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CHAPTER (III)

THERMOCHEMISTRY

Prepared by
Dr. Ehteram A. Noor
Associate Prof. of physical chemistry

Revised by
Dr. Salwa Al-Rashid
Associate Prof. of physical chemistry

Ehteram A. Noor- King AbdulAziz University

CHAPTER III
THERMOCHEMISTRY
Lecture (5-6) Outline

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III-1. Introduction
Thermochemistry is the study of the heat evolved (exothermic
process) or heat absorbed (endothermic process) in chemical
reactions. Thermochemistry, generally, is concerned with the
heat exchange accompanying transformations, such as mixing,
CHAPTER (III)

phase transitions, chemical reactions, etc., which include

calculations of such quantities as the heat capacity, heat of
combustion, heat of formation, etc. The laws of
thermochemistry rest on two statements:
(1)Lavoisier and Laplace's law (1782): the heat exchange
accompanying a transformation is equal in its value and
opposite in sign of the reverse transformation.
(2)Hess's law (1840): the heat exchange accompanying a
transformation is the same whether the process occurs in
one or several steps.
Both laws preceded the first law of thermodynamics.
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III-2. Heat in Chemical Reactions

In CHAPTER II we saw that q is a path function (not a state function). It
is much more convenient to discuss the energy changes accompanying
reactions in terms of state functions because they are independent of the
reaction path to know if the reaction carried out reversibly or not.

 Most of the chemical reactions occur at constant pressure, so the heat of

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the reaction (qp )can be presented by the enthalpy function, ∆H.

 The enthalpy change for the reaction, ∆H, is the difference between
the enthalpies of the different states or the reactants and products.

Figure (III-1): Energy diagram Ehteram A. Noor- King AbdulAziz University

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III-3. Stoichiometry of Thermochemical Equations

A thermochemical equation is the chemical equation for a reaction with the
enthalpy of reaction shown immediately after the equation.

H 2(g)  1/2O 2(g)  H 2 O (l ) H  285.840 kJ

In working with thermochemical equations you will find the following rules
CHAPTER (III)

helpful.

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In working with thermochemical equations you will find the following rules
helpful.
CHAPTER (III)

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III-4. Measuring Heat of Reactions

Heats of reaction can be measured in a device
called a calorimeter.


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Fig. (III-1) The calorimeter

The heat measured at constant pressure can be calculated then as


qP  m C T
where:
 m is the mass of the substance, Define the
 C is the specific heat which is a constant value for each specific heat.
substance and has units of J g-1 °C-1
∆T is the temperature difference
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Sometimes the mass of the calorimeter and it contents and the overall
specific heat are combined into a single number called the heat capacity, C.
Then the heat can be calculated as:

qP  CT
Define the heat
capacity??

The heat measured here is for the calorimeter and its contents.
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The heat for the reaction is of the same magnitude as the heat for the
calorimeter but of the opposite sign.

qreaction  qcalorimeter
In order to get the molar enthalpy change, ∆H, for the reaction we have to
divide the heat for the reaction by the number of moles (keeping limiting
reagent, LR, in mind).
qreaction
H reaction 
nLR
In this way we can calculate the molar enthalpy change for reactions that do
not occur at high temperatures
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Example
When 0.2006 g of oxalic acid (C2O4H2) is burnt in the calorimeter
whose heat capacity is 1.238 kJ/K. the temperature increased by 0.4577
K. Calculate dH°comb. (Mw (C2O4H2) = 90.03 g/mol)

Solution qP  CT
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qcalor.  1.238  0.4577  0.57kJ

qcomb.  qcalorimeter qcomb.  0.57kJ

qreaction
H reaction  n
0.2006
 2.23 103 mole
nLR 90.03

0.56
H comb.    251.12kJ
2.23 103
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III-5. Hess’ Law of constant heat summation

Hess’ Law is a restatement of the fact that enthalpies are state functions.
Hess’ Law says that :
If a series of reactions add up to give another reaction, then the enthalpies
of those reactions add up to give the enthalpy of the overall reaction. We
can show this in the following steps:
CHAPTER (III)

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CHAPTER (III)

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III-6. Standard Enthalpies of Formation, H of

An enthalpy of formation is the heat of reaction when one mole of
substance is formed from its elements in their standard states.

General remarks
The standard states are 1 atm pressure and 25°C
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The standard enthalpy of formation for all elements in their standard states
and reference forms is 0.00 kJ
The reference forms are the forms for elements with more than one
allotrope . An allotrope is one form of an element that has two or more
distinct forms. Examples of allotropes are Oxygen (O2, reference form)
and Ozone (O3), also Carbon has Diamond, Graphite (reference form),
and C60.
The general formula for the enthalpy change of a reaction obtained from
standard enthalpies of formation is:
H o   nH
products
o
f   mH
reactan ts
o
f

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In similar way, E ,o is given as

E o   nE
products
o
f   mE
reac tan ts
o
f
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CHAPTER (III)

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15 ‫الشريحة‬

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University

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III-7. The Temperature Dependence of

Reaction Enthalpies
The enthalpies of reactions calculated from a table of standard enthalpies of
formation usually apply to a temperature of 25 oC.
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For these data to be of a wider value, a means for determining the enthalpies
of reactions at other temperatures must be available. This can be done by
writing the enthalpy of the reaction as:

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CHAPTER (III)

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CHAPTER (III)

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III-8. Enthalpy of Phase Changes

Now we want to consider changes in phase; that
is, the system changes from phase to phase for
example, a solid to a liquid, Fig. (III-2).
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o o
Fig. (III-2) Heat curve for H2O from 25 C to 125 C
at 1 atm.

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The heating of ice at -25 oC to +125 oC

at constant pressure (1 atm) will exhibit
the following characteristics:
 Initially, the heat input is used to
increase the temperature of the ice, but
the ice does not change its phase
(remains a solid)
 As the temperature approaches
some critical point (i.e. the melting
temperature of ice), the kinetic energy o o
Fig. (III-2) Heat curve for H2O from 25 C to 125 C
of the molecules of water is sufficient
at 1 atm.
to allow the molecules to begin sliding
one phase past e to another.
 As the ice begins to melt, additional input of heat energy does not raise
the temperature of the water, rather it is used to overcome the
intermolecular attraction during the phase change from solid to liquid

 Once the water is completely in a liquid phase, the amount of

heat input raises the temperature of the liquid water

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 As the temperature approaches

another critical point (the
vaporization, or boiling, temperature
of water) the kinetic energy of the
molecules is sufficient to allow the
separation of molecules into the gas
phase
 As the liquid begins to boil,
additional input of heat energy does o o
not raise the temperature of the water, Fig. (III-2) Heat curve for H2O from 25 C to 125 C
rather it used to overcome the at 1 atm.
intermolecular attractions during the
phase change from liquid to gas

 Once the water molecules is completely exist in the gas phase, additional
heat input raises the temperature of the water vapor

Note: greater energy is needed to vaporize water than to

melt it (Explain)
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Heating ice, water and water vapor

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CHAPTER (III)

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II-9. Problems

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Text resources
J. M. Seddon and J. D. Gale, Thermodynamics and Statistical Mechanics, The Royal
Society of Chemistry, (2001)
G. W. Castellan, Physical Chemistry, 2nd Edn. (1971), Adison-Wesley Publishing
Company, Amesterdam
I. Tinoco, Jr, K. Sauer and J. C. Wang, Physical Chemistry, (1978), Prentice-Hall, Inc.,
New Jersey
W. J. Moore, Basic Physical Chemistry, (1983), Prentice-Hall, Inc., New Jersey
J. R. Wan and A. P. H. Peters, Concise Chemical Thermodynamics, 2nd Edn. (1996),
Taylor & Francis e-Library.http://www.ebookstore.tandf.co.uk/.”
R. J. Silbey and R. A. Alberty, Physic al Chemistry, 3rd Edn. (2001), John wiley &
Sons, New York.
I. N. Levine, Physical Chemistry, 5th Edn. (2003), McGraw-Hill, New York.

Electronic Web resources

http://www.statemaster.com/encyclopedia/Thermochemistry
David Ronis, The Second Law of Thermodynamics, Chemistry CHEM
213W.http://ronispc.chem.mcgill.ca/ronis/chem213/hnd7.pdf
http://www.chem.arizona.edu/~salzmanr/480a/480ants/2ndlawap/2ndlawap.html
http://www.chem.arizona.edu/~salzmanr/480a/480ants/mixing/mixing.html
http://staff.um.edu.mt/jgri1/teaching/che2372/notes/04/g_a/g_a.html#p1
http://www.mikeblaber.org/oldwine/chm1045/notes/Forces/State/Forces04.htm
http://scienceaid.co.uk/chemistry/physical/images/entropychange
http://www.elcamino.edu/faculty/pdoucette/Thermochemistry-practice-problems-key.pdf
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