METALLURGICAL ENGINEERING

Thermodynamics
THERMODYNAMICS AND RATE PROCESSES
CONTENTS
CHAPTER DESCRIPTION PAGE NO

NOTES
1 Thermodynamics
1
1.1. Definitions
1.2. Laws of Thermodynamics
1.2.1. Zeroth Law of Thermodynamics
1.2.2. First Law of Thermodynamics
1.3. Chemical Equilibrium
1.3.1. Dynamic Equilibrium
1.3.2. Writing the Equilibrium Expression
1.3.3. Calculating the Equilibrium Constant
1.3.4. Significance of the Equilibrium Constant
1.4. Rate Equation
1.4.1. The concept of rare controlling to develop overall rate
expression
1.4.2. Rate equation for physical absorption
1.4.3. Rate equation for absorption with chemical reaction
1.4.4. Hatta number (mh)
1.5. Phase equilibria
1.5.1. Gases, liquids and solids
1.5.2. The one-component phase diagram
1.5.3. Phase rule and equilibrium
1.5.4. H vs T PHASE DIAGRAM
1.5.5. Energy changes
1.5.6. Entropy and free energy
1.5.7. F vs T
1.6. Phase diagrams (two-component systems)
1.6.1. Solid solutions
1.6.2. Construction of equilibrium phase diagrams of two-
component systems
1.6.3. Cooling curves
 1.6.4. Solid solution equilibrium diagrams
1.6.5. Interpretation of phase diagrams
1.6.6. Isomorphous System
1.6.7. Ellingham diagrams

2 Chemical Kinetics
66
2.1 Introduction
2.2 Rate Equation
2.3 Rate Determining Step
2.4 Methods for determining of rate law
2.4.1 Isolation method
2.4.2 Initial rates method
2.4.3 Integrated rate laws
2.4.3.1 First order reactions
2.4.3.2 Second order reactions
2.4.3.3 Third order reactions
2.4.3.4 nth order reaction
2.5 Molecularity and order of reaction

3 Electrochemistry
81
3.1 Introduction
3.2 Electrolytes
3.3 Faraday‟s law of electrolysis
3.4 Electrolytic cell
3.5 Electrode potential
3.6 Electrochemical cell

4 Corrosion
89
4.1 Definition
4.2 The consequences of corrosion
4.3 Chemistry of Corrosion
4.4 Factors that control the corrosion rate
4.5 Corrosion prevention
5 Heat Transfer
97
5.1 Conduction
5.1.1 Fourier‟s Law of Heat Conduction
5.1.2 General conduction equation based on Cartesian
coordinates
5.1.3 Heat transfer through a wall
5.1.4 Composite Wall (Materials in Series)
5.1.5 Composite Wall (Materials in Parallel)
5.1.6 Plane wall with internal heat generated
5.1.7 Overall heat transfer coefficient
5.2 Convection
5.2.1 Newton‟s law of cooling
5.2.2 Film heat transfer coefficients
5.2.3 Heat transfer to a flowing fluid
5.2.4 Types of convection heat transfer
5.2.4.1 Natural convection
5.2.4.2 Forced convection
5.3 Radiation
5.3.1 Black Body Radiation
5.3.2 Radiation Laws
5.3.2.1 Planck‟s Law
5.3.2.2 Stefan-Boltzmann Law
5.3.2.3 Wien‟s Displacement Law
5.3.3 Radiation Properties
5.3.3.1 Emissivity
5.3.4 Radiation Heat Transfer
5.3.5 Net Radiation between two surfaces

6 Mass Transfer
118
6.1 Diffusion
6.1.1 Fick‟s Law
6.1.2 Relation among molar fluxes
6.1.3 Diffusivity
6.1.3.1 Diffusivity in Gases
6.1.3.2 Diffusivity in Liquids
6.1.3.3 Diffusivity in Solids
6.1.4 Steady State Diffusion
 6.1.5 Transient Diffusion
6.2 Mass Transfer Theories

7 Momentum Transfer
136
7. 1 Fluid properties
7.1.1 The fluid as a continuum
7.1.2 Fluid properties: mass density, specific weight, and
specific gravity
7.1.3 Compressibility and bulk modulus
7.1.4 Viscosity
7.1.5 Surface Tension and Capillarity
7.1.6 Capillary or Meniscus Effect
7.1.7 Vapour Pressure
7.2 Newtonian and Non-Newtonian fluid
Solved Examples
7.3 Fluid Dynamics
7.3.1 Euler‟s equation along a streamline
7.3.2 Euler‟s equation in Cartesian co-ordinates
7.3.3 Bernoulli‟s theorem: Integration of Euler‟s equation
7.4 Turbulent flow and flow through the pipes
7.4.1 Flow Losses in Pipes
7.4.2 Darcy equation for head loss due to friction
7.4.3 Empirical correlations for coefficient of friction

8 Misc Topics 186

9 Section Tests 207
1. Thermodynamics

1.1. Definitions
Thermodynamics: This is the branch of Physics in which we deal with internal
macroscopic state of the system.
System: Any portion of matter which is considered as separated from its
surrounding is called system.
Surrounding: All these things which are outside the system and influence its
behaviour are known as surrounding.
Thermodynamics system: A thermodynamic system is one which may interact with
its surrounding in atleast two distinct ways and one of these necessarily a transfer of
heat (In or out of the system) and the other may be some other means of transfer of
energy say be performance of mechanical work by or on the system through
electromagnetic interaction.
Example: Gas contained in a cylinder, vapour in contact with its liquid stretched wire.
Equilibrium: If there is no change in the property of the system w.r.t. time, the system
is called in equilibrium.
1. Mechanical equilibrium: When there is no unbalanced force interior of the system
and between the system and surrounding then the system is in mechanical
equilibrium.
Example: Ideal gas inside a container.
2. Chemical equilibrium: If the system has no tendency to undergo a change in
internal structure and also has no tendency to transfer matter from one part to
another part then it is said to be in chemical equilibrium.
3. Thermal equilibrium: If there is no temp difference between any part of the
system and also not between the system & surrounding then the system is in thermal
equilibrium.
4. Thermodynamic equilibrium: A system is said to be in thermodynamic
equilibrium if its state doesn‟t change in any way i.e. mechanical, chemical & thermal
equilibrium.
If however the conditions for nay one of three type of equilibrium are not satisfied then
the system is said to be in non-thermodynamic equilibrium. If all are not satisfied then
system is called in non-equilibrium.
Microscopic parameter: The parameter of the order of atomic level are called
microscopic parameter. There are parameters that describes the internal structure of
the system or associated with the constituent of the system. The parameter S can be
directly measured in laboratory and can‟t be experience by our sense of perception.
Example: pressure, volume, temp, entropy
Microstate: The state of the system associated with the stated of all constituents of
the system is called microstate or microscopic state.
Macroscopic State: The state of the system associated with the parameters of the
whole system is called macrostate. The macrostate is called thermodynamic state.
When a thermodynamic system is taken from initial to final state the work done by the
system is given by
dW  FdS  PAdS  PdV
final f

W   dW   pdV
2. initial i

3.
Work done on the system is ve
Work done by the system is ve
Work done = Area under the curve
Work done depends on the path and can‟t be written as perfect differential
similarly heat also depend on path and can‟t be written as perfect differential.
P, V, T, U, S are exact or perfect differential (state or point function)
Cyclic process: When a system undergoes a change from initial state to another final
state through different state and come back to initial state then the process is called
cyclic process.
Work done in cyclic process is equal to urea enclosed by the cycle. If the cycle is traced
anticlockwise work done is –ve i.e. work done on the system. If the cycle is traced
clockwise then work done is +ve i.e. work done by the system.
Internal energy: The internal energy is the energy associated with microscopic
mechanical energy I.E = K.E + P.E
It is impossible to divide internal energy into a thermal and mechanical part
Let Q be the heat absorbed by the system and W be the work done by the system
during the process that leads the system from initial state to final state Q –W is
calculated the Q–W is same for different path although Q & W individually are
different for different path. Then this is called change in internal energy dU.

4. dU  Q  W
Q–W depend only on state (Initial & final) and not on the path the internal energy of a
system in a given state is a function of that state only and doesn‟t at all depend upon
the way by which that states has been acquired. Hence we can‟t tell whether the
internal energy of the system has been acquired by heat transferred or by performance
of mechanical work or by both.

1.2. LAWS OF THERMODYNAMICS

1.2.1. ZEROTH LAW OF THERMODYNAMICS
If two system are separately in thermal equilibrium with a third system they are also
in thermal equilibrium with each other.
This law enabled us to compare the temp of two system with the help of third system.
This law can be used to define temp.
The temp of a system is the property which determines whether or not the system are
in thermal equilibrium with other system.
 1.2.2. FIRST LAW OF THERMODYNAMICS
The first law of thermodynamics is simply the principle of conservation of energy apply
to the system.
Whenever other forms of energy converted into heat & Vice versa there is a fix ration
between quantities of energy & heat thus converted.
If an infinitesimal amount of heat dQ is given to the system then some part of it is
used to do work (dw) & other remaining part is used to change the internal energy
dQ  dU  dW
Significance: This law signifies that
(i) Heat is a form of energy.
(ii) Energy is conserved in thermodynamic system.
(iii) Every thermodynamic system in equilibrium state possess internal energy
which is a function of state only. This law signifies the exact relation between heat &
other energy. It follows directly from this law that it is impossible to derive any work
without expenditure of an equal amount of energy in some other form.
First law of Thermodynamics in different process:
(i) Cyclic Process:
dQ  dU  dW
For cyclic process dU  0 , because internal energy depends only on the state.

 dQ   dW
(ii) Isochoric Process: (volume constant)
dQ  dU  dW but because V  constant dQ  dU

If heat is given to the system internal energy incease & heat is given by the
system internal energy decrease.

(iii) Adiabatic Process: (Q = constant)

dQ  dU  dW or Q  constant  dQ  0
dU  dW  0 or dU  dW  PdV
It work done by the system (in adiabatic process) then internal energy decreases &
vice-versa.
(iv) Free expansion:
If a system say a gas expands in such a way that no heat enters or leave the
system (adiabatic process) and also no work is done by or on the system then the
process is called free expansion.
For free expansion dQ = 0 and dW = 0
 dU  0 or U  constant
The initial and final state internal energy are same.

The second law of thermodynamics, Kelvin plank statement: No apparatus

can operate in such a way that its only effect is to convert heat absorbed by a
system completely in to work done by the system.

Reversible Process:

A process in which an infinitesimal change in the driving potential can reverse

the direction of the process.

Example: A piston expanding against an external pressure. The driving

potential is the pressure difference which is infinitesimal. At any stage, if the
external pressure is increased infinitesimally, the piston should start moving
the opposite way.
Or Else: Heat transfer occurring due to a temperature difference between two
bodies. The temperature difference between the two bodies is infinitesimal. If
the temperature of body receiving energy is changed infinitesimally, the
direction of heat transfer also changes.

NOTE: A reversible process is necessarily quasi-static though the opposite is

not true. For example, consider heat exchange between a really well insulated
vessel at temperature T1 and the surroundings which are at T2 far lesser than
T1. Changing either T1 or T2 does not reverse the direction of the process,
though it is slow enough to be quasi-static.

Entropy

Entropy, S, is the tendency towards randomness or disorder in a system - an

ordered arrangement of particles has a lower entropy/disorder than the same
number of particles in random arrangements
Entropy becomes more disordered with:

increase in T – more chaotic motion

increases of V of gases

change in physical State

From the 2nd law of thermodynamics, ΔSuniverse = ΔSsystem + ΔSsurr

At constant P,

ΔSsurr =  ΔHsys/T

Combing these two gives ΔSuniverse = ΔSsystem  (ΔHsys/T)

Multiplying both sides by T gives

TΔSuniverse = ΔHsys  TΔSsystem

Now, let us introduce a new term, free energy (G) that combines the system‟s
enthalpy and entropy so that G = H  TS.

The Gibbs free energy change of the system (ΔGsys) at constant T and P:
ΔGsys = ΔHsys  TSsys

= TSuniverse

The 2nd Law of Thermodynamics dictates

Suniverse > 0 for a spontaneous process

Suniverse < 0 for a nonspontaneous process

Suniverse = 0 for a process at equilibrium

Since T is always positive, TSuniverse > 0 for a spontaneous process.

It follows that

Gsys < 0 for a spontaneous process

(For a spontaneous process at constant T and P, the free energy of the system
always decreases.)
Gsys > 0 for a nonspontaneous process

Gsys = 0 for a process at equilibrium

Finally, we have a single criterion for spontaneity, G, whose sign tells if a
reaction is spontaneous.

Notes:

If a process is nonspontaneous in one direction (G > 0), it is spontaneous in

the opposite direction (G < 0).

The sign and magnitude of G tells us nothing about its rate.

A spontaneous reaction with a large ve G can proceed extremely slowly.

Physical Changes where an increase in S is found:

change in state (sl, sg, lg) or dissolving

water falling (i.e. rain)

solutes moving from high to low conc. until equil. is met

Chemical Changes where an increase in S is found:

more moles of products than reactants

complex molecule broken into simpler ones

change of state due to chemical change

Entropy is a state function

dS = dQrev/T

A change in entropy is calculated by subtracting the entropy of the reactants

from the entropy of the products
S = Sproducts - Sreactants

If S>0, Sproducts > Sreactants and S has increased (+)

If S<0, Sproducts < Sreactants and S has decreased (-)

Entropy changes for an ideal gas

S = nCpln(T2/T1)-nRln(P2/P1)
S=nCvln(T2/T1)+nRln(V2/V1)

Entropy changes of a reversible process

S > = 0 this is mathematical statement of second law.

For reversible process which is = 0 and for an irreversible process delta S > 0.
No process is possible for which total entropy less than 0.

Ssurr < 0 (heat absorbed from the surroundings) Therefore, Suniverse > 0,
spontaneous.

Now, how to measure Ssurr?

The essential role of the surroundings during chemical changes is to either add
heat to the system or remove heat from it. In essence, the surroundings function
as an enormous heat source, one so large that its T remains constant, although
its S changes through the loss or gain of heat. The surroundings participate in
the two possible types of enthalpy changes as follows:

(1) Exothermic change: Heat loss by the system is gained by the

surroundings. This heat gain increases the freedom of motion of
particles in the surroundings, hence Ssurr > 0.
qsys < 0, qsurr > 0, and Ssurr > 0

(2) Endothermic change: Heat gained by the system is lost by the

surroundings. Likely,
qsys > 0, qsurr < 0, and Ssurr < 0

The temperature of the surroundings at which the heat is transferred also

affects Ssurr.

If the same amount of heat is transferred to the surroundings of two different

temperature, its effect will be larger at lower T, since at lower T, there is
relatively little energy dispersed from the beginning (It is like depositing $10 to
a checking account that has $10 in it. A huge effect. The same transaction to
an account with $1000, has little effect.)

Ssurr is directly related to an opposite change in the heat of the system and
inversely related to the temperature at which the heat is transferred.
Hence,

Ssurr =  qsys/T
Recall qp = H at constant P (see above eq. ④), so

Ssurr =  Hsys/T

By making two separate measurements, Ssystem and Ssurr, we can predict

whether a reaction will be spontaneous. Now, can we have one criterion for
spontaneity that applies only to system?
Example:

Calculate the change in entropy when one gram of ice at 00C is converted into
steam at 1000C. Latent heat of fusion of ice = 80 cal/s. Latent heat of
vaporization=540 cal/g mean specific heat of water between 00C and 1000C=1.

Ice A Water B Water C Steam

0°C 0°C 100°C 100°C

λs = 80 cal/g λv = 540 cal/g

Basis = 1 g ice.

δQ 80 cal/g cal
Step A: - dsA = = = 0.293
T 273K gK

∴ For 1g = 0.293 cal/K

T2 cal 373 cal

Step B: - dsB = m cp ln = 1g × 1 ln = 0.312
T1 gK 273 K

1 cal
Step C: - dsC = 540 cal/g × × 1g = 1.447
373K K

∴ Total change in entropy = 0.293 + 0.312 + 1.447

= 2.052 cal/K
 Past GATE Question

1. The second law of thermodynamics states that,

(A) The energy change of a system undergoing any reversible process is zero.

(B) It is not possible to transfer heat from a lower temperature to a

higher temperature.

(C) The total energy of the system and surroundings remain constant.

(D) None of the above.

Solution to Gate Questions

1-C

Second law of thermodynamics (contd.)

Clausisus statement: No process is possible which consists solely in the

transfer of heat from one temperature level to a higher one.

Some spontaneous changes (water freezing) end up with lower entropy (liquid
to solid). If we consider changes in both the system and its surroundings, we
find that all real processes occur spontaneously in the direction that increases
the entropy of the universe (system plus surroundings).  the 2nd law of
thermodynamics
Suniverse = Ssystem + Ssurr > 0

(1) C6H12O6(s) + 6O2(g)  6CO2(g) + 6H2O(g) + heat

Ssystem > 0 (solid to gas)

Ssurr > 0 (heat produced) Therefore, Suniverse > 0, spontaneous.

(2) CaO(s) + CO2(g)  CaCO3(s) + heat

 Ssystem < 0 (gas to solid)

Ssurr >> 0 (heat produced) Therefore, Suniverse > 0, spontaneous.

(3) heat + Ba(OH)28H2O(s) + 2NH4NO3(s)  Ba2+(aq) + 2NO3(aq) + 2NH3(aq) + 10H2O(l)

Ssystem >> 0 (3 mol give 15 mol)

Energy Balances For Closed/ Open Systems

Energy balance on closed systems

 Balance equation

(Final System Energy) – (Initial System Energy)

= (Net Energy Transfer)

 Initial System Energy U i  E pi  Eki

Final System Energy U f  E pf  Ekf

 Net Energy Transfer U  E p  Ek  Q  W

 U depends on composition, state, temperature of the system. Nearly

independent of pressure for ideal gases, liquids, solids.
 Q = 0  Adiabatic process
 If there are no moving parts, W = 0
 Potential energy change  due to the changes in height
 Past GATE Questions

1. A closed system is cooled reversely from 1000C to 500C. If no work is done on

the system.

(A) Its internal energy (U) decreases and its entropy (S) increases,

(B) U and S both decrease,

(C) U decreases but S is constant,

(D) U is constant but S decreases,

2. The equation dU = TdS – PdV is applicable to infinitesimal changes occurring

in:

(a) an open system of constant composition,

(b) a closed system of constant composition,

(c) an open system with changes in composition,

(d) a closed system with changes in composition

Solution to Gate Questions

1-B 2-D
THE MAXWELL RELATIONS
The equations that relate the partial derivatives of properties P, v, T, and s of a
simple compressible system to each other are called the Maxwell relations.
Two of the Gibbs relations are expressed as
du = T ds - P dv
dh = T ds + v dP
The other two Gibbs relations are based on two new combination properties-the
Helmholtz function a and the Gibbs function g, defined as
a = u - Ts
g = h - Ts
Differentiating, we get
da = du - T ds - s dT
dg = dh - T ds - s dT
Simplifying the above relations by using Eqs., we obtain the other two Gibbs
relations for simple compressible systems:
da = -s dT - P dv
dg = -s dT + v dP
A careful examination of the four Gibbs relations reveals that they are of the
Form
dz = M dx + N dy
with
 T   P 
   
   x  s  y
Since u, h, a, and g are properties and thus have exact differentials. Applying
above Eq. to each of them, we obtain
 T   P 
    
   s  s 
 T    
   
 P  s  s  P
 s   P 
   
  T  T 
 s    
    
 P T  T  P
These are called the Maxwell relations. They are extremely valuable in
thermodynamics because they provide a means of determining the change in
entropy, which cannot be measured directly, by simply measuring the changes in
properties P, v, and T.

THE CLAPEYRON EQUATION

The Clapeyron equation is one such relation, and it enables us to determine the
enthalpy change associated with a phase change (such as the enthalpy of
vaporization hfg) from knowledge of P, v, and T data alone. Consider the third
Maxwell relation,
 s   P 
    
  T  T 
During a phase-change process, the pressure is the saturation pressure, which
depends on the temperature only and is independent of the specific volume. That
is, Psat = f (Tsat). Therefore, the partial derivative (∂P/∂T)v can be expressed as a
total derivative (dP/dT )sat, which is the slope of the saturation curve on a P-T
diagram at a specified saturation state.

The slope of the saturation curve on a P-T diagram is constant at a constant T or

P.

This slope is independent of the specific volume, and thus it can be treated as a
constant during the integration of Eq. 12–18 between two saturation states at the
same temperature. For an isothermal liquid–vapor phase-change process, for
example, the integration yields

 dP 
sg  s f    Vg  V f 
 dT  sat
 dP  s fg
  
 dT  sat V fg
During this process the pressure also remains constant. Therefore,
g g
dh  T ds  v dP 0
  dh   T ds  h fg  Ts fg
f f

Substituting this result into above Eq., we obtain

 dP  h fg
  
 dT  sat Tv fg
which is called the Clapeyron equation. This is an important thermodynamic
relation since it enables us to determine the enthalpy of vaporization hfg at a given
temperature by simply measuring the slope of the saturation curve on a P-T
diagram and the specific volume of saturated liquid and saturated vapor at the
given temperature. The Clapeyron equation is applicable to any phase-change
process that occurs at constant temperature and pressure.
Tds Relationship
The two-property rule can be used to define entropy as the following functional
relationship
s = S(V, T)

Hence
 s   s 
ds    dT    dv
 T v  v T
Now, by definition
 s 
Cv  T  
 T v
and from the max well relationshipe
 s   p 
   
 v   T v
Hence
 p 
Tds  Cv dT  T   dv
 T v

This is called the first Tds relationship.

The second Tds relationship can be derived in the following way. If it is assumed
that entropy is a function of temperature and pressure, then
s = s (T,p)
and
 s   s 
ds    dT    dp
 T  P  p T
By definition
 s 
Cp T  
 T  P
and from Maxwell relation
  s   v 
   
 p T  T  P
Thus, the sec ond Tds relationship is
 v 
Tds  cP dT  T   dp
 T  P
Thethird Tds relationship is derived by assu min g that
s  s  p, v 
 s   s 
ds    dp    dv
 p v  v  p
 s   s   v   s  1  T 
cp T   T         cp  
 T  P  v  P  T  P  v  P T  v  P

A similar expression can be derived for c,, and this enables the equation

 T   T 
Tds  cv   dp  c p   dv
 p v  v  P

to be obtained. This is the third Tds relationship.

Coefficient of Volume Expansion

A family of isopiestic curves can be obtained on V-T diagram by measuring the
variation of volume with temperature at constant pressure. The slope at any point
A on this curve is (∂V/∂T)p. If this divided by volume at that point than we get an
intensive property called coefficient of volume expansion which is represented by
β.

( )

Isothermal and Adiabatic Compressibility

Factor
Similarly like in volume expansion, isothermals can be plotted on v-p diagram,
then by dividing the slope (∂v/∂p) at any point by its volume at that point we get
another intensive property called isothermal compressibility, K, of the substance.

( )
Here negative sign is used to make it positive because (∂v/∂p) T is always negative.
If these slopes are calculated taking entropy as a constant then it becomes
adiabatic compressibility factor.

( )

Jolue-Thomson Coefficient
Valves, porous plugs, and orifices inserted into flow lines are examples of devices
through which the flow is isenthalpic. Even though the enthalpies upstream and
downstream of such devices are equal, the pressures are not. In fact, the main
practical purpose of these devices is to produce an abrupt reduction in pressure,
and for refrigerators, of temperature as well. For this reason, they are called
throttling devices.

If the fluid is a gas, the change in temperature across the device may be
positive, negative, or zero, depending on the equation of state and the upstream
temperature. The partial derivative (T/p)h representing this process is called the
Joule-Thompson coefficient. If the gas is ideal, no change in temperature occurs
because the enthalpy is constant.

The relation between the Joule-Thompson coefficient and the equation of state is
obtained by this equation.
T  1   v 
   T   v
  p  h C P    T  p 
Volumetric Properties of Fluids
PVT Behavior of Pure Substances

A fluid is the general term for all liquids, gases, vapors or supercritical phases.
Since the supercritical phase is neither a liquid, gas or a vapor, it is referred to
specifically as a "fluid."

A liquid can be vaporized to a gas phase without an abrupt phase change by

the path A-B. A sublimation curve represents the set of conditions where a
solid is in equilibrium with a gas while there is no liquid present. The 3 phases
only coexist at the triple point. A fusion curve represents the set of conditions
where a solid is in equilibrium with a liquid while there is no gas present. The
steep slope signifies that a solid/liquid equilibrium is not very sensitive to
changes in pressure at constant temperature, but is sensitive to changes in
temperature at constant pressure.

According to the phase rule, for 2 phases of a single component, F=2-2+1 = 1,

meaning that one and only one of the variables (P, T, and composition of the
phases) can be arbitrarily fixed to determine the intensive state of the system

3
A
. Supercritical
Fluid region

Pc
Fusion curve Liquid region
C
.
Solid Vaporization
region curve
B
.
Gas region
. Vapor region
2 Triple point

1
Sublimation
curve
Tc
Estimation of Thermodynamic Properties Using Equation of State

An equation of state exists relating pressure, molar or specific volume, and

temperature for any pure homogeneous fluid in equilibrium states.

An equation of state may be solved for any one of the three quantities P, V, or T
as a function of the other two.
Example
 V   V 
dV    dT    dP
 T  P  P T

1  V 
1  V     
Volume expansivity:    V  P T Isothermal compressibility
V  T  P
dV
 dT  dP
V

For incompressible fluid, both β and κ are zero.

For liquids β is almost positive (liquid water between 0°C and 4°C is an
exception), and κ is necessarily positive.

At conditions not close to the critical point, β andκ can be assumed constant:
V2
ln   (T2  T1 )   ( P2  P1 )
V1
Concept 1 Major Equations of State

For a given amount of substance contained in a system, the temperature,

volume, and pressure are not independent quantities; they are connected by a
relationship of the general form:

In the following equations the variables are defined as follows. Any consistent
set of units may be used, although SI units are preferred. Absolute
temperature refers to use of the Kelvin (K) or Rankine (°R) temperature scales,
with zero being absolute zero.

P = pressure (absolute)
V= volume

n = number of moles of a substance

Vm=V/n = molar volume, the volume of 1 mole of gas or liquid

T= absolute temperature

R= ideal gas constant (8.314472 J/(mol·K))

Pc= pressure at the critical point

Vc= molar volume at the critical point

Tc= absolute temperature at the critical point

(a) Ideal Gas Law

The classical ideal gas law may be written:

The ideal gas law may also be expressed as follows

where ρ is the density, γ = Cp / Cv is the adiabatic index (ratio of specific heats), e

= CvT is the internal energy per unit mass (the "specific internal energy"), Cv is the
specific heat at constant volume, and Cp is the specific heat at constant pressure.

(b) Van der Waals Equation of State

The Van der Waals equation of state may be written:

where Vm is molar volume, and a and b are substance-specific constants. They can
be calculated from the critical properties pc,Tc and Vc (noting that Vc is a the molar
volume at the critical point) as:
Also written as

Proposed in 1873, the van der Waals equation of state was one of the first to
perform markedly better than the ideal gas law. In this landmark equation a is
called the attraction parameter and b the repulsion parameter or the effective
molecular volume. While the equation is definitely superior to the ideal gas law
and does predict the formation of a liquid phase, the agreement with
experimental data is limited for conditions where the liquid forms. While the
van der Waals equation is commonly referenced in text-books and papers for
historical reasons, it is now obsolete. Other modern equations of only slightly
greater complexity are much more accurate.

The van der Waals equation may be considered as the ideal gas law, “improved”
due to two independent reasons:

Molecules are thought as particles with volume, not material points. Thus V
cannot be too little, less than some constant. So we get (V − b) instead of V.

While ideal gas molecules do not interact, we consider molecules attracting

others within a distance of several molecules' radii. It makes no effect inside
the material, but surface molecules are attracted into the material from the
surface. We see this as diminishing of pressure on the outer shell (which is
used in the ideal gas law), so we write (p + something) instead of p. To
evaluate this „something‟, let's examine an additional force acting on an
element of gas surface. While the force acting on each surface molecule is ~ρ,

the force acting on the whole element is ~ρ2~.

(c) Virial Equation of State

The virial expansion, also called the virial equation of state, is the most
interesting and versatile of the equations of state for gases. The virial
expansion is a power series in powers of the variable, n/V, and has the form,

The coefficient, B(T), is a function of temperature and is called the "second

virial coefficient. C(T) is called the third virial coefficient, and so on. The
expansion is, in principle, an infinite series, and as such should be valid for all
isotropic substances. In practice, however, terms above the third virial
coefficient are rarely used in chemical thermodynamics.

Notice that we have set the quantity pV/nRT equal to Z. This quantity (Z) is
called the "compression factor." It is a useful measure of the deviation of a real
gas from an ideal gas. For an ideal gas the compression factor is equal to 1.
Problem 1

One kilo mole CO2 occupies a volume of 0.381 m3 at 313 K. Compare the
pressure given by
a) Ideal gas equation
b) Vander waal‟s equation. Take the Vanderwaals constant to be a= 0.365
Nm4 / mol2 and b = 4.28 X10-5 m3 /mol.
Solution

The molar Volume of CO2 is V= 0381 x10-3 m3/mol

a) Ideal gas equation P= RT/V =8.314(313)/(0.318x10-3)= 68.30 x 105
N/m2= 68.30 bar
b) Vanderwaal‟s equation may be arranged as
P = (RT/ V-b)-a/V2= [8.314(313)/ (0.318 x 10-3)- (0.428 x 10-4)]-0.365/ (0.381x10-3)2

= 5.18 x105 N/m2 = 51.8 bar

Problem 2

Reported values for the virial coefficients of isopropanol vapor at 200°C are:

B = -388 cm3/mol and C = -26000 cm6/mol2. Calculate V and Z for isopropanol

vapor at 200 °C and 10 bar by (1) the ideal gas equation; (2) two-term virial
equation.
Solution:
(1) For an ideal gas, Z = 1:

RT 83.14  473.15 3
V   3934 cm
P 10 mol

(2) Two-term virial equation:

RT 3 PV
V  B  3934  388  3546 cm Z  0.9014
P mol RT

Past GATE Questions

1. Ideal gas law is applicable at,

(A) Low T, low P

(B) High T, high P

(C) Low T, high P

(D) High T, low P

2. The kinetic energy of gas molecules is zero at

(A) 00C, (B) 2730C,

(C) 1000C, (D) -2730C,

3. Which of the following is true for Virial equation of state

(A) Virial coefficients are universal constants,

(B) Virial coefficient B represents three body interactions,

(C) Virial coefficients are functions of temperature only,

(D) For some gases, Virial equations and ideal gas equations are the same

4. In van der Waals equation of state, what are the criteria applied at the
critical point in determine the parameters „a‟ and „b‟ ?

 P   2 P   V    2V 
(A)    0;  2   0 (B)    0;  2   0
 V T  V T  P T  P T
 P   2 P   V    2V 
(C)    0;  2  0 (D)    0;  2   0
 T V  T V  T  P  T  P

5. Match the following :

(a) Heat (i) State Function

(b) Internal energy (ii) Path Function

(c ) Work

(d ) Entropy

(A) (a)-(ii); (b)-(i); (c)-(i); (d)-(i) (B) (a)-(ii); (b)-(i); (c)-(ii); (d)-(ii)

(C) (a)-(ii); (b)-(ii); (c)-(i); (d)-(i) (D) (a)-(ii); (b)-(i); (c)-(ii); (d)-(i)

6. The molar density of water vapor at the normal boiling point of water is 33
mol/m3. The compressibility factor under these conditions is close to which
ONE of the following? R = 8.314 J/(mol K)

(A) 0.75 (B) 1 (C) 1.25 (D) 1.5

7. The state of an ideal gas is changed from (T1, P1) to T2, P2) in a constant volume
process. To calculate the change in enthalpy, Δh, ALL of the following
properties/variables are required.

(A) CV , P1 , P2 (B) CP , T1 , T2

(C) CP , T1 , T2 , P1 , P2 (D) CV , P1 , P2 , T1 , T2

8. Parameters „a‟ and „b‟ in the van der Waals and other cubic equations of state
represent

(A) a – molecular weight b – molecular polarity

(B) a – molecular size b – molecular attraction

(C) a – molecular size b – molecular speed

(D) a – molecular attraction b – molecular size

Solution to GATE Questions

1-D 2-A 3-C 4-A 5-D 6-B 7-B 8-D