Notes ‘AS Chemistry Unit 2 Notes ‘Shapes of molecules and fons ‘= Pairs of electrons will repel each other as far as possible (due to electrostatic repulsion) © Finding the shape: 1. Draw dot and cross 2. Count the numberof electron pis —bond pais and one pars 3 Decide the shape adopted by the electron pis 4 Lookat the number offone pars and decide the shape adopted by the atom 5, Draw shape, including bond angles OND ANGLES AND ELECTRON Pains suave examine 30 SHAPE 2 bond pairs Lineor Bec, :Cl—Be— 120° atondpsis | Tranter och Gr B. Se ‘er 120° ‘bond pis Tetrahedal ou qa Sond pairs | TrigonalBoyramidl Pe, i“ aah, an | uF Gy FalgF bond pars oetahedrt Fe aloe iN, F oo" ‘= Lone pairs repel more than bond pairs because they are attracted toa single nucleus and not shared by two atoms By Fatima KassimNotes ‘+ Lone pairs reduce bond angles between bonding pairs. Each lone pair reduces predicted bond angle between bonding electrons by 2.5 degrees. 4election pairs on the central atom — based on the tetrahedral shape: 4 bond pairs = tetrahedral (e.g, CHsand NH’) -108.5° Sees eatee |e rete nd dmx a 107° Organic molecules: ‘+ Tetrahedral around carbon if saturated e.g. C,H, or trigonal planar around carbon if there is C=C bond. H H In CGH., the double bond reduces the bond angle further its electron rich) wr e ‘+ Countas one bond pair of electrons for purpose of determining the shape. 1 H Multiple Bonds: © Eg, COpis linear: Carbon Structures: ‘+ Carbon has several allotropes ~ different molecular structures due to differences in bonding. ‘+ Diamond: Each carbon atom forms 4 identical bonds to neighbouring carbon atoms ‘ving a tetrahedral arrangement. Because of the strong covalent bonds, diamond has @ VERY high melting temperature, is extremely hard (the hardest known substance) and cannot conduct electricity ~no free e- '* Graphite: Carbon atoms in layers. Within a layer, each carbon atom is bonded to 3 aU, other carbons the 4" outer. is delocallsed and free to move: conducts electricity Layers of graphite are weakly bonded to each other ~ London forces. Also has a very high melting point. By Fatima KassimNotes Fy « Fallrenes: Const of 32+ carbon toms. Buckminterfulerene has 60 carbon & 3 atoms, Ballshaped molecules. The fourth outer e- is delocalized, so conduct CY SG? alert. i eiese mari Sueard unas te can vaeiuhe aa rate embeded in polymer they may podicematerals wth god eecrcal >, conductivity and strength. ee Intermediate bonding and bond polarity: ‘© Electronegatvity: ability of an atom to attract an electron pair in a covalent bond. Increases ‘ACROSS the period (Fluorine isthe most EN element) and decreases down groups. ‘© Differences in elecronegativity between two elements will result in electrons being pulled further to one end, and there will be POLARITY Inthe bondeg: H—CI ‘© Ifthe difference is large enough, electrons will be transferred IONIC BOND. ‘+ Small, highly charged cations (e.g. Al") are highly polarizing, and will pull electrons toward ‘then very strongly, especially from a large anion (e.g, resulting ina covalent bond (Ally) ‘+ If molecule is SYMMETRICAL, there is no overall polarity. E.g. CCl, The dipoles cancel out. ‘+ Unsymmetrical molecules containing polar bonds will be polar molecules ~ describes as having a permanent dipole. ‘+ Polar bonds will defiect a stream of water (because water is polar} e.g. CHsCI deflects, CCl, doesn't, Intermolecular Forces: +3 types of forces BETWEEN molecules: London forces/Van der Waals (weakest), Permanent Aipole-dipole and Hydrogen boning (strongest) 41. London/VaW: Found in ALL molecules. Caused by an unequal distribution of electrons which makes a temporary dipole. Ths affects surrounding atoms causing Induced dipoles. The net result is a weak attractive force. Everything has London forces andthe MORE electrons the STRONGER/LARGER the force. 2. Permanent dipole-ipoles: deltaplus of one moleculeis attracted to delta minus of another molecule: f—G-----H—G 3. Hydrogen boning: The attraction between a hydrogen attached to Fluorine, Oxygen or Nitrogen on one molecule and an F, 0, N atom on ‘another molecule. e.g. hydrogen bonding in water: ‘Trends in physical properties by intermolecular forces: na # Alkane boiling points increase with carbon chain length, because the number of electrons increases, so more London forces. By Fatima KassimNotes ‘+ Branched chain alkanes have LOWER boiling points than straight chains because they can't pack as closely together, whereas straight chains can pack together closely (greater surface area in contact) therefore the IMF forces are greater and they have higher boiling points ‘© Alcohols have very high boiling points (lower volatility ~ harder to evaporate] due to strong, hydrogen bonding, ‘© HF has a high boiling point due to hydrogen Peace eee bonding. The graph dips down to HCl, Har and HI, which all have dipole-dipole interactions but the number of electrons is increasing, so there are additional London forces which raise the boiling points Solubiliy: ‘+ Affected by bonding, and usually @ substance will only dissolve ifthe strength of the new ‘bonds formed is the same, or greater than the strength of the bonds that are broken, ‘+ Ionic compounds dissolve n polar substances such as water, because the ions are attracted to the polar molecules and they surround the ions and pull them away from the ionic lattice. This releases energy known as the hydration enthalpy. This can only happen if the hydration enthalpy is big enough to overcome the lattice enthalpy. (Hydration vs. Lattice) ‘Alcohols are soluble in water, because they form hydrogen bonds with It. ‘+ Non-polar molecules wont form hydrogen bonds with water, so don’t dissolve in it Eg hhalogenoalkanes lke chlorobutane. ‘© Generally ‘ike dissolves lke” Example question: State and explain the solubility of hexane in water Hexane molecules are held together by London forces. Water molecules are held together by hydrogen bonds. Hexane can’t make hydrogen bonds with water, so the two liquids do not mix or dissolve in each other — immiscible, Redox ‘© Oxidation number: the number of electrons that need to be lost or gained to become a neutral atom ‘© Uncombined elements are 0 ‘© Fis always 1, group 1 are +1, group 2 are +2, oxygen is -2 (except in peroxides Hs0s where its -1), His +1 (except metal hydrides where its -1) ‘© Oxidation numbers in a neutral compound add up to zero, and in a polyatomic ion add up to the charge. ‘+ Ionic half equations are used for redox processes ~ when oxidation and reduction take place together in a reaction. By Fatima KassimNotes lf species are reduced, electrons are on the LEFT ‘© IF species are oxidised, electrons are on the RIGHT ‘+ Half equations are then added together for the full redox equation ‘© Eg. The overall equation for the oxidation of Iions by MnO, ions is obtained from the two half equations: MnO; + 8H'+ Se” => mni*+ 44,0 And 2 > ye2€ ‘+ For oxidising agents that contain OXYGEN, e.g. MnO,’, you will need H+ on the LEFT and H,0 fon the RIGHT (oxygen can’t swim) ‘+ The MnO, half equation has Se but the F equation has 2e', so to make them both have the ‘same number of electrons (so they can cancel out when the equations are added together), the MnOs equation has to be multiplied by 2, and the f equation multiplied by 5, so that they both have 10e" ‘They are then added together to give: 2MnO, + 16H’ + 10" => 2Mn + BHO + Sls ‘+ _Disproportionation: when one species is both oxidised AND reduced at the same time eg: ChtH,0 > Hel+ HClO ° 1a The periodic table ~ Group 2 ‘+ Have their highest energy electrons in an s sub-shell, hence they are called s-block elements. lonization energy (LE) trends: ‘© Going down the group, there is an extra electron shell compared to the element above, and the atomic radius is increasing ‘+ The outer electrons are increasingly furthe force is less. way from the nucleus; therefore the attractive ‘© The extra Inner shells shield the outer electrons from the attraction of the nucleus ‘© Therefore, the ionization energies DECREASE down the group (gets easier to remove an €") Reactions of group 2 elements with Oxygen, Water and Chi 1. Burnin Onygen to form solid oxides, often burning with a bright flame e.g: 2Mgy+Or—q > 2ME0y By Fatima KassimNotes 2. React with water to form metal hydroxide and hydrogen: 2.6: Cay t2HOq —> Ca(OH) 2ia+ Hon Mg reacts rapidly with steam: Mgy,+H:Oq—> MgO Hy 3, React with chlorine to form solld metal chlor Reactions of group 2 OXIDES and HYDROXIDES: 82 Mgiy#Chig > MeChs Reactivity INCREASES own group, as the LE creases Be doesnt react ‘Ma wit steam costeaaiy Sr ft quick 8a rapialy 1. Group 2 oxides react with water to form metal hydroxides, which dissolve. They are also alkaline 2. Group 2 oxides and hydroxides are BASES eB: C20 9+ Hy => CA(OH 209 ‘+ They neutralise dilute acids eg.: HCl or HNO) + Form the corresponding salt and water Hydroxides are the same trends of 2g: MeO + 2HCl ay => MeCh joa + H20 €20p}+ 2HNOs(q) => Ca (NOsh i+ #20 roxides and sulphates: Ca (OH)2j¢ ZHClog > Me Choa + HO * Generally compounds of group 2 elements that contain singly charged negative ions (e.g. (OH) INCREASE in solubility down group + Compounds with doubly charged -ve ions (e.g. 0,"! DECREASE in solubility down group, By Fatima Kassim Solubility of HYDROXIDES INCREASES down the ‘group MeOH), Insoluble ca (0H), sr(OHle Ba (OH) Most soluble Solubility of SULFATES DECREASES down the group MgSO, Most soluble caso, 5:50, BaS0, InsolubleNotes ‘Thermal stabil ARE TR ‘+ Thermal decomposition: when a substance decomposes when heated ‘+The more thermally stable a substance is, the more heat it requires to break it down, ‘+ The carbonate and nitrate ions are LARGE and can be made UNSTABLE by a cation. The greater the polarising power of the cation, the greater the distortion and the LESS stable the anion, ‘+ The further down the group, the larger the cations and less distortion caused therefore the MORE stable the carbonate/nitrate anion. Thermal stability increases down a group. ‘© Group 2 compounds are LESS THERMALLY STABLE than group 1 (more distortion by +2 cation) Group ‘+ Carbonates: From sodium carbonate down group 1, the carbonates will NOT DECOMPOSE ‘on heating ~ thermally stable. ‘© Nitrates: From sodium nitrate down group 1, the nitrates decompose to form the nitrite and oxygen 82 KNOs) => 2KNO2y + Ory Potassium Potassium Nitrate Natrte Group 2 ‘+ Carbonates: Lithium and group 2 carbonates decompose to form an oxide and carbon dioxide © CaCO =D C2049 + COs UsCOy) =D Uy + Ore ‘+ Nitrates: Lithium and group 2 nitrates decompose to form the oxide, oxygen. 2 CAINO:)»4y D> 2C00 5+ AND: + On ALND) DP 20,046 NOs 9+ Ong Testing thermal stability of nitrates and carbonates: 1. Nitrate ‘+ How long it takes until a brown gas - NO;—Is produced. Its toxic, so must be done in fume cupboard 2. Carbonates: ‘= How long it takes for carbon dioxide to be produced — tested using imewater which turns cloudy. By Fatima KassimNotes Flame tests: 4. Mix small amount of compound with few drops of hydrochloric acid 2. Heat a platinum or nichrome wire in hot flame to clean t. 3. Dip the wire into the compound and hold it in hot flame. Electrons are being excited to higher energy levels by the heat energy. When the electrons, return to the lower energy levels, they emit energy inthe form of visible light. Flame colours of group 1 and 2 compounds: Group 1: tithium = RED Group 2: Magnesium — wie sodium - EON Calcium ~BRICK RED Potassium =LLAC Strontium ~CRIMSON RED Barium GREEN ‘The periodic table ~ group 7, the HALOGENS. ‘© Non-metallic elements, VERY reactive, ‘© Diatomic covalent molecules ‘+ OXIDISING agents (they are reduced themselves), and become less oxidising, or reactive down the group. Halogen Physical state and colour | Appearance in water | Appearance in hydrocarbon solvent Fluorine Pale yellow gas NA N/A Chiorine Green gas Pale yellow/green | Pale yellow/areen solution solution Bromine Red-brown liquid Red/brown/orange | Red/brown/orange Todine Grey solid Brown Pinkjvioiet Reactions of halogens: 1, Disproportionation with alkalis ~ NaOH or KOH COLD alkali to give halide and halate (ions: HOT alka to give halide and halate (V) ior Xy+2NAOH—> NaKO+NaX+H0 | 3X; +6NaCHC—> NaXO,+ SNaX +3H,0 Xngit 20H ing > XO pat King AHO | 3Xrgyt GOH af HOs pt SK+ HO os: 0 “a ° 6 eg ¥2NaOH =D NalO+ Nale H,0| 387+ 6NIOH => NaBrO, + SNaBr 34,0 fechas Shen Sedum Sore iedte() side bromate(V) bomete By Fatima KassimNotes Oxidise metals, non-metals and ions IMetals: e4 fluorine and chlorine react with iron to form iron I!) halides + Iron is oxidised: 2Fe ——> 2Fe* + 62 © Chlorine is reduced: 3Cl,+6e°—> 6c © Overall equation: 3Chig+ 2Feyy—=—> 2FeChe ‘+ Non metals: eg, chlorine reacts with sulphur to form sulphur (I) chloride. Sulphur is oxidised to #1 and chlorine is reduced to -1) © Saq)+ ACI SP 48:Chy ‘+ lonsie.g all halogens except iodine (weak oxidising agent) will oxidise iron (I) ions to iron (ll) fons in solution. The solution will change colour from green to orange. 8 2) > Fe yy 20 Reactions of Halides; 1. Potassium halides with concentrated sulphuric acid: React to give @ hydrogen halide. ‘+The trend in strength of the halide ions as reducing agents is: > Br > CI KCl and #80, © KCliy+ HsS0q > KHSO4y+ HCly But hydrogen chloride i nt a strong enough redicing agent to reduce the sulphurie acid, so reaction stops there. Misty fumes of hydrogen chloride gas will be seen when it comes into contact vith moisture in air. This is NOT a redox reaction ~O.S of halide and sulphur stay the some (1 and +5) Kar and S04: + KBr) 550g), > KHSO44:+ HO This reaction gives misty fumes of hydrogen bromide gas, and the HBr is strong enough to reduce the H,SO,in a redox rea ‘Then ths reaction: 2HBr + HsS0xqy —P> Bray? SOny)# 24:0 0S of Br: 4 ° OXIDATION. sors: +6 “ REDUCTION Ki with #50. + K+ H:S0qy => KHS0u + Hl # DHIFHS0u9 > ly S094 209 By Fatima KassimNotes '* Same first two reactions, but because iodine is a very strong reducing agent, it goes further, and reduces SOsto HS © GHlg)+S0rj), => HS.) + hy 2HOy OS of: a ° OXIDATION. OS of s: “ 2 REDUCTION 1+ HSisa toxic gas, and glves a bad egg smell 2. Hydrogen Halides with ammonia and water + Hydrogen halides are colourless gases. They are very soluble, and dissolve in water tomake STRONG acids HClig =D Hp +CF na (dissociation) + Hydrogen chloride forms hydrochloric acid; hydrogen bromide forms hydrobromic acid and so on. + With ammonia: react to form white fumes of the corresponding ammonium hal NHsig+ HCly => NaCl 3. Displacement by more reactive halogens ‘+ The oxididising strengths of the halogens can be seen in their displacement reaction with halides. + ce Bray 2Klgy => 2KB a+ a ‘© The bromine displaces the iodine ions (it oxidises them) giving iodine Inug and potassium bromide ‘+ Ahalogen will displace a halide from solution ifthe halide is below it in the periodic table 4, Silver nitrate solution, and silver halides solubility in ammonia and reactions with sunlight: To test for halides in solution: [Add dilute nitric acid ~ this removes ions that could interfere with test and ppt. {Add silver nitrate solution (ABNOsaa)) AA precipitate of the silver halide will form, the reaction i AB ea X ma => ARK The colour of precipitate identifies the halide, and they have different solubilty’s in ammonia solution: '¢ Chloride cr: White ppt which dissolves in dilute NH, .y and darkens in sunlight By Fatima KassimNotes ‘+ Bromide Br: Cream ppt, dissolves in concentrated NH ja and darkens in sunlight, ‘Iodide F: Yellow ppt, insoluble in concentrated NHS 4g and does NOT darken in sunlight. The reaction of silver halides with sunlight (decomposition) is fuori 2ngBr => 2Ag+ Br, ‘+ Number of electrons increases down group, so London forces wil increase. Astatine will bea solid and have the highest boiling temperature, ‘+ Electronegativity decreases down group, so astatine will have lowest EN value. ‘+ Fluorine will be most oxidising Kinetics ‘+ Reactions only happen when: Particles collide n the correct orientation, and they possess ‘the activation energy (minimum amount of kinetic energy particles need to react). This i the collsion theory. ‘© Enthalpy profile diagram: ‘+ Factors affecting the rate of reaction: concentration, temperature, pressure, surface area ‘and catalysis. Factor How it affects Explanation rate Concentration | increasing The particles become more crowded, therefore collide (solution) | conc-/pressure | more times which increases the reaction rate. Pressure (gas) | increases rate “Surface area | Increasing “The smaller the sizeof reacting particles, the greater the (Golids) | surface area__| total surface area. Increasing surface area means larger Increases rate _| area is exposed for reaction and more collsions. Increasing Increasing temperature means the average speed of Temperature | temperature | reacting particles increases, therefore more collisions per increases rate _| second, Speeds up the | Lower the activation energy by providing an alternative Catalyst | reaction route. If activation energy is lower, more particles will hhave enough energy to react. By Fatima KassimNotes Maxwell-Boltzmann distribution: ‘+ Shows distributions of molecular energies in a gas ‘+ When temperature is increased, particles will have more kinetic energy and move faster. This means that more particles wll have energies greater than the activation energy and will react. This changes the shape of the Maxwell Boltamann distribution curve pushing it to the right, with a peak lower than the original 7 (omrteoeraie R Higher temperature (niy molecules this regloncanreact~ molecules ve a higher eneray than the sactaton energy Ey eneny Total numberof gas molecules under the catalysts: ‘+ Increase the rate of a reaction by providing an alternative reaction pathway with a lower activation energy. Itis chemically unchanged at the end of the reaction, Ea wen eatays a (no catalya) ‘+ Homogenous catalysts: in the same state as the reactants, ‘© Forms intermediates with the reactants, which the products are then formed from. ‘© The activation energy needed to form the intermediates and the products from the intermediates is lower than that needed to make the products directly from the reactants. exon ae By Fatima KassimNotes Chemical Equilibia ‘+ Many reactions do not go to completion because the reaction is reversible, <> ‘+ Dynamic equilibrium: When the rates of the forward and reverse reactions are equal. I's ‘dynamic because individual molecules react continuously. Its at equilibrium because no net ‘change occurs (overall concentrations remain constant ‘+ Equilibrium can only happen in a CLOSED system. ‘The effect of conditions on the position of equilibrium: Table The eects various factors on equilibrium postion ‘© Controlled by Le Chateliers principle: When a [Fact | Effet on equilibrem portion system at equilibrium is subjected to a feces a ‘change, it will behave in such a way to ees a ‘counteract that change. 1 cone of products > moves to let ‘+ Temperature is a very important way to 1 cone of rodace = mover tonight ‘control industrial processes, because itis the most effective factor (general rule ~ comenber mevetolefimeas mer reseants crease ove tight mean sore rods) in 10K doubles the rate of reaction. < mew | teen siepebckuminrprmins + Pressure is very expensive to use in | prewme= movestside with ee pr sees equlbrium processes ‘© The red-brown gas NO» exists in equilibrium PRs cea ee cases on with pale yellow NO, stelcleencach de [Temperate | rrpertre = moves inthe destin of endotbemic NO, <== 2N0, ‘easton (AM postive) J eapenture = movesin the deena of xoheraie The forward reactions endothermic, Lo + the postion of equilibrium shifts to left the —————————— mixture pales + Ifthe position of equilibrium shift to right the mixture darkens ORGANICS Alcohols: * General formula: C.Hisxi0H where the functional group is C-OH Examples: CH,OH ~ Methanol ~ used for fuels and plastics. CCHyCH,OH ~ Ethanol ~fuels, alcoholic drinks (CH\CH,CH,OH —Propan-1-ol CH3CHOHCH- Propan-2-o| 4 4 ¢ ¢ + canbe primary secondary or tertiary alcohols: HG-O# C-E-oH c-E-oH c-E-ow Reactions of alcohols: By Fatima KassimNotes 1. Combustion of alcohols: CiHs0Hy +303) =D 2C04y #3H. 09 2. Reaction with Sodium: INayy4 CHYCHOHy =D 2CHCHONS+ Hy Sedlum ethanol => sodium ethoxide + hydrogen ‘And the longer the hydrocarbon chain, the less reactive with sodium, (Observations m: Sodium fizzes, bubbles form, sodium disappears, and white solid product forms 3. Substitution reactions to form halogenoalkanes: ‘Alcohols react with PCis (Phosphorus (v) Chloride}, releasing hydrogen chloride gas which forms misty fumes in ait CCHsCH:OH w+ PCle => CH.CHsCl . POC y+ HCl ‘+ The OH is swapped for the Cl, and this reaction can be used as atest for an -OH group. The steamy fumes that are produced turn blue litmus paper red (because HCI dissolves to form a strong acid) ‘+ Tomake a chloroalkane, just mix a tertiary alcohol (most reactive) and hydro together. This will give an impure chloroalkane which can be purified. 4, Oxidation of alcohols: 9 ° 9 q g q schlorie acid —t-H —¢— —C-on Must be familiar with these functional groups: acid ‘+ To oxidise alcohols we use acidified potassium dichromate solution, ‘© Thisis orange in colour and isa mixture of sulphuric acid, HzSO4 and K:CrsO>, ‘+ The orange colour is due to the Cr ions in KsCr.0. ‘+ Ifitoxidises (i. the Cr ions become reduced) then the solution turns green. Ching VUV— UWA carbonic ¥ ‘The results show that only primary and secondary alcohols can be oxidised, and tertiary alcohols cannot be oxidised, therefore remains orange. By Fatima KassimNotes Oxidation of primary alcohols: ‘+ Aprimary alcoho! can be ovicised to an aldehyde and then toa carboxylic ac This is carried out using an oxidising agent: Mixture of sulphuric ack, H,SO,(souce of H’) and potassium/sodium dichromate, Kr:0y + To stop oxidising at the aldehyde, you must’ allow the product to distil over” + To.get the carboxylic acid, you heat under reflux Primary 2 eee. tt akcoel to Temesaey™ FF aldehyde ' a eles © Thisis the distillation apparatus. + The aldehyde has to be distilled off as it forms asit can be oxidised further Distillation evaporates and condenses liquids at different temperatures. Collect the liquid you want around its boiling point and discard any others Keo Primary alcohol to carboxylic acid + 20) + When making the carboxylic acid the mixture is refluxed, * Heated strongly with an excess ofthe acidified potassium or sodium dichromate, and the alcohol will be completely oxidised passing through the aldehyde stage to form a carboxylic acid, By Fatima KassimNotes ‘+ Refluxing allows you to heat / boil volatile liquids for a long time. The condenser stops the volatile liquids evaporating off, because any vaporised compounds are cooled, condense and drip back down to the reaction mixture Oxidation of secondary alcohols: ‘© Secondary alcohols are oxidised to ketones ONLY. Do not undergo further oxidation. ‘© This can be done by refluxing the secondary alcohol with acidified sodium/potassium dichromate won ow eae | Kn /4804 po oy eae) Hom nn bind anon summary Primary alcohol ==> Aldehyde => Carboxylic acid Secondary alcohol C—=> Ketone => Noreaction Tertiary alcohol => —Noreaction Halogenoalkanes ‘+ Halogenoalkanes have the general formula CnH2n¢1X, Xis a halogen. ‘© Canalso be primary, secondary and tertiary lke alcohols. ‘© When naming, the halogen partis named frst (prefix ehloro-, bromo-,ledo-) followed by name of alkane + Eg. CliC1=Cloromethane CHCH,Br = Bromoethane ‘+ If there is more than one halogen di- and tri-are used to indicate the number of halogens present, © g, CHBrCH.8r = 1,2-dibromoethane Reactions of Halogenoalkanes: ‘+ Halogencalkanes contain polar bonds because the halogen is more electronegative than the carbon. Ths leaves a carbon with a delta + charge, making it open to attack by ‘nucleophiles. By Fatima KassimNotes ‘+ Nucleophiles: attracted to electron deficient atom, d+ and donate a pair of electrons to form a new covalent bond ‘+ The halogen will be replaced by the nucleophile, which gives a substitution reaction, giving 2 ew functional group. Halogenoalkanes react with aqueous alkalis to form ALCOHOLS ‘+ Aqueous hydroxide ions need to substitute the halogen. Sodium hydroxide NaOH, oF potassium hydroxide KOH. can be used +The reactions called hydrolysis and usually carried out under reflux + Hydrolysis i @ reaction with water or aq hydroxide ions that break a chemical compound into two compounds wr Ge 7 \ Mechanism: ee Water can act as a nucleophile too, but it is a much slower reaction: First step parts ‘The estates ania o, ‘The overall equation with water: R-Hal+ HO + RON +H + Har By Fatima KassimNotes ‘+ If water with dissolved silver nitrate is used, this can tell us about the reactivities of halogenoalkanes ‘© When water and an alcohol react, and an alcohol is formed, the silver nitrate wil react with the halide ions when they form giving a silver halide precipitate ‘© The precipitate that forms first indicates which halogenoalkanes hydrolyses frst: Tertiary halogenoalkanes ~ precipitate forms immediately Secondary halogenoalkanes ~ precipitate forms after several seconds Primary halogenoalkanes ~ precipitate forms after several minutes ‘© This shows that the reactivity is tertiary 3°> secondary 2°> primary 1° 2. Halogenoalkanes react with alcoholic ammonia to form amines ‘+ Ammonia NH; has a lone pair of electrons, and can therefore act as a nucleophile * Alcoholic ammonia ~ ammonia dissolved in ethanol. ‘© Heated under reflux ‘MECHANISM Inthe second step, and ammonia molecule removes hydrogen from the NHs {group to form an ammonium ion (NH) ‘This can then react with the Br jon from Br step 1, to form ammonium bromide: NHBr Overall reaction: with ethanol and under reflux 4 ‘tae as 3. Alcoholic alkali to form alkenes \When a halogenoalkane reacts with alcoholic alkall, e.g. potassium hydroxide, KOH in hot ethanol, an alkene is made eee eee ee < fested under rea ee send Fer + HO Uses of halogenoalkanes: ‘© Halogenoalkanes are used as fire retardants and refrigerants By Fatima KassimNotes ‘© Chlorofluorocarbons (CFCs) used to be used in the past because of their unique properties (non-toxic, non-flammable, unreactive), but it was found that they deplete the ozone layer Inthe atmosphere, so are being phased out (see notes later) ‘© Other halogenoalkanes such as hydrofluorocarbons (HFCs) are now used as safer alternatives, Mechanisms: Free radical ~ species with an unpaired electron Electrophile ~ species that accepts a pair of electrons Nucleophile~ species that donates a pair of electrons. Substitution ~ one species is replaced by another Addition — joining two or more molecules together to make a larger molecule Elimination ~ when a small specie is eliminated from a larger molecule (Oxidation — loss of electrons, Also is the gain of oxygen/loss of hydrogen Reduction ~ gain of electrons. Also Is the loss of oxygen/galn of hydrogen Hydrolysis ~ Splitting up using water (usually In form of OH Ions) Polymerisation — joining together monomers into long carbon-chain polymers. Redox any reaction where electrons are transferred between two species Bond breaking ~ homolytic and heterolytie: ‘= Homolytic— when the bond breaks evenly, and one electron moves to each atom. This forms two free radicals as both atoms now have an unpaired electron. The unpaired electron makes free radicals very reactive, ‘© Heterolytic — when the bond breaks evenly, and both electrons from the shared electron pair move to one atom. This forms two different species: a positively charged cation — an lectrophile, and a negatively charged anion ~ a nucleophile \When drawing curly arrows ~ double headed arrow shows movernent of electron pair; single headed arrow shows movement of single electron. Should be able to recall these reaction mechanisms from unit 1: Electrophilic addition and free radical substitution: Hydrogen bromide to alkenes: By Fatima KassimNotes wy > 20h 2) Ck 4CH, —> -CHy + He ‘© Free radical substitution of chlorine in alkanes: “cH, + Ck —> CHC 4 cr ‘+ Initiation, propagation, termination 3) ck 4 -CH; — cHycl a Predicting the type of mechanism: ‘+ Polar bonds always break heterolytically ‘= Anucleophile can attack the d” atom in a polar bond + Anelectrophile can attack an electron-rich part of a molecule ~e.g. the C=C bond in alkenes All reagents used in AS chemistry (helpful to learn them); ‘= Nucleophiles: OF i, NH sete, PC, NaBr/H,SO,0r PBYs,P/ly # Electrophiles: He X2, HX ‘© Oxidation [0]: KMn0, /H", K ,Cr:0;/H° cidified Other: KOH in hot ethanol, Cl/ uw light, RO ~OR/ u.v light (polymerisation) ‘+ Ozone molecules Os ‘© The ozone layer is at the edge of the stratosphere ‘+ Ie fiters out most of the harmful UV radiation which can damage DNA in cells causing skin cancer and can also cause eye cataracts. '* Ozone is formed when UV radiation from the sun hits oxygen molecules. This forms two free radicals, The free radicals then combine with other oxygen molecules to form ozone molecules 0,+UV => oF +0" 0.40" —> 0; i ree radical The ozone layer is constantly being replaced, and there is a natural balance between formation of new ozone and breakdown of ozone molecules: 0;+0* <== Os *Itwas discovered that the ozone layer i thinning in places, and a hole in the ozone was discovered over Antarctica this means that more harmful UV will reach the earth. The decrease in ozone concentrations Is due to CFCs ~ chlorafluorocatbons. Because of their un-reactivity, CFCs don’t decay and reach the upper atmosphere and the ozone layer, where several reactions happen: 1) CFCs are broken down by UV light, forming chorine free radicals CCiFayy) > CCLFg + Cig 2) The free radicals are catalysts, and react with ozone to form an intermediate ~ ClO*, and Os By Fatima KassimNotes “The fre aia regenerated ‘i = : and gos on toatack other one Cat Ong Oat Oty molecules. This shows that one . : (rc molecule can destroy ClO%4g + Ory > 20249) + Cle) ‘thousands of exene molecules 3) The overall reaction i 20s, D> 30,4 (Cis the catalyst) ‘+ Nitrogen oxides are produced from car an chlorine radicals, NO* also act as catalysts ireraft engines and thunderstorms. Like NO* +0; —=> 0, + NO,* No;*+0;—=> 20;+No* ‘+ Some molecules absorb energy from infrared radiation. This makes the bonds vibrate ‘+ Vibrations occur in one of 2 ways, a stretching vibration or a bending vibration ‘© Every bond vibrates at its own unique frequency depending on: 1. Bond strength Bond length 3. Mass of atom at either end of the bond ‘© Oxygen 0;, and Nitrogen N; don't absorb infrared radiation, but CO,, HO, nitric acid (NO) , and methane (CH) do absorb infrared radiation. They absorb IR because they change thelr polarity as they vibrate (due to the movement of dipoles in polar bonds) ‘+ Gases that do absorb IR radiation are called greenhouse gases ~ they stop some of the radiation emitted by the earth from escaping into space, ‘What the spectrum fook lke: ‘+The spectrum gives us ‘peaks! which are actually absorbance troughs. ‘+ These troughs are caused by a frequency of IR light being absorbed from a bond vibrating bond. + Each peak’ is characteristic to a specific bond / atoms By Fatima KassimNotes Identification of functional groups: ‘+ We have just seen that the peak on an IR spectra are due to specific bonds (and atoms} vibrating or stretching. ‘©The frequency at which you find an absorbance peak is therefore unique to bonds and ‘atoms at each end of the bond. ‘+ This means that functional groups will give specific peaks. fr i one Aldehydes, ketones, carboxylic acids 11640-1750, [=| ‘Organic compounds 2850 - 3100 2500-3300 Carboxylic acids (very broad) [| ‘Alcohols (hydrogen bonded) 3200 - 3550 (broad) Eset tl i aa Alcohols: ‘The IR spectrum for methanol, CH,OH is shown below: ‘+The peak at 3230 - 3500 represents an 0-H group in alcohols. ‘Aldehydes and ketones: ‘+The IR spectrum for propanal, CCHsCHO is shown: ‘+The peak at 1680-1750 represents @ C=O group in te aldehydes and ketones. By Fatima KassimNotes Aldehydes and ketones: ‘The IR spectrum for propanole acid, CCH:CH,COOH is shown: ‘+The peak at 2500 - 3300 represents an 0-H group in a carboxylic acid. ‘+The peak at 1680 - 1750 represents a C=O group ina carboxylic acid, er a a we ae we Mass spec ‘+ _Ionisation in a mass spectroscope Is usually done by electron bombardment. ‘+ Electron bombardment knocks another electron out of the molecule producing a positive ‘molecular ion -M'. GHOH +e > GHOH' +26 ‘+ The molecular ion has the same mass as the Mr ofthe molecule, ‘+ As we have a mass and a charge we can use a mass spectrometer to determine the Mr (rm/2) Fragmentation: ‘+ Excess energy from the ionisation process causes bonds in the organic molecule to vibrate and weaken. ‘+ This causes the molecule to split or fragment into smaller pieces. ‘+ Fragmentation gives 2 positively charged molecular fragment ion and a neutral molecule: CHOW > CH + CHOHT ‘+The fragment ion, CH,OH' has a mass and charge so we can use amass spectrometer to determine the Mr (m/z) of that fragment, ‘+ Fragment ions can be broken up further to give a range of m/z values. ‘+The m/z values cotrespond to the Mrs of the molecule and its fragments. ‘+The Mrof the molecule is always the highest m/z value - Le. this molecule has not been fragmented soit must have the highest Mr. ‘+The one below is for ethanol. it has a m/z of 4S which s also its Mr. uaa 48 0408 oneoeeen it lL » so 6 By Fatima KassimNotes Fragmentation patterns: ‘+ Mass spectroscopy Is used to identify and determine the structures of unknown compounds. ‘+ Although 2 isomers will have exactly the same M” peak, the fragmentation patterns will be Unique to that molecule, ikea fingerprint. “+ In practice mass spectrometers are linked to a database and the spectra is compared until an exact match Is found: I ; a TTT eters Tees ll tha ‘+ These are the mass spectra for pentane and a structural isomer of pentane, 2 methylbutane. ‘+ The M’ peaks the same for each but the fragmentation patterns are different. Identifying fragment io ‘+ When you look at a mass spectrum, other peaks seem to look more important than the M” peak. ‘+ These fragment peaks give clues to the structure of the compound. ‘+ Even simple structures give common peaks that can be identified: ‘m/z | Possible identity of the value | __ fragmention 18 cay 29 Cais 3 Gin? 57 Cat? 7 on" ‘+ Functional groups are a good place to start, OH = m/z of 17, ‘+ Some fragments are more difficult to identify as these will have undergone molecular rearrangement. Identification of organic structures: ‘+ Ammass spectrum will not only tell you the Mr (from the M’ peak), but it can also tell you some of the structural detai ‘+ These peaks have been labelled with a letter: By Fatima Kassim