Topic 5.

5 Organic chemistry analysis, synthesis and application

(a) Organic analysis(i) Functional groups functional group -C=C-Cl reagent conditions bromine in inert solvent warm with NaOH(aq) add HNO3 then AgNO3 then NH3 (aq) warm with NaOH(aq) add HNO3 then AgNO3 then NH3 (aq) warm with NaOH(aq) add HNO3 then AgNO3 then NH3 (aq) add solid PCl5 warm with acidified aqueous potassium dichromate K2Cr2O7 warm with acidified aqueous conc. potassium dichromate K2Cr2O7 result of positive test orange bromine decolourised white ppt. of AgCl soluble in dil. NH3 (aq) cream ppt. of AgBr soluble in conc NH3 (aq) yellow ppt. of AgI Insoluble in conc NH3 (aq) acrid steamy fumes of HCl orange colour changes to green product tests +ve for -CHO orange colour changes to green product does not test +ve for -CHO no change yellow ppt. of hydrazone no change in blue colour yellow ppt. of hydrazone red/brown ppt of Cu2O forms

-Br

-I -OH primary -CH2-OH secondary -CH-OH | tertiary | -C-OH | -C=O | -CHO

warm with acidified aqueous conc. potassium dichromate K2Cr2O7 add 2,4-dinitrophenylhydrazine warm with Fehling's solution add 2,4-dinitrophenylhydrazine warm with Fehling's solution

-COOH -C=O -CH-OH | | add iodine then aqueous NaOH CH3 CH3 ethanal ethanol

warm with AgNO3(aq) in NH3(aq) add NaHCO3

silver mirror forms effervescence CO2 formed yellow ppt. and antiseptic smell of iodoform

Task 5.5a.1 Complete a copy of the table below with names and structural formulae: functional group compound giving positive test similar compound with giving negative test

Task 5.5a.2 Write an equation for each of the reactions above. Task 5.5a.3 Predict the result of carrying out an iodoform test on the following compounds: methanol, ethanol, propan-1-ol, methanal, ethanal, propanone. (ii) Interpretation of physical data * A pure solid can be identified by its melting temperature, a pure liquid by its boiling temperature. Aldehydes and ketones produce solid derivatives with 2,4dinitrophenylhydrazine (hydrazones) which have high melting points. The melting points of these derivatives can be used to identify the original ketone or aldehyde. substance propanal pentan-2-one pentan-3-one boiling point/oC 48 102 102 melting point of hydrazone/oC 156 141 156

What 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. The percentage by mass of Carbon and Hydrogen in a hydrocarbon can be found by the following method; A known mass of the compound heated in a stream of pure, dry oxygen in the presence of copper (II) oxide when hydrogen and carbon are oxidised, to steam and carbon dioxide respectively. The steam absorbed in weighed calcium chloride tubes, and carbon dioxide absorbed in weighed bulbs of concentrated potassium hydroxide solution. The masses of carbon and hydrogen in the sample are found from the increases in mass. Draw suitable labelled apparatus for the above procedure. If 7.80g of a hydrocarbon causes calcium chloride to increase in mass by 5.40g and potassium hydroxide to increase in mass by 26.4g what was the formula of the hydrocarbon? 5.5a(iii)(a) interpret simple fragmentation patterns from a mass spectrometer An organic compound produces ions in a mass spectrometer. The ions generate pulses of electric current which are sent as signals to a computer (or chart plotter) to be displayed as a mass spectrum. On the spectrum the large peak on the right is the parent molecular ion and this indicates the relative molecular mass of the compound. In the spectrometer the molecules are fragmented into positive ions which form a pattern which depends on the structure of the molecule. e.g. ether

Another compound of relative molecular mass 46 also contains carbon, hydrogen and oxygen has the mass spectrum below. Identify each fragment and the structural

formula.

Sketch the mass spectrum of propanal showing the masses of each fragment. Task 5.5a(iii)a 5.5a (iii) (b) interpret simple infra-red spectra The bonds in organic molecule absorb infra-red radiation. This happens when the frequency of the radiation matches the natural frequency of vibrations in the bonds. These might be stretching, or bending vibrations. A spectrometer shines infra-red light at a sample of an organic material and measures how much of the light is absorbed. A measure of the frequency (wavenumber) is displayed in the spectrum. Each bond has its own frequency (wavenumber) and this can be used to identify the bonds present in a compound. bond
C-H C-C C=O C-O C-Cl O-H N-H

wavenumber/cm-1 seen on spectrum

2840 - 3095 1610 - 1680 1680 - 1750 1000 - 1300 700 - 800 3233 - 3550 2500 - 3300 3100 - 3500

Infra-red spectrum for propanone Is substance A in the infra-red spectrum below most likely to be ethyl ethanoate or

butane? Task 5.5aiiib 5.5a(iii)(c) Low resolution nuclear magnetic resonance spectra (NMR) Hydrogen atoms can be detected using this sort of spectrometry. The nucleus of a hydrogen atom, the proton, spins and so has a magnetic moment. This can be aligned or not aligned with a magnetic field . When electromagnetic radiation of the right frequency is applied resonance occurs and the protons flip from one state to the other and absorb energy. This absorption of energy is used to detect protons in organic compounds. The exact resonance frequency for a proton (hydrogen atom) depends on its environment. For example the frequency is different for hydrogen atoms in CH3, CH2 , C6H5- and in O-H. Trimethylsilane, TMS, is used as a standard. The distance in the spectrum from the TMS peak is called the chemical shift. Type of proton R-CH3 R-CH2 R-CH2-OC6H5-O-H Chemical Shift (ppm) 0.9 1.3 4.0 7.5 5.0

-CHO

9.5

To which functional groups do the protons in the following NMR spectrum belong? Identify the compound.

Sketch an NMR spectrum for propanal. An excellent guide to low resolution nmr. 5.5a (iii) (d) The interpretation of simple ultra-violet/visible spectra. Some chemical structures absorb electromagnetic radiation in the ultra violet part of

the spectrum. These include conjugated (contain alternate double and single bonds) dienes. E.g. 1,3-butadiene. The ultraviolet absorption spectrum for 2,5-dimethyl-2,4hexadiene is shown below.

Ultra-violet wavelengths are from about 200nm to about 400nm. Visible light has wavelength between 400nm and 800nm. -carotene, which gives carrots their orange colour absorbs at 497nm. Lycopene, which gives tomatoes their red colour, absorbs at 505nm. Both of these compounds have 11 conjugated double bonds. 5.5b(i)Pathways for organic synthesis
Alkanes Organic reactant Alkane ethane C2H6 Alkane ethane C2H6 Alkenes Organic reactant Alkene ethene C2H4 unsymmetric alkene prop-1-ene Reagent halogen bromine Br2 hydrogen halide hydrogen bromide Conditions inert solvent inert solvent Organic Products halogenoalkane 1,2-dibromoethane CH2BrCH2Br halogenoalkane 2-bromopropane Reagent halogen bromine Br2 halogen chlorine Cl2 Conditions UV light inert solvent UV light inert solvent Organic Products halogenoalkane bromoethane CH3CH2Br halogenoalkane chloroethane CH3CH2Cl

CH3CHCH2 Alkene ethene C2H4 Arenes Organic reactant arene benzene C6H6 arene methylbenzene C6H5CH3 arene benzene C6H6 arene benzene C6H6 arene benzene C6H6 diazonium salt benzen diazonium chloride C6H5N2+Cldiazonium salt benzene diazonium chloride C6H5N2+Clphenylamine C6H5NH2 nitrobenzene C6H6NO2 phenol C6H5OH phenol C6H5OH phenol C6H5OH

HBr potassium manganate(VII) KMnO4 alkaline solution

CH3CHBrCH3 ethane-1,2-diol CH2OHCH2OH

Reagent nitric acid sulphuric acid potassium manganate VII chloroalkane chloromethane CH3Cl acid chloride ethanoyl chloride CH3COCl halogen bromine Br2 phenol C6H5OH 2-naphthol nitrous acid HNO2 concentrated hydrochloric acid and tin HCl and Sn sodium hydroxide bromine ethanoyl chloride

Conditions heat under reflux below 60oC concentrated acids alkaline conditions heat under reflux anhydrous aluminium chloride as catalyst anhydrous aluminium chloride as catalyst anhydrous aluminium chloride as catalyst below 5oC

Organic Products nitrobenzene C6H5NO2 benzoic acid C6H5COOH arene methylbenzene C6H5CH3 ketone methylphenylketone C6H5COCH3
halogenoarene bromobenzene

C6H5Br azo dye C6H5N2C6H5OH azo dye C10H6(OH)N2C6H5 diazonium salt benzenediazonium chloride C6H5N2+Clphenylamine C6H5NH2 sodium phenoxide C6H5ONa 2,4,6-tribromophenol C6H2Br3OH ester ethylbenzoate

below 5oC below 5oC NaNO2 and dil HCl heat under reflux aqueous aqueous

C6H5COOC2H5 Primary alcohols Organic reactant primary alcohol ethanol C2H5OH primary alcohol ethanol C2H5OH primary alcohol ethanol C2H5OH primary alcohol ethanol C2H5OH primary alcohol ethanol C2H5OH primary alcohol ethanol C2H5OH primary alcohol ethanol C2H5OH Reagent aqueous potassium dichromate VI dilute sulphuric acid aqueous potassium dichromate VI dilute sulphuric acid hydrogen halide hydrogen bromide HBr Conditions Organic Products aldehyde ethanal CH3CHO carboxylic acid ethanoic acid CH3COOH halogenoalkane bromoethane C2H5Br halogenoalkane iodoethane C2H5I ester ethyl ethanoate CH3COOC2H5 ester ethyl ethanoate CH3COOC2H5 halogenoalkane chloroethane C2H5Cl

distil product mild conditions

boil under reflux forcing conditions

heat under reflux HBr formed in situ from KBr and conc. H2SO4

phosphorus and iodine

red phosphorus

carboxylic acid ethanoic acid CH3COOH acid chloride ethanoyl chloride CH3COCl phosporus pentachloride

concentrated H2SO4

.dry

Secondary alcohols Organic reactant secondary alcohol propan-2-ol Reagent aqueous potassium dichromate VI sulphuric acid Conditions conc. acid heat under reflux Organic Products ketone propanone CH3COCH3

CH3CH(OH)CH3 secondary hydrogen halide alcohol hydrogen bromide propan-2-ol HBr CH3CH(OH)CH3 secondary carboxylic acid alcohol ethanoic acid propan-2-ol CH3COOH CH3CH(OH)CH3 secondary acid chloride alcohol ethanoyl chloride propan-2-ol CH3COCl CH3CH(OH)CH3 secondary alcohol phosphorus and propan-2-ol iodine CH3CH(OH)CH3 secondary alcohol phosporus propan-2-ol pentachloride CH3CH(OH)CH3 Tertiary alcohols Organic reactant tertiary alcohol 2-methylpropan2-ol (CH3)3OH Reagent hydrogen halide hydrogen bromide HBr Conditions heat under reflux HBr formed in situ from KBr and conc. H2SO4 Organic Products halogenoalkane 2-bromo-2methylpropane (CH3)3Br ester CH3COOC(CH3)3 heat under reflux HBr formed in situ from KBr and conc. H2SO4 halogenoalkane 2-bromopropane CH3CH2(Br)CH3 ester 2-propylethanoate CH3COOCH(CH3)2 ester 2-propylethanoate CH3COOCH(CH3)2 halogenoalkane 2-iodopropropane CH3CH(I)CH3 halogenoalkane 2-chloropropane CH3CH2(Cl)CH3

concentrated H2SO4

red phosphorus

dry

tertiary alcohol carboxylic acid 2-methylpropanethanoic acid 2-ol CH3COOH (CH3)3COH

heat concentrated H2SO4

tertiary alcohol acid chloride 2-methylpropanethanoyl chloride . 2-ol CH3COCl (CH3)3OH tertiary alcohol 2-methylpropan- phosphorus and 2-ol iodine (CH3)3OH red phosphorus

ester CH3COOC(CH3)3 halogenoalkane 2-iodo-2methylpropropane (CH3)3I

tertiary alcohol 2-methylpropan- phosporus 2-ol pentachloride (CH3)3OH Carboxylic acids Organic reactant carboxylic acid ethanoic acid CH3COOH carboxylic acid ethanoic acid CH3COOH carboxylic acid ethanoic acid CH3COOH carboxylic acid ethanoic acid CH3COOH Primary amines Organic reactant primary amine ethylamine C2H5NH2 primary amine ethylamine C2H5NH2 Halogenoalkanes Organic reactant halogenoalkane bromoethane C2H5Br halogenoalkane bromoethane C2H5Br Reagent hydroxide ion sodium hydroxide NaOH hydroxide ion potassium hydroxide Reagent Reagent alcohol ethanol C2H5OH

dry

halogenoalkane (CH3)3Cl

Conditions heat concentrated H2SO4 dissolved in dry ether

Organic Products ester ethyl ethanoate CH3COOC2H5 alcohol ethanol C2H5OH acid chloride ethanoyl chloride CH3COCl salt sodium ethanoate CH3COONa

lithium aluminium hydride

phosphorus pentachloride sodium carbonate or sodium hydrogencarbonate

dry

Conditions aqueous solution

Organic Products salt alkyl ammonium chloride C2H5NH3+Clamide N-ethylethanamide CH3CONHC2H5

acid hydrochloric acid HCl acid chloride ethanoyl chloride CH3COCl

Conditions

Organic Products alcohol ethanol C2H5OH alkene ethene C2H4

aqueous solution

heat and distil off product ethanolic solution

KOH halogenoalkane bromoethane C2H5Br halogenoalkane bromoethane C2H5Br halogenoalkane bromoethane C2H5Br cyanide ion potassium cyanide KCN ammonia heat under reflux in ethanolic solution nitrile propanonitrile C2H5CN

amine heat with concentrated ammonia ethylamine etc in a sealed tube C2H5NH 2 ; (C2H5)2NH etc in solution in dry ether grignard reagent ethylmagnesiumbromide C2H5MgBr

magnesium Mg

Grignard reagent Organic reactant Reagent Conditions in ether solution followed by dilute acid in ether solution followed by dilute acid Organic Products primary alcohol propan-1-ol C2H5CH2OH secondary alcohol butan-2-ol CH3CH2CH(OH)CH3 tertiary alcohol 2-methylpropan-2-ol (CH3)3OH carboxylic acid propanoic acid C2H5COOH

grignard reagent methanal ethylmagnesiumbromide HCHO C2H5MgBr grignard reagent aldehyde ethylmagnesiumbromide ethanal C2H5MgBr CH3CHO

grignard reagent ketone in ether solution followed by ethylmagnesiumbromide propan-2-one dilute acid C2H5MgBr (CH3)2CO grignard reagent carbon ethylmagnesiumbromide dioxide C2H5MgBr CO2 Ketones Organic reactant ketone propanone (CH3)2CO ketone propanone (CH3)2CO ketone propanone Reagent Conditions in alkaline conditions potassium cyanide used as source of HCN dil. sulphuric acid in ether solution followed by dilute acid

Organic Products alcohol, nitrile 2-hydroxy -2methylpropanonitrile CH3C(OH)(CH3)CN 2,4dinitrophenyhydrozone C6H3(NO2)2NHNC(CH3)2 halogenoalkane tri-chloromethane

hydrogen cyanide 2,4dinitrophenylhydrazine C6H3(NO2)2NHNH2

iodine or sodium iodide and alkaline conditions chloate(I)

(CH3)2CO ketone propanone (CH3)2CO ketone propanone (CH3)2CO Aldehydes Organic reactant aldehyde ethanal CH3CHO aldehyde ethanal CH3CHO aldehyde ethanal CH3CHO aldehyde ethanal CH3CHO aldehyde ethanal CH3CHO aldehyde ethanal CH3CHO Reagent Conditions sodium borohydride NaBH4 aqueous solution

(iodoform) secondary alcohol propan-2-ol CH3CH(OH)CH3 secondary alcohol propan-2-ol CH3CH(OH)CH3

Lithium aluminium hydride dry LiAlH4 ether solution

Organic Products

hydrogen cyanide 2,4dinitrophenylhydrazine C6H3(NO2)2NHNH2 ammoniacal silver nitrate solution (Tollen's reagent)

in alkaline conditions alcohol, nitrile 2potassium cyanide hydroxypropanonitrile used as source of CH3CH(OH)(CN) HCN dilute sulphuric acid 2,4dinitrophenyhydrozone C6H3(NO2)2NHNCHCH3 carboxylic acid ethanoic acid CH3COOH halogenoalkane tri-chloromethane (iodoform) alcohol ethanol C2H5OH alcohol ethanol C2H5OH

warm in water bath

iodine or sodium iodide and alkaline conditions chlorate(I) sodium borohydride NaBH4 aqueous solution

Lithium aluminium hydride dry LiAlH4 ether solution

Acid chlorides Organic reactant acid chloride ethanoyl chloride CH3COCl acid chloride ethanoyl chloride CH3COCl Reagent water H2O alcohol ethanol CH3CH2OH Conditions . Organic Products carboxylic acid ethanoic acid CH3COOH ester ethyl ethanoate CH3COOC2H5

no water

acid chloride ethanoyl chloride CH3COCl acid chloride ethanoyl chloride CH3COCl Nitriles

ammonia NH3 primary amine phenylamine C6H5NH2

conc. ammonia

amide ethanamide CH3CONH2 amide N-phenylethanamide CH3CONHC6H5

Organic reactant Reagent nitrile ethanonitrile CH3CN nitrile ethanonitrile CH3CN nitrile ethanonitrile CH3CN Amides Organic reactant amide ethanamide CH3CONH2 amide ethanamide CH3CONH2 Esters Organic reactant ester ethyl ethanoate CH3COOC2H5 ester ethyl ethanoate CH3COOC2H5 Reagent water Conditions Reagent phosphorus V oxide water

Conditions acidic heat under reflux

Organic Products carboxylic acid ethanoic acid CH3COOH

water

salt alkaline heat under reflux sodium ethanoate CH3COONa amine ethylamine CH3CH2NH2

lithium aluminium hydride dry ether solution

Conditions .

Organic Products nitrile ethanonitrile CH3CN amine methylamine CH3NH2

bromine

aqueous alkali

Organic Products alcohol, acid ethanol, ethanoic acid C2H5OH, CH3COOH alcohol ethanol, sodium ethanoate C2H5OH, CH3COONa

conc. sulphuric acid

water

aqueous sodium hydroxide

5.5b (ii) Apparatus and safety in organic synthesis Organic compounds may be hazardous because of: Flammability. Use in small amounts avoids the undue risk of fire. Avoid naked flames. Use electrical heaters Toxicity The use of small amounts, fume cupboards, gloves and normal laboratory safety procedures reduces the risk of harmful amounts of a chemical entering the body by inhalation, ingestion or by skin absorption. Non-biodegradability Some substances do not decay naturally in the environment. The hazard is reduced by using small quantities, and pouring waste solvents in a suitable container rather than pouring it down the sink. When carrying out organic reactions safety goggles should always be worn. Some common apparatus for organic preparation: Quickfit apparatus such as a pear shaped flask

Liebig condenser T connector

thermometer holder

Separating funnel delivery tubes

5.5b (iii) Practical techniques Mixing can involve adding a liquid to a solid or another liquid using a separating funnel. Mixing can involve adding a gas to a liquid through a delivery tube into the liquid. boiling under reflux, Practice setting up reflux apparatus. (Needs Microsoft Word.)

fractional distillation,

Filtration under reduced pressure (filter pump and Buchner funnel an flask),

Recrystallisation This is used to purify an impure organic solid. 1. Choose a suitable solvent. The solvent is suitable if the product is insoluble in the cold solvent but soluble in the hot solvent. 2. Dissolve the impure sample in the minimum volume of hot solvent. 3. Filter the hot solution through hot apparatus and collect the filtrate. This removes solid impurities which were insoluble in the solvent. 4. Allow the filtrate to cool so that crystals of the product form. 5. Again filter the mixture under reduced pressure. Soluble impurities are now removed. 6. Wash the residue with a little cold solvent. 7. Dry the residue which should then be the pure product. Describe with a series of labelled diagrams how compound X can be purified using the information below. Solvent Solubility of X in cold solvent Solubility of X in hot solvent 0.02 gcm-3 0.06 gcm-3 3.65 gcm-3

water 0.01 gcm-3 50% water 50% ethanol 0.03 gcm-3 ethanol 0.06 gcm-3

Determination of melting temperature A pure solid has a sharp melting point which can be found in a data book. If a solid product has been purified it can be identified from its melting point or if we know what it is we can tell if it is pure. Impurities lower the melting point.

1. A liquid is chosen for the boiling tube so that its boiling point is well above the melting point of the solid. 2. The apparatus is set up as shown. 3. The apparatus is heated gently with stirring until the first solid is seen to melt when the temperature is recorded. 4. After the sample is melted it is allowed to cool. 5. When the first crystals of solid appear in the sample the temperature is recorded again. Comment on the purification of X by student A and B given the data below. MP of X in data book/oC MP of X by student A/oC 128 129 Mp of X by student B/oC 126

Determination of boiling temperature

In both apparatus the bulb of the thermometer is below the surface of the liquid but not touching the side of the glass. Heating with a variety of sources Heating with a naked Bunsen flame is a fire hazard with flammable organic compounds. Alternatives include using an electrically heated hot plate, using an electrical heating mantle which can surround a round bottom flask or using a water bath. Other apparatus 5.5b(iv) The principles of fractional distillation Raoult's Law Raoult's law states that the saturated vapour pressure of a component in a mixture is equal to the product of the mole fraction of that component and the saturated vapour pressure of that component when pure. For a mixture of A and B obeying Raoult's law pA = poA * XA where pA = partial vapour pressure of A in the solution poA = vapour pressure of pure A XA = mole fraction of A in the solution

mole fraction of A in mixture A+B, XA = nA/nA+nB nA= no. moles A nB= no. moles B. pT = poA * XA + poB * XB where pT = total vapour pressure This law is obeyed by mixtures of similar compounds. They form IDEAL SOLUTIONS. The substances A and B form an ideal solution if the intermolecular forces A----A, A----B, B----B are all equal. As these forces are alike the vapour pressure of an ideal mixture is not increased or decreased because the escape of molecules is neither helped nor hindered. Also for an ideal solution there is: (1) no enthalpy change on mixing; (2) no volume change on mixing. Diagrams for Idea Solutions

Task 5.5biv.1 Pure hexane has a vapour pressure of about 340 mmHg and pure pentane has a vapour pressure of about 310 mmHg. Sketch a vapour pressure composition graph and a boiling point composition graph for a mixture of these two compounds.

Fractional distillation This technique has a number of important applications: (1) used to separate the components of liquid air; The air is compressed and cooled to liquefy it. Fractions are oxygen -183oC, argon -186oC, and nitrogen -196oC. (2) used to separate fractions from petroleum; The fractions are bitumen >350oC, fuel oil 300 oC, diesel 240 oC, kerosene 200 oC, naptha 120 oC, petrol 40 oC, LPG <25 oC. (3) used to produce whisky and other alcoholic drinks. Fractions are ethanol 78 oC and water 100 oC. Principles of fractional distillation Fractional distillation relies on the fact that the composition of a two liquid mixture in equilibrium with its vapour is different in the liquid and vapour phases. Real mixtures are not ideal and show deviations from Raoult's law. The particles of one liquid surround those of the other and change the forces on them so affecting their tendency to escape from the liquid. (1) Negative from deviations Raoult's law: If the attractive forces between the different particles from the two liquids are stronger than the attractive forces in pure liquids, then the particles will be held in the liquid more strongly. Therefore fewer particles will escape, thus the vapour pressure will be lower than predicted by Raoult's law. Boiling points for any composition of this mixture will be higher than predicted.

(2) Positive deviations from Raoult's law: If the attractive forces between the different particles from the two liquids are weaker than the attractive forces in the pure liquids, then the particles will be held in the liquid less well. Therefore more particles will escape, thus the vapour pressure will be higher than predicted by Raoult's law. Boiling points for any composition of this mixture will be lower than predicted.

A plot of temperature against composition is needed to explain how fractional distillation works.

For a liquid mixture of composition C1 it will boil at temperature T. It will be in equilibrium with vapour at composition C2. Vapour C2 will condense and then boil to give a mixture richer again in B. Eventually the distillate will be pure B. The residue in the flask will be A. Task 5.5b(iv).2 Methanol has a boiling point of 338K and ethanol has a boiling point of 351K. Sketch a temperature composition curve for this mixture and use it to explain how they can be separated. State the names of the distillate and the residue. 5.5c(i) The solubility of pharmaceuticals Drugs can be made to target fatty tissue like lipids in the body. These chemicals will have a large number of CH3 or CH2 groups. The following pharmaceutical inhibits cholesterol synthesis and acts within fatty tissue.

Other pharmaceuticals like penicillin are targeted at non-fatty tissue and must be more water soluble. For this the molecules must contain hydroxyl groups to form hydrogen bonds to water or an ionic group. Penicillin-G shown below prevents the growth of cell walls in bacteria and so is an antibiotic. One draw back is that it is very soluble (due to its ionic group) and is eliminated very rapidly by the kidneys so has to be given in large doses.

Task 5.5c(i).1 Describe the inplications for solubility of ziagen, Aczone Gel and other drugs found at http://www.rxlist.com/drugs/alpha_a.htm 5.5c(ii) The use of organic fertilisers Inorganic fertilizers like ammonium nitrate and ammonium sulphate are very soluble, can be leached easily which may lead to the eutrophication of rivers and lakes. Other problems are that they decrease soil pH, and for osmotic reasons, cause burning and foliage decay in some plants. Urea is an organic fertilizer which only slowly releases nitrogen to the soil, has a high proportion of nitrogen and does not immediately change soil pH. It undergoes hydrolysis in the soil to form ammonia. H2N-CO-NH2 + H2O -----> CO2 +2NH3 The process is catalysed by urease made by soil bacteria. The ammonia is converted to nitrates in the soil which can then be absorbed by plants. Alternatives include manure, hoof and horn, or dried blood. Task 5.5c(ii).1 State steps in the process of eutrophication. Task 5.5c(ii).2 Explain equilibrium giving low pH. Task 5.5c(ii).3 Explain water loss to soil through osmosis. 5.5c(iii) 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. 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 || R-O-S-O-Na+ || O O || also R-C6H4-S-O-Na+ || 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. Disadvs: 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 5.5d(iii) 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. http://www.elmhurst.edu/~chm/vchembook/558detergent.html 5.5d(iv) Uses and properties of polymers
Monomer ethene CH2=CH2 Polymer polyethene -(CH2-CH2)nProperties low mp. soft, flexible Uses plastic bags, squeezy bottles, washing up bowls, buckets

propene CH3CH=CH2

polypropene -(CH(CH3) -CH2-)npolychloroethene (polyvinylchloride PVC) -(-CHCl-CH2-)npolytetrafluroethene -(-CF2-CF2-)n-

high tensile strength ropes, sacks water repellent carpets and curtains low melting point low density, ropes tougher than polyethene harder, less flexible than raincoats, guttering, floor polyethene, electrical tiles, packaging, covering insulator electrical wire low friction on surface non-stick coatings on frying pans moulded shapes coffee cups foam packaging

chloroethene (vinylchloride) CHCl=CH2 tetrafluroethene CF2=CF2 phenylethene (styrene) C6H5CH=CH2 ethane-1,2-diol H-O-CH2-CH2-OH benzene1,4-dicarboxylic acid H-O-COC6H5-COO-H hexanedioic acid HOOC-(CH2)4COOH 1,6-diaminohexane H2N-(CH2)6-NH2

poly(phenylethene) softens at low polystyrene temperature -(-CH(C6H5)-CH2-)n- thermal insulator

polyester terylene H-O-(COC6H5-COO-CH2-CH2-O)n-H

stability to light resistance to abrasion high tensile strength low melting point

net curtains conveyor and drive belts ropes, safety belts permanent pleating

polyamide (nylon6.6) HO-(OC-(CH2)4-COHN-(CH2)6-NH)n-H

high tensile strength low melting point low affinity for water resistance to abrasion

ropes, parachutes, stockings permanent pleating easy drying garments conveyor belts, brushes