Energy, Enthalpy, and

Thermochemistry
Lecture 6
郭修伯
 Contents
• 9.1 The Nature of energy
• 9.2 Enthalpy
• 9.3 Thermodynamics of Ideal Gases
• 9.4 Calorimetry
• 9.5 Hess’s Law
• 9.6 Standard Enthalpies of Formation
• 9.7 Present Sources of Energy
• 9.8 New Energy Sources
 The Nature of Energy
• Definition of Energy
– The capacity to do work or to produce heat
• The law of conservation of energy:
– Energy can be converted from one form to
another but can be neither created nor
destroyed.
• Energy classification:
– Potential energy
– Kinetic energy
 Potential Energy & Kinetic Energy
• Potential Energy:
– Energy due to position or composition
• Water behind a dam has potential energy
• The energy released when gasoline is burned
results from differences in the attractive forces
between nuclei and electrons in the reactants and
products.
• Kinetic energy:
– Due to the motion of the object and depends on the
mass of the object (m) and its velocity (v): 1 2
KE = mv
2
 Energy Transfer through…
• Work
– Defined as a force acting over a distance
• Heat
– Involves the transfer of energy between two objects
due to a temperature difference.
– NOT a substance contained in an object.
– Heat and temperature are decidedly different.
– Temperature is a property that reflects the random
motion of the particles in a particular substance. The
temperature of a monatomic ideal gas is an index of
the average random translational energy of the gas.
 A State Function (Property)
• refers to a property of the system that depends
only on its present state.
• does not depend in any way on the system’s
past (or future).
• the value of a state function does not depend on
how the system arrived at the present state
• Of the functions considered in our present
example, energy is a state function, but work
and heat are not state functions.
 Chemical Energy
• Exothermic reaction
– Exo- is a prefix meaning “out of”
– Energy flows out of the system.
• Endothermic reaction
– Reactions that absorb energy from the surroundings.
– When the heat flow is into a system, the process is
endothermic.
• Depends on the difference in potential energy
between the products and the reactants.
 Exothermic reaction
• Ex:

In any exothermic reaction, the potential energy stored in the chemical bonds
is being converted to the thermal energy (random kinetic energy) via heat.
 Endothermic reaction
• Ex:
 Chemical energy △(PE)
• Represents
– the change in potential energy stored in the
bonds of the products as compared with the
bonds of the reactants
– the difference between the energy required to
break the bonds in the reactants and the
energy released when the bonds in the
products are formed.
 △(PE)
• In an exothermic process
– the bonds in the products are stronger (on
average) than those of the reactants.
– i.e., more energy is released in forming the
new bonds in the products than is consumed
in breaking the bonds in the reactants.
• In an endothermic process
– The products have higher potential energy
(weaker bonds on average) than the reactants.
 Thermodynamics
• The study of energy and its interconversions
• The first law of thermodynamics:
– The energy of the universe is constant
– The internal energy of a system can be changed by a
flow of work, heat, or both:

• Where the internal energy (E) of a system can be defined

most precisely as the sum of the kinetic and potential
energies of all of the “particles” in the system
• The sign reflects the system’s point of view.
•The work accompanying a change in
volume of a gas is often called “PV work”.
•P in PΔV always refers to the external
pressure
 Example 9.1
• A balloon is inflated to its full extent by heating the air
inside it. In the final stages of this process the volume of
the balloon changes from 4.00 X 106 L to 4.50 X 106 L by
addition of 1.3 X 108 J of energy as heat. Assuming the
balloon expands against a constant pressure of 1.0 atm,
calculate △E for the process.
Solution:

P = 1.0 atm (the external pressure)

 Enthalpy
• Definition
– Since internal energy, pressure and volume
are all state functions, enthalpy is also a state
function.
• ΔH = q at constant pressure, where only
“PV” work is allowed:
 Change in enthalpy, ΔH
• At constant pressure (where only PV work is
allowed) the change in enthalpy (△H) of the
system is equal to the energy flow as heat.
• For reactions studied at constant pressure:
– The terms heat of reaction and change in enthalpy
are used interchangeably.

– At constant pressure exothermic reactions: ΔH < 0

– At constant pressure endothermic reactions: ΔH > 0
 Thermodynamics of Ideal Gases
• Assuming an ideal gas has no internal structure
(i.e., monatomic):
– The average, random, translational energy for 1 mole
of gas at a given temperature T: 3
( KE ) avg = RT
2
– Hence, the energy (“heat”) required to change the
energy of 1 mole of an ideal gas by ΔT is,
3
( KE ) avg = RΔT
2
 Molar Heat Capacity of a Substance

• Defined as the energy required to raise the

temperature of 1 mole of that substance by 1 K.
• Heating @ constant volume (i.e., rigid container)
– The energy that flows into the gas is used to increase
the translational energy of the gas molecules.
 Molar Heat Capacity of a Substance
• Heating @ constant pressure
– When an ideal gas is heated at constant pressure, its volume
increases and PV work occurs.
– Energy is supplied to both the translational energy of the gas
and to provide the work the gas does as it expands

= 3/2 R
per mole

ΔT = 1
5 PΔV = R
C P = CV + R = R
2
 Heating a Polyatomic Gas
• An ideal gas with monatomic molecule structure
– “Particles” that have no structure, Cv = 3/2 R
• An ideal gas with polyatomic molecule structure
– Polyatomic molecules absorb energy to excite
rotational and vibrational motions in addition to
translational motions (Note: any energy absorbed to
increase the vibrational and rotational energies does
not contribute directly to the translational kinetic
energy/temperature.)
– Cv >> 3/2 R
– Still, CP = CV +R
Molar Heat Capacities for Real Gases
 Heating a Gas: Energy Change
• The energy of an monatomic ideal gas can be changed
only by changing the temperature:
OR

When a gas is heated at constant volume, all the input energy (heat) goes
towards increasing E (no heat is needed to do work) .

When a gas is heated at constant pressure: the volume change and work occurs:

△E is nCv△T when an
ideal gas is heated
whether the process occurs
at constant volume or
constant pressure.
 Heating a Gas: Enthalpy Change
• By definition:
change in enthalpy

for ideal gas

ΔH = nCPΔT even though we have not assumed constant pressure (or volume)
 Ideal Gas Thermodynamic Properties

The only way to change H and E for an ideal gas is to change the temperature of
the gas. Thus, for any process involving an ideal gas at constant temperature,
ΔH = 0 and ΔE = 0.
 Example 9.2
• Consider 2.00 mol of a monatomic ideal gas that is taken
from state A (PA = 2.00 atm, VA = 10.0 L) to state B (PB =
1.00 atm, VB = 30.0 L) by two different pathways:

The PV diagram

Calculate q, w △E, and △H for both pathways

 • Step 1:
– expansion from 10.0 to 30.0 L at a constant pressure of 2.00 atm
– occur by heating the gas to produce some temperature change
△T (not specified in the given data).

△V = 30.0 L – 10.0 L

OR

w = − PΔV
 • Step 2:
– the gas pressure decreases from 2.00 atm to 1.00 atm at
constant volume.
– correspond to the cooling of the gas by a quantity △T

Cooling!

Since ΔV = 0; w2 = 0
• Step 3 :
• Step 4 :
 Summary
• Pathway one (steps 1 and 2):

• Pathway two (steps 3 and 4):

Work for two different pathways
• The work and heat are different for the two
pathways between states A and B
• Heat and work are both pathway-dependent.
 Calorimetry
• The science of measuring heat
• Based on observing the temperature change when a
body absorbs or discharges energy as heat
• Calorimeter:
– A device used to determine the heat associated with a chemical
reaction
• Heat capacity (C) of a substance:

– the specific heat capacity:

• per gram of substance; [J K－1g －1] or [J ºC－1 g －1].
– the molar heat capacity:
• per gram of substance; [J K－1mol －1] or [J ºC－1 mol －1].
 Example 9.3
• When 1.00 L of 1.00 M Ba(NO3)2 at 25.0ºC is
mixed with 1.00 L of 1.00 M Na2SO4 at 25ºC in a
calorimeter, the white solid BaSO4 forms and the
temperature of the mixture increases to 28.1ºC.
Assuming that the calorimeter absorbs only a
negligible quantity of heat, that the specific heat
capacity of the solution is 4.18 JºC－1g －1, and
that the density of the final solution is 1.0 g/mL,
calculate the enthalpy change per mole of
BaSO4 formed.
 Solution:
• The net ionic equation of the reaction
Ba 2 + (aq ) + SO42 − (aq ) → BaSO4 ( s )
• Temperature increases → exothermic → ΔH is negative

1.0 L of each solution is used,

total solution volume is 2.0 L

• 1.00 mol of solid BaSO4 is formed in this experiment. Thus the

enthalpy change per mole of BaSo4 formed is
ΔH = −2.6 × 10 4 J / mol = −26 kJ / mol
 Reactions involve volume change
• Ex:
– The volume change:
ΔV = V final − Vinitial
– The work:

– The internal energy

at constant pressure
 Example 9.4
• When 2.00 mol of SO2 (g) reacts completely with 1.00 mol of O2(g) to form
2.00 mol of SO3 (g) at 25ºC and a constant pressure of 1.00 atm, 198 kJ of
energy is released as heat. Calculate ΔH and Δ E for this process.
Solution:
• Constant pressure: ΔH = q P = −198kJ
• The internal energy:
Calorimetry experiments @ constant volume
• constant volume → no volume change → no work

• Bomb calorimeter:
– To study the energy
change in reactions under
conditions of constant
volume
– Weighed reactants are
placed inside the bomb and
ignited.
– The energy changed is
determined by measuring
the increase in the
temperature of the water
and other parts.
 Example 9.5
• It has been suggested that hydrogen gas obtained from
the decomposition of water might be a substitute for
natural gas (principally methane). To compare the
energies of combustion of these fuels, the following
experiment was carried out, using a bomb calorimeter
with a heat capacity of 11.3 kJ/ºC. When a 1.50-g sample
of methane gas was burned with excess oxygen in the
calorimeter, the temperature increased by 7.3ºC. When a
1.15-g sample of hydrogen gas was burned with excess
oxygen, the temperature increase was 14.3ºC. Calculate
the energy of combustion (per gram) for hydrogen and
methane.
Solution:

The energy released by the combustion of 1 g of hydrogen

is approximately 2.5 times that for 1 g of methane
 Hess’s Law
• In going from a particular set of reactants to a particular
set of products, the change in enthalpy is the same
whether the reaction takes place in one step or in a
series of steps.
• Ex: the oxidation of nitrogen to produce nitrogen dioxide

– can be carried out in two distinct steps:

– the sum of these two steps gives the net, or overall, reaction:
The principle of Hess’s law
 Characteristics of Enthalpy Changes

• Two characteristics of ΔH for a reaction:

– If a reaction is reversed, the sign of Δ H is
also reversed.
– The magnitude of Δ H is directly proportional
to the quantities of reactants and products in
a reaction. If the coefficients in a balanced
reaction are multiplied by an integer, the value
of Δ H is multiplied by the same integer (i.e.,
an extensive property)
 Example 9.6
• Diborane (B2H6) is a highly reactive boron hydride, which
was once considered as a possible rocket fuel for the
U.S. space program. Calculate ΔH for the synthesis of
diborane from its elements, according to the equation

• Using the following data:

Solution:
• This procedure can best be done by focusing on the
reactants and products of the required reaction:

Hydrogen?

Water ?
Standard Enthalpies of Formation ΔH o
f

• Not all the values ofΔH for the chemical

processes can be measured in a calorimeter.
– Calculate ΔH for chemical reactions and physical
changes by using standard enthalpies of formation
– The standard enthalpy of formation ( ΔH of ) of a
compound is defined as the change in enthalpy that
accompanies the formation of 1 mole of a compound
from its elements with all substances in their standard
states.
– The superscript zero on a thermodynamic function
indicates that the corresponding process has been
carried out under standard conditions.
 Standard State for a substance
• A precisely defined reference state:
– For a gas the standard state is a pressure of exactly 1 atm.
– For a substance present in a solution, the standard state is
a concentration of exactly 1 M at an applied pressure of 1
atm.
– For a pure substance in a condensed state (liquid or solid),
the standard state is the pure liquid or solid.
– For an element the standard state is the form in which the
element exists (is most stable) under conditions of 1 atm
and the temperature of interest (usually 25ºC).

* The International Union of Pure and Applied Chemistry (IUPAC) has

adopted 1 bar (100,000 Pa) as the standard pressure instead of 1 atm
(101,325 Pa). Both standards are now widely used.
 Standard Enthalpies of Formation
• Ex:

per mole of product with the

product in its standard state !!
 The change in enthalpy for the
overall reaction
• The enthalpy change for a given reaction can be
calculated by subtracting the enthalpies of
formation of the reactants from the enthalpies of
formation of the products:

– Elements are not included in the calculation since

elements require no change in form.
– We have in effect defined the enthalpy of formation of
an element in its standard state as zero.
 Key Concepts for Doing Enthalpy Calculations

• When a reaction is reversed, the magnitude of ΔH

remains the same, but the sign changes.
• When the balanced equation for a reaction is multiplied
by an integer, the value of Δ H for that reaction must be
multiplied by the same integer.
• The change in enthalpy for a given reaction can be
calculated from the enthalpies of formation of the
reactants and products:

• Elements in their standard states are not included in the

Δ Hreaction calculations. That is, △Hf° for an element in its
standard state is zero.
 Example 9.7
• Using the standard enthalpies of formation
listed in Table 9.4, calculate the standard
enthalpy change for the overall reaction
that occurs when ammonia is burned in air
to form nitrogen dioxide and water. This is
the first step in the manufacture of nitric
acid.
4 NH 3 ( g ) + 7O2 ( g ) → 4 NO2 ( g ) + 6 H 2 O (l )
Solution:
– The pathways:
Solution:
– Step (a): Decomposition of NH3(g) into elements

• Since

– Step (b): O2(g) is an element in its standard state:

ΔH (ob ) = 0
– Step (c): Synthesis of 4 mol of NO2 (g) from the elements:

• Thus,

– Step (d): Synthesis of 6 mol of H2O(l) from the elements:

• Thus,
• To summarize:
 Example 9.8
• Methanol (CH3OH) is sometimes used as
a fuel in high-performance engines. Using
the data in Table 9.4, compare the
standard enthalpy of combustion per gram
of methanol with that of gasoline. Gasoline
is actually a mixture of compounds, but
assume for this problem that gasoline is
pure liquid octane (C8H18).
 • The combustion of methanol

For 2 mol (or 64 g) of methanol

• The combustion of octane

For 2 mol (or 228.4 g) of octane

The enthalpy of combustion per gram of octane is

about twice that per gram of methanol !!
 Present Sources of Energy
• By the process of photosynthesis, plants store energy that can be
claimed by burning the plants themselves or the decay products that
have been converted to fossil fuels

Energy sources used in the United States

 Petroleum and Natural Gas
• Petroleum:
– a thick, dark liquid composed mostly of compounds
called hydrocarbons that contain carbon and
hydrogen. Most likely formed from the remains of
marine organisms that lived c.a. 500 million years ago.
– It consists mostly of hydrocarbons having chains that
contain from 5 to more than 25 carbons.
• Natural gas:
– usually associated with petroleum deposits, consists
mostly of methane but also contains significant
amounts of ethane, propane, and butane.
Hydrocarbons
 Coal
• From the remains of plants that were buried and subjected
to pressure and heat over long periods of time
• Coal “matures” through four stages: lignite, subbituminous,
bituminous, and anthracite. Each stage has a higher carbon-
to-oxygen and carbon-to-hydrogen ratio.

least valuable

most valuable
 Effects of Carbon Dioxide on Climate

• Radiant energy from the sun:

– ~ 30% is reflected into space by the atmosphere
– Some is absorbed by plants to drive photosynthesis
and by the ocean to evaporate water
– MOST is absorbed by soil, rock and water, resulting
an increase in the temperature of the earth’s surface.
(In turn radiated from the heated surface mainly as
infrared radiation (often called heat radiation))
• Molecules in the atmosphere, principally H2O
and CO2, strongly absorb infrared radiation,
trapping it in the earth’s atmosphere
 Greenhouse Effect
• H2O
– The atmosphere’s water content is controlled by the
water cycle (evaporation and precipitation) and the
average content remains constant over the years.
• CO2
– The increase of the CO2 concentration was 16% from
1880 to 1980.
– Some projections indicate that the CO2 concentration
may be double in the 21 century what it was in 1880.
The earth’s average temperature could increase by
3ºC.
FIGURE 9.14
The earth’s atmosphere is
transparent to visible light from the
sun. This visible light strikes the
earth, and part of it is changed to
infrared radiation. The infrared
radiation from the earth’s surface is
strongly absorbed by CO2, H2O,
and other molecules present in
smaller amounts (for example, CH4
and N2O) in the atmosphere. In
effect, the atmosphere traps some
of the energy, acting like the glass
in a greenhouse and keeping the
earth warmer than it would
otherwise be.
Diagram of Storage of CO2
 New Energy Sources
• Should consider economic, climatic and
supply factors.
• Several potential energy sources:
– The sun (solar)
– Nuclear processes (fission and fusion)
– Biomass (plants)
– Synthetic fuels
– Others
 Coal conversion
• Transportation costs for solid coal are high,
more energy-efficient fuels are being developed
→ gaseous fuel → convert coal from a solid to a
gas requires reducing the size of the molecules
• Coal gasification:
– A process which breaks down the coal structure.
– Many of the carbon-carbon bonds are replaced by
carbon-hydrogen and carbon-oxygen bonds as the
coal fragments react with the water and oxygen.
– The product consists of synthetic gas, or syngas (a
mixture of carbon monoixde and hydrogen) and
methane gas.
Coal Gasification
 Coal…
• In the gasification process:

exothermic

endothermic

• Methanol formation

– can be used in the production of synthetic fibers, plastics and gasoline

• Coal slurry
– Pulverized coal mixed with water
– Might replace solid coal and residual oil (a heavy oil from petroleum
accounting for 13% of U.S. petroleum imports.)
 Hydrogen as a Fuel
• The heat of combustion of H2(g) per gram is
about 2.5 times that of natural gas:

• Only water as the product

• Three main problems:
– The costs of production
– Storage and transport
• On metal surface, H2 decomposes to atoms, migrates into
the metal, causing structural changes that make its brittle
• Relative small amount of energy that is available per unit
volume of hydrogen (1/3 of methane)
 Hydrogen
• Current production:

– Highly endothermic; treating methane with steam is

not an efficient way
• Water splitting:

– requires 286 kJ per mole of liquid water; not

economically feasible. Other methods?
 Hydrogen from water
• Electrolysis of water
– Still too expensive
• Thermal decomposition of water

• Biological decomposition of water Lower temp?

– Only small-scale currently

 Other Energy Alternatives
• Oil shale
– Not fluid and cannot be pumped out
– Heating to 250ºC (expensive) and large quantities of
waste rock (environmental impact)
• Ethanol
– Mostly from corn fermentation process
– E85 gasohol (85% ethanol + 15% gasoline)
• Biodiesel
– Energy efficient: a 93% net energy gain (Note, the net
energy gain for ethanol is only about 25%)