write an equation for the reaction of barium oxide with water. Solution: (@) BaQJs) > e091 + [Jou (ans) (8) change n weight = =040¢ 23-383, No. of moles of 0,= 22 = 0.0125 0.0250 No. of moles of 80 Mole ratio of B20 : 0, =0.0250:0.0125 22:1 (c) Volume of 0, at s.t.p. = 0.0125 x 22.4 1.28 dm* (ans) (d) BaO(s) +H20(!) > BalOH)s(aq) (ans) 32 Gow 9-25More acid is neutralised by 1g of W than by 1 g of X ‘The metallic element in W reacts with water more quickly than the metallic element in Y. 3. Adding Zto a soil decreases the pH of the soil 1,2 and 3 are correct and 2 only are correct 2and 3 only are correct Jonly is correct on e> Solution: Answer: D 'W is magnesium oxide, which is used as a refractory lining material. Xis calcium carbonate, whichis used as building material When calcium carbonate is heated, it forms calcium oxide: CaCO;(s) —» CaO(s) + CO,(e) Hence Y is calcium oxide. Calcium carbonate, calcium hydroxide and calcium oxide are used as fertilizers for correcting acidity (liming). Hence 2 is calcium hydroxide 1. Group II metals (M) react with acid to form the corresponding salts and hydrogen gas, Mis) +2H"(aq) > M* (eq) +Hale) Since the molar mass of Mg is less than that of Ca, 1.g of Mg will contain more moles than 1 g of Ca. Hence more acid will have reacted, 2. Calcium reacts vigorously with water to form hydroxides, whereas magnesium does not react with water. 3. Calcium hydroxide is alkaline. Addingit to soil increases the pH. [Teachers’ Comments] 32% of candidates chose the correct answer, D. The most commonly chosen incorrect answer was C, chosen by 30% of candidates. X, ¥ and Zshould have been identified as calcium compounds; Z is therefore Ca(OH)>. When Ca(OH): is added to soil it neutralises acid, so the pH of the soil is increased, not decreased, so statement 3is incorrect. 3 GopiNote: Chemsey~ Chaleging (BEContent 93.1 The similarities and trends in te physical and chemical properties of chlorine, bromine and iodine |i) Characteristic physical properties lil) The elative reactivity ofthe elements as oxidising agents |i) Some reactions of tne halide ions liv) The wactions af chlorine with aqueous sodium hysroxide Learning Outcomes Candidates should be ableto: (2) describe the trends in volatility and colour of chlorine, bromine and iodine (6) _ analyse the volatility ofthe elements in terms of van der Waals’ forces (6) deserbe and deduce from E° values the relative reactivty ofthe elements as oxidising agents (4) describe and explain the reactions ofthe elements with hydrogen (9) (describe and explain the relative thermo! stabilities of the hydrides (i) interpret these retatve stabilities in terms of bond eneray (describe and explain the reactions of halide ions with: (aqueous siver ions fllowed by aqueous ammonia, (0) concentrated suifurc ace (a) describe and analysein terms of changes of oxidation number the with cold, and with hot, aqueous sodium hydroxideThe similarities and trends in the C&S @ physical and chemical properties of chlorine, bromine and iodine fundamental questions Example (a) Define halogens. (b)_ Describe the types of bonding that halogens take part in. (c}_ State and explain if all the halogens can expand their octet configuration. Solution: (a) Halogens are defined as the chemical elements either individually or collectively that constitute Group Vil of the Periodic Table. They are also commonly known as p-block elements. (ans) (b) The halogens have seven electrons in their outermost shell, with a configuration of ns*np’. Helogens will complete the octet by accepting an electron to form a halide ion, x", or bysharing an electron to form a covalent bond. (ans) {c) With the exception of fluorine, all halogens can expand their octet configuration. Fluorine does not have energetically accessible d orbitals for expansion of octet configuration to take place. All other halogens are able to promote electrons into the d orbitals and thus are able to form more than ‘one bond. (ans) Example 2 (a) State the colours of chlorine, bromine and iodine in their respective states at room temperature. (b) Describe the trend in volatility of the halogens, with reference to chlorine, bromine and iodine. Solution: (a) Chlorine — yellowish green gas Bromine ~ dark red liquid lodine — black solid (ans) {b) The boiling points of the halogens increase down the group as the number of electrons increases, resulting in an increase in the strength of the Van der Waal’ forces. Chlorine has the smallest number of electrons, thus it has the lowest boiling point, followed by bromine and iodine. This also explains the change in physical state of the halogens down the group — from gas to solid. Chlorine is a gas, bromine is a liquid and iodine is asolid. (ans) is 9-30 homey ~ Chaleaing (BEExample Explain why iodine is more soluble in aqueous potassium iodide than in water. Solution: lodine dissolves in aqueous potassium iodide solution to give a reddish-brown solution of soluble I, ions. 1s) +1-(aq) = Ls faq) (ans) a Fxamploa | (2) Halogens are oxidizing agents. Explain why the relative strength of oxidizing powers decreases down the group. (b) Explain how £° values can be used to deduce the relative reactivity of the halogens as oxidizing agents (0) State and explain what is seen when chlorine gas is passed through colourless potassium bromide. (4) Explain why the strength of the oxo-acids increases in the order HC/O< HCIO, < HCIO3 < HCIO,, Solution: (2) This is because the halogens become less reactive and the electron affinity decreases, thus decreasing their tendency to oxicize other elements. Thus fluorine is the strongest oxidizing agent while iodine is the weakest. ans) (b) The weaker the oxidizing strength, the less positive the E° values. For ‘example, bromine has an E° value of +1.07 V while iodine, which is lower in the group, has an E° value of +0.54 V. (ans) (€)_ The solution turns reddish brown. The chlorine gas is a stronger oxidising agent than bromine and thus it displaces the bromine from potassium bromide to form aqueous potassium chloride and bromine. Bromine is reddish brown in colour and gives the solution its colour. (ans) (4) All four oxo-acids dissociate in water to form protons and the corresponding anions. The strength of the O-H bond in the molecule determines the acid strength. The additional oxygen atoms exert an electron-withdrawing effect, ‘weakening the O-H bond. Thus the acid strength is in the order: HC/O < HCI0p < HCI03 CI-(aq) + C/O"(aq) +H20(!) (c)_ Will the products be different if chlorine has reacted with hot alkali instead? If 50, give the equation for the reaction and the corresponding changes in oxidation number. Solution (2) Disproportionation is the simultaneous oxidation and reduction of a substance reacting with itself, thereby forming two dissimilar ions, or an ion and an atom or molecule, (ans) (b) Chlorine (0) is simultaneously oxidized to chlorate(|) ions (+1) and reduced to chloride ions (-1). (ans) (c) Yes, 3C/,{g) + 60H (aq) > SCI (aq) + C/O (aq) + 3H20(I), Chlorine (0) is simultaneously oxidized to chlorate(V) ions (+5) and reduced to chloride fons (1). (ans) a Erample7 (hemsey~ Chaleging (BE (a) Describe the reaction of halogens with hydrogen gas. (b) Describe and explain the relative thermal stabilities of the compounds formed from the above reaction, (c)_ Describe the effect of heating on hydrogen chloride, hydrogen bromide and hydrogen iodide. Solution {a) Hydrogen halides are formed from the reaction of halogen with hydrogen. Taking X as the halogen, Hi +X, 2HX Hydrogen reacts vigorously with chlorine, less vigorously with bromine and very slowly with iodine. This can be attributed to the higher bond energy value of hydrogen chloride as compared to hydrogen bromide and hydrogen iodide. The heat energy given out by the formation of the hydrogen chloride bond is sufficient to provide the energy needed to break the hydrogen and chlorine gas bonds. However, this is not the case for hydrogen iodide. Thus the reaction does not go to completion. (ans)(b) () Bond energy can be used to compare relative thermal stabilities. The strength of the H-X bond decreases from hydrogen chloride to hydrogen iodide due to the increase in size of the halogen. This causes the thermal stability of the hydrogen halides to decrease down the group. (ans) Hydrogen chloride does not decompose. Hydrogen bromide decomposes slightly to produce some Brg). Hydrogen iodide decomposes most readily to form thick purple fumes of TA{g). (ans) a Bramples e) (b) Name the process that hydrogen halides undergo when concentrated sulfuric acid is added, Describe what happens when concentrated sulfuric acid is added to sodium chloride, sodium bromide and sodium iodide. Give equations for the reactions that occur. @ (b) Oxidation. (ans) For sodium chloride, steamy fumes of HCi{g) are produced, e.g. with NaCI. NaCilaq) + H,S0.(aq) > HCile) + NsHSO4(aq) For sodium bromide, orange-brown fumes of HBr are produced. NaBr(s) + H;SO4(aq) —> HBr(g) + NaHSO.(aq) HBr is oxidized to Br, Orange-brown fumes of Br; are produced. 2HBr(aq) + H2S0,(aq) —> Br:\g) +SOa(g) + 2420(!) ‘The bromide ion is more easily oxidized than the chloride ion, thus, concentrated sulfuric acid is strong enough to oxidize hydrogen bromide to bromine gas but not for hydrogen chloride. For sodium iodide, purple vapour of iodine is obtained. Nal(s) +H;50,(aq) -> Hi(g) + NaHSO,(aq) HL is readily oxidized to I; BHI(aq) + HSO«(aq) > 4I2(g) +H2S(g) +2H,0(I) (ans) Brampled) (a) (b) Compare the effect of acidified silver nitrate on sodium chloride, sodium bromide and sodium iodide. state what happens when the precipitate formed is exposed to light. Describe what happens when aqueous ammonia is added to the precipitates formed in (b). 33 Gran wi 9-33Solution: (a) For sodium chloride, a white precipitate of silver chloride is formed ‘Ag’(aq) +CI"(aq) > AgCi(s) Upon standing in the light, the white precipitate darkens quickiy. For sodium bromide, a pale yellow precipitate of silver bromide is formed. ‘Ag'(aq) + 8r (aq) — AgBr(s) Upon standing in the light, the precipitate darkens slightly. For sodium iodide, a yellow precipitate of silver iodide is formed. Ag (aq) +1 (aq) > Agl(s) There is no change when the precipitate is exposed to light. (ans) © The darkening effect isdue to the conversion ofsiver halide tosmal particles of metalic silver by light. (b) Silver chloride dissolves readily to give a colourless solution of diammine silver(t) ion. AgCl(s) +2NH3(aq) > [Ag(NHs)2] (aq) + Cl (aq) Silver bromide dissolves in concentrated ammonia solution to givea colourless solution. AgBr(s) + 2NH3(aq) — [Ag(NHs)2] (aq) + Br (aq) Silver iodide is insoluble in aqueous ammonia. (ans) Example 10 (a) Discuss the manufacture of chlorine. (b) Write equations for the reaction of chlorine with, (i) sodium hydroxide; (ii) hydrogen sulfide; and (iil) potassium iodide. Solution {a) Chlorine is produced in the mercury cathode cell and the diaphragm cell. Mercury cathode cell ~ brine is electrolysed using mercury as a cathode and graphite as anode. © Anode: 2Ci > Cl +2e © Cathode: 2Na +2e > 2Na Na+Hg — Na/Hg ‘An unreactive sodium amalgam is formed at the cathode. It will react with water to produce sodium hydroxide and hydrogen gas. 2Na/Hg +2H20 > 2NaOH +H, -+2Hg (hemsey~ Chaleging (BEDiaphragm cell © Anode: 2c! > Chy-+2e + Cathode: 2H +2 > Ha The anode compartment contains an excess of Na* ions while the cathode compartment contains an excess of OH” ions. The ions in excess are allowed to react as brine flows through the diaphragm, producing sodium hydroxide. (ans) (b) (i) Chale) +2NaOH(eq) > NaCilaq) + NaOCl(aql + H20(") (i) Ch{g) + H.S(aq) -> 2CI-[aq) + 2H°(aq) +5(s) (iil) Cla(g) + 2KI(aq) > I,(aq) + 2KCllaq) (ans) Example 11 (a) Three substances which contain chlorine include polychloroethene, sodium chlorate(!) and tetrachloromethane. state one use of each of these substances and the properties which make them suitable for such use. (b) Potassium chlorate(V) is used to make fireworks and matchstick heads (i) Suggest how it can be obtained from chlorine. (ii) Suggest what happens when potassium chlorate(V) is added to iron(II) sulfate (aq). Solution: (2) Polychloroethene is used to make pipes as it is chemically inert, durable and strong. Sodium chlorate(!) is used in bleach as itis a strong oxidising agent. Tetrachloromethane is used as an organic solvent as itis inert and not flammable. (ans) (b) (i) Itis obtained from chlorine by passing chlorine gas into hot aqueous KOH. 3Cla[g) + 6OH (aq) > SCI (aq) + C105 (aq) + 3H,0(!) (ii) From the Data Booklet, clos +6H' + 6e = Ci” +3H,0 eP=145V When iron(tl) sulfate is added, ClO; +6H* + 6Fe”* > Cl” +6Fe* +3H,0(I) Eq = 1.45 - 0.77 =0.68 V>0 Thus the reaction is feasible, and the solution changed colour from pale green to yellow. (ans) 33 Gran wi 9-35Example 12 [Examined in 2022) The following two experiments are carried out with anhydrous potassium chloride and observations X and Y are made at the end of each experiment. Concentrated sulfuric acid is added to the potassium chloride and the fumes produced are bubbled into aqueous potassium iodide solution ~ observation X. The potassium chloride is dissolved in aqueous ammonia and this is then added to aqueous silver nitrate — observation Y. What are the observations X and Y? brown solution | colourless solution brown solution | white precipitate colourless solution | colourless solution colourless solution | white precipitate Answer: The relevant product of the first reaction is HCI. conc 250, + 2KCI —> K:S0, +2HCl HC! will not react with kI(aq), hence observation X is “colourless solution”. The second reaction was between KC/ and AgNO; in the presence of ammonia solution, AgNO;+KCI > AgC!+KNO3 The expected product, AgCi, is soluble in ammonia solution, so observation ¥ Is also “colourless solution” [Teachers’ Comments] The most commonly chosen incorrect answers were B and D. The relevant product of the first reaction (conc HyS0« + KCI) is HCI. HCI will not react with kI(aq), so observation X is “colourless solution”. The second reaction was between KC/ and AgNO; in the presence of ammonia solution. The expected product, AgC!, is soluble in ammonia solution, so observation Y is also “colourless solution”. a (hemsey~ Chaleging (BE= Content 94.1 General physical and characteristic chemical properties ofthe frst set of transition elements titanium to copper 9.42 Colour of complexes Learning Outcomes Candidates should be able to (2) explain what is meart by a transition element, in terms of the d-blbek elements forming {ne or more stable ions with incomplete d orbitals (6) sate the electronic configuration ofa first row transition element and of its ions (0) _ state thatthe atomic radi, ionic radi and frst ionisation energies ofthe trarsition ‘loments ora (4) contrast, qualitatively the melting point; density; atomic radius; ionic radius; frst ionisation energy and conductivity of the transition elements with those of calcium asa typieal s-block element (6) describe the tendency of transtion slements to have variable oxidation states (0) predict from a given electronic configuration, the likely oxidation states of atransition (@)_descrbe and exolain the use of Fe”/Fe’", MnO. /Ma'* and C10," /Cr'*as examples of redoxsystems (see aso Section 6) (h) (explain the reactions of transition elements with igands to form complexes, includine the cemplexes of copner{l ions with water ard ammonia (i) describe the formation, and state the colour af, these complexes (predict, using & values, the likelhood of redox reactions (explain qualitatively that tgand exchange may occur, includirg CO/O in haemoglobin (explain how some transition elements and/or their compounds can act as catalysis (see also ai) (explain, interms of d orbital splitting, why transition elements are usually colouredGeneral physical and characteristic chemical properties of the first set of transition elements titanium to copper fundamental questions Erample (a). Define transition metal. (b) Complete the table below, Scandium 2 Titanium 2 Vanadium 23 Chromium 24 Manganese 25 iron 26 Cobalt 27 Nickel 28 Copper 29 Zinc 30 Soluti {a) A transition metalis one which forms some compounds in which the inner shell of d electrons is incomplete. It is also known as a d-block element. (ans) () Scandium 24 15°25'2p°3s?3p"3d" Titanium 22 1s"25'2p°3s"3p°3d°4s" Vanadium 23 15°23'2p°3s"3p"3d°4s" Chromium 24 18°2s'2p°3s"3p°3d°4s" Manganese 25 1s'2s'2p'3s"3p"3dhas iron 26 15225!2p%3s"3p°3d"a: Cobalt 27 1s'2s'2p%3s"3p"3d74s" Nickel 28 15°2s'2p°3s’3p"3d"4s" Copper 29 15°28'2p"3s'3p°30'°4s* Zine 30 1'28'2p"3s'3p"30""4s? 9-38 homey ~ Chaleaing (BEExample? State the trends in the atomic radii, ionic radii and first ionization energies of the first row transition elements. Solution: The physical properties of the d-block elements are generally very similar as there is only a smalll increase in effective nuclear charge. The extra electron is added to the 3d electron shell, which then shields the 4s electrons. This results in avery small increase in the attraction between the nucleus and the 4d electrons. Thus there is very little decrease in the atomic radii and ionic radii of d-block elements There is 2 very small increase in the ionization energy of first row transition elements. (ans) Exemple3 Compare the melting point; density; hardness; first ionization energy; electronegativity and conductivity of the transition elements with those of s- block elements. Solution: The table below shows the comparison in properties between transition elements and calcium, First ionization energy | transition elements have comparable first ionization energies Electronegativity transition elements have higher electronegativities than s-black elements Melting point transition elements have higher melting points than s-block elements Hardness transition elements are hard while s-block elements are soft. Density transition elements have high density while s-block elements have low density Conductivity transition elements are good conductors of heat and electricity Chromium has the outer electron configuration 34°4s" rather than 304s". Explain this phenomenon. Solution: The 3d°4s" configuration is at a lower energy level than 34s” (which has a spin pair of electrons in the 4s orbital) as the former has more unpaired electrons. 194 arinvoauante te chemiryaranaonelenente 9-39‘The paired electrons in 3d4s” gives rise to extra repulsion and this outweighs the small energy difference between the 3d and 4s levels. Thus the 34°45" configuration is more stable. (ans) Example 5 (a) The graph below shows the trend in relative atomic sizes for some transition elements. Explain the shape of the graph. [Atomic rads Dt Se Ti V Cr Mn Fe Co Ni Cu Zn (b) The graph below shows the trend in second ionization energy for some transition elements. Explain why chromium has such a high ionization energy in comparison to vanadium and manganese. Ionization energy (baton Se Ti V Gr Mn fe Co Ni Cu elements Soluti {a) From the graph, itcan be seen that the atomic radi first decreases, then remains almost constant before increasing slightly towards the end at copper and zinc. ‘The atomic radius is dependent on the effective nuclear charge. An increase in nuclear charge will result in a decrease in atomic size. However, as electrons are added to the inner d orbital, they increase the shielding effect between the nucleus and the outermost s electrons. This shielding effect results in 2 very small increase in effective nuclear charge, thus the decrease in atomic radius is very small from scandium to chromium. From chromium, to nickel, the atomic radius remains almost constant as the attraction force caused by the increased nuclear charge is balanced by the increased shielding effect. Copper and zinc shows an increase in atornic radius due to the completely filled d orbitals, where the effective shielding effect outweighs the increase innuclear charge. (ans) © can be concluded that the atomic redi are relatively inveriant. 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