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Energetics
Exothermic and endothermic reactions
5.2
5.3
Hesss law
5.4
Bond enthalpies
CORE
5.1
IBO 2007
135
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CORE
Chapter 5
Figure 502) assuming that the reaction occurs with no
change in temperature or pressure, or that these conditions
are restored to their initial values. If this is the case and any
other factors affecting a systems enthalpy do not change,
then H is equal to the change in the potential energy of
the chemical bonds. Strictly speaking the term enthalpy
change only applies to reactions that occur at constant
pressure, but in the laboratory using open beakers and
test tubes, this is most often the case.
Type of
reaction
Heat energy
change
Temperature
change
Relative
enthalpies
Sign of H
Exothermic
Heat energy
evolved
Becomes hotter
Hp < Hr
Negative ()
Endothermic
Heat energy
absorbed
Becomes colder
Hp > Hr
Positive (+)
H (H p H r )
is negative as
Hp < Hr
Reactants
H
Products
Exothermic
Products
H
Reactants
Endothermic
136
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Energetics
1.
NaHCO3 (s)
Na2CO3 (s) + H2O (l) + CO2 (g)
H = +45.8 kJ mol1
2.
If a reaction is endothermic
A
B
C
D
A
B
C
D
Enthalpy
3.
5.1
Exercise
CORE
2 NaHCO3 (s)
Na2CO3 (s) + H2O (l) + CO2 (g)
H = +91.6 kJ mol1
Products
Reactants
A
B
C
D
4.
137
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Chapter 5
5.
CORE
c)
d)
e)
5.2 Calculation
of enthalpy
changes
5.2.1 Calculate the heat energy change when
the temperature of a pure substance is
changed.
5.2.2 Design suitable experimental procedures
for measuring the heat energy changes of
reactions.
5.2.3 Calculate the enthalpy change for a
reaction using experimental data on
temperature changes, quantities of
reactants and mass of water.
5.2.4 Evaluate the results of experiments to
determine enthalpy changes.
IBO 2007
= 8360 J or 8.36 kJ
138
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Energetics
2 Mg(s) + O2 (g)
2 MgO(s)
H = 1200 kJ mol1
= 2508 J or 2.51 kJ
H+ (aq) + OH (aq)
H2O (l)
H =62.7kJ mol1.
CORE
139
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Chapter 5
6.
5.2
Exercise
CORE
2.
30 kJ
274 kJ
1370 kJ
6850 kJ
H2 (g) + O2 (g)
C
D
7.
8.
c)
A
B
C
D
10 kJ
40 kJ
160 kJ
320 kJ
A 25 2 15 4.18 kJ mol1
B 50 2 15 4.18 kJ mol1
4.18kJ mol1
____________
25 15
2
4.18
____________
50 15
kJ mol1
2 25
4g
32 g
64 g
128 g
b)
A
B
C
D
H2O (l)
5.
5 C
20 C
40 C
320 C
4.
A
B
3.
4.4 J
88 J
4400 J
88000 J
d)
e)
140
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Energetics
b)
c)
d)
e)
NaHCO3(s) + HCl(aq)
NaCl(aq) + CO2(g) + H2O(l)
H1
2 NaHCO3(s)
Na2CO3(s) + CO2(g) + H2O(l)
H3
2 NaHCO3(s) + 2 HCl(aq)
2 NaCl(aq) + 2 CO2(g) + 2 H2O(l)
Hesss Law states that the total enthalpy change for the two
stage reaction must be equal to the single stage process,
i.e.
2 H1 = H2 +H3
Note the factor of two occurs because the equation for
the direct reaction, as usually written involves only one
mole of NaHCO3 being converted to one mole of NaCl,
whereas the route via Na2CO3 would usually be written for
the conversion of two moles.
This may also be shown in the form of an enthalpy cycle.
Na2CO3(s) + 2 HCl(aq)
2 NaCl(aq) + CO2(g) + H2O(l)
CORE
a)
2H1
H2
141
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Chapter 5
Example
Calculate H1 for reaction
2 C(s) + 2 H2(g)
C2H4(g) given:
CORE
CO2(g);
C2H4(g) + 3 O2(g)
H = 395 kJ
H2O(l);
H = 287 kJ
2 CO2 (g) + 2 H2O(l);
H = 1416 kJ
Solution
2 CO2(g);
2H2 = 2 (395 kJ)
2 H2O(l);
2H3 = 2 (287 kJ)
C2H4(g)
C2H4(g) + 3 O2(g);
H4 = + 1416 kJ
2 C(s) + 2 H2(g)
H = 2H1 + 2H2 H3
= +52 kJ mol1
C2H4(g)
H f
+ 3 O2 (g)
2 C (s) + 2 H2 (g)
+ 3 O2 (g)
H ( J )
2 H2 + 2 H3
142
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Energetics
1.
2.
2 H2O2 (aq)
2 H2 (g) + O2 (g)
200 kJ mol1
400 kJ mol1
600 kJ mol1
800 kJ mol1
FeCl2 (s)
4.
5.
b)
c)
d)
5.3
CORE
Exercise
2 FeCl3 (s)
H = 800 kJ mol1
2 FeCl3 (s)
H = 120 kJ mol1
143
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Chapter 5
HCl (g)
H (g) + Cl (g)
The fact that they refer to gases, coupled with the fact
that bond enthalpy values are the average of that bond in
a range of compounds and hence are only approximately
constant, means that enthalpy changes calculated using
bond energies are less precise than those obtained by
other methods. Nevertheless, apart from a few exceptional
cases such as benzene (which is resonance stabilized), the
N2 (g) + 3 H2 (g)
2 NH3 (g)
CORE
8000
7000
6000
5000
4000
3000
2000
1000
0
1
10
Number of C atoms
144
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Energetics
Example
Use the data provided below to obtain the value for the
bond enthalpy of the CH bond.
CH4 (g); H1
C (g); H2
(2) C (graphite)
(3) H2 (g)
2H (g); H3
Solution
Doubling equation (3), then reversing it and equation
(2) and adding equation (1) gives the equation for the
formation of four CH bonds:
= 872 kJ
C (graphite); H2 = 725 kJ
CH4 (g); H1= 75 kJ
(4)
C (g) + 4H (g)
CORE
CH4 (g)
145
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Chapter 5
C (g) + 4 H (g)
Eq. (3): 4 H (g) m 2 H2 (g); $H3 = 2 (-436) = -872 kJ
Enthalpy, H
CORE
1672 = 418 kJ
4
Exercise
1.
5.4
2.
CO(g)
CO(g)
CO(g)
CO(g)
C(g) + O(g)
C(s) + O(g)
C(s) + O2(g)
C(g) + O2(g)
3.
4.
N2(g) + 2 O2(g)
A
B
C
D
2 NO2(g)
1
+716 kJ mol
+1135 kJ mol1
+1326 kJ mol1
+1631 kJ mol1
2NCl3 (g)
146
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Energetics
Consider the halogens (Cl2, Br2, I2) - the bond
enthalpies of the halogens given in the table below.
Explain the trend in these. Based on the data in
the table below, predict a value for the FF bond.
Compare this to the literature value, and explain any
discrepancy:
B.E. / kJ mol1
ClCl
BrBr
II
Na(s) + Cl2(g)
243
193
151
HIGHER LEVEL
15.1 Standard
enthalpy
changes of
reaction (AHL)
15.1.1 Define and apply the terms standard
state, standard enthalpy change of
formation (Hf) and standard enthalpy
change of combustion (Hc).
15.1.2 Determine the enthalpy change of
a reaction using standard enthalpy
changes of formation and combustion.
IBO 2007
NaCl(s)
H = 411 kJ mol1
H = Hf(products) Hf(reactants)
This same formula also results from a consideration of the
appropriate enthalpy cycle:
AHL
6.
Reactants
H f (reactants)
Products
H f (products)
147
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Chapter 5
the elements, and H3 is even more obviously Hf
(CH3COOC2H5 (l)) + Hf (H2O(l))], as it is the formation
of the elements from their compounds. Applying Hesss
Law:
H2 (g) + O2 (g)
H2O (l)
H1 = H2 +H3
AHL
NH4NO3(s)
N2O(g) + 2 H2O(l)
C (s) + O2 (g)
CO2 (g)
both Hcomb (C (s)) and Hf (CO2 (g))
Many covalent compounds will undergo combustion and
hence it is often easy to determine the standard enthalpy
change of combustion for molecules. An enthalpy cycle,
similar to that for enthalpy of formation can be constructed
using enthalpies of combustion, as shown in the example
below, and this can be used to calculate a value for the
enthalpy of formation:
Example
CalculateHf(C2H4 (g)), given: Hf(CO2(g))=395kJmol1,
Hf (H2O (l)) = 287 kJ mol1 and Hcomb (C2H4 (g)) =
1416 kJ mol1.
Solution
The enthalpy diagram for this example is illustrated below
C 2 H 4 (g)
H f (C 2 H4 (g))
2C(s)+2 H 2 (g)
Hf = Hf (products) Hf (reactants)
= [Hf (N2O(g)) + 2 Hf (H2O(l))]
[Hf (NH4NO3(s))]
= [(+82) + 2 (285)] [(366)]
= (488) (366)
= 122 kJ mol1
+3O
(g)
+ 3 O 2 (g)
H
/J
H comb (C 2 H4 (g))
2 H f (CO 2 (g)) +
2 H f (H 2 O(l))
2 C O 2 (g )
+ 2 H 2 O(l)
CH4(g) + 2 O2(g)
CO2(g) + 2 H2O(l)
Hcomb = 891 kJ mol1
H = Hf (products) Hf (reactants)
Hcomb (C2H4 (g)) = [2 Hf (CO2 (g)) + 2 Hf (H2O (l))]
[Hf (C2H4 (g)) + 3Hf (O2 (g))]
148
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Energetics
Since H of (O2 (g)) = 0, this may be rearranged to give:
Enthalpy of formation
$H f
$H comb (compound)
Example
Calculate the enthalpy change for the hydration of ethene,
given that the enthalpy of combustion of ethene and ethanol
are 1409 kJ mol-1 and 1371 kJ mol-1 respectively.
Solution
Example
Calculate the relative stabilities of propan-1-ol and propan2-ol from their enthalpies of combustion.
Solution
3 O2 (g)
Sum of enthalpies
of combustion of
the elements
C2H4 + H2O
CH3CH2OH
H = Hf (reactants) Hf (products)
H = 1409 (1371)
= 38 kJ mol1
(n.b. Hc for water is zero)
AHL
Component elements
2 C (s) + 3 H2 (g)
H+ (aq) + OH (aq)
H2O (l)
H = 57.9 kJ mol1
149
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Chapter 5
Exercise
1.
2.
AHL
15.1
A temperature of 298 K
A pressure of 101.3 kPa
All substances in the gaseous state
Elements present as the standard
allotrope
A
B
C
D
3.
2 NaHCO3 (s)
A
B
C
D
4.
8.
+84 kJ mol1
+864 kJ mol1
864 kJ mol1
84 kJ mol1
b)
c)
CH3COOH (l)
5.
A
B
C
D
+161 kJ mol1
+122 kJ mol1
122 kJ mol1
405 kJ mol1
9.
150
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Energetics
[Standard enthalpy of formation data, in kJ mol1:
CH2Cl2 (l) 121; HCl(g) 92;
b)
c)
d)
b)
c)
d)
15.2 Born-Haber
cycle (aHL)
15.2.1 Define and apply the terms lattice
enthalpy and electron affinity.
15.2.2 Explain how the relative sizes and
the charges of ions affect the lattice
enthalpies of different ionic compounds.
AHL
Na(s)
151
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Chapter 5
Gaseous anions and cations
Ionisation energy(ies)
Gaseous anions and metal atoms
Lattice enthalpy
Electron affinity(ies)
Elements as gaseous atoms
Enthalpies of atomisation
Enthalpy of formation
Solid compound
AHL
Cl2(g)
Cl(g) Hat = E (ClCl)
= (+242)
= +121 kJ mol1
Cl(g) + e
NaCl(s)
= 411 kJ mol1
= +103 kJ mol1
= +121 kJ mol1
= 364 kJ mol1
= +500 kJ mol1
+
(g)
+ Cl (g)
(g)
Lattice enthalpy
Electron affinity of Cl
Na (g) + Cl (g)
Sum of enthalpies
of atomisation
of Na and Cl
Na (s) + Cl2 (g)
Enthalpy of formation
NaCl (s)
Figure 513 The theoretical steps in the formation of sodium chloride from its elements in their standard states
152
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Energetics
L.E. = 411 + 103 + 121 364 + 500
Theoretical
value
(kJ mol1)
[Electrostatic
summing]
Sodium chloride
766
766
Potassium
bromide
672
667
Potassium iodide
632
631
Silver iodide
865
736
Compound
Lattice enthalpy
(kJ mol1)
Change from
NaCl
MgO
3889
Increased ionic
charge
NaCl
771
KBr
670
Larger ions
AHL
= + 771 kJ mol1
Compound
Empirical
value
(kJ mol1)
[BornHaber]
Gaseous ions
2+
Ca (g) + 2 Cl (g)
Lattice enthalpy
H latt (CaCl2 )
Solid compound
CaCl 2 (s)
Enthalpy of solution
Hsol (CaCl 2 (s))
Aqueous solution
2+
Ca (aq) + 2 Cl (aq)
153
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Chapter 5
Enthalpy of solution = Lattice enthalpy + Sum
of hydration enthalpies
Hsol(NaCl) = 4 kJ mol1
Hhyd(Na+) = 406 kJ mol1
= 120 kJ mol
AHL
Exercise
1.
2.
15.2
A
B
C
D
A
B
C
D
6.
Size of ions
Charge on ions
Large
Large
Large
Small
Small
Large
Small
Small
RbCl
CaS
BaI2
LiF
Ionisation enthalpy
Enthalpy of hydration
Lattice enthalpy
Enthalpy of atomisation
+774 kJ mol1
+766 kJ mol1
+46 kJ mol1
+38 kJ mol1
A
B
C
D
3.
154
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Energetics
Enthalpy of atomisation of calcium
+193 kJ mol1
FF bond enthalpy
+158 kJ mol1
solid liquid
Entropy
AHL
8.
gas
(ice)
(water)
(steam)
48.0
69.9
188.7 J K1 mol1
155
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Chapter 5
The entropy of a perfectly ordered crystal at absolute zero
is zero (that is there no randomness in the crystal or from
the movement of the particles) hence, unlike enthalpy (H),
absolute values of the entropy of a substance in a particular
state can be measured relative to this. Real substances
always have a greater randomness than this theoretical
stationary perfect crystal, hence standard molar entropies
of substances are always positive. The units of entropy are
J K1 mol1.
Exercise
1.
AHL
NH4Cl (s)
A
B
C
D
2.
S = S (Products) S (Reactants)
Consider the complete combustion of methane:
CH4(g) + 2 O2(g)
CO2(g) + 2 H2O(l)
2 NH3(g)
PbI2 (s)
S = 70 J K1 mol1
N2(g) + 3 H2(g)
15.3
A
B
C
D
3.
4.
129 J K1 mol1
198 J K1 mol1
+129 J K1 mol1
+198 J K1 mol1
Br2 (l)
Br2 (g)
Ag+ (aq) + Cl (aq)
AgCl (s)
2 NO2 (g)
N2O4 (g)
2 OH (aq) + CO2 (g)
H2O (l) + CO32 (aq)
H2 (g) + Cl2 (g)
2 HCl (g)
CuSO45H2O (s)
1
FeCl2(s) + Cl2(g)
1
FeCl3(s)
156
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Energetics
Universe
AHL
Surroundings
Heat
System
Figure 519 Illustrating the division into system and
surroundings
S measures the change in the entropy of the system. The
major effect of chemical changes on the entropy of the
surroundings results from the gain and loss of heat energy.
If chemical potential energy is converted to heat energy
which is then transferred to the universe (i.e. an exothermic
change), then this results in an increase in the entropy
157
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Chapter 5
Positive,
i.e.
endothermic
Depends on T
Positive,
i.e.
endothermic
Always positive
Never spontaneous
Negative, i.e.
exothermic
Always negative
Always spontaneous
Negative, i.e.
exothermic
Depends on T
Spontaneity
N.B. This assumes that the effect of temperature on the actual values of H and S is negligible
AHL
$H negative
Exothermic
T/ K
Spontaneous
($G<0)
Figure 521 The conditions for spontaneity and the effect of temperature on this
158
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Energetics
This will continue until G for any further change will be
zero (remember standard values only apply to standard
conditions, i.e. stoichiometric amounts), at which point
equilibrium will be established. If G is very negative then
this position will be so far to the right that the reaction
will effectively go to completion. Similarly if G is small
and positive then an equilibrium favouring the products
will occur, but if G is very positive the reaction will not
occur.
G =
H TS
Hf kJ mol1
S JK1mol1
CaCO3(s)
1207
93
CaO(s)
636
40
CO2(g)
394
214
H = Hf(Products) Hf(Reactants)
Therefore:
Substance
S = S(Products) S(Reactants)
= + 161 J K1 mol1.
G =
H TS
AHL
CaCO3 (s)
T = _______
177000
= 1 099 K
161
Gf = Gf (Products) Gf (Reactants)
Using this approach for the calcium carbonate example
above standard free energy of formation data for the
compounds in the appropriate state is:
Gf (CaCO3) = 1120 kJ mol1 ;
Gf (CaO) = 604 kJ mol1;
Gf (CO2) = 395 kJ mol1
Hence:
G = [(604) + (395)] [1120]
= +121 kJ mol1
159
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Chapter 5
1.
Positive
Positive
Positive
Negative
Negative
Positive
Negative
Negative
AHL
2.
3.
A
B
C
D
d)
Data:
Hf
kJ mol1
S
J mol1 K1
cisbut-2-ene
67.1
5.7
301
transbut-2-ene
64.1
10.1
296
5.
500
Temp /K
1500
1000
Pb
200
200 kJ mol
100 kJ mol1
40 kJ mol1
+40 kJ mol1
Hf / kJ mol1
S / J mol1 K1
Ethyne
227
201
Benzene
83
269
2500
H2
2000
Zn
4.
15.4
Exercise
CO
400
600
Al
800
1000
H2
Zn
Pb
Al
CO
160
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