ࡱ> '` wbjbjDD .&&o7777$9X29DB<B<B<B<=j?C@`X X X X X X X$Yh9\\DXB==BBDXB<B<YXRRRB B<B<XRBXRRRB<9 `P7MRU|oX0XR\Q\RR\S @vATRmADA@@@DXDXR @@@XBBBB$)$) Unit 4.8 Further Organic Chemistry 4.8.1. Isomerism 4.8.1a Structural and E-Z isomerism Structural isomers are compounds with the same molecular formula but different structural formulae. The atoms are arranged in a different order. e.g. CH3CH2CH2CH2Cl (1-chlorobutane) and CH3CHClCH2CH3 (2-chlorobutane) Task 4.8.1a(i) Make using models, name and write formulae for isomers of chloropropane, Name, write molecular formulae, draw structural formulae for the all of the structural isomers of C5H11Cl and heptane. Geometric isomers exist for some compounds with C=C double bonds in their molecules. They have the same molecular formula, the same structural formula but different arrangements of atoms in space. No rotation is possible around the double bond so different compounds result if different atoms or groups are in the positions on each side of a double bond. For example 1,2-dichlorethene can have its two chlorine atoms on the same side (cis) or opposite sides (trans) of the double bond. Z stands for the German word zusammen meaning together i.e. cis. Give atoms attached to one C atom high priority if they have higher atomic numbers. Take the atoms with highest priority either side of the double bond as cis or trans. Cl Clcis-2,3-dichlorobut-2-ene Cl CH3 trans-2,3-dichlorobut-2 ene \ /Z-2,3-dichlorobut-2-ene \ / E-2,3-dichlorobut-2-ene C=C C=C / \ / \ CH3 CH3 CH3 Cl  HYPERLINK "http://www.chemguide.co.uk/basicorg/isomerism/ez.html" Full explanation of E-Z system. Task 4.8.1a(ii): Draw and name both geometric isomers of 1,2-dibromopropene, 1,2-dichloroethene, 1,2 -dibromopent-1-ene. Make models of the first two examples. 4.8.1b Optical isomerism Optical isomers exist for compounds in which molecules have an asymmetric carbon atom. That is a carbon atom bonded to 4 different atoms or groups. These atoms or groups can be arranged in two ways in space. One arrangement is the mirror image of the other. The mirror image is non-superimposable on the first arrangement in the same way that your left and right hand cannot be superimposed.. This is called chirality. The carbon atom at the centre is called a chiral centre.The isomers are called enantiomers e.g. 2-hydroxypropanoic acid H COOH | HOOC H \ / | \ / C | C / \ | / \ CH3 OH | HO CH3 mirror Task 4.8.1b Draw the above structures showing the tetrahedral structure and the bond angles. Make, name and draw three more structures which will have optically active isomers and label their chiral centres. Observe each of your models in a mirror and make a model of the image. Draw both enantiomers.  HYPERLINK "http://www.drbateman.net/asa2sums/sum4.5/funcgpopt.xls" Functional group and chirality test. (Needs Excel.) 4.8.1c Optical activity and racemic mixtures Optical isomers differ only in the extent to which they rotate the plane of polarised monochromatic light.  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/sum4.51.gif" \* MERGEFORMATINET   INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/sum4.52.gif" \* MERGEFORMATINET  Optical isomers exist in two forms called enantiomers The dextrorotatory (+) form rotates light to the right (clockwise) but the laevorotatory (-) rotates light to the left. A sample of an optically active substance may contain both optically active isomers. An equimolar mixture does not rotate light at all as equal and opposite rotations cancel. This optically inactive mixture is called the racemic mixture or racemate. Task 4.8.1c Draw diagrams to show observations as light passes through first one then two pieces of polaroid material. Write explanations of what is seen. Draw the above diagram but show the effect of an optical isomer between the two pieces of polaroid. Draw both enantiomers for two different substances and label the chiral centres. Draw two enantiomers in a racemic mixture. Draw the above diagram showing the plane of rotated light with a laevorotatory enantiomer. 4.8.2. Carbonyl Compounds 4.8.2a The carbonyl functional group The carbonyl functional group is -C=O. In aldehydes | R-C=O | H Aldehydes: methanal, HCHO; ethanal; CH3CHO etc In ketones (where R= an alkyl group e.g. CH3) R-C=O | R Ketones: propanone, (CH3)2CO; pentan-2-one, CH3CH2CH2COCH3. Task 4.8.2a draw fully displayed structural formulae for the first 5 aldehydes and 5 ketones giving names in each case. 4.8.2b Physical properties of carbonyl compounds Benzaldehyde C6H5CHO smells of almonds Cinnamaldehyde C6H5CHCHCHO smells of cinnamon 3-methoxy-4-hydroxybenzaldehyde C6H5 (OCH3) (OH)CHO smells of vanilla The carbonyl group is polar so aldehydes and ketones have higher boiling points than hydrocarbons of the same relative molecular mass. However since carbonyl compounds cannot form strong hydrogen bonds with each other they have they have lower boiling points than corresponding alcohols. CH3CH2CH3 propane bp= -45oC, CH3CH2CHO propanal bp= 49oC CH3COCH3 propanone bp= 56oC, CH3CH2CH2OH propan-1-ol bp= 97oC Task 4.8.2b.1 State with a reason which of the following pairs have the highest boiling point: pentanal or pentan-1-ol, pentane or pentanal, pentan-2-one or pentan-2-ol. The oxygen atom in the carbonyl group allows aldehydes and ketones to form strong hydrogen bonds with water molecules. Low relative molecular mass aldehydes and ketones are therefore very soluble. Task 4.8.2b.2 State with a reason which of the following pairs of compounds is most soluble: butane or butanal, propanone or propane, butanal or ethanol, pentanal or ethanal. 4.8.2c(i) identification using oxidation with Fehlings solution or Benedicts (oxidation) Aldehydes (but not ketones) reduce Cu2+ to Cu+ giving a red brown precipitate of copper (I) oxide in this test. Drops of the carbonyl compound are added to equal volumes of Fehling's solutions A and B. The mixture is warmed in a water bath. (oxidation) RCHO(aq) + 2Cu2+(aq) + 2H2O(l) -----> RCOOH(aq) + 4H+(aq) +Cu2O(s)  HYPERLINK "http://www.drbateman.net/asa2sums/sum4.5/Photo_092305_005.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/Photo_092305_005_small.jpg" \* MERGEFORMATINET The blue Fehling's solutions forms a red/brown precipitate Task 4.8.2c(i).1 Write balanced chemical reactions and describe what would be seen if the following were treated with warmed Fehlings or Benedicts solution: ethanal, methanal, propanone, propanal. with Tollen's reagent (ammoniacal silver nitrate solution) (oxidation) Aldehydes (but not ketones) reduce Ag+ to Ag giving a silver mirror in this test. Drops of sodium hydroxide are added to silver nitrate solution followed by aqueous ammonia until the ppt. redissolves. The aldehyde is warmed in a water bath with the reagent. (oxidation) RCHO(aq) + 2Ag(NH3)2+(aq) + H2O + 2H+(aq) ( RCOOH(aq) + 2Ag(s) +4NH4+(aq) reduction half reaction 2H+(aq) +Ag(NH3)2+(aq) +2e- ( Ag(s) + 2NH4+(aq) oxidation half reaction RCHO +H2O(l) ( RCOOH(aq) +2H+(aq) + 2e- Task 4.8.2c(i).2 Write balanced chemical reactions and describe what would be seen if the following were treated with warmed Tollens reagent: ethanal, methanal, propanone, propanal.  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/agno3.jpg" \* MERGEFORMATINET   INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/addnaoh.jpg" \* MERGEFORMATINET  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/addnh3.jpg" \* MERGEFORMATINET  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/waterbath.jpg" \* MERGEFORMATINET  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/closesilver.jpg" \* MERGEFORMATINET  4.8.2c(ii) identification using LiAlH4 with sodium tetrahydridoborate(III) (sodium borohydride) or lithium tetrahydridoaluminate (lithium aluminium hydride (reduction) Aldehydes form primary alcohols and ketones form secondary alcohols with this reducing agent. NaBH4 in aquous solution is easier to use than LiAlH4 in dry ether solution. Lithium tetrahydridoaluminate(III) (lithium aluminium hydride) LiAlH4 does bring about the same reaction. CH3CHO + 2H. ( CH3CH2OH CH3COCH2CH3 + 2H. ( CH3CH(OH)CH2CH3 Task 4.8.2c(ii).3 Draw the starting material and name and draw structures for the products of dry LiAlH4 in ether or aqueous NaBH4 with methanal, propanone, propanal and pentan-3-one 4.8.2c(iii) nucleophilic addition reactions of HCN with hydrogen cyanide (nucleophilic addition) HCN made in situ from KCN and HCl. Alkali is added to ensure a reasonable concentration of CN- by shifting the following equilibrium to the left: CN- + H2O <-----> HCN + OH- CH3CHO + HCN ------> CH3CH(OH)CN ethanal 2-hydroxypropanonitrile (a cyanohydrin) Task 4.8.2c(iii).1 Draw diagrams showing the bond in each reactant and product above. This is a nucleophilic addition reaction with a two step mechanism. CH3 CH3  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/arrow2.gif" \* MERGEFORMATINET  |  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/arrow2.gif" \* MERGEFORMATINET  | N=C- C=O ------> N=C-C-O- slow step | | H H CH3 CH3 |  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/arrow2.gif" \* MERGEFORMATINET  | N=C-C-O- H+ ------> N=C-C-O-H fast step | | H HTask 4.8.2c(iii) Draw diagrams for mechanisms for reactions of propanone and methanal with HCN. 4.8.2c(iv) Describe and carry out reactions of carbonyl compounds with 2,4-dinitrophenylhydrazine (condensation) This is used as a test for the carbonyl group with a positive test giving a yellow/orange ppt of a hydrazone. (CH3)2C=O+ NH2-NH-C6H3(NO2)2---->(CH3)2C=N-NH-C6H3(NO2)2+ H2O propanone2,4-dinitrophenylhydrazine propanone-2,4-dinitrophenylhydrazone  HYPERLINK "http://www.drbateman.net/asa2sums/sum4.5/Photo_092305_006.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/Photo_092305_006_small.jpg" \* MERGEFORMATINET The yellow orange 2,4-dinitrophenylhydrazine solution forms a yellow orange precipitate. This is a condensation reaction (note water molecule formed). 4.8.2c(iv) Describe how, if at all, ethanal , ethanol and butan-2-one react with 2,4-dinitrophenylhydrazine using equations and describe what is seen. Hydrazones are derivatives (derived from the original aldehyde or ketone). Hydrazones are crystalline solids which can be purified easily. Their high melting points are easy to find and are used to identify the original carbonyl compound. Task 4.8.2c(iv) substancemelting point of hydrazone/oCethanal164propanal156pentan-2-one141pentan-3-one156cyclohexanone162What are the identities of the following: Compound A forms a yellow precipitate with 2,4-dinitrophenylhydrazine and an orange precipitate with Fehlings solution. When the yellow precipitate is purified it melts at 156oC. Compound B forms a yellow precipitate with 2,4-dinitrophenylhydrazine but does not form a silver mirror with Tollens reagent. When the yellow precipitate is purified it melts at 156oC. Compound C forms a yellow precipitate with 2,4-dinitrophenylhydrazine and an orange precipitate with Fehlings solution. When the yellow precipitate is purified it melts at 163oC. 4.8.2c(v) Describe and carry out the iodoform reaction with carbonyl compounds and iodine in the presence of alkali [or potassium iodide and chlorate(I)] (oxidation) Ethanal, ethanol or any methyl ketone can react in this reaction. A pale yellow precipitate of iodoform which has an antiseptic smell is the result of a positive test. There are 3 stages: (i) oxidation (this stage may not be needed) CH3CH(OH)- + I2 ----> CH3CO- +2H+ + 2I- (ii) substitution CH3CO- + 3I2 -----> CI3CO- + 3H+ + 3I- (iii) hydrolysis CI3CO- + OH- -----> CHI3 + -COO- iodoform A similar reaction occurs with KI and ClO- because ClO- can oxidise I- to I2 and CH3CH(OH)- to a methyl ketone.  HYPERLINK "http://www.drbateman.net/asa2sums/sum4.5/Photo_092305_007.jpg"  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/Photo_092305_007_small.jpg" \* MERGEFORMATINET A pale yellow precipitate of iodoform is formed. In summary the test detects the group CH3-C=O or a group which can be oxidised to this. | Task 4.8.2c(v) Describe how iodine reacts with ethanal, propanone, pentan-3-one and ethanol. 4.8.3. Carboxylic acids 4.8.3aThe carboxyl functional group  Task 4.8.3a Draw fully displayed structural formulae for the acids above and describe one with 5 carbon atoms. 4.8.3b Physical properties of carboxylic acids acidBoiling point/oCSolubility/(g/100g H2O)Pentanoic acid1874.97Hexanoic acid2051.08Octanoic acid2390.07 Carboxylic acids all have polar molecules. They can form strong hydrogen bonds with each other and with water. They therefore have high boiling points and the smaller molecules are very soluble. The first four are soluble in all proportions. The influence of hydrogen bonds decreases as molecules lengthen so solubility decreases. Task 4.8.3b State and explain the trends in boiling point and solubility in the acids in the table. 4.8.3c Preparation of carboxylic acids primary alcohol ethanol C2H5OHaqueous potassium dichromate VI dilute sulphuric acidboil under reflux forcing conditions HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/sum5.5.htm" \l "Carboxylic acids#Carboxylic acids" carboxylic acid ethanoic acid CH3COOHaldehyde ethanal CH3CHOaqueous potassium dichromate VI dilute sulphuric acidboil under reflux forcing conditions HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/sum5.5.htm" \l "Carboxylic acids#Carboxylic acids" carboxylic acid ethanoic acid CH3COOHnitrile ethanonitrile CH3CNwateracidic conditions heat under reflux HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/sum5.5.htm" \l "Carboxylic acids#Carboxylic acids" carboxylic acid ethanoic acid CH3COOHester ethyl ethanoate CH3COOC2H5waterconc. sulphuric acid HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/sum5.5.htm" \l "Primary alcohols#Primary alcohols" alcohol,  HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/sum5.5.htm" \l "Carboxylic acids#Carboxylic acids" acid ethanol, ethanoic acid C2H5OH, CH3COOHarene methylbenzene C6H5CH3potassium manganate VIIalkaline conditions heat under refluxbenzoic acid C6H5COOHgrignard reagent ethylmagnesiumbromide C2H5MgBrcarbon dioxide CO2in ether solution followed by dilute acid HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/sum5.5.htm" \l "Carboxylic acids#Carboxylic acids" carboxylic acid propanoic acid C2H5COOHacid chloride ethanoyl chloride CH3COClwater H2O. HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/sum5.5.htm" \l "Carboxylic acids#Carboxylic acids" carboxylic acid ethanoic acid CH3COOH Task 4.8.3c Write balanced equations for each of the reactions making acids with one more C atom than shown above. Give the displayed structural formula for each organic reactant and product. Draw suitable apparatus for one of the above preparations. 4.8.3d(i) Carboxylic acids with lithium aluminium hydride Lithium aluminium hydride, lithium tetrahydridoaluminate(III) reduces acids to alcohols. LiAlH4 is dissolved in dry ether. Water is added at the end of the reaction to destroy any remaining LiAlH4. This is a reduction reaction. CH3 COOH + 4H. -----> CH3 CH2OH + H2O Task 4.8.3d(i).1 Write equations to show how HCOOH and C3H7COOH react with LiAlH4 dissolved in dry ether? Task 4.8.3d(i).2 Write equations to show how you can make propan-1-ol and pentan-1-ol from carboxylic acids? 4.8.3d(ii) Carboxylic acids with sodium carbonate and sodium hydrogencarbonate The acid is neutralised in both cases with the formation of carbon dioxide. This can be used in analysis to detect carboxylic acids. These are neutralisation reactions. 2CH3COOH + Na2CO3 ---> 2CH3COONa + H2O + CO2 sodium ethanoate CH3COOH + NaHCO3 ---> CH3COONa + H2O + CO2 Task4.8.3d (ii) Write equations to show other examples of the neutralisation of carboxylic acids and name the organic reactants and products. Draw displayed structural formulae for the products in the reactions above. 4.8.3d(iii) Carboxylic acids with phosphorus pentachloride CH3COOH (l) + PCl5 (s) -------------> CH3COCl (l) + POCl3 (l) + HCl (g) ethanoyl chloride (an acyl halide)  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/ethanoicacid.jpg" \* MERGEFORMATINET   INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/addpcl5.jpg" \* MERGEFORMATINET   INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/addpcl52.jpg" \* MERGEFORMATINET   INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum4.5/steamyfumes.jpg" \* MERGEFORMATINET  4.8.3d(iv)Carboxylic acids with alcohols An ester is the product when acid and alcohol are heated under reflux with conc. H2SO4 catalyst. CH3 COOH + CH3 CH2OH -----> CH3 COOCH2CH3 + H2O ester (sweet fruity smell)  HYPERLINK "http://www.drbateman.net/asa2sums/sum4.5/tasks4.5/task4.5bii.htm" Task 4.8.3d(iv).1 4.8.4. Carboxylic acid derivatives 4.8.4a Derivative functional groups Acyl chlorides R-C=O e.g. ethanoyl chloride CH3-C=O | | Cl Cl Esters R-C=O e.g. methyl ethanoate CH3-C=O | | OR OCH3 Task 4.8.4a Give names and structural formulae for 5 acid chlorides and 5 esters. 4.8.4b Acyl chlorides These can be seen simply as nucleophilic substitutions. H O | || H-O: C Cl ( ( | ( CH3 However they can also be viewed as nucleophilic additions followed by elimination.  with water CH3COCl (l) + H2O (l) -------------> CH3COOH (l) + HCl (g) ethanoic acid with alcohols CH3COCl + C2H5OH ------------> CH3CO2C2H5 + HCl ethyl ethanoate with ammonia iii) CH3COCl + NH3 -----------> CH3CONH2 + HCl ethanamide with primary amines ii) CH3COCl + 2RNH2 ----------> CH3CONHR + RNH3Cl an amide Task 4.8.4b.1 Draw diagrams to show the electron distribution around CH3COCl, H2O, C2H5OH, NH3 and RNH2. Task 4.8.4b.1 Write equations to show reactions for ethanoyl chloride with methanol, methylamine, propan-2-ol. 4.8.4c(i) Esters hydrolysis with acid Hydrolysis of an ester is possible if conc. sulphuric acid catalyst is used. CH3COOCH2CH3 + H2O <-----> CH3COOH + C2H5OH This is a reversible reaction. Starting from either side results in an equilibrium position being established. 4.8.4c(ii) Esters hydrolysis with alkali The hydrolysis reaction above also takes place in the presence of an alkali such as sodium hydroxide. In this case however the ethanoic acid formed reacts with sodium hydroxide to form sodium ethanoate. The reaction now proceeds to completion as ethanoic acid is removed. CH3COOCH2CH3 + NaOH ( CH3COONa + C2H5OH The salt formed is a suitable soap if the carbon chain is long enough. Task 4.8.4c(ii).1 Write equations for the acid hydrolysis of ethyl methanoate and the alkaline hydrolysis of methyl ethanoate. Describe and explain the differences in yield in these reactions. Uses of esters, oils and fats Esters find a use as food flavourings because of their characteristic fruity smells. Ethyl methanoate is used in raspberry essence. 3-methylbutylethanoate is used in pear essence. Margarine is made from an ester of a long chain carboxylic acid containing carbon to carbon double bonds. This unsaturation makes the original ester a liquid oil. A typical source is peanuts or sunflower seeds. The amount of unsaturation is reduced in an addition reaction with hydrogen using a nickel catalyst. The resulting edible solid fat is margarine.  HYPERLINK "http://www.drbateman.net/asa2sums/sum5.5/Fatsnoils.ppt" The nature of fats and oils and saturation. (requires Powerpoint) Essential oils are so called because they are extracted from the essence of plants. The bark of Birch trees can be used to make oil of wintergreen, of use in relief of muscle pain. This is methyl-2-hydroxylbenzoate. Many of these essential oils are hydrocarbons or simple derivatives. Limonene can be separated from citrus peel. It is a methyl cyclohexene with a CH3CCH2 group attached. The chemistry involved in the production of soaps and soapless detergents Detergent- A substance that acts as a cleaning agent, improving the ability of water to wash things. Why is a detergent necessary? Though very effective at removing water-soluble dirt (hydrophilic), water is poor at removing material that does not dissolve in water (hydrophobic). The main problem is caused by greasy fats and carboxylic acids, which tend to bind other dirt particles to the skin or fabric. This prevents them being washed away by water. A detergent works by enabling water to mix with and remove greasy materials. Types of detergents (i) Soapy detergents (ii) Soapless detergents All detergents form a lather easily when shaken with PURE water. But the soapy detergent forms a lather with greater difficulty with tap water (tap water 300 mg/litre Ca2+ ); that is, a lather is only possible if a lot of soap is used, so in effect the soap is wasted in hard water. On the other hand, the soapless detergent forms a lather readily in hard water. These differences can be explained if the chemical nature of these materials is considered. Soapy detergents Animal fats are in fact esters made from long chain carboxylic acids and the compound glycerol. The alkaline hydrolysis or saponification (soap making) of animal fats gives glycerol and the sodium or potassium salt of the carboxylic acid. It is the salt which is the soap.  O //  R-C \ O-Na+ (R is the hydrophobic hydrocarbon chain) (e.g. toilet soap, gels in shampoos, shaving creams especially K+ salts) The charged -COO- group (carboxylate ion) at the end of a soap enables it to dissolve in water. Water molecules attach themselves to this end of the soap molecule via hydrogen bonds and the oil/ grease molecules attach around the alkyl with Van der Waals forces. The forces between water and grease are thus much increased, so that the grease is lifted off the surface in the form of small globules. These can be rinsed away. Advantages: Reaction of soap is more favourable with skin- more agreeable than with other detergents. Disadvantages: They do not remove some types of dirt well They do not clean very efficiently in hard water, as they react with calcium and magnesium ions to form insoluble calcium/ magnesium salts - scum. The scum is insoluble calcium or magnesium salt. 2R-COONa (aq) + Ca2+(aq) -----> Ca(R-COO)2(s) + 2Na+(aq) Made from vegetable/ animal fats - often expensive Soapless detergents These are very much synthetic materials, they work in a similar way to soaps but a sulphonate group (-SO2-O-) or sulphate group (-O-SO2-O) replace the carboxylate group as the hydrophilic component. The reaction of oil and concentrated sulphuric acid will produce a soapless detergent. O O || || R-O-S-O-Na+ also R-C6H4-S-O-Na+ || || O O (e.g. dishwasher powder, washing powder) The process of sulphonation gives rise to these detergents. Advs: The Ca2+/ Mg2+ compounds formed with soapless detergents are more soluble in water. Thus there is no wastage in hard water. Made from the by-products of oil refining, therefore quite cheap to make. Disadvantages: First soapless detergents were not biodegradable- the side chains cannot be degraded. Thus when discharged in rivers, the microorganisms present in the water can not destroy them. Thus causing foaming in rivers and streams. This has been overcome by modifying the structure of the detergents. Chains without branches were introduced which are biodegradable. Task 4.8.4c(ii).2 In the following molecules on the web page below explain if they are soapy or soapless, which part of the molecule dissolves in water and which part in oil and state what if anything would happen if calcium ions were present.  HYPERLINK "http://www.elmhurst.edu/~chm/vchembook/558detergent.html" http://www.elmhurst.edu/~chm/vchembook/558detergent.html 4.8.4c(iii) Transesterification This process changes one ester into a different ester through a reaction with an alcohol. The new ester can have more desirable properties. Biodiesel Chip fat has the advantages of a biofuel as it comes from plants e.g. Sunflowers and can be used as a form of diesel (after filtering out the burnt food). However it is a rough, viscous and smelly fuel. A better quality diesel is made by transesterification using NaOH as a catalyst. CH2OOCR CH2OH | | 3CH3OH + CHOOCR ( CHOH + 3RCOOCH3 | | CH2OOCR CH2OH Poor quality chip fat diesel gycerol Good quality diesel The glycerol is a valuable product of use in the cosmetics and pharmaceutical industries. The new ester (diesel) is purified by distillation. Low fat spread The hydrogenation of vegetable oils with a nickel catalyst can be used to make margarine. Healthy unsaturated fats in margarine can replace less healthy saturated fats in butter. However hydrogenation can form trans-fats where hydrogen has been added in the trans-position across a double bond. Trans-fats are now known to cause as much a problem as saturated fats. Transesterification changes liquid vegetable oils into solids suitable for margarine without forming trans-fats. ROH + R1COOR2 ( R1OH + RCOOR2 liquid oil solid fat Task 4.8.4c(iii) Explain the health and environmental benefits of transesterification. 4.8.4d Condensation polymers The formation of polyesters Molecules with two carboxyl groups can join to molecules with two hydroxyl groups to form polyesters. These polyesters are important for artificial fibres. nHOOCCH2(CH2)2CH2COOH + nHOCH2 (CH2)4CH2OH ------> monomer 1,6-hexandioic acid monomer hexan-1,6-diol -(OCCH2(CH2)2CH2COOCH2 (CH2)4CH2O)n- polymer polyhexylhexanoate ethane-1,2-diol H-O-CH2-CH2-O-H benzene- 1,4-dicarboxylic acid H-O-COC6H4-CO-O-Hpolyester terylene H-O-(COC6H4-CO- O-CH2-CH2-O)n-Hstability to light resistance to abrasion high tensile strength low melting pointnet curtains conveyor and drive belts ropes, safety belts permanent pleatingTask4.8.3d(iv).2 Redraw the full structures of the alcohols, acids and esters above showing all bonds. 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