Standard Enthalpies of

Formation
The standard enthalpy of formation of a
substance, denoted DH
f
o
, is the enthalpy
change for the formation of one mole of a
substance in its standard state from its
component elements in their standard
state.
Note that the standard enthalpy of formation for
a pure element in its standard state is zero.
Standard Enthalpies of
Formation
The law of summation of heats of
formation states that the enthalpy of a
reaction is equal to the total formation
energy of the products minus that of the
reactants.
S is the mathematical symbol meaning the
sum of, and m and n are the coefficients of the
substances in the chemical equation.
) reactants ( H m ) products ( H n H
o
f
o
f
o

D D D
A Problem to Consider
You record the values of DH
f
o
under the
formulas in the equation, multiplying them
by the coefficients in the equation.
- You can calculate DH
o
by subtracting the values
for the reactants from the values for the
products.
) 9 . 45 ( 4
) 0 ( 5 ) 3 . 90 ( 4 ) 8 . 241 ( 6
) g ( O H 6 ) g ( NO 4 ) g ( O 5 ) g ( NH 4
2 2 3

How is the heat of sublimation, DH
sub
, the enthalpy
change for the reaction:

H
2
O
(s)
H
2
O
(g)

related to DH
fis
and

DH
vap
?

Fuels
Food fills three needs of the body:
- It supplies substances for the growth and repair
of tissue.
- It supplies substances for the synthesis of
compounds used in the regulation of body
processes.
- It supplies energy. About 80% of the energy we
need is for heat. The rest is used for muscular
action and other body processes
Fuels
A typical carbohydrate food, glucose (C
6
H
12
O
6
)
undergoes combustion according to the following
equation.
) g ( O 6 ) s ( O H C
2 6 12 6
kJ -2803 H ); l ( O H 6 ) g ( CO 6
o
2 2
D
One gram of glucose yields 15.6 kJ (3.73 kcal)
when burned.
Fuels
A representative fat is glyceryl trimyristate,
C
45
H
86
O
6
. The equation for its combustion is:
) g ( O ) s ( O H C
2
2
127
6 86 45
kJ -27,820 H ); l ( O H 43 ) g ( CO 45
o
2 2
D
One gram of fat yields 38.5 kJ (9.20 kcal) when
burned. Note that fat contains more than twice the
fuel per gram than carbohydrates contain.
Figure 6.15:
Sources of
energy
consumed in
the United
States
(1996).
Fuels
Fossil fuels account for nearly 90% of the
energy usage in the United States.
Anthracite, or hard coal, the oldest variety of coal,
contains about 80% carbon.
Bituminous coal, a younger variety of coal,
contains 45% to 65% carbon.
Fuel values of coal are measured in BTUs (British
Thermal Units).
A typical value for coal is 13,200 BTU/lb.
1 BTU = 1054 kJ
Fuels
Natural gas and petroleum account for nearly
three-quarters of the fossil fuels consumed per year.
Purified natural gas is primarily methane, CH
4
, but
also contains small quantities of ethane, C
2
H
6
,
propane, C
3
H
8
, and butane, C
4
H
10
.
We would expect the fuel value of natural gas to be
close to that for the combustion of methane.
) g ( O H 2 ) g ( CO ) g ( O 2 ) g ( CH
2 2 2 4
kJ 802 H ;
o
D
Fuels
Petroleum is a very complicated mixture of
compounds.
Gasoline, obtained from petroleum, contains many
different hydrocarbons, one of which is octane,
C
8
H
18
.

) g ( O ) l ( H C
2
2
25
18 8
kJ -5,074 H ); g ( O H 9 ) g ( CO 8
o
2 2
D
This value of DH
o
is equivalent to 44.4 kJ/gram.

Fuels
With supplies of petroleum estimated to be 80%
depleted by the year 2030, the gasification of coal has
become a possible alternative.
First, coal is converted to carbon monoxide using
steam.

) g ( H ) g ( CO ) g ( O H ) s ( C
2 2

The carbon monoxide can then be used to produce
a variety of other fuels, such as methane.

) g ( O H ) g ( CH ) g ( H 3 ) g ( CO
2 4 2

Practice Problem 6.45
Practice Problem 6.46
States of Matter:
Liquids and
Solids
Chapter 11
Suggested Problems Chapter 11:

21, 23, 29, 34, 37, 39, 43, 45, 49, 51,

53, 55, 59, 61, 63, 67, 69, 71, 95, 97, 119
Online homework for Ch 5 and 6 due today

Exam Friday will cover Chapters 5 and 6 and
as much of 11 as we finish tomorrow.
Figure
11.1: Dry
ice.
Photo
courtesy of
American
Color.
States of Matter
Comparison of gases, liquids, and solids.
(see Figure 11.12)
Gases are compressible fluids. Their
molecules are widely separated.
Liquids are relatively incompressible fluids.
Their molecules are more tightly packed.
Solids are nearly incompressible and rigid.
Their molecules or ions are in close contact
and do not move.
Figure 11.2: Representation of
the states of matter.
Lattice energy
Changes of State
A change of state or phase transition is a
change of a substance from one state to
another. (see Table 11.1)
solid
liquid
gas
melting freezing
condensation boiling
sublimation
(see Figure 11.3)
condensation or
deposition
Figure
11.3:
A beaker
containing
iodine
crystals.
Photo
courtesy of
James
Scherer.
Figure 11.3:
Iodine has
appreciable
vapor
pressure
below its
melting
point.
Photo
courtesy of
James
Scherer.
Vapor Pressure
Liquids are continuously vaporizing.

If a liquid is in a closed vessel with space
above it, a partial pressure of the vapor state
builds up in this space.
The vapor pressure of a liquid is the partial
pressure of the vapor over the liquid,
measured at equilibrium at a given
temperature. (see Figure 11.4)
Figure 11.4:
Measurement
of the vapor
pressure of
water.
Figure 11.5: Distribution of kinetic energies
of molecules in a liquid.
Figure 11.6: Rates of vaporization and
condensation of a liquid over time.
Vapor Pressure
The vapor pressure of a liquid depends on
its temperature. (see Figure 11.7)
As the temperature increases, the kinetic
energy of the molecular motion becomes
greater, and vapor pressure increases.
Liquids and solids with relatively high vapor
pressures at normal temperatures are said to be
volatile.
Figure 11.7:
Variation of
vapor
pressure
with
temperature.
Boiling Point
The temperature at which the vapor pressure
of a liquid equals the pressure exerted on the
liquid is called the boiling point.
As the temperature of a liquid increases, the
vapor pressure increases until it reaches
atmospheric pressure.
At this point, stable bubbles of vapor form
within the liquid. This is called boiling.
The normal boiling point is the boiling point
at 1 atm.
Figure 11.8:
Boiling of a
liquid.
Freezing Point
The temperature at which a pure liquid
changes to a crystalline solid, or freezes, is
called the freezing point.
The melting point is identical to the freezing
point and is defined as the temperature at
which a solid becomes a liquid.
Unlike boiling points, melting points are
affected significantly by only large pressure
changes.

Heat of Phase Transition
To melt a pure substance at its melting
point requires an extra boost of energy to
overcome lattice energies.
The heat needed to melt 1 mol of a pure
substance is called the heat of fusion and
denoted DH
fus
.
kJ 01 . 6 H ); l ( O H ) s ( O H
fus 2 2
D
For ice, the heat of fusion is 6.01 kJ/mol.
Figure 11.9: Heating curve for water.
Heat of Phase Transition
To boil a pure substance at its melting
point requires an extra boost of energy to
overcome intermolecular forces.
The heat needed to boil 1 mol of a pure
substance is called the heat of vaporization and
denoted DH
vap
. (see Figure 11.9)
kJ 66 . 40 H ); g ( O H ) l ( O H
vap 2 2
D
For ice, the heat of vaporization is 40.66 kJ/mol.
A Problem to Consider
The heat of vaporization of ammonia is
23.4 kJ/mol. How much heat is required to
vaporize 1.00 kg of ammonia?
First, we must determine the number of moles of
ammonia in 1.00 kg (1000 g).
3
3
3
3
3
NH mol 8 . 58
NH g 0 . 17
NH mol 1
NH g 10 .00 1
A Problem to Consider
The heat of vaporization of ammonia is
23.4 kJ/mol. How much heat is required to
vaporize 1.00 kg of ammonia?
Then we can determine the heat required for
vaporization.
kJ 10 1.38 kJ/mol 23.4 NH mol 8 . 58
3
3

Figure 11.11: Phase
diagram for water
(not to scale).
Phase Diagrams
A phase diagram is a graphical way to
summarize the conditions under which the
different states of a substance are stable.
The diagram is divided into three areas
representing each state of the substance.
The curves separating each area represent the
boundaries of phase changes.
Phase Diagrams
Below is a typical phase diagram. It consists
of three curves that divide the diagram into
regions labeled solid, liquid, and gas.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
Phase Diagrams
Curve AB, dividing the solid region from the
liquid region, represents the conditions under
which the solid and liquid are in equilibrium.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
Phase Diagrams
Usually, the melting point is only slightly
affected by pressure. For this reason, the
melting point curve, AB, is nearly vertical.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
Phase Diagrams
Curve AC, which divides the liquid region
from the gaseous region, represents the boiling
points of the liquid for various pressures.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
Phase Diagrams
Curve AD, which divides the solid region from
the gaseous region, represents the vapor
pressures of the solid at various temperatures.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
Phase Diagrams
The curves intersect at A, the triple point,
which is the temperature and pressure where
three phases of a substance exist in equilibrium.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
Phase Diagrams
The temperature above which the liquid state of
a substance no longer exists regardless of
pressure is called the critical temperature.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
T
crit
Phase Diagrams
The vapor pressure at the critical temperature is
called the critical pressure. Note that curve AC
ends at the critical point, C.
B
temperature
p
r
e
s
s
u
r
e

A
C
D
solid liquid
gas
.
.
T
crit
P
crit
(see Figure 11.13)
Figure 11.13: Observing the critical
phenomenon.
Figure 11.12: Phase diagrams for carbon
dioxide and sulfur (not to scale).
Properties of Liquids; Surface
Tension and Viscosity
The molecular structure of a substance
defines the intermolecular forces holding
it together.
Many physical properties of substances are
attributed to their intermolecular forces.
These properties include vapor pressure and
boiling point.
Two additional properties shown in Table 11.3
are surface tension and viscosity.
Figure 11.18: A steel pin floating on the surface of water.
Figure 11.19: Liquid levels in capillaries.
Figure 11.20:
Comparison of the
viscosities of two
liquids. Photo courtesy of James Scherer.
Properties of Liquids; Surface
Tension and Viscosity
Surface tension is the energy required to
increase the surface area of a liquid by a
unit amount.
This explains why falling raindrops are nearly
spherical, minimizing surface area.
In comparisons of substances, as intermolecular
forces between molecules increase, the
apparent surface tension also increases.