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Chapter 1
Thermochemistry – Energy Flow and Chemical Change
Key terms
thermodynamics The study of heat (thermal
energy) and its interconversions.
thermochemistry The branch of
thermodynamics that focuses on the heat involved
in chemical and physical change.
internal energy (E) The sum of the kinetic and
potential energies of all the particles in a system.
heat (q) The energy transferred between objects
because of a difference in their temperatures only.
work (w) The energy transferred when an object
is moved by a force.
state function A property of the system
determined by its current state, regardless of how
it arrived at that state.
pressure-volume work (PV work) A type of
work in which a volume change occurs against an
external pressure.
isobaric process A thermodynamic process in
which the pressure stays constant.
isochoric process A thermodynamic process in
which the volume remains constant.
isothermal process A thermodynamic process in
which the temperature of a system remains
constant.
adiabatic process A thermodynamic process in
which no heat is gained or lost by the system.
first law of thermodynamics A basic
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observation that the total energy of the universe is
constant; thus, ΔEuniverse = ΔEsystem + ΔEsurroundings =
0.
enthalpy (H) A thermodynamic quantity that is
the sum of the internal energy plus the product of
the pressure and volume.
change in enthalpy (ΔH) The change in internal
energy plus the product of the constant pressure
and the change in volume: ΔH = ΔE + PΔV; the
heat lost or gained at constant pressure: ΔH = qP.
enthalpy diagram A graphic depiction of the
enthalpy change of a system.
exothermic process A process that occurs with a
release of heat to the surroundings and therefore a
decrease in the enthalpy of the system (ΔH < 0).
endothermic process A process that occurs with
an absorption of heat from the surroundings and
therefore an increase in the enthalpy of the
system (ΔH > 0).
heat capacity The quantity of heat required to
change the temperature of an object by 1 K.
specific heat capacity (c) The quantity of heat
required to change the temperature of 1 gram of a
material by 1 K.
molar heat capacity (C) The quantity of heat
required to change the temperature of 1 mol of a
substance by 1 K.
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General Chemistry II
calorimeter A device used to measure the heat
released or absorbed by a physical or chemical
process taking place within it.
stoichiometry The study of the mass-mole-
number relationships of chemical formulas and
reactions.
Hess’s law A law stating that the enthalpy change
of an overall process is the sum of the enthalpy
changes of the individual steps.
thermochemical equation A chemical equation
that shows the heat involved for the amounts of
substances specifed.
standard state A set of specifcations used to
compare thermodynamic data: 1 atm for gases
Dr. Truong Thanh Tu
behaving ideally, 1 M for dissolved species, or
the pure substance for liquids and solids.
standard enthalpy of reaction (ΔHorxn) (also
standard heat of reaction) The enthalpy change
that occurs during a reaction when all
components are in their standard states.
standard enthalpy of formation (ΔHof) (also
standard heat of formation) The enthalpy change
occurring when 1 mol of a compound forms from
its elements with all components in their standard
states.
bond energy (also bond enthalpy or bond
strength) The enthalpy change (always >0)
accompanying the breakage of a given bond in 1
mol of gaseous molecules.

Key Principles
• Chemical or physical change is always accompanied by a change in the energy content of the matter.
(Introduction)
• To study a change in energy (E), scientists conceptually divide the universe into the system (the part
being studied) and the surroundings (everything else). All energy changes occur as heat (q) and/or work
(w), transferred either from the surroundings to the system or from the system to the surroundings (E =
q + w). Thus, the total energy of the universe is constant (law of conservation of energy, or first law of
thermodynamics). (Section 1.1)
• Because E is a state function—a property that depends only on the current state of the system—E
depends only on the difference between the initial and final values of E. Therefore, the magnitude of E
is the same no matter how a given change in energy occurs. (Section 1.1)
• Enthalpy (H) is also a state function and is related to E. The change in enthalpy (H) equals the heat
transferred at constant pressure, qP. Most laboratory, environmental, and biological changes occur at
constant P, so H is more relevant than E and easier to measure. (Section 1.2)
• The change in the enthalpy of a reaction (Hrxn) is negative (< 0) if the reaction releases heat
(exothermic) and positive (> 0) if it absorbs heat (endothermic). (Section 1.2)
• The more heat a substance absorbs, the higher its temperature becomes, but each material has its own
capacity for absorbing heat. Knowing this capacity and measuring the change in temperature in a
calorimeter, we can find Hrxn. (Section 1.3)

• The quantity of heat released or absorbed in a reaction is related stoichiometrically to the amounts
(mol) of reactants and products. (Section 1.3)

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General Chemistry II Dr. Truong Thanh Tu
• Because H is a state function, we can find H of any reaction by imagining the reaction occurring as
the sum of other reactions whose enthalpies of reaction we know or can measure (Hess’s law). (Section
1.4)
• Chemists have specified a set of conditions, called standard states, to determine and compare
enthalpies (and other thermodynamic variables) of different reactions. Each substance has a standard
enthalpy of formation (Hof ), the enthalpy of reaction when 1 mol of the substance is formed from its
elements under these conditions. The Hof values for each substance in a reaction are used to calculate the
standard enthalpy of reaction (Horxn). (Section 1.5)

Learning Objectives
• Interconvert energy units; understand that E of a system appears as the total heat and/or work
transferred to or from its surroundings; understand the meaning of a state function.
• Understand the meaning of H, why we measure H, and the distinction between exothermic and
endothermic reactions; draw enthalpy diagrams for chemical and physical changes.
• Understand the relation between specific heat capacity and heat transferred in both constant-pressure
(coffee-cup) and constant-volume (bomb) calorimeters.
• Understand the relation between heat of reaction and amount of substance.
• Explain the importance of Hess’s law and use it to find an unknown H.
• View a reaction as the decomposition of reactants followed by the formation of products; understand
formation equations and how to use H°f values to find H°rxn.

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