TG

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Lecture Sl. No. 04

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Massive Open Online Course under NPTEL

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The Ministry of Human Resource Development (MHRD), Govt. of India

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Basic Principles and Calculations in

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Chemical Engineering

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Module-2: Process Variables and Rate

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Lecture 2.1: Variables and Properties of
fo p
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Prof. S. K. Majumder
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Chemical Engineering Department,

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Indian Institute of Technology Guwahati

ca cc

Guwahati-781039, India. Phone: +913612582265 (O)

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Email: [email protected] ; [email protected]

Welcome IIT Guwahati https://www.iitg.ac.in/chemeng/skm/home
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Present Lecture Includes:

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Process variables

t p rof
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System

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Physical and transport properties of

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material in system and mixtures

fo p
y co
Analysis of problem with solution
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Process Variables

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Variables to characterize the streams entering and leaving a process unit.

rp K
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t p rof
 State or Thermodynamic Variables:

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 Temperature, Pressure of the inlet and outlet streams

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 Dynamic variables:

i
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fo p
 Flow rates of inlet and outlet
y co
 Geometric Variables:
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in d

 Volume of unit, diameter, cross-sectional area, length etc.

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 Physical properties as variables

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 Density, surface tension, viscosity of the fluid

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nn um

 Others
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 Total amount of material in the inlet and outlet streams, composition

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of the inlet and outlet streams.

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What is System?

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 Any specified arbitrary portion or whole of a process analyzing the problem

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is defined as system.

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 It depends on what information is provided and what needs to be

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determined.

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 A system may contain more than one process unit.

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 In Figure the entire process is a system which consists of three process units.

fo p
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System
in d
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N2
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N 2, H2 NH3, N2, H2
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ot e
nn um
ca cc

Liquid NH3
H2 Mixer Reactor Condenser
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at -35 C
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Properties of Materials in System

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 Knowledge of the system properties is required for engineering design of

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equipment involving different processes.

t p rof
 There are two types of system properties which are physical and transport

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properties.

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fo p
Physical
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in d

Material
it un

Properties
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ot e
nn um

Transport
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Physical Properties

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A physical property is any property that is

t p rof
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measurable and its value describes a

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physical system's state.

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fo p
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Two types:
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Intensive properties
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Extensive properties
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Intensive properties:

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 Intensive property is a physical property of a system that does not depend

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on the system size or the amount of material in the system

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 Example, density is an intensive property of a substance because it does

ou P
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not depend on the amount of that substance.

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 Other intensive properties can be derived from the two known values.

i
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fo p
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ot e
nn um
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Extensive properties:

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 An extensive property is a physical quantity whose value is proportional to

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the size of the system it describes.

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 Extensive properties are the counterparts of intensive properties, which are

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intrinsic to a particular subsystem and remain constant regardless of size.

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 Dividing one type of extensive property by a different type of extensive

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property will in general give an intensive value.

fo p
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 For example, mass (extensive) divided by volume (extensive) gives density
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(intensive).
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nn um
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Analog of Intensive and Extensive

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Properties

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 There are a number of properties which have corresponding extensive and

t p rof
intensive analogs, many of which are thermodynamic properties.

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Corresponding extensive and intensive thermodynamic properties

i
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fo p
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Extensive property Symbol SI units Intensive property Symbol SI units
Volume Specific volume
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Internal energy U J Specific internal energy u J/kg
in d
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Entropy S J/K Specific entropy s J/(kg·K)

Enthalpy H J Specific enthalpy h J/kg
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Gibbs free energy G J Specific Gibbs free energy g J/kg

ot e

Heat capacity at Specific heat capacity at

nn um

constant volume CV J/K constant volume cv J/(kg·K)

Heat capacity at Specific heat capacity at
ca cc

constant pressure CP J/K constant pressure cP J/(kg·K)

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Transport Properties

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 These are molecular properties of a substance that indicate the rate at

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which specific (per unit volume) momentum, heat, or mass are transferred.

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fo p
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Definition of

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Some important properties

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rp K
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Concentration

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The concentration of a particular species in a multi-component

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mixture can be expressed in different ways.

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i
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fo p
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Mass concentration (Called Density):
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For a species i, the mass concentration ρi is defined as the mass (Wi) of
in d
it un

species i per unit volume (V) of the mixture.

e is
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nn um
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Mass fraction

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The mass fraction of species i present in the mixture is the

t p rof
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ratio of mass of species i to the total mass of the mixture

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and is given by

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i
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fo p
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in d
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For binary mixture of component A and B

us nt
ot e
nn um

𝑊 𝜌 𝑊 𝜌
𝜔 = = 𝜔 = =
ca cc

𝑊 +𝑊 𝜌 𝑊 +𝑊 𝜌
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Molar Concentration (Called Molar Density)

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 The molar concentration of species i, ci is defined as the number of

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moles of i present per unit volume of the mixture. The mass

t p rof
concentration and molar concentration are related by

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Mi is the molecular weight
of species i.

i
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fo p
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 When dealing with gas phase under conditions in which ideal gas
in d

law applies, the molar concentration is given by

it un
e is

pi is the partial pressure of

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ot e

species i in the mixture,

nn um

T is the absolute temperature

ca cc

R is the gas constant.

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Mole Fraction

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 The mole fraction of species i in a mixture is the ratio of

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moles of species i to the total number of moles in the

t p rof
mixture and is given by

ou P
ith @
w ght
For liquids & solids For gases

i
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fo p
y co
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in d
it un
e is
us nt
ot e
nn um

=
ca cc
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Specific gravity

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 The ratio of the density (mass of a unit volume) of a substance to the

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t p rof
density (mass of the same unit volume) of a reference substance at a
specific condition.

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 The reference substance is nearly always water at 4oC for liquids or air for

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gases. Temperature and pressure must be specified for both the sample

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and the reference.

fo p
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 Pressure is nearly always 1 atmosphere. Temperatures for both sample and
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reference vary from industry to industry.
in d
it un

True specific gravity can be expressed mathematically as:

e is
us nt
ot e
nn um

e.g.,
ca cc
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Example

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A 0.5 molar aqueous solution of sulfuric acid flows into a process unit at a rate of 1.25
m3/min. The specific gravity of the solution at 20 degree Celcius is 1.03

rp K
rio S
(a). Calculate the mass concentration of H2SO4 in kg/m3 (b) The mass flow rate of

t p rof
solution in kg/s, (c). The mass flow rate of H2SO4 in kg/s, (d). The mass fraction of H2SO4

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Solution: M.W of H2SO4 is 128.
0.5 Molar Aq. Sol. Of H2SO4 contains 0.5*128 g = 64 g H2SO4

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Mass concentration of H2SO4 is 64 g/l = 64 kg/m3 (Ans a)

fo p
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Mass concentration of solution
an er
in d

= Density of water x Specific Gravity of solution = 1000*1.03 = 1030 kg/m3

it un

The mass flowrate of solution = Mass concentration of solution x Volumetric

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flowrate = 1030*1.25 = 1287.5 kg/min = 1287.5/60 = 21.46 kg/s (Ans b)

us nt
ot e

Mass flowrate of H2SO4 = 64*1.25/60 = 1.33 kg/s (Ans c)

nn um

Mass fraction of H2SO4 = Mass concentration of H2SO4/Mass concentration

ca cc

of Solution = 64/1030 = 0.062

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Apparent specific gravity

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rp K
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 The apparent specific gravity is simply the ratio of the weights of equal

t p rof
volumes of substance and reference substance (water or air for liquid or

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gas):

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i
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fo p
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in d
it un
e is
us nt

is the weight of the substance and

ot e
nn um

is the weight of water or reference substance.

ca cc
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API gravity

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 The American Petroleum Institute gravity, or API gravity, is a measure

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t p rof
of how heavy or light petroleum liquid is compared to water.

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If its API gravity is greater than 10, it is lighter and floats on

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water;

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if less than 10, it is heavier and sinks.

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 It is used to compare the relative densities of petroleum liquids. The
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formula to obtain API gravity of petroleum liquids, from specific
in d
it un

gravity (SG), is:

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Example

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Prob.: 420 liters of 28 oAPI gas oil blended with 1200 liters of

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15 oAPI fuel oil. What is the density of the mixture in kg/m3?

t p rof
Assume that volumes are additive. The density of water at

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15 oC is 0.999 g/cm3.

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141.5

fo p
Solution 𝑺𝑮 =
y co API + 𝟏𝟑𝟏. 𝟓
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in d

SG of 28 oAPI = 141.5/(28+131.5) = 0.884,

it un

So density of gas oil = 0.884*0.999 = 0.883 g/l

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SG of 15 oAPI = 141.5/(15+131.5) = 0.962,

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nn um

So density of fuel oil = 0.962*0.999 = 0.961 g/l

ca cc

Density of Mixture = Total mass / Total Volume =

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(420*0.883+1200*0.961)/(420+1200) = 0.941 g/l

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Volume fraction in multiphase system

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 The volume fraction of phase is defined as the volume of each phase upon

t p rof
total volume of phases.

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 The volume fraction of phase is sometime referred as void fraction or

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holdup of phase which is represented by

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P for phase

fo p
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an er
L for liquid
in d

S for solid
it un

For gas-liquid mixture,

e is
us nt
ot e
nn um
ca cc
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For gas-liquid-solid mixture:

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Mixture density of multiphase system

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 The sum of the bulk densities for all the phases is called

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the mixture density

t p rof
ou P
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fo p
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 The bulk density is related to the true or absolute density
an er
in d

ρP as:
it un
e is
us nt

Gas bulk density Liquid bulk density Solid bulk density

ot e
nn um
ca cc
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Superficial velocity

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 For multiphase flow in a pipe, the superficial velocity of each phase

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(usp) is the volume flow rate (Q) of that phase divided by the pipe

t p rof
cross sectional area (A).

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ith @
 It is the velocity of the phase if the phase occupied the whole pipe

w ght
cross sectional area which can be defined by

i
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fo p
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Liquid
A = Crosssectional area
in d

or gas in
it un

at Q Liquid
e is

Only liquid or gas flow

or gas out
us nt

m3/s
ot e
nn um
ca cc
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Intrinsic or actual velocity

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 If in system, more than one phase is flowing

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simultaneously, the intrinsic or actual velocity of each

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phase is

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i
Liquid

r m yr
A = Crosssectional area

fo p
& gas in
y co at Q Gas flow Liquid
an er
Liquid flow & gas out
in d

m3/s
it un
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nn um
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Relative or slip velocity

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 The relative velocity between the two phases such as

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gas (G) and liquid (L) in case of two-phase is denoted

ith @
by ur,G-L which can be written as

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i
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fo p
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A = Crosssectional area
an er
& gas in
in d
it un

at Q Gas flow Liquid

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Liquid flow & gas out

m3/s
us nt
ot e
nn um
ca cc

For co-current sign is positive. For countercurrent sign is negetive

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The relative velocity is sometimes referred to as slip velocity

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Viscosity

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 Viscosity is a measure of the resistance of a fluid which is being

rp K
deformed by either shear stress or tensile stress.

rio S
t p rof
 It describes a fluid's internal resistance to flow and may be thought

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of as a measure of fluid friction

ith @
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shear stress

i
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(F/A)

fo p
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Velocity
Gradient
an er
(u/y)
in d
it un
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us nt

Dynamic viscosity, also absolute viscosity, the more

ot e

usual one (typical units Pa·s, Poise, P);

nn um
ca cc

μ is the proportionality Kinematic viscosity is the dynamic viscosity divided

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factor called viscosity by the density (typical units cm2/s, Stokes, St).
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Viscosity of gas

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 μ = dynamic viscosity in (Pa·s) at
 Sutherland's formula can be used to

t p rof
input temperature T,
derive the dynamic viscosity of an

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ideal gas as a function of the  μ0 = reference viscosity in (Pa·s)

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temperature at reference temperature T0,

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 T = input temperature in kelvins,

fo p
y co  T0 = reference temperature in
an er
kelvins,
in d
it un

 C = Sutherland's constant for the

gaseous material in question.
e is
us nt
ot e
nn um

Valid for temperatures between 0 < T < 555 K at below 3.45 MPa. For air C, T0 and µ0
are 120 K, 291.15 K and 18.27 µPa-s.
ca cc
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At 15.0 oC, the viscosity of air is 1.78×10−5 kg/(m·s), 17.8 μPa.s or 1.78×10−5 Pa.s.
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Viscosity of dilute gas

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rp K
where
Can be calculated by the

rio S
 T* = κT/ε — reduced temperature (dimensionless),

t p rof
Chapman-Enskog equation. The
equation requires three empirically  μ0 = viscosity for dilute gas (μPa.s),

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ith @
determined parameters: the  M = molecular mass (g/mol),

w ght
collision diameter (σ), the  T = temperature (K),

i
maximum energy of attraction

r m yr
σ = the collision diameter (Å),

fo p
divided by the Boltzmann constant 

y co
(є/к) and the collision integral  ε / κ = the maximum energy of attraction divided
an er
(ω(T*)). by the Boltzmann constant (K),
in d
it un

 ωμ = the collision integral.

e is

 The Boltzmann constant (k) is the physical

us nt

constant relating energy at the individual particle

ot e

level with temperature observed at the collective

nn um

or bulk level. It is : 1.380 648813×10−23 JK−1

ca cc
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Viscosity of liquid

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 The temperature dependence of liquid viscosity is

t p rof
ou P
usually expressed by the following model:

ith @
w ght
i
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fo p
y co
an er
in d
it un

where T is temperature and μ0 and b are coefficients

e is
us nt
ot e

The dynamic viscosity of water is 8.90 × 10−4 Pa. s or 8.90 × 10−3

nn um

dyn. s/cm2 or 0.890 cP at about 25 °C. Water has a viscosity of

ca cc

0.0091 poise at 25 °C, or 1 centipoise at 20 °C.

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Viscosity of blends of liquids

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m ju
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rp K
 The viscosity of the blend of two or more liquids can be estimated using the

rio S
Refutas equation

t p rof
ou P
ith @
w ght
 Where VBNBlend is the viscosity blending number of the blend.

i
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fo p
y co
an er
in d
it un
e is
us nt

where v is the kinematic viscosity in centistokes (cSt).

ot e
nn um

where x is the mass fraction of each component of the blend

ca cc
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Viscosity of slurry

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m ju
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rp K
 The term slurry designs mixtures of a liquid and solid particles that

rio S
retain some fluidity

t p rof
ou P
 In the case of extremely low concentrations of fine particles,

ith @
Einstein's equation is used:

w ght
i
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fo p
y co
an er
 In the case of very high concentrations, empirical equation
in d
it un

proposed by Kitano et al. (1981)

e is
us nt

A = 0.68
ot e
nn um

Kitano et al.,
Rheol. Acta. 20
ca cc

 = volume fraction of solid particles (1981) 207 - 209.

u do
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Conductivity

si d
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m ju
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rp K
rio S
The degree to which a specified material conducts electricity

t p rof
 Electrical conductivity: a measure of a material's ability to conduct

ou P
ith @
an electric current

w ght
 Electrolytic Conductivity: also the specific conductance, is a

i
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measurement of the electrical conductance per unit distance in an

fo p
y co
electrolytic or aqueous solution
an er
 Ionic conductivity: a measure of the conductivity through ionic
in d
it un

charge carriers
e is

 Hydraulic conductivity: a property of a porous material's ability to

us nt

transmit water
ot e
nn um

 Thermal conductivity: the intensive property of a material that

ca cc

indicates its ability to conduct heat

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Electrical conductivity

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m ju
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rp K
rio S
 Electrical conductivity or specific conductance is the reciprocal quantity,

t p rof
and measures a material's ability to conduct an electric current.

ou P
ith @
 It is commonly represented by the Greek letter σ (sigma), but κ (esp. in

w ght
electrical engineering) or γ are also occasionally used.

i
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 Its SI unit is siemens per metre (S/m) and CGSE unit is reciprocal of second

fo p
(1/s):
y co
an er
R is the electrical resistance of a uniform specimen of
in d
it un

the material (measured in ohms, Ω)

e is

l is the length of the piece of material (measured in

us nt
ot e

metres, m)
nn um

A is the cross-sectional area of the specimen

ca cc
u do

(measured in square metres, m²).

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Electrolytic conductivity

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rp K
 The conductivity (or specific conductance)

rio S
T is the temperature of the

t p rof
of an electrolyte solution is a measure of its sample,
ability to conduct electricity

ou P
ith @
Tcal is the calibration temperature,
 The SI unit of conductivity is Siemens per

w ght
meter (S/m). σT is the electrical conductivity at

i
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the temperature T,
 In many cases, conductivity is linked directly

fo p
y co
to the total dissolved solids (T.D.S.). High σTcal is the electrical conductivity
at the calibration temperature
an er
quality deionized water has a conductivity of
in d

about 5.5 μS/m, typical drinking water in the Tcal,

it un

range of 5-50 mS/m, while sea water about 5 α is the temperature

e is

S/m compensation slope of the

us nt

solution.
ot e
nn um
ca cc
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Thermal conductivity

si d
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m ju
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rp K
rio S
 Thermal conductivity, k, is the property of a material's ability to conduct

t p rof
heat. It appears primarily in Fourier's Law for heat conduction.

ou P
ith @
 In the International System of Units (SI), thermal conductivity is measured in

w ght
watts per meter kelvin (W/(m.K)).

i
r m yr
fo p
A correlation for thermal conductivity of
y co liquid n-alkanes based on the Vogel–
an er
Tammann–Fulcher–Hesse equation
in d
it un
e is
us nt
ot e
nn um

For paraffin hydro carbon of Molecular weight

ca cc

44 gives:
u do

1.94, 561, 1630 for Kc, Tc, and A respectively

Yo is
Th
 TG
. , II
on er
Diffusivity

si d
is m
m ju
er Ma
rp K
rio S
 Diffusivity or diffusion coefficient is a proportionality constant between the

t p rof
molar flux due to molecular diffusion and the gradient in the concentration

ou P
ith @
of the species.

w ght
 Molar flux is defined as flow rate of moles per unit area. Diffusivity is

i
r m yr
encountered in Fick's law and numerous other equations of physical

fo p
chemistry.
y co
an er
in d
it un
e is
us nt

J is the "diffusion flux" [mol/(m2.s)],

ot e
nn um

D is the diffusion coefficient or diffusivity in unit of [m2/s],

c (for ideal mixtures) is the concentration [mole/m3],
ca cc

x is the position in meter [m].

u do
Yo is
Th
 TG
. , II
on er
Diffusion coefficient for gases

si d
is m
m ju
er Ma
 The dependence of the diffusion coefficient on temperature for

rp K
rio S
gases can be expressed using the Chapman–Enskog theory

t p rof
ou P
ith @
w ght
i
r m yr
fo p
– the average collision diameter (Å)
y co
an er
in d
it un

A&B index the two kinds of molecules present in the gaseous mixture
e is

T temperature (K)
us nt

M molar mass (g/mol)

ot e
nn um

p pressure (atm)
Ω a temperature-dependent collision integral (dimensionless).
ca cc

D diffusion coefficient (which is expressed in cm2/s.

u do
Yo is
Th
 TG
. , II
on er
Diffusion coefficient for solvent

si d
is m
m ju
er Ma
rp K
 An approximate dependence of the diffusion coefficient on temperature in

rio S
t p rof
solvent can be found by using semi-empirical equation of Wilke-Chang
Equation

ou P
ith @
w ght
i
r m yr
fo p
DAB
φ
y co
is diffusivity of solute A in solvent B, m2/s,
is association factor
an er
in d

[for H2O =2.26; MeOH =1.9; EtOH =1.5; non-associated

it un

solvent=1.0];
e is

MB is molecular weight of B;
us nt

T is absolute temperature in K;
ot e
nn um

μB is solution viscosity, kg/m.s;

ca cc

A is solute molar volume at normal boiling point, m3/kmol

u do

[νA=0.0756 m3/kmol for H2O as solvent].

Yo is
Th
 TG
. , II
on er
The diffusion coefficient in solids

si d
is m
m ju
er Ma
rp K
 The diffusion coefficient in solids at different temperatures is often

rio S
found to be well predicted by Arrhenius equation:

t p rof
ou P
ith @
w ght
i
r m yr
fo p
D is the diffusion coefficient
D0
y co
an er
is the maximum diffusion coefficient (at infinite temperature)
in d
it un

EA is the activation energy (Activation energy is defined as the minimum energy

required to start a chemical reaction) for diffusion in dimensions of [energy (amount
e is

of substance)−1]
us nt
ot e
nn um

T is the temperature in units of [absolute temperature] (kelvins or degrees Rankine)

ca cc

R is the gas constant in dimensions of [energy temperature−1 (amount of

u do

substance)−1]
Yo is
Th
 TG
. , II
on er
Permeability

si d
is m
m ju
er Ma
rp K
 It (commonly symbolized as κ, or k) is a measure of the

rio S
ability of a porous material to allow fluids to pass through

t p rof
ou P
it.

ith @
w ght
 The SI unit for permeability is m2.

i
r m yr
 The concept of permeability is of importance in
fo p
determining y co
an er
in d

the flow characteristics of hydrocarbons in oil and

it un

gas reservoirs, and

e is
us nt

of groundwater in aquifers and

ot e
nn um

separation of solute by membrane.

ca cc
u do
Yo is
Th
 TG
. , II
on er
 Permeability is typically determined in the lab by application of

si d
is m
Darcy's law under steady state conditions.

m ju
er Ma
rp K
rio S
t p rof
ou P
ith @
Q = The total discharge, (units of volume per time, e.g., m3/s)

w ght
k =the permeability of the medium, (m2),

i
r m yr
A = the cross-sectional area to flow, (m2), and

fo p
Pb-Pa y co
=the pressure drop (Pa),
an er
μ = the viscosity, (Pa.s) and
in d
it un

L = the length over which the pressure drop is taking place.

e is
us nt

The negative sign is needed because fluids flows from high pressure to low pressure.
ot e
nn um

Measurement of permeability through sandstones and shales yielded values from

ca cc

9.010−19 m2 to 2.4  10−12 m2 for water and between 1.7  10−17 m2 to 2.6  10−12 m2
u do

for nitrogen gas

Yo is
Th
 TG
. , II
on er
Dielectric Constant

si d
is m
m ju
er Ma
rp K
rio S
 What is dielectric?

t p rof
 A dielectric is a material which has poor electrical conductivity

ou P
ith @
but inherits an ability to store an electrical charge (due to

w ght
Dielectric polarization).

i
r m yr
 Thus exhibiting only displacement current making it ideal to build

fo p
y co
a capacitor; to store and return electrical energy.
an er
 What is Dielectric Constant?
in d
it un

 Dielectric Constant of a substance can be defined as:

e is

The ratio of the permittivity of the substance to the permittivity

us nt
ot e

of the free space

nn um

 It expresses the extent to which a material can hold electric flux

ca cc
u do

in it.
Yo is
Th
 TG
. , II
on er
Further reading......

si d
is m
m ju
er Ma
rp K
Text Books:

rio S
t p rof
 R. M. Felder, Ronald W. Rousseau, Lisa G. Bullard, Elementary

ou P
ith @
Principles of Chemical Processes, 4th Ed., John Wiley & Sons,

w ght
Asia, 2017.

i
r m yr
 D. M. Himmelblau, J. B. Riggs, Basic Principles and Calculations in

fo p
y co
Chemical Engineering, 7/8th Ed., Prentice Hall of India, 2012.
an er
Reference Books:
in d
it un

 N. Chopey, Handbook of Chemical Engineering Calculations,

e is

4th Ed., Mc-Graw Hill, 2012.

us nt
ot e

 Olaf, K.M. Watson and R. A. R. Hougen, Chemical Process

nn um

Principles, Part 1: Material and Energy Balances, 2nd Ed., John

ca cc

Wiley & Sons, 2004.

u do
Yo is
Th
 Th
Yo is
u do
ca cc
nn um
ot e
us nt
e is
it un
in d
an er
y co
fo p
r m yr
i
w ght
ith @
ou P
t p rof
rio S
rp K
Thank You

er Ma
process

m ju
is m
si d
For any query:

on er
. , II
TG
Next Lecture:

Pressure and temperature of flow

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