Physical pharmacy

Lec.5 Dr. Hayder Kadhim Drais

Thermodynamics:
Thermodynamics deals with the quantitative relationships of interconversion of the various
forms of energy, including mechanical, chemical, electric, and radiant energy.

Although thermodynamics was originally developed by physicists and engineers interested in the
efficiencies of steam engines, the concepts formulated from it have proven to be extremely
useful in pharmacy.

Work and energy:

Let us begin with the mechanical concept of work as the product of a force and a displacement:

The units of work are consequently those of force and length. Now from Newton’s laws of
motion,

force therefore has the units : 1 kg ⋅ m/s2

, which is also called a newton, N. 1 N = 1 kg ⋅ m/s2

Hence the units of work are either 1 kg ⋅ m2/s2

Or N m.

Energy is defined as any property that can be produced from or converted into work
(including work itself ). Therefore work and energy have the same dimensions, although
different units may be used to describe different manifestations of energy and work. For
example, 1Nm =1 J ( joule), and energy is often given in joules or kilojoules. Here are
relationships to earlier energy units:

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Note: erg: Its name is derived from ergon, a Greek word meaning 'work' or 'task'.
Note: The work is a product of an intensive property (force) and an extensive property
(displacement). In general, work or energy can be expressed as this product:

Here are several examples of previous equation:

All forms of work are, at least in principle, completely interconvertible. For example, one
could use the electrical energy provided by a battery to drive a (frictionless) piston that converts
the electrical work to an equivalent amount of work of expansion.

Heat and energy:

Heat is that form of energy that is transferred from one place to another as a consequence of a
difference in temperature between the two places. Numerically heat is expressed in joules (J) or
calories (cal).
Heat is not ‘‘degree of hotness,’’ which, as we have seen, is measured by temperature.

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Since both work and heat are forms of energy, they are closely connected. Work can be
completely converted into an equivalent amount of heat (e.g., through friction). The
converse is not possible, however; it is found experimentally that heat cannot be completely
converted into an equivalent amount of work (without producing changes elsewhere in the
surroundings).

The chemical thermodynamics is concerned with the energy. This energy is a consequence
of the electronic distribution within the material, and of three types of atomic or molecular
motion:
1. Translation, the movement of individual molecules in space;
2. Vibration, the movement of atoms or groups of atoms with respect to each other within a
molecule; and
3. Rotation, the revolution of molecules about an axis.

If a material object is subjected to an external source of heat, so that the object absorbs heat and
its temperature rises, the atoms and molecules increase their translational, vibrational, and
rotational modes of motion.

Energy is the way of describing and measuring these molecular and atomic distributions
and motions, as well as the electronic distribution within atoms and molecules.

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Systems and states:
The system typically consists of a specified amount of chemical substance or substances,
such as a given mass of a gas, liquid, or solid. Whatever exists outside of the system is called
the surroundings. Several types of systems:

1. Isolated Systems: These systems are completely uninfluenced by their surroundings.

This means that neither matter nor energy can flow into or out of the system.
2. Closed Systems: Energy may be exchanged with the surroundings, but there can be no
transfer of matter across the boundaries of the system.
3. Open Systems: Both energy and matter can enter or leave the system.

We can also speak of a homogeneous system, which is completely uniform in composition;

or a heterogeneous system, which consists of two or more phases.

Thermodynamic processes and equilibrium:

A system whose observable properties are not undergoing any changes with time is said to
be in thermodynamic equilibrium. Thermodynamic equilibrium implies that three different
kinds of equilibrium are established:
1. Thermal equilibrium (all parts of the system are at the same temperature),
2. Chemical equilibrium (the composition of the system is not changing), and
3. Mechanical equilibrium (there are no macroscopic movements of material within the
system).

Many kinds of processes can be carried out on thermodynamic systems, and some of these
are of special theoretical or practical significance:

1. Isothermal processes: are those in which the system is maintained at a constant-

temperature. (This is easy to do with a constant-temperature bath or oven.) Maintaining a
constant temperature requires that the heat loss or gain by the surroundings. Thus an isothermal
process requires either a closed or an open system, both of these allowing energy to be
exchanged with the surroundings.
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2. An adiabatic process: is one in which no heat enters or leaves the system. An adiabatic
process requires an isolated system. Obviously if the process is adiabatic, the temperature of the
system may change.

3. A spontaneous process is one that occurs ‘‘naturally’’; it takes place without

intervention. For example, if a filled balloon is punctured, much of the contained gas
spontaneously expands into the surrounding atmosphere.

In an equilibrium chemical reaction, which we may write as:

it is conventional to consider the reaction as occurring from left to right as written. Thus if the
position of equilibrium favors M + N (the products), the reaction is said to be spontaneous. If the
reactants (A + B) are favored, the reaction is nonspontaneous as written.
4. The reversible process: Is one more important type of thermodynamic process. Suppose we
have a thermodynamic system at equilibrium, now let an infinitesimal alteration be made in one
of the thermodynamic variables (say, T or P) this will cause an infinitesimal change in the state
of the system. If the alteration in the variable is reversed, the process will reverse itself exactly,
and the original equilibrium will be restored. This situation is called thermodynamic
reversibility. Reversibility requires that the system always be at, or infinitesimally close to,
equilibrium.

The first law of thermodynamics:

The first law is a statement of the conservation of energy. It states that, although energy can be
transformed from one kind into another, it cannot be created or destroyed. Put in another
way, the total energy of a system and its surroundings remains constant during any operation.
This statement follows from the fact that the various forms of energy are equivalent, and when
one kind is formed, an equal amount of another kind must disappear.

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According to the first law, the effects of heat (Q) and work (W) in a given system during a
transformation from an initial thermodynamic state to a final thermodynamic state are related to
an intrinsic property of the system called the internal energy, defined as

Where:
E2 is the internal energy of the system in its final state and
E1 is the internal energy of the system in its initial state,
Q is the heat, and W is the work.

The change in internal energy ∆E is related to Q and W transferred between the system and its
surroundings. Equation (3–1) also expresses the fact that work and heat are equivalent ways of
changing the internal energy of the system.

Maximum work:
The work done by a system in an isothermal expansion process is at a maximum when it is
done reversibly.
No work is accomplished if an ideal gas expands freely into a vacuum, where P = 0, because
any work accomplished depends on the external pressure. Of course, if the external pressure
is continually increased, the gas is compressed rather than expanded, and work is done on the
system rather than by the system in an isothermal reversible process:

Hess’s law and heat of combustion:

It is not possible to directly measure the heats of formation of every known compound.
Incomplete or side reactions often complicate such determinations. However, Hess showed that
because ∆H( change in enthalpy) ∆H = Hproducts − Hreactants depends only on the initial
and final states of a system, thermochemical equations for several steps in a reaction could
be added and subtracted to obtain the heat of the overall reaction. The principle is known as
Hess’s law and is used to obtain heats of reaction that are not easily measured directly.
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The second law of thermodynamics:
In ordinary experience, most natural phenomena are observed as occurring only in one
direction. For instance,
heat flows spontaneously only from hotter to colder bodies.
gases expand naturally from higher to lower pressures, and
solute molecules diffuse from a region of higher to one of lower concentration.
These spontaneous processes will not proceed in reverse without the intervention of some
external force to facilitate their occurrence.

Although spontaneous processes are not thermodynamically reversible, they can be carried
out in a nearly reversible manner by an outside force.

The first law of thermodynamics simply observes that energy must be conserved when it is
converted from one form to another.
The second law refers to the probability of the occurrence of a process based on the observed
tendency of a system to approach a state of energy equilibrium.

The historical development of the thermodynamic property that explains the natural
tendency of the processes to occur, now called entropy.

Entropy:
Heat flows from objects of high temperature to objects at low temperature and this process
increases the disorder of the system. Entropy is a measure of a system’s disorder.
If an amount of heat Q flows into a system at constant temperature, then the change in entropy
(∆S) is:

Every irreversible process increases the total entropy of the universe. Reversible processes do
not increase the total entropy of the universe.

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The third law of themodynamics:
The third law of thermodynamics states that the entropy of a pure crystalline substance is zero
at absolute zero because the crystal arrangement must show the greatest orderliness at this
temperature

The consequences of the third law are that an absolute value for the entropy can be calculated,
based on absolute zero as a reference point. Given this definition, the absolute entropy can be
written as:

Where:
Spoly : is the entropy of the polymorphic/crystalline form at absolute zero.
Cp: the molar heat capacity at constant pressure.
If the substance is a perfect crystal, then Spoly=0.

Gibbs free energy G

There are two factors involved in determining the direction of chemical chang:

A. The system seeks to minimize its energy (ΔH)

B. The system seeks to maximize its entropy(ΔS)

Gibbs free energy ΔG, is a state function that links the first and the second law of
thermodynamics and determine the direction of chemical changes

oG =ΔH−TΔS

ΔG = 0 at constant (Temperature &Pressure) and the system is at equilibrium

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If ΔG is negative it means that the process is spontaneous
If ΔG is zero, it means that the system is at equilibrium
If ΔG is positive it means that the process is non-spontaneous

A more negative ΔH and more positive ΔS favors spontaneous reaction, by making ΔG more
negative.

If TΔS < ΔH, and ΔH is negative, then ΔG will be negative (the process is spontaneous).
If TΔS < ΔH, and ΔH is positive, then ΔG will be positive(the process is non spontaneous)

If TΔS > ΔH, then ΔG will be negative (i.e. the process is spontaneous regardless whether ΔH is
negative or positive

Example:

ΔH and ΔS for the transition from liquid water to ice at - 10°C and at 1 atm pressure are - 1343
cal/mole and -4.91 cal/mole deg, respectively. Compute Δ for the phase change at this
.temperature (-10°C = 263.2 K) and indicate whether the process is spontaneous

Answer:
oG =ΔH−TΔS

ΔG = -1343 - [263.2 X (-4.91)] = -51 cal/mole = -213 joules

The process is spontaneous, as reflected in the negative

value of ΔG.