ࡱ>      q` =bjbjqPqP !%::5d 44445dP.5$"7"7"7"7=>L?(rPtPtPtPtPtPtP$!RhT`P'@=@='@'@P"7"7kPGGG'@r"7"7rPG'@rPGGJK"75 =4DZKNO$P0PtKTGFT4KK8TKC?"e?G}??C?C?C?PPF C?C?C?P'@'@'@'@~'D ~'4^ 2.10 Organic chemistry 2.10.1 Alcohols 2.10.1a The alcohol functional group A homologous series with general formula CnH2n+1OH Methanol CH3OH, ethanol C2H5OH, propan-2-ol CH3CH(OH)CH3. Task2.10.1a.1 Draw displayed structural formulae for each of the alcohols above. Task2.10.1a.2 Name and represent a structural isomer of propan-2-ol. Task2.10.1a.3 Copy the following list and circle those which are alcohols: butan-1-ol, CH3CH2CH2OH, CH3CH2CH3, CH2=CHCH3 ,CH2=C(OH)CH3, propane-1,2-diol. 2.10.1b Displaying and classifying alcohols  INCLUDEPICTURE "http://upload.wikimedia.org/wikipedia/commons/1/19/Alcohol_examples.gif" \* MERGEFORMATINET  Source:  HYPERLINK "http://upload.wikimedia.org/wikipedia/commons/1/19/Alcohol_examples.gif" http://upload.wikimedia.org/wikipedia/commons/1/19/Alcohol_examples.gif A primary alcohol has 2 hydrogen atoms on the C holding OH. A secondary alcohol has 1 hydrogen atom on the C holding OH. A tretiary alcohol has 0 hydrogen atoms on the C holding OH. Task 2.10.1b Draw simple structural formulae, fully displayed structural formulae and skeletal formulae and name all of the alcohols possible with 4 carbon atoms. Label them as primary, secondary or tertiary. 2.10.1ci Combustion All alcohols are flammable and burn to form carbon dioxide and water. Incomplete combustion can lead to carbon monoxide or carbon as products. Small alcohol molecules burn efficiently with a blue or pale yellow flame as little soot is formed. 2CH3OH + 4O2 ( 2CO2 + 4H2O Task 2.10.1ci Write equations for the combustion of alcohols with 2, 3 and 4 carbon atoms. 2.10.1cii Reaction with sodium Sodium is such a reactive metal that it forces hydrogen in the hydroxyl group (OH) to behave like an acidic hydrogen. Sodium replaces hydrogen in this reaction. Compare: H-Cl sodium reacts with hydrochloric acid explosively, HO-H sodium reacts with water vigorously, H -OCH3 sodium reacts reacts with methanol steadily 2CH3OH + 2Na ( 2CH3ONa + H2 Sodium methoxide Task 2.10.1cii Write equations for the reaction of sodium with ethanol, propan-1-ol, propan-2-ol, butan-1-ol, propane-1,2-diol, 2.10.1ciii Substitution reactions HBr is made in situ from KBr and conc. H2SO4 . The alcohol forms a bromoalkane during heating under reflux. C2H5OH + HBr ----> C2H5Br + H2O Alkyl chlorides can be made by refluxing the alcohol with HCl (conc. HCl) in the presence of ZnCl2 C2H5OH (l) + HCl (g) ---------> C2H5Cl (l) + H2O (l) Phosphorus pentachloride produces white steamy fumes of HCl in forming an alkyl chloride. This is a test for the hydroxyl group. C2H5OH + PCl5 -----> C2H5Cl + POCl3 + HCl Iodoalkanes can be made in a reaction phosphorus triiodide made in situ from iodine and red phosporus. 3C2H5OH + PI3 ---> 3C2H5I +H3PO3 The relative reactivities of alcohols in halogenation are tertiary > secondary > primary alcohol. Task 2.10.1ciii Describe reagents and conditions, draw structural formulae for the organic products and reactants and give equations for the following reactions: The formation of 1-bromobutane. The formation of 2-chloropropane The formation of iodomethane. The treatment of of propan-2-ol with phosphorus pentachloride. 2.10.1civ Oxidation Potassium dichromate (VI) solution is acidified with sulphuric acid. It produces a colour change from orange to blue-green to show that the primary and secondary alcohols have undergone oxidation reactions. Primary alcohol (mild conditions of dil sulphuric acid and dichromate, heat and distil) ---> aldehyde C2H5OH + O -----> CH3CHO + H2O ethanol (primary alcohol) ethanal (aldehyde) Cr2O72- ----------> Cr 3+  HYPERLINK "http://www.drbateman.net/asa2sums/sum2.2/Photo_092305_004.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum2.2/Photo_092305_004_small.jpg" \* MERGEFORMATINET  Dichromate ions Cr2O72- are orange but chromium III ions Cr 3+ are blue Primary alcohol (forcing conditions of conc sulphuric acid and dichromate, heat under reflux) ---> carboxylic acid C2H5OH + 2O -----> CH3COOH + H2O ethanol (primary alcohol) ethanoic acid (carboxylic acid) Secondary alcohol (forcing conditions of conc sulphuric acid and dichromate, heat under reflux) --> ketone CH3CH(OH)CH3 + O -----> CH3COCH3 + H2O propan-2-ol (secondary alcohol ) propanone (ketone) Tertiary alcohol ---> no reaction Task 2.10.1civ.1 Draw and name the first 3 aldehydes, ketones and carboxylic acids. Task 2.10.1civ.2 Describe conditions, draw structural formulae for the organic products and reactants and give equations for the following reactions: Making propanal from an alcohol. Making butan-2-one from an alcohol Oxidation of methanol under forcing conditions Making propanoic acid from an alcohol 2.10.1d Preparation of organic liquids This apparatus shows heating under reflux. The reactants boil, so remain hot, but are condensed so not lost from the apparatus. A water bath is shown as direct heating with a naked flame may cause a hazard for flammable organic materials The products and reactants remain in the round bottomed flask and must be separated. Simple distillation is eventually used.  The reaction mixture may need to be purified before distillation. Solids in the mixture can be filtered out. Water can be removed if it forms a separate layer using a separating funnel. Task 2.10.1d Explain the function of each of the following 1: A heating device 2: Still pot 3: Still head 4: Thermometer/Boiling point temperature 5: Condenser 6: Cooling water in 7: Cooling water out 8: Distillate/receiving flask 9: Vacuum/gas inlet 10: Still receiver 11: Heat control 12: Stirrer speed control 13: Stirrer/heat plate 14: Heating (Oil/sand) bath 15: Stirring means e.g. magnetic follower (shown), anti-bumping granules or mechanical stirrer 16: Cooling bath. 2.10.2 Halogenalkanes 2.10.2a Nomenclature The names use fluoro for C-F, chloro for C-Cl, bromo for C-Br, iodo for C-I. If the C holding the halogen has 2 H atoms it is a primary halogenoalkane. If the C holding the halogen has 1 H atom it is a secondary halogenoalkane. If the C holding the halogen has 0 H atoms it is a tertiary halogenoalkane. e.g. CH3CH2CH2Br 1-bromopropane (primary) CH3 CH(I)CH3 2-iodopropane (secondary) (CH3)3CCl 2-chloro-2methylpropane (tertiary) CH3CH(Cl)CH2CH2Cl 1,2-dichlorobutane Task 2.10.2a Make and draw fully displayed structural formulae for the substances above. Give the structural formulae and names of one example of a compound with 5 carbon atoms which is a primary, secondary and tertiary halogenoalkanes. 2.10.2b Reactivity of primary, secondary and tertiary compounds The fewer hydrogen atoms on the carbon holding the halogen the faster the reaction. The order of reaction is tertiary>secondary>primary. Task 2.10.2b place the following in order of reactivity 3-bromohexane 3-bromo-3-methylpentane, 1-bromohexane and give a reason. 2.10.2c Preparation of halogenoalkane Halogenoalkanes can be made from alcohols in substitution reaction using hydrogen halides. The reaction takes place with heating under reflux. C2H5OH + HBr ( C2H5Br + H2O The HBr above is made in situ using KBr and conc H2SO4. The acid can be added through the top of a condenser. KBr +H2SO4 ( KHSO4 + HBr  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.5/sum5.52.jpg" \* MERGEFORMATINET   INCLUDEPICTURE "http://cms.ich.ucl.ac.uk/website/imagebank/images/clamp_holding_a_separating_funnel.jpg" \* MERGEFORMATINET  When the reaction is complete after about 30 minutes the mixture is separated by distillation.  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum5.5/distillation.JPG" \* MERGEFORMATINET  The distillate may contain reactants, products and side-products. The aqueous layer can be separated using a separating funnel, and the product redistilled. The product distilling at the boiling point (38oC for bromoethane) is collected. Task 2.10.2c Describe the preparation of 1-bromobutane by drawing a labelled diagram of suitable apparatus 2.10.2di with aqueous alkali Conditions: Heat under reflux in aqueous solution.Both NaOH or KOH are suitable. Reaction type: nucleophilic substitution C2H5Br + NaOH (aq) -------------> C2H5OH + NaBr Task 2.10.2di Write equations with structural formulae to show how aqueous KOH reacts with CH3I, 2-bromopropane, C2H5Cl, 2-bromo-2-methylbutane 2.10.2dii with alcoholic KOH Conditions: Heat under reflux with ethanol as solvent. Use KOH here. Reaction type: elimination CH3CH2Br -------------> CH2CH2 + HBr 2.10.2diii with aqueous silver nitrate Warming halogenoalkanes with aqueous silver nitrate leads to the formation of a silver halide precipitate. Hydroxide ions in water replace the halogen leaving halide ions in solution. E.g. C4H9I + OH- ( C4H9OH + I- I- (aq)+ Ag+ (aq)( AgI (s) AgCl is white, AgBr is buff, AgI is yellow. Heat sample of halogenoalkane with aqueous hydroxide ions. Acidify with dilute aqueous nitric acid. Add a few drops of aqueous silver nitrate. After 10 minutes a white precipitate soluble in dilute aqueous ammonia, indicates chloride In 2 minutes a buff precipitate insoluble in dilute aqueous ammonia but soluble in concentrated aqueous ammonia, indicates bromide. An immediate yellow precipitate insoluble in concentrated aqueous ammonia indicates iodide.  HYPERLINK "http://www.drbateman.net/asa2sums/sum2.2/sci_6.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum2.2/sci_6_small.jpg" \* MERGEFORMATINET   HYPERLINK "http://www.drbateman.net/asa2sums/sum2.2/sci_7.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum2.2/sci_7_small.jpg" \* MERGEFORMATINET   HYPERLINK "http://www.drbateman.net/asa2sums/sum2.2/sci_8.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum2.2/sci_8_small.jpg" \* MERGEFORMATINET   HYPERLINK "http://www.drbateman.net/asa2sums/sum2.2/sci_9.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum2.2/sci_9_small.jpg" \* MERGEFORMATINET  The order of reactivity is iodide>bromide>chloride This is explained by the different bond strengths. The large iodine atom gives a long weak bond so is easily broken and leads to a fast reaction. The reaction rate is high. The smaller chlorine atom gives a shorter stronger bond and leads to a slow reaction. Task 2.10.2diii Explain and describe what you would see if AgNO3(aq) was added to (a) 1-bromobutane (b) 1-iodobutane (c) 1-chloropropane (d) 2-bromobutane 2.10.2d(iv) with alcoholic ammonia Reagents: concentrated ammonia (in excess) in ethanol solution. Conditions: heat in a sealed tube. reaction type: nucleophilic substitution Mixtures of amines are formed: C2H5I + NH3 ---------> C2H5 NH2 + HI Ethylamine (amine) other products include: (C2H5)2NH and (C2H5)3N CH3CH2Br + 2NH3 ( CH3CH2NH2 + NH4Br CH3CH2Br + 2CH3CH2NH2 ( (CH3CH2)2NH + (CH3CH2)2N+HBr - And so on to give (CH3CH2)4N+Br-. Use of excess ammonia reduces the proportion of further substitution. Only primary halogenoalkanes give good yields; tertiary ones eliminate HX (as NH4X) and give alkenes. Task 2.10.2d(iv) Draw full structural formulae of above organic compounds and explain why this is nucleophilic substitution. Write equations to show how (C2H5)2NH and (C2H5)3N can be formed. 2.10.2e practical tests with part d See 2.10.2d(iii) 2.10.2f uses of halogenoalkanes Major uses include as solvents, as monomers for making polymers. They also have uses as intermediates in the preparation of organic compounds in the laboratory. CFCs are compounds of carbon chlorine and fluorine and carbon which were used as dry cleaning fluids, aerosol propellants, fire retardants and refrigerants. E.g. CFC-11CCl3FflurotrichloromethaneCFC-12CCl2F2diflurodichloromethaneThese release chlorine radicals in the upper atmosphere so destroying ozone. There use has been banned but existing CFCs will remain in the atmosphere for years as these compounds are non-biodegradable. Although concentrations are very low CFCs are 5000 time more effective as a greenhouse gas than CO2. CFCs have been replaced by hydrocarbons like butane although these are flammable. Other replacements include hydrochloroflurocarbons e.g. CHClF2 or hydroflurocarbons e.g. CH2F-CF3. The lack or absence of chlorine reduces the effect on ozone. Chloroethene, CH2=CHCl, is used to make poly(chloroethene) - usually known as PVC. Tetrafluoroethene, CF2=CF2, is used to make poly(tetrafluoroethene) - PTFE. (source  HYPERLINK "http://www.chemguide.co.uk/organicprops/haloalkanes/uses.html" http://www.chemguide.co.uk/organicprops/haloalkanes/uses.html) Halogenoalkanes are used as fire retardants as they inhibit reactions in flames. These reactions involve free radicals such as OH, CH2O, HCO and CH3. Halogen atoms and hydrogen halides react with radicals, removing them from a flame, and so slowing the burning process. Task 2.10.2f Use the table below to judge the best flame retardant. agentformulaRetardant powerLD50/ppmtetrachloromethaneCCl412.528000bromochloromethaneCH2BrCl4.565000bromochlorodifluromethaneCBrClF22.9324000bromotrifluromethaneCBrF35.6800000 Possible answer All retardants containing chlorine will threaten the ozone layer. CBrF3 has the highest LD50- so is safest. CCl4 has good retardant properties but CBrF3 is second best. 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