Lecture Presentation

Chapter 5

Thermochemistry

James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education, Inc.
 Energy
• Energy is the ability to do work or
transfer heat.
– Energy used to cause an object that has mass
to move is called work.
– Energy used to cause the temperature of an
object to rise is called heat.
• This chapter is about thermodynamics,
which is the study of energy
transformations, and thermochemistry,
which applies the field to chemical
reactions, specifically.
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 Kinetic Energy
Kinetic energy is energy an object
possesses by virtue of its motion:

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 Potential Energy
• Potential energy is
energy an object
possesses by virtue of
its position or chemical
composition.
• The most important
form of potential energy
in molecules is
electrostatic potential
energy, Eel:

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 Units of Energy
• The SI unit of energy is the joule (J):

• An older, non-SI unit is still in

widespread use, the calorie (cal):
1 cal = 4.184 J
(Note: this is not the same as the calorie
of foods; the food calorie is 1 kcal!)
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 Definitions: System and Surroundings

• The system includes the

molecules we want to
study (here, the hydrogen
and oxygen molecules).
• The surroundings are
everything else (here, the
cylinder and piston).

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 Definitions: Work
• Energy used to move
an object over some
distance is work:
• w=Fd
where w is work, F
is the force, and d is
the distance over
which the force is
exerted.

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 Heat

• Energy can also be

transferred as heat.
• Heat flows from
warmer objects to
cooler objects.

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 Conversion of Energy
• Energy can be converted from one type to another.
• The cyclist has potential energy as she sits on top of
the hill.
• As she coasts down the hill, her potential energy is
converted to kinetic energy until the bottom, where
the energy is converted to kinetic energy.

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 First Law of Thermodynamics
• Energy is neither created nor
destroyed.
• In other words, the total energy of the
universe is a constant; if the system
loses energy, it must be gained by the
surroundings, and vice versa.

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 Internal Energy
The internal energy of a system is the sum of all
kinetic and potential energies of all components
of the system; we call it E.

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 Internal Energy
By definition, the change in internal energy, E,
is the final energy of the system minus the initial
energy of the system:

E = Efinal − Einitial

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 Changes in Internal Energy

• When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
• That is, E = q + w.

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 E, q, w, and Their Signs

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 Exchange of Heat between System and
Surroundings
• When heat is absorbed by the system from the
surroundings, the process is endothermic.

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 EXERCISE

Pr. Ex. 5.2) Calculate the change in the internal energy for a
process in which a system absorbs 140 J of heat from the
surroundings and does 85 J of work on the surroundings.

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 Exchange of Heat between System and
Surroundings
• When heat is released by the system into the
surroundings, the process is exothermic.

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 State Functions
• Usually we have no way of knowing the internal
energy of a system; finding that value is simply too
complex a problem.
• However, we do know that the internal energy of a
system is independent of the path by which the
system achieved that state.
– In the system below, the water could have reached room
temperature from either direction.

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 State Functions
• Therefore, internal energy is a state function.
• It depends only on the present state of the
system, not on the path by which the system
arrived at that state.
• And so, E depends only on Einitial and Efinal.

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 State Functions
• However, q and w are
not state functions.
• Whether the battery is
shorted out or is
discharged by running
the fan, its E is the
same.
– But q and w are different
in the two cases.

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 Work

Usually in an open
container the only work
done is by a gas
pushing on the
surroundings (or by
the surroundings
pushing on the gas).

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 Work
We can measure the work done by the gas if
the reaction is done in a vessel that has been
fitted with a piston:
w = −PV

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 EXERCISE

Pr. Ex. 5.3/2) Calculate the work, in J, if the volume of a system

contracts from 1.55 to 0.85 L at a constant pressure of 0.985
atm.

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 Enthalpy
• If a process takes place at constant
pressure (as the majority of processes we
study do) and the only work done is this
pressure–volume work, we can account for
heat flow during the process by measuring
the enthalpy of the system.

• Enthalpy is a state function.

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 E = q + w
w = -P V
E = q - P V
At constant volume V = 0, so w = 0
E = q (at constant volume)
At constant pressure E = q - P V
Rearranged: E + P V = q
Defined: H = E + PV H: enthalpy
H = q (at constant pressure)
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 EXERCISE

Problem 5.35) Assume that the following reaction occurs at

constant pressure:

2Al(s) + 3Cl2(g)  2AlCl3(s)

If you are given H for the reaction, what additional

information do you need to determine E for the process?
Which quantity is larger for this reaction? Explain your
answer.

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 Endothermic and Exothermic

• A process is
endothermic
when H is
positive.
• A process is
exothermic when
H is negative.

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 Enthalpy of Reaction

The change in
enthalpy, H, is the
enthalpy of the
products minus the
enthalpy of the
reactants:

H = Hproducts − Hreactants

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 Enthalpy of Reaction
This quantity, H, is called the enthalpy of
reaction, or the heat of reaction.

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 The Truth about Enthalpy

1. Enthalpy is an extensive property.

2. H for a reaction in the forward
direction is equal in size, but opposite
in sign, to H for the reverse reaction.
3. H for a reaction depends on the state
of the products and the state of the
reactants.

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 EXERCISE

Pr. Ex. 5.5/2) Hydrogen peroxide can decompose to water

and oxygen by the reaction

2H2O2(l)  2H2O(l) + O2(g) H = -196 kJ

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 Heat Capacity and Specific Heat
The amount of energy required to raise the
temperature of a substance by 1 K (1 C) is its
heat capacity, usually given for one mole of the
substance.

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 Heat Capacity and Specific Heat

We define specific
heat capacity (or
simply specific heat)
as the amount of
energy required to
raise the temperature
of 1 g of a substance
by 1 K (or 1 C).

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 Heat Capacity and Specific Heat

• Specific heat, then, is

q = m x Cs x T or
Q = m x Cs x T

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 EXERCISE

Pr. Ex. 5.6/2) (a) Large beds of rocks are used in some solar-
heated homes to store heat. Assume that the specific heat of
the rocks is 0.82 J/gC. Calculate the quantity of heat
absorbed by 50.0 kg of rocks if their temperature increases
by 12.0 C.
(b) What temperature change would these rocks undergo if
they emitted 450 kJ of heat?

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 Calorimetry
• Since we cannot know
the exact enthalpy of the
reactants and products,
we measure H through
calorimetry, the
measurement of
heat flow.
• The instrument used to
measure heat flow is
called a calorimeter.
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 Constant Pressure Calorimetry
(coffee – cup calorimetry)
• By carrying out a reaction in
aqueous solution in a simple
calorimeter, the heat change for
the system can be found by
measuring the temperature
change for the water in the
calorimeter.
• qcal = (m  Cs  T)water
• qreaction = - qcal
(qreaction = H reaction)
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 EXERCISE

Ex: When 100.0 mL of 1.020 M HCl(aq) and 50.0 mL 1.988M

NaOH are mixed in a constant pressure calorimeter (coffee
cup calorimeter), the temperature of the mixture increases
from 24.5C to 33.4C. The temperature increase is caused by
the following reaction:

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

Calculate H for this reaction in kJ/mol NaCl. Assume that the

volume and the density of the solution is same as
water.Specific heat of water is 4.18 J/gC.

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 Thermochemistry

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 Bomb Calorimetry
• Reactions can be carried
out in a sealed “bomb”
such as this one.
• The heat absorbed (or
released) by the water is
a very good approximation
of the enthalpy change for
the reaction.
• qcal = Ccal × ∆T
• qreaction = - qcal
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 Bomb Calorimetry
• Because the volume
in the bomb
calorimeter is
constant, what is
measured is really the
change in internal
energy, E, not H.
• For most reactions,
the difference is very
small.
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 Hess’s Law

• H is well known for many reactions,

and it is inconvenient to measure H
for every reaction in which we are
interested.
• However, we can estimate H using
published H values and the
properties of enthalpy.

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 EXERCISE

Prac. Ex. 5.8/2) A 0.5865 g sample of lactic acid (HC3H5O3) is

burned in a bomb calorimeter whose heat capacity is 4.812
kJ/C. The temperature increases from 23.10C to 24.95 C.
Calculate the heat of combustion of lactic acid (a) per gram
and (b) per mole.

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 Hess’s Law
• Hess’s law: If a reaction is
carried out in a series of
steps, H for the overall
reaction will be equal to the
sum of the enthalpy changes
for the individual steps.
• Because H is a state
function, the total enthalpy
change depends only on the
initial state (reactants) and the
final state (products) of the
reaction.
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 EXERCISE

Pr. Ex. 5.10/2) Calculate H for the reaction:

NO(g) + O(g)  NO2(g)
Given the following information:
NO(g) + O3(g)  NO2(g) + O2 H = -198.9 kJ
O3(g)  3/2O2(g) H = -142.3 kJ
O2(g)  2O(g) H = 495.0 kJ

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 Enthalpies of Formation

An enthalpy of formation, Hf, is

defined as the enthalpy change for the
reaction in which a compound is made
from its constituent elements in their
elemental forms.

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 Standard Enthalpies of Formation
Standard enthalpies of formation, ∆Hf°, are
measured under standard conditions (25 ºC
and 1.00 atm pressure).

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 EXERCISE

Problem 5.69) For each of the following compounds, write

a balanced thermochemical equation depicting the
formation of one mole of the compound from its elements
in their standard states:

(a) NO2(g) (b) SO3(g) (c) NaBr(s) d) Pb(NO3)2(s)

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 Calculation of H using Hess Law
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)

• Imagine this as occurring

in three steps:

1) Decomposition of propane to
the elements:
C3H8(g)  3 C(graphite) + 4 H2(g)

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 C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)

• Imagine this as occurring

in three steps:

2) Formation of CO2:
3 C(graphite) + 3 O2(g) 3 CO2(g)

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 C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)

• Imagine this as occurring

in three steps:

3) Formation of H2O:
4 H2(g) + 2 O2(g)  4 H2O(l)

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 C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)

• So, all steps look like this:

C3H8(g)  3 C(graphite) + 4 H2(g)

3 C(graphite) + 3 O2(g) 3 CO2(g)
4 H2(g) + 2 O2(g)  4 H2O(l)

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 C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)

• The sum of these

equations is the overall
equation!
C3H8(g)  3 C(graphite) + 4 H2(g)
3 C(graphite) + 3 O2(g) 3 CO2(g)
4 H2(g) + 2 O2(g)  4 H2O(l)
C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Thermochemistry

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 Calculation of H

We can use Hess’s law in this way:

H = nHf,products – mHf°,reactants

where n and m are the stoichiometric

coefficients.

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 Calculation of H using Values from the
Standard Enthalpy Table
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)

H = [3(−393.5 kJ) + 4(−285.8 kJ)] – [1(−103.85 kJ) + 5(0

kJ)]
= [(−1180.5 kJ) + (−1143.2 kJ)] – [(−103.85 kJ) + (0 kJ)]
= (−2323.7 kJ) – (−103.85 kJ) = −2219.9 kJ

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 EXERCISE

Pr. Ex. 5.12/1) Calculate the enthalpy change for the reaction
2H2O2(l)  2H2O(l) + O2(g)
using enthalpies of formation:
∆Hf°[H2O2(l)] = -187.8 kJ/mol ∆Hf°[H2O(l)] = -285.8 kJ/mol

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 Energy in Foods
Most of the fuel in the food we eat comes
from carbohydrates and fats.

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 Energy in Fuels

The vast majority of the

energy consumed in
this country comes from
fossil fuels.
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Other Energy Sources
• Nuclear fission
produces 8.5% of the
U.S. energy needs.
• Renewable energy
sources, like solar,
wind, geothermal,
hydroelectric, and
biomass sources
produce 7.4% of the
U.S. energy needs.
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 END OF THE CHAPTER EXERCISES:

Chapter 5: 7, 13, 25, 29, 31, 32, 35, 36, 37, 41, 43, 45, 46,
51, 53a, 55, 56, 57, 58, 63, 67, 69, 70, 97

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