Chemistry CY1001
K. Mangala Sunder*
Professor Emeritus, Department of Chemistry
Indian Institute of Technology Madras
Chennai, India
*mangal@[Link]; mangalasunderk@[Link]
Contents outline
[Link] to systems and surroundings, open,
closed and isolated systems; reversible and
irreversible processes; First law of thermodynamics
[Link], Carnot cycle and the second law of
thermodynamics.
[Link] of second law of thermodynamics-
simple calculations involving entropy changes.
[Link] Equilibria and energy changes; a few simple
phase diagrams
Lecture1: Introduction to the first law of thermodynamics
• Surroundings-that which surrounds
• System: the object of the system and provides /receives
study, thermodynamic heat, energy, matter etc. and which is
measurement etc. separated from the system by a
boundary
• Universe =system plus surroundings
Three general types of systems are considered
Closed System: the system can exchange energy with the
surroundings through the boundary walls. The energy can be in
the form of electrical, mechanical, thermal etc. No change in the
number of particles nor are they allowed to exchange with the
surroundings.
Open System: the system can exchange energy and matter with
the surroundings through the boundary walls. It may also be
reactive with the number of particles changing continuously.
Isolated System: the system can not exchange energy and
matter with the surroundings. Universe as a system is an
example (No surroundings).
Examples for systems
★A gas or a mixture of gases not reacting with each
other chemically, and contained in an enclosure.
★ A solution containing dissolved substances which
do not undergo any chemical reaction and kept in the
open (vapours can escape to the surroundings)-
homogeneous
★ Immiscible liquids in contact with each other in an
enclosed space or a chemical reaction happening on a
solid-- heterogeneous
What is a thermodynamic state?
Thermodynamic state of a closed system is specified by the
values for pressure, volume and temperature. The total number of
particles is fixed.
For gases, specification of any
two of them will determine the
third through the equation of
state.
Example: If we know the
pressure and temperature,
we can determine the
volume through the gas laws
(ideal or non-ideal gas laws)
Ideal gas law: PV = nRT
van der Waals gas ⎛ n a⎞
2
(non-ideal) ⎜⎝ P + ⎟ (V − nb ) = nRT
V ⎠
2
a and b are assumed to be known. They
have different values for different gases.
Virial equation of state RT ⎧ B(T ) C(T ) ⎫
P= ⎨1+ + 2 +!⎬
(non-ideal) Vm ⎩ Vm Vm ⎭
Vm molar volume, B(T ) second virial coefficient
C(T ) third virial coefficient, etc.
Internal energy of a system (U)
=sum of all kinetic and potential energies of
all particles of the system
It is a function of the thermodynamic state
of the system
It is the sum of translational, rotational, vibrational,
electronic and spin energies of all molecules in the
system. One needs to use quantum mechanics and
statistical mechanics to calculate the total energy of the
system.
For gases, experiments lead to the conclusion that the
internal energy changes when
★mechanical work is done on the system or by the system
★when heat is added to the system or removed from the
system. (no molecular interpretation was known earlier)
Heat energy is often associated with thermal, random
motion and is an unorganized form of energy.
Mechanical work is often associated with organized form of
energy since it leads to net displacement of the system to a
larger or a smaller volume.
Other forms of work, chemical, electrical etc. will be used
to define other thermodynamic quantities later.
First law of thermodynamics (from experience)
ΔU = U 2 − U1 = q + w
read the equation as
The change in the heat
The internal energy
content of the system q
change when a system
goes from a thermo-
dynamic state 1 to
= +
another thermo-dynamic The amount of work
added to the system or
state 2 ΔU done by the system w
signs are very, very important.
What are the signs?
Work done on the system is a positive quantity
Work done by the system is a negative quantity
Heat energy added to the system is a positive quantity
Heat energy given out by the system is a negative quantity
change in the internal energy in the
transformation from state 1at P1 , V1, T1 to state
2 at P2 , V2, T2
ΔU = U 2 (P2 ,V2 ,T2 ) − U1 (P1 ,V1 ,T1 )
Examples
1. When 50 calories of heat are added to a system (it is heated) and
25 calories-equivalent of work is done on the system (it is
compressed), the internal energy change is
ΔU = 50 + 25 = 75
2. When 100 calories of heat are added to a system (it is heated)
and 40 calories-equivalent of work is done by the system (it is
expanding), the internal energy change is
ΔU = 100 + (−40) = 60
2. When 100 calories of heat are removed from a system (it is
cooled) and 100 calories-equivalent of work is done by the system (it
is expanding), the internal energy change is
ΔU = ( −100 ) + (−100) = −200
The differential form of the first law.
This form is used to indicate changes in internal
energy in an infinitesimally small change of the
thermodynamic state.
( P1,V1,T1 ) → ( P2 ,V2 ,T2 )
taken through infinite number of steps
( P1,V1,T1 ) → ( P1 + dP1,V1 + dV1,T1 + dT1 )
→ ( P1 + 2dP1 ,V1 + 2dV1 ,T1 + 2dT1 )
→ … → ( P2 ,V2 ,T2 )
dU = δ q + δ w
dU = δ q + δ w
Independent of Dependent of the Dependent of the
the path taken to path taken to go path taken to go
go from state 1 from state 1 to from state 1 to
to state 2 state 2 state 2
q1 = ∫ δq w=∫ δw q1 ≠ q2 ≠ q3 w1 ≠ w2 ≠ w3
path path
path1 ΔU = q1 + w1
path 2 ΔU = q2 + w2
P1 , V1, T1 P2 , V2, T2
path 3 ΔU = q3 + w3
What are the different paths?
Reversible: at each stage of the path the system is in equilibrium
with the surroundings: The process can be reversed by an
infintesimally small change of the conditions.
IDEAL PROCESS. NOT ACHIEVABLE IN PRACTICE.
Irreversible: several examples
Constant temperature process -isothermal
Constant pressure process -isobaric
constant volume process -isochoric
Constant heat content process-adiabatic process
Depending on the surroundings one or more of
the above can also be visualized under reversible
conditions.
In the next lecture we shall consider
various processes and obtain formulae
for reversible and irreversible work done
on a gaseous system-ideal or non-ideal.
Thank you. End of the lecture.
