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Chapter 5

Thermochemistry

Thermochemistry is an aspect of
thermodynamics involving the study of the
relationships between chemical reactions
and energy changes involving heat.

Work Heat
Energy used to Energy used to
cause an object that cause the
has mass to move. temperature of
an object to
w=Fxd increase.

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Energy -the capacity to do work or transfer heat.
Potential Energy, Ep:
Energy an object
possesses by virtue of
its position or chemical
composition.

Kinetic Energy, Ek -
Energy an object
possesses by virtue of
its motion. 1
Ek = ⎯ mv
2
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Thermal energy is kinetic energy in the form of random motion of the particles in
any sample of matter. As temperature increases, thermal energy increases.
Chemical energy is energy possessed by atoms as a result of their state of
chemical combination. The energy of 2 mol of H2 and 1 mol of O2 is different than
that of 2 mol H2O.

Units of Energy
• The SI unit of energy is the joule (J).
kg m2
1 J = 1 ⎯⎯
s2
• An older, non-SI unit is still in
widespread use: The calorie (cal).
1 cal = 4.184 J

• 1 kcal = 1 Calorie (food “calorie”)

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System and Surroundings
• The system includes the
molecules we want to
study (e.g. hydrogen and
oxygen molecules).
• The surroundings are
everything else (here, the
cylinder and piston).
• In thermochemistry we
study the exchange of
energy between the
system and surroundings.

Transferal of Energy

a) The potential energy of this ball


of clay is increased when it is
moved from the ground to the
top of the wall.

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Transferal of Energy

a) The potential energy of this ball


of clay is increased when it is
moved from the ground to the
top of the wall.
b) As the ball falls, its potential
energy is converted to kinetic
energy.

Transferal of Energy
a) The potential energy of this ball
of clay is increased when it is
moved from the ground to the
top of the wall.
b) As the ball falls, its potential
energy is converted to kinetic
energy.
c) When it hits the ground, its
kinetic energy falls to zero (since
it is no longer moving); some of
the energy does work on the ball,
the rest is dissipated as heat.

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Internal Energy
The internal energy of a system is the sum
of all kinetic and potential energies of all
components of the system; we call it E.

ΔE = Efinal − Einitial

Changes in Internal Energy

• When energy is
exchanged between the
system and the
surroundings, it is
exchanged as either
heat (q) or work (w).

ΔE = q + w

First Law of Thermodynamics


is obeyed

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ΔE, q, w, and sign convention
ΔE = q + w

(greater than zero) (less than zero)

System absorbed System released


energy from the energy to the
surroundings surroundings.

Exchange of Heat between


System and Surroundings
•When heat is absorbed
by the system from the
surroundings, the process
is endothermic.

•When heat is released


by the system to the
surroundings, the
process is exothermic.

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State Functions
The internal energy of a system is
independent of the path by which
the system achieved that state.

State Functions

• However, q and w
are not state
functions.
• Whether the battery
is shorted out or is
discharged by
running the fan, its
ΔE is the same.
– But q and w are
different in the two
cases.

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Work

WorkofGasExpansion.MOV

Enthalpy
• Enthalpy is a thermodynamic function equal to the internal
energy plus pressure*volume:
H = E + PV
When the system changes at constant pressure, the change in
enthalpy, ΔH, is
ΔH = Δ(E + PV)
This can be written
ΔH = ΔE + PΔV

Since ΔE = q + w and w = −PΔV, we can substitute these into


the enthalpy expression:
ΔH = ΔE + PΔV
ΔH = (q+w) − w
ΔH = q

The enthalpy change, ΔH, is defined as the heat gained or lost by


the system under constant pressure.

ΔH = qp

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Properties of Enthalpy

1. Enthalpy is a state function.


2. Enthalpy is an extensive property.
3. Enthalpy is reversible.
4. ΔH for a reaction depends on the
state of the products and the state
of the reactants.

Endothermic and Exothermic


ΔH = Hfinal – Hinitial or ΔH = Hproducts − Hreactants

• A process is
endothermic
when ΔH is
positive (>0).

•A process is
exothermic
when ΔH is
negative (<0).

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Enthalpies of Reaction
This quantity, ΔH, is called the enthalpy of
reaction, or the heat of reaction.

FormationofWater.MOV

Thermite.mov

A thermochemical equation is an equation for which ΔH is given:

CH4(g) + 2O2(g) Æ CO2(g) + H2O(l) ΔH = -890 kJ

N2(g) + O2(g) Æ 2NO(g) ΔH = +180.8 kJ

The enthalpy changes assume the coefficients are moles of the


substances
Enthalpy change is a stoichiometric quantity

Calorimetry
• Calorimetry, the
measurement of heat
released or absorbed by
a chemical reaction.
• A calorimeter is the
device used to measure
heat
• The quantity of heat
transferred by the
reaction causes a change
in temperature of the
solution.

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Heat Capacity and Specific Heat
• The amount of energy required to raise the
temperature of a substance by 1 K (1°C) is
its heat capacity (C in units of J/K).
q
C=
ΔT
• We define specific heat capacity (or simply
specific heat; Cs or s in units of J/gK) as the
amount of energy required to raise the
temperature of 1 g of a substance by 1 K.
heat transferred
Specific heat =
mass × temperature change
q
Cs = s =
m × ΔT

Constant Pressure Calorimetry

Indirectly measure the


heat change for the system

Because the specific


heat for water is well
known (4.184 J/mol-
K), we can measure
ΔH for the reaction
with this equation:
q = m × s × ΔT

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Example Calculation
A metal pellet with mass 100.0 g, originally
at 88.4 °C, is dropped into 125 g of water
originally at 25.1 °C. The final temperature
of both the pellet and the water is 31.3 °C.

Calculate the heat capacity C (in J/°C) and


specific heat capacity (in J/g°C) of the
pellet. The specific heat of water is 4.184
J/g°C.

Calorimetry Calculations

• The calorimeter and its contents are


the surroundings, so qsurr is found from
the mass, heat capacity, and
temperature change (q = msΔT)
• The chemical reaction is the system,
and qsys is ΔH
• The law of conservation of energy
requires that
qsurr + ΔH = 0 or ΔH = -qsurr

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Example Calculation
• When 200. g of a AgNO3 solution
mixes with 150. g of NaI solution,
2.93 g of AgI precipitates, and the
temperature of the solution rises by
1.34oC. Assume 350. g of solution
and a heat capacity (Cs) of 4.18
J/g•oC. Calculate ΔH for the equation
Ag+(aq) + I-(aq) Æ AgI(s)

Example Calculation

• When 200. g of a AgNO3 solution


mixes with 150. g of NaI solution,
2.93 g of AgI precipitates, and the
temperature of the solution rises by
1.34oC. Assume 350. g of solution
and a heat capacity of 4.18 J/g•oC.
Calculate ΔH for the equation
Ag+(aq) + I-(aq) Æ AgI(s)

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Bomb Calorimetry
• Because the
volume in the bomb
calorimeter is
constant, what is
measured is really
the change in
internal energy, ΔE,
not ΔH.
• For most reactions,
the difference is
very small.

Standard Enthalpy Values


ƒ ΔH is well known for many reactions, and
it is inconvenient to measure ΔH for every
reaction in which we are interested.
• However, we can estimate ΔH using ΔH
values that are published and the
properties of enthalpy.
• Most ΔH values are labeled ΔHo
• Measured under standard conditions
– P = 1 atm (but for gases P = 1 bar)
– T = usually 298.15 K (25 oC)
– (Concentration = 1 mol/L)

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Hess’s Law

Hess’s law states when two or


more thermochemical equations
are added, the enthalpy change of
the resulting equation is the sum
of those for the added equations

C(s) + O2(g) Æ CO2(g) ΔH = -393.5 kJ


CO2(g) Æ CO(g) + ½O2(g) ΔH = +283.0 kJ

C(s) + ½O2(g) Æ CO(g) ΔH = -110.5 kJ

Hess’s Law

Hess’s law states


that “If a reaction is
carried out in a
series of steps, ΔH
for the overall
reaction will be equal
to the sum of the
enthalpy changes for
the individual steps.”

ΔH is a state function.

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Hess’s Law Example
• Given the thermochemical equations
2WO2(s) + O2(g) Æ 2WO3(s) ΔH = -506 kJ
2W(s) + 3O2(g) Æ 2WO3(s) ΔH = -1686 kJ

calculate the enthalpy change for


2W(s) + 2O2(g) Æ 2WO2(s)

Enthalpies of Formation
• An enthalpy of formation, ΔHf, is defined as the
enthalpy change for the reaction in which a
compound is made from its constituent
elements in their elemental forms.

Standard Enthalpy of Formation


• Only one enthalpy value is needed for each
substance, called the standard enthalpy of
formation
• The standard enthalpy of formation is the
enthalpy change when one mole of a
substance in its standard state is formed from
the most stable form of the elements in their
standard states

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Standard State
• Enthalpy changes depend on the
temperature and pressure at which
they are measured
– When applying Hess’s law, all values must
refer to the same conditions of pressure
and temperature
• The standard state of a substance at
a specified temperature is the pure
form at 1 atm pressure
– Tabulated values for enthalpy refer to the
standard state, usually at a temperature of
25oC

Standard Enthalpies of Formation


Standard enthalpies of formation, ΔHf,
°
are measured under standard conditions
(25°C and 1.00 atm pressure).

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Calculation of ΔH
We can calculate ΔH in this way:

ΔH = Σ n ΔHf(products) - Σ m ΔHf(reactants)
where n and m are the stoichiometric coefficients.
°

Example Calculation:
Enthalpy of reaction

• Use standard enthalpies of formation


to calculate the enthalpy change for
the reaction
P4O10(s) + 6H2O(g) Æ 4H3PO4(s)
Substance ΔHfo (kJ/mol)
P4O10(s) -2940
H2O(g) - 242
H3PO4(s) -1279

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Standard Enthalpy of Formation

• The symbol used for standard enthalpy of


formation is ΔHfo, where the superscript o
designates standard state
– Some examples of standard enthalpies of
formation are:

C(graphite) + O2(g) Æ CO2(g) ΔHfo[CO2(g)]


H2(g) + ½O2(g) Æ H2O(l) ΔHfo[H2O(l)]
2Na(s) + Se(s) + 2O2(g) Æ Na2SeO4(s) ΔHfo[Na2SeO4(s)]
H2(g) Æ H2(g) ΔHfo[H2(g)] = 0

Calculation of ΔH
C3H8 (g) + 5 O2 (g) ⎯→ 3 CO2 (g) + 4 H2O (l)
•Imagine this as
occurring
in 3 steps:
C3H8 (g) ⎯→ 3 C(graphite) + 4 H2 (g)
3 C(graphite) + 3 O2 (g) ⎯→ 3 CO2 (g)
4 H2 (g) + 2 O2 (g) ⎯→ 4 H2O (l)

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Calculation of ΔH
C3H8 (g) + 5 O2 (g) ⎯→ 3 CO2 (g) + 4 H2O (l)
•Imagine this as
occurring
in 3 steps:
C3H8 (g) ⎯→ 3 C(graphite) + 4 H2 (g)
3 C(graphite) + 3 O2 (g) ⎯→ 3 CO2 (g)
4 H2 (g) + 2 O2 (g) ⎯→ 4 H2O (l)

Calculation of ΔH
C3H8 (g) + 5 O2 (g) ⎯→ 3 CO2 (g) + 4 H2O (l)
•Imagine this as
occurring
in 3 steps:
C3H8 (g) ⎯→ 3 C(graphite) + 4 H2 (g)
3 C(graphite) + 3 O2 (g) ⎯→ 3 CO2 (g)
4 H2 (g) + 2 O2 (g) ⎯→ 4 H2O (l)

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Calculation of ΔH
C3H8 (g) + 5 O2 (g) ⎯→ 3 CO2 (g) + 4 H2O (l)
• The sum of these
equations is:

C3H8 (g) ⎯→ 3 C(graphite) + 4 H2 (g)


3 C(graphite) + 3 O2 (g) ⎯→ 3 CO2 (g)
4 H2 (g) + 2 O2 (g) ⎯→ 4 H2O (l)

C3H8 (g) + 5 O2 (g) ⎯→ 3 CO2 (g) + 4 H2O (l)

Calculation of ΔH
C3H8 (g) + 5 O2 (g) ⎯→ 3 CO2 (g) + 4 H2O (l)
ΔH = [3(-393.5 kJ) + 4(-285.8 kJ)] - [1(-103.85 kJ) + 5(0 kJ)]
= [(-1180.5 kJ) + (-1143.2 kJ)] - [(-103.85 kJ) + (0 kJ)]
= (-2323.7 kJ) - (-103.85 kJ)
= -2219.9 kJ

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Enthalpy of reaction

ΔH = Σ n ΔHf(products) - Σ m ΔHf(reactants)

Example 1:
C(s) + O2(g) Æ CO2(g)
ΔHfo(CO2) = -393.5 kJ
The enthalpy of reaction is -393.5 kJ.

Example 2:
2C(s) + O2(g) Æ 2CO(g)
ΔHfo(CO) = -110.5 kJ
The enthalpy of reaction is 2*(-110.5 kJ) = -221.0 kJ.

Hess’ Law example


2H2(g) + O2(g) Æ 2H2O(l) ΔH = -572 kJ
C3H4(g) + 4O2(g) Æ 3CO2(g) + 2H2O(l) ΔH = -1937 kJ
C3H8(g) + 5O2(g) Æ 3CO2(g) + 4H2O(l) ΔH = -2220 kJ

Use Hess’ Law to calculate the enthalpy of the following


hydrogenation reaction:

C3H4(g) + 2H2(g) Æ C3H8(g)

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Calculate the standard enthalpy of formation of gaseous diborane
(B2H6) using the following thermochemical information:

4B(s) + 3O2(g) Æ 2B2O3 (s) ΔH° = -2509.1 kJ


2H2(g) + O2(g) Æ 2H2O(l) ΔH° = -571.7 kJ
B2H6(g) + 3O2(g) Æ B2O3(s) + 3H2O(l) ΔH° = -2147.5 kJ

Hess’s Law

• Calculate ΔH for
3 C2H2(g) Æ C6H6(l)

• Given the thermochemical equations:


ΔH(kJ)
2C2H2(g) + 5O2(g) Æ 4CO2(g) + 2H2O(l) -1692
2C6H6(l) + 15O2(g) Æ 12CO2(g) +6H2O(l) -6339

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Enthalpy Question

Consider the reaction:


2Mg(s) + O2(g) Æ 2MgO(s) ΔH = -1204 kJ

a) Exothermic or endothermic?
b) Calculate amount of heat transferred when 2.4 g of Mg(s) reacts
at constant pressure.
c) How many grams of MgO are produced during an enthalpy
change of -96.0 kJ?
d) How many kJ of heat are absorbed when 7.50 g of MgO(s) is
decomposed into Mg(s) and O2(g) at constant pressure?

Energy Resources
• Modern society requires large
quantities of energy that is
generated from the earth’s natural
resources. The three principal
sources of this energy are
– Fossil fuels
– Nuclear reactors
– Hydroelectric plants

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Fossil Fuels
• Fossil fuels originated from the decay of living
organisms millions of years ago, and account
for about 80% of the energy generated in the
U.S.
• The fossil fuels used in energy generation are
– Natural gas, which is 70 - 80% methane (CH4)
– Liquid hydrocarbons obtained from the distillation
of petroleum
– Coal - a solid mixture of large molecules with a
H/C ratio of about 1

Problems with Fossil Fuels


• Fossil fuels are nonrenewable
resources
– at current consumption rates, natural
gas and petroleum will be practically
depleted at some point.
• Impurities in fossil fuels are a major
source of pollution
• Burning fossil fuels produces large
amounts of CO2

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Air Pollution
• A large fraction of the fossil fuels (especially
coal) contains sulfur, which is converted into
SO2 when the fuel is burned
– Atmospheric SO2 is slowly converted into SO3 that
dissolves in water and forms sulfuric acid, a major
contributor to acid rain
• Chemical scrubbers can be used to treat stack
gases and remove the SO2
• Research is in progress to develop methods of
removing sulfur from fuels before they are
burned

Greenhouse Effect
• The earth receives energy from the sun,
and loses it by radiation
• The greenhouse effect results in the
warming of the environment, if more
energy is received than is radiated
• An increase in the carbon dioxide in the
atmosphere from burning fossil fuels
reduces radiation losses and contributes to
warming by the greenhouse effect

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Nuclear Energy
• Since the end of World War II nuclear power
plants have become the second most important
source of energy
– about 21% of electricity in the U.S. come from nuclear
power plants
– In France more than 80% of the electricity is generated
using nuclear energy

Pros and Cons of Nuclear Energy


• Relatively low fuel costs • Waste from nuclear reactors
• Nuclear plants do not remain dangerously radioactive
contribute to air pollution for several decades
• Since no CO2 is generated, • High cost of decommissioning
nuclear plants do not obsolete reactors
contribute to the greenhouse • Nuclear accidents, while rare,
effect have enormous potential for
damage

Solar Energy
• Only a very small fraction (< 0.1%) of
the energy provided by the sun, is
sufficient to meet the energy needs of
the world
• Currently, no practical way is available
to convert this energy into useful form
for most of the energy needs of
mankind
• In remote areas, when power
consumption is modest, current solar
energy technology is practical

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Fuels

The vast
majority of the
energy
consumed in
this country
comes from
fossil fuels.

Energy in Foods
Most of the fuel in the food we eat comes
from carbohydrates and fats.

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