UNIT IV

Shell mass balances and boundary conditions:

Diffusion problems are solved by making mass balances for a specific chemical species
over a thin shell of solid or fluid. One has to select an appropriate shell of the system and
the law of conservation of mass is written in the form:
{rate of mass of A in} – {rate of mass of A out} + {rate of production of mass of A by
homogeneous Chemical reaction} = 0. This conservation statement can also be expressed
in terms of moles. The chemical species A may enter or leave the system by means of
diffusion and by virtue of the over-all motion of the fluid. Also, species A may be produced
or destroyed by homogeneous chemical reactions. After the different terms of the above
equation are written and the various steps of developing the representative differential
equation are undergone one needs Boundary conditions emanating from Physical factors
for the evaluation of the integration constants associated with the solving of the
differential equation.
The boundary conditions are specified as per the points below:

i) The concentration at a surface can be specified. Say xA = xA0.

ii) The mass flux at a surface can be specified[ if the ratio (NA / NB) is known it is as good
as knowing the concentration gradient]; e.g. NA = NB.
iii) If diffusion is occurring in a solid, it may happen that at the solid surface substance A
is lost to a surrounding fluid stream according to the relation NA0 = kC (CA0 - CAf) in which
NA0 is the mass flux at the surface, CA0 is the surface concentration, CAf is the
concentration in the fluid stream, and the proportionality constant kC is a mass transfer
coefficient’ . This is analogous to ‘Newton’s law of Cooling’
iv) The rate of reaction at the surface can be specified. E. g. If substance A disappears
at a surface by a first order chemical reaction , N A0 = k1’’ CA; i. e. the rate of
disappearance at a surface is proportional to the surface concentration, the
proportionality constant k1’’ being a first order rate constant.

Mass transfer in respect of ‘diffusion through a stagnant film’:

Consider the diffusion system shown in Fig below. Liquid A is evaporating into gas B, and
we imagine that by some means the liquid level at z=z1, is maintained constant. Right at the Liq-
gas interface the gas phase concentration of A, expressed as mole fraction is xA1. This is taken to
be the gas phase concentration of A corresponding to equilibrium with the liquid at the interface:
i. e., xA1 is the vapour pressure of A divided by the total pressure, [PA(vap) /P], provided that A and
B form an ideal gas mixture. It is to be further assumed that the solubility of B in A is negligible.

At the top of the tube (at z = z2) a stream of gas mixture A-B of concentration XA2 flows past
slowly; thereby the mole fraction of A at the top of the column is maintained at xA2. The entire
system is presumed to be held at constant temperature and pressure. Gases A and B are assumed
to be ideal.

When this evaporating system attains steady state, there is a net motion of A away from the
evaporating surface and the vapour B is stationary. Hence we can use the expression for NAz as
given in the general molar flux equation with NBz =0 :

NAz = -c DAB( xA / z) + xA(NAz + NBz)

Becomes NAz = - c DAB (1 – xA) ( xA / z) ----[1]

A mass balance over an incremental column height z states that at steady stae:

S NAz|z - S NAz|z+ z = 0 ----- [2]

In which S is the cross sectional area of the column. Division by S z and taking limit as z 0
gives

dNAz / dz) = 0 ------ [3]

Substitution of Eqn[1] into Eqn[3] gives:

(d/dz) {[c DAB /(1- xA)](xA / z)} = 0 ---- [4]

For ideal gas mixtures at constant temperature and pressure, c is a constant and DAB is very
nearly independent of concentration. Hence Eqn. [4] becomes:

(d/dz) {[1/(1- xA)](xA / z)} = 0 ---- [5]

This is a second order differential equation for the concentration profile expressed as mole fraction
of A. Integration with respect to z gives:

[1/(1- xA)](xA / z)} =C1 ---- [6]

A second integration then gives:

- ln(1- xA) = C1 z + C2 ---- [7]

The two constants of integration may be determined using the boundary conditions:

B.C.1: at z = z1, xA = xA1 ---- [8]

B.C.2: at z = z2, xA = xA2 ---- [9]

On substituting the expressions for the integration constants the following expression for the
concentration profile is obtained:

[(1 – xA)/(1 – xA1)] = [(1 – xA2)/(1- xA1)] {(z-z1)/(z2-z1)}

Or (xB /xB1) = (xB2 /xB1) {(z-z1)/(z2-z1)}

Problems:

1.Glycerine is flowing through a horizontal tube of 0.5 m long and 3 mm inside

diameter. For a pressure drop of 3 atm., the flow rate is 0.0002 m3 / min. The density
of glycerine is 1.26 g / cc. From the flow data find the viscosity of glycerine.

Solution:

We know for laminar flow of fluids through circular pipes the Hagen-Poisuelle
equation is given as:

P R4P R4( ) (3X1.01325X103) (0.3/2)4

Q = ----------- ;  = ------------ ;  =--------------------------------------

8  L 8QL 8X(0.0002/60)106 x (0.5X100)

= 0.03624 CP

To substantiate the use of the Hagen Poisuelles equation it has to be checked whether the flow
is under laminar conditions for which only it is applicable. Reynolds number is to be determined.

D (vz)  4 Q  4 x (0.0002/60)106 x 1.26

Re = ------------- = ------------ = ------------------------------------- = 0.5944

 D  x (0.3/2) x 0.03624 (Dimensionless)

Thus the flow is laminar and hence the usage of Hagen – Poisuelle equation is justified.

Conservation laws:

The general law of conservation are: Law of conservation of momentum; law of conservation of energy
and law of conservation of mass.

The general law of conservation can be written as:

{Rate of the Quantity in} +

{Rate of the quantity out} +

{Rate of generation of the Quantity} = {Rate of accumulation of the quantity}

For determining the Momentum Flux distribution and Velocity distribution in a flow situation an
elemental thin shell of fluid is considered and momentum balance is made on that. The momentum
balance equation for the steady state flow is written as:

{ Rate of momentum in} + {Rate of momentum out} + {Sum of forces acting on system} = 0

Momentum may enter the system by momentum transfer according to Newtonian (or non-Newtonian)
expression for the momentum flux. Momentum may also enter by virtue of the over-all fluid motion. The
forces that one will be concerned with are the pressure forces that act on surfaces and gravity forces which
act on the volume as a whole.
 For determining the Thermal flux distribution and temperature distribution in solids and in laminar
flow, an elemental thin shell is considered and thermal energy balance is made on that. Such shell energy
balance equation for steady state can be written as follows:

{rate of thermal energy in} – {rate of thermal energy out} + {rate of thermal energy production} = 0

Thermal energy may enter or leave the system by the mechanism of heat conduction according to Fourier’s
law. Thermal energy may also enter or leave the system by virtue of the over all fluid motion;(This type of
transport is sometimes referred to as convective transport) and the energy entering and leaving this way is
commonly called the sensible heat in and out. Thermal energy may be ‘produced’ by the degradation of
electrical energy, by the slowing down of the neutrons and nuclear fragments liberated in the fission process,
by the degradation of the mechanical energy(viscous dissipation) and by conversion of chemical energy
into heat. It should be emphasized that this energy balance equation is restricted as no mention is made of
kinetic energy, potential energy or work.

Shell Mass balance equation for a specific chemical species can be written as follows:

{Rate of mass of ‘A’ in} – {Rate of mass of ‘A’ out} + {Rate of production of mass of ‘A’ by
homogeneous chemical reaction} =0

Partial time derivative:

Ans. For explaining the partial time derivative an example might be sighted in respect of an assignment to you to observe
and report the fish concentration in a river. As the fish will be moving themselves apart from the movement of the river, it can
be easily seen that the fish concentration ‘ c ‘ will be a function of position (x,y,z) and time ‘t’. One of the primary ways that it
would occur to one is to stand on a bridge on the river and observe to note how the fish concentration in the river below changes.
One will then be observing how the concentration changes with time at a fixed position in space. Hence the rate of change of
fish concentration c /t means that it is the partial of ‘c’ with respect to time keeping x.y.z ccnstant. This is thus the explanation
for partial derivative .

Total time derivative:

Ans. Instead of standing on the bridge and observing the fish concentration if the observer gets into a speed boat and sped
around the river , sometimes upstream and sometimes down stream and sometimes across the current. Thus if one reports the
change of fish concentration with respect to time , the numbers reported should reflect the motion of the boat. This, called total
time derivative is given by:
 dc / dt = c /t + (c /x) (dx/dt) + (c /y) (dy/dt)+ (c /z) (dz/dt)

in which dx/dt, dy/dt and dz/dt are the velocity components of the boat.

Equations of continuity for a binary mixture

Equation of continuity for a binary mixture is developed by applying law of conservation of mass of species ‘A’ to a
volume element xyz fixed in space, through which a binary mixture of A and B is flowing. Within this element, A
may be produced by chemical reaction at a rate rA (g cm-3 sec-1).

The different contributions to mass balance are :

{Time rate of change of

Mass of A in volume element} (A /t) xyz --------- [1]

{Input of A across face at x } nAx|xy z ---------- [2]

{Output of A across face at x+x} nAx|x+xy z ---------- [3]

{rate of production
of A by chemical reaction} rA xyz ----------- [4]

There are also input and output terms in the y- , and z-directions. When the entire mass balance is written down
and divided through by xyz, one gets, after letting the size of the volume element decrease to zero,

(A /t) +[( nAx /x) + ( nAy /y) + ( nAz /z) ] = rA ------- [5]

This is the equation of continuity for component A in a binary mixture. It describes the change of mass concentration of
A with respect to time at a fixed point in space, this change resulting from motion of A and chemical reactions producing
A. The quantities nAx , nAy , nAz are the rectangular components of the mass flux nA = A vA In Vector notation Eqn.[5]
may be written as:
(A /t) + ( . nA) = rA --------- [6]
(A /t) + ( . nA) = rA --------- [6]

Similarly the equation of continuity for component B is

(B /t) + ( . nB) = rB --------- [7]

Addition of these two equations [6] and [7] gives

(/t) + ( . v) = 0 --------- [8]

In arriving at [8] we have used the relations nA + nB = v and also rA + rB = 0

For a fluid of constant mass density Eqn.[8] reduces to: ( . v) = 0 --------- [9]

The above development could have been done in terms of molar units. The corresponding equations for [8] and [9] will
be:

(C/t) + ( . Cv* ) = (RA +RB) --------- [10]

( . v* ) = (1/C) (RA +RB) --------- [11]

Where RA and RB are the molar rates of Production of A and B respectively. V * is the molar average velocity.

Equation of Continuity in rectangular and cylindrical co-ordinates:

Rectangular co-ordinates (x,y,z) :

(/t)+[(vx )/x] +[(vy )/y]+[(vz )/z] = 0

Cylindrical co-ordinates :

( /t) +(1/r) [(rvr )/r]+ (1/r)(v /)+ (vz/z) = 0

The Navier – Stoke’s equation through shell momentum balances

1. Write the general momentum Balance equation in words

2. Draw the sketch of a three dimensional rectangular co-ordinated volume element x y z
3. Consider the x-component of the different terms like momentum entry and exit in respect of bulk flow and viscous
transport
4. write the pressure and gravity terms
5. Finally the accumulation of momentum term is to be written
6. Substitute all the different terms in the general momentum balance equation.
7. The resulting equation is divided by the volume element x y z and take limit as the volume element tends to zero.
The x-component of equation of motion is thus obtained.
8. Write down the y-component and z-component analogously.
9. The terms such as(  vxvy) are expanded and rearranged, using equation of continuity, and regrouped to get x-
component as:
(Dvx/Dt) =
10. Combine these three to write

 (Dv / D t) = - . p + µ 2 v + g
Derivation the Hagen–Poisueille equation by the application of Navier-Stoke’s equation:

The Navier Stokes equation as given by above is to be written down and then deduce the equation for flow in z-direction and go
ahead to find expressions for Velocity, Averag velocity and volumetric flow rate which is the Hagen Poiseuelle equation.

Q ={[ ( P 0 – P L )R4]/(8  L) }

The equation of Continuity from shell mass balances in three dimensional Cartesian co-ordinates

Equation of continuity is developed by applying law of conservation of mass to a volume element xyz fixed in space,
through which a fluid is flowing.

Write the general mass balance equation as :

{rate of mass accumulation} ={ rate of mass in} – {rate of mass out}

 Write the different terms of the above equation and insert them into the equation above and develop the differential
equation on limiting principleas:

(/t)= -[(/x) (vx )+ (/y) (vy) +(/z) (vz)]

And in the modified form as :

(D/Dt) = -  ( . v)

Stokes’ Law:

The sum of the form drag and the friction drag and the friction drag for flow of fluids past spherical particles given by
Fk ( the force associated with the fluid movement i.e the kinetic contribution) as = [6  * R *µ * v)

Euler’s Equation:

Euler equation is geven by :  (Dv / D t) = -  p + g

It is obtained from the Navier-Stokes equation when the viscous force terms are neglected. It is widely used to
describe the flow systems in which viscous .terms are relatively unimportant.

Blake Kozney equation:

Ans. V0 = [P0 - PL ] * { [ Dp2 * ε 3] / [150 * L* µ (1 - ε)2]}

Where ε is void fraction of the packed bed and Dp is the mean particle diameter.

Equation of motion:
r-component of the Equation of motion in Cylindrical co-ordinates:

{( vr/t)+vr( vr/r)+(v/r)(vr/)-(v2/r)+vz(vz/z)} = - (p/r) –

{(1/r)[(/r)(rrr)] +(1/r)[(/)(r)] – ( /r) +(rz/z)} + gr

-component of the Equation of motion in Cylindrical co-ordinates:

{( v vr/t)+vr(v/r)+(v/r)( v/)-(vrv/r)+vz(v/z)} =

-(1/r) (p/) – {(1/r2)[(/r)(r2r)] +(1/r)[(/)()] +(z/z)} + g

Continuity equation, Navier-Stoke’s equation, Euler equation and explain their field of application:

Equation of continuity: (/t)= -[(/x) (vx )+ (/y) (vy) +(/z) (vz)]

This describes the rate of change of density at a fixed point resulting from the changes in the mass velocity vector
‘v ’ . This may also be written as:

(/t) = - ( . v )

Here ( . v ) is called the divergence of v , sometimes called as div v . It is to be noted that the vector v is
the mass flux and its divergence is the net rate of mass flux per unit volume. It simply states that the rate of increase
of density within a small volume element is equal to the net rate of mass influx to the element divided by its volume.
It can be modified into: (D/Dt) = -  ( . v)

The equation continuity in this form describes the rate of change of density as seen by an observer ‘floating along’
with the fluid.
A very important special form of equation of continuity is that for a fluid of constant density as:

( . v ) = 0

Although no fluid is truly incompressible very frequently in engineering practice the assumption of constant density
results in considerable simplification and almost no error.

For constant density and constant viscosity, the equation of motion can be simplified using the Equation of
Continuity ( . v ) = 0 to get:

 (Dv/Dt) = -  p+ 2v + g

This is called the Navier-Stokes equation applicable for incompressible fluids of constant viscosity.
For flow systems in which viscous effects are relatively unimportant the equation motion reduces to:
 (Dv/Dt) = -  p+ g

This is the famous Euler’s equation

Problems:

A hollow steel sphere, 5 mm diameter with a mass of 0.05 g, is released in a column of liquid and attains
a terminal velocity of 0.5 cm/sec. The liquid density is 0.9 g/cc. The local acceleration due to gravity is
981 cm/s2. The sphere is far enough from the container walls so that their effect may be neglected.

(a) Compute the drag force; (b) Compute the drag co-efficient

(c) Determine the viscosity of the liquid.

Stokes law is applicable for spherical bodies with Reynolds number less than 0.1.

The expression is The force of gravity on the hollow sphere acts in the direction of fall, and
the buoyancy force and the force due to fluid motion act in the
opposite direction:

[(4/3)  R3s g] = [(4/3)  R3  g ] + [6  vt R]

Force of gravity Buoyancy force Force due to

Acting on sphere fluid motion

R: is the radius of the sphere; s is the density of the solid material [ 7.6 gm/cc]; is the density
of the liquid 0.9 gm/cc; vt is the terminal velocity; [(4/3)  R3s] is the mass of the
sphere 0.05g

Calculate the different forces and the viscosity of the liquid from the expression:
  = 2 R (s - )g/ 9 vt This expression is valid only if (Dvt/) is less than about 0.1[verify]

Calculate the drag coefficient or friction factor using the equation:

f = (4/3)(g D/v2)[ (s - )/]