Chemistry CY1001 Aug-Dec 2016

K. Mangala Sunder*
Professor, Department of Chemistry
Indian Institute of Technology Madras
Chennai, India

mangal@iitm.ac.in; mangalasunderk@gmail.com;
 Course outline as modules
Thermodynamics (5-8 lectures)
 Second law, entropy change accompanying various processes

 Absolute entropy and third law of thermodynamics

S  pontaneity. Gibbs free energy and standard Gibbs free energy of

formation.

 Thermodynamics functions and Maxwell’s relations

 Gibbs-Helmholtz equation and chemical potential; extent of reaction

 Equilibrium constants, Kp, Kc and relations.

  hase equilibria, phase rule, phase diagrams of water, carbon dioxide;

P
Clausius-Clapeyron equation

  Liquid-solid phase diagrams, eutectics and cooling curves

This lecture: Review of 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
measurement etc. is 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. For liquids and solids,
other parameters may be
needed.
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:

van der Waals gas

(non-ideal)

and are assumed to be known. They

have different values for different gases.

Virial equation of state

(non-ideal)
molar volume, second virial coefficient
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 experiments and experience)

Read the equation as

The change in the heat
The internal energy
content of the system
change when a system
goes from a thermo-
dynamic state 1 to
= +
The amount of work
another thermo-dynamic
added to the system or
state 2
done by the system

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 1 at to
state 2 at
 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

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

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
 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.

taken through infinite number of steps

 Independent of Dependent on Dependent on
the path taken to the path taken to the path taken to
go from state 1 go from state 1 go from state 1
to state 2 to state 2 to state 2

path1

path 2

path 3
 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
infinitesimally 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.
Calculations using the first law of thermodynamics

For an ideal gas, internal energy is a function only of its

temperature. It is independent of volume and pressure.

The change in internal energy as a function of temperature

is measured by an experimental quantity; heat capacity at
constant volume.
 Heat capacity at constant volume:
Rate of change of internal energy with respect
to temperature at constant volume

Classical kinetic theory of gases and mechanics have proposed

values for internal energies of ideal gases based on the
principle of equi-partition of energies. These are obviously
approximations useful for real and non-ideal gases.
For a monatomic gas:

Internal energy contribution Internal energy for one gm

due to translational motion atom, , Avogadro no.
in one direction

Internal energy for three dimensions

(for three translational degrees of
freedom)

diatomic and polyatomic molecules have other additional degrees of

freedom, namely rotations and vibrations

Internal energy contribution Internal energy contribution

for each rotational degree of for each vibrational degree
freedom of freedom
 Diatomic molecules have two rotational degrees of freedom. Rotation
about the bond axis does not have rotational energies as the moment of
inertia about that axis is zero. (point mass approximation for atoms)

Internal energy Internal energy

contribution due to contribution due to
diatomic molecular diatomic molecular
rotation vibration

Internal energy of a monatomic species

Internal energy of a diatomic species with 6 degrees of freedom (molar)

translational (3) Rotational (2) Vibrational (1)

 Polyatomic molecules with N atoms
have 3N degrees of freedom
Non-linear
Linear polyatomics polyatomics

3 translational 3 translational

2 rotational 3 rotational

3N-5 vibrational 3N-6 vibrational

Total Total
 The heat capacity at constant pressure is another experimentally
important quantity. It will be defined later after introducing
another thermodynamic function, enthalpy.
For this lecture use the definition, molar heat capacity of a gas at
constant pressure,

The ratio of the two heat capacities is another important quantity,

used in adiabatic processes.
Gas

He 3R/2=12.48 5R/2=20.78 1.67

Ar 3R/2=12.48 5R/2=20.78 1.67

O2 7R/2=29.11 9R/2=37.14 1.28

SO2 6R=49.89 7R=58.20 1.17

C 6H 6 33R=274.36 34R=282.68 1.03

 Calculations using first law for several processes
reversible process
Expansion of a gas in a cylinder at pressure P, if
the external pressure is less by an infinitesimally
small amount. The process is reversible.

P’ < P.
Gas will expand – Imagine a reversible process.
Gas expands so slowly that the gas pressure P
will approach a final pressure P’ infinitesimally
slowly. All other processes are irreversible.
Process at constant temperature- Isothermal process
Reversible work done on a system. By external pressure P, and
inducing a volume change dV in the system

isothermal reversible expansion

The entire shaded area

isothermal irreversible expansion against a

constant external pressure
The solid-blue shade
 Reversible isothermal expansion for an ideal gas

Reversible adiabatic expansion for an ideal gas

Temperatures will change since no heat can be

transferred for gas doing the work. Therefore, internal
energy will decrease,
 No heat is gained or lost by the gas during adiabatic
process. Hence the first law tells us that all the work
done by the gas leads to internal energy change

For only pressure-volume work

For an ideal gas, internal energy is only a function of the

temperature. During expansion the temperature drops.
 Processes at constant external pressure

Right hand side of the above equation depends only on initial and final states

is called the enthalpy of the system.

During the change the change in enthalpy is

The heat absorbed in a process at constant pressure is equal to the change
in the enthalpy of the system

Temperature and pressure dependent

This suggests that enthalpy may be considered a

function of temperature and pressure.

Heat capacity at constant pressure:

Rate of change of enthalpy with respect to
temperature at constant pressure
Adiabatic reversible processes for an ideal gas.
( P1, V1, T1 ) → ( P2 , V2 , T2 )
End of the Review Lecture.
Thank you.