CHM-222A: BASIC PHYSICAL CHEMISTRY

Debabrata Goswami
Jan 2017
IITK

COURSE CONTENT
Zeroth Law of Thermodynamics: Equilibrium, State Functions, Temperature, Equations of State.
First Law of Thermodynamics: Work, Heat, Internal Energy, Heat Capacity, Concept of Enthalpy.
Second Law of Thermodynamics: Reversible and Irreversible Process, Heat Engines, Carnot
Cycle, Different statements of the Second Law, Spontaneous Change, Entropy.
Third Law of Thermodynamics: Concept of the absolute zero temperature.
Free Energy and Standard States: Free energies and Thermodynamic potentials, Legendre
Transforms, Equilibrium and Non Equilibrium, Chemical Potentials, Free Energy, Standard States,
Reaction Thermodynamics, Equilibrium Constant.
Equilibrium Thermodynamics: Chemical Potential of Mixtures, Phase Equilibrium, Phase Rule,
Clapeyron Equation, Phase Diagram.
Real Gases: Equations of State, Phase Transitions.
Solutions: Molarity, Partial Molar Quantities, Mixing, Ideal Solutions, Non Ideal Solutions,
Electrolytes, Ionic activity and the Debye Hueckel Theory, the Nernst Equation, Colligative
properties, Multi component phase diagrams.
Kinetic Theory of Gases and Transport Processes.
Reaction Kinetics: Reaction Rates, Rate Laws, Reaction Mechanisms, Applications

COURSE EVALUATION
Attendance + Homework Assignments

10%

Quizzes

10%

1 Mid Semester Exam

30%

End Semester Exam (compulsory)

50%

THERMODYNAMICS
Study of Systems at equilibrium describing their macroscopic properties
Self Contained
Built on four Laws, observations and mathematics
Zeroth Law
1st Law

Defines Temperature (T)

Defines Energy (U)

2nd Law

Defines Entropy (S)

3rd Law

Gives Numerical Value to Entropy

These laws are UNIVERSALLY VALID , they cannot be circumvented.

DEFINITIONS
System : That part of the Universe, which we choose to study (Certain quantity of matter
within a boundary)
Surroundings : The rest of the Universe
Boundary : The surface dividing the System from the Surroundings
Systems can be
Open : Mass and Energy can transfer between the System and the Surroundings
Closed : Energy can transfer between the System and the Surroundings, but NOT mass
Isolated : Neither Mass nor Energy can transfer between the System and the Surroundings
System description requires
A few macroscopic properties: p, T, V, n, m,
Knowledge if System is Homogeneous or Heterogeneous
Knowledge if System is in Equilibrium State
Knowledge of the number of components

THERMODYNAMIC PROPERTIES

THERMODYNAMIC PROPERTIES (CONTD.)

Extensive : Depend on the size of the system
Intensive : Independent of the size of the system

(n, m, V,)
(T, P, r,)

The State of a System at Equilibrium:

Defined by the collection of all macroscopic properties that are described by State
variables (P, n, T, V,) [INDEPENDENT of the HISTORY of the SYSTEM]
For a one-component System, all that is required is n and 2 variables. All other
properties then follow.
V = f(n,P,T) or p = g(n,V,T)
Notation:
3 H2 (g, 1 bar, 100 C)
3 moles
(n=3)

gas

p =1 bar

T = 100C

THERMODYNAMIC TRANSFORMATIONS
Change of State:
Notation :
3 H2 (g, 5 bar, 100 C) = 3 H2 (g, 1 bar, 50 C)
initial state

final state

Path : Sequence of intermediate states

Process : Describes the Path

- Reversible (always in Equilibrium)
- Irreversible (defines direction of time)
- Adiabatic (no heat transfer between system
and surroundings)
- Isobaric (constant pressure)
- Isothermal (constant temperature)
- Constant Volume

THERMAL EQUILIBRIUM (HEAT STOPS FLOWING!)

Heat Flow Stops

Thermal equilibrium

When a hot object is placed in thermal contact with a cold object, heat flows from the
warmer to the cooler object. This continues until they are in thermal equilibrium (the heat
flow stops). At this point, both bodies are said to have the same temperature.
This intuitively straightforward idea is formalized in the zeroth Law of thermodynamics
and is made practical through the development of thermometers and temperature scales.

ZEROTH LAW

TEMPERATURE
Operational definition of temperature (T)
Need : (1) substance
(2) property that depends on T
(3) reference points
(4) interpolation scheme between reference points
Example : Ideal Gas Thermometer with the Celsius scale.

Summary: The Zeroth Law of Thermodynamics

We have already discussed the zeroth law,
and include it here for completeness:
If object A is in thermal equilibrium with
object C, and object B is separately in
thermal equilibrium with object C, then
objects A and B will be in thermal equilibrium
if they are placed in thermal contact.

THE IDEAL GAS LAW

PV nRT or PV RT , V V /n

Extensive vs. intensive properties

Units of pressure

Units of temperature

1 Pa 1 N m 2
1 atm 1.01325 105 Pa
1 bar = 105 Pa
1
1 torr =
atm
760

Triple point of water occurs at 273.16

K (0.01oC)

DEVIATIONS FROM IDEAL GAS BEHAVIOR

z

PV
RT

T=300K

compressibility factor

Ideal gas: z = 1
z < 1:

attractive intermolecular forces dominate

z > 1:

repulsive intermolecular forces dominate

VAN DER WAALS EQUATION

a

V b RT

2
V

At fixed P and T, V is the solution of a

cubic equation. There may be one or three
real-valued solutions.

The set of parameters Pc, Vc, Tc for which the number of solutions changes
from one to three, is called the critical point. The van der Waals equation has
an inflection point at Tc.

ISOTHERMS
(P VS. V AT CONSTANT T)
P
T Tc :
0

T
P

0 : unstable region
V T

Large V: ideal gas behavior.

Only one phase above Tc.

Unstable region: liquid+gas coexistence.

CRITICAL POINT OF VAN DER WAALS EQUATION

RT
2a
P

(V b) 2 V 3
V T
2a (V b) 2
0 for V
RT
3

(3 or 1 real roots)

2P
2 RT
6a

2
3
4
V T (V b) V
3a (V b)3
0 for V
RT
4

Both are satisfied at the critical (inflection) point, so...

Vc 3b
8a
Tc
27 Rb
a
Pc
27b 2

THE LAW OF CORRESPONDING STATES

Eliminate a and b from the van der Waals equation:
2
b 13 Vc , a 27b 2 Pc 3PV
c c ,

3
1 8
P

V TR
R
2 R
VR
3 3

PR

P
V
T
, VR , TR
"reduced" variables
Pc
Vc
Tc

All gases behave the same way under similar

conditions relative to their critical point.
(This is approximately true.)

VIRIAL COEFFICIENTS
Z

PV
B
B
1 2V 3V2 Virial expansion
RT
V
V

B2V : second virial coefficient,

B3V : third virial coefficient,etc.
Using partition functions, one can show that

B2V (T ) 2 N A

e u ( r ) / kBT 1 r 2 dr

u (r ): rotationally averaged intermolecular potential

THE LENNARD-JONES MODEL

c12 c6
u ( r ) 4 12 6
r
r

Attractive term: dipole-dipole, or dipole-induced dipole, or

induced dipole-induced dipole (London dispersion) interactions.

THERMODYNAMICS
Thermodynamics is the study of the effects of work, heat, and energy on a
system
Thermodynamics is only concerned with macroscopic (large-scale) changes and
observations

GETTING STARTED
All of thermodynamics can be expressed in terms of four
quantities
Temperature (T)
Internal Energy (U)
Entropy (S)
Heat (Q)

These quantities will be defined as we progress

CLASSICAL VS STATISTICAL
Classical thermodynamics concerns the relationships
between bulk properties of matter. Nothing is examined
at the atomic or molecular level.
Statistical thermodynamics seeks to explain those bulk
properties in terms of constituent atoms. The statistical
part treats the aggregation of atoms, not the behavior
of any individual atom

FIRST LAW
The first law of thermodynamics is an extension of the law
of conservation of energy
The change in internal energy of a system is equal to the
heat added to the system minus the work done by the
system
U = Q - W

PROCESS TERMINOLOGY
Adiabatic no heat transferred
Isothermal constant temperature
Isobaric constant pressure
Isochoric constant volume

ADIABATIC PROCESS
An adiabatic process transfers no heat
therefore Q = 0

U = Q W
When a system expands adiabatically, W is positive (the system does
work) so U is negative.
When a system compresses adiabatically, W is negative (work is done
on the system) so U is positive.

ISOTHERMAL PROCESS
An isothermal process is a constant temperature process. Any heat
flow into or out of the system must be slow enough to maintain
thermal equilibrium
For ideal gases, if T is zero, U = 0
Therefore, Q = W
Any energy entering the system (Q) must leave as work (W)

1.1.3 ISOBARIC PROCESS

An isobaric process is a constant pressure process. U, W, and Q
are generally non-zero, but calculating the work done by an ideal
gas is straightforward
W = PV
Water boiling in a saucepan is an example of an isobar process

1.1.4 ISOCHORIC PROCESS

An isochoric process is a constant volume process. When
the volume of a system doesnt change, it will do no work
on its surroundings (W = 0).
U = Q
Heating gas in a closed container is an isochoric process

1.2 HEAT CAPACITY

The amount of heat required to raise a certain mass of a
material by a certain temperature is called heat capacity
Q = mcxT
The constant cx is called the specific heat of substance x,
(SI units of J/kgK)

1.2.1 HEAT CAPACITY OF IDEAL GAS

CV = heat capacity at constant volume
CV = 3/2 R
CP = heat capacity at constant pressure
CP = 5/2 R
For constant volume
Q = nCVT = U
The universal gas constant R = 8.314 J/molK

The First Law of Thermodynamics

The first law of thermodynamics is a statement of the conservation of energy.
If a systems volume is constant, and heat is added, its internal energy increases.

The First Law of Thermodynamics

If a system does work on the external world, and no heat is added, its internal energy decreases.

The First Law of Thermodynamics

Combining these gives the first law of thermodynamics. The change in a systems
internal energy is related to the heat Q and the work W as follows:

It is vital to keep track of the signs of Q and W.

The First Law of Thermodynamics

The internal energy of the system depends only on its temperature. The work done
and the heat added, however, depend on the details of the process involved.

Thermal Processes
We will assume that all processes we discuss are quasi-static they
are slow enough that the system is always in equilibrium.
We also assume they are reversible:
For a process to be reversible, it must be possible to return both the
system and its surroundings to exactly the same states they were in
before the process began.

Thermal Processes
This is an idealized reversible process. The gas is compressed; the
temperature is constant, so heat leaves the gas. As the gas expands,
it draws heat from the reservoir, returning the gas and the reservoir
to their initial states. The piston is assumed frictionless.

Thermal Processes
Work done by an expanding gas, constant pressure:

Thermal Processes
If the volume stays constant, nothing moves and no work is done.

Thermal Processes
If the temperature is constant, the pressure varies inversely
with the volume.

Thermal Processes
The work done is the area under the curve:

Thermal Processes
An adiabatic process is one in which no heat flows into or out of the system.
The adiabatic P-V curve is similar to the isothermal one, but is steeper. One
way to ensure that a process is adiabatic is to insulate the system.

Thermal Processes
Another way to ensure that a process
is effectively adiabatic is to have the
volume change occur very quickly. In
this case, heat has no time to flow in
or out of the system.

Thermal Processes
Here is a summary of the different types of thermal processes:

Specific Heats for an Ideal Gas: Constant Pressure, Constant Volume

Specific heats for ideal gases must be quoted either at constant
pressure or at constant volume. For a constant-volume process,

Specific Heats for an Ideal Gas: Constant Pressure, Constant Volume

At constant pressure,

Specific Heats for an Ideal Gas: Constant Pressure, Constant Volume

Both CV and CP can be calculated for a monatomic ideal gas using
the first law of thermodynamics.

Specific Heats for an Ideal Gas: Constant Pressure, Constant Volume

Although this calculation was done for an ideal, monatomic gas, it works well for
real gases.

Specific Heats for an Ideal Gas: Constant Pressure, Constant Volume

The P-V curve for an adiabat is given by

where

The Second Law of Thermodynamics

We observe that heat always flows spontaneously from a warmer object to a
cooler one, although the opposite would not violate the conservation of energy.
This direction of heat flow is one of the ways of expressing the second law of
thermodynamics:
When objects of different temperatures are brought into thermal contact, the
spontaneous flow of heat that results is always from the high temperature
object to the low temperature object. Spontaneous heat flow never proceeds in
the reverse direction.

Heat Engines and the Carnot Cycle

A heat engine is a device that converts heat into work. A classic example is the
steam engine. Fuel heats the water; the vapor expands and does work against
the piston; the vapor condenses back into water again and the cycle repeats.

Heat Engines and the Carnot Cycle

All heat engines have:

a high-temperature reservoir
a low-temperature reservoir
a cyclical engine
These are illustrated schematically here.

Heat Engines and the Carnot Cycle

An amount of heat Qh is supplied from the hot reservoir to the engine during each
cycle. Of that heat, some appears as work, and the rest, Qc, is given off as waste
heat to the cold reservoir.

The efficiency is the fraction of the heat supplied to the engine that appears
as work.

Heat Engines and the Carnot Cycle

The efficiency can also be written:

In order for the engine to run, there must be a temperature

difference; otherwise heat will not be transferred.

Heat Engines and the Carnot Cycle

The maximum-efficiency heat engine is described in Carnots theorem:
If an engine operating between two constant-temperature reservoirs is to have
maximum efficiency, it must be an engine in which all processes are reversible.
In addition, all reversible engines operating between the same two
temperatures, Tc and Th, have the same efficiency.
This is an idealization; no real engine can be perfectly reversible.

Heat Engines and the Carnot Cycle

If the efficiency depends only on the two temperatures, the ratio of the
temperatures must be the same as the ratio of the transferred heats. Therefore,
the maximum efficiency of a heat engine can be written:

Heat Engines and the Carnot Cycle

The maximum work a heat engine can do is then:

If the two reservoirs are at the same temperature, the efficiency is zero; the
smaller the ratio of the cold temperature to the hot temperature, the closer
the efficiency will be to 1.

Refrigerators, Air Conditioners, and Heat Pumps

While heat will flow spontaneously only from a higher temperature to a lower
one, it can be made to flow the other way if work is done on the system.
Refrigerators, air conditioners, and heat pumps all use work to transfer heat
from a cold object to a hot object.

Refrigerators, Air Conditioners, and Heat Pumps

If we compare the heat engine and
the refrigerator, we see that the
refrigerator is basically a heat engine
running backwards it uses work to
extract heat from the cold reservoir
(the inside of the refrigerator) and
exhausts to the kitchen.

Note that
- more heat is exhausted to the kitchen than is removed from the refrigerator.

Refrigerators, Air Conditioners, and Heat Pumps

An ideal refrigerator would remove the most heat from the interior while
requiring the smallest amount of work. This ratio is called the coefficient of
performance, COP:

Typical refrigerators have COP values between 2 and 6. Bigger is better!

Refrigerators, Air Conditioners, and Heat Pumps

An air conditioner is essentially identical to a
refrigerator; the cold reservoir is the interior of the
house or other space being cooled, and the hot
reservoir is outdoors. Exhausting an air conditioner
within the house will result in the house becoming
warmer, just as keeping the refrigerator door open
will result in the kitchen becoming warmer.

Refrigerators, Air Conditioners, and Heat Pumps

Finally, a heat pump is the same as an air
conditioner, except with the reservoirs
reversed. Heat is removed from the cold
reservoir outside, and exhausted into the
house, keeping it warm. Note that the work
the pump does actually contributes to the
desired result (a warmer house) in this case.

Refrigerators, Air Conditioners, and Heat Pumps

In an ideal heat pump with two operating temperatures (cold and hot), the Carnot
relationship holds; the work needed to add heat Qh to a room is:

The COP for a heat pump:

Entropy
A reversible engine has the following relation between the heat transferred and
the reservoir temperatures:

Rewriting,

This quantity, Q/T, is the same for both reservoirs, and is defined as the change in
entropy.

Entropy

For this definition to be valid, the heat transfer must be reversible.

In a reversible heat engine, it can be shown that the entropy does not change.

Entropy
A real engine will operate at a lower efficiency than a reversible engine; this
means that less heat is converted to work. Therefore,

Any irreversible process results in an increase of entropy.

Entropy
To generalize:
The total entropy of the universe increases whenever an irreversible process
occurs.
The total entropy of the universe is unchanged whenever a reversible process
occurs.
Since all real processes are irreversible, the entropy of the universe continually
increases. If entropy decreases in a system due to work being done on it, a
greater increase in entropy occurs outside the system.

Entropy
As the total entropy of the universe increases, its ability to do work
decreases. The excess heat exhausted during an irreversible process
cannot be recovered; doing that would require a decrease in entropy,
which is not possible.

Order, Disorder, and Entropy

Entropy can be thought of as the increase in disorder in the universe. In this
diagram, the end state is less ordered than the initial state the separation
between low and high temperature areas has been lost.

Order, Disorder, and Entropy

If we look at the ultimate fate of the universe in light of the continual increase in
entropy, we might envision a future in which the entire universe would have come to
the same temperature. At this point, it would no longer be possible to do any work,
nor would any type of life be possible. This is referred to as the heat death of
the universe.

Order, Disorder, and Entropy

So if entropy is continually increasing, how is life possible? How is it that species
can evolve into ever more complex forms? Doesnt this violate the second law of
thermodynamics?
No life and increasing complexity can exist because they use energy to drive
their functioning. The overall entropy of the universe is still increasing. When a
living entity stops using energy, it dies, and its entropy can increase rather
quickly.

The Third Law of Thermodynamics

Absolute zero is a temperature that an object can get arbitrarily
close to, but never attain. Temperatures as low as 2.0 x 10-8 K have
been achieved in the laboratory, but absolute zero will remain ever
elusive there is simply nowhere to put that last little bit of
energy.
This is the third law of thermodynamics:
It is impossible to lower the temperature of an object to absolute
zero in a finite number of steps.

Summary: Thermodynamic
Laws
0

Temperature

Energy Conservation

Entropic Increase

Absolute Entropy

)0

0]

Summary
When two objects have the same temperature, they are in thermal
equilibrium.
The first law of thermodynamics is a statement of energy
conservation that includes heat.

The internal energy of a system depends only on its temperature,

pressure, and volume.
A quasi-static process is one in which the system may be
considered to be in equilibrium at all times.

Summary
In a reversible process it is possible to return the system and its
surroundings to their initial states.
Irreversible processes cannot be undone.
The work done during a process is equal to the area under the
curve in the PV plot.
The work done at constant pressure is
The work done at constant volume is zero.
The work done in an isothermal expansion is

Summary
An adiabatic process is one where no heat transfer occurs.
The value of the specific heat depends on whether it is at constant
pressure or at constant volume.
Molar specific heat is defined by:
For a monatomic gas at constant volume:

For a monatomic gas at constant pressure:

Summary
In a PV plot,

is constant, where

For a monatomic ideal gas,

The spontaneous flow of heat between objects in thermal
equilibrium is always from the hotter one to the colder one.
A heat engine converts heat into work.
Efficiency of a heat engine:

Summary
A reversible engine has the maximum possible efficiency,

The maximum possible work:

Refrigerators, air conditioners, and heat pumps use work

to transfer heat from a cold region to a hot region.

Summary
Coefficient of performance of a refrigerator:

Work done by an ideal heat pump:

Coefficient of performance for a heat pump:

Summary
Change of entropy during a reversible heat
exchange:

Total entropy of the universe increases whenever

an irreversible process occurs; total entropy is
unchanged after an ideal reversible process.
Entropy is a measure of disorder.
The heat death of the universe will occur when
everything is the same temperature and no more
work can be done.

Summary
It is impossible to lower the temperature of an object to
absolute zero in a finite number of steps.