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CHEM 1103
CHAPTER 5
THERMOCHEMISTRY

Energy and Energy Changes

• Energy
• Usually defined as the capacity to do work or transfer heat
• All forms of energy are either kinetic or potential
• Kinetic energy
• Energy that results from motion 1
Ek  mu2
• Calculated with the equation
2
• Where m is the mass of the object and u is its velocity
• Thermal energy
• Form of kinetic energy
• Energy associated with the random motion of atoms and molecules
• Monitor changes in thermal energy by measuring temperature changes

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Energy and Energy Changes

• Potential energy
• Energy possessed by an object by virtue of its position
• Chemical energy
• Energy stored within the structural units (molecules or polyatomic ions) of chemical
substances
• Amount of chemical energy in a sample of matter depends on the types and
arrangements of atoms in the structural units that make up the sample
• Electrostatic energy
• Potential energy that results from the interaction of charged particles
• Oppositely charged particles attract each other, whereas particles of like charges repel
each other
• Magnitude of the resulting electrostatic potential energy is proportional to the product of
the two charges (Q1 and Q2) divided by the distance (d) between them QQ
E  el
1 2

Energy and Energy Changes

• Kinetic and potential energy are interconvertible
• Dropping an object and allowing it to fall converts potential energy to
kinetic energy
• Likewise, a chemical reaction that gives off heat converts chemical
energy (potential) to thermal energy (kinetic)
• Law of conservation of energy
• Although energy can assume many different forms that are
interconvertible, the total amount of energy in the universe is
constant
• When energy of one form disappears, the same amount of energy
must appear in another form or forms

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Energy and Energy Changes

• Energy Changes in Chemical Reactions
• System
• Specific part of the universe that is of interest to us
• Surroundings
• Rest of the universe outside the system

• Heat
• Transfer of thermal energy between two bodies that are at different
temperatures
• Although the term heat by itself implies the transfer of energy, we
customarily talk of “heat flow,” meaning “heat absorbed” or “heat
released,” when describing the energy changes that occur during a process
• Thermochemistry
• Study of heat (the transfer of thermal energy) in chemical reactions

Energy and Energy Changes

• Exothermic process • Endothermic process
• Process that gives off heat • Process that absorbs thermal energy
as heat

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Energy and Energy Changes

• Units of Energy
• Joule (J)
• SI unit of energy
• Amount of kinetic energy possessed by a 2-kg mass moving at a speed of 1 m/s

1 1
Ek  mu2   2 kg 1m/s  1kg  m2 /s2  1 J
2

2 2
• Can also be defined as the amount of energy exerted when a force of 1 newton (N) is
applied over a distance of 1 meter

1 J  1 Nm
1 N  1 kg  m/s2

Energy and Energy Changes

• Another unit used to express energy is the calorie (cal)
• 1 Cal ≡ 4.184 J
• 1 Cal ≡ 1000 cal
• 1 Cal ≡ 4184 J

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Introduction to Thermodynamics
• Thermodynamics
• Scientific study of the interconversion of heat and other kinds of
energy
• Open system
• Can exchange mass and energy with its surroundings
• Closed system
• Allows the transfer of energy but not mass
• Isolated system
• Does not exchange either mass or energy with its surroundings

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Introduction to Thermodynamics
• States and State Functions
• In thermodynamics, we study changes in the state of a system
• Defined by the values of all relevant macroscopic properties
• Composition, energy, temperature, pressure, and volume
• State Function
• Properties that are determined by the state of the system, regardless of how that
condition was achieved
• Energy, pressure, volume, and temperature

Introduction to Thermodynamics
• First Law of Thermodynamics
• Based on the law of conservation of energy
• States that energy can be converted from one form to another but
cannot be created or destroyed
Usys  Usurr  0
Usys  Usurr
• Change in internal energy of a system, ∆𝑈, is given by

• ∆U = Uf − Ui

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Introduction to Thermodynamics
• Energy
• Defined as the capacity to do work or transfer heat
• When a system releases or absorbs heat, its internal energy changes
• Likewise, when a system does work on its surroundings, or when the
surroundings do work on the system, the system’s internal energy
also changes

Introduction to Thermodynamics
• Overall change in the system’s internal energy is given by
• ∆U = q + w
• q is heat (released or absorbed by the system)
• w is work (done on the system or done by the system)
• Neither q nor w is a state function
• Each depends on the path between the initial and final states of the
system
• U is a state function
• Does not depend on the path between initial and final states

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Introduction to Thermodynamics
TABLE 5.1 Sign Conventions for Heat (q) and work (w)
Process Sign
Heat absorbed by the system (endothermic process) q is positive
Heat released by the system (exothermic process) q is negative
Work done on the system by the surroundings (for example,
w is positive
a volume decrease)
Work done on the system by the surroundings (for example,
w is negative
a volume increase)

Introduction to Thermodynamics

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SAMPLE PROBLEM 5.2

Calculate the overall change in internal energy, U, (in joules)
for a system that absorbs 188 J of heat and does 141 J of work
on its surroundings.

Enthalpy
• Reactions Carried Out at Constant Volume or at Constant
Pressure
2NaN3(s) → 2Na(s) + 3N2(g)

• W = −P∆V

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Enthalpy
• Reactions Carried Out at Constant Volume or at Constant
Pressure
• For a system that can do only PV work:
• ΔU = q − P∆V
• If volume is constant:
• qv = ∆U because P∆V = 0
• If pressure is constant:
• qp = ∆U + P∆V

Enthalpy
• Enthalpy (H)
• Thermodynamic function of a system
• H = U + PV
• H is a state function
• For any process, the change in enthalpy is given by
• ∆H = ∆U + ∆(PV)
• At constant pressure:
• qp = ∆H

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Enthalpy
• Heat exchanged between the system and surroundings is
equal to the change in enthalpy for the process
• Because most laboratory reactions are constant-pressure processes
• Change in enthalpy (ΔH)
• Enthalpy of reaction
• Difference between the enthalpies of the products and the
enthalpies of the reactants
• ∆H = H (products) − H (reactants)

Enthalpy
• Exothermic process • Endothermic process
• Process that gives off heat • Process that absorbs thermal energy
as heat

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Enthalpy
• Thermochemical Equations
• Chemical equations that show the enthalpy changes as well as the
mass relationships
• CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = −890.4kJ∕mol
• ΔH value of –890.4 kJ/mol can be expressed in any of the
following ways:

890.4 kJ 890.4 kJ 890.4 kJ 890.4 kJ

1 mol CH4 2 mol O2 1 mol CO2 2 mol H2O

SAMPLE PROBLEM 5.3

Given the thermochemical equation for photosynthesis,
6H2O(l) + 6CO2(g) → C6H12O6(s) + 6CO2(g) ∆H = +2803 kJ/mol

calculate the solar energy required to produce 75.0 g of

C6H12O6.

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Calorimetry
• Heat Capacity (C)
• Amount of heat required to raise the temperature of an object by 1°C
• For an object with heat capacity C:
• q = C∆T

• Specific Heat Capacity (s or Cs)

• Amount of heat required to raise the temperature of 1 g of the substance
by 1°C
• For a substance with specific heat Cs and mass m:
• q = Csm∆T

• Molar Heat Capacity (Cm)

• Amount of heat required to raise the temperature of 1 mol of the
substance by 1°C

Calorimetry
• For example, we can use the specific heat of water, 4.184
J/(g  °C), to determine the heat capacity of a kilogram of
water:
4.184 J
heat capacity of 1 kg of water   1000 g  4184
1 g  °C
or 4.184  103 J/°C

• Note that specific heat has the units J/(g  °C) and heat
capacity has the units J/°C.

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Calorimetry
TABLE 5.2 Specific Heat Values of Some Common Substance
Substance Specific Heat (J/g  °C) Substance Specific Heat (J/g  °C)
Al(s) 0.900 Fe(s) 0.444
Au(s) 0.129 Hg(l) 0.139
C(graphite) 0.720 H2O(l) 4.184
C(diamond) 0.502 C2H5OH(l)(ethanol) 2.46
Cu(s) 0.385

SAMPLE PROBLEM 5.4

Calculate the amount of heat (in kJ) required to heat 255 g of
water from 25.2°C to 90.5°C.

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Calorimetry
• Constant-Pressure Calorimetry
• Coffee Cup Calorimeter
• ∆Hrxn = qrxn/molrxn = - qsurr /molrxn =
(-Csm∆T)/ molrxn

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Calorimetry
Table 5.3 Heats of Some Typical Reactions and Physical
Processes Measured at Constant Pressure
Type of Reaction Example ΔH (kJ/mol)
Heat of neutralization HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq) −56.2
Heat of ionization H2O(l) → H+(aq) + OH−(aq) +56.2
Heat of fusion H2O(s) → H2O(l) +6.01
Heat of vaporization H2O(l) → H2O(g) +44.0*
• *Measured at 25°C. At 100°C, the value is +40.79 kJ.

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SAMPLE PROBLEM 5.5

A metal pellet with a mass of 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) of the pellet.

Calorimetry
• Constant-Volume Calorimetry
• Bomb Calorimetry
• Because no heat enters or leaves
the system during the process, the
heat change of the system overall
(qsystem) is zero and we can write
• qcal = − qrxn

• qcal = Ccal∆T

• qrxn = −Ccal∆T
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SAMPLE PROBLEM 5.6

A Famous Amos bite-sized chocolate chip cookie weighing 7.25
g is burned in a bomb calorimeter to determine its energy
content. The heat capacity of the calorimeter is 39.97 kJ/°C.
During the combustion, the temperature of the water in the
calorimeter increases by 3.90°C. Calculate the energy content
(in kJ/g) of the cookie.

Hess’s Law
• Hess’s law
• Because enthalpy is a state function, the change in enthalpy that
occurs when reactants are converted to products in a reaction is the
same whether the reaction takes place in one step or in a series of
steps

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Hess’s Law
• The following guidelines are helpful in interpreting, writing,
and manipulating thermochemical equations:
• Always specify the physical states of all reactants and products,
because they help determine the actual enthalpy changes.
• In the equation for the combustion of methane changing the liquid water product to
water vapor changes the value of ∆H.
• If we multiply both sides of a thermochemical equation by a factor n,
then ΔH must also change by the same factor
• H2O(s) → H20(l) ∆H = +6.01 kJ/mol
• 2H2O(s) → 2H2O(l) ∆H = 2(6.01 kJ/mol) = +12.02 kJ/mol
• When we reverse a chemical equation, we change the roles of
reactants and products. Consequently, the magnitude of ΔH for the
equation remains the same, but its sign changes.
• CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = −890.4 kJ/mol
• CO2(g) + 2H2O(l) → CH4(g) + 2O2(g) ∆H = +890.4 kJ/mol

SAMPLE PROBLEM 5.7

Given the following thermochemical equations,
• NO(g) + O3(g) → NO2(g) + O2(g)
• ∆H = −198.9 kJ/mol
3
O3 (g)  O2 (g)
2
• ∆H = −142.3 kJ/mol
• O2(g) →2O(g)
• ∆H = +495 kJ/mol
Determine the enthalpy change for the reaction
• NO(g) + O(g) → NO2(g)

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Standard Enthalpies of Formation

• There is no way to measure the absolute value of the
enthalpy of a substance
• Only changes in enthalpy are measureable
• Only values relative to an arbitrary reference can be determined
• Chemists have agreed on an arbitrary reference point for enthalpy
• Standard enthalpy of formation (∆Hf°)
• Defined as the heat change that results when 1 mole of a compound
is formed from its constituent elements in their standard states

Standard Enthalpies of Formation

• Readily calculate the standard enthalpy of reaction (∆H°rxn),
defined as the enthalpy of a reaction carried out under
standard conditions

aA  bB  c C  dD

Hrxn   cHf  C  d Hf D   aHf  A   bHf B 

Hrxn   nHf product   mHf reactants

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SAMPLE PROBLEM 5.8

Using data from Appendix 2, calculate ∆H°rxn for

Ag+(aq) + Cl−(aq) → AgCl(s).

SAMPLE PROBLEM 5.9

• Given the following information, calculate the standard
enthalpy of formation of acetylene (C2H2) from its
constituent elements:
• C graphite + O 𝑔 → CO 𝑔 ∆𝐻° = −393.5 kJ/mol 1
• H 𝑔 + O 𝑔 →H O 𝑙 ∆𝐻° = −285.8 kJ/mol 2
• 2C H 𝑔 + 5O 𝑔 → 4CO 𝑔 + 2H O 𝑙
∆𝐻° = −2598.8 kJ/mol 3

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Areas to Study for Weekly Quizzes

• Chapter 5 Summary
• Chapter 5 Key Words
• Checkpoint Questions
• 5.1.3, 5.1.4, 5.1.6
• 5.2.1, 5.2.2, 5.2.3, 5.2.4
• 5.3.1, 5.3.2
• 5.4.1, 5.4.2, 5.4.3. 5.4.4
• 5.5.1, 5.5.2, 5.5.3, 5.5.4
• 5.6.1, 5.6.2, 5.6.3, 5.6.4

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