SEMINAR PENINGKATAN PENCAPAIAN PELAJAR-PELAJAR KIMIA STPM 2011

Essay
4. (a) Arrange the following compounds in order of increasing acidity. Explain.

CH2ClCOOH, CH3COOH, CH3CH2OH, CH2FCOOH, CHF2COOH [6 marks]

Reference(Ace Ahead STPM Text Chemistry Vol.2 by Oxford Fajar )

i. Effect of structure and delocalisation of electrons on the relative strengths of acids. Acidity of alcohols (pg 167) Acidity of carboxylic acid (pg 169) ii. Effect of substituents on acidity of carboxylic acids (pg 171)

(a) Order of increasing acidity: CH3CH2OH < CH3COOH < CH2ClCOOH < CH2FCOOH < CHF2COOH (1m)

Not accepted: CHF2COOH > CH2FCOOH > CH2ClCOOH > CH3COOH > CH3CH2OH

CH3CH2OH is the weakest acid because it has electron releasing group CH3CH2which strengthens O-H bond , and thus the equilibrium position shifts to left side of the following equation:

CH3CH2OH + H2O CH3CH2O- + H3O+

(1m)

The strength of CH3COOH can be explained using inductive effect

CH3COOH acid is stronger than CH3CH2OH because the oxygen atom in the carbonyl group of CH3COOH acid is electronegative and acts as a powerful electron-withdrawing atom which makes the carbonyl group electron withdrawing. (1m) The withdrawal of electrons away from the carboxyl hydrogen atom weakens the O-H bond which makes the carboxyl group to lose a proton readily (1m)

Or can be explained using resonance effect of carbonyl group CH3COOH is a stronger acid than CH3CH2OH because its anion, CH3COO- is resonance stabilised, and thus equilibrium position shifts to the right of the following equation:
CH3COOH + H2O CH3COO- + H3O+ (1m)

Resonance stabilisation:
1m

CH2ClCOOH, CH2FCOOH and CHF2COOH are stronger acids than CH3COOH because the halogens chlorine and flourine are strong electron withdrawing group( exert greater negative inductive effect) due to their high electronegativity values. (1m)

Among three acids CH2ClCOOH is a weaker acid because Chlorine is less electronegative than Fluorine. CHF2COOH is the strongest acid because presence of two Fluorine atoms (1m)

4(b) Hydrolysis of compound U, C4H9NO gives compound V, C4H8O2. Reaction of V with excess methanol in the presence of sulphuric acid produced W.Reaction of W with LiAlH4 followed by hydrolysis gives X and Y. Draw the structures of U, V, W, X and Y. Give IUPAC name of W.

[9 marks]

Reference(Ace Ahead STPM Text Chemistry Vol.2 by Oxford Fajar )

Acid hydrolysis of primary amide page 427 Esterification/ Preparation of ester page 411 Reduction of ester page 417

 Presence of nitrogen and oxygen shows U is an amide compound. Hydrolysis of U(amide) produces carboxylic acid,V, with same number of carbon atoms. Hence U will be primary amide U = CH3CH2CH2CONH2 V = CH3CH2CH2COOH (1m) (1m)

Chemical equation: CH3CH2CH2CONH2 + H2O + H+ CH3CH2CH2COOH + NH4+ (1m)

REVISION
Primary amide: O RCNH2 Tertiary amide: O RCNR R Secondary amide: O RCNH R

REVISION
Acid hydrolysis of 10 amide: CH3CH2CH2CONH2 + H2O + H+ CH3CH2CH2COOH + NH4+ Acid hydrolysis of 20 amide: CH3CH2CONHCH3 + H2O + H+ CH3CH2COOH + CH3NH3+ Acid hydrolysis of 30 amide: CH3CONH(CH3)2 + H2O + H+ CH3COOH + (CH3)2NH2+

 V which reacts with methanol in presence of sulphuric acid will undergo esterification process. Hence W is an ester

W = CH3CH2CH2COOCH3
Chemical equation: H2SO4 CH3CH2CH2COOH + CH3OH CH3CH2CH2COOCH3 + H2O

(1m)

(1m)

 Reduction of W which is an ester by LiAlH4 followed by hydrolysis will produce alcohol(s) as product. X = CH3CH2CH2CH2OH Y = CH3OH (2m) Chemical equation:
LiAlH4

CH3CH2CH2COOCH3 + 4[H] CH3CH2CH2CH2OH + CH3OH (1m)

IUPAC name of W is methyl butanoate

CH3CH2CH2COOCH3
butanoate methyl

THANK YOU
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