CHEMISTRY

The Central Science

9th Edition

Chapter 5
Thermochemistry

David P. White
Prentice Hall © 2003 Chapter 5
 The Nature of Energy
Kinetic Energy and Potential Energy
• Kinetic energy is the energy of motion:

1 2
Ek  mv
2
• Potential energy is the energy an object possesses by
virtue of its position.
• Potential energy can be converted into kinetic energy.
Example: a bicyclist at the top of a hill.

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 The Nature of Energy
Kinetic Energy and Potential Energy
• Electrostatic potential energy, Ed, is the attraction
between two oppositely charged particles, Q1 and Q2, a
distance d apart:
Q1Q2
Ed 
d
• The constant  = 8.99  109 J-m/C2.
• If the two particles are of opposite charge, then Ed is the
electrostatic repulsion between them.
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 The Nature of Energy
Units of Energy
• SI Unit for energy is the joule, J:

1 2 1
Ek  mv   2 kg 1 m/s  2
2 2
 1 kg - m/s 2  1 J

We sometimes use the calorie instead of the joule:

1 cal = 4.184 J (exactly)
A nutritional Calorie:
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1 Cal = 1000 cal = 1 kcal
Chapter 5
 The Nature of Energy
Systems and Surroundings
• System: part of the universe we are interested in.
• Surroundings: the rest of the universe.

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 The Nature of Energy
Transferring Energy: Work and Heat
• Force is a push or pull on an object.
• Work is the product of force applied to an object over a
distance:
w  F d
• Energy is the work done to move an object against a
force.
• Heat is the transfer of energy between two objects.
• Energy is the capacity to do work or transfer heat.

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 The First Law of
Thermodynamics
Internal Energy
• Internal Energy: total energy of a system.
• Cannot measure absolute internal energy.
• Change in internal energy,
E  Efinal  Einitial

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 The First Law of
Thermodynamics
Relating DE to Heat and Work
• Energy cannot be created or destroyed.
• Energy of (system + surroundings) is constant.
• Any energy transferred from a system must be transferred
to the surroundings (and vice versa).
• From the first law of thermodynamics:
when a system undergoes a physical or chemical change, the
change in internal energy is given by the heat added to or
absorbed by the system plus the work done on or by the
system:
E  q  w
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The First Law of
Thermodynamics
 The First Law of
Thermodynamics
Exothermic and Endothermic Processes
• Endothermic: absorbs heat from the surroundings.
• Exothermic: transfers heat to the surroundings.
• An endothermic reaction feels cold.
• An exothermic reaction feels hot.

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 The First Law of
Thermodynamics
State Functions
• State function: depends only on the initial and final states
of system, not on how the internal energy is used.

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State Functions
 Enthalpy

• Chemical reactions can absorb or release heat.

• However, they also have the ability to do work.
• For example, when a gas is produced, then the gas
produced can be used to push a piston, thus doing work.
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
• The work performed by the above reaction is called
pressure-volume work.
• When the pressure is constant,
w   PV
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Enthalpy
 Enthalpy

• Enthalpy, H: Heat transferred between the system and

surroundings carried out under constant pressure.
H  E  PV
• Enthalpy is a state function.
• If the process occurs at constant pressure,
H   E  PV 
 E  PV

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 Enthalpy

• Since we know that

w   PV
• We can write
H  E  PV
 qP  w
• When DH, is positive, the system gains heat from the
surroundings.
• When DH, is negative, the surroundings gain heat from
the system.
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 Enthalpy

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 Enthalpies of Reaction

• For a reaction:
H  H final  H initial
 H products  H reactants
• Enthalpy is an extensive property (magnitude DH is
directly proportional to amount):
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) DH = -802 kJ
2CH4(g) + 4O2(g)  2CO2(g) + 4H2O(g) DH = - 1604 kJ

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 Enthalpies of Reaction

• When we reverse a reaction, we change the sign of DH:

CO2(g) + 2H2O(g)  CH4(g) + 2O2(g) DH = +802 kJ
• Change in enthalpy depends on state:
H2O(g)  H2O(l) DH = -88 kJ

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 Calorimetry
Heat Capacity and Specific Heat
• Calorimetry = measurement of heat flow.
• Calorimeter = apparatus that measures heat flow.
• Heat capacity = the amount of energy required to raise
the temperature of an object (by one degree).
• Molar heat capacity = heat capacity of 1 mol of a
substance.
• Specific heat = specific heat capacity = heat capacity of 1
g of a substance.
q   specific heat    grams of substance   T
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 Calorimetry
Constant Pressure Calorimetry
• Atmospheric pressure is constant!
H  qP
qrxn  qsoln   specific heat of solution 
  grams of solution   T

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 Calorimetry
Constant Pressure Calorimetry

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 Calorimetry
Bomb Calorimetry (Constant Volume
Calorimetry)

• Reaction carried out under

constant volume.
• Use a bomb calorimeter.
• Usually study combustion.

qrxn  Ccal  T

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 Hess’s Law

• Hess’s law: if a reaction is carried out in a number of

steps, H for the overall reaction is the sum of H for
each individual step.
• For example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H = -802 kJ
2H2O(g)  2H2O(l) H = -88 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) H = -890 kJ

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 Hess’s Law

Note that:
H1 = H2 + H3

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 Enthalpies of Formation

• If 1 mol of compound is formed from its constituent

elements, then the enthalpy change for the reaction is
called the enthalpy of formation, Hof .
• Standard conditions (standard state): 1 atm and 25 oC
(298 K).
• Standard enthalpy, Ho, is the enthalpy measured when
everything is in its standard state.
• Standard enthalpy of formation: 1 mol of compound is
formed from substances in their standard states.
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 Enthalpies of Formation

• If there is more than one state for a substance under

standard conditions, the more stable one is used.
• Standard enthalpy of formation of the most stable form of
an element is zero.

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 Enthalpies of Formation

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 Enthalpies of Formation
Using Enthalpies of Formation of Calculate
Enthalpies of Reaction
• We use Hess’ Law to calculate enthalpies of a reaction
from enthalpies of formation.

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 Enthalpies of Formation
Using Enthalpies of Formation of Calculate
Enthalpies of Reaction
• For a reaction
H rxn   nH f  products    mH f  reactants 

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 Foods and Fuels
Foods
• Fuel value = energy released when 1 g of substance is
burned.
• 1 nutritional Calorie, 1 Cal = 1000 cal = 1 kcal.
• Energy in our bodies comes from carbohydrates and fats
(mostly).
• Intestines: carbohydrates converted into glucose:
C6H12O6 + 6O2  6CO2 + 6H2O, DH = -2816 kJ
• Fats break down as follows:
2C57H110O6 + 163O2  114CO2 + 110H2O, DH = -75,520 kJ

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 Foods and Fuels

Foods
• Fats: contain more energy; are not water soluble, so are
good for energy storage.

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 Foods and Fuels
Fuels
• In 2000 the United States consumed 1.03  1017 kJ of
fuel.
• Most from petroleum and natural gas.
• Remainder from coal, nuclear, and hydroelectric.
• Fossil fuels are not renewable.

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Foods and
Fuels

Prentice Hall © 2003 Chapter 5

 Foods and Fuels
Fuels
• Fuel value = energy released when 1 g of substance is
burned.
• Hydrogen has great potential as a fuel with a fuel value
of 142 kJ/g.

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 End of Chapter 5:
Thermochemistry

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