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Thermodynamics)
Thermodynamics)
Enthalpy change when 1 mole of a substance is formed from its constituent elements with all reactants and products in
standard states under standard conditions.
H2O(l) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
NH3(g) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
C2H5OH(l) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
CH3Br(l) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
Na2O(s) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
Enthalpy change when 1 mole of a substance is completely burned in oxygen with all reactants and products in standard
states under standard conditions.
H2(g) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
C2H6(g) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
C2H5OH(l) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
Na(s) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
C6H14(l) <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<.
A B
e.g. the enthalpy change to go from A → B direct is
the same as going from A → C → B
• If the enthalpy of formation for the reactants and products in a reaction are known, the overall enthalpy change is easy to
calculate.
Example
Calculate the overall enthalpy change for this reaction: CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l)
∆Hf CH4(g) = -75, CO2(g) = -393, H2O(l) = -286 kJ/mol
Calculate the enthalpy of formation of ethanol (C2H5OH) given the following enthalpies of combustion.
∆Hc C(s) = -393, H2(g) = -286, C2H5OH(l) = -1371 kJ/mol
• Bond enthalpy is the enthalpy change to break one mole of covalent bonds in the gas phase.
• For most bonds (e.g. C-H, C-C, C=O, O-H, etc.) the value for the bond enthalpy is an average taken from a range of
molecules as the exact value varies from compound to compound. For some bond enthalpies (e.g. H-H, H-Cl, O=O, etc)
the value is exact as only one molecule contains that bond.
• Enthalpies of reaction that have been calculated using mean bond enthalpies are not as accurate as they might be
because the values used are averages and not the specific ones for that compound.
• This cycle works for any question that involves bond enthalpies, whether to find a bond enthalpy or ∆H for a reaction.
• Remember that substances must be in the gas state before bonds
are broken, and so ∆H to go to the gas state is needed for solids and ∆H
liquids. (Note - ∆H vaporisation is the enthalpy change to convert a reactants products
liquid to a gas) (∆H→gas) + (∆H→gas) +
bond enthalpies bond enthalpies
• As with other cycles, the sum of the clockwise arrows equals the sum
gas atoms
of the anticlockwise arrows. Be careful to ensure that arrow
directions and number of moles are correct.
Example
Ethanol has the formula C2H5OH and is used as a fuel (e.g. for cars in Brazil). It burns in the following reaction for which the
enthalpy change is -1015 kJ/mol.
Calculate the C-C bond enthalpy in ethanol given the following bond enthalpies and enthalpy of vaporisation of ethanol.
Bond enthalpies: C-H 412, O-H 463, C-O 360, C=O 743, O=O 498 kJ/mol
Enthalpy of vaporisation of ethanol, C2H5OH(l) = 44 kJ/mol
-1015
C2H5OH(l) + 3 O2(g) 2 CO2(g) + 3 H2O(g)
44
C-C
5(412) 4(743)
463 6(463)
360
3(498)
2 Find ∆H for the following reaction using the data below. C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)
-1
∆Hf: C3H8(g) = –104, CO2(g) = –394, H2O(l) = –286 kJ mol
3 Find ∆H for the following reaction using the bond enthalpy data below. C2H6(g) + 3½ O2(g) → 2 CO2(g) + 3 H2O(g)
-1
C-C = 348, C-H = 412, O=O = 496, C=O = 743, O-H = 463 kJ mol
6 Find ∆H for the hydrogenation of propene using the data below. CH3CH=CH2(g) + H2(g) → CH3CH2CH3(g)
-1
∆Hc: CH3CH=CH2(g) = –2059, H2(g) = –286, CH3CH2CH3(g) = –2220 kJ mol
7 0.55 g of propanone was burned in a calorimeter containing 80 g of water. The temperature rose by 47.3ºC.
-1 -1
Calculate ∆Hc for propanone given the specific heat capacity of water is 4.18 J mol K .
3 -3 3 -3
8 25 cm of 2.0 mol dm nitric acid was reacted with 25 cm of 2.0 mol dm potassium hydroxide is an insulated cup.
The temperature rose from 20.2ºC to 33.9ºC. Calculate ∆H for the reaction given the specific heat capacity of water
-1 -1
is 4.18 J mol K .
9 The engines of the lunar module of Apollo 11 used methylhydrazine (CH3NHNH2) and dinitrogen tetraoxide. They
react as follows:
4 CH3NHNH2(l) + 5 N2O4(l) → 4 CO2(g) + 12 H2O(l) + 9 N2(g)
Calculate the enthalpy change for the reaction using the following data:
-1
∆Hf: CH3NHNH2(l) = +53, N2O4 (l) = -20, CO2(g) = -393, H2O(l) = -286 kJmol
12 Calculate the average C-C bond enthalpy in benzene (C6H6) given the following data.
-1
∆Hf (C6H6(l)) = +49 kJmol
-1
C(s) → C(g) ∆H = +715 kJmol
-1
H2(g) → 2 H(g) ∆H = +436 kJmol
-1
C6H6(l) → C6H6(g) ∆H = +31 kJmol
-1
E (C-H) = +413 kJmol
-1 -1 -1 -1
Bond kJmol Bond kJmol Bond kJmol Bond kJmol
-1
∆Ha (kJ mol ): C(s) +715; S(s) +223
-1
∆Hf (kJ mol ): NH3(g) –46; H2O(l) –286; C2H5OH(l) –278; SO2(g) –297
-1
∆Hvap (kJ mol ): H2O(l) +42; C2H5OH(l) +44
Enthalpy of Enthalpy change when one mole of a substance is formed Exothermic (-ve) for e.g. Na2O(s) 2 Na(s) + ½ O2(g) → Na2O(s)
formation (∆Hf): from its constituent elements with all substances in their most substances
standard states
Enthalpy of Enthalpy change when one mole of a substance undergoes Exothermic (-ve) e.g. hydrogen H2(g) + ½ O2(g) → H2O(g)
combustion (∆Hc) complete combustion in oxygen with all substances in
standard states
Enthalpy of Enthalpy change when one mole of gaseous atoms is Endothermic (+ve) e.g. iodine ½ I2(s) → I(g)
atomisation (∆Ha) produced from an element in its normal state.
Bond dissociation Enthalpy change when one mole of covalent bonds is broken Endothermic (+ve) e.g. I-I bond I2(g) → 2 I(g)
enthalpy (∆Hdis) in the gaseous state.
2+ -
Lattice enthalpy of Enthalpy change when one mole of a solid ionic compound is Exothermic (-ve) e.g. magnesium chloride Mg (g) + 2 Cl (g) → MgCl2(s)
formation (∆HL) formed from into its constituent ions in the gas phase
2+ -
Lattice enthalpy of Enthalpy change when one mole of a solid ionic compound is Endothermic (+ve) e.g. magnesium chloride MgCl2(s) → Mg (g) + 2 Cl (g)
disociation (∆HL) broken up into its constituent ions in the gas phase
For each of the following reactions, name the enthalpy change. There may be more than one possible answer to some.
Some answers may involve more than one enthalpy change!
+ -
1) Ca(g) → Ca (g) + e <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
- 2-
2) S(g) + 2 e → S (g) <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
3+ 2-
3) Al2O3(s) → 2 Al (g) + 3 O (g) <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
+ -
4) NaBr(s) → Na (aq) + Br (aq) <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
2+ 2-
8) Ca (g) + O (g) → CaO(s) <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
3+ -
13) Al(g) → Al (g) + 3 e <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
2+ 2+
14) Ca (g) → Ca (aq) <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
2+ -
15) Mg(s) → Mg (g) + 2 e <<..<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<..
Example
Calculate the enthalpy of solution of magnesium chloride given that the lattice enthalpy of formation of magnesium chloride is
-1 -1
-2493 kJmol and the enthalpies of hydration of magnesium and chloride ions are -1920 and -364 kJmol respectively
∆Hsol 2+ -
MgCl2(s) Mg (aq) + 2 Cl (aq) -2493 + ∆Hsol = -1920 + 2 (-364)
∆Hsol = -1920 + 2 (-364) + 2493
-2493 -1920 -1
2(-364) ∆Hsol = -155 kJ mol
Mg2+(g) + 2 Cl-(g)
• The lattice enthalpy of a compound is an indication of the strength of the ionic bonding. The greater the magnitude of the
lattice enthalpy, the stronger the bonding.
• Generally speaking, compounds with smaller ions and ions with higher charges have stronger attractions and so greater
lattice enthalpy.
+ +
e.g. NaCl has a higher lattice enthalpy than KCl as they Na ion is smaller than the K ion.
2+ +
e.g. MgCl2 has a higher lattice enthalpy than NaCl as the Mg ion has a higher charge and is smaller than the Na ion.
• A Born-Haber cycle is a cycle that includes all the enthalpy changes in the formation of an ionic compound.
electron
ionisation
energy/ies of affinity/ies of
non-metal
metal atom(s)
GASEOUS ATOMS atom(s)
GASEOUS IONS
atomisation of
metal and non-
metal ELEMENTS IN
NORMAL STATES
lattice
enthalpy of
enthalpy of formation
formation
Calculate the lattice enthalpy of formation of magnesium chloride given the following data:
Enthalpy of formation of magnesium chloride = –642 kJ mol-1 1st ionisation enthalpy of magnesium = +736 kJ mol-1
Enthalpy of atomisation of magnesium = +150 kJ mol-1 2nd ionisation enthalpy of magnesium = +1450 kJ mol-1
Enthalpy of atomisation of chlorine = +121 kJ mol-1 1st electron affinity of chlorine = –364 kJ mol-1
Example
Calculate the enthalpy of formation of sodium bromide given the following data:
Lattice enthalpy of formation of sodium bromide = –733 kJ mol-1
Enthalpy of atomisation of sodium = +109 kJ mol-1
Enthalpy of atomisation of bromine = +112 kJ mol-1
1st ionisation enthalpy of sodium = +494 kJ mol-1
1st electron affinity of bromine = –342 kJ mol-1
kJmol-1 K Ca Al Co Cu Br I O Cl
enthalpy of atomisation 90 193 314 427 112 107 248 121
1st ionisation energy 418 590 577 757 745
2nd ionisation energy 3070 1150 1820 1640 1960
3rd ionisation energy 4600 4940 2740 3230 3550
1st electron affinity -342 -142 -364
2nd electron affinity +844
1) Calculate the enthalpy of formation of potassium chloride given that the lattice enthalpy of formation of potassium
-1
chloride is -710 kJmol .
2) Calculate the enthalpy of formation of calcium bromide given that the lattice enthalpy of formation of calcium bromide
-1
is -2125 kJmol .
3) Calculate the lattice enthalpy of formation of aluminium oxide given that the enthalpy of formation of aluminium oxide
-1
is -1669 kJmol .
4) Calculate the lattice enthalpy of formation of calcium oxide given that the enthalpy of formation of calcium oxide is -
-1
635 kJmol .
5) Calculate the first electron affinity of iodine given that the lattice enthalpy of dissociation of calcium iodide is +2054
-1 -1
kJmol and its enthalpy of formation is -535 kJmol .
-1
6) Calculate the enthalpy of atomisation of copper given that the enthalpy of formation of CuO is -155 kJmol and its
-1
lattice enthalpy of formation is -4149 kJmol .
7) The lattice enthalpy of formation of the three possible chlorides of cobalt are given:
-1
CoCl -700; CoCl2 -2624; CoCl3 -5350 kJmol .
1 a) The symbol ∆H is often used. Explain what the ∆H and each mean. (2)
c) What will be the first step in the mechanism for the reaction for the formation of HCl? (1)
3 Calculate a value for the mean bond enthalpy of the O-H bond in water using the data below.
-1
H2(g) → 2 H(g) ∆H = +436 kJ mol
-1
O2(g) → 2 O(g) ∆H = +496 kJ mol
-1
H2(g) + ½ O2(g) → H2O(g) ∆H = -242 kJ mol (Total 3)
4 Hydrogen sulphide, H2S, is a liquid at room temperature. Calculate the average H-S bond enthalpy in hydrogen
-1
sulphide given that the enthalpy of formation of hydrogen sulphide is –20 kJ mol and the following data.
-1
H2(g) → 2 H(g) ∆H = +436 kJ mol
-1
S(s) → S(g) ∆H = +223 kJ mol
-1
H2S(l) → H2S(g) ∆H = +19 kJ mol (Total 3)
-1
5 a) The standard enthalpy of formation of propane is -104 kJ mol . Given that the standard enthalpies of formation
-1
of carbon dioxide and water are -394 and -286 kJ mol respectively, calculate the standard enthalpy change of
combustion of propane. (3)
b) Using bond enthalpies only, calculate the standard enthalpy of combustion of propane.
-1
C-C 348, C-H 412, O=O 496, C-O 360, C=O 743, H-O 463 kJ mol (3)
c) Compare your answers to (a) and (b) and comment on any difference. (2)
(Total 8)
6 What is the sign (+ or -) of the following standard enthalpy changes (justify your answer)?
a) condensing steam b) combustion of octane c) boiling ethanol (Total 3)
-1
8 The standard enthalpy change of combustion of propanoic acid is -1574 kJ mol . Given that the standard
-1
enthalpies of formation of carbon dioxide and water are -393 and -286 kJ mol respectively, calculate the
standard enthalpy change of formation of propanoic acid. (Total 3)
9 Calculate the enthalpy of hydration of bromide ions given that the hydration enthalpy of barium ions is
-1 -1
-1360 kJ mol , the lattice enthalpy for BaBr2 is -1937 kJ mol and the enthalpy of solution of BaBr2 =
-1
-38 kJmol . (Total 3)
b) For each pair of compounds, predict which will have the lattice enthalpy of greatest magnitude, and explain why.
i) LiF or NaF ii) CaO or MgO iii) NaCl or MgCl2 (6)
(Total 7)
12 Show why calcium and chlorine react together to form CaCl2 rather than CaCl or CaCl3 (you will need three
Born-Haber cycles to do this). The lattice enthalpies of formation of the chlorides are: CaCl =
-1
-719; CaCl2 = -2218; CaCl3 = -4650 kJ mol . You will also need to use data in the table in question 5.
(Total 10)
13 In each of the following questions you should draw a clear Born-Haber cycle and use data from the table below.
kJ mol-1 Na Al Hg Ca Cl Br I O
enthalpy of atomisation 109 314 61 193 121 112 107 248
1st ionisation energy 494 577 1010 590
2nd ionisation energy 4560 1820 1150
3rd ionisation energy 6940 2740 3300 4940
1st electron affinity -364 -314 -142
2nd electron affinity +844
a) Calculate the lattice enthalpy of formation of aluminium oxide given that its enthalpy of formation is -1669 kJ/mol. (6)
-1
b) Calculate the enthalpy of formation of sodium iodide given that its lattice enthalpy of formation is -684 kJ mol . (6)
c) Calculate the first electron affinity of bromine given that the lattice enthalpy of formation of calcium bromide is -
-1 -1
2148 kJ mol and the enthalpy of formation is calcium bromide is -675 kJ mol . (6)
d) Calculate the second ionisation energy of mercury given that the lattice enthalpy of dissociation of mercury (II)
-1 -1
chloride is +2625 kJ mol and the enthalpy of formation is mercury (II) chloride is -230 kJ mol . (6)
(Total 24)
15 Lattice enthalpy gives us useful information about the structure of an ionic compound.
b) Using the sizes and charges of ions and the laws of electrostatics, theoretical values can be calculated for lattice
enthalpies. The table below shows a comparison between values measured using experimental data with Born-
Haber cycles, and theoretical values.
For many substances, the measured and theoretical values are very similar, such the as the sodium halides, but
for some substances there is a significant difference, such as the silver halides. Account for this difference. (2)
(Total 5)
16 Use the following data to calculate the average C-S bond energy in CS2(l).
-1
Enthalpy of atomisation of sulphur = + 223 kJ mol
-1
Enthalpy of atomisation of carbon = + 715 kJ mol
-1
Enthalpy of formation of CS2(l) = + 88 kJ mol
-1
Enthalpy of vaporisation of CS2(l) = +27 kJ mol i.e. CS2(l) → CS2(g) (Total 4)
-1
17 The enthalpy of hydration of magnesium and sodium ions are -1920 and -406 kJ mol respectively. Explain why
2+ +
the enthalpy of hydration of Mg has a greater magnitude than that of Na . (Total 2)
What is entropy?
• Entropy (S) is disorder. The more disordered (or random) something is, the greater the entropy.
• Gases have the most entropy (particles are move rapidly and randomly) whereas solids have least entropy (particles
vibrating about fixed positions).
• There is a tendency for entropy to increase, i.e. for things to become more disordered.
• The higher the temperature, the faster the particles vibrate/move and so the greater the entropy (disorder).
• Gases have the most entropy (particles are move rapidly and randomly) whereas solids have least entropy (particles
vibrating about fixed positions).
S (gas) > S (liquid) > S (solid)
Temperature
Calculate the entropy change for this reaction: C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(l)
-1 -1
Entropy: C2H5OH(l) = 161, O2(g) = 205, CO2(g) = 214, H2O(l) = 70 J mol K
• In the same way as a decrease in enthalpy (∆H -ve) is a driving force in making reactions go, so is an increase in
entropy (∆S +ve), i.e., an increase in disorder is favourable.
• For many reactions it is possible to tell whether entropy will increase or decrease by looking at the equation.
one mole of solid gives three moles of gas ∴ far more disorder ∴ ∆S +ve
S ∆Hf S ∆Hf
substance substance
(J mol-1 K-1) (kJ mol-1) (J mol-1 K-1) (kJ mol-1)
H2O(g) 189 -242 Fe(s) 27
H2O(l) 70 O2(g) 205
H2(g) 131 Fe2O3(s) 90 -822
Cl2(g) 223 C(graphite) 5.7
HCl(g) 187 CO2(g) 214 -394
NaHCO3(s) 102 -948 N2(g) 192
Na2CO3(s) 136 -1131 NH3(g) 193
C3H8(g) 270
1) a) Predict the sign of ∆S for the following reactions, where possible, giving your reasoning for each one.
i) H2O(g) → H2O(l)
ii) H2(g) + Cl2(g) → 2 HCl(g)
iii) C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)
2) a) Sketch a graph to show how the entropy of water varies with temperature.
• Gibbs free energy (G) combines the two thermodynamic factors of enthalpy (H) and entropy (S).
∆G = ∆H - T∆
∆S
What is the connection between Gibbs free energy change and thermodynamic feasibility?
-ve -ve ∆G –ve at low T, +ve at high T Reaction feasible at low T, not feasible at high T
+ve +ve ∆G +ve at low T, -ve at high T Reaction not feasible at low T, feasible at high T
Melting
• A substance cannot melt below its melting point as ∆G for melting is +ve below the melting point.
• At the melting point, ∆G = 0 and so melting is feasible and the substance melts.
Boiling
• A substance cannot boil below its boiling point as ∆G for boiling is +ve below the boiling point.
• At the boiling point, ∆G = 0 and so boiling is feasible and the substance boils.
∆S ∆G = ∆H - T∆S
-1 -1
∆H = 70 - 298 (85) = +44.7 J mol K
1000
c) ∆G = ∆H - T∆S
when ∆G = 0, ∆H - T∆S = 0 ∴ T = ∆H = +70 = 824 K
+85
∆S ( /1000)
The reaction is spontaneous when T ≥ 824 K
Example 2
-1
The enthalpy of vaporisation of ethanol is +43.5 kJ mol . The boiling point of ethanol is 78°C. Calculate the entropy change
for the vaporisation of ethanol.
∆G = ∆H - T∆S
-1 -1 -1 -1
At boiling point, ∆G = 0, ∆H - T∆S = 0 ∴ ∆S = ∆H = +43.5 = 0.124 kJ mol K = 124 J mol K
T 351
S ∆Hf S ∆Hf
substance substance
(J mol-1 K-1) (kJ mol-1) (J mol-1 K-1) (kJ mol-1)
H2O(g) 189 -242 Fe(s) 27
H2O(l) 70 O2(g) 205
H2(g) 131 Fe2O3(s) 90 -822
Cl2(g) 223 C(graphite) 5.7
HCl(g) 187 CO2(g) 214 -394
NaHCO3(s) 102 -948 N2(g) 192
Na2CO3(s) 136 -1131 NH3(g) 193
C3H8(g) 270
3
4) For the reaction: 2 Fe(s) + /2 O2(g) → Fe2O3(s)
a) Calculate ∆H and ∆S.
b) Calculate ∆G at 298 K.
c) Calculate the temperature range over which the reaction is feasible.
6) a) Calculate ∆H, ∆S and ∆G for the following reaction at 298 K:
Fe2O3(s) + 3 H2(g) → 2 Fe(s) + 3 H2O(g)
b) Will this reaction be feasible at 298K?
c) Calculate the temperature range over which the reaction is feasible.
b) Potassium chloride dissolves readily in water at 298 K. Deduce the sign of the entropy change for this reaction, and
explain your reasoning.
c) Explain, in terms of the behaviour of particles, why the entropy change has the sign given in your answer to (b).
d) Use your answer to (a) to calculate the smallest possible entropy change there must be when potassium chloride
dissolves in water at 298 K, given that it is a feasible change.
a) A reaction that can be made to take place by changing the conditions is:
CaCO3(s) → CaO(s) + CO2(g)
i) Calculate ∆H for this reaction. (1)
ii) Calculate ∆S for this reaction. (1)
iii) Calculate ∆G for this reaction at 298 K. (1)
iv) Is the reaction spontaneous at 298 K? (1)
v) Will increasing or decreasing the temperature help to make ∆G more negative? (1)
vi) At what temperature will ∆G equal zero? (3)
vii) Give the temperature range in which the decomposition of CaCO3 is spontaneous. (1)
viii) How can this reaction be spontaneous even though it is endothermic? (1)
b) Repeat your calculations for the decomposition of MgCO3 to find the temperature at which is undergoes
similar decomposition. (4)
c) i) Use your results to compare the thermal stability of MgCO3 and CaCO3. (1)
ii) Suggest a reason for the difference in thermal stability of MgCO3 and CaCO3. (1)
(Total 16)
10) State the sign of the entropy change in the following reactions (or whether it stays roughly constant), justifying
your answer in each case.
+ -
a) CO(g) + H2O(g) → CO2(g) + H2(g) c) NaCl(s) + aq → Na (aq) + Cl (aq)
b) N2(g) + 3 H2(g) → 2 NH3(g) d) I2(s) → I2(g) (Total 4)