E x a m in at io n a n s we

1.1 Rings, polymers and analysis

1 (a) Structure:

rs

(iii)

Br

Br2

HBr

(iv) Bromobenzene (b)

Br H Br Step 2 Br

Empirical formula: CH (b) Concentrated nitric acid and concentrated sulfuric acid. (c) (i) NO2+ (ii) HNO3 + H2SO4 NO2+ + HSO4 + H2O (iii) NO2 ON H
NO2
2

Step 1

Intermediate

(c) (i)

Cyclohexene H H H H Benzene H H H H H p orbitals H H overlap H H H H H H H p orbitals overlap to give a H bond above and below the H two carbon atoms H See diagram 00.00.00.00 H

2 (a) (i) I: Br2, II: NaOH (ii) Dye, colouring or indicator. (iii) Add phenylamine to sodium nitrite and hydrochloric acid below 10 C. Add this product to an alkaline solution of phenol. (b) H H H H
C H C C H C H H C C H H C C C H C C C H

The p orbitals overlap above and below the plane of the ring structure. The electrons are delocalised and spread across all six carbon atoms. In benzene all the bonds are the same length between the lengths of the single and double bonds. henol is more reactive because the ring is P activated. The lone pair from the oxygen on the ring is delocalised into the ring so electrophiles are more attracted to the ring than in benzene. 3 (a) (i) FeBr3 or AlBr3 (ii) Halogen carrier.

(ii) n benzene the electrons are spread over the I whole ring structure, as they are delocalised. When cyclohexene is reacted with bromine the bromine is polarised by the double bond. However, when benzene is reacted with bromine, the bromine cannot be polarised by the ring as the electrons are spread over the molecule. Electrophiles are less attracted to the benzene. Greater energy is needed to break the cloud in benzene than in cyclohexene. 4 (a) (i) D = Propanone (ii) E = Propanal (b) (i) eagent(s): 2,4-dinitrophenylhydrazine. R Observation: orange precipitate. (ii) eagents: Tollens reagent. Observation for D: R no change. Observation for E: Silver mirror formed.

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5 (a) CH3CHO + 2[H] CH3CH2OH (b)

O C CH3 H H

8 (a)
H H O
H

H C H

H C H

H C H

H C H H H C H H H C H H OH OH H C H H C H H C O H H C H H

NaBH4 Step 1 CH3 H

O H H

O C H

Butan-1-ol

Intermediate
H H C H CH3 C H

Ethanal

Step 2

Butan-2-ol

CH3

H C C OH H H C H H

2-methylpropan-1-ol

H Organic product

(iii) An electron-pair donor (iv) he nucleophile is attracted to the positive T charge. Lone pair of electrons forms a dative bond. An electron pair from the double bond goes to the oxygen atom. The bond in the carbonyl bond breaks. (c) Hydrogen does not have a lone pair of electrons. 6 (a) O
O Z-but-2-enal cis but-2-enal E-but-2-enal (trans)

2-methylpropan-2-ol

(b) (i) dd Tollens reagent. Heat reaction in a water A bath. But-2-enal gives a silver precipitate or silver mirror. (ii) Aldehydes can be oxidised but ketones cannot. (c) (i) CH3CH=CHCH2OH (ii) Redox reaction/reduction or addition. (d) C4H6O + 5O2 4CO2 + 3H2O 7 (a) (i) eagent: Tollens reagent. Observation: silver R mirror formed. Organic product: butanoic acid. (ii) eagent: bromine. Observation: decolourises. R Type of reaction: electrophilic addition. (b) Recrystallise the product in order to purify the orange precipitate. Measure the melting points of the crystals. Compare known melting points with data tables.

(b) (i) Butan-1-ol can be oxidised to produce butanal and further oxidised to give butanoic acid. This occurs as primary alcohols can be oxidised. Butan-2-ol can be oxidised to produce butanone. No further oxidation occurs as ketones cannot be oxidised. 2-Methylpropan-2ol cannot be oxidised as it is a tertiary alcohol and is not oxidised. 2-Methylpropan-1-ol can be oxidised to produce 2-methylpropanal and further oxidised to give 2-methylpropanoic acid. D: 2-methylpropan-1-ol. E: 2-methylpropanoic acid. (ii) (CH3)2CHCOOH + C2H5OH (CH3)2CHCOOC2H5 + H2O (c) H H H H O
HO C H C H C H C H C ONa

9 (a) (i) Methyl butanoate. (ii) Heat/boil/warm/reflux with aqueous HCl or aqueous NaOH. (b) (i)
HO

(ii)

HO or

HOCH2CH2 C H C

C2H5

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(iii)

O C H3C O CH2 CH2 C H C H CH2CH3

12 (a) Stage 1: React phenylamine with sodium nitrite and hydrochloric acid at 10 C or below. This forms a diazonium salt which is unstable and must be kept below 10 C. Stage 2: React the diazonium salt with an alkaline solution of phenol below 10 C.
NH2 N2Cl

10 (a) (i) Concentrated H2SO4. (ii) his is to prevent the loss of reactants and T products by evaporation. (b) (i) H
H H C H O C H O H H C C C C H H H H H

2 HCI NaNO2

NaCl 2 H2O (Diazonium salt)

N2

Cl

OH

NaOH

(c) 11 (a) (b) (c)

(ii) Butan-2-ol. Flavourings or perfumes. A compound containing nitrogen where the nitrogen is attached to one carbon atom only. + C2H5NH2 + H+ C2H5NH3 (i) tage I: Sn, conc. HCl. Stage II: NaNO2, HCl. S Stage III: Phenol, NaOH. (ii) Stage I
NO2 NH2

HO

N OH

NaCl H2O

(b) (i)

N N SO3Na

6[H]

2 H2O

SO3Na E110

CH3 Stage III N2Cl OH

CH3

(ii) 16 carbon atoms and 10 hydrogen atoms. (c) NaOH(aq) OH (d)

H2N Amine

SO3Na

CH3

NaOH SO3Na

CH3

OH NaCl H2O

Phenol

(iii) Dyes.

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13 (a) Diamino compound contains two amine groups 1,4 shows the position of the amine groups on the benzene ring. (b) (i) Reduction/redox reaction. (ii) Tin and concentrated HCl. Heat under reflux. (iii)
O2N NO2 12[H]

(iii) Use a naturally occurring amino acid. (iv) higher dose would be required. The other A stereoisomer may have side effects. 2 (a) (i) RCH(NH2)COOH (ii) H H H
H H C H N H H C C C H H C H C O H O H

H2N

NH2 4H2O

(c) (i) he amino group accepts H+ using its lone pair T or electrons on the nitrogen and forming a co-ordinate bond. (ii)
ClH3N
NH Cl 3

(b) (i) n ion which has both a positive and a negative A charge. The overall charge is zero. (ii) A proton is transferred from the acidic COOH group to the basic NH2 group.
H N H R C H C O H O H H H N

R C H C

14 (a)

CH3(CH2)6CH2 C H C

CH2

(CH2)6COOH

(b) (i) Oleic acid: C18H34O2. Ethanol: C2H6O. Ethyl oleate: C20H38O2 (ii) C18H34O2 + C2H6O C20H38O2 + H2O (c) Hydrolysis using hot aqueous HCl.

Heat with HCl (aq). Hydrolysis. Ammonia in ethanol. Leucine synthesised in the laboratory contains a mixture of two optical isomers. Leucine from meat (a natural source) contains only one of the isomers. 3 (a) For L: (c) (i) (ii) (d) (i) (ii)

1.2 Polymers and synthesis

1 (a) (i) Hydrochloric acid. Aqueous acid heated under reflux. (ii) Amino acids. H H (iii) O
H

H C H C H O C H H C OH C O O O O C O H O C O O C H C OH H O

N H

C H

C O H

(or equivalent)

For M:
H

(iv) A reaction with water which breaks down a compound into smaller sub-units. In the reaction above the peptide bond is broken. (b) (i) For stereoisomerism in compound A, there must be a chiral centre, which is a carbon atom with four different groups attached to it. Stereoisomerism occurs when there is a different spatial arrangement of the groups. Two mirror images that are non-superimposable are observed. (ii) he molecule contains two chiral centres and T each chiral centre has two isomers.

(b)

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(c) t is a condensation reaction. When the reaction I occurs a small molecule such as water is lost. (d) Fibres/clothing. 4 (a) (i) H H H H H H
C C H3C CH3 C H3C CH3 C C H3C CH3 C

I n condensation polymerisation, a polymer such as PET is formed when monomers in this case ethane-1,2-diol and benzene-1,4-dicarboxylic acid join together and lose a small molecule for each bond that forms. In the case of this polyester, a water molecule forms for each ester linkage that forms between OH and HOOC.
Addition: Monomer ethene H n H Condensation H HO C H H C H OH HO O C O C OH C C H H H C H H C H H C n H H C H

(ii) CH2 (iii) H

C H H C O N C

CH3

(b) (i) Name of functional group: peptide.

(ii) Condensation. (iii) Displayed formula of H:

H N H H C H C O H N H2N O OH H N H C H O C O H O

H O C H

H C H CH3 O

O C

O C n H2O

(b) (i)
H C H C H O

Skeletal formula of H:

(ii) Reagents: HCl (aq). Conditions: Heat and reflux (iii) CH3COOH (c)
O C OH HO C O HO H C H H C H OH

(iv) No. of moles of glycine = 1.40/75.0 = 0.0187 moles. Expected no. of moles of dipeptide = 0.0187/2 = 9.33 103 mol. Expected mass = 9.33 103 132 = 1.232 g. % = (1.10/1.232) 100. Percentage yield 89.3% H H (v) O
Cl H

N H

C H

C OH

6 (a)

O C Cl (CH2)4
C

H N H 1,6-diaminohexane (CH2)6
N

5 (a) In addition polymerisation, the C=C double bond in an unsaturated molecule (monomer), such as ethene, breaks open and the monomer adds on to a growing polymer chain. The monomers add one at a time to form a long polymer such as poly(ethene), HDPE.

Cl Hexanedioyl dichloride
O C (CH2)4 O C N

(CH2)6

N H

HCI

H Repeat of unit polymer

Other product

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(b) (i)
HO

O C

O C OH

(iv)
H

H C

Cl

O O

H O C H Cl

CH3
H C H H

H N H N H H

(ii) he intermolecular forces in Nomex are T stronger than in nylon. 7 (a)

NO2

9 (a) C10H10O5 (b) (i) Reagent(s): K2Cr2O7 (aq). Conditions: heat with H+. Organic product:
O C H CH2 CH2 O O C O C OH

(b) CH3COOH and CH3OH (c) H CH3 O H

N H C H C N H C C6H5

O C OH

(ii) Reagent(s): HCl (aq). Conditions: aqueous. Organic products:

O HO CH2CH2 OH HO C O C OH

H N H

H C C6H5

O C N H

CH3 C H C

(iii) Reagent(s): NaOH (aq). Conditions: none. Organic product:

O O C ONa HO CH2CH2 O C

OH

8 (a) (i) NaOH (aq) (ii) Substitution. (iii) C6H5CH2Cl + NaOH C6H5CH2OH + NaCl H H O (b) (i)
H C H C O C H

(ii) C6H5CH2OH + CH3COOH CH3COOCH2C6H5 + H2O (iii) Flavourings.

10 (a) HOOC(CH2)4COOH and H2N(CH2)6NH2. (b) condensation polymerisation small molecule, H2O, is eliminated. (c) Structural similarity Both have peptide or amide links Both form H-bonds between molecules. Chemical similarity Both can be hydrolysed back to monomers by reaction with hot aqueous acid or alkali: e.g. CO(CH2)4CONH(CH2)6NH HOOC(CH2)4COOH + H2N(CH2)6NH2 Differences Protein can be water-soluble, nylon-6,6 not. Proteins are biodegradable, nylon-6,6 is not. Nylon-6,6 has a regular chain of alternating monomers. Proteins are made from 20 different amino acids.

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COOH COOH O2N O2N N N N N OH OH

11 (a) (i)

H C H C

CH3

H C

CH3 C H n

(c)
O2N O2N N N N N

COONa COONa

OHNa OHNa

(ii) ddition: The monomer has a C=C double A bond. The double bond breaks and no substance is lost. Condensation: A small molecule such as water is lost. (b)
Cl Cl

(d) Tin and concentrated hydrochloric acid, reflux.

COOH COOH O2N O2N N N N N OH 6[H] OH 6[H]

(c) (i)

CH3 CH3

CH3 CH3

O H2N H2N N N N N

COOH COOH

(ii) H reacts with NaOH, poly(propene) does not. H is an ester and is polar so will be hydrolysed by NaOH. Poly(propene) is non-polar. 12 (a)
O2N O2N N N N N OH OH COOH COOH

C CH CH C O CH2 O CH2

CH CH O CH2 CH2

OH 2 H2O OH 2 H2O

1.3 Analysis

1 (a) (i) Paper, column or thin-layer chromatography. (ii) The Rf value. (iii)
Solvent front

(b)
O2N O2N NH2 NH2 NaNO /HCI NaNO2/HCI 2 Below 10 C Below 10 C x y

x Rf y

Start point

O2N O2N

N2Cl N2Cl COOH COOH

(b) (i) Retention time. (ii)

Detection
OH OH

NaOH NaOH

Retention time
COOH COOH O2N O2N N N N N OH OH

Start

COONa COO Na

O2N O2N

N N N N OHNa OHNa

(c) (i) Relative solubility in liquid stationary phase or adsorption to solid stationary phase. (ii) Each component distributes itself between the mobile phase (carrier gas) and the stationary phase. Different components are held more or less strongly on the stationary phase and this leads to separation. his depends upon molecular size, volatility and T extent of bonding to the stationary phase.
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2 (a) Adsorption at 1700 cm1 shows the presence of C=O. Adsorption at 1200 cm1 shows the presence of CO. No broad adsorption at 25003500 cm1 so does not contain OH. (b) The mass spectrum shows an M+ peak at 116 therefore 116 32 (2 oxygen atoms) = 84 therefore 6 carbon atoms maximum. Molecular formula of X = C6H12O2. Base peak = 57 CH3CH2C=O. NMR. peak areas show 12H atoms and four different proton environments. = 0.9 ppm suggests CH3 next to CH2 (triplet) = 1.2 ppm suggests 2 CH2 next to CH (as split into a doublet). = 2.3 ppm CH2 next to CH3 (quartet) Other CH2 next to C=O = 4.1 ppm is CH next to 2 CH3.
H C H H C H O C O H H

(e) Correct structure of compound Y:

H H C H O C O H C H H

Peak at = 2.1 ppm is due to COCH3 Peak at = 3.7 ppm is due to OCH3 elative peak areas 1:1 as both groups have the R same number of carbon atoms. Peaks show no splitting as there are no protons on the neighbouring carbon atoms. 4 (a) Low boiling point. (b) dd 2,4-DNP (2,4-dinitrophenylhydrazine) to the A aldehyde or ketone. Purify or recrystallise the orange precipitate. Measure the melting point of the crystals. Compare the results with known values from a data table. (c) (i) H
H Absorption of energy C C C C H OH H H O H H

C CH3

CH3

3 (a) Compound has a molecular mass of 74. elative empirical formulae mass = 74 R (3 12 + 6 + 2 32) therefore empirical formula = molecular formula = C3H6O2.
100 80 Relative intensity 60 40 20 0 10 15 20 25 30 35 40 45 50 55 60 65 70 75 m/e

11

10

7 6 5 4 3 2 Chemical shift/ n.m.r. spectrum of 3-hydroxybutanone

(b) (i) Compound X is not an aldehyde or a ketone. (ii) Compound X does not contain C=C and is not a phenol. (c) Structure 1: ethyl methanoate. Structure 3: propanoic acid. (d) Peak at 1750 cm1 indicates presence of C=O. Peak at 1250 cm1 indicates presence of CO. No peak at 25003500 cm1 means it does not contain OH group. It cannot be structure 3.

(ii) e-run the spectrum having added D2O to the R sample. The peak due to OH will disappear. (iii) Peak at = 1.4 ppm (doublet): (1:1) due to one proton on adjacent carbon atom. peak at = 4.3 ppm (quartet): (1:3:3:1) due to three protons on the adjacent carbon atom. (iv) See graph answer to (c)(i). (v) he number of protons in the same chemical T environment. H OH 5 (a) (i) O O
C HO C H CH2COOH H HO C COOH HOOC C* H C OH CH2COOH C OH H

(ii)

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Relative abundance (%)

(b) (i)

100 80 60 40 20 0 40 60 80 m/e 100 120 140

(protons) on the carbon under investigation: the splitting pattern (singlet, doublet, triplet or quartet) is one greater than the number of adjacent protons. D2O is used to identify the presence of OH groups. (ii)
CH3CH2COOCH2CH(CH3)2

(ii) Molecular ion peak would be at 90. (c) (i)

Absorption of energy

S
3

12

11

10

7 6 5 4 Chemical shift/

(ii) 4 as OH protons would now be visible. O H H (d) (i) O

H C H C H C O H C H H C H H

(ii) More fruity because of ester/less sour as acid is used up. 6 (a)
H H C H H C H O C O H C H H H C C H H

7 (a) (i) Find the m/z value of the peak furthest to the right with highest m/z value. (ii) C2H3O2 has an empirical mass of 59. therefore 118/59 = 2 2 empirical formula = C4H6O4. (b) (i) OH peak disappears. (ii) Peak at = 3.3 ppm identifies CH group. It shows as a quartet splitting pattern showing presence of three protons on the adjacent carbon atom. There is only one hydrogen in this environment. Peak at = 1.2 ppm identifies CH3 group. It shows doublet splitting showing the presence of one proton on the adjacent carbon atom. There are three protons in this environment. elative peak areas show the number of R hydrogens (protons) in the environment.
H O H C HO C C H H C OH O

H C H H

(b) CH3CH2COOH + (CH3)2CHCH2OH CH3CH2COOCH2CH(CH3)2 + H2O Alcohol: 2-methylpropan-1-ol Carboxylic acid : propanoic acid. Heat the alcohol and the carboxylic acid with some concentrated sulfuric acid in a water bath. (c) Mass spectrometry. Use the molecular ion peak, the m/z value for the peak at highest mass. (d) (i) he value or chemical shift indicates the type of T proton or chemical environment. The number of peaks gives the number of different types of proton or the different numbers of chemical environments. The relative ratio of peak areas shows the number of protons of each type. Splitting patterns give information about the number of neighbouring hydrogen atoms

(iii) here would be one peak with no splitting as all T four protons are in the same environment. 8 (a) Infrared: X and Y both have C=O at 16801750 cm1. X and Y both have CO at 10001300 cm1. X and Y both have OH in range 25003300 cm1. Only Y has an absorption at 31003500 cm1 for NH. Both have different fingerprint regions. Mass spectrum: X and Y have different M peaks, X = 88 and Y = 89. X and Y have some similar fragments, e.g. CH3CH+ at m/z = 28, COOH+ at 45, CHCOOH+ at 58, CH3CHCOOH+ at 73. X and Y have some different fragments, e.g. X has CH3CHCH3+ at m/z = 43 or (CH3)2CHCO+ at 71; Y has H2NNCH+ at 29, H2NCHCH3+ at 44, CH3(NH2)CHCO+ at 72 or NH2+ at 16.

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(b) Proton Chemical Splitting Relative environment shift, /ppm pattern peak area OCH3 CH2CO CH3C 3.34.3 2.02.9 0.71.6 singlet quartet triplet 3 2 3 3

2.1 Rates, equilibrium and pH

1 (a) H2O2 + 2I + 2H+ I2 + 2H2O (b) (i) xperiment 2 has twice [I] of Experiment 1 and E the rate has quadrupled, so order = 2 with respect to I. Experiment 3 has twice [H+] of Experiment 2 and the rate is unchanged, so order = 0 with respect to H+. (ii) rate = k [H2O2] [I]2 (iii) k = rate/[H2O2][I]2 Experiment 1: k = 1.15 106/(0.01)(0.01)2 = 1.15 102 dm6 mol2 s1 (c)

Rate of reaction

Straight line increasing Through 0/0

[H2O2(aq)]/mol dm3

(d) (i) 2H2O2 2H2O + O2 (ii) 1 dm3 H2O2 20 dm3 O2 amount of O2 = 20/24 mol concentration of H2O2 = 2 20/24 = 1.67 mol dm3 2 From the graph, there is a constant half-life. Therefore, order = 1 with respect to [CH3COCH3]. From the table, the rate doubles when [H+] doubles. Therefore order = 1 with respect to [H+]. From the table, the rate stays the same when [I2] doubles. Therefore order = 0 with respect to [I2]. The rate equation is: rate = k[H+][CH3COCH3] 2.1 109 rate k = _______________ = _______________ [H+][CH3COCH3] 0.02 1.5 103 = 7.0 105 dm3 mol1 s1 The rate-determining step involves the species in the rate equation: H+ and CH3COCH3.

A possible two-step mechanism is: Step 1: CH3COCH3 + H+ CH3COHCH3+ Step 2: CH3COHCH3+ + I2 CH3COCH2I + HI + H+ H+ is used up in the first step and is regenerated in the second step so H+ is a catalyst. [CH3COOC2H5] [H2O] (a) Kc = ___________________ [CH3COOH] [C2H5OH] (b) (i) CH3COOH, 1.0 mol; C2H5OH, 7.5 mol CH3COOC2H5, 5.0 mol; H2O, 5.0 mol 55 (ii) Kc = _______ = 3.3 (no units) 1 7.5 (c) he experiment could be left longer to reach T equilibrium. he compositions of the mixtures could be analysed T at time intervals until the compositions do not change any more. (d) (i) here would be more CH3COOC2H5 and H2O T There would be less CH3COOH he equilibrium shifts to the right to counteract T the effect of increasing the ethanol concentration. (ii) Kc stays the same. (e) he composition stays the same because the catalyst T does not shift equilibrium position. he rates of the forward and reverse reactions are T increased by the same amount. (f) (i) A decrease in Kc results in more reactants and fewer products. The equilibrium therefore shifts to the left in response to the new value of Kc. (ii) ncreasing the temperature moves the equilibrium I to the left to counteract the effect of the increase in energy. The forward reaction is exothermic and the reverse reaction is endothermic. [Hl]2 (a) Kc = ______ [H2] [l2] (b) (i) H2, 0.14 mol; I2, 0.04 mol; HI, 0.32 mol 0.322 (ii) Kc = ___________ = 18.285 714 29 0.14 0.04 = 18 (to 2 sig. figs), no units (c) Kc is constant because all volumes cancel and the temperature is constant. he composition is the same as there are the same T number of gas moles on either side of the equation. (d) he forward reaction is exothermic. The equilibrium T moves to the left to compensate for the increase in temperature. (e) (i) I2(aq) + H2S(g) 2HI(aq) + S(s) (ii) amount of I2 reacted = 1.89 mol, Therefore amount of HI formed = 3.44 mol Theoretical amount of HI produced = 3.78 mol 3.44 100 % yield = __________ = 91.0% 3.78

10

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3.44 1000 ___________ = 4.59 mol dm3 (iii) [HI] = 750 pH = log 4.59 = 0.66 5 (a) (i) A BrnstedLowry acid is a proton donor. (ii) A weak acid is partially dissociated. (iii) pH = log[H+] (iv) A buffer solution minimises changes in pH after addition of small amounts of both acids and alkalis. (b) n the equilibrium H2CO3(aq) Y H+(aq) + HCO3(aq) I Hydrogencarbonate, HCO3, reacts with any added acid: HCO3 + H+ H2CO3 he equilibrium moves to the left to counteract T increased [H+]. H+ reacts with any added alkali: H+ + OH H2O he equilibrium moves to the right to counteract a T decrease in H+. [H+][HCO3(aq)] (c) Ka = _____________ [H2CO3(aq)] [H+] = 10pH = 107.4 = 3.98 108 mol dm3 [HCO3(aq)] Ka 4.17 107 __________ = ____ = __________ = 10.5 + [H2CO3(aq)] [H ] 3.98 108 6 (a) A weak acid partially dissociates: e.g. HCOOH Y H+ + HCOO (b) (i) pH = log (1.55 103) = 2.81 [H+] deals with negative indices over a very wide range. [H+(aq)][HCOO(aq)] (ii) Ka = _________________ [HCOOH(aq)] [H+(aq)]2 (1.55 103)2 (iv) Ka = ____________ = ____________ 0.015 [HCOOH(aq)] = 1.60 104 mol dm3 pKa = log Ka = log (1.60 104) = 3.80 (1.55 103) 100 Percentage dissociating = _________________ 0.015 = 10.3% HCOOH + NaOH HCOONa + H2O n(HCOOH) = 0.0150 25.00/1000 = 3.75 104 mol From the graph, the rapid rise in pH takes place after addition of 30 cm3 of NaOH(aq). Therefore 30 cm3 of NaOH(aq) are required for neutralisation. T herefore [NaOH] = 3.75 104 1000/30 = 0.0125 mol dm3 Kw = [H+(aq)][OH(aq)] pH = log(1 1014/0.0125) = 12.10

7 (a) (b)

(c)

(d)

8 (a) (b)

(c)

(v) (c) (i) (ii)

(d)

9 (a) (b)

(iii)

(iv) metacresol purple he indicators pH range coincides with the pH T change during the sharp increase in pH in the titration curve. The extent of dissociation of the acid (i) H2SO3(aq) + CH3COOH(aq) Y HSO3(aq) + CH3COOH2+(aq) acid 1 base 2 base 1 acid 2 (ii) CH3COOH is a stronger acid than C6H5OH. Therefore, CH3COOH will donate H+ to C6H5OH CH3COOH(aq) + C6H5OH(aq) Y CH3COO(aq) + C6H5OH2+(aq) + For HCl, pH = log[H ] = log 0.045 = 1.35 ________________ For CH3COOH, [H+] = (Ka [CH3COOH]) [H+] = 8.75 104 mol dm3 pH = log 8.75 104 = 3.058 2 mol of each acid produce 1 mol of H2 Mg + 2HCl MgCl2 + H2 Mg + 2CH3COOH (CH3COO)2Mg + H2 HCl is the stronger acid and in solution [H+] in HCl > [H+] in CH3COOH. HCl will therefore react quicker as its [H+] is greater. (i) Kw is the ionic product of water (ii) Kw = [H+(aq)] [OH(aq)] 5.00 103 21.35 amount of HCl = __________________ 1000 = 1.067 104 mol 1.067 104 amount of Ca(OH)2 = ___________ 2 = 5.34 105 mol concentration of Ca(OH)2 = 40 5.34 105 = 2.136 103 mol dm3 3 [OH ] = 2 2.7 10 = 5.4 103 mol dm3 Kw 1.0 1014 [H+(aq)] = ________ = __________ [OH (aq)] 5.4 103 = 1.85 1012 mol dm3 pH = log (1.85 1012) = 11.73/11.7 [H+] [OH] = 1014 mol2 dm6; I f [OH] is 100 (102) greater than [H+], [OH] must be 106 and [H+] must be 108 pH = 10pH, so pH = 8 (i) a weak BrnstedLowry acid is a proton donor that partially dissociates [HCOO][H+] [H+]2 Ka = ___________ = _________ [HCOOH] [HCOOH] _____________________ [H+] = {(1.58 104) (0.025)} = 1.99 103 mol dm3 pH = log[H+] = log 1.99 103 = 2.70

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(c) (i) A buffer solution minimises pH changes. (ii) sodium methanoate, HCOONa HCOONa supplies HCOO as the conjugate base. (iii) he pH of the buffer solution depends upon the T extent of dissociation given by the Ka value and the relative concentrations of the weak acid and conjugate base. 1400 65 (d) Mass of HNO3 = __________ / 910 g 100 910 amount of HNO3 = ____ = 14.4 mol 63 pH = log[H+] = log 14.4 = 1.16

(e) 2HNO3 + CaCO3 Ca(NO3)2 + CO2 + H2O (f) A conjugate acidbase pair is two species differing by H+ acid 1: HNO3; base 2: NO3 acid 2: HCOOH2+; base 2: HCOOH (g) (i) 6HNO3 + S H2SO4 + 6NO2 + 2H2O or 4HNO3 + S H2SO4 + 4NO2 + H2 (ii) he oxidation number of N decreases from +5 in T HNO3 to +4 in NO2.

2.2 Energy

1 (a) (i) nergy is needed to overcome the force of attraction between outer electrons and nucleus E (ii) lectron affinity involves a neutral atom gaining of an electron by attraction from the nucleus E (b) (i) Ca2(g) O2(g)
Ca2(g) O(g) 2e HEA1 141 kJ mol Ca(g) O(g) e HI1 590 kJ mol1 Ca(g) O(g) Ha 249 kJ mol1 Ca(g) O2(g) HLE 3459 kJ mol1
1

HEA1 798 kJ mol1 Ca2(g) O(g) e

HI2 1150 kJ mol1

Ha 178 kJ mol1 0

Ca(s) O2(g) Hf CaO(s)

(ii) Hf = +178 + 249 + 590 + 1150 + (141) + 798 + (3459) = 635 kJ mol1 (iii) attice enthalpy of FeO is more negative and more L exothermic than lattice enthalpy of CaO. Ionic radius of Fe2+ must be less than that of a Ca2+ ion. This leads to greater attraction between Fe2+ ions and O2 ions than between Ca2+ ions and O2 ions.

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2 (a) Lattice enthalpy is the enthalpy change that accompanies the formation of one mole of an ionic compound from its gaseous ions under standard conditions. Mg2+(g) + 2Cl(g) MgCl2(s) (b) Mg2(g) 2Cl(g) 2e
2 349 HI2 1451 kJ mol1 Mg(g) HI1 738 kJ mol1 Mg(g) 2Cl(g) 2 Ha 2 123 kJ mol1 2Cl(g) e Mg2(g) 2Cl(g)

Mg(g) Cl2(g)

HLE

Ha 148 kJ mol1 0

Mg(s) Cl2(g) Hf 641 kJ mol1 MgCl2(s)

641 = +148 + 2 123 + 738 + 1451 + 2 (349) + HLE HLE = 641 (+148 + 2 123 + 738 + 1451 + 2 (349)) = 2526 kJ mol1 (c) Na+ has a larger radius than Mg2+ and Br has a larger radius than Cl Na+ has a smaller charge than Mg2+ Br experiences less attraction than Cl Na+ experiences less attraction than Mg2+ herefore there is much less attraction between Na+ ions and Br ions than between Mg2+ ions and Cl ions. T One mark for correct spelling, punctuation and grammar in at least two sentences. 4 (a)
NH4(g) Cl(g) Hydration of NH4 NH4(aq) Cl(g) Lattice enthalpy

3 (a) (i) H1 = Enthalpy change of formation of magnesium oxide H2 = Enthalpy change of atomisation of magnesium H3 = First ionisation energy of magnesium (ii) Mg2+(g) + O2(g) (iii) he electron being gained is repelled by the T negative charge of the O(g) ion. (b) (i) 602 = 149 + 736 + 1450 + 248 + 650 + HLE HLE = 602 (149 + 736 + 1450 + 248 + 650) = 3835 kJ mol1 (ii) Lattice enthalpy of barium oxide is less exothermic than that of magnesium oxide. This is because Mg2+ has a smaller ionic radius than Ba2+ so there is a stronger attraction between the positive and negative ions. (c) Magnesium oxide has a high melting point because it has a highly exothermic lattice enthalpy resulting from strong attractive forces between Mg2+ and O2 ions.

Hydration of Cl
NH4(aq) Cl(aq) Enthalpy change of solution

NH4Cl(s)

(b) Hhyd(NH4+) + Hhyd(Cl) = HLE(NH4Cl) + Hs(NH4Cl) Hhyd(NH4+) + (364) = 689 + 15 Rearranging: Hhyd(NH4+) = (+364) + 689 + 15 Hhyd(NH4+) = 310 kJ mol1 (c) There is an increase in disorder on dissolving. Increase in entropy outweighs increase in enthalpy. 5 (a) Energy lost = mcT = 108.48 4.18 12.5 = 5668 J = 5.668 kJ 8.48 m __ mount of LiCl dissolved = = ___________ A m (6.9 + 35.5) = 0.200 mol 1.60 ______ = 28.34 kJ mol1 Hsolution = 0.200
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(b) here is an increase in disorder on dissolving. T Increase in entropy outweighs increase in enthalpy. (c) (i) X: Lattice enthalpy of LiCl; Y: Enthalpy change of hydration of Li+ (ii) Li+ ions are smaller than Na+ ions. Small ions exert more attraction on water molecules and more energy is released. 6 (a) n Equation 1, S is +ve because a gas is released. I n Equation 2, S is ve because the number of gas I molecules decreases. (b) G = H TS. (c) (i) ncrease in entropy from formation of a gas I outweighs increase in enthalpy. verall, balance between enthalpy and entropy O is such that H TS < 0. (ii) At high temperatures, decrease in entropy from decrease in the number of gas molecules outweighs decrease in enthalpy because TS becomes more significant. verall, balance between enthalpy and entropy O is such that H TS > 0. 7 (a) S is positive as the forward reaction results in an increase in the moles of gas molecules. (b) S = S (products) S (reactants) = (198 + 3 131) (186 + 189) = +216 J K1 mol1 (c) G = H TS At room temperature, G = +210 298 0.216 = +145.632 kJ mol1 For a reaction to take place, G < 0 kJ mol1 (d) When G =0, 0 = H TS 210 H T = ___ = ______ = 972 K = 699 C S 0.216 8 (a) he standard electrode potential of a half cell, E, is T the e.m.f. of a half cell compared with a standard hydrogen half cell, measured at 298 K with solution concentrations of 1 mol dm3 and a gas pressure of 100 kPa (1 atmosphere). (b) (i) Electrons
V Salt bridge Cu(s) Ag(s)

(c)

9 (a)

(b) (c)

(d)

10 (a)

(iv) Cu + 2Ag+ Cu2+ + 2Ag E for Fe3+/Fe2+ is less positive than for Cl2/Cl. T herefore the Fe2+ has a greater tendency to lose electrons than Cl. E for I2/I is less positive than for Fe3+/Fe2+. T herefore the I has a greater tendency to lose electrons than Fe2+. T he standard electrode potential of a half cell, E, is the e.m.f. of a half cell compared with a standard hydrogen half cell, measured at 298 K with solution concentrations of 1 mol dm3 and a gas pressure of 100 kPa (1 atmosphere). Standard cell potential = 1.52 1.36 = 0.16 V (i) 2MnO4 + 10Cl + 16H+ 2Mn2+ + 5Cl2 + 8H2O (ii) Cl from 1 to 0 Mn from +7 to +2 (iii) Cl has been oxidised Mn in MnO4 has been reduced Standard electrode potential applies only to a concentration of 1 mol dm3, and potentials give no information about rates. When concentration of Cl decreases, equilibrium moves towards Cl, and Cl2/Cl half cell potential becomes less negative. The difference between the electrode potentials becomes smaller and the Cl2/Cl potential may even become more positive than the MnO4/Mn2+ potential. The reaction will then not be feasible. Electrons (i)
V T 298 K Salt bridge Cr(s) Cd(s)

Cr3(aq) (1 mol dm3)

Cd2(aq) (1 mol dm3)

Cu2(aq)

Ag(aq)

(ii) Direction from Cu(s) to Ag(s) shown near to wire (iii) Standard cell potential = 0.80 0.34 = 0.46 V

(ii) Direction from Cr(s) to Cd(s) shown near to wire (iii) Cr half cell E value is more negative. (b) 2Cr(s) + 3Cd2+(aq) 2Cr3+ (aq) + 3Cd(s) (c) (i) Standard cell potential = 0.40 (0.74) = 0.34 V (ii) Concentration of Cr3+ decreases so equilibrium moves towards Cr3+ and Cr half-cell becomes more negative. Therefore there is a bigger difference between the electrode potentials and the cell potential will increase.

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11 (a) he standard electrode potential of a half-cell, E, T is the e.m.f. of a half-cell compared with a standard hydrogen half-cell, measured at 298 K with solution concentrations of 1 mol dm3 and a gas pressure of 100 kPa (1 atmosphere). (b) (i) solution A = 1 mol dm3 HCl(aq) (or 1 mol dm3 H+(aq)) solid B = platinum electrode (ii) Direction from hydrogen half-cell along wire to S2O82 half-cell (iii) S2O82 + H2 2SO42 + 2H+ (c) molar mass of Na2S2O8 = 238.2 g mol1 molar mass of Na2SO4 = 142.1 g mol1 23.82 g of Na2S2O8 and 14.21g of Na2SO4 (d) Concentration of SO42 decreases so equilibrium moves towards SO42 and S2O82/SO42 half-cell becomes more positive. Therefore there will be a bigger difference between electrode potentials and the cell potential will increase. 12 (a) (i) moles of Cu = 0.68 5/1000 = 0.0034 mass of Cu = 0.0034 63.5 = 0.216 g % Cu = 0.216/0.28 = 77% (ii) Ratios Cu : N : O : H = 26.29/63.5 : 11.6/14 : 59.63/16 : 2.48/1 = 0.414 : 0.829 : 3.73 : 2.48 = 1:2:9:6 Empirical formula of A = CuN2O9H6 (iii) Formula usually shown as: Cu(NO3)23H2O (b) Cu Cu2+: Cu from 0 to +2 NO3 NO: N from +5 to +2 ratio of Cu : N in equation is 3 : 2 3Cu + 8H+ + 2NO3 3Cu2+ + 2NO + 4H2O (c) (i) moles of A = 90/24000 = 3.75 103 Mr of A = 0.24/ 3.75 103 = 64 Gas is SO2 (ii) Cu + 2H2SO4 CuSO4 + SO2 + 2H2O

mass FeSo47H2O = 2.1168 103 277.9 = 0.588 g 0.588 % purity = ______ 100 = 89.8% 0.655 2 (a) (i) Blue to green to yellow solution. (ii) he lone pair on the chloride ion is donated to T the copper(II) ion. A co-ordinate (dative covalent) bond is formed. (b) A light blue precipitate forms, which is soluble in excess ammonia forming a deep blue solution. (c) Ammonia molecule has one lone pair of electrons and three bonding pairs. The lone pair repels the bonding pairs more than they repel each other, reducing the bond angle. Each ammonia ligand bonded to copper has four bond pairs. So equal repulsion between bonding pairs. Angle larger, at 109.5. 3 Transition elements are d block elements that have an ion with an incomplete d sub-shell. Cu2+ 1s2 2s2 2p6 3s2 3p6 3d9 Note that the d sub-shell is incomplete.
OH2 H2O H 2O Cu OH2 OH2 OH2 2

2.3 Transition elements

1 (a) dd aqueous sodium hydroxide which gives a rusty A brown precipitate. (b) (i) Cr2O72 + 14H+ + 6Fe2+ 2Cr3++ 7H2O + 6Fe3+ (ii) No. of moles of Cr2O72 = cv/1000 = (0.0180 19.6)/1000 = 3.528 104 moles Moles of iron(II) 3.528 104 6 = = 2.1168 103 = 0.002118 moles FeSo47H2O = moles Fe2+ = 2.1168 103 mol M(FeSo47H2O) = 277.9 g mol1

The shape is tetrahedral. Water molecules are ligands (electron-pair donors) and these form co-ordinate bonds to the central metal. The Cu2+ ion is an electron-pair acceptor. ransition metals have variable oxidation states, for T example Cu2+ and Cu+. ransition metals form coloured compounds: CuCl42 T is yellow. [Cu(H2O)6]2+ is blue. ransition metals and their ions act as catalysts. Iron T is a catalyst for the Haber process. 4 (a) 1s2 2s2 2p6 3s2 3p6 3d5 ron has an incomplete d sub-shell in the Fe3+ ion. It I is a transition metal. (b) 1 Variable oxidation state. 2 Forms coloured compounds. (c) Fe2+ reacts with hydroxide ions to form a green precipitate whereas Fe3+ reacts with hydroxide to form an orange-brown precipitate. (d) 4Fe2+ + O2 + 4H+ 4Fe3+ + 2H2O (e) (i) Copper may react with MnO4. Copper reacts with Fe3+ reducing it back to Fe2+. (ii) Mn in MnO4 changes from oxidation state +7 to +2 in Mn2+ (it is reduced). Fe changes from Fe2+ (+2) to Fe3+ (+3) and is oxidised.

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(iii) No. of moles of MnO4 = (22.5 0.02)/1000 = 4.50 104 2+ Moles of Fe = 5 4.50 104 = 2.25 103 Mass of Fe2+ = 2.25 103 55.8 = 0.1256 g Percentage = (0.1256/0.675) 100 = 18.6% 5 (a) A pale blue solution forms a light blue precipitate which is soluble in excess ammonia to give a deep blue solution. (b) 2 OH2
H2O Cu H2O OH2 OH2 OH2

8 (a) (i) +3 (ii)

Cl

Cl OH2 Ru

Cl

OH2 OH2 Ru

H2O OH2 Cis

OH2

H2O OH2 Trans

Cl

(iii) (b) (i) (ii) 9 (a) (i)

(c) ater has 2 lone pairs and 2 bonding pairs. The W two lone pairs repel the bonding pairs more than the bond pairs repel each other. Bond angle is 104.5 but in the ligand a lone pair is used to form a co-ordinate bond to the metal. Water ligand has 3 bond pairs and one lone pair. There is less repulsion. So the bond angle is greater than in a water molecule. 6 (a) Transition elements are catalysts. (b) (i) 2 Cl
109.5 Cl Cl Cl C

Cistrans. HCl(conc). Ligand substitution. T his is the number of co-ordinate bonds formed by ligands to the transition metal ion. (ii) Square planar. (b) (i) Ligand substitution. (ii) x = 2 y=0 (c) (i) O O
Cl Cl Pt NH3 Cl Pt NH3 Cl NH3 H 3N

(ii) Cistrans. (iii) Cis-platin binds with DNA and prevents cell division, stopping the growth of tumours. 10 (a) (i) [Fe(NH3)4Cl2]+ (ii)
NH3 NH3 H3N Cl NH3 Cis Fe NH3 Cl H3N Cl NH3 Trans Cr Cl NH3

Cl Concentrated hydrochloric acid. [Cu(H2O)6]2+ + 4Cl CuCl42 + 6H2O T his is a reaction where one ligand is replaced by another. Here H2O is replaced by Cl. 7 (a) Oxygen changes from 1 (H2O2) to 2 (in H2O): it is reduced. Oxygen changes from 1 (H2O2) to 0 (O2): it is oxidised. (b) (i) 2MnO4 + 6H+ + 5H2O2 2Mn2+ + 8H2O + 5O2 (ii) No. of moles of MnO4 = (17.5 0.02)/1000 = 0.00035 No. of moles of H2O2 = (0.00035/2) 5 = 0.000875 0.000875 = (concentration 25)/1000 Concentration = 0.0350 mol dm3 (c) Name of reagent used: NaOH Observation: Redbrown precipitate. (ii) (iii) (iv)

(b)

11 (a) (b) (c) (d) (e)

(iii) 6 Cis platin is an anti-cancer drug. It binds to DNA and prevents replication, stopping the growth of tumours. +2 No. of moles of S2O32 = (0.100 22.0)/1000 Answer: 000220 mol No. of moles of I2 = 0.00220/2 = 0.0011 Answer: 000110 mol No. of moles of Cu2+ = 0.00110 2 Answer: 000220 mol 0.00220 = (concentration 25.0)/1000 Answer: 0.0880 mol dm3

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12 (a) (i) From pink to blue (ii) Tetrahedral (iii) Ligand substitution (b) H H H H
N H H H C H C N H C C N H N

H (c) (i) Optical isomerism 3 (ii) NH

2

H H

3 H2 N H2N H2 N Co H2N 2 NH Co 2 NH

H2N

Co H2N H2N 2 N NH H2 N NH2 H2

H2N Co

NH2 2 NH

NH2

NH2 NH2

N 2N H2 HN H2 H2N

14 (a) MoO3 + 2Al Mo + Al2O3 (b) [Kr]4d3, which has an incompletely filled d sub-shell, meaning it is a transition metal ion. (c) Cr2O72(aq) + 2H+(aq) + 3MoO2(s) 3MoO42(aq) + 2Cr3+(aq) + H2O(l) (d) (i) K2FeO4 (ii) Moles of KOH = 4.00 10.0/1000 = 0.0400 mol Moles of Fe2O3 = 1.00/159.6 = 0.00627 mol From the equation, 1 mol Fe2O3 reacts with 10 mol OH 10 mol KOH 0.00400 mol Fe2O3 reacts with 0.0400 mole KOH. Fe2O3 is in excess by 0.00227 mol.

13 (a) 1s2 2s2 2p6 3s2 3p6 3d6; Fe2+ has an incompletely filled d subshell. (b) (i) [Fe(H2O)6]2+ 2 (ii) OH2
H2O Fe H2O OH2 OH2 90 OH2

(c) (d)

(e) (f)

(iii) Each ligand donates an electron pair to the metal ion to form a coordinate (dative covalent) bond. [Fe(H2O)6]3+ + 4Cl Y [FeCl4]2+ + 6H2O FeCl2 gives a green precipitate and FeCl3 gives a brown-red precipitate. Fe2+(aq) + 2OH(aq) Fe(OH)2(s) Cr changes from +3 to +6, which is oxidation; Fe changes from +6 to +3, which is reduction. 4FeO42 + 20H+ 4Fe3+ + 3O2 + 10H2O

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