Lesson 4

Energy Changes in Chemical

Reactions
Bioenergy. The sugars in
sugarcane, produced from CO2,
H2O, and sunshine via
photosynthesis, can be
converted into ethanol, which
is used as an alternative to
gasoline. In certain climates,
such as that in Brazil, the
sugarcane crop replenishes
itself rapidly, making cane-
based ethanol a sustainable
fuel source.
The Central Science, 12th ed, 2013
Prentice-Hall International
Brown, T.L., Lemay, H.E., and Burnsten
 Lesson Outline
A. The Nature of Energy
- Kinetic Energy and Potential Energy; Units of Energy;
Systems and Surroundings; Transferring Energy: Work
and Heat
B. The First Law of Thermodynamics
- Internal Energy; Relating ΔE to heat and work;
Endothermic and Exothermic processes; State Functions
C. Enthalpy and Enthalpies of Reaction
D. Calorimetry
- Constant-Pressure Calorimetry; Bomb Calorimetry
(Constant – Volume Calorimetry)
E. Hess’s Law
F. Enthalpies of Formation
 The Nature of Energy

Energy is the ability to do work or transfer heat.

Thermodynamics is the study of energy and its

transformations.

Thermochemistry is the study of chemical

reactions and the energy changes that involve heat.

 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.
 The Nature of Energy
Kinetic Energy and Potential Energy
Electrostatic potential energy, Ed, is the attraction
between two oppositely charged particles, Q1 and
Q2, a distance d apart:
Q1Q2
Ed =
d
The constant  = 8.99  109 J-m/C2.
If the two particles are of opposite charge, then Ed is
the electrostatic repulsion between them.
 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
We sometimes use the calorie instead of the joule:
1 cal = 4.184 J (exactly)
A nutritional Calorie:
1 Cal = 1000 cal = 1 kcal
Systems and Surroundings
System: part of the universe we are
interested in.
Surroundings: the rest of the universe.
In thermochemistry we study the
exchange of energy between the system
and surroundings.
open system – matter and energy can be
exchanged with the surroundings
closed system – exchange energy--but not
matter—with the surroundings.
isolated system – neither matter nor
energy may be exchanged with
surroundings.
 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.
 The First Law of
Thermodynamics
Energy can be neither created nor destroyed. Any energy that
is lost by a system must be gained by the surroundings, and
vice versa. This important observation—that energy is
conserved
Internal Energy
• Internal Energy: total energy of a system.
• Cannot measure absolute internal energy.
• Change in internal energy,

E = Efinal − Einitial
The First Law of
Thermodynamics
By definition, the
change in
internal energy, ΔE, is
the final energy of the
system minus the
initial energy of
the system:
ΔE = Efinal− Einitial
ΔE < 0, Efinal <Einitial
the system released
energy to the
surroundings.
 Thermodynamic Quantities:
Three Parts
1) A number, 2) a unit, 3) a sign
– A positive ΔE results when the system gains energy from the
surroundings.
– A negative ΔE results when the system loses energy to the
surroundings.

• When energy is exchanged between the system and the

surroundings, it is exchanged as either heat (q) or work
(w).
• That is, ΔE = q + w.
 The First Law of
Thermodynamics
Relating ΔE 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
The First Law of
Thermodynamics
The First Law of
Thermodynamics
 The First Law of
Thermodynamics
Exothermic and Endothermic Processes
• Endothermic: absorbs heat from the surroundings.
• Exothermic: transfers heat to the surroundings.
• An endothermic reaction feels cold.
• An exothermic reaction feels hot.
 The First Law of
Thermodynamics
State Functions
• The internal energy of a system is independent of the path by
which the system achieved that state.
• State function: depends only on the initial and final states of
system, not on how the internal energy is used.
The First Law of Thermodynamics:
State Function
q and w are not state
functions.

ΔE is the same
whether the battery is
shorted out or is
discharged by
running the fan.
– q and w are
different in the two
cases.
Work
 Enthalpy and Enthalpies of
Reaction
• Enthalpy is a thermodynamic function equal to the internal
energy plus pressure x volume: H = E + PV
• Enthalpy is a state function.
• If the process occurs at constant pressure :
H = ( E + PV )
= E + PV
• Since we know that
w = − PV
• We can write
H = E + PV
= qP + w
 Enthalpy and Enthalpies of
Reaction
• 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
• When ΔH, is positive, the system gains heat from the
surroundings.
• When ΔH, is negative, the surroundings gain heat from the
system.
Enthalpy
Properties of Enthalpy
 Enthalpies of Reaction
• For a reaction:
H = H final − H initial
= H products − H reactants

• Enthalpy is an extensive property (magnitude ΔH 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
 Enthalpies of Reaction
• When we reverse a reaction, we change the sign of
H:

CO2(g) + 2H2O(g) → CH4(g) + 2O2(g) H = +802 kJ

• Change in enthalpy depends on state:

H2O(g) → H2O(l) H = -88 kJ

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
 Heat Capacity and Specific
heat
• The amount of energy required to raise the temperature of a
substance by 1 K (10C) is its heat capacity (C in units of
J/K).

• We define specific heat capacity (or simply specific heat;

Cs or s in units of J/g.K) as the amount of energy required
to raise the temperature of 1 g of a substance by 1 K.
• If the amount is one mole, it is the molar heat capacity.
Heat Capacity and Specific
heat
 Constant-Pressure
Calorimetry
Indirectly measure the heat change for the system
• Atmospheric pressure is constant!
H = qP
qrxn = −qsoln = −(specific heat of solution )
 (grams of solution )  T
• The calorimeter and its contents
are the surroundings, so qsoln is
found from the mass, heat
capacity, and temperature
change.
Constant-Pressure
Calorimetry
 Bomb Calorimetry ( Constant-
Volume Calorimetry)

• Reaction carried out

under constant volume.
• Use a bomb calorimeter.
• Usually study
combustion.

qrxn = −Ccal  T
Bomb Calorimetry ( Constant-
Volume Calorimetry)
 Hess’s Law
• ΔH is known for many reactions, but it is inconvenient to
measure ΔH for every reaction in which we are interested.
• However, we can calculate ΔH using published ΔH values
and the properties of enthalpy.
• 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
 Hess’s Law
• Most ΔH values are labeled Δ𝐻 𝑜 , and measured under
standard conditions
– P = 1 atm (but for gases P = 1 bar)
– T = usually 298.15 K (25.0 oC)
– Concentration = 1 mol/L
• Using Hess’s law - when two or more thermochemical
equations are added, the enthalpy change of the resulting
equation is the sum of those for the added equations.
Hess’s Law
 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.
• 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.
 Enthalpies of Formation
• Standard conditions (standard state): 1 atm
and 25 oC (298 K).
• Standard enthalpy, Ho, is the 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.
• 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.
Enthalpies of Formation
 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.
• For a reaction
H rxn =  nH f (products) −  mH f (reactants)

Where:
n and m are the stoichiometric
coefficients