CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Questions on Alkanes
1. State the balanced equations for the complete combustion (under standard conditions) of 2-methylbutane, C5H12 (boiling point: 28 oC), 3-methylpentane, C6H14, and octane, C8H18. 2. If the ratio of air to gasoline (petrol) entering a car engine is reduced then the amount of air pollution caused by oxides of nitrogen emitted in the exhaust gas is lowered. However, the concentration of two other air pollutants is increased. Identify these two pollutants and explain how they arise. 3. The first step in the reaction between methane and chlorine in the presence of ultraviolet light is the homolytic fission of the chlorine to chlorine single bond, ClCl(g), in gaseous chlorine. (a) Explain the meaning of the term homolytic fission. (b) Explain why homolytic fission occurs with the Cl-Cl bond in chlorine and not the C-H bond in methane. (c) State the name of the product formed when the Cl-Cl bond is broken homolytically and give its electron arrangement. (d) Explain why only a few homolytic fission reactions involving chlorine need to be successful in order to bring about the complete reaction between chlorine and methane to form chloromethane and hydrogen chloride.

4. The reaction between bromine and ethane occurs in the presence of ultraviolet light. (a) Explain why ultraviolet light is necessary for the reaction to proceed. (b) Describe, using equations, the stepwise mechanism of the reaction between one mol of bromine and one mol of ethane to form one mol of bromoethane and one mol of hydrogen bromide. (c) Describe how you could make pure 1,2-dibromoethane from bromine and ethane.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Answers
1. C5H12(l) + 8O2(g) 5CO2(g) + 6H2O(l) 2C6H14(l) + 19O2(g) 12CO2(g) + 14H2O(l) 2C8H18(l) + 25O2(g) 16CO2(g) + 18H2O(l) 2. The two pollutants are carbon monoxide and particles of solid carbon (particulates). They are formed as there is insufficient oxygen (present in the air inside the combustion chamber in the car) to bring about complete combustion of the gasoline. 3. (a) During homolytic fission the bond breaks symmetrically so that one electron forming the bond between two atoms becomes attached to one of the atoms and the other electron becomes attached to the other atom resulting in the formation of two radicals. (b) The ultraviolet light provides the energy to break the Cl-Cl bond homolytically. This energy, 243 kJ mol-1, is much less than the 413 kJ mol-1 of energy required to break a C-H bond. (c) The product is a chlorine (free) radical. The electron arrangement is 2.8.7. (d) Once a chlorine free radical is formed it reacts with a methane molecule to produce hydrogen chloride and a methyl radical. This methyl radical can react with another chlorine molecule to form chloromethane and generate a new chlorine radical which can then repeat the process. This is a propagation step. The formation of new radicals will only stop when a termination reaction occurs. (A termination step may be between two radicals or between a radical and an impurity or the walls of the reaction vessel). 4. (a) The ultraviolet light provides the energy to break the Br-Br bond in bromine homolytically. (b) Initiation: Br2(g) + ultraviolet light 2Br (g) . . Propagation: Br (g) + C2H6(g) C2H5 (g) + HBr(g) . . Propagation: C2H5 (g) + Br2(g) C2H5Br(g) + Br (g) . . Termination: C2H5 (g) + Br (g) C2H5Br(g) (there are other possible termination reactions) (c) React ethane with excess bromine in the presence of ultraviolet light. This would give a mixture of brominated products. For example, 1,1dibromoethane, 1,2 dibromoethane, 1,1,1- tribromoethane etc. The desired product, 1,2dibromoethane, would need to be separated from the mixture using fractional
.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

distillation (as they all have different boiling points) or by using some form of chromatography, e.g. HPLC, GC or GLC, (as they will all have different retention times).

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Questions on Alkenes
1. State the equation and name the organic product when propene reacts with: (a) hydrogen using a nickel catalyst at 180 oC. (b) chlorine gas in the absence of water.

2. Describe how you could distinguish practically between hexane and hex-3-ene by using a simple chemical reaction. Describe what you would observe in each case and state any relevant equations and name any products formed.

3. Ethanol is increasingly being produced commercially by the fermentation of crops in order to use as a biofuel in place of/in addition to gasoline (petrol). This is ecologically friendly in terms of greenhouse gas emissions but it is using up vast areas of land which could be used for food production. Ethanol can also be made by the hydration of ethene. State the equation for the hydration of ethene and state the necessary conditions for the reaction to occur.

4. (a) State the equation and name the organic product when but-2-ene reacts with hydrogen iodide. (b) Unlike the reaction with but-2-ene, the reaction of but-1-ene with hydrogen iodide is not on the IB Core. This is because in theory it can give two different organic products although in practice only one of them is formed. Deduce the identity of the two possible products.

5. (a) Draw the structure of the repeating unit of poly(chlorethene). (b) Deduce the structure of the repeating unit of poly(tetrafluoroethene). (c) Poly(tetrafluoroethene) is also known as Teflon or non-stick and it is used to make artificial joints for humans as well as coat frying pans. Suggest a reason why it is so unreactive.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Answers
1. (a) CH3CH=CH2(g) + H2(g) CH3CH2CH3(g) Product: propane. (b) CH3CH=CH2(g) + Cl2(g) CH3CHClCH2Cl(l) Product: 1,2-dichloropropane

2. Add a small amount of bromine water to each substance. The bromine will dissolve in the hexane to form a yellow-brown solution but no reaction takes place. The hex-3-ene solution will decolourise the bromine water. This is due to the addition of the bromine water to the double bond of the hex-3-ene to form 4bromohexan-3-ol. CH3CH2CH=CHCH2CH3(l) + Br2(aq) + H2O(l) CH3CH2CHBrCH(OH)CH2CH3(l) + HBr(aq) (The IB would also accept 3,4-dibromohexane, CH3CH2CHBrCHBrCH2CH3, as the product as this would be formed if no water is present).

3. H2C=CH2(g) + H2O(g) C2H5OH(l) Conditions: High temperature (usually about 570K) High pressure (usually about 60-70 atmospheres) Catalyst (concentrated H3PO4 on a surface of silicon dioxide)

4. (a) CH3CH=CHCH3(g) + HI(g) CH3CHICH2CH3(l) Product: 2-iodobutane (b) 1-iodobutane, CH2ICH2CH2CH3 and 2-iodobutane, CH3CHICH2CH3 5. (a) (CH2CHCl)n (b) (CF2CF2)n (c) The very strong C-F bond is difficult to break or the structure is such that there is no room around each carbon atom for other atoms to approach.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Questions on Alcohols
1. State the equations for the complete combustion of: (a) ethanol (b) propan-2-ol

2. Propan-2-ol and propan-1-ol can both be oxidized by a warm acidified solution of potassium dichromate(VI). (a) Describe what would be observed in both cases.

(b) State the IUPAC name of the product from the oxidation of propan-2-ol and state the simplified equation (use [O] to represent the oxygen from the acidified potassium dichromate(VI) solution).

(c) The half-equation for the reduction of the acidified dichromate(VI) ion is: Cr2O72(aq) + 14H+(aq) + 6e 2Cr3+(aq) + 7H2O(l) Deduce the full equation for the oxidation of propan-2-ol using acidified Cr2O72 ions. (d) State the IUPAC name of the two organic products that can be formed when propan-1-ol is oxidized by warm acidified potassium dichromate(VI) solution. (e) Explain why propan-1-ol can form two different organic products whereas propan-2-ol only forms one organic product when oxidized by acidified potassium dichromate(VI) solution. (f) Describe how you could separate the two organic products formed from the oxidation of propan-1-ol.

3. The precise use of language is important in chemistry. Many books state that tertiary alcohols, such as 2-methylpropan-2-ol, (CH3)3COH, are not readily oxidized. Evaluate this statement.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Answers
1. (a) C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) (b) CH3CH(OH)CH3 + 4O2(g) 3CO2(g) + 4H2O(l)

2. (a) In both cases the colour of the solution will turn from orange to green. A distinct smell due to the volatile organic products may be smelt. (b) Propanone CH3CH(OH)CH3(l) + [O] CH3COCH3(l) + H2O(l) (c) The two half-equations are: Cr2O72(aq) + 14H+(aq) + 6e 2Cr3+(aq) + 7H2O(l) and CH3CH(OH)CH3(l) CH3COCH3(l) + 2H+(aq) + 2e So the overall equation is: 3CH3CH(OH)CH3(l) + Cr2O72(aq) + 8H+(aq) 2Cr3+(aq) + 3CH3COCH3(l) + 7H2O(l) (d) Propanal and propanoic acid (e) Propan-1-ol is a primary alcohol whereas propan-2-ol is a secondary alcohol but this does not really explain it. The correct explanation is that, once the two hydrogen atoms have been removed from propan-2-ol to form the ketone, the carbon atom bonded to the oxygen atom contains no more hydrogen atoms to be removed so cannot be oxidized further. However in the case of propan-1-ol, the aldehyde formed, CH3CH2CHO, still contains a hydrogen atom bonded to the carbon atom attached to the oxygen. This means that further oxidation can occur as this hydrogen atom is removed to form a carboxylic acid. (f) Because carboxylic acids have hydrogen bonding and aldehydes do not the boiling point of the carboxylic acid is much higher than the boiling point of the aldehyde so they can be separated by simple (or fractional) distillation. They could also be separated by GLC or HPLC.

3. In fact tertiary alcohols can be readily oxidized just set fire to them! However the carbon chain is then completely broken down as carbon dioxide is formed. What chemists normally mean by not readily oxidized is that they cannot be oxidized whilst still retaining the carbon chain length.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Questions on Halogenoalkanes
1. (a) State the equation for the reaction of 1-bromopropane with warm dilute sodium hydroxide solution and name the organic product. (b) Identify whether this reaction proceeds by an SN1 or SN2 mechanism and explain why it goes by one of the mechanisms and not the other one. (c) Explain the mechanism by using curly arrows to represent the movement of pairs of electrons.

2. Suggest a reason why tertiary halogenoalkanes undergo nucleophilic substitution with hydroxide ions much faster than primary halogenoalkanes.

3. (a) Describe the difference between homolytic fission and heterolytic fission. (b) State one example of a reaction where chloromethane undergoes homolytic fission and one example of a reaction where chloromethane undergoes heterolytic fission. (c) State the equations for the two examples you have given in (b) and describe the necessary conditions for the reactions to occur.

4. (a) Explain why the substitution of primary halogenoalkanes by hydroxide ions could also be classed as a Lewis acid-base reaction. (b) Explain whether the reaction of tertiary halogenoalkanes with hydroxide ions could also be classed as a Lewis acid-base reaction.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Answers
1. (a) CH3CH2CH2Br + NaOH CH3CH2CH2OH + NaBr propan-1-ol)

(organic product:

(b) SN2 mechanism. It is a primary halogenoalkane. There is room to accommodate five groups around the central carbon atom in the transition state as the carbon to bromine bond is breaking and the carbon to oxygen bond is being formed simultaneously. It does not go by SN1 as it cannot readily form a primary carbocation as there is only one alkyl group exerting a positive inductive effect. (c)

2. The presence of three alkyl groups around the central carbon atom in tertiary halogenoalkanes increases the ability of the carbon to halogen bond to break. This is because the tertiary carbocation formed is stabilised by the positive inductive effect of the three alkyl groups. Once the carbocation is formed the reaction with the negative hydroxide ions is very fast. 3. (a) Homolytic fission: one of the electrons in the bond goes to one of the atoms and the other electron goes to the other atom which formed the bond to produce free radicals. Heterolytic fission: both of the electrons in the pair forming the bond go to one of the atoms and not to the other atom forming positive and negative ions. (b) Homolytic fission: Free radical substitution with chlorine gas. Heterolytic fission: Nucleophilic substitution with sodium hydroxide. (c) CH3Cl + Cl2 CH2Cl2 + HCl Conditions: ultraviolet light. CH3Cl + NaOH CH3OH + NaCl Conditions: warm, dilute aqueous sodium hydroxide solution. 4. (a) With primary halogenoalkanes the hydroxide ion is donating a pair of electrons to the carbon atom (which is accepting a pair of electrons) when it forms the transition state. (b) The second step in the SN1 mechanism with tertiary halogenoalkanes can

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

also be considered a Lewis acid-base reaction as the intermediate carbocation behaves as a Lewis acid when it accepts a pair of electrons from the hydroxide ion (which is behaving as a Lewis base).

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Questions on core Reaction pathways

1. Deduce two-step syntheses of the following products from the given starting materials. Include any necessary experimental conditions and give the equations for each step. (a) propanone from 2-chloropropane (b) 1,1,1,2-tetrachloroethane from ethene (c) 2-methylpropanoic acid from 1-chloro-2-methylpropane (d) butanal from 1-chlorobutane (e) ethanoic acid from ethene (f) butan-2-ol from butane (g) 1,2,3-tribromopropane from propene

2. One way of making butan-2-ol from but-2-ene is to react the but-2-ene with hydrogen bromide then react the product formed with sodium hydroxide solution. (a) State the IUPAC name of the intermediate formed and give the equations for the two steps. (b) Describe how butan-2-ol could be obtained directly from but-2-ene by a onestep reaction.

3. Suggest two different ways in which 1,2-dichloropropane could be synthesised from propene. State all the necessary equations and determine with an explanation which of the two different ways is likely to result in a higher yield of 1,2dichloropropane.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

Answers
1. (a) React 2-chloropropane with warm dilute aqueous sodium hydroxide solution. CH3CHClCH3 + NaOH CH3CH(OH)CH3 + NaCl Oxidize the product (propan-2-ol) with warm acidified potassium dichromate(VI) solution. CH3CH(OH)CH3 + [O] CH3COCH3 + H2O (b) Add chlorine gas to ethene (or chlorine dissolved in a non-polar solvent). CH2CH2 + Cl2 CH2ClCH2Cl React the product (1,2-dichloroethane) with excess chlorine in ultraviolet light. CH2ClCH2Cl + 2Cl2 CCl3CHCl + 2HCl (other chlorinated compounds will also be formed) (c) React 1-chloro-2-methylpropane with warm dilute aqueous sodium hydroxide solution. CH3CH(CH3)CH2Cl + NaOH CH3CH(CH3)CH2OH + NaCl Reflux the product (propan-2-ol) with hot acidified potassium dichromate(VI) solution. CH3CH(CH3)CH2OH + 2[O] CH3CH(CH3)COOH + H2O (d) React 1-chlorobutane with warm dilute aqueous sodium hydroxide solution. CH3CH2CH2CH2Cl + NaOH CH3CH2CH2CH2OH + NaCl Oxidize the product (butan-1-ol) with warm acidified potassium dichromate(VI) solution. CH3CH2CH2CH2OH + [O] CH3CH2CH2CHO + H2O (e) React ethene with steam at 570K/70 atm with a catalyst of phosphoric acid, H3PO4 or with water in the presence of a sulfuric acid catalyst. CH2CH2 + H2O CH3CH2OH Reflux the product (ethanol) with hot acidified potassium dichromate(VI) solution. CH3CH2OH + 2[O] CH3COOH + H2O (f) React butane with chlorine in ultraviolet light. CH3CH2CH2CH3 + Cl2 CH3CH2CHClCH3 + HCl (CH3CH2CH2CH2Cl will also be formed) React the required product (2-chlorobutane) with dilute aqueous sodium hydroxide solution. CH3CH2CHClCH3 + NaOH CH3CH2CH(OH)CH3 + NaCl (g) Add bromine liquid to propene (or bromine dissolved in a non-polar solvent). CH3CHCH2 + Br2 CH3CHBrCH2Br React the product (1,2-dibromopropane) with bromine in ultraviolet light. CH3CHBrCH2Br + Br2 CH2BrCHBrCH2Br + HBr (other brominated compounds will also be formed)

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

2. (a) 2-bromobutane CH3CH2CHCH2 + HBr CH3CH2CHBrCH3 CH3CH2CHBrCH3 + NaOH CH3CH2CH(OH)CH3 + NaOH (b) React but-2-ene with water in the presence of a sulfuric acid catalyst. (Reacting but-2-ene with steam in the presence of concentrated sulfuric acid as a catalyst is also acceptable.)

3. (i) React propene directly with chlorine in a non-polar solvent. CH3CHCH2 + Cl2 CH3CHClCH2Cl (ii) React propene with hydrogen chloride to give 2-chloropropane then react that with chlorine in ultraviolet light. CH3CHCH2 + HCl CH3CHClCH3 CH3CHClCH3 + Cl2 CH3CHClCH2Cl + HCl (other chlorinated compounds will also be formed) The first method will give the highest yield as it is a one-step reaction and is the only possible chlorinated organic product that can be formed.

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

PAPER 1 TYPE QUESTIONS. For each question choose the answer you consider to be the best.

1. What is the IUPAC name of the following hydrocarbon?

A. B. C. D.

hexane 2-methylpentane 2,2-dimethylbutane ethylbutane

2. Which is the correct formula for 2-bromo-3-methylbutane? A. B. C. D. CH3CBr2CH(CH3)CH3 CH3CHBrCH2CH(CH3)2 CH3CBr2C(CH3)2 CH3CH(CH3)CHBrCH3

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

3. How many structural isomers are there with the molecular formula C4H10? A. B. C. D. 2 3 4 5

4. A. B. C. D.

What is the IUPAC name for CH3CH2CH2CH2CHO ? pentan-1-ol pentanone pentanoic acid pentanal

5. Identify the functional group present in HCOOCH3. A. B. C. D. carboxylic acid ester ketone aldehydes

6. Which three compounds form part of a homologous series? A. B. C2H2, C2H4, C2H6 CH3OH, C2H5OH, C3H7OH

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

C. D.

CH3CH2CH2CH2OH, CH3CH2CH(OH)CH3, CH3CH(CH3)CH2OH CH3CH2CHO, CH3COCH3, CH3CH2CH2OH

7. Which products are most likely to be formed if excess butane is burned in a limited supply of air? A. B. C. D. hydrogen and carbon water and carbon monoxide hydrogen and carbon dioxide hydrogen and carbon monoxide

8. Which of the following contribute to the low reactivity of alkanes? I. II. The relatively strong C-H bond The very low polarity of the C-H and C-C bonds

III. The tetrahedral shape of the molecules A. I and II only B. I and III only C. II and III only D. I, II and III

9. Which species is a free radical? A. B. Cl. Cl+

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

C. D.

Cl Cl:

10. Which reaction could be a termination step in the reaction of ethane and chlorine in the presence of ultraviolet light? A. B. C. D. CH3CH2+ + Cl- CH3CH2Cl CH3CH2. + Cl2 CH3CH2Cl + Cl. CH3CH2. + CH3CH2. CH3CH2CH2CH3 CH3CH3 + Cl. CH3CH2. + HCl

11. Which is/are the products when but-2-ene reacts with hydrogen bromide? A. B. C. D. CH3CH2CHBrCH3 + H2 CH3CHBrCHBrCH3 + H2 CH3CH2CH2CH2Br CH3CH2CHBrCH3

12. Which can react to form addition polymers? I. II. H2C=CH(CH3) H2C=CH2

III. H2C=CHCl A. I and II only B. I and III only

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

C. II and III only D. I, II and III

13. Which of the following reactions can alkenes undergo? I. II. Nucleophilic substitution Combustion

III. Hydrogenation A. I and II only B. I and III only C. II and III only D. I, II and III

14. Which compound is a tertiary alcohol? A. B. C. D. butan-1-ol butan-2-ol 2-methylpropan-2-ol 2-methylpropan-1-ol

15. What process occurs when ethanol is made industrially from ethene? A. B. C. Hydrogenation Hydration Substitution

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

D.

Polymerisation

16. Which is a correct statement about alcohols? A. B. C. D. Secondary alcohols are formed by the oxidation of ketones. Tertiary alcohols can be readily oxidised to carboxylic acids. Primary alcohols can be formed by the reduction of carboxylic acids. Secondary alcohols can be oxidised to form aldehydes.

17. What will be the major organic product formed when propan-2-ol is reacted with a warm acidified solution of potassium dichromate(VI)? A. B. C. D. Propan-1-ol Propanal Propanoic acid Propanone

18. What do curly arrows show when used to illustrate a nucleophilic substitution reaction mechanism? A. The movement of an electron. B. C. D. The movement of a pair of electrons The homolytic fission of a bond The formation of the organic product

CHEMISTRY IB

TOPIC 10. ORGANIC CHEMISTRY

19. Which of the following will undergo reaction with sodium hydroxide solution via an SN2 mechanism? I. II. CH3CH2CH2CH2Br CH3CH(CH3)CH2Br

III. C(CH3)3Br A. I and II only B. I and III only C. II and III only D. I, II and III

20. Which two step synthesis could be used to convert ethane into ethanol? A. B. C. D. Addition of hydrogen followed by reaction with water. Substitution with water and removal of hydrogen. Substitution with chlorine followed by substitution with sodium hydroxide. Addition of chlorine followed by hydration with water.

Answers
1. C,
11. D,

2. D,
12. D,

3. A,
13. C,

4. D,
14. C,

5. B,
15. B,

6. B,
16. C,

7. B, 8. A,
17. D, 18. B,

9. A,
19. A,

10. C,
20. C