MUCLecture 2021 112940914
MUCLecture 2021 112940914
MUCLecture 2021 112940914
Physical pharmacy 1
Lecture4
In physics, thermodynamics (from the Greek, therme, meaning "heat and, dynamis,
meaning "power") is the study of the transformation of energy into different forms and
its relation to macroscopic variables such as temperature, pressure, and volume. Its
underpinnings, based upon statistical predictions of the collective motion of particles
from their microscopic behavior, is the field of statistical thermodynamics, a branch of
Thermodynamics is based on three “laws” or facts of experience that have never been
proven in a direct way, in part due to the ideal conditions for which they were derived
statistical mechanics .
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Thermodynamics:
The study of heat and its transformations. or, Thermodynamics is the study of energy
transformations
Temperature: measure of hotness and coldness in terms of any arbitrary scales and
indicating the direction which energy spontaneously flows (from a hotter body to a
colder one)
System:
The part of the universe of interest
Surroundings:
Everything else (relevant to system)
Universe:
System + surroundings
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System, surroundings and boundary
System: A quantity of matter or a region in space chosen for
study.
Surroundings: The mass or region outside the system
Boundary: The real or imaginary surface that separates the
system from its surroundings
The three types of systems that are frequently used to describe
thermodynamic properties.
an open system in which energy and matter can be exchanged with the
surroundings.
closed systems, in which there is no exchange of matter with the surroundings,
that is, the system’s mass is constant. However, energy can be transferred by
work or heat through the closed system’s boundaries
last a system in which neither matter nor energy can be exchanged with the
surroundings; this is called an isolated system
Physical properties of a system-
1.Intensive properties- e.g. – temperature, pressure, viscosity,
surface tension, refractive index, specific heat, density, etc.
2.Extensive properties- e.g.- mass, volume, energy, heat capacity,
entropy, Gibb’s free energy, ect.
Thermodynamic process
Reversible
Isothermic [T]
irreversible
Isobaric [p]
Isochoric [V]
Adiabatic [Q]
Work (W) and heat (Q) also have precise thermodynamic meanings
Work is a transfer of energy that can be used to change the height of
a weight somewhere in the surroundings
and heat is a transfer of energy resulting from a temperature difference
between the system and the surroundings. It is important to consider that
both work and heat appear only at the system’s boundaries where the
energy is being transferred
Law’s of thermodynamics
Zeroth Law of thermodynamics
Thermal contact
Thermal equilibrium
If two objects are in thermal equilibrium
with a third, then they are in thermal
equilibrium each other
(Zeroth Law of thermodynamics)
Two objects are defined to have the
same temperature if they are in thermal
equilibrium with each other
Law’s of thermodynamics
ΔU = Q + W
According to the first law, the effects of Q and 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, or U), defined as
ΔU = Uf – Ui = Q + W
Q is the energy transferred to the system by
heat
W is the work done on the system
ΔU is the change in internal energy
nonspontaneous
reversible process: evaporation and condensation of water at 1
atm in a closed system.
(a) System at equilibrium with P ex=1 atm;
(b) expansion is infinitesimal;
(c) compression is infinitesimal.
In thermodynamics, an irreversible process is defined as a process
that cannot be reversed, process, that cannot return both the system and the
surroundings to their original conditions.
During irreversible process the entropy of the system increases.
Isobaric Process
• An isobaric process is a constant pressure process. ΔU, W, and
Q are generally non-zero, but calculating the work done by an
ideal gas is straightforward
W = P·ΔV
W = -P·ΔV
• Water boiling in a saucepan is an example of an isobar process
the maximum work done in the expansion as well as the heat absorbed
because
Q = E −W
E is equal to zero for an ideal gas in an isothermal process.
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, equation can be
Example1
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 is
about 9720 cal/mole. What are the values of the three first-
lawterms Q, W, and ΔE? Now, V1 is the volume of 1 mole of liquid water at
100◦C, or about 0.018 liter
W = −nRT ln(V2/V1).
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 non covalent forces of
attraction
Example2
Calculate the work done when 1.0 mole water at 373K vaporizes against
an atmospheric pressure of 1.0 atmosphere. Assume ideal gas behavior.
ANSWER
against an atmospheric pressure
w=−P ×ΔV
V2˃˃V1
1.0×0.0821×373
V2= =30.6 liter
1.0
V1 is negligible w.r.t. V2
w=−P × ΔV=−(1.0)×(30.6)liter−atm
=−30.6
Example3
ANSWER
W =−P×ΔV
=−1×(13−3)=−10atm 𝑑𝑚3
Example4
1.73×0.0821×373
V2= =77.909 liter
0.68𝑎𝑡𝑚
77.909-0.03114=77.87L
W=-P ΔV
W=-77.87X0.68=52.95liter .atm