Peco tne MeN ReaD Seiko arrest ec n TL Ames eC + allow students to focus on most examined concepts - cut study Acute Ine Mutegs-—iaira ra, Bae eaet eee eared roe ree gt ie pe ee cote eee ecie ta cae ie cleus Een ete Rare ela ane Lear res ee rag complete and concise eBook editions available Eres CES mre eae cm ae irate updated edition SE A ELSSHIAVVed§ ED,CHEMISTRY ADVANCED LEVEL complete guide Updated Edition Thomas Bond yatcannb) Chris Hughes ws<(.anan) + according to syllabus for exam up to year 2016 + first to provide exam data-mining in study guide * allow students to focus on most examined concepts ~ cut study time and increase efficiency * an expert guide to lead one abstract knowledge and wisdom * provides exact, accurate, complete and independent self-education © the only guide currently that covers Planning Questions * advanced trade book ‘© complete and concise ebook editions available © also suitable for © Cambridge Gce AL (H1/H2) = Cambridge Internctional A & AS Level"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. 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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 ts own costs, one-time only ainting 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94 92 93 94 95 96 97 10.1 Reaction kinetics 8.1 Simple rate equations; orders of reaction; rate constants 8.2 Concept of activation energy 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 Aluminium 9.6.1 Properties of aluminium and its compounds Nitrogen and sulfur 9.7.1 Properties and uses of nitrogen 9.7.2. Properties and uses of sulfur 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 x bonds 10.15 Isomerism: structural; geometrical; optical10.2 10.3 10.4 10.5 10.6 10.7 108 10.9 ut Hydrocarbons 10.2.1 Alkanes (exemplified by ethane) 10.2.2 Alkenes (exemplified by ethene) 10.2.3 Arenes (exemplified by benzene and methylbenzene) 10.2.4. Hydrocarbons as fuels Halogen derivatives 10.3.1 _Halogenoalkanes and halogenoarenes 10.3.2 Relative strength of the C-Hal bond Hydroxy compounds 10.4.1 Alcohols (exemplified by ethanol) 10.4.2. Phenol Carbonyl compounds 105.1 Aldehydes and ketones Carboxylic acids and deri 10.5.1 Carboxylicacids (exemplified by ethanoic acid and benzoic acid) 10.5.2 Acyl chlorides (exemplified by ethanoy! chloride) 10.6.3 Acid anhydrides 10.5.4 Esters (exemplified by ethyl ethanoate and phenyl benzoate) tives Nitrogen compounds 10.7.1 Amines (exemplified by ethylamine and phenylamine) 10.7.2 Amides (exemplified by ethanamide) 10.7.3. Aminoacids (exemplified by aminoethanoic acid) 10.7.4 Proteins Polymeris: 10.8.1. Addition polymerisation 10.8.2 Condensation polymerisation Summary of tests for functional groups 10.9.1. Tests for functional groups Planning, Analysis and Evaluation 11.1 The Planning Questions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.Redemption Coupon As an original purchaser of our fine publications, you are now entitled to purchase a copy of the print editions listed on the redemption list (please refer to www.yellowreef.com for details and prices). Please send us the required cheque payment (made payable to: themis publishing) or via PayPal by following the payment instructions at www.yellowreef.com and the original copy of the purchase receipt of this book. New book title / ISBN (& price payable): Name: tson $ Your Delivery address: (optional incase of mail oss, please also scan receipt and email to: eBooks@yellowreef.com fold here Themis Publishing VBox 888862 Singapore 919191Content 11 _Relabve masses of atomsand molecules 1.2 The mole, the Avogadro constant 13. The caleulationof empirical and melecular formulae 14 Reacting masses and volumes (of solutions ard gases) Learning Outcomes [the term relative molecular mass or M, vill be useé for ionic compounds) Candiéates should be ableto: (2) define the terms relative atomic, isetopic, molecular ané formula masses, based on the "C scale (b) define the term mole in terms of Avogadio constant (9 calculate the relative atomic mass of an element given the relative abundances of Its Isotopes (@) define the terms empirical and molecular formula (@)aleulate empircal and molecular formulze using combustion dats or composition by mass (() write and/or construct balanced equations (@)_serform calculations, including use of the mole corcept, involving (reacting masses (from formulse and equatiors) (i) volumes of gases (eg, Inthe burning of hydrocarbons) (i) volumes and concentrations of solutions [when pertorming calculations, candidates’ answers should reflect the number of significant figures given or asked for inthe question} (h) deduce stoichiometric relationships from calculations such as those in (g) 1 ons mole nd echonetyRelative masses of atoms and molecules Define Atoms The study of atoms can be used to explain structures and bonding as well as predict the properties of matter. © The mass of an atom is very small (approximately 10” g). } Thusarelative atomic mass scale, the "C scale, is employed to compare the masses of different atoms. Anatom of “C isotope is assigned a mass of 12.000 units on the “*C scale. % Being a solid at room temperature, carbonis easy to transport and store. Molecules % Examples of molecules include O2, HO and NH. Isotopes } Examples of isotopes include “0, 0 and “o. % Unstable isotopes undergo radioactive decay to form daughter nuclei, emitting radiation in the process. ‘* Three main types of partides/radiation ~ alpha, beta and gamma are given off. ‘© Alpha particles resemble the nucleus of a helium atom; beta particles are high-energy electrons while gamma radiation is an electromagnetic radiation of high frequency. © The order of their penetrating power: alpha particles < beta-particles < gomma radiation. 1-2 FL cheisoy ~ Gnplte ui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.‘Mass of propane = nM, = 0.33222 (44.0) = 14.6 g (3 sf) (ans) (f)_ No. of carbon atoms in 1 molecule of propane = 3 No. of carbon atoms in 1 mole of propan (6.02 x 10%) =1.81%10" (ans) (a) Calculate the concentration (in mol dm *) of the solution obtained by dissolving 2.0 ¢ of glucose, CcH:20x, in water to make 250 cm’ of solution. (b) Calculate the concentration (in mol dm *) of the solution obtained by diluting 10.0 cm? of a 1.5 mol dm™ hydrochloric acid with water to give 250 cm’. Solution: (a) Number of moles of glucose = ———__20__ [6(12.0) +12(2.0) +6(16.0)) _ 20 © 180.0 =0.0111 1010 cenceraton = 22%). oonss = 0.0444 mol dm* (ans) (c)_ Let the concentration of the diluted solution be c. 100) _— (22) 1000 1000 ¢=0.06 mol dm? (ans) Chlorine has two isotopes with mass numbers and relative isotopic masses of 35 and 37. 75% of chlorine is “C/ and 25%is "'C/. Determine the relative atomic mass of chiorine. Solution: 3 (isotopic mass x percentage abundance) = (7535) +(2537) = 3550 3550 100 =35.5 (ans) Relative atomic mass of an atom (4,) 1-10 FL cheisoy ~ Gnplte ui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.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.Sketch a graph to show the first ionisation energies across Period ||. Explain the trend in the graph. Solution: The ionisation energy is influenced by the atomic number. The greater the number of protons, the stronger is the force of attraction and the higher is the ionisation energy. Actoss a period, the ionisation energy should increase; however, there are certain exceptions. 1. The lowest icnization energy is for lithium because 2) it has only 3 protons in the nucleus b) it can lose its outer 25" electron easily because it will then have a full 1s? sub-shell which is very stable. 2. The highest ionization energy is for neon because a) ithasa full 2p” sub-shell b) thas 10 protonsin its nucleus 3. Boron has lower ionization energy than Beryllium even though there is a greater nuclear attraction in Boron because 2) Boron loses its 2p" electron from thesub-shell easily to gain a full 2s sub-shell b) Beryllium has a full 2s” sub-shell giving it extra stability and therefore making it more difficult to remove an electron 4. Oxygen has lower ionization energy than Nitrogen because 2) Oxygen loses its 2p* electron in its sub-shell easily to gain a half full 2p° sub-shell which is more stable. b) Nitrogen has its outer electrons in a half full 2p? sub-shell giving it extra stability and therefore making it more difficult to remove an electron, (ans) lonisation cenergy/ki mol* Ne Atomic 345678910 number 7 some nese 2-2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.Solution: (a) The noble gases are elements with atomic number 2 and 10. (ans} (b) (i) The element with an atomic number of 4 has the electronic configuration of 1s"2s” while the element with an atomicnumber of § has the electronic configuration of 1s°2s'2p' ‘The 2s subshell is nearerto the nucleus than the 2p subshell. Therefore the force of attraction between the nucleus and the outermost electrons is higher for the 2s subshell. It becomes harder to remove electrons from the 2s subshell and the first ionization energy is higher. ‘As we continue across to the other elements with increasing atomic number, the electrons are going into the same sublevel and we see the ionization energy increasing. (ans) (ii) In the element with an atomic number of 7, all of the 2p orbitals are half-filled. When we go next to the next element the electron must be placed in one of the half-filled orbitals. But it requires some extra energy to place two electrons into the same orbital due to the electronic repulsion between the electrons. Similariy, the repulsion between the paired electrons also means that less energy is needed to remove one of the paired electrons, so there is a small decrease in the first ionization energy. (ans) (c)_ The second ionization energy is the energy required to remove a second electron from a +1 cation in the gaseous state. It is always greater than the first ionization energy as the first electron is removed from a neutral atom, while the second is removed from a positive ion. The increased positive charge binds the electron more tightly, so more energy is required to overcome the attraction. (ans) (4) N'(g)-+enerey > N*(g)+e (ans) {e)_ The element with the atomic number of 4 has the greatest third ionization energy. This is because as the first two ionizations removes p electrons while the 3 removes the electron from the 1s orbital which is closer to the nucleus. Thus a large amount of energy will be needed to remove that 3° electron. (ans) a Which of the following particles has a half electron? Cc oN St oP led set of p orbitals after it gains an Solution: The particle has a halt-filled set of p orbitals => p’. Co: 4s'2s*2p! => Cs 1s'2s'2p? N 1s2s'2p* = Nz 1s2s'2p* s 18°2s°2p°3s3p> => Si? :—1s°2s'2p°3s"3p* P 15°2s°2p"3s°3p> => P : 15°2s'2p°3s°3p” 7 some nese 2-25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 31 32 a3 a4 as 36 Ionic (lectrovalent) bonaing Covalont and co-ordinate (dative covalart) bonding (). The shapes of simple molecules (i) Bond energies, bond lengths and bend polarities Intermolecular forces, including hydrogen bonding Metalic bonding Bonding ard physical properties The solid state Learning Outcomes ‘Candidates should be ableto: Oo o 0 w 0 (m) o © Aescrbe ionic (electrovalent) bonding. asin sodium chloride and magnesium oxide, Inclucing the use of dot-and-cross dagrams escrbe, including the use of dot-and-cross diagrams, () covalent bonding, as in hydrogen; exygen; nitrogen; chlorine; hydrogen chloride; carben dioxide; methane; ethene (i) co-ordinate (dative covalent) bonding, as in the formation of the ammonium ion and in the All, melecule ‘explain the shapes of, and bond angles in, molecules such as 8 (trigonal planar); CO; {imear; Ch (tetrahedral); NH, (trigenal pyramidal) H,O (non-linear); SF. (octahedral) by ‘using the Valence Shall Electron Pai Repulzion theory describe covalent bonding in terms of orbital overlap, gving @ and bonds (see aso Section 10.1) prediet the shapes of, and bond angles in, molecules analogous tothose specified in (¢) docerbe hydrogen bonding, using ammonia and water a examples of molecules containing -NH and -OH groups. «explain the terms bond energy, bond length and bond polarity anduse them to compare ‘reactivities of covalent bonds escrbe intermolecular ferces van der Waals forces), based on permanent and induced Aipoles, asin CHC) Brit) and the liquid noble gases. describe metallic bordingin terms ofa lattice of positive fons surrounded by matte electrons describe, interpret and/or predict the effect of different types of Londing (inic bonding; covalent bonding; hydrogen bonding; other intermolecular interactions; metalic bonding) ‘on the physical properties of substances educe the type of bonding present from given information show understanding of chemical reactions in terms of energy transfers associated with the breaking and making of chemical bonds Aescrbe, in simple terms, the lattice structure of a crystalline solid which i (i) ‘onic, asin sodium chloride, magnesium oxide (0) simple metecular, asin oaine (ii) piantmolecular, as in graphite: diamond (uv) hydrogen-bonded, a5 in ice (0) metallic, sin copper [the concept ofthe ‘unit cal isnot required] cutline the importance of hydrogen bonding to the physical properties of substances, Inclucing ice and water suggest from quoted physical data the type of structureand bonding present in a substance 3 chal boning 3-1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.Ag apt yaar ALO: | + OF > (283) aig oo fap Cm Electron affinity The addition of the first electron is known as first electron affinity, the addition of the second electron known as second electron affinity and so on. Due to the incomplete screening of the nucleus by its own electrons, an electron is able to attract a neutral atom. Therefore most first electron affinities are exothermic. © The first electron affinity of chlorine is shown below. Cigite > Cig) AH =-349 kJ mol? Lattice enthalpy J Lattice energy is a good indicator of the strength of an ionic bond. Generally 2s lattice energy increases, the stronger is the ionic bond. > Factors affecting the magnitude of lattice energies are ionic charge, ionic radius and the arrangement of ions in the crystal structure. LEA rete lattice energy = where q-and q, are the charges on the cation and the anion respectively and and ra refer to the ionic radius of the cation and the anion respectively. @ The lattice energy for sodium chloride is shown below Na’ (g) + F(g)->NaF(s) AH =-919 kd mol” 3 chal boning 3-5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.{i Summary of procedure for drawing ‘dot and ~ cross’ diagrams Count total number of electrons in all the atoms | Draw the skeletal structure | Place 2electronsin each bend | Identify terminal atoms (usualy hydrogen atoms) | subtract no, of used electrons from total no. of electrons. Any electrons let? «fT Place electrons on central atem Do all atoms have ectets? Yes Form muttiplebones sencededto complete octets Asatsfactory Lewis structure is obtained @ The ‘dot and cross’ diagrams for some covalent compounds are shown below, (a) Hp Hot «HHH Hydrogen has 1 valence electron. Therefore it shares the electron with another hydrogen atom to obtain aduet of electrons. (b) 0, 208 +20% > 808 20% Oxygen has 6 valence electrons. Therefore each oxygen atom shares 2 electrons to form a double bond (2 covalent bonds) and achieve an octet structure. © ch $+ .dy + gcrecl: Chlorine has 7 valence electrons. Therefore each chlorine atom shares 1 electron to obtain octet structure. (@) No SN°+. NE ONSEN Nitrogen has 5 valence electrons. Thus each nitrogen atom shares 3 electrons with another nitrogen atom to obtain octet structure. {ans} 3 chal boning 3-9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.% Electronegativity is a measure of the tendency of an atom in a covalent bond to attract a bonding pair of electrons. The more electronegative atom pulls the electrons of the covalent bond ‘towards itself and acquires a small negative charge while the other atom acquires a small positive charge. Polarisation is the unequal sharing of electrons, forming polarized covalent bonds which have dipoles (separate regions of charge). 4 Acovalent bond between two identical atoms is not polarised as the electrons are equally shared. 4 ‘Apolar molecule with a dipole moment has polarised bonds and is not symmetrical, & ‘The dipole moment of a molecule is the vector sum of all the individual dipole moments of the covalent bonds in the molecule. J Anon-polar molecule has no dipole moment. Anon-uniform electrostatic field such as a charged rod is able to deflect the flow of liquids containing polar molecules. No deflection will be observed for non-polar molecules. © The H-F bond is poler as the bonding pair of electrons in the covalent bond is attracted towards the more electronegative fluorine atom. wo H—F % Apolar molecule has a digole moment if it contains polarised bonds and is not symmetrical. The dipole moment is the vector sum of all individual dipoles of the covalent bonds in a molecule. @ Individual dipole of CC! cancel each other, thus the molecule has no dipole moment. ca It Cm Py ca 3 chal boning 3-3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.Tetrabedral che tetranecral 4 HGH i trigonal pyramical 107 Ho ye wen bent 105" Trigoral bi pyramidal PCle cl ict nhl a? trigonal bipyramidal 120° and 90" SF distorted tetrahedron Fs F Le oie F T-shaped 20° Yer, i ore i) F 180" 3 chal boning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 © the shape of the molecule, © Long, unbranched molecules have a greater surface area for intermolecular forces to exist. ‘As the strength increases, the boiling point and melting point also increase. For example, bromine is liquid at room temperature while fluorine is a gas. The bromine atom is heavier than fluorine, hence more likely to have induced dipole-dipole interactions, resulting in stronger dispersion forces between molecules. To become @ gas, bromine requires more energy to overcome the Van Der Waals’ forces. Induced dipole-dipole interactions occur even in monatomic molecules such as the noble gases. At any instance, the electrons round an atom will be unevenly distributed round the nucleus, causing a temporary dipole. This temporary dipole can induce a dipole in a neighbouring atom Noble gases become liquid at low temperatures. Helium has 2 lower boil point of -269°C, as compared to radon at ~62°C. Radon has a larger atom than helium, hence have to overcome greater Van der Waals’ forces. ‘The intermolecular forces in anionic bond is termed ion-ion bond asthe concept of a ‘ingle molecule becomes blurred asthe solid crystals ext as one continuous system. The forces between molecules re comparable to the forces within the molecule. Permanent dipole-dipole forces a 2 & ‘This type of interactions usually occurs in polar molecules. ‘They arise due to permanent dipole attraction. One end of the molecule has partial positive charge while the other has a partial negative charge. The oppositely charged ends attract each other. ‘The molecules will orientate themselves to maximise attraction, producing a system with the lowest potential energy. ‘These forces also occur in some non-polar molecules such as carbon dioxide in the solid state. ‘These forces are weaker than covalent and ionic bonds but stronger than the van der Waals’ forces. ‘An example of permanent dipole-dipole interactions occur in CHC/s, which is polar because their dipole moments do not cancel each other. 3 chal boning 3-21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 CH,CH, < CH,C(CH,),CH, < CH,CH,CH,CH,CH, < CH,C(CH,),CH,OH < HOH,CC(CH3))CH,0H (ans) Explain the following phenomenon. (2) The density of ice is smaller than water. (b) Boiling points of hydrides tend to increase down a group due to an increase in relative molecular masses, However, the hydrides of the first member of Group V, VI and VII are higher than expected. (c)_ The viscosity of a diol (alcohol with two OH groups) is greater than that with a single OH group. (4) 2-nitrophenol has a higher boiling point that 4-nitrophenol. (a) Inice the hydrogen bonds hold the molecules together ina 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 VII, 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 toa hydrogen atom. More energy is required to overcome the hydrogen bonds as compared to molecules with only Van der Waals’ forces. (ans) (c)_ Adiol 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. ans) (4) Hydrogen bonding accounts for the difference in boiling points of the two isomers, 4-nitrophenol and 2-nitrophenol. Intramolecular hydrogen bonds are formed between the atoms in a molecule e.g,, 2-nitrophenol. | intramolecular ° oO eo on . oo 0 4-nitrophenol cannot form intramolecular hydrogen bonds as the hydrogen atom is too far from the oxygen atom. It can only form intermolecular hydrogen bonds with another molecule. This causes the boiling point of 4- nitrophenol to be lower than that of 2-nitrophenol._ (ans) . 3 chal boning 3-25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.i Characteristics of covalent compounds Simple molecular solids © Poor conductors of heat and electricity ©The electrons shared between the atoms are not mobile. © Low melting and boiling points © little energyis required to break the weak intermolecular forces of attraction. © Generally soft © The molecules can be separated easily as the intermolecular forces are weak. © Soluble in non-polar solvents © Non-polar solvents are able to penetrate the simple molecular solid and solvate the molecules. © Insoluble in polar solvents ©The molecules of simple molecular solids cannot penetrate polar solvents as the solvent-solvent attractions are much stronger, thus they are insoluble. (Examined in 201391.5] Giant molecular solids © Poor conductors of heat and clectricity © The electrons shared between the atoms are not mobile, © High melting and boiling points © Alotoof energy is required to break the strong covalent bonds. © Insoluble in all solvents ©The strong covalent bonds mean that the solvent molecules cannot penetrate the lattice and thus cannot solvate it. © Slippery 0 The Van der Waals’ forces between the layers are relatively weak and thus they can slide over one another. (Examined in 2013p1.5) 3 chal boning 3-29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.az (Ges:20%) = 6.0% 10% molt ‘Avogadro constant The coordination number depends on the relative sizes of the ions in the lattice. > Alarge ion can fit more ions around it than a small one. 4 There are three kinds of unit cells: © A simple cube where atoms are placed one at each corner. © A face-centred cubic structure has a cubic unit cell where atoms are located at each of the corners and the centres of all the cube faces. ‘An example is sodium chloride which shows a 6 :6 co-or ion. © A body centred cubic structure has a cubic unit cell where atoms are located at all eight corners and a single atom at the cube centre. ‘An example is caesium chloride which shows an 8 : 8 co-ordination, Simple molecular solid Alattice of discrete molecules is held together by weak intermolecular forces of attraction. Examples include iodine, carbon dioxide, sulphur dioxide and methane Giant molecular solid Alattice of atoms is held together by strong covalent bonds. 4 The entire erystal isa giant molecule. 3 chal boning 3-33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.Diamond has a structure which is very strong and rigid due to the strong ¢-C bonds and tetrahedral arrangement of atoms. This prevents movement of the atoms. Silicon (IV) oxide (giant covalent) a a 4 Silicon (IV) oxide has a giant, covalent structure, Each silicon atom is covalently bonded to four oxygen atoms which are held at the comers of a regular tetrahedron. Each oxygen atom is covalently bonded to two silicon atoms. ‘Thus the Si: O ratio is 1:2 Ice (hydrogen bonding) Each water molecule is bonded to four ather water molecules to form a b wate as tend tctratedal arrangement Hydrogen bonding in ice results in it te— Hydrogen having an open rigid structure, causing = wee "Ge bond ice to be less dense than water. > When ice melts, the rigid structure is ye 4 o broken andthe water moleculesmoe =, “Ke OH closer together, thus water will have 9 higher density. Therefore ice floats on water. Water has a high boiling point due to the presence of hydrogen bonding. Therefore it exists as a liquid under normal atmospheric conditions. % The extensive hydrogen bonding forms a lattice across the surface of water, giving it@ high surface tension. Copper (metallic) Copper has a giant metallic structure, with a face centred cubic close-packed structure and a coordination number of 12. |} Delocalised electrons move randomly throughout the metallic lattice of regularly spaced positively charged ions Iron (metallic) a Iron exists in the a-form (body-centred cubic] below 906°C. 3 chal boning 3-37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.Solution: (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 ithas a high melting point. The ions are only mobile in the molten state, thus it can only conduct electricity in the molten state, (ans) {b) tis hard and brittle and only soluble in polar solvents. (ans) Compare the similarities and differences between the properties of simple molecular and gient molecular solids. Solution: Melting and Low High boiling points Conductors of Good conductors Non-conductors electricity Solubility Soluble in non-polar solvents | Insoluble in all solvents but insoluble in polar solvents 3 chal boning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 41 Kinetic molecular modet 42 doalgas behaviour and coviations ‘rom it 43° pV =aRTand its usein determininga value for M, Learning Outcomes ‘Candidates should be ableto: (0) statethe basic assumptions ofthe hinetic theory as applied to an ideal gas. (©) explain qualitativelyin terms of intermolecular forces and molecular sie: |i) the conditions necessary for agas to approach ideal behaviour [ithe imitations of ideality at very high pressures and very low temperatures (0) stateand use the general gas equation pV = nT incalculations, including the determination of M,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.and forces of attraction between particles cannot be assumed to be negligible. © temperature © At lower temperatures, the intermolecular attractions are not negligible as the gas particles do nat have enough energy to overcome it. & real gas behaves most lke an ideal gas at low pressures and high ‘temperatures, €xamined in 2013p1.6) Differentreal gases deviate to a different extent from ideal gas behaviour. Polar molecules deviate more from ideality as compared to non-polar molecules due to the stronger forces of attraction > Significant attractive forces are present in a real gas, decreasing the force with which the molecule collides with the wall. This results in a reduction in pressure. With an increase in atomic size and number of electrons, there will be an increase in the intermolecular attractive forces. Worked Example (2) 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. Solution: (2) When airis expanded into a region of lower pressure, it is an endothermic process. This is because at low pressure, the molecules are further apart from one another and energy is required to overcome intermolecular attractions. Thusit isendothermic. (ans) (b) When pressure is increased, the gaseous particles become closer to one another. There will come a point when the pressure is so high such that the particles can no longer move around freely. The gas has condensed into a liquid. (ans) (c)_ Since the average kinetic energy of a gas is dependent on the temperature, as temperature increases, the average kinetic energy will increase until the particles cannot be held within the volume of the liquid even though the increase in pressure is pushing the particles together. The temperature at which this occurs is the critical temperature. The increase in intermolecular attraction is not enough to hold the particles within a fixed volume due to their high kinetic energies of the particles above the critical temperature. 4 thepsour sate 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.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) Let V; be the new volume. PM _ PVe oth PVs = Pas 4000 0.172= 4500 « Vs Vp =0.153 m’ (3 sf) (ans) When 5.2 of a substance was completely vaporized at 25°C and 35000 Pa, 0.006 m’ of vapour was produced. Calculate the relative molecular mass of the substance. Solution: pV=nRT (7298.15 8.314) ™ 35000 x 0,006 M, M, 41.804m 1.804 «5.2 =61.4(3 sf) (ans) 4% thepou state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 51 __Enthalpy changes: AH, of formation; combuston; hydration; solution; neutralisation; atomisation; bend energy; lattice eneray; electron affinty 52 Hess’ Law, including Born Haber cycles 53 Entropy and Free Energy Learning Outcomes ‘candicates should be ableto: (2) explain that some chemical reactions are accompanied by energy changes, grincipaly in the form of heat energy; the energy charges can be exothermic (AH, negative) or endothermic (4, postive) (©) explain ané use the tems (0) enthalpy change of reaction and standard conditions, wth particular reference to: formation; combustion; hydration; solution; neutralisation; stomisation (i) bond energy (4 postive ie. bond breaking) (i) lattice energy (AP negative, Le. gaseous fons 1 sold lattice) (0 aleulate enthalpy changes from appropriate experimental results, including the use ofthe telationshio heat change=mcAT () explain, in quatkative terms, the effec of ionic charge and of onicradius on the numerical magnitude of alattice energy (6) apply Hess’ Law to construct simple energy cycles, ¢.g. Born-Haber cycle, and cary out «aleulations involving such eyeles and relevant eneigy terms fineluding ionisation enersy and electron affinity, with particular reference to: (determining enthalpy changes that cannot be found by direct experiment, eg. an enthalpy change of formetion from enthalpy changes of combustion (i) the formation ofa simpleionic solid and of its aqueous solution (ii) average bond energies (9 construct and interpreta reaction pathway diagram, in terms of the enthalpy change of the reaction and ofthe activation enerey (@) explain and use the term entropy (b) discuss the effects on the entropy ofa chemical system by the following: (change in temperature (change in phase (ii) change in number of particles (especially for gasecus systems) (uv) mixing of particles quantitative treatment is not required} (predict whether the entropy change for a given process or reaction is positive or negative define standard Gibbs free eneray change of reaction by means ofthe equation AG? = AMP = TAS® (k) calculate 46° for a reaction using the equation AG® = AH? —TAs® [the calculation of standard entropy change, AS, for a reaction using standard entropies, 5°, isnot required) (sate whether areaction or precess will be spontaneous by using the sign of AG (m)_ predict ne ettect of eemperature change on the spontaneity ofa reaction, gen standard enthalpy and entropy changes 5 eemialenwete s-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.Standard enthalpy change of combustion ‘The standard enthalpy change of combustion is always a negative value as heat is always evolved, It indicates the energy values of foods and fuels, and is measured using a “bomb calorimeter’ © S(s) +Osle) > Orla) Standard enthalpy change of hydration The standard enthalpy change of hydration is always a negative value as, heat is always evolved when the bonds are formed between the ions and the dipoles on the water molecules. {Examined in 2012p1.6] The hydration energies of compounds can be obtained by adding the hydration energies of the constituent ions. ‘The hydration energies of ions depend on: © Charge of the ion The higher the charge, the greater is the hydration energy. © | Size of the ion ‘The smaller the size of the ions, the greater is the hydration eneray. * Na‘(g)+aq — Na‘(aq) MHlnyd® =—390 kd mol * Br(e)+aq — Br (aq) AHlngi® =—351 KI mol ¢ Na‘(g)+B8r (g)+aq — Na‘(aq)+Br (aq) AHyd? =—741 kJ mol? Ld 5 eemialenwete 5-5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.. Adocrease in temperature follows an endothermic reaction while the converse is true for an exothermic reaction. where m =mass of the solution ¢ =spetificheat capacity of solution AT=change in temperature Worked Examples State if the following reactions are exothermic or endothermic. (2) Addition of hydrochloric acid to sodium hydroxide (b) Combustion of natural gas (c)_ Photosynthesis (4) Addition of concentrated sulphuric acid to water. Solution: (2) Exothermic. (ans) (b) Exothermic. (ans) () Endothermic. (ans) (4) Exothermic. (ans) In an experiment, the temperature of a bomb calorimeter is raised by 4.8°C when 2.25 g of sucrose CizHlz20: is burnt in it. Given thet 16.5) of energy is required to raise the temperature of the calorimeter and its content by 1°C, determine the enthalpy change of combustion of sucrose. Also, calculate the theoretical amount of energy released when 15.0 g of sucrose undergoes complete combustion Name a common source of error in calorimetric experiments. Solutio CiHyOns(s) +120,(g) > 12C0,(g) + 11H,0(1) Heat released by reaction = heat gained by calorimeter and its contents = 16.5(4.8)= 79.2) 225 (2201242241611) = 6.5790 x 107 mol (5 sf} Amount of CH220. = 5 eemialenwete 5-9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 further up the line a system is located, the greater enthalpy the enthalpy content of the system. ' |_tigh eneray Arrows pointing upwards indicate positive enthaloy values while arrows pointing downwards indicate i a [tow eneray negative enthalpy values. The dissolution of an ionic solid occurs in two steps: [taro energy © Breakdown of the crystal lattice to form gaseous ions ‘An amount of energy equal to the lattice energy is absorbed to break the intermolecular bonds. © Hydration of gaseous ions ‘An amount of energy equal to the hydration energy is evolved in forming bonds between the ions and water. J The salt dissolves readily in water if the enthalpy change of solution is negative (hydration energy > lattice energy). 4 The salts relatively insoluble in water if the enthalpy change of solution is. positive (hydration energy < lattice energy). Worked Examples ‘The standard enthalpy change for the reaction below is 178.1 kl. CaCOx(s) —> Cad{s)+CO,(e) Calculate the standard enthalpy of formation of CaCO3.. C (s) + 02 (g) > CO: (a) 393.5 Ca(s) +0.5 0; |g) > Ca0 (1) 635.5 Solution: The overall equation can be written as the sum of three formation reactions: CaCO,(s) > Cals) +C(s} + 0,(8) + Cls)+O2\g) > COz\8) + Cals)+0.50,g) > Ca0(I) (aCO4(s) > Ca0{s) + CO.(8) 178.1 = (-393.5) + (-635.5) ~AH¢* (CaCO) AH? (CaCOs) = -1207.1 ki mol * (ans) 5 eemialenwete 5-13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.\ Ei Entropy and free energy Define Entropy & Nature tends towards maximum entropy in isolated systems. The larger the value of the entropy, the larger is the degree of randomness of the system. {tis an intrinsic property of a system, functionally related to the measurable coordinates which characterise the system. © _ teowes ts existence to the second law of thermodynamics. & ‘The entropy of a chemical system is dependent on these factors: © Change in temperature Entropy increases with an increase in temperature as molecules in solids vibrate faster while those in liquids and gases move more rapidly. © Change in phase Seas >> Siquit » Scots. Entropy is affected by the orderliness of the molecules in each phase. (examined in 2012p1.6,2013p2.23] © change in number of particles Entropy increases with an increase in the number of particles in a system. This is especially true in gaseous systems. © Particle mixing Entropy increases ina mixing process which is random and homogeneous. Entropy change & The entropy change is given by the sum of the entropies of the products of a chemical change minus the sum of the entropies of the reactants. 4 Entropy change shows the change in the degree of disorder of a system. 5 eemialenwete s-17Entropy change is positive when a system becomes less orderly. Its negative when a system becomes more orderly. {€xamined in 2012p1.6, 2013p1.8, 201392.28] Entropy isa state function. It depends only on the state of the system, and therefore a change in entropy, AS, is independent of the path from start to finish Gibbs free energy o 2 s AL ches Gonplee ue Redistribution of matter and heat change take place in all chemical reactions. ‘The Gibbs free energy of a system at any moment in time is defined as the enthalpy of the system minus the product of the temperature and the entropy of the system. G=H-TS where T= temperature in K The Gibbs free energy of the system is a state function because it is defined in terms of thermodynamic properties that are state functions. ‘The change in the Gibbs free energy, AG, of the system that occurs during a reaction is therefore equal to the change in the enthalpy of the system minus the change in the product of the temperature and the entropy of the system. AG = MM ~A(TS) At constant temperature, AG = AH —TAS Free energy change, AG, is the driving force of a change. ‘The standard Gibbs free energy change of reaction is the change in Gibbs free energy taken at standard conditions. AGe = AM! — TAS: ‘© The value of AG* is highly dependent upon temperature. ‘©The reaction is feasible when AG* is negative. For example, organic combustion reactions, condensation and freezing, electrolysis and decomposition. © The reaction not feasible when \G°is positive. For example, photosynthesis. These reactions have to be driven. ©The reaction is at equilibrium when AG* iszero. {examined in 2013p1.8, 2013p2.2a} The spontaneity of a reaction depends on the AG® while the reaction rate depends on the activation energy.A + AG of a reaction= where AG= AG; (product) ~ 5 AG*; (reactant) standard free energy of formation Worked Examples State whether the entropy for the following processes is positive or negative. (a) Expansion of a gas into vacuum (b) Generation of a gas from liquid reactants (c) Freezing of aliquid (4) Condensation of a gas (2) Positive. (ans) (b) Positive. (ans) (€) Negative, (ans) (4) Negative. (ans) Explain how the following factors influence the entropy of a system. (2) temperature (b) phase (c)_ number of particles (4). mixing of particles Solutio (a) An increase in temperature will lead to an increase in entropy, as the molecular motion increases, leading to greater disorder in the system. (ans) (b) A change in phase will affect the entropy of a system. In the solid phase, the entropy is the lowest as the solid particles vibrate about 2 fixed position. In the liquid state, entropy is higher as the liquid particles are able to move about slightly. In the gaseous states, entropy is highest as the gas particles can move freely in all directions, leading to greater disorder. (ans) (c)_ An increase in the number of particles will increase the entropy of a system as there is greater disorder, especially in a gaseous system. (ans) (d)_ The mixing of particles will increase entropy as there will be greater disorder. (ans) 5 eemialenwete 5-19Explain how the spontaneity of a reaction can be indicated by the standard Gibbs free energy change of a reaction, AG°. Solution: Because of the way standard Gibbs free energy change of a reaction is defined, it is negative for any reaction in which AH° is negative and AS” is positive. Thus any reaction for which AG* is negative is a spontaneous reaction. (ans) = Given that AH® = -92.2 kl mol and AS= = -198.8 JK-*mol ”, predict whether the ‘manufacture of ammonia in the Haber process is spontaneous at 25°C or 500°C. Solution: At25°C, AG® = AH® ~TAS* (-92.2 10°) ~ (25 + 273)(-198.8) = 33.0 kJ (spontaneous) At500°C, AG® = AH® ~TAS* = (92.2 10°) - (500 +273)(-198.8) = +61.5 KJ (non-spontaneous) (ans) In an experiment, SOCh is added to Ba(OH),. A vigorous reaction occurs and the temperature drops by 25°C. What are the signs of AG and AS for this reaction? Solution: ‘Temperature drop indicates an endothermic reaction —> AH =+ve Vigorous reaction indicates a spontaneous reaction —> AG=-ve (ans) AG=AH ~TAS Hence TASistve = ASis tye (ans) [Gcamined in 2013p1.8] 5-20 AL ches Gonplee uej Worked Problems =a (2) Explain whatis meant by AH being a function of state, (b) State when the change in enthalpy is equal to the heat change in a reaction. {c)_ The complete combustion of propane is given by CH,CH2CH3(@) + 502g) > 3CO4(g) + 4H,0()) Given that AH. = a kJ/mol, AH/ H,0 = b ki/mol and Hy CO; =cki/mol, derive an expression for \H/* C3Hs (2) It means that the change in enthalpy is determined by the initial and final states and is independent of the path taken from the initial to the final states. (ans) (b) Constant pressure. (ans) (c) = 3c) +4(b) — ANP CHe AH) CsHy = 3e+4b—0 (a). State the factors that affect the dissolving of an ionic salt in water. (b) Aluminum fluoride is virtually insoluble in water. With reference to the factors in (a), explain why this is so. Solution: (2) The factors involved in dissolving an ionic salt in water are the lattice energy Of the ionic solid and the enthalpy change of hydration of the ions. (ans) (b) Aluminium fluoride is highly insoluble in water asit has a high lattice energy caused by the small and highly charged aluminium ions and small fluoride ions, The energy released during the hydration of the ions is insufficient to compensate for the energy required to overcome the lattice energy. (ans) Calcium reacts with oxygen to form calcium oxide, (a). Given the following information, sketch the energy diagram for the reaction. 5 eemialenwete s-2t‘Atomization energy of Ca (s) +77 First ionization energy of Ca (g) +590 ‘Second ionization energy of Ca (g) +1100 Atomization energy of oxygen +249 First electron affinity of oxygen -141 Second electron aifinity of oxygen +790 Enthalpy change of formation of calcium oxide 636 (b) Calculate the lattice energy of calcium oxide. Solution: (a) Cals) +0.50(e) > CaO{s) ca” ig (a) +0 +649 | Ca** (p) + 0 ig) +1100 Ca’ {g) +O (g) can] Mia a Ca (g) +0 (a) +249 f Ca (g) +0.50, (g) a7 | Ca(s) +0.50>(g) (b) -636 = 177 +249 + 590 +1100 + 649 + AH, AMig: = ~3401 kJ mol (ans) Calculate the enthalpy change of hydration of the chloride jon using the Information given below. Enthalpy change of solution of NaCI (s) Enthalpy change of hydration of Na’ (g) Lattice energy of sodium chloride 5-22 AL ches Gonplee ueNaCl (s)_ 2+ na" (aq) +!" (oe) 22 | eo Na*(g)+ Cl (g) ‘MH +(-390) = 722-2 AH = ~334 ki mol” (ans) 2NO.{g) — N20,(g) (2) Predict the change in enthalpy for the reaction above. Explain your answer. (b) If the AH NOz = 33.2 ki/mol and AH/ N203 = 9.2 ki/mol, calculate the standard change in enthelpy. (c) Ifthe change in entropy is -0.176 kJ/mol, calculate the temperature at which the equilibrium constant, K, = 1.0. |AG= = 0) Solution: (2) The change in enthalpy should be negative as the reaction involves bond making, thus energy is released and it is an exothermic reaction. (ans) (b) AHP (ce) AG? = AH® —TAS® =-57.2—T-0.176) = 325K (ans) Using the information provided in the table below, determine the enthalpy change of combustion of propane. CH 4413 cc 4347 0-0 +498 c=0 +805 H-O +464 Solutio CH{CH,CH,(g) + 50,(@) > 3C0,\g) + 4H,0(1) 5 eemialenwete 5-23nergy required for bond breaking — energy given out from bond forming =8(413) + 2(847) + 5(498) — 6(@05) 8/464) =-2054 kJ mot (ans) (a) Calculate the standard enthalpy change for the combustion of 1 mol of CeHe(I), to COa\g) and H20(|). {b) State if the combustion of C.Hi(!) is endothermic or exothermic and explain why. {c) Compare the quantity of heat produced by combustion of 1.00 g propane to that produced by 1.00 g CeH(!). (standard enthalpy of combustion of, propane is ~2220 ki/mol) (2) cot+ Bove) > 6¢0,6) +3H,000 The overall equation can be written as the sum of three formation reactions: Celle) > 6C(s) + 3H-(g) + 6C\s)+60,g) > 6C0,(8) + Hie) 20,6) > 34,00) 15 CeHelg) + 5 O2{8) —> 6CO2(g) + 3H,0(!) Enthalpy change of combustion = ~49,04 +6(-393.5) +3(-285.8) = -3267 KI mol” (3 sf) (ans) (b) The reaction is exothermic as the amount of energy released from formation of bonds is greater than the energy required to break the bonds. (ans} (c)_ To determine the heat of combustion per gram of each substance, we use the molecular weights to convert moles to grams: 3267 CHe= >" = -41.9 ke 78 = Cota = 2220 = -505 kig? 7 Therefore CsHy produces more heat than C.Hg per gram of hydrocarbon and it is more effective asa fuel. (ans) 176 kJ mol * for the dimerisation of nitrogen dioxide, estimate the temperature at which the reaction is at ‘equilibrium. Also, state how the values of AH® and \S° relate to molecular changes. 5-24 AL ches Gonplee ueSolutio: Since AG*=0 at equilibrium, \H°= TAS* AH® as> (-87.2x103) ~Ci76) =325K AH is exothermic due to the formation of a new N-N bond. This value is slightly negative as the bond formed is weak. No bonds are broken in this reaction. .AS® is negative as there is a decrease in the number of particles. Thus the system. becomes more orderly and the entropy is decreased. (ans) a Taken together, nitrogen and oxygen make up 99% of the air. Oxygenis by far the more reactive of the two gases, and most of the substances that react with air combine with the oxygen rather than with the nitrogen. (a) State one reason why the molecule of nitrogen, Nz, isso unreactive. [1] Despite the apparent lack of reactivity of Nz, nitrogen atoms have been found to form bonds with almost all of the elements in the Periodic Table. Lithium metal reacts with nitrogen gas at room temperature to give lithium nitride, LisN. Magnesium produces magnesium nitride, Mg:Nz2, as well as magnesium oxide, when heated in air. (b) Calculate the lattice energy of magnesium nitride using the following data, in addition to relevant data from the Data Booklet. BB] atomisation of Mg(s) +148 total of electron affinities for the change N(g) —> N° (g) 42148 enthalpy of formation of MaiNals) “Ast {c)_ Lithium reacts readily with nitrogen, and because of this LiN has been considered as a possible intermediate in the ‘fixing’ of nitrogen to make ammonia-based fertilisers Nag) —Y> Lian #25 NHs +A (i) Construct an equation for the reaction between LisN and H20, and hence identify compound A. (ii) Using your knowiedge of the Haber process, consider one advantage and one disadvantage of using lithium asa means of fixing nitrogen, rather than the Haber process. 1 (@) Another possible advantage of LisN is that it contains a large percentage by mass of nitrogen, Another fertiliser that containsa large percentage by mass of nitrogen is urea, NH;CONH>. 5 eemialenwete 5-25{i) Calculate and compare the percentages by mass of nitrogen in LijN and NH,CONH,. (ii) What class of organic compound is urea? (iil) Write an equation for the production of ammonia by the reaction between urea and water. {iv) Urea can be applied directly to the soil either before or during the growing of crops. What would be a major disadvantage of using lithium nitride in this way? 5] {[Total: 12] Solution: {a)_NEN triple bond isvery strong (ans) (b) 3Mg(s) > 3Me""(e) Ma = 3 x 148 +3 x 2186 = 7002 Nag) > 2N" (g) AH, = 994 +2 «2148 =5290 LE = AH, — AH, ~461 = ~12,753 I mol * (ans) © (ii) advantage: disadvantag iN +3H;0 > NH3+3LIOH (ans) no high pressure used (ans) Lis expensive (ans) (4) () WN: 100% 4 =40%N (ans) urea: 100 47% N (ans) aie (ii) amide (ans) (iil) NHzCONH, +H20 > 2NHs+CO; (ans) {iv) The LiOH would be strongly alkaline (ans) AL ches Gonplee ueor NH,CONH, +2H20 > 2NHs+ HCO, fl (iv) The LOH would be strongly alkaline or would increase the pH of the or would ‘burn’ the crops/reduce plant growth/stunt plants ‘or would contaminate the environment i (Total: 12) © Teachers’ Comment (a) Candidates were generally aware of the triple bond in a nitrogen molecule, but not all went on to say that this was a strong bond or required considerable energy to break it. (b)_ This calculation was completed only by the more able candidate, with ‘others missing out terms. Even ifall the terms were present, multipliers were often incorrect. The most common errors were omitting the bond energy of No (or doubling it), using just the second Tonisation energy of Mg, rather than the sum of the first two, and not multiplying the atomisation and ionisation energies by three. Candidates might have been more successful if they had drawn out the energy diagram for the process. (©) (Although this was a relatively easy equation, a large number of candidates thought that LizO was a product rather than LiOH. (ii) Most candidates were able to give an advantage of the method, but fewer gave ¢ reasonable disadvantage. Examiners were expecting candidates to think about the cost of lithium, the need to remove the LiOH, or its strongly basic nature, (d) (i) Most candidates carried out these calculations successfully. (ii) A number of candidates gave amine rather than amide here. (iii) Most candidates were able to give a correct equation. {iv) Answers to this part were often too vague to be awarded credit. Some candidates referred to lithium metal or lithium nitride rather than lithium hydroxide in their answers. Baampie 10 Inthe Contact process, SO, is oxidised using a vanadium(V) oxide catalyst. S02 (g) +%402(8) = SOs (8) o At the temperature of 298K, AH(* {SO,) =-297 kJ mol * Hg (S03) = -396 KJ mol * AS® =-93.5 JK “mol * Deducing AH? for reaction @, AH? = EAH/? produas) ~ EAM (eacents) = (396) - (297+ 0) -99 kJ molDeducing AG for reaction AG AWe = TAS {-99000) ~ (298)(-93.5) 72.1k) mol? [Examined in 2012922] AL ches Gonplee ue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6.1 | Redox processes Define Redox reactions % The oxidising agent is the reactant that causes oxidation and itis reduced in & The reducing agent is the reactant that causes reduction and itis o the process. sed in the process. Redox reactions involve the transfer of electrons. ‘+ Whena substance loses electrons, itis said to be oxidised. © Whena substance gains electrons, itis said to be reduced. lation state 8 FL cheisoy ~ Gnplte ui Oxidation involves an increase in oxidation number. Reduction involves a decrease in oxidation number. Free atoms have an oxidation number of zero. For example, Fe, H2 and Cl, Covalent compounds, ionic compounds and ions have an oxidation number which is similar to that of the charge on the ion. For example, Li’, Mg”’and oO. For uncharged molecules, the sum of the oxidation numbers of all atoms is, zero. For example, in $O,, the charge of S is +4 and that of 0 is ~2. Sum of oxidation numbers = +4 +2(-2)=0 For charged molecules, the sum of the oxidation numbers of the atoms is the same as the charge of the ion. For example, in NO,’, the charge of N is +45 and that of O is~2. Sum of oxidation numbers = +5 + 2(-2) = +1 Most elements, apart from the transition elements, always exhibit only one oxidation state in its compounds. For example, all Group | elements always have an oxidation number of +1. (Examined in 2012p1.35, 2013p1.34]Disproportionation [€xaminedin 20139134) Worked Example Ea) (2) For the following reaction, determine which substance has been oxidized and which one has been reduced in terms of electron transfer. Cals) + 2HCllaq) —> CaClas) + Hols) (b) For the following reaction, determine which substance has been oxidized and which one has been reduced in terms of oxidation number. Mg(s) + 2HCi(aq) > MgCls(s) + Hag) (a) When a substance loses electrons, itis said to be oxidized. Calcium has been oxidized because it has lost electrons to form calcium ions. ca > Ca 420" When a substance gains electrons, it is said to be reduced. Hydrochloric acid has been reduced because the hydrogen ions have gained electrons to form a hydrogen molecule, 2H’ +2e > Hy (ans) (b) Magnesium has been oxidized because it has undergone an increase in oxidation number from Oto +2. Mg -> Zn** Hydrochloric acid has been reduced because it has undergone a decrease in oxidation number from +1 to0. 2H’ > Hp ans) © leroehenry6.2 | Electrode potentials Define Electrochemical cell a & FL cheisoy ~ Gnplte ui The flow of electricity is possible in an electrochemical cell due to the following reasons. ‘© When a metal is placed ina solution of its ions, the metal atoms loses electrons to form its corresponding ions. ‘¢ Atthe same time, the ions in the solution gain electrons te form the metal. ‘©The position of equilibrium depends on the relative ease with which the metals lose their electrons, e.g., for more reactive the metal, the equilibrium lies to the right. X(s) = X"(aq)+ne © Consequently, a double layer of positive and negative charges develops at the interface between the metal electrode and solution. It is called the Helmholtz double layer. ‘© Apotential difference known as the electrode potential is thus set up between the double layer. ‘+ When the two haif-cells are connected together, electrons will flow from the more reactive electrode to the less reactive electrode. ‘The anode is the negative electrode where oxidation occurs while the cathode is the positive electrode where reduction occurs. The electrode potential may be positive or negative depending on the position of equilibrium. An example of an electrochemical cell is a Galvanic/voltaic cell. Electrochemical cells can be represented by a cell diagram The left hand side is where oxidation occurs * [represents phase boundaries. * /{represents the salt bridge. Reduced form/oxidized form // oxidized form/reduced form (oxidation) (reduction)© The cell diagram for the electrochemical cell consisting of Ag /Ag and cu*'/Cu half cell is Cu/Cu* // Ag'/Ag. Electromotive force & The unit of electromotive force is volts 4 The greater the potential difference, the greater the tendency of redox reactions to occur. Standard electrode potential When a metal is placed in a solution of its ions, two reactions can happen, «The metal atoms may lase electrans and go into solution. ‘+The metal cations may gain electrons and form the metal. ‘© An equiliorium is established between the metal and its ions. At this eq m, a potential difference is set up between the metal and an aqueous solution of its ions. Thisis called electrode potential M™(aq)+ne = M(s) Factors affecting the electrode potential include: © Temperature and pressure. © Nature of metal. © Concentration of ions. ‘The standard conditions used in determining the cell potential of these electrodes are: © Temperature of 298 K. © Partial pressure of any gas involved is at 1 atm © Concentration of ions involved is at 1M. a Standard electrode potentials are measured by comparing with the standard hydrogen electrode (reference electrode). © leroehenry 65> Astandard hydrogen electrode (SHE) is an olectrode that is used as reference on all half-cell potential reactions. The value of its standard electrode potential is zero, which forms the basis one needs to calculate cell potentials using different electrodes or different concentrations. Adiagram of the standard hydrogen electrode is shown below. Platinum wire Salt bridge Ha (g) at 25 °Cand 1 atm — Patinized platinum electrode Glass has holes for H:(g) toescape < Amol dn Hq) * An equilibrium is established between the hydrogen gas and the hydrogen ions. 2H'(ag) +2e° = Hie) * The potential difference is arbitrarily set to be OV. © silver /silver chloride electrode is used as a reference electrode in a laboratory as itis difficult to maintain the pressure of hydrogen gas at 1 atm in the standard hydrogen electrode. © The standard electrode potential provides the following information. © The magnitude of the electrode potential indicates the tendency of the electrode reduction reaction to proceed from left to right (reduced). The higher the magnitude, the greater is the tendency to be reduced. lezomined in 201393.10] © The sign of the electrode potential indicates the feasibility of the reaction. A negative electrode potential will mean that the reaction is energetically not feasible while a positive electrode potential will mean that the reaction is energetically feasible, [Examined in 2013p2.261 © The direction of electron flow can be predicted. Inthe external circuit, electrons flow from the electrode with the more negative E° value to ‘the more positive E° value Methods to measure standard electrode potentials & annie ie Standard electrode potentials are measured using the standard hydrogen electrode as a reference. The standard electrode potential is used for metals or non-metals in contact with their ions in aqueous solution. For haif-cells that contain ions of the same element in different oxidation states, the potential is termed standard redox potential@ To determine the standard electrode potential of Zn” (aq)/Zn(s) half cell: The apparatus is set up as shown below. (v)} frat 7 wire salt bridge Hs(g) at 25°C and 1 atm —o= peace Platnized platinum slectrode 7 anotdn’ vt eq —| 41 mol dn zn (2g) A salt bridge connects the standard hydrogen haif-cell to the zinc halt- cell. The electrodes are connected by a high-resistance voltmeter. The reactions at the electrodes are: 2H'(aq) +26 > Hale) 2n(s) > 2n?*(aq) +267 Overall reaction: Zn(s) +2H"(aq) > Zn”"(aq) +Hale) The voltmeter reading is -0.76 V. Cell diagram is Zn(s)/2n™*(aq) // H"(aq)/Ho(g)/Pt(s) lexemined in 2013p1.23] © To determine the standard electrode potential of Clz\g)/CI”(aq) half cell The apparatus is set up as shown below. v f= Pistiun 7 wire Hy (g) at 25 salt bridge Latm| Platinized — platinum — electrode hig) 325°C and atm platinum electrode mol div? H* (aq) Amol dm? cl (2g) The reactions at the electrodes are Hale) > 2H"(aq) +267 Chg) +20" > 2CI"(aq) Overall reaction: Chig) +Halg) > 2C/"(aq)+2H"(aa) The voltmeter reading is +1.36 V. Cell diagram is Pt(s)/Ha(8),H (aq) // Cla(g)/Cl (aq)/Ptts).. © leroehenry 6-7© Todetermine the standard redox potential of Fe®’{aq)/Fe” (aq) half cell: ‘The apparatus is set up as shown below. (} — Ha a) a825°Cand Salt bridge tam Flatinaed slatium | —— 4 |4 stectrode platinun electrode mot Lmoldm” H” (a9) and Fe’ (a9) The reactions at the electrodes are: Ha(e) > 2H (aq) + 26° FeM(aq) +e” > Fe*(aq) Overall reaction: 2Fe”'(aq) +H2(g) > 2Fe”' (aq) +2H'(aq) (e1amined in 201392.26] The voltmeter reading is +0.77 V. Cell diagram is Pt(s)/H,(g),H" (aq) // Fe*(aq)/Fe**(aq)/Pt(s), Electrochemical series ‘The more reactive the metal, the higher its tendency towards oxidation. Reactive metals are placed high in the series. & .% Ametal can displace any metal below it in the series from its corresponding ‘compound. Apart of the series showing the more common metals: Calcium ~287 Sodium 2 Magnesium =2.38 ‘Aluminium =1.66 Zine =076 tron 0.04 ‘Nickel 025 Lead -013 Copper +034 6-8 FL cheisoy ~ Gnplte uiElectrochemical cells a & Chemical reactions convert chemical energy to electrical eneray in electrochemical cells. ‘The anode (negative electrode) is where oxidation occurs while the cathode (oositive electrode) is where reduction occurs. Electrons flow from the negative to positive electrode in the external circuit. Standard cell potential Itis the may um potential difference between the electrodes. Feet = Ered + Eee Reactions with positive standard cell potentials are thermodynamically feasible. However, the reactions might not occur if they have high activation energies or if they are not performed under standard conditions, Electrons flow from the negative to positive electrode. The standard cell potential has the same uses as the standard electrode potential However, they do not give any information about reaction rates, and only apply to standard conditions. To calculate the electrode potential of an electrochemical cell when redox half-equations are given in the Data Booklet: © Write the half-cell with the more positive standard electrode potential as the reduction process. © The half-cell with the less positive standard electrode potential is the oxidation process. The sign of its standard electrode potential has to be changed, © Add up the standard electrode potential of the two half-cells, To calculate the electrode potential of an electrochemical cell when redox half-equations are not given in the Dota Booklet: © Write the formula of the oxidant, reductant, conjugate oxidant and conjugate reductant. © Balance all other elements before that of oxygen and hydrogen. * For reactions in acidic medium, balance O using #20, and H using H. © leroehenry 6-9‘+ For reactions in alkaline medium, balance O using OH, and H using 0. © Balance charges using electrons. @ Ag'(aq)+e > Agis) e 40.20 Cu(aq) +26" > Cule) f= 4034 ‘As Ag’ is more positive it's reduced and Cu is oxicizea F qq) = 0.80 ~ (0.34) = 40.46 V ® Half-equation for the oxidation of S03" to SO,” under alkaline conditions: 80,7" +20H” > SO," +H,0 +20" Nernst equation (supplementary topic) The equation shows the variation of the electrode potential with the concentration of ions. where E° = standard electrode potential n= number of electrons transferred from reduced to oxidized form % The same equation can be also expressed as: where Q= reaction quotient or eq! © 2H +2e > H, ibrium constant Calculate the e.mf. for the reduction of H’ at 1.0 x 10” mal dm *to Hy at LOatm, at 298K ) (ogo | —P# H 6-10 FL cheisoy ~ Gnplte uiaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Batteries and fuel cells & Batteries (electrochemical cells) are portable sources of electricity. > Primary cells are discarded once the electrical energy is used up and cannot be recharged. Secondary cells can be recharged and re-used many times before being discarded. Dry cell © The dry cell is a primary cell and generates between 1.25V and 1.50V. The electrolyte is @ paste of ammonium chloride, zinc chloride and water with azine casing as the anode and a carbon rod surrounded by a layer of manganese (IV) oxide as the cathode. The half reactions are: & © Anode: Zn(s) > Zn”"(aq) +26” © Cathode: 2Mn0,(s) +2NH,'(aq) +2e > 2NHs(aq) + 2MnO(OHY(s) The overall reaction is Zn(s) + 2MnO,{s) + 2NHq'(aq) —> Zn" (aq) + 2NH,(aq) + 2Mn0(OH)(s} 4 The advantages include: © Tightly sealed © Noleakage & The disadvantages include: © Not rechargeable @ Voltage drop during rapid discharge © Corrosion of zinc by acidic electrolyte Lead-acid accumulator The lead-acid accumulator is a secondary cell, and the half-reactions at the electrodes are easily reversible. < It'is made up of a lead anode and a grid of lead packed with lead(IV) oxide as the cathode. The electrolyte is sulphuric acid. The half reactions are: © Anode: Pb{s)+S0,>(aq) <> PbSO,(s) +2e + Cathode: PbO,(s) + 4H"(aq) +0," (aq) + 2e7 <2 PbSO,(s) + 2H,0() The overall reaction is PbO-(s) + Pb(s) + 250,” (ag) +4H'(aq) = 2PbSO¢(s) + 242011) 6-2 AL chemo ~ Complete GuideA The reactants lead and lead(IV) oxide serves as electrodes. As they are solids, there is no need for separation into different compartments. & ‘The accumulator is charged by applying a current from an external source, which reverses the electrode reactions. + The state of charge in the battery is indicated by the relative density of sulphuric acid. The relative density of sulphuric acid is decreased upon gischarge as sulphuric acid is consumed in the anode and cathode. The advantage is that it is rechargeable while its disadvantage is that itis heavy. Fuel cell J Afuel cellis primary cell where the reactants are continuously replaced as they are used up and the products are continuously removed as they are produced, J Chemical energy from conventional fuels is converted into electrical energy by oxidation with oxygen. This process is direct and continuous. © Afigure of a fuel cell (using hydrogen and oxygen gas| is shown below. voltmeter a E stream of kor Stream of races | (aa) __ oxygen gas “1 I dlectrodes In this cell, hydrogen gas and oxygen gas are bubbled through porous carbon electrodes (which contain a platinum catalyst) into a concentrated solution of an alkali such as potassium hydroxide. © The half-reactions are: © Anode: Hylg) +20H"(aq) > 2H,0(l) +2€ + Cathode: O,{g) +2H,0(I)+4e" > 40H (aq) > The overall reaction is 2H,(g)+O,(g) —> 2H,0(I) The advantages include © High efficiency © Pollution free © Work indefinitely as long as the reactants are supplied continuously + The disadvantages include: © Expensive to operate as platinum is costly © High temperature needed © leroehenry 6-13Other types of cells Electric cars have many advantages over fossil fuel engine cars, such as pollution free, quiet and easy to maintain. > However, there are several limitations in electric cars: short driving range, long recharge time, heavy and expensive batteries, > New types of cells are being developed, including fuel cells and lithium ion batteries, to improve battery performance: © smaller size © lower mass © higher voltage Corrosion % Itisa chemical process whereby a metal is oxidized to its oxide, An example would be the rusting of iron (electrolytic process). ‘* Iron reacts with water and oxygen to form hydrated iron (Ill oxide, Fe,03.xH1;0, known as rust. * Attheanode: Fe(s) > Fe”"(aq) +2e © Atthe cathode: 0,(aq) +2H,0(I)+4e" > 40H (aq) ‘* The iron({l) ions then react with the hydroxi hydroxide, Fe™'(aq) + 20H (aq) > Fe(OH),\s) ions to form iron(|) ‘* The iron(tl) hydroxide is ovidized by air to form iron({t!) hydroxide which is converted to rust. 4Fe(QH)2(5) + O2(aq) +2H,0(l) —> 4Fe(OH)3(s) 2Fe(GH)a(s) > Fez0,.x#;0 + (3—x)H,0 Various methods are employed to prevent rusting. They are formation of alloy, formation of a barrier and the electrochemical method (sacrificial rusting). Worked Examples ‘State some of the imitations in using standard cell potentials to predict the feasibility of a reaction. Solution © The reaction has a very high activation energy, thus although it has a positive standard cell potential, the reaction does not occur. 6-14 FL cheisoy ~ Gnplte ui© The conditions of the reaction may not be standard conditions, thus the standard cell potential will not apply. © Standard cell potentials do not indicate rate of reactions. (ans) Calculate the E°.x: of the following reactions and predict whether they are spontaneous under standard conditions. (a) Chg) + 2F (aq) > 2CI(aq) + Fils) {b) H,02{aq) + Ci(g) —> 2H"(aq) + 2C/"|aq) + O.(g) Solution: (2) Ch+2e — 2cI~ = +1.36V 2F > Fp t2e F=42.87V Therefore the reaction is not feasible. (ans) (b) Ch+2e° > 2c” F=+136V H,0. + 2H’ +2e +02 E& =+0.68V Eco = 41.36 - 0.68 = 0.68V>0 Therefore the reaction is spontaneous. (ans) Note that the e.m.f. values only determine if a reaction is spontaneous and does not show the rate of reaction. a Calculate the E°,.i for the concentration cell containing silver ions at concentrations of 1.0 mol dm * and 0.001 mol dm *. Solution: Feat 0.0592, 0.001 85 10 =0.178V (ans) a © leroehenry(ee Electrolysis Define Electrolysis % Ina typical electroiytic cel, electrical energy is converted to chemical energy. Anelectrolyte is a solution or molten compound which conducts electricity. Atthe anode (positive electrode), the anions from solution give up electrons and become oxidized, % Atthe cathode (negative electrode), the cations from solution take in electrons and become reduced. & Electrons travel from the positive to negative electrode. & Battery |- Cathode (-) electroite Only one element can be deposited at each electrode at a time. The factors affecting the identity of substances liberated during electrolysis are: © State of electrolyte © Position of ions in the redox series © Cation with the most positive E* is discharged first. © Anion with the most negative E” is discharged first. Cation Product atathede | Anion Productat anode K Hydrogen > chlorne from water Ne Bromine s TF ipdine Reaciiy Me ofmetal ar 3 decreases SO! Oxygen from Ni Nickel water Po lead NOx Oxygen from ; water au Copper Ae siver FL cheisoy ~ Gnplte uiaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.> The Foraday is the charge carried by one mole of electrons. where Avogadro constant = charge on the electron (1.60 x 10 °C) Ch{g) + 26° Cathode : Hydrogen gas is produced. Sodium hydroxide is also produced. (reduction) 2H,0(I) +22" —> 20H (aq) +H2(e) Overall reaction : 2NaC/+2H,0 > Cl,+H,+2NaQH Anodising of aluminium Aluminium is coated with a layer of aluminium oxide during electrolysis with the aluminum metal as the anode. Graphite or any inert electrode is used as the cathode, while the electrolyte is dilute sulphuric acid. Anode : Oxygen gasiis liberated. 20H (aq) > H,0(!) +0.50;(e) + 2e” ‘The oxygen gas then reacts with the aluminium anode to form aluminum oxide, 2Al(s) + 1.502(8) > AlO3 ‘The anodic layer resists corrosion, absorbs dyes and is a good electrical conductor, Electrolytic purification of copper Imp! uri ies reduce the electrical conductivity of copper and thus it has to be id, ‘The Impure copper Is the anode, pure copper is the cathode while the electrolyte is copper(tl) sulphate. +[ Batery |- Anode : The impure copper dissolves. Culs) > Cu?*(aq) +267 Impurities with less positive & values also dissolve as ions, while progels) | | cathode (+) those with more positive E° values Impure Pure copper are undissolved and are collected at “PPS pede sat © leroehenry 6-19the bottom of the container as anode sludge. Cathode : Copper ions from the solution are discherged. cu(aq) +26" > culs} [Examined ip 2013p2.4e] % Inthis way, the pure copper cathode increases in size while the anode decreases in size. & The concentration of the electrolyte remains the same. Graphite is used as the anode, and graphite with a steel casing acts as the cathode. The electrolyte is pure aluminium oxide dissolved in cryolite (Na3AVF<). > Cryolite is added to reduce the melting point of aluminium oxide (from 2045°C to 950°C) and to produce a good conducting electrolyte. ‘Anode : Oxygen gas evolved reacts with the carbon anodes to give carbon dioxide gas. 20° () > O,(e) + 4e7 Cathode : Liquid aluminium collected at he cathode is tapped off. Al (aq) +3e > All) Anodes must be continually replaced since they are burnt off. Fluorine compounds such as hydrogen fluoride gas which are toxic may be produced. Worked Examples Give the equations of the reactions at the cathode and anode for the following electrochemical cells. {a) Dilute Naci (aq) using graphite electrodes {b) CuSO, (aq) using graphite electrodes (c) CuSO, (aq) using copper electrodes Solution: {a) The ions present in solution are Ne”, Cl", H’ and OH”. Cathode: Na{aq)+e > Nals) =-217V 2H'(eq)+2e > Hig) B=0v H’ hasa more posttive E> value, thus it is reduced at the cathode. Anode: Cl, +2e" > 2CI” P=+136V 0.{g) + 2H.0|l) +4e" > 40H (aq) = +0.40V 6-20 FL cheisoy ~ Gnplte uiaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Solution: (a) Q=10(40) =400 C (ans) (b) Number of moles of electrons = ‘96500 .00518 mol (3 sf). (ans) Aqueous sulphuric 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" > Hig) Anode: 40H (aq) — 0,{g) + 2H,0\I) + 4e~ ‘The oxygen gas produced reacts with the graphite electrode to form carbon monoxide and carbon dioxide. 2C(g) +Ofg) —» 2CO(g) Clg) +0, > COXe) (ars) {b) fan inert anode is used, the overall reaction will be: 4H'(aq) +40H (aq) > 02(g) + 24,01!) +2H2le) Oxygen gas, water and hydrogen gas are formed ina ratio 1:2:2. (ans) Electrolysis can be used in industrial applications such as the electrolytic purification of copper. Describe how this process is carried out. Solution: Copper ores contains many impurities. These impurities are refined or purified electrolytically to obtain pure copper. A rectangular iron tank is used as the electrolytic cell. Aqueous copper (I) sulphate solution is used as electralyte (containing traces of 1% HS, solution to increase its conductivity). The electrodes are: * Cathode ~ pure cooper metal in the form of sheets. '* Anode ~ Impure thick blocks of copper metal, 6-22 FL cheisoy ~ Gnplte ui| Pure copper shest en (cathode) — y ese Copper sulphate {anode) Purification of copper Electrolytic procedur © As current is passed through the electrolyte, pure copper metal from the impure blocks dissolves from the anode and is deposited on the cathode. © As the electrolysis process proceeds, the impure blocks of copper (anode) are used up and the thin sheets of pure copper metal (cathode) get thicker with deposition of pure copper. ©The impurities of the anode either dissolve in the electrolyte, or settle at the bottom of the cell, and are called anode mud or slime. Insoluble impurities like silver or gold are recovered fromit. The purity of copper can reach 99.9%, Electrolytic reactions: Copper II) sulphate (CuSO,) dissociates to produce copper(I!) ions (Cu) and sulphate ions (SO," }. Water (H;0) dissociates as hydrogen (H") ion and hydroxyl (OH’) ion, CuSO, -» Cu” +S0,° 0 > H’+OH Reaction at the cathode: Positive copper (Il) ions (Cu), due to their lower discharge potential over hydrogen ions (H'), migrate to the cathode. They are then discharged as metallic copper (Cu) and are deposited on the cathode. cu +2e Cu Reaction at the anode: Negatively charged sulphate (SO,") ions and hydroxyl ions (OH } migrate to the anode but neither of them is as easily discharged as copper atoms from the anode. (Nature of electrode playsan important role in selective discharge.) cu-2e > cue ‘As the copper atoms of the anode pass into the solution as Cu”" ions, the weight of anode decreases and an equivalent amount is deposited at the cathode. The concentration of copper (il) sulphate remains constant throughout. (ans) {examinedin 201392.4c] © leroehenry 6-23Two electrolysis experiments were carried out under the same temperature and pressure. Electrolysis 1 ~ Molten copperill) chloride was electrolysed for yielding 100cm’ of chlorine from the anode. minutes, Electrolysis 2 ~ Aqueous sulfuric acid was electrolysed for five minutes, yielding 20cm’ of oxygen from the anode. Given the current used in Electrolysis 1 was J, deduce the current used in electrolysis 2. Solution: Electrolysis 1 Cathode: Cu(aq)+2e > Culs) Anode: 2cr (aq) > Chg) +2e Current used = Electrolysis 2 Cathode: 4H'(aq)+4e > 2H,(g) Anode: 40H (aq) — 0.(g) + 2H,O(I) + 4e” Current used = 2/ However, the amount of oxygen gas collected is twice that of chlorine gas. Hence current used in Electrolysis 2 is 4. [Gcamined in 201291.7) FL cheisoy ~ Gnplte uiaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Solution: {a) Distilled water do not have ions, thus it cannot conduct electricity. (ans) (b) Copper can be used asit is lower in the reactivity series as compared to zinc, (ans) BS (i teanates Calculate the Avogadro constant when a current of 0.25 A was passed through dilute aqueous sodium chloride for 32 min 10 s. 56 cm’ of gas was evolved at the cathode ats.tp. Solution Q xt =0.25 x [(32 x 60) + 10] 482.5 No.of motes of gas eveled = 55 _- o00250 p20?) ‘The gas evolved at the cathode is hydrogen. Mole ratio of "Hz = 2:1 No. of Faraday = 2 « 0.00250 = 0.00500 F 482.5 0.00500, = 96500 C mol 96500 (260.10) =6.03 x 10" (ans) (a) Zinc metal and copper metal are placed separately in hydrochloric acid. With reference to the Data Booklet, state and explain whether they will dissolve in the acid, (b) These two metals are now used as electrodes in a Daniell cell. The zinc rods, immersed in 1M zinc sulphate solution while the copper rod isimmersed in 1M copper (I!) sulphate solution. (i) Give the half equations that will occur at the electrodes. (ii) State the direction of electron flow in the external circuit. (iii) Calculate the e.m4 produced in the cell. (iv) Ifthe zinc rodis placed in a solution of copper (Il) sulphate, describe and explain the observations. 6-26 FL cheisoy ~ Gnplte uiA (v) If the zine rod is placed in sulphuric acid, describe and explain what can be seen, (a) From the Data Booklet, the E° values for Zn, H and Cu are -0.76 V, OV and 40.34 V respectively. For the metal to dissolve in the acid, the F°,q) must be greater than 0. Between Zn and H’, E°<9i=0~ (-0.76) = +0.76 V>0 Thus the reaction is energetically feasible and zinc dissolves in the acid to form aqueous zinc chloride. Between Cu and H", E°.=0-0.34=-0.34<0 Thus the reaction is not energetically feasible and copper does not dissolve in the acid. (ans) {b) (i) Copper electrode: Cu**(aq)+2e —> Culs) Zincelectrode: Zn(s) > Zn” (aq) +2e” (ans) (ii) tewil flow from the zinc electrode to the copper electrode as electrons are produced at the zinc electrode and used up at the copper electrode. fans) (ii) Ecay= 0.34 ~ (0.76) = 1.10.V (ans) {iv) A pink coat of metal will form on the zinc rod and the blue colour of the copper (!!) sulphate solution will fade. This is because the zinc metal has displaced copper from the selution. (ans) (v)_ Zine metal will dissolve in the acid and effervescence can be seen. The metal has reacted with the acid to produce hydrogen gas. (ans) a (a) State and explain the variation in the oxidation numbers of the chlorides of the elements Na, Mg, A/ and Si fe} (b) Describe the reaction of phosphorus(V) chloride with water, and write an equation for the reaction. 2] (c)_ When microwave raciation is passed through phosphorus(tll) chloride, PCI, at low pressure, a new chloride of phosphorus, B, is formed. B contains 69.6% by mass of chlorine and 30.4% by mass of phosphorus, and its M, is approximately 200. (i) Calculate the empirical and molecular formulae of 8. (i) Assuming phosphorus and chlorine show their typical valencies, draw the displayed formula of B, showing all bonds and lone pairs. (iii) Calculate the oxidation number of phosphorus in B. © leroehenry 6-27{iv) One mole of B reacts with four moles of water. ‘Suggest the structure of the phosphorus-containing product of this reaction, (6) [Total: 10] ‘Solution: (a) (442; (492; (493; (44 (ans) (b) PCls fixzes PClz+4H,0 > HPO. +SHCI (ans) = 1.96 PCI, (ans) (c) (i) P= 338=0,98; cl= SE ‘Thus Empirical formula M,(PCI;) = 102, so.2 x PCI; = 204 = 200 Thus molecular formula =P2Ci;_ (ans) i) cr. cl pee? \ 7 (ens) (iii) O.N. = (2 (ans) (iv) (HO),P-P(OH), (ans) © Mark Scheme (a) (a; (2; 43; 4 a) Oxidation number corresponds to the no. of electronsin outer/ valence shell/lost (1) (b] PCI. fizzes or white/misty fumes or heat evolved fet) PCls +4H,0 -> H3PO, + SHCI or PCI; + 3H,0 > HPO; + SHC! (allow partial hydrolysis: PC/; + HO > POC/2 + 2HC/) fa (c) () P= 84=0.98; cl= G8 =1.96 fa] ‘Thus Empirical formula = PC/, ) M,(PCh,) = 102, so 2 x PCI; = 204 = 200 Thus molecular formula = PCI, ie3) (ii) dv. ; wet >: a” (ignore tone pairs on Cl) 1] (iii) Oxidation number = (+)2 iba iv) (HO),P-PIOH}, or H(HO)P(=0}-P(=O)(OH)H ecf from structure in (i) [1] Allow HO—P—OH or HO—P=0. H © ecf—error carried forward [Total: 10] FL cheisoy ~ Gnplte ui° Teachers’ Comment (a) Candidates gave mixed answers here, with a surprising number omitting to state the oxidation numbers of the four elements. Even, those who did do so often did not relate these to the number of ‘outer/valency electrons lost. (b) Many candidates did not answer the question here to des ‘observations. Examiners were expecting answers including the formation of misty fumes, the evolution of heat or some ‘fizzing’. there ‘was also some uncertainty about the product of the reaction or writing a balanced equation. Acceptable products were HsPOs, HPO; andthe partially hydrolysed POCIs, (©) (i) Lotsof candidates gained full credit here, although some unfortunately used a correct empirical formula of PCI, to get an incorrect molecular formula of PC. (ii) A pleasing number of candidates were able to draw a correct structure. The most common error was to omit the lone pairs on the phosphorus atoms, (iii) Most candidates correctly deduced that the oxidation number was 42. (iv) This proved a trickier question with only more able candidates suggesting a correct structure, which could be obtained by ‘replacing all four C/ atoms in P2C/, by OH groups. © leroehenryNote: ‘A. Ghemiey ~ Cone GideA Content 2.1 Chemical equioria: reversible reactions; dynamic equilibrium |i) Factors affecting chemical equilibria |i) Equilibrium constants lit) The Haber process 7.2 lonicequilbria |) Bronsted-towry theory of aciés and bases lil) Acid dissociation constants, K, and the use of pk. lid) Base disseciation constants, K, andthe use of Pky liv) The ionic product of water, Ky Iv) pH: choice of pi indicators |Mi) Buffer solutions [wil Solubility product; the common ion effect 73 Phase equilibria (plementary op) |i) Phase diagrams IN) Partiion coefficient, solvent extraction Iii) Cheomateeraphy Learning Outcomes Candidates should be ableto: (0) explain, interms of rates ofthe forward and reverse reactions, whatis meant by @ reversible reaction and dynamic equilibrium (0) state Le Chatelier's Principle and apply it to deduce qualtatively (rom appropriate Information) the effects of changes in temperature, concentration or pressure, on a system at equlfrium (0) educe whether changes in concentration, pressure or temperature or the presence of a catalyst affect the value ofthe equilbrium corstant fer a reaction (4) deduce expressions for equilibrium constantsin terms of concentration, K., and partial pressure, hy [treatment of the relationship between K. and K, not required.) (6) calculate the values of equilibrium constants in terms of concentrations or partial pressures rom appropriate data (1) calculate the quantities present at equilibrium, given appropriate data [such calculations ill not require the zolving of quadratic equations) (8) escribe and explain the conditions usedin the Haber process, as an example of the Importance of an understandirg of chemical equilibrium in the chemical industry () snow understanding of, and apply, the Bronsted-Lowry theory of acids and bases, inclucing the concept of conjugate acids and conjugate bases (explain qualitatively the differences in behaviour between strong and weak acids and basesin terms of the extent of dissociation (explain the terms pH K. pk Ki: Ki: K. and apply them in calculations, including the relationship Ky = Kiki (8 Gleulate [H(aql] and pl values for strong acids, weak monobasic (moropretic) acids, strong bases and weak monoacidic bases (explain the choice of suitable indicators for acid-base tivations, given appropriate data {m) describe the changesin pi during acid-base trations and explain these changes in terms of the strengths of acids end bases (©) (explain how buffer solutions contra pH (i) describe and explain their uses, incliding the role of H,CO,/!CO, in controling pH in biooe (0) cleulste the pit of butforsolutions, given appropriate data 7 aia 1©) (a) " (s) © w) show understanding of, ané apply the concept of solubility product. Ky calculate K. from concentrations and vice verse show understanding ofthe common ion effect cexalain the phase diagramsincluding the triple and critical point (unserer pi) calculate the partion coefficient in solvents (applamentary eis) show understanding of chromatograghy (spsenentay tpi) AL ches Complete Gezi Chemical equilibrium Define Reversible reaction & a The reaction is never complete, reaching an equilibrium whereby both the reactants and products are present. Equilibrium exists only in closed systems where substances cannot be added or removed. ‘The activation energy of the reaction determines whether it is reversible. li the activation energy of the backward reaction is very high, the backward reaction will be unfavourable and the reaction is described as irreversible. The reactants and products are separated bya two-ended arrow, => © Br3(2q) +H20(I) => H"(aq) + Br (aq) + HOBr ‘The above reaction is an example of a reversible reaction. Br,(2q) is yellowish brown while all the ions on the right-hand side are colourless. When OH is added, the bromine water becomes colourless as the hydroxide ions react with the hydrogen ions to form water. This. causes the concentration of hydrogen ions to decrease and the equilibrium will shift to the right to counter the reduction. This causes the bromine water to turn colourless. When H’ is added, the equilibrium shifts to the left to counter the increase in concentration of hydrogen ions, and the yellowish-brown colour of bromine water reappears. Ss * ‘The substances are still reacting, but there is no change in the concentrations of both reactants and products. Itcan only be achieved in a closed system. 7 ealiria 3© For the reaction N(g) +O.) = 2NO(e), When nitrogen and oxygen are mixed, the reaction is very fastat first. However as the concentration of nitrogen and oxygen decreases, the rate of forward reaction, R,, also decreases. Initially, there is no nitrogen oxide. Thus the rate of the backward reaction, Ro, is zero. However, as the forward reaction progresses, more and more nitrogen oxide is produced and thus R, increases. After some time, Ry = R3. The rate of forward reaction is now equal to the rate of backward reaction. This is known as dynamic equilibrium (as indicated by the flat portion of the graph on the extreme ght). concentration concentration concentration Ne reactant product equilib product reactant Characteristics of dynamic equilibrium © The system is reversible. © The composition of any substance (reactant or product) is unchanged at equilibrium © The enthalpy change of a reaction at equilibrium is equal to zero. The equilibrium law > For any reversible reaction aA+bB = cC+ dD, the equilibrium constant, Kis (ctor larisr where [Al, [6] [C], 1D] are the equiibrium concentrations a,b, ¢, dare the coefficients in the chemical equation K, 14 AL ches Gonplee ueA Keisa constant at a particular temperature and itis independent of the volume and initial composition. The expression contains only concentration terms of liquids and gases and excludes concentration of solids and solvents (as these are constants and are already taken into account in K,).. For gaseous reactions, the equilibrium constant, K,, is written in terms of partial pressure. & For any reversible reaction ah +bB => cC +dD, the equilibrium constant, K, is (Pc). (Pola (Px), *(Pa), where pis the partial pressure of the gas (product of its mole fraction and the total pressure, pr) a (rq +74) Pa 2, b,c, dare the coefficients in the chemical equation © CH,CO,H(aq) + GHsOH(aq) = CHCO,CH;(I) +H,0(I) acd slcohol ester water _[esterl]iwater] Tacdilaconon (Units) [acid] {alcohol} © CaCO,(s) = CaO(s) + COp{g) K, ICO,} or K,=(Peo,) (units = mol dm” or Pa) J The equilibrium constant, K, gives an indication of the position of equilibrium, and whether there is a larger proportion of reactants or products, * Ifthe value of K. s less than 10, the equilibrium mixture contains mostly reactants and the position of equilibrium lies to the left. © Ifthe value of K; is between 10” and 10°, the proportion of reactants and products is about the same. © Ifthe value of K,is greater than 10%, the equilibrium mixture contains mostly products and the position of equilibrium lies to the right. Examinedin 2012p2.2¢) 4K. gives no information about the reaction rate. J The equilibrium constants, K-and K, are only affected by changes in temperature For any reversible reaction A+B == C+D, 7 aia ns+ Ifthe reaction is exothermic, K: oF K; increases as the temperature decreases as the position of equilibrium shifts to the right, forming more products. ‘© Ifthe reaction is endothermic, K. or K, increases as the temperature increases as the position of equilibrium shifts to the right, forming more products, F The equilibrium constants, Ke and K, are not affected by changes in pressure, concentration or the addition of a catalyst. Catalysts increase the reaction rate without changing the composition of an equilibrium mixture. © For the reaction: CH,CH,OH(I) + CH,CO;H(I]_ = CH,CO,CH,CH3() + H,0(I) Calculate the mass of ethanoic acid that must be mixed with 2.0 mol of ethanol to produce 1.5 mol of ethyl ethanoate at equilibrium, Let x be the number of moles of ethanoic acid required. The equilibrium concentration can be represented as follow: ICHsCH.0H], -15 [CH3CH.OH), [CHsCO;H], = x “15 [CHsCO,H]e =x 1.5 [CH,CO,CH,CH,]o = 0 1s [CH,CO,CH.CH,]e = 1.5 [H20]o=0 1s [M20] =1.5 Substituting the equilibrium concentrations into the equilibrium expression: [cH,co,cH,cH, |[+,0] [cH,cH,on][cH,c0,4] aes viv FV) osy,_15 v v x=2.625 Mass of ethanoic acid = 2.625 x [12.0 + 3(1.0) + 12.0 + 2(16.0) + 10] = 158g 40= where V = volume of the vessel (dm*) Le Chatelier’s Principle [Examined ip 2023p2.2a) AL ches Gonplee ue. Changes in concentration, temperature and pressure and addition of a catalyst can influence the equilibrium of a system. ‘Since the system cannot completely remove the effect of the change, it will move in such a way as to minimize the change. Concentration + 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. 8 ‘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. J It products are removed from a system in equilibrium, the position of equilibrium will shift right in order to produce more productsat the new equilibrium. © For the reaction No(g) + On(g]_ == 2NO(g), IF Nis 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 Ny and 02 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 again. ‘The result isa shift in equilibrium to the right. Alternatively, if the concentration of N, is decreased, the equilibrium s to the left. Thus the equilibrium position moves in such a way as to oppose the change. Acchange in concentration does not affect the value of the equilibrium constant, K. Temperature <7 When the temperature of a system is increased, the rates of both the forward reaction and the backward reactions will increase. 4 However, the increase in rate will not be the same for both reactionsas 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. 7 aia m7‘+ Fora reaction with low activation energy, a temperature increase will result in a small increase in the proportion of molecules with eneray greater than the activation energy, as most of the molecules already possess the required energy. * An increase in temperature will cause a greater increase in reaction rate for a reaction with higher activation energy. > Thus the rate of forward reaction is no longer equal to the rate of backward reaction and the equilibrium must shift so as to make the rates equal again. Increased temperatures favour endothermic reactions while decreased temperatures favour exothermic reactions. [Examined in 2013p2.28] A change in temperature will change the value of the equilibrium constant, ke © The reaction N,O.{g) = 2NOz(g) is an exothermic reaction. Ifthe temperature of the system is increased, the equilibrium will counter the change by absorbing the added heat, therefore the equilibrium shifts to the left. Conversely, if the temperature is decreased, the equilibrium will counter the change by producing more heat, therefore the equilibrium shifts to the right. © For the endothermic reaction Na(e) +0,(e) = 2NO(@), the opposite is true. If the temperature of the system is increased, the equilibrium 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, Generally, if the forward reaction of an equilibrium reaction is exothermic, K.will decrease as temperature increase: ‘© For an exothermic reaction, the activation energy of the backward reaction is greater than the forward reaction. © The temperature increase will cause the rate of backward reaction to increase more than the rate of forward reaction. rate constant of forward reaction © Since K, = Sore rate constant of backward reaction K. will become smaller, & Similarly, if the forward reaction of an equilibrium reaction is endothermic, K.will increase as temperature increases. AL ches Gonplee ueThe relationship between temperature and K for exothermic and endothermic reactions is shown below. AH In K= constant RT Where K=equilibrium constant ‘AH = change in enthalpy (AH > 0 for endothermic reactions; AH< Ofor exothermic reactions) R=gas constant T =absolute temperature + Foran exothermic reaction, with an increase in temperature, In K decreases as AH , “ar becomes less positive, Hence, Kor K, decreases. ‘The converse is true when the temperature is decreased. * Foran endothermic reaction, with an increase in temperature, In K AH increases as -~ becomesless negative. Hence, Kor K, increases. The converse is true when the temperature is decreased, Pressure > Changesin pressure affect only gaseous systems. g ‘There are two ways in which pressure can be applied to a system — by physical compression or by addition of an inert gas. The equilibrium. constant, K, is not affected, J Ifthe 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. 7 tthe pressure of a system in equilibrium is increased, the position of ‘equilibrium will shift in such a way as favouring the reaction producing a fewer number of moles of gas. @ ‘For the reaction Na(g) +O2(g) = 2NO(g), (ok (P.) If the partial pressure of Nz is increased, itis equivalent to an increase in the concentration of Np and the rate of forward reaction also increases. [Examinedin 2013p2.23] P To counter the change, the equilibrium shifts to the right. ithe total pressure is changed, the equilibrium position of the system will also be changed, 7 aia 9© For the reaction N(g) +O.) = 2NO(e), (Fo) Py iPo,) If the total pressure is doubled, the equilibrium will shift ina direction that will decrease the total number of moles of gases. K, Conversely, if total pressure is decreased, the equilibrium will shift in 2 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 2 change in pressure will have no effect on the equilibrium position. % The effect of an addition of an inert gas depends on the conditions at which itis added, ‘© Ifthe inert gasis added at constant volume, the total pressure increases, but the partial pressure of each component gas is unchanged, thus the equilibrium position does not shit. © Ifthe inert gasis added at constant pressure, the volume will increase (dilution effect) and the equilibrium position will shift in the direction that increases the total number of moles of gas Changes in pressure have no effect on equilibrium reactions which have no difference in the number of moles of gases in both the forward and backward reactions. For example, 2HBr <=> Hz + Br Catalyst % A catalyst speeds up both the rate of forward and backward reactions equally. 8 Therefore there is no change in K, oF Ky. Only the rate at which equilibrium is attained is increased. Haber Process J Ammoniais a very important compound and itis formed from nitrogen and hydrogen in a process known as the Haber process. Na(g) + 3H2(g) = 2NHa(g) AH = -92 KJ mol” ‘© Nitrogen is obtained from the fractional distillation of liquid air while hydrogen is obtained from the catalytic cracking of hydrocarbons or asa by-product from the electrolysis of brine. ‘¢ The reaction is a reversible one and it carried out at an optimum temperature and pressure of 500°C and 200 atm, 7-10 AL ches Gonplee ue© Too high a pressure will result in a higher maintenance cost while too low a temperature will result in a slow reaction. Finely divided iron is used as a catalyst. Promoters such as aluminium oxide can be added to increase the efficiency of the catalyst. «Catalysts are used to increase the rate at which equilibrium is reached. ‘+ Under these conditions, the yield of ammonia is only about 10%. Thus the unreacted gases are recycled in order to reduce wastage. SOa(g) 280,(g) + O4g) => 250,(g) AH =~197 ki mol $0,(g) +H,S04(I) > H,S202(I) H,5,0;(I) +H,0() > 2H,S0,(aq) Inthe first stage, liquid sulfur is burnt by hot air at 100°C to produce sulfur dioxide. * Sulfur dioxide is formed and not sulfur trioxide, as sulfur trioxide has much higher activation energy compared to sulfur dioxide. [Examinedin 2012p2.2c] Sulfur dioxide then reacts reversibly with oxygen to form sulfur trioxide. * Sulfur trioxide is then absorbed into concentrated acid to produce oleum. © Oleum is diluted with water and distilled fractionally to give sulfuric acid. © Too high a pressure will result in a higher maintenance cost while too low a temperature will result in a slow reaction, © Vanadium (V) oxide is used as a catalyst. ‘© Catalysts are used to increase the rate at which equilibrium is reached. (Examined in 2022p2.2c) * Under conditions of 450°C and 1 atm, almost 95% conversion is achieved, 7 ealiria rau- Factors to consider in selecting conditions of reactions: © Cost © Reaction rate ‘+ Production of an optimum amount of products Worked Examples Dinitrogen tetroxide decomposes in the gaseous state to form gaseous nitrogen dioxide. NO4(g) = 2NO2(g) AH<0 ‘At equilibrium, the pressure of N2O, was 3.62 atm and the equilibrium constant Kyis 0.24. {a) Calculate the equilibrium pressure of NO- (g). (b) State, and explain, the effect of the following changes on the equilibrium constant, Ko, (i) Increase in temperature (ii) Increase total pressure by adding an inert gas Solution: fo? fra? (a) 024= 2 = 20 Fao, 362 ao, = 0.932 atm (3 sf] (ans) {b) (i) Asthe reaction is an exothermic reaction, by Le Chatelier’s principle, an increase in temperature will cause the equilibrium to shift to the left. K, will decrease. (ans) (ii) An increase in total pressure by adding an inert gas will have no effect on the K, of the reaction as it has no effect on the partial pressure of the substances. (ans) a For the reaction 2S0;(g) +02(s) +2 250s{g), the following data about the equi 400 450 500 0.44 0.32 0.26 (a) Deduce if the reaction is endothermic or exothermic. (b) State, and explain, the effect of a decrease in pressure on the reaction. im constant, K., and temperature is obtained. 7-12 AL Chemisty - Complete Guide(2) The reaction is exothermic as an increase in temperature results in a decrease in K. This shows that the rate of forward reaction decreases with temperature. (ans) (b) By Le Chatelier’s principle, a decrease in pressure will cause the equilibrium, to shift to the left as there is a greater number of moles of substances. Thus the yield of SO: will decrease, while SO; and 02 will increase. (ans) ‘A(g) and B(g) react reversibly to form Cig). (2) From the graph below, deduce the equilibrium constant, K,, for the reaction. 5 3 OF hae = os 2 ete) Eos 3 cle) 2 02 & 10 2030 Time/min (b) Compare the rates of forward reaction and backward reaction at the 5"" min and the 20” min. (c) Ifthe 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? Soluti (a) From the graph, it can be sent that one mole of A(g) reacts with 2 moles of B(g) to form 1 mole of Clg). { 2 (alis} (b) At the 5" minute, the rate of forward reaction is greater than the backward reaction as Cle) 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) {@)_ The amount of C{g) produced will increase. A decrease in volume will increase the total pressure. By Le Chatelier’s principle, the equilibrium will shift to the right as there is a lesser number of moles of gas. (ans) s 7 aia 73For a chemical reaction between Ax(g) and B2(g), the following mechanism was proposed. Step 1: Azle) = 2A(e) Step 2: 2A(g) +B,(¢) = 2AB(g) (a) Write an expression for the equilibrium constant, K. for Step 1 (b) If Step 2 is the rate determining step, find the order of reaction with respect to Ax(g) and B{g). Solution: P fa) Ke a (ans) (b) The rate determining step will give the rate of the overall reaction. Rate = K(A]"(B:] Substituting the equation in (a) into the rate equation, Rate = kk {A2](B2] = ki{A2][82) From this equation, it can be seen that the reaction is first order with respect to both Az{g) and B2(g). (ans) © _ The magnitude of K; (or K,) indicates the postion of equilibrium. When K.is very small, there islikely to be a higher proportion of reactants. When K. is very high, there is lkely to bea lower proportion of reactants 2 For the synthesis of hydrogen iodide from hydrogen and iodine, 1 mol of H; and 2 mol of Iz are mixed in a 4 dm’ container. If the equilibrium constant, K., at this temperature is 2.5 x 10°, calculate the equilibrium concentration of each ‘component in the system. Solution: The reaction can be represented by: Hale) + Ife) = 2HI(e) (Hi ][2] The initial concentrations are: 1 HiJo= ~ = 0.25 mol drm (Hl 7 Ke=2.5 x10! 2 [lo= = =0.5 mol div a [HI] = 0 mol dm”? Let x be the number of moles per dm” of H, consumed. The equilibrium concentration can be represented as follows: 7-4 AL ches Gonplee ue[Hy]o=0.25 [Hale =0.25-x [hle= 0.5-« 42x (HI},= 2x Substituting the equilibrium concentrations into the equilibrium expression: Px? [re][b] (025-x)(05-x) 2.5%4107(0.25— x)(0.5—x)=4x? (2sxat)(0125-075x+4)=ax¢ K.=2.5 «10° (0.125-0.75x +x?) -0.016x° =0 0.984x? -0.75x +0.125=0 x=0.516 mol or 0.246 mol (to 3 sf) ‘The value x =0.516 mole cannot be valid as itis greater than the initial concentration, therefore x = 0.246 mol. ‘The equilibrium concentrations are: [Hz] = 0.25 -0.246 = 0.004 mol dm™ [1] = 0.50246 = 0.254 mol dm? [HI] = 2(0.246) =0.492 mol dm? (ans) ‘The Haber process is used to produce ammonia, Nog) + 3H2(g) = 2NH3(a) AH = -92ki/mol (a) State the sources of nitrogen gas and hydrogen gas. (b) Describe and explain the conditions for this process. Solution: (a) Nitrogen is obtained from the fractional distillation of liquid air while hydrogen is obtained from the catalytic cracking of hydrocarbons or as a by- product from the electroiysis of brine. (ans) (b) Le Chatelier’s Principle predicts that @ lower temperature and a higher pressure will result in a higher yield. However, a low temperature will make the reaction too slow and a high pressure will increase the costs of operating the plant, ‘Thusa compromise is reached by carrying out the reaction at an optimum temperature and pressure of 500°C and 200 atm. Finely divided iron is used as a catalyst to increase the rate of reaction. (ans) a 7 siaIonic equilibria Define Acid Base Degree of dissociation The pH of an acid can be found by using the formula pH = logo IH") > The pH of an acid depends on the concentration as well as the degree of dissociation. & Its value changes with concentration. Therefore, a more reliable method for the determination of the pH of a solution is to use its dissociation constant, as the value is constant at all dilutions and varies only with temperature. o Universal indicators or a pH meter can be used to determine the pH ofa solution. H0°(aql + Cl-(aq) © Ethanoic acid is a weak acid. A solution of ethanoic acid contains alow concentration of ions and is a poor electrolyte. CHsCOOH|aq) + H,0(!) = H,0"(aq) + CHsCOO (aq) Acid dissociation constant For a weak acid HA, HA(aq) +H20()) = H30°(aq) +A (aq), the acid dissociation constant, {H,0'}A] [HA] PK, = logo [Ka] mol dm? (Examined in 2012p1.10] J The acid dissociation constant is a given value at a constant temperature. % Itis a more accurate measurement of the pH of an acid. © The stronger the acid, the greater the K, (or the smaller the pk). © The dissociation constant, K,, of ethanoic acid is 1.8 x 10° mol dev The dissociation constant, Ks, of nitrous acid is 4.6 x 10“ mol dm” ‘Thus nitrous acid is a stronger acid than ethanoic acid. 7-18 AL ches Gonplee uei Base dissociation constant For aweak base B, B(aq) +H,0(l) = BH'(aq) +OH [aq), the base dissociation constant, k, = BHEHOH ot am? [8] pK, = —logso [Kel The base dissociation constant is a given value ata constant temperature. ‘The stronger the base, the greater the K; (or the smaller the pki). © The dissociation constant, Ki, of ammonia is 1.8 x 10° mol dm. The dissociation constant, Ky, of methylamine is 4.0 x 10 mol dm. ‘Thus methylamine is a stronger base than ammonia. Dissociation of water Water is an amphoteric substance as it sable to behave as an acid or a base. The equation for the autoionisation (self-ionisation) of water is shown below. 2H,0(!) = H30°(aq) +OH (aq) AH = +58 kJ mol* The ionic product of water, Ky, at 25°C is given as Ky = [HsO'J[OH] = [HOH] = 1.0.x 10 “mo? dm © Kw = 0810 [Ky] = 14 % Since the reaction is endothermic, K,,increases with an increase in temperature. + In pure water, the number of hydrogen ions and hydroxide ions are always equal. That means that pure water remains neutral, even if its pH changes. % Pure water at 25'C has a pH ~ 7. The pH of pure water falls as the temperature increases, Note that the neutral value of pHis calculated from Ky. If that changes, then the neutral value for pH changes as well. For example, the pH of pure water at 100°C is 6.14. This is the neutral point on the pH scale at 100°C. lExeminedin 2013p1.11] J The ionic product of water, Ky, is related to K, and Ki, KK Ke 7 aia 7-19© Todetermine if 1.0 x 10.” QH is acidic or basic, K,= [HOH] 10x10" SONTE — =10x107M 10x10 HT Since [OH] = [H’] the solution is neutral. Calculations of pH of weak acids and weak bases The pil of acid or base solutions can be calculated if the dissociation constant is known, } Ostwald dilution law gives the relationship between concentration, degree of dissociation and the dissociation constant. & Fora weak acid HA, HA(aq) =H (aq) + A (aq) Initial concentration/mol dm™ x 0 ° Equilibrium concentrationfmoldm® = x(1- a) xa xa (HWA) _ xcrxnce [HA] x(1—a) Since w<< 1, (1 — a) can be assumed to be 1. wT 2 [oH x & For a weak base B, Ky = x0 © Calculate the pH and degree of dissociation, « of a 0.01 M weak acid HA given thatits K, = 1.8 « 10°. IK, hax10 * xP => a= => a= {—~—— x 0.01 c= 0.0424 (3 sf) x -HE & ieee oon(texo*) tH) pH = logo [H'] =3.37 k, 24 x 10 “mol dm? (Examined in 2013p2.3b] 7-20 AL ches Gonplee uej Define Buffered solution & a o There are twa types of buffered solutions © Acidic buffer, which contains a weak acid anc the sodium (potassium) salt of that acid. It hes a pH less than 7. © Alkaline buffer, which contains a weak base and a salt of that base. It has a pH greater than 7. Abuffer is most effective at its maximum buffering capacity. where its pH= pK, or POH = pKy (as indicated by the centre of the buffer region on a pH curve). One of the most important buffer systems is to maintain our blood pH The main buffer system in blood consists of hydrogen carbonate and carbonic acid which is associated with the gaseous exchange of carbon dioxide in our lungs. + Blood can absorb the acids and bases produced in biological reactions without changing the pH. © Thisis very important as cells can only work in a small pH range of 7.35 ~ 745, Acidic buffers 4 When hydroxide ions are added to an acidic buffer, 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. ‘From the expression for the dissociation constant, =[r HA] sdistondependson tL [*] [Ha] + When hydroxide ions are added, [A] increases and the ratio 1 i] [Ha] Ste] it can be seen that the pH of the (HA) decreases. 7 aia ra‘+ However, if the amounts of HA and A” are very large compared to the [Ha] amount of hydroxide ions added, the change in ratio is minimal. [=] Thus [H"] remains virtually 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. © Anexample of an acidic buffer is a solution of ethanoic acid and potassium ethanoate Ethanoic acid is partially dissociated. CHsCOOH = CHsCOO™ +H. Potassium ethanoate is fully dissociated, CHaCOOK > CH:COO+K’ When Ht ions are added, they are removed by CH,COO™ so that the pH remains virtually unchanged. H! +CHsCOO” = CH;COOH When OH "ions are added, they are removed by CH;COOH so that the pH remains virtually unchanged. OH” +CH,COOH = CH,COO” +H,0 Alkaline buffers > When protons are added to an alkaline buffer, the protons react with the base, thus the pH of the solution remains unchanged, When hydroxide ions are added, they react with the salt and once again the pH remains virtually unchanged © Anexample of an alkaline bufter is a solution of a solution of aqueous ammonia and ammonium chloride. Ammonia is partially dissociated. NH3+H,0 == NHq + OH” Ammonium chloride is fully dissociated. NH4Ci > NHe +CI~ When H’ ions are added, they are removed by NH; so that the pH remains virtually unchanged. H+ NH == NH 7-2 AL ches Gonplee ueWhen OH ions are added, they are removed by NH,’ so that the pH remains virtually unchanged. OW+NH, => NH. +H20 Calculating pH of buffer solutions Inanacidic buffer, K, ‘Two assumptions are made, © [HA] = [acid]: Since the acid is only slightly dissociated. © (A) = [salt] as the salt is fully dissociated and the amount of A” from the acid is negligible. (acid) [salt] 4 {HJ of buffer solution = K, x = ~e6 071 =o +{ ono BEM) =pH=pk, +(e fal ) iacig} Simiarty for akatne butters, pOH=pK, sora 24h) © Calculate the pH of an acidic buffer prepared by 0.02 M sodium ethanoate and 0.01 M ethanoic acid. (K, of ethanoic acid = 1.8 x 10° mol dm”) pH =5.05 (3sf) Define Indicator Each indicator has a pH range over which it changes colour. They have an acid colour (HIn) and an alkaline colour (In). 7 ealiria yaDefine ‘The pH ranges of some common indicators are shown below. Methyl orange red yellow 31-44 Phenoipthalein colourless red 8.3- 10.0 Bromothymol blue yellow blue 60-76 For an acid indicator, Hin(aq) +H0(I) == H30'(aq) +1n"aq) ‘* Inan acidic solution, the concentration of H;0" is high and the equilibrium shifts to the left, thus resulting in the acid colour. * _ Inan alkaline solution, the H:0" ions are removed and the above equilibrium shifts to the right, resulting in the alkaline colour. Indicators are used in acid-base titrations to mark the end-point of the titration, ‘+ The choice of indicator depends on the pH of the end-point. ‘+ The indicator should change colour sharply on addition of one or two drops of liquic. Therefore the end-point should be within the pH range of the indicator chosen. Indicator normally change colour over the range of 2 pH units. Appropriate indicators can be used for most titrations except that between weak acids and weak bases. The dissociation constant of the indicator, Kin: [Ho] 0] 0° Tatay and pK, =10B:oKi, ‘The indicator is at the mid-point of its colour change when [Hin] Kio = 1H,0°] oF pin = pH. Titration og 7-28 AL ches Gonplee ue Ina titration, a fixed volume is measured out by a pipette into a flask, then drops of liquid are added from a burette until the end-point (equivalence point) is reached. At the equivalence point of a titration, the molar ratio of the two reactants is, equal to the molar ratio specified by the reaction equation,Titration curve © There are mainly four different types of titrations. e ° ° a The Strong acid-strong base titration, e.g., hydrochloric acid and sodium hydroxide Weak acid-strong base titration, e.g., ethanoic acid and sodium hydroxide. Strong acid-weak base titration, e.g., hydrochloric acid and ammonia. Weak acid-weak base titration, e.g., ethanoic acid and ammonia titration curves for the four types of titrations are shown below. Strong base (0.1 M NaOH) titrated with strong acid (0.1 M HC/) © Thetitration curve starts at 14, indicating that the base is strong. © ASHCIis added, it neutralizes an equal volume of NaOH to form salt and water, © The pH decreases as the remaining acidis diluted by the increase in volume of water, thus reducing [H') © Thesharp decrease in pH indicated the end-point of the titration. At this point, the solution is neutral (pH = 7). © As more HClis added, [H*] increases and the solution becomes acidic. ‘Strongacid with strong base 4 R 10 Endpoint Volume of acd © Most indicators can be used in such titrations Weak base (0.1 M NH.) titrated with strong acid (0.1 M HC/) © Thetitration curve starts below 14, indicating that the base is weak. © ASHClis added, it neutralizes an equal volume of NH; to form salt and water. © ThepH decreases as the remaining acid is diluted by the increase in volume of water, thus reducing [H"} © Theend:-point is less than 7. © Suitable indicators include methyl red and methyl orange. Strongacid with weak base pH 4 8 6 <— endpoint 4 Volume of add 7 sia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.= 0.0025 mol Number of moles of HC/ after reaction = 0.005 ~ 0.0025 0.0025 mol Number of moles of NaOH after reaction = 0 mol _ 0.0025 WI 1000 = 0,025 M pH =—log 0.025 = 1.60 (3 sf) When 100 cm* of NaOH has been added, 50 = (01 000°") .005 mol Number of moles of HC/ before reactior Number of moles of NaOH before reaction = 22° (0.05) 1000 =0.005 mat Number of moles of HC/ after reaction = 0.005 ~ 0.005 0 mol Number of moles of NaOH after reaction = 0 mol ar) {H’] = —~1000 =0M 150 pH=7 When 150 cm’ of NaOH has been added, 50 ——(0.1) 1000 = 0.005 mol Number of moles of HCI before reaction 150 Number of moles of NaOH before reaction = ——(0.05) 1000 =0.0075 mol Number of moles of HC/ after reaction = 0.005 ~0.005 =0 mol Number of moles of NaOH after reaction = 0.0075 — 0.005 = 0.0025 mol fon) = 2°°5.,1000 =0.0125 Mm 200 “ y= 22220 - gox10 0.0125 pH =—log (80x 10")=12.1 (3sf) ‘When 209 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 7 aia 7-35=001 mol Number of moles of HC/ after reaction = 0.005 ~ 0.005 =0mol Number of moles of NaOH after reaction = 0.01 ~ 0.005 = 0,005 mol fon] = 22°. 1000 = 0.02 M 250 w= 2220 goa 0.02 pH =-log (5.0 10") 12.3 (3sf) The graph looks like thi pH a4 2 50. 100 150 200 Volume of NaQH added {em’) {b) The pH curves changes very gradually at first as there is a relatively large amount of H’ at first, and addition of OH” resutts in a smalll 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 His relatively small, 50 addition of OH will result in a large change in pH. (ans) (c) 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) (a) Explain how to determine the equivalence point of an acid-base titration using an acid-base indicator. (b)_A few drops of an acid-base indicator Hin (K, =1.0x 10°*) where Hin 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. 7-36 AL ches Gonplee ueSolutio: (a) An acid-base indicator works by marking the end point of a titration by changing colour. It is important to choose the right indicator will ensure that the equivalence point of a titration is virtually the same as the end point (ans) (b) () The solutionis blue initially. (ans) [iw] [Hin] 10° ‘Assuming that the colour change is visible when ut retocant el] 10 IH] =1.0 x 107 pH =—log (1.0 10’) =7 Therefore the colour change will occur at pH7. ans) (a) Silver iodide has a solubility of 1.2 x 10* mol/L at 25°C. Calculate the K.. value. {b) Zinc carbonate has a solubility product of 1.8 x 10”*° at 25°C. Calculate its solubility at 25°C {c) Calculate the solubility of BaF, (K., = 2.4 x 10°) in a 0.01 M NaF solution. Solutio (a) Agl(s) = A8'(aq) +1 (2a) Ky = (Ag TIT) Equilibrium concentrations: [Ag'] = [Ag"]o + change to reach equilibrium =0 +1.2« 10° =041.2%108 [71 =101, + change to reach equilibriu Key =1AB'II T= (1.2 x 10°( 1.2 x 10°) =1.44x 10 “mor/L? (ans) (b) 2nCO,(s) = Zn” (aq) + CO2*(aq) Kup =[2n" J[CO."] = 1.8 «10 Equilibrium concentrations: [2n*"] = [2n*'Jp +change to reach equilibrium =0+x=x [CO5*] = [CO;* Jo + change to reach equilibrium = 0 +x=x 1.8 x10" =[2n" ]ICO,' x= 134 10° mol/L 7 aia 7-37Thus the solubility is 1.34 x 10° mol/L. (ans) (c) BaF,(s) = Ba” (aq) +2F' (aq) (eae K, 2.410% Equilibrium concentrations: [Ba = [Ba""Jo + change to reach equilibrium =0+x=x IF 1= IF Jot change to reach equilibrium =0.01 + 2x 2.4 x 10°° = [Ba YF] =x(0.01 + 24)" Assuming that 2x 2.4.x 10° = x(0.01)? x= 0.24 mol/L negligible as compared with 0.01 (since Kip is small), Thus 0.24 mol of BaF dissolves per litre of 0.01 M NaF solution. (ans) ‘A sample of iron ore weighing 11.15g is crushed, weighed and the ironi(tll) oxide is dissolved in aqueous acid. The Fe™ (aq) ions are then reduced to Fe”"(aq) ions by reaction with an excess of aqueous tin(I) chloride, SaCl, The solution is then mixed with dilute sulfuric acid and made up to a volume of exactly 250.0cm’ in a volumetric flask. 25.0cm’ portions of this solution are then titrated 0.100 mol dm ° aqueous potassium dichromate(Vl) using a suitable indicator. The results are given below 1 2 3 0.00 21.85 0.00 21.85 43.25 | 21.50 Complete the table and use the results to calculate the number of moles of potassium dichromate(VI) needed to react with the Fe” ions in 25.0cm’ of the solution, Solution: 1 2 3 21.85 21.40 | 21.50 Titration number 2 and 3 are chosen for getting the average values.as their titre values are within +10cm’. 21.40+21.50 1L.45em* 2 Average volume of titre used = 21.45 No, of moles of KCr20y used = 5» 0.100 = 2.145 » 10 mol (Examined in 2013p2.2c) AL ches Gonplee ueIn an experiment, a student mixed 0.0040 mo! HCl(aq] with 0.0025 mol NaOH(aq) to form a1 dm’ solution. Deduce the pH of the solution. Solution: HCi(aq) +NaOH(aq) >» NaCi(aq) + H20(!) HCI(aq) Ismixed in excess, pH of NaC/(aq) and H,0 is7. Hence pli of solution is determined by unreacted excess HCI(aq). Unreacted excess HCi(aq) = 0.0040 ~ 0.0025 = 0.0015 mol Hei(aq) > H'(ae) + CF (aq) [H'] = [Hci] =0.0015 mol dm* pH =~logio [H'] =1og30 [0.005] 82 (Examinedin 2012p1.11) 7 sia7.3 | Phase equilibria (suppiementary topic) Define Phase diagram 2 Itis a plot of experimentally determined results over a wide range of pressures and temperatures. Typical phase diagram Bos 5 AL ches Gonplee ue ‘An exemple would be that of carbon dioxide. Line AB is the sublimation curve where Pressure /atm solid CO2 is in equilibrium with its vapour, solid liquid Line BC is the vapour pressure curve co, where liquid CO is in equilibrium with 5.1 its vapour, gaseous Line BD is the melting point curve where me solid CO, is in equilibrium with its liquid. 56 Temperature /'C Solid CO» is denser than liquid CO,, and its melting point increases with an increase in pressure. Thus line BD slopes to the right. Point B is the triple point where the three phases co-exist in equilibrium. Point Cis the critical point beyond which the liquid phase cannot exist Liquid CO; exists only at temperatures > 56°C and pressures > 5.1 atm, Therefore, the pressure inside an unopened fire extinguisher is above 60 atm. There is a drop in temperature and pressure when the nozzle is opened, forming a finely-divided solid Solid CO; sublimes at atmospheric pressure to form ‘dry ice’Atypical phase diagram o & a ‘An example would be that of water. Pressure / atm Point B is the ¢riple point where the three phases co-exist in equilibrium Point Cis the critical point beyond which the water cannot exist: Line BD is the melting point line and is sloping to the left es waters denser than ice, and its melting wo 647 point decreases with an increase in a Temperature /°C pressure The melting point boundary slopes to the left if the liquid is denser than the solid, Ifthe solid is denser than the liquid, the melting point boundary slopes to the right. The melting point boundary is parallel to the vertical axis if the solid and liquid have the same density cooling curve is obtained when a gaseous substance is cooled at a constant pressure to forma solid. A heating curve is obtained when a solid substance is heated at constant pressure to forma vapour. Liquid/vapour equilibrium a \Vapour pressure increases with an increase in temperature as more molecules escape from the liquid into the vapour phase when a liquid is. heated. The ligquid/vapour equilibrium is a dynamic equilibrium where the rate of condensation is equal to the rate of vapourisation Boiling occurs when the saturated vapour pressure is equal to the external, pressure, A liquid with a lower saturated vapour pressure boils at a higher temperature than one with a higher saturated vapour pressure. ‘The enthalpy change of vapourisation is the energy required to convert one mole of a substance from its liquid to vapour state at its boiling point. For chemically similar molecules with similar intermolecular forces, the relationship between the enthalpy change of vapourisation and the boiling point (in K) isapproximately linear, 7 aia rataa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.‘The total vapour pressure of the system is the sum of the vapour pressures of the pure liquids. Examples include the mixture formed from mixing methanol and water, and that with hexane and heptane. Raoult’s law ‘The partial pressure exerted by a liquid A in a mixture is the product of the mole fraction of A in the mixture and the vapour pressure of A, at the same temperature. where Xq= mole fraction of A P°, = vapour pressure of A Non-ideal mixture a ‘There are two types of non-ideal mixtures: minimum boiling point azeotrope and maximum boiling point azeotrope. ‘An azeotropic mixture has a fixed composition and boiling point, and distils out with the same composition. Minimum boiling point azeotrope — intermolecular forces of attraction are weaker in the mixture than in the pure liquids. ‘+ Heats absorbed as some of the A~A or B-B interactions are replaced by weaker A-B interactions. © Volume increases upon mixing as the intermolecular distance between the weaker A-B interactions are greater. © An example would be propan-1-ol and water. Maximum boiling point azeotrope — intermolecular forces of attraction are stronger in the mixture than in the pure liquids. + Heatis evolved end volume decrease: * Liquid molecules escape less easily into the vapour phase. ‘An example would be methanoic acid and water. Asolution shows positive deviation from Raoult’s law when the total vapour pressure of a solution of two miscible liquids is higher than that calculated using Raoult’s law. A solution shows negative deviation from Raoult’s law when the total vapour pressure of a solution of two miscible liquids is lower than that calculated using Raoult’s law. 7 aia 743Mixture of immiscible liquids Each liquid exerts its own vapour pressure, independent of each other. } The total pressure of the mixture at a temperature T is the sum of the saturated vapour pressure of A and B at the same temperature. Prot = P°at Pos Measurement of the boiling point of liquids Athermometer is placed directly into the liquid. A water condenser helps prevent changes to the composition and prevent toxic fumes from being released into the surroundings. J Adisadvantage is that it is difficult to judge if the liquid is actually boiling, Simple distillation & Itis used to separate a volatile solvent from a non-volatile solute, The volatile component is collected as the distillate, Fractional distillation % Itis used to separate mixtures of completely miscible liquids using their difference in boiling points. % This is especially useful if their boiling points are close. J The vapour given off is richer in the more volatile component in the mixture (lower boiling point) <} Vapourisation and condensation will take place continuously in the fractionating column and the more volatile component is collected as the distillate. Azeotropic mistures are not separated completely by fractional distillation. © Glass beads in the fractionating column provide a larger surface area of contact between the descending liquid and the ascending vapour. 7 Fractionating columns should be long and densely packed with glass beads Fractional distilation should be carried out slowly to maintain a steady temperature gradient. Steam distilla n % tis used to separate liquids with high boiling points which may decompose on direct heating. 7-48 AL ches Complete GeAsolution of water and phenylamine has to be separated by this method as phenylamine decomposes before it boils. J Steam whichis passed into the mixture condenses, giving off the latent heat of vaporization. This indirectly heats the mixture. 2 The distillate will contain both water and phenylamine. 4 The composition of the distillate can be calculated as follows: mass of A M,= relative molecular mass of A Partition coefficient } When a solid distributes itself between two immiscible solvents, its concentrations in the two solvents has a constant ratio ata fixed temperature X,Y = solvent partition coefficient + Kis constant provided © temperature is constant; * solutions are dilute; * solute has the same molecular form in both solvents. © These steps are taken to determine the partition coefficient in the laborato + shake the mixture thoroughly till equilibrium is reached ‘© maintaining a constant temperature + allowing for the separation of the two layers with the one which is less dense floating on the other; + withdrawing a known volume from each layer; and + titrating with a standard alkali to determine the equilibrium concentration of the acid in each layer. 7 ealiria 7-45© Given that the concentration of acid in the aqueous and organic layers are 0.350 mol dm? and 0.0250 mol dm * respectively. Calculate the partition coefficient for the acid distributed between the organic solvent and water. 0.350 0.0250 Partition coefficient Solvent extraction o It is the partial removal of a molecular solute from one liquid into another immiscible liquid. Ether is most commonly used to extract an organic compound from an aqueous solution as it is chemically unreactive, is immiscible with water, has a high solubility for organic compounds, and is very volatile. A disadvantage of using ether ‘sits flammability. Continuous extraction using portions of the extracting solvent at a time is recommended. Chromatography a & AL ches Gonplee ue ‘The components adsorb and partition between a stationary and mobile phase Different solubilities in the solvent and different affinities for the stationary phase cause molecules to move at different speeds. This leads to separation of the molecules. ‘The stationary phose Is the chromatography paper itself while the mobile phases any suitable liquid solvent which will give a good separation of components. A spot is made of the mixture to be analysed, and is placed slightly above mobile phase. Equilibrium is set up when the solvent rises and reaches the spot. The components are repeatedly partitioned. The more soluble component will move further up the paper. ‘The solvent front almost reaches the top of the paper. The retention factor, Ry, is given byAspray reagent identifies colourless components. Two-way chromatography + Itallows for a more in-depth analysis of a spot of mixture. 4 Iwo different solvents are used, and the first chromatogram is tuned through 90° after the first separation. J ‘The spots are more dispersed on the final chromatogram. Thin-layer chromatography NO; (aq) + H;0(!) AL ches Gonplee ueAmount before reaction: HNO; = 0.01 mol on = 2 (0.1) = 0.001 000 Amount after reaction: Initial concentrations: {HNO} = 222 INO To= IH'l=0 (1000) = 0.15 M 0167 M Let xbe the change in concentration of HNO, that is needed to attain ‘equilibrium. Equilibrium concentratior [HNO,] = 0.15 -x [NO,] = 0.0167 +x [H)]=x= 10 *5 = 0.031623 M (5 sf) [#'J[soo"] _ (w(o.0167+x) [rNO,] ois-x = 0.00352 (3 sf}. (ans) Determine which of the following acids is most suitable for preparing a buffered solution of pH 5.5. (a) Acid A (K, = 2.0108) (b) Acid B (kK, (0) Acid C (K, = 2,0x10°) 2.0x10°*) Solutio From the Henderson-Hasselbalch equation, * Itcan be seen that the most effective buffering will occur when [HA] is equal to fw) pH = ~log[H’] =5.5 7 sia[H'] = 3.162310 Use the exoression [1] =X, [#4] to cateuate the rato of [M4] foreach acid A Ie [ed ia ie] [Ha] I] (b) 3.162310" = 2.016 58 © Since the rt ratio for acid B is closest to 1, it should be the acid used in A the buffered solution, (ans) Describe how to prepare an acidic buffer solution of pHi 3.0. (Use methanoic acid, which has a pK, value of 3.75.) Solution ten] H= pK, + logy PH= Bk + 18:0 Fa) Substituting the values of pH and pk, A [Ha] 3.0= 3.75 + 1089 [a a ee esa From the ratio obtained, it can be seen that for every 1 mole of the acid used, 0.17783 mole of the corresponding conjugate base must be used. ‘Therefore the mole ratio of methanoic acid : sodium methanoate =1 : 0.178 (to 3 sf) (ans) a 7-82 AL ches Gonplee ue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 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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.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.- Asthe electronegativity difference between the element and oxygen decreases, the bonds in the oxides change from ionic to covalent. The table below gives a summary of the reactions with water. Nao Naz0, Sodium monoxide reacts vigorously with water to give sodium hydroxide Na,0(s) + H,O(I] > 2NaOH(aq) pH=13, Sodium peroxide reacts vigorously with water to give hydrogen peroxide, Na,O,(s) +2H,0(I) —> 2NaOH(aq) + H,0,(aq) Oxides of sodium react readily with acids to form salt and water. Na,0(s) + 2HCi()) > 2NaCi(aq] + H20(1) Mgo Magnesium oxide is insoluble in water and does not react with water due to its high lattice energy. However it reacts with acids to form salts. MgO\s) +2HCi(aq) > MgCl,(aq) + H,0(1) pH=6 Al; Aluminium oxide is insoluble in water, but being amphoteric, it can react with acids or alkalis. Ai,04(s) +6HCl(aq) > 2A/C/,(aq) + 3H,0(1) N,0,{s) +2NaOH(aq) + 3420|l) > 2NaA(OH)d(aq) SiO, Silicon (IV) oxide does not react with water, butit reacts with boiling alkalis to form silicates (IV). SiO2(s)+ 2NaOH(aa) > NazSiOa(aq) + H20(1) P.Os PxOr0 Phosphorus trioxide reacts slowly with cold water to form phosphorus acid, PO¢(s) + 6H20(I] > 4H,PO; (aq) Phosphorus pentoxide reacts vigorously with cold water to give polyphosphoric (V) acid P,O,o(s) + 6H20()) > 4H5PO,(aq) Phosphorus pentoxide reacts with alkalis to form the corresponding salt and water. P.Orols) +12NaOH(aq) > 4HNasPO,(aq) + 6H20(!) Solutions formed are strongly acidic with pH = 2. FL cheisoy ~ Gonpiee ui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.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.The 4s electrons are removed first to form positive ions, There are two exceptions. @ Chromium has the electronic configuration [Ar] 30°4s" instead of [Ar] das’. © Hund’s rule states that forces of repulsion between electrons are reduced if each orbital of a subshell is half filled, © Thus the electronic configuration [Ar] 3¢°4s' is more stable. © Copper has the electronic configuration [Ar] 3d"°4s* instead of [Ar] 30°45”. Atomic and metallic radii The first row transition elements are all metals. The physical properties of the d-block elements are generally very similar as there is only a small increase in effective nuclear charge. ©The extra electron is added to the 3d electron shell, which then shields the 4s electrons. ‘© This results in a very small increase in the attraction between the nucleus and the 4d electrons. + Thusthere is very little decrease in the atomic radii of d-block elements. lonization energy examined in 201201.17 & There is 2 very small increase in the ionization energy of first row transition elements. 4 Successive ionization energies of the d-block elements show a steady increase as the energy levels of the 3d and 4s subshells are similar.Comparison of the physical properties of d and s block elements <} The table below shows the comparison of properties of d and s block elements (e.g. calcium). Atomic radius d-block elements have more protons than s- block elements. This leads to an increase in effective nuclear charge and the attractive force between the nucleus and the outer electrons increases, thus the atomic radii are less than s-block elements. (Examined in 2013p2.4a] lonization energy d-block elements have comparable ‘onization energies to s-block elements. The 3d and 4s orbitals are similar in energy. Electronegativity d-block elements have higher electronegativities than s-block elements. An increased nuclear charge effect is exhibited by the d-block elements, Melting point d-block elements have higher melting points. than s-block elements due to stronger metallic bonding, [Examined in 2012p1.17, 2013p2.46] Hardness d-block elements are hard while s-block elements are soft as d-block elements are small in size and are closely packed. Density ‘@-block elements are closely packed in a metallic lattice and thus have high density while s-block elements have low density {examined in 201291.17, 201392.43¢) Reaction withwater | d-block elements do not react with water while s-block elements react vigorously with water. The outer electrons of d-block elements are held more tightly by the nucleus, Electrical and heat d-block and s-block elements are good conductivity conductors of heat and electricity due to the presence of mobile electrons d-block elements have smaller ionic radius than s-block elements and thus have higher charge density and polarizing power. & Similar to s-block elements, the ionic radii of d-block elements are smaller than their atomic radi, This is because their cations have one shell less than their neutral atoms. Hence the outer electrons are more strongly attracted by the nucleus. [Examined in 2012p1.36) 9-48 FL cheisiy ~ GnpleeGuie© Copper(t) nitrate decomposes at a lower temperature than calcium nitrate. ‘The higher charge density and polarizing power of the Cu” ion distort the NO; electron cloud to a greater extent than the Ca” ion, causing the N-O bond to be weakened and hence require less energy to break up. [Examinedin 201393 7 a Characteristic chemical properties of the transition elements or their compounds include: formation of coloured ions and complexes, catalytic activity, exhibit variable oxidation states, and paramagnetism. Variable oxidation states + Alltransition metals with the exception of zinc and scandium are able to show variable oxidation states. * Both zinc and scandium ions do not have partially filled 3d subshells, thus they can only form one oxidation state each ~ Sc”* and Zn”. © Zincand scandium also giffer from other transition elements in that they have lower densities and melting points. (examined in 2012p1.36] 4 Transition metals are able to form variable oxidation states due to the similarity of the energy levels of the 4s and 3d electrons, thus transition metals can form ions of comparable stability by losing different number of electrons. The number of oxidation states of a transition element can be deduced from their electronic configurations. © The number of 3s and 4d electrons affects the possible oxidation states. ‘* The table below shows the possible oxidation states of some transition metals. Titanium 4 41to+4 Vanadium 5 41t045 | Chromium 6 +1to +6 Manganese 7 411047 tron 8 41t046 Cobalt 9 41t045 Nickel 10 tod Copper fn +1t043 194 arinvoautanto te chemiryaranaionelenente+ For higher oxidation states, the metal may exist as covalently bonded ‘0xo-compounds instead of atomic ions. The highly-charged ion would polarize water molecules. Two common oxidising agents used in the laboratory contain transition elements. They are acidified KMnO,(aq) and acidified K>Cr,0,(aq) ‘* Redox potential of MnO,” / Mn? = +1.52V ‘© Redox potential of Cr,0,? / Cr = 41.33 V (Examined in 2012p1.36} The +2 oxidation states of manganese and cobalt are more stable than the +3 oxidation states which oxidize water to oxygen gas. However, for iron, chromium, vanadium and titanium, the converse is true as the +2 oxidation states of the metals are oxidized by oxygen in air. Use of transition metals in redox systems } The +2 and +3 oxidation states of the metals are usually simple ions while the higher oxidation states exist as oxo-ions. These oxo-ions are all strong oxidizing agents. % Acidified potassium manganate (Vil) and acidified potassium dichromate are common oxidizing agents. ‘+ Acidified potassium mangenate (Vl) is reduced to manganese ions when it is added to Fe”’, while the Fe”" is oxidized to Fe”. The purple solution is decolourised. MnO. (aq) +5fe” (aq) + 8H'(aq) > Mn”"(aq) + 5Fe™"(aq) +4H,0(0) [Examined in 2013p1.15] © Acidified potassium dichromate is reduced to chromium ions when it is added to Fe”, while the Fe” is oxidized to Fe*. The colour of the solution changes from orange to green. r,0;* (aq) + 14H'[aq) + 6Fe*(aq) > 2Cr* (aq) + 6Fe* (aq) +7H20() © Predict the outcome of the reaction between Sn” (aq) and acidified H,03. Redox potential of Sn“ / Sn” =-0.15V Redox potential of H0, / H,0=+1.77V. H,0, +Sn” + 2H" — Sn* +2H,0 Cell potential = +1.62 V > 0, feasible Uses of transition metals Titanium is used in the making of aircraft bodies and space capsules as its light and does not corrode. % Cobalt and manganese are used in alloy making. 9-50 chemin angie ie =‘metals can form ions of comparable stability by losing different number of electrons. (ans) (b) Both zinc and scandium do not have partially filled 3d subshells, thus they can only form one oxidation state each — Sc" and Zn** (ans) (c) Vanadium has 5 3s and 4d electrons, thus it can lose up to 5 electrons. Possible oxidation states range from +1 to +5. Chromium has 6 3s and 4d electrons, thus it can lose up to 6 electrons. Possible oxidation states range from +1 to +6. (a) The graph below shows the trend in relative atomic sizes for some transition elements. Explain the shape of the graph. ‘tomic radias Se Ti V Cr Mn Fe Co Ni Cu Zn element (b) The graph below shows the trend in second ionization energy for some transition elements. Explain why chromium has such high ionization energy in comparison to vanadium and manganese. (mel) Ieniation enorey Seow YG Mn Fe Co Ni GW Zn clement Solution: (a) From the graph, it can be seen that the atomic radii 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. Acheson ~ GnpleeGude ace Colour of complexes Complex formation % Transition elements are able to form complexes due to the availability of vacant orbitals. The molecules or ions attached to the metal atom are known as ligands and they have at least one lone pair of electrons available for donation to the central ion, . These can be considered to be attached to the central ion by co-ordinate (dative covalent) bonds. CulOH)2(s) + 6420 On adding excess NHs{aq), the precipitate dissolves to form a deep blue solution, which is caused by the complex ion [Cu(NH3).(H20)2}”"- Cu(OH), +4NH, +2H,0 — [Cu(NH;)s[H20),1" + 20H" © when concentrated hydrochloric acid is added to aqueous copper(I) chloride, the colour of the solution eventually becomes yellow. When water is added to this yellow solution, it becomes blue. Copper (II) salts are soluble in water and they form a blue solution, which is caused by the ion [CulH,0)<]”". chemin angie ie =When excess CI” ions from concentrated hydrochloric acid are added, the solution turns yellow, due tothe formation of a tetrahedral complex through ligand, exchange reaction. [Cu(Hz0)6]”" + 4c = [CuCl] (s) + 6H0 Notice that the reaction is reversible. The addition of water causes the equilibrium to shift towards the left. The chloride ions are then replaced as ligands by the water molecules to form [Cu(H,0)¢]" ions. Hence the solution turns back to blue. {Examinedin 2012p2.3c} Stops for the naming of complexes: + The ligands’ names are given first, followed by that of the metal ion with its oxidation state in brackets + ligands are named in alphabetical order. * For anions, the metal ion’s name is changed to contain ~ate. © - [CulWH,}.}50, is known as tetrammine copper (Il) sulfate while K,{PtCle] is known as potassium hexachloroplatinate (V). as The oxidation state of the metal ion in the complexes is always positive, while the number of co-ordinate bonds from the ligands to the metal ion determines the coordination number. * The net charge on the complex takes into account the charge contributions from the ligands and metal ion. © Common co-ordination numbers are 4 and 6. + The shape of the complex is determined by the number of surrounding ligands. Examples are given in brackets. * Co-ordination number 2 - linear {[CuCl2] ) * Co-ordination number 4 ~ tetrahedral ({CoCi.)*} or sauare planar (INi(CN))”) * Co-ordination number 6 - octahedral ({Fe(CN}«]*) } gands which are able to form more stable complexes are favoured, and can displace “weaker” ligands. Isomerism in complexes + Structural isomers have the same molecular formula but different structural formula. * An-example would be the three isomers of CrC/,(4,0).. Their formulae are [Cr(H2O)3]°".3Cl-, [Cr(H20)sCi]"*2Cl-.H,0 and {Cr(H0).Chy .C-.2H.0. 194 arinvoautanto te chemiryaranaionelenente 9-55Geometricisomers have the same molecular formula and same structural formula but different spatial arrangement of the ligands. ‘* An example would be the two isomers of [Cr(NH3),Ch]". The chlorine atoms could be on the same side (cis-) or on apposite sides (trans-| of the horizontal plane. ‘* These isomers have different dipole moments, producing polar and nor polar molecules. Optical isomers have the same molecular formula and same structural formula but different spatial arrangement of the ligands. © Asymmetrical molecules are produced. * Anexample would be [Cr(C.0,)3}* and [(Cr(HaNCH:CH:NH)3)” ‘+ Achiral complex has no plane of symmetry and forms non superimposable mirror images. Displacement of ligands Two factors affect ligand exchange ~ competing equilibria and stability constants. Cu(OH),s) Gu?" (aq) + 4NHs(eq) <> [Cu(NHs),”° The stability constants, K,,., of the complexes also determine which ligands are preferred. v The greater the value of the stability constants, the greater the stability of the complex ion. } The displacement of a weaker ligand by a stronger ligand will make the E value less positive as the new oxidation state of the metal cation is stabilized © Ammonia can displace water in a nickel complex as the Kins for [Ni(NHs)<]”* is greater than that for [Ni(H20)<]” [Ni(H,0)¢”* +6NH(aq) —> [Ni(NH5)_]”* (aq) +6H,0(I) FL cheisiy ~ GnpleeGuie a© Chloride ions can displace water in a cobalt complex as the Kay for } ICoCl,)* is greater than that for [Co(H,0)<]” [CofH0)¢]”"[aq) + 4C/ (aq) + [Codi] [aq) + 6H20(1) © Ligand exchange may also occur in haemoglobin. The carbon monoxide ligand displaces the oxygen in oxyhaemoglobin to form dative bonds with the iron atoms in haemoglobin, thus reducing the supply of oxygen to the body. The iron-CO bond is stronger than the iron-O, bond. This could lead to carbon monoxide poisoning, a Determination of the stoichiometry of complexes 4 Two methods can be performed to give the relative ratio of ion : ligand. ‘They are the partition and colorimetric methods. Partition method Add an excess of ligand X to the aqueous ions. A complexis then formed with ligand X. & ‘The solution containing both free and complexed ligand X is shaken with CHCI; and allowed to stand. According to the Partition Law, the free ligand X distributes itself between the aqueous and CHCI; layers at equilibrium. 4 The concentration of ligand X in the aqueous and CHCI; layers can be found by titration with hydrochloric acid. The partition coefficient, K, gives the concentration of free ligand X. [free ligand x] [free tigand X].,.,, Hligand Xleonpieses ~ (ligand Xhou ~ [free ligand XIaq Colorimetric method + Itinvolves the measurement of the colour intensities of solutions containing different proportions of the ligand and metal ion. J light which can be absorbed by the coloured complex is passed through 2 solution of the coloured complex. 4 Absorbance « concentration of complex ion 4 Absorbance of the mixtures is measured using a colorimeter. 194 arinvoautanto te chemiryaranaionelenente 9-87aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Worked Examples Give the oxidation states of vanadium in the following ions. Also, state the colours of each ion. (a) vor" (aa) (b) Vo (aq) (©) (M{H.0}4)* (d) (V(H.0).)” Solution: {a) +5. Yellow. (ans) (b) +4. Blue. (ans) {c) +3.Green. (ans) (d) +2. Violet. (ans) {a) Explain why transition metal complexes are coloured using copper (I!) ian as an example. (b) Give two examples of transition metals that do not form coloured complexes and explain why. (c)_ Name some factors affecting the colour of transition metal complex ion. Solution: {a) Complex ions containing transition metals are usually coloured. When the ligands bond with the transition metal ion, there is repulsion between the electrons in the ligands and the electrons in the d orbitals of the metal ion, That raises the energy of the d orbitals and splits them into ‘two groups. Using Cu ion as an example, the diagram below shows the arrangement of the d electrons in a Cu” ion before and after six water molecules bond with it. ite] (te) ite] ite) it | —— Hf | changein oon i) The size of the energy gap between them (shown by the arrow on the diagram) varies with the nature of the transition metal ion, its oxidation state (whether it is +3 or +2, for example), and the nature of the ligands. ‘When white light is passed through a solution of this ion, some of the energy inthe light is used to promote an electron from the lower set of orbitals into ‘a space in the upper set. FL cheisiy ~ GnpleeGuie a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.M'" ions are not formed as the ionisation energy would be too high. ‘Therefore compounds involving the +4 oxidation state are covalent. The strength of the covalent bonds formed with other elements decrease down the group, decreasing the stability of the +4 oxidation state, and increasing the stability of the +2 oxidation state. Therefore, lead forms mainly ions of the +2 oxidation state while the rest of the Group IV elements preferentially form ions of the +4 oxidation state. Tetrachlorides Tetrachlorides with the formula of XCi,, are tetrahedral and have a simple molecular structure. Discrete molecules are held together by weak van der Waals’ forces of attraction. They have low meiting and boiling points due to the weak bonding between molecules. Thus they are volatile liquids at room temperature. F The boiling point of tetrachlorides increase down the group as the strength of the van der Waals’ forces increase with an increase in molecular size. Reaction of the tetrachlorides with water Asthe elements become more metallic in nature down the group, the ease of hydrolysis decreases, % Tin (IV) chloride and lead (IV) chloride are partially hydrolysed while carbon tetrachloride does not react with water. % ‘Silicon (IV) chloride reacts vigorously with water producing fumes of hydrogen chloride and a white precipitate of silicon (IV) oxide. ‘Silicon can accept lone pair of electrons from water molecules as it has empty d-orbitals, allowing for the formation of dative bonds. ‘+ Carbon, however, does not have ¢-orbitals, and thus cannot form dative bonds with water molecules. © The equation for the reaction of silicon (IV) chloride with water is as follows: SiCl,+2H,O > SiO, + AHCI 9-68 FL cheisoy ~ Gonpiee ui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.Physical properties 4 Pure nitric acid isa colourless and viscous liquid. % Concentrated nitric acid is yellowish due to photochemical decomposition and the subsequent dissolution of nitrogen dioxide in the acid. {tis aweak electrolyte which ionizes to produce NO2’ and NO; . Chemical properties > Nitric acid is a strong acid which dissociates completely in water. It neutralizes bases; liberates carbon dioxide from carbonates and hydrogencarbonates; and disolaces weak acids from their salts. Nitric acid reacts with metals to form nitrates only as hydrogen is being oxidised, However, cold dilute nitric acid liberates hydrogen when reacted with magnesium and calcium. Nitric acid is a strong oxidizing agent. It gives different products when reacted in its dilute or hot, concentrated form, as different redox equilibria are used depending on the redox potentials of reactants. # Dilute nitric acid can o» acids C+4HNOs -> H,COs+4NO; +H20 12 certain non-metals such as carbon to their 7 Concentrated nitric acid forms an impervious layer of oxide with some metals such as aluminium. This acts as a protective layer. Uses Uses of nitric acid include: = manufacture of nitrate fertilizers; and © manufacture of explosives (T.N.T.) and dyes (nitrobenzene). Catalytic converters Catalytic converters are installed in cars to remove the harmful exhaust gases (oxides of nitrogen, unburnt hydrocarbons and carbon monoxide). © Removal is by decomposition to nitrogen and oxygen or the reduction of carbon monoxide and unburnt hydrocarbons over a rhodium catalyst. 2CO+2NO -> 2CO, +N, * Leadrenders the catalyst useless. 3) ogy ander 9-87aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Worked Problems Ee) The combustion of fue's in motor vehicles, trains, aeroplanes and power stations produces the pollutant gas N (a) Write an equation to show how NO; is formed in these situations. fa) (b) (i) How is the NO2 removed from the exhaust gases of motor vehicles? (ii) Write an equation for this process. re] (c) Suggest whether the production of the pollutant NO; would be reduced if fossil fuels were replaced by hydrogen as @ fuel for combustion. Explain your answer. a) (d) Inthe atmosphere, NO, acts as a catalyst for the oxidation of SO, to SOs. $0,(8)+%0,(¢) “> sOxle) (i) Whatis the environmental significance of this reaction? The oxidation takes place in two steps. The initial reaction is that between NO, and SO,. reaction 1 NO,(g)+SO2\g) => NO(g) +SO3(g) AH 168 kJ mol * Write an equation to show how the NO: is regenerated in the second step of the oxidation. {iil) Write an expression for the equilibrium constant, K, for reaction 1, stating its units. {iv) Itequal amounts of NO,(g) and SO,(g) are allowed to react at room temperature, itis found that 99.8% of the gases have been converted into products at equilibrium. Calculate a value for K,, (v) The temperature of the atmosphere decreases with height. How will this affect the position of the equilibrium in reaction 1? Explain your answer. 71 (Total: 11) ‘Solution: {a) Na+ 202 -» 2NO, (ans) (b) (i) catalytic converter and passing the exhaust gases over a catalyst. (ans) (ii) NO, +20 — %Ny+2CO, (ans) (c)_ No, it would not be reduced. Because the reaction in (a) does not presuppose a particular fuel_ (ans) (a) (I) $03 produces acid rain. (ans) (ii) NO+%0, + NO, (ans) Rok (Fo) ay (.o,Fo,) (99.8) (0.2)° (i) K, (iw K, =2.5%10° (ans) FL cheisoy ~ Gonpiee uiFL cheisoy ~ Gonpiee ui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.© CHsCH2CHs is an unbranched aliphatic compound. CH | @ CHCHCHCHSCH, is a branched aliphatic compound, c Alicyclic compounds © An alicyclic compound contains rings of ~CHy- units joined by single bonds. Their general formula Is C,H2,, the simplest member being cyclopropane (CsHo). ° oO {eyelopentane) is an alicyclic compound. Aromatic compounds ° (benzene) is an aromatic compound. [Examined in 2012p2.4b] Carbon nits pure form carbon exists as diamond or graphite, Carbon has a unique nature in that it is able to catenate and form millions of ‘organic compounds. © Catenate refers to the ability to form bonds with its own atoms to produce long chain molecules, 10-6 chemin Conpiee ue =Displayed formula © The structural formule of benzene General formula Alkane Gina ‘yelalkane Gin Alkene Gn Halogenoaikane Coan where X isthe halogen atom Halogenoarene & where Xsthe halogen atom ‘Alechol CHiniH Phenol on Aldehyde ® Nexo iZ where R= H oran aly! or ary group. Ketone R Ne ® where R= alkyl or aryl group. Carbone ace ° a— ton where R=H, alkyl or phenyl Add chore ° ata where R, f= ay! or phenyl FL cheisoy ~ Gonpiee uiM n— tov where RR’ = alkylor phenyl Amine Cite Nas amide ° 1 R—C—NM, where RR’ = alkylor phenyl ‘Amine ec H | CoN I cooH where R= H or avarlety of groups Nari CliaN Worked Examples Draw the displayed formula of the following organic compounds. (2) butane (b) ethene (0) chlorobutane (d) benzene (e) chlorobenzene () butanol (@) phenol (h) methanal () methanoic acid () methanoy! chloride @ HHH A a H-C-C—C—C—H Prt f "hon (ans) ( 4 4 \ cHc 7 \ " x (ans) 103 organ daniry-invoditoryonee 10-9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.Give the systematic name for each of the follo () CH; er (b) () | CH,CHCH,COOH Solutior (a) 3-bromo-2-methylpentane. (ans) (b) 4-chlorocycichexanol. (ans) (c) 4-aminobutanoic acid. (ans) ing organic compounds. Give the systematic name for each of the following organic compounds. (2) CH,CH,CH=CHCH, (b) CHCHEH CH, c ) Br | CHsCHCHCH3 I Br Solu (a) Pent-2-ene. (ans) (b) 2-chlorobutane. (ans) (c)_2,3-dibromobutane. (ans) 103 organ daniry-invoditoryonee 10-15EQ Characteristic organic reactions Organic reactions Organic reactions can be classified according to the type of reagent being used * Nucleophilic reactions in which nucleophiles are involved. ‘*Flectrophilic reactions in which electrophiles are involved. F Organic reactions can also be classified according to what happens when the reaction is over. + Addition reactions in which atoms) or group have been added. ‘Substitution reactions in which atom(s) ot group have been replaced, ‘© Elimination reactions in which atoms from two neighbouring carbon atoms have been lost. + Organic reactions take place in three stages — the initiation stage, the propagation stage and the termination stage. Homolytic fission 4 Free radicals are atoms or groups of atoms with an unpaired electron and are very reactive, A-B YY Ae+Be (free radicals) © The #OH free radical is formed by the decomposition of hydrogen peroxide, H,0>. WON" — 2 [examined in 2013925 Heterolytic fission % Carbocations (carbonium ions) are carbon species that carry a positive charge. 103 organ daniry-invoditoryonee 10-17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.© Functional isomers: HoH HOH a H-—C—C—C—C—OoH (CH;CH»—O—CH.CH3 Proll HoH OH OH The different types of structural isomers have varying physical and chemical properties. Stereoisomers There are two types of stereoisomers. © Geometric (cis-trans) isomers, where the isomers have restricted rotation about a double bond, thus giving rise to two ways of arranging the four groups across the double bond. © Geometric isomers exist in pairs but they have different physical properties. © Geometric isomers have similar chemical properties (react with the same reagents but at different rates) ‘9 The cis isomer has the two groups on the same side of the double bond but the trans isomer has the two groups on different sides of the double bond. © Geometric isomerism cannot occur if either carbon has two identical groups. ‘© The cis isomer generally has a higher boiling point due to its higher polarity. It also has a lower melting point as itis not as symmetrical, forming less regular crystal lattices. (Examined in 201392.31 © Optical isomers, where the isomers differ in their symmetry and are able to rotate the plane of polarization of plane-polarised light. © This cccurs when the four covalent bonds formed by a central carbon atom (chiral carbon) are tetrahedrally arranged around it. There is no plane of symmetry in the compounds, © This results in two optical isomers that are mirror images of each other and are non-superimposable upon each other. © Ifthe central carbon atom has more than 1 identical group, itis superimposable on its mirror image and thus does not exhibit optical isomerism, Thus the compound is optically inactive. 10-30 FL cheisoy ~ Gonpiee ui(Examined in 2012p2.42, 2013p1.19) Optical isomers can be grouped in 2 ways: © Optical isomers which are mirror images of each other and are non- superimposable are termed enantiomers. © They have identical physical and chemical properties but they differ in their effect on plane polarized light. They will rotate the plane of polarized light by equal amounts in opposite directions. © Theenantiomers rotate plane polarized light by equal angles but in two different directions — dextrorotatory enantiomer (d or +) rotates plane polarized light to the right while the laevorotatory enantiomer (/ or) rotates plane polarized light to the left. © Ifa mixture contains equal amounts of dand / enantiomers (racemic mixture), they are optically inactive as the effects cancel out one another and the mixture is unable to rotate plan polarized light. Inliving organisms, compounds are usually chiral and only one enantiomer is found in the same biological system. Generally, only one enantiomer can be Used by an organism, Different stereoisomers have different biological actions. One enantiomer could be a useful drug while the other enantiomer may be ineffective or cause serious side effects. + Chiral drugs are developed for efficiency and protection against the side effects of its mirror image form, © Geometric isomers: oe or 8 4 \ 7% \ L =e 7 ™ SON 4 W W a cis isomer Transisomer © Optical isomers: , 4 4 | | c= OH HOC aN i ar ‘i ci Note that the three-dimensional structure of optical isomers should be Indicated according to the convention used in this example. 103 organ daniry-invoditoryonee 10-31Worked Examples Isomerism refers to molecules having the same molecular formula but different arrangements of their atoms. {a)_ Distinguish between structural isomers and stereoisomers {b) Draw the structural isomers of the organic compound with the formule CsHiz and name them. {c) By changing the position of the functional group in C;H,,C/, deduce the number of structural isomers that are possible, Draw their structures and name them. (a) Structural isomers are organic compounds with the same molecular formula but different structural formulae, while stereoisomers are organic compounds with the same molecular and structural formulae but differ in the orientation of the atoms or groups of atoms in space. Structural isomers consist of chain, positional and functional group isomers, while stereoisomers consist of geometrical and optical isomers. (ans) (b) These are known as chain isomers. (ans) Hoon a hid tet i | Ah 8 -t-n 1 4 2-methybutane , i a—t—n tit iy aon 1 i ctloropentane 2-chloropentane HoH Go oH # 3.chloropentane 10-32 FL cheisoy ~ Gonpiee ui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.ERB anes Define Hydrocarbon & Alkanes, alkenes, alkynes and arenes are hydrocarbons. Alkanes Alkanes form a homologous series and have the general formula CHan.2 Each member differs from the next by a CH. unit % The table below shows the members of the alkane family up to 8 carbon atoms. Methane CHa CHa Gas Ethane Gos CHsCHs Gas Propane GH CH;CH2CH3 Gas Butane Caso CHs(CH2):CHs Gas Pentane GHz CHs(CH2)sCHs Liquid Hexane Cotta CHs(CH2):CHs Liquid Heptane Gti CHs(CHa)sCHs Liquid Octane Cotta CHs(CHa).CHs Liguid Cycloalkanes Cycloalkanes forma homologous series and have the general formula CyH.z». © The carbon atoms are joined by single bonds and they have ring structures. 2 Cyclobutane (C,H,) and cyclohexane (C,H,,) are examples of cycloalkanes. 10-38 A Ghomiany — Conplee Ge =aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.- The products of fractional distillation of crude oil are shown below. Gas <40 Gn6s Natural gas fuel Gasoline | 40-180 G-Go Automobile fuel Naphtha | 100-200 G-Go Solvent Kerosene | 190-250 Cu- Cs Jet and diesel fuel Gas oil 250-350 Cs— Ce Fuel oil Wax oil 300-400 Cie— Coo Lubricants Wax 350-500 Cio ~ Cas Paraffin wax Residue >400 >Cs Tar, bitumen in asphalt Cracking } Cracking produces smaller and more volatile molecules from large hydrocarbon molecules. These smaller molecules can be used as fuels. & Incatalytic cracking, vaporized hydrocarbon is passed over a silica catalyst at 500°C. Inthermal cracking, the temperature required is much higher. J Cracking is an important source of alkenes. Reactions of alkanes Alkanes are chemically inert as the C—H bond is not polarized. -% Two common reactions that alkanes undergo are combustion and halogenation (free-radical substitution). Combustion Alkanes burn in excess oxygen to form carbon dioxide and water. Thus they undergo complete combustion. {€romined in 2032p2.23) & This isan exothermic reaction and thus alkanes can be used as fuels. ‘+ The amount of heat produced increases with relative molecular mass. © Alkanes are easily burnt. Only alkanes in the gaseous state will burn, thus solid and liquid alkanes ‘must be converted to the gaseous states for combustion to occur. 10-40 A Ghomiany — Conplee Ge =