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13
Energy and thermochemistry
Answers to worked examples
WE 13.1 Types of system: the Breitling Orbiter
What type of system is the Space Shuttle in orbit around the Earth?
Strategy
Consider whether energy, either as heat or work, or matter is transferred
between the Space Shuttle, as the system, and the surroundings. Hence decide
whether the Space Shuttle is an open, closed or isolated system.
Solution
The skin of the Shuttle is highly heat insulating to allow it to re-enter the Earths
atmosphere, so energy transfer should be negligible. As long as the door stays
shut, no matter will leave the shuttle under normal conditions and it can be
regarded as an isolated system. Of course, if any of the thrusters or engines are
working, there will be a transfer of both work and heat. Under these conditions,
it is an open system.
Solution
Rearranging Equation 13.1
) *(
)+
)+
) (
The kettle is rated at 3 kW, meaning that it can deliver 3 kJ s1. Thus, the time
taken to deliver 2261 kJ is
(
) (
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)+
) (
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Solution
The reaction
P (s) + 2.5 Cl2 (g) PCl5 (g)
( )
(
(
(
)
)
(
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where the terms i are the stoichiometric coefficients of the products and
reactants, so that
{
( ))
( ))}
(
(
( ))
(
)+
then
(
( ))
( ))}
( ))
( ))}
( ))
then, rearranging,
(
( ))
( ))
( ))}
( ))
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)
(
)
)+
(
)
)+
)
(
)
)+
)+
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The enthalpy change for the overall reaction is the difference between the bond
enthalpies of the products and reactants,
(
As written, the reaction involves the formation of water vapour. The standard
state of water at 298 K is, of course, the liquid phase, so that to calculate the
standard enthalpy of combustion of methanol would require us to know the
enthalpy of vaporisation of water.
fHo298 / kJ mol1
Mean Cp / J K1 mol1
SO2
SO3
296.8
392.9
46.4
56.1
O2
31.4
Strategy
Write a balanced chemical equation for the gas-phase oxidation of sulfur dioxide.
Calculate the enthalpy change for the reaction at 298 K, using Equation 13.6 and
the stoichiometric coefficients from the chemical equation. Then use Equation
13.10 to determine the enthalpy change at 798 K, using Equation 13.11 to
determine the change in the mean heat capacity.
Solution
The oxidation of sulfur dioxide may be written as
SO2 (g) + O2 (g) SO3 (g)
Thus, using Equation 13.6,
)
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( ))
( ))
( ))}
*(
)+
)
{
)
(
)}
*(
)+
so that
(
(
)
)
*(
)+
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then
(
where q is the heat transferred to the system and w the work done on the
system,
(
The system absorbs heat and has work done on it, so the change in the internal
energy is positive.
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Thus, the difference between the enthalpy and internal energy change for a
reaction depends upon the change in the amount of gas, through Equation 13.19
and so, if
then
*(
)+
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Solution
If a change of 20.250 kJ of energy causes and increase in temperature of 1.890 K,
then the amount of energy required to cause a change of 1.000 K is
(
) (
This calibration factor is equivalent to the heat capacity of the calorimeter and its
contents. Thus, a temperature change of 2.424 K must correspond to a change in
internal energy of
(
)+
) (
) (
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Solution
Writing a balanced chemical equation for the reaction
CH3CO2CH3 (l) + 3.5 O2 (g) 3 CO2 (g) + 3 H2O (l)
shows that
(
)
*(
)+
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Answers to boxes
Box 13.1 James Joule and the equivalence of heat and work
In a reproduction of the Joule experiment, a stirrer paddle is connected to a mass
of 1.0 kg that can fall through a height of 2.0 m. It takes 4200 J to heat 100 g of
water by 10C. How many times must the mass be dropped to cause this heating?
Strategy
Calculate the change in the potential energy of the mass when it falls using
Equation 1.16. Determine the number of times that the mass must be dropped as
a ratio of the total energy change required to the energy change for each drop.
Solution
The potential energy lost by the mass on each fall is given by Equation 1.16,
(
) (
then the hot water may freeze first. Hot water evaporates at a faster rate than
cold water. Evaporation causes cooling, because it requires heat to be
transferred from the water to the surroundings. Thus, for the hot water, energy
is lost through both evaporation and thermal conduction. If thermal conduction
through the walls of the cup is negligible, because the material is a good
insulator, then the hot water will cool at a faster rate that the cold water and may
freeze first.
If the cups have lids on, the cold water is likely to freeze first. The lids minimise
evaporation and thermal conduction is the most significant way that energy is
lost.
Fuel
Typical
Mr
composition
cH
Energy density
/ kJ mol1
/ kJ g1
Petrol
C8H18
114
5470
48.0
Diesel
C20H42
282
8090
28.7
Natural gas
CH4
16
890
55.6
Hydrogen
H2
286
143.0
Methanol
CH3OH
32
726
22.7
Ethanol
C2H5OH
46
1367
29.7
MTBE**
CH3OC4H9
88
3369
38.3
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Strategy
Consider the energy density of each of the fuels to determine which would be the
most efficient for applications where the mass of fuel is important.
Solution
(a) Hydrogen is the most efficient in terms of energy per unit mass of fuel and is
therefore used in the Space Shuttle.
(b) Formula 1 racing cars are more efficient than Indy cars, because the energy
density of petrol is greater than that of methanol. However, engine designs do
differ so that this is a rather crude comparison.
(c) A sample of fuel that contains 90% petrol and 10% MTBE, by mass has an
energy density
)+
)+
Thus, the petrol and MTBE mixture has a lower energy density than petrol, that
is less energy is released per unit mass of fuel if combustion is complete.
However, the mixture burns more completely in car engines, so that, in practice,
the energy actually obtained per unit mass may be higher than with petrol.
Solution
Mg (s) + 2 H2O (l) Mg(OH)2 (aq) + H2 (g)
(a)
(
{
) (
(
,(
))
( ))}
( ))
( ))}
(
-
)+-
because the enthalpies of formation of Mg(s) and H2(g) are 0, as the substances
are in their standard states.
(b) The heat needed to raise the temperature of 300 g water from 20 C to 80 C
is given by Equation 13.1. Thus, assuming that the heat capacity of the food is
the same as that of water, so that
then
(
) (
The molar mass of magnesium is 24.4 g mol1, so that this amount is equivalent
to a mass
(
)
( ))
(
( ))}
( ))
{
)
)
(
(
( ))
( ))}
)+
because the enthalpies of formation of N2(g) and O2(g) are 0, as the substances
are in their standard states. The enthalpy change is for the equation as written,
which has 4 mol of nitroglycerine.
(ii) If the chemical equation is, instead, written for the reaction of 1 mol of
nitroglycerine then the enthalpy change will be a quarter of that calculated in
part (a)
(
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(b) (i) The work done on expansion is, from Equation 13.14.
so that
( )
( )
( )
Thus,
(
Note that the work done on the system is negative because the system itself does
work in expansion through the creation of the gas.
(ii) Using Equation 13.19,
)
*(
)+
Notice that even with the large volume change in this reaction, the difference
between rH298 and rU298 is relatively small.
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2.
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Solution
(a) The volume of the room is
) (
3.
(
)
)
*
*(
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)+
Because
then
(
)
(
*
)
+
(
*
)
+
(
which is equivalent to
4.
Calculate the enthalpy change when 100 g of water freezes at 0 C. (The standard
enthalpy change of fusion of water is 6.01 kJ mol1.)
Strategy
Calculate the molar mass of water and hence determine the amount that is
equivalent to a mass of 100 g. Hence determine the enthalpy change as a
multiple of the molar enthalpy change.
Solution
The molar mass of water is
*
)+
) (
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5.
Calculate the energy needed to melt 750 kg of sodium metal at 371 K. (The
standard enthalpy change of fusion of sodium is 2.60 kJ mol1.)
Strategy
Determine the amount of sodium that corresponds to a mass of 750 kg. Hence
determine the enthalpy change as a multiple of the molar enthalpy change.
Solution
The molar mass of sodium is
) (
6.
)+
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) (
The enthalpy change when the temperature 10 g of water increases from 273 K
to 373 K is, from Equation 13.2,
7.
, of solid KrF2.
Strategy
Divide the reaction that forms solid KrF2 into two steps: the first, in which
gaseous KrF2 is formed, and the second, in which the gaseous KrF2 sublimes to
solid KrF2. Calculate the enthalpy change for the first process as the reverse of
the enthalpy change for the decomposition reaction. Note that because the data
is given for a reaction at constant volume so that the heat transferred is
equivalent to the internal energy change, it is necessary to use Equation 13.19 to
determine the enthalpy change. The enthalpy change for the sublimation of
gaseous to solid KrF2 is the reverse of the enthalpy change given for sublimation
from gas to solid.
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Solution
The reaction
Kr (g) + F2 (g) KrF2 (s)
may be separated into two steps
Kr (g) + F2 (g) KrF2 (g) KrF2 (s)
The first step is equivalent to the formation of gaseous KrF2 from its elements in
their standard states. For a reaction that occurs at constant volume, the heat
released is equivalent to the internal energy change. Thus, for the decomposition
reaction
KrF2 (g) Kr (g) + F2 (g)
*(
)+
(
The enthalpy of sublimation
the conversion of solid to gaseous KrF2. The enthalpy change for the conversion
of gaseous to solid KrF2 is thus
(
( )
( ))
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( ))
(
(
8.
( ))
)
(
(
( )
( ))
Use the following enthalpy changes to calculate the standard enthalpy change of
formation of HNO3 (l).
H2O2 (l) + 2 NO2 (g) 2 HNO3 (l)
Ho = 226.8 kJ mol1
Ho = +66.4 kJ mol1
Ho = 187.8 kJ mol1
Strategy
Combine the three chemical equations in such a way that the combination is
equivalent to the formation of HNO3 (l) from its elements in their standard states.
Calculate the standard enthalpy of formation by combining the enthalpy changes
for the individual reactions in the same way.
Solution
The reaction
H2 (g) + N2 (g) + 3 O2 (g) 2 HNO3 (l)
which corresponds to the formation of HNO3(l), is equivalent to the sum of the
three individual reactions listed
H2O2 (l) + 2 NO2 (g) 2 HNO3 (l)
Ho = 226.8 kJ mol1
Ho = +66.4 kJ mol1
Ho = 187.8 kJ mol1
When the components that occur as both reactants and products are cancelled,
the combination
{H2O2 (l) + 2 NO2 (g)} + {N2 (g) + 2 O2 (g)} + {H2 (g) + O2 (g)}
2 HNO3 (l) + 2 NO2 (g) + H2O2 (l)
is equivalent to
H2 (g) + N2 (g) + 3 O2 (g) 2 HNO3 (l)
for which the enthalpy change is
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As written, this is the enthalpy change for the formation of 2 mol of HNO3(l). The
standard molar enthalpy of formation of HNO3(l) is therefore half this value
(
9.
The reaction
2 Al (s) + Fe2O3 (s) 2 Fe (s) + Al2O3 (s)
is known as the thermite reaction and is a spectacular demonstration of an
exothermic chemical reaction. Use data from Appendix 7 to calculate the
enthalpy change when 54.0 g of aluminium reacts at 298 K (25C).
Strategy
Use Equation 13.6 to calculate the enthalpy change of reaction from the
enthalpies of formation for the products and reactants. Determine the amount of
aluminium that corresponds to a mass of 54.0 g from the molar mass of
aluminium. Hence calculate the enthalpy change for the sample as a proportion
of the molar change.
Solution
Using Equation 13.6
(
where the terms i are the stoichiometric coefficients of the products and
reactants, so that
{
(
{
( ))
(
( ))
*(
( ))}
( ( ))}
)+
*(
)+
where the enthalpy of formation of Fe(s) and Al(s) are zero, because they are the
standard states for the elements.
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so that a mass of 54 g
contains an amount
(
) (
10.
(2)
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11.
( )
( ))
( )
)+
( ( ))
( ))
When 1.54 g solid biphenyl, ((C6H5)2), was burned in excess oxygen at 298 K in a
bomb calorimeter to form CO2 (g) and H2O (l), 64.23 kJ of heat was released.
Calculate
for biphenyl.
Strategy
Calculate the amount of biphenyl and hence the molar change in the internal
energy from the heat transferred at constant volume. Determine the enthalpy
change for the combustion process using Equation 13.19. Use Equation 13.6 to
express the enthalpy change for the reaction in terms of the enthalpies of
formation of the products and reactants. Substitute the values for the enthalpies
of reaction, and the enthalpies of formation of CO2(g) and H2O(l). Rearrange to
determine the value of the unknown enthalpy of formation of biphenyl.
Solution
The combustion of biphenyl corresponds to the reaction
(C6H5)2 (s) + 14.5 O2 (g) 12 CO2 (g) + 5 H2O (l)
The heat transferred at constant volume is equivalent to the change in internal
energy
)+
) (
) (
)
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)
*(
)+
where the terms i are the stoichiometric coefficients of the products and
reactants, so that
{
( ))
(
{
((
*(
) ( ))
)
((
( ))}
( ))}
) ( ))
)+
(
)}
Rearranging,
((
12.
) ( ))
Calcite and aragonite are two forms of calcium carbonate. Calculate the enthalpy
change for the transition from calcite to aragonite. (fH (calcite) =
1206.9 kJ mol1 and fH(aragonite) = 1207.1 kJ mol1.)
Strategy
Use Equation 13.6 directly.
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Solution
Using Equation 13.6, the standard enthalpy change for the reaction
CaCO3 (calcite) CaCO3 (aragonite)
is
(
(
(
13.
)
)
(
)
)
)
Calculate the enthalpy change when gaseous benzene, C6H6, dissociates into
gaseous atoms at 298 K. Carry out the calculation by two different methods
using the data in (a) and (b). Comment on the difference in the values you obtain
by the two methods.
(a) Assuming benzene molecules contain three single and three double
carboncarbon bonds and use mean bond enthalpy data. (Mean bond
enthalpies / kJ mol1: CC, 347; C=C, 612; CH, 412.)
(b) The enthalpy change of combustion of liquid benzene at 298 K is
3267.4 kJ mol1. The enthalpy change of vaporization of benzene is
33.9 kJ mol1. (fHo298 / kJ mol1: CO2 (g), 393.5; H2O (l), 285.8; C (g), 716.7;
H (g), 218.)
Strategy
(a) Calculate the sum of the mean bond enthalpies for all of the bonds that are
broken.
(b) Write the dissociation process as a series of steps for which all of the
enthalpy changes are known. Calculate the enthalpy change for the process as a
sum of the enthalpy changes for the individual steps.
Solution
(a) If the CC bonds within benzene are considered as an alternating series of
single and double bonds, then to dissociate benzene into atoms, it is necessary to
break 3 CC bonds, 3 C=C bonds and 6 CH bonds. Bond breaking is
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endothermic so the enthalpies all have positive values. The total enthalpy
required is thus
)+
)+
)+
(2)
(3)
(4)
6 C(s) 6 C (g)
(5)
3 H2 (g) 6 H (g)
for which the enthalpy changes are known. The first step, in which gaseous
benzene condenses to liquid benzene, is the reverse of vaporization, so that
(
( ))
The third step corresponds to the reverse of the reactions that form of CO2 (g)
and H2O (l), so that
[{
,*
( ))}
)+
(
*
( ))}]
)+-
The fourth step corresponds to the formation of gaseous carbon from solid
carbon so that
( ( ))
and the fifth to the formation of hydrogen atoms from hydrogen molecules,
( ( ))
)
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)
)
)
)
Comparing the values calculated using the two methods shows that using mean
bond enthalpies results in an underestimate of the enthalpy change on
dissociation. This implies that it takes more energy to break up benzene to its
constituent atoms than if it were an assembly of single and double bonds. This
additional energy is often known as the energy conjugation or resonance.
14.
Use Equation 13.11 to determine the change in the heat capacity at constant
pressure on reaction. Then use the Kirchoff equation, Equation 13.10, to
determine the enthalpy of reaction at 800 K.
Solution
From Equation 13.10,
(
{
*
(
(
)
)}
{ (
)
)+
)
(
)}
*(
)+
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where we have been careful to include the various stoichiometric numbers for
the components.
(
15.
*(
)+
*(
The value is positive, which is to be expected, since work must be done on the
gas in order to compress it.
16.
For a reaction at constant pressure, the enthalpy change is +30 kJ. During the
reaction, the system expands and does 25 kJ of work. What is the change in
internal energy for the reaction?
Strategy
Use Equation 13.14 and Equation 13.18 to write an expression for the difference
between the internal energy and enthalpy change in terms of the work done.
Solution
From Equation 13.18,
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The magnitude of the work done on the system is negative for an expansion.
Combining the two equations and rearranging
Thus, for a gaseous expansion, the change in internal energy is less than the
change in enthalpy.
17.
Calculate the energy transferred as work, w, for a system that releases 450 J of
heat in a process for which the internal energy decreases by 135 J.
Strategy
Apply Equation 13.15, which is a statement of the first law of thermodynamics.
Solution
Rearranging Equation 13.15, which equates the change in the internal energy to
the work done and the heat transferred
then
18.
A 100 W electric heater is used to heat gas in a cylinder for 10 min. The gas
expands from 500 cm3 to 21.4 dm3 against a pressure of 1.10 atm. What is the
change in internal energy, U, of the gas?
Strategy
Calculate the energy transferred as heat from the power of the heater and the
time for which it operates. Then determine the energy transferred as work as
the gas expands using Equation 13.14. Finally, use Equation 13.15, to determine
the change in the internal energy as the sum of the energy transferred as heat
and as work. It will be necessary to pay close attention to the units and signs of
the various quantities.
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Solution
Power is the rate at which energy may be supplied. Thus if the power of the
electric heater is 100 W 100 J s1, and if the heater operates for a time period
of 10 min = 600 s, then the energy transferred as heat to the system is
When a system expands, the work done on the system is, according to Equation
13.14,
Thus,
(
19.
0.10 mol of calcium carbonate reacts with excess dilute hydrochloric acid at
298 K. Calculate the energy transferred as work.
Strategy
Write a balanced chemical equation for the reaction and use it to determine the
amount, and hence the volume, of gas produced by the reaction. Then use
Equation 13.14 to determine the work done.
Solution
Hydrochloric acid reacts with calcium carbonate to liberate carbon dioxide
2 HCl (aq) + CaCO3 (s) CO2 (g) + CaCl2 (aq) + H2O (l)
From the stoichiometry of the reaction, 0.01 mol CaCO3 (s) will produce 0.01 mol
of CO2 (g). There are no other gaseous components, so that
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Assuming that the change in the volume of the solid and liquid components is
negligible, then the work done may be approximated as
20.
The molar heat capacity of water at constant pressure is 75.6 J K1 mol1 at room
temperature. Calculate the mass of methanol that must be burned to heat 1 dm3
of water from 20.0C to 50.0C. (Assume the density of water is 1.0 g cm3).
Strategy
Determine the enthalpy of combustion of methanol using Equation 13.6 and the
data for the enthalpies of formation of the various products and reactants of the
combustion reaction from Appendix 7. Calculate the mass, and hence the
amount of water present from the volume and density. Determine the heat that
must be transferred in order to increase the temperature of this amount of
water. Assuming that the transfer of heat from the combustion of methanol to
the water is 100% efficient, determine the amount, and hence mass, of methanol
that would be needed for an enthalpy change on combustion equivalent to the
heat transferred.
Solution
The enthalpy of reaction for the combustion of methanol
CH3OH (l) + 1 O2 (g) CO2 (g) + 2 H2O (l)
may be determined using Equation 13.6
where the terms i are the stoichiometric coefficients of the products and
reactants, so that
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( ))
( ))}
(
( ))
*(
( ))}
)+
(
)+
)+
) (
The energy is needed to heat the water from 20.0C to 50.0C, which is an
increase of +30 K, is, from Equation 13.2
(
The amount of methanol which would be required to provide this heat through
combustion is thus
(
) (
)+
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21.
A slice of banana weighing 2.7 g was burned in oxygen in a bomb calorimeter and
produced a temperature rise of 3.05 K. In the same calorimeter, the combustion
of 0.316 g of benzoic acid produced a temperature rise of 3.24 K. cU for benzoic
acid is 3251 kJ mol1. If the average mass of a banana is 125 g, how much
energy in (a) kJ and (b) Calories (kcal) can be obtained on average from a
banana? (1 Calorie = 4.18 J).
Strategy
Determine the amount of benzoic acid burnt, and hence the heat that causes a
unit rise in temperature. Hence determine the heat transferred when the slice of
banana is burnt.
Solution
The molar mass of benzoic acid, C6H5COOH, is
*(
)+
) (
The heat released by the combustion of the sample of benzoic acid is thus
(
*(
) (
)+
This is the heat transferred by burning a 2.7 g slice of banana. The heat that
could be obtained from a whole banana is thus
*(
) (
)+
which is equivalent to
(
22.
Car safety airbags inflate when the car undergoes a sudden deceleration, setting
off a reaction which produces a large amount of gas. One of the reactions used is
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(b) An airbag system is inflated by 2.4 mol (around 60 dm3) of N2 (g). Calculate
the enthalpy change when this amount of nitrogen is produced at 298 K.
(c) Assuming this energy all goes into heating the N2 (g), what will be the final
(Cp for N2 (g) = 29.1 J K1mol1)
(a) Use Equation 13.6, which relates the enthalpy of reaction to the enthalpies of
formation for the various reactants and products.
(b) Determine the amount of NaN3 (s) necessary to produce the amount of N2 (g)
that fills the air bag and hence the enthalpy change as an equivalent proportion
of the molar enthalpy change of reaction.
(c) Use Equation 13.1 to determine the temperature rise that this enthalpy
change could produce.
Solution
(a) From Equation 13.6,
(
(
( ))}
( ))
( ))
( ))
because the enthalpy of formation of both Na(s) and N2(g) are zero as the
elements are in their standard states. Thus
(
( ))
(b) Using the stoichiometry of the reaction, 2.4 mol of N2 arises from
(
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so that
23.
) *(
)+
Strategy
Apply the Kirchoff equation, Equation 13.10, using the data for the heat
capacities of ethanol in the liquid and vapour phase from Appendix 7.
Solution
Applying Equation 13.10
(
then
{ (
(
,*(
Using values of
)}
)
(
24.
)+
) -
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Solution
The oxidation of liquid ethanol to ethanoic acid by molecular oxygen may be
written as
C2H5OH(l) + O2(g) CH3COOH(l) + H2O(l)
Thus, applying Equation 13.6,
(
( ))
(
{
*(
( ))}
(
( ))
(
)
( ))}
)+
*(
( )+
to calculate the equivalent value for the enthalpy change at 310 K. The change in
the heat capacities on reaction is
(
{ (
*(
( ))
(
)
*(
( ))}
{ (
( ))
( ))}
)+
)
)+
and so
(
(
25.
)
)
*(
)+
50.0 cm3 of HCl(aq) of concentration 1.0 mol dm3 is mixed with 50.0 cm3 of
NaOH(aq) of concentration 1.0 mol dm3 at 25 C in a constant pressure solution
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calorimeter. After the reactants are mixed the temperature increases to 31.8 C.
Assuming that the solutions have the same density and specific heat capacity as
water, calculate the enthalpy change for the neutralisation reaction. (Section
13.5)
Strategy
Calculate the mass of the reaction mixture from the known volumes by assuming
that the density of both solutions is the same as water. Use Equation 13.1 to
calculate the heat released for the increase in temperature by assuming that the
specific heat capacity of the mixture is the same as that of water. For a reaction at
constant-pressure, the heat released is equal to the change in enthalpy. Use the
concentrations to express the result as a molar quantity.
Solution
The neutralisation reaction may be written as
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
The mass of the reaction mixture is
(
( )(
(
(
(
(
*(
))
)+
Thus, if we assume that no heat is absorbed by the calorimeter, and note that an
increase from 25 C to 31.8 C is equivalent to a change of
(
then rearranging Equation 13.1, the heat supplied to the reaction mixture is
The heat used to increase the temperature of the reaction mixture is equal in
magnitude to the enthalpy of reaction
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26.
)
( ))
(
(
( ))}
(
{
( ))
( ))
( ))}
( ))}
)
{
( ))
( ))}
( ))
(
[{
(
( ))
( ))}
(
(
)]
( ))}
)]
where the terms in the enthalpies of formation of CO2 and H2O cancel.
We may calculate the enthalpies of combustion from the calorimetry data. If
12.54 kJ of energy resulted in a temperature rise of 1.000 K, then the
temperature rise of 5.017 K caused by the combustion of the sample of 0.02 mol
of methylpropane must be the result of the release of heat
(
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)
)
)
)
Note that it is good practice to indicate explicitly that the quantity is positive,
implying that the isomerization is endothermic.
27.
A chemist is trying to measure the enthalpy change for the hydration reaction:
Na2CO3(s) Na2CO310H2O(s)
Calibration of a solution calorimeter shows that 357.9 J of heat raises the
temperature by 1.00 K. When 2.500 g of anhydrous sodium carbonate, Na2CO3,
was dissolved in 100.00 cm3 of water, the temperature increased by 1.550 K. On
dissolving 3.500 g of sodium carbonate decahydrate, Na2CO310H2O in
100.00 cm3 of water, the temperature decreased by 2.310 K. calculate the
enthalpy change of hydration of sodium carbonate
Strategy
Determine the molar enthalpy changes for the dissolution of anhydrous sodium
carbonate and sodium carbonate decahydrate by calculating the heat released
and the amount of each substance present. Then calculate the molar enthalpy
change for the hydration reaction as the difference between these two quantities.
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Solution
We may calculate the heat released in each reaction from the measured rise in
temperature and the calibration factor, C. Thus, the molar enthalpy change for
the dissolution of anhydrous sodium carbonate
Na2CO3(s) Na2CO3(aq)
is
( ))
) (
(
(
(
)
)
)
)
) (
( ))
(
28.
( ))
(
)
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where the molar mass of benzoic acid, C6H5COOH, is M = 122.12 g mol1. Thus,
the heat released is
(
*(
)
) (
(
)+
)
(
)
)
, so that the
calibration constant is
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The molar mass of -D-glucose, C6H12O6, is 180.16 g mol1, so that the standard
molar enthalpy of combustion of -D-glucose at 298 K is therefore
(
) (
[{
( ))}
{
( ))
[ (
*
( ))}]
*(
( ))}]
)+
)+
and so
(
(
29.
)
)
*(
)+
A mixture of sulfur dioxide and air containing 10% (by volume) SO2 is passed
over a catalyst at 700 K at a rate of 100 mol min1. If, at constant pressure, all of
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the SO2 is converted to SO3, what is the rate of evolution of heat? Use relevant
data from Appendix 7. (Section 13.3)
Strategy
Use Equation 13.6 to calculate the molar enthalpy of reaction at 298 K for the
oxidation of SO2 to SO3. Then apply the Kirchoff equation, Equation 13.10, to
calculate the molar enthalpy of reaction at 700 K. Use this value to calculate the
rate of evolution of heat, knowing the rate at which SO2 flows over the catalyst.
Solution
For the complete oxidation of SO2,
SO2(g) + O2(g) SO3(g)
the standard enthalpy of reaction is given by Equation 13.6,
(
( ))
( ))
*(
(
)
( ))}]
)+
( ))
[ (
)
( ))
*(
( ))}]
)+
so that
(
(
)
)
*(
)+
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10 per cent of the gas is SO2 by amount of substance. If the rate at which the
mixture flows over the catalyst is 100 mol min1, then the rate at which heat is
evolved is
(
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