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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Chapter 5
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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Chapter 5
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:
1 Cal = 1000
cal = 1 kcal
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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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Chapter 5
The Nature of Energy
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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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Chapter 5
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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Chapter 5
The First Law of
Thermodynamics
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Relating E 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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Chapter 5
The First Law of
Thermodynamics
The First Law of
Thermodynamics
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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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Chapter 5
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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Chapter 5
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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Chapter 5
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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Chapter 5
Enthalpy
• Since we know that
w   PV
• We can write
H  E  PV
 qP  w
• When H, is positive, the system gains heat from the
surroundings.
• When H, is negative, the surroundings gain heat from
the system.
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Chapter 5
Enthalpy
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Chapter 5
Enthalpies of Reaction
• For a reaction:
H  H final  H initial
 H products  H reactants
• Enthalpy is an extensive property (magnitude H is
directly proportional to amount):
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)
H = -802 kJ
2CH4(g) + 4O2(g)  2CO2(g) + 4H2O(g) H = 1604 kJ
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Chapter 5
Enthalpies of Reaction
• When we reverse a reaction, we change the sign of H:
CO2(g) + 2H2O(g)  CH4(g) + 2O2(g)
H = +802 kJ
• Change in enthalpy depends on state:
H2O(g)  H2O(l) H = -88 kJ
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Chapter 5
Calorimetry
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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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Chapter 5
Calorimetry
Constant Pressure Calorimetry
• Atmospheric pressure is constant!
H  qP
qrxn  qsoln  specific heat of solution 
 grams of solution   T
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Chapter 5
Calorimetry
Constant Pressure Calorimetry
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Chapter 5
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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Chapter 5
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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Chapter 5
Hess’s Law
Note that:
H1 = H2 + H3
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Chapter 5
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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Chapter 5
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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Chapter 5
Enthalpies of Formation
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Chapter 5
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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Chapter 5
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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Chapter 5
Foods and Fuels
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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, H = -2816 kJ
• Fats break down as follows:
2C57H110O6 + 163O2  114CO2 + 110H2O, H = -75,520 kJ
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Chapter 5
Foods and Fuels
Foods
• Fats: contain more energy; are not water soluble, so are
good for energy storage.
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Chapter 5
Foods and Fuels
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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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Chapter 5
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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Chapter 5
End of Chapter 5:
Thermochemistry
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Chapter 5