Lecture 1

A. Ramanan
Department of Chemistry

aramanan@chemistry.iitd.ac.in
MS719
Why Thermodynamics?

Let us consider a few everyday experiences that we encounter

with chemical reactions.
Think about melting and refreezing ice transformation of H2O
between the two phases solid and liquid. Crystallization of ice
requires removing some heat. Do you notice water remains as
liquid even below 0oC!
Why does NaCl dissolve in water? Does it give off heat? Does it
require energy? Can we separate NaCl from sea water?
How is it that diamond, a high pressure form of C, can coexist
with the low pressure form, graphite, at Earth's surface? Do
diamond and graphite both have the same energy? If you burn
graphite and diamond, which gives you more energy?
When dynamite explodes, why does it change into a rapidly
expanding gas, which provides the energy release, plus a few
solids?
Chemical thermodynamics provides us with a means of
answering these questions and more.
 Thermodynamics allows you to predict how chemical systems
should behave - but not how chemical systems will behave. It only
relates to the state of a system, and says nothing about the path
taken by the system in changing from one state to another.
What actually drives chemical reactions? Is it Energy? Can we just
calculate or measure the energy difference of Reactants and
Products and know which way the reaction will go?
For many years people felt that chemical reactions occurred
because the reactants had some kind of energy to give up (i.e., use
to do work) and that therefore the energy of the products would be
less than the energy of the reactants. However, we all know that
when ice melts it consumes rather than releases heat!
 H2(g) + O2(g) H2O(l)

H2(g) and O2(g) mixes violently

when initiated liberating heat
~240kJ/mol (irreversible
process)

Calculate the heat change at

constant pressure when the
same reaction is carried out in
an electrochemical cell
(reversible process).

E ~ 2.3 eV
 Spontaneous Processes
A process that is spontaneous in one direction is not
spontaneous in the opposite direction.
The direction of a spontaneous process can depend
on temperature:

Ice turning to water is spontaneous at T > 0C

Water turning to ice is spontaneous at T < 0C

 Reversible Processes
A reversible process is one that can go back and forth
between states under exactly the same conditions (the
definition of equilibrium!).

When 1 mol of water is frozen at 1 atm at 0C to form

1 mol of ice, q = Hfus of heat is removed.
[Note: ice cannot be crystallized at 273K but only below
273K]
To reverse the process, q = Hfus must be added to
the 1 mol of ice at 0C and 1 atm to form 1 mol of
water at 0C.
Therefore, converting between 1 mol of ice and 1 mol
of water at 0C is a reversible process.

Chemical systems in equilibrium are reversible.

 Irreversible Processes

When 1 mol of ice melts spontaneously in a

warm room, it is an irreversible process;
water does not freeze in a warm room!

In any spontaneous process, the path

between reactants and products is
irreversible.
 Spontaneous Processes

Thermodynamics predicts the direction of a

spontaneous process; it cannot predict the
speed at which the process will occur.

Most spontaneous processes are exothermic;

they "roll down the enthalpy hill".

But some spontaneous processes are not

exothermic; WHY?
Thermodynamics is most relevant to the
understanding of processes on spatial scales large
enough to neglect individual atoms and
timescales long enough to neglect kinetics, so
that the predictions of thermodynamics describe
to good approximation the actual state of nature,
rather than the expected state at infinite time.
All kinetic processes go faster with increasing
temperature, and hence the tools of
thermodynamics are most useful
But even for kinetically limited things (like
life), thermodynamics tells which way it is
favorable for processes to run.
 Definitions

System: the region of interest, of sufficient size that

average properties like temperature are well-defined; to be
distinguished from the environment (i.e., the rest of the
universe)
Open system: exchange of energy and matter
Closed system: exchange of energy but not matter
Isolated system: can exchange neither energy nor
matter
Thermodynamic State Properties
Extensive: These variables or properties depend
on the amount of material present (e.g. mass or
volume).
The ratio of any two extensive variables is always
an intensive variable. V/n = molar volume, V
Intensive: These variables or properties DO
NOT depend on the amount of material (e.g.
density, pressure, and temperature).
Phase: a physically homogeneous and
mechanically separable part of the system,
e.g. a vapor, liquid, or mineral
A system may be
homogeneous (one phase)
or
heterogeneous (multiple phases).
Component: a basis for expressing compositional
variations in thermodynamic systems; e.g., H2O,
sea water, conc. H2SO4.
Choice of components is often arbitrary but number of
components is not.
E.g.: System H2O is a one-component system if the only
phases of interest are pure water, ice, and vapor, and if we
need not consider electrolysis (i.e. separation into H2 and
O2) or acid-base chemistry (i.e. separation into H+ and
OH).
System: NaCl solution is a two-component system if we
are only concerned with NaCl and water. We need to
know the amount of both NaCl and H2O. Satd NaCl
solution and Con H2SO4 (saturated solution) are one
component systems.
Equilibrium: a state in which macroscopic
physical properties do not change during the
period of observation.
Microscopic processes are still occurring, but
the rate of every process is exactly balanced by
the rate of the reverse process.
A stable equilibrium is a global minimum in
potential energy. Subject to applied constraints,
the system cannot achieve lower energy in any
way. The system responds to small
perturbations by returning to the stable
equilibrium state.
A metastable equilibrium is a local
minimum in potential energy. The
equilibrium is stable with respect to small
perturbations and does not evolve
spontaneously, but it might respond to a large
perturbation by evolving away from the
metastable equilibrium towards a lower
energy state elsewhere.e.g.:diamond at 1atm
and 300K & super-cooled liquid

unstable
not at equilibrium

metastable

stable
Stable describes a system or phase
in its lowest energy state at a particular T & p.
Metastable" describes a system or phase in
any other energy state (refer the figure
a mechanical analogue of a ball rolling on ups
and downs.

Ice and liquid water are stable phases at 260

and 280K respectively.

Liquid water (super cooled water) at 260K is

metastable.

Ice and water can occur at equilibrium only at 0oC and 1 bar. A metastable
system will transform to a stable system even with a small disturbance a
spontaneous transformation to a stable state.

Discuss the stability of supercooled water at 260K in a closed system kept at

260K and an isolated system with suitable calculations (calculate H, S & G
for the process).
Reversible: an idealized process that proceeds
through a sequence of equilibrium states as the
parameters (p, V, T, n) are varied externally,
without any finite deviation from equilibrium.
Spontaneous: a real process (or natural
process), where the internal state of a system
changes in order to approach equilibrium from
an initially non-equilibrium state
 Work, w

Work : transfer of energy that can cause motion

against an opposing force
w, the transfer of mechanical energy
between objects at different initial pressures.

w = -pextdV

Note: Only opposing force

 Conventions
w, the work is negative when the system does work on
the surrounding, i.e. it expands into low-pressure
surroundings;
w, the work is positive when work is done on the
system by surrounding, i.e., high-pressure surroundings
compress the system.
Expansion work: mechanical w = - p.dV

Non-expansion work: electrical w = .dQ;

surface w = .dA, elastic w = f.dl
 Heat, q
Heat: Transfer of energy as a result of Temp
difference between System & Surrounding
Heat change (q): that which is transferred
from hot bodies to cold ones during
equilibration. Convention: heat transfer into
the system from hot surroundings is positive;
heat transfer by the system to cold
surroundings is negative.
For a closed system from an initial state (p1, V1, T1)
to a new state (P2, V2, T2), ..
and back to (P1, V1, T1)
that the sum of q and w transferred across the
boundaries of the system is zero.
Neither q nor w is a variable of state; the
quantities exchanged around closed paths of both
heat and work can be non-zero; only the sum is
conserved.
We can, however, define a variable of state U, the internal
energy, whose change for a closed system is given by
dU = q + w = q - pdV
This is the First Law of Thermodynamics. Note:
absolute values of U are arbitrary; only its changes dU
are significant
 First Law of Thermodynamics
The increase in internal energy as a result of
heat absorbed is diminished by the amount of
work done on the surroundings:

dU = q + w = q - pdV

By convention, heat added to the system, q,

is positive and work done by the system, w,
on its surroundings is negative.

This is also called the Law of Conservation of Energy

Idealized Thermodynamic Processes
Irreversible: Initial system state is unstable or metastable
and spontaneous change in the system yields a system with a
lower-energy final state.

Reversible: Both initial and final states are stable

equilibrium states and the path between them is a continuous
sequence of equilibrium states. NOT ACTUALLY
REALIZED IN NATURE.
w for an irreversible isothermal process

w pext dV
f

wirrev pext dV
i

irreversible & const. pressure

f f

w p dV
i
ext
i

wirrev pext (V f Vi )
 Reversible, isothermal expansion work, wrev

w p dV ext

w p dV (reversible ); pV nRT (ideal..gas )

rev system

dV
w nRT rev

V
dV
w nRT
f f

rev
i
V i

V
w nRT ln
rev
f

V i
w for an irreversible adiabatic process
q w pext dV
q 0(adiabatic )
w pext dV
f f f

w
i
irrev dU pext dV
i i

irreversible & const. pressure

f f

C
i
V dT pext dV ( for .ideal ..gas U f (T )only )
i
f f
dT
i CV T pext i dV
 Calculating w in an Adiabatic
Reversible Process
q w p dV ext

q 0(adiabatic)
TV 1
cons tan t
w p dV ( 1 ) /
cons tan t
ext

TP
w p dV
f f

cons tan t
ext

PV
i i

reversible ,
C
nRT P

p p
ext
(ideal..gas )
system
C
V V

dT dV
nR
f f

C V
i
T V i
 Enthalpy

Enthalpy is equal to the internal energy of a

system plus the PV product of the system.
H = U+PV
The change in enthalpy of a system, H
can be found using the relationship:
H = U + (PV), and if P = 0 (constant
pressure), H = U + PV, therefore:
H = qP for a system at constant pressure
and the only work is PV work.
At constant pressure and if the only work is done
against the atmosphere, i.e. pdV work, then
(for infinitesimal process)
w = -pdV
dHp = qp

and q is now an exact differential - that is

independent of path.
Enthalpy of Melting
For example, consider the burning of graphitic carbon in
oxygen, the change in enthalpy is:

Cgraph + O2 CO2
Ho -350 kJ/mol
In the combustion of 1 mole (12 g) of pure carbon as
graphite (a reasonable approximation of coal) 350kJ are
released. This is enough to raise the temperature of 1.0
L of water 350 K.

The superscript stands for standard conditions (1.00

atm). Because we started with elements in their
standard state H = Hfo the standard heat of
formation for CO2.
The burning of graphitic carbon might proceed
through formation of CO:
Ho or Hfo
Cgraph + O2 CO2 -350 kJ/mol
Cgraph + 1/2 O2 CO -110
CO + 1/2 O2 CO2 -250
----------------------------------------------------
NET Cgraph + O2 CO2 -350 kJ/mol

This is Hess' law the enthalpy of a reaction is

independent of the path. The units of kJ are commonly
used because Hfo is usually measured with Dewars flask
and change in water temperature.
 Heat capacity
The amount of heat required to produce a one degree
change in temp in a given substance.

C = q/dT
Cp = (q/T)p = (H/T)p
Cv = (q/T)v = (U/T)v

Because qp = dH and qv = dU
For an ideal gas PV = nRT
Cp = Cv + R

Where R = 8.31 J/mol.K

For an ideal monatomic gas
CV = 3R/2 and CP = CV+R & U=nCV T
(all the energy going into heating the gas, no
work is being done because V = 0) &
H = U + (PV) or H = U + nRT or
H = nCV T + nRT = n(CV+R) T or
H = nCP T
Note: CV was defined for ideal monatomic
gases. For polyatomic gases CV is always
larger because heat can be stored
internally as vibrations and rotations, not
just as linear motion. For example,

gas H, Ne, H2, N2 CO2 C2H6

Ar

CV 12.5 20.6 29.0 44.6

ENTHALPY OF REACTIONS

The heat of a reaction is the sum of the heats of

formation of the products minus the sum of the
heats of formation of the reactants.

Hrxn = Hfo(products) - Hfo(reactants)

The change of enthalpy of a reaction is fairly

independent of temperature.

EXAMPLE: ENTHALPY CALCULATION