Unit -III

Material balance in steady and unsteady reaction

systems

Dr. Ranjeet singh

Deptt. of Biotechnology
IET Bundelkhand University Jhansi
1. Steady State and Equilibrium

“If all properties of a system, such as temperature, pressure, concentration, volume, mass, etc. do
not vary with time, the process is said to be at steady state”.

Thus, if we monitor any variable of a steady-state system, its value will be unchanging with
time.

According to this definition of steady state, batch, fed- batch and semi-batch processes cannot
operate under steady-state conditions.

Mass of the system is either increasing or decreasing with time during fed-batch and semi-
batch processes; in batch processes, even though the total mass is constant, changes occurring
inside the system cause the system properties to vary with time. Such processes are called
transient or unsteady-state processes.

On the other hand, continuous processes may be either steady state or transient. It is usual to run
continuous processes as close to steady state as possible; however, unsteady-state conditions
will exist during start-up and for some time after any change in operating conditions.
 M̂i M̂o
System
kg h-I
kg h -I
kg h-I
Glucose Glucose

Figure 1. Flow system for mass balance on glucose

 In continuous processes at steady state, mass is constantly exchanged with the surroundings;
this disturbance drives the system away from equilibrium so that a net change in both the
system and the universe can occur. Large- scale equilibrium does not often occur in
engineering systems; steady states are more common.

4.2 Law of Conservation of Mass

Mass is conserved in ordinary chemical and physical processes. Consider the system of
Figure 1 operating as a continuous process with input and output streams containing
glucose.
The mass flow rate of glucose into the system is M̂i kg h-1; the mass flow rate out is M̂o kg
h-I and if M̂i and M̂0are different, there are four possible explanations:
(i) measurements of M̂i and M̂0 are wrong;
(ii) the system has a leak allowing glucose to enter or escape undetected;
(iii) glucose is consumed or generated by chemical reaction within the system; or
(iv) glucose accumulates within the system.
If we assume that the measurements are correct and there are no leaks, the difference
between M̂i and M̂0 must be due to consumption or generation by reaction, and/or
accumulation. A mass balance for the system can be written in a general way to account for
these possibilities:
A mass balance for the system can be written in a general way to account for these
possibilities

{mass in through system boundaries}- {mass out through the system boundaries}+ {mass
generated within the system}={mass accumulated within the system} --(1)

The accumulation term in the above equation can be either positive or negative; negative
accumulation represents depletion of pre-existing reserves. Eq. (1) is known as the general
mass-balance equation.

General Mass-Balance Equation

Eq. (1) can be simplified in certain situations. If a continuous process is at steady state, the
accumulation term on the right-hand side must be zero. This follows from the definition of
steady state: because all properties of the system, including its mass, must be unchanging
with time, a system at steady state cannot accumulate mass.
Under these conditions, Eq. (1) becomes:

mass in + mass generated = mass out + mass consumed-----------(2)

Eq. (2) is called the general steady-state mass-balance equation. Eq. (2) also applies over
the entire duration of batch and fed-batch processes; 'mass out' in this case is the total
mass harvested from the system so that at the end of the process there is no
accumulation.
2. Unsteady-State Material-Balance Equations

When mass of a system is not constant

how the mass varies as a function of time ?

To evaluate the rate of change of mass in the system, let us first return to the
general mass-balance equation

{mass in through system boundaries}- {mass out through the system boundaries}
+ {mass generated within the system}={mass accumulated within the system}
The flow system of Figure 6.1 in which reactions are taking place. Species A is
involved in the process; M is the mass of A in the system. Using the 'hat' symbol
̂ to denote rate, let

M̂i be the mass flow rate of A entering the system,

M̂o the mass flow rate of A leaving.

RG is the mass rate of generation of species A by chemical reaction

RC is the mass rate of consumption by reaction.

The dimensions of M̂i, M̂o, RG and RC are MT-1, with units such as g s-1, kg h-1, lb
min-1, etc.
 M̂i System
MRg Rc M M̂o

Figure 2. Flow system for unsteady state mass balance

All of the variables: M̂I, M̂o, RG and Rc, may vary with time.

However, let us focus on an infinitesimally-small Time interval interval of time. At

between times t and t + Δt. Even though the system variables may be changing.

If it is sufficiently small we can treat the flow rates M and rates of reaction R as if
they were constant during this period. the terms of the general balance equation
may be written as follows.

(i) Mass in. During period Δt, the mass of species A trans- ported into the system is M̂i Δt.

(ii) Mass out. Similarly, the mass of species A transported out during time Δt is M̂o Δt.

(iii) Generation. The mass of A generated during Δt is RG Δt.

(iv) Consumption. The mass of A consumed during At is RCΔt.

(v) Accumulation. Let ΔM be the mass of A accumulated in the system during Δt. ΔM may
be either positive (accumulation) or negative (depletion).
Entering these terms into the general mass balance

ΔM = M̂i Δt - M̂oΔt + RG Δt - RC Δt.

Divide both sides of Eq. (1) by Δt to give

ΔM/ Δt = M̂i - M̂o + RG - RC -----------(II)

Eq. (II) applies when Δt is infinitesimally small. If we take the limit as Δ t approaches zero, i.e. as t
and t + Δt become virtually the same, Eq. (II) represents the system at an instant rather than over
an interval of time. Mathematical techniques for handling this type of situation are embodied in
the rules of calculus. In calculus, the derivative of y with respect to x, dY/dx, is defined as:
dy/dx = lim ΔX→0 Δy/ ΔX (III)
lim ΔX→0
represents the limit as Axapproaches zero. As Eq. (6.2) is valid for Δt---> 0,

dM/dt = lim Δt→0 ΔM/ Δt = M̂i - M̂o + RG - RC (IV)

dM/dt = M̂i - M̂o + RG – RC (V)

At steady state there can be no change in mass of the system, so the rate of change, dM/dt must be
zero
Thanks