SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

Equations of State

An equation of state is an equation which relates the variables of state (T, P, V, and n). It's
particularly useful when you want to know the effect of a change in one of the variables of state

• Solids and Liquids: If the pressure on a solid or liquid is increased, the volume does not
change much. If the temperature is increased, the volume doesn't change much either.
Therefore, an appropriate equation of state describing such systems would be: V(T,P) =
constant.

• Gases: In contrast, changing the pressure or temperature of a gas will have an easily
observable effect on the volume of that gas. For an ideal gas (no intermolecular
interactions and no molecular volume) n appropriate equation of state would be: V(T,P,n)
= (nRT)/P.

• There are many equations of state describing real gases. These equations take in
consideration molecular volume and interactions. The most well-known such equations is
probably the Van der Waals equation.

Ideal and real gases

An ideal gas is one which follows the ideal gas equation of state, namely

PV = (m/M) (MR) T = n Ru T

The universal gas constant has a value of 8.314 J/mol K or kJ/kmol K and is related to the
specific gas constant by the relation Ru = (R /M)
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

The ideal gas equation of state can be derived from the kinetic theory of gases where the
following assumptions are made:

1. The molecules are independent of each other. In other words, there are no attractive
forces between the molecules.

2. The molecules do not occupy any volume. That is the volume occupied by the molecules
is quite negligible compared to the volume available for motion of the molecules.

The internal energy of an ideal gas is a function of temperature only and is independent of
pressure and volume. That is,

u= u(T)

(∂u/∂P)T =0, (∂u /∂v)T = 0

Enthalpy and specific heat

h = u+ Pv

For an ideal gas u = u(T) only and PV = mRT and hence h = h(T) only.

The specific heat at constant volume is defined as the amount of energy transferred as heat at
constant volume, per unit mass of a system to raise its temperature by one degree. That is,

Cv = (dq/dT)v
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

The specific heat at constant pressure is defined as the energy transferred as heat at constant
pressure, per unit mass of a substance to raise its temperature by one degree. That is Cp =
(dq/dT)P

For a constant pressure process dq = du + dw = du + Pdv = du+ Pdv +vdP(since dP=0 for a
constant pressure process)

Or dq= du+d(Pv) = d(U+ Pv) = dh

or dq=dh

CP = (∂h/∂T)P

The ratio of specific heat (γ) is given by

γ= C P/Cv

For mono-atomic ideal gases γ = 1.67 and for diatomic gases γ= 1.4.

Relation between two specific heats:

The two specific heats are related to each other.

h= u + Pv or dh = du + d(Pv)

For an ideal gas, the above equation reduces to

dh = du + d(RT) = du + RdT or

dh/dT = du/dT+R or CP = Cv+ R

or CP –Cv =R for an ideal gas.

 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

γ= CP /Cv or CP = R/(γ-1) and Cv = Rγ/(γ-1)

Real gases:

The ideal gas law is only an approximation to the actual behavior of gases.

At high densities, that is at high pressures and low temperatures, the behavior of actual or real
gases deviate from that predicted by the ideal gas law. In general, at sufficiently low pressures or
at low densities all gases behave like ideal gases.

Van der Waals Equation of State

An equation of state taking account the volume occupied by the molecules and the attractive
forces between them.

(P+a/v2 )(v-b) = RT

where a and b are van der Waals constants.

The equation is cubic in volume and in general there will be three values of v for given values of
T and P.

However in some range of values of P and T there is only one real value v.
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

For T >Tc (critical temperature) there will be only one real value of v and for T< Tc there will be
three real values.

In Figure, the solid curve represents the value predicted by the van der Waals equation of state
and the points represent the experimentally determined values.

It can be observed that at temperatures greater than critical, there is only one real value of
volume for a given P and T.

However at temperatures less than the critical, there are three real values of volume for a given
value of P and T.

The experimental values differ from those predicted by van der Waals equation of state in region
2345 if T<Tc.

One can use the criterion that the critical isotherm (isotherm passing through the critical point)
shows a point of inflexion. Stated mathematically

(∂P/∂v)T=Tc= 0 and (∂2P/∂v2)T=Tc = 0

(∂P/∂v)T=Tc = -RTc/(vc –b)2 + 2a/vc3 = 0

or

RTc/(vc –b)2 = 2a/vc3

(∂2P/∂v2)T=Tc = 2RTc/(vc-b)3 -6a/vc4 = 0

or

2RTc/(vc-b)3 = 6a/vc4
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

Therefore

2/(vc –b) = 3/vc or vc = 3b

At the critical point, the van der Waal’s equation is given by

Pc = RTc/(vc – b) – a/vc2

From these equations,

a = 27R2Tc2/64 Pc and b = RTc/8Pc

Compressibility Factor:

The deviation from ideal behavior of a gas is expressed in terms of the compressibility factor Z,
which is defined as the ratio of the actual volume to the volume predicted by the ideal gas law.

Z = Actual volume/volume predicted by ideal gas law = v/RT/P = Pv/RT

For an ideal gas Pv = RT and hence Z = 1 at all temperatures and pressures.

 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

The experimental P-v-T data is used to prepare the compressibility chart.

Reduced pressure, PR = P/Pc,

Reduced temperature, TR = T/Tc

Reduced volume, vR = v/vc

Where Pc, Tc and vc denote the critical pressure, temperature and volume respectively.

These equations state that the reduced property for a given state is the value of this property in
this state divided by the value of this same property by at the critical point.

The striking fact is that when such Z versus Pr diagrams are prepared for a number of different
substances, all of them very nearly coincide, especially when the substances have simple,
essentially spherical molecules.

We need to know only critical temperature and critical pressure to use this basic generalized
chart.

In general it can be noted that idealized gas behavior for very low pressures as compared to
critical) regardless of temperature. Furthermore, at high temperatures (greater than twice Tc), the
ideal-gas model can be assumed to good accuracy to pressures as high as 4-5 times Pc.

GRAPHICAL REPRESENTATION OF DATA

 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

1. Pressure versus temperature (P-T)

2. Pressure vs. volume (P-v)

3. Temperature vs. volume (T-v)

4. Temperature vs. entropy (T-s)

5. Enthalpy vs. entropy (h-s)

6. Pressure vs. enthalpy (P-h)

The term saturation temperature designates the temperature at which vaporization takes place.

For water at 99.6 C the saturation pressure is 0.1 M Pa, and for water at 0.1 Mpa, the saturation
temperature is 99.6 C.

If a substance exists as liquid at the saturation temperature and pressure it is called saturated
liquid.

If the temperature is of the liquid is lower than saturation temperature at the existing pressure it
is called sub-cooled liquid or compressed liquid.

1. When a substance exists as part liquid and part vapor at the saturation temperature, its
quality is defined as the ratio of the mass of vapor to the total mass.

2. If a substance exists as vapor at the saturation temperature, it is called a saturated vapor.

3. When the vapor is at a temperature greater than the saturation temperature, it is said to
exist as superheated vapor.

4. At the critical point, the saturated liquid and saturated vapor state are identical.
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

5. At supercritical pressures, the substance is simply termed fluid rather than liquid or
vapor.

6. If the initial pressure at –200C is 0.260 kPa, heat transfer results in increase of
temperature to –100C. Ice passes directly from the solid phase to vapor phase.

7. At the triple point (0.6113 kPa) and a temperature of –200C, let heat transfer increase the
temperature until it reaches 0.010C. At this point, further heat transfer may cause some
ice to become vapor and some to become liquid. The three phases may be present
simultaneously in equilibrium.

Tables of Thermodynamic Properties

Tables of thermodynamic properties of many substances are available, and in general, all these
have same form.

Steam tables are selected because steam is used extensively in power plants and industrial
processes.

The steam tables provide the data of useful thermodynamic properties like T, P, v, u, h and s for
saturated liquid, saturated vapor and superheated vapor.

Since the properties like internal energy, enthalpy and entropy of a system cannot be directly
measured; they are related to change in the energy of the system.

Hence one can determine ∆u, ∆h, ∆s, but not the absolute values of these properties. Therefore it
is necessary to choose a reference state to which these properties are arbitrarily assigned some
numerical values.

For water, the triple point (T = 0.01o C and P = 0.6113 kPa) is selected as the reference state,
where the internal energy and entropy of saturated liquid are assigned a zero value.

In the saturated steam tables, the properties of saturated liquid that is in equilibrium with
saturated vapor are presented.
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

During phase transition, the pressure and temperature are not independent of each other. If the
temperature is specified, the pressure at which both phases coexist in equilibrium is equal to the
saturation pressure.

Hence, it is possible to choose either temperature or pressure as the independent variable, to

specify the state of two-phase system.

Depending on whether the temperature or pressure is used as the independent variable, the tables
are called temperature or pressure tables.

The two phases- liquid and vapor can coexist in a state of equilibrium only up to the critical
point.

Therefore the listing of the thermodynamic properties of steam in the saturated steam tables
ends at the critical point (374.15o C and 212.2 bar).

If the steam exists in only one phase (superheated steam), it is necessary to specify two
independent variables, pressure and temperature, for the complete specification of the state. In
the superheated steam tables, the properties- v, u, h, and s- are tabulated from the saturation
temperature to some temperature for a given pressure.

The thermodynamic properties of a liquid and vapor mixture can be evaluated in terms of its
quality. In particular, the specific volume, specific internal energy, specific enthalpy and specific
entropy of a mixture of quality X are given by

v = (1-X)vf + Xvg, u = (1-X)uf + Xug, h = (1-X)hf + Xhg = hf + Xhfg, s = (1-X)sf + Xhg

where hfg = hg - hf = latent hat of vaporization.

Temperature-volume diagram
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

The locus of all the saturated states gives the saturated liquid curve AC and the locus of all the
saturated vapor states gives the saturated vapor states gives the saturated vapor states gives the
saturated vapor curve BC.

The point C represents the critical point. The difference between vg and vf reduces as the
pressure is increased, and at the critical point vg = vf .

At the critical point, the two phases-liquid and vapor- are indistinguishable.

Pressure-volume diagram

The pressure-volume (P-V) diagram for a pure substance is shown in Figure. The curves AC and
BC represent the saturated liquid curve and saturated vapor curve, respectively, and C is critical
point.

The area under the curve represents the two-phase region. Any point M in this region is a
mixture of saturated liquid (shown as f) and saturated vapor (g).

Mollier (h-s) Diagram

The h-s diagram was introduced by Richard Mollier and was named after him.

It consists of a family of constant pressure lines, constant temperature lines and constant volume
lines plotted on enthalpy versus entropy coordinates.

In the two-phase region, the constant pressure and constant temperature lines coincide.

T-s diagram
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

First Law Analysis to Non-flow Processes

Constant Volume process:

1. Heating of gas enclosed in a rigid vessel:

dU = dQ or U2- U1 , Q = m Cv (T2 – T1)

2. Shaft work done on a system at constant volume

dU = dQ- dW = dQ – (dWpdv + dWs)

or dU = - dWs or -Ws = U2- U1

3. Constant volume process involving electrical
work:
- Ws = U2- U1

For an adiabatic process the work is done is

independent of path.
Constant Pressure Process

1. Reversible heating of a gas

 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

2. Phase Change at constant pressure(Rev.)

3. Shaft work at constant pressure

4. Electrical work at constant pressure

W = P (V2 –V1)

dU = dQ-dW = dQ- PdV = dQ- d(PV)

or, dQ = dU + d(PV) = d(U+ PV) = dH

Q = ∆H the heat interaction is equal to increase

in enthalpy
Constant Temperature Process

dU = dQ-dW = dQ- PdV

for an ideal gas u= u(T) then dU = 0

dQ = PdV = RT (dv/v)

Q = W = RT ln (v2/ v1)

Reversible Adiabatic Process

dU = -dW or W = -∆U
This equation is true for reversible as well as irreversible process.

Cv dT = -Pdv = -RT/v dv
 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

dT/T = -R/Cv dv/v

R/Cv = γ - 1
dT/T = -(γ-1) dv/v
T2/T1 = (v1/v2) (γ-1) Tv(γ-1) = constant
Also Pv γ = Constant using perfect gas relation
Polytropic Process

W = ∫ cdv/ vn

w = (P1v1- P2v2)/(n-1)

du = dq – dw

u2 – u1 = q - (P1v1- P2v2)/(n-1)

u2 – u1 = Cv (T2 – T1) = q – w

q = R(T2 – T1)/(γ-1) + (P1v1- P2v2)/(n-1)

= R (T1 – T2){1/(n-1) – 1/(γ-1)}

=(P1v1- P2v2)/(n-1) {(γ -n)/(γ-1)}

=w.{ (γ -n)/(γ-1)}

Problem: Air (ideal gas with γ = 1.4) at 1 bar and 300K is compressed till the final volume is
one-sixteenth of the original volume, following a polytropic process Pv1.25 = const. Calculate (a)
the final pressure and temperature of the air, (b) the work done and (c) the energy transferred as
heat per mole of the air.

Solution: (a) P1v11.25 = P2v21.25

 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

P2 = P1(v1/v2)1.25 = 1(16)1.25 = 32 bar

T2 = (T1P2v2)/(P1v1) = (300 x 32 x 1)/(1x16)

= 600K

(b) w = (P1v1- P2v2)/(n-1)

= Ru(T1 – T2)/(n-1)

= 8.314 (300 – 600)/(1.25-1) = -9.977 kJ/mol

(c) q = w.{ (γ -n)/(γ-1)}

= -9.977 (1.4 – 1.25)/(1.4-1)

= -3.742 kJ/mol

Problem: A rigid and insulated container of 2m3 capacity is divided into two equal
compartments by a membrane. One compartment contains helium at 200kPa and 127oC while the
second compartment contains nitrogen at 400kPa and 227oC. The membrane is punctured and the
gases are allowed to mix. Determine the temperature and pressure after equilibrium has been
established. Consider helium and nitrogen as perfect gases with their Cv as 3R/2 and 5R/2
respectively.

Solution: Considering the gases contained in both the compartments as the system, W= 0 and Q
= 0. Therefore, ∆U = 0 (U2 = U1)

Amount of helium = NHe = PAVA/RuTA

 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

= 200 x 103 x 1/(8.314 x400)

= 60.14 mol.

Amount of nitrogen = NN2 = PBVB/RuTB

= 400 x 103 x 1/(8.314x500)

= 96.22 mol.

Let Tf be the final temperature after equilibrium has been established. Then,

[NCv(Tf-400)]He + [NCv(Tf-500)]N2 = 0

Ru[60.14(Tf-400)3 + 96.22(Tf-500)5 ] /2 = 0

Or, Tf = 472.73 K

The final pressure of the mixture can be obtained by applying the equation of state:

PfVf = (NHe + NN2)Ru Tf

2Pf = (60.14 + 96.22) 8.314 (472.73)

 SCHX1014 – Chemical Engineering Thermodynamics –Unit 3

or, Pf = 307.27 kPa