General Chemistry I

Dr. PHAN TI HUN

Faculty of Food Science and Technology
Nong Lam University

Module 4:
Chemical Thermodynamics
Zeroth Law of Thermodynamics.
First Law of Thermodynamics (state quantities: internal
energy, enthalpy, heat capacity and work; heat of
combustion, bond energies).
Second Law of Thermodynamics (state quantities: entropy,
free energy; chemical potential, chemical equilibrium).

What is Thermodynamics?
Thermodynamics can be defined as the science of energy.
The name thermodynamics stems from the Greek words
therme (heat) and dynamis (power), which is most
descriptive of the early efforts to convert heat into power.
In thermodynamics we study the energy changes that
accompany physical and chemical processes.

Some thermodynamic terms

A system is defined as a quantity of matter or a region in
space chosen for study. The mass or region outside the
system is called the surroundings. The universe is the
system plus its surroundings.
The real or imaginary surface that separates the system from
its surroundings is called the boundary. The boundary of a
system can be fixed or movable.

Systems may be considered to be closed or open.

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A closed system
A closed system (also known as
a control mass) consists of a
fixed amount of mass, and no
mass can cross its boundary. But
energy, in the form of heat or
work, can cross the boundary;
and the volume of a closed
system does not have to be fixed.
If even energy is not allowed to
cross the boundary, that system
is called an isolated system.
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An open system
An open system (also known as a
control volume) is a properly
selected region in space.
Both mass and energy can cross the
boundary of a control volume.

Properties of a system
Any characteristic of a system is called a property. Some
familiar properties are pressure, temperature, volume, and
mass, viscosity, thermal conductivity...
Properties are considered to be either intensive or
extensive.
Intensive properties are those that are independent of the
mass of a system, such as temperature, pressure, and
density.
Extensive properties are those whose values depend on
the size (or extent) of the system. Total mass, total volume,
and total momentum are some examples of extensive
properties.
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State and equilibrium

The word state refers to the
condition of a system as described
by its properties. Since there are
normally relations among the
properties of a system, the state
often can be specified by providing
the values of a subset of the
properties.
Thermodynamics
deals
with
equilibrium states. A system in
equilibrium experiences no changes
when it is isolated from its
surroundings.
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Process, path and cycle

Any change that a system undergoes
from one equilibrium state to another is
called a process, and the series of states
through which a system passes during a
process is called the path of the
process.
To describe a process completely, one
should specify the initial and final
states of the process, as well as the path
it follows, and the interactions with the
surroundings.
A thermodynamic cycle is a sequence
of processes that begins and ends at the
same state.
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State functions
The properties of a system, such as P, V, T, are called state
functions. The value of a state function depends only on the
state of the system and not on the way in which the system
came to be in that state. A change in a state function
describes a difference between the two states. It is
independent of the process or pathway by which the change
occurs.
The most important use of state functions in thermodynamics
is to describe changes. We describe the difference in any
quantity, X, as:
X = Xfinal - Xinitial

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The zeroth law of thermodynamics

When an object is brought into contact with another object
that is at a different temperature, heat is transferred from
the object at higher temperature to the one at lower
temperature until both objects attain the same temperature.
The zeroth law of thermodynamics states that if two
objects are in thermal equilibrium with a third object, they
are also in thermal equilibrium with each other.

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The first law of thermodynamics

According to the first law of thermodynamics, The total
amount of energy in the universe is constant.
The Law of Conservation of Energy is just another
statement of the First Law of Thermodynamics.Energy is
neither created nor destroyed in ordinary chemical
reactions and physical.
Based on this law, we can say that the energy is just taken
from one form and converted to another form.

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Energy
Energy is the capacity to do work or to transfer heat.
We classify energy into two general types: kinetic and
potential.
Kinetic energy (KE) is the energy of motion.
Ekinetic= mv2
Potential energy (PE) is the energy that a system
possesses by virtue of its position or composition.
The total internal energy of a system (E) is the sum of its
potential and kinetic energies.
Etotal = KE + PE
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Forms of energy

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Forms of energy

If we drop a rock, its

potential energy is
converted into kinetic
energy as it falls, and it
could do work on
something it hits.

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Forms of energy
The chemical energy in a fuel
or food comes from potential
energy stored in atoms due to
their arrangements in the
molecules.
This stored chemical energy
can
be
released
when
compounds undergo chemical
changes, such as those that
occur in combustion and
metabolism.
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Forms of energy
CH4(g) + 2O2(g) => CO2(g) + 2H2O(l) + 890 kJ

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Enthalpy and enthalpy changes

Enthalpy (H) is defined as:
H = E + PV
Enthalpy is also a state function. It is not necessary to
know the absolute enthalpy (heat content) of a system.
However, we are interested in the change in enthalpy.
The quantity of heat transferred into or out of a system as it
undergoes a chemical or physical change at constant
pressure, qp, is defined as the enthalpy change, H, of the
process.
H = Hfinal - Hinitial
H = Hsubstances produced Hsubstances consumed
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Thermochemical equations
We always interpret H as the enthalpy change for the
reaction as written; that is, as (enthalpy change)/(mole of
reaction), where the denominator means for the number of
moles of each substance shown in the balanced equation.
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) + 1367 kJ
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) H= -1367 kJ/mol rxn

(mole of reaction = abbreviate mol rxn.)

The negative sign indicates that this is an exothermic reaction
(i.e., it gives off heat).

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Calorimetry
The energy change associated with a chemical or physical
process can be determined by using an experimental
technique called calorimetry.
This technique is based on observing the temperature
change when a system absorbs or releases energy in the
form of heat.
The experiment is carried out in a device called a
calorimeter, in which the temperature change of a known
amount of substance (often water) of known specific heat is
measured.
This heat capacity of a calorimeter is sometimes called its
calorimeter constant.
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Calorimeter
Bomb calorimeter
Coffee-cup calorimeter

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Exercise
Use electric heater to add 3.358 kJ of heat to a calorimeter
that contains 50g of water. The temperature of the water
and the calorimeter, originally at 22.34C, increases to
36.74C. Calculate the heat capacity of the calorimeter in
J/C. The specific heat of water is 4.184 J/g C.
Ans:

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Exercise
A 50 mL sample of 0.4 M copper(II) sulfate solution at 23.35C
is mixed with 50 mL of 0.6 M sodium hydroxide solution, also at
23.35C, in the coffee-cup calorimeter (previous exercise). After
the reaction occurs, the temperature of the resulting mixture is
measured to be 25.23C. The density of the final solution is 1.02
g/mL. Calculate the amount of heat evolved. Assume that the
specific heat of the solution is the same as that of pure water,
4.184 J/g C.
CuSO4(aq) + 2NaOH(aq) Cu(OH)2(s) + Na2SO4(aq)
Ans:

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The thermodynamic standard state

The thermodynamic standard state of a substance is its
most stable pure form under standard pressure (1 atm) and at
specific temperature (25C or 298 K).
Keep in mind the following conventions for thermochemical
standard states.
1. For a pure substance in the liquid or solid phase, the standard
state is the pure liquid or solid.
2. For a gas, the standard state is the gas at a pressure of one
atmosphere; in a mixture of gases, its partial pressure must be
one atmosphere.
3. For a substance in solution, the standard state refers to onemolar concentration.

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12

Standard enthalpy changes

The standard enthalpy change, H0axn, for reaction
reactants products
refers to the H when the specified number of moles of
reactants, all at standard states, are converted completely to the
specified number of moles of products, all at standard states.
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) H0rxn = - 1367 kJ/mol rxn

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Standard molar enthalpies of formation, HOf

The standard molar enthalpy of formation, Hf0 , of a
substance is the enthalpy change for the reaction in which
one mole of the substance in a specified state is formed
from its elements in their standard states.
By convention, the Hf0 value for any element in its
standard state is zero.
H2(g) + 1/2O2(g) H2O(l)

Hf0 = - 285.8 kJ/mol rxn

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13

Selected Standard Molar Enthalpies of

Formation at 298 K

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Exercise
The standard molar enthalpy of formation of ethanol,
C2H5OH(l), is - 277.7 kJ/mol. Write the thermochemical
equation for the reaction for which H0rxn = - 277.7 kJ/mol rxn.
Ans:

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H0axn vs Hf0
The enthalpy change for a balanced equation that gives a
compound from its elements does not necessarily give a
molar enthalpy of formation for the compound.

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Hesss law
Many reactions are difficult to calculate with the standard
enthalpies of formation or calorimetry. Enthalpy is a state
function that means that the calculation is independent of
the pathway or calculation.
Hesss Law states that The enthalpy change for a reaction
is the same whether it occurs by one step or by any series
of steps.
It means that an enthalpy change for a reaction can be
calculated from the sum of two or more reactions.
H0rxn = H0a+ H0b + H0c + ...
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15

Exercise
Use the thermochemical equations shown here to determine
H0axn at 25C for the following reaction.

Ans

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Hesss law
Another interpretation of Hesss Law lets us use tables of
Hf0 values to calculate the enthalpy change for a reaction.
H0axn = n H0f products - n H0f reactants

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Exercise

Ans:

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Bond energies
The bond energy (B.E.) is the amount of energy necessary to
break one mole of bonds in a gaseous covalent substance to
form products in the gaseous state at constant temperature and
pressure.

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Bond energy and Hesss law

A special case of Hesss Law involves the use of bond
energies to estimate heats of reaction (the enthalpy change
for a reaction).
H0axn = B.E.reactants - B.E.products (only in gas phase)

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Single bond energies (kJ/mol of bonds)

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Single and multiple bond energies

(kJ/mol of bonds)

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Exercise
Estimate the heat of reaction at 298 K for the following
reaction:
N2(g) + 3H2(g) 2NH3(g)
Ans:

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Change in internal energy, E

The internal energy of a system can be changed by flow of
work, heat or both.
E = Efinal Einitial = Eproducts Ereactants = q + w
The terms q and w represent heat and work, respectively.
Based on the above equation, these conventions are followed:
q is positive: Heat is absorbed by the system from the
surroundings.
q is negative: Heat is released by the system to the surroundings.
w is positive: Work is done on the system by the surroundings.
w is negative: Work is done by the system on the surroundings.
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Change in internal energy, E

The only type of work involved in most chemical and
physical changes is pressurevolume work.
From dimensional analysis we can see that the product of
pressure and volume is work.

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Change in internal energy, E

When energy is released by a reacting system, E is negative;
energy can be written as a product in the equation for the
reaction.
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) + 887 kJ
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
E= - 887 kJ
When the system absorbs energy from the surroundings, E is
positive; energy can be written as a reactant in the equation.
CO2(g) + 2H2O(l) + 887 kJ CH4(g) + 2O2(g)
CO2(g) + 2H2O(l) CH4(g) + 2O2(g)
E= + 887 kJ

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Change in internal energy, E

E = Efinal Einitial = Eproducts Ereactants = q + w
When a gas is produced against constant external pressure,
such as in an open vessel at atmospheric pressure, the gas
does work as it expands against the pressure of the
atmosphere. If no heat is absorbed during the expansion,
the result is a decrease in the internal energy of the system.
On the other hand, when a gas is consumed in a process,
the atmosphere does work on the reacting system.
The work done on or by a system depends on the external
pressure and the volume.
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Change in internal energy, E

When the external pressure is constant during a change, the
amount of work done is equal to this pressure times the
change in volume. The work done on a system equals -PV
or -P(V2 - V1).
Compression (volume decreases)
Work is done by the surroundings on the system, so the
sign of w is positive.
V2 is less than V1, so V = (V2 - V1) is negative.
W = -PV is positive
Can be due to a decrease in number of moles of gas (n
is negative).
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Change in internal energy, E

Expansion (volume increases)
Work is done by the system on the surroundings, so the
sign of w is negative
V2 is greater than V1, so V = (V2 - V1) is positive.
W = -PV is negative
Can be due to an increase in number of moles of gas (n
is positive).
In constant-volume reactions, no P V work is done. The
change in internal energy of the system is just the amount of
heat absorbed or released at constant volume, qv.
E = qv
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Change in internal energy, E

Predict the sign of w and tell whether work is done on or by
the system.
a) 2NH4NO3(s) 2N2(g) + 4H2O(g) + O2(g)
b) H2(g) + Cl2(g) 2HCl(g)
c) 2SO2(g) + O2(g) 2SO3(g)
Ans:

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Exercise
A 1 gram sample of ethanol was burned in a bomb
calorimeter whose heat capacity had been determined to be
2.71 kJ/C. The temperature of 3000 grams of water rose
from 24.284C to 26.225C. Determine E for the reaction
of ethanol. The specific heat of water is 4.184 J/g C. The
combustion reaction is
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)
Ans:

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Relationship between H and E

The fundamental definition of enthalpy, H, is
H = E + PV
For a process at constant temperature and pressure:
H =
E
+PV
H = q + w
+PV
H = q + (-P V)
+PV
H = qp (constant T and P)
For a reaction studied at constant pressure, the flow of heat is a
measure of the change in enthhalpy for the system. Therefore,
the terms heat of reaction and change in enthalpy are used
interchangeably for reaction studied at constant pressure.
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Relationship between H and E

H = E + PV
(1)
The difference between E and H is the amount of expansion
work (PV work) that the system can do. Unless there is a
change in the number of moles of gas present, this difference is
extremely small and can usually be neglected.
For an ideal gas, At constant temperature and constant pressure,
PV = (n)RT.
H = E + (n)RT
(2)
The form (1) is very useful for physical changes that involve
volume changes, such as expansion or compression of a gas.
When a chemical reaction occurs and causes a change in the
number of moles of gas, it is more convenient to use the
relationship in the form (2).
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Spontaneity of physical and chemical changes

Reactants Products
Which would be more stable at the given conditionsthe
reactants or the products?
A change for which the collection of products is
thermodynamically more stable than the collection of
reactants under the given conditions is said to be productfavored, or spontaneous, under those conditions.
A change for which the products are thermodynamically
less stable than the reactants under the given conditions is
described as reactant-favored, or nonspontaneous, under
those conditions.
A spontaneous chemical reaction or physical change is one
that can happen without any continuing outside influence.
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Entropy, S
The energy needed to cause a small temperature change in a
sample of matter is a measure of the dispersal of matter, or
disorder in that sample. This measure is a thermodynamic
function called entropy, S.
S = kB ln
where
kB = Boltzmanns constant, the gas constant per molecule (R/NA)
= the number of microstates corresponding to a given state
(including both position and energy).
S = Sfinal - Sinitial
The greater the disorder of a system, the higher is its entropy.
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Entropy, S

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Entropy
The entropy of a substance at any condition is its absolute
entropy, also called standard molar entropy (often at 1atm,
298 K - S0298 or S0). Standard molar entropy values are
usually expressed in units of J/K.mol.
The entropy of a pure, perfect crystalline substance
(perfectly ordered) is zero at absolute zero (0 K) (The third
law of thermodynamics).
At 298 K, any substance is more disordered than if it were in
a perfect crystalline state at absolute zero, so S0298 values for
compounds and elements are always positive (unlike Hf0 for
element is zero).
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Standard entropy change

The standard entropy change, S0, of a reaction can be
determined from the absolute entropies of reactants and
products. The relationship is analogous to Hesss Law.
S0rxn = n S0products - n S0reactants
Absolute entropies at 298 K for a few common substances

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The second law of thermaldynamics

In spontaneous changes, the universe tends toward a state
of greater disorder (If the entropy of a system increases
during a process, the spontaneity of the process is favored
but not required.)
The Second Law of Thermodynamics says that the entropy
of the universe (not the system) increases during a
spontaneous process.
Suniverse = Ssystem + Ssurroundings > 0 (spontaneous process)

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Example
Because the ideal gas samples (below) do not interact with
the surroundings, so the entropy of the surroundings does
not change. In this case Suniverse = Ssystem.
unmixed gases mixed gases

Suniverse = Ssystem > 0.

mixed gases unmixed gases

Suniverse = Ssystem < 0.

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Example

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Exercise
Calculate the entropy change at 25C and 1 atm pressure
for the reaction of hydrazine with hydrogen peroxide. Do
you think the reaction is spontaneous?

Ans:

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Attention
Suniverse is positive for all spontaneous (product-favored)
processes. Unfortunately, it is not possible to make direct
measurements of Suniverse. Consequently, entropy changes
accompanying physical and chemical changes are reported
in terms of Ssystem. The symbol S refers to the change in
enthalpy of the reacting system.
Because changes in the thermodynamic quantity entropy
may be understood in terms of changes in molecular
disorder, we can often predict the sign of Ssystem.

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Predictable entropy changes for the system

Phase changes: melting vaporization and sublimation take
place with large increases in disorder, and hence with
increases in entropy. For the reverse processes of freezing,
condensation, and deposition, entropy decreases because
order increases.
Temperature changes: as any sample is warmed, the
molecules undergo more (random) motion; hence entropy
increases as temperature increases.
Volume changes: when the volume of a sample of gas
increases, the molecules can occupy more positions, and
hence are more randomly arranged than when they are
closer together in a smaller volume.
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Predictable entropy changes for the system.

Mixing of substances, even without chemical reaction.
Situations in which the molecules are more mixed up are
more disordered, and hence are at higher entropy.
Increase in the number of particles: any process in which
the number of particles increases results in an increase in
entropy.
Changes in the number of moles of gaseous substances:
processes that result in an increase in the number of moles
of gaseous substances have Ssystem > 0.

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Free energy change and spontaneity

Free energy (G) is a thermodynamic function, related to
spontaneity and is especially useful in dealing with the
temperature dependence of spontaneity. It is defined as:
G = H TS (Gibbs-Helmholtz equation)
The Gibbs free energy change, G, at constant temperature and
pressure, is
G = H - TS
(constant T and P)
The amount by which the Gibbs free energy decreases is the
maximum useful energy obtainable in the form of work from
a given process at constant T and P.
It is also the indicator of spontaneity of a reaction or physical
change at constant T and P. If there is a net decrease of useful
energy, G is negative and the process is spontaneous.
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Free energy change and spontaneity

G is positive Reaction is nonspontaneous (reactantfavored).
G is zero System is at equilibrium.
G is negative Reaction is spontaneous (product-favored).

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The standard state for G0

The standard state for G0 is the same as for H0 - 1 atm
and the specified temperature, usually 25C (298 K).
The standard free energy of formation of a compound,
G0f, is analogous to the enthalpy of formation, H0f. It is
defined as the free energy change per mole when a
compound is formed from the elements in their stable states
at 1 atm.

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The standard state for G0

Values of G0f can be used to calculate free energy
changes for reactions.
G0rxn = nG0f products - nG0f reactants
The value of G0rxn allows us to predict the spontaneity of a
very special hypothetical reaction that we call the standard
reaction.
In the standard reaction, the numbers of moles of reactants
shown in the balanced equation, all at standard conditions,
are completely converted to the numbers of moles of
products shown in the balanced equation, all at standard
conditions.

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Exercise
Evaluate G0 for the following reaction at 298 K. Is the
standard reaction spontaneous?

Ans:

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Calculation of G0 at other temperature

To a good degree of approximation, the temperature
variation of H0 and S0 can be neglected in the GibbsHelmholtz equation.
G0 = H0 - TS0
at temperature other than 25C, only the value of T needs to
be changed. The quantities of H0 and S0 can be calculated
in the usual way.

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Exercise
Make the same determination as in the previous Exercise,
using heats of formation and absolute entropies rather than
free energies of formation.

Ans:

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Exercise
Estimate the normal boiling point of bromine, Br2.
Assume that H and S do not change with temperature.

Ans:

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The temperature dependence of spontaneity

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Examples

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Exercise
Estimate the temperature range for which the following
standard reaction is product-favored.

Ans:

71

Summary
After you have finished studying this module 4, you should
be able to
Understand the terminology of thermodynamics, and the
meaning of the signs of changes.
Use the concept of state functions.
Carry out calculations of calorimetry to determine changes in
energy and enthalpy.
Use Hesss Law to find the enthalpy change, H, for a
reaction by combining thermochemical equations with
known H values.
Use Hesss Law to find the enthalpy change, H, for a
reaction by using tabulated values of standard molar
enthalpies of formation.
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Summary
Use the First Law of Thermodynamics to relate heat, work,
and energy changes.
Relate the work done on or by a system to changes in its
volume.
Use bond energies to estimate heats of reaction for gas
phase reactions.
Understand what is meant by a product-favored process; by
a reactant-favored process.
Understand the relationship of entropy to the order or
disorder of a system.
Understand how the spontaneity of a process is related to
entropy changesthe Second Law of Thermodynamics.
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Summary
Use tabulated values of absolute entropies to calculate the
entropy change, S.
Calculate changes in Gibbs free energy, G, (a) from values
of H and S and (b) from tabulated values of standard molar
free energies of formation.
Use G to predict whether a process is product-favored at
constant T and P.
Understand how changes in temperature can affect the
spontaneity of a process.
Predict the temperature range of spontaneity of a chemical
or physical process.

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