EXAMPLE

The Sprowls Method

• A further simplification of the method of White and Vincent was introduced by
Sprowls. He recognized that the equation of White and Vincent could be used to
construct a table of values of (V) when the weight of the drug, w, was arbitrarily
fixed.
• Sprowls chose as the weight of drug 0.3 g, the quantity for 1 fluid ounce of a 1%
solution. The volume, V, of isotonic solution that can be prepared by mixing 0.3 g
of a drug with sufficient water can be computed for drugs commonly used in
ophthalmic and parenteral solutions. The table can be found in the United States
Pharmacopeia.
 THERMODYNAMICS

• Thermodynamics deals with the quantitative relationships of inter-

conversion of the various forms of energy, including mechanical,
chemical, electric, and radiant energy.

Basic definitions:
• A system in thermodynamics is a well-defined part of the universe
that one is interested in studying.
• The system is separated from surroundings, the rest of the universe
and from which the observations are made, by physical (or virtual)
barriers defined as boundaries
We need to distinguish three types of
system:
• An open system can exchange both
energy and matter with its
surroundings.
• A closed system is a system that can
exchange energy but not matter with its
surroundings.
• An isolated system is a system that can
exchange neither matter nor energy
with its surroundings.
• Energy is that property that determines what molecules can
form, what reactions can occur, how fast they can occur, and in
which direction a reaction has a tendency to occur.

So we can say,
• Energy is the capacity to do work, and
• Work is the process of moving against an opposing force.
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 immediate 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.
• 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 (E),
defined as

where E is the internal energy of the system in its final state and E
2 1

is the internal energy of the system in its initial state, Q is the heat,
and W is the work.
• The internal energy is related to the microscopic motion of the
atoms, ions, or molecules of which the system is composed.

• Knowledge of its absolute value would tell us something about the

microscopic motion of the vibrational, rotational, and translational
components.

• In addition, the absolute value would also provide information about

the kinetic and potential energies of their electrons and nuclear
elements, which in practice is extremely difficult to attain. Therefore,
change of internal energy rather than absolute energy value is the
concern of thermodynamics.
• A system does work when it causes motion against an
opposing force. We can identify when a system does work by
noting whether the process can be used to change the height
of a weight somewhere in the surroundings.

• Heating is the process of transferring energy as a result of a

temperature difference between the systems and its
surroundings.
• It is common to say that ‘energy is transferred as work’ when the
system does work and ‘energy is transferred as heat’ when the
system heats its surroundings (or vice versa).

Note:
For an infinitesimal change in the energy dE, the equation is written as
dE = dq + dw

where dq is the heat absorbed and dw is the work done during the
infinitesimal change of the system. Capital letters Q and W are used
for heat and work to signify finite changes in these quantities.
Sign conventions

• When a system does work, such as by raising a

weight in the surroundings, the energy
transferred as work is reported as a negative
quantity. When work is done on the system is
reported as a positive quantity.

• Similarly, when a system releases heat into the

surroundings is reported as a negative quantity
and when the system absorbs heat from the
surroundings is reported as a positive quantity.
Sign conventions

• The sign convention in thermodynamics: w and q

are positive if energy enters the system (as work
and heat, respectively) but negative if energy
leaves the system.
The molecular interpretation of work and heat
• The clue to the molecular nature of work comes from thinking about
the motion of a weight in terms of its component atoms. When a
weight is raised, all its atoms move in the same direction.

• This observation suggests that work is the transfer of energy that

achieves or utilizes uniform motion in the surroundings.

• Whenever we think of work, we can always think of it in terms of

uniform motion of some kind. Electrical work, for instance,
corresponds to electrons being pushed in the same direction
through a circuit. Mechanical work corresponds to atoms being
pushed in the same direction against an opposing force.
• Now consider the molecular nature of heating. When energy is
transferred as heat to the surroundings, the atoms and molecules
oscillate more rapidly around their positions or move from place to
place more vigorously.

• The key point is that the motion stimulated by the arrival of energy
from the system as heat is random, not uniform as in the case of
doing work. This observation suggests that heat is the mode of
transfer of energy that achieves or utilizes random motion in the
surroundings. A fuel burning, for example, generates random
molecular motion in its vicinity.
Isothermal and Adiabatic Processes
• When the temperature is kept constant during a process, the reaction
is said to be conducted isothermally. An isothermal reaction may be
carried out by placing the system in a large constant-temperature
bath so that heat is drawn from or returned to it without affecting the
temperature significantly.

• When heat is neither lost nor gained during a process, the reaction is
said to occur adiabatically. A reaction carried on inside a sealed
Dewar flask or “vacuum bottle” is adiabatic because the system is
thermally insulated from its surroundings.
• In thermodynamic terms, it can be said that an adiabatic process is
one in which dq = 0, and the first law under adiabatic conditions
reduces to

dw = dE

• Accordingly, when work is done by the system, the internal energy

decreases, and because heat cannot be absorbed in an adiabatic
process, the temperature must fall.
Expansion Work
• Expansion work is the work done when a system expands against
an opposing pressure.

• Expansion work is done in any chemical reaction that involves

gases, such as the oxidation of fuels and photosynthesis, and for a
proper analysis of energy resources it must be taken into account.
• Imagine a vapor confined in a
hypothetical cylinder fitted with a
weightless, frictionless piston of area A ,
as shown in the figure.

• If a constant external pressure Pex is

exerted on the piston, the total force is
P x A because P = Force/Area.
ex
• The vapor in the cylinder is now made to
expand by increasing the temperature, and
the piston moves a distance h . The work
done against the opposing pressure in one
single stage is:

• Now A x h is the increase in volume, ΔV =

V2 − V1 , so that, at constant pressure,
• According to this equation, the external pressure determines how
much work a system does when it expands through a given
volume:

the greater the external pressure, the greater the

opposing force and the greater the work that a system
does.

• When the external pressure is zero, w = 0. In this case, the

system does no work as it expands because it has nothing to push
against. Expansion against zero external pressure is called free
expansion.
Example: A gas expands by 0.5 liter against a constant
pressure of 0.5 atm at 25◦C. What is the work in ergs and in
joules done by the system?
Maximum work
• How can we achieve the greatest work for a given change in volume?

• According to the above equation, the system does maximum work

when the external pressure has its maximum value. The force opposing
the expansion is then the greatest and the system must exert most
effort to push the piston out.

• However, that external pressure cannot be greater than the pressure (P)
of the gas inside the system, for otherwise the external pressure would
compress the gas instead of allowing it to expand. Therefore, maximum
work is obtained when the external pressure is only infinitesimally
less than the pressure of the gas in the system.
• In effect, the two pressures must be adjusted to be the same at all
stages of the expansion: the external pressure must be progressively
reduced so that it remains only infinitesimally lower than the pressure
of the gas at each stage.

• This balance of pressures corresponds to a state of mechanical

equilibrium. Therefore, we can conclude that a system that remains
in mechanical equilibrium with its surroundings at all stages of the
expansion does maximum expansion work.
• In another word, when a system is in a state of mechanical
equilibrium, an infinitesimal change in the pressure results in opposite
directions of change.

• A change that can be reversed by an infinitesimal change in a variable

—in this case, the pressure—is said to be reversible.

• In everyday life ‘reversible’ means a process that can be reversed; in

thermodynamics it has a stronger meaning—it means that a process
can be reversed by an infinitesimal modification in some variable
(such as the pressure).
• For ideal gases, the external pressure can be replaced by the pressure of
an ideal gas, P = nRT/V, and by ensuring that the temperature of the gas
remains constant during the change of state (isothermal process); then

• The maximum work in an isothermal reversible expansion may also be

expressed in terms of pressure because, from Boyle’s law, V2/V1 = P1/P2
at constant temperature. Therefore, the equation can be written as
Example: one mole of water in equilibrium with its vapor is converted into
steam at 100◦C and 1 atm. The heat absorbed in the process (i.e., the heat
of vaporization of water at 100◦C) is about 9720 cal/mole. What are the
values of the three first-law terms Q, W, and ΔE?

The amount of heat absorbed is the heat of vaporization, given as 9720

cal/mole. Therefore,
Q = 9720 cal/mole

The work W performed against the constant atmospheric pressure is

obtained by using the equation, W = −nRT ln(V2/V1).
Now, V1 is the volume of 1 mole of liquid water at 100◦C, or about 0.018
liter. The volume V2 of 1 mole of steam at 100◦C and 1 atm is given by
the gas law, assuming that the vapor behaves ideally:

V2 = RT/P = 0.082 x 373 /1= 30.6 liters

It is now possible to obtain the work,

W = −(1 mole) (1.9872 cal/K mole) (398.15 K) ln(30.6/0.018)

W = −5883 cal

The internal energy change ΔE is obtained from the first-law expression,

ΔE = 9720−5883 = 3837 cal
• Therefore, from the 9720 cal of heat absorbed by 1 mole of water, 5883 cal is
employed in doing the work of expansion, or “PV work,” against an external
pressure of 1 atm. The remaining 3837 cal increases the internal energy of the
system. This quantity of heat supplies potential energy to the vapor molecules,
that is, it represents the work done against the noncovalent forces of attraction.
Enthalpy

• Where a change occurs in a system at constant pressure as, for

example, in a chemical reaction in an open vessel, then the
increase in internal energy is not equal to the energy supplied
as heat because some energy will have been lost by the work
done (against the atmosphere) during the expansion of the
system.

• A property that is equal to the heat supplied at constant

pressure is called the enthalpy (H).
• Enthalpy is related to the internal energy of a system by the
relationship

• The increase in enthalpy, ΔH, is equal to the heat absorbed at

constant pressure by the system. It is the heat required to increase
the internal energy and to perform the work of expansion. So, the
first law can be written as,
THE SECOND LAW OF THERMODYNAMICS

• The first law, as we have seen, deals with the conservation of

energy as the system changes from one state to another, but it
does not specify which particular changes will occur
spontaneously.

• The reason why some changes have a natural tendency to occur

is not that the system is moving to a lower-energy state but that
there are changes in the randomness of the system.
• This can be seen by considering a specific example: the diffusion
of one gas into another occurs without any external intervention
– i.e. it is spontaneous – and yet there are no differences in either
the potential or kinetic energies of the system in its equilibrium
state and in its initial state where the two gases are segregated.

• The driving force for such spontaneous processes is the tendency

for an increase in the chaos of the system – the mixed system is
more disordered than the original.
• A convenient measure of the randomness or disorder of a system
is the entropy (S). When a system becomes more chaotic owing to
its molecular motion, its entropy increases in line with the degree
of increase in disorder caused. This concept is encapsulated in the
second law of thermodynamics, which states that the entropy of
an isolated system increases in a spontaneous change.

• Accordingly, in a spontaneous process, the entropy change of the

total system or universe (a system and its surroundings) is always
positive, we write,
• If the process is spontaneous, the total entropy will be a
positive value. If the system is at equilibrium, there is no
tendency for the process to occur, and the total entropy
change will be zero. Finally, if the process is not spontaneous,
the total entropy change will be negative.
• The second law, then, involves entropy change, ΔS, and this is defined
as the heat absorbed in a reversible process, q , divided by the
_rev

temperature (in kelvins) at which the change occurred. For a finite

change

• By a ‘reversible process’ we mean one in which the changes are carried

out infinitesimally slowly, so that the system is always in equilibrium with
its surroundings. In this case we infer that the temperature of the
surroundings is infinitesimally higher than that of the system, so that the
heat changes are occurring at an infinitely slow rate, so that the heat
transfer is smooth and uniform.
• The entropy of a substance will also change when it undergoes a
phase transition, since this too leads to a change in the order.
For example, when a crystalline solid melts, it changes from an
ordered lattice to a more chaotic liquid and consequently an
increase in entropy is expected. The entropy change
accompanying the melting of a solid is given by

• where ΔHfus is the enthalpy of fusion (melting) and T is the melting

temperature.
• Similarly, we may determine the entropy change when a liquid
vaporizes

• where ΔHvap is the enthalpy of vaporization and T now refers to

the boiling point.
Example:
THE THIRD LAW OF THERMODYNAMICS

• At absolute zero all the thermal motions of the atoms of the

lattice of a crystal will have ceased and the solid will have no
disorder and hence a zero entropy. This conclusion forms the
basis of the third law of thermodynamics, which states that
the entropy of a perfectly crystalline material is zero
when T = 0.
FREE ENERGY

• The criterion for spontaneity given by the second law

requires the knowledge of the entropy changes both in the
system and the surroundings as stated above. It may be very
useful, however, to have a property that depends only on the
system and nevertheless indicates whether a process occurs
in the natural direction of change, which is the Gibbs free
energy (G).
• The change in the free energy (ΔG) at constant
temperature and constant pressure arises from changes in
enthalpy and entropy, that is:

• Also, the change in Gibbs free energy at constant

temperature and pressure equals the useful or maximum
network that can be obtained from the process.
• When network can no longer be obtained from a process,
G is at a minimum, and ΔG = 0. This statement signifies
that the system is at equilibrium.

• On the other hand, a negative free energy change written

as ΔG < 0 signifies that the process is a spontaneous one. If
ΔG is positive (ΔG > 0), it indicates that net work must be
absorbed for the reaction to proceed, and accordingly it is
not spontaneous.