General Chemistry: Atoms First: Thermochemistry: Chemical Energy

John E. McMurry • Robert C.
Fay
General Chemistry: Atoms First
Chapter 8
Thermochemistry: Chemical Energy
Lecture Notes
Alan D. Earhart
Southeast Community College • Lincoln, NE
Copyright © 2010 Pearson Prentice Hall, Inc.

Energy and Its Conservation
Energy: The capacity to supply heat or do work.
Kinetic Energy (EK): The energy of motion.
Potential Energy (EP): Stored energy.
Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/2

Law of Conservation of Energy: Energy cannot be

created or destroyed; it can only be converted from one
form to another.

Total Energy = EK + EP
Thermal Energy: The kinetic energy of molecular

motion, measured by finding the temperature of an
object.
Heat: The amount of thermal energy transferred from

one object to another as the result of a temperature
difference between the two.

First Law of Thermodynamics: Energy cannot be

created or destroyed; it can only be converted from one
form to another.

Internal Energy and State
Functions
First Law of Thermodynamics: The total internal
energy of an isolated system is constant.
∆E = Efinal - Einitial
Functions
Functions
Functions
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) + 802 kJ energy
∆E = Efinal - Einitial = -802 kJ
802 kJ is released when 1 mole of methane, CH4, reacts

with 2 moles of oxygen to produce 1 mole of carbon
dioxide and two moles of water.

Functions
State Function: A function or property whose value
depends only on the present state, or condition, of the
system, not on the path used to arrive at that state.
Expansion Work
Work = Force x Distance

w=Fxd
Expansion Work
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)

6 mol of gas 7 mol of gas
Expansion Work
Expansion Work: Work done as the result of a volume

change in the system. Also called pressure-volume or
PV work.
Energy and Enthalpy
∆E = q + w
q = heat transferred w = work = -P∆V
q = ∆E + P∆V
Constant Volume (∆V = 0): qV = ∆E
Constant Pressure: qP = ∆E + P∆V

Energy and Enthalpy
qP = ∆E + P∆V = ∆H
Enthalpy change
or
Heat of reaction (at constant pressure)
Enthalpy is a state function whose

∆H = Hfinal - Hinitial
value depends only on the current
state of the system, not on the
= Hproducts - Hreactants
path taken to arrive at that state.

The Thermodynamic Standard
State
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g) ∆H = -2044 kJ
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) ∆H = -2220 kJ
Thermodynamic Standard State: Most stable form of a

substance at 1 atm pressure and at a specified
temperature, usually 25 °C; 1 M concentration for all
substances in solution.
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g) ∆H° = -2044 kJ

Enthalpies of Physical and
Chemical Change
Enthalpy of Fusion (∆Hfusion): The amount of heat
necessary to melt a substance without changing its
temperature.
Enthalpy of Vaporization (∆Hvap): The amount of heat

required to vaporize a substance without changing its
temperature.
Enthalpy of Sublimation (∆Hsubl): The amount of heat

required to convert a substance from a solid to a gas
without going through a liquid phase.

Chemical Change
Chapter 8/20
Chemical Change
2Al(s) + Fe2O3(s) 2Fe(s) + Al2O3(s) ∆H° = -852 kJ
Exothermic: Heat (enthalpy) flows from the

system to the surroundings.
Ba(OH)2 •8H2O(s) + 2NH4Cl(s)

BaCl2(aq) + 2NH3(aq) + 10H2O(l) ∆H° = +80.3 kJ
Endothermic: Heat (enthalpy) flows from the

surroundings to the system.

Chemical Change
2Al(s) + Fe2O3(s) 2Fe(s) + Al2O3(s) ∆H° = -852 kJ
Exothermic: Heat (enthalpy) flows from the

system to the surroundings.
2Fe(s) + Al2O3(s) 2Al(s) + Fe2O3(s) ∆H° = +852 kJ

Endothermic: Heat (enthalpy) flows from the
surroundings to the system.

Calorimetry and Heat Capacity
Measure the heat flow at constant pressure (∆H).

Measure the heat flow at constant volume (∆E).

Heat Capacity (C): The amount of heat required to raise

the temperature of an object or substance a given
amount.
q = C x ∆T
Molar Heat Capacity (Cm): The amount of heat required
to raise the temperature of 1 mol of a substance by 1 °C.
q = (Cm) x (moles of substance) x ∆T

Specific Heat: The amount of heat required to raise the
temperature of 1 g of a substance by 1 °C.
q = (specific heat) x (mass of substance) x ∆T

Assuming that a can of soda has the same specific

heat as water, calculate the amount of heat (in
kilojoules) transferred when one can (about 350 g) is
cooled from 25 °C to 3 °C.
q = (specific heat) x (mass of substance) x ∆T

J
Specific heat = 4.18
g °C
Mass = 350 g
Temperature change = 25 °C - 3 °C = 22 °C

Calculate the amount of heat transferred.

4.18 J x 350 g x 22 °C
Heat evolved = = 32 000 J
g °C
32 000 J x 1 kJ
= 32 kJ
1000 J

Hess’s Law
Hess’s Law: The overall enthalpy change for a reaction

is equal to the sum of the enthalpy changes for the
individual steps in the reaction.
Haber Process: 3H2(g) + N2(g) 2NH3(g) ∆H° = -92.2 kJ
Multiple-Step Process
2H2(g) + N2(g) N2H4(g) ∆H°1 = ?
N2H4(g) + H2(g) 2NH3(g) ∆H°2 = -187.6 kJ
3H2(g) + N2(g) 2NH3(g) ∆H°1+2 = -92.2 kJ

Hess’s Law
∆H°1 + ∆H°2 = ∆H°1+2
∆H°1 = ∆H°1+2 - ∆H°2

= -92.2 kJ - (-187.6 kJ) = 95.4 kJ
Standard Heats of Formation
Standard Heat of Formation (∆H°f ): The enthalpy

change for the formation of 1 mol of a substance in its
standard state from its constituent elements in their
standard states.
Standard states
C(s) + 2H2(g) CH4(g) ∆H°f = -74.8 kJ
1 mol of 1 substance

Chapter 8/32
∆H° = ∆H°f (Products) - ∆H°f (Reactants)
aA + bB cC + dD
∆H° = [c ∆H°f (C) + d ∆H°f (D)] - [a ∆H°f (A) + b ∆H°f (B)]
Products Reactants

Using standard heats of formation, calculate the

standard enthalpy of reaction for the photosynthesis of
glucose (C6H12O6) and O2 from CO2 and liquid H2O.
6CO2(g) + 6H2O(l) C6H12O6(s) + 6O2(g) ∆H° = ?
H° = [∆H°f (C6H12O6(s))] - [6 ∆H°f (CO2(g)) + 6 ∆H°f (H2O(l))]
∆H° = [(1 mol)(-1273.3 kJ/mol)] -

[(6 mol)(-393.5 kJ/mol) + (6 mol)(-285.8 kJ/mol)]
= 2802.5 kJ
6CO2(g) + 6H2O(l) C6H12O6(s) + 6O2(g) ∆H° = 2802.5 kJ

(1) (2) (3)
Why does the calculation “work”?
1. Reverse the “reaction” and reverse the sign on

the standard enthalpy change.
C(s) + O2(g) CO2(g) ∆H° = -393.5 kJ
Becomes
CO2(g) C(s) + O2(g) ∆H° = 393.5 kJ


(1) (2) (3)
1. Multiply the coefficients by a factor and multiply

the standard enthalpy change by the same factor.
CO2(g) C(s) + O2(g) ∆H° = -393.5 kJ
Becomes
6CO2(g) 6C(s) + 6O2(g) ∆H° = 6(393.5 kJ) = 2361.0 kJ


(1) (2) (3)
2. Reverse the “reaction” and reverse the sign on

the standard enthalpy change.
1
H2(g) + O2(g) H2O(l) ∆H° = -285.8 kJ
2
Becomes
1
H2O(l) H2(g) + O2(g) ∆H° = 285.8 kJ
2


(1) (2) (3)
2. Multiply the coefficients by a factor and multiply

the standard enthalpy change by the same factor.
1
H2O(l) H2(g) + O2(g) ∆H° = 285.8 kJ
2
Becomes
6H2O(l) 6H2(g) + 3O2(g) ∆H° = 6(285.8 kJ) = 1714.8 kJ


(1) (2) (3)
6C(s) + 6H2(g) + 3O2(g) C6H12O6(s) ∆H° = -1273.3 kJ
6CO2(g) 6C(s) + 6O2(g) ∆H° = 2361.0 kJ
6H2O(l) 6H2(g) + 3O2(g) ∆H° = 1714.8 kJ
6CO2(g) + 6H2O(l) C6H12O6(s) + 6O2(g)

∆H° = 2802.5 kJ
Bond Dissociation Energies
Bond Dissociation Energy:

• The amount of energy that must be supplied to
break a chemical bond in an isolated molecule in
the gaseous state and is thus the amount of energy
released when the bond forms.
or
• Standard enthalpy changes for the corresponding

bond-breaking reactions.

H2(g) + Cl2(g) 2HCl(g)
∆H° = D(Reactant bonds) - D(Product bonds)
∆H° = (DH-H + DCl-Cl) - (2DH-Cl)
∆H° = [(1 mol)(436 kJ/mol) + (1mol)(243 kJ/mol)] -

(2mol)(432 kJ/mol)
= -185 kJ

Fossil Fuels, Fuel Efficiency,
and Heats of Combustion
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
∆H°c = [∆H°f (CO2(g)) + 2 ∆H°f (H2O(l))] - [∆H°f (CH4(g))]
= [(1 mol)(-393.5 kJ/mol) + (2 mol)(-285.8 kJ/mol)] -
[(1 mol)(-74.8 kJ/mol)]
= -890.3 kJ

Fossil Fuels, Fuel Efficiency,
and Heats of Combustion
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
An Introduction to Entropy
Spontaneous Process: A process that, once

started, proceeds on its own without a continuous
external influence.
Entropy (S): The amount of molecular randomness
in a system.
Spontaneous processes are
• favored by a decrease in H (negative ∆H).
• favored by an increase in S (positive ∆S).
Nonspontaneous processes are

• favored by an increase in H (positive ∆H).
• favored by a decrease in S (negative ∆S).
An Introduction to Free Energy
Gibbs Free Energy Change (∆G)
∆G = ∆H - T ∆S
Enthalpy of Temperature Entropy

reaction (Kelvin) change

Gibbs Free Energy Change (∆G)
∆G = ∆H - T ∆S
∆G < 0 Process is spontaneous
∆G = 0 Process is at equilibrium
(neither spontaneous nor nonspontaneous)
∆G > 0 Process is nonspontaneous


General Chemistry: Atoms First: Thermochemistry: Chemical Energy

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

General Chemistry: Atoms First: Thermochemistry: Chemical Energy

Uploaded by

Copyright:

Available Formats

John E. McMurry • Robert C.

General Chemistry: Atoms First

Copyright © 2010 Pearson Prentice Hall, Inc.

Energy: The capacity to supply heat or do work.

Kinetic Energy (EK): The energy of motion.

Potential Energy (EP): Stored energy.

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/2

Law of Conservation of Energy: Energy cannot be

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/3

Thermal Energy: The kinetic energy of molecular

Heat: The amount of thermal energy transferred from

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/5

First Law of Thermodynamics: Energy cannot be

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/6

∆E = Efinal - Einitial = -802 kJ

802 kJ is released when 1 mole of methane, CH4, reacts

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/10

Work = Force x Distance

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)

Expansion Work: Work done as the result of a volume

q = heat transferred w = work = -P∆V

Constant Volume (∆V = 0): qV = ∆E

Constant Pressure: qP = ∆E + P∆V

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/15

Enthalpy is a state function whose

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/17

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) ∆H = -2220 kJ

Thermodynamic Standard State: Most stable form of a

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g) ∆H° = -2044 kJ

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/18

Enthalpy of Vaporization (∆Hvap): The amount of heat

Enthalpy of Sublimation (∆Hsubl): The amount of heat

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/19

Exothermic: Heat (enthalpy) flows from the

Ba(OH)2 •8H2O(s) + 2NH4Cl(s)

Endothermic: Heat (enthalpy) flows from the

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/21

Exothermic: Heat (enthalpy) flows from the

2Fe(s) + Al2O3(s) 2Al(s) + Fe2O3(s) ∆H° = +852 kJ

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/22

Measure the heat flow at constant pressure (∆H).

Measure the heat flow at constant volume (∆E).

Heat Capacity (C): The amount of heat required to raise

q = (Cm) x (moles of substance) x ∆T

q = (specific heat) x (mass of substance) x ∆T

Assuming that a can of soda has the same specific

q = (specific heat) x (mass of substance) x ∆T

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/27

Calculate the amount of heat transferred.

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/28

Hess’s Law: The overall enthalpy change for a reaction

Haber Process: 3H2(g) + N2(g) 2NH3(g) ∆H° = -92.2 kJ

N2H4(g) + H2(g) 2NH3(g) ∆H°2 = -187.6 kJ

3H2(g) + N2(g) 2NH3(g) ∆H°1+2 = -92.2 kJ

∆H°1 + ∆H°2 = ∆H°1+2

∆H°1 = ∆H°1+2 - ∆H°2

Standard Heat of Formation (∆H°f ): The enthalpy

C(s) + 2H2(g) CH4(g) ∆H°f = -74.8 kJ

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/31

∆H° = ∆H°f (Products) - ∆H°f (Reactants)

∆H° = [c ∆H°f (C) + d ∆H°f (D)] - [a ∆H°f (A) + b ∆H°f (B)]

Copyright © 2010 Pearson Prentice Hall, Inc. Chapter 8/33

Using standard heats of formation, calculate the