Introduction of

Thermodynamics
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 study the energy effect of
chemical reaction

Chemical reaction energy changes are utilized

to :
◼ Calculate the heat balance of industrial
processes;
◼ Determine the energy of bonds;
◼ Establish the direction of processes.

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 Chemical system
is characterized by

Parameters Functions of state

Absolute values can’t be
can be measured
measured

Mass m,
Internal energy E,
Temperature T,
Enthalpy H,
Pressure P,
Entropy S,
Amount of substance n,
Gibbs free energy G
Concentration c 3
 Chemical
reaction

Exothermic Q>0 (ΔHm<0) Endothermic Q<0 (ΔHm>0)

Heat is liberated Heat is absorbed from

into the surroundings the surroundings

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◼ The energy cannot be created nor destroyed.

Q = ΔU + A,
where Q – an amount of heat;
ΔU – changes in internal energy;
A – a work resisting external forces:
A = PΔV . 5
◼ If a system is exchanged with surroundings by
heat its’ internal energy and enthalpy are
changed:
◼ Q > 0 (heat is liberated) ΔU < 0, ΔH < 0;
◼ Q < 0 (heat is absorbed) ΔU > 0, ΔH > 0.
◼ The value of ΔH is corresponding to the amount
of the heat Q which is absorbed or evolved in
any chemical reaction:
Q = – ΔH
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◼ The standard enthalpy of formation ΔHf
is the enthalpy change when 1 mol of a
pure substance is formed from its elements.
◼ Each element must be in the physical and
chemical form which is most stable at
normal atmospheric pressure (101325 Pa
or 1 atm) and a specified temperature
(usually 298 K or 25 °C).

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Compound ΔHf/kJ·mol–1 Compound ΔHf/kJ·mol– Compound ΔHf/kJ·mol–
1 1

AgCl(s) –127.068 CaO(s) –635.09 KCl(s) –436.747

AgN3(s) +620.6 CaCO3(s) –1206.92 KBr(s) –393.798
Ag2O(s) –31.0 CuO(s) –157.3 MgO(s) –601.7
Al2O3(s) –1675.7 Fe2O3(s) –824.2 NH3(g) –46.11
Br2(l) 0.0 HBr(g) –36.4 NO(g) +90.25
Br2(g) +30.907 HCl(g) –92.307 NO2(g) +33.18
C(s), graphite 0.0 HI(g) +26.48 N2O4(g) +9.16
C(s), diamond +1.895 H2O(g) –241.818 NF3(g) –124.7
CH4(g) –74.81 H2O(l) –285.8 NaBr(s) –361.062
CO(g) –110.525 H2O2(l) –187.78 NaCl(s) –411.153
CO2(g) –393.509 H2S(g) –20.63 O3(g) +142.7
C2H2(g) +226.73 HgO(s) –90.83 SO2(g) –296.83
C2H4(g) +52.26 I2(s) 0.0 SO3(g) –395.72
C2H6(g) –84.68 I2(g) +62.438 ZnO(s) –348.28
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C6H6(l) +49.03
• A spontaneous process is one that takes place
without energy from an external source.

• Heat flows from a hotter object to a colder one.

• An iron object rusts in moist air.
• Sugar dissolves in a cup of coffee.

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• A spontaneous process is one that takes place without energy from an
external source. For a chemical reaction to be spontaneous, it should
proceed as written (from left to right), without an input of energy.
• Examples of Reactions:
• Combustion of methane
• CH4 + 2O2 —> 6CO2 + 2H2O ΔHo = 890.4 kJ/mol

* This reaction is exothermic and is not reversible.

• Solid to liquid phase transition of water
• H2O (s) —> H2O (l) ΔHo = 6.01kJ/mol
• * Ice melting above 0oC and ammonium
nitrate dissolving in water are both
spontaneous process yet endothermic.
Processes that are
spontaneous in one
direction are
nonspontaneous in the
reverse direction.

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◼ Processes that are spontaneous at one
temperature may be nonspontaneous at other
temperatures.
◼ Above 0C it is spontaneous for ice to melt.
◼ Below 0C the reverse process is spontaneous.

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Second Law of Thermodynamics

• states that the state of entropy of the entire universe,

as an isolated system, will always increase over time.
The second law also states that the changes in the
entropy in the universe can never be negative.
• One of the most important implications of
the second law is that it indicates which way time
goes - time naturally flows in a way that increases
disorder.
• The Second Law of Thermodynamics deals with
entropy. It tells whether a process or chemical
reaction can occur. The connection between entropy
and the spontaneity of a reaction is expressed by the
second law of thermodynamics:
• It states that:
“The entropy of the universe increases in a
spontaneous process and remains unchanged in an
equilibrium process.”
• The energy change in the system cannot solely tell
whether a chemical reaction will occur spontaneously.
To make this kind of prediction, another
thermodynamic quantity is needed:

ENTROPY
• It is a quantity that is generally used to describe the
course of a process, that is, whether it is a
spontaneous process and has a probability of
occurring in a defined direction, or a non-
spontaneous process and will not proceed in the
defined direction, but in the reverse direction.
• The unit of entropy is joules per Kelvin (J/K)
• The spreading out of more concentrated molecules and the
spreading out of more concentrated energy are changes from
more order to more random. The changes that occur are the
ones that lead to an increasing randomness of the universe.
Entropy is sometimes referred as the measure of randomness
and disorder.

• At high enough temperature, the spontaneous change is from

Solid Liquid Gas; gas is more random than liquid and liquid is
more random than solid. There is an increase in entropy (S) of
the system by going from solid to liquid to gas.
 Conceptual Example

• Consider putting an ice cube into a cup with water at

room temperature. The water gives off heat to melt
the ice cube, as a result, the entropy of the water
decreases. The ice cubes absorb the same amount of
heat, therefore its entropy increases.
◼ Entropy can be thought of as a measure of
the randomness of a system.
◼ It is related to the various modes of motion in
molecules.
◼ Molecules exhibit several types of motion:
◼ Translational: movement of the entire molecule
from one place to another.
◼ Vibrational: periodic motion of atoms within a
molecule.
◼ Rotational: rotation of the molecule on about an
axis or rotation about  bonds.
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 Entropy
Changes
◼ In general, entropy
increases when
◼ Gases are formed from
liquids and solids.
◼ Liquids or solutions are
formed from solids.
◼ The number of gas
molecules increases.
◼ The number of moles
increases.
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 What general rules apply to
predicting whether an entropy
change is negative or positive?
• :General rules for predicting entropy change of the
system
• 1. If the reaction produces more gas molecules than it
consumes, ΔS° is positive.
• 2. If the total number of gas molecules diminishes, ΔS° is
negative.
• 3. If there is no net change in the total number of gas
molecules, ΔS° may be positive or negative, but will
• be relatively small numerically.
Entropy on the Molecular
Scale

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◼ Each thermodynamic state has a specific number of
microstates, W, associated with it.
◼ Entropy is
S = k lnW
where k is the Boltzmann constant, 1.3810−23 J/K.

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 The entropy of the universe increases
for spontaneous processes:

ΔS > 0

Each system is tended to a randomization

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◼ The number of microstates and, therefore,
the entropy tends to increase with increases
in
◼ Temperature.
◼ Volume (gases).
◼ The number of independently moving
molecules.

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◼ Entropy increases
with the freedom of
motion of
molecules.
◼ Therefore,
S(g) > S(l) > S(s)

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Larger and more complex molecules have
greater entropies.

Standard Entropies

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Entropy changes for a reaction can be calculated
the same way we used for H:

ΔS = ∑ iS0 (products) – ∑ jS0 (reactants)

S°for each component is found in a table.

Note for pure elements:

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• If  G is negative,
the forward
reaction is
spontaneous.
• If ΔG is 0, the
system is at
equilibrium.
• If G is positive,
the reaction is
spontaneous in the
reverse direction.
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 Free Energy and Temperature
◼ There are two parts to the free energy
equation:
▪ H – the enthalpy term
▪ TS – the entropy term

◼ The temperature dependence of free energy

comes from the entropy term.

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