Biothermodynamics - (BT 202)

Dr. Selvaraju Narayanasamy,

Associate Professor,
Biochemical and Environmental Engineering Laboratory,
Department of Biosciences and Bioengineering,
Indian Institute of Technology Guwahati,
Guwahati, Assam, India - 7​81039.
PVT behaviour of pure
substances
 PURE SUBSTANCE
➢A substance that has a fixed
chemical composition throughout
➢Pure Substance does not have to be
made of Single chemical
element/compound.
➢A mixture of various chemical
elements/compounds can be treated
as Pure Substance.
➢Condition : Homogeneous
PROPERTIES OF PURE SUBSTANCE

➢A mixture of 2 or more phases of a

Pure Substance is still a Pure
Substance
➢Condition : As long as the
Chemical Composition of ALL
phases stays the same
PHASES OF A PURE SUBSTANCE

The arrangement of atoms in different phases: (a) molecules

are at relatively fixed positions in a SOLID, (b) groups of
molecules move about each other in the LIQUID phase, and
(c) molecules move about at random in the GAS phase.
Phase-Change Processes of Pure Substance

T-υ Diagram
T, °C

υ, m3/kg
 Phase-Change Processes of Pure Substance

State 1

Initial condition of liquid

T = 20oC
P = 1 atm

❖ Heat is added until temperature increase to

T = 40oC

❖ Compressed Liquid or subcooled liquid’ - not started

to vaporize
Phase-Change Processes of Pure Substance
T, °C
T-υ Diagram

300

100

20
compressed

υ, m3/kg
 Phase-Change Processes of Pure Substance

State 2

heat is added until

T = 100oC
P = 1 atm

➢Any addition of heat will cause vaporize

❖ Saturated Liquid -liquid about to vaporize

Phase-Change Processes of Pure Substance
T, °C T-υ Diagram

300

100

20

υ, m3/kg
Phase-Change Processes of Pure Substance

State 3
➢ ‘saturated liquid-vapor mixture’
➢ T constant until completely vaporized
➢ decrease liquid level, increase vapor
Phase-Change Processes of Pure Substance
T, °C
T-υ Diagram

300 Adding heat here

convert liq > vap

Saturated Liq-Vap

100
mixture

20

υ, m3/kg
 Phase-Change Processes of Pure Substance

State 4
➢ ‘saturated vapor’
➢ more heat until last liquid vaporizes
➢ Any heat loss, vapor start to condense
become liquid
Phase-Change Processes of Pure Substance

State 5
more heat
T >100oC
P = 1 atm

➢ vapor not about to condense even

there’s loss of heat.

Superheated Vapor
Phase-Change Processes of Pure Substance
T-υ Diagram
T, °C

300 Adding heat here

convert liq > vap

Saturated Liq-Vap

100
mixture

20

υ, m3/kg
 Phase-Change Processes of Pure Substance

▪ Compressed liquid or a subcooled liquid:

A liquid that is not about to vaporize.
▪ Saturated liquid: A liquid that is about to
vaporize.
▪ Saturated vapor: A vapor that is about to
condense.
▪ Saturated liquid-vapor mixture: the liquid
and vapor phases coexist in equilibrium.
▪ Superheated vapor: A vapor that is not
about to condense
 Adding heat here
converts liquid to
vapour –”Latent Heat”

Adding heat here raises

temperature –”Sensible
Heat

T-v diagram for the heating process of water at

constant pressure.
 Phase-Change Processes of Pure Substance
▪ Saturated temperature, Tsat: At a given pressure,
the temperature at which a pure substance
changes phase.
▪ Saturated pressure, Psat: At a given temperature,
the pressure at which a pure substance changes
phase.
▪ Latent heat: the amount of energy absorbed or
released during a phase-change process.
▪ Latent heat of fusion: the amount of energy
absorbed during melting.
▪ Latent heat of vaporization: the amount of energy
absorbed during vaporization.
 PVT BEHAVIOR OF PURE SUBSTANCES/ FLUIDS
Critical point: The point at
which the saturated liquid and
saturated vapor states are
identical.

The 2-C line, also known as

vaporization curve is where
liquid-vapor is in equilibrium

Triple point, three

phases exist in
The 1-2 line, also The 2-3 line, also known as
equilibrium (F=0)
known as sublimation fusion curve is where solid-
curve is where solid- liquid is in equilibrium
vapor is in equilibrium
 Critical Point
▪ When the temperature is increased to Tc , the saturated liquid and
saturated vapour becomes indistinguishable.
▪ The liquid state changes to vapour state without any discontinuity at
the critical point.
▪ The critical properties of water as follows:
Tc = 647.3 K ; Pc = 220.5 bar.
▪ If the temperature is less than the critical value, the substance is called
vapour. Above its critical temperature , the substance is called gas.
▪ A vapour can be condensed to a liquid by compression at constant
temperature or by cooling at constant pressure.
▪ A gas can be condensed only by reduction of temperature at constant
pressure. It cannot be condensed by compression at constant
temperature.
▪ If the temperature and pressure greater than its critical value, the
substance is in the fluid region and it can neither be condensed by any
of the above method nor can it be vaporized by reduction in pressure.
PV diagram

❖Boundaries in PT diagram
becomes region when
illustrate with PV diagram

Critical point becomes peak of the

curve

Triple point becomes horizontal line

 Compressed liquid region
Saturated liquid line at boiling
temperature

Superheated vapor region

Saturated vapor line at
condensation temperature

T >Tc, the line do not cross the

boundary

Isotherm: a curve on a diagram Isotherms in sub-cooled/ compressed lliquid

joining points representing region are steep, because liquid volumes
states of equal temperature change little with large changes in pressure
 SINGLE PHASE REGION
➢ At single phase regions in PV diagram, there is a relation
connecting P,V and T.
➢ This relation known as equation of state; f(P,V,T)=0
➢ If V is considered as a function of T and P, then V=V(T,P)

 V   V 
dV =   dT +   dP
 T  P  P T
1  V 
   Volume exp ansivity
V  T  P
1  V 
−    isothermal compressibility
V  P T
 dV
The combination will yield; =  dT − dP
V

➢ The isotherms on the left side of PV diagram are very steep,

both β and κ are small.
➢ Because of that, the liquid is known as incompressible fluid,
where both constants are equal to zero
➢ However, this is just idealization, and in incompressible fluid,
no equation of state exist, since V is independent of T and P

❖If, we still want to calculate, for liquids, Integration of 3.4

yield
V2
ln =  (T2 − T1 ) −  ( P2 − P1 )
V1

Check out Ex 3.1

For liquid acetone at 20°C and 1 bar
β = 1.487 × 10-3 °C-1 ; κ = 62 × 10-6 bar-1 ; v = 1.287 cm3 g-1
Find:
𝜹𝑷
(i) The value of ,
𝜹𝑻 𝒗

(ii) The pressure generated by heating at constant v from 20°C and 1 bar
to 30°C,
(iii) The change in volume for a change from 20°C and 1 bar to 0°C and
10 bar

Solution:
𝑑𝑣
i At constant Volume: = 𝛽𝑑𝑇 − 𝜅𝑑𝑃 = 0
𝑣

𝛿𝑃 𝛽 1.487×10−3
_ = = = 23.98 °C-1 bar
𝛿𝑇 𝑉 𝜅 62×10−6
 𝑑𝑣
ii At constant Volume: = 𝛽𝑑𝑇 − 𝜅𝑑𝑃 = 0
𝑣
𝛽
_ ∆𝑃 = ∆𝑇 = 23.98°C-1 bar × 30 − 20 °𝐶 = 239.8 𝑏𝑎𝑟
𝜅

_ ∆𝑃 = 𝑃2 − 𝑃1 _ 𝑃2 = 𝑃1 + ∆𝑃

_ 𝑃2 = 1 + 239.8 = 240.8 𝑏𝑎𝑟

𝑑𝑣 𝑣2
iii = 𝛽𝑑𝑇 − 𝜅𝑑𝑃 = 0 _ 𝑙𝑛 = 𝛽 𝑇2 − 𝑇1 − 𝜅(𝑃2 − 𝑃1 )
𝑣 𝑣1

𝑣2
_ 𝑙𝑛 = 1.487 × 10−3 × (0 − 20) − 62 × 10−6 × (10 − 1)
𝑣1
𝑣2
_ = 0.9704 _ 𝑣2 = 0.9704𝑣1
𝑣1
_ 𝑣2 = 0.9704 × 1.287 = 1.249 cm3 g-1

_ ∆𝑣 = 𝑣2 − 𝑣1 = 1.249 − 1.287 = −0.038 cm3 g-1

 IDEAL GAS
➢ There are several Equations of State, some are simple while
others are very complicated.
➢ The simplest and the best known Equation of State for
substance in GAS phase is the Ideal Gas Equation Of
State.
➢ The Equation of State predicts P, T and v behaviour of a
GAS quite accurately but within some properly selected
region, i.e. it has limitation.

PV = nRT or Pυ = RT
140 kg of nitrogen at a pressure 4.052 × 105 Pa is stored in a cylinder of
volume 30 m3. It is desired to keep the gas temperature below 25°C. Does
the cylinder need cooling if nitrogen behaves like an ideal gas.
Solution:
Number of moles of nitrogen = 140/28 = 5 kmol = 5000 mol

𝑃𝑉 4.052 × 105 ×30

_ 𝑇= = = 292.42 K
𝑛𝑅 5000×8.314

Therefore, the cylinder does not require cooling.

Implied Property Relations for an Ideal Gas
Isochoric (or isometric) process:
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 _ 𝑑𝑊 = 𝑃𝑑𝑉 =0
𝑑𝑈
_ 𝑑𝑄 = 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 _ 𝐶𝑉 =
𝑑𝑇
Isobaric process:
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
𝑑𝐻
_ 𝑑𝑄 = 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 _ 𝐶𝑃 =
𝑑𝑇
Enthalpy:
𝐻 = 𝑈 + 𝑃𝑉 For 1 mole of ideal gas: _ 𝐻 = 𝑈 + 𝑅𝑇
𝑑𝐻 𝑑𝑈
_ 𝑑𝐻 = 𝑑𝑈 + 𝑅𝑑𝑇 % by dT _ = +𝑅
𝑑𝑇 𝑑𝑇
_ 𝐶𝑃 = 𝐶𝑉 + 𝑅 _ 𝐶𝑃 −𝐶𝑉 = 𝑅
Implied Property Relations for an Ideal Gas
Isothermal process:
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 _ 𝑑𝑈 = 0

_ 𝑑𝑄 = 𝑑𝑊 = න 𝑃𝑑𝑉 For 1 mole of ideal gas:

𝑅𝑇 𝑑𝑉
_ 𝑑𝑄 = 𝑑𝑊 = න 𝑑𝑉 = 𝑅𝑇 න
𝑉 𝑉
𝑉2
_ 𝑄 = 𝑊 = 𝑅𝑇 𝑙𝑛
𝑉1
For an ideal gas at constant temperature:
𝑉2 𝑃1 𝑃1
𝑃1 𝑉1 = 𝑃2 𝑉2 _ = _ 𝑄 = 𝑊 = 𝑅𝑇 𝑙𝑛
𝑉1 𝑃2 𝑃2
Adiabatic process:
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 _ 𝑑𝑄 = 0 _ 𝑑𝑈 = − 𝑑𝑊 = − 𝑃𝑑𝑉
& 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
𝐶𝑉 𝑑𝑇 = − 𝑃𝑑𝑉

For 1 mole of ideal gas: _ 𝐶𝑉 𝑑𝑇 = − 𝑅𝑇

𝑉
𝑑𝑉

𝑑𝑇 𝑅 𝑑𝑉 𝑑𝑇 𝐶𝑃 −𝐶𝑉 𝑑𝑉
_‫׬‬ =− ‫𝑉 ׬‬ _‫׬‬ =− ‫𝑉 ׬‬
𝑇 𝐶𝑉 𝑇 𝐶𝑉

𝑑𝑇 𝐶𝑉 𝐶𝑃 𝑑𝑉 𝐶𝑃 𝑑𝑇 𝑑𝑉
_න = − න 𝛾= _න = (1 − 𝛾) න
𝑇 𝐶𝑉 𝐶𝑉 𝑉 𝐶𝑉 𝑇 𝑉

𝛾−1 𝛾−1
𝑇2 𝑉1 𝑇2 𝑃2 𝛾
_ = _ = _ 𝑃1 𝑉1 𝛾 = 𝑃2 𝑉2 𝛾 =P𝑉 𝛾 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇1 𝑉2 𝑇1 𝑃1
Adiabatic process:
Work done: 𝑑𝑊 = − 𝐶𝑉 𝑑𝑇
𝑅
_ 𝑊 = 𝐶𝑉 (𝑇1 − 𝑇2 ) & 𝐶𝑉 =
𝛾−1

𝑅𝑇1 − 𝑅𝑇2 𝑃1 𝑉1 − 𝑃2 𝑉2
_ 𝑊= _ 𝑊=
𝛾−1 𝛾−1
1
𝑃1 𝑉1 𝑃2 𝑉2 𝛾
_ 𝑊= 1− 𝑃1 𝑉1 𝑃2 𝑃1
𝛾−1 𝑃1 𝑉1 _ 𝑊= 1−
𝛾−1 𝑃1 𝑃2

γ−1
𝑃1 𝑉1 𝑃2 𝛾
_ 𝑊= 1−
𝛾−1 𝑃1
Polytropic process:

𝐺𝑒𝑛𝑒𝑟𝑎𝑙𝑙𝑦 𝑛 𝑣𝑎𝑙𝑢𝑒 𝑙𝑖𝑒𝑠 PV n = const

𝑏𝑒𝑡𝑤𝑒𝑒𝑛 1 𝑎𝑛𝑑 γ
An ideal gas is undergoing a series of three operations: The gas is heated at
constant volume from 300 K and 1 bar to a pressure of 2 bar. It is
expanded in a reversible adiabatic process of 1 bar. It is cooled at constant
pressure of 1 bar to 300 K. Determine the heat and work effects for each
step. Assume CP = 29.3 kJ/kmol K.
Solution:
𝐶𝑃 − 𝐶𝑉 = 𝑅 _ 𝐶𝑉 = 𝐶𝑃 − 𝑅

𝑘𝐽
_ 𝐶𝑉 = 29.3 − 8.314 = 20.986
𝑘𝑚𝑜𝑙 𝐾

Step 1: Volume remains constant. 𝑊 = 0 & 𝑄 = 𝐶𝑉 𝑑𝑇

𝑇2 𝑃2 2
Also, = = =2
𝑇1 𝑃1 1

_ 𝑇2 = 2 × 300 = 600 𝐾

𝑘𝐽
𝑄 = 20.986 × 600 − 300 = 6295.8
𝑘𝑚𝑜𝑙
Step 2: Adiabatic process. Q = 0 & 𝑊 = − 𝐶𝑉 𝑑𝑇
𝛾−1
𝑇2 𝑃2 𝛾
Also, =
𝑇1 𝑃1

𝐶𝑃 29.3
_ 𝛾= = = 1.4
𝐶𝑉 20.986

𝛾−1 1.4−1
𝑃2 𝛾 1 1.4
_ 𝑇2 = 𝑇1 = 600 × = 492.2 𝐾
𝑃1 2

𝑘𝐽
𝑊 = 20.986 × 600 − 492.2 = 2262.3
𝑘𝑚𝑜𝑙
Step 2: Isobaric process.
Q = Δ𝐻 = 𝐶𝑃 𝑑𝑇

𝑘𝐽
𝑄 = 29.3 × 300 − 492.2 = − 5631.5
𝑘𝑚𝑜𝑙

Δ𝑈 = 𝐶𝑉 𝑑𝑇

𝑘𝐽
Δ𝑈 = 20.986 × 300 − 492.2 = −4016.2
𝑘𝑚𝑜𝑙

First Law: Δ𝑈 = 𝑄 − 𝑊 _ 𝑊 = 𝑄 − Δ𝑈

𝑘𝐽
_ 𝑊 = − 5631.5 − −4016.2 = −1615.3
𝑘𝑚𝑜𝑙