CHEMICAL ENGINEERING PROCESS

ANALYSIS

CATUC BAMENDA
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INTRODUCTION
Chemical engineering involves the production and manufacturing of products through chemical processes.
This includes designing equipment, systems, and processes for refining raw materials and for mixing,
compounding, and processing chemicals.
The main role of chemical engineers is to design and troubleshoot processes for the production of chemicals,
fuels, foods, pharmaceuticals, and biologicals, to name just a few.
Chemical Engineering Analysis demonstrates the use of mass and energy balances for the analysis of
chemical processes and products

Course Goals and Overview:

Material and Energy Balances form the foundation for nearly all future chemical engineering courses and
analysis. The process of account for mass and energy is akin to “chemical accounting” and in this course we
will learn how to formulate the balances that govern systems in which mass and energy are exchanged. Included
in this analysis are both reactive and nonreactive systems. An overview of physical behaviour will be included
to provide an introduction to energy balances. Overall, this course will provide an introduction to the principles
and calculation techniques used in the field of Chemical Engineering as well as provide an exposure of the
various areas and facets of current Chemical Engineering research. This course is designed to:
 Provide you with the fundamentals of material and energy balances as applied to chemical
engineering to enable the analysis of a chemical process
 Develop efficient methods of and life-long skills for problem solving through exercise problems
and thought experiments
 Offer practice in defining problems, collecting data, analyzing data
 Help you decide if you have chosen the right field

FUNDAMENTAL PROCESS VARIABLES

What is a process? A process is a series of operations involving the physical, chemical, or biological
transformation of an input material for the purpose of achieving a desired product material.”
Types of Chemical Processes
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input (but energy may be input or withdrawn), while the process runs.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.
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Continuous Process: In this type of process, raw materials continuously enter and product continuously
leaves the process.

Semi continuous (Semi batch) Process: A semibatch process does not fall fully under either “batch” or
“continuous” classification.

What is a (chemical) process variable? Any measurement used to characterize or describe a chemical process.
The fundamental process variables include:
1. Measurements to quantify a material or specify a chemical composition. E.g. Mass, Volume, and Mole
2. Measurements used to specify process conditions. E.g Pressure and Temperature
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Mass and Volume: Conservation Principles

Conservation Law for Mass: “Matter is neither created nor destroyed”

For volume, there is no generalized conservation law.

Mass and Volume: Density and Specific Gravity

Density (ρ) Ratio of mass per unit volume. Used as a factor for interconversion of mass and volume.

1. Densities of gases depend on pressure and temperature.

2. Densities of solids and liquids do not change significantly with pressure at ordinary conditions with pressure
but change with temperature.
Mass and Volume: Density and Specific Gravity
Specific Gravity (sp gr) Ratio of two densities – that of the substance of interest to that of a reference substance.

The Mole
 Refers to a certain number of molecules, atoms, or subatomic particles.
 “The amount of substance that contains as many elementary entities as there are atoms in 0.012 kg of
carbon 12” – 1969 International Committee on Weights and Measures Contains Avogadro’s number of
entities (molecule, atom, or any particles) – 6.02 x 1023
 Amount of a chemical species whose mass is equal to its molecular weight.
The Mole Unit
A gmol is the standard unit for mole and contains 6.02 x 1023 molecules or atoms. But the following units can
also be used for mole: 1 kmol = 1000 gmol or 1lbmol = 454.54 gmol
To convert the number of moles to mass, we make use of the molecular weight (MW):

If the molecular weight of H2O is 18, then:

1 gmol contains 18 g of H2O (MW = 18 g/gmol)
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1 kmol contains 18 kg of H2O (MW = 18 kg/kmol)

1 lbmol contains 18 lbm of H2O (MW = 18 lbm/lbmol)

Quantifying Materials in a Continuous Chemical Process

For continuous process, it is best to use flow rates to measure the amount of materials flowing through the
process:

Chemical Composition
In a mixture of two or more components, the composition may be expressed as:

For liquids and solids, it will always be assumed that the composition is on a weight basis unless otherwise
stated. For gases, it will be assumed to be in molar basis. Other methods of expressing concentration include:
1. Molarity (mol/L) and normality (equivalents/L).
2. Parts per million (ppm) and parts per billion (ppb)
– normally used for expressing concentration of extremely dilute solutions.
3. Partial pressure – a method to express the concentration of a gas mixture.
Example – Mass and Volume Calculations
The specific gravity of gasoline is approximately 0.70.
a. Determine the mass (kg) of 50.0 litres of gasoline.

Relative and Absolute Temperature Scales

 Temperature: The average kinetic energy possessed by the substance.
 Relative Temperature Scale – Celsius and Fahrenheit The zero value is preset at some arbitrarily defined
level.

 Absolute Temperature Scale – Kelvin and Rankine

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A temperature scale on which a reading of zero coincides with the theoretical absolute zero (zero entropy
configuration).

 Unit Temperature Difference

When temperature is used as a unit difference, then the following relationship is used:

Whether temperature is used as a unit temperature difference must be interpreted from the context of the
equation or sentence being examined.

CHEMICAL EQUATION AND STOICHIOMETRY

What can we learn from a chemical equation?

1. What information can we get from this equation?

A chemical equation provides both qualitative and quantitative information
2. What is the first thing we need to check when using a chemical equation?
Before using a chemical equation, make sure that it is balanced.
3. What do you call the number that precedes each chemical formula?
The number that precedes a compound is known as the stoichiometric coefficient.
4. How do we interpret those numbers?
The stoichiometric coefficient may be interpreted as number of moles or molecules.
The Stoichiometric Coefficient
The stoichiometric coefficients tell us the mole (not mass) relationships (stoichiometric ratios) of the compounds
participating in the reaction. For the chemical equation shown previously,

1 gmol of C7H16 reacts with 11 gmol of O2 to yield 7 gmol of CO2 and 8 gmol of H2O

Is it possible to establish the mass relationships from the stoichiometric coefficients? Consider: If 10 kg of C7H6
react completely with the stoichiometric quantity, how many kg of CO2 will be produced?

Limiting and Excess Reactants

Limiting Reactant
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The reactant that is present in the smallest stoichiometric amount. It is the compound that will be consumed first
if the reaction proceeds to completion.
Excess Reactant
The chemical species whose amount supplied is higher than the stoichiometric requirement. The percentage
excess is then computed as:

Limiting and Excess Reactants

Consider a balanced chemical reaction:

Suppose x moles of A and y moles of B are present and they react according to the above reaction,

Conversion and Degree of Completion

Conversion
The fraction (or percentage) of the reactants that actually reacted during the reaction.

Degree of Completion
The fraction (or percentage) of the limiting reactant converted
into products.

Yield and Selectivity

Yield
The actual amount of products formed relative to what is actually expected from the reaction.

Selectivity
The ratio of the moles of the desired product produced to the moles of undesired product (by-product).

For example, methanol (CH3OH) can be converted into ethylene (C2H4) and propylene (C3H6) by the reaction:
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If the desired product is ethylene, then the selectivity is computed as:

Extent of Reaction (ε)

The extent of the reaction (ε) is an extensive quantity describing the progress of a chemical reaction. Depends
on the degree of completion of the reaction.

MATERIAL BALANCE CONCEPT

Material balance analysis

 Material balances are nothing more than the application of the law of conservation of mass
 Material balance calculations are almost invariably a prerequisite to all other calculations in the
solution of both simple and complex chemical engineering problems
 Material balance analysis is simply an account of all materials flowing, generated, or consumed in a
chemical process
System and control volume
A system is any arbitrary portion of a process set out specifically for analysis.
A control volume is any imaginary or tangible boundary which encloses the system.
Types of systems
Closed system: a system is closed if there is no mass passing through the volume during the period of
analysis.
Open system: a system is open if mass can passs through the control volume during the period of analysis.
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The steady state process

In a steady-state process, the values of all variables in the process (such as chemical composition,
temperature, pressure etc.) do not change with time. Otherwise, it’s an unsteady- state process.
For a steady state process

The mass balance equation

Consider the control volume

Possible scenarios for B

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The general mass balance equation can be written as

For a steady state process, there is no accumulation or depletion of materials.

If there is no chemical reaction, there is no means for a material to be generated or consumed.

If there is no chemical reaction and steady state conditions exist, then

Degree Of Freedom(DF) Analysis

The procedure of determining whether enough information is given to solve the problem is th degree of
freedom analysis. To determine DF
DF= U-V
Where U= number of unknown variables to be solved
V= number of independent equations relating the unknown variables
Possible cases depending on the value of DF
DF= 0 there are equal number of unknowns and independent equations and the problem in principle can be
solved.
DF> 0 there are more unknowns than independent equations and the problem is underspecified and has
infinitely many solutions.
DF<0 there are more independent equations than unknowns and the problem is over specified and has no
exact solutions.
Possible sources of equations in material balance analysis
1. Material balance equations
2. Stoichiometric relationships based on chemical reactions (particularly useful when solving reactive
processes)
3. Energy balance equations
4. Physical constraints on some variables
5. Process specifications
6. Physical properties and laws
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Solving Material Balances Problems Involving Non-Reactive Processes

Component and Overall Material Balances
Consider a steady-state distillation process,

Since the process is at steady-state condition and no chemical reaction is involved, the material balance
equation becomes
Input = Output
This balance equation can be applied to:
1. The total mass entering and leaving the process
2. Mass of individual component entering and leaving the process.

Total Mass (Overall Material Balance)

m1 = m2 + m3
Component A Balance
mA1 = mA2 + mA3
m1xA1 = m2xA2 + m3xA3
Component B Balance
mB1 = mB2 + mB3
m1xB1 = m2xB2 + m3xB3
For the given process, 3 material balance equations can be written:
Total Balance: m1 = m2 + m3 ……………………. (1)
A-Balance: mA1 = mA2 + mA3……………….…….. (2)
B-Balance: mB1 = mB2 + mB3……………….…….. (3)
Are these material balances independent equations? If (E1) and (E2) are added, what does the resulting
equation represents?
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Consider the unsteady-state extraction process:

Extraction is a physical process in which a component of a mixture is extracted using an immiscible solvent.
Writing the material balance equations:

The total balance can also be obtained by adding the last 3 equations and is no longer independent.
Number of Independent Material Balance Equations in Process without Chemical Reaction
For processes with no chemical reaction,
Nm = Ni
where Nm = number of independent material balance equations.
Ni = total number of chemical species (or components) involved in the process.
Method for Preparing Process Flow Chart
The identification and drawing up a unit operation/process is prerequisite for energy and material balance. The
procedure for drawing up the process flow diagrams is explained below.
Flow charts are schematic representation of the production process, involving various input resources,
conversion steps and output and recycle streams. The process flow may be constructed stepwise i.e. by
identifying the inputs / output / wastes at each stage of the process, as shown in the Figure
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Inputs of the process could include raw materials, water, steam, energy (electricity, etc);
Process Steps should be sequentially drawn from raw material to finished product. Intermediates and any
other byproduct should also be represented. The operating process parameters such as temperature, pressure,
% concentration, etc. should be represented.
The flow rate of various streams should also be represented in appropriate units like m3/h or kg/h. In case of
batch process the total cycle time should be included.
Wastes / by products could include solids, water, chemicals, energy etc. For each process steps (unit
operation) as well as for an entire plant, energy and mass balance diagram should be drawn.
Output of the process is the final product produced in the plant.

Example. Mixing of Methanol-Water Mixtures

Two methanol-water mixtures are contained in separate tanks. The first mixture contains 40.0 wt% methanol
and thesecond contains 70.0 wt% methanol. If 200 kg of the first mixture is combined with 150 kg of the second,
what are the mass and composition of the product?
Step 1. Draw a flowchart to visually organize the data.

Step 2. Determine the degrees of freedom (DF)

Number of unknowns (U): 3 unknowns (m3, xM3, xW3) Number of independent equations (V):
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Step 3. Write down the equations

Material Balances (Steady-State, Non-Reactive Process):

(choose only 2 equations since one of them is no longer independent)

Physical Constraint (applied to mixture 3):
xM3 + xW3 = 1.00
Step 4. Solve the unknowns (m3, xM3, xW3)
Always start with the equation with the least number of unknowns if possible and minimize solving equations
simultaneously.

4. MATERIAL BALANCES ON MULTIPLE UNIT PROCESSES

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Consider the following process

The entire process can be analysed as 1 unit.

or portions of the entire process is analyzed

5. MATERIAL BALANCES ON REACTIVE PROCESSES

Material balances on processes involving chemical reactions may be solved by applying:
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1. Molecular Species Balance – a material balance equation is applied to each chemical compound appearing in
the process.
2. Atomic Species Balance – the balance is applied to each element appearing in the process.
3. Extent of Reaction – expressions for each reactive species is written involving the extent of reaction.
Molecular and Elemental Balances
For steady-state reactive processes,

The generation and consumption terms in the molecular balance equation is usually obtained from chemical
stoichiometry.
But for an atomic balance, for all cases
Input = Output
Example Dehydrogenation of Ethane
Consider the dehydrogenation of ethane in a steady-state continuous reactor,

Multiple Reactions, Yield and Selectivity

In a chemical process, our objective is to produce a certain product (desired product), but there may be several
unwanted reactions which will produce undesirable by products. Therefore, we must maximize the production
of a desired product in the process. Two quantities, yield and selectivity, are used for this purpose and they are
defined as follows,
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Consider the following pair of reactions.

A  2B (desired) A  C (undesired)
100 moles of A are fed to a batch reactor and the final product contains 10 mol of A, 160 mol of B and 10 mol of C.
Calculate (1) percentage yield of B, (2) the selectivity of B relative to C.

Extent of Reactions
When we have multiple reactions, the remaining amount or flow rate will be given by
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Example: for the question above calculate the extent of the reaction

Atomic and Molecular Balances

In a chemical process, molecules are either generated (produced) or consumed. Therefore, one should take
into account the amounts (moles) generated, consumed, fed and remaining in molecular balances.
Example In a steady state process, 100 moles ethane (C2H6) react to produce ethylene (C2H4) and hydrogen
(H2) according to C2H6C2H4 + H2.. Product gas shows 40 moles of hydrogen remaining. Perform molecular
balances for all species.

Solution:

Then, the molecular balance of H2 is as follows,

input + generated (produced) = output + consumed (reacted) input = 0.0

output = 40
consumed = 0

0 + generated (produced) = 40+ 0  H2 (generated) = 40 moles.

Molecular balance of C2H6 is as follows,

input + generated (produced) = output + consumed (reacted) input = 100

generated = 0 output = q1

100 + 0 = q1 + consumed  C2H6 (consumed) = 100-q1

H2 (generated) = 40 moles=C2H6 (consumed) = 100-q1  q1 = 60 moles Molecular balance

of C2H4 is as follows,

input + generated (produced) = output + consumed (reacted) input = 0

output = q2 consumed = 0
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0 + generated = q2 + 0  C2H4 (generated) = q2

C2H4 (generated) = q2 = H2 (generated) = 40 moles  q2 = 40 moles

EXAMPLE: For the same problem as above, do atomic balances?

Solution

Atomic carbon balance: 1002 = q12 + q22 Atomic hydrogen balance

1006 = 402 + q16 + q24

Solving these two atomic balance equations, you will get the same answer as above.

Recycle, Bypass, & Purge Calculations

A multistage system refers to a system consisting of multiple components, stations or stages required to finish
the final product or service. Multistage systems are very common in practice and include a variety of modern
manufacturing and service systems. Almost all modern manufacturing processes (e.g., assembly, machining,
semiconductor fabrication, pharmaceutical manufacturing) fit this category;
Overall and Single Pass Conversion

Find the overall and single pass conversion of A ?

Recycle Stream
Recycle stream is a term denoting a process stream that returns material from downstream of a process unit
back to the process unit.
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Bypass Stream
Bypass stream is a stream that skips one or more stages of the process and goes directly to another
downstream stage.

Purge Stream
Purge stream is a stream bled off to remove an accumulation of inerts or unwanted material that might
otherwise build up in the recycle stream.

Example.
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1. Distillation of Benzene and Toluene

A distillation column separates 10,000 kg/hr of a mixture containing equal mass of benzene and toluene. The
product D recovered from the condenser at the top of the column contains 95% benzene, and the bottom W
from the column contains 96% toluene. The vapor V entering the condenser from the top of the column is
8000 kg/hr. A portion of the product from the condenser is returned to the column as reflux R, and the rest is
withdrawn as the final product D. Assume that V, R, and D are identical in composition since V is condensed
completely. Find the ratio of the amount refluxed R to the product withdrawn D.
2. Dehydrogenation of Propane

Propane is dehydrogenated to from propylene in a catalytic reactor

C3H8  C3H6  H2

The process is to be designed for a 95% overall conversion of propane. The reaction products are separated into two
streams: the first, which contains H2, C3H6, and 0.555% of the propane that leaves the reactor, is taken off as product;
the second stream, which contains the balance of the unreacted propane and 5% of the propylene in the product
stream, is recycled to the reactor. Calculate the composition of the product, the ratio (moles recycled)/(moles
fresh feed), and the single-pass conversion.

6. ENERGY BALANCES
Energy takes many forms, such as heat, kinetic energy, chemical energy, potential energy but because of
interconversions it is not always easy to isolate separate constituents of energy balances. However, under
some circumstances certain aspects predominate. In many heat balances in which other forms of energy are
insignificant; in some chemical situations mechanical energy is insignificant and in some mechanical energy
situations, as in the flow of fluids in pipes, the frictional losses appear as heat but the details of the heating
need not be considered. We are seldom concerned with internal energies.
Therefore practical applications of energy balances tend to focus on particular dominant aspects and so a heat
balance, for example, can be a useful description of important cost and quality aspects of process situation.
When unfamiliar with the relative magnitudes of the various forms of energy entering into a particular
processing situation, it is wise to put them all down. Then after some preliminary calculations, the important
ones emerge and other minor ones can be lumped together or even ignored without introducing substantial
errors. With experience, the obviously minor ones can perhaps be left out completely though this always
raises the possibility of error.
Energy balances can be calculated on the basis of external energy used per kilogram of product, or raw
material processed, or on dry solids or some key component. The energy consumed in food production
includes direct energy which is fuel and electricity used on the farm, and in transport and in factories, and in
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storage, selling, etc.; and indirect energy which is used to actually build the machines, to make the packaging,
to produce the electricity and the oil and so on. Food itself is a major energy source, and energy balances can
be determined for animal or human feeding; food energy input can be balanced against outputs in heat and
mechanical energy and chemical synthesis.
In the SI system there is only one energy unit, the joule. However, kilocalories are still used by some
nutritionists and British thermal units (Btu) in some heat-balance work.
The two applications used in this chapter are heat balances, which are the basis for heat transfer, and the
energy balances used in analysing fluid flow.
Heat Balances
The most common important energy form is heat energy and the conservation of this can be illustrated by
considering operations such as heating and drying. In these, enthalpy (total heat) is conserved and as with the
mass balances so enthalpy balances can be written round the various items of equipment. or process stages, or
round the whole plant, and it is assumed that no appreciable heat is converted to other forms of energy such as
work.
Enthalpy (H) is always referred to some reference level or datum, so that the quantities are relative to this
datum. Working out energy balances is then just a matter of considering the various quantities of materials
involved, their specific heats, and their changes in temperature or state (as quite frequently latent heats arising
from phase changes are encountered). Figure 4.3 illustrates the heat balance.

Heat is absorbed or evolved by some reactions in processing but usually the quantities are small when
compared with the other forms of energy entering into food processing such as sensible heat and latent heat.
Latent heat is the heat required to change, at constant temperature, the physical state of materials from solid to
liquid, liquid to gas, or solid to gas. Sensible heat is that heat which when added or subtracted from materials
changes their temperature and thus can be sensed. The units of specific heat are J/kg K and sensible heat
change is calculated by multiplying the mass by the specific heat by the change in temperature, (m x c x ΔT).
The units of latent heat are J/kg and total latent heat change is calculated by multiplying the mass of the
material, which changes its phase by the latent heat. Having determined those factors that are significant in the
overall energy balance, the simplified heat balance can then be used with confidence in industrial energy
studies. Such calculations can be quite simple and straightforward but they give a quantitative feeling for the
situation and can be of great use in design of equipment and process.
Example:Dryer heat balance
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A textile dryer is found to consume 4 m3/hr of natural gas with a calorific value of 800 kJ/mole. If the
throughput of the dryer is 60 kg of wet cloth per hour, drying it from 55% moisture to 10% moisture, estimate
the overall thermal efficiency of the dryer taking into account the latent heat of evaporation only.
60 kg of wet cloth contains
60 x 0.55 kg water = 33 kg moisture
and 60 x (1-0.55) = 27 kg bone dry cloth.
As the final product contains 10% moisture, the moisture in the product is 27/9 = 3 kg
And so Moisture removed / hr = 33 - 3 = 30 kg/hr
Latent heat of evaporation = 2257 kJ/K
Heat necessary to supply = 30 x 2257 = 6.8 x 104 kJ/hr
Assuming the natural gas to be at standard temperature and pressure at which 1 mole occupies 22.4 litres
Rate of flow of natural gas = 4 m3/hr = (4 x 1000)/22.4 = 179 moles/hr
Heat available from combustion = 179 x 800 = 14.3 x 104 kJ/hr
Approximate thermal efficiency of dryer = heat needed / heat used
= 6.8 x 104 / 14.3 x 104 = 48%
Example: Autoclave heat balance in canning
An autoclave contains 1000 cans of pea soup. It is heated to an overall temperature of 100 oC. If the cans are
to be cooled to 40 oC before leaving the autoclave, how much cooling water is required if it enters at 15 oC
and leaves at 35 oC?
The specific heats of the pea soup and the can metal are respectively 4.1 kJ/ kg oC and 0.50 kJ/ kg oC. The
weight of each can is 60g and it contains 0.45 kg of pea soup. Assume that the heat content of the autoclave
walls above 40 oC is 1.6 x 104 kJ and that there is no heat loss through the walls.
Let w = the weight of cooling water required; and the datum temperature be 40oC, the temperature of the cans
leaving the autoclave.
Heat entering
Heat in cans = weight of cans x specific heat x temperature above datum
= 1000 x 0.06 x 0.50 x (100-40) kJ = 1.8 x 103 kJ
Heat in can contents = weight pea soup x specific heat x temperature above datum
= 1000 x 0.45 x 4.1 x (100 - 40) = 1.1 x 105 kJ
Heat in water = weight of water x specific heat x temperature above datum
= w x 4.186 x (15-40)
= -104.6 w kJ.
Heat leaving
Heat in cans = 1000 x 0.06 x 0.50 x (40-40) (cans leave at datum temperature) = 0
Heat in can contents = 1000 x 0.45 x 4.1 x (40-40) = 0
Heat in water = w x 4.186 x (35-40) = -20.9 w
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Other Forms of Energy

Motor power is usually derived, in factories, from electrical energy but it can be produced from steam engines
or waterpower. The electrical energy input can be measured by a suitable wattmeter, and the power used in the
drive estimated. There are always losses from the motors due to heating, friction and windage; the motor
efficiency, which can normally be obtained from the motor manufacturer, expresses the proportion (usually as
a percentage) of the electrical input energy, which emerges usefully at the motor shaft and so is available.
When considering movement, whether of fluids in pumping, of solids in solids handling, or of foodstuffs in
mixers. the energy input is largely mechanical. The flow situations can be analysed by recognising the
conservation of total energy whether as energy of motion, or potential energy such as pressure energy, or
energy lost in friction. Similarly, chemical energy released in combustion can be calculated from the heats of
combustion of the fuels and their rates of consumption. Eventually energy emerges in the form of heat and its
quantity can be estimated by summing the various sources.
EXAMPLE Refrigeration load
It is desired to freeze 10,000 loaves of bread each weighing 0.75 kg from an initial room temperature of 18oC
to a final temperature of –18oC. The bread-freezing operation is to be carried out in an air-blast freezing
tunnel. It is found that the fan motors are rated at a total of 80 horsepower and measurements suggest that they
are operating at around 90% of their rating, under which conditions their manufacturer's data claims a motor
efficiency of 86%. If 1 ton of refrigeration is 3.52 kW, estimate the maximum refrigeration load imposed by
this freezing installation assuming (a) that fans and motors are all within the freezing tunnel insulation and (b)
the fans but not their motors are in the tunnel. The heat-loss rate from the tunnel to the ambient air has been
found to be 6.3 kW.
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HEATS OF SOLUTION AND MIXING

Heats of Solution, Dissolution, and Mixing
Up to this chapter we have assumed that when a stream consists of several components, the total properties
of the stream are the appropriately weighted sum of the properties of the individual components. For such
ideal solutions, we could write down for the heat capacity of an ideal mixture, for example

In particular, mixtures of gases have been treated as ideal solutions. However, you must take into
consideration other types of mixtures. You can prepare various kinds of binary solutions or mixtures:

a. gas-gas

b. gas - liquid

c. gas - solid

d. liquid - liquid

e. liquid - solid

f. solid - solid

You can ignore the energy changes that occur on mixing for cases a, c, and f. They are negligible. The
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other mixtures comprise real solutions. When a gaseous or solid solute (the compound to be dissolved) is
mixed with a liquid solvent (the compound in which the solute is dissolved), the energy effect that occurs
is referred to as the heat (really enthalpy) of solution. When a liquid is mixed with a liquid, the energy effect
is called the heat (enthalpy) of mixing. The negative of the heat of solution or mixing is the heat (enthalpy)
of dissolution. The heat of solution can be positive (endothermic) or negative (exothermic).

You can treat heats of solution/mixing in the same way you treat chemical reactions. In the
energy balance, you can (a) merge the heats of solution/mixing of the

compounds in the system with the heats of formation, or (b) consolidate the effects of the heats
of solution/mixing in one lumped term analogous to a heat of reaction term. For example, let
us represent the solution of 1 g mol HCI(g) into 5 g mol of H2O (l) by the following chemical
equation:

HCl(g) + 5H2O(1) = HC1[5H2O]

If you carry out experiments to measure the heat transfer from an apparatus at a constant 25°C and 1 atm
by successively adding water to HCl, and arrange the experiments so that the energy balance reduces to Q
= ΔH, then the values of ΔH would be the tabulation in the third column of Table 28.1 below. (The values
incorporate a slight adjustment in the measured values of Q at the vapor pressure of the solution to adjust
them to 1 atm, the standard state.) If you cumulate each incremental change in ΔH, you would obtain the
fourth column in Table 28.1.
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HUMIDITY

The air surrounding us is a mixture of dry air and moisture and it contains a certain amount of heat. We are
used to hearing about air temperature, relative humidity, and the dewpoint in discussions of weather
conditions. All these properties and more are contained in a psychrometric chart. Chart shape and complexity
take some getting used to. Refer to Figures 1 and 2. You will find that the upper curved boundary of the chart
has one temperature scale, yet can represent three types of temperature: wet-bulb, dry-bulb, and dewpoint.
This upper curved boundary also represents 100 percent relative humidity or saturated air.
Dry-bulb temperature
is the commonly measured temperature from a thermometer. It is called "dry-bulb" since the sensing tip of the
thermometer is dry (see "wet bulb temperature" for comparison). Dry-bulb temperature is located on the
horizontal, or x-axis, of the psychrometric chart and lines of constant temperature are represented by vertical
chart lines. Since this temperature is so commonly used, assume that temperatures are dry-bulb temperatures
unless otherwise designated.
Relative humidity
is a measure of the amount of water that air can hold at a certain temperature. It is "relative" to the amount of
water that air, at that same temperature, can hold at 100 percent humidity, or saturation. Air temperature (dry-
bulb) is important because warmer air can hold more moisture than cold air. Air at 60 percent relative
humidity contains 60 percent of the water it could possibly hold (at that temperature). It could pick up 40
percent more water to reach saturation. Lines of constant relative humidity are represented by the curved lines
running from the bottom left and sweeping up through to the top right of the chart. The line for 100 percent
relative humidity, or saturation, is the upper, left boundary of the chart.
Humidity ratio
of moist air is the weight of the water contained in the air per unit of dry air. This is often expressed as pounds
of moisture per pound of dry air. Since the humidity ratio of moist air is not dependent on temperature, as is
relative humidity, it is easier to use in calculations. Humidity ratio is found on the vertical, y-axis with lines of
constant humidity ratio running horizontally across the chart.
Dewpoint temperature
It indicates the temperature at which water will begin to condense out of moist air. Given air at a certain dry-
bulb temperature and relative humidity, if the temperature is allowed to decrease, the air can no longer hold as
much moisture. When air is cooled, the relative humidity increases until saturation is reached and
condensation occurs. Condensation occurs on surfaces which are at or below the dewpoint temperature.
Dewpoint temperature is determined by moving from a state point horizontally to the left along lines of
constant humidity ratio until the upper, curved, saturation temperature boundary is reached.
Enthalpy
It is the heat energy content of moist air. It is expressed in Btu per pound of dry air and represents the heat
energy due to temperature and moisture in the air. Enthalpy is useful in air heating and cooling applications.
The enthalpy scale is located above the saturation, upper boundary of the chart. Lines of constant enthalpy run
diagonally downward from left to right across the chart. Lines of constant enthalpy and constant wet-bulb are
the same on this chart, but values are read from separate scales. More accurate psychrometric charts use
slightly different lines for wet-bulb temperature and enthalpy.
Wet-bulb temperature
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It is determined when air is circulated past a wetted sensor tip. It represents the temperature at which water
evaporates and brings the air to saturation. Inherent in this definition is an assumption that no heat is lost or
gained by the air. This is different from dewpoint temperature, where a decrease in temperature, or heat loss,
decreases the moisture holding capacity of the air, causing water to condense. Determination of wet-bulb
temperature on this psychrometric chart follows lines of constant enthalpy, but values are read off the upper,
curved, saturation temperature boundary.
Specific volume
indicates the space occupied by air. It is the inverse of density and is expressed as a volume per unit weight
(density is weight per unit volume). Warm air is less dense than cool air, which causes warmed air to rise.
This phenomena is known as thermal buoyancy. By similar reasoning, warmer air has greater specific volume
and is hence lighter than cool air. On the psychrometric chart, lines of constant specific volume are almost
vertical lines with scale values written below the dry-bulb temperature scale and above the upper boundary's
saturation temperature scale. On this chart, values range from 12.5 to 15.0 cubic feet/ pound of dry air. Greater
specific volume is associated with warmer temperatures (dry-bulb).

The psychrometric chart

A psychrometric chart packs a lot of information into an odd-shaped graph. If we consider the components piece
by piece, the usefulness of the chart will be clearer. Boundaries of the psychrometric chart are a dry-bulb
temperature scale on the horizontal axis, a humidity ratio (moisture content) scale on the vertical axis, and an
upper curved boundary which represents saturated air or 100-percent moisture holding capacity. The chart
shows other important moist air properties as diagrammed in Figure : wet-bulb temperature; enthalpy; dewpoint
or saturation temperature; relative humidity; and specific volume. See the Definitions Sidebar for an explanation
of these terms. Moist air can be described by finding the intersection of any two of these properties. This is
called a "state point." From the state point all the other properties can be read. The key is to determine which
interest. Some practice with examples will help. Use Figures 2 and 3 with the psychrometric chart in Figure 1
to verify whether you can find each air property.

An understanding of the shape and use of the psychrometric chart will help you diagnose air temperature and
humidity problems. Note that cooler air (located along the lower, left region of the chart) will not hold as much
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moisture (as seen on the y-axis' humidity ratio) as warm air (located along right side of chart). A rule of thumb
for inside typical greenhouses or animal buildings during winter conditions is that a 10°F rise in air temperature
can decrease relative humidity 20 percent. Use of a psychrometric chart will show that this is roughly true. For
example, to decrease relative humidity in a winter greenhouse during a critical time period, we could heat the
air.
Use of Psychrometric Chart
Example 1 Find air properties
A sling psychrometer* gives a dry-bulb temperature of 78°F and a wet-bulb temperature of 65°F. Determine
other moist air properties from this information. Two useful air properties for environmental analysis in
agricultural buildings would be relative humidity and dewpoint temperature. Relative humidity is an indicator
of how much moisture is in the air compared to desirable moisture conditions, and dewpoint temperature
indicates when condensation problems would occur should the (dry-bulb) temperature drop.

Find the intersection of the two known properties, dry-bulb and wet-bulb temperatures, on the psychrometric
chart, Figure 1. The dry-bulb temperature is located along the bottom horizontal axis. Find the line for 78°F,
which runs vertically through the chart. Wet-bulb temperature is located along diagonal dotted lines leading to
scale readings at the upper, curved boundary marked "saturation temperature." The intersection of the vertical
78°F dry-bulb line and the diagonal 65°F wet-bulb line has now established a state point for the measured air.
Now read relative humidity as 50 percent (curving line running from left to right up through the chart) and
dewpoint temperature as 58°F (follow horizontal line, moving left, toward the curved upper boundary of
saturation temperatures). This example is shown in Figure 3 so you may check your work.
What might we conclude from this information? The relative humidity of 50 percent is acceptable for most
livestock and greenhouse applications. If we allowed the air temperature (dry-bulb) to decrease to 58°F
(dewpoint) or below, the air would be 100 percent saturated with moisture and condensation would occur. The
humidity ratio, as seen on the vertical, y-axis scale, is a reliable indicator of air moisture level since it reflects
the pounds of moisture contained in a pound of dry air and does not fluctuate with dry-bulb temperature readings
as does relative humidity. The humidity ratio for air in this example is about 0.0104 lb moisture/ lb dry air
(move right horizontally from state point to humidity ratio scale).
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Example 2 Winter ventilation

Often air is heated before it is introduced into greenhouse or young-livestock building environments. Consider
an application where outdoor air at 40°F (dry-bulb) temperature and 80 percent relative humidity is heated to
65°F (dry-bulb) before it is distributed throughout the building.

Find the state point for the incoming cool air on the lower left portion of the psychrometric chart (point A in
Figure 4). Note that other properties of the 40°F air include a wet-bulb temperature of 38°F, a dewpoint
temperature of about 34°F and humidity ratio of 0.0042 lb moisture/ lb dry air. Heating air involves an increase
in the dry-bulb temperature with no addition or reduction in the air's water content. The heating process moves
horizontally to the right along a line of constant humidity ratio. See Figure 4 for this heating process between
points A and B. Heating the air to 65°F (dry-bulb) has resulted in decreasing the relative humidity to about 32
percent. The heated air entering the building is dry enough to be useful in absorbing moisture from the plant or
animal environment. (Verify that the heated air at point B continues to have a dewpoint of 34°F and humidity
ratio of 0.0042 lb moisture/ lb dry air.) The heated air, with its lower relative humidity, can be mixed with moist,
warm air already in the building. As fresh air moves through an animal environment, it will pick up additional
moisture and heat before it reaches the ventilation system exhaust. We might measure the exhausted air
conditions at 75°F (drybulb) and 70 percent relative humidity, represented by point C in Figure 4. Note that in
this exhausted air, the humidity ratio has tripled to 0.013 lb moisture/ lb dry air. This means that much more
water is ventilated out of the building in the warm, moist exhaust air than is brought in by the cold, high relative
humidity incoming air. Removing moisture from the plant or animal environment is one of the major functions
of a winter ventilation system.

Figure . Diagram of Example 2. Outdoor air at 40°F, 80 percent relative humidity (point A is heated to 65°F (point B) for
use in ventilation. Exhaust air (point C) at 75°F and 70% relative humidity contains three times the moisture of the fresh
air (point A and B).

Example 3 Evaporative cooling

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Evaporative cooling uses heat contained in the air to evaporate water. Air temperature (dry-bulb) drops while
water content (humidity) rises to the saturation point. Evaporation is often used in hot weather to cool ventilation
air. The process moves upward along the line of constant enthalpy or constant wet-bulb temperature, for
example, from point D to point E in Figure 5. Notice that hot dry air (points D to E with a 24° F temperature
drop) has more capacity for evaporative cooling than hot humid air (points F to G with only a 12° F temperature
decrease).

Figure. Diagram of Example 3. Evaporative cooling process with hot dry air from points D to E and with hot
humid air from points F to G. Notice greater evaporative cooling capacity with dry air.