Thermochemistry Problems

Problem 1. Enthalpy and Phase Change

a) If a bathtub contains 160. L of water at 37C (body temperature), what mass of ice (at 0C)
would you need to add in order to end up with water at a uniform temperature of 25C?
Since the bathtub water has a higher temperature than the ice, it will transfer its heat into the
ice. This will first melt the ice to water at 0C, and then warm this melted ice from 0C up to
25C. As the bath water gives up its heat to the ice, it will cool from 37C to 25C. We
assume that all of the heat lost by the bath water is gained by the ice to (1) melt the ice and
(2) warm the melted ice:

q H 2O + (q melt + q warm ) = 0

q H 2O = (q melt + q warm )

or

The amount of heat given up by the bath water would be:

1000mL 1.00 g 4.184 J

(25 37 )K = 8.03 10 6 J
q H 2O = m H 2O C H 2O TH 2O = 160 L

1L 1mL gK

For the ice, the first part involves a change of state (use enthalpy of fusion), while the
second involves a change of temperature (use specific heat capacity) of the melted ice:
Heat to melt ice:

Heat to warm:

q melt = mice H fus ,ice = mm.ice (333 J g )

4.184 J
(25 0)K = mm.ice (104.6 J g )
q warm = mm.ice C m.ice Tm.ice = mm.ice
gK

Plugging these three q expressions into the original energy balance equation above gives:

8.03 10 6 J = mice (104.6 J g ) + mice (333 J g )

We can then solve for the mass of ice:

mice (104.6 J g + 333 J g ) = 8.03 10 J or

6

Chem 131

mice =

8.03 10 6 J
437.6 J g

Solutions to Thermochemistry Problems

= 18,350 g = 18 kg

Page 1

b) Repeat the analysis, but this time for a coffee cup that contains 250. mL of water at 95C.
same process as previous, but different numbers for qH2O

1.00 g 4.184 J
(25 95)K = 7.32 10 4 J
q H 2O = m H 2O C H 2O TH 2O = 250mL

1mL gK

mice =

7.32 10 4 J
437.6 J g

= 170 g

c) When you finish taking a hot shower, the air in the 1.0m x 2.0m x 3.0m shower enclosure is
saturated with water vapor (i.e., 100% relative humidity) at 45C. How much total heat is
released from the condensation of this water vapor as the air cools to 25C? (Note: ignore
any energy changes associated with the temperature change; focus on the energy from the
phase change.)
In this problem, the heat comes from one particular processthe condensation of water
vapor:

H2O (g) H2O (l)

H = Hvap = 40.7 kJ/mol

The challenge in this problem is to figure out how many moles of water condense. The way
to do this is to determine the number of moles of water vapor in the air initially, and the
number in the air at the end. The difference between the two gives the number that are no
longer in the air (i.e., the number of moles that condensed).
Note that the air in the shower stall is a gas mixtureit contains (primarily) N2, O2, and H2O
gases. We can determine the number of moles of water in the air in each case using the
ideal gas law, if we know the partial pressure of water PH2O in each case.

n H 2O =

PH 2OV
RT

We can determine PH2O in each case by recognizing that the air is saturated with water
vapor, meaning that the partial pressure of water corresponds to the vapor pressure of water
at that temperature (you can look these up in Appendix G):
PH2O (@45C) = 71.9 torr and PH2O (@25C) = 23.8 torr
The volume V of the gas (the moist air in the shower enclosure) is 6.0m3 = 6.0 x 106 cm3 =
6.0 x 106 mL = 6.0 x 103 L. Applying the ideal gas equation:

Chem 131

Solutions to Thermochemistry Problems

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n H 2O (45C ) =

PH 2OV
(71.9 torr ) 6.0 10 3 L 1 atm = 21.8 mol H O
=
2
760 torr
L atm
RT

0.08206
(318 K )
mol K

PH 2OV
(
23.8 torr ) 6.0 10 3 L 1 atm

= 7.7 mol H 2 O
n H 2O (25C ) =
=
L atm
RT
760 torr

(298 K )
0.08206
mol K

So, the amount of water that condenses is 21.8 7.7 mol H2O = 14.1 mol H2O. The
corresponding amount of heat released is therefore:

q cond = n H 2O ( H vap , H 2O ) = (14.1 mol )( 40.7 kJ mol ) = 570 kJ

Or, in other words, 570 kJ of heat is released from the condensation of the water vapor.

Problem 2. Energy Conversion

A typical incandescent light bulb emits approximately 10kJ of useful (i.e., visible) light energy
over a 1-hour period of use.
a) List all of the conversions between different forms of energy needed to provide this light,
assuming that the electricity is supplied from a natural-gas fired power plant.
If we start with the natural gas, the chemical potential energy of the natural gas is converted
during combustion into the thermal energy of the products (CO2 and water vapor). This
thermal energy is then converted into the mechanical (kinetic) energy of the spinning
turbine. This is converted in the generator into electrical energy, which then travels over the
transmission and distribution wires to your home. At the light bulb, the electrical energy is
converted into light (electromagnetic radiation), as well as into a lot of thermal energy in
heating the light bulb filament to high temperatures. (Note that we could start all the way at
the beginningnuclear potential energy is converted into thermal energy and light in the
fusion reactions of the sun, the light is then converted into chemical potential energy by
plants during photosynthesis, this chemical potential energy is then altered slightly during
decomposition chemical reactions that result in the formation of natural gas, then )
b) If we assume natural gas to be 100% methane (CH4), what mass of methane is needed to
provide the light energy above? Assume the following efficiencies: 33% for generation of
electricity from the methane, 90% for electricity transmission and distribution, 2% for the light
fixture and bulb. Note that the enthalpy of combustion of methane is:

CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)

Chem 131

Solutions to Thermochemistry Problems

kJ
Hrxn = 802.30 mol
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Working backwards, 10kJ of light requires

the light fixture. This requires
plant. This requires

556 kJ

500 kJ

0.33

0.90

10 kJ

0.02

= 500 kJ of electrical energy entering

= 556 kJ of electrical energy leaving the power

= 1680 kJ of chemical potential energy in the methane. We

can see from the combustion reaction of methane above that we get about 800 kJ of energy
for each mole of methane burned, so roughly speaking, we would need about 2 moles
(~32g). More precisely:

1 mol CH 4
1680 kJ
802.30 kJ

16.0 g CH 4

1 mol CH 4

= 34 g CH 4

Problem 3. Coal Gasification

The water gas reaction can be used to produce hydrogen by treating carbon (from coal) with
high temperature steam:

C (s) + H2O (g) CO (g) + H2 (g)

a) Use heats of formation to determine the enthalpy change for this reaction. Is the reaction
endothermic or exothermic?

Hrxn = p Hf(P) r Hf(R)

Hrxn = Hf[CO (g)] + Hf[H2 (g)]
Hrxn = (110.525 kJ mol-1) +
Hrxn = + 131.31 kJ mol-1

Hf[C (g)] Hf[H2O (g)]

0

(241.83 kJ mol-1)

Since Hrxn is positive, the reaction is endothermic.

b) In practice, the energy needed to drive this reaction is usually supplied by burning (i.e.,
combusting) some additional carbon (to produce CO2). What mass of carbon needs to be
combusted in order to provide the energy needed to convert 1.0kg of carbon in the watergas reaction?
Since the water-gas reaction is endothermic, an input of energy is needed in order to
convert C in this reaction. From the Hrxn value calculated above, we can determine the
amount of energy needed for 1.0kg C. The problem statement indicates that all of this
energy will be provided from a second reaction, the combustion of carbon, which is
exothermic. We can write a reaction equation for this combustion, and then use heats of
formation to find the Hrxn of this reaction. Finally, we can determine how much C needs to
be combusted in this second reaction to provide the total amount of energy needed.

Chem 131

Solutions to Thermochemistry Problems

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Energy needed to convert 1.0 kg C in water-gas reaction:

1000 g C 1 mol C 1 mol rxn 131.31 kJ

= 1.09 10 4 kJ

1.0 kg C
1
kg
C
12
.
01
g
C
1
mol
C
1
mol
rxn

Balanced reaction equation for combustion of carbon:

C (s) + O2 (g) CO2 (g)

Hrxn = Hf[CO2 (g)] Hf[C (s)] Hf[O2 (g)]

Hrxn = (393.5 kJ mol-1)

= 393.5 kJ mol-1

The heat from this combustion reaction will provide all of the energy to supply the energy
needs of the water-gas reaction, or in other words, qcomb = qwg rxn = 1.09 x 104 kJ. We can
then determine how many moles of combustion reaction are needed for this amount of
energy, and in turn, the corresponding moles and mass of carbon in the reaction:

1 mol rxn 1 mol C 12.01 g C 1 kg C

= 0.33 kg C
1.09 10 4 kJ

393
.
5
kJ
1
mol
rxn
1
mol
C
1000
g
C

Problem 4. Heats of Formation/Calorimetry

Some camping stoves use ethanol (C2H5OH) as fuel.
a) Write a balanced equation for the combustion of ethanol.

C2H5OH (l)

+ 3 O2 (g)

2 CO2 (g)

3 H2O (l)

b) Use these heats of formation to calculate H for the combustion of ethanol.

kJ ,
Hf C2H5OH (l) = 277.7 mol

kJ ,
Hf CO2 (g) = 393.5 mol

kJ
Hf H2O (l) = 285.8 mol

kJ ) + 3 (285.8 kJ ) 1 (277.7 kJ ) 3 (0)

Hrxn = 2 (393.5 mol
mol
mol

= 1366.7 kJ

c) If 66% of the heat released by the burning ethanol is absorbed by a pot of water on the
stove, how is qwater mathematically related to qreaction?
qwater = 0.66 qreaction

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Solutions to Thermochemistry Problems

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d) How many grams of ethanol must burn to melt 500. g of ice (at 0C) and raise the
temperature of the liquid water to 100C?
For the ice (water), the first part involves a change of state (use enthalpy of fusion), while
the second involves a change of temperature (use specific heat capacity) of the melted ice:
Heat to melt ice: q melt = mice H fus ,ice = (500.g )(333 J g ) = 166,500 J = 166.5 kJ

4.184 J
(100 0)K = 209,200 J = 209.2 kJ
gK

Heat to warm: q warm = mm.ice C m.ice Tm.ice = (500.g )

Total heat input to water: qwater = qmelt + qwarm = 375.7 kJ

1 q
1
qreaction = 0.66
water = 0.66 (375.7 kJ) = 569 kJ

569 kJ

1 mol C2H5OH 46.07 g C 2H5OH

= 19 g C2H5OH
1 mol C2H 5OH
1366.7 kJ

Problem 5. Enthalpy of Reaction/Hesss Law

Because the following chemical reactions occur in solution, their enthalpies of reaction can be
easily measured in a calorimetry experiment without loss of heat to the surroundings:
Rxn 1:

Mg (s) + 2 HCl (aq) MgCl2 (aq) + H2 (g)

Rxn 2:

MgO (s) + 2 HCl (aq) MgCl2 (aq) + H2O (l)

a) Using heats of formation, calculate the reaction enthalpy that should result for each of
Reactions 1 and 2 above. (The heat of formation of aqueous MgCl2 is 801.15 kJ mol-1; all
others can be found in your textbook.)

Hrxn1 = Hf[MgCl2 (aq)] + Hf[H2 (g)] Hf[Mg (s)] 2 Hf[HCl (aq)]

Hrxn1 = (801.15 kJ mol-1) + 0 0 2 (167.159 kJ mol-1) = 466.83 kJ mol-1
Hrxn2 = Hf[MgCl2 (aq)] + Hf[H2O (l)] Hf[MgO (s)] 2 Hf[HCl (aq)]
Hrxn2 = (801.15 kJ mol-1) + (285.83 kJ mol-1) (601.24 kJ mol-1) 2 (167.159 kJ mol-1)

= 151.42 kJ mol-1

Chem 131

Solutions to Thermochemistry Problems

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b) The formation of water from its elements can be represented by the reaction:
Rxn 3:

2 H2(g) + O2(g) 2H2O(l)

H = -572 kJ

Using only the reaction enthalpies for Reactions 1, 2, and 3 above, use Hesss Law to
calculate the enthalpy of the following reaction (the burning of a strip of magnesium metal):
2 Mg(s) + O2(g) 2 MgO(s)
The strategy here is to rearrange reaction equations 1, 2, and 3 in such a way that they can
be combined together to produce the reaction above. First, look for substances in the
combined reaction that only appear in one of the 3 reactions; this will automatically dictate
how that particular reaction must be written. In this case, all 3 substances in the combined
reaction fall into this category.
Since Mg(s) only appears in Rxn 1, we know that Rxn 1 must be written in its current
direction, but multiplied by 2 to get matching stoichiometric coefficients.
Since O2(g) only appears in Rxn 3, this reaction must be written as is.
Since MgO(s) only appears in Rxn 2, we know that Rxn 2 must be reversed (so that MgO
will appear on the product side of the reaction), and it must be multiplied by 2.
In each case, we can manipulate the Hrxn values appropriately:
2 x Rxn1:

2 Mg(s) + 4 HCl(aq) 2 MgCl2(aq) + 2 H2(g)

-2 x Rxn2:

2 MgCl2(aq) + 2 H2O(l) 2 MgO(s) + 4 HCl(aq)

1 x Rxn3:

2 H2(g) + O2(g) 2H2O(l)

2 x H1 = 933.66 kJ
2 x H2 = 302.84 kJ
1 x H3 = 572 kJ

When we combine these reactions together, we confirm that all of the necessary substances
cancel out in order to give the correct overall reaction, and we calculate the overall H by
combining the 3 values above to get 1203 kJ mol-1.
c) How much heat could theoretically be released from the burning of 2.00g of magnesium
metal in 1.75L of air at a pressure of 760 torr and 25C?
Here, we are in essence given amounts of both reactants (Mg and O2), so this must be a limiting
reactant problem. In order to determine the total amount of heat released, we will need to know
how many moles of reaction will occur based on the amount of limiting reactant. Since Mg is a
solid, we are given the amount as a mass, which we will need to convert as usual to moles Mg,
and then to moles of reaction.

1 mol Mg 1 mol rxn

= 0.04114 mol rxn

2.00 g Mg
24.305 g Mg 2 mol Mg

Chem 131

Solutions to Thermochemistry Problems

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Since O2 is a gas, we will need to use the ideal gas equation. Moreover, O2 is present in a gas
mixture (air), so we will need to use partial pressures. Note that air is 21% O2 on a per mole
basis, and thus the partial pressure of O2 in air will be 21% of the total pressure (alternately, you
could calculate the total number of moles of gas in the air sample, and then take 21% of that).

1 atm
= 0.21 atm
PO2 = (0.21)(760 torr )
760
torr

nO2 =

PO2 V
RT

(0.21 atm )(1.75 L )

L atm

0.08206
(298 K )
mol K

= 0.0150 mol O2

1 mol rxn
= 0.0150 mol rxn

1
mol
O
2

Thus, oxygen is the limiting reactant, and only 0.015 moles of reaction will occur. Finally, since
we know the number of moles of reaction, we can determine the amount of heat released:

1203 kJ
= 18 kJ (or, 18 kJ of heat will be released)
q rxn = (0.015 mol rxn )
1 mol rxn

Chem 131

Solutions to Thermochemistry Problems

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