CH 6403 CHEMICAL PROCESS CALCUALATIONS

Unit II
Introduction to Material Balances, Material balance problems for single units, Stoichiometry and Chemical Reaction
equations, Material balance for processes involving bypass, recycle Operations.
Introduction to Material Balances:
Material balances: material balances express the constraint of conservation of mass, as applied to a process.
Batch process: In a batch process, raw materials are fed into the process at the outset. The process then runs for some
length of time, producing product, but no product is removed, and no additional raw materials are input (but energy
may be input or withdrawn), while the process runs. At the end, the product is removed. The bottom line is that no
mass enters or leaves while the process is running.
Continuous process: In this type of process, raw materials continuously enter and product continuously leaves the
process.
Semi batch process: A semi batch process does not fall fully under either batch or continuous classification.
Steady-state operation: Under steady-state, the values of all variables associated with the process do not change with
time. That is, at any given location in the process, the values of temperature, pressure, composition, and flow rates,
etc. are independent of time. Even though a process may be steady state, it is important to realize that temperature,
flow rates, or other variables may, and typically do, change from one location to another (e.g. from one process stream
to another).
Transient or unsteady-state operation: If some process variables change with time, then the process is transient. A
process must be either steady-state or transient. Batch and semi batch processes must be transient. Continuous
processes may be transient or steady-state.
General Material Balance Equation
Input + generation output consumption = accumulation
Input: enters through system boundaries
Generation: is produced within the system
Output: exits through system boundaries
Consumption: is used up within the system
Accumulation: is built up within the system
Under steady state Input = Output.
There are three general method of solving material balance problems for systems involving no chemical reactions.
(i). Balancing the tie material. Tie material is one whose quantity does not change during the particular operation.
Ex: Dissolved solids in an evaporator problem.
(2). Balancing the inert chemical species which do not take part in the operation.
Ex: Nitrogen in combustion process.
(3). Individual component balances to generate equal number of equations as that of unknowns.
Before solving any material balance problem a definite basis is to be assumed. Often the basis is defined in the
statement of the problem itself. If this basis is not convenient a new more convenient basis can be selected. Using
this basis, the problem must be solved with consistent units.
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Material Balances involving Chemical Reactions

Chemical reactions play a vital role in the manufacturing processes. The material balance and energy balance
calculations, helps in design by specifying the flow rates and temperatures of various streams.
The law of conservation of mass, holds good for the material balances involving chemical reactions also.
Total mass entering the reactor = Total mass of products leaving the reactor
It should be noted that in chemical reactions, the total mass of the input remains constant, but the total number of
moles may or may not remain constant.
Ex: CO + H2 O CO2 + H2 ..(i).
N2 + 3H2 2NH3 .(ii).

Here mole balance is valid.

Here mole balance in not valid.

Stochiometric equation is a statement which indicates the number of moles of reactants and products that take
part in the chemical reaction and are balanced equations.
In reaction (i). One mole of carbon monoxide is equivalent to one mole of water, one mole of Hydrogen and one mole
of Carbon dioxide.
The above equalities decide the Stochiometric requirements of the components.
Limiting reactant: The component that present in less quantity than its Stochiometric proportion with respect to
other reacting components is known as limiting reactant.
Excess reactant: The component that is present in excess quantity than its Stochiometric proportion with respect to
other reacting components is known as excess reactant.
Ex: CH4 + H2 O CO + 3H2
In the reforming reaction of Methane with steam, usually steam that is fed to the reformer is in excess of the
Stochiometric requirement.

Conversion, Selectivity and Yield:

Conversion is defined as the ratio of the reacting amount of a component to its initial amount. It is the
measure of the degree of completion of the chemical reaction.
The side reactions occur during the production of the desired product by reacting raw material. These side
reactions may result in the production of other components or undesired products and affect the economy of the
process.
The yield and selectivity are the measure of the degree of the desired reaction predominates over other side
reactions.
The yield is defined as quantity of limiting reactant reacted to produce the desired product expressed as
percentage of the total quantity of limiting reactant reacted.
2

Moles of A reacted to produce P in final Product

Yield P = ------------------------------------------------------------- x 100
Moles of A totally reated
For a reaction A + B P ( Desired Product)
A + P R ( Undesired Product)

Moles of P in Final Product

Selectivity of P relative to R = ----------------------------------------Moles of A totally reacted
Recycle and Bypass Operations
Feeding back the part of the product steam leaving the reactor along with fresh feed is termed as recycling
operation.
Recycling helps in
(i). Product enrichment.
(ii). Waste minimizing by maximum utilization of raw material
(iii). Increase in the yield of the product.
(iv). Energy saving.
Purging is the operation in which inert component is (bleed off) taken off from the recycle stream. If the
recycled stream contains the inert material it leads to accumulation of such material, which is not desirable. The
accumulation of inert material may cause decrease in conversion, decrease in yield by causing the side reactions.
Quantity of recycle feed
Recycle ratio = --------------------------------Quantity of fresh feed
Quantity of A mixed feed
Combined feed ratio = ----------------------------------Quantity of A in fresh feed
Quantity of A in purge stream
Purge ratio = -------------------------------------------Quantity of A in recycle stream
Bypassing operation is one in which the process stream skips one or more stages of the process and goes
directly to another stage with the purpose controlling the composition of a final exit stream.
Ex: In ammonia synthesis by passing is carried out to control the reactor bed temperature.

PROBLEMS
MATERIAL BALANCES WITH CHEMICAL REACTIONS
1. SO2 is produced by the reaction between Copper and Sulphuric acid. How much Copper must be used to get
10 Kg of SO 2
Cu + 2H2 SO4 SO2 + 2 H2O
As per the above stoichiometry, 1 mole of Copper reacts with 2 moles of Sulphuric acid to produce one mole of
Sulphur dioxide.

We know

Mass of the Chemical

Moles = --------------------------Molecular weight

Hence Mass of the Chemical = (Moles) x Molecular Weight

Mass of 1 mole of Copper = (1) x 63.54 = 63.54 Kg
Mass of 1 mole Sulphur dioxide = (1) x 64 = 64 Kg.
That is 63.54 gms of Copper produces 64 gms of Sulphur diaoxide.
To produce 10 Kg of Sulphur dioxide: (64/63.54) = 9.93 Kg Ans.
2. What is the weight of Iron and water required for the production of 100 Kg of Hydrogen.
3 Fe + 4 H2 O Fe 3O4 + 4 H2
167.52 72
231.52 8
As per the stoichiometry.,
167.52 Kg of Iron Produces 8 Kg of Hydrogen.
For 100 Kg of Hydrogen, Iron required = (167.52/8) x 100 = 2094 Kg. Ans
72 Kg of water is needed to produce 8 Kg of Hydrogen.
For 100 Kg of Hydrogen, water required = (72/8) x 100 = 900 Kg. Ans

3. The gas Acetylene is produced according to the following reaction.

CaC2 + 2 H2O C2 H2 + Ca(OH)2
Calculate the number of hours of service that can be derived from 1 Kg of Calcium carbide, in an acetylene
lamp burning at the rate of 60 liters per hour at a temperature of 20 deg C and a pressure of 740 mm Hg.
CaC2 + 2 H2O C2 H2 + Ca(OH)2
64

26

64 Kg Calcium carbide produces 26 Kg of Acetylene.

1 Kg of Calcium carbide produces = (26/64) x 1 = 0.406 Kg.
4

Kg mole of Acetylene = Mass/ Mol Wt = n = 0.406/26 = 0.156 gr mole.

Estimation of R in mm Hg, liters and Kelvin:

At 760 mm Hg, 273 K, 1 gr mole of idel gas occupies 22,400 liters.
For ideal gas Pv = nRT
(760) x (22400)
R = Pv/RT = --------------------- = 62,358.9 mm Hg liters per gr mole Kelvin.
273
Assuming Acetylene to behave as Ideal gas, Pv = nRT
Volume of acetylene produced in liters at the operating pressure of 740 mm Hg and operating temperature of 20 deg
C, that is 293 K.,
= v = nRT /P
(0.156) (62,358)( 293)
= -------------------------------740
= 385. 8 Lit.
Lamp burns at the rate of 60 liters per hour.
With 385.6 Liters of number of Hours of service obtainable = 385.8/60
= 6.43 Hours.
4. 200 Kg pure Sulphur is burnt with 25% excess air, to convert it to Sulphur dioxide. In the process 4.5% of
it, gets oxidized to Sulphur trioxide. Calculate the composition of the gas, leaving the burner.
Basis: 200 Kg of Sulphur.
Reactions: S + O2 SO2
32

32

and

64

S + 1.5 O 2 SO3
32

48

80

1 K atom of Sulphur requires 1 K mole of Oxygen.

200 Kgs, that is 200/32 ., 6.25 K atom of Sulphur requires 6.25 K moles of Oxygen.
We know that air contains 21 mole% of Oxygen and 79 mole% of Nitrogen.
Therefore Air required = 6.25 /0.21 = 29.76 Moles.
It is given that 25% excess air is fed to the system.
Total air entering = (29.76) + (29.76) x 25/100 = (29.76) x (1.25) = 37.2 Kg mol.
Hence Nitrogen entering = (37.2) x 0.71 = 29.39 K mol.
(Which is coming out through the exhaust gases)
1 K atom of sulphur produces 1 Kg mole of SO 2 , by reacting with 1 Kg mole of Oxygen.
95.5 % of Sulphur gets converted to Sulphur dioxide
SO2 formed = (6.25) x 0.955 = 5.97 Kg mol.
Oxygen utilized in this conversion = 5.97 Kg mol. ..(i).
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1 K atom of sulphur produces 1 Kg mole of SO 3 , by reacting with 1.5 Kg mole of Oxygen.

4.5% of Sulphur gets converted to Sulphur trioxide
SO3 formed = (6.25) x 0.045 = 0.28 Kg mol.
Oxygen utilized in this reaction = (1.5) x 0.28 = 0.42 Kg mol.(ii).
Total O2 consumed = (i) + (ii) = 5.97 + 0.42 = 6.39 Kg mol.
Oxygen unreacted = O2 fed O2 reacted = (37.2) x 0.21 - 6.39 = 1.42 Kg mol.
Exhaust gas analysis:
Component

Mol

Mole%

SO2

5.97

16.11

SO3

0.28

0.76

O2

1.42

3.83

N2

29..39

79.30

37.06

100

Total

5. A mixture of pure Carbon dioxide and Hydrogen is passed over a nickel catalyst. The analysis of gases
leaving the reactor showed 57.1% CO 2, 14.1% H 2 , 1.68% CH4 and 0.12% CO by volume on a dry basis. The
reactions taking place in the reactor are
CO2 + 4H2 CH4 + 2H2 O .(i).
CO2 + H2 CO + H2O ...(ii).
Find the conversion of CO 2 and the yield of CH 4 in terms of CO2 reacted?
Basis: 100 Kg moles of dry product gas.
Kg moles of CH4 produced = 1.68
Kg moles of CO Produced = 0.12
Kg moles of CO2 unreacted = 57.10
Kg moles of H2 unreacted = 41.1
From reaction (i). 1 Kg mole of CO 2 produced 1 Kg mole of CH4
Therefore 1.68 Kg moles of CH 4 should have consumed 1.68 Kg mole of CO 2
From reaction (ii). 1 Kg mole of CO is produced from 1 Kg mole of CO 2
Therefore 0.12 Kg mole of CO should have consumed 0.12 Kg mole of CO 2
CO2 totally reacted = 1.68 + 0.12 = 1.80 Kg mole
CO2 supplied = CO2 reacted + CO2 unreacted
= 1.80 + 57.1 = 58.9.
Therefore % conversion of CO 2 = (1.80/58.9) x 100 = 3.06%
Yield of CH4 = (CO2 reacted to give CH4 / CO2 totally reacted ) x 100
= (1.68/1.80) x 100
= 93.28%
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6. In the manufacture of Chlorine a dry mixture of hydrochloric acid gas and air is passed over a heated
catalyst which promotes oxidation of the acid. Air is used in 30% excess of that theoretically required.
(a). Calculate the weight of air supplied per kg of acid.
(b). Calculate the composition by weight of the gas entering the reaction chamber.
(c). Assuming that 60% of the acid is oxidized in the process, calculate the composition by weight of the
gases leaving the chamber.
Solution: Basis: 1 Kg of dry HCl gas.
Reaction: 4HCl + O2 2Cl2 + 2H2 O
4 x 36.5 Kg of HCl require 32 Kg of O 2
1 Kg require 32/146 = 0.219 Kg.
Theoretical air = 0.219 (100/23) = 0.953 Kg
Air supplied (30% excess) = 0.953 x 1.3 = 1.24 Kg. Ans (a).
Ans (b).

Analysis of the gas entering reaction Chamber:

Constituents

Amount Kg

Wt%

HCl

1.00

44.66

O2

0.285

12.73

N2

0.955

42.61

Total

2.24

100.0

Ans (c) : Composition of the gases leaving the reaction chamber:

Reaction is 60% complete
Chlorine formed = 142/146 x 0.6 = 0.583 Kg
Water Vapor = 36/146 x 0.6 = 0.148 Kg
Oxygen Used = 32/146 x 0.6 = 0.132 Kg
Oxygen Left = 0.285 0.132 = 0.153 Kg
Analysis of Gases leaving:
Constituents

Wt. , Kg

Wt %

HCl

0.400

17.87

O2

0.153

6086

N2

0.955

42.62

Cl2

0.583

26.04

H2 O

0.148

6.61

Total

2.239

100.00

Humidification Operations
Psychometry is the subject which deals with the properties of gas-vapor mixtures. One of the most important
Psychometric operations is the air-water operations. These operations are also referred to as Humidification
operations.
Definitions: (i). Dry bulb temperature: The temperature of the vapor gas mixture, recorded by the immersion of a
thermometer in the mixture is termed as dry bulb temperature (DB)
(ii). Absolute Humidity: The weight of water present in a unit weight of dry air is termed as absolute humidity.
H = Mass of Vapor/Mass of dry air.
(iii). Absolute Molar Humidity: This is defined as ratio of moles of water vapor present to the moles of dry air.
Hm = nA / nB = P A /P B

{PA V = nART., P BV = nBRT

Therefore nA = PA ; nB = P A }

Again H = WA /WB = nA MA / nBMB = Hm {MA /MB}

We know A is water hence MA = 18, and B is air, its average molecular wt MB = 29
H = Hm {MA /MB} = Hm {18/29} = Hm 0.622

or Hm = 1.60 H

If PA is the partial pressure of water vapor and P is the total pressure of the mixture,
Then H = 0.622 (P A / P - P A )
(iv). Saturation Humidity: The absolute humidity at 100% saturation is called saturation Humidity (Hs). When the
air is fully saturated, then P A = Ps, the vapor pressure of water at DB,
Hs = 0.622 (Ps / P Ps)
(iv)Percentage Humidity or Percentage Absolute humidity: It is defined as the ratio of the actual absolute humidity
to the saturation humidity.
% Humidity: = {H/Hs} x 100
(v): Relative Humidity or Percentage relative humidity: It is the ratio of the partial pressure of water vapor in air to
the vapor pressure of water at the dry bulb temperature.
RH = { P A / Ps } x 100
(vi). Humid Heat: It is defined as the heat capacity of 1 kg dry gas and the moisture contained in it. It is the heat
required to rise the temperature of unit mass of gas and its accompanying vapor by one degree at constant pressure.
Cs = CA H + CB where CA and CB are specific heat of water and air.
Cs = 1.84 H + 1.006
(vii). Humid Volume: It is the volume of unit mass of dry gas and its accompanying vapor at the prevailing
temperature and pressure.
VH = RT/ pA MA

and

VHs = RT/ ps MA

(viii). Dew Point: It is the temperature at which the air water vapor mixture becomes saturated when the mixture is
cooled at constant total pressure in the absence of liquid water.

(ix). Wet bulb Temperature: If a thermometer having the bulb covered with a wet wick is kept in air-water vapor
mixture, it will read a steady value after a few seconds. This temperature is called the wet bulb temperature. It
represents the dynamic equilibrium of the heat transfer by convection to the surface and the mass transfer to the
surroundings from the surface.
Wet bulb temperature is always lower than or equal to dry bulb temperature.
At 100% saturation DB = DP = WB
(x). Adiabatic Saturation Temperature: Adiabatic process is the one in which no heat flows into or out of the
system but during which thermal changes usually occur within the system. When a definite quantity of water is
allowed to evaporate in a stream of air adiabatically, the dry bulb temperature of the gas decreases and the Humidity
of the air increases. The final temperature of the intimately mixed stream is adiabatic saturation temperature. For air
water systems WB and AST are practically same.
(xi). Enthalpy of Humid air: It is the sum of the enthalpies of each constituent as its partial pressure and common
temperature.
i = 1.006(T 273.15) + H h Where h is the total enthalpy of water vapor at TDB KJ/Kg

Problem:
The dry bulb temperature and dew point of ambient air were found to be 29 deg C and 18 deg C respectively.
The barometer reads 100.0 KPa. Partial pressure of water was found to 2.0624 KPa and saturated partial
pressure of water at this temperature is 4.004 KPa.
Compute (i). The absolute molar humidity.
(ii). Absolute Humidity.
(iii). % RH
(iv). % Saturation.
(v). Humid Heat and
(vi). Humid volume.
(i).Molar Humidty=

PA
2.0624
=
= 0.2106 K mol H 2O vap / K mole dry air.
P PA 100 2.0624

(ii). H = 0.622 Hm = (0.622) x 0.2106 = 0.0131 Kg moisture/ Kg dry air

(iii). At Saturation DB = WB = DP
% RH = (P A /P B ) x 100 = (2.0624/4.004) x 100 = 51.5%
(iv). Hs =

Ps
4.004
x 0.622 = (
) x 0.622 = 0.02594 Kg of H2 O / Kg dry air
P Ps
100 4.0004

% saturation = ( H/Hs ) x 100 = (0.0131/0.02594) x 100 = 50.49.

(v). Humid Heat = Cs = 1.006 + 1.84 H = 1.006 + 1.84 (0.0131) = 1.03 KJ/Kg dry air.
(vi). Humid Volume
H
1
DB
101.325
VH = ( ----- + ------- ) x 22.416 x (--------) x ( ------------)
9

MA

MB

273

= (0.00073 + 0.03448) (22.4136) ( 1.1062)

= 0.8846 m3 /Kg dry air.
==============================================================
(2). Air at a temperature of 200 C and 750 mm Hg has a relative humidity of 80%.
Calculate (i). The total humidity of the air.
(ii).The molal Humidity of this air if its temperature is reduced to 100 C and
Pressure increased to 2000 mm Hg condensing out some amount of water.
(iii). Weight of water condensed from 1000 liter of the original wet air.
Given Vapor pressure of water at 20 0 C = 17.5 mm Hg.
Vapor pressure of water at 10 0 C = 9.2 mm Hg.
RH = 0.8 at 20 o C and 750 mm Hg
Solution:
RH = (P/Ps) = 0.8.
Partial pressure of water at 20o C, P A = 0.8 (Ps) = 0.8 (17.5) = 14 mm Hg.
(i). Molal Humidity at 20o and mmHg Hm =

PA
14
=
P PA
750 14

= 0.019 mol H2O/Mol dry Air

(ii).

Molar

Humidity

at

10o

and

2000

mm

Hg

PA
P PA

9.2
2000 9.2

= 4.6 x 10 -3 mol H2O/Mol dry Air

(iii). Basis: 1000 Lit of Original Wet air
1 gr mol occupies 22.414 liters at NTP, which is 273 K and 760 mm Hg
1000 Lit at 293 K and 750 mm Hg, corresponds to How many number of Moles?

1000 750 273

= 37.66 gr moles.
24.414 760 293

gr mol of Wet air =

gr mol of dry air = (37.66)x(1/1.019) = 36.95 gr moles.

Water condensed = (Difference in Humidity) (Total Dry air) (Mol Wt)
= (0.019- 1.6 x 10-3 ) x 36.95 x 18
= 11.57 gr.

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