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Law of Thermodynamics

State Variables

State variables describe the state of a system

In the macroscopic approach to

thermodynamics, variables are used to

describe the state of the system

Pressure, temperature, volume, internal energy

These are examples of state variables

They are linked by the Equation of State PV = nRT

The macroscopic state of an isolated system

can be specified only if the system is in

thermal equilibrium internally

Transfer Variables

The quantities Q and W are called transfer

variables.

Transfer variables are zero unless a process

occurs in which energy is transferred across

the boundary of a system

Transfer variables are only associated with

changes in the state of the system, not the

states themselves.

Example of heat: we can only assign a value of

the heat if energy crosses the boundary by heat

Work in Thermodynamics

Work can be done on a deformable system,

such as a gas, as we can apply a force in

which the system changes a dimension, ie

there is a change in distance in the direction

of the force

We cannot do work on a stiff (non-

deformable) body. Why?

Consider a cylinder with a moveable piston

A force is applied to slowly compress the gas

The compression is slow enough for all

the system to remain essentially in

thermal equilibrium

This is said to occur quasi-statically

Work, 2

The piston is pushed downward by a

force F through a displacement of dr:

dW F dr Fˆj dyˆj Fdy PA dy

A.dy is the change in volume of the gas,

dV

Therefore, the work done on the gas is

dW = -P dV

Work, 3

Interpreting dW = - P dV

If the gas is compressed, dV is negative

and the work done on the gas is positive

If the gas expands, dV is positive and the

work done on the gas is negative

If the volume remains constant, the work

done is zero

Vf

The total work done is: W Vi

P dV

PV Diagrams

PV diagrams are used when

the pressure and volume are

known at each step of the

process

The state of the gas at each

step can be plotted on a

graph called a PV diagram

This allows us to visualize the

process through which the gas

is progressing

The curve is called the path

PV Diagrams, cont

The work done on a gas in a quasi-

static process that takes the gas from

an initial state to a final state is the

negative of the area under the curve on

the PV diagram, evaluated between the

initial and final states

This is true whether or not the pressure

stays constant

The work done does depend on the path

taken

Work Done By Various Paths

and final states

The work done differs in each process

The work done depends on the path

Work From a PV Diagram,

Example 1

The volume of the

gas is first reduced

from Vi to Vf at

constant pressure Pi

Next, the pressure

increases from Pi to

Pf by heating at

constant volume Vf

W = -Pi (Vf – Vi)

Work From a PV Diagram,

Example 2

The pressure of the

gas is increased from

Pi to Pf at a constant

volume

The volume is

decreased from Vi to

Vf

W = -Pf (Vf – Vi)

Work From a PV Diagram,

Example 3

The pressure and the

volume continually change

The work is some

intermediate value

between –Pf (Vf – Vi) and

–Pi (Vf – Vi)

To evaluate the actual

amount of work, the

function P (V ) must be

known

Heat Transfer, Example 1

The energy transfer, Q, into or

out of a system also depends on

the process

The energy reservoir is a

source of energy that is

considered to be so great that a

finite transfer of energy does

not change its temperature

The piston is pushed upward,

the gas is doing work on the

piston

Heat Transfer, Example 2

This gas has the same initial

volume, temperature and

pressure as the previous

example

The final states are also

identical

No energy is transferred by

heat through the insulating

wall

No work is done by the gas

expanding into the vacuum

Energy Transfer, Summary

Energy transfers by heat, like the work

done, depend on the initial, final, and

intermediate states of the system

Both work and heat depend on the path

taken

Neither can be determined solely by the

end points of a thermodynamic process

The First Law of

Thermodynamics

The First Law of Thermodynamics is a special

case of the Law of Conservation of Energy

It takes into account changes in internal energy

and energy transfers by heat and work

Although Q and W each are dependent on the

path, Q + W is independent of the path

The First Law of Thermodynamics states that

DEint = Q + W

All quantities must have the same units of measure

of energy

The First Law of

Thermodynamics, cont

One consequence of the first law is that there

must exist some quantity known as internal

energy which is determined by the state of

the system

For infinitesimal changes in a system dEint =

dQ + dW

The first law is an energy conservation

statement specifying that the only type of

energy that changes in a system is internal

energy

Isolated Systems

An isolated system is one that does not

interact with its surroundings

No energy transfer by heat takes place

The work done on the system is zero

Q = W = 0, so DEint = 0

The internal energy of an isolated

system remains constant

Cyclic Processes

A cyclic process is one that starts and ends in the

same state

This process would not be isolated

On a PV diagram, a cyclic process appears as a

closed curve

The change in internal energy must be zero since

it is a state variable

If DEint = 0, Q = -W

In a cyclic process, the net work done on the

system per cycle equals the area enclosed by the

path representing the process on a PV diagram

Adiabatic Process

An adiabatic process is one

during which no energy

enters or leaves the system

by heat

Q=0

This is achieved by:

Thermally insulating the walls of

the system

Having the process proceed so

quickly that no heat can be

exchanged

Adiabatic Process, cont

Since Q = 0, DEint = W

If the gas is compressed adiabatically,

W is positive so DEint is positive and the

temperature of the gas increases

If the gas expands adiabatically, the

temperature of the gas decreases

Adiabatic Processes, Examples

Some important examples of adiabatic

processes related to engineering are:

The expansion of hot gases in an internal

combustion engine

The liquefaction of gases in a cooling

system

The compression stroke in a diesel engine

Adiabatic Free Expansion

This is an example of adiabatic

free expansion

The process is adiabatic because

it takes place in an insulated

container

Because the gas expands into a

vacuum, it does not apply a force

on a piston and W = 0

Since Q = 0 and W = 0, DEint = 0

and the initial and final states are

the same

No change in temperature is

expected

Isobaric Processes

Here pressure is held constant

The values of the heat and the work are

generally both nonzero

The work done is the area under the

curve in the PV diagram, given simply

by

W = P (Vf – Vi) where P is the

constant pressure

Isovolumetric Processes

Here the volume is fixed

Since the volume does not change, W =

0

From the first law, DEint = Q

If energy is added by heat to a system

kept at constant volume, all of the

transferred energy remains in the

system as an increase in its internal

energy

Isothermal Process

Here the temperature is constant

Since there is no change in

temperature, DEint = 0

Therefore, Q = - W

Any energy that enters the system by

heat must leave the system by work

Isothermal Process, cont

At right is a PV

diagram of an

isothermal expansion

The curve is a

hyperbola

The curve is called an

isotherm

Isothermal Expansion, Details

The curve of the PV diagram indicates

PV = constant

The equation of a hyperbola

Because it is an ideal gas and the

process is quasi-static, PV = nRT and

Vf Vf nRT V f dV

W P dV dV nRT

Vi Vi V Vi V

Vi

W nRT ln

Vf

Special Processes, Summary

Adiabatic

No heat exchanged

Q = 0 and DEint = W

Isobaric

Constant pressure

W = P (Vf – Vi) and DEint = Q + W

Isothermal

Constant temperature

DEint = 0 and Q = -W

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