THEMODYNAMICS

ENERGY : WORK AND HEAT

THE FIRST LAW
0 1
 DEFINITION OF TERMS
Historically: physicists and engineers interested in the efficiency of steam engines

Thermodynamics : The study of the transformations of energy and, in particular,

heat work
Thermodynamics is conducted under a system-centered view of the universe.

 The sample is the system of interest

 The rest of the world is its surroundings.

 The universe = the system + the surroundings.

 The surroundings are where we make our observations

 DEFINITION OF TERMS CONTINUE…..

thermodynamic system, ( working substance), is defined as that part of the universe

that is under study.

Thermodynamics is basically concerned with the flow and balance of energy and matter in
a thermodynamic system.

A hypothetical boundary separates the system from the rest of the universe, which is
referred to as the environment, or surroundings.
 SYSTEMS AND SURROUNDINGS

Need to distinguish three types of systems.

Systems can be:

 Open : Mass and Energy can transfer between the System and the Surroundings,
.  e.g the ocean
 A boundary allowing matter exchange is called permeable

 Closed : Energy can transfer between the System and the Surroundings, but NOT mass

 e.g Closed flask

 Isolated : Neither Mass nor Energy can transfer between the System and the Surroundings

 e.g. insulated gas cylinder or dewa.

 THE CONSERVATION OF ENERGY

Energy: is the capacity/ ability to do work.

Work : is done to achieve motion against an opposing force

Work = (force opposing the motion) x (distance moved)

process results in raising the object above the ground, then the process is doing work.

Law of conservation of energy: Energy can be neither created nor destroyed but merely
converted from one form into another
 WORK AND MEASUREMENT OF WORK
Energy can be transferred between a system and its surroundings in two distinct ways:
WORK
HEAT or both

‘work’ and ‘heat’ are modes of transfer of energy, not forms of energy.

More than one kind of work may be associated with a process

w  wcompression  welectrical  wsurface  ...

When energy leaves a system as work, (system does work on the surroundings) then work (w)
is negative (w < 0)

When energy enters a system as work, (work is done onto the system) then the work is
positive (w > 0)
 PRESSURE-VOLUME (P-V) WORK
A very common form of work associated with chemical reactions is the work of expansion or
compression against a restraining pressure.
A gas is placed in a cylinder fitted with a rigid frictionless piston, of cross-
sectional area A.
Expansion Work: system expands against an opposing pressure.

The final states are indistinguishable,

You cannot tell whether the gas

reached The final state by being
heated or having Work done on it.
When a system is in a state of mechanical equilibrium, an infinitesimal change in the
pressure results in opposite directions of motion.

A process that can be reversed by an infinitesimal change in a variable — in this case,

the pressure — is said to be reversible.

Work done is defined as:

If the force opposing the expansion is greatest, ie. reached its maximum value then, the
system must exert most effort to push the piston out

maximum work is obtained when the external pressure is only infinitesimally less than the
pressure of the gas in the system.

A system that remains in mechanical equilibrium with its surroundings at all stages of the
expansion does maximum expansion work.

Mechanical equilibrium (Pext =P)

Suppose that and the piston is driven downwards by a very small distance
The work done by the surroundings on the system is:

Corresponds to the decrease in the volume of the gas.

The decrease in the volume V of the gas is:

This is a useful expression for the calculation of the work

Of expansion or compression against restraining pressure

 This equation is applicable to system of any shape.

 Though the equation was derived for a gas, it is applicable to any state of matter
 The pressure appearing in this expression is the External Pressure, NOT internal pressure
This is because work is evaluated in terms of the changes brought about in the surrounding
NOT changes taking place in the system.
The surroundings are where we make our observations
This equation is applicable to system undergoing an infinitesimal changes

The external pressure determines how much work a system does when it expands through
a given volume

The greater the external pressure, the greater the opposing force and the greater the work
that a system does.
Mathematically, this process corresponds to the process of integration.
 MAXIMUM WORK DONE
Reversible Expansion / Compression

 When a system is in a state of mechanical equilibrium, an infinitesimal change in the

pressure results in opposite direction of change.

 A change that can be reversed by an infinitesimal change in a variable (in this case the
pressure) is said to be reversible.
 Maximum expansion work is achieved in a reversible change.
Mechanical equilibrium: P  P
in ex
For an infinitesimal expansion
because Pext = Pin = P)
For an infinitesimal reversible expansion
V2
Total work done in a reversible expansion: wrev    pdV
V1
Expansion at constant pressure, (i.e. a reversible expansion (with dp = 0.)

V2 V2
wrev    pdV   p  dV   p(V2  V1 )   pV
V1 V1

An isothermal reversible expansion. That is, dT = 0

 IRREVERSIBLE EXPANSION

For measurable work done:

V2 V2
wirr    pext dV   pext  dV   pext (V2  V1 )
V1 V1
VACUUM
System expands against no
Restraining pressure

At all stages during this expansion, the

Total work done is:

No work is done during free

expansion
An indicator diagram is a useful and concise way of describing processes in which a substance
Changes its variables of state (p, V, T, etc.)

However there are many different pathways by means of which that very same system could have
Been taken from the specified initial state to the specified final state.
TOTAL WORK DONE DURING ISOTHERMAL EXPANSION
TOTAL WORK DONE DURING ALTERNATIVE PATHS
 HEAT AND MEASUREMENT OF HEAT
Heat is energy in transit between two bodies at different temperatures.
It is only called heat when in transit
Supply of heat to a body results in a rise in temperature. Heat capacity (C) [J/K]
Specific heat = C/m [J/K.g]
Molar heat capacity = C/n
[J/K.mol]

For infinitesimal changes :

T2
Total heat transferred q   dq   CdT This applicable if C = f(T)
c T1
What happens during Isothermal expansion?

For an isothermal expansion of a gas, the energy left as work is put back in the form of heat.

For an isothermal expansion of an ideal gas, q= -w

 THE INTERNAL ENERGY
Energy is supplied into or out of the system as work or heat.
Once energy is inside the system, it is stored as internal energy, regardless of how the
energy was supplied as work or as heat.
James Joul showed that heat and work are equivalent:

The same rise in

temperature of a given
amount of water is brought
about by transferring a
given quantity of energy
either as heat or work.
U = sum of all Ek and Ep contributions to the energy of all the atoms, ions and molecules
in a system.
Cannot measure the total energy of the sample .

know and measure the change in internal energy (U) because we can determine those by
monitoring the energy supplied or lost as heat or work.
 THE FIRST LAW OF THERMODYNAMICS
The internal energy of an isolated system is constant. i.e. for an isolated system, U = 0)

Mathematical form of the first law: U = w + q

For infinitesimal changes: dU = dw + dq

Ideal gas, Isothermal expansion, U = 0.

At constant Volume, U = q , Commonly written as: U = qv

  U 
The heat capacity at constant volume can be defined as : CV   
 T V
The molar heat capacity at constant volume, Cv,m = Cv/n, is the heat capacity per mole of
material and is an intensive property.

dU= CvdT (at constant volume)

U = qv = CvT (at constant volume, no additional work)

 ENTHALPY OF THE SYSTEM
The enthalpy of the system is defined as : H = U + pV , ( H is extensive property.)

Hm = H/n, molar enthalpy is an intensive property.

pV is always > 0 (positive), then enthalpy of the system is greater than its internal energy

Hm = Um + pVm

At constant Pressure, dH = dq , At constant Pressure, H = qp

q = CpT or dH = CpdT
 THE ADIABATIC CHANGES
an adiabatic process is a type of thermodynamic process that occurs without
transferring heat between the thermodynamic system and its environment

U = w + q. for adiabatic expansion, q = 0, U = wad

U = CvT
wad =CvT (adiabatic expansion of a gas)
final temperature of a perfect gas that undergoes reversible adiabatic expansion (reversible
expansion in an insulating container) can be calculated from .
1c
 Vi 
T f  Ti   CV ,m
V  c
 f  R
the pressure of a perfect gas that undergoes reversible adiabatic expansion from a volume V i
to a volume Vf is related to its initial pressure

 
p f V f  piVi 
CV ,m
C p ,m