Chapter 6 Notes

CHEM 1411 General Chemistry Chemistry: A Molecular Approach by Nivaldo J. Tro

6 Thermochemistry
Chapter Objectives:
• Understand potential and kinetic energy, and the
first law of thermodynamics.
• Learn how to use specific heat to perform
calculations involving energy changes.
• Understand the concept of enthalpy, and use
standard heats of formation and Hess’s Law to
calculate enthalpy changes.
Mr. Kevin A. Boudreaux
Angelo State University 1
www.angelo.edu/faculty/kboudrea

Thermodynamics and Thermochemistry

• Why do chemical reactions occur? One major
driving force for reactions is stability: Substances
that are high in energy are generally less stable and
more reactive, while substances that are lower in
energy are generally more stable and less reactive.
• Thermodynamics is the study of heat and its
transformations.
• Thermochemistry is the branch of thermodynamics
that deals with the relationships between chemistry
and energy.

C(s) + O2(g) → CO2(g) + heat

2KClO3(s) + heat → 2KCl(s) + 3O2(g)

2
Chapter 6 Notes

Energy

Energy, Work, and Heat

• Energy is the capacity to supply heat or to do work.
Energy can be exchanged between objects by some
combination of either heat or work:
Energy = heat + work
ΔE = q + w
• Work is done when a force is exerted
through a distance:
Work = force × distance
• Heat is the flow of energy caused by
a temperature difference.

4
Chapter 6 Notes

Kinetic and Potential Energy

• Kinetic energy (EK) is the energy due to the motion
of an object with mass m and velocity v:
EK = ½ mv2
– Thermal energy, the energy associated with the
temperature of an object, is a form of kinetic
energy, because it arises from the vibrations of
the atoms and molecules within the object.
• Potential energy (EP) is energy due to position, or
any other form of “stored” energy. There are several
forms of potential energy:
– Gravitational potential energy
– Mechanical potential energy
– Chemical potential energy (stored in chemical
bonds) 5

Kinetic and Potential Energy

• Potential energy increases when things that attract
each other are separated or when things that repel
each other are moved closer.
• Potential energy decreases when things that attract
each other are moved closer, or when things that
repel each other are separated.
• According to the law of conservation of energy,
energy cannot be created or destroyed, but kinetic
and potential energy can be interconverted.

6
Figure 6.1 Figure 6.2
Chapter 6 Notes

Kinetic and Potential Energy

• Water falling in a waterfall exchanges gravitational
potential energy for kinetic energy as it falls faster
and faster, but the energy is never destroyed.

high EP decreasing EP low EP EK converted to

low EK increasing EK high EK thermal energy
and sound 7

The System and the Surroundings

• A system is the particular set of substances (a
chemical reaction, a phase change, etc.) that we
focus on in an experiment.
• The surroundings include everything else outside
the system — the flask, the room, the building, etc.
• If the system loses energy, the surroundings gain
energy, and vice versa.
• We have an isolated or closed system when energy
cannot cross the boundary in any direction.
surroundings

Solution of A + B
surroundings surroundings
system
energy flow
boundary
across boundary
8
surroundings
Chapter 6 Notes

Units of Energy
• From the expression for kinetic energy it can be seen
that energy has units of kg·m2/s2 (kg m2 s-2)
• The SI unit of energy is the joule (J):
[James Prescott
1 J = 1 kg m2 s-2 Joule, 1818-1889]

– Since joules are fairly small units, kilojoules (kJ)

are frequently used instead.
• A calorie (cal) is the amount of energy needed to
raise the temperature of 1 g of water by 1°C.
1 cal = 4.184 J (exact)
• The nutritional unit Calorie (Cal) is actually a
kilocalorie (kcal):
1 Cal = 1000 cal = 1 kcal = 4184 J
9

Units of Energy
• The watt (W) is a unit of power, the rate at which
energy is used:
1 W = 1 J s-1
• Kilowatt-hours (kWh) are the unit that is usually
reported on electrical bills:
1 kWh = 3.60×106 J

10
Chapter 6 Notes

Examples: Kinetic Energy

1. What is the kinetic energy (in kJ) of a 2300. lb car
moving at 55.0 mi/h?

Answer: 315 kJ
11

12
Chapter 6 Notes

The First Law of

Thermodynamics

13

The First Law: Conservation of Energy

• The law of conservation of energy, also known as
the first law of thermodynamics, states that energy
cannot be created or destroyed; it can only be
converted from one form into another.
• In other words, the total energy of the universe is a
constant.
ΔEuniverse = ΔEsystem + ΔEsurroundings = 0
• Potential and kinetic energy are interconvertible, but
for a particular system the total amount of potential
and kinetic energy is a constant.
• One of the implications of the first law is that the
best you can do with energy is to break even: a
perpetual motion machine, which would continually
create energy with no energy input, cannot exist.
14
Chapter 6 Notes

Internal Energy, E, and State Functions

• The internal energy (E) of a system is the sum of
all the kinetic and potential energies for every
particle in the system.
• The internal energy is a state function, which is
dependent only on the present state of the system,
and not on the pathway by which it got to that state.
• Some examples include energy (and many other
thermodynamic terms), pressure, volume, altitude,
distance, etc.
• An energy change in a system can occur by many
different combinations of heat (q) and work (w), but
no matter what the combination, ΔE is always the
same — the amount of the energy change does not
depend on how the change takes place.
15

State Functions

16
Chapter 6 Notes

Change in Internal Energy

• For an isolated system, with no energy flowing in or
out of the system, the internal energy is a constant.
– First Law of Thermodynamics (restated): The
total internal energy of an isolated system is
constant.
• It is impossible to completely isolate a reaction from
its surroundings, but it is possible to measure the
change in the internal energy of the system, ΔE, as
energy flows into the system from the surroundings
or flows from the system into the surroundings.
ΔE = Efinal - Einitial
ΔE = Eproducts - Ereactants

17

Energy Flow
C(s) + O2(g) → CO2(g)
• In this reaction, energy is released from the system
to the surroundings.
– The reactants have a higher E than the products,
so ΔE for the system is negative.
– This energy is gained by the surroundings, where
ΔE is positive. (ΔEsystem = -ΔEsurroundings)

Energy lost
to surroundings

18
Chapter 6 Notes

Energy Flow
CO2(g) → C(s) + O2(g)
• If the reaction is reversed, energy is absorbed by the
system from the surroundings.
– The reactants have a lower E than the products, so
ΔE for the system is positive.
– This energy is lost by the surroundings, where ΔE
is negative.

Energy gained
from surroundings

19

Energy Flow: Sign Conventions

• By convention, energy changes are measured from
the point of view of the system.
– Any energy that flows from the system to the
surroundings has a negative sign:
Efinal < Einitial
ΔE < 0
– Any energy that flows to the system from the
surroundings has a positive sign:
Efinal > Einitial
ΔE > 0

20
Chapter 6 Notes

Energy Flow: Sign Conventions

• Energy exchanges between the system and
surroundings take place through a combination of
heat (q) and work (w):
ΔE = q + w
• Energy going into the system, whether it’s heat
energy or work energy, has a positive sign, and
energy leaving the system, whether it’s heat energy
or work energy, has a negative sign:
q is (+) Heat is absorbed by the system
q is (-) Heat is released by the system
w is (+) Work is done on the system
w is (-) Work is done by the system
21

State Function — A Chemical Example

C8 H18 (l) + 25
2 O 2 (g) → 8CO 2 (g) + 9H 2O(g)
initial state ( Einitial ) final state ( Efinal )

• For a given change, ΔE (q + w) is constant, even

though the specific values of q and w can vary.
• Heat and work are NOT state functions, but ΔE is.
22
Chapter 6 Notes

State Functions and Reversibility

• Another characteristic of state functions is their
reversibility.
– Climbing back down Mount Everest, your final
position is now identical to your initial position,
and the value of the change in altitude is 0 miles.
– The overall change in a state function is zero
when the system returns to its original condition.
• For a nonstate function, the overall change is not
zero even if the path returns the system to its
original condition.
– For instance, the money spent on a trip or time
expended during traveling does not reappear.

23

Examples: Energy Flow

2. When gasoline burns in a car engine, the heat
released causes the products CO2 and H2O to
expand, which pushes the pistons outward. Excess
heat is removed by the car’s cooling system. If the
expanding gases do 451 J of work on the pistons
and the system loses 325 J to the surroundings as
heat, calculate the change in energy in J, kJ, and
kcal. (sim. to Ex. 6.1)

Answer: -776 J, -0.776 kJ, -0.185 kcal 24

Chapter 6 Notes

Measuring Heat
and Work

25

Heat and Temperature

• Heat and temperature are not the same thing!
– Heat is the exchange of thermal energy between a
system and its surroundings. Temperature is a
measure of the thermal energy of a sample.
– A fresh cup of coffee is hotter than a swimming
pool, but a swimming pool holds more heat than
the coffee. If you pour a 200°F cup of coffee into
a 100°F pool, the pool won’t become 150°F.
• Heat flows from higher temperatures to lower
temperatures, until the two regions reach the same
temperature, and are at thermal equilibrium.
• All forms of energy can be converted quantitatively
into heat, so it is possible to use heat as a measure of
energy for any chemical or physical process.
26
Chapter 6 Notes

Heat Capacity
• The thermal properties of a substance are those
that describe its ability to absorb or release heat
without changing chemically.
• The heat capacity (C) of an object is the amount of
heat (q) required to change its temperature by a
given amount (ΔT):
q
C = q = C ΔT
ΔT

ΔT = Tf - Ti
– Heat capacity has units of J/°C (or J/K), and is an
extensive property, depending on the sample size.
27

Specific Heat
• The specific heat (c, or specific heat capacity, Cs in
book) of an object, is the quantity of heat required to
change the temperature of 1 gram of a substance by
1 °C (or K):
q
c = q = c m ΔT
m ΔT
– Specific heat has units of J / g °C, and is an
intensive property, which is independent of the
sample size.
• The molar heat capacity (Cm), is the quantity of
heat required to change the temperature of 1 mole of
a substance by 1 °C (or K):
q
Cm = q = Cm moles ΔT
moles ΔT 28
Chapter 6 Notes

Specific Heats of Some Common Substances

29

Examples: Specific Heat

3. If a gold ring with a mass of 10.00 g changes in
temperature from 25.00°C to 28.00°C, how much
energy in joules has it absorbed? How much
energy is absorbed by 10.00 g of H2O under the
same conditions? (sim. to Ex. 6.2)

Answer: qAu = 3.87 J, qH2O = 125 J

30
Chapter 6 Notes

Examples: Specific Heat

4. What is the specific heat of the (fictional) element
dilithium if it takes 2.51 kJ to raise the temperature
of 42.0 g of dilithium by 10.0°C?

Answer: 5.98 J/g°C

31

Examples: Specific Heat

5. What is the final temperature of a 100.0 g sample of
water initially at 25.0°C after 25.1 kJ of heat energy
is added? (The specific heat of water is 4.18
J/g°C.) (sim. to For More Practice 6.2)

Answer: 85.0°C
32
Chapter 6 Notes

Work
• Work (w) is defined as the force (F) that produces
the movement of an object through a distance (d):
Work = force × distance
w=Fd
• Work also has units of J, kJ, cal, kcal, Cal, etc.
• The two most important types of chemical work are:
– the electrical work done by moving charged
particles.
– the expansion work done as a result of
a volume change in a system, particularly
from an expanding or contracting gas.
This is also known as pressure-volume
work, or PV work.
33

Pressure-Volume Work
• When propane, C3H8, is burned, 7 moles of gas are
produced for every 6 moles of reactants:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
– If the reaction takes place in a container with a
movable piston, the greater volume of gas product
will force the piston outward against the pressure
of the atmosphere, thus doing work on the piston.
– Pressure-volume work is equal to the pressure
(P) times the change in volume (ΔV); the sign is
negative because work is being done by the
system (work energy is leaving the system):
w = - PΔV
• The units of PV work are L·atm; 1 L·atm = 101.3 J.
34
Chapter 6 Notes

Expansion Work w = F d ; P = F/A

w = PAd
w = PAΔh
w = PΔV
w = -PΔV

35
Figure 6.5 MOV: Work of Gas Expansion

Expansion Work
w = - PΔV
• If the gas expands, ΔV is positive, and the work term
will have a negative sign (work energy is leaving the
system).
• If the gas contracts, ΔV is negative, and the work term
will have a positive sign (work energy is entering the
system).
• If there is no change in volume, ΔV = 0, and there is
no work done. (This occurs in reactions in which
there is no change in the number of moles of gas.)

36
Chapter 6 Notes

Examples: PV Work
6. Calculate the work done (in kJ) during a reaction in
which the volume expands from 12.0 L to 14.5 L
against an external pressure of 5.00 atm. (sim. to
Ex. 6.3)

Answer: -1.3 kJ 37

Constant-Volume Calorimetry: Measuring ΔE

• For any chemical reaction, the energy change is the
sum of the heat and work energies:
ΔErxn = q + w = q - PΔV
• Under conditions of constant volume, w=0, and the
energy change of the reaction is dependent only on
heat evolved at constant volume, qV:
ΔErxn = qV
• The heat change — and therefore the energy change
— in a chemical reaction occurring at constant
pressure can be measured in a bomb calorimeter, in
which a sample is sealed in a “bomb” surrounded by
a water bath, in which the temperature change can
be measured precisely.
38
Chapter 6 Notes

A Bomb Calorimeter
• The amount of heat
absorbed by the water in
the calorimeter is equal to
the energy that is released
by the reaction (but
opposite in sign).

qcal = Ccal ΔT

qrxn = −qcal

39
Figure 6.6

Examples: Constant-Volume Calorimetry

7. When 1.010 g of sucrose (C12H22O11) undergoes
combustion in a bomb calorimeter, the temperature
rises from 24.92°C to 28.33°C. Find ΔErxn for the
combustion of sucrose in kJ/mol sucrose. The heat
capacity of the bomb calorimeter (determined in a
separate experiment) is 4.90 kJ/°C. (You can
ignore the heat capacity of the small sample of
sucrose because it is negligible compared to the
heat capacity of the calorimeter) (Ex. 6.4)

Answer: -5660 kJ/mol C12H22O11

40
Chapter 6 Notes

Enthalpy

41

Energy Changes at Constant Pressure; Enthalpy

• Most reactions are not done in sealed containers:
they are carried out in open vessels at constant
pressure, with the volume capable of changing
freely, especially if the reactants or products of the
reaction involve gases.
• In these cases, ΔV ≠ 0, and the energy change may
be due to both heat transfer and PV work.
• In order to eliminate the contribution from PV work,
a quantity called enthalpy, H, is defined as internal
energy (E) plus the product of pressure and volume:
H = E + PV
• The change in enthalpy (ΔH) is:
ΔH = ΔE + PΔV
42
Chapter 6 Notes

Enthalpy; Heats of Reaction

• By doing a little algebra, we can see the relationship
between ΔH and energy:
ΔErxn = q + w ΔErxn = q - PΔV
ΔH = ΔE + PΔV
ΔH = q - PΔV + PΔV
ΔH = qP
• Therefore, the change in enthalpy equals the heat
evolved at constant pressure, qP.
• The enthalpy change, ΔH, is also called the heat of
reaction for the process. It is also a state function:
ΔH = Hfinal - Hinitial = Hproducts - Hreactants
43

Enthalpy vs. Energy

• While ΔE is a measure of the entire energy change
of a system (heat and work), ΔH is a measure of
only the heat exchanged at constant pressure.
• Most reactions do take place at constant (i.e.,
atmospheric) pressure, so ΔH is a good measure of
energy changes in most thermodynamic systems.
• In reactions that do not involve gases, volume
changes are approximately zero, and ΔH ≈ ΔE.
• When the number of moles of gas doesn’t change,
ΔV = 0, and ΔH = ΔE.
• Even in reactions in which the number of moles of
gas does change, qP is usually much larger than
PΔV, so ΔH ≈ ΔE.
44
Chapter 6 Notes

Examples: Enthalpy vs. Energy

8. The reaction of nitrogen with hydrogen to make
ammonia has ΔH° = -92.2 kJ
N2(g) + 3H2(g) → 2NH3(g); ΔH° = -92.2 kJ
What is the value of ΔE (in kJ) if the reaction is
carried out at a constant pressure of 40.0 atm and
the volume change is -1.12 L? (sim. to Conceptual
Connection 6.4)

Answer: -87.7 kJ
45

Exothermic vs. Endothermic Processes

• A chemical reaction can either release or absorb heat
energy:
– An endothermic process absorbs heat energy and
results in an increase in the enthalpy of the system
(the products have more enthalpy than the
reactants).
– An exothermic process releases heat energy and
results in a decrease in the enthalpy of the system
(the products have less enthalpy than the
reactants).
Hfinal < Hinitial ΔH < 0 exothermic
Hfinal > Hinitial ΔH > 0 endothermic

46
Chapter 6 Notes

Enthalpy Diagrams

Products Reactants
Enthalpy/
Energy

Reactants Products
Heat is absorbed Heat is released
endothermic exothermic
ΔH > 0 ΔH < 0

47

Where Does the Energy Come From?

• When an exothermic reaction occurs, the chemical
potential energy that used to be stored in the
chemical bonds in the reactants. The higher energy
bonds break and lower energy bonds form, and the
system goes from a higher potential energy to a
lower potential energy. The energy difference is
usually emitted in the form of heat or light.
• When an endothermic reaction occurs, the energy
that is absorbed by the system allows new bonds
with higher energies to be formed, and the potential
energy of the system is raised.

48
Chapter 6 Notes

Constant-Pressure Calorimetry: Measuring ΔH

• Energy changes at constant pressure are measured in
an insulated vessel with a stirrer, thermometer, and a
loose-fitting lid that keeps the contents at
atmospheric pressure. The data obtained allows us
to calculate ΔH. (In undergraduate labs, this device
is approximated by a coffee cup.)

qsoln = csoln msoln ΔT

qrxn = −qsoln

49
Figure 6.7

Examples: Constant-Pressure Calorimetry

9. A 25.64 g sample of a solid was heated in a test
tube to 100.00°C in boiling water and carefully
added to a coffee-cup calorimeter containing 50.00
g water. The water temperature increased from
25.10°C to 28.49°C. What is the specific heat
capacity of the solid? (Assume all the heat is
gained by the water.)

Answer: 0.387 J/g°C

50
Chapter 6 Notes

Examples: Constant-Pressure Calorimetry

10. Aqueous silver ion reacts with aqueous chloride
ion to yield a white precipitate of solid silver
chloride:
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
When 10.0 mL of 1.00 M AgNO3 solution is added
to 10.0 mL of 1.00 M NaCl solution at 25.0°C in a
calorimeter, a white precipitate of AgCl forms and
the temperature of the aqueous mixture increases
to 32.6°C. Assuming that the specific heat of the
aqueous mixture is 4.18 J/g°C, that the density of
the mixture is 1.00 g/mL, and that the calorimeter
itself absorbs a negligible amount of heat, calculate
ΔH (in kJ) for the reaction. (sim. to Ex. 6.7)
Answer: -64 kJ
51

Examples: Constant-Pressure Calorimetry

11. The reaction of hydrochloric acid and sodium
hydroxide is exothermic. The equation is
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
In one experiment, a student placed 50.0 mL of
1.00 M HCl at 25.50°C in a coffee cup calorimeter.
To this was added 50.0 mL of 1.00 M NaOH
solution also at 25.50°C. The mixture was stirred,
and the temperature quickly increased to a
maximum of 32.40°C. What is the energy evolved
in kilojoules per mole of HCl? (Because the
solutions are relatively dilute, we can assume that
their specific heats are close to that of water, 4.18 J
g-1 °C-1, and that their densities are 1.00 g mL-1.)
Answer: 57.8 kJ/mol
52
Chapter 6 Notes

Thermochemical Equations
• A thermochemical equation is a balanced equation
that also states the heat of reaction (ΔH).
• The reaction of 1 mole of N2 and 3 moles of H2 to
form 2 moles of NH3 releases 92.38 kJ of energy:
N2(g) + 3H2(g) → 2NH3(g); ΔH = -92.38 kJ
– This ΔH value is true only when the coefficients
are taken to mean the number of actual moles
they express for that particular reaction, with the
reagents in those particular physical states.
– For other amounts of reactants or products, the
energy change of the reaction can be calculated
by using the ΔH term in the same way that the
coefficients are used.
53

Examples: Thermochemical Equations

13. How much heat (in kJ) is evolved when 5.00 g of
aluminum reacts with a stoichiometric amount of
Fe2O3 in the thermite reaction? (WE 8.3)
2Al(s) + Fe2O3(s) → 2Fe(s) + Al2O3(s); ΔH° = -852 kJ

Answer: 78.8 kJ
54
MOV: Thermite
Chapter 6 Notes

Examples: Thermochemical Equations

14. If aluminum is produced by the thermal
decomposition of bauxite (mostly Al2O3), how
many grams of Al can form when 1.000 × 103 kJ
of heat is transferred?
Al2O3(s) → 2Al(s) + 3/2O2(g); ΔH = +1676 kJ

Answer: 32.20 g Al
55

56
Chapter 6 Notes

Relationships
Involving ΔHrxn

57

Manipulating Thermochemical Equations

• If a chemical equation is multiplied by some factor,
then ΔHrxn is multiplied by the same factor.
2H2(g) + O2(g) → 2H2O(g); ΔH = -483.6 kJ
4H2(g) + 2O2(g) → 4H2O(g); ΔH = -967.2 kJ
H2(g) + ½O2(g) → H2O(g); ΔH = -241.8 kJ
• If a chemical equation is reversed, the sign of ΔHrxn
is reversed. (This is equivalent to multiplying the
equation by -1.)
2H2O(g) → 2H2(g) + O2(g); ΔH = +483.6 kJ
H2O(g) → H2(g) + ½O2(g); ΔH = +241.8 kJ

58
Chapter 6 Notes

Examples: Thermochemical Equations

12. Given the following thermochemical equation
N2(g) + 3H2(g) → 2NH3(g); ΔHrxn = -92.38 kJ
What is the ΔHrxn for the reactions shown below?
a. 2NH3(g) → N2(g) + 3H2(g); ΔH =

b. 2N2(g) + 6H2(g) → 4NH3(g); ΔH =

c. 1/2N2(g) + 3/2H2(g) → NH3(g); ΔH =

d. 4NH3(g) → 2N2(g) + 6H2(g); ΔH =

e. 6NH3(g) → 3N2(g) + 9H2(g); ΔH =

f. 2NH3(aq) → N2(g) + 3H2(g); ΔH = 59

Two Paths to CO2

• We can imagine two paths leading from 1 mole of
carbon and oxygen (O2) to 1 mole of carbon dioxide:

One-Step Path:
C(s) + O2(g) → CO2(g); ΔH° = -393.5 kJ

Two-Step Path:
C(s) + 1/2O2(g) → CO(g); ΔH° = -110.5 kJ
CO(g) + 1/2O2(g) → CO2(g); ΔH° = -283.0 kJ

60
Chapter 6 Notes

Enthalpy Diagram for the Formation of CO2

C(s) + O2(g)

ΔH° = -110.5 kJ

ΔH° = -393.5 kJ CO(g) + 1/2O2(g)

ΔH° = -283.0 kJ
CO2(g)
ΔH
61

Hess’s Law
• Since ΔH is a state function, the path which leads
from the starting materials to the products should be
irrelevant to the overall energy change.
• This is generalized into Hess’s Law: if a reaction
can be expressed as the sum of a series of steps, then
ΔH for the overall reaction is the sum of the ΔH’s of
the individual steps.
A + B → C; ΔH = - 100 kJ
C → D; ΔH = + 30 kJ
A + B → D; ΔH = - 70 kJ
• We can use this property to determine the ΔH’s of
reactions which are difficult to measure directly, by
writing the reaction as the sum of reactions with
known ΔH’s. 62
Chapter 6 Notes

Examples: Hess’s Law

15. Calculate the value of ΔH° for the hypothetical
reaction
2A → 3D
Use the following equations to determine the value
of ΔH°. (sim. to Ex. 6.8)
A → B ΔH° = +10 kJ
3C → 2B ΔH° = -40 kJ
D → C ΔH° = -20 kJ

63

Examples: Hess’s Law

16. Hydrogen peroxide, H2O2, decomposes into water
and oxygen by the following equation.
H2O2(l) → H2O(l) + 1/2O2(g)
Use the following equations to determine the value
of ΔH° for the decomposition of hydrogen
peroxide. (sim. to example on p. 314)
H2(g) + O2(g) → H2O2(l); ΔH° = –188 kJ
H2(g) + 1/2O2(g) → H2O(l); ΔH° = –286 kJ

Answer: -98 kJ
64
Chapter 6 Notes

Examples: Hess’s Law

17. Carbon monoxide is often used in metallurgy to
remove oxygen from metal oxides and thereby
give the free metal. The thermochemical equation
for the reaction of CO with iron(III) oxide, Fe2O3,
is
Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g); ΔH°=-26.7 kJ
Use this equation and the equation for the
combustion of carbon monoxide,
CO(g) + 1/2O2(g) → CO2(g); ΔH° = –283.0 kJ
to calculate the value of ∆H° for the following
reaction.
2Fe(s) + 3/2O2(g) → Fe2O3(s)
Answer: -822.3 kJ 65

Examples: Hess’s Law

18. Use Hess’s law to calculate the value of ΔH° for the
reaction of tungsten with carbon:
W(s) + C(s) → WC(s)
Use the following thermochemical equations:
2W(s) + 3O2(g) → 2WO3(s); ΔH° = -1680.6 kJ
C(s) + O2(g) → CO2(g); ΔH° = -393.5 kJ
2WC(s) + 5O2(g) → 2WO3(s) + 2CO2(g); ΔH° = -2391.6 kJ

Answer: -38.0 kJ 66
Chapter 6 Notes

Thermodynamic Standard States

• The enthalpy change is the amount of heat released
or absorbed when reactants are converted to
products at the same temperature and in the molar
amounts represented by coefficients in the balanced
equation. The physical states must also be specified,
since a substance in the gas phase has a different
heat content from one in the liquid phase.
• In order to compare thermodynamic measurements
from different reactions, a set of conditions called
the thermodynamic standard state is defined: the
most stable form of a substance at 1 atm pressure
and 25°C, 1 M for all substances in solution.
• When ΔH is measured with all substances in their
standard states, it is called the standard enthalpy
(heat) of reaction, ΔH°.
67

Some Important Types of Enthalpy Change

• Heat of fusion (ΔHfus) — enthalpy change when 1
mole of a substance melts.
H2O(s) → H2O(l); ΔH = 6.01 kJ/mol at 0°C
• Heat of vaporization (ΔHvap) — enthalpy change
when 1 mole of a substance vaporizes.
H2O(l) → H2O(g); ΔH = 40.7 kJ/mol at 100°C
• Heat of sublimation (ΔHsubl) — enthalpy change
when 1 mole of a substance sublimes (converts
directly from the solid phase to the vapor phase).
• Heat of combustion (ΔHc) — enthalpy change
when 1 mole of a substance combines with O2 in a
combustion reaction.
C4H10(l) + 13/
2O2(g) → 4CO2(g) + 5H2O(l) 68
Chapter 6 Notes

Standard Enthalpy of Formation (ΔHf°)

• The standard enthalpy (heat) of formation, ΔHf°,
is the enthalpy change for the formation of 1 mole of
a substance in its standard state from its constituent
elements in their standard states.
• The most stable form of any element in its standard
state has ΔHf° = 0 kJ. This establishes a baseline
from which to calculate the ΔHf° for other
compounds.
• The elements must be in their standard states at
25°C. That is, elements which are diatomic must be
in the diatomic form; physical states must be
reasonable for that element at 25°C, etc.
• In most cases, ΔHf° for a compound is negative (i.e.,
a compound is usually more stable than its
elements.) 69

Standard Enthalpies of Formation

70
Appendix II-B on pages A-7 through A-12 lists thermodynamic properties of more substances.
Chapter 6 Notes

Determining ΔH° from ΔHf°

• The standard enthalpy of reaction can be calculated
by subtracting the sum of the heats of formation of
all reactants from the sum of the heats of formation
of all products, with each ΔHf° multiplied by the
appropriate coefficient in the balanced equation:

nr reactants → np products
o =
ΔH rxn ∑ n ΔH o (products) - ∑ n ΔH o (reactants)
p f r f

• This process is really an application of Hess’s Law.

• Thus, to calculate the ΔH° for any reaction, we write
the balanced equation, and look up the ΔHf°’s of all
of the reactants and products.
71

Examples: Standard Heats of Formation

19. Do the following reactions represent a ΔHf°
equation?

CO(g) + 1/2O2(g) → CO2(g); ΔH° = –283.0 kJ

2H(g) + O(g) → H2O(l); ΔH° = -971.1 kJ

2H2(g) + O2(g) → 2H2O(l); ΔH° = –571.8 kJ

H2(g) + 1/2O2(g) → H2O(l); ΔH° = –285.9 kJ

72
Chapter 6 Notes

Examples: Standard Heats of Formation

20. What equation must be used to represent the
formation of NaHCO3(s) when we want to include
its value of ΔHf°? (sim. to Ex. 6.9)

73

Examples: Standard Heats of Formation

21. Some chefs keep baking soda, NaHCO3, handy to
put out grease fires. When thrown on the fire,
baking soda partly smothers the fire and the heat
decomposes it to give CO2, which further smothers
the flame. The equation for the decomposition of
NaHCO3 is
2NaHCO3(s) → Na2CO3(s) + H2O(l) + CO2(g)
Use the data in Table 6.5 or Appendix II-B to
calculate the ΔH° for this reaction in kilojoules.
(sim. to Ex. 6.10)

Answer: 91.6 kJ
74
Chapter 6 Notes

Examples: Standard Heats of Formation

22. Use the data in Table 6.5 to calculate ΔH for the
combustion of ethanol, C2H5OH (l), at 25ºC.

Answer: -1234.8 kJ
75

Examples: Standard Heats of Formation

23. Use the data in Table 6.5 to calculate the standard
heat of vaporization of water.

Answer: +44.0 kJ
76
Chapter 6 Notes

Fuelin’ Around

77

Fuels
• Most common fuels (except for H2) are organic
compounds whose energy is ultimately derived from
the Sun through the conversion of CO2 and water
into glucose by the process of photosynthesis in
plants (and some bacteria).
• Coal, natural gas, and petroleum are collectively
known as fossil fuels, the remains of organisms
which have been decaying for millions of years.
– Coal, which is primarily of vegetable origin, is
mainly graphite-like carbon compounds, and can
be burned without much refinement.
– Petroleum is a viscous liquid mixture of
hydrocarbons primarily of marine origins.

78
Chapter 6 Notes

Petroleum Refining
• Petroleum is refined primarily by
distillation — the separation of a
complex mixture of compounds
by differences in boiling points:
– gasoline (30-200°C), C5-C11
– kerosene (175-300°C), C11-C14
– gas oil (275-400°C), C14-C25
– lubricating oils are high bp
compounds with a large
number of carbon atoms
– asphalt is the residual tar that
remains after the distillation
process

79

Fuel Consumption
• Most energy in the U.S. is derived from fossil fuels.

80