Week 2 Answers 28 December 2016

The number of marks expected to be allocated to each question is given in square brackets on the right-hand margin of the page.

Question 1

Benzene is an aromatic hydrocarbon compound with the molecular formula C6H6. A number of
other cyclic hydrocarbon compounds also containing six carbon atoms are given below. In
benzene, the C=C double bonds can move around the ring as if all C–C bonds were equivalent.
The imaginary compound cyclohexa-1,3,5-triene is a hypothetical situation in which all of the
C=C bonds are “locked” in place. This imaginary compound is supposed to be an analogue of
benzene, and comparing the theoretical properties of cyclohexa-1,3-triene to those of benzene
can be done to establish novel features of benzene’s aromatic structure.

Consider the following set of enthalpies of hydrogenation.

cyclohexane

∆H1 ∆H3
+ H2 + 3H2

imaginary compound
cyclohexene
+ 2H2 “cyclohexa-1,3,5-triene”
+ 3H2
∆H2 ∆H4

cyclohexa-1,3-diene benzene

∆H1 = –119.5 kJ mol–1

∆H2 = –231.5 kJ mol–1

a. Based purely on the values of ∆H1 and ∆H2 given above, give an estimate for the value of
∆H3, the enthalpy of hydrogenation (to cyclohexane) of the imaginary compound
cyclohexa-1,3,5-triene. Give your reasoning.

The enthalpy change of hydrogen of cyclohexene is –119.5 kJ mol–1. One C=C double
bond is hydrogenated to get from cyclohexene to cyclohexane.
In the imaginary compound “cyclohexa-1,3,5-triene”, three C=C double bonds are
hydrogenated.
Therefore, the expected enthalpy of hydrogenation of “cyclohexa-1,3,5-triene” is three
times the enthalpy of hydrogenation of cyclohexene.
3 × –119.5 ≈ 3 × –120 = –360 kJ mol–1.

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Week 2 Answers 28 December 2016

b. The actual value of ∆H4, the enthalpy of hydrogenation of benzene to cyclohexane is:

∆H4 = –206 kJ mol–1.
(a) Comment on this value, and determine the aromatic stabilisation energy of benzene.

The expected enthalpy of hydrogenation of “cyclohexa-1,3,5-triene” is –360 kJ mol–1. The

actual enthalpy of hydrogenation of benzene 150 kJ mol–1 less negative (i.e. less
exothermic) than “cyclohexa-1,3,5-triene”. This means that benzene is more stable than
would be anticipated for “cyclohexa-1,3,5-triene” by approximately 150 kJ mol–1.

(b) Use a Hess cycle to determine the enthalpy of conversion of cyclohexa-1,3-diene to

benzene.
Hess cycle:
cyclohexa-1,3-diene cyclohexane

(red dotted line shows + 2H2

the path required to
∆H2
calculate enthalpy
of conversion of
cyclohexa-1,3-diene + 3H2
to benzene) ∆Hconv ∆H4

benzene

∆H2 = –231.5 kJ mol–1; ∆H4 = –206 kJ mol–1.

∆Hconv = ∆H2 — ∆H4 (∆H4 is negative since reaction path is going in
opposite direction to arrow for ∆H4.)

∆Hconv = –231.5 — (–206) = –231.5 + 206 = –25.5 kJ mol–1.

(c) Comment on the relative thermodynamic stabilities of cyclohexa-1,3-diene and

benzene in light of your result.

∆Hconv is negative which implies that benzene is more thermodynamically stable than
cyclohexa-1,3-diene.

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Week 2 Answers 28 December 2016

Question 2

Consider the following reaction scheme:

(i) KOH (aq)
KMnO4 (aq) (ii) ∆
*

Reactant A Product X Product Y

In an initial step, 1.42g of Reactant A was treated (oxidised) with aqueous potassium
permanganate to give Product X. A time-resolved 13C NMR experiment was then performed
using Product X during a titration with aqueous potassium hydroxide. By measuring the
intensity of the NMR peak of the carboxylic acid carbon atom marked with an asterisk relative
to that of its carboxylate anion, it is possible to accurately measure the extent of deprotonation
when Product X is treated with a solution of a base. From the relative peak intensities, it is
therefore possible to spectroscopically measure the endpoint of the titration. The solution of the
carboxylate intermediate from the titration deprotonation step was then heated to finally give
Product Y.

a. In the titration step, 35.0 cm–3 of a 0.200 mol dm–3 solution of KOH was added to Product
X. Assuming that the KOH deprotonated all of the Product X in the reaction mixture, what
was the percentage yield for the initial oxidation step?

Calculate number of moles of KOH used during titration:

concentration (mol dm–3) = moles (mol) ÷ volume (dm3) (c = n ÷ v)

moles (mol) = concentration (mol dm–3) × volume (dm3) (n = c × v)

nKOH = 0.200 × (35.0 ÷ 1000) = 7.00 × 10–3 moles.

mole ratio of KOH : X = 1 : 1 (because Product X only has one

carboxylic acid group)

So 7.00 × 10–3 moles of X produced from reaction.

Initial number of moles of Reactant A:

mass (g) = moles (mol) × relative molecular mass (g mol–1) (m = n × Mr)

moles (mol) = mass (g) ÷ relative molecular mass (g mol–1) (n = m ÷ Mr)

nX = 1.42 ÷142.197 = 9.99 × 10–3 moles

Yield = (number of moles of X produced ÷ initial number of moles of A) × 100

Yield = (7.00 ÷ 9.99) × 100 = 70.1%.

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Week 2 Answers 28 December 2016

b. When Product X is deprotonated, it gives an anionic carboxylate intermediate. If this

intermediate is heated sufficiently, CO2 (g) is given off (“decarboxylation”).

The reaction vessel containing this anion intermediate is heated to 150°C. 97.78 cm3 of CO2
(g) is given off.
(i) Calculate the percentage yield for the decarboxylation step, and calculate the mass
of Product Y obtained from the reaction.
Calculate number of moles of CO2 produced during decarboxylation:

pressure (Pa) × volume (m3) =

number of moles (mol) × gas constant R (J K–1 mol–1) × temperature (K)
(pV = nRT)

pV = nRT ⇒ n = pV ÷ RT

p = 1 × 105 Pa; V = 97.78 cm3; R = 8.3145; T = 423.15 K.

nCO2 = (1 × 105 × (97.78 ÷ 1,000,000)) ÷ (8.3145 × 423.15)

nCO2 = 2.78 × 10–3 moles.

Mole ratio of CO2 : Y = 1 : 1

So nY = 2.78 × 10–3 moles

Percentage yield for decarboxylation step is number of moles of Product Y produced

divided by number of moles of Product X initially used multiplied by 100.
Yield = (nX ÷ nY) × 100
Yield = 2.78 ÷ 7 = 39.7%.

mY = nY × Mr(Y) = 2.78 × 10–3 × 128.18 = 0.356g

(ii) What is the yield for the overall synthesis?

Overall yield for synthesis is number of moles of Product Y produced divided by number
of moles of Reactant A initially used multiplied by 100.
Overall yield = (nY ÷ nA) × 100
Overall yield = 2.78 ÷ 9.99 = 27.8%

c. The enthalpy of hydrogenation of the final Product Y (“naphthalene”) to Product Z (given

below) is –355 kJ mol–1. Using the data given in Question 1, and by considering the
mesomeric possibilities of benzene compared to those of naphthalene, provide a brief
explanation of this value, stating the nature of any assumptions made.

∆H5 = –355 kJ mol–1

+ 5H2

Molecular masses: Constants:

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Week 2 Answers 28 December 2016

Naphthalene contains 5 C=C double bonds. The average enthalpy of hydrogenation of

the double bonds in napthalene is therefore –355 ÷ 5 = –71 kJ mol–1.
Benzene contains 3 C=C double bonds. The average enthalpy of hydrogenation of the
double bonds in benzene is therefore –206 ÷3 = –68.7 kJ mol–1. This means that the
aromaticity in benzene is slightly stronger than that in naphthalene.
In benzene, the three pairs of electrons in the C=C double bonds can be pushed around
the ring and lead to an equivalent structure.

However, in napthalene, trying to push all five pairs of electrons around the double ring
leads to an impossible pentavalent carbon mesomer (marked with an asterisk).

This suggests that naphthalene is better treated as two separate aromatic systems.

Reactant A: 142.197 g mol–1 Assume an atmospheric pressure of 1 bar (1 bar = 105 Pa)
Product X: 172.18 g mol–1 Gas constant R: 8.314598 J K–1 mol–1
Product Y: 128.18 g mol –1

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Week 3 Answers 28 December 2016

The number of marks expected to be allocated to each question is given in square brackets on the right-hand margin of the page.

Question 1

a. State Le Chatelier’s principle for systems in dynamic equilibrium. In particular, consider

how the position of equilibrium varies when small amount of a compound involved in the
equilibrium is added to the equilibrium mixture.
Le Chatelier’s principle states that if a change (or “perturbation”) is introduced into a
system in dynamic equilibrium, then the system will act to counteract the effect of the
perturbation.
For example, in an equilibrium A + B C + D, if a small amount of A is added, then
the system will act to remove the extra A by producing more of C and D.

Consider the following equilibrium, describing the dissociation of a generic (Brønsted) acid HA
in water:

HA + H2O A⊖ + H3O⊕.

b. How is pH related to the concentration of H3O⊕ or H⊕ species?

pH = —log10[H⊕]

c. Give the expression for the equilibrium constant, Kc, for the dissociation in terms of the
concentrations of all of the species involved in the reaction.

Kc = [H3O⊕] [A⊖] / [HA] [H2O]

d. Making and stating an appropriate assumption, give the expression for Ka, the acid
dissociation constant.

Assuming that HA is a weak acid that only partially dissociates in water means that we
can also assume that the concentration of H2O remains effectively constant.
⇒ Ka = [H3O⊕] [A⊖] / [HA]
e. By taking an appropriate logarithm, derive the Henderson-Hasselbalch equation:
[A⊖]
pH = pKa + log10 —— .
[HA]

Ka = [H3O⊕] [A⊖] / [HA]

log10Ka = log10[H3O⊕] + log10([A⊖]/[HA]) –log10Ka = pKa; –log10[H3O⊕] = pH
–pKa = –pH + log10([A⊖]/[HA])
pH = pKa + log10([A⊖]/[HA])

f. Ethanoic acid, CH3COOH, has a pKa of approximately 4.75. Chloroethanoic acid,

CH2ClCOOH, has a pKa of approximately 2.87. Dichloroethanoic acid, CHCl2COOH, has a
pKa of approximately 1.26. Trichloroacetic acid, CCl3COOH, has a pKa of approximately
0.66.

(i) Draw the structures of all four of the above named compounds.
(ii) Which compound is the strongest acid? Provide an explanation for your answer,
based on the structure of the compound.
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Week 3 Answers 28 December 2016

Trichloroacetic acid is the strongest acid since it has the lowest pKa. This can be
explained by considering the effect of the chlorine atoms on the stability of the negatively
charged conjugate base of trichloroacetic acid.
Chlorine is a highly electronegative element, so it is able to inductively stabilise negative
charge. As more chlorine atoms are substituted onto acetic acid, the stability of the
negative charge increases, hence the parent acid becomes more acidic.

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Week 3 Answers 28 December 2016

Question 2

a. Outline the purpose of a buffer solution, and briefly explain the mechanism through which
a buffer solution performs this purpose.

Buffer solutions are used to control the pH of an environment by removing the excess
H⊕ or OH⊖ ions introduced if a small volume of acid or alkali is added.
Acidic buffer solutions contain an excess of the conjugate base of a weak acid, so when a
small volume of acid is added, the H⊕ ions from the added acid protonate the excess
conjugate base instead of remaining free in solution (i.e. are immediately removed), thus
the pH remains virtually constant.

b. The Ka value for the dissociation of propanoic acid, CH3CH2COOH, in water is

approximately 1.34 × 10–5. Calculate its pKa.
pKa = –log10Ka
pKa = –log10(1.34 ×10–5)
pKa = 4.87

c. 0.74g of propanoic acid is added to 100 cm3 of water. 2.88g of sodium propionate is
subsequently added.

(i) Calculate the pH of the resulting solution, ignoring any changes in the volume of the
solution upon the addition of propanoic acid and sodium propionate.
Calculate concentration of propanoic acid:
moles (mol) = mass (g) ÷ relative molecular mass (g mol–1)
n = m ÷ Mr
n = 0.74 ÷74.078 = 9.99 × 10–3 mol.

c (mol dm–3) = n (mol) ÷ v (dm–3)

c = (9.99 × 10–3) ÷ (100 ÷ 1000)
c = 9.99 × 10–2 mol dm–3.

Calculate concentration of sodium propionate:

n = m ÷ Mr
n = 2.88 ÷ 96.060
n = 3.00 × 10–2 mol.

c=n÷v
c = 0.3 mol dm–3.

Using Henderson-Hasselbalch:
pH = pKa + log10([A⊖]/[HA])
pH = 4.87 + log10(0.3/(9.99 × 10–2))
pH = 5.35.

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Week 3 Answers 28 December 2016

(ii) What is the pH of the solution if 1 cm3 of 1.00 moldm–3 HI (hydroiodic acid — a
very strong acid) is added?

HI is very strong acid — assume it fully dissociates. Neglect any changes in the volume
of the solution.

By contrast, assume that propanoic acid is a weak acid, and that all protons from HI
protonate propionate anions.

0.03 moles of propionate (A⊖) in buffer solution before addition of HI.

0.00999 moles of propanoic acid (HA) in buffer solution before addition of HI.

Number of moles of H⊕ added with HI:

n = c × v = 1.00 × (1 ÷ 1000) = 0.001

The 0.001 moles of H⊕ added upon addition of HI are removed by 0.001 moles of
propionate anions:

final number of moles of propionate anions = 0.029

final [A⊖] = 0.29 mol dm–3
and
final number of moles of undissociated propanoic acid = 0.01099
final [HA] = 0.1099 mol dm–3

Now use Henderson-Hasselbalch:

pH = pKa + log10([A⊖]/[HA])

pH = 4.87 + log10(0.29/0.1099)

pH = 5.29

For initial buffer solution, pH = 5.35 ⇒ only a change in pH of 0.06.

For interest only, compare to pure water: pure water has a pH of 7.00. If 1 cm3 of 1.00
mol dm–3 HI were added to 100 cm3 pure water, the final pH would be 3.

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Week 3 Answers 28 December 2016

d. The pKa of ethanoic acid, CH3COOH, is 4.75. 50 cm3 of a 0.100 moldm–3 solution of
ethanoic acid is prepared (in water).

(i) What mass of sodium ethanoate, CH3COONa, must be added to produce a buffer
solution with a pH of 4.95?

Using Henderson-Hasselbalch:

pH = pKa + log10([A⊖]/[HA])

4.95 = 4.75 + log10([CH3COONa]/0.1)

⇒ log10([CH3COONa]/0.1) = 0.20

⇒ [CH3COONa]/0.1 = 100.20 = 1.58

⇒ [CH3COONa] = 1.58 × 0.1

⇒ [CH3COONa] = 0.158 mol dm–3.

Calculate number of moles of CH3COONa in 50 cm3 solution:

n=c×v
n = 0.158 × (50 ÷ 1000)
n = 7.92 × 10–3.

Calculate mass:

mass = moles × Mr
m = (7.92 × 10–3) × 82.034
m = 0.65 g.

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Week 3 Answers 28 December 2016

(ii) A second buffer solution of 0.100 mol dm–3 ethanoic acid and sodium ethanoate has
a pH of 4.55. Which buffer solution containing ethanoic acid and sodium ethanoate
produces the largest change in pH upon the addition of 0.6 cm3 of 2.00 moldm–3
HCl?
HCl is very strong acid — assume it fully dissociates. Neglect any changes in the volume
of the solution. Assume that ethanoic acid is a weak acid, and that all protons from HCl
protonate ethanoate anions.

Buffer solution 1:

7.92 × 10–3 moles of ethanoate (A⊖) in buffer solution 1 before addition of HCl.
0.100 × (50 ÷ 1000) = 5 × 10–3 moles of ethanoic acid (HA) in buffer solution before
addition of HCl.

Number of moles of H⊕ added with HI:

n = c × v = 2.00 × (0.6 ÷ 1000) = 1.2 × 10–3 = 0.0012 moles

The 0.0012 moles of H⊕ added upon addition of HCl are removed by 0.0012 moles of
ethanoate anions:

⇒ final number of moles of ethanoate anions = 6.72 × 10–3

⇒ final [A⊖] = 0.134 mol dm–3
and
⇒ final number of moles of undissociated ethanoic acid = 6.2 × 10–3
⇒ final [HA] = 0.124 mol dm–3

Now use Henderson-Hasselbalch:

pH = pKa + log10([A⊖]/[HA])

pH = 4.75 + log10(0.134/0.124)

pH = 4.78

For initial buffer solution 1, pH = 4.95 ⇒ change in pH of 0.17.

For buffer solution 2: repeat entire process.

From Henderson-Hasselbalch pH = pKa + log10([A⊖]/[HA])

4.95 = 4.75 + log10([CH3COONa]/0.1)
⇒ log10([CH3COONa]/0.1) = –0.20
⇒ [CH3COONa]/0.1 = 10–0.20 = 0.631
⇒ [CH3COONa] = 0.0631 mol dm–3.
Calculate number of moles of CH3COONa in 50 cm3 solution:
n = c × v = 0.0631 × (50 ÷ 1000)
n = 3.15 × 10–3 moles.

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Week 3 Answers 28 December 2016

3.15 × 10–3 moles of propionate (A⊖) in buffer solution 1 before addition of HCl.
0.100 × (50 ÷ 1000) = 5 × 10–3 moles of ethanoic acid (HA) in buffer solution before
addition of HCl.
0.0012 moles of H⊕ added upon addition of HCl are removed by 1.2 × 10–3 moles of
ethanoate anions:
⇒ final number of moles of ethanoate anions = 1.95 × 10–3
⇒ final [A⊖] = 0.0391 mol dm–3
and
⇒ final number of moles of undissociated ethanoic acid = 6.2 × 10–3
⇒ final [HA] = 0.124 mol dm–3

Now using Henderson-Hasselbalch again: pH = pKa + log10([A⊖]/[HA])

pH = 4.75 + log10(0.0391/0.124)
pH = 4.25
For initial buffer solution 2, pH = 4.55 ⇒ change in pH of 0.20.

Buffer solution 2 undergoes a larger change in pH than buffer solution 1 upon addition
of a small volume of HCl.

Molecular masses:
Propanoic acid: 74.078 g mol–1
Sodium propionate: 96.060 mol–1
Sodium ethanoate: 82.034 g mol –1

∼ "12 ∼ AP