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Nanyang Junior College

H2 Chemistry (9647)

JC2 2015

Tutorial: Carboxylic Acids and Derivatives
Section A: Review Questions
1. Complete the following summary table of reactions of carboxylic acids.

OH

O

H3C C H

H3C C

H

Cl

10

7

8

5

4
O

1

H3C C N

H3C

O

6

C

H3C C
H

OH

2

9

3

H

O
H3C

C

C
-

O Na

Rxn

CH3
C

+

H3C

Reagents and Conditions
(Type of reaction)

Rxn

1

6

2

7

3

8

4

9

5

10

1

H

Reagents and Conditions
(Type of reaction)

. (i) butanoic acid ………………………………………………………………………………………… ………………………………………………………………………………………… (ii) pentanoic acid ………………………………………………………………………………………… ………………………………………………………………………………………… (iii) propanoic acid ………………………………………………………………………………………… ………………………………………………………………………………………… (iv) butanoyl chloride ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… 3. Give the reagents and conditions for each step. as well as indicate the type of reaction..2. to convert O (i) OH into OH ………………………………………………………………………………………… ………………………………………………………………………………………… (ii) ethanol into phenyl ethanoate ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………. Suggest reagents and conditions. Strategy for general synthesis questions: Check the difference between reactants and products – is there a change in carbon length? What functional groups are involved in the reaction? Recall reagents and conditions for the reactions that occur. and intermediate if necessary. Problem Solving Skill Set (PS3) for Q2 & 3 1. 2 . Describe how bromobutane can be converted to the following compounds.

Strategy for reaction questions involving arithmetic calculations: students must be able to recall and balance reactions involving all the functional groups. CH3CH2OCOCH2CH3 undergoes acidic hydrolysis in the presence of H218O. 3 . 5.or –OCO-. and ethanoyl chloride. Note that formula of ester functional group is either written as –COO. Which compound might X be? A CH3CH2CH2CH2OH B (CH3)3OH C CH3CH2CH2CO2H D CH3CH( OH)CO2H Problem Solving Skill Set (PS3) 1. H atom is added to the alcohol and the 18OH is added to the acid. Recall that each mole of –OH and –CO2H will react with each mole of Na to give ½ mole of H 2. 1 mol of a compound X gives 1 mol of H2 (g). Which of the following products are formed? (18O is an isotope of oxygen) 1 CH3CH218OH 2 CH3CH2CO18OH 3 CH3CH2OH Problem Solving Skill Set (PS3) 1. There is no ester written in the form –OOC-. In its reaction with sodium. Which one of the following is a product of the reaction between phenylmethanol.4. 6. Strategy for ester synthesis questions: students must be able to draw the structural formula of the given reactants and hence give the esters required. CH3COCl ? A OCOCH3 B CH2OCOCH3 C COOCH2CH3 D CH2COOCH3 Problem Solving Skill Set (PS3) 1. Student must note that when an ester undergoes acidic hydrolysis. Ethyl propanoate.

Must recall that comparisons can be between different functional groups and also between different acids.7. ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… Problem Solving Skill Set (PS3) 1. 4 . ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… (b) Explain why chloroethanoic acid is more acidic than ethanoic acid. (a) Explain why ethanoic acid is more acidic than ethanol. Student should be familiar with factors affecting stability of conjugate anion and relate stability of anion to strength of acids.

What bonds are broken/formed. One industrial preparation of ethanoic acid is the direct carbonylation of methanol using a rhodium catalyst CH3OH + OH rhodium CH3 CO C catalyst O CO 2H HC CH 2CO 2H Which compound could be expected to produce CH 2CO 2H A OH HC C CO 2H B CH 2OH HC OH HC CH 2OH ? CH 2CO 2H CO 2H D CH 2CO 2H OH HC CH 2CO 2H CH 2CO 2H CH 2OH Problem Solving Skill Set (PS3) Strategy for solving reactions not found in syllabus: 1. what is the type of reaction? 2. HOCH2CO2H excess CH3NH2 excess PCl5 compound Q compound R heat What are the formulae for compounds Q and R? Compound Q HOCH2COCl ClCH2CO2H ClCH2COCl ClCH2COCl A B C D Compound R HOCH2CONHCH3 CH3NHCH2CO2H CH3NHCH2COCl CH3NHCH2CONHCH3 9. Hydroxyethanoic acid reacts as shown. Observe the patterns in the reaction.Section B: Discussion Questions 8. What are the products formed from this reaction? 5 . How is the CO group added to the alcohol? 3.

then adding CH3CO2H Problem Solving Skill Set (PS3) Strategy for solving questions that involve the largest yield of ester: 1. starting from ethanoic acid. Recall the order of ease of hydrolysis of different functional groups. 6 . Which procedure gives the best yield of ethyl ethanoate. 2. CH 3CO2CH2CH3. then adding CH3CO2H refluxing a mixture of CH3CO2H and CH3CH2OH with NaOH (aq) refluxing CH3CH2OH with concentrated H2SO4. Identify the functional group present.g. a larger yield)? 3. CH3CH2OH? A B C D reacting CH3CO2H with SOCl2. 11. then adding CH3CH2OH reacting CH3CH2OH with SOCl2. CH3CO2H. Recall reactions of functional groups in the above reactions and understand why 3 out of 4 options give a poor or no yield of ester. Which set gives a compete reaction (e.10. Which compound is most readily hydrolysed by water? A B C D CH3COCH2Cl C6H5CH2COCl CH3CHClCO2H Cl Cl COCH 3 Cl Problem Solving Skill Set (PS3) Strategy for solving questions that involve the largest yield of ester: 1. Recall the 2 different sets of reagents and conditions to yield esters 2. and ethanol.

7 . CO2Na CN OCOCH3 HCl(aq) OCOCH3 NaOH(aq) CO2H OCOCH3 reflux Suggest what is wrong with the scheme and propose a correction to the scheme to successfully get aspirin. ………………………………………………………………………………………………… ………………………………………………………………………………………………… (b) Draw the structural formulae of the organic molecules produced when A reacts with i. 2-hydroxybenzoic acid. A.12. (a) Suggest suitable reagents and conditions for reaction II. iii. is a useful intermediate for making aspirin (an analgesic) and “oil of wintergreen” (used in ointments). Br2 (aq) (c) A student proposes the following synthetic route to get aspirin. Na ii. Na2CO3 SOCl2 iv.

2..………………………………………………………………………………… (d) When an aspirin tablet was crushed up in water and titrated with 0. 13.1 mol dm -3 sodium hydroxide. hence determine the mass of aspirin in the tablet? Problem Solving Skill Set (PS3) 1.9 cm3 of alkali was required to neutralise its acidity. all moles of –COOH will be reacted away.. How can we determine mole ratio of aspirin to NaOH? Note that during neutralisation reaction. ………………. Consider how the reaction would change if heat was supplied? 8 . ……………….Error in the proposal: ………………………………………………………………………. Write a balanced equation for the reaction between aspirin and sodium hydroxide..………………………………………………………………………………… Correction to the scheme: …………………………………………………………………..

………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… 9 . (ii) Suggest why aspirin is insoluble in water whereas its calcium salt is soluble. (i) What reagent could you use to convert aspirin into its calcium salt? Write an equation to illustrate your answer. Draw a suitable diagram to illustrate the solubility of the salt.(e) A “soluble aspirin” contains the calcium salt of aspirin.

L P (b) Compound P can be synthesized from compounds Q and N through the following synthesis process. and benzoic acid. and is used in perfumes. and benzoic acid. Q. N. Hydrolysis of L produces equimolar amounts of phenylmethanol. 10 . Hydrolysis of P produces 4-methylphenol. M. (a) Suggest structures for L and P. Compound L is used medicinally as an anti-spasmodic agent. Compound P is an isomer of L.13. N.

NaOH is used to generate the phenoxide anion. Note in the first step. 2. You may find it helpful to make a comparison to nucleophilic substitution mechanism of RX. 11 . Problem Solving Skill Set (PS3) 1. In your answer.(i) Suggest reagents and conditions from steps (I) and (II). a stronger nucleophile than phenol (to subsequently attack the benzoyl chloride). show any relevant charges. Step (I): ……………………………………………………………………… Step (II): ……………………………………………………………………… (ii) State the type of reaction that has taken place in step (II). ……………………………………………………………………… (iii) Hence suggest a possible mechanism for step (II). lone pairs of electrons and movement of electrons.

9. 70. C.3 x 10-5 COOH Carbonic acid H2CO3 4. Structure of E1 Structure of E2 12 .8 x 10-5 Phenol (a) Ka / mold m-3 formula 1. Values of the acid dissociations. ……………………………………………………………………… When the aromatic ester E is hydrolysed with NaOH (aq) and the resulting mixture acidified with a mineral acid such as sulfuric acid.5 x 10-7 Ethanoic acid CH3CO2H 1. 23. Draw the displayed formulae of your compounds in the boxes below. K a. methanoic acid. acid Benzoic acid 6. O.0. for some weak acids are given below. is not among the products.6. suggest molecular formula of E. HCO 2H. (ii) Given that Mr of E is 136.3 x 10-10 OH An aromatic ester E has the following percentage composition by mass.5 (i) Calculate the empirical formula of E.N2009/II/5 modified 14. (b) (i) Use this information and your answer to (a)(ii) to suggest two possible structural formulae for the ester E. 5. H.

If nothing is formed. E1 produces E2 produces Explain your answer: ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… 13 . give the structural formulae of the organic products that would be formed on heating it under reflux with an excess of NaOH (aq).(ii) For each of your compounds E1 and E2. write ‘no reaction’. E1 produces (c) E2 produces Suggest what will be formed if CO2 is bubbled through each of the mixtures formed in (b)(ii).

state the reagents and conditions. and state what would be observed with each compound. (a) CH3COCl and CH3CH2Cl ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… (b) O O O O Compound A and Compound B (Hint: need to break linkage before distinguishing test can be done) ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… (c) CH3COOH.15. For each test. CH3CH2OH and CH3COOCH3 (Hint: more than 1 test required) ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… 14 . Describe simple chemical tests which would enable you to distinguish the following compounds.

Student should be familiar with factors affecting stability of conjugate anion and relate stability of anion to strength of acids. ………………………………………………………………………………………………… 15 . Must recall that comparisons can be between different functional groups and also between different acids. Students may make reference to the diagram on the below showing electron dispersion of benzoate anion to deduce stability of the benzoate ion. phenol benzoic acid ethyl ethanoate ethanoic acid Problem Solving Skill Set (PS3) for Qn 12 2.. Arrange the following organic compounds in order of increasing pH of solution formed when the same amount of each compound is dissolved separately in water. Explain your answer. ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………………… ………………………………………………………………………………………….…….. 3.16.

C5H6O4 when refluxed with acidified potassium dichromate (VI). C5H10O2 which is soluble in water and neutral to litmus. C3H4O4. with the aid of equations where appropriate. Compound H readily forms compound I. ether reflux K KCN ethanol + L i) H (aq). Strong oxidation of H by hot acidified potassium manganate (VII) causes it to form only one organic product M. CHOCH2Cl LiAlH 4. *Please write your explanation in a piece of foolscape paper. C5H11O3Br and decolourized bromine water. Explain the chemistry of the reactions described. compound H produced compound J.17. On reaction with aqueous bromine. Compound I forms a diester when warmed with 2 moles of ethanol and concentrated sulphuric acid. reflux M Deduce the structures of compounds H to M. This question is about compound H. H I J K L M 16 . M can be synthesized as indicated in the following reaction scheme. heat 2- + ii) Cr2O7 /H .

MHA. (b) Explain why this acid is a much stronger acid than ethanoic acid. was much used up to the middle of this century as a drug and a stimulant. CH3CH2CH2C(CH3)=CHCO2H MHA (a) Draw the structures of possible organic products when MHA reacts with the reagents in the table below. 3-methylhex-2-enoic acid. In 1991. in dry ether Type of reaction: (iv) Hot acidified KMnO4 Type of reaction: Type of reaction: [8] 17 . (i) SOCl2 (ii) HBr Type of reaction: (iii) LiAlH4. Trichloroethanal (choral). CCl3CHO. was identified as one factor responsible for the offensive odour of human sweat.. (a) Draw a displayed formula of trichloroethanoic acid.Nanyang Junior College H2 Chemistry (9647) JC2 2015 Carboxylic Acids and Derivatives Assignment Name: ……………………………………………………. and state the type of reaction in each case. [2] ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………[2] 19. 18. Choral is easily oxidised to trichloroethanoic acid.. CT Marks: 15 : 14 …….

(b) The odour of MHA is removed by reacting it with aqueous sodium carbonate. using ethanoyl chloride as an example (c) explain the acidity of carboxylic acids and of chlorine-substituted ethanoic acids in terms of their structures (d) describe the hydrolysis of acyl chlorides (e) describe the reactions of acyl chlorides with alcohols. and hence suggest why it has no odour. aldehydes and nitriles (b) describe the reactions of carboxylic acids in the formation of (i) salts (ii) esters on reaction with alcohols. phenols and primary amines (f) describe the relative ease of hydrolysis of acyl chlorides. ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………… ………………………………………………………………………………………[3] 1 (a) describe the formation of carboxylic acids from alcohols. Draw the structure of the organic product of this reaction. using phenyl benzoate as an example (h) describe the acid and base hydrolysis of esters 2 3 4 5 6 7 8    9 10 11 12 13 14 15 16                19          18 18     17  . alkyl chlorides and aryl chlorides (g) describe the formation of esters from acyl chlorides. using ethyl ethanoate as an example (iii) acyl chlorides.