Chapter 8

Thermochemistry: Chemical Energy

Chapter 8

Chemical Thermodynamics
Chemical Thermodynamics is the study of the energetics of a
chemical reaction.
Thermodynamics deals with the absorption or release of energy (generally
as heat) that accompanies chemical reactions.

These dynamics generally give us an idea of whether a reaction

will be spontaneous
Spontaneous describes a process that can occur without outside
intervention (i.e. changing the temperature, pressure or concentration)
Spontaneity does not imply that the process occurs quickly, but rather
describes a capability to proceed.
If a chemical reaction is found to be spontaneous in one direction, then
under the same conditions, the reverse reaction will be non-spontaneous
This does not mean that the reaction cannot occur, but that it will need
some outside help.
Chapter 8

Evisdom

Energy
Energy is the capacity to do work, or
supply heat.

Energy = Work + Heat

Potential energy, PE, is stored
energy; it results from position or
composition.
Kinetic energy, KE, is the energy
matter has as a result of motion.

KE = 1/2 mv2
Units for KE:
1 Joule = 1 kgm2/s2 OR 1 calorie = 4.184 J
Chapter 8

Units of Energy
The SI unit for energy is the
Joule (J)
The joule is a small amount of
energy so scientists generally
refer to Kilojoules (kJ)
The calorie (cal) is another unit
of energy.
It is defined as the amount of
energy needed to raise the
temperature of 1.00 g of water by
one degree Celsius

1 cal = 4.184 J
Chapter 8

KE, Temperature & State

All substances have kinetic energy no matter
what physical state they are in.
Solids have the lowest kinetic energy, and gases
have the greatest kinetic energy.
As you increase the temperature of a substance,
its kinetic energy increases.

Chapter 8

Forms of Energy
There are six forms of energy:
Heat, Radiant, Electrical, Mechanical, Chemical and Nuclear
We can convert among these types of energy

Chapter 8

Thermal Energy
Thermal Energy is the kinetic energy of molecular motion
(translational, rotational, and vibrational).
We measure this energy by finding the temperature of an object

Thermal energy is proportional to the temperature in degrees

Kelvin

Ethermal T(K)

Chemical Energy is the PE of a chemical compound where

the chemical bonds act as storage containers for the energy

Chapter 8

The System and the Surroundings

The system is the specific part of the universe that is of interest to us
(i.e. the reaction with reactants & products)
The surroundings is the rest of the universe
When performing experiments, we measure changes to the
surroundings then apply those findings to the system.
Energy is transferred between the system and the surroundings
Energy that is transferred from the system to the surroundings has a negative sign
Energy that is transferred from the surroundings to the system has a positive sign

Chapter 8

E = Efinal - EInitial

State Functions
A State Function is a function or property whose value
depends only on the present state (condition) of the system not
the path used to arrive at that condition.
The change in a state function is zero when the system returns to its
original condition.
For non-state functions, the change is not zero if the path returns to the
original condition

Chapter 8

State Functions
Heres an example with a chemical reaction:
The two paths below give the same final state:
N2H4(g) + H2(g) 2 NH3(g) + heat (188 kJ)
N2(g) + 3 H2(g) 2 NH3(g) + heat (92 kJ)
State properties include for the formation of NH3:
temperature, total energy, pressure, density, and
[NH3]
Non-state properties include for the formation of
NH3: heat and reactants used
Chapter 8

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Work
Work (w) is the application of a force (F) through a distance (d)
This work produces an objects movement
If the system performs work on the surroundings, the sign of w is negative.
If the surroundings perform work on the system, the sign of w is positive.

Work = Force Distance

w = Fd
Units for w:
Newton-meters (N-m) or Joules (J)
1 J = 1 N-m

A system that contains one or more gases performs a specific type

of work called PV Work or expansion work.
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Expansion Work

A system that contains a gas can perform work as the gas expands against an
opposing pressure (P) exerted by the surroundings.

This type of work is called Expansion Work or PV Work

w = - PV
V = VFinal - VInitial

1 L atm = 101 J

When a gas expands, w is negative because the system transfers energy to the
surroundings

When a gas contracts, w is positive because the surroundings transfer energy to the
system

Chapter 8

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Work
How much work is done (in kilojoules), and in
which direction, as a result of the following
reaction?

Chapter 8

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Heat
Heat (q) is the energy that
flows from a warmer object
(higher temperature) to a cooler
object (lower temperature)
Heat is associated with the
movement of particles
The faster the particles are
moving, the more heat you
generate (and vice versa)
If the system gives heat to the
surroundings, the sign of q is
negative.
If the surroundings give heat to the
system, the sign of q is positive.
Chapter 8

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The First Law of Thermodynamics

In a reaction, energy is conserved. It is neither created nor destroyed.
It can be converted into a different type of energy though!
The energy change in a system equals the work done on the system + the
heat added.

Total Energy of Reactants = Total Energy of Products

Chapter 8

E = Efinal Einitial = q + w

15

Energy and Enthalpy

Most chemical reactions are performed in containers that are open to
the atmosphere.
The volume of the system is allowed to change but the pressure
(atmospheric pressure) remains constant.
If the work performed is limited to PV work, a state function called
Enthalpy (H) can be defined.

H = E + PV
The change in enthalpy (H) is equal to the heat absorbed by the
system under conditions of constant pressure.

H = E + PV
Chapter 8

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Energy and Enthalpy

The following reaction has E = 186 kJ/mol.
Is the sign of PV positive or negative?
What is the sign and approximate magnitude of
H?

Chapter 8

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Enthalpy Changes: Physical Change

There are two types of Enthalpy changes:
The Enthalpy of Physical Change.
The Enthalpy of Chemical Change

The Enthalpy of Physical Change is the amount of heat

required to change the state of matter

Chapter 8

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Enthalpy Changes: Chemical Change

The Enthalpy of Chemical change deals with the energy
requirements of chemical reactions.
The Heat of the Reaction (Hrxn) gives the amount of heat
absorbed or released due to a chemical reaction at constant
pressure.

Hrxn = Hproducts Hreactants

If a reaction has more than one step, the Hrxn is the sum of
the H for each individual reaction.
(1) Reactants Elements
(2) Elements Products
(Overall) Reactants Products

Heat Absorbed = H1
Heat Absorbed = H2
Heat Absorbed = Hrxn

Chapter 8

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Enthalpy Changes: Chemical Change

In an Exothermic reaction, the reaction
releases energy in the form of heat to the
surroundings (you feel the reaction get hot!)
The energy of the reactants is greater
than that of the products.

Reactants

Products

C (s) + O2 (g) CO2 + Energy

In an Endothermic reaction, the reaction
absorbs energy in the form of heat from the
surroundings (you feel the reaction get cold!)
The energy of the products is greater than
that of the reactants.
Chapter 8

2 H2O (l) + Energy 2 H2 (g) + O2 (g)

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Enthalpy Changes: Chemical Change

The reaction between hydrogen and oxygen to yield
water vapor has H = 484 kJ. How much PV work
is done, and what is the value of E (in kilojoules)
for the reaction of 0.50 mol of H2 with 0.25 mol of O2
at atmospheric pressure if the volume change is 5.6
L?
The explosion of 2.00 mol of solid TNT with a
volume of approximately 0.274 L produces gases
with a volume of 489 L at room temperature. How
much PV (in kilojoules) work is done during the
explosion? Assume P = 1 atm, T = 25C.
2 C7H5N3O6(s) 12 CO(g) + 5 H2(g) + 3 N2(g) + 2
C(s)
Chapter 8

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Stoichiometry and Enthalpy Changes

How much heat (in kilojoules) is evolved or absorbed in each of the
following reactions? State whether the reactions are endothermic or
exothermic.
Burning of 15.5 g of propane:
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l) H = 2219 kJ

Reaction of 4.88 g of barium hydroxide octahydrate with ammonium

chloride:
Ba(OH)28 H2O(s) + 2 NH4Cl(s) BaCl2(aq) + 2 NH3(aq) + 10 H2O(l) H = +80.3 kJ

Chapter 8

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Standard State
To insure a standardization of enthalpy measurements
from different experimental sources, a standard set of
conditions has been selected.
Thermodynamic Standard State:
Most stable form of a substance at 1 atm pressure and 25C
1 M concentration for all substances in solution.

Measurements made under these conditions are indicated

by a superscript to the symbol of the quantity reported.
Standard enthalpy change is indicated by the symbol
H.
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Hesss Law
Hesss Law: The overall enthalpy change for a
reaction is equal to the sum of the enthalpy
changes for the individual steps in the reaction.
3 H2(g) + N2(g) 2 NH3(g) H = 92.2 kJ

Chapter 8

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Hesss Law
Reactants and products in individual
steps can be added and subtracted to
determine the overall equation.
(a) 2 H2(g) + N2(g) N2H4(g)

H1 = ?

(b) N2H4(g) + H2(g) 2 NH3(g)

H2 = 187.6 kJ

(c) 3 H2(g) + N2(g) 2 NH3(g)

H3 = 92.2 kJ

H1 = H3 H2 = (92.2 kJ) (187.6 kJ) = +95.4 kJ

Chapter 8

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Manipulating Chemical Enthalpy Changes

Reversing a reaction changes the sign of H for a reaction:
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l) H = 2219 kJ
3 CO2(g) + 4 H2O(l) C3H8(g) + 5 O2(g) H = +2219 kJ
Multiplying a reaction increases H by the same factor
because H is also stoichiometrically related to the coefficients
of the balanced chemical equation:
3(C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l) H = 2219 kJ)
3 C3H8(g) + 15 O2(g) 9 CO2(g) + 12 H2O(l) H = 6657 kJ
Chapter 8

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13

Hesss Law
The industrial degreasing solvent methylene
chloride (CH2Cl2, dichloromethane) is prepared
from methane by reaction with chlorine:

CH4(g) + Cl2(g) CH2Cl2(g) + HCl(g)

Use the following data to calculate H (in
kilojoules) for the above reaction:
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) H = 98.3 kJ
CH3Cl(g) + Cl2(g) CH2Cl2(g) + HCl(g) H = 104 kJ
Chapter 8

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Hesss Law

What is the equation and H for the net reaction?

Which arrow on the diagram corresponds to which step and which arrow
corresponds to the net reaction?

The diagram shows three energy levels. The energies of which substances
are represented by each?

Chapter 8

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Standard Heats of Formation

Where do all of these H values come from that we
have been using? Has someone determined these
values for all of these reactions?
Standard Heats of Formation (Hf): The enthalpy
change for the formation of 1 mole of substance in its
standard state from its constituent elements in their
standard states.
C (s) + 2 H2 (g) CH4 (g) Hf = -74.5 kJ

The standard heat of formation for any element in its

standard state is defined as being ZERO.
Hf = 0 for an element in its standard state
Chapter 8

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Standard Heats of Formation

The standard enthalpy change for any chemical reaction is
found by subtracting the sum of the heats of formation of
all reactants from the sum of the heats of formation of all
products
H = Hf (Products) Hf (Reactants)
For a balanced equation, each heat of formation must be
multiplied by the stoichiometric coefficient.

aA + bB cC + dD
H = [cHf (C) + dHf (D)] [aHf (A) + bHf (B)]
Chapter 8

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Standard Heats of Formation

Calculate H (in kilojoules) for the reaction of ammonia with

O2 to yield nitric oxide (NO) and H2O(g), a step in the
Ostwald process for the commercial production of nitric acid.
Calculate H (in kilojoules) for the photosynthesis of glucose
from CO2 and liquid water, a reaction carried out by all green
plants.
Chapter 8

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Bond Dissociation Energy

There are over 18 million chemical compounds known at this
time. Who do you think is making all of the Hf
determinations for those compounds?
It is possible to get an approximate Hf for a compound
based on the bonds present.
The Bond Dissociation Energy can be used to determine an
approximate value for Hf .

Hf = D (Bonds Broken) D (Bonds Formed)

Hf = D (Reactant Bonds) D (Product Bonds)
Chapter 8

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Bond Dissociation Energy

To work these problems you will have to draw the Lewis
Structures of the reactants and products. Refer to your
notes from Chapter 7
For the reaction between H2 and Cl2 to form HCl:
H2 (g) + Cl2 (g) 2 HCl (g)
Hf = D (Bonds Broken) D (Bonds Formed)
Hf = (DH-H + DCl-Cl) 2(DHCl)
= (436 kJ/mol + 243 kJ/mol) 2(432 kJ/mol)
= -185 kJ
Chapter 8

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Bond Dissociation Energy

Calculate an approximate H (in kilojoules) for the synthesis of ethyl

alcohol from ethylene:
C2H4(g) + H2O(g) C2H5OH(g)
Calculate an approximate H (in kilojoules) for the synthesis of hydrazine
from ammonia:
Chapter 8

2 NH3(g) + Cl2(g) N2H4(g) + 2 HCl(g)

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Calorimetry and Heat Capacity

The Bond energies and Heats of Formation give us an
approximate idea of Hf.
How do we experimentally measure the amount of heat
transferred during a reaction?
Calorimetry is the science of measuring heat changes (q)
for chemical reactions. There are two types of
calorimeters:
Bomb Calorimetry: A bomb calorimeter measures the heat
change at constant volume such that q = E.
Constant Pressure Calorimetry: A constant pressure calorimeter
measures the heat change at constant pressure such that q = H.
Chapter 8

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Calorimetry and Heat Capacity

Constant Pressure
Chapter 8

Bomb
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Calorimetry and Heat Capacity

Heat capacity (C) is an extensive
property that gives the amount of heat
required to raise the temperature of an
object or substance a given amount.
The greater the Heat Capacity, the greater
the amount of heat needed to increase the
temperature

Specific Heat (SH): The

amount of heat required to raise
the temperature of 1.00 g of
substance by 1.00C.

q = SH m T

q
C=
T
Units: J/K or J/C

Molar Heat Capacity (CM):

The amount of heat required to
raise the temperature of 1.00
mole of substance by 1.00C.

q = CM n T

Chapter 8

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Calorimetry and Heat Capacity

What is the specific heat of lead if it takes 96 J to
raise the temperature of a 75 g block by 10.0C?
When 25.0 mL of 1.0 M H2SO4 is added to 50.0 mL
of 1.0 M NaOH at 25.0C in a calorimeter, the
temperature of the solution increases to 33.9C.
Assume specific heat of solution is 4.184 J/(gC),
and the density is 1.00 g/mL, calculate H for the
reaction.
Chapter 8

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Calorimetry and Heat Capacity

A 12.6 g block of Iron has a temperature of 25.3C.

What is the final temperature of the block if 106.2 J
of heat are added?
Chapter 8

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Introduction to Entropy
We have stated that chemical and physical processes occur
spontaneously only if they go downhill energetically (give off
energy) so that the final state is more stable and lower in energy
than the initial state.
However, we know that reactions that require energy (endothermic
reactions) will also occur.
This is possible because energy is more than just heat. There are
other forms of energy present in reactions that allow it to be
spontaneous despite absorbing heat.
Another factor that effects spontaneity of a reaction is the molecular
disorder of the reaction.
The amount of molecular disorder (or randomness) in a system is called
the systems Entropy (S)
Chapter 8

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Entropy
Entropy has units of J/K (Joules per Kelvin).

S = Sfinal Sinitial
Positive value of S indicates increased disorder.
Negative value of S indicates decreased disorder.

Second Law of
Thermodynamics:
Reactions proceed in the
direction that increases the
entropy of the system plus
surroundings.
Chapter 8

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Entropy

2 CO(g) + O2(g) 2 CO2(g)

CaCO3(s) CaO (s) + CO2(g)
2 C2H6(g) + 7 O2(g) 4 CO2(g) + 6 H2O(g)
Chapter 8

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Entropy and Enthalpy

To decide whether a process is spontaneous,
both enthalpy and entropy changes must be
considered:
Spontaneous process: Decrease in enthalpy (H).
Increase in entropy (+S).
Nonspontaneous process: Increase in enthalpy (+H).
Decrease in entropy (S).

Chapter 8

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Introduction to Gibbs Free Energy

Gibbs Free Energy Change (G) weighs the relative
contributions of enthalpy and entropy to the overall
spontaneity of a process.

G = H TS

Chapter 8

G < 0
G = 0
G > 0

Spontaneous
Equilibrium
Non-spontaneous

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Gibbs Free Energy

G = H TS

Chapter 8

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Gibbs Free Energy

Which of the following reactions are spontaneous
under standard conditions at 25C?
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq) G = 55.7 kJ

2 C(s) + 2 H2(g) C2H4(g) G = 68.1 kJ

N2(g) + 3 H2(g) 2 NH3(g) H = 92 kJ; S = 199 J/K

Chapter 8

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Gibbs Free Energy at Equilibrium

Equilibrium (G = 0): Estimate the temperature
at which the following reaction will be at
equilibrium. Is the reaction spontaneous at room
temperature?

N2(g) + 3 H2(g) 2 NH3(g)

H = 92.0 kJ
S = 199 J/K

Chapter 8

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Gibbs Free Energy

Benzene, C6H6, has an enthalpy of vaporization,
(Hvap) equal to 30.8 kJ/mol and boils at 80.1C.
What is the entropy of vaporization, Svap, for
benzene?

C6H6 (l) C6H6 (g)

Chapter 8

Hvap = 30.8 kJ/mol

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