.2.
3 Moles and Mole Fraction
2.4 Method of Expressing the Composition of
Mixtures
2.5 Equivalent Weight
2.6 Concept of Normality, Molarity and Molality
There are three ways of expressing the concentration of solution containing either solid or
liquid solute, namely
1. Normality
2. Molarity
3. Molality
2.7 Concept of PPM (Parts Per Million)
It is the short form of parts per million, i.e. parts of one substance present in million parts of
another substance, especially solvent. It is commonly used as a unit of concentration.
2.9.1 Ideal Gas Law
2.10 Dalton’s Law
2.11 Amagat’s Law
2.13 Relationship between Partial Pressure,
Mole Fraction of Component Gas to Total
Pressure
2.14 Average Molecular Weight of Gas Mixture
2.15
Density of Gas Mixture
For calculating the density, one must know the average molecular weight of the gas mixture.
From the ideal gas law, we know that,
2.17
Gas–Liquid System
The approximate relationship that governs the distribution of a substance between a gas and a
liquid phase are Raoult’s and Henry’s laws which assume reasonably accurate results in
many cases.
2.17.1 Raoult’s Law
2.18
Vapour Pressure
It may be defined as the absolute pressure at which the liquid and its vapour are in
equilibrium at a given temperature. When the liquid is heated, evaporation takes place.
During the evaporation, two opposing process occurs.
1. The process of vaporisation.
2. The process of condensation.
As the vaporisation proceeds, the pressure of vaporisation increases and the rate of
condensation also increases. The moment at which the rate of vaporisation is equal to the
rate of condensation, a sort of dynamic equilibrium exists and the vapour remains
unchanged. The pressure exerted by the vapour at this condition is termed vapour
pressure of the liquid. All liquids and solids exhibit a definite vapour pressure at a given
temperature.
2.18.1 Saturated Vapour Pressure
When the vapour of a liquid exists under conditions so that its partial pressure is equal to the
equilibrium vapour pressure, then it is called saturated vapour pressure. That means, at this
condition the vapour is ready to condense.
2.18.2 Unsaturated Vapour Pressure
When the vapour of a liquid exists under conditions, such that its partial pressure is less than
the equilibrium vapour pressure, then it is called unsaturated vapour pressure. That means, at
this condition the vapour is not ready to condense. It is also called superheated vapour.
2.18.3 Boiling Point
The temperature of the liquid at which the equilibrium vapour pressure is equal to the total
pressure surrounding the liquid surface is called boiling point.
2.23
Humidity
Humidity may be defined as the ratio of mass of water vapour present in the air in kg to mass
of dry air in kg. Mathematically, humidity can be expressed under any given set of condition
as,
Normally, the amount of water present in the air is measured in terms of partial pressure, but
not in terms of weight. Let the partial pressure of water vapour present in the air sample is pA.
Then, the humidity may be expressed as,
Since, the molecular weight of water vapour and air is 18 and 29 respectively. Therefore, the
humidity at a given temperature and pressure may be expressed as,
2.23.1 Saturated Humidity
If the vapour pressure of water in air is in equilibrium with the liquid vapour, then the air is
said to be saturated at a given temperature and pressure. Mathematically, saturated humidity
can be expressed as,
2.23.4 Humid Volume
The volume occupied by a unit mass of dry gas and its associated vapour is called Humid
volume. It is denoted by VH.
2.23.5 Humid Heat
The amount of heat required to rise the temperature of unit mass of dry air and its associated
vapour by 1°C at no change in pressure is called Humid heat. Mathematically, it can be
expressed as,
HH = CA + HCW………(2.62)
Where,
HH = Humid heat
CA = Heat capacity of air (kJ/kgmol K)
H = Humidity
CW = Heat capacity of water vapour (kJ/kgmol K)
2.23.7 Dry Bulb Temperature
It is the temperature of the moist air measured by ordinary thermometer. It is commonly
referred as DBT.
2.23.8 Wet Bulb Temperature
It is the temperature of the moist air measured by ordinary thermometer when the bulb of the
thermometer is covered by wet cloth or wick. It is commonly referred as WBT.
2.24
Humidity Chart
Humidity chart gives the information of amount of moisture present in unit mass of dry air at
any given temperature. This properties of mixture of air water vapour is necessary in
designing the humidifier. It is also known as psychrometry chart. This chart mainly consists
the plots of four curves.
1. Humidity vs Temperature curve
2. Humidity vs Humid heat line
3. Specific volume vs Temperature curve
4. Adiabatic cooling lines.
2.24.1 Humidity vs Temperature Curve
In this plot, humidity is plotted on y-axis and temperature is plotted on x-axis at atmospheric
pressure. The humidity is expressed in kg of water per kg of dry air. There are many curves in
this plot and each curve represents a definite relative humidity value. The following
information may be obtained from this plot.
1. Any point on the curved line represents the temperature and humidity of the sample of air.
2. The curved line marked 100% gives the relative humidity of saturated air at various
temperature.
3. There is no air and water vapour mixture to the left of the 100% relative humidity curve.
4. There are many curves representing between 90% to 10% to the right of 100% relative
humidity curved line.
A typical humidity chart is shown in Figure 2.7.
2.24.2 Humidity vs Humid Heat Line
In this plot, humid heat is plotted against the humidity. It is observed from the chart that it is
a straight line which started from the bottom of the chart and reached the top with an angle of
60°. This plot is useful in designing the air conditioner.
2.24.3 Specific Volume vs Temperature Line
In this plot specific volume of dry air is plotted against the temperature. It is observed from
the chart that it is a straight line which started from the one end of y-axis and reached the
other end of the y-axis with an angle of 30°. The humid volume of a sample of air may be
determined at a given temperature and humidity by linear interpolation of the humidity
temperature line.
2.24.4 Adiabatic Cooling Lines
In this plot, a group of lines are plotted with a negative slope from the 100% relative
humidity curve. These lines are also called Adiabatic cooling lines. This plot is useful for two
purposes. Firstly, they can be used to determine the humidity from the knowledge of dry bulb
temperature and wet bulb temperature.
2.24.5 Application of Humidity Chart
Humidity chart represents the source data of a definite air-water mixture. A simplified portion
of humidity chart is shown in Figure 2.8.
The application of humidity chart is explained by using point A. The following data can
be obtained from the humidity chart:
1. Humidity: From point A moving horizontally towards the y-axis, gives an intercept point
B, which is the humidity of the sample air.
2. Dew point: From point A moving horizontally towards the left to the 100% relative
humidity line, gives an intersection point C. Moving vertically downwards from this point,
we get point D. This is the dew point, which represents temperature t2.
3. Adiabatic saturation temperature: From point A moving along the adiabatic cooling line
towards the 100% relative humidity curve, gives an intersection point E. Moving vertically
downwards from this point, we get point F. The line drawn from E to F is called Adiabatic
cooling line. It represents the adiabatic saturation temperature t3.
4. Humidity at adiabatic saturation: From point E moving horizontally right towards the y-
axis gives an intersection point G. The point G represents the humidity at adiabatic saturation
line. In similar way, humid volume, humid heat can be determined using humidity chart.
Material Balance without Chemical Reactions
The law of conservation of mass is the basis for material balance calculations. It states that
the total mass of various components involved in a unit process remains constant. Thus, for
any unit process,
3.2
Classification of Material Balance without
Chemical Reaction
The material balance problems without chemical reaction can be classified as follows:
1. Material balance at steady state operation.
2. Material balance at unsteady state operation.
3.4
Various Important Operations Carried Out in
Industry
The various important operations carried out in industry are as follows:
1. Distillation
2. Absorption
3. Extraction
4. Crystallization
5. Drying
6. Mixing
7. Evaporation.
3.4.1 Distillation
It is a method of separation of mixture based on differences in volatilities of components in a
boiling liquid mixture. It is a unit operation or physical separation process. Fractional
distillation can give almost pure product. The product obtained from the top is called
distillate or overhead product. The product removed from the bottom is called residue or
bottom product.
3.4.2 Absorption
It is a method of separation of solute gas component from its mixture using another
component gas with the help of suitable liquid solvent in which solute gas is absorbed. The
component gases help to remove solute gases is termed an inert gas with respect to
absorption. Packed column is commonly used for absorption.
3.4.3 Extraction
It is a method of separation of solute constituent present in solid or liquid by using a solvent.
It is used in industry for separation of components of liquid mixture with the help of suitable
liquid solvent.
3.4.4 Crystallization
It is a process for the formation of solid crystals from a homogeneous solution. In solids,
particles are present randomly due to thermal agitation. In liquids it is moderate and in gases
the disorderlines is highest. The liquids can transform into crystalline form whenever
attraction forces between particles are strong enough to overcome the disorderlines. Crystals
are commonly obtained from liquid state.
In the absence of seed crystals, supersaturation is necessary to initiate the crystallization
through the
formation of nuclei. The rate of formation of crystals, particle size, its uniformity and
distribution
depends on the following two largely independent processes:
1. Nucleation
2. Growth of nuclei.
There are different types of crystallizers in commerical practice:
1. Agitated batch crystallizer
2. Swenson walker crystallizer
3. Krystal crystallizer
4. Vacuum crystallizer.
3.4.5 Drying
Drying is the process of removal of small amount of moisture or other liquid from a solid
substance by the application of heat. The water or other liquid may be removed from the solid
substances either mechanically by filtration or by thermal vaporization. The process of
removal of water from the solid surface is cheaper by mechanical process rather than thermal
process. Therefore, it is advisable to reduce the water present in the solid as much as it is
possible before subjecting to the drying process.
The various drying equipments industrially used are:
1. Tray dryer
2. Drum dryer
3. Spray dryer
4. Fluidised bed dryer
5. Vacuum dryer
6. Freeze dryer.
3.4.6 Mixing
It is a process of putting together of two or more dissimilar particles within a system. Mixing
may be of the following different types:
1. Solid-solid
2. Liquid-liquid
3. Gas-gas
4. Solid-liquid.
Liquid-liquid mixing is a simple operation. It involves the formation of homogeneous system.
Gas-gas mixing is seldom difficult, whereas solid-solid and solid-liquid mixing is quite
difficult, because it involves the application of shear force.
3.4.7 Evaporation
It is the process of removal of relatively large amounts of water from solution under boiling
condition. The process may be of single effect or multiple effect. It is the unit operation used
in process industry for concentrating weak liquor to produce thick liquor by evaporating a
portion of the solvent. Some industrially used evaporators are:
1. Vertical tube evaporator
2. Horizontal tube evaporator
3. Steam jacketted kettle.
3.5
Bypass Operation
The operation in which the fraction of the feed stream is diverted without chemical reaction
to combined with output stream is called bypass. It is practiced in chemical industry to
maintain the composition and properties of the products. For example, consider the process of
concentrating the fruit juice. In this process, if the concentration of the product is higher, then
the feed stream is bypassed to combine with product stream to get the desired concentration.
3.6
Recycle Operation
We feed reactants into the reactor. But all reactants do not take part in the reaction. Some of
them remains unreacted in the reactor. We take out the products and adopt a suitable method
to separate the unreacted reactant from it. The unit operation in which the unreacted reactant
sent back to combined with fresh feed is called Recycle Operation. The recycling is a
common practice in chemical industry. This method is adopted in unit operation to maximize
the utilization of raw material and to reduce the wastage.
3.7
Purging Operation
Consider, two or more reactants are continuously fed into a reactor to produce the products.
Also, consider one of the reactants is impure. It contains some unwanted material. At the
completion of the reaction, this unwanted material remains in a recycle stream rather than
being carried out as a products. This unwanted material goes on increasing, as the substance
would continuously enter the process along with fresh feed.
In this situation, if nothing were done about the unwanted material, then the attainment of
steady state condition for the process is highly impossible. At this stage, a portion of the
recycle stream is withdrawn and steady state condition is maintained. The withdrawal of
recycle stream under this situation is called purging operation.
Combustion of Fuels
Therefore, fuels release heat energy during the combustion process. Fuels are generally used
for heating and producing energy. Fuels can be classified as:
1. Solid fuels
2. Liquid fuels and
3. Gaseous fuels.
5.2
Calorific Value of Fuels
The net calorific value (NCV) is also known as low heating value (LHV). It is the calorific
value of the fuel which is determined in the presence of water. It is expressed in kJ/kg.
The gross calorific value (GCV) is also known as high heating value (HHV). It is the calorific
value of the fuel which is determined in the absence of water vapour. It is expressed in unit of
kJ/kg. The relation between HHV and LHV may be expressed as:
Where,
HHV = High heating value (kJ/kg)
LHV = Low heating value (kJ/kg)
n = Number of moles of water vapour
HV = Heat of vaporisation of water (kJ/mol)
But, we know that
Where,
m = Mass of water (kg)
l = Latent heat of water vapour (kJ/kg)
5.3
Analysis of Fuel
The analysis of fuel can be made by the following method:
1. Ultimate analysis
2. Proximate analysis.
5.3.1 Ultimate Analysis
When analysis of fuel involves the determination of carbon, nitrogen, hydrogen, sulphur and
oxygen, it is called ultimate analysis.
5.3.2 Proximate Analysis
When analysis of fuel involves the determination of ash, moisture, volatile matter and fixed
carbon, it is called proximate analysis.
Energy Balances
The important forms of energy are:
1. Internal energy
2. Kinetic energy
3. Potential energy.
6.1.1 Internal Energy
Energy possessed by the system by virtue of translation and rotation of molecules is called
Internal energy. It is denoted by the symbol U. Its unit is kJ/kg.
6.1.2 Kinetic Energy
Energy possessed by the system by virtue of its motion is called kinetic energy. It is denoted
by the symbol Ek. Its unit is kJ/kg.
6.1.3 Potential Energy
Energy possessed by a system by virtue of its position is called potential energy. It is denoted
by the symbol Ep. Its unit is kJ/kg. The heat and work are the forms of energy. These are
evident only as energy in transition.
6.2
General Steady State Energy Balance Equation
A system in which mass as well as energy transfer may take place is called an open system. A
system in which no mass transfer but energy transfer may take place is called a closed
system. The energy balance equation for closed system is given by,
6.4
Thermochemistry
It is the branch of science which deals with energy changes involved in chemical reactions.
Almost all chemical reactions are accompanied by change in energy. This change in energy
of chemical reactions is in the form of absorption or evolution of heat. According to
thermochemistry, chemical reactions may be classified into two categories; Endothermic
and Exothermic chemical reactions.
A chemical reaction that proceeds with the absorption of heat is called an
endothermic chemical
reaction. For example, consider the photosynthesis reaction.
In this chemical reaction, 15 MJ of energy is absorbed from the sunlight to produce 1 kgmol
of glucose. Hence, it is an endothermic chemical reaction.
A chemical reaction that proceeds with the evolution of heat is called an exothermic chemical
reaction. For example, consider the chemical reaction,
In this chemical reaction, 411 kJ of energy is produced during the formation of 2 kgmol of
NaCl. Hence, it is an exothermic reaction.
The majority of chemical reactions proceed at constant pressure, hence the work performed
by chemical reaction is PV. Therefore, the heat exchanged during the course of reaction is
equal to the change in enthalpy. The heat exchanged for chemical reactions proceed at
constant volume is equal to the change in internal energy. The enthalpy and internal energy
are related through the equation,
H=U +(PV ) (6.11)
Where,
H = change in enthalpy (J/kg)
U = Change in internal energy (J/kg)
(PV ) = Change in work performed (J/kg)
Since (PV ) is very small as compared to H and U . Hence, it may be neglected. In this case,
Eq.(6.11) may be written as,
H=U (6.12)
In the case of gaseous reaction, (PV ) may be important due to the number of moles of gas
changes as a result of reaction. Then, from the ideal gas equation, we have,
PV =n (RT ) (6.13)
n=moles of product −moles of reactant
H=U + n(RT ) (6.14)
6.5
Heat Capacity
Heat capacity is defined as the amount of heat required to raise the temperature of one
kilogram of substance of the system by one degree centigrade. Its unit is kJ/kg°C. Heat
capacity is of two types:
1. Heat capacity (or specific heat) at constant pressure
2. Heat capacity (or specific heat) at constant volume.
6.5.1 Heat Capacity at Constant Pressure
From the first law of thermodynamics, we know that,
Substituting Eq. (6.16) in Eq. (6.15), we get,
Heat capacity of gases at constant pressure
The heat capacity of gases at constant pressure is given by,
Integrating Eq. (6.20) between the temperature limits T1 and T2, we get,
Heat capacity of gaseous mixture
The calculation of heat capacity of gaseous mixture of known composition in the case of
heating or cooling is very much essential in unit operation. This calculation may be
performed in a simplified way by the equation,
6.5.2 Heat Capacity at Constant Volume
6.6
Enthalpy
The total heat content of a substance is called enthalpy. Mathematically, it may be expressed
by the equation as,
During the chemical reaction, heat may be absorbed or evolved. The amount of heat absorbed
or evolved during a chemical reaction plays a major role in economics of the process. The
enthalpy change of a chemical process may be positive or negative. When the enthalpy
change associated with a chemical reaction is positive, then heat must be added to the process
to keep the reaction temperature from dropping. When the enthalpy change associated with a
chemical reaction is negative, then heat must be removed from the process to keep the
reaction temperature from shooting up.
6.6.1 Heat of Formation