Name : ________________________ Class : ________________________ 2012 JC2 H2 Chemistry Term 3 Week 6 (SPA Banded) Topic: Thermochemistry Time allocation:

18 minutes (Gp A) Modified MJC Prelim 2006 1 (a) The compound furan, (CH)4O, is unsaturated and has a structure in which the four carbon atoms and one oxygen atom are connected together in a ring. It is a liquid at room temperature with a boiling point of 31oC. It is used to make solvents and nylon. The displayed formula of furan is as follows: HCCH || || HC CH O (i) By constructing an appropriate energy cycle, calculate the enthalpy of the following reaction of furan at 298K in kJ mol-1 (CH)4O (l) 4C (g) + 4H (g) + O (g) Use the following given enthalpy values: Hf[(CH)4O] = -62 kJ mol-1 Hat (C) = +717 kJ mol-1 Hat (H) = +218 kJ mol-1 Hat (O) = +250 kJ mol-1 Hrxn (CH)4O (l) Hf[(CH)4O] 4C (g) + 4H (g) + O (g) 4Hat (C) + 4Hat (H) + Hat (O) 4C(s) + 2H2(g) + O2(g) [2 marks for completed energy cycle]

By Hess Law, Hrxn = - Hf[(CH)4O]+ 4Hat (C) + 4Hat (H) + Hat (O) = -(-62) + (4 X 717) + (4 X 218) + 250 = +4052 kJ mol-1 (ii) [1/2]
Ans in J mol
-1

Either one correct [1/2]

[0]

It is also possible to calculate the value of the enthalpy change for the reaction above by using appropriate bond energy values from the Data Booklet. The value calculated using this method differs from that calculated by using the Hess Law approach in part (ai). By considering the bonding in furan and the definition of bond energy, suggest one reason for the difference in enthalpy values. Furan is a liquid at room temperature and bond energy is applicable for gaseous molecules. [1] OR Bond energy values from the Data Booklet are average values. [1] OR Delocalisation effect in furan is not considered. [1]

(iii)

Liquid furan is transported by road tankers. Briefly explain why an explosion may happen during transportation if precautions are not taken. [5] Liquid furan has a low boiling point. Therefore, it can be easily vapourised [1/2] to the gaseous state. This causes an increase in pressure [1/2] within the drum. This may lead to an explosion. (b) Iron(II) oxide is a black-coloured oxide used for glazing. (i) What do you understand by the term lattice energy of an ionic compound? Lattice energy of an ionic compound is the energy released when 1 mole of the ionic compound is formed from its constituent gaseous ions under standard conditions. [1 or 0]

(ii)

Construct and label carefully a Born-Haber cycle for the formation of iron(II) oxide from its elements. Use the cycle to calculate the lattice energy of iron (II) oxide. Incorporate the relevant data from the table below as well as relevant data from the Data Booklet. (Ans: -3913Jmol-1) Enthalpy term Standard enthalpy change of formation of FeO Standard enthalpy change of atomisation of Fe First electron affinity of O Second electron affinity of O H / kJ mol-1 -278 +416 -141 +790

Fe2+ (g) + O2- (g) Fe2+ (g) + 2e + O (g) 2nd IE(Fe) Fe+ (g) + e + O (g) 1st IE(Fe) Fe (g) + O (g) Hat(0)or BE 0=0 + O2 (g) Hat(Fe) 0 Fe (s) + O2 (g) Hf(FeO) FeO (s) [2 for Born-Haber Cycle] Hlatt(FeO) Fe (g) 1st EA(O) Fe2+ (g) + e + O- (g) 2nd EA(O)

Total: [2] ; Anything wrong [-1/2] No/wrong state symbol each time Never write H expression / wrong H expression each time Arrow did not touch the line -once Wrong arrow direction each time Did not indicate O for formation level -once Use pencil for drawing ( only lines and arrow acceptable) once

By Hess Law Hf(FeO) = Hat(Fe) + Hat(O) + 1st IE(Fe) + 2nd IE(Fe) + 1st EA(O) + 2nd EA(O) + Hlatt(FeO) - 278 = 416 + 496/2 + 762 + 1560 - 141 + 790 + Hlatt(FeO) Hlatt(FeO) = -3913 kJ mol-1 [1/2] (iii) Explain qualitatively how you would expect the numerical magnitude of the lattice energy, and hence the relative stability, of iron(II) oxide compared with that of iron(II) phosphide.
Either one correct [1/2]

q+q [1/2] r+ + r o Ionic radius of O2- < P3Hlatt

[1/2]

o Ionic charge of P3- > O2 [1/2] o Hlatt of Fe3P2 > FeO [1/2] o Lattice energy of Fe3P2 is more exothermic than FeO [1/2] o Fe3P2 is more stable than FeO [1/2]

Concept : Mathematically - Ionic charge factor overrides the ionic size factor Time allocation: 15 minutes (Gp A) 2 (a) Ammonium nitrate is widely used as an explosive. When ignited, it decomposed to given nitrogen, oxygen and steam. (i) Write an equation with state symbols for the decomposition of ammonium nitrate. NH4NO3 (s) N2 (g) + 2H2O (g) + O2 (g) [1]

(ii)

Given that the enthalpy change of atomisation of ammonium nitrate is + 2928 kJ mol-1 and using bond enthalpy data from the Data Booklet. Calculate the enthalpy change of decomposition of ammonium nitrate with the aid of a suitable energy level diagram to one decimal place.

2N (g) + 4H (g) + 3O (g)

B.E(NN) + 4 x B.E(O H) +

x B.E(O = O)

Hatom (NH4NO3)

NH4NO3 (s)

Hdecomp(NH4NO3)

N2 (g) + 2H2O (g) + O2 (g) [2 marks for energy level diagram] Using Hess Law,
Hat (NH4NO3) - Hdecomp(NH4NO3) = B.E(NN) + 4 x B.E(O H) + x B.E(O = O)

Hdecomp(NH4NO3) = Hatom (NH4NO3) - B.E(NN) - 4 x B.E(O H) - x B.E(O = O) Hdecomp(NH4NO3) = +2928 994 4(460) - (496) [1/2] = - 154.0 kJmol-1 ( to one decimal place) [1/2] * Not to 1 dp -0 marks (iii) Give two reasons why the decomposition of ammonium nitrate is explosive. [6] Hdecomp(NH4NO3) is relatively exothermic resulting in heat given out during decomposition. [1] The decomposition of NH4NO3 gives products which are gaseous resulting in great expansion of volume. [1]

(b) Ammonium nitrate is also used in commercial cold packs where ammonium nitrate is packed together with water in separate compartments. To use the cold pack, the cold pack is rubbed which ruptures the compartments containing ammonium nitrate and water. On dissolution of ammonium nitrate in water, the temperature decreases. (i) The standard enthalpy change of hydration of ammonium ions and nitrate ions are 132 kJ mol-1 and 207 kJ mol-1 respectively and the lattice energy of ammonium nitrate is 365 kJ mol-1. Calculate the standard enthalpy change of solution of ammonium nitrate. Hsoln(NH4NO3) = Hhyd(NH4+) + Hhyd(NO3-) Hlatt(NH4NO3) = - 132 + (- 207) (- 365) = + 26 kJmol-1 [1/2] (ii) Calculate the minimum temperature that can be obtained if a commercial cold pack containing 20.0g of ammonium nitrate and 60 cm3 of water is used. The exterior temperature is 25.0 C and the specific heat capacity of water is 4.2 J g-1 K-1.
Either one correct [1/2]

No. of moles of NH4NO3 =

20 = 0.25 [1/2] 14.0 + 1.0 4 + 14.0 + 3 16.0

Q, amt of heat absorbed by dissolution of 20.0g of NH4NO3 = 0.25 x 26 = 6.50 kJ Q = mcT = (60)(4.2)(25 - T) [1/2] 6.5 10 3 25 - T = [1/2] 60 4.2 Minimum temperature T = - 0.79 C [1/2] (iii) Give a reason why that in practice, the temperature obtained is usually higher than the temperature calculated in (ii). [4] Heat is gained from the surrounding so that temperature obtained is higher. [1] OR Insufficient water is present to completely dissolve the ammonium nitrate used. [1]

Time allocation: 15 minutes (Gp A) MJC Prelim 2005 3(a) Sodium phosphate (V), Na3PO4, has been used by painters as a heavy duty degreaser and all purpose cleaner. Na3PO4 is formulated for removing grease, soot, and lead paint dust cleanup. A washing of surfaces prior to painting helps insure a good clean "bite" for the finish coats of paint. Sodium phosphate (V) is formed by the neutralisation of sodium hydroxide with phosphoric acid. (i) Draw the dot and cross diagram to show the bonding in phosphate (V) ion, [1] PO43-. 3 O P O O [1] O Draw an appropriate energy level diagram to determine the lattice energy of Na3PO4. The following enthalpy changes are given: Enthalpy change of hydration of sodium ion = - 406 kJmol-1 Enthalpy change of hydration of phosphate(V) ion = - 290 kJ mol-1 Enthalpy change of solution of sodium phosphate (V) + 52 kJmol-1 3Na+ (g) + PO43- (g) 3 x Hhyd(Na+) + Hhyd(PO43-) 3Na+ (aq) + PO43- (aq) Hsoln(Na3PO4) Na3PO4 (s) By Hesss Law, 3 x Hhyd(Na+) + Hhyd(PO43-) = Hlatt(Na3PO4) + Hsoln(Na3PO4) 3(-406) + (- 290) = = Hlatt(Na3PO4) + (52) Hlatt(Na3PO4) = -1560 kJ mol-1 [1/2] 7
Either one correct [1/2]

(ii)

Hlatt(Na3PO4)

[1 marks for energy level diagram]

(iii)

Explain how you would expect the standard enthalpy change of hydration of caesium ion to compare with that of sodium ion.
Hhydration
q+ r+

Ionic radius: Cs+ > Na+ [1/2] Charge density: Na+ > Cs+ [1/2] [1/2]

Strength of interaction with water molecules : Na+ > Cs+

Hhydrationof Na+ > Hhydrationof Cs+

Hhydration of Na+ is more exothermic than Hhydration of Cs+ [1/2]

(b)

Nitroglycerine (C3H5N3O9) is a flammable and explosive oil produced by the action of nitric and sulphuric acids on glycerol. When heated it undergoes a rapid, highly exothermic reaction which results in large increase in pressure and temperature. It is commonly used in the preparation of dynamite, cordite, and other high explosives. Given: Enthalpy change of combustion of N2 (g) Enthalpy change of combustion of C (s) Enthalpy change of combustion of H2 (g) Enthalpy change of formation of C3H5N3O9 (l) (i) = + 68 kJ mol-1 = - 394 kJ mol-1 = - 242 kJ mol-1 = - 354 kJ mol-1

Combustion of nitrogen produces an oxide of nitrogen, NO2. With respect to N2(g), explain the difference between enthalpy change of combustion of nitrogen and enthalpy change of formation of NO2(g). Explain how these two enthalpy changes relate to each other N2 (g) + O2 (g) 2NO2 (g) N2 (g) + O2 (g) NO2 (g) Hc(N2) = + 68 kJ mol-1 Hf(NO2) = + 34 kJ mol-1 . [2]

Enthalpy change of combustion of nitrogen refers to the combustion of 1 mole of nitrogen with excess oxygen. [1/2] Enthalpy change of formation of nitrogen dioxide refers to the formation of 1 mole of nitrogen dioxide from its constituent elements. [1/2]

Hc(N2) = 2 x Hf(NO2)

[1]

(ii)

Nitroglycerine (C3H5N3O9) undergoes combustion to give CO2(g), NO2(g) and H2O(g) as products. Using the above data, construct a thermochemical cycle to calculate the standard enthalpy change of combustion of nitroglycerine. (Ans: -1331kJmol-1) [3]

C3H5N3O9 (l) + 11/4 O2 (g) 3 x Hc(C) Hf (C3H5N3O9) + 3O2 (g)

3CO2 (g) + 3NO2 (g) + 5/2H2O (g) 3/2 x Hc(N2) + 3O2 (g)

5/2 x Hc(H2) + 5/2O2 (g)

3C (s) By Hesss Law,

3/2 N2 (g) + 5/2 H2 (g) + 9/2 O2 (g) [2 mark for energy cycle]

Hf (C3H5N3O9) + Hc(C3H5N3O9) = 3 x Hc(C) + 3/2 x Hc(N2) + 5/2 x Hc(H2) - 354 + Hc(C3H5N3O9) = 3 (-394) + 3/2 (+68) + 5/2 (-242) Hc(C3H5N3O9) = - 1331 kJ mol-1 [1/2]

Either one correct [1/2]

Time allocation: 9 minutes (Gp B/C) TYS : N00/P2/Q1 4 Dinitrogen pentoxide, N2O5, can be produced by the following reaction sequence. I II III (a) + O2 (g) N2 (g) NO (g) + O2 (g) 2NO2 (g) + O2 (g) 2NO(g) NO2(g) N2O5(g) H = + 180 kJ mol-1 H = - 57 kJ mol-1 H = - 55 kJ mol-1

Explain why reaction I occurs in car engines. There is large amount of nitrogen in the air [1/2]. Hence, nitrogen will react with oxygen to form nitrogen oxide at high temperature in the car engines. [1/2]

(b)

Suggest why reaction I is endothermic. Reaction I : N2 (g) + O2 (g) 2NO(g)

The energy released by the formation of N = O bond is insufficient to compensate [1/2] for the large amount of energy required to break the strong N N and O = O [1/2]. Hence, reaction I is endothermic. (c) What is meant by the standard enthalpy change of formation of a compound? Standard enthalpy change of formation (Hf) of a substance is the energy absorbed or released when one mole of the substance is formed from its elements at 298K and 1 atm. [1] (d) Write equation which corresponds to the enthalpy change of formation of dinitrogen pentoxide.

N2 (g) +

5 O2 (g) 2

N2O5(g)

[1]

(e)

Use the data given to calculate the enthalpy change of formation of dinitrogen pentoxide to one decimal place.

N2 (g)
H Reaction (I)

5 O2 2

(g)

N2O5(g) H Reaction (III) + O2 (g)

2NO (g) +

2 x H Reaction (II) 3 O (g) 2NO2 (g) 2 2

[1 for the completed energy cycle]

By Hess Law, Hf(N2O5) Hf(N2O5) = HReaction I + 2 x HReaction II + HReaction III

= + 180 + 2(-57) 55 [1/2] = + 11.0 kJmol-1 ( to 1 dp ) [1/2] * 0 marks if not to 1 dp 10

(f)

Draw the displayed formula showing the correct shape for a molecule of dinitrogen pentoxide. [6]

O N O O

O N O
[1]

Type : Born-Haber Cycle: Time allocation: 9 minutes (Gp B/C) 5(a) Draw a labelled Born-Haber cycle for silver(I) oxide and use it to calculate the lattice energy for silver(I) oxide in J mol-1. The following values are given :
H Hat(Ag) Hf(Ag2O) 1st IE(Ag) 1st EA(O) 2nd EA(O)

Value / kJ mol-1 +286 -31 +710 -141 +790

11

2Ag+(g) + 2e- + O2-(g)

2nd EA (O) 2Ag+(g) + O(g) 2 x 1st IE (Ag) 1st EA (O) 2Ag+(g) + e- + O-(g) 2Ag(g) + O(g)
Hat(O)

2 Ag(g) + O2(g) 2 x Hat(Ag) 0 2 Ag(s) + O2(g)

Hf(Ag2O) Hlatt(Ag2O)

Ag2O (s) [3 marks for Born-Haber Cycle] By Hesss Law,

Hf(Ag2O) = 2Hat(Ag) + Hat(O) + (2X1st IE(Ag)) + 1st EA(O) + 2nd EA(O) + Hlatt (Ag2O) Hlatt(Ag2O) = -((2 X 286) + (248) + (2 X 710) + (-141) + (790) - (-31))
Either one correct [0]

= -2920 kJ mol-1 = (b)

-2920000 J mol-1

[1/2] * Final answer in kJ mol-1 [0]

Explain qualitatively how the lattice energy of copper (I) oxide compares with that of silver(I) oxide. [6] q q Hlatt + r+ + r o Ionic radius of Cu+ < Ag+ [1/2] o Hlatt of Cu2O > Ag2O [1/2]

12

o Lattice energy of Cu2O is more exothermic than Ag2O [1] Type : Energy level diagram : Time allocation: 5 minutes (Gp B/C) 6
1

The standard enthalpy changes of atomisation of silicon and hydrogen are 338 kJ moland 218 kJ mol-1 respectively while the standard enthalpy change of formation of gaseous silane, SiH4, is 70 kJ mol-1. With the aid of an energy level diagram, calculate the standard enthalpy change of atomisation of silane (involving breaking all the covalent bonds in one mole of the compound in the gaseous state). Hence deduce the average bond energy of Si-H bond in silane. [3]

Hatom (SiH4)

Hatom (Si) + 2 x Hatom (H)

Si (s) + 2H2 (g)

Hf(SiH4)

SiH4 (g) [1 for the energy level diagram] By Hesss Law,

Hf(SiH4) + Hatom (SiH4) = Hatom (Si) + 2 x Hatom (H)

- 70 + Hatom(SiH4) = 338 + 2(218)

Hatom(SiH4) = + 844 kJ mol-1 [1/2] Hatom (Si) = 4 x B.E(Si H)

[1/2]

B.E(Si H) =

844 [1/2] = 211 kJ mol-1 [1/2] 4

13

Type : Energy cycle of Aqueous solution : Time allocation: 7 minutes (Gp B/C) 7(a) The standard enthalpy changes of hydration of calcium and fluoride ions are 1650 kJ mol-1 and 506 kJ mol-1 respectively while the standard enthalpy change of solution of calcium fluoride is 22 kJ mol-1. Calculate the lattice energy of calcium fluoride with the aid of an appropriate energy cycle.

CaF2 (s)

CaF2 (aq)
Hhyd(Ca2+) + 2 x Hhyd(F-)

- Hlatt(CaF2)

Ca2+ (g) + 2 F- (g) [1 mark for the energy cycle] By Hesss Law,
Hsoln(CaF2) = Hhyd(Ca2+) + 2 x Hhyd(F-) - Hlatt(CaF2)
Either one correct [0]

- 22 = -1650 + 2(-506) Hlatt(CaF2)

Hlatt(CaF2) = - 2640 kJmol-1 [1]

(b)

How would the hydration value of chloride ion compare with that of the iodide ion and explain the significance of the comparison ? [5]

Hhyd

q r

[1/2]

o Ionic radius of I- < Cl- [1/2] o Charge density of Cl - > I [1/2] I- [1/2]

o Strength of interaction with water molecules : Cl- > o I H hyd I : Cl - > I

Hhydration of Cl - is more exothermic than Hhydration of I - [1/2]

14

Time allocation: 15 minutes (Gp B/C) RJC Prelim 2006/P2/Q2 8 Pyridine, C5H5N, is widely used as a solvent and an intermediate in the synthesis of insecticides, herbicides and pharmaceuticals. Pyridine is a simple heterocyclic aromatic organic compound that is structurally related to benzene and is a liquid at room temperature with a boiling point of 115 C.

N
Pyridine (a) (i) Experimentally the enthalpy change of atomisation of pyridine has been found to be +5130 kJ mol1. Write an equation to represent this reaction. [1]

C5H5N (l) 5 C (g) + 5 H (g) + N (g) [1]

(ii) Using relevant bond energy data from the Data Booklet, calculate another value for the enthalpy change of atomisation of pyridine. [2] Enthalpy change of atomisation of pyridine = 2BE(CC) + 2BE(C=C) +B E(CN) +BE(C=N) + 5BE(CH) = 2(350) + 2(610) + 305 + 610 + 5(410) [1] = + 4885 kJ mol1 [1]

(iii) Suggest a reason for the difference between the value given in (i) and that calculated in (ii). [1] The bond energy data from the Data Booklet are average values which may differ from with the actual values unique to the pyridine structure. [1]

(b)

(i)

Define standard enthalpy change of combustion of pyridine.

[1]

Standard enthalpy of combustion of pyridine is the enthalpy change when one mole of pyridine is completely burnt in oxygen at 298K and 1 atm. [1/2]

C5H5N (l) +

29 5 O2 (g) 5CO2 (g) + H2O (l) + NO2 (g) [1/2] 4 2

15

(ii)

When 1.13 g of pyridine was combusted in a calorimeter, the procedure heated 100 g of water from 25 C to 87 C. This process was known to be only 65% efficient. Calculate the enthalpy change of combustion of pyridine. [3] 1 1 (Specific heat capacity of water: 4.20 J g K )

Molar mass of pyridine = 79.0 g mol-1 No of of pyridine burnt =

1.13 = 0.01430 mol 79.0

Heat absorbed by the water, Q = 100 4.2 (8725) = 26.04 kJ [1/2] Heat released by the combustion, Q = 0.65 x heat absorbed by the water, Q

Heat released by the combustion = 26.04 100/65 = 40.06 kJ [1/2] Enthalpy change of combustion = 40.06 / 0.0143 [1/2] = 2800 kJ mol1 [1/2]

(iii)

Use the value calculated in (ii) and the data below to calculate the enthalpy change of hydrogenation of pyridine. [2]
H

N
(l) + 3 H2 (g)

N
(l)

Data: Enthalpy change of combustion of C5H11N = Enthalpy change of combustion of H2 =

3356 kJ mol1 285.8 kJ mol1

16

H N

(l) + 3 H2 (g)

(l)

Hc

3H

Hc

5CO2 (g) +

11 2 H2O (l) + NO2 (g)

[2 marks for the energy cycle] By Hess Law,

Hhyd = Hc(pyridine) + 3Hc(hydrogen) Hc(C5H11N) Hhyd = -2800 + 3(-285.6) - (-3356) Hhyd = - 301 kJ mol1 [1/2]
Either one [1/2]

17