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Thermochemistry
Thermodynamics is the science of the
relationship between heat and other
forms of energy.
Thermochemistry is the study of the quantity
of heat absorbed or evolved by chemical
reactions.
Energy
Types of Energy
1. Kinetic energy
2. Potential energy
3. Chemical energy
4. Heat energy
5. Electric energy
6. Radiant energy
Energy
There are three broad concepts of
energy:
Kinetic Energy is the energy associated with an
object by virtue of its motion.
Potential Energy is the energy an object has by
virtue of its position in a field of force.
Internal Energy is the sum of the kinetic and
potential energies of the particles making up a
substance.
Energy
Kinetic Energy: An object of mass m
and speed or velocity has kinetic
energy Ek equal to
Ek
1 mv 2
2
A Problem to Consider
Consider the kinetic energy of a person
whose mass is 130 lb (59.0 kg)
traveling in a car at 60 mph (26.8 m/s).
Ek
1 ( 59.0 kg ) ( 26.8 m / s ) 2
2
4
2
2
Ek 2.12 10 kg m / s
4
Ek 2.12 10 J
The SI unit of energy, kg.m2/s2, is given the name
Joule.
Energy
Potential Energy: This energy
depends on the position (such
as height) in a field of force
(such as gravity).
For example, water of a given
mass m at the top of a dam is at
a relatively high position h in the
gravitational field g of the earth.
Ep mgh
A Problem to Consider
Consider the potential energy of 1000 lb
of water (453.6 kg) at the top of a 300
foot dam (91.44 m).
2
Ep 4.06 10 kg m / s
5
Ep 4.06 10 J
Energy
Internal Energy is the energy of the particles
making up a substance.
The total energy of a system is the sum of its
kinetic energy, potential energy, and internal
energy, U.
Etot Ek Ep U
Energy
The Law of Conservation of Energy:
Energy may be converted from one
form to another, but the total quantities
of energy remain constant.
Heat of Reaction
In chemical reactions, heat is often
transferred from the system to its
surroundings, or vice versa.
The substance or mixture of substances
under study in which a change occurs is
called the thermodynamic system (or
simply system.)
The surroundings are everything in the
vicinity of the thermodynamic system.
Heat of Reaction
Heat is defined as the energy that flows into
or out of a system because of a difference in
temperature between the system and its
surroundings.
Heat flows from a region of higher
temperature to one of lower temperature; once
the temperatures become equal, heat flow
stops.
(See Animation: Kinetic Molecular Theory/Heat Transfer)
Heat of Reaction
Heat is denoted by the symbol q.
The sign of q is positive if heat is absorbed
by the system.
The sign of q is negative if heat is evolved
by the system.
Heat of Reaction is the value of q
required to return a system to the given
temperature at the completion of the
reaction.
Heat of Reaction
An exothermic process is a
chemical reaction or physical
change in which heat is evolved
(q is negative).
An endothermic process is a
chemical reaction or physical
change in which heat is
absorbed (q is positive).
Heat of Reaction
Exothermicity
out of a system
Surroundings
Energy
System
q < 0
Endothermicity
into a system
Surroundings
Energy
System
q > 0
H H (products) H ( reactants )
H q p
U qp w
(See Animation: Work vs. Energy Flow)
In chemical systems, work is defined as a change in
volume at a given pressure, that is:
w PV
U H P V
So H is essentially the heat obtained or absorbed
by a reaction in an open vessel where the work
portion of U is unmeasured.
Thermochemical Equations
A thermochemical equation is the
chemical equation for a reaction
(including phase labels) in which the
equation is given a molar interpretation,
and the enthalpy of reaction for these
molar amounts is written directly after
the equation.
N 2 (g ) 3H 2 (g ) 2NH 3 (g ); H -91.8 kJ
Thermochemical Equations
In a thermochemical equation it is
important to note phase labels because
the enthalpy change, H, depends on
the phase of the substances.
2H 2 (g ) O 2 (g ) 2H 2O(g ) ; H o - 483.7 kJ
o
2H 2 (g ) O 2 (g ) 2H 2O(l ) ; H - 571.7 kJ
Thermochemical Equations
The following are two important rules for
manipulating thermochemical equations:
When a thermochemical equation is multiplied
by any factor, the value of H for the new
equation is obtained by multiplying the H in the
original equation by that same factor.
When a chemical equation is reversed, the value
of H is reversed in sign.
Thermochemistry
6.5 Applying Stoichiometry to
Heats of Reactions
6.6 Measuring Heats of
Reactions
6.7 Hesss Law
6.8 Standard Enthalpies of
Formation
6.9 FuelsFoods, Commercial
and Rocket Fuels
890.3 kJ
1mol
CH 556 kJ
4
q CT
A Problem to Consider
Suppose a piece of iron requires 6.70 J
of heat to raise its temperature by one
degree Celsius. The quantity of heat
required to raise the temperature of the
piece of iron from 25.0oC to 35.0oC is:
o
q s m T
A Problem to Consider
Calculate the heat absorbed when the
temperature of 15.0 grams of water is
raised from 20.0oC to 50.0oC. (The
specific heat of water is 4.184 J/g.oC.)
q s m T
q
o
J
(4.184 go C ) (15.0g ) (50.0 20.0 C)
3
q 1.88 10 J
Heats of Reaction:
Calorimetry
A calorimeter is a device
used to measure the heat
absorbed or evolved
during a physical or
chemical change.
The heat absorbed by the
calorimeter and its contents
is the negative of the heat of
reaction.
qcalorimeter q rxn
A Problem to Consider
When 23.6 grams of calcium chloride, CaCl2, was dissolved
in water in a calorimeter, the temperature rose from 25.0oC
to 38.7oC.
If the heat capacity of the solution and the calorimeter is 1258
J/oC, what is the enthalpy change per mole of calcium chloride?
q cal CT
o
o
J
(1258 o C ) ( 38.7 C 25.0 C)
q cal 1.72 10 J
Now we must calculate the heat per mole of
calcium chloride.
(1 mol CaCl 2 )
( 23.6 g CaCl 2 )
0.212 mol CaCl 2
111 .1 g
Now we can calculate the heat per mole of
calcium chloride.
q rxn
17.2 kJ
H
81.1 kJ / mol
mol CaCl 2 0.212 mol
Hesss Law
Hesss law of heat summation states
that for a chemical equation that can be
written as the sum of two or more steps,
the enthalpy change for the overall
equation is the sum of the enthalpy
changes for the individual steps.
(See Animation: Hesss Law)
Hesss Law
For example, suppose you are given the
following data:
o
S(s ) O 2 (g ) SO 2 (g ); H -297 kJ
o
2S(s ) 3O 2 (g ) 2SO 3 (g ); H o ?
Hesss Law
If we multiply the first equation by 2 and
reverse the second equation, they will
sum together to become the third.
o
A Problem to Consider
Large quantities of ammonia are used
to prepare nitric acid according to the
following equation:
A Problem to Consider
You record the values of Hfo under the
formulas in the equation, multiplying them by
the coefficients in the equation.
5( 0)
4(90.3)
Table 6.2
Table 6.2
Table 6.2
6( 241.8)
Table 6.2
A Problem to Consider
Using the summation law:
H
o
o
nH f (products )
o
mH f (reactants )
H 906 kJ
Be careful of arithmetic signs as they are a
likely source of mistakes.
Fuels
A fuel is any substance that is burned to
provide heat or other forms of energy.
In this section we will look at:
Foods as fuels
Fossil fuels
Coal gasification
and liquefaction
Syngas
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 (C6H12O6)
undergoes combustion according to the following
equation.
C6 H12O 6 (s ) 6O 2 (g )
Fuels
A representative fat is glyceryl trimyristate,
C45H86O6. The equation for its combustion is:
Metabolic Energy
The complex of biochemical reactions that make food energy
available for use by living organisms is called metabolism.
A kilocalorie (4.2kj) is the amount of heat needed to change the
temperature of 1 kg of water by 1 C; it is equal to one dietary
"calorie."
Food
kcal
1 raw onion
5
1 dill pickle
15
1 gum drop
35
1 poached egg
75
1 banana
120
1 cupcake
130
1 broiled hamburger patty 150
1 glass of milk
165
1 cup bean soup
190
1 cup tuna salad
220
1 ice cream soda
325
broiled chicken
350
1 lamb chop
420
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, CH4, but
also contains small quantities of ethane, C2H6,
propane, C3H8, and butane, C4H10.
We would expect the fuel value of natural gas to be
close to that for the combustion of methane.
CH 4 (g ) 2O 2 (g ) CO 2 (g ) 2H 2O(g ) ; H 802 kJ
o
Fuels
Petroleum is a very complicated mixture of
compounds.
Gasoline, obtained from
petroleum, contains
many different
hydrocarbons, one of
which is octane, C8H18.
C8 H18 (l ) 252 O 2 (g )
o
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.
CO(g ) 3H 2 (g ) CH 4 (g ) H 2O(g )