36 G9) A-Level Step-by-Step F ocus Chemistry (Higher 2) Essential Summaries a CS Toh Edition H2.2A-Level Focus — Chemistry — Edition H2.2 Book edition: First published in 2017 Published by Step-by-Step International Pte. Ltd. My Mail Box 889128, Singapore 919128 Copyright © 2017 Step-by-Step International Pte. Ltd. All rights reserved. No part of this book 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 prior written permission of the Publisher. No patent liability is assumed with respect to the use of the information contained herein. Every reasonable effort has been made to contact the holders of copyright material, but if any have been inadvertently overlooked, the Publisher will be pleased to make the necessary arrangements atthe first opportunity. Conditions of Sale ‘This publication and the materials included therein are provided on an “as is", “as available” basis without warranty of any kind, either expressed or implied While all reasonable care have been taken in the preparation of this publication, to the fullest extent permitted by law, the Publisher does not warrant and hereby disclaims any warranty as to its accuracy, correctness, reliability, timeliness, non-infringement, title, merchantability or fitness for any particular purpose. Its availability or updates are also not guaranteed, ‘The Publisher, the editors of, the contributors to this publication and anyone else involved in creating, producing or delivering this publication, shall not be liable for any damages or losses, including any general, special, incidental or consequential damages or losses, arising out of your use or inability to use this publication, even if the relevant parties have been advised of the possibility of such damages or losses. For the avoidance of doubt, the sale of this publication exeludes pro} otherwise ng it in any other form or media, electronic or Important! By purchasing this publication, you are deemed to have agreed to these conditions. For information on distributors, please visit Please send feedback to: Debgagga 08+ comistep-by-step Bapssg ey SP bY step@post-l comContents Definitions Section 1 Core Idea 1 - Matter LI Atomic Structure Section 2 Core Idea 2~ Structure & Properties 2.1 Chemical Bonding, 22 The Gaseous State 23 Theories of Acids & Bases 24. The Periodic Table Section 3 Core Idea 3— Transformation 3.1 The Mole Concept & Stoichiometry 3.2. Chemical Energetics 33. Reaction Kinetics, 34. Chemical Equilibria Section 4 Extension Topics 4.1 Chemistry of Aqueous Solution 42 Electrochemistry 43 Introduction to Transition Elements Section 5 Extension Topics — Organic Chemistry 5.1 Introduetion & Isomerism 5.2. Mechanisms 5.3. Hydrolysis, 5.4 Oxidation & Reduction Section 6 Extension Topics ~ Organic Chemistry 6.1 Characteristic Reactions 62 Distinguishing Tests 63 Acidity & Basicity 6.4 Amino Acids Preface 10 4 16 18 24 26 30 32 33 35 38 40 42 46 48 ‘© This publication gives concise summaries, intended as a quick reference for readers who are studying A-Level Chemistry (or its equivalent), and are preparing for the examinations. It contains essential information/concepts that most readers should want to focus on when revising for the examinations. We recommend that readers review the relevant updates at our website before using this book. ‘The updates contain late-breaking information that became available after the book was printed, evel Focus - Chemisty Please check for supplements and updates at: http://www. post-I.com/step-by-step edDefinitions Definitions Mole Concept & Stoichiometry Chemical Energetics © Relative atomic mass, A, of an element is defined as the ratio of the average mass of one atom of the element to > the mass of an atom of isotope, expressed on the '°C seale. © Relative isotopic mass, A,.. of a particular isotope is defined as the ratio of the mass of one atom of the isotope to the mass of an atom of "C isotope, expressed on the '°C scale. © Relative molecular mass, M,, of & substance is defined as the ratio of the average mass of one molecule of the substance to zb the mass of an atom of °C isotope, expressed on the "°C scale © Relative formuta mass of an ionic compound, M,. is defined as the ratio of the average mass of one formula unit of the compound to 7 the mass of an atom of “C isotope, expressed on the °C scale. © Empirical formula of a compound is the simplest formula which shows the ratio of the atoms of the different elements in the compound © Molecular formula of a compound is ‘one which shows the actual number of atoms of each element present in one molecule of a compound © One mole of any substance is the amount of substance containing a number of particles equal to the Avogadro constant, L (6.02 x 10°, © Standard enthalpy change of formation, Ni1;°, of « compound is defined as the enthalpy change when one mole of the compound is formed from its elements under standard conditions (at 25°C, | bar) © Standard enthalpy change of combustion, AH”. is defined as the enthalpy change when one mole of a substance is completely burnt in oxygen under standard conditions (at 25°C, | bar). © Standard enthalpy change of hydration, MHfiys, of an ion is defined as the enthalpy change when ‘one mole of the gaseous ions is dissolved in a large amount of water under standard conditions (at 25°C, 1 bar, © Standard enthalpy change of solution, Ni. is defined as the enthalpy change when one mole of a substance dissolves in such a large volume of solvent that addition of more solvent produces no further heat change under standard conditions (at 25°C, 1 bar). © Standard enthalpy change of atomisation, AH... is defined as the enthalpy change when an element or a compound is converted into one mole of free gaseous atoms under standard conditions (at 25°C, 1 bar) © Standard enthalpy change of neutralisation, AH, is defined as the enthalpy change when one mole of water is formed in the neutralisation between an acid and an alkali, the reaction being carried out in aqueous solution under standard conditions (at 25°C, 1 bar). Note: 1 bar = 110° Pa; 25°C = 298 K ‘Lael Fous~ ChemistyDefinitions 3 Definitions Pi Chemical Energetics Reaction Kinetics © Lattice energy of an ionic crystal is the heat energy evolved when one mole of crystalline solid is formed from its separate gaseous ions under standard conditions (at 25°C, 1 bar) ‘© First ionisation energy (LE,) of an element is defined as the amount of energy required to remove one electron from each atom in a mole of gaseous atoms producing one mole of gaseous cations X@>X +e AW= ILE © First electron affinity E.A.) of an element is the enthalpy change when an electron is added to each atom in a mole of gaseous atoms to form singly- charged negative ions Xgte+X@) AH I"EA © Bond energy (of dissociation) is the energy required to break one mole of a covalent bond between two atoms in the gaseous state. ‘¢ Hess? Law states that the enthalpy change in a chemical reaction is the same whether the change is brought about in one stage or through intermediate stages, © Entropy, S, is a measure of the disorder (or randomness) in a system. ‘© Standard Gibbs free energy, NG* state function of a system and is defined by means of the equation, AG* = AH*-TAS* where T= temperature in K © A state function (or function of state) ‘is one whose value is determined solely by the state of the system (ce. the amount of substance, its temperature and its pressure) and is independent of how the change is brought about (or the route of the change). Rate of reaction is defined as the change in concentration of reactants or products per unit time; ie, rate oc ZL Rate equation shows exactly how the rate of reaction is dependent on the concentration of reactants; ic. rate = ke" where k= rate constant n= order of reaction c= [reactant] Order of reaction with respect to a given reactant is defined as the power to which the concentration of that reactant is raised to in the experimentally determined rate equation. For the general equation, aA+bB - products the rate equation is given by rate = k[A]"[B]" where k = rate constant 'm = order of reaction w.r.t. A n= order of reaction w.r.. B m+n = overall order of reaction Rate constant. k, is a constant of proportionality in the rate equation. Itis constant for a given reaction at a particular temperature Half-life of a reaction, t, is the time taken for the initial concentration of a reactant to fall to halfits value Rate-determining step (14.5, is the slowest step in the reaction mechanism and it determines the rate of the entire multi-step process, Activation energy is the minimum amount of energy that reactant particles must possess in order to react. Michaelis constant, Km. is defined as the concentration of substrate needed to achieve 4 maximal rate of reaction (ie. 4 Vinax). evel Focus - ChemistyDefinitions Definitions (continued) Equilibria Equilibrium Constants * A reversible reaction is one which can proceed in both directions (and is indicated by using the sign = in the equation), © Dynamic equilibrium refers to @ reversible reaction in which the rates, of forward and reverse reactions have become equal and there is no change in the concentrations of the reactants and the products. © Le Chatelier’s Principle states that if a change is made to a system in equilibrium, the system reacts in such away as to tend to oppose the change, and a new equilibrium is formed. © An Arrhenius acid is substance which dissociates in water to give hydrogen ions (H") An Arrhenius base is a substance which dissociates in water to give hydroxide ions (OH) ‘* A Bronsted-Lowry acid is a species which donates proton (H’) to a base: ie. a proton donor. A Bronsted-Lowry base is a species which accepts proton (H1") from an acid; ie. a proton acceptor * A Lewis acid is a substance which accepts an electron pair. i.e. a lone pair acceptor. A Lewis base is a substance w donates an electron pair; i.e. alone pair donor © Degree of dissociation or ionisation (a) is the fraction or percentage of molecules that dissociate into ions. © A buffer solution is a solution whose pH remains almost unchanged when small amounts of acid or base are added to it Consider the equilibrium, aA+bB = cC+dD equilibrium constant, Kis given by = (cp i* K. = FEET andisa constant, [APB ata given temperature Consider the equilibrium, aA@+bBe@) = cC@+dD@) equilibrium constant, Kp, is given by _ (eo) (Po) (Pa)? x(pa)” constant, at a given temperature . and is a For a weak acid HA, HA@g+ H0@) = 10% aq) + Aan the acid dissociation constant, Ky, is given by _ [HO IA-} [HA] is a constant at a given temperature. Ky mol dm and, For a weak base B, Beaqy + H0() = BH"(aq) + OH (a) the base dissociation constant, Ky, is given by PPA UOH sot dm and, [B] is a constant at a given temperature. Ky For a sparingly soluble salt, A,By, at equilibrium, A.Byo = ZRa decays to give only an element X and a high energy particle (He), which |S. targets the cancer cells. Ra {He+X How many protons and neutrons are present in clement X? S. massno. of X= 223-4=219 proton no, of X = 88 = 2= 86 no. of protons =86 (ans) no. of neutrons = 219 — 86 (ans) Direction of deflection depends on charge of particles: ~ positive ions deflected to -ve plate; ~ negative ions deflected to +ve plate. ctorge magnitude of deflection 2 22. A beam of protons, when passed through an electric field of constant strength, was deflected by an angle of 12° towards the negative plate protons Te Under identical conditions, a beam of particles Y, each with 24 times the ‘mass of a proton, Was deflected by an angle of 1° towards the positive plate What is the overall charge on a particle of Y? Deflection of ¥ towards the positive plate suggests that Y is negatively charged Since angle of deflection o “28, for protons, | |= + & angle = 12° for angle See y= ob for Y,| |= 824 and angle since angle = 1°, -, S882 = 4 or Jeharge|= charge on ¥=—2. (ans) a ‘Lael Fous~ Chemisty §1.1 Atomic Structure 9 1.1 Atomic Structure Pi Electronic Configurations Ionisation Energies (1.E.) ‘* sorbitals are spherical in shape. oO Is orbital 2s orbital ‘+ p orbitals are dumb-bell shaped. prorbital —p,orbital ~—_p orbital © five types of d orbitals. Ae of 58 dy, orbital 4, orbital d.,, orbital of dy.) orbital | orbital must include x, y= and z-axes in diagram) ‘© Inwriting electronic configuration, 4s orbital (lower energy) is filled first before filling the 3d orbitals. Exceptions: Cr [Ar] 34° 4s" Cu [Ar] 3d"? 4st ‘* To form ions, 4s electrons are removed first before removing 3d electrons. ‘© Isoelectronie species have the same number of electrons, Isotopic species have same number of protons. Isotonie species have same number of neutrons. Down a group. LE. decreases (despite higher nuclear charge) due to increasing atomic size and increasing shielding effect (each subsequent element has one more shell of 7), hence valence e” are less strongly attracted by the nucleus, «. less energy required to remove the electron Across a period, LE. increases due to increasing nuclear charge and decreasing atomic radius (shielding effect remains about the same). + increase is step (not linear) Start from Group 1 (Ist LE.) start from Group? 2" LE.) LE. (kd mol) proton no. Z) I" dip at A/is due to €* removed from orbital (3p) further away from nucleus (less strongly attracted by nucleus); less energy required. 2™ dip at S is due to e" removed from paired 3p electron, which experiences inter-electron repulsion: less energy required. Successive LE, increases because as each electron is removed, remaining electrons are held more strongly by the constant nuclear charge Deduced from ‘biggest’ jump in successive LE. value - the Group to which an element belongs. ~ state that "biggest" jump is between rn and (+1) LE. values; ~ infer that (ir+1) electron is removed from next inner quantum shell; :. element has n valence electrons and so, belongs to Group n evel Foss - Chemisty2.1 Chemical Bonding 2.1 Chemical Bonding Types of Bonding "Dot-and-Cross' Diagrams ‘© Atoms form bonds (loses, gains or shares electrons) to achieve a stable, noble gas type of & configuration, © Tonic bond is the electrostatic forces of attraction between two oppositely charged ions formed as a result of the complete transfer of one ot more electrons from one atom to another. * Covalent bond is electrostatic forces of attraction that two neighbouring nuclei have for a localised pair of electrons shared between them © Dative covalent (or co-ordinate) bond forms when both electrons in covalent bond come from only one of the atoms. © Sigma (c) bond is formed when orbitals from two atoms overlap end-on (ie. collinear or head-to-head overlapping) © Pi (m) bond is formed when the Pp orbitals of the two atoms overlap sideways (i.e. collateral or side-to-side overlapping). ‘This only occurs after a bond has formed between two atoms. ‘© Instantaneous dipole-induced dipole “forces (id-id) are forces of attraction between non-polar molecules (€.g Br,), which arise due to induced (temporary) dipole attraction. © Permanent dipole-permanent dipole forces (pd-pd) are forces of attraction, between polar molecules (e.g. HCI, CHCA), which arise due to permanent dipole attraction. ‘© Hydrogen bonding (H-bonding) is the forces of attraction between an electron deficient H atom (attached to N,O or F) and a lone pair on another N, O or F. © Metallic bonds ate electrostatic forces of attraction that two neighbouring ‘metal ions (cations) have for the delocalised electrons between them. Use ‘dots’ and ‘cross’ only, and show only valence electrons: eg 2 ose (o4e)"" [£93] ‘Must show all lone pairs of electrons. ENEINS or NaN Must show clearly type of bonding (covalent or dative covalent), ¢.g AdgCI, dimer For polyatomic ions, use open circle to represent electrons from cation (e denotes e from cation) Period 2 elements cannot expand octet, (hold maximum 8 ¢” in valence shell). [only 7° 2 around N} Elements in Period 3 and beyond ean expand octet to accommodate more than 8 electrons in valence shell (because low lying d-orbitals are available to accept electrons). eg. PCls; SF¢; BrFs General guide for types of bonding in ompounds: For each negative charge, draw — All other O atoms are =O. 1290" on o Nor 0 crs ‘Lael Fous~ Chemisty §2.1 Chemical Bonding ul 2.1 Chemical Bonding Shapes of Molecules & Bond Angles Intermolecular Forces & Boiling Points ‘* Shape of a molecule is determined by number of bond pairs (bp) and lone pairs (Ip) around the central atom. 2bpO Ip = linear —+~ 3 bp Olp => trigonal planar 1, 2bp | Ip= V-shaped AX, 4bpOlp => tetrahedral = Ay 3 bp 1 Ip => trigonal pyramidal Ay 2 bp 2Ip = V-shaped bp O lp = trigonal bipyramidal fr 4 bp 1 Ip => see-saw oft 3 bp 2 Ip => T-shaped -k 2 bp 3Ip = linear 6 bp 0 lp = octahedral 2K S bp 1 Ip => square pyramidal f° 4 bp 2 Ip = square planar Af? ‘* Bond angle depends on repulsion between Ip and bp: Ip-Ip > Ip-bp > bp-bp > bp-lone & i go ap 0. Xo WH Aas Nor ‘* Compounds with same shape but have different bond angles because the more electronegative central atom draws the bonding eto itself, hence repulsion between bond pairs t; bond angle *. ak oe H Ags 1 BN H [Ois more sma ‘than S} g g Si a Xn Hom 94° 2 [electronegativity: N > P > As] ‘© Strength of intermolecular forces: H-bonding > pd-pd > id-id ‘© To determine type of intermolecular forces that exist in given compound: first check if H-bonding is possible; if not H-bonding, then check if permanent dipole-dipole attractions possible; if not pd-pd, then id-id © Criteria for intermolecular H-bonding: - € deficient H attached to N, O or F - lone pair of e" on another N, O or F [must show 5+ and 6 in drawing H-bonding] © Polar molecules have intermolecular permanent dipole-dipole attractions. © Strength of id-id T due to tin no. of electrons (not larger M,) or larger surface area of contact (e.g. straight chain molecules have larger surface area of contact than branched isomer; hence stronger id-id forces) © Boiling points * as strength of intermolecular forces © Melting points T as strength of intermolecular forces *, and with better packing. © Water has much higher bp. than NH due to more extensive intermolecular H-bonding (on average, each water molecule forms 2 H-bonds while each NH; molecule forms only 1 H-bond). © Compounds with intramolecular hydrogen bonding have lower bp. — because less chances of forming intermolecular H-bond (mainly weak intermolecular id-id forces). ‘ntramolecular “ORT indrogen bond PH rainyaroxy bp. 240°¢ MAihydroxy bp. 286°C ALetel Fors ~ Chemisty2.1 Chemical Bonding Lattice Structure of Solids iant Ionic ‘Simple Molecular © lattice particles: +ve and -ve ions lattice force: strong electrovalent (ionic) bonds e.g. NaCi(s) has a giant ionic structure = consists of Na* and C/~ ions arranged alternatively in a crystal lattice and are held together by strong electrostatic attractions (ionic bonds). Physical properties: © high melting point (and boiling point) = large amount of energy needed to overcome strong ionic bonds in the solid (and molten liquid) © good electrical conductor when molten ~ due to presence of mobile (or free) ions to carry current © non-conductor of electricity when solid — because ions are fixed (hence no mobile charge carriers). © hard and brittle — ions held rigidly in lattice by strong ionic bonds, when stress is applied t0 a particular plane, layers of ions displaced such that ions of similar charge come together and so, repel each other causing the crystal to cleave. ‘© soluble in polar solvents (e.g. water) = forms ion-dipole interactions; releases sufficient energy to separate the oppositely charged ions from the lattice. ‘© insoluble in non-polar solvents (e.g hexane) ~ forms weak intermolecular forces with solvent molecules, insufficient energy released to overcome the strong ion-ion attraction; solvent molecules cannot penetrate the ionic lattice and so, cannot solvate it * lattice particles: discrete molecules lattice force: weak intermolecular forces of attraction [must state the type of intermolecular forces present; i.e. instantaneous dipole-induced dipole forces (id-id), permanent dipole-dipole attractions (pd-pd) or hydrogen bonding.| 1,66) has a simple molecular structure ~ consists of a lattice of discrete I; molecules held together by weak intermolecular instantaneous dipole- induced dipole forces of attraction eg Physical properties: © low melting point (and boiling point) little energy needed to overcome the weak intermolecular forces. © non-conductor of electricity when solid, liquid or solution —no free ions /electrons to earry the current (no mobile charge carriers). © usually soft — molecules are held together by weak intermolecular forces and so, can be separated easily © soluble in non-polar solvents (e.g. benzene) ~ interactions with solvent molecules are similar in strength; releases sufficient energy to separate the solvent and solute molecules; thus non-polar solvent molecules ean penetrate into the simple molecular solid and solvate the molecules. ‘© insoluble in polar solvents (e.g. water) —forms weak intermolecular forces with water molecules; insufficient energy released to overcome the strong hydrogen bonding between water molecules. ‘Lael Fous~ Chemisty2.1 Chemical Bonding Lattice Structure of Solids Giant Molecular Giant Metal * lattice particles: atoms lattice force: strong covalent bonds e.g. diamond, graphite, silicon dioxide covalent band (134 nm) diamond covalent bond | (0182 am) atom wea va A samy 00d elestcal conduction graphite : conduction g. Diamond has a giant molecular structure — consists of a lattice of carbon atoms held together by strong covalent bonds. Physical properties: ‘© high melting point (and boiling point) — large amount of energy needed to overcome the strong covalent bonds. ‘© non-conductor of electricity = no free ions electrons to carry the current (no mobile charge carriers). Exception: Graphite conducts electricity in the plane of the layers (but not at right angles to them) very hard atoms held rigidly in lattice by strong covalent bonds in a 3-D network which prevents the atoms from translational motion Exception: Graphite is soft & slippery because id-id forces between the layers are weak and so, the layers can slide over one another. © insoluble in all solvents = solvent molecules cannot penetrate the giant molecular lattice because of the strong covalent bonds between atoms and so, cannot solvate it, © lattice particles: metal atoms (cations) lattice force: metallic bonds Positive ‘metal ions Delocalised ‘sea’ of valence electrons e.g. Cu(s) has a giant metallic structure — consists of a lattice of metal ions with outer e° forming a sea of delocalised electrons. Electrostatic forces of attraction exist between the delocalised electron cloud and the ‘metal ions (metallic bonds). Physical properties: © high melting point (and boiling point) — large amount of energy needed to overcome the strong metallic bonds. © goodelectrical conductor ~ due to presence of mobile (or free) electrons to carry the current © malleable and ductile the delocalised electrons are highly mobile and so, atoms can slide over one another without breaking the metallic bonds. (malleable: easily rolled into sheets or hammered into different shapes) (ductile: easily drawn into wires) © insoluble in all solvents = solvent molecules cannot penetrate the giant metallic lattice because of the strong metallic bonds and so, cannot solvate it ALetel Fors ~ Chemisty esr 134 2.2 The Gaseous State 2.2 The Gaseous State Assumptions of Kinetic Theory Deviation from Ideal Gas Behaviour © Basic assumptions 1. gas particles or molecules have negligible size (or volume). 2. gas particles have negligible intermolecular forces of attraction 3. gas particles are in continuous random motion. 4. Collisions between gas particles are perfectly elastic. [must use the term ‘particles’ or ‘molecules’] ‘© Real gas is most like an ideal gas at: ~ low pressures (gas particles far apart and so, particle size is negligible); ~ high temperatures (gas particles have high kinetic energy and so, intermolecular forces, are negligible), QI. The following graph is obtained for a real gas Z at 273K (where p = pressure; ?? p= density of gas). y What is the M, of Z o P (in terms of Y)? s. since m = ie since p= 2 As approaches 0, real gas Z behaves more like an ideal gas and p/p = ¥. >= ¥ or M,=RTY = 31273)" =2269Y (ans) Real gas deviates from ideal gas behavior because real gas particles have significant size and significant intermolecular for ~ below horizontal line (ideal gas), deviation is due to intermolecular forces being significant; = above horizontal line (ideal gas), deviation is due to size of gas particle being significant. Real gas deviates most from ideality at ~ high pressures, (gas particles close together and so, particle size is significant), ~ low temperatures (gas particles have low kinetic energy and so, intermolecular forces are significant) br ‘Lael Fous~ Chemisty §2.2 The Gaseous State 15 2.2_The Gaseous State Ideal Gas Equation Partial Pressures © pl'=nRT where p = pressure in Pa (or Nm™) 831K mol! temperature in K R r Shapes of graphs for ideal gases For fixed mass of ideal gas ae ih BaP TT constant (at constant temperature) Ba or KO 0 vio ¢ + £=constant (at constant pressure) rt where m= mass in g [volume, I, must be in m*] 02 3. ie. Partial pressure is the pressure that a gas would exert if it alone occupied the container, e.g. In a mixture of two gases A and B, partial pressure of A, px = 545% pr where 7, Datton’s Law states that in a mixture of gases which do not react chemically, the total pressure, pr, is equal to the sum of the partial pressures of all the gases making up the mixture; ie. pr= pat pot pot ‘A mixture of gases contains 64 g of CH, 64 g of O; and 64 g of SO. The pressure of the mixture is 210 kPa, What is the expected partial pressure (in kPa) of CH? mol of CH,= = 35 =4 mol of 0, = 7 mol of St total mol of gas in mixture = 4+2+1 =7 Pox, = mole fraction * total pressure ‘Two identical bulbs, at the same temperature, contain ideal gases A and B separately. The density of gas A is twice that of gas B and the molecular mass of gas A is half that of gas B ‘What is the ratio of the pressure of gas Ato that of gas B? nRT=3F-RT since n = x =m aL, ar am P= FRAP i, Since p= F Given px = 2p3 and (M,); ratio py: pa= Pa iE! pa i 10. of moles of gas A = no. of moles of gas B mole fraction of gas A nm Taint 4%210=120kPa (ans) AM)e conversion: 1 om*=1 «10m? gonversion: = 2p, i ar Idm'= 1% 107m? = Ppa Fase PO, = 4:1 (as) evel Focus - Chemisty16 2.3 Theories of Acids and Bases 2.3, Theories of Acids and Bases Arrhenius Theory Bronsted-Lowry Theory © Arrhenius acid is a substance which dissociates in water to give hydrogen ions (H"); ie. an Arrhenius acid inereases [H"] in an aqueous solution. HA +H,0 > 30° + A7 eg. HCI, HNOs, H.S0,, CHsCO:H (Arrhenius acids must have H* ions ) © Arrhenius base is a substance which dissociates in water to give hydroxide ions (OH); ie. an Arrhenius base increases [OH] in an aqueous solution. BOH +H,0 + BY + OH e.g. NaOH, KOH, Ca(OH)2, Fe(OH), (Atmhenius bases must have OH" ions.) Limitations: 1, restricted to compounds that have H” or OFF ions; eg ~ does not explain why compounds that do not contain H* ions (e.g. COs, AICI) can form acidie solution in ‘water. ~ does not explain why compounds that do not contain OH” ions (e.g Na;COs, Na,O) can form basic solution in water. 2. restricted to reactions in aqueous solutions (not for non-aqueous solvents or gas phase), e.g. ~ reaction of NH,(g) with HCi(g) is not considered as an acid-base reaction since there are no H” ions or OH ions in solution. © Bronsted-Lowry acid is a species which donates proton (H"*) to a base; ie. aproton donor. e.g. HCI, HNOs, H:80,, CH;CO.H (Bronsted-Lowry acids must have H*) © Bronsted-Lowry base is a species which accepts proton (H*) from an acid, ie. a proton acceptor. e.g, HO, NHs, H.S0,, CHsCO. (Bronsted-Lowry bases must hav pairs to accept H*,) Jone © Conjugate base is the particle left when the acid has given away its H* Conjugate acid is the particle formed when the base has accepted the proton © Conjugate acid-base pair refers two particles (molecules or ions) that differ by one proton. Hig) + H20() — CI(aq) + H30%(aq) Biacid B.base c base acid [vy NH,(g) + H200) = NH,"(aq) + OH (aq). B.base B.acid c.acid —_«, base H,0() + H,00) > OH (aq) + H0%(aq) Boacid B.base base ¢ acid Limitations 1. restricted to acids that have HI ions = does not explain why compounds that do not contain H” ions (¢.g, AICI, BF) ean behave as acids 2. restricted to reactions in protic solvents (eg. water, ammonia); ~ does not explain acid-base reactions that occur in an aprotic solvent (Solvent that does not donate proton; eg. benzene, dioxane). coarse ‘Lett Fos ~ Chemisty2.3 Theories of Acids and Bases 7 2.3_ Theories of Acids and Bases Lewis Theory Terms associated with Acids/Bases © Lewis acid is a substance which pts an electron pair, i.e. a lone pair acceptor. (Lewis acids must have vacant orbitals to accept electron pair.) ¢ — Lewis base is a substance which donates an electron pair, i.e. a lone pair donor. (Lewis bases must have lone pairs.) Examples of Lewis acid-base reactions > Ch + AICh > CI* + AIC” L base Lacid +or > BF; + NH; > BF,.NHs Lacid Lbase adduct HF T” coyiet Naw A, a PP » Ins) + Taq) > Is(aq) Lacid L base > Ag’ + 2NH; > [H:N>Age-NH,] Lacid L base ‘complex ion > Mg” + 6H,O — [Mg(H:0)<)** Lacd Lbase ——hydratedion Limitations 1. too general; no distinct difference between a Lewis acid-base reaction and a redox reaction that involves transfer of two electrons 2. restricted to reactions that do not involve proton transfer. Monoprotic (or monobasic) acid refers to an acid that can donate one proton. eg. HCl +H" +CI” Diprotic (or dibasic) acid refers to an acid that can donate two protons. eg. H,SO,> 2H’ +S0,> Triprotic (or tribasic) acid refers to an acid that can donate three protons. eg. H,PO,> 3H" +PO,> Monoprotic (or monoacidic) base refers to a base that can accept one proton. eg. NaOH +H" > Na’ +H, Diprotic (or diacidic) base refers to a base that can accept two protons. e.g. NasCO; + 2H” > HyCO, + 2Na* Amphiprotie ~ substance that can acts as both a proton donor and a proton, acceptor, e.g. H,0 + H,0 + OH” + H;0° acid base NH, + NH, > NH + NH,” acid base Amphoteric — substance that behaves as both an acid and a base. All amphiprotic substances are also amphoteric, In general, these are negative ions with at least one proton (€g. HCO;) or water. HCO; +H* > H,CO, asbase (HF acceptor) HCO; + OH > CO;* +H,0 asacid (donor) Not all amphoteric substances are amphiprotic. e.g. A/;0; is amphoteric (can react as both acid and base), but it is not amphiprotic since the oxide has no protons (H’ ions) to donate. evel Focus - Chemisty18, 2.4 Periodic Table 2.4 The Perios Table Periodicity in Physical Properties Oxides of Period 3 Elements © Atomic radii ¥ across the period due to 7 in nuclear charge and weak screening effect as successive electrons are added to the same quantum shell. Melting point trend across Period 3: explain in terms of structure & bonding si Me, 4, ‘melting point P x a & Tt a sae Tproton no. Na, Mg, Al- giant metallic structure Si- giant molecular structure P4, Ss, Ch, Ar- simple molecular str mop. of Na (98°C) << Si (1410 °C) => metallic bonds in Na much weaker than covalent bonds in Si mp. of Naelose to mp. of Py (44°C) => metallic bonds in Na not much stronger than id-id forces in P, mp. of Py > Cls (-101 °C) => stronger id-id forces in P, (due to 1 no. of polarisable electrons), Trend in electrical conduct ~ high for metals, lower for metalloids, almost negligible for non-metals. ‘conductivity Moga Ps ot © 4Na+0;—2Na,0 (yellow flame) «© 2Mg+O,->2MgO (brilliant white) * 4A/+30;— 2A10, * Si+0:,—>Si0, © Py +30, POs Py +502 > PxOo © S+0;580, 2802+ 02+ 2805 (yellow flame) (vellow flame) (blue flame) Reaction of oxides with water: © Na,O(s) + H,0() > 2NaOH(aq) (pH=13) * Mg0(s) + H.00) + Mg(H);(a) (pH=9) * ALO & SiO; do nor dissolve in Ha due to high lattice energies. © POYP{O,p & SO,/SOs dissolve in H,0; give acidie solutions (pH = 2) P,Og{s) + 6H,0(1) + 4HPOs(aq) P.O,o(s) + 6HO(1) > 4H;PO,(aq) S0,(g) + H,0() > H2SO,(aq) SO,(g) + H,0() > H,SO,¢aq) Acid/base behaviour ‘ides: © Na,O and Mg0 are basic oxides. Na,O + 2HC/ > 2NaC/ + H;0 MgO + 2HCI—> MgCl + HO © AhOs is an amphoteric oxide ALO3 + 6HCI— 2AICh + 310 Al, +2NaOH +3H,0 > 2NaAKOH), © SiO, is an acidic oxide; reacts with fused NaOH at high temperature (no reaction with aqueous alkalis), SiO. + 2NaOH ~ Na,SiO; + H,0 © P,O¢PsOio, SO2/SO, are acidic oxides P.O, +8NaOH -> 4NasHPO, + 2H,0 P {Oy + 12NaOH — 4Na,PO, + 6H,0 SO, + 2NaOH — Na;SO; + H0 SO, + 2NaOH — Na;SO,+H;0 ‘Lett Fos ~ Chemisty2.4 Periodic Table 2.4 The Periodic Table Chi ides of Period 3 Elements Trends: Oxides & Chlorides ‘* NaClis ionic; dissolves in water to give neutral solution (pH = 7), NaCi(s) + aq > Na*(ag) + CI(aq) * MgCl is ionic; dissolves in water with slight hydrolysis; gives slightly acidic solution (pH 6.5). MgCh +aq — [Mg(H.0).]°* + 2C/~ [Mg(H,0),)"* = [Ma(H,0)OF]" +H" * AICI is covalent; dissolves in water with hydrolysis; gives acidic solution (pH = 3), AICIs(s) + aq > [AI(H;0)<}°* + 3C/- [AME:0)<)"* [AKH0)(OH)]* +H” high charge density of A/** ion polarises surrounding H;0 molecules and causes them to give up H’ ions). ‘*SiC/, and PClyPCIs are covalent; complete hydrolysis in water to give strongly acidic solutions (pH = 2), and steamy fumes of HCI observed. SiCI, + 2H,0 > SiO, + 4HCI PCI; +3H,0 > HPO; + 3HCI PCls +4H,0 > HPO, + SHCI * PCs reacts with water in two stages: 1. with limited water, in the cold: PCis + H,0 - POCIs + 2HC/ 2. with excess water: POCK, + 3H,0 > H,PO, + 3HCI © HyPO,, acts as a dibasic acid (only H atom from i} -OH ionised) R no* WH OH When heated, HPO; undergoes disproportionation 4H:PO,(aq) > 3H;PO,(aq) + PHA(g) Trend in melting point of oxides ~ explain in terms of structure & bonding mp. of oxide Na;O, MgO- giant ionic structures AlOs- ionic with marked degree of covalent character (-. lower mp.) SiO, giant molecular structure P,O¢P,Oy0; SOs/SO3- simple molecular structures pH of solutions of oxides in water: on [ALO & SiO, are insoluble in water (hence, pH =7).] pH of solutions of chlorides in water: pH 1 MMA's Pa [Chlorides become more acidie across the period as the nature of chlorides changes from ionic to covalent ] evel Focus - Chemisty berry20 2.4 Periodic Table Group 2 Elements Reactions Thermal Decomposition © 2Mg+0.—>2MgO (brilliant white flame) 2Ca +02 2CaO (brick-red flame) 28r +02» 2SrO (crimson red flame) 2Ba + 02> 2BaO (apple-green flame) © Reducing power (and reactivity) of Group 2 elements T down the group; as atomic size increases down the ‘group, it becomes easier to lose the outer electrons. © All (except Be) react with water to give hydroxide and H(g). M(s) + 2,0 > M(H): + Hg) ~ Be has no reaction with cold water or steam. - Mg reacts with steam only ~ Ca, Srand Ba react vigorously with cold water. © Allreact with acids to give H.(g). M(s) + 2H"(aq) > M*(aq) + Hoe) ~ Be reacts slowly, no reaction at rt ~ Mg, Ca, Sr and Ba react vigorously. Acid/base nature of oxides: © BeO is amphoteric (high charge density of Be** ion; polarises O anion resulting in covalent character in BeO) BeO + 2H* > Be +H,0 BeO + 20H” +H,0 > Be(OH) * MgO, CaO, S10, BaO are basic oxides ~ react with acids to give salt + HO. e.g. MgO +2H* > Mg™* +H.0 Reaction of oxides with water: © BeO(s) is insoluble in water ‘© MgOis slightly soluble in water. MgO(s) + 1:00) —* Mg(OH)a(aq) (pH=9) * CaO, S10 & BaO dissolve in water, give alkaline solutions (pH 10-13), eg. CaO +H,0 > Ca(OH): ‘quick lime slaked lime Trend: Thermal decomposition of Group 2 salts 4 down the group. (or thermal stability 7 down the group) Explain in terms of polarising power of cation and polarisability of anion: Down the group, cationic size T => charge density 4; and so, polarising power of cation J. => anion electron cloud is less polarised; so compound is more thermally stable. Decomposition of Group 2 nitrates © All Group 2 nitrates decompose on heating; give oxide, NO,(g) and O3(g). M(NOs): > MO + 2NO; +402 Observations: - brown NO,(g), and ~ Oxg) relights a glowing splint. Decomposi of Group 2 ¢: mates: © All Group 2 carbonates decompose on heating; give oxide and COx(g) MCO,(s) > MO(s) + CO.(g) Observations: = CO,(g) gives white precipitate with limewater, Decomposition of Group 2 hydroxi * All Group 2 hydroxides decompose on heating; give oxide and H,0(g). M(OH):(s) > MO(S) + H.0(8) Q ‘Lett Fos ~ Chemisty2.4 Periodic Table Group 2 Elements Thermal Decomposition Solubility of Group 2 salts For Group 1 salts: © Only LINO, decomposes like Group 2 nitrates (due to high charge density of Li’ ion). ALINO; ~> 2L.i,0 + 4NO,(g) + Ox(2) + Allother Group 1 nitrates decompose to give nitrite salt and O,(g), eg, 2NaNO; +> 2NaNO: + O,(g) * Only LixCO, and LiOH decompose on heating. LisCO, > Li,0 + CO; 2LiOH > Li,0 + H;0 All other Group 1 carbonates and hydroxides are stable to heat, Q. Sketch a graph to show how the volume of gas collected varies with time when separate 1.0 g samples of powdered MgCO, and powdered BaCO, are heated at the same temperature, Explain your answer. vol of ges. Meco, ° Baco, a time/s Since M, of MgCOs mol of BaCO; => Larger volume of CO.(g) is collected from heating 1.0 g of MgCO, Since cationic size of Mg”* MgCO; decomposes at a faster rate than BaCOs, (ans) Solubility of Group 2 sulfates: © — Solubility 4 down the group. BeSO, & MgSO, are soluble in water, CaSO, is only sparingly soluble, SrSO, & BaSO, are insoluble in water. Reason: AHjsi = AFfiya ~ Fat Down the group, cationic size T => Affiyg ¥ (less exothermic), but lattice energy (LE.) remains almost constant (due to the large size of SO,” anion). => Fla, becomes less exothermic. ‘* BaSOj is insoluble in water and so, is, not poisonous when consumed. In hospitals, BaSO, is used as "barium meal” in taking X-rays of alimentary canal, It is mixed with food and eaten by the patient before the X-ray photographs are taken. Solubility of Group 2 hydroxid © Solubility t down the group. Mg(OH), & Ca(OH), are only sparingly soluble Reason: AHyi = AH nya ~ AH at Down the group, cationic size T => Mfiyg ¥ (less exothermic) and LE. 4 (less exothermic); but 4 in L-E. is greater (due to the much smaller size of OH), => Alfa becomes more exothermic. evel Focus - Chemisty 2122 2.4 Periodic Table Group 17 Elements Physical properties of Xz Chemical properties of Xz © Fs —pale yellow gas ly ~ yellow-green gas Bry ~ dark-red liquid I, —black solid; insoluble in water ‘© 1,(aq) is prepared by dissolving I,(s) in K(aq); gives a reddish-brown solution, I,(8) + Taq) = Ty (aq) © Identity of X; can be determined by its colour in organie solvent. Ch gives a yellow organic layer. Bry gives orange-brown organic layer. 1, gives violet/purple organic layer. * Test for C/a(g) ~ pungent gas, turns ‘moist blue litmus paper red and then bleaches it Ch +H,0 > CI" + C107 + 2H" (bleaching action is due to C/O” ions) © Boiling point of X; down the group = due to in strength of id-id with increasing no, of e” as size of X: 7. bp 4 Gh Bn hy © Volatility of X: 4 down the group as boiling point of X; 7 * F-F bond energy does not follow the trend shown by other halogens. ond ney | 7, BG Bah - Fisa very small atom; ~ lone pairs of electrons in F> repel Oxidising power: F, > Cl, > Br. > Ip (indicated by E* (X,/X°) becoming less positive down the group) een [Ve ch > . atomic no Each halogen can oxidise the halide ion below it - Ch can oxidise Br and I (Ch + 2NaBr > Br, + NaCl (Cl; + 2Nal > Tp + 2NaCI ~ Br, can only oxidise T Br, + 2Nal > 1; + 2NaBr Cl; & Br, can oxidise $,0,*" to SO,- (ON. of S changes from +2 10 +6) ACI. + $,03° + SHO > 280, + 10H" + 8C/- 1 oxidises NayS,0; to Na:S,Ox (ON. of S changes from +2 to +2%) 1, + 28,0;* > 8,06" +20 Ci; and Br, can oxidise Fe** to Fe™. Ch, + 2Fe™* > 2CI" + 2Fe* Br + 2Fe™ — 2Br+ 2Fe™ I, cannot oxidise Fe** to Fe** (Ea <0). Halogens undergo disproportionation reaction with ag.NaOH. cold, aqueous NaOH at 15°C Cl, + 2NaOH -> NaCl + NaC/O +H,0 hot, aqueous NaOH at 70°C: 3C1, + 6NaOH - SNaCI + NaC/O, more strongly than those of other +310 halogens. Hence, F-F bond is longer and weaker than CI-C/ bond, [bond energy: F-F < CECI] caetro ‘Lett Fos ~ Chemisty §