Laws of Thermodynamics
 The first law of thermodynamics, which is
Introduction to Thermodynamics
Thermochemistry is part of a broader subject
called thermodynamics, which is the scientific
study of the interconversion of heat and other
kinds of energy.
The laws of thermodynamics provide
useful guidelines for understanding the
energetics and directions of processes. In this
section we will concentrate on the first law of
thermodynamics,
which is study of particularly relevant to the
thermochemistry.
 In thermodynamics, we study changes in
the state of a system, which is defined by
the values of all relevant macroscopic
properties, for example, composition,
energy, temperature, pressure, and volume.
 Energy, pressure, volume, and temperature
are said to be state functions —
properties that are determined by the state
of the system, regardless of how that
condition was achieved.
 In other words, when the state of a system
changes, the magnitude of change in any
state function depends only on the initial
and final states of the system and not on
how the change is accomplished.
The state of a given amount of a gas is specified
by its volume, pressure, and temperature.
Consider a gas at 2 atm, 300 K, and
1 L (the initial state). Suppose a process is
carried out at constant temperature such that
the gas pressure decreases to 1 atm. According
to Boyle’s law, its volume must increase to 2 L.
The final state then corresponds to 1 atm, 300 K,
and 2 L. The change in volume ( V ) is
where Vi and Vf denote the initial and final
volume, respectively. No matter how we arrive
at the final state (for example, the pressure of
the gas can be increased first and then
decreased to 1 atm), the change in volume is
always 1 L. Thus, the volume of a gas is a state
function. In a similar manner, we can show
that pressure and temperature are also state
functions.
Energy is another state function. Using potential
energy as an example, we find that the net
increase in gravitational potential energy when
we go from the same starting point to the top
of a mountain is always the same, regardless of
how we get there.
The 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†. How do we know this is so?
It would be impossible to prove the
validity of the first law of
thermodynamics if we had to determine
the total energy content of the universe.
 Even determining the total energy content
of 1 g of iron, say, would be extremely
difficult. Fortunately, we can test the
validity of the first law by measuring
only the change in the internal energy of
a system between its initial state and its
final state in a process. The change in
internal energy E is given by
where Ei and Ef are the internal energies of the
system in the initial and final states,
respectively.
 The internal energy of a system has two
components: kinetic energy and potential
energy.
 The kinetic energy component
consists of various types of molecular
motion and the movement of electrons
within molecules.
 Potential energy is determined by the
attractive interactions between electrons
and nuclei and by repulsive interactions
between electrons and between nuclei in
individual molecules, as well as by
interaction between molecules.
 It is impossible to measure all these
contributions accurately, so we cannot
calculate the total energy of a system
with any certainty. Changes in energy, on
the other hand, can be determined
experimentally

to light the bulb of a flashlight), and surface
work (blowing up a soap bubble).
In this section we will concentrate on
mechanical work.
In thermodynamics, work has a broader meaning
that includes mechanical work (for example, a
crane lifting a steel beam), electrical work (a
battery supplying electrons to light the bulb of
a flashlight), and surface work (blowing up a
soap bubble).
 One way to illustrate mechanical work is to
study the expansion or compression of a
gas.
 Many chemical and biological
processes involve gas volume changes.
Breathing and exhaling air involves the
expansion and contraction of the tiny sacs
called alveoli in the lungs.
 Another example is the internal
combustion engine of the automobile.
The successive expansion and compression
of the cylinders due to the combustion of
the gasoline-air mixture provide power to
the vehicle.
 Figure 6.5 shows a gas in a cylinder fitted
with a weightless, frictionless movable
piston at a certain temperature, pressure,
and volume. As it expands, the gas pushes
the piston upward against a constant
opposing external atmospheric pressure P.
The work done by the gas on the
surroundings is
For gas expansion (work done by the system),
Equation derives from the fact that pressure x
volume can be expressed as (force/area) x
volume; that is,
According to Equation, the units for work done
by or on a gas are liters atmospheres. To
express the work done in the more familiar
unit of joules.
Example shows that work is not a state function.
Although the initial and final states are the
same in (a) and (b), the amount of work done
is different because the external, opposing
pressures are different. We cannot write
for a change. Work done depends not only on
the initial
state and final state, but also on how the process
is carried out, that is, on the path.
Heat
 The other component of internal energy is
heat, q . Like work, heat is not a state
function.
 For example, it takes 4184 J of energy to
raise the temperature of 100 g of water
from 20°C to 30°C. This energy can be
gained (a) directly as heat energy from a
Bunsen burner, without doing any work on
the water; (b) by doing work on the water
without adding heat energy (for example,
by stirring the water with a magnetic stir
bar); or (c) by some combination of the
procedures described in (a) and (b).
 This simple illustration shows that heat
associated with a given process, like
work, depends on how the process is
carried out. It is important to note that
regardless of which procedure is taken, the
change in internal energy of the system,
E , depends on the sum of ( q + w).
 If changing the path from the initial state to
the final state increases the value of q,
then it will decrease the value of w by the
same amount and vice versa, so that E
remains unchanged. In summary, heat and
work are not state functions because they
are not properties of a system. They
manifest themselves only during a
process (during a change). Thus, their
values depend on the path of the process
and vary accordingly.
Enthalpy of Chemical Reactions
Our next step is to see how the first law of
thermodynamics can be applied to processes
carried out under different conditions.
Specifically, we will consider two situations
most commonly encountered in the laboratory;
one in which the volume of the system is kept
constant and one in which the pressure applied
on the system is kept constant.
For any process, the change in enthalpy
according to Equation is given by
We see that for a constant-pressure process, qp =
H . Again, although q is not a state
function, the heat change at constant pressure is
equal to H because the “path” is defined and
therefore it can have only a specific value.
This analogy assumes that you will not
overdraw your bank account.
The enthalpy of a substance cannot be
negative.
is that while you always know your exact bank
balance, there is no way to know the enthalpies
of individual products and reactants. In practice,
we can only measure the difference in their
values. Now let us apply the idea of enthalpy
changes to two common processes, the first
involving a physical change, the second a
chemical change.
of melting ice. Therefore, physical change is
H is a positive quantity. The equation for this
equal to enthalpy change and
H must have a negative sign. Again,
Standard Enthalpy of Formation and Reaction
SPONTANEITY
Exothermicity favors the spontaneity of a
reaction but does not guarantee it. Just as it is
possible for an endothermic reaction to be
spontaneous, it is possible for an exothermic
reaction to be nonspontaneous.
In other words, we cannot decide whether or not Standard entropy is the absolute entropy of a
a chemical reaction will occur spontaneously substance at 1 atm and 25°C. (Recall that the
solely on the basis of energy changes in the standard state refers only to 1 atm. The reason
system. To make this kind of prediction we need for specifying 25°C is that many processes are
another thermodynamic quantity, which turns carried out at room temperature.) The units of
out to be entropy. entropy are J/K or J/K·mol for 1 mole of a
substance.
Entropy
To determine the spontaneity Entropies of elements and compounds are all
thermodynamic quantity called positive (that is, S° >0).
considered.
of the reaction, a Entropy
entropy must be For different substances in the same phase,
Entropy (S) is described as a measure of how molecular complexity determines which ones
spread have higher entropies.
among the contain out or dispersed the energy of
a system is different possible waysthat For example, both diamond and graphite are
system can energy. solids, but diamond has a more ordered
The greater the randomness, the greater the structure and hence a
entropy. smaller Therefore,
Most processes are accompanied by a number diamond
entropy. of microstates. has a smaller
standard entropy than graphite.
Entropy
In 1868 Boltzmann showed that the entropy of Consider the natural gases methane and ethane.
a system is related to the natural log of the Ethane has a more complex structure and
number of microstates (W): hence more ways to execute molecular
motions, which also increase its microstates.
S = k(lnW)
Both helium and neon are monatomic gases,
where k is called the Boltzmann constant (1.38 which cannot execute rotational or vibrational
x 10-23 J/K). Thus, the larger the W, the motions, but neon has a greater standard
greater is the entropy of the system. And entropy than helium because its molar mass is
entropy as a state function, it can be greater.
measured as, Ethane has a greater standard entropy than
ΔS = Sf – Si methane.
where Si and Sf are the entropies of the system
in the initial and final states, respectively. Entropy
 EXAMPLES
Entropy  Predict whether the entropy change is
Or can be translated to, greater or less than zero for each of the
ΔS = k(lnWf) – k(lnWi) following processes:
= kln( / )  freezing ethanol
where Wi and Wf are the corresponding  evaporating a beaker of liquid bromine at
numbers of microstates in the initial and final room temperature
state.  dissolving glucose in water
Thus, if Wf > Wi, ΔS > 0 and the entropy of  cooling nitrogen gas from 80°C to 20°C.
the system increases  Strategy: To determine the entropy change
in each case, we examine whether the
Changes in Entropy number of microstates of the system
 A system with fewer microstates (smaller increases or decreases. The sign of ΔS
W) among which to spread its energy will be positive if there is an increase in
(small dispersal) has a lower entropy. the number of microstates and negative if
 A system with more microstates the number of microstates decreases.
(larger W) among which to spread its Entropy
energy (large dispersal) has a higher  Solution
entropy  Upon freezing, the ethanol molecules are
held rigid in position. This phase
Entropy transition reduces the number of
 microstates and therefore the entropy
decreases; that is, ΔS < 0.
 Evaporating bromine increases the number
of microstates because the Br2 molecules
can occupy many more positions in nearly
empty space. Therefore, ΔS > 0.
 Glucose is a nonelectrolyte. The solution
process leads to a greater dispersal of
matter due to the mixing of glucose and
water molecules so we expect ΔS > 0.
 The cooling process decreases various
molecular motions. This leads to a
decrease in microstates and so ΔS < 0.

Gibbs† free energy (G), or simply free energy:

G = H – TS
All quantities pertain to the system, and T is the
temperature of the system.
You can see that G has units of energy. Like H
and S, G is a state function.
The change in free energy (ΔG)of a
system for a constant-temperature
process is
ΔG = ΔH – TΔS

The standard free-energy of reaction (ΔGo) is

the free-energy change for a reaction when it
occurs under standard-state conditions.
1 mole of the compound is synthesized from its
elements in their standard states.

Law of Thermodynamics
Example
Calculate the standard free-energy
changes for the following reactions at
25°C.
(a) CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
(b) 2MgO(s) 2Mg(s) + O2(g)
Solution
(a)ΔG°rxn = [ΔG°f(CO2) + 2ΔG°f(H2O)] -
[ΔG°f(CH4) + 2ΔG°f(O2)]
=[(-394.4 kJ/mol) + (2)(-237.2 kJ/mol)] -
[(-50.8 kJ/mol) + (2)(0kJ/mol)]
= -818.0 kJ/mol

(b) ΔG°rxn = [2ΔG°f (Mg) + ΔG°f(O2)] -

[2ΔG°f(MgO)]
=[(0 kJ/mol) + (0 kJ/mol)] -
[ (2)(-569.6kJ/mol)]
=1139 kJ/mol