ENGINEERING THERMODYNAMICS I

Prof. J F Kanyua

Module 4 (Part 1)

1) Boyle’s Law

Date 1662

In France, Boyle’s Law may be referred to as Edme Mariotte Law.

During a change of state in which the mass and the temperature remain constant, the
volume varies inversely as the pressure.

P = Constant/V

pV = Constant (at Constant Temperature)

pdV + Vdp = 0

−𝑝𝑑𝑉 −𝐶 𝑑𝑉 𝑑𝑉
dp = = = −𝐶 𝑉 2
𝑉 𝑉 𝑉

𝑑𝑝 −𝐶
=
𝑑𝑉 𝑉2

As V 0 , P ∞

As V ∞ , P 0

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 P
dp c
dv v²

P vs V

P vs 1/V

1/V

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 P

P1 1

2
P2

3
P3

V
V1, V2 , V3

P1V1 = P2V2 = P3V3 = Constant

P = C/V

1/V

2) Charles’s Law

Jacques Charles (1747 - 1823)

Derived in 1787 (Before Laws of Thermodynamics)

It is also known as Gay-Lussac (1778 – 1850) Law.

The specific volume of gas (permanent) at constant pressure increases linearly with
the temperature measured on a uniformly divided mercury-in-glass thermometer.

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𝑣 P1
p2
p3

3) Charles’s Law and Absolute Temperature

P1
v P2

P3

Origin

V0 V0

V0

t
T

V = Ct + V0 (Vo = Volume at t = 0 for particular P). t = Celsius

−𝑉0
At V = 0 (hypothetical) t =
𝐶

Select temperature scale (T) so that V = CT where T is the temperature reckoned

from the new origin. The new origin is t = - 2730 𝐶.

Therefore T = t + 273K

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T is the absolute temperature. The new origin is the absolute zero of temperature.

Extrapolation gives an “Origin” at which v = 0. This is the same for all gases and is

at – 273.16 0C.

Expressing v as linear function of T:

V = CT

T = (t + 273.16) 0Kelvin

Origin is referred to as absolute zero of temperature. If v = 0, no further reduction is

possible since there is nothing left to reduce in temperature.

Charles’s Law based on absolute temperature: During the change of state of any gas
in which mass and pressure remain constant, the volume varies in proportion with
absolute temperature.

p
Boyle’s Law

2
A
Charles’s Law

Boyle’s Law: P1V1 = PAVA

 VA = P1V1/PA

From Charles’s Law (Process A to 2) :

P2 = PA

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𝑉2 𝑉
= 𝑇𝐴
𝑇2 𝐴

T1 = TA (Boyle’s Law process 1 to A)

𝑉𝐴 𝑉
 = 𝑇2
𝑇1 2

But VA= P1V1/PA

𝑃1𝑉1 𝑉2
 =
𝑇1 𝑃2 𝑇2
𝑃1𝑉1 𝑃2 𝑉2
Or =
𝑇1 𝑇2

i.e. PV/T = Constant

V = mv (mass x specific volume)

𝑝𝑉
 =C
𝑇
𝑝𝑣𝑚
=C
𝑇
𝑝𝑣 𝐶
=𝑚
𝑇

If we make m = 1kg, C/m = Another constant which is unique for each gas (say R)

 pv = RT

Or pV =mRT

This is known as the ideal gas law and is closely obeyed by real gases:

R is known as the gas constant and has different values for different gases.

Units of R:

𝑝𝑣 𝑁
R = =( 𝑚2 ) ( m3/ kg) (1/K)
𝑇

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 = N.m /kg – K

= J/ kg – K
The ideal gas law now allows us to predict the behaviour of a gas if:

➢ The volume remains constant

➢ The temperature remains constant
➢ The pressure remains constant

Units of Pressure

P = Force/Area = N/m2

Pascal = 1N/m2

Kilo-Pascal (kPa) = 1000 N/m2 =1 kN/m2

Mega-Pascal (MPa) = 106 N/m2 = 1000 kN/m2 = MN/m2

Bar = 105 N/m2 = 105 Pascal = 100 kPa

 1 Bar = 0.1 MN/ m2 = 0.1 MPa

From pv =RT or PV = mRT

Apply Avogadro’s hypothesis:

The volume of 1 mole of any gas is the same as the volume of 1 mole of any other
gas, when the gases are at the same temperature and pressure.

PV = mRT = NMRT

PV/NT = MR is Constant for all gases.

MR is given the symbol MR = R0 where R0 is the universal gas constant (or the molar
gas constant).

Units of R0 = :

pV = mRT = NMRT = (MR) NT

= R0NT

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R0 = PV/NT = (N/m2)(m3)/ mole – K

 R0 = N- m / mole –K

 R0 = 1000 N – m /1000 mole – K

 R0 = 1000 Joule /1000 mole – K

 R0 = kJ /kmole – K

R0 = 8.3143 kJ /kmole – K
Note:

pV = NMRT = NROT

V = NROT/ P

vN = ROT/ P (Volume of 1 mole)

If T and P are constant, vN is the same for all gases.

If we plot pv versus T with NRo = constant by taking, say N = 1 kmole; then the
Charles’s Law plots of V versus t for constant P will collapse into a single line with a
gradient equal to (NRo).

Thus the ideal gas law can be used to determine absolute 0 of temperature and the
unit of Kelvin Degree.

4) Kelvin Scale
➢ Kelvin Scale is designed so that zero degrees Kelvin is defined as absolute zero,
which is a hypothetical temperature at which all molecular movement ceases.
➢ Celsius Scale
AKA Centigrade Scale
Named after Anders Celsius (1701 – 44) who was the inventor of the scale. Lower
Reference fixed point: Melting point of pure ice – (Designated 0C)
Upper Reference point: Boiling point of pure water (Designated 100 0C)
➢ Boiling and freezing Points are defined for 1 standard atmosphere (because
boiling and freezing temperature is influenced by the pressure).

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➢ The Kelvin: Defined as the fraction 1/273.16 of the thermodynamic temperature
of the triple point of water (Exactly 0.01 0C). In other words it is defined such that
the triple point of water is exactly 273.16 0K.

Note:

The gas laws presented hereinbefore are applicable at relatively low pressures and
relatively high temperatures.

PV

P0V0

K
T0 = 273.160K
Taz = 00K t0 = 00C

taz = - 273.160C

pV = R0NT

Slope = poV0/T0 = R0N

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 Dalton’s Law

Each gas in a mixture of gases has the same properties as if it alone filled/occupied
the total volume (container)

Characteristics Equation of a Perfect Gas

General changes of state of a gas in which p, υ and T are allowed to change (unlike
in Boyle’s Law and Charles’s Law)

P
1

2
3

V
Process 1 -2: Boyle’s Law

𝑃1 𝑉1
𝑃1 𝑉1 = 𝑃2 𝑉2 ∴ 𝑉2 = 𝑃2

Process 2 – 3: Charles’s Law

𝑉3 𝑇3
=
𝑉2 𝑇2

During process 1 – 2, 𝑇1 = 𝑇2

𝑉3 𝑇3 𝑉3 𝑇1
∴ = ∴ 𝑉2 =
𝑉2 𝑇1 𝑇3

𝑃1 𝑉1 𝑃1 𝑉1
𝑉2 = =
𝑃2 𝑃3

𝑉3 𝑇1 𝑃1 𝑉1
∴ 𝑉2 = =
𝑇3 𝑃3

𝑉3 𝑃3 𝑃1 𝑉1 𝑃2 𝑉2
Or = = −−−−−−−−
𝑇3 𝑇1 𝑇2

𝑃.𝑉
I.e. = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇

V = mυ υ = Specific Volume

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 𝑃𝑚υ
∴ = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇
𝑃υ 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
= = 𝑅: 𝑆𝑝𝑒𝑐𝑓𝑖𝑐 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑓𝑜𝑟 1𝑘𝑔 𝑜𝑓 𝑔𝑎𝑠
𝑇 𝑚
𝑃υ
=𝑅
𝑇
𝑃V
= 𝑚𝑅 𝑜𝑟 𝑝𝑉 = 𝑚𝑅𝑇
𝑇
𝑁
𝑃𝑉 .𝑚3 𝑁−𝑚
𝑚2
Units: 𝑚 = =
𝑇 𝐾.𝑘𝑔 𝐾−𝑘𝑔

𝐽
R=
𝑘𝑔−𝐾

R = Work done when 1 kg of gas is heated at constant pressure through 1 degree rise
of temperature.

𝑚𝑅𝑇 𝑃2 𝑇2
➢ Constant Volume Pressure p = = 𝐶𝑇, =
𝑉 𝑃1 𝑇1

𝑚𝑅𝑇 𝑉2 𝑇2
➢ Constant Pressure Process: 𝑉1 = = 𝐶𝑇 , =
𝑃 𝑉1 𝑇1

➢ Constant Temperature Process: PV =C , 𝑃2 𝑉2 = 𝑃1 𝑉1

Polytropic Process

The constant volume, and constant pressure processes are limiting cases of a more
general type of process in which υ and p change but in a specified manner.

In many real processes, expansion or compression may be described by 𝑝υ𝑛 =

𝐶𝑜𝑛𝑡𝑎𝑛𝑡 where n is the index of expansion or compression.

𝑝υ𝑛 = 𝐶𝑜𝑛𝑡𝑎𝑛𝑡 is the polytropic process

Case 1: 𝑛 = 0: 𝑝υ0 = 𝐶𝑜𝑛𝑡𝑎𝑛𝑡 , υ0 = 1 ∴ 𝑝 = 𝐶𝑜𝑛𝑡𝑎𝑛𝑡

1
𝐶𝑜𝑛𝑡𝑎𝑛𝑡
Case 2: n=∞ 𝑝υ𝑛 = 𝐶𝑜𝑛𝑡𝑎𝑛𝑡 𝑝 𝑛 υ = 𝐶𝑜𝑛𝑡𝑎𝑛𝑡 υ= 1
𝑝𝑛

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 1
if n = ∞ , 𝑝∞ 𝑃0 = 1 ∴ υ = Constant

Case 3: n = 1 𝑝υ𝑛 = Constant 𝑝υ1 = Constant pυ = Constant = mRT

∴ 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠

P n

n=0

n=∞

Availability and Gibbs Function

Josiah Willard Gibbs

Born 1839

Died 1903

Physics Chemistry, Mathematics

Gibbs Entropy

Gibbs Free Energy

Gibbs-Helmholtz Equation

Gibbs-Durham Equation

Gibbs Isotherm

Gibbs Inequality

Availability

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Recall: In the most engines studied, heat was rejected at condenser temperature and
pressure. Heat rejection is at a temperature higher than the temperature of the
surroundings.

If the surroundings are at constant temperature T0 and pressure P0, the maximum
work which can be done by the system interacting with the environment is if the
heat rejection is at (T0, P0).

Availability: Availability is a measure of this maximum theoretical useful work (w net)

Recall: Heat reservoir – A heat source of infinite capacity and therefore invariably at
temperature.

Recall: Heat is a system of infinitely large capacity and therefore its condition
remains at (T0, P0).

Recall: Carnot Cycle: Heat input at constant upper temperature (T) and heat rejection
at constant lower temperature (T0).

Recall Carnot Cycle Efficiency: is the highest possible.

ηcarnot= (Q1-Q2)/Q1 =1- Q2/Q1

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Q2/Q1 = T2/T1

∴ ηcarnot= 1- (T2/T1)

Availability is the Wnet done in a Carnot Cycle when heat source is at T1 and makes
available heat amount Q1

∴ Availability = ηCARNOT x Q1

= Q1 x (T1-T2)/T1

Recall: Power cycles studied so far involve a secondary fluid (working fluid) being
taken in a cycle while the complete system is not undergoing a cycle process.

When working fluid has reached (T0, P0) i.e. at equilibrium with surroundings the
working fluid is not able to produce further work.

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Availability for Closed System

Consider cylinder and piston system.

Consider initial state as (T1, P1)

Surroundings at (T0, P0)

Recall Reversible Non-flow Energy Equation:

Q- W = dU

Applying this equation to the working fluid:

W1 = Q- dU = Q-(U0-U1)

The piston does work on the surroundings equal to:

W’= p0(V0- V1)

The useful work fluid done on the piston is:

W = W1-W’

= Q-( U0-U1) - p0(V0- V1)

= Q-( U0+ p0V0) –( U1 + p0V1)

Recall: Principals of increase in entropy of the system (dS) and of the surroundings
(dS0)

dS + dS0 ≥ 0

Q = ≤ T0 +(S0-S1)

Equality holds if the process is irreversible.

W = Q -(U0+ p0V0) + (U1 + p1V1)

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If Q ≤ T0(S0-S1)

Then W ≤ - (U0+ p0V0) + (U1 + p1V1) + T0 (S0-S1)

W ≤ (U1 + p1V1 - T0 S1) – (U0+ p0V0 - T0 S0)

Equality holds if process is reversible.

∴ Wmax = (U1+ p1+v1- T0 S1) – (U0+ p0V0 - T0 S0)

∴ Wmax = A1 – A0

A = U + P0V - T0S Non-flow availability function

A is a property of the system and also a property of the surroundings.

Gibbs function

G = H – TS

G 0 = HO - T 0 S 0

= U0 + p0V0 - T0 S0

= A0

Example

1) Application to case where initial state (p0 T1) = (p0 T0)

This represents successive isentropic compression and expansion of a gas
yielding zero net work.
2) Application to case where saturated liquid is changed to saturated vapour at
constant p & T.
Wmax = (ufo + p0vfo- T0 Sf0) – (ugo+ p0vgo- T0 Sgo)
h= pv-u

Wmax = (hfo- hgo) - ToSfo + T0 Sgo

= -((hgo- hfo) + To(Sgo – Sfo)

Wmax = - (hfgo - T0 Sfgo)

Wmax = hfgo = T0 Sfg

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∴ Wmax = 0 i.e. no useful work can be derived from this process.

Availability for Steady –Flow Open System

Recall: Q = W = m(dh+dc2/2 + gdz)

W = - m (dh + dc2/2 + gdz) + Q

W = - m[ (h0 – h1) +( C02 – C12)/2 + g(z0 – z1]

= +Q

W= - m(h0 + C02/2 +gzo)

- m(h1 + C12/2 + gz1) + Q

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Q = T0(S0-S1)

∴ W ≤ - (H0 – H1) +T0(S0-S1)

∴ Wmax = (H1 - T0 S1) – (H0 – T0S0)

= B1-B0

Note:

B and A differ in the pressure term.

B= H - T0S = U +Pv- T0S

A= U +p0V - T0S

When state 1 is the same as state 0, then A = B = G

Helmholtz Function

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