3.

The first law of thermodynamics

3.1

Work done

Mechanical work = force applied distance (displacement)

dW = F cos ds
3.2

(applied to a point centre of gravity)

Work done to a surface :

P = pressure of gas ;

Pe = external pressure applied on the system

P > Pe

the gas expands

P < Pe

the gas is compressed

dW = Pe A ds
or

dW = Pe dA ds

Write

dV = dA ds
dW = Pe dV

Work done to change the volume by dV

Sign convention :
dV = +ve (expansion)
dW = +ve
dV = -ve

Work done by the system

(compression)

dW = -ve

Work done to the system

If the compression is performed quasistatically so the process is reversible,

then the externally applied pressure Pe = P, the pressure of the gas
then

dW = P dV

In a finite reversible process, to change the volume from Va to Vb ,

Vb

total work done required:

Wa b =

PdV

Va

W can be obtained by expressing P in terms of V using the equation of state.

Example 1 : Ideal gas

PV = nRT

W = nR PdV

(a) If the process is isothermal,

then Wa b is represented by the area under
Vb

the P V curve, hence

Wa b = nRT

(b) If the process is isobaric, then

Vb

Wa b = P dV = P (Vb Va )
Va

Vb
1

dV
=
nRT
ln
V
Va
Va

Example 2 :

Paramagnetic substance

Consider cylindrical paramagnet being magnetised

by current flowing through coil wound around it
(solenoid)
L : length ;

A : cross-sectional area

N : number of turns of the coil

I : current flowing through the coil
The magnetic field intensity produced by I flowing through the coil is

H=

NI
L

Magnetic flux density,

B=

= o H
A

B = o (H + M )

if centre of coil is free space

if centre of coil is filled with paramagnetic
material

dB = o (dH + dM) ; M is the magnetic moment per unit

volume

If B is varying with time, an electromagnetic force (emf) will be induced

emf, = NA

dB
dt
A

= I = ( NI )A

The power input :

Work done on the system :
The term

dB
dB
V dB
= ( HL )
= HV
dt
dt
L dt
NI

dW = dt = I dt = HV dB = oVH dH oVH dM

oVH dH is the work done required for free space

oVH dM is the work done required to magnitise the paramagnet by dM

Unit:

H - ampere per m ( A m-1 )

M A m-1
o = 4 10-7 henry per meter ( H m-1 )
oVH dM henry ampere2 ( H A2 ) joules ( J )

Work of magnitization,

dWm = H dM, M = oV dM

Example 3 :

Surface tension

Take a "U" shape wire frame with another

wire placed on top to form a closed rectangle
Dip the wire frame into soap water so that
a thin film of soap is formed inside the frame
: surface tension ( N/m )
The wire will experience a force due to this
surface tension given by
F=2 L

( 2 because the film has 2 surfaces)

If we pull the wire so as to increase x by dx , the work done required is

dW = 2 L dx = dA
[Note: We use ve sign here since work is done to the system]

3.3

Work done to change the state of a system depends on path

The total work done to change the state of a system from a to b :
b

W = dW
a

For a P-V-T system, take isothermal process, the path taken from a to b can be
represented by

P = f (V )
Vb

and the work done to perform the process is

W=

PdV

which is the area under the

Va

curve P = f (V ) on the P-V surface

The state of the system can change from a to b through different path, each on
represented by a different function. We can see that if 2 paths are different, the areas
under the 2 curves will be different. Hence,
Vb

Vb

WI =

f I (V )dV

Va

W II =

f II (V )dV

Va

WI WII 0

WI WII

II

Va

Vb

This means that if the state of the system is changed from a to b through path I and then
return to a through path II, there will be a net work done by the system [ W = +ve ]
Net work
Hence,

W = dW = PdV

dW is an inexact differential

= +ve

The work done in the expansion (by the system) and compression (to the system) of a gas
is an example of the configuration work
Note that in this case,

P is an intensive variable
V is an extensive variable

In general, if a system has a set of intensive variables Y1 , Y2 , Y3 ...........

and
a set of extensive variables X1 , X2 , X3 ...........
then, the configuration work is dW = (Y dX)
If a gas expand into vacuum , no work is required

free expansion

If there is energy loss during a process , the work done to bring about the process is said
to be dissipative work
All dissipative work is always irreversible
Example of dissipative work: Electric current flowing through resistor
Dissipative work :

W = I2 R dt

3.4 Internal energy

For adiabatic process ( no heat flow in or out of the system ), the work done (by the
system or to the system) to change the state of the system will go into the internal energy
of the system.
Since

work done by the system is

work done to the system is

+ve
-ve

We write internal energy, dU = - dW

because we expect the internal energy to increase when work is done to the system.
In the P-V-T system,

dU = - PdV
Ub

For process from state a and state b ,

dU = U b U a = dW = Wa b

Ua

Thus when a gas expand adiabatically, its internal energy will decrease
Whereas if the gas is compressed adiabatically, its internal energy will increase

3.5 Heat flow

For nonadiabatic process, there is heat flow into the system or out of the system.
Write dQ to be the amount of heat flow during a process, and define
dQ = +ve

heat flow into the system

dQ = - ve

heat flow out of the system

Heat flow from region of high temperature to region of low temperature

Hence, during a nonadiabatic process, the total work done W is given by
W = Wadiabatic + Q
That means

or

Wadiabatic = W Q = Ua Ub

Ub Ua = Q W

Differential form (for small Q and W),

dU = dQ dW

For a P-V-T system,

dU = dQ PdV

In general,

dU = dQ YdX

Since dU does not depend on path, while dW depends on path, so dQ also depends on path

3.6 First Law of Thermodynamics

The expression

dU = dQ dW

is the differential form of the First Law of Thermodynamics, which states that
In any process in which there is no change in the kinetic and potential
energy of the system, the increase in internal energy of the system equals
the net heat flow into the system minus the total work done by the system.
In a more general form, the First Law of Thermodynamics states that
The total work is the same in all adiabatic processes between any two
equilibrium states having the same kinetic and potential energy.
Generalised by including the kinetic and potential energy, we can write
dE = dQ dW ,

where

dE = dU + dEK + dEP

3.7

Unit of heat
1 calorie heat required to flow into 1 gram of water to raise its temperature by 1C
[

1 15-degree calorie temperature raised from 14.5 to 15.5 C

1 BTU heat required to flow into 1 lb of water to raise its temperature by 1 F

Joule's experiment (1940 1978) : Mechanical work Heat

1 calorie of heat 4.19 joules of work done

or

1 BTU of heat 778.28 ft-lb

3.8

Heat capacity
For processes without change of phase, the temperature change of a system T is
proportional to the heat flow into or out of the system,
Q
i.e.
where C is a constant called Heat Capacity of the system
= C,
T
Q dQ
For infinitely small change in temperature,
( J K-1 )
C = lim
=
T 0 T
dT
where Q is given as a function of T ( Note: NOT a function of T )
The heat capacity of a P-V-T system is different for isobaric and isochoric processes.
For isobaric process (constant P ),
For isochoric process ( constant V ),

Specific heat capacity,

T2

Heat flow :

Q = CdT
T1

dQ

dT
c=
m

dQ
C P =

dT

P
dQ
CV =

dT V
or

dQ

dT

c=
n

Copper at P = 1 atm

Mercury at T = 0 C

3.9

Heats of transformation; enthalpy

During an isobaric process, the volume is changed from v1 to v2 .
If a phase change has occured, the heat flow (into or out of the system) is called
the heat of transformation
Using the first law,

du = dq dw

Write

dw = P( v2 v1 )
dq = l

heat of transformation

du = u2 u1
then
The quantity
Hence

u 2 u 1 = l P ( v2 v1 )
( u + P v ) is called the enthalpy h,
l = h2 h1

l = ( u2 + P v2 ) (u1 + P v1 )
h=u+Pv

3.10 Energy equation of steady flow

As an example for the application of the first law of thermodynamics, consider the
following system :

Processes:

piston 1 pushed to the right with velocity v1 and by x1

piston 2 pulled to the right with velocity v2 and by x2
heat Q flow into the system

Result from these processes

Work done by the pistons :

P2V2 P1V1

Water flows from position z1 to z2

Piston movement

Work done output through the shaft : Wsh

change in potential energy, Ep = mg ( z2 z2 )

change in kinetic energy, Ek = m (v22 v12 )

Total work done of the system :

W = Wsh + (P2V2 P1V1)

First Law of Thermodynamics :

U + Ek + Ep = Q W ,

U = m ( u2 u1 )

m( u2 u1 ) + 12 m( 22 12 ) + mg ( z2 z1 ) = Q Wsh ( P2V2 P1V1 )

In terms of specific quantities : ( u2 u1 ) + 12 ( 22 12 ) + g( z2 z1 ) = q w sh ( P2v2 P1v1 )

Or,

( u2 + P2v2 + 12 22 + gz2 ) ( u1 + P1v1 + 12 12 + gz1 ) = q w sh

This is the
For a Bernoulli flow,

energy equation of steady flow

wsh = 0 ,

assuming adiabatic flow

( u2 + P2v2 + 12 22 + gz2 ) ( u1 + P1v1 + 12 12 + gz1 ) = 0

u + Pv + 12 2 + gz = constant