Thermodynamics and Equilibria

CHAPTER 4

The Nature of Energy

Energy

capacity to do work or to
transfer heat
Work energy used to cause an object

with mass to move against a force

Heat energy used to cause
temperature of an object to increase

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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, Eel - the
attraction between two oppositely charged
particles, Q1 and Q2, a distance d apart:
Q1Q2
Eel

constant = 8.99 109 J-m/C2.

If the two particles are of opposite charge,
then Eel is the electrostatic repulsion
between them.
The

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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/s2 1 J
Widely

use, non-SI unit - 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. Surrounding
Surrounding

System
Surrounding

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Chapter 5

Surrounding

The Nature of Energy

Systems
Open system: matter and
energy can be exchanged
with the surroundings matter

System

energy

Closed system :
exchange energy but not
matter with its
surroundings

System

energy

Isolated system: neither

energy nor matter can be
exchanged with the
surroundings.

System

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Chapter 5

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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Chapter 5

The First Law of

Thermodynamics
Energy can be neither created nor
destroyed energy is conserved

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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. U U U
final
initial
Change in internal
energy,

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Chapter 5

The First Law of

Thermodynamics
Relating U 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
Thermodynami
cs

The First Law of

Thermodynamics
Exothermic and
Endothermic
Processes
Endothermic:
absorbs heat from
the surroundings
cold
Exothermic:
transfers heat to
the surroundings
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 PV
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Chapter 5

Enthalpy

Prentice Hall 2003

Chapter 5

Enthalpy

Enthalpy, H: Heat transferred

between the system and
surroundings carried out under
constant pressure.
H U PV

Enthalpy is a state function.

If the process occurs at constant
H U PV
pressure,

U PV

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Chapter 5

Enthalpy

Since we know that

w PV , U q w

We can writeH U PV

q P w w q p

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

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Chapter 5

Enthalpies of Reaction
1.

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

2.

When we reverse a reaction, we change the

sign of H:
CO2(g) + 2H2O(g) CH4(g) + 2O2(g)

3.

H = +802 kJ

Change in enthalpy depends on state:

H2O(g) H2O(l)

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Chapter 5

H = -88 kJ

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
C s m T
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Chapter 5

Calorimetry

H q p

qrxn qsoln
specific heat
of solution
Constant
Pressure
grams
of solution T
Calorimetry

Atmospheric pressure
is constant!
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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

Hesss Law

Hesss 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

Hesss Law
Note
that:
H1 =
H2 +
H3

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Chapter 5

Enthalpies of Formation
of formation, Hf : enthalpy
change from a formation of a compound
from its constituent.
Standard conditions (standard state): 1 atm
and 25 oC (298 K).
Standard enthalpy, H: 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.
Enthalpy

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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

Write as the sum of 3 formation reactions:

For each reactions, check table 5.3 for value H

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Chapter 5

Enthalpies of Formation
Using Enthalpies of Formation of
Calculate Enthalpies of Reaction
For

a reaction

H rxn nH f products mH f reactants

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Chapter 5

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, 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

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