Unit 2: Energetics, Group Chemistry, Halogenoalkanes and Alcohols Topic 6: Energetics Students will be assessed on their ability to: 61 know that the enthalpy change, AH, is the heat energy change measured at constant pressure and that standard conditions are 100 kPa and a specified temperature, usually 298 K Enthalpy is a measure of the total energy of a system 6.2 know that, by convention, exothermic reactions have a negative enthalpy change and endothermic reactions have a positive enthalpy change Exothermic: heat energy is transferred from system to surroundings Endothermic: heat energy is transferred from surroundings to system 6.3 be able to construct and interpret enthalpy level diagrams, showing exothermic and endothermic enthalpy changes Activation, ‘61003 Progress of Reaction Progress of Reaction Exothermic: AH is negative Endothermic: AH is positive 6.4 know the definition of standard enthalpy change of: i reaction, A:H: the enthalpy change which occurs when equation quantities of materials react under standard conditions ii formation, Ai: the enthalpy change measured at 100kPa and a specified temperature, usually 298K, when one mole of a substance is formed from its elements in their standard states ii combustion, Ac#: the enthalpy change measured at 100kPa and a stated temperature, usually 298K, when one mole of a substance is completely burned in oxygen iv neutralisation, Anes: the enthalpy change measured at 100kPa and a stated temperature, usually 298K, when one mole of water is produced by the neutralization of an acid with an alkali v_ atomisation, As: the enthalpy change measured at a stated temperature, usually 298K, and 100kPa when one mole of gaseous atoms is formed from an element in its standard stateIonisation is always endothermic cH: the enthalpy change which occurs when equation quantities of materials react under standard conditions ‘ih: the enthalpy change measured at 100kPa and a specified temperature, usually 298K, when one mole of a substance is formed from its elements in their standard states Common examples: C(s) + 2H2(g) + CHaCa) 2C(s) + 3H2(g) + ¥202(g) —* C2HsOH(!), ‘cH: the enthalpy change measured at 100kPa and a stated temperature, usually 298K, when one mole of a substance is completely burned in oxygen (always exothermic) ‘AneuHt: the enthalpy change measured at 100kPa and a stated temperature, usually 298K, when one mole of water is produced by the neutralization of an acid with an alkali (always exothermic) ‘ov: the enthalpy change measured at a stated temperature, usually 298K, and 100kPa when one mole of gaseous atoms is formed from its elements in their standard state (always endothermic) Common examples: *aCla(a) —* CIC) YaBra(l) — Br(g) Na(s) — Na(g) You can write standard conditions instead of 298K and 100kPa be able to use experimental data to calculate: i energy transferred in a reaction recalling and using the expression: energy transferred (3) = mass (g) x specific heat capacity (J g-* °C) x temperature change (°C) ii enthalpy change of the reaction in k} mol This will be limited to experiments where substances are mixdd in an insulated container and combustion experiments using a suitable calorispeter. For a reaction in solution, we can use: mis the mass of solution Q=mcar Tis the amount in moles aye of the limiting reagent a 6.6 know Hess’s Law and be able to apply it to: i constructing enthalpy cycles ii calculating enthalpy changes of reaction using data provided, or data selected from a table or obtained from experiments Hess's Law states that the total enthalpy change of a reaction is independent of the route (path) taken in converting reactants into products, provided that the initial and final conditions are the same in each case 2H (9) + 20a) ~ x (On an energy level lagram the drectons of the arrows can how the diferent routes @ reaction can proceed by In this example one cute fs arrow a H, +01, b ‘The second routes shown by artows AM plus arom b! ta Pearson Edexcel international Advanced Subsidiary in ChemistryHess’s Law is often used to calculate enthalpy change for reactions that cannot be determined directly by experiments (mostly enthalpy changes of formation) Instead, alternative reactions are carried out that can be measured experimentally In general, you can use this enthalpy cycle to calculate enthalpy changes of reaction from enthalpy changes of formation AH [reactants | ZArH ZMH reactants products Elements in standard states ArH= EArH products — ZArH reactants In general, you can use this enthalpy cycle to calculate enthalpy changes of reaction — enthalpy el of combustion [ reactans fult [ products | TAH \t02 reactants EAcH products combustion products A-H= EAcH reactants — AcH products 6.7 | CORE PRACTICAL 2 Determination of the enthalpy change of a reaction using Hess's Law. 6.8 be able to evaluate the results obtained from experiments and comment on sources of error and uncertainty and any assumptions made in the experiments Students will need to consider experiments where substances are mixed in an insulated container and combustion experiments using, for example, a spirit burner and be able to draw suitable graphs and use cooling curve corrections, Calorimetric Method General method ‘washes the equipment (cup and pipettes etc) with the solutions to be used + dry the cup after washing ‘+ putpolystyrene cup in a beaker for insulation and support + Measure out desired volumes of solutions with volumetric pipettes and transfer to insulated cup ‘damp thermometer into piace making sure the thermometer bulb is immersed in solution ‘© measure the initial temperatures of the solution or both solutions if 2 are used. Do this every minute for 2-3 minutes ‘+ Atminute 3 transfer second reagent to cup. Ifa solid reagent is used then add the solution to the cup first and then add the solid weighed out on a balance. Musing a solid reagent then use ‘before and after’ weighing method stirs mixture (ensures that all of the solution is at the same temperature) Record temperature every minute after addition for several minutesIf the reaction is slow then the exact temperature rise can be difficult to obtain as cooling occurs simultaneously with the reaction To counteract this we take readings at regular time intervals, and exirapolate the temperature curve/ine back to the time the reactants were added together Temperature (°C ‘We also take the temperature of the reactants for a few minutes before they are added together to get a better average temperature. If the two reactants are solutions then ° the temperature of both solutions need to be measured Tene (in before addition and an average temperature is used. Errors in this method + energy transfer from surroundings (usually loss) + approximation in specific heat capacity of soliton. The method assumes all solutions have the heat capacity of water ‘neglecting the specific heat capacity of the calorimeter- we ignore any energy absorbed by the apparatus. + reaction or dissolving may be incomplete or slow. + Density of solution is taken to be the same as water. Calculating the enthalpy change of reaction, AH, from experimental data ‘Tho haat capacty of watorie 4181 "Kh ay reaction General method where the reactants are 4. Using g= mx, x AT calculate energy change for quantiies used Sisolved in water we assume ee — that the heat capacty ithe Work out the moles of the reactants used same as pure water 2 3. Divide by the number of moles of the reactant not in excess to give AH ‘Ato assume fat the solitons: 1 4 have the density of water 4, Add a sign and unit (divide by a thousand to convert Jmol to kImot ache igen eg abc) wl weigh 259 6.9 understand the terms ‘bond enthalpy’ and ‘mean bond enthalpy’, and be able to use bond enthalpies to calculate enthalpy changes, understanding the limitations of this method Bond enthalpy is the enthalpy change when one mole of a specific bond in the gaseous state is broken Mean bond enthalpy is the average enthalpy change when one mole of a specific (covalent) bond in the gaseous state averaged over many different molecules, is broken Mean bond enthalpy is more often used because the bond enthalpy of specific bonds varies with its environment To calculate enthalpy changes from bond enthalpies, we can use: ArH = 3(bonds broken) — 3(bonds formed) 6.10 be able to calculate mean bond enthalpies from enthalpy changes of reaction 6.11 understand that bond enthalpy data gives some indication about which bond will break first in a reaction, how easy or difficult it is and therefore how rapidly a reaction will take place at room temperature Bonds with high bond enthalpy require more energy to break them so reactions are more likely to require heating and/or catalyst Bond with low bond enthalpy require less energy to break them so are easier to break and thus, more likely to break first in a reaction and is more likely to take Place at room temperatureFurther suggested practicals: the enthalpy change for the decomposition of calcium carbonate using the enthalpy changes of reaction of calciurn carbonate and calcium oxide with hydrochloric acid the enthalpy change of combustion of an alcohol the enthalpy change of the reaction between zinc and copper(II) sulfate solution the enthalpy of hydration of anhydrous copper(II) sulfate{a-k.a) non-bonded interactions Topic 7: Intermolecular Forces Students will be assessed on their ability to: 74 In general, understand the nature of the following intermolecular forces: i London forces (instantaneous dipole-induced dipole) li permanent dipole-permanent dipole interactions iii_hydrogen bonds et Intra_olecular forces pee Cat Permanent os a tendon Forces Inter olecular forces Itis better to assume the strength of each type of intermolecular force depends ‘on whether thelr interaction is favorable in each case Note that Hydrogen bonding occurs In addition to London forces London (Dispersion) Forces This (Instantaneous dipole-Induced dipole interaction) occurs because in any molecule, the electrons are moving constantly and randomly and so the electron density fluctuates over time which results in a temporary dipole being formed. These temporary dipoles induce more dipoles in neighbouring molecules. When this happens, the d° end in one molecule and the 8 end in the neighbouring molecule are attracted to each other ‘They occur between ail types of molecules whether polar or non-polar and between separate atoms In noble gases. They do not occur in lonic substances Main Factors that affect size of London Forces + Number of electrons: The more electrons there are in a molecule, the greater the fluctuations in electron density and so the larger the instantaneous and induced dipoles created. This makes London forces stronger between the molecules and more eneray will be needed to break them apart so boiling point will increase + Shape & Size of molecule: The more points of contact there are between the molecules, the greater the overall London force as instantaneous dipole-induced dipole forces exist at each point of contact between the molecules. That is why Long straight chain alkanes have stronger London forces as they have a larger surface area of contact between molecules compared to spherical shaped branched alkanes Permanent dipole-dipole forces This (Permanent dipole-Permanent dipole interaction) is stronger than London forces and so the compounds have higher boiling points They occur between polar molecules. The 5*and 5 regions of neighbouring polar molecules attract each other and hold the molecules together in a lattice-like structure Polar bonds form due to a difference in electronegativity Hydrogen Bonding This is an intermolecular interaction (in which there is some evidence of bond formation) between a hydrogen atom of a molecule (or molecular fragment) bonded to an atom which is more electronegative than hydrogen and another atom in the same ora different molecule. They act most often between compounds that have a hydrogen atom attached to one of the three most electronegative atoms, Nitrogen, Oxygen and Fluorine which all must have a lone pair of electrons Hydrogen Bonding through Nitrogen +All compounds containing an -N-H group can form intermolecular hydrogen bonds + Primary Amines can form intermolecular hydrogen bonds Hydrogen Bonding through Oxygen 3 a + All compounds containing an -O-H group form ©) intermolecular hydrogen bonds «Alcohols form intermolecular hydrogen bonds Hydrogen Bonding through Fluorine . + _ Only hydrogen fluoride forms intermolecular hydrogen bonds7.2 understand the interactions in molecules, such as *H,0, liquid NH; and liquid HF*, which give rise to hydrogen bonding Alcohols (Q-H bond), ammonia (N-H bond), amines (N-H bond), carboxylic acids (0-H bond), hydrogen fluoride (H-F bond), proteins (N-H bond) can form hydrogen bonds 7.3 understand the following anomalous properties of water resulting from hydrogen bonding: li the density of ice compared to that of water its high melting and boiling temperature when compared with similar molecules 1. Water can form four hydrogen bonds per molecule, because the electronegative oxygen atom has two lone pairs of electrons on it and two hydrogen atoms Thus, it can form stronger hydrogen bonds and needs more energy to break the bonds, leading to a higher melting and boiling point 2. Density of ice at 0°C is less than that of water at 0°C because the molecules in ice are arranged in rings of six, mo, held together by hydrogen bonds. The structure creates large areas of open space and when ice melts, the ring structure is destroyed and the average distance between molecules decreases, resulting in an increase in density 7.4 be able to predict the presence of hydrogen bonding in molecules analogous to those mentioned in 7.2 75 understand, In terms of intermolecular forces, physical properties shown by ‘substances, including: i the trends in boiling temperatures of alkanes with increasing chain length ji the effect of branching in the carbon chain on the boiling temperatures of alkanes iii the relatively low volatility (higher boiling temperatures) of alcohols compared to alkanes with a similar number of electrons iv _ the trends in boiling temperatures of the hydrogen halides HF to HI ‘As chain length increases, : 1, molecular mass increases and so does the number of electrons per molecule which causes an increase in instantaneous = dipole-induced dipoles and 2. the number of contact points between molecules increases which means greater overall London forces, resulting in an increase in boiling point !Note there are only London forces in alkanes The more branching in the molecule, the fewer the points of contact between adjacent molecules This leads to a decrease in overall intermolecular force of attraction between molecules and hence, a decrease in boiling temperature ‘AHvap is 3 Measure ‘As alcohols contain an -OH group, they can form hydrogen bonds in addition to London forces. This means, compared to equivalent alkanes with similar chain length and number of electrons, the boiling point of alcohols would be higher due to the hydrogen bonding. This additional force of attraction increases energy required to separate the molecules of the energy change that is required to completely separate the molecules of a liquid and convert it into a gas at the same temperature‘A direct measure of the strength of intermolecular interactions would be the enthalpy change of vaporization ‘The greater the enthalpy change of vaporization, the greater the force of attraction between molecules iv The anomalously high boiling points of 106 H,0, NH3 and HF are due to the hydrogen bonding between the molecules in eas addition to the London forces already i present, making it require more energy to break these forces of attraction £ a ‘The general increase in boiling point from © HCI to HI is caused by the increasing 100 number of electrons per molecule, thereby resulting in an increase in London forces = 8% Wo as All hydrogen halides have London forces Molecular mass and permanent dipole-permanent dipole forces between Its molecules Only HF has hydrogen bonding in addition to these forces 7.6 | understand factors that influence the choice of solvents, including: i water, to dissolve some ionic compounds, in terms of the hydration of the ions ii water, to dissolve simple alcohols, in terms of hydrogen bonding lil water, as a poor solvent for compounds (to include polar molecules such as halogenoalkane), in terms of inability to form hydrogen bonds iv non-aqueous solvents, for compounds that have similar intermolecular forces to those in the solvent For a substance to dissolve, + The solute particles must be separated from each other and then become surrounded by solvent particles * The force of attraction between the solute and solvent particles must be strong enough to overcome the solvent-solvent forces and the solute-solute forces When an ionic lattice dissolves in water, the bonds in the lattice are broken and new bonds are formed between the ions and the water molecules The energy required to separate the ions in the solid is either completely or partially supplied by the hydration of ions The negative ions are attracted to the 5* hydrogen ends of the polar water molecules ‘The positive ions are attracted to the 8 oxygen ends of the polar water molecules In general, the greater the ionic charge, the less soluble an ionic compound is The solubility of alcohols in water decreases with increasing hydrocarbon chain length as London forces predominate between the alcohol molecules ‘Compounds that cannot form hydrogen bonds with water include * Non-polar molecules such as the alkanes + Some polar molecules such as ethoxyethane and halogenalkanes “Like dissolves like” meaning compounds that have similar intermolecular forces to those in the solvent will generally dissolve Non-polar solutes will dissolve in non-polar solvents (like hydrocarbons) Polar solutes generally dissolve in polar solventsFurther suggested practicals: i the solubility of simple molecules in different solvents li measuring the enthalpy change of vaporisation of water iii_ measuring temperature changes when substances dissolveTopic 8: Redox Chemistry and Groups 1, 2 and 7 8A: Redox chemistry Students will be assessed on th ability to: 8.1 know what is meant by the term ‘oxidation number’ and understand the rules for assigning oxidation numbers Monoatomic ion means an ion consisting of one atom Oxidation number is the charge that an ion has, or the change it would have if the species were fully ioni Rules for assigning oxidation numbers The oxidation number of any uncombined element | Hz, Zn, O (Free state) is zero ‘Sum of the oxidation numbers of all the elements ina | In NaCl, Na= +4, Cl= neutral compound is zero Sum = +1-1=0 The oxidation number of any monoatomic ion is equal | Zn®* = 2+ to its ionic charge Fee" = 3+ ‘Sum of the oxidation numbers of all the elements in | SO,” an ion is equal to the charge on the ion Oxidation no. of S = +6 Oxidation no. of © = 4x-2 Sum = -2 The more electronegative element in a substance is | F20, aS Fis more given a negative oxidation number electronegative, F = 2x -1 O=+24 Gp.1 elements are always +1 ur Gp.2 elements are always +2 Mg?* Fluorine is always +1 Hydrogen is +1, except when combined with a less electronegative element (i.e. in metal hydroxides) Oxygen is -2, except in peroxides where it is -1 and when combined with fluorine where it is +2 ==] 8.2 be able to calculate the oxidation number of elements in compounds and ions, Including in peroxides and metal hydrides Eg. of metal hydrides: NaH Hydrogen atom is present as a hydride ion, 1 Eg. of peroxides: hydrogen peroxide, H)0, Oxygen must have an oxidation state of -1 8.3 be able to indicate the oxidation number of an element in a compound or an ion, using a Roman numeral When the element has a variable oxidation number, the number is written afterwards in ROMAN numerals In IUPAC convention, the various forms of sulfur, nitrogen and chlorine compounds where oxygen is combined are all called sulfates, nitrates and chlorates with relevant oxidation number given in roman numerals. If asked to name these compounds remember to add the oxidation number: NaCiO: sodium chlorate(I) K2S0;: potassium sulfate(IV) NaCiOs: sodium chlorate(V) NaNOs: sodium nitrate(V) K,SO4:_ potassium sulfate(VI) NaNO»: sodium nitrate(III) 8.4 be able to write formulae given oxidation numbers8.5 understand oxidation and reduction in terms of electron transfer and changes in oxidation number, and the application of these ideas to reactions of s-block and p- block elements Oxidation Reduction Addition of Oxygen Loss of Oxygen Loss of Hydrogen ‘Addition of Hydrogen Loss of electrons Gain of electrons t cs Balanced equation Mated + CBD, la) 2 MgO. (09) + Gals) Mgt) + CaP Cag) + $047Goq) —> MY" Cag) + SBC) + Gals) g. ong agent) Tene eqalion oidalien Creduerg ogi 2 U fMq(s) + Gu" leq) — My Cyd + Culs) [a a ae ) redoclion Condang aged) dW a7 Mg — Mg" + 20° Gi" 4 2 > Ca Half euabion Mg loses electrons so it has been Cu’* gains electrons so it has oxidized been reduced The reducing agent is the Mg as it The oxidising agent is the Cu** is an electron donor ion asitis an electron acceptor Oxidation no. of reducing agent Oxidation no. of oxidising agent increases decreases S-block (consisting mainly of metals) generally form positive ions by losing electrons with an increase in oxidation number P-block (consisting mainly of non-metals) generally form negative ions by gaining electrons with a decrease in oxidation number 8.6 know that oxidising agents gain electrons and reducing agents lose electrons 8.7 | understand that a disproportionation reaction involves an element in a single species being simultaneously oxidised and reduced HANGE BOX No= 37 GRE CL ATOM HAS BEEN OXDISED f ¥ Cl, + H,0 ——> HCl + HCLO ° 4-2 +44 atet-2 MANGE W OX No=—A ONE CL ATOM HAS BEEN REDUCED 8.8 | know that oxidation number is a useful concept in terms of the classification of reactions as redox and as disproportionation A redox reaction is a reaction in which both oxidation and reduction are simultaneously occurring at the same time A disproportionation reaction {s a reaction in which a single species is being simultaneously oxidized and reduced at the same time 8.9 | understand that metals, in general, form positive ions by loss of electrons with an increase in oxidation number whereas non-metals, in general, form negative ions by gain of electrons with a decrease in oxidation number 8.10 be able to write ionic haif-equations and use them to construct full ionic equations8B: The elements of Groups 1 and 2 Students will be assessed on their ability to: 8.11 | understand reasons for the trend in ionisation energy down Groups 1 and 2 8.12 _ | understand reasons for the trend in reactivity of the elements down Group 1 (Lito K) | and Group 2 (Mg to Ba) onisation energy increases down the group because: Increased shielding from inner Color is shown based on flame color electrons + larger distance between outermost electron and the nucleus outweigh the increase in nuclear charge Reactivity increases down the group because: COPAY Z "A 40 ALIGN|OS The outermost electron gets further away from the nucleus so there is increased shielding and weaker forces of attraction which require little energy to overcome d8 ayy UMop aseassap idq 9 Id dhoi8 ayy umop aseanou! sayenju pue dnou8 ayy umop aseaiou! AYANIeOH sareuogie> z pue T “do Jo Aayigeas jewwau, aseauoap sareyns 2 "dd jo AUNGHIOS dnoJ8 ayy umop aseasouy K@zaua uoNeZ|U0) 8.13 | know the reactions of the elements of Group 1 (Lito K) and Group 2 (Mg to Ba) with oxygen, chlorine and water | Seton General equations for Group 1: 4M(s) + 02(9) -+ 2M,0(s) Group 2: 2M(s) + 02(9) -+ 2MO(s) yeh crusting? General equations for Group 1: 2M(s) + CI(g) + 2MCK(s) Group 2: M(s) + Ci(g) - 2MO(s) Observations: A white solid is formed Reactions with Water: General equations for Group 1: 2M(s) + 2H20(I) -» 2MOH(aq) + Ha(9) Group 2: M(s) + 2H,0(1) -- M(OH),(aq) + H2(9) !Note Mg reacts slowly with water to form Mg(OH)2 but reacts vigorously with steam to form a white solid MgO (even producing a bright white flame) Observations: Fizzing (more vigorous down the group) Metal getting smaller and disappearing (faster down the group) Solution getting warmer (exothermic reaction) and Is alkaline 8.14 | know the reactions of: | oxides of Group 1 and 2 elements with water and dilute acid ii hydroxides of Group 1 and 2 elements with dilute acid i Reaction of oxides with water For Group 1 oxides: M,0(s) + H:0(I) —- 2MOH(aq) For Group 2 oxides: MO(s) + H20(I) + M(OH)2(aq) Group 1 and 2 metal (basic) oxides react with water to produce a colorless alkaline solutioni Reactions of oxides and hydroxides with acid All of the Group 1 and 2 oxides and hydroxides react with acids in a neutralization reaction to form salts and water Observations: a white solid reacts to form a colorless solution Solution gets warmer (exothermic reaction) 8.15 | know the trends in solubility of the hydroxides and sulfates of Group 2 elements Solubility of Group 2 hydroxides increase down the group: Magnesium hydroxide is insoluble in water (used in medicine) Calcium hydroxide is reasonably soluble in water (used in agriculture) Barium hydroxide is very soluble Solubility of Group 2 sulfates decrease down the group 8.16 | understand the reasons for the trends in thermal stability of the nitrates and the carbonates of the elements in Groups 1 and 2 in terms of the size and charge of the cations involved ‘Thermal stability is a measure of the extent to which a compound decomposes when If compound heated (i.e. how stable a compound is when heated) goes net |__| Thermal Stability of Nitrates isthermally All of Group 1 & 2 nitrates are white solids stable When they are heated, they all decompose to nitrites or oxides, and give off nitrogen dioxide (brown fumes) and/or oxygen (and steam too if it contains water of crystallization) If brown fumes are observed, this indicates a greater decomposition: metal nitrate —- metal oxide + nitrogen dioxide + oxygen a pester) | | pow mes are observe, tisindetes 8 ese deamposton metal nitrate —+ metal nitrite + oxygen The only Gp.1 nitrate that decomposes in the same way as Gp.2 nitrates is Lithium nitrate Group 1 ALINOx(s) —* 2Li,0(s) + 4NO2(g)+ O2(g)_ + The rest of the Gp.1 nitrates decompose in this way = aa ee 2XNOx(s) —* 2XNO2(s) + 02(9) done in fume cupboards as Do note that each have to be at a certain temperature to undergo the reaction nitrogen Group 2 Siaide itoxle All Gp.2 nitrates decompose in this way: 2X(NOz)2~» 2X0 + 4NO2 + O2 The smail positive |] Greater decomposition occurs when: ion attracts the ‘+ The cation has a 2+ charge (all of Gp.2 nitrates) delocalised + The cation has a 1+ charge and is also the smallest in Gp.1 (i.e. Lithium) nitrate or carbonate ion towards itself ‘As you go down the group, more heat is needed to break down the carbonate and nitrate ions: The higher the ‘Thermal stability of Gp.1 and Gp.2 nitrates increases down the group charge and the + The smaller positive ions at the top of the groups will polarize the anions more smaller the ion than the larger ions at the bottom the nigner the + The more polarized they are, the more likely they are to thermally decompose polarising power as the bonds in the carbonate and nitrate ions become weaker Pearson Edexcel International Advanced Subsidiary in ChemistryDown the group, both the nitrates ‘& carbonates require more ‘Thermal Stability of Carbonates All of Group 1 and 2 carbonates are white solids. When they are heated, they either do not decompose at all or decompose to oxides and give off carbon dioxide As the gas given off is colorless and both the carbonate and oxide are white solids, no observations can be made [Group 4 Group 1 carbonates do not decompose at Bunsen temperature with the exception of Lithium as it has the smallest size of ion among Gp.1 elements and so it has a greater charge density resulting in it being more polarizing of the C-O bond The rest of the Gp.1 carbonates only have +1 charges and so they don’t have a big enough charge density to polarize the carbonate lon. Li,CO,(s) + LiO(s) + CO.(9) Gp.1 carbonates have more thermal stability than Gp.2 carbonates Group 2 All Gp.2 carbonates decompose in this way: XCOx(s) > XO(s) + CO2(9) The thermal stability of Group 2 carbonates increases down the group because as heating to you go down, the size of cation increases but has the same overall charge which decompose means a decrease in charge density of cation down the group. This means the cation Is less polarising of the C-O bond (electron cloud of anion is distorted less) This means stronger (C-O) covalent bonds in the carbonate ion, hence more energy required to break the bonds Decomposition occurs when: + The cation has a 2+ charge (all of Gp.2 carbonates) + The cation has a 1+ charge and is also the smallest Gp.1 cation (only lithium carbonate) 8.17 | understand the formation of characteristic flame colours by Group 1 and 2 compounds in terms of electron transitions Students will be expected to know the flame colours for Group 1 and 2 compounds. Ina flame test, the heat vemos ‘causes the electron to ut Red absorb eneray and move to Ne Ee a higher energy level ‘ (excited state) K rs ‘The electron is unstable at Rb Roos) the higher energy level and cs* rene so drops back down to a sor ASoCe lower energy level, during — which energy is emitted in Mg** No colour the form of visible light Ca (Brick) red energy with the wavelength s* (cane of the observed light 7 Ba (yee 8.18 | know experimental procedures to show: i patterns in the thermal decompo: ‘ion of Group 1 and 2 nitrates and carbonates Students will be expected to know tests for carbon dioxide and oxygen; and to recognise nitrogen dioxide by its colour and acidic pH. ll flame colours in compounds of Group 1 and 2 elements Pearson Edexcel Intemational Advanced Subsidiary in Chemistry8.19 know reactions, including ionic equations where appropriate, fo fentifying: i carbonate ions, CO”, and hydrogencarbonate ions, HCO” using an aqueous acid to form carbon dioxide (and testing the gas with limewater) ji sulfate ions, SO*, using acidified barium chloride solution iii ammonium ions, NH., using sodium hydroxide solution and warming to form ammonia (and testing with litmus and HCI fumes) ‘Add dilute hydrochloric acid to a test tube to be tested Test the gas released by bubbling it through limewater Carbon dioxide produced turns limewater milky ‘Add dilute hydrochloric acid (or dilute nitric acid) and then add barium chloride (or nitrate) solution Ifa sulfate Is present, white precipitate (barium sulfate) will be produced Dissolve the solid salt in distilled water and put it in a test tube ‘Add aqueous sodium hydroxide solution and warm (using a water bath) Test the gas released- Ammonia gas produced turns damp red litmus paper blue (or) you could react the ammonia gas with hydrogen chloride gas (from conc. HCI) white smoke (ammonium chloride) will be produced 8.20 be able to calculate solution concentrations, in mol dm and g dr, including simple acid-base titrations using the indicators methyl orange and phenolphthalein CORE PRACTICAL 3 Finding the concentration of a solution of hydrochloric acid. 8.22 understand how to minimise the sources of measurement uncertainty in volumetric analysis and estimate the overall uncertainty in the calculated result Readings (one judgement) Measurement (two judgements) The values found from a single The values found as the difference judgement when using a piece of between the judgements of two values equipment Eg: burette in titration Uncertainty is at least +1/2 of smallest Uncertainty is at least +1 of smallest scale reading scale reading ‘Apparatus Capacity Measurement uncertainty Burette 50cm? £0.05cm? (but since it is read twice(final and initial volume), total measurement uncertainty Is 0.05 x 2 = 0.10cm? Pipette 25cm3 £0.1¢em? Volumetric flask | 250cm> +0.4cm* total_ unc ainty Calculating percentage uncertainty: percestage uncertainty x 100 measured value How to reduce uncertainties in a titration - Replace measuring cylinders with pipette or burette which have greater resolution Which will lower uncertainty and thus, lower error - To reduce uncertainty in burette readings, increase the size of measurement (titre) made either by increasing the mass/volume/conc, of the substance in the conical flask or decreasing the volume/conc. of substance in the burette How to reduce uncertainties in measuring mass - Use a more accurate balance or a larger mass - Weigh the sample before and after addition and calculating the difference 8.23 CORE PRACTICAL 4 Preparation of a standard solution from a solid acid and use it to find the concentration of a solution of sodium hydroxide.Further suggested practicals: i experiments to study the thermal decomposition of Group 1 and 2 nitrates and carbonates ii flame tests on compounds of Group 1 and 2 iii simple acid-base titrations using the indicators methyl orange and phenolphthalein to calculate solution concentrations in g dm-3 and mol dm? iv the solubility of calcium hydroxide by titration v__ determination of moles of water of crystallisation by titration How to carry out a flame test - Clean a platinum or nichrome wire by dipping it into concentrated hydrochloric acid and then into a flame until no colour shows = Then, dip the loop of wire into the solid sample and hold it at the edge of a non- luminous blue Bunsen flame: Inorgal chemistry of Group 7 (limited to chlorine, bromine and iodine) Students will be assessed on their al ity to: 8.24 understand reasons for the trends for Group 7 elements in: i melting and boiling temperatures and physical state at room temperature ii electronegativity ili reactivity down the group Black Solid ‘State & Color at rep Color in solution | Mp Bipt | Electronegatvty/Reactivity - : alz 2 Yellow Gas ala & Pale Green Gas | & Pale Green A 2 z ele 3 E f ale 8 Red-Brown Liquid | © orange £ ale 2 (orange vapour) | @ & a8 3 g “ 2|2 & Grey Solid 3 Dark grey oe als s (Purple vapour) | ® Dark brown 3 sig 2 3 ao Halogens are non-metals and exist as diatomic molecules at room temp. and they have weak simple molecular structures Melting and boiling temperatures increase down the group as there are more electrons which results in greater instantaneous dipole-induced dipole forces, in other words stronger London forces between molecules As the strength of intermolecular forces increases, more energy is required to be put in to overcome these forces !Note no covalent bonds are broken Electronegativity decreases down the group as (although the nuclear charge increases) the atomic radii increases due to the increasing number of shells which means the distance between nucleus and electron increases The electron to be added will experience more shielding down the group The halogen’s oxidizing power(ability to accept an electron) decreases down the group Reactivity decreases down the group as the outershell electron gets further away from the nucleus and are more shielded by the inner electrons So it is harder for the halagen to attract and accept electrons 8.25 understand the trend in reactivity of Group 7 elements in terms of the redox reactions of Cl, Br2and 12 with halide ions in aqueous solution Students are expected to know the colours of the elements in standard conditions, in aqueous solution and in a non-polar organic solvent. EE BIT eee eee Trisuiediatta solution and in non-polar organic xc x ‘erssver | fest" |) solvent such as cyclohexane Noveccten || (Which is useful as the halogens are more soluble in this layer) lodine is brown in solution but purple in non-polar organic solvent Pearson Edexcel International Advanced Subsidiary in Chemistry8.26 understand, In terms of changes In oxidation number, the following reactions of the halogens: i oxidation reactions with Group 1 and 2 metals (redox reactions) ll the disproportionation reaction of chlorine with water and the use of chlorine in water treatment iii the disproportionation reaction of chlorine with cold, dilute aqueous sodium hydroxide to form bleach iy the disproportionation reaction of chlorine with hot alkali (70°C) v__reactions analogous to those specified above Halogens react with Gp.1 and 2 metals to form metal halide salts (ionic compounds that are usually white) ‘The halogens act as oxidizing agents and the metals are being oxidized - Reactions are most vigorous between metals at the bottom of Gp.1 and 2 with the elements at the top of Gp.7 s [ A disproportionation reaction is a reaction in which an element in a single species is being simultaneously oxidized and reduced ] CHANGE IY Ox Ne ONE Cl ATON oe + H,0 > HCL # nao reeled formed sterilizes water by ° 4-2 ee aaanne illing bacteria Lt CHANGE IN OX Ne=—1 ONE Ci ATOM HAS BEEN REDUCED Reaction goes like this: Cl(aq) + 2NaOH(aq) — NaCl(aq) + NaClO(aq) + H20(I) Cl,fagl + 2OH (aq) —> CI (aq) + CLO” faq) + H,0%aq) 2 a ” REDUCTION h (OXIDATION This is a disproportionation reaction as chlorine is being simultaneously oxidized and reduced Chlorine gets oxidized as there is an increase in oxidation number from 0 in Cl to +5 in Clos Chlorine gets reduced as there is a decrease in oxidation number from 0 in Cla to -1 in Cl Reaction goes like this: 3Ci(aq) + 6NaOH(aq) + SNaCi(aq) + NaClO3(aq) + 3H20(1) Cl,faq) + GOH aq) —> SCI (aq) + CLO; fag) + HOW) ° =“ 4 REDUCTION dn * OXIDATION Chlorine gets oxidized as there Is an increase In oxidation number from 0 in Cl: to +5 in Clos Chlorine gets reduced as there is a decrease in oxidation number from 0 in Cl2 to -1 in CeItdoesn't have to be NaCl but also KCl or KBr Reactions of Cl, Br, I- ions with concentrated sulfuric acid General Equation: HaSOu{I) + X-(aq) -» HX(g) + HSO+(aq) You should know these typical observations made and products formed when sulfuric acid is added to the three halides Halide | Observations Products Naci | misty fumes Hydrogen chloride, HCI NaBr | misty fumes Hydrogen bromide, HBr brown fumes Bromine, Brz colorless gas with choking smell__| Sulfur dioxide, SO2 Nar | misty fumes Hydrogen iodide, HI purple fumes or black solid Iodine, 12 colorless gas with choking smell | Sulfur dioxide, SO» yellow solid Sulfur, S colorless gas with rotten egg smell | Hydrogen sulfide, H2S. 8.27 understand the following reactions: i solid Group 1 halides with concentrated sulfuric acid, to illustrate the trend in reducing ability of the hydrogen halides ii precipitation reactions of the aqueous anions Cl-, Br and I- with aqueous silver nitrate solution and nitric acid, and the solubility of the precipitates in aqueous ammonia solution hydrogen halides with ammonia gas (to produce ammonium halides) and with water (to produce acids) Check out 2022 Jan U2 6 marker t= Halide Ion Tests! Add dilute nitric acid and then adg silver nitrate solution to the unknown solution, followed by ammonia solution ‘The halide ions will react like this: Ag'(aq) + X (aq) > AgX(s) Cr fons Br ions T-jons ‘Add silver nitrate White precipitate | Cream precipitate | Yellow precipitate | solution ‘Add dilute aq. ammonia | soluble insoluble insoluble ‘Add concentrated aq. | soluble soluble insoluble ammonia Hydrogen halides react with ammonia gas to produce ammonium halides HCI(g) + NHa(g) —» NHCI(s) Hydrogen halides react with water to produce acids = Hydrogen chloride dissolves in water to form hydrochloric acid 8.28 be able to make predictions about fluorine and astatine and their compounds, in terms of knowledge of trends in halogen chemistry You can use the trends to make predictions but do note this exception: AgF is soluble so we cannot use silver nitrate solution to test for F- ions Pearson Edexcel Intemational Advanced Subsidiary in ChemistryFurther suggested practicals: i reaction of solid potassium halides with concentrated sulfuric acid ii__ precipitation reaction for halides and other anions